JPH05271135A - Production of bisphenol, and bisphenol - Google Patents

Abstract

PURPOSE: To obtain a partly novel bisphenol by reacting 2,6-di-tert. butylphenol or 2,6-di-tert. amylphenol with a dihalide in the presence of a base and subjecting the reaction product to debutylation or diamylation by way of a partly novel intermediate.

CONSTITUTION: The 2,6-di-tert. butylphenol or the 2,6-di-tert. amylphenol is reacted with a dihalide of formula Hal-R-Hal (R is a bivalent hydrocarbon) in the presence of the basic material, to obtain the partly novel intermediate of formula I (A is tert. butyl, tert. amyl). This intermediate is then subjected to debutylation or diamylation, to obtain the partly novel bisphenol of the formula II. The compsns. of the formula I and the formula II are novel when R therein is -(CH₂)_n- ((n) is 4 to 12), formula III, formula IV, formula V, formula VI, formula VII. The basic material in the reaction is sodium isopropylate, NaOH, etc. The first stage is preferably executed at a temp. of 0 to 100°C and the second stage at a temp. of 80 to 400°C by using isopropanol, ethanol, etc., as a solvent.

COPYRIGHT: (C)1993,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention has a chemical formula

[Chemical 8] [In the formula, R represents a divalent hydrocarbon group. ] And a novel intermediate and a novel bisphenol itself. The bisphenol is
2,6-ditertiary butylphenol or 2,6-ditertiary
It is prepared in the process according to the invention in two steps starting from the primary amylphenol and the dihalide.

[0002]

2. Description of the Related Art German Patent Application No. 3,527,862 (A1) (German Patent Application Publication DE 35278)
62) in the first step reacting a phenol with an alkanedicarboxylic acid or its acid chloride in the presence of a fluorine-containing organic sulfonic acid to give a di (4-hydroxyphenyl) -substituted alkanedione and in the second step A method of making a bis-hydroxyphenyl-n-alkane by hydrogenating a dione is disclosed. This German patent application No. 3,527,862 further mentions aluminum chloride as the acidic catalyst in the first reaction step.

[0003]

It is said that when 2,6-ditertiary butylphenol or 2,6-ditertiary amylphenol is reacted with a dihalide, the basic catalyst works well in the first reaction step. Things have just been discovered. In the next step, a debutylation or deamination step yields the above bisphenol. The advantage of this method is that strongly acidic corrosive media are avoided and that the reaction can be carried out in a more general manner (because the dihalide in the starting material may contain more versatile hydrocarbon groups). Is.

[0004]

The present invention provides a chemical formula

[Chemical 9] [In the formula, R represents a divalent hydrocarbon group. ] In the method for producing bisphenol, in the first step, in the presence of a basic substance, 2,6-ditertiary butylphenol or 2,6-ditertiary butylphenol is used.
6-di tertiary amylphenol is a dihalide Hal
-R-Hal (wherein Hal is a halogen atom and R has the meaning given above);

[Chemical 10] [In the formula, A represents a tertiary butyl group or a tertiary amyl group. ] Intermediate product and debutylating or deamylating said intermediate product in a second step.

The divalent hydrocarbon radical can be considered to be derived from alkanes, cycloalkanes, alkenes, cycloalkenes or aromatic hydrocarbons. These alkanes and alkenes may be linear or branched. Examples of divalent hydrocarbon groups are of the formula - (CH _{2) n} - (wherein, n 1 and 1
2 is preferably an integer of 4 to 12. Is a linear alkylene group having R is

[Chemical 11] Also suitable are linear or branched alkenes such as

Other preferred R groups are:

[Chemical 12] Is. Corresponding dihalide Hal-R-Hal
Is preferably dichloride or dibromide.

As already pointed out, basic substances are required to carry out the present reaction process. Alcoholates or hydroxides are preferably used. Alkali metals such as sodium and potassium are the preferred ions. The preferred basic substances used are sodium isopropylate, sodium ethoxylate, sodium hydroxide or sodium hydride. Corresponding potassium compounds may also be used. They can also be used when they are prepared in situ. Suitable solvents are alcohols such as ethanol, isopropanol or tertiary butanol. Other suitable solvents include pentanols, other branched alcohols such as secondary butanols, ethers,
It can be benzene or toluene. The first reaction step for producing the intermediate is preferably carried out at temperatures between 0 ° C. and 100 ° C., but higher temperatures are not excluded. The second step, the debutylation step, depends on whether only thermal cleavage or a catalyst is used.
It is carried out at a temperature of 0 ° C to 400 ° C. In Example 1, three methods are disclosed. The bisphenol obtained is suitable as a starting material in the production of resins, polycarbonates and polyesters. A large number of said intermediates and said bisphenols are new compounds.

