JPS6210030A - Production of 6,6'-dihydroxy-3,3,3',3'-tetramethyl-1,1'-spirobiindane - Google Patents

Abstract

PURPOSE:To obtain the titled compound useful as a raw material of resin, rationally in high efficiency, by heat-treating 2,2-bis(4-hydroxyphenyl)propane in the presence of a catalytic amount of perfluoroalkanesulfonic acid. CONSTITUTION:Objective 6,6'-dihydroxy-3,3,3',3'-tetramethyl-1,1'-spirobiindane of formula can be produced by heating 2,2-bis(4-hydroxyphenyl)propane at 50-200 deg.C, preferably about 60-160 deg.C in the presence of a catalytic amount of a perfluoroalkanesulfonic acid (especially preferably trifluoromethanesulfonic acid, and its amount is 0.05-20wt%, especially 0.1-10wt% based on the raw material). EFFECT:The process is free from the load such as the waste liquid disposal, etc., and has industrial advantage.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention provides 6,6-cyhydroxy-3.3,3.3-1
．． The present invention relates to a novel method for producing 1°-spirobiindane.

More details: 2,2-bis(4-hydroxyphenyl)
The present invention relates to a method for producing 6,6'-dihydroxy-3,3,3,3-tetramethyl-1,1-spirobiindane, which comprises heat-treating furopane in the presence of perfluoroalkanesulfonic acid.

6,6-Sihydroxy-3.3,3.3-1tramethyl-1,1-spirobiindane is an extremely useful substance as a resin raw material.

(Prior Art) Conventionally, regarding the production method of 6,6-cyhydroxy-3.3.3',3'-tetramethyl-1,1-spirobiindane, 2,2-bis(4-hydroxyphenyl)propane was A method of manufacturing by treating in approximately twice the amount of sulfuric acid at 140°C for 6 hours (US Pat. No. 3,271°463).

2. A method for producing 2-bis(4-hydroxyphenyl)propane by treating it in a large excess of hydrobromic acid under reflux for 7 hours (Journal Op Chemical Society (J
, Chem, Soc, 1962.415)).

There is also a method for producing 2,2-bis(4-hydroxyphenyl)propane by treating it with concentrated hydrochloric acid at 100° C. for 24 hours in an autoclave (US patent).

No. 3.271.463), etc. are known.

However, these methods use a large amount of sulfuric acid or hydrobromic acid for the raw material 2,2-his(4-hydroxyphenyl)propane.

Furthermore, when using concentrated hydrochloric acid, the desired product is manufactured in an autoclave, but the yield is extremely low.

Not practical. Thus, the known manufacturing method is sulfuric acid.

Alternatively, since a large amount of hydrobromic acid is used, the volumetric efficiency is poor, and the processing load for pollution-free treatment such as treatment of waste liquid becomes large. In addition, these methods require equipment that is resistant to corrosion, making them industrially unreasonable and extremely difficult to carry out.

(Problems to be Solved by the Invention) The problem to be solved by the present invention is to solve such 6,6-cyhydroxy-3
．． A completely new 6 that solves the problems of the conventional technology for producing 3,3.3-tetramethyl-1,1-spirobiindane.
, 61-dihydrokycu-3.3,3.3-tetramethyl-1,1-spirobiindane.

(Means for Solving the Problems) The present inventors have made extensive studies to achieve the above-mentioned problems. As a result, by heat-treating the raw material 2,2-bis(4-hydroxyphenyl)propane in the presence of a catalytic amount of novel fluoroalkanesulfonic acid, it was possible to achieve a rational and efficient method of <6.6'-dihydroxy- 3,3,3,3-
The present inventors discovered that tetramethyl-1,1'-spirobiindane can be obtained and completed the present invention. That is,
The present invention is characterized in that 2,2-bis(4-hydroxyphenyl)propane is heat-treated in the presence of perfluoroalkanesulfonic acid.
, 3,3° 3-tetramethyl-1,1-spirobiindane.

