JPH1129529A - T-butyl esters of hydro-aromatic carboxylic acid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain new compounds useful as an intermediate for a dissolution suppressant for chemical amplification type resist using various radiations such as argon fluoride excimer resists and various synthetics. SOLUTION: The compounds are represented by formula I [(n) is 2-4], formula II [X is OH, (trifluoro)methyl, t-butyl or methoxy; (p) is 1-4], formula III [(m) and (n) are each 0-2 and (m+n) is 1 or 2], formula IV [(m) and (n) are each 0-4 and (m+n) is 1 41, formula V [Y is O, carbonyl or hexafluoroisopropylidene; (m) and (n) are each 0-4 and (m+n) is 1-41] etc., e.g. t-butyl 1,2-cyclohexanedicarboxylate. The compounds represented by formula I to V, etc., can be produced by hydrogenating the aromatic nucleus of butyl aromatic carboxylates corresponding to the objective t butyl hydro-aromatic carboxylates in the presence of a noble metal (supporting) catalyst or a noble metallic complex catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel hydroaromatic carboxylic acid t-butyl ester, and more particularly, to various kinds of various compounds represented by argon fluoride (ArF) or krypton fluoride (KrF) excimer resists. The present invention relates to hydroaromatic carboxylic acid t-butyl esters which are useful as dissolution inhibitors for chemically amplified resists using radiation and are useful as intermediates for various synthetic products.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Argon Fluoride (ArF)
Alternatively, as a dissolution inhibitor for krypton fluoride (KrF) excimer resist, the transmittance (transparency) to an ArF or KrF laser in a short wavelength ultraviolet region is used.
There is a demand for a compound which is excellent in etching and improves the etching resistance of the image area during development.

Conventionally, organic compounds containing a benzene ring have been known as a dissolution inhibitor having high etching resistance, but have low transmittance to ArF or KrF lasers in a short wavelength ultraviolet region. In particular, because of low permeability to ArF laser, it is difficult to use a benzene ring-containing organic compound as a dissolution inhibitor for an ArF excimer resist.

An alicyclic organic compound has been proposed as a material for the dissolution inhibitor having the above etching resistance and transparency. In particular, hydroaromatic carboxylic acid t-butyl ester is desirable, but since it is difficult to convert a carboxyl group directly bonded to a hydroaromatic ring into t-butyl ester, such organic compounds have hardly been studied. In particular, compounds in which a plurality of t-butyl ester groups are bonded to a hydroaromatic ring have not been studied because their synthesis becomes extremely difficult.

[0005] Accordingly, there is a demand for the appearance of novel hydroaromatic carboxylic acid t-butyl esters useful as a material for the dissolution inhibitor, particularly compounds having a plurality of t-butyl ester groups bonded to a hydroaromatic ring. .

[0006]

The object of the present invention is to provide an argon fluoride (Ar
F) or t-butyl hydroaromatic carboxylate useful as a dissolution inhibitor for chemically amplified resists such as krypton fluoride (KrF) excimer resists, and as an intermediate of various synthetic products. The purpose is.

[0007]

SUMMARY OF THE INVENTION The hydroaromatic carboxylic acids t-type according to the invention
The butyl esters include the following general formulas [I], [II], [III], [III] ', [IV], [IV], which contain a hydroaromatic ring having at least one t-butoxycarbonyl group.
V] ', [V], or [V]'.

[0008]

Embedded image

Wherein n is an integer of 2 to 4. ]

[0010]

Embedded image

Wherein X is a hydroxyl group, a methyl group, a t-butyl group, a methoxy group or a trifluoromethyl group;
p is an integer of 1 to 4. ]

[0012]

Embedded image

Wherein m and n are each an integer of 0 to 2, and m + n is 1 or 2. ]

[0014]

Embedded image

[0015]

Embedded image

[In the formula, m and n are each an integer of 0 to 4, and m + n is an integer of 1 to 4. ]

[0017]

Embedded image

[0018]

Embedded image

Wherein Y is an oxygen atom, a carbonyl group,
Or a hexafluoroisopropylidene group, m and n are each an integer of 0 to 4, and m + n
Is an integer of 1 to 4. ]

[0020]

Embedded image

Wherein Y is an oxygen atom, a carbonyl group,
Or a hexafluoroisopropylidene group. As the hydroaromatic carboxylic acid t-butyl esters, the following compounds are preferred. (1) Hydroaromatic carboxylic acid t-butyl esters wherein n = 2 in the general formula [I]. (2) In the above general formula [II], X is a methoxy group or a trifluoromethyl group.
t-butyl esters. (3) In the formula [III], hydroaromatic carboxylic acid t-butyl esters wherein n = 2. (4) Hydroaromatic carboxylic acid t-butyl esters wherein n = 2 in the above formula [IV]. (5) In the formula [V], hydroaromatic carboxylic acid t-butyl esters wherein n = 2.

