United States Patent (19) [11] 3,884,963 Daniher et al. (45) May 20, 1975

54 ADDITION OF N,N-DICHLORO-N-ACYL 2,395,750 2/1946 Muskat et al...... 260/482 X COMPOUNDS TO DENES 3,477,933 1 1/1969 Stamm et al...... 260/482 C (75) Inventors: Francis A. Daniher, Westfield; FOREIGN PATENTS OR APPLICATIONS Alexis A. Oswald, Mountainside, 1,203,534 6/1962 Germany...... 260/482 C both of N.J. Primary Examiner-Lorraine A. Weinberger 73) Assignee: Exxon Research & Engineering Assistant Examiner-Paul J. Killos Company, Linden, N.J. Attorney, Agent, or Firm-J. N. Blauvelt; J. P. (22) Filed: Dec. 6, 1967 Corcoran 21 ) Appl. No.: 688,308 57) ABSTRACT (52) U.S. Cl...... 260/482 C; 260/404; 260/465.4; N,N-Dichloro-N-acyl compounds, such as N,N- 260/468 E; 260/471 C; 260/481 C; 260/482 dichlorocarbamates, sulfonamides and amidosulfona B; 260/556 A; 260/556 N; 260/556 AR; mides selectively react with conjugated dienes to yield 260/556 B; 260/556 C; 424/300; 424/314 the corresponding 1,4-monoadducts, i.e. N-chloro-N- (51) Int. Cl...... C07c 125/06 chlorocrotyl compounds. The N-chloro group of these Field of Search ...... 260/482 C, 482 B monoadducts can be selectively reduced by aqueous (58) sodium sulfite. Both the original and the reduced ad 56 References Cited ducts are novel compositions useful as biologically ac UNITED STATES PATENTS tive compounds and vulcanizing agents. 1964,654 6/1934 Ulrich et al...... 260/482 X 27 Claims, No Drawings 3,884,963 1. 2 ADDITION OF N,N-DCHLORO-N-ACYL acts in the same manner with two moles of a conjugated COMPOUNDS TO DENES diene as per the following equation; e.g., THE INVENTION O The present invention relates to a novel, selective 5 diene addition process resulting in new, useful carba R’ OCNCl2 + 2 CH2=CH-CH mates heretofore unavailable in the art. More particu larly, this invention describes the selective addition of N,N'-dichloro-acyl compounds, such as N,N- dichlorocarbamates, N,N-dichlorosulfonamides, N,N- O dichloroamidosulfonamides to conjugated dienes yield O ing N-chlorocrotyl acyl compounds. t N-Acyl compounds such as carbamates and sulfona =CH2 -> R, OCNCH2CH=CHCH2Cl mides are a known useful class of compounds. For ex C 2 ample, carbamates or urethanes are a widely known 15 type of compounds. Some of them are extremely useful in the pesticide, pharmaceutical and polymer industry. The resulting N-chloro-N-chlorocrotyl carbamates The importance of selected members of N-acyl com could be reduced by sodium sulfite to yield a surpris- . pounds has stimulated interest in new types of carba ingly high yield of the corresponding N-chlorocrotyl mates, sulfonamides and amidosulfonamides and novel 20 carbamate, e.g. methods of preparing such compounds. The addition of N-chloro dialkylamines to a conju gated diene, 1,3-butadiene was reported to occur in O acidic medium to yield up to 60% of the corresponding 1,4-adducts (R. S. Neale and R. L. Hinman, J. Am. 25 RpCNCH2 CH=CHCH2 Cl -- Na2SO3+H2O -9 Chem. Soc. 85, 2666 (1963)). HSO Cl RNC1 + CH, = CH-CH = CH, HoAce RNCHCH = CHCHCl 30 The addition of N,N-dichlorocarbamates to a variety of O monoolefins has been recently reported to yield the t corresponding anti-Markovnikov adducts in yields gen RpCNCH2CH=CHCH2Cl + NaHSO-NaCl erally ranging from 25-65%. (One high yield exception t was the addition to styrene where an 80% yield was ob-, H tained): 35 O O O t NaHSO3 ROCNCl2 + CH2 = CHR" -> ROCNCH2CH2R' --> ROCNCH2CH2R.' Cl Cl H Cl In the present invention, it has been found surpris The reduction of the N-chloro group of carbamates ingly that the addition of N,N-dichlorocarbamates to with sodium hydrogen sulfite is a known process. It was 1,3-butadiene in neutral media gives a quantitative 45 found that for the reduction of our chlorocrotyl car yield of the corresponding monoadducts in a spontane bamate adducts the use of sodium sulfite is much pref ous reaction. erable.

O O O ROCNCl2 + CH2=CH-CH= CH2--> RpcNCH2 CH=CHCH2Cl + Rp CN CH2 CH2 CH=CH2 Cl Cl 85% l5% Characteristic of the addition to 1,3-butadiene and The addition of other N,N-dichloro-acyl compounds, other conjugated dienes is the fact that the predomi such as N,N-dichloro sulfonamides and N,N-dichloro nant mode of addition to the diene is 1,4-addition with dialkylamidosulfonamides to conjugated dienes was out formation of diaddition products to the diene. go also found to occur with a surprising ease and selectiv ity as shown for butadiene additions by the following Similarly, one mole of a difunctional carbamate re reaction equations: RSO2NCla + CH2=CH-CH=CH2-9 RSO2NCH2CH=CHCH2Cl Cl NCla-CH=CH-CH=CH-Y- H a RENSO2NCH-CH=CHCH2Cl) Cl 3,884,963 3 4 These N-chloro-N-chlorocrotyl adducts can be again wherein R2 to Rt. are the same as previously defined. advantageously reduced by sodium sulfite to the corre- R1 is an alkyl or substituted alkyl group having from 1 sponding N-chlorocrotyl compounds: to 30 carbon atoms, such as a simple alkyl group exem - plified by methyl, ethyl, isopropyl, tertiary butyl, dode RSO2NCH2 CH=CHCH2Cl+Na2SO3 5 cyl, hexadecyl, etc. and a substituted alkyl group where C the substituents are selected from the group consisting of halo, nitro, sulfone, carboxylic ester having 2 to 6 carbon atoms, etc. +H2O-) RSO2NCH2 CH=CHCH2Cl+NaHSO+NaCl Bis-N,N-dichloro carbamates can be also added to . 10 conjugated dienes to yield the following novel composi H tions:

