ALKYLATION
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R. NORRIS SHREVE PURDUE UNIVERSITY, LAFAYETTE, IND.
This year the same headings are employed in the alkylation review as were used last year; these are based on the chemical change. The subheadings of Carbon-Carbon Aromatic A l k y lations: Alumina-Silica Catalysts, and Other Catalysts have been placed under Miscellaneous Catalysts. Literature references are separated in the same divisions as is the text, but the text does not include every reference found under alkylation during the year 1953 of Chemical Abstracts. Those references judged to b e of lesser importance are not included. A study of the alkylation references revealed fewer alkylations with the carbon-sulfur bonding; however, many studies were published on alkylations involving the carbon-silicon bonding.
XLY a small amount of research was conducted on the basic aspects of alkylation, and this pertained to specific reactions. Jones and Neuworth ( 7 A ) studied the thermal cracking of pure alkylplienols. By assuming a firstorder reaction, they determined the activation energies for ocresol, 2,4-xylenolJ and m-cresol. The rate determining step was the free radical rupture of the carbon-hydrogen bond in the methyl group. The primary products of cracking and their mole per cent conversions were given. De la Mare and Vernon ( 4 A) found that the reaction of dichloropropene with the ethoxy ion of ethanol consisted mainly of the two simultaneous bimolecular reactions leading to the formation of diethoxy propene and of cis- and trans-chloroethoxypropene. The second-order rate coefficients, activation energies, and yields were also calculated. Some theoretical aspects of orientation in the dialkylation of benzene by electrophilic substitution are discussed by Hennion and associates ( 6 A ) ; hyperconjugation plays only a minor role in the stabilization of ionic intermediates, and the ortho to meta to para ratio is strongly affected by steric features of the transition states. Hypsochromic shifts produced by methyl substitution in certain unsaturated hydrocarbons are interpreted in terms of simple molecular orbital theory by LonguetrHiggins and Sowden ( 9 A ). The shifts can occur only if one or more odd-membered rings are present. The theory was applied to methylated aaulene and fulvene. Methylation of stilbestrol of diasomethane in the presence of methanol containing the tracer atom C14 was carried out by Weygand and Kirchner (ZOA). All details of the preparation are presented. The methylation was carried out in diethyl ether and the methanol did not appear in the end product. The effects of alkyl groups upon orientation was the subject of three articles. Buu-Ho'i and associates ( $ A ) investigated the orienting influence of the methyl group in m-methylacetanilide and m-methylanisole. Studies of the steric effect of methylene groups by Arnold and associates ( I A ) showed that the steric effect of an o-methylene group in a 6-membered ring is greater than that in a corresponding 5-membered ring. A presentation by Crawford and Stewart ( S A) stated that although toluene and xylene may be substituted in both positions ortho to the alkyl group, tert-butylbenaenes bearing a substituent in one ortho position resist substitution in the other. Two reviews containing the unit process of alkylation appeared. The first, by Kiddoo ( 8 A ) , reported on the technology of the major processes used to make industrial chemicals from petroleum and natural gas hydrocarbons. The second ( 6 A ) reviewed the substitution reactions of unsaturated compounds,
lysts was studied by Schneider and Kennedy ( I b B ) . In the treatment of isobutanc with the catalyst, the self alkylation to form trimethylpentanes is the predominant reaction. Donne11 and Kennedy ( 7 B ) quantitatively investigated the self-alkylation of isobutane a t -80' C. as promoted by isopropyl fluoride and boron trifluoride, in order to explain the relation between the amounts of boron trifluoride charged and the total amount of reaction 0,btained. The addition of more than 0.5 mole of boron trifluoride per mole of isopropyl fluoride produced no additional reaction. Pines (11B) received a patent for a new method of alliylation of isoparaffins with olefins, in which the olefin is first treated under isomerizing conditions to produce an olefin having a more centrally located double bond. Paushkin and associates (IOB) studied the destructive alkylation of pentane a t 350' to 450' C., and found that the maximum yield of the liquid products was obtained a t the high temperature. The best reaction time was 2 hours; a longer reaction period led to lower yields of liquid products. Schmerling and West ( I @ ) studied the halogen exchange between tert-butyl halides and aluminum halides during the condensa+tionwith ethylene. A chain mechanism, involving abstraction of the chloride ion by a carbonium ion, is proposed to explain the data. A British patent was granted to Anglo Iranian Oil Co. Ltd. (ZB)for the production of a low temperature lubricant from the residue remaining from the alkylation of isobutane with butanes. Kosolapoff ( 8 B ) investigated the possibility of alkylating the csters of methanediphosphonic acid with an alkyl halide. Crawford ( 6 B ) received a patent for the preparation of a solvent by alkylating isobutane with butene. This solvent is suitable for use in the refining of wood rosin. An alkylated polyvinyl alcohol for use as a surface-active agent was made from acetyl bromide by Saliurada ( I S B ) . Boyd and Kelly ( $ B ) studied the alkylation of aliphatic nitro compounds by allyl-type halides. The alkyl group was attached directly to the carbon, without the formation of an intermediate nitronic ester. Plate and Savel'eva (12B) investigated the effect of temperature on the alkylation of 1-methyl cycloprntane by the Butlerov-El'tekov method. A series of alkylated derivatives of phthalylhydrazine was prepared by Buu-Hol and associates (4B). Braude and associates ( S B ) employed lithium alkenyls as the alkylating agent in thp synthesis of 6,6-dimethylcyclohexenyl derivatives. A patent issued to hlrstili ( 9 B ) describes an alkylation process in which the fresh isoparaffin, olefin, and acid are brought into contact in several high velocity jets for a short contact time, followed by a longer second contact zone. This prevented the acid-olefin complex from reacting with fresh olefin to form undesirable side products. A patent by Darragh and Johnson ( 6 B ) reports a method for deodorizing the products from the catalytic alkylation of a long chain olefin by contact with a silica-alumina adsorbent.
CARBON-CARBON ALIPHATIC ALKYLATIONS
CARBON-CARBON AROMATIC ALKYLATIONS
The self-alkylation, isomerization, and disproportionation of isoparaffins as induced by alkyl fluoride-boron trifluoride cata-
Alkylbenaenes, having a long alkyl side chain with 12 to 20 carbon atoms and a short alkyl side chain with 1 to 3 carbon
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INDUSTRIAL AND ENGINEERING CHEMISTRY
atoms, were synthesized by t'he usual methods and their physical properties determined by Toda and Kosaka ( I 6 C ) . I n like manner the physical properties of five p-alkylbutylbenzenes were determined by Ogawa (If C). The alkyl groups investigated were the met'hyl, ethyl, butyl, hexadecyl, and oct'adecyl groups. A German patent was granted to the Chemische Fabrik Griesheim ( 4 C ) for the manufacture of higher-molecular allcylbenzenesulfonates. These sulfonates were prepared by treating benzene sulfonyl chloride with solution of alkali-m&tal hydroxidss in the higher alcohols. The products are suihble for use as softening or alkylating agents and solvents. -4 revie\Y containing 15 references was published by Sherwood ( 1 3 C ) pertaining to the commercial alkylation of benzene to produce ethylbenzene, cumene, and synthetic detergent intermediates. m-tert-Butylphenol was alkylated with isobutylchloride to yield 2,5-di-tert-butylphenol according to Hart and Voshurgh (5C). The nuclear methylation of a large group of phenolic compounds is discussed by Moran and associates (SC). Yield and melting point data are included. Morton and Brachman (9C) investigated the alkylation of toluene by amyl chloride in the presence of sodium a t 20" C. Addition of insoluble salts to the mixture usually increased the yield of hexylbenzene. Of the metal halide salts, cesium chloride is the most effective. Of the allcoxide salts, the secondary ones are more influential. Higher monoallcylnaphthalenes prepared by condensation of higher alcohols and naphthalene were structurally identified by Matsukam and Kuwata ( 7 C ) . Through a p)-rolysis and oxidation procedure these compounds were found to be 2-(2-naphthyl)-alkanes. Rinderknecht 112C) found that alkylation of diphenylacetone leads to both carbon and oxygen substitution. The ratjio of carbon t o oxygen alkylation is governed by steric factors where methylation gives predominant,ly the carbon substit,ution, whereas quaternary ethylene-imonium chlorides furnish almost exclusively basic enol-et,hers. Other alkyl halides occupy an *intermediate position. Borkowski and Wagner (8C)investigated the methylation of aromatic amines by the Kallach method. They observed that without acid only negligible condensation occurs. Benzyl nitrile was condensed with a variety of alkyl halides to the corresponding substitut,ed phenylacetonitriles by Tagmann and associates (14C). Melting and boiling points of the various products were given. Wasson and Smith ( 1 6 C ) studied t,he effects of alkyl substitution on the antioxidant propert,ies of phenols. They found tertiary butyl groups to be most effective. I n line with this, Jones, Jones, and Strickland (6C) claim 2,6-di-tert-butyl-4-methylphenol to be an excellent stabilizer for aviat'ion gasoline, tetraethyllead concentrates, and treated cracked gasolines because of its resistance to oxidation, thermal decomposition, and insolubility in aqueous solutions, These properties are attributed t'o the steric hindrance of the tertiary butyl groups. Van Battum (1C) obtained a patent for the product,ion of a lubricating oil from a mixture of low boiling aromatics that' have been alkylated n-ith high boiling olefins and high boiling aromatics that have been alkylated with the low boiling olefins. A Dutch patent vias issued to N.V. de Bataafsche Petroleum Maatschappij (1OC) for the same process. A British patent vias taken out by the California Research Corp. (SC) for the preparation of propene polymers, mainly tetramers and pentamers by the interaction of propene and its polymers in the presence of liquid phosphoric acid. These polymers are superior alkylating agents in the preparation of detergents of the sulfonated alkylbenzene type. FRIEDEL-CRAFTS TYPE C A T A L Y S T S (Aluminum Chloride)
Aluminum chloride was the original Friedel-Crafts catalyst and is st,ill the most prominent. Ferro ( 7 D ) obtained a patent for an apparatus used in feeding aluminum chloride catalyst in connection with the alkylation of isobut,ane with ethylene. The finely divided solid catalyst is suspended in isobutane and fed int'o the reaction zone. An apparat,us for the continuous alkylation of
Vol. 46, No. 9
