JPS6087247A - Production of 1,3-bis(3-aminophenoxy)benzene - Google Patents

Abstract

PURPOSE:To obtain the titled compound useful as a raw material for heat-resistant high polymer monomers, particularly polyamide and polyimide, by condensing a 1,3,5-trihalogenobenzene with 3-aminophenol, and dehalogenating the resultant condensate by catalytic reduction. CONSTITUTION:A 1,3,5-trihalogenobenzene of formula I (X1, X2 and X3 are Cl or Br) is condensed with 3-aminophenol in the presence of a dehydrohalogenating agent, e.g. potassium hydroxide, to give a 1,3-bis(3-aminophenoxy)-5-halogenobenzene of formula II, which is then catalytically reduced in the presence of a reducing catalyst to afford the aimed substance. EFFECT:The reaction can be easily carried out under mild conditions by easy water removing operation without using a copper compound which is a reaction accelerator, and the aimed substance is obtained in high yield.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing 1,6-bis(3-aminophenoxy)benzene.

More specifically, the dehalogenation of 1,3.5-L)rehalogenobenzene and 3-aminephenol represented by the general formula (1) (wherein Xl, X2, and X3 represent a chlorine atom or a bromine atom) General formula (1) obtained by reaction in the presence of a hydrogen agent (in the formula,
X represents a chlorine atom or a bromine atom);
The present invention relates to a method for producing 1,3-bis(3-aminophenoxy)benzene, which comprises dehalogenating 3-bis(3-aminophenoxy)-5-halogenobenzene by catalytic reduction.

1.3-His(3-aminophenoxy)benzene (hereinafter abbreviated as APB) is an important substance that is a raw material for heat-resistant polymer monomers, especially polyamides and polyimides.

For example, an acetylene-terminated polyimide made from APB, 5.3ζ4,4'-benzophenonetetracarboxylic dianhydride, and 3-aminophenyl acetylene is
It is known that it is a polymer with the highest heat resistance among polyimides (U, S, P, 3
．． 845.018, U, S, P, 3,879.34
9).

APB is conventionally produced by condensing resorcin and 1-promo-6-nitrobenzene and reducing it (G Hayashi 0
2.4S2.112) and a method for producing 3-aminopheshield 1,3-dibromobenzene by condensation (W, pitrA et al., H, eJ-y, OJLLm,
ACk, 51971 (1968), U, S, p, 4.
222. q62) is known.

In the above method for producing APR, in the reaction of resorcin and 3-nitrobromobenzene, first, after treating resorcin with sodium methoxide in a large amount of benzene,
A dehydration operation is performed while recovering benzene by distillation to produce resorcinina), which is then mixed with 6-nitropromobenzene in a large amount of pyridine solvent in the presence of cuprous chloride under an argon stream. 1,6-bis(6-nitrophenoxy)benzene was obtained in a yield of 41 cm, and the nitro compound was then reduced with ferrous sulfate to produce the desired product.

In addition, in the production method by condensing 3-amine phenol and 1,3-dibromobenzene, the two are reacted at 200 to 280°C in the presence of copper powder, or cuprous chloride is reacted in a large amount of pyridine. Although the desired product is produced by reacting in the presence of the compound, the yield is as low as 45-65%.

In this way, the known production method for APR uses a large amount of reaction solvent, which is difficult to handle due to its odor, such as pyridine, and also uses dehydrated solvents such as benzene to suppress side reactions such as hydrolysis. Strict water removal operations are required using a large amount of solvent, and since reaction accelerators such as copper powder and cupric chloride are used, care must be taken to remove coloration and copper ions. Furthermore, it is extremely difficult to implement these methods from the viewpoint of manufacturing operations and pollution-free waste, such as carrying out the reaction under an inert gas.

The present inventors have made extensive studies on a method for manufacturing APR that does not have the above-mentioned drawbacks. As a result, by condensing 1j,5-trihalogenobenzene and 3-aminoneenol, which are widely used as agricultural and pharmaceutical raw materials and solvents, 1
, 6-bis(3-aminophenoxy)-5-halogenobenzene is produced, and then this 1,3-bis(3-aminophenoxy)-5-halogenobenzene is dehalogenated by catalytic reduction to produce APR. The present invention was completed by discovering a method for producing in high yield.

