AT366664B

N-(Arylthiocarbamoyl)-2-amino-1H-isoindole-1,3-(2H)diones, processes for their preparation and their use as plant growth regulators.

Abstract

This record has no abstract on file.

AT366664B, drawing sheet 1 — Sheet 1 of 9

Term

Term ended

Expired 7 March 2000, 26.5 years ago.

3 claims: 2 independent, 1 dependent

1
Verfahren zur Herstellung von neuen N-(3-Aryl-thioureido)-phthalimiden der allgemeinen Formel FATENTANS (I) worin 5 R 1 für Wasserstoff, Ci-C k -Alkyl oder -Alkoxy, Nitro oder Halogen steht;n eine ganze Zahl von 1 bis 4 bedeutet, wobei bei n = 2 bis 4 die Substituenten gleich oder verschieden sein können;R 2 und R 3 unabhängig voneinander für Wasserstoff, Cj-C^-Alkyl oder Benzyl stehen und R·* für Adamantyl, C 3 -C 4 -Alkyl oder -Alkenyl, Halogenbenzyl, Naphthyl oder Phenyl 10 steht, welch letzteres gegebenenfalls ein- bis dreifach durch gleiche oder verschiedene Reste aus der Reihe Cyan, Benzyloxy, Nitro, Brom, Chlor, Trifluormethyl, C,-C ,-Alkyl, -Alkenyl, -Alkoxy, -Alkylthio oder -Dialkylamino substituiert ist, dadurch gekennzeichnet, daß man ein l-(o-Carbobenzoyl)-thiosemicarbazid der allgemeinen Formel (II) 15 worin X OH oder O-Alkyl bedeutet, in einem nichtreaktiven organischen Lösungsmittel durch Einwirken eines Kondensationsmittels oder von Hitze einer Ringschlußreaktion unterwirft, wobei das Kondensationsmittel einer Base oder im Falle, daß -X für die Gruppe -OH steht, ein dehydratisierendes Mittel sein kann.
2
Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man auf ein l-(o-Carbalkoxyben20 zoyl)-thiosemicarbazid der allgemeinen Formel worin R für Methyl oder Äthyl steht, bei etwa Raumtemperatur in Gegenwart eines polaren organischen Lösungsmittels ein gehindertes aliphatisches Amin einwirken läßt.
3
Verfahren nach den Ansprüchen 1 und 2, dadurch gekennzeichnet, daß man als Lösungs25 mittel Aceton, Äthylacetat oder Tetrahydrofuran und als Amin tert.Butylamin einsetzt. Druck:Ing.E.Voytjech, Wien

Independent claims3

258 paragraphs, as filed

In the application of numerous chemical substances to plants, plant growth-regulating effects have been observed. In general, only very few of these substances can be used to advantage for the plants covered by the treatment. In most cases, the beneficial effects, if any, are minor and the major effects are so dramatic that the compounds can only be used to destroy the plants. Examples of plant growth-regulating compounds having drastic effects which have become useful as herbicides include 2,4-D, EPTC and alachlor. Among the possible uses for plant growth regulating compounds with less drastic effects, the following uses may be mentioned:

Increased flowering or flowering (pineapple);

Propagation of inflorescences, pods or pods, seed stems and / or inflorescences (prevention of stagnation of inflorescences or exudation or withering of flowers);

Increasing the size (magnification) of fruits, vegetables, seeds and / or tubers (grapes, 15 soybeans, sugar beet, etc.);

Reducing the size of fruits, vegetables, seeds and / or tubers (potatoes, grapefruit);

Increase in the number of root sprouts (cereals);

Increasing the number of shoots from a seed crown or from a root neck (alfalfa);

stronger branching (soybeans) or further spreading of branches (apples);

Reduction of height (shortening of stalks between nodes) in crops and ornamentals (cereals and mums);

Growth inhibition (lawn, cotton, perennial legumes in root-sprouted maize);

Increase in yields of corn by larger pistons, better filled pistons and / or more 25 pistons per plant;

Increase the nutritional value of seeds, fruits, vegetables, forage plants, etc. (protein content);

Reduction of perspiration (resistance to dryness);

Reduction of respiration (potatoes or sugar beets during storage).

We have now discovered a group of novel compounds which have a large number of growth-regulating properties and thus show utility for many applications, including the applications mentioned above. The invention thus relates to the creation of these new compounds.

