CA1082721A - Herbicidally active thiocarbamates and sulfoxides - Google Patents
Herbicidally active thiocarbamates and sulfoxidesInfo
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- CA1082721A CA1082721A CA273,155A CA273155A CA1082721A CA 1082721 A CA1082721 A CA 1082721A CA 273155 A CA273155 A CA 273155A CA 1082721 A CA1082721 A CA 1082721A
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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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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
Abstract of the Disclosure Herbicidally active S-cycloalkylmethyl thiocarbamates and their sulfoxide derivatives are described herein. The compounds have the following general structural formula:
Description
Description of the Invention This invention is directed to a novel class of thio-carbamates, certain sulfoxide derivatives thereof and to the use of said thiocarbamates and sulfoxides in controlling undesirable vegetation. The compounds of the present invention are represented by the following general structural formula:
(R) n p / Rl R-CH2-S ~ -N \
R2 . ' ' .
wherein n is 0 or 1; R is selected from the group consisting of tertiary butyi, cyclopropyl, cyclobutyl and cyclopentyl; and Rl and R2 are individually selected from the group consisting of alkyl, alkenyl, cyclopropylmethyl, cyclohexyl, phenyl and benzyl or Rl and R2 together form an alkylene group or an alkyl substituted alkylene group.
The term "alkyl" is meant to include straight and branched chain alkyl groups having 1-6 carbon atoms. The term "alkenyl" is meant to include straight and branched chain alkenyl groups having 2-6 carbon atoms. The term "alkylene" is meant to include alkylene groups containing 4-7 carbon atoms.
- The thiocarbamates, i.e. compounds of the above formula wherein n equals 0, can be prepared by any of the known methods of synthesis of thiocarbamates. Typical methods of preparing thiocarbamates are disclosed in U.S. Patents No. 2,913,327,
(R) n p / Rl R-CH2-S ~ -N \
R2 . ' ' .
wherein n is 0 or 1; R is selected from the group consisting of tertiary butyi, cyclopropyl, cyclobutyl and cyclopentyl; and Rl and R2 are individually selected from the group consisting of alkyl, alkenyl, cyclopropylmethyl, cyclohexyl, phenyl and benzyl or Rl and R2 together form an alkylene group or an alkyl substituted alkylene group.
The term "alkyl" is meant to include straight and branched chain alkyl groups having 1-6 carbon atoms. The term "alkenyl" is meant to include straight and branched chain alkenyl groups having 2-6 carbon atoms. The term "alkylene" is meant to include alkylene groups containing 4-7 carbon atoms.
- The thiocarbamates, i.e. compounds of the above formula wherein n equals 0, can be prepared by any of the known methods of synthesis of thiocarbamates. Typical methods of preparing thiocarbamates are disclosed in U.S. Patents No. 2,913,327,
2,983,747, 3,101,263, 3,133,947, 3,175,897 and 3,185,720. A
?articularly preferred method for preparing the thiocarbamates is to react the appropriate chlorothioformate with the desired amine. Appropriate starting materials for the preparation of the individual thiocarbamates will be readily apparent to one skilled in the art.
The sulfoxide derivatives of this invention, i.e. com-pounds of the above formula wherein n = 1, can be prepared by reacting an oxidizing agent such as peracetic acid or m-chloro-peroxybenzoic acid with the thiocarbamate defined above. The reaction is carried out in the presence of a solvent such as chloroform, methylene chloride, benzene or toluene and at a reduced temperature of from about -25C to about 65C. The amount of oxidizing agent used must be at least 1 molar equivalent.
The carbamyl sulfoxides of this invention are excellent herbicides and exhibit improved thermal stability The following examples serve to illustrate the prepara-tion of typcal thiocarbamate and sulfoxide compounds of this invention and demonstrate their herbicidal activity.
EXAMPL~
This example illustrates the preparation of S-cyclo-propylmethyl di-n-propyl thiocarbamate.
To a solution of 6.0 g (0.040 mole) of cyclopropylmethyl chlorothioformate in 50 ml benzene is added 8.5 g (0.084 mole) of di-n-propyl amine dissolved in 25 ml benzene while maintaining the temperature below 30C. The reaction mixture was stirred for 30 minutes, then washed with 50 ml 0.05 M hydrochloric acid ~nd then twice with 50 ml pcrtions of water. The solution wa8 then dried over anhydrous msgnesium sulfate, filteret and the volatiles stripped off. A yield of 7.9 g (theory ~ 8.5 g) of protuct having an N30 ~ 1.4S83 was obtained. The ~ructure of the product was confirmed by NMR and IR.
This example illustrates the preparstion of S-cyclo- -propylmethyl n-butyl cyclopropylmethyl thiocarbamate.
A solution of 3.44 g (0.021 mole) of n-butyl cyclopropyl-methyl amine hydrochloride and 40.5 g (0.04 mole) of triethylamine in 100 ml water is formed. Then, 3.0 g (0.020 mole) of cyclo-propylmethyl chlorothioformate was added dropwise with stirring ~hile maintaining ~he temperature below 30C. Strring was continued for 1 hour. The reaction mixture was then washed with 50 ml (0.05 mole) hydrochloric acid and twice with 50 ml portions of water. The solution was dried over anhydrous magnesium sulfate, filtered and the volatiles stripped off. A yield of 4.4 g (theory 4.8~ g) of product having ND30 : 1.4797 was obtained. Structure of the product was conf~rmed by NMR and IR.
EXAMP~E 3 This example illustrates the preparation of S-cyclo-propylmethyl n-butyl cyclopropylmethyl thiocarbamate sulfoxide.
A solution was formed by dissol~ing 4.3 g (0.0178 mole) of S-cyclopropylmethyl n~bucyI cyclopropylmethyl thiocarbamate, prepared as described in Example 2, in 75 ml methylene chloride `L~7;~1 in a 250 ml three-necked flask equipped with a mechanical stir-rer. The solution was cooled to 0C and 3,08 g (0,0178 mole) of meta-chloroperoxybenzo~c acid was added in portions so as to maintain the temperature between 0 snd 5C, The reaction m~xture was allowed to warm to room temperature with stirring and stirring was continued for about 90 minutes, After about 30 minutes starch/potassium iodide test psper indicated complete disappear-ance of peroxide from the reaction solution. The solution was washed with ~0 ml of 5% potassium carbon~te and then twice with 50 ml portions of water, The solution was dried over anhydrous mhgnesium sulfate, f~ltered and stripped of volatiles, A yield of 4,5 g (theory - 4,6 g) of a product having N30 _ 1,4890 was obtained, The structure of the product was confirmed by NMR and IR.
This example illustrates the preparation of cyclobutyl-methyl di-n-propyl thiocarbsmate, In a 250 ml three-necked, round-bottom flssk equipped with a mechanical stirrer and thermometer was placed a solution of 1.6 g (0,04 mole) sodium hydroxide in 75 ml water and 4,05 g (0,04 mole) di-n-propylamine, Rapid stirring was commenced and 6,57 g (0,04 mole) S-cyclobutylmethyl chlorothioformate was added dropwise at a rate to maintain the temperature below 40C, Following the addition the solution was stirred for one hour at room temperature. The reaction mixture was separated into an 2S organic layer and a water layer and the water layer was washed ~-with benzene. The resulting benzene layer was combined with the organic layer ~nd washed with 50 ml lN hydrochloric ~c~t snd with water snd the resul ing solution dried over anhytrous magnesium sulfste. A yield of 8.6 g (theory ~ 9.17 g) of product having an N30 1.4688 wss obtained Structure of the product W~8 confirmed by NMR and IR.
This example illustrates the prep~ration of S-c~clo butylmethyl di-n-propyl thioc~rbamate ~ulfoxide.
A solution was formed by dissolving 4.57 g (0.020 mole) of S-cyclobutylmethyl di-n-propyl thiocarbamate, prepared as described in Example 4, in 75 ml methylene chloride ~n a 250 ml three-necked flask equipped with a mechanical stirrer. The solution W8S cooled to 0C and 3.56 g (0.020 mole) of meta-chloro-peroxybenzoic acid was added in portions so as to maintain the temperature between 0 snd 5C. The reaction mixture was allowed to wanm to room temperature with stirring ~nd stirring was - continued for about 90 minutes. After about 30 minutes starch/
potassium iodide test psper indicated complete disappearance of peroxide from the reaction solution. The solution was washed with 70 ml of 5% potassium carbonate and then twice with 50 ml portions of water. The solution was drie~ over anhydrous magnesium sulfate, filtered, and stripped of volatiles. A yield of 4.7 g (theory = 4.9 g) of product having ~ = 1.4793 was obtained. The~tructure of the product was conf~rmed by NMR.
This example illustrates the preparation of S-cyclo-pentylmethyl di-n-propyl thiocarbamate.
, .
f ~1 In a 250 ml three-necked round-bottom flask equipped with a mecnanical st'rrer and thermometer were placed a solution of 0.8 (0.02 mole) sodium hydroxide in 75 ml water and 2.02 g (0.02 mole) di-n-propylamine. Rapid stirring was commenced and
?articularly preferred method for preparing the thiocarbamates is to react the appropriate chlorothioformate with the desired amine. Appropriate starting materials for the preparation of the individual thiocarbamates will be readily apparent to one skilled in the art.
