DE2330308A1 - NON-LINEAR POLYMERIZED AS CATALYST PRECURSOR AND ITS USE IN A CATALYST COMPOSITION - Google Patents

Description

PATENT LAWYERS

. P. WlRTH - Dr. V. SCHMIED-KOWARZIK Opting. G. DANNENBERG Dr. P. WEINHOLD Dr. D. GUDEL

281134 β FRANKFURT AM MAIN

287014 GR ESCHENHEIMER 8ΤΒΑββΕ 3β

Oaee C-9080-G

UNION CARBIDE CORPORATION New York, N.Y./USA

Non-linear polymer as a catalyst precursor and their use in a catalyst composition

The invention relates to a new non-linear polymer and its use in a catalyst composition for heterogeneous catalysis. .

The homogeneous catalysis in chemical synthesis represents an important development in technical chemistry. The chemical synthesis processes in which this type of catalysis is applied depend on the use of transition metals, those with different electron dioriori ligands Form complexes and are used in solution. Some of the important homogeneous catalytic processes that are used on a large scale be carried out, UBd, the; ida ^ in commonly used Transition metals are the oxo process (cobalt, rhodium), the

- 309881/1228

Production of acetic acid from methanol (rhodium), the ■ Production of acetaldehyde from ethylene (palladium), the Production of propylene oxide by hydroperoxide oxidation (molybdenum, vanadium), the production of vinyl chloride and Vinyl acetate made from ethylene (copper), the manufacture of phenol from toluene via benzoic acid (copper), hydrogenation process (Platinum, palladium, cobalt), olefin disproportionation or dismutation processes (tungsten) and oxidation processes (Nickel, copper).

A feature common to these processes using homogeneous catalysis is that therein a relatively expensive metal compound is used as a catalyst. To be economical, in the process effectively exploits the metal. This is generally achieved by having a very high Catalyst productivity (high conversion) achieved, catalyst losses avoids or substantially reduces and recovers the spent metal cheaply and effectively. To the Improvement of the profitability of the above-mentioned processes while maintaining high catalyst productivity one has had in industrial research in the field of catalysis tried to replace the homogeneous catalysts used so far by heterogeneous catalysts au or replace the known methods of recovery of the metal used. From time to time some improvements have been made, an optimization however, either direction has proven difficult.

The aim of the present invention is therefore to provide a new transition metal catalyst composition to schafff ⁿ can be while maintaining high productivity in heterogeneous catalysis, rather than used in homogeneous catalysis, can be considerably reduced whereby the catalyst losses. The aim of the invention is also for it

309881/1228

useful new catalyst precursors or compositions in the form of one of these precursors to develop, which is used to recover the used metal that is in the homogeneous Catalysis is used, can be used. Further Objects, features and gate parts of the invention will appear from the following description.

The invention relates to a new catalyst precursor as well as a new catalyst with a high productivity.

The invention relates in particular to:

I.) a new non-linear polymer as a catalyst precursor, which is characterized in that it consists essentially of a recurring unit of the following Structural formula

R ¹

ι ■ ■

where mean:

R is a non-substituted or substituted, straight-chain en or branched, divalent, saturated Alkylene radical with 1 to 10 carbon atoms or a non-substituted or substituted diva-

en
Lenten Ary & est with 1 to 3 benzene rings, where the alkylene radical can be substituted by halogen or a phenyl radical and the Ary & est by halogen or straight-chain or branched-chain saturated alkyl radicals with 1 to 5 carbon atoms and

a non-substituted or substituted, straight chain or branched or cyclic, monovalent

309881/1228

th, saturated alkyl radical with 1 to 10 carbon atoms or a non-substituted or substituted, monovalent aryl radical with 1 to 3 benzene rings, the alkyl radical being replaced by halogen or a phenyl radical and the aryl radical by halogen or straight-chain or branched-chain, saturated alkyl radicals with 1 up to 5 carbon atoms can be substituted; as

II.) A catalyst composition, which is characterized is that it consists essentially of the catalyst precursor defined above, each phosphorus atom bound (coordinated) in the polymer to a transition metal atom with the charge O or a positive charge is, with each positively charged transition metal atom a sufficient number of negatively charged organic or has inorganic, functional group-free radicals bonded to the valence of the transition metal atom to saturate, and in which the radicals from the group of halogens, nitrates, sulfates, the straight-chain alkoxy or acyloxy radicals having 1 to 10 carbon atoms and the aryloxy radicals having 1 to 3 benzene rings are selected.

With regard to the term “transition elements” or “transition metals” used here and with regard to their oxidation states reference is made to the Periodic Table of the Elements, as stated on the inside cover of the "Handbook of Chemistry and Physics", 46th edition, published by the company The Chemical Rubber Co., 1965 »is indicated ·

In the process of making the first and second precursors and the final catalyst are customary processes; however, there is no general method of manufacture of each first precursor, various methods are therefore proposed below by way of example, all of which are used for

309881/1228

Preparation of at least some of the compounds that fall under the general formula are satisfactory

Two general routes to the synthesis of the first catalyst precursor (RO) ₅ -Si-R -P- (R) ₂ can be followed. The first route is via the formation of, for example, functional grouped diphenylphosphine, which is then coupled to a silane; the second way proceeds via the reverse process, ie first a silicon derivative is provided with functional groups, then it is linked, for example, with a diphenylphosphine group.

The second catalyst precursor, a polymer that is im essentially consists of repeating units of the following structural formula

-O-Si-

can be referred to as poly-silsesquioxane (the unit can be referred to as silsesquioxane) and it is made by conventional hydrolysis of the first precursor. The hydrolysis * can be effected by simply mixing the first forerun with water and ^{heating it to temperatures within the range from about 25 to about 200 °} C. at atmospheric pressure or higher pressures. A practical method of performing the hydrolysis is to reflux the mixture. It is also possible to use other hydrolysis media, such as, for example, acids or water containing alkalis and polar organic solvents which contain dissolved water, acids or bases. The polymer obtained in this way is generally

30988171228

a glass-like, infusible solid with a melting point above 300 ° 0, which is insoluble in most common solvents, but soluble in acetone, dimethylformamide and dimethyl sulfoxide. It has a pronounced degree of thermal stability in the range of 300 to 35O ⁰ G, however, tends to be tacky at these temperatures. For this reason and also because of the caking in the presence of some active solvents, the polymer can be diluted with a silica gel or crosslinked by joint hydrolysis of the first precursor with, for example, tetrafunctional silicate esters. Theoretically, the hydrolyzable radical R defined above achieves an end blocking, but these radicals are difficult to determine analytically, especially in the polymers with a higher molecular weight.The non-linear nature of the polymer, which is mixed with it when crosslinking agents are used, contributes to this Difficulty with. The networking is explained in more detail below.

The catalyst is produced by introducing a suspension the second precursor, i.e. the polymer, in a medium such as methanol in a solution of a transition metal salt, e.g. of platinum (IV) chloride hexahydrate dissolved in methanol. The metal atoms coordinate with the phosphorus atoms of the precursor and a complex is formed which can be used in heterogeneous catalysis. Alternatively the same suspension of the second precursor can be introduced into a solution that is a spent homogeneous Catalyst composition similar to the transition metal salt mentioned above, dissolved in water or alcohol. Here, too, complex formation occurs and the platinum coordinates with the phosphorus in the same way. Since the transition metals have 1 to 6 coordination sites.

