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. ' Patented-0x339“ . r 3 2,411,961] i Yum'ranv * 2,411,961 '‘ - raocEss non cA'rALYmn ABNORMAL 1 , ADDITION nnac'rrons . ’ I Theodore W. ’ Evans, Oakland, and William E. I .. Vaughan and Frederick F. ‘Rust, Berkeley, ' v(lali?, asslgnors to Shell Development Com- ' pany, San Francisco, Calif” a corporationoi Delaware . No Drawing. Application June 26, 1944, -_ Serial No. 542,242 12 Claims. "(01. 204-463) 1 ' i _ c 2 compounds, contrary to the course suggested by This invention relates to an improved method ; for the addition of. hydrogen sul?de and/or mer- ' the Markownikofi rule, by‘ effectingthe reaction at normal temperatures or even at considerably captans to symmetrical or unsymmetrical organic ~» compounds containing one or more unsaturated linkages of aliphatic character.v In one ‘of its lower temperatures, under the deliberate in?uence of ultraviolet radiations having wavelengths of below about 2900 to 3000 Angstrom units._ It is known that the presence of peroxides or of per more speci?c embodiments, the invention pertains to a novel method of effecting a controlled reac tion between hydrogen sulfide or a mercaptan oxide-forming compounds in unsaturated organic compounds, e. g. unsaturated hydrocarbons, is and unsymmetrical organiccompounds contain ing at least one unsaturated linkage of aliphatic 10 undesirable; The processes involving the‘abnor mal addition of hydrogen sul?de and/or of mer character, i. e. an ole?nic or acetylenic bond, to captans to unsaturated organic com-pounds under produce addition products of predetermined char the deliberate in?uence of ultraviolet radiations acter. \_ _ T necessitate the use of special equipment which This application is a continuation-in-part of _ . the copending application, Serial No. 432,048, ?led 15 is capable of transmitting rays of the de?ned low wavelengths.~ In'vother words, in order‘ to February 23, 1942, now Patent No. 2,376,675, dated efiectthe desired reaction it is necessary to em May 22, 1942. , ' ' ploy reaction vessels and/or lamps of quartz or It is known that mercaptans and thio-ethers. other suitable materials, e. g. calcium ?uoride, may be produced by reacting hydrogen sul?de or , which are capable of transmitting the de?ned a suitable mercaptanwith an unsaturated organic ' 20 ‘short wavelengths of 2900 to 3000 Angstrom units, compound, e. g. unsaturated hydrocarbon, at and below. elevated temperatures in the approximate range _ It has now been discovered that unsaturated organic compounds of the class more fully de reactions were effected at superatmospheric pres-_ ‘sures. .When hydrogen sul?de is reacted with, 25 scribed hereinbelow may be reacted with hydro gen sul?de or mercaptans. to e?ect directional unsaturated organic compounds under the out-] addition thereof via the above-de?ned “abnor _ lined conditions, the sulfhydryl group attaches to mal” addition, this reaction being effected with the unsaturated carbon atom containing the less-rr out the necessity of resorting to high tempera er number of hydrogen atoms attached thereto, so that, as clearly brought out' by Jones and 30 tures and/or elevated pressures, and in the ab Reid (Journal American Chemical Society. vol. - sence of undesirable peroxides-or peroxide-‘form; ing compounds. It has also been discovered that 60, pp. 2452-2455‘), the" addition takes‘place ac this reaction according to this invention may be cording to Markowniko?’s rule. Therefore, when \of from 200°i C. to 750° C. ‘~1n some cases such , effected without the necessity of employing any 35. special equipment or apparatus capable of trans mittihg very low ultraviolet rays. such as radia terminally unsaturated ole?ns are thus reacted , with hydrogen sul?de, the ‘reaction product pre dominates in secondary mercaptans and/or sec ondary thio-ethers. When the unsaturated or ganic compounds have been reacted with the mercaptans at the aforementioned elevated tem-‘ peratures. the sulfur; atom of the mercapto radical 40 attached predominantly ‘to the unsaturated car bon atom holding the most hydrogen atoms so '. that this addition was contrary to