The new class of plant growth regulating compounds corresponds to the general structural formula

wherein

R1 is hydrogen, C 1 -C 4 alkyl or alkoxy, nitro or halogen;

n is an integer from 1 to 4, wherein when n = 2 to 4, the substituents may be the same or different;

R2 and R3 independently of one another represent hydrogen, C 1 -C 4 -alkyl or benzyl and

R1* for adamantyl, C3C ,, alkyl or alkenyl, halobenzyl, naphthyl or phenyl, the latter optionally mono- to trisubstituted by identical or different radicals selected from cyano, benzyloxy, nitro, bromo, chloro, trifluoromethyl, Cj-C ^ alkyl , Alkenyl, alkoxy, alkylthio or dialkylamino.

The compounds mentioned above are used to regulate the growth of plants by applying an effective amount to the plants, seeds or soil, preferably

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- 3 is applied in combination with an inert carrier or diluent and a surfactant, the usual methods are met.

The novel compounds can be prepared according to the invention by reacting a 1- (o-carbobenzoyl) -thiosemicarbazide of the general formula

wherein X is OH or O-alkyl, in a non-reactive organic solvent by the action of a condensing agent or heat of a ring-closing reaction, wherein the condensing agent may be a base or in the event that -X is the group -OH, a dehydrating agent.

The success of the method of preparation of the invention depends on the avoidance of competing reactions that can occur if the specialized conditions are not met. In general, the method can be carried out within the limits of daytime ambient temperatures. At temperatures above 50 ° C, however, a different reaction occurs in which an aryl isothiocyanate by-product is released. To achieve the best

Results are preferred to room temperature, ie the temperature of the rooms for human habitation.

The solvent should be polar so that the amine used to promote the reaction can develop the desired weakly basic conditions. However, the solvent should not be reactive in the system. Alcohols are for example unsuitable and dimethoxyethane 20 leads to impure products. As suitable solvents, ethyl acetate, toluene, acetone and tetrahydrofuran have been found.

The amine should have sufficient base strength to promote ring closure. However, a non-hindered, primary or secondary basic amine will compete with the amide nitrogen in the starting material and prevent ring closure. For example, piperidine and n-propylamine 25 react to form the corresponding amides and thus effectively prevent ring closure. With pyridine no reaction is observed. As examples of suitable amines, there may be mentioned tert-butylamine, diisopropylamine, triethylamine, 1,4-diazabicyclo [2,2,2] octane and isopropylamine. The structures of these amines are hindered in amide formation as a competing reaction.

Among the suitable reaction solvents and hindered aliphatic amines, certain combinations are more desirable than others. For example, the use of tert-butylamine together with acetone, ethyl acetate or tetrahydrofuran as the solvent is preferred. Acetone is the preferred solvent when using triethylamine.

When the reaction time is prolonged in the above-described procedure, ring closure also occurs in some cases and results in good yields of the desired end product. However, the method is not equally satisfactory for all compounds of this class. It is also possible to carry out the ring closure of the product in the above method under strongly basic conditions, for example in ethanolic sodium hydroxide, but only greatly reduced yields of the desired product are achieved in this way.

The improved method for preparing the compounds according to the invention is a general method which is not limited to the preparation of only those compounds which are within the strict limits stated above. The nature of the substituent groups that may be critical to the properties of the desired compounds,

No. 4,666,664 is not particularly critical to the applicability of the improved synthetic method.

By selecting suitable amines and solvents, an experienced chemist will be able to use the improved ring closure method to produce a large number of isoindole dione compounds.

Application of plant growth regulators

For highly effective compounds, the phytotoxic effects of pre-on-run and post-emergence treatment are often readily apparent. These effects can be demonstrated using the exemplary methods described below .

Preemergence treatment

Disposable paper cups about 6.3 cm deep were filled with soil and sprayed with aqueous spray mixtures in an amount of about 5.5 kg of active chemical / ha of sprayed area, then seeded with 6 kinds of plant seeds, and then about 0.6 cm covered soil. The spray mixtures were prepared by dissolving the appropriate amount of plant growth regulating compound in 15 ml of acetone, adding 4 ml of a solvent-emulsifier mixture consisting of 60% by weight of a commercial polyoxethylated Pf 1 anzenölemulgators (96 wt .-% active ingredient, Emulphor EL-719), 20% by weight of xylene and 20% by weight of deodorized kerosene, and adjusting the total volume to 60 ml by adding warm water. 21 Days after sowing and treatment, the plants are checked and the damage to the plants is evaluated according to the following classification:

Extent of effect = no effect = slight effect, plants recover = moderate effect, damage 26 to 75% = strong effect, damage 76 to 99% of leaves = maximum effect (all plants dead).