That is, the method of the present invention provides 1,3.5-)! represented by the general formula (I)3 (where xl, x2 and J/・1 represented by general formula (II) (wherein, X represents a chlorine atom or a bromine atom) obtained by reacting logenobenzene and 3-aminophenol in the presence of a dehydrohalogenating agent
, 1,6-bis(3-aminophenoxy), which is characterized by obtaining 3-bis(6-aminophenoxy)-5-halogenbenzene and then dehalogenating it by catalytic reduction.
This is a method for producing benzene.

In the method O of the present invention, first, 1.3.5-)rehalogenobenzene and two molecules of 3-aminophenol are reacted in an organic solvent in the presence of a dehydrohalogenating agent.
-aminophenoxy)-5-halogenobenzene, and then the 1.6bis(3-aminophenoxy)-
This is a method for producing 1,3-bis(6-aminophenoxy)benzene (APR) by dehalogenating 5-halogenbenzene by catalytic reduction.

According to the method of the present invention, TJL1m of the reaction between 1,6-dibromobenzene and 3-amine phenol described above can be improved.
In the nz reaction, the reaction proceeds easily under mild conditions without using a copper compound, which is generally used as a reaction promoter, and by a simple operation to remove water.
1,3-bis(6-aminophenoxy)-5- in high yield
It is characterized by the ability to produce halogenobenzene.

The raw materials used in the method of the present invention are 1,3,5-trihalogenobenzene and 3-aminephenol represented by the general formula (1), and 1,3,5-trihalogenobenzene has a chlorine atom, It is a benzene derivative substituted with bromine and chlorine atoms, respectively.

For example, 1j,5-trichlorobenzene, 1,3-dichloro-5-bromobenzene, 1,3-Schiff"lomo5-
Chlorobenzene and H1.3.5-) IJ Bromobenzene.

The target product is 1,3.5-trichlorobenzene, 1,3-dichloro-5-bromobenzene, 1,6-bis(6
-aminophenoxy)-5-chlorobenzeneteary, 1
．． In the case of 3-dibromo-5-chlorobenzene, the main product is 1,3-bis(ro-aminophenoxy)-5-chlorobenzene. In the case of 'L 3+ 5-trichlorobenzene, it is 1,3-bis(3-aminophenoxy)-5-bromobenzene.

3-aminophenol is used in an amount of 2 to 5 times the molar amount of 1,5.5-trihalogenobenzene, preferably 2.
Use 1 to 3 times the molar amount.

Dehydrochlorination agents used in the process of the invention are alkali metal hydroxides, carbonates, bicarbonates and alkoxides, such as potassium hydroxide, sodium hydroxide, lithium hydroxide, potassium carbonate, carbonate Examples include sodium, lithium carbonate, potassium bicarbonate, sodium bicarbonate, potassium ethoxide, potassium isopropoxide, sodium methoxide, sodium ethoxide, and lithium ethoxide. These may be used alone or in combination of two or more.

These dehydrohalogenating agents may be used in an amount equivalent to that of 3-aminophenol as a raw material, preferably in an amount of 1 to 15 equivalents.

Next, an aprotic polar solvent is used as the reaction solvent in this method. Examples of the aprotic polar solvent include N-methylformamide, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, dimethylsulfone, sulfolane, N-methylpyrrolidone, 1,3-dimethyl-2-imidazo Examples include lysinone and phosphoric acid hexamethyltriamide. The amount of these solvents used is not particularly limited, but it is usually sufficient to use 1 to 10 times the weight of the raw materials.

A general embodiment of the reaction to obtain 1,3-bis(3-aminophenoxy)-5-halogenobenzene using the above raw materials and reactants includes a predetermined amount of 3-amine phenol, a dehydrohalogenating agent, and solvent,
After converting 3-aminephenol into an alkali metal salt, 1
1315)'! The reaction is carried out by adding J-halogenobenzene, or alternatively, all the raw materials containing 1,3.5-)-rehalogenobenzene may be added at the same time, and the reaction may be carried out by raising the temperature. Of course, the present invention is not limited to these examples, and can be implemented in other ways as appropriate.

When water is generated in the reaction system, there is a method to remove it by gradually discharging it out of the system during the reaction by aerating nitrogen gas, etc., but the most common methods are benzene, toluene, xylene, and chlorobenzene. etc. is used in small amounts to remove it from the yarn by azeotropy (this method is often used).

The reaction temperature is usually in the range of 120 to 240°C,
Preferably it is in the range of 140 to 200°C.

After the reaction is completed, the desired product is obtained by concentrating or directly discharging into water or the like.

The end point of this reaction can be determined by thin layer chromatography or high performance liquid chromatography while observing the reduction of unreacted intermediate (monoaminophenoxy compound).