the course suggested by the Markowniko? ‘rule. This con tions having wavelengths of 2900' to 3000 Ang-‘ strom units. and below. According to the present process, this abnormal addition of mercaptans and/or hydrogen sul?de isattained by effecting the reaction under irradiating conditions (par ticularly under the‘ deliberate in?uence of rays which will not otherwise dissociate any one of the reactants), and in the presence of certain dition was designated-as “abnormal”. addition 45 catalysts having-de?nite and speci?c character istics which promote the abnormal addition but‘ on the assumption that mercaptans should add‘ like halogen acids. vWith reference to'the addi tion of mercaptans to unsaturated organic com the presence of which in the unsaturated organic ' compounds is not detrimental. Generally speak pounds, it is known that the abnormal addition - ' ing; these catalysts or reaction sensitizers com maybe catalyzed by free oxygen, air, ozone, per 50 prise compounds which yield free radicals under ‘ the photochemical ‘conditions employed to effect oxides, ascaridole and the like, while compounds the addition reaction. of the type of hydroquinone and piperidine act The term “free radical.” as employed herein, as reaction inhibitors. It has recently been discovered that hydrogen ' refers to an organic compound in which all of sul?de may be added to ‘unsaturated organic 55 the valences are not saturated (see Hackh’s 2,411,961 ,- 3 I . _ . Chemical Dictionary, second edition, page 397). These free radicals are electrically neutral mole-, .. 4 ~ . pounds, via abnormal addition, to produce- com pounds in which both terininalgcarbon atoms have sulfhydryl or mercapto radicals attached cules possessing one unpaired electron and ex hibiting an unsaturated ‘behavior. These prop thereto. Another group of organic compounds which may be employed as the primary material erties distinguish the free radicals from ions (such as those obtained by ionization of certain salts or in electrical discharges in gases). It has also been discovered that catalysts of the class more fully described 'herein' and con-‘ comprises or includes organic compounds where in an ole?nic linkage is in non-terminal position between two carbon atoms having a dissimilar number of hydrogen atoms attached to each of sisting of or comprising free radicals of the type 10 said unsaturated carbon atoms due, for example, de?ned - hereinbelow,- will catalyze and control to various substituents attached thereto. For the reaction between an unsaturated organic instance, the double bond may be between two compound and a mercaptan or hydrogen sul?de carbon atoms which are of secondary and ter so that the reaction will occur via the so-called tiary character, respectively. Another example "abnormal" addition at ordinary or even sub normal temperatures and without the necessity of employing special equipment or apparatus which will transmit ultraviolet.v radiations having 15 is a compound in which the unsaturated carbon‘ atoms are both primary or both secondary, but have unequal numbers of halogen atoms, such as chlorine, bromine, ?uorine and/or iodine atoms wavelengths 01' 2900 to 3000 Angstrom units, or below. _ ' . Broadly stated, the present invention resides attached to them. 20 - Any su?iciently stable mercaptan is suitable as a reactant to be employed in the photochemical addition ‘thereof to the above-de?ned class of ' in a photochemical process of effecting the ad dition of suitable mercaptans or hydrogen sul?de , - unsaturated organic compounds. A suitable in the presence of _ metallo-hydrocarbon com mercaptan may contain one or more sulfhydryl groups or radicals, and be of alkyl, aralkyl, a1 pounds and under the deliberate in?uence of light capable of photochemically dissociating ' said kenyl, arallrenyl or aryl character. The mer catalyst or sensitizer, this reaction being effected ‘at normal temperatures, i. e. in the neighborhood 01' from about 25° C. to about 15° C., or even at ' capto radical may be linked to an aliphatic or, an aromatic carbon atom. In the majority of_ ' cases it is preferable to employ the normal or considerably lower temperatures. vAs stated, this 30 iso alkyl chain mercaptans of primary, secondary photochemical'addition,‘ according to the present or tertiary character, particularly‘ those con invention, occurs contrary to the course suggested tained in or derived from petroleum and petrol by Markowniko?’ for the ‘addition of hydrogen leum products. The methyl, ethyl, butyl, amyl, halides, and in accordance with the rule‘ pro-_ "hexyl, heptyl, octyl and the like mercaptans, as posed by Posner (Berichta'vol. 38, p. 646 (1904)) 35 well as their homologues, analogues and substi concerning the addition of mercaptans todouble tution products, may be employed with excellent results. Another group of mercaptans which _ bonds. The unsaturated organic compounds which may be treated according to the process of this may be employed as one of the two reactants ' comprises or includes the dimercaptans, and par invention include hydrocarbons containing one‘ 40 ticularly the polymethylene dimercaptans of the, or more ple?nic and/or acetylene linkages.- Ex general formula HS(CH2)nSH. This group of mercaptans may be reacted with, for example, aliphatic hydrocarbons containing a plurality of unsaturated linkages to produce thio-ethers hav . amples of such hydrocarbons are ethylene, pro-, pylene, butene-l, butene-Z, isobutylene,‘pentene 1,'pentene‘-2, hexene-‘J, 4-methyl-pentene-1, 4,45 dimethyl-pentene-l, 4-methyl-pentene-2, octene 1, decene-l, cetene-l, styrene, cyclohexene, 3 methyl-cyclohexene, 1,4-diphenyl-butene-2, bu‘ i5 ing a high molecular weight. ’ Of the metallo-hydrocarbon compounds which ‘ , may be used to promotethe abnormal addition 'tadiene-1,3, pentadiene-L3, pentadiene-l/i, hex reaction in accordance with the process of the adiene-l,5, vhexadiene-“lgt', acetylene, propyne, present invention, it is preferable to use those "butyne-l, pentyne-2,_hexyne-1, cetyne-l, octyl- 50 which may be readily dissociated by light. Withacetylene, phenyl-acetylene, cyclopentadiene, and out any intention of being limited'by the com the like. The above compounds, and their ‘ various homologues, may be substituted inv the nucleus and/or in the substituents in varying degrees. 'For instance, the unsaturates may‘ 65 contain one or more halogen atoms attached to saturated and/or unsaturated carbon atoms. Representative examples of these ‘compounds are: vinyl halides, allyl halides, crotyl halides, pounds enumerated herein, it may be stated that representative compounds of this class or group include substances ofgthe type of tetraethyl lead’, tetramethyl lead,‘ tetraphenyl lead, tetraethyl tin, dimethyl-diethyl tin, tetramethyl tin, mi methyl-ethyl tin, tetraethyl germanium, diphenyl } germanium, di- and trivalent organo-tin com pounds of both the aliphatic and aromatic series, 60 as triphenyl tin anddiethyl tin, organo-lead com amples of- substituted unsaturated hydrocar pounds containing di- and trivalent lead, and bons are methyl acrylate, methyl methacrylate, the like, their homologues and analogues. Al divinyl ether, diallyl ether, dimethallyl ether, ‘ though the above organo-metallic or metallo-hy " methallyl halides, and the like. . Other ex and the like; _ drocarbon compounds cover substances in which A particularly suitable group of organic com 65 a carbon atom of the organic radical is united pounds’ which may be reacted with mercaptans directly to a metal'at m of the fourth group or hydrogen sul?de via abnormal addition com of the periodic table, it is to be understood‘ that prises the compounds, and particularly the hy organo-metallic compounds containing metals of drocarbons, in which the unsaturated linkage is other groups are also suitable catalysts. Thus, in terminal or alpha position. Also,v aliphatic 1o dimethyl cadmium, dipropyl cadmium, diethyl hydrocarbons and their'various-substituted de mercury, trimethyl lanthalum, trimethyl Ibis? rivatives, e. g. halosubstituted derivatives, con muth, triphenyl bismuth, tetraphenyl. chromiumy. taining unsaturated linkages both in alpha ‘and hexaphenyl disilane, and similar compounds may - omega positions (1. e. terminal pdsitions), may be employed ‘as the catalysts which will cause be readily reacted with the above-outlined com-I 78 the abnormal addition of mercaptans or hydrogen ' 2,411,961. . sul?de to unsaturated organic compounds. In fact, a description and discussion of organe action vessel was then sealed and illuminated for a period of about six minutes by radiations ema metallic compounds (suitable as such promoting agents) may be found in ‘,‘Organlc Chemistry.