Chemical structure

[Chemical 13] [Where A has the meanings given above and R is-(CH ₂ ).
_n − (where n is 11 or 12),

[Chemical 14] Is. The compound of [] is new.

Chemical structure

[Chemical 15] [Where R is

[Chemical 16] Is. ] Bisphenol is new.

The first reaction step is terminated by adding an acid to the reaction mixture, preferably an inorganic acid such as HCl (generally in the form of an aqueous solution). Although this is not essential, acidification of the reaction mixture is preferred because otherwise the alkali metal salt of the phenol formed acts as a strong reducing agent in combination with the tertiary butyl group. .. Once the reaction mixture has been acidified, in effect neutralized, the organic compound is extracted with an organic solvent such as chlorinated hydrocarbons or ethers. The extract is washed with water to remove residual inorganic salts and dried, for example on calcium dichloride. Organic solvent used and 2,6-ditertiary butylphenol (or 2,6-ditertiary amylphenol)
Is distilled off, and the impure intermediate product can be further purified by crystallization. The intermediate may be liquid, as can be seen in Example 3, although some of these are solid products.

[0011]

【Example】

Example 1 A. 41.2 g in 100 ml isopropanol
4.6 g (0.2 mol) of 2,6-di-tert-butylphenol (abbreviated DTBP) in a stirred solution was added.
5 mol of sodium metal under an inert atmosphere (N ₂ )
It was added in 15 minutes at a temperature of 0 ° C. After complete dissolution of the sodium, 16.1 g (0.066 mol) of 1,6-dibromohexane was added over 1 hour. The resulting mixture is 6
Stir at 0 ° C. for 16 hours, then stir the reaction mixture for 20 hours.
Cooled to ° C and added hydrochloric acid (25 weight percent HCl in aqueous solution) until the color of the reaction mixture changed from greenish blue to yellow. 200 ml of dichloromethane were then added and the whole reaction mixture was extracted twice with 500 ml of water. The organic phase (extracted with water) is dried over calcium chloride, the solvent is subsequently evaporated and 20
Excess 2,6-di-tert-butylphenol was distilled off while maintaining a bath temperature of 0 ° C. and a pressure of 133 Pa.
250 ml of methanol were then added to the residue and the resulting mixture was heated to 70 ° C. After cooling to 20 ° C., white crystals of 1,6-bis (4-hydroxy-3,5-ditertiarybutylphenyl) hexane formed and were collected (13 grams), the melting point being 147 ° C. , ¹
1 H-NMR (CDCl ₃ , ppm) shows 1 to 1.7 (44
H), 2.5 (4H), 5.0 (2H), 6.99 (4
H).

B. Debutylation of bisphenol was performed by the following method. 1. The tertiary butylphenol produced in A was added to 47
Reflux for 6 hours as a 10% solution in% HBr / acetic acid (75:15 by volume). 2. Thermal cleavage at 380 ° C. for 3 hours. 3. Catalysis of aluminum ethoxide (1% by weight) at 280 ° C. under N _{2 for} 3 hours. Debutylation according to Method 1 was carried out in 67% of the theoretical amount of 1,6-
This resulted in 4,4'-hexamethylene bisphenol, also called bis (4-hydroxyphenyl) hexane. Physical Properties: Melting point 146 ° C. ¹ H-NMR: 1.0 to 1.5 (8H) 2.32 (4H) 4.60 (2H) 6.62 (4H) 6.84 (4H) Debutylation by Method 2. Gave 56% of theoretical yield. Debutylation by Method 3 resulted in 65% of theoretical yield.

Example 2 A. reaction

[Chemical 17] Sodium metal (0.6 mol, 13.8 g) was dissolved under N _{2 in} a stirred solution of 2,6-ditertiary butylphenol (1 mol, 206 g) in 500 ml of ethanol. The above dibromide (0.25 mol, 66 g) was then added in about 45 minutes keeping the solution at 0 ° C. The resulting mixture is stirred at 0 ° C. for 2 hours and subsequently at 25 ° C.
Stirred at 16 hours and at 60 ° C. for another 2 hours. The mixture is then cooled to 25 ° C. and 33% H
It was acidified with aqueous Cl, during which the color of the mixture changed from green to yellow. 300 for the resulting reaction mixture.
ml diethyl ether was added and the mixture was added to 2
It was extracted 5 times with 00 ml of water. The ether solution was then dried over magnesium sulfate. Furthermore, the solvent and excess 2,6-di-tert-butylphenol were distilled off.
The residue obtained is recrystallized from methanol and has a melting point of 15
¹ H-NMR at 2 ° C .: 59 g (68% of theoretical yield) of 1.41 (36 H) 3.87 (4 H) 5.04 (2 H) 6.98 (4 H) 7.12 (4 H) product. Obtained.

