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UNIT PROCESSES REVIEW
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II ALKYLATION I I
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L K Y L I I T I O S research and interest increased during the past year if the number of publications is a true indic.ition. Several studies are reported on free radicals and their role in alkylation. Levy and Szwarc (8'1) studied the reactions of the methyl radicals in a mixture of iso-octane and aromatic compounds. T h e methyl radical presumably reacted either Xvith iso-octane to form inethane plus an iso-oct>.l free radical or \vith the aromatic to form a methyl alkylated aromatic plus a hydrogen free radical. Various aromatics \yere tested and their reactivities rvith the methyl radical were compared. Pritchard, Pritchard, and Trotman-Dickenson (70-lketone, and di-tert-butyl peroxide. Rcacrions of free radicals in cumene, cyclohexene, and benzene-rubber solutions were studied by Dolgoplosk, Erusalimskii, and others (3.4). hllyl, crotyl, benzyl, and tert-butyl free radicals are almost unreacrive Lvith respect to cumene. LYealily active free radicals d o not cause structure formation in rubber. T h e reactivities of a large number of free radicals were rated. Ford, Hunt, and Waters (4A) also studied the properties and reactions of free radicals in solut i o ~ ~ Their . present study is limited to AV-halo anilides, and they found that mesomeric acylamino radicals yield coupling products Ivith C-C or S-C but not K-IY bonds. T h e reactions of inethyl, methoxy, and ethoxy free radicals in solutions were reported by 1 I c Bay, Tucker, and hfilligan (9.4). A correlation has been made of the per cent cleavage attack, and the nature of the attacking free radical and the solvent molecule being attacked. A repulsion theory is proposed. T h e system consisting of methyl radicals. isoprop>-l iodide, and helium !\'as studied a t 8 to 9 mm. and 300' to 330' C. b!- Franklin and Shepherd (5.4). Iodine displacement \vas detected by a silver gauze. LVith primary methyl radicals: the expected extraction (of hydrogen and perhaps iodine) reactions predominated over the displacement of iodine. Several alkyl I
Iiydroperosidr s and dialk>-l pei.osides were produced by Davics. Foster, and \\-bite (2&4), T h e peroxides re used to produce several alkylated compounds. \vhose principal physical properties are i eported. Free radical additions involving fluorine compounds are reported by Tarrant and Lovelace ( 7 7.4). Ne\? methods of producing several halogenated compounds are reported. A l k ~ h t e dstyrenes are reported in a patent issued to Gamrath and Hatton (6.4) to be usrful in formulating force transmission fluids and synthetic lubricants. T h e alkylated polystyrene is produced by reacting polystyrene whose molecular weight is 60:OOO to 80,000 ivith 0.2 to 0.8 parts by weight of olefins containing 5 to 15 carbon atoms. Alk>-l amates are reported by Campbell ( 7 A ) to be useful as plasticizers of elastometers. Twenty-one new amates were prepared and tested in several different types of rubbers. T h e data are tabulated. Kovacic (7.1) has presented a bisalkylation theor)- or neoprene vulcanization. T h e supposition is that the vulcanization of the untreated neoprene involves bisalkylation of the cross linking (vulcanizing)
agent \\.hich may be a diaminr.. dih>.dric. phenol. aminophenol, thiourea: or thioamide. The reactions occur at the active chlorine centers of the neoprene.
CARBON-CARBON ALIPHATIC ALKYLATIONS The rates of addition of mcth\.l frre radicals to unsaturatcd hydrocarbons are reported by Xlandelcorn and Steacie (5B).T h e free radicals were formed by photolysis of acetone a t 124' to 140' C . The products obtained from ethyleiie ivere propane, prop!-lene, and a trace of C 4 materials. Acetylene yielded ethylene, prop)-lene, and butylenes. Activation energies were determined for various reactions. Kondo ( I B ) prepared octano1 and butyric acid by condensation of butanol in the presence of sodium with temperatures of 320' C. Bacchetti (7B) has reported a new method of preparing methyl ketones using diazo ketones. A method of manufacturing caproic acid from cyanoacetic ester is outlined by Sunagawa and Oyamada (70B). T h e steps in this method are discussed. hlono- and disodium adducts of stilbene
LYLE F. ALBRIGHT Purdue University, Lafayette, Ind. LYLE F. ALBRIGHT, associate professor o f chemical engineering a t Purdue, became a member o f the staff in 1 9 5 5 . Several year's experience h a d been obtained previously in both industrial and academic positions. H e received B.S.E., M.S., and Ph.D. degrees from the University o f Michigan. Albright's research interests include organic processes, chemical kinetics, and thermodynamics. H e is a member o f ACS, AIChE, Sigma Xi, Tau Beta Pi, and Phi Lambda Upsilon.
R. NORRIS SHREVE Purdue University, Lafayette, Ind. R. NORRIS SHREVE was graduated from H a r v a r d University in 1907 and far the next 23 years worked in the chemical industry, bath as technologist and consultant. In 1 9 3 0 he b e g a n his academic career a t Purdue and served os h e a d o f the School o f Chemical and Metallurgical Engineering from 1 9 4 7 to 1 9 5 1 . His work has l e d to the publication o f many articles and books. The 2nd edition o f his "Chemical Process Industries" has recently been published.
VOL. 48, NO. 9, PART II
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UNIT PROCESSES REVIEW were alkylated by Reesor, Sniith, a n d SVright (7B). T h e alkylation of cyclopropyl phenyl ketone ivas studied by Piehl and Bro\cn (6B). cu-Hydrogen atoms are replaced normally in benzylation and carbethoxylation with sodium amide a n d triphenylmethyl sodium as condensing agents. I t is concluded that the cycloprop>-1-typeanion can be formed when no alternative mode of reaction is possible and is stable with respect to isomerization to acyclic anion except in bifunctional types. T h e Kellogg Cascade reactor used for alkylating olefins lvith isobutane is described by Stiles (YB). A patent was issued to R u p p (8B)for a n alkylator for reacting isobutane \rith butylene. Bailey and lfadoff ( 2 B ) discuss a method for separating tetraalkylared ketones obtained by the reaction of ketones with sodium amide and alkali halides. Both extraction and distillation steps are involved. T h e method of Horeczy and Boynton (3B) \vas patented for removing the primary alkyl halide from hydrocarbons in the gasoline boiling range. This step which is useful in a n alkylation process consists of t\vo steps in Lvhich the mixture is contacted with bauxite a t 500” to ?003 F. for 0.01 to 1.0 second. T h e effluent gases are then subjected to hydrolysis Lvith caustic soda.
hinders alkylation. Rodionov, Belov. and Kore (SCj studied the effect of the orientation of the lert-butyl group upon its introduction into a n aromatic nucleus. Free radicd aromatic substitution \vas reported by Dannley and Gregg (2C). The reactivities toivard phenyl radical attack was measured for scveral aromatic compounds. Hydratroponitrile \\-as alkylated Isith butyl halides by Goerner and It’orkman 13C). T h e conversions for butyl chloride, bromide, a n d iodide !\-ere 61: 61, and 62Yc’,,respectively, \Then sodiutn amide \vas used. Boekelheide and Goldman ( 7 C ) made a study of the methylation and tautomerism of 8-methylpcri naphthene. Their results are discuss:d in detail.
Friedel-Crafts Type Catalysts Friedel-Crafts type catalysts continuc. to be popular for alk;-lations. Raha (770) reports on the action of aluminum
chloride as a catalyst for several alkylation reactions. A patent issued to Kilpatrick (5D)discusses a method for recovering aluminum halide from the complex formed during alkylation. T h e complex is contacted lvith a moving bed of hot refractory solids maintained a t 1000’ to 3500° F. T h e aluminum halide is recoiwed by destructive distillation. .Z process for alkylating isoparaffins ivith a n olefin is dcscrihed in a patent to hfanne (80). A tivo-stage process is used with bauxite-supported aluminum chloride as a catalyst. Petrov and Leets ( 7 4 0 ) studied the addition of tertiary alkyl halidrs to divinyl and vinylacetylene in the presence of zinc chloride. a-Chloro etliers Irere al!+lat:~d \$:ith ethylene hydrocarbons 11~.Pishnamazzade ( 7 6 0 ) . T h e haloqcn atom adds to the least hydroqenatcd carhon atom of the olefin. Formation of alkyl chlorides accompanird thir rcaction as does the formation of tars; thc former ma!- h- r x p l a n i 4 11>. thc addilion
CARBON-CARBON AROMATIC ALKYLATIONS Several theoretical studies of aromatic alkylations have been made by H a r t and associates. A study (6C) of the stereochemistry under alkaline conditions showed that the C-alkylation accompanying the 0-alkylation in the usual Claisen preparation of alkyl phenol ethers proceeds by direct displacement with stereochemical inversion and a high degree of retention of optical activity. T h e C-alkylation of phenol and p-cresol with optically active methyl phenyl chloromethane does not proceed via the ether but rather directly. Hart, Spliethoff, and Eleuterio (7C) found that methyl phenyl chloromethane alkylates phenols nuclearly and spontaneously, without a n added catalyst; optically active methyl phenyl chloromethane gave products which were also optically active. T h e mechanism of the reaction is discussed. T h e kinetics rates for the nuclear alkylation of phenol and o-cresol with triphenylmethyl chloride were studied bv H a r t and Cassis ( 5 C ) . T h e kinetic curves were 5‘-shaped, which is typical for autocatalytic reactions. The probable reaction steps are discussed. Hart, Cassis, and Bordeaux ( 4 C )reported that dioxane inhibits the nuclear alkylation of phenol with trimethyl chloromethane. They suggest that h>-drogen bonding between phenol and dioxane
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Hydrofluoric acid alkylation unit a t Phillips Petroleum Co. refinery, Phillips, Tex.
