PatentedUNITED’ Apr.v22,_,>1947'-" STATES > PATENT' ‘ 'v TOFFICE

‘2,419,488 " PRODUCTION OF MoNocnLoRo DERIVA- ‘ ~ ' 'rrvns 0F UNSATUBATED NITRILES - ' Harris A. Dutcher, Borg'cr', ‘_Tex_., asslgnor 'to_ 4 Phillips Petroleum Company,.a corporation of

‘.Delaware> f . . . ' ' > v No Drawing. Application June 5,1944, I, > Serial No. 538,880 ‘ , ' 11 Claims. (01. zed-464$

, . . 2 . The present invention relates to the production - Heretofore, a-chloroacrylonitrile has been pro of chlorine derivatives of unsaturated nitriles by ' duced as a by-product oi.‘ the direct substitutive the reaction of acetylene or acetylenic hydrocar- chlorination of acrylonitrile in the vapor phase bons with . More particularly over active carbon at a temperature between ap the invention relates to the production of 3- 5 proximately 200° and approximately 550° C. chloroacrylonitrile - ‘ . (Long, U. S. Patent No. 2,231,363). The process (Z-chloroviny] ,‘ C1__CH___CH_CN) yields 2-chloroacrylonitrile as the principal prod uct. vNo other methods for the production of 3 rgldsl?ltlgfesmigoilxgr196ii?ggtggesagty‘gfgtg; chloroacrylonitrile or other monochloro deriva acetylenic hydrocarbons and cyanogen chloride 10 tives of unsaturatednitriles are known. ‘ ' ’ I have found that acetylene and acetylenic hy is 2281322232”; ‘13355;:ffgléetggesggtdilrgggi? . drocarbons may be reacted with cyanogen halides . . I . . v to produce.monohalogen-substituted unsaturated monochloro derivatives of unsaturated mtnles, . . . . 1 such as 3-chloroacrylonitrile by there'action of- 1 mtr?es' The reactlon 1.5 facihtated ‘by certain ’ - » >15 catalysts which are referred to more speci?cally acetylene and cyanogen chloride. , hereinafter _ provideAnother a categlyst ob'ect (1201‘f thpfoggtiiirgtthevggg?lo?rg- e ‘n ' ' ‘ o Cyanogen' ‘ihlmd‘?. 157a readny.condens1ble. . . gas action of cyanogen chloride and acetylenic hydro- ' havmg a.memng pom? of approximately _6'5° Q‘ carbons and a boiling point within the range of approxi ‘ . mately 12.5 to 15.5“ C,‘ Itis very soluble in water, Other obJects- and advantages of the invention,. s alcohol and etherk Cyanogen chloride may‘ be‘ some of which are referred to-more speci?cally. readily prepared by the action‘ of chlorine on hy_ ‘ - ' ‘ hereinafter, will beapparent to thoseskilled 1n drogen cyanidek Investigations!“ methods for the art to which the invention pertains. , - . . . _ . Monochloro derivatives of unsaturatednitriles, ' the. preparatlon of .cya?nogen chlomde were de such as s_chlomacrylonitr?e : . 25 scribed by ‘T. Slater Price and Stanley-J. Green » - '- (J . ‘Soc. ,Chem.'Ind., 1920; vol. 39, pages 98-101T; <2-°h10r°vmy1 cyanide, 1-<>yan0-.2-"v . 11; ' Chem. Abs. 1920 vol. 14,-page‘ 2056). It has been chloroethylenei C1_CITI:CH,_CN)» reported that at 37°‘ C. cyanogen chloride ‘does 3-phenyl-3-chloroacrylonitrile _ - . not-react with ethylene (Ronald B. Mooney and ' (2-phenyl-2-chloro-vinyl cyanide, " I 30 Hugh G. Reich-J. Chem. Soc. (London), 1931, -- ' ;‘ _'_'._ ,-pase2597>-' ' I’ . CGHS 1 (in-CH1 CI?!) ' -: 1 Reactions similar to those of cyanogen chloride and z'chloro'l?'butadlenm cyatmvdevv ' ' occur with other- cyano'gengh'alides, such as 'cyé - (3-chloro-2,4-pentadienenitrile, > I ‘wan'ogen. bromide and , but the I_' CH2=CH__C(:¢1)=C I‘ 35 products are not at present of as‘v‘great industrial- interest as .the chloro' derivatives of unsaturated v1 and similar compounds, are products ofpoten-V * nitr?es , , I , , v v . tial industrial interest. They p'ossessrrmany of the ' . v I?aécordance withi*a[spe-ci?c'ém?bdinljent of ' I properties which make acrylonitrile desirable as the process of my invention-v'cyanog'e?'chloridé is. _ a material for copolymerization with 1,3,-,b_uta-' ,n voiatilized and’ passed,th;.ough"a; solution vof ; ' diene to form synthetic rubber. .Copolymersjof f1“- ace-tylene in an inert solventsuchhexane Orr butadienesaturated andmmles’ such withmonochloro Pr. without. derivatives apr'y 1091191111? of un_; 7' - v chloroacrylonitrilemaybeother saturated'hydm-carbens. separatedjfrorn _ The“ resulting the 1m}. 