CA1038404A - N-chlorothio ureas and pesticidal derivatives thereof - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

N-chlorothio ureas are produced by the reaction of sulfur dichloride and a urea having at least one hydrogen substituted on a urea nitrogen atom in the presence of an acid acceptor. The N-chlorothio ureas are useful intermedi-ates in the preparation of pesticides.

Description

103~9 04 DESCRIPTI0~1 o~P PRIOR ART

N-chlorothio-N,N'N'-trimethy]urea is a known compound which is prepared by the reaction of an N-silylated urea and sulfur dichloride~ as diselosed by E. Kuhle, S~nthesis, 11, 573 (1970). N-chlorothio-N~N'-N'-, triorgano-substituted ureas are also disclosed in German Patent 2,045,440, published March 23, 1972.
; Processes for producing sulfenyl chloride derivatives of compounds having active hydrogen atoms substituted on nitrogen are also known.
; E. Kuhle, S~thesis, 561 (1970)~ discloses the preparation of sulfenyl - 10 halide derivatives of sulfoamides and amines. U.S. Patent 3,699~122 of Gustave Ko Kohn, issued October 17, 1972, discloses the preparation of sulfenyl halide derivatives of amidesO

DESCRIPTION OF THE INVEN~:E01 The N-chlorothio ureas of the invention are represented by the - formula (I): `~

R " ~R (I) R2 SCl wherein R, Rl and R2 individually are hydrogen or alkyl of 1 to ~ carbon ~ -. - .
atoms, alkoxy of 1 to 4 earbon atoms, cyeloalkyl of 3 to 10 earbon atoms, ` --earbocyelie mononuclear or binuclear aryl of 6 to 12 earbon atoms 20 substituted with up to 2 (0 to 2) substituents seleeted from fluorine, ehlorine, bromine, trifluoromethyl, triehloromethyl~ nitro or alkoxy of 1 to 4 earbon atoms, with the proviso that at least one of R, Rl and R2 is hydro-genO
Representative alkyl groups whieh R, R and R2 may represent include -methyl~ ethyl, n-propyl, isopropyl, n-butyl~ t-butyl~ n-pentyl and n-hexyl.
The preferred alkyl group is methyl.
.:

-- 2 -- -, ., . , ,~ , . , '' - .,: , - 1038404 ~
; Representative alkoxy groups which R, Rl and R2 may 80 represent incluae methoxy, ethoxy, propoxy and butoxy. 91 ~ Representative cycloalkyl groups which R, Rl and RZ 82 ; ; may represent include monocyclic groups such as cyclopropyl, 83 cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 4-methylcyclo- 84 :
hexyl, cycloheptyl, and cyclooctyl; and bicyclic groups such as 85 bicyclor3.2.0]heptyl, bicyclot2.2.1]heptyl, bicyclo[3.3.0]- 86 octyl, bicyclo[4.2.0]octyl, bicyclo~3.3.03Octyl, and bicyclo- 87 ~3.2.1]octyl. Cycloalkyl groups preferably are monocyclic 89 groups having S to 6 carbon atoms. 90 Representative hydrocarbyl aryl groups which R, Rl 91 and R2 may represent include phenyl; naphthyl; alkylphenyl of 7 93 to lO carbon atoms such as 2-methylphenyl, 3-methylphenyl, 4- 94 ethylphenyl, 2,4-dimethylphenyl, 3,4-dimethylphenyl, 3-sec- f butylphenyl; and phenylalkyl of 7 to 10 carbon atoms such as 95 benzyl, 3-phenylpropyl, and 4-phenylbutyl. 97 Representative substituted aryl groups which R, Rl 98 and R2 may represent include phenyl, alkylphenyl or phenylalkyl 100 substituted with l to 2 of the same or different substituents 101 on the phenyl ring, such as 2-fluorophenyl, 4-fluorophenyl, 2- 102 chlorophenyl, 3-chlorophenyl, 3,4-aichlorophenyl, 4-trifluoro- 103 methylphenyl, 3-chloro-4-bromophenyl, 2-chloro-4-methylphenyl, lOS

