JPS61243033A - Method for hydrogenating organic carbonyl compound - Google Patents

Abstract

PURPOSE:To hydrogenate efficiently an organic carbonyl compound selected from carboxylic acids, carboxylic acid anhydrides and carboxylic acid esters, by using a catalyst consisting of rhenium or a compound thereof and an organic amine. CONSTITUTION:An organic carbonyl compound selected from aliphatic and aromatic carboxylic acids, carboxylic acid anhydrides and carboxylic acid esters is efficiently hydrogenated with hydrogen in the presence of a catalyst containing (a) rhenium or a compound thereof and (b) an organic amine, preferably a tertiary amine, particularly an amine having >=7.0pKa value, preferably in the respective ratios as follows; 0.0001-0.01mol, expressed in terms of Re atom, based on one mol above-mentioned raw material, component (a) and 10-1,000mol, based on one mol Re atom, component (b). Since the above- mentioned catalyst contains a homogeneous system in at least part of the activity producing part thereof, it has higher activity and selectivity for the aimed compound than the conventional rhenium based catalysts.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for hydrogenating organic carbonyl compounds. Specifically, the present invention relates to a method for efficiently reacting aliphatic and aromatic carboxylic acids, carboxylic acid anhydrides, or carboxylic esters with hydrogen.

[Conventional technology]

Many techniques have been known for a long time regarding the hydrogenation reaction of organic carbonyl compounds. Typical examples include the use of catalysts supported on carriers such as copper-zinc, copper-chromium, nickel, cobalt, palladium, and platinum catalysts, which are also widely used in actual industrial processes.

It is also known to use rhenium compounds, especially oxides and sulfides, etc. as hydrogenation catalysts for organic carbonyl compounds. For example, H. El, Broadbent;
Journal of American Ohem
ical 8oaiety.

Volume 76, page 1Sl (/year 71I); same magazine, vol.
3617 pages (7969); Journal of
Organic Chemistry Volume 2q, page 1 (/?j de year); same magazine, volume 1, page 17700 and page 02 (1?6 year); same magazine, volume 2g, page 3 1. Many examples of using rhenium compounds in the solid state as catalysts are described on page 5IIz and page 41 (Ill. 1963).

[Problem that the invention seeks to solve]

As mentioned above, various heterogeneous catalysts are known for the hydrogenation reaction of organic carbonyl compounds, and efforts are being made to improve the performance of each.

However, it has not necessarily reached a sufficient level in terms of selectivity to the target product and catalyst life. In order to precisely control the selectivity to the desired product, it is generally considered desirable to use a homogeneous catalyst.

[Means for solving problems]

Taking the above facts into consideration, the present inventors conducted intensive studies on a catalytic reaction that can efficiently hydrogenate organic carbonyl compounds, and as a result, they used a catalytic system that combines a rhenium component and an organic amine. The inventors have discovered that good results can be obtained by doing so, and have arrived at the present invention.

That is, an object of the present invention is to provide a method for efficiently hydrogenating an organic carbonyl compound in the presence of a catalyst such as rhenium or a compound thereof and an organic amine.

The present invention relates to a method for hydrogenating an organic carbonyl compound, which comprises reacting an organic carbonyl compound selected from the group consisting of carboxylic acids, carboxylic acid anhydrides, and carboxylic esters with hydrogen.

Hereinafter, the present invention will be explained in detail.

A feature of the catalyst system of the present invention is that at least a part of its active part is in a homogeneous system, that is, in a solution state, and as a result, the performance is higher than that of conventional rhenium-based catalysts. It has high activity and high selectivity for the target product.

The organic carbonyl compounds used as raw materials in the process of the invention are aliphatic and aromatic carboxylic acids, carboxylic anhydrides and carboxylic esters.

Aliphatic carboxylic acids include formic acid, acetic acid, glopionic acid,
Lauric acid, glycolic acid, cyclohexanecarboxylic acid% phenylacetic acid, succinic acid, glutaric acid, adipic acid,
Examples include maleic acid. Aromatic carboxylic acids include benzoic acid, p-)silic acid, phthalic acid, naphthalene-
Examples include 26-one carboxylic acid.