— An Advanced Treatise," by H. Gilman and others, second edition, volume I, pages 489 to. 590. The abnormal addition reaction between the de?ned compounds according to the process of An analysis of the contents from the reactor showed that only about 4% of thepropylene re nating from a mercury quartz lamp. The reactor was maintained at a temperature of about 0° C. acted. ’ " Example I! the present invention may be e?ectedin the vapor The experiment described inExample I was or liquid phase, or in a two-phase liquid—vapor 10 repeated. However, prior to the' sealing of the - system. Since the abnormal addition reaction reactor, tetraethyl lead was added in such an occurs photochemically, or under the in?uence of catalysts or sensitizers which are dissociated to _ amount that. the volumetric ratio of propylene,v ' hydrogen sulfide and tetraethyl lead in the re produce radicals which initiate the reaction, no heating is necessary. In fact, in many instances 15 actor was 7.4:7.4:1. After the six-minute illumi nation the reaction mixture was distilled to evap the reaction, although it may be realized at tem crate the unreacted compounds. It was then peratures of about 25° C., is preferably effected at ‘found that about 75% of the propylene reacted temperatures which are even below 0°C. Also. it was discovered that the abnormal addition of . mercaptans‘cr hydrogen vsul?de, when the reac via abnormal addition, the reaction product con-‘ . 20 sisting of about 80 weight percent of n-propyl‘ mercaptan and about 20 weight percent of di-n tion is effected under the in?uence of the above de?ned class of- catalysts or sensitizers, proceeds I propyl sul?de. - - '~ Example 111 ?lm in the reaction zone. Although the reaction described herein may be promoted or effected by 25 -, When a substantially equivolumetric mixture of propylene.‘ and n-prcpyl mercaptan, which mix using the whole range of ultraviolet radiations, it ture contains about 3% tetraethyl lead, is dis has been pointed out above that the presence of regardless of the presence or absence of ‘a liquid posed in a Pyrex glass container and is subjected at a temperature of about 0° Cftc the action of reactants) eliminates the necessity of using radi 30 ultraviolet radiations ‘emanating from a quartz mercury lamp, the reaction product contains sub ations having very short wavelengths. In other the de?ned catalysts or sensitizers (which, inci dentally, do not have a deterimental e?'ect on the .words, whereas abnormal addition of, for example, ' ' stantial amounts of di-n-propyl sul?de. hydrogen sul?de to an unsaturated organic com pound would require ultraviolet radiations having wavelengths of below about 2900 to 3000 Angstrom units, the addition of even small amounts, e. g. from about 1% to about 10%, of a compound of the class ‘of catalysts or sensitizers de?ned above permits effective addition even when the radia tions have longer wavelengths‘, provided such rays will cause the initial dissociation of the catalyst or sensitizer, so that the free radicals thus formed may initiate the chain mechanism and at the same ‘time control the reaction to effect "abnor nal" addition. For example, in the case of tetra ethyl lead, this catalyst-may be dissociated by light of about 3600 Angstrom units, which is ordi narily ine?ective in initiating the reaction. The abnormal reaction according to the present _ process may be effected in a batch, intermittent or continuous manner. When the process is exe cutedbatchwise, the reactants, together with a suitable amount of the catalyst or sensitizer of the de?ned class, may be conveyed under any‘ suitable or opt um pressure and temperature into a suitable container which is then illumi Ewamplc IV . Propylene, hydrogen-sul?de