JPH01221342A - Novel hydroxy compound and production thereof - Google Patents

Abstract

NEW MATERIAL:The compound of formula II (Y is H, benzyl, 2,3- dihydroxypropyl, hydrocarbon group or lower alkyl having spiran ring; Z is same as Y excluding H and benzyl; n is 1-3). EXAMPLE:1-(4-Hydroxyphenoxy)-3-[4-(2,3-dihydroxy-1-propanoxy)phenoxy]-2- propanol. USE:A constituent component for polyester resin, alkyd resin, etc. It has excellent compatibility with polyester resin and gives an alkyd resin, polyester resin, etc., having excellent adhesivity, gas-barrierness, water-resistance, heat-resistance, etc. PREPARATION:A compound of formula II wherein Y is benzyl, Z is 2,3- dihydroxypropyl and n is 1 can be produced by reacting the compound of formula I with the compound of formula III in a solvent in the presence of a catalyst under heating. The catalytic hydrocracking of the obtained compound gives another compound of formula II wherein Y is H.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel hydroxy compound and a method for producing the same, and more specifically, a novel hydroxy compound useful as a constituent component of polyester resins or alkyd resins, and a method for producing the same. Regarding.

In the mouth<',・t and 1Question 1Aliphatic hydroxy compounds or alicyclic hydroxy compounds are polyesters such as saturated polyester resins, unsaturated polyester resins or alkyd resins, polycarbonate resins, epoxy resins, polyurethanes, etc. It is widely used as a raw material for various polymer materials.

Resins obtained from the above aliphatic hydroxy compounds or alicyclic hydroxy compounds have various physical properties such as adhesiveness, gas barrier properties, R-mechanical strength, heat resistance, weather resistance, and water resistance, depending on the respective use. There is a need for improvement.

For example, epoxy resins are used as adhesives in the manufacture of composite materials and are required to have high adhesive properties.

By the way, when manufacturing composite materials using adhesives,
It is known that aliphatic hydroxyl groups in adhesives play an important role in improving adhesiveness with substrates.

However, even compounds with aliphatic hydroxyl groups, such as aliphatic polyhydric alcohols, can be used for adhesives, but even when used to modify polyester resins, they are not compatible with polyester resins. In addition, conventionally, when producing epoxy resin, hydroquinone, resorcinol,
Monocyclic dihydric phenols such as catechol or 2,2-bis(4-hydroxyphenyl)propane [bisphenol A], 1,1-bis(4-hydroxyphenyl)ethane [bisphenol AD], bis(4-hydroxyphenyl), Bicyclic dihydric phenol compounds such as hydroxyphenyl)methane [bisphenol F] are used, but
Epoxy resins or polycarbonate resins obtained using such monocyclic or bicyclic dihydric phenol compounds have excellent heat resistance and dimensional stability. None of these have aliphatic hydroxyl groups. Therefore, for example, epoxy resin adhesives obtained using such monocyclic and bicyclic dihydric phenols have a problem of poor adhesion to substrates. Ta.

By the way, as a compound having an aliphatic hydroxyl group and a hydroquinone skeleton in the molecule, 1,3-bis(2-
Hydroxyphenoxy)-2-propanol (D, G,
Parsons, J, chem, Soc, Perkin
Trans. (5) 451-5 (1978) or 3-(4-hydroxyphenoxy)-1,2-propanediol (Fahren holtz).

Kennett+ E, cA 92(11); 9443
4u) is known.

However, epoxy resins obtained using these compounds have a problem in that they do not have sufficiently satisfactory physical properties such as adhesiveness and gas barrier properties.

The present invention is intended to solve the above-mentioned problems, and the adhesiveness, gas barrier, etc.
It can provide epoxy resins, polycarbonate resins, polyurethane, polyester resins, etc. with excellent properties, water resistance, heat resistance, etc., and also has excellent compatibility and can easily modify base polymers such as polyester resins. The object of the present invention is to provide a novel hydroxy compound having an aliphatic hydroxyl group and a hydroquinone skeleton, and a method for producing the same.

