JPH03167150A - Production of alpha-diketone and/or alpha-hydroxyketone - Google Patents

Abstract

PURPOSE:To efficiently and safely obtain the subject compounds useful as an intermediate for medicines, agricultural chemicals, perfumes, etc., in one stage by bringing a silane derivative into contact with a chain acetylene and an oxygen-containing gas in the presence of a cobalt complex of a beta-dicarbonyl compound. CONSTITUTION:A compound expressed by formula II (R<7> to R<9> are H or at least one thereof is 1-10C alkyl, aryl, lower alkoxy or arylalkyl) is brought into contact with a compound expressed by formula III (R<10> and R<11> are R or R<10> and R<11> together may form a ring) and an oxygen-containing gas in the presence of a cobalt complex expressed by formula I (R<1>, R<2>, R<5> and R<6> are H, R, aryl having F, CF3, alkylcarbonyl, alkylcarbonyl or CONH2; R is 1-10C alkyl, cycloalkyl, aryl or arylalkyl; R<3> and R<4> R or alkylcarboxy) to safely and advantageously afford the objective compounds expressed by formulas IV and/or V in high yield in one stage without using a highly toxic catalyst and decomposing functional groups.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing α-diketones and/or α-hydroxyketones using cobalt complexes.

Traditionally, σ-diketones and α-hydroxyketones have been used as pharmaceuticals, agricultural chemicals, and fragrances. However, these methods are highly toxic and extremely harmful to the human body. The problem lies in the use of reagents such as hexavalent manganese and osmium tetroxide.j4 On the other hand, α-hydroxyketones are usually produced using ketones as raw materials. That is, 1. After converting the ketone to a lithium enolate with a strong base such as lithium diisopropylamide, -7
Various oxygenating agents (e.g. 1!,
It can be converted to a-hydroxyketone by reacting with molecular oxygen, peracetic acid derivatization, molybdenum oxide, etc.).

However, such a method requires complicated operations such as using a strong base that is dangerous to handle and carrying out the reaction while keeping the reaction temperature low. The purpose is to solve the problems associated with the technology, and to provide a method that can efficiently and safely produce a-diketones and/or a-hydroxyketones from compounds using cobalt complexes. There is.

The manufacturing method of the present invention is a method for manufacturing an a-diketone represented by the following formula [rvl] and/or an a-hydroxyketone represented by the formula [V].

However, in the above formula [■], RIB and R11 conversion
Each independently represents a group selected from the group consisting of &-lower alkyl group, aryl group, arylalkyl group, and cycloalkyl group, and l, , Rle and R1+ may jointly constitute a ring.

However, in the above formula [V], R@ and R each independently represent a group selected from the group consisting of a lower alkyl group, an aryl group, an arylalkyl group, and a cycloalkyl group. It may form a ring.

The method according to the present invention for producing an a-diketone and/or an α-hydroxyketone as described above includes a cobalt complex of a β-dicarbonyl compound represented by the following formula [I]; R1, R2, R6 and R6
are selected from the group consisting of a hydrogen atom, a lower alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, an aryl group, an arylalkyl group, an aryl group having a fluorine atom, a trifluoromethyl group, an alkoxycarbonyl group, an alkylcarbonyl group, and a carbamoyl group. Represents an atom or group I R3 and RA iL
Each independently represents a group selected from the group consisting of a lower alkyl group having 1 to 10 carbon atoms, an arylalkyl group, an arylalkyl group, and a cycloalkyl group. ] In the presence of the primary formula [nl], a silane derivative represented by the primary formula [nl;
L each independently represents a hydrogen atom, a lower alkyl group having 1 to 10 carbon atoms, an aryl group, a group or an atom selected from the group consisting of a lower alkoxy group and an arylalkyl group;
At least one group is a group other than a hydrogen atom. and the following formula [chain acetylene expressed in ml; n-c=c-
n” ・・・・・・・・・[rrl] [However, the above formula [I
II], R, 10= and R14 each independently represent a group selected from the group consisting of 1, lower alkyl, aryl, 5, arylalkyl group, and cycloalkyl group. 1, , R1@ and R1+ together form a ring. You may do so. ] is brought into contact with an oxygen-containing gas.

According to the method for producing a-diketones and/or a-group hydroxyketones according to the present invention, since a specific cobalt complex is used as a catalyst, σ-diketones and/or α-hydroxyketones can be produced from acetylene in one step. Can be synthesized. This reaction is highly safe because it does not require the use of highly toxic catalysts such as osmium oxide as in conventional reactions.

Day 1 Next, the present invention will be specifically explained.

