JPH0920728A - Carbonate compound and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a new readily handleable carbonate compound useful as a protecting agent for especially hydroxyl group, further mercapto, amino groups, etc., and an active esterifying agent for carboxyl group without causing side reaction. SOLUTION: This carbonate compound of formula I (R<1> is an alkyl, an aryl, an alkenyl, etc.; R<2> is an alkyl; R<3> is an alkyl, an alkoxy, an aryl, an aralkyl, etc.), e.g. 4-t-butoxycarbonyloxy-3-penten-2-one. The compound of formula I is obtained by reacting, e.g. a carbonyl compound of formula II with a dicarbonate compound of formula III in the presence of a base.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention is a novel carbonate compound which is particularly useful as a protective agent for hydroxyl groups, and is also useful as a protective agent for mercapto groups, amino groups, etc., and as an active esterifying agent for carboxyl groups. Regarding

[0002]

2. Description of the Related Art At present, as carbonate type hydroxyl group protecting agents which are widely used, acid halide type protecting agents represented by benzyloxycarbonyl chloride and di-t-butyl dicarbonate represented by di-t-butyl dicarbonate. Mention may be made of carbonate type protective agents.

[0003]

However, since the acid halide type protective agent has the property of reacting with moisture in the air to generate hydrochloric acid gas, it is necessary to handle it with extreme caution. However, the dicarbonate-type protective agent has a problem in that, when it reacts with alcohol, a carbonate compound consisting of two molecules of alcohol as a raw material is by-produced. Therefore, it has been strongly desired to develop a new hydroxyl-protecting group that is easy to handle and can suppress side reactions as much as possible.

[0004]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that a carbonate compound represented by the following general formula is an excellent hydroxyl group protecting agent having the above properties. As a result, they have completed the present invention.

That is, the present invention provides the following general formula (I)

[0006]

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(Wherein R ₁ is an alkyl group, an aryl group which may have a substituent, an alkenyl group or an aralkyl group which may have a substituent, R ₂ is an alkyl group, and R ₃ Is an alkyl group, an alkoxy group, an aryl group which may have a substituent, an aralkyl group which may have a substituent, an aryloxy group which may have a substituent, an aralkyl which may have a substituent. An oxy group or an amino group which may have a substituent, and R ₂ and R ₃ may together form a ring.) And a method for producing the same.

In the above general formula (I), R ₁ represents an alkyl group, an aryl group which may have a substituent, an alkenyl group or an aralkyl group which may have a substituent. The alkyl group may be linear, branched or cyclic, and the carbon number thereof is not particularly limited. In general, an alkyl group having 1 to 8 carbon atoms is suitable because of easy availability of raw materials. Specific examples of suitable alkyl groups in the present invention include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, t-butyl group, iso-butyl group. Group, t-amyl group and the like.

The aryl group which may have a substituent is not particularly limited in carbon number, but preferably has 6 to 10 carbon atoms from the viewpoint of easy availability of raw materials. As the substituent, the alkyl group as described above is preferable. Specific examples of such an aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group and a naphthyl group.

The number of carbon atoms of the alkenyl group is not particularly limited, but it is preferably one having 2 to 5 carbon atoms from the viewpoint of easy availability of raw materials. Specific examples of the alkenyl group include:
A vinyl group, an allyl group, a 1-propenyl group, a 1-butenyl group and the like can be mentioned. Further, the aralkyl group which may have a substituent is not particularly limited in the number of carbon atoms,
The carbon number is preferably 7 to 11 from the viewpoint of easy availability of raw materials. As the substituent, the alkyl group as described above is preferable. Specific examples of such an aralkyl group include:
Examples thereof include a benzyl group, a methylbenzyl group and a phenethyl group.

In the general formula (I), R ₂ represents an alkyl group. The alkyl group may be linear, branched or cyclic, and the carbon number thereof is not particularly limited. In general, an alkyl group having 1 to 8 carbon atoms is suitable because of easy availability of raw materials. Specific examples of suitable alkyl groups in the present invention include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, t-butyl group, iso-butyl group. Group, t-amyl group and the like.

In the general formula (I), R ₃ is
Alkyl group, alkoxy group, aryl group which may have a substituent, aralkyl group which may have a substituent, aryloxy group which may have a substituent, aralkyloxy which may have a substituent A group or an amino group which may have a substituent is shown. The alkyl group may be linear, branched or cyclic, and the carbon number thereof is not particularly limited. In general, an alkyl group having 1 to 8 carbon atoms is suitable because of easy availability of raw materials. Specific examples of suitable alkyl groups in the present invention include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, t-butyl group, iso-butyl group. Group, t-amyl group and the like.

