DE19924159A1 - Preparation of alkene from acetylene and amino, hydroxyl or carboxyl compounds in the presence of cesium fluoride and alkali hydroxide catalyst - Google Patents

Abstract

Preparation of alkene compounds from acetylene and amino, hydroxyl or carboxyl compounds using a mixed CsF/alkali hydroxide catalyst in the absence of DMSO.

Description

The invention relates to processes for the preparation of alkene compounds by Implementation of compounds containing amine, hydroxyl, carboxyl and / or nitrile Have groups with compounds containing a C-C triple bond, in the presence of basic catalysts.

The base-catalyzed formation of new carbon or carbon Carbon-heteroatom bonds are an important synthetic tool. Additions are particularly attractive in this category of implementations Carbon-carbon multiple bonds without the formation of Side products can be carried out and are therefore nuclear economical. For example, the metal-catalyzed addition of alkynes to carbonyl Compounds for the preparation of propargyl alcohols from technical Importance. Implementation of these implementations using a stoichiometric amount of base such as organolithium or organomagnesium Compounds to form a metal acetylide intermediate have been around known for a long time.

W. Reppe, Liebigs Anm. Chem. 1955, 596, pages 1 to 3, the Carbonylation of acetylene with carbonyl compounds in the presence of Acetylidene of the heavy metals of the first subgroup of the periodic table Elements described in THF.

Pages 6 to 11 and 25 to 38 describe that ethynylation of ketones in aqueous media using alkali hydroxides, Alkaline earth metal hydroxides, alkali carbonates or tertiary amines as catalysts  can be carried out. Copper acetylide can also be used as a catalyst become. In the examples, the production of methyl butinol from acetone and acetylene in water with potassium hydroxide as a catalyst.

J.H. Babler et al., J. Org. Chem. 1996, 61, pages 416 to 417 describe the Alkoxide-catalyzed addition of terminal alkynes to ketones. The Reaction with tert-butoxide as a catalyst in DMSO as a solvent carried out.

M. Makosza, Tetrahedron Lett. 1966, pages 5489 to 5492, describes the Vinylation of phenylacetonitrile compounds in the presence of a system Sodium hydroxide, DMSO and triethylbenzylammonium chloride.

In B.A. Trofimov, Russion Journal of Organic Chemistry, vol. 31, no. 9, 1995, Pages 1233 to 1252 are different reactions with acetylene described. Among others, ethynylations are using the Superbase systems KOH / DMSO listed.

In B.F. Kukharev et al., Russian Journal of Organic Chemistry, vol. 29, no. 12, 1993, pages 2005 to 2012 is the nucleophilic addition of 1,2-aminoalkanols on phenylacetylenes. Besides other alkali metal hydroxide cesium hydroxide solvent-free or in DMSO as solvent be used. The alkenylation takes place on the hydroxyl group of the 1,2- Aminoalkanol.

Dimethyl sulfoxide (DMSO) is disadvantageous for technical processes since it is expensive and toxicologically unobjectionable and thermally unstable.

The object of the present invention is to provide improved and general process for the preparation of alkene compounds by reacting organic compounds, the amino, hydroxyl,  and / or nitrile groups, with compounds containing acetylenic groups (-C∼C-H) have.

The object is achieved by a process for the preparation of alkene compounds of the general formula (IV)

R ³ -HC = CR ² -R ⁴ (IV)

with the meaning
R ² , R ^{3 are} independently H, NH ₂ or C _1-20 hydrocarbon radical which is substituted one or more times by C _1-6 alkyl and / or halogen and / or are interrupted by non-adjacent heteroatoms and / or CC double bonds can contain
R ⁴ R ⁵ R ⁶ N-, R ⁵ R ⁶ C (Z) - or R ⁷ -O- with
R ⁵ , R ⁶ , R ⁷ independently as defined for R ³ with the exception of H,
Z CN, COOR with R = H or C _1-6 alkyl
by reacting compounds of the general formula (V)

R ⁴ -H (V)

with compounds of the general formula (III)

R ² -C∼CR ³ (III)

in the presence of a basic catalyst, being the basic catalyst CsF / alkali hydroxide is used and the reaction preferably in one Solvent based on N-methylpyrrolidone (NMP) is carried out.  