and tetraphenyl lead are introduced into a Pyrex glass container in such amounts that the liquid volumetric ratio of said ingredients is l2:l2:1. The illumination of the mixture at a temperature of about 25° C. with ultraviolet radiations from a quartz mer cury lamp results in the formation of substantial amounts of n-propyl mercaptan and some di-n- ' ' ' propyl sul?de. Substantially the same results' are obtained when diethyl mercury is employed in lieu of tetra phenyl lead as the catalyst or sensitizer. Example V . When hexene-l is reacted with‘ hydrogen sul ?de in the presence of a‘ minor amount of tetra ethyl lead in accordance with the process de- - scribed in Example II, the, reaction product con tains n-hexyl mercaptan and. di-n-hexyl sul?de. ’ The yield of the desired products of the abnor mal addition depend in part on the amount of 7 catalyst employed and the time during which the reactants and the catalyst are subjected to the nate'd, preferably with ultraviolet light, for a illumination, _ period of time su?lcient to effect the desired addi We claim as our invention: Y tionreaction. Although containers of quar'tz'cr 1. In a process of reacting propylene with hy the like may belemplcyed, so as to permit light 60 . drogen sul?de to form products of addition, the waves of between 2900 and 3000 Angstrom units improvement which'ccmprises directly control therethrough, it is possible to employ ordinary ling the reacticn-to produce predominantly nor- ' glass or Pyrex glass, since wavelengths passing mal prcpyl mercaptan by adding a minor amount through this typeeof glass will also dissociate the of tetraethyl lead to .the reactants and subject 65 sensitizer or catalyst and thus initiate and e?ect ing the mixture, at a temperature'not in excess of the desired reaction. , ‘ ' about 25° 0., .to the action of photochemical Although there is no intention of being limited radiations above 3000 Angstrom units but capable by any details therein, the following illustrative of dissociating tetraethyl lead. examples represent speci?c embodiments of the 2. In a process of producing normal propyl 70 present invention. Example I Propylene and hydrogen sul?de were ‘intro duced in the liquid state and in equal Volumetric proportions into a Pyrex glass reactor. The re mercaptan, the steps of mixing propylene with hydrogen sul?de and tetraethyl lead and effect ing the reaction in the liquid state and at a tem perature not in excess of about 25° C. under the in?uence of photochemical radiatlcns'abcve 3000 2,411,961 . 7 Angstrom units but capable of dissociating tetra ethyl lead. 3. In a proces of e?ecting abnormal addition of hydrogen sul?de, the steps of mixing an ali phatic hydrocarbon containing an alpha unsatu rated linkage with hydrogen sul?de and tetra‘ ethyl lead and effecting the reaction at a temper 8 carbon compound in which a carbon atom of the hydrocarbon radical is united directly to a metal of the fourth group of the periodic table which metallo-hydrocarbon is decomposed by photo chemical radiations above 3000 Angstrom units to the in?uence of photochemical radiations above 3000 Angstrom units but capable of decomposing ature not' in excess of about 25° C. and under the said metallo-hydrocarbon compound. in?uence of photochemical radiations above 3000 10. In a .process of producing thio-ethers, the Angstrom units but capable of dissociating tetra 10 steps of contacting an unsaturated hydrocarbon ethyl lead. having at least one unsaturated linkage between 4. In a process of effecting abnormal addition two carbon atoms having a dissimilar number of of hydrogen sul?de, the steps of mixing an alpha hydrogen atoms attached thereto with a mer unsaturated hydrocarbon with hydrogen sul?de captan, maintaining the reactants at a tempera and tetraethyl lead and effecting the reaction ture not in excess of about 25° C. and in the photochemically under the in?uence of photo absence of peroxides, and subjecting the reactants chemical radiations above 3000 Angstrom units in .the presence of a metallo-hydrocarbon'com but capable of dissociating tetraethyl lead. pound in which a carbon atom of the hydrocarbon 