US3707557A - Sulfonyl and sulfinyl phenyl ureas - Google Patents
Sulfonyl and sulfinyl phenyl ureas Download PDFInfo
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- US3707557A US3707557A US88213A US3707557DA US3707557A US 3707557 A US3707557 A US 3707557A US 88213 A US88213 A US 88213A US 3707557D A US3707557D A US 3707557DA US 3707557 A US3707557 A US 3707557A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/26—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
- C07C317/32—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C317/34—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring
- C07C317/38—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring with the nitrogen atom of at least one amino group being part of any of the groups, X being a hetero atom, Y being any atom, e.g. N-acylaminosulfones
- C07C317/42—Y being a hetero atom
Definitions
- R is hydrogen or alkyl of 1 to 4 carbon atoms, R isalkyl of one to four carbon atoms, R is hydrogen or alkyl of one to four carbon atoms, X and Y are hydrogen, halogen of atomic number nine to 35, alkyl of one to four carbon atoms or alkoxy of one to four carbon atoms and m is one or two.
- the compounds are herbicides.
- the present invention is related to substituted ureas which are useful as herbicides. More particularly, the present invention is directed to arylsulfinylaryl ureas and arylsulfonylaryl ureas.
- N-substituted ureas have found use in a variety of commercial applications dependingupon the nature and number of the N-substituents.
- N,N-dialkyl-N-4-(phenoxy) and (phenylthio)phenyl ureas and related ureas are disclosed in US. Pat. No. 3,060,235 as herbicides.
- N,N-alkyl-N'-alkyl-sulfonyl and sulfinylphenyl ureas and related compounds are disclosed in US. Pat. No. 3,326,663, as being useful herbicides.
- N,N-dialkyl-N-4-(arylsulfinyl or sulfonyl)aryl ureas of the formula atoms R is alkyl of one tofour carbon atoms
- R is hydrogen oralkyl of one to four carbon atoms
- X and Y are hydrogemhalogen of atomic number nine to 35
- m is one or two are .excellent herbicides and in many applications are unexpectedly superior to the prior art compounds.
- R - is hydrogen or alkyl of one to fourcarbon atoms, preferably methoxy.
- Y is preferably in the para position.
- halogen substituents of the compounds'of the present invention are preferably chlorine or fluorine.
- radicals which R and R may represent are methyl, ethyl, 'n-propyl, isopropyl, n-butyl and isobutyl.
- radicals which R may represent are hydrogen, methyl, ethyl, n-propyL-isopropyl, n-butyl and isobutyl.
- Typical radicals which X-and Y may represent are hydrogen, fluorine, chlorine, bromine, methyl, ethyl, n-
- the compounds of the present invention may be represented by the following formula I o
- R is hydrogen or alkyl of one to four carbon atoms
- R is alkyl of one to four carbon atoms
- R is hydrogen or alkyl of one to four carbon atoms
- X and Y are hydrogen, halogen of atomic. number 9 to 35 (fluorine, chlorine or bromine), alkyl individually of one to four carbon atoms or alkoxy individually of one to four carbon atoms (X and Y may be the same or different)
- m is l or 2.
- the compounds of the present invention may be represented by the above formula wherein R is hydrogen or alkyl of one to two carbon atoms, preferably hydrogen or methyl, R is alkyl of one to two carbon atoms, preferably methyl, R is hydrogen or alkyl of one to two carbon atoms, preferably hydrogen or methyl, Y is hydrogen, halogen of atomic number nine to 35 or alkyl of one to four carbon atoms, preferably methyl,.
- X is hydrogen, halogen of atomic number nine to 35, alkyl of one to four carbon atoms preferably methyl, or alkoxy of one to four carbon fonyl )phenyl urea.
- the ureas of the present invention may be prepared as follows. v
- the initial urea intermediate is most conveniently made by adding the appropriate phenylor substitutedphenyl isocyanate to a dialkylamine, such as dimethylamine, in a relatively non-polar solvent, such as benzene or toluene. Thereaction may be written as A temperature of 2550C. usually is sufficient, but
- amine may be added to the isocyanate.