benzene mas described by Tsukervanik and Taveeva ( 2 6 0 ) . Alcohols in the presence of aluminum chloride were the alkylating agents. Alcohols used and their respective alkylbenzene yields were isopropyl, 66%; butyl, 60%; ethyl, 35 to 40%. The change in the catalytic action of aluminum chloride on the alkylation of heptane in the presence of varying amounts of water was studied by Tarama and Kubota ( 2 4 0 ) . The presence of a large amount of water produces a reactmion,and the presence of a much larger amount of water produces a reaction, and the prerence of a much larger amount of water produces no reaction, probably oIving to the interference of the formation of the ionic intermediate complex. Messina and B r o m (160)investigated the alkylation of 2,5-dimethylthiophene with various alkyl halides and aluminum chloride. They found only a minor amount of polymerizat,ion when tert-butyl chloride was the alkylating agent. With less active alkyl halides polymerization increased. By the addition of 1-methylcyclopentanol and benzene with aluminum chloride, Sidorova and Dudnilrova ( 2 1 D ) ohtained a t 43% yield of 1-methyl-1-phenylcyclopentane. . I French patent was granted t'o Compagnie franpise de raffinage ( 6 0 ) for a continuous process for treating an aromatic hydrocarbon with an alkyl halide in the presence of aluminum chloride, When dibenzyl and butyl chloride are reacted, hydrogen chloride gas and an oil-aluminum chloride complex are the products. JVelch ( 2 8 0 ) obtained a patent for the production of a polystyrene-type, pour point depressant. Two consecut'ive FriedclCrafts reactions in the presence of aluminum chloride are carried out on polystyrene by the action of 1-octadecene and subsequently, mixed amylenes. Optimum pour point depression is obtained iYith 0.01 to 5.0% depressant to a waxy mineral oil. Horeczy ( 8 0 ) received a patent for alkylating toluene or benzene with 12 carbon olefins in the presence of an aluminum chloride catalyst promoted mith hydrogen chloride. After sulfonation the products are useful as det'ergents. A Dut'ch patent was granted to N.V. de Bataafsche Petroleum Maatschappij ( 1 6 D ) for the alkylation of aromatic compounds boiling above 210' C. with olefins having a straight or branched chain of a t least 8 carbons. The alkylation was carried on in the presence of an aluminum chloride catalyst a t temperatures under 100" C. The products are suitable for use as cylinder oil. A Japanese patent was issued to Kanao and Toyoda (1OD) for t'he formation of 4-isohexylresorcinol by the reaction of resorcinol and an acyl chloride of isohexane in the presence of aluminum chloride. A yield of 30 to 33% was obt'ained. A British patent was taken out by Ruhrchemie A-G. (WOD) for the preparation of long chain alkylbenzenes by the condensation of monochlorinated aliphatic fractions with benzene in the presence of aluminum chloride. The products were subsequently sulfonated to form detergents for laundering delicate fabrics. Ross and Markarian ( I Q D ) prepared 1,3,5-triethylbenzene by alkylating benzene with ethyl bromide and aluminum chloride. This product was subsequently chlorinated and copolymerized with styrene. Lagidze and Petrov ( 1 4 0 ) alkylat,ed benzene with 2-butyne-1,4-diol diacetate in the presence of aluminum chloride and obtained a 20% yield or semicarbazone. A French patent, was issued t,o Standard franFaise des pktroles (OBD) for a process in which low boiling dihalogenated aliphatic compounds mere condensed with aromatic hydrocarbons. The product was then alkylated with butyl or amyl chlorides in the presence of aluminum chloride. Other metallic halides are also used as catalyst in Friedel-Crafts reactions. Chief among t,hese are zinc chloride and boron trifluoride. Degering and associates (6D) alkylated o- and p-cresol and 0- and p-chlorophenol with octyl, duodecyl, and hexadecyl alcohols in the presence of zinc chloride. Yields, boiling and melting points, densities, and refractive indices for products Erom all combinations of these compounds are given. Kuchlcarov ( f S D ) showed t,hat alcohols combine with zinc chloride to form complexes. It is probable that alkylation of aromatic nuclei proceeds through such complexes in the form of acids that cleave
September 1954
INDUSTRIAL AND ENGINEERING CHEMISTRY
into an olefin and the actual alkylation propagator. A maximum yield of 70% was obtained by Kodama, Fukui, and Takei ( 1 2 0 ) in the alkylation of resorcinol with butyl and hexyl alcohol in the presence of zinc chloride together with phosphorus pentoxide. Kennedy and Schneider ( 1 1 0 ) patented a process in which aromatics were instantaneously alkylated with isoparaffins by the simultaneous action of a tert-fluoride and boron trifluoride. The reaction occurs in the homogeneous phase, and agitation is unnecessary. Burwell and associates ( I D ) investigated the effect of promoters on the alkylation of benzene by sec-butyl methyl ether in the presence of boron trifluoride. They found that the addition of small amounts of water, sulfuric acid, or chlorosulfonic acid greatly increases the rate of reaction. The same investigators ( 2 0 ) discovered that the alkylation of benzene by optically active sec-butyl methyl ether in the presence of boron trifluoride yields sec-butylbenzene of inverted configuration and optical purity of 1.1 to 14%. Drastic racemization occurs during the alkylation step, Alkylation of isopropylbenzene with acetylene was carried out with the aid of phosphoric acid-boron trifluoride and mercuric oxide catalysts by Va'Lser and Polikarpova (27D). Optimum yields a t temperatures below 70" C. were obtained in 7 hours using 10: 1 isopropylbenzene to catalyst ratio. Yields a t 100' C. were 34%. Several methods for preparing tert-amylbenzene were investigated by Inatome and associates ( 9 0 ) . The reaction of isoamyl chloride with benzene, catalyzed with anhydrous ferric chloride, is best from the standpoint of yield and purity. Aluminum chloride gave a product containing mostly isomeric amylbenzenes. Pines and Kvetinskas ( 1 8 0 )obtained a patent for the production of alkenylthiophenes by treatment of a thiophene with a diolefin containing one tertiary double bond and one nontertiary double bond. The reaction was carried on a t temperatures ranging from -20' to 175' C. in the presence of tin tetrachloride. The products are used in the preparation of medicinals, bactericides, insecticides, and plastics. The reactions between ethyl acetate and aluminum bromide a t 20' C. were studied by Takegami and Shingu ( 2 5 0 ) . These two constituents are the alkylating agent and catalyst in the Friedel-Crafts alkylation of benzene. Ethyl acetate was decomposed only 4 to 9% even in the presence of excess aluminum bromide without any formation of ethyl bromide. Kinetic studies showed the rate of acylation to be first order with respect to the ester and its rate constant proportional to the concentration of free aluminum bromide. Taylor and Watts ( 2 5 0 ) acetylated p-tert-butyltoluene by the FriedelCrafts procedure. -4French patent was issued to Champagnat ( S D ) for the preparation of synthetic lubricants that have impro-.Ted resistance to high temperature oxidation. They are produced by the condensation of unsaturated fatty animal or vegetable oils with aromatic nuclei employing the FriedelCrafts reaction. Viscosity may be kept low by premixing methyl or ethyl esters of the fatty acids with the fatty oils. A French patient was also granted to Compagnie franpaise de raffinage ( 4 0 ) for the manufacture of synthetic lubricants. Cyclohexane or cyclohexene were condensed with a dihalogenated hydrocarbon with a Friedel-Crafts catalyst. The products were then mixed with other oils or condensed with halogenated hydrocarbons, olefins, or themselves. The change of electrical conductivity of phosphoric acid-boron trifluoride in the course of alkylation of benzene was measured by Paushkin and Kurashev (17D). There was very little change in the concentration of the catalyst. Generally, conductivity varies parallel with the density and the titratable concentration of catalyst. SULFURIC A C I D CATALYSTS
Nickels ( S E )patented a method for separating 1-and 2-methylnaphthalenes. This was done by alkylating with a tertiary olefin in the presence of sulfuric acid, and then separating the tert-alkylmethylnaphthalenes by distillation or crystallization.
1791
Welch and Smith ( 8 E ) performed acid-catalyzed condensation of paraformaldehyde with a number of substituted benzenes, obtaining yields of u p to 86% of the substituted diphenylmethanes. They found that further condensation formed dihydroanthracenes. Stevens ("E) obtained a patent on the alkylation of substituted phenols with tertiary alkyl groups in order to change the position of substitution of succeeding groups from that which would normally be expected. 4-Methylcyclohexanol was cycloalkylated by Sidorova and Grebenyuk (5E) to give a 60% yield of trans-1-methyl-4phenylcyclohexane.Buu-Hoi and associates ( $ E )investigated the arylalkylation of phenols and naphthols and their derivatives with styrene. Anglo-Iranian Oil Co. Ltd. ( 1 E ) obtained a British patent on a process for the recovery of spent sulfuric acid such as is used for the catalyst in the alkylation of toluene by propylene tetramer. The basic steps of the process are extraction with a mixture of cresols and a steam-stripping of the raffinate. A method of analysis of the spent acid from alkylation processes was proposed by Weiss, Jungnickel, and Peters ( 7 E ) . It included the determinations of total acidity, titratable acidity, free acid, water, and neutral oils. Persyn ( 4 E ) patented a system for the continuous determination of the strength of the acid in a hydrocarbon-sulfuric alkylation process. OTHER A C I D CATALYSTS
There was a number of references to alkylation reactions carried out in the presence of hydrogen fluoride. Pines and associates (QF) made a study of the isomerization accompanying the alkylation of benzene with amyl alcohol. A list of the amounts of the various isomers is included. I n a patent issued to Hanmer ( S F ) , the alkylation of benzene viith a high molecular weight olefin in the presence of liquid hydrogen fluoride is essentially a two-step process. I n the first reactor, impurities are removed and only 5 to 10% of the alkylation occurs, and the feed stream is then passed to a second reactor where the remainder of the reaction takes place. A British patent issued to the Dominion T a r and Chemical Co. Ltd. ( 2 F ) disclosed that saturated aliphatic aldehydes, alcohols, and ethers condense with benzene, toluene, and xylene in the presence of a hydrofluoric and fluosulfonic acid 20 catalyst. These reactions occur a t temperatures between and 35" C. A patent by Bloch and Hoffman ( I F ) described a procedure for obtaining improved drying oils from acid sludges produced in olefin alkylation reactions. This was done by reacting the oils with less than the theoretical amount of acid catalyst required to form catalyst-hydrocarbon complexes. An article by VaIser and Polikarpova ( Q F )described the alkylation of ethylbenzene with acetylene in the presence of a mixed catalyst of phosphoric acid. The viscous layer from the reaction appeared to consist of polymers of vinyl derivatives. Sidorova ( 8 F ) studied the alkylation of phenol with butyl and isobutyl alcohols with a phosphoric acid catalyst. I n the case of the isobutyl alcohol, partial dealkylation occurred a t the end of the reaction. Rosenwald ( 6 F ) reported that the butylation of guaiacol with teri-butyl alcohol and a phosphoric acid catalyst yielded the 4-, 5-, and 6- isomers of tert-butyl guaiacol. Plummer ( 6 F ) described the production of phenol from cumene. The cumene was obtained by the alkylation of benzene with propylene using a U.O.P. phosphoric acid catalyst. A patent issued to Schulze ( 7 F ) described the alkylation with benzene of an olefin stock, which contains from 7 to 20 carbon atoms per molecule. This is done a t a high enough pressure to maintain a liquid phase.
