ALKYLATION mg
R. NORRIS SHREVE
PURDUE UNIVERSITY, LAFAYETTE, IND.
Alkylation i s classified this year entirely under the bonding-i.e., carbon to carbon, carbon to oxygen, carbon to nitrogen, carbon to sulfur, carbon to silicon, and carbon to metal. Supplementing this classification, some of the references are arranged under dealkylation. Under these subheads, there are various catalyst divisions. As was true last year, there has been found increasing study of alkylation involving carbon to sulfur, carbon to silicon, and carbon to various metals. Also in this past year patents continue to be a very important part of the compilation.
HE basic aspects of alkylation continue to receive some
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study. The mechanism of alkylation was discussed in two references. Topchiev and Nametkin (231) studied the relationship between catalyst activity and electrical conductivity, found no correlation, and concluded that a complex formation with the catalyst rather than carbonium ion formation was the source of catalytic action. Marschner and Carmody (146) analyzed the product,s of reactions of isoalkanes and olefin precursors with sulfuric acid catalyst. The analyses indicated the reaction t o be 2C, isoalkane plus C, alkene going to Czn alkane plus C, alkane rather than C, isoalkane plus C, alkene going to C, and C, alkane. The kinetics of the Grignard reaction of methyl magnesium halides with methyl esters of acids were measured by Wichterle and Esterka (244). Catalysts were the subject of several references. Allen (6) describes a process for catalyst recovery in hydrogen fluoride alkylation. Lee (128) mixed the products from an aliphatic and from an aromatic alkylation which resulted in a more rapid separation of the catalyst from the hydrocarbon. The decrease of catalyst activity was measured by Topchiev, Paushkin, Vishnyakova, and Kurashov (232) using electrical conductivity. Several catalyst preparations were described. Mavity (147) mixed a phosphoric acid with an adsorbent such as diatomaceous earth, calcined this mixture, and then heated this product with a solution of a volatile phosphorus salt. Another phosphoric acid catalyst was made by Bielawski ( 1 8 )from the acid and a cellulosic material such as bagasse. Several phosphoric acids were reacted with boron trifluoride by Topchiev and Paushkin (230) to give alkylation catalysts. Eberle (71 ) prepared catalysts from metals below hydrogen in the electromotive force series and phosphoric, chromic, or tungstic acids which could be used in alkylation. A general review of catalysis of hydrocarbon reactions, including alkylation, was made by Grosse (88). Another review on rccent trends in refining processing was presented by Bolles (23).
CARBON-CARBON ALIPHATIC ALKYLATION
In previous years this section has been entitled “Carbon-Carbon Petroleum Alkylations.” As the present emphasis in the literature is not on such aliphatic alkylation, it was thought better to broaden this section. Linn (136)received a patent on the production of 2,8dimethylalkanes in the presence of a hydrofluoric acid catalyst below -10” C. Elsner and Paul (72) have used lithium alkynls in the synthesis of long chain dialkylacetylenes. The reaction t o form octadecynes was carried out in liquid ammonia or dioxane. Catalytic transformations of isoparaffins under pressure, including alkylation of isobutane with propylene and self-alkylation of isopentene, have been studied by Kennedy and Schneider (114). They noticed that with higher isoparaffins, lower temperatures favor self-alkylation, while higher temperatures favor disproportionation with the same degree of branching as the starting
material. The products of the reactions of sodium vapor with methyl iodide and ethyl iodide vapors have been analyzed by Comstock and Rollefson (47). They also discovered that, at higher temperatures, disproportionation reactions and reactions of the radicals with other molecules become the dominant ones. A patent was issued to Hinds, Meerbott, and Reno (98) concerning the production of a propylene tetramer from a hydrocarbon gas fraction containing propane, propene, and isobutane. A solid-type phosphoric acid polymerization catalyst was employed for the three different methods proposed to make the tetramer. Nerdel and Spaeth (160) prepared some dialkyl acetaldehydes from dialkyl ketones and alkyl chloroacetates. In an article on the production of high octane gasoline components, Draeger, Gwin, Leesemann, and Morrow (68) describe briefly many petroleum processes ineluding the conversion of light ends by alkylation. Goldsby (85)received a patent on the acid alkylation of isoparaffins. Another patent on the alkylation of isoparaffins was issued to PllcAllister (139). Isomerized olefins are used in the alkylation t o produce high octane motor fuel paraffins. Carnell (43) also received a patent on treatment for improvement of lubricating oils. Mineral lubricating oils are treated with a mixture of anhydrous hydrofluoric acid, a saturated aliphatic alcohol with from 2 to 18 carbon atoms, and water to produce an oil of improved viscosity and color. The stability of the finished product, however, is not so good as that of the untreated oil.
CARBON-CARBON AROMATIC ALKYLATIONS D e BennevilIe and Bock (56) alkylated benzene with propene dimer to give hexylbenzene. This was chlorinated and added to a tertiary amine t o form the quaternary salt. Morris and Smith (154)used the process of alkylation to purify a hydrorarbon solvent of olefins. Linn and Xewman (136) alkylated aromatic hydrocarbons with olefins in the presence of anhydrous liquid hydrogen bromide. As an addition t o waxes to produce compositions for impregnating fibrous products, Butler (33)alkylated polystyrene lmolecular weight 60,000 t o 1,000,000j with the trimer of propylene. Cristol and Ovcrhaults (52)reacted phenyl sodium with methylallyl chlorides to give the allylbenzene. Their results indicate that this type of process may be the second step in a Wurtz-Fittig reaction. Indole was carbon-alkylated with propiolactone and diketene, according to Harley-Mason ( 9 1 ) ; although structurally similar, the two alkylating agents reacted differently. Shechter and Kaplan (206) treated a solution of sodium and nitropropane in alcohol with p-nitrobenzyltrimethylammonium iodide. The reaction involved removal of the amine group and formation of a carbon-carbon bond, the product being 2-methyl-2-nitro-l-(p-nitrophenyl) propane. Kutz, Nickels, McGovern, and Corson (126) investigated the effect of different catalysts and conditions on ethylation of benzene. The N. V. de Bataafsche Petroleum Maatschappij (168)improved certain characteristics of lubricating oils containing aromatic hydrocarbons by alkylating the aromatic constituents with straight chain olefins catalytically, purifying this alkylate, and then mixing i t with nonalkylated oil.
1903
1904
INDUSTRIAL AND ENGINEERING CHEMISTRY
ALUMINUM CHLORIDE CATALYST
Elwell ( 7 3 ) uses aluminum chloride in concentrations of 0.015 to 0.036 mole of catalyst per mole of xylene in ethylating the latter with ethylene. Elwell and Castro ( 7 4 ) alkylated m-xylene with ethylene and 2% aluminum chloride to produce principally 5ethyl-na-xylene. In preparing i n s u l a h g and transformer oils, the S. I-.de Bataafsche Petroleum Maatschappij (161) alkylated the aromatic constituents of a kerosine with olefins of 6 to 12 carbon atoms using 1.0 to 1.5y0aluminum chloride. Okada and Watabe (170) alkylated liquid benzene with gaseous ethylene; the liquid contained a residue of polyalkyl complex from distillation of benzene and monoalkylbenzene with or without aluminum chloride. il Frie $el-Crafts reaction \vas reported by SocietA Robert Zapp ( 2 1 5 ) for reacting alkyl halides with benzene. Netallic aluminum is included to regenerate the catalyst. 3,4-Dichloro-a-methylstyrenewas made by Stempel (219) by alkylating dichlorobenzene wit'h either propylene, isopropyl alcohol, or isopropyl chloride in the presence of aluminum chloride and dehydrogenating the product. Sidorova (212) used aluminum chloride as catalyst when alkylating benzene w-ith l-methylcyclohexanol. Both mono- and dialkylation occurred. Using aluminum chloride as catalyst, Lagidze (127) alkylated benzene with l-chloro-3-acetoxybutane, splitting out hydrogen chloride to form thee arbon-carbon bond. Pines, Huntsman, and Ipatieff (179) alkylated benzene with methyl-, ethyl-, and dimethyl cyclopropanes using different catalysts and observing their effect on isomerization of the alkylating agent. Condon and Burgoyne ( 4 9 ) show that' the product from aluminum chloride alkylation of benzene n-ith isobutene was the dibutyl derivative, not the butylisopropyl derivative, as was once suspected. A process for purifying ethylene for alkylation by removing propylene was discussed by Upham (239), involving selective hydrochlorination ,over aluminum chloride to give propyl chloride, which is used to alkylate benzene to cumene. Shishido and Furuya (211) fouiid that phenol and it,s derivatives are hard to alkylate by FriedelCraft's met,hods. SULFURIC ACID CATALYSl
The N. I-.de Bataafsche Petroleum Maatschappij (166) prepared compounds suitable for use as detergents and wetting agents by alkylating aromatic hydrocarbons with twelve carbon aliphatics containing 15 t o 30% alkenes and using sulfuric acid as the catalyst. The products are sulfonated t o give the hydrophyllic action. The reaction between ethylene and benzene with sulfuric acid and mercuric sulfate gave bibenzyl as reported by Ichikawa, Tozaki, and Ueki (106). Hart and Cassis ( 9 3 ) alkylated phenols in the ortho position using sulfuric acid as the catalyst. The relative rates of reaction were noted. The nT. V. de Bataafsche Petroleum hlaatschappij (165)used sulfuiic acid as an alkylation catalyst in a process for purifying di- and polyalkylphenols. Truffault and blonteils (634) disclosed the optimum conditions for alkylation of benzene with allyl bromide using sulfuric acid as the catalyst. 4-tert-butyl-3-methylphenol is prepared by Stevens and Bowman ($20) using 0.001 to 0.1% concentrated sulfuric acid as the catalyst in alkylating m-cresol TTith isobutylene.
