JPH11269131A - Production of 1-acyloxy-2-propanol - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce the subject compound useful as an intermediate for producing a synthetic antimicrobial agent according to a simpler method in a higher yield than those in a conventional method by reacting a specific carboxylic acid with propylene oxide in the presence of a specified metal complex catalyst. SOLUTION: A carboxylic acid represented by the formula: RCOOH (R is a 1-20C alkyl or the like) (e.g. benzoic acid or p-nitrobenzoic acid) is reacted with propylene oxide in the presence of a metal complex catalyst represented by the formula R<1> is a 1-20C alkylene or the like; X<1> to X<10> are each H, a halogen, an alkyl or the like; M is M<1> (M<1> is a bivalent metal atom or a bivalent metal ion), M<2> -A<1> (M<2> is a bivalent metal atom or a trivalent metal atom; A<1> is a ligand) or M<3> -A<2> (M<3> is a trivalent metal ion; A<1> is a counterion), preferably M<1> and especially preferably when M<1> is a bivalent cobalt atom [CoII]} to thereby afford the objective compound represented by the formula: CH3 CH (OH)CH2 OCOR.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing 1-acyloxy-2-propanol useful as an intermediate of a synthetic antibacterial agent and the like and an optically active substance thereof.

[0002]

2. Description of the Related Art Conventionally, the following method has been proposed as a method for synthesizing 1-acyloxy-2-propanol. (1) A method of reacting benzoic acid and propylene oxide in the presence of a chromium complex catalyst (Cuihua Xuebao, vol. 3, p. 30)
3 (1982)). (2) Method of reacting benzoic acid and propylene oxide on the alumina catalyst surface (Angew. Chem. Intl. E
d.Engl., vol. 17, p. 487 (1978)). (3) A method for oxidatively opening 1,3-dioxolane which is a cyclic acetal (Synthetic Communication, vol. 20, p. 1563 (1990). J. Ch.
em.Soc.Perkin Trans.2, p.2175 (1993) .J.Chem.Soc.Che
m. Commun., p. 1245 (1983)). (4) A method of reacting 1,2-propanediol with a substituted benzoyl chloride (JP-A-3-204873).

Further, the following method has been proposed as a synthesis method when 1-acyloxy-2-propanol is a method for synthesizing optically active 1-acyloxy-2-propanol. (5) Asymmetric reduction of 1-acyloxy-2-propanone with an organoaluminum reducing agent using a tin (II) chloride catalyst and a chiral amine ligand (Chem. Lett., P.13)
59 (1985)). (6) Asymmetric reduction method of 1-acyloxy-2-propanone using Baker's yeast (Bull. Chem.
Soc. Jpn., Vol. 65, p. 631 (1992)). (7) A method of reacting an optically active 1,2-propanediol with a substituted benzoyl chloride (JP-A-3-204873).

[0004]

However, the above method has the following problems. The method (1) has a low yield. The method (2) has a problem that isomers are generated. All of the methods (3) are peroxides,
There is a problem that requires an oxidizing agent such as a manganese compound and iodine chloride which has problems in handling and working environment. (4)
The method has a problem that an acylated isomer is generated.
The method (5) has a problem in that an organoaluminum compound having a problem in handling and working environment is used as a reducing agent, and a problem in which the asymmetric yield is as low as 53% ee (enantioexcess). Since the method (6) is an enzymatic reaction, there is a problem that the volume efficiency is low and only an arbitrary optical isomer cannot be produced. In some cases, only unnecessary enantiomers are generated. The method (7) has a problem that a substitution position isomer is generated. As described above, the conventional method has low practicality,
There is a problem in industrial implementation.

[0005]

The present invention has been made to solve the above-mentioned problems, and provides a method for producing 1-acyloxy-2-propanol which is useful as an intermediate such as a synthetic antibacterial agent. .

That is, in a method for producing a 1-acyloxy-2-propanol represented by the following formula 2 by reacting a carboxylic acid represented by the following formula 1 with propylene oxide, a metal complex catalyst represented by the following formula 3 is prepared. The present invention provides a method for producing 1-acyloxy-2-propanol, wherein the reaction is carried out in the presence.

