CA1081701A - 3-benzyl-2-methylimino-5-phenyl-.delta..sup.4-1,3,4- thiadiazolines and method of combating undesired plant growth - Google Patents
3-benzyl-2-methylimino-5-phenyl-.delta..sup.4-1,3,4- thiadiazolines and method of combating undesired plant growthInfo
- Publication number
- CA1081701A CA1081701A CA277,042A CA277042A CA1081701A CA 1081701 A CA1081701 A CA 1081701A CA 277042 A CA277042 A CA 277042A CA 1081701 A CA1081701 A CA 1081701A
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- delta
- methylimino
- thiadiazoline
- benzyl
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Abstract
ABSTRACT OF THE DISCLOSURE
3-benzyl-2-methylimino-5-phenyl-.DELTA.4-1,3,4-thiadiazolines of general formula
3-benzyl-2-methylimino-5-phenyl-.DELTA.4-1,3,4-thiadiazolines of general formula
Description
~al8:~L70~
3-BENZYL-2-METHYLIMINO-5-PHENYL- ~ -1J3,4-THIADIAZOLINES AND
METHOD OF COMBATING UNDESIRED PLANT GROWTH
Descriptlon of the Invention A class of tautomeric alkyliminothiadiazolines has been disclosed in U. S. patent 3,522,267 to be useful as herbicides, one compound being dlsclosed to be parti cularly useful for combating weeds in root crops, such as sugarbeets or onions.
I have discovered that a novel class of non-tautomeric methyliminothiadiazolines have distinctly different phytotoxic selectivity and are particularly use-ful in combating weeds in grains~ particularly ln wheat and rice fields~ being effective at application rates of less than 4 lb per acre ~4.S kg. per hectare). The novel herbicidal agents are effective against broadleaf weeds belonging to families of which sugar beets, radishes, tomato, alfalfa and coxcomb are representative species~as~well as many pestiferous grasses.
Briefly, my method of combating weeds in grain fields comprises applying to the area where the combating effect is desired a herbicidally effective amount of a compound of the formula:
3-BENZYL-2-METHYLIMINO-5-PHENYL- ~ -1J3,4-THIADIAZOLINES AND
METHOD OF COMBATING UNDESIRED PLANT GROWTH
Descriptlon of the Invention A class of tautomeric alkyliminothiadiazolines has been disclosed in U. S. patent 3,522,267 to be useful as herbicides, one compound being dlsclosed to be parti cularly useful for combating weeds in root crops, such as sugarbeets or onions.
I have discovered that a novel class of non-tautomeric methyliminothiadiazolines have distinctly different phytotoxic selectivity and are particularly use-ful in combating weeds in grains~ particularly ln wheat and rice fields~ being effective at application rates of less than 4 lb per acre ~4.S kg. per hectare). The novel herbicidal agents are effective against broadleaf weeds belonging to families of which sugar beets, radishes, tomato, alfalfa and coxcomb are representative species~as~well as many pestiferous grasses.
Briefly, my method of combating weeds in grain fields comprises applying to the area where the combating effect is desired a herbicidally effective amount of a compound of the formula:
-2-~, i ~ .
N-CH~ ~
R
in which R is methyl or chloro and R' is hydrogen, methyl, trifluoromethyl, benzyloxy, chloro or fluoro, said compound beiny applied either in unmodified form or in the ~orm of a salt with an acid, in combination with a carrier. Water is a preferred carrier, although other liquia and finely divided solid carriers may be used. The invention also comprises the novel 3-benzyl~
methylimino-5-phenyl-~4-1,3,4-thiadiazolines defined above. ~ ~ -la Preparation of the Herbicides ~
,:.. ;.:.: : .:
The compounds of this invention may be pre-pared from commercially available intermediates by means of the procedures which are specifically exempli- -fied below. ~;
2-Methylamino-5-(3-chlorophenyl)-1,3,4-thiadiazole .: , ~::
A well-stirrea mixture of 125 g (0.8 mole~ of
N-CH~ ~
R
in which R is methyl or chloro and R' is hydrogen, methyl, trifluoromethyl, benzyloxy, chloro or fluoro, said compound beiny applied either in unmodified form or in the ~orm of a salt with an acid, in combination with a carrier. Water is a preferred carrier, although other liquia and finely divided solid carriers may be used. The invention also comprises the novel 3-benzyl~
methylimino-5-phenyl-~4-1,3,4-thiadiazolines defined above. ~ ~ -la Preparation of the Herbicides ~
,:.. ;.:.: : .:
The compounds of this invention may be pre-pared from commercially available intermediates by means of the procedures which are specifically exempli- -fied below. ~;
2-Methylamino-5-(3-chlorophenyl)-1,3,4-thiadiazole .: , ~::
A well-stirrea mixture of 125 g (0.8 mole~ of
3-chlorobenzoic acid and 84 g (0.8 mole) of 4-methyl- -thiosemicar~aziae in 700 ml of diox2ne was heated until the solution ~as homogeneous. Phosphorus oxychloride ~123 g, 0.8 mole~ ~7as added dropwise to the resultins solution at a rake to maintain the dioxane at gentle refluxO ,, . :~,. .. .
