JP2000159712A - Production of dihydroxy compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce the subject high-purity compound useful as a raw material intermediate, etc., for polymers excellent in hue and good in optical characteristics, heat resistance, mechanical properties, etc., by reacting a reducing agent when carrying out a reaction. SOLUTION: This compound represented by formula I [R1 is a (substituted) alkyl, a (substituted)alkoxy or the like; R2 is H or methyl; (k) is 0-3; (l) and (m) are each 0-10] is obtained by reacting a reducing agent (preferably a sulfite, etc.), when carrying out a reaction. The reaction is preferably carried out by reacting a spiroindanol derivative represented by formula II with β-halohydrins, alkylene carbonates or alkylene oxides in the presence of a catalyst (e.g. amines). The reducing agent is used in an amount of preferably 0.01-5 wt.% based on the compound represented by formula I. The alkylene carbonates are used in an amount of preferably 0.8-20 mol based on 1 mol of the compound represented by formula II. The catalyst is used in an amount of preferably 0.01-5 mol% based on 1 mol of the compound represented by formula II.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a dihydroxy compound, and more particularly to a method for producing a dihydroxy compound having a high purity and good hue by allowing a reducing agent to act upon the production of the dihydroxy compound. It is about. The dihydroxy compound has excellent optical properties (such as low birefringence) and is a very useful compound as a raw material intermediate for polymers having good heat resistance, good mechanical properties and the like.

[0002]

2. Description of the Related Art Inorganic glass is used in a wide range of fields as a transparent material because of its excellent properties such as excellent transparency and small optical anisotropy. However,
There are problems such as being heavy and easy to break, poor productivity, and the like. In recent years, development of a transparent polymer in place of inorganic glass has been actively conducted. As a transparent polymer, for example,
Polymethyl methacrylate, polycarbonate, and the like are excellent in transparency and mechanical properties (for example, impact resistance, etc.), and are excellent in workability and moldability. Therefore, they are an alternative field of inorganic glass, for example, transparent parts and lenses for automobiles. Etc. are used. In recent years, the use of optical disks for recording and reproducing information such as sound, images, characters, and the like using laser light has been rapidly expanding. However, in an optical disc used as an information recording medium, not only is it transparent because a laser beam passes through the disc body, but also optical homogeneity is strongly required to reduce an error in reading information. .

For example, when a known polymer such as polycarbonate is used, thermal stress, molecular orientation, and the like generated in the process of cooling and flowing the resin at the time of molding the disk substrate are described.
Residual stress due to a change in volume near the glass transition point causes birefringence when the laser beam passes through the disk substrate. The large optical non-uniformity caused by the birefringence is a fatal defect for an optical component such as an optical disc substrate, for example, an error in reading recorded information occurs. Although polymethyl methacrylate has good optical properties, it is hard to say that it has practically sufficient performance in terms of heat resistance, water absorption and the like. For this reason,
In optical components such as the above-described optical disc substrate, a novel polymer material having high optical characteristics, that is, having low birefringence, and having good performance in terms of heat resistance, mechanical properties, and the like, is used. It has been demanded.

In view of the above-mentioned requirements, the present inventors have studied and found that a polymer was produced by using a certain dihydroxy compound as a raw material intermediate (monomer) for a polymer. Has birefringence,
In addition, they have found that they have good heat resistance and mechanical properties and are optimal for the above-mentioned optical parts and the like, and have filed an earlier application (Japanese Patent Application No. 9-19609). However, it has been found that the presence of impurities in the monomer (dihydroxy compound) adversely affects the physical properties of the polymer, and that the presence of a coloring component deteriorates the hue of the polymer. Therefore, in order to produce a polymer used for the optical component or the like, a high-purity monomer is required.

[0005]

An object of the present invention is to provide a method for producing a dihydroxy compound having a high purity and a good hue, which is useful as a raw material intermediate for polymers and the like.

[0006]

Means for Solving the Problems The present inventors have made intensive studies in order to solve the above problems, and as a result, have reached the present invention. That is, the present invention relates to a method for producing a dihydroxy compound represented by the general formula (1) (formula 3), wherein a reducing agent is allowed to act upon the reaction.