INDUSTRIAL AND ENGINEERING CHEMISTRY
ALKYLATION of zinc chloride to the olefin. Siederhauser ( 7 7 0 ) patented a method for alkylating tertiary aliphatic halides with butadiene using a Friedel-Crafts type catalyst (zinc chloride is mentioned as a n examplr) , T h e resulting compounds contain a quaternar)- carbon atom. I t is suggested that the materials \vi!] be useful as intermediates in the preparation of amines, acids, detergents, and bactericides. Isopcntane \vas alkylated by Topchicv: Xndreev. and Krentsel ( 2 6 0 ) with isoprop!-l chloride and iz,rt-butyl chloride in the presence of a complex of aluminum chloride and sulfuric acid. Yields and operating conditiors are rcported. T h e y also used a similar catalj-st to aik>-lale benzene \cith isopropJ-l chloride ( 2 7 0 ) and \t-ith propyl and but)-] chlorides (O’U). Benzene and toluene \cere alkylated by E r o ~ c nand Selson ( 7 0 ) ; and a study was made 0:‘ tiit. isomer distribution in the product. The high proportion of nietaisomers observed in the alkylation of monoalkylbenzenes in the Friedel-Crafts reaction under nonisomcrizing conditions are regarded as not anomalous. An examination of the data on rhe isomer distribution for toluene clearly denionstrated that there is no sharp division between reactions Lchich give a high proportion of rniia-substitution and those which give litrle or none. T h e relative reactivitics of benzene and toluene \cere measured. I t is proposed that the activity of attacking specics is related to the nzeta-substiturion. Vdovtsova and Tsukervanik (280)reported that a free radical mechanism explains the dimerization and reduction of the halides Lvhich occur Ichen aromatic conipounds are alkylated in the presence of aluminum chloride. Depending on the experimental conditions, alkylations in the presence of aluminum can occur either ionically or by a radical route. They (290)also studicd conditions necessary for alkylation by a free radical route. Schmerling and \\.est (?OD)found that isomerization accompanied the alkJ-lation of benzene Lvith I-chloro-3$3- and with 2-chloro-2~3-dimethyibutane. Catalysts used included aluminum cliloride. aluminum bromide, zirconium chloride: and ferric chloride, Contrary to the general opinion, the)- concluded that the aluminurn chloride-catalJ-zed alkylarion of benzene yields sec-alkylbenzene rather than tert-alkylbenzene as the major product. Paltz and Tegge (720) in a patent discuss a n improved technique for handling the aluminum chloride catalyst when benzene is alkylated with propylene. Intact alkylation of benzene and toluene Lvith diisobutene is reported by Sanford? Kovach, and Friedman ( 7 9 0 ) . They used aluminum chloride and nitrobenzene as a catalyst in one case and aluminum chloride and nitromethanc in
another. .Alkylated aromatic hydrocarbons ivere produced by Sledcalf and \-riens (90)when they alkylated azeotropic mixtures of alkanes and aromatic hydrocarbons. T h e alkylated material \vas separated, and the unrcacted material \vas rccirculated through the alkylator. Sidorova, Tsukervanik, and Pak (L’-iD) refluxed a mixture of benzene, alkyl halide: and aluminum until a reaction commenced. T h e n the). added a n olefin and the product obtainrd \\-as a monoalkylbmzene. Several olefins reacted \cith the aromatic by such a procedure. A British patent ( 7 8 0 ) dcscribes operating details for a proccss in \vhich aromatic hydrocarbons bcrre alkylated Lc-ith alkyl halides using aluminum chloride as a catalyst. Detergents were synthesized b). Kunugi and Kudo (70)who reacted monochlorokerosine and niethylnaphthalene in the presence of anhydrous aluminum chloride. Yields varied Ooni 70 to 88%. T h e alkplated products were then sulfonated. Pedreira (730) condensed CS to Cl8 alkyl bromides bcith toluene in the presence of aluminum chloride. Sulfonation of the products yielded detergrnts. Petrova (750)studied the GustavsonFriedel-Crafts reaction. T h e reaction of benzene ivith halogen derivatives is much less catalyzed Lvith antimony pentach!oride than by aluminurn chloride, although in some cases rather good yields were obtained. Several fluorocarbon aromatic ketones were prepared by Simons, Black, and Clark (250)by bubbling the appropriate fluorinated acid chloride through a mixture of aromatic compounds and aluminum chloride. Benzylations and alkylations were performed by Buu-Hoi’, Eckert. and Demerseman (20)in the presence of zinc chloride. Zinc chloride has been used for t \ i o studies of aromatic alkylations. Shuikin, Kuchkarev, and Pozdnyak (220) alkylated benzene with diethyl ether. ethyl alcoho!, or isopropyl alcohol in the 1-apor phase a t pressures from about 20 to GO atmospheres. Temperatures srudied varied from 250’ to 400’ C . They { 2 3 0 ) also studied alkylations 1,cith isopropyl alcohol a t someivhat different operating Conditions. Yields were reported. Dobryanskii and Kornilova ( 3 0 ) used the esters of dicarboxylic acids YO alkylate aromatic hydrocarbons. .\luminum ch!oride {vas the catalyst used. as it \vas in the study by Vig and Sandhu (300) Lvho alkylated o-xylene with eth>-l allylacetate and allylacetone. Alkylnaphthalenes were prepared using aluminum chloride by Mukherji. Vig. and others ( 7 0 0 ) . Several such compounds were produced in yields of about 90%. €ley and Sl’atts (40) prepared aluminum halide complexes with pyridine, tri-
methylamine, and triethylamine. Halides used were chlorides, bromides, and iodides. Dissociation energies of the complexes were measured, as \vel1 as the heats of solutions for the aluminum halides. T h e results \Yere interpreted on a charge-steric basis. Octadecylbenzene was prepared by Shirley and Zietz (270). Benzene and octadecyl p-toluenesulfonate lvere reactrd ivith aluminum chloride as a catal>-st. ?‘here was no rearrangement of the side chain.
Hydrogen Fluoride Catalysts T h e advantages of hydrogeu fluoride alkylation as pertaining to thc Cosden Petroleum Corp. are discussrd by O r r (4E). Hydrogen fluoride consumption is kept loiv (0.19) barrelsibarrel of alkylate) by a high isobutane to o1~~fi.n ratio (9:1), high purity of the hydrosen fluoride (over 90%), and by placing the dcfluorinators behind the deisoburanizcr to reduce the amount of fluorides brought into contact with the alumina. .A new Phillips Petroleum Co. process io;. hydrofluoric acid alkylation is discussed by Peters and Rogers (5E).T h e properte are reported. .i Sun is described in a patent by Schneider (GE). rcrtiar:. paraffin hydrocarbons were fooui-ld to alkylate Lvhen h>-drofluoric acid is used as a catalyst and a tertiary olefin is a hydrogen acceptor. Yields !\err highrr \then isobutene was used instead of 1 -butene. Goodhue and Tissol ( 7 E ) have patented a process for producing highly branched isoparaffinic hydrocarbons, lchich are effective carriers for defoliants. groivth regulators, and selective herbicides. Isobutane Leas alkylated in this process with mixed butenes; di-isoprop)-l heavy ends; and hydrofluoric acid-heavy alkylate, made by alkylating butant- Lcith ethylene. A Dutch patent ( J E ) describes the alkylation of lubricating oils. Liquid hl-drofluoric acid, sulfuric acid: or a Gustavson compound are catalysts. T h e quality of the oil is improved by the process. A process dealing Lvith the disproportionation of mono- and d i - t d butylbenzene has been patented by LfcCaulay and Lien ( 2 E ) . b - h e n hydrogen fluoride is used as a catalyst, disproportionation occurs without isomerization of the tert-butyl groups. Other
Acid Catalysts
Boron trifluoride has been used as a c a t a l y t for several alkylation processes. Patents to Kennedy and Schneider (217) describe the alkylation of olefins with alkyl fluorides, containing a t least 2. carbon atoms in the presence of boron trifluoride and a n alkylcyclopentane containing from 1 to 3 alkyl groups. T h e olefin is alkylated and the alkylcy-
VOL. 48, NO. 9, P A R T II
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UNIT PROCESSES REVIEW clopentane is simultaneously dimerized. Various alkyl fluorides were used. Mixtures of phosphoric acid and boron trifluoride have been used by Topchiev, Kurashev, and Paushkin (QF) as catalysts for the alkylation of benzene with propylene. Yields were measured over a wide range of operating conditions. Zavgorodnii and Gostev (73F) alkylated anisole with 2-butene using boron trifluoride as a catalyst. T h e best yield (83%) was obtained a t room conditions. The alkylation of alkyl phenyl ethers by olefins in the presence of boron trifluoride and its compounds is the subject of a paper by Zavgorodnif ( 7 7F). The principal site of alkylation is the ortho-position, with relatively low (3 to 25%) yirlds of disubstituted products. The effect of temperature and yields arc discussed. Zavgorodnii and Faustova (7.'F) alkylated 0- and p-clilorophenols with 2-pentene in the presence of boron trifluoride etherare. Several products ivere obtained. Topchiev, Tumerman, and others (70F) prepared mixtures of boron trifluoride and diethyl ether, phosphoric acid, sodium acetate, or lead acetate. T h e catalytic activities of the mixtures were evaluated for the alkylation of phenol. T h e ether mixture was most active. Sulfuric acid was used as a catalyst by Krentsel, Topchiev, and Andreev (31;) for the alkylation of isopentane xrith isopropyl chloride and tert-butyl chloride. The reaction showed a definite induction period and thus it cannot be explained merely by the decomposition of the chloride into a n olefin and hydrogen chloride. T h e formation of an intermediate compound appears more probable. A British patent ( 7 F ) describes the alkylation of benzene with a CSto Clz interpolymer. T h e alkylated product is suitable for sulfonation to yield detergents. Lenneman, Hites, and Komarewsky ( 5 F ) have also used sulfuric acid as a catalyst ivhen benzene was alkylated with high molecular 1-alkenes. Chlorobenzene was alkylated by Mamedaliev and Veliev ( 6 F ) with olefins in the presence of sulfuric acid. A propene-butene mixture of gas was used. The best yields, 84.5y0, were obtained a t 4:l to 5:l ratios of chlorobenzene to olefin. Solid phosphoric acid was used as a catalyst by Egloff and Welnert ( 7 F ) for obtaining iso-octenes from propylenes and butylenes. The iso-octenes when hydrogenated have a n octane rating of 90 to 96. Langlois and \Valkey ( 4 F ) discuss a similar process for converting light olefins to high octane motor gasoline. Romadane and Rodin: ( 8 F ) alkylated naphthalene Lrith isoamyl chloride and isoamyl alcohol in the presence of phosphoric acid, boron trifluoride, or zinc
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chloride. T h e products and yields of these three catalysts varied.
Miscellaneous and General Catalysts Alumina has found use for catalyzing several alkylation reactions. Freidlin, Balandin, and Nazarova (7G) report that butane and propylene react when passed over aluminum oxide in a continuous floiv-t>-peapparatus. Operating conditions investigated were from 400' to 500' C. a t 300 to 1500 atmospheres. Most of the products (60 to 70%) boiled under 175' C., and the main reactions were alkylation and polymerization. Polymerization was predominant at 400' C., but alkylation yields rose as the temperature was increased. Alumina catalysts were also used by Sidorova: Tsukervanik, and Abidova (74G) lvho alk>-latedbenzene or toluene \\.ith several chloro- and bromoalkyls. Smith and Masterton ( 7 9 2 ) patented a process for alkylating phenols with methyl alcohol using alumina as a catalyst. Improved yields of monoalkylated products are claimed. Steam is used as a dilurnt i n the reactor. Several alkylation investigators used aluminosilicate catalysts. For example, Dolgov and Cherkasov (6G) reacted benzene with either a n alcohol or alkyl halide to obtain alkylbenzenes. The highest yields tvere obtained u i t h propyl alcohols or propyl halides at optimum conditions of 300' to 320' C. with a feed rate of 0.25 to 0.50 ml./ml. of catalyst/ hour. Yields were from about 50 to 747,. Lower yields were obtained with ethyl or isobutyl compounds. If propylene is used, the catalyst loses its activity. Benzene was alkylated urith butyl alcohol by Turova-Pol!ak, Danilova, and Treshchova (7QG). Atmospheric pressures were employed and optimum yields \vue obtained a t about 300' C. which seems to agree !vel1 with the results of Dolgov and Cherkasov. Shuikin and Pozdnyak (72G) have theorized that alkylations of benzene krith acetals with aluminosilicate catal>-stsis a free radical reaction. T h e esters or ethers they used were probablv the active agents. Acetals used as alkylating agents appeared to react through intermediac>r of ethers resulting from their pyrolysis. They (73G) also studied the alkylation of benzene \.rith ethylal (diethyl formal), diethyl acetal, and diethyl ether. A process for alkalating phenols \vith a silica-alumina catalyst !vas patentcd by Offutt ( 7 l G ) . The liquid phenols flow downward through a column containing the catalyst and contact the gaseous olefins Aoiving upward. hIamedaliev and L7cliev (70G) alkylated chlorobenzene tvith Ca-CA olefins. The operating condi-
INDUSTRIAL AND ENGINEERING CHEMISTRY
tions and methods for preparing the synthetic aluminosilicate catalyst are discussed. Aromatic hydrocarbons are alkylated with methyl alcohol, dimethyl ether, or olefins a t elevated temperatures and pressures in the presence of catalysts prepared from kieselguhr, zinc oxide, and phosphoric acid. The method of producing the catalyst and the operating conditions are reported in a German patent (2G). Ethylbenzene \vas synthesized from benzene and ethylene by Tsutsumi. Yoshijima, and Koyama (78G). The catalyst used was a mixture of cupric oxide and phosphoric acid. Mixtures of phosphoric acid and zinc oxide, nickel oxide, or cadmium oxide did not exhibit any catall-tic effect. Cumene was produced from benzene and propylcne. Kindler (QG) in a German patent reports that the kno\vn process of preparing benzylated phenols useful as bactericides by treating phenols ivith benzyl chloride or its substitution products in the presence of catalytic metals can be improved. .\ small amount of ferric oxide: ferric phosphate, or stannic chloride is used as a catal!-st. Numerous benzylated phenols were produced and identified. A Swedish patent by Tiganik (76G) describes an alkylation catalyst consisting of an alkali metal alloyed tvith a small amount of copper, tin, or silver. This catalyst is effective for reacting organic compounds with alkali chlorides. Topchiev and Bogomolova (77G) tested silicon tetrafluoride as a catalyst for the alkylation of benzene Fvith alcohols. S o alk)-lation was detected for the methyl alcohol-silicon tetrafluoride complex. In the case of ethyl alcohol the degree of alkylation \vas very low and partial hydrolysis of the silicon tetrafluoride and polymerization of the formed ethylene took place. In experiments with isopropyl and isobutyl alcohols, total decomposition of the complexes occurred and alkylation of benzene took place with the olefins produced. hroniatic and olefinic hydrocarbons Irere alkylated by Cauquil, Barrera, and Barrera (3G) with alkyl perchlorates. Conia ( 4 G ) successfully applied the method of alkylating labile saturated ketones through the intermediate of sodium tertiary amylate to the alkylation of unsaturated krtones. He (5G) also applied this mcthod to eth:-lenic ketones. Alkylation of compounds containing a mobile hydrogen atom was accomplished by Babayan, Gambaryan, and Gambaryan ( I G ) in an aqueous medium in the presence of quaternary nitrogen salts and aqueous alkali. T h e reaction OCcurred exclusively a t the expense of the alkyl halide? and the alkyl group of the quatrrnary salt did not participate i n the reaction. Thus the reaction is distinct from alkylations by quaternary salts in
ALKYLATION nonaqueous media a t high temperatures. Trifluoroacetic acid was used as a condensing agent by Henne and Tedder (8G) for carboxylic acids and alkenes or alkynes to produce acyl olefins or 8diketones. respectively.
