DE1618698A1 - Organosilicon compounds and processes for their preparation - Google Patents

Description

DR. E. BOEITNER

. Pdlentiiv.v.ilte

Mt- M CU EN 8 -ν.

Lucüe-üratan-otraße 39
Telephone 443755

H3.P.U8

Midland Silicones Limited, Reading, Berkshire * England

Organosilicon compounds and processes see below Manufacturing

The present invention relates to a method for door Manufacture of organosilicon compounds, and si «refers also focus on certain new organosilicate compounds.

The process for the preparation of the organoeilioium compounds according to the present invention is characterized in that one
(1) an Organosllioii connection of the general Ponael

in which each symbol R is a monovalent hydrocarbon rest, a monovalent hydrocarbonoxy radical or represents a monovalent halogenated hydrocarbon radical tj, a is a number worth 1, 2 or 3 1st, Z is a divalent saturated aliphatic, or

cycloaliphatic! " Means hydrocarbon residue and Y stands for a Kalogenatoa »» it (2) an association of the general Fbrael

attaches, in which each of the syaboles X is a hydrogen atom, an alkyl or aryl radical means old the proviso that not much as one X is hydrogen is »and Q is an AlkallBetallatoa.

In that given above for the organosilicon reaction component General formula can make the best R monovalent Hydrocarbon radicals be «for example alkyl radicals, such as Methyl, methyl, propyl, ootyl or quetadecyl groups, also alkylkenyl radicals, such as vinyl, allyl or cyolohexenyl groups " and aryl radicals, such as phenyl or naphthyl or TbKärlgruppen, monovalent halogenated carbons such as chloropienyl or trifluoropropyl groups, and equivalent Kohl enwasaers toffoxy groups, such as; Alkoxy radicals.

The triwelwertlge remainder Z _9, which connects the stickatoffatoe of the aeinogroup with the ailiolumatoai, can be made from a »

dear divalent aliphatic or oycloaliphatic Consist of a hydrocarbon residue, e.g. a methylene, Xthylene · », propylene ,. Polymethylene or cyclohexylene group. Z should preferably have 1 to 18 carbon atoms.

For example, suitable representatives of the compounds that as components (1) in the «method of the present Br-

ias0Ofl / aoai ^ original

can find application are chlorates thyi-trlmethylallan, Di- (bron3ethyl) -dibutylsilane, γ-chloropropyl- «ethyldioctylsilane and o * ~ CMorbutyl-triethylBilane.

Working methods sur preparation of halogenkohlenwaeeerstoff-substituted Organosilioiumverbindungen used as Realctionekomponente (1) in which erflndungsgemKeen method "include ma to the prior art. This includes the reaction of vinyl or allyl halides with organosilicate compounds containing silicon-bonded water-based substances, a process which is generally carried out in the presence of a platinum catalyst. The Orgastoslleluenrerbindungen, which for the production of the Aalno-Organosllleiumverbindungen to ^ of the process of the ¥ orifeg®iad invention to ^ often come into question, are those in tetsn the Hmi © imfeG® ¥ mm a chlorate ”consists.

The compound (2) used in the method according to the present invention Invention sur applied corresponds to the general formula

in which every syebol X has a hydrogen atom, an alkyl radical, e.g. an «ethyl, ethyl, propyl or octadecyl group, or an arylreat, ae.B. a phenyl or caphthyl group, means since the NaSgAbe that no more than an X represents a hydrogen ate *. As a precaution, X represents an aryl radical. In the general formula given

Q stands for an alkali metal atom, preferably for a sodium, potassium or lithium atom.

Compounds d * le as a reaction component (2) for use can be prepared by any known method, a preferred route in question to oil such compounds consists in using an alkyl or aryl lithium compound, such as phenyllithium or butyllithium, with the appropriate amino compound, for example a Dlarylamine, such as Dlphenylamln to implement. According to a In a modified method, the alkali derivative can be prepared by treating, for example, the diarylamine with sodium amide implements.

01 · implementation of halocarbon-Organoeiliclumverbindung (1) with the Alkallverbindung (2) for the manufacture of the desired Amlno-Organoslliciumverblndungen can be carried out at any temperature between about 30 ⁰ C and the reflux tempera door of the reaction mixture generally. In some cases, however, the reaction proceeds so slowly at temperatures below about 60 ° C. that it is of no practical importance, and it is therefore advisable to carry out the reaction at about the reflux temperature of the reaction mixture Bobee. Diethylene relative proportions, are where dl · Reaktlonskomponenten reacted are not critical, although the best results are generally obtained when applying the alkaline Amlnoverbindung (2) low in a · "etöchiometrisehen excess.