After the addition ~:as completed, the mixture was heated at Yeflux an adaîtional 45 minutes. The .
" . .
7~1 reaction mixture was allowed to cool to room temperature and the dioxane was decanted into 1,000 ml of 13 percent aqueous sodium hydroxide solution. The remaining in-soluble mass was transferred to a mortar where it was pulverized. The powdered material was added to the aqueous sodium hydroxide-dioxane mixture and the latter was allowed to stir at room temperature for 150 min.
Sufficient water was added to the mixture to produce a final volume of 3,500 ml. The solution was allowed to stir at room temperature for 75 min. and the insoluble material was collected on a Buchner funnel. Recrystalliza-tion of the crude product from 95 percent ethanol afforded 108 ~ of the desired product. m.p. 141-43.
2-Methylimino-3-(44methylbenzyl)-5-(3-chlorophenyl)-~ -1 ! 3,4-thiadiazoline A well-stirred mixture of 150.0 g (0.67 mole) of 2-methylamino-5-(3-chlorophenyl)-1,3,4-thiadiazole, 150.0 g (l.Q7 mole) of a-chloro-p-xylene and 300 ml of dioxane were heated at reflux for 24 hr. The reaction mixture was cooled and approximately 400 ml of hexane was added. The insoluble material was separated by vacuum filtration. The crude salt was added to 600 ml of 10%
methanolic potassium hydroxide. The mixture was allowed to stir at room temperature for 24 hr. The resulting solution was dilutèd to 3,000 ml with water and the in-soluble material was separated by filtration. Recrystalli-zation of the crude material gave 182 g of the title compound. m.p.~94-97.
,. .~ .
After the addition ~:as completed, the mixture was heated at Yeflux an adaîtional 45 minutes. The .
" . .
7~1 reaction mixture was allowed to cool to room temperature and the dioxane was decanted into 1,000 ml of 13 percent aqueous sodium hydroxide solution. The remaining in-soluble mass was transferred to a mortar where it was pulverized. The powdered material was added to the aqueous sodium hydroxide-dioxane mixture and the latter was allowed to stir at room temperature for 150 min.
Sufficient water was added to the mixture to produce a final volume of 3,500 ml. The solution was allowed to stir at room temperature for 75 min. and the insoluble material was collected on a Buchner funnel. Recrystalliza-tion of the crude product from 95 percent ethanol afforded 108 ~ of the desired product. m.p. 141-43.
2-Methylimino-3-(44methylbenzyl)-5-(3-chlorophenyl)-~ -1 ! 3,4-thiadiazoline A well-stirred mixture of 150.0 g (0.67 mole) of 2-methylamino-5-(3-chlorophenyl)-1,3,4-thiadiazole, 150.0 g (l.Q7 mole) of a-chloro-p-xylene and 300 ml of dioxane were heated at reflux for 24 hr. The reaction mixture was cooled and approximately 400 ml of hexane was added. The insoluble material was separated by vacuum filtration. The crude salt was added to 600 ml of 10%
methanolic potassium hydroxide. The mixture was allowed to stir at room temperature for 24 hr. The resulting solution was dilutèd to 3,000 ml with water and the in-soluble material was separated by filtration. Recrystalli-zation of the crude material gave 182 g of the title compound. m.p.~94-97.
,. .~ .
- 4 S-555 .
::-,. .
