. Los Angeles 7, California THIONYL CHLORIDE

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1 * This review was prepared In conjunction with studies supp Office of Scientific Research, United States Air Force, Contract AV' Aa-ffl..71A.- A &I.-n Qbf..tt..q r~ - - %ft #FOS)- P. 040& " INORGANIC SULFUR REAGENT3; I THE THIONYL HAUDES By Charles M. Buess, Norman Kharasch and Robert B. Langford Chemist~ry Department, L~niversity of Southern Califor. Los Angeles 7, California m Our studies of organic sulfur compounds have made us increasingly aware of the inorianic sulfur reagents, While it is clear that many compounds of this group have now become of greatest theoretical and practical interest, yet there has been a lack of correlative and review papers which would serv6 to focus attention on them. Since we had much of the required literature at hand. it seemed desirable to prepare a series of brief articles, each of which would give a thorough entry to the literature on a selected group of these substances. The present paper concerns the thionvl haiide, SOX 2. The known examples of this group of compounds are shown in Table I, together with the. other known compounds of sulfur and halogen, and of sulfur, oxygen and halogen. Part II of this series will present the sulfuryl halides, SO 2 X 2. Iv Physical Propertie. THIONYL CHLORIDE Thionyl chloride, SOCd, melts at , boils at 78.80, has a density (at ) of g./ml. and a refractive index, n1, of * Pure thionyl chloride is a colorless, fuming, toxic, irritating liquid which in miscible with benzene, carbon tetrachloride, chloroform and most inert organic solvents. Studies involving force constants,, infrared,, 6 Raman, 7-10 and ultraviolet spectra, magnetic rotatory power, 12 magnetic susceptibility13, and dielectric constants and dipole moments 14 ' 15 have been carried out. Its physical properties have suggested its frequent use as an ionizing solvent. The heat of formation of thionyl chloride in Xcal. /mole. 2 1 The first preparations of thionyl chloride employed the reactions of Podium sulfite with phosphorus pentachloride22 and of calcium sulfite widti phosphorus oxychloride.23 Industrial methods, described in the "ID C Uterature, 25=31 have sought less exp~nslve syntheses, exam /I are shown in the following equations: SEP

2 (az4,3s "SbC13. (-1 sci. +so 3 so + soca, (2) 25 S C S0o + 3 C 1 2 S 4 SOC, (3)26 Co + $02 s SOCIZ + COC (4)27 2S CL - catalyst 2 SOC1 2, 2s68. 9 so +coc 1G3 (5), s20 + CCI SOCh + ('OC1 2 In the process of equation 1. sulfur dichloride may be prepared.insitju from sulfur monochloride and chlorine (CISSCI + Cl -- Z CISCI). The sulfur trioxide is usually intro&dced by using fuming sulfuric acid. Excess sulfur trioxide must be avoided because of the easy formation of the so-called 'lyrosulfuryl chloride" (equation 6). (6) SOC so03 S-osC1Z + SOZ If radioactive SCIZ is used in th method of equation 1# the tagged sulfur is found mainly in the thionyl chloride. 32 Considering the reaction of equation 2: sulfur dichloride may be substituted for sulfur monochloride and part of the chlorine, and sulfuryl chloride may be used as a source of SO2 and %;I,. The reaction is best carried out at With recycling of the sulfur chlorides. SO 2 and SOCl. which are formed, nearly 100%, cunversion is reported. At high temperatures (500 ), the decomposition of thionyl chloride is nearly complete. At intermediate temperatures (1980 and 2380). the system. SOzC1 2 + SCI! 2 SOCI 2. represents & reversible reaction. 3 0 The oxidation of SCI, with oxygen, to give sulfuryl chloride is Irreversible under these conditions. Equation 7 represents an overall procedure which has been used to prepare thionyl chloride. 3 0 (7) a SC)Iz + 03 C(activated) z SOC1 2 Phosgene may also be employed in reaction 3. Is reaction 5, the yield of thionyl chloride is 72%. Substitution of chloroform or pentachioroethane for carbon tetrachloride lowcre the yield to 40% and 6%, respectively. ai a This chlorinolysis of the sulfur-sulfur bond Is a very general reaction. and has found many applications in organic chemistry. The products obtained are sulfenyl chlorides: 2 RSSR + Cl RSCl. Cf. e.g., Organic Sulfur Compounds, Vol. 1. edited by N. Kharaschg Pergamon Press (1960): Cho. 31.and 12.

