AU477366B2 - Herbicide compositions - Google Patents

Description

59,2 35 n2

This invention is directed to a novel group of

compounds which may be generally described as sulfoxide and

sulfone derivatives of thiocarbamates which are highly

active herbicides. The compounds of the present invention

are represented by the generic formula: 0 /R -0-NI R2

wherein n can be 1 or 2; R can be selected from the group

consisting of lower alkyl, haloalkyl, alkoxyalkenyl and

alkenyl; R, and R2 can be the same or different and can be

selected from the group consisting of lower alkyl,

2 477,3 66

59.235. n 3

cycloalkyl having 3-8 carbon atoms, ae1yoyoa!

alkenyl and alkynyl.

The above-noted compounds can be prepared by

reacting an oxidizing agent such as peracetic acid or

m-chloroperoxybenzoic acid with a thiocarbamate compound

corresponding to the following formula:

0 R3 11 R-S-C-N

^2

wherein R,R, and R2 have been defined above. The reaction

is carried out in the presence of an inert solvent such as

chloroform, methylene chloride, benzene, and toluene, and 0 The at a temperature of from about -25 C. to about 600C.

amount of oxidizing agent used must be at least one molar

equivalent to form the 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. However, the use of these thiocarbamates as

reactive intermediates to form other compounds that have

pesticidal activity is unexpected.

In order to illustrate the merits of the present

invention, the following examples are provided: 3 477,3 66

59,2 35 13 ELA-PLE 1 0 0 n-C 7

02H n-Of7

g. A mixture was formed which contained 12.2

(0.06 mole) of m-chloroperoxybenzoic acid in 200 cc. of

chloroform. This solution was then cooled in an ice bath

to 300C. Then, 9.5 go (0.05 mole) of S-ethyl dipropylthio-

carbamate was rapidly added and the temperature rose

rapidly to 3500°C. and then decreased. The flask containing for the reaction mixture was placed under refrigeration were observed. about an hour wherein white solid crystals 24 hours and The solution was kept under refrigeration for It was then then was filtered while in the cold condition. The combined washed with chloroform and then was dried. of 5% sodium filtrate was washed with 3 portions of 100 cc. cc. of water, dried carbonate solution, 1 portion of 100 on a rotary over magnesium sulfate and concentrated to yield 10.1 g. of evaporator under water pump vacuum, product, n3 1.4834. EXAMPLE 2

0 0 i-0 H9

0 2 H 5 -S-0-N S 4 H9

g. of A solution was formed containing 17.2

m-chloroperoxybenzoic acid in 200 cc. of methylene chloride.

Thereafter, 10.9 g. (0.05 mole) of S-ethyl diisobutylthio- temperature of the carbamate was added rapidly when the

solution was 180°C. The solution rose rapidly to a

4 477,3 66

59,235 73

temperature of 30°C., wherein the reaction mass was placed

in an ice bath to reduce the temperature. 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 of 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, L0- 1.4718.

E ALE 3

0 0 C2 H

A solution was formed in a reaction vessel which

contained 22.3 g. (0.11 mole) of m-chloroperoxjbenzoic 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 35°C. The temperature rose to

41°C., wherein the temperature began to decrease and additional heat was applied to maintain the tenperature of

41°C. 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

sodium carbonate solution and then 2 portions of 100 cc.

of water, dried over magnesium sulfate and concentrated in

a rotary evaporator, first under water pump vacuum and

finally under high vacuum to produce llo9 g. of product,

nfi0 1.4911.

5 477.3 66

59,235 n 4EC.-PLE 4

00 C C2 H 5 -S- d-N 2 M

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 cyclohexyl-

ethylthiocarbamate was added rapidly when the temperature 0 was at -15.5 C. The temperature was allowed to rise to

-14.5 0 and maintained for 2 hours. Thereafter, the

temperature was allowed to reach 19.5°C. The mixture was

filtered and the cake was washed with 2 portions of 25 cc.

methylene chloride and dried in the oven. The combined

filtrate was washed with 4 portions of 100 cc. of 5% solu-

tion of sodium carbonate and 2 portions of 100 cc. of water,

dried over magnesium sulfate and concentrated in a rotary

evaporator, first under water pump vacuum and finally under

high vacuum to yield 10.4 g. of product, n0 1.5120.