Examples of the carboxylic anhydride include anhydrides of the above-mentioned carboxylic acids.

Examples of carboxylic acid esters include aliphatic alcohol esters and aromatic 7)v call esters of the above-mentioned carboxylic acids. Examples of the aliphatic alcohol include methyl alcohol, ethyl alcohol%n-propyl alcohol, n-7'thyl alcohol, -monoethylhexano~#,
Examples include cy/lohexyl alcohol and the like. Examples of the aromatic alcohol include phenol and p-cresol. Furthermore, lactones, which are intramolecular esters, can be mentioned as the above-mentioned carboxylic acid esters. The lactones include β-propiolactone, r-butyrolactone, r-
Nokurero 71) nb δ-valerolactone, g-
Examples include 7'rolactone, coumarin, dihydrocoumarin, and the like.

The source of hydrogen used in the method of the present invention is not particularly limited. Hydrogen containing some inert gas, such as carbon dioxide or nitrogen, can also be used.

In the method of the invention, the reaction between an organic carbonyl compound and hydrogen is carried out in the presence of a catalyst containing a rhenium component and an organic amine.

Rhenium components include metal rhenium.

Nyrenium trioxide, rhenium dioxide, rhenium trioxide,
Rhenium oxides such as cellified rhenium, ammonium perrhenate, L/Nium chloride.

Sodium hexachlororhenate, nato-2-acetatodichlorodyrenium, bis(triphenylphosphine)trichlorooxyrhenium, decacarbonyldyrenium,
Examples include heptahydridobis(triphenylphosphine)rhenium.

The amount of rhenium component used is usually 0.0000 rhenium atoms per 7 moles of the raw organic carbonyl compound.
/-0.1 mole, preferably 0.0li07-0001
It is in the molar range.

Examples of the organic amines mentioned above include trimethylamine, triethylamine, tri-n-propylamine, and tri-n-propylamine.
-butylamine, dimethylcyanomethylamine, tricyclohexylamine, dimethylbenzylamine, tris(J-hydroxyethyl)amine, N, N, N'
, Aliphatic chain amines such as N'-tetramethylethylenediamine; N-methylpyrrolidine, N-methylpiperidine, N-ethylpiperidine, quinacridine, N-methylmorpholine%N, N'-dimethylpiperazine, N-
Aliphatic cyclic amines such as methylimidazole, trimethylene dimorpholine, subartein, /jtI-diazabicyclo (jl, rioctane% l, t-diazabicyclo[jl, O]Townsen; N, N-dimethylaniline,
N,N-diethylaniline, N,N-dimethyl-m-1
0roaniline, N,N-dimethyl-p-chloroaniline, N,N-dimethyl-p-methoxyaniline, t,g-
Aromatic compounds such as bis(dimethylamino)s7talene; pyridine, α-picoline, β-picoline, 1-k”
Choline, 2,6-lutidine, 3-methyl-guethylpyridine, Hiro-methoxypyridine, α-picolinic acid,! ,
4(,6-)limethylpyridine, 3,! -dimethylpyridine, 3-cyanopyridine, -monohydroxypyridine,
Examples include pyridine derivatives such as U-(dimethylaminocopyridine, quinoline, isoquinoline, quinaldine, acridine, 2,2'-dipyridyl, /, 10-7 enanthroline, pyrazine, pyrimidine, pteridine, etc.).Primary amines and secondary amines such as methylamine, n-butylamine, aniline.

Alkylamines such as di-n-butylamine and diphenylamine, arylamines, dialkylamines, diarylamines, etc. can also be used effectively, but tertiary amines are more preferred. Further, among the above organic amines, amines having a pKa value of 7.0 or more are particularly preferred.

The amount of organic amine to be used is usually 0.1 mole of rhenium atom. /~io, ooo moles, preferably lO~/,
000 moles. It is also possible to use these amines as a solvent or part of a solvent. When used as a solvent, the amount used does not need to be within the above range.

