JPS61194055A - Production of bis(3-aminophenoxy) compound - Google Patents

Abstract

PURPOSE:To produce the titled compound useful as a raw material of heat- resistant adhesive, economically on an industrial scale, by condensing a 4,4'- bisphenol with m-dinitrobenzene in an aprotic polar solvent in the presence of a base, and reducing the condensation product. CONSTITUTION:The objective compound of formula III can be produced by condensing the 4,4'-bisphenol of formula I [X is 1-10C bivalent hydrocarbon group, -C(CF3)2-, -CO-, -S-, -SO-, etc.] with m-dinitrobenzene in an aprotic polar solvent (e.g. N-methylformamide) in the presence of a base (e.g. NaOH), and reducing the resultant bis(3-nitrophenoxy) compound of formula II. The condensation reaction proceeds without addition of a reaction accelerator such as a phase-transfer catalyst. Various kinds of the compound of formula III can be produced by this process. The objective compound is obtained in high yield by conventional reduction process. The amount of the solvent is usually 1-10 times weight based on the raw material.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing a bis(3-aminophenoxy) compound.

More specifically, the general formula (IinHO+X+OH(I) (wherein, X is a divalent hydrocarbon group having 1 to 10 carbon atoms,
C(CF3)2-1-CO-1-S-1-SO-1-8
4,4'-bisphenols represented by O2- or 0 divalent (X may be directly bonded with a single bond) and m-dinitrobenzene in an aprotic polar solvent in the presence of a base. The bis(3-nitrophenoxy) compound represented by the general formula (Il) (wherein, X has the same meaning as in the general formula (1)) obtained by condensation in the compound is then reduced. The present invention relates to a method for producing a bis(3-aminophenoxy) compound having the general formula (III) (wherein, X has the same meaning as in the general formula (1)).

The bis(3-aminophenoxy) compound represented by the general formula (ill) is an important compound as a monomer for heat-resistant polymers, particularly as a raw material component for polyamide, polyimide, polyamideimide, and the like. For example, general formula (II
Polyamide-imide copolymers (Japanese Unexamined Patent Publication No. 58-79019), polyimidehydantoin (Unexamined Japanese Patent Application No. 52-63998), and polyimide (Unexamined Japanese Patent Unexamined Publication No. 58-76425) using the compound represented by I) as raw materials have been disclosed. It has already been reported that it can be used as a resin with properties. In addition, the present inventors discovered that an adhesive having excellent heat resistance could be obtained from polyimide containing this compound as a diamine component, and filed an application earlier.

(Prior Art) Conventionally, regarding the production method of a bis(3-aminophenoxy) compound having an amine group at the m-position of the ether bond represented by the general formula (III), in the general formula (ml), X is -SO Regarding 4,4'-bis(3-aminophenoxy)diphenylsulfone, which is (J.

Schramm et al., Liebigs, Ann, C.
hem,, E40.169 (1970), Special Publication 1978-
35990). However, in general formula (Ill), X is -C(CF3)2-1 C(CH3)2-1
Regarding the compound which is a divalent group of -co-1-S-1-SO2- or -〇-, the manufacturing method thereof is not clear.

By the way, if it is possible to produce the bis(3-nitrophenoxy) compound represented by the general formula (n), the bis(3-aminophenoxy) compound represented by the general formula (III) can be produced by reducing it. You can manufacture words.

However, the following is known regarding the production of the bis(3-nitrophenoxy) compound represented by the general formula (I[). That is, in aromatic nitro compounds, many examples are known regarding the substitution reaction of the nitro group of a compound activated by an electron-withdrawing group at the O- or p-position with alcohols and phenols. (e.g. H, M, Reles et al., J
, Polym, Sci,, Polym.

Chem, Ed, 15.2441 (1977),
J, R, Beck et al.

J, Org, Chem, 39.1839 (19
74), T. Takekoshi et al., J. Po
lym, Sci, Polym, Chem, E
Papers such as d., 18°3069 (1980) and J.
, R, Beck, Tetrahe-dron, 3
There is a review article in 4.2057 (1978)). However, regarding the reactions of unactivated nitro groups such as Nacala and m-dinitrobenzene, only a few examples of substitution reactions using alcohols are known.

