CA1155135A - Herbicide compositions - Google Patents
Herbicide compositionsInfo
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- CA1155135A CA1155135A CA000178727A CA178727A CA1155135A CA 1155135 A CA1155135 A CA 1155135A CA 000178727 A CA000178727 A CA 000178727A CA 178727 A CA178727 A CA 178727A CA 1155135 A CA1155135 A CA 1155135A
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Abstract
IN THE UNITED STATES PATENT OFFICE
HERBICIDE COMPOSITIONS
Abstract of the Disclosure Herbicidal active sulfoxide and sulfone compounds are described herein. The compounds have the following generic formula:
HERBICIDE COMPOSITIONS
Abstract of the Disclosure Herbicidal active sulfoxide and sulfone compounds are described herein. The compounds have the following generic formula:
Description
li5S135 Description of th~ Invention This invention is directed to a novel group of compounds which may be generally described as sulfoxide and sulfone deri-vàtives of thiocarbamates which are highly active herbicides.
The compounds of the present invention are represented by the generic formula: ~ / R
-R-S()n-C~N\
wherein n can be 1 or 2; R can be selected from the group con-sisting of halophenyl, phenalkyl, substituted phenalkyl, wherein said substituents can be selected from halogen, alkyl and halo-alkyl; Rl and P~2 can be the same or different and can be selected from the group consisting of lower alkyl, cycLoallcyl, alkenyl, alkynyl and benzyl.
The above-noted compounds can be prepared by reacting an oxidizing agent such as peracetic acid cr m-chloroperoxy-benzoic acid with a thiocarbamate compound corresponding to the following formula: ~ ~ R
R-S-C-N \
wherein R, Rl and R2 have been defined above. The reaction is carried out in the presence of a ~olvent such as chloroform, methylene chloride, benzene or toluene, and at a reduced tempera-ture of from about -25C. to about 65C. The amount of oxidizing agent used must be at least one molar equivalent to form the sul-foxide derivative and at least two molar equivalents to form the sulfone derivatives.
~2-,.
The thiocarbamate compounds are known herbicides and their method of synthesis is known; see U.S. Patents 2,913,327,
The compounds of the present invention are represented by the generic formula: ~ / R
-R-S()n-C~N\
wherein n can be 1 or 2; R can be selected from the group con-sisting of halophenyl, phenalkyl, substituted phenalkyl, wherein said substituents can be selected from halogen, alkyl and halo-alkyl; Rl and P~2 can be the same or different and can be selected from the group consisting of lower alkyl, cycLoallcyl, alkenyl, alkynyl and benzyl.
The above-noted compounds can be prepared by reacting an oxidizing agent such as peracetic acid cr m-chloroperoxy-benzoic acid with a thiocarbamate compound corresponding to the following formula: ~ ~ R
R-S-C-N \
wherein R, Rl and R2 have been defined above. The reaction is carried out in the presence of a ~olvent such as chloroform, methylene chloride, benzene or toluene, and at a reduced tempera-ture of from about -25C. to about 65C. The amount of oxidizing agent used must be at least one molar equivalent to form the sul-foxide derivative and at least two molar equivalents to form the sulfone derivatives.
~2-,.
The thiocarbamate compounds are known herbicides and their method of synthesis is known; see U.S. Patents 2,913,327,
2,983,747, 3,133,947, 3,175,897 and 3,185,720-~for example.
However, the use of these thiocarbamates as reactive intermediates to form other compounds that also have pesticidal activity is unexpected.
In order to illustrate the merits of the present inven-tion the following examples are provided:
xample 1 O O
Cl ~ CE2-1-C-N
A solution was formed containing 7.5 g. of m-chloro-peroxybenzoic acid in 100 cc. of methylene chloride in a reactionvessel. The temperature of this solution was regulated to 30C., wherein 4.4 g. (0.017 mole) of S-4-chlorobenzyl diethylthiocar-bamate was added over a period of one minute. At the end of the addition, a rapid reflux began and the temperature rose to 41C.
The reaction was allowed to take place for about 40 minutes, wherein the mixture was cooled and filtered and the cake was washed with two portions of 25 cc. of methylene chloride. The combined filtrate was washed with four portions of 50 cc. of 5%
sodium carbonte solution and two portions of 50 cc. of water, then dried over magnesium sulfate and concentrated in a rotary evaporator, first under a water pump vacuum and finally under high vacuum to yield 4.4 g. of product, n30 _ 1.5425. ~fter standing for a short period, the liquid crystallized to yield a product of 4.4 g. having a m.p. of 64-72C.
~ 1~5S135 Example 2 O O
Cl ~ - CH2-S-C-~ 2 5 ~ solution was formed containing 10.7 g. (0.0525 mole) of m-chloroperoxybenzoic acid in 200 ec. of methylene chloride.
This solution was cooled to -16C., wherein 12.9 g. (0.05 mole) of S-4-chlorobenzyl diethylthiocarbamate was added over a period of four mintues. The reaction was allowed to take place for one hour, wherein the temperature was allowed to go to -5C. The temperature was held at 5C. for another 30 mintues, wherein the temperature was allowed to reach 21.5C. The solution was ~hen cooled in an ice bath, wherein the cold mixture was filtered and the cake was washed with two portions of 25 cc. of methylene chloride. The combined filtrate was washed with four portions of 100 cc. of 5% solution of sodium carbonate and two portions of 100 cc. of water, dried over magnesium sulfate and concentrated in a rotary evaporator, first under water pump vacuum and finally 15 under high vacuum to yield 12.3 g. of product, n30 ~ 1.5678.
This product was further distilled to yield 10.6 g. of product, n30 _ 1.5680.
~xample 3 O O
~ 2 - i-C H
In a 500 ml. 3-necked flask equipped with a thermometer, mechanical stirrer, and addition device were placed 250 ml. of 20 methylene chloride and 12.6 g. ~0.05 mole) of S-benzyl ethyl-isobutylthiocarbamate dissolved in 25 ml. of methylene chloride.
Stirring was begun and the temperature lowered to -30C. with dry 1~55~3S
ice. Then, 8.7 g. (0.05 mole) of m-chloroperoxybenzoic acid was rapad,ly added and the temperature held at -30C. for 15 minutes.
The temperature then was allowed to rise to 0C. over a 30-minute period and then up to 4C. The cold mixture was filtered and the filtrate washed with three 50 ml. portions of 5~ potassium carbo-nate solution, two 50 ml. portions of water and then dried over magnesium sulfate and stripped to obtain a colorless viscous liquid product weighing 13.5 g., n30 _ 1.5403.
Example 4 O O
C-M ~ 2 5 ~ 2 ¦l i-C4H9 A solution was formed containing 17.3 g. (0.10 mole) of m-chloroperoxybenzoic acid in 300 ml. of methylene chloride.
This mixture was warmed to 30C. whereupon 12.6 g. (0.05 mole) of S-benzyl ethylisobutylthiocarbamate in 25 ml. of methylene chloride was added at a rate such that gentle reflux was maintained. Stir-ring at reflux was carried out for thirty minutes and then the solution waC cooled to 5C. in an ice bath. The solid was filtered off and washed with cold methylene chlorlde. The combined por-tions of filtrate were washed with three 50 ml. portions of 5%
potassium carbonate solution, two 50 ml. portions of water, dried over magnesium sulfate, and then stripped to obtain 14.0 g. of product, n30 - 1.5255~
Other compounds were prepared in an analogous manner starting with the appropriate starting materials as outlined above.
" `` 1155135 The following is a table of compounds representative of those embodied by the present invention. Compound numbers have been assigned to them and are used for identification throughout the balance of the specification.
TABT~E I
R-S(O)n-C-N
Compound No. R -1 -2 n -CH2 ~ Cl -C2H5 -C2H5 -CH2 ~ Cl C2~5 -C2H5
However, the use of these thiocarbamates as reactive intermediates to form other compounds that also have pesticidal activity is unexpected.
In order to illustrate the merits of the present inven-tion the following examples are provided:
xample 1 O O
Cl ~ CE2-1-C-N
A solution was formed containing 7.5 g. of m-chloro-peroxybenzoic acid in 100 cc. of methylene chloride in a reactionvessel. The temperature of this solution was regulated to 30C., wherein 4.4 g. (0.017 mole) of S-4-chlorobenzyl diethylthiocar-bamate was added over a period of one minute. At the end of the addition, a rapid reflux began and the temperature rose to 41C.