CARBON-CARBON ALKYLATIONS Grignard Reagents Grignard reagents continue to be popular for synthesis of hydrocarbons. For example. Lukovnikov, Neiman, Bag, Rodionova, Samoukina, and Bliznyak a t the (7.23) produced pentanes Ivith first and third positions. I n addition, Levina, Shabarov, and Skvarclienko ( 7 7 H ) s!-nthesized several enyne hydrocarbons, most of which were a t least provisionally identified. Hydrocarbon products from the reactions of metliyllithium and ethylmagnesium bromide with heavy-metal salts were investigated by Gilman, Jones, and \\-oods ( 6 H ) . O n the basis of the reactions with methyllithium: the metal halides were divided into three groups: Group 1 , which reacts to produce methane almost exclusively; group 2, Mhich forms ethane predominantly; and group 3, which gives a mixture of methane and ethane. I n reactions \vith ethylmagnesium broThe mide, four groups were found. first produces ethane almost exclusively, the second produces mostly ethane but also some ethylene, the third produces similar amounts of ethane and ethylene, and the fourth gives butane, ethane, and ethylene. A free radical mechanism with disproportionation is suggested. Pctrov and Chernyshev (73H) have prepared tetrapropylmethane, tetrabutylmethane, and tetrahexylmethane, tetrapropylsilane, tetrabutylsilane. and tetrahex!-lsilane. T h e physical properties of the compounds were compared. I n general, the boiling points of the silanes are higher and their freezing points are lower. L-nsymmetrical tetraalkylmethanes containing a minimum of 16 carbon atoms \cere prepared by Rab,john and Latiria (76H) w!io coupled Grignard reagents \vith tertiary alk>-l bromide. T h e coupling procrss \vas not clran-cut and the yields of desired hydrocarbons were lox,. Prout, Huang. and others (75H) have examined the reaction of alkyl. aryl> and benz).l organometallic reagcnts with five isopropylidene conjugated systems. T h e 1,4-addition products were the main products in all cases except one. Grignard reagents of sulfones have been studied by Field and NcFarland ( 4 H ) . Frequently, the reactivit!, of these reagents is comparable to that of normal Grignard reagents. Lapkin, Puchkin, and Lykov (70H)have prepared
several ketones by the reactions of acyl halides with organomagnesium compounds. -4 new general method for preparing a-diketones is presented by Cuvigny and Yorman t (2"). Several compounds were prepared and their physical properties are reported. Dreux ( 3 H ) used a Grignard technique to prepare saturated ketones, a-ethylenic tertiary alcohols: and diketones. A series of reactions was carried out by Landrum and Lester ( 9 H ) with alkyl aryl ketones and isopropyl magnesium bromide. T h e degree of the enolization type reaction, of the reduction, and of the addition were determined for se\reral systems. Fuson and Freeman (527)have alkylated duryl phenyl ketone irith a Grignard reagent. The structures of the product were determined. A number of a,Punsaturated a-methyl aldehydes were prepared by Ahmad and \Veedon ( 7 H ) who used a modification of the Inhoffen method. Monomethyldiphenylmethanes and monomethyldicyclohexylmethanes were synthesized by Larnneck and Wise (6"). Several arylmagnesium halide compounds were prepared as intermediates in this investigation. T h e addition of Grignard reagents to fluoro-olefins was studied by Tarrant and [Varner (77H). .An addition reaction first occurs, and then the resulting adduct 10sc.s magnesium dihalide to give an olefinic-type compound Lvith a longer carbon chain than the original. Pohland and Sullivan ( 7 4 " ) prepared five disubstituted carbinamines by the lithium aluminum hydride reduction of Grignard-nitrile adducts. Several alkylated products were obtained in this study. Ginzburg (7H) found that aminotriphenylcarbinols react u i t h Grignard reagents to form hydrocarbons and dyes Lvhose structures are reported.
Complex Alkylations A large increase was noted i n the number of complex alkylation investigations this year. \Vichterle and Cerny (283) studied the chloromethylation of styrene. Eth!-l benzene? formaldehyde, and hydrogen chloride did not react to form new side chains on the aromatic ring. Rather the chloromethyl group increased the length of the side chain. A patent to Jones ( 7 7 ; ) described the process for the chloromethylation of polystyrene. T h e resulting resin can then be transformed to a quaternary ammonium salt which is useful for removing anions. Rabjohn (232) has chlorornethylated toluene. The resulting 0 - and p-xyIyI chlorides have been chlorinated in the side chain. The p-isomer can then be separated from the mixture and converted to terephthaloyl chloride. A VOL. 48,
method for bromoethplation of tert-butylbenzene was investigated by Krausz (7%). Yields u p to 73.8% are reported. Gudriniece, Rozite, and Lepika (Qi) have chloromethylated l-chloronaphthalene. They used glacial acetic acid, concentrated hydrochloric acid, a n d 8jYG phosphoric acid. Chloromethylated arylaminoanthraquinones are the subject of a patent to Randall and Renfrew (242). T h e materials are used as dye intermediates. Quelet (222) has studied the application of chloromethylation to the synthesis of polyalkoxyphenylacetic acids. A procedure for the synthesis is described. Lichtenberger, Muller, and Huguet ( 7 4 ) chloromethylated fluorobenzene without any difficulty with formaldehyde, hydrogen chloride, and zinc chloride. Diphenylmethane was treated by hfaquin and Gault (75i) with trioxymethylene, hydrogen chloride, and phosphoric acid in a n acetic acid solution. T h e products were p-chloromethyl-diphenylmethane and p-p '-di-
chloromethyl-diphenylmethane. Partially cyanoethylated cottons were studied by several investigators. They \yere prepared by D a d , Reinhardt, and Reid (5i). Materials and methods, the effect of operating variables on the reaction: the preparation of partially cyanoethylated cotton, the recovery of acrylonitrile, and the hydrolyis of the modified cotton are considered. T h e properties of cyanoethylated cottons (7i) are discussed in regard to dyes, fastness of dyeing, and to microorganisms. Grant, Greathouse, and others (8i)present a progress report on cyanoethylated cottons. Increases in the breaking strength or elongation of the yarns results from changes in frictional forces. Compton, hfartin, and others (4)have reported on the pilot plant production and properties of the cyanoethylated cotton. T h e results in general seem promising, and commercial applications appear probable. Cyanoethylation of cyclohexanone a n d 1-methyl-2-cyclohexanone was investigated by Terent'ev, Klabunovskii, a n d Budovskil (27i) in the presence of optically active quartz. The quartz was coated with sodium, potassium, or lithium eth>-late. Products bvere of the asymmetric reaction with maximum rotations achieved being 0.07' for the cyclohexanone reacrion, and 0.1 57' for the methyl derivative. T h e activity of the catalysts passes through a maximum, and then declines because of the poisoning of the cyclohexanols formed, Bruson and Riener (32) found that the reported resistance of isophorone to cyanoethylation with acrylonitrile was caused by acidic impurities which poisoned the catalyst. A large increase of the yield of monocyanoethylated ketonic compounds NO.
9, PART II
SEPTEMBER 1956
1555
UNIT PROCESSES REVIEW was found by Baumgarten and Eifert (22) when they used a 1O:l ratio of ketone to acrylonitrile in the presence of the catalyst (Triton B). Cyclic and heterocyclic ketones were cyanocthylated by Sazarov, Shvekhgefmer, and Rudenko (772). Their operating conditions are outlined. T h e cyanoethylation of cyclic B-diketones was investigated by Sazarov ar.d Zav'yalov (78i). Other cyanoethylation processes reported include those for alkyl-substituted acetoacetic esters ( 76i) and glycylglycine and dioxopiperazines (26i). Graft copolymers of nylon and ethylene oxide \\-ere prepared by Haas! Cohen, and others (704. The copolymers have higher melting points and greater flexibility than the unsubstituted nylon. In addition, they are more hyprophilic and stable. A hydroxyethyl nylon 66 with 507, ethylene oxide added has a melting point of 221' C. and a glasspoint temperature below -40' C. Nylons 6 and 610 have also been tested. Hydroxyalk>.lation in a n aqueous medium was investigated by Gault (74. T h e condensation of two carbonyl compounds (identical or different) in a n aqueous alcohol takes p!ace betxveen the enolate of one and the hydrate of the other. Prevost, Seguin: and others, (202) have studied hydroxyalkylation reactions in anhydrous mediums. Their procedures are reported. The reversibility of the aminoalkylation reaclion is reviewed by Larramona and Tchoi:bar (73;). T h e addition of water or excess amine reverses the reaction. Dimethylaminomethylation of 2-naphthol )vas investigated b>- Dzbanovskii, hIarochko, and Kost (62). T h e acetoxymethylation reaction was conducted for several aromatic compounds by Summers (25). Lower temperatures or shorter reaction times led to optimum yields of the monomeric ester. Higher temperatures led to polymers as the almost exclusive product. Compared to the chloromethylation, this acetoxymethylation reaction differs chiefly in the greater tendency toward polymer formation. Petrov (792) reports that alkyl hypobromites add to chloroprene and bromoprene predominantly in the 3,4position. Alkyl hypochlorites add predominantly in the 1,4-position. This difference is caused by steric effects. T h e phosphonethylation reaction involving the addition of malonic cyanacetic, and acetoacetic ester and their homologs to vinylphosphonic ester is discussed by Pudovik and Denisova (27i).