The method of the invention is carried out in the liquid phase. As reaction medium it is possible to use the raw materials or the products themselves, but it is also possible to use other solvents.

Examples of such solvents include ethers such as diethyl ether, anisole, tetrahydro7rane, ethylene glycol dimethyl ether, and dioxane; ketones such as acetone, methyl ethyl ketone, and acetophenone; methanol, ethanol, n-7' tanol, benzyl alcohol, and phenol. Alcohols such as , ethylene glycol and diethylene glycol; Carboxylic acids such as formic acid, acetic acid, propionic acid and toluic acid: Methyl acetate and n-acetate
Butyl, benzyl benzoate and other esters; benzene,
Aromatic hydrocarbons such as toluene, ethylbenzene, tetralin; aliphatic hydrocarbons such as n-hexane, n-octane, cyclohexane; dichloromethane, trichloroethane, chlorobenzene, etc.;
Nitro compounds such as nitromethane and nitrobenzene; tertiary amines such as triethylamine, tri-n-7"f amine, benzyldimethylamine, pyridine, α-picoline, and -monohydroxypyridine; N,N-dimethylformamide, N, Amides such as N-dimethylacetamide, hexamethylphosphoric triamide, N-methyl-coimidazolidinone; N,N'-dimethyl-coimidazolidinone, N,N,N',N'-tetramethylurea, etc. Ureas; Sulfones such as dimethyl sulfone and tetramethylene sulfone; Sulfoxides such as dimethyl sulfoxide and diphenyl sulfoxide; γ-butyrolactone,
Lactones such as ε-caprolactone; tetraglyme,
Examples include polyethers such as /r-crown-6; non-nitriles such as acetonitrile and benzonitrile; carbonic acid esters such as dimethyl carbonate and ethylene carbonate.

Among the above-mentioned examples, tertiary amines can be used as a solvent having a function as a catalyst component.

Using the reaction medium as described above, the reaction of the present invention can be carried out uniformly.
It can be carried out either in a system or in a heterogeneous suspension system. The reaction temperature is usually ioo~,
The condition of 700'Q is adopted, more preferably 1
It is in the range of 50-50°C. The reaction pressure is usually
/ kid or more is adopted, but from a practical point of view, preferably / 0-/, 97 di for 000
preferably in the range of 5 to 0 kcV
cr/1% is particularly preferably in the range of 50 to 9/cri.

By the method of the present invention, compounds or derivatives thereof such as esters, alcohols, ethers, etc., are mainly produced in which the carbonyl group of the raw organic carbonyl compound is converted into a methylene group.

The reaction product obtained according to the invention is separated from the reaction liquid by distillation, but the residual reaction liquid containing the catalyst can be recycled to one reaction zone. Although the catalyst can exhibit sufficient activity even if it is used repeatedly, it is also possible to additionally use a new catalyst.

〔Example〕

Next, embodiments of the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded.

Example 1 A screw (
) Riphenylphosphine) Trichlorooxylenium A
Re 0O1a (PJ2'sn, o, i mm
olh Prepare 8 o mmol of tri-n-butylamine and j Ommol of acetic acid, and add hydrogen! After filling to 0 kg/aA, the temperature of the autoclave was raised to 200°C and the pressure was increased to 10 kg/aA. The reaction was carried out as it was for S time. Cool the autoclave and react
When the substance was analyzed by gas chromatography, the aroma of ethanol and ethyl acetate was /, /9&, and 9.096, respectively.
who have been confirmed to be producing with a yield of .

Comparative Example 1 The same reaction as in Example 1 was carried out except that tri-n-butylamine was not used, and the yields of ethanol and ethyl acetate were both +7%.

Example)! The same reaction as in Example 1 was carried out except that the amount of j-n-butylamine used was 0.0 mmol, and the yields of ethanol and ethyl acetate were /, A%, and /3, respectively.
．． It was θ.

Example J The amount of n-butylamine used is io.