The reaction was allowed to take place for about 40 minutes, wherein the mixture was cooled and filtered and the cake was washed with two portions of 25 cc. of methylene chloride. The combined filtrate was washed with four portions of 50 cc. of 5%
sodium carbonte solution and two portions of 50 cc. of water, then dried over magnesium sulfate and concentrated in a rotary evaporator, first under a water pump vacuum and finally under high vacuum to yield 4.4 g. of product, n30 _ 1.5425. ~fter standing for a short period, the liquid crystallized to yield a product of 4.4 g. having a m.p. of 64-72C.
~ 1~5S135 Example 2 O O
Cl ~ - CH2-S-C-~ 2 5 ~ solution was formed containing 10.7 g. (0.0525 mole) of m-chloroperoxybenzoic acid in 200 ec. of methylene chloride.
This solution was cooled to -16C., wherein 12.9 g. (0.05 mole) of S-4-chlorobenzyl diethylthiocarbamate was added over a period of four mintues. The reaction was allowed to take place for one hour, wherein the temperature was allowed to go to -5C. The temperature was held at 5C. for another 30 mintues, wherein the temperature was allowed to reach 21.5C. The solution was ~hen cooled in an ice bath, wherein the cold mixture was filtered and the cake was washed with two portions of 25 cc. of methylene chloride. The combined filtrate was washed with four portions of 100 cc. of 5% solution of sodium carbonate and two portions of 100 cc. of water, dried over magnesium sulfate and concentrated in a rotary evaporator, first under water pump vacuum and finally 15 under high vacuum to yield 12.3 g. of product, n30 ~ 1.5678.
This product was further distilled to yield 10.6 g. of product, n30 _ 1.5680.
~xample 3 O O
~ 2 - i-C H
In a 500 ml. 3-necked flask equipped with a thermometer, mechanical stirrer, and addition device were placed 250 ml. of 20 methylene chloride and 12.6 g. ~0.05 mole) of S-benzyl ethyl-isobutylthiocarbamate dissolved in 25 ml. of methylene chloride.
Stirring was begun and the temperature lowered to -30C. with dry 1~55~3S
ice. Then, 8.7 g. (0.05 mole) of m-chloroperoxybenzoic acid was rapad,ly added and the temperature held at -30C. for 15 minutes.
The temperature then was allowed to rise to 0C. over a 30-minute period and then up to 4C. The cold mixture was filtered and the filtrate washed with three 50 ml. portions of 5~ potassium carbo-nate solution, two 50 ml. portions of water and then dried over magnesium sulfate and stripped to obtain a colorless viscous liquid product weighing 13.5 g., n30 _ 1.5403.
Example 4 O O
C-M ~ 2 5 ~ 2 ¦l i-C4H9 A solution was formed containing 17.3 g. (0.10 mole) of m-chloroperoxybenzoic acid in 300 ml. of methylene chloride.
This mixture was warmed to 30C. whereupon 12.6 g. (0.05 mole) of S-benzyl ethylisobutylthiocarbamate in 25 ml. of methylene chloride was added at a rate such that gentle reflux was maintained. Stir-ring at reflux was carried out for thirty minutes and then the solution waC cooled to 5C. in an ice bath. The solid was filtered off and washed with cold methylene chlorlde. The combined por-tions of filtrate were washed with three 50 ml. portions of 5%
potassium carbonate solution, two 50 ml. portions of water, dried over magnesium sulfate, and then stripped to obtain 14.0 g. of product, n30 - 1.5255~
Other compounds were prepared in an analogous manner starting with the appropriate starting materials as outlined above.
" `` 1155135 The following is a table of compounds representative of those embodied by the present invention. Compound numbers have been assigned to them and are used for identification throughout the balance of the specification.
TABT~E I
R-S(O)n-C-N
Compound No. R -1 -2 n -CH2 ~ Cl -C2H5 -C2H5 -CH2 ~ Cl C2~5 -C2H5
3 ~ Cl C3 7 3 7
4 -CEI2 ~ -CH3 -CH(CH3)-C-CH
5 -CH2 ~ -C2H5 i-C4H9
6 -CH2 ~ n C3H7 n-c3H7 -CH2 ~ 3 7 n-C4H9 ~5S~3S
TABLE I (Cont~ ) Compound No. R Rl R2 n C24~ C3H7 3 7 3 6~ C 3 7 3 7 -CH2~9 -C2H5 i C4EI9 2 11 -CH;~ C3 7 12 -CH2~ -(~2H5 -C2H5 .
13 -CH2 ~ 3 7 3 7 14 -CH2~--Cl C3H7 n C3H7 -CH2 {~Cl -C2H5 n-C4H9 16 -CH2--~ 3 7 n~C3H7 2 ~ i!
155~35 TABLE I (Con t . ) Compound No. R R R n n-C3H7 n C3H7 2 18 -CH2~3 -C2H5 -CH2~
19 -CH2~CH3 -C2H5 -CH2CH=CH2 -CH2~CH3 n-C3H7 n~C3H7 2 21 -CH2~ -C2H5 -CH
22 -CH2~ -C2H5 -C2H5 23 -CH2~3 -n-C4Hg -n-C4Hg 24 -CH2~3 -n-C4Hg -i-C4H9 -CH2~3 -n-C4Hg -sec-C4H9 26 -CH2~3 -i-C4Hg ~sec-C4Hg 27 -CH2~ -C2H5 -n-C4H9 2 28 -CH2~ -C2H5 -sec-C4H9 2 29 -CH2~ ~ C4H9 -n-C~Hg 2 ~55~35 TABLE I (Cont.
Compound ~. R ~ R2 -CH~ ~ -n-C4Hg -i-C4H9 2 31 -CH2 ~ -n-C4Hg -sec-C4H9 2 32 -CH2 ~ -i-C4Hg -i-C4H9 2 33 -CH2 ~ C4~9 -sec~C4H 2 .
34 -CH2 ~ -C2H5 -n-C4H9 -CH2 ~ -C2H5 -sec-C4H9 36 -CH2 ~ -C2H5 -t-C4H9 37 -CH2 ~ -n-C3H7 -i-C4H9 .
38 -CH2 ~ -n-C3H7 -sec-C4Hg 39 -CH2 ~ -i-C3~17 ~n-C~Hg -CH2 ~ i-C3H7 i C4~9 41 -CH2 ~ F3 -C2H5 -n-C4H9 ,CF
42 -CH2 ~ -C2H5 -i-C4H9 43 -CH2 ~ CF3 -n-C4Hg -n C4H9 1155~35 TABLE I (~
Compound No. R Rl R2 n 44 -CH2~ -C2H5 ~
-CH2~Cl -C2H5 -i-C4Hg 1 46 -CH2~Cl -n-C4Hg -n-C4H9 47 -CH2~3Cl -C2H5 {~ 1 48 -CH2~3cH3 C2H5 -n-C4H9 49 -CH2 g3CH3 -C2H5 -i-C4Hg -CH2~CH3 -n-C3H7 -n-C3H7 51 -CH2~CH3 -n-C4Hg -n-C4Hg 52 -CH2g3CEl3 C2H5 53 -CH2~ i-C3H7 n C4H9 2 54 -CH2~ C3H7 - i-C3H7 2 -CE~2~ -CH3 -CH3 56 -CH2~ -C2H5 -n-C5Hll 1 57 -CH2~ -C2H5 -sec-C5Hll 1 1~5513S
~ Cont.