EAIMPLE 00 CH2-CH=CH 2

02 n-0 3 7

A solution was formed containing 10.7 g. of

m-chloroperoxybenzoic acid in 200 cc. of methylene chloride.

The solution was then placed in a dry ice bath to maintain a

temperature of -160°C. Thereafter, 9.4 g. (0.05 mole) of ma S-ethyl allylpropylthiocarba te was added rapidly and the

temperature rose to -14.5°C. The reaction was allowed to

6 477,3 66

59.2 35 73

carry out for 2 hours. During the reaction the temperature was allowed to go to 15.5°C. arnd thereafter was taken back dowm to 1°C. 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

solution of sodium carbonate and 2 portions of 100 cc. of water, dried over magnesium sulfate and concentrated in

a rotary evaporator, first under water pump vacuum and finally under high vacuum to yield 9.0 g. of product,

n 1.5015.

MAXLLE 6 oIIIIo CH-CH=Ca c

CH2 -CH=CH 2

A solution was formed containing 10.7 g. (0.525 mole) of m-chloroperoxybenzoic acid in 200 cc. of methylene

chloride in a reaction vessel. The solution was cooled to wherein 9o3 g. (0.05 mole) of S-ethyl diallyl- thiocarbamate was added rapidly. Then, the solution rose to -15°C. The reaction was allowed to be carried out for

hours. At the end of this time the reaction was allowed to reach 18.5°C. 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 100 cc. of 5% sodium carbonate solution and 2 portions

of 100 cc. of water, dried over ragnesiun sulfate and

concentrated in a rotary evaporator to yield 8.8 g. of

product, n0 1.5144.

7 477.3 66

59,235 173 ECA.LE 7

0 0 ,CH3

4(CH 3 =CH

A solution was formed containing 200 co.

methylene chloride with 10.7 g. (0.0525 mole) of m-chloro-

percxybenzoic acid dissolved therein. This solution was

cooled to wherein 8.6 g. (0.05 mole) of S-ethyl

methyl-c-methylpropargylthiocarbamate was added rapidly.

At the end of 2 hours the reaction was removed from the ice bath and allowed to reach 21.500C., wherein the reaction was worked up in a similar manner as set forth in the previous 0 example to yield 6.9 g. of product, n 1.5147. EXAKFLE 8

CICH 2 -CH 2 -CH 2 2

A solution was formed containing 200 cc. of

methylene chloride and 11.6 g. of S-3-chloropropyl- diethylthiocarbanate dissolved therein. This solution was

cooled to -17 0 in a 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 0 allowed to reach 18.5 C. wherein the reaction was worked- up in a similar manner as set forth in the previous example 0 to yield 11.1 g. of product, nb 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

8 477,3 66

59, 2 3 5 i-, representative of those embodied by the present invention.

Cozound numbers have been assisned to then and are used for identification throu,-hout the balance of the s~ecifica- vion.

TABLE I 0 ,B R-S(0) -C-N

2 Compound PhySical llunber R Constnt 30 or C. -2 n nb

1 -C 05 n-C3 H7 n-C3 H7 1 1.4834 2 -C 2H5 i-C H i-C4 H 2 1.4718 3 -C2H n-C3 H7 n-C 3H7 2 1.4574

4 -C2H i-C4 H i-C H 1 1.4834 '49 4 9 n-C 3 H7 n-C H9 1 1.4847 6 n-C3H n-C4 H 9 -C2H5 2 1.4657 7

7 -C2 5 -C2H5 2 1.4-911

8 -C 2H5 -C2 H5 1 1.5122

9 n-C 3H7' n-C3 H 1.4842 7 n-C 3H7 n-C 3H7 n-C 3 n-C,H 7 1*4652 7 3-1 -C2H5 -CH2 -CH=CH =C CH -CH1 -CH 2 2 2 -CH3 1 1.5015 12 n-C 3H7 -C 2 H -C2H 1 1.4888

