UNIT PROCESSES
Oxidation-Liquid Phase
Tm
use of air or oxygen upon organic compounds for introducing functionality presents a n appetizing carrot to the chemical industry. I t is inexpensive and readily available, but not necessarily sufficiently selective. O n e of the broad objectives of research in this field today is to improve this selectivity. Activity is divided into two approaches: a search for better catalysts and conditions which will permit utilization of the oxygen directly, and the use of other oxidizing agents which themselves may be regenerable with oxygen. T h e latter, although involving a n added processing step, has the potential merit of high selectivity in the point of attack and in the nature of the product. Both approaches received about equal attention during the past year. Production of the phthalic acids continues to make news. Amoco a n nounced completion of a new plant for catalytically air oxidizing the xylenes. Mitsui Petrochemical Industries in Japan is operating a similar plant to produce terephthalic acid for Terylene. IC1 in Great Britian is rumored to have taken a license to use the Amoco process. Oronite is now marketing terephthalic acid made by the process used for Isophthalic, which reportedly employs inorganic sulfur species as a chemical oxidant. ~~~~~
W. G. TOLAND is a senior research associate with the California Research Corp., where he has been a member of the staff since receiving his Ph.D. from Purdue in 1944. Particularly concerned with exploratory research, he has been most active in the field of oxidation of organic compounds, in which he has been granted a number of patents and has several publications. He is a member of ACS, Phi Lambda Epsilon, and Alpha Chi Sigma.
1 130
A plant for a broad range of normal primary alcohols was announced by Continental Oil. T h e Ziegler process is to be used to make the aluminum alkyls, which a r e then oxidized to the alcoholates and hydrolyzed. Throughout the field of liquid phase oxidation can be noted a n increased interest in the use of emulsion systems to avoid solubility problems, increase interfacial contact, and control reaction rates. Autoxidalions
Our present understanding of the fundamental processes of autoxidations, including the mechanism of the chain reactions involved, was brought u p to date in a recent article by Russell (47A). Some of the macroscopic steps have been considered (33A). T h e nature of trace metal catalysis has been discussed ( 3 A , 79A) Aromatics
Aromatic Acids, Oxidation of alkyl aromatics to favor the phthalic acid isomers continues to receive attention. Two polybasic aromatic acids have appeared on the market, trimellitic (77A) and pryomellitic. Patents reveal modifications in conditions for oxidizing diisopropylbenzenes, such as mixed manganese and lead catalysts (44A): cobalt and cerium (40A), and use of a n aqueous alkaline medium (43A), which is applicable to complete the oxidation of crude oxidates from other alkylbenzenes as well especially in emulsion form (3gA). Concentrations of both formic acid and water are claimed to be critical in alkylbenzene oxidations (344). Fatty acids tend to decarboxylate when present during isopropylbenzene oxidation (37A). I n the oxidation of the xylenes in a solvent such as acetic acid, reaction can be initiated by ozone (27A). hlethyl ethyl ketone aids such oxidations ( 6 A ) . probably through its ability tu maintain chain reactions through peroxidation. Esters are claimed to be
INDUSTRIAL AND ENGINEERING CHEMISTRY