The novel hydroxy compound according to the present invention is as follows - Tsuzuriyo [
A] H...[A] [Wherein, Y is a hydrogen atom, a benzyl group, a 2,3-dihydroxypropyl group, a hydrocarbon group, or a lower alkyl group having a spiran ring, and Z is 2. It is either a 3-dihydroxy 117 pyl group, a hydrocarbon group, or a lower alkyl group having a spiran ring. Y and Z may be the same or different, n is a repeating unit, and n=1 to 3. ] It is expressed as .

Furthermore, among the novel hydroxy compounds according to the present invention, 1
-(4-benzyloxyphenoxy)-3-[4-(2
,3-dihydroxy-1-propanoxy)phenoxy]
-2-propanol is 0-benzyl-0°-(2,3
-epoxypropyl)hydroquinone and 0-(2,3-
Propanediol) is produced by reacting with hydroquinone.

Furthermore, among the novel hydroxy compounds according to the present invention, 1
-(4-hydroxyphenoxy)-3-[4-(2,3
-dihydroxy-1-propanoxy)phenoxy]-2
-10panol is produced by catalytic hydrogenolysis of 1-(4-benzyloxyphenoxy)-3-(4-(2,3-dihydroxy-1-propanoxy)phenoxy-1-2-propanol) .

Furthermore, among the novel hydroxy compounds according to the present invention, 1-(4-(1,4-dioxaspiro<4.5>decyl-2-methyloxy-))phenoxy-3-(4-
Hydroxyphenoxy)-2-propanol is 1-(
It is produced by reacting 4-hydroxyphenoxy)-3-[4-(2,3-dihydroxy-1-propanoxy)phenoxy]-2-propanol and cyclohexanone.

The novel hydroxy compound according to the present invention is represented by the above-mentioned general formula [A], and has an aliphatic hydroxyl group and a hydroquinone skeleton in the molecule, so it has excellent compatibility with polyester resins, etc. In addition to being able to easily modify polymers, epoxy resins obtained using this new hydroxy compound,
Polycarbonate resins, polyurethane, saturated polyester resins, unsaturated polyester resins, alkyd resins, and the like have excellent adhesive properties, gas barrier properties, water resistance, heat resistance, and the like.

1. The novel human 11x compound [A] according to the present invention will be specifically described below.

The novel hydroxy compound according to the present invention is the following - Tsuzuriyo [
A]...[A] [Wherein, Y is a hydrogen atom, a benzyl group, a 2,3-dihydroxypropyl group, a hydrocarbon group, or a lower alkyl group having a spiran ring, and Z is 2.3 - Dihydroxypropyl group, hydrocarbon group or lower alkyl group having a spiran ring. Y and Z may be the same or different, and n is an a unit, and n=1 to 3. ] It is expressed as .

Specifically, in the novel hydroxy compound represented by the above general formula [A], Y in the -spelling [A] is a benzyl group, Z is a 2,3-dihydroxypropyl group, and n= 1, 1-(4-benzyloxyphenoxy)-3[4-(2,3-dihydroxy-1-propanoxy)phenoxy]-2-propanol [IV], where Y is a hydrogen atom in formula [A], 1-(4-
hydroxyphenoxy)-3-[4-(2,3-dihydroxy-1-propanoxy)phenoxy 1-2-propanol [Vl, in formula [A], Y and Z are 2,3-dihydroxypropyl groups, and n= 1, 3-bis-[4-(
2,3-dihydroxy-1-propanoxy)phenoxy]-2-propanol, In the open formula [A], Y is a hydrogen atom, and 2 is phenoxy-3-(4-hydroxyphenoxy)-2-propanol [Vl], In addition, n=2, 1-(4-(1,4-dioxaspirox4.5>decyl-2-methyloxy-))phenoxy-3-14(2hydroxy-3-(4hydroxyphenoxy)1 -propanoxy) phenoxy 1-2 propatool [Vll, etc.

As described above, all the hydroxy compounds according to the present invention have an aliphatic hydroxyl group and a hydroquinone skeleton in their molecular skeletons. Therefore, the hydroxy compound according to the present invention has excellent compatibility, and can easily modify base polymers such as polyester resins. Polyesters such as polyester resins and alkyd resins, polycarbonate resins, epoxy resins, polyurethanes, and the like exhibit excellent performance in terms of heat resistance, water resistance, adhesiveness, gas barrier properties, etc., depending on their respective uses.