Compou~d No. R Rl -2 58 -CH2 ~ -C2H
~1 ' 59 -CH2~ -n-c3~7 -n-c3H7 C~
C~
CH2 ~ -C2H5 n C4H9 61 CH2 ~ -C2H5 -sec-C4H9 62 -CH2 ~ -CH3 sec C H
63 -CH2 ~ -CH3 -sec-C5Hll 1 64 -CH2 ~ -CH3 -CH(CH3)-C~(c~3)2 -CH2 ~ -C2H5 -i-C3H7 66 -CH2 ~ -C2H5 67 -CH2 ~ -C2H5 -cH(cH3)-cH(cH3)2 68 -CH2 ~ -i-C3H7 -i-C3H7 .1 69 -CH2 ~ -i-C3H7 n C5Hll 115513~
TABL.E I (Cont . ) Compound No, R Rl R2 n CH2~3 i C3H7 -sec-C5H11 1 71 -CH2~3 -i-C4Hg -i-C4H9 72 -CH2~3 -sec-C4H9 -sec-C4H9 73 -CH2~ -c2l~5 -CH2-CH=CH2 L
74 -CH2~3 -C2H5 -i-C4H9 C
-CH2~ -i-C4Hg -i-C4H9
TABLE I (Cont~ ) Compound No. R Rl R2 n C24~ C3H7 3 7 3 6~ C 3 7 3 7 -CH2~9 -C2H5 i C4EI9 2 11 -CH;~ C3 7 12 -CH2~ -(~2H5 -C2H5 .
13 -CH2 ~ 3 7 3 7 14 -CH2~--Cl C3H7 n C3H7 -CH2 {~Cl -C2H5 n-C4H9 16 -CH2--~ 3 7 n~C3H7 2 ~ i!
155~35 TABLE I (Con t . ) Compound No. R R R n n-C3H7 n C3H7 2 18 -CH2~3 -C2H5 -CH2~
19 -CH2~CH3 -C2H5 -CH2CH=CH2 -CH2~CH3 n-C3H7 n~C3H7 2 21 -CH2~ -C2H5 -CH
22 -CH2~ -C2H5 -C2H5 23 -CH2~3 -n-C4Hg -n-C4Hg 24 -CH2~3 -n-C4Hg -i-C4H9 -CH2~3 -n-C4Hg -sec-C4H9 26 -CH2~3 -i-C4Hg ~sec-C4Hg 27 -CH2~ -C2H5 -n-C4H9 2 28 -CH2~ -C2H5 -sec-C4H9 2 29 -CH2~ ~ C4H9 -n-C~Hg 2 ~55~35 TABLE I (Cont.
Compound ~. R ~ R2 -CH~ ~ -n-C4Hg -i-C4H9 2 31 -CH2 ~ -n-C4Hg -sec-C4H9 2 32 -CH2 ~ -i-C4Hg -i-C4H9 2 33 -CH2 ~ C4~9 -sec~C4H 2 .
34 -CH2 ~ -C2H5 -n-C4H9 -CH2 ~ -C2H5 -sec-C4H9 36 -CH2 ~ -C2H5 -t-C4H9 37 -CH2 ~ -n-C3H7 -i-C4H9 .
38 -CH2 ~ -n-C3H7 -sec-C4Hg 39 -CH2 ~ -i-C3~17 ~n-C~Hg -CH2 ~ i-C3H7 i C4~9 41 -CH2 ~ F3 -C2H5 -n-C4H9 ,CF
42 -CH2 ~ -C2H5 -i-C4H9 43 -CH2 ~ CF3 -n-C4Hg -n C4H9 1155~35 TABLE I (~
Compound No. R Rl R2 n 44 -CH2~ -C2H5 ~
-CH2~Cl -C2H5 -i-C4Hg 1 46 -CH2~Cl -n-C4Hg -n-C4H9 47 -CH2~3Cl -C2H5 {~ 1 48 -CH2~3cH3 C2H5 -n-C4H9 49 -CH2 g3CH3 -C2H5 -i-C4Hg -CH2~CH3 -n-C3H7 -n-C3H7 51 -CH2~CH3 -n-C4Hg -n-C4Hg 52 -CH2g3CEl3 C2H5 53 -CH2~ i-C3H7 n C4H9 2 54 -CH2~ C3H7 - i-C3H7 2 -CE~2~ -CH3 -CH3 56 -CH2~ -C2H5 -n-C5Hll 1 57 -CH2~ -C2H5 -sec-C5Hll 1 1~5513S
~ Cont.
Compou~d No. R Rl -2 58 -CH2 ~ -C2H
~1 ' 59 -CH2~ -n-c3~7 -n-c3H7 C~
C~
CH2 ~ -C2H5 n C4H9 61 CH2 ~ -C2H5 -sec-C4H9 62 -CH2 ~ -CH3 sec C H
63 -CH2 ~ -CH3 -sec-C5Hll 1 64 -CH2 ~ -CH3 -CH(CH3)-C~(c~3)2 -CH2 ~ -C2H5 -i-C3H7 66 -CH2 ~ -C2H5 67 -CH2 ~ -C2H5 -cH(cH3)-cH(cH3)2 68 -CH2 ~ -i-C3H7 -i-C3H7 .1 69 -CH2 ~ -i-C3H7 n C5Hll 115513~
TABL.E I (Cont . ) Compound No, R Rl R2 n CH2~3 i C3H7 -sec-C5H11 1 71 -CH2~3 -i-C4Hg -i-C4H9 72 -CH2~3 -sec-C4H9 -sec-C4H9 73 -CH2~ -c2l~5 -CH2-CH=CH2 L
74 -CH2~3 -C2H5 -i-C4H9 C
-CH2~ -i-C4Hg -i-C4H9
7 6 -CH2~ -C~3 - i-C3H7 77 -CH2~3 -CH3 -n-C6H13 78 -CH2~ -C2H5 -n-C3H7 79 -CH2~3 ''C2H5 -n-C6H13 -CH2~3 -n-C3H7 -n-C5H11 1 81 -CH2~3 -n-C3H7 -sec-C5H11 1 1155~3S
TABLE I (Cont.) Compound No. R R R2 n --1 _ 82 -CH2 ~ -n C3H7 -CH(CH3~-CH(CH3)2 83 -CEI2 ~ -CH3 -CH
84 -CH2 ~ -n-C3H7 -i-C3H7 -CEI2 ~ C1 -CE~3 -CH2- ~ 1 86 -CH2 ~ C1 -C2EI5 -CH2 ~
87 -CH2 ~ Cl -C2H5 -CH2- ~ 1 88 -CEI2 ~ Cl -n-C3~I7 -CH
89 -CH2 ~ -C2H5 -CH
Herbicidal Screening Tests .
As previously mentioned, the novel compounds herein des-cribed are phytotoxic compounds which are useful and valuable in controlling various plants species. Compounds of this invention are tested as herbicides in the following manner.
Pre-emergence Herbicide Screening Test Using an analytical halance, 20 mg. of the compound to be llS5~3S
tested is weighed out on a piece of glassine weighing paper. The paper and compound are placed in a 30 ml. wide-mouth bottle and 3 ml. of acetone containing 1% Tween 20~ is added to dissolve the compound. If the material is not soluble in acetone, another solvent such as water, alcohol or dimethylformamide (DMF) is used instead. When DMF is used, only 0.5 ml. or less is used to dissolve the compound and then another solvent is used to make the volume up to 3 ml. The 3 ml. of solution is sprayed uni-formly on the soil contained in a small Styrofoam flat one day after planting weed seeds in the flat of soil. A Mo. 152 DeVilbiss atomizer is used to apply the spray using compressed air at a pressure of 5 lb./sq. in. The rate of application is
TABLE I (Cont.) Compound No. R R R2 n --1 _ 82 -CH2 ~ -n C3H7 -CH(CH3~-CH(CH3)2 83 -CEI2 ~ -CH3 -CH
84 -CH2 ~ -n-C3H7 -i-C3H7 -CEI2 ~ C1 -CE~3 -CH2- ~ 1 86 -CH2 ~ C1 -C2EI5 -CH2 ~
87 -CH2 ~ Cl -C2H5 -CH2- ~ 1 88 -CEI2 ~ Cl -n-C3~I7 -CH
89 -CH2 ~ -C2H5 -CH
Herbicidal Screening Tests .
As previously mentioned, the novel compounds herein des-cribed are phytotoxic compounds which are useful and valuable in controlling various plants species. Compounds of this invention are tested as herbicides in the following manner.
