JPS58159436A - Etherification method of phenolic hydroxyl group - Google Patents

Abstract

PURPOSE:To etherify a phenolic hydroxyl group in high purity and yield, by keeping an organic compound having the phenolic hydroxyl group and a halogenated organic compound previously in an inert organic solvent at a refluxing temperature, and adding an alkali metal slowly thereto. CONSTITUTION:An organic compound having one or more phenolic hydroxyl groups in one molecule, e.g. phenol or novolak resin, and a halogenated organic compound of the formula RX R is alkyl, alkynyl, aralkyl or formula (R' is monofunctional organic group; R'' is 1-8C bifunctional organic group; n is 0 or a positive integer 1-10); X is halogen are dissolved in an inert organic solvent, and kept at a reflux temperature. An alkali metal or a compound thereof is slowly added to the solution and reacted while removing the water in the system or produced water in the form of an azeotropic mixture with the inert solvent to etherify the phenolic hydroxyl groups. USE:The post-treatment is carried out easily without using a polar solvent, and the reaction time can be reduced.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improved and novel method for etherifying phenolic hydroxyl groups.

Conventionally, 5 methods have been used to etherify phenolic hydroxyl groups.
For example, it is preferable to react phenoxylates for alkali metal by reacting an alkali metal compound with phenols in advance, separating and obtaining the alkali metal phenoxylates produced therein, and then reacting or producing the alkali metal phenoxylates with an alkyl halide. A method in which an alkyl halide is added and reacted without removing or removing water in the electrolyte in the same solvent without obtaining 1llIt in minutes.In history, the coexistence of alkyl halides, phenols, and alkali metal compounds is known. The following reaction methods are known.

However, in any of the above-mentioned methods, when completely etherifying a high degree of polymerization such as a phenol novolac resin, the alkali metal groups of the phenol novolac are not dissolved in the hydrocarbon yarn bath medium, and therefore the diminutive The disadvantage is that it is necessary to use local polar solvents such as tersulfoside, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone. Also? '＋
The resin obtained by the method described above has the disadvantage that it is black and rots in color, so it tends to be transparent, which limits its field of application.

The present invention aims to provide a novel method for etherifying a phenolic hydroxyl group that eliminates the above-mentioned disadvantages and disadvantages. ) and the general formula % formula % (1) [wherein R is an alkyl group, an alkenyl group, an aralkyl group, or a formula (where R' is a substituted or unsubstituted monovalent organic group, R''
is a C1-6 divalent organic group, n is D or a positive integer of 1-10), and X is a halogen atom. When reacting in the presence of M'
l Nrf = dissolving the organic compound (4) and the halogenated organic compound (B) in an inert organic solvent, maintaining the reaction thread at the reflux temperature, and reacting while constantly adding an alkali metal or alkali metal compound. It is characterized by:

According to the method of the present invention, even in the complete etherification of highly polymerized resins such as phenol novolac resins, the reaction can proceed satisfactorily by using ordinary hydrocarbon solvents without using polar solvents such as dimethyl sulfoxide or dimethyl formamide. However, since it is sufficient to use a common hydrocarbon thread solvent, post-treatment is easy and the reaction time can be shortened.Furthermore, the etherified product obtained by this method has a low degree of coloration. Because it is very small and has good transparency/? ! The effect is that it can be widely applied to f-type uses.

The method of the present invention will be explained in detail below.

First, the organic compound (A) having one wave group of phenol water used in the present invention has at least one wave group in one molecule.
As long as it has a phenolic hydroxyl group, it can be used as a target;

Examples of such organic compounds (A) include catechol, resorcinol, hydroquinone, phenol tetramers such as 70-loglucin, 2.2-bis(2-hydroxyphenyl)propane, 2.4-dihydroxydiphenylmethane, 2. 2-bis(4-hydroxyphenyl)propane, tl-bis(4-hy)”roxyphenyl)
Ethane, 1.1-bis(4-hydroxyphenyl)furopane, 2.2-bis(4-hydroxyphenyl)pentane, 4.4-dihydroxybiphenyl, 4.4-dihydroxybenzophenone, 4.4-dihydroxydiphenylsulfone, 4. Dihydric phenols such as 4-dihydroxydiphenyl sulfide, phenol novolak-1 fatty acids synthesized from phenol derivatives toformaldehyde, and phenol resins such as resol type phenol resins can be used.