3 0 9881/1228

it is clear that a transition metal atom has 1 to 6 phosphorus atoms or 1 to 6 repeating units of the Can coordinate polymer. In the other case, the transition metal can be displaced from the acid or on another usual way or the complex can be used in heterogeneous catalysis If a heterogeneous catalyst is desired, the catalyst composition prepared in this way is to be separated off only a simple decantation required.

An example of a complex made by reacting sodium chloride palladite with polydiphenylphosphinylethyl silsesquioxane is formed with five repeating units and can be represented by the following formula

and for a complex that can be prepared in a similar manner using sodium chloroplatinite, can be found on the same whiteness can be represented, simply replacing the palladium with platinum in the above formula.

In the general structural formulas given above, the best have the following meanings:

R can be an organic, organometallic or inorganic radical which is selectively hydrolyzable at the R-CW bond _f where the organic and organometallic radicals are monovalent and the inorganic radical is in an oxidation state of. +1 is present, the radicals having 1 to 25 atoms in their molecular structure and being free of functional groups that could prevent hydrolysis at the RO bond or react with phosphorus. The only radicals R that can remain in the second precursor and in the catalyst

309881/12 28

are those in the end blocking positions. The remaining radicals R are of course hydrolyzed and optionally separated in this form from the desired product, for example as sodium hydroxide or ethyl alcohol. The definition of R is extremely difficult, since it is difficult to imagine a radical which, if it is hydrolyzable, cannot be used here. In order to avoid problems that could arise in various complexes and exotic molecules, an arbitrary restriction has been made here. The simplest radicals R include the straight-chain or branched-chain, substituted or unsubstituted alkyl radicals having 1 to 10 carbon atoms, for example methyl, ethyl and isopropyl. On the inorganic side, elements of Group 1a of the Periodic Table of the Elements, such as sodium, potassium and lithium, are representative examples · Other examples of the radicals R are acetyl (CH ₅ CO- ') and phenyl (CgHn-).

R is defined as non-substituted or unsubstituted _t straight or branched, divalent, geeättigter alkylene radical having 1 to 10 carbon atoms or a non-substituted or substituted, divalent aryl group having 1 to 3 benzene rings, where the alkylene radical by halogen or a phenyl radical and the Aryirest can be substituted by halogen or straight-chain or branched-chain saturated alkyl radicals with 1 to 5 carbon atoms.In its broadest sense, the radical R means a radical that does not contain any functional groups that could interfere with or react with the phosphorus atom in the formula, such as this for example a carboxyl residue would do. Examples of the radicals r '' are - (CHg) ₂ -, ^ ₁ p-phenylene, ie / \,

309881/1228

(\ 1,6-Dinaphthyl® ⁿ

ie CX 3- ^{and 1}

A substituent for the alkylene or aryl radicals can also

2 2

-P (B) 2, where R is as defined above. Unsubstituted, straight-chain alkylene radicals with 2 to 5 methylene

2 1

groups are preferred · R is defined similarly to R,. but with the exception that it is monovalent. He can be defined are called unsubstituted or substituted, straight-chain or branched-chain or cyclic mono- ■ valent, saturated alkyl radical with 1 to 10 carbon atoms or as unsubstituted or substituted, monovalent aryl radical with 1 to 3 benzene rings, the alkyl radical being replaced by halogen or a phenyl radical and the aryl radical substituted by halogen or straight-chain or branched-chain, saturated alkyl radicals having 1 to 5 carbon atoms could be. Here, too, it is the broadest

In the case of the Best R, meaning that it is not functional Contains groups that interfere with or with the phosphorus atom in the Formula, such as carboxyl. A preferred radical is the phenyl radical, other examples of the radicals R are methyl, ethyl, benzyl or cyclohexyl.

It should be noted that those given above are limited Definitions for R, R and R are arbitrary and only therefore were chosen to reflect the complexity of the precursors and the catalytic converter. In theory there is no reason to have the number of atoms or benzene rings below Do not get twice or three times as high to get similar results.

The number of repeating units or the molecular weight the second precursor, in view of its nonlinear nature, is difficult to determine · generally lies the number of units within the range of about 3 to

changed to -4. 309881/1228

about 1,000 and the molecular weight is within the range from about 750 to about 3,500,000. However, it is an object of the invention to provide a solid, polymeric catalyst composition which is insoluble in the reaction medium used. Higher molecular weights, if they are desired to be obtained in that heating the hydrolyzed products for extended periods to temperatures of between 100 and ⁰ JOO C. In the same plant, mixed compositions of one or more polymers of different particle size and complexity can be used to make the catalyst or recover the spent metal.

The polymer according to the invention is a non-linear or branched homopolymer whose most frequently recurring bond is that between Si and is 0. As stated, sufficient residues R can remain in the hydrolysis to remove the polymer at the terminals to block or complete. If desired, mixtures of the first precursors can be used to prepare the second precursor may be used, although this is not preferred. As indicated, can be shared with the first precursor Crosslinking agents, such as tetrafunctional silicate esters, can be hydrolyzed. The copolymer obtained in this way contains crosslinking units of the following structural formula

R ⁵ O
-0-Si-

in which Br is defined as R. The crosslinking units can be present in amounts from about 1 to about 20 mol-> o. This can be achieved in a simple manner by jointly

309881/1228

jointly hydrolyzing the crosslinking agents in an amount from about 1 to about 20 Mo 1- $ based on the number of Moles of the hydrolyzed first precursor »by use The crosslinking agent eliminates the tackiness of low molecular weight polymers and the number of phosphorus atoms in the final polymer is decreased if less complex formation is desired. A preferred amount of crosslinking agent is about 5 to about 15 Mo 1-%. The end blocking is theoretically the same as the second precursor. Examples of crosslinking agents are tetraethyl orthosilicate, QJetraphenylorthosilicate, silicon tetrachloride and methyltrichlorosilane The crosslinking agents are arbitrary at any intervals between the units of the polymer (statistically distributed) arranged

The catalyst composition according to the invention consists in essential from the second forerunner (that of being networked can be designated), in which each phosphorus atom in the Polymer is coordinated with a transition metal atom with a charge 0 or a positive charge, each positively charged transition metal atom a sufficient number of negatively charged organic or inorganic, has bests free of functional groups that are bound to it in order to saturate the valence of the transition metal atom, and being the best from the group of halogens, nitrates, sulfates, straight-chain alkoxy or aeyloxy radicals having 1 to 10 carbon atoms and the aryloxy radicals having 1 to 5 benzene rings. Since every transition metal atom 1 to 6 coordination sites and a phosphorus atom has a coordination site, a transition smet al latom 1 to 6 recurring units of the polymer saturate · The transition metal can be any of those listed in the Periodic Table of the Elements Transitional elements act or there can be two or

3098B1 / 1228

be several different transition metals. In general, a metal is made according to the method in which the Catalyst to be used is selected, platinum, palladium and platinum / palladium are preferred. Examples for other transition metals are vanadium, chromium, cobalt, nickel, rhodium, and tungsten. So long no functional ones Groups are available, the most varied of transitional

will·
Metal Compounds Used / In general, the inorganic metal compound or the organometallic compound used in the complex formation process is withdrawn from solution by the second precursor and becomes part of the catalyst composition by coordinating the phosphorus atom with the transition metal atom, or becomes a complex by coordinating the phosphorus atom with the transition metal atom . The best ones which form the transition metal compound together with the transition metal are mentioned above. Examples of such radicals are 01, Br, NO ,, acetate, propionate, butyrate and sulfate. An example where both alkoxy and acyl are present is the important acetylacetonate residue.