Post-emergence treatment In disposable foam trays, some plant species are grown in potting soil. Tomatoes are grown in 10 cm pots in the glasshouse. Aqueous spray formulations are prepared and the growing plants are sprayed at a spray volume of about 560 l / ha and at a rate of about 5.5 kg / ha. The spray mixtures are prepared in the manner indicated above. For comparison purposes, the plants are also sprayed in an amount of about 560 1 / ha with a spray mixture containing no plant growth regulator. The damage to the plant is again evaluated by the above-mentioned scale, and the observation of the plant growth-regulating effect is evaluated according to the following scale:

<td>effect</td><td>Abbreviation in the tables</td>

<td>Format effect</td><td>F</td>

<td>epinasty</td><td>e</td>

<td>growth inhibition</td><td>G</td>

<td>no emergence</td><td>K</td>

<td>necrosis</td><td>N</td>

In a typical example, the reaction of the invention is carried out at low temperature of about 2 to 5 ° C in the presence of NN1Dicyclohexylcarbodiimide, after which the reaction mixture is allowed to warm to room temperature upon standing. The yields can be up to about 60%, as illustrated in the following specific example.

N- (l-methyl-3-phenyl-thioureido) phthalimide

To an ice-cold solution of 8.25 g (0.025 mol) of 1- (2-carboxybenzoyl) -2-methyl-4-phenylthiosemicarbazide in 225 ml of 1,2-dimethoxyethane at ätwa 2 ° C is added a solution of 5.5 g (0.027 mol) of N, Ν'-dicyclohexylcarbodiimide was added dropwise with stirring at a temperature below 5 ° C. The mixture is stirred in an ice bath and then allowed to stand at room temperature overnight.

- 5.Nr.366664

The mixture is filtered to separate Ν, Ν'-dicyclohexylurea and the filtrate is placed under

Evaporated vacuum below 40 ° C to give a yellow amorphous solid, which is stirred in 100 ml of dry ether and heated moderately. The ether solution is allowed to stand for a few hours and filtered to yield 4.6 g (59%) of whitish-yellowish crystals of melting point 142 to 144 ° C. By recrystallization from ethyl acetate / hexane whitish crystals of mp. 151 to 153 ° C are obtained.

Mass spectrum: M+ 311

In the preparation of N- (3-aryl-thioureido) -phthalimides of the general formula (I) by ring closure of a corresponding 1- (o-carboxybenzoyl) -thiosemicarbazide greatly improved yields are achieved when the cyclization of a corresponding o-carbo - (C 3 -C ") alkoxybenzoyl thiosemicarbazide under very mild basic conditions in the presence of a non-reactive polar organic solvent and a reaction promoting amount of a hindered aliphatic

Amines undergo.

The embodiment of the production method according to the invention is explained in more detail in the following specific examples,

Example 1: To a solution of 3.0 g (0.0087 mol) of 1- (o-carbomethoxybenzoyl) -2-methyl-4-phenylthiosemicarbazide in 75 ml of tetrahydrofuran is added 0.065 g (0.00087 mol) of t-butylamine added and the reaction mixture is stirred at room temperature for 16 h. The solvent is removed under reduced pressure, the yellow residue dissolved in a small amount of acetone ge20 and the product is precipitated with dilute hydrochloric acid. The resulting solid is collected, stirred in water, filtered and dried to give 2.4 g (88%) of N- (1-methyl-3-phenylthioureido) -phthalimide, m.p. 150-153 ° C.

Examples 2 to 7: The above method is repeated with various o-carboalkoxybenzoyl-thiosemicarbazides according to the following scheme.

The table shows the results obtained.

<td>examples game</td><td>R</td><td>R2</td><td>Y</td><td>yield</td><td>Mp ° C</td>

<td></td><td></td><td></td><td></td><td>not isolated)</td><td> 151-153</td>

<td></td><td></td><td></td><td></td><td>not isolated)</td><td> 151-153</td>

<td> 5</td><td>CH 3</td><td>benzyl</td><td>H</td><td> -100%</td><td></td>

In the following example, the use of larger amounts of reaction components and the

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Use of acetone as solvent illustrated.

Example 8: Into a 5 liter reaction flask are introduced the following components:

1000 ml of acetone

280 g l- (o-carbomethoxybenzoyl) -2-methyl-4-phenyl-thiosemicarbazide and

8.6 ml of tert-butylamine

In about 20 minutes, a complete solution is achieved. The mixture is then stirred at room temperature overnight. At the end of this period some solids can be detected in the reactor. There are added 2 1 of water, whereby the temperature rises to 35 ° C. The reaction mixture is then cooled to 10 ° C and the solid product is recovered by filtration. The product is washed on the filter with water, then with isopropyl alcohol and then again with water and dried in an oven at 50 ° C. 213.1 g of N- (1-methyl-3-phenylthioureido) phthalimide (84% yield) of melting point 155.degree. To 156.degree. C. are obtained.