Examples of phenol visiting conductors that can be used as raw materials for these resins include monohydric or polyhydric phenols such as phenol, resorcinol, and bisphenol A, or substituted substances of these phenols in the m form, such as cresol, xylenol, propylphenol, amylphenol,
Butylphenol, octylphenol, etc. can be used, and in the present invention, halogen-substituted phenol can also be used.

The substitution position of the substituent atom or substituent group in these substituted phenols may be any position from 0 to 5 m- or p-position with respect to the phenolic hydroxyl group.

In addition, formaldehyde includes formaldehyde,
There are no restrictions on the type of material, and any material that can supply formaldehyde, including paraformaldehyde, formalin, etc., can be used.

Furthermore, in the present invention, isopropenylphenol oligomers or polyparavinylphenols represented by the following chemical formula can be used.

CH3CHs 1 (t; an integer of 0 to 18) (m; an integer of 20 to 70) In the present invention, the other compound (B) used as a starting material together with the organic compound [Co., Ltd.] has the general formula described above. In the formula, R is an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an alkenyl group such as a vinyl group, an allyl group, a 1-propenyl group, It is an aralkyl group such as a benzyl group, or an organosilyl group-substituted organic group represented by the above-mentioned formula.

The monovalent organic group represented by R' in formula (i) includes an alkyl group, an alkenyl group, an aralkyl group, an aryl group, an alkoxy group, an acyloxy group, or a hydrogen atom of these groups is partially halogen. Examples include groups substituted with atoms or arbitrary organic groups. Also, the self-6 indicated by R”
Examples of divalent organic groups include alkylene groups, arylene groups, and yuzu groups.

X in formula (1) is a halogen atom, and a chlorine atom, a bromine atom, an iodine atom, etc. can be substituted for this.

As the compound (B) represented by the general formula RX, the following compounds can be used.

CtCH2S I (CH3)3. CtCH2S i
(CH3)2・C2H5tCtCH2S I (CH
3) Two fists C' H= CHz, Ct CH2S i(C
H3) 2・CH, CH=CH2, CtcH2s i
(CIlH5)20C1(8, CtCH2S l (C
H3)2・OCH3, C1cHxSl (CH”CH2
)2・CH3゜CLCH2CH2CH2S i (CH
3) 2・CH=CH2゜CLCH2CH2CH2S i
(CH3)2・CmiCH.

CtCH2CH,CH,S l<CH,>26 C1,
CH=CH2゜CH3CH3 1 C1CH2-8l-0-81-CH=CH21 CH3CH3 CH3CH3 I CLCH2-8l-0-8i -CH2C)1=CH2
1 CH3CH3 CH3CH3 1 B rcHzcHzcHz-8l -0-S i -C
H=CH21 CH-=CH2CHs Furthermore, examples of alkali metals that can be used in the present invention include lithium, potassium, and sodium, and examples of alkali metal compounds include alkali metal hydrides and alkali metal hydroxides. , alkali metal bicarbonates, alkali metal alkoxides, alkali metal alkylation products, etc., among which alkali metal hydroxides are particularly preferred in the present invention.

Examples of the non-oil organic solvents used in carrying out the method of the present invention include methanol, ethanol, n-
Alcohol thread solvents such as butanol, hydrocarbon solvents such as toluene, xylene, hexane, ethyl ether, n-
Ether solvents such as butyl ether, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, dimethyl formamide, dimethyl acetamide, dimethyl sulfoxide, hegisamethylene phosphoramide% N-methyl-2-pyrrolidone, dimethyl sulfone, Examples include polar solvents such as N-acetyl-2-pyrrolidone.

Note that two or more kinds of these inert organic solvents may be used.

In addition, in the method of the present invention, since it is necessary to azeotropically remove water produced by the reaction or water contained in the reaction system, the inert organic solvent should not form an azeotrope with water. It is preferable to use the obtained products singly or in combination.

In the method of the present invention, the above-described compound (4) and compound (B) are reacted in the presence of an alkali metal or an alkali metal compound.