It has been found according to the invention that the reaction for a large number of Compounds with improved catalyst activity and yield carried out can be used if CsF / alkali hydroxide is used as the basic catalyst. The reaction can be solvent-free or in suitable solvents respectively. The reaction in a solvent is particularly preferred Base of N-methylpyrrolidone (NMP). The expression "based on" means that solvent mixtures can also be used, which essentially NMP included. For example, amounts of up to 20% by weight, preferably up to 10% by weight, in particular up to 5% by weight of others Solvents are tolerated. So that the solvent preferably a content of at least 80% by weight, particularly preferably at least 90 % By weight, in particular at least 95% by weight, of NMP. The rest of the rest the solvent is inert to the reactions. examples are DMSO and THF and mixtures thereof. Especially preferred is essentially or completely used NMP as a solvent.

The use of CsF / alkali hydroxide is also related to other solvents such as DMSO, THF or mixtures of THF and DMSO or possible without using solvents. Achieved particularly good results However, when combining CsF / alkali hydroxide with NMP as Solvent.

According to the invention, the system CsF / alkali hydroxide is used as the catalyst. Alkali hydroxides of lithium, sodium and potassium are particularly preferred preferably sodium and potassium. The molar ratio CsF is: Alkali hydroxide preferably 1:10 to 10: 1, particularly preferably 1: 3 to 3: 1, especially about 1: 1.

CsF is inexpensive to obtain and contains no water. The same applies to the Alkali hydroxides, so that an anhydrous catalyst system is inexpensive can be produced that despite the poor solubility of CsF to homogeneous Catalysis is suitable.  

The reaction mixture in which the catalyst system is present is preferably at the beginning of the reaction for at least 100 seconds to at least 100 ° C heated.

The catalyst system according to the invention is much more active than, for example KOH alone.

The catalyst system according to the invention is based on CsF and the Compound to be reacted with alkyne, preferably in an amount of 0.1 to 40, particularly preferably 5 to 30, in particular 10 to 20 mol-y used.

The temperature during the reaction is preferably from -20 to 200 ° C., particularly preferably 40 to 160 ° C, in particular 80 to 120 ° C.

The pressure in the reaction system is preferably 1 to 25 bar (abs), particularly preferably 1 to 10 bar, in particular 1 to 1.4 bar. It is preferred Continuously pressed acetylene.

If a solvent is used, the proportion is Solvents, based on the compound to be reacted with the alkyne, preferably 1 to 99% by weight, particularly preferably 20 to 80% by weight.

The implementation can be continuous or discontinuous in all of them suitable reactors are carried out.

Compounds of the general formula (III)

R ² -C∼CR ³ (III)

used with the above meaning for R ³ .

In addition to acetylene and phenylacetylene, functionalized ones can also be used Alkynes such as propargylamine can be used.

The invention is illustrated by the following examples.

Examples example 1 Vinylation of heptanol

0.3 mol of heptanol were placed in a 1 liter rotating steel autoclave together with the specified amounts of catalyst. Acetylene was introduced into the autoclave at room temperature at a pressure of 12 to 16 atm and the reaction mixture was heated to the reaction temperature with stirring. After the stated reaction time, the mixture was cooled to room temperature, the reaction mixture was removed from the autoclave and distilled. The results are shown in Table 1 below.

Example 2

Different alcohols were vinylated with the CsF-NaOH catalyst system. The procedure described in Example 1 was carried out using 0.3 mol of alcohol and an initial pressure of acetylene at an ambient temperature of 10 to 14 atm. The results are shown in Table 2.

