Patent GB-1076426-A (GB)
Title: Improvements in "organosilicon materials and a method for making them"
IPC: C07F17/00
Filed: 1964-04-29
Abstract: Compounds of Formula (I) <FORM:1076426/C4-C5/1> wherein Q11 is H, an electron donating radical (as defined) or an electron withdrawing radical (as defined), M is vanadium, chromium, molybdenum, tungsten or manganese, n is 1-5, m is 0-4, m + n = 5, x is 2 or 3 depending on the valency of M, R is H, halogen, alkoxy, hydrocarbon, halohydrocarbon or cyanoalkyl, R1 is -CH-, -(divalent hydrocarbon radical)-CHOH-or -R11-Y-, where R11 is a divalent hydrocarbon radical of at least two carbon atoms, Y is a divalent methylene, carbonyl, carbinol, carbamino or carbazido radical, and A is R or -O 1/2 , may be used as lubricants.ALSO:The invention comprises compounds of Formula (1) <FORM:1076426/C3/1> wherein Q11 is H, an electron donating radical (as defined) or an electron withdrawing radical (as defined), M is vanadium, chromium, molybdenum, tungsten or manganese, n is 1-5, m is 0-4, m + n = 5, x is 2 or 3 depending on the valency of M, R is H, halogen, alkoxy, hydrocarbon, halohydrocarbon or cyanoalkyl, R1 is -CH2-, -(divalent hydrocarbon radical)CHOH -or-R11-Y-, where R11 is a divalent hydrocarbon radical of at least two carbon atoms, Y is a divalent methylene, carbonyl, carbinol, carbamino or carbazido radical, and A is R or -O 1/2 -.  The compounds wherein Y is carbonyl may be prepared by reacting a compound of Formula (2) (R)3-Si-R11-CO-X with a carbonyl of Formula (3) H5- mQ11mM (CO)x in the presence of a Friedel-Crafts catalyst; the carbonyl group Y in the product may be converted to the other Y groups by conventional reactions. Compounds wherein R1 is methylene may be prepared by (a) reacting the methylene lithiate of a compound of Formula (3) (see Division C2) with a halosilane; or (b) reacting the quaternized product of an aldehyde, secondary amine and a compound of Formula (3) with a substituted silyl metallic. Compounds wherein R1 is -CH2CH(OH)-may be prepared by reacting a metal carbonyl of Formula (3) substituted by a formaldehydic radical with, for example, a Grignard reagent of a halomethyl trimethyl silane. Disiloxanes, i.e. compounds wherein A is O 1/2 may be prepared by the hydrolysis of the corresponding monomer having a hydrolysable group bonded to the silicon atom.  The compounds of the invention may be used as heat stabilizers for siloxane polymers.  In Example 7 a polydimethyl siloxane is mixed with (CH3)3Si(CH2)3CO -[C5H4Mn(CO)3] fumed silica and benzoyl peroxide, and cured.ALSO:Metallocene carbonyl complexes of formula H5- mQ111C5M(CO)x wherein M is vanadium, chromium, molybdenum, tungsten or manganese, Q11 is H or an electron-donating or electron-withdrawing radical (as defined), m is 1-5, and x is 3 in the case of manganese and 2 in the case of the other metals, are subjected to the following reaction sequences:  (a) acetylation, conversion of the acetyl radical to a -COOH radical by hypohalite reduction, reduction of the carboxylate by LiAlH4 to the carbinol, methoxylation of the carbinol, and metalation of the methoxy compound by butyl lithium to the methylene lithiate-no examples are given; (b) condensation with a mixture, or reaction product, of an aldehyde and a secondary amine, in the presence of phosphoric acid or PCl3, and quaternization of the product with an alkyl halide-in Example 2, cyclopentadiene manganese tricarbonyl is condensed with bis-(dimethylamino)-methane to yield dimethylaminomethyl cyclopentadienyl manganese tricarbonyl, which is then quaternized with CH3I.