DE1693165A1 - Process for the preparation of mono- and bis-trialkylsilylphenylferrocenes - Google Patents

Description

Process for the preparation of mono- and bis-trialkylsilylphenylferrocenes The invention relates to a process for the preparation of mono- and bis-trialkylsilylphenylferrocenes. It also extends to trimethylsilylphenylferrocene and 1,1'-bis- (p = trimethylsilylphenylferrocene.

French Patent 1,396,272 describes certain metallocenyl-substituted organosilicon compounds and a process for their preparation. These compounds are prepared by acylating metallocenes, for example ferrocene, with a silylic acid halide of the formula wherein R is hydrogen, a halogen radical, a monovalent hydrocarbon radical, a halogenated monovalent hydrocarbon radical, a cyanoalkyl radical or a fluoroalkyl radical, R 'is a divalent radical having at least 2 carbon atoms, namely a hydrocarbon radical or a halogenated hydrocarbon radical, and X is a halogen radical.

Since the process of the cited patent is a Friedel-Crafts acylation reaction contains the received At least acylated netallocene a carbonyl group in feasibility for the metallocene core.

It has been found that the use of many metallocenyl-substituted Organosilicon compounds as described in the aforementioned property right, based on their solubility properties in various solvents.

For example, silicon-containing I etallocenes have been found in the generally used as valuable antioxidants and additives to improve the sliding or lubricity, however, the analogous carbonyl-containing compounds often have only limited effectiveness. It was found that these carbonyl-containing organosilicon compounds in hydrocarbons are much less well tolerated because they are strong Have polarity. Another application where the compatibility important with solvents is the use of silicon-containing metallocenes as an agent for the absorption of ultraviolet rays = -; in organopolysiloxanes.

If not satisfactory compatibility of this silicon-containing Metallocenes in organopolysiloxane, e.g. in an organopolysilo varnish, achieved the silicon-containing metallocene can migrate, thereby reducing its effectiveness as a Ultraviolet ray absorbent deteriorates. Jile has custody also taught that the compatibility of carbonyl-containing metallocenylorganosilicon compounds in non-polar solvents, e.g. hydrocarbon oils, by reducing the Carbon 1 group to methylene can be improved. In these cases the received Metallocenylorganosilicon compounds, however, have a poorer resistance to oxidation in cases in which R 'of the formula (I) is an arylene, due to the formation an arglenomethylene bridge between the silicon atom and the metallocene core.

The ferrocenes produced according to the invention are thereby marked, because they contain one or two silylphenyl radicals of the formula (A) SiR "- (2), the are bonded to a ferrocene nucleus, where A stands for an alkyl radical and R ″ Is phenylene radical. The ferrocene suitable for the purposes of the invention consists of Iron chemically linked to two cyclopentadienyl radicals, their free valences except for the valences saturated with the silylphenyl radical of the formula (2) with monovalent ones Residues are saturated from the hydrogen, electron emitting organic Residues, electron-absorbing organic residues and mixtures thereof Group selected sin @.

To the ferrocenylphenyl-substituted prepared according to the invention Organosilicon compounds include silanes of the formula A SiR "Z (3) and bis (silylorgano) ferrocenes of the formula (A SiR ") 2Z '(4) in which A and Rit have the meaning already mentioned, Z is a monovalent ferrocenyl radical and Z 'is a divalent ferrocenyl radical.

For the purposes of the invention, ferrocene can be used to introduce the monovalent radical Z mentioned above and the divalent radical Z 'of the formulas (3) and (4) which have the formula saben, where @ stands for a monovalent, chemically bonded to a cvelopentadienyl radical from the group consisting of hydrogen, monovalent, electron accepting radicals and monovalent electron donating radicals, n an integer from 1 to 4 and n an integer from 1 to 5 is.

Monovalent electron donating radicals for which Q in formula (5) are aryl radicals, hydroxyaryl radicals, e.g. B. phenyl, tolyl and hydroxyphenyl, aliphatic radicals including alkyl radicals, alkenyl radicals, cycloaliphatic, carboxyaliphatic Residues and nitroaliphatic residues. The monovalent ones represented by Q in the formula (5) electron-accepting radicals are aliphatic ayl radicals, e.g. formyl, acetyl, propionyl, Arylacyl such as benzoyl, etc .; Carbo-: y, aldehyde, sulfo, carboxyaryl, such as carboxyphenyl, Carboxytolyl, etc.; Nitroaryl, such as nitrophenyl, haloaryl, such as chlorophenyl, bromotolyl etc.; halogenated aliphatic radicals such as chloromethyl, chloroethyl, etc .; @ can always be the same remainder or any two in consecutive units or more of the aforementioned electron donating or electron accepting Represent remains.