The alkoxy group may also be linear, branched or cyclic, and the carbon number thereof is not particularly limited. Generally, the number of carbon atoms is 1 due to easy availability of raw materials.
It is preferable that the alkoxy group is ~ 8. Specific examples of suitable alkoxy groups in the present invention include methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, t-
Butoxy group and the like.

The aryl group which may have a substituent is not particularly limited in carbon number, but preferably has 6 to 10 carbon atoms from the viewpoint of easy availability of raw materials. As the substituent, the alkyl group as described above is preferable. Specific examples of such an aryl group include a phenyl group and a naphthyl group.

The number of carbon atoms of the aralkyloxy group which may have a substituent is not particularly limited, but it is preferable that the number of carbon atoms is 7 to 11 in view of easy availability of raw materials. As the substituent, the alkyl group as described above is preferable. Specific examples of such an aralkyloxy group include a benzyloxy group, a methylbenzyloxy group and a phenethyloxy group.

The aryloxy group which may have a substituent is not particularly limited in carbon number, but preferably has 6 to 10 carbon atoms from the viewpoint of easy availability of raw materials. As the substituent, the alkyl group as described above is preferable. Specific examples of such an aryloxy group include a phenyloxy group, a methylphenyloxy group, an ethylphenyloxy group and a naphthyloxy group.

The aralkyloxy group which may have a substituent is not particularly limited in the number of carbon atoms, but preferably has 7 to 11 carbon atoms from the viewpoint of easy availability of raw materials. As the substituent, the alkyl group as described above is preferable. Specific examples of such an aralkyloxy group include a benzyloxy group, a methylbenzyloxy group and a phenethyloxy group.

Further, the amino group which may have a substituent is not particularly limited, but it is a primary amine and a secondary or tertiary alkylamino group having 1 to 10 carbon atoms because of easy availability of raw materials. Preferably there is. Specific examples of the amino group which may have a substituent include an unsubstituted amino group, a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group and a diisopropylamino group.

Further, R ₂ and R ₃ may be joined together to form a ring. The ring size and the like are not particularly limited, but a cyclic compound having a structure represented by the following general formula (IV) is preferably used.

[0020]

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(However, n is an integer of 2 to 7) Further, in consideration of easiness of synthesis and the like, a cyclic compound having a structure represented by the following formula (V) is preferably used.

[0022]

[Chemical 6]

