3,639,471 United States Patent Office Patented Feb. 1, 1972 2 In this reaction (i), therefore, an intramolecular 3,639,471 splitting off occurs of hydrogen chloride from the car PROCESS FOR THE PREPARATION OF SULFEN bamic acid chloride molecule. YLATED CARBAMIC ACD FLUOR DES Erich Klauke, Odenthal-Hahnenberg, and Engelbert It has not hitherto been known, or successfully carried Kuhle, Bergedorf, Gladbach, Germany, assignors to out, that in monosubstituted carbamic acid chlorides the Farbenfabriken Bayer Aktiengesellschaft, Leverkusen, hydrogen atom on the nitrogen atom can be reacted with Germany acid chlorides, that is, that the hydrogen atom can be re No Drawing. Filled July 3, 1968, Ser. No. 742,176 placed by an acid radical. In this second case, an inter Claims priority, application Germany, July 5, 1967, molecular, rather than an intramolecular, splitting off of F 52,861 0. hydrogen chloride would be necessary. Int. C. C07c51/58, 101/10, 125/00 'If monosubstituted carbamic acid chlorides are reacted U.S. C. 260-544 C 20 Claims with acid-binding agents, such as triethylamine, and sul fenic acid chlorides, such as trichloromethyl-sulfenyl chloride, there is also obtained the appropriate isocyanate, ABSTRACT OF THE DISCLOSURE 5 since the trichloromethyl-sulfenyl chloride does not react. Reacting N-mono-(substituted- and unsubstituted-ali Thus, there occurs here again an intramolecular, in phatic, e.g. lower alkyl, -cycloaliphatic, e.g. C5-6 cyclo stead of an intermolecular, splitting off of hydrogen alkyl; and -aromatic, e.g. phenyl and halo-, nitro-, lower chloride. alkyl-, lower alkoxy-, lower alkylmercapto- and/or tri The second case reaction can be represented for ex fluoromethyl-phenyl)-substituted carbamic acid fluoride 20 ample by the following formula scheme: with (substituted- and unsubstituted-alkyl, e.g. haloalkyl; and -aryl, e.g. halo-, alkyl- and/or nitro-aryl, especially -phenyl)-sulfenic acid chloride or sulfur dichloride or di CO-Cl sulfur dichloride, in the presence of a tertiary amine as (ii) -N -- (CF3)3N -- ClS-CCl3 -> acid binding agent, e.g. at a temperature of about 0-100 25 H C., optionally in the presence of an inert organic solvent, (A) using about one mol of the carbamic acid fluoride per mol of said sulfenic acid chloride or at least two mols per mol of the sulfur dichloride or disulfur dichloride, to form the corresponding aforesaid N-(substituted- and 30 (B) (IIbb) unsubstituted-aliphatic, -cycloaliphatic and -aromatic)- N-(substituted- and unsubstituted-alkyl and -aryl)-sul If monosubstituted carbamic acid fluorides are reacted fenyl-carbamic acid fluoride and bis(N-substituted- and with an acid-binding agent, such as trimethylamine, and unsubstituted-aliphatic, -cycloaliphatic or -aromatic-N- a carboxylic acid chloride, such as acetic acid chloride, fluorocarbonyl)-amino-sulfide and -disulfide, which are the appropriate isocyanate in this third case is again ob particularly new compounds which possess arthropo tained. Here, too, there occurs merely an intramolecular dicidal, e.g. insecticidal and acaricidal, as well as fungi splitting off of hydrogen fluoride, but no intermolecular cidal properties, and which may be used as intermediates splitting off of hydrogen chloride. in organic synthesis. The course of this third case reaction can be represented 40 for example by the following formula scheme: The present invention relates to and has for its objects the provision for particular new methods of producing sulfenylated carbamic acid fluorides, and more particularly (iii) { X-NCcof -- (CBI)3N -- CH-CO-Cl -> N-(lower alkyl, C5-6 cycloalkyl, phenyl and halo- and 45 lower alkyl-substituted phenyl)-N-(halolower alkyl and H phenyl)-sulfenyl]-carbamic acid fluorides and bis-(N- (Iaa) (C) lower alkyl, C.s 6 cycloalkyl, phenyl and halo- and lower alkyl - substituted phenyl-N-fluorocarbonyl)-amino-sul { X-N=C=o -- (CH3) N.HCl -- CH-COF fides and -disulfides, which are particularly new com 50 pounds which possess arthropodicidal and fungicidal (B) (D) properties and which may be used as intermediates in organic synthesis, e.g. in a simple single step reaction, It has now been