In addition, the hydroxy compound according to the present invention can be used as various additives such as lubricants, plasticizers, and antistatic agents useful for improving various physical properties such as moldability of various polymeric materials such as polyolefins and vinyl chloride, or as various additives. It is useful as a raw material for manufacturing agents. For example, soft vinyl chloride contains a large amount of plasticizers such as di-2-ethylhexyl phthalate and dihebutyl phthalate, but if the higher fatty acid ester of the hydroxy compound according to the present invention is used instead of these plasticizers, It is possible to improve the retention performance of soft vinyl chloride, such as nonvolatility, extraction resistance, water resistance, and water absorption.

Furthermore, the hydroxy compound according to the present invention can be used as an additive for various oil-based products such as lubricating oil and brake oil.
Performance such as lubricity of these products can be improved.

Next, the method for producing the novel hydroxy compound according to the present invention will be explained.

(1) 1-(4-benzyloxyphenoxy)-3[
4-(2,3-dihydroxy-1-propanoxy) phenoxy-2-propanol IV
In the binding margin [A], Y is a benzyl group, and Z is 2.
1-(4-benzyloxyphenoxy)-3[4-(2,3-dihydroxyphenoxy-1) which is a 3-dihydroxypropyl group and is represented by the following formula [IV] where n-=1
-Propanoxy) A method for producing phenoxy 1-2-propanol will be explained.

... [IV] In the production of the above hydroxy compound [IV], as represented by the following reaction formula (a), 0-benzyl-0°
-(2,3-epoxypropyl)hydroquinone [I]
and 0-(2,3-dihydroxy)propanediolhydroquinone [1] are used as raw materials. These raw materials themselves are synthesized as described below in (4).

[I] [1[[][IV] ...[Reaction formula-A] The reaction represented by the above reaction formula (A) theoretically has a molar ratio of [I]/[I[[]-1 /1 of the compound [I
] and [111] as raw materials, but in this reaction (a), the molar ratio of [I] and [111] is [
I]/[I[[]-0, preferably used in the range of 8/1 to 110.8, particularly 0.95/1 to 110.95
It is preferable to set it within the range of.

The reaction represented by the above reaction formula (a) can be efficiently proceeded by heating the compound [I] and [DI] in the presence of a catalyst.

Examples of the catalyst used in the reaction represented by the above reaction formula (a) include alkali metal hydroxides and onium salts. Specific examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, etc. Among them, inexpensive sodium hydroxide is preferably used.

As the onium salt, specifically, tetraethylammonium hydroxide (EAH), tetramethylammonium chloride, tetramethylsulponium iodide, methyltriphenylphosphonium iodide, etc. are used.

Such a catalyst is used in an amount of 0.05 parts by weight per 100 parts by weight of raw materials.
Preferably, it is used in an amount of 0.5 to 0.5 parts.

Such a catalyst can also be used as an aqueous solution, in which case it is used as an aqueous solution with a concentration of about 10 to 50%.

The reaction represented by the above reaction formula (a) can be carried out without using a solvent, but can also be carried out in the presence of a solvent if necessary. When the reaction represented by the above reaction formula (a) is carried out in the presence of a solvent, aromatic hydrocarbons, ethers, ketones, etc. are used as FiiJX. Specifically, toluene, xylene, etc. are used as aromatic hydrocarbons. As ethers,
Dioxane, tetrahydrofuran, etc. are used. Examples of ketones include aliphatic ketones having lower to higher alkyl groups, ketones with aryl groups such as phenyl groups (aromatic ketones), and cyclic ketones such as cyclohexanone, and cyclohexanone is preferably used. It will be done.

Such a solvent may be used in an amount of 100 to 100 parts by weight per 100 parts by weight of the raw material.
It is used in an amount of 500 parts by weight.

The reaction represented by the above reaction formula (in) can be carried out by heating the compounds [I] and [1] with stirring in the presence of the above-mentioned catalyst.