The use of the catalyst compositions according to the invention in suitable processes is advantageous insofar as thereby the problems of recovery and recycling of the coatable metals that occur in homogeneous catalysis, are essentially cleared out; continuous reactions are facilitated by having the reactants passes the catalyst composition through a pixel bed; the removal of the catalyst from the products is avoided; the Heat removal and, consequently, the control of the reaction are simplified; the economy of the catalyst will be improved; a special product can be made at lower cost and the sales, the amount of Product in kg obtained when using 1 kg of catalyst (metal itself) is increased.

309881/1228

As indicated above, the second precursor, i.e. the polymer itself, can be used in addition to the preparation of the catalyst composition also used to recover valuable metals after they have been used in homogeneous catalysis will. The second precursor is used in the manner of an ion exchange body, the catalyst metal being used containing liquid (fluid) flows from a homogeneous catalytic process through the second precursor and connects to it in a complex manner. The regeneration of the second precursor and the metal recovery can then in the usual way, for example by displacement, by heating or even by ashing and leaching with acids, be performed.

The second precursor can be viewed as a carrier polymer with a silicate backbone and an alternative Formula for the repeating unit can be given as follows

-O _5/2 Si-R ¹ -P (R ² ) ₂

where the number 3 means the other functions of Si _1, ie the number of oxygen atoms, and the denominator 2 indicates that each oxygen atom is generally shared with another Si atom.

The catalyst composition according to the invention is suitable for the hydroformylation of olefins including the oxo process, for the hydrogenation of olefins, dienes and Acetylenes, for the isomerization of olefins, for the polymerization of dienes or acetylenes, for the acetoxylation of olefins, for the silylation of olefins, for addition reactions at the double bond, for oligomerization addition to the double bond in dienes, for Addiüonseligiinierungsreaktionen and for the hydrocyanic change of olefins.

309881/1228

The following reaction schemes illustrate the complexity of the reactions involved in the preparation of the first and second precursors. The title indicates the final silsesquioxane, the second precursor. The index means the number of theoretically recurring units. The endblocking residues are not indicated. In the following reaction schemes: 0 = phenyl, Et = ethyl, Ac = acetyl, Bu = butyl, Me = methyl.

309881/1228

309881/1228

• rl M

cn

η φ

CQ H • Η

3098.81 / 122 8

»Ο

H H H

CQ

M Φ

ta H

• Η (Q

ft

r-r

bo

ac υ

■ 8

2 "

IO

309881/1228

• Η Ι W H

309881/1228

The following examples illustrate the preparation of the inventive Described precursor compounds and the use of the catalyst composition containing them are intended to explain the invention in more detail without, however, restricting it thereto. The analytical ones specified therein Data were determined in the usual way.

example 1 D, i "pheny lpho sphin

(5.17 mol) Diphenylphosphinigsäurechlorid- were taken under added to 1400 ml of distilled water with rapid stirring. The temperature rose to 70 ° C. The solution was 1 hour refluxed for a long time and then cooled. The lower organic layer was separated from the water, dried and distilled in vacuo, 207 β diphenylphosphine (yield 70%), b.p. 151 ° O / 10 mm »obtained. From the 327 g of residue were obtained by crystallization from ethanol Diphenylphosphonic acid (95% yield) was obtained.

B. From sodium diphenylphosphide ^ To a suspension of 4 * 6 g (0.2 g atom) of sodium grit in 100 ml of ^{anhydrous dioxane heated to 65 to 70 °} C. under nitrogen, a solution of anhydrous dioxane was added over the course of one hour. The solution was heated to reflux temperature (100 ° C.) for 4 hours until all of the sodium was consumed. Then, after cooling to 10 ° C., 30 ml of anhydrous ethanol were added dropwise, then 25 ml of water were added in order to dissolve the sodium chloride. The organic layer was separated and the water was extracted with ether. The organic layers were dried and vacuum distilled to give 14.14 g of diphenylphosphine (yield 76 %) .

^ j. \
'(diphenylphosphinous chlorides)

309881/1228

Example 2 2 ~ (Diphenylphosphinyl) ethyl ~ triethoxysilaii

To 18.6 g (1.0 mol) under nitrogen to 140 ⁰ G heated diphenylphosphine a mixture of 19 »g • ν (1.0 mol) Vinyltriäthoxysilan- and 1.92 g of di-t-butyl peroxide was added with stirring. The solution was kept at 140 to 160 ^° C. for a further hour. After the distillation in vacuo, 24.7 g of product (yield 65.7%), b.p. 162 ° 0 / 0.3 mm,

27
Up 1.5370. The degree of conversion _ at the base of the consumed

Vinyl silane was 93%. The H'mS ^ fCc ^) 0.8 (m, 2H), 1.12 (t, 9H), 2.24 (m, 2H), 3.76 (q, 6H} and 7.0-7.7 (m, 10H) agreed with the expected structure.

Example 3 Poly-2- (diphenylphosphinyl) ethyl silsesquioxane

A.) 37.6 g (0.1 mol) of 2- (diphenylphosphinyl) ethyl-triethoxysilane, dissolved in 100 ml of acetic acid with 10 drops of concentrated hydrochloric acid, were heated to reflux temperature for 2 hours. The solvents were removed by distillation and 26.5 S silica gel having a particle size of 0.074 mm (200 mesh) was added to the residue. The mixture was dried under nitrogen at 300 ^° C. for 4 hours and then pulverized after cooling. The yield was 47 g, 88.7 % of theory. Their analytical values were as follows: 1.48 mlqu. P / g, calc. For P - 5.85%, found: P - 4.59 %.

B.) 37.6 g (0.1 mol) of 2- (diphenylphosphinyl) ethyl-triethoxysilane and 2.08 g (0.01 mol) of tetraethyl orthosilicate were hydrolyzed together in an identical manner. This gave 26 g of a pesticide with an analysis of 11.04 % P

309881/1228

(3.56 m & qu. P / g). The infrared spectrum showed absorption bands consistent with the functional groups of the expected structure. The H'NMR spectrum showed broad resonance peaks at S (acetone d ₆ ) 0.7 (2H, Si-CH ₂ -), 2.1 (2H ₁ Si-C-CH ₂ -), 6.3 ( 1OH).

Example 4

1 «2-dibromoethyl-triethoxysilane

16 g (0.1 mol) of bromine, dissolved in 150 ml of carbon tetrachloride, were added to 19.0 6 (0.1 mol) of vinyltriethoxysilane, dissolved in 150 ml of carbon tetrachloride, containing 0.5 g of NaBr and cooled to ^{0 ° C.} Dark added over a period of 7 hours, waiting after each addition until the bromine color had practically disappeared. The material was distilled in vacuo and 32 g of product were obtained (yield 91.4%), boiling point 88 ° C./1 mm, ηψ 1.4620, the H'NMR spectrum: 6 (CD Cl ₃ ) 1.24 (t, 9H), 3.19-4.15 (m, 3H), 3.9 (q, 6H) was consistent with the expected structure.

example 5

2- (Diphenylphosphinyl) ethyl-triethoxysilane anion, neutralized

with H ⁺ _; [

19 , 0 g (0.1 mol) of vinyltriethoxysilane was added. There was a slight increase in temperature. The temperature was maintained by adjusting the feed rate of the vinyl silane at 30 ⁰ C. After 3 hours, 5 ml of anhydrous ethanol was added. The yellow color of the anion immediately disappeared. The solution

309881/1228

~ 22 -

was filtered to remove the inorganic salts. Gas chromatographic analysis confirmed the presence of diphenylphosphine and 2- (diphenylphosphinyl) ethyltriethoxysilane. After neutralization with carbon dioxide, the liquid was distilled and 6.3 g of 2- (diphenylphosphinyl) ethyl-triethoxysilane (yield 16.7 %) and 3.0 g of diphenylphosphine (yield 16.3 #) were obtained. The H ¹ NHR spectrum of the silane was identical to that of the addition product of diphenylphosphine on vinyltriethoxysilane with a free radical initiator.

