DE2249389A1 - PROCESS FOR THE CATALYTIC PRODUCTION OF LINEAR MONOUNESAIDATED DICARBONIC ACID DERIVATIVES - Google Patents

Description

Process for the catalytic production of linear monounsaturated Dicarboxylic Acid Derivatives The invention relates to a process for catalytic production linear monounsaturated dicarboxylic acid derivatives of the general formula ROC - CH2 - CH2 - CH = CH - COR, in which R is a lower alkoxy radical, an aryl radical, means an acyloxy radical or an optionally substituted amino radical, or the corresponding # 3 derivatives.

The linear monounsaturated dicarboxylic acid derivatives are important Intermediates for the manufacture of polymers.

It is known that methyl acrylate by heating with palladium (II) or Rhodium (III) compounds are dimerized to form mixtures of # 2 and # 3 dihydromuoanoic acid esters can be. The disadvantage here is that because of the relatively high reaction temperatures Working under pressure is arforderiloh and that the yields are below 70%.

It is also known that acrylanide by rhodium (III) chloride in boiling alcoholic solution can be dimerized. This reaction takes place very slowly and with yields of around 25%. It is also known that acrylonitrile and acrylic acid esters with the aid of ruthenium compounds under hydrogen pressure higher temperatures lasa @ n dimerize to dihydromuconic acid derivatives, as nee products This always results in saturated di- and non-carboxylic acid derivatives, especially propionitrile respectively.

Propionic acid ester.

It is also known that certain basic compounds, especially tertiary phosphines, phosphites and bicyclic tertiary amines, the dimersation of Aoryl acid derivatives are able to catalyze. This is preferably the effect of catalysts the formation of branched dimers of the type of α-methylene glutars @@ rsderivate.

The invention is based on the task of presenting the other disadvantages mentioned method to ve @.

and a catalyst system with high activity selectivity for to develop the production of linear, monoun, saturated dicarboxylic acid derivatives.

This object is achieved by a method for catalytic production linear monounsaturated dicarboxylic acid derivatives of the general formula ROC - CH2 - CH2 - CH = CH - COR, in which R is a lower alkoxy radical, an aryloxy radical, a Aeyloxy radical or an optionally substituted ami @ radical, or the corresponding # 3 derivatives according to the invention solved by unsaturated Carboxylic acid derivatives of the general formula CH2 = CH - COR, in which R is the above Has meaning in the presence of soluble palladium (II) complexes in combination with quinones at temperatures from 0 ° C to the boiling point of the substrate used dimerized under normal pressure.

The following can be used as soluble palladium (II) complexes, for example: Bis (benzonitrile) palladium (II) chloride, bis (mesitonitrile) palladium (II) chloride, Bis (p-dimethylaminobenzonitrile) palladium (II) chloride and others substituted Nitrile complexes of palladium (II) chloride; Palladium (II) chloride olefin complexes such as bis-ethylene palladium (II) chloride, bis-atyrene palladium (II) chloride, # -allyl palladium (II) chloride and tetrahalopalladate (II) complexes such as sodium tetrachloropalladate (II).

As cocatalysts p- and @ -quinones can be used, for example p-Benzoquinone, p-Naphthochione and their substitution products, derivatives of o-Benzoquinone and o-naphthoohinons.

The molar ratio of carboxylic acid derivative to palladium (II) complex lies in the ranges from 1000: 1 to 10: 1 and that ven Palladtum (II) complex to Chinen within the limits of 1: 1 to 1: 10.

The application of solution @@ itteln is for liquid carboxylic acid derivatives Usually not necessary, it can be used with black soluble catalysts be beneficial. In this case, numerous very polar solvents are suitable, preferably Ac @ ton or chloroform.

The combination of the cocatalysts with the palladium (II) complexes mentioned leads to a significant improvement in the activity and selectivity in an increase in the yields of lenticular sera monounsaturated dicarbonaäu @ derivatives until it is over 90% expressed.

The invention is to be explained using @iaiger example.

Example 1 A mixture of 383.5 mg (1 mäol) bis (banzonitrile) palladium (II) chloride, 1081 mg (10 mmol) of p-banzoquinone and 8.83 ml (100 mmol) of methyl arylaate with stirring slowly to the boil and kept for 15 hours in the Siaden. The gas chromatographic Analysis of the reaction product reveals an overall yield of dimeric esters of 91.6%, of which 28.1% # 2 and 64.0% # 3 dihydromucenoic acid esters.

After a reaction time of 7 hours, the total expansion of diacid @@ starn b @ rsits at 62.3%.

Without the addition of p-benzoquinone, the yields of dimers can be increased Estarn not 40%, with the molar ratio of # 2-: # 3-Dihydromu @@ nsäuredimethylastar about 1: 1.

Analogously to Example 1, those in Table 1 (Examples 2 to 7) are summarized Acrylic acid @@ ster dimerisiart.