Vol. 45, No. 9
Ethylnaphthalene was made by alkylation of naphthalene with ethylene, as disclosed by Kickels and Kutz (162). The catalyst was silica 99%, alumina 1yo. Silica with only a trace of alumina was used by Gorin and Gorin ( 8 7 ) in the reaction between benzene and an alkyl chloride. Mahan (143) reacted toluene with propylene on a n acid-activated clay catalyst to produce principally the m- and p-cymenes. PHOSPHORIC ACID CATALYSTS
Ethylbenzene is made by Universal Oil Products Co. ( 2 3 7 ) from ethylene and an excess of benzene. The catalyst is pyrophosphoric acid on diatomaceous earth. Pines and Vesely (182) used a phosphoric acid-ether catalyst a t -10" to 100" C. to alkylate phenols with branched dienes, the products being alkenylphenols. A study of various reactions and products in the alkylation of phenols and thiophenols was made by Buu-Hoi, Bihan, Binon. and Xuong (S4), mho used phosphoric acid as the catalyst. In a process to make alkylbenzene sulfonates to be used as detergents, Davidsohn (54)polymerized gaseous olefins in the presence of phosphoric acid and used the resulting longerchain olefins to alkylate benzene, using an excess of the latter. Universal Oil Products Co. (638) performs a similar reaction to get toluene-olefin condensates. OTHER CATALYSTS
Hydrogen fluoride mas used by Butler ( 3 2 ) to catalyze the alkylation of polystyrenes of high molecular !%-eightwith alkyl halides or olefins. An alkylation process was disclosed by Lien, Hill, and Deters (134)where aromat,ic hydrocarbons are alkylated with Synthol, prepared by hydrogenation of carbon monoxide, in t,he presence of hydrogen fluoride. The California Research Corp. ( 3 7 ) reported the alkylation of benzene or ot,her aromatic hydrocarbons with propylene polymers using hydrogen fluoride as the catalyst. When boron trifluoride is used as the catalyst in the alkylation of benzene by see-but~ylmethylet'her, an act.ivator such as water or certain acids must be preeent in trace amounts, according to Burwell and Elkin (31). In an alkenylation process, aromat'ic hydrocarbons and diolefins are heated in the presence of 5 to 50% of alkane sulfonic acids as reported in a pat,ent by Proell (185). Adams, Proell, and Ballweber ( 1 ) use a liquid alkanesulfonic acid t o give a liquid phase for the reaction of 6- t o 10-carbon aromatic compounds with 7- to 16-carbon olefins. Pratt, Preston, and Draper (183) found that a deficiency of p-tolylsulfonic acid when using alcohols as alkylating agents gave the ether of bhe alcohol. Correct' proportions gave good yields of alkylated product's. Metal derivatives were used as catalysts by some investigators. For the alkylation of phenols, Kooijman (120) employed 0.2 t o 2% zinc oxide and hydrogen chloride. Prutton (186) used acid-activated clay and zinc chloride in the reaction of chlorinated paraffin wax and diphenyl oxide. hletal molybdite salts were recommended by Famcett and Hawk ( 7 6 ) to catalyze the alkylation of aromatic compounds with olefins between 90' and 350" C. Propylbenzene was produced by Mazume and Kobayashi (148) using tungstic and molybdic acids to catalyze t,he react,ion.
CARBON-CARBON ALKYLATIONS ALUMINA-SILICA CATALYSTS
Ipatieff and Pines (107) employed an activated alumina which had been treated with hydrogen halide t o catalyze the alkylation of aromatic hydrocarbons by butene. A combination silicaalumina-gel type catalyst was used by Robinson (198) t o produce monoalkylphenols from olefins and phenol. Arnold (9) converted o-alkylphenols to p-alkylphenols using silica-alumina-gel for alkylation and subsequent dealkylation. Corson and Kutz (61)used the same catalyst to convert a mixture of polyalkyl and unsubstituted aromatics to the monosubstituted aromatic. 2-
GRIGNARD REAGENT
An important number of investigations have been made on the use of the Grignard reagent as an alkylating agent. iMany of these investigations concern alkylations which are a part of the synthesis of long-chain alcohols. For instance, Huston and Tiefenthal (106) published an article on the reactions of 1,2epoxypropane with alkylmagnesium chlorides. A table of the alcohols formed using different alkylmagnesiurn chlorides is given in this article; the yield of alcohols increases when the reaction mixtures are heated in benzene. Drahowzal(69) compares
September 1953
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INDUSTRIAL AND ENGINEERING CHEMISTRY
the reaction products obtained when pyridine and butyraldehyde are added to butylmagnesium bromide with the products obtained when butylmagnesium bromide is reacted with pyridine before the butyraldehyde is added. A 36% yield of 4-octanol resulted when the pyridine and butyraldehyde were added simultaneously. A discueaion of the reaction of Grignard compounds with derivatives of ethylene oxide together with the constitution of the resulting products is presented by Ribas (190). Brault (26) published a paper on the reaction of isobutylene oxide with some alkylmagnesium bromide solutions. Tiefenthal (224) gave a similar paper on the reaction of propylene oxide with various alkylmagnesium chlorides. Freedman and Becker (‘77) have studied the reaction of Grignard reagents with 3,4-epoxy-lbutene to form straight or branched-chain alcohols. In order t o evaluate the controlling factors which lead to the formation of these alcohols, an attempt was made to isolate all the products formed in the reaction of ethylmagnesium bromide and 3,4-epoxyI-butene. Searles (202)outlines a procedure for the reaction of trimethylene oxide with Grignard reagents and organolithium compounds t o give a product which is hydrolyzed with saturated ammonium chloride t o give the desired alcohol, The preparation of bis(alkylpheny1) alkenes fr‘dm the Grignard reaction of an aryl halide with an alkylaryl ketone and the dehydration of the intermediate alcohol is covered in a patent to Pines and Tpatieff (180). The reaction of methyl p-tolyl ketols with organomagnesium compounds was studied by Temnikova and Petrova ($28). These investigators found that the introduction of a p-methyl group enhances enolization and raises the yields of “abnormal” reaction products. Several reactions of Grignard reagents are concerned with the replacement of a halogen atom by an alkyl group. One such reaction has been studied by Schliessler, Speck, and Dixon (198)the reaction of benzyl chloride with n-heptylmagnesium bromide. Pudovik and Mukhamedova (187) investigated the action of organomagnesium compounds on dimethyl (vinyl-ethynyl)chloromethane. They discovered that the reaction goes in part through an acetylene-alkene rearrangement, possibly by a monomolecular route, with the intermediate formation of the carbonium ion. An article by Barber and English ( I S ) gave the procedure in the preparation of 3,5-diethylcyclopentene from 3,5-dibromocyclopentene and ethylmagnesium bromide. Replacement of the bromine atom by a methyl group was investigated by Chancel (44)in an article on the action of organometallic compounds on acetoxydibromoethane. The mechanism of the reaction between organomagnesium compounds and 1,4-dichlorides of conjugated diene hydrocarbons was studied by Levina and Skvarchenko (129). The reaction of the dichloride with alkylmagnesium halides is believed to proceed by cleavage of two chlorine atoms, which, in reacting with the Grignard compound, yield the twinned hydrocarbon. Levina, Skvarchenko, and Tantsyreva (130) have obtained 20% yields of 3,bdimethylcyclopentene by reacting cyclopentadiene 1,4-dichloride with methylmagnesium bromide. The replacement of the alkoxy group of 2-alkoxyquinolines by reacting them with benzylmagnesium chloride was described in an article by Fuson, Jackson, and Grieshaber (78). Malm and Summers (144) described the procedure in the reaction of benzylmagnesium halide with alkyl-haloalkyl ethers. Maximum rearrangement takes place in this reaction when the halogen atom of the benzylmagnesium halide is bromine. Bromohydrins and ketones are the principal products in the reaction of oc-bromoaldehydes with organomagnesium compounds as pointed out by Kirrmann and Chancel (118). The preparation of pyridine derivatives from halopyridines by means of the Grignard reaction was presented in an article by de Jonge, den Hertog, and Wibaut (111). Maginnity and Cloke (142) have investigated the action of methylmagnesium iodide on substituted pyrrolines and related substances, The addition reactions of organomagnesium compounds to 1,l-
1905
dimethylallyl acetate are explainable \yithout a dissociative mechanism, according to Nesmeyanov, FrIedlina, and Kochetkov (161). By steric effects one can direct the point of reaction to the desired atom. Musgrave (158)presents some Grignard reactions with 4-choleston-3-one. A synthesis of P-acetylenic alcohols and or,P’-acetylenic diols is given by Gaudemar (79). In the synthesis of propene-2-04 a Grignard type reaction is used as an intermediate reaction, as reported by Neiman, Lukovnikov, and Iofa (169). COMPLEX ALKYLATION