The carbomethoxybenzoyl thiosemicarbazide starting material for the present process 15 can be easily obtained by reacting the corresponding methylphthaloyl chloride with a suitable thiosemicarbazide. Both of these reagents can be used after common

Methods are presented. In the following, a method will be explained in more detail.

Synthesis of 1- (o-carbomethoxybenzoyl) -2-methyl-4-phenylthiosemicarbazide

A solution of 45.3 g (0.25 mol) of 2-methyl-4-phenylthiosemicarbazide and 19.8 g (0.25 mol) of pyridine in 800 ml of 1,2-dimethoxyethane is stirred at room temperature while 49 , 8 g (0.25 mol) of methylphthaloyl chloride in 100 ml of 1,2-dimethoxyethane are added dropwise over 2 h. The resulting reaction mixture is stirred for 16 h at room temperature. Then the contents of the flask are poured into ice water. The precipitate formed is collected and amounts to 73.3 g (85%), mp 153.5 to 154 ° C.

25 The following table lists numerous compounds obtained by the method according to the invention, as well as the pre-emergence and post-emergence herbicidal activity and plant growth-regulating activity.

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Impact on plant species

<td rowspan="6">Before on-effect</td><td>Sugar- turnip</td><td>rl Cd ι-rH CO N Ο C5 Ο Ο Ο o CM Cd t-1 ι-H I-1 CO I-I crj d) fn XX fl) fl) Ο Ο XX</td>

<td>radish</td><td>03 co oa co oooo it rH Cd iH CO cd CO XO h B) fi) (X) ο ο XX</td>

<td>millet</td><td>Tt CO CO CO 1-1 CO 0 0 0 0 0 o 03 co co co 03 co H-ι o o Hm © Hm Hm © Hm Hm</td>

<td>brome</td><td>ι-M 03 0 0 0 CO rM rl 03 rH W 03 CO X XXX fl) XX ο XX</td>

<td>cockfights Comb</td><td>03 CO 03 03 0 0 0 0 CO i-1 03 CO CO 03 03 fl, © 0 0 E Hm O © Hm Hm</td>

<td>Bouquet- grass</td><td>03 il τ-f 03 CO CO 0 0 0 0 0 0 CO rM rl 03 CO CO Hm © Hm Hm © E HmOHmHm</td>

<td colspan="2">u O &. hl</td><td>CO WWW Century BC Wm P pn at 03 m CO φ © o 03 S 03 O 03 1-1 τΗ NNNN £ © S il rl 1 1 1 1 1 1 2 o © in in r © © © ©50 η ο oo * m ο? o oo τ-i 'Ή rl i- <«H i-li-l r-1 rl rl</td>

<td colspan="2">encryption binding No.</td><td>TM © © rl 03 O * 03 03 © co m co com com in co t> «3 <« 3 * CO Ο * 0 * Ο * O * 03 03 03 03 03 03 03 03 03 03</td>

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Effect on plant species

<td colspan="2">Notes bez. usefulness</td><td>Growth reduction, increased fruit set. growth impairment growth impairment Growth reduction, oppression of foxtail and millet. growth impairment Cotton defoliants. Promotes the stocking of rice, Oats, cereals. prevents Blooming in tassels. Preemergence herbicide Post-emergence growth regulator Growth promoter (oats and tomatoes) increases fruit on tomatoes. Pre-emergence herbicide.</td>

<td rowspan="6">After 1 on Ef fect</td><td>tomatoes</td><td>rH CO WW t-1 r-1 rM 09 rH CO 00 to 2 o 2 oto otototo-</td>

<td>Sugar- turnip</td><td>rt 09 τ-Η tH C9 0 0 to 0 0 CO 09 C9 C9 09 «Cf ♦ - (09 09 to 2 to 2 otototo</td>

<td>radish</td><td>«-H Ή Oto 0 rt 09 09 iH τ-ί r-l fcOUdfc 2 1 ο o fc</td>

<td>alfalfa</td><td>09 CO CO 0 0 0 CO 09 rl CO CO W 09 CO to to to 22 otototo</td>

<td>millet</td><td>09 0 C9 CO tH rl to ooo o2 o to to</td>

<td colspan="2">encryption binding No.</td><td>rl Ο O rH 09 «θ 'C-0030 co to co co co in co m r co 0- o- o- fr » 09 09 09 09 C9 09 09C9 09 C9</td>