3_ 01' “her unsaturatfid Mme’ Possess SOme ‘its-W1“ ‘ reacted acetylene and solyentby distinatiomprer-a- I ~ I ' advantages over simple copolymers of butadiene 45'_erab1y in the- presence.dfia.siibstancgiaapablé'pf . . .. and acrylonitrile and over copolymers of buta-v _ - . an - ioXida-n't» {inhibitor-‘01:0 _ _> ." diene and dichloro' derivatives of acrylonitrile and ' friggélaiigg * t 1035,; a "1', “1y _' I‘ °V.er. 9011mm“ 0? blltt'diene and Styrene con" ' Insteadof'using the foregoing‘procedurej'soine-.'f’ - taming chloropropmmtrlles as comonomers. ~ ~ . what bet-ter- yieldis’are bbtainedr when catalysts These monochloro derivatives of unsaturated 5bxwhi‘ch prombte the additidn reaction‘ar-e used’ H nitriles may be hydrolyzed in' conventional‘ man ' -,Cuprous chloride issuchlas‘ a catalystand may1 ’ ner to produce the corresponding monochl'oroQun saturated acids,' for example, z-chloroac'rylic' "d; e-ujsea' asffol-lowsi' _Iknto_-ian__-agueous solution or" ' , and they may be hydrogenated to yield; ,c rolls-chloride qr'f‘examplego eicqnsistingior" ‘' chloro saturated nitriles, such asQ3'7-chlo 0'11; pionitrile, in the'presence'of catalysts such op _ er,v 15 cckoflconcentrated‘hydrochloric-‘acidand’ " 1,891,055) and Raney nickel (Winan's,,U._ff$;iPat-§ > ~- 51‘200cc', of‘water, are passed; streams ‘of acetylene - ent No. 2,334,140). The resulting hydrogenated . >_""and>cyai1ogen"chloride atsuch?owjrates'thatan beproduct, dehydrochlorinated for example, 3-chloropropionitrile,' to yield) acrylonitrile can 60'j approximatelymaintained. The‘ equimolecular'ratio catalyst solution o1ismaintalned}; reactants is '

-(Pieroh, U. S. ‘g’atent No. 2,174 756). _‘ i v - _ ' ' preferably ata.temperatureof'approxiinately _ 2,419,488 3 . 4 to 210° F. The chloroacrylonltrile that is formed able for extensive investigation and since the re may collect as an oily layer or may be volatilized action products are rather complex and have not with the unreacted acetylene and cyanogenrchlo heretofore been identified in other reactions, so ride, depending on the reaction temperature. If . that their separation and identi?cation cannot be volatilized, it can be separated from the eiliuent readily accomplished. In the reaction of meth vapors by fractional condensation. The con ylacetylene and cyanogen chloride, for example, densed crude chioroacrylonitrile may then be sub it has not been established conclusively whether sequently puri?ed by fractional‘distillation, using ' the resulting product is a polymerization inhibitor in this operation. Al ternatively, the total effluent may be condensed CH:—C=OH—-CN ' and the chloroacrylonitrile recovered therefrom , l and from‘ other products formed in the reaction 8-chloro-3-methylacrylonitrile by fractional distillation. O1‘ - In accordance with another method for the CH:—O=CH_—C1 practice of my invention, which is preferred for 15 N certain purposes, cyanogen chloride and acetyl 3-ehloro-2-methylacrylonitrile ene, with or without a diluent gas such as nitro gen, are passed in approximately equimolecular because of the di?iculty of separation and iden proportions over a solid contact catalyst which ti?cation of the products. promotes the reaction at a temperature within 20 Although the foregoing description is directed the range of approximately 100° to 400° C. Solid particularly to the reaction of cyanogen chloride cuprous chloride or cuprous cyanide is a suitable with acetylene, in both vapor and liquid phase, catalyst, although cyanide, sodium cya to produce 3-chloroacrylonitrile, it will be obvious nide, , and similar alkali and that by suitable conventional modification the alkaline-earth metal may be used. processes can be readily adapted to the produc Such solid contact catalytic materials, when used tion of other monochloro derivatives of unsat in the process of my invention, are preferably urated nitriles by the' reaction of cyanogen chlo deposited or coated on such adsorbent supporting ride and acetylenic hydrocarbons. Suitable acet or carrier materials as charcoal, bauxite, fuller’s ylenic hydrocarbons for use in such processes are earth and the like. Conventional methods may 30 methylacetylene (propyne, allylene), ethylacet be used for preparing'such supported catalytic ylene (l-butyne), dimethylacetylene (Z-butyne, materials. For example, a barium cyanide cata crotonylene), vinylacetylene (3-buten-l-yne) as lyst suitable for use in the process is prepared well as aromatic acetylenic hydrocarbons such by impregnating activated charcoal with an aque as phenylacetylene and the like. In connection ous solution of barium cyanide and thereafter with acetylenes containing a double bond in the I heating the resulting material to remove water; molecule, such as vinylacetylene, it is desirable such alternate impregnation and drying may be tovmaintain the reaction conditions within more repeated as often as necessary to obtain a cata critical limits in order to obviate any possible lytic material with the desired content of barium reaction of the double bond. However, a rather cyanide. ’ 40 Wide latitude is permitted between reaction con Wide variation is permissible in the proportions ditions which favor the reaction of a triple bond of the reactants which are used in the process. as in acetylene and those which promote sub These will largely be preselected with a view stantial reaction of a double bond. toward minimizing or obviating the polymeriza Examples of preferred methods of practicing tion of one or another of.the particular reactants. 