3 -m3- The reaction of boron trichloride with the sulfur dioxide, in which the latter acts as solvent, is extremely slow unless chloride ion is present. 3 3 It has been suggested that the catalytic effect of chloride ion may involve the iot, SOaCl" (8) Z C SoC BZ0 3 Technical grade thionyl chloride contains about 7% impurities, mainly sulfur monochloride, sulfuryl chloride and sulfur dioxide. 3 4 Sulfur monochloride may be removed after reaction with sulfur, and the sulfuryl chloride may be taken out by means of its selective reaction with other substances. 3 4 Reagent grade thionyl chloride is also available. Chemical Properties Above its boiling point, thionyl chloride decomposes to sulfur chloride, sulfuryl chloride, sulfur dioxide, and chlorine. The photochemistry of Sthionyl chloride does not rsem to have been investigated in detail, but seems worthy of study, especially in comparison with sulfuryl chloride. Rapid sulfur exchange between S*OCk,-SOBra and SOCI 2 -S OBr 2 in SO2 solution at -50 or in mixtures of pure compounds at -20 has been observed. 3 5 Similarly, chlorine exchanges rapidly between Cl!-labelled pyridinium chloride and SOCI in chloroform at Z0. 36 These results may be accounted for by the ionization of the thionyl halides or the formation of addition complexes and are in mnarked contrast to results wherein the lack of exchange between SOClZ and SOZC1 2 has been noted. 3 5 Thionyl chloride reacts with metals, such as antimony, sodium, aluminium, magnesium, and iron. The reactions are generally slow in the absence of acids 37 (except in the case of antimony) and this explains the use of iron containers for storage of the th)ronyl chloride. Glass, lead, and nickel containers are also used for storage. With phosphorus, selenium and tellurium, reaction with thionyl chloride yields the respective chlorides. "Hydrated chlorides, such as MgC1Z. 6 H.O, are conveniently dehydrated with SOC1 2, since the products, HCI and SO., are gases.39 Mustard gas 40 may also be dried in this way. In some of its inorganic reactions, thionyl chloride acts as an omddising agent, e.g.: (9) 4 HM + 2A 0CIZ HCI + SOZ + S (10) Z H 2 SOC1 AIC13 -) 4 HCI + SO +3S

4 . "4, In other reactions. however, It functions as the reducing agent: (11) 7. HNO 3 + SOCIl - H SO 4 + NO C1 + NOCI (12) N 2 o 4 + SOC1-- ZNoCl + S03 0 The reaction with silver nitrate yields silver chloride and CISONOz, while with ammonia, polymeric thionylimine, (HNSO)x, is reported as the product.41 The preparation of chromyl chloride using Cr0 3 or K. Cr0 7 has been mentioned. 42 The best known reactions of thionyl chloride in organic chemistry involv, the replacemant of hydroxyl groups. in alcohols and carboxylic acids, by chlorine. The conversion of alcohols to alkyl halides often occurs with retention of configuration. This is not, however, always the case. The steps involved in the reaction converts the alcohol to chlorsulfinates and. in some instances, to sulfites. Under certain conditions these intermediates can be isolated. 0" (13) ROH---) RO-[-l ---. R *R0OR The elimination of sulfur dioxide from the chlorosulfinates may occur through different transition states. The detailed mechanism and stereochemistry has been studied in a number of Investigations with alcohols, 32, 46, 47, 48 with small ring alcohols 4 with chlorocyclohexanols, with allylic alcohols, 51 with acylamino alcohols$ 2 and with sterols. 5 3, I The widely used reaction for conversion of acids to acid chlorides has been shown to occur through the carboxylic anhydride when pyridine in employed. 5 Sulfonic acids and carboxylic acids, which do not normally react with thionyl chloride, do so in the presence of dimethy1formamide.5 6 The ionized salt (CH 3 )znchcl+ci', is formed. Another Interesting application involves the estimation of the number of carboxyl groups in gelatin with SOC1 2 and CH 3 OH Naphthoic acid, heated with thionyl chloride at , yields 1, 6-dichloronaphthalene. Mercapto groups are replaced by chlorine and some ketones are converted to vinyl chlorides by SOCIZ. 59 Ethylene oxides yield Z-chloro sulfite.6o while A 61 aliphatic A -lactones give 3-chloroalkanoyl chlorides. (12) 1 H C - CH + 30C1 2 4 (CH ClCH 0430 (13) CH CHzOCO +SOCk - CH. CH COC1 + so 2