Example 3 Reaction of secondary alcohols with acetylene

Reaction conditions:
0.3 mol alcohol, CsF-NaOH 10/10 mol%, 138 to 140 ° C, initial pressure of acetylene at ambient temperature 12 to 14 atm

Table 3

Example 4 Reaction of heptanone with acetylene at ambient pressure

Reaction conditions:
0.05 mol heptanol, 50 ml DMSO, 100 ° C, acetylene flow about 2 l / h

Table 4

Example 5 Vinylation of primary alcohols

Reaction conditions:
0.05 mol alcohol, CsF-NaOH 10/10 mol%, 50 ml DMSO, 100 ° C, acetylene flow about 2 l / h

Table 5

Example 6 Vinylation of secondary alcohols

Reaction conditions:
0.05 mol alcohol, CsF-NaOH, 10/10 mol%, 50 ml DMSO, 100 ° C, acetylene flow about 2 l / h

Table 6

Example 7 Reaction of 1,4-butanediol with acetylene

Reaction conditions:
Initial pressure on acetylene at ambient temperature 10 to 12 atm

Example 8 Reaction of 1,3-diols with acetylene

Reaction scheme

Reaction conditions:
Initial pressure of acetylene at ambient temperature 10 to 12 atm

Example 9 Reaction of diols with acetylene

Reaction conditions:
Initial pressure of acetylene at ambient temperature 10 to 12 atm

Example 10 Reaction of 1,2-diols with acetylene

Reaction scheme

Reaction conditions:
Initial pressure of acetylene at ambient temperature 14 atm, 138 to 140 ° C, 0.5 l stirred autoclave

Example 11 Reaction of diols with acetylene

Reaction conditions:
0.05 mol, 50 ml DMSO, 100 ° C, acetylene flow about 2 l / h

Table 11

Example 12 Reaction of pentaerythritol with acetylene

Reaction conditions:
0.045 mol pentaerythritol, 50 ml DMSO, initial pressure of acetylene at ambient temperature 14 atm, 3 h

Table 12

Example 13 Reaction of pentaerythritol with acetylene

Reaction conditions:
0.045 mol pentaerythritol, 85 ml DMSO, 6 h, acetylene flow about 5 l / h

Table 13

Example 14 Vinylation of alcohols and polyols

Reaction conditions:
100 ° C, initial pressure of acetylene at ambient temperature 10 to 12 atm

Table 14

Claims (5)

1. Use of CsF / alkali metal hydroxide as a catalyst in the alkenylation of organic compounds which contain groups -NH, -OH or <CH-Z with Z = CN, COOR with R = H, C ₁₆ -alkyl, by reacting the groups with organic compounds containing a CC triple bond. 2. Process for the preparation of alkene compounds of the general formula (IV)
R ³ -HC = CR ² -R ⁴ (IV)
with the meaning
R ² , R ^{3 are} independently H, NH ₂ or C _1-20 hydrocarbon radical which is substituted one or more times by C _1-6 alkyl and / or halogen and / or are interrupted by non-adjacent heteroatoms and / or CC double bonds can contain, as defined in claim 4,
R ⁴ R ⁶ N-, R ⁵ R ⁶ C (Z) - or R ⁷ -O- with
R ⁵ , R ⁶ , R ⁷ independently as defined for R ³ with the exception of H,
Z CN, COOR with R = H, C _1-6 alkyl
by reacting compounds of the general formula (V)
R ⁴ -H (V)
with compounds of the general formula (III)
R ² -C∼CR ³ (III)
in the presence of a basic catalyst, characterized in that CsF / alkali metal hydroxide is used as the basic catalyst. 3. The method according to any one of claim 2, characterized in that the Reaction is carried out in a solvent based on NMP. 4. The method according to any one of claims 2 or 3, characterized in that the molar ratio CsF: alkali hydroxide is 1:10 to 10: 1. 5. The method according to any one of claims 2 to 4, characterized in that the reaction mixture at least at the beginning of the reaction for at least Is heated to at least 100 ° C for 100 s.