For example, (1) m-dinitrobenzene and sodium methoxide are mixed with hexamethylphosphotriamide (HMPA).
) A method for producing m-nitroanisole by reacting in a solvent at 25 °C for 16 hours (N, Kornblum et al., J
, Org, Chem, , 4, 1560 (1
976) ) (2) A method for producing m-nitrophenyl alkyl ether by reacting m-dinitrobenzene with an alkali metal alkoxide in a polar organic solvent in the presence of a macrocyclic polyether (Toyoda et al., JP-A-Sho 54=390
30') (3) A method for producing m-nitroanisole by reacting m-dinitrobenzene and sodium methoxide in chlorobenzene in the presence of a phase transfer catalyst (F, Mont
anari et al., Chem, & Ind., 19
82.412) is known. However, (1
In method ), the HMPA solvent used is special and expensive, while in methods (2) and (3), it is necessary to use expensive raw ethers and quaternary ammonium salts, which are difficult to recover. There are problems in some respects.

Recently, as a method for improving these, m-dinitrobenzene and alcohols are reacted in the presence of alkali metal carbonate, hydrogen carbonate, trialkali metal phosphate, or carbon dioxide gas to form m-nitrophenyl alkyl. A method for producing ether has also been reported←Japanese Patent Application Laid-Open No. 1804-1983
61, 59-25353 and 59-44343
).

On the other hand, regarding the substitution reaction of m-dinitrobenzene with phenols, conventionally, in the presence of a macrocyclic polyether,
The only known method is to produce 3-nitrodiphenyl ethers by reacting m-dinitrobenzene with an alkali metal salt of phenol in a polar organic solvent (
JP-A-54-39030).

However, in this case, it is necessary to use an expensive or special reagent such as raw ether as a reaction accelerator, and furthermore, it has the drawback that it is difficult to recover. As described above, the substitution reaction of m-dinitrobenzene with phenols is expected to be considerably more difficult than that with alcohols, and there has been no prior example of this reaction under normal industrial conditions.

(Problems to be Solved by the Invention) An object of the present invention is to develop an industrial method for producing a bis(3-aminephenoxy) compound represented by the general formula (In), which is useful as a raw material for heat-resistant adhesives. It is to provide.

(Means for Solving the Problems) Therefore, in order to solve the problems of the present invention, the present inventors conducted extensive studies on a method for producing a bis(3-aminophenoxy) compound. As a result, when 4,4'-bisphenols represented by the general formula (1) and m-dinitrobenzene are reacted in an aprotic polar organic solvent in the presence of a base, the -%j formula (■) is obtained. The screw represented by (3
-nitrophenoxy) compound can be obtained in good yield, and by reducing this compound, it has been found that the bis(3-aminophenoxy) compound represented by the general formula (III) can be industrially advantageously produced, and the present invention is based on the present invention. I was able to complete it.

That is, the present invention provides 4 represented by the general formula (1),
The bis(3-nitrophenoxy) compound represented by the general formula (II) obtained by condensing 4'-bisphenols and m-dinitrobenzene in an aprotic polar solvent in the presence of a base is then reduced. The present invention relates to a novel method for producing a bis(3-aminophenoxy) compound represented by the general formula (11[1).

The compound produced by the method of the present invention has the general formula (l[l
It is a bis(3-aminophenoxy) compound represented by l. Specifically, 4,4'-bis(3-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)diphenylmethane, 2,2-bis(4-(3-aminophenoxy)phenyl)propane , 2.4-bis(
4-(3-aminophenoxy)phenyl-2-methylpentane, 2,2-bis[4-(3-aminophenoxyraphenyl]-hexafluoropropane, 4,4'-bis(3-aminophenoxy)benzophenone , 4.4'
-bis(3-aminophenoxy) diphenyl sulfide, 4.4'-bis(3-aminophenoxy) diphenyl sulfoxide, 4.4'-bis(3-aminophenoxy) diphenyl sulfone, 4.4'-1:' Examples include (3-aminophenoxy)diphenyl ether.