- the insoluble urea product is isolated by filtration and generally is pure enough to be used without further purification.
- the urea intermediate can be made from a suitable substituted aniline and a dialkyl carbamyl chloride, using a basic acceptor, such as triethylamine.
- reaction may be'written-as The N,N-dialltyl-N'-phenyl"or .substituted :phenyl urea, in a solvent which at least partially dissolves the urea intermediate, isthen reacted with an appropriate sulfenylchlor ide, such as phenylsulfenyl chloride or pchlorophenylsulfenylchloride.
- Di -methylformamide is suitable as a solvenLA' tertiary amine, such as pyridine or triethylamine, may be used as a basic acceptor.
- reaction is carried out at temp ratures in theran'ge of C. to 50C., preferably '2030C.' Reactions usually require from 0.5 to l hours to complete.
- the reac tion is usually completed at high'temperatures. Dilution of the product-solution with water results in precipita tion of the product, which may be filtered and washed with water to remoye' any amine.
- hydrochloride..'lhe product may be-purified byflrecrystallization from an aromatic hydrocarbon or acetonitrile.
- Oxidizers for this reaction include hydrogen peroxide, peracetic acid, perbenzoic acid, etc. m-Chloroperbenzoic acid is preferred. Netherlands Pat. No. 65/12259 teaches the pe'rbenzoic acid oxidation of sulfides.
- the sulfides are oxidized to sulfoxides or sulfones by adding 1 or 2 moles, respectively, of oxidizing agent to the sulfide in a suitable solvent.
- oxidizing agent 1 or 2 moles, respectively, of oxidizing agent to the sulfide in a suitable solvent.
- m-Chloroperbenzoic acid in chloroform or hydrogen peroxide in glacial acetica'cid may be used to effect these oxidations.
- the oxidations are usually carried out at temperatures in the range of 0C. to 50C. Low temperatures are preferred.
- the reactants no longer give a positive potassium iodide test.
- the product is a solid material, which may be recovered by filtration and purified by crystallization from asolventsuch as acetonitrile.
- N,N-dimethyl-N-3-methyl-4-(4- chlorophenylt hio)phenyl urea Twenty g. of N,N -dimethyl-N -m-tolylurea and 10 ml. pyridine werecombined in ml. dimethylforma mide and stirred in an ice bath while 22 of pchlorophenylsulfenyl chloride was added slowly. After being stirred one hour at room temperature, the reac tion mixture was added to-750 ml. of ice and water plus a little mixed hexane.
- Seeds of the test vegetation were planted in a pot of soil and the urea solution was sprayed uniformly onto the soil surface at a-dose of 100 micrograms per cm
- the pot was watered and placed in a greenhouse at a temperature of about 80-85F.
- the pot was watered intermittently and was observed for-seedling emergence, health of emerging seedlings, etc. for a 3-week period.
- the herbicidal effectiveness of the urea was rated based onthe physiological i observations.
- a 0 'to 100 scale was used; 0 representing no phytotoxicity, 100 representing complete kill.
- the test urea was formulated in the same manner as 1 described above for the pre-emergence test.
- the conureas of the present invention will be applied directly to centration of the urea in this formulation was 5000 ppm.
- This formulation was uniformly sprayed on the pot containing 24-day-old plants (approximately 15 to 25 plants per pot) at a dose of 100 micrograms per cm.
- the pots were then placed in a greenhouse at a temperature of 85F. and then watered intermittently attheir bases as needed. The plants were observed periodically for phytotoxic effects and physiological and morphological responses to the treatment. After 3 weeks the herbicidal effectiveness of the urea was rated based on these observations. A 0 to 100 scale was used; I
- the general location'of application i.e., sheltered areas such .a's-greenhouses as compared to exposed areas such as field, as well as the desired type vof control.
