JPS5942660B2 - Ketone production method - Google Patents

Description

[Detailed description of the invention] The present invention relates to a method for increasing the carbon number of ketones.

Ketones are usually produced by oxidation or dehydrogenation of secondary alcohols, but it is not possible to freely produce various ketones.

The present invention is a method for producing a ketone with a larger number of carbon atoms from a ketone with a relatively lower number of carbon atoms, and is a method in which a ketone, an aldehyde, and hydrogen are catalytically reacted as shown in the following formula.

CH3COR+R'CHO+H2→ RCOCH2CH2R'+H2O... (1)
CH3COCH3+ 2RCHO+ 2H2→R'CH
2CH2COCH2CH2R'+2H2O・・・・・・
(2) (However, R is a methyl group or a phenyl group, R'
(represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms containing a straight chain, branched or cyclic moiety)
The reaction of formula 1) occurs, but when R is a methyl group, the reaction of formula (2) also occurs depending on the conditions.

Reaction products other than those of this formula can also be obtained as by-products. The method of the present invention will be further explained with reference to a case in which, for example, acetone is selected as the starting ketone and reacted with an aldehyde and hydrogen. For example, when formaldehyde is selected as the aldehyde, methyl ethyl ketone is selected, and when acetaldehyde is selected, methyl-n-propyl ketone is used.
In the case of propionaldehyde, methyl-n-butyl ketone is mainly obtained.

Depending on the conditions, diethyl ketone, dipropyl ketone, and dibutyl ketone can be obtained respectively. Furthermore, depending on the conditions, a ketone with an even greater number of carbon atoms is produced from the produced ketone. All of these ketones have higher added value than acetone, which is the starting material, and are industrially useful.

On the other hand, in addition to being consumed in the above-mentioned ketone production, the aldehyde used is also partially consumed in the hydrogenation reaction to produce the corresponding alcohol, but these by-products are also not industrially useful. Yes, it will never go to waste. In the present invention, Group 8 elements serving as main catalysts include iron, cobalt, nickel, ruthenium, rhodium, palladium, and osmium, among which cobalt is excellent.

These elements can be used alone or as a compound, and are used in a dispersed or dissolved state in the reaction system.

Compounds used include oxides, hydroxides, carbonates, sulfates, sulfides, nitrates, halides, organic acid salts,
Examples include organometallic complexes and carbonyl compounds. Although these main catalyst elements can be used alone or in combination to advance the reaction of the present invention, the method of the present invention can be further enhanced by using them in combination with iodine or bromine and an organic phosphine. It can be suitably implemented. The iodine or bromine used here may be any of iodine or bromine molecules, iodine or bromate acids, or iodine or bromine compounds such as metal salts of iodine or bromate.

Moreover, a combination of both components, iodine and bromine, can also be used.
When the main catalyst used is iodide or bromide,
Although the above-mentioned iodine or bromine component may be newly added, it can be used as is without any particular addition. As the organic phosphine, for example, alkyl phosphines such as tributylphosphine, arylphosphines such as triphenylphosphine, phosphine oxides, etc. are used.

The molar ratio of ketone and aldehyde used in the present invention is 0.1 to 2, preferably 0.1 to 1 mole of ketone.
．． 2 to 1,2.

Although the reaction of the present invention proceeds outside this range, the above range is preferred from the viewpoint of suppressing side reactions of aldehydes. Although carbon monoxide is not required in the reaction formula of the present invention, the presence of carbon monoxide is essential for the catalyst used in the method of the present invention to function. The necessary carbon monoxide partial pressure is practically in the range of 20 to 200 k9/Cl. If the amount is less than this, the reaction will proceed, but the speed will be slow, and if it is more than this, there will be no harm to the reaction, but it will be economically disadvantageous.
As shown in the above reaction formula, the reaction of the present invention requires the presence of hydrogen, and the necessary hydrogen partial pressure is 5 to 200 k
9/d1 is preferably in the range of 20 to 150k9/d.

If the amount is less than this, the reaction will proceed, but the speed will be slow, and if it is more than this, alcohol by-product reaction from aldehyde will easily occur, which is not preferable. The carbon monoxide and hydrogen used in the present invention may be mixed with an inert gas, such as argon, nitrogen, carbon dioxide, methane, orthane, as long as the above-mentioned partial pressure ranges can be maintained.

The amount of the catalyst to be used for suitably carrying out the reaction of the present invention is 0.1 to 200 milligram atoms of Group 8 elements, preferably 5 to 50 milligram atoms, and 0.1 milligram atoms of iodine or bromine per mole of raw material ketone. -500 milligram atoms, preferably 5-100 milligram atoms, and the phosphorus compound has O as phosphorus atoms, 1-500 milligram atoms, preferably 5-200 milligram atoms.

When the above range is exceeded, the reaction proceeds at least at a slower rate, and above the above range there is no adverse effect on the reaction, but the above range is practically sufficient. The reaction of the present invention varies depending on the type of catalyst used and other reaction conditions, but is generally carried out in the range of 150 to 300'C.

Although the reaction proceeds at lower temperatures, it is not practical in terms of reaction rate, and too high temperatures are undesirable because side effects are likely to occur. The reaction of the present invention does not require the presence of a solvent, but depending on the type of catalyst used, it may be necessary to disperse or dissolve the catalyst, to recover the catalyst after the reaction, or to suppress side reactions. You can also use

The solvents used include various amides, nitriles, aliphatic or aromatic hydrocarbons, and organic acid esters. The method of the present invention can be carried out in either a batch method or a continuous method.