2-fluoro-4-methylphenyl, 4-chlorobenzyl, 4-fluorobenzyl, 2-~2- 106 fluorophenyl)ethyl, 4-methoxyphenyl, 4-ethoxyphenyl, q-methoxy- 109 2-methylphenyl, 4-methoxybenzyl, 2-nitrophenyl, 4-nitrophenyl, 113 4-nitrobenzyl, 2~methoxy-4-chlorophenyl, and 2-chloro-4- 115 nitrophenyl. Preferred substituted aryl groups are halo- 116 substituted phenyls, especially those having 1 to 2 fluorine or 117 chlorine substituents. 118 Preferably R is alkyl of l to 6 carbon atoms, 119 especially methyl. 120 --~ -` 1038~04 Preferably R~ is phenyl or phenyl substituted with l 121 to 2 fluorine, chlorine, trifluoromethyl, nitro, alkyl of l to 122 :

2 carbon atoms, or alkoxy of l to 2 carbon atoms. 124 RZ is preferably hydrogen. 126 , .
- A preferred class of N-chlorothio ureas of formula 127 :
(I) is that wherein at least one R, Rl or R2 group is hydrogen~ 128 Preferably R2 is hydrogen. 129 ; Another preferred class of N-chlorothio ureas is that 131 wherein ~2 is hydrogen, R is alkyl of l to 6 carbons and Rl is 132 as defined above. 133 Representative N-chlorothio ureas of formula (I) are: 135 - ' .
N-chlorothio urea, 137 N-chlorothio-N-methyl urea, 138 N-chlorothio-N,N'-dimethyl urea, 139 ' N-chlorothio-N-methyl-N',N'-dimethyl urea, 14G
... . . .
N-chlorothio-N-methyl-N'-cyclohexyl-N'-methyl urea, 141 ,' N-chlorothio-N-cyclopentyl-N',N'-diethyl urea, 142 .. . . . .
N-chlorothio-N'-methyl-N,N'-dimethoxy urea, 143 N-chlorothio-N-(2-norbornyl)-N'-phenyl urea, 144 ; N-chlorothio-N-butyl-N'-benzyl urea, 145 N-chlorothio-N-(2-methylcyclohexyl)-N'-phenyl urea& 146 ` N-chlorothio-N-methyl-N'-(2-fluorophenyl) urea, 147 - N chlorothio-N-methyl-N'-(3,4-dichlorophenyl~ urea, 148 ~ N-chlorothio-N-(3-trifluoromethylphenyl)-N',Ni-dimethyl 149 urea, 150 N-chlorothio-N-phenyl-N',N'-dimethyl urea, 151 N-chlorothio-N-(3,4-dichlorophenyl)-N'-methoxy-N'-methyl 152 urea, ~ 153 N-chlorothio-~-(3-chloro-4-bromophenyl~-N'-methoxy-N~- 154 methyl urea, 155 N-chlorothio-N'-(4-bromophenyl~-N,N'-dimethoxy urea, 156 N-chlorothio-N-(4-chlorophenyl~-N7,N'-dimethyl urea, 157 - , , . ; , , "~ . : ..

' .'."'~, ' '.

N-chlorothio-N-(3,4-dichlorophenyl)-N'-methyl-N-~utyl urea, 158 j N-chlorothio-N-(hexahydro-4,7-methanoinden-S-yl)-N',N'- 159 dimethyl urea, 160 N-chlorothio-N-(2-fluorophenyl~-N'-phenyl-N'-methyl urea, 161 N-chlorothio-N-(2-fluorophenyl)-N'-benzyl-N'-methyl urea, 162 M-chlorothio-N-(2-fluorophenyl)-N'-methyl-N'-propyl urea, 163 N-chlorothio-N-(2-fluorophenyl)-N'-(2-fluorophenyl)-N'- 164 methyl urea, 165 N-chlorothio-N-methyl-N'-(4-nitrophenyl)-N'-methyl urea, 166 N-chlorothio-N-methyl-N'-(4-methoxyphenyl)-N'-methyl urea, 167 N-chlorothio-N-I3,4-dichlorophenyl)-N',N'-dimethyl urea, 168 N-chlorothio-N-(2-fluorophenyl)-N',N'-dimethyl urea, 169 N-chlorothio-N-(4-methoxybenzyl)-N',N'-dimethyl urea, and 170 N-chlorothio-N-(2-methylphenyl)-N',N'-dimethyl urea. 171 . .
The N-chlorothio ureas are prepared in accordance 173 with the following reaction (l): 174 ~ .
. . , ~N-C-N~ + SC12 ~ B -~ ~N-C-N + B-HCl `.(II) (I) (1) . .