- sheltered areas such .a's-greenhouses as compared to exposed areas such as field
- desired type vof control for pre-emergent control of most plants dosages in the range of about 0.5 to 20 lbs. per acre will be-used. Such administration will give a concentration .of about 2 to 80 ppm. ure'a distributed throughout 0.1 acre-foot.
- compositions containing about 0.5 to 8 lbs. urea per 100 gal. spray will be used.'Such application is equivalent to about 0.5 to 20 lbs. urea per acre.
- the herbicidal compositions of this invention comprise a herbicidal amount of one or more of the above described ureas intimately admixed with a biologically inert carrier.
- the carrier may be a liquid diluent such as water or acetone or a solid.
- the solid may be in the form of dust powder or granules.
- These compositions will also usually contain adjuvants such as a wetting or dispersing agent to facilitate their penetration into the plant growth media or plant tissue and generally enhance theireffectiveness.
- These compositions may also contain other pesticides, stabilizers, conditioners,
- R is hydrogen or methyl
- R is methyl
- X and Y are hydrogen, fluorine, chlorine, methyl or methoxy.
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Abstract
Compound of the formula
WHEREIN R1 is hydrogen or alkyl of 1 to 4 carbon atoms, R2 is alkyl of one to four carbon atoms, R3 is hydrogen or alkyl of one to four carbon atoms, X and Y are hydrogen, halogen of atomic number nine to 35, alkyl of one to four carbon atoms or alkoxy of one to four carbon atoms and m is one or two. The compounds are herbicides.
WHEREIN R1 is hydrogen or alkyl of 1 to 4 carbon atoms, R2 is alkyl of one to four carbon atoms, R3 is hydrogen or alkyl of one to four carbon atoms, X and Y are hydrogen, halogen of atomic number nine to 35, alkyl of one to four carbon atoms or alkoxy of one to four carbon atoms and m is one or two. The compounds are herbicides.
Description
United States Patent Brown, deceased SULFONYL AND SULFINYL PHENYL UREAS Inventor: Melancthon Starr Brown, late of Berkeley, Calif. by Gustave K. Kohn, administrator Assignee: Chevron Research Company, San
Francisco, Calif.
Filed: Nov. 9, 1970 Appl. No.: 88,213
U.S. c1. ..260/553 A, 71/120 Int. Cl ....'.C07c 127/18 Field'of Search ..260/553 A References Cited UNITED STATES PATENTS Martin et al. ..260/553 A [451 Dec. 26, 1972 Primary Examiner-LeoniZitver Assistant Examiner-Michael W. Glynn Attorney-G. F. Magdebur'geg john Stoner, Jr
J. A; Bucharianjrfand kaymond Owyang wherein R is hydrogen or alkyl of 1 to 4 carbon atoms, R isalkyl of one to four carbon atoms, R is hydrogen or alkyl of one to four carbon atoms, X and Y are hydrogen, halogen of atomic number nine to 35, alkyl of one to four carbon atoms or alkoxy of one to four carbon atoms and m is one or two. The compounds are herbicides.
7 Claims, No Drawings SULFONYL AND SULFINYL PHENYL UREAS BACKGROUND OF THE INVENTION 1. Field I The present invention is related to substituted ureas which are useful as herbicides. More particularly, the present invention is directed to arylsulfinylaryl ureas and arylsulfonylaryl ureas. I
2. Prior Art N-substituted ureas have found use in a variety of commercial applications dependingupon the nature and number of the N-substituents. Thus, for example, N,N-dialkyl-N-4-(phenoxy) and (phenylthio)phenyl ureas and related ureas are disclosed in US. Pat. No. 3,060,235 as herbicides. Also N,N-alkyl-N'-alkyl-sulfonyl and sulfinylphenyl ureas and related compounds are disclosed in US. Pat. No. 3,326,663, as being useful herbicides.
