NL8800770A - New phosphide(s) phosphine(s) and di:phosphine(s) - used in catalyst for co-polymerisation of carbon mono:oxide and olefinically unsatd. cpds. - Google Patents

Abstract

(i) Phosphides of formula R9PMY (I) are prepd. by reacting an alkali metal (M) with a phosphine of formula R7R8R9P, in liq. NH3. (ii) Diphosphines of formula R9HP-R-PR9H (II) are prepd. by (a) reacting (I) with a proton donor to give the corresp. monophosphine R9PH2 (III), (b) converting (III) to the corresp. Li phosphide, R9PLiH (IV) by reaction with an alkyl-Li cpd., and (c) reacting (IV) with a di-halo cpd. of formula X-R-X. (iii) Diphosphines of formula R9R10P-RPR9R10 (V) are prepd. by (a) converting (II) to the corresp. Li diphosphide of formula R9LiP-R-PR9Li (VI) by reaction with an alkyl-Li cpd., and (b) reacting (VI) with a monohalo cpd. of formula X-R10, or by (c) reacting (IV) with a monohalo cpd. of formula X-R10, to give a monophosphine of formula R9R10PH (VII), (d) converting (VII) to the corresp. Li phosphide of formula R9R10PLi (VIII) by reaction with an alkyl-Li cpd., and (e) reacting (VIII) with a dihalo cpd. X-R-X. (iv) New phosphides of formula (I), and new phosphines of formula (VII) and R9R10R11P, and phosphines obtd. by reacting the specifically claimed phosphides with a proton donor are claimed. In the formulae, M = alkali metal; Y = H or Me; R9 = aryl gp., opt. with polar substit.; in the new cpds., R9 is polar-substd.; R7, R8 = aryl gps. with polar substit(s). in the o- or m-position w.r.t. P, and at least 1 substit. in the o-position; hydrocarbon gps. opt. polar-substd., with a C=C gp. linked to P through an aliphatic C; or H, but are not both H; X = halogen; R = divalent organic bridging gp. with at least 2C; R10, R11 = aliphatic hydrocarbon gp., opt. polar-substd.

Description

T 356 NET

PREPARATION OF PHOSPHIDS

The invention relates to a process for the preparation of phosphides which are suitable for use in the preparation of dlphosphines. The latter compounds find use as a component in catalyst compositions intended for the preparation of polymers of carbon monoxide with one or more olefinically unsaturated compounds.

High molecular weight linear polymers of carbon monoxide with one or more olefinically unsaturated compounds (for the sake of brevity denoted as A) in which the monomer units 1 - (CO) - and the units -A '- derived from the monomers A used - can be prepared alternately using catalyst compositions based on a) a palladium compound, b) an anion of an acid with a pKa of less than 6, and c) a diphosphine of the general formula R.] R2P-R-PR3R4 wherein R 1 to R 4 are equal or represent several aromatic hydrocarbyl groups and R is a divalent organic bridging group containing at least two carbon atoms in the bridging.

20

Very suitable diphosphines for use as component c) in the catalyst compositions are those of the general formula (Ri) 2R-RR (R1) 2 * Such compounds can be prepared in a simple manner by reaction in liquid ammonia of an alkali metal M with a Tri (hydrocarbyl) phosphine (Rj ^ P, followed by reaction of the

alkali metal di (hydrocarbyl) phosphide (R-1 / PM) thus obtained

with a dihalogen compound X-R-X. For example, 1,3-bis (diphenylphosphino) propane can be prepared by reaction in liquid ammonia of sodium with triphenylphosphine followed by reaction of the sodium diphenylphosphide obtained in quantitative yield with 1,3-dichloropropane.

In the past, the Applicant has conducted an investigation into the above catalyst compositions.

It has been found that in some cases their behavior can be improved by adding a diphosphine at .8800770 as component c).

«I

- 2 - to be taken with the general formula R ^ RjP-R-PRjRg wherein R ^ represents an aromatic hydrocarbyl group and R5 represents an aliphatic hydrocarbyl group. When comparing the behavior of catalyst compositions containing as component c) a diphosphine of the general formula (R ^) 2P-RP (R ^) 2 such as 1,3 "bis (diphenylphosphino) propane with that of corresponding catalyst compositions which, however, component c) a diphosphine of the general formula R1R5P-R-PR2R5 such as 1,3-bis (phenyl, n-butylphosphino) propane, it appears that at a reaction temperature equal for both compositions with the latter compositions higher molecular weight polymers be obtained. Furthermore, it has been found that diphosphines of the general formula R ^ R ^ PR-PR ^ R ^ in which R5 instead of an aliphatic hydrocarbyl group represents a hydrogen-15 atom, such as 1,3-bis (phenylphosphino) propane, are very suitable for to be used as component c) in the catalyst compositions.

The Applicant has conducted a study on the preparation of diphosphines of the general formula R-jRjP-R-PR-^ 20 in which R- represents an aromatic hydrocarbyl group and R5 represents an aliphatic hydrocarbyl group or a hydrogen atom. In view of the high yields obtained in the past in the preparation of diphosphines of the general formula (^ 1) 2 ^ - ^ - ^ (^ 1) 2 by reaction in liquid ammonia of an alkali metal M with a tri (hydrocarbyl ) phosphine (Rj ^ P followed by reaction of the thus obtained alkali metal di (hydrocarbyl) phosphide (R ^ ^ PM with a dihalogen compound XRX), an initial attempt was also made to also use the diphosphines of the general formula R1R5P-R-PR ^ R5 wherein R5 represents an aliphatic hydrocarbyl group to be prepared in this way, starting from tri (hydrocarbyl) phosphines of the general formula (R5 RsP.) The investigation has shown that this preparation method is not very attractive, due to the low yield of alkali metal di For example, starting from diphenyl, isopropyl phosphine by reaction in liquid ammonia with sodium, the .8800770-3 - desired sodium phenyl, isopropyl phosphide was obtained in a yield of less than 15% (hydrocarbyl) phosphide.