found, in accordance with the present using readily available starting materials whereby to at invention, that sulfenylated carbamic acid fluorides, i.e. tain outstanding yields, with other and further objects 55 N-(lower alkyl, C5-6 cycloalkyl, phenyl and halo- and of the invention becoming apparent from a study of the lower alkyl- substituted phenyl)-N-(halolower alkyl and within specification and accompanying examples. phenyl)-sulfenyl-carbamic acid fluorides and bis-(N- It is known that monosubstituted carbamic acid lower alkyl, C5-6 cycloalkyl, phenyl and halo- and lower chlorides can be converted smoothly into isocyanates with alkyl- substituted phenyl-N-fluorocarbonyl)-amino-sul fides and -disulfides, which are particularly new com acid-binding agents such as trimethyl amine (cf. Ann. 60 pounds which possess arthropodicidal, i.e. insecticidal and 562, 78 (1949). The course of the reaction can be acaricidal, as well as fungicidal properties, and which may represented for example by the following formula Scheme: be used as intermediates in organic synthesis, having the CO-C formula 65 co F (i) () (, -- (CH3)3N --> R-N (I) S-R2 (A) in which R1 is selected from the group consisting of lower ()-N=C=o -- (CH3)3N.HCl 70 alkyl, cycloalkyl having 5-6 ring carbon atoms, phenyl, (B) and substituted phenyl which is substituted with substitu 3,639,471 3 4 ents selected from the group consisting of lower alkyl and The starting materials are clearly characterized by the 1-3 halo, and Ra is selected from the group consisting above-mentioned Formulae IIa and IIb and even typify of halo lower alkyl, phenyl, the radical the analogous use of sulfur dichloride and disulfur di COF chloride. The carbamic acid fluorides (IIa) mentioned as start ing materials are already known (compare Soc. 1945, 864). As examples, there may be mentioned: methyl, and the radical butyl, isopropyl, cyclohexyl, phenyl, 4-chlorophenyl, 3 methylphenyl, 3-nitro-phenyl, 4-ethoxy-3-chloro-phenyl, O 3-trifluoromethyl-phenyl, 4-methylmercapto-phenyl, naph -S-N (ii) N thyl isocyanate, and the like. R The sulfenic acid chlorides to be used are also known in which the last-mentioned two R1 symbols are the same As examples there may be mentioned: sulfur dichloride, as defined above, can be obtained simply, that is in a disulfur dichloride, methyl-sulfenylchloride, perchloro one-step reaction, in high purity and with outstanding methylmercaptan, fluoro-dichloro-methyl-sulfenylchloride, yields, by the process which comprises reacting mono phenyl-sulfenylchloride, 4-chlorophenyl-sulfenylchloride, substituted carbamic acid fluorides, i.e. N-mono-(lower 4-tolylsulfenylchloride, 2-nitrophenyl-sulfenylchloride, and alkyl, C5-6 cycloalkyl, phenyl and halo- and lower alkyl the like. substituted phenyl)-substituted carbamic acid fluorides The reaction is expediently, though optionally, carried having the general formula 20 out in the presence of an organic solvent. COF As solvents (which term includes a mere diluent) which / may optionally be used in accordance with the process of R-N (IIa) the present invention, all inert organic solvents and mix H tures thereof are suitable. Preferred solvents include hy drocarbons, especially aliphatic and aromatic hydrocar in which R1 is the same as defined above, with a member bons and mixtures thereof, such as petroleum ether frac selected from the group consisting of sulfenic acid chlo tions, benzene, toluenes, and/or xylenes; chlorinated hy rides having the formula drocarbons, especially chlorinated aliphatic and chlori R2a-S-Cl (IIb) nated aromatic hydrocarbons and mixtures thereof, such in which R2 is halo lower alkyl or phenyl, sulfur dichlo 30 as carbon tetrachloride, methylene chloride, 1,1,2,2-tetra ride and disulfur dichloride, in the presence of a tertiary chloroethane, chlorobenzene, o-dichlorobenzene and/or a amine as acid-binding agent, for example at a temperature chloronaphthalene; ethers, especially aliphatic ethers, par substantially between about 0-100° C. Thus, in the last ticularly lower alkyl ethers, such as diethyl ether, cyclo mentioned formula R2a actually contemplates not only aliphatic ethers, such