SUMMARY OF THE INVENTION It has now been found that N,N-dialkyl-N-4-(arylsulfinyl or sulfonyl)aryl ureas of the formula atoms, R is alkyl of one tofour carbon atoms, R is hydrogen oralkyl of one to four carbon atoms, X and Y are hydrogemhalogen of atomic number nine to 35, alkyl of one to four carbon atoms or alkoxy of one'to four carbon atoms and m is one or two are .excellent herbicides and in many applications are unexpectedly superior to the prior art compounds.
DESCRIPTION OF THE INVENTION wherein R -is hydrogen or alkyl of one to fourcarbon atoms, preferably methoxy. Y is preferably in the para position.
The halogen substituents of the compounds'of the present invention are preferably chlorine or fluorine.
Examples of radicals which R and R may represent are methyl, ethyl, 'n-propyl, isopropyl, n-butyl and isobutyl. f
Representative radicals which R may represent are hydrogen, methyl, ethyl, n-propyL-isopropyl, n-butyl and isobutyl.
Typical radicals which X-and Y may represent are hydrogen, fluorine, chlorine, bromine, methyl, ethyl, n-
propyl, isopropyl, n-butyl, isobutyl, methoxy, ethoxy,
' N-methyl-N-ethyl-N-3-ethoxy-4-(o-chlorophenylsul- The compounds of the present invention may be represented by the following formula I o In wherein R is hydrogen or alkyl of one to four carbon atoms, R is alkyl of one to four carbon atoms, R is hydrogen or alkyl of one to four carbon atoms, X and Y are hydrogen, halogen of atomic. number 9 to 35 (fluorine, chlorine or bromine), alkyl individually of one to four carbon atoms or alkoxy individually of one to four carbon atoms (X and Y may be the same or different), and m is l or 2.
Preferably the compounds of the present invention may be represented by the above formula wherein R is hydrogen or alkyl of one to two carbon atoms, preferably hydrogen or methyl, R is alkyl of one to two carbon atoms, preferably methyl, R is hydrogen or alkyl of one to two carbon atoms, preferably hydrogen or methyl, Y is hydrogen, halogen of atomic number nine to 35 or alkyl of one to four carbon atoms, preferably methyl,.X is hydrogen, halogen of atomic number nine to 35, alkyl of one to four carbon atoms preferably methyl, or alkoxy of one to four carbon fonyl )phenyl urea.
The ureas of the present invention may be prepared as follows. v
The initial urea intermediate is most conveniently made by adding the appropriate phenylor substitutedphenyl isocyanate to a dialkylamine, such as dimethylamine, in a relatively non-polar solvent, such as benzene or toluene. Thereaction may be written as A temperature of 2550C. usually is sufficient, but
.temperature up to reflux may be used. Alternately, the
amine may be added to the isocyanate. The insoluble urea product is isolated by filtration and generally is pure enough to be used without further purification.
In the event that the desired isocyanate is not available, the urea intermediate can be made from a suitable substituted aniline and a dialkyl carbamyl chloride, using a basic acceptor, such as triethylamine. Thus:
X a... M
' reaction may be'written-as The N,N-dialltyl-N'-phenyl"or .substituted :phenyl urea, in a solvent which at least partially dissolves the urea intermediate, isthen reacted with an appropriate sulfenylchlor ide, such as phenylsulfenyl chloride or pchlorophenylsulfenylchloride. Di -methylformamide is suitable as a solvenLA' tertiary amine, such as pyridine or triethylamine, may be used as a basic acceptor. The
The reactionis carried out at temp ratures in theran'ge of C. to 50C., preferably '2030C.' Reactions usually require from 0.5 to l hours to complete. When the reactants are mixed at low temperatures, the reac tion is usually completed at high'temperatures. Dilution of the product-solution with water results in precipita tion of the product, which may be filtered and washed with water to remoye' any amine. hydrochloride..'lhe product may be-purified byflrecrystallization from an aromatic hydrocarbon or acetonitrile.
The'oxidation-of the sulfide to a sulfoxide or to a sul-' Several methods are available for carrying out this conversion,'such as oxidation by nitric acid, potassium permanganate, potassium dichromate, etc.; but the preferred'method is by'peroxidic oxidation. Oxidizers for this reaction include hydrogen peroxide, peracetic acid, perbenzoic acid, etc. m-Chloroperbenzoic acid is preferred. Netherlands Pat. No. 65/12259 teaches the pe'rbenzoic acid oxidation of sulfides.