Pre-emergence Herbicide Screening Test Using an analytical halance, 20 mg. of the compound to be llS5~3S
tested is weighed out on a piece of glassine weighing paper. The paper and compound are placed in a 30 ml. wide-mouth bottle and 3 ml. of acetone containing 1% Tween 20~ is added to dissolve the compound. If the material is not soluble in acetone, another solvent such as water, alcohol or dimethylformamide (DMF) is used instead. When DMF is used, only 0.5 ml. or less is used to dissolve the compound and then another solvent is used to make the volume up to 3 ml. The 3 ml. of solution is sprayed uni-formly on the soil contained in a small Styrofoam flat one day after planting weed seeds in the flat of soil. A Mo. 152 DeVilbiss atomizer is used to apply the spray using compressed air at a pressure of 5 lb./sq. in. The rate of application is
8 lb./acre and the spray volume is 143 gal./acre.
On the day preceding treatment, the Styrofoam flat, which is 7 inches long, 5 inches wide and 2.75 inches deep, is filled to a depth of 2 inches with loamy sand soil. Seeds of seven different weed species are pla~ed in individual rows using one species per row across the width of the flat. The seeds are covered with soil so that they are planted at a depth of 0.5 inch. The seeds used are hairy crabgrass (Di~itarla ~ ), yellow foxtail (Sertaria ~lauca), redroot pigweed (~maranthus retroflexus), Indian mustard (~rassica juncea) and curly dock (Rumex crispus). ~mple seeds are planted to give about 20 to 50 seedlings per row after emergence depending on the size of the plants.
After treatment, the flats are placed in the greenhouse at a temperature of 70 to 85F. and watered by sprinkling. Two weeks after treatment the degree of injury or control is deter-mined by comparison with untreated check plants of the same age.
The injury rating from 0 to 100% is recorded for each species as percent control with 0% representing no injury and 100% represent-ing complete kill.
!~ -14-" 1~55~35 Post-emergence Herbicide Screening Test Seeds of six plant species, including hairy crabgrass, watergrass, red oat, mustard, curly dock and Pinto beans (Phaseolus vulgaris) are planted in the Styrofoam flats as des-cribed above for pre-emergence screening. The flats are placed in the greenhouse at 70 to 85F. and watered daily with a sprinkler. About 10 to 14 days after planting when the primary leaves of the bean plants are almost fully expanded and the first trifoliate leaves are just starting to form, the plants are sprayed. The spray is prepared by weighing out 20 mg. of the test compound, dissolving it in 5 ml. of acetone containing 1~
Tween 20~ and then adding 5 ml. of water. The solution is sprayed on the foliage using a No. 152 DeVilbiss atomizer at an air pressure of 5 lb./sq. in. The spray concentration is 0.2 and the rate is 8 lb./acre. The spray volume is 476 gal./acre.
Injury ratings are recorded 14 days after treatment.
The rating system is the same as described above for the pre-emergence test. The injury symptoms are also the same as listed above for the pre-emergence test, except that IG (inhibited ger-mination) is not used since the seeds have alread~ germinatedbefore treatment in the post-emergence screening test.
The results of these tests are shown in Table II.
.,.
~L15513~
TABLE II
HERBICIDAL ACTIVITY - SCREENING RESULTS
Per Cent Control~' at 8 lb./A
Compound No. Pre-emer~ence Post-emergence 2 89 ` 88 99.7 93 6 99.9 87
On the day preceding treatment, the Styrofoam flat, which is 7 inches long, 5 inches wide and 2.75 inches deep, is filled to a depth of 2 inches with loamy sand soil. Seeds of seven different weed species are pla~ed in individual rows using one species per row across the width of the flat. The seeds are covered with soil so that they are planted at a depth of 0.5 inch. The seeds used are hairy crabgrass (Di~itarla ~ ), yellow foxtail (Sertaria ~lauca), redroot pigweed (~maranthus retroflexus), Indian mustard (~rassica juncea) and curly dock (Rumex crispus). ~mple seeds are planted to give about 20 to 50 seedlings per row after emergence depending on the size of the plants.
After treatment, the flats are placed in the greenhouse at a temperature of 70 to 85F. and watered by sprinkling. Two weeks after treatment the degree of injury or control is deter-mined by comparison with untreated check plants of the same age.
The injury rating from 0 to 100% is recorded for each species as percent control with 0% representing no injury and 100% represent-ing complete kill.
!~ -14-" 1~55~35 Post-emergence Herbicide Screening Test Seeds of six plant species, including hairy crabgrass, watergrass, red oat, mustard, curly dock and Pinto beans (Phaseolus vulgaris) are planted in the Styrofoam flats as des-cribed above for pre-emergence screening. The flats are placed in the greenhouse at 70 to 85F. and watered daily with a sprinkler. About 10 to 14 days after planting when the primary leaves of the bean plants are almost fully expanded and the first trifoliate leaves are just starting to form, the plants are sprayed. The spray is prepared by weighing out 20 mg. of the test compound, dissolving it in 5 ml. of acetone containing 1~
Tween 20~ and then adding 5 ml. of water. The solution is sprayed on the foliage using a No. 152 DeVilbiss atomizer at an air pressure of 5 lb./sq. in. The spray concentration is 0.2 and the rate is 8 lb./acre. The spray volume is 476 gal./acre.
Injury ratings are recorded 14 days after treatment.
The rating system is the same as described above for the pre-emergence test. The injury symptoms are also the same as listed above for the pre-emergence test, except that IG (inhibited ger-mination) is not used since the seeds have alread~ germinatedbefore treatment in the post-emergence screening test.
The results of these tests are shown in Table II.
.,.
~L15513~
TABLE II
HERBICIDAL ACTIVITY - SCREENING RESULTS
Per Cent Control~' at 8 lb./A
Compound No. Pre-emer~ence Post-emergence 2 89 ` 88 99.7 93 6 99.9 87
9 88 60 . 90 76 9~ 72 ~L~55~35 TABLÆ II (Cont.~
.
Gompound No Pre-emerg~ence Post-emer~ence 38 - g8 gl 39 ~4 87 .
gO 75 47 ~1 7~
53 0 ` 32 54 4g 57 ~15S~35 TABI,E II (Cont~
~.
Per Cent Control'; at 8 lb. /A
- Compound __ No. Pre emer~ence Post-emergence ~3 99 81 6~ g9.9 93 67 100 ~0 72 100 88 `
~9.6 85 ~.
llSS135 T~BLE II (Cont.~
Per Cent Control* at 8 lb./A
Compound No. Pre-emer~ence Post-eme~
Per Cent Control at 20 lb./A
Compound No. Pre-emer~ence Post-emer~ence * Average for seven plant species in the pre-e~er~ence test '`
and for six plant species in the post-emerg~nce test.
The compounds of the present invention can be used in any convenient form. Thus, the compounds can be made into emul-sifiable liquids, emulsifiable concentrates, liquid, wettable po~-der, powders, granular or any other convenient fo~rm, and applied to the soil to control the undesired vegetation.
The terms lower alkyl, alkenyl and alkynyl are meant t~
include those compounds having straight or branched chain coni-gurations having from 1 to 6 carbon atoms, inclusive.
.
Gompound No Pre-emerg~ence Post-emer~ence 38 - g8 gl 39 ~4 87 .
gO 75 47 ~1 7~
53 0 ` 32 54 4g 57 ~15S~35 TABI,E II (Cont~
~.
Per Cent Control'; at 8 lb. /A
- Compound __ No. Pre emer~ence Post-emergence ~3 99 81 6~ g9.9 93 67 100 ~0 72 100 88 `
~9.6 85 ~.
llSS135 T~BLE II (Cont.~
Per Cent Control* at 8 lb./A
Compound No. Pre-emer~ence Post-eme~
Per Cent Control at 20 lb./A
Compound No. Pre-emer~ence Post-emer~ence * Average for seven plant species in the pre-e~er~ence test '`
and for six plant species in the post-emerg~nce test.
The compounds of the present invention can be used in any convenient form. Thus, the compounds can be made into emul-sifiable liquids, emulsifiable concentrates, liquid, wettable po~-der, powders, granular or any other convenient fo~rm, and applied to the soil to control the undesired vegetation.
The terms lower alkyl, alkenyl and alkynyl are meant t~
include those compounds having straight or branched chain coni-gurations having from 1 to 6 carbon atoms, inclusive.
