CA1155125A - Herbicidal compositions - Google Patents
Herbicidal compositionsInfo
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- CA1155125A CA1155125A CA000178728A CA178728A CA1155125A CA 1155125 A CA1155125 A CA 1155125A CA 000178728 A CA000178728 A CA 000178728A CA 178728 A CA178728 A CA 178728A CA 1155125 A CA1155125 A CA 1155125A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
- C07D295/20—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carbonic acid, or sulfur or nitrogen analogues thereof
- C07D295/21—Radicals derived from sulfur analogues of carbonic acid
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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
1:~551ZS
Description of the Invention This invention is directed to a novel group of compounds which may be generally described as sulfoxide and sulfone deriva-tives of thiocarbamates which are highly active herbicides.
The compounds of the present invention are represented by the generic formula:
R-S(O)n-~-N
wherein n can be 1 or 2; R can be selected from the group consis-ting of lower alkyl, haloalkyl, alkoxyalkenyl and alkenyl; ~1 and R2 can be the same~or different and can be selected from the group consisting of lower alkyl, cycloalkyl having 3-8 carbon atoms, alkylcycloalkyl, alkenyl and alkynyl.
.
The above-noted compounds can be prepared by reacting an oxidizing agent such as peracetic acid or m-chloroperoxy-benzoic acid with a thiocarbamate compound corresponding to the following formula:
R-S-C-N
whe~ein R, Rl and R2 have been defined above. The reaction is carried out in the presence of an inert solvent such as chloro-form, methylene chloride, benzene, and toluene, and at a temperature of from about -25C. to about 60C. The amount of oxidizing agent used must be at least one molar equivalent to form the ~ - 2 -~5~5 sulfoxide derivative and at least two molar equivalents to form the sulfone derivatives. The reaction is completed when no oxidizing agent is left within the reaction mass.
The thiocarbamate compounds are known herbicides and their method of synthesis is known; see U.S. Patents 2,913,327,
Description of the Invention This invention is directed to a novel group of compounds which may be generally described as sulfoxide and sulfone deriva-tives of thiocarbamates which are highly active herbicides.
The compounds of the present invention are represented by the generic formula:
R-S(O)n-~-N
wherein n can be 1 or 2; R can be selected from the group consis-ting of lower alkyl, haloalkyl, alkoxyalkenyl and alkenyl; ~1 and R2 can be the same~or different and can be selected from the group consisting of lower alkyl, cycloalkyl having 3-8 carbon atoms, alkylcycloalkyl, alkenyl and alkynyl.
.
The above-noted compounds can be prepared by reacting an oxidizing agent such as peracetic acid or m-chloroperoxy-benzoic acid with a thiocarbamate compound corresponding to the following formula:
R-S-C-N
whe~ein R, Rl and R2 have been defined above. The reaction is carried out in the presence of an inert solvent such as chloro-form, methylene chloride, benzene, and toluene, and at a temperature of from about -25C. to about 60C. The amount of oxidizing agent used must be at least one molar equivalent to form the ~ - 2 -~5~5 sulfoxide derivative and at least two molar equivalents to form the sulfone derivatives. The reaction is completed when no oxidizing agent is left within the reaction mass.
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. How-ever, the use of these thiocarbàmates as reactive intermediates to form other compounds that have pesticidal activity is unexpected.
In order to illustrate the merits of the present inven-tion, the following examples are provided:
.xample 1 ~ R n-C3H7 C2~5-S-C N
n C3 7 A mixture was formed which contained 12.2 g. (0.06 mole) of m-chloroperoxybenzoic acid in 200 cc. of chloroform. This solution was then cooled in an ice bath to 3C. Then, 9.5 g.
(0.05 mole) of S-ethyl dipropylthiocarbamate was rapidly added and the temperature rose rapidly to 35C. and then decreased.
The flask containing the reaction mixture was placed under re-frigeration for about an hour wherein white solid crystals were observed. The solution was kept under refrigeration for 24 hours and then was filtered while in the cold condition. It was then washed with chloroform and then was dried. The co~bined filtrate was washed with 3 portions of 100 cc. of 5% sodium carbonate solution, 1 portion of 100 cc. of water, dried over magnesium sulfate and concentrated on a rotary evaporator under water pump vacuum, to yield 10.1 g. of product, n30 _ 1.4834.
In order to illustrate the merits of the present inven-tion, the following examples are provided:
.xample 1 ~ R n-C3H7 C2~5-S-C N
n C3 7 A mixture was formed which contained 12.2 g. (0.06 mole) of m-chloroperoxybenzoic acid in 200 cc. of chloroform. This solution was then cooled in an ice bath to 3C. Then, 9.5 g.
(0.05 mole) of S-ethyl dipropylthiocarbamate was rapidly added and the temperature rose rapidly to 35C. and then decreased.
The flask containing the reaction mixture was placed under re-frigeration for about an hour wherein white solid crystals were observed. The solution was kept under refrigeration for 24 hours and then was filtered while in the cold condition. It was then washed with chloroform and then was dried. The co~bined filtrate was washed with 3 portions of 100 cc. of 5% sodium carbonate solution, 1 portion of 100 cc. of water, dried over magnesium sulfate and concentrated on a rotary evaporator under water pump vacuum, to yield 10.1 g. of product, n30 _ 1.4834.
- 3 -l~SS~!l2S
Example 2 O O
C4E~g C H -S-C-N
2 5 11 \i-C4Hg A solution was formed containing 1~.2 g. of m-chloro-peroxybenzoic acid in 200 cc. of methylene chloride. There-after, 10.9 g. (0.05 mole) of S-ethyl diisobutylthiocarbamate was added rapidly when the temperature of the solution was 18C.
The soIution rose rapidly to a temperature of 30C., wherein the reaction mass was placed in an ice bath to reduce the tempera-ture. After a period of 3 hours the cold mixture was filtered and the cake was washed with 2 portions of 25 cc. of methylene chloride. The combined filtrate was washed with 4 portions of 100 cc. of 5% solution bf sodium carbonate, then 2 portions of 100 cc. of water, dried over magnesium sulfate and concentrated in a rotary evaporator under water pump vacuum to yield 11.0 g.
of product, nD ~ 1.4718.
Example 3 ¦1 ~1 ~C2EI5 C2H5-~ -C-N~3 ~, .
A solution was formed in a reaction vessel which con-tained 22.3 g. (0.11 mole) of m-chloroperoxybenzoic acid in 300 cc. of methylene chloride. `Then, 10.8 g. (0.05 mole) of S-ethyl cyclohexylethylthiocarbamate was added rapidly when the temperature was 35C. The temperature rose to 41C., wherein the temperature began to decrease and additional heat was applied to maintain the temperature of 41C. The cold mixture was filtered and the cake was washed with 2 portions of 25 cc. of methylene ~1~5~S
chloride. The com~ined filtr~te w~s washed with 4 por~ions of 100 cc. of 5/O sodlum carbonate solution and then 2 portions of 100 cc, o water, dried over magnesium sulfate and concentrated in a rotary evaporator, irst under water pump vacuum and finally under high vacuum to produce 11.9 g. of product, n30 _ 1.4911.