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M I S C E L L A N E O U S CATALYSTS
A German patent issued to Badische Anilin- CP: Soda-Fabrik (dG) described the condensation products prepared by heating an aromatic compound with ethers and carbon monoxide in the presence of catalysts, preferably carbonyl-forming metals such as iron, cobalt, nickel, and their salts or oxides. The main fraction of the product consists of a mixture of alkylated hydrogenated
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INDUSTRIAL AND ENGINEERING CHEMISTRY
1792
benzenes. Hervert and Bloch (5G) patented a process for the alkylat,ion of a mono-olefin by reaction n i t h an alkylbenzene in liquid phase in the presence of a calcined composite of a free acid of phosphorus and a siliceous adsorbent. A patent by Wagner ( 6 G ) described the production of alkylated quinolines and their derivatives with an olefin in a silica-alumina type catalyst. The resulting alkylquinoline can be dehydrogenated to the corresponding alkenyl quinoline. 1 continuous process, v i t h flow diagram, is proposed for the production of 2-vinylquinoline by this method. A Japanese patent issued to Fujiaalti and Ogawara ( 4 G ) disclosed that passing a misture of benzene and ethylene through a porcelain tube filled with aluminum, aluminum carbide, and silica gave a mixture of ethyl benzene and mixed xylenes. When carried out a t temperatures between 300" and 800" C., this reaction gave a 5 i % yield. Another J:tpanese patent issued to Yamamoto and Oku ( 7 G ) described the preparation of styrene by treating a mixture of benzene and butadiene with ethylene in the presence of a complex nickel carbonyl catalyst'. This gives a 26% yield of the styrene. Cannon and Whidden (YG)studied the acylation of methyl cyclopropyl ketone. Several reactions were carried out in the presence of a basic catalyst. A German patent issued to Badische Anilin- & Soda-Fabrik (1G)describes a process for t,he preparation of silica-containing catalysts or carriers useful in preesure reactions such as hydrogenat,ion and alkylation. Waterglass and one or more metal salts are mixed in the presence of nitric acid, and the gel is precipitated and calcined. Passing a middle-oil fraction over this catalyst gives a 32% yield of gasoline.
CARBON-CARBON ALKYLATIONS GRIGNARD REAGENT
A substantial number of alkylations employing the Grignard reagent appeared again this year. Gault, Ecb-Tridon, Suprin, and Ritter ( d H ) describe a Soshlet,-type continuous reactor for the preparation of Grignard reagents and its use in the synthesis of ethylmagnesium bromide and its condensation with toluene. The reaction of isopropplmagncsium bromide Jyith ethyl formate was found by Sokolova ( 1 d H ) to yield 40% diisopropyl methanol. Similarly, the same Grignard reagent with iaovaleryl chloride yielded a variety of compounds, chief of which was 2,5-dimethyl3-hexanol. DBcombe (1H) described the basic product obtained from the condensation of ethylmagnesium bromide with glutaronitrile and postulated its molecular structure. Grummitt and associates (YH) discussed the analysis and properties of bis(pchlorophenyl) methyl carbinol. It is prepared from bis(pchlorophenyl) carbinone and mcthylmagnesiuin bromide. The product is marketed as a miticide under the name D M C or dimite. The interaction of certain Grignard reagents and nitriles has been investigated by Henze and associates (.5H), X great number of products are given along with their densit,ies, refractive indices, boiling and melting points, and ot,her physical properties. An important st,ep in the synthesis of 3,s-dimethylheptane, as performed by Levina and associates (9N)was the addition of a butylmagnesium bromide Grignard reagent to ethyl formate to yield 6OY0 3,5-dimethy1-4-heptanol. McBee, Higgins, and Pierce (ZUH) investigated the reactions of alkyl aldehydes, methyl alkyl ket,ones, and ethyl alkyl ester with alkylmagnesiuni halides as a means of preparing a series of alkyl substituted ethylenes. Kormal addition products were obtained as well as materials formed by the reduction of the aldehyde or ketone. Woods and Plapinger ( 1 4 H ) prepared rn-dialkylbenzenes from 3-allryl-~i~-cyclohexenonea by means of the Grignard reaction followed by dehydrogenation over palladium on carbon. The products were qualified by sulfonation, extraction, and hydrolysis. Yields, boiling points, and refractive indices are given. The typical procedure for the Grignard syntheeis of tetraalkylmethanes with 12 to 19 carbon atoms is described by Petrov and Chernyshev (11H). Yields, flash and boiling points, refractive
VoI. 46, No. 9
indices, and densities are given for isoprop3rlpropyldibuty1, tripropylbutyl, tripropylamyl, ethyltributyl, propyltributyl, isopropyltributyl, and amyltributyl methane. Henae and Swett ( 6 H ) found that cinnamonitrile reacts readily with ethylmagnesium chloride, allylmagnesium bromide, and phenylmagnesium bromide by 1,2 addition to t'he nitrile group. According to Wessely and associates ( 1 3 H ) ,the reaction of an alkylmagnesium halide (or phenyl lithium) with an o-quinol acetate followed by splitting out water, yields of phenol with the alkyl or phenol group in the meta position. Krutman (SH) reacted ethyl chloroformate with several alkylmagnesium bromides. The allylmagnesium bromide yields 66% triallylcarbinol, butyl yields 81 % tributyl carbinol, and isoamyl yields 88% triisoamyl carbinol. Branched aliphatic ketones were prepared by Heilmann and de Gaudcmaris ( 4 H ) from Grignard reagent with cadmium chloride through an intermediate dialkyl cadmium which then reacts with a branched acyl halide to yield the ketone. Yields are 40 to 50%. Xirrmann and Berschandy ( 7 H ) carried out the conversion of long-chain alkyl bromides to higher homologs by heating the Grignard derivatives with w-methoxyalkane nitriles, rcducing the resulting methosy ketone, and splitting the met'hoxy group off with hydrogen bromide. An alkyl bromide containing 23 carbon atoms was obtained in 90y0 yield. COMPLEX ALKYLATIONS
Several studies were made of reactions in which the alkylatitg agent contained an amino, cyano, or halide group. Mann and Millar (84 studied the cyanoethylation of aryl phosphines. The cyanoethylation of phenyl phoephine occurs without a catalyst whereas that of the phenyl amines is acid-catalyzed and that of phenyl arsine is catalyzed with bases. Terent'ev and Butskus (17i)cyanoethylated the esters of several 0-amino acids. This was done under various conditions, with yields ranging from 20 to 7oY0. Semonskj. (16i)studied the aminomethylation of 1-narcotine a t room temperature. Clauson-Kaas and associates (42')reported the electrolytic methoxylation of furan and several of its derivatives. Furan was electrolyzed for 16 hours in ~2 cell with a current of about 3.0 amperes arid a t a temperatme of -16" C. A British patent issued t o C I B S Ltd. (3i) descrilxs the preparation of several alkylated derivatives of fluoranthcrie by alkali condensation with alkyl halides bearing a, tert-amino group. These compounds were found to have powerful spasmolytic propert'ies. Orito (1Oi) found that a temperature of 40" C. and a time of 4 hours were the optimum conclitions for the condensation of butyraldehyde in sodium hydroxirlc to form ethylhertanol. Petrov and associates ( I l i ) studied the order of addition of alkyl hypohalites to tertiary vinylacetylenic alcohols. The addition of methyl hypoiodite to t'he alcohols occurs largrly a t the ethylenic bond. .4 Brit'ish patent issued to Dow Chemical Co. (6i)disclosed t'hat by allowing polystyrene polymer or copolymer t o swell first or dissolve either in a nonreactive liquid such as carbon disulfide or in the halomethylating agent a smooth halomethylation reaction occurs on the addition of a cat'alyst and sufficient reagent. This halomethylating agent can also be used to impregriat,e porous rock. McMaster (7i)patented a preparation of anion exchange resins by the halomethylation of vinyl aromatic resins. Several treatments are proposed to reduce the tendency tonard crumbling of t,hese resins. Schmid and Schultcs ( I / i i ) byomomethylated acetophenone with hydrogen bromide in the presence of zinc chloride, The reaction mas accompanied by continuous ice-cooling. A Japanese pat,ent, to Shishido (1Bi) described the passage of dry hydrogen chloride int'o a solution of hydrochloric acid, formalin, and mixed xylenes. The product of this reaction, after subsequent reduction with zinc and sodium hydroxide, gave a 58% yield of 1,3,4-trimethylbenzene. Maquin and Gault (Si) treated diphenylmethane with a mixture of formaldehyde and hydrochloric acid in a phosphoric acid mediup. This produced an 85% conversion to the p-chloromethylated product.
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September 1954
INDUSTRIAL AND ENGINEERING CHEMISTRY
1793
A British patent issued to De Benneville and Bock (6i)chloromethylated higher aromatic hydrocarbons with formaldehyde and hydrogen chloride in the presence of a zinc chloride catalyst. The product was then used to prepare various quaternary ammonium compounds. Pines (Ili) patented a process to chloromethylate haloalkylthiophenes, giving an 88% yield. Pines and Vesely (1%) reacted a thiophene with a diene and hydrogen chloride in the presence of a phosphoric acid catalyst to form a chloroalkyl thiophene. Cagniant and Cagniant (li) chloromethylat6d ethylthiophene in the presence of glacial acetic acid. This can be used as a colorless, malodorous refrigerant. Chiavarelli (di) described the chloromethylation of aliphatic arylamines. The method is briefly given without experimental details, MISCELLANEOUS CARBON-CARBON ALKYLATIONS
Included hereunder are all alkylations that did not appropriately fall into any one of the specific divisions. Bloch ( 2 J ) patented a reaction between hydrofluoric acid and isoparaffins and olefins with 3 to 12 carbon atoms. The product when decomposed by water gives a mixture of unsaturated substituted 5 carbon ring hydrocarbons that are useful as plasticizers and extenders for rubber, They vulcanize with sulfur. Rubber and rubberlike copolymers in cured and uncured stages are stabilized by the reaction products of an alkyl halide and an olefin-alkylated cresylic acid according to a patent obtained by Kitchen ( 8 J ) . The addition of this stabilizer produces a nondiscoloring, better age-resistant, and improved flex-life stock for white sidewall stock than commercial stabilizers. I t may be added to latex or coagulum in a mill or Banbury mixer after vulcanizing. Catalysts for its preparation are metallic halides and sulfuric acid. A French patent was granted to Compagnie franpaise de raffinage ( 6 J )for the preparation of lubricants of low iodine index. Rosin oil, alone or mixed with fatty oils, is first acrylated by benzene, toluene, or xylene, and then alkylated by ethylene or like olefin, or a chlorinated hydrocarbon like ethylene dichloride. A German patent was issued to Chemische Werke Albert (45)for the manufacture of l-hexyl-3,7-dimethylxanthine by the treatment of theobromine with a hexyl halide in the usual manner. The product is a chemotherapeutical agent of sedative and spasmolytic activity. Bettini and Boccacci ( I J ) claim the phenyl esters of iodoacetic and chloroacetic acid and the dodecyl ester of chloroacetic acid are good contact insecticides for flies that are resistant to DDT, chlordan, and the like. Boekelheide and Weinstock ( Y J ) found Reissert compounds of both the isoquinoline and quinoline series could be readily alkylated with alkyl halides. The Michael condensation between ketones and 2-vinylpyridine was effected with sodium by Levine and Wilt ( 9 J ) . They found that with methyl ethyl ketone condensation occurs a t the a-methyl group while with methyl isobutyl ketone condensation takes place a t the a-CHz group. Yields and products from condensation with a number of ketones are given. Methyl lithium was prepared under nitrogen in 95% yield, and a number of methyl ketones were obtained in high yield by its action on carboxylic acids by Tegner ( 1 4 J ) . The yields were the same whether the free acid or its lithium salt was used. A Japanese patent was issued to Momoi (IOJ) for the preparation of certain alkylated barbituric acid derivatives. 5-Ethyl-5-isoamyl-6-iminobarbituric acid was prepared in 70% yields and ethylisoamylbarbituric acid was prepared in 80% yields. The methylenation of D-mannitol by Fletcher and Diehl ( 7 J ) with formaldehyde and hydrogen chloride gave an addition to the 1,3:4, 6-di- and IJ3:2,5:4,6-tri-methy1ene derivatives, small quantities of 3,4- and 1,3-dimethylene and 1,4-anhydro-2, 3-methylene-~-mannitol. The synthesis of acetic acid 1- and 2-alkylated-2-phenyl hydrazides was investigated by Stuhmer and Elbrachter ( I Y J ) . Acetic acid phenylhydrazide gave 2alkylated products when treated with methyl or ethyl iodide and 1-alkylated products when treated with propyl or butyl iodides.