[0007]

Embedded image

The symbols in the formula have the following meanings. R: an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group, an aryl group having a substituent, an aralkyl group, or an aralkyl group having a substituent. R ¹ : an alkylene group having 1 to 20 carbon atoms, an alkylene group having 1 to 20 carbon atoms having a substituent, a cycloalkylene group having 3 to 20 carbon atoms, an arylene group, or an arylene group having a substituent. X ^{1 to} X ¹⁰ : may be the same or different, and each may be a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, a hydroxy group,
An amino group, a nitro group, a carbamoyl group, a carboxyl group, or an optionally substituted silyl group. M: M ¹ (where M ¹ represents a divalent metal atom or a divalent metal ion), M ² -A ¹ (where M ² is a divalent metal atom or a trivalent metal atom, and A ¹ is a coordinator) Indicates a child.),
Or M ³ -A ² (where M ³ is a trivalent metal ion, A
² represents a counter ion. ).

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. In the carboxylic acid (Formula 1), R is a group having 1 to 1 carbon atoms.
20 represents an alkyl group, a cycloalkyl group having 1 to 20 carbon atoms, an aryl group, an aryl group having a substituent, an aralkyl group, and an aralkyl group having a substituent.

The alkyl group (R) having 1 to 20 carbon atoms may have a linear structure or a branched structure, and preferably has a linear structure. The alkyl group (R) has 1 to 20 carbon atoms.
Is particularly preferable, and 1 to 6 are particularly preferable. Alkyl group (R)
Specific examples of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t
-Butyl group, n-pentyl group, n-hexyl group, etc., and particularly preferred are methyl group and ethyl group.

C3-C20 cycloalkyl group (R)
Is preferably a cycloalkyl group having 3 to 10 carbon atoms. Specific examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopropyl group, a cyclohexyl group, and the like.

As the aryl group (R), a phenyl group,
Examples include groups such as a naphthyl group, and a phenyl group is preferable.
The aryl group having a substituent (R) refers to a group in which at least one hydrogen atom of the aryl group has been substituted with a substituent. Examples of the substituent include a nitro group, a methyl group, a methoxy group, and a halogen atom. No. Specific examples of the aryl group having a substituent include an (o-, m-, or p-) nitrophenyl group, an (o-, m-, or p-) methoxyphenyl group, an (o-, m-, or p-) chlorophenyl group,
(O-, m-, or p-) fluorophenyl group,
(2,3-, 2,4-, 2,5-, 2,6-, 3,4
-Or 3,5-) dinitrophenyl group and the like, and an (o-, m-, or p-) nitrophenyl group is preferable. As the aralkyl group (R), a benzyl group is preferable.

The substituted aralkyl group (R) is a group in which at least one hydrogen atom of the aralkyl group is substituted with a substituent, and the substituent is a substituted aryl group. The same groups as the groups are preferred. Examples of the substituted aralkyl group (R) include (o-, m-,
Or groups such as p-) nitrobenzyl.

As the carboxylic acid (formula 1), acetic acid, propionic acid, butanoic acid, benzoic acid, p-methoxybenzoic acid, o-methoxybenzoic acid, p-nitrobenzoic acid, o-
Nitrobenzoic acid, p-chlorobenzoic acid, o-chlorobenzoic acid, p-fluorobenzoic acid, o-fluorobenzoic acid,
Or 2,4-dinitrobenzoic acid is preferred. further,
In the carboxylic acid (formula 1), R is preferably an aryl group or an aryl group having a substituent, particularly preferably benzoic acid, p-nitrobenzoic acid or 2,4-dinitrobenzoic acid.

In the present invention, a carboxylic acid (formula 1) is reacted with propylene oxide. Since propylene oxide has an asymmetric carbon atom, optically active propylene oxide, that is, R-propylene oxide and S-propylene oxide may be present. The propylene oxide used in the present invention contains both of these,
Only one of them may be used. In the reaction of the present invention, the steric structure of the asymmetric carbon of propylene oxide is maintained as it is, and an optically active 1-acyloxy-2-propanol having the same steric structure is obtained.

That is, the present invention relates to a carboxylic acid (formula 1)
And optically active propylene oxide to react with 1-
In a method for producing acyloxy-2-propanol (formula 2), a method for producing 1-acyloxy-2-propanol is provided, wherein the reaction is performed in the presence of a metal complex catalyst (formula 3).

When the propylene oxide is an optically active propylene oxide, the resulting 1-acyloxy-2-propanol (formula 2) becomes an optically active 1-acyloxy-2-propanol (formula 2). That is,
When R-propylene oxide is used, (2R) -1
When -acyloxy-2-propanol uses S-propylene oxide, (2S) -1-acyloxy-2-propanol is generated. Optically active propylene oxide is disclosed in known literature (Science, vol. 277, p. 936 (199).
It can be easily synthesized according to a method such as the kinetic resolution method described in 7)).