A number of studies were made on complex alkylations whereby a halide, amino, or cyano group is part of the alkyl group which is linked t o another carbon in the alkylation process. The chloromethylation of hydroxyacetophenones leading to the formation of hydroxy, methoxy, and methyl chloride derivatives was investigated by Trave (233). For instance, he prepared @-chloromethyl-p-hydroxyacetophenone by passing hydrogen chloride gas through p-hydroxyacetophenone, formaldehyde, and hydrogen chloride solution for 7 to 8 hours. Ishiwata and Takada (108) presented an article on the chloromethylation of methoxybenxaldehydes. Another article was written by Murahashi and Matsukawa (166) on the chloromethylation of naphthalene by formaldehyde and hydrogen chloride. This reaction was studied to determine the effect of the formation of bis(chloromethyl) compounds on the simultaneous formation of naphthalene-formaldehyde resins, Shacklett and Smith (204)showed that the chloromethylation reaction could be applied to the synthesis of certain polymethyl benzenes. Increased yields of polymethylbenzenes can be obtained by recycling the monochloromethylated hydrocarbon before the replacement of the chlorine atom by treatment with lithium aluminum hydride. Polymethyl-benzyl esters of water-soluble acids are also prepared through the chloromethylation of a petroleum fraction of high aromatic content, according to a patent granted to Kozacik and Sachanen (122). The products are useful as plasticizers and high boiling solvents. Schmerling (199) received a patent on the haloalkylation of thiophene by treating a thiophene with a haloolefin in the presence of a haloalkylation catalyst such as boron trifluoride. A series of compounds was prepared by Semonskf (203’) in the aminomethylation and the hydroxymethylation of hydrocotarnine. These compounds were prepared to determine how far the individual variously substituted components of 1-CYnarcotine would retain the physiological acti Jity of the starting substance. A patent was given to Howk and Langkammerer (103) concerning the use of cross-linked polyquaternary ammonium hydroxide resins as catalysts in cyanoethylation reactions. Tomita, Uyeo, Otaya, Maekawa, Fukuda, Echigo, Mizukami, and Matsui ( 2 W ) prepared pamaquine (Plasmochin) by the Leuckart reaction. The aminoalkylation of aromatic amines was catalyzed by hydroxy compounds. MISCELLANEOUS CARBON-CARBON ALKYLATIONS
There are many alkylations which are not definitely aromatic or definitely aliphatic carbon-carbon alkylations. Outstanding in this group is the alkylation of cyclic compounds such as thiophene. Gerald and Donaldson (81) have received a patent discussing the alkylation of thiophene by means of olefins, alcohols, alkyl halides, ethers, esters, or mercaptans in the presence of phosphoric acid catalysts. Separation of thiophene from hydrocarbons, especially of the aromatic type, is done by the preferential alkylation of thiophene, according to a patent granted to Vesely (240). The alkylation is accomplished by reaction with an olefin (preferably a tertiary) with a Friedel-Crafts type catalyst under moderate nitrogen pressure. Pines and Kvetinskas (181) report on the condensation of thiophenes with bicycloalkenes to yield products of value in the production of germicides, medicinals, and insecticides. Alkenylthiophenes are
1906
INDUSTRIAL AND ENGINEERING CHEMISTRY
Vol. 45, No. 9
venient svnthesis for monoalkylpyridines has been investigated by Brow711 and Murphey (29). They developed the reaction of methyl chloride with 2-, 3-, and 4picoJine in the presence of sodamide into this synthesis for monoalkylpyridines, which were isolated in a high state of purity. Klein and Spoerri ( 1 1 9 ) have studied the action of organolithivm compounds on 2,5-dimethylpyrazine. Thiazolidinedione or ouazolidinedione with or without substituents a t the 5 position is mrthylated by diazomethane to obtain the 1-methyl compound, according t o a patent received by Iwaya (109). Balaban and Wilde ( 1 1 ) report on their studies on the alkylation of dibutyl malonate with 2-bromobutane, followed by ethyl bromide or diethyl sulfate. Petrov and Ponomarenko (176) have developed a, synthesis of symmetric tetraisopropylethane. The preparation of l-alkyl-3,4dihydro-2( 1H)-naphthalenones is described in a patent granted t o Organon ( 1 7 1 ) . The naphthalenones are monoalkylated in the form of their alkali metal derivatives suspended in anonsolvent; by the usual methods t n o alkyl groups would have been introduced. T w o methylations of 0-methyl glucoside with Purdie reagents give 4,6-dimethyl-pmethylglucoside. This and other preparations of @-methyl glucoside derivatives are reported by Dennison and RlcGilvray (6s). A patent concerning the preparation of alkylated cresylic acids for Ethyl Corp.'s N e w Plant at Houston, Tex., for Production OF Antiknock Compounds use as nondiscoloriny, flex-cracking, and aging inhibitom for natural rubber was received by At le& is sodium area; in foreground are parts of ethyl chloride and ethylene dichloride units. and at right center are tetraethyllead manufacturine and process buildings. The "golf hall" ii B 100,000Smith (214). Alk>lation of 2,6-dimethyl-1,4gallon water tower pyran-4-thione a i t h benzyl iodide and dimethyl dimethyl-4benzylmercapto~yrylium ketone gave - _. iodide. This reaction and other preparations of substituted obtairiecl by the alkylation of tliiophene with OlefinQ in tlw mercaptopyrylium salts have been investigated by King, Ozog, presence of a silicon dioxide-aluniiriuin ohide catalyst ace01rliiig and Moffat ( 1 1 7 ) . to a patent received by Wagner (241). An article by Homing and Fiiielli ( 1 0 2 ) describes the preparation of substituted cyclohexanones by a l k j lating cyclohexanoneu CARBON-OXYGEN ALKYLATIONS with ethyl iodide in a benzene solution. Agarwal and DeshaShirley and Reedy (209) used p-toluene sulfonates to alkylate paride (f?)report a method of alhylation of ketones with arm1 phenolic groups with long chain alkyl groups. Drahowzal and bromide. Cyclohexanone, cycl opent anone, and 3-methyl-c ycloKlaniann (70) carried out the same reartion to prepare a series of pentanone are treated with sodamide and amyl bromide in d r j alkoxy compounds. T h r mono ethers of dihydroxybenzenes were diethyl ether and benzene. The addition of ketene to cyclic made by Oka (169)using p-toluenesulfonic esters. Some dialkylaconjugated dienes to make unsatuiated bicyclic ketones is distion occurred, the yields of mono- and dialkyls being 50 to 60% cussed by Blomquist and Kwiatek (19). Synthetic studies i n and 20 to 25%, respectively. Ethyl e-bromosorbate was used as the series of alkaloids of Ispecacuartha and the quinine tree have an alkylating agent for phenol by Ungnade and Hopkins (286) been made by Preobrazhenskil, Evstigneeva, Levchenko, and D e Groote and Keiser (58-61) obtained patents on a series of Fedyushliina (184). This woik i s an extension of the developproducts to be used as de-emulsifiers, detergents, flotation agents, ment of alkaloid synthese.; from glutaconates to the formation of etc. Intermediates with phenolic hydroxyl groups, often of a einetinelike piperidine derivatives. M ikon ($46) has an article polimeric nature, were hydroxy-alkylated with ethylene oxide or on ihe aminoallrylation of phenyl-substituted acetones. Foi other alkylene oxides. D e Gi oote (57),working alone, obtained example, he reacted phenyl acetone mith 1-dimethylamino-Zother patents for products manufactured by a process which in. rhloroethane in a solution of sodamide and benzene to give volved alkylation of hydroxy groups with alkylene oxides. 5-dimethylamino-3-phenq I-2-pentnnone. Campbell, Hopper, and Campbell ( 4 1 ) investigated the best ronA synthesis of ephedrine IS repoi fed by LMurahashi and Hagiditions for methylenation of the two hydroxy groups of catechol. haia (155); the preparation is carried out with the following The sjnthesis of p-phenetidine mas reported by Yukava (246) alkylation as the first step: BzH+C~H2-.PhCH(OTI)C : CHunder pressures of 14 to 45 atmospheres. Braude and Coles (94) and by bIurnkami and Yiikawa (167) as being accomplished bv the simultaneous reduction and ethoxylation of nitrobenzene Rith have reported on allrenglation emplojing lithium allrenyls, a plonizgnesium and ethyl alcohol, respectively. Tsuruta, Kuroki, cedure on the formation of the cis-propenyl lithium, and some 01 and Xishio (9.95)oxygen-alkylated polyvinyl alcohol catall tical13 its reactions are given also. The industrial importance of the M ith vinylnitrile, which introduces cyanoethyl groups on the reactions of acetylene with compounds containing hydrox) 1, oxygen. Rehberg (188)uses this same alkylating agent on alkyl amino, and carbonyl groups is distussed by Guzmftn and dlberola lactates,. Sodium metal is used to catalyze the reaction. As one (89) with special reference to the catalysts employed. A preparastep in preparing 2-methyl-2,3-dihydrobenzofuran, Entel, Ruof, tion of some diallc.ylcyanoacetamides from cyanoacetamide or monoalkylacetamide is described by Doerge and Wilson (66). and Howard (75)proposed alkylation of phenol with allyl chloride in the presence of sodium methoxide. Overberger and Hoyt The steric effect of displacement reactions in relation to a con-
September 1933
INDUSTRIAL AND ENGINEERING CHEMISTRY
(172, 173) studied the alkylation of a thiophene derivative, 2,5diphenyl-3,4-dihydroxythiophene-l,l-dioxide, with respect to different alkylating agents, principally methylating agents. The reaction of phenol with dibromobutane is accomplished with sodium by Peyron and Peyron (177) to give 1-bromo-4-phenoxybutane which is used in further reactions. Copenhaver (60) made acetals of trihalopropionaldehyde by reacting alcohols with 1-halo-3-trihalopropyl ethers. Diazomethane was used by Shimiau and Ohta (608) to methylate rutin to rhamnetin. Delaby, Sekera, Chabrier, and Piganiol(66) prepared derivatives of 0-hydroxyalkylurethans by reacting them with acetyl chloride and benzyl chloride, producing the acetates and benzoates of the hydroxyl group. Hodge, Karjala, and Hilbert (99) investigated the methylation and ethylation of cornstarch, amylose, and amylopectin in liquid ammonia. Doering and Rhoads (67) studied the alkylation of &keto esters with 2-dimethylaminoethyl chloride.