Example 4 C2H5-RS_~_N~ 2H5 Y~
A solution was formed containing 11.2 g. (0,055 mole) of m-chloroperoxybenzoic acid in 200 cc. of methylene chloride.
Then, 10,8 g. (0.05 mole) of S-ethyl cyclohexylethylthiocarbamate was added rapidly when the temperature was at -15,5C. The temper-ature was allowed to rise to -14.5C. and maintained for 2 hours.
Thereafter, the temperature was allowed to reach 19.5C. The mix-ture was filtered and the cake was washed with 2 portions of 25 cc.
methylene chloride and dried in the oven. The combined filtrate wàs washed with 4 portions of 100 cc. of 5% solution of sodium car~onate and 2 portions of 100 cc, of water, dried over m~gn~sium sulfate and concen~rated in a rotary evapora~or, first under water pump vacuum and finally under high vacuum to yield 10,4 g. of pro-duct, n30 _ 1 5120.
Example 5 ~ R ,Cl~2-cl~=cH2 C2H5 ~n-C3H7 A solution was formed containing 10.7 g. of m-chloro-peroxybenzoic acid in 200 cc. of methylene chloride, The solution 1~55~S
was then placed in a dry ice bath to maint~in a temper~ture of -16C. Thereafter, 9.4 g. (0.05 mole) of S-ethyl allylpropyl-thLocarbamate was added rapidly and the temperature rose to -14.5C.
The reaction was allowed to carry out for 2 hours. During the . reaction the te~perature was allowed to go to 15.5C. and there-after was taken back do~n to 1C. The mixture was filtered and .
the cake was washed with 2 portions of 25 cc. methylene chloride.
` The combined filtrate was washed with 4 portions of 100 cc. of 5~/
. solution of sodium carbonate and 2 portions of 100 cc. of water, ~10 dried over magnesium sulfate and concentrated in a rotary evapora-`~ tor, first under water pump vacuum and finally under high vacuum to yield 9.0 g. of product, n30 _ 1.5015.
ExamPle 6 ' O O
C2H5~ _N ~CH2 CH=CH2 -CH=CH2 ~ ~, A solution was fonmed containing 10.7 g. (0.525 mole) ; of m-chloroperoxybenzoic acid in 200 cc. of methylene chloride in 1~5 a reaction vessel. The solution was cooled to -16.5C., wherein . .
9.3 g. (0.05 mole) of S-ethyl diallylthiocarbamate was added rapidly. Then, the solution rose to -15C. The reaction was allowed to be carried out for 105 hours. At the end of this time ~` the reaction was allowed to reach 18.5C. The cold mixture was filtered and the cake washed with 2 portions of 25 cc. of methylene chloride. The combined filtrate was washed with 4 portions of lO0 cc. of 5% sodium carbonate solution and 2 portions of 100 cc.
of water, dried over magnesium sulfate and concentrated in a rota-~
evaporator to yield 8.8 g. of product, n30 _ 1.5144.
~55~5 Example 7 O O
CH(cH8)-c-cH
A solution was formed containing 200 cc. methylene chloride with 10.7 g. (0.0525 mole) of m-chloroperoxybenzoic acid dissolved therein. This solution was cooled to -15C., wherein 8.6 g. (0.05 mole) of S-ethyl methyl-~.methylpropargylthiocar-bamate was added rapidly. At the end of 2 hours the reactionwas removed from the ice bath and allowed to reach 21.5C., where-in the reaction was worked up in a similar manner as set forth in the previous example to yield 6.9 g. of product, nD - 1.5147.
Example 8 O O
ClCH2-CH2-CH2-S-C-N ~ 2 5 A solution was formed containing 200 cc. of methylene chloride and 11.6 g. of S-3-chloropropyldiethylthiocarbamate dis-solved therein. This solution was cooled to -17C. in dry ice bath, wherein 10.0 g. of m-chloroperoxybenzoic acid was added rapidly. After 2 hours the reaction was removed from the dry ice bath and allowed to reach 18.5C. wherein the reaction was worked-up in a similar manner as set forth in the p~evious example to yield 11.1 g. of product, nD - 1.5107.
Other compounds were prepared in an analogous manner starting with the appropriate starting materials as outlined above. 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.
~ - 7 -~1~5~5 TABLE I
Il R
Physic~l Const~nt Compound ~0 Number R Rl R2 - n~ or o r, 1 -C2H5 3 7 n-C3H7 1 1,4834 2 -C2H5 i~C4Hg i-C4H9 2 1 G 4718 3 2 S 3 7 n C3 7 2 1.4574
Example 2 O O
C4E~g C H -S-C-N
2 5 11 \i-C4Hg A solution was formed containing 1~.2 g. of m-chloro-peroxybenzoic acid in 200 cc. of methylene chloride. There-after, 10.9 g. (0.05 mole) of S-ethyl diisobutylthiocarbamate was added rapidly when the temperature of the solution was 18C.
The soIution rose rapidly to a temperature of 30C., wherein the reaction mass was placed in an ice bath to reduce the tempera-ture. After a period of 3 hours the cold mixture was filtered and the cake was washed with 2 portions of 25 cc. of methylene chloride. The combined filtrate was washed with 4 portions of 100 cc. of 5% solution bf sodium carbonate, then 2 portions of 100 cc. of water, dried over magnesium sulfate and concentrated in a rotary evaporator under water pump vacuum to yield 11.0 g.
of product, nD ~ 1.4718.
Example 3 ¦1 ~1 ~C2EI5 C2H5-~ -C-N~3 ~, .
A solution was formed in a reaction vessel which con-tained 22.3 g. (0.11 mole) of m-chloroperoxybenzoic acid in 300 cc. of methylene chloride. `Then, 10.8 g. (0.05 mole) of S-ethyl cyclohexylethylthiocarbamate was added rapidly when the temperature was 35C. The temperature rose to 41C., wherein the temperature began to decrease and additional heat was applied to maintain the temperature of 41C. The cold mixture was filtered and the cake was washed with 2 portions of 25 cc. of methylene ~1~5~S
chloride. The com~ined filtr~te w~s washed with 4 por~ions of 100 cc. of 5/O sodlum carbonate solution and then 2 portions of 100 cc, o water, dried over magnesium sulfate and concentrated in a rotary evaporator, irst under water pump vacuum and finally under high vacuum to produce 11.9 g. of product, n30 _ 1.4911.
Example 4 C2H5-RS_~_N~ 2H5 Y~
A solution was formed containing 11.2 g. (0,055 mole) of m-chloroperoxybenzoic acid in 200 cc. of methylene chloride.