109809/2091 ^ßAD

If desired, the reaction mixture can be one or more Contain solvents. According to one embodiment of the method according to the invention, it has proven to be expedient proved «the alkali derivative of diarylatin in a solvent such as diethyl ether and then the halocarbon organosilicon compound to add to the solvent solution of the aroin derivative and let the reaction kick in. After the completion of the reaction, the desired product can be prepared according to any of the conventional methods can be obtained, for example by Brsatz the solvent of the solvent solution of the product by another solvent, after which the solution then fractionated to obtain the desired organosilicon compound. '

If a low-boiling solvent, such as diethyl ether, is used, it may be necessary to switch off the reaction below Carry out excess pressure in order to achieve the desired reaction temperature. The application of high pressure © can. however, in some cases it can be avoided by using all or part of the low-boiling point Solvent with a solvent to reflux Brings boiling, which takes place at a higher temperature.

Some of the organosilicon compounds which can be prepared according to the process of the present invention are new and the invention therefore encompasses as novel compounds those of the general formula “.-.

1Q.HOd / -jO01-

in which R, Z and a have the meaning given above and each symbol X represents an aryl radical.

The amino-organosilicon compounds which are produced according to the process of the present invention can be used industrially for the formation of water-repellent coatings on fiber materials or as finishes for glass fibers. The new organosilicate solder compounds defined above have proven to be particularly useful as additives in organic or organic compounds
/ Organoeilielum-Materlallen in so far as they remarkably improve the thermal and oxidatlve stability of the same «As was found» it is by. It is possible to add small amounts of these new compounds to hydrocarbon lubricants to significantly improve their stability against oxidation. With regard to this special property, those compounds according to the invention are particularly advantageous in which the radicals R of the formula given are selected in such a way that they make the organoellicium compound compatible with the organic material into which they are incorporated. For example, such organosilicate compounds can be used with particular advantage as additives for increasing the oxidation stability of mineral lubricating oils in which at least some of the substituents are R-butyl groups or higher molecular weight hydrocarbon radicals.

BATH ORIGINAL

109809/2091

The invention is further illustrated by the following examples.

example 1

Diphenylamine (50.1 g, corresponding to 0.3 hol) in 100 μl of diethyl ether was placed in a flask which contained n-butyllithium, which was obtained by reacting lithium (4.2 g, corresponding to 0.6 gram atom) old butylbroald (41 »4 g, corresponding to 0.3 NoI) .was obtained, and the mixture was then refluxed for every hour. Then chloroethyrl-dibutyl-ethyl-ailane (29 g, corresponding to 0.1U Hol) was added, the ethereal solvent was replaced by xylene and the oil was heated under reflux for 40 hours. After complete heating, the reaction mixture was allowed to cool, water was added, and the organic layer was isolated and dried. After eltter Vakuuadestillatlon to remove the xylenes this layer Diphenylanlnomthyl ~ swtliyl- "dlbutylBllan which _{n has} a boiling point of Kp., _{Λ R} 16o-l / O ° C and a Brechungsiridex of r ^ ⁵ 1,5Ί85 provided comprising.

Example 2

Phenyllithium was made in a flask by reacting Lithium in pill form (4.05 g, equivalent to 0.58 * mol) old BroBbenzol (* 3 # 6 g, corresponding to 0.278 mol) in dry Diethyl ether produced at reflux temperature.

BATH

109809/2091

To the PhenyllithlumlUsung Dlphenylamin was (* 7 S, corresponding to 0.278 mol) in 100 ml of diethyl ether gradually, keeping the temperature of the mixture was maintained by external cooling to 20 to 25 ⁰ C. When the addition of the diphenylamine was complete, the mixture was heated to reflux temperature for 6 1/2 hours, then stirred for a further 16 hours at room temperature, and then trimethylbromoethylsilane (50 g, corresponding to 0.278 mol) was added, with little heat being generated during this Addition was made. After the mixture had been stirred for 30 hours and left to stand for 65 hours, it was poured into an ice / water mixture and the organic layer was then separated and dried over MgSO ^ .H _g 0.