When 11 with mmo 'i was subjected to the same reaction as in Example 1, the yields of ethanol and ethyl acetate were 89% and 11%, respectively. It was a friend.

Examples N, N, N', in place of n-butylamine
N'-tetramethylethylenediamine/, ommO:
When the same reaction as in Example 1 was carried out except that L was used, the yields of ethanol and ethyl acetate were 1. They were Ochi, J, and Flathead.

Example S When the same warping as in Example was carried out except that t-bis(dimethylaminoconaphthalene/, ommO1) was used instead of tri-n-butylamine, the yields of ethanol and ethyl acetate were as follows. 8.0% and t, S 俤 is nine.

Example 6 Rhenium trichloride RIBO40-/mmolh F ream- was placed in a 351!11 Hastelloy 0 autoclave.
Butylamine 8 o mmox b acetic acid s o mmol
and 10 ru of tetraglyme as a solvent,
When the same reaction as in Example 1 was carried out, the yields of ethanol and ethyl acetate were 3.2% and 211.4 tons, respectively.

Comparative Example The same reaction as in Example 6 was carried out except that Cotley n-butylamine was not used, and the yields of ethanol and ethyl acetate were both o.oqb.

Example 7 - The same reaction as in Example 6 except that dioxane (Example 7), benzene (Example t), and sulfolane (Example 9) were used in place of tetraglyme as desolvents. The yields of ethanol and ethyl acetate were determined as shown in the following table.

7. 7.4%
22.2fir /, 3
Person in charge Koko, 0 yen 9 Ko, Kochi /
6.6 Example 10 The same reaction as in Example 7 was carried out except that triethylamine was used in place of tri-n-butylamine.
The yields of ethanol and ethyl acetate were 9% and 9%, respectively.

Example // In a 35d Hastelloy O autoclave, nyrenium trioxide Os/mmol-Re, ) ethylamine O,
/mmol'l and acetic acid/00 mmol were charged and the same reaction as in Example 1 was carried out, the yields of ethanol and ethyl acetate were 0.00 mmol, respectively. Zayou and Ko 0. He was in charge of J.

Example 1 The same reaction as in Example // was carried out except that the amount of cotriethylamine used was 80 mmol, and the yields of ethanol and ethyl acetate were /, 0 and 1, respectively. .

Example 13 The same reaction as in Example // was carried out except that the amount of triethylamine used was /0.0 mmol.
The yields of ethanol and ethyl acetate were 1, 7 and 3, respectively.
! F, 0chi was rare.

Example 1 The same reaction as in Example 11 was carried out except that the amount of datriethylamine used was 4t O, Ommol.
Ko, it was 6 inches.

Example/j Substitute for nyrenium trioxide LK rhenium trioxide (7e/m
The same as Example 3 except that mol-Re was used.

Example 16 The reaction product suspension of Example 15 was treated with a glass filter to remove solid components, and the liquid component was distilled to almost completely remove acetic acid, ethyl acetate, and ethanol.

To this, acetic acid/00 mmol was added again and Example i
When the reaction was carried out under the same conditions as s, the yields of ethanol and ethyl acetate were /, 0% and is, o@, respectively. The reaction solution was substantially colorless and homogeneous. From this experiment, it is understood that at least a part of the catalytically active portion is in a homogeneous state.

When experiments corresponding to Examples /j and /6 were conducted without using an amine, the yields of ethanol and ethyl acetate were both 0.0%.

Example 1 The same reaction as in Example 3 was carried out except that di-n-butylamine was used in place of di-n-butylamine. The yields of ethanol and ethyl acetate were 7% and 4 tl, respectively. Met.

The same reaction as in Example 3 was carried out except that mono-n-butylamine was used in place of tri-n-butylamine in Example 1. The yields of ethanol and ethyl acetate were 7.
It was 1 and 3,8 ri.