The compound produced as an intermediate in the method of the present invention is a bis(3-nitrophenoxy) compound represented by the general formula fll). Specifically, 4.4'-bis(3-
Nitrophenoxy)biphenyl, 4,4'-bis(3-
nitronenoxy)diphenylmethane, 2,2-bis(
4-(3-nitrophenoxy)phenyl]propane, 2
．． 4-bis(4-(3-nitrophenoxy)phenyl-2-methylpentane, 2,4-bis(4-(3-nitrophenoxy)phenyl)-4-methyl-1-pentene, 2,2-bis(4 -(3-=)lophenoxy)phenyl]-hexafluoropropane, 4.4'-bis(3-
nitrophenoxy)benzophenone, 4,4'-bis(
3-nitrophenoxy)diphenylsulfi)”, 4.
Examples thereof include 4'-his(3-nitrophenoxy)diphenyl sulfoxide, 4,4'-bis(3-nitrophenoxy)diphenylsulfone, and 4,4'-bis(3-nitrophenoxy)diphenyl erthyl.

The starting materials used in the method of the present invention are m-dinitrobenzene and 4,4'-bisphenols represented by the general formula (1). Specific examples of 4.4'-bisphenol include 4.4'-dihydroxybiphenyl;
4= dihydroxydiphenylmethane, 2゜2-bis(
4-hydroxyphenyl)propane, 2,4-bis(
4-hydroxyphenyl)-2-methylpentane, 2.
4-bis(4-hydroxyphenyl)-4-methyl-1
-Pentene, 2.2-bis(4-hydroxyphenyl)-hexafluoropropane, 4.4'-dihydroxybenzophenone, 4.4'-dihydroxydiphenyl sulfide, 4.4'-dihydroxydiphenyl sulfoxide, 4.4 Examples include '-dihydroxydiphenyl sulfone and 4,4'-dihydroxydiphenyl ether.

The amount of these raw materials to be used is not particularly limited, but is usually used in a molar amount of 1.5 to 4.0 times the amount of m-dinitrobenzene and 4,4'-bisphenols.

The method of the present invention uses 4,4' represented by the general formula (1) above.
- A reaction for producing a bis(3-nitrophenoxy) compound represented by the general formula (Il) by condensing bisphenols and m-dinitrobenzene in the presence of a base in an aprotic polar solvent (hereinafter referred to as (referred to as a one-stage reaction) and
Furthermore, two types of reactions (hereinafter referred to as second-stage reactions) are performed to reduce this bis(3-nitrophenoxy) compound to produce a bis(3-aminophenoxy) compound represented by the general formula (III). Consists of reactions.

The bases used in the first stage reaction are alkali metal oxides, hydroxides, carbonates, bicarbonates, hydrides and alkoxides. Specifically, sodium oxide, lithium oxide, potassium hydroxide, sodium hydroxide, lithium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, sodium hydride, potassium-1-butoxide, sodium methoxide. , sodium ethoxide, etc. are used. These may be used alone or in combination of two or more.

There is no particular restriction on the amount of base, and it is sufficient that it is 1 to 5 times the mole of bisphenols used as raw materials, preferably 1.5
~3 times the mole is sufficient.

During this reaction, quaternary ammonium salts, quaternary phosphorus salts, macrocyclic polyethers such as crown ethers, nitrogen-containing macrocyclic polyethers such as cributate, nitrogen-containing chain polyethers, polyethylene glycol, and their alkyl ethers are used. Phase transfer catalysts such as copper powder, copper salts, etc. may be added as reaction promoters.

As the reaction solvent, an aprotic polar solvent is used. Specifically, N-methylformamide, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, dimethylsulfone, sulfolane,
■-Methyl-2-pyrrolidinone, 1,3-dimethyl-2
-imidazolidinone, N,N,N:N'-tetramethylurea, hexamethylphosphotriamide and 1.3-
Dimethyl-3,4,5,6-titrahydro-2 (IH)
-pyrimidine, etc. The amount of these solvents used is not particularly limited, but usually 1 to 10 times the weight of the raw materials is sufficient.

When carrying out the reaction, there are no particular restrictions on the charging method of the raw materials, but for example, (1) after preparing the alkali metal salt of bisphenols in advance by charging a predetermined amount of bisphenols, a base, and a solvent, m - There is a method of adding dinitrobenzene to cause the reaction, or (2) a method of charging all the raw materials containing m-dinitrobenzene from the beginning and allowing the reaction to proceed as is. Not limited.