After de "Fraktionleren under vacuum the organic layer afforded l-Dlphenylanlno-2-irimethylsilyläthan whose boiling point at Kp. Q £ is 107 ° C and its refractive index is 1.5671"

When analyzing the product, the following values were determined: Si 10.82 % i C 75 * 9 % and H 8.66 %. The values calculated for the compound SiC,., H ₂ , N are: Si 10.4 £; C 75 # 8 % and H 8.55 %>

Example "5

Dlphenylaain (50.1 g, corresponding to 0.3 hol) in 100 al diethyl ether was placed in a flask containing n-butyllithium contained which according to that described in Example 1

109809/2091 ^8AD

Method was prepared "and the mixture was refluxed for two hours. Then γ-chloropropi-methyl-dibutylsilane (50 g, corresponding to 0.176 mol) was added to the flask and the reaction mixture was refluxed for 40 hours. At the end of this heating period, the mixture was allowed to cool and water was added. The organic layer was then collected, dried and fractionated so as to obtain 1-diphenylatnino-3-methyl-dibutylsilylpropane with a boiling point of ₀ ... 170-173 °.

Example 4

Aniline (28.9 S * corresponding to 0.3 mol) in 50 al of ether was added to a solution of phenyllithium (0.3 hol) in ether and the mixture was refluxed for two hours. Then 1-broin-2-trimethylsilylethane (36.2 g, corresponding to 0.2 mol) was added, the ether was replaced by tetrahydrofuran and the mixture was refluxed for 20 hours.

The mixture was allowed to cool, water was added and the dried organic layer fractionated to βο l-phenylamino-2-trimethylsilyläthan (18.5 g, corresponding to a yield of 49 $) of Kp. Win _{2 5} 106 °.

BATH

Claims (1)

Claims Process for the production of organosilicon compounds, marked daduroh, daJ «on (1) an organosilicon compound of the general formula in which each synbol R oxy group is a monovalent hydrocarbon radical "is a monovalent hydrocarbon · or dare divides a monovalent halogenated hydrocarbon radical, a is a number with a value of 1 · 2 or jj let, Z represents a divalent saturated aliphatic or cyoloaiiphatischen hydrocarbon radical 'and Y. a Halogenatoa is «Alt (2) a compound of the general formula uasetxt. In which every Syebol X "in Wasseratoffato", represents an alkyl or arylate »with the proviso that there is no longer any one X hydrogen "and Q means an Alkaliftetallato «). 2 "Method according to claim 1 _9, characterized in that those compounds of the general formula given there under (2) are converted" where X denotes an aryl radical. 3 * Process in accordance with Claims 1 and 2, characterized in that such compounds are "grounded" in accordance with the general formula given in Claim 1 under (1) 103 * 09/2031 • ORIGINAL BATHROOM where the bed Z contains 1 to 18 carbon atoms * 4. The method genX3 any of the preceding claims, characterized characterized that such compounds of the general hair dryer specified in claim 1 under (2) ·! are implemented in which the Syabol Q sodium, Means potassium or lithium. 5- Method according to each of the preceding claims, thereby marked that the killing is in the present is carried out by one or more solvents. 6. The method according toKB claim 5, characterized in that the solvent consists of dläthjlKtber. 7 * Method gwaäfl Any «of the preceding claims, thereby marked that the (tea set at the reflux temperature of the Reaktlonageaisobe is carried out 8. Method geaXB any «of the preceding claims, characterized indicated that component (2) is used in a small excess of equilibrium. 9 · Organosllioiuav «rbinds, as they are after the procedure • Have been made in ·· each of the preceding claims. BATH 109809/2091 10. OrganoeiliciujBverbindungen of the general formula in which each symbol R represents a monovalent hydrocarbon rest, a monovalent hydrocarbon oxyreet or is a monovalent halogenated hydrocarbon radical, a is a number with a value of 1, 2 or 3 1st, Z is a divalent one represents saturated aliphatic or cycloaliphatic hydrocarbon radical and each symbol X stands for an aryl radical. 11. organosilicon compounds according to claim 10, characterized marked that each of the symbols X in the specified there general formula represents a phenyl radical and each of the symbols R represents an alkyl radical ⁰⁴⁰ 109809/2091