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CARBON-NITROGEN ALKYLATION
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Included hereunder are alkylbtions involving both trivalent and pentavalent nitrogen linkages. Lewis (132) has patented a process for the alkylation of aromatic amines through the condensation of an aliphatic halide with a primary or secondary aromatic amine. Hill, Shipp, and Hill (97), in their investigations of catalytic vapor phase reactions of aromatic amines, have shown that in continuous alkylations with alcohols under low pressures, the most efficient catalyst is aluminum oxide. All of the catalysts investigated effected more nuclear alkylation than had been anticipated. The preparation of N-alkyl-substituted anilines was studied by Hetzner and Rutherford (96); an alumina-molybdenum catalyst was used and the reactions were carried out in the vapor phase. Dicyanoethylation of aromatic primary amines has been investigated by Mann and Braunholtz (146). An article has been presented by Nogami, Hasegawa, and Tanaka ( 163) on the diethylaminoethylation of primary amines. A study of the reaction mechanism of the methylation of arylamines with tosyl ester was made by N6grBdi and Vajda (164). They found that the reaction in the presence of potassium carbonate occurs in two stages: formation of N-tosylarylamine potassium salt and methylation as an ionic reaction. A Danish patent to Aktieselskabet “Ferrosan” ( 4 ) on the preparation of quaternary ammonium compounds describes alkylation of complex esters by quaternizing with methyl, ethyl, propyl, and isopropyl compounds, particularly the halides, sulfates, phosphates, and sulfonates. The alkylated compounds have increased spasmolytic activity and decreased toxicity. Harris, Shelton, Van Campen, Andrews, and Schumann (92) have prepared quaternary ammonium salts by reacting equimolar quantities of pyridine and a primary alkyl halide in a closed vessel. These salts possess Outstanding germicidal properties. A French patent to Horclois and Robert (101) describes the preparation of quaternary ammonium derivatives of aminophenols. N-dimethylanilines, having in the benzene ring an OR group, in which R is hydrogen or a radical, are treated with dihaloaliphatic hydrocarbons to give quaternary ammonium compounds having a paralyzing effect similar to that of curare. B. F. Goodrich (17) obtained a patent on the preparation of p(dipheny1amino)-propionic acid which may be used as an intermediate, as & weed killer, or to propagate root systems. A Swedish patent to RosdahI (194) describes the preparation of 4alkylamino-2-hydroxybenzoic acid by treating 4-amino-2-hydroxybenzoic acid or an ester or ether thereof with a dialkyl sulfate to form the corresponding N-alkyl derivative. Geigy (80)received a patent on the preparation of the basic ether of p-substituted benzhydrol. The alkylation of ethyl acetamidocyanoacetate with esters has been studied by Tatsuoka, Kinoshita, and Nakamori I22S). Dimethyl sulfate has been used by Medved and Kabachnik (1.49) to alkylate aminomethanephosphoric acid. A
1907
Norwegian patent issued to Aktieselskapet Apothekernes Laboratorium for Special Preparater (6)discusses the preparaa compound tion of 3-ethyl-5,5-dimethyl-2,4-oxazolidinedione, which is useful for the treatment of epilepsy. The reaction is carried out by treating 5,5-dimethyl-2,4oxazoIidinedione with dimethyl sulfate. Lorenz (138) also alkylated this same compound with alkyl halides in the presence of sodium ethoxide. Kaye and Kogon (116) have shown that reductive alkylation of amines with aldehydes and formic acid gives better yields of poorer products than alkylation with corresponding bromides and a condensing agent. An extranuclear N-alkylation of a 2-aminobenzothiazole is described in an article by Kaye and Parris (113). Hall and Burckhalter (90) have indicated a procedure for the displacement of the benzhydryl group of 2-(benzhydrylamino) pyridine by an alkyl group. Fairly good yields of N,N‘-dimethyl-n-butyl-p-phenylenediaminewere obtained by Capinjola (4.3) using dibutylsulfate as an alkylating agent. Tris(hydroxymethyl)-amino-methane was N-alkylated 12 to 15 hours a t 110”C. in glass tubes with equimolar amounts of the alkyl bromide or chloride by Pierce and Wotiz (178). A patent to Comte (48) describes the methylation of substituted uracil with dimethyl sulfate. The action of alkyl halides on magnesium nitride has been investigated by Khomenko (116). Cyanoethylation of aromatic amines, an acid-catalyzed reaction, is described in an article by Bauer and Cymerman (15). Levis (131)was given a patent for the preparation of alkylated aromatic amines by a condensation reaction, with metal oxides and hydroxides being used t o catalyze the reaction between the amine and an aliphatic halide.
CARBON-SULFUR ALKYLATIONS One type of reaction which is used to make carbon-sulfur compounds is the addition of an -SH group across a double bond. van Riemsdijk, van Steenis, and Waterman (191)added hydrogen sulfide to isopentene under the influence of aluminum chloride. The resulting mercaptan could again be added to more olefin. Khomenko (116)reacted isoamyl mercaptan with acetylene under slight pressure and in basic aqueous medium. Three products observed were isoamylthioethylene, di-isoamylsulfide, and the double addition product. Another reaction involving an acetylenic bond was investigated by Holmberg (100). Thioglycolic acid was added to phenylacetylene to give the two unsaturated isomers and the double addition product. The latter has both sulfur bonds attached to the same carbon atom. Ross and Raths (196) made the addition products of phenylmercaptan and benzylmercaptan to I-cyanocyclohexene. The production of thiophene from hydrocarbons and a sulfurbearing molecule was studied by several men. Kreuz (1%) used metalloid oxides, sulfides, and mixtures as catalysts to condense hydrocarbons having a t least two carbons with sulfur dioxide in a vapor phase reaction. The products are substituted thiophenes depending on the hydrocarbon used. Sulfur dioxide was also used by Devaney, Clarke, and Culnane (66)with butane over an alumina-chromia catalyst. The yield was about 30% with the product being 95% thiophene. Appleby and Sartor ( 7 , 8) produced thiophene compounds from hydrogen sulfide and monoolefins. The catalysts were metal oxides such as alumina, and no mercaptans were detectable in the product. Caesar and Branton (56)were interested in the by-products of the reaction between sulfur and butane. Besides 40% thiophene, the product includes 3-thiophenethiol, thiolanedithione, and a polymeric butyl disulfide. Polysulfide resins were made by Dazzi (66) by the addition of an alkylene oxide such as ethylene oxide ,to tertiary alkyl mercaptans to produce intermediates-tert-alkylmercaptoalkanols-which are polymerized by acid catalysts. Shirley and Reedy ($10) used long-chain p-toluenesulfonates as alkylating agents for mercaptans and thiophenols. Octadecyl-p-toluene-sulfonate and p-nitrothiophenol gave p-nitrophenyl octadecyl sulfide.
1908
I N D U S T R I A L AND’ E N G I N E E R I N G C H E M I S T R Y
Vol. 45, No. 9
(150) to be 1,3-diphenyl-l-phenyImercaptopropane.Lewis and Archer (182) prepared sulfonium salts by way of a reaction between toluene thiols and alkyl halides, followed by oxidation. The sulfonium salts were later shown to be suitable for the alkylation of mercaptans.
CARBON-SILICON A L K Y L A T I O N
Tetraethyllead Distillation a t Baton Rouge, La., Plant Ethyl Carp.
OF
Reaction products from autoclaves are distilled to separate tetraethyllead; product is also washed and aerated before being blended with other chemicals to form Ethyl antiknock fluid
Sulfur is introduced into carbon molecules by several reagents. Stahly (218) added thiocyanate radicals to unsaturated bonds under the influence of copper sulfate. Two radicals are added. Thus, vinylnaphthalene and sodium thiocyanate give 1,2dithiocyanoethylnaphthalene. Tertiary alkyl trithiocarbonates were made by Crouch, Crosnoe, and Werlrman (59)by the addition of alkyl mercaptans to carbon disulfide. Badische Anilin- & Soda-Fabrik (10)patented a similar process for both alcohols and mercaptans with carbon disulfide. Halides and base can be substituted for the alcohol. The products are used as addition agents for lubricants. Elemental sulfur is added directly t o unsaturated bonds in two references. Schmitt and Lespagnol (WOO) investigated the behavior of aromatic compounds with ethylenic side chains toyard sulfur. The sulfur did not attack the double bond but formed rings which included the double bond, sulfur atoms, and other carbon atoms when they were available. Spindt, Stevens, and Bald$$in ( 2 1 7 ) reacted sulfur with aliphatic unsaturated hydrocarbons. Similar cyclic compounds were made. Two sulfur atoms formed a ring with the carbon chain and a third formed a thione group. A common reaction for the alkylation of sulfur atoms was that of mercaptans or their metal salts with alkyl halides. Gilman and Bee1 (82) made an intermediate from p-methylthiophenol and lead acetate which gave 2-(p-methylthiopheny1)quinoline when treated with 2-chloroquinoline. The reaction involves the breaking of the lead-sulfur bond and formation of the sulfur-carbon bond. One step in a series of reactions used by Cagniant and Cagniant (36) t o determine a molecular structure m-as the reaction of p-bromothiophenol with p-bromopropionic acid, with hydrogen bromide being split out by caustic. Barker ( 1 4 ) made bis( amylthioethyl) ether from amylmercaptan and 2,2’-dichlorodiethyl ether foruse as anadditive to a lubricant. A synthesis in which the carbon-sulfur bond becomes part of a ring structure is used by Zubarovskil and Fidel (648)to prepare 2-alkylnaphthol (2,l) thiazoles from the potassium salt of 2-amino-1-mercaptonaphthalene and acyl chlorides. GonzAlea and Fernhdez-Bolafios (86) alkylated mercaptoglucimidazoles with chloroacetic acid. Shikanova (207) alkylated cystine with dibromoethane. Analysis of the product showed that an ethylene bridge had been established between two molecules of cystine. Use of 1,3-dibromopropane gave a trimethylene bridge. The product of the reaction of I-cyclohexyl-2-benzoyl-3-phenylethylenimine with thiophenol was found by Meguerian and Clapp
Several investigators have studied the preparation of organosilanes, organohalosilanee, and othcr reactions involving the bonding of a silicon atom to a carbon atom, thus following the trend which was pointed out in last year’s review of alkylation. Schwenker (601) has received a patent claiming improved yields of phenylchlorosilanes by treating chlorobenzene with silicon t o which is added sodium chloride t o reduce the decomposition during the subsequent isolation operations. Aryl halosilanes, such as phenyltrichlorosilanes, used in the preparation of silicone oils, greases, and resins, are made from an aromatic hydrocarbon, a hydrogen halide, and silicon in conjunction with the preformed aromatic halide, according to Coe and Schwenker (46). A synthesis of phenyl silicone is given in an article by Ahsan and Xhundkar ( 3 ) . A patent to Clark (45) outlines a procedure for the condensation of phenylsilanes with a minor amount of aluminum chloride toproducea product in whichthesiliconatomsare linked together through phenylene radicals. -4nother patent t o Brewer (66) describes a preparation of phenyltrichlorosilane in a pressure vessel from dichlorosilane, silicon tetrachloride, benzene, and boron trichloride A direct synthesis of phenylbromosilanes by passing bromobenzene vapor over silicon and powdered copper is reported by Topchiev, Kametkin, and Zhmykhova (220) A British patent has been granted to the Libbey-Owens-Ford Glass Co. (I%’), concerning the preparation of diethyldichlorosilane from ethylene and silicochloroform. Bluestein ( 2 0 ) has studied the reaction of a pyridyl halide with silicon over copper, silver or copper-silver alloy catalysts to give products useful in the preparation of oils, resins, rubbers, and emulsifying and ion exchange agents. Kagner and Strother (242) reacted trichlorosilane with acetylene under a pressure of 17 atm. to give vinyl silane. High yields of niethylbromosilanes a ere obtained by Topchiev and Kametkin (298) by passing methyl bromide through a tube filled with a mixture of 80% silicon and 20% reduced copper The Grignard reaction has been used successfully by Petrov and Chernysheva (176). Another preparation illustrating the use of the Grignard method was discussed by Kumada ( l d 5 ) ; he synthesized several organosilicon compounds by this method. Another article by Topchiev and Nametkin ( a m ) discusses the action of phenylmagnesium bromide on tetraethoxysilane. Swiss and Arntzen (221)patented a process for preparing allylalkylsilanes which are hydrolyzed to polysiloxanes used for insulating conductors. The Grignard method is used here, also. Tertiary-butyl silicon compounds have been made by Sommer (216) by treating a silane with a tertiary-butyl lithium compound. Gilman, Plunkett, and Dunn (84)have prepared some organosilicon compounds containing the p-dimethylaminophenyl group. A typical reaction has Ph$3iCl reacting with MezNCeHJ,i followed by hydrolysis t o yield triphenyl (p-dimethyl aminophenyl) silane. Boldebuck ( 2 2 ) has prepared esters of ethynylsiliconic acid by treating organic derivatives of silicon halides with alkali metal acetylides in a polar solvent. D e Pree, Barry, and Hook (64) have patented a process to make chlorosilyl benzenes by treating a polyhalo aromatic hydrocarbon with a monohydrochlorosilane a t 250’ to 460” C. under sufficient pressure so that at least some of the reaction mixture is in the liquid phase. A British patent granted to Shafer and Wagner (606) describes the technique t o prepare alkyl silicon compounds. Alkanes and trichlorosilane in the presence of a Friedel-Crafts catalyst give alkyltrichlorosilanes. Mohler and Sellers (169) heated the by-products of the reaction of methyl chloride with silicon and a copper catalyst, with chlorobenzene t o methyl,
September 1953
I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY
phenyl dichlorosilane. A patent was received by Lipscomb (137’) in which he claims that organohalosilanes may be prepared by heating a halosilane with a n o l e h in the presence of a compound containing an acyclic azo group.
