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States Patent 0 a 3,426,052 States Patent 0 " 1C@ Patented Feb. 4, 1969 1 2 a yellow green, ?uorescence comparable to that of zinc 3,426,052 FIVE MEMBERED ZIRCONIUM, BORON, or cadmium sul?des. The ?uorescent spectrum can be THALLIUM AND GOLD HETEROCY often shifted to the corresponding oxide thereby making CLIC COMPOUNDS it possible to variably provide a ?uorescent compound and Karl W. Hubel and Emile H. Braye, Brussels, Belgium, the particular ?uorescent spectrum desired. assignors to Union Carbide Corporation, a corporation The hetero-containing compounds of this invention also of New York behave as dienes and can, therefore, be involved in Diels No Drawing. Continuation-in-part of application Ser. No. Alder reactions. For example, the reaction of pentaphenyl 18,805, Mar. 31, 1960. This application June 15, 1960, phosphole with the dimethyl ester of acetylene dicar Ser. No. 36,132 Claims priority, application Great Britain, Apr. 7, 1959, boxylic acid yields the dimethyl ester of tetraphenyl 11,679/59 phthalic acid in almost quantitative amounts. A normal U.S. Cl. 260—429 7 Claims adduct is also obtained by Diels-Alder addition with Int. 'Cl. C07f 1/12, 7/00, 5/02 maleic .anhydride. Another general use for the metal containing com~ This invention relates to novel organic compounds and 15 pounds prepared by the process of this invention is as more particularly to novel ?ve-membered heterocyclic anti-knock additives in motor fuels either alone or in compounds. conjunction with other organo-metallic compounds. They This application is a continuation-in-part of our co could also be used as metal-plating agents. For this use pending application Ser. No. 18,805, ?led Mar. 31, 1960, the metal containing compounds obtainable by the process and now U.S. Patent No. 3,280,017, entitled, “Process 20 of this invention are contacted with a platable substrate for the Preparation of Hetero-Atom Containing Organic at a temperature above the decomposition temperature Compounds and Products Resulting Therefrom.” of the metal containing compound, either in solution or The compounds of this invention can be conveniently in a vapor phase. A platable substrate will be, for in represented by the following general formula: stance, glass cloth, a metal or a plastic surface or the like. 25 The novel compounds of this invention can be pre pared by the process described in copending applications Ser. No. 18,805, ?led in the names of K. W. Hubel and E. H. Braye, ?led Mar. 31, 1960, now U.S. Patent No. 3,280,017; Ser. No. 36,131, ?led concurrently herewith, wherein R represents a member selected from the class 30 in the names of K. W. Hubel and E. H. Braye, now U.S. consisting of hydrogen, and the hydroxyl, halogeno, car Patent No. 3,149,101; and Ser. No. 36,130, ?led con boalkoxy, substituted ‘and unsubstituted alkyl, substituted currently herewith in the names of K. W. Hubel, E. H. and unsubstituted aryl, cycloaliphatic, alkoxy, phenoxy, Braye and I. Caplier, now U.S. Patent No. 3,151,140, and silyl groups, B represents an element selected from the descriptions thereof being incorporated herein by the group consisting of gold, zinc, cadmium, mercury, reference. The reactions disclosed in these copending boron, aluminum, gallium, indium, thallium, the lantha applications shall be hereinafter designated, for con nides, silicon, germanium, tin, lead, titanium, zirconium, venience only, as Process A, Process B and Process C. hafnium, phosphorus, arsenic, antimony, bismuth, vana Generally speaking, Process A comprises the reaction dium, niobium, tantalum, iron, cobalt, nickel, platinum of an organo-metallic complex having the formula: and palladium; R’ is hydrogen, and the hydroxyl, halo 40 Mx(CO)y(R'C2R")Z(Q)w with an element belonging to geno, carboalkoxy, substituted and unsubstituted alkyl, Groups I-II—A, IV~A, VA or Vl-A of the Periodic Ta substituted and unsubstituted aryl, cycloaliphatic, alkoxy, ble, or a compound containing at least one of the ele phenoxy, silyl, cyclobutadienyl, and cyclopentadienyl ments of those Groups. In the above referred to organo groups; and m represents an integer having a value of metallic complexes, M represents a transition metal be from 0 to 2. longing to the VI, VII or VIII sub-groups of the Periodic It is to be understood that the presence of an R'm Table, CO represents a carbonyl group, R’ and R" may be group will be determined by the remaining un?lled the same or different and represent hydrogen, halogeno, valency, if any of E, i.e. the representation of in may carboalkoxy, alkyl, aryl, cycloaliphatic, alkoxy, or silyl be expressed as m=valency of E-2. ‘groups and the like, including the substitued derivatives Among those compounds preferred in the practice of 50 thereof, C2 represents a carbon to carbon bonding, Q this