Again in view of the high yields obtained in the past in the preparation of monophosphides of the general formula (R ^ PM by reaction in liquid ammonia of an alkali metal M with a tri (hydrocarbyl) phosphine (R ^) gP, then attempted to use this preparation method for the preparation of diphosphides of the general formula RjMP-R — PRjM starting from 10 diphosphines of the general formula (Ry) 2P-RP (¾) 2 · The underlying idea was that from the diphosphides thus obtained the desired diphosphines of the general formula R ^ R ^ PR-PRj ^ could be prepared in a simple manner, namely diphosphines in which R5 represents a hydrogen atom by reacting the diphosphides with a proton donor or diphosphines in which R5 represents an aliphatic hydrocarbyl group by reaction of the diphosphides with an aliphatic hydrocarbyl halogen compound R5-X. The investigation has shown that this preparation method is also not very attractive, in view of the low yield of diphosphide R - [_ MP-R-PR] _M.

For example, starting from 1,3-bis (diphenylphosphino) propane by reaction in liquid ammonia with sodium, the desired 1,3-bis (sodium phenylphosphido) propane was obtained in a yield of less than 10%.

Further research on this subject has now found that monophosphides of the general formula R ^ PMY wherein Y represents a hydrogen atom or an alkali metal M, which monophosphides are suitable to serve as starting materials in the preparation of diphosphines of the type described above R ^ High-yield PR-PR-1 can be obtained by applying the alkali metal cleavage reaction in liquid ammonia to a monophosphine of the general formula RjRyRgP wherein Ry and Rg represent equal or different groups selected from BSO 0770. - 4 - a) aryl groups containing one or more polar substituents which can only occupy the ortho and meta positions with respect to the phosphorus atom and at least one of which is ortho-standing with respect to phosphorus, 5 b) optionally polar substituted hydrocarbyl groups which have a> C- = C <group which is attached to the phosphorus atom via only one aliphatic carbon atom, and c) hydrogen, with the proviso that Ry and Rg do not simultaneously represent hydrogen.

The monophosphides obtained in this way generally consist of mixtures of alkali metal phosphides of the general formula R 1 P (M) 2 and alkali metal phosphides of the general formula R 1 PMH.

In the investigation it was further found that the above-described preparation method is also very suitable for the preparation of monophosphides of the type R-PMY in which the aromatic hydrocarbyl group is polarly substituted and is, for example, a 2-methoxyphenyl group or a 2,6-dimethoxy-phenyl group. . In the further argument, the optionally polar substituted aryl group which occurs in the monophosphides to be prepared will be referred to as Rg.

The present patent application therefore relates to a process for the preparation of phosphides, wherein phosphides of the general formula RgPMY are prepared by reacting in liquid ammonia an alkali metal M with a phosphine of the general formula RyRgRgP, in which general formulas Y is a hydrogen atom or an alkali metal represents M, Rg is an optionally polar substituted aryl group and Ry and Rg represent equal or different groups selected from a) aryl groups containing one or more polar substituents which can occupy only the ortho and meta positions relative to the phosphorus atom and at least one of which occurs ortho-to phosphorus, b) optionally polar substituted hydrocarbyl groups containing a> CC <group attached to the phosphorus atom via only one aliphatic carbon atom, and c) hydrogen, with the proviso that Ry and Rg do not represent hydrogen at the same time.

.8800770 - 5 -

To the extent that in the phosphides of the general formula RgPMY the group Rg contains one or more polar substituents, these phosphides are new compounds. Also new compounds are the phosphines which can be obtained from these phosphides by reacting them with a proton donor. The present patent application also relates to these new compounds. Examples of these new phosphides and phosphines are sodium (2-methoxyphenyl) phosphide and 2-methoxyphenylphosphine, sodium (4-methoxyphenyl) phosphide and 4-methoxyphenylphosphine, sodium (2,6-dimethoxyphenyl) phosphide and 2,6-dimethoxyphenylphosphine, sodium (2-methoxy-5-methylphenyl) phosphide and 2-methoxy-5-methyl-phenylphosphine, sodium (2,5-dimethoxyphenyl) phosphide and 2,5-dimethoxyphenylphosphine, sodium (2-dimethyl-15-aminophenyl) phosphide and 2- dimethylaminophenylphosphine and sodium (2-dimethylaminomethylphenyl) phosphide and 2-dimethylaminomethylphenylphosphine.

The monophosphides of the general formula RgPMY prepared according to the invention are primarily intended for use in the preparation of diphosphines of the general formula RgHP-R-PRgH. To this end, the monophosphides can first be converted by reaction with a proton donor into the corresponding monophosphines RgP1 ^, then converted by reaction with an alkyl lithium compound to the corresponding lithium phosphides RgPLiH and the latter compounds react with a dihalogen compound X-R-X.

The monophosphides of the general formula RgPMY are further intended to be used in the preparation of diphosphines of the general formula RgR ^ QP-R-PRgR ^ Q wherein Rg represents an optionally polar substituted aliphatic hydrocarbyl group. This preparation can take place in two ways. On the one hand, the diphosphines RgHP-R-PRgH prepared in the manner described above can be converted by reaction with an alkyl lithium -8800770-6 to the corresponding lithium diphosphides RgLiP-R-PRgLi and the latter compound reacted with a monohalogen compound X-R] _q. On the other hand, the lithium phosphides RgPLiH prepared in the manner described above can first be converted by reaction with a monohalogen compound XR-^ q into monophosphines R ^ R ^ qPH, then converted by reaction with an alkyl lithium compound to the corresponding lithium phosphides RgR ^ QPLi and the latter compounds react with a dihalo compound XRX.