[0022]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the t-butyl hydroaromatic carboxylate according to the present invention will be described in detail.

The hydroaromatic carboxylic acid t-butyl esters according to the present invention contain a hydroaromatic ring having at least one t-butoxycarbonyl group, represented by the following general formulas [I], [II] and [III]. , [III] ', [IV], [I
V] ', [V] or [V]'.

[0024]

Embedded image

In the general formula [I], n is an integer of 2 to 4. Specific examples of the hydroaromatic carboxylic acid t-butyl ester represented by the general formula [I] include 1,2-cyclohexanedicarboxylic acid t-butyl ester and 1,3-cyclohexanedicarboxylic acid t-butyl ester. And 1,4-cyclohexanedicarboxylic acid t-butyl ester, 1,2,4-cyclohexanetricarboxylic acid t-butyl ester, 1,2,4,5-cyclohexanetetracarboxylic acid t-butyl ester and the like.

[0026]

Embedded image

In the general formula [II], X is a hydroxyl group, a methyl group, a t-butyl group, a methoxy group or a trifluoromethyl group, and p is an integer of 1 to 4. The above general formula [II]
As the hydroaromatic carboxylic acid t-butyl esters represented by, specifically, 2-methyl-1-cyclohexanecarboxylic acid t-butyl ester, 3-methyl-1-cyclohexanecarboxylic acid t-butyl ester, 4 -Methyl-1-cyclohexanecarboxylic acid t-butyl ester, 4-t-butyl-1-
Cyclohexanecarboxylic acid t-butyl ester, 4-methoxy-1-cyclohexanecarboxylic acid t-butyl ester, 2-
Trifluoromethyl-1-cyclohexanecarboxylic acid t-butyl ester, 4-trifluoromethyl-1-cyclohexanecarboxylic acid t-butyl ester, 2-hydroxy-1-cyclohexanecarboxylic acid t-butyl ester, 4-hydroxy
-1-cyclohexanecarboxylic acid t-butyl ester and the like.

[0028]

Embedded image

In the general formula [III], m and n are each an integer of 0 to 2, and m + n is 1 or 2. Specific examples of the hydroaromatic carboxylic acid t-butyl ester represented by the general formula [III] include 1-decahydronaphthalene carboxylic acid t-butyl ester and 2-decahydronaphthalene carboxylic acid t-butyl ester , 2,7-decahydronaphthalenedicarboxylic acid t-butyl ester, 1,
4-decahydronaphthalenedicarboxylic acid t-butyl ester and the like.

[0030]

Embedded image

Specific examples of the hydroaromatic carboxylic acid t-butyl ester represented by the general formula [III] ′ include 7-hydroxy-2-decahydronaphthalenecarboxylic acid
t-butyl ester, 5-hydroxy-2-decahydronaphthalenecarboxylic acid t-butyl ester, 6-hydroxy-1-decahydronaphthalenecarboxylic acid t-butyl ester and the like.

[0032]

Embedded image

In the general formula [IV], m and n are each an integer of 0 to 4, and m + n is an integer of 1 to 4. Specific examples of the hydroaromatic carboxylic acid t-butyl ester represented by the general formula [IV] include 4-dicyclohexylcarboxylic acid t-butyl ester, 4,4′-dicyclohexyldicarboxylic acid t-butyl ester, 3,3 ', 4
-Dicyclohexyltricarboxylic acid t-butyl ester,
3,3 ′, 4,4′-dicyclohexyltetracarboxylic acid t-butyl ester and the like.

[0034]

Embedded image

Specific examples of the hydroaromatic carboxylic acid t-butyl ester represented by the general formula [IV] ′ include 4′-hydroxy-4-dicyclohexylcarboxylic acid t-butyl ester.
Butyl ester and the like.

[0036]

Embedded image

In the general formula [V], Y represents an oxygen atom, a carbonyl group, or a hexafluoroisopropylidene group (-
_{(F 3 C) C (CF} 3) - a group). m and n are each an integer of 0 to 4, and m + n is an integer of 1 to 4.

