3,151,140 United States Patent Office Patented Sept. 29, 1964 2. However, it has been found that when a tetrafunctional 3,155,140 reactant is employed, i.e. in which x is equal to 4, and HETEROLINEAR TETRAPHENYBTADENE when E has a valency of 4, the following spiro compounds COMPOUNDS AND PROCESS OF PRESPAR are formed: NG SAME m Karl W. Eube, Ernie H. Braye, and Agnace H. Capier, es Brussels, Belgia, assignCE's to Union Carbide Corpora 1 tion, a corporation of New York E No Drawing. Fied June 15, 1960, Sei, No. 36,130 7 Cains. (C. 269-431) gs is O Among the general classes of reactants particularly pre This invention relates to the preparation of organic ferred for the practice of this invention are those in which compounds and to products resulting therefrom. More X is a halogen and in which R is a lower alkyl or phenyi particularly, it relates to a process for the preparation of group. However, in the practice of this invention, a heterolinear and heterocyclic organic compounds. broad range of mono and polyfunctional reactants may The present invention greatly facilitates the synthesis 5 be employed. of hetero-atom containing organic compounds in that it In this regard, exemplary of the monofunctional re provides a new and general one-step method for this pur actants useful in the practice of this invention are methyl pose. The lack of such a general method has heretofore beryllium iodide (CHBeI), ethyl magnesium chloride sharply restricted the number of heterolinear and hetero (C2H5MgCl), methyl zinc chloride (CHaZnCl), ethyl cyclic compounls (particularly the latter) to a relatively 20 cadmium chloride (CHCdCl), phenyl mercury chloride Small amount. (CHHgCl), diphenyl boron chloride (C6H5)2BCI, di According to this invention, a process for the prepara methyl aluminum halide (CH3)2AIX, dimethyl gallium tion of heterolinear and heterocyclic organic compounds chloride ((CH3)6aCl), diphenyl indium chloride comprises reacting a 1,4-dilithio-tetraphenyl butadiene with a reactant represented by the formula: 25 diethyl thalium chloride (CH5)2T1Cl, tri-alkyl and tri-aryl silicon halides, such as wherein X represents a member selected from the class consisting of halogens, hydroxy, alkoxy and phenoxy (CH3)3Six and (CH) SiX groups; E represents an element selected from the group 30 dimethyl isopropy germanium bromide, trimethyl tin consisting of gold, zinc, cadmium, mercury, boron, alumi bromide (CH) Snbri, triphenyl lead bromide num, gallium, indium, thallium, the lanthanides, silicon, (C6H5)3PbBril germanium, tin, lead, titanium, zirconium, hafnium, nitro gen, phosphorus, arsenic, antimony, bismuth, Vanadium, triphenyl lead hydroxide niobium, tantalum, oxygen, sulfur, selenium, tellurium, 35 (CH) Pb(OH)1, CHSONCNa iron, cobalt, nickel, palladium and platinum; R represents a member selected from the class consisting of Substituted diphenyl chlorophopsine (C6H5)2PCl), diphenyl chloro and unsubstituted alkyl, aryl, cyclopentadienyl, phosphino, arsine (C6H5)2AsOll, diphenyl chloro stibine cyclobutadienyl and cyclooctatetraenyl groups; R repre sents a member selected from the class consisting of OXy 40 gen, sulfur, selenium, tellurium, and a carbonyl group; X diphenyl chloro bismuthine, sulfuryl halides, dichloro is an integer having a value of from 1 to 4; y is an integer selenoxide (SeOCl). m having a value of from 0 to 4; and W is an integer having Exemplary of the polyfunctional reactants useful in the a value of from 0 to 2. Obviously, the value of x, y and practice of this invention are IP (CH3)3]2NiCl2, w is such that the valence of E is satisfied. 