First, the cobalt complex used as a catalyst in the production method of the present invention will be explained.

The cobalt complex used in the present invention is a cobalt complex of a β-dicarbonyl compound, and this cobalt complex has the following formula [! ].

... [I1 In the above formula [I], R1, R2, and RJURa each independently represent a hydrogen atom, a lower alkyl group having 1 to 1° of carbon atoms, a cycloalkyl group, an aryl group having a fluorine atom, an aryl group having a fluorine atom, and a hydrogen atom. Fluoromethyl group represents an atom or group selected from the group consisting of alkoxycarbonyl penta-alkylcarbonyl group and carbamoyl group. Further, Rs and R41 each independently represent a group selected from the group consisting of a lower alkyl group having 1 to 10 carbon atoms, an aryl group, an alkylcarboxy group, an arylalkyl group, and a cycloalkyl group.

The above-mentioned lower alkyl group is an alkyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and this alkyl group may be linear or branched. Specific examples of such alkyl groups include methyl pentaethyl & n-
Propyl pig Isopropylmin-n-butyl & 5ec-
Butyl & L-Butyl Isobutyl An-Pentyl &
n-hexyl & n-heptylLn-octyl An octyl group and an n-nonyl group may be mentioned.

Among these lower alkyl groups, R1, R1, R% and R@ are preferably alkyl groups having 1 to 6 carbon atoms, particularly ethyl in-butyl5, 7-butyl5 isobutyl in-hexyl group, and R3 Preferred alkyl groups as R4 and R4 are alkyl groups having 1 to 6 carbon atoms.
Especially ethyl in-butyl & 1-butyl group isobutyl &
It is an n-hexyl group.

Further, specific examples of the cycloalkyl group include cyclohexyl, pentacyclopentyl, cyclohebutyl, and cyclooctyl groups. In addition, as mentioned above, the cycloalkyl group may have a substituent on the cycloalkyl ring.

Among these cycloalkyl groups, preferred cycloalkyl groups as R1, R2, R% and R are 1-methylcyclopentyl, 1-methylcyclohexyl &4-t
-butylcyclohexyl group. Also R3 and R
A preferred cycloalkyl group as 4 is a 1-methylcyclopentyl 11-methylcyclohexyl group.

The hydrogen atom on the aromatic ring may be substituted with another atom such as a halogen atom, or a substituent, etc., and a specific example of such an aryl group is L.
p-bromophenyl group etc. halogenated phenyl group
Octyl group Phenyl group) a Formula (1) described below
) to (20) can be mentioned.

r-■Σ-(14) F-1-...(15) φΣ...(I6) CFs-ζΣ...(17) (D(bean Σ...(13) Among these aryl groups, Preferred aryl groups as R1, R2, R5 and R6 are groups represented by formula (1), formula (151, formula (101), formula (17), formula (10), formula (19) and formula (20), Preferable aryl groups as R3 and R4 include formula (1), formula (8) and formula (8).
3, Equation (gradient, Equation (9), Equation (0, Equation ('7), Equation (mark, Equation (9, Equation (10), Equation (11), Equation (12) and Equation (1
3).

Further, examples of the arylalkyl group include groups represented by the following formula.

However, in the above formula, R represents a hydrogen atom or an alkyl group, m is an integer of 0 to 3, preferably 0 to 1, and n is an integer of 1 to 4, preferably 1 to 3.

Further, the hydrogen atom on the aromatic ring in the above formula may be substituted with another atom such as a halogen atom, or a substituent.

Specific examples of these groups include the following formula (2
Examples include groups represented by 1) to (39).

Preferred arylalkyl groups as R1, 21% RS and R6 of these aryl groups are formula (2g), formula (
30, formula (31), formula (3ri, formula (33), formula (3IO1
It is a group represented by three formulas: formula (3Q1), formula (37), formula (38), and formula (39).

E. Examples of the alkoxycarbonyl group include groups represented by the following formula.

C, H, , , 0-CO- However, in the above formula, ρζ represents an integer from 1 to 6. Specific examples of such alkoxycarbonyl groups include 1 methoxy group, ethoxy5n-propoxy group,
Mention may be made of an alkoxycarbonyl group in which the alkoxy group is an n-butoxy group and an n-pentoxy group.

Among these alkoxycarbonyl groups, R1, R1,
Preferred groups as RS and R6 A methoxy group Ethoxy group An alkoxycarbonyl group such as a propoxy group and a butoxy group.

Further, the alkylcarbonyl group is a group in which the alkyl group constituting the above-mentioned alkoxycarbonyl group is directly bonded to a carbon atom constituting the carbonyl group.

Further, the carbamoyl group can be represented by the following formula.

