Bactericide composition and method of controlling plant disease
Abstract
A bactericide composition which, when applied to crop plants infected with plant diseases, is stably and highly effective in controlling pests. The bactericide composition is characterized by containing, as active ingredients, (a) a benzoylpyridine derivative represented by the formula (I): (I) (wherein X is halogeno, nitro, an optionally substituted hydrocarbon group, optionally substituted alkoxy, optionally substituted aryloxy, optionally substituted cycloalkoxy, hydroxy, optionally substituted alkylthio, cyano, optionally esterified or amidated carboxy, or optionally substituted amino; n is 1, 2, 3, or 4; R<1> is optionally substituted alkyl; R<2'> is optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryloxy, optionally substituted cycloalkoxy, or hydroxy; p is 1, 2, or 3; and R<2"> is optionally substituted alkoxy or hydroxy; provided that at least two of the R<2'>s and R<2"> may form a fused ring containing oxygen) or a salt of the derivative and (b) at least one other bactericide.

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6 claims: 5 independent, 1 dependent
- 1What is claimed is:[1] (a) type (I) [-izing 1]The inside of [type and X are a halogen atom, a nitro group, a substitution good alkoxy group, and a substitution good Arryoxy machine. a substitution good cycloalkoxy machine, a hydroxyl group, a substitution good hydrocarbon group, a substitution good alkylthio group, and a cyano group -- even if etherification or Amidy dani is carried out -- Yo A Carboxyl machine or substitution good Amino It is a machine and n is 1, 2, 3, or 4;R1It is a Is a replaceable alkyl machine and is R.2' -- substitution good Al they are a kill machine, a substitution good alkoxy group, a substitution good Arryoxy machine, substitution good cycloalkoxy machine , or a hydroxyl group -- p -- 1, 2, or 3 -- it is -- a substitution good alkoxy group or hydroxyl group Yes or R2'and R2- The benzoyl pyridine derivative expressed with at least two forming the condensed ring containing an oxygen atom], or its salt, (b) A Le [ A strike mouth Bill Lynn system compound and Hazo - ] system compound, the Morf Orrin system compound, A Pyrimidinamine system compound, guar gin system compound , a chlorinated organic compound, An imidazole series compound, an antibiotic, a pillage Namin system compound, Kino Oxaline system compound, A dithiocarbamate system compound, a Siano acetamide series compound, Hue- Luamide system compound, Sulh A The acid system compound, a copper system compound, an isoxazole system compound, and organophosphorus compound, N -- A halogeno Thioalkyl system compound, dicarboxyimide system compound The Ben Zwa-Lido system compound, a Piperazine system compound, a pyridine system compound, Carbinol system A compound, a piperidine series compound, organic tin series compound, A urea system compound, thinner Mick acid system A compound, fail Kaaba mate system compound, a Cyanobi roll system compound and Oxazolidinone a system -- a compound, a thia Zole carboxamide system compound, a silylamide system compound, and Amino -- acid an amide Cano mate system compound, an imidazolidine system compound, No, and an id -- a mouth Kishia - Lido system compound and Oxim ether system compound, A Phenoxy amide system compound, a benzophenone series compound, isoprothiolane, Pyroquilon, dichlomedin, quinoxyfen, proper Mocalp chloride salt, Chloropicrin, Dazomet, carbam sodium salt, Nico biphen-, diclocymet, and pro Group power which consists of Kinazides At least one sort of disinfectants chosen are made into an active ingredient, and are contained. Disinfectant constituent carrying out. 請求の範囲 [1] (a) 式 (I) [化 1] 〔式中、 Xはハロゲン原子、ニトロ基、置換可アルコキシ基、置換可ァリールォキシ基 、置換可シクロアルコキシ基、水酸基、置換可炭化水素基、置換可アルキルチオ基、 シァノ基、エステル化若しくはアミドィ匕されてもょ ヽカルボキシル基又は置換可ァミノ 基であり、 nは 1、 2、 3又は 4であり; R1は置換可アルキル基であり、 R2'は置換可アル キル基、置換可アルコキシ基、置換可ァリールォキシ基、置換可シクロアルコキシ基 、又は水酸基であり、 pは 1、 2又は 3であり、 は置換可アルコキシ基又は水酸基で あり、或いは R2'及び R2-の少なくとも 2つが酸素原子を含む縮合環を形成してもよい〕 で表されるベンゾィルピリジン誘導体又はその塩と、(b)スト口ビルリン系化合物、ァゾ ール系化合物、モルフオリン系化合物、ピリミジナミン系化合物、グァ-ジン系化合物 、有機塩素系化合物、イミダゾール系化合物、抗生物質、ピリジナミン系化合物、キノ キサリン系化合物、ジチォカーバメート系化合物、シァノアセトアミド系化合物、フエ- ルアミド系化合物、スルフ ン酸系化合物、銅系化合物、イソキサゾール系化合物、 有機リン系化合物、 N—ハロゲノチォアルキル系化合物、ジカルボキシイミド系化合物 、ベンズァ-リド系化合物、ピぺラジン系化合物、ピリジン系化合物、カルビノール系 化合物、ピぺリジン系化合物、有機スズ系化合物、尿素系化合物、シンナミック酸系 化合物、フエ-ルカーバメート系化合物、シァノビロール系化合物、ォキサゾリジノン 系化合物、チアゾールカルボキサミド系化合物、シリルアミド系化合物、ァミノアシッド アミドカーノメート系化合物、イミダゾリジン系化合物、ノ、イド口キシァ -リド系化合物 、ォキシムエーテル系化合物、フエノキシアミド系化合物、ベンゾフエノン系化合物、 イソプロチオラン、ピロキロン、ジクロメジン、キノキシフェン、プロパモカルプ塩酸塩、 クロルピクリン、ダゾメット、カーバムナトリウム塩、ニコビフェン、ジクロシメット及びプロ キンアジドからなる群力 選択される少なくとも 1種の殺菌剤とを有効成分として含有 することを特徴とする殺菌剤組成物。 (b)の殺菌剤がタレソキシムメチル、ァゾキシストロビン、メトミノフェン、トリフロキシス トロビン、ピコキシストロビン、オリザストロビン、ジモキシストロビン、フルォキサストロビ ン、エポキシコナゾール、トリフルミゾール、ォキスポコナゾールフマル酸塩、テブコナ ゾール、イミベンコナゾール、テトラコナゾール、トリアジメホン、ビテルタノール、エタ コナゾ一ノレ、プロピコナゾーノレ、ペンコナゾ一ノレ、フノレシラゾーノレ、マイクロブタニノレ、 シプロコナゾ一ノレ、へキサコナゾーノレ、ファーコナゾ一ノレシス、プロクロラズ、メトコナ ゾール、シプコナゾール、プロチォコナゾール、シメコナゾール、トリシクラゾール、プ 口べナゾール、フルキンコナゾール、トリアジメノール、フェンプロピモノレフ、スピロキサ ミン、メパニピリム、ピリメサニル、シプロジニル、ィミノクタジン、クロロタロニル、フサラ イド、キントゼン、シァゾフアミド、べノミル、チオファネートメチル及びカーベンダジム、 ポリオキシン、フノレアジナム、キノメチォネート、マンネブ、ジネブ、マンゼブ、ポリカー バメート、メチラム、プロビネブ、シモキサニノレ、メタラキシル、メタラキシル M、ォキサ ジキシル、オフレース、ベナラキシル、フララキシル、シプロフラム、ジクロフルアニド、 水酸化第二銅、有機銅、ヒメキサゾール、ホセチルアルミニウム、トルコホスメチル、 S 一べンジル O, O—ジイソプロピルホスホロチォエート、 O—ェチル S, S—ジフエ-ル ホスホロジチォエート、アルミニウムェチルハイドロゲンホスホネート、キヤプタン、キヤ プタホル、フオルペット、プロシミドン、ィプロジオン、ビンクロゾリン、、フルトラ-ル、メ プロニル、ゾキサミド、チアジニル、トリホリン、ピリフエノックス、フエナリモル、フルトリ ァフオル、フェンプロビジン、フェンチンヒドロキシド、フェンチンアセテート、ペンシキ ュロン、ジメトモルフ、フルモルフ、ジエトフェンカルプ、フルジォキソ -ル、フェンピク ロニル、ファモキサドン、エタボキサム、シルチオファム、ィプロバリカルプ、ベンチア バリカルプ、フエナミドン、フェンへキサミド、フルスルフアミド、シフルフエナミド、フエノ キサニノレ、イソプロチオラン、ピロキロン、ジクロメジン、キノキシフェン、プロパモカノレ ブ塩酸塩、スピロキサミン、クロルピクリン、ダゾメット、カーバムナトリウム塩、ニコビフ ェン、メトラフエノン、ジクロシメット及びプロキンアジドカもなる群力も選択される少なく とも 1種である請求項 1記載の殺菌剤組成物。 [3] (b)の殺菌剤がスト口ビルリン系化合物、ァゾール系化合物、モルフオリン系化合物 、ピリミジナミン系化合物、グァ-ジン系化合物、有機塩素系化合物、イミダゾール系 化合物、抗生物質、ピぺリジン系化合物及びべンゾフ ノン系化合物からなる群から 選択される少なくとも 1種である請求項 1記載の殺菌剤組成物。 The disinfectants of (b) are Taresoki SIMM methyl, a Azoxy straw bottle, and Metminophen, Trifloxystrobin, pico Xystrobin, the Oriza straw bottle, A Dimoxy straw bottle, Fluoxastrobin, epoxyconazole, Triflumizole, Oxpoconazole fumaric acid salt, Tebuconazole, Imibenconazole, tetraconazole, triadimefon, Bitertanol, Etah Konazo 1 Nollet, pro pico Nazonore, pen Konazo 1 Nollet, Funoresilazonore, micro pig Ninore and Cipro Konazo -- passing 1 Nollet -- Kisaconazonore, Fur Konazo 1 Noresis, prochloraz, Metconazole, Cipconazole, Pro Choco Nazor, simeconazole, tricyclazole, Lipstick Nazor, Full Kinko Nazor, triazimenol, a Fenpropi mono-reflex, Spiroxa Min, Mepanipyrim, Pyrimethanyl, cyprodinil, a Iminok tajine, chlorothalonil, Fusara An id, quintozene, cyazofamid, Benomyl, thiophanate-methyl and a car vendor gym, the poly oxine, Funoreginam, chinomethionat, maneb, Zineb, mancozeb, polycarbamate, metiram, pro Vineb, Simoxaninore, Metalaxyl, metalaxyl M, Oxa dixil, ofurace, Benalaxyl, furalaxyl, cyprofuram, dichlofluanid, and the second copper of water oxidization, Organic copper, Himexazole, aluminum tris(ethoxyphosphinate), Turkish hoss methyl, S1Benzil[ Phosphorodithioate, ] O and O -- Diiso propyl phosphorothioate and O -- The Le ctilS and S -- Jihue-Le Aluminum ethylhydrogen phosphonate, captan, Captahol, Folpet, procymidone, Ipro dione, vincrozoline, Hult La-Le, Me Pro nil, Zoxamide, tiadinil, trifolin, pyrifenox, Fenarimol, Full Trial, Fen pro Vidin, fentin hydroxide, Fentinacetate, Pencillon, dimethomorph, full morph, Dietofencalp, full dioxo - Le, Fenpiclonyl, famoxadone, Ethaboxam, a Silthio femme, Ipvari Balik, Bencher They are Xamide, flusulfamide, cyflufenamid, and Fenno to Bali Culp, Fenamidone, and Feng. Kisanore, isoprothiolane, pyroquilon, dichlomedin, quinoxyfen, proper Mocha no rev chloride salt, Spiroxamine, chloropicrin, Dazomet, carbam sodium salt, and Nikobif group power which Yen, Metrov enone, diclocymet, and pro Kinjidoka also become is also chosen -- few -- Both -- disinfectant constituent of the claim 1 statement which is one sort. [3] The disinfectants of (b) are a strike mouth Bill Lynn system compound, a Azole system compound, and the Morf Orrin system compound. a Pyrimidinamine system compound and aargh -- a gin system compound, a chlorinated organic compound, and imidazole series A compound, an antibiotic, a piperidine series compound, and Benzov a non system -- from the group which consists of compounds Disinfectant constituent of the claim 1 statement which is at least one sort chosen.
- 2[4] (b)の殺菌剤がタレソキシムメチル、ァゾキシストロビン、エポキシコナゾール、トリフ ルミゾール、ォキスポコナゾールフマル酸塩、テブコナゾール、イミベンコナゾール、 テトラコナゾール、シプロコナゾール、メトコナゾール、フルキンコナゾール、トリアジメ ノーノレ、フェンプロピモノレフ、スピロキサミン、メパニピリム、ィミノクタジン、クロロタロニ ル、シァゾフアミド、ポリオキシン、フェンプロビジン及びメトラフエノン力もなる群から選 択される少なくとも 1種である請求項 3記載の殺菌剤組成物。 [4] The disinfectants of (b) are Taresoki SIMM methyl and a Azoxy straw bottle, Epoxyconazole, triflumizole, Oxpoconazole fumaric acid salt, Tebuconazole, imibenconazole, tetraconazole, cyproconazole, metoconazole, full Kinko Nazor, and doria -- Jimenore and a Fenpropi mono-reflex, Spiroxamine, mepanipyrim, a Iminok tajine, chloro Taroni From the group which Le, cyazofamid, the poly oxine, Fen pro Vidin, and Metrov enone power also become to Selection Disinfectant constituent of the claim 3 statement which is at least one sort by which Choice is carried out.
- 3[5] A benzoyl pyridine derivative is formula ():[5] ベンゾィルピリジン誘導体が式 ( ): [-izing 2]B is CX when A is - N =, the inside of [type, and.4= Be;B is N = when A is - CH =;X1And X2They are a halogen atom, an alkoxy group, a hydroxyl group, and Archi to Are each independence. It is a Le machine, CF machine, or an alkylthio group, and is;X.3It is Is a hydrogen atom, a halogen atom, three alkoxy one, a Alkyl machine, CF machine, or an alkylthio group, and is;X.4They are Is a hydrogen atom, a halogen atom, 3 alkoxy groups, a Alkyl machine, CF machine, or an alkylthio group;R1a Is alkyl machine -- three Ah;R2'is an alkoxy group;p is 1, 2, or 3;R2"and R2The disinfectant constituent of Claim 1 which is a compound expressed with "' being an alkoxy group]. [化 2] 〔式中、 Aがー N =である場合、 Bは CX4 =であり; Aがー CH =である場合、 Bは N =であり; X1及び X2はそれぞれ独立にハロゲン原子、アルコキシ基、水酸基、アルキ ル基、 CF基又はアルキルチオ基であり;X3は水素原子、ハロゲン原子、アルコキシ 3 基、アルキル基、 CF基又はアルキルチオ基であり;X4は水素原子、ハロゲン原子、 3 アルコキシ基、アルキル基、 CF基又はアルキルチオ基であり; R1はアルキル基であ 3 り; R2'はアルコキシ基であり; pは 1、 2又は 3であり; R2"及び R2" 'はアルコキシ基である 〕で表される化合物である請求項 1の殺菌剤組成物。 A benzoyl pyridine derivative is a formula: (1'1) ベンゾィルピリジン誘導体が式 (1' 1): [-izing 3][X1And X2They are a halogen atom, an alkoxy group, a hydroxyl group, a Alkyl machine, a C F machine, or an alkylthio group at Are each independence;X3They are Is a hydrogen atom, a halogen atom, an alkoxy group, an Al 3 kill machine, CF machine, or an alkylthio group;R1It is a Is alkyl machine;R2'is alkoxy [ three ];p is 1, 2, or 3;And R2compound expressed with "being an alkoxy group] it is -- disinfectant constituent of Claim 5. [化 3] 〔X1及び X2はそれぞれ独立にハロゲン原子、アルコキシ基、水酸基、アルキル基、 C F基又はアルキルチオ基であり; X3は水素原子、ハロゲン原子、アルコキシ基、アル 3 キル基、 CF基又はアルキルチオ基であり; R1はアルキル基であり; R2'はアルコキシ 3 基であり; pは 1、 2又は 3であり; 及び R2"はアルコキシ基である〕で表される化合物 である請求項 5の殺菌剤組成物。 A benzoyl pyridine derivative is a 3-(2, 3,4-trimethoxy-6-methylbenzoyl)-4-Bromo- 5-Cros mouth. - 2-methoxy pyridine, 3- (2,3,4-Trimethoxy 6-Methylbenzoyl) -5-Cros Mouth - 4-The Le ctil-2-Methoxy Pyridine, 3- (4,5-Dimethoxy 2-Methylbenzoyl) -4,5-Dichloro 2-Methoxy Pyridine, 3-(5-ethoxy-4-methoxy-2-methylbenzoyl)-4, 5-dichloro 2-Mexixipi lysine, 3-(2,3,4-trimethoxy-6-methylbenzoyl)-4-Bromo-5-Cros mouth - 2-Etoxypyridine, 3-(2,3,4-trimethoxy-6-methylbenzoyl)-5-Cros mouth - 2-ethoxy-4-methyl Pyridine, 3-(2,3,4-trimethoxy-6-methylbenzoyl)-5-Bromo-4-Cros mouth - 2-ethoxy pyridine, 3-(2,3,4-trimethoxy-6-methylbenzoyl)-4-Cros mouth - 5-Eord-2-methoxy pillage The and 3-(2,3,4-trimethoxy-6-methylbenzoyl)-5-Eord-2,4-dimethoxy pyridine, 3-(2, 3, 4-trimethoxy-6-methylbenzoyl)-5-Cros mouth - 2-methoxy-4-methyl Thiopi lysine 3-(2,3,4-trimethoxy-6-methylbenzoyl)-5-Cros mouth-2,4-dimethoxy pyridine, 3-(2,3,4-trimethoxy-6-methylbenzoyl)- 4,5-dibromo 2-methoxy pyridine and 3-(2,3,4-trimethoxy-6-methylbenzoyl)- 4-Bromo-2-methoxy-5-methyl pyridine, 3-(2,3,4-trimethoxy-6-methylbenzoyl)-5-Bromo-4-trifluoromethyl-2 - Methoxy Pyridine, 3-(2,3,4-trimethoxy-6-methylbenzoyl)- 4,5-dichloro 2-methoxy pyridine, 3-(2,3,4-trimethoxy-6-methylbenzoyl)-2,4-dichloro 5-methyl pyridine, 3_(2,3,4- trimethoxy-6-methylbenzoyl)-2,4-dichloro 5-Eord pyridine, 3-(2,3,4-trimethoxy-6-methylbenzoyl)-2-Fluolo- 4-Eord-5-methyl pyridine, 3-(2, 3, 4-trimethoxy-6-methylbenzoyl)-2-Fluolo- 4, 5-Zimechi kana lysine, 3-(2, 3, 4-trimethoxy-6-Methyl benzoyl)-2 - methoxy -- 4 and 5-Zimechi kana lysine, 3-(2-ethoxy 3 and 4-dimethoxy-6-Methylbenzoyl)-2-ethoxy 4, 5-Zimechi kana lysine, and 3 -(2,3,4-trimethoxy-6-Methyl benzoyl)- 4, 5-Dimethyl-2-methyl Thiopi lysine, 3 - (2,3,4-trimethoxy-6-methyl benzo Ill) -5-Bromo-4-Cros mouth - 2-methoxy pyridine, 3 -(2,3,4-trimethoxy-6-methyl Benzoyl)- 4-Cros mouth - 2-methoxy-5-methyl pyridine, 3-(2,3,4-trimethoxy-6-methylbenzoyl)-2-Cros mouth - 5-trifluoromethyl-4-methyl pyridine, 3 -(2,3,4-trimethoxy-6-Methyl benzoyl)- 5-trifluoromethyl-2-methoxy-4-methyl pyridine, 3-(2,3,4-trimethoxy 6- methylbenzoyl)-2,4-dichloro 5-trifluoromethyl pyridine, 3-(2,3,4-trimethoxy-6-methylbenzoyl)-4-Cros mouth - 5-trifluoromethyl-2-methoxy pyridine, 3-(2,3,4-trimethoxy-6-methylbenzoyl)-5-Cros mouth - 4-Ethinil-2-methoxy pyridine and 3-(2,3,4-Trimethoxy-6-methylbenzoyl)-5-Cros mouth - 4-Fluolo methyl-2-methoxy pyridine, 3-(2, 3, 4-trimethoxy 6-methylbenzoyl)-5-Bromo-4-Fluolo methyl-2-Methoxypyri Gin, 3-(2, 3, 4-trimethoxy-6-methylbenzoyl)- 4-Fluolo methyl-2-methoxy-5-Mechi Kana lysine, 3-(2,3,4-trimethoxy-6-methylbenzoyl)-5-Cros mouth - 4-difluoromethyl-2-methoxy pyridine, 3 -(2,3,4-trimethoxy-6-methylbenzoyl)- 5-The Le ctil-4-Trifluoromethyl-2-methoxy pyridine, 3 -(2,3,4-trimethoxy-6-methylbenzoyl)- 5-Cros mouth-2-methoxy-4-methyl pyridine and 3 -(2,3,4-trimethoxy-6-methylbenzoyl)- 5-Bromo-2-methoxy-4-methyl pyridine, 3-(2,3,4-trimethoxy-6-methylbenzoyl)-4-Trifluoromethyl-2-methoxy-5-methyl pyridine and 3-(4, 5-dimethoxy-2-methylbenzoyl)-5-Cros mouth - 2 - Methoxy -It is at least one sort as which Group power which 4-methyl pyridine power also comprises is also chosen, and is Ah. Disinfectant constituent of Claim 6. ベンゾィルピリジン誘導体が、 3-(2, 3,4-トリメトキシ -6-メチルベンゾィル )-4-ブロモ -5-クロ口- 2-メトキシピリジン、 3- (2,3,4-トリメトキシ- 6-メチルベンゾィル )-5-クロ口- 4- ェチル -2-メトキシピリジン、 3- (4,5-ジメトキシ- 2-メチルベンゾィル )-4,5-ジクロロ- 2- メトキシピリジン、 3-(5-エトキシ -4-メトキシ -2-メチルベンゾィル )-4,5-ジクロロ- 2-メト キシピリジン、 3-(2, 3,4-トリメトキシ -6-メチルベンゾィル )-4-ブロモ -5-クロ口- 2-ェトキ シピリジン、 3-(2,3,4-トリメトキシ -6-メチルベンゾィル )-5-クロ口- 2-エトキシ -4-メチル ピリジン、 3-(2,3,4-トリメトキシ -6-メチルベンゾィル )-5-ブロモ -4-クロ口- 2-エトキシピ リジン、 3-(2,3,4-トリメトキシ -6-メチルベンゾィル )-4-クロ口- 5-ョード -2-メトキシピリジ ン、 3-(2,3,4-トリメトキシ -6-メチルベンゾィル )-5-ョード -2,4-ジメトキシピリジン、 3-(2,3,4-トリメトキシ -6-メチルベンゾィル )-5-クロ口- 2-メトキシ -4-メチルチオピリジン 、 3-(2,3,4-トリメトキシ -6-メチルベンゾィル )-5-クロ口- 2,4-ジメトキシピリジン、 3-(2,3,4-トリメトキシ -6-メチルベンゾィル )-4,5-ジブロモ -2-メトキシピリジン、 3-(2,3,4-トリメトキシ -6-メチルベンゾィル )-4-ブロモ -2-メトキシ -5-メチルピリジン、 3-(2,3,4-トリメトキシ -6-メチルベンゾィル )-5-ブロモ -4-トリフルォロメチル -2-メトキシ ピリジン、 3-(2,3,4-トリメトキシ -6-メチルベンゾィル )-4,5-ジクロロ- 2-メトキシピリジン、 3-(2,3,4-トリメトキシ -6-メチルベンゾィル )-2,4-ジクロロ- 5-メチルピリジン、 3_(2,3,4- トリメトキシ -6-メチルベンゾィル )-2,4-ジクロロ- 5-ョードピリジン、 3-(2,3,4-トリメトキシ -6-メチルベンゾィル )-2-フルォロ- 4-ョード -5-メチルピリジン、 3-(2,3,4-トリメトキシ -6-メチルベンゾィル )-2-フルォロ- 4,5-ジメチルビリジン、 3-(2,3,4-トリメトキシ -6-メチ ルベンゾィル )-2-メトキシ- 4,5-ジメチルビリジン、 3-(2-エトキシ- 3,4-ジメトキシ -6-メ チルベンゾィル )-2-エトキシ- 4,5-ジメチルビリジン、 3-(2,3,4-トリメトキシ -6-メチルベ ンゾィル)- 4,5-ジメチル -2-メチルチオピリジン、 3-(2,3,4-トリメトキシ -6-メチルベンゾ ィル) -5-ブロモ -4-クロ口- 2-メトキシピリジン、 3-(2,3,4-トリメトキシ -6-メチルベンゾィ ル)- 4-クロ口- 2-メトキシ -5-メチルピリジン、 3-(2,3,4-トリメトキシ -6-メチルベンゾィル )-2-クロ口- 5-トリフルォロメチル -4-メチルピリジン、 3-(2,3,4-トリメトキシ -6-メチルベ ンゾィル)- 5-トリフルォロメチル -2-メトキシ -4-メチルピリジン、 3-(2,3,4-トリメトキシ- 6- メチルベンゾィル )-2,4-ジクロロ- 5-トリフルォロメチルピリジン、 3-(2,3,4-トリメトキシ -6-メチルベンゾィル )-4-クロ口- 5-トリフルォロメチル -2-メトキシピリジン、 3-(2,3,4-ト リメトキシ -6-メチルベンゾィル )-5-クロ口- 4-ェチニル -2-メトキシピリジン、 3-(2,3,4-ト リメトキシ -6-メチルベンゾィル )-5-クロ口- 4-フルォロメチル -2-メトキシピリジン、 3-(2,3,4-トリメトキシ -6-メチルベンゾィル )-5-ブロモ -4-フルォロメチル -2-メトキシピリ ジン、 3-(2,3,4-トリメトキシ -6-メチルベンゾィル )-4-フルォロメチル -2-メトキシ -5-メチ ルビリジン、 3-(2,3,4-トリメトキシ -6-メチルベンゾィル )-5-クロ口- 4-ジフルォロメチル -2-メトキシピリジン、 3-(2,3,4-トリメトキシ -6-メチルベンゾィル )- 5-ェチル -4-トリフル ォロメチル -2-メトキシピリジン、 3-(2,3,4-トリメトキシ -6-メチルベンゾィル )- 5-クロ口 -2-メトキシ -4-メチルピリジン、 3-(2,3,4-トリメトキシ -6-メチルベンゾィル )- 5-ブロモ -2-メトキシ -4-メチルピリジン、 3-(2,3,4-トリメトキシ -6-メチルベンゾィル )-4-トリフル ォロメチル -2-メトキシ -5-メチルピリジン及び 3-(4,5-ジメトキシ -2-メチルベンゾィル )-5-クロ口- 2-メトキシ -4-メチルピリジン力も成る群力も選択される少なくとも一種であ る請求項 6の殺菌剤組成物。 A benzoyl pyridine derivative is a formula: (I, 1 2) ベンゾィルピリジン誘導体が式 (I,一 2): [-izing 4][X1And X2They are a halogen atom, an alkoxy group, a hydroxyl group, a Alkyl machine, a C F machine, or an alkylthio group at Are each independence;X3They are Is a hydrogen atom, a halogen atom, an alkoxy group, an Al 3 kill machine, CF machine, or an alkylthio group;X4They are Is a hydrogen atom, a halogen atom, an Alcokey 3 Si machine, a Alkyl machine, CF machine, or an alkylthio group;R1It is a Is alkyl machine;R2'is 3 alkoxy groups;p is 1, 2, or 3;R2"and R2"' is an alkoxy group] -- a table -- Disinfectant constituent of Claim 5 which is a Be compound. [化 4] 〔X1及び X2はそれぞれ独立にハロゲン原子、アルコキシ基、水酸基、アルキル基、 C F基又はアルキルチオ基であり; X3は水素原子、ハロゲン原子、アルコキシ基、アル 3 キル基、 CF基又はアルキルチオ基であり; X4は水素原子、ハロゲン原子、アルコキ 3 シ基、アルキル基、 CF基又はアルキルチオ基であり; R1はアルキル基であり; R2'は 3 アルコキシ基であり; pは 1、 2又は 3であり; R2"及び R2" 'はアルコキシ基である〕で表さ れる化合物である請求項 5の殺菌剤組成物。
