N-acylamino oxazolidinones

Patent Board

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The Netherlands © ATerinlalagging © 8004584 © NL © Heterocyclic compounds and methods for the preparation and use of these compounds.

© lnt.CI³C07D263 / 26, C07D413 / 12, A01N43 / 76.

© Applicant: Sandoz AG in Basel, Switzerland.

© Av .: Ir. CMR Davidson et al

Vriesendorp &amp; Gaade patent office Kuyperstraat 6

2514 BB The Hague.

© Application Nr. 8004584.

© Submitted on August 13, 1980.

© Priority from August 16, 1979, April 25, 1980, April 25, 1980, April 25, 1980.

© Country of priority: Great Britain (GB).

© Numbers of the priority requests: 7928603.8013719.8013720, 8013721.

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© Laid available for inspection on 18 February 1981.

The documents attached to this sheet are a print of the originally submitted description with claim (s) and any drawing (s).

Heterocyclic compounds and methods for preparing and using these compounds.

The invention provides compounds useful for controlling phytopathogenic fungi.

The invention relates in particular to compounds of formula 1, wherein R 1 represents a group of formula 1 b, wherein R 1 and R 8, independently of one another, an alkyl group with at most 4 carbon atoms, a halogen atom or an alkoxy group with also at most 4 carbon atoms and R ^ represent a hydrogen atom, an alkyl group with at most 4 carbon atoms or a halogen atom, R 8 represents a -CO-Ε ^ θ group, where R_1Q a C₁ alkoxy-C 1-6 alkyl group, alkyl-thioalkyl group, 2-furyl group, 2-tetrahydrofuryl group, a halogenated 2-furyl group, a halogenated 2-tetrahydrofuryl group, a 1-imidazolylmethyl group, a 1-pyrrazolylmethyl group, a 2-tetrahydrofuryloxymethyl group, a 2-tetraxhropyran or a 2 -loxloxymran represents a haloalkyl group and R ^, R ^, R ^ and Rg represent, independently of each other, a hydrogen atom or an alkyl group with at most 4 carbon atoms, as well as methods for preparing and using these compounds.

If one of the substituents R9, R8, R8, R8, R8, R8 or R8 represents an alkyl group or contains an alkyl group (for example an alkoxy group), then this is preferably an alkyl group with at most 3 carbon atoms, which is i.e. the methyl, ethyl, n-propyl or i-propyl group.

If one of the substituents R 1 or R 8 represents a halogen atom, then this is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, in the blunder chlorine or bromine, especially chlorine.

4 5 84

If one of the substituents R 1 or R 4 represents a halogen atom or contains such an atom, then it is a fluorine, chlorine, bromine or iodine atom, preferably a fluorine, chlorine or bromine atom, in particular a chlorine - or bromine atom.

Recommended halogenated 2-furyl groups of R₁₀ are a mono-halogenated 2-furyl group, for example 5-chloro-2-furyl and 5-bromo-2-furyl.

Preferred haloalkyl meanings of R ^ g are a chloroalkyl group or a bromoalkyl group, for example the chloromethyl, bromomethyl and C₂H ^ CHBr group.

Preferred halogenated 2-tetrahydrofuryl meanings of R.sub.2 are mono-halogenated 2-tetrahydrofuryl groups, in particular a monochlorinated or mono-brominated 2-tetrahydrofuryl group, for example the 5-chloro-2-tetrahydrofuryl group.

Recommended C 1-6 alkoxy-C 1-6 alkyl meanings of R₁₀ are the alkoxymethyl group, in particular the

CH ^ OCH3 and C ^ H ^ OCH ^ group.

Preferred alkylthio-C 1-6 alkyl meanings of R ^ q are alkylthiomethyl groups, e.g., the CH 3 SCH₂-group.

It is recommended that R 1 is an alkoxy-alkyl group, 2-furyl group or 5-halogen-2-furyl group.

If one of the substituents R 8 or R 8 represents an alkyl group with at most 4 carbon atoms, then the other is preferably a hydrogen atom.

If one of the substituents R 1 or R 8 represents an alkyl group with at most 4 carbon atoms, then the other is preferably a hydrogen atom.

A recommended group of compounds is therefore formed by compounds of formula 1a, wherein R

-COCH₂OCH₃, -COCH₂OC₂H₅, -C0- (2-furyl) or -CO- (5-halo-2-furyl), R ^ 'and Rg' independently represent a methyl group, a chlorine or bromine atom and R ^ 'represents a hydrogen - is a chlorine or bromine atom or a methyl group, where R and R 9 'are preferably the same.

According to another aspect of the invention, the compounds of formula 1 are prepared by intramolecular condensation of a compound of formula 2, wherein Rp R4, Rp R, Rg and R_1Q have the meanings indicated above and Y is a halogen atom. Y is preferably a chlorine or bromine atom, in particular a chlorine atom.

This intramolecular condensation can be carried out in a conventional manner. The reaction is exothermic.

It can be carried out, for example, in a water-free environment using an ether such as dimethoxyethane, a hydrocarbon such as toluene as a solvent or another solvent inert under the reaction conditions.

The reaction temperature is not critical and can be between approximately 0 ° C and 100 ° C. Since the reaction is exothermic, the reaction is suitably commenced at room temperature and the reaction temperature is allowed to rise gradually.

The reaction is conveniently carried out in the presence of an acid-binding agent such as sodium hydride, sodium amide or a sodium alcoholate, for example sodium ethylate.

The intramolecular condensation can also be carried out in an aqueous-organic two-phase system in the presence of an inorganic base, for example sodium hydroxide and optionally a catalytic amount of a phase transfer catalyst. The organic phase may contain any suitable, inert, water-immiscible solvent such as hydrocarbons or halogenated carbon compounds, for example xylene, toluene, o-dichlorobenzene or dichloromethane. Suitable phase transfer catalysts are quaternary ammonium compounds, such as benzyl trimethyl ammonium bromide, quaternary phosphonium compounds, such as benzyl triphenyl phosphonium chloride and crown ethers.₍such as 18-crown-6.

The compounds of formula 2 are new. They can be obtained by acylation of a compound of formula 3, wherein Rp R4, Rp R4, Rg and Y

4 Have 84 meanings, with a compound of formula 4, wherein R₁₀ has a meaning indicated above and Z represents a halogen atom, in particular a chlorine atom, or -O-COR ^, wherein R ^ has a meaning indicated above.

Suitable solvents for this acylation reaction are hydrocarbons such as toluene or halogenated hydrocarbons such as chlorobenzene. The reaction is suitably carried out at a temperature between about 5 ° and about 120 ° C, for example 80 ° C.