It is necessary to dissolve compound (A) and compound (B) in a solvent in advance and heat it to the reflux temperature of the reaction thread. 11 (frL (jl = degree varies depending on the compound (A), compound (B) and type of solvent, but energization is 5
The temperature range is from 0 to 200°C, preferably from 80 to 150°C. This is because the reaction is slow below 50℃, and at 200℃
This is because undesirable side reactions will occur if the reaction is more than that. When the reaction system reaches reflux temperature, the etherification reaction is carried out while gradually adding the alkali metal or alkali metal compound as it is or as an aqueous solution. The reaction needs to be carried out in a substantially anhydrous state, and for this reason, it is preferable to remove the water produced or contained by azeotropy. When an alkali metal compound is used in the form of an aqueous solution or when an alkali metal hydroxide is used,
It is essential to maintain one reaction thread in a nearly anhydrous state by adjusting the addition rate of the alkali metal compound in accordance with the azeotropic temperature of water. By carrying out the reaction under such conditions, the reaction can be carried out at a pH of 10 or less, which makes it possible to obtain a product with few side reactions and no coloration.

The ratio of compound (A) and compound (1) used in the method of the present invention can be arbitrarily selected depending on the desired etherification rate of compound (A).
Therefore, in order to completely etherify the phenolic hydroxyl group of compound (A), it is sufficient to use 1 mole or more of compound (B) per equivalent of phenolic hydroxyl group. In addition, when the compound (A) is a phenol novolak resin, the phenolic hydroxyl group and the compound (B
) The ether ratio of the phenol novolak &I Bh can be varied over a wide range.

The amount of the alkali metal or alkali metal compound used is equivalent to the amount of phenolic hydroxyl group to be etherified. The reaction time varies depending on the reaction temperature and the dropping rate of the alkali metal or alkali metal compound, but for example, at a temperature of 80 to 150°C, culm is maintained for 6 to 10 hours. If the reaction is to be further accelerated, this can be easily achieved by using a compound such as dimethyl sulfoxide or dimethyl formamide or a compound such as crown ether with φV.

Compared to general etherification reaction conditions, the method of the present invention has fewer side reactions because the reaction thread is nearly neutral, and can perform etherification with high purity and high yield.
It is considered to be an extremely advantageous manufacturing method industrially.

Next, examples of the present invention and comparative examples will be given.

Example 1゜Phenol novolak resin (phenolic hydroxyl & 2.7
2k) 3oor, allyl chloride 4a, 3t
(0.6 s mol), n-butanol 400V, and toluene 1501V were charged into a reaction vessel, and heated to 90V
50% NaO from the lower funnel when heated to ~95℃
H aqueous solution (0.42 mol as NaOH) 33.6
f was gradually added dropwise over a period of 5 hours.

At the same time as the dropwise addition was started, water was continuously removed from the reaction system (pH 9) by azeotropic dehydration, and after the dropwise addition was completed, the reaction was allowed to proceed at reflux temperature for 5 hours to complete the reaction. Then, the aqueous solution obtained by filtering the generated NaCt aqueous solution was washed with water and dried, and the solvent was distilled off. As a result, a pale yellow transparent arylated phenol novolac resin 2 in which about 15% of the phenolic hydroxyl groups were allylated was obtained.
I was able to get 809. The Gardner hue of this product was 5.

Example 2 Phenol novolak resin (phenolic hydroxyl group α45
4 of) 5 of.

CH, CH3 1 CH3CH3 (0.6 mol)% dimethyl sulfoxide 250? and 150v of toluene were charged into a reaction vessel, and heated to 11
After refluxing at 0 to 120°C, Ko
An aqueous solution of n3or (purity 855%, 0457 mol) dissolved in water 302 was gradually added dropwise over a period of 5 hours, and at the same time as the addition of one drop was started, water was continuously removed from the reaction system (pH 9) by azeotropic dehydration. After the dropwise addition was completed, the reaction was carried out at reflux temperature for 5 hours to complete the reaction. The resulting aqueous KC1 solution was then filtered, the resulting aqueous solution was washed with water and dried, and the solvent was distilled off, yielding 120v of a pale yellow transparent etherified phenol novolak resin in which almost 100% of the phenolic hydroxyl groups were etherified. Ta. The Gardner hue of this product was 6.

Example 5 CH3 Le 4+! 4: *m focus n RI A A-W)? II
n, h rv = i v1534 (2,0 mol), toluene 100v and n-butanol 400? was charged into a reaction vessel, heated to reflux at 75°C, and then added with a dropping funnel J: 50 KOH48.7r (purity 85%) to 50% water.
7 was gradually added dropwise over a period of 4 hours, and at the same time as the start of one drop, water was continuously removed from the reaction system (pH 9) by azeotropic dehydration, and after the dropwise addition was completed, the mixture was heated under reflux temperature for 6 hours. The reaction was completed after a few minutes of reaction.