[0007]

Embedded image (Wherein, R ₁ is a straight-chain, branched or cyclic alkyl group optionally having a substituent, a straight-chain, branched or cyclic alkoxy group optionally having a substituent, a nitro group or a halogen atom Wherein R ₂ represents a hydrogen atom or a methyl group, k represents an integer of 0 to 3, l and m each independently represent an integer of 0 to 10, and l + m represents 1 to 20.
Represents an integer. )

Further, the present invention relates to a method for preparing a spirobiindanol derivative represented by the general formula (2) (Formula 4) by reacting a β-halohydrin, an alkylene carbonate or an alkylene oxide in the presence of a catalyst. Wherein the reducing agent is a sulfite, a bisulfite, a thiosulfate, a dithionite or a pyrosulfite.

[0009]

Embedded image (Wherein, R ₁ is a straight-chain, branched or cyclic alkyl group optionally having a substituent, a straight-chain, branched or cyclic alkoxy group optionally having a substituent, a nitro group or a halogen atom And k represents an integer of 0 to 3.)

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The present invention is a method for producing a dihydroxy compound represented by the general formula (1), wherein a reducing agent is allowed to act upon the reaction.

In the general formula (1), R ₁ represents a linear, branched or cyclic alkyl group which may have a substituent, or a linear, branched or cyclic alkoxy group which may have a substituent. , A nitro group or a halogen atom. Preferably, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 20 carbon atoms which may have a substituent, a nitro group or halogen Represents an atom. Examples of the substituent of the alkyl group or the alkoxy group include, for example, an alkoxy group, an alkoxyalkoxy group, a cycloalkyl group, a heteroatom-containing cycloalkyl group, a cycloalkoxy group, a heteroatom-containing cycloalkoxy group, an aryloxy group, and an aryloxy group. Examples include an alkoxy group and a halogen atom.

Preferred examples of R ₁ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-pentyl, Hexyl group, 2-ethylhexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-tetradecyl group, n-octadecyl group, cyclopentyl group, cyclohexyl group, 4-tert-butylcyclohexyl group, cycloheptyl group A cyclooctyl group, a cyclohexylmethyl group, a cyclohexylethyl group, a tetrahydrofurfuryl group, a 2-methoxyethyl group, a 2-ethoxyethyl group, a 2-n-butoxyethyl group, a 3-methoxypropyl group, a 3-ethoxypropyl group, 3-n-propoxypropyl group, 3-n-butoxypropyl group, 3-n-f Sill propyl group, 2-
Methoxyethoxyethyl group, 2-ethoxyethoxyethyl group, 2-phenoxymethyl group, 2-phenoxyethoxyethyl group, chloromethyl group, 2-chloroethyl group, 3
-Chloropropyl group, 2,2,2-trichloroethyl group,

Methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, n-pentyloxy, n-
Hexyloxy group, 2-ethylhexyloxyl group, n
-Octyloxy group, n-decyloxy group, n-dodecyloxy group, n-tetradecyloxy group, n-octadecyloxy group, cyclopentyloxy group, cyclohexyloxy group, 4-tert-butylcyclohexyloxy group, cycloheptyloxy group , Cyclooctyloxy group, cyclohexylmethoxy group, cyclohexylethoxy group, 2-methoxyethoxy group, 2-ethoxyethoxy group, 2-n-butoxyethoxy group, 3-methoxypropoxy group, 3-ethoxypropoxy group, 3-n- Propoxypropoxy group, 3-n-butoxypropoxy group, 3-
n-hexyloxypropoxy group, 2-methoxyethoxyethoxy group, 2-phenoxymethoxy group, 2-phenoxyethoxyethoxy group, chloromethoxy group, 2-chloroethoxy group, 3-chloropropoxy group, 2,2,2-
Examples include a trichloroethoxy group, a nitro group, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The substituent R ₁ is more preferably an unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms, an unsubstituted linear or branched alkoxy group having 1 to 10 carbon atoms or a chlorine atom. More preferably, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, methoxy group,
Ethoxy, n-propoxy, isopropoxy, n
-Butoxy, isobutoxy, tert-butoxy or chlorine. Particularly preferably, R ₁ is a methyl group or a chlorine atom.

In the general formula (1), R ₂ independently represents a hydrogen atom or a methyl group. In the general formula (1), k represents an integer of 0 to 3, preferably k is 0, 1 or 2, and more preferably k is 0. In the general formula (1), l and m each independently represent an integer of 0 to 10, and 1 + m is 1 to 2
It is an integer of 0. l and m are preferably an integer of 0 to 8, more preferably an integer of 0 to 6, and still more preferably an integer of 0 to 4. However, l and m never become 0 at the same time.