Claims (187)
1. A compound represented by the following generic formula:
.
wherein n is 1 or 2; R is selected from the group consisting of halophenyl, phenalkyl, substituted phenalkyl, wherein said sub-stituents can be selected from halogen, alkyl and haloalkyl; R1 and R2 can be the same or different and can be selected from the group consisting of lower alkyl, cycloalkyl, alkenyl, alkynyl and benzyl with the proviso that when R is benzyl R1 and R2 are not both-sec-C4H9.
.
wherein n is 1 or 2; R is selected from the group consisting of halophenyl, phenalkyl, substituted phenalkyl, wherein said sub-stituents can be selected from halogen, alkyl and haloalkyl; R1 and R2 can be the same or different and can be selected from the group consisting of lower alkyl, cycloalkyl, alkenyl, alkynyl and benzyl with the proviso that when R is benzyl R1 and R2 are not both-sec-C4H9.
2. The compound as set forth in Claim 1 wherein R is , R1 is -C2H5, R2 is -C2H5 and n is 2.
3. The compound as set forth in Claim 1 wherein R is , R1 is -C2H5, R2 is -C2H5 and n is 1.
4. The compound as set forth in Claim 1 wherein R is , R1 is n-C3H7, R2 is n-C3H7, and n is 1.
5. The compound as set forth in Claim 1 wherein R is , R1 is -CH3, R2 is -CH(CH3)-C?CH and n is 1.
6. The compound as set forth in Claim 1 wherein R is , R1 is -C2H5, R2 is i-C4H9 and n is 1.
7. The compound as set forth in Claim 1 wherein R is , R1 is n-C3H7, R2 is n-C3H7 and n is 1.
8. The compound as set forth in Claim 1 wherein R is , R1 is n-C3H7, R2 is n-C4H9 and n is 1.
9. The compound as set forth in Claim 1 wherein R is , R1 is n-C3H7, R2 is n-C3H7 and n is 1,
10. The compound as set forth in Claim 1 wherein R is , R1 is n-C3H7, R2 is n-C3H7 and n is 1.
11. The compound as set forth in Claim 1 wherein R is , R1 is -C2H5, R2 is i-C4H9 and n is 2.
12. The compound as set forth in Claim 1 wherein R is , R1 is n-C3H7, R2 is and n is 1.
13. The compound as set forth in Claim 1 wherein R is , R1 is -C2H5, R2 is -C2H5 and n is 1.
14. The compound as set forth in Claim 1 wherein R is , R1 is n-C3H7, R2 is n-C3H7 and n is 1.
15. The compound as set forth in Claim 1 wherein R is , R1 is n-C3H7, R2 is n-C3H7 and n is 1.
16. The compound as set forth in Claim 1 wherein R is , R1 is -C2H5, R2 is n-C4H9 and n is 1.
17. The compound as set forth in Claim 1 wherein R is , R1 is n-C3H7, R2 is n-C3H7 and n is 2.
18. The compound as set forth in Claim 1 wherein R is , R1 is n-C3H7, R2 is n-C3H7 and n is 2.
19. The compound as set forth in Claim 1 wherein R is , R1 is -C2H5, R2 is and n is 1.
20. The compound as set forth in Claim 1 wherein R is , R1 is -C2H5, R2 iS -CH2CH=CH2 and n is 1.
21. The compound as set forth in Claim 1 wherein R is , R1 is n-C3H7, R2 is n-C3H7 and n is 2.
22. The compound as set forth in Claim 1 wherein R is , R1 is -C2H5, R2 is and n is 1.
23. The compound as set forth in Claim 1 wherein R is , R1 is -C2H5, R2 is -C2H5 and n is 1.
24. The compound as set forth in Claim 1 wherein R is , R1 is -n-C4H9, R2 is -n-C4H9 and n is 1.
25. The compound as set forth in Claim 1 wherein R is , R1 is -n-C4H9, R2 is -i-C4H9 and n is 1.
26. The compound as set forth in Claim 1 wherein R is , R1 is -n-C4H9, R2 is -sec-C4H9 and n is 1.
27. The compound as set forth in Claim 1 therein R is , R1 is -i-C4H9, R2 is -sec-C4H9 and n is 1.
28. The compound as set forth in Claim 1 wherein R is , R1 is -C2H5, R2 is -n-C4H9 and n is 2.
29. The compound as set forth in Claim 1 wherein R is , R1 is -C2H5, R2 is -sec-C4H9 and n is 2.
30. The compound as set forth in Claim 1 wherein R is , R1 is -n-C4H9, R2 is -n-C4H9 and n is 2.
31. The compound as set forth in Claim 1 wherein R is , R1 is -n-C4H9, R2 is -i-C4H9 and n is 2.
32. The compound as set forth in Claim 1 wherein R is , R1 is -n-C4H9, R2 is -sec-C4H9 and n is 2.
33. The compound as set forth in Claim 1 wherein R is , R1 is -i-C4H9, R2 is -i-C4H9 and n is 2.
34. The compound as set forth in Claim 1 wherein R is , R1 is -i-C4H9, R2 is -sec-C4H9 and n is 2.
35. The compound as set forth in Claim 1 wherein R is , R1 is -C2H5, R2 is -n-C4H9 and n is 1.
36. The compound as set forth in Claim 1 wherein R is , R1 is -C2H5, R2 is -sec-C4H9 and n is 1.
37. The compound as set forth in Claim 1 wherein R is , R1 is -C2H5, R2 is -t-C4H9 and n is 1.
38. The compound as set forth in Claim 1 wherein R is , R1 is -n-C3H7, R2 is -i-C4H9 and n is 1.
39. The compound as set forth in Claim 1 wherein R is , R1 is -n-C3H7, R2 is -sec-C4H9 and n is 1.
40. The compound as set forth in Claim 1 wherein R is , R1 is -i-C3H7, R2 is -n-C4H9 and n is 1.
41. The compound as set forth in Claim 1 wherein R is , R1 is -i-C3H7, R2 is -i-C4H9 and n is 1.
42. The compound as set forth in Claim 1 wherein R is , R1 is -C2H5, R2 is -n-C4H9 and n is 1.
43. The compound as set forth in Claim 1 wherein R is ,R1 is -n-C2H5, R2 is -i-C4H9 and n is 1.
44. The compound as set forth in Claim 1 wherein R is , R1 is -n-C4H9, R2 is -n-C4H9 and n is 1.
45. The compound as set forth in Claim 1 wherein R is , R1 is -C2H5, R2 is , and n is 1.
46. The compound as set forth in Claim 1 wherein R is , R1 is -C2H5, R2 is -i-C4H9 and n is 1.
47. The compound as set forth in Claim 1 wherein R is , R1 is -n-C4H9, R2 is -n-C4H9 and n is 1.
48. The compound as set forth in Claim 1 wherein R is , R1 is -C2H5, R2 is -n-C4H9 and n is 1.
49. The compound as set forth in Claim 1 wherein R is , R1 is -C2H5, R2 is -n-C4H9 and n is 1.
50. The compound as set forth in Claim 1 wherein R is , R1 is -C2H5, R2 is -i-C4H9 and n is 1.
51. The compound as set forth in Claim 1 wherein R is , R1 is -n-C3H7, R2 is -n-C3H7 and n is 1.
52. The compound as set forth in Claim 1 wherein R is , R1 is -n-C4H9, R2 is -n-C4H9 and n is 1.
53. The compound as set forth in Claim 1 wherein R is , R1 is C2H5, R2 is and n is 1.
54. The compound as set forth is Claim 1 wherein R is , R1 is i-C3H7, R2 is -n-C4H9 and n is 2.
55. The compound as set forth in Claim 1 wherein R is , R1 is -i-C3H7, R2 is -i-C3H7 and n is 2.
56. The compound as set forth in Claim 1 wherein R is , R1 is -CH3, R2 is -CH3 and n is 1.
57. The compound as set forth in Claim 1 wherein R is , R1 is -C2H5, R2 is -n-C5H11 and n is 1.
58. The compound as set forth in Claim 1 wherein R is , R1 is -C2H5, R2 is -sec-C5H11 and n is 1.
59. The compound as set forth in Claim 1 wherein R is , R1 is -C2H5, R2 is and n is 1.
60. The compound as set forth in Claim 1 wherein R is , R1 is -n-C3H7, R2 is -n-C3H7 and n is 1.
61. The compound as set forth in Claim 1 wherein R is , R1 is -C2H5, R2 is -n-C4H9 and n is 1.
62. The compound as set forth in Claim 1 wherein R is , R1 is -C2H5, R2 is -sec-C4H9 and n is 1.
63. The compound as set forth in Claim 1 wherein R is , R1 is -CH3, R2 is -sec-C4H9 and n is 1.