The compounds of the formula III can be obtained by reacting a compound of the formula VI wherein R has the meaning indicated above, with a compound of the formula VI, wherein R4, R4, R4, R8 and I have the meanings indicated above and X is a halogen atom, in particular a chlorine atom.

This reaction can be carried out at a temperature between about 0 ° C and about 10 ° C in water or in an organic solvent which is inert under the reaction conditions, suitably in the presence of a base, for example an organic amine or sodium hydrogen carbonate.

The starting materials and reagents used in the processes described above are known or, as far as possible. . . .

is not the case, in a manner analogous to the methods described or known methods described herein.

The compounds according to the invention of formula I have useful fungicidal properties, in particular against phytopathogenic fungi, in particular against fungi of the Oomycetes order, as evidenced by the potent action described in the following tests.

Test A: fungicidal action against Phytophthora infestans

Young potted potato plants (at the 3-5 leaf stage) were sprayed with an aqueous, sprayable suspension containing 0.003% (w / v) of a compound of formula 1, for example 2-methoxy-N- (2,6-dimethylphenyl). -N- (2-oxo-3-oxazolidinyl) acetamide (formulated according to preparation example I).

4 5 84

Two hours later, the treated plants were inoculated with a spore suspension of Phytophthora infestans and then transferred to a tent in which a relative humidity of 100%, a temperature of 16 ° C and a day length of 16 hours prevailed. The degree of control of the condition was performed 4-5 days later by comparing the treated plants with untreated, similarly inoculated, plants. Using the aforementioned tested compound, a significant control of the fungal infection was observed, without any signs of phytotoxicity in the host plants. Test B: Fungicidal action against Plasmonara viticola

Young potted plants from the vine (at the 3-6 leaf stage) were sprayed with an aqueous sprayable suspension containing 0.0008% (w / v) of a compound of formula 1, for example 2-methoxy-N- ( 2,6-dimethylphenyl) -N- (2-oxo-3-oxazolidinyl) -acetamide (prepared according to preparation example i). 2 hours later the treated plants were inoculated with a spore suspension of Plasmopara viticola and then transferred to a tent in which a relative humidity of 100% at a temperature between 15 and 22 ° C (fluctuating over a 24-hour period) and a day length of 16 hours. The disease control was assessed 6 days after grafting by comparing the treated plants with untreated, similarly inoculated, plants. Substantial control of fungal infection was observed with the aid of the compound tested, without any signs of phytotoxicity being observed in the host plants.

Test C; Curative fungicidal effect against Plasmopara viticola

Young potted plants were grafted from the vine (at the 3-6 leaf stage) in the same manner as described in Test B, but the compound, e.g. 2-methoxy-N (2,6-dimethylphenyl) -N- (2-oxo) was served -3-oxazolidinyl) -acetamide (formulated according to preparation example I) only after 3 days after grafting. Further incubation conditions were the same as described in test B. The control of the condition was assessed for the

4 In the same way as described in test B. With the aid of the compound tested a considerable control of the fungicidal infection was observed.

Test D: Exterminating fungicidal action against Plasmopara viticola_

The method for evaluating this type of effect was done in the manner described in test C, except that the treatment was not performed until 6 days after the inoculation, when spore formation on the surface of the lower sheets was already apparent. The evaluation of the control of the condition which, 7 days after administration of, for example, 0.012 l of the compound 2-methoxy-N- (2,6-dimethylphenyl) -N- (2-oxo-3-oxazolidinyl) acetamide (composed according to preparation example I ), showed an inhibitory effect on already spore-forming zones, completely eliminating spore formation.

Test E: Translocation in treated leaves of the vine

Cut leaves of the vine were treated with an aqueous, sprayable suspension containing 0.012% of a compound of formula 1, for example 2-methoxy-N- (2,620 dimethylphenyl) -N- (2-oxo-3-oxazolidinyl) -acetamide ( composed according to preparation example i), such that only the lower half of such leaves were treated.

Two hours later, the entire leaf was inoculated with a spore suspension of Plasmopara viticola, after which the leaves were incubated in a tent in which a humidity of 100 # prevailed under the conditions described in Test B. Although only the lower half of the leaves were treated with the test compound, as mentioned above, significant control of the entire grafted leaf was observed, also if only the upper half of the leaves were treated.

From this test it thus appears that 2-methoxy-N- (2,6-dimethylphenyl) -N (-oxo-3-oxazolidinyl) -acetamide (composed according to preparation example I) was spread both above and below in the leaf. Test F: Treatment of the earth.

In vivo, using Pythium aphanidermaturn

800 4 5 84

The fungus was grown in a steri / mixture of sand and wheat flour (97: 3, vol / vol), to which water was added in an amount of about 1: 4 (vol./vol.) And the fungus was cultivated for 4 days. 25 ° C. The fungus was then mixed in a semi-sterile mixture of peat and sand, which was then treated with a suspension containing the composite active ingredient until a concentration of 10 to 160 ppm. (e.g. 10, 40 or 160 ppm) calculated per volume of substrate. The substrate was then placed in pots with a diameter of 5 cm, in which cucumber seeds were sown. The planted pots were then incubated for 7 days at a temperature of 24 ° C and a relative humidity of 60-70% in an incubation chamber, after which the fungal attack was determined by comparing the number of healthy, hatched plants with those in untreated, grafted control pots. The compound of Example I below, used in a wettable, powdered preparation, gave complete control of the fungus.

Tests corresponding to those in test F gave similar results with peas and sugar beets.

Each of the compounds listed in the following examples was found to have fungicidal properties, meaning that they are useful as fungicides.

According to the tests described above, a particularly effective fungicidal activity was found to have the compounds of formula Ia, in which R8 'is a -COCH3OC3H4 group, R3'. and R 9 'represents a methyl group and R 4' represents a hydrogen atom, wherein R 9 'represents a -C 0 (2-furyl) group, R 4' and R 9 'represent a methyl group and R 4' represents a hydrogen atom, wherein R 9 'represents a -CO- (5-bromo-2-furyl) group, R 7 ' and R 8 represents a methyl group and R 8 represents a hydrogen atom, wherein R 8 represents a -COCH 6 OCH 4 groups, R? " and Rg 'represents a chlorine atom and R' represents a hydrogen atom or wherein R_n'a -COCIL · ydd

OCH 3 group, R y 'and R 8' represent a methyl group and R 3 'represents a 3-bromine atom and in particular the compound of formula 1a, wherein R 8' is a -COCH 8 OCH 3, R 4 'and R 8' a methyl group and R 3 'a

4 5 84 hydrogen atom.