- 5[10] (a)のベンゾィルピリジン誘導体又はその塩と、(b)の殺菌剤との混合重量比が 1 :1 0000— 10000: 1である請求項 1に記載の殺菌剤組成物。 [10] The mixed weight ratio of the benzoyl pyridine derivative of (a) or its salt, and the disinfectant of (b) is 1. : 1 0000 -- 10000 : Disinfectant constituent given in Claim 1 which is 1.
- 6[11] claim 11 -- using a disinfectant constituent given in either of 10 for a plant -- the feature and The Control method of Plant disease. [11] 請求項 1一 10のいずれかに記載の殺菌剤組成物を植物に施用することを特徴とす る植物病害の防除方法。
Independent claims5
638 paragraphs in 3 sections, as filed
Specification
A disinfectant constituent and a control method of plant disease
Technical field
Agriculture and horticulture as for which plant disease raised prevention and Z, or the effect to treat markedly as for the [oooi] present invention A disinfectant constituent useful as a for disinfectant, and control method of plant disease using the constituent It is related.
Background art
[0002] Benzoyl pillage which is an active ingredient of the disinfectant constituent of the present invention WO02Z2527 It is indicated that a A derivative is useful as a disinfectant, necessity is accepted, and it is Mixed with other disinfectants. There is a description that the for combined use [ - ] is possible. carry out, and the constituent of the present invention is notably excellent, carrying out power having Bactericidal effect is known [ ] -- ,
[0003] Patent documents 1 : International publication WO02Z2527
The indication of an invention
Object of the Invention
[0004] The benzoyl pyridine derivative denoted by after-mentioned type (I) is respectively set in the plant disease control effect, the effect is enough to specific plant disease -- Strong force and Residual effect -- comparatively -- short -- cutting, or rainproofness being weak and receiving plant disease in a certain application scene -- practically -- un--- Do not show and a thing have only sufficient control effect.
Means for solving problem
[0005] These artificers are Use at independent about each compound, when mixed use of the benzoyl viridin derivative denoted by after-mentioned type (I) and the specific disinfectant is carried out, as a result of inquiring that the above-mentioned problem should be solved. Profitable in the knowledge of the outstanding bactericidal effect which cannot be expected being acquired as compared with the case where for is carried out
The present invention was completed.
[0006] That is, the present invention is (a) type (I). : [0007] [-izing 1]
<img file="WO2005041663A1_D0001.tif" />
[0008] The inside of [type and X are a halogen atom, a nitro group, and a substitution good hydrocarbon group, a substitution good alkoxy group and substitution a good Ally Oxy machine, a substitution good cycloalkoxy machine, a hydroxyl group, a substitution good alkylthio group, and a cyano group -- even if etherification or Amidi A is carried out -- Yo It is a carboxyl machine or a substitution good Amino machine, and n is 1, 2, 3, or 4; R<sup>1</sup>it is a Is replaceable alkyl machine -- IT -- substitution good Al they are a kill machine, a substitution good alkoxy group, a substitution good Ally Oxy machine, substitution good cycloalkoxy machine , or a hydroxyl group -- p -- 1, 2, or 3 -- it is -- a substitution good alkoxy group or hydroxyl group There or R<sup>2</sup>'and R<sup>2</sup>- The benzoyl pyridine derivative expressed with at least two forming the condensed ring containing an oxygen atom], or its salt, (b) A Le [ A strike mouth Bill Lynn system compound and Azo - ] system compound, the Morf Orrin system compound, A Pyrimidinamine system compound, guar gin system compound , a chlorinated organic compound, An imidazole series compound, an antibiotic, a pillage Namin system compound, Kino Xyline system compound, A dithiocarbamate system compound, a Shano acetamide series compound, Hue- Luamide system compound, Sulh A A acid system compound, a copper system compound, an isoxazole system compound, and organophosphorus compound, N -- A halogeno Thioalkyl system compound, dicarboxyimide system compound The Ben Zua-Lido system compound, a Piperazine system compound, a pyridine system compound, Carbinol system A compound, a piperidine series compound, organic tin series compound, A urea system compound, thinner Mick acid system A compound, fail Kaaba mate system compound, a Shanobi roll system compound and Oxazolidinone a system -- a compound, a thia Sol carboxamide system compound, a silylamide system compound, and Amino -- acid an amide Kano mate system compound, an imidazolidine system compound, A, and an id -- mouth Kisa - Lido system compound and Oxim ether system compound, A Phenoxy amide system compound, a benzophenone series compound, and isoprothiolane, Pyroquilon, dichlomedin, quinoxyfen, proper Mocarp chloride salt, Chloropicrin, Dazomet, carbam sodium salt, Nico biphen-, diclocymet, and pro Group force which consists of Kin Azides At least one sort of disinfectants chosen are made into an active ingredient, and are contained. It is related with the disinfectant constituent carrying out. The present invention is the above-mentioned disinfectant constituent. It is related with the control method of the plant disease using it for a plant.
[0009] As a halogen atom in formula (I), fluoride, chlorine, bromine, or iodine is used and it is Desirable. Is, for example, the fluoride, chlorine, or bromine to spread is used.
[0010] As a hydrocarbon portion of the substitution good hydrocarbon group in formula (I), it is C Alkyl (metaphor), for example.
1-6
C, such as The methyl, Ethyl, propyl, isopropyl, butyl, isobutyl, and t butyl
2-6 Alkenyl (for example, Vinyl, Allyl, Isopropenyl)<sub>3</sub>- methyl 2 -- c, such as butenyl
2-6 Alkynyl (for example, Ethynyl and 1 Propynyl and 2 -- Propynyl Etc.), C Cycloalkyl
3-6
(for example, cyclo propyl, cyclopentyl and cyclohexyl), C A riel, etc. -- mentioning
6-10
To be. As a secondary substitution machine of a substitution good hydrocarbon group, they are A riel, Ally Oxy, Hyd mouth Ix, nitroglycerine, Nitroxy, halogen (for example, fluoride, chlorine, bromine, iodine, etc.), and Haaru. Cocksail (for example, C haloalkoxy, such as CF 0 and HCF O), cycloalkyl, friend ON A
3 2 1-4
Lukilchio and Shano power Group force 1 thru/or 5 same or different substitution chosen A machine is mentioned. the inside of these substitution good hydrocarbon groups -- a substitution good Alkyl machine -- Desire -- better -- Tooth Especially a Alkyl machine is desirable also in it. In a Alkyl machine, it is C Alkyl machine.
1-4
Is the most is also desirable.
[0011] As Alkyl portions of the substitution good Alkyl machine in formula (I), a substitution good alkoxy group, and a substitution good alkylthio group, it is C Alkyl (for example, methyl, Ethyl, propyl, isopropyl, The).
1-6
Chill, isobutyl, t butyl, etc. are desirable -- the inside of it -- C Alkyl -- Desire -- better -- , Again
1-4
As a secondary substitution machine of these substitution machines, they are A riel and Ally Oxy, Hydroxy , nitroglycerine, Nitroxy, halogen (for example, fluoride, chlorine, bromine, iodine, etc.), haloalkoxy (for example, C haloalkoxy, such as CF 0 and HCF O), cycloalkyl, friend ON Alkylthio and
3 2 1-4
Bianno power power -- Group force 1 thru/or 5 same or different substitution machines chosen mention. , -- To be . the inside of the substitution machine which has these Alkyl portions -- an unreplaced substitution machine -- Desire -- better -- Tooth C Alkyl -- especially -- Desire -- better -- , the inside of it -- methyl -- most -- Desire -- better! /
1-4
[0012] Power in which a condensed type polycyclic type machine like Naff Chill besides fail is mentioned as a A riel portion of the substitution good Ally Oxy machine in formula (I) Phenyl is desirable. As the secondary substitution machine of these substitution good machines, As the cycloalkyl portion of the substitution good cycloalkoxy machine in [0013] type (I) to which halogen, Alkyl, and alkoxy , hydroxy etc are mentioned, Generally it is carbon number 3. -- It is Ix to the thing of 10, for example, cyclo propyl, cyclo butyl, cyclopentyl, and cyclo. Power in which a condensed type polycyclic type machine besides monocycle type machines, such as Le and Cycloctil, etc. is mentioned A monocycle type machine is desirable. Halogen, Alkyl, Alcoxy, and hydroxy etc are mentioned as a secondary substitution machine of these substitution good machines. Also in a cycloalkoxy portion, cyclohexyl Oxy is the most desirable.
[0014] As a carboxyl group in formula (I) by which S-Telui-A(ing) or Amidi A may be carried out, it is C Alcokey Cicar ball machine (for example, a methoxy Carbo-Le machine, an ethoxy Carbo-Le machine), for example.
1-6
a propoxy Carbo-Le machine, an isopropoxy Carbo-Le machine, and a Butoxycal ball machine -- iso -- Nitrooxy c alkoxy friends, such as a Butoxycal ball machine and t Butoxycal ball machine
1-4
A Nokaru ball machine (for example, 2 -- a 2 Trooki Schetky Cicar ball machine and 3 -- 2 Trooxyproboxyl ball machine etc.), a fail C Alcokey Cicar ball machine (for example, Venice)
1-4
the Cal Bo-Le machine, a phenethyloxy Carbo-Le machine, etc. -- etc. -- even if etherified -- , a Cal Boxil machine; power Luba Moyle machine, and c monoalkyl friend Nokaru ball machine (for example, Methyl)
1-6
Di C alkylamino Carbo-Le machines, such as the Minot carbonyl group, a Tetraminocar ball machine, a propyl friend Nokaru ball machine, an isopropyl friend Nokaru ball machine, a butylamino Carbo-Le machine, an iso butylamino Carbo-Le machine, and t-butylamino Carbo-Le machine (for example, Dimethy)
1-6
Nitrooxy C alkylamino Carbo-Le machines, such as a Ruminocal ball machine, a diethylamino Carbo-Le machine, a dipropylamino Carbo-Le machine, a diisopropylamino Carbo-Le machine, a dibutylamino Carbo-Le machine, and an iso dibutylamino carbonyl group (for example, 2 -- 2 Trooki)
1-4
A Shetylaminol ball machine and 3 --- Fail C alkylamino Carbo-Le machines, such as a Trooxys propylamino Carbo-Le machine (for example, a benzylamino Carbo-Le machine, Phenethyl)
1-4
C [ machine / Aminol ball ] cycloalkyl friend Nokaru ball machine (for example, cyclo Prop)
3-6
It is a Kisylamino carbonyl group etc. to a Ruminocal ball machine, a cyclopentylamino Carbo-Le machine, and cyclo, Annular friend Nokaru ball machines (for example, a morpholino carbonyl machine, a piperidino Carbo-Le machine, a pylori Zinocal ball machine, a thiomorpholino Carbo-Le machine, etc.), Aminol Carboxyl groups by which Amidi A may be carried out, such as a Bonyl machine, are mentioned.
[0015] As a substitution good Amino machine in formula (I), they are an amino group; monoalkylamino machine and Sial, for example. Alkylamino groups, such as a kill amino group, etc. are mentioned. A of the above-mentioned alkylamino group As a Lukil portion, C Alkyl is desirable. The secondary substitution machine of a substitution good Amino machine
1-4
If it carries out, they are A riel, Ally Oxy, hydroxy , nitroglycerine, Nitroxy, halogen (for example, Hook base, chlorine, bromine, iodine, etc.), and haloalkoxy (for example, C Halos, such as CF 0 and HCF O).
3 2 1-4 alkoxy group, cycloalkyl, friend ON Alkylthio, and Shano power it is chosen -- the same -- again -- it differed -- one -- it and five substitution machines are mentioned.
[0016] In addition, the definition of the A riel portion in the secondary substitution machine of each above-mentioned substitution machine, a cycloalkyl portion, and a Alkyl portion applies to the definition of each substitution machine.
[0017] The compound denoted by formula (I), Even if it forms salt with acid things, they are Well, for example, chloride salt, hydrobromic acid salt, an phosphate, sulfate or inorganic acid salt; acetate like a nitrate, and benzoic acid. Salt, rho -- It is like toluenesulfonic acid salt, methanesulfonic acid salt, or propanesulfonic acid salt. Organic acid salt can be formed.
[0018] it comes out to obtain with the compound denoted by formula (I) and the manufacturing method indicated by WO02/2527 -- last . To Up, it is Journal of Organic Chemistry., 58, and 7832 (1993), It is Made also with the method according to European Journalof Organic Chemistry., 7, 1371-1376 (2001), or after-mentioned each synthetic example. Construction can be carried out.
[0019] As a strike mouth Bill Lynn system compound, For example, kresoxim-methyl (Kresoxim- Methyl), A A Zoxy straw bottle (Azoxystrobin), Metominophen (Metominofen), Trifloxystrobin (Trifloxystrobin), pico Xystrobin (Picoxystrobin), Oriza straw bottle (Oryzastrobin), a Jimoxy straw bottle (Dimoxystrobin), and Fluoxa straw bottle (Fluoxastrobin) are Behavior. To be. Also in it, kresoxim-methyl and a Azoxy straw bottle are desirable.
[0020] Kresoxim-methyl is The Pesticide Manual (the 12nd edition of The; BRITISH CROP).
PROTECTION COUNCIL The 568 -- It is a compound of a 569-page statement. AZOXIS TROBIN is The Pesticide Manual. The (the 12nd edition of The; BRITISH CROP PROTECTION COUNCIL) 54 -- It is a compound of a 55-page statement.
[0021] As a Azole system compound, they are epoxyconazole (Epoxiconazole), Triflumizole (Triflumizole), and Kiss poconazole fumaric acid salt (Oxpoconazole), for example.
fumarate, Abconazo'~~Nollet (Tebuconazole A) Í Strange Conan~~Nollet (Imibenconazole A, tetraconazole (Tetraconazole)) Triadimefon (Triadimefon), Vitertano 1 Le (Bitertanol), Ethaconazo 1 Nollet (Etaconazole), pro pico Nazonole (Propiconazole), pen Conazo 1 Nollet (Penconazole), Funore Shirazonore (Flusilazole), micro pig -Noori (Myclobutanil), and Cipro Conazo -- passing 1 Nollet (Cyproconazole) -- Xaconazonore
Hexaconazole, Fa~~Conan~~Norresis (Furconazole -- cis), Off mouth Crouchs (Prochloraz) and Metoconazonore (Metconazole), Sipconazonore (Sipconazole), pro Chiokonazonore (Prothioconazole), Memekonan~~Nollet (; meconazole), Trink Phung~~Nollet (Tricyclazoie), Pro What Nazor (Probenazole), full Kinko Nazor, and (Fluquinconazole) Triadimate Knoll (Triadimenol) is mentioned. Also in it, they are epoxyconazole and truffe Lumizo. Le, Kiss poconazole fumaric acid salt, tebuconazole, imibenconazole, Tetraconazole, cyproconazole, metoconazole, full Kinko Nazor, and triazimenol It is desirable.