' The sulfides are oxidized to sulfoxides or sulfones by adding 1 or 2 moles, respectively, of oxidizing agent to the sulfide in a suitable solvent. m-Chloroperbenzoic acid in chloroform or hydrogen peroxide in glacial acetica'cid may be used to effect these oxidations. The oxidations are usually carried out at temperatures in the range of 0C. to 50C. Low temperatures are preferred. Upon completion of the reaction, the reactants no longer give a positive potassium iodide test. The product is a solid material, which may be recovered by filtration and purified by crystallization from asolventsuch as acetonitrile.
"Also see U.S. Pat..No. 3,060,235 for disclosure as to' the preparation 'of certain N,N-dialkyl-N' phenylthiophenyl'ureas.
the following examples. EXAMPLE '1 N ,N-'di me thyl N-m-chlorophenyl a..-
1 'Eighteen g; (0.4 mole) 'of dimethylaminewas added gradually to 50 g. (0.33- mole) of m-chlorophenylisow The preparationof the compounds of the presentinvention is illustrated more particularly by reference to cyanate in 500 cc benzene, cooling slightly to maintain a temperature of about 30C. The mixture was allowed to stir overnight at room temperature. The product was collected'on a Buchner funnel, washed with benzene, and dried. The :62 g. of product, which meltedat l44l47C., represents a percent yield.
EXAMPLE 2 N,N-dimethyl-N-3-methyl-4-(4- chlorophenylt hio)phenyl urea Twenty g. of N,N -dimethyl-N -m-tolylurea and 10 ml. pyridine werecombined in ml. dimethylforma mide and stirred in an ice bath while 22 of pchlorophenylsulfenyl chloride was added slowly. After being stirred one hour at room temperature, the reac tion mixture was added to-750 ml. of ice and water plus a little mixed hexane. The solid product was collected on a Buchner funnel, washed with'water and hexane, then recrystallized from acetonitrile. There 1 wasrecovered 36 g. of product melting at l 65 -168C., which represents 64 percent yield. The analysis was:
Found Calculated S 10.00 9.74 Cl I 1.39
EXAMPLE 3 -'N,N-dimethyl-N-3-methyl-4-(4- chloro-phenylsulfinyl)phenyl urea the residual crude product was purified by recrystallization from acetonitrile. There was recovered 6.3 g. of solid, which melted at l6817lC. and analyzed as follows:
Calculated I Found S 9.49 9.52 CI 10.53 10.48
EXAMPLE4 7 N,N-dimethyl-N 3 methyl-4-(4- chloro -phenylsulfonyl)phenyl urea Eight g. of
was stirred as' 10.5 g. m-chloroperbenzoic acid was added in increments with a slight exothermicity. The
reaction mixture was stirred overnight at room tem- N,N-dimethylI-N'--3-methyl-4 (4- chlorophenylthio)phenyl urea in 250 cc chloroform perature. It was then washed with saturated aqueous Calculated Found s 9.07 8.86 Cl 10.05 10. 19
Other compounds of the present invention were prepared in similar fashion to the above examples and are tabulated in Table l.