The invention thus also provides a method for controlling phytopathogenic fungi, in particular of the Oomycetes order, in plants, seeds or in the soil, which method comprises treating the plants, seeds or soil with a fungicidally effective amount of one or a number of compounds according to the invention of formula 1.

Fungi of the order of Oomycetes, for which the method according to the invention is particularly effective, are those of the Phytophthora genus in plants such as potatoes, tomatoes, tobacco, citrus, cocoa, rubber, apples, strawberries, vegetables and ornamental plants, for example Phytophthora infestans in potatoes and tomatoes, of the genus Plasmopara viticola in the vine, of the genus Peronospora in plants, such as tobacco, for example Peronospora tabacina in tobacco, of the genus Pseudoperonospora in plants, such as hops and cucumber, for example Pseudoperonosnora humuli in hops, of the genus Bremia in plants, such as lettuce, for example Bremia lactucae in lettuce, of the genus Pythium, which causes smoldering and root fire in a large number of plants, such as vegetables and sugar beets, ornamental plants and conifers, for example Pythium anhanidermatum in sugar beets, of the genus Sclerosnora in plants, such as sorghum and wheat, for example Sclerosnora sorghis in sorghum millet.

For use in the invention, the amount of the composition to be used will vary depending on factors such as the type of fungus to be controlled, the time and method of administration and the amount and type of compound of formula 1 used in the composition.

In general, however, satisfactory results are obtained if on a piece of land, for example a crop or the soil, a dosage of between 0.05 and 5 kg, preferably between 0.3 and 3 kg, of one or more compounds according to the invention of formula 1 treated per hectare, which treatment can be repeated if desired. If the preparation with the seed is used, satisfactory results are obtained

4 84 results obtained if an amount of between about 0.05 to 0.5, preferably between about 0.1 and 0.3 g of the compound of the invention of formula I per kg of seed is used.

According to a preferred embodiment of the invention, the compound (s) according to the invention of formula I is used together with fungicides which are effective against phytopathogenic fungi against which the compounds according to the invention of formula 1 are not or not sufficiently effective; this method makes it possible to treat a larger range of phytopathogenic fungi than the use of the compounds according to the invention of formula 1 alone.

According to a particularly recommended embodiment of the invention, effective amounts of a component a) containing a compound of formula I and of a component b) selected from a component b1 a copper fungicide, or a component b2 are applied to the area to be treated. ) captan or folpet, or a component b3) mancozeb or maneb. Examples of copper fungicides that are suitable for use as component hl) are copper (II) carbonate, copper (II) calcium sulfate, copper (II) calcium oxychloride, tetracuprioxychloride-Bordeaux mixture, Burgundy mixture, cuprous oxide, cupric hydroxide, copper (II5oxychloride) and also copper complexes , such as copper triethanolamine, hydroxide of formula / (Cu (NiCH3 CH3 OH) ^ 7- (OH)₂, commercially available under the K-Lox brand, or bis (ethylenediamine) copper (II) sulfate of formula / C 12 H 18 CH 3 CH 3 O 3 ^ 7 SO 4, commercially available under the Komeen brand and mixtures thereof, in particular cuprous oxide, copper (II) oxychloride, cupric hydroxide and a mixture of copper (II) calcium sulfate and copper (II) oxychloride.

Captan, Folpet, Mancozeb and Maneb are the usual names for protective fungicides that are effective

800 4 5 84 against leaf diseases (Pesticide Manual, 5th Ed., By H. Martin and CR Worthing, pp. 76, 281, 328 and 329).

The method according to the invention wherein component a) and component b) are used is effective against a wide variety of phytopathogenic fungi.

Component a) is preferably used in an amount of 100-400 g / hectare and component b) in an amount of 200-2000 g per hectare.

The amount by weight of component a) to component b) will preferably be between 1: 1 and 1:10, in particular between 1: 2 and 1:10, especially between 1: 2 and 1: 7.

The method according to the invention in which component a) and component b) are used is particularly effective against phytopathogenic fungi in plants, such as potatoes, tomatoes and other Solanaceae, tobacco, citrus, cocoa, rubber, apples, strawberries, vegetables and ornamental plants, for example against fungi of the genus Plasmopara, for example Plasmopara viticola in the vine, of the genus Guignardia, for example Guignardia bidwelli in the vine of the genus Phoma in the vine, of the genus Pseudopeziza, for example Pseudopeziza tracheiphila in the vine, of the genus Gloeosporium, for example Gloeosporium ampelophagum in the vine of the genus Botrytis in the vine and lettuce, for example Botrytis cinerea in the vine, of the genus Phytophthora, Phytophthaceae tomatoes, or Tomatoes of the genus , Phytophthora parasitica in tomatoes or other Solanaceae, Phytophthora cryptogaea in tomatoes and other Solanaceae, Phytophthora mexicana in tomatoes and other Solanaceae, Phytophthora nicotianae in tobacco and Phytophthora palmivora in rubber or cocoa, of the genus Peronospora, for example Peronospora tabacina in tobacco, of the genus Pseudoperonospora, for example Pseudoperonospora humuli in hops, of the genus Bremia lettuce, for example Bremia lactucae, from the genus Pythium, for example Pythium aphanidermatum in sugar beet, from the genus Alternaria, for example Alternaria solani in potatoes, tomatoes and other Solanaceae, Alternaria tenuis

800 45 84 in tobacco, from the genus Spondylocladium, for example Spondylocladium atrovirens in potatoes, from the genus Rhizoctonia, for example Rhizoctonia solani in potatoes, tomatoes and other Solanaeeae, from the genus Cladosporium, for example Cladosporium fulvum in tomatoes or other Solanaeeaet, from the genus Collususum in plants, such as cocoa or tomatoes, for example Colletotrichum atramentarium in tomatoes or other Solanaeeae, of the genus Glomerella, for example Glomerella lycopersici in tomatoes and other Solanaeeae from Corticium spp in tomatoes and other Solanaeeae, from the genus Botryodiplodia, for example Botryodiplodia theobromae in cocoa.

The method according to the invention also makes it possible to combat a considerably greater variety of fungal diseases than when only one of the components is used.

In general, a greater than additive effect, thus a synergistic effect, of the components is observed, in particular when treated with concentrations of component a) and component h), resulting in a nearly complete, more than 80 #, control of the fungi becomes possible, in particular if copper (II) oxychloride, cuprous oxide, captan, mancozeb or maneb is used as component b), especially when used against phytopathogenic fungi of the order of Oomycetes, in particular against Qomycetes of the genus Phytophthora for example Phytophthora infestans, of the genus Plasmopora for example Plasmopora viticola _?of the genus Peronospora, for example Peronospora tabaccina of the genus Pseudoperonospora for example Pseudoperonospora humuli ^ of the genus

Bremia, for example Bremia lactucae and of the genus Pythium, for example Pythium aphanidermatum.

