DE2009928C3 - Process for the preparation of saturated aliphatic alcohols, carboxylic acids, their esters, lactones, nitriles or amides - Google Patents

Description

and or

- C - C - CRTl'T

I I

Examples of suitable organic halogen compounds are chlorohydrins, such as ethylene and propylene chlorohydrin, chlorine and bromoacetic acids and their esters, nitriles and amides.

When the organic halogen compound is a carboxylic acid or a derivative, for example an ester, a lactone is obtained:

C = C + XCR'R'COOR
/ \

> C — C-CRR "

I-O-CO

Lactone formation takes place without oxidation of the metal.

If an epoxide is present as a reaction component in the process, the reaction proceeds as follows:

C = C + CC

C — C — C — C — OH

The invention relates to a process for the preparation of saturated aliphatic alcohols, Saturated aliphatic carboxylic acids, their esters, lactones, nitriles or amides, characterized in that that he

a) a substituted paraffin of the general formula X (CH ₂ ) “Y, in which X is a chlorine or bromine atom and Y is a hydroxyl, carboxyl, carboxyalkyl, nitrile or amide group and η is 1 to 10, or

b) a compound of the formula XCR'R "Y, wherein CR'R "form an aromatic ring and X and Y have the aforementioned meaning, or

c) a C ₂ - to C ₄ alkylene oxide with an α-olefin containing 2 to 20 carbon atoms, in the presence of a transition metal compound in the reduced state, which is suitable for carrying out one-electron oxidation-reduction reactions, optionally in the presence of one inert organic diluent converts.

The course of the process using the organic halogen compounds defined above

d. i.e., the product is an alcohol.

In this case, the product as a whole is essentially saturated, whereby the oxidation of the Metal.

The alkylene oxides used in the process of the invention are in particular ethylene oxide and propylene oxide

and butylene oxide into consideration.

The α-olefin used as a reaction component in the process is, for example, hexene-1. Oc: ten-1, dodecene-1 and tetradecene-1.
The lower α-olefins are preferred reaction components, in particular ethylene and propylene, which can enter into a telomerization reaction, with the ethylene or propylene forming a higher molecular weight product of the structure

C-C CR'R'T

and or
HC-CI CR'R "Y

or

HC-C C-C-OH

nrin η has the meaning given above, iirt. For example, ethylene can form the product (CH ₂ CH ₂ JgCRTrY and / -R ^ or

I ι

H (CH ₂ CHA-CC-GH

Eaters When the lower α-olefins are used as reaction components, both the pressure of the olefin and the reaction temperature are important factors in determining the ketiene length of the products obtained. In general, increasing olefin pressure or partial pressure increases the chain length of the products. Olefin pressures up to 1000 at can be used, however pressures of 5 to 500 at, especially 5 to 100 at, and especially 10 to 50 at are preferred. Under these circumstances the product contains a mixture of chain lengths with a distribution around an average which increases with increasing olefin pressure. The preferred maximum temperature for this embodiment of the invention is 200 ° C., with 75 to 150 ° C. being a preferred range. A certain decomposition of the product takes place above 200 ^° C., and there is a tendency towards the generation of an increased amount of branched-chain by-products.

Ethylene is preferred as the .z-olefin, since it is a straight-chain one Product is obtained and because straight-chain alcohols and esters together are important in detergent production and in the production of plasticizer esters for polyvinyl chloride. Likewise, ethylene oxide is preferred to propylene or butylene oxide. It can Omega-haloalkanoic acids or their derivatives Instead of chloroacetic or bromoacetic acid or their esters can be used. However, because the latter is easier are available, they are preferred. In general, the most valuable products come from the lower ones "-Olefins obtained, where η is preferably in the range

from »to 8 lies. .

A one-electron oxidation-reduction reaction is a reaction in which an electron is transferred to or from the metal. In order to be able to undergo such a transfer, the metal must therefore be capable of occurring in two adjacent valency states. Metals suitable for this purpose are iron, copper, titanium, vanadium and uranium, preferably chromium. The metal can be used as such, but is generally used as a salt or complex compound, e.g. B. as a halide, for example a chloride such as vanadium chloride, as an alkanoate, for example an alkanoate with up to 20 carbon atoms, such as titanium stearate or vanadium acetate, or as carbonyl, ζ. Β. Chromium carbonyl applied. Mixtures of metals or mixtures of compounds of different metals, e.g. B. a mixture of a chromium compound and a vanadium compound can be used in the method of the invention. Generally speaking, are catalytic amounts of the metal compound for use in the method, for example, 1 x 10 ^"4 to 1 molar, preferably

A polar liquid is generally preferred as the inert organic diluent. When such diluents include alcohols, e.g. B. Ethanol, propanol and the butanols, lower alkanoic acids, like acetic acid; Acid derivatives, ζ. Β. Amides such as dimethylformamide, N-methylacetamide, dimethylacetamide; Nitriles such as acetonitrile, propionitrile and benzonitrile; Esters, especially the lower ones Alkanoic acids, e.g. B. methyl acetate, benzyl acetate, ethylene glycol diacetate, Methyl propionate and ethyl butyrate; Ketones such as acetone, methyl ethyl ketone and cyclohexanone; Esters such as 1,2-dimethylethane and tetrahydrofuran; and various organic polar ones Liquids such as dimethyl sulfoxide, diphenyl sulfoxide and sulfates can also be considered. Water can also be used can be used as a diluent.