Example 6 Implementation with Methyl.jodid

A diphenylphosphide anion suspension prepared under nitrogen from 4.6 g (0.2 g atom) of sodium and 22.0 g (1 mol) of diphenylphoaphynous acid chloride in 100 ml of dry toluene was added to 19.0 g (0.1 mol) of vinyltriethoxysilane 30 ° C added. After brief stirring, 14.19 g (0.1 mol) of methyl iodide were slowly added. The temperature rose rapidly to 40 ° C and was lowered to 25 ° C by cooling with ice water. The addition was complete within half an hour, during which time the light yellow solution turned into a light gray solution. The precipitated inorganic salt was filtered off under nitrogen in a drying cabinet and the toluene was concentrated in vacuo, 25 g of a pale yellow liquid being obtained. The material was distilled in vacuo and 1- (diphenylphosphinyl) propyl-2-triethoxysilane, boiling point 148 ° to 150 ° C./0.1 mm, was obtained. The H ¹ NMR spectrum 6 (C ₆ Dg) 0.6 (d, 3H), ~ Ό, 8 (m, H), 1.14 (t, 2.24 (m, 2H), 3.75 ( q, 6H), 6.9 to 7.6 (m, 10H) agrees with the structure (C ₆ Hc) ₂ PCH ₂ CH (CH) ₅ Si (OG ₂ H ₅ ).

309881/1228

Example 7 Allyldiphenylphosphine

A solution of a Grignard reagent in 250 ml of diethyl ether was prepared using 12.2 g (0.5 g atom) of magnesium turnings and 60.5 g (0.5 mol) of multiply distilled allyl bromide. The solution was forced with nitrogen through a glass tube with a final fine fritted glass filter into a 500 ml loading funnel. The analysis of the solution showed a content of 0.4 mol (80%) allylmagnesiurabromide. This solution was over a period of 3 1/2 hours to a solution of 75 added to a nitrogen atmosphere. The reaction was completed by refluxing the mixture for an additional 2 hours. Then it was cooled to 5 ° C. and, still under nitrogen, poured into a mixture of ice and a 20% strength ammonium chloride solution. The product was separated off in a nitrogen atmosphere, the ingress of air being avoided as far as possible. The ether layer was extracted three times with 25 ml of ether each time. The ether layers were combined with one another, washed with water, dried over anhydrous magnesium sulfate and finally distilled. The material boiling at 177 ° C./0.1 mm was collected (61.5% yield 80%), leaving a residue of 7 g. The residue was recrystallized from chloroform, mp 195 ° C. The residue consisted largely of diphenylphosphonic acid, evidently from the hydrolytic disproportionation (dismutation) of unreacted diphenylphosphinous acid chloride. The H'NMR spectrum of the distilled liquid: 6 (C ₆ D ₆ ) 2.75 (d, 2H, J «8 Hb) derived from ®; 4.9 (dd, 2H, J = 14, 3 Hz), derived from ®; 5.75 Ga, H) © ; 7.2 (m, 10H) ©, confirmed the structure

309881/1228

There was also an impurity which gave a complicated resonance spectrum in the vicinity of S 7j4- , which was probably due to diphenylphosphonic acid in a small amount.

Example 8 Implementation of diphenylphosphine with 3-bromopropyl-triäthox, ysilane

A solution of 18.6 g (0.1 mol) of diphenylphosphine and 28.5 g (0.1 mol) of 5-bromopropyltrimethylsilane in 100 ml of dry toluene was refluxed for one hour. After cooling the solution, 10% sodium hydroxide (0.1 mol) were added. The toluene layer was separated, washed with water and dried. The clear liquid separated into two layers on standing , the lower one of which eventually crystallized. The solid (0.746 g) was filtered off. It had a melting point of above 300 ⁰ O and probably represented the hydrobromide product. The filtrate was distilled in vacuo and 31 g of 5- (diphenylphosphinyl) propyltriethoxysilane (yield 79-5%) with a boiling point, a refractive index and a was obtained gas-liquid Ohromatographie retention time were identical with the corresponding values of the material prepared from hiumdiphenylphosphid Lit.

Example 9

3- (Diphen.Ylphosphinyl) propyl-triethoxysilane

To 18.0 6 (0.097 mol) diphenylphosphine, which under a stick

309881/1228

Substance atmosphere was heated to 140 ° C, a mixture of 19.8 g (0.097 mol) of allyltriethoxysilane and 1.86 g of dit-butyl peroxide was added within 3/4 hours. Heating was continued for one hour after the addition was complete. Analysis of the liquid showed the presence of unreacted phosphine and allylsilane, so 2.0 g of di-t-butyl peroxide was added and heating was continued for an additional 2 hours. This analysis, addition and heating were repeated once more, after which only a trace of diphenylphosphine was present. The liquid reaction mixture was distilled and 11.2 g of product were obtained (yield 30%), boiling point 180 to 184 ° C./0.7 mm, ηψ 1.5340. '

Example 10 3- (Diphenylphosphin.Yl) propyl ~ triethoxysilane

To 2.76 g (0.4 g atom) of lithium chips in 200 ml of dry tetrahydrofuran, 44 g (0.2 mol) of multi-distilled diphenylphosphinous acid chloride, dissolved in 100 ml of tetrahydrofuran in a dry nitrogen atmosphere, were added over the course of one hour, during which Addition was vigorously stirred at tree temperature. The idthium metal dissolved to form a blood red solution of lithium diphenyl phosphide. 50.8 g (0.18 mol) of 3-bromopropyl-triethoxysilane were added to this solution at 22 to 25 ° C. over the course of one hour. When the addition was complete, the solution turned pale yellow in color. Analysis of this solution by gas-liquid chromatography (305 cm (10 feet) x 0.635 cm (1/4 inch) SE-30 from Chromosorb W at 200 ^° C.) showed 1.8 % unreacted silane and 97.35 % 3- (triethoxysilyl) propyldiphenylphosphine. The tetrahydrofuran was removed in vacuo

309881/1228

distilled, and benzene was added to precipitate lithium chloride, which was filtered off. Pas filtrate was distilled in vacuo to give 44 ^ 6 g of product (yield 63.3%), bp 155 to 157 ^Q C / O, 2 mm, a. | ² ' ⁵ 1.5258. The H'ME spectrum 6 (O ₆ D ₆ ) 1.13 (t, 9H), 4.22 (q, 6H), 0.85 (t, 2H), 1.3-2.0 (p, 2H), 2.02 (t, 2H) ₅ 7.0 to 7.7 (m, 10H) was consistent with the expected structure. A similar experiment on a larger scale (0.5 mol) gave a yield of 76 %.

In a corresponding manner, 3-chloropropyltriethoxysilane was used for the reaction with lithium diphenylphosphide and the product was obtained in a yield of 62.2% (58.1 % distilled) and a degree of conversion of 100%, based on the silane used.