Then, 10,8 g. (0.05 mole) of S-ethyl cyclohexylethylthiocarbamate was added rapidly when the temperature was at -15,5C. The temper-ature was allowed to rise to -14.5C. and maintained for 2 hours.
Thereafter, the temperature was allowed to reach 19.5C. The mix-ture was filtered and the cake was washed with 2 portions of 25 cc.
methylene chloride and dried in the oven. The combined filtrate wàs washed with 4 portions of 100 cc. of 5% solution of sodium car~onate and 2 portions of 100 cc, of water, dried over m~gn~sium sulfate and concen~rated in a rotary evapora~or, first under water pump vacuum and finally under high vacuum to yield 10,4 g. of pro-duct, n30 _ 1 5120.
Example 5 ~ R ,Cl~2-cl~=cH2 C2H5 ~n-C3H7 A solution was formed containing 10.7 g. of m-chloro-peroxybenzoic acid in 200 cc. of methylene chloride, The solution 1~55~S
was then placed in a dry ice bath to maint~in a temper~ture of -16C. Thereafter, 9.4 g. (0.05 mole) of S-ethyl allylpropyl-thLocarbamate was added rapidly and the temperature rose to -14.5C.
The reaction was allowed to carry out for 2 hours. During the . reaction the te~perature was allowed to go to 15.5C. and there-after was taken back do~n to 1C. The mixture was filtered and .
the cake was washed with 2 portions of 25 cc. methylene chloride.
` The combined filtrate was washed with 4 portions of 100 cc. of 5~/
. solution of sodium carbonate and 2 portions of 100 cc. of water, ~10 dried over magnesium sulfate and concentrated in a rotary evapora-`~ tor, first under water pump vacuum and finally under high vacuum to yield 9.0 g. of product, n30 _ 1.5015.
ExamPle 6 ' O O
C2H5~ _N ~CH2 CH=CH2 -CH=CH2 ~ ~, A solution was fonmed containing 10.7 g. (0.525 mole) ; of m-chloroperoxybenzoic acid in 200 cc. of methylene chloride in 1~5 a reaction vessel. The solution was cooled to -16.5C., wherein . .
9.3 g. (0.05 mole) of S-ethyl diallylthiocarbamate was added rapidly. Then, the solution rose to -15C. The reaction was allowed to be carried out for 105 hours. At the end of this time ~` the reaction was allowed to reach 18.5C. The cold mixture was filtered and the cake washed with 2 portions of 25 cc. of methylene chloride. The combined filtrate was washed with 4 portions of lO0 cc. of 5% sodium carbonate solution and 2 portions of 100 cc.
of water, dried over magnesium sulfate and concentrated in a rota-~
evaporator to yield 8.8 g. of product, n30 _ 1.5144.
~55~5 Example 7 O O
CH(cH8)-c-cH
A solution was formed containing 200 cc. methylene chloride with 10.7 g. (0.0525 mole) of m-chloroperoxybenzoic acid dissolved therein. This solution was cooled to -15C., wherein 8.6 g. (0.05 mole) of S-ethyl methyl-~.methylpropargylthiocar-bamate was added rapidly. At the end of 2 hours the reactionwas removed from the ice bath and allowed to reach 21.5C., where-in the reaction was worked up in a similar manner as set forth in the previous example to yield 6.9 g. of product, nD - 1.5147.
Example 8 O O
ClCH2-CH2-CH2-S-C-N ~ 2 5 A solution was formed containing 200 cc. of methylene chloride and 11.6 g. of S-3-chloropropyldiethylthiocarbamate dis-solved therein. This solution was cooled to -17C. in dry ice bath, wherein 10.0 g. of m-chloroperoxybenzoic acid was added rapidly. After 2 hours the reaction was removed from the dry ice bath and allowed to reach 18.5C. wherein the reaction was worked-up in a similar manner as set forth in the p~evious example to yield 11.1 g. of product, nD - 1.5107.
Other compounds were prepared in an analogous manner starting with the appropriate starting materials as outlined above. 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.
~ - 7 -~1~5~5 TABLE I
Il R
Physic~l Const~nt Compound ~0 Number R Rl R2 - n~ or o r, 1 -C2H5 3 7 n-C3H7 1 1,4834 2 -C2H5 i~C4Hg i-C4H9 2 1 G 4718 3 2 S 3 7 n C3 7 2 1.4574
4 C2H5 i-C4Hg i-C4H9 1 1.4834 r.-C3H7 4 4 -C2H5 1 1.4847 6 n C3H7 n C4H9 -C2H5 2 1.4657 7 -C2H5 - ~ -C2H5 2 1.4911 8 C2H5 ~ -C2H5 1 1.5122 9 n-C3H7 n-C31~7 n 3 7 1 1.4842 n C31~7 n C3~7 n C3H7 2 1.4652 11 -C2H5CH2 CH CH2 -CH2-CH2-CH3 1 1.5015 12 n C3 7 -C2H5 -C2H5 1 1.4888 13 n~C3H7 -C2H5 _ ~ 1 1.5099 14 -C2H5-CH2-CH=CH2 -C~2-CH=CH2 1 1.51L4 -C2H5 -CH3 -cH(cH3)-c-~ 1 1.5147 TA13l,~ I (Cont.) Physical Constant Compound Number R Rl R2 n n30 or C
16 -CH2-CH=CH2 -CH2-c~=cH2 -CH2-CH=CH2 2yello~ oil 17 n-C3H6-Cl -C2H5 -C2H5 11.5107 l& n-C3~16~Cl 3 7 n~C3H7 11.5032 19 -cH=cHo-c2Hs n~C3H7 n C3H7 11.5082 n-C3H6-Cl -CH3 - ~ l82-90C.
21 n C3 6 Cl -C2H5 -C~H5 11.5107 22 n C3 6 Cl -n-C3H7 -n-C3H7 11.5032 23 3 6 l -C2H5 -n-C4H9 11.5019 24 3 6 -i-C3H7 -i-C3H7 11.5065 n C3H6 Cl -n-C4Hg -n-C4H9 11.4986 26 C3 6 Cl -i-C4Hg -i-C4H9 11.4977 27 n C3H6 Cl C2H5 ~ 11.5250 28 -n-C4H6 -C~3 -CH2 ~ 11,5088 29 -i-C4Hg -CH3 -CH2 ~ 168.5-74,0C.