Specific examples of the hydroaromatic carboxylic acid t-butyl ester represented by the general formula [V] include 4- (t-butoxycarbonyl) dicyclohexyl ether, 4,4 '-(di-t -Butoxycarbonyl) dicyclohexyl ether, 3,4,4 '-(tri-t-butoxycarbonyl)
Dicyclohexyl ether, 3,3 ', 4,4'-(tetra-t-butoxycarbonyl) dicyclohexyl ether, 4,4'-
(Hexafluoroisopropylidene) -1-dicyclohexylcarboxylic acid t-butyl ester, 4,4 ′-(hexafluoroisopropylidene) -1,1′-dicyclohexyldicarboxylic acid t-butyl ester, 4,4 ′-(hexafluoro Isopropylidene) -1,1 ', 2-dicyclohexyltricarboxylic acid t-
Butyl ester, 4,4 '-(hexafluoroisopropylidene) -1,1', 2,2'-dicyclohexyltetracarboxylic acid t-
Butyl ester, 4,4 ′-(di-t-butoxycarbonyl) dicyclohexyl ketone, 3,3 ′, 4,4 ′-(tetra-t-butoxycarbonyl) dicyclohexyl ketone and the like.

[0039]

Embedded image

Y in the general formula [V] 'is the same as Y in the general formula [V]. Specific examples of the hydroaromatic carboxylic acid t-butyl ester represented by the above general formula [V] ′ include 4-hydroxy-4′-t-butoxycarbonyldicyclohexyl ether and the like.

Hydroaromatic carboxylic acid t-butyl ester
Method of synthesizing the above general formulas [I], [II], [III], [III] ', [I
The hydroaromatic carboxylic acid t-butyl esters represented by V], [IV] ′, [V] and [V] ′ are, for example, aromatic corresponding to the desired hydroaromatic carboxylic acid t-butyl esters. It can be synthesized by hydrogenating an aromatic nucleus of a carboxylic acid butyl ester in the presence of a noble metal catalyst, a noble metal supported catalyst or a noble metal complex catalyst.

The t-butyl aromatic carboxylate corresponding to the t-butyl hydroaromatic carboxylate represented by the general formula [I] is represented by the following formula [Ia].

[0043]

Embedded image

In the formula [Ia], n is an integer of 2 to 4. Specific examples of the aromatic carboxylic acid t-butyl ester represented by the above formula [Ia] include 1,2-benzenedicarboxylic acid t-butyl ester (= phthalic acid di-t-butyl ester), 3-benzenedicarboxylic acid t-butyl ester (= isophthalic acid di-t-butyl ester), 1,4-benzenedicarboxylic acid t-butyl ester (= terephthalic acid di-t-butyl ester)
-t-butyl ester), 1,2,4-benzenetricarboxylic acid
t-butyl ester (= tri-meritic acid tri-t-butyl ester), 1,2,4,5-benzenetetracarboxylic acid t-butyl ester (= pyromellitic acid tetra-t-butyl ester)
And the like.

An aromatic carboxylic acid t-butyl ester corresponding to the hydroaromatic carboxylic acid t-butyl ester represented by the general formula [II] is represented by the following formula [IIa].

[0046]

Embedded image

In the formula [IIa], X represents a hydroxyl group, a methyl group,
It is a t-butyl group, a methoxy group or a trifluoromethyl group, and p is an integer of 1-4. Examples of the aromatic carboxylic acid t-butyl ester represented by the above formula [IIa] include:
Specifically, o-toluic acid t-butyl ester, m-toluic acid t-butyl ester, p-toluic acid t-butyl ester, 4-t-butylbenzoic acid t-butyl ester, 4-methoxybenzoic acid t -Butyl ester, 2-methoxybenzoic acid t-butyl ester, 2-trifluoromethylbenzoic acid t-butyl ester, 4-trifluoromethylbenzoic acid t-butyl ester, 2-hydroxybenzoic acid t-butyl ester, 4- Hydroxybenzoic acid t-butyl ester and the like.

The aromatic carboxylic acid t-butyl ester corresponding to the hydroaromatic carboxylic acid t-butyl ester represented by the general formula [III] is represented by the following formula [IIIa].

[0049]

Embedded image

In the formula [IIIa], m and n are each 0
And m + n is 1 or 2. Specific examples of the aromatic carboxylic acid t-butyl ester represented by the above formula [IIIa] include α-naphthoic acid
t-butyl ester, β-naphthoic acid t-butyl ester,
Examples include t-butyl 2,6-naphthalenedicarboxylic acid and t-butyl 1,4-naphthalenedicarboxylic acid.

The aromatic carboxylic acid t-butyl ester corresponding to the above-mentioned general formula [III] 'hydroaromatic carboxylic acid t-butyl ester is represented by the following formula [IIIa]'.