In the compound represented by the general formula (1),
The substitution position of the substituent containing a hydroxy group on the spirobiindane ring is the 4-position, 5-position, 6-position or 7-position, and the substitution position of the other substituent is 4'-position, 5'-position, 6-position. 'Position or 7' position. Among these, preferred dihydroxy compounds represented by the general formula (1) are compounds represented by the general formulas (1-A) to (1-D) (formula 5), and more preferably, General formulas (1-A), (1-
C) or a compound represented by the general formula (1-D).
Of these structures, general formula (1-C) or general formula (1
The compound represented by -D) is particularly preferred.

[0017]

Embedded image (In the formula, R ₁ , R ₂ , k, l and m are the same as described above.) As the dihydroxy compound represented by the general formula (1),
Typically, dihydroxy compounds shown in the following Table 1 (Tables 1 to 8) can be exemplified, but of course, the present invention is not limited to these.

[0018]

[Table 1]

[0019]

[Table 2]

[0020]

[Table 3]

[0021]

[Table 4]

[0022]

[Table 5]

[0023]

[Table 6]

[0024]

[Table 7]

[0025]

[Table 8]

The reaction for producing the dihydroxy compound represented by the general formula (1) of the present invention is carried out in the presence of a catalyst in the presence of a spirobiindanol derivative represented by the following formula (2) (formula 6) and ethylene oxide: , Alkylene oxides such as propylene oxide, cyclic alkylene carbonates such as ethylene carbonate and propylene carbonate, 2-
It reacts with β-halohydrins such as bromoethanol, 2-chloroethanol and 2-bromo-1-propanol. Among these methods, the reaction is preferably performed using an alkylene oxide or an alkylene carbonate.

[0027]

Embedded image (Wherein, R ₁ and k are the same as described above)

When the reaction is carried out using alkylene oxides, depending on the reaction conditions, in addition to the formation reaction of the dihydroxy compound represented by the general formula (1), a side reaction due to the self-addition reaction of the alkylene oxides may occur. It is particularly preferable to use alkylene carbonates because of problems such as generation of products. The spirobiindanol derivative represented by the general formula (2) can be obtained by a known method, for example,
It is produced according to the method described in JP-A-62-10030, that is, a method in which 2,2-bis (4-hydroxyphenyl) propane is heated in the presence of perfluoroalkanesulfonic acid.

In the production method of the present invention, a reducing agent
Is made to act. Of the present invention
Specific examples of the reducing agent used in the production method include Na_TwoS
O_Three, K_TwoSO_Three, CaSO_Three, (NH_Four)_TwoSO_Threeetc
Of sulfite, NaHSO_Three, KHSO _Three, Ca (HSO
_Three)_Two, NH_FourHSO_ThreeSuch as bisulfite, Na_TwoS_Two
O_Three, BaS_TwoO_Three, (NH_Four)_TwoS_TwoO_ThreeThiosulfur such as
Acid salt, Na_TwoS_TwoO_FourDithionite, Na_TwoS_Two
O_Five, K_TwoS_TwoO_FiveSuch as pyrosulfite, Na_TwoS, Na
SH and the like. Preferably, Na_TwoSO_Three, K_Two
SO_Three, NaHSO_Three, KHSO_Three, Na_TwoS _TwoO_Three,
Na_TwoS_TwoO_Four, Na_TwoS_TwoO_Five, K_TwoS_TwoO_FiveIn
And more preferably Na_TwoSO_Three, K_TwoSO_Three, Na
HSO_Three, KHSO_Three, Na_TwoS_TwoO_Three, Na_TwoS_TwoO
_FourAnd more preferably Na_TwoSO_Three, K_TwoSO
_Three, NaHSO_Three, KHSO_Three, Na_TwoS_TwoO_FourIn
Na_TwoS_TwoO_FourIs most preferred. These reducing agents
May be used alone or as a mixture of two or more
May be. The amount of reducing agent used is determined by the general formula
0.0 to the dihydroxy compound represented by (1)
01% by weight to 10% by weight is preferable, and more preferably,
It is 0.01% by weight to 5% by weight. The reducing agent is
In time, it may be dissolved or suspended without dissolving
Is also good.