(2R) -1-acyloxy-2-propanol or (2S) -1-acyloxy-2-propanol, that is, optically active 1-acyloxy-2-propanol
Propanol is represented by the following formula 4. CH ₃ C ^* H (OH) CH ₂ OCOR Formula 4 where the symbols in the formula have the following meanings. R: Same meaning as R in Formula 2. C ^* : asymmetric carbon atom.

The amount of propylene oxide used in the reaction is preferably from 10 to 1000 mol%, particularly preferably from 50 to 300 mol%, based on the carboxylic acid (formula 1).

In the present invention, the reaction between carboxylic acid (formula 1) and propylene oxide is carried out by a metal complex catalyst (formula 3).
It is characterized in that it is carried out in the presence of R ^{1 in} Formula 3
Represents an alkylene group having 1 to 20 carbon atoms, an alkylene group having 1 to 20 carbon atoms having a substituent, a cycloalkylene group having 3 to 20 carbon atoms, an arylene group, or an arylene group having a substituent.

When R ¹ is an alkylene group having 1 to 20 carbon atoms, examples thereof include a methylene group, an ethylene group, a trimethylene, a propylene group, a tetraethylene group and a pentaethylene group. When R ¹ is an alkylene group having 1 to 20 carbon atoms having a substituent, an alkylene group substituted with an alkyl group or an alkylene group substituted with an aryl group is preferable, and an alkylene group substituted with an aryl group is particularly preferable. Particularly, a 1,2-diphenylethylene group and the like are preferable. When R ¹ is a C 3-20 cycloalkylene group, a 1,2-cyclohexylene group is preferred. When R ¹ is an arylene group, a 1,2-phenylene group or a 1,3-phenylene group is preferred. When R ¹ is an arylene group having a substituent, a 3,6-di-t-butyl-1,2-phenylene group is preferred.

X ^{1 to} X ^{10 in} Formula 3 may be the same or different, and each represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group,
It represents an alkynyl group, a hydroxy group, an amino group, a nitro group, a carbamoyl group, a carboxyl group, or a silyl group which may be substituted. Here, examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom, and a fluorine atom and a chlorine atom are preferable. As the alkyl group, an alkyl group having 1 to 20 carbon atoms is preferable. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-butyl group and a t-butyl group. As the cycloalkyl group, a cycloalkyl group having 3 to 20 carbon atoms is preferable, and a cyclopentyl group and a cyclohexyl group are particularly preferable. The alkenyl group is preferably an alkenyl group having 2 to 20 carbon atoms, particularly preferably a vinyl group. As the alkynyl group, an alkynyl group having 2 to 20 carbon atoms is preferable, and an ethynyl group is particularly preferable.

M in the formula 3 is M ¹ (where M ¹ represents a divalent metal atom or a divalent metal ion), M ² -A ¹
(Where M ² is a divalent or trivalent metal atom, A
¹ represents a ligand. ) Or M ³ -A ² (where M
³ represents a trivalent metal ion, and A ² represents a counter ion. ).

As M ¹ (a divalent metal atom or divalent metal ion), Co ^II , Mn ^II , Ni ^II or these ions are preferable, and Co ^II is particularly preferable.

Examples of M ² (divalent metal atom or trivalent metal atom) in M ² -A include Co ^II , Mn ^II , Ni ^II ,
Co ^III , Mn ^III , Cr ^III , Ni ^III , Al ^{III and the} like are mentioned, and Co ^II or Co ^III is preferable. A ¹
Examples of (ligand) include an ether compound and an alcohol compound, and tetrahydrofuran and ethanol are preferable.

M ³ (trivalent metal ion) in M ³ -A ² includes Co ^III , Mn ^III , Cr ^III , Ni
^III , Al ^{III and the} like, and Co ^III is preferable. A
Examples of ² (counter ion) include a halogen anion and a carboxylate anion, and particularly preferably an anion (RCOO ⁻ ) of a carboxylic acid (formula 1) used in the reaction.

In the metal complex catalyst (formula 3), M is M ¹
(A divalent metal atom or a divalent metal ion), and particularly preferably M ¹ is a divalent metal atom.
It is particularly preferable that M ¹ is a divalent cobalt atom [Co ^II ].