B. The product of A (22 g) was debutylated by heating in a fluidized sand bath at 380 ° C. for 1 hour under N ₂ until gas evolution ceased. The resulting debutylated product was recrystallized from chloroform (62 g = 50% of theoretical yield) and had the following chemical formula:

[Chemical 18] Physical properties: Melting point 187 ° C. ¹ H-NMR: 3.0 to 3.5 (2H) 3.79 (4H) 6.76 (4H) 6.95 (4H) 7.02 (4H)

Example 3 In a manner similar to that described in Example 1, the following was prepared. 1,12-bis (4-hydroxy-3,5-ditertiary butylphenyl) dodecane, liquid 1,11-bis (4-hydroxy-3,5-ditertiary butylphenyl) undecane, liquid 1, 8-bis (4-hydroxy-3,5-ditertiary butylphenyl) octane, liquid 1,5-bis (4-hydroxy-3,5-ditertiary butylphenyl) pentane, liquid excess DTBP and After the solvent was distilled off under reduced pressure at 200 ° C., methanol was added to the obtained residue. An oily substance separated. The yields were 70%, 82%, 56% and 62% of theoretical yield, respectively, calculated on the dibromoalkane. The above product was subsequently converted to the corresponding debutylated compound by Method B1 as in Example 1.

1,12-bis (4-hydroxyphenyl) dodecane
Melting point 136 ° C. ¹ H-NMR: 1.2 (16H) (acetone) 1.6 (4H) 2.5 (4H) 7.0 (4H) 6.7 (4H) 1,11-bis (4-hydroxy) Phenyl) undecane Melting point 101 ° C. ¹ H-NMR: 1.3 (14H) (acetone) 1.6 (4H) 2.5 (4H) 6.7 (4H) 7.0 (4H) 1,8-bis ( 4-hydroxyphenyl) octane
Melting point 134 ° C. ¹ H-NMR: 1.4 (8H) (acetone) 1.6 (4H) 2.5 (4H) 6.75 (4H) 7.00 (4H) 8.0 (2H) 1,5 -Bis (4-hydroxyphenyl) pentane
Melting point 89 ° C ¹ H-NMR: 1.4 (2H) (acetone) 1.6 (4H) 2.4 (4H) 6.8 (4H) 7.0 (4H) and the corresponding dibenzoate at 96 ° C. It had a melting point.

Example 4 A. In a manner similar to that described in Example 2, but using 1,4-dibromobutene-2 as the dihalo compound in D
Reacted with TBP to give 1,4-bis (hydroxy-3,
5-Ditertiary butylphenyl) -butene-2 was prepared. Physical Properties: Melting point 142 ° C. ¹ H-NMR: 1.44 (36H) 3.31 (4H) 5.0 (2H) 5.68 (2H) 7.00 (4H) isomer 1,2-bis (4-) Hydroxy-3,5-di third
Secondary butylphenyl) -butene-1 is also produced.

B. 4.92 g of the above product in 100 ml
Dissolved in ethanol and 0.5 g of 5% Pd / C was added to this solution. A small stream of hydrogen was passed through the reaction mixture for 16 hours, after which the 5% Pd / C was filtered off and the ethanol was distilled off. The yield of 1,4-bis (4-hydroxy-3,5-ditertiarybutylphenyl) butane was 4.2 g (94% of theory) and the melting point was 124 ° C. ¹ H-NMR: 1.3 to 1.8 (40H) (CDCl ₃ ) 2.50 (4H) 5.20 (2H) 7.00 (4H)

C. This product was used as Method B2 in Example 1.
Debutylation in accordance with the procedure gave 1,4-bis (4-hydroxyphenyl) butane, mp 156 ° C. ¹ H-NMR: 1.25 (4H) CDCl ₃ / pyridine d ₅ 2.20 (4H) 6.55 (4H) 6.65 (4H)

Example 5 A. Ortho-dichloromethylbenzene was reacted with DTBP in a manner similar to that described in Example 2 and worked up in the same manner. Chemical formula

[Chemical 19] ¹ H-NMR having a melting point of 127 ° C .: 1.41 (36H) 3.95 (4H) 5.03 (2H) 6.94 (4H) 7.0 to 7.25 (4H) Was obtained in a yield of 57% of theory.