Hereinafter, the reaction of the spirobiindanol derivative represented by the general formula (2) with an alkylene carbonate such as ethylene carbonate and propylene carbonate will be described in detail. Ethylene carbonate, the use amount of alkylene carbonates such as propylene carbonate,
Depending on the number of desired oxyalkylene groups added, that is, the number of l and m in the general formula (1),
Usually, it is 0.3 to 60 mol, preferably 0.5 to 50 mol, more preferably 0.8 to 1 mol of the spirobiindanol derivative represented by the general formula (2).
２０20 mol. The reaction catalyst is not particularly limited, but is typically a basic organic compound such as an amine, an alkali metal compound, an alkaline earth metal compound, or an inorganic or organic various metal compound such as an organic acid metal salt. Can be exemplified.

The amines are preferably tertiary amines having no active hydrogen. Examples thereof include aliphatic amines such as triethylamine, tripropylamine and tributylamine, aralkylamines such as benzyldimethylamine, and alicyclic amines such as triethylenediamine. The formula amine can be exemplified. Alkali metal compounds and alkaline earth metal compounds include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, calcium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, hydrogenated Sodium, calcium hydride, metallic sodium, metallic potassium, sodium methoxide, sodium ethoxide, potassium
tert-butoxide and the like. Examples of the metal salts of organic carboxylic acids include various aliphatic carboxylic acids, sodium salts, potassium salts of aromatic carboxylic acids, and other metal salts. Further, a sodium or potassium salt of a spirobiindanol derivative represented by the general formula (2) can also be used.

The use amount of these reaction catalysts is preferably 0.001 mol% to 10 mol%, more preferably 0.1 mol%, per 1 mol of the spirobiindanol derivative represented by the general formula (2). It is from 01 mol% to 5 mol%. These reaction catalysts may be used alone or as a mixture of two or more.

In this reaction, the reaction may be carried out using a reaction solvent or without a solvent. When the reaction is performed in the absence of a solvent, it is desirable that the reaction be performed by melting at a temperature higher than the melting point of the reaction compound. When a reaction solvent is used, various known solvents which are inert to the reaction can be used. As such a reaction solvent, for example, benzene, toluene, xylene, aromatic hydrocarbon solvents such as mesitylene, hexane,
Aliphatic hydrocarbon solvents such as octane, acetone, methyl ethyl ketone, methyl propyl ketone, diethyl ketone, methyl isobutyl ketone, diisopropyl ketone,
Ketone solvents such as methyl amyl ketone, diisobutyl ketone, cyclohexanone and methyl cyclohexanone; ester solvents such as ethyl acetate, butyl acetate and amyl acetate; ether solvents such as dioxane, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether; N, N-dimethyl Examples include aprotic polar solvents such as formamide, N-methylpyrrolidone, N, N-dimethylimidazolidinone, and dimethyl sulfoxide.

Preferred solvents are aromatic hydrocarbon solvents, ester solvents and ketone solvents, more preferably toluene, xylene, mesitylene, amyl acetate, diethyl ketone, methyl isobutyl ketone, diisopropyl ketone, methyl amyl Ketone, diisobutyl ketone, cyclohexanone, and methylcyclohexanone, more preferably xylene and mesitylene. These solvents may be used alone or as a mixture.

The amount of the reaction solvent used is not particularly limited. However, if the amount is too large, it is not preferable in terms of production efficiency and the like, and the spirobiindanol derivative represented by the general formula (2) is usually used. And 300 times by weight or less, preferably 100 times by weight or less, and more preferably 2 times by weight or less with respect to the total weight of the alkylene carbonates.
It is not more than 0 times the weight.

The reaction may be performed in an air atmosphere or an inert gas atmosphere, but is performed in an atmosphere of an inert gas such as nitrogen or argon in order to suppress coloring of the reaction product. It is preferred. The reaction temperature varies depending on the reaction catalyst and the reaction solvent used.
To 200 ° C., more preferably 50 to 180 ° C.
° C. The reaction time varies depending on the type of the reaction catalyst, the charged amount of ethylene carbonate and propylene carbonate, the reaction temperature and the like, but usually 0.5 to 50 hours is sufficient.