Miscellaneous Indole was nitroethylated by Koland and Hartman (ZJ). They obtained 3(2-nitroethyl) indole. T h e experimen-
1556
tal details are outlined. A British pathianabe and Hiyama (70K) obtaintd ent (3-7)outlines a process for producethers in the reaction between p-nitroing alcohols with higher number of carchlorobenzene and ethyl or methyl alcobon atoms from alkenes. For examplr. hol in the presence of sodium hydroxide, a mixture of ethylene, Lvater, and h>-potassium hydroxide, sodium ethoxide or drogen \vas passed as a vapor at atmosmethoxide. T h e results indicate that pheric pressure through a glass ozonizer. tile reaction was second order in regard T h e silent discharges in the ozonizer opto the concentration of the p-nitrochloroerated at a potential of 20,000 volts and benzene and the sodium or potassium a frequency of 50 c!-cles per second. The ion. The presence of water or glycol dedried mixture contained 1-butanol. pricreased the reaction velocity, but methyl mary hexanol. and ethanol. Other alcohol increased it. T h e mechanism of alcohols that have bern produced include the reaction luas discussed. Tlie kinetisopropanol and highly branched alcoics of the reaction between chloronitrohols ivith 6 to 8 carbons. T h e higher naphthalenes and sodium alcoholatcs alcohols are useful as solvents for lacquers ivere studied by Simonetta and Favini and resins and as chemical intermediatcs. (781%~). They found this reaction \vas Several alkyl derivatives of di-. tri-. and also second order. Patai and Benrov tetrasalicylides !rere prepared by Baker. (73K) found that the transesterification Harborne, and others ( 7 4 . The prinof methyl methacrylate with 2-naphthol cipal physical properties are reported. yielded, instead of the expected Sidorova ( 4 1 ) mixrd 2-methylcycloester, 2-naphthyl methyl ether. The hexanol and benzene in the presence of reasons for the ether formation are aluminum chloride. T h e mixture \vas discussed. heated a t 100' C. until hydrogen chloGlycerol guaiacyl ether was prepared ride gas \\-as evolved. The product conby Astoul ( 3 K ) bvho treated alkali phe1-meth>-1-1-phenylcyclohexane. nolates with chlorohydrins, Enol ethrm tained Several other products \';ere obtained and have been prepared by Chase and identified. \Valker (611). Operating details are described. S2;illiams and Freyermuth (2CIK) have patented some fluorescent agents which contain a n oxygen-alkyl CARBON-OXYGEN ALKYLATIONS linkage. Inhoffen? Briickner, and Grundel ( 7 K ) describe their method for [!le -4 large number of carbon-oxygen partial synthesis of isotachysterol methyl alkylation investigations has been reerher. rchich is involved in the prcparaported this ycar. Burtle and Tureli iion of vitamin D. By the use oi in( 5 K ) synthesized diethyl ether containing frared and ultraviolet spectra. \Vtmkcrt, carbon-14. Ethyl iodide containing carBow. and Reid ( 7 i K ) !lave proved the bon-14 \;-as reacted r\-ith sodium correct structure for the o-alkylation of ethoxide. T h e reactions of lithium. soj-acylosindoles. hIorphine ethers are dium. and potassium ethoxide \\-it11 2obtained in better yields b y using nonethylheu)-l bromide \\-as investigated in aqueous solvent svstcms. Operating deethanol by Smvman and Evans ( 7 2 K ) . tails are explained in a British 1".ntrnt The >-ieldsof 2-ethylhexyl ethyl ether and ( CK). the olefins formed are reported for each Heterogeneously methylated cclluloses ethoxide. Scleznev and Balakirev (16K) l \ w e in\-estigated by Xhe. LIatsuzaki, synthesized 2-chloroethers from unsatuand others ( 7 K ) . I n the initial stages a n rated hydrocarbons, ethyl alcohol, and intermicellar reaction occurs. In later ether in a vertical column fillrd with stages a permutoid reaction is apmarble or limestone chips. The product proached. The effect of the distribucan be used for the deparaffinization of tion of methoxy groups upon some of the aviation oil. Aryl methyl ethers ivere textile properrirs of methylated cotton produced by hIatsuura (77K) \rho had fibers is reported by Reeves, Armstrong, added sodium in a methyl alcohol soluand others (75K). For the retention of tion to phenol and dimethyl oxalate to the desirable textile properties and the obtain the ether. \Vhen octadecyl !Iimprovement of rot-resistant qualities, toluenesulfonate was refluxed with absos!ibstitution in the range of 0.25 to 1.0 lute ethanol and potassium cyanidc. inehoxy group per glucose unit should Shirley and Zietz (7711) produced both preferably be carried out under minioctadecyl ethyl ether and octadec!-l niIIIUIII swelling conditions. Aiethylated trile. T h e effect of water on the resugars have been separated by Lindberg action was reported. Petrie and Britand \\'ickberg ( 9 K ) chromatographically ton (74K) have patented a process for in a carbon column. Details of the graproducing hydroq- aralkylene ethers of dient elution technique are given. Adler arene sulfonic acids. These materials, and Gierer ( 2 K ) have alkylated lignin which are useful as emulsifying and surlvith alcoholic hydrochloric acid. Etherface active agents, are formed by conification and transetherification reacdensing aralkylene oxide with hydroxy tions probably occur. Borodina and arene sulfonic acid.
INDUSTRIAL AND ENGINEERING CHEMISTRY
ALKYLATION ~~
Shchukina ( J K ) discuss the alkylation of the ethyl ester of P-hydroxycapric acid.
a t the amino nitrogen. T h e aminoacetanilide has methyl groups in position-2 or -6, is either unsubstituted or substituted with a meth>-l or butyloxy group in position-4 of the benzene ring, and has a n CARBON-NITROGEN alkyl group of not more than 3 carbon ALKYLATIONS atoms or two groups having not more than 4 carbon atoms on the nitrogen. Tertiary amines were prepared b!. Bolle, llousseron, and Bourgeois (5L). .Alkylation agents that are suitable inclbde halides or sulfates cf loxver alkyls in Dodecyl w a s one of the alkyl groups of the presence of a suitable solvent such as the amine and the other tbvo contained methyl, ethyl, or propyl alcohol; ace1 to 4 carbon atoms. Alkyl chlorides add to the tertiary amines to yield quatone; benzene; or nirrobenzene. T h e products possess local anesthcric properternary ammonium deri\yatives. The ties. Pratt and Frazza (27L) have properties of some of these derivatives were measured. Humphreys (75L)patstudied the -Y-alkylation of anilines with primary alcohols. S\-ith @-substituted ented a process for preparing amides of the type R S H A I , xchere R is a n alkJ.1 beaz!.l alcohols, the reaction rates dcgroup containing 1 to 18 carbon atoms crease ivirh the decreasing ability of the or is a n alk>-l-substiruted cycloalk>.l substituent to release electrons. T h e regroup. .If is a n alkali metal. I n a verse order was obtained ivhen p-subtypical example, sodiuni amide was restiruted anilines were tested. 2--Alkylacted with primary butyl amine to form naphthalimides were prepared by Allen the product. Alcohols, halides, and and Reynolds (3L). Lvho rrfluxed naphoxygen must be excluded from the rethalic anhyiride with e s c w an-ine for action \,essel. .A new method for the re1 hour. moval of alkyl groups from -Y-alk>.l Indole \vas alk)-latcd b y Plieninger amides (and -V-alkyl anilides) of car(7,PL) in liquid ammonia in a nitrogen boxylic acids has been reported b!. atmosphere. 13). proper control of the Klamann and Schaffer (76L). Pyridine operating variables either 1-benzylindole h)-drociiloride is heated Ivith the amides or 2-benzylindole can be prepared. (or anilides) to remove the alkyl group. Potts and Saxton (20L) nirthJ-lated inAbe, Tsukamoto, and Ishimura ( I L ) dole in a liquid ammonia solution of sosynthesized several aliphatic iV-monodium to obtain l-methylindolc. Xlethyl alk!.lamino acids. Their procedure i s iodide \cas the alkylation agent. Liquid outlined. aixmonia solutions have also been used '1Vard a n d Lamb (13L) describe a ne\$' by Shimo and Asami (22L) for benz)-laprocedure for the a\--alk!-lation of arorion of hydantoin and benz!.larion and matic aniinrs? ivhich are produced by inerhylation of glycine anhydride. trearing an aromaiic amine: nitro: or .% realkylation reaction \vas studied b>nitroarnino compound ivith hydrogen Baba)-an, Gambaryan, and Gambaryan and a dialkyl ketone containing a t least ( J L ) . Terriary amines can be made to 4 carbon atoms. -An aqueous distribuexchange their methyl group for a chlorotion cut from the final product comprisbutenyl radical. Hamor and Soine ing the water-ketone azeotrope is rei73L) have prepared several ?-dialkylcycled in the process. .A copper chroaminoalkyl derivatives of saccharine mite catalyst is used. Pochinok anti using isoprop)-l alcohol as a solvent. Portnyagina (19L) discuss the alkylaThey refluxed sodium saccharine tvith tion of benzoic acid and 2-naphthol by h e desired alkyl halide. Riinvrstigaalkyl-2-nap!itIiyltriazines. Operatins detion by Herbst and Percival ( 7 J L ) of the tails are presented. An oxidation inalkylarion of 1-alkyl-5-aminotetrazoles hibitor for materials such as gasoline. sholvs that 1,4-dialk!.l-S-imino-4: j-dihylard, and rubber has been patented by drotetrazoles are formed instead of 1 , j Chenicek (SL). X phen)-lenediamine is dialkylamino-tetrazoles as previously reacted I v i t h a n acid-type metal deactiA dissertation by Cook supposed. vator. X 3 to 5 carbon alk>-lradical re(7OL) concerns the alkylations with places a hydrogen atom on one or more of quaternary salts of 2-aminometh>-linthe nitrogen atoms. S,S-Di(n-alkyl) dolts. Coffman, Hochn, and Maynard derivativcs of phenethylaniine have been ( 9 L ) have announced a neiv class of prepared and tested by Zamboni and polyamines. T h e polyamines are preVitali (2JL). T h e materials indicate pared batchlvise by the reductive aminaadrenolytic activity. .A neiv procedure rion of polyketones. T h e products have for the preparation of alkylanilines is essentially the structure of a long-chain presented by Gerrard and Jeacocke h!-drocarbon Ivith lateral primary, sec(72L). ondary, or tertiary amine groups atThe h-alkylation reaction of aniline and propylene oxide has been studied by tached. T h e polyamines range in physical properties from liquids to \vases. Petrov (77L). A British patent (2Lj describes the process details for preparing Silver sulfate was used by Cast and amino anilides having alkyl substituents Stevens (7L) as a c a t a l y t for the A'-
alkylation of nitriles. Eichenberger, Staehelin, and Druey (71L) have studit d the alkylation and rearranqcment of hydrazide derivatives. A study by Bridges (6L) has shown that methyl bromide, a fumigant, reacts with wheat. T h e main reaction consists of the methylation of the imadazole rings of the histidine residues. Under typical fumigation conditions the amount of reaction occurring is too small to result in an appreciable loss of essential amino acids.
CARBON-SULFUR ALKYLATIONS Liquid-phase reactions between frre radicals and aldehydcs lvcre studied by Barrett and Waters (7,If). Free alkyl radicals readily react Lvirh aliphatic thiols to give alkylthio radicals. These latter radicals attack aliphatic aldehydcs much more readily than alk)d radicals. Beach and Barnett ( 2 M )have patented a prccess for preparing alkyl mercaptans. Alcohols and sulfides arc caused to react in a vapor-phase process a t about 400' C. in the presence of a catalyst, cadmium sulfide. T h e preparation and properties of some organosilicon sulfides and sulfones rvere investigated by Cooper (4.M). T h e sulfides xvere obtained by the reaction of a suitable chlorosilane or chlorosiloxane with sodium mercaptidcs. T h e corresponding sulfones were prepared by oxidizing the sulfides. Alkyl aminocycloalkyl sulfides are prepared by a patented process of Malian (&VI). Aliphatic mercaptans are reacted with selected alkyl hydrogen sulfate in the presence of a base. Enimons and Ferris ( 5 A f ) have improved the preparation of alkyl sulfonates by the silver salt method \vhrn rhc>- used mrthyl nitrilt: as a solwrit. The reaction is limited to primary alk)-l halidcs. T\-ith secondary or tertiary halides. dth!-drohalogenation usually takes place. The action of alkyl halides and allyl bromides on dibut1.l sodium rhiophosphites was investigated by Pudovik and Kovyrzina (7121). .Alkyl groups replaced hydrogen on the sulfur atom. Bordivell, Xndersen, and Pitt (3.11) have reported that alk!-l- and aryllirhiuni reagents react Lvith thiacylopropanes ro produce olefins and lithium mercaptides. T h e reactions probably can best be formulated as a n attack of the alkyl- or arylcarbanion on the sulfur atom. This is facilitated by the coordination of the sulfur Lvith the lithiuni cation. T h e breaking of the carbon-sulfur bond gives risc to a n electron pair \vhich can simultaneously or subsequently iniriate a 1,2-elimination reaction to form an olefin and liberate the sulfur in the form of the lithium mercaptide.