Cl 15 2 c = c - c = c - L''22.OCNC. +H2O-9 R2NSO2NCH2CH=CHCH2Cl+Na2SO+NaClt R3 R7 H The above addition and reduction processes lead to 20 novel types of acyl compounds as shown by the follow ing reaction scheme:

R. R. Rs. Rs R R. R. Rs 25 O R2 R) R5 R6 C-C-C-C AcNC, AcN-C-C-C-C-Cl Nasos RoCN - C -6 =6 - - - Cl Na2SO3 R R C R R Cl R3 R7 2 R. R. R. R 30 R2 R. R5 R6 AcN-C-C-C-C-Cl R OCN - C - C = C - C - Cl H R R H R3 R7 2 35 wherein Ac is an acyl group such as carboalkoxy, wherein R to R are the same as previously described, R'OCO, hydrocarbylsulfonyl R'SO, dialkylamidosul- R" is a bivalent alkylene or substituted alkylene radical fonyl, (R'),NSO, R2 to R7 are hydrogen, chlorine, having from 1 to 12 carbon atoms such as ethylene, fluorine, an alkyl group having from 1 to 30 carbon 0 hexamethylene, xylylene, etc. atoms such as methyl, ethyl, propyl, isopropyl, butyl, Furthermore, the addition of N,N-dichloro sulfona isobutyl, heptyl, decyl, dodecyl, tridecyl, hexadecyl, mides to conjugated dienes specifically produces novel eicosyl, etc.; substituted alkyl where the substituents monooadducts which can be reduced with sodium sul are selected from the group consisting of halo, nitro, fite as shown in the following: sulfone, -COR; aryl having from 6 to 10 carbon 45 atoms such as phenyl; substituted aryl such as aralkyl, including benzyl, beta-phenethyl, and other substituted R2 Rly. Rs R6 theforms group of aryl consisting wherein theof substituentshalo, nitro, arecarboxyl, selected CO.R, from C - C - C 1- C - RSONC.'''2'''2. etc., phenyl and substituted phenyl having 6 to 10 car- 50 bon atoms such as nitrophenyl, chlorophenyl, xylyl, R3 R7 etc. More particularly, the addition of N,N-dichloro car bamates, i.e. dichlorourethanes to conjugated dienes R2 R. R5 R6 and the reduction of the resulting monoadducts yields 55. NaSO the following types of novel compositions: R"SO2N - C -- C = CC-C - C - C 2V3 C. R3 R7 R. R. R. Rs O O R. R. R. R. R. R. R. R. y f 60 2 4. 5 6 --armrem-3 R'SO2N - C - C = C - C - Cl Ra R C. R. R t NaSO H R3 R7