Specific examples of the carbonate compound of the present invention represented by the general formula (I) include 4-t-butoxycarbonyloxy-3-penten-2-one and 4-methoxycarbonyloxy-3-pentene- 2-on, 4
-Ethoxycarbonyloxy-3-penten-2-one, 4-iso-propoxycarbonyloxy-3-penten-2-one, 4-phenyloxycarbonyloxy-3-penten-2-one, 4-allyloxycarbonyloxy -3-Penten-2-one, 4-benzyloxycarbonyloxy-3-penten-2-one, 3-
methyl t-butoxycarbonyloxy-2-butenoate,
Methyl 3-methoxycarbonyloxy-2-butenoate,
Methyl 3-ethoxycarbonyloxy-2-butenoate,
Methyl 3-iso-propoxycarbonyloxy-2-butenoate, methyl 3-phenyloxycarbonyl-2-butenoate, methyl 3-benzyloxycarbonyl-2-butenoate, methyl 3-allyloxycarbonyloxy-2-butenoate , 3-t-butoxycarbonyloxy-2
-Ethyl butenoate, 3-methoxycarbonyloxy-2
-Ethyl butenoate, 3-ethoxycarbonyloxy-2
-Ethyl butenoate, ethyl 3-iso-propoxycarbonyloxy-2-butenoate, ethyl 3-phenyloxycarbonyl-2-butenoate, ethyl 3-benzyloxycarbonyl-2-butenoate, 3-allyloxycarbonyloxy- Ethyl 2-butenoate, phenyl 3-t-butoxycarbonyloxy-2-butenoate, phenyl 3-methoxycarbonyloxy-2-butenoate, phenyl 3-ethoxycarbonyloxy-2-butenoate, 3-is.
Phenyl o-propoxycarbonyloxy-2-butenoate, phenyl 3-phenyloxycarbonyl-2-butenoate, phenyl 3-benzyloxycarbonyl-2-butenoate, phenyl 3-allyloxycarbonyloxy-2-butenoate, 3 -T-butoxycarbonyloxy-2
-Benzyl butenoate, 3-methoxycarbonyloxy-
Benzyl 2-butenoate, benzyl 3-ethoxycarbonyloxy-2-butenoate, benzyl 3-iso-propoxycarbonyloxy-2-butenoate, benzyl 3-phenyloxycarbonyl-2-butenoate, 3-benzyloxycarbonyl- Benzyl 2-butenoate, 3-allyloxycarbonyloxy-2-benzyl benzylate, 3-
t-butoxycarbonyloxy-2-butenoic acid amide,
3-methoxycarbonyloxy-2-butenoic acid amide,
3-ethoxycarbonyloxy-2-butenoic acid amide,
3-iso-propoxycarbonyloxy-2-butenoic acid amide, 3-phenyloxycarbonyl-2-butenoic acid amide, 3-benzyloxycarbonyl-2-butenoic acid amide, 3-allyloxycarbonyloxy-2-butenoic acid amide , N-methyl-3-t-butoxycarbonyloxy-2-butenoic acid amide, N-methyl-3-methoxycarbonyloxy-2-butenoic acid amide, N-methyl-3-ethoxycarbonyloxy-2-butenoic acid amide , N-methyl-3-iso-propoxycarbonyloxy-2-butenoic acid amide, N-methyl-3-phenyloxycarbonyl-2-butenoic acid amide, N-methyl-
3-benzyloxycarbonyl-2-butenoic acid amide,
N-methyl-3-allyloxycarbonyloxy-2-
Butenoic acid amide, N, N-dimethyl-3-t-butoxycarbonyloxy-2-butenoic acid amide, N, N-dimethyl-3-methoxycarbonyloxy-2-butenoic acid amide, N, N-dimethyl-3- Ethoxycarbonyloxy-2-butenoic acid amide, N, N-dimethyl-3-is
o-Propoxycarbonyloxy-2-butenoic acid amide, N, N-dimethyl-3-phenyloxycarbonyl-2-butenoic acid amide, N, N-dimethyl-3-benzyloxycarbonyl-2-butenoic acid amide, N, N-dimethyl-3-allyloxycarbonyloxy-2-butenoic acid amide, N, N-diethyl-3-t-butoxycarbonyloxy-2-butenoic acid amide, N, N-diethyl-3-methoxycarbonyloxy-2 -Butenoic acid amide, N, N-diethyl-3-ethoxycarbonyloxy-2-butenoic acid amide, N, N-diethyl-3-iso
-Propoxycarbonyloxy-2-butenoic acid amide,
N, N-diethyl-3-phenyloxycarbonyl-2
-Butenoic acid amide, N, N-diethyl-3-benzyloxycarbonyl-2-butenoic acid amide, N, N-diethyl-3-allyloxycarbonyloxy-2-butenoic acid amide, 1-t-butoxycarbonyloxy- 2-cyclohexen-3-one, 1-methoxycarbonyloxy-2-cyclohexen-3-one, 1-ethoxycarbonyloxy-2-cyclohexen-3-one, 1-is
o-Propoxycarbonyloxy-2-cyclohexen-3-one, 1-phenyloxycarbonyloxy-2
-Cyclohexen-3-one, 1-benzyloxycarbonyloxy-2-cyclohexen-3-one, 1-allyloxycarbonyl-2-cyclohexen-3-one, 1-t-butoxycarbonyloxy-2-cyclopentene-3- On, 1-methoxycarbonyloxy-2
-Cyclopenten-3-one, 1-ethoxycarbonyloxy-2-cyclopenten-3-one, 1-iso-
Propoxycarbonyloxy-2-cyclopentene-3
-One, 1-phenyloxycarbonyloxy-2-cyclopenten-3-one, 1-benzyloxycarbonyloxy-2-cyclopenten-3-one, 1-allyloxycarbonyl-2-cyclopenten-3-one, etc. You can

The structure of the compound represented by the general formula (I) can be confirmed by the following means. (1) by measuring the ¹ H- nuclear magnetic resonance spectra ⁽¹ H-NMR), it is possible to know the binding mode of the hydrogen atoms present in the compounds represented by the general formula (I).

(2) By measuring the infrared absorption spectrum (IR), the characteristic absorption derived from the functional group of the compound represented by the general formula (I) can be observed, and particularly 1700 cm ^-1. Characteristic absorption derived from a carbonyl group can be observed in the vicinity.

(3) Mass spectrum (MS) is measured,
A molecular ion peak of the general formula (I) (hereinafter abbreviated as M ⁺ ) is observed. Therefore, the molecular weight can be determined.

(4) By the elemental analysis, the weight% of oxygen can be calculated by subtracting the sum of the weight% of carbon, hydrogen, nitrogen, and each element from 100. Therefore, the composition formula can be determined.

The compound represented by the general formula (I) has the following general formula (II)

[0029]

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(Wherein R ₂ is an alkyl group, R ₃ is an alkyl group, an alkoxy group, an aryl group which may have a substituent, an aralkyl group which may have a substituent, and a substituent which may have a substituent). It is an optionally substituted aryloxy group, an optionally substituted aralkyloxy group or an optionally substituted amino group, and R ² and R ³ may be taken together to form a ring. ) And a general formula (II
I)

[0031]

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(Wherein R ₁ is an alkyl group, an aryl group which may have a substituent, an alkenyl group or an aralkyl group which may have a substituent) and a dicarbonate compound as a base. It can be obtained by reacting in the presence. (Hereinafter, abbreviated as reaction (A).) As the carbonyl compound used in the reaction (A), the compound represented by the general formula (II) can be used without any limitation.