5 Thionyl chloride cleaves cyclic ethers and related compounds to afford dichloro derivatives. Examples are the reaction with tetrahydrofuran and 4-phenyl-l, 3-dioxane.63 AMother interesting ether cleavage involves the (14) + soclz M. IClCHzCHzCl C 6 H 5 65 conversion of r-methoxyvaleric acid to methyl I-chlorovalerate with Inversion at the Y'-carbon atom.64 The products of the reaction of SOCI 2 with phenols are dependent on the conditions. In some instaixces sulfites can be obtained and under other conditions ring substitution occurs. The reactions of this type have been reviewed. 6 5 In general, the Friedel-Crafts reaction with SOC1 2 is not very successful, but 9-fluorenyl66 and a-acetamidopheny167 sulfoxide may be preapared in this way. In the presence of copper, SOC1? and substituted phenols (4-hydroxycoumarin, 68 4-propionylresorcinol, 6 69 Zhydroxy.5- methylacetophenone, and the naphthols yield symmetrical sulfides by ring substitution and attendant reduction. Thionyl chloride is an effective agent for intramolecular removal of the elements of water. Examples are the dehydration of 1, 1, l-trichloro-zmethyl-z-propanol, which occurs A; the chlorosulflnate and which is catalyzed by amines, 7Z and ethyl 2-carborxiethoxy-l-hydroxy-Z-methyl cyclohexylacetate.73 The units of alcohol are similarly removed from a substituted phthalamic acid 7 4 and water is removed intermolecularly from ,77 oxanilic acid.* 5 Urea is converted to cyanuric acid and other products. (15) CONR 0 O ", COOH " F 0 : O1N, C6H5 (16) COOH N11.1% 21 0m a CXO CONHC 6 H 5 0 a C I / 0 C6H The intermolecular condensation of glucose is also effected through the use of thionyl chloride. 7 8 Chlorination of compounds with thionyl chloride is illustrated by the reaction with dimethyl sulfide.79 For these purposes, thionyl chloride Is a less vigorous *gent than sulfuryl chloride and promotes formation of mono and dichloro derivatives, rather than higher chlorinated products. The

6 -6 addition of chlorine to benzene is activated by the presence of thionyl chloride and the amount of the gamma isomer of hexachlorocyclohexane may be 'affected by its presence 800 8a In the special case of I1 l-diarylethyleneq, s5flnic acid is obtained 2 after hydrolysis of the product. Chloropheno (17) Ar C a CHl 4+ SOCI.--- Ar 2 C w CHSOH thiasines are chlorinated by thionyl chloride. 3 Alternatively, the phenothiauine ring may be closed with the chlorination by the action of thionyl chloride on diphenylamine. The oxidative character of thionyl chloride in sometimes exhibited in organic reactions. The cleavage of substituted 69,9 "-bixanthenes to xanthones84o 85, 86 and the dehydrogenation of a highly hindered acrylic acid. cis'of :41 S-(l' a'-naphtho)-3-pyrazolyl3 cinnamic acid, to the corresponding. (18) / ~ 1) SOCl 2 * III ~ ~2) Hi 20 propiolic rcidg 7 are examples. Thionyl chloride in not usually the best reageut for effecting the Beckmaann rearrangement because it initiates cleavage reactions.8 8 The conversion of cyclohexanone oxime to epsilon-caprolactam with thionyl chloride occurs with fair results, however. 89 Primary aromatic amines are converted to thionylimines. ArN a SO, with 5OC Thiapurines are obtained by the reaction of thionyl chloride with S5 6-diaminouracils. 9 1 Other thiadiazoles are obtained through the ust of orthodiamiines.9 2 The cleavage of sulfinyl esters by SOC 9 3 and its addition to ketene to give after methanolysi. (MeOOCCH 2 ) 2 S 94 are further interesting applicauons. Its reaction with phenylaersine to givee C 6 H 5 AsS9S contrasts with the reaction of phenylphosphine with SOCIZ, which yields (C 6 HsPSO) 96 C 6 HsAs(MgBr), and SOCl 2 gives C 6 HsAsSO. A possible application of thicayl chloride. which has not been exploited fully an yet, Is its chain terminating properties. It has been shown that SOCI acts in this way in the sulfoxidation of cyclohexane (reaction with SO 3 and 029 under irradiation). 9 7 Reviews on the early chemistry of SOC1 2 * 2 3 the reaction with phenol,, 5 with raminobensoic acid#9 synthetic applications$ and technology10 have appeared.