TABLE I Element Analysis----% 7 S C1 Melting Compound calc.- found calc. found Point C. N,N-dimethyI-N'-4-(pchlorophenylsulfinyl) phenyl urea N,N-din1ethyl-N'-4-(pchlorophenylsulfonyl) phenyl urea N,N-dimethyl-N'-3- methyl-4-(p-tolylsulfinyl)phenyl urea N.N-dimethyl-N-3- methyl-4-(p-tolylsulfonyl)phenyl urea 1 N,N-dimethyl-N'-3- methyl-4-(phenylsulfinyl) phenyl urea N,N-dimethy1-N'3- methyl-4-(phenylsulfonyl)phenyl urea N,Ndimethyl-N-3- methoxy-4-(pchlorophenylsulfinyDphenyl urea N,N-dimethyl-N'-3- methoxy-4-(p-chlorophenylsulfonyl)phenyl urea N,N-dimethyl-N'-3- -chloro4-(p-chlorophenylsulfonyl)phenyl urea N-methyl-N'-methyl- N'-4-(p-chlorophenylsulfonyl)phenyl urea N-methy1-N'-methyl N'-2-fluoro-4- (p-chlorophenylsulfonyl)phenyl urea 9.00 9.94 ;l0.28l10-1l4 nitrogen UTILITY and seedlings. For post-emergence applications the Preand post-emergence herbicidal tests on representative ureas of this invention were made using the following methods:
PRE-EMERGENCE TEST An acetone solution of the test ureas. was prepared by mixing 750 mg. urea, 220 mg.- of a nonionic surfactant and 25 ml. ofacetone.- This solution was added to approximately 125 ml. of water, containing 156 mg. of
surfactant.
Seeds of the test vegetation were planted in a pot of soil and the urea solution was sprayed uniformly onto the soil surface at a-dose of 100 micrograms per cm The pot was watered and placed in a greenhouse at a temperature of about 80-85F. The pot was watered intermittently and was observed for-seedling emergence, health of emerging seedlings, etc. for a 3-week period. At the endof'this period the herbicidal effectiveness of the urea was rated based onthe physiological i observations. A 0 'to 100 scale was used; 0 representing no phytotoxicity, 100 representing complete kill.
POST-EMERGENCE TEST The test urea was formulated in the same manner as 1 described above for the pre-emergence test. The conureas of the present invention will be applied directly to centration of the urea in this formulation was 5000 ppm. This formulation was uniformly sprayed on the pot containing 24-day-old plants (approximately 15 to 25 plants per pot) at a dose of 100 micrograms per cm. The pots were then placed in a greenhouse at a temperature of 85F. and then watered intermittently attheir bases as needed. The plants were observed periodically for phytotoxic effects and physiological and morphological responses to the treatment. After 3 weeks the herbicidal effectiveness of the urea was rated based on these observations. A 0 to 100 scale was used; I
0 representing no phytotoxicity, 100 representing complete kill.
The'results of these testsappear in Table II.
TABLE II Herbicidal Effectiveness Pre/Post CompoundO W C M P L N,N-dimethyl-N'-4- (p-chlorophenylsulfinyl) phenyl urea 99/ 100/ 100/ 100/'100/100 100/100 100 100 100 100 N,N-dimethyl-N'-4- (p-chlorophenylsulfonyl) phenyl urea 99/ 96/ 100/ 100/ 100/100 100/100 100 100 N,N-dimethyl -N-3- methyl-4-(p-chlorophenylsulfinyl)phenyl urea 78/ 78/ 99/ 100/ 100/100 100/100 100 100 100 I00 N,N-dimethyl-N'-3- -methyl-4 phenylsulfonyl)phenyl urea 1 90/100 100100! 100 100/100 100/100 60 100 60 100 N,N-dimethyl-N'-3- methyl-4-(p-tolylsulfinyl)phenyl urea /90 60/ 78/ 100/ 100/100 100/100 90 90 I00 N,N-dimethy1-N'-3-' methyl-4-(p-tolylsulfonyl) phenylurea- 100/ 60/ 100/ 100/100 100/ 100/100 N.N-'dimethyl-N-3- methyl-4-(phenylphenyl urea N,N-dimethyl-N'.-3- methyl-4-(phenyl- I sulfonyl) phenyl urea t 96/ 100/ 100/ /100 100/100 -l00. l 00100 N,N-dimethyl-N'-3- 3 methoxy-4-(pchlorophenylsulfinyl )phenyl I 78/100 -methoxy'-4-(pchlorophenyli I sulfinyhphenyl urea N.N-di'mcthyl-'N"-3 "/l60/ 78/96 100/ 100/1 00 methoxy-4-( p-chloro 100 Y 100 v 7 s 47 s 155;- 100/ 1 0 100 100/1'00 O Wild Oats (Avgnafama):
W Watergrass (Echinochlod crusgalli) C Crabgrass (Digimria sanguinalis) M Mustard (Braxsica arvensis) L Lambsquarter (C henopodium albuni) Compoundsof the present invention are, in general,
significantly [superior to the phenylthiophenyl urea compounds of the prior art. Thus, for example, the many: compounds of the present invention are significantly more effective as preand post-emergence herbicides at lower application concentrations than related compounds of the .prior art. Thus using the procedures of the above tests, but using smaller dosages, .the following representative results were obtained as shown in Table Ill.
