JPS5883651A - Diphenyl carbonate derivative and its preparation - Google Patents

Abstract

NEW MATERIAL:The diphenyl carbonate derivative of formulaI(X is halogen). EXAMPLE:Bis(4-chloromethylphenyl)carbonate. USE:Useful as a precursor of 4-hdroxyphenyl acetonitrile useful as an intermediate of a modifying agent for pharmaceuticals and anti-biotics. 4-Hydroxyphenyl acetonitrile can be synthesized from the titled compound easily, in high yield, at a low cost. PROCESS:The compund of formulaIcan be prepared by reacting diphenyl carbonate of formula II with a halogenomethyl lower alkyl ether usually at 20-100 deg.C, preferably at 40-70 deg.C, in a solvent such as N,N-dimethylformamide, etc. in the presence of a catalyst such as zinc chloride. The 4-hydroxyphenyl acetonitrile of formula III can be synthesized by the reaction of the compound of formulaI with a cyaniding agent such as sodium cyanide at room temperature.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a diphenyl carbonate derivative represented by the formula (wherein, X represents a halogen atom) and a method for producing the same.

The diphenyl carbonate derivative represented by the above formula (I) (hereinafter simply referred to as the compound of the present invention) is.

This is a new compound that has not been published in any literature, and is a useful compound as a precursor of 4-hydroxyphenylacetonitrile, which is a known compound.

4-Hydroxyphenylacetonitrile is a very useful compound as an intermediate for pharmaceutical and antibiotic modifiers.

The conventional method for producing 4-hydroxyphenylacetonitrile is as follows.

(4) A method of reacting 4-hydroxyphenylglycine with a cyanating agent (see JP-A-54-148744) (B) A method of reacting 4-acetoxybenzyl halide with a cyanating agent (% -90052) etc. are known.

The ((conversion) method and φ) method reaction formula is as follows.

(B)
0W (In the formula, Y represents a halogen atom.) (A
) In the method (a), 4-hydroxyphenylglycine represented by (a) is quite difficult to manufacture.

The yield is low, and therefore it is a fairly expensive compound, and when obtaining Mayuko's compound (a) 4t cyanating agent ((J-) color reaction to 4-hydroxyphenylacetonitrile), relatively high temperatures are required. (120°C or higher).

On the other hand, in method (B), the production of 4-acetoxybenzyl halide represented by (b) requires many reaction steps, the yield is low, and therefore this compound (b) is also expensive. It is difficult to say that it is an advantageous method for industrial implementation.

As a result of repeated research into industrially advantageous manufacturing methods for 4-hydroxyphenylacetonitrile, the present inventors have discovered a new manufacturing process that is completely different from conventional methods, and have completed the present invention. .

That is, the present invention provides a method for producing 4-hydroxyphenylacetonitrile using inexpensive and easily available raw materials via the novel substance compound (I) of the present invention.

The process of the present invention is shown in the following reaction formula (n) (wherein, X represents a halogen atom and R represents a lower alkyl group). ) as shown.

Diphenyl carbonate and halogen 9 represented by (2)
Tsumethyl lower alkyl? By reacting, high visibility can be obtained. Further, the raw materials diphenyl carbonate and halogenomethyl lower alkyl ether are easily available and inexpensive compounds.

That is, the two compounds (I) of the present invention can be obtained at very low cost.

Next, as shown in reaction formula (2), the compound (I) of the present invention and 77
4-Hydroxyphenylacetonitrile (IF) can be obtained in a good yield by the reaction with a dioxidizing agent (for example, sodium cyanide, etc.) usually at room temperature.

Of course, it is also possible to use formaldehyde and hydrogen halide instead of halogenomethyl lower alkyl ether in reaction formula (1) and react with diphenyl carbonate to obtain Compound (I) tl- of the present invention. be.

In the reaction formula (1) of the present invention, X is chlorine or bromine.