However, in the above formula, R14 and R15 each independently represent an atom or group selected from a hydrogen atom, a lower alkyl group, and a cycloalkyl group. Furthermore, R14 and 21% may jointly form a ring, in which case -0--8 to -NH+4 (wherein R is a lower alkyl group or a hydrogen atom),
Alternatively, RI4 and R1% may be linked via -N= to form a ring.

Here, examples of the lower alkyl group and the cycloalkyl group include the groups exemplified above.

Specific examples of such carbamoyl groups include dimethylaminocarbamoyl group, methylaminocarbamoyl group, diethylaminocarbamoyl group, dipropylaminocarbamoyl group, methylethylaminocarbamoyl group, and dipropylaminocarbamoyl group.
Piperazinocarbamoyl group Piperazinocarbamoyl group Morpholinocarbamoyl group Ethylaminocarbamoyl group, cyclohexylaminocarbamoyl group, cyclohexylethylaminocarbamoyl group, and the like.

Among these carbamoyl groups, R1 in the formula [rl
, R2, R% and R@ are particularly preferred groups (9-diethylaminocarbamoyl group, piperazinocarbamoyl group
They are a piperazinocarbamoyl group and a morpholinocarbamoyl group.

These formulas [R1 in rl. R2, R% and R6
may be the same or different.

Further, E, R' and R4 may be the same or different.

In the present invention, h of the cobalt complex represented by the above formula [I] is used as a compound exhibiting particularly excellent catalytic activity.
The following formula [I-1], [r -2], [+ -3], [
I-4] and [I-5].

... [r -1] However, in the above formula [l-11, R111RITR
+s and R'eJ4 each independently methyl &, n
-propyl We, 5ec-butylmi t-butylmi n
- Lower alkyl groups such as pentyl group; trofluoromethyl group; phenyl group, pentafluorophenyl & p-bromophenyl group; substituted or unsubstituted aryl group such as methoxyphenyl group; cycloalkyl group such as cyclohexyl group; hydrogen atom: Preferably, it is either a pig or an atom.

... [r −2] However, in the above formula [5-23, R2@R21R2
2 and R2*Jf, each independent simimethyl group
Lower alkyl groups such as ethyl & n-propyl & t-butyl groups and n-butyl groups are preferred.

...[l-3] However, in the above formula [I-33, R24R218H
ay and R2 are preferably lower alkyl groups such as ethyl 1 5ec-butyl and t-butyl;
Methoxy group Ethoxy L Lower alkoxy groups such as 5ec-butyl group and 7-butyl group; Methyl group Preferably a lower alkyl group such as ethyl group. Note that the two R211's may be the same or different.

... [I-4 madashi In the above formula [r-4], Rln R31
R34 and R”IL each independently
Lower alkyl group such as ethyl group or R31 and R”
It is preferable that R'l, H, and za incorporate a nitrogen atom to form a group consisting of a heterocyclic ring such as a piperidine group, a piperazine group, a morpholino group, and Rit and R21114 each independently, t- Preferably, it is a lower branched alkyl group such as a butyl group.

... [Summer-5] However, in the above formula [I-5], R26 and R2
At least one of e is preferably a group containing a fluorine atom such as trifluoromethyl group or p-)trifluoromethylphenyl group, and Rtt and RJI14 p-methylphenyl Lm-
Methoxyphenyl & 2.4.6-)limethylphenyl2.4-dimethoxyphenyl1-naphthyl5
Preferably, it is an aromatic group such as 2-naphthyl group.

Among the compounds represented by the above formula [I], the compounds represented by the following formulas (50) to (94) are particularly preferable as the catalyst used in the present invention.