The reaction temperature is 50-150°C, preferably 90-120°C.
It is desirable that the temperature is ℃.

The reaction time varies depending on conditions such as the catalyst used, but is usually 0.1 to 10 hours.

After the above reaction, the product [IV] is separated and purified from the resulting mixture. When performing this separation and purification, general methods such as extraction, concentration, and crystallization can be used.

In the above manner, a compound [IV] of the formula [A] in which Y is a benzyl group, Z is a 2,3-dihydroxypropyl group, and n=1 is obtained.

Furthermore, in order to obtain a compound in which Y and Z are the same as in the case of compound [IV] and furthermore, n=2.3, when n=2, in the reaction formula (a) above, in place of compound 2
) is produced according to reaction formula (a) by using the compound described below.

(2) 1-(4-hydroxyphenoxy)-3-(4
-(2゜3-dihydroxy-1-propanoxy)phenoxy 1-2-propanol [V] manufacturing method (formula [A]
, Y is a hydrogen atom, 2 is a 2°3-dihydroxypropyl group, and n=1, 1-(4-hydroxyphenoxy)-3-[4-(2,
3-dihydroxy-1-propanoxy) phenoxy 1-
2-propanol is produced as follows.

That is, 1-(4-hydroxyphenoxy)-3-[4
-(2,3-dihydroxy-1-propanoxy)phenoxy-1-2-propanol is the compound [IV] obtained in the above (1), that is, 1-(4-benzyloxyphenoxy)-3(4-(2, It is obtained by catalytic hydrogenolysis of 3-dihydroxy-1-propanoxy)phenoxy 1-2-10panol.

This reaction formula is shown below.

[IV] [V] ... [Reaction formula - mouth] The reaction represented by the above reaction formula (b) is carried out in the presence of a catalyst,
The reaction is carried out at a temperature of room temperature to 150° C. by blowing hydrogen into the reaction system or by sealing hydrogen under pressure in a pressure-resistant container. As the catalyst, palladium carbon, palladium black, etc. can be used.

Although the reaction represented by the above reaction formula (b) can be carried out in the absence of a solvent, it is usually carried out in the presence of a solvent. When this reaction is carried out in the presence of a solvent, esters such as ethyl acetate and propyl acetate, carboxylic acids such as acetic acid and acetic acid 10-pionic acid,
Ethers such as dioxane, ethylene glycol, and monomethyl ether are used.

After completion of the reaction represented by the above reaction formula (b), compound [V] is separated and purified from the reaction mixture. When carrying out the 11i1 purification of compound [V], the catalyst can be first removed from the reaction mixture, and then common methods such as extraction, condensation, and crystallization can be used.

In the above manner, a compound [V] in the formula [A] in which Y is a hydrogen atom, 2 is a 2,3-dihydroxy 10-byl group, and n=1 is obtained. Similarly, a compound represented by the formula n=2.3 can also be obtained according to the above n=1.

(3) 1-(4(1,4-dioxaspiro<4.5>
Decyl-2-methyloxy-))phenoxy-3-(4
-hydroxyphenoxy)-2-propanol [VI]
Production method 1-(4(1,4-dioxyspiro<4.5
>Decyl-2-methyloxy-))phenoxy-3-(
4-Hydroxyphenoxy)-2-propanol is produced as follows. The method for producing this compound [VI] will be explained below.

Compound [V] obtained by the above (2), that is, 1-(
It is obtained by reacting 4-hydroxyphenoxy)-3-(4-(2,3-dihydroxy-1-propanoxy)phenoxy]-2-propanol and cyclohexanone.

This reaction formula is shown below.

[V]...[Reaction formula-c1 The reaction represented by the above reaction formula (c) is theoretically carried out using equimolar numbers of compound [V] and cyclohexanone, but this reaction In this case, it is preferable to use cyclohexanone in excess of the theoretical value.

-E The reaction represented by reaction formula (c) uses a protonic acid as a catalyst and is carried out at a temperature of 50 to 200°C, preferably 80 to 15°C.
The process proceeds efficiently by heating and stirring at a temperature of 0°C, usually for 1 to 5 hours.