VOL. 48, NO. 9, PART II
SEPTEMBER 1956
1557
UNIT PROCESSES REVIEW CARBON-SILICON ALKYLATIONS Based on the large number of siliconcarbon alkylation studies reported within the last year, interest in the subject and i n silicones appears to be increasing. Procedures for preparing various types of silico-organic compounds are reviewed by Smith (22-V). T h e properties of many such compounds are also reported. Several investigators have reported on the so-called direct method for preparing methylchlorosilanes. Fukukawa (5-Y, 6-V) has prepared several such silanes using cuprous chloride as a catalyst. Iron impurities u p to 2% did not affect the yields, but 8Yc iron lowered it. The combined yields of methylchlorosilanes were as high as 111 to 121%-, based on methyl chloride. D a u d t ( 3 5 ) of Dow Corning Corp. has patented a process for producing alkyltrichlorosilanes. Xfethane, hydrogen chloride, and silicon were contacted in a bomb a t 450' C. under pressure or a t 800' C. a t atmospheric pressure. Organohalosilanes were prepared by Sekino and Hani ( 2 7 5 ) by the direct method a t 300' C. in the presence of aluminum powder. Methods for producing effective silicon-copper catalysts for alkylchlorosilane productions are reported by Trambouze and Imelik (X-V), Mertens (70.Y), Takahashi and Shigeniwa (21-Y)?and Koll and Simons ( 73X). T h e reaction of silane with several hydrocarbons has been investigated by IVhite and Rochow (26.2'). I n a circulating system, silane plus methane, ethane, propane, or isobutane a t 440' to 600' C. produced only disilane, trisilane, and tetrasilane. Ethylene plus silane a t 456' to 51 1' C. react to produce ethyl- and diethylsilane and ethyldisilane. Photochemical activation produced among other compounds butylsilane and 1,4-disilylbutane. Acetylene reacts with silane a t 460' to 514' C. to give some vinylsilane but more divinylsilyl acetylene. Irradiation of silane plus vinylsilane produces several compounds including polyvinylsilane, a white solid. free-radical mechanism is proposed and discussed. Schott and Berge ( 2 0 5 ) have reported that ethyltrichlorosilane is produced when a mixture of ethylene and silicochloroform are excited in the gas phase \vith ultraviolet irradiation. Small amounts of ether act as a catalyst, and in a continuously working apparatus the ethylene adds quantitatively to the silicochloroform. The yields obtained by thermal synthesis are in general greater than those obtained by photosynthesis. The product produced by the latter method is characterized by higher purity. Several organosilicon compounds were prepared by Andreev ( 7 N ) . H e passed a silent discharge through a mixture of silicon tetra-
1558
chloride and cyclohexane (or benzene) roethoxysilanes are reported by Raat atmospheric pressure. Products obthouskf. Chvalovskg, and Baiant (7g.Y). tained include cyclohexyl- and phenylKuniada (7~1~) has prepared organopolytrichlorosilane plus some resinous comsiloxanes by the reaction of trimethl.1pounds. -4 free radical mechanism \vas bromosilane and the corresponding ethsuggested. oxysilanes in a sealed vessel with a pyriTetraarylsilanes were produced by dine catalyst. Yields lvere as high as Brook and Gilman (2.Y). Lvho reacted ?7yc. (Triorganosilyl)phenyl phosrriarylsilanes. High yieids were obphorus derivatives are prepared by a tained and the course of the reaction \vas process patented by Frisch and Lyons investigated. Maienthal; Hrllmann. (JAY). T h e products are drscribed as and others (9.Y) also preparcd some arylbeing useful in flameproofing, antifoanisilanes by using a Grignard reagent. ing applications, lubricant additivrs. and T h e syntheses of seven neir compounds plasticizers. having the trimeth!-lsilylmethyl group directly linked to silicon are described by Sominer. hfurch. and hlitch (23.Y). It METAL ALKYLATIONS is concluded that in reactions involving Several patents !\-ere issued in the last the attack of bulky reagents, the steric year for alkyllead processes. The Eth!.l effects of the trimethylsilylmethyl group are of a magnitude intermediate between Corp. (3P)has patented a procedure for thosr of n-alk!-l and tertiary butyl groups. obtaining highly active sodium-lead alloys. T h e alloys are produced in the Petrov and Sikishin (76.Y) s)-nthesized form of flakes having a maximum dimenand mrasured the properties of several isobutcnylsilanes, isopropenylsilanes. and sion of 9 to inch. T h e use of thew methylsiliconeopcntylacetylene, A Griflakrs is also patented (JP).Liquid alkyl halides or sulfates are contactcd \vith the gnard reag,.nt \viis used in these p r ~ p flakes at 70' to 100' C . to give a tctraarations. ethyl compound. Yields are six times as .Aromatic 11)-drocarbons were alkylated by Petrov. XLlironov, Ponomarenko. 1arg.e as those obtained \vith the usual and Chernyshev (75.\-Jvith sodium-lrad alloys. The improved reac) the products tivity of the flake alloy results from thr. obtained by the substitution chlorination of alkylsilanes and disilane chlorides. preponderance of projecting natura! cr!.std fac:s. Hobbs ( Q P ) has patented Aluminum chloride was used as a cataa p r o c ~ wto prevent agglomeration of the lyst. Namctkin, Topchiev, and Zetkin solid products obtained in the reaction (72-Y) reacted dichloromethane irith a betLveen sodium-lead alloys and ethyl silicon-copper mixture and obtained chloride. , i n oil-soluble surface active 1 1, ~,~.~,j-hexachlorocyclotrimethyleneagent is used. T h e yield of tetraethyltrisilane. This \vas treated \vith alkJ-l lead. based on the sodium-lead allo>magnesium halides to produce various used, was 8SYc. deri\*atives. The reactions of (chloroT h e syntheses of organosilicon, -tin) alkyl) silyl derivatives Ivith trimethyland -lead compounds Ivhich contain a amine have been studied by Sozakura halogen on an aromatic nucleus have ( 7 . 1 5 ) . Pierce! hlcBee, and Cline (77-Y) been reported by Zasosov and Kocheshhave synthesized several fluorine-conkov (22P). Their operating procedures taining organosilanes in which the perare outlined. Ireland (70P)has patented fluoroalkyl group is scparated from the a new process for preparing organotin silicon atom by a n ethylene group. The compounds using a magnesium-tin alloJ-. action of propylmagnesium bromide on T h e alloy \vas poIvdered, rubbed Xvith silicon tetrabromide \vas studied b!' mercury, and rrfluxed \vith cthyl broNametkin, Topchiev, and Kartasheva mide and cyclohexane. Tetraethyltin ( 7 7;Y). They obtained several com\cas produced. V a n der Krrk and pounds including tripropylbroinosilane: Luij ten (73P, 71P) have also prepared a tetrapropylsilane, and a linear pol!-silnumber of organotin compounds. Their oxane. The reaction of propyl bromide procedure for producing tetraethyltin rcith a mixture of silicon and copper a t was similar to that of Ireland. They 300' C. yielded some propyltribromosilalso produced butyltin compounds by a ane. Several organobroinosilanes \ v e x prepared by LlcCusker and Reilly (8-V). I\-urtz reaction. Thz direct s)-nthesis of organotin halides is reported by Smith A new reaction in silicone chemistry was and Rochow ( 7 Y P ) . Copper \vas found observed in the preparation of triphen)-1to be the best catalyst. and silver and bromosilane by the reaction of silicon gold showed some catalytic acti\rity. A tetrabromide and triphenylsilanol. Raserics of other metals did not. hlethyl thouskf, Raiant, and Sorm (78.Y) have chloride was passed through the moltcn measured the reactivity of sweral alktin containing various amounts of copper. oxysilanrs to\vard Grignard reagents. Temperatures of 300' to 350" C. were The reactivity decreased Ivith increased optimum. molecular weight and Ivith branching. Erhylene dialkylborinates tvcre preT h e preparation of methylrthoxysilpared by Letsinger and Skoog (7iiP) by anes and methylpolysiloxanes from chlo~
INDUSTRIAL AND ENGINEERING CHEMISTRY
ALKYLATION means of a Grignard reagent and Icere isolated as the ethylene esters. Schechter ( I S P ) has patented a process for producing trimethyl borate. Boron oxide is added slo\vly with cooling to methyl alcohol at 30' to 60' C. Adding methyl alcohol to boron oxide yields no trimethyl borate. .-by1 titanates icere prepared by Hanic (8P)by heating a mixture of alkyl titanates Lvith phenol for 15 minutes on a steam bath. Yoshida (ZIP) has reviexved tetraalk!-l orthoritanatrs. Organoantimony compounds in which the organic radicals are aromatics \cere synthesized by Glushkoira. Talalaeva. and others ( 7 P ) . .i roentgenographic study was made of the crystals produced. Kuz'min and Kamai (75P)drtermined the values of the parachors and the structurcs of some organic derivatives of arsenic. Somc general rules ivere presented for predicting values of parachors. T h e action of alkyl iodides on esters of phenylalkylarsonous acids \cas determined by Starshov and Kamai (ZOP). hIethyl iodide \vas used for most of the study, but reactions were also run \vith ethJ-1, propyl: and butyl iodides, Several halophosphines \%'ereprepared by Sacco (77Pj icho alkylated phosphorus halides. Phosphorus tribromide was found to be more reactive than p!:osphorus trichloride. ,ilkylation agents include tetraethyltin and -lead. .I patent of Jensen and Clayton ( 7 7 P ) describes the preparation of organic phosphony1 dichlorides. The subsrances are prepared by the action of o x y e n on mixtures of suitable hydrocarbons Lvith phosphorus trichloride. The preferred reaction temperature is 0' to -5' C. Kerosine and lubricating oil fractions are among the most suitable hydrocarbons, and air can he used in place of pure
oxygen. Jensen and Clayton (72P) have also patented a similar process for producing organophosphonyl dichlorides from organic halides. Gamrath ( 6 P ) has patented a procrss for producing alkyl phenyl phosphoric acids and their salts. .ilkylphosphoryl dichlorides are reacted with sodium phenolates \vliile maintaining the reaction mixture alkaline to phenolphthalein. Alkyl phosphites are produced by the patented process of Baker and Broivn ( 7 P ) . Alcohols containing more t!ian three carbons in the chain are reacted lcith phosphoric acid under azeotrope-forming conditions. The resulting {vater is removed in the azeotrope \virh a n inert organic solvent. Fuson: Hammann, and Smith (5P)have prepared a-duio~-lphenyllithium,a ketonic organolithiurn compound. Isopropyllithiurn and tert-butyllithium were prepared by Bartlert. Friedman, and Stiles ( 2 P ) . T h e organic portions of the products \cere found to be highly reactive to simple olrfins.
DEALKYLATIONS -4 process for the dealkylation of alkylated aromatic hydrocarbons has been patented by the Standard Oil Development Co. ( 8 0 ) . The hydrocarbons are brought into contact \vith 1 to 5 moles of hydrogen per atom of alkyl carbon at 300 to 1000 pounds square inch and 1100" to 1800' F. The reaction is preferab!y accomplished in a fluidized bed to maintain temperature control. Benzene, toluene, or &carbon aromatics can be produced as desired. Saivyer (74) has also patented a dealkylation process for aromatic hydrocarbons. T h e h>-drocarhons to be dealk>-lated are
mixed \vith hydrogen a t 500' to 600' C. and at pressures above 100 atmospheres in the presence of a catalyst composed 01 equimolar amounts of the oxides of zinc, molybdenum, and magnesium. S a p h thalene was obtained by Hetzel (34) in a 23Yc yield by passing monomethylnaphthalenes over a heated catalyst in the presence of hydrogen. .4 nickelcobalt catalyst \vas used. Hoatson and Rosenivald (54) have patented a thermal dealkylation process for & j - t e r t alkylphenols. The trrt-alkyl group in the 5-position is removed. The dealkylation of dialkylhydroquinone diacstates with aluminum chloride was studied by \\-ilhams (704). Bruce and Sutcliffr (70) have investigated the reaction of several polymethoxyphenylcyclohes-1-enes with aniline hydrochloride and 48yo hydrogen bromide. They observed that demethylation was accompanied by the fission of the carbon-carbon bond linking the aromatic and alicyclic rings. The reaction of Grignard reagents with @.y-unsaturated ethers \cas investigated by Hill. Haynes, and others (-14). The products obtained \cere unsaturated hydrocarbons and alcohols. The composirion and structure of these reaction products indicate that the Grignard reagents cleave the ethers by 1,2- and 1,l-addition mechanisms. hlanulkin, Tatarenko. and Yusupov (64) have investigated rhr cleavage of radica!s from organometallic compounds by the action of bismuth trichloride. The ease of cleavage of' phenyl groups decreases in the following series: triphenyl bismuth. diphenyl mercury. and triphenyl antimony. I n a n inert atmosphere. onl>-dearylation takes place but in the absence of a protective atmosphere, the reacriori with triphenyl anti-
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"Alkylation continues to assume increasing importance in the petroleum industry. The alkylation of isobutane which played a major role in the production of aviation gasoline during World W a r II has achieved new significance as a means of obtaining isoparaffins to be added to catalytically reformed gasoline rich in aromatics, thus both balancing its composition and maintaining its octane number. Alkylation of aromatic compounds yields oxidation inhibitors for gasoline and food products and antioxidants for rubber, as well as intermediates for the preparation of such diversified compounds as alkylbenzenesulfonates, styrene, phenol, and acetone." Louis Schmerling, Coordinator Exploratory Research Division Universal Oil Products Co.