wherein R, Rl and R2 have the same significance as prevously 176 - defined~and ~ is an acid acceptor. 177 : , :
The acid acceptor is an organic base such as a pyri- 178 dine compound or a trialkylamine compound. Suitable pyridine 180 compounds are pyridine and pyridine compounds of 6 to lO carbon 181 atoms and of 1 to 2 al~yl groups such as 2-methylpyridine, 2- 182 ethylpyridine, 3-methylpyridine, 3,S-dimethylpyridine, and 2- 183 butylpyridine. Suitable trialkylamines are those wherein the 185 alkyl group contains individually 1 to 4 carbon atoms, such as 186 .:
:, '~ ,' ' . ' ', trimethylamine, triethylamine, tripropylamine and tri- 187 butylamine. 188 Generally, commercially available sulfur dichloride 189 of reasonable purity, e.g., greater than 90~98% purity, is 190 suitably employed. The sulfur dichloride may contain small 192 amounts of an inhibitor such as tri~utylphosphate or triethyl- 193 phosphate. 194 The sulfur dichloride and the urea compound are em- 195 ployed in substantially equimolar amounts, e.g., the molar 196 ratio of sulfur dichloride to the urea compound generall~ 197 varies from about l.5:1 to l:l.S, although molar ratios of 198 sulfur dichloride to the urea compound of 1.4:1 to l.l:l are 199 preferred. The molar ratios of acid acceptor to sulfur 200 dlchloride is also substantially equimolar, e.g., the molar 201 ratio of acid acceptor to sulfur dichloride varies from about 202 1.2:1 to 1:1.2, although molar ratios of acid acceptor to 203 sulfur dichloride of l:l to 1:1.2 are preferred. 204 . .~ .
!, In general, the reaction is accomplished by reacting 205 the urea and the sulfur dichloride in the presence of the acid 206 acceptor compound in an inert diluent. The reaction is 208 suitably conducted by adding the sulfur dichloride to a mixture 209 of the urea and the acid acceptor in an inert diluent.
~; Alternatively, the reaction is conducted by adding a mixture of 211 _ the urea and acid acceptor to a solution of the sulfur di-chloride in an inert diluent. However, the preferred method 213 for conducting the reaction comprises reacting the urea and 214 sulfur dichloride in the presence of a limited amount of free 215 uncomplexed acid acceptor. This is suitably accomplished by 216 the addition of the acid acceptor to a substantially equimolar 218 mixture of the urea and the sulfur dichloride so that the mols 219 of free acid acceptor to the total mols of urea reactant and N- 220 chlorothio urea product is less than 0.2:1, preferably lass 221 . :

.