Epoxyconazole is The Pesticide Manual (the 12th edition; BRITISH CROP).
PROTECTION COUNCIL The 349 -- It is a compound of a 350-page statement. Triflumizole (Triflumizole) is The Pesticide Manual (the 12th edition; BRITISH CROP PROTECTION).
COUNCIL The 940 -- It is a compound of a 941-page statement. Kiss poconazole fumaric acid salt (Oxpoconazole !Umarate) * Up and The Pesticide Manual It is a compound of a statement with a The (the 12nd edition of a younger brother; BRITISH CROP PROTECTION COUNCIL) of 699 pages. Tebuconazole (Tebuconazole) is The Pesticide Manual (the 12th edition; BRITISH CROP).
PROTECTION COUNCIL The 864 -- It is a compound of an 865-page statement. Imibenconazo 1 Le (Imibenconazole) is The Pesticide Manual (the 12th edition; BRITISH CROP).
PROTECTION COUNCIL The 535 -- It is a compound of a 536-page statement. Tetraconazole (Tetraconazole) is The Pesticide Manual (the 13th edition; BRITISH CROP).
PROTECTION COUNCIL The 945 -- It is a compound of a 946-page statement. Cipro Conazo 1 Le is ThePesticide Manual (the 13th edition; BRITISH CROP PROTECTION).
COUNCIL The 248 -- It is a compound of a 249-page statement. Metoconazole is The Pesticide.
Manual The (the 13th edition; BRITISH CROP PROTECTION COUNCIL) 643 -- It is an account to 644 pages. It is a compound of Loading. Full Kinko Nazor is The Pesticide Manual. The (the 13rd edition of The; BRITISH CROP PROTECTION COUNCIL) 472 -- which is a compound of a 473-page statement. Triazimenol is The Pesticide Manual (the 13th edition; BRITISH CROP).
PROTECTION COUNCIL The 987 -- It is a compound of a 989-page statement.
[0023] As a Morf Orrin system compound, fenpropimorph (Fenpropimorph) and Spiroxamine (Spiroxamine) are mentioned, for example. Fenpropimorph is The Pesticide Manual. The (the 12th edition; BRITISH CROP PROTECTION COUNCIL) 399 -- It is an account to 400 pages. It is a compound of Loading. Spiroxamine is The Pesticide Manual. The (the 12nd edition of The; BRITISH CROP PROTECTION COUNCIL) 842 -- It is a compound of an 843-page statement.
[0024] As a Pyrimidinamine system compound, Mapper-Pirim (Mepanipyrim), the Pirie Mesa-Le (Pyrimethanil), and SHIPRO Zeile (Cyprodinil) are mentioned, for example. Also in it, it is Mapper-Pirim. It is desirable. Mapper-Pirim is The Pesticide Manual. The (the 12nd edition of The; BRITISH CROPPROTECTION COUNCIL) 596 -- It is a compound of a 597-page statement.
[0025] Aargh, as a gin system compound, a Iminok tajine (Iminoctadine) is mentioned, for example.
A Iminok tajine is The Pesticide Manual. The (the 12nd edition of The; BRITISH CROP PROTECTION COUNCIL) 539 -- It is a compound of a 541-page statement.
[0026] As a chlorinated organic compound, Chlorota mouth-Le (Chlorothalonil), fthalide (Fthalide), and quintozene (Quintozene) are mentioned, for example. the inside of it -- chlorothalonil -- Desire better -- There. Chlorota mouth-Le is The Pesticide Manual. The (the 12nd edition of The; BRITISH CROP PROTECTION COUNCIL) 168 -- It is a compound of a 169-page statement.
[0027] As an imidazole series compound, cyazofamid (Cyazofamid), Benomir (Benomyl), thiophanate-methyl, and (Thiophanate-Methyl) car vendor gym (Carbendazim) are Behavior. To be. Also in it, cyazofamid is desirable. Cyazofamid is The Pesticide Manual. The (the 12nd edition of The; BRITISH CROP PROTECTION COUNCIL) 523 -- It is an account to 524 pages. It is a compound of Loading.
[0028] As an antibiotic, the poly oxine (Polyoxins) is mentioned, for example. The poly oxine and the 12nd edition of The Pesticide ManuaK The; It is a compound of a statement with a BRITISH CROP PROTECTION COUNCIL The of 752--754 pages. [0029] As a pillage Namin system compound, fluazinam (Fluazinam) is mentioned, for example.
[0030] as a quinoxaline system compound, chinomethionat (Quinomethionate) mentions, for example , -- To be .
[0031] As a dithiocarbamate system compound, For example, maneb (Maneb), Zineb (Zineb), mancozeb (Mancozeb), the poly Kano mate (Polycarbamate), metiram, and (Metiram) Probeneb (Propineb) is mentioned.
[0032] As a Shano acetamide series compound, the Simo A kiss-Le (Cymoxanil) is mentioned, for example. To.
[0033] As a fail amide system compound, they are metalaxyl (Metalaxyl) and metalaxyl M, for example.
(Metalaxyl M), Oxadixil (Oxadixyl), ofurace (Oforace), benalaxyl (Benalaxyl), furalaxyl, and (Furalaxyl) cyprofuram (Cyproforam) are mentioned.
[0034] as a sulfenic acid system compound -- dichlofluanid (Dichlofluanid) -- mentioning -- To be.
[0035] As a copper system compound, they are the second copper of Hydroxic acid, and (Cupric hydroxide) organic copper, for example.
Oxine Copper is mentioned.
[0036] As an isoxazole system compound, Hymexazol (Hymexazol) is mentioned, for example.
[0037] As an organophosphorus compound, it is aluminum tris(ethoxyphosphinate) (Fosety ♪ A1), for example, Turkey Hoss Methyl (Tolcofos- Methyl) and S [ -- EthylS and S / -- Jihue-Le phosphorodithioate and aluminum Nium Etchiruhide mouth / Genphosphonate is mentioned. ] -- Ben Jill O and O -- Diiso propyl phosphorothioate and O
[0038] N -- As a No roge nothio alkyl system compound, they are Captan (Captan) and A cap, for example. Tahor (Captafol) and folpet (Folpet) are mentioned.
[0039] As an dicarboxyimide system compound, they are procymidone (Procymidone) and Ipro, for example. Dione (Iprodione) and vincrozoline (Vinclozolin) are mentioned.
[0040] As a Ben Zua-Lido system compound, the Hult La-Le (Flutolanil), Mepro-Le (Mepronil), Zoxamide (Zoxamid), and thia Di-Le (Tiadinil) are mentioned, for example.
[0041] As a Piperazine system compound, trifolin (Triforine) is mentioned, for example. [0042] As a pyridine system compound, pyrifenox (Pyrifenox) is mentioned, for example.
[0043] As a carbinol system compound, they are fenarimol (Fenarimol) and full Tria, for example. Orr (Flutriafol) is mentioned.
[0044] As a piperidine series compound, Fen pro Vidin (Fenpropidine) is mentioned and Ru Fen pro Vidin is The Pesticide Manual (the 13th edition; BRITISH CROP), for example.
PROTECTION COUNCILThe4191 -- it is a compound of a 420-page statement.
[0045] As an organic tin series compound, it is fentin hydroxide (Fentin Hydroxide) And, for example. Facial expression fentinacetate (Fentin Acetate) is mentioned.
[0046] As a urea system compound, pen Ciccuron (Pencycuron) is mentioned, for example.
[0047] As a thinner Mick acid system compound, they are dimethomorph (Dimethomorph) and Furumo, for example. Rough (Flumorph) is mentioned.
[0048] As a fail Kaaba mate system compound, it is Dietofencarp (Diethofencarb), for example.
It is mentioned.
[0049] As a Shanobi roll system compound, they are a full Jioki sole (Fludioxonil) and Hue, for example. A Emp roll (Fenpiclonil) is mentioned.
[0050] as a Oxazolidinone system compound -- famoxadone (Famoxadone) -- mentioning -- To be.
[0051] As a thia Sol carboxamide system compound, Ethaboxam (Ethaboxam) is, for example. It is mentioned.
[0052] As a silylamide system compound, Siltio femme (Silthiopham) is mentioned, for example.
[0053] As a Amino acid Amideca mate system compound, it is Diplovaricalp, for example.
Iprovalicarb and benthiavalicarb (benthiavalicarb) are mentioned.
[0054] As an imidazolidine system compound, Fenamidon (Fenamidone) is mentioned, for example.
[0055] As a Hyde mouth Kisa - Lido system compound, Ximid (Fenhexamid) is Behavior to Feng, for example. To be.
[0056] As a benzene sulfonamide series compound, flusulfamide (Flusulfamid) is, for example. It is mentioned. [0057] As a Oxim ether system compound, cyflufenamid (Cyflufenamid) is Behavior, for example. To be.
[0058] As a Phenoxy amide system compound, the Fenno A kiss-Le (Fenoxanil) is mentioned, for example. To.
[0059] As a benzophenone series compound, Metrov enone (Metrafenone) is mentioned, for example. To. Metrov enone is AG CHEM NEW COMPOUND REVIEW and VOLUME 21-2003. It is a compound of a statement with a The of 17 pages.
[0060] As other compounds, it is isoprothiolane (Isoprothiolane), for example, Pyroquilon (Pyroquilon), dichlomedin (Diclomezine), Quinoxyfen (Quinoxyfen), proper Mocal chloride salt (Propamocarb Hydrochloride), Chronolepicrin (Chloropicrin), Dazomet (Dazomet), Carbam sodium salt (Metam- sodium), - Cobi Feng (Nicobifen), Dichrome simet (Diclocymet) and pro Kin Azide (Proquinazid) are mentioned.
[0061] What was listed above is mentioned as a disinfectant of (b) which is an active ingredient of a present invention disinfectant constituent. Also in it, they are a strike mouth Bill Lynn system compound, a Azole system compound, and a Morpholine system compound, a Pyrimidinamine system compound, a guanidinium system compound, a chlorinated organic compound, an imidazole series compound, an antibiotic, a piperidine series compound, and a Benzov enone system compound -- from Group power It is desirable to use at least one sort chosen. Taresoki SIMM methyl, Azuki Sisto Robin, epoxyconazole, Triflumizole, Kiss poconazole fumaric acid salt , tebuconazole, Imibenconazole, tetraconazole, cyproconazole, metoconazole, Full Kinko Nazor, Troazimenol, fenpropimorph, Spiroxamine, Mepanipyrim, a Iminok tajine, chloro Taroninole, cyazofamid, the poly oxine, Fenro It is further to use at least one sort as which Group force which Vidin and Metoraf non power also turn into is also chosen. It is desirable.
EFFECT OF THE INVENTION
[0062] the disinfectant constituent of the present invention receives the cultivated crop infected with plant disease -- it was stabilized -- high It is what has a bactericidal effect. Plant disease can be controlled using this constituent. The best form for inventing In manufacturing the compound of the above-mentioned formula (I), or its salt, a desirable method is illustrated below.
(1) Formula (A 1)
[0064] [-izing 2]
<img file="WO2005041663A1_D0002.tif" />Substituted benzene aldehyde come out of and expressed (inside of a formula)<img file="WO2005041663A1_D0003.tif" />R<sup>2</sup>R<sup>2</sup>"and p -- the above-mentioned passage -- it is -- formula (nupi -- 1):
[0065] [-izing 3]
^ '
N
the (inside of a formula and X are as above-mentioned -- zeta is a metal atom or its compound salt --) -- substitution expressed making metal salt of a pyridine derivative react -- formula (X) :
[-izing 4]
<img file="WO2005041663A1_D0004.tif" />
(Inside of a formula, and X)<img file="WO2005041663A1_D0005.tif" />R<sup>2</sup>', R<sup>2</sup>", n, and p -- the above-mentioned passage -- it is -- the Hue- kana lysyl- expressed -- meta--- manufacturing Knoll -- following -- -- coming out and carrying out acid Y of this thing -- the compound of the above-mentioned formula (I), or its salt -- How to manufacture.
[0067] (2) types (VI -- 2): [0068] [-izing 5]<img file="WO2005041663A1_D0006.tif" />Metal salt of the substituted benzene derivative come out of and expressed (inside of a formula)<img file="WO2005041663A1_D0007.tif" />R<sup>2</sup>', R<sup>2</sup>"and p are as above-mentioned There and Z -- a metal atom or its compound salt -- it is -- formula: (VII -- 2)
[0069] [-izing 6]<img file="WO2005041663A1_D0008.tif" />
How to manufacture the phenyl pyridyl methanol which makes the substitution pyridyl aldehyde expressed with (the inside of a formula, and X and n are as above-mentioned) react, and is denoted by and formula (X), and to manufacture the compound of the above-mentioned formula (I), or its salt by subsequently carrying out acid Y of this thing.
[0070] it sets to the above-mentioned process (1) and (2) -- as the metal atom denoted by Z -- lithium and Magnee Transition metal atoms, such as type metal atom; palladium, such as Shum, zinc, and copper, and ruthenium, etc. are mentioned. It can replace with a metal atom and can use Le [ The compound salt of a metal atom, for example (art complex) Giary, - ] copper lithium, triallyl copper lithium, etc.
[0071] The compound of the above-mentioned formula (VI -- 1), and the compound of a formula (VII -- 2), (Usually, publicly known method 6847, for example, 57 Journal of Organic Chemistry The first, -- It can manufacture according to the method indicated in 6852 pages and 1992.)
[0072] Phenyl pyridyl methano denoted by formula (X) manufactured by the above-mentioned process (1) and (2) Le, By a publicly known means, they are metal oxidizers, such as manganese dioxide and chromic acid, for example, It oxidizes by the Swern oxidizing method (dimethyl sulfoxide + oxalyl chloride), a ruthenium oxidation method (tetra-pro Pilamo - Um pearl tenate +N methyl morpholine N -- Oxide), etc., and is changed into the compound denoted by formula (I).
[0073] The compound of the formula (VII -- 1) in a process (1) is formula (VIII) : [0074] [-izing 7]<img file="WO2005041663A1_D0009.tif" />
[0075] the inside of [type, and X and n are as above-mentioned -- Hal is a halogen atom. compound denoted by] Formula (IX): Ar -- it can obtain by making the compound denoted by Z ( the inside of a formula and Ar are a Alkyl machine or a A riel machine -- Z is as above-mentioned and there is) react. This reaction is a solvent. Under existence -- 100"C -- It is desirable to be carried out with the reaction temperature of 120"C. It is considered as Ar~Z. The are isopropyl magnesium chloride and isopropyl magnesium Bromley, for example. Do, methyl lithium, butyl lithium, fail lithium, Diiso propyl magnesium, etc. It is mentioned. Or lithium Diiso propyl amide, lithium 2, 2, and 6, 6-tetra-Methylpi It can also obtain by a hydrogen-metal exchange reaction using metal amide, such as Perazide.
[0076] The compound and formula (XI) of (3) above-mentioned type (VIII):
[0077] [-izing 8]
[type<img file="WO2005041663A1_D0010.tif" /><sup>2</sup>"and p are as above-mentioned -- combination denoted by] whose M is a metal atom Method of manufacturing the compound of the above-mentioned formula (I), or its salt by making a thing reacting under transition metal catalyst existence and carbon monoxide atmosphere.
[0078] the above-mentioned process (3) -- as , The, and a metal atom -- hydroxy boron and Alphabet -- base and ARC Koxihou -- base, halogenation magnesium, zinc halide, alkyltin, Alkylsilane, alkoxysilane, etc. are mentioned. As a transition metal catalyst, it is A. Radium, rhodium, ruthenium, etc. are mentioned. This reaction is singleness or mixed Inert fusion. The bottom of existence of intermediation, and 0"C -- It is desirable to be carried out with the reaction temperature of 200"C. 1 acid Y of normal pressure This which may be sufficient under a carbon atmosphere and which carries out and it makes react in the state of 1 acid Carbon pressurization using a resisting pressure reaction apparatus Both -- it is possible.
[0079] The compound and formula (XII) of the (4) above-mentioned types (VII- 1) [0080] [-izing 9]
Inside of [type<img file="WO2005041663A1_D0011.tif" />Facial expression p is as above-mentioned --] whose Y is a desorption machine
By coming out and making the compound expressed react, the compound of the above-mentioned formula (I) or its salt is manufactured. How to carry out.
[0081] as the desorption machine expressed with , The, and upsilon to the above-mentioned process (4) -- halogen and Xia ON alkoxy etc. -- it is mentioned. This reaction passes and is fatty series carbonization water, such as Xan and octane, to Xan and cyclo. Matter; Diiso propyl ether, Ether system Melting, such as a tetrahydro franc and dimethoxyethane Bottom of existence of singleness [ of intermediation ] or mixed inactive solvent, and-100"C -- With the reaction temperature of 120"C It is desirable to be carried out. It is also possible by making transition metal complexes, such as nickel, palladium, and iron, exist catalytically to promote a reaction more.
[0082] (5) type (XIII):
[0083] [-izing 10]<img file="WO2005041663A1_D0012.tif" />
[0084] The compound expressed with [the inside of a formula, and X and n are as above-mentioned], and formula (XIV):
[0085] [-izing 11]
[0086] [type<img file="WO2005041663A1_D0013.tif" />R<sup>2</sup>the compound by which "and p are expressed with] which is as above-mentioned -- Lewis acid -- or -- Method of making it reacting under existence of a dehydrator and manufacturing the compound of the above-mentioned formula (I), or its salt.
[0087] the reaction of a process (5) -- the bottom of existence of a solvent, and 0"C -- being carried out with the reaction temperature of 200"C -- Desire -- better it is -- . As Lewis acid or a dehydrator, they are P o, a Oxy phosphorus chloride, polyphosphoric acid, and sulfuric acid, for example,
2 5
Xyloca report diimide (DCC) etc. are mentioned to Dicyclo. moreover -- if it does not participate in a reaction as a solvent, even if it will use which solvent -- Well -- for example Aromatic hydrocarbon, such as halogenated hydrocarbon, such as 1, 2-dichloro ethane, and salt Y methylene, benzene, Cros mouth benzene, dichlorobenzene, and nitrobenzene, etc. are mentioned, and the mixture of these solvents is used. A little.
[0088] They are a compound of (6) above-mentioned type (I), or a manufacturing method of the salt,
(a) Make the compound and halogenation agent of the above-mentioned formula (XIII) react, and it is formula (XV):
[0089] [-izing 12]<img file="WO2005041663A1_D0014.tif" />
[0090] the inside of a formula, and X and n [are as above-mentioned -- compound by which Hal is expressed with] which is a halogen atom The 1 process to acquire -- and
(b) Flea Dell Kula of the compound of formula (XV) obtained at The 1 process, and the compound of the above-mentioned formula (XIV) Method constituted from The 2 process of obtaining the compound of the above-mentioned formula (I) by the Bud reaction.
[0091] The reaction of The 1 process of a process (6) can be adapted in the usual acid Halogen reaction. this reaction -- the bottom of existence of an inactive solvent or nonexistence -- zero -- being carried out with the reaction temperature of 200"C -- Desire better -- There. As a halogenation agent used at this reaction, they are a fluorinating agent, a chlorinating agent, and bromination. Although an agent etc. are mentioned, they are chlorinating agents, such as salt I - Le, a Oxy phosphorus chloride, and oxalyl chloride. It is desirable to use it. The Friedel craft reaction of The 2 process of a process (6) is Existence of a catalyst. It is -78"C with in Shimo, the inside of a solvent, or a non-solvent. -- It is desirable to carry out with the reaction temperature of power 0 °C 1 100-degreeC which can be performed with the reaction temperature of 200"C. As a catalyst which can be used at this reaction, they are Lewis acid catalysts, such as FeCl, A1C1, SnCl, ZnCl, TiCl, SbCl, BF, and BiCl, and trifluoro.
3 3 4 2 4 5 3 3
Methanesulfonic acid and graphite are mentioned. Power in which an un-active solvent is used under reaction conditions as a solvent, for example, 1, 2-dichloro ethane, a methylene chloride, Cros mouth benzene, Dichlo mouth benzene, nitrobenzene, etc. are mentioned The mixture of these solvents may be used. Friede ♪ Crafts Chemistry (01ah, G.A. work) can be manufactured from composition or guidance-izing * This to reference.
[0092] The compound of the above-mentioned formula (XIII) used as materials for manufacture of a process (5) and a process (6) is obtained by carrying out acid Y of the compound of the above-mentioned formula (VII-2). As an oxidizer, the usually used inorganic matter or an organic oxidant can be used. React to dry ice directly, or the compound of the above-mentioned formula (VII- 1) is made to react to the Krol carbonic acid Ethyl, and it is obtained by subsequently hydrolyzing. Or it is a direction of literature known about substitution pyridinecarboxylic acid or its derivative. It is a method and is composition or guidance-ized To to reference, for example about J.Heterocycli Chem., 36, and 653 (1999). It can manufacture from To * This. The 4th edition of The edited by the Chemical Society of Japan can manufacture "experimental science lecture 22, organic synthesis IV, and 1992" composition or by guidance-izing to reference.
[0093] Also in the benzoyl pyridine derivative denoted by formula (I), it is formula ():
[0094] [-izing 13]
<img file="WO2005041663A1_D0015.tif" />
[0095] B is CX when A is - N =, the inside of [type, and.<sup>4</sup>= Be; B is N when A is - CH =.