Next, the reaction between the spirobiindanol derivative represented by the general formula (2) and an alkylene oxide such as ethylene oxide and propylene oxide will be described in detail. The reaction of a spiroobiindanol derivative with an alkylene oxide is described, for example, in US Pat. No. 3,794,617,
A method similar to the method described in JP-B-60-5578 and JP-A-6-10151, that is, a reaction of a spirobiindanol derivative represented by the general formula (2) with an alkylene oxide in the presence of a catalyst. It is implemented by having

The amount of ethylene oxide and propylene oxide used depends on the number of the desired oxyalkylene group added, that is, the number of l and m in the general formula (1), but is usually represented by the general formula (2) The amount is 0.3 to 60 mol, and preferably 0.5 to 50 mol, per 1 mol of the spirobiindanol derivative.

The reaction catalyst is not particularly limited, but is typically a basic organic compound such as an amine, or an inorganic or organic compound such as an alkali metal compound, an alkaline earth metal compound, or an organic acid metal salt. Examples of the catalyst include the same catalysts as in the case of the above-mentioned alkylene carbonates such as various metal compounds. The use amount of these reaction catalysts is preferably 0.001 mol% to 10 mol%, more preferably 0.01 mol%, based on 1 mol of the spirobiindanol derivative represented by the general formula (2). ~ 5 mol%. These reaction catalysts may be used alone or in combination of two or more.

In the reaction, a reaction solvent may be used, or the reaction may be performed without a solvent. When the reaction is performed in the absence of a solvent, the reaction is preferably performed by melting at a temperature equal to or higher than the melting point of the reaction compound. When a reaction solvent is used, various known solvents which are inactive as in the case of the above-mentioned alkylene carbonates can be exemplified. There is no particular limitation on the amount of the reaction solvent used. However, if the amount is too large, it is not preferable in terms of production efficiency and the like.
Is not more than 300 times by weight, and preferably not more than 100 times by weight, based on the total weight of the spirobiindanol derivative and alkylene oxides represented by

The reaction temperature varies depending on the reaction catalyst and reaction solvent used, but is preferably from 30 to 200 ° C., more preferably from 50 to 180 ° C. The reaction pressure cannot be limited because it varies depending on the heat removal capacity and pressure resistance of the reactor, but it is usually preferable to carry out the reaction at normal pressure to 10 kg / cm ² G,
More preferably, the pressure is from normal pressure to 5 kg / cm ² G. The reaction time varies depending on the type of catalyst, the charged amounts of ethylene oxide and propylene oxide, the reaction temperature, the reaction pressure conditions, and the like, but usually 0.5 to 50 hours is sufficient.

After completion of the reaction, if necessary, the reducing agent and the reaction catalyst used are filtered, washed with water, or neutralized with a mineral acid (for example, hydrochloric acid or sulfuric acid) or an organic acid (for example, acetic acid or propionic acid). For example, it can be removed by processing according to a conventional method. When the reaction catalyst is an inorganic salt, washing with water is preferable, and when the reducing agent is an inorganic salt, it is particularly preferable to wash with water because many of them are water-soluble. The method of washing with water is roughly divided into two types, a method of performing crystallization filtration and then washing with water, and a method of washing the solution after the reaction with water.

In the former method, for example, after the reaction (method a), the desired dihydroxy compound crystallized is separated by filtration or the like, and the filter cake wet with a solvent or dried is added to water. Heating and stirring as necessary, or (b method) heating and dissolving the dihydroxy compound separated by filtration or the like in a mixture of water and an organic solvent miscible with and soluble in water. There is a method of crystallization by cooling.

The latter method is a method in which water is added to the solution of the dihydroxy compound after the reaction, and if necessary, the mixture is heated, stirred and washed with water. In this case, the operation method differs depending on whether the reaction solvent used is water-soluble or water-insoluble. For example, when the reaction solvent is water-soluble, the desired dihydroxy compound is precipitated by gradually adding water, so that crystallization is performed simultaneously with washing with water (method c). When the reaction solvent is water-insoluble, the solution layer and the aqueous layer of the dihydroxy compound are separated, so that the mixture is washed with water by stirring, separated, the aqueous layer is removed, and then the crystallization operation is performed. (D method). Note that the washing method is not limited to the above method.