as dioxan; ketones especially ali halo lower alkyl and phenyl radicals corresponding to phatic ketones, particularly lower alkyl ketones, such as R of Formula I but also a chloro or chlorothio (i.e. methyl-isobutyl ketone; and esters, especially aliphatic Cl-S-) group, whereupon in the latter two cases two ether-aliphatic carboxylic acid esters including low mols of the mono-substituted carbamic acid fluoride should er alkoxy lower alkyl esters of lower alkanoic acids, such be used rather than one mol with the C1-S-Cl or as glycolmonomethyl ether acetate, i.e. methylglycol ace Cl-S-S-Cl reactant to obtain corresponding formula 40 tate, and glycolmonoethyl ether acetate; mixtures of the (I) compounds having the radicals foregoing; and the like. As acid-binding agents, all tertiary organic amines cus COF cof tomarily used for this purpose are suitable. These include -N and -S-N N N tertiary aliphatic, aromatic, mixed aliphatic-aromatic, and R R 45 heterocyclic amines such as trilower alkyl amines, tri for R2. phenyl amine, mixed lower alkyl and phenyl amines, tri The reaction may optionally take place in the presence benzyl amine, mixed lower alkyl, phenyl and benzyl of an inert organic solvent or diluent. amines, 5-membered heterocyclic amines, etc., for exam Advantageously, as aforesaid, by means of the instant ple trimethyl amine, triethyl amine, pyridine and dimethyl process the particular new carbamic acid fluorides of the 50 benzyl amine. present invention may be obtained in one step and with The reaction temperatures can be varied within a fairly high yields. wide range. In general, temperatures are substantially be It is very surprising that in accordance with the pro tween about 0 to 100 C., preferably from about 10 to duction process of the present invention the hydrogen 40° C. atom on the nitrogen of the carbamic acid fluoride is In the production process according to the present inven replaced by the sulfenic acid radical, with an intermolecu tion equivalent amounts of the reactants may in principle, lar splitting off of hydrogen chloride. It would certainly be used. The same applies to the acid-binding agents. have been expected that an intramolecular splitting off of When using sulfur dichloride and disulfur dichloride, hydrogen fluoride would occur and thus that the appro however, 2 mols of carbamic acid fluorides are used per priate isocyanate would be formed instead. 60 mol of such sulfenyl chlorides. If for example N-phenylcarbamic acid fluoride and For the reaction, the procedure can be that the two fluoro-dichloro-methyl-sulfenyl chloride are used, the reactants are provided as a mixture, and the acid-binding typical reaction according to the present invention can agent is then added to them. However, it is also possible be represented by the following formula scheme: first to form an adduct from the sulfenic acid chloride 65 COE and the tertiary amine and to react this intermediate prod uct with the starting monosubstituted carbamic acid fluo (iv) { X-NC -- ClS-CFC -- (CH3)3N - ride. Yi The products produced by the instant process can be (IIaa) (ilba) 70 purified by recrystallization and/or distillation. COF The sulfenylated carbamic acid fluorides are used in the main as intermediate products for further organic { X-NC synthesis. However, the particular new compounds of Ys-c FC the present invention themselves also exhibit insecticidal, . (l) 75 acaricidal and fungicidal properties. 3,639,471 5 6 The Substances obtainable by the process of the present a dispersible carrier liquid, e.g. organic solvent and/or invention exhibit strong insecticidal, acaricidal and fungi Water, preferablwy including a carrier vehicle assistant, cidal properties with comparatively low toxicity to warm e.g. Surface-active agent, such as an emulsifying agent blooded animals and low phytotoxicity. The insecticidal and/or a dispersing agent, and an amount of the active and acaricidal effect sets in rapidly and is long-lasting. compound which is effective for the purpose in question The active compounds produced can therefore be used and which is generally between about 0.001 and 95%, with good results for the