Next obtained 1,5-bis(3-aminophenoxy)
-Dehalogenation of 5-halogenobenzene.

In this reaction, a catalytic reduction reaction is carried out in a solvent in the presence of a reduction catalyst. The 1,3-bis(3-aminophenoxy)-5-halogenobenzene obtained in the above reaction may be isolated from the reaction mixture and carried out in the next reaction, or the next reaction may be carried out without isolation. Also good. In this case, the dehydrohalogenating agent may or may not be present. In either case, the reaction proceeds easily, produces no by-products, and can produce a highly purified target product in high yield. Therefore, it is suitable as an industrial production method without the drawbacks of conventional methods such as low yield and requiring complicated operations in reaction and purification.

As the reduction catalyst used in this reaction, metal catalysts generally used in catalytic reduction, such as nickel, palladium, platinum, rhodium, ruthenium, cobalt, copper, etc., can be used.

Industrially it is preferred to use palladium catalysts.

Although these catalysts can be used in the metallic state, they are usually activated carbon, barium sulfate, silica gel,
It may be used by being attached to the surface of a carrier such as alumina, or nickel, cobalt, copper, etc. may be used as a Raney catalyst. The amount of catalyst used is 0.0 as metal relative to 1,3-bis(5-aminophenoxy)-5-halogenobenzene.
It ranges from 1 to 101 to 10% by weight, and usually ranges from 1 to 10% by weight when used in a metal state, and from 0.05 to 1% by weight when attached to a carrier.

In this dehalogenation reaction, hydrogen halide is produced by a catalytic tooth root reaction. A dehydrohalogenating agent may be used for the purpose of capturing this hydrogen halide.

The dehydrohalogenating agent is an alkali metal or alkaline earth metal oxide, hydroxide, carbonate, bicarbonate, lower fatty acid salt or ammonia or the usual organic amines.

For example, calcium carbonate, sodium hydroxide, magnesium oxide, ammonium bicarbonate, calcium oxide, lithium hydroxide, barium hydroxide, potassium carbonate, potassium hydroxide, sodium acetate, potassium prohionate, ammonia, triethylamine, tri-n-butylamine,
Examples include triethanolamine, pyridine and N-methylmorpholine. These bases may be 2 if necessary.
More than one type may be mixed and used.

The base may be used in an amount of 1 equivalent or more relative to 1,3-bis(6-aminophenoxy)-5-halogenobenzene, and is usually used in an amount of 1 to 3 equivalents.

The reaction solvent in this reaction is not particularly limited as long as it is inert to the reaction, and examples include alcohols such as methanol, ethanol, and impropatol, and glycols such as ethylene glycol and phlopylene gelylcol. ethers, ethers such as dioxane, tetrahydrofuran, and methylpyrrolidone, aliphatic hydrocarbons such as hexane and cyclohexane, aromatic hydrocarbons such as benzene and toluene, esters such as ethyl acetate and butyl acetate, chloroform, 1 .2-dichloro” -33
6 2 Ethane, halogenated hydrocarbons such as 1,1.2-)jlchloroethane, N, N'-dimethylformamide, N
-Methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, water, etc. can be used.

The amount of solvent used is sufficient to suspend or dissolve 1,6-bis(3-aminophenone-1-xy)-5-halogenobenzene, and is not particularly limited. 1,6-bis(6-aminophenoxy)-5
-05 to 10 times the weight of halogenobenzene is sufficient.

A common embodiment of this reaction involves adding 1,6-
A catalyst is added to bis(6-aminophenoxy)-5-heronly1 genobenzene in a dissolved or suspended state, and a catalytic reduction reaction is carried out at a predetermined temperature to effect dehalogenation.

On the other hand, when using a dehydrohalogenating agent, the catalytic reduction reaction can be carried out in the same way, but in this case, the dehydrogenating agent is added in advance and the reaction is carried out, or
Any method of sequential addition during the reaction may be used.

4 The temperature of this reaction is not particularly limited. Generally, 20~
A range of 200°C, particularly 20 to 100°C is preferred.

Further, the reaction pressure may generally be normal pressure to 50'y/i.

The end point of the reaction can be determined by quantifying the amount of hydrogen uptake.

After the reaction, if it is in a dissolved state, remove the catalyst etc. by filtration.
There are methods such as precipitating it as crystals by concentration, dilution, etc., or precipitating it as a mineral salt by adding a mineral acid, and neutralizing it to obtain the desired product. In addition, if it is in a precipitated state, it can be heated and dissolved, the catalyst and the like removed by heating, and after cooling, the precipitated crystals of the target product can be obtained.