The metal complex catalyst may be an optically active metal complex catalyst or an optically inactive metal complex catalyst. The optically inactive metal complex catalyst (formula 3) is a metal complex catalyst (formula 3) having a structure having no asymmetric center, asymmetric axis, or asymmetric surface, and N, N'-bis (salicylidene)
Ethylenediaminocobalt ^II [Co ^II (salen)], N,
N'-bis (salicylidene) -1,2-benzenediaminocobalt ^II [Co ^II (salphen)] and the like.

The optically active metal complex catalyst is a metal complex catalyst having a structure having an asymmetric center, an asymmetric axis or an asymmetric carbon atom (formula 3), wherein R ¹ is 1,2-cyclohexylene. And the like. When R ¹ is a 1,2-cyclohexylene group, the metal complex catalyst (formula 3) is
It can be optically active because it has an asymmetric axis. Examples of the optically active metal complex catalyst (formula 3) include (1R, 2R)-
N, N'-bis (3,5-di-tert-butylsalicylidene) -1,2-cyclohexanediaminocobalt ^II , (1S, 2S) -N, N'-bis (3,5-di-
(t-butylsalicylidene) -1,2-cyclohexanediaminocobalt ^II is preferred.

The metal complex catalyst (formula 3) of the present invention is described in known literature (Tetrahedron Letters, vol. 38, p. 773 (1997)), and a commercially available product can be easily obtained.

When an optically active metal complex catalyst is used as the metal complex catalyst (formula 3), R-propylene oxide or S-propylene oxide can react preferentially.
That is, the present invention provides an optically active 1-acyloxy-2 characterized by reacting a carboxylic acid (formula 1) with propylene oxide in the presence of an optically active metal complex catalyst.
-To provide a method for producing propanol.

The reaction of the present invention basically proceeds while maintaining the stereostructure of the asymmetric carbon in propylene oxide. Therefore, when propylene oxide is optically active, it is an optically active metal complex catalyst. However, an optically active metal complex may be used. When propylene oxide is optically inactive and an optically active compound is desired to be obtained, an optically active metal complex catalyst may be used. Whether the metal complex catalyst is optically active or optically inactive is used depending on whether or not the starting propylene oxide is optically active and whether or not the target compound is optically active. Can be changed.
The three-dimensional structure and type of the metal complex catalyst can be appropriately changed according to the reaction rate, the reaction yield, and the like.

The amount of the metal complex catalyst (formula 3) is preferably from 10 ^{-5 to} 100 mol%, particularly preferably from 0.001 to 10 mol%, based on the carboxylic acid (formula 1).

The reaction of the present invention is preferably carried out in the presence of a base, since the reaction rate is accelerated. The base is preferably an organic base, particularly preferably a trialkylamine, particularly preferably triethylamine or diisopropylethylamine. The amount of the organic base is preferably from 0 to 200 mol% with respect to the carboxylic acid (formula 1), particularly preferably 8 to 200 mol%.
0-130 mol% is preferred.

The reaction may be carried out in the presence of a reaction solvent or in the absence of a reaction solvent. When a reaction solvent is used, it is preferably selected from those not directly involved in the reaction in the present invention, and an organic solvent is preferable. Examples of the organic solvent include hydrocarbon solvents (eg, hexane, benzene, toluene, xylene, chlorobenzene, cyclohexane, etc.), chlorinated solvents (eg, dichloromethane, chloroform, dichloroethane, etc.),
Ether solvents (eg, diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether,
Ethylene glycol diethyl ether, diisopropyl ether, methyl-t-butyl ether, etc.). Organic solvents include dichloromethane, methyl-t
-Butyl ether, hexane, toluene or xylene are particularly preferred.

The amount of the reaction solvent is preferably from 0 to 2000 ml, more preferably from 0 to 120 ml, per mol of the carboxylic acid (formula 1).
0 ml is preferred. Reaction temperature is -20 ° C to + 100 ° C
Is preferable, and 0 ° C. to 30 ° C. is particularly preferable. The reaction time is preferably 0.5 to 100 hours, particularly 0.5 to 40 hours.
Time is preferred.

In the reaction of the present invention, 1-acyloxy-2-propanol (formula 2) is produced. In general, the reaction product is preferably subjected to a post-treatment to have a high purity. As the post-treatment, a method of extracting the reaction product after the reaction with an organic solvent and concentrating the organic solvent extract is preferable.

Specific examples of 1-acyloxy-2-propanol (formula 2) which is the target compound of the present invention include the following compounds. The following compounds are 2R-form, 2S-form
It may be any of a body or a mixture of a 2R form and a 2S form. 1- (p-nitrobenzoyloxy) -2-propanol, 1- (p-nitrobenzoyloxy) -2
-Propanol, 1-benzoyloxy-2-propanol, 1- (o-nitrobenzoyloxy) -2-propanol, 1- (m-nitrobenzoyloxy) -2-
Propanol, 1- (p-methoxybenzoyloxy)
-2-propanol.