Specific examples of the carbonyl compound preferably used in the reaction (A) include 2,4-pentanedione, methyl 3-oxobutanoate, ethyl 3-oxobutanoate, isopropyl 3-oxobutanoate, and 3 -Phenyl oxobutanoate, benzyl 3-oxobutanoate, 3
-Oxobutanoic acid amide, N-methyl-3-oxobutanoic acid amide, N, N-dimethyl-3-oxobutanoic acid amide, N, N-diethyl-3-oxobutanoic acid amide,
2,4-hexanedione, methyl 3-oxopentanoate, 3-oxopentanoic acid amide, 1,3-cyclopentanedione, 1,3-cyclohexanedione and the like can be mentioned.

As the dicarbonate used in the reaction (A), the compound represented by the general formula (III) can be used without any limitation. Specific examples of these compounds include di-t-butyl dicarbonate,
Examples thereof include di-t-amyl dicarbonate, dimethyl dicarbonate, diethyl dicarbonate, di-iso-propyl dicarbonate, diallyl dicarbonate and dibenzyl dicarbonate.

The amount of these dicarbonates to be used is not limited in any way, but if it is used in a too large amount, it is not economically advantageous and it hinders the purification of the product. II-) to the carbonyl compound represented by 0.9-3.0 times equivalent, and further 1.0-
It is preferably in the range of 2.0 times equivalent.

The catalyst used in this reaction is
Usual bases can be used without any restrictions. Specific examples thereof include pyridine, 4-N, N-dimethylaminopyridine, 4-N, N-diethylaminopyridine and 4-
Organic aromatic tertiary amines such as piperidinopyridine, 4-pyrrolidinopyridine, N-methylimidazole; tributylamine, methyldiisopropylamine, N, N,
N ', N'-tetramethylethylenediamine, N, N,
N'N'-tetraethylethylenediamine, N, N,
Organic aliphatic tertiary amines such as N ′, N′-tetramethylpropylenediamine; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate and the like Examples thereof include alkali metal carbonates.

In the reaction (A), the amount of the base used is not particularly limited, but if it is used in an excessively large amount, the reaction system becomes colored and it is difficult to separate it from the product. Therefore, it is 0.0001 to 1 times equivalent to the carbonyl compound represented by the general formula (II), and more preferably 0.1.
It is preferably in the range of 0005 to 0.8 times equivalent.

The reaction (A) proceeds efficiently both in the absence of solvent and in organic solvents. When using an organic solvent,
Generally, a general organic solvent can be used without any limitation.

Specific examples of the solvent which can be preferably used in the reaction (A) include aliphatic hydrocarbons such as hexane, heptane, octane and cyclohexane; benzene,
Aromatic hydrocarbons such as toluene and xylene; halogenated aliphatic hydrocarbons such as carbon tetrachloride, chloroform, methylene chloride and 1,2-dichloroethane; tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, etc. Ethers; Nitriles such as acetonitrile; Esters such as ethyl acetate, propyl acetate, butyl acetate; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; Carbonates such as dimethyl carbonate; Amides such as dimethylformamide, dimethylacetamide Dimethyl sulfoxide and the like can be mentioned. Even if these organic solvents are used alone, 2
It is safe to mix more than one type.

The reaction temperature is preferably in the range of -20 to 70 ° C, more preferably -10 to 50 ° C in order to maintain an appropriate reaction rate and prevent decomposition of the dicarbonate at a high temperature. The reaction can be carried out under any of atmospheric pressure, increased pressure and reduced pressure, and the time required for the reaction varies depending on the reaction temperature, the type of carbonyl compound and the type of organic solvent, but is usually 0.1 to 60. Time is enough.

The method for isolating the carbonate compound represented by the general formula (I) obtained by the reaction (A) is not particularly limited. For example, the reaction solvent is distilled off and the residue is purified by column chromatography. By doing
The desired product can be obtained.

[0042]

EFFECT OF THE INVENTION The compound represented by the general formula (I) of the present invention is easy to handle and can protect the hydroxyl group in the reaction with alcohol without by-producing a carbonate compound consisting of two molecules of the starting alcohol. . It is also useful as a protective agent for mercapto groups, amino groups, etc., and as an active esterifying agent for carboxyl groups.

[0043]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Example 1 To a 100 ml eggplant-shaped flask, 1.10 g (11 mmol) of 2,4-pentanedione and 0.24 g (0.2 mmol) of 4-N, N-dimethylaminopyridine were added,
Dissolve in 30 ml of methylene chloride. 2.18 g (10 mmo of di-t-butyl dicarbonate was added to this reaction solution.
1) is added dropwise, and the mixture is stirred at room temperature for 3 hours.