The sulfoxide derivatives of this invention, i.e. com-pounds of the above formula wherein n = 1, can be prepared by reacting an oxidizing agent such as peracetic acid or m-chloro-peroxybenzoic acid with the thiocarbamate defined above. The reaction is carried out in the presence of a solvent such as chloroform, methylene chloride, benzene or toluene and at a reduced temperature of from about -25C to about 65C. The amount of oxidizing agent used must be at least 1 molar equivalent.
The carbamyl sulfoxides of this invention are excellent herbicides and exhibit improved thermal stability The following examples serve to illustrate the prepara-tion of typcal thiocarbamate and sulfoxide compounds of this invention and demonstrate their herbicidal activity.
EXAMPL~
This example illustrates the preparation of S-cyclo-propylmethyl di-n-propyl thiocarbamate.
To a solution of 6.0 g (0.040 mole) of cyclopropylmethyl chlorothioformate in 50 ml benzene is added 8.5 g (0.084 mole) of di-n-propyl amine dissolved in 25 ml benzene while maintaining the temperature below 30C. The reaction mixture was stirred for 30 minutes, then washed with 50 ml 0.05 M hydrochloric acid ~nd then twice with 50 ml pcrtions of water. The solution wa8 then dried over anhydrous msgnesium sulfate, filteret and the volatiles stripped off. A yield of 7.9 g (theory ~ 8.5 g) of protuct having an N30 ~ 1.4S83 was obtained. The ~ructure of the product was confirmed by NMR and IR.
This example illustrates the preparstion of S-cyclo- -propylmethyl n-butyl cyclopropylmethyl thiocarbamate.
A solution of 3.44 g (0.021 mole) of n-butyl cyclopropyl-methyl amine hydrochloride and 40.5 g (0.04 mole) of triethylamine in 100 ml water is formed. Then, 3.0 g (0.020 mole) of cyclo-propylmethyl chlorothioformate was added dropwise with stirring ~hile maintaining ~he temperature below 30C. Strring was continued for 1 hour. The reaction mixture was then washed with 50 ml (0.05 mole) hydrochloric acid and twice with 50 ml portions of water. The solution was dried over anhydrous magnesium sulfate, filtered and the volatiles stripped off. A yield of 4.4 g (theory 4.8~ g) of product having ND30 : 1.4797 was obtained. Structure of the product was conf~rmed by NMR and IR.
EXAMP~E 3 This example illustrates the preparation of S-cyclo-propylmethyl n-butyl cyclopropylmethyl thiocarbamate sulfoxide.
A solution was formed by dissol~ing 4.3 g (0.0178 mole) of S-cyclopropylmethyl n~bucyI cyclopropylmethyl thiocarbamate, prepared as described in Example 2, in 75 ml methylene chloride `L~7;~1 in a 250 ml three-necked flask equipped with a mechanical stir-rer. The solution was cooled to 0C and 3,08 g (0,0178 mole) of meta-chloroperoxybenzo~c acid was added in portions so as to maintain the temperature between 0 snd 5C, The reaction m~xture was allowed to warm to room temperature with stirring and stirring was continued for about 90 minutes, After about 30 minutes starch/potassium iodide test psper indicated complete disappear-ance of peroxide from the reaction solution. The solution was washed with ~0 ml of 5% potassium carbon~te and then twice with 50 ml portions of water, The solution was dried over anhydrous mhgnesium sulfate, f~ltered and stripped of volatiles, A yield of 4,5 g (theory - 4,6 g) of a product having N30 _ 1,4890 was obtained, The structure of the product was confirmed by NMR and IR.
This example illustrates the preparation of cyclobutyl-methyl di-n-propyl thiocarbsmate, In a 250 ml three-necked, round-bottom flssk equipped with a mechanical stirrer and thermometer was placed a solution of 1.6 g (0,04 mole) sodium hydroxide in 75 ml water and 4,05 g (0,04 mole) di-n-propylamine, Rapid stirring was commenced and 6,57 g (0,04 mole) S-cyclobutylmethyl chlorothioformate was added dropwise at a rate to maintain the temperature below 40C, Following the addition the solution was stirred for one hour at room temperature. The reaction mixture was separated into an 2S organic layer and a water layer and the water layer was washed ~-with benzene. The resulting benzene layer was combined with the organic layer ~nd washed with 50 ml lN hydrochloric ~c~t snd with water snd the resul ing solution dried over anhytrous magnesium sulfste. A yield of 8.6 g (theory ~ 9.17 g) of product having an N30 1.4688 wss obtained Structure of the product W~8 confirmed by NMR and IR.
This example illustrates the prep~ration of S-c~clo butylmethyl di-n-propyl thioc~rbamate ~ulfoxide.
A solution was formed by dissolving 4.57 g (0.020 mole) of S-cyclobutylmethyl di-n-propyl thiocarbamate, prepared as described in Example 4, in 75 ml methylene chloride ~n a 250 ml three-necked flask equipped with a mechanical stirrer. The solution W8S cooled to 0C and 3.56 g (0.020 mole) of meta-chloro-peroxybenzoic acid was added in portions so as to maintain the temperature between 0 snd 5C. The reaction mixture was allowed to wanm to room temperature with stirring ~nd stirring was - continued for about 90 minutes. After about 30 minutes starch/
potassium iodide test psper indicated complete disappearance of peroxide from the reaction solution. The solution was washed with 70 ml of 5% potassium carbonate and then twice with 50 ml portions of water. The solution was drie~ over anhydrous magnesium sulfate, filtered, and stripped of volatiles. A yield of 4.7 g (theory = 4.9 g) of product having ~ = 1.4793 was obtained. The~tructure of the product was conf~rmed by NMR.
This example illustrates the preparation of S-cyclo-pentylmethyl di-n-propyl thiocarbamate.
, .
f ~1 In a 250 ml three-necked round-bottom flask equipped with a mecnanical st'rrer and thermometer were placed a solution of 0.8 (0.02 mole) sodium hydroxide in 75 ml water and 2.02 g (0.02 mole) di-n-propylamine. Rapid stirring was commenced and
3.58 g (0.02 mole) of S-cyclopentylmethyl chlorothioformate was added dropwise at a rate to maintain the temperature below 40C.
Following the addition, the solution was stirred for one hour at room temperature. The reaction mixture was separated into an -organic layer and a water layer and the water layer washed with benzene. The resulting benzene layer was combined with the organic layer and washed with 50 ml LN hydrochloric acid and with water and the resulting solution dired over anhydrous magnesium sulfate. A yield of 4.6 g (theory = 4.87 g) of product having N30 = 1.4719 was obtained. Structure of the produce was confirmed by N~ and IR.
This example illustrates the preparation of S-neopentyl butylethyl thiocarbamate.
In a 250 ml flask were placed a solution of 1.6 g (0.04 mole) NaOH in 100 ml water and 4 0 g (0.04 mole) of butyl-ethylamine. The mixture was stirred rapidly while 6.7 g (0.~4 mole) of neopentylchlorothioformate was added dropwise, at a rate such that the temperature was maint~ined at a maximum of 40C. After the addition was complete, the mixture was stirred at room temperature for 1 hour. The organic layer was separated, the aqueous layer was washed with benzene and the combined organic phases were washed with 50 ml of lN HCl, water, and dried over MgSO4. There was obtained 7.2 g (78~/o g theoretical yield) of S-neopent~l butylethyl-thioc~rbamate, N30 _ 1.4499.
EXA~fPLE 8 This example illustrates the preparation of S-neopentyl hexahydro-lH-azepinecarbothioate sulfoxide.
In a 250 ml flask were placed 4.6 g (0.02 mole) S-neopentyl hexahydro-lH-azepinecarbothioate and 75 ml methylene chloride. The mixture was cooled to 5C with an ice/acetone bath, and 3~5 g (0.02 mole) m-chloroperoxvbenzoic acid was added. The reaction mixture was allowed to warm up to room temperature, then further warmed to about 35-40C~ washed with 2 portions each of 50 ml of 5% aqueous potassiu.~ carbonate, followed by 2 portions each of 50 ml water, dried over MgS04 and stripped of solvent.
There was obtained 4~3 g (86~/o of theoretical yield), of S-neopentyl hexahydro-lH-azepinecarbothioate sulfoxide, N30 _ 1.4619.
Other compounds were prepared in an analagous manner starting with the appropriate starting materials as outlined above. The following Table I lists compounds representative of those embodied by the present invention, including those whose preparation is described above. Compound numbers have been assigned ~o them and are used for identification throughout the balance of this specification.
a~
TABLE I
()n 8~Rl \R2 Com-pound No. R Rl ~ n D- -C2H5 ~ C4H9 2 D- -C2H5 g C4H9 3 D- -n-C3H7 n C3H7 0
Following the addition, the solution was stirred for one hour at room temperature. The reaction mixture was separated into an -organic layer and a water layer and the water layer washed with benzene. The resulting benzene layer was combined with the organic layer and washed with 50 ml LN hydrochloric acid and with water and the resulting solution dired over anhydrous magnesium sulfate. A yield of 4.6 g (theory = 4.87 g) of product having N30 = 1.4719 was obtained. Structure of the produce was confirmed by N~ and IR.