Specific examples of the protonic acid used as a catalyst include paratoluenesulfonic acid hydrate, hydrochloric acid, sulfuric acid, phosphoric acid, chloroacetic acid, and sulfonic acid.

Although the reaction represented by the above reaction formula (c) can be carried out in the absence of a solvent, it is usually carried out in the presence of a solvent. As the solvent, aromatic hydrocarbons such as benzene and toluene are used.

After the reaction represented by the above reaction formula (c), in order to separate and purify the compound [Vl] produced from the resulting reaction mixture, first remove the catalyst from the reaction mixture, then extract...
Common methods such as cotton crystallization can be used.

In the above manner, a compound [VI] having Yn=1 in the formula [A] is obtained.

Similarly, by reacting compound formulas n=2 and 3 synthesized according to the above (2) with cyclohexanone according to "Reaction formula-c", a compound having a spirone ring at the corresponding terminal can be obtained. can.

Furthermore, the human 1 represented by the formula [A] according to the present invention
7xy compounds in which the combination of Y and Z is other than those mentioned above, where n=1 to 3, can be obtained by the production method of (1) to (3) as described above or using the raw materials as described below. It is easily produced by using synthesis method (4).

For example, 1,3-bis-[4-(2,3-dihydroxy-1-propanoxy)phenoxy 1-2-117 panol is a compound that adds the compound [VI] obtained in (3) above to glycidol ( Reaction represented by reaction formula (d)-〇 in raw material synthesis method (4) as shown below)
can be obtained in the same way.

(4) Raw materials 0-benzyl-〇'-(2,3-epoxypropyl)hydroquinone [I] and 0-(2,3-
Next, the raw materials used in reaction (a) in (1) above, namely 0-benzyl-○'-(2,3-epoxypropyl)hydroquinone [I] and 0- A method for synthesizing (2,3-propanediol)hydroquinone [III] will be explained.

First, as shown in reaction formula (d)-■ below, using hydroquinone monobenzyl ether [al and shrimp helohydrin [b] as starting materials and reacting them, O-benzyl-0°- (2,3-epoxypropyl)hydroquinone [I] is obtained.

[al [b] [I] ...[Reaction formula (d)-■] (In the formula, X is C1 or B") On the other hand, as shown in the following reaction formula (2)-■, starting Hydroquinone monobenzyl ether [al and glycidol [C] are used as raw materials.
] When both are reacted, 0-benzyl-0'-(2,3-propanediol)hydroquinone [nl is obtained.

[al [c] [II] ... [Reaction formula (d)-〇] In the reaction between hydroquinone monobenzyl ether [al and epiherohydrin [b] shown in the above reaction formula (d)-〇, [ In the reaction between hydroquinone monobenzyl [al and glycidol [C] shown in the above reaction formula (d)-0, an excess molar amount [bl is used relative to 311 mol]. Use the amount of [C].

In the reactions represented by the above reaction formulas (iv)-■ and (iv)-■, the above raw materials and the same catalysts as alkali metal hydroxides, onium salts, etc. described in (1) above are used. and stirred with PA at a reaction temperature of 50 to 110°C for 0.1 to 10 hours to form the compound [al
Compound [C] is ring-opened and added to compound [bl or compound [al]. In this case, the compound [al and the compound [C
] is subjected to ring-opening addition to obtain compound [11], that is, O-benzyl-0°-(2,3-dihydroxypropyl)hydroquinone. In the reaction between compound [al and compound [bl], as described above, [bl is once ring-opened and added to [al], and then an aqueous alkali metal hydroxide solution is added dropwise to the reaction system all at once or continuously. Then, when the ring-opening addition reaction product of compound [al and [bl] is ring-closed to form an epoxy ring, compound [I], that is, 0-benzyl-0°-
(2,3-epoxypropyl)hydroquinone is obtained.

When the reaction of the above reaction formula (d)-○ is carried out in the presence of shrimp herohydrin, by removing the water contained in the aqueous alkali metal hydroxide solution and the water produced by the reaction from the reaction system, 0-benzyl-0°-(2,3-
The production reaction of epoxypropyl)hydroquinone [I] can proceed efficiently.