Examples of suitable metal compounds among the compounds represented by the formula [x-11; 8-tetramethyl-4,
6-tunandionato) cobalt (++) Ruto (n) bis(2,4-hexanedionato) cobalt(51) bis(1,3-dicyclohexyl-1,3
-propanedionato) cobalt(,n) (54) bis[I,3-bis(4-methoxyphenyl)-1,3-propanedionato]:Ibalt([I)
Bis(1-pentafluorophenyl-2 bis(4,4-dimethyl-1-phenyl-1,4-butanedionato)cobalt([I), 3-pentanedionato) cono(ruto(n) bis[I-( 4-Bromophenyl) -4,4-bis(4,4-dimethyl-1-pentafludimethyl-1,3-pentanedionato)cobalt (rl) Orophenyl-1,3-pentanedionato)cobalt (■) Bis (2,4-nonanedionato) Cobalt bis(1,1,1-trifluoro-2,4-pene(n) tandionato) Cobalt(a) Bis(2,2-dimethyl-3,5-hexanebi,su(1 -Phenyl-1,3-butanedionadionato) Cobalt(n) Cobalt(n) Bis[4,6-nonanedionato) Cobalt(a) Bis(acetylaceto(n) To) Formula [I - 2] Among the compounds represented by, examples of suitable bis(1-n-methoxycarbonyl-1,3 compounds; monomethyl-1,3-butanedionato) cobalt(n) bis(1-ethoxycarbonyl-1,3-butanedionato) ) Cono(rut(n) bis(1-methoxycarbonyl-4,4-bis(1-n-butoxycarbonyl-4,4dimethyl-1,
3-pentanedionato) cobalt (■) 1-dimethyl-1,3-pentanediona) cobalt (n) bis(1-ethoxycarbonyl-4,4-) Preferred compounds among the compounds represented by the formula [■-3] Dimethyl-1,3-pentanedionato)cobalt(n) Example of coalescence: (7l) Bis(2-ethoxycarbonyl-1-phenyl-1,3
-butanedionato) Cobalt bis(1-n-propoxycarbonyl-4,4-dimethyl-1,3-pentanedionato)
Cobalt(n) Bis(2-acetyl-1-phenyl-2,4-bis(2-sec-butoxycarbonyl-pentanediono) Cobalt (n) Cobalt (n) 1,3-Butanedionato) Cobalt (n) Bis(2-71ptoxycarbonyl 1.3 Bis(2-methoxycarbonyl-1,3--butanedionato) Cobalt ([l) Butanedionato) Cobalt ([I) Bis(2-ethoxycarbonyl-1,3-butanedionato) cobalt ([I) Among the compounds represented by the formula [I-4], examples of suitable bis(1-diethylaminocarbamoy compounds; Ru 4 .4-dimethyl-1,3-pentanedionato)cobalbis(1-piperidinocarbamoyl-4to(n), 4-dimethyl-1,3-pentanedionato)cobalt(ri) (8l) bis(1 -piperidinocarbamoyl-4,4-dimethyl-1,3-pentanedionato)cobaltbis(1-dimethylaminocarbamoy(n)-4,4-dimethyl-1,3-pentanedionato)cobalt(n) ) (82) Bis(1-morpholinocarbamoyl-4
,4-dimethyl-1,3-pentanedionato)cobalt (■) Examples of preferred compounds among compounds represented by formula [r-5]; (84) Bis[I,1,1-)refluoro- 5-(
(4-methylphenyl)-2,4-pentanedionato]kobal) (n) (83) (1-dimethylaminocarbamoyl-4
,4-dimethyl-1,3-pentanediocad)(1-piperazinocarbamoyl-4,4-dimethyl-1,3-pentanedionato)cobalt (■) (85) Bis[I,1,1- Trif, fluoro-5-
(4-Methoxyphenyl)-2,4-pentanedionato]kobal)(n) (86) Bis[I,1,1-)lifluoro-5-(
3-trifluoromethylphenyl)-2,4-pentanedionato]cobalt (n) (88) bis[I,1,1-)lifluoro-4-<
2.4゜6-drimethylphenyl)-2,4-butanedionato]cobalt(n) (87) Bis[I,1,1-)lifluoro-4-(
4-methylphenyl)-2,4-butanedionato]cobalt(I]) (89) bis[I,1,1-)lifluoro-4-(
2,4-dimethoxyphenyl)-2,4-butanedionato]cobalt (n) (90) Bis[I,1,1-trifluoro-4-(
1-naphthyl)-2,4-butanedionato]cobalt (
[I) (92) Bis[I-(4-methylphenyl)
-3-(4-trifluoromethylphenyl)-1,3
-propanedionato] cobalt (n) (91) bis[I,1,1-)refluoro-4-(
2-naphthyl)-2,4-butanedionato]cobalt (
n)enyl)-3-(2,4,6-)limethylphenyl)-1,3-propanedionato]cobalt(n) (94) Bis[I-(2,4-dimethoxyphenyl)-3- (4-)lifluoromethylphenyl)-1,3
-propanedionato]cobalt (n) It can be obtained by adding a cobalt compound such as cobalt.

In addition, a cobalt complex (a hydrate or a salt) of the β-dicarbonyl compound may also be present.

In the present invention, the expression "cobalt complex of an a-dicarbonyl compound" also includes hydrates and salts of cobalt complexes of an a-dicarbonyl compound.