This example illustrates the preparation of S-neopentyl butylethyl thiocarbamate.
In a 250 ml flask were placed a solution of 1.6 g (0.04 mole) NaOH in 100 ml water and 4 0 g (0.04 mole) of butyl-ethylamine. The mixture was stirred rapidly while 6.7 g (0.~4 mole) of neopentylchlorothioformate was added dropwise, at a rate such that the temperature was maint~ined at a maximum of 40C. After the addition was complete, the mixture was stirred at room temperature for 1 hour. The organic layer was separated, the aqueous layer was washed with benzene and the combined organic phases were washed with 50 ml of lN HCl, water, and dried over MgSO4. There was obtained 7.2 g (78~/o g theoretical yield) of S-neopent~l butylethyl-thioc~rbamate, N30 _ 1.4499.
EXA~fPLE 8 This example illustrates the preparation of S-neopentyl hexahydro-lH-azepinecarbothioate sulfoxide.
In a 250 ml flask were placed 4.6 g (0.02 mole) S-neopentyl hexahydro-lH-azepinecarbothioate and 75 ml methylene chloride. The mixture was cooled to 5C with an ice/acetone bath, and 3~5 g (0.02 mole) m-chloroperoxvbenzoic acid was added. The reaction mixture was allowed to warm up to room temperature, then further warmed to about 35-40C~ washed with 2 portions each of 50 ml of 5% aqueous potassiu.~ carbonate, followed by 2 portions each of 50 ml water, dried over MgS04 and stripped of solvent.
There was obtained 4~3 g (86~/o of theoretical yield), of S-neopentyl hexahydro-lH-azepinecarbothioate sulfoxide, N30 _ 1.4619.
Other compounds were prepared in an analagous manner starting with the appropriate starting materials as outlined above. The following Table I lists compounds representative of those embodied by the present invention, including those whose preparation is described above. Compound numbers have been assigned ~o them and are used for identification throughout the balance of this specification.
a~
TABLE I
()n 8~Rl \R2 Com-pound No. R Rl ~ n D- -C2H5 ~ C4H9 2 D- -C2H5 g C4H9 3 D- -n-C3H7 n C3H7 0
4 D- -n-C4Hg _n-C4H9 D- -n-C4Hg -CH2~
6 D- -i-C4H9 -i-C4H9 D- ~ CH2--CH2 i 2 8 D- -C2H5 -CH2~
g D- -n-C3H7 CH2<¦ 0 D~ C3H7 11 D -CH2CH-CH2 CH2<1 12 C~ -s-C4H9 2-'a 13 D~- -CH2~ -CH2~<1 o 7f~1 TAB~E I (con ' t) Com-potmd No. R Rl --2 D- C2H5 ~
16 D- -C2H5 ~
17 D- -C2H5 CH2~
18 ~ -n-C3H7 i-C3H7 19 D- -S-C4Hg ~ C4Hg . O
D- ~2H5 0 ~H--CH2 2 21 ~ -i-C4Hg -s-C4H9 22 D- -CH2-<1 CH2-<1 . O
~ ~ CH2 CH2~U2'--CH2 ~, 24 D- -n-C3H7 -n-C3H7 C'~ -C2H5 -CH2CHSCH2 26 C>- -C2H5 -n-C4H9 27 D- -C2H5 -s-C4H9 -io-l~'f ~
TABLE I (con't) Com-pound No. R Rl ~2 n - 28 ~- -C2H5 -CH2~
29 ~ -C2H5 _~ 1 ~ -C2H5 ~
31 D- -C2H5 -CH2~3 1 32 D- -n-C3H7 -i-C3H7 33 D- -n-C3H7 CH2 34 D- -i-C3H7 -CH
D- ~H2CH8CH2 -CH2-~1 36 D; . n-C4Hg -CH2<¦ 1 37 D- i-C4Hg i-C4H9 38 ~ s-C4Hg ~-C4H9 D- 8-C4Hg -CH
D- -CH2<~ -CH~
~H--CH2 42 D- CH2~H2 I H2 ~CH2--CH2--C~2 -Ll-TABLE I ~con't) Co~-pound No. R ~1 R2 43 ~ -i-C4Hg -s-C4Hg 44 ~ -CH2 ~ -CH
~~ CH2----CH2 C2H5 -n-C4H9 47 ~ -C2H5 -s-C4Hg O
48 ~ C2H5. ~
49 ~ . -n-C3H7 -n-C3H7 O
O~ -n-C4Hg -CH2~
51 ~ -i-C4Hg -i-C4H9 ~:
52 -s-C4Hg -8-C4H9
6 D- -i-C4H9 -i-C4H9 D- ~ CH2--CH2 i 2 8 D- -C2H5 -CH2~
g D- -n-C3H7 CH2<¦ 0 D~ C3H7 11 D -CH2CH-CH2 CH2<1 12 C~ -s-C4H9 2-'a 13 D~- -CH2~ -CH2~<1 o 7f~1 TAB~E I (con ' t) Com-potmd No. R Rl --2 D- C2H5 ~
16 D- -C2H5 ~
17 D- -C2H5 CH2~
18 ~ -n-C3H7 i-C3H7 19 D- -S-C4Hg ~ C4Hg . O
D- ~2H5 0 ~H--CH2 2 21 ~ -i-C4Hg -s-C4H9 22 D- -CH2-<1 CH2-<1 . O
~ ~ CH2 CH2~U2'--CH2 ~, 24 D- -n-C3H7 -n-C3H7 C'~ -C2H5 -CH2CHSCH2 26 C>- -C2H5 -n-C4H9 27 D- -C2H5 -s-C4H9 -io-l~'f ~
TABLE I (con't) Com-pound No. R Rl ~2 n - 28 ~- -C2H5 -CH2~
29 ~ -C2H5 _~ 1 ~ -C2H5 ~
31 D- -C2H5 -CH2~3 1 32 D- -n-C3H7 -i-C3H7 33 D- -n-C3H7 CH2 34 D- -i-C3H7 -CH
D- ~H2CH8CH2 -CH2-~1 36 D; . n-C4Hg -CH2<¦ 1 37 D- i-C4Hg i-C4H9 38 ~ s-C4Hg ~-C4H9 D- 8-C4Hg -CH
D- -CH2<~ -CH~
~H--CH2 42 D- CH2~H2 I H2 ~CH2--CH2--C~2 -Ll-TABLE I ~con't) Co~-pound No. R ~1 R2 43 ~ -i-C4Hg -s-C4Hg 44 ~ -CH2 ~ -CH
~~ CH2----CH2 C2H5 -n-C4H9 47 ~ -C2H5 -s-C4Hg O
48 ~ C2H5. ~
49 ~ . -n-C3H7 -n-C3H7 O
O~ -n-C4Hg -CH2~
51 ~ -i-C4Hg -i-C4H9 ~:
52 -s-C4Hg -8-C4H9
5~ ~ -i~C4Hg -s-C4Hg o ~CH2--CH2~CH2 '' ~ -CH2 ~ C~2 ~
56 ~
~CH2 --C~
~ CH2 7~
TABLE I (con't) Com-pound No. R Rl --2 57 <~ / 2~H2~
58 0 ~CH2--CH2 IH2 ~C~2--C~2~2 59 O- -CH2~ -CH2~
. 6 ' ,[~ -C2115 n C4~19 0 61 O~ S-C4H9 62 O- -C2~15 ~ O
63 O- -n-C3H -n C3H7 64 l~ -i-C4119 i-c4n9 ~_ -CH2~ -CH2~<1 0 66 O- -~-C4H9 67 O~ -s-C4Hg -s-C4Hg O
68 O ~CH2~H2 1CH2 ~CH2--CH2~H2 ~,r ~~ 1 3.~
Table I (con't) Com-pound No. R Rl R2 n _ 69 U f2H5 0 CH2~
~CH2 7H~12 U` -n-C4Hg -n-C4Hg O
71 0 / CH2---CH2--C ~ O
~ CH2 CH2--CH2~H2 ~ ICH3 ~ .
72 CH3-C- C2H5n-C4Hg O
CH ' _ ~
73 CH3 ~ C2H5i C4H9 74 CH3-C- C2H5 sec.-C4H9 O
ICH3 .
C 3 IC 3 7 n-C3H7 O
76 CH3-C- n C3H7 i-C3H7 ~ . " ~ .
. . . . . .
'7~1 TABLE I (con't) Com-pound No. R Rl R2 ICH ~
77 CH3 IC allyl allyl 0 78 CH3-C- i C3H7 i C4H9 79 CH3-C- i-C4Hg i-C4H9 ~H3 CH3-C- sec.-C4Hg sec.-c4H9 0 81 CH3-F- i C4H9 sec.-C4Hg 0 ICH3 ~CH2-CH2-CH2 82 CH3-1C- \ ¦ 0 CH
83 CH3-C- C2H5 allyl 84 CH3-C- ' C2H5 cyclohexyl 0 CH3-C- n-C4Hg cyclopropyl- 0 B.. ,.!~ -- 15 7~1 TABLE I (con't) Com-pound No. R RlC H R2 n l2 5 ,CH3 CH2- CH
CH
87 C 3 cyclopropyl- cyclopropyl- O
CH3 methyl . . methyl ICH3 ~ CH2-CH? -C~
88 CH3-C- ~ CH2 0 ~H3 89 CH3-C- C2H5 seC.-c4H9 CH3 C i C4H9 sec.-C4H9 91 CH3-C- C2H5 n-C4H9 92 CH3-C- C2H5 i C4Hg ÇH3 93 CH3-C- C3H7 i 3 7 94 CH3-C- i C3H7 i-C4H9 .B.~.