obtained directly if a n alcohol is present (37A). Sufficient selectivity in the oxidation of mixed Cs aromatics is claimed to permit separation of unreacted xylene from the products ( 7 A ) . A study was made of the by-products obtained from liquid phase air oxidation of xylene and their effects on autoxidation (47A). Oxidation of intermediates was studied. Conversion of monobasic to dibasic acids can be catalyzed by nitrogen dioxide, nitrohydrocarbons: and hydrocarbyl nitrites (78A). I n another approach, a toluic acid may be first esterified and then co-oxidized with more xylene (70Aj or oxidized in an ester solvent ( 3 2 A ) . Toluic acid may be converted to a nitrile first and then oxidized to give a cyanobenzoic acid (55A). Under certain conditions, benzaldehyde oxidizes more rapidly as an emulsion than in solution ( 7 A ) . Conversion of phthalaldehydic acid to phthalic acid was studied (23A). Monohalogenated xylenes will yield dibasic acids when oxidized as an aqueous suspension in the presence of a base and oxygen and proper catalysts ( 4 A ) . Polyxylylene peroxide oxidizes to carboxylic acids (28A). Autoxidation of p-methylacetophenone gives good yields of p-acetylbenzoic acid (50A). Simple cobalt salt catalysis permits 2-methy1-2(p-tolyl) 4-pentanone to be oxidized to thep-carboxyphenyl compound ( 2 4 ) . Peroxidation of Aromatics. Variations and improvements in cumene peroxidation, so important in this route to phenol and acetone, continue 10 appear ( 2 6 4 ) . Small percentages of methanol (38A), (ethylenedinitrilo) terraacetic acid (25A), copper, ( 5 A ) : or a metal phthalocyanine (46A) are claimrd to aid hydroperoxidation. A diluent such as tert-butylbenzene has been used (2,3A), as well as emulsion systems (36A). Temperature is critical (53Aj. Rates of both peroxidation and hydioperoxide decomposition were studivd (58.L),Other alkyl aromatic perosidations (42.4) include those to obtain dihydroperoxides from diisopropylbcn-
zene ( S A ) and di-set-butylbenzenes (77A, 60A), conversion of ethylbenzene to a-methylbenzyl hydroperoxide ( 74A), and autoxidation of p-cymene and p-sec butyltoluene ( 7 6 A ) , cyclohexyl , and cyclohexylidinephenylmethanes (57A). Partially hydrogenated naphthalene derivatives can be peroxidized in \vater emulsions (8A) o r with lightsensitizable organic dyes such as chlorophyll or phthalocyanins (24.4). Hexahydrofluorene was autoxidized (56A). Functional groups may be present on the ring; hydroperoxides can be obtained from p-acetylcumene (49'4) and pnitrocumene (38A).
Miscellaneous Aromatic Oxidations. In a class to themselves are oxidations of anthracene and tetracene in acetic anhydride and similar solvents with air and ultraviolet light to give the 9,lOand 5,12-quinones, respectively (20.4). They are base-catalyzed and not inhibited by sodium hydrogen sulfite, suggesting no chain reaction is involved. T h e kinetics and mechanism of dihenzyl and dicyclohexylethane oxidation were determined ( 5 2 A ) . .4 methylene group bound to the aromatic ring was autoxidized to obtain phenylglyoxalic acid esters (57A). -4new process for tetralinic acid from Tetralin via tetralone by autoxidation followed by the use of nitric acid is described t.354). Interest continues in methods for converting benzene directly to phenol by oxidation (72A. 45.4) The mechanism of autosidation of benzenesulfinic acid was studied (29.4), Oxidative phosphorylation is described ( .?gA4 J. Activity continues to improve the hydrogen peroxide process from alkylanthraquinones (73.4> 75'4. 30.4, 544). rlinthraquinonesulfonic acid esters can also be used to vary solubility relationships (27-4).