By precipitating only the desired dihydroxy compound at the time of crystallization and leaving the compounds other than the dihydroxy compound (impurities (residues of raw materials, by-products), reducing agents, reaction catalysts, etc.) dissolved, By filtering this, a highly pure dihydroxy compound is obtained. Therefore, specifically, the purity is more improved when the crystallization is performed so that the crystals of the dihydroxy compound grow slowly than when the crystals are rapidly performed. In the aforementioned washing method,
In the (a) method, the inorganic salts incorporated in the crystals during the crystallization are hardly removed by the subsequent washing with water, and in the (c method), water, which is a poor solvent, is added, so that the crystallization is difficult to be performed slowly. Easy to take in impurities. For this reason, as the water washing method, (method b) and (method d) are preferable, and (method d) is more preferable in the above-described examples.

When drying the dihydroxy compound wet with a solvent, which is taken out by filtration or the like, the drying temperature is preferably from 20 to 150 ° C., more preferably from 30 to 150 ° C.
100 ° C. At this time, the reaction may be performed under an air atmosphere, under an inert gas atmosphere, or under reduced pressure.However, in order to suppress coloring or the like due to oxidation, the reaction may be performed under an inert gas atmosphere such as nitrogen or argon, or It is preferable to reduce the pressure to a vacuum.

The general formula (1) obtained by the production method of the present invention
The dihydroxy compound represented by is highly pure and excellent in hue, and is very useful as a raw material for polymers having good optical properties (such as low birefringence), heat resistance and mechanical properties. .

[0048]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. The evaluation of the hue was made according to JIS as follows.
The Hazen color index was determined from the APHA standard colorimetric liquid according to the description in K-1557. Evaluation of hue: 30 g of the dihydroxy compound represented by the general formula (1) was precisely weighed and completely dissolved in 70 g of N, N, -dimethylformamide (reagent for spectrum) in a 300 ml stoppered Erlenmeyer flask. This solution was put into a colorimetric tube up to the marked line, and the color of the APHA standard chromaticity sequence was compared with the naked eye.

Example 1 In a reaction vessel, 6,6′-dihydroxy-3,3,3 ′,
3'-tetramethyl-1,1'-spirobiindane 308
g (1.0 mol), 185 g of ethylene carbonate
(2.1 mol), 6.9 g (50 mmol) of potassium carbonate
l), 0.8 g of sodium bisulfite and 850 g of mixed xylene were charged, and the mixture was heated under reflux for 10 hours. After cooling,
The resulting solid was filtered off and the cake was stirred in water at 50 ° C.
After filtration, washing with water and drying, 329 g (yield 83%) of the desired dihydroxy compound represented by the formula (3) (Formula 7) was obtained as a white solid. The melting point of this compound is 154-15
8 ° C. and a Hazen color index of 6.

[0050]

Embedded image

Example 2 A reaction vessel was charged with 6,6′-dihydroxy-3,3,3 ′,
3'-tetramethyl-1,1'-spirobiindane246
g (0.8 mol), ethylene carbonate 308 g
(3.5 mol), 4.2 g of sodium carbonate (40 mm
ol), 4.5 g of sodium dithionite and 2.4 kg of mixed xylene, and heated under reflux for 10 hours. 9
After cooling to 0 ° C, 500 g of water was added and stirred at 90 ° C,
After the stirring was stopped and the liquid was separated, the aqueous layer (lower layer) was removed. Similarly, washing with 500 g of water was repeated three times to remove the aqueous layer and then allowed to cool. After cooling to room temperature, the resulting solid was filtered and dried to obtain 306 g (yield 79%) of the desired dihydroxy compound represented by the formula (4) (formula 8) as a white solid. This compound had a melting point of 126 to 130 ° C. and a Hazen color index of 5.

[0052]

Embedded image

Example 3 A reaction vessel was charged with 6,6′-dihydroxy-3,3,3 ′,
3'-tetramethyl-1,1'-spirobiindane246
g (0.8 mol), 173 g of propylene carbonate
(1.7 mol), 5.5 g of potassium carbonate (40 mmol)
l), 3.0 g of sodium sulfite and mixed xylene 5
Then, the mixture was heated to reflux for 8 hours. After cooling to 85 ° C., 500 g of methyl isobutyl ketone and 500 g of water were added, and the mixture was stirred at 83 ° C., stopped stirring, and separated to remove the aqueous layer (lower layer). Similarly, washing with 500 g of water was repeated twice to remove the aqueous layer and then allowed to cool. After cooling to room temperature, the resulting solid was filtered and dried to obtain 265 g of the desired dihydroxy compound represented by the formula (5) (yield: 78).
%) As a white solid. The melting point of this compound is 19
The temperature was 6 to 199 ° C, and the Hazen color index was 7.