control of mites (Acarina), and preferably 0.01 and 95%, by weight of the mixture. Diptera, etc. Such active compounds also inhibit fungi Furthermore, the present invention contemplates meth which attack plants from the soil. ods of Selectively controlling or combating pests, i.e. in The active compounds produced according to the in 10 Sects, acarids and fungi, which comprises applying to stant invention can be utilized, if desired, in the form of at least one of (a) such pets and (b) their habitat, i.e. the usual formulations or compositions with diluents or the locus to be protected, a combative or pesticidal extenders, i.e. dispersible carrier vehicles, such as solu amount, i.e. an insecticidally, acaricidally and/or fungi tions, emulsions, suspensions, emulsifiable concentrates, cidally effective amount, of the particular active com Spray powders, pastes, soluble powders, dusting agents, 15 pound of the invention alone or together with a carrier granules, etc. These are prepared in known manner, for vehicle as noted above. The instant informulations or com instance by extending the active compounds with dispers positions are applied in the usual manner, for instance ible liquid diluent carriers and/or dispersible solid car by spraying, atomizing, vaporizing, scattering, dusting, riers optionally with the use of carrier vehicle assistants, Watering, sprinkling, pouring, and the like. e.g. Surface-active agents, including emulsifying agents It will be realized, of course, that the concentration and/or dispersing agents, whereby, for example, in the of the particular active compound utilized in admixture case where water is used as diluent, organic solvents may with the carrier vehicle will depend upon the intended be added as auxiliary solvents (cf. Agricultural Chemicals, aplication. Therefore, in special cases, it is possible to March 1960, pages 35-38). The following may be chiefly go above or below the aforementioned concentration considered for use as carrier vehicles for this purpose; 25 ranges. dispersible liquid diluent carriers, including inert organic The insecticidal, acaricidal and fungicidal properties solvents, such as aromatic hydrocarbons (e.g. benzene, of the particular new compounds produced in accordance toluene, Xylene, etc.), halogenated especially chlorinated, with the present invention are illustrated, without limita aromatic hydrocarbons (e.g. chlorobenzenes), paraffins tion, by the following examples. (e.g. petroleum fractions), chlorinated aliphatic hydro 30 carbons (e.g. methylene chloride, etc.), alcohol (e.g. meth EXAMPLE 1. anol, ethanol, propanol, butanol, etc.), amines (e.g. etha Phaedon test nolamine, etc.), ethers, etheralcohols (e.g. glycol mono methyl ether, etc.), amides (e.g. dimethyl formamide, Solvent: 3 parts by weight dimethyl formamide etc.), sulfoxides (e.g. dimethyl sulfoxide, etc.), ketones Emulsifier: 1 part by weight alkylaryl polyglycol ether (e.g. acetone, etc.), and/or water; as well as dispersible To produce a suitable preparation of the particular finely divided solid carriers, such as ground natural min active compound, 1 part by weight of such active com erals (e.g. kaolins, alumina, silica, chalk, i.e. calcium pound is mixed with the stated amount of solvent con carbonate, talc, kieselguhr, etc.) and ground synthetic taining the stated amount of emulsifier, and the result minerals (e.g. highly dispersed silicic acid, silicates, e.g. 40 ing concentrate is diluted with water to the desired final alkali silicates, etc.); whereas the following may be chiefly concentration. considered for use as carrier vehicle assistants, e.g. sur Horse-radish leaves (Cochlearia armoratia) are face-active agents, for this purpose; emulsifying agents, sprayed with the preparation of the given active com such as non-ionic and/or anionic emulsifying agents (e.g. pound until dripping wet and then infested with mustard polyethylene oxide esters of fatty acids, polyethylene ox 45 beetles (Phaedon cochleariae). ide ethers of fatty alcohols, alkyl sulfonates, aryl sul After the specified period of time, the degree of de fonates, etc., and especially alkyl aryl-polyglycol ethers, struction is determined as a percentage: 100% means magnesium stearate, sodium oleate, etc.); and dispersing that all the beetles are killed; 0% means that none of agents, such as lignin, sulfite waste liquors, methyl cellu the beetles are killed. 