9f R. R. R. R. 65 ROCN-C-C-C-C-C wherein R, to R7 are the same as previously defined, H Ra R R' is a hydrocarbyl or a substituted hydrocarbyl having 3,884,963 S 6 1 to 30 carbon atoms such as methyl, hexadecyl, tri In a preferred embodiment of this invention, N,N- chloromethyl benzyl, phenyl, methylsulfonylphenyl, dichloro acyl compounds can be reacted with 1,3- chlorophenyl, trichlorophenyl, nitrophenyl, naphthyl, butadiene at low temperatures, e.g. between -10° and tolyl, chlorotolyl, etc. . 20°C. Other conjugated dienes may be used. The pre The invention specifically includes the compounds 5 ferred dienes include isoprene, 1,3-butadiene; chloro derived by the addition of N,N-dichloro N',N'-dialkyl prene, l-phenylbutadiene, 1,4-diphenylbutadiene; 2,3- sulfamides to conjugated dienes and by the subsequent dimethylbutadiene; piperylene; 2,3-dichloro-1,3- reduction of the adducts: butadiene; 2-ethyl-1,3-butadiene; 1,3-hexadiene; 2,4- hexadiene, 2-methyl-1,3-pentadiene; 4-methyl-1,3- R 10 pentadiene. Other, less preferred, dienes that are suit R2 R. Rs R6 able for use in this invention include 13 C - C - C - c (R')2NSO2NCl2 cyclohexadiene, 1-chloro, 1,3-butadiene; cyanoprene; --> fluoroprene, 1,3-cyclooctadiene; 2,5-dimethyl-2,4- R3 R7 hexadiene; cyclopentadiene, etc. The foregoing enu 15 meration of dienes is merely intended to be a represen R. R. R. R. tative, and not exhaustive, listing of dienes suitable for 2 l. 5 6 application within the scope of this invention. (R")2NSO2N - C - C - C - C - Cl Na2SO As N,N-dichloro acyl compounds N,N-dichloro car Cl R3 R7 bamates may be used. Examples of suitable N,N- 20 dichlorocarbamates are the following: N,N- dichloroethyl carbamate, N,N-dichlorohexadecyl car bamate, N,N-dichloro-i-propyl carbamate, N,N- R")2NSO2N - C - C = C-C-Cl dichlorocyclohexyl carbamate, N,N-dichloro-2- chloroethyl carbamate, N,N-dichloro-2-nitroethyl car H R3 R7 25 bamate, N,N-dichlorotrifluoroethyl carbamate, N,N- wherein R to R are the same as previously defined, dichloromethylsulfonylethyl carbamate, N,N- R' is an alkyl group having from 1 to 20 carbon atoms dichlorotrichloromethyl carbamate, N,N-dichlorocar such as methyl, isopropyl, hexadecyl. bomethyloxyethyl carbamate, N,N-dichlorobenzyl car The novel reactions described in the present inven bamate. Any alkyl or substituted alkyl ester of N,N- tion produce the following types of novel compositions: dichlorocarbamic acid can be used as a starting mate rial as long as the alkyl portion does not contain any substituent which would react with the N,N- O R2 R. R5 R6 dichlorocarbamate group. For example, vinyl-, mer ROCN - C - C = C - C - Cl capto-, or amino- substituted dichloro carbamates l t 35 would not be suitable. X R3 R7 Suitable bis-N,N-dichloro carbamate reactants in clude ethylene bis-N,N-dichloro carbamate, hexameth Carbamates ylene N,N-dichloro carbamate, p-xylylene N,N- R2 R4 R5 R6 40 dichloro carbamate, etc. t Another class of N,N-dichloro acyl compound reac R"SO2N - C - C = C - C - Cl tants consists of N,N-dichloro sulfonamides. Suitable N,N-dichloro sulfonamides are exemplified by the fol X R3 R7 lowing: N,N-dichloro methanesulfonamide, N,N- 45 dichloro trichloromethanesulfonamide, N,N-dichloro Sulfonamides chloroethanesulfonamide, N,N-dichloro dodecanesul fonamide, N,N-dichloro benzenesulfonamide, N,N- dichloro 4-chlorobenzenesulfonamide, N,N-dichloro O 2,4,5-trichlorobenzene sulfonamide, N,N-dichloro 4 2 R, R5Rs 50 toluenesulfonamide, N,N-dichloro 2 ROCN - C - C = C - C - C naphthalenesulfonamide. X R3 R7 A third class of N,N-dichloro acyl compounds which 2 can be added to conjugated dienes according to the Bis-Carbamates present invention is represented by N,N-dichloro 55 amidosulfonamides. Suitable N,N-dichloro dialkyl R2 R. R5 R6 amidosulfonamides are N,N-dichloro dime t thylamidosulfonamide, N,N-dichloro diso (R"')2NSON - C - C = C - C - Cl propylamidosulfonamide, N,N-dichloro dihex X R3 R7 adecylamidosulfonamide. 60 Sulfamides In general, any N,N-dichloro acyl compound will add to conjugated dienes under appropriate conditions. With liquid and gaseous reactants the reaction is usu wherein R to R, Ru, R', R', R'' are as previously de ally carried out in the absence of solvents at low tem fined and X is chlorine and hydrogen. In the pesticide 65 peratures. Solid reactants such as higher molecular and medicinal compositions of the present invention, X weight N,N-dichloro carbamates and dienes may re is chlorine and hyrogen while in the vulcanization addi quire elevated temperatures or suitable solvents to sat tives X is always chlorine. isfactorily effect reaction. 3,884,963 7 8 The general reaction conditions that may be utilized with at least one material of the group consisting of in the addition process of this invention comprise tem finely-divided solids, inert granular solids, and surface peratures ranging from about -80 to about 100°C., active dispersing agents. preferably from about -20 to about -30°C. The reac The expression "surface active dispersing agent' as tion time is dependent upon the rate of addition and it herein employed is intended to include all agents which may vary from spontaneous reaction to about 8 hours, are capable of acting at the interfacial surface between depending upon the choice of reactants and the reac the aforesaid carbamate derivative or composition and tion conditions but may take as long as about 24 hours, water or organic solvents as the dispersion dispersant assuming proper mixing of reactants. Ordinarily, how media, facilitating thereby the dispersion of the toxi- . ever, the reaction should take no longer than about 1 10 cant in water or organic solvents to form aqueous and hour. emulsified concentrate. The term is inclusive of solid Pressures ranging from 1 to 10 atmospheres can be emulsifying agents such as finely divided bentonite, py used. Preferably, however, the reaction is conducted at rophyllite, fuller's earth, attapulgite, silica, other clays atmospheric pressure. and mineral carriers, as well as liquid and solid ionic Preferably, the ratio of reactants is equimolar; how 15 and non-ionic wetting and dispersing agents, alkaline ever, excess diene can be used. In general, the ratio of metal caseinates, alkyl aryl sulfonates, sulfonated oils, reactants can vary from 1:1 to about 5:1 moles of diene complex organic ester derivatives, condensation prod per mole of N,N-dichloro acyl compound. While an ex ucts of alkene alkaline oxides and organic acids, ma cess of N,N-dichloro compound could be used, this is hogany soaps, etc. not at all preferred since any excess of this reactant 20 Other suitable surface active dispersing agents may constitutes a waste thereof. From the previous equa be found in "Detergents and Emulsifiers, Up to Date", tions, it is manifest that, with a difunctional carbamate, written and published by John W. McCutcheon, Inc., a minimum of two moles of the diene reactant is re New York, 1962. quired. The term “finely divided inert solids' as herein em Various solvents useful in the foregoing process, 25 ployed refers to material whose primary function is not preferably inert solvents, include such solvents as par as dispersant of the present N-chlorocrotyl derivatives affinic and aromatic hydrocarbons and their halo deriv in water or organic solvents, but as carrier for dust atives, such as, for example, dichloromethane, carbon compositions. Illustrative of such carriers are materials tetrachloride, benzene, xylene, chlorobenzene, chloro such as chalk, talc, gypsum, etc. form, methylene chloride, pentane, iso-octane, decalin, 30 The term “inert granular solids' refers to mineral or etc. Preferred solvents include the aliphatic and alicy other inert carriers which are suitable for dry applica clic hydrocarbons and their chlorinated derivatives tion and which include corn cobs, sand, and other ma such as cyclohexane, etc. In general, any suitable sol terials which differ primarily in particle size from the vent that is either inert or substantially inert under the finely divided inert solids. reaction conditions such that it does not react with the 35 According to the present invention, any of the appro reactants to any substantial extent is useful within the priate crotyl derivatives disclosed herein may be com purview of this invention. pounded with any of the finely divided solids to form In the reduction process the temperature is from dust compositions by grinding, mixing, or wetting the -20 to 100°C., preferably from 0 to 50°C. The sodium finely divided carrier with a solution of the toxicant and sulfite reducing agent is preferably used in the form of 40 a volatile organic solvent. Similarly, dust compositions a concentrated aqueous solution. An inert organic sol containing the aforesaid carbamate derivatives may be vent such as a chlorinated hydrocarbon is used as a sol compounded from any one or more of the solid surface vent for the N-chloro-N-(4-chlorocrotyl-1) compound active dispersing agents previously mentioned, such as to be reduced. The reduction is effected while the reac bentonite, fuller's earth, attapulgite, and other clays. tion mixture is vigorously stirred. The reduction usually 45 Depending upon the proportions of ingredients, these requires several hours. The completion of the reaction dust mixtures may be employed either as treating com is usually established using a potassium iodide test for positions or as concentrates to be subsequently diluted the disappearance of the N-chloro group. with additional solid surface active dispersing agent or As previously noted, the N-chlorocrotyl compounds with talc, chalk, gypsum, etc., to obtain the desired of this invention are useful as pesticides. One aspect of 50 amount of toxicant in a composition adapted to be ap such pesticidal application is as a herbicide, preferably plied to plants, plant growth media, or fungi thereon, as post-emergent, or as a fungicide. When used as a for the suppression of plant growth of said fungi. Also, fungicide or herbicide, the compositions of this inven such concentrate dust compositions may be dispersed tion may be used to control plant growth or fungi in water or organic solvent with or without the aid of thereon either applying to foliage or plant growth me 55 additional dispersing or emulsifying agent to form spray dia, a growth- or fungi-controlling dosage of the pres mixtures. ent acyl compound or of concentrated compositions Dust concentrates, such as above-described, or, al prepared from many of the aforesaid compounds (as an ternatively, appropriate crotyl derivative compounds active ingredient) in intimate admixture with at least one material of the group consisting of finely-divided 60 may be intimately mixed with liquid or solid ionic or inert solids, granular solids, surface active dispersing non-ionic dispersing agents to form spray concentrates. agents, beeswax, paraffin waxes, water, organic Sol Such concentrates are readily dispersible in liquid car vents, nitrogen fertilizers, potassium fertilizers, meta riers to form sprays containing the crotyl derivative in phosphates, etc. Particularly contemplated as desirable any desired amount. concentrate compositions are those which comprise 65 ; : Any of the above crotyl compounds of this invention the aforesaid novel chlorocrotyl compounds of this in may also be compounded with suitable water-miscible vention as active ingredients in an intimate admixture or water-immiscible organic liquid and surface active 3,884,963 9 O dispersing agents, provided that they do not react with weather effects. An additional factor to be considered the N-chlorocrotyl compounds, to produce liquid con is the plant species to be treated, as well as the presence centrates which may be further formulated with water or absence of desirable plants together with the unde and/or oil to prepare spray mixtures in the form of sirable species. Thus, selective grass control may be aqueous dispersions or oil-in-water emulsion composi 5 achieved by administering sufficient N-chlorocrotyl de tions. The exact step to be employed in preparing such rivatives of this invention to eradicate grasses without compositions is within the knowledge of those skilled affecting broad base leaf. in the art. Preferred water-immiscible organic liquids Effective control of terrestrial plants in soil may be include petroleum oil and distillates, toluene, Xylene, readily achieved by the administration of varies N O chlorocrotyl derivatives of this invention. cumene and other aromatic hydrocarbon solvents, The administration of the present compounds or chlorinated aliphatic hydrocarbons, isoparaffin oil and compositions thereof to plant or plant growth media other alliphatic hydrocarbon solvents. may be carried out in any manner known to those skilled in the art and may be carried out by using dust When the aforesaid crotyl derivatives of this inven 15 compositions, sprays or any other modification pro tion are alkali metal, ammonium, or amine salts, aque vided that an effective dosage is supplied. It is to be un ous concentrate compositions are readily prepared. derstood that the total volume or weight of the treating The salts may be first compounded in a water-miscible composition to be employed is not critical so long as organic solvent and added to a minimal amount of wa the critical amount of the aforesaid crotyl compound is ter, or they may be directly compounded in water or in 20 supplied, which is, in the present instance, about 0.5 to a water-organic solvent mixture. Usually the use of a 50 pounds per acre. Frequently, the desirability of a procedure which includes addition of a small amount more concentrated or dilute composition depends of a water-miscible organic solvent is preferred. More upon a method of application and the area to be cov over, in the case of salt compositions, the salt need not ered; hence, the selection of the concentration and be preformed but may be prepared during the com 25 total volume or weight may be made by those of ordi pounding process. Thus, the desired N-chlorocrotyl nary skill in the art in view of the foregoing teachings. compound and desired amine or inorganic base may be The present invention is further illustrated in greater mixed together in appropriate amounts in an aqueous detail by the following examples, but it is to be under organic solvent mixture. stood that the present invention, in its broadest aspects, 30 is not necessarily limited in terms of the specific tem The present composition may also contain other peratures, residence times, reactants, pressures, sol plant growth modifying agents either as adjuvants or vents, analytical techniques, separation techniques, supplementary materials for both terrestrial and and other process conditions by which the compounds aquatic applications. and compositions described and claimed in this inven In carrying out the methods of the present invention, 35 tion are prepared and used. as they pertain to the growth control of fungi or of plant growth or vegetation, the crotyl derivatives of this in EXAMPLE I vention are administered to foliage, plant parts, or growth media of the plant species whose pesticide con 40 trol is desired. The exact amount to be administered va The Addition of N,N-Dichloro Methyl Carbamate to ries with the particular type of growth control to be Conjugated Dienes achieved. It further varies with method of application, i.e., whether the application is to be made to foliage, food, flower, or particular plant part, or to soil or other. The N,N-dichloro methyl carbamate was added growth media, and the overall site of application: a dropwise to a stirred nitrogoen purged solution of an sheltered area, such as a greenhouse; or an exposed equimolar amount of conjugated diene in methylene area, such as fields, etc. Thus, as for example, in the chloride solution cooled to between -10 and -20°C by treatment of grass and weeds, soil application is pre a dry ice-isopropanol bath. The rate of addition of the ferred to foliage application and the amounts are gov carbamate was such that the internal temperature was erned thereby. Also, weeds present in sheltered areas maintained between -20 and 0°C. After addition was are more responsive to treatment and minimal dosages complete the reaction mixture was allowed to warm to are usually adequate whereas field applications often room temperature. The solvent was removed at aspira times require higher dosages to counteract adverse tor pressure at ambient temperature to yield the crude TABLE PREPARATION OF N-CHLORO-N-(4-CHLOROCROTYL) METHYL CARBAMATES