Aliphatics and Alicyclics
Paraffins. O n e of the fee\v examples of selective oxidation of a normal paraffin gives secondary alcohols almost exclusively, according to Russian investigators (2B-4B). Oxidation is conducted with boric acid present to esterify the alcohols as formed, and limited oxygen concentrations minimize competitive reactions leading to the usual mixture of products. Ordinarily mixtures are formed even from pure nparaffins (23B). Fatty acids can be favored if removed before further oxidation occurs (38B, 44B). Older theories of such autoxidations have been severely questioned (2019:2 2 3 ) . Further studies on initiating these chain reactions with S O ? show appreciable reductions in induction periods (5B). The role of
catalysts is discussed (25B). Improved performance is claimed for a combination of manganese and a Group IV metal (49B). Increasing hydrocarhon-air contact aids oxidation (32B, 43B). T h e froth phase has been utilized for this purpose (37B). A variety of specific paraffinic structures oxidized photocatalytically demonstrated that is0 structures generally have higher oxidation capacity than normal analogs and that this capacity decreases with increasing molecular weight ( 7 2 3 ) . T h e isomeric heptane hydroperoxides obtainable from n-heptane autoxidation (336') and oxidation of 2-ethylhexane were examined (30B). Several of the above effects are noted in the noncatalytic liquid phase oxidation of isobutane to favor tert-butyl hydroperoxide and tertbutyl alcohol (48B). Olefins. Elucidation of the products from autoxidation of unsaturated compounds begins to put order into a confused area. T h e effect of structure on formation of epoxides and hydroperoxides is reported (27B). A new interpretation of such oxidations suggests existence of a n equilibrium among oxygen, peracid, a radical, and water (7B). I n a new direct route to acetaldehyde from ethylene, reaction is effected in a n aqueous solution of palladium chloride ( S B ) . Hydroxyisobutyric acid can he obtained from isobutane using a plumbate catalyst (4.5B). T h e peroxides and epoxides formed from styrenes (74B, 28B). phenylcyclohexene ( 75B),and vinylcyclohexene (6B) were studied. Specific cyclic olefinic systems received attention: including oxidation of cyclohexene in acetic and propionic anhydrides to give esters (4OB). of carene: pinene. and limonene (39B. r17B). Hydroperoxides can be favored by co-oxidizing olefins rvith an aldehyde (77B). Scission of oleic acid to pelargonic and azelaic acids is accomplished b\. oxidation in acetic acid with a metallic catalyst follo\ved by oxidation \vith nitric acid (29B). Aliphatic Peroxides. Formarion of peroxides from oxidation of functional groups as \vel1 as from olefins and paraffins continues to gain interest. .4bout 25 organic peroxides are produced comnirrciallv. This field has been reviewed (34B). Alcohols yield peroxides when zinc oxide as a photocatalyst is irradiated at room temperature at 366 microns (26B). Certain acetals will give acetal hydroperoxides (35B). Superior catalysts for peracetic acid formation from acetaldehyde are claimed for the chlorides and bromides of copper and cobalt (42B). O n the other hand. by catalyst modification. the corresponding acid rather than the peracid can be favored (-16B).
Further disclosures of the hydrogen peroxide process from 2-propanol oxidation were made (36B). Catalysts of copper and heavy metals and a stabilizer are helpful ( 3 7 B ) , as is staging of the oxidation (47B). Recovery involves careful control of the fractional distillation of the products (79B).
Miscellaneous Aliphatic Oxidations. Organic sulfides can be oxidized to sulfoxides such as tert-butyl ethyl sulfoxide using as catalysts mixtures of oxides of nitrogen and copper halides (24B). Cyclohexanone oxime can he obtained from nitrocyclohexane by first hydrogenating to .V-cyclohexylhydroxylamine and then oxidizing with oxygen in aceiic acid containing cyclohexane, using a copper acetate catalyst (76B). Aluminum alkyls will oxidize substantially completely to the corresponding aluminum alcoholate (27B). The over-all synthesis of primary alcohols from 1olefins via the Ziegler process utilizes this operation. Alicyclics. Processes for dibasic acids such as adipic continue IO be improved. Catalytic decomposition of any hydroperoxides formed during cyclohexane oxidation is claimed to help (8B). Cyclohexanol and -one can be oxidized in nitric acid solution \vith air and a catalyst (786'). This may involve reoxidation. of nitric oxide to nitrogen dioxide ( 1 3 8 ) . v-hich can be used with oxygen for naphthene oxidation in acetic acid solvent containing some sulfuric acid ( 70B). hlethyl adipic acid results from oxidation of methylcyclohexane when treated ivith a cycloaliphatic ketone using first air and then nitric acid to complete the rraction ( 7 IB). T h e kinetics of the radiochemical oxidation of cyclohesene \verr determined ( 7 B ) .