7 "-7 THIONYL FLUORIDE Thlonyl fluoride, SOF., melts at o and boils at Raman, 02lOZ10, infrared, and microwave 105 spectra, dipole moment 105 and force constant stadies have been carried out. Thionyl fluoride Is obtained by the reaction of thionyl chloride with AsFy 3 SbF 3 y 106, 107 -F, 108 or KSO 2 Ft 10 9 ' 11 0 by reaction of S 4 N 4 with aqueous HF and CuO, 111 and by reaction of SO 2 'with VF 5,112 A 77% yield was obtained recently by reaction of sodium fluo.ide with thionyl chloride in acetonitrile.13 Thionyl fluoride hydrolyzes slowly, but completely at room temperature, furming sulfurous and hydrofluoric acid. Thel'mally, however, It is quite stable With SiS 2 at 4000p thionyl fluoride gives SiF 4 and SOV. Mixtures of SOFa and 0., submitted to an electric discharge, give peroxy compounds. U4 THIONY L CHLOROFLUORIDE Thionyl chlorofluoride, SOCIF, boils at 12.20, melts at , and has a liquid density of g./ml It is prepared by the action of SbF 3 and 3bClI 101 or IF,.115 on SOCIZ. The chlorofluoride reacts with mercury and copper, at room temperature, and with iron at 700. overall reaction is represented by equation 19. (M w metal). (19) 4SOCIF + 3M--2- SOF 2 + SO 2 + MC MS 1 Disproportionation may occur first; if so, the products are those of the reaction of SOC1 2 with the metal THIONYL BROMIDE Thionyl bromide, SOBr 2, melts at -520, boils at 1380 (decompn.), it atmospheric pressure or at 42.5 at 16 mm. press-are, has a density at ISO of and is an orange-yellow liquid.11a Raman spectrum s 118t 119 Thionyl bromide is prepared by the reaction of HBr or KBr with SOCI Reports of the existence of SOC1Br are probably incorrect. Thionyl bromide decomposes slowly at room temperature (4 SOBr 2---* S.Br SOa + 3 Br.) and is rapidly hydrolyzed by water. Thionyl bromide converts carboxy-ic acids to acid bromides and substituted alcohols to the corresponding bromides., 1 9, 120 A general method involving conversion of alcohols to sulfites with SOCI 2 and cleavage of the (RO) 2 SO.-ith thionyl bromide is recommended for the preparation of alkyl bromides Thionyl bromide reacts with pyridinium halides to give C HSNH+ XBr 2 " along vith S and SO2.12@ 123 Sulfur exchange between sulfur dioxide and thionyl bromide Is slow124 unless ionic halides or catalysts are present ' 126 The

8 A review of the synthetic uses of sulfuryl bremide has been made. 99 THIONYL IODIDE Thionyl iodide, SOI., is unstable. Its formation by reaction of thionyl chloride in carbon tetra-:hloride solution with potassium iodide, 127, 128 has been reported and Its decomposition was followed by spectroscopic means. It is decomposed by light. Dilute solutions in the dark are claimed to be stable for eight hours.127 It has been considered to be an intermediate in the following reactions: 129 (20) (C 2 H 5 O) 2 SO + 6 HI H 2 S + 2 C 2 H 5 OH + H (Z1 SOC1Z + 6H1- HzS + H Z HC The results probably bear reinvestigation, since quaternary ammonium iodides, when treated with thionyl chloride, yield malts as follows: 130 (22) SoC ic" + SO? + s 3 Iodine is liberated when potassium iodide is added to these salts. ra * *

9 (I iii' * I Si Jjj ] 2' U U a V I 'a U 0@ "A, ii Pb, 9 0 p E

10 REFERENCE3 TO TAULE I (1). General references: (a) T. Moeller, '1norfanic Chernistry"t John Wiley, New York, 1952 pp. 518 ff.; (b) A. B. Burg, 'Iluorine Chemistry", J.H. Simons, ed., Academic Press, New York# 1950, Vol. I, pp. 77 ft.; (c) D.M. Yost and H. Russell, Jr., '1vetematic Inorganic Chemistry-" Prentice- Hall, New York 1944, pp. 295 if. (2)M M. Centnerszwer and C. Strenk, Chem, er. n 914 (1925); M. Troutz and K. Ehrmann, 3. 2rakt. Chem. I 79 (1935); L.M. Dubmikovand N.I. Zorin, 3. Gen. Chem.. U.S.S.R, JL 185, (1947); rghem. AbSt..j, 57 (1936). (3). L.M. Dubnikov and N.I. Zorin, reference 2; D. Edelson, CA. Bieling, and G.T. Kohman, Ind. Eng. Chem L 2094 (1953). (4)o F. Brown and P.L. Robinson, T. Chem, 3oce ; M. Bartlett and P.L. Robinson, Proc. Chem. Soc. 230; F. Seel and 0. Detmer, Z. anora. u. allgam. Chem. 113 U (1959). (5). W.C. Schumb, Inorg. Snth Il, 119 (1950). (6). K.G. Denbigh and R. Whytlaw-Gray, J. Chem. 92c ; W.R, Trost and R.L. McIntosh, a J. he 508 (1951). (?}. K.J. Palmer, J. Am. Chem. Soc. 60l 2360 (1938); M. Schmidt and-b. Wirwoll, Z. anora, u. _llzem. Chem. 177 (1960). (8). G.H. Whiting, J. ADolied Chem. L 390 (1952), (9). T.M. Lowry and G. Jessop, I. Chem, Soc. I= 782. (10). F. Fehe'r and G. Rempe, Z Naturforsc. 688 (1953); F. Feher, I. Naused, and H. Weber, Z. anorg. u1. allgem. Chem, & 303 (1957) and preceding articles. (11). F. Fehir, J. Kraemer and G. Rempe, Z. angorg u. IaLlem. Che, m, , (1955). (12), A.R. Vasudeva Murthy, Proc. Indian Acad. S v. IAfl 17 (Ir53); Chem. Abstr. A As intermediates. (13)i See text. (14). F. Seel and L. Riel, Z. anora. u. allem,. Chem. 2i82, 293 (1955). (15). E. Hayek and A. Csaloun, Mgn ats. IL 790 (1956); E. Hayek, (16a) A. Aignesberger, and A. Engelbrecht# Mot. s 735 (1955). S.S. Sandhu, B.S. Chaklul, and G.S.'Sandhut I.-Indian Chern. v., 3Z9 (1960)....