After completion of the reaction, methylene chloride was distilled off, and the residue was separated and purified by silica gel column chromatography to give 1.70 g of 4-t-butoxycarbonyloxy-3-penten-2-one (yield 85.0. %)Obtained.

As a result of measuring the infrared absorption spectrum of this product, an absorption based on a carbonyl group was obtained at 1759 cm ^-1 . Its elemental analysis values C59.72%, C59.98% is calculated values for the composition formula A _{H8.24% C 10 H 16 O 4} (200.23), in good agreement to H8.06%. In addition, as a result of measuring the mass spectrum (CI method),
A peak corresponding to (M + 1) ⁺ was shown at m / e 201.

Further, the result of measurement of ¹ H-nuclear magnetic resonance spectrum (δ: ppm: tetramethylsilane standard; deuterated chloroform solvent) was as follows.

[0048]

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A singlet corresponding to nine protons is shown at 1.53 ppm, which corresponds to the proton of the t-butyl group in (a).
A singlet for three protons is shown at 2.22 ppm,
Corresponding to the methyl proton in (d). A singlet for three protons was shown at 2.33 ppm, which corresponds to the methyl proton in (b). A singlet for each proton is shown at 6.18 ppm, which corresponds to the methine proton of (c).

From the above results, it was revealed that the isolated product was 4-t-butoxycarbonyloxy-3-penten-2-one.

Example 2 The same operation as in Example 1 was carried out except that methyl 3-oxobutanoate was used in place of 2,4-pentanedione. As a result, 3-t-butoxycarbonyloxy-2
-1.92 g of methyl butenoate (yield 88.8%) was obtained.

As a result of measuring the infrared absorption spectrum of this product, an absorption based on a carbonyl group was obtained at 1761 cm ^-1 . Its elemental analysis values C55.38%, C55.55% is calculated values for the composition formula A _{H7.66% C 10 H 16 O 5} (216.23), in good agreement to H7.46%. In addition, as a result of measuring the mass spectrum (CI method),
A peak corresponding to (M + 1) ⁺ was shown at m / e 217.

[0053]

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Further, the result of measurement of ¹ H-nuclear magnetic resonance spectrum (δ: ppm: tetramethylsilane standard; deuterated chloroform solvent) was as follows. 1.52
The singlet for nine protons is shown in ppm, and t- of (a)
Corresponding to the proton of the butyl group. A singlet for three protons was shown at 2.38 ppm, which corresponded to the methyl proton in (b). A double line for three protons was shown at 3.70 ppm, which corresponded to the methyl proton in (d). 6.78p
A singlet for each proton is shown in pm, which corresponds to the methine proton in (c).

From the above results, it was revealed that the isolated product was methyl 3-t-butoxycarbonyloxy-2-butenoate.

Example 3 Instead of 2,4-pentanedione, N, N-dimethyl-
The same operation as in Example 1 was performed except that 3-oxobutanoic acid amide was used. As a result, N, N-dimethyl-3
2.07 g (yield 90.5%) of -t-butoxycarbonyloxy-2-butenoic acid amide was obtained.

As a result of measuring the infrared absorption spectrum of this product, an absorption based on a carbonyl group was obtained at 1759 cm ^-1 . The elemental analysis values are C57.71%, H8.22%,
N 6.28% and the composition formula C ₁₁ H ₁₉ N ₁ O ₄ (229.
27) calculated values for C57.63%, H8.3
It was in good agreement with 5% and N6.11%. In addition, as a result of measuring the mass spectrum (CI method), m / e 230 was calculated as (M +
1) A peak corresponding to ⁺ was shown.

Further, the results of measurement of ¹ H-nuclear magnetic resonance spectrum (δ: ppm: tetramethylsilane standard; deuterated chloroform solvent) were as follows.

[0059]

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A singlet corresponding to nine protons is shown at 1.52 ppm, which corresponds to the proton of the t-butyl group in (a).
A singlet for three protons is shown at 2.22 ppm,
Corresponding to the methyl proton in (b). A double line for six protons is shown at 2.99 ppm and 3.05 ppm,
It corresponds to the methyl protons in (d) and (e). 6.00
A singlet for each proton is shown in ppm, which corresponds to the methine proton in (c).

From the above results, it was revealed that the isolated product was N, N-dimethyl-3-t-butoxycarbonyloxy-2-butenoic acid amide.

Example 4 The same operation as in Example 1 was carried out except that 1,3-cyclohexanedione was used instead of 2,4-pentanedione. As a result, 3-t-butoxycarbonyloxy-
1.66 g of 2-cyclohexen-1-one (yield 7
8.3%) was obtained.