To the extent that in the monophosphines RgR 1 gPH obtained in the above-described intermediate manner, the group Rg contains one or more polar substituents, these monophosphines are new compounds. Also new compounds are the monophosphines of the general formula 9 9 10 10 11 11 waarin in which the group Rg contains one or more polar substituents and R _ q and R voorstellen represent identical or different optionally polar substituted aliphatic hydrocarbyl groups and which can be obtained by the monophosphines RgR-gPH prepared in the manner described above by reacting with an alkyl lithium compound the corresponding lithium phosphides RgR-gPLl and reacting the latter compounds with a monohalogen compound XRq. The present patent application also relates to these new compounds. Examples of these new phosphines are 2-methoxyethyl, 2,6-dimethoxyphenylphosphine, di- (2-methoxyethyl), 2,6-dimethoxyphenylphosphine, and dibutyl, 2,6-dimethoxyphenylphosphine.

The present patent application further relates to catalyst compositions based on a) a palladium compound, b) an anion of an acid with a pKa of less than 6, and c) one of the diphosphines of the general formula RgHP prepared as described above -R-PRgH or R9R10P-R-PR9R10.

The present patent application finally relates to the use of these catalyst compositions in the preparation of carbon monoxide polymers with one or more olefinically unsaturated compounds, as well as to the polymers and molded articles thus prepared which are at least partly made from these polymers. to exist.

In the process of the invention, compounds of the general formula RgPMY are prepared from compounds of the general formula RyRgRgP. As groups R7 and Rg which may occur in the compounds of the general formula RyRgRgP are eligible in the first place aryl groups which contain one or more polar substituents which can only occupy the ortho and meta positions with respect to the phosphorus atom and of which at least one prevents ortho-position with respect to phosphorus. Examples of such groups are the 2,6-dimethoxyphenyl group, the 2-methoxyphenyl group, the 2-methoxy-5-methylphenyl group, the 2,5-dimethoxyphenyl group, the 2-dimethylaminophenyl group and the 2-dimethylaminomethylphenyl group. If compounds RyRgRgP are used in which the groups R7 and / or Rg belong to this category, preference is given to phenyl groups which are ortho-relative to

Phosphorus contains one or two alkoxy groups and more particularly to phenyl groups in which these alkoxy groups are methoxy groups.

Also suitable as groups R7 and Rg which may exist in the compounds of the general formula RyRgRgP are optionally polar substituted hydrocarbyl groups which contain a> C-C <group which is bound to the phosphorus atom via only one aliphatic carbon atom.

If compounds RyRgRgP are used in which the groups R7 and / or Rg belong to this category, the benzyl group and the allyl group are preferred. Finally, compounds RyRgRgP can be used in which R7 or Rg represents hydrogen.

The process according to the invention preferably starts from compounds RyRgRgP in which at least two of the groups R7 to Rg are equal and which can therefore be represented by the general formulas (Ry ^ RgP and 87 (89) 2 ^ Examples of compounds which may be represented by the general formula (Ry ^ RgP are phenyldi-benzylphosphine and 4-methoxyphenyldibenzylphosphine. Examples 5 of compounds which can be guaranteed by the general formula RyiRg ^ P are di (2 , 6-dimethoxyphenyl) phosphine and di (2-dimethylaminophenyl) phosphine.

In the process of the invention, particular preference is given to the use of compounds RyRgRgP in which the groups Ry through Rg are equal and which can therefore be represented by the general formula (Rg) 3P. Examples of such compounds are tri ((2,6-dimethoxyphenyl) phosphine, tri (2-methoxyphenyl) phosphine, tri (2-methoxy-5-methylphenyl) phosphine, tri (2,5-dimethoxyphenyl) phosphine, tri (2 dimethylaminophenyl) phosphine and tri (2-dimethylaminomethylphenyl) phosphine.

The conversion of phosphides of the general formula RgPMY 20 prepared according to the invention into phosphines of the general formula RgPH2 can take place by reacting the phosphides with a proton donor such as water, an acid, an alcohol or ammonium chloride.

The phosphides according to the invention are prepared by reacting in liquid ammonia an alkali metal M with a phosphine. Lithium, potassium and sodium can be used as alkali metals. Preference is given to the use of sodium as the alkali metal. The amount of alkali metal used in the cleavage can vary within wide limits. More than two equivalents of alkali metal are preferably used per hydrocarbyl group to be cleaved.

In view of the yield of desired phosphide, it is preferable to carry out the addition of the amount of the alkali metal to be used in two or more steps, prior to each subsequent addition of the previously formed 8800770-9 phosphide by reaction with a proton donor is converted into the corresponding phosphine. The amount of liquid ammonia can vary within wide limits. Preferably 1 to 125 ml and in particular 10 to 40 ml of liquid ammonia are used per mmole of alkali metal. In view of the fact that liquid ammonia boils at atmospheric pressure at about -33 ° C, the process, if conducted at atmospheric pressure, should take place below -33 eC. Preferably, the process is carried out at a temperature from 10 -100 to -35 ° C and in particular from -80 to -35 ° C. If the process is carried out under pressure it is possible to work at temperatures above -33 ° C if desired.