7~1 Preparation of the hydrochloride salt of 24methylimino-3-benzyl-5-(3-chlorophenyl)--1,3,4-thiadiazoline - :
A well stirred mixture of 13.0 g (0.058 mole) of 2-methylamino-5-~3-chlorophenyl)-1,3,4-thiadiazole, 13.0 g (0.10 mole~ of benzyl chloride and 25 ml of dioxane were heated at reflux for 18 hr. The reaction mixture was cooled, treated with 30 ml of hexane and the insoluble material collected by vacuum filtration. The ;~
crude product was recrystallized from a mixture of chloro-form-hexane to afford 11~5 g of the desired compound.
m p 96-98. ~
Preparation of the 'ri~hloroacetic a~id - -salt of 2-methy~imino-3-benzyl-5-(3-chlorophenyl)~A -1,3,4-thiadiazoline -To a cold solution of 8.0 g (0.025 mole) ;~
2-methylimino-3-benzyl-5-(3-chlorophenyl)-~4-1,3,4-thiadiazoline in 25 ml of benzene was added a solution of 4.1 g (0.025 mole) of trichloroacetic acid in 20 ml - -of benzene. The mixture was allowed to stir at room temperature for 60 minutes and the resulting insoluble material was separated by filtration, affording 11.0 g of the desired salt with a melting point 107-08~.
,,~, . .....
Compounds which have been prepared by the above-described procLdures are listed in Table 1.
' ;
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TABLE I
COMPOUNDS OF THE FORMULA
m p.C or COMPOUND ~BP C/mm Hg) NUMBER R R _ _ 1 chloro hydrogen 72-73 2 chloro 3-methyl 77-78 3 chloro 4-methyl 92-94 4 methyl 3-chloro 78-80 methyl 4-methyl room temp. ;
6 chloro 3-fluoro 77-79 :
7 chloro 4-fluoro 98-100 8 methyl 4-fluoro (HC1 194-96 9 methyl 4-fluoro 53-54 ~ethyl methyl lHCl 193-94 salt) 11 methyl 3-tr fluoro- room temp~
12 chloro hydrogen (HCl 196-98 13 chloro 3-tr fluoro 206-08 salt) 14 chloro 3-trif1uoro- 98-101 chloro 4-methyl (HCl~ 193 96 16 chloro 3-fluoro (HCl 203-05 17 chloxo hydrogen (CCl~CO2H 107~08 18 chloro ~benzyloxy 121-123 ; 19 methyl 4-benzyloxy 91-9 '~
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33L7~1 Use of the Herbicides to Combat Weeds Rice was grown in 4 inch Tufflite (polystyrene foam) pots placed on electric heating mats. The weed species were grown in 12 inch x 3 inch Tu~flite flats.
Greenhouse potting soil was used in both pots and flats.
~ ach herbicide was formulated for application by mixing with a solvent-emulsifier mixture to form a water-dispersible concentrate to which water was then added to form a spray mixture. The solvent emulsifier mixture consisted of 60 percent of a commercial emulsifier sold for agricultural use, 20 percent xylene and 20 percent kerosene, ~ he compounds were applied at various rates, both pré- and post-emergently to different pots and flats 15 at the same time. Application was made at a spray volume -of 40 gal/A with a 6501 nozzle. Herbicides were incorporated in the soil in pre-emergent tests by adding 1/4 inch of soil over the sprayed surface. The tests were evaluated ~our weeks after spraying.
The results were scored on the following numerical scale:
0 = ~o observable injury 1 = temporary injury 2 = some permanent injury ~5 3,- severe injury, some plants died 4 ~ all plants died .
The results are tabulated in Table II. :
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The herbicides of this invention do not present unique formulation problems and may be readily formulated by conventional techniques, employing solvents, diluents, solid carriers and surface active agents which are commer-cially available and are approved for agricultural use.The herbicides of this invention are all nitrogen bases which readily form salts with strong acids and in fact are most conveniently prepared as hyclrohalide salts. They .j, .
may be formulated and applied in salt form if it is more convenient to do so. However, by converting the salt form to the free base as illustrated in procedures disclosed above, a product is obtained which is soluble in a greater variety of organic solvents. This may be considered more desirable from the standpoint of formulation economy. It should be kept in mind that the salt form has a greater weight, mole for mole, than the free base and this must be taken into account in formulating to a desired concentration of active agent.
Some of the compounds listed in Table I have outstanding utility of certain specific types. Compounds numbered 1, 9, 12 and 16 may be used to particular advantage in combination with the commercial hexbicide barban to give broad spectrum weed control in wheat. Compounds numbered ;.. "... ..