In this way, an aqueous alkali metal hydroxide solution is used to form an epoxy ring in the reaction represented by reaction formula (d)-■. In particular, aqueous solutions of alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide are preferably used, and among them, an inexpensive aqueous solution of sodium hydroxide is particularly preferably used. This aqueous sodium hydroxide solution preferably has a concentration of 5 to 50% by weight.

The reactions represented by reaction formulas (d)-■ and (d)-■ can be carried out in the absence of a solvent, but aromatic hydrocarbons such as xylene and toluene, dioxane,
It can also be carried out in the presence of the same solvent as in (1) above, such as ethers such as tetrahydrofuran.

Even in the case where the product [I] is separated and purified from the reaction mixture obtained by the reaction represented by reaction formula (d)-■ as described above, the reaction represented by reaction formula (d)-■ The product [11] from the reaction mixture obtained by
In the case of separating and purifying , general methods such as extraction and crystallization are used.

In this way, 0-benzyl 0'-(2,3-epoxypropyl) as a raw material for one of the two used in (1)
Hydroquinone [I] is obtained.

In addition, 0-(2,3-
0-benzyl-0°-(2,3
-propanediol) by catalytic hydrogenolysis of hydroquinone [I[].

This reaction formula is shown below.

[U] [11[] ... [Reaction formula - E] This reaction can be carried out in the same manner as in (2) above.

After completion of the reaction represented by the above reaction formula (e), compound [1] is separated and purified from the reaction mixture. When separating and purifying compound [1], the catalyst can be first removed from the reaction mixture, and then general methods such as extraction, concentration, and crystallization can be used.

The thus obtained compound [11[] i.e. 0-
(2,3-propanediol)hydroquinone and the compound [I] obtained by the reaction represented by the reaction formula (d)-■, that is, 0-benzyl-0°-(2,3-epoxypropyl)hydroquinone, are (1) 1-
(4-benzyloxyphenoxy)-3[4-(2,3
-dihydroxy-1-propanoxy)phenoxy]-2
-Used as a raw material in producing propanol [IV].

The novel hydroxy compound according to the present invention is represented by the above-mentioned general formula [AI, and has an aliphatic hydroxyl group and a hydroquinone skeleton in the molecule, so it has excellent compatibility with polyester resins, and has excellent compatibility with polyester resins. Epoxy resins, polycarbonate resins, polyurethanes, saturated polyester resins, unsaturated polyester resins, alkyd resins, etc., obtained using this new hydroxy compound, can be easily modified into base polymers such as Depending on the application, it has excellent physical properties such as adhesiveness, gas barrier properties, water resistance, and heat resistance.

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

In the Examples below, the analytical conditions of gel chromatography (GPC) and liquid chromatography (LC) used for reaction tracking and purity analysis are shown below.

GPC analysis conditions Toyo Soda HLC-801A, polystyrene gel column: G2000X2+G3000XTIIF melting wax: 12m
1/min Column temperature: 40°C.

LC analysis conditions 0D34.6m+φX25cm (reversed phase column) Elution rate: 1ml/min Detector: UV 282n1m Gradient conditions = A solution (CH3CN) and B solution (C
H3CN/water = 1.4 water content, weight ratio (A/B
) = 15/85, A/B was changed continuously, and after 35 minutes it was changed to 85/15, and the developing solution was sent to the column at the same ratio for 50 minutes.

1-(4-benzyloxyphenoxy)-
3-[4-(2,3-dihydroxy-1-propanoxy)phenoxy-2-propano-I] By reacting hydroquinone monobenzyl ether with glycidol, 0-benzyl-0°-(2 ,3-dihydroxypropyl)hydroquinone is produced, and then hydrogen gas is added to this 0-benzyl-o'-(2,3-dihydroxypropyl)hydroquinone to produce 0-(2-dihydroxypropyl)hydroquinone, which is used as a raw material in the following reaction. ,3-dihydroxy)10panediolhydroquinone (III).

This reaction formula is shown below.

In addition, as shown in the reaction formula below, hydroquinone monobenzyl ether and epichlorohydrin are reacted in the presence of sodium hydroxide, and Q-
Benzyl-0°-(2,3-epoxypropyl)hydroquinone [I] was obtained.