As stated above, the present patent application also relates to catalyst compositions for the preparation of polymers of carbon monoxide with one or more olefinically unsaturated compounds, which catalyst compositions are based on a) a palladium compound, b) an anion of an acid with a pKa of less than 6, and c) one of the diphosphines of the general formula R9HP-R-PR9H or R9Ri0P-R-PR9Rio prepared in the manner described above

The palladium compound used as component a) in the catalyst compositions is preferably a palladium salt of a carboxylic acid and in particular palladium acetate. As component b), an anion of an acid with a pKa of less than 4 (measured in aqueous solution at 18 ° C) is preferably used in the catalyst compositions, and in particular an anion of an acid with a pKa of less than 2. More particularly preferred is an anion of a sulfonic acid such as para-toluenesulfonic acid or an anion of a carboxylic acid such as trifluoroacetic acid. Component b) can be included in the catalyst compositions in the form of an acid and / or in the form of a salt. The salts include, among others, non-precious transition metal salts such as .8800770 - 10 - copper salts. As the component c), a diphosphine is preferably used in the catalyst compositions in which the divalent bridge group R is a - (0 ^) 3 group. In addition to components a), b) and c), the catalyst compositions may also contain 5 promoters. A 1,4-quinone, and in particular a 1,4-naphthoquinone, is preferably used for this purpose.

As olefinically unsaturated compounds which can be polymerized with carbon monoxide using the catalyst compositions described above are both compounds consisting exclusively of carbon and hydrogen and compounds containing one or more heteroatoms in addition to carbon and hydrogen. Preference is given to the preparation of polymers of carbon monoxide with one or more olefinically unsaturated hydrocarbons. Examples of suitable hydrocarbon monomers are ethylene and other α-olefins such as propylene, butene-1, hexene-1 and octene-1. The catalyst compositions of the invention are especially suitable for use in the preparation of copolymers of carbon monoxide with ethylene and for the preparation of terpolymers of carbon monoxide with ethylene and with another olefinically unsaturated hydrocarbon such as propylene. The polymerization is preferably carried out at a temperature of 30-130 eC and a pressure of 20-250 bar. The polymerization is usually carried out by contacting the monomers with a solution of the catalyst composition in a diluent in which the polymers are not or practically insoluble. If desired, the polymerization can also be carried out in the gas phase.

The invention is now illustrated by the following examples.

Example 1

Phenylphosphine was prepared as follows. To 100 ml of liquid ammonia contained in a mechanically stirred reaction vessel held at 35 -78 ° C were added sequentially. 8 * 770 µl of mmol sodium and 4 mmol of phenyldibenzylphosphine. To convert the formed phosphide into the corresponding phosphine, 16 mmol of ammonium chloride was added after 2 hours. Ammonia was removed and 50 ml of dichloromethane 5 were added to the residue. The mixture was filtered and the solvent was removed.

Analysis of the residue showed that the phenyldibenzylphosphine was 57% converted to phenylphosphine.

Example 2 Phenylphosphine was prepared as follows. To 100 ml of liquid ammonia present in a mechanically stirred reaction vessel maintained at -78 ° C were added successively 8 mmole sodium and 4 mmole phenyldibenzylphosphine. After 1 hour, 8 mmoles ammonium chloride and 9.1 mmoles sodium were added successively. To convert the formed phosphide into the corresponding phosphine, 17.1 mmol ammonium chloride was added after 1 hour. Ammonia was removed and 50 ml of dichloromethane were added to the residue. The mixture was filtered and the solvent was removed.

Analysis of the residue showed that the phenyldibenzyl phosphine had been quantitatively converted to phenylphosphine.

Example 3 4-Methoxyphenylphosphine was prepared essentially in the same manner as the phenylphosphine in Example 2, but with the following differences a) to the ammonia 4mmol 4-methoxyphenyldibenzylphosphine was added instead of phenyldibenzylphosphine, b) after 1½ hours were added sequentially 8mmol ammonium chloride and 13mmol sodium instead of 9.1mmol, 30 and c) after 2 hours, 13mmol ammonium chloride was added instead of 17.1mmol after 1 hour.

Analysis of the residue showed that the 4-methoxyphenyldibenzylphosphine was 77% converted to 4-methoxyphenylphosphine.

, 6800770 - 12 -

Example 4 2,6-dimethoxyphenylphosphine was prepared essentially in the same manner as the phenylphosphine in example 1, but with the following differences 5 a) to the ammonia, 12 mmol sodium was added successively instead of 16 mmol and 4 mmol tri (2.6 dimethoxy-phenyl) phosphine hydrochloride instead of phenyldibenzylphosphine, and b) after 4 hours, 12 mmole ammonium chloride was added instead of 16 mmole after 2 hours.

Analysis of the residue showed that the tri (2,6-dimethoxyphenyl) phosphine hydrochloride was 40% converted to 2,6-dimethoxyphenylphosphine.

Example 5 2,6-dimethoxyphenylphosphine was prepared essentially in the same manner as the phenylphosphine in example 1, but with the following differences a) to the ammonia were added successively 20mmol sodium instead of 16mmol and 4mmol tri (2, 6-dimethoxy-phenyl) phosphine hydrochloride instead of phenyldibenzylphosphine, and b) after 4 hours, 20 mmole ammonium chloride was added instead of 16 mmole after 2 hours.

Analysis of the residue showed that the tri (2,6-dimethoxyphenyl) phosphine hydrochloride was 65% converted to 2,6-dimethoxyphenylphosphine.

Example 6 2.6-dimethoxyphenylphosphine was prepared essentially in the same manner as the phenylphosphine in example 1, but with the following differences a) to the ammonia, 32mmol sodium was added successively instead of 16mmol and 4mmol tri (2.6- dimethoxy-phenyl) phosphine hydrochloride instead of phenyldibenzylphosphine, and b) after 4 hours, 32mmol ammonium chloride was added instead of 16mmol after 2h.