-sec-C4Hg -CH3 -CH2 ~ 11,5122 115S~L~5 TA~L!~' I (collt-.~
Physical Const~nt Compound 30 Number R Rl R2 n nD or C, 31 -n-C3H6-Cl -CH3 -CH2 ~ ' 1 1.5272 32 -CH2-CIICl C~2Cl C~13 -CH2 ~ 1 Pasty solid 33 -CH(CH2C1)2 -CH3 -CH2 ~ 1 1.5346 34 -n-C3H7 -i-C3H7 -i-C3H7 1 1.4901 -C2H5 -n-C4Hg -n-C4Hg 1 1,4861 36 -n-C4Hg -i-C3H7 -i-C3H7 1 1.4821 37 -C2H5 -n-C3H7 -i-C4H9 1 1.4839 38 -i-C3H7 -n-C3H7 -i-C4H9 1 1.4840 39 -C2H5 -C2H5 -i-C4H9 1 1,4829 -n-C3H7 -i-C4Hg - C 2H5 1 1.4791 41 -C2H5 -i-C4Hg -i-C3H7 1 1.4801 42 -n-C3H7 -i-C3H7 n C4H9 1 1.4828 43 -CH3 C2H5 -CH2 ~ 1 1.5130 44 -i-C3H7 -C2H5 -CH2- ~ 1 1.5052 -n-C4~9 -C2H5 -CH2 ~ 1 1.5040 ` 1155~12S
TA13LE l ~ont. 2 Physic?.l Conc;t ~.n~
Comp~und ~-Number R Rl R2 n nD or C.
46 -i-C4Hg -C2~5 -CH2 ~ 1 1.5049 47 -n-C3H6-Cl -C2H5 -CH2 ~ 1 1,5168 48 -CH2-CHCl-CH2Cl -C2H5 -CU2 ~ 1 1.5288 49 -i-C3H7 -n-C3H7 -CH2 ~ 1 1.5053 -n-C4Hg -n-C3H7 -CH ~ 1 1. 50G9 51 -L-C4Hg -n-C3H7 -CH2 ~ 1 1.5035 52 -sec-C4H9 -n-C3H7 -CH2 ~ 1 1.5042 53 -n-C3H6-Cln C3H7 -CH ~ 1 1.5142 54 -CH2-CHCl-CH2Cl -n-C3H7 -CH2- ~ 1 1.52jS
-n-C3H7 -C2H5 -CH2 ~ 1 1.5068
16 -CH2-CH=CH2 -CH2-c~=cH2 -CH2-CH=CH2 2yello~ oil 17 n-C3H6-Cl -C2H5 -C2H5 11.5107 l& n-C3~16~Cl 3 7 n~C3H7 11.5032 19 -cH=cHo-c2Hs n~C3H7 n C3H7 11.5082 n-C3H6-Cl -CH3 - ~ l82-90C.
21 n C3 6 Cl -C2H5 -C~H5 11.5107 22 n C3 6 Cl -n-C3H7 -n-C3H7 11.5032 23 3 6 l -C2H5 -n-C4H9 11.5019 24 3 6 -i-C3H7 -i-C3H7 11.5065 n C3H6 Cl -n-C4Hg -n-C4H9 11.4986 26 C3 6 Cl -i-C4Hg -i-C4H9 11.4977 27 n C3H6 Cl C2H5 ~ 11.5250 28 -n-C4H6 -C~3 -CH2 ~ 11,5088 29 -i-C4Hg -CH3 -CH2 ~ 168.5-74,0C.
-sec-C4Hg -CH3 -CH2 ~ 11,5122 115S~L~5 TA~L!~' I (collt-.~
Physical Const~nt Compound 30 Number R Rl R2 n nD or C, 31 -n-C3H6-Cl -CH3 -CH2 ~ ' 1 1.5272 32 -CH2-CIICl C~2Cl C~13 -CH2 ~ 1 Pasty solid 33 -CH(CH2C1)2 -CH3 -CH2 ~ 1 1.5346 34 -n-C3H7 -i-C3H7 -i-C3H7 1 1.4901 -C2H5 -n-C4Hg -n-C4Hg 1 1,4861 36 -n-C4Hg -i-C3H7 -i-C3H7 1 1.4821 37 -C2H5 -n-C3H7 -i-C4H9 1 1.4839 38 -i-C3H7 -n-C3H7 -i-C4H9 1 1.4840 39 -C2H5 -C2H5 -i-C4H9 1 1,4829 -n-C3H7 -i-C4Hg - C 2H5 1 1.4791 41 -C2H5 -i-C4Hg -i-C3H7 1 1.4801 42 -n-C3H7 -i-C3H7 n C4H9 1 1.4828 43 -CH3 C2H5 -CH2 ~ 1 1.5130 44 -i-C3H7 -C2H5 -CH2- ~ 1 1.5052 -n-C4~9 -C2H5 -CH2 ~ 1 1.5040 ` 1155~12S
TA13LE l ~ont. 2 Physic?.l Conc;t ~.n~
Comp~und ~-Number R Rl R2 n nD or C.
46 -i-C4Hg -C2~5 -CH2 ~ 1 1.5049 47 -n-C3H6-Cl -C2H5 -CH2 ~ 1 1,5168 48 -CH2-CHCl-CH2Cl -C2H5 -CU2 ~ 1 1.5288 49 -i-C3H7 -n-C3H7 -CH2 ~ 1 1.5053 -n-C4Hg -n-C3H7 -CH ~ 1 1. 50G9 51 -L-C4Hg -n-C3H7 -CH2 ~ 1 1.5035 52 -sec-C4H9 -n-C3H7 -CH2 ~ 1 1.5042 53 -n-C3H6-Cln C3H7 -CH ~ 1 1.5142 54 -CH2-CHCl-CH2Cl -n-C3H7 -CH2- ~ 1 1.52jS
-n-C3H7 -C2H5 -CH2 ~ 1 1.5068
5~
Herbicidal Screening Tests ~ s previously mentioned, the novel compounds herein described are phytotoxic compounds which are useful and valuable in controlling various plant species. Compounds of this inven-tion are tested as herhicides in the following manner.
Pre-emergence Herbicides Screening Test Using an analytical balance, 20 mg. of the compound to be 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 dis-solve 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 ano~her solvent is used to make the volume up to 3 ml. The 3 ml. of solution is sprayed uniformly on the soil contained in a small styrofoam flat one day after planting weed seeds in the flat of soi~ No. 152 DeVilbiss atomizer is used to apply the~spray using compressed air at a pressure of 5 lb./sq. inch. 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 planted 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 (Digitaria sanguinalis~, yell~7foxtail (Setaria qlauca), watergrass (Fchinochloa crus~alli), red oat ~155~Z5 (Avena sativa), redroot pigweed (~aranthus retroflexus), Indian mustard (Brassica 2~ncea) and curly dock (Rumex crispus). Ample 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 per cent control with 0% representing no injury and 100%
representing complete kill.
Post-emergence Herbicide Screening Test;
Seeds of six plant species, including hairy crabgrass, watergrass, red oat, mustard, curly dock and Pinto bean (Phaseolus vulgaris) are planted in the styrofoam flats as described above for pre-emergence screening. The flats are placed in the greenhouse at 70-85~. and watered daily with a sprinkler.
About lO 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,20R and then adding 5 ml. water. The solution is sprayed on the foliage using a No. 152 DeVilbiss atomizer at an air pressure of 5 lb./sq. inch. 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.
~ - 13 -~l ~5~S
The res~lts of thcse tests are st-o~m in Table II.