45 Employing a monofunctional reactant, i.e. where X is CHPi, chlorine monoxide, -sulfur halides such as equal to 1, the compounds formed by the process of this SC1, SC1, sulfuryl halides such as SO3Cl2, selenium invention will have the following structure: halides such as SeaCl, selenoxides such as SeOCl, tel 50 lurium halides such as TeCl4, Tefs, N,N-dichloro-p- R-E-C=C-C=C-E-R toluene-sulfonamide, phenyldichlorophosphine, wherein R and E have the meanings defined above. (C6H5PC) . Employing a bi- or tri-functional reactant, i.e. where ethyl dichlorophosphine (CHPCl2), trichlorophosphine is is equal to 2 or 3, or a tetrafunctional reactant where (PCs), dibromo fluoro phosphine (PBrF), benzyl di the element E has a valency of other than four, the com chloro-phosphine (C6H5CH2PCl2), C6H5P(S) Cl2 pounds formed will have the following structure: (CH5)2P(S) Cl - methyl diiodo phosphine (CHPI2), phosphorus penta halides such as PBrs, PCls, phenyl dichloro arsine 60 (C6H5ASCla) phenyl dichloro stibine (C6H5SbCl2), phenyl dichlorobis muthine (CHBiCl2), bis-cyclopentadienyl-vanadium di wherein E, R, and R also have the meanings defined chloride (C5H5)2VCl2, bis-cyclopentadienyl-niobium above. It is to be understood that the number of Substitu tribromide (C5H5)2NbBr, bis-cyclopentadienyl - tanta ents of R and/or R', if any, bonded to E will be deter 65 lum tribromide (C5H5)2TaBra), silicon tetrachloride, di mined by that necessary to satisfy the remaining unfilled phenyl-silicon dichloride (C6H5)2SiCl2), germanium tet valency of E. For instance, if E has a Valency of 2, the rachloride dimethyl-germanium-dichloride, tin tetrachlo structure will have the formula: ride, dimethyl-tin-diiodide (CH3)2Snlal, diphenyl-lead-di bromide, lead tetrachioride, bis-cyclopentadienyl-titanium 70 dichloride (C5H5)2TiCl2), bis-cyclopentyldienyl zirconi NE y-d um dichloride (C5H5)27rCl), bis-cyclopentadienyl-hafni S. c. um dichloride (C5H5)2HfCl2, borontrichloride, tri-alk 3,151,140 3 4. oxyboron such as IB(OCH), phenylborondichloride wherein E represents silicon, germanium, tin, lead, ti (C6H5BC12), alkyl and aryl aluminum dichloride, methyl tanium, zirconium or hafnium. gallium dichloride (CHGaCl), methylindium dichloride Exemplary of such spiro structures are the following (CHInCl2), indium chloride (InCl2), phenyl thallium two representative compounds: dichloride, zinc chloride, cadmium chloride, mercury Octaphenyl-spiro-bicyclosilole halides such as HgEra, phenyl gold dichloride, gold trichlo Octaphenyl-spiro-bicyclostannole ride. For the practice of this invention, it is preferable to The invention may be further illustrated by the fol employ at least stoichiometric amounts of the starting lowing examples: materials. The reaction is also usually carried out in a O EXAMPLE 1. polar or non-polar organic solvent such as ether, di 3 g. (16.9 mM.) diphenylacetylene and 0.6 g. clean methoxyethane, tetrahydrofurane, dioxane and the like. lithium shavings were shaken in 8 ml. dry diethylether The process of this invention is generally carried out in an inert atmosphere (nitrogen). After an induction at temperatures of between -50° C. and 200 C. While period varying between ten and twenty minutes, the operation at such temperature ranges is generally ac reaction mixture became brownish red. Shaking was ceptable, it should be noted that when preparing hetero continued for one to two hours. In some cases, the cyclic systems containing silicon, that heating above room 1:4-dilithio-tetraphenylbutadiene precipitated out. Fifty temperature is highly preferable, i.e. heating of the order ml. dry ether was added and the floating Li-shavings of between 60 C. and 120° C. were removed mechanically; the mixture was thereupon The pressures required by the process of this invention cooled at about -40 C. and a solution containing 8.8 are not highly critical. However, it is preferable, when mM. SeaBr2 in 50 ml. benzene was added