JPH0761982A - Production of lactone - Google Patents

Abstract

PURPOSE:To produce a lactone from a cyclic ketone in high yield and in high selectivity by using an inexpensive acetaldehyde. CONSTITUTION:In a method for producing a lactone by reacting a cyclic ketone with an oxygen containing gas in the presence of an aldehyde having >=2 carbon, a hetero polyacid or its salt is used as a catalyst.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing lactones. More specifically, it relates to a method for producing a lactone by reacting a cyclic ketone with an oxygen-containing gas in the presence of an aldehyde.

[0002]

2. Description of the Related Art A technique for obtaining a lactone and a carboxylic acid by reacting a cyclic ketone with an aldehyde in the presence of an oxygen-containing gas is already known (for example, Japanese Patent Publication Nos. 41-6330 and 41-8930). , Shokoku Sho 4
2-10844, Japanese Patent Publication No. 43-16145). These reactions usually require a catalyst, for example cobalt, manganese, copper, platinum or palladium. Japanese Patent Publication No. 57-47896 discloses a method for producing ε-caprolactone and acetic acid using cyclohexanone as a cyclic ketone, acetaldehyde as an aldehyde, and a soluble iron compound as a catalyst. However, these reactions have the drawbacks that the lactone yield with respect to the aldehyde used is low and that adipic acid and the like are by-produced.

[0003]

SUMMARY OF THE INVENTION The present invention has been made to solve the above drawbacks in the production of lactones, and effectively promotes the reaction of cyclic ketones, aldehydes and oxygen-containing gas. Then, it aims at providing the method of manufacturing the target lactone with a high yield and a high selectivity.

[0004]

According to the present invention, the object of the present invention is to provide a method for producing a lactone by reacting a cyclic ketone with an oxygen-containing gas in the presence of an aldehyde having 2 or more carbon atoms. Has been found to be achieved by a method characterized in that is carried out in the presence of a heteropolyacid or a salt thereof.

The cyclic ketone which can be used in the present invention is not particularly limited, and is usually a 4- to 13-membered ring, preferably a 4- to 8-membered ring ketone. The cyclic ketone may be substituted with 4 or less, preferably 2 or less, alkyl groups or allyl groups. As these cyclic ketones,
For example, cyclobutanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, cyclodecanone, cycloundecanone, cyclododecanone,
Cyclotridecanone, cerumbone, 2-methylcyclobutanone, 2-ethylcyclobutanone, 2-propylcyclobutanone, 2,2-dimethylcyclobutanone, 2,3-
Dimethylcyclobutanone, 3-methylcyclobutanone,
2-methylcyclopentanone, 3-methylcyclopentanone, 2-ethylcyclopentanone, 2-ethylcyclopentanone, 2-propylcyclopentanone, 2-butylcyclopentanone, 2,2-dimethylcyclopentanone 2,3-dimethylcyclopentanone, 3,4-dimethylcyclopentanone, 2,4-dimethylcyclopentanone, 2,5-dimethylcyclopentanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methyl Cyclohexanone, 2-ethylcyclohexanone,
2-propylcyclohexanone, 2-butylcyclohexanone, 2,2-dimethylcyclohexanone, 2,3-dimethylcyclohexanone, 2,4-dimethylcyclohexanone, 2,5-dimethylcyclohexanone, 2,6-dimethylcyclohexanone, 3,4-dimethyl Cyclohexanone, 3,5-dimethylcyclohexanone, 2-methylcycloheptanone, 3-methylcycloheptanone, 4
-Methylcycloheptanone, 2-ethylcycloheptanone, 2-propylcycloheptanone, 2-butylcycloheptanone, 2,2-dimethylcycloheptanone, 2,3
-Dimethylcycloheptanone, 2,4-dimethylcycloheptanone, 2,5-dimethylcycloheptanone, 2,6
-Dimethylcycloheptanone, 2,7-dimethylcycloheptanone, 3,4-dimethylcycloheptanone, 3,5
-Dimethylcycloheptanone, 3,6-dimethylcycloheptanone, 4,5-dimethylcycloheptanone, 2-
Methylcyclooctanone, 3-methylcyclooctanone, 4-methylcyclooctanone, 5-methylcyclooctanone, 2-ethylcyclooctanone, 2-propylcyclooctanone, 2-butylcyclooctanone, 2,
2-dimethylcyclooctanone, 2,3-dimethylcyclooctanone, 2,4-dimethylcyclooctanone, 2,
5-dimethylcyclooctanone, 2,6-dimethylcyclooctanone, 2,7-dimethylcyclooctanone, 2,
8-dimethylcyclooctanone, 3,4-dimethylcyclooctanone, 3,5-dimethylcyclooctanone, 3,
6-dimethylcyclooctanone, 3,7-dimethylcyclooctanone, 4,5-dimethylcyclooctanone, 4,
6-dimethylcyclooctanone, 4-ethylcyclohexanone, 1,2-cyclohexanedione, 1,3-cyclohexanedione, 1,4-cyclohexanedione, 2-
Phenylcyclobutanone, 3-phenylcyclobutanone, 2-phenylcyclopentanone, 3-phenylcyclopentanone, 2-phenylcyclohexanone, 3-phenylcyclohexanone, 4-phenylcyclohexanone, 2-phenylcycloheptanone, 3-phenylcycloheptanone , 4-phenylcycloheptanone, 2-phenylcyclooctanone, 3-phenylcyclooctanone, 4-phenylcyclooctanone, 5-phenylcyclooctanone and the like. Further, as the polycyclic ketones, α-cyperone, β-cyperone, cholestane-4-
On, cholestane-1-one, tetrahydro-α-cyperone and the like.