64. The compound as set forth in Claim 1 wherein R is , R1 CH3, R2 is -sec-C5H11 and n is 1.
65. The compound as set forth in Claim 1 wherein R is , R1 is -CH3, R2 is -CH(CH3)-CH(CH3)2 and n is 1.
66. The compound as set forth in Claim 1 wherein R is , R1 is C2H5, R2 is -i-C3H7 and n is 1.
67. The compound as set forth in Claim 1 wherein R is , R1 is C2H5, R2 is -CH2-CH=CH2 and n is 1.
68. The compound as set forth in Claim 1 wherein R is , R1 is -C2H5, R2 is -CH(CH3)-CH(CH3)2 and n is 1.
69. The compound as set forth in Claim 1 wherein R is , R1 is -i-C3H7, R2 is -1-C3H7 and n is 1.
70. The compound as set forth in Claim 1 wherein R is , R1 is -i-C3H7, R2 is -n-C5H11 and n is 1.
71. The compound as set forth in Claim 1 wherein R is , R1 is -i-C3H7, R2 is -sec-C5H11 and n is 1.
72. The compound as set forth in Claim 1 wherein R is , R1 is -i-C4H9, R2 is -i-C4H9 and n is 1.
73. The compound as set forth in Claim 1 wherein R is , R1 is -C2H5, R2 is -CH2-CH=CH2 and n is 1.
74. The compound as set forth in Claim 1 wherein R is , R1 is -C2H5, R2 is -i-C4H9 and n is 1.
75. The compound as set forth in Claim 1 wherein R is , R1 is -i-C4H9, R2 is -i-C4H9 and n is 1.
76. The compound as set forth in Claim 1 wherein R is , R1 is -CH3, R2 is -i-C3H7 and n is 1.
77. The compound as set forth in Claim 1 wherein R is , R1 is -CH3, R2 is -n-C6H13 and n is 1.
78. The compound as set forth in Claim 1 wherein R is , R1 is -C2H5, R2 is -n-C3H7 and n is 1.
79. The compound as set forth in Claim 1 wherein R is , R1 is -C2H5, R2 is -n-C6H13 and n is 1.
80. The compound as set forth in Claim 1 wherein R is , R1 is -n-C3H7, R2 is -n-C5H11 and n is 1.
81. The compound as set forth in Claim 1 wherein R is , R1 is -n-C3H7, R2 is -sec-C5H11 and n is 1.
82. The compound as set forth in Claim 1 wherein R is , R1 is -n-C3H7, R2 is -CH(CH3)-CH(CH3)2 and n is 1.
83. The compound as set forth in Claim 1 wherein R is , R1 is -CH3, R2 is and n is 1.
84. The compound as set forth in Claim 1 wherein R is , R1 is -n-C3H7, R2 is -i-C3H7, and n is 1.
85. The compound as set forth in Claim 1 wherein R is , R1 is -CH3, R2 is and n is 1.
86. The compound as set forth in Claim 1 wherein R is , R1 is -C2H5, R2 is and n is 1.
87. The compound as set forth in Claim 1 wherein R is , R1 is -C2H5, R2 is and n is 1.
88. The compound as set forth in Claim 1 wherein R is , R1 is -n-C3H7, R2 is and n is 1.
89. The compound as set forth in Claim 1 wherein R is , R1 is -C2H5, R2 is and n is 1.
90. The method of controlling undesirable vegetation comprising applying to the locus where control is desired an herbicidally effective amount of a compound represented by the following generic formula:
wherein n is 1 or 2; R is selected from the group consisting of halophenyl, phenalkyl, substituted phenalkyl, wherein said sub-stituents can be selected from halogen, alkyl and haloalkyl; R1 and R2 can be the same or different and can be selected from the group consisting of lower alkyl, cycloalkyl, alkenyl, alkynyl and benzyl with the proviso that when R is benzyl R1 and R2 are not both sec C4-C9.
wherein n is 1 or 2; R is selected from the group consisting of halophenyl, phenalkyl, substituted phenalkyl, wherein said sub-stituents can be selected from halogen, alkyl and haloalkyl; R1 and R2 can be the same or different and can be selected from the group consisting of lower alkyl, cycloalkyl, alkenyl, alkynyl and benzyl with the proviso that when R is benzyl R1 and R2 are not both sec C4-C9.
91. The method as set forth in Claim 90 wherein R is , R1 is -C2H5, R2 is -C2H5 and n is 2.
92. The method as set forth in Claim 90 wherein R is , R1 is -C2H5, R2 is -C2H5 and n is 1.
93. The method as set forth in Claim 90 wherein R is , R1 is n-C3H7, R2 is n-C3H7, and n is 1.
94. The method as set forth in Claim 90 wherein R is , R1 is -CH3, R2 is -CH(CH3)-C?CH and n is 1.
95. The method as set forth in Claim 90 wherein R is , R1 is -C2H5, R2 is i-C4H9 and n is 1.
96. The method as set forth in Claim 90 wherein R is , Rl is n-C3H7, R2 is n-C3H7 and n is 1.
97. The method as set forth in Claim 90 wherein R is , R1 is n-C3H7, R2 is n-C4H9 and n is 1.
98. The method as set forth in Claim 90 wherein R is ,R1 is n-C3H7, R2 is n-C3H7 and n is 1.
99. The method as set forth in Claim 90 wherein R is , R1 is n-C3H7, R2 is n-C3H7 and n is 1.
100. The method as set forth in Claim 90 wherein R is , R1 is -C2H5, R2 is i-C4H9 and n is 2.
101. The method as set forth in Claim 90 wherein R is , R1 is n-C3H7, R2 is and n is 1.
102. The method as set forth in Claim 90 wherein R is , R1 is -C2H5, R2 is -C2H5 and n is 1.
103. The method as set forth in Claim 90 wherein R is , R1 is n-C3H7, R2 is n-C3H7 and n is 1.
104. The method as set forth in Claim 90 wherein R is , R1 is n-C3H7, R2 is n-C3H7 and n is 1.
105. The method as set forth in Claim 90 wherein R is , R1 is -C2H5, R2 is n-C4H9 and n is 1.
106. The method as set forth in Claim 90 wherein R is , R1 is n-C3H7, R2 is n-C3H7 and n is 2.
107. The method as set forth in Claim 90 wherein R is , R1 is n-C3H7, R2 is n-C3H7 and n is 2.
108. The method as set forth in Claim 90 wherein R is ,R1 is -C2H5, R2 is and n is 1.
109. The method as set forth in Claim 90 wherein R is , R1 is -C2H5, R2 is -CH2CH=CH2 and n is 1.
110. The method as set forth in Claim 90 wherein R is , R1 is n-C3H7, R2 is n-C3H7 and n is 2.
111. The method as set forth in Claim 90 wherein R is , R1 is -C2H5, R2 is and n is 1.
112. The method as set forth in Claim 90 wherein R is , R1 is -C2H5, R2 is -C2H5 and n is 1.
113. The method as set forth in Claim 90 wherein R is , R1 is -n-C4H9, R2 is -n-C4H9 and n is 1.
114. The method as set forth in Claim 90 wherein R is , R1 is -n-C4H9, R2 is -i-C4H9 and n is 1.
115. The method as set forth in Claim 90 wherein R is , R1 is -n-C4H9, R2 is -sec-C4H9 and n is 1.
116. The method as set forth in Claim 90 wherein R is , R1 is -i-C4H9, R2 is -sec-C4H9 and n is 1.
117. The method as set forth in Claim 90 wherein R is , R1 is -C2H5, R2 is -n-C4H9 and n is 2,
118. The method as set forth in Claim 90 wherein R is , R1 is -C2H5, R2 is -sec-C4H9 and n is 2.
119. The method as set forth in Claim 90 wherein R is ' R1 is -n-C4H9, R2 is -n-C4H9 and n is 2.
120. The method as set forth in Claim 90 wherein R is , R1 is -n-C4H9, R2 is -i-C4H9 and n is 2.
121. The method as set forth in Claim 90 wherein R is , Rl is -n-C4H9, R2 is -sec-C4H9 and D is 2.
122. The method as set forth in Claim 90wherein R is , Rl is -i-C4H9, R2 is -i-C4H9 and n is 2.
123- The method as set forth in Claim 90wherein R is , Rl is -i-C4H9, R2 is -sec-C4H9 and n is 2,
124. The method as set forth in Claim 90wherein R i , Rl is -C2H5, R2 is -n-C4H9 and n is 1.
125- The method as set forth in Claim 90wherein R is , Rl is -C2H5, R2 is -sec-C4H9 and n is 1.