O R Rs O R. Rs N / y CHOCNCl + / C-C-C-C CHOCN-C-C-C-C-Cl N R R. Rs R CE R. R. R. R. % Adduct% somers, C% H% N% R,R,R,R,R,R, Yield b.p.C.(mm) n by 1,2 nmr, 14 Calcd. Found Calcd. Found Calcd Found H, H., H., H., H., H., 91 52-6(0.005) 14930 14 86 36.38 36.27 4.58 473 7.07 6.98 H, H, CH, H, H, H, 82 72-4(0.065) 1.4964 85(a) 39.64 39.55 5.23 5.35 6.60 6.63 H, H, CH, CH, H, H 80 83 (0.006) 4996 100 42.49 42.41 5.80 5.99 6.19 6.12 H, H, C, H, H, H 82 78 (0.003) 15095 100 30.99 306 3.47 3.90 6.02 6.05 H, H, H, H, H, CH 84 65 (0.01) 1.4852 27 730) 39.64 39.28 5.23 5.32 6.60 6.23 to 15% 4, 1-addition 3,884,963 1. 12 product as an oil. The product was then purified by (0.15 mole) of N,N-dichloro isopropyl carbamate in 25 vacuum distillation. ml of methylene chloride solution cooled to -10°C. The results obtained using this procedure or its con The rate of addition was such that the internal tempera verse, i.e., adding the conjugated diene to a solution of ture was maintained between 0 and 5°C. After addi 5 tion was completed, the reaction was slowly warmed to the N,N-dichloro methyl carbamate in methylene chlo room temperature. The solvent was evaporated to give ride solution, are summarized in Table I. 36 g. of crude product. Distillation gave a 94% yield of mono adduct b.p. 85°-7°C (0.007 mm), ni' 1,4814. EXAMPLE 2 An examination of the nmr spectrum of this mono ad 10 duct indicated that the material consisted of an 85:15 The Addition of N,N-Dichloro Methyl Carbamate to mixture of 1,4- and 4, 1-adducts. 1,3-Butadiene Calcd. for CHCl,NO: C, 52.55; H, 7.84; N, 6.81. 1,3-Butadiene (54 g, 1.0 mole) was diluted with ni Found: C, 55.32; H, 8.16; N, 6.81. trogen and slowly passed with stirring into 140 g (0.98 15 mole) of N,N-dichloro methyl carbamate cooled to -1- EXAMPLE 6 0°C. by a dry ice-acetone bath. The rate of addition was such that the internal temperature was maintained be The Addition of N,N-Dichloro Isopropyl Carbamate to tween 5 and 10°C. After addition was complete the re 2,3-Dimethyl-1,3-Butadiene. action was warmed slowly to room temperature. The 20 The reaction 0.08 mole of N,N-dichloro isopropyl yield of product was 192 g. A gc analysis indicated a carbamate with 0.08 mole of 2,3-dimethyl-1,3- purity of 98% and a 90:10 ratio of 1,4- to 1,2-adducts. butadiene using the above procedure gave 15.4 g (0.065 mole, 82%) of N-chloro-N-2,3-dimethyl-4- EXAMPLE 3 25 chlorobut-2-ene-(1) isopropyl carbamate b.p. 81-3°C. (0.005 mm), n° 1.4850. Calcd. for CHClNO: C, 47.25; H, 6.75, N, 5.51. The addition of N,N-Dichloro Methyl Carbamate to Found: C, 47.30; H, 7.06; N, 5.30. 1,3-Butadiene 1,3-Butadiene (5.4g, 0.1 mole) was diluted with ni 30 trogen and passed into a stirred solution of 14.2 g (0.1 EXAMPLE 7 mole) of N,N-dichloro methyl carbamate in 35 ml of benzene cooled by an ice water bath. The rate of addi The Addition of N,N,N',N'-Tetrachloro Ethylene tion was adjusted to maintain the internal temperature Glycol Bis Carbamate to Chloroprene between 5 and 10°C. After addition was complete the 35 A solution of 9.8 g (0.034 mole) of N,N,N', N'- solution was slowly warmed to room temperature. The tetrachloro ethylene glycol bis carbamate in 15 ml of benzene was evaporated to yield 19.6 g. of oil. A go methylene chloride solution was added dropwise with analysis indicates a 90:10 ratio of 1,4- to 1,2-adducts. stirring to a solution of 6.1 g (0.068 mole) of freshly Analysis by nmr indicates a 88:12 ratio of the same ad distilled chloroprene in 15 ml of methylene chloride ducts. 40 cooled to -20°C. in a dry ice-acetone bath. The rate of addition was such that the internal temperature re EXAMPLE 4 mained below -10°C. After addition was complete the The addition of N,N-Dichloro Isopropyl Carbamate to reaction was warmed slowly to room temperature and Butadiene-1,3 45 the solvent evaporated to yield 15.8 g of oily adduct. 1,3-Butadiene (10.6 g., 0.2 mole) was diluted with ni The material was homogeneous on tic. The nmr indi trogen and passed into 34.0 g (0.2 mole) of N,N- cated exclusive 1,4-addition with a small amount of dichloroisopropyl carbamate cooled to -10°C. by a dry methylene chloride as the chief contaminant. A sample ice-acetone bath. The rate of addition of diene was ad was stored under high vacuum at room temperature for justed so as to maintain the internal temperature be 50 15 hours and then submitted for elemental analysis. tween 5 and 10°C. After addition was complete the re Calcd. for CHCNO: C, 31.12; H, 3.05; N, 6.05 action was warmed slowly to room temperature. The Found: C, 30.74; H, 3.25; N, 6.08. product weighed 43.2g. A gc analysis showed an 89:11 EXAMPLE 8 ratio of 1,4 to 1,2-adducts and a purity of 98%. The product was purified by vacuum distillation to give an 55 The Addition of N,N,N',N'-Tetrachloro Ethylene 85% yield of adduct, b.p. 75-7°C. (0.006 mm), no Glycol Bis Carbamate to 1,3-Butadiene 1.4762. The reaction was performed as described in Example Calcd. for CHCl2.No.:C, 42.49; H, 5.80; N, 6.20. 3 to give 73 g. of adduct as an oil from 53.6 g. of Found: C, 42.53; H, 5.85; N, 6.32. N,N',N',N'-tetrachloroethylene glycol bis carbamate. 60 An nmr spectrum of this material indicated that it con EXAMPLE 5 sisted of an 85:15 mixture of 1,4- and 1,2-adducts. Calcd. for CHCl2NO: N, 7, 11 Found: N, 7.14 The Addition of N,N-Dichloro Isopropyl Carbamate to EXAMPLE 9 Isoprene 65 Isoprene (10.2 g, 0.15 mole) was added dropwise General Procedure for the Reduction of N-Chloro-N- with stirring to a nitrogen purged solution of 25.8 g. (4-chlorocrotyl-(1) Carbamates. 3,884,963 13 14 A solution of N-chloro-N-(4-chlorocrotyl-(1)) Cas EXAMPLE 1 1 bamate in methylene chloride was vigorously stirred at The Addition of N,N-Dichloro Methanesulfonamide to ambient temperature with an aqueous solution of a Chloroprene three-fold excess of sodium sulfite until the organic layer failed to give a positive potassium iodide test. The 5 A solution of 30.0 g (0.183 mole) of N,N-dichloro layers were separated and the methylene chloride methanesulfonamide in 75 ml of methylene chloride phase was washed with water and dried over anhydrous was added dropwise to a stirred solution of 16.2 g potassium carbonate. The methylene chloride was (0.183 mole) of chloroprene in 50 ml of methylene evaporated at ambient temperature to yield the re chloride and cooled to -20°C. in a dry ice-isopropanol duced product as a liquid or solid which was then puri 10 bath. The rate of addition was controlled so that the in fied by the appropriate method. The results are listed ternal temperature of the reaction mixture remained in Table II. between -10 and 0°C. After addition was complete the reaction mixture was allowed to slowly come to TABLE II room temperature. The solvent was removed at aspira Reduction of N-Chloro-N-Crotyl Carbamates with Sodium Sulfite 15 tor pressure to yield 46 g of solid. Recrystallization O O from carbon tetrachloride gave 41.1 g (89%) of 1,4- adduct m.p. 70-2C. . ROCN-R - NaSOs ROCNHR

