JP3345637B2 - Method for producing hydroxy compound and catalyst for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a hydroxy compound by selectively removing an acetyl group or a formyl group from an acetate or formate, and a catalyst used in the production method.

[0002]

2. Description of the Related Art When producing a hydroxy compound using an ester as a raw material, a method is known in which the ester is hydrolyzed in the presence of an acid or a base. However, in this method, since a mineral acid or an alkali is used, waste liquid treatment has been a major problem.

[0003]

Accordingly, the present invention provides
An object of the present invention is to provide a method for producing a hydroxy compound and a catalyst used in the production method, which have no problem of waste liquid treatment.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in view of the above problems, and as a result, have found that the above problems can be solved by using a specific copper salt solid acid catalyst. Reached. That is, the present invention relates to: (1) a compound represented by the formula (I): ROCOCH ₃ (where R is an aliphatic alcohol residue or an aromatic alcohol)
Indicates the residue. ) In the presence of a solid acid catalyst,
Reaction with aliphatic alcohol to remove acetyl group
Process for producing a hydroxy compound by
Hydroxy, characterized by using copper chloride as a medium
Processes for the preparation of compounds, (2) (II) ROCOH (wherein, R represents an aliphatic alcohol residue or an aromatic alcohol
Indicates the residue. ) In the presence of a solid acid catalyst,
Reaction with aliphatic alcohol to remove acetyl group
Process for producing a hydroxy compound by
Hydroxy, characterized by using copper chloride as a medium
(3) The method for producing a compound, wherein the copper chloride is anhydrous cupric chloride.
The method for producing a hydroxy compound according to the above (1) or ( 2), wherein I will provide a
Things.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION
Ter is an acetic acid ester represented by the above formula (I) or a compound represented by the formula
It is a formate represented by (II). Formula (I) and
The alcohol residue represented by R in (II) is an aliphatic group
Or any of aromatic groups. Aliphatic alcohol residue
The group may be saturated or unsaturated, and may be linear, branched, or cyclic.
Any shape may be used. Preferably primary or secondary alkyl
And preferably has 1 to 20 carbon atoms, more preferably
Or 6-18. For example, n-
Octadecyl, n-decyl, isohexyl, neopentine
, S-butyl, hexenyl, heptynyl and the like.
It is. In addition, as the cyclic one, for example, cyclohexyl
, Cyclopentyl, cyclobutyl, decahydronaphthy
And cyclohexenyl. Represented by R
The aromatic alcohol residue preferably has 6 to 20 carbon atoms.
For example, phenyl, benzyl, phenethyl, naph
Tyl, phenanthryl, naphthacenyl, etc.
You.

These alcohol residues may have a substituent as long as the substituent does not inhibit the reaction in the present invention. Examples of such a substituent include an alkyl group which may be further substituted or Aryl group, oxygen, nitrogen, heterocyclic group containing a hetero atom such as sulfur, hydroxyl group, alkoxy group, aryloxy group, acyl group (formyl, acetyl etc.), carboxyl group, alkoxycarbonyl group,
Carbamoyl group, halogen atom, nitro group, amino group,
Acylamino group, azo group, cyano group, mercapto group, alkylthio group, arylthio group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group,
An arylsulfonyl group, a sulfo group, a sulfino group and the like can be mentioned. R in the formulas (I) and (II) represents an acyloxy group (—OCOCH ₃ or —O
In addition to COH), it may have one or more acyloxy groups as substituents, which may be the same or different from the acyloxy groups shown in the formula. Further, it may have a residue of a sugar, steroid, terpene, alkaloid, peptide, protein, or the like as a substituent.

In the present invention, the above formula (I) or (II)
The aliphatic alcohol to be reacted with the compound represented by
It is preferably a saturated aliphatic alcohol, and preferably has 1 to 8, more preferably 3 or 4, carbon atoms. Examples of the aliphatic alcohol that can be used in the present invention include 1-propanol, 1-butanol, isobutyl alcohol, and the like.