, 880 077 0 - 13 -

Analysis of the residue showed that the tri (2,6-dimethoxyphenyl) phosphine hydrochloride was 81% converted to 2,6-dimethoxyphenylphosphine.

Example 7 5 2,6-dimethoxyphenylphosphine was prepared essentially in the same manner as the phenylphosphine in Example 2, but with the following differences a) to the ammonia were added successively 20mmol sodium instead of 8mmol and 4mmol tri (2, 6-dimethoxy-phenyl) phosphine hydrochloride instead of phenyldibenzylphosphine, b) after 1 hour, 19 mmol ammonium chloride and 3 mmol sodium were added in succession respectively.

8 mmol and 9.1 mmol, and 15 c) after 1 hour, 3 mmol ammonium chloride was added instead of 17.1 mmol after 1 hour.

Analysis of the residue showed that the tri (2,6-dimethoxyphenyl) phosphine hydrochloride had been quantitatively converted to 2,6-dimethoxyphenylphosphine.

Example 8 2.6-dimethoxyphenylphosphine was prepared essentially in the same manner as the phenylphosphine in example 1, but with the following differences a) to the ammonia, 8 mmol of sodium was sequentially added instead of 16 mmol and 4 mmol of di (2.6 dimethoxyphenyl) phosphine in place of phenyldibenzylphosphine, and b) after 1 hour, 8mmol ammonium chloride was added instead of 16mmol after 2h.

Analysis of the residue showed that the di (2.6-30 dimethoxyphenyl) phosphine was 84% converted to 2,6-dimethoxyphenylphosphine.

Example 9 2-Methoxyphenylphosphine was prepared essentially in the same manner as the phenylphosphine in Example 1, but with the following differences 8800770 - 14 - a) to the ammonia, 20mmol sodium was added sequentially instead of 16mmol tri and 4mmol tri ( 2-methoxy-phenyl) phosphine instead of phenyldibenzylphosphine, and b) after 2 hours, 20 mmol ammonium chloride was added instead of 16 mmol after 2 h.

Analysis of the residue showed that the tri (2-methoxy-phenyl) phosphine was 60% converted to 2-methoxyphenylphosphine. Example 10 2-Methoxyphenylphosphine was prepared essentially in the same manner as the phenylphosphine in Example 2, but with the following differences a) to the ammonia which was at -33 eC, 8 mmol sodium and 4 mmol tri were added successively. (2-methoxyphenyl) phosphine instead of 15-phenyldibenzylphosphine, b) after 1 hour at -33 ° C, 8 mmoles ammonium chloride and 12 mmoles sodium were added successively instead of 9.1 mmoles, and c) after 2 hours at -78 ° C C, 12mmol ammonium chloride 20 was added instead of 17.1mmol after 1 hour.

Analysis of the residue showed that the tri (2-methoxy-phenyl) phosphine was 88% converted to 2-methoxyphenylphosphine. Example 11 2-Methoxy-5-methylphenylphosphine was prepared essentially in the same manner as the phenylphosphine in Example 2, but with the following differences a) to the ammonia, 8 mmol of sodium and 4 mmol of tri (2-methoxy-5 were successively added -methylphenyl) phosphine instead of phenyldibenzylphosphine, 30 b) after 3 hours instead of after 1 hour 8 mmol ammonium chloride and 16 mmol sodium instead of 9.1 mmol were added successively, and c) after 3 hours 16 mmol ammonium chloride was added instead of 17.1 mmol after 1 hour.

.8800770 - 15 -

Analysis of the residue showed that the tri (2-methoxy-5-methylphenyl) phosphine was 87% converted to 2-methoxy-5-methylphenylphosphine.

Example 12 5 2,5-dimethoxyphenylphosphine was prepared essentially in the same manner as the phenylphosphine in example 1, but with the following differences a) to the ammonia, 16 mmol sodium and 4 mmol tri (2,5-dimethoxyphenyl) phosphine were added sequentially in place of phenyldibenzylphosphine, and b) the addition of ammonium chloride occurred after 4 hours instead of after 2 hours.

Analysis of the residue showed that the tri (2,5-dimethoxyphenyl) phosphine was 69% converted to 2,5-dimethoxy-15-phenylphosphine.

Example 13 2.5-dimethoxyphenylphosphine was prepared essentially in the same manner as the phenylphosphine in example 1, but with the following differences 20 a) to the ammonia, 40 mmol sodium was added successively instead of 16 mmol and 4 mmol tri (2.5- dimethoxy-phenyl) phosphine instead of phenyldibenzylphosphine, and b) after 2 hours, 40 mmole ammonium chloride was added instead of 16 mmole after 2 h.

Analysis of the residue showed that the tri (2,5-dimethoxyphenyl) phosphine was 80% converted to 2,5-dimethoxy-phenylphosphine.

Example 14 2.5-dimethoxyphenylphosphine was prepared essentially in the same manner as the phenylphosphine in example 2, but with the following differences a) to the ammonia were added successively 20mmol sodium instead of 8mmol and 4mmol tri (2.5- dimethoxy-phenyl) phosphine in place of phenyldibenzylphosphine, 8800770 - 16 - b) after 1 hour, 20 mmol of ammonium chloride and 20 mmol of sodium were added in succession, respectively.

8 mmole and 9.1 mmole, and c) after 1 hour, 20 mmole ammonium chloride was added instead of 17.1 mmole after 1 hour.

Analysis of the residue showed that the tri (2,5-dimethoxyphenyl) phosphine had been quantitatively converted to 2,5-dimethoxyphenylphosphine.