Example 11

Implementation of 3-bromopropyl trimethoxysilane with lithium diphenyl phoaphid

22 g (0.1 mol) Diphenylphosphinigsäurechlorid were slowly (within 1 2/3 hours) was added to a suspension of 1.38 g (0.2 g-atom) of lithium metal in 100 ml of dry tetrahydrofuran at 15 to 2O ⁰ C, while a nitrogen atmosphere was maintained over the liquid. To the blood-red solution 24.3 g (0.1 mol) were added over a period of 1 hr. At 22 to 25 ⁰ C 3-bromopropyl-trimethoxysilaib dissolved in 50 ml of dry tetrahydrofuran was added. The color changed to light yellow shortly before the addition of the silane was complete. The precipitated lithium salts were filtered off under a dry nitrogen atmosphere. The gas-liquid chromatography (200 ⁰ C, 305 cm (10 feet) x 0.635 cm (1/4 inch), 10 % SE-30 on a Chromosorb W column, 50 ml / min.

309881/1228

Helium) showed two main peaks at a retention time of 1.6 minutes, which were identified as unreacted bromosilane, the other peak occurring at a retention time of 18 minutes. The solvent was removed under vacuum and the bromosilane was recovered by distillation under reduced JDruck, wherein a in acetone, chloroform, benzene, üfcher, water and tetrahydrofuran and below 50O ⁰ G non-melting glass-like residue remained "The infrared spectrum of the solid showed strong bands at 2.93 and 6.15 microns, which returned to water, and bands at 3.4-, 3.28, 6.3, 6.75, 6,%, 8.4-7, 9.0 , 9, A-, 13.45, 13.93 and 14.47 microns, but no methyl band at 12.3 microns. The H'MR spectrum (hot G ₂ D ₅ OD) confirmed the absence of the methyl group and its presence the polymer structure

Example 12 Allyl diphenylphosphine oxide

A mixture of 11 g (0.05 mol) of diphenylphosphine chloride and 2.9 g (0.05 mol) of allyl alcohol in 50 ml of anhydrous ether was stirred at room temperature, while 4.0 g (0.05 mol) of Fyridifi. «Were given. After 40 minutes the pyridine hydrochloride was filtered off and the Xfcher was removed by distillation. The liquid residue was heated to 15O ⁰ G, an exothermic reaction started, so that the temperature rose rapidly to 178 ⁰ C · Then, the material Xp 168-175 ° C / 0.4 was distilled, mm, whereupon it crystallized, F, iq8 ° G. It was identical to the AlIyI ^ diphenylpbosphinoxyd, which had been prepared by oxidation of allyldiphenylphosphine, Ep. 200-202 ⁰ C / 2mm, F. 94-95 ⁰ C. '

Example 13 Reduction of Diphenylphosphine Oxide by Trichlorosilane

11.8 g (0.05 mol) of allyldiphenylphosphine oxide in 50 ml of dry Benzene was stirred under a nitrogen atmosphere while 13.5 g (0.1 mol) of trichlorosilane were slowly added. The temperature rose to 45 ° C. during the addition. the Solution was heated to reflux temperature for 2 hours, then cooled and filled with a 40% aqueous sodium hydroxide solution neutralized. The benzene layer was washed until neutral, dried over sodium sulfate and distilled, Bp 128 to 135 ° C / O, 2 mm, yield 9.1 g, 81% of theory. The H'NMR spectrum agreed with the allyldiphenylphosphine structure and with the material made from allyl magnesium bromide.

Example 14 Poly (3-diphenylphosphonyl) propyl-sesquioxane

39 g (0.1 mol) of (3-diphenylphosphinyDpropyl-triethoxysilane dissolved in 100 ml of acetic acid with 10 drops of concentrated aqueous HCl ₁ were refluxed for 2 hours. The ethyl acetate and acetic acid were distilled off and the residue was placed on a hot plate The glassy solid was pulverized and mixed with 30 g of silica gel with a particle size of 0.40 to 0.074 µm (38 to 200 mesh) and pulverized again. It was heated ^{in an oven at 200 ° C. overnight} The white solid had a phosphorus content of 4.47%, corresponding to 1.44 meq. P / g. The yield was 86.5% of theory. The infrared spectrum showed absorption bands at 3.26 microns (aromatic CH), 6.31.6 , 75, 6.97 microns (aromatic

309881/1228 "

see double blinding), 13.6, 14.5 microns (monosubstituted Phenyl), 3.42, 7.08 (methylene) and a strong broad absorption band at 9-11 microns, which is for the Si-O group is characteristic.

In a second preparation as above, but in which 2.08 g (0.01 mol) of tetraethyl orthosilicate were added as a crosslinking agent, a pesticide was obtained with an active material content of 3.5 rr / g.
Analysis: found P = 10.50%
calculated P β 10.87%

The infrared spectrum showed absorption bands identical to those of the first-mentioned material.

Example 15 Hydrolysis of 3- (diphenylphosphinyl) propyl-triethoxysilane

5.0 g (0.0128 mol) of the compound was refluxed in 25 ml of distilled water for 4 hours. The water was evaporated and the residue was dried in an oven under nitrogen at 300 ° C. A glassy pesticide (2.5 g) was obtained. The material had an infrared spectrum identical to that of the product of the trans-esterification reaction and an H ¹ NMR spectrum: £ (acetone-

d _c ): 0.55 (m, 2H), 1.42 (m, 2H), 1.95 (m, 2H), 7.0 to 8.0 o

(m, 10H), which with poly- (3-diphenylphosphinyl) propyl-silsesqui-

oxane [0-P (GH ^) - Si) ,, _]. It was in acetone, i ι ii / ζ η

Dimethylformamide, dimethyl sulfoxide soluble, but in water, Ethanol and methanol insoluble.

309881/122 8

Example 16 3- (Diphenylphosphinyl) propyl-trimethoxysilane

4.6 g (0.2 g atom) of sodium metal were dispersed in 100 ml of dry toluene, heated to 65 to 70 ° C. and, with vigorous stirring, 22 g (0.1 mol) of diphenylphosphinous acid chloride were added over the course of 3 1/2 hours while a dry nitrogen atmosphere was maintained above the liquid. After stirring overnight, the sodium was consumed and a deep yellow suspension of (CgH -) _ PNa and sodium chloride was obtained. 24.3 g (0.1 mol) of 3-bromopropyltrimethoxysilane were added over the course of 1 hour. A slight exotherm occurred and the liquid was kept at 40 ° C by cooling. After the addition, the reaction mixture was heated for 30 minutes to reflux. The color changed to light gray. The solution was cooled, filtered to remove the salts and concentrated in vacuo. The residue was distilled and 23 g of product were obtained (yield 66%), boiling point 174 ° C./0.8 mm. The H ¹ NMR spectrum £ (C _g D ₆ ): 0.83 (m, 2H), 1.60 (m, 2H); 2.00 (m _f 2H), 3.40 (S, 9H) and 6.98 to 7.65 (m, 10H) were consistent with the structure of the expected product .