In the present invention, the above-mentioned acetate acetate
Ter or formate and aliphatic alcohol
The reaction is performed in the presence of a catalyst. The catalyst of the present invention comprises a solid acid
Copper chloride having the following properties: Such a copper salt
For example, anhydrous cupric chloride, cupric chloride dihydrate
Which is preferably used. The amount of the catalyst of the present invention can be appropriately determined, but is usually represented by the formula (I) in a weight ratio.
Or 0.2 to 1, based on the compound 1 represented by the formula (II),
Preferably it is 0.3-0.6. This is reacted with the compound of the formula (I) or the formula (II) and an aliphatic alcohol by heating and stirring. The reaction temperature is preferably from 60 to 130.
° C, more preferably 90 to 100 ° C, and the reaction time is usually 4 to 30 hours. In the present invention, the catalyst can be removed by performing a simple filtration operation after the reaction,
By removing the solvent from the obtained filtrate, the desired hydroxy compound can be obtained without particularly requiring an extraction operation or the like.

This reaction can be carried out in a solvent or without a solvent, and is preferably carried out in a solvent. When a solvent is used, the solvent may be used by using an excess of the aliphatic alcohol, or a solvent other than the aliphatic alcohol may be used.As the solvent other than the aliphatic alcohol, for example,
Hydrocarbon solvents (hexane, heptane, etc.), ether solvents (tetrahydrofuran, dioxane, etc.), halogen solvents (chloroform, carbon tetrachloride, etc.), aromatic solvents (benzene, toluene, etc.), aprotic polar solvents ( Acetonitrile, dimethylformamide, etc.) can be used.

When the reaction is carried out in this manner, a transesterification reaction proceeds between the ester and the aliphatic alcohol, and the ester represented by the formula (I) or (II) is converted into an acyl group (acetyl group, formyl group). ) Is eliminated to form a hydroxy compound (ROH). After the reaction, the target hydroxy compound can be obtained by removing the solvent by filtration or the like, and performing separation and purification as necessary.

According to the production method of the present invention, in the compound represented by the formula (I) or (II), the acetyl group and the formyl group bonded to the oxygen atom are eliminated, but the aromatic acyl group is eliminated. Do not release. Further, an acylamide group in which an acyl group is bonded to a nitrogen atom (acetic acid amide group (—NH—COC
Neither the acyl group of H ₃ ) nor the like is eliminated. Therefore, when the method of the present invention is performed on a compound having an aromatic acyl group or an acylamide group in a molecule together with an acetyl group or a formyl group, only an acetyl group or a formyl group bonded to an oxygen atom is selectively eliminated. be able to. Further, when an ester compound having a cyano group or a carbamoyl group is hydrolyzed by a conventional method, these substituents are converted to a carboxyl group, but according to the method of the present invention, the cyano group and the carbamoyl group are not changed. Can be left. Therefore, according to the method of the present invention, it is possible to produce a hydroxy compound (for example, a hydroxy compound having an aromatic acyl group, an acylamide group, a cyano group, or the like as a substituent) that could not be obtained by conventional ester hydrolysis. It is possible. It is considered that such selective hydrolysis can be performed because the hydrolysis reaction condition of the present invention is mild, and thus the carbon at the α-position of the carbonyl group is easily sterically affected.

[0012]

Next, the present invention will be described in more detail with reference to examples. Example 1 Benzyl acetate (0.132 g), anhydrous cupric chloride (0.
035 g), 1-propanol (5 ml)
Stirred at 92 ° C. for 7 hours. After the reaction, the catalyst was removed by filtration, and the solvent was removed from the filtrate under reduced pressure. The residue was purified by silica gel chromatography to give 0.086 g (91%) of benzyl alcohol as a colorless oil. The IR spectrum and NMR spectrum of the product corresponded to the spectra described in the spectrum collection of Aldrich, and it was confirmed that the product was benzyl alcohol.