invention are those in which R is a lower alkyl or represents a member selected from the group consisting phenyl group, E is gold, mercury, boron, thallium, silicon, of hydrogen, mercury, halogen, alkyl, aryl or acyl, x and zirconium, and R’ is a halogen, a lower alkyl, a represents an integer of from 1 to 4, y represents an integer from 1 to 10, z represents an integer of from 1 phenyl or a cyclopentadienyl group. It should be noted 55 that the oxides and other derivatives of these and the to 6, and w represents an integer of from '0 to 4. It is to other novel compounds of this invention can also be pre be noted that Process A is useful for the preparation of pared with facility and such are, therefore, within the the aforesaid elements of Groups III-A, ‘IV-A, VAA or scope of this invention. VI—A of the Periodic Table. The heterocyclic systems prepared employing the Generally speaking, Process B comprises the reaction process of this invention are important intermediates for of a butadiene derivative having the formula: many organic systems. For example, they may be used in the preparation of dyes, pigments, pharmaceuticals, or “it for the preparation of organo-metallic complexes in a manner similar to that disclosed in copending application X‘re-Ce’ X Ser. No. 784,040, ?led in the names of K. W. Hubel and E. Weiss, and now abandoned. wherein X represents a halogen and wherein R represents a member selected from the class consisting of hydrogen, In addition, many of the ?ve-membered heterocyclic and alkyl and aryl groups; with a reactant represented compounds are strongly ?uorescent materials and may by the formula: be employed as such. Exemplary of such ?uorescent het 70 erocyclic systems are the arsoles, phospholes, stiboles, and (A)XE(R')y siloles. In this regard, these compounds generally exhibit wherein A represents a member selected from the group 3,426,052 4 consisting of an alkali metal, and an alkaline earth metal; Ti .bis (cyclopentadienyl) -tetraphenyl-titanole E represents an element selected from the group consist Hf.bis (cyclopentadienyl) -tetraphenyl—hafniole ing of gold, zinc, cadmium, mercury, boron, aluminum, The following examples serve to illustrate the practice gallium, indium, thallium, the lanthanides, silicon, ger manium, tin, lead, titanium, Zirconium, hafnium, nitrogen, of this invention further. phosphorus, arsenic, antimony, lbismuth, vanadium, ni EXAMPLE I obium, tantalum, oxygen, sulfur, selenium, tellurium, iron, cobalt, nickel, palladium, and platinum; R’ repre 1 g. of FCZ(CO)6(CGH5CZCGH5)Z and 5 ml. Of sents a member selected from the class consisting of hy C5H5PC12 drogen and alkyl and aryl groups; x is an integer having 10 were heated for 30 minutes at about 140° C. A pale yel a value of from 1 to 2; and y is an integer having a value low organic substance having a M.P. of 255—256° C. was of from 0 to 4. obtained in a 66% yield. Analysis showed that this com Generally speaking, Process C comprises a reaction of pound has a formula C3iH25P. a 1,4-dilithio butadiene with a reactant represented by Analysis.—Theoretical calculated for C34H25P: C, the formula: 15 87.93; H, 5.43; P. 6.68. Found: C, 87.47; H, 5.27; P, 6.34. EXAMPLE II wherein Q represents a member selected from the class consisting of halogens, hydroxy, alkoxy, and phenoxy ml.)1 C5H5CH2PBr2 and 20 ml. CGHS were heated for 15 groups; B represents an element selected from the group 20 hours at 170° C. in a sealed tube. Besides 0.14 gram consisting of gold, zinc, cadmium, mercury, boron, Fe(CO)3(C6H5C2C6H5)2 and 0.09 grams tetracyclone, aluminum, gallium, indium, thallium, the lanthanides, 0.07 gram of a yellow-, strongly ?uorescent P-benzyl-P silicon, germanium, tin, lead, titanium, zirconium, hat oxide-tetraphenyl-phosphole having an M.P. of 220-227” nium, nitrogen, phosphorus, arsenic, antimony, bismuth, C. was isolated by chromatography. This phosphole-oxide vanadium, niobium, tantalum, oxygen, sulfur, selenium, 25 was formed by air oxidation of the primarily formed P tellurium, iron, cobalt, nickel, palladium, and platinum; benzyl-tetraphenyl-phosphole. R represents a member selected from the class consist Analysis.—Theoretical calculated for C35H27OP: C, ing of substituted and unsubstituted alkyl, aryl, cyclo 85.01; H, 5.10. Found: C, 84.35; H, 5.46. pentadienyl, phosphino, cyclobutadienyl and cycloocta EXAMPLE III tetraenyl groups; R’ represents a member selected from 30 the class consisting of oxygen, sulfur, selenium, tellurium, A solution of 1.46 grams (2.3 mM.) (millimoles) and a carbonyl group; x is an integer having a value of F€2(C0)6(C6H5c2C6H5)2lml. CHzClz was irradiated andfor 22 hoursC6H5A$Cl2 in a quartz in vessel from 1 to 4; y is an integer having a value of from 0 to 4; w is an integer having a value of from 0 to 2.
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