11 (16). H.S. Booth and C.V. Hermann, 3. Am. Chem. Soc. 63(1936); F. Seel and L. Riehi, Z. ano7g. ui allrem. Chem. 1"l. 293 (1955). (17). F.B.D. Dudley and G.4. Cady, J. Am. Chem, Socr (1957). ( 89), R.B. Harvey and S.H. Bauer,'-. &Am. Chem. Soc, 859 (1954). (19). (a) i-.b. Dudley, G.H. Cady, and D.F. Eggers, J. Atn. Chem. Soc. a 290, 1553 (1956); (b) F.B. Dudley, 3.N. Shoolery, and G.H. Cady, 3. Am. Chem. Soc. _., 568 (1956); (c)f. Seel and 0. Detmer, Z. anora. u. aliem. CheM. 0J (1959). (20). H.S. Booth and C.V. Hermann, J. AM. Chem. S9oc, 1 63 (1936). (21). H.R. Aller and R.H. Maxson, Inora. Synth. I 114 (1939). (22). M. Sveda, Inorg. Synth. 111, 124 (1950). (23). H.A. Lehmann and G. Ladwig, Chem Tegh & 455 (1953). (24). H. Jonas, Z. anoru. u. allaem. Chem. AA j 273 (1951). (25). M.R.A. Rao, Proc. Indian Acad,J. IA. 354 (1940); -Chem Abstr.,., (1941). (26). 1. Wasson, J.-Chem, Soc ; 1. Wauson and C. Argument, J. Chem, Soc. 18jQ 1702; M.T. Kikindai, Comot, rendo. 873 (1955); A.A. Woolf, Chemistry and bdua~strr Szo.