= Be; X<sup>1</sup>And X<sup>2</sup>They are a halogen atom, an alkoxy group, a hydroxyl group, and An alkyl to Are independence. It is a Le machine, CF machine, or an alkylthio group, and is;X.<sup>3</sup>Is a hydrogen atom, a halogen atom, Alkoxy
3
It is a basis, a Alkyl machine, CF machine, or an alkylthio group, and is;X.<sup>4</sup>Is a hydrogen atom, a halogen atom,
3
They are an alkoxy group, a Alkyl machine, CF machine, or an alkylthio group; R<sup>1</sup>It is a Is alkyl machine and is Ah.
3
Ri; R<sup>2</sup>'is an alkoxy group; p is 1, 2, or 3; R<sup>2</sup>"and R<sup>2</sup>"' is an alkoxy group.
The compound denoted by ] is Desirable .
[0096] A is - CH= at the compound denoted by the above-mentioned formula (gamma), and it is B - The compound in the case of being N =, i.e., a formula, (gamma -- 1):
[0097] [-izing 14]
<img file="WO2005041663A1_D0016.tif" />
[X<sup>1</sup>X<sup>2</sup>X<sup>3</sup>,<img file="WO2005041663A1_D0017.tif" />R<sup>2</sup>R<sup>2</sup>"and R<sup>2</sup>A is - N = and B is [ the compound expressed with 'being as above-mentioned], and ] CX.<sup>4</sup>(= The compound, i.e., the formula, in a certain case : (I, 1 2) [0098] [-izing 15])
<img file="WO2005041663A1_D0018.tif" />
[X<sup>1</sup>x<sup>2</sup>x<sup>3</sup>x<sup>4</sup>,<img file="WO2005041663A1_D0019.tif" />R<sup>2</sup>', R<sup>2</sup>"and R<sup>2</sup>The compound expressed with '" being as above-mentioned] is Ah. To.
[0099] In the inside of the compound denoted by the above-mentioned formula (gamma 1), 3 -(2,3,4-trimethoxy-6-methyl Benzoyl)- 4-Bromo-5-Cros mouth - 2-methoxy pyridine (CompositeNo.1), 3- (2,3,4-Trimethoxy 6-Methyl benzoyl) -5-Cros Mouth - 4-Ethyl-2-Methoxy Pyridine (CompositeNo.2), 3-(4,5-Dimethoxy-2-methylbenzoyl)- 4,5-dichloro 2-methoxy pyridine (CompositeNo.3), 3-(5-Ethoxy-4-methoxy-2-methylbenzoyl)- 4,5-dichloro 2-methoxy pyridine (CompositeNo.4), 3-(2,3,4-trimethoxy-6-methylbenzoyl)-4-Bromo-5-Cros mouth - 2-ethoxy pyridine (compound No.5), 3- (2, 3, 4-Trimethoxy 6-Methylbenzoyl) -5-Cros Mouth - 2-Ethoxy 4-Melpi Lysine (CompositeNo.6), 3 -(2,3,4-trimethoxy-6-methylbenzoyl)- 5-Bromo-4- Cros mouth - 2-ethoxy pyridine (CompositeNo.7), 3-(2,3,4-trimethoxy-6-methylbenzoyl)-4-Cros mouth - 5-Ode-2-methoxy pyridine (CompositeNo.8), 3-(2,3,4-trimethoxy-6-methylbenzoyl)-5-Ode-2,4-dimethoxy pyridine (CompositeNo.9), 3-(2, 3, 4-trimethoxy-6 - methylbenzoyl)-5-Cros mouth - 2-methoxy-4-methyl Thiopi lysine (CompositeNo.10), 3-(2,3,4-trimethoxy-6-methylbenzoyl)-5-Cros mouth - 2,4-dimethoxy pyridine (Composite item No. l l), 3-(2, 3, 4-trimethoxy-6-methylbenzoyl)-4, 5-dibromo -2-methoxy pyridine (compound No.12) and 3-(2, 3,4-trimethoxy-6-methylbenzoyl)- 4-Bromo-2-methoxy-5-methyl pyridine (CompositeNo.13), 3-(2, 3,4-trimethoxy-6-methylbenzoyl)- 5-Bromo-4-trifluoromethyl-2-methoxy pyridine (CompositeNo.14), 3-(2,3,4-trimethoxy-6-Methyl benzoyl)- 4,5-dichloro 2-methoxy pyridine (CompositeNo.15), 3-(2,3,4-Trimetuki Si-6-methylbenzoyl)-2, 4-dichloro 5-methyl pyridine (CompositeNo.16), 3-(2,3,4-Trimethoxy-6-methylbenzoyl)-2,4-dichloro 5-Ode pyridine (CompositeNo.17), 3-(2,3,4-trimethoxy-6-methylbenzoyl)-2-Fluoro- 4-Ode-5-methyl pyridine (CombinationNo.18), 3-(2, 3, 4-trimethoxy-6-methylbenzoyl)-2-Fluoro- 4, 5-Dimethy kana lysine (CompositeNo.19), 3-(2,3,4-trimethoxy-6-methylbenzoyl)- 2-methoxy 4,5-Di Methyl pyridine (CompositeNo.20), 3-(2-ethoxy 3, 4-dimethoxy-6-methylbenzoyl)-2-ethoxy 4, 5-Dimethy kana lysine (CompositeNo.21), 3 -(2,3,4-trimethoxy-6-Methyl benzene)- 4, 5-Dimethyl-2-methyl Thiopi lysine (CompositeNo.22), 3-(2,3,4-trimethoxy-6-methylbenzoyl)-5-Bromo-4-Cros mouth - 2-methoxy pyridine (CompositeNo.23), 3-(2,3,4-trimethoxy-6-methylbenzoyl)-4-Cros mouth - 2-methoxy-5-methyl pyridine (CombinationNo.24), 3-(2, 3,4-trimethoxy-6-methylbenzoyl)-2-Cros mouth - 5-truffe Luoromethyl-4-methyl pyridine (CompositeNo.25), 3-(2, 3,4-trimethoxy-6-methylbenzoyl)-5-Tri-Fluro methyl-2-methoxy 4-methyl pyridine (CompositeNo.26), 3-(2,3,4-trimethoxy-6-methylbenzoyl)-2,4-dichloro 5-trifluoromethyl pyridine (CompositeNo.27), 3-(2,3,4-trimethoxy-6-methylbenzoyl)-4-Cros mouth - 5-trifluoromethyl-2 - Methoxy Pyridine (CompositeNo.28), 3-(2, 3,4-trimethoxy-6-methylbenzoyl)-5-Cros mouth - 4-Ha - roux 2-methoxy pyridine (CompositeNo.29), 3-(2,3,4-trimethoxy-6-methylbenzoyl)-5-Cros mouth - 4-Fluoro methyl-2-methoxy pyridine (CompositeNo.30), 3-(2,3,4-Trimetuki Si-6-methylbenzoyl)- 5-Bromo-4-Fluoro methyl-2-methoxy pyridine (Composite item No. 31), 3-(2, 3, 4-trimethoxy-6-methylbenzoyl)- 4-Fluoro methyl-2-methoxy-5-Methi Kana lysine (CompositeNo.32), 3-(2, 3,4-trimethoxy-6-methylbenzoyl)-5-Cros mouth - 4-Gifuro methyl-2-methoxy pyridine (CompositeNo.33), 3 -(2,3,4-trimethoxy-6-Methyl benzene)- 5-Ethyl-4-trifluoromethyl-2-methoxy pyridine (CompositeNo.34), 3-(2,3,4-trimethoxy-6-methylbenzoyl)-5-Cros mouth - 2-methoxy-4-methyl pyridine (CombinationNo.35), 3-(2, 3, 4-trimethoxy-6-methylbenzoyl)- 5-Bromo-2-methoxy-4-Methi Kana lysine (CompositeNo.36), 3-(2, 3,4-trimethoxy-6-methylbenzoyl)-4-trifluoro Methyl-2-methoxy-5-methyl pyridine (CompositeNo.37) and 3-(4, 5-dimethoxy-2-methyl benzoyl)-5-Cros mouth - It is still more desirable to use at least one sort of compounds chosen from the group which comprises 2-methoxy-4-methyl pyridine (CompositeNo.38).
In the inside of the compound denoted by the above-mentioned formula (I, 1 2), 4 -(2,3,4-trimethoxy-6-methylbenzoyl)- 2,5-dichloro 3-trifluoromethyl pyridine (CompositeNo.39), 4 (2,3,4 [ -- Methylbenzoyl ] -- Trimethoxy -- Six) -- 2 Chloro 3 -- Trifluoromethyl 5 -- Methoxy Pyridine (CompositeNo.40), 4 (2,3,4 -- Trimethoxy 6 Methylbenzoyl) -- [ Roux 5 -- Methoxy Pyridine (CompositeNo.41), ] Two -- Bromo 3 -- Truffe Luolomethi 4-(2,3,4-trimethoxy-6-methylbenzoyl)-2,3,5-Tori Cros mouth pyridine (CompositeNo.42), 4-(2,3,4-trimethoxy-6-methylbenzoyl)-3,5-dichloro pyridine (CompositeNo.43) and 4-(2,3,4-trimethoxy-6-methylbenzoyl)-3-Cros mouth - 5-methoxy pyridine (CompositeNo.44), 4 - (benzo[ 2, 3, / 4-trimethoxy-6-methyl ]) A ring -2 Bromo-3-Cros mouth - 5-methoxy pyridine (CompositeNo.45) and 4--(2,3,4 [ Methylbenzoyl ] -- trimethoxy -- six) 3 -- From the group which Bromo 5 methyl pyridine (CompositeNo.46) power also comprises It is still more desirable to use at least one sort of compounds chosen.
[0101] Especially the disinfectant constituent of the present invention is useful as a disinfectant for agriculture and horticulture. As a disinfectant for agriculture and horticulture, it is Japanese noodles This disease of rice blast [ of a rice ], Cochliobolus miyabeanus, and sheath blight; wheat, for example, Red Disease, a rust disease, Snow mold disease, loose smut, Pseudocercosporella herpotrichoides, Septoria tritici, Leptosphaeria nodorum; sunspot disease of a citrus, So Illness; the A 2 rear disease of an apple, Japanese noodles This disease, a spot brown stem rot, a failure disease; failure disease of a pear, Purple blotch; The brown rot of a peach, a failure disease, Phomopsis rot; black and Disease of Budo, * Rot, Japanese noodles This disease, and Be and illness; the anthrax of power , a brown stem rot; anthrax of © Li, Japanese noodles This disease, Mycosphaerella melonis, Be and illness; tomato A ring spot, leaf mold, an epidemic; the purple blotch of brassica family vegetables, the early blight of a potato, an epidemic; Í Japanese noodles This disease of Chigo; effective in control of disease, such as a gray mold disease of various crops, and sclerotinia rot. The control effect which was especially excellent in Japanese noodles This disease of wheat and greenstuff and the rice blast of a rice is shown. Up It is effective also in control of the soil disease caused with plant pathogenic microbes, such as a La [ It was, a fusarium bacillus, the Pythium bacillus, a Rhizoctonia, the Bertie Psium bacillus, and Plasmodioho - ] bacillus.
[0102] A plurality of active ingredients which constitute a present invention disinfectant constituent are the same as that of the conventional agricultural-chemicals tablet, each -- mixing a seed auxiliary agent -- various forms, such as a powder agent, a grain agent, granulation wettable powder, wettable powder, a water suspension, oily suspension , an aqueous agent, an emulsion, liquid medicine, a paste agent, an aerosol agent, and very-small-quantity dusting powder, -- Made It is used, an agent's carrying out. however -- using in the field concerned usual only in the power which suits the object of the present invention , -- Being done -- oh, it can be made a loose tablet form. As an auxiliary agent used for a tablet, it is Silica. Algae soil, slaked lime, calcium carbonate, Talc, white carbon, kaolin, bentonite, power A cage night and mixture of an auction site, Solid carriers, such as clay, sodium carbonate, bicarbonate of soda, Glauber's salt, zeolite, and starch; water, toluene, xylene, solvent naphtha, dioxane, and acetone , It is Xan to iso holon, methyl isobutyl ketone, Cros mouth benzene, and cyclo, Dimethylsulfoxide, Dimethylform amide, Dimethylaceto amide, N -- Methyl 2 -- A pylori boss, Al Solvents, such as Kohl; fatty acid salt, Benzoic acid salt, Alkyl sulfo succinic acid salt, Dialkyls lehosuccine acid chloride, Polycarboxylic acid salt, alkyl-sulfuric-acid ester salt, alkyl sulfate, Alkir reel sulfate, Alkyl diglycol ethereal sulfate salt, alcoholic sulfuric acid S Tell salt, Alkyl-sulfonic-acid salt, alkylarylsulfonic acid, A riel sulfonic acid Salt, rig-A sulfonic acid salt, Alkyl jefe-Le ether disulfon acid chloride, Pori Stille Rurin [ Nonson acid chloride, Alkyl phosphorus acid ester salt, an alkyl aryl phosphate, and Styli Lari - ] acid chloride, Polyoxyethylene-alkyl-ether sulfate ester salt, poliomyelitis Kishe Thiren alkyl aryl ethereal sulfate salt, Polyoxy ethylene Alkylaryle Tell sulfate ester salt, polyoxyethylene-alkyl-ether phosphate, Poliomyelitis Kisech Ren Alkyla reel phosphate, salt of a Naphthalene sulfonic acid formalin condensation thing Surface-active agent Na spreader of a negative ion system [ like ]; sorbitan fatty acid ester glycerin fat Fatty acid ester and a fatty acid Polyda reseller -- an id and fatty acid alcoholic Polyda recall ether, Acetylene glycol, acetylene alcohol, Oxyalkylene block polymer, Polyoxy ethylene alkyl ether, polyoxyethylene alkyl aryl ether, Polyoxy ethylene Styrill reel ether, polyoxy-ethylene-glycol Alkyl ether, Polyoxy ethylene fatty acid ester, polyoxy ethylene sorbitan fat Acid ester Polyoxyethylene glycerine fatty acid ester, polyoxy ethylene hardening Hi surfactant exhibition of a non-ion system like Massey oil and polyoxypropylene fatty acid ester Adhesive; Olive oil, kapok oil, castor oil, palm oil, camellia oil Palm oil, sesame oil, Corn They are [ Si oil rice-bran oil, peanut oil, cottonseed cake oil, soybean oil, rapeseed oil, linseed oil, and ] oil and liquefied Para as. Vegetable oil, mineral oil, etc., such as a fin, are mentioned. These auxiliary agents deviate from the object of the present invention. Unless it carries out, it can choose from what was known for the field concerned, and can use. moreover -- increase -- Connoisseurs, such as a quantity agent, a thickener, an antisettling agent, an antifreeze, dispersion stabilizer, a medical-harm mitigation agent, and an antifungal agent The various auxiliary agents by which usual state use is carried out can also be used. an active ingredient compound and various auxiliary agents a combination rate -- general -- 0.005:99.995 -- 95 : 5 -- desirable -- 0.2 : 99.8 -- 90 : It is 10. this , -- a tablet -- or it uses it as it is on the occasion of actual use -- or diluents, such as water, -- predetermined -- dark -- It can dilute to a degree, and can add and use various spreading agents if needed.
[0103] Plant disease using the disinfectant constituent of the present invention for the plant for agriculture and horticulture A control method is also included in the present invention. the operating concentration of the disinfectant constituent from a book -- object crops and use although it changes with differences between a method, a tablet form, the amount of application, etc. and cannot generally specify -- forage place common per active ingredient, when it is Reason -- 0.1 -- 10,000 ppm -- desirable -- 11 -- it is 2,000 ppm. the case of soil processing -- usually -- 10 -- it is desirable 100,000 g/ha -- 200 -- It is 20,000 g/ha.
[0104] Various tablets of a present invention disinfectant constituent, or the application of the dilution thing, Usually, generally it is Line. The application method, i.e., spraying, which has broken, soil application (for example, spraying, spraying, misting, Atomizing, Scattering, water surface application, etc.) (mixing, irrigation, etc.), surface application (an application, Dressing, covering, etc.), etc. can perform. It can also be used by what is called the super-high concentration small-quantity sprinkling method (ultra low volume). Containing an active ingredient 100% in this method It is possible.
[0105] The suitable mixed weight ratio of the benzoyl pyridine derivative expressed with !, The, and formula (I) by the disinfectant constituent of the present invention or its salt, and other disinfectants, general -- 1:10000 -- 10000 : 1 and Desire better -- To -- 1:1000 -- 1000 : 1 -- further -- desirable -- 1 : 200 -- 200 : It is 1.
EXAMPLE
[0106] Although the synthetic example concerning the present invention is indicated below, these do not limit the present invention.
[0107] Synthetic example 1
3-(2,3,4-trimethoxy-6-methylbenzoyl)- composition of 4,5-dichloro 2-methoxy pyridine (CompositeNo.15)
(a) the inside of the solution which dissolved 34.2 g (340mmol) of diisopropylamine in 400 ml of tetrahydro francs - 20"C -- n-butyl lithium (it is Xan solution to 1.57 mol/l) 222 ml is dropped -- agitating for 1 hour It was. solution - it cools to 78"C -- the solution which dissolved 32.0 g (330mmol) of 2-Fluoro pyridine in 50 ml of tetrahydro francs is added -- agitating for 4 hours and preparing 2-Fluoro- 3-pyridyl lithium It was. Subsequently, solution which dissolved iodine 87. lg (341mmol) in this solution at 150 ml of tetrahydro francs It added and agitated for 1 hour. 200 ml of water is added to a mixture, a reaction is stopped, and they are the bottom of decompression, and Tetra. Dollo Fran was distilled off. drying and filtering an organic layer with sodium sulfate after extraction with ether a solvent is distilled off under decompression -- 2-Fluo mouth - 67.4 g (92% of rough yield) of rough products of 3-Ode pyridine It obtained.
1 H-NMR (CDC1, 400muetazeta) : delta = (ppm) 6.91 -- 6.88 (m, lH), 8.08 -- 8.12 (m, 2H)
3
[0108] Inside of the solution which dissolved 30.2 g (302mmol) of (b) diisopropylamine in 380 ml of tetrahydro francs - It is n-butyl lithium (it is Xan solution to 1.57 mol/l) at 20"C. 189 ml is dropped and it agitates for 1 hour. It was. Solution - 2-Fluo mouth which cooled to 78"C and was acquired at the process (a) - The rough raw of 3-Ode pyridine The solution which dissolved 67.4 g (302mmol) of products in 100 ml of tetrahydro francs is added, It agitated for 1 hour and made 2-Fluoro- 4-Ode-3-pyridyl lithium carry out opposite-sex Y of and the 2-Fluoro- 3-Ode-4-pyridyl lithium generated in early stages. 300 ml of water is added to a reaction mixture, a reaction is stopped, and it is a decrease. Pressing down and a tetrahydro franc were distilled off. ether -- after extraction and an organic layer -- sodium sulfate -- Dry it Dry and filters and distills off a solvent under decompression -- 2-Fluo mouth - 59.3 g (89% of rough yield) of rough products of 4-Ode pyridine were obtained.
^ -NMRCCDCl, 400 MHz : delta = (ppm) 7.33 (d, 1H, J= 2.8 Hz), 7.51 (d, 1H, J= 5.2 Hz),
3
7.88(dd, 1H, J=5.2Hz, 2.8Hz)
[0109] 59.4 g (253mmol) of rough products of the 2-Fluoro- 4-Ode pyridine obtained at the (c) process b -- meta--- adding Knoll 500ml and making it dissolve -- 21.5 g (398mmol) of sodium methoxide -- mosquito Scare 3-hour heating It flowed back. 300 ml of water was suspended for the mosquito Scare reaction, and methanol was distilled off under decompression. Ether The organic layer was dried and filtered with sodium sulfate after extraction, the solvent was distilled off under decompression, and 56.7 g (91% of rough yield) of rough products of 4-Ode-2-methoxy pyridine were obtained.
1 H-NMR (CDC1, 400muetazeta) : delta = (ppm) 3.86 (s, 3H), 7.12-7.16 (m, 2H), 7.79 (d, lH, J= 5.6 Hz)
3
[0110] 50.6 ml (2 mol/l tetrahydrofuran solution) of (d) isopropyl magnesium chloride is ice-cooled, It is Tetra about 19.8 g (84.3mmol) of rough products of the 4-Ode-2-methoxy pyridine obtained at the process (c). The solution which dissolved in 80 ml of Dollo Fran is added, it agitates at 1 hour 0 degreeC and 1 hour of room temperature -- 2-Metoki See 4-pyridyl magnesium chloride was prepared. Then, 16.9 g (127mmol) of N-Cros mouth succinic acid imide was added gradually, and it agitated at room temperature for 1 hour. 100 ml of water is suspended for mosquito Moe and a reaction. It carried out and distilled off the tetrahydro franc under decompression. ether -- after extraction and an organic layer -- sulfuric acid Satellite it dries and filters by Beam and distills off a solvent under decompression -- 4-Cros mouth - Rough product ll.Og (91% of rough yield) of 2-methoxy pyridine was obtained. (ppm) H-NMR(CDC1, 400 MHz) delta =3.91 (s, 3H), 6.70 (d, 1H, J= 2.0 Hz), 6.81 (dd) :
3
1H, J=6.0Hz, 2.0Hz), 7.99(d, 1H, J=6.0Hz)
[0111] 4-Cros mouth acquired at the (e) process (d) - It is Di about 10.0 g (69.9mmol) of rough products of 2-methoxy pyridine. It is made to dissolve in 100 ml of methyl Holm amide. It is a Powerhouse room about 37.2 g (279mmol) of N-Cros mouth succinic acid imide. It agitated by Warm for 12 hours. 400 ml of water is added, a reaction is stopped, and they are after extraction and an organic layer with ether. A saturation salt solution washes, it dries and filters with sodium sulfate, a solvent is distilled off under decompression, and it is 4,5. - 9.10 g (73% of rough yield) of rough products of dichloro 2-methoxy pyridine were obtained.