CARBON-METAL ALKYLATIONS
a
-
Lead is the metal most often studied in carbon-metal alkylations. Calingaert and Shapiro (58-40) obtained patents for the preparation of tetraalkyl lead compounds. Their process reacts metallic lead, the alkyl or aryl radical from a molecu!e with a negative radical, and either zinc, lithium, or cadmium. The latter metals react with the negative radical while the alkyl or aryl part goes to the lead. McDyer and Closson ( 1 4 1 ) convert hexaalkyldile~d compounds to the corresponding tetraalkyllead compounds using 0.2 to 5% of one of several catalysts of the silica type. Metallic lead is another product. The same conversion was patented by Krohn and Shapiro (164). The reaction is brought about by heating the lead compound with alkyl iodides or bromides. Rodekohr and Blitzer (193)patented a continuous process for making tetraethyllead. The lead, as the sodium alloy, is dropped into a rising stream of ethyl chloride which carries the reaction product out of the reactor. Organolithium compounds are prepared by two means: reaction of a halide with the metal, or interconversion between a simple organolithium compound and a more complex organic halide. Jones and Gilman (110)studied the latter in preparing organolithium compounds which were more active than the corresponding Grignard reagents. The interconversion is reversible, the lithium tending to go to the more electronegative organic group. Mikhallov and Chernova (151) used the interconversion reaction to prepare polynuclear lithium compounds from the halide and butyl lithium. The desired compounds could not be made by direct reaction. Preparation of l,2-benaathracene lithium compounds also cannot be done directly, MikhaIlov and Koaminskaya (166)reported. Butyl or phenyl lithium is used in the interconversion reaction. Renaud (189)used ultrasonic rays to disperse the metal in a preparation of organometallic compounds. In a procedure disclosed as general for uni- or multivalent atoms or radicals and illustrated with silicon, Tiganik (666) patented a process for alkylating compounds of the formula X ( O R ) , by substituting an alkyl group for an alkoxy group. Tetraethylsiloxane and chlorobenzene plus sodium in toluene give triethoxyphenylsilane and the polysubstitution products. Many other metals were also the subject of investigations of organometallic compounds a?d reactions. Weisburger, Weisburger, and Ray (243) formed a compound described as a molecular complex by treating 2-aminofluorene with mercuric acetate to get acetamido-3-(acetoxyercuri)fluorene. As disclosed by Yushchenko (84‘7‘),magnesium and vinyl iodide gave only 5% of the Grignard, although 80% of the halide reacts. The reaction of the Grignard with acetylene from the halide is stated to be the main course of the reaction. Acetylene, ethylene, and butadiene are evolved from the ether solution. Briggs and Polya ($7) investigated the preparation of naphthyl cobalt compounds and their reaction with acetyl chloride to give acetylated naphthalene. The synthesis and properties of organoindium compounds were studied by Runge, Zimmermann, Pfeiffer, and Pfeiffer (197), who prepared a complex between trimethyl indium and ether by treating indium trichloride with a methyl Grignard reagent. Other alkyl indium compounds were prepared similarly. Smith and Kraus (613)reacted sodium triphenyl germanide with organic polyhalides. The products were of several classes: the expected alkyl germanium products, a bis-triphenyl germanium oxide, and hexaphenyldigermanide. The germanium compound will not substitute for aromatic halides but hydrogenates the nucleus instead. Some of the reactions of 2-pyridylmetallic compounds were studied by Gilman, Gregory, and Spatz (83),lead and lithium being the metals covered most.
1909
Alkylations involving phosphorus involved mainly the addition
of phosphines and phosphonates to double bonds. Brown (68) patented a process for preparing phosphines by adding phosphine to olefins with a nonoxidizing acid catalyst. Less than 10% of the dialkyl compound is found. Examples of catalysts are hydrogen fluoride and trifluoroacetic acid. Phenyldichlorophosphine was made by Buchner and Lockhart (30)from phosphorus trichloride, benzene, aluminum chloride, and phosphorus oxychloride, The yield was about 75%. Bochwic and Michalski ( E l ) reacted phosphonates or phosphinates with double bonds activated by cyano- and carboxy- groups to form compounds with carbon-phosphorus bonds by cleavage of the hydrogen-phosphorus bond followed by addition. Kosolapoff (121) states that one method of preparing phosphonic and phosphinic acids is that of alkylation of phosphites or other tervalent esters.
DEALKYLATION The formation of quinones by oxidative demethylation is the subject of a patent received by Balakrishna, Seshadri, and Viswanath ( l a ) . An article by Hearon, Lackey, and Moyer (94) discusses the isomerization and demethylation of conidendrin t o two crystal isomers, 01- and 8-norconidendrin. The demethylation of thioanisole to thiophenol is reported by Hughes and Thompson (104)who also give a short explanation of the mechanism of this reaction. N-demethylation by potassium ferricyanide has been studied by Perrine (1’7’4); certain tertiary amines are demethylated to the corresponding secondary amines. Berg, Kindschy, Reveal, and Saner ( 1 6 ) have investigated the use of a hydrofluoric acid-activated alumina as a dealkylation catalyst for aromatic hydrocarbons. Benzene was found to be the ultimate dealkylation product of every aromatic hydrocarbon containing two or more carbon atoms in every branch chain, while toluene was the ultimate dealkylation product of any aromatic hydrocarbon containing only one carbon atom in any of its branched chains. A patent to McAteer and Morrell (140) covers the catalytic vapor phase interaction of alkylated aromatic hydrocarbons and alicyclic compounds effecting dealkylation of the aromatic derivatives and dehydrogenation of the alicycliccompounds. A review of the transformation of trialkyl phosphates to dialkyl phosphates is presented by Rumpf (196). Catalytic reactions of aromatic amines have been studied by Hill and Hill (96). The rearrangement of alkyl groups was also investigated by these two men and it was found that ethyl groups rearranged more readily than methyl groups.
ACKNOWLEDGMENT It is a real pleasure to acknowledge the valuable help in searching, checking, and abstracting the literature contributed by Robert S. Bailey, James E. Marberry, and Elizabeth Prentiss.
LITERATURE CITED (1) Adams, C. E., Proell, W. A., and Ballweber, E. G. (to Standard Oil Co. of Indiana), U. S. Patent 2,585,983 (Feb. 19, 1952). (2) Agarwal, R. R., and Deshapande, S. S., J. I n d i a n Chem. Soc., 28. 65-8 (1951). (3) Ahsan, A. M., and Khundkar, M. H., Pakistan J. Sci. Research 3, 10-15 (1951). (4) Aktieselskabet “Ferrosan,” Danish Patent 73,667 (Jan, 21, 1952). (5) Aktieselskapet Apothekernes Laboratorium for Special Prepmater, Norw. Patent 79,643 (Feb. 4, 1952). (6) Allen, J. G. (to Phillips Petroleum Co.), U. S. Patent 2,574,006 (Nov. 6, 1951). (7) Appleby, W. G., and Sartor, A. F. (to Shell Development Co.), Ibid., 2,558,507 (June 26, 1951). (8) Ibid., 2,558,508 (June 26, 1951). (9) Arnold, P. M. (to Phillips Petroleum Co.), Ibid., 2,553,538 (May 22, 1951). (10) Bedische Anilin- & Soda-Fabrik,German Patent 809,813 ( h g . 2, 1951). (11) Balrtban, I. E., and Wilde, B. E. (to Geigy Co., Ltd.), Brit. Patent 649,682 (Jan. 17, 1951).