. 1038~a(P4 than 0.1:1, and more preferably less than 0.05:1. In other 222 words, during the course of the reaction between the sulfur 223 dichloride and the urea reactant, there should be at least 5 224 mols of the urea reactant and the N-chlorothio urea product per 225 mol o~ acid acceptor which is not complexed with hydrochloric 226 acid. Provided that the reaction is conducted with the 227 restricted amount of acid acceptor indicated above, the 228 . .
~ contacting of the acid acceptor with the mixture of the urea 229 .~, and the sulfur dichloride can be conducted by a variety of 230 procedures. In one modification, the acid acceptor is added in 231 increments, e.g., dropwise, in an inert diluent, if desired, to 232 a mixture of the urea and sulfur dichloride in an inert 233 diluent. In another modification, the acid acceptor is added 234 continuously to a mixture of the urea and sulfur dichloride in 235 - ., an inert diluent. 236 Suitable inert diluents for the reaction include 237 alkanes of 5 to 10 carbon atoms, such as hexane, isooctane and 239 decane; aromatic compounds such as benzene and chlorobenzene, 240 oxygenated hydrocarbons such as acyclic alkyl ethers, e.g., 241 dimetho~yethane and dibutyl ether; and cycloalkyl ethers, e.g., 242 dioxane, tetrahydrofuran and tetrahydropyran. Other suitable 243 diluents include nitriles such as acetonitrile and 244 propionitrile, dialkylamides such as dimethylformamide and 245 dialkylsulfoxides such as dimethylsulfoxide. Preferred 247 diluents are chlorinated hydrocarbons of 1 to 2 carbon atoms, 248 such as methylene dichloriae, chloroform, carbon tetrachloride 249 and ethylene dichloride. Generally, the amount of diluent 250 employed ranges from l-tc 50 mols per mol of sulfur dichloride. 252 The reaction is suitably conducted at a temperature 253 between -20C. and the boiling point of the diluent, although 254 temperatures between 0C. and 50C. are preferred. The 256 reaction is conducted at or above atmospheric pressure. 257 . 10~89L04 It is appreciated, of course, that the N-chlorothio 258 urea product of the invention is formed by the substitution of 2S9 ; a hydrogen substituent on a urea nitrogen atom by a sulfenyl 260 chloride group. When the urea reactant has more than one 262 hydrogen substituted on a urea nitrogen, a mixture of mono- 263 chlorothio derivatives is therefore generally formed (unless 264 the urea reactant is symmetrical, i.e., one Rl or R2 is hydro- 265 gen and the other Rt or RZ is the same as R). However, it has 267 been found that when one R, Rl or ~2 group is alkyl, the urea 268 ,. . . .
compound is preferentially sulfenylated at the nitrogen atom 269 bearing the alkyl group. 270 .,, ~ ,~ ~ ,. .. ..
The preparation of the N-chlorothio ureas of the 271 invention is illustrated by the following examples: 272 EXAMPLES ! 275 _xample_l -- Pre~arati_ _of ~-chl_rothio-N- 276 meth~l=N'-2-fluoro~he~yl u__a 277 a 5~7-g (O.OS5 mol) sample of sulfur dichloride ~as 275 added dropwise to a mixture of 8.4 g (0~05 mol) N-methyl-N'-2- 280 fluorophenyl urea and 4.7 g (0.06 mol) pyridine in 50 ml 282 methylene chloride cooled in an ice bath. After the completion 284 of the addition, the pyridine hydrochloride formed during the 285 reaction was filtered. Hexane was added to the filtrate to 286 precipitate adaitional pyridine hydrochloride, which was 287 removed`by filtration. Evaporation of the resulting filtrate 288 gave a clearred oil. The nuclear magnetic resonance (NMR) 289 spectrum of the oil showed an N-methyl singlet at 3.5 ppm 290 (relative to tetramethylsilane). Elemental analysis showed: 291 %S, Calc. 13.6, found ~3.6; ~Cl, calc. lS.l, found 15.4. 293 Exam~le 2_=_ PreParatio_ of N=chlorothi_ N- 296 - r3 4__ichloro~h_~yl)-N_~N'-dimethyl urea 297 A 5.7-g (0.055 mol) sample of sulfar dichloride was 299 added dropwise to a mixture of 11.7 g (O.OS mol) of N-(3,4-di- 300 . . .

:. -: . , , ~............... .
: :. : .. ' . ~: .

