United States Patent (19) (11) 3,884,951 Oswald (45) May 20, 1975

54 THIOETHER ISOCYANATE ADDUCTS 56) References Cited 75 Inventor: Alexis A. Oswald, Mountainside, UNITED STATES PATENTS

N.J. 2,340,757 3/1938 Kaase et al...... 260/453 3,215,701 1 1/1965 Pomot...... 260/453 X (73) Assignee: Exxon Research & Engineering 3,409,631 1 1/1968 Hollschmidt et al...... 260/453 X Company, Linden, N.J. 3,519,686 7/1970 Nair...... 260/453 X 22 Filed: Jan. 18, 1971 FOREIGN PATENTS OR APPLICATIONS (21) Appl. No.: 107,474 981,346 1/1965 United Kingdom Related U.S. Application Data Primary Examiner-Lewis Gotts 62) Division of Ser. No. 759,200, Sept. 11, 1968, Pat. Assistant Examiner-Dolph H. Torrence No. 3,597,341. Attorney, Agent, or Firm-J, P. Corcoran; R. J. Baran 52 U.S. Cl...... 260/453 A; 71/98; 71/100; (57) ABSTRACT 711 Si6.9: S. i.E.A.S.; Novel thioether isocyanates and isothiocyanates can 260/454; 260/455 A: 260/470, 260/481 c: be produced by the addition of thiols to the olefinic y y 4241298. 424 1302 bonds of allyl isocyanates and isothiocyanates. They 51) Int. Cl coc 119/04 are useful as pesticides, especially as post-emergence is 8 Field of S.260/453AE433A453AR herbicides, and as polymer intermediates. 3 Claims, No Drawings 3,884,951 2 THIOETHER ISOCYANATE ADDUCTS to or smaller than p and the meaning of the various R groups is defined in the following CROSS-REFERENCE TO OTHER APPLICATIONS R' is a mono-, di- or polyvalent organic radical se This application is a divisional of an application bear lected from the group consisting of unsubstituted and ing U.S. Ser. No. 759,200, filed Sept. 11, 1968, U.S. 5 substituted C6 to Coo, preferably C to Cao, hydrocar Pat. No. 3597,341 in the name of Alexis A. Oswald. bon radicals whose substituents are sulfur, oxygen and silicon. The ' hydrocarbon radicals can be open PRIOR ART chain and cyclic aliphatic, and aromatic radicals. It is, It is known that isocyanates and isothiocyanates react however, preferred that they should be selected from with thiols under ionic conditions, especially at ele O saturated open chain aliphatic radicals and nonfused vated temperatures, to yield thiourethanes. For refer benzenoid radicals, such as phenylene with possible ences see H. L. Snape, Ber. Vol. 18, pages 24-32 phenyl and alkyl substituents, respectively. The nonhy (1885); E. Dyer and J. F. Glenn, J. Am. Chem. Soc., drocarbon substituents of these radicals are preferably Vol. 79, p. 366 (1957); U.S. Pat. No. 2,764,592. selected from the group consisting of chlorine, bro mine, C1-C4 alkylthio, hydroxy, C-C alkyloxy, C-C, R - N - C = X + R'SH --> alkylsulfonyl, phenylsulfonyl, cyano, C-C carboalk R - N - C - SR" oxyalkyl, acetyl, nitro. Examples of the various R' polyvalent radicals are H X provided in the specification when discussing monova R.R" = organic radical; X = O.S 20 lent radicals R, divalent radicals R', trivalent radicals Such formation of thiourethanes is accelerated by R'' derived from mono-, di- and trithiol reactants. Ex ionic catalysts and heating. amples of higher valent radicals are CH(CH), de However, the prior art has not been cognizant of the rived from durene tetrathiol, C(CHOCOCHCH) de selective low temperature reaction of the olefinic group rived from methane (tetracarbomethoxyethanethiol), 25 polyvalent hydrocarbon radicals derived from polypro of unsaturated isocyanates and/or isothiocyanates with pylene, polybutadiene, polypropyleneoxide, polypro thiols under free radical conditions to form novel, use pylenesulfide. ful anti-Markovnikov type adducts. R to Rs are monovalent radicals selected from the FIELD OF THE INVENTION group of hydrogen, methyl, chlorine, cyano, C to C1, This invention relates to novel thiol adducts of allylic 30 preferably C to C alkylthio substituted methyl, phe isocyanates and isothiocyanates, formulations or com nylthio substituted methyl and combination thereof. It positions thereof, and process or methods for preparing is, however, preferred that at least 3 of the above R rad and using same. More particularly, this invention re icals be hydrogen. Furthermore, it is preferred that the lates to novel thioether isocyanates, produced by the two remaining radicals be selected from the group of selective free radical addition of thiols to the olefinic 35 hydrogen and methyl radicals. double bond of allylic isocyanates and isothiocyanates. Preferably, the reaction is carried out with allyl isocy Such adducts are useful as pesticides, particularly as anate or allyl isothiocyanate as indicated by the follow post-emergence herbicides and as polymer intermedi ing scheme ates, particularly polyurethane intermediates. 40 R' (SH) + q CH = CH-CH - N = C = X-> SUMMARY OF THE INVENTION (HS) R' (S-CH - CH-CH, -N = C=X) The novel anti-Markovnikov adducts of this inven wherein the meaning of the symbols is the same as tion are generally prepared in the course of a free radi given at the earlier equation. cal addition process wherein a variety of thiols can be It is more preferred to react all the thiol groups of the added to the olefinic double bond of a variety of allylic 45 polythiol as shown by the following schemes isocyanates and isothiocyanates. In general, the reaction can be depicted by the fol Rl R3 R4 lowing reaction scheme l. 3 R4 50 R" (SH) + q - C - G --> R"" (SH) p + q C - C - C - N - C - X --> R2 R5 R2 R5 55 R. R3 R4 R l R3 R4 R" S - C - C - C - N = C is X r s (HS)p-R S N - C - X 60 R2 H R5 q R2 H Rs R' (SH) + q CH = CH - CH - N = C = X-> R'' (S - CH-CH - CH - N = C = X) wherein X is oxygen and sulfur, preferably oxygen, and 65 wherein p equals q. In general, this reaction may be ill p and q are each a positive integer from 1 to 30, prefer lustrated with allyl isocyanate and is thiocyanate in ac ably 1 to 5, most preferably 1 to 3, with q being equal cordance with Equation 1 below. 3,884,951 3 4 When a dithiol is reacted with an allyl isocyanate or EOUATION 1 isothiocyanate one or both thiol groups may participate in the addition reaction to the allylic double bond, as is shown in Equation 3 below. 5 EOUATION 3

