JPS62167732A - Hydrolysis of aromatic iodide - Google Patents

Abstract

PURPOSE:To obtain an aromatic hydroxyl compound in high selectivity, by hydrolyzing 4,4'-diiododiphenyl, etc., in the presence of a copper compound, etc., and an alkali metal hydroxide under mild condition using dimethylsulfoxide as a solvent. CONSTITUTION:The objective compound is produced by hydrolyzing a 4,4'- diiododiphenyl-type aromatic iodide of formula I (X is -O-, -, -CH2-, -SO4- or group of formula II) in dimethylsulfoxide solvent in the presence of a copper compound such as CuI, Cu2O, etc., or an iron compound such as FeO, an alkali metal hydroxide such as KOH and optionally water in solubilized state preferably at 80-250 deg.C, especially 100-180 deg.C. The amount of dimethyl-sulfoxide is preferably 2-40pts. per 1pt. of the compound of formula I and the molar ratios of the copper compound and the alkali metal hydroxide to the compound of formula I are preferably 0.05-10 and 1-20, respectively.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention provides an aromatic hydroxy compound by hydrolyzing a 4,4'-short diphenyl type aromatic iodide represented by the general formula (1). The present invention relates to a method for manufacturing.

[Conventional technology]

Conventionally, as a method for hydrolyzing a compound similar to the aromatic halide represented by the general formula (1), 4,4'-dibromodiphenyl ether was treated in an aqueous caustic solution in the presence of an alkali metal peroxide and a copper halide. There is a method to obtain 4,4'-dihydroxydiphenyl ether by hydrolysis (USP 3290386), and
, 4'-dibromodiphenyl in the presence of a copper compound catalyst,
Alkaline water? A method for obtaining 4,4'-dihydroxydiphenyl by hydrolysis in $t&
4).

However, there are still no methods for hydrolyzing aromatic iodides represented by general formula (1) having iodine at the 4.4' position.
Not disclosed.

[Problem that the invention seeks to solve]

One of the major characteristics of aromatic halogen compounds is that the reactivity of the halogen is much lower than that of aliphatic compounds.

Therefore, in the conventional method, hydrolysis is carried out at 180 to 250° C. in an aqueous alkaline solution in the presence of a copper compound catalyst.

When this conventional method is applied to the hydrolysis reaction of the aromatic iodide represented by the general formula (1) (hereinafter simply referred to as aromatic iodide), thermal decomposition such as deiodination reaction occurs, and hydrolysis products You can't get anything at all.

The present inventors have conducted intensive research to develop a method for highly selective hydrolysis and decomposition at low temperatures and in a short time. It was discovered that it is easily hydrolyzed in the presence of an alkali and converted into the target aromatic hydroxy compound, and based on this finding, the present invention was completed.

[Means and effects for solving the problems] In the present invention, it is essential to use dimethyl sulfoxide as a reaction solvent. By using dimethyl sulfoxide as a solvent, the aromatic iodide as a substrate,
Copper or iron compounds, caustic and water or
It is presumed that the caustic alkali alone is solubilized, and as a result, the hydrolysis reaction proceeds even under mild conditions. The dimethyl sulfoxide solvent may be used alone, or may be used in combination with a tertiary amine and/or a phase transfer catalyst, such as a quaternary ammonium halide, for the purpose of increasing the solubility of the catalyst. The amount of dimethyl sulfoxide used is not particularly limited, but in practice it is preferably about 2 to 40 times the amount of the aromatic iodide.

In the present invention, the general formula (1
) In the aromatic iodide represented by -X- is not particularly limited, but -〇-2-, -CH2-,
-3o□- or -〇- etc. are suitable.

The catalyst used in the present invention is copper alone, a copper compound excluding iron alone, or an iron compound. These compounds may be used alone or in combination of two or more.

An example of this is as follows.

CL120. CuO, Cu(Olf)g, CuzOs
, CuF, CuC1, CuBr.

Cul+CuCN,? I:l' (C1l(CN)4)
(M' is a monovalent cation) *CuF z +
CuC121CuBr 2 + Cu (CN) z
+ M z ' (Cu (CN) 4) tCu
SO4, Cu(NOz)z, Cu(C)lzcOO)z
, CuC0+, Cu+(POt)z+Fed, Fe
(OH)z, Fe2O3+ Fed(OH), Fe
S, Fe5z, FeFz+M'FeFi+ Mz'
FeFa + FeF3. M'FeF4, Mz
'FeF3. Mz 'FeF,,.

Mz' (FeFs(HzO)), FeC1,, M
'FeCl3. M,'FeC1,.

M4'FeC16, FeC1=, M'FeCl4+
MZ' (FeC1s(HzO)) +FeBrz,
FeBr:+, Fe1z, Fe(ClO2)z+
Fe(C104)+.