The ferrocenylphenyl substituted silanes of formula (3) can be prepared are made by reacting the Grignard compound of halophenylferrocenes of the formula ZR "MgX (6) with halosilanes of the formula A3SiX (7) where A, R", Z and X are already have given meaning.

The Grignard compound of halophenylferrocenes of formula (6) can be made according to the procedure described by William F. Little et al In Journal of Organic Chamistry, 20, page 713, March 1964, is described. the Halophenylferrocenes can be produced according to the procedure by Victor Weinmayer, Journal of the American Chemical Society 77 012 (1955) Condensation of a diazonium salt of a halogenated aromatic hydrocarbon with a ferrocene in the presence of concentrated sulfuric acid. The corresponding Dihalophenylferrocenes, which are used to make the orano-silicon compounds of the formula (4) can be used by using 2 moles of the diazotized halogenated aromatic hydrocarbon per mole of ferrocene in the above process manufactured by Victor Weinmayer. The Di-Grignard compounds of the formula XMgR "Z'R" MgX (8) can be obtained from the corresponding Dihalophenylferrocenes are produced. The implementation between the Di-Grignard connection of formula (8) and the halosilane of formula (7) gives the organosilicon compounds of formula (4).

The silanes of the formula (5) include, for example, p-trimethylsilylphenylferrocene and p-chloromethyldimethylsilylphenylferrocene. To the bis (silylor ;; ano) -ferrocenes of the formula (4) includes, for example, 1,1'-bis (p-trimethylsilylphenyl) ferrocene.

The halosilanes of the formula (7) include, for example, trimethylchlorosilane.

Ferrocenylphenyl-substituted polymers can be made from some of the ferrocenylphenyl-substituted Organosilicon compounds according to the invention by the method of the French Patents 1,96,271 and 1,396,274.

These polymers can be filled with fillers such as those obtained from the gas phase Silica, silica airgel, non-reinforcing Fillers, such as ground quartz, zinc oxide, etc., can be mixed. The hardening of this linear Polymers can be made with organotriacyloxysilanes, such as methyltriacetoysilane, or under Use of ethyl orthosilicate and a metallic soap according to the method of the US patent 2 843 555 can be made. Can be used in combination with the other components Heat stabilizers and plasticizers can be used.

The ferrocenylphenyl-substituted ones prepared according to the invention Organosilicon compounds can be used directly in organosiloxane polymers and ordganosiloxane copolymers to stabilize these polymers e. ; en degradation by ultra-violet radiation, heat, Oxidation, etc. can be used. You can also improve the lubricating properties organic liquids and the anti-knock properties of fuels Based on hydrocarbons.

To carry out the method according to the invention, the Grignard compound of halophenylferrocenn of the formula (6) with a halosilane of the formula (7) implemented. The obtained ferrocenylphenyl-substituted silane or bis (silylorgano) ferrocene, those in the following description sometimes as ferrocenylphenyl-substituted silanes are designated, e can be determined according to the nature of the radicals bonded to the silicon Production of polymers and copolymers are further hydroxysed.

The reaction between the Grignard verbis1dune of the halophenylferrocenes and the halosilanes can be carried out by conventional methods. The experience has taught that # a temperature in the range of 30-100 ° C anx, ewenuet can graze. organic solvents such as tetrahydrofuran, dimethoxyethane, di-n-butyl ether, etc., can be used.

The ferrocenylphenyl-substituted silanes can be deposited directly according to the usual extraction methods, a.B.

Chromatography. are in the following examples all parts parts by weight.

Example 1 In a solution of 100 parts of ferrocene and 500 parts of 96% strength Sulfuric acid was stirred into a mixture at about 250.degree. C., which was obtained by diazotization of 86 parts of p-bromoaniline in 500 parts of 20% sulfuric acid at (-5 ° C had been.