Salt Purification Equipment a t Ethyl Corp. on Houston Ship Channel High purity salt is used to produce metallic sodium required in manufacture of antiknock c o m w m d r
Alkylation in the presence of sodium-xylene gave 10 to 14% yields; sodium amide-xylene, 19 to 24%, and sodium ethoxideethyl alcohol, 65 to 86% yields. Reid and Yost ( 1 1 J ) discussed the preparation of ethyl a-sec-butylacetonedicarboxylate in a sodium-ethyl alcohol solution. Methods for the production of certain alkanes, alkenes, acids, and lactones with bis(ethylsu1fony1)methane were described by Cronyn ( S J ) . Melting point and yield data are included. Stoppani and associates ( 1 Z J ) investigated the inactivation of carboxylase with various alkylating agents. Incubation times for the various agents are ethyl iodoacetate, 10 minutes; iodoacetic acid, 20 minutes; bromobenzyl cyanide, 30 minutes; and chloroacetophenone, 30 minutes.
CARBON-OXYGEN ALKYLATIONS An article by Klages and Meuresch ( I l K )described the preparation of trialkoxyloxonium salts by the alkylation of dialkyloxonium salts. A patent by Chabrier and aEsociates ( 6 K )reports the preparation of several derivatives of morphine that have a low toxicity and are useful as anticough medicines. Pyridylcarbinol ethers were prepared from an aryl p) ridylcarbinol and an aminoallryl halide salt in a patent by Cusic ( 8 K ) . These compounds are useful as antispasmodics, antihistiminics, or antiallergic agents. An article by Lehmann ( 1 8 K )also describes the synthesis of a series of new antihistaminic derivatives, but no experimental data or physical constants are given. Bavin and associates ( S K ) obtained the alkyl ethers of salicylamide by boiling with the corresponding alkyl bromide in ethanol in the presence of sodium ethoxide. Most of the ethers thus prepared showed greater analgesic action than the salicylamide. Von der Haar and Porninski ( l 7 K ) described the methylation of gossypurpurin, in a series of articles about the pigments of cottonseed. Zal’kind, Venus-Danilova, and Mikhailova ( 1 9 K ) prepared the methyl and ethyl ethers of diphenylhutynediol. The yields of ether obtained ranged from 70 to 80%.
1794
INDUSTRIAL AND ENGINEERING CHEMISTRY
Miyagawa and Ando (14K) discussed the synthesis of tertbutyl ethyl ether from tert-butyl and ethyl alcohols in the presence of sulfuric acid. Its characteristics as a blended fuel were compared with those of iso-octane and methyl ether. Wheatley and Cheney (18K) discovered that under suitable experimental conditions, alkylations with neopentylhalides react with the same velocity as primary halides, and not necessarily with rearrangement. A French patent to the Societe Nobel franCaise (15K) gives a process for the introduction of ethylene oxide or its homologs on polyvinyl acetals. The products are useful as sizings, primers, and adhesives. llatsuura and Sakakibara ( 1 S K ) describe the alkylation of phenol or cresol by diallryl oxalate. The special feature of this method is the use of atomic sodium or potassium. Astle and Zaslondiy ( 2 K ) found that quaternary ammonium-type ion exchange resins were effective catalysts for the cyanoethylation of primary and secondary alcohols. Keakly basic amine-type resins were not suitable. A number of references were found for the alkylation of cellulose or its derivatives. Stephens (IOK) described the preparation and properties of methylcellulose, and gives enamples of its use in a great variety of industries. -4British patent issued 'co Gevaert Photo-Producten N.Y. ( 9 K ) disclosed that cellulose carboxyalkyl ethers and their salts can be prepared by treating cellulose esters with one or more monohalogen fatty acids in the presence of an alkali hydroxide. Such ethers and snits are suitable for the preparation of photographic-film bases. An article b y Goncharov (10K) discusses the factors involved in the manufacture of a high quality benzylcellulose and their effect on the physical propeities of the product. -4British patent by Courtaulds Ltd. and Macgregor ( 7 K ) describes the preparation of water soluble mixed ethers of cellulose containing cyanosthyl groups and an alkyl group. Modifications and variations of the process are discussed, Ethylcellulose v a s prepared from alkali cellulose and ethyl chloride 171th eodium phenoxide, in a Japanese patent by Aimi (111). I n a patent by Branan and associates (4K), water-soluble sodium carboxymethylcellulose is prepared by treating cellulose granules with an etherifying agent in the presence of aqueous alkali. Mtc1 ieacting for 30 minuteq, x 48% yield of the water-soluble material was obtained. The preparation and properties of the propyl. butyl, hexyl, and benzyl ethers and ester derivatives of hydronyethyl cellulose arc described in an article by Cohen and associates (OK). Films of some of the ethers shon- good low temperature performance.
CARBON-NITROGEN ALKYLATIONS The catalytic alkylation of ammonia by halides of alkanes and cyclanes was studied by Nekrasova and ShuIlrin (18L). Catalysts based on magnesium oxide n-ere satisfactory. The yields from butyl chloride were 39.2% primary, 18.1% secondary, and 2.7% tertiary amine; from hexyl chloride 45, 13, and 2.5%, respectively; heptyl chloride 50.5, 9.0, and 1.5%; octyl 58>4.2, and 0.8%; nonyl 69, 8.0, and negligible %, and decyl 70.8, 8.0, and negligible %, respectively. The effect of the nature of the halogen and its position in the molecule for the same reactions were also determined (19L). Hunig (11L) methylated p methylaniline n-ith dimethyl sulfate in the presence of sodium bicarbonate to yield 95% p-methyl-dimethylaniline. I n similar reactions 755'4 o-methyl-dimethylaniline, 94% p-chlorodimethylaniline, and 76% p-hydroxyl-dimethylaniline were obtained. Certain tertiary acetylenic amines were prepared by Campbell, Fatora, and Campbell ( 6 L )and their base strength determined in order to study the influence of each functional group on the properties of the other. Heating chlorides of dialkyl phosphates with various amines yielded the corresponding alkylated amines according to Lugovkin and Arbuzov ( f 4 L ) . The reaction v a s even extended to benzylamine. Carbazole did not react. Sprules and Bell (2dL)patented the preparation of amines of the benaylaminetype by mixing a t atmospheric pressure and 5" to 50" C. an
Vol. 46, No. 9
aralkyl halide with an aqueous solution of a nitrogen containing compound. The nitrogen compound may be ammonia, primary aliphatic amines containing 1 to 4 carbons, or secondary aliphatic amines containing 1 to 4 carbons in each alkyl radical. Stuhmer and Kaupmann (2SL) investigated the catalytic alkylation of cyclohexylamine with a,p unsat'urated ketones; 10% platinumbarium sulfate catalyst was used. Quaternary ammonium compounds received considerable attention. A British patent was issued to the Monsanto Chemical Co. (16L) for the preparation of isomeric 2-tert-tetradecylthioethylpyridinium chlorides. These compounds are useful as germicides. Another British patent was granted to Gysin and Hagenbach ( 3 L ) for the preparation of long chain quaternary ammonium compounds that are useful as disinfectants and wetting or dispersing agents. Dipolar ions formed by cleavage of a proton from a nitrogen-hydrogen group react readily viit,li alkyl and acyl halides to form quaternary ammonium salts according to Simonov (W1L). Melamed and Croxall ( 1 5 L ) patented a process for producing quaternary ammonium salts from dialkylamino acetones and alkylbenzyl halides. The salts are useful as bactericides. A German pabent was obtained by Farbwerke Hoechst vormals Meister Lucius &. Bruning ( 7 L ) for producing diquaternary ammonium compounds by the action of alkyl halides. The products are valuable chemotherapeutical agentr with a higher muscular-relaxing activit'y than curare. They are prepared by hydrogenating 4,4'-diaminodiphenylalkanes with folloxing or preceding alkylation of t'he amino radicals. A4 British patent was granted to Elpern and Ruddy (BL) for the preparation of quat,ernary compounds which are valuable antispasmodic agents and process anticholinergic activity similar to that of atropine. Britton ( 4 L )patented a process for producing pyridinium quaternary ammonium compounds that are useful as fungicides, germicides, and insecticides. Dyes of the 1-alkylamino-2-alkoxyanthraquinone type were synthesized by Naiki and Tsuruolra ( 1 7 L ) by alkylation of 1amino-2-alkoxyanthraquinones. I n the dyeing and fastness tests nTith acetate rayon the dimethyl derivatives were the best, followed by the ethylamino and methylamino in t'hat, order. A Japanese patent was granted to Ishihara and Ito ( 1 2 L ) for the preparation of lJ5-dimethy1-4-dimethylamino-2-phenyl-3pyrazolone by an electrolytic reductive procedure. A 96.G% yield was obtained. The hlannich reaction of 1-methyl- and 1-phenylpyrrole wibh formaldehyde and amines was invest,igated by Herz and Rogers (1OL). The methiodides of the resulting bases are fairly active alkylating agents. Theoretical and experimental data from the mork of Fuortes and Moutagnani ( 8 L ) on the alkylation of aniline tvith methanol, dimethyl ether, and diethyl ether demonstrated the stronger methylating action of dimethyl ether over methanol. Treatment of aniline with dimethyl ether yielded 93 to 96% dimethylaniline and 4 to 7 % methylaniline; methanol yielded 71 to 75% dimethylaniline and 22 to 24% methylaniline. An aluminum oxide catalyst 11-as used. Breusch and Baykut ( 3 L ) prepared a number of 4'alkyl-N-methylanilines to investmigatet'he influence on hemolysis of alkyl side chains on higher tertiary amines. A British patent ( 1 L ) and a German patent ( d L ) were granted to Asta-l17erke Akt. Ges., Chemische Fabrik. for the manufacture of N-alliylateda-phenylglycine esters. The process involved treating aphenylglycine esters with hydrogen chloride salts of dialliylaminoalkyl chlorides such as dimethyl- or diethylaminoethyl chloride. I n the absence of solvents the products of such reactions possessed valuable chemotherapeutical properties, in particular, antispasmodic properties. Saha and associates (2OL) presented new syntheses for alkylated isoquinoline derivatives. Some of the derivatives prepared were 1,4-dimethyl-3,4-dihydroisoquinoline and 1,4,7-trimethyl and l-phenyl-4-methyl-3,4dimethydroisoquinoline. Taguchi and Nakayama (24L) found that reaction of diethylamine and cyclohexene oxide gave the cis-form of 2-diethylaminocyclohexanoland not the trans-form
September 1954
INDUSTRIAL AND ENGINEERING CHEMISTRY
as has had been previously reported, An Austrian patent was obtained by Kubicsek (131,) for the condensation of nitriles of aromatic, aliphatic, or mixed carboxylic acids with imidazolines or salts thereof to produce 2-substituted imidazolines. Among the condensing agents used were zinc chloride and ammonium chloride. The products are useful as disinfectants and pharmaceuticals or as starting materials in the manufacture of fuch compounds.
