CS208745B2 - Method of making the complex compounds - Google Patents

Description

(54) A method for producing complex compounds

The invention relates to a process for the preparation of complex compounds of the formula I

(I) in which

R, R *, R ** _f R *** and R 4 ^V , identical or different, denote methyl or phenyl radicals, x denotes 1 or 2 and δ denotes 0 or 1, by reaction of a compound of formula II

Pd (

in which

R *, R **, R *** and R ^ ^V are as defined above, with carbon monoxide in the presence of an alcohol of formula III

(II)

R-OH in which

R is as defined above. ,

The reaction is carried out at temperatures ranging from 0 to 40 ° C and preferably in the presence of methane.

Said complex compounds are valuable catalysts for the carboinlation reactions of olefins in an alcoholic medium. The products of these reactions are esters of succinic acid or substituted succinic acids, or .beta.-alkoxycarbonyl ethers, optionally also esters of acrylic acid or substituted acrylic acids. The palladium complex compounds according to the invention can also be used as catalysts for the carbonylation reactions of alcohols to di-alkylcarbonyl and dialkyloxylates.

In more detail, the compounds of the present invention are fastened to the production of maltic acid derivatives.

Násce ^^! ' The examples of the process according to the invention serve to illustrate the invention without the nature of the invention.

Example 1

O li

0.580 g of the compound of the formula Pdd-O-C-CH 3 CP phenyl 3) was stirred in 10 ml of methanol and stirred for 4 hours under pressure of carbon monoxide at 20 ° C.

The solution was filtered and precipitated with ether to give a white, air-stable solid, which was then recrystallized from a mixture of dichloromethane and pentane.

0.278 g (48% yield) of the compound with a decomposition temperature of 129-136 ° C was obtained. The compound showed, in the infrared spectroscopy, the following characteristics of the bands:

⁶⁵⁵ cm '1 ⁰ 7 ⁰ cm to ⁶⁰⁵ cm metoxykartonyl "' ¹ and ²⁵ cm 3 for ¹ monoden karrboxy ^ rs ^ ski Vou yne ^p ·

At NMR spectroscopy ZH (CIS11 standard, HMSS standard), the compound exhibited two muULplets, at 7.6 S and 7.3 S, cheakateistic for the trans-configuration of triphenylphosphines in the square plane and two singlets at the 2.42 S position and - 0.87 S, characteristic of aetoaxyl and - methyl protons.

The signal integration ratio corresponds to formula II.

These values are not applicable to the following formula:

Analysis: Calculated: C, 64.1; H, 4.9; O, 8.5; Found: 63.7 ° C, H 4.8%, 8.5% O.

Example 2

O

II

To 0.840 g of the compound of formula Pd (-CO-CH ₃ ) (C1) (P fen), dissolved in 20 ml of dichloromethane, was added 0.190 g of silver acetate at room temperature, followed by stirring under nitrogen for 30 minutes. The silver chloride formed was filtered off.

The solution was further concentrated in vacuo and pentane was added to the reaction mixture. The precipitated compound exhibited the same properties as the compound prepared by the procedure described in the previous Example 1.

Yield 0.72 g (83% of theory).

PPikl a d 3

II

To 0.225 g of the compound of formula Pd (-C-OHH ₃ ) (I) (P phenyl) in 15 ml of dichloromethane was added 0.046 g of silver acetate, and the reaction mixture was then stirred for 30 minutes at room temperature. removed by filtration and the solution concentrated by evaporation. The reaction mixture was precipitated with pentane type II (II).

Yield: 0.170 g (83% of theory).

Example 4

II

0.65 g of the compound of formula R8 (-1-O-N) (R) (R) was stirred in 15 ml of methanol under a positive pressure of carbon monoxide at 0 DEG C. 0.200 g of sodium methoxide were then added to the reaction mixture. After four hours, the solid, melted on the filter and the tetrotreformed at low temperature from a mixture of dichloromethane and pentane, exhibited the following property:

Melting point: 118 DEG-134 DEG

1hartrttetstické infaačervené bands: 1630 cm and 1010 CMJ chaam eeistické ^ ro ^{p e} Me oxycarbonyl group. ^The NMR- ^Z H analysis (in 1DC1-, HMDS standard) showed the muutiplets at 7.6 S and 7.3 S, respectively, aromatic protons, and single at 2.44 S (mmtosyl). protons) with an integration ratio.

to the offspring (III).

The yield was 0.65 g (96% of theory). ,

Elemeeneal analysis corresponded to the following empirical sample derived from formula III:

140H ₃ 6 ^o 4P2P

PPikl a d 5

II

0.570 g of the compound of formula (Pdd-10-CСн) (R) was stirred in 15 m of methanol under carbon monoxide pressure and at 0 ° C in the presence of excess sodium methoxide (0.100 g). for 4 hours at 0 [deg.] C. The solid obtained was collected by filtration, eluting with a mixture of dichloromethane and pentane and identifying as a compound of formula (III).

Yield 0.49 g (88% of theory).

Example '6

1.00 g of the compound of formula PdCl 2 (P phenyl) was stirred in 30 ml of methanol under carbon monoxide pressure at 0 ° C in an excess of sodium methoxide (0.30 g), and the mixture was stirred for 6 hours. on a filter and recrystallized from a mixture of dichloromethane and pentane whose composition corresponds to a compound of formula (III).

Yield 0.78 g (73% of theory).

Claims (2)

SUBJECT OF THE INVENTION 1. A process for producing kompleerních compounds of formula I (I, ^R jj Pd (-C-OR) (-O-C-R *) (P <^ -R ') 2 x ^ ^ RV (I) in which R, R *, R **, R ***, R ^IV , the same or different, denote methyl or phenyl radicals, x denotes 1 or 2 and y denotes 0 or. 1, a characterized in that a compound of formula (IIf) is reacted Pd (-OCR *) ₂ (P ——- R ') ₂ \ _R IV (II) in which ^R *, R **, R *** and ^rIV are as defined above ^, with carbon monoxide in the alcohol present of formula III R-OH in which R. as defined above, wherein the reaction is carried out at a temperature in the range of 0 to 40 ° C. 2. The process according to claim 1, wherein the reaction is carried out in the presence of methane.