UNIT PROCESSES REVIEW mony is essentially a n oxidation-reduction with some dearylation. Additional studies by Cooke, Gerrard, and Green ( Z Q ) have been reported on the removal of alkyl groups from esters of phosphorus acids with a hydrogen halide. T h e weight of the alkyl halide indicates the progress of the dealkylation. Tsuda, Sato, a n d Saeki ( S Q ) have studied the migration of the benzyl group from nitrogen to the carbon of the methyl group of a- a n d y-picolines. T h e i r operating procedures and results are outlined.
Acknowledgment
(20D) Schmerling, L.:\Vest: J. P., Ibid., 7 6 , 191--21 (1954). (10B) Sunagawa, G., Oyamada, K., Ann. (21D) Shirley, D. .A,. Zietz, J . R., Zbid., Rejt. Takamine Lab. 3 , 28-30 7 5 , 6333-4 (1353:. /rncr \ ( I Y J I ). 122D) Shuikin. h-.I . . Kuchkarev. A. B.. Pozdnyak, k. .A,. IZLCS~. Akad: .)-auk S.S.S.R., Otde!. Khirn, .Vauk: 1954, pp. 904-10. CARBON-CARBON AROMATIC (23D) Shuikin: N. S.:Kuchkarev, A , B., ALKYLATIONS Pozdnyak, N. A , , Doklady Akad. -Vmk S.S.S.R. 9 2 , 785-8 (1953). ( I C ) Boekelheide. V., Goldman, XI.. J . (24D) Sidorova. N. G.: Tsukervanik, I. Org. Chcm. 1 9 , 5-3-86 (1954). P.: Pak. E.: Zhur. ObshchPi Khirn. ( 2 C ) Dannlev, K. L., Greys, E. C., J. 2 4 , 94-6 ii954). .lm. Cixm. Scc. 7 6 , 2997-3000 (2SD) Simons. J. H.: Black. I V . T., Clark, (1934). R . F., J . Ani. Chem. Soc. i5, (3C; Goerner, G. L.: LVorknian, i1’. R., 3621-2 11933 1 . J. 078. Cficm. 1 9 , 37-40 (1954). (26D) Topchiev, .I,V...\ntireev, L. N , , ( 4 C ) Hart. H., Cassis, F. A , Bordeaux. Krentsel. B. A.. D d l a d y Akad. J . .J., J . A m . Chem. Soc. 7 6 , 1639-41 .VUU/: S.S..S.R. 9 2 , i”-80 (1953). i 1 9 54),. (2-D) Topchiev, .4. V..Krentsel, B. A, (5‘2) Hart. H., Cassis, F. h.,Ibid., 7 6 , ;\ndreev, L. S., Ibid.. 9 2 , 781-4 1634-9 (1954). (1953). (6C) Hart. H.. Eleuterio, H. S.: Ibiii.. (2871 j Vdovtsova! E. -4.: Tsukervanik, 7 6 , 516-19 (1954). I. P., Sboriiit Sta!/iObsfichei Khim. 17Cj Hart. H.. Spliethoff. 1V. L.. Illeii2 , 1027-34(1953:. terio. H. ‘S,>Ibid:, 7 6 , 4547-50 (29D) Vdovtsova. E. A , , Tsukervanik, (1954). I. P..Dol;la(v Akad. +YaukS.S.S.R. (8C) Rodionov. V. 11.. Belov. 1’. 3.; 8 0 , 61-4 (1951). Kore. S. .A,. Zhur. Obsiirhfi Lhini. (30DJ Vig, 0. P., Sandhu: S. S., Science 2 3 , 1802-8 ( 1 9 3 3 ) . and Culture (India) 1 9 , 311-12 (1953). (9B) Stiles,
R., Petroleum Rq5ner S o . 2, 103-6 (1955).
34,
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It is a pleasure to acknolvledge the valuable assistance in searching, checking, and abstracting the literature contributed by Pa Huong Sheng and Elizabeth Prentiss.
BIBLIOGRAPHY ( I A ) Campbell, A. \v., I N D . ENG.C H E X . 4 7 , 1213-16 (1955). (2A) Davies, A. G.. Foster, R . V., White, A. XI., J . Chem. Soc., 1954, pp. 2200-4. (3A) Dolgoplosk, B. A , Erusalimskii, B. L.. others. Zhur. Obshchei Kiiim. 2 4 , f775-82 (1954). (4A) Ford, M ,C . . Hunt, L. J., LVaters, 11’. A . , J . Chem. Soc., 1953, pp. 3529-33. ( 5 A ) Franklin, J . L.. Shepherd, G. R . L.. J . A m . Cfzem. Soc. 7 6 . 609-10 (1954). Gamrath. H. R., Hatton, R . E. (to Slonsanto Chemical Co.), U. S . Patent 2,707,176 (April 26, 1955). Kovacic, P., IND. EYG. CHEX.4 7 , 1090-4 (19%). Levv, hf., Szwarc, X I . , J . Chttm. Phys. 2 2 , 1621-2 (1954). McBay, H. C., Tucker, O., Milligan, .4., J . o r g . Chem. 1 9 , 100317 (1954). Pritchard, G. O., Pritchard, H. O., Trotman-Dickenson, A. F., J . Chem. Soc., 1954, pp. 1425-8. (11.4) Tarrant, P.: Lovelace, A. ?*I J . A m . Chem. Soc. 7 6 , 3466-8 (1&4).
CARBON-CARBON ALIPHATIC ALKYLATIONS (1B) Bacchetti. T., Chimica e industria (Xlilan) 3 5 , 619-21 (1953). (2B) Bailey, \V. J., Ivladoff, hI., J . Am. Chem. Soc. 7 6 . 2707-8 (1954). (3B) Horeczy, J. T:, Boynton, H. G. (to Standard Oil Development C o . ) , U .S. Patent 2,690,460 (Sept. 28,1854). (4B) Kondo, S. (to Organic Synthetic Chemical Industries Co.), Japan. Patent 5312 (1953). (5B) Mandelcorn, L., Steacie, E. W.R., Can. J . Chem. 3 2 , 474-84 (1954). (6B) Piehl, F. J., Brown? W.G., J . A m . Chem. Soc. 7 5 , 5023-6 (1953). (7B) Reesor, J. TY. B.! Smith, J. G., M‘right, G. F.: J . Org. Chem. 1 9 , 940-56 (1954). (8B) Rupp? W. H . (to Standard Oil Development Co.), U. S . Patent 2,701,184 (Feb. 1, 1955).
1560
Friedel-Crafts Type Catalysts (1D) Broivn, H. C., Nelson. I Akad. JVauk S.S.S.R. 1 , 322-4 (1953). (4D) Eley, D. D., 11’atts. H.. J . Chem. SOC.,1954, pp. 1319-24. (5D) Kilpatrick, XI. 0. (to Phillips Petroleum C0.l: U. S. Patent 2,701,181 (Feb. 1, 1955). (6D) Krentsel, B. .A,, Topchiev, .A. V., .\ndreev, L. S.,Doklady Akcid. .\‘auk S.S.S.R. 9 8 , 75-8 (1954). (7D) Kunugi, T., and Kudo. H . ; J . Chem. Soc. Japan, Znd. Chem. Sect. 5 7 , 728-31 (1954). (8D) Sianne. R. S. (to Standard Oil Development C o . ) , C . S. Patent 2 , 6 7 4 , 6 3 7 (April 6, 1954). (9D) Sledcalf. E. C., Vrien;, G. S . (to .American Cyanainid Co. ), Ibid., 2,694,095 (Kov. 9, 1954:. (10D) Xlukheiji: S. SI,,Vi?. 0. P..others. J. Org. Chem. 1 3 , 1139-1505 (1953). (11D) Xiederhauser, \V. n.(to Rohm A Haas C o . ) , U. S. Patent 2,689,873 (Sept. 21: 1954). (12D) Paltz, I V . J.: Tegze: B. R. (t; Standard Oil Development C o . ,, Z6id., 2,667,519 (Jan. 26, 1934). (13D) Pedreira: J. N. (to Laboratories Espaaolas “Zeltia“ S.X.), Span. Patent 202,470 (Dec. 22. 1953). (14D) Petrov, A. A , , Leets, K. V.? Do/;lady ilkad. .\‘auk S.S.S.R. 9 5 , 285-8 (1954). (15D) Petrova, A . hl., Zhur. Obshchei Khim. 2 4 , 491-3 (1954). (16D) Pishnamazzade, B. F., Trudy Znst. Kfiim., Akad. Sauk Azerbaidzhan. S.S.R. 1 3 , 49-89 (1954). (17D) Kaha. C . R . , J.A m . Chem. Soc. 7 6 , 622-3 (1954). (18D) Ruhrchemie .I.-G., Brit. Patent 711,793 (July 14, 1954). (19D) Sanford. R. A , ; Kovach, S. hi., Friedman, B. S., J . A m . Chem. SOC.7 5 , 6326-7 (1953).
INDUSTRIAL AND ENGINEERING CHEMISTRY
Hydrogen Fluoride Catalysts (1E) Goodhue, L. D., Tissol, C. E. (to Phillips Petroleum Co.), U. S. Patent 2,704,246 (.\larch 15, 1955). ( 2 E ) SlcCaulay. D. :I., Lien, A . P. [to Standard Oil Co. (Indiana)], Ibid., 2,700,689 (.Jan. 2 5 . 1955) ( 3 E ) N. V. de Battaafsche Petroleum Xlaatschappij, Dutch Patent 77,119 ( J a n . 15; 1955). (4E) O r r , .A. R.. Oil Gas .J. 5 4 , N o . 13. 102-4 11933’t. (5E) Peters. 11’.‘D., Rogers. C. L.. Petroleum ReJiner 3 4 , S o . 9 , 126-8 (1955). (6E) Schneider, A. (to Sun Oil Co.), U. S. Patent 2,712,033 (June 28, 1955).
Other Acid Catalysts (1F) Egloff: G.. \Velnert: P. C., Proc. 3rd Tl-orld Petro!evnz Conzr.,Hague 1951, Sect. IV. pp. 301-14. (2F) Kennedy, K. Sl., Schneider, A. (to Sun Oil C o . ) , U. S . Patent 2,683,75-4 ( J u l y 13. 1954). (3F) Krentsel, B. X.. Topchiev, A. V., Andreev. L. N., Ooklady Akad. S a u k S.S.S.R. 9 2 , 319-22 (1953). (4F) Langlois, G. E., LValkey, J. E., Petroleum Rt9ril.r 3 1 , S o . 8. 7983 (1952:. (5F) Lenneman, \V. L., Hites. R. D., Komarmvsky. V. I.: J . Org. Chem. 1 9 , 463-8 (1954). (6F) llamedaliev, Y.G.:Veliev, S . V., Doklady .4l:ad. .Yauk S.S.S.R. 9 2 , 325-8 (1953). (7F) N. V. de Bataafsche Petroleum Slaatschappij? Brit. Patent 706 ,653 (>larch 31, 1954). (8F) Romadane. I., RodinS, E., Latvijas PSR Zinitnu Akad. fistis 1954, No. 6: pp. 115-18. (OF) Topchiev. A. V.: Kurashev, X I . V., Paushkin, Y. l l . , Doklady Akad. .Vauk S.S.S.R. 9 3 , 839-42 (1953). (10F) Topchiev, A. V., Tumerman, B. I f , , others, .\-e,ftyanoe Khor. 3 2 , No. 7 , 6 5 4 (1954). (11F) Zavgorodnii, S . V., Doklady Akad. Xauk S.S.S.R. 9 7 , 257-9 (1954).