HS-R -SH CH2=CH-CH-NCX wherein X is O or S, product I is formed in major amounts, and product II is formed in minor amounts, R being C-C20 hydrocarbyl moiety such as C1 to Co alkyl, C to Co monosubstituted alkyl, C to C20 disub CH=CH-CH-NCX stituted alkyl, Cs to Co aryl, Cs to Co monosubstituted aryl, Cs to Cao disubstituted aryl. The aliphatic moiety 15 XCN-CH2-CH-CH2-S-R'-S-CH-CH-CH-NCX has preferably C to C. carbon atoms. The aromatic moiety is preferably phenyl. Preferable substituents are wherein R' is a divalent organic radical such as C-Co chlorine, bromine, C-C alkylthio, hydroxy, C-C al alkylene, C-C phenylene, C6-Cio phenalkylene, e.g. kyloxy, C1-C4 alkylsulfonyl, phenylsulfonyl, cyano, xylylene. The alkylene group can also contain hetero C1-C4 carboalkoxy alkyl, acetyl, nitro, etc. Substitu 20 atoms such as S, SO, O, Si(CH) groups in which the ents, which catalyze the reaction of the thiol groups maximum carbon number of the continuous alkylene with the isocyanate or isothiocyanate groups must be unit is twenty, the number of alkyleneheteroatomic absent. Such substituents are all strongly basic and group units (n) being 0 to 100, e.g.: acidic groups such as alkylamino, sulfonic acid, phos phonic acid, etc. 25 In like manner, substituted allylic isocyanates and isothiocyanates can be reacted with thiols in accor Typical, non-limiting dithiol reactants include 1,3- dance with the following equation, Equation 2. propanedithiol, 1,6-hexanedithiol, cyclooctanedithiol, cyclododecanetrithiol, 1,2-ethanedithiol, benzenedi EOUATION 2 30 thiol, xylylene dithiol, 2-thio-bis-ethanethiol, 2-sulfonyl-bis-ethanethiol, 3-oxy-bis-propanethiol, R. R3 R4 3-hydroxy-1,2-propanedithiol, 3-chloro-1,2- propanedithiol, polyethylenethioetherdithiol, polye RSH + C a C - C - NECsx - thyleneoxidedithiol, polyethylenesulfonedithiol, polyp R2 R5 35 ropylenethioetherdithiol, etc. The monoadduct intermediate of the dithiol-allyl iso cyanate intermediate can undergo a polyselfaddition R. R3 R4 R3 R4 initiated by heat and/or ionic catalysts to form a poly RS-C - C - C - NCX + RS-C - C - NCX 40 thiourethane, as shown in Equation 4 below. R H R CH R EOUATION 4 2 5 R.1 R 5 II n+1 HS - R - S - CH2-CH2-CH-N-C-X-> 45 wherein X is O or S, product I is again the major prod uct, and product II is the minor product, R to Rs being X such moieties as hydrogen, CH3, Cl, CN, and C-C al HS-R terriers kylthio substituted methyl, phenylthio substituted methyl, C6-C10 monosubstituted phenylthio substituted 50 wherein n is 1 to 500, preferably 20 to 200. methyl, etc. Alternatively, the diadduct may be reacted with a Typical; non-limiting thiol reactants include such thi diol or dithiol to yield a polyurethane, as shown in ols as methanethiol, propanethiol, hydroxyethanethiol, alphatoluenethiol, benzenethiol, xylenethiol, chloro Equation 5. benzenethiol, t-butanethiol, 3-chloropropanethiol, hex 55 EOUATION 5 adecanethiol, naphthalenethiol, phenanthrenethiol, an thracenethiol, trichlorobenzenethiol, bromobenzene thiol, 3-hydroxypropanethiol, carbomethoxyethane thiol, 2-methylthioethanethiol, nitrobenzenethiol, methanesulfonylbenzenethiol, cyclohexanethiol, 2 60 acetylethanethiol, 12-hydroxydodecanethiol, 18 carboethoxyoctadecanethiol, 5,6-dichlorohexanethiol, 2-butenethiol, 2,3-epoxypropanethiol, etc. Typical, non-limiting isocyanate and isothiocyanate reactants of this invention include crotyl isocyanate, 65 rteritains,X X 2-methallyl isocyanate, 4-methylthiocrotyl isothiocya nate, 4-phenylthiocrotyl isocyanate, 4-chlorophenylthi ocrotyl isocyanate, 4-nitrophenylthiocrotyl isocyanate, In the case of trithiol reactants, the selective addi 2-chloroallyl isothiocyanate, xylylthiocrotyl isocya tions to allyl isocyanate and isothiocyanate can be car nate. ried out to various degrees, as shown in Equation 6. 3,884,951 S 6 EOUATION 6 Without wishing or intending to be bound by any the ory, it is nevertheless believed, from the structure of CH2=CHCH2NCX the adducts obtained, that the selective additions of this R"(SH) ---> invention take place by means of a free radical type chain mechanism and in accordance with the following postulated reaction mechanism. Initiation RSHa-) RS. 10 wherein (1) R' is a trivalent unsubstituted organic rad initiator ical containing from 6 to 500 carbon atoms, which radi cal can be substituted by such atoms as sulfur, oxygen and silicon, illustrative examples of these substituted Propagation radicals including polythioether, polyether, and polysi Step (1) lane trithiols, etc.; and (2) X is O and S, preferably O. Typical, non-limiting trithiol reactants include RS.--CH=CH-CH-NCO trimercaptoethyl cyclohexane, tri-mercaptoethylthio RS-CH-CH-CH-NCO cyclododecane, the tri-mercaptoacetic acid ester of tri Step (2) hydroxymethyl methane, the tetra-mercaptopropionic 20 acid ester of pentaerythritol, polypropylenethioether RS - CH-CH-CH-NCO -- trithiol, the di-mercaptoacetic ester of pentaerythritol, RSH RS-CH-CH-CH-NCO -- RS.--> the polythiol resulting from polybutadiene excess hy drogen sulfide addition, the hexathiol resulting from REACTION CONDITIONS trivinyl cyclohexane-hydrogen sulfide addition, the tri 25 The reaction temperatures employed in this inven thiol resulting from polypropylene thioether-dithiol tion are preferably kept below 100°C., most preferably trivinyl cyclohexane addition, etc. below about 50°C, in order to avoid concurrent ionic In the case of polythiols the number of allyl isocya reactions of the isocyanate group which result in the nate molecules reacted per molecule of polythiol can formation of by-products. The lower limit of the reac 30 tion temperature range is defined by the freezing point equal up to the number of thiol groups in the polythiol. of the reaction mixture employed, reaction initiation, The general reaction is shown by Equation 7. and the cost of refrigeration. Reaction temperatures EQUATION 7 are between about -150 and about --100°C., prefera R' (SH) + q CH=CHCHNCX-> (HS).R' bly between about-80 and about+50°C. For the initi (SCH2CH2CHNCX) wherein (1) R' is a poly 35 ation of the low temperature, selective free radical re valent organic radical containing from 6 to 200 carbon actions, nonchemical initiators are preferred, such as atoms, which radical can be substituted by such atoms as ultraviolet light, gamma radiation, etc. However, chem sulfur, oxygen and silicon, illustrative examples of these ical initiators can also be used below the temperature substituted radicals including polythioether, polyether, limits of the reactions. For example, chemical initiators 40 such as peroxides, derived from boron alkyls are suit and polysilane polythiols, etc.; (2) p and q are 3 to 30, able low temperature initiators. Other chemical initia with q being equal to or smaller than p, and (3) X is O tors include azo compounds, such as bis-azo-i- . or S, preferably O. butyronitrile, etc. Preferred dithiols are polymethylene and polyme Usually the reactions of this invention are carried out thylenethioether dithiols each of which can be reacted 45 with equivalent amounts of reactants in the liquid with allyl isocyante in accordance with Equation 8. phase at atmospheric pressures. If the thiol reactant is gaseous at the reaction temperature, superatmospheric EOUATION 8 pressure can be used to keep it in the liquid state. Alter in HS--(CH) S-- (CH) SH-- n+1 natively, such a thiol as, e.g., ethanethiol, can be slowly CH=CHCHNCO -> ONC (CH)aS-t- (CH) 50 introduced into the radiated, liquid allylic isocyanate S--(CH), S(CH)NCO compound. In general, the isocyanate reactants are wherein l is 1 to 12. good solvents for the thiols. Solid thiols can essentially A preferred trithiol is the triaddition product of the be dissolved in the isocyanate reactants to obtain liquid reaction of polymethylene and polymethylenethioether reaction mixtures. However, the use of nonreactive sol 55 vents at times can be desirable. Exemplary of suitable dithiols with trivinyl cyclohexane, which reaction is solvents are the open-chain and cyclic hydrocarbons shown in Equation 9. such as heptane, cyclohexane, benzene, xylene, etc.; EQUATION 9 aliphatic sulfides such as dimethyl sulfide; dialkyl Oft's (Ch.), (CH2 is), + 3CH-CHCH2NCO-> G-acts (t), (c),(cha).co) 3 When allylic isocyanates or isothiocyanates of this ethers such as diethyl ether; esters such as ethyl ace invention are reacted with polythiols, it is to be under tate; dialkyl sulfones such ad diethyl sulfone, etc. stood that the resulting reaction can be either a partial Although the reactants are usually employed in one or can be run until completion. equivalent amounts, an excess of either reactant be 3,884,951 7 8 Illustrative nonlimiting examples of R include methyl, yond the stoichiometric requirements can be used with octadecyl, t-butyl, phenyl, naphthyl, anthryl, cyclo beneficial results. For example, an excess of methane hexyl, 3-chloropropyl, trichlorophenyl, hydroxyethyl, thiol can be used to increase the rate of the overall ad nitroaphthyl, methanesulfonylphenyl, carboethoxy dition reaction to allyl isocyanates. Upon completion of methyl, epoxypropyl, cyanoethyl, acetylphenyl, etc. the free radical addition, the excess thiol can be re 5 The preferred monothiol adducts include ethylthio moved or used for anionic addition to the isocyanate propyl isocyanate, ethylthiopropyl isothiocyanate, group to form the corresponding thiourethane in accor cyanoethylthiopropyl isothiocyanate, dichloropropyl dance with the following equation, Equation 10. thiopropyl isothiocyanate, hexadecylthiopropyl iso EOUATION 10 O thiocyanate, naphthylthiopropy isothiocyanate, etc. In general, the dithiol adducts of this invention are CH3SH characterized by the following formulae: (l) CH2=CH-CH2-NCO excess } HS-R'-S(CH)NCX; XCN(CH)S-R'-S(CH)NCX; 15 Monoadduct Diadduct (2) CH3S(CH2) NCO - CHSH"3" ) and 20 I HS-R (CH2) 3NH-g-s-R (CH2 ) NCX O X The dithiol reactants of this invention such as e.g., Polyadduct ethane dithiol, can be reacted with half of the stoichio 25 metric requirements of allyl isocyanate to yield a thiol wherein R', X, and n are as previously defined in Equa isocyanate product which is itself subject to polyauto tions 3 and 4. addition to thereby result in a polyurethane product in Illustrative, nonlimiting examples of R' include prop accordance with the following equation, Equation 1 1. ylene, trimethylene, ethylene, xylylene, phenylene, 30 polyethylene thioether, polypropylenethioether, polye EQUATION | 1 thyleneoxide, polyethylenedimethylsilane, polyethy lenesulfone, polydodecamethylenethioether, etc. In general, the trithiol adducts of this invention are in HS (CH2)2SH + n CH2=CHCH2NCO --> characterized by the following formula: 35 R' (SCHCHCHNCX) wherein R' is as previously defined in Equation 6. The polythiol adducts of this invention are generally described by the following formula: 40 (HS) R' (SCHCHCHNCX) Alternatively, trithiols such as polythioether trithiols wherein R', p, q, and X are as previously defined in can be reacted with an excess of allyl isocyanate to con Equation 7. vert them to the corresponding polythioether triisocya The anti-Markovnikov adducts of this invention are nates. The excess allyl isocyante is then removed by 45 valuable intermediates which can themselves undergo distillation. all the customary reactions undergone by isocyanates In general, the monothiol adducts of this invention and isothiocyanates in general with such typical reac are characterized by the formulae: tants as alcohols, thiols, acids, amines, oximes, water, . etc. Moreover, the products derived from the reaction R 50 of dithiols, and polythiols with allylic isocyanates are in R3 R4 especially useful in polymer chemistry as monomers RS - C - C - C - N=C=X and cross-linking agents. t The diisocyanate, triisocyanate and polyisocyanate R2 H R5 containing adducts of di-, tri-, and polythiols are mainly and 55 utilized in polymer chemistry as monomer components with diols, triols, polyols and diamines, triamines, poly R3 R4 amines, and water. Their reaction as monomer compo RS - C - C - N=CsX nents leads to polyurethanes and polyureas. Difunc t tional diisocyanates when reacted with diols and di CH. R. 60 amines yield linear polymers. Polyfunctional isocya nates are useful as crosslinking agents. RY As previously noted, the anti-Markovnikov adducts of this invention are also useful as pesticides, particu larly as post-emergence herbicides. For pesticidal uses wherein R, R-Rs and X are as previously defined in 65 it is preferable that the adduct be derived from a mono Equation 2. or dithiol. As the other component an allylic isothio The preferred monothiol adducts of this invention cyanate is preferred. It is furthermore preferred that have the formula - the pesticidal adduct should have a molecular weight of RS-CH-Cha-CH-N=C=X less than 500. The dithiol used in the preparation of 3,884,951 9 10 pesticides is preferably a C to C4 polymethylene di for example, from about 5 to about 95 percent by thiol. weight of the active ingredient, preferably from about When used as post-emergence herbicides, the biolog 20 to about 80 weight percent. These concentrates can ically active ingredients are preferably formulated with be diluted with the same or a different carrier to a con a suitable carrier or diluent or combinations thereof. centration suitable for application. The compositions The term “carrier' or "diluent' as used herein of this invention can also be dilute compositions suit means a material, which can be inorganic or organic able for application. In general, concentrations of and synthetic or of natural origin, with which the active about 0.1 to about 10 percent by weight of the active ingredient of this invention can be mixed or formulated material based on the total weight of the composition, to facilitate its storage, transportation and handling, 10 are satisfactory, although lower and higher concentra and application to the plants, e.g., weeds, to be treated. tions can be applied if necessary. The carrier is preferably biologically and chemically The compositions of this invention can also be for inert and, as used, can be a solid or a fluid. When solid mulated as