50 The particular active compounds tested, their concen lose,Such etc. active compounds produced according to the in tration, the evaluation time and the results obtained can stant invention may be employed alone or in the form of be seen from the following Table 1. mixtures with one another and/or with such solid or liquid TABLE 1.--PLANT-DAMAGING INSECTS dispersible carrier vehicles and/or with other known. Phaedon larvae) 55 Concentra- Degree of compatible active agents, especially plant protection tion of destruction agents, such as other acaricides, insecticides, fungicides, active in percent herbicides, bactericides, etc., if desired, or in the form of compound after particular dosage preparations for specific application Active compound in percent 3 days made therefrom, such as solutions, emulsions, suspen (V1).--- COF 0.2 100 sions, powders, pastes, and granules which are thus ready 60 / for use. C- -N As concerns commercially marketed preparations, S CFC these generally contemplate carrier composition mix (V) - - - - C COF 0.2 00 tures in which the active compound is present in an amout substantially between about 0.1-95% by weight, Cl- -N and preferably 0.5-90% by weight, of the mixture, SCF Cl whereas carrier composition mixtures suitable for direct application or field application generally contemplate EXAMPLE 2. those in which the active compound is present in an 70 Tetranychus test amount substantially between about 0.001 and 5%, pref erably 0.01 and 0.5%, by weight of the mixture. Thus, Solvent: 3 parts by weight dimethyl formamide the present invention contemplates over-all composi Emulsifier: 1 part by weight alkylaryl polyglycol ether tions which comprise mixtures of a dispersible carrier To produce a suitable preparation of the particular vehicle such as (1) a dispersible carrier solid, or (2) 75 active compound, 1 part by weight of such active com 3,639,471 7 8 pound is mixed with the stated amount of solvent con diameter. The Petri dishes remain at 20° C. for 3 days taining the stated amount of emulsifier and the resulting for incubation. concentrate is diluted with water to the desired final con After this time, the inhibiting action of the active centration. compound on the mycelium growth is determined in Bean plants (Phaseolus vulgaris), which have a height categories, taking into account the untreated control. 0 of approximately 10-30 cm., are sprayed with the prepara means no mycelium growth, either on the treated sub tion of the given active compound until dripping wet. strate or on the inoculum, the symbol-means mycelium These bean plants are heavily infested with spider mites strate or on the inoculum, the symbol - means mycelium (Tetranychus urticae) in all stages of development. growth on the inoculum only with no spread to the After the specified period of time, the effectiveness of O treated Substrate, and the symbol -- means mycelium the preparation of active compound is determined by growth from the inoculum onto the treated substrate, counting the dead mites. The degree of destruction thus similar to the spread to the untreated substrate of the obtained is expressed as a percentage: 100%, means that control. all the spider mites are killed whereas 0% means that The particular active compounds tested, their con none of the spider mites are killed. centration, the test fungi and the inhibition effects The particular active compounds tested, their concen 5 achieved can be seen from the following Table 3. TABLE 3.- A GAR PLATE TEST Concentra tion of active con pound in Sclero the sub- Corti- tinia Verti. Thielavi- Phytoph- Fusariuin. strate in citin, sclero cilium opsis thora Fusarium Fusarium solanif. Active compound p.p.m. rolfsii liot, alboatrum basicola cactorum, ctimorum oatg8porum pisi Untreated.------(IV3).--- COF 100 0 O O O / C- -N N SCFC (V3).----. C OO 0 O O O -- COF Y C-( >-N SCFC (VI)-...- C OF OO 0 O O 0 O O O