12 References i). D. N. Yost and H. Russell, Jr., "Systematic Inorganic Chemistryp" Prentice-Heall, Inc., Nev York, p. 307 (1944)..H. Siebert, Z. anorg. u. allgem. Chem. 274, 24 (1953). 3. K. Venkateevarlu and S. Sundaramp j.. chim. phys. L4. i02 (.1957); CA 51, ).K. C. Schrelber, Anal. Chem. 21, n168 (19i9). 5). D. Z. Martz and R. T. Lamgeanii J. Chem. Phys. 22, 1193 (195%). S.R. N. Haszeldine and J. M4. Kcidd, J. Chem. Ieoc M. Goebring., Chem. Ber. 80, 2 1 (1947).. R. Vogel-H41ger, Acta Phys. Autriaca 1, 323 (1948); Chem. Abet. 42, 6663 (1908).?I. C. A. MeDve el, Trans. Farad-y Soc. _, 371 (1953). ) 0. Alen and C. A. McDowell, J.Ce.hn (15) I B. P.le.,Chem. Sc 199,,34 D. Voigt, Ann. chim. (12) 4, 393 (1949); Chem. Abst.45, 4980 (1939). S..barmatti, Proc. Indian Acad. Sci. 13A, 359 (1941); Chem.Abst. 36, 361 (1942). 1). M. Beysert and F. Govaert, Natuurv. Tijdschr. 20, 119 (1938); Chem. 32,6517 (1938). Abet. I. 1). Z. Coop and L. E. Sutton, Trans. Faraday Soc. 35, 505 (1939). ;).x. Bn. czo, Mitt. chem. Forsch.-Insts. Wirtsch. -sterr. 1t 104 (1953); tbem. Abst. 48., 5013 (1954).,). H. SpanJau and E. Brunneck, Z. anorg. u. ailgem. Chem. 270, 201 (1952). 5). B. J. Masters., N. D. Potter, D. B. Asher, and T. H. Norris, J. Am. Chem. Soc. 18, 4252 (195). )). L. E. D. Pease,.Jr., and W. E. Luder, J. Am. Chem. Soc. 7j, 5195 (1953). V.Gtmann, 1.bnatsh. 85, 286 (1954). E. Neale and L. T. D. Williams, J. Chem. Soc, 1954., M..Persoz, Compt rend. 28, 86 (18 4 9); L. Carius, Ann. 70, 297 (1849). The early chemistry of SCl is excellently summarized by C. A. Silberrad, Chemistry and Industry, 45, 36, 55 (1926); cf. also R. Cherton, Bull. soc. roy. sci. Liege 11,!X (l2);-chem. Abst. 38, 3209 (1944). Cf. also, "InYerscience E-cycl. of Chem. Tech." Vol. 13, pp (195). J. 3. P. Edwards (to Hooker Electrochem. Co.), U.S. 2,362,057, Nov. 7, 1944; Chem. Abet. 39, 2386 (1945); Farbenfabriken Bayer A.-O. (H. Jonas and P. Lueg, inventors) Ger. 939,571, Feb. 23, 1956; Chem. Abet. 52,14113 (1958). ). A. Pechukas (to Pittsburgh Plate Glass Co.), U.S. 2,431,823, Dec. 2, 1947; Chem. Abst. 42, 2409 (194). E). F. Fricke (to Allied Chem. & Dye Corp.), U.S. 2,471,946, May 31, 1949; Chem. Abet. 42, 720o (1948). ). Badische Anilin- & Soda- Fabrik (by K. Wintersberpr and G. Ibudela), Ger. 803,4n11, Apr. 2, 1951; Chem. Abet. 45, 6357 (1951). ). A. T. Hallowell and 0. T. Vaala (to E. I du Pont de Nemoure & Co.), U.s. 2,393,247, Jan. 22, 1946; Chem. Abst. 40, 1980 (1946). I). C. Z. Frank, A. T. 2allowell, C. W. Theobald, and 0. T. Vaals, Ind. Eng. Chem. 41i, 2061 (1949). 3: A. 0. Evans and 0. V. Meadows, Trans Faraday Soc. 3, 667 (1947). W. H. Salzenberg and M. Sveda (to E. I. Du Pont de Nemours & Co.), U.S. 2,42o,623, May 13, 1947; Chem. Abet. 41, 5696 (1947). ).. Daudel, Bull. soc. chim. France I9, E23 (1952); R. 14zunrt, P. Daudel and B. Doscardin, J. ch ,s, (1949); Chem. Abet. 4, 2831 (1950). ) A. B. Burg and _. R. BLrnbaum, J. Inorg. & Nuclear Chem. 1, 146 (1958); Cf. H. Hecht, R. Greese, and 0. Jander, Z. anorg, u allah.m Chem. 269,. 265 (1952). ) T. Harrinton and T. H. oyd, J. Soc. Chem. Ind. t, 209 (195); Chem. Abet. ). L. F. Jonson, Jr., and T. H. Norris, J. Am. Chem. Soc (1957); D. s. Butge and T. H. Norris,. Am. Chem. Soc. M.. (1959).