1-acyloxy-2-propanol (formula 2) is a useful compound as a raw material or an intermediate of another compound. In particular, a quinolone antibacterial agent can be produced using the compound as an intermediate.

[0040]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples.

Example 1 Synthesis Example of 1- (p-Nitrobenzoyloxy) -2-propanol N, N'-bis (salicylidene) ethylenediaminocobalt ^II [M in the formula 3 was placed in a 200 ml glass reactor. C
o ^II , R ¹ is an ethylene group and X ^{1 to} X ¹⁰ are hydrogen atoms] 600 mg (2.1 mmol), p
10.0 g (60 mmol) of -nitrobenzoic acid and 40 ml of methyl-t-butyl ether were charged, and the mixture was stirred at room temperature under an air atmosphere for 2 hours. Methyl-t-butyl ether was distilled off under reduced pressure, and the reactor containing the dried brown solid was purged with nitrogen. 8.4 g (65 mmol) of diisopropylethylamine, 8.8 g (152 mmol) of optically inactive propylene oxide, and 40 ml of toluene were added to this reactor at room temperature, and the mixture was stirred at room temperature under a nitrogen atmosphere for 10 hours. At this point, the conversion of p-nitrobenzoic acid was 97%.
Met.

Further, 50 ml of water and 50 ml of methyl-t-butyl ether were added, and the mixture was stirred and allowed to stand still for liquid separation. The upper organic phase was washed successively with a saturated aqueous solution of sodium hydrogen carbonate (30 ml), 1N hydrochloric acid (30 ml) and water (30 ml), dried over 3 g of magnesium sulfate, filtered, concentrated, and concentrated to remove the solvent. The remaining pale yellow solid was recrystallized from toluene-hexane, and 11.0 g of 1- (p-nitrobenzoyloxy) -2-propanol (49 m
mol). The yield based on p-nitrobenzoic acid was 81%.

Example 2 Synthesis Example of (2R) -1- (p-nitrobenzoyloxy) -2-propanol In a 200 ml glass reactor, 600 mg of N, N'-bis (salicylidene) ethylenediaminocobalt ^{II was} placed.
(2.1 mmol), 10.0 g of p-nitrobenzoic acid
(60 mmol), 40 m of methyl-t-butyl ether
and stirred at room temperature under an air atmosphere for 2 hours. Methyl-t-butyl ether was distilled off under reduced pressure, and the reactor containing the dried brown solid was purged with nitrogen. 8.4 g of diisopropylethylamine (65 mm) was added to the reactor at room temperature.
ol), (R) -propylene oxide (optical purity 99.
8% ee) 5.2 g (90 mmol), toluene 40 m
and stirred at room temperature for 8 hours under a nitrogen atmosphere. At this point, the conversion of p-nitrobenzoic acid was 89%.

Further, 50 ml of water and 50 ml of methyl-t-butyl ether were added, and the mixture was stirred and allowed to stand still for liquid separation. The upper organic phase was washed successively with a saturated aqueous solution of sodium hydrogen carbonate (30 ml), 1N hydrochloric acid (30 ml) and water (30 ml), dried over 3 g of magnesium sulfate, filtered, concentrated, and concentrated to remove the solvent. The remaining pale yellow solid was recrystallized from toluene-hexane to give (2R) -1- (p-nitrobenzoyloxy) -2-propanol 9.7 g.
(43 mmol) was obtained. The yield based on p-nitrobenzoic acid was 72%. The light intensity is [α] _D ²⁰
-17.5 ° (c = 1, methanol). In addition,
The optical rotation of (2R) -1- (p-nitrobenzoyloxy) -2-propanol having an optical purity of 99.8% ee is [α] _D ²⁵ -18.2 ° (c = 1, methanol).
(Value described in JP-A-3-20873).