TABLE I I
~n_ HERBICIDAL ACTIVITY - SCREENING RESULTS
Per Cent Control-~ at 8 lb . /A
Compound Number Pre-emergence Post-emer~ence 99.7 63
Herbicidal Screening Tests ~ s previously mentioned, the novel compounds herein described are phytotoxic compounds which are useful and valuable in controlling various plant species. Compounds of this inven-tion are tested as herhicides in the following manner.
Pre-emergence Herbicides Screening Test Using an analytical balance, 20 mg. of the compound to be 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 dis-solve 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 ano~her solvent is used to make the volume up to 3 ml. The 3 ml. of solution is sprayed uniformly on the soil contained in a small styrofoam flat one day after planting weed seeds in the flat of soi~ No. 152 DeVilbiss atomizer is used to apply the~spray using compressed air at a pressure of 5 lb./sq. inch. 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 planted 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 (Digitaria sanguinalis~, yell~7foxtail (Setaria qlauca), watergrass (Fchinochloa crus~alli), red oat ~155~Z5 (Avena sativa), redroot pigweed (~aranthus retroflexus), Indian mustard (Brassica 2~ncea) and curly dock (Rumex crispus). Ample 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 per cent control with 0% representing no injury and 100%
representing complete kill.
Post-emergence Herbicide Screening Test;
Seeds of six plant species, including hairy crabgrass, watergrass, red oat, mustard, curly dock and Pinto bean (Phaseolus vulgaris) are planted in the styrofoam flats as described above for pre-emergence screening. The flats are placed in the greenhouse at 70-85~. and watered daily with a sprinkler.
About lO 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,20R and then adding 5 ml. water. The solution is sprayed on the foliage using a No. 152 DeVilbiss atomizer at an air pressure of 5 lb./sq. inch. 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.
~ - 13 -~l ~5~S
The res~lts of thcse tests are st-o~m in Table II.
TABLE I I
~n_ HERBICIDAL ACTIVITY - SCREENING RESULTS
Per Cent Control-~ at 8 lb . /A
Compound Number Pre-emergence Post-emer~ence 99.7 63
6 0 43
7 o 30
8 95 50
9 98 47 o 49 1 99.9 78 12 9~-7 13 loo 85 67 67`
22 go 84 ~ 5 T~r,T,], II ~Con t ~ ) Compound _I'er. CCTlt Con~rol* at 8 lb./A
Number Pre-e_n_r~ence Po~s~-emerp~cnce ~ .. . _ gg 28 . 95 77 * Average for sevcn plant species in the pre-emergence test ~nd for si~ plant species in the post-emergence test.
~5~5 TAnl,T' II (Cont.) Per C~nt Control ~t 20 ]b/Q
Compound ~ . _ _ .
~umber Pre-emer~,ence Post-emer~ence 7 0 __ 3 ~~
Average for seven plant species in the pre-emergence test and for six plant species in the post-emergence 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 powder, powders, granular or any other convenient form, and applied to the soil to control the undesired vegetation.
The terms lower alkyl, alkenyl and alkynyl are meant to include those compounds having straight or branched chain con-figurations having from 1 to 6 carbon atoms, inclusive.
22 go 84 ~ 5 T~r,T,], II ~Con t ~ ) Compound _I'er. CCTlt Con~rol* at 8 lb./A
Number Pre-e_n_r~ence Po~s~-emerp~cnce ~ .. . _ gg 28 . 95 77 * Average for sevcn plant species in the pre-emergence test ~nd for si~ plant species in the post-emergence test.
~5~5 TAnl,T' II (Cont.) Per C~nt Control ~t 20 ]b/Q
Compound ~ . _ _ .
~umber Pre-emer~,ence Post-emer~ence 7 0 __ 3 ~~
Average for seven plant species in the pre-emergence test and for six plant species in the post-emergence 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 powder, powders, granular or any other convenient form, and applied to the soil to control the undesired vegetation.
The terms lower alkyl, alkenyl and alkynyl are meant to include those compounds having straight or branched chain con-figurations having from 1 to 6 carbon atoms, inclusive.
Claims (127)
1. A compound represented by the following generic formula:
wherein n is 1 or 2; R is selected from the group consisting of lower alkyl, haloalkyl, alkoxyalkenyl and alkenyl; R1 and R2 can be the same or different and can be selected from the group con-sisting of lower alkyl, cycloalkyl, alkylcycloalkyl, alkenyl and alkynyl.
wherein n is 1 or 2; R is selected from the group consisting of lower alkyl, haloalkyl, alkoxyalkenyl and alkenyl; R1 and R2 can be the same or different and can be selected from the group con-sisting of lower alkyl, cycloalkyl, alkylcycloalkyl, alkenyl and alkynyl.