B. This compound was used as Method B2 in Example 1.
Debutylate according to

[Chemical 20] Have, ¹ H-NMR mp 141 ° C.: product of 3.86 (4H) 6.81 (4H) 6.93 (4H) 7.13 (4H) 8.17 (2H) is, theoretical amount Was obtained in a yield of 78%.

C. The corresponding ortho-dibromomethylbenzene was used in place of ortho-dichloromethylbenzene with essentially the same results.

Example 6 A. Para-dibromomethylcyclohexane was reacted with DTBP in a manner similar to that described in Example 2. Chemical formula

[Chemical 21] ¹ H-NMR having a melting point of 202 [deg.] C .: 1.48 (36H) 0.95-1.9 (10H) 2.43 (4H) 5.05 (2H) 6.96 (4H). Was obtained in a yield of 46% of theory.

B. This product was debutylated according to Method B3 of Example 1 to give the chemical formula

[Chemical formula 22] Having a melting point of 226 ° C., ¹ H-NMR: 0.90 (4H) 1.40 (2H) 1.70 (4H) 4.00 (2H) 6.87 (4H) 6.99 (4H). The product was obtained in a yield of 67% of theory.

Example 7 In a manner similar to that described in Example 2, methallyl dichloride

[Chemical formula 23] Was reacted with DTBP. Chemical formula

[Chemical formula 24] Have, ¹ H-NMR mp 146 ° C.: product of 1.46 (36H) + 3.22 (4H ) 4.80 (2H) 5.05 (2H) 6.96 (4H) is the theoretical Obtained in a yield of 58% of the quantity. The product was hydrogenated and subsequently debutylated.

Example 8 To a stirred solution of 206 g (1 mol) of 2,6-ditertiary butylphenol in 500 ml of isopropanol,
40 g (1 mol) of sodium hydroxide was added under nitrogen atmosphere. After complete dissolution of the sodium hydroxide, 81.
3 g (0.33 mol) of 1,6-dibromohexane was added in 60 minutes with stirring. The resulting mixture is
It was further stirred at 60 ° C. for 16 hours. The reaction mixture was worked up in the same manner as in Example 1A, then 65 g
There was obtained (yield of 40% of theory) of 1,6-bis (4-hydroxy-3,5-ditertiarybutylphenyl) hexane with a melting point of 147 ° C.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location C07C 39/23 9159-4H // C07B 61/00 300 (72) Inventor Hueke De Jong Netherlands Country 1031 CM Amsterdam, Bathoeusuehi 3

Claims (10)

[Claims] 1. A chemical formula: [In the formula, R represents a divalent hydrocarbon group. ] In the method for producing bisphenol, in the first step, in the presence of a basic substance, 2,6-ditertiary butylphenol or 2,6-ditertiary butylphenol is used.
6-di tertiary amylphenol is a dihalide Hal
-R-Hal (wherein Hal is a halogen atom and R has the meaning given above) and is reacted with the chemical formula: [In the formula, A represents a tertiary butyl group or a tertiary amyl group. ] To the intermediate product and debutylating or deamylating the intermediate product in the second step. 2. A process according to claim 1, wherein the divalent hydrocarbon radical R is derived from alkanes, cycloalkanes, alkenes, cycloalkenes or aromatic hydrocarbons. 3. A divalent hydrocarbon group R is — (CH ₂ ) _n—
(Here, n is an integer of 4 to 12.), The method according to claim 1 or 2, wherein 4. The method according to claim 1, wherein the basic substance is an alcoholate or a hydroxide. 5. The method according to claim 5, wherein the basic substance is sodium isopropylate, sodium ethoxylate, sodium hydroxide or sodium hydride. 6. The method according to claim 1, wherein alcohol is used as a solvent. 7. Isopropanol, ethanol or third
6. The method according to any one of claims 1 to 5, wherein a grade butanol is used. 8. The first reaction step is carried out at a temperature of 0 ° C. to 100 ° C. and the second reaction step is 80 ° C. to 400 ° C.
The method according to any one of claims 1 to 7, which is carried out at the temperature of. 9. A chemical structure: [Where A is tert-butyl or tert-amyl and R is-(CH ₂ ) _n- , where n is 11 or 12), Is. ] New compound. 10. A chemical structure: [Where R is Is. ] New compound.