' p-chlorophenylthio) chlorophenylthio)phenyl urea (Comparison compound) TABLE 111(0 Post ,Conc. Compound meglcm I r 33 .72 100-100* methyl-A- I (p-chlorophenylsulfinyl)phenylurea N,N-dimethyl-N 33' 88 -93" .3-methyl-4- (p-chlorophenylsulfonyl)phenyl urea N,N-dimethyl-N' 33 j -40 .17 33* 3-me'thyl-4-, (p-chlorophenylithio)phenyl urea (Comparison compound) g N,N-dimethyl-N'- 33 100 100 3-methyl-4- (ply s fi yh' phenyl urea N,N-dimethy1-N-' 33 95 67 3-methy1-4- (p-tolylsulfonyl) phenylurea" N,N-dimethyl-N' 33 13 3 0 88 50 -3-methyl-4- g (p-tolylthio) phenyl urea (Comparison compound)- The amount of the urea administered will vary with the particular plant part or. plant growth medium which i is to be contacted, the general location'of application, i.e., sheltered areas such .a's-greenhouses as compared to exposed areas such as field, as well as the desired type vof control. For pre-emergent control of most plants dosages in the range of about 0.5 to 20 lbs. per acre will be-used. Such administration will give a concentration .of about 2 to 80 ppm. ure'a distributed throughout 0.1 acre-foot. For post-emergence application, such as foliar spray application, compositions containing about 0.5 to 8 lbs. urea per 100 gal. spray will be used.'Such application is equivalent to about 0.5 to 20 lbs. urea per acre.
' The herbicidal compositions of this invention comprise a herbicidal amount of one or more of the above described ureas intimately admixed with a biologically inert carrier. The carrier may be a liquid diluent such as water or acetone or a solid. The solid may be in the form of dust powder or granules. These compositions will also usually contain adjuvants such as a wetting or dispersing agent to facilitate their penetration into the plant growth media or plant tissue and generally enhance theireffectiveness. These compositions may also contain other pesticides, stabilizers, conditioners,
fillers and the like..'
. As will be evident to those skilled in the art, various modifications on this invention can be made or ,followed, in the light of the foregoing disclosure anddiscussion, without departing from the spirit or scope ,of. the disclosure or from the scope of the following claims.
What is claimed is: 1, A compound of the formula wherein alkyl of one to four carbon atoms, R is alkyl of one to four carbon atoms R is methyl, R is methyl and R is hydrogen or methyl.
4. A compound of claim 2 wherein X is hydrogen, halogen of atomic number nine to 35, alkyl of 1 to 4 carbon atoms, or alkoxy of one to four carbon atoms and Y is hydrogen, halogen of atomic number nine to 35, or alkyl of one to four carbon atoms.
5 A compound of claim 1 wherein the halogens are of atomic number 9 to 17.
6. A compound of claim 1 wherein R is hydrogen or methyl, R is methyl, R is hydrogen or methyl, X and Y are hydrogen, fluorine, chlorine, methyl or methoxy.
7. A compound of-claim 6 wherein m' is l, R and R are methyl, R and X are hydrogen, and R is p.-chl0ro.
Claims (6)
- 2. A compound of claim 1 wherein R1 is hydrogen or alkyl of one to two carbon atoms, R2 is alkyl of one to two carbon atoms and R3 is hydrogen or alkyl of one to two carbon atoms.