. " ~, .
r~ ~
a~
TABLE I (con~t) Com-pound No. R Rl R2 n CH3-C~- sec.-C4Hg sec.-C4H9 ~H3 96 CH3-CI- C ~ CH=CH2 CH2CH=CH2 97 CH3-C- n~C3H7 n C3H7 98 CH3-~- C2H5 CH2CH-CH2 99 CH3-C- C2H5 cyclohexyl 100 CH3 C4Hg methyl ~C 2H5 ~jCH3 / ~CH2 C ~
101 CH3-C- ~ ~ CH2 CH3 ICI~ C 2 iCH3 102 CH -IC- cyclopropyl- cyclopropyl-3 CH3 methyl methyl .~ -17-7~
TABLE I (con ' t Com-R Rl 2 103 CH3-C- iC4H9 i-C4Hg C! H3 /CH2-CH2-CH2 ~H3 CH2 CH2 CH2 Cl H3 ~CH2-CH2~
105 CH3-C- \ H2 ~J ~" .
~ 7~1 .
Herbicidal Screenin~ Test A~ previously mentioned, the novel thiocarbamates and sulfoxides herein descr~bed are phytotoxic compounds which are useful and valuable in controlling various plant species. Com-pounds of this invention are tested as herbicides in the fol-lowing manner.
Pre-emer~ence Her~icide Screenin~ Test Using an analytical balance, 20 mg. of the compound to be tested i8 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~ (a polyoxyethylene sorb~tan monolaurate) is added to d~ssolve the compound. If the material is not soluble in acetone, another solvent such as water, alcohol or dimethylformamide (DMF) is uæed instead. When DMF is used, only 0.5 ml or less is used to dissolve the co~pound snd then another 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 soil. A No. 152 DeVilbiss atomizer is used to apply the spray using compresset air at a pre~sure 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 wlth loamy sand soil. Seeds of seven different weed species are planted in individual rows using one specles per row across the width of the flat. The ~ -L9-.
seeds are covered with soil so that they are planted at a depth of 0.5 inch. The seeds used are hairy crabgrass (Di~itaria san~uinalis), yellow foxtail (Setaria ~lauca), redroot pigweed ~Amaranthus retroflexus), Indian mustard (Brassica ~uncea~, S curly dock (Rumex crispus), watergrass (Echinochloa crus~alli), and red oat (Avena _ativa). 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 in~ury or control is deter-mined by comparison with untreated check plants of the same age.
The in3ury rating from 0 to 1007o is recorded for each species as percent control with ~/O representing no in~ury and 1007o representing complete kill.
Post-emer~ence Herbicide Screenin~ Test Seeds of six plant species, including hairy crabgrass, watergrass, red oat, mustard, curly dock End Pinto beans (Phaseolus vul~ar~s) 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 tri-foliate leaves are just starting to fonm, 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 ... . .
': ' , . ' L~
using a No. 152 DeVilbiss atomizer at an air pressure of 5 lb/
8q . in. The spray concentration is 0.2 and the rate i8 8 lb/acre.
The spray volume is 476 gal/acre. In~ury ratings are recorded 14 days after treatment. The rating sys~em i8 the same as des-ibed abovè in the pre-emergence test, The results of these tests are shown in Table II.
TABLE II
Per cent contral at 8 lb/A . -Compound Pre-Emer~ence ~ Post-Emergence 2 ~ 55 5 , . ....... . . . . . ..
4 - 54 ~ 43
56 ~
~CH2 --C~
~ CH2 7~
TABLE I (con't) Com-pound No. R Rl --2 57 <~ / 2~H2~
58 0 ~CH2--CH2 IH2 ~C~2--C~2~2 59 O- -CH2~ -CH2~
. 6 ' ,[~ -C2115 n C4~19 0 61 O~ S-C4H9 62 O- -C2~15 ~ O
63 O- -n-C3H -n C3H7 64 l~ -i-C4119 i-c4n9 ~_ -CH2~ -CH2~<1 0 66 O- -~-C4H9 67 O~ -s-C4Hg -s-C4Hg O
68 O ~CH2~H2 1CH2 ~CH2--CH2~H2 ~,r ~~ 1 3.~
Table I (con't) Com-pound No. R Rl R2 n _ 69 U f2H5 0 CH2~
~CH2 7H~12 U` -n-C4Hg -n-C4Hg O
71 0 / CH2---CH2--C ~ O
~ CH2 CH2--CH2~H2 ~ ICH3 ~ .
72 CH3-C- C2H5n-C4Hg O
CH ' _ ~
73 CH3 ~ C2H5i C4H9 74 CH3-C- C2H5 sec.-C4H9 O
ICH3 .
C 3 IC 3 7 n-C3H7 O
76 CH3-C- n C3H7 i-C3H7 ~ . " ~ .
. . . . . .
'7~1 TABLE I (con't) Com-pound No. R Rl R2 ICH ~
77 CH3 IC allyl allyl 0 78 CH3-C- i C3H7 i C4H9 79 CH3-C- i-C4Hg i-C4H9 ~H3 CH3-C- sec.-C4Hg sec.-c4H9 0 81 CH3-F- i C4H9 sec.-C4Hg 0 ICH3 ~CH2-CH2-CH2 82 CH3-1C- \ ¦ 0 CH
83 CH3-C- C2H5 allyl 84 CH3-C- ' C2H5 cyclohexyl 0 CH3-C- n-C4Hg cyclopropyl- 0 B.. ,.!~ -- 15 7~1 TABLE I (con't) Com-pound No. R RlC H R2 n l2 5 ,CH3 CH2- CH
CH
87 C 3 cyclopropyl- cyclopropyl- O
CH3 methyl . . methyl ICH3 ~ CH2-CH? -C~
88 CH3-C- ~ CH2 0 ~H3 89 CH3-C- C2H5 seC.-c4H9 CH3 C i C4H9 sec.-C4H9 91 CH3-C- C2H5 n-C4H9 92 CH3-C- C2H5 i C4Hg ÇH3 93 CH3-C- C3H7 i 3 7 94 CH3-C- i C3H7 i-C4H9 .B.~.
. " ~, .
r~ ~
a~
TABLE I (con~t) Com-pound No. R Rl R2 n CH3-C~- sec.-C4Hg sec.-C4H9 ~H3 96 CH3-CI- C ~ CH=CH2 CH2CH=CH2 97 CH3-C- n~C3H7 n C3H7 98 CH3-~- C2H5 CH2CH-CH2 99 CH3-C- C2H5 cyclohexyl 100 CH3 C4Hg methyl ~C 2H5 ~jCH3 / ~CH2 C ~
101 CH3-C- ~ ~ CH2 CH3 ICI~ C 2 iCH3 102 CH -IC- cyclopropyl- cyclopropyl-3 CH3 methyl methyl .~ -17-7~
TABLE I (con ' t Com-R Rl 2 103 CH3-C- iC4H9 i-C4Hg C! H3 /CH2-CH2-CH2 ~H3 CH2 CH2 CH2 Cl H3 ~CH2-CH2~
105 CH3-C- \ H2 ~J ~" .
~ 7~1 .
Herbicidal Screenin~ Test A~ previously mentioned, the novel thiocarbamates and sulfoxides herein descr~bed are phytotoxic compounds which are useful and valuable in controlling various plant species. Com-pounds of this invention are tested as herbicides in the fol-lowing manner.
Pre-emer~ence Her~icide Screenin~ Test Using an analytical balance, 20 mg. of the compound to be tested i8 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~ (a polyoxyethylene sorb~tan monolaurate) is added to d~ssolve the compound. If the material is not soluble in acetone, another solvent such as water, alcohol or dimethylformamide (DMF) is uæed instead. When DMF is used, only 0.5 ml or less is used to dissolve the co~pound snd then another 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 soil. A No. 152 DeVilbiss atomizer is used to apply the spray using compresset air at a pre~sure 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 wlth loamy sand soil. Seeds of seven different weed species are planted in individual rows using one specles per row across the width of the flat. The ~ -L9-.
seeds are covered with soil so that they are planted at a depth of 0.5 inch. The seeds used are hairy crabgrass (Di~itaria san~uinalis), yellow foxtail (Setaria ~lauca), redroot pigweed ~Amaranthus retroflexus), Indian mustard (Brassica ~uncea~, S curly dock (Rumex crispus), watergrass (Echinochloa crus~alli), and red oat (Avena _ativa). 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 in~ury or control is deter-mined by comparison with untreated check plants of the same age.
The in3ury rating from 0 to 1007o is recorded for each species as percent control with ~/O representing no in~ury and 1007o representing complete kill.
Post-emer~ence Herbicide Screenin~ Test Seeds of six plant species, including hairy crabgrass, watergrass, red oat, mustard, curly dock End Pinto beans (Phaseolus vul~ar~s) 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 tri-foliate leaves are just starting to fonm, 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 ... . .