As a result of measuring the infrared absorption spectrum of this product, an absorption based on a carbonyl group was obtained at 1764 cm ^-1 . Its elemental analysis values C62.13%, C62.25% is calculated values for the composition formula A _{H7.83% C 11 H 16 O 4} (212.25), in good agreement to H7.60%. In addition, as a result of measuring the mass spectrum, m / e21
3 shows a peak corresponding to (M + 1) ⁺ .

Further, the ¹ H-nuclear magnetic resonance spectrum (δ: ppm: tetramethylsilane standard; deuterated chloroform solvent) was measured and the results were as follows.

[0065]

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A singlet corresponding to nine protons was shown at 1.52 ppm, which was the proton of the t-butyl group in (a).
A multiplet of two protons was shown at 2.00 to 2.10 ppm and corresponded to the methylene proton of (c). 2.32-
A multiplet of two protons is shown at 2.44 ppm,
Corresponding to the methylene proton in (b). 2.50-2.
A multiplet of two protons was shown at 61 ppm, which corresponds to the methylene proton of (d).

From the above results, it was revealed that the isolated product was 3-t-butoxycarbonyloxy-2-cyclohexen-1-one.

Example 5 The same operation as in Example 1 was carried out except that dimethyl dicarbonate was used instead of di-t-butyl dicarbonate. As a result, 4-methoxycarbonyloxy-3-
1.26 g (yield 79.9%) of penten-2-one was obtained.

As a result of measuring the infrared absorption spectrum of this product, an absorption based on a carbonyl group was obtained at 1759 cm ^-1 . Its elemental analysis values C53.02%, C53.16% is calculated values for the composition formula A _{H8.00% C 7 H 10 O 4} (158.15), in good agreement to H6.37%. In addition, as a result of measuring the mass spectrum (CI method),
A peak corresponding to (M + 1) ⁺ was shown at m / e 159.

Further, the result of measurement of ¹ H-nuclear magnetic resonance spectrum (δ: ppm: tetramethylsilane standard; deuterated chloroform solvent) was as follows.

[0071]

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A singlet for three protons is shown at 2.24 ppm, which corresponds to the methyl proton in (d). 2.33
A singlet for three protons is shown in ppm and corresponds to the methyl proton in (b). A singlet for three protons was shown at 3.80 ppm, which corresponded to the methyl proton in (a). A singlet for one proton is shown at 6.17 ppm,
It corresponds to the methine proton in (c).

From the above results, it was revealed that the isolated product was 4-methoxycarbonyloxy-3-penten-2-one.

Example 6 The same operation as in Example 1 was carried out except that diallyl dicarbonate was used instead of di-t-butyl dicarbonate. As a result, 4-allyloxycarbonyloxy-
1.25 g of 3-penten-2-one (yield 68.1
%)Obtained.

As a result of measuring the infrared absorption spectrum of this product, an absorption based on a carbonyl group was obtained at 1760 cm ^-1 . The elemental analysis values were C58.47% and H6.70%, which were in good agreement with the calculated values C58.69% and H6.57% for the composition formula C ₉ H ₁₂ O ₄ (184.19). In addition, as a result of measuring the mass spectrum (CI method),
A peak corresponding to (M + 1) ⁺ was shown at m / e 185.

Further, the result of measurement of ¹ H-nuclear magnetic resonance spectrum (δ: ppm: tetramethylsilane standard; deuterated chloroform solvent) was as follows.

[0077]

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A singlet for three protons is shown at 2.24 ppm, which corresponds to the methyl proton in (f). 2.33
A singlet for three protons is shown in ppm, which corresponds to the methyl proton in (d). A multiplet corresponding to two protons was shown at 4.50 to 4.65 ppm and corresponded to the methylene proton of (c). A multiplet for one proton was shown at 5.15 to 5.25 ppm, which corresponded to the methine proton in (b). A multiplet of two protons was shown at 5.30 to 6.20 ppm, which corresponded to the methylene proton of (a). 6.
A singlet for each proton is shown at 17 ppm, which corresponds to the methine proton of (e).

From the above results, it was revealed that the isolated product was 4-allyloxycarbonyloxy-3-penten-2-one.

Example 7 The same operation as in Example 1 was carried out except that diphenyldicarbonate was used instead of di-t-butyldicarbonate. As a result, 1.10 g of 4-phenyloxycarbonyloxy-3-penten-2-one (yield 50.
0%).

As a result of measuring the infrared absorption spectrum of this product, an absorption based on a carbonyl group was obtained at 1764 cm ^-1 . The elemental analysis values were C65.19% and H5.70%, which were in good agreement with the calculated values C65.45% and H5.49% for the composition formula C ₁₂ H ₁₂ O ₄ (220.22). In addition, as a result of measuring the mass spectrum (CI method),
A peak corresponding to (M + 1) ⁺ was shown at m / e 221.