On the other hand, the aldehyde having 2 or more carbon atoms which can be used in the present invention is also not particularly limited, and an aliphatic or aromatic aldehyde having 2 to 10 carbon atoms is preferable. Specific examples thereof include Examples thereof include acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, isovaleraldehyde, 2-ethylbutyraldehyde, cyclohexanecarboxaldehyde and benzaldehyde.

In the reaction of the present invention, a heteropoly acid or a salt thereof is used as a catalyst. A preferred catalyst is a heteropoly acid or salt thereof containing at least one metal of Group V and Group VI of the Periodic Table. More preferred is a heteropoly acid containing at least one metal selected from the group consisting of molybdenum, tungsten, chromium, vanadium and niobium, or a salt thereof. Above all, a heteropoly acid containing molybdenum, tungsten, or both, or a salt thereof is particularly preferable. Specific examples of the heteropoly acid include, for example, phosphotungstic acid, phosphomolybdic acid, phosphovanadic acid, phosphoniobic acid, silicotungstic acid, silicomolybdic acid, silicovanadic acid, siliconiobic acid, phosphomolybdotungstic acid, phosphomolybdovanadic acid, lanthanum. Gustovanadic acid, phosphotungstoniobic acid, phosphomolybdniobic acid, phosphovanadydoniobic acid, silico molybdo vanadic acid, silico molybdo tungstic acid, silico molybdo niobic acid, silico tungstovanic acid, silico tonstoniovic acid, silico vanadide Niobic acid, copper molybdic acid, copper tungstic acid, copper vanadic acid, copper niobate, nickel tungstic acid, nickel vanadic acid, nickel molybdic acid, nickel niobate,
Cobalt molybdic acid, cobalt tungstic acid, cobalt vanadate, cobalt niobate, iron tungstate, iron molybdate, iron vanadate, iron niobate, manganese molybdate, manganese tungstate, manganese vanadate, manganese niobate, chromium molybdenum acid,
Chromotungstic acid, chrome vanadic acid, chrome niobate, phosphocopper molybdic acid, phosphocopper tungstic acid, phosphocopper vanadic acid, phosphocopper niobate, phosphonickel tungstic acid, phosphonickel vanadic acid, phosphonickel molybdate, phosphonickel niobate Phosphorus cobalt molybdic acid, Phosphorus cobalt tungstic acid, Phosphorus cobalt vanadate, Phosphorus cobalt niobate, Phosphorus iron tungstate, Phosphorus iron molybdic acid, Phosphorus iron vanadate, Phosphorus iron niobate, Phosphorus manganese molybdate, Phosphomanganese tungstate , Phosphomanganese vanadic acid, phosphomanganese niobate, phosphochrome molybdic acid, phosphochrome tungstic acid, phosphochrome vanadate, phosphochrome niobate,
Phosphomolybdungstovanadic acid, Phosphomolybdungston niobate, Phosphomolybdvanazidniobate, Phosphotungstovanazidniobate, Bismuth molybdic acid, Bismuth tungstic acid, Bismuth vanadic acid, Bismuth niobate, Arsenic molybdate and arsenic Tungstic acid etc. can be illustrated.