18 and 19 are broadly useful in combating weeds in a number of small grain crops, including wheat, oats and ricP. The latter two compounds are readily prepared by the reaction of the commercially available 4-benzyloxybenzyl chloride ;
with either 2-methylamino-5-(3-methylphenyl)-1,3,4-~hiadia- - -zole or 2 methylamino-5 ~3-chlorophenyl)-1,3,4-thiadiazole ~ -24 S-555 - ~ . ~ , . :
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.. ....... . .. . . .
by procedures described above. The reaction is conveniently carried out in refluxing dioxane as a reaction solvent, followed by neutralization of the resulting mixture with methanolic sodium hydroxide and recovery of the product as in the procedure exemplified above for the corres-ponding 4-methylbenzyl compound. The compounds mentioned above which have specific utility for weed control in wheat were evaluated in the greenhouse in comparative tests on wheat and ive associated weed species by the pro-cedure described above and results were rated accordingto the same schedule employed in Table II. The results appear below in Tables III and IV. In areas in which s1lgar hee~,s rape and small grains are grown r a small group of particularly troublesome weeds and volunteer crop plants often flourish in competition with the crops and each other. Compounds 18 and 19 were used pre-emergently according to above-described procedures on sugar beets, ~ape and a small number of associated weeds. Results appear in Table .~ .
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7~1 Preparation of the hydrochloride salt of 24methylimino-3-benzyl-5-(3-chlorophenyl)--1,3,4-thiadiazoline - :
A well stirred mixture of 13.0 g (0.058 mole) of 2-methylamino-5-~3-chlorophenyl)-1,3,4-thiadiazole, 13.0 g (0.10 mole~ of benzyl chloride and 25 ml of dioxane were heated at reflux for 18 hr. The reaction mixture was cooled, treated with 30 ml of hexane and the insoluble material collected by vacuum filtration. The ;~
crude product was recrystallized from a mixture of chloro-form-hexane to afford 11~5 g of the desired compound.
m p 96-98. ~
Preparation of the 'ri~hloroacetic a~id - -salt of 2-methy~imino-3-benzyl-5-(3-chlorophenyl)~A -1,3,4-thiadiazoline -To a cold solution of 8.0 g (0.025 mole) ;~
2-methylimino-3-benzyl-5-(3-chlorophenyl)-~4-1,3,4-thiadiazoline in 25 ml of benzene was added a solution of 4.1 g (0.025 mole) of trichloroacetic acid in 20 ml - -of benzene. The mixture was allowed to stir at room temperature for 60 minutes and the resulting insoluble material was separated by filtration, affording 11.0 g of the desired salt with a melting point 107-08~.
,,~, . .....
Compounds which have been prepared by the above-described procLdures are listed in Table 1.
' ;
~5~ S-555 .
TABLE I
COMPOUNDS OF THE FORMULA
m p.C or COMPOUND ~BP C/mm Hg) NUMBER R R _ _ 1 chloro hydrogen 72-73 2 chloro 3-methyl 77-78 3 chloro 4-methyl 92-94 4 methyl 3-chloro 78-80 methyl 4-methyl room temp. ;
6 chloro 3-fluoro 77-79 :
7 chloro 4-fluoro 98-100 8 methyl 4-fluoro (HC1 194-96 9 methyl 4-fluoro 53-54 ~ethyl methyl lHCl 193-94 salt) 11 methyl 3-tr fluoro- room temp~
12 chloro hydrogen (HCl 196-98 13 chloro 3-tr fluoro 206-08 salt) 14 chloro 3-trif1uoro- 98-101 chloro 4-methyl (HCl~ 193 96 16 chloro 3-fluoro (HCl 203-05 17 chloxo hydrogen (CCl~CO2H 107~08 18 chloro ~benzyloxy 121-123 ; 19 methyl 4-benzyloxy 91-9 '~
~ . ''~ ' .' . . .
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33L7~1 Use of the Herbicides to Combat Weeds Rice was grown in 4 inch Tufflite (polystyrene foam) pots placed on electric heating mats. The weed species were grown in 12 inch x 3 inch Tu~flite flats.
Greenhouse potting soil was used in both pots and flats.
~ ach herbicide was formulated for application by mixing with a solvent-emulsifier mixture to form a water-dispersible concentrate to which water was then added to form a spray mixture. The solvent emulsifier mixture consisted of 60 percent of a commercial emulsifier sold for agricultural use, 20 percent xylene and 20 percent kerosene, ~ he compounds were applied at various rates, both pré- and post-emergently to different pots and flats 15 at the same time. Application was made at a spray volume -of 40 gal/A with a 6501 nozzle. Herbicides were incorporated in the soil in pre-emergent tests by adding 1/4 inch of soil over the sprayed surface. The tests were evaluated ~our weeks after spraying.