1910
INDUSTRIAL AND ENGINEERING CHEMISTRY
(12) Balakrishna, K. J., Seshadri, T. R., and Viswanath, G., Proc. I n d i a n Acad. Sei., 30A, 163-72 (1949). (13) Barber, G. W., and English, J., J. Bm. Chwn. SOC.,73, 746-9 (1951). (14) Barker, G. E. (to the EIgin Xational Watch Co.), U. S. Patent 2,566,157 (Aug. 28, 1951). (15) Bauer, L., and Cymerman, J., Chen~istry&. Industru, 1951, 615-16. (16) Berg, L., Kindschy, E. O., Reveal, W. S.,and Saner, 13. A , , Chem. Eng. Progr., 47, 469--72 (1951). (17) B. F. Goodrich Co., Brit. Patent 651,972 (April 11, 1951). (18) Bielawski, M. S. (to Universal Oil Products Co.), U. S. Patent 2,580,647 (Jan. I , 1952). (19) Blomquist, A. T., and Kwiatek, J., J . Am. Chem. Soc., 73, 2098-2100 (1951). (20) Bluestein, B. A. (to the Gener:tl Electric Co.), U. S. Pstent 2,584,665 (Feb. 5, 1952). (21) Bochwic, B., and Michalski, J., Nature, 167, 1035 (1951). (22) Boldebuck, E. M. (to the Pittsburgh Plate Glass Co.), U. S. Patent 2,551,924 (May 8, 1951). (23) Bolles, W. L., Petroleum Refiner, 30, No, 9, 1950-1 (1931). (24) Braude, E . A., and Coles, J. d.,J . Chem. Soc., 1951, 2078-84. (25) Brault, R. G., Microflnc Abstr., 11, KO. 2, 246-7 (1951). (26) Brewer, S. D. (to the General Electric Co.), U. S. Patent 2,594,860 (April 29, 1952). (27) Briggs, D. A. E., and Polya, J. B., J . Chem. Soc., 1951, 1615-IG. (28) Brown, H. C. (to Standard Oil Co. of Indiana), U. S. Patent 2,584,112 (Feb. 5, 1952). (29) Brown, H. C., and Murphey, W. A , , J . Am. Clie7ri.. Soc., 73, 3308-12 (1951). (30) Buchner, B., arid Lockhart, L. B., Jr., Org. Sgntheses, 31, 88-90 (1951). (31) Burwell, R. L., Jr., and Zlkin, L. M., J . Am. Chem. SOC.,73, 502 (1951). (32) Butler, J. M. (to Monsanto Chemical Co.), U. S. Patent 2,569,400 (Sept. 25, 1951). (33) Ibid., 2,580,996 (Jan. 1, 1952). (34) Buu-Hoi, S g . Ph., Bihan, 3.L., Binon, F., and Xuo~lg,Kg. D., J . Ora. Chem.. 16. 988-94 (1951). (35) Caesar,-P. D., 'and Branton, P. D., INU.ERG. C r i r x . , 44, 122-5 (1952). (36) Cagniant, P., and Cagriiaut, hIrne. P., Conzpt. l e n d , 231, 1508-10 (1950). (37) California Research Corp., Brit. Patent, 663,068 (Dee. 19, 1951). (38) Calinaaert. G., and Shapiro. I1 (to Ethyl Corp.),U. S.Patent 2,5&,207 (June 26, 1951). (39) Ibid., 2,562,856 (July 31, 1951). (40) Ibid., 2,591,509 (April 1, 1952). (41) Campbell, K. N., Hopper, P. F., and Campbell, H. IC.,J . O w . Chem., 16, 1736-41 (1951). (42) Capinjola, J. V., J . Am. Chem. Soc., 73, 1849 (1951). (43) Carnell, P. H. (to Phillips Petroleum Co.), 1;. 9. Patent 2,529,484 (Nov. 14, 1950). (44) Chancel, P., Bull. SOC. china. Prajice, 1951, 228-30. (45) Clark, H. A. (to Dow Corning L'o.), U. 9. Patent 2,557,782 (June 19, 1951). (46) Coe, J. T., and Schwenker, W. A. (to General Electric C o . ) , Ibid., 2,595,767 (May 6. 1952). (47) Comstock. A. A.. and Rollefson, G. R.,J . Chenz. Phus., 19, 441-6 (1951). (48) Comte, F. (to hlonsanto Che~nicalCo.), U. S.Patent 2,642,795 (Feb. 20, 1951). (49) Condon, r.E., and Burgoy~~e, E. E., J . Am. Chem. Soe , 73, 4021-2 (1951). (50) Copenhaver, J, W. (to General Aniline h Film Corp.), U. 9. Patent 2,556,905 (June 12, 1951). (511 Corson. B. B., amd Kuta, UT.M. (to Koppers Co., In(:.), I h i d . , 2,589,057 (h'larch 11, 1952). 152) Cristol, S. J., and Overhaults, W. C., J . Am. C'hem. Soc., 73, 2932-3 (1951). (53) Crouch, W. W., Crosnoe, T. F., and Werkman, R . T. (to Phillips Petroleunl Co.), U. S.Patent 2,600,737 (June 17, 1952). (54) Davidsohn, A., I d . Chemist, 28, 198-203 (1952). (55) Dazzi, J. (to Monsanto Chcrnical Co.), U. S. Patent 2,563,686 (Aug. 7, 1951). (56) De Benneville, P. I,., and Bock, L. H. ( t o Rohm 81 Ham C o . ) , Ibid., 2,569,408 (Sept. 25, 1951). (57) De Groote, M. (to Petrolite Corp., Ltd.), Ibid., 2,574,817 (Nov. 13, 1951). (58) De Groote, M., and Keiser, 13.. Ibid., 2,571,120 (Oct,. 16, 1951). (59) Ibid., 2,568,118-19 (Sept. 18, 1951). (GO) Ibid., 2,589,062 (March 11, 1962). (61) Ibid., 2,598,234 (May 27, 1952). (62) Delaby, R., Sekera, A , , Chabrier, P., and Piganiol, P., RidZ. SOC. c h i m . France, 1951, 392 -7. ~I
~I
Vol. 45, No. 9
(63) Dennison, J. C., and McGilvray, D. I., J . C h a . SOC.,1951, 1616. (64) De Pree, L., Barry, A. J., and Hook, D. E. (to Dow Chemical Co.), E. S.Patent 2,580,169 (Dee. 25, 1951). (65) Devaney, L. W., Clarke, J. T., and Culnane, C. H. (to Texas Co.), Ibid., 2,558,716 (July 3, 1951). (66) Doerge, R. F., and Wilson, C. O., J. Am. Pharm. Assoc. Sei. Ed., 40, 407-9 (1951). (67) Doering, W. v. E., and Rhoads, S.J., J. Am. C h a . Soc., 73, 30824 (1951). (68) Draeger, A. A,, Gwin, G. T., Leesemann, C. J. G., and Morrow, M. R., Petrolenm Kefiner, 30, No. 9, 107-11 (1951). (69) Drahowsal, F., Monatsh., 82, 794-8 (1951). (70) Drahowsal, F., and Klamann, D., Ibid., 82, 588-93 (1951). (71) Eberle, J. F. (to Phillips Petroleum Co.), I J . S. Patent 2,570,925 (Oct. 9, 1951). (72) Elsner, B. B., and Paul, P. F. M.,J . Ciiem. SOC.,1951, 893-7. (73) Elwell, W. E. (to California Hesearch Corp.), U. 8. Patent 2,578,294 (Dee. 11, 1951). (74) Elwell, W. E., and Cast,ro, A. J., Ibid., 2,563,826 (Aug. 14, 1951). (75) Entel, J., Ruof, C. I-I., and Howard, H. C., J . Ani. Chem. SOC., 73. 2365 (1951). (76) Fawdett, F.'S., and Hawk, B. W. (to E. I. du Font de Nemouis & Co.), U. S. Patent 2,572,019 (Oct. 23, 1951). (77) Freedman, R. W., and Becker, E. I., J. Org. Chem., 16,1701-11 (1951). (78) Fuson, R. C., Jackson, H. L., and Grieshaber, E. W., J . Ora. Chem., 16, 1529-35 (1951). (79) Gaudemar, >I., Conzpt. rend., 233, 64-6 (1951). (80) Geigy, J. R., Swiss Patent 264,135 (Dee. 16, 1949). (81) Gerald, C. F., and Donaldson, G. R. (to Universal Oil Products '20.1, U. S.Patent 2,570,542 (Oct. 9, 1951). (82) Gilman, H., and Beel, J. A , , J . Am,. Chem. SOC.,73, 774--7 (1951). (83) Gilman, H., Gregory, W.A,, and Spats, S. M., J. 01.9. Cliern., 16, 1788-91 (1951). (84) Gilman, H., Plunkett, M. .4.,and Dunn, G.. E., J . A n ? . Chem. Soc.. 73, 1686-8 (1951). (85) Coldsby, A. R. (to Texas Co.), U. S. Pateut 2,567,283 (Sept. 11, 1951). (80) GonsBles, F. G., and Bern&ndea-Bola5os, J., AnaEes real SOC: espufi. fis. y quim. ( M a d r i d ) ,45B, 1527--30 (1949). (87) Gorin, M. H., and Gorin, E. (to Socony-Vacuum Oil Co., Inc.), U. S. Patent 2,581,014 (Jan. 1, 1952). (88) Grosse, A. V., Record Chem. Progy., 13, 55-04 (1952). (89) GuzmBn, G. M., and Alberola, A. R., Rev. cienc. apl. ( M a d ~ i d ) , 4, 507-26 (1950). (90) Ilall, L. A. R., and Hurckhalter, J. H., J . Am. Chem. Soc., 73, 4 7 3 4 (1951). (91) Harley-Mason, J., C h e m i s t y g & Industry, 1951, 886-7. (92) Harris, G . H., Shelton, R. S., Van Campen, M , G., Andrews, E. R., and Schumann, E. Id., J . Am. Chem. SOC.,73, 3959-63 (1951). (93) Hart. H.. and Cassis, F,A , Jr., J . Am. Che/rc. Soc.. 73, 3179 4 2 (1961). (94) Hearon, W. &I., Lackey, Fi. B., and Moyer, W. W., .J. A m Chem. Soc., 73, 4005-7 (1951). (95) Hetaner, H. P., and Rutherford, J. T. (to California Research Corp.), U. S.Patent 2,665,4.28 (Aug. 21, 1951). (96) Hill, A. G., and Hill, A. J . , ISD. ENG.CHEST.,43, 1583-5 (1951). (97) Hill, A. G., Shipp, J. H., and Hill, A. J . , I b i d , , 43, 1579--83 (1951). (98) Hinds, G . P., Jr., hIeerbott, 77'. K., and Reno, G. ,J. (to Shell Development C o . ) , I;. 8. Patent 2,572,724 (Oct. 23, 1951). (99) Hodge, J. E., Karjala, S.A , , and Hilbert, G. E,, J . Am. Chem. SOC., 73, 3312 -16 (1951). (100) Holmberg, B., A ~ k i vKemi, 2, 567-79 (1950). (101) Horclois, E. J., and Robert, J. G., French Patent 959,Trl.l (April 6, 1950). (102) .Homing, E. C., and Finelli, A. F., J . AIYL. Chem. Soc., 73, 3741 (1951). (103) Howk, B. W.,and Langkanimerer, C. &I. (to E. I. du Font de Nemorirs h C o . ) , U. S. Patent 2,579,580 (Dec. 25,1951). (104) Hughes, G. K., and Thompson, E. 0. P., .J. Proc. Rou. SOC. N . S.Wales, 83, 269-74 (1949). (105) Huston, R. C., and Tiefenthal, H. E., J . Org. Chem., 16, 673-8 (1951). (106) Ichilrawa, K., Toaaki, IT., Ueki, I., and Shingu, II., J . Ch,em. SOC.J a p a n , Pure Chem. Sect., 72, 267-9 (1951). (107) Ipatieff, V. N., and Pines, H. (to Universal Oil Products Co.), U. S.Patent 2,584,103 (E'eb. 5, 1952). (108) Tshiwata, S., and Takada, T., J . Pharm. Soc. Japan, 71, 1254-6 (1951).