There. p-bromoaniline was diazotized by adding to a solution of p-bromoaniline in 20% sulfuric acid a stoichiometric I-ienge sodium nitrite in the form of a aqueous solution at about 0-5 ° C @ was added.

After 24 hours the solids were filtered off from the mixture.

The mixture was extracted with benzene. To the filtrate were l @@ feile Zinc dust given. The resulting mixture was stirred for about 1 hour and washed with ether extracted. The ether was driven off and the residue to remove was not converted ferrocene is distilled with steam. The product was again with ether e extracted and recrystallized from 90% acetic acid. This resulted in 45 parts of product obtained from melting point 124-126 ° C. Due to the manufacturing method and the mfrarovspekorum what the product p-bromophenylferroccn.

A mixture of 17 parts of p-bromophenylferrocene. 3.7 Parting drier Magnesium turnings, 7.1 parts of Kethyl iodide and 750 parts of Tetraa; drofuran turned 48 Heated to reflux under nitrogen for hours. The reaction mixture would then settle out calmly. It was freed from magnesium by filtration and made into one in bulk Solution of 54 parts of trimethylchlorosilane and 50 parts of tetrahydrofuran given. When the addition was complete, the reaction mixture was brought to the reflux temperature heated and held at this temperature for a further 5 hours. The reaction mixture was cooled and poured onto ice. The organic phase was separated off, dried, concentrated and chromatographed on aluminum oxide. The main gang was with Heran eluted. As a result, 0.8 part of an organic solid became melting point 109-110 ° C obtained.

Because of the manufacturing method and the infrared spectrum, that was Product trimethylsilylphenylferrocene.

The solubility of trimethylsilylphenylferrocene and trimethylsilylbenzoylferrocene in 2, 2,4-trimethylpentane and octamethylcyclotetrasiloxane was compared. That Trimethylsilylbezoylferrocene was made according to the method of the aforementioned French Patent 1,396,272. The results obtained are in the following Called table. The solubility is in parts by weight of ferrocenylarylsilane per 100 Expressed parts by weight of solvent at 250 ° C.

2,2,4-trimethyl-octamethylcyclopentane, tetrasiloxane, trimethylbenxoylferrocene 1.8 0.16 Trimethylsilylphenylferrocene 4 1.4 Example 2 A mixture of diazotized p-Bromophenylaniline and ferrocene are prepared in the manner described in Example 1.

Before the reduction with zinc powder, the mixture is extracted with gasoline. The roll product is recrystallized from high-boiling petroleum ether. Here is 1,1'-bis (p-bromophenyl) ferrocene obtained, its structure by its infrared spectrum is confirmed.

A solution of 4.9 parts of the l, l'-bis (p-bromophenyl) ferrocene, 2.8 Parts of methyl iodide, 1.4 parts of magnesium and 750 parts of anhydrous tetrahydrofuran is refluxed for 48 hours under nitrogen. The liquid and the salts are then dated by decanting the mixture using a separating funnel Magnesium separated. The liquid phase becomes a solution of 65 parts dropwise Trimethylchlorosilane and 60 parts of tetrahydrofuran were added. The reaction mixture is heated to the reflux temperature and refluxed for a further 5 hours.

The resulting mixture is then poured onto ice and the organic Phase separated from the aqueous phase. The organic layer is dried, filtered and chromatographed. An organic fraction is obtained that contains a 1: 1 mixture of He; = an and benzene is eluted. The product becomes after crystallization filtered. Based on the manufacturing method and its infrared spectrum it is l, lt-bisp-trimethylsilylphenyl) ferrocene.

The ferrocenylphenyl-substituted ones prepared according to the invention ranosilicon compounds are suitable for a wide variety of applications in which Materials are required that are highly compatible in hydrocarbon oils are, as well as for the production of organopolysilo: anes. In addition, they are suitable due to the fact that arylsilicon bonds are highly resistant to oxidation are for numerous applications in which materials are used that are at experience no change at elevated temperatures.

Claims (3)

Claims 1. Process for the preparation of mono- and bis-trialkylsilylphenylferrocenes, characterized in that one uses the Grignard compound of a Mcno- or di-halophenylferrocene with a trialkylhalosilane. 2. Trimethylsilylphenylferrocene. 3. 1,1 'bis (p-trimethylsilylphenyl) ferrocene.