[0052]

Embedded image

Specific examples of the aromatic carboxylic acid t-butyl ester represented by the above formula [IIIa] ′ include 5-hydroxy-1-naphthoic acid t-butyl ester and 6-hydroxy-2-naphthoic acid t-butyl ester, 4-hydroxy-1-
And naphthoic acid t-butyl ester.

An aromatic carboxylic acid t-butyl ester corresponding to the hydroaromatic carboxylic acid t-butyl ester represented by the general formula [IV] is represented by the following formula [IVa].

[0055]

Embedded image

In the formula [IVa], m and n are each 0
Is an integer of 1 to 4, and m + n is an integer of 1 to 4. Specific examples of the aromatic carboxylic acid t-butyl ester represented by the above formula [IVa] include 4-biphenylcarboxylic acid t-butyl ester, 4,4′-biphenyldicarboxylic acid t-butyl ester, 3 ', 4-biphenyltricarboxylic acid t-butyl ester, 3,3', 4,4'-biphenyltetracarboxylic acid t-butyl ester and the like.

An aromatic carboxylic acid t-butyl ester corresponding to the above-mentioned hydroaromatic carboxylic acid t-butyl ester represented by the general formula [IV] ′ is represented by the following formula [IVa] ′.

[0058]

Embedded image

Specific examples of the aromatic carboxylic acid t-butyl ester represented by the above formula [IVa] 'include 4'-
And hydroxy-4-biphenylcarboxylic acid t-butyl ester.

The t-butyl aromatic carboxylate corresponding to the t-butyl hydroaromatic carboxylate represented by the general formula [V] is represented by the following formula [Va].

[0061]

Embedded image

In the formula [Va], Y is an oxygen atom, a carbonyl group, or a hexafluoroisopropylidene group. m and n are each an integer of 0 to 4, and m + n is an integer of 1 to 4.

Specific examples of the aromatic carboxylic acid t-butyl ester represented by the above formula [Va] include 4- (t-butyl ester).
Butoxycarbonyl) diphenyl ether, 4,4 '-(di-t
-Butoxycarbonyl) diphenyl ether, 3,4,4'-
(Tri-t-butoxycarbonyl) diphenyl ether,
3,3 ', 4,4'-(tetra-t-butoxycarbonyl) diphenyl ether, 4,4 '-(hexafluoroisopropylidene)
-1-diphenylcarboxylic acid t-butyl ester, 4,4 ′-(hexafluoroisopropylidene) -1,1′-diphenyldicarboxylic acid t-butyl ester, 4,4 ′-(hexafluoroisopropylidene) -1, 1 ', 2-diphenyltricarboxylic acid t-butyl ester, 4,4'-(hexafluoroisopropylidene) -1,1 ', 2,2'-diphenyltetracarboxylic acid t-butyl ester, 4,4'-( Di-t-butoxycarbonyl) benzophenone, 3,3 ', 4,4'-(tetra-t-butoxycarbonyl)
Benzophenone, and the like.

The aromatic carboxylic acid t-butyl ester corresponding to the hydroaromatic carboxylic acid t-butyl ester represented by the general formula [V] ′ is represented by the following formula [Va] ′.

[0065]

Embedded image

In formula [Va] ′, Y
a] 'is the same as Y. Specific examples of the aromatic carboxylic acid t-butyl ester represented by the above formula [Va] ′ include 4-hydroxy-4′-t-butoxycarbonylphenyl ether.

As the metal hydride catalyst used in this synthesis method, a noble metal catalyst, a noble metal supported catalyst and a noble metal complex catalyst are preferable. In particular, a noble metal-supported catalyst is industrially preferable from the viewpoint of the price and recovery of the catalyst.

As the noble metal catalyst components of the noble metal catalyst, the noble metal supported catalyst and the noble metal complex catalyst, specifically, rhodium (Rh), ruthenium (Ru), palladium (P
d), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), and silver (Ag).

Further, specific examples of the carrier used for the noble metal-supported catalyst include carbon, alumina, silica and the like. In this synthesis method, a noble metal-supported catalyst such as rhodium carbon, palladium carbon, ruthenium carbon, rhodium alumina, palladium alumina, or ruthenium alumina is preferably used.

The noble metal catalyst and the noble metal supported catalyst are used in an amount of 0.1 to 50 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the aromatic carboxylic acid t-butyl ester. .

In this synthesis method, when a starting material is an aromatic carboxylic acid t-butyl ester that melts at the reaction temperature, it is not necessary to use a solvent, but an aromatic carboxylic acid t-butyl that does not melt at the reaction temperature is used. When butyl esters are used as a raw material, a solvent that can dissolve the aromatic carboxylic acid t-butyl esters is used.