dusts. These comprise an admixture of the carriers are used, they are preferably particulate, gran active ingredient and a finely powdered solid carrier ular, or pelleted; however, other shapes and sizes of 15 solid carriers can be employed as well. Such preferably such as aforedescribed. The powdered carriers can be solid carriers can be naturally occurring minerals- al oil-treated to improve adhesion to the surface to which though subsequently subjected to sieving, sieving they are applied. These dusts can be concentrates, in purificaation, and/or other treatments, including for which case a highly sorptive carrier is preferably used. example, gypsum; tripolyte; diatomaceous earth; min These require dilution with the same or a different eral silicates such as mica, vermiculite, talc, and pyro finely powdered carrier, which can be of lower sorptive phyllite; clays of the montmorillonite; kaolinite, or atta capacity to a concentration suitable for application. pulgite groups; calcium or magnesium limes; or calcite The compositions of this invention can also be for and dolomite etc. Carriers produced synthetically, as mulated as wettable powders comprising a major pro for example, synthetic hydrous silica oxides and syn 25 portion of the active ingredient mixed with a disper thetic silicates can also be used, and many proprietary sant, i.e., a deflocculating or suspending agent, and, if products of this type are available commercially. The desired, a finely divided solid carrier and/or a wetting carrier can also be an elemental substance such as sul agent. The active ingredient can te in particulate form fur or carbon, preferably an activated carbon. If the or adsorbed on the carrier and preferably constitutes at carrier possesses intrinsic catalytic activity such that it 30 least about 10 percent, more preferably at least about would decompose the active ingredient, it is advanta 35 percent by weight of the final pesticidal composi geous to incorporate a stabilizing agent, as for example, tion. The concentration of the dispersing agent should polyglycols such as diethylene glycol to neutralize this in general be between about 0.5 and about 5 percent activity and thereby prevent possible decomposition of by weight of the total composition, although larger or the active and anti-Markovnikov ingredient. 35 smaller amounts can be used if desired. For some purposes, a resinous or waxy carrier can be The dispersing agent used in the composition of this used, preferably one which is solvent soluble or ther invention can be any substance having definite disper moplastic, including fusible. Examples of such carriers sant, i.e., deflocculating or suspending properties as are natural or synthetic resins such as coumarin, resin, distinct from wetting properties, although these sub rosin, copal, shellac, dammar, polyvinyl chloride, sty 40 stances can also possess wetting properties as well. rene polymers and copolymers, a solid grade of poly The dispersant or dispersing agent used can be pro chlorophenol such as is available under the registered tective colloids such as gelatin, glue, casein, gums, or trademark "Arochlor,' a bitumen, an asphalite; a wax, a synthetic polymeric material such as polyvinyl alco for example, beeswax, or a mineral wax such as a paraf 45 hol and methyl cellulose, etc. Preferably, however, the fin wax or Montan wax, or a chlorinated mineral wax, dispersants or dispersing agents used are sodium or cal or a micro-crystalline wax such as those available under cium salts of high molecular weight sulfonic acids, as the registered trademark "Mikrovan wax." Composi for example, the sodium or calcium salts of lignin de tions comprising said resinous or waxy carriers are rived from sulfite cellulose waste liquors. The calcium preferably in granular or pelleted form. 50 or sodium salts of condensed aryl sulfonic acids, for ex Fluid carriers can be liquids, as for example, water, ample, the products known as 37 Tamol 731," are also or an organic fluid, including a liquefied normally va suitable. porous or gaseous material, and can be solvents or non The wetting agents used can be nonionic type surfac solvents for the active material. For example, the horti tants, as for example, the condensation products of cultural petroleum spray oils boiling in the range of 55 fatty acids containing at least 12, preferably 16 to 20, from about 275 to about 575°F., or boiling in the range carbon atoms in the molecule, or abietic acid or nap of from about 575 to about 1,000°F. and having an un thenic acid obtained in the refining of petroleum oil sulfonatable residue of at least about 75 percent and fractions with alkylene oxides such as ethylene oxides preferably of at least about 90 percent, or mixtures of or propylene oxides, or with both ethylene oxides or 60 propylene oxides, as, for example, the condensation these two types of oils are particularly suitable liquid product of oleic acid and ethylene oxide containing CatleS. about 6 to 15 ethylene oxide units in the molecule. The carrier can be mixed or formulated with the ac Other nonionic wetting agents like polyalkylene oxide tive material during its manufacture or at any stage sub polymers, commercially known as "Pluronics' can be sequently. The carrier can be mixed or formulated with used. Partial esters of the above acids with polyhydric the active material in any proportion depending upon alcohols such as glycerol, polyglycerol, Sorbitol, manni the nature of the carrier. One or more carriers, more tol, etc., can also be used. over, can be used in combination. Suitable anionic wetting agents include the alkali The compositions of this invention can be concen metal salts, preferably sodium salts of sulfuric acid es trated, suitable for storage and transport and contain, ters or sulfonic acids containing at least 10 carbon 3,884,951 11 12 atoms in a molecule, for example, the sodium secon Into a quartz pressure tube equipped with a magnetic dary alkyl sulfates, dialkyl sodium sulfosuccinates stirrer and a Teflon screw valve, 49.8 grams (0.6 mole) available under the registered trademark “Teepol,' so of allyl isocyanate was placed. Then, 38.4 grams (0.8 dium salts of sulfonated castor oil, sodium dodecylben mole) of methanethiol was condensed to it, using a dry Zene sulfonate, etc. ice bath. The tube containing the reaction mixture was Granulated or pelleted compositions comprising a placed into a water bath, thermostated at 15°C., and suitable carrier having the active ingredient incorpo mounted upon a magnetic stirrer drive. The stirred re rated therein are also included in this invention. These action mixture was then irradiated from a distance of can be prepared by impregnating a granular carrier 5 centimeters by