These heteropolyacids are preferably used as salts, and examples of the salts include alkali metal salts, alkaline earth metal salts and ammonium salts.
The metal and ammonium forming these salts are not particularly limited, but examples of the alkali metal include sodium, potassium and cesium, and examples of the alkaline earth metal include calcium, strontium and barium. . As ammonium, ammonium, methylammonium, ethylammonium, propylammonium, butylammonium, hexylammonium, octylammonium,
1 such as cetyl ammonium and benzyl ammonium
Substituted ammonium; 2-substituted ammonium such as dimethylammonium, diethylammonium, dipropylammonium, dibutylammonium, dihexylammonium, dioctylammonium, diphenylammonium and dibenzylammonium; trimethylammonium, triethylammonium, tripropylammonium, tributylammonium, trihexylammonium. , Trioctylammonium, triphenylammonium, tribenzylammonium and the like, trisubstituted ammonium; tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, tetrahexylammonium, tetraoctylammonium, tetradecylammonium, trimethylbenzylammonium 4-substituted ammonium such as monium, decyltrimethylammonium, benzylcetyldimethylammonium, cetyldimethylethylammonium and phenyltrimethylammonium; and other pyridinium, N-ethylpyridinium, N-butylpyridinium, N-hexadecylpyridinium, N-cetylpyridinium and Examples include pyridinium such as 4-dimethylaminopyridinium.

The heteropolyacid or salt thereof is not particularly limited as long as it is an amount sufficient to allow the reaction to proceed, but is preferably 0.0001 to 10% by weight based on the cyclic ketone used in the reaction. It is preferably used in the range, particularly preferably in the range of 0.0001 to 1% by weight.

The reaction in the present invention may be carried out continuously in a liquid phase or batchwise, and at this time, a solvent may be used so as to keep the reaction liquid in a liquid phase state. . As such a solvent, an aldehyde or a cyclic ketone as a reaction raw material, a lactone or a carboxylic acid as a reaction product can be used. It is also possible to use a solvent inert to the reaction, for example, an organic solvent such as benzene, chlorobenzene, dichlorobenzene, ethyl acetate, acetonitrile, chloroform acetate, 1,2-dichloroethane or acetone.

The reaction temperature depends on the raw materials used, but is usually preferably in the range of 0 to 100 ° C. If the reaction temperature is lower than the above range, the reaction rate becomes slow, while if it is higher than the above range, the ratio of side reaction increases and the selectivity of lactones decreases. The reaction time depends on the raw materials used and the reaction temperature, but is usually about 0.5 to 10 hours. If the reaction pressure is sufficient to keep the reaction system in the liquid phase,
It is not particularly limited to normal pressure or increased pressure. As the oxygen-containing gas used in the reaction, pure oxygen, air, or a gas obtained by diluting oxygen with nitrogen, helium, argon or the like can be used.

After completion of the reaction, the reaction solution is subjected to operations such as distillation and extraction to easily obtain the desired lactone.

[0013]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1 Cyclohexanone 1 was placed in a 100 ml autoclave.
7.4 g, ammonium phosphotungstate 2 mg, acetaldehyde 2.6 g were added, and oxygen gas was 5 kg / c.
It was filled with m ² and stirred in warm water at 50 ° C. for 4 hours.
After the stirring was stopped, the reaction solution was filtered, and the reaction solution from which the catalyst was removed was quantitatively analyzed by gas chromatography. As a result, the yield of ε-caprolactone based on the consumed acetaldehyde was 45%, and the selectivity was 99%. ε-
The caprolactone yield was calculated based on the following formula.

[0015]

[Equation 1]

Comparative Example The same procedure as in Example 1 was carried out except that iron acetylacetonate (III) complex and bipyridyl were used as the catalyst. As a result, the yield of ε-caprolactone was 12% and the selectivity was 69%.

Examples 2 to 7 The same procedure as in Example 1 was carried out except that another heteropolyacid or a salt thereof was used as the catalyst. The results are shown in Table 1.

[0018]

[Table 1]

[0019]

According to the method of the present invention, it becomes possible to produce lactones in high yield and high selectivity by using heteropolyacid or its salt.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical display location B01J 27/198 X 9342-4G C07D 307/33 309/30 D 313/18 // C07B 61/00 300 (72) Inventor Shigeru Isayama 6-1-2 Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture Mitsui Petrochemical Industry Co., Ltd. (72) Shinya Hirokane 6-1-2 Waki, Waki-cho, Yamaguchi Prefecture Mitsui Petrochemical Industry Co., Ltd. (72) Inventor Masahiro Kuwahara 6-1-2 Waki, Waki-cho, Kuga-gun, Yamaguchi Mitsui Petrochemical Industry Co., Ltd.

Claims (2)

[Claims] 1. A method for producing a lactone by reacting a cyclic ketone with an oxygen-containing gas in the presence of an aldehyde having 2 or more carbon atoms, wherein the reaction is carried out in the presence of a heteropolyacid or a salt thereof. how to. 2. The method according to claim 1, wherein the heteropolyacid or a salt thereof is a heteropolyacid containing at least one metal selected from the group consisting of molybdenum, tungsten, chromium, vanadium and niobium, or a salt thereof. .