September 1953
INDUSTRIAL AND ENGINEERING CHEMISTRY
(109) Iwaya, K. (to Shionogi Drug Manufg. Co.), Japan. Patent 179,660 (July 18, 1949). (110) Jones, R. G., and Gilman, H., “Organic Reactions,” Vol. VI, pp. 336-9, New York, John Wiley & Sons, Inc., 1951. (111) de Jonge, A. P., den Hertog, H. J., and Wibaut, J. P., Rec trav. chim., 70, 989-96 (1951). (112) Kaye, I. A,, and Kogon, I. C., Rec. trav. chim., 71, 309-17 (1952). (113) Kaye, I. A,, and Parris, C. L., J . Org. Chem., 16, 1859-63 (1951). (114) Kennedy, R. M., and Schneider, A. (to Sun Oil Co.), U. S. Patent 2,557,113 (June 19, 1951). (115) Khomenko, A. Kh., Izvest. A k a d . N a u k S.S.S.R., Otdel. K h i m N a u k , 1951, 280-3. (116) Ibid., pp. 806-8. (117) King, L. C., Ozog, F. J., and Moffllt, J., J . Am. Chem. Soc., 73, 300-2 (1951). (118) Kirrmann, A,, and Chancel, P., Bull. SOC. chim. France, 1951, 227-8. (119) Klein, B., and Spoerri, P. E., J . Am. Chem. Soc., 73, 2949-51 (1951). (120) Kooijman, E. C. (to Shell Development Co.), U. S. Patent 2,567,848 (Sept. 11, 1951). (121) Kosolapoff, G. M., “Organic Reactions,” Vol. VI, pp. 273-338, New York, John Wiley & Sons, Inc., 1951. (122) Kozacik, A. P., and Sachanen, A. N. (to Socony-Vacuum Oil Co.), U. S. Patent 2,554,709 (May 29, 1951). (123) Kreuz, K. L. (to Texas Co.), Ibid., 2,557,664 (June 19, 1951). (124) Krohn, I. T., and Shapiro, H. (to Ethyl Corp.), Ibid., 2,555,891 (June 5, 1951). (125) Kumada, M., J. Inst. Polytech. Osaka City Univ. Ser. C., 2, NO. 1, 11-18 (1951). (126) Kutz, W. -MI., Nickels, J. E., McGovern, J. J., and Corson, B. B.,J. Org. Chem., 16, 699-703 (1951). (127) Lagidze, R. M., Doklady A k a d . N a u k S.S.S.R., 77, 1023-6 (1951). (128) Lee, H. H. (to Phillips Petroleum Co.), U. S.Patent 2,582,047 (Jan. 8, 1952). (129) Levina, R. Ya., and Skvarchenko, V. R., Vestnik Moskou. Univ. 6 , N o . 6,Ser. Fiz.-Mat. i. Estestven. N a u k , No. 3, 91-5 (1951). (130) Levina, R. Ya., Skvarchenko, V. R., and Tantsyreva, T. I., V e s t n i k , Moskov. Univ. 6, hTo. 2 , Ser. Fiz.-Mat. i. Estestven. N a u k , No. 1, 137-8 (1951). (131) Levis, W. W., Jr. (to Sharples Chemical Co.), U. S. Patent 2,541,655 (Feb. 13, 1951). (132) Lewis, T. R., and Archer, S., J . Am. Chem. Soc., 73, 2109-13 (1951). (133) Libbey-Owens-Ford Glass Co., Brit. Patent 669,189 (March 28, 1952). (134) Lien, A. P., Hill, P., and Deters, J. F. (to Standard Oil Co. of Indiana). U. S. Patent 2,564,072 (Aug. 14, 1951). (135) Linn, C. B. ( t o Universal Oil Products Co.), Ibid., 2,570,574 (Oct. 9, 1951). (136) Linn, C. B., and Newman, R. J., Ibid., 2,563,050 (Aug. 7, 1951). (137) Lipscomb. R. D. (to E. I. du Pont de Nemours & Co.), Ibid., 2,570,462 (Oct. 9, 1951). (138) Lorenz, R., Austrian Patent 171,712 (1952). (139) McAllister, S. H. (to Shell Development Co.), U. S. Patent 2,591,367 (April 1, 1952). (140) McAteer, J. H., and Morrell, C. E., (to Standard Oil Development Co.), Ibid., 2,577,788 (Dec. 11, 1951). (141) McDyer, T. W., and Closson, R. D. (to Ethyl Corp.), Ibid., 2,571,987 (Oct. 16, 1951). (142) Maginnity, P. M., and Cloke, J. B., J . Am. Chem. SOC.,73, 49-51 (1951). (143) Mshan, J. E. (to Phillips Petroleum Co.), U. 8. Patent 2,564,488 (Aug. 14, 1951). (144) Malm, L., and Summers, L., J . Am. Chem. SOC.,73, 362-3 (1951). (145) Mann, F. G., and Braunholtz, J. T., Chemistry & Industry, 1951, 1066. (146) Marschner, R. F., and Carmody, D. R., J . Am. Chem. SOC.,73, 604-7 (1951). (147) Mavity, J. M. (to Universal Oil Products Co.), U. S. Patent 2,584,102 (Feb. 5 , 1952). (148) Mazume, T., and Kobayashi, E. (to the Bureau of Industrial Technics), Japan. Patent 181,442 (Jan. 23, 1950). (149) Medved, T. Ya., and Kabachnik, M. I., Izuest. A k a d . N a u k S.S.S.R., Otdel. Khim. N a u k , 1951, 6204. (150) Meguerian, G., and Clapp, L. B., J. Am. Chem. Soc., 73, 486 (1951). (151) Mikhallov. B. M.. and Chernova. N. G., Doklady A k a d . N a u k S.S.S.R.’, 78, 489-92 (1951). (152) Mikhallov, B. M., and Kozminskaya, T. K., Zhur. Obshchel Khim., 21, 1276-83 (1951). ~I
1911
(153) Mohler, D., and Sellers, J. E. (to General Electric Co.), U. S. Patent 2,598,434 (May 27, 1952). (154) Morris, L. C., and Smith, F. M. (to Phillips Petroleum Co.), Ibid., 2,604,494 (July 22, 1952). (155) Murahashi, S., and Hagihara, N., Proc. J a p a n Acud., 23, 147-8 (1947). (156) Murahashi, S., and IMatsukawa, H., Bull. Inst. Phys. Chem. Research ( T o k y o ) , 21, 509-19 (1942). (157) Muiakami, M., and Yukawa, Y., M e m . Inst. Sci. and Ind. Research Osaka Univ., 7, 116-20 (1950). (158) Musgrave, 0. C., J . Chem. Soc., 1951, 3121-3. (159) Neiman, M. B., Lukovnikov, A. F., and Iofa, B. Z., Doklady Akad. N a u k S.S.S.R., 78, 493-6 (1951). (160) Nerdel, F., and Spaeth, I., Chem. Ber., 84, 971-2 (1951). (161) Nesmeyanov, A. N., Friedlina, R. Kh., and Kochetkov, A. K., Izvest. Akad. N a u k S.S.S.R. Otdel. K h i m . N a u k , 1951, 273-9. (162) Nickels, J. E., and Kutz, W. M. (to Koppers Co., Inc.), U. S. Patent 2.570.263 iOct. 9. 1951). (163) Nogami, H., Hasegawa, J:, and’ Tanaka, A., J . Pharm. SOC. J a p a n , 71, 1496-7 (1951). (164) N6gr&di, T., and Vajda, M., Magyar K h . L a p j a , 4, 709-11 (1949). (165) N. V. de Bataafsche Petroleum Maatachappij, Brit. Patent 655,715 (Aug. 1, 1951). (166) Ibid., Brit. Patent 661,383 (Nov. 21, 1951). (167) Ibid., 664,095 (Jan. 2, 1952). (168) Ibid., Dutch Patent 69,044 (Deo. 15, 1951). (169) Oka, S., Bull. Inst. Chem. Research, Kyoto Univ., 25, 73 (1951). (170) Okada, T., and Watabe, S. (to Nippon Nitrogenous Fertilizers Co.), Japan. Patent 173,864 (Oct. 14, 1946). (171) Organon, N. V., Dutch Patent 67,888 (May 15, 1951). (172) Overberger, C. G., and Hoyt, J. M., J . Am. Chem. Soc., 73, 3305-8 (1951). (173) Ibid., pp. 3957-8. (174) Perrine, T. D., J . Org. Chem., 16, 1303-7 (1951). (175) Petrov, A. D., and Chernysheva, T. I., Izvest. A k a d . N a u k S.S.S.R. Otdel. Khim. N a u k , 1951, 820-2. (176) Petrov, A. D., and Ponomarenko, V. A., Doklady A k a d . N a u k S.S.S.R., 74, 739-42 (1950). (177) Peyron, L., and Peyron, J., Bull. SOC. chim. France, 1950, 10624. (178) Pierce, J. S., and Wotiz, J., J . Am. Chem. Soc., 73, 2594 (1951). (179) Pines, H., Huntsman, W. D., and Ipatieff, V. N., Ibid., 73, 4343-7 (1951). (180) Pines, H., and Ipatieff, V. N. (to Universal Oil Products Co.), U. S. Patent 2,578,207 (Dec. 11, 1951). (181) Pines, H., and Kvetinskas, B., Ibid., 2,553,785 (May 22, 1951). (182) Pines, H., and Vesely, J. A., Ibid., 2,578,206 (Dec. 11, 1951). (183) Pratt, E. F., Preston, R. K., and Draper, J . D., J . Am. Chem. SOC.,72, 1367-9 (1950). (184) Preobrazhenskii, N. A., Evstigneeva, R. P., Levchenko, T. S., and Fedyushkina, K. M., Doklady A k a d . Naulc S.S.S.R., 81, 421-3 (1951). (185) Proell, W. A. (to Standard Oil Co. of Indiana), U. S. Patent 2,564,077 (Aug. 14, 1951). (186) Prutton, C. F. (to Lubri-Zol Corp.), Ibid., 2,555,370 (June 5, 1951). (187) Pudovik, A. N., and Mukhamedova, L. A., Zhur. Obshchel K h i m . , 21, 1472-6 (1951). (188) Rehberg, C. E. (to the United States of America, as represented by Secy. of Agr.), U. S. Patent 2,559,660 (July 10, 1951). (189) Renaud, P., Bull. soc. chim. France, 1950, 1044-5. (190) Ribas, I., Anales real soc. espaii. fts. y qu6m. ( M a d r i d ) , 47B, 82340 (1951). (191) Riemsdijk, A. J. van, Steenis, J. van, and Waterman, H. I., J. Inst. Petroleum, 37, 265-9 (1951). (192) Robinson, S. P. (to Phillips Petroleum Co.), U. S. Patent 2,578,597 (Dec. 11, 1951). (193) Rodekohr. H. M.. and Blitzer. S. M. (to Ethvl Corm). , Ibid.. 2,574,759 (Nov. 13, 1951). (194) Rosdahl, K. G. (to Aktieselskabet “Ferrosan”). Swed. Patent 133,598 (Nov. 20, 1951). (195) Ross, R. M., and Raths, F. W., J . Am. Chem. SOC.,73, 129-30 (1951). (196) Rumpf, P., Bull. SOC. chim. France, 1951, C128-32. (197) Runge, F., Zimmermann, W., Pfeiffer, H., and Pfeiffer, I , Z. anorg. u. allgem. Chem., 267, 39-48 (1951). (198) Schliessler, R. W., Speck, R. M., and Dixon, J. A., J . A m . Chem. SOC.,73, 3524-6 (1951). (199) Schmerling, L. (to Universal Oil Products Co.), U. S. Patent 2,563,073 (Aug. 7, 1951). (200) Schmitt, J., and Lespagnol, A , , B u l l . SOC. chim. France, 1950, 459-63. (201) Schwenker, W. A. (to General Electric Co.), U. S. Patent 2,579,341 (Dec. 18, 1951).