ALKYLATION (12F) Zavgorodnii, S. V., Faustova, E. hi., Zhur. Obshchef Khim. 2 3 , 1651-4 (1953). (13F) Zavgorodnii, S. V., Gostev, hl. SI., Zhur. Obschei Khim. 2 4 , 2002-6 (1954).
Miscellaneous and General Catalysts (1G) Babayan, A. T., Gambaryan, X: Gambarpan, K. P., Zhur. Obshchei Ahini. 2 4 , 1887-93 (1954). (2G) Badisclie tinilin Br Soda-Fabrik, Gcr. Parent 767,794 (July 20, 1954). (3G) Caiiquil, G., Barrera: H.: Barrera, R., Bull. SOC. chim. France, 1953, D D . 1111-16. (4G) Cdn'ia, J. 51.: Compt. rend. 237, 91U-12 (1953). ( j G ) Conia, J . l l . >Bull. soc. chim. France, 1954, pp. 943-8. (6G) Dolgov. B. S . , Cherkasov, .A. S., Zhur. Ohshchei Khim. 2 4 , 825-33 (1994). ( 7 G ) Freidlin, L. K., Balandin, A. A . , Sazarova, N. hl., Doklady Akad. .\-auk S.S.S.R. 9 6 , 1011-14 (1954). (8G) Henne, A. L., Tedder, J. Sl., J . Chem. Soc., 1953, pp. 3628-30. (9G) Kindler, h.;Ger. Patent 824,058 (Dec. 10: 1951). (10G) Slamedaliev, Y. G.: L'eliev, S. V.: DoiJady d k a d . .\-auk S.S.S.R. 9 2 , 573-511953). (11Gj OKurr. LV. C . (to Gulf Research &r De:.elopment C o . ) , U. S. Patent 2 , 6 8 4 , 3 8 9 (July 20: 1954). (12G) Shuikin. N. I., Pozdnyak, X. A , Sbornil, Statei Obshchei Khim. 2 . ioos-13 (1953). (13G) Ibid., pp. 1014-19 (1953). (14G) Sidorova, S. G., Tsukervanik, I. P., Abidova, Z. K., Doklady Al;ad. .\-auk L-zbek. S.S.R., 1953, S o . 5. pp, 33--. (15G) Smith, \V. C., Slasterton, B. (to Shell Development C o . ) . L.S. Patent 2,678,551 (hIay 18; 1954). (16G) Tiganik, L. (to Uddeholms Aktiebolag), Sxved. Patent 145,290 ( S h y 18,1934). (17G) Topchiev, .A. V.: Bogomolova, Pi. F.: D d l a d y Airad. .\-auk S.S.S.R. 8 8 , b91-2 (1953.1. (18G) Tsutsunii. S., Yoshijima, T., Koyama, K., J . Furl SOC.Japan. 34,145-50(1955j. (19G) Turova-Pollak: 11, B., Danilova, S , V.,Treshchova, E. G., Zhur. O b r i i c h e i ~ i i i m . 2 1 , 1 5 5 8 - 6 2(1954).
CARBON-CARBON ALKYLATIONS Grignard Reagents Ahmad, R., LVeedon, B. C. L., J . Chcm. SOC.,1953, pp. 2125-9, Cuvignp, T., Sormant, H., Compt. rend. 2 3 7 , 815-17 (1953). Dreus: J., Bull. SOC. chim. France, 1954, pp. 1309-12. Field, L.: SIcFarland, J. TV., J . A m . Chem. Sac. 7 5 , 5582-6 (1953). Fuson, R. C., Freeman, J. P., Ibid., 7 6 , 911-12 (1954). Gilman, H., Jones, R . G., Woods, L. A , Ihid., 7 6 , 3615-17 (1954). Ginzburg, 0. F., Zhur. Obshchei Rhinz. 2 3 , 1682-5 (1953). Lamneck, J. H., 'Wise, P. H., J . A m . Chem. Sod. 7 6 , 1104-6 (1954).
i 9 H i Landrum. B. F.. Lester. C. T.. Ihid., 7 6 , 5797:8 (1954j. (10H) Lapkin, I. I.: Puchkin, iY. hi.? Lykov, P. .I.,Sbornik Statei Ohshchei Khim. 2,823-7 (1953). (11H) Levina, R . Y . , Shabarov., Y. S., Skvarchenko, V. R.. Vestnik .Maskois. C n i i . 9 , No. 2 , Ser. Fi:, M a t . i. EstestLen. .Vaui; KO. 1: 63-7 (1954). 112H) \ - ~ - - - * Lukovnikov. A. F.. Xeiman. SI. B.] others, Doklady Akad. '>Yauk S.S.S.R. 8 8 , 297-300 (1953). ( l 3 H ) Petrov, A . D., Chernyshev, E. X., Trudy T-sesoyu:. So&hchaniya po Khim. i. Pereraboth ;L'ejti., 1951, Akad. ' V a d dzerhaidzhan. S.S.R., 1953, pp. 39-43; Referat. Zhur. Khim.. 1954. No. 23354. (14H) Pohland, A , , 'Sullivan, H. R.. J . .4m. Chem. SOC. 7 5 , 5898-9 \
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I
119i?) \ - - - - / .
( l 5 H ) Prout, F. S., Huang, E., others, Ibid., 7 6 , 1911-13 (1954). (16H) Rabjohn. N., Latina, 51. J.. Ibid., 7 6 , 1389-90 (1954). (17H) Tarrant. P.. iVarner. A. D., Ihid. 76,1624-j (1954).
Complex Alkylations ( l i ) .Am, Asioc. Textile Chemists Colorists: Rhode Island Section, A m . Djes?uf Reptr. 4 3 , Proc. A m . Assoc. Tastile Chern. Colorists, P774-9
(1954). (2ij Baumgarten. H. E., Eifert, R . L.: J . d i n . Chem. Soc. 7 5 , 3015-16
(2Oi) Prevost, C., Seguin, P., others, Bull. soc. chim. France, 1953, KO. 10, (219-22. (21i) Pudovik, A. S . , Denisova, G. ?vi., J . Gen. Chcm. (L-.S.S.R.) 2 3 , 2736 (1953). (22i) Quelet, R., Bull. SOC. chim. France, 1953, NO. 10, C 46-8. (23i) Rabjohn, N., J . A m . Chem. SOC.7 6 , 5479-81 11954). (24ij Randall, D: I.. Renfrew, Is. E. (to General Aniline &r Film Corp.), U. S. Patent 2,662,902 (Dec. 15, 1953). 76, (25i) Summers. L.. J . Am. Chcm. SOC. 3481-4( 1954). (26i) Terent'ev, A. P., Butskus, P. F., Doklady Akad. 'Vauk S.S.S.R. 9 7 , 851-3 (1954). (27i) Terent'ev, A. P., Klabunovskii, E. I., and Budovskii, E. I . , Sb07nik Statei Ohshchei Khim. 2 , 1521-9 (1953). (28i) LVichteile. O., Cerny, J., Chem. Listy 4 9 , 1038-40 (1955).
Miscellaneous (1J) Baker. L\-., Harbornc, J. B., others, J . Chem. Sac., 1954, pp. 2042-6. (23) Noland, I\-. E., Hartman, P. J., J . Am. Chem. SOC. 7 6 , 3227-8 (1954). 13J) N. V, de Bataafsche Petroleum llaatschappij, Brit. Patent 695,076 (Aug. 5,1953). (45) Sidorova, S . G., Zhur. Ohshchei Khim. 2 4 , 255-9 (1954). \
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11953 1.
(3i) Bruson: H. A . , Rimer; T. \I-., Ibid.: 75,3585-6(1953). (4i) Compton. 3.. Xlartin, \V. H.. others, Textiie Rescarch J . 2 5 , 58-75 (1955;. ( j i ) Daul, G. C . : Reinhardt, R. SI., Reid: J. D.: Ibid., 2 5 , 246-53 (1955). ( 6 i ) Dzbanovskii, K. .A,. Sfarochko, S. V.. Kost. A . S . . Sbornil, Siatei Obshchei Khim...4/;a'd. ithuk S.S.S.R: 1 , 60'-9 (1953). (;ill Gault. H.. Bull. SOC. chim. France, 1953, SO.10, C6-C-. (8i) Grant. J. I.,Greathouse, I>. H., others. Textile Research J . 2 5 . 76-83 (1955). (9i) Gudriniece. , E . , Rozite, L.,Lepika, E.: L a t i c a s P S R Zinatnu Akad. l k d s 1954, KO. 11 (\\'hole NO. 88'1 - - , D D . 111-14. ( 1 O i ) Haas, H. C.: Cohen, S. G., others, J . Poiymer Sci. 1 5 , 427-46 (1955). ( l l i ) Jones, G. D. (to Dow Chemical Co.), U. S. Patent 2,694,702 ( S o v . 16, 1954). (12i) Krausz, F., Bull. sac. chim. France, 1953, SO.10, C51-2. (13i) Larramona, H., Tchoubar, B., Bull. SGC. chim. France, 1953, No. 10, (253-8. (14i) Lichtenberger, J., lIuller? P., Hup e t , SI,, Ihid.: 1953, No. 10, C45-6. (15i) Xiaquin, C., Gault, H., Ibid.. 1953, C48-9. (16i) Misra, G. S.,Shukla, J. S.. J . Indian Chem. SOC.2 9 , 455-7 (1952). (17i) Nazarov, I. N., Shvekhgeimer, G. A., Rudenko. V. A. Zhur. Obshchei Khim. 2 4 , 319-29 (1954). (18i) Piazarov, I. N., Zav'yalov, S. I., Zhur. Ohshchei Khim. 2 4 , 469-74 (1954). (19i) Petrov, A. A., Sbornik Statei Obshchei Khim., Akad. h'auk S.S.S.R. 1 , 362-8 (1953). I ~ I
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CARBON-OXYGEN ALKYLATIONS ( 1 K ) Abe, T., SLatsuzaki, K., others, Textile Research J . 2 5 , 254-6 11955) -\ - -
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( 2 K ) hdler, E., Gierer, J., Acta Chem. Scmd. 9 , 84-93 (1955). ( 3 K ) Xstoul. R . R., Span. Patent 212,920 (March 18, 1954). (4K) Borodina, G. l l , , Shchukina, Sf. N.. Shornik Statei Ohshchei Khim., d X a d . .Vauk S.S.S.R. 1 . 382-4 (1953). (5R) Burtle. J. G.. Turek, Lt'. S . , J . A m , Chem. SOC.7 6 , 2498 (1954). ( 6 K ) Chase. B. H., [Valker, J., J . Chem. SOC..1953, pp. 3518-25. (7K) Inhoffen. H. H., Bruckner, K., Grundel. R.. Chem. Ber. 8 7 , 1-13 (1954). (81;) Laboratories Dausse. Brit. Patent 717,900 ( S o v . 3, 1954). (9K) Lindberg, B.: IVickberg, B., Acta Chem. Scnnd. 8 , 569-73 (1954). (10K) Manabe, O., Hiyama, H., J . Chcm. Soc. Japan, I d . Chem. Sect. 5 7 , 164-6 (1954). (11K) hlatsuura, T.. Japan. Patent 4920 (Sept. 30,1953). (12K) Newman, hl. S., Evans, F. J., J . A m . Chem. SOC. 7 6 , 4187-8 (1954). (13K) Patai. S., Bentov, M.,Ihid., 74, 6118 (1952). (14K) Petrie, P. S., Britton, E. C. (to DOW Chemical Co.), L. S. Patent 2,694,087 (Nov. 9, 1954). ( l 5 K ) Reeves, R. E., Armstrong, A. c., others, Textile Research J . 25, 257-61 (1955). (16K) Seleznev, A. K., Balakirev, A. A., Zhur. Priklad. Khim. 27, 650-5 (1954). (17K) Shirley, D. A,, Zietz, J. R., J . Org. Chem. 18, 1591-3 (1953).