The results were scored on the following numerical scale:
0 = ~o observable injury 1 = temporary injury 2 = some permanent injury ~5 3,- severe injury, some plants died 4 ~ all plants died .
The results are tabulated in Table II. :
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The herbicides of this invention do not present unique formulation problems and may be readily formulated by conventional techniques, employing solvents, diluents, solid carriers and surface active agents which are commer-cially available and are approved for agricultural use.The herbicides of this invention are all nitrogen bases which readily form salts with strong acids and in fact are most conveniently prepared as hyclrohalide salts. They .j, .
may be formulated and applied in salt form if it is more convenient to do so. However, by converting the salt form to the free base as illustrated in procedures disclosed above, a product is obtained which is soluble in a greater variety of organic solvents. This may be considered more desirable from the standpoint of formulation economy. It should be kept in mind that the salt form has a greater weight, mole for mole, than the free base and this must be taken into account in formulating to a desired concentration of active agent.
Some of the compounds listed in Table I have outstanding utility of certain specific types. Compounds numbered 1, 9, 12 and 16 may be used to particular advantage in combination with the commercial hexbicide barban to give broad spectrum weed control in wheat. Compounds numbered ;.. "... ..
18 and 19 are broadly useful in combating weeds in a number of small grain crops, including wheat, oats and ricP. The latter two compounds are readily prepared by the reaction of the commercially available 4-benzyloxybenzyl chloride ;
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by procedures described above. The reaction is conveniently carried out in refluxing dioxane as a reaction solvent, followed by neutralization of the resulting mixture with methanolic sodium hydroxide and recovery of the product as in the procedure exemplified above for the corres-ponding 4-methylbenzyl compound. The compounds mentioned above which have specific utility for weed control in wheat were evaluated in the greenhouse in comparative tests on wheat and ive associated weed species by the pro-cedure described above and results were rated accordingto the same schedule employed in Table II. The results appear below in Tables III and IV. In areas in which s1lgar hee~,s rape and small grains are grown r a small group of particularly troublesome weeds and volunteer crop plants often flourish in competition with the crops and each other. Compounds 18 and 19 were used pre-emergently according to above-described procedures on sugar beets, ~ape and a small number of associated weeds. Results appear in Table .~ .
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Claims (26)
1. The method of combating weeds in grain fields which comprises applying to the area where the combating effect is desired a herbicidally effective amount of a compound of the formula in which R is methyl or chloro and R' is hydrogen, methyl; trifluoromethyl; benzyloxy, chloro or fluoro, said compound being applied either in unmodified form or in the form of a salt with an acid in combination with a carrier.
2. The method according to Claim 1 which comprises applying to the area where the combating effect is desired a herbicidally effective amount of 3-benzyl-5-(3-chlorophenyl)-2-methylimino-.DELTA.4-1,3,4-thiadiazoline in combination with a carrier.
3. The method according to Claim 1 which comprises applying to the area where the combating effect is desired a herbicidally effective amount of 5-(3-chloro-phenyl)-3-(3-methylbenzy1)-2-methylimino-.DELTA.4-1,3,4-thia-diazoline in combination with a carrier.
4. The method according to Claim 1 which comprises applying to the area where the combating effect is desired a herbicidally effective amount of 5-(3-chloro-phenyl)-3-(4-methylbenzyl)-2-methylimino-.DELTA.4-1,3,4-thia-diazoline in combination with a carrier.
5. The method according to Claim 1 which comprises applying to the area where the combating effect is desired a herbicidally effective amount of 3-(3-chloro-benzyl)-2-methylimino-5-(?-tolyl)-.DELTA.4-1,3,4-thiadiazoline in combination with a carrier.
6. The method according to Claim 1 which comprises applying to the area where the combating effect is desired a herbicidally effective amount of 3-(4-methyl-benzyl)-2-methylimino-5-(?-tolyl)-.DELTA.4-1,3,4-thiadiazoline in combination with a carrier.
7. The method according to Claim 1 which comprises applying to the area where the combating effect is desired a herbicidally effective amount of 5-(3-chloro-phenyl)-3-(3-fluorobenzyl)-2-methylimino-.DELTA.4-1,3,4-thia-diazoline in combination with a carrier.
8. The method according to Claim 1 which comprises applying to the area where the combating effect is desired a herbicidally effective amount of 5-(3-chloro-phenyl)-3-(4-fluorobenzyl)-2-methylimino-.DELTA.4-1,3,4-thia-diazoline in combination with a carrier.