126 . The method as set forth in Claim 90wherein R is , Rl is -C2H5, R2 is -t-C4H9 and n is 1.
127. The method as set forth in Claim 90 wherein R is , Rl is -n-C3H7, R2 is -i-C4H9 and n is 1.
128- The method as set forth in Claim90 wherein R is , Rl is -n-C3H7, R2 is -sec-C4H9 and n is 1.
129. The method as set forth in Claim90 wherein R is , Rl is -i-C3H7, R2 is -n-C4H9 and n is 1.
130, The method as set forth in Claim90 wherein R is , Rl is -i-C3H7, R2 is i C4H9 and n is
131. The method as set forth in Claim 90 wherein R is , Rl is -C2H5, R2 is -n-C4H9 and n is 1.
132. The method as set forth in Claim 90wherein R is , Rl is -C2H5, R2 is -i-C4Hg and n is 1.
133. The method as set forth in Claim 90wherein R is , Rl is -n-C4H9, R2 is -n-C4H9 and n is 1.
134 The method as set forth in Claim90 wherein R is , Rl is -C2H5, R2 is and n is 1.
135 . The method as set forth in Claim90 wherein R is , Rl is -C2H5, R2 is -i-C4H9 and n is 1.
136 , The method as set forth in Claim90 wherein R is , Rl is -n-C4H9, R2 is -n-C4H9 and n is 1.
137. The method as set forth in Claim 90wherein R is , R1 is -C2H5, R2 is and n is 1.
138 . The method as set forth in Claim 90wherein R is , Rl is -C2H5, R2 is -n-C4H9 and n is 1.
139 . The method as set forth in Claim 9owherein R is , Rl is -C2H5, R2 is -i-C4H9 and n is 1.
140. The method as set forth in Claim90 wherein R is , R1 is -n-C3H7, R2 is -n-C3H7 and n is 1.
141. The method as set forth in Claim 90 wherein R is , R1 is -n-C4H9, R2 is -n-C4H9 and n is 1.
142. The method as set forth in Claim 90 wherein R is , R1 is -C2H5, R2 is and n is 1.
143. The method as set forth in Claim 90 wherein R is , R1 is i-C3H7, R2 is -n-C4H9 and n is 2.
144. The method as set forth in Claim 90 wherein R is , R1 is -i-C3H7, R2 is -i-C3H7 and n is 2.
145 . The method as set forth in Claim 90 wherein R is , R1 is -CH3, R2 is -CH3 and n is 1.
146. The method as set forth in Claim 90 wherein R is , R1 is -C2H5, R2 is -n-C5H11 and n is 1.
147 . The method as set forth in Claim 90 wherein R is , R1 is C2H5, R2 is -sec-C5H11 and n is 1.
148 . The method as set forth in Claim 90 wherein R is , R1 is -C2H5, R2 is and n is 1.
149. The method as set forth in Claim 90 wherein R is , R1 is -n-C3H7, R2 is -n-C3H7 and n is 1.
150. The method as set forth in Claim 90wherein R is , Rl is -C2H5, R2 is -n-C4H9 and n is 1.
151. The method as set forth in Claim90 wherein R is , Rl is -C2H5, R2 is -sec-C4Hg and n is 1.
152. The method as set forth in Claim90 wherein R is , Rl is -CH3, R2 is -sec-C4Hg and n is 1.
153. The method as set forth in Claim 90wherein R is , Rl is -CH3, R2 is -sec-C5Hll and n is 1.
154. The method as set forth in Claim 90wherein R is , Rl is -CH3, R2 is -CH(cH3)-cH(cH3)2 and n is 1.
155. The method as set forth in Claim90 wherein R is , Rl is -C2H5, R2 is -i-C3H7 and n is 1.
156. The method as set forth in Claim 90wherein R is , Rl is -C2H5, R2 is -CH2-CH=CH2 and n is 1.
157. The method as set forth in Claim 90wherein R is , Rl is -C2H5, R2 is -CH(CH3)-CH(CH3)2 and n is 1.
158 . The method as set forth in Claim 90 wherein R is , R1 is -i-C3H7, R2 is -i-C3H7 and n is 1.
159 . The method as set forth in Claim 90 wherein R is , R1 is -i-C3H7, R2 is -n-C5H11 and n is 1.
160 . The method as set forth in Claim 90 wherein R is R1 is -i-C3H7, R2 is -sec-C5H11
161. The method as set forth in Claim 90 wherein R is , R1 is -i-C4H9, R2 is -i-C4H9 and n is 1.
162. The method as set forth in Claim 90 wherein R is , R1 is -C2H5, R2 is -CH2-CH=CH2 and n is 1.
163. The method as set forth in Claim 90 wherein R is , R1 is -C2H5, R2 is -i-C4H9 and n is 1.
164. The method as set forth in Claim 90 wherein R is , R1 is -i-C4H9, R2 is -i-C4H9 and n is 1.
165 . The method as set forth in claim 90 wherein R is , R1 is -CH3, R2 is -i-C3H7 and n is 1.
166. The method as set forth in Claim 90 wherein R is , R1 is -CH3, R2 is -n-C6H13 and n is 1.
167 . The method as set forth in Claim 90 wherein R is , R1 is -C2H5, R2 is -n-C3H7 and n is 1.
168. The method as set forth in Claim 90 wherein R is , R1 is -C2H5, R2 is -n-C6H13 and n is 1.
169. The method as set forth in Claim 90 wherein R is , R1 is -n-C3H7, R2 is -n-C5H11 and n is 1.
170 . The method as set forth in Claim 90 wherein R is R1 is -n-C3H7, R2 is -sec-C5H11 and n is 1.
171. The method as set forth in Claim 90 wherein R is , R1 is -n-C3H7, R2 is -CH(CH3)-CH(CH3)2 and n is 1.
172. The method as set forth in Claim 90 wherein R is , R1 is -CH3, R2 is and n is 1.
173. The method as set forth in Claim 90 wherein R is , R1 is -n-C3H7, R2 is -i-C3H7, and n is 1.
174 . The method as set forth in Claim 90 wherein R is , R1 is -CH3, R2 is and n is 1.
175 . The method as set forth in Claim 90 wherein R is , R1 is -C2H5, R2 is and n is 1.
176 . The method as set forth in Claim 90 wherein R is , Rl is -C2H5, R2 is , and n is 1.
177. The method as set forth in Claim 90 wherein R is , Rl is -n-C3H7, R2 is and n is 1.
178. The method as set forth in Claim 90 wherein R is Rl is -C2H5 R2 is and n is 1.
179 . A process for manufacturing a compound having the formula:
wherein n is 1 or 2; R is selected from the group consisting of halophenyl, phenalkyl, substituted phenalkyl wherein said substi-tuents are selected from halogen, alkyl and haloalkyl; Rl and R2 can be the same or different and can be selected from lower alkyl, cycloalkyl, alkenyl, alkynyl and benzyl, with the ,proviso that when R is benzyl Rl and R2 are not both sec C4Hg, comprising the steps of:
a) reacting an oxidizing agent with a thiocarbamate;
said thiocarbamate having the formula:
wherein said R, Rl and R2 have been previously defined; 40 b) said reaction being carried out at a temperature of between -25°C. and 65°C.;
c) said oxidizing agent being present in an amount of at least one molar equivalent.
wherein n is 1 or 2; R is selected from the group consisting of halophenyl, phenalkyl, substituted phenalkyl wherein said substi-tuents are selected from halogen, alkyl and haloalkyl; Rl and R2 can be the same or different and can be selected from lower alkyl, cycloalkyl, alkenyl, alkynyl and benzyl, with the ,proviso that when R is benzyl Rl and R2 are not both sec C4Hg, comprising the steps of:
a) reacting an oxidizing agent with a thiocarbamate;
said thiocarbamate having the formula:
wherein said R, Rl and R2 have been previously defined; 40 b) said reaction being carried out at a temperature of between -25°C. and 65°C.;
c) said oxidizing agent being present in an amount of at least one molar equivalent.