The raw material used in the method of the present invention is 2,2-bis(4-hydroxyphenyl)furopane. Mata.

In the method of the present invention, the treatment may be carried out without a solvent or in a solvent. The solvents used are aromatic and halogenated hydrocarbons, examples of which include benzene, toluene, xylene, ethylbenzene,
Trimethylbenzene.

Chlorobenzene, bromobenzene, anisole.

Examples include naphthalene, biphenyl, diphenyl ether, and the like. As a halogenated hydrocarbon solvent.

For example, 1,1"-dichloroethane, carbon tetrachloride, 1
．． 2-dichloroethane, 1,1,1-toIJ chloroethane, 1,1.2-)lichloroethane, 1,
1,1,2-tetrachloroethane, 1,1,2.2
-Tetrachloroethane.

1.2-dichloroethylene, trichloroethylene.

Examples include tetrachlorethylene. The amount of these solvents used is not particularly limited, but 1 to 10
A double magnification is sufficient.

The perfluoroalkanesulfonic acid used in the method of the present invention is a sulfonic acid represented by the general formula CnF2n-1-1SO3H (n is an integer of 1 to 8), specifically trifluoromethanesulfonic acid (CF35O3H).

Pentafluoroethanesulfonic acid (C2F5SO3H)
.

Heptafluoropropane sulfone rll (C3F7S
O3H).

nonafluorobutanesulfonic acid (C4F9SO3H),
Untecafluoropentanesulfonic acid (CsFlt 5
O3H).

Tridecafluorohexane sulfonic acid (C6F13SO
3H), pentadecafluorohebutanesulfonic acid (C,
F, 5SO3H), heptadecafluorooctane sulfonic acid (C8F17803H), etc., and are used industrially.

Trifluoromethanesulfonic acid (CF3S03H) has a strong resistance. This Relabel fluoroalkanesulfonic acid is used in an amount of 0.05 to 20% by weight based on the raw material, preferably 0.05 to 20% by weight based on the raw material.
．． 1 to 10% by weight is used.

The reaction temperature is usually in the range of 50 to 200'C, preferably in the range of 60 to 160'C.

The reaction time is 1 to 20 hours.

As a general embodiment of the method of the present invention, C. 2
．． 2-1: Charge (4-hydroxyphenyl)propane and perfluoroalkanesulfonic acid and heat treat. The end point of this reaction can be determined by high performance liquid chromatography while observing the decrease in raw material. After the reaction is complete, either an aqueous alkali solution is added immediately to precipitate the alkali metal salt, or the solvent is distilled off, and the by-product thunol is distilled off under reduced pressure to recover it, and an aqueous alkali solution is added to precipitate the alkali metal salt. , or the precipitated alkali metal salt is taken out and neutralized with mineral acid,
Obtain the desired crude product. There is a method of recrystallizing the crude product using a solvent to obtain the desired product.

(Functions and Effects) According to the method of the present invention, the desired product can be easily produced by heat-treating 2,2-bis(4-hydroxyphenyl)propane in the presence of a catalytic amount of perfluoroalkanesulfonic acid.

Therefore, there is no burden such as treatment of waste liquid, and the target product can be produced rationally and efficiently in manufacturing operations, and 6,6°-dihydroxy-3,3, which is extremely advantageous for industrial implementation.
This is a method for producing 3,3-tetramethyl-1,1-spirobiindane.

(Example) Hereinafter, the method of the present invention will be explained in more detail with reference to Examples.

Example 1 1e (2,2-bis(4-hydroquinophenyl)propane 25 (1 (1,1 mol)) and trifluoromethanesulfonic acid 19 were charged in a bulk flask and heated to 140-150°C
React for 5 hours. After the reaction is complete.