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

Example 1 6- to 21 flasks equipped with a stirrer and a water separator
120 g (1.1 mol) of amine phenol, 75 g (1.15 mol) of granular potassium hydroxide (purity 86%), 1.
Charge 500 ml of 3-dimethyl-2-imidazolidinone (abbreviated as DMI) and 50 ml of xylene, raise the temperature while stirring and bubbling nitrogen, and remove the moisture in the reaction system while the xylene is refluxing. It was removed by a water separator. The amount of water distilled out was 20.5 ml.

Next, DMI250mA! and 1.3.5-) A solution of 91 g (0.5 mol) of dichlorobenzene was added over 1 hour, and the temperature was increased from 145 to 15 mol while distilling off the xylene in the system.
It was kept at 0°C for 5 hours. Then, increase the temperature to 170-180℃
The temperature was increased to 150 mL, and the reaction was allowed to proceed for 18 hours.

Immediately after the reaction is complete, use an aspirator to reduce the vacuum to 5 degrees.
The solvent DMI was distilled off and recovered under a pressure of 0 to 70 mmH9. The recovered DMI was 690ml.

The recovered residue was poured into 1,51 mL of vigorously stirred water to separate the brown oil into a lower layer. This brown oil was crude 1,3-bis(3-aminophenoxy)-5-chlorobenzene, and its purity by high performance liquid chromatography was 92.3%.

5 After standing still and tilting to separate the brown oil, 6N hydrochloric acid water bath solution 5209 (2.5 mol) was added and dissolved by heating.

By allowing the mixture to cool, 1,3-bis(3-aminophenoxy)-5-chlorobenzene hydrochloride was precipitated, which was filtered, washed with IO1 brine, and then dried.

The yield was 174.4 g (yield 87.3%).

In addition, this 1,3-bis(3-aminophenoxy)-5
- Recrystallization of chlorobenzene hydrochloride from 2% aqueous isopropanol yielded pure white needle crystals. The melting point of this product was 268-272°C, and the results of elemental analysis are as follows.

Calculated value (4) 54.09 4.29 7.01 26
．． 61 Then, the above 1,3-bis(3-aminophenoxy)-5-chlorobenzene hydrochloride 4. y (o, oi mol), granular hydroxide) IJum (purity 96%) 1.259 (0.03 mol), 5 tyroPd-cO, 08 g and methanol 2 oml were charged, and hydrogen was added with vigorous stirring. introduced.

When the reaction temperature was 25-30℃ for 3 hours, 220
ml of hydrogen was absorbed and no further absorption was observed, so the reaction was terminated. Next, the reaction solution was thoroughly filtered to remove the catalyst, etc., and concentrated hydrochloric acid 207111 was added to the solution, resulting in 1.3-bis(6-aminophenoxy)benzene (AP).
White needle-like crystals of the hydrochloride of R) were precipitated. It was filtered, washed with isopropanol, and dried. Yield 3.5. ! i
+ (yield 95.9 h/v 1,3-bis(3-aminophenoxy)-5-chlorobenzene hydrochloride).

Furthermore, when this APR hydrochloride was dissolved in water and neutralized with dilute ammonia water, a white precipitate was deposited.

APR was obtained by filtering, washing with water, and drying.

The purity determined by high performance liquid chromatography was 98.2%.

By recrystallizing this APR with isopropanol, pure white needle crystals were obtained. Melting point is 105-107
℃, the elemental analysis values are as follows.

Elemental analysis (QIBH16N202) 0, HN calculated value @ 73.95 5.52 9.58 measured value (4)
73.88 5.7 9.51 Example 2 6-amine phenol 12.9 was added to the same apparatus as in Example 1.
'(0.11 mol), granular sodium hydroxide (purity 96
H) 46.9 (0.11 mol), toluene IQWA' and DMI5 (1/2) were charged, and the temperature was raised while stirring and nitrogen gas was passed through the reaction system to remove the moisture in the reaction system under the reflux state of toluene. It was removed by a separator.

Next, 15.7.9 (0.05 mol) of DMI50m/1.3.5-)lipromobenzene was added, and the reaction was carried out for 20 hours at a temperature of 0 to 160°C while distilling off toluene in the system. I let it happen.