a 75 watt Hanau ultraviolet immersion with a solution of an active ingredient or by granulating 10 lamp having a high pressure mercury arc emitting a a mixture of a finely divided carrier and the active in wide spectrum radiation. gredient. The carrier used can contain a fertilizer or a The reaction mixture was sampled during the irradia fertilizer mixture, such as, for example, a super phos tion to determine the progress of the addition. Nuclear phate. magnetic resonance spectroscopy (nmr) was found to 15 be suitable, semiquantitative tool for the analysis of the The compositions of this invention can also be for samples. It showed that 80 percent of the allyl isocya mulated as solutions of the active ingredient in an or nate reacted in the first y2-hour irradiation time. A total ganic solvent or mixture of solvents, such as, for exam of 3 hours ultraviolet irradiation resluted in more than ple, alcohols, ketones, especially acetones; ethers; hy 95 percent conversion of the isocyanate. Nimr also drocarbons; etc. 20 showed that all the addition took place at the olefinic Where the toxicant itself is a liquid these materials bond. It could also be determined by nmr that 90 per can be sprayed upon crops without further dilution. cent of the addition took place in an anti-Markovnikov Petroleum hydrocarbon fractions used as solvents manner to yield 3-methylthiopropyl isocyanate. About should preferably have a flash point about 73°F., an ex 10 percent of the adduct was of the opposite orienta ample of this being a refined aromatic extract of kero 25 tion, i.e., 2-methylthiopropyl isocyanate. The absence Sene. Auxiliary solvents such as alcohols, ketones, and of ionic thiourethane adducts indicated that both ad polyalkylene glycol ethers and esters can be used in ducts were formed by a selective, free radical mecha conjunction with these petroleum solvents. nism. Compositions of the present invention can also be Distillation of the reaction mixture in vacuo yielded formulated as emulsifiable concentrates which are con 30 centrated Solutions or dispersions of the active ingredi 71.5 grams (91 percent) of the isomeric adduct mix ent in an organic liquid, preferably a water-insoluble tures as a clear, colorless, mobile liquid, boiling at organic liquid containing an added emulsifying agent. 33-35°C. at 0.2 mm pressure. A fractional distillation These concentrates can also contain a proportion of resulted in an enrichment of the branched adduct iso water, for example, 50 percent by volume, based upon 35 mer in the early fractions. the total composition to facilitate the solution with wa Elemental Analysis - Calculated for CHNOS: C, ter. Suitable organic liquids include, e.g., the above pe 45.78; H, 6.91; S, 24.44; N, 10.67. Found: C, 45.52; H, troleum hydrocarbon fractions previously described. 7.05; S, 24.38; N, 10.66. The emulsifying agents can be of the type producing EXAMPLE 2 water-in-oil type emulsions which are suitable for appli 40 cation by low volume spraying, or an emulsifier of the Gamma Irradiation-Initiated Addition of Methanethiol type producing oil-in-water emulsions. Oil-in-water to Allyl Isothiocyanate emulsions can be used, producing concentrates which can be diluted with relatively large volumes of water for CHSH + CH=CHCHNCS-> CHS(CH)NCS(major product) application by high volume spraying or relatively small 45 volumes of water for low volume spraying. In such -- emulsions, the active ingredient is preferably in a non CHSCH(CH)CHNCS aqueous-phase. (minor product) The present invention is further illustrated in further detail by following examples, but it is to be understood 50 A mixture of 69.3 grams (0.7 mole) of distilled allyl that the present invention, in its broadest aspects, is not isothiocyanate and 32.4 grams (0.675 mole) of me necessarily limited in terms of the reactants or specific thanethiol was reacted in a Pyrex pressure tube under temperatures, residence times, separation techniques, the effect of gamma irradiation. The reaction was initi and other process conditions, etc.; or dosage levels, ex ated from 10 cm distance with 4 Coplates emitting posure times, test plants used, etc., by which the com 55 about 4,500 curies. Five hours irradiation resulted in pounds and/or formulations described and claimed are about 40 percent conversion of the methanethiol to preferred and/or used. yield the allylic adducts. About 90 percent of the iso meric adducts was 3-methylthiopropyl isothiocyanate, EXAMPLE 1 while 10 percent was the branched 2-methylthiopropyl isothiocyanate. Ultraviolet Light-Initiated Addition of Methanethiol to 60 The crude reaction product was distilled in vacuo to Allyl Isocyanate yield the isomeric mixture as a clear, light yellow liquid boiling at 76-78°C. at 0.6 mm pressure. CHSH + CH-CHCHNCO-). CHS(CH)NCO Elemental Analysis - Calculated for the distillate, (major product) 65 CHNS: C, 40.78; H, 6.16; S, 43.55. Found: C, 40.38, -- H, 6.34; and S, 43.57. CHSCH (CH)CHNCO A reaction of equimolar amounts of reactants under (minor product) the above conditions resulted in 53 percent conversion 3,884,951 13 14 in 16 hours. The isomeric adduct mixture consisted of 52.80; H, 8.22; N, 8.79; S, 20.14. Found: C, 52.52; H, about 91 percent 3-methylthiopropyl isothiocyanate 8.28; N, 8.93; S, 19.81. and 9 percent 2-methylthiopropyl isothiocyanate. EXAMPLE 5 EXAMPLE 3 5 Ultraviolet Light-Initiated Addition of Ultraviolet Light-Initiated Addition of Methanethiol to 2-Methyl-2-Propanethiol to Allyl Isocyanate Allyl losthiocyanate. (CH)CSH + CH=CHCHNCO -> (CH) CS(CH)NCO CHSH + CH2 =HCHNCS --> CH3S (CH2 ) NCS A mixture of 84.2 g (1.01 mole) of distilled allyl iso (major product) cyanate and 89.3 g (0.99 mole) of 2-methyl-2- propanethiol was irradiated as described in the previ ous example. Nimr spectroscopy of samples, taken at periodic intervals from the reaction mixture, indicated CHSCH ( CH3 ) CHNCS 5 allyl isocyanate conversions of 64 percent after 4 hours (minor product) and of 93 percent after 64 hours irradiation. After the removal of the volatile reactants in vacuo, nmr analysis of the crude reaction product indicated that it was mos tly 3-t-butylthiopropyl isocyanate. 20 Distillation of the crude product at 0.05 mm yielded CH2=CHChangcha 152 g of the clear, colorless liquid boiling between S 37-39°C. This represents a 95 percent yield based on (minor product) the converted reactants. Nmir indicates a 95 percent minimum of the major isomeric adduct. A mixture of 69.3 grams (0.7 mole) of distilled allyl 25 Elemental Analysis - Calculated for CHOSN: C, isothiocyanate and 33.6 grams (0.7 mole) of methane 55.46; H, 8.72; N, 8.08; S, 18.5. Found: C, 55.31; H, thiol was irradiated with two 75 watt Hanau immersion 8.81; N, 8.08; S, 18.48. lamps for 127 hours at 16°C., resulting in 90 percent reaction of the methanethiol. An nmr spectrum of the EXAMPLE 6 crude reaction mixture indicated that 80 percent of the 30 Ultraviolet Light-Initiated Addition of Benzenethiol to adduct was 3-methylthiopropyl isothiocyanate. Eleven Allyl Isocyanate percent was the branched adduct, 2-methylthiopropyl isothiocyanate. About 9 percent of the adduct was N allyl-S-methyldithiocarbamate, which resulted by the (-)-sh + CH2=CHCH2NCO --> addition of the thiol to the isothiocyanate group. 