45 the invention are set forth hereinafter, but it Generally equimolecular proportions of the re is to be understood that these examples are actants are used although, when an excess of merely illustrative and are not to be construed one reactant is used, it preferably is the acet as limitations of the scope of the invention. ylenic hydrocarbon, which is generally less read Example 1 _ ily polymerized than the cyanogen chloride. In 50 vapor-phase reactions, the use of an inert dil Into a concentrated solution of acetylene in uent gas such as nitrogen is generally desirable commercial solvent hexane is passed a slow since the temperatures which are used in such stream of cyanogen chloride gas while the reac reactions are substantially higher than those tion mixture is maintained at a temperature of used in the liquid-phase processes of the inven approximately 20° C. After substantial amounts of cyanogen chloride pass through the mixture tion. . The reaction which is involved in the produc without being. absorbed, the resulting products tion of monochloro derivatives of unsaturated are recovered. nitriles is believed to be that expressed by the To recover the 3-chloroacrylonitrile which is following equation: . ' formed in the reaction, the product is distilled 60 in the presence of hydroquinone as a polymeriza X-—CEC—Y + Cl-GN -_+ x-(I;=('3-Y tion inhibitor, through a fractional distillation 01 ON column. The unconverted acetylene and cy anogen chloride are expelled first and thereafter in which X and Y are hydrogen or alkyl radicals the solvent hexane and 3_-chloroacrylonitrile are and Y is the shorter or has the lower molecular 65 recovered. A substantial yield of the latter is weight of the two, if they are not identical. The obtained. » cyanide radical of the cyanogen chloride is be Example 2 lieved to add to that carbon atom that is con nected to the triple bond to which the shortest Cuprous chloride solution is prepared by or the lightest molecular weight substituent is 70 adding 500 grams of cuprous chloride, 250 grams attached and the chlorine is believed to add to of ammonium chloride, 30 grams of copper metal the carbon atom adjacent that to which the eye; powder, and 15 cc. of concentrated hydrochlo nide radical adds. However, I am not at all ric acid to 1200 cc. of water. The solution is certain that such is invariably the rule, since placed into a flask provided with a stirrer and alkyl-substituted acetylenes are not readily avail 75 two gas inlet tubes discharging beneath the sur 2,419,488 5 6 . face of the solution and an outlet tube.‘ The 3-chloroacrylonitrile which comprises reacting a ?ask is heated to approximately 95° C. and main mixture of phenylacetylene and cyanogen chlo tained at that temperature while slow streams of ride at a temperature in the range from 20° to methylacetylene and cyanogen chloride preheat 400° C. I ed to approximately 50° C. are passed into the 6. A process for the production of a mono ?ask at about equal gas ?ow rates. After a sub chloro derivative of an unsaturated nitrile which stantial portion of an oily material has been comprises reacting a mixture of acetylenic hy formed, the passage of the gases to the mixture drocarbon and cyanogen chloride in the presence and the stirring are stopped. The oily layer is of a cuprous salt at a temperature in the range separated and the chloro derivatives of methyl 10 from 20° to 400° C. acrylonitrile are recovered by fractional distilla '7. A process for the production of a mono tion. chloro derivative of an unsaturated nitrile which Example 3 comprises reacting a mixture of acetylenic hy drocarbon and cyanogen chloride in the presence Acetylene and cyanogen chloride preheated to of a solid contact catalyst comprising a sub approximately 200° C. are charged at approxi stance selected from the group consisting of cu mately equal volumetric rates to a mixing zone prous chloride, cuprous cyanide, and alkali and where the combined