Table 1 Examples 2 to 7 The following are always added: 1 mmol of bis (bensonitrile) palladium (II) chloride, 10 mmol p-bemoquinone, 100 mmol aoryl acid @ ester, reaction time: 10 hours on the example CH2 = CH-COOR Yield of dimaric esters (%) @r. of which a total of # 2- # 3- # Dihydromuoonsäureseate @ 2 C2H3- 86.3 28.0 64.5 3 n-C3H7- 71.5 28.5 71.5 4 iso-C3H7- 79.6 27.5 53.5 5 n-C4H9- 81.3 26.5 75.0 6 iso-C4H9- 82.0 25.7 74.0 7 C6H5- 70.3 27.0 12 @ Repiel 8 A mixture of 383.5 mg (i mmol) bis (benzonitrile) palledium (II) chloride, 763.7 mg (7 mmol) of p-benzoquinone and 3.83 ml (100 mmol) of aoxylic acid methyl ester Shaken at 20 ° C for about 100 hours.

Overall yield of dimeric estarn: 91%, of which 33.0% # 2 and 67.0 % # 3-dihydromuoic acid ester.

Example 9 383.5 mg (1 mmol) of bis (benzonitrile) palladium (II) chloride are dissolved in 5 ml of aoetone and heated to 50 ° C. 8.83 ml (100 mmol) methyl aorylate, in which 540.5 mg (5 mmol) of p-benzoohinone are dissolved, Langaam added and kept for several hours at the boiling temperature of the acetone.

After 10 hours of reaction time, dimeric esters are obtained in one overall configuration of 86%, of which 33.0% are # 2 and 67.0%, # 3 dihydromuoic acid esters.

After 15 hours the total expansion of dimeric esters is 92.7 %, thereof 33.0% # 2 and 67.0% # 3 dihydromuconic acid ester.

When using chloroform instead of Aoston as a solvent the results are the same.

Example 10 467.3 mg (1 mmol) of bis (mesitonitrile) palladium (II) chleride are dissolved in 5 ml of asetone and warmed to 50 ° C. With stirring, 8.83 ml (100 mmol) methyl aorylate, in which 540.5 mg (5 mmol) of p-benzoquinone are dissolved, Slowly give hi @ sug and keep it simmering for 10 hours.

Total expansion of dimaric esters: 30.5%, of which 27.1% # 2 and 72.9 % # 3-Dihydr @@@@@ m @@@ nr @@ ster.

If the wall is smooth, bis (p-dimethylaminobensonitrile) palladium (II) chloride instead of bis (m @ sitonitrile) palladium (II) @ chloride, the results are the same.

Example 11 365.8 mg (1 mmol) of # allyl palladium (II) chloride are produced dissolved in 5 ml of Ac @ ton. With stirring, 8.83 ml (100 mmol) of methyl aorylaate, in to which 540.5 mg (5 mmol) of p-bezechinine are galöst, slowly given hi @@@@ and 10 hours kept simmering.

Official yield of dimeric Setera: 35.6%, thereof 24.5% # 2- and 68.3 % # 3-Dihydr @@ uo @@ aänreester.

Example 12 383.5 mg (1 mmol) of bis (b @ nsonitrile) palladium (II) chloride was dissolved in 5 ml of Ao @ ton. In the cold, with stirring, 8.83 ml (100 mmol) Methyl aorylate, in which 712.5 mg (5 mmol) of monochloropbenzoquinone are dissolved, go in slowly and hold for II hours at the boiling temperature of acetone.

Overall yield of dimeric esters: 89.5%, of which 28.5% # 2 and 71.5 % # 3-Dihydromuoo @ acid ester Beisplel 13 408.2 mg (1 mmol) of bis-ethylene palladium (II) chloride are dissolved in 10 ml chlorine form. 8.83 ml (100 mmol) of Aoryla @ ur @ mathylastar, 540.5 mg (5 mmol) of p-H @ msochi @ an are dissolved in then, slowly add and 10 Kept in the boil for hours.

Overall yield of the diseram ester: 46.8%, of which 29.2% # 2 and 63.4 % # 3 dihydromucosic acid ester.

Claims (1)

Claim: Process for the @atalytischan decomposition of linear mo @ unsaturated Dioarboxylic acid derivatives of the general formula ROC - CH2 - CH2 - CH = CH - COR, in the R is a different alkoxy radical, an aryloxy radical, an acyloxy radical or a Gegenbananfalls substituted on Ami @ rest means, or the corresponding # 3 derivatives, gekannzeichnst that one unsaturated carboxylic acid @ derivatives of the general Formula CH2 = CH - COR, in which R has the meaning given above, in the presence of Löalichen palladium (II) complexes in combination with quinone @@ at temperatures dimerized from 0 ° C to the boiling point of the substrate used under normal pressure.