': ' , . ' L~
using a No. 152 DeVilbiss atomizer at an air pressure of 5 lb/
8q . in. The spray concentration is 0.2 and the rate i8 8 lb/acre.
The spray volume is 476 gal/acre. In~ury ratings are recorded 14 days after treatment. The rating sys~em i8 the same as des-ibed abovè in the pre-emergence test, The results of these tests are shown in Table II.
TABLE II
Per cent contral at 8 lb/A . -Compound Pre-Emer~ence ~ Post-Emergence 2 ~ 55 5 , . ....... . . . . . ..
4 - 54 ~ 43
6 55 25
- 7 59 52
8 87. 37
9 77 53 -Zl-'7~1 TABLE II (con't) Per cent control at 8 lb/A
Compound Pre-Emergence Post-Emergence No.
~4 ~8 63 - 25 67 ~5 .
. -22-. . .
TABLE II (con1t) Per cent control at 8 lb/A
Compound _ N0. Pre-emer~ence Post-emer~ence 46 .. 40 42 48 . 51 46 5~ 51 35 57 . 68 81 63 30 41 ~
TABLE II (con't) Per cent control at 8 lb/A
Compound No. Pre-emer~ence Post-emer~ence 78 58 ^ O
~0 31 0 ~4 33 43 gO 83 74 -TABLE II (con't) Per cent control at 8 lb/A
Compound No. Pre-emergence Post-emer~ence Average for seven plant species in the pre-emergence test and for six plant species in the post-emergence test.
The herbicidal compounds of this invention are applied to soil to control the growth of undesirable vegetation in th2 form of compositions or formulations containing the compound and an inert carrier. Herbicidal formulations generally take the form of dusts, wettable powders, granules, solutions, or emulsifiable concentrates.
Dusts are free-flowing powder compositions containing the herbicidal com?ound imprPgnated on a particulate carrier.
The ?articule size of the carrier is usually in the range of from about 30 to 50 microns. Examples of suitable carriers are talc, .
bentoinite, diatomaceous earth, and pyrophyllite. Anticaking and antistatic agents can be added, if desired. The composition generally contains up to 50% of active ingxedient.
Wettable powders are finely divided compositions com-prising a particulate carrier impregnated with the herbicidal compound and additionally contain one or more surface active agent. The surface active agent promotes rapid dispersion of the powder in aqueous medium to form stable, sprayable suspensions.
A wide variety of surface active agents can be used, for example, long chain fatty alcohols and alkali metal salts of the sulfated fatty alcohols; salts of sulfonic acid; esters of long chain fatty acids; and polyhydric alcohols, in which the alcohol groups are free, omega-substituted polyethylene glycols of relatively long chain length. A list of surface active agents suitable for use in agriculture formulations can be found in Pesticide Formulations by Wade Van Valkenburg, Marcel Dekker, Inc., N.Y.
1973 at pages 79-84.
Granules comprise the herbicidal compound impregnated on a particulate inert carrier having a particle size of about 1 to 2 millimeters in diameter. The granules can be made by spraying a solution o the active ingredient in a volatile sol-vent onto the granular carrier. Suitable carriers in preparation of granules include clay, vermiculite, sawdust, granular carbon, and the like.
The herbicidal compounds can also be applied to the soil in the form of a solution in a suitable solvent. Solvents frequently used in her~icidal formulations include kerosene, fuel oil, xylene, petroleum fractions with boiling ranges above xylene, and aromatic petroleum fractions rich in methylated naphthalenes.
Emulsifiable concentrates consist of an oil solution of the herbicide along with an emulsiying agent. Prior to use the concentrate is diluted with water to form a suspended emulsion of oil droplets. The emulsifiers used are usually a mixture of anionic and nonionic surfactants. Other additives such as spreading agents and stickers can be included in the emulsifiable concentrate.
The compositions are applied to the soil to control the growth of undesirable vegetation at a rate to provide 1-50 pounds per acre of active herbicidal ingredient. The amount of actual ingredient used per acre will depend on overall cost and desired result. It will be readily apparent to one skilled in the art that compounds exhibiting lower herbicidal activity will require a higher dosage rate for the same degree of control than more active compounds.
Compound Pre-Emergence Post-Emergence No.
~4 ~8 63 - 25 67 ~5 .
. -22-. . .
TABLE II (con1t) Per cent control at 8 lb/A
Compound _ N0. Pre-emer~ence Post-emer~ence 46 .. 40 42 48 . 51 46 5~ 51 35 57 . 68 81 63 30 41 ~
TABLE II (con't) Per cent control at 8 lb/A
Compound No. Pre-emer~ence Post-emer~ence 78 58 ^ O
~0 31 0 ~4 33 43 gO 83 74 -TABLE II (con't) Per cent control at 8 lb/A
Compound No. Pre-emergence Post-emer~ence Average for seven plant species in the pre-emergence test and for six plant species in the post-emergence test.
The herbicidal compounds of this invention are applied to soil to control the growth of undesirable vegetation in th2 form of compositions or formulations containing the compound and an inert carrier. Herbicidal formulations generally take the form of dusts, wettable powders, granules, solutions, or emulsifiable concentrates.
Dusts are free-flowing powder compositions containing the herbicidal com?ound imprPgnated on a particulate carrier.
The ?articule size of the carrier is usually in the range of from about 30 to 50 microns. Examples of suitable carriers are talc, .
bentoinite, diatomaceous earth, and pyrophyllite. Anticaking and antistatic agents can be added, if desired. The composition generally contains up to 50% of active ingxedient.
Wettable powders are finely divided compositions com-prising a particulate carrier impregnated with the herbicidal compound and additionally contain one or more surface active agent. The surface active agent promotes rapid dispersion of the powder in aqueous medium to form stable, sprayable suspensions.
A wide variety of surface active agents can be used, for example, long chain fatty alcohols and alkali metal salts of the sulfated fatty alcohols; salts of sulfonic acid; esters of long chain fatty acids; and polyhydric alcohols, in which the alcohol groups are free, omega-substituted polyethylene glycols of relatively long chain length. A list of surface active agents suitable for use in agriculture formulations can be found in Pesticide Formulations by Wade Van Valkenburg, Marcel Dekker, Inc., N.Y.
1973 at pages 79-84.
Granules comprise the herbicidal compound impregnated on a particulate inert carrier having a particle size of about 1 to 2 millimeters in diameter. The granules can be made by spraying a solution o the active ingredient in a volatile sol-vent onto the granular carrier. Suitable carriers in preparation of granules include clay, vermiculite, sawdust, granular carbon, and the like.
The herbicidal compounds can also be applied to the soil in the form of a solution in a suitable solvent. Solvents frequently used in her~icidal formulations include kerosene, fuel oil, xylene, petroleum fractions with boiling ranges above xylene, and aromatic petroleum fractions rich in methylated naphthalenes.
Emulsifiable concentrates consist of an oil solution of the herbicide along with an emulsiying agent. Prior to use the concentrate is diluted with water to form a suspended emulsion of oil droplets. The emulsifiers used are usually a mixture of anionic and nonionic surfactants. Other additives such as spreading agents and stickers can be included in the emulsifiable concentrate.
The compositions are applied to the soil to control the growth of undesirable vegetation at a rate to provide 1-50 pounds per acre of active herbicidal ingredient. The amount of actual ingredient used per acre will depend on overall cost and desired result. It will be readily apparent to one skilled in the art that compounds exhibiting lower herbicidal activity will require a higher dosage rate for the same degree of control than more active compounds.
Claims (211)
1. A compound having the general structural formula:
wherein n is 0 or 1; R is selected from the group consisting of tertiary butyl, cyclopropyl, cyclobutyl and cyclopentyl; and R1 and R2 are individually selected from the group consisting of alkyl, alkenyl, cyclopropylmethyl, cyclohexyl, phenyl and benzyl or R1 and R2 together form an alkylene group or an alkyl substituted alkylene group.
wherein n is 0 or 1; R is selected from the group consisting of tertiary butyl, cyclopropyl, cyclobutyl and cyclopentyl; and R1 and R2 are individually selected from the group consisting of alkyl, alkenyl, cyclopropylmethyl, cyclohexyl, phenyl and benzyl or R1 and R2 together form an alkylene group or an alkyl substituted alkylene group.