Immediately, the by-produced phenol is distilled off and recovered by vacuum distillation, cooled, and 150 d of isopropanol (IPA) is charged and dissolved. Next, 9 caustic soda aqueous solution 5109
When charging) IJium salt crystals precipitate. This was filtered and further heated with 25% IPA aqueous solution at 80-83°C.
for 30 minutes, cooled, filtered and neutralized with aqueous ammonia in a 15% IPA aqueous solution. Separate the precipitated crystals by P,
After washing with water, drying and azeotropic dehydration in benzene,
Filter and dry to obtain 6,6-cyhydroxo3.3,3.3
-Tetramethyl-1,1-spirobiindane white crystals were obtained. Yield 81.57 mp 215-217°C MS: 308 (M+), 293 (M-CH3
) + Example 2 11 In a separable flask, 2,2-bis(4-hydroxyphenyl)propa:y 1259 (0.55 mol), trifluoromethanesulfonic acid 1.29 and toluene 375 were charged, React under reflux for 9 hours. After the reaction was completed, the toluene was immediately distilled off, the by-product phenol was distilled off and recovered under reduced pressure, and the same procedure as in Example 1 was carried out to obtain 6,6'-dihydroquine-3,3,3.
, 3-tetramethyl-1,11-spirobiindane was obtained as white crystals. Yield 39ri, mp 215-217°
C Example 3 In a separable flask, 125 g (0.55 mol) of 2,2-bis(4-hydroxyphenyl)furopane
Todorifluoromethanesulfone [1,29] and tetrachloroethylene 375- are charged and reacted under reflux for 7 hours. After the reaction was completed, 6,6-cyhydroxy-3,3,3,3-te, tramethyl-1,1 was obtained by the same operation as in Example 2.
- White crystals of spirobiindane were obtained. Yield 40ml
p 215-217°C Example 4 125 ml of 2,2'-bis(4-hydroxyphenyl)propane in a 500-separable flask! ;I (0,5
5 mol) topentafluoroethanesulfone (tRo, 5
9 and reacted at 140-150'C for 6 hours. After the reaction was completed, white crystals of 6,6"-dihydroxy-3,3,3,3-tetramethyl-1,1-spirobiindane were obtained by the same operation as in Example 1. Yield: 42 mp 2
15-217°C Example 5 2,21-bis(4-hydroxyphenyl)propane 125'7 (0,55
0.59 mol) of toberfluorohebutanesulfonic acid was charged and reacted at 140-150°C for 5 hours. After completion of the reaction, 6,6-cyhydroxy-3 was prepared in the same manner as in Example 1.
．． White crystals of 3,3,3-tetramethyl-1,1-spirobiindane were obtained. Yield 4 (1mp215~217°
C Example 6 A 21 separable flask was charged with 5009 (2.2 mol) of 2,2-bis(4-hydroxyphenyl)propane and 0.5 mol of trifluoromethanesulfonic acid.
React at 60°C for 8 hours.

After the reaction was completed, the same procedure as in Example 1 was carried out to obtain white crystals of 6,61-dihydroxy-3,3,3,3-tetramethyl-1,1-spirobiindane. Yield 1609mp
215-217°C Patent applicant Mitsui Toatsu Chemical Co., Ltd. 1) + 1111 Spider Dragon Flute Q 11 1;
Knee 91 Proceeding Proceeding Authorization (Spontaneous) December 17, 1985 1. Indication of the case 1985 Patent Application No. 149166 2. Name of the invention 6.6'-dihydroxy-3,3,3'; 3. Process for producing 3°-tetramethyl-1,1-spirobiindan 3 and its relationship to the amended case Patent applicant address 3-2-5 Kasumigaseki, Chiyoda-ku, Tokyo Name (312) Mitsui Toatsu Chemical Co., Ltd. Co., Ltd. Muj-/llN110) Furitatatsuta 1511--l ノ/1-Jha" is corrected to read "hydrochloric acid aqueous solution."

that's all

Claims (1)

[Claims] 1) Formula (1) characterized in that 2,2'-bis(4-hydroxyphenyl)propane is heat-treated in the presence of perfluoroalkanesulfonic acid ▲ Numerical formula, chemical formula, table, etc. Yes ▼ (1) 6,6'-dihydroxy-3,3,3'
, 3'-tetramethyl-1,1'-spirobiindane.