Although the process is preferably carried out as a homogeneous liquid phase reaction, it can also run heterogeneously in the liquid or gas phase. So can the metal or the metal compound in the liquid phase either alone or on an inert support, e.g. B. silica, pumice-Ϊ5 stone, asbestos, magnesia-aluminum oxide or carbon. Likewise can a gaseous olefin and olefin oxide or carboxylic acid or carboxylic acid derivative in the vapor phase be passed over the metal or the metal compound as such or located on a carrier. the the latter reaction can be used in the manufacture of the products for reasons of expediency, which are volatile at the reaction temperature and which are therefore easily removed from the reaction zone be able.

The process can be accomplished by incorporating a metal complexing agent into the reaction mixture be improved, which is preferably 3 to 10 times the molar concentration of the metal. Suitable

Nete complexing agents are ethylenediamine, ethylenediaminetetraacetic acid and the ethanolamines. Other complexing agents that can be used in a similar concentration are amines, ζ. B. the ethylamines, phosphines, ζ. B. Triphenylphosphine and Arsine, z. B. Diphenyl

45 ethyl arsine. The complexing agents are useful because they complex with the metal ion form.

As ν previously described, the production of saturated> derivatives leads to the consumption of the catalyst,

50 so dal: Viii.-fig is advantageous a reducing agent for the conversion of the metal into the reduced To * ..;. I * J to be provided. Such reducing agents can be applied in situ or at a later stage. Suitable reducing agents are zinc in

55 Presence of acid as well as hydrazine. The reductive Regeneration can also be carried out electrolytically.

In general, the method can be performed over a wide temperature range at-60 play from -50 to 300 ⁰ C, preferably 0 to 200 ⁰ C.

The products of the process are long-chain aliphatic Alcohols or aliphatic carboxylic acids and their derivatives, which are valuable chemical compounds represent products.

Butyrolactone, which is made from ethylene and a haloacetic acid can be obtained at low ethylene pressures is also a valuable chemical

Intermediate product for the production of N-methylpyrrolidone.

The invention is illustrated in more detail by the following examples

example 1

200 ml of aqueous dimethylformamide, containing 1.6 -HT ² mol chromium (H><: chloride and 2.0 ml of ethylenediamine, were converted into a mixture of? .0 ml of 1-octene and 1.0 ml of ethyl bromoacetate in the course of one hour under a nitrogen atmosphere added. During the addition the solution was stirred rapidly at 2O ⁰ C. After complete addition the solution was stirred for 1 hour and then poured into a large amount of water. the reaction products were extracted with ether, the extract * washed wiederho ¹ with water, Anhydrous, dried in magnesium sulfate and concentrated to a small volume The concentrate was examined by gas-liquid chromatography and found to ^{contain 0.5 x 10 -3} moles of ethyl decanoate and a trace of y-decane lactone isolated

Example 2

Example 1 was repeated with the exception that the chromium (II) chloride solution was added to a mixture of 20 ml of 1-octene and 10 ml of ethyl bromoacetate. In the reaction, 0.26 × 10 ^-2 mol of ethyl-n-decanoate, and 0.28 · 10 ^-2 mol y-Decanlacton prepared.

Example 3

Example 1 was repeated with the exception that the chromium (II) solution was added to 20 ml of 1-octene and 20 ml of ethyl bromoacetate. The yields of ethyl-n-decanoate and y Öecanlacton were, respectively, 0.32 · 10 ^-2 or 0,58 · 10 ^-2 mol. In the product was a little ethyl-dec-4-ehoat (0.8 * 10 " ³ moles) were found.

Example 4

Example 1 was again repeated, with the chromium was .ugegeben (II) solution at 70 ml to a stirred ⁰ C mixture of 20 ml of octene-1 and 10 Äthylchloracetat '. The reaction products were 0.13 x 10 ^-2 mole Athyldecanoat and traces of y-Decanlacton.

Example 5

0.3 × 10 ' ² mol of vanadiutn (II) chloride in dimethylformamide, containing about 20% water (100 ml), were added dropwise under a nitrogen atmosphere to a mixture of 20 ml of 1-octene, 10 ml of ethyl chloroacetate and stirred at 70.degree 50 ml of dimethylformamide were added. After the reaction products had been worked up, 0.1 × 10 ^-3 mol of ethyl decanoate and 0.65 × 10 ^-3 mol of γ-decane lactone were obtained.