Further, the result of measurement of ¹ H-nuclear magnetic resonance spectrum (δ: ppm: tetramethylsilane standard; deuterated chloroform solvent) was as follows.

[0083]

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A singlet for three protons is shown at 2.23 ppm, which corresponds to the methyl proton in (d). 2.35
A singlet for three protons is shown in ppm and corresponds to the methyl proton in (b). A singlet for three protons was shown at 3.80 ppm, and a singlet for one proton was shown at 6.17 ppm, which corresponded to the methine proton of (c).
A multiplet of five protons was shown at 7.08 to 7.50 ppm, which corresponds to the proton of the benzene ring in (a).

From the above results, it was revealed that the isolated product was 4-phenyloxycarbonyloxy-3-penten-2-one.

Example 8 The same operation as in Example 1 was carried out except that dibenzyl dicarbonate was used instead of di-t-butyl dicarbonate. As a result, 1.14 g of 4-benzyloxycarbonyloxy-3-penten-2-one (yield 48.
8%).

As a result of measuring the infrared absorption spectrum of this product, an absorption based on a carbonyl group was obtained at 1760 cm ^-1 . The elemental analysis values were C 66.48% and H 6.21%, which were in good agreement with the calculated values C 66.66% and H 6.02% for the composition formula C ₁₃ H ₁₄ O ₄ (234.25). In addition, as a result of measuring the mass spectrum (CI method),
A peak corresponding to (M + 1) ⁺ was shown at m / e 235.

Further, the result of measurement of ¹ H-nuclear magnetic resonance spectrum (δ: ppm: tetramethylsilane standard; deuterated chloroform solvent) was as follows.

[0089]

Embedded image

A singlet for three protons is shown at 2.24 ppm, which corresponds to the methyl proton of (e). 2.33
A singlet for three protons is shown in ppm and corresponds to the methyl proton in (c). A singlet for two protons is shown at 5.11 ppm, which corresponds to the methylene proton in (b). A singlet for one proton is shown at 6.17 ppm,
Corresponding to the methine proton in (d). A singlet of five protons was shown at 7.34 ppm, which corresponded to the proton of the benzene ring in (a).

From the above results, it was revealed that the isolated product was 4-benzyloxycarbonyloxy-3-penten-2-one.

Example 9 The same operation as in Example 1 was carried out except that phenyl 3-oxobutanoate was used instead of 2,4-pentanedione. As a result, 3-t-butoxycarbonyloxy-2
-2.38 g (yield 85.5%) of phenyl butenoate was obtained.

As a result of measuring the infrared absorption spectrum of this product, an absorption based on a carbonyl group was obtained at 1761 cm ^-1 . The elemental analysis values were C 64.80% and H 7.38%, which were in good agreement with the calculated values C 64.74% and H 6.52% for the composition formula C ₁₅ H ₁₈ O ₅ (278.30). In addition, as a result of measuring the mass spectrum (CI method),
A peak corresponding to (M + 1) ⁺ was shown at m / e 279.

[0094]

Embedded image

Further, the result of measurement of ¹ H-nuclear magnetic resonance spectrum (δ: ppm: tetramethylsilane standard; deuterated chloroform solvent) was as follows. 1.52
The singlet for nine protons is shown in ppm, and t- of (a)
Corresponding to the proton of the butyl group. A singlet for three protons was shown at 2.38 ppm, which corresponded to the methyl proton in (b). A singlet for one proton is shown at 6.78 ppm, which corresponds to the methine proton of (c). 7.00
A multiplet of 5 protons is shown at 7.50 ppm,
It corresponds to the proton of the benzene ring in (d).

From the above results, it was revealed that the isolated product was phenyl 3-t-butoxycarbonyloxy-2-butenoate.

Example 10 The same operation as in Example 1 was carried out except that benzyl 3-oxobutanoate was used in place of 2,4-pentanedione. As a result, 3-t-butoxycarbonyloxy-2
-2.54 g (yield 87.0%) of benzyl butenoate was obtained.

As a result of measuring the infrared absorption spectrum of this product, an absorption based on a carbonyl group was obtained at 1760 cm ^-1 . The elemental analysis values are C65.598%, H6.76%
C65.74% a calculated value for a in formula _{C 16 H 20 O 5 (292.33} ) in, in good agreement to H6.90%. Further, as a result of measuring a mass spectrum (CI method), a peak corresponding to (M + 1) ⁺ was shown at m / e 293.

[0099]

Embedded image

Further, the result of measurement of ¹ H-nuclear magnetic resonance spectrum (δ: ppm: tetramethylsilane standard; deuterated chloroform solvent) was as follows. 1.55
The singlet for nine protons is shown in ppm, and t- of (a)
Corresponding to the proton of the butyl group. A singlet for three protons is shown at 2.37 ppm, which corresponds to the methyl proton in (b). A singlet for two protons was shown at 5.14 ppm, which corresponded to the methylene proton of (d). 6.78
A singlet for each proton is shown in ppm, which corresponds to the methine proton in (c). A singlet for five protons was shown at 7.40 ppm, which corresponds to the proton of the benzene ring in (e).