CH-N SCFC tration, the evaluation time and the results obtained can The production process in accordance with the present be seen from the following Table 2. 40 invention is illustrated, without limitation, by the follow ing further examples. TABLE 2. -PLANT DAMAGING MITES Tetranychus EXAMPLE 4 Concentra- Degree of tion of destruction active in percent 45 compounds after (III) Active compounds in percent 48 hours S CF C1 (EV2) --- coF 0.2 100 27.8 g. N-phenylcarbamic acid fluoride and 34 g. fluoro C-K. Y-NC dichloro-methane-sulfenyl chloride are dissolved in 200 SCF Cl 50 ml. toluene, and 21 g. triethyl amine are added dropwise (V2).--- C 0.2 O COF at room temperature. The temperature is allowed to rise / to about 30° C. Stirring is effected for a time, suction Cl -N filtration from the amine salt (27 g.) is effected, the fil S CFC 55 trate is concentrated in a vacuum and the residue is dis tilled. 20 g. of the above compound, i.e. N-fluoro-dichlo EXAMPLE 3 ro-methyl-sulfenyl-N-phenyl-carbamic acid fluoride, are obtained of B.P. 133 to 136 C./12 mm. Hg, M.P. 53 Agar plate test 55° C. Test for fungitoxic effectiveness and breadth of the In the same manner, the following compounds are activity spectrum. 60 obtained. Solvent: Acetone Parts by weight: 100 (VII) C OF B.P. 147 to 150° C.112 mm. To produce a suitable preparation of the particular / E.g. 65 CH3- -N active compound, 1 part by weight of such active com N pound is taken up in the stated amount of solvent. SCEC The preparation of the given active compound is added (IV) C OF B.P. 159 to 160° C.1111mm. to potato dextrose agar (which has been liquefied by / Hg. heating) in such an amount that the desired concentra C- -N tion of active compound is set up therein. After thorough 70 SCFC (V) COE B.P. 175 to 177 C.110mm. shaking to achieve a uniform dispersion of the active / Hg. compound, the agar is poured into Petri dishes under C1 -N sterile conditions. When the mixture of substrate and N W active compound has solidified, test fungi from pure SCFC cultures are inoculated on to it in small discs of 5 mm. 75 C 3,639,471 9 O EXAMPLE 5 O (VI) COF the radical / COF CH3-N / SCF Cl2 -S-N 85 g. fluoro-dichloro-methane-sulfenyl chloride are dis Y, solved in 200 ml. ether, and 52 g. triethylamine are added in which the corresponding R is the same as defined at 10 to 20 C., with ice cooling. 38 g. N-methyl-carbamic above for R1 and especially lower alkyl, e.g. C-4 al acid fluoride are then added dropwise at the same tem kyl, particularly methyl, e.g. N-methyl-N-fluoro-car perature, suction filtration from the amine salt is effected, 10 bonyl-amino and -amino-thio. and the ether is evaporated. The residue is distilled in a In accordance with preferred embodiments of the vacuum. 53 g. of the above compound, i.e. N-fluoro-di invention: chloro-methyl-sulfenyl-N-methyl-carbamic acid fluoride, R1 is lower or C-4 alkyl; C5-6 cycloalkyl; mono- or di of B.P. 57 to 60° C./11 mm. Hg are obtained. chloro-phenyl; and lower or C-4 alkyl-phenyl; and In the same manner, there are obtained: Ra is halo lower or C-4 alkyl, especially with 1-3 and particularly 3 chloro and/or fluoro substituents; phen (VIII) COF B.P. 86 to 89° C.111 mm. Eig; yl; or the radical M.P. 38 to 39° C. CH-N CO SCCl3 20 (IX) COF B.P. 124 to 129° C.111 mm. Y, N in which R1 is lower or C14 alkyl. N It will be realized that the starting sulfenic acid chlo S CFC ride according to Formula Elb above contemplates for (X) COF BE; 135 to 140° C.111 mm. Raa not only the aforementioned haloalkyl and phenyl radicals but also in effect chloro and chlorothio (i.e. CH-N 2. 