Examples of such a solvent include ethers such as tetrahydrofuran (THF), dioxolan and dioxane; alcohols such as methanol, isopropyl alcohol and butanol; polyhydric alcohols such as ethylene glycol; And esters such as butyl acetate. These solvents may be used as appropriate in accordance with the solubility and reactivity of the raw materials. For those having particularly poor reactivity, t-butanol is preferably used to increase the reaction rate.

The above-mentioned solvent is an aromatic carboxylic acid t-
0 to 50 times, preferably 0 to 50 times the amount of butyl esters used
Used in 10 times the amount. Regarding the reaction conditions for hydrogenating the aromatic nucleus of the aromatic carboxylic acid t-butyl ester, the reaction temperature is room temperature to 200 ° C., preferably 50 to 1 ° C.
50 ° C., and the reaction pressure is from normal pressure to 100 kg / c.
m ² , preferably about 30 to 70 kg / cm ² , more preferably about 50 kg / cm ² , and the reaction time varies depending on the reaction temperature and the reaction pressure, but is several tens to several tens of hours, preferably several tens of minutes. A few hours.

The above general formulas [Ia], [IIa] and [III]
a], [IIIa] ′, [IVa], [IVa] ′, [Va] or an aromatic nucleus of an aromatic carboxylic acid t-butyl ester represented by [Va] ′, under the above reaction conditions, Hydrogenation in the presence of a noble metal catalyst, a noble metal supported catalyst or a noble metal complex catalyst produces the hydroaromatic carboxylic acid t-butyl esters according to the present invention. The reaction yield varies depending on the material before hydrogenation, but is 50 to 100%.

After the above-mentioned hydrogenation, through the steps of removing the catalyst, removing the solvent and concentrating the product, the obtained hydroaromatic carboxylic acid t-butyl ester of the present invention can be directly used as a product. .

After the above steps, the hydroaromatic carboxylic acid esters can be purified by recrystallization or distillation by further adding a solvent, and the purified product can be used as a product.

The product properties are crystalline or bulk solid,
It is a candy-like solid or liquid.

[0078]

According to the present invention, the hydroaromatic carboxylic acid t-
Butyl ester products are argon fluoride (Ar
It is very useful as a dissolution inhibitor for chemically amplified resists such as F) or krypton fluoride (KrF) excimer resists. Furthermore, other than ArF and KrF,
It is also useful as a dissolution inhibitor for various radiation resists such as electron beams, X-rays and ultraviolet rays.

Further, since the t-butyl ester of the hydroaromatic carboxylic acid can easily remove the t-butyl ester group with an acid, an intermediate of various synthetic products using the hydroaromatic carboxylic acid, For example, they are useful as intermediates for pharmaceuticals and agricultural chemicals, functional dyes, functional materials, resins such as polyester, polyimide, and polyamide, and various additives.

[0080]

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

[0081]

Example 1 [Production of 2,7-decahydronaphthalenedicarboxylic acid t-butyl ester] 2,6-naphthalenedicarboxylic acid t-butyl ester as a raw material
25 g of butyl ester, 200 g of tetrahydrofuran as a solvent, and 2 g of 5% rhodium carbon (50% wet product) as a noble metal supported catalyst, 500 ml with stirring
A stainless steel autoclave with a capacity of 10
The mixture was stirred at 0 ° C. and a hydrogen pressure of 20 kg / cm ² G for 4.5 hours.

After completion of the reaction, the obtained reaction mixture was cooled to room temperature, taken out of the autoclave, the catalyst was separated by filtration, the solvent was distilled off, and 2,7-decahydronaphthalenedicarboxylic acid represented by the following formula was obtained. 25.2 g of t-butyl ester
Was obtained as a white bulky solid. The purity of this 2,7-decahydronaphthalenedicarboxylic acid t-butyl ester was 96.8% as a result of measurement by high performance liquid chromatography (HPLC, RI detector).

[0083]

Embedded image

The identification of 2,7-decahydronaphthalenedicarboxylic acid t-butyl ester was carried out by H ¹ -NMR, mass spectrum and infrared absorption spectrum. The measurement data is shown below. (1) H ¹ -NMR (60 MHz)

[0085]

[Table 1]

(2) Mass spectrum (DI method) Molecular ion peak (m / e): 338 Fragment peak: 283, 227, 208 (3) Infrared absorption spectrum C = O: 1720 cm ^-1 C-OC: 1160 cm ^-1

[0087]

Example 2 [Production of 3,3 ', 4,4'-dicyclohexyltetracarboxylic acid t-butyl ester] As a raw material, 3,3', 4,4'-biphenyltetracarboxylic acid t-butyl ester 30 g, solvent 200 g of tetrahydrofuran and 3 g of 5% rhodium carbon (50% wet product) as a noble metal-supported catalyst were charged into a 500 ml stainless steel autoclave with stirring at a temperature of 100 ° C. and a hydrogen pressure of 30 kg / cm ² G for 30 minutes. And stirred.