Examples

Example 5 was repeated with the exception that a vanadium (II) solution was added to a mixture, stirred at 40 ° C., of 20 ml of 1-octene and 10 ml of ethyl bromoacetate. In the reaction, 0.15 x 10 ~~ ³ moles Athyldecanoat and 0.5 x 10 ~ ⁴ mol y-Decanlacton were prepared.

Example 7

A solution of ^{0.5-10 "2} mol of titanium (III) sulfate and 0.2 ml of ethylenediamine in 150 ml of dimethylformamide was added dropwise to a mixture of 20 ml of 1-octene and 10 ml of ethyl chloroacetate in 50 ml of dimethylformamide with stirring at 70 ° ° C. After work-up, 0.1 · 10 ^-3 mol of ethyl decanoate and a trace of y-decane lactone were found in the ίο products.

Example 8 A chromium (II) solution was obtained as in Example 1

manufactured except that ethylenediamine

was omitted. This solution was in the course

one hour to a mixture of 20 ml octene-1 and 10 ml of ethyl bromoacetate at 2O ⁰ C were added.

There were 0.23 x 10 " ² moles of ethyl decanoate and

0.26 · 10 ^-3 moles of y-decane lactone in the reaction

m> manufactured.

Example 9

1.6 x 10 " ² mol of chromium (II) chloride, dissolved in 100 ml of dimethylformamide, containing 2 ml of ethyl diamine,

“Five became one in half an hour Solution of 10 ml of ethyl bromoacetate, which is heated to -20 ° C cooled and saturated with ethylene was given. The reaction was carried out under an atmosphere of ethylene. The reaction mixture was finally up

Allowed to warm to room temperature, the products described in Example 1 were obtained. 0.1 · ^{10 ~ 2} mol of ethyl n-butyrate and a trace of γ-butyrolactone were found in the products.

J ₅ example 10

Example 8 was repeated using ethyl alcohol as the solvent in place of an aqueous dimethylformamide solution. The yield of ethyl decanoate was 0.11-10 " ² mol and the yield of y-decane lactone was 0.33 · 10" ² mol.

Example 11 A solution of 1.6 · 10 ~ ² moles of vanadium (II) -

chloride in 150 ml of aqueous dimethylformamide became a mixture over the course of an hour of 10 ml of 3-chloropropan-1-ol and 20 ml of hepten-1 added under an argon atmosphere at 70 ° C.

The mixture was kept at 70 ° C for an additional hour

left standing for a long time, and then the products were

so by ether extraction, as described in example 1,

isolated. In the reaction mol, 0.12 x 10 ~ ² Obtain n-decanol.

Example 12

SS Example 11 (1.6 x 10 ^-2 mol) and ethylenediamine repeated, replacing the vanadium chloride by chromium (II) chloride (2.0 ml). The yield of n-decanol was 0.14 x 10 ^"2 moles.

_to example 13

1.6 x 10 ^-2 mole of chromium (II) chloride and 2 ml of ethylenediamine in 40 ml of dimethylformamide and 80 ml of ethanol were over one hour in a nitrogen atmosphere to a stirred at 70 ° C • 5 mixture of 20 ml of octene-1 and 1 ml of ethylene chlorohydrin was added. The product was isolated by extraction of ether as described in Example 1. The product found was n-decanol.

Example 14

Example 13 was repeated with the exception that the ethylene chlorohydrin was replaced by 1 ml of ethylene bromohydrin was replaced. The reaction was carried out at 20 ° C., the product found being n-decanol would.

Example IS

1.6 × 10 ² mol of chromium (II chloride in 100 ml of water was added over half an hour to a vigorously stirred mixture of 10 ml of ethyl bromoacetate and 20 ml of 1-octene. The reaction was carried out at 25 ° C. under an argon atmosphere. The organic layer was diluted with ether, the ethereal solution was dried, the ether was evaporated and the residue was found to contain ethyl decanoate and decane lactone by means of a gas-liquid chromatographic analysis.

Example 16

1.6 ^{× 10 2} mol of chromium (II) chloride in 200 ml of dimethylformamide, containing 2 ml of ethylenediamine, was added over the course of one hour to a mixture of ImI chloroacetonitrile and 20 ml of Ocien-l. The product was worked up by ether extraction as in Example 1 and was found to contain n-nonyl cyanide.