Chemical Oxidants
Peroxides. Epoxidations of olefinic double bonds with hydrogen peroxide can be catalyzed by tungstic and molybdic acids (37C'j and their salts (79C, 89C, g2C). ,4liphatic peracids can be obtained from the carboxylic acid and hydrogen peroxide by reaction in a n organic solvent while removing water azeotropically (72C, 3SC). Peracids can be used in thc presence of acid acceptors ( 7 7 7C). Il'here olefin and peracid are immiscible: countercurrent flow can be employed (63C). Formic acid-hydrogen peroxide mixtures will convert cyclo-octene TO 1 &epoxycyclo-octane (66C)and ethylenic glycols to polyols ( 7 70C). Peracetic acid oxidizes cyclo-octatetraene to phenylacetaldehyde (28C). Unsaturated fatty acid esters give the corresponding epoxides with acetic anhydride-hydrogen peroxide reagent (82C). Perbenzoic
VOL. 51, NO. 9 , PART I I
SEPTEMBER 1959
1 13 1
Either primary or secondary alcohols can now be favored by direct liquid phase oxidation processes acid was tried on a varieq- of unsaturated compounds (88C). The utility of hydrogen peroxide is broader than simple epoxide formation, With optically active alcohols. the corresponding optically active hydroperoxides can be made and the stereochemistry studied ( 3 7 C ) . This agent has been studied on furfural ( 2 C ) , benzidine (IC), amines (5XC), and orthoquinones (6QC). Polyacroleins are completely degraded (SSC). Neopentyl and neophyl systems have been studied in the peracid oxidation of ketones (772C). Certain organic peroxides will react with diolefins to give carboxylic acids ( 4 6 C ) . By a redox reaction between hydrogen peroxide and a reducing agent. cyclohexanone yields w-hydroxycaproic acid (57C). Chlorocarboxylic acids can be made in a somewhat analogous manner (62C), A number of phenolic ethers were converted by peroxyacetic acid to 1,4and 1,2-quinones, the latter oxidizing further with ring cleavage (30C) Peracid oxidations Tvere studied with naphthalene derivatives (33C) and conjugated pyridines (45Cj. Pyrocatechol yielded muconic acid (73C). Aromatic amines were oxidized with perphosphoric acids (75C). Kinetics of hydrogen peroxide Oxidation of organic sulfide were determined (57C). Nitric Acid. This agent continues to find wide application where carboxylic acids are the desired oxidation products (Q5C). I t can also be used in conjunction with oxygen and recovered essentially unchanged by contact of evolved gases \crith oxygen in a nitric acid packed tower ( 7 IC. 7 2 2 ) . At about 200°, dilute nitric oxidizes a variety of alkyl aromatics to the corresponding aromatic acids (59C). Chloromethylated toluenes lvere oxidized to the phthalic acids (3QC). Under milder conditions, ol,ol-dichloro-~-xylene gave terephthalaldehyde and terephthalaldehydic acid (70C). .4liphatic dibasic acids can be favored by oxidation of saturated higher fatty acids and esters (47C, 67C,68C), ketones such as 5,16-octadecanedione (86C, H C ) , and ketoacids such as 12-ketostearic acid (96C). Even asphalt yields some succinic acid if first sulfurized and then treated with nitric acid (35C). Carboxylic compounds cleave to dibasic acids (76C, 37C), while substituted pyridines such as 4-ethyl pyridine undergo side chain oxidation (52C) and quinoline gives nicotinic acid