^ -NMRCCDCl, 400muetazeta: delta = (ppm) 3.90 (s, 3H), 6.85 (s, lH), 8.14 (s, lH)
3
[0112] which trickled 15.1 ml of n-butyl lithium (it is Xan solution to 1.57 mol/l) by and -20-degreeC into the solution which dissolved 2.40 g (23.7mmol) of (f) diisopropylamine in 30 ml of tetrahydro francs, and was agitated for 1 hour. Solution - 4,5-dichloro 2-methoxy pyridine which cooled to 78"C and was obtained at the process (e)
the solution which dissolved 4.22 g (23.6mmol) in 20 ml of tetrahydro francs is added -- it agitated for 2 hours and prepared 4 and 5-dichloro 2-methoxy-3-pyridyl lithium. Come out and it is 2, 3, and 4-Trimet to this solution. 5.00 g (23.8mmol) of Toxy-6-methyl benzaldehyde was dissolved in 20 ml of tetrahydro francs. Solution was added and it agitated for 30 minutes. 50 ml of water is added to a mixture, a reaction is stopped, and they are the bottom of decompression, and tetra. The hydronalium franc was distilled off. an organic layer is dried and filtered with sodium sulfate after extraction with ether -- distilling off a solvent under decompression Silica gel column chromatography refined and it obtained 4.66 g (51% of yield) of methanol (4 (2, 3, 4-Tori methoxy-6-methyl failure), 5-dichloro 2-methoxy 3-pyridyl).
(ppm) 1 H-NMR(CDC1, 400 MHz) delta =2.32 (s, 3H), 3.52 (s, 3H), 3.77 (s, 3H), 3.82 (s) :
3
3H), 4.11(s, 3H), 5.32(d, 1H, J=10.0Hz), 6.21(d, 1H, J=10.0Hz), 6, 55(s, 1H), 8.07(s, 1H)
[0113] it was obtained at the (g) process (f) (2, 3, 4-trimethoxy-6-methyl failure) -- the solution in which 30 ml of toluene was made to dissolve 4.66 g (12.0mmol) of methanol (4, 5-dichloro 2-methoxy - 3-pyridyl), 2 oxidization Mosquito Moe and 2-hour heating at reflux were performed for 13.8 g (159mmol) of manganese. Celite after cooling to room temperature After using and removing 2 acid Y manganese, Toluene is distilled off under decompression and it is silica gel Column. Mouth Matography 1 refines and it is 3-(2, 3,4-trimethoxy-6-methylbenzoyl)-4,5-Dichlo. Mouth - 2.98 g (65% of yield) of 2-methoxy pyridine was obtained. (ppm) H-NMR(CDC1, 400 MHz) delta =2.46 (s, 3H), 3.45 (s, 3H), 3.74 (s, 3H), 3.90 (s) :
3
3H), 4.00(s, 3H), 6.55(s, 1H), 8.13(s, 1H)
[0114] Synthetic example 2
3-(2, 3, 4-trimethoxy-6-methylbenzoyl)-2 - methoxy -- composition of 4 and 5-Dimethy kana lysine (CompositeNo.20)
(a) the inside of the solution which dissolved 4.02 g (39.8mmol) of diisopropylamine in 70 ml of tetrahydro francs - 78"C -- n-butyl lithium (it is Xan solution to 1.57 mol/l) 26.5 ml is dropped -- it agitated for 30 minutes. this solution -- 2-Fluo mouth - the solution which dissolved 4.42 g (39.8mmol) of 5-methyl pyridine in 18 ml of tetrahydro francs is added -- it agitates for 4 hours -- 2-Fluoro- 5-methyl-3-pyridyl lithium It prepared. subsequently -- dissolving 10.1 g (39.8mmol) of iodine in this solution at 27 ml of tetrahydro francs Solution is added -- it agitated for 2 hours. 16 ml of water and 120 ml of sodium subsulfite solution are supplied. drying and filtering an organic layer with magnesium sulfate after extraction with ether -- the bottom of decompression -- solvent the rough product obtained by distilling off is refined in silica gel chromatography -- 3.15 g (33% of yield) of 2-full Oro- 3-Ode-5-methyl pyridine was obtained.
^ -NMRCCDCl, 400 MHz : delta = (ppm) 2.27 (s, 3H), 7.95 (m, 2H)
3
[0115] Inside of the solution which dissolved 1.34 g (13.3mmol) of (b) diisopropylamine in 27 ml of tetrahydro francs - which trickled 8.90 ml (it is Xan solution to 1.57 mol/l) of n-butyl lithium, and was agitated by 78"C for 30 minutes. It agitates for 1 hour, after adding the solution which dissolved 3.15 g (13.3mmol) of 2-Fluoro- 3-Ode-5-methyl pyridine obtained at the process (a) in this solution at 5 ml of tetrahydro francs, To the first stage 2-Fluoro- 4-Ode-5-methyl-3-pyridyl lithium was made to carry out opposite-sex Y of the generated 2-Fluoro- 3-Ode-5-methyl-4-pyridyl lithium. the solution which dissolved 2.79 g (13.3mmol) of 2, 3, and 4-trimethoxy-6-methyl benzaldehyde in the reaction mixture at 5 ml of tetrahydro francs -- Addition is carried out -- it agitated for 2 hours. They are after extraction and an organic layer with mosquito Moe and ether after Temperature rising and about 50 ml of water to room temperature. It dries with magnesium sulfate, He is Si about the rough product obtained by filtering and distilling off a solvent under decompression. It refines in Rica Gel chromatography, (2, 3, 4-trimethoxy-6-methyl failure) (2-full Aro- 4-Ode-5-methyl-3-pyridyl) 4.45 g (75% of yield) of methanol was obtained.
^ (ppm) -NMRCCDCl and 400MHzdelta =2.21 (s, 3H), 2.42 (s, 3H), 3.72 (s, 3H), 3.79 (s) :
3
3H), 3.81(s, 3H), 4.97(d, 1H, J=10.0Hz), 6.08(d, 1H, J=10.0Hz), .46(s, H), .86(s, H)
[0116] it was obtained at the (c) process (b) (2, 3, 4-trimethoxy-6-methyl failure) -- solution in which 130 ml of toluene was made to dissolve 4.35 g (9.70mmol) of methanol (2-Fluoro- 4-Ode-5-methyl - 3-pyridyl) Into Mosquito Moe and 2-hour flowing-back heating were performed for 17.3 g (0.18 mol) of 2 acid Y manganese. distilling off the bottom toluene of decompression, after removing 2 acid Y manganese using Celite after [ ] cooling to room temperature -- Silica gel chromatography -- it Purification gruffy -- 3-(2, 3, 4-trimethoxy-6-methylbenzoyl)- 2-Fluo<img file="WO2005041663A1_D0020.tif" />; Melting point 140-141" 2.80<sub>Section</sub>(65% of yield) was obtained.
^ -NMRCCDCl, 00 MHz : delta = (ppm) 2.41 (s, H), .50 (s, H), 3.42 (s, 3H), 3.90 (s, 3H),
3
3.74(s, 3H), 6.57(s, 1H), 7.94(s, 1H)
[0117] 1.50 g (3.37mmol) of 3-(2,3,4-trimethoxy-6-methylbenzoyl)-2-Fluoro- 4-A-Do- 5-methyl pyridine obtained at the (d) process (c), 1.40 g (10.1mmol) of potassium carbonate, and 0.39 g (0.34mmol) of tetrakis palladium (the Tori fail phosphine), 15 ml of dioxane, and 50% Trimethylboro 0.42 g (1.67mmol) of A xin are mixed -- flowing-back heating was performed for 6 hours. Celite after cooling to room temperature It filters and is after washing at acetic acid Ethyl and a tetrahydro franc, distilling off a solvent under decompression -- profit refining a Was done rough product in silica gel chromatography -- 3- (2, 3, 4-trimethoxy-6-Methyl benzoyl) -2-Fluoro- 4 and 0.79 g (70% of yield) 5-Dimethy kana lysine (CompositeNo.19) It obtained.
^ (ppm) -NMRCCDCl and 00MHzdelta =2.28 (s, 3H), 2.32 (s, 3H), 2.42 (s, 3H), 3.35 (s) :
3
3H), 3.74(s, 3H), 3.90(s, 3H), 6.57(s, 1H), 7.94(s, 1H)
[0118] 3-(2, 3,4-trimethoxy-6-methylbenzoyl)-2-full Oro- 4,5 obtained at the (e) process (d) - In the solution in which 2.5 ml of methanol was made to dissolve 0.20 g (0.60mmol) of Dimethyl pyridine, 60% hydrogenation The solution in which methanol lml was made to dissolve 0.06 g (1.5mmol) of sodium is dropped, and it is 16-hour Reflux. It became hot. After cooling to room temperature, 5 ml of water is added, and it weak-acidity-izes with dilute hydrochloric acid, and is after extraction with ether, Food It washes with salt water, an organic layer is dried and filtered with magnesium sulfate, and a solvent is distilled off under decompression, the obtained rough product is refined in silica gel chromatography -- 3-(2, 3, 4-trimethoxy-6-methylbenzoyl)-2 - methoxy -- 89.0 mg (43% of yield) of 4 and 5-Dimethy kana lysine was obtained. ^-NMRCCDCl , 400MHz) : delta (ppm)=2.19(s, 3H), 2.21(s, 3H), 2.39(s, 3H), 3.24(s, 3H), 3.70(s, 3H), 3.74(s, 3H), 3.87(s, 3H), 6.53(s, 1H), 7.87(s, 1H)
[0119] Synthetic example 3
3-(2,3,4-trimethoxy-6-methylbenzoyl)-5-Bromo-4-Cros mouth - Composition of 2-methoxy pyridine (compound No.23)
(a) 5.76 g (40.1mmol) of 4-chloro 2-methoxy pyridine is dissolved in 20 ml of Dimethylformamide -- the Dimethylform amide solution (20 ml) of 8.01 g (a 98% article and 44.1mmol) of N-Bromo succinic acid imide was dropped over 30 minutes. Since unreacted materials were checked after agitating for two days at room temperature, 2.85 g (a 98% article and 16mmol) of N-Bromo succinic acid imide was further agitated at mosquito Moth room temperature on the 3rd. The reaction mixture was poured into 250 ml of water, and ether (100 ml each) extracted 3 times. an organic layer -- water (100 ml) and sodium subsulfite solution (100 ml) -- subsequently a saturation salt solution (100 ml) washes -- Sulfur It dried and filtered with acid magnesium and distilled off the bottom solvent of decompression. the obtained rough product -- silica gel chromatography refines -- 5-Bromo-4-Cros mouth - 7.10 g (80% of yield) of 2-methoxy pyridine was obtained.
^ -NMRCCDCl 400MHZ: delta = (ppm) 3.91 (s, 3H), 6.89(s, lH)ゝ 8.28 (s, lH)
3,
[0120] (b) 3.84 g (27mmol) of 2, 2, 6, and 6-tetramethylpiperidine was dissolved in 36 ml of tetrahydro francs. It is under an argon air current to solution, 18.3 ml (they are Xan solution and 27mmol to 1.57 mol/l) of n-butyl lithium is dropped by 0 degreeC -- it agitated by 0"C for 30 minutes. Obtained solution - It cools to 78"C and is a 5_Bromo-4-Cros mouth. - Solution which dissolved 6.10 g (27mmol) of 2-methoxy pyridine in 24 ml of tetrahydro francs Attach mosquito A is carried out, It agitates at the temperature for 2 hours, and is a 5-Bromo-4-Cros mouth. - 2-methoxy-3-pyridyl lithium It prepared. Subsequently, he is Thet about 2, 3, and 4-trimethoxy-6-methyl benzaldehyde 5.50g (26mmol). The solution which dissolved in 24 ml of La hydro francs was added, and it agitated at the temperature for 1 hour. Reaction mixture They are after Temperature rising and acetic acid to mosquito Moe and room temperature about 37 ml of saturation chlorination Ann A-Um solution, and then 150 ml of water. It extracted 3 times by Ethyl (150 ml each). A saturation salt solution (100 ml) washes an organic layer, and it is a sulfuric acid mug. It dried and filtered by Nessim and distilled off the solvent under decompression. It is silica gel about the obtained rough product. It refined in chromatography and obtained 6.53 g (56% of yield) of methanol (5(2, 3, 4-trimethoxy-6-methyl failure)-Bromo-4-Croro- 2-methoxy 3-pyridyl).
^ -NMRCCDCl 400MHZ: delta = (ppm) 2.33 (s, 3H), 3.54 (s, 3H), 3.79 (s, 3H), 3.84 (s, 3H)
3,
3.98 (s, 3H), 5.32 (d, lH J = 9.6 Hz), 6.23 (d, lH J = 9.6 Hz), 6.49(s, lH)ゝ 8.21 (s, lH) [0121] meta-(5(2, 3, 4-trimethoxy-6-methyl failure)-Bromo-4-Cros mouth - 2-methoxy 3-pyridyl) -- Knoll 2.21g (5.1mmol) Mosquito Moe and 1-hour flowing-back heating were performed for 4.55 g (an 88% article and 46mmol) of manganese dioxide in the solution dissolved in 70 ml of toluene. 4.55 g (an 88% article and 46mmol) of manganese dioxide is added -- flowing-back heating was performed for 1 hour. S after cooling a reaction mixture to room temperature The bottom toluene of removal and decompression was distilled off for 2 acid Y manganese using the light. Obtained rough generation A thing is refined in silica gel chromatography and it is 3. - (2,3,4-trimethoxy 6-methyl Benzoyl) -5-Bromo - 4-Cros mouth - 1.90 g (87% of yield) of 2-methoxy pyridine (melting point 84-87"C) was obtained. ^ -NMR CCDCl 400MHZ: delta = (ppm) 2.48 (s, 3H), 3.45 (s, 3H), 3.75 (s, 3H), 3.87 (s, 3H)
3,
3.91 (s, 3H), 6.57(s, lH)ゝ 8.27 (s, lH)
[0122] Synthetic example 4
3 - (2,3,4-Trimethoxy - 6 - Methylbenzoyl) - 5 - Cros Mouth - 2 Composition of - Methoxy-4-Methyl Pyridine (CombinationNo.35)
(a) N of 8.0 g (65mmol) of 2-methoxy-4-methyl pyridine, N-Dimethylform amide
(DMF) 9.2 g (69mmol) of N-Cros mouth succinic acid imide is supplied in 15-ml solution -- it agitated for 18 hours. Water is added to reaction solution and it is a saturation salt solution after extraction and about an organic layer at diethylether in a water layer. The bottom solvent of filtration and decompression was distilled off after dryness with washing and anhydrous sodium sulfate. He is Thilly about a rough product. It refines in power gel column chromatography, and is 5. - Cros mouth - 2 8.5 (Fusion point 32-33"C) g (82% of yield) of - methoxy-4-methyl pyridine was obtained.
1HNMR(CDC1, 300 MHz): delta -- 2.32 (s, 3H), 3.89 (s, 3H), 6.62 (s, lH), and 8.05 (s, lH)
3
[0123] (b) 5-Cros mouth - 20.2 g (114mmol) of N-Bromo succinic acid imide is supplied in N of 7.2 g (46mmol) of 2-methoxy 4-methyl pyridine, and 15 (DMF) ml of N-Dimethylform amide solution, It is 20 hours at 50 degreeC. It agitated. Rare sodium subsulfite solution is added to reaction solution, and it is diethylether about a water layer. It extracted. A saturation salt solution washes an organic layer, the bottom solvent of filtration and decompression is distilled off with a silica gel cake after dryness with anhydrous sodium sulfate, and it is 3. - Bromo - 5 - Cros mouth - 2 - methoxy-4-methyl pillage 10.6 g (97% of yield) of A (melting point 44- 45"C) were obtained.
1HNMR(CDC1, 300 MHz): delta -- 2.51 (s, 3H), 3.98 (s, 3H), and 8.01 (s, lH)
3
[0124] (c) isopropyl magnesium chloride (2.0 mol/l tetrahydrofuran solution) They are 4 ml of tetrahydro francs to 2.2 ml (4.4mmol), 0.62 ml (4.4mmol) of Triethylamine are cooled to mosquito Moe and 0 degreeC, 3-Bromo- 5-Cros mouth - It is Melting to 5 ml of tetrahydro francs about 1.0 g (4.2mmol) of 2-methoxy 4-methyl pyridine. After the solution made to understand is dropped, It agitates for 3 hours and is 5-Cros mouth. - 2-methoxy-4-methyl-3-pyridyl Magnesium chloride was prepared. the solution in which 5 ml of tetrahydro francs were made to dissolve 0.89 g (4.2mmol) of 2, 3, and 4-trimethoxy-6-methyl benzaldehyde is dropped into reaction solution -- 1-hour Stirring After carrying out Stirring, room temperature was raised, and also it agitated for 1 hour. Water is added to reaction solution and it is stop about a reaction. It gives up and they are washing and anhydrous magnesium sulfate with a saturation salt solution after extraction and about an organic layer at acetic acid Ethyl. The solvent was distilled off under filtration and decompression after dryness. It is a silica gel column chromatograph about a rough product. It refined by Í 1 and obtained methanol (5 (2, 3, 4-trimethoxy-6-methyl failure) - Cros mouth - 2-methoxy-4-methyl-3 - pyridyl) (light yellow oily matter) l.lg (70% of yield).
1HNMR (CDC1, 300 MHz) : delta 2.26 (s, 3H), 2.27 (s, 3H), 3.54 (s, 3H), 3.80 (s, 3H),
3
3.84(s, 3H), 3.94(s, 3H), 5.32(d, 1H, J=9.0Hz), 6.12(d, 1H, J=9.0Hz), 6.47(s, 1H) , 8.02(s, 1H)
[0125] (d) Me (5(2, 3, 4-trimethoxy-6-methyl failure)-Cros mouth - 2-methoxy-4-methyl 3-pyridyl) It is mosquito Moe about 4 g of active manganese dioxide to 15 ml of toluene solution of 0.64 g (1.7mmol) of Tanol, Heating It agitated under flowing back for 1 hour. Reaction solution is filtered using Celite, the bottom solvent of decompression is distilled off, and it is 3. -(2,3,4-trimethoxy-6-methylbenzoyl)-5-Cros mouth - 0.57 (94.5 - 95.5 degrees of melting points C) g (90% of yield) of 2-methoxy-4-methyl pyridine was obtained.
1HNMR (CDC1, 00 MHz) : delta 2.31 (s, 3H), 2.40 (s, 3H), 3.30 (s, 3H), 3.73 (s, 3H),
3
3.74(s, 3H), 3.88(s, 3H), 6.54(s, 1H), 8.06(s, 1H)
[0126] Synthetic example 5
3-(2,3,4-trimethoxy-6-methylbenzoyl)- 4-trifluoromethyl-2-methoxy-5-methyl Composition of pyridine (CompositeNo.37)
(<sub>a</sub>The solution which dissolved 5.05 g (27.8mmol) of 2-chloro 4-trifluoromethyl pyridine and 3.59 g (66.5mmol) of sodium methoxide in 40 ml of methanol was agitated under heating at reflux for 4 hours. Water After stopping a reaction in addition and extracting with diethylether, it is anhydrous sulfuric acid Satellite about an organic layer. It filtered with dryness and a silica gel cake by Beam. a solvent is distilled off under decompression -- 4-truffe Luorome 4.19 g (85% of yield) of Chill-2-methoxy pyridine was obtained.
^ -NMRCCDCl, 400 MHz : delta = (ppm) 3.96 (s, 3H), 6.95 (s, 1H), 7.05 (d, 1H, J= 5.2 Hz), 8.29 (d, 1H, J= 5.2 Hz)
[0127] 8.21 g (46.4mmol) of 4-trifluoromethyl-2-methoxy pyridine obtained at the (b) process (a), Vinegar To the solution which dissolved 7.98 g (97.3mmol) of acid sodium in 15 ml of acetic acid, it is 4.00 ml (78. lmmol) of bromine. It was dropped and agitated for four days. Potassium hydrate solution is added, a reaction is stopped and it is Jetyl Ae. After extracting by Tell, an organic layer is filtered with dryness and a silica gel cake with anhydrous sodium sulfate. It carried out. a solvent is distilled off under decompression -- 5-Bromo-4-trifluoromethyl-2-methoxy pyridine -- original -- 5.81 g (molar-ratio 55 : 45) of mixtures with the 4-trifluoromethyl-2-methoxy pyridine of a charge were obtained. ^ -NMRCCDCl, 400muetazeta: delta = (ppm) 3.94 (s, 3H), 7.03 (s, lH), 8.37 (s, lH)
3
[0128] Inside of the solution which dissolved 3.80 ml (27. lmmol) of (c) diisopropylamine in 50 ml of tetrahydro francs It is n-butyl lithium (it is Xan solution to 1.57 mol/l) at 0"C. 17.1 ml was dropped and it agitated for 30 minutes. Solution - It cools to 78"C, 5-Bromo-4-trifluoromethyl 2-Metoki obtained at the process (c) 5.81 g (molar-ratio 55 : 45) of mixtures of Shipiridine and 4-trifluoromethyl-2-methoxy pyridine The solution which dissolved in tetrahydro franc 10mL is added, It agitates for 45 minutes and is 5-Bromo-4-trifluoro. Methyl-2-methoxy-3-pyridyl lithium and 4-Trifluoro methyl-2-methoxy-3-pyridyl Lithium The mixture of Beam was prepared. the solution which dissolved 5.51 g (26.2mmol) of 2, 3, and 4-trimethoxy-6-methyl benzaldehyde in tetrahydro franc 15mL is added -- it agitated for 1 hour. It is Addition about water to a mixture. It obtained, the reaction was stopped and the bottom of decompression tetrahydro franc was distilled off. They are after extraction and organicity at acetic acid Ethyl. The layer was dried and filtered with anhydrous sodium sulfate, and the solvent was distilled off under decompression. a rough product -- Thilly it refines in power gel column chromatography (2, 3, 4-trimethoxy-6-methylphenyl) -- 5.02 g of methanol (5- Bromo-4-trifluoromethyl-2-methoxy 3-pyridyl) was obtained.