over a period employing highly volatile reactants, to employ a closed of 10 minutes to the lithium derivative. The temperature system and an inert atmosphere. was allowed to increase to room temperature. Red The reactions product are easily removable from the amorphous Selenium was formed. By shaking for one reaction mixture after completion of the reaction using night, the selenium crystallized and was filtered off (1.3 g; convenitonal techniques such as, for example chromato 93%). The filtrate was washed with water. From the graphy. However, the technique will of course vary organic layer, there was obtained 2.39 g. (65% based according to the nature of the reaction product. Suitable on diphenylacetylene) of tetraphenylselenophene (M.P. proven condition will be further illustrated in the specific 182 C.) which may be represented by the structure: examples hereinafter described relating to the present 30 invention. C Cas As mentioned previously, the process of this invention will result in a wide variety of compounds. In this regard, o, C6H similar hereto-containing compounds have been produced Se by the process described in copending application S.N. EXAMPLE 2 18,805, filed in the name of K. W. Hubel and E. Braye, on March 31, 1960. In that application the suffix A similar amount of 1:4-dilithio-tetraphenyl-butadiene “ole' was employed to generally designate the five-mem was prepared as described in Example 1. 60 ml. ether bered heterocyclic systems. Such nomenclature will also were thereupon added and then 0.8 g. (2.7 mM.) be hereinafter employed to refer to many of the hetero 40 TeCl4, whereby a vigorous reaction took place. After cyclic compounds produced by the process of this in refluxing one hour, water and benzene were added. vention. This nomenclature will be more apparent from Chromatography of the reaction products on aluminum the following list of purely representiative heterocyclic oxide, gave 0.61 g. (20% based on tolane) 1:2:3:4-tetra compounds which may be produced by the process of this phenyl-butadiene and 0.7 g. (53.5% calculated on TeCI) invention. tetraphenyltellurophene. 45 This compound, crystallized in colourless needles from Hexaphenylzirconole Tetraphenylselenophene a mixture of methylene chloride and ethanol, melted at Tetraphenyltellurophene 240-241. C. Pentaphenylphosphole Anaylisis Pentaphenylphosphole-S- 50 Benzyltetraphenylphosphole and the oxide thereof Theoret, calculated p. Methyl-p. oxide-tetraphenylphosphole Found for Case Pentaphenylarsole (M.W. =484.08) Pentaphenylstibole and the oxide thereof C------70.3 69. 48 Hexaphenylsilole H------42 4.17 Tetraphenyl-mercurole 55 Te------23, 45 26.35 Zr bis(cyclopentadienyl)-tetraphenyl-zirconole Aur chloro-tetraphenyl-aurole EXAMPLE 3 Pentaphenyl-borole A Suspension of 1:4-dilitho-1:2:3:4-tetraphenylbuta Pentaphenyl-thallole 60 diene was prepared from 18 g. (100 mM.) diphenyl Hexaphenyl-Stannole acetylene, according to the procedure of Example 1. Exemplary of hetero-linear compounds obtainable by The volume of the reaction mixture was brought to 500 the process of this invention are ml. by adding dry ether. Under stirring, a solution of 1,4-di(phenyl-mercury) 1,2,3,4-tetraphenyl-butadiene 10 ml. (about 73 mM.) phenyldichloro-phosphine in 100 65 ml. ether was added slowly. After another 5 min, stir 1,4 bis(chloro Sulfonyl) 1,2,3,4-tetraphenyl-butadiene. ring, 50 ml. water was added. The fine yellow precipitate Also with respect to the products obtainable by the was filtered off, and washed with methanol and ether. A process of this invention, of particular note is the prepara yield of 14.46 g. (62%) of pentaphenylphosphole (M.P.: tion of a heretofore undisclosed class of compounds 255-256.5) was obtained, which may be represented by namely spiro systems having the following structure: 0. the structure: s b ps C Css