From the above results, it was revealed that the isolated product was benzyl 3-t-butoxycarbonyloxy-2-butenoate.

Examples 11 to 22 The same operations as in Example 1 were carried out except that the carbonyl compound, base and organic solvent shown in Table 1 were used. The results are shown in Table 1. The obtained compound was subjected to elemental analysis, ¹ H-nuclear magnetic resonance spectrum, mass spectrum and infrared absorption spectrum.

As a result, in Examples 11, 12 and 13, the same 4-t-butoxycarbonyloxy-3- as in Example 1 was obtained.
Penten-2-one, Examples 14 and 15 are methyl 3-t-butoxycarbonyloxy-2-butenoate similar to Example 2, and Examples 16 and 17 are N and N similar to Example 3. N-dimethyl-3-t-butoxycarbonyloxy-2-butenoic acid amide, Examples 18, 19,
It was confirmed that 20 was the same 3-t-butoxycarbonyloxy-2-cyclohexen-1-one as in Example 4. Further, Example 21 is the same as Example 9 in 3-t-.
It was confirmed that it was phenyl butoxycarbonyloxy-2-butenoate, and that Example 22 was benzyl 3-t-butoxycarbonyloxy-2-butenoate similar to Example 10.

[0104]

[Table 1]

Application Example 1 0.40 g (2 mmol) of 4-t-butoxycarbonyloxy-3-penten-2-one synthesized in Example 1
And phenethyl alcohol 0.27g (2.2mmo
l), 4-N, N-dimethylaminopyridine 0.024
g (0.2 mmol) was dissolved in 10 ml of methylene chloride and reacted at 40 ° C. for 10 hours. Then, after returning to room temperature and distilling off the solvent, 0.41 g (yield 92.0%) of Ot-butoxycarbonylphenethyl alcohol was obtained by separating and purifying the residue by column chromatography. At this time, no by-product of diphenylethyl carbonate was found.

Use Examples 2 to 26 The carbonate compounds and alcohols shown in Table 1 were subjected to the same operations as in Use Example 1. The results are shown in Table 1. At this time, no by-product of diphenylethyl carbonate was found.

[0107]

[Table 2]

Comparative Application Example 1 4-t-Butoxycarbonyloxy-3-pentene-2
The same reaction as in Application Example 1 was carried out except that the reaction was carried out at room temperature using di-t-butyl dicarbonate instead of -one. As a result, the production of Ot-butoxycarbonylphenethyl alcohol was 0.27 g (yield 61.5).
%), And 0.17 g (yield 31.4%) of diphenylethyl carbonate was further produced.

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[Procedure amendment]

[Submission date] August 29, 1995

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claim 2

[Correction method] Change

[Correction contents]

Embedded image (However, R ₂ is an alkyl group, R ₃ is an alkyl group, an alkoxy group, an aryl group which may have a substituent, an aralkyl group which may have a substituent, and a substituent which may have a substituent. An aryloxy group, an aralkyloxy group which may have a substituent or an amino group which may have a substituent, R ₂
And R ₃ may together form a ring. ) And a general formula (III) shown below.

Embedded image (However, R ₁ is an alkyl group, an aryl group, an alkenyl group or an aralkyl group.) Is reacted with a dicarbonate compound in the presence of a base to produce the carbonate compound according to claim 1. Method.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical display location // C07B 61/00 300 C07B 61/00 300

Claims (2)

[Claims] (1) The following formula (I): (However, R ₁ is an alkyl group, an aryl group which may have a substituent, an alkenyl group or an aralkyl group which may have a substituent, R ₂ is an alkyl group, R ₃ is an alkyl group, An alkoxy group, an aryl group which may have a substituent, an aralkyl group which may have a substituent, an aryloxy group which may have a substituent, an aralkyloxy group which may have a substituent or a substituent A carbonate compound which is an amino group which may have a group, and R ₂ and R ₃ may together form a ring. 2. The following general formula (II): (However, R ₂ is an alkyl group, R ₃ is an alkyl group, an alkoxy group, an aryl group which may have a substituent, an aralkyl group which may have a substituent, and a substituent which may have a substituent. An aryloxy group, an aralkyloxy group which may have a substituent or an amino group which may have a substituent, R ₂
And R ₃ may together form a ring. ) And a carbonyl compound represented by the following general formula (III): (However, R ₁ is an alkyl group, an aryl group, an alkenyl group or an aralkyl group.) Is reacted with a dicarbonate compound in the presence of a base to produce a carbonate compound according to claim 1. Method.