2. A compound according to Claim 1 wherein R is , R1 is -C2H5, R2 is -n-C4H9, and n is 0.
3. A compound according to Claim 1 wherein R is , R1 is -C2H5, R2 is , and n is 0.
4. A compound according to Claim 1 wherein R is , R1 is -n-C3H7, R2 is -n-C3H7, and n is 0.
5. A compound according to Claim 1 wherein R is , R1 is -n-C4H9, R2 is , and n is 0.
6. A compound according to Claim 1 wherein R is , R1 is -n-C4H9, R2 is , and n is 0.
7. A compound according to Claim 1 wherein R is , R1 is -i-C4H9, R2 is -i-C4H9, and n is 0.
8. A compound according to Claim 1 wherein R is , R1 and R2 together are and n is 0.
9. A compound according to Claim 1 wherein R is , R1 is -C2H5, R2 is , and n is 0.
10. A compound acoording to Claim 1 wherein R is , R1 is -n-C3H7, R2 is , and n is 0.
11. A compound according to Claim 1 wherein R is , R1 is -i-C3H7, R2 is , and n is 0.
12. A compound according to Claim 1 wherein R is , R1 is -CH2CH=CH2, R2 is , and n is 0.
13. A compound according to Claim 1 wherein R is , R1 is -s-C4H9, R2 is , and n is 0.
14. A compound according to Claim 1 wherein R is , R1 is , R2 is , and n is 0.
15. A compound according to Claim 1 wherein R is , R1 is -C2H5, R2 is -CH2CH=CH2, and n is 0.
16. A compound according to Claim 1 wherein R is , R1 is -C2H5, R2 is , and n is 0.
17. A compound according to Claim 1 wherein R is , R1 is -C2H5, R2 is , and n is 0.
18. A compound according to Claim 1 wherein R is , R1 is -C2H5, R2 is , and n is 0.
19. A compound according to Claim 1 wherein R is , R1 is -n-C3H7, R2 is i-C3H7, and n is 0.
20. A compound according to Claim 1 wherein R is , R1 is -s-C4H9, R2 is -s-C4H9, and n is 0.
21. A compound according to Claim 1 wherein R is , R1 and R2 together are and n is 0.
22. A compound according to Claim 1 wherein R is , R1 is -i-C4H9, R2 is -s-C4H9, and n is 0-
23. A compound according to Claim 1 wherein R is , R1 is , R2 is , and n is 0.
24. A compound according to Claim 1 wherein R is , R1 and R2 together are and n is 0.
25. A compound according to Claim 1 wherein R is , R1 is -n-C3H7, R2 is -n-C3H7, and n is 1.
26. A compound according to Claim 1 wherein R is , R1 is C2H5, R2 is -CH2CH=CH2, and n is 1.
27. A compound according to Claim 1 wherein R is , R1 is -C2H5, R2 is -n-C4H9, and n is 1.
28. A compound according to Claim 1 wherein R is , R1 is C2H5, R2 is -s-C4H9, and n is 1.
29. A compound according to Claim 1 wherein R is , R1 is -C2H5, R2 is , and n is 1.
30. A compound according to Claim 1 wherein R is , R1 is -C2H4, R2 is , and n is 1.
31. A compound according to Claim 1 wherein R is , R1 is -C2H5, R2 is , and n is 1.
32. A compound according to Claim 1 wherein R is , R1 is -C2H5, R2 is , and n is 1.
33. A compound according to Claim 1 wherein R is , R1 is -n-C3H7, R2 is -i-C3H7, and n is 1.
34. A compound according to Claim 1 wherein R is , R1 is -n-C3H7, R2 is , and n is 1.
35. A compound according to Claim 1 wherein R is , R1 is -i-C3H7, R2 , and n is 1.
36. A compound according to Claim 1 wherein R is , R1 is CH2CH=CH2, R2 is , and n is 1.
37. A compound according to Claim 1 wherein R is , R1 is n C4H9, R2 is , and n is 1.
38. A compound according to Claim 1 wherein R is , R1 is i-C4H9, R2 is i-C4H9, and n is 1.
39. A compound according to Claim 1 wherein R is , R1 is s-C4H9, R2 is s-C4H9, and n is 1.
40. A compound according to Claim 1 wherein R is , R1 is s-C4H9, R2 is , and n is 1.
41. A compound according to Claim 1 wherein R is , R1 is , R2 is , and n is 1.
42. A compound according to Claim 1 wherein R is , R1 and R2 together are and n is 1.
43. A compound according to Claim 1 wherein R is , R1 and R2 together are and n is 1.
44. A compound according to Claim 1 wherein R is , R1 is -i-C4H9, R2 is -s-C4H9, and n is 1.
45. A compound according to Claim 1 wherein R is , R1 is , R2 is , and n is 1.
46. A compound according to Claim 1 wherein R is , R1 and R2 together are , and n is 1.
47. A compound according to Claim 1 wherein R is , R1 is -C2H5, R2 is -n-C4H9, and n is 0.
48. A compound according to Claim 1 wherein R is , R1 is -C2H5, R2 is -s-C4H9, and n is 0.
49. A compound according to Claim 1 wherein R is , R1 is -C2H5, R2 is , and n is 0.
50. A compound according to Claim 1 wherein R is , R1 is -n-C3H7, R2 is -n-C3H7, and n is 0.
51. A compound according to Claim 1 wherein R is , R1 is -n-C4H9, R2 is , and n is 0.
52. A compound according to Claim 1 wherein R is , R1 is -i-C4H9, R2 is -i-C4H9, and n is 0.
53. A compound according to Claim 1 wherein R is , R1 is -s-C4H9, R2 is -s-C4H9, and n is 0.
54. A compound according to Claim 1 wherein R is , R1 is -i-C4H9, R2 is -s-C4H9, and n is 0.
55. A compound according to Claim 1 wherein R is , R1 and R2 together are and n is 0.
56. A compound accordlng to Claim 1 wherein R is , R1 is , R2 is , and n is 0.
57. A compound according to Claim 1 wherein R is , R1 and R2 together are , and n is 0.
58. A compound according to Claim 1 wherein R is , R1 and R2 together are and n is 1.
59. A compound according to Claim 1 wherein R is , R1 and R2 together are and n is 1.
60. A compound according to Claim 1 wherein R is , R1 is , R2 is , and n is 1.
61. A compound according to Claim 1 wherein R is , R1 is -C2H5, R2 is n-C4H9, and n is 0.
62. A compound according to Claim 1 wherein R is , R1 is -C2H5, R2 is -s-C4H9, and n is 0.
63. A compound according to Claim 1 wherein R is , R1 is C2H5, R2 is , and n is 0.
64. A compound according to Claim 1 wherein R is , R1 is -n-C3H7, R2 i3 -n-C3H7, and n is 0.
65. A compound according to Claim 1 wherein R is , R1 is -i-C4H9, R2 is -i-C4H9, and n is 0.
66. A compound according to Claim 1 wherein R is , R1 is , R2 is , and n is 0.
67. A compound according to Claim 1 wherein R is , R1 is -i-C4H9, R2 is -s-C4H9, and n is 0.
68. A compound according to Claim 1 wherein R is , R1 is -s-C4H9, R2 is -s-C4H9, and n is 0.
69. A compound according to Claim 1 wherein R is , R1 and R2 together are and n is 0.
70. A compound according to Claim 1 wherein R is , R1 is -n-C4H9, R2 is -n-C4H9, and n is 0.
71. A compound according to Claim 1 wherein R is , R1 and R2 together are and n is 0.
72. A compound according to Claim 1 wherein R is , R1 is C2H5, R2 is n-C4H9 and n is 0.
73. A compound according to Claim 1 wherein R is , R1 is C2H5, R2 is i-C4H9, and n is 0.
74. A compound according to Claim 1 wherein R is , R1 is C2H5, R2 is sec.-C4H9, and n is 0.
75. A compound according to Claim 1 wherein R is , R1 is n-C3H7, R2 is n-C3H7, and n is 0.
76. A compound according to Claim 1 wherein R is , R1 is n-C3H7, R2 is i-C3H7, and n is 0.
77. A compound according to Claim 1 wherein R is , R1 is allyl, R2 is allyl, and n is 0.
78. A compound according to Claim 1 wherein R is , R1 is i-C3H7, R2 is i-C4H9, and n is 0.
79. A compound according to Claim 1 wherein R is , R1 is i-C4H9, R2 is i-C4H9, and n is 0.
80. A compound according to Claim 1 wherein R is , R, is sec.-C4H9, R2 is sec.-C4H9, and n is 0.
81. A compound according to Claim 1 wherein R is , R1 is i-C4H9, R2 is sec.-C4H9, and n is 0.
82. A compound according to Claim 1 wherein R is , R1 and R2 taken together are , and n is 0.
83. A compound according to Claim 1 wherein R is , R1 is C2H5, R2 is allyl, and n is 0.
84. A compound according to Claim 1 wherein R is , R1 is C2H5, R2 is cyclohexyl, and n is 0.
85. A compound according to Claim 1 wherein R is , R1 is n-C4H9, R2 is cyclopropylmethyl, and n is 0.
86. A compound according to Claim 1 wherein R is , R1 and R2 together are , and n is 0.
87. A compound according to Claim 1 wherein R is , R1 is cyclopropylmethyl, R2 is cyclopropyl methyl, and n is 0.
88. A compound according to Claim 1 wherein R is , R1 and R2 taken together are , and
89. A compound according to Claim 1 wherein R is , R1 is C2H5, R2 is sec.-C4H9, and n is 1.
90. A compound according to Claim 1 wherein R is , R1 is i-C4H9, R2 is sec.-C4H9, and n is 1.
91. A compound according to Claim 1 wherein R is , R1 is C2H5, R2 is n-C4H9, and n is 1.
92. A compound according to Claim 1 wherein R is , R1 is C2H5, R2 is i-C4H9, and n is 1.
93. A compound according to Claim 1 wherein R is , R1 is i-C3H7, R2 is i-C3H7, and n is 1.
94. A compound according to Claim 1 wherein R is , R1 is i-C3H7, R2 is i-C4H9, and n is 1.
95. A compound according to Claim 1 wherein R is , R1 is sec.-C4H9, R2 is sec.-C4H9, and n is 1.
96. A compound according to Claim 1 wherein R is , R1 is9 CH2CH=CH2, R2 is CH2CH=CH2, and n is 1.
97. A compound according to Claim 1 wherein R is , R1 is n-C3H7, R2 is n-C3H7, and n is 1.
98. A compound according to Claim 1 wherein R is , R1 is C2H5, R2 is CH2CH=CH2, and n is 1.
99. A compound according to Claim 1 wherein R is , R1 is C2H5, R2 is cyclohexyl, and n is 1.
100. A compound according to Claim 1 wherein R is , R1 is C4H9, R2 is cyclopropylmethyl, and n is 1.
101. A compound according to Claim 1 wherein R is , R1 and R2 taken together are and n is 1.
102. A compound according to Claim 1 wherein R is , R1 is cyclopropylmethyl, R2 is cyclopropylmethyl, and n is 1.
103. A compound according to Claim 1 wherein R is , R1 is i-C4H9, R2 is i-C4H9, and n is 1.
104. A compound according to Claim 1 wherein R is , R1 and R2 taken together are , and n is 0.
105. A compound according to Claim 1 wherein R is , R1 and R2 taken together are , and n is 0.
106. A method of controlling undesirable vegetation which comprises applying to the soil an effective amount of a compound having the general structural formula wherein n is 0 or 1, R is selected from the group consisting of tertiary butyl, cyclopropyl, cyclobutyl and cyclopentyl; and R1 and R2 are individually selected from the group consisting of alkyl, alkenyl, cyclopropylmethyl, cyclohexyl, phenyl and benzyl or R1 and R2 together from an alkylene group or an alkyl substituted alkylene group.