C 20 O EXAMPLE 12 f RO-C-NH-R Addition of N,N-Dichloro Sulfonamides TO R R Yield, m.p. (b.p), “C. Conjugated Dienes in General 25 N,N-dichlorobenzene sulfonamide,-4-chlorobenzene CH CH-CH=CH-CHCI 89 3-3 sulfonamide, and methane sulfonamide were reacted with butadiene and chloroprene in a manner described CH in Example 5. m CH CH-C=CH-CH,Cl 76 31-2 Pertinent data regarding the preparation of the result 30 ing N-chloro-N-crotyl sulfonamides are given in Table C III. CH CH-C=CH-CHCI 78 58-9 CHCH TABLE III PREPARATION OF N-CHLORO-N-CROTYL SULFONAMIDES CH CH-C = C-CHC 84 52-3 35 CH-CH=CH-CH-Cl R'SONCl-CH-C-CH=CH, R'SONCH-C=CHCHCl CH (846°C/ f CH CH-CH=CH-CH-C 82 0.004mm) X Cl X R'' X % Yield m.p.C. CH 40 CHs H T6 53-5 i-CH CH-CH=CH-CH.Cl 78 61-2 Cshs Cl 90 51-2 pCl-CH H. 85 26-7 CH pCl-CH C 85 87-8 CH H 85 52-3 . i-CH CH-CeCH-CH.Cl 81 51-2 CH, Cl 89 70-2. -- - - - 45