Cobalt complex L of a-dicarbonyl compound as above
For example, as shown below: An alcoholic or aqueous solution in which a dicarbonyl compound or its salt corresponding to the ligand of the complex to be obtained is dispersed or dissolved 1 While stirring, an aqueous sodium hydroxide solution is added dropwise to this solution. The reaction between the β-dicarbonyl chloride compound and the cobalt compound is usually carried out by adjusting the pH value of the reaction solution to be alkaline within the range of 8 to 12. This reaction is usually completed in 0.1 to 2 hours at a reaction temperature of 0 to 50°C.

The cobalt complex produced as described above has the above formula [! ] is usually a compound in which R1 and R@, R2 and R%, and R3 and R3 are the same group with the cobalt atom as the point of symmetry.

The cobalt complex let of the present invention may be a compound having symmetry as described above, but it does not need to have symmetry. 2ffl of cobalt complex with
It can be produced by preparing two or more types of cobalt complexes, mixing these two or more types, and refluxing the mixture in the presence of a reaction solvent such as toluene. Examples of the above reactions are shown below.

It can be obtained by

As the β-dicarbonyl compound used in producing the cobalt complex as described above, L can be used without any particular restriction as long as it is a compound that can form the above cobalt complex. A specific example of such a β-dicarbonyl compound is 3,7-dimethyl-4,6-
Nonanedione, 1,3-dicyclohexyl 1,3-propanedione, 2,2.8.8-tetramethyl-4,6-
Nonanedione, 1,3-butanedione, 1,3-his(4-methoxyphenyl)-1,3-propanedione, 1-pentafluorophenyl-1,3-butanedione,
4.4-dimethyl-1-pentafluorophenyl-1,
3-pentanedione, 4.4-dimethyl-1-phenyl-1,3-Tpentanedione, 1-(4-bromophenyl)-4,4-dimethyl-1,3-pentanedione, 2.4-nonanedione , 2,2-dimethyl-3,5-hexanedione, 4.6-
Nonanedione, 1-ethoxycarbonyl-1,3-butanedione, 1-
n-butoxycarbonyl-4,4-dimethyl-1,3-
Pentanedione, 1-n-methoxycarbonyl-4,4-dimethyl-1,
3-butanedione, 1-methoxycarbonyl-1,3-butanedione, 1-
Methoxycarbonyl-4,4-dimethyl-1,3-pentanedione, 1-ethoxycarbonyl-4,4-dimethyl-1,3-
Pentanedione, 1-n-propoxycarbonyl-4,4-dimethyl-1
,3-pentanedione, 2-ethoxycarbonyl-1-phenyl-1,3-butanedione, 3-ethoxycarbonyl-2,4-pentanedione, 2
-acetyl-1-phenyl-1,3-butanedione, 2
-Methoxymethyleneacetoacetic acid methyl ester, 2-ethoxymethyleneacetoacetic acid methyl ester, 2-methoxymethyleneacetoacetic acid 5ec-butoxy ester 2-t-hydroxymethyleneacetoacetic acid-7-butyl ester, 1,1.1-) Refluoro- 5-(4-methylphenyl)-24-pentanedione 1,1,1-trifluoro-5-(4-methoxyphenyl-2,4-pentanedione, 1-piperidinocarbamoyl-4,4-dimethyl- 1,
3-pentanedione, 1-dimethylaminocarbamoyl-4,4-dimethyl-
1,3-pentanedione, 1-diethylaminocarbamoyl-4,4-dimethyl-
1,3-pentanedione, 1-piperazinocarbamoyl-4,4-dimethyl-1,
3-pentanedione, 1-morpholinocarbamoyl-4,4-dimethyl-1
゜3-pentanedione, 1,1.1-)lifluoro-5-(4-methylphenyl)-2,4-pentanedione, 1,1.1-)lifluoro-5-(4-nitrophenyl)-2 , 4-pentanedione, 1, 1. i-trifluoro-5-(3-)lifluoromethylphenyl)-2,4-pentanedione, 1,1.
1-) Lifluoro-4-(4-methylphenyl)-
2,4-butanedione, 1,1.1-)lifluoro-4-(2,4,6-trimethylphenyl)-2,4-butanedione, 1.1.1-)lifluoro-4-(2,4- dimethoxyphenyl)-2,4-butanedione, 1,1.1-)lifluoro-4-(1-naphthyl)-
2,4-butanedione, i, i, 1-trifluoro-5-(2-naphthyl)-2,4-butanedione, 1-(4-methylphenyl)-3-(4-)lifluoromethylphenyl)- 1,3-propanedione, 1-(4
-) fluoromethylphenyl) -3-(2,4゜6
-trimethylphenyl 1-(2.4-dimethoxyphenyl)-3-(4-)lifluoromethylphenyl) (, 3-propanedione, and 1-phenyl-1.3-propanedione. These β-dicarbonyl compounds can be used alone or in combination.