Thereafter, treatment was performed in the same manner as in Example 1 to obtain 1,6-bis(
Hydrochloride of 3-aminophenoxy)-5-bromobenzene was obtained. This hydrochloride was recrystallized with 2 liters of water-containing isopropanol, dissolved in water, and neutralized with dilute aqueous ammonia to yield 1,3-9 bis(3-aminophenoxy)-5-bromobenzene as a slightly brown oil. was released. This was extracted with ether and then dried under vacuum to form a slightly brown oily 1,3-bis(3-aminophenoxy)-
5-promobenzene was obtained.

This was used in the next reaction, but when stored separately in a cool place, it crystallized. The crystals obtained have a melting point of 68-69°C.
The elemental analysis values were as follows.

Elemental analysis (01aH1 play 202Br) Calculated value (Rage 5
B, 24 4. [177, 5521, 53 measurement direct (4)
58,09 4.18 7.48 21.45 Next, 3.7 g (0.01 mol) of the above slightly brown oily 1,6-bis(3-aminophenoxy)-5-bromobenzene
, granular potassium hydroxide (purity 86%) 0.659 (
0,+11 mol), 0.19 mol of 5% d-c catalyst, and 10 ml of isopropanol were placed in a closed glass container.
Hydrogen was introduced with vigorous stirring. Reaction temperature 50-6
When the reaction was carried out at 0°C for 2 hours, 228d of hydrogen was absorbed. Next, the reaction solution was filtered hot at the same temperature as 0, and warm water was added to the solution and allowed to cool to precipitate white needle-like APR. R filter, wash with water and dry.2.8
1. The target product of ji+ was obtained (yield 96.2 ti/pair 1,3
-bis(3-aminophenoxy)-5-bromobenzene). Purity by high performance liquid chromatography is 98.9
%Met. The melting point was 103-106°C, and the elemental analysis values were as follows.

OHN Calculated value (To) 73.95 5.52 9.58 Measured value (4) 73,62 5.58 9.24 Example 6 3-Aminophenol 12.9 (
0.1 mol), 1,5-dibromo-5-chlorobenzene 13.5.9 (0.05 mol), potassium carbonate, 10.
49 (0,075 mol) and dimethyl sulfoxide 1
00 ml was charged, and the reaction was carried out for 24 hours at a temperature of 150 to 170° C. while stirring and bubbling nitrogen.

Thereafter, treatment was performed in the same manner as in Example 1 to obtain 1,3-bis(
The hydrochloride of 3-aminophenoxy)-5-halogenobenzene was obtained.

After neutralization, analysis by high performance liquid chromatography revealed that 1,6-bis(3-aminophenoxy)-5
The ratio of -chlorobenzene to 1,3-bis(6-aminophenoxy)-5-bromobenzene was 3 to 70.

Next, 1, 3, which is a mixture of this chloride and bromo body,
Using the hydrochloride of -his(3-aminophenoxy)-5-halogenobenzene, reduction reaction and post-treatment were carried out under the same conditions as in Example 1 to obtain the target product APR. The yield calculated from the raw material composition ratio was 96 cm.

Example 4 The hydrochloride of 1,3-bis(3-aminophenoxy)-5-chlorobenzene obtained in Example 1 was dissolved in water and neutralized with dilute aqueous ammonia, resulting in a slightly brown oily 1.3- Bis(3-aminophenoxy)-5-chlorobenzene was liberated. After extracting this with ether, it was dried under vacuum to form a slightly brown oily 1,3-bis(3-aminophenoxy)-5.
-Chlorobenzene was obtained.

The obtained 1,6-bis(3-aminophenoxy)-5-
The chlorobenzene was subjected to dehalogenation, but the oil was separately left in a cold place to crystallize.

The melting point of this product was 72-73°C, and the elemental analysis values were as follows.

Elemental analysis 01eHi5N2chol Measured value (%) 66.00 4.82 B, 39 10
．． 78 Then, the above slightly brown oily 1,3-bis(3-
33 g (aminophenoxy)-5-chlorobenzene (0,
01 mol), 5tiPd2C catalyst 0.15II and 30
% dioxane aqueous solution was charged into a glass sealed container, and hydrogen was introduced while stirring vigorously.

When the reaction temperature was 70-80℃ for 6 hours, 2121
1 Ll of hydrogen was absorbed. Next, the reaction solution was filtered to remove the catalyst, neutralized with dilute aqueous ammonia, and left to stand to precipitate white needle-like crystals.

After filtering and washing with water, drying is 2.75,! 90 The target product APR was obtained (yield 94.2 h/v.1,6-bis(3-
(aminophenoxy)-5-chlorobenzene).