'Cl-S-) so as to cover specifically sulfur dichloride C1-S-Cl (chloro sulfenic acid chloride) and disulfur s–{ X dichloride Cl-S-S-C1 (chlorothio-sulfenic acid chlo EXAMPLE 6 30 ride) in which instances twice the quantity of the mono substituted carbamic acid fluoride will be used to produce (XI) CH-N-s-s-N-CH, the corresponding desired compounds of Formula I hav COE d OF ing the appropriate radical R2 in accordance with the pro 27 g. disulfur dichloride (0.2 mol) in 31 g. N-methyl duction process of the present invention. carbamic acid fluoride (0.4 mol) are dissolved in 150 ml. 35 It will be realized by the artisan that all of the fore toluene and 42 g. triethyl amine are added at 10 to 15° C. going compounds contemplated by the present invention, Stirring is effected for a time, the triethyl amine hydro i.e. produced by the instant process, possess the desired chloride formed is filtered off with suction, the filtrate is strong and selective insecticidal, acaricidal and fungicidal concentrated in a vacuum and the residue is distilled. By properties for combating insects, acarids and fungi, as re-distillation there are obtained 7 g. of the above prod 40 well as a comparatively low toxicity toward warm uct, i.e. bis-(N-methyl-N-fluorocarbonyl)-amino-disulfide, blooded creatures and a concomitantly low phytotoxicity, of B.P. 112 to 114 C./11 mm. Hg. enabling such compounds to be used with corresponding Using corresponding molar amounts of sulfur dichlo ly favorable compatibility with warm-blooded creatures ride and N-methyl-carbamic acid fluoride, with triethyl and plants for more effective control and/or elimination amine in toluene, in accordance with the procedure of Ex 45 of insects, acarids and fungi by application of such com ample 6, the corresponding bis(-N-methyl-N-fluorocar pounds to such pests and/or their habitat. bonyl)-amino-sulfide is obtained. It will be appreciated that the instant specification and Advantageously, in accordance with the present inven examples are set forth by way of illustration and not limi tion, in the foregoing formulae: tation, and that various modifications and changes may R represents 50 be made without departing from the spirit and scope of lower alkyl, especially alkyl having 1-4 carbon atoms, the present invention which is to be limited only by the such as methyl, ethyl, n- and iso-propyl, n-, iso-, sec.- scope of the appended claims. and tert-butyl, and the like, particularly methyl; What is claimed is: cycloalkyl having 5-6 ring carbon atoms, such as cy 1. Process for the production of sulfenylated carbamic clopentyl, cyclohexyl, and the like, particularly cy 55 acid fluorides having the formula clohexyl; phenyl; or COF substituted phenyl which is substituted with lower al kyl as defined above, particularly monomethyl, or Ys-R, 1-3 halo such as chloro, bromo, iodo and/or fluoro, 60 in which R1 is selected from the group consisting of lower particularly 1-2 chloro groups; alkyl, cycloalkyl having 5-6 ring carbon atoms, phenyl, R2 represents and substituted phenyl which is substituted with substit halo lower alkyl such as chloro, bromo, iodo and/or uents selected from the group consisting of lower alkyl fluoro substituted methyl, ethyl, m- and iso-propyl, and 1-3 halo, and R2 is selected from the group consist n-, iso-, sec- and tert-butyl, and the like, especially 65 haloalkyl having 1-4 carbon atoms and 1-3 halo ing of halo lower alkyl, phenyl, the radical groups, more especially chloro and/or fluoro-C-4 al COF kyl and particularly trichloro- and fluoro-dichloro -N methyl; phenyl; 70 the radical and the radical CO / -N N R1 75 3,639,471 11 12 in which last-mentioned instances R is the same as de alkyl and 1-3 halo, and R2 is selected from the group fined above, which comprises reacting mono-substituted consisting of halo lower alkyl, phenyl, the radical carbamic acid fluoride having the formula COE Yi in which R is the same as defined above, with a member and the radical selected from the group consisting of sulfenic acid chlo 0 COF ride having the formula -S-N N R in which Ra is selected from the group consisting of halo in which last-mentioned instances R1 is the same as de lower alkyl and phenyl, sulfur dichloride and disulfur di fined above. chloride, in the presence of a tertiary amine as acid 12. Compound according to claim 11 wherein R is binding agent, the tertiary amine contacting the mono selected from the group consisting of C-4 alkyl, C5-6 substituted carbamic acid fluoride reactant no sooner cycloalkyl, mono- and di-chloro-phenyl and C-4 alkyl than the sulfenic acid chloride. phenyl, and R2 is selected from the group consisting of 2. Process according to claim 1 wherein said reacting 20 trichloro-C-4 