There is no particular restriction on the cobalt compound used to produce the cobalt complex of the present invention together with the above-mentioned β-dicarboxy compound.8 Cobalt compounds that can be used in the present invention include, for example, inorganic cobalt such as CoCQz. Compounds and Co (C HsC O O
) V, etc., and these cobalt compounds can be used alone or in combination.

Although this reaction between the β-dicarboxylic acid and the cobalt compound can be carried out in water, it is preferable to carry out the reaction in a mixed solvent of water and alcohol.

Reaction solvent used in the present invention. Weight ratio of water and alcohol inside; 9 Usually 10:90-100'
It is within the range of 0.

The method for producing σ-diketones and/or a-hydroxyketones according to the present invention involves contacting a silane derivative, an acetylenic hydrocarbon compound, and an oxygen-containing gas in the presence of a cobalt complex of a β-carbonyl compound as described above. It is characterized by allowing

The silane derivative used in the present invention has the following formula [I1
].

However, in formula [r1], R', R' and R.
Each independently represents a group or atom selected from the group consisting of a hydrogen atom, a lower alkyl group having 1 to 10 carbon atoms, a lower alkoxy group, and an arylalkyl group.

However, in the above formula [nl, R? , R@ and R9
Among them, at least one group is a group other than a hydrogen atom. Therefore, in the present invention, SiH4 is not used.

These lower alkyl melons having 1 to 10 carbon atoms
Specific examples of the lower alkoxy group and the arylalkyl group include the groups exemplified in the description of the cobalt complex represented by formula [I] above.

Specific examples of the silane derivative represented by the above formula [II] include methylsilane, ethylsilane, phenylsilane, diethylsilane, dimethylsilane, bentylsilane, diphenylsilane, methylethylsilane, methylphenylsilane, trimethylsilane, triethyl. Silane, tri-n-propylsilane, dimethylphenylsilane, diethylphenylsilane, dimethylethylsilane, dimethylsilane, 7-butyldiethylsilantoxysilane, ethoxysilane, methylmethoxysilane,
Mention may be made of diethylmethoxysilane, phenylmethoxysilane, phenylethoxysilane, methyldimethoxysilane and diethylmethoxysilane. These silane derivatives can be used alone or in combination.

Among these silane derivatives, dimethylsilane, diethylsilane, trimethylsilane, triethylsilane, dimethylphenylsilane, methyldiphenylsilane, diethylmethoxysilane, dimethylethoxysilane,
Particularly preferred are t-butyldimethylsilane and phenylsilane, etc. I/1 Acetylenic hydrocarbon compound used in the present invention: 9 Usually an acetylenic hydrocarbon compound having 2 to 30 carbon atoms, preferably 4 to 20 carbon atoms. , for example, can be expressed by the following formula [I111.

R-C"EC-R--1-... [ml However, in the above formula [[+1], R11R1+ is
Each is independently a group selected from alkyl groups, aryl groups, and alkylaryl groups. In addition, these)
II RI 114 may be the same or different, and R1@ and R eyes may jointly form a ring.

Such acetylene hydrocarbon compounds represented by the above formula [ml include aliphatic acetylene compounds, alicyclic acetylene compounds, and aromatic acetylene compounds.

These compounds may have a substituent. In the method of the present invention, the triple bond contributing to the reaction may be located at a portion other than the end of the main chain, for example, near the center of the main chain, or may be located at a portion other than the end of the side chain, for example, near the center of the side chain. It may be located in

The olefinic hydrocarbon compound used in the present invention is usually a compound having at least one triple bond that is active in the reaction of the present invention, as shown by the above formula [ml]. Compounds having 2@ or more of such triple bonds can also be used. Furthermore, when having two or more triple bonds, these triple bonds do not need to exhibit the same activity in the reaction of the present invention.

Even if an acetyrene hydrocarbon compound having such a functional group is used, according to the production method of the present invention, the functional group does not receive the shape of the a-diketone and/or the a-diketone and/or the a-diketone.
-Hydroxyketones can be produced.

As the oxygen-containing gas used in the present invention, not only oxygen itself can be used, but also a gas containing components other than oxygen such as air can also be used. When using a gas containing components other than oxygen, a gas in which the concentration of oxygen in the gas is 5% by volume or more is preferably used in consideration of the economic efficiency of the reaction.

In the method for producing a-diketone and/or σ-hydroxyketone of the present invention, it is not necessary to use a reaction solvent, but a reaction solvent may be used.