CARBON-SULFUR ALKYLATIONS ’
A marked decline from last year was noted in the number of articles pertaining to alkylations forming a carbon-sulfur bond. A patent issued to Linn ( 6 M ) described the alkylation of thiophene with a long-chain carbon group in the presence of a FriedelCrafts-type catalyst. The product was then sulfonated and neutralized to give a useful laundry detergent. The monoalkylation of thiophenes was also discussed in a patent by Zimmerschied and Arnold ( 8 M ) . Brintzinger and associates ( Z M )replaced mobile hydrogen atoms on organic compounds with alkylsulfur groups. I n some cases it was necessary to use a FriedelCrafts catalyst. Thompson and associates (’?’If) added thiols, dithiols, or hydrogen sulfide to unsaturated compounds to form the corresponding alkylmercaptoketones, and similar compounds, which have good antioxidant properties in lard and gasoline. These mere tested and the results listed as “AOM time.” Larsson (6M) synthesized 2-triethylsilylethylthioacetic acid after allowing a week for the reaction to take place. A simple method for pre-’ paring DL-cystine from acrylonitrile was described by Gundermann and Micheel (SM).Most of the reaction was carried out sulfur-alkylated a t temperatures less than 40’ C. Jones (4M) 2-mercaptoimidazole with a series of esters. The use of the ethyl ester gave a 28% yield of the 2-ethylsulfur compound. Brandt and associates ( 1 M ) treated trifluoro-iodo methane to give a 60% yield of bis( trifluoromethy1)disulfide.
CARBON-SILICON ALKYLATIONS The carbon-silicon compounds have become of increasing importance due to the many uses that are being found for silicones. D a Fano ( 2 N ) patented a heat transfer fluid that consists of isoalkyl aryl orthosilicates. I t is to be used as a coolant for automobile radiators, as it is resistant to hydrolysis in the presence of water. A mixture of aryl and alkyl alcohols is added to silicon tetrachloride and heated to drive off the resultant hydrogen chloride. Yields are 95% of the theoretical value. A British patent was issued to the John B. Pierce Foundation ( 1 6 N ) for another heat transfer medium consisting of tetraaryl orthosilicates. It remains liquid over a wide temperature range a t atmospheric pressure. It is prepared by heating a silicon tetrahalide with a mixture of monohydric phenols to yield 62% product. The preparation of organic halogenated silanes is important as these compounds are intermediates in the formation of higher alkylated silicones. A Japanese patent was granted to Yamada and Yasunaga ( 2 5 N ) for the preparation of alkyl or aralkylchlorosilanes. Silicon powder, tableted with copper hydroxide and reduced with hydrogen, was added to benzene and/or alkylchlorides, Two other Japanese patents were taken out by the same investigators. The first (%$AT) concerned a catalyst for the direct synthesis of alkyl-aryl, aryl, or alkyl halosilanes. Copper chloride dihydrate was reacted with caustic solution and the precipitate mixed with powdered silicon, dried, and tabulated. The second (26iV) was for the reaction of methyl chloride, methane, and hydrogen chloride over powdered silicon which yielded 45% of a condensation product consisting of dimethyldichlorosilane, methyltrichlorosilane, and tetrachlorosilane. Ranbo and Sugimoto ( 1 6 N ) were granted a Japanese patent for the preparation of methyltrichlorosilane. Methyl chloride was passed over a cuprous chloride-silicon powder. According to a
1795
British patent issued to Dow Corning Ltd. ( S N ) , alkylchlorosilanes were converted to shorter chain alkylchlorosilanes by pyrolytic cracking. Petroleum cracking catalysts may be used. The reaction between silane and vinyl chloride was the subject of an investigation by Fritz (6lV). The reaction a t a temperature of 450’ C. yields a mixture of ethyl- and methylchlorosilanes, ethylene, ethyl chloride, and stable polysilane residues. A Japanese patent for the preparation of methyltrichlorosilane was received by Yojimoto ( 1 O f l ) . The reaction consisted of heating silicon and cuprous chloride to form tetrachlorosilane and a copper-silicon residue. This residue was then treated with methyl chloride to give 70% of the desired product. The alkylation of chlorosilanes of the type mentioned above by the replacement of a halogen atom was of major importance. Petrov and Chernysheva (12N) reacted the Grignard reagent of naphthyl bromide with tetrafluorosilane to yield 26% trinaphthylfluorosilane. Similarly, some trialkylsilyl anthracenes were formed by the action of trialkylchlorosilane on a solution of anthracene and lithium in benzene. Petrov and Mironov (1SiV) discussed the mechanism of the reaction of alkilmagnesium halides with p-silicohalides, They found conditions under which 2-halosilanes suffer only partial decomposition and can react with alkylmagnesium halides a t the halogen atom. The course of the reaction depends on the nature of the Grignard reagent used and on the nature of the radical to which the halogen is joined. Examples of the reaction are given in which alkylated silanes are further alkylated with the allyl Grignard reagent. Hatcher and Bunnell (8N)obtained a patent for the preparation of organosilanes by the reaction of a halogenated alkylsilane with an aromatic hydrocarbon or its halogenated derivative in the presence of a Friedel-Crafts catalyst. The same investigators received another patent ( 7 N ) covering the increased yield obtained from the identical reaction. Treatment of the distillation residues of the above products with aluminum halides accounted for the increased yield. 1-Naphthyl bromide was added to several alkylchlorosilanes in the presence of lithium by Petrov and Sadykhaade (14N). All chlorine atoms were replaced by 1-naphthyl groups. Flash and boiling points, densities, and refractive indices of alh products were included. The reaction of alkylmagnesium compounds with salts of fluosilicic acid by Soshestvenskaya (18N)i gave tetraalkylsilanes in yields of 29 to 48%. An excess of fluosilicate served to improve the yield very significantly. Petrov and Chernyshev (11N) synthesized tetraalkylsilanes with 14 to 32 carbon atoms by use of magnesium Grignard reagents and tetrachlorosilane. Yields and physical properties of the various products are given. Treatment of ethyltrichlorosilane with allylmagnesium halide by Yakovlev and Vinogradova (2ZN) yielded 60% triallylethylsilane. Topchiev, Nametkin, and Zetkin (ZON) prepared disilylmethane and reacted it with alcohols to the corresponding hexaalkoxy derivatives. Alcohols with 3 to 5 carbons were used. The same investigators ( 5 N ) also used alcohols containing 6 to 9 carbon atoms. The products had to be distilled in a nitrogen atmosphere. The reactions of silicon tetrahalides with diazoalkanes was the subject of a presentation by Yakubovich and Ginsburg (2SN). They discovered that silicon tetrabromide and tetrachloride react to form primary, secondary, and tertiary haloalkyl derivatives of silicon while silicon tetrafluoride does not react. The bromine derivatives were found to be more reactive than chlorine derivatives. Topchiev, Nametkin, and Solovova ( 1 5 N ) catalyzed the reaction between tribromosilane and certain unsaturated hydrocarbons with ultraviolet irradiation. Reaction with hexene yielded 71 % hexyltribromosilane, heptene gave 75% heptyltribromosilane, cyclohexene 70% cyclohexyltribromosilane, and l-methylcyclopentene 70% methylcyclopentyltribromosilane. Reaction of thylene with hydrosilane gave various methylated and ethylated silanes according to Fritz ( 6 N ) . Reaction with polysilane and siloxene gave similar products in smaller yields. Acetylenic silico-hydrocarbons and chlorosilanes were prepared by Frisch
1796
INDUSTRIAL AND ENGINEERING CHEMISTRY
and Young ( 4 N ) from acetylenic Grignard reagents and chlorosilanes in the presence of cuprous chloride as a catalyst. The acetylenic chlorosilanes were converted first to the acetoxysilanes or were directly hydrolyzed to the corresponding silanols or siloxanediols without rupture of the carbon-silicon bond. Yields and boiling points are given for several products of this type of reaction. Sanin and Petrov ( I 7 N ) found that reaction of p-methylphenylmagnesium bromide with 1 - napht,hyltriethoxysilane yielded 70% bis(p-met'hylpheny1)-1-naphthylethoxysilane,They also showed that further reaction of the product with alkyl Grignard reagents led to the substitution of an alkyl group for the ethoxy group. Ethoxyphenylsilanes and ethoxymethylphenylsilanes were produced by Capuccio and Pirani ( I N ) by a modified Grignard reaction between phenyl chloride and o-tetraethyl silicate or between phenyl chloride and methyltriethoxysilane. Catalytic amounts of mercury were employed. The various products and their physical properties Tvere included. A yield of dimethylpropylethoxysilane and 9% dimethyldipropylsilane mas obtained by Westermark (BIY) in his reaction of dimethyldiethosysilane with propylmagnesium chloride. Similar treatment of methyltriethoxysilane yielded 57% methyldipropylethoxysilane and 13% methylt'ripropylsilane.