2. The compound as set forth in Claim 1 wherein R is -C2H5, R1 is n-C3H7, R2 is n-C3H7 and n is 1.
3. The compound as set forth in Claim 1 wherein R is -C2H5, R1 is i-C4H9, R2 is i-C4H9 and n is 2.
4. The compound as set forth in Claim 1 wherein R is -C2H5, R1 is n-C3H7, R2 is n-C3H7 and n is 2.
5. The compound as set forth in Claim 1 wherein R is -C2H5, R1 is i-C4H9, R2 is i-C4H9 and n is 1.
6. The compound as set forth in Claim 1 wherein R is n-C3H7, R1 is n-C4H9, R2 is -C2H5 and n is 1.
7. The compound as set forth in Claim 1 wherein R is n-C3H7, R1 is n-C4H9, R2 is -C2H5 and n is 2.
8. The compound as set forth in Claim 1 wherein R is -C2H5, R1 is , R2 is -C2H5 and n is 2.
9. The compound as set forth in Claim 1 wherein R is -C2H5, R1 is , R2 is -C2H5 and n is 1.
10. The compound as set forth in Claim 1 wherein R is n-C3H7, R1 is n-C3H7, R2 is n-C3H7 and n is 1.
11. The compound as set forth in Claim 1 wherein R is n-C3H7, R1 is n-C3H7, R2 is n-C3H7 and n is 2.
12. The compound as set forth in Claim 1 wherein R is -C2H5, R1 is -CH2-CH=CH2, R2 is -CH2-CH2-CH3 and n is 1.
13. The compound as set forth in Claim 1 wherein R is n-C3H7, R1 is -C2H5, R2 is -C2H5 and n is 1.
14. The compound as set forth in Claim 1 wherein R is n-C3H7, R1 is -C2H5, R2 is and n is 1.
15. The compound as set forth in Claim 1 wherein R is -C2H5, R1 is -CH2-CH=CH2, R2 is -CH2-CH=CH2 and n is 1.
16. The compound as set forth in Claim 1 wherein R is -C2H5, R1 is -CH3, R2 is -CH(CH3)-C=CH and n is 1.
17. The compound as set forth in Claim 1 wherein R is -CH2-CH=CH2, R1 is -CH2-CH=CH2, R2 is -CH2-CH=CH2 and n is 2.
18. The compound as set forth in Claim 1 wherein R is n-C3H6-C1, R1 is -C2H5, R2 is -C2H5 and n is 1.
19. The compound as set forth in Claim 1 wherein R is n-C3H6-C1, R1 is n-C3H7, R2 is n-C3H7 and n is 1.
20. The compound as set forth in Claim 1 wherein R is -CH=CHO-C2H5, R1 is n-C3H7, R2 is n-C3H7 and n is 1.
21. The compound as set forth in Claim 1 wherein R is n-C3H6-C1, R1 is -CH3, R2 is and n is 1.
22. The compound as set forth in Claim 1 wherein R is -n-C3H6-C1, R1 is -C2H5, R2 is C2H5 and n is 1.
23. The compound as set forth in Claim 1 wherein R is -n-C3H6-C1, R1 is -n-C3H7, R2 is -n-C3H7 and n is 1.
24. The compound as set forth in Claim 1 wherein R is -n-C3H6-C1, R1 is -C2H5, R2 is -n-C4H9 and n is 1.
25. The compound as set forth in Claim 1 wherein R is -n-C3H6-C1, R1 is -i-C3H7, R2 is -i-C3H7 and n is 1.
26. The compound as set forth in Claim 1 wherein R is -n-C3H6-C1, R1 is -n-C4H9, R2 is -n-C4H9 and n is 1.
27. The compound as set forth in Claim 1 wherein R is -n-C3H6-C1, R1 is -i-C4H9, R2 is -i-C4H9 and n is 1.
28. The compound as set forth in Claim 1 wherein R is -n-C3H6-C1, R1 is -C2H5, R2 is and n is 1.
29. The compound as set forth in Claim 1 wherein R is -n-C4H6. R1 is -CH3, R2 is -CH2 and n is 1.
30. The compound as set forth in Claim 1 wherein R is -i-C4H9, R1 is -CH3, R2 is and n is 1.
31. The compound as set forth in Claim 1 wherein R is -sec-C4H9, R1 is -CH3, R2 is and n is 1.
32. The compound as set forth in Claim 1 wherein R is -n-C3H6-C1, R1 is -CH3, R2 is and n is 1.
33. The compound as set forth in Claim 1 wherein R is -CH2-CHC1-CH2C1, R1 is -CH3, R2 is and n is 1.
34. The compound as set forth in Claim 1 wherein R is -CH(CH2C1)2, R1 is -CH3, R2 is and n is 1.
35. The compound as set forth in Claim 1 wherein R is -n-C3H7, R1 is -i-C3H7, R2 is -i-C3H7 and n is 1.
36. The compound as set forth in Claim 1 wherein R is -C2H5, R1 is -n-C4H9, R2 is -n-C4H9 and n is 1.
37. The compound as set forth in Claim 1 wherein R is -n-C4H9, R1 is -i-C3H7, R2 is -i-C3H7 and n is 1.
38. The compound as set forth in Claim 1 wherein R is -C2H5, R1 is -n-C3H7, R2 is -i-C4H9 and n is 1.
39. The compound as set forth in Claim 1 wherein R is -i-C3H7, R1 is -n-C3H7, R2 is -i-C4H9 and n is 1.
40. The compound as set forth in Claim 1 wherein R is -C2H5, R1 is -C2H5, R2 is -i-C4H9 and n is 1.
41. The compound as set forth in Claim 1 wherein R is -n-C3H7, R1 is -i-C4H9, R2 is -C2H5 and n is 1.
42. The compound as set forth in Claim 1 wherein R is -C2H5, R1 is -i-C4H9, R2 is -i-C3H7 and n is 1.
43. The compound as set forth in Claim 1 wherein R is -n-C3H7, R1 is -i-C3H7, R2 is -n-C4H9 and n is 1.
44. The compound as set forth in Claim 1 wherein R is -CH3, R1 is -C2H5, R2 is and n is 1.
45. The compound as set forth in Claim 1 wherein R is -i-C3H7, R1 is -C2H5, R2 is and n is 1.
46. The compound as set forth in Claim 1 wherein R is -n-C4H9, R1 is -C2N5, R2 is and n is 1.
47. The compound as set forth in Claim 1 wherein R is -i-C4H9, R1 is -C2H5, R2 is and n is 1.
48. The compound as set forth in Claim 1 wherein R is -n-C3H6-C1, R1 is -C2H5, R2 is and n is 1.
49. The compound as set forth in Claim 1 wherein R is -CH2-CHC1-CH2C1, R1 is -C2H5, R2 is and n is 1.
50. The compound as set forth in Claim 1 wherein R is -i-C3H7, R1 is -n-C3H7, R2 is and n is 1.
51. The compound as set forth in Claim 1 wherein R is -n-C4H9, R1 is -n-C3H7, R2 is and n is 1.
52. The compound as set forth in Claim 1 wherein R is .
-i-C4H9, R1 is -n-C3H7, R2 is and n is 1.
-i-C4H9, R1 is -n-C3H7, R2 is and n is 1.
53. The compound as set forth in Claim 1 wherein R is -sec-C4H9, R1 is -n-C3H7, R2 is and n is 1.
54. The compound as set forth in Claim 1 wherein R is -n-C3H6-C1, R1 is -n-C3H7, R2 is and n is 1.
55. The compound as set forth in Claim 1 wherein R is -CH2-CHC1-CH2C1, R1 is -n-C3H7, R2 is and n is 1.
56. The compound as set forth in Claim 1 wherein R is -n-C3H7, R1 is -C2H5, R2 is and n is 1.
57. 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 lower alkyl, haloalkyl, alkoxyalkenyl and alkenyl; R1 and R2 can be the same or different and can be selected from the group con-sisting of lower alkyl, cycloalkyl, alkylcycloalkyl, alkenyl and alkynyl.
.
wherein n is 1 or 2; R is selected from the group consisting of lower alkyl, haloalkyl, alkoxyalkenyl and alkenyl; R1 and R2 can be the same or different and can be selected from the group con-sisting of lower alkyl, cycloalkyl, alkylcycloalkyl, alkenyl and alkynyl.