Example 15 2-Dimethylaminophenylphosphine was prepared essentially in the same manner as the phenylphosphine in Example 2, but with the following differences a) to the ammonia which was at -60 ° C, 8 mmol sodium and 15 4 were successively added. mmol tri (2-dimethylaminophenyl) phosphine instead of phenyldibenzylphosphine, b) after 1 hour at -60 eC, 8 mmol ammonium chloride and 12 mmol sodium instead of 9.1 mmol, and 20 c) were added after 1 h at -78 ° C, 12 mmol of ammonium chloride was added instead of 17.1 mmol.

Analysis of the residue showed that the tri (2-dimethyl-aminophenyl) phosphine was 62% converted to 2-dimethylaminophenylphosphine.

Example 16 2-Dimethylaminophenylphosphine was prepared essentially in the same way as the phenylphosphine in Example 1, but with the following differences

a) to the ammonia which is at a temperature of -33 ° C

30 mmoles of sodium instead of 16 mmoles and 4 mmoles of di (2-dimethylaminophenyl) -phosphine instead of phenyldibenzylphosphine were added successively, and b) after 1 hour at -33 eC, 8 mmoles ammonium chloride was added instead of 16 mmoles.

8800770 - 17 -

Analysis of the residue showed that the di (2-dimethyl-aminophenyl) phosphine was 85% converted to 2-dimethylamino-phenylphosphine.

Example 17 5 2-dimethylaminomethylphenylphosphine was prepared essentially in the same manner as the phenylphosphine in Example 2, but with the following differences a) to the ammonia which was at -60 eC, 16 mmol sodium 10 were added successively instead of 8 mmole and 4 mmole tri (2-dimethylaminomethylphenyl) phosphine instead of phenyldibenzylphosphine, b) after 1 hour at -60 eC, 16 mmole ammonium chloride and 16 mmole sodium were added successively. 8 mmol and 9.1 mmol, and 15 c) after 1 hour at -78 eC, 16 mmol ammonium chloride was added instead of 17.1 mmol.

Analysis of the residue showed that the tri (2-dimethyl-aminomethylphenyl) phosphine was 29% converted to 2-dimethyl-aminomethylphenylphosphine.

20 Example 18

Example 1 was essentially repeated, however with the following differences a) in the reaction vessel, at -78 ° C, a mixture of 50 ml of liquid ammonia and 25 ml of tetrahydrofuran was added, b) to this mixture were successively added 16 mmoles of sodium and 3, 2 mmol diphenylphosphine in place of phenyldibenzylphosphine, and c) the cooling was turned off and after stirring for 3 hours the reaction mixture was again cooled to -78 eC, after which 16 mmol of ammonium chloride was added.

Analysis of the residue showed that no conversion of diphenylphosphine to phenylphosphine had taken place.

Example 19

To 20 ml of tetrahydrofuran, present in a stirred reaction vessel, was added successively 2.3 mmoles of tri (2-dimethyl-8800770-18-aminophenyl) phosphine and 8 mmoles of lithium. After stirring for 17 hours, 25 ml of water and 25 ml of diethyl ether were added to the reaction mixture. The organic layer was separated and dried. After removal of the solvent, the residue 5 was analyzed. It was found that no conversion of the tri (2-dimethylaminophenyl) phosphine to 2-dimethylaminophenylphosphine had occurred, but that the tri (2-dimethylaminophenyl) phosphine had been quantitatively converted to di (2-dimethylaminophenyl) phosphine.

10 Example 20

Example 19 was essentially repeated, except that tri (3-dimethylaminophenyl) phosphine was used instead of tri (2-dimethylaminophenyl) phosphine.

Analysis of the residue showed that no conversion of 15 tri (3-dimethylaminophenyl) phosphine to 3-dimethylaminophenyl phosphine had occurred, but that the tri (3-dimethylamino-phenyl) phosphine had been converted to di (3-dimethylamino-) phenyl) phosphine.

Example 21 20 1,3-bis (2,6-dimethoxyphenylphosphino) propane was prepared as follows. To a solution of 0.3 mole of 2,6-dimethoxyphenylphosphine in 400 ml of diethyl ether contained in a stirred reaction vessel, 190 ml of a 1.6 molar solution of n-butyl lithium in n-hexane was added over 20 minutes at room temperature. . After 30 minutes, the reaction mixture was cooled to -78 ° C and a solution of 0.15 mole 1,3-dibromopropane in 150 ml diethyl ether was added over 20 minutes. After 20 minutes, the reaction mixture was warmed, refluxed for 1 hour and cooled to room temperature. 100 ml of water and 300 ml of ethyl acetate were added to the reaction mixture. The organic layer was separated, washed and dried. After removal of the solvent, the residue was analyzed. It was found that the 2,6-dimethoxyphenylphosphine had been 80% converted to 1,3-bis (2,6-dimethoxyphenylphosphino) propane.

.8800770 - 19 -

Example 22 2-methoxyethyl, 2,6-dimethoxyphenylphosphine was prepared as follows.

To a solution of 11.6 g of 2,6-dimethoxyphenylphosphine in 100 ml of diethyl ether contained in a stirred reaction vessel, 51 ml of a 1.6 molar solution of n-butyl lithium in n-hexane were added over 10 minutes at room temperature. After 30 minutes, the reaction mixture was cooled to -78 ° C and a solution of 11.1 g of 1-bromo, 2-methoxyethane in 100 ml of diethyl ether was added over 10 minutes. After the reaction mixture had warmed to room temperature, 100 ml of water added The organic layer was separated, washed and dried After removal of the solvent, the residue was analyzed It was found that 63-dimethoxyphenyl-15-phosphine had been converted to 2-methoxyethyl, 2,6 dimethoxyphenylphosphine.