(83C). n-Octane with white fuming nitric acid a t low temperatures forms alkyl nitrates and then 2-octanone. which at higher temperatures cleaves to acids (QC).Propylene is convertible to lactic
1 132
acid and isobuiane to hydroxyisobutyric acid if the initial oxidate is hydrolyzed (77C. 78C). Tetralone yields o-carboxyhydrocinnamic acid (76C). Chloropentenes give mixed chlorinated and acidic products ( 7 73C). Sulfur Compounds. This field has been reviewed admirably ( 708C). A combination of elemental sulfur and a n aqueous base is capable of oxidizing many organic compounds to carboxylic acids. the technique being most nseful on alkyl aromatics such as xylene. toluic acid. and sulfobcnzoic acid (700C). Diacetylbenzenes give phenylene diacetic acids (550. .Aqueous ammonium thiosulfate performs this function also ( 7U2C). Trimesic acid is produced from isodurene by oxida~ionu i t h Lvater-soluble sulfates (70.3C). Thioamides can be obtained in improved yields from organic compounds such as mcthylbenzcnes. sulfur. and anhydrous ammonia by reacting with the sulfur at abovc 400" 1 3 (707C). Sulfur dioxide oxidizes mercaptans and disulfidrs to alcohols and ethers (,jJC t , Ozone. .4 recent reviexv gives a good picture of this field (3C). Diphenic acid can be obtained from phenanrhrene by ozonization followed by hydrolysis (3C. 7OC). Addition of dichromate ion to water-parafin mixtures below pH 3 improves carboxylic acid yields upon ozonation (27C). tut-Butylc)-clohexane gives alkyl adipic acids (22C). Anthracene yields not only- anthraquinone but also naphthalene-2..3-dicarboxylicand phthalic acids (25C). Cyclic olefin ozonides oxidize to aliphatic dibasic acids when treated v i t h oxygen in the presence of pvarer and a metal catalyst (G7C). Lnsaturared fatty acids behave similarly. oleic acid giving azelaic and nonylic acids (.iSCj. Oxidation of the aldehyde intermediates was studicd (5GC1, A sulfide is converted to a sulfone in the case of carboxymethylmrrcaptosuccinic acid ozonization to carboxymethylthionylsuccinic acid ( 7JC). In thiourea the sulfur is oxidized to give thiourea dioxide (7dC). Miscellaneous Agents. Considerable study was made of the mechanism of chromic acid oxidations on a variety of compounds (93C), including methylcyclohexane (7SC). a pentamethylheptene (32C). amino alcohols :65C).secondary alcohols (87C). tertiary alcohols (BUC)? formaldehyde (2UC). and benzaldehyde (38C, 7U9C). Citric acid esters oxidize to acetone dicarboxylic acid esters (QdC) with this agent or permanganate. Potassium permanganate and manganic salts provoke interesting theoretical studies, including oxidation of toluene (704C). olefins as oil-water emulsions ( 2 3 C ) , fluoro-olefins (78C). tertiary alcohols ( 7 9 3 , alcohols and ketones (8QC),