alkyl, monofluoro-dichloro-C-4 alkyl, is carried out at a temperature substantially between phenyl, and about 0-100 C. 3. Process according to claim 1 wherein said reacting COF is carried out in the presence of an inert organic solvent. --S-N 4. Process according to claim 3 wherein said inertor ganic solvent is selected from the group consisting of 25 Y, aliphatic hydrocarbons, aromatic hydrocarbons, chlori in which R1 in the last-mentioned instance is C1-4 alkyl. nated aliphatic hydrocarbons, chlorinated aromatic hy 13. Compound according to claim 11 wherein R is drocarbons, aliphatic ethers, cycloaliphatic ethers, ali selected from the group consisting of methyl, cyclohexyl, phatic ketones, aliphatic ether-aliphatic carboxylic acid 30 monochlorophenyl, dichlorophenyl and methylphenyl, esters, and mixtures thereof. and R2 is selected from the group consisting of trichloro 5. Process according to claim 1 wherein said tertiary methyl, fluoro-dichloromethyl, phenyl and N-methyl-N- amine is selected from the group consisting of tertiary fluorocarbonyl-amino-thio. aliphatic, aromatic, mixed aliphatic-aromatic, and hetero 14. Compound according to claim 11 wherein such cyclic amines. compound is N-phenyl-N-fluoro-dichloro-methyl-Sulfenyl 6. Process according to claim 1 wherein said reacting carbamic acid fluoride having the formula is carried out with about one mol of said mono-substi tuted carbamic acid fluoride per mol of said sulfenic acid cof chloride. 7. Process according to claim 1 wherein said reacting 40 { X-NCS-CFC is carried out with at least two mols of said mono-Substi tuted carbamic acid fluoride per mol of the member se 15. Compound according to claim 11 wherein such lected from the group consisting of sulfur dichloride and compound is N-3,4-dichloro-phenyl-N-fluoro-dichloro disulfur dichloride. methyl-sulfenyl-carbamic acid fluoride having the formula 8. Process according to claim 1 wherein R is selected 45 C from the group consisting of C-4 alkyl, C5-6 cycloalkyl, C OF mono- and di-chloro-phenyl and C-4 alkyl-phenyl, and -N R is selected from the group consisting of trichloro-C1-4 e N alkyl, monofluoro-dichloro-C-4 alkyl, phenyl, and SCE C1 COF 50 / 16. Compound according to claim 11 wherein such -S-N compound is N-methyl-N-fluoro-dichloro-methyl-sulfen N R yl-carbamic acid fluoride having the formula in which R1 in the last-mentioned instance is C-4 alkyl. COF 9. Process according to claim 1 wherein R is selected 55 / from the group consisting of methyl, cyclohexyl, mono CH-N chlorophenyl, dichlorophenyl and methylphenyl, and Raa SCF C1 is selected from the group consisting of trichloromethyl, fluoro-dichloromethyl, phenyl and N-methyl-N-fluorocar 17. Compound according to claim 11 wherein such bonyl-amino-thio. 60 compound is N-methyl-N-trichloro-methyl-sulfenyl-car 10. Process according to claim 1 wherein the sulfenic bamic acid fluoride having the formula acid chloride member and tertiary amine are used in the form of an adduct and such adduct is reacted with said cof mono-substituted carbamic acid fluoride. CH-N 11. Sulfenylated carbamic acid fluoride having the for 65 mula Ysco1, COF 18. Compound according to claim 11 wherein such / compound is N-cyclohexyl-N-fluoro-dichloro-methyl-sul O fenyl-carbamic acid fluoride having the formula R-N S-R2 in which R is selected from the group consisting of lower alkyl, cycloalkyl having 5-6 ring carbon atoms, COF phenyl, and substituted phenyl which is substituted with substituents selected from the group consisting of lower 5 { X-NC S CF C. 3,639,471 19. Compound acid 3. claim 11 wherein such re Cited compound is N-methyl-N-phenyl-sulfenyl-carbamic acid UNITED STATES PATENTS fluoride having the formula 3,499,030 3/1970 Kuhle ------260- 551 CF 5 FOREIGN PATENTS CH-N? 301,285 9/1965 Netherlands ------260-543 H Ys-{ X OTHER REFERENCES Reid: Organic Chemistry of Bivalent Sulfur, vol. 1 pp. 20. Compound according to claimo 11 wherein such 0 279-281. compound is bis-(N-methyl-N-fluorocarbonyl)-amino- LEWIS GOTTS, Primary Examiner disulfide having the formula E. J. GLEIMAN, Assistant Examiner CH-N-s-s-N-CH, 5 U.S. C. X.R. (of COF 260-453 A; 424-319