Example 17

5 moles of dimethylformamide and 1 mole of ethylene oxide were placed in a stainless steel autoclave at 120.degree heated under an ethylene pressure of 34 at. It became an anhydrous solution of 0.05 mol of chromium (II) chloride fed to a reactor in 5 moles of dimethylformamide in the course of 2 hours. The solution was treated with water and the product extracted with ether. The yield of alcohols was: Ethyl alcohol: 3.3%. n-butyl alcohol: 6.1%, n-hexyl alcohol: 2.5%, n-octyl alcohol: 1.1%, n-decyl alcohol: 0 6%. i.e. the higher pressure resulted in an increased yield of longer chain products.

Example 18

0.18 mol of ethyl bromoacetate and 3.5 mol of dimethylformamide were at 120'C under an ethylene pressure heated by 29.2 at. A solution of 0.05 mol of hydrated chromium (II) chloride in 5 mol Dimethylformamide fed to an autoclave in the course of 2 hours. Through analysis it was found that the resulting solution is 12.9% ethyl acetate, 14.5% ethyl n-butyrate, 12.1% ethyl n-hexanoate, 43% Ethyl 2-ethylhexanoate contained 10.2% ethyl n-octanoate and 3.9% ethyl n-decanoate, all yields are based on added chromium (II) salt.

Example 19

Example 18 was at 100'C and an ethylene pressure repeated from 32.3 at. The yields of ethyl esters were: 7.3% ethyl n-hexanoate, 1.2% Ethyl 2-ethyl hexanoate, 3.3% ethyl n-octanoate, 2.5% ethyl n-decanoate.

Example 20

ίο 100ml dimethylformamide containing 1.6 x 10 ^"2 moles of vanadium trichloride were / was added over I ¹ hours to a mixture of 10 g of chloroacetic acid. 20 ml Ocjen-l and 50 ml of dimethylformamide at 70 ⁰ C. The product was isolated by stirring rapidly at 20 ° C. during the addition of the solution ^{and, after the addition was complete, stirring the solution for 1} hour and then pouring it into a large amount of water, whereupon the reaction products were extracted into ether and the extract was repeatedly washed with water anhydrous magnesium sulfate and concentrated to a small volume to reveal that the product contained ethyl decanoate and γ-decane lactone.

»5. Example 21

150 mils of dimethylformamide containing 1.6 x 10 ² moles of chromium (III) chloride was added to 10 ml of ethyl bromoacetate and 10 ml of octene-1 at ambient temperature over the course of one hour. The products were extracted with petroleum ether at a ratio of 100/120 to find that the extract contained ethyl decanoate in a 3.7% yield based on chromium.

3 ml of concentrated hydrochloric acid was added to the dimethylformamide solution added after extraction. Child's solution was in a zinc amalgam column run downhill. The chromium (II) solution that emerged from the column became a mixture from 20 ml of ethyl bromoacetate and 20 ml of 1-octene

. give, a 10.2% yield of ethyl decanoate based on chromium was obtained.

The dimethylformamide solution of chromium <III) chloride was reduced and reused as before, resulting in a 1 l, 4% yield of ethyl decanoate based on chromium.

Example 22

A mixture of 30 ml octene-1, 25 ml ethyl bromoacetate, 22 g chromium hexacarbonyl and 250 ml Dimethylformamide was kept at 120 ° C for 8 hours heated under nitrogen. The resulting solution was worked up as in Example 20 1.45 g of ethyl decanoate and 3.0 g of y-decane lactone were obtained.

40964Ä / 275

Claims (5)

Patent claims: 1. Process for the preparation of saturated aliphatic alcohols, saturated aliphatic Carboxylic acids, their esters, lactones, nitriles or amides, characterized in that that he a) a substituted paraffin of the general formula X (CHj) ₁₁ Y, in which X is a chlorine or bromine atom and Y is a hydroxyl, carboxyl, carboxyalkyl, nitrile or amide group and π is 1 to 10, or b) a compound of the formula XCR ¹ R ¹ T, in which CR ¹ R "form an aromatic ring and X and Y have the aforementioned meaning, or c) a C ₂ - to Q-alkylene yd with an α-olefin containing 2 to 20 carbon atoms, in the presence of a transition metal compound in the reduced state, which is suitable for carrying out one-electron oxidation-reduction reactions, optionally in the presence of an inert one organic diluent converts. 2. The method according to claim 1, characterized in that there is used as the paraffinic halogen compound of the formula X (CH ₂ ) "Y ethylene chlorohydrin, propylene chlorohydrin, chloro- or bromoacetic acid ethyl ester or a nitrile of these halocarboxylic acids. 3. The method according to claim 1 and 2, characterized in that there is ethylene as the α-olefin or octene-1 is used. 4. The method according to claim 1 to 3, characterized in that there is used as transition metal compounds in the reduced state vanadium (II) or chromium (II) chloride or chromium hexacarbonyl used. 5. The method according to claim 1 to 4, characterized in that the reaction is carried out in the presence of ethylenediamine as a metal complexing agent for the transition metal compound. tion can be represented schematically as follows: ^N C = C <+ XCR'R'T