- 3. A compound of claim 1 wherein R1 is hydrogen or methyl, R2 is methyl and R3 is hydrogen or methyl.
- 4. A compound of claim 2 wherein X is hydrogen, halogen of atomic number nine to 35, alkyl of 1 to 4 carbon atoms, or alkoxy of one to four carbon atoms and Y is hydrogen, halogen of atomic number nine to 35, or alkyl of one to four carbon atoms.
- 5. A compound of claim 1 wherein the halogens are of atomic number 9 to 17.
- 6. A compound of claim 1 wherein R1 is hydrogen or methyl, R2 is methyl, R3 is hydrogen or methyl, X and Y are hydrogen, fluorine, chlorine, methyl or methoxy.
- 7. A compound of claim 6 wherein m is 1, R1 and R2 are methyl, R3 and X are hydrogen, and R4 is p-chloro.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US8821370A | 1970-11-09 | 1970-11-09 |
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| US3707557A true US3707557A (en) | 1972-12-26 |
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| US88213A Expired - Lifetime US3707557A (en) | 1970-11-09 | 1970-11-09 | Sulfonyl and sulfinyl phenyl ureas |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3978123A (en) * | 1973-07-12 | 1976-08-31 | Chevron Research Company | Herbicidal n-alkylsulfoxymethyl-and-n-alkylsulfonyl-methyl-n-aryl |
| US3988300A (en) * | 1973-05-31 | 1976-10-26 | American Cyanamid Company | Benzophenone ureas and method for utilizing the same |
| US4026697A (en) * | 1973-05-31 | 1977-05-31 | American Cyanamid Company | Method for utilizing benzophenone ureas |
| EP0036390A2 (en) * | 1980-03-18 | 1981-09-23 | Ciba-Geigy Ag | Diphenyl ether ureas with herbicidal activity |
| US4315768A (en) * | 1978-08-25 | 1982-02-16 | Sumitomo Chemical Company, Limited | Oximecarbamate derivatives, and their production and use |
| US4838924A (en) * | 1985-08-05 | 1989-06-13 | Mitsui Petrochemical Industries, Ltd. | Aromatic urea derivatives and their use as herbicide |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3060235A (en) * | 1959-08-05 | 1962-10-23 | Ciba Ltd | Phenyl ether-ureas |
-
1970
- 1970-11-09 US US88213A patent/US3707557A/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3060235A (en) * | 1959-08-05 | 1962-10-23 | Ciba Ltd | Phenyl ether-ureas |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3988300A (en) * | 1973-05-31 | 1976-10-26 | American Cyanamid Company | Benzophenone ureas and method for utilizing the same |
| US4026697A (en) * | 1973-05-31 | 1977-05-31 | American Cyanamid Company | Method for utilizing benzophenone ureas |
| US3978123A (en) * | 1973-07-12 | 1976-08-31 | Chevron Research Company | Herbicidal n-alkylsulfoxymethyl-and-n-alkylsulfonyl-methyl-n-aryl |
| US4315768A (en) * | 1978-08-25 | 1982-02-16 | Sumitomo Chemical Company, Limited | Oximecarbamate derivatives, and their production and use |
| EP0036390A2 (en) * | 1980-03-18 | 1981-09-23 | Ciba-Geigy Ag | Diphenyl ether ureas with herbicidal activity |
| EP0036390A3 (en) * | 1980-03-18 | 1982-03-17 | Ciba-Geigy Ag | Diphenyl ether ureas with herbicidal activity |
| US4376646A (en) * | 1980-03-18 | 1983-03-15 | Ciba-Geigy Corporation | Herbicidal N-[4-(3'-alkoxyphenoxy)-phenyl]-N'-methylureas |
| US4838924A (en) * | 1985-08-05 | 1989-06-13 | Mitsui Petrochemical Industries, Ltd. | Aromatic urea derivatives and their use as herbicide |
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