Using an oxide or hydroxide of Al7 as a base, the water trapped in the reaction system can be gradually removed from the system during the reaction by, for example, bubbling nitrogen gas. Alternatively, a method is used in which a small amount of benzene, toluene, xylene, chlorobenzene, etc. is used and removed from the system as an azeotrope. On the other hand, when carbonates, hydrogen carbonates, etc. are used, no particular dehydration operation is required.

The reaction temperature is usually 100 to 240°C, preferably 12
The temperature ranges from 0 to 180°C, and the reaction time ranges from 5 to 30 hours. The end point of the reaction can be determined by thin layer chromatography, high performance liquid chromatography, and the like. After the reaction is complete, the target crude product can be obtained by distilling off the solvent or by directly discharging the reaction solution into water. This crude product can be purified by recrystallization etc.
Usually, it can be used as is in the second stage reaction.

The reduction method used in the second stage reaction is not particularly limited, and is usually a method of reducing a nitro group to an amino group (for example, New Experimental Chemistry Course, Vol. 15, Oxidation and Reduction [■], Maruzen (19
77) ) can be applied, but catalytic reduction or hydrazine reduction is preferred industrially. In the case of catalytic reduction, metal catalysts commonly used in catalytic reduction, such as nickel, palladium, platinum, rhodium, ruthenium, cobalt, and copper, can be used as the reduction catalyst. Industrially it is preferred to use palladium catalysts.

Although these catalysts can be used in the metal state, they are usually supported on the surface of a carrier such as carbon, barium sulfate, silica gel, alumina, or celite, and nickel, cobalt, copper, etc. Also used as a catalyst. The amount of the catalyst used is not particularly limited, but it is in the range of 0.01 to 10% by weight as a metal based on the raw material bis(3-nitrophenoxy) compound, and usually when used in the metal state, The content ranges from 2 to 8% by weight, and from 0.1 to 5% by weight when supported on a carrier.

The reaction solvent is not particularly limited as long as it is inert to the reaction, and examples thereof include alcohols such as methanol and ethanolisopropyl alcohol, glycols such as ethylene glycol and fluoropylene gellicol,
Ethers such as ether, dioxane, tetrahydrofuran, methyl cellosolve, aliphatic hydrocarbons such as hexa7, cyclohexane, aromatic hydrocarbons such as benzene, toluene, xylene, esters such as ethyl acetate, butyl acetate, dichloromethane, Chloroform, carbon tetrachloride,
■, 2-dichloroethane, 1. 1, 2-) Norogenated hydrocarbons such as dichloroethane and tetrachloroethane, N,N-dimethylformamide, dimethylsulfoxide, etc. can be used. Note that when using a reaction solvent that does not mix with water, if the reaction progresses slowly, it can be accelerated by adding a commonly used phase transfer catalyst such as a quaternary ammonium salt or a quaternary phosphonium salt.

The amount of the solvent to be used is not particularly limited as it is sufficient to suspend or completely dissolve the raw materials, but usually 0.5 to 10 times the weight of the raw materials is sufficient.

The reaction temperature is not particularly limited. Generally 20-200
℃ range, especially 20 to 100℃ is preferred.

Moreover, the reaction pressure is usually normal pressure to 501i/cr! -G
That's about it.

The reaction is usually carried out by adding a catalyst to the raw material dissolved or suspended in a solvent, and then introducing hydrogen at a predetermined temperature with stirring to carry out a reduction reaction. The end point of the reaction can be determined by the amount of hydrogen absorbed, or by thin layer chromatography, high performance liquid chromatography, etc.

On the other hand, in the case of hydrazine reduction, hydrazine is usually
The reduction reaction may be carried out in a small excess amount, preferably 1.2 to 2 times the amount of the theoretical needle.

As the catalyst, the above-mentioned metal catalyst that is generally used for catalytic reduction is used. Industrially, catalysts in which palladium/carbon, platinum/carbon or ferric chloride is adsorbed on activated carbon are preferred. There is no particular restriction on the amount of catalyst used;
Usually, the metal content is in the range of 0.01 to 30% by weight based on the raw material bis(3-nitrophenoxy) compound.

As the reaction solvent, the same solvent as in the case of catalytic reduction can be used. The reaction temperature is not particularly limited (generally 20 to 150°C, preferably 40 to 100°C).