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Table (continued)

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Table (continued)

<td colspan="2">Notes bez. usefulness</td><td>M i £ 03 03 03 4-4 4-4 cd cd cd EXE J, CC 3 2 Ο 0 O CD >>> μ ccc Ä ®. 8 · 8 2. 07 Ό * ?? Ό i 7> ί Ό μ <μι i C μι μι μ <μ <μ ω · ϊ W * ± cd ο) · εο fö cd cd α: cd d cd cd cd cd 03 ^ 03 ^ 1-irnF-iRji-Mr-IrHQ. rl rt (-1 1 -i ri »-1 mtimhSmfc'Ssssin 3333 3 3 3 ®TlD ® StoHObD (DM hl bs M 60 hoωΕωΕθ3ωΕχ! Βθ (Β ^ CD CD CD CD CD ID d 1 | L [C i Cti ll W H H &* *"1 ** S ΐ 3 m 53 «C» Bi to co cn co to to «3Ε 3 £ εΕΕ £ -εεεε ee ^ 24-.2 3 ^ 2α3 3 3ο, ω 3 3 3 3 3 333332 SsEcnmcnE ^ mcnmra ra to OidOcd '^ Ocdicd-ß'GÄjcü ^' C-CÄXJ Λ £ 3 £££££££ ^ £££ ^ £££ οο 0 0 sOOiOorojQQQjcdcucuQjscdcdcdcd cd cd H<> fL,> 5fn> CQg5 £ fQ, h '£ 55S: £ 3</td>

<td rowspan="6">, Postemergence effect</td><td>tomatoes</td><td>04 CQ r-1 ri «i Ο 0 0 0 CO CQ CQ CO 04 ii i rH ti W WH fe [L til 0 ti 0 2 0 0 0 £ 9 ti</td>

<td>Sugar- turnip</td><td>CQ 04 04 03 ti 04 03 ti 03 ti ti 0 0 O0O 0 0 0 0 0 0 CQ CQ 04 03 04 03 04 03 04 04 04 ti r-1 EEEEEEEEEE or EEE</td>

<td>radish</td><td>04-04 04 0 0 0 0 CQ 04 ri r-1 r- (04 ti ti rH ti EE oE Z oEE 2 E 0 0 EE</td>

<td>alfalfa</td><td>CQ 04 04 »-1« -1 ti r-1 OO OO E OO CQ RH CQ ti 04 04 ti ri 04 ti »i 04 EWE EE ο ο ZEE ° EEE</td>

<td>millet</td><td>CQ 04 04 0 0 0 CQ 04 03 Ti ti ti ti 0 Ph 0 2 0 00Z 0022 0,0</td>

<td colspan="2">encryption binding No.</td><td>»I 04 0 * 0 * CO CO CO Ο * O CQ in 0 0 0 mm cd co 0 00040 * o * o * 0 * 0 * 0 * 03 CO COCOO 03 03 03 03 03 03 04 04 03 04 03 03 03 04 Ο4Ο4Ο4Ο3 04 04</td>

Nr.366664

Table (continued)

<td rowspan="6">Pre-emergence effect</td><td>Sugar- turnip</td><td>03 above co co 0 0 0 0 0 ec «-i ec co co o oPnoPhOoPm ^ PhPhO</td>

<td>radish</td><td>oa oa co oa 0 0 0 0 rH ri 03 CO CO CO ο ΟΟ ^ οΡηΟΟΕχμ ^ ΡΝΡμΟ</td>

<td colspan="2">cc</td><td>1 1 , '> -11 1 _, rt M} rt r * i rt _ λ X> ->, , g >>>. 'S, 5 r Λ Τ' ·0 Ε1?,·15 - l S Λ Ä _ C 4J .3 rt T -U 4J 4J • fi 2 eo «o EC tu r. , o, o o * 2 o - J2 E_ C Ε _ Η ® Ε- -o place> - 'iE "E rt S * S g1 ΐ Q £ E 3 £ ft S * .5 c S £? C? c fi z in ® CQ co® ® m ® £ in ® ® μ 2 JE Ο® 1 lb £ X r- <ca CL <e * ca CU <oa (X ca m-> oa Pm Ph + j O <co l co Pt co 0 «Pm</td>

<td colspan="2">CM IX</td><td>32 O 1-1 N rS N « n eq «η ß η nm« «32 32 BffiKQifflKKKÄO 32 CG 32 0 KO Ο O fflOO O OO -</td>