Note that sodium chloride produced by this reaction was removed from the system.

A 500 ml round bottom flask equipped with a stirrer, thermometer, dropping funnel and reflux condenser was prepared, and o-(2,3
-dihydroxy)propanediolhydroquinone [I
[[] 118.4gQ-benzyl-0°-(2,3-
23 epoxypropyl)hydroquinone [I] and 150 ml of cyclohexane were charged.

Next, 20% aqueous tetraethylammonium hydroxide solution (EAI()O66t) was added to the raw material mixture charged in the flask while stirring at a temperature of room temperature to 60°C. After the addition of EAH, the mixture was heated to 110°C with stirring. The reaction was carried out for 8 hours at temperature.

The progress of this reaction can be determined by GPC analysis of the starting compound [
I] by tracking the decrease.

The reaction was then terminated with the disappearance of the starting compound [I].

After the reaction was completed, 70 ml of cyclohexanone was distilled off from the resulting reaction mixture using a rotary evaporator at a temperature of 70° C. and a reduced pressure of 300 to 400 μHg.

After distilling off 70 IIIl of cyclohexanone, the residue in the flask was cooled to a temperature of 10° C. to precipitate crystals.

Next, the crystals deposited in the flask were collected by filtration. The separated crystals were further washed with toluene 50011 and then dried to obtain 30 g of colorless powder.

As a result of LC analysis, this colorless powder has a purity (area ratio) of
was 97.8%, and the melting point was 121.5-124°C.

Moreover, the molecule Jit (MW) of this colorless powder was 440 as a result of mass spectrometry. Moreover, this molecular weight coincided with MW440 calculated from the large amount of.

K151 l-(4-hydroxyphenoxy)-3[4-(2,3
-dihydroxy-1-propanoxy)phenoxy]-2
- Propanol - 300 m1 with stirrer, gas inlet and reflux condenser
A round bottom flask was prepared, and in this flask were placed 28.4 g of the compound [IV] produced in Example 1, and 1 portion of ethyl acetate.
30 ml and palladium (5%)-activated carbon catalyst (Pd
At the same time, 3.8 g of catalyst) was charged, and nitrogen gas was introduced through a gas blowing pipe to replace the inside of the reaction system with a nitrogen atmosphere.

Then, using an oil bath, the contents of this flask were heated to 75%
The temperature was raised to ℃.

Then, at this temperature, hydrogen gas was introduced into the reaction system through the gas blowing pipe while stirring, and the contents of the flask were subjected to a hydrogenation reaction.

The progress of the reaction was checked by LC analysis to determine whether unreacted compounds [IV
] by tracking the decrease in From the time when the hydrogenation reaction of the contents of the flask approached completion, LC analysis was performed as described above at 30 minute intervals. Immediately after Compound [IV] disappeared, the introduced gas was switched from hydrogen gas to nitrogen gas to stop the reaction.

After cooling the flask contents to a temperature of 50°C,
The above P with a glass filter using diatomaceous filter aid
The d/c catalyst was removed from the flask contents and the reaction P
The liquid was separated.

Ethyl acetate was completely distilled off from the reaction mixture to obtain 21.9 tons of a pale gray, transparent viscous substance. The ethyl acetate was distilled off using a rotary evaporator, and finally at a temperature of 90°C and 10oC for 1 hour.
The system was maintained at mHIJ pressure.

When the above viscous substance was analyzed by LC, the purity (area ratio)
was 97.9%, and mass spectrometry showed that the molecular weight (MW
) was 350. Moreover, this molecule Jl (MW) coincided with MW350 calculated from a large amount of.

This viscous substance is also a compound This was also confirmed by proton NMR.

The spectrum of proton NMH is shown in FIG.

Further, as a result of mass spectrometry of this compound, the mass spectrum obtained is shown in FIG.

1-(4-(1,4-dioxaspiro<4.5>de, sil-2-methyloxy-))phenoxy)-3-(4hydroxyphenol 2-propanol Vl I)
An IJ round bottom flask equipped with a stirrer, a thermometer, and a reflux condenser with a water collector was prepared, and Example 2 was added to the flask.
100 g of the compound [Vl] produced by [Vl], 66.1 r of cyclohexanone, 600 ml of benzene, and 0.3 g of p-toluenesulfonic acid monohydrate were charged, and the reaction was carried out under benzene reflux for 5 hours.