13 I. I * He. Jo Frazer, J. Chem. Soc. 1957, It. A. Hubbard, 2nd. and W. F. Luder, J. Am. Chem. Soc. 3l, 1327 (1951). 38. H. Hecht, 0. Jander, and H. Schlapmann, Z. anorg. Chem._ 255 (1947). 39. H. Hecht, z. rg Chem.?24 37 (1947) * 40. L. 2. simer (tou.s.a.). U.S. 2.,681,307, June 15, 1954.;Chem. Abet. 48, P. W. Schenk, &r. 75, 94 (19042) J. H. Freeman and C. E. C. Richards, J. Inorg. and Nfuclear Chem (1958) P. D. Bartlett and H. F. Herbrandson, J. Am. Chem. Soc., 5971 t1952) W. Gerraix and B. D. Shepherd, J. Chem.'Soc Plodor and J. Kiss, J. Chem. Soc.1 52, D. J. Cram, J. Am. Chem. Soc. 75, ). (47. D. Y. Curtin and D. B. Kellom, J. Am. Chem. Soc. 75, 6011 (1953). Q 48 C. C. Lee and J. V. T. Spinks, Can. J.- Chem. L~, 1005 (1954). 49. J. D. Rberts and R. H. Mazur, J. Am. Chem. Soc. 73, 2509 (1951). 50O- H. C. Stevens and 0. Orummitt, J. Am. Chem. Soc. 7, 4876 (1952). F. F. Caserio, 0. N. Dennis, R. H. DeWolfe and w. G. Young, J. Am. Chem. Soc. 77, 4182 (1955). (52). J. Sicher and M4. Pankova, Chem. Listy ý2x 1336 (1955). 53). H. B. Henbest and R. A. L. Wilson, J. Chem. Soc. 1256, (54). R. Z. Ireland, T. I. Wrigley and W. 0. Young, J. Am. Chem. Soc. 80, 4604 (1958). (55). W. Gerrard and A. M. Thrush, J. Chem. Soc. 1952, 741; Cf. M. Y. Kraft and V. V. Katyahkina, Daklady Akad. S.S. '.M 312 (1956), Proc. Acad. S. U.S.S.R., Sect. Chem. 109, 361 (1956); Chem. Abut. 51, 1832-(1957). (56). H. H. Bosshard, R. Mory, M. Schmid, and H. Zollinger, Helv. Chim. Acta 42, 1653 (1959). 57). J. Bello, Biochir. Biophys. Acta 20, 426 (1956). 8)Kulkarni and G. V. Jadhav, J7 Karnatak Univ. 1, 19 (1956); Chem. Abut. 52, 8107 (1958). (59). 0. Lloyd, W. B. Whalley and R. B. Travers, J. Chem. Soc. 19%, (60). A. Pechukas (to Pittsburgh Plate Glass Co.), U.S. 2,576,13-, Nov. 27, 1951; Chem. Abst. 46, 5615 (1952). 6f.T. L. Greuham, J. E. Jansen and F. W. Shaver, 3- Am. Chem. Soc. 72, 72 (1950). V. 1. Lutkova, N. I. Kutsenko, and M. I. Itkir.; Zhur. ObshcheR Iim (1955); Chem. Abst. 50, 8584 (1956). (63)- N. V. Shorygina, Zhur. Cbshchel Xhim. 26, 1460 (1956); Chem. Abut. 50, (1956). (64). K. B. Wiberg, J. Am. Chem. Soc. 74), 3957 (1952). (65). D. Libermann, Bull. soc. chim. France 1951, C141. (66). C. Courtot and N. Kozertchouk, Compt. rend. 218, 973 (1944). 67). S. SgasMva and K. Sakurai, J. A arm. Soc. Japan 60, 22 (1940); Chem Abat. 34, (68). j. Kfosa, Arch. flarm. 286, 348 (1953). (69). V. J. Dalvi and G. V. Jadhav, 3. Indian Chem. Soc. l, 440 (1956); Chem Abeut. 51, 2625 (1957). (70). V. 0. Kulkarni and 0. V. Jadbav, J. Indian Chem. Soc. 33, 266., 519, 818 (1956); 34, 324 (1957); Chem. Abet. 51, 1068, (1957); 52, 2796, ). (71). Ibid., p. 738; Chem. Abet. 51, 8706 (1957). (72). 1).-0. Kundiger,, H. Pledger and L. E. Ott, J. Am'. Chem. Soc. 7,6659 (1955). ( C. Kiimur and K. Takiura, Ann. Rept. Takeda Research 1-ab.h- m (1949); Chiem. Abut. 47, 6359 (1953). 74). V. Norsk, Chem. Liut,, 43, 209 (1949); Chem. Abet. 45, 542 (1951). 75).* D. Buckley and H. B. Henbest, J. Chem. Soc. 19% ). A. I. A. Werner and J. Gray, Sci. Proc. Roy. Dublin Soc. 24, 111 (1946); cem. Abut. 41, 710 (1947).- (77). S. a. Oable and 0. W. Kerr, U.S. 2,729,637, Jan. 3, 1956; Chem. Abet. 50,