After the completion of the reaction, the obtained reaction mixture was cooled to room temperature, taken out of the autoclave, the catalyst was separated by filtration, and the solvent was distilled off to obtain 3,3 ′, 4,4 ′ represented by the following formula. -Dicyclohexyltetracarboxylic acid t-butyl ester 3
0.1 g was obtained as a white mass.

The purity of the 3,3 ′, 4,4′-dicyclohexyltetracarboxylic acid t-butyl ester was measured by high performance liquid chromatography (HPLC, RI detector).
95.1%.

[0090]

Embedded image

The identification of 3,3 ′, 4,4′-dicyclohexyltetracarboxylic acid t-butyl ester was carried out by using H ¹ -NM
R, mass spectrum and infrared absorption spectrum were used. The measurement data is shown below. (1) H ¹ -NMR (60 MHz)

[0092]

[Table 2]

(2) Mass spectrum (DI method) Molecular ion peak (m / e): 566 (weak) Fragment peak: 334, 307 (3) Infrared absorption spectrum C = O: 1710 cm ^-1 C-OC: 1160cm ^-1

[0094]

Example 3 [Production of 1,3-cyclohexanedicarboxylic acid t-butyl ester] isophthalic acid di-t-butyl ester 20 as a raw material
g, 200 g of tetrahydrofuran as a solvent and 2 g of 5% rhodium carbon (50% wet product) as a noble metal-supported catalyst were charged into a 500 ml stainless steel autoclave with stirring, at a temperature of 100 ° C. and a hydrogen pressure of 50%.
The mixture was stirred for 20 minutes under the condition of kg / cm ² G.

After completion of the reaction, the obtained reaction mixture was cooled to room temperature, taken out of the autoclave, the catalyst was filtered off, and the solvent was distilled off to obtain 1,3-cyclohexanedicarboxylic acid t-formula represented by the following formula. 20.1 g of butyl ester was obtained as a colorless transparent liquid.

The purity of this 1,3-cyclohexanedicarboxylic acid t-butyl ester was measured by high performance liquid chromatography (HPLC, RI detector) to find 96.7%
Met.

[0097]

Embedded image

The above 1,3-cyclohexanedicarboxylic acid
Identification of t-butyl ester was performed by H ¹ -NMR, mass spectrum, and infrared absorption spectrum. The measurement data is shown below. (1) H ¹ -NMR (60 MHz)

[0099]

[Table 3]

(2) Mass spectrum (DI method) Molecular ion peak (m / e): Undetectable Fragment peak: 211, 173, 155 (3) Infrared absorption spectrum C = O: 1730 cm ^-1 C-OC: 1160cm ^-1

[0101]

Example 4 [Production of t-butyl 2-trifluoromethylcyclohexanecarboxylate] 20 g of t-butyl 2-trifluoromethylbenzoate as a raw material, 200 g of t-butanol as a solvent, and 5% rhodium as a catalyst supported on a noble metal 4 g of carbon (50% wet product) with stirring 500
The mixture was charged in a stainless steel autoclave having a capacity of 100 ml and a temperature of 100 ° C. and a hydrogen pressure of 100 kg / cm ² G.
Stir for 30 minutes.

After completion of the reaction, the obtained reaction mixture was cooled to room temperature, taken out of the autoclave, the catalyst was separated by filtration, and the solvent was distilled off to give 2-trifluoromethylcyclohexanecarboxylic acid represented by the following formula. -Butyl ester 2
0.1 g was obtained as a colorless transparent liquid.

The purity of this t-butyl 2-trifluoromethylcyclohexanecarboxylate was 99.9%, as measured by high performance liquid chromatography (HPLC, RI detector).

[0104]

Embedded image

The identification of the above-mentioned 2-trifluoromethylcyclohexanecarboxylic acid t-butyl ester is based on H ¹ -NM
R, mass spectrum and infrared absorption spectrum were used. The measurement data is shown below. (1) H ¹ -NMR (60 MHz)

[0106]

[Table 4]

(2) Mass spectrum (DI method) Molecular ion peak (m / e): undetectable Fragment peak: 224, 209, 179 (3) Infrared absorption spectrum C = O: 1730 cm ^-1 C-OC: 1140cm ^-1

[0108]

Example 5 [Production of 4-methoxy-1-cyclohexanecarboxylic acid t-butyl ester] 4-methoxybenzoic acid t-butyl ester 20 g as a raw material and tetrahydrofuran 200 as a solvent
g and 5% rhodium carbon 2 as a noble metal supported catalyst
g (50% wet product) was charged into a 500 ml stainless steel autoclave with stirring, at a temperature of 100 ° C.
The mixture was stirred for 2 hours under the condition of a hydrogen pressure of 50 kg / cm ² G.