The melting point was 106-106°C.

Examples 5 to 8 In Example 1, the reaction was carried out by changing the dehydrochlorination agent and solvent during reduction as shown in Table 1 to obtain the target product APR. The dehydrochlorination agent and solvent used and the yield of APB (vs. 1,3-bis(3-aminophenoxy)-5-
chlorobenzene hydrochloride) are shown in Table-1.

Table 1 Potassium 5 carbonate Methanol 91,66 Triethylamine Tetrahydrofuran 8917 Sodium acetate Ethyl acetate 84.48 Magataceae oxide Methanol 94.94 Example 9 The slightly brown oily 1,3-bis(6) obtained in Example 1 -aminophenoxy)-5-chlorobenzene9,89 (0
, 03 mol), 10% Ptc 0.29.30 thiammonia water 3.4 ml, S+ (0.06 mol) and 75 ml of benzene were charged into an autoclave, hydrogen was introduced with vigorous stirring and the pressure was increased to 5 to 7 Ic9. /CIl・G
I kept it. After reacting at an internal temperature of 40 to 50° C. for 6.5 hours, the reaction solution was filtered to remove the catalyst, concentrated, and allowed to stand, resulting in the precipitation of white prism crystals. This was filtered and dried to obtain the desired product, APR. Yield 6.85 (
Yield: 78.2%/1,3-bis(6-aminophenoxy)-5-chlorobenzene). Melting point is 104-106.
The temperature is 5°C.

Example 10 Calcium hydroxide as dehydrochlorination agent, 1,1°2- as solvent
APR of the target product was obtained by carrying out the same procedure as in Example 9 except that trichloroethane and Raney nickel were used as a catalyst (yield 76.6 H/v 1,3-bis(3-aminophenoxy)-5-chlorobenzene). .

Example 11 A condensation reaction was carried out in exactly the same manner as in Example 1, and then the reaction solution was filtered to remove precipitated potassium chloride. The reaction solution after filtration was charged into 21 sealed glass containers, and 5
% Pd-04.9 g and 100 g (0.6 mol) of an aqueous solution of 60% potassium hydroxide were added, and hydrogen was introduced with vigorous stirring. When the reaction was carried out for 8 hours at an internal temperature of 30 to 35°C, 11.051 hydrogen atoms were absorbed. more than this,
The treatment was discontinued because absorption was no longer observed. Next, the reaction solution was filtered to remove the catalyst and the like, and concentrated under reduced pressure to recover the solvent DMI. The amount of DMI recovered was 670d. 1.5 liters of warm water was added to the residue after concentration, and after stirring, the mixture was allowed to stand still and the upper layer of water was removed with a slant.

The tar-like substance in the lower layer was the target product, APR, and its purity as determined by high performance liquid chromatography was 936%.

This tar-like substance was heated and dissolved in a 650d impropat tool, and 3I activated carbon was added thereto, followed by hot filtration. When the P solution was allowed to cool, white needle-like crystals were precipitated.

The desired product was obtained by filtration and drying.

Yield 117.21 (total yield 802%), melting point 103
~106°C.

Example 12 A condensation reaction was carried out in exactly the same manner as in Example 1, and the DM of the solvent was
After collecting I, 3501nl of the remaining tar-like substance
of ingropanol and filtered to remove insoluble matter.

This was charged into 11 glass airtight containers, and 5 chips p (1 c
3.2 g and granular hydroxide (purity 96%) 219 (0.5 mol) were added, and hydrogen was introduced with vigorous stirring. When the reaction was carried out at an internal temperature of 50 to 60°C for 5 hours, 11.11 of hydrogen was absorbed.

The procedure was terminated because no further absorption was observed. Immediately, the catalyst and the like were removed by hot filtration, and upon cooling, white needle-like crystals precipitated. This was filtered and dried to obtain the target product, APR. Yield 121.8g (total yield 83
．． 3).

Patent applicant: Mitsui Toatsu Chemical Co., Ltd. 7 340-

Claims (1)

[Claims] 1) 1,3,5-)rehalogenobenzene and 3-aminophenol represented by the general formula (1) (wherein Xl, X2 and X3 represent a chlorine atom or a bromine atom); General formula (IT) obtained by reaction in the presence of a dehydrohalogenating agent (in the formula,
X represents a chlorine atom or a bromine atom);
A method for producing 1,3-bis(3-aminophenoxy)benzene, which comprises dehalogenating 3-bis(3-aminoneenoxy)-5-halogenobenzene by catalytic reduction.