58. The method as set forth in Claim 57 wherein R is -C2H5, R1 is n-C3H7, R2 is n-C3H7 and n is 1.
59. The method as set forth in Claim 57 wherein R is -C2H5, R1 is i-C4H9, R2 is i-C4H9 and n is 2.
60. The method as set forth in Claim 57 wherein R is -C2H5, R1 is n-C3H7, R2 is n-C3H7 and n is 2.
61. The method as set forth in Claim 57 wherein R is -C2H5, R1 is i-C4H9, R2 is i-C4H9 and n is 1.
62. The method as set forth in Claim 57 wherein R is n-C3H7, R1 is n-C4H9, R2 is -C2H5 and n is 1.
63. The method as set forth in Claim 57 wherein R is n-C3H7, R1 is n-C4H9, R2 is -C2H5 and n is 2.
64. The method as set forth in Claim 57 wherein R is -C2H5, Rl is , R2 is -C2H5 and n is 2.
65. The method as set forth in Claim 57 wherein R is -C2H5, R1 is , R2 is -C2H5 and n is 1.
66. The method as set forth in Claim 57 wherein R is n-C3H7, R1 is n-C3H7, R2,is n-C3H7 and n is 1.
67. The method as set forth in Claim 57 wherein R is n-C3H7, R1 is n-C3H7, R2 is n-C3H7 and n is 2.
68. The method as set forth in Claim 57 wherein R is -C2H5, R1 is -CH2-CH-CH2, R2 is -CH2-CH2-CH3 and n is 1.
69. The method as set forth in Claim 57 wherein R is n-C3H7, R1 is -C2H5, R2 is -C2H5 and n is 1.
70. The method as set forth in Claim 57 wherein R is n-C3H7, R1 is -C2H5, R2 is and n is 1.
71. The method as set forth in Claim 57 wherein R is -C2H5, R1 is -CH2-CH-CH2, R2 is -CH2-CH-CH2 and n is 1.
72. The method as set forth in Claim 57 wherein R is -C2H5, R1 is -CH3, R2 is -CH(CH3)-C?CH and n is 1.
73. The method as set forth in Claim 57 wherein R is -CH2-CH=CH2, R1 is -CH2-CH=CH2, R2 is -CH2-CH=CH2 and n is 2.
74. The method as set forth in Claim 57 wherein R is n-C3H6, R1 is -C2H5, R2 is -C2H5 and n is 1.
75. The method as set forth in Claim 57 wherein R is n-C3H6, R1 is n-C3H7, R2 is n-C3H7 and n is 1.
76. The method as set forth in Claim 57 wherein R is -CH=CHO-C2H5, R1 is n-C3H7, R2 is n-C3H7 and n is 1.
77. The method as set forth in Claim 57 wherein R is n-C3H6-C1, R1 is -CH3, R2 is and n is 1.
78. The method as set forth in Claim 57 wherein R is -n-C3H6-C1, R1 is -C2H5, R2 is C2H5 and n is 1.
79. The method as set forth in Claim 57 wherein R is -n-C3H6-C1, R1 is -n-C3H7, R2 is -n-C3H7 and n is 1.
80. The method as set forth in Claim 57 wherein R is -n-C3H6-C1, R1 is -C2H5, R2 is -n-C4H9 and n is 1.
81. The method as set forth in Claim 57 wherein R is -n-C3H6-C1, R1 is -i-C3H7, R2 is -i-C3H7 and n is 1.
82. The method as set forth in Claim 57 wherein R is -n-C3H6-C1, R1 is -n-C4H9, R2 is -n-C4H9 and n is 1.
83. The method as set forth in Claim 57 wherein R is -n-C3H6-C1, R1 is -i-C4H9, R2 is -i-C4H9 and n is 1.
84. The method as set forth in Claim 57 wherein R is -n-C3H6-C1, R1 is -C2H5, R2 is and n is 1.
85. The method as set forth in Claim 57 wherein R is -n-C4H6, R1 is -CH3, R2 is and n is 1.
86. The method as set forth in Claim 57 wherein R is -i-C4H9, R1 is -CH3, R2 is and n is 1.
87. The method as set forth in Claim 57 wherein R is -sec-C4H9, R1 is -CH3, R2 is and n is 1.
88. The method as set forth in Claim 57 wherein R is -n-C3H6-C1, R1 is -CH3, R2 is and n is 1.
89. The method as set forth in Claim 57 wherein R is -CH2-CHC1-CH2C1, R1 is -CH3, R2 is and n is 1.
90. The method as set forth in Claim 57 wherein R is -CH(CH2C1)2, R1 is -CH3, R2 is and n is 1.
91. The method as set forth in Claim 57 wherein R is -n-C3H7, R1 is -i-C3H7, R2 is -i-C3H7 and n is 1.
92. The method as set forth in Claim 57 wherein R is -C2H5, R1 is -n-C4H9, R2 is -n-C4H9 and n is 1.
93. The method as set forth in Claim 57 wherein R is -n-C4H9, R1 is -i-C3H7, R2 is -i-C3H7 and n is 1.
94. The method as set forth in Claim 57 wherein R is -C2H5, R1 is -n-C3H7, R2 is -i-C4H9 and n is 1.
95. The method as set forth in Claim 57 wherein R is -i-C3H7, R1 is -n-C3H7, R2 is -i-C4H9 and n is 1.
96. The method as set forth in Claim 57 wherein R is -C2H5, R1 is -C2H5, R2 is -i-C4H9 and n is 1.
97. The method as set forth in Claim 57 wherein R is -n-C3H7, R1 is -i-C4H9. R2 is -C2H5 and n is 1.
98. The method as set forth in Claim 57 wherein R is -C2H5, R1 is -i-C4H9, R2 is -i-C3H7 and n is 1.
99. The method as set forth in Claim 57 wherein R is -n-C3H7, R1 is -i-C3H7, R2 is -n-C4H9 and n is 1.
100. The method as set forth in Claim 57 wherein R is -CH3, R1 is -C2H5, R2 is and n is 1.
101. The method as set forth in Claim 57 wherein R is -i-C3H7, R1 is -C2H5, R2 is and n is 1.
102. The method as set forth in Claim 57 wherein R is -n-C4H9, R1 is -C2H5, R2 is and n is 1.
103. The method as set forth in Claim 57 wherein R is -i-C4H9, R1 is -C2H5, R2 is and n is 1.
104. The method as set forth in Claim 57 wherein R is -n-C3H6-C1, R1 is -C2H5, R2 is and n is 1.
105. The method as set forth in Claim 57 wherein R is -CH2-CHC1-CH2C1, R1 is -C2H5, R2 is and n is 1.
106. The method as set forth in Claim 57 wherein R is -i-C3H7, R1 is -n-C3H7, R2 is and n is 1.
107. The method as set forth in Claim 57 wherein R is -n-C4H9, R1 is -n-C3H7, R2 is and n is 1.
108 . The method as set forth in Claim 57 wherein R is -i-C4H9, R1 is -n-C3H7, R2 is and n is 1.