INDUSTRIAL AND ENGINEERING CHEMISTRY
allyl alcohols (iUC). and acetylenic alcohols (442). (&~inoline yields nicotinic acid (83C). The rate of periodate oxidations of several types of bonds was determined (26C). Kinetics and mechanism for diketone oxidation \vere measured (Q7C). Its action 011 polyols (6C: 27C), glucose (4OC). and monosaccharides (43C, 705C) was studied. Hypohalires Irere examined as oxidants for unsaturated aldehydes (842) and ketones (37C). and in the degrada[ion of 8-amino acids (73C). T h e usefulness of selenium dioxide \vas reviewed (6JC) and specific studies made on unsaturated fatty acids (707C), azulenes ( 706C). inethylisoquinoline (8C). and dimethylphenanthroline (YUC). A comprehensive review of lead tetraacetate oxidations Lvas completed (2YC). This agent !vas applied to oxidize cuinene hydroperoxide (42C) and cyclo-octatetraene (36'Cj Less common ag-enrs include copper oxide to give phenols from aromatic acids (7Cj or ketones (98C). oxidation of hindered phenols [vith f e r r i c y i i d e (24C), Oppenaur oxidations (YYC). a variation of the latter to yield 12keto-oleic acid from castor oil (60c'), oxidation of a ketc stearic acid to a dibasic acid \vith aqueous alkali and cadmium and zinc oxide ( 9 7 C ) , and the use of quinones to oxidize amines ( 77C) of silver ion on acetylenic alcohols (77C). and ofradiation i5C). literature Cited
Autoxidation of Aromatics (1A) Appell, H. R. (to Universal Oil Products C o . ) , U. S. Patent 2,874,098 (Feb. 17, 1 9 5 9 ) . (2.4) Ardis, A . E., Bruson, H. A. (to O l i n Mathieson Chemical Corp.), Ibid., 2,857,428 (Oct. 21, 1958). (3A) Bawn, C. E. H., Moran, D. P.: J . Inst. Petrol. 44,290-5 (1958). (4A) Binapfl, J. (to Farhenfahriken Bayer A.G.), U. S. Patent 2,850,527 (Sept. 2, 1958). (5A) Boer, J. H. de, Fortuin, J. P., Lt'aterman, H. I., Koninkl. Ned. Akad. Wetenschup. P70C. GlB, 170-5 (19581. (6A) Brill, W. F. (to Olin Mathieson Chemical Corp.), C . S. Patent 2,853,514 (Sept. 23, 1958). (7.4) Carless, J. E., Nixon, J. R., J . Pharm. andPharmacol. 9, 963-73 (1957). (8.4) Closson, R. D., Ligett, h'. B., Kolka, A. J. (to Ethyl Corp.), U. S. Patent 2,868,842 (Jan. 13, 1959). (9A) Conner, J. C.? Jr., Verplanck, V. (to Hercules Powder Co.), Ibid., 2,856,432 (Oct. 14,1958). (10.4) Dietz, F. C. (to California Research Corp.), I6id.,2,851,487 (Sept. 9,1959). (11A) Eiszner, J. K., Taylor, R. S., Bolton, B, h., Paint Varnish Production 49, 54-8 (1959). (12A) Emanuel, N. M., Denisov, E. T.. Doklady Akad. Nauk S.S.S.R.117, 458-61 (1957). (13.4) Engineering 186,812-3 (1958).
OXIDATION-LIQUID PHASE
.......................................