stream is further mixed alkaline earth cyanides at a temperature in the with nitrogen gas preheated to approximately range from 100° to 400° C. 200° C. in the proportion of 2 volumes of nitro 20 8. A process for the production of a mono gen to each volume of mixed reactant stream. chloro derivative of an unsaturated nitrile which The combined streams are then passedover a comprises passing in vapor phase a mixture of catalyst consisting of barium cyanide deposited an acetylenic hydrocarbon and cyanogen chlo on adsorbent charcoal that is disposed in a cat ride at a temperature within the range 0! ap alyst tube. The e?luent is fractionally con 25 proximately 100° to approximately 400° C. into densed, so that the 3-chloroacrylonitrile pro contact with a solid contact catalyst comprising duced is separated from the lower-boiling acet a substance selected fromthe group consisting ylene, cyanogen chloride and nitrogen. of cuprous chloride. cuprous cyanide and alkali The crude condensed 3-chloroacrylonitrile is and alkaline-earth metal cyanides. subsequently subjected to fractional distillation 9. A process for the production of 3-chloro in the presence of a polymerization inhibitor, acrylonitrile which comprises passing in vapor whereby a good yield of the desired product is phase a mixture of acetylene and cyanogen chlo obtained. ride at a temperature within 'the range of ap Example 4 proximately 100° to approximately 400° C. into Phenylacetylene is substituted for acetylene in 35 contact with a solid contact catalyst comprising Example 3 and the process is conducted substan a substance selected from the group consisting tially as described in Example 3. The product of cuprous chloride, cuprous cyanide and alkali obtained contains a substantial proportion of 3 and alkaline-earth metal cyanides. phenyl-B-chloroacrylonitrile. 10. A process for the production of 3-chloro 40 acrylonitrile which comprises passing in vapor Example 5 phase a mixture of acetylene and cyanogen chlo ride at a temperature within the range of ap By substituting a catalyst consisting of cuprous proximately 100° to approximately 400° 0. into cyanide deposited on bauxite for the catalyst of contact with a solid contact catalyst consisting Example 3 and otherwise conducting the process 45 of cuprous cyanide deposited on bauxite. as therein described, a good yield of 3-chloro 11. A process for the production of 3-chloro acrylonitrile is obtained. acrylonitrile which comprises passing in vapor Although the foregoing description comprises phase a mixture of equal volumes of acetylene preferred embodiments of my invention. it is to and cyanogen chloride diluted with nitrogen in be understood that variations and modifications 50 the proportion of 2 volumes to each volume of may be made therein without departing sub acetylene and cyanogen chloride at a tempera stantially from the scope of the invention or the ture of 200° C. over a catalyst consisting of cu appended claims and that the invention is not prous cyanide deposited on bauxite. and recov to be limited except as speci?ed in the appended ering 3-chloroacrylonitrile so produced from the claims. 55 resulting effluent. - I claim: I HARRIS A. BUTCHER. 1. A process for the production of a monohalo derivative of an unsaturated nitrile which com REFERENCES CITED prises reacting a mixture of acetylenic hydrocar bon and a cyanogen halide at a temperature in The following references are of record in the the range from 20° to 400° C. 60 file of this patent: 2. A process for the production 'of a mono UNITED STATES PATENTS chloro derivative of an unsaturated nitrile which comprises reacting a mixture of acetylenic hy Number Name Date drocarbon and cyanogen chloride at a tempera 2,326,095 D’Ianni ______. Aug. 3, 1943 ture in the range from 20° to 400° C. 65 2,325,984 Sarbach ______-- Aug. 8, 1943 3. A process for the production of _3-chloro 2,324,854 Kurtz et a1. ______.._ July 20, 1943 acrylonitrile which comprises reacting a mixture 2,322,696 Kurtz et a1 ______-_ June 22. 1943 of acetylene and cyanogen chloride at a temper FOREIGN PATENTS ature in the range from 20° to 400° C. 4. A process for the production of a mono 70 Number Country Date chloro derivative of methylacrylonitrile which 116,654 Australian ______Mar. 11, 1943 comprises reacting a mixture of methylacetylene and cyanogen chloride at a temperature in the OTHER REFERENCES range from 20° to 400° C. - Auwers et al., Liebig’s Annalen, vol. 492, pp. 5. A process for the production of 3-phenyl 75 283-292, 1932.