14 (78). P V. Kent., Piochem, J. 55, 361.(1.953). gq) w.,. Truce, 0. H. Birun and Z. T. McSee, J. Am. Chem. Soc (1952). 80)9 R. P(rst, J. Lang, and P. P. Pamelt, Chem. Tech. 1P 359 (195-3); chem. Abet. 47, (1953) BR. Nicolaisen (to Olin Mathieson Chem. Corp), U.S. 2,731,109, Jan. 17, at and A. Patchornik, J. Am. Chem. Soc. 4, 4494 (1952). SS. 83 '. 2 Nam 6d M.Fji)to fam. _.ul. (Tbkyo), 389 (1951); Che. Abet., 54(6 (1960). 85-A. Schonberg and W. Asker., J.. Chem. Soc. 1,242, 725. (1939); Chem. Abet. 33, 8603 (1939). 3R.E. Lyle and Lyle, J. Org. Chem. 18, 1058 (1953). 9 N. Tokura, R. Asami, and R. Tada, Sc1. epdto,. Research Inste., Tohoku Univ., Ser. A 8, 149 (1956); Chem. Abst. 51, Chem. Abst. 51, 4947 (1957). (90). H.E. Pierz-David, L. Blangey and E. Merism, Helv. Chim. Acta, L4, 846 (1951.) (Leading reference). 91). F.. Blicke and H. C. Godt, J. Am. Chiem. Soc. 76, 2798 (1950). 82).V.0. Pesin, A. N. Khaletakii,, and C. Chac, Thur. Obahchel Thim. 27, 1570 (1957); Chem. Abet. 52, 3790 (1958). (93). H. F. Herbrandson, R. T. Dickerson, Jr., and J.. Weinstein, J. Am. Chem. Soc. I 2576 (1956). (94). F. SMrm, J. &wt, and J. Beranek, Chem. Usity -, 573 (1955); Chem. Abet. 50, 2429 (1956). (95). L. Anschutz and H. Wirth,?Naturvi.senschaften ýb 59 (1956). (96. * hid., p R. H oraf., Ann. _ 50 (1952). 198). R. Mess, Rev. facultad humanidad y ciene. (Montevideo) 2, do. 3, 65 (1948); Chem. Abet. 43, 1744 (1949). (99). 0. Machell, Chem. Products 12, 307, 356 (1956); Chem. Abet. 50, 14501, 1%09 (1956). (200). "Encyclopedia of Chemical Technology," Vol. 13, Interecience Publishers, Nev York p. 406 (1954). (101).H. 8. Booth and F. C. Mericola, J. Am. Chem. Soc. 62, 64o (19i4). (102). D. M. Yoat,. Proc. Indian Acad. S 2. 2A, _3( '8)Chem. bst. 33, 4873 (1939). (103). P. Bender and J. N. Wood, Jr., J. Chem. Thys. 23, ) (104). J. K. ioane and M. K. Wilson, J. Chem. Phys. 2j, 1313 R1955)- (105). I. C. Ferguson, J. Am. Chem. Soc. L (195,+). (106). H. Moissan and P. Lebeau, Copt. rend., 130, 1436 (1900)., 107). W. Steinkopf and J. Herold, J. rakt. Chem. 101, 79 (1920). (108). K. Wiechert, Z. anorg. h 26, 310 T195o). 109). F. See and L. Riehl. Z. whor'g.-'u. allgem. Chem. 282, 293 (1955). 10.F. Seel,9 H. Jonas, L. Riehi,, and J. Langer, Angew. Chem. 1, 32 (1955). o. Ruf and K. Thiel, ser., 3, 49 (1905). 112). H. C. Clark and H. J. Eaeleus, J. Chem. Soc. 195, U. Wanna'w. and F. Mennicken, Z. anorg. u. algem. Chem (1955). 3.14l-~ n..cfmnn. g.(e.~ 20 6 (160) (155 5). H. Jonas, Z. anorg. u. il.gem. Chem. 265, 273 (1951) A. Hayes and J. R. Partingt~on, J. Che-' Soc. 1" H 8tammreleh,, J. Chem. Phys.. U 177T(1956). _ 118) H. Hibbert and J. C. Plmanp, Inorganic Syntheses." Vol. I, E.g. Booth, ed., Mcarav-Hill Book Co., N.Y. p jn 0.. M. J. Fraszer and W. Gerrard, Chemistry and Industry, R..ELderfield et al., J. Am. Chem. Boa., 1579 (1946).

15 AP. D. 2. Ames and R. 9. Bowman, J. Chem. W1 Soc. 2) 19 M. 06. J. Frazer, W. Gerrard, 0. Machell, and Industry, B. D. Shepherd, 1954., 931. Chemistry and (123). R4. J. Frazer and W. Gerrard, Research Correspondence, Diprl. to Research (London), No. 4, S27-8 (1954); Chem. Abet. -49, 8962 (1955); J. Chem. Soc. 1955, (12). I-. Johnson, T. H. Norris, and J. L. Huston, J. Am. Chem. Soc. L3, 3052 (1953). -,. (125). R. H. Herber., T. H. Norris, and J. L. Huston, J. Am. Chem. Soc. 76, 2015 (1954). (126) B. X. Masters and T. H. Norris, J. Am. Chem. Soc. U, (1955).,7 M. R. A. Rao Proc Indian Aced. Si. 11A, 195, 201 (1940); Chem. Abet. 34, 7200 (19 4 0o). He~ Spandau and 3, Bruneck., Z. anorg. u. allgem. Chem. 278 ~ 197 (1955)..A. R. V. rthy, Po_. a _.. E.U, 17, (ff), Chaem. Abet. 47, (1953). (130). V. B. &owwe and L. C. King, J. Am. Chem. Soc. 71, '926 (1949). \