(ppm) 1 H-NMR(CDC1, 400 MHz) delta =2.35 (s, 3H), 3.29 (s, 3H), 3.74 (s, 3H), 3.82 (s) :
3
3H), 3.92(s, 3H), 4.87(d, 1H, J=10.8Hz), 6.21(d, 1H, J=10.8Hz), 6.51(s, 1H), 8.31(s, 1H)
[0129] it was obtained at the (d) process (c) (2, 3, 4-trimethoxy-6-methyl failure) -- 4.80 g (10.3mmol) of methanol (5 - Bromo-4-Trifluoro methyl-2-methoxy-3-pyridyl) It dissolves in toluene llOmL. In Solution, 20.0 g (230mmol) of 2 acid Y manganese was agitated under mosquito Moth heating at reflux for 1 hour. Room Celite filtration of the mixture was carried out after cooling to Warm, and the bottom solvent of decompression was distilled off. a rough product -- silica it refines in gel column chromatography -- 3-(2,3,4-trimethoxy-6-methylbenzoyl)- 3.93 g (82% of yield) 5-Bromo-4-trifluoromethyl 2-methoxy pyridine (CompositeNo.31) It obtained.
(ppm) 1 H-NMR(CDC1, 400 MHz) delta =2.57 (s, 3H), 3.36 (s, 3H), 3.75 (s, 3H), 3.86 (s) :
3
3H), 3.93(s, 3H), 6.59(s, 1H), 8.38(s, 1H)
[0130] 3-(2, 3,4-trimethoxy-6-methylbenzoyl)-5-Bromo- 4-truffe obtained at the (e) process (d) 0.60 g (1.29mmol) of Luolo methyl-2-methoxy pyridine, Tetrakis The (truffe yell phosphine) To the inside of the solution which dissolved 0.10 g (0.09mmol) of radium in 10 ml of tetrahydro francs, It is Dimethy at 0 degreeC. Le zinc (it is Xan solution to 1.0 mol/l) 3.80 ml (3.80mmol) is dropped and they are after natural I warmed up. and room temperature. It agitated for eight days. Water was added, the reaction was stopped and the bottom of decompression tetrahydro franc was distilled off. Vinegar An organic layer is dried and filtered with anhydrous sodium sulfate after extraction by acid Ethyl, and the bottom solvent of decompression is distilled off. It carried out. refining a rough product in silica gel column chromatography -- 3-(2,3,4-trimethoxy-6-methylbenzoyl)- 0.50 g (96% of yield) of 4-trifluoromethyl-2-methoxy-5-methyl pyridine was obtained.
^ (ppm) -NMRCCDCl and 00MHzdelta =2.41 (s, 3H), 2.56 (s, 3H), 3.29 (s, 3H), 3.74 (s) :
3
3H), 3.83(s, 3H), 3.91(s, 3H), 6.58(s, 1H), 8.05(s, 1H)
[0131] Synthetic example 6
4 (2, 3, 4 -- Trimethoxy 6 -- Methylbenzoyl) 2, 5 [ Composition of Gin (CompositeNo.39) ] -- Dichloro 3 -- Trifluoro Methyl pyri
(a) the inside of the solution which dissolved 3.6 ml (25mmol) of diisopropylamine in 60 ml of diethylether -- and 0 degreeC -- n butyl lithium (it is Xan solution to 1.5 mol/l) 17 ml (25mmol) is dropped -- it agitated for 45 minutes. solution - it cools to 78"C -- 2,3,6 -- the Tori Cros mouth -- 5 -- trifluoromethyl pyridine
Attach mosquito A of the solution which dissolved 6.0 g (24mmol) in 8 ml of diethylether is carried out, It agitates for 25 minutes and is 2, 3, and 6. - The Tori Cros mouth - After preparing 5-trifluoromethyl-4-pyridyl lithium, 2, 3, 4 -- Trimethoxy -- Attach mosquito A of the solution which dissolved 5.0 g (24mmol) of 6 methyl benzaldehyde in 12 ml of toluene was carried out, and it was agitated for 1 hour. 30 ml of water is added to a mixture, a reaction is stopped, and it is a water layer after extraction at acetic acid Ethyl. The organic layer was dried and filtered with anhydrous sodium sulfate, the solvent was distilled off under decompression, and Methano (2 (2, 3, 4 -- Trimmety 6 -- methyl failure), 3, 6 [ Pyridyl ] -- Trichloro 5 -- trifluoromethyl 4) - Le (melting point 131 -- 135"C) was obtained. [0132] 2, 3, 4 which were obtained at the (b) process (a) -- In the solution which dissolved trimethoxy 6 methyl failure (2, 3, 6 -- Trichloro 5 -- Tri-Fluro methyl 4 pyridyl) methanol in 200 ml of methanol, Trier It is 14-hour Stirring under mosquito Moe and a hydrogen atmosphere about 2.7 ml (19mmol) of Chilmin, and 0.9 g of 5% palladium carbon. Stirring was carried out. The mixture was filtered and bottom methanol of mosquito Scare decompression was distilled off for 30 ml of water. Acetic acid Ethyl The organic layer was dried and filtered with anhydrous sodium sulfate after extraction, and the solvent was distilled off under decompression. A rough product is refined in silica gel column chromatography, (2, 3, 4 -- Trimethoxy 6 -- Me Chill Feer) 2.38 g (24% of yield) methanol (melting point 162 -- 165"C) was obtained (2, 5 -- dichloro 3 -- trifluoromethyl 4-pyridyl).
[0133] it was obtained at the (c) process (b) (2, 3, 4 -- trimethoxy 6 methyl failure) -- 3.5 g (8.2mmol) of methanol (2, 5 [ -- Truffe Luolo methyl 4-pyridyl ] -- Dichlo mouth -- 3) In the solution which dissolved in 100 ml of toluene 14 g of manganese dioxide was added and it agitated under heating at reflux for 6 hours. The cooling back fault of the mixture is carried out, and it is a decrease. Pressing-down toluene was distilled off. A rough product is refined in silica gel column chromatography, and it is 4 (2, 3, 4 -- trimethoxy 6 methylbenzoyl). 2, 5 [ Gin (melting point 106 -- 109"C) 3.1 g (89% of yield) was obtained. ] -- Dichloro 3 -- Trifluoro Methyl pyri
[0134] Synthetic example 7
4 (2, 3, 4 -- Trimethoxy 6 Methylbenzoyl) Two Cros Mouth -- 3 [ Composition of Kishipi Lysine (CompositeNo.40) ] -- Trifluoromethyl 5 -- Met
(a) the inside of 120 ml of diethylether solution of 15.0 ml (107mmol) of diisopropylamine -- 0"C -- n butyl lithium (it is Xan solution to 1.5 mol/l) 70.0 ml (106mmol) is dropped -- it agitated for 1 hour. solution is cooled to 78 degreeC -- 2,3 -- dichloro 5 -- carrying out Attach mosquito A of the 10 ml of diethylether solution of 22.1 g (102mmol) of trifluoromethyl pyridine It agitates for 30 minutes and is 2 and 3-dichloro 5-truffe Luolomethi. After preparing roux 4-pyridyl lithium, it is 2, 3, and 4. -- Trimethoxy 6 -- 40 ml of toluene solution of 21.0 g (100mmol) of methyl benzaldehyde was added, and it agitated for 2 hours. 30 ml of water is added to a mixture. A reaction is stopped and they are dryness and Filtration with anhydrous sodium sulfate after extraction and about an organic layer at acetic acid Ethyl in a water layer. It passed and distilled off the solvent under decompression. It is silica gel column chromatography about a rough product. It refines, (2, 3, 4 -- Trimethoxy 6 -- Methyl failure) 24.8 g (58% of yield) methanol (melting point 95 -- 98"C) was obtained (2, 3 [ -- Trifluoromethyl 4 pyridyl ] -- Dichlo mouth -- 5).
[0135] it was obtained at the (b) process (a) (2, 3, 4 -- trimethoxy 6 methyl failure) -- 24.8 g (58. lmmol) of methanol (2, 3 -- Dichlo mouth 1 5 -- truffe Luolo methyl 4 pyridyl), Into 200 ml of methanol solution of 9.50 ml (68.2mmol) of Triethylamine, 5% palladium carbon 2. lg is added, and it is A hydrogen atmosphere. It agitated under The atmosphere for 4 hours. A mixture is filtered and methanol is distilled off for 50 ml of water under mosquito Moth decompression. It carried out. The water layer was extracted by acetic acid Ethyl, the organic layer was dried and filtered with anhydrous sodium sulfate, and the solvent was distilled off under decompression. A rough product is refined in silica gel column chromatography, and it is Me (3 (2, 3, 4 -- trimethoxy 6 -- methyl failure) chloro 5 -- trifluoromethyl 4 pyridyl). 15.9 g (70% of yield) Tanol (melting point 102 -- 105"C) was obtained.
[0136] It was obtained at the (c) process (b). (2, 3, 4 -- Trimethoxy 6 Methyl failure) He is 2 oxidization Ma in 220 ml of toluene solution of 15.9 g (40, 6mmol) of methanol (3 chloro 5 -- Trifluo Methylou 4 pyridyl). 45 g of Negan were added and it agitated under heating at reflux for 2 hours. A mixture is filtered and it is Distant about a solvent under decompression. The past is carried out and it is 4 (2, 3, 4 -- trimethoxy 6 -- methylbenzoyl). 3 -- Cros mouth -- 5 -- Trifluoro Methylpi 14.9 g (94% of yield) lysine (melting point 75 -- 77"C) was obtained.
(d) 4 (2,3,4 -- trimethoxy 6 -- methylbenzoyl) obtained at the process (c) 3 [ -- Tori / It passes and 18.5 g (47.5mmol) of Fluoro methyl pyridine is Xamethyllin acid Triamide. ] -- Cros mouth -- Five
16.4 g (304mmol) of sodium methoxide was agitated for 30 minutes under the Callot Huh and heating at reflux in 16.6 ml (95.4mmol) of 150 ml of toluene solution. After adding water and stopping a reaction, it is acetic acid Ethyl about a water layer. It extracted, the organic layer was dried and filtered with anhydrous sodium sulfate, and the solvent was distilled off under decompression. rough -- refining output in silica gel column chromatography -- 4 (2,3,4 -- trimethoxy 6 -- Methyl benzoyl) 5 -- 3 -- methoxy -- 11.7 g (64% of yield) of trifluoromethyl pyridine (melting point 103 -- 106"C) was obtained.
[0137] (e) 4 -- (2, 3, 4 -- trimethoxy 6 methylbenzoyl) 5 -- 3 -- methoxy -- trifluoro Methyl pyri Inside of the Cros mouth Holum 100-ml solution of 5.6 g (15mmol) gin (CompositeNo.l22), It is m Cros Mouth at 0 degreeC. After adding 6.1 (m-CPBA) g (28mmol) of benzoic acid, it agitated at room temperature for 18 hours. Reaction solution It washes in Hydroxic acid sodium solution, and distills off a solvent under decompression, 4(2,3,4 -- methylbenzoyl)-- six -- trimethoxy--3 -- methoxy -- 5 -- trifluoromethyl pyridine N -- 5.8 g (99% of yield) talent Xide (melting point 128 -- 134"C) was obtained.
[0138] To the inside of 4 ml of (f) toluene, and 8 ml of Dimethylform amide, 0 After Agitating 1.8 Ml (19Mmol) of Oxy Phosphorus Chlorides by °C for Callot Huh 10 Minutes, 4-(2,3,4-trimethoxy-6-methylbenzoyl)-3 - methoxy -5 -- trifluoromethyl pyridine N -- 4.0 g (10mmol) of talent Xide were agitated for the Callot Huh 20 minutes. To room temperature After agitating for The 2 hours, reaction solution was thrown in in ice water and the reaction was stopped. It is acetic acid Ha about a water layer. An organic layer is dried and filtered with anhydrous sodium sulfate after extraction by Le, and a solvent is distilled off under decompression. It was. A rough product is refined in silica gel column chromatography, and it is 4 (2,3,4 -- trimethoxy 6 methylbenzoyl). 2 [ -- 3.57 g (85% of yield) methoxy pyridine (melting point 1171119degreeC) was obtained. ] -- Chloro 3 -- Trifluoromethyl 5
Synthetic example 8
3-(2,3,4-trimethoxy-6-methylbenzoyl)-5-Cros mouth - Composition of 2-methoxy-4-methyl pyridine (CombinationNo.35)
(a) 45.6 g (217mmol) of 2, 3, and 4-trimethoxy 6-methyl Bennswald were dissolved in 130 ml of dimethyl sulfoxide, and 5.2g (44mmol) of phosphoric acid 2 hydrogen sodium solution (50 ml) was dropped over 20 minutes. 28g (305mmol) of sodium chlorite solution (180 ml) is dropped over 3 hours by -- it agitated for 2 hours. After adding saturated sodium bicarbonate solution and agitating for 1 hour until it stops foaming, he is Callot about 2 times washing, the occasion, and concentrated hydrochloric acid at 50 ml of acetic acid Ethyl in reaction solution. It obtained, the water layer was acidified and it extracted by acetic acid Ethyl. A saturation salt solution washes an organic layer and it is anhydrous. It dried and filtered with sodium sulfate and distilled off the bottom solvent of decompression. It passes through the obtained crystal and is Xan. Washing is carried out and 45.6 (melting point 95-97"C) g (93% of yield) of 2, 3, and 4-trimethoxy-6-methylbenzoic acid is obtained. It was.
1HNMR: delta -- 2.56 (s, 3H), 3.86 (s, 3H), 3.91 (s, 3H), 4.03 (s, 3H), and 6.60 (s, lH)
(b -- 1) Isopropyl magnesium chloride (2M tetrahydrofuran solution) 6.8 ml (13.6mmol) is cooled to 0 degreeC, 3 - Bromo - 5 - Cros Mouth - 2 It is Tetra about 1.6 G (6.6Mmol) of - Methoxy 4-Methyl Pyridine. Solution in which 5 Ml of Dollo Fran was Dissolved is Dropped, it agitates at the temperature for 3 hours -- 5-Cros mouth - 2-Metoki See 4 - methyl - 3 - pyridyl magnesium chloride was adjusted. Reaction solution - 78"C It cools and is tetrahydro about copper cyanide (I)1.2g (13.3mmol) and chlorination lithium 1.15g (27.1mmol). The solution in which 15 ml of francs were dissolved is dropped, 5-Cros mouth - 2-methoxy 4-methyl-3-pyridyl copper The reaction agent was adjusted. On the other hand, 3.2 g (14.3mmol) of 2, 3, and 4-trimethoxy-6-methylbenzoic acid compounded at the (a) process is heated at reflux in 7 ml of chlorination Chi - Le for 3 hours, It is a decrease about superfluous chlorination Chi-Le. It is a tetrahydro franc about the 2, 3, and 4-trimethoxy-6-methylbenzoic acid chloride which carried out pressing-down distilling off and was adjusted. Solution in which 7 ml was dissolved, the inside of the pyridyl copper reaction agent adjusted previously - it is dropped by 78"C -- 1 hour After agitating, room temperature was raised, and also it agitated for 2 hours. They are water and an ammonia solution to reaction solution. In addition, the reaction was stopped and it extracted by acetic acid Ethyl. It is Dry with anhydrous magnesium sulfate about an organic layer. The solvent was distilled off under filtration and decompression after Dry. It is silica gel column chromatography about a rough product. It refines in 1 and is a 3-(2, 3, 4-trimethoxy-6-methylbenzoyl)-5-Cros mouth. - 2-methoxy-4-Methi 2.6 (melting point 85-88"C) g (57% of yield) of kana lysine is obtained, The compound was identified in 1HNMR.
(b-2) Isopropyl magnesium chloride 1M tetrahydrofuran solution llml (11.0mmol), 3- Bromo - 5-Cros Mouth - Using 2.5 G (10.6Mmol) of 2-Methoxy 4-Methyl Pyridine -- Process (B -- 1) -- Said -- Him -- Reacting Copper cyanide (1), It is tetra instead of a chlorination lithium tetrahydrofuran solution. 1.25 g (l. lmmol) of kist Ref-Le phosphine palladium is used, and it is 2, 3, and 4-trimethoxy 6-methyl. 2.4 g (10.6mmol) of benzoic acid, and 2, 3, 4-trimethoxy-6-methyl which were adjusted from 5 ml of chlorination Chi - Le Benzoic acid chloride it is dropped over 2 hours by 0 degreeC, and agitates at the temperature for 15 hours -- 3-(2,3,4-Tori methoxy-6-methylbenzoyl)-5-Cros mouth - 1.7 g (43% of yield) of 2-methoxy-4-methyl pyridine it obtains -- the compound was identified in 1HNMR.
(b -- 3) By the same reaction as a process (b -- 2), it is isopropyl magnesium chloride 1M tetra-Hydro. They are 22 ml (22.0mmol) of isopropyl magnesium chloride 0.5M tetrahydrofuran solutions instead of run solution, 1.14 g (11.5mmol) of copper chlorides are used instead of tetrakis Torhue-Le phosphine palladium, 3-(2,3,4-trimethoxy-6-methylbenzoyl)- 1.7 g (43% of yield) of 5-Cros mouth-2-methoxy 4-methyl pyridine is obtained -- the compound was identified in 1HNMR.
Synthetic example 9
3-(2,3,4-trimethoxy-6-methylbenzoyl)-5-Cros mouth - Composition of 2-methoxy-4-methyl pyridine (CombinationNo.35)
(a) Solution which dissolved 5.0 g (19mmol) of 2-Bromo-3, 4, and 5-trimethoxy toluene in 50 ml of diethylether - It cools to 78"C, n-butyl lithium (it is Xan solution to 1.6M) 15 ml (24mmol) is dropped, it agitates for 1.5 hours -- 2, 3, and 4-trimethoxy-6-methyl-2-fail lithium was generated -- back -- 4.9 ml (43mmol) of boron acid Trimethyl were dropped, and also it agitated for 1 hour. adding dilute sulfuric acid a reaction is stopped -- water was added after agitating for 30 minutes. extracting a water layer by acetic acid Ethyl, and drying and filtering an organic layer with washing and anhydrous magnesium sulfate with a saturation salt solution -- bottom solvent of decompression it distills off -- 3.26 (melting point 99-102"C) g (75% of yield) of 2, 3, and 4-trimethoxy-6-methyl failure boron acids were obtained.
1HNMR: delta -- 2.52 (s, 3H), 3.83 (s, 3H), 3.88 (s, 3H), 3.94 (s, 3H), and 6.56 (s, lH)
(b) It is a 3-Bromo-5-Cros mouth to 200ml autoclave. - 2-methoxy 4-methyl pyridine l.Og (4.3mmol), 2, 3, 1.2 g (5.4mmol) of 4-trimethoxy-6-methyl failure boron acids, 147 mg (0.52mmol) of Xyl phosphine and 40 ml of tetrahydro francs were put in to potassium carbonate 1.8g (13mmol), 46 mg (0.26mmol) of palladium chlorides, and tricyclo one, 10 atmospheres of carbon monoxide gas was enclosed, and it agitated by 120 degreeC for 20 hours. Celite filtration of the reaction solution is carried out, water is added, and it is a bottom of decompression tetrahydro hula. A was distilled off. A water layer is extracted by acetic acid Ethyl, and an organic layer is dried with anhydrous magnesium sulfate. It filtered and the back distilled off the bottom solvent of decompression. It is silica gel column chromatography about a rough product. It refines and is a 3-(2,3,4-trimethoxy-6-methylbenzoyl)-5-Cros mouth. - 2-methoxy-4-methyl 0.31 (melting point 92-94"C) g (20% of yield) of pyridine is obtained, The compound was identified in 1HNMR.
Synthetic example 10
3-(2,3,4-trimethoxy-6-methylbenzoyl)-5-Cros mouth - Composition of 2-methoxy-4-methyl pyridine (CombinationNo.35)
(a) In the 500-m Drawing mouth flask provided with the stirrer, the condensator, the thermometer, and the nitrogen balloon, mug teaching 5.4g (222mmol) of Nessim, and 95 ml of tetrahydro francs -- a system -- maintaining the degree of internal temperature at 40 degreeC While -- 17.3 g (220mmol) of isopropyl chloride was dropped, and -* churning of was done. then, inside of a system while maintaining temperature below at 0 degreeC -- 3-Bromo-5-Cros mouth - 95 ml of tetrahydro franc solution of 47.3 g (200mmol) of 2-methoxy-4-methyl pyridine is dropped -- inside of after 3-hour churning and dry ice Reaction liquid was dropped.
Reaction liquid is thrown in in 300 ml of water, and after liquid separation, chloride water is dropped at a water layer, and it acidifies, and is Jesse. It extracted by Ruetel. The bottom solvent of decompression is distilled off and it is 5-Cros mouth. - 2-methoxy-4-methyl Nicochi 26 (melting point 127-129"C) g (65% of yield) of A acid was obtained.