(14.4) Erickson, F. B., others (to Monsanto Chemical C o . ) , U. S . Patent 2,867,666 (Jan. 6, 1959). i 15.A) Etat Francais, SociktC d’Electrochimie d’Electrometallurgie et des Acieries Electriques d’Ugine, Brit. Patent 799,756 (.4ug. 13, 19581. (16.i)Fedorova, V. V., Sergee\-. P. G., Zhur. Obshchei Khim. 28, 2547-51 (1958). (17.A) Zbid., p. 2552-5. 118.4) Fetrerly, L. C. (to Shell Development Co.), U. S . Patent 2,839,575 [June 17, 1958). I19.A) Friedin, B. G., J . A @ / . Chenz. C‘.S.S.R. 30, 808-14 (1957) (Eng. trans.) (20.4) Fugassi, P.. hlasciantonio, P., Trammel, R.? 134th Meeting, ACS, Division of Gas and Fuel Chemistry, Chicago, Ill., Sept. 10-11: Abstracts, pp. 133-7, 1958. 121.4) General Electric Co., Brit. Patent 798,619 (July 23, 19581. 122.4) Greene. J . L., Jr., Hagemeyer, H. J . , .Jr. (to Eastman Kodak- C o . ) , c‘. S. Patent 2,820,064 (Jan. 14, 1958). (23‘4) Griehl, W., Goltnrt, W.: Ger. (East! Patent 10,918 (Dec. 6. 1955). (24.41 Heise, R . (to Dehydag, Deutsche Hydrierwerke G.m.b.H.), U . S. Patent 2,861,031 (Nov. 18, 19581. !25.4) Hiratsuka, K . (to Edogawa Kagaku K o q o Kabushiki Kaisha), U. S. Patent 2,861,107 (Nov. 18, 1958). (,26.A) hiratsuka, K,, Yonemitsu. E. (to Edogawa Kagaku Kogyo Kabushiki Kaisha)! Japan, Patent 6361 (Aug. 17, 19571. 127‘4) Hopkins, H . B. (to Laporte Chemicals). Brit. Patent 803,121 (Oct. 15, 1 9 58 ‘1 . (28.4) Hopwood, S. L., Jr., Errede, L. h. (to Lfinnesota Mining and Mfg. Co.), U. S. Patent 2,864,855 (Dec. 16, 1958). i,29Xi Horner, L., Basedow, 0 . H., Ann. 612, 108-31 (1958). (3OA) Jenney, T. M. (to Olin Sfathieson Chemical Corp.), U. S. Patent 2,837,411 (June 3, 1958). (31.4) Johnson, W.B. (to E. I. du Pont de Kemours 8: CO.’I, Zbid., 2,879,289 (March 24,1959). ( 3 2 X Knobloch, J. 0. [to Standard Oil Co. (Indiana!], Ibid., 2,880,237 (March 31! 1959). I 33.i) Knorre, D. G., others, Associated Research Service Translation RJ-1097. (34.4) Landau, R., Egbert, R. B., Saffer, A . (to Mid-Century Corp.), U . S. Patent 2,858,334 (Oct. 28, 1958). 135.4) Lecoq, J. C., Re?,.inst. franc. petrole 13, 1725-38 (1958’1. (36.4) Leszcynski, Z., Radoniewicz, H., Tizechert, .4., Przemysl Chem. 13, 664-9 (1957). (37.4) Mitskevich, N. N., Soroko, T. I., Erofeev, B. V., Proc. h a d . Sci. C.S.S.R. Sect. Chcm. 115, 679-83 (1957) (Eng. trans.). (38.4) Katta, G., Beati, E. (to Montecatini Societi. Generale per 1‘Industria Mineraria e Chimica), U. S . Patent 2,843,633 (July 15, 1958). (39.4) Newby, H. (to Chemische Werke Huls A. G J , Brit. Patent 801,562 (Sept. 17, 1958). (40’4) K. V. de Bataafsche, Petroleum Maatschappij, Zbid., 808,118 (Jan. 28, 1959). (41.4) Ogata, K., Itagaki, H., Yamashita, G., KBgy6 Kagaku Zasshi 59, 1156-60 (1956). (42A) Ohta, N., Tokyo Kdgy6 Shikensho H6koku 52,409-12 (1957). (43A) O’Neill, W. A,, Nesbitt, P. (to Imperial Chemical Industries). Brit. Patent 797,213 (June 25,1958).