When a reaction solvent is used in the present invention, any usable reaction solvent may be used without particular limitation as long as it has no activity against the reaction raw materials. Examples of solvents that can be used as reaction solvents in the present invention include hydrocarbon solvents such as hexane, benzene, and toluene.

Halogenated hydrocarbon solvents such as dichloromethane, ethylene dichloride, and chloroform; Ester solvents such as methyl formate, ethyl formate, methyl acetate, ethyl acetate, and butyl acetate; Ether solvents such as tetrahydrofuran, dimethoxyethane, dioxane, and diethyl ether. can be mentioned. These solvents can be used alone or in combination.

Among these solvents, benzene, toluene, dichloromethane, ethylene dichloride or tetrahydrofuran are preferably used.

In the method for producing a-diketone and/or a-hydroxyketone according to the present invention, the cobalt complex of the β-dicarbonyl compound is usually 0°001-1 mol per mol of the acetylenic hydrocarbon compound used. , preferably in an amount within the range of 0.01 to 0.02 mol. In the present invention, the cobalt complex may be used alone or supported on a carrier. In this case, commonly used carriers can be used.

In addition, the silane derivative is an acetylene hydrocarbon compound 1
For moles, usually IL 0. 3 to 50 mol, preferably 0. It is used in amounts ranging from 5 to 3.0 moles.

Further, the amount of oxygen-containing gas introduced into the reaction system may be 2 mol or more per 1 mol of the acetylenic hydrocarbon compound used, and it is usually introduced in excess into the reaction system. Form of supply of oxygen-containing gas to the reaction system: There is no particular restriction as long as the reaction raw materials such as Dai silane derivatives and acetylene hydrocarbon compounds and the cobalt complex acting as a catalyst are in a form that allows contact with oxygen-containing gas, and oxygen atmosphere A method of stirring the mixture downward, a method of bubbling oxygen-containing gas into the reaction liquid, etc. can be adopted.

This reaction can be carried out under either reduced pressure or increased pressure, and is usually 0. 1 to 50 atmospheres, 0. It is preferable to carry out the reaction at a pressure within the range of 2 to 2 atmospheres.

The reaction temperature for the above reaction varies depending on other conditions, but is usually -70 to 200°C, preferably -10 to 1
The temperature is set within a range of 50°C.

By reacting at such a temperature, usually 0.
The reaction is completed in 5 to 50 hours, preferably 1 to 20 hours.

The above reaction IL can be carried out in various forms such as a fixed bed, a fluid bed, and a moving bed.

By reacting in this manner, an a-diketone represented by the following formula [■] and a σ-hydroxyketone represented by the formula [vl] can be obtained.

However, in formula [N], RII and R++ (1 each represent a group selected from the group consisting of an independent stain, a lower alkyl group, an aryl group, an arylalkyl group, and a cycloalkyl group, and RI and R++ jointly constitute a ring. You may do so.

However, in the above formula [vl, RII and R1 each independently represent a group selected from the group consisting of 1, lower alkyl group, aryl group, arylalkyl group, cycloalkyl group, and RIe and RI jointly constitute a ring. Good too.

Specific examples of lower alkenyl groups in the above formula [rvl and formula [vl] are the same as the groups exemplified in formula [ml].

a-diketone/α obtained by the production method according to the present invention
-Hydroxyketone 1 reaction intermediate water Highly useful as a solvent, fragrance, etc.

According to the method for producing σ-diketone and/or σ-hydroxyketone according to the present invention, 1! Since a cobalt complex is used as a catalyst, a-diketone and/or a+ hydroxyketone can be synthesized from acetylene in one step. Furthermore, this reaction is highly safe because it does not require a highly toxic catalyst such as osmium oxide, unlike conventional reactions.

Moreover, by using the above catalyst, σ-diketone and/or σ-hydroxyketone can be produced in high yield using acetylene having a functional group as a raw material.

Furthermore, even if the acetylenic hydrocarbon compound has a functional group, the functional group will not be decomposed, and therefore an a-diketone having such a functional group can be converted from an acetylenic hydrocarbon compound having a functional group. and/or a-
Hydroxyketones can be produced.

Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples.

1.2-diphenyl-1,2-ethanedione-1 and 1
．． Synthesis of 2-diphenyl-1-hydroxy-2-ethano1-2 Diphenylacetylene 178. @ (1 mmol) and triethylsilane 456. (4 mmol), bis(
Acetylacetonato) cobalt complex 26W@(0.1 mmol) was dissolved in 5 mmol of 1,2-dichloroethane and stirred at room temperature (approximately 20°C) for 24 hours under an oxygen atmosphere of 1 atm. After the reaction was complete, 1 Normal aqueous hydrochloric acid solution (410 ml) was added and stirred well. After extracting the organic matter with dichloromethane, the organic layer was washed twice with aqueous sodium bicarbonate and once with brine, and the remaining 8i layer was dried over anhydrous magnesium sulfate, and then a By purifying with degenerate thin layer chromatography (silica gel) and operating as above, 100W of 1,2-diphenyl-1,2-ethanedione was obtained (yield 48%).
). Yellow oil.