(b) In the 50-m Drawing mouth flask provided with the stirrer, the condensator, the thermometer, and the nitrogen balloon, 5-Cros 1.0 g (4.96mmol) of mouth-2-methoxy 4-methyl nicotinic acid, 20 ml of 0.9 g (4.94mmol) of 3, 4, and 5-trimethoxy toluene, 1, and 2-Dichloroethane and 7.1 g (50.0mmol) of 5 oxidization 2 Rin were taught, and it agitated under flowing back for 1 hour. Reaction liquid is thrown in in 50 ml of water, Alkaline B of the Hydroxic acid sodium solution is added and carried out, and it is a part. The bottom solvent of decompression was distilled off after liquid. crystal which passed to obtained Leftovers, added 5 ml of Xan, and deposited it filters -- 0.4 g (22% of yield) of objects were obtained.
[0142] Synthetic example 11
3-(2,3,4-trimethoxy-6-methylbenzoyl)-5-Cros mouth - Composition of 2-methoxy-4-methyl pyridine (CombinationNo.35)
To the 20pi* eggplant flask provided with the reflux condenser, it is 5-Cros mouth. - 2-methoxy-4-methyl nicotinic acid 1.0g (5.0mmol), 60"C after teaching 10g of 1 and 2-Dichloroethane, and 0.62 g (5.0mmol) of oxalyl chloride and agitating by 25 degreeC for 20 minutes -- It heated by 65"C for 2 hours. reaction after cooling to 25 degreeC a mixture -- 3, 4, 0.80 g (4.4mmol) of 5-trimethoxy toluene, and 0.70 g (5.2mmol) of anhydrous-salts-ized aluminum -- in addition, it agitated by 25"C for 3 hours.
Water and acetic acid Ethyl are added to a reaction mixture, and it is sodium sulfate after extraction and liquid separation and about an organic layer. It dried and distilled off the solvent under decompression. Xan is added to the depositing solid to n-, and it filters and dries. 0.66 g (36.1% of yield) of objects were obtained.
[0143] Synthetic example 12
3-(2,3,4-trimethoxy-6-methylbenzoyl)-5-Cros mouth - Composition of 2-methoxy-4-methyl pyridine (CombinationNo.35)
(a) After agitating 10 ml of chlorination Chi - Le under the Callot Heat to reflux for 4 hours to 6.0 g (26.6mmol) of 2, 3, and 4-trimethoxy-6-methylbenzoic acid, superfluous salt A Chionil was distilled off under decompression. It will be there at bottom of mosquito Moth heating at reflux 16:00 about 20 ml of toluene, 8 ml of Asset nitril, and copper cyanide (I)3.1g (34.5mmol). It agitated in between. Reaction solution was filtered by Celite after cooling to room temperature, and the bottom solvent of decompression was distilled off. a rough product is refined in silica gel column chromatography -- 2, 3, and 4-trimethoxy-6-Methi It obtained 2.8 g (yield45 %) of Reuben Zoru seared.
1HNMR: delta -- 2.44 (s, 3H), 3.85 (s, 3H), 3.95 (s, 3H), 4.14 (s, 3H), and 6.53 (s, lH)
[0144] (b) Solution in which 20 ml of tetrahydro francs were made to dissolve 1.9 g (8.0mmol) of 2, 3, and 4-trimethoxy-6-methylbenzoyl seared - It cools to 10"C and they are 0.32g of iron (III) Cetyl acetonate.
(0.91mmol) was added and it agitated for 20 minutes. 4 ml of tetrahydro francs are added to another reaction vessel at 4.1 ml (8.2mmol) of isopropyl magnesium chloride 2M tetrahydrofuran solutions, and it cools to 0 degreeC, 3- Bromo - 5-Cros Mouth - It is in 5 Ml of Tetrahydro Francs about 1.0 G (4.2Mmol) of 2-Methoxy 4-Methyl Pyridine. After Dissolved Solution is Dropped, It agitates for 3 hours and is 5-Cros mouth. - 2-methoxy-4-methyl-3-pillage Le Magnesium chloride was generated. 2, 3, 4-trimethoxy-6-Methylbenz which adjusted the point The pyridyl magnesium chloride solution adjusted to the Zoru seared iron mixed solution was dropped, and it agitated for 3 hours. Salt Y Ann A-Um solution is added to reaction solution 10%, a reaction is stopped, and it is vinegar. They are after extraction and an organic layer after dryness with washing and anhydrous magnesium sulfate at a saturation salt solution in acid Ethyl. It filtered and distilled off the solvent under decompression. a rough product -- silica gel column chromatography Purification is carried out -- 1.7 g (58% of yield) of objects were obtained.
[0145] Example 1 of intermediate composition
(a) In the 2Lfour mouth flask provided with the stirrer, the thermometer, and the gas introducing pipe (ON), Degree of system internal temperature after preparing 324g (3.00 mol) of 2-Amino- 4-methyl pyridine, and 485 g of methanol and carrying out the mixed dissolution 10 - 361.4 g (9.90 mol) of hydrogen chloride gas was introduced over 1 hour and 30 minutes, maintaining at 30"C. next, a stirrer, a thermometer, a dropping funnel and a gas plant, and Gaz Y Reactor -- connection -- 2Lfour mouth flask provided with the introducing pipe with a Did air-bubbles counter (appearance), nitrous acid Satellite mixing 414 g (6.00 mol) of Beam, 211g (6.60 mol) of methanol, and 454 g of water -- a system -- 812.4 g (3.15 mol) of sulfuric acid solution was dropped over 5 hours 38%, maintaining the degree of internal temperature at 20-30 °C.
It is considerable nitrous acid at the same time 38% sulfuric acid solution is dropped in a methyl nitrite generator. Methyl gas is emitted, a cellular counter is led and it is introduced into a diazotization reaction device.
On the other hand, diazotization reaction Well and The were water-cooled so that the degree of system internal temperature could be maintained to 20-30"C. After the end of methyl nitrite gas introduction, it agitated in the Warm for 13 hours, and terminated the reaction. After carrying out decompression distilling off of the methanol, water 648 g is supplied, and also it is 40% Hydroxic acid Nato below in 30 degreeC. 518 g of Rium solution was dropped and pH in a system was adjusted to 12.
generation oil is extracted with 910-g diethylether, and the bottom solvent of decompression is distilled off after liquid separation -- oil of 375.3 g was obtained. Composition of this oil (rough product) is 2-Cros mouth. - 4-methyl pillage A 70.7% (69.5% of yield), and 2-methoxy-4-methyl pyridine 26.6% (27.2% of yield), and 2-Amino- 4-Methi It is kana lysine 2.6% and is Oh.
[0146] In 2L four mouth flask provided with the (b) stirrer, the thermometer, the condenser tube, and the dropping funnel, Methano While teaching 356 g of Le and maintaining below at bottom 50-degreeof churning C, it is 237.6 g (4.4 mol) of sodium methoxide. After supplying, It is the degree of system internal temperature 60 - 2-Cros mouth acquired at the above-mentioned process while maintaining at 70"C - 4-Methi 375.3 g (a 70.7% article and 2.2 mol) of rough products of kana lysine were dropped over 3 hours.
It heated at reflux after the end of dropping for 3 hours, distilling off methanol. (The amount of distilling off of methanol in the meantime was 120g.)
After carrying out decompression distilling off of the residual methanol after the end of a reaction, and in a system, 750 g of water is thrown in, and it is mineral salt. It dissolved.
generation oil is extracted with 1050-g diethylether, and the bottom solvent of decompression is distilled off after liquid separation -- oil (rough product) of 370 g was obtained. The purity of the obtained 2-methoxy-4-methyl pyridine was 95%. (Two-step yield from 2-Amino- 4-methyl pyridine is 95%)
[0147] Example 2 of intermediate composition
5-Cros mouth - Composition of 4-methyl-2-methoxy nicotinic acid
(a) 4 and 4-dicyano-3-methyl-3-buthenal Jimechiruase tar, 1, and 1-dicyano-4-Met Composition of the mixture of Ix-2-methyl-1 and 3-butadiene
2.28 g (37mmol) of acetic acid is added to 100 ml of toluene solution of 3.15 g (37mmol) of piperidine, and it is room temperature. It is mosquito Scared about 20 ml of toluene solution of 49.3 g (373mmol) of Assetilasset aldehyde Jimechiruase tar after agitating for 1 hour. 30 ml of toluene Melting with a Marono- trill of 24.65 g (373mmol) In addition, churning was slowly performed for liquid for five days at room temperature over 20 minutes. A reaction mixture is distilled off with 50 ml of water, the bottom solvent of dryness and decompression is distilled off after washing and with magnesium sulfate, and it is 4 and 4-dicyano-3-methyl-3. - Buthenal Jimechiruase tar, 1 1-dicyano-4-methoxy-2-methyl-1, 3-butadiene 69.35 g of mixtures were obtained.
[0148] (b) Composition of 3-Shano-4-methyl pyridone
4 and 4-dicyano-3-methyl-3-buthenal Jimechiruase tar obtained by (a), 69.35 g of mixtures of 1 and 1-dicyano-4-methoxy-2-methyl-1 and 3-butadiene are applied for 3 hours so that 30 degreeC may not be exceeded to 113 g of strong sulfuric acid, and they are Tough and mosquito Scared. it Temperature rising to 50"C after agitating at room temperature for 20 minutes -- churning was performed at the temperature for 2 hours. It is water about the reaction mixture after radiational cooling. They are notes slowly to ice (500 ml). The crystal obtained by Addition(ing) was separated and the crystal was washed with 100 ml of water. a crystal is dried for 8 hours by bottom 70-degreeof one-week air-drying and also decompression C -- the rough crystal of 34.2 g (68% of two-step yield) of 3-Shano-4-methyl pyridone was obtained.<sup>1</sup>H-NMR (400 MHz, DMSO- d6) : delta 2.35 (ppm) (s, 3H), 6.29 (d, J= 6.4 Hz, lH) 7.64 (d, J= 6.4 Hz, lH)
[0149] (c) 2-Cros mouth - Composition of 3-Shano-4-methyl pyridine
14 g (104mmol) of 3-Shano-4-methyl pyridone was slowly added to the mixture of 6.52 g (31.3mmol) of phosphorous pentachloride, and 30 ml (48 g, 313mmol) of Oxy phosphorus chlorides, and the bottom of 70 minutes and then heating at reflux and 2-hour churning were performed at room temperature. Ice - water (400 ml) is filled after radiational cooling and with a reaction mixture, and it is a superfluous reaction. After decomposing an agent, 100 ml of dichloromethane performed extraction 3 times. a dichloromethane solution -- Satiated washing is distilled off with 100 ml of Japanese-style food salt water, and the bottom solvent of dryness and decompression is distilled off with magnesium sulfate -- rough crystal 15. lg of 2-Cros mouth-3-Shano- 4-methyl pyridine was obtained. NMR (400 MHz, DMSO- d6) : delta 2.86 (ppm) (s, 3H), 7.89(d, J= 5.6-Hz, lH)ゝ 8.86 (d, J= 5.6 Hz, lH)
[0150] (d) Composition of 3-Shano-4-methyl-2-methoxy pyridine
2-Cros mouth - acquired by (c) rough crystal 15. lg of 3-Shano-4-methyl pyridine is dissolved in 150 ml of non-aqueous methanol -- 24.9 g (129mmol) of methanol solution of 28% sodium methoxide was agitated for two days at mosquito Moe and room temperature. The reaction mixture was poured into 200 ml of saturation salt solutions, and it extracted 3 times by 100 ml of acetic acid Ethyl. They are dryness and Celite with magnesium sulfate about acetic acid Ethyl solution. Silica It filtered through the gel column and fully washed the column by acetic acid Ethyl. Filtrate and cleaning fluid -- Simultaneously the bottom solvent of Reduced pressure is distilled off -- obtaining the rough crystal of 14.04 g of 3-Shano-4-methyl-2-methoxy pyridine It was. -- NMR (400MHzゝ CDC1) : delta 2.51 (ppm) (s, 3H), 4.03 (s, 3H), 6.84 (d, J= 5.2 Hz, lH)
3
8.18 (d, J= 5.2 Hz, lH)
[0151] (e) 5-Cros mouth - Composition of 3-Shano-4-methyl-2-methoxy pyridine
14.04 g (95mmol) of 3-Shano-4-methyl-2-methoxy pyridine obtained by (d) is dissolved in 100 ml of Dimethylform amide -- 25.4 g (190mmol) of N-chloro succinic acid imide was added, and churning was performed at room temperature on the 3rd. since survival of materials saw and was stopped when advance of the reaction was checked by thin layer chromatography, 22 hours were performed by 50"C and churning was performed by 60 degreeC for 22 hours. 300 ml of water was filled with the radiational-cooling back and a reaction mixture, and extraction was performed 3 times by 100 ml of acetic acid Ethyl. Acetic acid Ethyl Solution is washed one by one with 150 ml of water with 2 times and then 100 ml of saturation salt solutions, and it is magnesium sulfate. The bottom solvent of dryness and decompression was distilled off. a silica gel column refines obtained Leftovers -- 5 - 13.68 g (79% of three-stage yield) of Cros mouth-3-Shano-4-methyl-2-methoxy pyridine was obtained.<sup>1</sup>
H -- NMR (400MHzゝ CDC1) : delta 2.56 (ppm) (s,3H), 4.03 (s,3H), 8.23 (s, lH) [0152] (f) 5-Cros mouth - Composition of 3-Hol mill- 4-methyl-2-methoxy pyridine
5-Cros mouth - 3-Shano - 4-methyl - 2.47 g (13.5mmol) of 2-methoxy pyridine -- anhydrous dichloro -- meta--- Dissolve in 50 ml of A. -It is toluene Melting of the cooling back and a 1M diisobutyl aluminum hydride to 78 degreeC. 20.3 ml (20.3mmol) of liquid was dropped slowly. -After half[ 2 hours and ]-agitating by 78 degreeC, it is A room gradually. It Temperature rising(ed) to Warm and performed churning for three days at the temperature. The obtained solution was cooled by the ice bath, 30 ml of water was added slowly, and the reaction was made to end. A reaction mixture is poured into 150 m of 1N chlorides, and it is It was done about 2 times extraction with 100 ml of dichloromethane. They are 100 ml of saturation salt solutions about Jig mouth Lome Than solution. The bottom solvent of dryness and decompression is distilled off with washing and magnesium sulfate, and it is a rough 5-Cros mouth. - 3-Hol mill- 4-Methi Roux 2-methoxy pyridine was obtained. NMR (400 MHz, CDC1) : delta (ppm) 2.65 (s, 3H),
3
4.03 (s, 3H), 8.25(s, lH)ゝ 10.48 (s, lH)
[0153] (g) 5-Cros mouth - Composition of 4-methyl-2-methoxy nicotinic acid
Rough 5-Cros mouth acquired by (f) - 3-Hol mill- 4-methyl-2-methoxy pyridine is dissolved in 14 ml of dimethyl sulfoxide, 20 ml of solution (a 79% article and 18.9mmol) was slowly dropped for 5.7 ml of 0.33g (2.7mmol) of phosphoric acid 2 hydrogen sodium solution over 3 hours mosquito Moe and also 2.16 g of sodium chlorite. The obtained mixture is agitated for five days at room temperature, and 50 ml of saturated bicarbonate-of-soda water is added, and it agitates overnight. It carried out. It is acid at concentrated hydrochloric acid about the water layer after washing the obtained solution twice by 50 ml of acetic acid Ethyl. The sex was used and extraction was performed 3 times by 70 ml of acetic acid Ethyl. 50 ml of saturation salt solutions washed acetic acid Ethyl solution, the bottom solvent of dryness and decompression was distilled off with magnesium sulfate, and the rough crystal was obtained. It is a rough crystal again. It dissolves in 50 ml of acetic acid Ethyl, and is acidity at concentrated hydrochloric acid about 2 times back extraction and a water layer with 50 ml of saturated bicarbonate-of-soda water. It carried out and performed extraction 3 times by 70 ml of acetic acid Ethyl. They are 50 ml of saturation salt solutions about acetic acid Ethyl solution. It washed, the bottom solvent of dryness and decompression was distilled off with magnesium sulfate, and the white crystal was obtained. It passes and is A kiss. They are air-drying after washing a crystal, and 5-Cros mouth at 50 ml of A. - 0.55 g (20% of two-step yield) of 4-methyl-2-methoxy nicotinic acid was obtained.<sup>1</sup>H-NMR (400 MHz, CDC1) : delta 2.46 (ppm) (s, 3H), 3.99 (s, 3H),
3
8.16(s, lH)ゝ
[0154] Although the example of an examination concerning the present invention is indicated below, these do not limit the present invention.
[0155] Example 1 of an examination
Wheat Japanese noodles This disease preventive effect examination Wheat (variety: agriculture and forestry No. 61) is grown in the poly bowl 7.5 cm in diameter -- the time of reaching at 1.5 leaf terms -- each For It is equivalent to 200 L/ha with a spray gun in the mixed medical fluid which adjusted trial Composite item to predetermined concentration. It obtained and sprinkled. after a medical fluid dries, the part student spore of Japanese noodles Pathogenic bacteria is sprinkled and inoculated -- 20"C It maintained at the homoiothermal interior of a room. Spore formation area is investigated eight days after inoculation 6, and it is for the following formula. It asked for Disease incidence rate and the result was shown in The 1 table 1 The 53 table. Average lesion of an unprocessed division The Operation same except having replaced area with the medical fluid and having sprinkled water with the spray gun as a processing division It asked by performing Work.
Attack rate = (a/b) X 100
a : average lesion area of a processing division
b: Average lesion area of an unprocessed division
The theoretical value was calculated by Colby's formula. It is a from book when an experimental value is lower than a theoretical value. The disinfectant constituent of Ming has a synergistic effect about a Wheat Japanese noodles This disease preventive effect examination. Like this The theoretical value by the formula of Colby at the time of saying is combined in () of The 1 table 1 The 53 table, and it is Show. It carried out.
[0156] [-- table 1]
(1st Table)
<img file="WO2005041663A1_D0021.tif" />
[0158] [-- table 3] (The 3 table) <img file="WO2005041663A1_D0022.tif" />
[0159] [-- table 4]
(4th Table)
<img file="WO2005041663A1_D0023.tif" />
[0160] [-- table 5]
(5th Table)
<img file="WO2005041663A1_D0024.tif" />
[0161] [-- table 6]
(6th Table)
<img file="WO2005041663A1_D0025.tif" />
[0162] [-- table 7]
(7th Table)
The amount of compound No. 39 dropping medicine
Amount of Chill dropping medicine 12. 5 g/ha 6. 3 g/ha 3. lg/ha Og/ha
100g/ha 0 (1. 7) 0 (3. 0) 2. 5 (3. 0) 5. 0
50g/ha 0 (5. 2) 2. 5 (9. 0) 2. 5 (9. 0) 15. 0
25g/ha 0 (10. 5) 5. 0 (18. 0) 30. 0 30. 0
Og/ha 35.0 60.0 60.0 [0163] [Table 8]
(8th Table)
<img file="WO2005041663A1_D0026.tif" />
[0164] [-- table 9]
(9th Table)
<img file="WO2005041663A1_D0027.tif" />
[0165] [-- table 10]
(The 1 0 table)
<img file="WO2005041663A1_D0028.tif" />
[0166] [-- table 11]
(The 1 1 table)
<img file="WO2005041663A1_D0029.tif" />
[0167] [-- table 12] (The 1 2 table)
<img file="WO2005041663A1_D0030.tif" />
[0168] [-- table 13]
(The 1 3 table)<img file="WO2005041663A1_D0031.tif" />
[0169] [-- table 14]
(The 1 4 table)
<img file="WO2005041663A1_D0032.tif" />
[0170] [-- table 15]
(The 1 5 table)
<img file="WO2005041663A1_D0033.tif" />
[0171] [-- table 16] (The 1 6 table) <img file="WO2005041663A1_D0034.tif" />
[0172] [-- table 17]
(The 1 7 table)
<img file="WO2005041663A1_D0035.tif" />
[0173] [-- table 18]
(The 1 8 table)
<img file="WO2005041663A1_D0036.tif" />
[0174] [-- table 19]
(The 1 9 table)
<img file="WO2005041663A1_D0037.tif" />
[0175] [-- table 20] (The 2 0 table) <img file="WO2005041663A1_D0038.tif" />
[0176] [-- table 21]
(The 2 1 table)<img file="WO2005041663A1_D0039.tif" />
[0177] [-- table 22]
(The 2 2 table)
<img file="WO2005041663A1_D0040.tif" />
[0178] [-- table 23]
(The 2 3 table)
<img file="WO2005041663A1_D0041.tif" />
[0179] [-- table 24] (The 2 4 table)
<img file="WO2005041663A1_D0042.tif" />
[0180] [-- table 25]
(The 2 5 table)
<img file="WO2005041663A1_D0043.tif" />
[0181] [-- table 26]
(The 2 6 table)<img file="WO2005041663A1_D0044.tif" />
[0182] [-- table 27]
(The 2 7 table)
<img file="WO2005041663A1_D0045.tif" />
[0183] [-- table 28] (The 2 8 table)
<img file="WO2005041663A1_D0046.tif" />
[0184] [-- table 29]
(The 2 9 table)
<img file="WO2005041663A1_D0047.tif" />
[0185] [-- table 30]
(The 3 0 table)
<img file="WO2005041663A1_D0048.tif" />
[0186] [-- table 31]
(The 3 1 table)
<img file="WO2005041663A1_D0049.tif" />
[0187] [-- table 32]
(The 3 2 table)
Triage Mennonite The amount of compound No. 39 dropping medicine Amount of Le dropping medicine 6. 3 g/ha 3. l g/ha Og/ha
6. 3g/ha 5 (13. 5) 2. 5 (29. 3) 45. 0
3. l g/ha 30. 0 17. 5 (42. 3) 65. 0
Og/ha 30.0 65.0 [0188] [Table 33]
(The 3 3 table)<img file="WO2005041663A1_D0050.tif" />
[0189] [-- table 34]
(The 3 4 table)<img file="WO2005041663A1_D0051.tif" />
[0190] [-- table 35]
(The 3 5 table)
<img file="WO2005041663A1_D0052.tif" />
[0191] [-- table 36]
(The 3 6 table)<img file="WO2005041663A1_D0053.tif" />
[0192] [-- table 37] (The 3 7 table)
<img file="WO2005041663A1_D0054.tif" />
[0193] [-- table 38]
(The 3 8 table)
<img file="WO2005041663A1_D0055.tif" />
[0194] [-- table 39]
(The 3 9 table)
<img file="WO2005041663A1_D0056.tif" />
[0195] [-- table 40]
(The 4 0 table)
<img file="WO2005041663A1_D0057.tif" />
[0196] [-- table 41]
(The 4 1 table)
Full Quinconazo The amount of compound No. 40 dropping medicine Amount of - Le dropping medicine 3. l g/ha 1. 6g/ha Og/ha
50g/ha 0 (6. 0) 10. 0 (13. 5) 30. 0
Og/ha 20.0 45.0 [0197] [Table 42]
(The 4 2 table)
<img file="WO2005041663A1_D0058.tif" />
[0198] [-- table 43]
(The 4 3 table)<img file="WO2005041663A1_D0059.tif" />
[0199] [-- table 44]
(The 4 4 table)
<img file="WO2005041663A1_D0060.tif" />
[0200] [-- table 45]
(The 4 5 table)<img file="WO2005041663A1_D0061.tif" />
[0201] [-- table 46] (The 46 table)
<img file="WO2005041663A1_D0062.tif" />
[0202] [-- table 47]
(47th Table)
<img file="WO2005041663A1_D0063.tif" />
[0204] [-- table 49]
(49th Table)
<img file="WO2005041663A1_D0064.tif" />
[0205] [-- table 50]
(The 5 0 table)
Te ♪ Laconasoe The amount of compound No.23 dropping medicine Amount of Le dropping medicine 6. /ha 3. l/ha Og/ha
6.3g/ha 0 (1.75) 5.0(10.5) 35.0
3. lg/ha 2.5 (4.0) 7.5 (24.0) 80.0
Og/ha 5.0 30.0 [0206] [Table 51]
(The 5 1 table)<img file="WO2005041663A1_D0065.tif" />
[0207] [-- table 52]
(The 5 2 table)<img file="WO2005041663A1_D0066.tif" />
[0208] [-- table 53]
(The 5 3 table)<img file="WO2005041663A1_D0067.tif" />
[0209] Example of examination 2 Curie Japanese noodles This disease preventive effect examination
curie (variety: four leaves) is grown in the poly bowl 7.5 cm in diameter -- when it reached at 1.5 leaf terms, mixed medical fluid 10mL which adjusted the present invention compound to predetermined concentration was sprinkled with the spray gun. medical fluid after drying, spraying inoculation of the part student spore suspension of Japanese noodles Pathogenic bacteria is carried out -- it maintains at the homoiothermal interior of a room of 20"C It was. inoculation 6 -- in 11 days, spore formation area is investigated and an attack rate is searched for like example 3 of an examination -- the result was shown in 54th table 1 The 96 table. The average lesion area of an unprocessed division is replaced with a medical fluid. The same operation as a processing division is performed except having sprinkled water with the spray gun. It asked.