- - - C P J-CH = 1 = is gis p sp 75 CH 3,151,140 6 EXAMPLE 4 of water, a greenish yellow precipitate was filtered off, and 5.4 g. CH5-P(S) Cl2 was dissolved in 50 ml, ether. washed with alcohol and ether. This product 4.0 g.:56% A suspension of 1.4 di-lithio-1:2:3:4-tetraphenylbuta based on diphenylacetylene) is strongly fluorescent, melts diene prepared from 5 g. tolane (as in Example 1) was at 213-214.5 C. and according to analysis and I.R. spec then slowly added. Beside pentaphenylphosphole, one tra, is penta-phenyl-arsole. This compound may be rep isolated penthaphenylphosphole-sulphide (M.P. 196), presented by the structure: - - - identical with the compound obtained from the sulfuration of pentaphenyl-phosphole. -CHs Analysis O o J. As Theoretically calcu Cas Found lated for C4H2S (M.W.s 496.61) Analysis C------82. 82,23 M 5.3 5.08 Theoretic. calcu 6.29 6.24 Found lated for C34E5As 6, 10 6, 45 (M.W. =508.48) This substances may also crystallize with one mole C------79.22 80.30 methylene chloride, which is lost at 100-120° C. 20 H------4.77 4.96 EXAMPLE 5 EXAMPLE 8 To a suspension of 1:4-dilithio-1:2:3:4-tetraphenylbuta diene, prepared from 2 g. (11.24 mM.) tollane and Li in To a suspension of 1:4-dilithio-1:2:3:4-tetraphenyl accordance with the procedure of Example 1, a solution butadiene, 1.84 g. CHSbO2, dissolved in about 50 ml. of 1.5 m. CHCHPCl2 (about 10 mM.) was added. dry ether, was added. The reaction mixture was refluxed After 15 min. Water was added, the organic layer dried, for 5 hours. After addition of water, the organic prod evaporated, and the residue taken up in benzene. This ucts were extracted with benzene, the dried organic layer solution was chromatographed over aluminum oxide. evaporated and the residue, dissolved in benzene, was 30 chromatographed on silica gel. The fraction eluted with Elution with benzene yielded 0.85 g. (32%) P-benzyl a mixture of benzene/petroleum ether, yielded 0.8 g. tetraphenylphosphole, crystallizing into yellow, strongly (14.4%) of big greenish yellow crystals of M.P. 162 fluorescent leaflets, of M.P. 203-213 (microsc.), 190 170° C. (decomposition). (Kofler hot stage). The I.R. spectra showed analogy with the correspond Analysis ing phosphor- and arsenic-heterocyclic compounds and was also fluorescent (greenish shade). This compound Theoretic. calcu Was fairly easily oxidized in solution. The correspond Found lated for C3H3P ing yellow oxide was not fluorescent and melted under (M.W. s.478, 6) decomposition at 250-255 C. C------87. O6-87.00 87.86 40 H------5. 64-5, 56 5.27 Analysis

Elution with ethyl acetate yielded in small amounts Theoret, calculated the corresponding oxide which crystallized in needles Found for C3H25OSb (from petroleum ether) or leaflets (from diethylether (M.W.F571.33) or petroleum ether), M.P.: 228-230 C, C------2.12 7.47 H------4.65 4.4 Analysis O------2.74 2.80 Theoretic, calcu Found lated for C3H7OP EXAMPLE 9 (M.W. =494.6) Tolane (3 g; 16.9 mM.) was shaken with excess Li for C------84.35 85.01 1 hour in 8 ml. ether as in Example 1. Dioxane (60 mi.) H------5.46 5.0 and SiCA (0.34 ml. =0.505 g. =3 mM.) was added. The diethylester was removed by distillation. After one hour EXAMPLE 6 reflux (at 100 C.), water and benzene were added. By The same di-lithium-compound obtained from 2 g. chromatography, there was separated 0.59 g. (27% based diphenyl-acetylene was treated as in Example 4 with 1 on SiCl4) yellow nonfluorescent crystals, melting from m. CHPI. By chromatography, P-methyl-P-oxide-tetra 140 to 280° C. This compound may be represented by phenylphosphole, a slightly fluorescent and pale yellow the structure: C6H5 CIS C6H5 Css product of M.P.: 240.5-241.5° C. (from chloroform N / / and ether) was obtained. Si Analysis 7 \ C6H CE5 CH5 CEIs Theoretic, calcu Foad lated for Ceg3OP Analysis (M.W. c.418.48)