VOL. 48, NO. 9, PART II
SEPTEMBER 1956
156 1
UNIT PROCESSES REVIEW (18K) Simonetta, hi.: Favini, G., Atti accad. nazl. Lincei, Rend., Classe sci.js., mat. e nat. 16, 84-8 (1954). (19K) Wenkert, E., Bose, .4.K.: Reid, T. L., J . A m . Chem. Soc. 75, 5514-16 (1953). (20K) \Villiams, \V. W.,Freyermuth, H . B. (to General Aniline gi Film Cor‘p.). U. S. Patent 2,713,046 (July 12, 1955).
CARBON-NITROGEN ALKYLATIONS (1L) Abe, K.? Tsukamoto, Y . , Ishimura, A , J . Pharm. Sac. Japan 73, 1319-22 (1953). (2L) Aktiebolaget Astra Apotkarnes Kemiska Fabriker, Brit. Patent 705,460 (March 10, 1954). (3L) Allen, C. F. H . , Reynolds, G. A , , J . A m . Chem. SOC.74, 5801 (1952). (4L) Babayan, A. T., Gambaryan, N. P.: Gambaryan, N.,Doklady Akad. ,Vauk Armyan. S.S.R. 17, No. 2, 39-44 (1953). (5L) Bolle, J., llousseron, M., Bourgeois, L., M e m . seroices chim. &at (Paris) 38, 147-57 (1953). (6L) Bridges, R. G., J . Sci. Food Agr. 6,261-8 (1955). ( 7 L ) Cast, J.; Stevens, T . S., J . Chem. SOC.,1953, pp. 4180-1. (8L) Chenicek, J. A . (to Universal Oil Products C o . ) , U. S. Patent 2,700,612 (Jan. 25, 1955). (9L) Coffman, D. D., Hoehn, H . H., Llaynard, J. Y.,J . Am. Chem. Soc. 76, 6394-9 (1954). (1OL) Cook, P. L., Cniti. .Microjims Publ. No. 10,461, 58 pp.; Dissertation Abstr. 15, 37-8 (1955). (11L) Eichenberger, K., Staehelin, A , Druey, J., Heli. Chim. Acta 37, 837-48 (1954). (12L) Gerrard, I%’., Jeacocke, G. J., Chemistry t Y Zndustrj, 1954, pp. 1538. (13L) Hamor: G. H., Soine, T. O., J . A m . Pharm. Assoc., Sci. Ed. 43, 120-3 (1954). (14L) Hirbs;, ’R, XI., Percival, D. F., J . Org. Chem. 19, 439-40 (1954). (15L) Humphreys, D. D. (to Sharples Chkmic’als Inc.), U. S. Patent 2,685,604 (Aug. 3, 1954). (16L) Klamann, D., Schaffer, E., Chcm. Bpi. 87, 1294-1300 (1954). 117L) Petrov. K. D.. Sbornik State; Obshchei Khtm., Akad. ,Vaui, S.S.S.R. 1, 374-7 (1953) Plieninger, H., Chem. Ber. 87, 1279 (1954). Pochinok, V. Y . , Portnyagina, V. A., Ckrain. Khim., Zhu;. 18, 6314 (1952). (20L) Potts, K. T.: Saxton, J. E., J . Chem. SOC.? 1954, pp. 2641-3. (21L) Pratt, E. F., Frazza, E. J., J . A m . Ciiern. Soc. 76, 6174-9 (1954). (22Lj Shimo, K., Asami? R . , Bull. Chem. \
I
Research Inst. >\-on--dq.
Solns., 4,
69-’3 (1954). (23L) LVard, S.:Lamb, S. A. (to Imperial Chemical Industries Ltd.), Brit. Patent 716,239 (Sept. 29, 1954). (24L) Zaniboni, P., Vitali. T., I1 Farmaco, Ed. Sci. (Pavia) 8, 590-605 (1953).
CARBON-SULFUR ALKYLATIONS (151) Barrett. K . E. J . , and \Vatem. W. A , ; Discussions Faraday SOC.,1953, SO.14, pp. 221-7.
1562
(2M) Beach, L. K., Barnett, A. E. (to Standard Oil Development Co.), U. S. Patent 2,667,515 (Jan. 26, 1954). (3M) Bordwell. F. G., Andersen, H. hi., Pitt, B. lf., J . d m . Chem. SOC. 76, 1082-5 (1954). (4M) Cooper, G. D., Ibzd., 76, 3713-16 (1 \ 954 ). , ( 5 M ) Emmons, \V. D., Ferris, .4. F., Zbid., 75,2257 (1953;. ( 6 h l ) hfahan, J. E. (to Phillips Petroleum Co.)?U. S.Patent 2,689,867 (Sept. 21,1954). (751) Pudovik, A. N., Kovyrzina, K. A , , Zhur. Obshchei Khim. 24. 30711 (1954).
CARBON-SILICON ALKYLATIONS ( 1 s ) Andree\r. D. N., Doklady AXad. S a u k S.S.S.R. 100, 263-5 (1955). (2K) Brook. A . G.. Gilman. H., J . A m . Chem. Soc. 76, 2333-8 (1954). ( 3 N ) Daudt. L‘;. H . (to Don Corning Corp. 11; E. S. Patent 2,672,475 (5larch 1 6 , 1954). Frisch, K. C., Lyons. H. (to General Electric Co.), Zbid.. 2,673,210 (March 23, 1954). Fukukawa, S., Science and Ind. ( J a p a n ) , 28, 71-4 (1954). Ibid., pp. 75-6. Kumada, hi., J. Chem. Sac. Japan, Ind. Chem. Sect. 55, 752-4 (1952). McCusker, P. A , , Reilly, E. L., J . A m . Chem. SOC. 75, 1583-5 (1953). Plfaienthal. 51., Hellmann, h f . , others, Zbid., 76, 6392-3 (1954). hfertens. LV., Ger. Patent 823,450 (Dec. 3: 1951). Nametkin, iY.S.:Topchiev: .4.V., Kartasheva. L. I., Doklady ,4kad. Al’auk S.S.S.R. 93, 66--9 (1953). Nametkin, N. S.,Topchiev, A. V.: Zetkin, V. I., Ibid.. 93, 1045-7 (1953). ( 1 3 5 ) Noll. LV., Simons. P.; Ger. Patent 824,049 (Dec. 10. 1951). (14N) Xozakura. S.,J . Chem. SOC.Japan: Pure Chem. Sect. 75, 421-31 (1954). (15K) Petrov, A . D., hlironov: V. F., others, Doklady Akad. .Vauk S.S.S.R. 97, 687-90 (1954). (16N) Petrov, 4.D., Xikishin; G. I . ; Zbid., 93, 1049-52 (1953). R., hIcBee. E. T.. Cline, (17N) Pierce, 0. R. E., J . A m . Chem. Soc. 75, 5618-20 11953). (18N) Rathousk$,‘J.. Baiant. V.. Sorm, F.. Chem. Listy 48, 1197-1204 11954). (19N) Rathousk$. J., Chvalo\sk$. V., Baiant, V., Zbid.. 47, 1387-93 (1953). (20N) Schott. G.: Berqe. H.. Chern. Tech. (Berlin) 6 , 503-4 (19541. (21N) Sekino. hi.. Hani. H. (to Xsahi Glass Co: 1. Japan. Patent 421 (Jan. 29. 19341. ( 2 2 9 ) Smith. Bengt, lloktorsaihandl. Chalmers T e k . HopsLula. S o . 6, 154 ~. pp, (1951 1. (23N) Sommer, L , H.. lfurc!1. R. hf., hfitch. F. -4.. J. Am. Chem. SOC. 76, 1619-21 (1334). ( 2 4 2 ) Takahashi. Haruo: Shiqeniwa. Y. (to Hidachi Xianufg C o . ) , Japan. Patent 2962 (\lay 29. 1954). (25N) Tramliouze. P.. Imelik. B., J . chiin. p h i s . 51, 505-14 (1354). (26N) LVhite: D. G.. Kocho;v. E. G.. J . A m . Cheni. SOC. 76, 3897-3902 (1954).
INDUSTRIAL AND ENGINEERING CHEMISTRY
’
METAL ALKYLATIONS Baker, A. A,, Brown, J. H. (to Oldbury Electro-Chemical Co.), C . S. Patent 2,670,368 (Feb. 23, 1954). Bartlett, P. D., Friedman, S., Stiles, hi., J . Am. Chem. SOL.75, 1771-2 (1953). Ethyl Corp., Brit. Patent 707,074 (April 14, 1954). Zbid., 707,075 (April 14, 1954). Fuson, R . C.. Hammann, \V. C., Smith, W. E., J . Org. Chem. 19, 674-7 (1954). Gamrath, H. R. (to hfonsanto Chemical Co.), U. S. Patent 2,656,374 (Oct.’20: J953). (7P) Glushkova. V. P., Ialalaeva, T. V.. others. Sbornik Stntei Obshchei Khim. 2, 992-6 (1953). (8P)Hanic, F., Chem. Listy 49, 370-2 (1955). (9P) Hobbs; C . L. (to E. I. du Pont de Nemours 6r C o . ) . L.S. Patent 2,686,799 (Aug. l’, 1954). (1OP) Ireland, J.: Brit. Patent 713,727 (Aug. 18, 1954). (11P) Jensen, W. L.: Clayton, 3. 0.(to California Research Corp.), U. S. Patent 2,683,168 (July 6, 1954). (12P) Zbid., 2,683,169 (July 6, 1954). (13P) Kerk, G. J. If. van der, Luijten, J. G. A , , J . Applied Chem. (Londonj4, 301-’(1954). (14P) Zbid.: pp. 307-13. (15P) Kuz’min. K. I., Kamai, G., Sbornik Statei Ohshchei Khim., Akad. Nauk S.S.S.R. 1, 223-8 (1953). (16Pj Letsinger, R . L., Skoog, I.; J . A m . Chem. Soc. 76. 4174-6 11954). (17P) Sacco, A , , “itti accad. nazl. Lincei, Rend., Classe sci. j s . , mat. e nat. 11, 101-5 (1951). (18P) Schechter, \V. H . (to Callery ChemC o14: . ) ,1954). L. S. Patent 2,689,259 (Sept. ical (19P) Smith, r\. C., Rochow, E. G., J . ;Im.Chem. SOC.75, 4103-5 (1953). (2OP) StarshoLS; I. X i . > Kamai, G., Z h r . Obshchei Khim. 24. 2044-9 (1954). (21P) Yoshida, I.; Kagaku no Ry8tki 5 , 414-16 (1951). (22P) Zasosoir. V. X., Kocheshkov, K. A., Sbornik Statei Objhrhei Khim., Akad. .\‘auk S.S.S.R. 1, 278-84 (1953).
DEALKYLATIONS (1Q) Bruce, J. At., Sutcliffe, F. K., Chemistry & Industry, 1955, p. 7, 4,I.5
(2Q) Cooke, V. F., Gerrard, W.,Green, M‘. J., Zbid., 1953, pp. 351-2. ( 3 4 ) Hetzel, S. J. (to Sun Oil C o . ) , U. S . Patent 2,698,869 (Jan. 4, 1955). (4Q) Hill, C . hf.. Havnes, L., others, J. A m . Chem. Soc. 75, 5408-9 (1953). (5Q) Hoatson, J. R.. Rosenivald, R. H. (to Universal Oil Products Co.), 1 - S. Patent 2.676.191 (April io.1954). Slanulkin, Z. hl.. Tatarcnko. A. N.; Yusupov, F.. Sbornik State? Obshchei Khim.2, 1308-14 (1953). SaLvyer. E. 1%‘. (to Imperial Chemical Industries Ltd.). Brit. Patent 704,535 (Feh. 24. 1354). Standard Oil Development Co., Zbid., 712,440 (July 21, 1954). Tsuda, K.. Sato, Y.. Sacki. S . , Pharm. Bu!i. 1, 30’-19 (1953). Williams. .J. L. R.. J. A m . Cliem. Soc. 74, 6132-3 (1952). I
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