The method according to the invention in which the components a) and b) are used is particularly indicated for controlling or preventing fungi in vine, tomatoes and other Solanaeeae and in cocoa if a compound b1) is used, in vine if a compound b2) is used and is added to vine, potatoes, tomatoes and other Solanaeeae, tobacco and hops

4 5 84 applied.

The compounds a) and h) can be used in the form of a preparation and, for example, as a mixture or applied separately. However, they are preferably used in mixed form in the form of an aqueous sprayable preparation or a concentrated oil-based preparation.

The useful fungicidal action obtained after treatment with a component a) and a component b) is illustrated by the following tests.

Test G: The fungicidal action against Phytophthora infestans

This test was carried out in the manner described in test A, in which the plants were treated with a mixture of an aqueous sprayable suspension containing component a) and component b) in the concentrations given in Tables A ^ -Ag below. The control was assessed 4-5 days later by comparing its results with the effect that would have been obtained if only an additive effect had occurred. As shown in the following tables

Ag is a more than additive effect.

Table A o ft o ra ra ft Ή ra - 'u component a) of the following

<td></td><td>0</td><td>2</td><td>8</td><td>32</td>

<td>0</td><td>0</td><td>30</td><td>70</td><td>90</td>

<td></td><td>0</td><td>40</td><td>80</td><td>100</td>

<td>2</td><td></td><td>(30)</td><td>(80)</td><td>(100)</td>

<td></td><td>20</td><td>6o</td><td>90</td><td>100</td>

<td>8</td><td></td><td>(45)</td><td>(90)</td><td>(90)</td>

<td></td><td>6o</td><td>80</td><td>100</td><td>100</td>

<td>32</td><td></td><td>(70)</td><td>(90)</td><td>(95)</td>

800 4 5 84

Table Ag component a) of Example I below (in npm)

<td colspan="2"></td><td>0</td><td>2</td><td>8</td><td>32</td>

<td></td><td rowspan="2">0</td><td>0</td><td>Ho</td><td>80</td><td>100</td>

<td></td><td></td><td></td><td></td><td></td>

<td>Ό z-.</td><td></td><td></td><td></td><td></td><td></td>

<td>e N &amp;</td><td></td><td>0</td><td>50</td><td>100</td><td>100</td>

<td>O ft O</td><td>2</td><td></td><td>(HO)</td><td>(80)</td><td>(100)</td>

<td>O</td><td></td><td>30</td><td>80</td><td>100</td><td>100</td>

<td>ft · - · 3 cm</td><td>8</td><td></td><td>(6o)</td><td>(85)</td><td>(100)</td>

<td>you</td><td></td><td>75</td><td>90</td><td>100</td><td>100</td>

<td></td><td>32</td><td></td><td>(85)</td><td>(95)</td><td>(100)</td>

() calculated additive effect (1) in the commercially available Copper-Sandoz form (2) in the commercially available Cage 101 form

Table A ^ component a) of Example I below (in ppm)

<td></td><td colspan="2">0</td><td>2</td><td>8</td><td>32</td>

<td></td><td>0</td><td>0</td><td>30</td><td>80</td><td>100</td>

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

<td>&amp;</td><td></td><td>20</td><td>50</td><td>100</td><td>100</td>

<td>e</td><td>2</td><td></td><td rowspan="2">(H5)</td><td rowspan="2">(85)</td><td rowspan="2">(100)</td>

<td>• H</td><td></td><td></td>

<td></td><td></td><td>Ho</td><td>80</td><td>100</td><td>100</td>

<td>ft ft</td><td>8</td><td></td><td>(60)</td><td>(90)</td><td>(100)</td>

<td>O</td><td></td><td></td><td></td><td></td><td></td>

<td></td><td></td><td>70</td><td>90</td><td>100</td><td>100</td>

<td></td><td>32</td><td></td><td>(80)</td><td>(95)</td><td>(100)</td>

Table A ^

<td colspan="6">component a) of Example I below (in npm)</td>

<td rowspan="2">e</td><td></td><td>0</td><td>2</td><td>8</td><td>32</td>

<td></td><td></td><td></td><td></td><td></td>

<td rowspan="2">ft &amp; c</td><td>0</td><td>0</td><td>HO</td><td>80</td><td>100</td>

<td></td><td></td><td></td><td></td><td></td>

<td>• H</td><td>2</td><td>30</td><td>70</td><td>90</td><td>100</td>

<td rowspan="2"></td><td></td><td></td><td>(Ho)</td><td>(80)</td><td>(100)</td>

<td></td><td></td><td></td><td></td><td></td>

<td>&lt;</td><td></td><td>20</td><td>90</td><td>100</td><td>100</td>

<td>O</td><td>8</td><td></td><td>(50)</td><td>(85)</td><td>(100)</td>

<td></td><td></td><td>80</td><td>100</td><td>100</td><td>100</td>

<td></td><td>-21.</td><td></td><td>(90)</td><td>(95)</td><td>(100)</td>

800 4 5 84

1H

Table component (a) of Example I below (in ppm)

<td></td><td colspan="2">0</td><td>2</td><td>8</td><td>32</td>

<td>e</td><td>0</td><td>0</td><td>20</td><td>80</td><td>95</td>

<td>ft ft</td><td></td><td>20</td><td>80</td><td>100</td><td>100</td>

<td>β • H</td><td>d</td><td></td><td>(35)</td><td>(85)</td><td>(95)</td>

<td>43</td><td rowspan="2">8</td><td>Ho</td><td>90</td><td>100</td><td>100</td>

<td></td><td></td><td>(50)</td><td>(90)</td><td>(100)</td>

<td>0</td><td></td><td></td><td></td><td></td><td></td>

<td>you §</td><td rowspan="2">32</td><td>75</td><td>95</td><td>100</td><td>100</td>

<td>S</td><td></td><td>(80)</td><td>(95)</td><td>(100)</td>

Table Ag

<td colspan="6">component a) of Example I below (in note)</td>

<td></td><td></td><td>0</td><td>2</td><td>8</td><td>32</td>

<td></td><td>0</td><td>0</td><td>30</td><td>70</td><td>95</td>

<td>s, ft</td><td>O</td><td>30</td><td>70</td><td>90</td><td>100</td>

<td>β</td><td>d</td><td></td><td>(50)</td><td>(80)</td><td>(100)</td>

<td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td rowspan="2">8</td><td>Ho</td><td>85</td><td>100</td><td>100</td>

<td>g</td><td></td><td>(60)</td><td>(80)</td><td>(100)</td>

<td>β</td><td></td><td></td><td></td><td></td><td></td>

<td>"3 s</td><td rowspan="2">32</td><td>85</td><td>100</td><td>100</td><td>100</td>

<td></td><td></td><td>(90)</td><td>(95)</td><td>(100)</td>

() calculated additive effect.