Example 17

5- (diphenylphosphinyl) pentyl-triethoxysilane

Magnesium To the solution of one of 9.7 g (0.4 g-atom) / in 46.0 g (0.2 mol) 1,5-dibromopentane made Di-Grignard reagent in 600 ml anhydrous ether, containing 0.172 equivalents (43%) under a nitrogen atmosphere, 22.0 g (0.1 mol) Diphenylphoshinigsäurechlorid, dissolved in 100 ml tetrahydrofuran,

309881/122 8. original inspected

added under nitrogen at 15 ° C. with stirring over the course of 2 hours. The solution was then refluxed for 1/2 hour. The solution was cooled and forced into a loading funnel by nitrogen through a fine glass filter rod. Analysis showed a Grignard content of 0.0952 equivalents. This solution was added under nitrogen and with stirring over the course of 11/2 hours to a solution of 83 g (0.4 mol) of repeatedly distilled tetraethyl orthosilicate in 100 ml of tetrahydrofuran. The solution was then refluxed for 2 hours. The liquid was washed with a solution of 30 g of ammonium chloride in ice water. The organic layer was separated, washed twice with water, dried and then concentrated in vacuo. A small amount of solid was removed by filtration and the liquid was fractionated in vacuo under nitrogen. After Abdestlllieren excess ethyl silicate of the residue (12.7 g) had a boiling point within the range of 165 to 21O ° C / _f O 2 mm. Gas-liquid chromatography showed that it contained 3 compounds with retention times of 11.8, 15.3 and 42.5 minutes, the first and third compounds being the main components. Each of these compounds was collected and their H'NMR spectrum was determined. The less volatile compound from the spectrum i (CCl ₄ ): 1.15 it ', 3H), 3.70 (q, 2H) was identified as a lower polymer of ethyl silicate. The more volatile compound with the spectrum J (GgDg) s 0.72 {dd, 2H), 0.4 to 1.7 (m, 6H), 1.15 (t, 9H), 1.90 (splitting t, 2H), 3.72 (q, 6H), 6.8 to 7.7 (m, 10H) had the structure of 5- (diphenylphosphinyl) pentyl-triethoxysilane.

Example 18 4-chloropheny1-dipheny-phosphine

Aue 191 g (1.0 mol) of 1-bromo-4-chlorobenzene and 24.34 V (1 g-AtOtt) magnesium in 600 ml of dry ethyl ether was used on the * usual *

309881/1228

Wise a Grignard reagent prepared, but this time the temperature was kept below +2 ⁰ C to avoid the formation of a di-magnesium compound. 220.5 g (1.0 mol) of diphenylphosphinous acid chloride in 100 ml of dry ether below 10 ° C. were added to this solution over the course of 11/2 hours. The solution was refluxed for 1/2 hour. The precipitated salts were dissolved by adding 100 ml of a saturated ammonium chloride solution. The ether was separated off, dried and distilled, and 248 g of a product were obtained (yield: 83%) which was homogeneous in gas-liquid chromatography, boiling point 157 C / 25

0.08 mm, n _Q 1.6608. Its H ¹ NMR spectrum showed only characteristic aromatic protons. The infrared spectrum with bands at 3.26, 5.12, 5.27, 5.30, 5.52, 5.69, 6.31, 6.35, 6.75, 6.97, 9.2, 9 , 75, 9.88, 12.25, 13.57 and 14.43 microns confirmed the 4-chlorophenyldiphenylphosphine structure. Analysis! calcd. C ₁₈ H ₁₄ PCl: C 72.86%, H 4.76%, P 10.44%, Cl 11.95% found. C 72.83% H 4.85% P Io, 17%, Cl 11.69%,

Example 19

t 4-bromophenylphenyl phosphine

To a mono-Grignard reagent solution, prepared in 79% yield (by titration) from 236 g (1.0 mol) of p-dibromobenzene and 27.5 g (1 # 15 g atom) of magnesium in 1150 ml of dry diethyl ether 173.8 g (0.79 mol) of diphenylphosphinous acid chloride in 100 ml of ethyl ether were added over a period of 1 1/2 hours at -10 to 0 ° C. After the addition, the reaction mixture was heated to reflux temperature. The precipitated salts were dissolved with 350 ml of a saturated aqueous ammonium chloride solution and ice. The ether layer was separated, washed and dried and de-

309881/1228

distilled and one (Yield 71.8% based on the Grignard reagent) was 193.5 g of 4-bromophenyl-diphenyIphosphin, bp. 188 ⁰ CZClO mm and F. 71 to 73 ° C.

Example 20 4- (triethoxysilyl) phenyl-dipheny! Phosphine

54 g (0.21 mol) of tetraethyl orthosilicate were added to a Grignard reagent solution prepared from 36 g (0.1 mol) of 4-bromophenyIdiphenyIphosphine and 2.43 g (0.10 g atom) of magnesium in 130 ml of dry tetrahydrofuran the solution was heated to 55 ° C for 4 hours. The solvent was removed in vacuo leaving 27 g of a clear liquid containing 50% product as shown by gas-liquid chromatography. A sample taken therefrom gave an H'NMR spectrum £ (C _g D _g ): 8.84 (t, 9H), 3.74 (q, 6H), 6.90 to 7.90 (m, 14H) _t that matched the expected structure. The yield was 32%.

Example 21

4-bromophenyl-triethoxysilane

Made to a filtered Mono-Grignard reagent solution in 78.2% yield from 236 g - (1 mol) p-dibromobenzene and 27.5 g (1.15 g atom) of magnesium in 1175 ml of dry ether, were 487 g (2.34 mol) of tetraethyl orthosilicate within 15 minutes added in 400 ml of dry ether, while a nitrogen protective atmosphere above the liquid was maintained. The temperature rose from 24 to 37 ° C. Then the mixture became for 1 hour heated to reflux. The reflux condenser was replaced by one with a downward distillation

309881/1228

and the ether was removed while replacing it by adding 800 ml of dry toluene to the reaction mixture. Magnesium salts were precipitated in this procedure. These were filtered off under a nitrogen atmosphere. The filtrate was freed from toluene and the residue was distilled in vacuo, 161.5 g (yield 64.6%, based on the Grignard reagent) of 4-bromophenyltriethoxysilane being obtained, b.p. 90 ° C / O, 3 mm, 115 ° C / 1.9 mm, n _n 1.4872. The H'NMR spectrum 0 (C _ß D ₆ ): 1.18 (t, 9H),

3.82 (q, 6H), 7.5o (m, 4H) was for the expected structure characteristic.

Example 22 4- (Diphenylphosphinyl) phenyl-triethoxysilane

14.5 g (0.045 mol) of 4-bromophenyltriethoxy were added to a lithium diphenylphosphide solution prepared under nitrogen from 0.6246 g (0.09 g atom) of lithium and 9.92 g (0.045 mol) of diphenylphosphinous acid chloride in 50 ml of dry tetrahydrofuran , dissolved in 50 ml of dry tetrahydrofuran, added within 1 hour. The blood-red solution changed its color to light brown, with a small amount of a white solid becoming visible. The solution was filtered under nitrogen, diluted with benzene to precipitate the remaining lithium bromide and filtered again. Analysis of the solution by gas-liquid chromatography showed a content of unreacted bromosilane of 3.88 g, 0.0122 mol. After distillation in vacuo, 13 g of 4- (diphenylphosphinyl) phenyl-triethoxysilane (yield 68, 1%), bp 164 to 167 ° c / 0.1 mm. The H ¹ NMR spectrum was identical to that of the material prepared from 4- (diphenylphosphinyl) phenylmagnesium bromide and tetraethyl orthosilicate. The degree of conversion, based on the consumed

309881/1228

Bromosilane, was 93.4%.