EXAMPLE 10 Satisfactory elemental analyses were obtained on all 50 adducts. The Addition of N,N-Dichloro Benzenesulfonamide to 1,3-Butadiene EXAMPLE 13 1,3-Butadiene (1.6g, 0.03 mole) was diluted with ni 55 trogen and slowly distilled into a stirred solution of General Procedure for the Reduction of N,N-Dichloro N,N-dichlorobenzenesulfonamide (5.9 g, 0.026 mole) Sulfonamide-Conjugated Diene Adducts in 15 ml of methylene chloride cooled to -10°C. by a dry ice-isopropanol bath. The rate of addition was such A solution of adduct in methylene chloride was vigor that the internal temperature of the reaction remained 60 ously stirred at room temperature with an aqueous so between 0° and 5. After addition was complete the re lution containing a threefold excess of sodium sulfite action mixture was allowed to slowly come to room until the organic layer failed to give a positive potas temperature. The solvent was removed at ambient tem sium iodide test. The organic layer was separated, dried perature at aspirator pressure to give 7.4 g of oil which over sodium sulfate, filtered and evaporated to give the solidified on standing. Recrystallization from a carbon 65 reduced product which was then purified by recrystalli tetrachloride-pentane mixture gave 5.7 g (76%) of 1,4- zation. Pertinent data regarding the reduction of N adduct m.p. 53-5°C. chloro-N-crotyl sulfonamides are given in Table IV. 3,884,963 1S 16 and 5°C. After addition was complete the reaction was TABLE IV warmed slowly to room temperature and the solvent REDUCTION OF N-CHLORO-N-CROTYL SULFONAMIDES evaporated to yield an oil. The oil was dissolved in car - NaSO bon tetrachloride and pentane was added to the cloud R'SONCH-C=CHCHCI- a2SU point. Upon cooling 15.0 g, 84%, of 1,4-adduct m.p. C X 36-8°C. crystallized. An analytical sample had a m.p. R'SONHCHC=CHCHCI 38° 40°C. Anal. Calcd. for CHClNOS: C, 25.59; H,3.94, N., X 9.95; S, 11.39. Found: C, 25.64; H, 3.91; N, 10.65; S, () 1.46. R" X % Yield m.p.C. CHs H 82 Oil CHs. C 80 83-4 pClC6H4 H 78 78-9 pCCH C 78 81-2 CH H 82 26-7 15 FXAMPLE 15 CH Cl 85 57-8 Use of N-Chloro-N-Crotyl Carbamates and Their Satisfactory elemental analyses were obtained on all Reduction Products as Soil Fungicides reduction products. 20

Using standard techniques both the N,N-dichloro EXAMPLE 14 methyl carbamate-1,3-butadiene adduct and its re 25 duced derivative were screened by the Wisconsin Alumni Research Foundation as soil fungicides. The Addition of N,N-Dichloro-N',N'-Dimethylsulfamide test organism used for cucumbers was Pythium sp., for to Chloroprene cotton, Rhizoctonia solani and for tomatoes, Fusarium oxysporum. The data obtained are listed in Table IV. A solution of 12.2 g (0.063 mole) of N,N-dichloro 30 The data showed that both the adduct and its re N',N'-dimethylsulfamide in 50 ml of methylene chlo duced derivative show a fungicidal effect. For example, ride was added dropwise to a stirred solution of 5.6 g in the case of the N,N-dichloro methyl carbamate ad (0.063 mole) of freshly distilled chloroprene in 25 ml duct treated soil eight of the cotton plants survived of methylene chloride cooled to -15°C. by a dry ice even though they were inoculated with Pythium sp. In isopropanol bath. The rate of addition was regulated so 35 contrast, in the untreated but inoculated soil, none of that the internal temperature remained between -10 the cotton plants survived.