107. A method according to Claim 106 wherein R is , R1 is -C2H5, R2 is -s-C4H9, and n is 0.
108. A method according to Claim 106 wherein R is , R1 is -n-C3H7, R2 is -n-C3H7, and n is 0.
109. A method according to claim 105 wherein R is , R1 is -n-C4H9, R2 is -n-C4H9, and n is 0.
110. A method according to Claim 106 wherein R is , R1 is -n-C4H9, R2 is , and n is 0.
111. A method according to Claim 106 wherein R is , R1 is -i-C4H9, R2 is -i-C4H9, and n is 0.
112. A method according to Claim 106 wherein R is , R1 and R2 together are and n is 0.
113. A method according to Claim 106 wherein R is , R1 is -C2H5, R2 is , and n is 0.
114. A method according to Claim 106 wherein R is , R1 is -n-C3H7, R2 is , and n is 0.
115. A method according to Claim 106 wherein R is , R1 is -i-C3H7, R2 is , and n is 0.
116. A method according to Claim 106 wherein R is , R1 is -C2H5, R2 is -n-C4H9, and n is 0.
117. A method according to Claim 106 wherein R is , R1 is -CH2CH=CH2, R2 is , and n is 0.
118. A method according to Claim 106 wherein R is , R1 is -s-C4H9, R2 is , and n is 0.
119. A method according to Claim 106 wherein R is , R1 is , and R2 is , and n is 0.
120. A method according to Claim 106 wherein R is , R1 is -C2H5, R2 is -CH2CH=CH2, and n is 0.
121. A method according to Claim 106 wherein R is , R1 is -C2H5, R2 is , and n is 0.
122. A method according to Claim 106 wherein R is , R1 is -C2H5, R2 is , and n is 0.
123 A method according to Claim 106 wherein R is , R1 is -C2H5, R2 is , and n is 0.
124. A method according to Claim 106 wherein R is , R1 is -n-C3H7, R2 is i-C3H7, and n is 0.
125. A method according to Claim 106 wherein R is , R1 is -s-C4H9, R2 is -s-C4H9, and n is 0.
126. A method according to Claim 106 wherein R is , R1 and R2 together are and n is 0.
127. A method according to Claim 106 wherein R is , R1 is -i-C4H9, R2 is -s-C4H9, and n is 0.
128. A method according to Claim106 wherein R is , R1 is , R2 is , and n is 0.
129. A method according to Claim 106 wherein R is , R1 and R2 together are and n is 0.
130. A method according to Claim 106 wherein R is , R1 is -n-C3H7, R2 is -n-C3H7, and n is 1.
131. A method according to Claim 106 wherein R is , R1 is -C2H5, R2 is CH2CH=CH2, and n is 1.
132. A method according to Claim 106 wherein R is , R1 is -C2H5, R2 is -n-C4H9, and n is 1.
133. A method according to Claim 106 wherein R is , R1 is -C2H5, R2 is -s-C4H9, and n is 1.
134. A method according to Claim 106 wherein R is , R1 is -C2H5, R2 is , and n is 1.
135. A method according to Claim 106 wherein R is , R1 is -C2H5, R2 is , and n is 1.
136. A method according to Claim 106 wherein R is , R1 is -C2H5, R2 is , and n is 1.
137. A method according to Claim 106 wherein R is , R1 is -C2H5, R2 is , and n is 1.
138. A method according to Claim 106 wherein R is , R1 is -n-C3H7, R2 is -i-C3H7, and n is 1.
139. A method according to Claim 106 wherein R is , R1 is -n-C3H7, R2 is , and n is 1.
140. A method according to Claim 106 wherein R is , R1 is -i-C3H7, R2 is , and n is 1.
141. A method according to Claim 106 wherein R is , R1 is CH2CH=CH2, R2 is , and n is 1.
142. A method according to Claim 106 wherein R is , R1 is n-C4H9, R2 is , and n is 1.
143. A method according to Claim 106 wherein R is , R1 is i-C4H9, R2 is i-C4H9, and n is 1.
144. A method according to Claim 106 wherein R is , R1 is s-C4H9, R2 is s-C4H9, and n is 1.
145. A method according to Claim 106 wherein R is , R1 is s-C4H9, R2 is , and n is 1.
146. A method according to Claim 106 wherein R is , R1 is , R2 is , and n is 1.
147. A method according to Claim 106 wherein R is , R1 and R2 together are and n is 1.
148. A method according to Claim 106 wherein R is , R1 and R2 together are and n is 1.
149. A method according to Claim 106 wherein R is , R1 is -i-C4H9, R2 is -s-C4H9, and n is 1.
150. A method according to Claim 106 wherein R is , R1 is , R2 is , and n is 1.
151. A method according to Claim 106 wherein R is , R1 and R2 together are and n is 1.
152. A method according to Claim 106 wherein R is , R1 is -C2H5, R2 is -n-C4H9, and n is 0.
153. A method according to Claim 106 wherein R is , R1 is -C2H5, R2 is -s-C4H9, and n is 0.
154. A method according to Claim 106 wherein R is , R1 is -C2H5, R2 is , and n is 0.
155. A method according to Claim 106 wherein R is , R1 is -n-C3H7, R2 is -n-C3H7, and n is 0.
156. A method according to Claim 106 wherein R is , R1 is -n-C4H9, R2 is , and n is 0.
157. A method according to Claim 106 wherein R is , R1 is -i-C4H9, R2 is -i-C4H9, and n is 0.
158. A method according to Claim 106 wherein R is , R1 is -s-C4H9, R2 is -s-C4H9, and n is 0.
159. A method according to Claim 106 wherein R is , R1 is -i-C4H9, R2 is -s-C4H9, and n is 0.
160. A method according to Claim 106 wherein R is , R1 and R2 together are and n is 0.
161. A method according to Claim 106 wherein R is , R1 is , R2 is , and n is 0.
162. A method according to Claim 106 wherein R is , R1 and R2 together are and n is 0.
163. A method according to Claim 106 wherein R is , R1 and R2 together are , and n is 1.
164. A method according to Claim 106 wherein R is , R1 and R2 together are and n is 1.
165. A method according to Claim 106 wherein R is R1 is , R2 is , and n is 1.
166. A method according to Claim 106 wherein R is , R1 is -C2H5, R2 is n-C4H9, and n is 0.
167. A method according to Claim 106 wherein R is , R1 is -C2H5, R2 is -s-C4H9.
168. A method according to Claim 106 wherein R is , R1 is -C2H5, R2 is , and n is 0.
169. A method according to Claim 106 wherein R is , R1 is -n-C3H7, R2 is -n-C3H7, and n is 0.
170. A method according to Claim 106 wherein R is , R1 is -C4H9, R2 is -i-C4H9, and n is 0.
171. A method according to Claim 106 wherein R is , R1 is , R2 is , and n is 0.
172. A method according to Claim 106 wherein R is , R1 is -i-C4H9, R2 is -s-C4H9, and n is 0.
173. A method according to Claim 106 wherein R is , R1 is -s-C4H9, R2 is -s-C4H9, and n is 0.
174. A method according to Claim 106 wherein R is , R1 and R2 together are and n is 0.
175. A method according to Claim 106 wherein R is , R1 and R2 together are and n is 0.
176. A method according to Claim 106 wherein R is , R1 is -n-C4H9, R2 is -n-C4H9, and n is 0.
177. A method according to Claim 106 wherein R is , R1 and R2 together are and n is 0.
178. A method according to Claim 106 wherein R is , R1 is C2H5, R2 is n-C4H9, and n is 0.
179. A method according to Claim 106 wherein R is , R1 is C2H5, R2 is i-C4H9, and n is 0.
180. A method according to Claim 106 wherein R is , R1 is C2H5, R2 is sec.-C4H9, and n is 0.
181. A method according to Claim 106 wherein R is , R1 is n-C3H7, R2 is n-C3H7, and n is 0.
182. A method according to Claim 106 wherein R is , R1 is n-C3H7, R2 is i-C3H7, and n is 0.
183. A method according to Claim 106 wherein R is , R1 is allyl, R2 is allyl, and n is 0.
184. A method according to Claim 106 wherein R is , R1 is i-C3H7, R2 is i-C4H9, and n is 0.