Then, the aqueous solution obtained by filtering the generated KC1 water bath solution was washed with water and dried, and unreacted allyl chloride and the solvent were distilled off. As a result, approximately 100% of the phenolic hydroxyl groups were present, and an allylized pale yellow d> bright allyl chloride was obtained. A good amount of etherified bisphenol A could be obtained, and the Gardner hue of this product was 2.

Example 4 Phenol novolak resin (phenolic hydroxyl group 0.8
16 Yuushin) 89.8f, allyl chloride 15 loli (2
,0 mol), n-butanol 400v and toluene 1
After charging 00v into a reaction vessel and refluxing it at 75°C by heating, add KOH48.7r (purity 85
%, 0.86 mol) dissolved in 50 liters of water was distilled for 5 hours and gradually added dropwise, and at the same time as the start of the γ reaction, water was continuously removed from the reaction system (pH 9) by azeotropic dehydration. After 5 dropwise additions, the reaction was further carried out at reflux temperature for 4 hours to complete the reaction. Then, the water bath solution obtained by filtering the produced KC1 water bath solution was washed with water, dried, and unreacted allyl chloride and the solvent were distilled off.
922% allylated pale yellow transparent allylated phenolic novolak resin was obtained.

The cardner hue of this product was 4.

Comparative Example 1゜Phenol novolak resin (phenolic hydroxyl thickness 272
t-:) 300f, n-butanol 4002,) le x
N150? , and 50% NaOH aqueous solution (NaO
After charging 33.6 y (0.42 mol as H) into a reaction vessel and completely removing water present in the reaction system by azeotropic dehydration from the reaction system at pH 14, the reaction system was adjusted to 95-10
Heated to 0°C and added 48.3 r of allyl chloride to it.
was added dropwise from the dropping funnel over a period of 3 hours, and then reacted at reflux temperature for 5 hours to complete 5 reactions. Next, the aqueous solution obtained by filtering the generated NaCL aqueous solution was washed with water and dried, and the solvent was distilled off.
% allylated blackish brown transparent allylated phenolic phenolic a [1f27! I got M'. The Gardner hue of this product was 18.

Comparative Example 2゜Phenol novolac resin (phenolic hydroxyl group 2.7
2/11) 300F, allyl chloride 48.3f (
0.63 mol), n-butanol 400? and 150v of toluene into a reaction vessel, and heated to 90-95%
After refluxing at ℃, 35.6 r of a 50% NaOH water bath solution (0.42 mo# as NaOH) was gradually added dropwise from the dropping funnel over 5 hours, and the mixture was allowed to react at reflux temperature for 5 hours. The reaction was completed.

When the solvent was then distilled off by washing with water and drying, about 15% of the phenolic hydroxyl groups were allylated.

Dark brown transparent allylated phenolic novolac resin 275
I got 1. The Gardner hue of this product was 14.

Patent applicant: Etsu Chemical Industry Co., Ltd.

Claims (1)

[Claims] 1. An organic compound (A) having at least one phenolic hydroxyl group in one molecule and the general formula [wherein R is an alkyl group, alkenyl group, aralkyl group, or Monovalent organic group, R“
is a C1-6 divalent organic group, n is 0 or a positive integer of 1-10), and X is a halogen atom]. When reacting in the presence of an alkali metal or an alkali metal compound, the organic compound (4) and the halogenated organic compound (B) are dissolved in advance in an inert organic solvent, the reaction system is maintained at reflux temperature, and the alkali metal Alternatively, a method 2 for etherifying a phenolic hydroxyl group characterized by reacting while gradually adding an alkali metal compound, when using an aqueous solution of an alkali gold wire compound or an alkali wide range hydroxide as the alkali metal compound,
V! Organic means that the water present in the reaction system or the water produced is azeotropically removed with an inert organic solvent and then reacted directly. 1 - Method for etherifying a phenolic hydroxyl group according to item 1 in parentheses (e) of claim 3. W, w, wherein the organic compound is an equilibrated or unsubstituted phenol novolak resin, resol resin or polyparavinylphenol. Method 4 for etherifying a phenolic hydroxyl group as described in Item 1. Method 4 for etherifying a phenolic hydroxyl group as described in Item 1, wherein the alkali metal compound is an alkaline range hydroxide.