[0054]

Embedded image

Example 4 A reaction vessel was charged with 6,6′-dihydroxy-3,3,3 ′,
3 ', 5,5', 7,7'-octamethyl-1,1'-
218 g (0.6 mol) of spirobiindane, 114 g (1.3 mol) of ethylene carbonate, 4.1 g (30 mmol) of potassium carbonate, 2.2 g of sodium dithionite and 218 g of p-xylene were charged and heated under reflux for 12 hours. After cooling, the resulting solid was collected by filtration, recrystallized from a methanol-water mixture and purified, and the desired compound of the formula (6)
203 g (89% yield) of a dihydroxy compound represented by the following formula (III) was obtained as a white solid. This compound had a melting point of 129 to 132 ° C. and a Hazen color index of 5. .

[0056]

Embedded image

Example 5 A reaction vessel was charged with 6,6′-dihydroxy-3,3,3 ′,
3'-tetramethyl-1,1'-spirobiindane 308
g (1.0 mol), 185 g of ethylene carbonate
(2.1 mol), 6.9 g (50 mmol) of potassium carbonate
l), 1.0 g of sodium thiosulfate and 700 g of mixed xylene were charged, and heated under reflux for 9 hours. After cooling, the resulting solid was collected by filtration, and the filter cake was stirred in water at 50 ° C., filtered, washed with water, and dried to obtain 337 g of the desired dihydroxy compound represented by the formula (3) (yield: 85%). ) Was obtained as a white solid. This compound had a melting point of 154 to 158 ° C and a Hazen color index of 8.

Example 6 In a reaction vessel, 6,6′-dihydroxy-3,3,3 ′,
3'-tetramethyl-1,1'-spirobiindane246
g (0.8 mol), 443 g of ethylene carbonate
(6.3 mol), 5.5 g of potassium carbonate (40 mmol)
l), 3.0 g of sodium dithionite and 500 g of mixed xylene were charged and heated under reflux for 9 hours. After cooling to 85 ° C., 500 g of methyl isobutyl ketone and 50 g of water
After adding 0 g and stirring at 83 ° C., stirring was stopped and liquid separation was performed, and then the aqueous layer (lower layer) was removed. Similarly, washing with 500 g of water was repeated twice to remove the aqueous layer and then allowed to cool. After cooling to room temperature, the resulting solid was filtered and dried to obtain the desired dihydroxy compound 348 represented by the formula (7).
g (76% yield) was obtained as a white solid. This compound had a melting point of 122 to 125 ° C. and a Hazen color index of 6.

[0059]

Embedded image

Comparative Example 1 The reaction was carried out in the same manner as in Example 1 except that sodium hydrogen sulfite was not used, to obtain a compound represented by the formula (3). The melting point of this compound is 155-158
C. and a Hazen color index of 13. Comparative Example 2 The reaction was carried out in the same manner as in Example 2 except that sodium dithionite was not used, to obtain a compound represented by the formula (4). The melting point of this compound is 126-12.
The temperature was 9 ° C. and the Hazen color index was 11. Comparative Example 3 The reaction was carried out in the same manner as in Example 3 except that sodium bisulfite was not used, to obtain a compound represented by the formula (5). This compound had a melting point of 197 to 201 ° C. and a Hazen color index of 14. Comparative Example 4 The reaction was carried out in the same manner as in Example 4 except that sodium dithionite was not used, to obtain a compound represented by the formula (6). The melting point of this compound is 128-132 ° C.
And a Hazen color index of 11. Reference Example 1 A stirrer, a reflux condenser,
A dip tube for phosgene (carbonyl chloride) blowing was attached. In this flask, 198 g (0.5 g) of the dihydroxy compound represented by the formula (3) obtained in Example 1 was added.
0 mol) and 100 g of dichloromethane. To this mixture, 104 g of phosgene (1.0
5 mol) over 60 minutes and the reaction mixture was stirred and mixed for an additional 2 hours. After the completion of the reaction, nitrogen gas was blown in, and excess phosgene and hydrogen chloride produced as a by-product were distilled off. Thereafter, dichloromethane was distilled off under reduced pressure, and bischloroformate 26 represented by the following formula (8) (Formula 12) was obtained.
0 g (0.50 mol) were obtained.