After completion of the reaction, the obtained reaction mixture was cooled to room temperature, taken out of the autoclave, the catalyst was separated by filtration, and the solvent was distilled off to obtain 4-methoxy-1 represented by the following formula.
-Cyclohexanecarboxylic acid t-butyl ester 19.7
g was obtained as a colorless transparent liquid.

The purity of this 4-methoxy-1-cyclohexanecarboxylic acid t-butyl ester was measured by high performance liquid chromatography (HPLC, RI detector).
It was 8.3%.

[0111]

Embedded image

The identification of the above-mentioned 4-methoxy-1-cyclohexanecarboxylic acid t-butyl ester was carried out by H ¹ -NMR, mass spectrum and infrared absorption spectrum.
The measurement data is shown below. (1) H ¹ -NMR (60 MHz)

[0113]

[Table 5]

(2) Mass spectrum (DI method) Molecular ion peak (m / e): Undetectable Fragment peak: 159, 141, 126 (3) Infrared absorption spectrum C = O: 1730 cm ^-1 C-OC: 1150cm ^-1

[0115]

Example 6 [Production of 4,4 '-(di-t-butoxycarbonyl) dicyclohexyl ether] 20 g of 4,4'-(di-t-butoxycarbonyl) diphenyl ether as a raw material, 200 g of t-butanol as a solvent and a noble metal 4 g of 5% rhodium carbon (50% wet product) as a supported catalyst was stirred for 50 minutes.
In a 0 ml stainless steel autoclave, the temperature was 70 ° C. and the hydrogen pressure was 50 kg / cm ² G.
Stirred for 0 minutes.

After completion of the reaction, the obtained reaction mixture was cooled to room temperature, taken out of the autoclave, the catalyst was separated by filtration, and the solvent was distilled off to obtain 4,4 ′-(di-t) represented by the following formula. -
18. Butoxycarbonyl) dicyclohexyl ether
7 g were obtained as a colorless transparent liquid.

The purity of this 4,4 ′-(di-t-butoxycarbonyl) dicyclohexyl ether was determined by high performance liquid chromatography (HPLC, RI detector).
It was 4.0%.

[0118]

Embedded image

The above 4,4 ′-(di-t-butoxycarbonyl) dicyclohexyl ether was identified by using H ¹ -NM
R, mass spectrum and infrared absorption spectrum were used. The measurement data is shown below. (1) H ¹ -NMR (60 MHz)

[0120]

[Table 6]

(2) Mass spectrum (DI method) Molecular ion peak (m / e): Undetectable Fragment peak: 326, 309, 270 (3) Infrared absorption spectrum C = O: 1730 cm ^-1 C-OC: 1150cm ^-1

Claims (14)