Example 23 Use of the 4-chlorine compound

To a suspension of 2.1 g (0.3 g-atom) lithium in 150 ml anhydrous tetrahydrofuran kept under nitrogen was, a solution of 26.2 g (0.1 mol) of triphenylphosphine in 150 ml of dry was over a period of 1/2 hour Tetrahydrofuran added. The temperature rose from 25 to 55 ° C. The solution turned blood red and within 3 hours Almost all of the lithium in it dissolved. To this solution, 9.3 g (0.1 NoI) were added to destroy the phenyllithium t-butyl chloride added. The solution was filtered and her 27.5 g (0.1 mol) of 4-chlorophenyltriethoxysilane were dissolved in 50 ml of dry tetrahydrofuran, and the solution was refluxed for 4 hours. The red color was not completely gone at this point because of the slow nucleophilic displacement of the aryl " Chloride. The excess lithium diphenyl phosphide was destroyed by the addition of 25 ml of ethanol and finally by water. The solvents were removed in vacuo. the Liquid was taken up in toluene and filtered to remove the precipitated lithium chloride. The gas-liquid chromatographic Analysis of this solution showed the presence of recovered chlorophenylsilane, triphenylphosphine and only a small amount of 4- (Diphenylphosphhlnyl) -phenyl-triäthoxysilan (Yield about 15%).

Example 24 4-chlorophenyl-trchlorosilane
One under nitrogen from 38.3 g (0.2 mol) of l-bromo-4-chloro

309881/1228

233Ö308

benzene and 4.867 g (0.2 g atom) of magnesium prepared Grignard reagent solution in 300 ml of anhydrous diethyl ether was forced under nitrogen pressure through a glass filter rod into a graduated loading funnel, through which it was poured into a stirred solution of 102 g (0.6 mol) of multiply distilled silicon tetrachloride was introduced into 200 ml of dry ether. The solution was refluxed for an additional 2 hours, then cooled and filtered under nitrogen. If not sealed from air, the solution turned red and lower yields were obtained. The ether and excess silicon chloride were concentrated in vacuo and the residue was distilled in vacuo under nitrogen. In this case, 17 g of 4-chlorophenyltrichlorosilane (yield 35%), bp 83-85 was obtained. ° C / 3.4 mm, n £ ^{7 '5} l, 54OO, and 6.2 g of bis (4-chlorophenyl) dichlorosilane (Yield 20%), b.p. 146 to 150 ° C / 0.4 mm, m.p. 60-61 ° C.

Example 25 4-chlorophenyl-trimethoxysilane

To a solution of 49.1 g (0.2 mol) of 4-chlorophenyl-trichlorosilane in 27.6 g (0.86 mol) of anhydrous methanol, which had been heated to 65 ° C., a solution of 47.5 g was added (0.6 mol) of anhydrous pyridine in 150 g of dry benzene was added, the temperature being kept at 65 ° C. after the addition was complete. The pyridine hydrochloride was removed by filtration and the filtrate was distilled in vacuo to give 33.4 g of 4-chlorophenyltrimethoxysilane (yield 72%), the H'NMR spectrum of which (CCl ₄ ): 3.56 (s, 9H) , 7.41 (m _f 4H) agreed with the expected structure.

309881/122 8

Example 26

4-chlorophenyl-triethoxysilane from (i) 4-chlorophenyltrichlorosilane : This was prepared by the same procedure as the corresponding methoxysilane, but this time 27/6 g (0.6 mol) of anhydrous ethanol were used instead of methanol. After the distillation, 55 g of product were obtained (yield 100%), boiling point 105-107 ° C./2 ^{mm, n ^ 5} ' ^{5 l, 4740}

H ¹ NMR Spectrum J (CgDg): 0.33 (t, 9H), 3.89 (q, 6H), 7.55 (m,% H); and (ii) 4-chlorophenyl magnesium bromide: A Grignard reagent solution prepared in 63% yield from 114.9 g (0.6 mol) of 1-chloro-4-bromobenzene was added to a solution of 249.6 g (1.2 mol ) repeatedly distilled tetraethyl orthosilicate in 300 ml of anhydrous ether at 0 to 10 ° C within 2 1/2 hours. After the addition was complete, the mixture was heated to reflux temperature for 2 hours, then cooled and filtered under a nitrogen blanket. After the ether had been removed, the product (78 g, 85% yield) was distilled in vacuo, boiling point 121 123 ° C./5 mm.

Example 27 4- (Diphenylphbsphinyl) phenyl-silsequioxane

24.3 g (0.1 mol) of 4-chlorophenyltrichlorosilane were hydrolyzed with 200 ml of a 10% strength aqueous hydrochloric acid at 20 ^° C. for 4 hours. The white solid formed (16 g) was collected by filtration. It has a melting point of over 300 ° C. and was insoluble in all common organic solvents and in water.

The 4-chlorophenyl-silisequioxane prepared above was along with 1.4 g (0.2 g atom) lithium and 250 ml dry

309881/1228

Place tetrahydrofuran in a flask and reflux for 16 hours. It was cooled to 25 ° C. and 8.8 g (0.04 mol) of diphenylphosphinous acid chloride, dissolved in 50 ml of tetrahydrofuran, were added dropwise over the course of 11/2 hours. The solution is refluxed for an additional 2 hours. At this point a homogeneous solution was obtained. The solvent was removed in vacuo, leaving 28 g of a white solid which was soluble in ethanol and tetrahydrofuran but insoluble in water and common organic solvents. The solid was separated from the enclosed lithium chloride by repeated dissolution in tetrahydrofuran and precipitation with n-hexane, and 16 g were obtained, mp> 300 ^° C. The infrared spectrum of this solid showed absorption bands at 3.27, 6.29 and 6.70 Microns (aromatic), 12.25 microns (p-substituted aromatic), 13.23, 13.79 and 14.44 microns (mono-substituted aromatic), 8.80 microns (Si-phenyl) and 9.17 microns (Si-O). The elemental _analysis was: Calculated for C 18 H ₁₄ SiPO _3/2 : C 68.99% H 4.50% Si 8.96% P 9.88% found. C 66.07% H 4.77% Si - P 9.92%

Example 28

Coupling of p-halophenyl-triethoxysilane and p-halophenyl-dipheny! Phosphine

A *) Mit_Lithiummetal 1: To a suspension of 1.44 g (0.2 g atom) of lithium powder with a particle size of 150 R in 50 ml of anhydrous tetrahydrofuran under nitrogen and cooled to 0 C, 27, 5 g (0.1 mol) of p-chlorophenyltriethoxysilane, dissolved in dry tetrahydrofuran, were added. The solution turned deep red when the lithium dissolved. There were 29.7 g (0.1 mol)

309881/1228

233G30 "

p-Chlorophenyl-diphenylphosphine, dissolved in tetrahydrofuran, and 100 mg (0.001 mol) of anhydrous copper (I) chloride were added and the mixture was heated to reflux temperature for 2 hours. The solution remained dark in color, but turned lighter on standing. The precipitated salts (8g) were filtered off and washed with benzene. The solvents were removed by concentration in vacuo leaving a dark yellow syrup containing a small amount of a pesticide. The liquid was redissolved in benzene, the solids were removed by filtration and the solution was concentrated to 30 g of a yellow oil. The gas-liquid and thin-layer chromatography showed that the oil consists of a small amount of unreacted chlorine. silane and chlorophosphine and a larger amount of a high-boiling component. The volatile components were removed by distillation under high vacuum, leaving 24 g of a dark yellow solid which is insoluble in most solvents. There was no chlorine present. The H'NMR spectrum £ (DMF-d7) 1.10 (t, 9H), 3.74 (q, 6H), 6.9-8, O (m, 18H) confirmed the expected structure ^(C 6 ^H 5> 2 ^ 6 ^Η 4 · ^α ₆ ^Η 4 ⁸

i ^ g A mixture of 14.9 g (0.0467 moles) 4-bromophenyl-triethoxysilane, 10.3 g (0.0302 mole) of 4-bronphenyldiphenylphosphine and 1.0 g of copper powder was heated to 250 ° C for 3 hours. During this time a solid separated out and this was recovered by filtration (26 g) leaving 10 g of a light yellow liquid. the Liquid contained, as gas-liquid chromatography showed, 0.011 mol of unreacted silane and 0.001 mol of phosphine. The solid was insoluble in common solvents, in Dimethylformamide, however, is soluble. The copper was removed from the DMF solution by filtration. Thin layer chromatography (Ethyl acetate) showed that the solid was mainly

309881/1228

borrowed from one component, (R _f = 0.16) and smaller amounts of lighter materials (R _f = 0.4, 0.6, 0.97) consisted. The H ¹ NMR spectrum of the R _f 0.16 material obtained by chromatography was similar to that of the above material.