[0061]

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Contents 3 equipped with stirrer and reflux condenser
In a 00 ml flask, 52.1 g (0.10 mol) of the obtained bischloroformate represented by the formula (A) and 39.6 g (0. 0 mol) of the dihydroxy compound represented by the formula (3) were obtained.
10 mol) and 200 g of dichloromethane.
To this mixture, 17.4 g (0.22 mol) of pyridine was added dropwise over 30 minutes under ice cooling, and the mixture was further stirred at the same temperature for 2 hours. After the completion of the polymerization reaction, a dilute hydrochloric acid aqueous solution was added to the reaction mixture, and the mixture was stirred. After removing excess pyridine, the dichloromethane phase was washed with ion-exchanged water until neutral, and separated. Dichloromethane was distilled off from the dichloromethane solution of the obtained polycarbonate to obtain a solid polycarbonate. The weight average molecular weight of this polycarbonate was 48,000. Also,
A press sheet of this polycarbonate was prepared for hue evaluation. After heating without pressure at 280 ° C for 5 minutes, 1 minute
A press sheet having a thickness of 500 μm was obtained by applying a pressure of 00 kg / cm ² . The YI (yellow index) value of this sheet measured 1.9.

Reference Example 2 The same operation as in Reference Example 1 was carried out except that the compound prepared in Example 1 was used instead of the compound prepared in Example 1 as the dihydroxy compound represented by the formula (3). As a result, a polycarbonate having a weight average molecular weight of 44000 was obtained. The YI value of this polycarbonate press sheet was 4.2.

As described above, the polycarbonate obtained by using the dihydroxy compound produced by the production method of the present invention as a raw material has excellent hue, low birefringence, heat resistance, mechanical properties and the like. Also had good performance. Furthermore, polymers such as polyesters and polyurethanes obtained using the dihydroxy compound produced by the production method of the present invention as raw materials also have excellent optical properties (low coloration, that is, high transmittance, and low birefringence), and It was found that heat resistance, mechanical properties and the like were also good.

[0065]

According to the present invention, high purity and good hue having excellent optical properties (such as low birefringence) and useful as a raw material for polymers having good heat resistance and mechanical properties are provided. It has become possible to provide dihydroxy compounds.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07C 201/12 C07C 201/12 205/37 205/37 // C07B 61/00 300 C07B 61/00 300 ( 72) Inventor Tatsunobu Urakami 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Inside of Mitsui Chemicals Co., Ltd. 1190 Kasama-cho, Sakae-ku, Yokohama-shi F-term (reference) in Mitsui Chemicals, Inc. 4H006 AA02 AC43 BA02 BA06 BA29 BA32 BA36 BA51 BE63 BE90 GN03 GN04 GN06 GN08 GP01 GP03 GP10 GP22 4H039 CA61 CD10 CD20 CD90 CH70

Claims (3)

[Claims] 1. A method for producing a dihydroxy compound represented by the general formula (1), wherein a reducing agent is allowed to act during the reaction. Embedded image (Wherein, R ₁ is a straight-chain, branched or cyclic alkyl group optionally having a substituent, a straight-chain, branched or cyclic alkoxy group optionally having a substituent, a nitro group or a halogen atom Wherein R ₂ each independently represents a hydrogen atom or a methyl group, k represents an integer of 0 to 3, l and m each independently represent an integer of 0 to 10, and
l + m represents an integer of 1 to 20. ) 2. The reaction is carried out in the presence of a catalyst by the general formula (2)
A spirobiindanol derivative represented by the following formula (2);
-Reacting with a halohydrin, an alkylene carbonate or an alkylene oxide.
The manufacturing method as described. Embedded image (Wherein, R ₁ is a straight-chain, branched or cyclic alkyl group optionally having a substituent, a straight-chain, branched or cyclic alkoxy group optionally having a substituent, a nitro group or a halogen atom And k represents an integer of 0 to 3.) 3. The method according to claim 1, wherein the reducing agent is a sulfite, a bisulfite, a thiosulfate, a dithionite or a pyrosulfite.