180. The process of claim 179 wherein said oxidizing agent is m-chloroperoxybenzoic acid.
181. Compounds of the class of carbamoyl sulphoxides having the general formula:
wherein R is selected from:
- halophenyl; and - benzyl which may be substituted in the phenyl group with alkyl containing 1 to 4 carbon atoms and halogen;
and wherein R1 and R2 can be the same or different and can be selected from:
- alkyl containing 1 to 4 carbon atoms; and - cycloalkyl containing 4 to 7 carbon atoms with the proviso that when R is benzyl R1 and R2 are not both sec C4H9.
wherein R is selected from:
- halophenyl; and - benzyl which may be substituted in the phenyl group with alkyl containing 1 to 4 carbon atoms and halogen;
and wherein R1 and R2 can be the same or different and can be selected from:
- alkyl containing 1 to 4 carbon atoms; and - cycloalkyl containing 4 to 7 carbon atoms with the proviso that when R is benzyl R1 and R2 are not both sec C4H9.
182. A process for manufacturing a compound having the general formula:
wherein R is selected from:
- halophenyl; and - benzyl which may be substituted in the phenyl group with alkyl containing 1 to 4 carbon atoms and halogen;
and wherein R1 and R2 can be the same or different and can be selected from:
- alkyl containing 1 to 4 carbon atoms; and -cycloalkyl containing 4 to 7 carbon atoms with the proviso that when R is benzyl R1 and R2 are not both sec C4H9, comprising the steps of:
(a) reacting an oxidizing agent selected from:
(i) peracetic acid; and (ii) m-chloroperoxybenzoic acid with a thiocarbamate, said thiocarbamate having the general formula:
wherein R, R1 and R2 have been previously defined;
(b) said reaction being carried out at a temperature between -25°C and 50°C; and (c) said oxidizing agent being present in an amount of one molar equivalent.
wherein R is selected from:
- halophenyl; and - benzyl which may be substituted in the phenyl group with alkyl containing 1 to 4 carbon atoms and halogen;
and wherein R1 and R2 can be the same or different and can be selected from:
- alkyl containing 1 to 4 carbon atoms; and -cycloalkyl containing 4 to 7 carbon atoms with the proviso that when R is benzyl R1 and R2 are not both sec C4H9, comprising the steps of:
(a) reacting an oxidizing agent selected from:
(i) peracetic acid; and (ii) m-chloroperoxybenzoic acid with a thiocarbamate, said thiocarbamate having the general formula:
wherein R, R1 and R2 have been previously defined;
(b) said reaction being carried out at a temperature between -25°C and 50°C; and (c) said oxidizing agent being present in an amount of one molar equivalent.
183. A method of controlling undesirable vegetation compris-ing applying to the locus where control is desired an effective amount of a compound represented by the general formula:
wherein R is selected from:
- halophenyl; and - benzyl which may be substituted in the phenyl group with alkyl containing 1 to 4 carbon atoms and halogen;
and wherein R1 and R2 can be the same or different and can be selected from:
- alkyl containing 1 to 4 carbon atoms; and - cycloalkyl containing 4 to 7 carbon atoms with the proviso that when R is benzyl R1 and R2 are both not sec-C4H9.
wherein R is selected from:
- halophenyl; and - benzyl which may be substituted in the phenyl group with alkyl containing 1 to 4 carbon atoms and halogen;
and wherein R1 and R2 can be the same or different and can be selected from:
- alkyl containing 1 to 4 carbon atoms; and - cycloalkyl containing 4 to 7 carbon atoms with the proviso that when R is benzyl R1 and R2 are both not sec-C4H9.
184. The method as set forth in claim 183 wherein R is , R1 is n-C3H7 and R2 is .
185. The method as set forth in claim 183 wherein R is , R1 is n-C3H7 and R2 is n-C3H7.
186. The method as set forth in claim 183 wherein R is , R1 is i-C4H9 and R2 is i-C4H9.
187. The method as set forth in claim 183 wherein R is , R1 is i-C3H7 and R2 is i-C3H7.
Applications Claiming Priority (12)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US28039272A | 1972-08-14 | 1972-08-14 | |
| US28039172A | 1972-08-14 | 1972-08-14 | |
| US28039372A | 1972-08-14 | 1972-08-14 | |
| US280,392 | 1972-08-14 | ||
| US280,393 | 1972-08-14 | ||
| US280,391 | 1972-08-14 | ||
| US37133273A | 1973-06-18 | 1973-06-18 | |
| US37133073A | 1973-06-18 | 1973-06-18 | |
| US371329A US3897492A (en) | 1972-08-14 | 1973-06-18 | Method of making carbamoyl sulfoxide derivatives |
| US371,329 | 1973-06-18 | ||
| US371,330 | 1982-04-23 | ||
| US371,332 | 1989-06-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1155135A true CA1155135A (en) | 1983-10-11 |
Family
ID=27559551
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000178727A Expired CA1155135A (en) | 1972-08-14 | 1973-08-14 | Herbicide compositions |
Country Status (10)
| Country | Link |
|---|---|
| AR (1) | AR206996A1 (en) |
| AU (1) | AU476219B2 (en) |
| CA (1) | CA1155135A (en) |
| CH (2) | CH581431A5 (en) |
| DE (1) | DE2340517A1 (en) |
| FR (1) | FR2196119B1 (en) |
| GB (1) | GB1385171A (en) |
| IL (1) | IL42975A (en) |
| IT (1) | IT990248B (en) |
| NL (1) | NL7311191A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FI844547L (en) * | 1983-12-05 | 1985-06-06 | Stauffer Chemical Co | HERBICIDBLANDNINGAR OCH FOERFARANDE FOER KONTROLL AV OGRAES. |
-
1973
- 1973-01-01 AR AR24956273A patent/AR206996A1/en active
- 1973-08-09 GB GB3779473A patent/GB1385171A/en not_active Expired
- 1973-08-10 DE DE19732340517 patent/DE2340517A1/en not_active Withdrawn
- 1973-08-14 CH CH1169973A patent/CH581431A5/xx not_active IP Right Cessation
- 1973-08-14 CH CH1021376A patent/CH602620A5/xx not_active IP Right Cessation
- 1973-08-14 CA CA000178727A patent/CA1155135A/en not_active Expired
- 1973-08-14 IT IT5201273A patent/IT990248B/en active
- 1973-08-14 AU AU59189/73A patent/AU476219B2/en not_active Expired
- 1973-08-14 FR FR7329767A patent/FR2196119B1/fr not_active Expired
- 1973-08-14 IL IL42975A patent/IL42975A/en unknown
- 1973-08-14 NL NL7311191A patent/NL7311191A/xx not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| AU476219B2 (en) | 1976-09-16 |
| FR2196119B1 (en) | 1977-02-25 |
| AR206996A1 (en) | 1976-09-09 |
| GB1385171A (en) | 1975-02-26 |
| DE2340517A1 (en) | 1974-02-28 |
| NL7311191A (en) | 1974-02-18 |
| CH602620A5 (en) | 1978-07-31 |
| FR2196119A1 (en) | 1974-03-15 |
| IL42975A (en) | 1976-11-30 |
| CH581431A5 (en) | 1976-11-15 |
| AU5918973A (en) | 1975-02-20 |
| IL42975A0 (en) | 1973-11-28 |
| IT990248B (en) | 1975-06-20 |
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| MKEX | Expiry |