Flll(NO3)21 Fe(No:+)a, Fe
SO41Fez(SO4)a, Fe2O3+Mt'
CFe(CN)b〕+lb' (Fe(CN)b) +
Fe5(PO4)z.

FePO,, Fe(C1l=COO) 2+ Fe(C
I, C00) 3+, among which halides and oxides are particularly preferred industrially. There is no particular restriction on the amount of these copper compounds or iron compounds used, but in practice it is 0.05 to 1O per aromatic iodide.
It is preferably about twice the molar amount.

The amount of caustic alkali used in the present invention is practically preferably about 1 to 20 times the mole of the aromatic iodide.

Although the presence of water is not an essential condition in the present invention, it is preferable to add 0.5 to 3 times the amount of water to the caustic alkali in order to increase the solubility of the caustic alkali in dimethyl sulfoxide.

In the present invention, the reaction temperature is preferably 80 to 250°C in order to obtain the desired aromatic hydroxy compound. If the temperature is low, not only will the reaction not proceed, but the selectivity of the hydrolysis product will also be low.

In addition, if the temperature is high, thermal decomposition such as deiodination reaction occurs,
The selectivity of hydrolysis products is also lower. Particularly preferably,
The temperature is 100°C to 180°C.

In the present invention, the reaction time is determined by the reaction temperature and the target aromatic bitroxy compound, and is not particularly limited.

After or before extraction in the alkaline aqueous solution containing the reaction product obtained in the method of the present invention using dimethyl sulfoxide or an insoluble extractant, neutralization with a mineral acid, Becomes free.

In the method of the present invention, there are no particular limitations on the method for freeing, isolating, and purifying the reaction product.

〔Effect of the invention〕

As described above, according to the present invention, by using dimethyl sulfoxide as a solvent in the presence of a copper compound or an iron compound and a caustic alkali, the aromatic iodide represented by the general formula (1) can be mildly treated. It becomes possible to perform highly selective hydrolysis under certain conditions.

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 300 g (0,71) mol) of 4,4'-short diphenyl ether was placed in a 3000 ml glass flask.
, cuprous iodide 30g sodium hydroxide 239g (
4.27 mol), 156 g of water, and 1500 g of dimethyl sulfoxide were charged, and the mixture was stirred at a temperature of 150° C. for 2 hours while blowing nitrogen into the system.

After the reaction, the undissolved catalyst and the reaction liquid are separated after cooling to room temperature. Next, it was neutralized to weak acidity with phosphoric acid.

As a result of analyzing and quantifying the product by gas chromatography and liquid chromatography, the conversion rate of 4.4'-short diphenyl ether was 100%, 4+4''; hydroxydiphenyl ether was 129.3 g (yield 90%).
, 4-hydroxy, 4'-iododiphenyl ether is 1). 1 g (yield 5%) of each was obtained.

The results are shown in Table 1.

Examples 2 to 1) The compositions shown in Table 1 were used to obtain the results shown in Table 1. However, for Examples in which the reaction was carried out at a temperature higher than the boiling point of the reaction solution used, a 5US316 autoclave was used and the reaction was carried out in a pressurized system after purging with nitrogen.

Reference Example 4. An example of a reaction when the conventional technique using 4'-dibromodiphenyl is applied to an aromatic iodide is shown.

4.22 g of 4.4'-short diphenyl ether (0.01 mo
1), copper oxide 4.0 g %' 20 wt % - sodium hydroxide aqueous solution 100 ++ 1 was charged, the space was sealed, the air in the space was replaced with nitrogen, the temperature was raised, and the temperature was stirred at a temperature of 220° C. for 5 hours.

After the reaction, the mixture was cooled to room temperature and neutralized with phosphoric acid.

After extracting the freed reaction products and unreacted substances with chloroform, they were analyzed and quantified by gas chromatography and liquid chromatography. As a result, the conversion rate of 4.4'-short diphenyl ether was 100%, but the conversion rate of 4.4'-short diphenyl ether was 100%. .4'-
Dihydroxy diphenyl ether and 4-hydroxy, 4
'-Iododiphenyl ether was rarely obtained.

Margin below

Claims (1)

[Claims] 1) A 4,4'-short diphenyl type aromatic iodide represented by general formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼... (1) A method for hydrolyzing an aromatic iodide, characterized by hydrolysis in a dimethyl sulfoxide solvent in the presence of a copper compound or an iron compound and a caustic alkali 2) In an aromatic iodide represented by the general formula (1) - X- is -O-, -, -CH_2-, -SO_4-,
or ▲There are mathematical formulas, chemical formulas, tables, etc.▼The method according to claim 1 3) The method according to claim 1 in which the hydrolysis is carried out at a temperature of 100 to 180°C