<td colspan="2">encryption binding No.</td><td>co cn t-η cc coco 05 o oa co «3 * m cot *» t · * |> in CO rl tH 05 05 0 0 0 0 Ο O0 Ci Ci Ο © rl KH rl 03 03 03 «Τ Ό W 03 co coco coco co co coco co cooco co</td>

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Table (continued)

<td colspan="2">Notes bez. usefulness</td><td>growth regulator growth regulator growth regulator</td>

<td rowspan="6">Postemergence effect</td><td>tomatoes</td><td>rt 03 i-ico 03 03 co 03 03 Ph © ® 2 Ph © o Ph © Ph Ph Ph Ph ©</td>

<td>Sugar- turnip</td><td>tH rt 03 rt 03 rl rH τ- (rt Ü O OOOÜ OOO 03 ri 03 03 03 03 03 rt © 03 rt © 03 Pm O Pm Ü. Op. Pm [i. P Pm Pm Pm P p, p</td>

<td colspan="2">encryption binding No.</td><td>co © w 03 co © © © oJcottf m © oo- 0> © © rt rt © © © © © © © © © © © O 1-1 rt rl rt 03 03 03 ςΡ «3« rP rt 03 © © © © © © © © © © © © © ©</td>

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Table (continued)

<td rowspan="6">Pre-run effect</td><td>Sugar- turnip</td><td>CS i-1 Ή 0 0 0 0 CO CS CS CS iH fr fr fr fr oooo fr fr fro O ©</td>

<td>radish</td><td>CS W CS t-1 00 0 d CO CS CS CS sf fr o oo ooo fr fr o oo</td>

<td>millet</td><td>co cs cs 0 0 o CO CO tH CS CO frfro 0 oooo fr o fr o oo</td>

<td>brome</td><td>co cs co cs 0 0 00 CS CO CO CS Ti * i-1 1-1 fr fr o fr oooo fr fr X fr o fr</td>

<td>cockfights Comb</td><td>CS rl 0 ü cs CS «J * frfro oo ooo fr o fro oo</td>

<td>Bouquet- grass</td><td>CS tH 1-1 ri 000 0 cs cs t-1 cs bhob cs CJ CJ CJ oobo oo</td>

<td colspan="2">c X</td><td>1 05 ΐ M> 0>> r -f co £ - in co XX "· over XXXXXXX MX XX</td>

<td colspan="2">encryption binding No.</td><td>β cs co co co> 05 ο ow ι-s in cor * » O i-l 05 CSCS CS CS CO 1-1 rH CS CS CS CS << cor »» r% c * · r * »co co co co co co cococo coco co co co co co cooco coco</td>

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Table (continued)

<td colspan="2">Notes bez. usefulness</td><td></td>

<td rowspan="6">Postemergence effect</td><td>tomatoes</td><td>i-1 0 cn tl rd C3 ί-1 cn P <Ph ο ο Z ο o o Ph Ph pq o Ph O</td>

<td>Sugar- turnip</td><td>ca-ca »-ί, -h cn 0 0 0 Ü 0 cn cn r-ι -h ca ca t-π th cn ca cn w ih L. 0 fc fc fc pt, fc fc pu, fc fc fco</td>

<td>radish</td><td>about ca w oo 0 0 0 0 ca ca ca cn m Ph PhO OO Ο Ο ο Ph Ο Ph Ο Ph O</td>

<td>oats</td><td>t- (approx 0 0 * - (approx OOO OOO OOO PhO pH ooo</td>

<td>alfalfa</td><td>cn »-π cn 0 0 0 NOO »-H ca W CO t-4 rH pH Ph Ο Ο Ph Ο Ο O Ph Ph Ph O PP</td>

<td>millet</td><td>cn 0 ca OOO oo ooo OO PhO io</td>

<td colspan="2">encryption binding No.</td><td>co ca co co co s ο o o th ii tn co s · Or-ιο caca ca ca caca caca «Ar co s S» IS co co co co co co cn cn cn cn cn cn cn cn cn cn cn cn cn cn</td>

Nr.366664

Table (continued)

<td>radish</td><td>rl rl rd 04 o cd cd cd 04 rd rd 04 o UU Ul o Ul</td>

<td>brome</td><td>CQ CD rd 04 rl rd «Φ hhh oh Ü 1</td>

<td>ü O ά H</td><td></td><td>CQ C0 © © © © r-1 © © O 'T1 © CO © © CQ © © CQCOCQ ©©© CDCQ © rd rd rd rd rd [> rd O4rd © rd rdrdO4 II 2 II 1 II II III III ό © 0 * CQ © O 0 * © CO CQ 0- © 04 © CO © QO © © © © © C3COCOO © © © © C3COCOO rd rd rd rd rd r-1 04 rd ^ d rd 04</td>