In addition, 34W of 1,2-diphenyl-1-hydroxy-2-ethanone was obtained (yield: 16%). Colorless oil.

In addition, Examples 2 to 17 in which 30 W of benzoic acid was obtained. 1, 2- generated by operating as above
Diphenyl-1,Z-ethanedione...(1)1.
2-diphenyl-1-hydroxy-2-ethanone...
The yield of (2) is shown in Table 1.

Table 1 X Example silane compound 1! Esohi L piece j luck % number
Raw Ift product (1) Product (2) 2 Triethylsilane 3 FII above 4 Same as above 5 Same as above 6 Same as above 7 Same as above - 3 - From the same group Monophenylsilane lO Same as above 11 FBI above 12 Same as above! -夛---------pH 14 Diethylsilane 15 Same as above 1-6----------F11 17 Ethoxydimethylsilane removal port F118 1-phenyl-1,2-propanedione Synthesis of 凰 and 1-phenyl-2-hydroxy-1-propanone-4 1-
Phenyl-1-propyne, 116.1 (1 mmol) and phenylsilane, 216. (2 mmol), complex with bis(trifluoroacetylacetonato)conocle (
No. 62) Dissolve 32 (0.1 mmol) in 5 ml of 1°2-dichloroethane and stir vigorously for 12 hours at room temperature in an oxygen atmosphere of -atmosphere. After a specified period of time, the product was analyzed by gas chromatography. When analyzed using
The yields of phenyl-1,2-propanedione-3 and 1-phenyl-2-hydroxy-1-propanone-4 are:
50% and 30%, respectively, and t4 11 Examples 19 to 21 Except for Example 18, in which 1 mmol of the specified acetylene derivative listed in Table 2 was used instead of 1-phenyl-1-propyne and the reaction was carried out for a specified period of time. is done in the same way t4
The results are shown in Table 2.

Claims (1)

[Claims] (1) Cobalt complex of β-dicarbonyl compound represented by the following formula [I]; ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[I] [In the above formula [I], R^1, R^ 2, R^5 and R^6 are each independently a hydrogen atom, a carbon number of 1 to
Represents an atom or group selected from the group consisting of 10 lower alkyl groups, cycloalkyl groups, aryl groups, arylalkyl groups, aryl groups having a fluorine atom, trifluoromethyl groups, alkoxycarbonyl groups, alkylcarbonyl groups, and carbamoyl groups. , R^3 and R^
4 each independently represents a group selected from the group consisting of a lower alkyl group having 1 to 10 carbon atoms, an aryl group, an alkylcarboxy group, an arylalkyl group, and a cycloalkyl group. ], a silane derivative represented by the following formula [II]; ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・[II] ^8 and R
^9 each independently represents a group or atom selected from the group consisting of a hydrogen atom, a lower alkyl group having 1 to 10 carbon atoms, an aryl group, a lower alkoxy group, and an arylalkyl group, and R^7, R^ At least one group among 8 and R^9 is a group other than a hydrogen atom. ] and a linear acetylene represented by the following formula [III]; R^1^0-C≡C-R^1^1...[III
][However, in the above formula [III], R^1^0 and R^1^1 each independently represent a group selected from the group consisting of a lower alkyl group, an aryl group, an arylalkyl group, and a cycloalkyl group. The expressions R^1^0 and R^
1^1 may jointly constitute a ring. ] and an oxygen-containing gas, a method for producing an α-diketone represented by the formula [IV] and/or an α-hydroxyketone represented by the formula [V]; ▲Mathematical formula, chemical formula, table, etc. There is▼・・・・・・・・・［I
V] [However, in formula [IV], R^1^0 and R^1
^1 each independently represents a group selected from the group consisting of a lower alkyl group, an aryl group, an arylalkyl group, and a cycloalkyl group, and R^1^0 and R^1^1 jointly constitute a ring. You may do so. ] ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・［
V] [However, in the above formula [V], R^1^0 and R
^1^1 each independently represents a group selected from the group consisting of a lower alkyl group, an aryl group, an arylalkyl group, and a cycloalkyl group, and R^1^0 and R^1^
1 may jointly form a ring. ].