Test H; Fungicidal effect against Plasmopara viticola

This test was carried out in the manner described in test B, in which the plants were treated with a mixture of an aqueous sprayable suspension containing component a) and component b) at the concentrations given in the tables below. The observed effect is reported in the following tables B-Bg.

800 4 5 84

Table _B] cyprohydroxide (2) I cuprous oxide (1) (in ppm) component a) of Example I below (in ppm)

<td></td><td>0</td><td>2</td><td>8</td><td>32</td>

<td>0</td><td>0</td><td>30</td><td>T0</td><td>100</td>

<td></td><td>10</td><td>30</td><td>70</td><td>100</td>

<td></td><td></td><td>(35)</td><td>(75)</td><td>(100)</td>

<td rowspan="2">8</td><td>50</td><td>60</td><td>100</td><td>100</td>

<td></td><td>(65)</td><td>(85)</td><td>(100)</td>

<td rowspan="2">32</td><td>80</td><td>85</td><td>100</td><td>100</td>

<td></td><td>(85)</td><td>(95)</td><td>(100)</td>

Table component a) of the following

<td colspan="5">following example I (in ppm)</td>

<td></td><td>0</td><td>2</td><td>8</td><td>32</td>

<td>0</td><td>0</td><td>40</td><td>70</td><td>100</td>

<td></td><td>20</td><td>40</td><td>70</td><td>100</td>

<td>2</td><td></td><td>(45)</td><td>(75)</td><td>(100)</td>

<td rowspan="2">8</td><td>40</td><td>60</td><td>100</td><td>100</td>

<td></td><td>(60)</td><td>(80)</td><td>(100)</td>

<td rowspan="2">32</td><td>70</td><td>80</td><td>100</td><td>100</td>

<td></td><td>(80)</td><td>(90)</td><td>(100)</td>

() calculated additive effect (1) in the commercially available Copper-Sandoz form.

(2) in the commercially available Cage 101 form.

800 4 5 84

I ft si • H

Uh

H ft fc

O ft

Table B₃ component (a) of Example I below (in nm)

<td></td><td>0</td><td>2</td><td>8</td><td>32</td>

<td>0</td><td>0</td><td>40</td><td>80</td><td>100</td>

<td>2</td><td>40</td><td>6o (65)</td><td>100 (90)</td><td>100 (100)</td>

<td>8</td><td>70</td><td>8o (80)</td><td>100 (95)</td><td>100 (100)</td>

<td>32</td><td>100</td><td>100 (100)</td><td>100 (100)</td><td>100 (100)</td>

<td></td><td></td><td colspan="2">Table B</td><td></td>

<td colspan="3">component a)</td><td>from the</td><td>after this</td>

£ ft a

• rl a

E $ ft &lt;

o following example I (in ppm)

<td></td><td>0</td><td>2</td><td>8</td><td>32</td>

<td>0</td><td>0</td><td>40</td><td>70</td><td>100</td>

<td></td><td>0</td><td>40</td><td>80</td><td>100</td>

<td>2</td><td></td><td>(40)</td><td>(70)</td><td>(100)</td>

<td rowspan="2">8</td><td>70</td><td>95</td><td>100</td><td>100</td>

<td></td><td>(80)</td><td>(90)</td><td>(100)</td>

<td rowspan="2">32</td><td>100</td><td>100</td><td>100</td><td>100</td>

<td></td><td>(100)</td><td>(100)</td><td>(100)</td>

go

a • rl • s «

O υ

Table B_? component (a) of Example I below (in ppm)

<td></td><td>0</td><td>2</td><td>8</td><td>32</td>

<td>0</td><td>0</td><td>40</td><td>80</td><td>100</td>

<td></td><td>20</td><td>6o</td><td>100</td><td>100</td>

<td>2</td><td></td><td>(50)</td><td>(85)</td><td>(100)</td>

<td rowspan="2">8</td><td>70</td><td>95</td><td>100</td><td>100</td>

<td></td><td>(80)</td><td>(95)</td><td>(100)</td>

<td rowspan="2">32</td><td>90</td><td>100</td><td>100</td><td>100</td>

<td></td><td colspan="2">(95) (100)</td><td>(100)</td>

80045 84

Table Bg component a) of Example I below (in ppm)

<td></td><td>0</td><td>2</td><td>8</td><td>32</td>

<td>0</td><td>0</td><td>35</td><td>8o</td><td>100</td>

<td></td><td>20</td><td>50</td><td>90</td><td>100</td>

<td></td><td></td><td>(50)</td><td>(85)</td><td>(100)</td>

<td>□</td><td>6o</td><td>90</td><td>100</td><td>100</td>

<td>0</td><td></td><td>(75)</td><td>(90)</td><td>(100)</td>

<td rowspan="2">32</td><td>95</td><td>100</td><td>100</td><td>100</td>

<td></td><td>(100)</td><td>(100)</td><td>(100)</td>

() calculated additive effect.

The compounds according to the invention of formula I are suitably used, if desired together with carriers and / or diluents acceptable in the agricultural field, in the form of fungicidal preparations. The invention is therefore also directed to a method for the preparation of a preparation with fungicidal action by one or more compounds according to the invention of formula I, optionally together with a suitable carrier and / or diluent, in a dosage form suitable for such an application and to the molded compositions obtained by this method.

The compositions may contain, in addition to a compound according to the invention of the formula I, as active ingredient, other active agents, such as fungicides, in particular a fungicide selected from the group comprising component b), as defined above. They can be used in both solid and liquid preparation forms, for example in the form of a wettable powder, a concentrated emulsion, a concentrated, water-dispersible, suspension (liquid), a spray powder, a granular preparation, a preparation whose active ingredients are about be released for a long period of time, which preparations contain suitable carriers, diluents and / or additives, if desired,

800 4 5 84

Such compositions may be prepared or prepared in a conventional manner.

The compositions according to the invention containing both components a) and b) can be obtained, for example, by mixing said components a) and b), optionally together with a carrier and / or other components.

In particular, compositions which will be sprayed, such as water-dispersed, concentrated or wettable powders, may contain surface-active agents such as wetting and dispersing agents, for example the condensation product of formaldehyde and naphthalene sulfonate, an alkylaryl sulfonate, a lignin sulfonate, a higher alkyl sulfate an ethoxylated alkyl phenol and an ethoxylated higher alcohol.