<td colspan="2">CC</td><td>rd rd Γ1 rd rd rd TL 1 >> >> r >> C 1 , c ι £ s ι £ ~ 7 t, ί d S'ä.ort © 'r'eiÄsrt'd ^ S-Si ^^ QH.dx μ 0 CU η 3 CU μ 0 _ E ^^ 5 ^ tr, o □ .2 TL E 0 £ bL bL 'S t Λ £ Ο>? 5 *3ο ^ * 3 ° ^ 22'§5 JC Md rj | I LQJXJ fi) I ß QipTXJ + J >> ._ ß) d .fl Λ -Mrd IX ö 'μ § 4 * 2 & £ ö 22 2 LoSS-HU ^ ÜqcHtjQSwJk't'O ι ΰ 2 * 2 ι ι ä · 4- 4- ι ι ι ι ι ι E - £ £ £ £ £ £ £ £ £ £ £ £ «= R | £ 04 CU 04 E «© CL h © CU © + J 04 1 <0 fl * 0 E * 0 1 Ό 04 © TJ</td>

<td colspan="2">encryption binding No.</td><td>it is not eo oo os os co co eomo NN m mm r »π <« i in mmm in m co © © © © © © © © © © © © © © © © © © © © © © © © © © © © © ©</td>

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Table (continued)

<td colspan="2">Notes bez. usefulness</td><td></td>

<td rowspan="6">Postemergence effect</td><td>tomatoes</td><td>Ή CM vH ί -1 CO vH v CM CM vH vH Fe fez fe O fe fe fe fe fe fe</td>

<td>Sugar- turnip</td><td>CM vH vH co vH CM vH vH OO OO O OO O * - <CO tH fH CO CO fH CM CM vH vH CO CM CM CO vH bb 2 bb Fe Fe Ph b Ph bbbbbb</td>

<td colspan="2">encryption binding No.</td><td>CO © vH CM CO © CO © LO CD ¢ -. CO © O CM CM CO CO CO t> «Φ tO IO tO in in IO in CD © © © © CO 03 © CT! © CD © © © © © © © © © co co co co co co coo co © © © ©</td>

Nr.366664

106 members in 25 offices

This recordMember, by publication datePriority claim15 more offices are in the list below

Priority claims2

Priority claims
Document	Office	Kind	Date
1906579	United States of America	A	1979-03-09
11552880	United States of America	A	1980-02-11