Comparative Example 1 The operation was carried out in exactly the same manner as in Example 1 except that the reaction was carried out without using anhydrous cupric chloride. As a result, the reaction did not proceed at all.

Examples 2 to 13 Reactions were carried out in the same manner as in Example 1 except that various esters shown in Tables 1 and 2 were used instead of benzyl acetate, and various hydroxy compounds were synthesized. The compounds obtained and the yields are shown in Tables 1 and 2. The physical properties of the products and the MS, IR, and NMR spectra of the products in each Example were consistent with the hydroxy compounds shown in Tables 1 and 2. In addition IR,
When the NMR spectrum was compared and identified with the spectrum described in the spectrum collection of Aldrich, it was confirmed that the compound was a hydroxy compound shown in Tables 1 and 2. Almost the same results were obtained when the reaction was carried out using a solid acid catalyst other than anhydrous cupric chloride.

[0015]

[Table 1]

[0016]

[Table 2]

[0017]

EFFECTS OF THE INVENTION In the production method of the present invention, elimination of an acyl group is carried out selectively with respect to a specific acyl group bonded to an oxygen atom, so that an acetate ester having another acyl group or the like in one molecule. Alternatively, when a formate is used, a hydroxy compound that cannot be obtained by conventional hydrolysis can be produced. Further, if the catalyst of the present invention is used, there is no problem of waste liquid treatment that occurs when a mineral acid or an alkali is used as a catalyst, and it is possible to hydrolyze an acetate ester or a formate ester in a high yield and to obtain a target hydroxy compound. Can be manufactured at low cost. Furthermore, this catalyst has high catalytic activity,
It has an excellent effect that post-treatment after the reaction is facilitated.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI C07C 33/22 C07C 33/22 35/08 35/08 51/367 51/367 65/10 65/10 67/29 67/29 67/31 67/31 69/78 69/78 69/84 69/84 69/94 69/94 201/12 201/12 205/44 205/44 231/12 231/12 233/25 233/25 235 / 60 235/60 253/30 253/30 255/53 255/53 C07H 15/203 C07H 15/203 // C07B 61/00 300 C07B 61/00 300 (56) References JP-A-9-25266 (JP, A) Jonathan Wright, A Convergent Synthesis of Triquinane Sesterterpens. Enantioselective Synthesis of (−)-Retige ranic Ac, J. et al. Am. Chem. Soc. 1988, Vol. 110, pp. 5806-5817 (58) Fields investigated (Int.Cl. ⁷ , DB name) C07C 27/02 B01J 27/122 C07B 41/02 C07C 29/128 C07C 31/125 C07C 33/22 C07C 35/08 C07C 51 / 367 C07C 65/10 C07C 67/29 C07C 67/31 C07C 69/78 C07C 69/84 C07C 69/94 C07C 201/12 C07C 205/44 C07C 231/12 C07C 233/25 C07C 235/60 C07C 253/60 C07C 255/53 C07H 15/203 C07B 61/00 300 CA (STN) CASREAT (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. A compound of the formula (I) ROCOCH _{3 wherein} R is an aliphatic alcohol residue or an aromatic alcohol.
Indicates the residue. ) In the presence of a solid acid catalyst,
Reaction with aliphatic alcohol to remove acetyl group
Process for producing a hydroxy compound by
Hydroxy, characterized by using copper chloride as a medium
A method for producing a compound. 2. A compound of the formula (II): ROCOH wherein R is an aliphatic alcohol residue or an aromatic alcohol.
Indicates the residue. ) In the presence of a solid acid catalyst,
Reaction with aliphatic alcohol to remove acetyl group
Process for producing a hydroxy compound by
Hydroxy, characterized by using copper chloride as a medium
A method for producing a compound. 3. The method according to claim 1, wherein the copper chloride is anhydrous cupric chloride.
The hydroxy compound according to claim 1 or 2,
Production method.