C------82.79 83.22 Theoretically cal H------5.44 5.54 Found . . Cuiated for 70 C5HoSi. (M.W. = 741.03) EXAMPE 7 90.7 90.76 To a suspension of 1:4-dilithio-tetraphenyl-butadiene 5.78 5. 44 prepared according to Example 1, from 5 g. diphenyl 2.45 3.80 acetylene, 2 ml. CHAsCl2 was added. After addition 75 3,151,140 7 8 EXAMPLE 10 amounts), and dissolved in 200 ml. dioxane. Beside LiCl, HgCl2, Hg, (C6H5)2Pig and 1.5 g. unreacted To a suspension of 1:4-dilithio-1:2:3:4-tetraphenyl CHHgCl, there was obtained in fairly good yield, a butadiene prepared from 9 g. (50 mM.) diphenylacetyl pale yellow compound, M.P. 145 C. Its I.R. spectrum ene, 300 ml. pure tetrahydrofurane (T.H.F.) and 5.2 ml. and analysis indicate a formula of: (6.3 g.=2.5 mM.) diphenyl-dichloro-silane were added. 5 1:4-bis(phenylmercuri)-1:2:3:4-tetraphenyl-butadiene. The diethylether was distilled off and the reaction mixture refluxed for four hours. Water and benzene were there Analysis upon added. 6.7 g. (50%) pale greenish yellow strongly fluorescent crystals were obtained with M.P.: 190-191 C. (from isopropanol). The structure may be called O Found Theoretic, calculated hexaphenyl-silole and may be represented as follows: for C40H80Higa C C6H5 56.74. 52. 69 3.69 3.32 38.98 43.99 Cols CEIs. I s N CE CES EXAMPLE 1.4 Analysis 1.6 g. bis-cyclopentadienyl-zirconium dichloride, dis Theoretic. calcu 20 solved in the necessary amount of ether, was added to a Found lated for suspension of the above-mentioned dilithium-compound C40H80Si prepared from 3 g. tolane. Orange square plates crystal (M.W. =538.73) lized out immediately with LiCl. The mixture was fil 88.97 89.18 tered, washed quickly with water and immediately dried in 5.67 5, 6 25 vacuum. The yield varied between 45% and 65%. am me - 5.22 5.21 Alcoholysis or hydrolysis yielded cyclopentadiene, tetra phenylbutadiene and zirconiumoxide. The compound, EXAMPLE 11 which decomposes at 140-170 C., may be represented as To a suspension of 1:4 dilithio-1:2:3:4-tetraphenyl follows: butadiene, prepared from 3 g. (16.9 mM.) tolane, in 30 ether, 0.33 ml, (6 mM.) SnCl4 was added. After 1 hour C6Hs reflux, 0.95 g. (19%) yellow crystals of M.P. 265-272 C. were obtained after chromatography on silica gel. . J. Z The structure of the compound obtained is analogous to 7. R. the one obtained in Example 9 with the exception that Cp Cp Sn is Substituted for Si. Cp = cyclopentadienyl Analysis EXAMPLE 1.5 Theoretic. calcu A solution of 0.77 g. AuCl3, dissolved in 200 ml. ether, Found lated for 40 C56H40Sn was added to Li-CPh=CPh-CPh=CPh-Li. After (M.W. =831.64) one hour reflux, the reaction mixture was filtered off, the filtrate evaporated and the residue, dissolved in a mini 80.36 80.87 mum amount of benzene, chromatographed on silicagel. 4.60 4,85 The fraction eluted with benzene yielded yellow brown Sn- 4, 24 4.27 crystals, which after recrystallization from CHCl2, gave 45 needles of M.P. 185-192 C. (decomposition). This EXAMPLE 12 compound contained chlorine and the content of gold, 2 g. (7.4 mM.) HgCl2, dissolved in 100 m. ether, were estimated by X-ray fluorescence, indicated a percentage added slowly and under cooling to a suspension of 1:4- of about 30%. The structure may be represented as dilithio-tetraphenylbutadiene, prepared from 3 g. (16.9 50 follows: mM.) tolane, in ether. ps Following the procedure previously outlined, minor amounts of tetraphenylbutadiene and, in a good yield, a 2 N yellow compound of M.P. 188-190° C. (from CHCI A and ethanol) was obtained. This product contained a 55 C great percentage of mercury; its I.R. spectrum, analysis and M.P. indicate a structure which may be represented Analysis as follows: Theoretic. calculated Cas Found for C28H2AuCl HC J. 60 (M.W. =588.93) C------58.28 57.10 Yi, H------3.64 3.43 Analysis All------35.0 33.6 65 Theoretic. calculated Found for C28H20g EXAMPLE 16 (M.W.