CARBON-METAL ALKYLATIONS A number of studies were made of alkylations involving lead. -4patent by Gilbert (80) noted that the production of lead alkyls from sodium lead alloy with alkyl chlorides is improved by the addition of a small amount of iodine as such, or as a metal iodide. The additive functioned to prevent the agglomeration of the lead particles. A patent issued to Kolka and Krohn (130)described the preparation of hydrocarbon lead compounds from a sodium lead alloy and an alkylating agent in liquid ammonia, a t temperatures ranging from -35" to -60" C. Shapiro (200) patented an improved method of alkylating lead sodium alloy, by reducing the particle size of the alloy, using an excess of the alkylating agent, and raising the temperature. Shapiro and Krohn (810)patented a process for preparing tetraalkyllead compounds from a calcium lead alloy and an ester of an inorganic acid such as ethyl chloride. A British patent issued to the Ethyl Corp. (60)describes a similar process, with the addition of a Grignsrd-type reagent to the reaction mixture. A British patent by Rodekohr and Blitzer (190) described another process for the preparation of alkyl lead compounds. Summers ( y o ) studied the mechanisms or react,ions involved in the preparation of organolead compounds containing water-solubilizing groups. These were formed by reacting a lead halide with an organolithium compound. Panov and Kocheshkov (180) synthesized a series of simple aryllead halides using organic salts of lead as intermediates in place of the commonly employed halides. There were several references to alkylation react'ions of tin. Smith ($20) patented a preparation of methgltin chlorides by passing methyl chloride through molten tin a t an elevated temperature. They can also be made by treating a copper tin alloy in a fluid-bed system, but this results in only a 17% conversion. A patent by Burt (So) describes a method for t'he preparation of dibutyltin dialkoxides. These are used as heat stabilizers for vinyl chloride polymers. Two methods for the preparation of trialkyltin monoalkyloxides are described in a patent by Faulkner and Milne (70). Johnson and Church (90) patented a series of redistribution reactions of organot,in compounds. Tetrabutyltin and tetraphenyltin were heated in the presence of aluminum chloride, producing various phenylbutyltin compounds. An article by Cos and Winter (40) described the direct preparation of polymeric butyl titanate for heat and corrosion resistant paints from titanium chloride on a pilot plant scale. This is very suitable for paint vehicles, having good films, dry to touch, and hard enough to handle in 30 minutes. Aluminum ethylate was prepared from aluminum foil and ethyl alcohol in the pres-
Vol. 46, No. 9
ence of aluminum and ferric chlorides in a Japanese patent by Yamaguchi ($60). Kusama and Koike (160)studied the synthesis of diethylzinc by the Grignard reaction in a series of solvents. Albers and Lange ( l o ) studied the formation of alkylammonium uranyldithiocarbaminates from various uranium compounds. -4patent' by Kharasch and Weinhouse (100)described the preparation of ethyldichloroarsine and related compounds in high yields from tetraethyllead and the corresponding chloride, either with or without a solvent. These compounds are useful as chemical warfare agents. In another patent by Xharasch and Weinhouse ( I l o ) , alkyldihnloarsine was prepared by treating arsenic trichloride with tetraslkyllead in a nitrogen atmosphere. Nardelli and Chierici (160) prepared a series of alkyl-phenyl selenides and determined many of their physicochemical properties, such as density, refractive index, surface tension, and viscosity. Auten and Kraus (20) studied the reactions of compounds containing the dibutyl boron group. The reaction of dimethylmercury with phenol was investigated by Roton ( 1 4 0 ) . The product was found to be rather stable, except in the presence of catalysts such as gold chloride. Stiles, Rust, and Vaughan ($30)prepared a series of prirnuy, secondary, and tertiary alkyl phosphines by the free radical sensit,ized addition of phosphine to various unsaturated compounds. The reaction took place in small quartz tubes, and its progress measured by the decrease in the liquid volume. I n a British patent issued to N.V. de Bataafsche Petroleum Maatschappij (170) similar compounds were prepared from tervalent phosphorous derivatives and unsaturat'ed compounds in the presence of organic peroxides. Kinnear and Perren (120) formed organophosphorous compounds by the reaction of alkyl chlorides with phosphorous trichloride in the presence of aluminum chloride. A large number of these compounds were prepared and analyzed, and evidence mas presented for the formation of complex saltlike intermediates. Wiley and Jarboe (260) found that dimethyl p-ethylbenzenephosphate was obtained with ethylbenzcne and phosphorous trichloride in the presence of aluminum trichloride in a methanol medium. The reaction cited gave a titi% yield. d German patent was issued to Farbcnfabriken Bayer ( 6 0 ) for an improved process for the preparation of tetraalkyl dithiopyrophosphates. They used alkali-metal carbonates as the alkylating agents, and worked a t temperat'ures between 40" and 90" C.
DEALKYLATIONS Topchiev and associates ( 8 P ) found that pentane, when subjected to a high temperature destructive alkylation on an aluminosilicate catalyst, yielded a variety of products, including higher boiling hydrocarbons. As compared with the noncatalytic pyrolysis, the catalyzed reaction produces more branched hydrocarbons and favors cyclization and aromatization. Typical aromatization catalysts, aluminum-chromium and aluminunimolybdenum, did not appreciably alter the product composition as compared with the noncatalytic reaction. A British patent was issued to the Standard Oil Development Co. ( 7 P )for a process involving the concurrent dealkylation of aromatic hydrocarbons and dehydrogenation of naphthenic hydrocarbons. The dealkyiation of alkyl phosphites, phosphates, and phosphonates was studied by Gerrard and associates ( 3 P ) . Dealkylating agent, time of reaction, and temperature of reaction were all varied. Dealkylating agents were hydrogen chloride, bromide, and iodide. Debenzylation of quaternary compounds and tertiary amines is about 10 to 20 times as fast as debenzylation of secondary to primary amines according to Dahn and Solms ($P). The best catalyst for splitting with hydrogen is palladium-animal charcoal. Raney nickel and platinum tend to hydrogenate the ring. A Japanese patent was issued to Amemiya and Suzuki ( I P ) for a process in which hydrogen or hydrogen sulfide was used as a splitting agent in converting 2-methylpyridine to
INDUSTRIAL AND ENGINEERING CHEMISTRY
September 1954
pyridine. Yield was 21%. The optimum conditions for dealkylation of retene by aluminum chloride in benzene were found by Kirjakka and Voutilainen (4P). Yields were 81.5% cumene and 11.5% 1-methylphenanthrene. Dihydroretene yielded the same products under the same conditions. Matsukawa and Kuwata ( 5 P ) pyrolyzed higher alkylnaphthalenes in the presence of acid clay to give lesser alkylated naphthalenes, olefins, and naphthalenes. Postulated reactions are included. A British patent was granted to Soci6t6 des usines chimiques Rh8ne-Poulenc ( 6 P ) for the preparation of 6-propyl-2-thiouraci1, a compound of value in the treatment of hyperthyroidism. It ie produced by the demethylation of 6-propyl-2-methylthiouracil.
ACKNOWLEDGMENT
It is a real pleasure to acknowledge the valuable help in searching, checking, and abstracting the literature constributed by Robert P. Bringer, Daniel E. Collins, and Elizabeth Prentiss. LITERATURE CITED ilrnold, R. T., and associates, J . Am. Chem. Soc., 74, 368-71 (1952). Buu-Hol, S g . Ph., and associates. J . Org. Chem., 17, 1463-5 (1952). Crawford, ;\I.,and Stewart, F. H. C., iVature, 170, 322-3 (1952). De la Mare, P. H. D., and Vernon, C. A,, J . ChenL. Soc., 1952, pp. 3325-31. Dombrovskii, A. V., Uspekhi Rhim., 22,777-820 (1953). Hennion, G. F.,and associates, J . Org. Chem., 17, 1102-6 (1952). Jones, B. IT., and Neuworth, X I , B., ISD.ENG.CHEM.,44, 2872-6 (1952). Kiddoo, G., Chem. Eng., 59, KO. 9, 149-68 (1952). Longuet-Higgins, H. C . , arid Sowden, R. G., J . Chenl. Soc., 1952, pp. 1404-8. Weygand, F., and Kirchner, K. D., Angew. Chem., 64, 203 (1952). CARBON-CARBON ALIPHATIC
(1B) Anglo-Iranian Oil Co. Ltd., Brit. Patent 692,427 (June 3, 1953). (2B) Boyd, R. N., and Kelly, R. ,J,, J . Am. Chens. Soc., 74, 4600-2 (1952). (3B) Braude, E. .i.,and associates, ,J. Chenz. SOC.,1952, pp. 1419-25. (4B) BuLI-HoY,Xg. Ph., and associates, Rec. t ~ a e chim., . 70, 10991104 (1951). (5B) Crawford, C. C. (to Phillips Petroleum Co.), U. S. Patent 2,625,540 (Jan. 13, 1953). (6B) Darragh, J. L., and Johnson, G. U. (to California Research Corp.),Ibid., 2,626,967 (Jan. 27, 1953). (7B) Donnell, C. K., and Kennedy, R. bl., J . Am. Chem. Soc., 74, 4162-4 (1952). (8B) Kosolapoff, G. M., Ibid., 75, 1500-1 (1953). (9B) XIrstik, A. T'. (to Sinclair Refining C o . ) ,U. S.Patent 2,618,669 (Nov. 18, 1952). (10B) Paushkin, Ya. M., and associates, Doklady Akad. h'auk S.S.S.R., 86, 321-3 (1952). (11B) Pines, €1. (to Universal Oil Products Co.), U. S. Patent 2,594,343 (April 29, 1952). (12B) Plate, A. F., and Savel'eva, R. I., Dolclady Akad. :\'auk S.S. S.R., 82,919-22 (1952). (13B) Sakurada, I. (to High Molecular Chemical Assoc.), Japan, Patent 137 ('52) (Jan. 18, 1952). (14B) Schmerling, L., and West, J. P., J . Am. Chem. Soc., 74, 3592-4 (1952). (15B) Scineider, il., and Kennedy, R. A I . , Ibid., *J. Am. Chem. Soe., 73, 5013-18 (mi). CARBON-CARBON AROMATIC-GENERAL
(1C) Battum, Care1 & van 'I.(to Shell Development Co.), V. S. Patent 2,622,112 (Dee. 16, 1952). (2C) Borkowski, W. L., and Wagner, E. C., J. 070. Chem., 17, 1128-40 (1052). (3C) California Research Corp., Brit. Patent 672,101 (May 14, 1952). (4C) Chemische Fabrik Griesheim, Ger. Patent 840,240 (May 29, 1952).