Example 3 Synthesis Example of (2R) -1- (p-nitrobenzoyloxy) -2-propanol (S, S) -N, N 'was placed in a 200 ml glass reactor.
-Bis (3,5-di-t-butylsalicylidene) -1,
2-cyclohexanediaminocobalt ^II [M in Formula 3 is C
o ^II , R ¹ is a 1,2-cyclohexylene group, X ³ , X ⁵ , X ⁸ and X ¹⁰ are t-butyl groups, X ¹ , X ² , X ⁴ , X ⁶ , X ⁷ and X ⁹ being hydrogen atoms] 363 mg (0.6 mmol), p-
Nitrobenzoic acid 10.0 g (60 mmol), methyl-
40 ml of t-butyl ether was charged and stirred at 5 ° C. for 2 hours under an air atmosphere. The solvent, methyl-t-butyl ether, was distilled off under reduced pressure, and the reactor containing the dried brown solid was purged with nitrogen. At room temperature, 8.4 g (65 mmol) of diisopropylethylamine, 7.0 g (120 mmol) of propylene oxide,
After adding 0 ml, the mixture was stirred at 5 ° C. for 6 hours under a nitrogen atmosphere. At this point, the conversion of p-nitrobenzoic acid was 84%.

50 ml of water cooled to 5 ° C., methyl-t-
After adding 50 ml of butyl ether and stirring, the mixture was allowed to stand and liquid separation was performed. The upper organic phase was washed with a saturated aqueous sodium hydrogen carbonate solution (30 ml), 1N hydrochloric acid (30 ml), and water (30 ml).
, And after drying and filtration by adding 3 g of magnesium sulfate, the mixture was concentrated and the solvent was distilled off. The remaining pale yellow solid was recrystallized from toluene-hexane to give (2R) -1-
4.9 g (22 mmol) of (p-nitrobenzoyloxy) -2-propanol were obtained. The yield based on p-nitrobenzoic acid was 37%. [Α] _D ²⁰ -1
6.1 ° (c = 1, methanol). Optical purity 9
The optical rotation of (2R) -1- (p-nitrobenzoyloxy) -2-propanol with 9.8% ee is [α] _D ²⁵
-18.2 ° (c = 1, methanol) (JP-A-3-20
4873).

[0047]

According to the method of the present invention, 1-acyloxy-2-yl is obtained in a higher yield and a simpler method than the conventional method.
Propanol can be produced. Further, by using optically active propylene oxide or using an optically active metal complex catalyst, an optically active 1- as a target compound can be obtained.
Acyloxy-2-propanol can be obtained.
Since the production method of the present invention has excellent stereoselectivity, the obtained optically active 1-acyloxy-2-propanol has a high yield and is also high in optical purity, so that complicated optical resolution is required. There are no benefits.

Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C07C 201/12 C07C 201/12 205/57 205/57 // C07B 61/00 300 C07B 61/00 300 C07M 7:00

Claims (7)

[Claims] A carboxylic acid represented by the following formula 1 and propylene
To react with 1-acid represented by the following formula 2.
In a method for producing ruoxy-2-propanol,
The reaction is performed in the presence of a metal complex catalyst represented by the following formula 3.
1-acyloxy-2-propanol
Manufacturing method. Embedded imageHowever, the symbols in the formula have the following meanings. R: an alkyl group having 1 to 20 carbon atoms, a C 3 to 20 carbon atom
Cycloalkyl group, aryl group, aryl having a substituent
Group, aralkyl group, or alkyl group having a substituent
Le group. R¹ : Having an alkylene group having 1 to 20 carbon atoms and a substituent
C1-20 alkylene group, C3-20 cycle
Having a loalkylene group, an arylene group, or a substituent
Arylene group. X¹ ~ X^Ten: May be the same or different
Hydrogen, halogen, alkyl, cycloal
Kill group, alkenyl group, alkynyl group, hydroxy group,
Amino group, nitro group, carbamoyl group, carboxyl
Or a silyl group which may be substituted. M: M¹ (However, M¹ Is a divalent metal atom or divalent metal
Indicates an ion. ), M ^Two -A¹ (However, M^Two Is divalent
Group atom or trivalent metal atom, A¹ Represents a ligand. ),
Or M^Three -A^Two (However, M^Three Is a trivalent metal ion, A
^Two Represents a counter ion. ). 2. The method according to claim 1, wherein the propylene oxide is an optically inactive propylene oxide. 3. The method according to claim 1, wherein the propylene oxide is an optically active propylene oxide. 4. The method according to claim 1, wherein the metal complex catalyst is an optically active metal complex catalyst. 5. The method of claim 1, wherein the 1-acyloxy-2-propanol is
The production method according to claim 3 or 4, wherein the production method is an optically active 1-acyloxy-2-propanol. 6. The method according to claim 1, wherein M is divalent cobalt. 7. The production method according to claim 1, wherein the reaction is carried out in the presence of a base.