Example 29 Palladium complex of diphenylphosphinylethylsilsequioxane

The 5P: 1 Pd complex was made by making a solution of 0.5363 g (1.56 mol) of sodium chloropalladite tetrahydrate in 80 ml of anhydrous ethanol with 2.0O3 g of the polymer with a phosphorus content of 3.56 mSq./g for 3 hours Reflux was boiling. After cooling, the solids were filtered off on a Buchner filter, washed with ethanol and dried. 2.2516 g of a pale lemon yellow solid were obtained.

Example 30 Platinum complex of diphenylphosphinylethylsilsequioxane

A solution of 0.890 g of sodium bisulfite in 10 ml of distilled Water was added to a solution of 0.7388 g of chloroplatinic acid hexahydrate in 40 ml of anhydrous ethanol. the • The solution was warmed to drive off the sulfur dioxide. The 3.56 m & qu. P / g containing polymer (2.046 g, suspended in 40 ml of ethanol) was then added and the mixture was refluxed for 3 hours. After cooling down the solids were separated by filtration, washed twice with 6 ml portions of distilled water and dried. 2.4970 g of a light orange - yellow solid were

309881/1228

hold, which was the 5 Pil Pt coraplex.

Example 31

Use of the platinum complex of Dlphenylphosphinyläthylsllseguioxan as Silylierungskatalysatori

A mixture of 6.72 g (0.05 mole) allyl chloride and 2.4 mg (1.66 mmol) of the catalyst were placed in a thick walled 2.54 cm (1 inch) x 20.32 cm (8 inches) glass test tube inserted and sealed with a pressure cap. The pipe was Shaken in a 70C water bath for 8 hours. A sample was taken from the liquid and placed on his 3-chloropropyltrichlorosilane content analyzed that it contains was included. Its presence was confirmed by comparing the sample with an authentic material and chromatographing the mixture together. The product liquid was completely removed from the catalyst and replaced with a fresh mixture of allyl chloride and trichlorosilane and the experiment was repeated. After 4 hours of reaction, 3-chloropropyltrichlorosilane was again in the liquid established. The liquid was again removed, replaced with fresh reactants, and the experiment was repeated twice repeated. Each time the condensation product became 3-chloropropyltrichlorosilane educated. This indicated that the solid was catalyzing the silylation and was in the reactants or in was not soluble in the products.

Example 32

Use of the palladium complex of Diphenylphosphhlnyläthylsilsequioxan as a catalyst for the octadienol synthesis:

A mixture of 0.309 g of the catalyst (the 220 mmol

309881/1228

Palladium contained), 182.5 mg of diphenylphosphinylethylsilsequioxane, 5.0 g {108.5 mmol) ethanol, 1.0 ml (55.5 mmol) distilled Water and 3.0 g (55.5 mmoles) of 1,3-butane were packed into a thick walled 2.54 cm (1 inch) x 20.32 cm (8 inches) Glass test tube inserted and closed with a pressure lock. The tube was placed in a water bath for 2 hours shaken at 70 ° C. Gas-liquid chromatography analysis showed the presence of 2,7-octadienol-1 and ethyl-2,7-octadienyl ether. The liquid was removed, replaced with fresh reactants, and the experiment was put into use of the same catalyst carried out again. Also here were receive the same products.

The abbreviations used in the above examples have the following meanings:

g = gram, bp = boiling point, mm = millimeter Hg, H ¹ NMR = nuclear magnetic prcton resonance spectrum, s = singlet, d = doublet, t = triplet, g = quintet, m = multiplet, mSqu. = Milliequivalents, ml - milliliter, J = coupling constant, Hz = vibrations per second, D = deuterium, SE-30 = a silicone rubber rubber, Chromosorb W = a silicon-containing diatomaceous earth absorbent from John-Manville Corp., calcined with a flux .

309881/1 228

Claims (8)

Claims 1. Non-linear polymer (as a catalyst precursor), characterized in that it consists essentially of one repeating unit consists of the following structural formula (E ² ) ₂ P
R ¹ -0-Si t 0
ι where mean: R is a straight chain which is not substituted or substituted or branched-chain, divalent, saturated Alkylene radical with 1 to 10 carbon atoms or a non-substituted one or substituted, divalent aryl radicals having 1 to 3 benzene rings, the alkylene radical being replaced by halogen or a phenyl radical and the Ary3a * est by halogen or straight-chain or branched-chain, saturated alkyl radicals may be substituted by 1 to 5 carbon atoms, and ρ
R is an unsubstituted or substituted, straight-chain or branched-chain or cyclic, monovalent, saturated alkyl radical having 1 to 10 carbon atoms or an unsubstituted or substituted, monovalent aryl radical having 1 to 3 benzene rings, the alkyl radical. can be substituted by halogen or a phenyl radical and the aryl radical by halogen or straight-chain or branched-chain, saturated alkyl radicals having 1 to 5 carbon atoms. 309881/1228 2. Polymer according to claim 1, characterized in that the non-linear polymer has 1 to 20 Mo 1- $ crosslinking units of the following structural formula contains E ⁵ O
-0-Si- 0
• ι in which R ^ is defined as E in claim 1, to achieve the crosslinking are arranged at any distance between the units of the polymer in any distribution. 3. Polymer according to claim 1 / pTäaiTurch characterized by that the polymer contains 5 to 15 mol% of crosslinking units. 4th Polymer according to claim 1 / f "characterized in that that in the structural formula R is an alkylene radical with 1 to Carbon atoms or a non-chlorinated or chlorinated 2nd phenylene or diphenylene radical and R is an alkyl radical with 1 to 5 carbon atoms or one non-chlorinated or chlorinated phenyl or diphenyl radicals. 309881/1228 5 x catalyst composition, characterized in that _t that it consists essentially of a non-linear polymer according to claim 1 to 4 ", is coordinated in which each phosphorus atom in the polymer with a transition metal atom with the charge 0 or a positive charge, each positively charged Transition metal atom has a sufficient number of negatively charged organic or inorganic radicals free of functional groups, which are bonded to it to saturate the valence of the transition metal atom, and wherein the radicals are selected from the group of halogens, nitrates, sulfates, straight-chain alkoxy - Or acyloxy radicals with 1 to 10 carbon atoms and the aryl-r oxy radicals with 1 to 5 benzene rings. 6. Catalyst composition according to claim 5, characterized characterized in that it contains chloride as a negatively charged residue. 7. Catalyst composition according to one of claims 5 or 6, characterized in that it contains a metal from the group of platinum, palladium or mixtures thereof as the transition metal. 8. Catalyst composition according to claim 5-7, characterized characterized in that they have a 1 - 20, preferably 5 - 15, Mol-? S a crosslinking agent according to claim 2. Dar patent attorney . Sohmiett-Kowarzlk 309881/4228