INDUSTRIAL AND ENGINEERING CHEMISTRY Searles, S., J . Ant. Chem. SOC.,73, 124-5 (1951). Semonskp, M., Collection Czechoslov. Chem. Communs., 15, 1024-36 (1951).
Shacklett, C. D., and Smith, H. A , , J . Am. Chem. SOC.,73, 7 6 6 8 (1951).
Shafer, P. W., and Wagner, G. H. (to Linde Air Products Co.), Brit. Patent 662,916 (Dee. 12, 1951). Sheohter, H., and Kaplan, R. B., J . Am. Chem. SOC.,73, 1883 (1951).
Shikanova, I. A., J . Appl. Chem. (U.S.S.R.), 23, 703-9 (1950). Shimizu, IM., and Ohta, G., J . Pharm. Soc. Japan, 71, 879-82 (1951).
Shirley, D. A., and Reedy, W.H., J . Am. Chem. SOC., 73, 458-9 (1951). Ibid., pp. 4885-6.
Shishido, K., and Furuya, S.,J . Chem. I n d . (Japan),46, 151B (1943).
Sidorova, N. G., Zhur. ObshcheZ Khim., 21, 869-74 (1951). Smith, F. B., and Kraus, C . d.,J . Am. Chem. Soc., 74, 1418-20 (1952).
Smith, G. E. P. (to Firestone Tire and Rubber Co.), U. S. Patent 2,581,906 (Jan. 8, 1952). Societ&Robert Zapp., Ital. Patent 459,251 (Sept. 1 , 1950). Sommer, L. H. (to Don. Corning Co.), Brit. Patent 657,442 (Sept. 19, 1951). Spindt, R. S.,Stevens, D. R., and Baldwin, W.E., J . An?. Chem. Soc., 73, 3693-7 (1951).
Stahly, E. E, (to Koppers Co., Inc.), U. S. Patent 2,539,493 (Jan. 30, 1951). Stempel, G. H., Jr. (to General Tire and Rubber Co.), Brit, Patent 652,618 (April 26, 1951). Stevens, D. R., and Bowman, R. S. (to Gulf Research and Development Co.), U. S. Patent 2,560,666 (July 17, 1951). Swiss, J., and Arnteen, C. E. (to Westinghouse Electric Corp.), Ibid., 2,595,729 (May 6 , 1952). Tatsuoka, S.,Kinoshita, T., and Nakamori, R., J . Pharm. SOC.Japan, 71, 702-4 (1951).
Temnikova, T. I., and Petrova, L. il., Zhur. Obshchei Iihim., 21, 1877-83 (1951).
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(225) Tiganik, L. (to Uddeholms Aktiebolag), Swed. Patent 132,873 (Sept. 11, 1951). (226) Tomita, &I., Uyeo, S., Otaya, H., Maekawa, H., Fukuda, M., Echigo, S., Mieukami, S., and Matsui, T., J. Pharm. SOC. J a p a n , 71, 829-34 (1951). (227) Topchiev, 4.V., and Nametkin, N. S.,Dokludy A k a d . Naulc S.S.S.R., 80, 897-8 (1951). (228) Ibid.. 78. 295-7 11951). (229) Topehie;, A. Y., Kametkin, K. S., and Zhmykhova, N. RI., Ibid., 78, 497-500 (1951). (230) Topchiev, A. I-., and Paushkin, Ya. hI., Ibid., 58, 1057-60 (1947). (231) Topchiev, A. V., Paushkin, Ya. >I., Vishnyakova, T. P., and Kurashov, 31. V., Ibid., 80, 381-4 (1951). (232) Ibid., pp. 611-13. (233) Trave, R., Gam. chim. itnl., 81, 773-81 (1951). (234) Truffault, R . , and Nonteils, Y., Bull. soc. chim. France, 1951, 230-3. (235) Tsuruta, M., Kuroki, N., and Nishio, M,, Chem. High Polymers ( J a p a n ) , 7 , 129-31 (1950). (236) Ungnade, H. E., and Hopkins, T. R., J . Am. Chem. SOC.,73, 3091-3 (1951). (237) Gniversal Oil Products Co., Brit. Patent 655,395 (July 13, 1961). (238) Ibid., 669,657 (April 9, 1952). (239) Upham, J. D. (to Phillips Petroleum Co.), U. S. Patent 2,570,407 (Oct. 9, 1951). (240) Vesely, J. A. (to Universal Oil Products Co.), Ibid., 2,563,087 (Aug. 7, 1951). (241) Wagner, C. R. (to Phillips Petroleum Co.), Ibid., 2,560,010 (July 17, 1951). (242) Wagner, G . H . , and Strother, C. 0. (to Linde Air Products Co.), Brit. Patent 670,617 (April 23, 1952). (243) Weisburger, E. K., Weisburger, J . H., and Ray, F. E., J . Org. C ~ ~ W Z16. . . 1697-1700 (1951). (244) Wichterle, O., and Esterka, F., Collection Czechoslov. Chem. Communs., 15, 1021-3 (1951). (245) Wilson, W., J. Chem. SOC.,1952, 6-9. (246) Yukawa, Y., J . Chem. SOC.Japan, P u r e Chem. Sect., 71, 547-9 (1950). (247) Yushchenko, Yu. I., Zhur. Obshchei Khim., 21, 1244-7 (1951). (248) Zubarovskii, V.AI.,and Fidel, 9. N., Ibid., 21, 2064-8 (1951).
Amination
mx
JESSE WERNER,
Vol. 45, No. 9
b y Reduction
GENERAL ANILINE
AND FILM CORPORATION, GRASSELLI, N. J .
A method has been developed for the very rapid reduction of steam-volatile nitro compounds by the Bhchamp (iron and acid) method, thus avoiding by-products. Various studies have been carried out on the effect of conditions on yields by catalytic hydrogenation. The reduction of various nitroheterocycles to the corresponding amines by catalytic hydrogenation has been described. A method has been developed for the preparation of relatively pure primary amines by catalytic reduction of oximes. A patent has been issued on the preparation of monoaminopolystyrene from the corresponding nitro compound by reaction with sodium disulfide under pressure. Studies have been carried out on the electrolytic reduction of various nitro compounds and nitriles to amines. Miscellaneous reductions were reported during the year relating to the use of zinc and acid, ferrous sulfate and potassium carbonate, stannous chloride and hydrochloric acid, sodium dithionate, and tetrahydronaphthalene. A patent has been issued on the use of aluminum instead of zinc for the preparation of hydrazobenzenes, intermediates in the manufacture of benzidines. A general method was also developed for the reduction of organic azides to primary amines by means of lithium aluminum hydride.
D
URIKG the 12-month period since the last review (@), a
limited amount of work relating to the unit process amination by reduction has been published in the patent and other technical literature. iis has been customary in the past, this paper will be divided into sections dealing with Bdchamp (iron and dilute acid), catalytic, sulfide, electrolytic, and miscellaneous reductions. As usual, most of the published work is
devoted to catalytic methods: in spite of the fact that other methods are used to a far greater extent in carrying out this unit process on a commercial scale a t the present time. Preparation of amines by catalytic reduction, however, provides a very versatile laboratory and plant tool for obtaining the widest variety of amines, most often in high yield and purity.
BECHAMP REDUCTION A very meager amount of chemical and chemical engineering work has been reported on this method during the past year in spite of the fact that i t is used to a greater extent than any other for the reduction of nitro compounds in industry. Von Bramer et al. (39) have been granted a patent for a very interesting method of reducing steam-volatile, aromatic nitro compounds re-