Example 23 di (2-methoxyethyl), 2,6-dimethoxyphenylphosphine was prepared as follows. To a solution of 2.5 g of 2-methoxyethyl, 2,6-di-20-methoxyphenylphosphine in 25 ml of ether contained in a stirred reaction vessel, 6.9 ml of a 1.6 molar solution of n- butyl lithium in n-hexane. After 15 minutes, the reaction mixture was cooled to -78 ° C and a solution of 1.53 g of 25 1-bromo, 2-methoxyethane in 50 ml of diethyl ether was added over 5 minutes. The reaction mixture was warmed, refluxed for 30 minutes and cooled to room temperature. After removal of the solvent, the residue was analyzed. It was found that the 2-methoxyethyl, 2,6-dimethoxyphenylphosphine was 95% converted to di (2-methoxyethyl), 2,6-dimethoxyphenylphosphine. Example 24 dibutyl, 2,6-dimethoxyphenylphosphine hydrochloride was prepared as follows. To a solution of 63 mmol of 2,6-dimethoxyphenylphosphine in 125 ml of tetrahydrofuran in a stirred reaction vessel, 40 ml of .8800770 - 20 - a 1.6 molar solution of n-butyl lithium in n-hexane was added in room temperature over 5 minutes. After 10 minutes, the reaction mixture was cooled to -50 ° C and a solution of 8.6 g of butyl bromide in 50 ml of tetrahydrofuran was added over 5 minutes. After warming up to room temperature, 40 ml of a 1.6 molar solution of n-butyl lithium in n-hexane was again successively added over 5 minutes, cooled after 10 minutes to -50 ° C and a solution of 8 ml was added in 5 minutes. 6 g of butyl bromide in 50 ml of tetrahydrofuran are added. After warming to room temperature, 200 ml of a 10 percent aqueous HCl solution was added to the reaction mixture. The water layer was separated, evaporated to 100 ml and extracted twice with 150 ml of dichloromethane each time. After combining the dichloromethane extracts and removing the solvent, 20.2 g of dibutyl, 2,6-dimethoxyphenylphosphine hydrochloride was obtained as a colorless oil.

Example 25

A carbon monoxide / ethylene copolymer was prepared as follows. 210 ml of methanol were placed in a mechanically stirred autoclave with a capacity of 300 ml. After the contents of the autoclave were brought to 90 eC, a 1: 1 carbon monoxide / ethylene mixture was pressed in until a pressure of 55 bar was reached. A catalyst solution consisting of 18 ml of methanol, 6 ml of toluene, 0.094 mmol of palladium acetate, 0.58 mmol of trifluoroacetic acid, and 0.113 mmol of 1,3-bis (2,6-dimethoxyphenylphosphino) propane was then introduced into the autoclave.

During the polymerization, the pressure was maintained at 55 bar by pressing a 1: 1 carbon monoxide / ethylene mixture. After 17.2 hours, the polymerization was terminated by cooling the reaction mixture to room temperature and releasing the pressure. The copolymer was filtered off, washed with methanol and dried at 50 ° C.

.8800770 - 21 - t

4.8 g of copolymer was obtained. The polymerization rate was 30 g copolymer / g palladium. hour.

The 2,6-dimethoxyphenylphosphine used as starting material in Examples 21-24 was obtained by a preparation method as indicated in Example 7. The 1,3-bis (dimethoxyphenylphosphino) propane which was used in the catalyst composition of Example 25 was obtained using a preparation method as indicated in Example 21.

Of Examples 1-25, Examples 1-17 and 21-25 are according to the invention. Examples 18-20 are outside the scope of the invention and are included in the patent application for comparison. In Example 18, an unsuitable starting phosphine was used. Although an appropriate starting phosphine was used in Example 19, the desired cleavage reaction was attempted in tetrahydrofuran rather than liquid ammonia. In Example 20, an unsuitable starting phosphine was used and, in addition, an attempt was made to carry out the desired cleavage reaction in tetrahydrofuran instead of liquid ammonia. Examples 1 and 2 concerned the one- and two-step preparation of phenylphosphine. In Examples 3-17, using different amounts of sodium and using both one- and two-step preparations, the following new compounds were obtained: 4-methoxyphenylphosphine, 2,6-dimethoxyphenylphosphine, 2-methoxyphenylphosphine, 2-methoxy-5- methylphosphine, 2,5-dimethoxyphenylphosphine, 2-dimethylaminophenylphosphine, and 2-dimethylaminomethylphenylphosphine.

In Example 21, 2,6-dimethoxyphenylphosphine prepared according to the invention was converted into 1,3-bis (2,6-dimethoxyphenyl-8800770-22-phosphino) propane. In Examples 22-24, starting from 2,6-dimethoxyphenylphosphine prepared according to the invention, the following new compounds were obtained: 2-methoxyethyl, 2,6-dimethoxyphenylphosphine, 5 di (2-methoxyethyl), 2,6-dimethoxyphenylphosphine, and dibutyl 2,6-dimethoxyphenylphosphine.

Finally, Example 25 concerns the preparation of linear alternating carbon monoxide and ethylene copolymers using a catalyst composition according to the invention.