The reaction is usually carried out by adding a catalyst to the raw material dissolved or suspended in a solvent, and then adding hydrazine dropwise at a predetermined temperature with stirring to carry out the reduction reaction. The end point of the reaction can be determined by thin layer chromatography, high performance liquid chromatography, etc.

After the reaction is completed, the catalyst is removed by heating the reaction solution, and then the solvent is distilled off, if necessary, to obtain a crude product of the desired bis(3-aminophenoxy) compound. This crude product can be purified by recrystallization or isolation as a hydrochloride.

(Functions and Effects) According to the method of the present invention, the condensation reaction between bisphenols and m-dinitrobenzene, which was thought to be difficult in the past, does not require the addition of a reaction promoter such as a phase transfer catalyst. 〈Various bis(3-nitrophenoxy)
Various bis(3-aminophenoxy) compounds can be produced relatively easily and in good yields by producing a compound and further reducing it by a conventional method. Therefore, the method of the present invention is an extremely excellent method from an industrial perspective.

(Example) Hereinafter, the present invention will be specifically explained with reference to Examples.

Example 1 4,4'-dihydroxybiphenyl 1867 (1.0 mol) and m-dinitrobenzene 4 were placed in a glass reaction vessel.
385' (2.6 mol), potassium carbonate 3631 and 200ml of N,N-dimethylformamide.
React at 45-150°C for 16 hours. After the reaction was completed, it was cooled and filtered to remove KNO2, and then the solvent in the r solution was distilled off under reduced pressure, cooled to 65°C, and methanol 200%
Charge 0ml and stir for 1 hour. The crystals were separated from F, washed with water, washed with methanol, and dried to obtain brown crystals of 4,4'-bis(3-nitrophenoxy)biphenyl. Yield 426
(yield 99.5%) Then, in a glass reaction vessel No. 11, crude 4,4'-bis(3-nitrophenoxy)biphenyl 1oo P (0.23 mol), activated carbon 101, and ferric chloride/6 water were added. Phase 11 and methyl cellosolve 500
ml and stirred for 30 minutes under reflux. Next 70~
At 80°C, 3 hydrazine aqueous phase 46P (0.92 mol)
Drip over time. After the dropwise addition was completed, the reaction was completed by stirring at 70 to 80°C for 5 hours. After cooling, filter to remove the catalyst, drain into 500 ml of water, and filter to remove crystals. Add 48p of 35% hydrochloric acid and 540ml of 50% ingrozoloalcohol (IPA)/water to this, dissolve by heating, and cool to form 4.4'-bis(3-aminophenoxy).
Biphenyl hydrochloride was precipitated.

After filtration, 540 g of water at 50% rpA was added and decomposed in a heating bath. 51 activated carbon was added and filtrated, neutralized with aqueous ammonia, and the crystals were filtrated, washed with water, and dried. ′−
Bis(3-aminophenoxy)biphenyl was obtained. Yield 72.0? (Yield 85%) Colorless crystals mp, 1
44-146°CHN Analysis value (%) 78.56 5.21 7.66*
) MS as C24H2ON202: 368
(M”), 340.184I R (KBr, cm-
): 3400 and 3310 (NH2 group), 12
40 (Ether bond) Example 2 The crude 4.4 obtained in Example 1 was placed in a sealed glass container of 11.
'-Bis(3-nitrophenoxy)biphenyl 100
P (0.23% #) was charged together with 350 ml of 5% Pd/C (manufactured by Nippon Engelhard) 1 haftyl cellosolve. Hydrogen was introduced at 60-65° C. with vigorous stirring, and no further absorption occurred in 8 hours, completing the reaction.

