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Haired States Pareto ' 2,882,288 Haired States Pareto ' " Patented Apr. 14, 1959,, 1 2 her and character of substituents on the cyclopentadienyl ' carbon ring may otherwise be varied at will. Suitable 2,882,288 organic compounds include hydrocarbon compounds hav QT ORGANO-VANADIUM HALIDES AND PROCESS ing the requisite alicyclic cyclopentadienyl carbon ring. , -' or PREPARATION Examples of such hydrocarbon compounds are cyclo 'John C. Brantley and Edward L. Morehouse, Snyder, pentadiene, its aliphatic derivatives as for example methyl, _-,- - N.Y.,>assignors to Union Carbide Corporation, a cor ' ethyl, allyl and vinyl cyclopentadiene, its aromatic derive ,I partition of New York atives as for example phenyl cyclopentadiene, indene and its comparable derivatives. a No Drawing. Application September 23, 1953 10 The formation of a dihalide according to this invention Serial No. 381,968 may be illustrated by the reaction between cyclopenta—_ 11 Claims. (Cl. 260-429) ' j dienyl magnesium chloride and VCl4. The Grignard re agent may be prepared by reacting magnesium turnings with a lower alkyl chloride in a solvent, ethyl ether, ben Ill-This invention relates to organo-metallic compounds 15 zene or the like for example, and reacting the'resulting containing vanadium as the metal component." The in solution with cyclopentadiene. The cyclopentadienyl vention includes correlated improvements and discoveries magnesium chloride thus formed is then reacted with‘ whereby such vanadium compounds having distinctive VCL; in a suitable liquid medium and the orgauoe properties vare obtained. vanadium dichloride (C5H5)2VCl2 may be recovered ; An object of the invention is to provide organo-metallict 20 from the reaction mixture. The same compound results compounds containing vanadium as the metallic compo~' from reaction of cyclopentadienyl magnesium chloride nent linked to the organic component by carbon to metal " ' with VOCl3. When the halide in the cyclopentadienyl‘ bonds. ' ' ' - carbon ring Grignard reagent is different from that in A further object of the inventionis to provide a method the vanadium halide the reaction product may contain a for producing such organo-vanadium compounds. 25 mixture of dihalides or a mixture of dihalides and mixed "Other objects of the invention will in part be"obvious . dihalide and will have an apparent average empirical and will-in part appear hereinafter. "iThei products of this invention have the general empir-~ I ' formula: ical 4 formula: 80 where X and X’ are different halogens and (y) and (z) are numbers which total 2, i.e. any such numbers be where R is a residue of an organic compound containing tween 0 and 2, depending on the proportions of the par a ?ve carbon ring, alicyclic in character, which is herein ticular halogens present in combined state. By reaction. afterldesignated‘ an “alicyclic cyclopentadienyl carbon with dilute aqueous HCl (C5H5)2VCl(y)Br(z) may bev ring”. and has the structure: ' 35 converted into (C5H5)2VCl2. The reaction of the cyclopentadienyl carbon ring Grignard reagent with vanadium halide is preferably initially conducted at temperatures between about 0° C. C=C/ and —90° C. At temperatures above 0° C. the initial X is halogen and n is 0, 1 or 2. ' 40 reaction of the vanadium halide with the Grignard re-‘ The alicyclic character of the carbon ring is essential agent results in a substantial amount of undesirable de for purposes of this invention. For example, both cyclo composition products and the yield is thus substantially. pentadiene and indene contain an alicyclic cyclopenta- ‘ ' reduced. The liquid medium in which the reaction takes dienyl ring structure; cyclopentadiene having no double place should thus be chosen to give ?uid‘ mixtures which‘ bond coordinately shared with an aromatic ring and 45 can easily be stirred at the low reaction temperatures; indene having only one double bond of the cyclopenta Ether or ether-toluene mixtures are Well adapted as sol dienyl ring coordinately shared with an aromatic ring. vents for this purpose. After the reaction has progressed In contrast, the ?ve carbon ring in ?uorene, where each ‘ ‘ sufficiently at the selected low temperature, it maybe of the double bonds in such ring is coordinately shared continued at a higher temperature, preferably between with an aromatic ring, is not alicyclic in character and 50 about 10° C. to 40° 0, whereby further reaction is pro: ?uorene thus does not contain an alicyclic cyclopenta moted. , dienyl ring structure. A wide range of ratios of reactants may be employed. In the practice of this invention an organo—magnesium Ratios of RgMgX to vanadium halide of from 1:1, or halide of an organic compound containing an alicyclic less, to 5:1, or higher, may be used. cyclopentadienyl carbon ring may be formed and then 55 The organo-metallic compounds of this invention may. reacted with a vanadium halide to produce the desired also be produced by formation of an alkali metal deriva-, organo-metallic compound. It is to be understood that tive of an organic compound containing the cyclopentar the term ‘ivanadium halide” as used herein includes oxy dienyl carbon ring and reaction of the resulting organo~_ halides as well as halides which contain no oxygen. Thus alkali metal compound with a vanadium halide as dis-, 1 included within the term are compounds having the gen 60 closed and claimed in co-pending application of Lynch eral formula VX2, VX3, VX4, VX5, VOXz and VOX3 and Brantley entitled “Process for Producing Organo-v where X is'halogen. ,- “ ~ ' ' ’_ -‘ ~ ' - metallic Compounds,” Serial No. 381,970 and ?led of .’ Theorgano-magnesium halide, hereinafter referred to even date. However the process there disclosed and p asa “cyclopentadienyl carbon ring Grignard reagent” has claimed forms no part of this invention. ' the general formula RMgX wherein R and X are as 65 In general, reaction according to that process of a described above. The organic compound containing the suitable organo-alkali metal compound with lower valence alicyclic cyclopentadienyl carbon‘ ring which is to be vanadium halides tends to result in production of an' reacted with a lower alkyl magnesium halide for produc organo-vanadium monohalide or non-halogenated organo-, tion of the cyclopentadienyl carbon ring Grignard reagent vanadium compounds. However these compoundsare'l should, before its combination in the Grignard reagent, 70 quite sensitive to oxidation, the dihalide's being much qontainaaireactive hydrogen on the methylene carbon of, more stable under oxidizing conditions. The mono the lalicycliccyclopentadienyl carbon ring, but tbenum- ‘ halides, have the general formula. RQVX while thenon~ 2,882,288 halogenated compounds have the general formula RgV. of compounds of this invention by methods disclosed and The organo-vanadium compounds of this invention are in claimed in the co-pending application of Lynch and general colored crystalline solids. The physical properties Brantley entitled “Process for Producing Organo-metallic Of the organorvanadium dihalides vary with variations in Compounds,” Serial No. 381,970, and ?led of even date. the halogen and in the organic component. They are sol 01 It is to be understood however that such methods of uble in water and acids, undergoing some decomposition. preparation form no part of the present invention. Their solubility in chloroform is very low although con A suspension of sodium cyclopentadiene. was prepared tinuous extraction of the dry halides in warm CHCla by adding 92 ml. vof cyclopentadiene to 22.4 grams‘of gives a method for puri?cation and recrystallization. In ?nely divided sodium sand in 450 ml. of ethylene glycol general, they decompose without melting and are in 10 dimethyl ether. A solution of vanadium tetrachloride soluble to very slightly soluble in most organic solvents. in ethylene glycol dimethyl ether was prepared by adding Variations in properties are also apparent in employ 94 grams of VCL; to 250 ml. of the solvent which was ment of alkyl or aromatic substituted cyclopentadiene or cooled in an ice water bath. The VCl4 solution was added indenes. Increased volatility, lower melting points and to the sodium cyclopentadiene suspension using an ice greater solubility in organic solvents is to be encountered 15 bath to control the temperature of the exothermic re with the his(alkylcyclopentadienyl) and bis(arylcyclo~ action. After warming to room temperature, the viscous pentadienyl)vanadium dihalides. reaction product was ?ltered. Succeeding operations The compounds of this invention may, by reason of were carried out without a protective atmosphere. The color, be employed as coloring agents. They may also ?lter cake of reaction solids was extracted with chloro; serve as oil driers and as oxidation catalysts. 20 form in a Soxhlet extractor. The ?ltrate from the re 7 As illustrative embodiments of a manner in which the action products was evaporated to dryness under a vacuum invention may be practiced, the following examples are and the solid residue was also extracted with chloroform presented. In each example an inert protective atmos in the Soxhlet extractor. Because of the low solubility phere of nitrogen or other inert gas was employed dur of (C5H5)2VCl, in chloroform the extractions required ing formation of the Grignard reagents and their reaction 25 several days. Green crystals of (CSHEJZVCI, were ob with vanadium halides. tained by crystallization from the chloroform extracts. Example I Example IV 1 mole of C5H5MgBr was prepared by reacting 24 A slurry of sodium cyclopentadiene was prepared ‘by grams of ?nely divided magnesium metal with 1.05 moles 30 suspending 11.9 grams of ?nely divided sodium sand in of methyl bromide in 400 ml. of ether and slowly adding 250 ml._of> ethylene glycol dimethyl ether and adding. to the reaction mixture 1 mole of cyclopentadiene. The 39.2 grams of cyclopentadiene at 20°-25° C. A slurry reaction mixture was then re?uxed for four hours to com of vanadium oxytrichloride was prepared in ethylene plete the reaction.
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