Water generated as the reaction progressed was removed from the system using a collector. The end point of this reaction was determined to be the point at which the theoretical amount of water was produced. Finally, the disappearance of the raw material compound [Vl was confirmed by analysis of [A and C], which was taken as the end point of this reaction.

Then, after cooling the contents of the flask (reaction mixture) to room temperature, transfer the reaction mixture to a separatory funnel. and,
The catalyst present in the reaction mixture was neutralized, washed and removed using water and 5% by weight aqueous NaOH solution.

Then, using a rotary evaporator, the benzene melt and cyclohexanone were removed from the #IN in the reaction mixture, finally at a temperature of 90 °C and 5 am HI
Completely distilled off under reduced pressure of J to give a pale orange viscous substance 113.
4g was obtained.

As a result of LC analysis of this viscous substance, the purity (area ratio) was 94.
, 8%, and as a result of mass spectrometry, the molecular weight (MW) was 4.
It was 30. Moreover, this molecular weight coincided with MW430 calculated by substitution. Figure 3 shows the mass spectrum obtained as a result of mass spectrometry of this viscous material.

Manako's viscous substance is a compound This was also confirmed by proton NMR.

The proton NMR analysis spectrum is shown in FIG.

[Brief explanation of the drawing]

Figure 1 shows the proton NM of the compound obtained in Example 2.
This is a spectrum due to R. FIG. 2 is a mass spectrum obtained as a result of mass spectrometry of the compound. FIG. 3 is a mass spectrum obtained by mass spectrometry of the compound obtained in Example 3. Figure 4 shows the result of proton NMR analysis of the compound.
“) is a rare spectrum. Agent: Patent Attorney Shunichi Suzuki

Claims (7)

[Claims] (1) General formula [A] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ... [A] [In the formula, Y is a hydrogen atom, a benzyl group, a 2,3-dihydroxypropyl group, a hydrocarbon group, or a spiran ring. Z is a lower alkyl group having a 2,3-dihydroxypropyl group, a hydrocarbon group, or a spiran ring; Y and Z may be the same or different; n may be a repeating unit, and n=1 to 3. ] A novel hydroxy compound represented by: (2) The hydroxy compound is 1-(4-benzyloxyphenoxy)-3-[4-
The hydroxy compound according to claim 1, which is (2,3-dihydroxy-1-propanoxy)phenoxy]-2-propanol; ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ... [A -1] (3) The hydroxy compound is 1-(4-hydroxyphenoxy)-3-[4-(2-
,3-dihydroxy-1-propanoxy)phenoxy]
Claim 1 characterized in that it is -2-propanol.
Hydroxy compounds described in section; ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ・・・[A-2] (4) The hydroxy compound is 1-{4(1,4-dioxaspiro<4,5>decyl-
2-Methyloxy-)}phenoxy-3-(4-hydroxyphenoxy)-2-propanol; ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ・... [A-3] (5) O-benzyl-O'(2,3-epoxypropyl)hydroquinone and O-(2,3-propanediol)
1-( characterized by reacting with hydroquinone)
4-benzyloxyphenoxy)-3-[4-(2,3
-dihydroxy-1-propanoxy)phenoxy]-2
- A method for producing propanol. (6) 1-(4-benzyloxyphenoxy)-3-[
1-(4-hydroxyphenoxy)-3 characterized by subjecting 4-(2,3-dihydroxy-1-propanoxy)phenoxy]-2-propanol to catalytic hydrogenolysis
-[4-(2,3-dihydroxy-1-propanoxy)
Method for producing phenoxy]-2-propanol. (7) 1-(4-hydroxyphenoxy)-3-[4-
1-{4-(1,4-dioxaspiro<4,5>decyl-2-methyloxy) characterized by reacting (2,3-dihydroxy-1-propanoxy)phenoxy]-2-propanol and cyclohexanone -)} A method for producing phenoquine-3-(4-hydroxyphenoxy)-2-propanol.