JPS60112731A - Novel biphenyl compound - Google Patents

Abstract

NEW MATERIAL:The biphenyl compound or formula I (R1 is hydroxy or acetoxy; R2 is hydroxy-2-proplyl or isopropenyl). EXAMPLE:4-Hydroxy-4'-(2-hydroxy-2-propyl)biphenyl. USE:Synthetic intermediate of pharmaceuticals, agricultural chemicals and dyes, and intermediate for the production of heat-resistant and chemical-resistant polymer. PREPARATION:The compound of formula I can be produced e.g. by acetylating 4-hydroxybiphenyl of formula A to obtain 4-acetoxybiphenyl of formula B, reacting the biphenyl compound with acetyl chloride or acetic anhydride in an inert solvent in the presence of a Friedel-Crafts catalyst, and subjecting the obtained 4-acetoxy-4'-acetylbiphenyl of formula C to the Grignard reaction.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel biphenyl compounds, and particularly to novel biphenyl compounds in which two tuniyl groups of biphenyl each represent a different functional group.

Biphenyl is a chemically stable compound, and polymers containing biphenyl groups are known to have excellent heat resistance and chemical resistance in fish.

By the way, in order to introduce a biphenyl group into a ψ compound, it is first necessary to synthesize a compound in which a highly reactive functional group is introduced into each of the two phenyl groups of biphenyl.

These functional biphenyl compounds can be used not only as materials for polymer synthesis, but also as medicines! ! It is also important as a synthetic intermediate for drugs and dyes.

Therefore, the present invention was made in view of the current situation, and a novel biphenyl compound represented by the following general formula is
The present invention was completed based on the discovery that it can be used as a synthetic intermediate for medicines, agricultural chemicals, dyes, etc., especially as an intermediate or raw material for the production of polymers.

The novel biphenyl compound of the present invention is represented by the following general formula.

However, in the formula, the substituent R1 is a hydroxyl group or an acetoxyl group, and the substituent WR2 is a 2-hydroxy-2-propyl group or an isopropenyl group.

The novel biphenyl compounds of the present invention include the following.

(1) 4-hydroxy-4--(2-hydroxy-2-
propyl)biphenyl(2) 4-hydroxy-4-isoprobenylbi(3)
4-Acetoxy-4--isopropenylbiphenyl The novel piphenyl compound (I) of the present invention can be prepared in various ways; for example, it can be obtained by acetylating 4-hydroxybiphenyl (A). 4-
Grignard reaction of 4-acetoxy-4-acetylbiphenyl (CC) obtained by reacting acetoxybiphenyl (F3) with acetic chloride or acetic anhydride in an inert solvent in the presence of a Friedel-Crafts catalyst with magnesium and methyl halide obtained by.

Obtained7. mIFT biphenyl compounds (I> are compounds with functional groups with different reactivities, such as phenolic OHM and alcoholic OH groups, and the production of heat-resistant and chemical-resistant silver compounds by utilizing these reactivity differences, It is expected to be used as an intermediate in the production of new agricultural chemicals and dyes.

Furthermore, the novel piphenyl compound (n) of the present invention is obtained by dehydration reaction of this novel piphenyl compound (T).

In the dehydration reaction, in the presence of alumina and potassium chloride,
Although there is a method of heating to a high temperature, a large amount of side reaction products are formed, making it difficult to isolate the novel piphenyl compound (IT), and the yield is low.

Therefore, in the present invention, by adopting a method using zinc chloride and trichloroacetic acid, the yield could be improved.

Furthermore, a new piphenyl compound (Ill) is obtained by reacting the new piphenyl compound (I[) with acetic anhydride.

The novel phenyl compound (II) or (m) obtained by the present invention has a polymerizable isoprobel group in one phenyl group of biphenyl, and a highly reactive phenolic OHN or acetoxyl group in the other phenyl group. Because it has a group, it can be used as a monomer especially in the production of functional polymer compounds.

Hereinafter, the present invention will be explained in detail based on examples.

Example 1 vI preparation of 4-human 0xy-4-(2-hydroxy-2-propyl)biphenyl (I).

5 g of dried magnesium and ether 801 were placed in a Mitsuro flask equipped with a reflux condenser, a W1 stirrer, and a calcium chloride drying tube, and the mixture was cooled to 0°C. Methyl iodide 15-1 was added with stirring and reacted for 3 hours. .

Then 4-acetoxy-4-acetylbiphenyl (C
) 10o dissolved in 100 ml of THE was added, and the mixture was reacted for 1 hour with stirring at room temperature.

1 reaction solution! The mixture was poured into ice water containing acid A to separate the precipitated crystals.

The separated yellow-white precipitate was recrystallized from benzene to obtain white 4-hydroxy-4=-(2- and droxy-2-propylene).
1 Pill) Crystals of biphenyl (I) 7.59 are 4 harps I.

1b: Rate 83.5% Melting point 187.5-189℃ Elemental analysis value 0% H% Theoretical value 78.92 7.06 Experiment [78,736,98 Characteristic infrared absorption OHIM construction 3350cm-'outer jM
R parameter (C13, DMSO) 125.3 (C
) 125.6 (D > 127.8 (D ) 13
1.3 (S) 138.1 (S) 148.8
(S) Example 2 4-hydroxy-4'-isopropenylbiphenyl (n
)Manufacturing of.

Add dimethyl sulfoxide to a numbered flask equipped with a condenser and a stirrer. 4-Hydroxy- obtained by Utsukurikai 1
4--(2-hydroxy-2-propyl)biphenyl (
After adding 100 g of zinc chloride to make a homogeneous solution, 2.5 g of zinc chloride was added and heated to 180°C, and the zinc chloride was dissolved and the reaction liquid turned yellow.

Next, 2.5 (l) of trichloroacetic acid 11j was added with stirring, and stirring was continued at 180° C. for 3 minutes.

The reaction solution was cooled to room temperature and poured into water to separate the precipitated crystals.

The crystals were dissolved in acetone, extracted with hexane, and the hexane was concentrated. The resulting crystals were recrystallized from benzene to obtain 5.3 g of a white product.

Yield 57.5% Melting point 199-201℃ Elemental analysis value 0% H% Theoretical value 85.68 6.71 Experimental value 85.32 6.57 1 Characteristic infrared absorption 0)-III4 structure 3400cmC;
-C118'Tj 1620cal-'NMR parameter (C13, DMSO) 125.8 (D)
127.6 (D) 130.4 (S) 138
．． 3(S) 139.4(S) 142.1(S) Example 3 4-acetoxy-4--isoprobelbiphenyl (I
II) lli construction.

10% of acetic anhydride in a flask equipped with a reflux condenser and a WI stirrer.
1 and then 4-hydroxy-4- obtained in Example 2.
10% of isobrobenyl biphenyl was added, and 10% of it was heated to 80℃.
The reaction was carried out by heating and stirring for hours. The reaction solution was poured into water, and the precipitated crystals were separated and recrystallized from methanol to obtain 0.7211 of white crystals of 4-acetoxy-4-isopropenylbiphenyl.

Yield 60% Melting point 131.0-131.5℃ Elemental analysis value 0% H% Theoretical value 80.93% 6.39% Experimental value 80.75% 6.23%-1

Claims (1)

[Claims] A novel biphenyl compound represented by the following general formula. However, during the ceremony, it was 11! fR1 represents a hydroxyl group or an acetoxyl group, R2 represents a 2-hydroxy-2-propyl group or an isopropenyl group, and 1°