chlorophenyl)-N,N'-dimethyl urea and 4.7 g (0.06 mol) pyridine 302 ~ in 50 ml methylene chloride cooled in an ice bath. After the 304 `~ completion of the addition, the pyridine hydrochloride was 305 ;.
filtered. ~exane ~as added to precipitate additional pyridine 306 hydrochloride, which was removed by filtration. Evaporation of 308 the resulting filtrate gave the product as a clear yello~ oil. 309 The NMR spectrum sho~ed an N',N'-dimethyl singlet at 3.0 ppm 310 (relative to tetramethylsilane). Elemental analysis sho~ed: 312 %S, calc. 19.7, found 10.7; %Cl, calc. 35.6, found 35.4; %C, 313 calc. 36.1, found 36.4; hH, calc. 3.0, found 3.2; %N, calc. 314 9.3, found 8.7.
ExamPl_ 3 =- PrePara_ion of N-chl_rothio= 317 N methyl-N'_3~-dichloroPhenvl ur_a 318 A 9.q8-g (0.12 mol) sample of pyridine was added 320 dropvise to a slurry of 21.9 (O.l mol) N-methyl-N'-(3,4-di- 321 chlorophenyl) urea and 11.3 g (0.11 mol) sulfur dichloride in 323 100 ml methylene dichloride at 25--30C. After the com~letion 325 of the addition, pyridine hydrochloride was filtered from the 326 reaction mixture. The NMR spectrum of the reaction mixture 327 showed a singlet at 3.5 ppm ~relative to tetramethylsilane) for 329 the N-methyl group of the N-chlorothio-N-methyl-N'-3,4- 330 dichlorophenyl urea product. 331 E__mple~_-- PrePa ation of N=chlorothio-~N'-dlmethyl_ur_a 334 v Pyridine (9.48 g, 0.12 mol) ~as added dropwise to a 336 solution of 8.8 g (0.1 mol) N,N'-dimethyl urea and 11.3 g O.ll 339 mol) sulfur dichloride at 25-30C. Pyridine hydrochloride was 341 then filtered from the reaction mixture to give a solution of 342 the N-chlorothio urea product in methylene chloride. The NMR 343 spectrum of the product showed a singlet at 3.5 ppm for the N- 344 methyl group and a doublet at 2.9S ppm for the N'-methyl group. 345 _ 9 _ 103B40,4 ~
i,,,i., , lJTIL TY 348 he N-chlorothio urea compounds of the invention are 350 .. ' useful intermediates for the preparation of pesticides. 351 Representative types of pesticides which can he prepared from 353 :~the N-chlorothio urea compounds are illustrated below: 354 -.;~P__Daration_of N_carb_alkQ~Yalkyld th_o urea_~ _uads 357 The N-chlorothio urea compounas react with mercapto- 359 alkanoate esters to form N-carboalkoxyalkyldithio urea com- 360 ~ pounds. In terms of the N-chlorothio urea compounds repre- 362 : sented by formola (I), the reaction can be depicted by the 363 :' following equation (2): 364 .. t . ..
i Rl o SCl : ~ :
t N-C-N+ I~S (CH2 ) n-CoR4 + B ) (2 ) . (I) N-C-N +BHC1 ~ ~:
.'. R2 (III) R
:`, ;, ~herein R, R~, R2 and B have the same significance as pre- 366 :, viously aefined and R~ is alkyl of l to 6 carbon atoms and n is 367 :~
l or 2. 368 .
ExamPle 5 -- Pr~ara ion of N-(2-carbomethoxY_ 371 .hyldithi~L-N-methvl-N'-~3,4-dl__lr_E~Yl UE_a 372 .1 N-chlorothio-N-methyl-N'-t3,4-dichlorophenyl) urea 374 _ (O.l mol) in lO0 ml methylene chloride was prepared in a manner 375 ~ :
identical to Example 3.' Methyl-3-mercaptopropionate (0.09 mol) 378 ~
. and pyridine t7.9 g, O.l mol) dissolved in lO ml methylene 379 -chloride ~as added to the chlorothio urea at 0C. The reaction 381 .. was stirred lO minutes_after the addition was completed and the 382 " .
mixture was washed ~ith water, washed ~ith sodium bicarbonate, 383 dried over magnesium sulvate and evaporated under reduced 384 -:~

., pressure to yield an oil. Chromatography over silica gel 385 ; (benzene eluent~ yielded the product, a dark gray oil. 386 :

; :, . .