9. The method according to Claim 1 which comprises applying to the area where the combating effect is desired a herbicidally effective amount of 3-(4-fluoro-benzyl)-2-methylimino-5-(?-tolyl)-.DELTA.4-1,3,4-thiadiazoline in combination with a carrier.
10. The method according to Claim 1 which comprises applying to the area where the combating effect is desired a herbicidally effective amount of 2-methyl-imino-5-(?-tolyl)-3-(3-trifluoromethyl)-benzyl-.DELTA.4-1,3,4-thiadiazoline in combination with a carrier.
11. The method according to Claim 1 which comprises applying to the area where the combating effect is desired a herbicidally effective amount of 5-(3-chloro-phenyl)-2-methylimino-3-(3-trifluoromethylbenzyl)-.DELTA.4-1,3,4-thiadiazoline in combination with a carrier.
12. The method according to Claim 1 which comprises applying to the area where the combating effect is desired a herbicidally ef ective amount of 3-(4-benzyl-oxybenzyl)-5-(3-chlorophenyl)-2-methylimino-.DELTA.4-1,3,4-thiadiazoline in combination with a carrier.
13. The method according to Claim 1 which comprises applying to the area where the combating effect is desired a herbicidally effective amount of 3-(4-benzyl-oxybenzyl)-2-methylimino-5-(p-tolyl)-.DELTA.4-1,3,4-thiadiazoline in combination with a carrier.
14. 3-benzyl-5-(3-chlorophenyl)-2-methylimino-.DELTA.4-1,3,4-thiadiazoline.
15. 5-(3-chlorophenyl)-3-(3-methylbenzyl)-2-methylimino-.DELTA.4-1,3,4-thiadiazoline.
16. 5-(3-chlorophenyl)-3-(4-methylbenzyl)-2-methylimino-.DELTA.4-1,3,4-thiadiazoline.
17. 3-(3-chlorobenzyl)-2-methylimino-5-(m-tolyl)-.DELTA.4-1,3,4-thiadiazoline.
18. 3-(4-methylbenzyl)-2-methylimino-5-(m-tolyl)-.DELTA.4-1,3,4-thiadiazoline.
19. 5-(3-chlorophenyl)-3-(3-fluorobenzyl)-2-methylimino-.DELTA.4-1,3,4-thiadiazoline.
20. 5-(3-chlorophenyl)-3-(4-fluorobenzyl)-2-methylimino-.DELTA.4-1,3,4-thiadiazoline.
21. 3-(4-fluorobenzyl)-2-methylimino-5-(m-tolyl)-.DELTA.4-1,3,4-thiadiazoline.
22. 2-methylimino-5-(m-tolyl)-3-(3-trifluoro-methyl)-benzyl-.DELTA.4-1,3,4-thiadiazoline.
23. 5-(3-chlorophenyl)-2-methylimino-3-(3-trifluoromethylbenzyl)-.DELTA.4-1,3,4-thiadiazoline.
24. 3-(4-benzyloxybenzyl)-5-(3-chlorophenyl)-2-methylimino-.DELTA.4-1,3,4-thiadiazoline.
25. 3-(4-benzyloxybenzyl)-2-methylimino-5-(m-tolyl)-.DELTA.4-1,3,4-thiadiazoline.
26. 3-benzyl-2-methylimino-5-phenyl-.DELTA.4-1,3,4-thiadiazolines of the general formula and salts thereof, wherein R is methyl or chloro, and R' is hydrogen, methyl, trifluormethyl, benzyloxy, chloro or fluoro.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA277,042A CA1081701A (en) | 1977-04-26 | 1977-04-26 | 3-benzyl-2-methylimino-5-phenyl-.delta..sup.4-1,3,4- thiadiazolines and method of combating undesired plant growth |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA277,042A CA1081701A (en) | 1977-04-26 | 1977-04-26 | 3-benzyl-2-methylimino-5-phenyl-.delta..sup.4-1,3,4- thiadiazolines and method of combating undesired plant growth |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1081701A true CA1081701A (en) | 1980-07-15 |
Family
ID=4108508
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA277,042A Expired CA1081701A (en) | 1977-04-26 | 1977-04-26 | 3-benzyl-2-methylimino-5-phenyl-.delta..sup.4-1,3,4- thiadiazolines and method of combating undesired plant growth |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1081701A (en) |
-
1977
- 1977-04-26 CA CA277,042A patent/CA1081701A/en not_active Expired
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