(44.1) O’Neill, W..\,, Robertson, J . S. M.3 Ibid., 798,342 (July 16, 1958). (45.4) Pospisil, J . , Chemir (Prague) 9, 885 (1957). L46.4) Ruhrchemir. .4, G., Brit. Patent 801,387 !Sept. 10. 19583. !47h1 Russell, G . .I.,J . Cheni. Educ. 36, 111--18 ( 1 9 5 9 ) . (48.4) Sergeev, P. G., Sladkov, A . M., J . Gen. Chein. C.S.S.R. 27, 607-8 (19581 (Eng. trans.). (49A) Zhid., pp. 609-10. (50Xl Zbid., pp, 893-4. (51.4) IbLd.: pp. 895-7. (52.4) Sergienko, S.R.. Chernyak, N. Ya., Proc. .$cad. .Sei. 1. .S.S. R . Sect. Chem. 113,223-6 (1957! (Eng. trans.l. ,53.4) Shiffler, W. H., Senger, J . F. (to California Research Carp.’), U . S. Patent 2,829,173 (.April 1, 19581. ,\54A) Sprauer, J. W., Williams, T. V., Jr. (to E. I. du Pont de Nemours & C O . ’ ~ , Brit. Patent 798,237 !July 16, 19581. (55.4) Suvorov. B. V., Rafikov, S . R . , Manoborskaya, L. G., U.S.S.R. Patent 111,891 (July 2, 1958). (56.V Triebs, h7., Hevner. E.. Chum. Ber. 90, 2283-90 (195-1. (57.4) Treibs. W..Schollner. R.. Zbid., 91, 2282--9 11958). (58’4) Tsunoda, Y . ,Matsumoto, K., Kato, T., Tokai Urnkyoku Giho 19, 41-5 (1958). (59.4) Wieland. T., Patterson, F.. .4ngere,. C h m . 70, 313-14 (1958i. (60.4) Yamada, S.,Matsumoto. Y., KdgyB KagaAu Z a s s h i 6 0 , 8 5 - 6 (19571, Autoxidation of Aliphatics (1B) Abel. E., .Makroniol. Chem. 27, 242-5 (1958). (2Bi Bashkirov. A. N., others, Proc. Acad. Sci. C.S.S.R. Cheru. Tech. Sect. 118, 119, 1-4 (19581 iEng. trans.). 1,3Bi Zbid.. 119, 247-9 (1958); Doklady Akad. S a d . S.S.S.R. 119, 705-7 (1958). (4B) Bashkirov: A. N., Kamedkin, V. V., Sokova, K. M., .4ndreeva, T. P., Khim. i Tekhnol. T o p l i m i Masel 3, 10-6 (1958). (5B) Blyumberg, E. X., Emanuel, N. M., Bull. h a d . Sci. 11.S.S.R. Diu. Chem. Sci. S.S.R. 3, 289-97 11957) E n g . trans.). (6B) Brill, M’.F . , J . Org. Chrm. 24, 257-9 (19591. (7B) Brun, 51., hlontarnal, R . , Conzpt. rend. 247, 2361-4 (1958). 1.8s) Cates, H. L., Jr., others [to E. I. du Pont de Nemours & C o . ) , C . S. Patent 2,851,496 (Sept. 9, 1958). (9B) Cheni. Tliek 84, 100 (April 11, 1959). (10B’ Clingman, W7.H., Jr. (to American Oil (20.1, U . S . Patent 2,830,084 (April 8; 1958). (llB’1 Du Pont, de Nemours 8i Co., E. I.? Brit. Patent 799,754 (.4ug. 13, 1958). (12B) Gavrileu, B. G., Zinoliyeva, G. V., J . Gen. Chem. U.S.S.R. 26, 3327-8 (1956)(Eng-.trans.). (13B) GoodGear Tire & Rubber Co., Brit. Patent 797,464 (July 2, 19581. (14B) Hock, H., Siebert, M., Chem. Ber. 87, 546-54 (1954). (15BI Ibid., pp. 554-60. (16B) Joris, G. G., Vitrone, V. (to Allied Chemical Rr Dye Corp.), U. S. Patent 2,829,163 (April 1, 1958). (17Bj Kahler, E. J . , Kinzer, G . W. [to Standard Oil Co. (Indiana)], Ibid., 2,831,023 (.April 15, 1958). (18B) Kamlet, J. (to Goodyear Tire and Rubber Co.), Zbid., 2,844,626 (July 22, 1958).
(19Bj -Keeler, W. R., Douslin, D. R., Deal, C. H., J r . (to Shell Development Co.), Ibid., 2,869,989 (Jan. 20, 1959). (20B) Kenner, J., Tetrahedron 3, 78-89
(1958 I . (2fB) Kirshenbaum, I., Mirviss, S. B.,
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