1797
(5C) Hart, H., and Vosburgh, W. G., J . Am. Chem. Soc., 73, 4983-4 (19511. (6C) JoAes, k. C. K., Jones, A. R., and Strickland, B. R., IND.ENQ. CHEX.,44, 2721-5 (1952). (7C) Matsukawa. T., and Kuwata, T., J . Soc. O r y . Synthetic Chem., Japan, 8, 27-9 (1950). (8C);\loran. W.J., and associakes, J . Am. Chem. Soc., 74, 127-9 (1952). (9C) Morton, A. A , and Brachman, A. I).,J . Am. Chem. Soc., 73, 4363-7 (1951) (1OC) K.V. de Bataafsche Petroleum LIaatschappij, Dutch Patent 71,112 (Kov. 15, 1952). (1lC) Ogawa, Rl., .I. Chem. Soc. Japan, Ind Chem. Scct , 54, 99-100 (1951). (12C) Rinderknecht, Heinrich, J . Am. Chem. Soc., 73, 5770-3 (1951). (lac) Sherwood, P. W., Petroleum R&w, KO.1, 97-103 (1953). (14C) Tagmann, E., and associates, Hela. Chzm. Acta, 35, 1541-8 (1952). (15'2) Toda, H., and Kosaka, Y., J . Chem. Soc. Japan, Ind. Chem. Sect.. 53. 89 -93 (1950). (l6C) Wasson, .J: I., and Smith, W.A I , INDENG.CHEY.,45, 197zoo (1953). CARBON-CAREON AROMATIC ALKYLATIONS (Friedel-Crafts Type Catalysts-Aluminum Chloride)
(1D) Burwell, R. L., and associates, J . Am. Chem. Soc., 74, 4507-70 (1952). , (2D) Ibid., pp. 4570-2. (3D) Champagnat, il., French Patent 893,179 (June 1, 1944). (4D) Comuagnie francaise de raffinage, Ibid., 977,589. (5D) Ibid.; 979,441 (April 26, 1951). (6D) Degering, E. F.,and associates, J . A h . Chem. Soc., 74, 3599601 11952). (7D) Ferro, b. J. (to Phillips Petroleum Co.), U. 9. Patent 2,622,935 (Dec. 23, 1952). (8D) Horeczy, J. T. (to Standard Oil Develoument Co.), Ibid., 2,612,531 (Sept. 30, 1952). (9D) Inatome, >I., and associates, J . Am. Chem. Soc., 74, 292-5 (1952). (10D) Kanao, S., and Toyoda, T., Japan Patent 3020 ('51) (June 12, 1951). (11D) Kennedy, R. M., and Schneider, A. (to Sun Oil C o . ) , U. 5. Patent 2,626,966 (Jan. 27, 1953). (12D) Kodama, S., and associates, J . Soc. Org. Synthetic Chem., Japan, 8, KO.11,23-5 (1950). (13D) Kuchkarov, A. B., Zhur. Obshchel Khim., 22, 1127-32 (1952). (14D) Lagidze, R. YI.. and Petrov, A. D., Doklady A k a d . Nauk S.S.S.R., 83,235-8 (1952). (15D) Messina, N., and Brown, E. V., J . Am. Chem. Soc., 74, 920-3 (1952). (16D) N.V. de Bataafsche Petroleum Rlaatschappij, Dutch Patent 70,427 (July 15, 1952). (17D) Paushkin, Y . M., and Kurashev, &I. V., Doklady Akad. iYauk S.S.S.R.,88,995-8 (1953). (18D) Pines, H., and Kvetinskas, B. (to Universal Oil Products Co.), U. S. Patent 2,616,897 (Nov. 4, 1952). (19D) Ross, Sidney D., and Markarian, M., J . Polymer Sci., 9, 219-28 (1952). (20D) Ruhrchemie A.-G., Brit. Patent 681,211 (Oct. 22,1952). (21D) Sidorova, N. G., and Dudnikova, E. A , , Zhur. Obshchel Khim., 23, 1399-1401 (1953). (22D) Standard francaise des pbtroles, French Patent 977,621. (23D) Takegami, Y., and Shingu, H., Bull. Inst. Chem. Research, Kyoto Univ., 24,84 (1951). (24D) Tarama, K., and Kubota, T., Ibid., 20, 59 (1950). (25D) Taylor, E. P., and Watts, G. E., J . C'hem. Sac., 1952, p. 5054. (26D) Tsukervanik, I. P., and Taveeva, K., Zhz~r.Obshchel Khim., 22, 966-9 (1952). (27D) Valser, V. L., and Polikarpova, il. M., Doklady A k a d . Arauk. S.S.S.R., 84, 71-2 (1952). (28D) Welch, L. hil. (to Standard Oil Development Co.), U. S. Patent 2,614,080 (Oct. 14, 1952). \ - - -
CARBON-CARBON ALKYLATIONS (Sulfuric Acid Catalysts)
(1E) Anglo-Iranian Oil Co. Ltd., Brit. Patent 686,605 (Jan. 28, 1953). (2E) Buu-Hol, W. P., and associates, J . 0 7 0 . Chem., 17, 1122-7
(1952). (3E) Nickels, J. E. (to Koppers Co., Inc.), U. S. Patent 2,598,715 (June 3, 1952). (4E) Persyn, C. L. (to Tide Water Associated Oil Co.), Ibid., 2,592,063 (April 8 , 1952). (5E) Sidorova, N. G., and Grebenyuk, A. D., Zhur. Obschchel Khim., 22. 1550-2 (1952'). (BE) Stevens, D. R. (to'Gulf Research & Development Co.), U. S. Patent 2,603,662 (July 15, 1952).
INDUSTRIAL AND ENGINEERING CHEMISTRY
1798
(7E) Weiss, F. T., and associates, Anal. Chem., 25,277-84 (1953). (8E) Welch, C. M., and Smith, H. A , , J . Am. Chem. Soc., 73,4391-3 (1951). C A R B O N - C A R B O N A L K Y L A T I O N S (Other A c i d Catalvsts)
Bloch, H.S., and Hoffman, A. E. (to Univeisal Oil Product. Co.), U. 8 . Patent 2,644,847(July 7, 1953). Dominion Tar 6;. Chemical Co. Ltd., Brit. Patent 668,283 (March 12,1952). Hanmer, R. S. (to Phillips Petroleum Co.), U. S. Patent 2,559,818(July 10,1951). Pines, H., and absociates, J . Am. Chem. Soc., 73,4483 (1951). Plummer, H. S.,Petroleum Engr., 25,Yo. 10,C-27-32(1953). Rosenwald, R.H., J . Am. Chem. SOC., 74,4602-3(1952). Schulee, IT. A. (to Phillips Petroleum Co.), U. S. Patent 2,645,672(July 14,1953). Sidorova, S . G., Zhur. Obshehei Khim., 22,962-6 (1952). Vaiser, V. L.,and Polikarpova, A. >I., Doklady Akad. S a d S.S.S.R., 85,85-6(1952). C A R B O N - C A R B O N A L K Y L A T I O N S (Miscellaneous Catalysts)
(IG)Badische Aniliii- &. Sodafabrik, Ger. Patent 843,251 (July 7, 1952). (2G) Ibid., 856,436(Nov. 20,1952). (3G) Cannon, G. W., and Whidden, H. L., J . 0 7 0 . Chem., 17,685-92
(1952). (4G) Fujisaki, T., and Ogawara, T. (to Bureau of Industrial Technics), Japan. Patent 287 ('51)(Jan. 30,1951). (5G) Hervert, G. L., and Bloch, H. S. (to Universal Oil Products CO.),U.S.Patent 2,589,253(illarch 18, 1962). (6G) Wagner, C. R. (to Phillips Petroleum Co.), Ibzd., 2,592,625 (April 15,1952). (7G) Yamamoto, K., and Oku, AI. (to RIitsui Chemical Industries Co.). Japan. Patent 5360 ('52)(Dee. 17,1952). C A R B O N - C A R B O N A L K Y L A T I O N S (Grignard Reagent)
DBcombe, Jean, Compt. rend., 237,289-71 (1953). Gault, H., and associates, Chimie & industrie, 67, 749-52
(1952). Grummitt, O., and associates, Anal. Chem.,24,702-8(1952). Heilmann, R., and de Gaudemaris, G., Compt. rend., 233, 874-5 (1951). Henee, H. R., and associates, J . Am. Chem. Soc., 73,4915-18 (1951). Henee, H.R., and Swett, L. R., Ibid., 73,4918-20(1951). Kirrmann, A,, and Berschandy. S., Compt. rend., 234,1373-4 (1952). Krutman, A. I., Zhw.Obshchet Rhim., 22,1342-6 (1952). Levina, R. Y., and associates, Vestnik Moslcozi. Unit,., 7, No.2,Ser. Piz. M a t . iEstestven. Xauk No.1, 105-8 (1952). McBee, E.T., Higgins, J. F., and Pierce, 0. R., J . Am. Chew. SOC.,74,1387-90 (1962). Petrov, A. D., and Chernyshev, E. A,, Doklady Akad. S a d ; S.S.S.R., 86,957-9 (1952). Sokolova, E. B., Zhur. Obshchel Khinz., 22,1941-3 (1952). Wessely, I. F.,and associates, Monatsh., 83,1253-73 (1952). Woods. G. F..and Plapinger, R. E., J . Bm. Chem. SOC.,73, 5603-5 (1951). C A R B O N - C A R B O N A L K Y L A T I O N S (Complex Alkylations)
Cagniant, P., and Cagnlant, Llme. P., Bull. soc. chim. Fiar ce 1952,pp. 713-19. Chiavarelli, S.,Rend. u t . super. sanzth, 14,692-6 (1951). CIBA Ltd., Brit. Patent 651,268(Maich 14,1951). Clauson-Kaas, S . ,and associates, Acta Chem. Scand , 6 , 531 4 (1952). De Benneville, P. La R., and Bock, L. H. (to Rohm 6;. Haas Co.), Brit. Patent 659,353(Oct. 24,1951). Don, Chemical Co., Brit. Patent 677,350(Aug. 13,1952). MchIaster, E. L. (to Dow Chemical C o . ) , U. S. Patent 2,616,877(Kov. 4,1952). Mann, F. G., and hlillar, I. T., J . Chem. Sue., 1952,pp. 4453-7. Maquin, C., and Gault, H., Compt. rend., 234,629-31 (1952). Orito, Y.,J . Soc. Org. Synthetzc Chem., Japan, 10, 495-8 f> l- O B 2 \,.
Petrov, A. A, and associates, Zhur. Obshchei Khim., 23, 1120-4 (1953). Pines, H. (to ZiniversaI OiI Products Co.), U. S. Patent 2,613,214(Oct. 7,1952).