The theoretical value by Colby's formula was combined in () of The 54 table 1 The 96 table, and was shown.
[0210] [-- table 54] Truffe Rumizo 1 Le Compound No. 23 concentration Concentration 8ppm 4ppm 2ppm Oppm
31ppm 0 (2. 0) 0 (2. 1) 0 (2. 4) 2. 4
16ppm 54. 3 (57. 9) 64. 2 64. 2 (69. 1) 69. 1
Oppm 83. 9 88. 9 100
[0211] [-- table 55]
(The 5 5 table)
<img file="WO2005041663A1_D0068.tif" />
[0212] [-- table 56]
(The 5 6 table)
<img file="WO2005041663A1_D0069.tif" />
[0213] [-- table 57]
(The 5 7 table)
<img file="WO2005041663A1_D0070.tif" />
[0214] [-- table 58]
(The 5 8 table)
<img file="WO2005041663A1_D0071.tif" />
[0215] [-- table 59] (The 5 9 table)
<img file="WO2005041663A1_D0072.tif" />
[0216] [-- table 60]
(The 6 0 table)
<img file="WO2005041663A1_D0073.tif" />
[0217] [-- table 61]
(The 6 1 table)<img file="WO2005041663A1_D0074.tif" />
[0218] [-- table 62]
(The 6 2 table)<img file="WO2005041663A1_D0075.tif" />
[0219] [-- table 63]
(The 6 3 table)
<img file="WO2005041663A1_D0076.tif" />
[0220] [-- table 64] (The 6 4 table) <img file="WO2005041663A1_D0077.tif" />
[0221] [-- table 65]
(The 6 5 table)<img file="WO2005041663A1_D0078.tif" />
[0222] [-- table 66]
(The 6 6 table)<img file="WO2005041663A1_D0079.tif" />
[0223] [-- table 67]
(The 6 7 table)
<img file="WO2005041663A1_D0080.tif" />
[0224] [-- table 68]
(The 6 8 table)<img file="WO2005041663A1_D0081.tif" />
[0225] [-- table 69] (The 6 9 table)
<img file="WO2005041663A1_D0082.tif" />
[0226] [-- table 70]
(The 7 0 table)
<img file="WO2005041663A1_D0083.tif" />
[0227] [-- table 71]
(The 7 1 table)<img file="WO2005041663A1_D0084.tif" />
[0228] [-- table 72]
(The 7 2 table)
<img file="WO2005041663A1_D0085.tif" />
[0229] [-- table 73]
(The 7 3 table)
Polyoxin concentration Compound No.35 concentration
4ppm 2ppm lppm Oppm
125rhorhopiiota 0 (2.5) 4.4 (14.2) 11.7 (17.3) 21.6
63ppm 16.7 31.4 31.4(37.0) 46.1
3 lppm 16.7 31.4(52.8) 60.8 (64.6) 80.4
Oppm 11.7 65.7 80.4 [0230] [Table 74]
(The 7 4 table)
<img file="WO2005041663A1_D0086.tif" />
[0231] [-- table 75]
(The 7 5 table)
<img file="WO2005041663A1_D0087.tif" />
[0232] [-- table 76]
(The 7 6 table)
<img file="WO2005041663A1_D0088.tif" />
[0233] [-- table 77]
(The 7 7 table)<img file="WO2005041663A1_D0089.tif" />
[0234] [-- table 78] (The 7 8 table)
<img file="WO2005041663A1_D0090.tif" />
[0235] [-- table 79]
(The 7 9 table)
<img file="WO2005041663A1_D0091.tif" />
[0236] [-- table 80]
(The 8 0 table)
<img file="WO2005041663A1_D0092.tif" />
[0237] [-- table 81]
(The 8 1 table)
<img file="WO2005041663A1_D0093.tif" />
[0238] [-- table 82]
(The 8 2 table)
Chloro Saronil concentration Compound No. 39 concentration
16 A customer 8ppm 4ppm Oppm
125ppm 2. 5 (12. 0) 30. 0 30. 0 (48. 0) 60. 0
63ppm 2. 5 (16. 0) 20. 0 (24. 0) 30. 0 (64. 0) 80. 0
31ppm 5. 0 (16. 0) 20. 0 (24. 0) 45. 0 (64. 0) 80. 0
Oppm 20. 0 30.0 80.0 [0239] [Table 83]
(The 8 3 table)
<img file="WO2005041663A1_D0094.tif" />
[0240] [-- table 84]
(The 8 4 table)
<img file="WO2005041663A1_D0095.tif" />
[0241] [-- table 85]
(The 8 5 table)
<img file="WO2005041663A1_D0096.tif" />
[0242] [-- table 86]
(The 8 6 table)
<img file="WO2005041663A1_D0097.tif" />
[0243] [-- table 87]
(The 8 7 table)
Imibenconazo 1 Le Compound No. 40 concentration Concentration 2ppm lppm Oppm
16ppm 35. 6 (64. 3) 60. 4 (80. 2) 80. 2
8ppm 60. 4 (80. 2) 80. 2 (100) 100
Oppm 80. 2 100 [0244] [Table 88]
(The 8 8 table)<img file="WO2005041663A1_D0098.tif" />
[0245] [-- table 89]
(The 8 9 table)<img file="WO2005041663A1_D0099.tif" />
[0246] [-- table 90]
(The 9 0 table)<img file="WO2005041663A1_D0100.tif" />
[0247] [-- table 91]
(The 9 1 table)<img file="WO2005041663A1_D0101.tif" />
[0248] [-- table 92]
(The 9 2 table)<img file="WO2005041663A1_D0102.tif" />
[0249] [-- table 93] (The 9 3 table) <img file="WO2005041663A1_D0103.tif" />
[0250] [-- table 94]
(The 9 4 table)<img file="WO2005041663A1_D0104.tif" />
[0251] [-- table 95]
(The 9 5 table)<img file="WO2005041663A1_D0105.tif" />
[0252] [-- table 96]
(The 9 6 table)<img file="WO2005041663A1_D0106.tif" />
[0253] the amount of tablets in the present invention although the example of a tablet of the present invention is indicated below, a drug design, etc. -- written example what is limited to seeing -- [ Then. ],
Example 1 of a tablet
(a) 78 weight sections of kaolin
(b) 2 weight sections of Naphthalene sulfonic acid soda formalin condensation things
(c) 5 weight sections of polyoxy ethylene alkyl aryl sulfate
(d) 15 weight sections of hydrous amorphous silica dioxides
They are a mixture of each above ingredient, a compound of formula (I), and epoxy Conazo 1 Le 8 : 1 : It mixes with the weight percentage of 1 and wettable powder is obtained.
[0254] Example 2 of a tablet
(a) 0.5 weight sections of compounds of formula (I)
(b) epoxy Conazo 1 -- Nollet 0. 5 weight section
(c) 20 weight sections of bentonites
(d) 74 weight sections of kaolin
(e) rig-A sulfonic acid soda
A proper quantity of Granulation necessary water is added to each above ingredient, it mixes and Granulation and a grain agent is obtained.<sub>c</sub>
[0255] Example 3 of a tablet
(a) 2 weight sections of present invention compounds
(b) 3 weight sections of epoxyconazole
(c) 95 weight sections of talc
Each above ingredient is mixed uniformly and a powder agent is obtained.
Contents3
110 sheets
Sheet 1 Sheet 2 Sheet 3 Sheet 4 Sheet 5 Sheet 6 Sheet 7 Sheet 8 Sheet 9 Sheet 10 Sheet 11 Sheet 12 Sheet 13 Sheet 14 Sheet 15 Sheet 16 Sheet 17 Sheet 18 Sheet 19 Sheet 20 Sheet 21 Sheet 22 Sheet 23 Sheet 24 Sheet 25 Sheet 26 Sheet 27 Sheet 28 Sheet 29 Sheet 30 Sheet 31 Sheet 32 Sheet 33 Sheet 34 Sheet 35 Sheet 36 Sheet 37 Sheet 38 Sheet 39 Sheet 40 Sheet 41 Sheet 42 Sheet 43 Sheet 44 Sheet 45 Sheet 46 Sheet 47 Sheet 48 Sheet 49 Sheet 50 Sheet 51 Sheet 52 Sheet 53 Sheet 54 Sheet 55 Sheet 56 Sheet 57 Sheet 58 Sheet 59 Sheet 60 Sheet 61 Sheet 62 Sheet 63 Sheet 64 Sheet 65 Sheet 66 Sheet 67 Sheet 68 Sheet 69 Sheet 70 Sheet 71 Sheet 72 Sheet 73 Sheet 74 Sheet 75 Sheet 76 Sheet 77 Sheet 78 Sheet 79 Sheet 80 Sheet 81 Sheet 82 Sheet 83 Sheet 84 Sheet 85 Sheet 86 Sheet 87 Sheet 88 Sheet 89 Sheet 90 Sheet 91 Sheet 92 Sheet 93 Sheet 94 Sheet 95 Sheet 96 Sheet 97 Sheet 98 Sheet 99 Sheet 100 Sheet 101 Sheet 102 Sheet 103 Sheet 104 Sheet 105 Sheet 106 Sheet 107 Sheet 108 Sheet 109 Sheet 110
Every citation, both ways
| Document | Relation | Office | Category | Cited during |
|---|---|---|---|---|
| JP2013006826A | Cited by | Japan | – | Examiner |
| WO2012165266A1 | Cited by | World Intellectual Property Organization (WIPO) | – | Applicant |
| CN103355303A | Cited by | China | – | Search report |
| US7572808B2 | Cited by | United States of America | – | Applicant |
| JP2013010743A | Cited by | Japan | – | Search report |
| RU2507746C2 | Cited by | Russian Federation | – | Search report |
| US10015964B2 | Cited by | United States of America | – | Applicant |
| US10172357B2 | Cited by | United States of America | – | Applicant |
| WO2013187526A1 | Cited by | World Intellectual Property Organization (WIPO) | – | Applicant |
| WO2013008604A1 | Cited by | World Intellectual Property Organization (WIPO) | – | Applicant |
| CN103858883A | Cited by | China | – | Search report |
| EP2529627A1 | Cited by | European Patent Office (EPO) | – | Applicant |
| WO2012161235A2 | Cited by | World Intellectual Property Organization (WIPO) | – | Applicant |
| WO2008004596A1 | Cited by | World Intellectual Property Organization (WIPO) | – | International search |
| JP2002356474A | Cites | Japan | X | International search |
62 members in 14 offices
Priority claims12
| Document | Office | Kind | Date |
|---|---|---|---|
| 2003371863 | Japan | A | |
| 2003371863 | Japan | A | |
| 2004006355 | Japan | A | |
| 2004006355 | Japan | A | |
| 2004210174 | Japan | A | |
| 2004210174 | Japan | A | |
| 2003371863 | – | – | – |
| 2004006355 | – | – | – |
| 2004210174 | – | – | – |
| JP20030371863 | – | – | – |
| JP20040006355 | – | – | – |
| JP20040210174 | – | – | – |
Members62
| Document | Office | Kind | |
|---|---|---|---|
| AU2004285363A1 | Australia | A1 | |
| WO2005041663A1This record | World Intellectual Property Organization (WIPO) | A1 | |
| JP2006052195A | Japan | A | |
| EP1679003A1 | European Patent Office (EPO) | A1 | |
| US2006194849A1 | United States of America | A1 | |
| IL175266A0 | Israel | A0 | |
| KR20060113908A | Republic of Korea | A | |
| CN1874680A | China | A | |
| BRPI0415555A | Brazil | A | |
| CN101199274A | China | A | |
| CN101215260A | China | A | |
| IL190635A0 | Israel | A0 | |
| AU2009202568A1 | Australia | A1 | |
| AU2009212886A1 | Australia | A1 | |
| KR20090101390A | Republic of Korea | A | |
| US2009247763A1 | United States of America | A1 | |
| AU2004285363B2 | Australia | B2 | |
| CN100581362C | China | C | |
| CN101822253A | China | A | |
| AU2009202568B2 | Australia | B2 | |
| AU2009212886B2 | Australia | B2 | |
| AU2011201943A1 | Australia | A1 | |
| EP1679003A4 | European Patent Office (EPO) | A4 | |
| EP2338335A1 | European Patent Office (EPO) | A1 | |
| CN102165961A | China | A | |
| JP2011225622A | Japan | A | |
| JP2011225623A | Japan | A | |
| US2011280959A1 | United States of America | A1 | |
| JP2012006952A | Japan | A | |
| IL190635A | Israel | A | |
| KR101128194B1 | Republic of Korea | B1 | |
| CN101822253B | China | B | |
| JP4918215B2 | Japan | B2 | |
| AU2011201943B2 | Australia | B2 | |
| US2012135088A1 | United States of America | A1 | |
| KR101163242B1 | Republic of Korea | B1 | |
| AU2012216657A1 | Australia | A1 | |
| CN101199274B | China | B | |
| AU2012216657B2 | Australia | B2 | |
| JP2013213065A | Japan | A | |
| CN102165961B | China | B | |
| JP5341962B2 | Japan | B2 | |
| JP5341963B2 | Japan | B2 | |
| US8609150B2 | United States of America | B2 | |
| CN103478142A | China | A | |
| US8653113B2 | United States of America | B2 | |
| US8653277B2 | United States of America | B2 | |
| JP5450526B2 | Japan | B2 | |
| US2014107138A1 | United States of America | A1 | |
| CN101215260B | China | B | |
| JP5639230B2 | Japan | B2 | |
| EP1679003B1 | European Patent Office (EPO) | B1 | |
| DK1679003T3 | Denmark | T3 | |
| ES2535705T3 | Spain | T3 | |
| PT1679003E | Portugal | E | |
| IL175266A | Israel | A | |
| PL1679003T3 | Poland | T3 | |
| HUE025041T2 | Hungary | T2 | |
| CN103478142B | China | B | |
| US9655362B2 | United States of America | B2 | |
| US2017188579A1 | United States of America | A1 | |
| BRPI0415555B1 | Brazil | B1 |
18 legal events, as 3 offices reported them to INPADOC
Over the term
Point at a mark for the eventEvents
| Event | Code | Office | |
|---|---|---|---|
| Wipo information: entry into national phaseWWE | WWE | WO | |
| Entry into the national phaseENP | ENP | BR | |
| Wipo information: published in national officeWWP | WWP | WO | |
| Wipo information: published in national officeWWP | WWP | WO | |
| Entry into the national phaseENP | ENP | AU | |
| Wipo information: entry into national phaseWWE | WWE | WO | |
| Wipo information: entry into national phaseWWE | WWE | WO | |
| Wipo information: published in national officeWWP | WWP | WO | |
| Wipo information: entry into national phaseWWE | WWE | WO | |
| Wipo information: entry into national phaseWWE | WWE | WO | |
| Wipo information: entry into national phaseWWE | WWE | WO | |
| Wipo information: entry into national phaseWWE | WWE | WO | |
| Wipo information: entry into national phaseWWE | WWE | WO | |
| Ep: the epo has been informed by wipo that ep was designated in this application121 | 121 | WO | |
| Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed from 20040101)DPEN | DPEN | WO | |
| Designated statesAK | AK | WO | |
| Designated countries for regional patentsAL | AL | WO | |
| Wipo information: entry into national phaseWWE | WWE | WO |
Numbers
- Publication
- 2005/041663
- Publication, DOCDB
- 2005041663
- Publication, EPODOC
- WO2005041663
- Application
- 16156
- Application, DOCDB
- 2004016156
- Application, EPODOC
- WO2004JP16156
Titles2
- English
- BACTERICIDE COMPOSITION AND METHOD OF CONTROLLING PLANT DISEASE
- French
- COMPOSITION BACTERICIDE ET PROCEDE DE LUTTE CONTRE LA MALADIE DES PLANTES
Classification
- CPC, 6
- A01N43/653
- A01N43/40
- C07D213/64
- A01N43/50
- A01N47/40
- A01N55/00
- IPC, 12
- A01N35 04
- A01N37 06
- A01N37 34
- A01N43 08
- A01N43 40
- A01N43 50
- A01N43 54
- A01N43 653
- A01N43 84
- A01N47 38
- A01N47 42
- A01N47 44
Designated states125
- Regional, 71
- African Regional Intellectual Property Organization (ARIPO)
- Botswana
- Ghana
- Gambia
- Kenya
- Lesotho
- Malawi
- Mozambique
- Namibia
- Sudan
- Sierra Leone
- Eswatini
- United Republic of Tanzania
- Uganda
- Zambia
- Zimbabwe
- Eurasian Patent Organization (EAPO)
- Armenia
- Azerbaijan
- Belarus
- Kyrgyzstan
- Kazakhstan
- Republic of Moldova
- Russian Federation
and 47 moreShow fewer
- Tajikistan
- Turkmenistan
- European Patent Office (EPO)
- Austria
- Belgium
- Bulgaria
- Switzerland
- Cyprus
- Czechia
- Germany
- Denmark
- Estonia
- Spain
- Finland
- France
- United Kingdom
- Greece
- Hungary
- Ireland
- Italy
- Luxembourg
- Monaco
- Netherlands (Kingdom of the)
- Poland
- Portugal
- Romania
- Sweden
- Slovenia
- Slovakia
- Türkiye
- African Intellectual Property Organization (OAPI)
- Burkina Faso
- Benin
- Central African Republic
- Congo
- Côte d’Ivoire
- Cameroon
- Gabon
- Guinea
- Equatorial Guinea
- Guinea-Bissau
- Mali
- Mauritania
- Niger
- Senegal
- Chad
- Togo
- National, 54
- United Arab Emirates
- Antigua and Barbuda
- Albania
- Australia
- Bosnia and Herzegovina
- Barbados
- Brazil
- Belize
- Canada
- China
- Colombia
- Costa Rica
- Cuba
- Dominica
- Algeria
- Ecuador
- Egypt
- Grenada
- Georgia
- Croatia
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- Israel
- India
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- Democratic People’s Republic of Korea
- Republic of Korea
- Saint Lucia
- Sri Lanka
- Liberia
- Lithuania
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- North Macedonia
- Mongolia
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- Ukraine
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- Saint Vincent and the Grenadines
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- Yugoslavia, later Serbia and Montenegro (until 2006)
- South Africa