Example 19 Nyrenium trioxide! r mmol-Re, ) So n-butylamine II Ommol, acetic acid/00
Pour mmol into an autoclave and add hydrogen to Okg/
After filling to cr/l, the temperature was raised to 200°C and a reaction was carried out for 3 hours. After filtering and distilling the reaction solution, the resulting catalyst solution (
Re 3000ppm) /,! r, 9 (Re O
,02'1mmol1) and acetic acid/00 mmol were placed in an autoclave and heated to %200℃. ;kg/Cr
When the reaction was carried out for S hours in A, the yields of ethanol and ethyl acetate were 0, e, and /j, 41, respectively.

Example-〇 Example /? except that the reaction temperature was /A O'C. When the same reaction as above was carried out, the yields of ethanol and ethyl acetate were 0, oes and 3.0, respectively. It was a flathead.

Example / Example except that the reaction temperature was set to 10°C. When the same reaction as above was carried out, the yields of ethanol and ethyl acetate were 3. / Ji and Ji, r %.

Example: Example/' except that the reaction pressure was 3 gkg/cIIl
When the same reaction as in 1 was carried out, the yields of ethanol and ethyl acetate were 0°OS and 6.6%, respectively.

Example 23 The same reaction as in Example 1 was carried out except that the reaction pressure was 150 kg/aA, and the yields of ethanol and ethyl acetate were 1, 3, and 3, respectively.

It was a lot.

Example cog nyrenium trioxide 8! r mmol-Re% tree n
-Butylamine 4IO mmol b Acetic acid 300 mmo
1 and tetraglyme 1Iow were placed in an autoclave and filled up to 10 kl//ctd of hydrogen.

The temperature of the autoclave was raised to 0.degree. C. and the reaction was carried out for S hours, after which the contents were cooled and filtered to obtain a homogeneous solution.

This solution is distilled to obtain approximately qo of rhenium-containing homogeneous catalyst solution substantially free of acetic acid, ethanol, and ethyl acetate.
I got l.

The above rhenium-containing homogeneous catalyst solution s, ot was placed in an autoclave.
t (λlI as a rhenium atom, *mol) h Benzoic acid/Ommol is charged, hydrogen is added/t 0klV
Filled to atl. After a 5 hour reaction at -4IoC,
When the contents of the autoclave were analyzed, it was found to be 8 tons of benzyl alcohol. mmol and benzyl benzoate OJ
It was confirmed that I OmmoIL was generated.

Example S The rhenium-containing homogeneous catalyst solution S, oti and methyl benzoate/Ommol described in Example S were charged into an autoclave and reacted for S hours at 200°C and ttOK9/crll, resulting in benzyl alcohol O, It was confirmed that mmol of Koda was produced.

Example-6 rmmol of succinic anhydride was used in place of methyl benzoate, and the reaction pressure was adjusted to 1/1. When the same reaction as in Example 2S was carried out except that OK/cr/I was used, it was confirmed that 2t mrnol was produced in addition to a small amount of tetrahydrofuran (THP) to γ-butyrolactone.

Example The same reaction as Example 2S was carried out except that maleic acid/Ommol was used instead of methyl benzoate. In addition to a small amount of THF, 0.1 r-butyrolactone was added.
It was confirmed that 10 mmol was produced.

Example λg Cono-phosphoric acid/Ommol was used in place of methyl benzoate, the reaction temperature was 2'10°C, the reaction pressure was it, oK/
The same reaction as in Example 3 was carried out except that cIit was used, and THF was about 0. It was confirmed that γ-butyrolactone was produced in Aj, 7 mmol in addition to γ-butyrolactone.

〔Effect of the invention〕

By the method of the present invention, carboxylic acids, carboxylic acid anhydrides, and carboxylic esters can be efficiently hydrogenated.

Patent applicant: Mitsubishi Chemical Industries, Ltd. Representative Patent Attorney Hase - 1 other person

Claims (1)

[Claims] (1) It is characterized by reacting an organic carbonyl compound selected from the group consisting of carboxylic acid, carboxylic acid anhydride, and carboxylic acid ester with hydrogen in the presence of a catalyst consisting of rhenium or a compound thereof and an organic amine. Method for hydrogenating organic carbonyl compounds.