TABLE VI SOIL FUNGICIDAL ACTIVITY OF N-CHLORO-N-CROTYL CARBAMATES AND REDUCED DERVATIVES : 36 **Number of Plants Surviv. Reference Structure Conc. Soil Cotton Cucumber Tomato Table CH3OCN-CH2CH=CH-CH2Cl O.5. Inoc. * 8 9 ill O. 5 Uninoc. * 9 O 6 C Table IT CHOCNHCH-CH=CH-CH.Cl o. 5 Inoc. 9 O 6 Uninoc. 9. O 2O

9 Table III CHOCNHCH2C=CHCH2Cl O. l. Uninoc.noc. 8O 67 178 CH 3 Untreated -- Inoc. O O 6 -- Uninoc. 8 9 l6 Inoculated Uninoculated * Each flat both inoculated and uninoculated was seeded with cotton, l0 cucumber and 20 tomatoe seeds. 3,884,963 17 18 EXAMPLE 16 EXAMPLE 17 Use of N-Chloro-N-Crotyl Carbamates and Their Use of N-Chloro-N-Crotyl Sulfonamides as Soil Reduction Products on Herbicides Fungicides 5 Samples of unknown activity are tested at a concen- The N,N-dichloro methyl sulfonamide-chloroprene tration equivalent to 20 lbs. per acre. Atrazine and adduct was screened by the Boyce Thompson Institute 2,4-D are used as positive standards. for Plant Research, Inc. as a soil fungicide. The follow ing procedure was used. Pre-emergence tests - Duplicate paper pots filled O with a Soil mixture are seeded with snap beans, cotton, Separate lots of sterilized soil were inoculated with corn, wheat, mustard, pigweed, crabgrass and foxtail. Pythium, Fusarium, and Rhizoctonia. The inoculated Immediately after seeding the soil is sprayed with the soil was placed in 4 oz. dixie cups and 2 to 5 days later Sample solution. Growth occurs under artificial light the cups were drenched with 30 ml of a formulation with overhead irrigation. The plants are observed for 15 containing sufficient chemicals to give a dose rate of 50 about 10 days and an injury rating is given in compari lbs./acre or 25 ppm in the soil. The treated cups were son with untreated controls. incubated for 2 days at 70F. The amount of mycelial growth on the soil surface was then rated on a scale of Post-emergence tests - Duplicate paper pots filled 1-5, where l = no control and 5 F complete control of with vermiculite are seeded with the same plants em 20 mycelial growth. ployed in the pre-emergence tests. Growth occurs under artificial light with irrigation provided by placing the porous pots in a small amount of water in stainless The mycelial growths on Pythium, Fusarium and Rhi steel trays. After about ten days when the test plants Zoctonia were rated 5, 4,3 indicating from complete to reach a suitable size they are sprayed with the sample. 25 substantial control. Observations are made for ten days and an injury rating is given in comparison with untreated controls. it will be understood that the foregoing description is merely illustrative of preferred embodiments and spe The results are shown in Table VI. The data show cific examples of the present invention and that varia that although the N-chlorocrotyl carbamates of the 30 tions may be made in such embodiments and examples TABLE VI POST-EM FRGFNCE HERBICIDA, TEST DATA FOR N-CHIORO-N-CROTYL CARBAMATES AND THEIR REDUCTION PRODUCTS

Reference Conc. Mustard Pigweed Crah-Grass Foxtail Corn Wheat Cotton Beans Table Structure Aca) Post Post Post.* Post.* Post.* Post.* Post ost

I CHOCN(CI)CHCH=CHCHCl ().5 SG 5G 5 3T 4T 3T 4G 4G t 4W 5W 5W 2U O CHOCNHCHCH=CHCHCl ().5 5G SG 4T 3. 5T 3T 4G 3G f 4W 5W 2W L 3W L 3U ()

(HOCNC is + CH=CHCH=CHCH 0.5 4W4G 4W5G 2L3T 2.3. 2L2T 2.2T 3LS 2C2L O CHOCN (Cl)CHC(CH)=CCH ().5 4G SG 3. 4. 4T 2L 2,1S 3. t M 4N 5W 2. 2. 3W 2T 3G 2G () CHCI

CHOCNHCHC(CH)=f CHCHCl ().5 2G 4W4G 2 2LI 21. 2T2. 2.1S 2G3. () intreated () () () () () () () () () Legend - Degree of injury Type of injury () - nine 3 - moderately severe C - Chlorosis NG - No Growth TB - Termina Bud - slight 4 - severe E - Epinasty R - Reduction U - Leaf Curl Upward 2 - Moderate 5 - clath G - General Necrosis RG - Reduced Germination W - Wilting H - Hypertrophy S - Stunting L - local Necrosis SS - Stem Swelling M - Mottle SC - Stem Curling NF - Nodule Formation T - Tip burn "').5' cance utritis in c. I respont's ti) ; rate (fir x. (ths, cre. irr to testing, no egree if injury was resent in mergents.