109. The method as set forth in Claim 57 wherein R is -sec-C4H9, R1 is -n-C3H7, R2 is and n is 1.
110. The method as set forth in Claim 57 wherein R is -n-C3H6-C1, R1 is -n-C3H7, R2 is and n is 1.
111. The method as set forth in Claim 57 wherein R is -CH2-CHC1-CH2C1, R1 is -n-C3H7, R2 is and n is 1.
112. The method as set forth in Claim 57 wherein R is -n-C3H7, R1 is -C2H5, R2 is and n is 1.
113. A process for manufacturing pesticidal active com-pounds corresponding to the following formula:
wherein n is 1 or 2; R is selected from the group consisting of lower alkyl, haloalkyl, alkoxyalkenyl and alkenyl; R1 and R2 can be the same or different and can be selected from the group con-sisting of lower alkyl, cycloalkyl, alkylcycloalkyl, alkenyl and alkynyl; comprising the steps of:
a. combining an oxidizing agent and a thio-carbamate compound in a solvent system; said thio-carbamate having the following formula:
wherein R, R1 and R2 have been defined above;
b. maintaining the temperature between -15°C.
and 60°C.;
c. said oxidizing agent being present in an amount of at least one stoichiometric equiva-lent and not more than two stoichiometric equivalents.
wherein n is 1 or 2; R is selected from the group consisting of lower alkyl, haloalkyl, alkoxyalkenyl and alkenyl; R1 and R2 can be the same or different and can be selected from the group con-sisting of lower alkyl, cycloalkyl, alkylcycloalkyl, alkenyl and alkynyl; comprising the steps of:
a. combining an oxidizing agent and a thio-carbamate compound in a solvent system; said thio-carbamate having the following formula:
wherein R, R1 and R2 have been defined above;
b. maintaining the temperature between -15°C.
and 60°C.;
c. said oxidizing agent being present in an amount of at least one stoichiometric equiva-lent and not more than two stoichiometric equivalents.
114. The process as set forth in Claim 113 wherein said oxidizing agent is selected from peracetic acid and m-chloro-peroxybenzoic acid.
115 Compounds of the class of carbamoyl sulphoxides having the general formula:
wherein R is selected from:
- alkyl containing 1 to 4 carbon atoms;and - haloalkyl containing l to 4 carbon atoms;
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.
wherein R is selected from:
- alkyl containing 1 to 4 carbon atoms;and - haloalkyl containing l to 4 carbon atoms;
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.
116 The compound having the formula:
.
.
117 The compound having the formula:
.
.
118 The compound having the formula:
.
.
119 The compound having the formula:
.
.
120 The compound having the formula:
.
.
121 A process for manufacturing a compound having the general formula:
wherein R is selected from:
- alkyl containing 1 to 4 carbon atoms; and - haloalkyl containing 1 to 4 carbon atoms;
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.
comprising the steps of:
(a) reacting an oxidizing agent selected from:
(i) peracetic acid; and (ii) m-chloroperoxybenzoic acid and a thiocarbamate, said thiocarbamate hav-ing the general formula:
wherein R, R1 and R2 have been previously defined;
(b) said reaction being carried out at a temperature between -15°C and 50°C; and (c) said oxidizing agent being present in an amount of one molar equivalent.
wherein R is selected from:
- alkyl containing 1 to 4 carbon atoms; and - haloalkyl containing 1 to 4 carbon atoms;
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.
comprising the steps of:
(a) reacting an oxidizing agent selected from:
(i) peracetic acid; and (ii) m-chloroperoxybenzoic acid and a thiocarbamate, said thiocarbamate hav-ing the general formula:
wherein R, R1 and R2 have been previously defined;
(b) said reaction being carried out at a temperature between -15°C and 50°C; and (c) said oxidizing agent being present in an amount of one molar equivalent.
122 A method of controlling undesirable vegetation com-prising applying to the locus where control is desired an effective amount of a compound represented by the general formula:
wherein R is selected from:
- alkyl containing 1 to 4 carbon atoms; and - haloalkyl containing 1 to 4 carbon atoms;
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.
wherein R is selected from:
- alkyl containing 1 to 4 carbon atoms; and - haloalkyl containing 1 to 4 carbon atoms;
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.
123 The method as set forth in claim C21 wherein R is -C2H5, R1 is n-C3H7 and R2 is n-C3H7.
124 The method as set forth in claim C21 wherein R is n-C3H7, R1 is n-C3H7 and R2 is n-C3H7.
125 The method as set forth in claim C21 wherein R is -C2H5, R1 is i-C4H9 and R2 is i-C4H9.
126 The method as set forth in claim C21 wherein R is n-C3H7, R1 is n-C4H9 and R2 is -C2H5.
127 The method as set forth in claim C21 wherein R is n-C3H7, R1 is -C2H5 and R2 is .
Applications Claiming Priority (12)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US28037172A | 1972-08-14 | 1972-08-14 | |
| US28037272A | 1972-08-14 | 1972-08-14 | |
| US28037372A | 1972-08-14 | 1972-08-14 | |
| US280,371 | 1972-08-14 | ||
| US280,373 | 1972-08-14 | ||
| US280,372 | 1972-08-14 | ||
| US37132773A | 1973-06-18 | 1973-06-18 | |
| US371,326 | 1973-06-18 | ||
| US371,328 | 1973-06-18 | ||
| US371,327 | 1973-06-18 | ||
| US371326A US3896169A (en) | 1972-08-14 | 1973-06-18 | Method of making carbonoyl sulfoxide derivatives |
| US371328A US3928436A (en) | 1972-08-14 | 1973-06-18 | Carbamoyl sulfoxide derivatives |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1155125A true CA1155125A (en) | 1983-10-11 |
Family
ID=27559546
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000178728A Expired CA1155125A (en) | 1972-08-14 | 1973-08-14 | Herbicidal compositions |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS5636166B2 (en) |
| CA (1) | CA1155125A (en) |
| CH (1) | CH584004A5 (en) |
| DE (1) | DE2341119A1 (en) |
| FR (1) | FR2196120A1 (en) |
| IT (1) | IT990471B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AR219067A1 (en) * | 1976-03-29 | 1980-07-31 | Stauffer Chemical Co | NEW HERBICIDES COMPOUNDS DERIVED FROM S-METHYL SUBSTITUTED THIOCARBAMATE AND SULFOXIDES THEREOF |
| JPS5823602A (en) * | 1981-08-04 | 1983-02-12 | Asahi Chem Ind Co Ltd | Thiolcarbamate herbicidal composition for paddy field |
-
1973
- 1973-08-14 DE DE19732341119 patent/DE2341119A1/en not_active Withdrawn
- 1973-08-14 JP JP9124973A patent/JPS5636166B2/ja not_active Expired
- 1973-08-14 IT IT8627373A patent/IT990471B/en active
- 1973-08-14 CA CA000178728A patent/CA1155125A/en not_active Expired
- 1973-08-14 CH CH1170073A patent/CH584004A5/xx not_active IP Right Cessation
- 1973-08-14 FR FR7329768A patent/FR2196120A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| CH584004A5 (en) | 1977-01-31 |
| JPS5012233A (en) | 1975-02-07 |
| AU5923573A (en) | 1975-02-20 |
| FR2196120A1 (en) | 1974-03-15 |
| IT990471B (en) | 1975-06-20 |
| DE2341119A1 (en) | 1974-02-28 |
| JPS5636166B2 (en) | 1981-08-22 |
| FR2196120B1 (en) | 1978-03-10 |
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| Date | Code | Title | Description |
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| MKEX | Expiry |