In general, the compositions will contain from 0.01 to 90% by weight of active ingredient, which active ingredient will consist of at least one compound of formula 1 or mixtures thereof with other active agents, such as fungicides, for example a component b) as defined above. .

Concentrated preparation forms will generally contain between about 2 and 80% by weight, preferably between about 5 and 70% by weight, of active ingredient. Liquid preparation forms may contain 0.01-30% by weight, preferably 0.01-5% by weight, of active ingredient.

The parts and percentages given in the following examples are resp. parts by weight and weight percentages.

Example example I:

Wet hair powder

50 parts of 2-methoxy-N- (2,6-dimethylphenyl) -N- (2-oxo-3-oxazolidinyl) -acetamide were milled with 2 parts of lauryl sulfate, parts of sodium lignin sulfate and U5 parts of finely divided kaolinite until the average particle size was less than 5 micron.

The wetted powder thus obtained was then diluted before use with water to a concentration of between 0.01 and 5% active ingredient. The sprayable liquid obtained can be used either

800 4 5 84 by spraying the foliage and when applied through roots.

Example example 2:

Grains

In a tumbler mixer, 94.5 parts of quartz sand were sprayed with 0.5 parts of a binder (non-ionic surfactant) and these components were mixed thoroughly. Then 5 parts of powdered 2-methoxy-1- (2,6-dimethylphenyl) -N- (2-oxo-3-oxazolidinyl) -acetamide were added and these components were again intimately mixed, whereby a granular preparation with a particle size between 0 and 3 and 0.7 mm. These granules can be used by incorporation into the soil in addition to the plants to be treated.

Example examples 3-6:

(wettable powders) w / s

<td>Example</td><td>3</td><td>4</td><td>5</td><td>6</td>

<td>component a)¹</td><td>12.65</td><td>6.25</td><td>12.5</td><td>6.25</td>

<td>copper (ii) oxychloride</td><td></td><td></td><td></td><td></td>

<td>(-56% Cu)</td><td>4?</td><td>47</td><td></td><td></td>

<td>cuprous oxide (az88% Cu)</td><td></td><td></td><td>29</td><td>29</td>

<td>sodium lauryl sulfate</td><td>1</td><td>1</td><td>1</td><td>1</td>

<td>lignin sulfonate</td><td>10</td><td>10</td><td>10</td><td>10</td>

<td>kaolin</td><td>29.5</td><td>35.75</td><td>39.5</td><td>45.75</td>

(¹) e.g. 2-methoxy-N- (2,6-dimethylphenyl) -N- (2-oxo-3-oxazolidinyl) acetamide.

All components of the preparation were mixed, milled and mixed again in a conventional manner.

45 84

Application examples 7-9 (wettable powders) wt. 1&gt;

<td>example</td><td>7</td><td>8</td><td>9</td>

<td>component a)</td><td>25</td><td>12.5</td><td>6.25</td>

<td>component b2</td><td>50</td><td>50</td><td>50</td>

<td>sodium oleoyl methyltauride</td><td>2</td><td>2</td><td>2</td>

<td>the condensation product of C 1-6 alkyl naphthalene sulfonate and formaldehyde</td><td>5</td><td>5</td><td>5</td>

<td>silica gel</td><td>5</td><td>5</td><td>5</td>

<td>kaolin</td><td>13</td><td>25.5</td><td>31.75</td>

(&gt;&gt; 2-methoxy-N- (2,6-dimethylphenyl) -N- (2-oxo-3-oxazolidinyl) acetamide (2).

"" e.g. Folpet

All components of the preparation were mixed, milled and mixed again in a conventional manner.

Application examples 10 - 12 (wettable poodle by weight. Example 10 11 12

<td>component a) ^</td><td>25</td><td>12.5</td><td>6.25</td>

<td>component b3)</td><td>50</td><td>50</td><td>50</td>

<td>Na-lauryl sulfate</td><td>1</td><td>1</td><td>1</td>

<td>lignin sulfonate</td><td>4</td><td>4</td><td>4</td>

<td>silica gel</td><td>5</td><td>5</td><td>5</td>

<td>kaolin</td><td>15</td><td>27.5</td><td>33.75</td>

(^ e.g. 2-methoxy-N- (2,6-dimethylphenyl) -N- (2-oxo-3-oxazolidinyl) acetamide ^ ^ e.g. mancozeb

The preparation was obtained by mixing the ingredients in a conventional manner, then grinding the resulting mixture and finally mixing this mixture again.

800 4 5 84

Example I:

2-methoxy-N- (2, 6-dimethylphenyl) -II- (2-oxo-3-oxazolidinyl) -acetamide

In portions, at room temperature and in a nitrogen atmosphere, 11.8 g (0.0375 mol) of 2-chloroethyl were added

2- (methoxyacetyl) -2- (2,6-dimethylphenyl) -hydrazine carboxylate to a suspension of 2.0 g of sodium hydride (in the form of about 55% by weight in mineral oil) in 100 ml of absolute toluene. During this addition, the reaction temperature gradually rose to 40 ° C. After the addition, the mixture was stirred for another 30 minutes.

without cooling and then with cooling to 10 ° C. The unreacted sodium hydride was then decomposed with ethanol, the resulting solution washed with water, dried over magnesium sulfate and the solvent distilled off under reduced pressure to obtain the title compound which was recrystallized from ethanol. Thus, the title compound was obtained as colorless crystals with a melting point of 103-104 ° C.

Example Ia:

2-chloroethyl 2- (methoxyacetyl) -2- (2,6-dimethylphenyl) hydrazine carboxylate

The starting material used in Example I was obtained as follows:

A mixture of 14.7 g (0.06 mol) was stirred

2-chloroethyl 2- (2,6-dimethylphenyl) hydrazine carboxylate and

16.2 g (0.1 mole) methoxyacetic acid anhydride (CH 4 OC 11 4 00) 7 for 1 hour at 80 ° C in 100 ml dry toluene. After cooling, the solution was washed successively with water, a 5% solution of an aqueous sodium hydrogen carbonate and again with water.

Drying the resulting solution over magnesium sulfate and removing the solvent under reduced pressure gave the title compound of Example 1a.

Example lb:

2-chloroethyl 2- (2,6-dimethylphenyl) hydrazine carboxylate

To a mixture of 127 g (0.935 mol) of 2,6-dimethylphenylhydrazine, 102.5 g (1.3 mol) of pyridine and 400 ml of water at a temperature between 0 and 5 ° C was added 133.5 g (0.935 mol) of the β-chloroethyl ester of chloroformic acid. After the addition, the mixture was stirred at room temperature for 2 hours, the precipitate formed was filtered off, washed with water and dried. Recrystallization of the thus-obtained title compound from toluene gave colorless crystals with a melting point of 74-75 ° C.