present invention are not active as pre-emergence her- 5 by those skilled in the art without departing from the bicides, they are highly active as post-emergence herbi- spirit and purview thereof. cides when used at a concentration of 0.5% which is What is claimed is: equivalent to 20 lbs. per acre. 1. A selective monoaddition process for the prepara 3,884,963 19 20 tion of C to Cao alkyl N-chloro-N-(4-chlorocrotyl-1) wherein R is a C to Cao alkyl with a conjugated diene carbamate compounds, comprising reacting a C to Cao of the formula N,N-dichloro alkyl carbamate compound with a C to Cao conjugated diene at a temperature of between about -80 and about 100°C. and pressures about 1 5 R2 R. R5 Rs and about 10 atmospheres in the liquid phase in the ab C = C - C C sence of added catalyst. f 2. A process for the preparation of C to Cao alkyl N-chloro-N-(4-chlorocrotyl-1) carbamate compounds R3 R7 comprising reacting a C to Cao alkyl N,N-dichloro car 10 bamate with a C4 to Cao conjugated diene at a tempera wherein R2 to R7 are hydrogen, chlorine, fluorine, ture of between about -80 and about 100°C. and pres methyl at a temperature of between about -80° and sures of between about 1 and about 10 atmospheres in about 100°C. and pressures about 1 and about 5 atmo the liquid phase. Spheres using a 1:1 to 1:5 ratio of the above reactants 3. A process according to claim 2 wherein said car 15 bamate is selected from the group consisting of C to in the absence of added catalysts. Cao alkyl carbamates and C to C1 alkylene bis carba 8. A selective monoaddition process according to nateS. claim 7 wherein R is methyl and R, to R are hydrogen. 4. A process according to claim 1 wherein said conju 9. A selective monoaddition-reduction process for gated diene is selected from the group consisting of iso-20 the preparation of N-(4-chlorocrotyl-1) carbamate prene, chloroprene, 1,3-butadiene, piperylene, 2,3- compounds comprising adding an N,N-dichloro car dimethyl butadiene, 2,3-dichloro-1,3-butadiene, bamate compound of the formula 2,4-dimethyl-1,3-pentadiene, 2-ethyl-1, 3-butadiene, 1,3-hexadiene, 2,4-hexadiene, 2-methyl-1,3- O pentadiene, and 4-methyl-1,3-pentadiene. 25 5. A process according to claim 1 wherein the reac tion step is conducted in the presence of a suitable sol Went. wherein R1 is a C to Cao alkyl radical, to a conjugated 6. A selective monoaddition process for the prepara diene of the formula tion of C, to Cao N-chloro-N-(4-chlorocrotyl-1) car 30 bamate compounds comprising reacting an N,N- dichloro carbamate compound having the formula R2 R4 R5 R6 C = C - C - C O 35 ROCNCl2 R3 R7 wherein R is a C to Cao alkyl, a C to Cao alkyl substi 40 wherein R2 to R7 are hydrogen, chlorine, fluorine, tuted with halo, with a C to Cao conjugated diene of the methyl at a temperature of between about -80 and formula about 100°C. in the absence of added catalyst and pres sures about 1 and about 10 atmospheres in the liquid phase to obtain a major amount of a monoadduct of the R2 R4 R5 R6 45 formula C is C - C = C R3 R7 9 R2 R R5 6 50 ROCN - C - C = C - C - Cl wherein R2 to R are monovalent radicals selected from t the group consisting of hydrogen, chlorine, fluorine; Cl Cl R3 R ( to Cao alkyl; C to Cao alkyl substituted with halo, phe nyl, Cs to Co phenyl substituted with halo, at a temper ature of between about -80 and about 100°C. and 55 and reducing the N-chloro group of said monoadduct pressures about 1 and about 10 atmospheres in the liq with sodium sulfite at a temperature of -20° to 100°C. uid phase using a 1 to l to l to 5 mole ratio of the above 10. A selective monoaddition-reduction process ac reactants in the absence of added catalysts. cording to claim 9 wherein R is methyl, R to R are 7. A selective monoaddition process for the prepara hydrogen. tion of N-chloro-N-(4-chlorocrotyl-1) carbamate com 60 11. Compounds having the formula pounds comprising reacting an N,N-dichloro carbam ate compound of the formula O 65 F2 R4 R5 Rs O Riocy - C - C = C - C - C. t RiOCNCla 21 3,884,963 22 wherein R is C to Cao alkyl, R., to R are hydrogen, wherein R is an aliphatic radical having from 1 to 30 chlorine, fluorine, C to Cao alkyl. carbon atoms and selected from the group consisting of 12. Compounds according to claim 11 wherein R is unsubstituted alkyl and halo, substituted alkyl radicals; methyl, ethyl, propyl and R2 to R are hydrogen, chlo and X is selected from the group consisting of hydrogen rine, fluorine, methyl. 5 and chlorine. 13. Compounds having the formula 18. Compounds having the formula O R.2 R.2. R.5 R 6 ROCN - C - C = C - C - Cl O

w A. R R7 J , O CH wherein R is one selected from the group consisting of ROC - N - CH - CH = CHCH2Cl C1 to Cao alkyl, a C to Cao alkyl substituted with halo, 15 R2 to R7 are monovalent radicals selected from the X group consisting of hydrogen, chlorine, fluorine, C to Cao alkyl, C1 to Cao alkyl substituted with halo, and X is selected from the group consisting of chlorine and hydrogen. 20 14. Compounds having the formula wherein R1 is an aliphatic radical having from 1 to 30 carbon atoms and selected from the group consisting of unsubstituted alkyl and halo, substituted alkyl radicals; O and X is selected from the group consisting of hydrogen ROC, - CH2 - CH = CHCH2Cl 25 and chlorine. wherein R is an aliphatic radical having from 1 to 30 19. Compounds having the formula carbon atoms and selected from the group consisting of O unsubstituted alkyl and halo, substituted alkyl radicals, t and X is selected from the group consisting of hydrogen and chlorine. ROC - N - CH2 - CH = CH - CH - Cl 15. Compounds having the formula X CH 35 O wherein R1 is an aliphatic radical having from 1 to 30 carbon atoms and selected from the group consisting of R1OCN - CH2 - CC1 = CHCH2Cl unsubstituted alkyl and halo, substituted alkyl radicals; and X is selected from the group consisting of hydrogen X 40 and chlorine. wherein R is an aliphatic radical having from 1 to 30 20. N-(4-chlorocrotyl-(1) methyl carbamate and carbon atoms and selected from the group consisting of the N-chloro derivative thereof. unsubstituted alkyl and halo, substituted alkyl radicals: 21. N-4-chlorocrotyl-(1)]isopropyl carbamate and and X is selected from the group consisting of hydrogen 4s the N-chloro derivative thereof. and chlorine. 16. Compounds having the formula 22. N-(2-methyl-4-chlorobut-2-ene (1) methylcarbamate and the N-chloro derivative thereof. O 50 23. N-(2-methyl-4-chlorobut-2-ene-(1) isopropyl ROC - CH2 - G = CH - CH2Cl carbamate and the N-chloro derivative thereof. X CH3 24. N-(2,3-dimethyl-4-chlorobut-2-ene-(1)) methyl carbamate and the N-chloro derivative thereof. 55 wherein R is an aliphatic radical having from 1 to 30 25. N-2,3-dimethyl-4-chlorobut-2-ene-(1)) isopro carbon atoms and selected from the group consisting of pyl carbamate and the N-chloro derivative thereof. unsubstituted alkyl and halo, substituted alkyl radicals; 26. N-2,4-dichlorobut-2-ene-(1) methyl carbamate and X is selected from the group consisting of hydrogen 60 and the N-chloro derivative thereof. and chlorine. 27. A compound of the formula 17. Compounds having the formula O t O CH, CH 3 65 CHOCN-CH2-CH=CH-CH-Cl3 ROC - N - CH2 - C - C - CH-Cl Cl CH3