5. The process according to claim 4 wherein radical is united directly to a metal of the fourth te-traethyl lead is employed in an amount of from group of the periodic table which metallo-hydro about 1% to about 10% of the total mixture sub, carbon is decomposed by photochemical radiations jected to reaction. ' above 3000 Angstrom units to the in?uence of 6. In a'process of effecting abnormal addition photochemical radiations of above 3000 Angstrom of hydrogen sul?de, the steps of mixing an alpha units but capable of decomposing the, metallo unsaturated hydrocarbon with hydrogen sul?de 25 hydrocarbon compound under the operating con and a metallo-hydrocarbon compound in which a carbon atom of the hydrocarbon radical is united directly to a metal of the fourth group , ditions. 11. In a process of eifecting reactions via ab normal addition, the steps of reacting an un of the periodic table which metallo-hydrocarbon saturated hydrocarbon having at least one un is decomposed by photochemical radiations above 30 saturated linkage between two carbon atoms hav 3000 Angstrom units, and eirecting the reaction photochemically under the in?uence of photo-. chemical radiations above 3000 Angstrom units but capable of ‘dissociating the metallo-hydro carbon compound. 7. In a process of producing abnormal addition of hydrogen sul?de, .the step of reacting an un saturated organic compound containing an un saturated linkage between two carbon atoms hav ing a. dissimilar number of hydrogen atoms attached thereto, with a compound selected from the class consisting of hydrogen sul?de and mer captans in the presence of a metallo-hydrocar bon compound in which a carbon atom of the hydrocarbon radical is united directly to a metal of the fourth group of the periodic table which - metallo-hydrocarbon is decomposed by photo-. chemical radiations above 3000 Angstrom units, ing a dissimilar number of hydrogen atoms 40 and effecting the reaction photochemically in the attached .to each of said unsaturated carbon absence of peroxides and under the deliberate in atoms with hydrogen sul?dein the presence of a ?uence of photochemical radiations above 3000 metallo-hydrocarbon compound in which a car Angstrom units but capable-of decomposing said bon atom of the‘ hydrocarbon radical is united directly to a metal of the fourth group of the . periodic table which metallo-hydrocarbon is de composed by photochemical radiations above 3000 Angstrom units and under the deliberate in ?uence of photochemical radiations above 3000 Angstronr'units but capable of dissociating said metallo-hydrocarbon compound. 8. In a process of producing di-normal propyl thio-ether, the steps of mixing propylene with normal propyl mercantan and tetraethyl lead and e?ecting the reaction in the liquid state at a - temperature of below about 25° C. and under the deliberate in?uence of photochemical radiations above 3000 Angstrom units but capable of disso ciating tetraethyl lead. _ ‘ i 9; In a processof producing thio-ethers, the 60 steps of contacting an aliphatic hydrocarbon con taining an alpha-unsaturated linkage with a mercaptan and subjecting said mixture in the ' liquid state at a temperature of below about 25° C. and in the presence of a metallo-hydro metallo-hydrocarbon compounds. . 12. Ina process for effecting reactions via ab normal addition, the steps of reacting an~un~ saturated organic compound containing an un saturated linkage between two carbon atoms hav ing a dissimilar number of hydrogen atoms at tached thereto, with a compound selected from the class consisting of hydrogen sul?de and mer captans in the presence of a. metallo-hydrocarbon compound in which a carbon atom of the hydro carbon radical is united directly to a metal of the fourth group of the periodic table which metallu hydrocarbon ‘is decomposed by photochemical radiations above 3000 Angstrom units, and e?ectw ing the reaction photochemically in the absence of peroxides and under the deliberate in?uence of photochemical radiations above 3000 Angstrom units but capable of decomposing said metallo hydrocarbon compounds. THEODORE W. EVANS. WILLIAM E. VAUGHAN. FREDERICK F. RUST.