35 Distillation of the crude reaction product in vacuo yielded a mixture of the 3- and 2-methylthiopropyl iso ()-s(cha )NCO thiocyanate as a liquid distillate identical with the prod (major product) uct of the previous example. -- 40 EXAMPLE 4 Ultraviolet Light-Initiated Addition of 2-Propanethiol KY- SCH (CH3)CHNCO to Allyl Isothiocyanate (minor product) 45 (CH4). CHSH + -> (CH4),CHS(CH,);NCO CH=CHCHNCO (major product) cha-chchall-is-() O (CH),CHSCH(CH)CHNCC) 50 A stirred mixture of 55 grams (0.5 mole) of benzene (minor product) thiol and 43.6 grams (0.525 mole) of allyl isocyanate was irradiated in a quartz reaction vessel with a 75 watt A mixture of 80.7 g (0.97 mole) of distilled allyl iso Hanau immersion lamp at 15°C. Four hours irradiation cyanate and 73.9 g (0.97 mole) 2-propanethiol was ir resulted in about 50 percent conversion of the isocya radiated with two Hanau lamps as described in the pre 55 nate as indicated by nmr. A total of 24 hours irradiation vious example. Nimr indicated that 5 hours of irradia resulted in about 75 percent conversion to the two iso tion resulted in 79 percent, and 24 hours of total irradi meric adducts resulting by addition to the olefinic ation in 93 percent, reaction of the allyl isocyanate. bond. Nimr of the reaction mixture also indicated that After the removal of the unreacted volatile compo the relative percentages of the adducts were 93 percent nents of the mixture under 0.1 mm pressure, it could be 60 3-phenylthiopropyl isocyanate and 7 percent 2-phenyl estimated by nmr that the residue consisted of 95 per thiopropyl isocyanate. cent 3-i-propylthiopropyl isocyanate and 5 percent Fractional distillation of the mixture in vacuo yielded 2-i-propylthiopropyl isocyanate. 55 grams (57.5 percent) of the isomeric adducts as a Distillation of the crude residual product at 0.05 mm clear, colorless, mobile liquid boiling at 87°-90°C. at pressure yielded 140 g of the clear colorless liquid 65 0.1 mm. It was observed during distillation that the product boiling between 34–36°C. Based on the re heating caused some reaction of the thiol with the iso acted amounts of starting materials, this amount corre cyanate group. sponds to an isolated yield of 97 percent for the iso Elemental Analysis: Calculated for CHONS: C, meric mixture of olefinic adducts. 62.15; H, 5.73; N, 7.25; S, 16.59. Found: C, 62.28; H, Elemental Analysis - Calculated for CHOSN: C, 5.89; N, 7.19; and S, 16.74. 3,884,951 1S 16 irradiated in a quartz tube at 15°C. by a 75 watt Hanau a EXAMPLEto 7 ultraviolet immersion lamp. One hour irradiation- re Gamma Irradiation-Initiated Addition of Benzenethiol sulted in the conversion of 55 percent of the isocya to Allyl Isothiocyanate nate. A total of 5 hours irradiation converted about 85 5 percent of the isocyanate. Removal of the excess allyl SH -- R C isocyanate by distillation gave a quantitative yield of a ()- H + CH2 CHCHNCs-) ()- S(CH2) 3N S crude, residual product having an nmr spectrum corre sponding to that of a mixture containing 92 percent of (olefinic product) straight diadduct, ethylene-bis-3-thiopropyl isocyanate, 10 and 8 percent of the corresponding partially branched -- diadduct. Distillation of the crude product in vacuo vielded CH=H2=CHCH2NHCS2 -()/ v. 161.2 grams (62 percent) ofp the diadduct as ay color (cyanate adduct) less, clear liquid, distilling at 147-150°C. at 0.2 mm 15 pressure. Nimr indicated that the rest of the product, -- which was a brown residue, also consisted mainly of the M \, same diadduct. S(CH2)3NHCS2 -() Elemental Analysis - Calculated for CoH16N2O2S: C, 46.13; H, 6.19; N, 10.76; and S, 24.63. Found: C, (diadduct) 20 46.39; H, 6.32; N, 10.62; and S, 24.56. A mixture of 89 grams (0.9 mole) allyl isothiocya nate and 99.25 grams (0.9 mole) benzenethiol was irra diated by gamma rays in the manner described in Ex EXAMPLE 9 ample 2. Nimr analysis of a sample after 19 hours irradi - 25 uct. A totalal O h StateOurS radiationt 9 press an clini OUISad Ultraviolet Light-InitiatedAllyl Isothiocyanate Addition of Ethanedithiol to standing without irradiation resulted in the formation of byproducts, i.e. diadduct and cyanate adduct as indi catedAn attemptedby nmr. distillation of the reaction mixture at 30 HS(CH, SH + 2 SCN(CH)S(CH)S(CH)NCS- 0.1 mm pressure from a bath of 135°C. resulted in the CH=CHCHNCS - (olefinic diadduct) decomposition of the by-products according to the fol -- lowing reaction schemes: CH=CHCHNHCS(CH,)SCNHCHCH=CH CH2=CHCH-NHCs2-() -) 35 (cyanate diadduct)

CH2=CHCH2NCS + HS-() A mixture of 29.7 grams (0.3 mole) of allyl isothio NHCS -> 40 cyanate and 14.1 grams (0.15 mole) of ethanedithiol ()-s(CH2) 3 2-() was irradiated in the manner described in the previous example. Nmir showed that 120 hours irradiation re CH) NCS + HS-( ) sulted in the reaction of 45 percent of the allylic double ()-st 2 )3 bonds to form the corresponding allylic adducts. About The volatile decomposition products were removed 45 22 percent of the thiocyanate groups also reacted to by distillation. Nimr indicated that the residual product form the cyanate adducts. (65 g) was mostly the olefinic adduct, i.e., 3-phenylthi opropyl isothiocyanate. Based on the amount of start- EXAMPLE 10 ing materials this corresponds to a yield of 35 percent. Elemental Analysis - Calculated for CoHSN: C, 50 57.38; H, 5.28; N, 6.69; S, 30.64. Found: C, 57.11; H, Gamma Irradiation-initiated Addition of Ethanedithiol 5.46; N, 7.04; S, 30.45. to Allyl Isothiocyanate EXAMPLE 8 A mixture of 99 grams (1 mole) of allyl isothiocya a - o nate and 47 grams (0.5 mole) of ethanedithiol was re Ultraviolet Light-Initiated Addition of Ethanedithiol to 55 acted with initiation from a gamma ray source as de Allyl Isocyanate scribed in Example 2. Nimr indicated that 22 hours ra diation resulted in 32 percent reaction of the allylic gr HS(CH),SH + OCN(CH)S(CH)S(CH)NCO oup. Subsequent irradiation for 70 hours plus 8 days 2CH=CHCHNCO - (major product) to standing57 percent resulted of the inallylic a final and reaction 18 percent mixture, of the in isocya which -- nate double bonds were reacted. ocNccHscHscHCHCH. An attempted distillation of the reaction mixture NCO from a bath at 135°C. at 0.2 mm pressure resulted in (minor product) is the decomposition of the dithiocarbamate groups formed by isothiocyanate addition. For example, the A stirred mixture of 94 grams (1.0 mole) of ethanedi- decomposition of the isothiocyanate diadduct can be thiol at 182.6 grams (2.2 mole) of allyl isocyanate was indicated by the following scheme: 3,884,951 17 18 CH=CHCHNHCSCHCHSCNHCHCH=CH and A solution of 41.5 grams (0.5 mole) of allyl isocya 2 CH=CHNCS -- HSCHCHSH The volatile decom nate and 72.25 grams (0.5 mole) of p position products were removed by distillation. An nmr chlorobenzenethiol in 50 ml dimethyl sulfide was irra spectrum of the residual product ( 120 g) indicated that diated with an ultraviolet lamp in the manner described it was mostly the olefinic diadduct, i.e. 5 in Example 1. Nimr indicated that in 48 hours 32 per 3-(ethylene)-bis-thiopropyl isothiocyanate. Based on cent of the allylic double bonds reacted with the thiol the amount of starting materials, the residual adduct to form the allylic monoadduct, i.e. 3-p-chlorophenyl was obtained in a yield of 82 percent. thiopropyl isocyanate. No other products could be ob EXAMPLE ll served. O An attempt to fractionally distill the reaction mixture Ultraviolet Light-Initiated Addition of Ethyl at 0.1 mm from a 160°C. bath resulted in the formation Mercaptoacetate to Allyl Isocyanate of the diadduct as a residual product. EXAMPLE 13 15 CHO.COHSH + CH=CHCHNCO - CHOCCHS(CH)NCO Gamma Irradiation-Initiated Addition of Polythioether (major product) Dithiol to Allyl Isocyanate -- HS--(CH)SCHCH (CH)S--(CH),SH + 2 CH=CHCHN CH=CHCHNHCOSCH COCH OCN(CH)S--(CH)SCHCH (CH (minor product) )S--(CH2)S(CH)NCO (allylic diadduct) A magnetically stirred mixture of 20 grams (0.24 A mixture of 83 grams (1 mole) of allyl isocyanate mole) of allyl isocyanate and l 10 grams (0.1 mole) of and 20 grams (1 mole) of ethyl mercaptoacetate was 25 polythioether (PTE) dithiol of the above formula was irradiated by two ultraviolet lamps as described in Ex irradiated with gamma rays for 16 hours in the manner ample 1. Nimr analysis showed that most of the thio re described in Example 3. The crude reaction product acted in an hour. About 75 percent thiol addition oc was then heated at 130°C. for 2 hours under 0.05 mm curred to the allylic double bond. To complete the re to remove the excess allyl isocyanate. A study of the action, the reaction mixture was irradiated for 14 more 30 nmr spectrum of the residual product indicated that a hours. The volatile components of the mixture were complete and selective addition of the PTE dithiol to then removed at 0.05 mm. As a residual product, 190 form the allylic diadduct took place. A number average grams (93 percent) of crude adduct was obtained. Nimr molecular weight determination of the product in ben indicated that it contained 80 percent of the major zene solution by a vapor pressure osmometer gave a product, i.e. 3-carboethoxymethylthiopropyl isocya 35 nate and about 15 percent of the minor product, i.e. value of 1,268. The calculated molecular weight of the ethyl S-(N-allyl)-carbamoyl thiolacetate. diadduct is 1,266. An attempted distillation of the crude adduct yielded Elemental Analysis - Calculated for CH3NO2S4 some 3-carboethoxymethylthiopropyl, isocyanate, as a (diadduct of 1,168 molecular weight): C, 48.33; H, clear colorless liquid distilling at 97c. under 0.5 mm 40 8.12; N, 2.39; S, 38.43; Found: C, 48.13; H, 8.02; N, pressure with decomposition. 2.40; S, 38.90. Elemental Analysis - Calculated for CHNOS: C, EXAMPLE 14 47.28; H, 6.44; N, 6.89; S, 15.77. Found: C, 47.05; H, Ultraviolet Light-Catalyzed Addition of Allyl 6.46: N, 6.75; S, 15.63. 45 Isocyanate to Polythioether Tetrathiol

flasheche(Tetrathiol) Ochseischachsh): 2 +4 CH-CHCH2NCO EXAMPLE 12 55 Molecular Weight Calculated 795.5. Found 897 Ultraviolet Light-Initiated Addition of Number of SH Groups per Molecule Calculated 4.0. p-Chlorobenzenethiol to Allyl Isocyanate Found 4.4

60 cl-()-sh + CH2=CHCH2CO-> Cl-)-8 (CH3)3CO (allylic monoadduct) n-Q- SH Cl-)-s(CH) Cos-y-Cl (diadduct) 3,884,951 19 20 CH2CH2SCH2CH2S (CH2) 3NCO H2SCH2CH2 -O >

(Diadduct) -cischacha CH2CH28Ci2Cl23 ( CH2 ) THC (SCH2CH2 SC:CH2?ichachsch

(Crosslinked Polythioether Thiourethane) A magnetically stirred mixture of 32.12 grams (0.39 EXAMPLE 16 mole) of allyl isocyanate and 80.7 grams (0.09 mole) 20 o theof idioishii, addition of ethanedithiol PTE). to 1,2,4-trivinylSCR. cyclohex- E.O. "IonicCHCHNco if Thiolacetic mo Acid AlliateSE S ane, was irradiated with an ultraviolet lamp in the man- (cyanate adduct) ner described in Example 3. The progress of the allylic To 43.6 grams (0.525 mole) of stirred allyl isocya addition reaction was followed by nmr spectroscopy. In 25 nate 38 grams (0.5 mole) of thiolacetic acid was added 28 hours, 69 percent of the allyl isocyanate reacted. A dropwise below 33°C. in 15 minutes. An exothermic liquid product mixture consisting of a major amount of reaction started immediately with the addition of the triadduct and a minor amount of diadduct was formed. acid, which required icewater cooling during the addi The unreacted allyl isocyanate was removed from this tion. The excess allyl isocyanate was subsequently re mixture at 0.2 mm at room temperature. Subsequent 30 moved at 0.25 mm overnight. The nmr spectrum of the heating of the liquid residual product at 135°C. for 2 liquid, residual product showed that a quantitative hours resulted in crosslinking. This is due to a thermally yield of the ionic adduct derived by, addition to the iso induced ionic reaction of the thiol groups with the iso- cyanate group was obtained. Cyanate groups to form thiourethane bonds. The cross linked product is a very tough, hard polymer insoluble 35 EXAMPLE 7 in benzene. Ultraviolet Light-Catalyzed Addition of EXAMPLE 1.5 n-Dodecanethiol to Allyl Isocyanate CH(CH),SH + d CH(CH)S(CH)NCO Ultraviolet Light-Initiated Addition of CH=CHCHNCO (3-Hydroxyethanethiol to Allyl Isocyanate 40 (olefinic adduct) A mixture of 16.6 grams (0.2 mole) of allyl isocya Eco ... no HOCHSSCH.) nate and 40.4 grams (0.2 mole) of n-dodecanethiol is 2 (allylic monoadduct) irradiated by an ultraviolet lamp in the manner de scribed in Example 1 for 24 hours. An nmr spectrum HOCHCHS 45 of the resulting reaction product shows that it is mostly -(CH2)NHCOCH2CH2S--(CH)NCO the straight chain olefinic adduct, i.e. 3-n-dodecylthio (polythioether polyurethane polyadduct) propyl isocyanate. A mixture of 91.3 grams (1.1 mole) of allyl isocya- EXAMPLE 1.8 nate and 78 grams (1 mole) of hydroxyethanethiol was 50 Ultraviolet Light-Catalyzed Addition of Ethanethiol to irradiated with an ultraviolet lamp in the manner de- Allyl Isocyanate scribed in Example 1 for 100 minutes. Nmir spectros- CHSH + CH=CHCHNCO mo CHS(CH)NCO copy indicated that allylic monoaddition took place (olefinic adduct) with a reactant conversion of 95 percent. The unre- A mixture of 16.6 grams (0.2 mole) of allyl isocya acted volatile components of the mixture were re- 55 nate and 12.4 grams (0.2 mole) of ethanethiol is irradi moved under diffusion pump vacuum at 1.5 x 10 ated at -30°C. for 24 hours in the manner described in mm. The resulting residual product is 3-ghydroxyethyl- Example 1 to yield the olefinic adduct, i.e. 3-ethylthio thiopropyl isocyanate, a clear, colorless, mobile liquid. propyl isocyanate as the major product. Duringuring 72 h ours standingtandi at room temperature,t it was EXAMPLE 1.9 converted into a linear polythioether polythiourethane 60 of 7589 number average molecular weight by self- Ultraviolet Light-Catalyzed Addition of Xylenethiol to polyaddition. 