Vol. 46,No. 9
(131) Pines, H.. and Vesely, J. A. (to Universal Oil Products Co.), Ibzd., 2,625,553(Jan. 13,1953). (14i) Schmid, L., and Schultes, H., Monatsh., 83,1184-6 (1952). (1.5) Semonskg, M., Collection CzechosZoL. Chem. Communa., 16, 35-65 (1951). (18i) Shishido. K. (LO Nippon Chemical Industries Co.), Japan. Patent 3719 ('50)(Oct. 27,1950). i 17i) Terent'ev, A. P., and Butskus, P. F., Zhur. Obshchd Iihim., 23, 1230-4 (1953). C A R B O N - C A R B O N A L K Y L A T I O N S (Miscellaneous)
(1J) Bettini, Sergio, and Boccacci, Xario, Riu. parassitol., 13, 165-7;Rend. ist. super. sanith 15,609-11 (1952). (2J) Bloch, H. S. (to Universal Oil Products Co.), U. S. Patent
2,615,856(Oct. 28,1952). (85) Boekelheide, V., and Weinstock, J., J . Am. Chem. Soc., 74, 660-3 (1952). (451 Chemische Werke Albert. Ger. Patent 860.217(Dee. 18.1952). (5J) Compagnie francaise de raffinage, French Patent 977,025 (March 27,1951). (6J) Cronyn, RIarshall W.,J . Am. Chein Soc., 74,1225-30(1952). (75) Fletcher, H. G., Jr., and Diehl, H. W., Ibid., 74, 3799-803 (1952). (85) Kitchen, L. J. (to Pirestone Tire &- Rubber Co.), U. S. Patent 2,605,252(July 29,1952). (9J) Levine, R., and Wilt, 11. H., J . Am. Chem. Soc., 74, 343-4 (1952). (10J) AIomoi, XI,, and associates, Japan. Patent 1562 ('51) (March 27,1981). (IIJ) Reid, E. B., and Yost, J. F., J . Am. Chem. Soc., 73,4995-6 (1951). (12J)Stoppani, A. 0.M., and associates, Anales Asoc. guim. argenlina, 40,260-72 (1952). (135) Stuhmer, W., and Elbrkchter. E. -4.. Arch. Pharm., 285,161-5 (1952). (145) Tegner, C., Acta Chem. Scand.. 6 , 782-90 (1952). CARBON-OXYGEN ALKYLATIONS
(1K)Aimi, M., and associates, Japan. Patent 2138 ('52)(June 10, 1952). (2K) Astle, 11. J., and Zaslowsky, J. -%., IXD.ENG.CHEM., 44, 2867-9 (1952). (3K) Bavin, E.>I., and associates, J . Pharm. and Pharmacol., 4, 872-8 (1952). (4K) Branan, W.JI., and associates (to E. I. du Pont de Nemours 6: Co.), U. S . Patent 2,636,879(April 28,1953). (5K) Chabrier, P., and associates (to Laboratoires Dausse), Ibid., 2,619,485(Iiov. 25,1952). (6K) Cohen, S. G., and associates, IKD. ENG.CHEM.,45, 200-3 (1953). (7K) Courtaulds Ltd., and Alacgregor, J. H., Brit. Patent 683,069 (Nov. 19,1952). (8K) Cusic, J. W.(to Wm. S. Merrell Co.), U. S. Patent 2,606,193 (Aug. 5,1952). (9K) Gevaert Photo-Producten K.V., Brit. Patent 679,184(Sept. 17,1952). (10K) Goncharov, S. V., T r u d y Konferents. Vysokomolekulyar Soedineniyam (High hIol. Compds.) 4% Konf. h,Ioscow, 98-122 (1948). (11K) Klages, F., and Meuresch, II., Chena. Ber., 85, 863-6 (1952). Chimie & industrie, 63, KO,3,474-7(1950). (l2K) Lehmann, R., (13Ii) hlatsuura. T., and Sakakibara, Y., J . Chem. Soc. J a p a n , Pure Chem. Sect., 73,367-8 (1952). (1410 Miyagawa, I., and Ando, E., Menz. Fac. Eng. Unto. Nagoya 1, 54430 (1949). (l5K) SociBte Nobel franpaise, French Patent 895,994 (Feb. 8, 1945). (16K) Stephens, H.K., Chern. Products, 16, 299-303 (1953). (17K) Von der Haar. P., and Pominski, C. H., J . Org. Chem., 17, 177-80 (1952). (MK) Wheatley, 1%'. B., and Cheney, L. C., J . Am. Chem. Soc., 74, 1359-61 (1952). (19K) Zal'kind, Y. E., Venus-Danilova, E. D., and AIikhadova, V. S . ,Zhur. Obshchei I22,1832-8 (1952). CARBON-NITROGEN ALKYLATIONS
(1L) Asta-Werke Akr. Ges., Chemische Fabrik., Brit. Patent
688,331 (March 4,1953).
(2L) Asta-Werke Akt. Ges., Chemische Fabrik., Ger. Patent
842,206 (June 23,1952). (3L) Breusch, F. L., and Baykut, F., Ret. lac. sci. univ. Istanbul,
16A,221-5 (1951).
September 1954
IND USTRIAL AND ENGINEERING CHEMISTRY
Britton, E. C. (to Dow Chemical Co.), U. S. Patent 2,621,185 (Dee. 9, 1952). Campbell, K. N., and associates, J . Org. Chem., 17, 1141-8 (1952). Elpern, B., and Ruddy, A. W., Brit. Patent 673,859 (June 11, 1952). Farbwerke Hoechst vormals Meister Lucius & Briining, Ger. Patent 838,892 (May 12, 1952). Fuortes, C., and Montagnani, S.,Ann. chim. (Rome), 41, 515-33 (1951). Gysin, H., and Hagenbach, R. E., Brit. Patent 680,476 (Oct. 8, 1952). Herz, W., and -Rogers, J. L., J . Am. Chem. SOC.,73, 4921-3 (1951). Hunig, S., Chem. Ber., 85, 1056-60 (1952). Ishihara, K., and Ito, T., Japan. Patent 2668 ('50) (Sept. 12, 1950). Kubicsek, G., Austrian Patent 167,100 (Nov. 10, 1950). Lugovkin, B. P., and Arbueov, B. A., Zhur. Obshche! Khim., 22, 2041-7 (1952). Melamed, S.,and Croxall, W.J. (to Rohm & Haas Co.), U. S. Patent 2,605,286 (July 29, 1952). Monsanto Chemical Co., Brit. Patent 679,382 (Segt. 17, 1952). Naiki, K., and Tsuruoka, S.,J . SOC.Sgnthetic Chem., Japan, 11, 113-17 (1953). Nekrasova, V. A,, and Shuikin, N. I., Izvest. Akad. Nauk S.S.S.R., Otdel. Iihim. Nauk 1952, PO. . 495-7. Ibid., pp. 646-8. Saha, K. N., and associates, Science and Culture (India),18, 152-3 (1952). Simonov, A. M., Zhur. Obshchel Khim., 22, 2006-10 (1952). Sprules, F. J., and Bell, Jr., J. B. (to NOPCO Chemical Co.), U. S. Patent 2,608,584 (hug. 26, 1952). Stuhmer, W., and Kauwmann, W.,Arch, Pharm., 285, 120-2 (1952). (24L), Taguchi, T., and Nakayama, M., J . Am. Chem. SOC.,73, 5679-81 (1951). CARBON-SULFUR ALKYLATIONS
(ZM) Brandt, R. A., and associates, J . Chem. Soc., 1952, pp. 2198205. (2W Brinteinger, H., and associates, Angew. Chem., 64, 398 (1952). (3M) Gundermann, D., and blicheel, F., Ann., 578,45-8 (1962). (4M) Jones, R. G., J . Am. Chem. SOC., 74,1084-5 (1952). (5LI) Larsson, E., Trans. Chaliners Univ. Technol., Gothenburg, A'o. 115,21-3 (1951). (611) Linn, C. B. (to Universal Oil Products Co.), U. S. Patent 2,624,742 (Jan. 6, 1953). ENG.CHEM.,44,1659-62 (731) Thompson, R. B., and associates, IND. (1952). (811) Zimmerschied, W.J., and Arnold, R. C. (to Standard Oil Co. of Indiana), U. S.Patent 2,585,292 (Feb. 12, 1952). CARBON-SILICON ALKYLATIONS
(1N) Capuccio, V., and Pirani, R., Chimica e industria (Milan),33, 282-3 (1961). (2") Da Fano, E. (to John B. Pierce Foundation), U. S. Patent 2,647,874 (Aug. 4. 1953). (3N) Dow Corning Ltd., Brit. Patent 677,462 (Aug. 13, 1952). (4N) Frisch, K. C., and Young, R. B., J . Am. Chem. Soc., 74, 4853-6 (1952). (5N) Fritz, G. Z., Nahrj'oorsch., 7b, 207-16 (1952). (6N) Ibid., pp. 379-85. (7N) Hatcher, D. B. (to Libbey-Owens-Ford Glass Co.), . S. Patent 2,618,647 (Nov. 18, 1952). (8N) Hatcher, D. B., and Bunnell, R. H. (to Libbey-Owens-Ford Glass Co.),Ibid., 2,618,646 (Nov. 18, 1952). (9N) Nametkin, W. S., and associates, Doklady Akad. hraukS.S.S.R., 84, 513-14 (1952). ( 1 0 s ) Nojimoto, E., and associates, Japan. Patent 4518 ('51) (Aug. 16, 1951). (11N) Petrov, A. D., and Chernyshev, E. A., Doklady Akad. 'Va'azrk S.S.S.R., 86,737-40 (1952). (12s) Petrov, A. D., and Chernysheva, T. I., Ibid., 84, 515-18 (1952). (13N) Petrov, A. D., and Mironov, V. F., Izvest. Akad. Nauk S.S. S.R., Otdel, Khim.Nazck, 1952, pp. 635-45. (14N) Petrov, A. D., and Sadykheade, S. I., Doklady Akad. Kazck S.S.S.R., 85,345-7 (1952). (15N) Pierce, John B., Foundation, Brit. Patent 664,488 (Jan. 9, 1952). (16N) Ranbo, J., and Sugimoto, Masayuki, Japan. Patent 4716 ('52) (Nov. 14, 1952).
1799
(17N) Sanin, P. S.,and Petrov, A. D., Zhur. ObshcheX Khim., 22, 1124-7 (1952). (18N) Soshestvenskaya, E. M., Ibid., 22, 1122-4 (1952). (19N) Topchiev, A. V., Nametkin, N. S.,and Solovova, 0.P., Doklady Akad. Nauk S.S.S.R., 86, 965-8 (1952). (20K) Topchiev, A. V., Nametkin, N. S.,and Zetkin, V. I., Ibid., 83, 423-5 (1952). (21N) Westermark, H., Ssensk Kem. Tid., 64, 283-4 (1962). (22N) Yakovlev, B. I., and Vinogradova, N. V., Zhur. Obshchel Khim., 22,1464-5 (1952). (23N) Yakubovich, A. Y . , and Ginsburg, V. A,, Ibid., 22, 1783-7 (1952). (24") Yamada, Sadakichi, and Yasunaga, E., Japan. Patent 3965 ('51) (July 24, 1951). (2%) Ibid., 5567 ('51) (Sept. 21, 1951). (26N) Ibid., 6162 ('51) (Oct. 15, 1951). CARBON-METAL ALKYLATIONS
(lo) Blbers, H., and Lange, S.,Chem. Ber., 85, 278-85 (1952). (20) Auten, R. W., and Kraus, C. A., J . Am. Chem. Soc., 74, 3398-401 (1952). (30) Burt, S. L. (to Union Carbide & Carbon Corp.), U. S.Patent 2,583,084 (Jan. 22,1952). (40) Cox, A. B., and Winter, G., Australia Dept. Supply and Develop. Defence Research Labs., Inf. Circ. KO.13, 1-19 (1953). (50) Ethyl Corp., Brit. Patent 673,440 (June 4, 1952). (60) Farbenfabriken Bayer, Ger. Patent 848,812 (Sept. 8, 1952). (70) Faulkner, D., and blilne, J. S . (to Distillers Co. Ltd.), U. S. Patent 2,583,419 (Jan. 22, 1952). (80) Gilbert, 0. G. (to Ethyl Corp.), Ibid., 2,621,199 (Dee. 9,
-
14.59) " __, .
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