13 n-CI3- 1 1.5099

14 -C 2H5 -CH 2 -CH=CHi -C114CH=CH2 2 1 1.5144

-9- 4 7 7.3 66

9 2 3 5 n3 TBEI(Cont'd) Phys i cal Cor~moufld Constant an3 or0 C. Number R R -CH CCr-3 -C -CH 11.5147 -C2H5 -CH3 CH2 -CE-C H2 2 yellow Oil 16 2 -CH=CH 2 -CH1 2 -CRT,4H IC 2 1 1.5107 17 n-CRH-l -C 1.5032 1 18 n-C 3 6 -C1 n-0 3 H7 n- 3 H7 1 1.5082 19 -CT-HoR00 2H 5 n-C 3 H7 1 82-90O0. n-'C3 6 -cl -CR3

10 4773 66

59.2 35 /13

Herbicidal Screening Tests As previously mentioned, the novel compounds herein described are phytotoxic compounds which are useful

and valuable in controlling various plant species. Com,pounds of this invention are tested as herbicides in the following manner. Pre-emergence Herbicide 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 is added to dissolve the compound. If the material is not soluble in acetone, another solvent such as water, alcohol or dimethylformamide (DMF) is used instead. When DIh is used, only 0.5 ml. or less is used to dissolve the compound and then another solvent is used to make the volume up to 3 ml. The 3 ml. of solution is sprayed 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 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 iles with loamy sand soil. i, 477,3 66

59,2 35 n3 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 saniguinalis), yellow foxtail (Setaria glauca), watergrass (Echinochloa crusgalli), red oat (Avena sativa), redroot pigweed (Amaranthus retroflexus), Indian mustard (Brassica juncea) and curly dock (Rumex crisous) Ample seeds are planted to give about 20 to 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 850 F. and watered by sprinkling. Two weeks after treatment, the degree of injury or control is determined by comparison with un- treated 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 0 flats are placed in the greenhouse at 70-85 P. and watered daily with a sprinkler. About 10 to 14 days after planting when the primary leaves of the bean plants are almost fully expanded and the first trifoliate leaves are just starting to form, the plants are sprayed. The spray is prepared by weighing out 20 mg. of the test compound, dissolving it in 12. 477.3 66

59,235 ml. of acetone containing 15 Tween 20 and then adding

rl. of water. The solution is sprayed on the foliage

using a io. 152 DeVilbiss atomizer at an air pressure of

The spray concentration is 0.2% and the lb./sq. inch. 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 preemergence test. The results of these tests are shown in Table II.

TABLE II HEPBICIDAL ACTIVITY SCREEIIG RESULTS

Compound Per Cent Control at 8 lb./A

Number Pre-emergence Post-emergence

1 99.7 63

2 74

3 0 33 99 71 4 99 64

6 0 43

7 0 8 95 9 98 47 0 49

11 99.9 78

12 99.7 13 100 88 62 14 39 23

16 0

81 57 17 13 477.3 66

59.2 TABLE II (Cont't) Compound Per Cent Control" at 8 lb. A N7umber Pre-cergence Post-emergence 18 90 84 19 44 67 67

477.3 66

59.2 35

in the pre-emergence test Average for seven plant species the post-emergence test. and for six plant species in TABLE II (Cont'd)

Compound per Cent Control* at 20 Ib/A.

Prefergefce Post-emergence Nunber 2 56

3 19

6 13 0 7 3

in the pre-omergence test Average for seven plant species in the post-emergence test. and for six plant species invention can be used The compounds of the present the compounds can be made in any convenient form. Thus, concentrates, into enulsifiable liquids, emulsifiable other powders, granular or any liquid, wettable powder, 477.3 66

59, 2 3 5 n3 convenient form, and applied to the soil to control the ufliesiire! .ve-e tation.

term's lowir alkyl, alkenyl and alkynyl are to those4ee-e4! havi g straight or branched chain configurations having from 1 to 6 carbon atoms, inclusive.

477,3 66

59.235 n3

The clains defining the invention are as follows: e1. A compound represented by the following generic

formula: 0 R, R-S(0)n-C-N

wherein n is 1 or 2; R is selected from the group consist-

ing of lower alkyl, haloalkyl, alkoxyalkenyl and alkenyl;

R1 and R2 can be the sane or different and can be selected

from the group consisting of lower alkyl, cycloalkyl,

lt'alcyc' oan~'cy1 alkenyl and alkynyl.