[Claims] 1. The following general formulas [I] and [I] containing a hydroaromatic ring having at least one t-butoxycarbonyl group.
I], [III], [III] ', [IV], [IV]', [V],
Or the hydroaromatic carboxylic acid t- represented by [V] '
Butyl esters; [Wherein, n is an integer of 2 to 4]. [Wherein, X is a hydroxyl group, a methyl group, a t-butyl group, a methoxy group or a trifluoromethyl group, and p is 1 to 4
Which is an integer of [Wherein, m and n are each an integer of 0 to 2,
And m + n is 1 or 2.] Embedded image [Wherein, m and n are each an integer of 0 to 4,
And m + n is an integer of 1 to 4], Embedded image [Wherein, Y is an oxygen atom, a carbonyl group, or a hexafluoroisopropylidene group, m and n are each an integer of 0 to 4, and m + n is an integer of 1 to 4], Embedded image Wherein Y is an oxygen atom, a carbonyl group, or a hexafluoroisopropylidene group. 2. The hydroaromatic carboxylic acid t-butyl ester according to claim 1, wherein n = 2 in the general formula [I]. 3. The hydroaromatic carboxylic acid t-butyl ester according to claim 1, wherein in the general formula [II], X is a methoxy group or a trifluoromethyl group. 4. The hydroaromatic carboxylic acid t-butyl ester according to claim 1, wherein in the general formula [III], n = 2. 5. The t-butyl hydroaromatic carboxylate according to claim 1, wherein in the general formula [IV], n = 2. 6. The t-butyl hydroaromatic carboxylate according to claim 1, wherein in the general formula [V], n = 2. 7. The compound represented by the general formula [I]
1,2-cyclohexanedicarboxylic acid t-butyl ester,
3-cyclohexanedicarboxylic acid t-butyl ester, 1,4-
Cyclohexanedicarboxylic acid t-butyl ester, 1,2,4-
2. The hydroaromatic carboxylic acid t-butyl ester according to claim 1, which is cyclohexanetricarboxylic acid t-butyl ester or 1,2,4,5-cyclohexanetetracarboxylic acid t-butyl ester. 8. A compound represented by the general formula [II]:
2-methyl-1-cyclohexanecarboxylic acid t-butyl ester, 3-methyl-1-cyclohexanecarboxylic acid t-butyl ester, 4-methyl-1-cyclohexanecarboxylic acid t-butyl ester, 4-t-butyl-1- Cyclohexanecarboxylic acid t
-Butyl ester, 4-methoxy-1-cyclohexanecarboxylic acid t-butyl ester, 2-trifluoromethyl-1-cyclohexanecarboxylic acid t-butyl ester, 4-trifluoromethyl-1-cyclohexanecarboxylic acid t-butyl ester, The hydroaromatic carboxylic acid t-butyl ester according to claim 1, which is 2-hydroxy-1-cyclohexanecarboxylic acid t-butyl ester or 4-hydroxy-1-cyclohexanecarboxylic acid t-butyl ester. Kind. 9. A compound represented by the general formula [III]:
1-decahydronaphthalenecarboxylic acid t-butyl ester,
2-decahydronaphthalenecarboxylic acid t-butyl ester,
The hydroaromatic carboxylic acid t-butyl ester according to claim 1, which is 2,7-decahydronaphthalenedicarboxylic acid t-butyl ester or 1,4-decahydronaphthalenedicarboxylic acid t-butyl ester. Kind. 10. The compound represented by the general formula [III] ′ is a compound of the formula: 7-hydroxy-2-decahydronaphthalenecarboxylic acid
t-butyl ester, 5-hydroxy-2-decahydronaphthalenecarboxylic acid t-butyl ester, or 6-hydroxy
The hydroaromatic carboxylic acid t-butyl ester according to claim 1, which is -1-decahydronaphthalenecarboxylic acid t-butyl ester. 11. The compound represented by the above general formula [IV] is 4-dicyclohexylcarboxylic acid t-butyl ester,
4,4'-dicyclohexyldicarboxylic acid t-butyl ester, 3,3 ', 4-dicyclohexyltricarboxylic acid t-butyl ester or 3,3', 4,4'-dicyclohexyltetracarboxylic acid t-butyl ester The hydroaromatic carboxylic acid t-butyl ester according to claim 1, characterized in that: 12. The compound according to claim 1, wherein the compound represented by the general formula [IV] ′ is 4′-hydroxy-4-dicyclohexyltetracarboxylic acid t-butyl ester.
12. The hydroaromatic carboxylic acid t-butyl esters according to the above. 13. The compound represented by the above general formula [V] is 4- (t-butoxycarbonyl) dicyclohexyl ether, 4,4 ′-(di-t-butoxycarbonyl) dicyclohexyl ether, 3,4,4 ′ -(Tri-t-butoxycarbonyl)
Dicyclohexyl ether, 3,3 ', 4,4'-(tetra-t-butoxycarbonyl) dicyclohexyl ether, 4,4'-
(Hexafluoroisopropylidene) -1-dicyclohexylcarboxylic acid t-butyl ester, 4,4 ′-(hexafluoroisopropylidene) -1,1′-dicyclohexyldicarboxylic acid t-butyl ester, 4,4 ′-(hexafluoro Isopropylidene) -1,1 ', 2-dicyclohexyltricarboxylic acid t-
Butyl ester, 4,4 '-(hexafluoroisopropylidene) -1,1', 2,2'-dicyclohexyltetracarboxylic acid t-
2. A butyl ester, 4,4 '-(di-t-butoxycarbonyl) dicyclohexyl ketone, or 3,3', 4,4 '-(di-t-butoxycarbonyl) dicyclohexyl ketone. Hydro-aromatic carboxylic acid t- according to
Butyl esters. 14. The hydroaromatic carboxylic acid t according to claim 1, wherein the compound represented by the general formula [V] ′ is 4-hydroxy-4′-t-butoxycarbonyldicyclohexyl ether. -Butyl esters.