-557.08) 1.6 ml. CHBC12, dissolved in 20 ml. ether, was added C------55. 32 60.27 to an ethereal (30 ml.) suspension of the dilithium-com H------3.28 3, 62 70 pound prepared from 3.6 g. diphenylacetylene. The re action mixture was kept 20 hours at room temperature and then filtered. The filtrate was evaporated to dryness, EXAMPLE 3 the residue taken up in benzene, and chromatography on The same lithium-compound, prepared from 5 g. tolane, silica gel yielded among other, 2.65 g. of a yellow product was reacted with 8.77 g. CHHgC (stoichiometric 75 of M.P.150-155° C. 3,151,140 Anaysis indicates the structure to be as follows: Analysis

C E. s U.B y-d Found------75, 98 4.65 p Calcul, for C40H80Sn, M.W. =629.38.------76.33 4.81 Analysis The hetrocyclic systems prepared employing the Theoretic, calculated process of this invention are important intermediates for Found for C3H58 (M.W. many organic syntheses. For example, they may be used =444.39) in the preparation of dyes, pigments, pharmaceuticals, or

for the preparation of organo-metallic complexes in a 92.6 989 6,04. 5, 67 manner similar to that disclosed in copending application ------2.44 56,366, filed in the names of K. W. Hubel and E. Weiss 5 on September 16, 1960 and now abandoned. EXAMPLE 1.7 In addition many of the five-membered heterocyclic compounds are strongly fluorescent materials and may be By reacting C6H5TICl in accordance with the proce employed as such. Exemplary of such fluoroscent dure previously outlined, heterocyclic systems are the arsoles, phospholes, stiboles Li-CPh=CPh. CPhocCPh-Li and silioles. In this regard, these compounds generally pentaphenyl-thallol was obtained which had a faintly yel exhibit a yellow-green fluorescence comparable to that of zinc or cadmium sulfides. The fluorescence spectrum can low color. The structure may be represented as follows: be often shifted to the corresponding oxide thereby mak ing it possible to variably provide a fluorescent compound having the particular fluorescent spectrum desired. th- y-s The hetero-containing compounds of this invention also T behave as dienes and can, therefore, be involved in Diels p Alder reactions. For example, the reaction of penta phenylphosphole with the dimethyl ester of acetylene di M.P.: 165-169 (decomp.) 30 carboxylic acid yields the dimethyl ester of tetraphenyl Analysis phathalic acid in almost quantitative amounts. A normal adduct is also obtained by Diels-Alder addition with ion Theoret. calculated maleic anhydride. The linear hetero-atom containing for C32T1 compounds are also useful as intermediates for drug and pharmaceutical preparations. C------62. 12 640 Another general use for the metal containing com ------3,83 3.95 pounds prepared by the process of this invention is as anti-knock additives in motor fuels either alone or in conjunction with other organo-metallic compounds. They EXAMPLE 1.8 40 A solution of 1:4-dilithio-tetraphenylbutadiene, pre could also be used as metal-plating agents. For this pared in 10 ml. ether from 3 g. diphenylacetylene and an use, the metal containing compounds obtainable by the excess of Li, was diluted with ether to 60 ml. and added process of this invention are contacted with a platable slowly to a solution of 2 ml. sulfurylchloride in 80 ml. Substrate at a temperature of more than the decomposi ether, at a tempearture of -50 C. The temperature was tion temperature of the metal containing compound, either allowed to increase to room tempearture, water was added, 45 in solution or