According to a recommended, alternative form of example I, Ia and lb, the procedure was as follows:

Example II:

2-methoxy-N- (2,6-dimethylphenyl) -N- (2-oxo-3-oxazolidinyl) -acetamide

236.1 g (0.75 mol) of 2-chloroethyl were stirred

2- (methoxyacetyl) -2- (2,6-dimethylphenyl) hydrazine carboxylate,

375 ml of xylene and 187 ml of water with external cooling while adding 82.5 ml (0.82 mol) of an aqueous sodium hydroxide solution (containing from 0.4 g NaOH per ml) with such. ._O the internal temperature was maintained at approximately 20 ° C.

After the addition, the mixture was stirred for an additional 1 hour at 20 ° C and then for 2 hours at 0 ° C. By filtration of the solid product obtained, washing out with 150 ml of water and drying, the title compound was obtained as a slightly colored solid with a melting point of 102-103 ° C.

Example Ila:

2-chloroethyl 2- (methoxyacetyl) -2- (2,6-dimethylphenyl) hydrazine carboxylate

200 g (0.825 mol) of 2-chloroethyl 2 (2,6-dimethylphenyl) -hydrazine carboxylate in 500 ml of xylene were heated to 8 ° C and this mixture was added to a warm (80 ° C) solution of

800 4 5 84

2-methoxyacetyl chloride in 250 ml of xylene prepared in situ by treating 73.5 g (0.826 mol) of 2-methoxyacetic acid in 250 ml of xylene with 107.1 g (0.9 mol) of thionyl chloride for 2 hours at 80 ° C . After this mixture was heated at 80 ° C for 30 minutes, it was worked up in the manner described in Example 1a.

Example Ilb:

2-chloroethyl 2- (2,6-dimethylphenyl) hydrazine carboxylate

A mixture of 17.7 g (0.1 mol) was stirred

2,6-dimethylphenylhydrazine hydrochloride, 21.2 g (0.2 mol) of sodium carbonate in 50 ml of water and 50 ml of xylene for 30 minutes at room temperature and then cooled this mixture to 5 ° C. Then 14.3 g (0.1 mol) of the 2-chloro15 ethyl ester of chloroformic acid were added over an hour, with the temperature kept at 5 ° C. The mixture was then stirred for another hour at 5 ° C, after which 100 ml of water were added, the precipitate thus formed was filtered, washed with water and dried. The further work-up took place as described in example Ib.

In a similar manner as described in the preceding Examples I and II, the following compounds according to the invention of formula I have also been prepared.

800 45 84

<td>In front of- statue</td><td>^R3</td><td>«Η</td><td>^R5</td><td>^κ6</td><td>^Ητ</td><td>^R8</td><td>^S9</td><td>^R, 0</td><td>m.p.</td>

<td>III</td><td>Η</td><td>Η</td><td>Η</td><td>Η</td><td>ch₃</td><td>^CH3</td><td>H</td><td>οη₂οο_Λ</td><td>62-4</td>

<td>IV</td><td>Η</td><td>Η</td><td>Η</td><td>Η</td><td>^CK3</td><td>Cl</td><td>H</td><td>CHgOCl ^</td><td>99-100</td>

<td>V</td><td>Η</td><td>Η</td><td>Η</td><td>Η</td><td>ch₃</td><td>^CH3</td><td>H</td><td>til</td><td>190-1</td>

<td>VI</td><td>Η</td><td>Η</td><td>Η</td><td>Η</td><td>dig</td><td>^CH3</td><td>4-ci</td><td>CH₂0CH₃</td><td>107-9 ·</td>

<td>VII</td><td>Η</td><td>ch₃</td><td>οκ₃</td><td>Η</td><td>CH₃</td><td>^CH3</td><td>H</td><td>CH₂0CH₃</td><td></td>

<td>VIII</td><td>Η</td><td>Η</td><td>Η</td><td>Η</td><td>CH₃</td><td>^CH3</td><td>H</td><td>CHgSCH</td><td>113-5</td>

<td>IX</td><td>Η</td><td>Η</td><td>Η</td><td>Η</td><td>cs₃</td><td>^CH3</td><td>H</td><td>CH₂C1</td><td>134-6</td>

<td>X</td><td>Η</td><td>Η</td><td>Η</td><td>Η</td><td>^CK3</td><td>Cl</td><td>H</td><td>ch₂ci</td><td>135-6</td>

<td>XI</td><td>Η</td><td>Η</td><td>Η</td><td>Η</td><td>ch₃</td><td>CH₃</td><td>H</td><td>CH₂0CH (CH₃)</td><td>2</td>

<td>XII</td><td>Η</td><td>Η</td><td>Η</td><td>Η</td><td>ch₃</td><td>Cl</td><td>H</td><td>CH₂0CH (CH₃)</td><td>2</td>

<td>XIII</td><td>Η</td><td>Η</td><td>Η</td><td>Η</td><td>^CK3</td><td>Cl</td><td>H</td><td>ti</td><td>166-7</td>

<td>XIV</td><td>Η</td><td>Η</td><td>Η</td><td>Η</td><td>ch₃</td><td>ch₃</td><td>H</td><td>CH₂SC ^ H₉(n)</td><td>oil</td>

<td>XV</td><td>Η</td><td>Η</td><td>Η</td><td>Η</td><td>^CS3</td><td>Cl</td><td>H</td><td>CH₂SC_youH₉(n)</td><td>oil</td>

<td>XVI</td><td>Η</td><td>Η</td><td>Η</td><td>Η</td><td>ch₃</td><td>CH₃</td><td>H</td><td>oh-c₂h₅Bro</td><td>123-4</td>

<td>XVII</td><td>Η</td><td>Η</td><td>Η</td><td>Η</td><td>^CIi3</td><td>^CS3</td><td>H</td><td>CH-CH t 3 Cl</td><td>147-8</td>

<td>XVIII</td><td>Η</td><td>Η</td><td>Η</td><td>Η</td><td>ch₃</td><td>OH3</td><td>H</td><td>CH₂Bro</td><td>143-4</td>

<td>XIX</td><td>Η</td><td>Η</td><td>Η</td><td>Η</td><td>^CH3</td><td>^CI3</td><td>H</td><td>tr^Bro</td><td>119-20</td>

<td>XX</td><td>Η</td><td>Η</td><td>Η</td><td>Η</td><td>Cl</td><td>Cl</td><td>H</td><td>CH₂OCH₃</td><td>107-9</td>

<td>XXI</td><td>Η</td><td>Η</td><td>Η</td><td>Η</td><td>Cl</td><td>Cl</td><td>H</td><td>CH-C1</td><td>142-4</td>