. β 8 0 0 7 7 0

Claims (28)

1. Process for the preparation of phosphides, characterized in that phosphides of the general formula RgPMY are prepared by reacting in liquid ammonia an alkali metal M with a phosphine of the general formula RyRgRgP, in which general formulas Y is a hydrogen atom or a alkali metal M represents, Rg is an optionally polar substituted aryl group and Ry and Rg represent equal or different groups selected from a) aryl groups containing one or more polar substituents which only occupy the ortho and meta positions relative to the phosphorus atom and of which at least at least one occurs ortho-to phosphorus, b) optionally polar substituted hydrocarbyl groups containing a> CC <group attached to the phosphorus via only one aliphatic carbon atom, and c) hydrogen, with the proviso that Ry and Rg are not simultaneously hydrogen. 2. Process according to claim 1, characterized in that of the groups Ry and Rg at least one is a phenyl group which contains one or two alkoxy groups, such as methoxy groups, ortho-to the phosphorus atom. Process according to claim 1, characterized in that of the groups Ry and Rg at least one is a benzyl group or allyl group. 4. Method according to one or more of claims 1-3, characterized in that of the groups Ry to Rg, at least two are connected to one another. A method according to claim 4, characterized in that the groups Ry to Rg are the same. Process according to one or more of Claims 1 to 5, characterized in that the alkali metal M used is sodium. .6 * 00 770 - 24 - Process according to one or more of Claims 1 to 6, characterized in that more than two equivalents of alkali metal are used per hydrocarbyl group to be cleaved. 8. Process according to one or more of claims 1-7, characterized in that the addition of the amount of the alkali metal to be used is carried out in two or more steps, wherein prior to each subsequent addition the previously formed phosphide is first reacted with a proton donor is converted into the corresponding phosphine. Process according to one or more of Claims 1 to 8, characterized in that 1-125 ml of liquid ammonia are used per mole of alkali metal. Process according to claim 9, characterized in that 10-40 ml of liquid ammonia are used per mole of alkali metal. 15 Process according to one or more of claims 1 to 10, characterized in that the reaction is carried out at a temperature of -100 to -35 ° C. 12. Process according to claim 11, characterized in that the reaction is carried out at a temperature of -80 to -35 ° C. A process for the preparation of phosphides according to claim 1, substantially as described above and in particular with reference to examples 1-17. Phosphides prepared according to claim 1. 15. New phosphides of the general formula RgPMY, wherein R9 represents a polar substituted aryl group, M is an alkali metal and Y represents a hydrogen atom or an alkali metal M, as well as new phosphines which can be obtained from these phosphides by reacting them with a 30 proton donor. 16. As new phosphides according to claim 15, sodium (2-methoxyphenyl) phosphide, sodium (2,6-dimethoxyphenyl) phosphide, sodium (2-methoxy-5-methylphenyl) phosphide, & 80077 - 25 - sodium (2,5- dimethoxyphenyl) phosphide, sodium (2-dimethylaminophenyl) phosphide, and sodium (2-dimethylaminomethylphenyl) phosphide. 17. As novel phosphines according to claim 15, the phosphines which can be obtained from the phosphides according to claim 16 by reacting them with a proton donor. 18. Process for the preparation of diphosphines of the general formula RgHP-R-PRgH, characterized in that a monophosphide of the general formula RgPMY prepared according to claim 1 is first converted by reaction with a proton donor to the corresponding monophosphine R9PH2, which this monophosphine is then converted by reaction with an alkyl lithium compound to the corresponding lithium phosphide RgPLiH and the latter compound is reacted with a dihalogen compound XRX wherein X represents a halogen atom and R is a divalent organic bridging group containing at least two carbon atoms in the bridge contains. 19. Process for the preparation of diphosphines of the general formula RgR10 -k-PRgR10, characterized in that a diphosphine of the general formula RgHP-R-PRgH prepared according to claim 18 is converted by reaction with an alkyl lithium compound into the corresponding lithium diphosphide RgLiP-R-PRgLi and the latter compound is reacted with a monohalogen compound XR ^ q wherein X represents a halogen atom and R ^ is an optionally polar substituted aliphatic hydrocarbyl group. 20. Process for the preparation of diphosphines of the general formula RgR ^ QP-R-PRgR ^ Q, characterized in that a lithium monophosphide of the general formula RgPLiH prepared as described in claim 18 is first reacted with a monohalogen compound XR ^ q * where * -n X represents a halogen atom and R ^ q is an optionally polar substituted hydrocarbyl group, it is converted to a monophosphine RgR ^ gPH. That this monophosphine is subsequently converted by reaction with a .8800770 V-26-alkyl lithium compound into the corresponding lithium phosphide R-gR-gnd- and that the latter compound is reacted with a dihalogen compound XRX in which X represents a halogen atom and R represents a divalent 5 is an organic bridge group which contains at least two carbon atoms in the bridge. 21. Novel phosphines of the general formula RgR ^ gPH and R9R10RnP wherein Rg represents a polar substituted aryl group and R ^ q and Rn are the same or different optionally polar substituted aliphatic hydrocarbyl groups. The novel phosphines of claim 21, 2-methoxyethyl, 2,6-dimethoxyphenylphosphine, di (2-methoxyethyl), 2,6-dimethoxyphenylphosphine, and dibutyl, 2,6-dimethoxyphenylphosphine. Catalyst compositions, characterized in that they are based on a) a palladium compound, b). an anion of an acid with a pKa less than 6, and c) a diphosphine prepared according to any one of claims 18-20. A process for the preparation of polymers, characterized in that a mixture of carbon monoxide with one or more olefinically unsaturated compounds is polymerized using a catalyst composition according to claim 23. 25. Process according to claim 24, characterized in that a catalyst composition is used which is based on a) a palladium salt of a carboxylic acid such as palladium acetate, b) an anion of a sulfonic acid such as para-toluenesulfonic acid or of a carboxylic acid such as trifluoroacetic acid, c ) a diphosphine in which the divalent bridge group R is a - (CH 2) 3 - group, and d) optionally a promoter such as a 1,4-quinone. 26. Process according to claim 24 or 25, characterized in that the olefinically unsaturated compounds used are hydrocarbons such as ethylene or a mixture of ethylene with another olefinically unsaturated hydrocarbon such as propylene. Polymers prepared according to a method as described in one or more of claims 24-26. 28. Molded articles which consist at least in part of the polymers according to claim 27, 8800770