2-Methallyl Isocyanate Cis-(y-s: + CH2--CH-NCO -c{-s-cha-ch-sco CH3 CH CH3 3 Elemental Analysis - Calculated for CHNOS: C, A mixture of 27.6 grams (0.2 mole) of xylenethiol 49.63; H, 7.63; N, 9.64; S, 22.08. Found: C, 49.75; H, and 16.6 grams (0.2 mole) of 2-methallyl isocyanate is 7.48; N, 8.78; S, 21.68. irradiated as described in Example 1 for 24 hours. An 3,884,951 2. 22 examination of the reaction mixture by nmr shows that 2-pounds per acre rate, respectively. The results are the methallylic adduct, i.e. 3-xylylthiopropyl isocya given in Table I below, and show that the adducts of nate, is formed. this invention are effective post-emergence herbicides. While not wishing or intending to be bound by any the EXAMPLE 2.0 5 ory, it is, nevertheless, believed that, or acceptable bio Azo-bis-isobutyronitrile- Catalyzed Addition of logicalE. activity,SN theo presenceis necessary; of both theallyl thioether isocyanate and Methanethiol to Allyl Isothiocyanate shows little activity. It is to be further noted that the A magnetically stirred mixture of 29.7 grams (0.3 isothiocyanate adduct of methanethiol is more active mole) of allyl isothiocyanate, 15.4 grams (0.31 mole) 10 than the corresponding isocyanate adduct and that the of methanethiol and 3.3 grams (0.02 mole) of azo-bis- aromatic thioether isocyanates seem to be preferable to isobutyronitrile was heated for 24 hours at 40°C. A sub- the corresponding aliphatic thioethers. TABLE I POSTEMERGENCE ERBICIDA, ACTIVITY OF ISOCYANATES AND ISOTHOCYANATES -YOORSPhysiological Responsepole-at of Plants Initury to Crops Injury to Weeds Overall Barna Response Example Chemical Rate Sugar Soy Yellow yard Crab Buck- Morning Crop 'c' (d No. Structure Lbs. Acre Beets Corn Oats Clover Beans Cotton Mustard Foxtail Grass Grass wheat - Glory Index ridex CHSCF CHCHNCS 10 8 C 6 C 3 c iO C 9 C 0 C 9 C 10 C O C 10 C 3 C 10 C 7.6 8.6 2 CHSch CHCHNCO 10 5 C 3 C 3 C 9 C 9 C 8 C C 6 C 5 C O C 6 C 5 C 6. 6.5 t ()-s h.ch.ch, NCO 10 9 C 7 c. 7 c 10 c 9 c 10 c 10 c 0 c 10 c 10 c 10 C 10 C 8.6 10.0 8 {r,sch.ch.ch.co), lO 0 - 6 C c 6 C 6 C 4 C 9 C 10. C 8 C 10 c 10 C 8 C 4.8 9. 1 Control CH=CHCH, NCO 10 2 C 0 - 0 - 3 - 5 - 0 - 3 C 2 C 3 C 5 C O - O - i. 6 2.1 Control ci-C-occola 2 i0 D 0 - O - 10 D 8 D 9 C 0 C 0 - 0 - 0 - 10 D 10 D 6. l 5.0 Cl (ii) 0: No visible effect. 1-3: Slight injury; plant usually recovered with little or no reduction in top growth. 4-6: Moderate injury; plan: s usually recovered but with reduced top growth. 7-9: Severe injury; plants usually did not recover. 10: All plants killed. C: Caustic. D: Distorted. sequent examination of the reaction mixture showed EXAMPLE 22 that a free radical addition to form 3-methylthiopropyl Pesticidal Spectrum of 3-Methylthiopropyl isocyanate occurred with 30 percent conversion. In 96 Isothiocyanate houurs the conversion was 70 percent. 3-Methylthiopropyl isothiocyanate, the product of 35 Example 2, was examined in various standard pesticidal screening tests for its pesticidal activity. EXAMPLE 2. An aqueous emulsion containing 0.05 percent of the Thiol-Allylic Isocyanate and Isothiocyanate Adducts as active chemical was found to kill, as a systemic poison, Post-Emergence Herbicides pea asphids. 40 When applied as an acetone solution at a rate of 100 A number of the adducts from those prepared in the lbs. active material per four-inch deep acre, the chemi previous examples were evaluated for post-emergence cal completely controlled the root knot nematode on herbicidal activity in this example. The test procedure tomatoes. employed was as follows: When tested as a foliar fungicide on 6-8 inch high Appropriate crop plant and weed species were wheat plants, an acetone solution containing 0.5 per seeded by growth-time requirement schedules in indi 45 cent of the chemical completely protected the plants vidual disposable four-inch square containers, watered against the cereal leaf rust, Puccinia recondita. as required, and maintained under greenhouse condi As a soil fungicide, the chemical was active against tions. When all crop plants and weeds had reached suit Rhizoctonia from cotton and Fusarium from tomato. able growth development, generally first true leaf stage, For a positive effect, the compound was applied as an plants and weeds appropriate to pertaining test require 50 acetone solution at a rate of 36 lbs. per acre active ma ments were selected for uniformity of growth and de terial to the soil. velopment. One four-inch container of each plant and It should be understood from the foregoing that the weed, averaging six (Corn) to fifty (Crabgrass) or more above description is merely illustrative of the preferred plants or weeds per individual container, was then embodiments and specific examples of the present in 55 vention and that in all of which embodiments and ex placed on carrying tray for treatment. Generally, six amples, variations, such as, e.g. those previously de crop and six weed containers were used in each evalua scribed, can be made by those skilled in the art without tion. departing from the spirit and purview thereof, the in Candidate compounds were dissolved in acetone vention being defined by the following claims. and, as appropriate, diluted in water containing wetting What is claimed is: and emulsifying agents. Although isocyanates can react 60 1. Compounds of the general formula Otch.chasi (Chaslach),scha), N = C = o). with water the results were not significantly influenced 65 wherein l is a positive integer of from 1 to 12, and n when, instead of the acetone solutions, aqueous emul is a positive integer of from 1 to 100. Sions were used for spraying the containers. 2. Compound of the formula The application rate was ten pounds per acre and, as CH - S - CH - CH - CH2 N = C = O. 'controls,' allyl isocyanate and the sodium salt of 2,4- 3. 3-6-hydroxyethylthiopropyl isocyanate. dichlorophenoxy acetic acid were used at the ()- and ck x: sk