2. The compound as set forth in Claim 1 wherein

R is -02R 5 R is n-, 3 H7 R2 is n-C3 H7 and n is 1.

3. The compound as set forth in Claim 1 wherein

R is -0 2 H 5 R is i-C 4 H9 R2 is i-C 4 H9 and n is 2.

4. The compound as set forth in Claim 1 wherein

R is -C 2 H 5 RI is n-C,3H7 R2 is n-C0 H and n is 2.

The compound as set forth in Claim 1 wherein

R is -C2 H 5 R, is i- is i-C 4 H9 and n is 1. 4 H9 2

6. The compound as set forth in Claim 1 wherein

R is n-C 3 R1 is n-0CH 9 is -C 2 H 5 and n is 1. 7

7. The compound set forth in Claim 1 wherein

R is n-C 3 H, R1 is n-C4 H 9 is -02 H 5 and n is 2.

8. The compound set forth in Claim 1 wherein

R is 2 H5 R is R is -C2 H5 and n is 2.

9. The compound as set forth in Claim 1 wherein

0i R2 is -C2 H 5 and n is 1. R is -C2H 5 is

The compound as set forth in Claim 1 wherein

11 477.3 66

59. 235 n3 R is n-C3, 1 is n-C 3 H,7 PR is n-0 3 H, and n is 1. 11. The compound as set forth in Claim 1 wherein Ris n-C 3 R1 is n-C3H7 R2 is n-C 3- l and n is 2. 12. The compound as set forth in Claim 1 wherein R is 2 H5 R1 is -C -CH=CH 2 2 2 is -CH2 -CH2 -CH and n is 1. 13. The compound as set forth in Claim 1 wherein R is n-08 R1 is -02 5 R is -C2H 5 and n is 1. 14. The compound as set forth in Claim 1 wherein

R is n-C 3 H7, R, is -0 2 H 5 is and n is 1.

The compound as set forth in Claim 1 wherein R is -C 2 H5 R is -C2-CH=CH 2, R2 is -CH 2 -HCH=H 2 and n is 1.

16. The compound as set forth in Claim 1 wherein R is -C 2 H5 R1 is -CH 3 R2 is -CH(CH 3 and n is 1.

17. The compound as set forth in Claim 1 wherein

R is -CH2-CH=CH2, R1 is -OH 2 -OH=CH 2 R2 is -CH2-CH=CH 2 and

n is 2. 18. The compound as set forth in Claim 1 wherein

R is n-0 3 Hg-C1, R1 is -C2H5, R2 is -C 2 H5 and n is 1.

19. The compound as set forth in Claim 1 wherein

R is n-0 3 H6 -C1, R1 is n-C 3H, R2 is n-C H7 and n is 1. The compound as set forth in Claim 1 wherein R is -CH=CHO-0 2 H5 is n-C 3 H7 R2 is n-0 3 H7 and n is 1.

21. The compound as set forth in Claim 1 wherein

R is Hg- 1, R1 is H3, R2 is and n is 1.

4 7 7.3 6 6

9 2 35 173

5?~The method of controlling undesirable vegetation co-Toxasi-rg a-p*lving to the locus where co--trol is desired an 'nerbicidally effective amount of a con-polnd

477.3 66

59., 235 n3 represented by the following generic formula: 0 R1 R-S(O)n--

R2

wherein n is 1 or 2; R is selected from the group consisting

of lower alkjl, haloalkyl, alkoxyalkenyl and alkenyl; R1 from and R can be the same or different and can be selected 2

the group consisting of lower alkyl, cycloalkyl, .aJ4- zyfGe4af v1 alkenyl and alkynyl.