Members106

Family members, oldest first
Document	Office	Kind
PT70894A	Portugal	A	1980-04-01
IL59465A0	Israel	A0	1980-05-30
BE882084A	Belgium	A	1980-09-05
DK100080A	Denmark	A	1980-09-10
FI800693A	Finland	A	1980-09-10
AU5586580A	Australia	A	1980-09-11
AU5586580A	Australia	A	1980-09-11
NL8001392A	Netherlands (Kingdom of the)	A	1980-09-11
EP0016571A1	European Patent Office (EPO)	A1	1980-10-01
FR2450815A1	France	A1	1980-10-03
BR8001308A	Brazil	A	1980-11-04
JPS55153765A	Japan	A	1980-11-29
GB2048246A	United Kingdom	A	1980-12-10
ES489301A0	Spain	A0	1981-02-16
ES8106293A1	Spain	A1	1981-02-16
US4264502A	United States of America	A	1981-04-28
GR67236B	Greece	B	1981-06-25
DK255880A	Denmark	A	1981-08-12
ES490960A0	Spain	A0	1981-09-01
ES8106890A1	Spain	A1	1981-09-01
ATA128480A	Austria	A	1981-09-15
ZA801139B	South Africa	B	1981-09-30
DD152714A5	German Democratic Republic (until 1990)	A5	1981-12-09
CA1122212A	Canada	A	1982-04-20
AT366664BThis record	Austria	B	1982-04-26
CA1122978A	Canada	A	1982-05-04
US4330322A	United States of America	A	1982-05-18
US4339382A	United States of America	A	1982-07-13
AR226696A1	Argentina	A1	1982-08-13
DD157557A5	German Democratic Republic (until 1990)	A5	1982-11-17
YU59280A	Yugoslavia, later Serbia and Montenegro (until 2006)	A	1983-02-28
GB2048246B	United Kingdom	B	1983-05-18
HU184770B	Hungary	B	1984-10-29
ATA268281A	Austria	A	1985-08-15
US2007091713A1	United States of America	A1	2007-04-26
US2007098379A1	United States of America	A1	2007-05-03
WO2007051147A2	World Intellectual Property Organization (WIPO)	A2	2007-05-03
US2007115378A1	United States of America	A1	2007-05-24
US2007116119A1	United States of America	A1	2007-05-24
WO2007062404A2	World Intellectual Property Organization (WIPO)	A2	2007-05-31
WO2007076198A2	World Intellectual Property Organization (WIPO)	A2	2007-07-05
US2007249900A1	United States of America	A1	2007-10-25
US2007255098A1	United States of America	A1	2007-11-01
WO2007126429A2	World Intellectual Property Organization (WIPO)	A2	2007-11-08
WO2007133276A2	World Intellectual Property Organization (WIPO)	A2	2007-11-22
US2008033247A1	United States of America	A1	2008-02-07
WO2007076198A3	World Intellectual Property Organization (WIPO)	A3	2008-04-10
WO2007051147A3	World Intellectual Property Organization (WIPO)	A3	2008-04-17
WO2007062404A3	World Intellectual Property Organization (WIPO)	A3	2008-04-24
US2008117968A1	United States of America	A1	2008-05-22
US2008143822A1	United States of America	A1	2008-06-19
WO2007133276A3	World Intellectual Property Organization (WIPO)	A3	2008-07-03
US2008170846A1	United States of America	A1	2008-07-17
WO2008089041A1	World Intellectual Property Organization (WIPO)	A1	2008-07-24
EP1949448A2	European Patent Office (EPO)	A2	2008-07-30
EP1952307A2	European Patent Office (EPO)	A2	2008-08-06
EP1952635A2	European Patent Office (EPO)	A2	2008-08-06
EP1974240A2	European Patent Office (EPO)	A2	2008-10-01
CN101305613A	China	A	2008-11-12
WO2007126429A3	World Intellectual Property Organization (WIPO)	A3	2008-11-27
DE06848892T1	Germany	T1	2009-01-22
CN101365986A	China	A	2009-02-11
ES2311444T1	Spain	T1	2009-02-16
US7495993B2	United States of America	B2	2009-02-24
JP2009513283A	Japan	A	2009-04-02
WO2009046167A1	World Intellectual Property Organization (WIPO)	A1	2009-04-09
JP2009517138A	Japan	A	2009-04-30
JP2009517139A	Japan	A	2009-04-30
CN101449573A	China	A	2009-06-03
JP2009531072A	Japan	A	2009-09-03
US2009322865A1	United States of America	A1	2009-12-31
EP1949448A4	European Patent Office (EPO)	A4	2010-07-21
EP1952635A4	European Patent Office (EPO)	A4	2010-08-11
EP1974240A4	European Patent Office (EPO)	A4	2010-08-18
US2010220179A1	United States of America	A1	2010-09-02
US2010220180A1	United States of America	A1	2010-09-02
US7792344B2	United States of America	B2	2010-09-07
US7796870B2	United States of America	B2	2010-09-14
CN101365986B	China	B	2011-02-09
US2011085021A1	United States of America	A1	2011-04-14
US2011085022A1	United States of America	A1	2011-04-14
US7940973B2	United States of America	B2	2011-05-10
US7974454B1	United States of America	B1	2011-07-05
US7983458B2	United States of America	B2	2011-07-19
US2011249105A1	United States of America	A1	2011-10-13
WO2011142794A1	World Intellectual Property Organization (WIPO)	A1	2011-11-17
US8073223B2	United States of America	B2	2011-12-06
US8150124B2	United States of America	B2	2012-04-03
US2012086771A1	United States of America	A1	2012-04-12
US8213698B2	United States of America	B2	2012-07-03
US2012301124A1	United States of America	A1	2012-11-29
CN102883648A	China	A	2013-01-16
CN101449573B	China	B	2013-02-27
EP2568866A1	European Patent Office (EPO)	A1	2013-03-20
US2013129334A9	United States of America	A9	2013-05-23
US8472795B2	United States of America	B2	2013-06-25
JP2013529950A	Japan	A	2013-07-25
EP1974240B1	European Patent Office (EPO)	B1	2013-12-18
JP2013255820A	Japan	A	2013-12-26
EP2568866A4	European Patent Office (EPO)	A4	2014-04-16

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Legal events, newest first
	Event	Code
1996-04-15	Publication of translation of european patent specificationUEP	UEP
1985-06-15	Ceased due to non-payment of the annual feeCeasedELJ	ELJ

N-(Arylthiocarbamoyl)-2-amino-1H-isoindole-1,3-(2H)diones, processes for their preparation and their use as plant growth regulators.

Abstract

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