10384~4 Elemental analysis showed: %S, calc. 17.3, found 1~.2; %Cl, 387 calc. 19.2, found 19.6. 389 ~y a similar procedure the urea compounds tabulated 390 in Table I were prepared. 391 The ~-carboalkoxydithio urea compounds are, in gene- 392 ral, herbicidal in both pre- and post-emergent applications. 393 For pre-emergent control of undesirable vegetation, these ureas 394 will be applied in herbicidal quantities to the locus or 395 environment of said vegetation, e.g., soil infested with seeds 396 and/or seedlings of such vegetation. Such application will 398 inhibit the growth of or kill the seeds, germinating seeds and 399 seedlings. For post-emergent applications, the N- 400 carboalkoxydithio urea compounds will be applied directly to 401 the foliage and other plant parts. Generally they are 403 effective against weed grasses as well as broadleaved weeds. 404 Some may be selective with respect to type of application 406 and/or type of weed. 407 Pre- and post-emergent herbicidal tests on the N- 409 carboalkoxyalkyldithio urea compounds prepared above were made 410 using the following methods: 411 Pre-Emerqent_Te_t 414 An acetone solution of the-test urea compound was 416 prepared by mixing 750 mg urea, 220 mg of a nonionic surfactant 419 and 25 ml of acetone. This solution was added to approximately 421 125 ml of water containing 156 mg of surfactant. 422 Seeds of the test vegetation were planted in a pot of 424 soil and the urea solution was sprayed uniformly onto the soil 425 surface at a dose of 3~ mcg/cmZ. The pot was ~atered and 426 placed in a greenhouse. The pot was watered intermittently and 42 was observed for seedling emergence, health of emerging 428 seedlings, etc., for a 3-week period~ At the end of this 43C
period, the herbicidal effectiveness of the urea was rated 431 based on the physiological observations. A 0-to-lO0 scale was 433 used, 0 representing no phytotoxiclty and lO0 representing 434 complete kill. 435 Post-~merqent_Test 438 The test urea was formulated in the same manner as 440 described above for the pre-emergent test. The concentration 444 of the urea in this formulation was 5000 ppm. This formulation 445 was uniformly sprayed on 2 similar pots of 24-day-old plants 446 (approximately 15 to 2S plants per pot) at a dose of 33 447 mcg/cmZ. After the plan~s had dried, they ~ere placea in a 448 greenhouse and then ~atered intermittently at their bases as 450 needed. The plants were observed periodically for phytotoxic 451 effects and physiological and morphological responses to the 453 treatment. After 3 ~eeks, the herbicidal effectivenes of the 4S~
urea was rated based on these observations. A 0-to-lO0 scale 456 was used, 0 representing no phytotoxicity and lO0 representing 457 complete kill. The results of these tests appear in Table II. 459 ~ he herbicidal compounds described herein are applied 460 in herbicidally effective amounts to the locus or environment 461 of undesirable vegetation, or directly to the foliage and ~ther 462 plant parts. They can be used alone as herbicides. However, 465 it is generally desirable to apply the compounds in herbicidal 466 compositions comprising one or more of the herbicidal compounds 467 intimately admixed with a biologically inert carrier. The 469 carrier may be a liquid diluent or a solid, e~g., in the form 470 of dust po~der or granules. In the herbicidal composition, the 471 active herbicidal compounds can be from about O.Ol to 95% by 472 weight of the entire composition. 473 Suitable liquid diluent carriers include water and 474 organic solvents, e.g., hydrocarbons such as benzene, toluene, 475 kerosene, diesel oil, fuel oil, and petroleum naphtha. 47 Suitable solid carriers are natural clays such as kaolinite, 477 .,: - .. . . : . ~ . .
. .

:
' .~ 1~384 B4 atalpulgite, and montmorillonite. In addition, talcs, 479 pyrophillite, diatomaceous silica, synthetic fine silicas, 480 calcium aluminosilicate and tricalcium phosphate are suitable 481 carriers. Organic materials such as walnut-shell flour, 482 cottonseed hulls, wheat flour, ~ood flour or red~ood-bark flour 483 may also be used as solid carriers. 485 The herbicidal composition will also usually contain 486 a minor amount of a surface-active agent. Such surface agents 488 are those commonly known as wetting agents, dispersing agents 489 and emulsifying agents, and can be anionic, cationic or 490 nonionic in chaaracter. The herbicidal compositions may also 491 contain other pesticides, adjuvants, stabilizers, conditioners, 492 fillers, and the like. 493 The amount of herbicidal compound or composition 494 administered will vary with the particular plant part or plant 496 growth medium ~hich is to be contacted, the general location of 497 application -- i.e., sheltered areas such as greenhouses, as 498 compared to exposed areas such as fields -- as ~ell as the 499 desired type of control. Generally, for both pre- and post- 500 emerge~nt control, the herbicidal compounds of the invention are 501 applied at rates of 2 to 60 kg/ha, and the preferred rate is in 502 the range of 5 to 40 kg/ha. 503 .:
.~

:' , ''~
. :