185. A method according to Claim 106 wherein R is , R1 is i-C4H9, R2 is i-C4H9, and n is 0.
186. A method according to Claim 106 wherein R is , R1 is sec.-C4H9, R2 is sec.-C4H9, and n is 0.
187. A method according to Claim 106 wherein R is , R1 is i-C4H9, R2 is sec.-C4H9, and n is 0.
188. A method according to Claim 106 wherein R is , R1 and R2 taken together are , and n is 0.
189. A method according to Claim 106 wherein R is , R1 is C2H5, R2 is allyl, and n is 0.
190. A method according to Claim 106 wherein R is , R1 is C2H5, R2 is cyclohexyl, and n is 0.
191. A method according to Claim 106 wherein R is , R1 is n-C4H9, R2 is cyclopropylmethyl, and n is 0.
192. A method according to Claim 106 wherein R is , R1 and R2 taken together are and n is 0.
193. A method according to Claim 106 wherein R is , R1 is cyclopropylmethyl, R2 is cyclopropylmethyl, and n is 0.
194. A method according to Claim 106 wherein R is , R1 and R2 taken together are , and n is 0.
195. A method according to Claim 106 wherein R is , R1 is C2H5, R2 is sec.-C4H9, and n is 1.
196. A method according to Claim 106 wherein R is , R1 is i-C4H9, R2 is sec.-C4H9, and n is 1.
197. A method according to Claim 106 wherein R is , R1 is C2H5, R2 is n-C4H9, and n is 1.
198. A method according to Claim 106 wherein R is , R1 is C2H5, R2 is i-C4H9, and n is 1.
199. A method according to Claim 106 wherein R is , R1 is C3H7, R2 is i-C3H7, and n is 1.
200. A method according to Claim 106 wherein R is , R1 is i-C3H7, R2 is i-C4H9, and n is 1.
201. A method according to Claim 106 wherein R is , R1 is sec.-C4H9, R2 is sec.-C4H9, and n is 1.
202. A method according to Claim 106 wherein R is , R1 is CH2CH=CH2, R2 is CH2CH=CH2, and n is 1.
203. A method according to Claim 106 wherein R is , R1 is n-C3H7, R2 is n-C3H7, and n is 1.
204. A method according to Claim 106 wherein R is , R1 is C2H5, R2 iS CH2CH=CH2, and n is 1,
205. A method according to Claim 106 wherein R is , R1 is C2H5, R2 is cyclohexyl, and n is 1.
206. A method according to Claim 106 wherein R is , R1 is C4H9, R2 is cyclopropylmethyl, and n is 1.
207. A method according to Claim 106 wherein R is , R1 and R2 taken together are , and n is 1.
208. A method according to Claim 106 wherein R is , R1 is cyclopropylmethyl, R2 is cyclopropylmethyl, and n is 1.
209. A method according to Claim 106 wherein R is , R1 is i-C4H9, R2 is i-C4H9, and n is 1.
210. A method according to Claim 106 wherein R is , R1 and R2 taken together are , and n is 1.
211. A method according to Claim 106 wherein R is , R1 and R2 taken together are , and n is 1.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US67122676A | 1976-03-29 | 1976-03-29 | |
| US67121976A | 1976-03-29 | 1976-03-29 | |
| US671,226 | 1976-03-29 | ||
| US68110576A | 1976-04-28 | 1976-04-28 | |
| US681,105 | 1976-04-28 | ||
| US671,219 | 1991-03-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1082721A true CA1082721A (en) | 1980-07-29 |
Family
ID=27418223
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA273,155A Expired CA1082721A (en) | 1976-03-29 | 1977-03-03 | Herbicidally active thiocarbamates and sulfoxides |
Country Status (21)
| Country | Link |
|---|---|
| JP (1) | JPS52118425A (en) |
| AR (1) | AR219067A1 (en) |
| AU (1) | AU502225B2 (en) |
| BR (1) | BR7701644A (en) |
| CA (1) | CA1082721A (en) |
| CH (1) | CH629652A5 (en) |
| CS (1) | CS209881B2 (en) |
| DD (1) | DD129610A5 (en) |
| DE (1) | DE2712760A1 (en) |
| DK (1) | DK137777A (en) |
| EG (1) | EG12513A (en) |
| ES (1) | ES457286A1 (en) |
| FR (1) | FR2346328A1 (en) |
| GB (1) | GB1537991A (en) |
| IL (1) | IL51750A (en) |
| NL (1) | NL7703325A (en) |
| NZ (1) | NZ183691A (en) |
| PH (1) | PH14094A (en) |
| PL (1) | PL104608B1 (en) |
| RO (1) | RO73259A (en) |
| SU (1) | SU638235A3 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8007849B2 (en) | 2005-12-14 | 2011-08-30 | International Flavors & Fragrances Inc. | Unsaturated cyclic and acyclic carbamates exhibiting taste and flavor enhancement effect in flavor compositions |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3804873A (en) * | 1971-03-18 | 1974-04-16 | Gulf Research Development Co | Process for manufacturing a liquid thiocarbamate |
| IT972188B (en) * | 1972-10-09 | 1974-05-20 | Montedison Spa | CARBAMOIL SULPHOXIDE COMPOUNDS |
| FR2196120A1 (en) * | 1972-08-14 | 1974-03-15 | Stauffer Chemical Co | Sulphonyl and sulphinyl thiocarbamates - useful as pre or post emergence herbicides, prepd by oxidn of corresp thiocarbamates |
| PH10781A (en) * | 1973-03-29 | 1977-09-06 | Stauffer Chemical Co | Process of manufacturing sulphoxides |
-
1977
- 1977-02-28 AR AR266722A patent/AR219067A1/en active
- 1977-03-02 AU AU22856/77A patent/AU502225B2/en not_active Expired
- 1977-03-03 CA CA273,155A patent/CA1082721A/en not_active Expired
- 1977-03-07 GB GB9420/77A patent/GB1537991A/en not_active Expired
- 1977-03-17 RO RO7789688A patent/RO73259A/en unknown
- 1977-03-17 BR BR7701644A patent/BR7701644A/en unknown
- 1977-03-23 DE DE19772712760 patent/DE2712760A1/en not_active Withdrawn
- 1977-03-23 JP JP3121777A patent/JPS52118425A/en active Pending
- 1977-03-24 NZ NZ183691A patent/NZ183691A/en unknown
- 1977-03-24 CH CH378577A patent/CH629652A5/en not_active IP Right Cessation
- 1977-03-25 FR FR7708955A patent/FR2346328A1/en not_active Withdrawn
- 1977-03-28 NL NL7703325A patent/NL7703325A/en not_active Application Discontinuation
- 1977-03-28 PH PH19595A patent/PH14094A/en unknown
- 1977-03-28 IL IL51750A patent/IL51750A/en unknown
- 1977-03-28 CS CS772050A patent/CS209881B2/en unknown
- 1977-03-28 DD DD7700198100A patent/DD129610A5/en unknown
- 1977-03-29 SU SU772466802A patent/SU638235A3/en active
- 1977-03-29 DK DK137777A patent/DK137777A/en not_active Application Discontinuation
- 1977-03-29 PL PL1977197001A patent/PL104608B1/en not_active IP Right Cessation
- 1977-03-29 ES ES457286A patent/ES457286A1/en not_active Expired
- 1977-03-29 EG EG176/77A patent/EG12513A/en active
Also Published As
| Publication number | Publication date |
|---|---|
| PL104608B1 (en) | 1979-08-31 |
| BR7701644A (en) | 1978-01-03 |
| CH629652A5 (en) | 1982-05-14 |
| NZ183691A (en) | 1979-03-16 |
| DK137777A (en) | 1977-09-30 |
| PL197001A1 (en) | 1978-01-02 |
| CS209881B2 (en) | 1981-12-31 |
| JPS52118425A (en) | 1977-10-04 |
| SU638235A3 (en) | 1978-12-15 |
| AR219067A1 (en) | 1980-07-31 |
| AU2285677A (en) | 1978-09-07 |
| DD129610A5 (en) | 1978-02-01 |
| NL7703325A (en) | 1977-10-03 |
| IL51750A0 (en) | 1977-05-31 |
| ES457286A1 (en) | 1978-06-16 |
| PH14094A (en) | 1981-02-10 |
| FR2346328A1 (en) | 1977-10-28 |
| RO73259A (en) | 1981-06-26 |
| GB1537991A (en) | 1979-01-10 |
| DE2712760A1 (en) | 1977-10-20 |
| IL51750A (en) | 1982-01-31 |
| AU502225B2 (en) | 1979-07-19 |
| EG12513A (en) | 1979-06-30 |
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