83s;. The method as set forth in Claim/.5T wherein R is -0 2 H5 is n-B37' R2 is n-C H and n is 1l 1 zx 59-. The method as set forth in Claimk 57wherein R is -0 2 is i-C4 9 P is i-C H and n is 2. 2 4 9 5 1 The method as set forth in Claim 5? wherein R

is -C 2 H5, is n-C H 3 7 R2 is n-0H7 and n is 2. 1 )61. The method as set forth in Claimt7 wherein R

is -025v B1 is R2 is i-C eg and n is 1. i-C4 9 The method as set forth in Claime7 wherein R n is 1. is n-C.H 7 R 1 is n-C4H 9 E2 is -C2H5 and The method set forth in Claim47 wherein R

is n-C3 H, R1 is n-C4 9 is -C2 H5 and n is 2.

'2q64 The method set forth in Claim,5 7wherein R

R is SR is 2 Hi5 and n is 2. is -C2 H5 R S6 The method as set forth in ClaimT wherein

is -C2 H5 1 is R2 is -C 2 H5 and n is 1.

R c7-&6- The mnethod as set forth in ClainrT,5wherein is n-CE R2 is n-C3 7 and n is 1. R1 is n-C3 H7 7 20 477,366

9 2 3 5f2, ~-1r(heren 1 .32,r, The nethod as set forth in Claim

C3 I is n-C 1 R is n- C F,7 an d n is 2 is R Y3 j&B- as set forth in Claim !,;Tktherein The net~hcd -CTq2-CH-CH3 and n i s is -C w5' P, is _W,2CpHCp 2 R2 is Claim Wgherefin R 3S3e-f %Themethod as set forth in

is n-C 3H' R1 is -C?5g, 2 is -C25- and n is 2 1. as set forth in Claim 5nwherein R The method

F 2 is -jJS and n is 1. is n-C3 H7, Pl is -C2 H 5

Claim T-71wherein R The method as set forth in -C2-CHC=CG 2 and n 1is is -C Rl is -CH2 -CHCH 2 R2 is Claim ?rTwherein R The method as set forth in is CH(CH CE and n is 1. isC 2Hg, B~ is -CE, 1R in Clain wherein 1 The method as set forth 4

R2 is CH2 -CE-CH 2 and n is -CH 2 -CH_CH 2 F1 is -CH-CHCH 2 is 2. in Claim .57twherein R The method as set forth

is n-C 31 1 is -CE 5 R 2 is -C2 5 and n isl1eZ2 in Claim wherein R The method as set forth P1 is n-C 3 112 is n-C H7 and n is 1. is n-C3 H 6 Claim wherein R The method as set forth in R, is n-C3 H7 R2 is n-C3 H7 and n is 1. is CH=CHO-C2 HX5 whereif R as set forth in Claim The method

-CE 3 112 is and n is l. is n-C3 H6 Cl P is

2 o)jwheel 11 s 78. The rethod as set forth in Clai P1 is -C2H, R2 is C2 5 and n isilo is n-C 6 Claim wherein R I5q set forth in 44LJZ9< The method as is -n-C 3 i. 7 and n is 1. is -r-C16-Cl, R, is -n-C 3 H 7 P2 pesticidal active 4 5.1~3A process for manufacturing the following formula: compounds corresponding to 0 R, 11 n-C-Il R2 21' 4777.3 66t

59, 2 3 5 3

wherein n is 1 or 2; R is selected from the group consisting of lower alkyl, haloalkyl, alkoxyalkenyl and alkenyl; R1 and R can be the sane or different and can be selected from the group consisting of lower alkyl, cyclo- alkyl, alkyleyeclkylj alkenyl and alAynl; comprising the

steps of: a. combining an oxidizing agent and a thio- carbar-ate compound ina 4solvent system; said thiocarbamate

having the following formula:

R2

wherein R, Il and R2 have been defined above b. maintain-

ing the temperature between -150C. and 600C.; c. said oxidizing agent being present in an amount of at least one stoichiometric equivalent and not more than two stoichio- metric equivalents. .14.The 4& process as set forth in Claim/15 wherein said oxidizing agent is selected from peracetic acid and n-chloroperoxybenzoic acid.

DATED this FOURTEETTH day of AUGUST, 1973 STAUFFER CHEIMICAL COMPAINY REGENTS OF TIE UIIVESITY OF CALIFORTIA

Patent Attorneys for the Applicant SP'j7SOy PERGUSON

477.3 66