:':. 103~41~4 'i'' .' :............ ~: ~ ~ o I
0~ ~ O CO U~
~ ~ ~ o ~ o I ~ o a~
~ Z U) E
O ::~ ~ 0 ~ ' , X
O r~ ' o O O 0 0 0 0 U
u~ ~ \~\\\\\~ ~ O E
. ' , . o o o o o o o o U~
., ~,) ~ o ~ o o~ O O o o o o o o ;.' ~ ~ ' ~ o~
. . o o o o o o o o r~
o I L~ V o o o o o o o o t~
U~ P~ \ \ \ \ \ \ \ \ U~
. ., ~ L'') ~ ~--1 ~ O O O
., ~ ~ O L'`) ~ ~D ~ O O Ln a) ~ ~ ~ ~ ~ ~ ~ ~ E O
~; ~ ~,, . . oOoooooo ~ ~:r I o o o o o o o o t~
. ~ H ¦ I Ul ~ \ \ \ \ \ \ ~ ~ ~ 3 Q., ~ I ~ ~qo o o o o o o o ',: ml ~ o ~ o o o ~ o o o o . " !~ I ~ O H .
.: I ~ ~ ~ ~ N --' ~,) lil ~,) O O O O
I r~ I -- ~ m ~ c~ o O O L~ O ~ \ \ ~ L

V~ ~ .C L ~ V ~ c~ o o o~ o o o o ~ _, U ~ Z; U ,~ '2 Ln co o L L O O L (~
O rC~ ~ h ,~ U ¦ o o O O ~a S
C ~ ~ ~ ~ ^~C

X --~ 13 ~ C, ~ / C ~ U O ~ \. \ \ \ \ \ \ \ ~ Ul , . G" ~ O n O ci~ G~ LD ~J ~q U ~ .~ S X S S Q U C C S~ U Q X ~ r~ Q
,.~Q ~ h~ E; I Q P ~, pLQ I S ol H ~ ~ ~r Ln ~ 1--G~ 3 .

I ~ --t~ ~ ~ ~ S ~ ,~ 3 Z æ z Z zzzz - o I ~ ~ ~ ~r Ln ~D 1` CO

: - 14 --.

` .: . ` . ` ,, ' ' '

Claims (9)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. An N-chlorothio urea of the formula wherein R, R1 and R2 individually are hydrogen, alkyl of 1 to 10 carbon atoms, cycloalkyl of 3 to 10 carbon atoms, alkoxy of 1 to 4 carbon atoms, carbocyclic mononuclear or binuclear aryl of 6 to 12 carbon atoms substituted with up to 2 substituents selected from fluorine, chlorine, bromine, trifluoromethyl, trichloromethyl, nitro or alkoxy of 1 to 4 carbon atoms, with the proviso that at least one R, R1 or R2 group is hydrogen.

2. The urea of Claim 1 wherein R2 is hydrogen.

3. The urea of Claim 1 wherein R is alkyl of 1 to 6 carbon atoms and R2 is hydrogen.

4. The urea of Claim 1 wherein R is alkyl of 1 to 6 carbon atoms, R1 is alkyl of 1 to 6 carbon atoms and R2 is hydrogen.

5. N-chlorothio-N,N'-dimethyl urea, according to Claim 4.

6. The urea of Claim 1 wherein R is phenyl, alkylphenyl of 7 to 10 carbon atoms, phenylalkyl of 7 to 10 carbon atoms or phenyl, alkylphenyl or phenylalkyl substituted with 1 to 2 fluorine, chlorine, bromine, trifluoromethyl, trichloromethyl, nitro or alkoxy of 1 to 4 carbon atoms, R1 is alkyl and R2 is hydrogen.

7. The urea of Claim 1 wherein R is alkyl, R1 is phenyl, alkylphenyl of 7 to 10 carbon atoms, phenylalkyl of 7 to 10 carbon atoms, or phenyl, alkylphenyl or phenylalkyl substituted with 1 to 2 fluorine, chlorine, bromine, trifluoromethyl, trichloromethyl, nitro or alkoxy of 1 to 4 carbon atoms and R2 is hydrogen.

8. The urea of Claim 7 wherein R1 is phenyl or phenyl substituted with 1 to 2 fluorine, chlorine, bromine, trifluoro-methyl, trichloromethyl, nitro or alkoxy of 1 to 4 carbon atoms.

9. The urea of Claim 8 wherein R1 is phenyl substituted with 1 to 2 fluorine, chlorine or bromine.