φ means a halogen atom such as fluorine or iodine; from an economical point of view, a chlorine atom is particularly desirable. R means a lower alkyl group such as a methyl group, an ethyl group, or a globyl group, and from an economical point of view, a methyl group is preferable.

The reaction temperature is not particularly limited.

Usually, the reaction progresses at a temperature of 20°C to 100°C, preferably about 40°C to 70°C.

Although the reaction proceeds without a solvent, it is also possible to use a common solvent such as N, N-methylalumpamide, dimethyl sulfoxide, or ethylene chloride. Friend, the reaction will proceed even without a catalyst, but if a catalyst such as zinc chloride or aluminum chloride is used.

Anti-δ progresses smoothly and favorable results are obtained.

Next, a method for producing one of the compounds of the present invention will be specifically explained by giving examples. However, two things about the present invention.

It is not limited only to these.

IHilli Example 1 Synthesis of bis(4-chloromethylphenyl)carbonate Into a 100-mm reaction flask equipped with a reflux condenser was added 1-2.19 (uυ56 moles) of diphenyl carbonate 5 (49 ( α62 mol).

Anhydrous aluminum chloride8. Add f(0.0d%) and stir at 50-55°C for 4 hours. After the reaction was completed, 50 d of ethyl acetate and 56 ml of water were added, and the mixture was shaken vigorously.
The organic layer was washed twice with 50 m of water. After drying the organic layer with anhydrous sulfuric acid (IJum).

To 1 and 8 vol of a viscous oily substance obtained by distilling off the solvent, 50 W 1 t of ethyl acetate and 200 ml of n-hexane were added, and the mixture was heated at 50°C.
After stirring, the brown lower layer and white upper layer were separated, and the upper layer was left overnight.

The precipitated crystals were collected as a collection F and dried as white crystals to obtain the title compound of the present invention 14.19 ((10453 mol). Yield 81%. A part of the above white crystals was analyzed to obtain the title compound of the present invention. It was confirmed that the compound was a compound of the present invention.

Melting point: 88-89.5°C NMR (ODC), ): 64.53 (4H),
67.22 (J=8.8HJ at d, 4), δ7.5
9(d, 4H,, T=8.8H7)IR(KBr)1
401L 1764150a 125 & 842.15
60 (JlK-"Elemental Analysis" C10HI3 'h (
Calculated value as δ2 (%) 57c9o 3.8
9 22.79 Measured value (%) 57.82 3.75
22.89 Next, using the nine compounds of the present invention synthesized in Example 1.

The method for synthesizing 4-hydroxyphenylacetonitrile will be specifically explained by giving reference examples.

-Synthesis of a-hydroxyphenylacetonitrile (bis(4-chloromethylphenyl)carpone)! L
1 f (0.01 mol), 5011t of N, N-)
2.Thorium sia7ide was dissolved in methylformamide. of (0041 mol) was added and stirred at room temperature for 2 hours.

After finishing the treatment, add 100ml of 10% hydrochloric acid to the reaction mixture.

50 ml of ethyl acetate was added, stirred vigorously, and the organic layer was further washed twice with 50 sd of water. After drying.

When the solvent is distilled off and the residue is distilled under reduced pressure, the boiling point is 154.
~b friend.

A portion of this fraction was analyzed and confirmed to be 4-hydroxyphenylacetonitrile.

Yield 7'3% Melting point: 67-68℃ NMR (DMSO-d, +〇DC!,): δ168
ca, 2H) δ480 (d, 2H, J=8.5H#)
δ7.15 (d, 2H,, T=8.5H#) δ9.1
(BS, IH) Patent applicant Nissan Chemical Industries, Ltd.

Claims (1)

[Scope of Claims] A diphenyl carbonate derivative represented by the formula (wherein, X represents a halogen atom). (2) A method for producing a diphenyl carbonate derivative represented by the formula (in the formula, ! represents a halogen atom), which comprises reacting 9-phenyl carbonate and a halogenomethyl lower alkyl ether.