in a vapor phase. A platable substrate will and the yellow precipitate, consisting of 0.230 g. tetra be, for instance, glass cloth, a metal or a plastic surface phenylthiophene-dioxide, M.P. 286-288 C., was filtered or the like. off. The filtrate was extracted with benzene, the organic What is claimed is: layer dried over Na2SO4, evaporated to dryness, and the 1. A process for the preparation of heterolinear organ residue was recrystallized from ethanol/petroleum ether, 50 ic compounds which comprise reacting a 1,4-dilithio-tetra yielding 0.620 g. colourless crystals of M.P.: 157-159 phenyl-butadiene with a reactant represented by the C.(dec.) consisting of 1:4-bis(Chlorosulfonyl-) 1:2:3:4- formula: tetraphenyl-butadiene. XE(R), (R)w wherein X is halogen, bonded to E; E represents an ele C1-SO-CPh=CPh-CPh=CPh-SOCJ 55 ment selected from the group consisting of gold, zinc, Analysis cadmiurn, mercury, boron, aluminum, gallium, indium, thallium, the lanthanides, silicon, germanium, tin, lead, C H O titanium, zirconium, hafnium, nitrogen, phosphorus, arsenic, antimony, bismuth, vanadium, niobium, tanta Found------6,94 3.88 j.14 60 lum, Sulfur, Selenium, and tellurium; R represents a mem Calcul. for C28H20Cl2OS2, M.W.s. ber bonded to E selected from the class consisting of 555.51------60.54 3.63 1.52 phenyl and lower alkyl; R is oxygen bonded to E; y is an integer having a value of from 0 to 4; and w is an This compound is transformed easily into tetraphenyi integer having a value of from 0 to 2; the values of y and thiophene-dioxide by merely melting the compound. 65 w being such that the valence of E is satisfied. 2. A process according to claim 1, in which stoichio EXAMPLE 19 metric amounts of the reactants are employed. To an ethereal solution of 1:4-dilithio-tetraphenylbuta 3. A process according to claim 1, in which the re diene, prepared from 3 g. diphenylacetylene, 3 g. action is carried out at a temperature of between -50 PhSnCl2 (50% excess), dissolved in 50 ml. ether, were 70 and 200 C. added. After the vigorous reaction has ceased, water is 4. A process according to claim 1, in which E is silicon, added and the reaction mixture is treated according to and the reaction is carried out at temperatures of be previous methods. Hexaphenylstannole, (slightly fluores tween '60' C. and 120° C. cent yellow greenish crystals) M.P. 172-3 C. was 5. A process according ot claim 1, in which the reaction obtained in a yield of 2.15 g. (40% based on tolane). 75 is carried out in an organic solvent selected from the 3,151,140 2 group consisting of ether, dimethoxyethane, tetrahydro Patterson et al.: "The Ring Index' (1940), pub. by furane and dioxane. Reinhold Publishing Corp. (N.Y.), A.C.S. Monograph 6. 1,4-di(phenyl-mercury) 1,2,3,4 tetraphenylbuta Series, pages 43 and 44. West: “Journal of The American Chemical Society,' "1,4-bis(chloro-sulfonyl) 1,2,3,4 tetraphenylbuta 5 vol. 76, No. 23, Dec. 5, 1954, pp. 6013-6017. diene. Bergmann et al.: "justus Liebig's Annalen der Chemie, vol. 500, No. 2, jan. 20, 1933, pages 122-136. References (Cited in the file of this patent Kuivila et al.: "Journal of The American Chemical UNITED STATES PATENTS Society, vol. 80, No. 13, July 5, 1958, pages 3250-3253. 2,160,915 Schreiber ------June 6, 1939 0. Smith et al.: "Journal of The American Chemical 2,839,566 Letsinger et al. ------June 17, 1958 Society,” vol. 63, No. 5, May 1941, pages 1184-1187. Gilman et al.: "Journal of The American Chemical FOREIGN PATENTS Society,' vol. 77, No. 23, Dec. 5, 1955, pages 6380-6381. 885,847 Germany ------July 8, 1949 Henry et al.: “Journal of The American Chemical OTHER REFERENCES 5 Society, vol. 82, No. 5, Feb. 5, 1960, pages 561-563. Leavitt et al.: J.A.C.S. 81, No. 12, pages 3163-3164. (June 20, 1959).