As described above, the present invention provides a new and industrially useful method for easily producing various ketone compounds.

Aspects of the present invention will be explained in more detail with reference to the following examples.

Example 1 Acetone 109, acetaldehyde 7.59, iodine cobalt 19 and tributylphosphine 29 as catalysts were added to a stainless steel shaking autoclave with an internal volume of 100 m1 (the same one was used in the following examples), and hydrogen and tributylphosphine were added. Gas mixture with carbon monoxide (H2/CO=1
) 180k9/DG was injected and reacted at 200°C for 3 hours.

As a result, the acetone reaction rate was 40.3 mol%, and the selectivity for each ketone was 81.2% for methyl-n-propyl ketone.
, 6.3% of methyl-1-butyl ketone, and 9% of methylpentyl ketone. The rest was mainly i-propanol. Moreover, the acetaldehyde reaction rate was 86.4%, and the reaction rate of acetaldehyde was 86.4%, and the reaction rate of acetaldehyde was mainly ethanol, except that it was involved in ketone formation.

Example 2 The same conditions as in Example 1 were repeated except that rhodium chloride 19 and iodine 0.59 were used instead of cobalt iodide.

As a result, the acetone reaction rate was 25.2 mol%, and the selectivity for each ketone was 36.6 mol% for methyl-n-propyl ketone.
%, methyl-1-butyl ketone 12%, and methylpentyl ketone 14.7%. The rest was mainly i-propanol. Also, the acetaldehyde reaction rate is 99.7
%, and other than the above ketones were mainly ethanol.

Example 3 Acetone 109, 35% formaldehyde aqueous solution 109, nickel iodide 19 and triphenylphosphine 29 were charged into an autoclave, and reacted under the same conditions as in Example 1.

As a result, the acetone reaction rate was 23.6 mol%, and the selectivity to each ketone was 20.8% for methyl ethyl ketone, 16.4% for diethyl ketone, and 2 for methyl-1-butyl ketone.
It was 1%. In addition to the above-mentioned ketone production, formaldehye K was consumed in the production of a polymer with acetone. Example 4 Propionaldehyde 109 instead of acetaldehyde
The reaction was carried out under the same conditions as in Example 1 except that .

As a result, the acetone reaction rate was 48.6 mol%, and the selectivity to each ketone was 43.4 mol% for methyl-n-butyl ketone.
%, methyl-1-butyl ketone 42%, and methylpentyl ketone 11.7%. Others were mainly i-propanol. The propionaldehyde reaction rate was 54.
It became 6 mol%, and became propanol except for ketone formation. Example 5 Acetophenone 129, acetaldehyde 69, cobalt chloride 0.59, ruthenium chloride 19 in an autoclave
, iodine bromide 19 and tributylphosphine 29 were charged, and a gas mixture of hydrogen and carbon monoxide (H2/CO=
1) 200k9/~G was injected and reacted at 220°C for 3 hours.

As a result, at an acetophenone reaction rate of 21 mol%,
A selectivity to phenylpropyl ketone of 78.5% was obtained.
The rest was mainly phenylethanol. Further, the acetaldehyde reaction rate was 90 mol%, and ethanol was mainly produced except for ketone production. Comparative Example 1 In Example 1, only hydrogen was used instead of the gas mixture.
0k9/~ was press-fitted, and everything else was done in exactly the same manner.

As a result, the acetone reaction rate was 41.5%, and the selectivity to each ketone was 2.5% for methyl-n-propyl ketone and 11% for methyl-1-butyl ketone. Moreover, the acetaldehyde reaction rate was 94.7%, and other than ketone production, it changed to a high boiling point component.

Comparative Example 1 Example 1 was carried out in exactly the same manner as in Example 1 except that only carbon monoxide (190k9/CTi) was injected under pressure instead of the gas mixture.

As a result, the acetone reaction rate was 40 mol%, and the selectivity for each ketone was 7.5% for methyl-n-propyl ketone, 18.2% for methyl-1-butyl ketone, and 5% for methylpentyl ketone. Also, the acetaldehyde reaction rate is 99%
In addition to ketone formation, it changed to a high-boiling point component. Comparative Example 3 A reaction was carried out under the same conditions as in Example 1 except that CO2 (CO) 819 was used alone as a catalyst, and the acetone conversion rate was 21.5 mol%, and the selectivity to each ketone was methyl- n-propyl ketone 45%, methyl-1-
Butyl ketone 12.5%, methylpentyl ketone 6.3%
It was %. At the same time, a large amount of i-propanol and polymers were produced as by-products.

Comparative Example 4 CO2 (CO)81f11 was used as a catalyst in Example 1.
When the reaction was carried out under the same conditions except that 0.69% of copper acetate was used, the acetone reaction rate was 25.4 mol%, and the selectivity to various ketones was 3.3% for methyl-n-propyl ketone,
The concentrations were 13.0% methyl-1-butyl ketone and 4.1% methylpentyl ketone.

Claims (1)

[Claims] 1 Under pressure of carbon monoxide, the general formula CH_3COR
The ketone represented by
represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms containing a straight chain, branched or cyclic moiety) and, together with hydrogen, (1) an element from Group 8 of the periodic table, (2) iodine or bromine, and (3) ) organic phosphine, general formula RCOCH_2CH_2, characterized in that it is brought into contact with a catalyst consisting of
When the ketone represented by R' or R is a methyl group, the general formula R'CH_2CH_2COCH_2CH_2R
A method for producing a ketone represented by .