800 4 5 84

<td>In front of- statue</td><td>^b3</td><td>^Byou</td><td>^B5</td><td>^B6</td><td>^BT</td><td>^H8</td><td>^R9</td><td>. ^R10</td><td>m.p.</td>

<td>XXII</td><td>H</td><td>H</td><td>H</td><td>H</td><td>Cl</td><td>Cl</td><td>H</td><td>you</td><td>173-4</td>

<td>XXIII</td><td>H</td><td>H</td><td>H</td><td>H</td><td>^CH3</td><td>^CH3</td><td>H</td><td></td><td>139-41</td>

<td>XXIV</td><td>H</td><td>H</td><td>H</td><td>H</td><td>^CH3</td><td>^CH3</td><td>4-OH₃</td><td>CH₂OCH₃</td><td>oil</td>

<td>XXV</td><td>H</td><td>H</td><td>H</td><td>H</td><td>CH₃</td><td>^C.2^H5</td><td>H</td><td>ch₂ci</td><td>oil</td>

<td>XXVI</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>CH₃</td><td>3-C1</td><td>CH₂0CH₃</td><td>90-2</td>

<td>XXVII</td><td>H</td><td>H</td><td>H</td><td>H</td><td>^CH3</td><td>®3</td><td>3-Br</td><td>CHgOCH</td><td>96-7</td>

<td>XXVIII</td><td>H</td><td>H</td><td>H</td><td>H</td><td>^CH3</td><td>^CH3</td><td>3-Br</td><td>CH 3 Cl</td><td>182-3</td>

<td>XXIX</td><td>H</td><td>H</td><td>H</td><td>H</td><td>^CS3</td><td>ch₃</td><td>3-Br</td><td></td><td>145-8</td>

<td>XXX</td><td>H</td><td>H</td><td>H</td><td>H</td><td>^CH3</td><td>Bro</td><td>4-CH₃</td><td>CH₂0CH₃</td><td>125-6</td>

<td>XXXI</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>Bro</td><td>4-CH₃</td><td>ch₂ci</td><td>124-6</td>

<td>XXXII</td><td>H</td><td>H</td><td>H</td><td>H</td><td>Oh₃</td><td>Bro</td><td>4-CH₃</td><td>you</td><td>193-4</td>

<td>XXXIII</td><td>H</td><td>H</td><td>H</td><td>H</td><td>CH₃</td><td>^CH3</td><td>H</td><td>CHOCH i 3^CH3</td><td>90-4</td>

<td>XXXIV</td><td>H</td><td>H</td><td>H</td><td>H</td><td>^CH3</td><td>ch₃</td><td>H</td><td></td><td>149-52</td>

<td>XXXV</td><td>H</td><td>H</td><td>H</td><td>H</td><td>Oh₃</td><td>^CK3</td><td>4-C1</td><td>ch₂ci</td><td>gum</td>

<td>XXXVI</td><td>H</td><td>H</td><td>H</td><td>H</td><td>CH₃</td><td>^CH3</td><td>4-ci</td><td>Ί0</td><td>164-5</td>

<td>XXXVII</td><td>H</td><td>H</td><td>H</td><td>H</td><td>^C.2^H5</td><td>^C.2^H5</td><td>H</td><td>ch₂oh₃</td><td>109-12</td>

<td>XXXVIII</td><td>H</td><td>H</td><td>H</td><td>H</td><td>CH₃</td><td>^CH3</td><td>H</td><td colspan="2">CH 2 H (n) oil</td>

800 45 84 r

aé

<td>In front of- statue</td><td>^R3</td><td></td><td>^E5</td><td>^R6</td><td>^RT</td><td>^R8</td><td>^R9</td><td>^R10</td><td>m.p.</td>

<td>XXXIX</td><td>H</td><td>H</td><td>H</td><td>H</td><td>CH₃</td><td>^CH3</td><td>H</td><td>CH₂OC_youH₉(n)</td><td></td>

<td>XL</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ce₃</td><td>ch₃</td><td>H</td><td>ch₂och-c₂h₅^OH3</td><td></td>

<td>XLI</td><td>H</td><td>H</td><td>H</td><td>H</td><td>CH₃</td><td>CH₃</td><td>H</td><td>CH₂0CH₂CH = CH₂</td><td>98-100</td>

<td>XLII</td><td>H</td><td>H</td><td>H</td><td>H</td><td>CH₃</td><td>ch₃</td><td>H</td><td>CHpOCHpC = CH</td><td>91-93</td>

CH10

<td>XLIII</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>^CH3</td><td colspan="2">Η</td><td>107-8</td>

<td>XLIV</td><td>H</td><td>H</td><td>^CH3</td><td>H</td><td>ch₃</td><td>^CH3</td><td>H</td><td>ch₂oh₃</td><td>79-80</td>

<td>XLV</td><td>H</td><td>H</td><td>H</td><td>H</td><td>^CH3</td><td>CH₃</td><td>H</td><td>a = -n</td><td>56</td>

<td>XLVI</td><td>H</td><td>H</td><td>H</td><td>H</td><td>^C.2^H5</td><td>c₂h₅</td><td>H</td><td>"Ώ</td><td>142-4</td>

<td>XLVII</td><td>H</td><td>H</td><td>H</td><td>H</td><td>^C.2^H5</td><td>^C.2^H5</td><td>H</td><td>ch₂ci</td><td>88-9</td>

<td>XLVIII</td><td>H</td><td>H</td><td>H</td><td>H</td><td>Bro</td><td>Bro</td><td>H</td><td>CH₂OCH₃</td><td>150-2</td>

<td>XLIX</td><td>H</td><td>H</td><td>H</td><td>H</td><td>Cl</td><td>Cl</td><td>4-C1</td><td>CHgOCH</td><td>128-9</td>

<td>L.</td><td>H</td><td>H</td><td>H</td><td>H</td><td>c₂h₅</td><td>^C.2^H5</td><td>4-C1</td><td>CH₂OCH₃</td><td>114-6</td>

<td>LI</td><td>H</td><td>H</td><td>H</td><td>H</td><td>Bro</td><td>Cl</td><td>4-CH.</td><td>3 ch₂oh₃</td><td>131-4</td>

<td>Lil</td><td>H</td><td>H</td><td>H</td><td>H</td><td>^CH3</td><td>^C.2^H5</td><td>H</td><td>CHgOCH</td><td>96-8</td>

<td>LAZY</td><td>H</td><td>H</td><td>H</td><td>H</td><td>cn₃</td><td>cn₃</td><td>4-Br</td><td>ch₂oh₃</td><td>137-8</td>

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