Post-treatment and purification were carried out in the same manner as in Example 1.
, 4'-his(3-aminophenoxy) and phenyl were obtained. Yield: 70.3 P (Yield: 83%) Colorless crystals m
p, 144-b Purity 99.3% (by high performance liquid chromatography) Example 3 85.6% (0,375 mol) of 2,2-bis(4-hydroxyphenyl)propane in a 11 glass reaction vessel
, m-dinitrobenzene 151.2% (0.9 mol), potassium carbonate 124.6 ? and 660 ml of N,N-dimethylform (7mm)', 145~
React at 150°C for 10 hours. After the reaction was completed, it was cooled and filtered to remove KNO2, and then the solvent of the liquid was distilled off under reduced pressure, cooled to 65°C, and methanol 45oTLl was added.
and stir for 1.0 hour. Separate the crystals, wash with water,
After washing with methanol and drying, yellowish brown crystals of 2,2-bisC4-(3-nitrophenoxy)phenyl]propane were obtained. Yield 164.8 P (yield 93.5%) Then,
Crude 2.2-bis(4-
(3-nitrophenoxy)phenyl]propane 100
! i' (0.21 mol), activated carbon 105', chloride chloride
Charge iron hexahydrate IP and 300 ml of methyl cellosolve, and stir under reflux for 30 minutes. Then 70-80°C
Then hydrazine hydrate 42 P (0.84 mol) was added dropwise over a period of 2 hours. The mixture is further stirred at 70-80°C for 5 hours. After cooling, filter to remove the catalyst and methyl cellosolve 15
Distill 0ml. Add 270 t of 20% aqueous hydrochloric acid solution,
Furthermore, when salt 309- is added and the mixture is cooled to 20 to 25° C. with stirring, crystals are precipitated. After dividing this into r, 30% IP
A/Crystals precipitate when neutralized with aqueous ammonia in water. This was filtered, washed with water, dried, and then recrystallized from a mixed solvent of benzene and n-hexane.
3-Aminophenoxy)phenyl]propane was obtained. Yield 69.2P (yield 75%) Colorless crystals mp, 106-108°C Purity 99.5
% (by high performance liquid chromatography) HN Analysis value (%) 79.21 6.40 6.71 MS as C, 7H2, N2O2: 470
(M”), 455 (M -CH3) +IR (KB
r, crn'): 3460 and 3370 (N
H2 group), 1220 (ether bond) Example 4 Crude 2,2-bis(:4-(3-nitrophenoxy)phenyl)propane 507 produced by the same method as Example 3 was placed in a 300D glass sealed container. (0.11 mol) at 5%
Charge with Pd/C2, 5% and 150 ml of methyl cellosolve. Hydrogen was introduced at 60-65° C. with vigorous stirring, and no further absorption occurred in 8 hours, completing the reaction.

Post-treatment and purification were carried out in the same manner as in Example 3, and 2
．． 2-bis[:4-(3-aminophenoxy)phenyl]propane was obtained. Yield: 36.6 ft (yield: 79%)
) Colorless crystals mp, 106-108°C Purity 99.
6% (by high performance liquid chromatography) Example 5 In a 200 ml glass reaction vessel, 20% of 2,2-bis(4-hydroxyphenyl)-hexafluoropropane was added.
(0,059 mol), m-dinitrobenzene 24% (
0.14 mol), potassium carbonate 19.4P and N,
N'-dimethylformamide 1oomA! Charge 1
React at 40-150°C for 7 hours. After the reaction was completed, it was cooled and discharged into 100% water (IJ) to give crude 2,2-bis[:4-(3
-nitrophenoxy)phenyl]-hexafluoropropane was separated as a tar. This tar-like substance was dissolved in benzene, washed with water, the benzene layer was dehydrated with magnesium sulfate, and column chromatography was performed using silica gel to obtain a yellow oil-like purified 2,2-bis(4-
28.3 P (yield: 83%) of (3-nitrophenoxy)phenyl]-hexafluoropropane was obtained.

Next, in a 300 ml glass reaction vessel, 205+- (0,035 mol) of crude 2,2-bis(4-(3-nitrophenoxy)phenyl]-hexafluoropropane, 2J of activated carbon, and ferric chloride/6 water were added. 0.21 of hydrazine hydrate and 100 ml of isopropyl alcohol are charged and stirred for 30 minutes under reflux.Next, 754 ml of hydrazine hydrate (
0.14 mol) was added dropwise over 2 hours, and further 5 mol was added under reflux.
Stir for an hour. After cooling, the catalyst is removed by filtration, and all 601 nl of isopropyl alcohol is distilled off. When 17.5% hydrochloric acid 8051- is added and further added common salt 101 and cooled to 20 to 25° C. with stirring, crystals are precipitated. After filtering this, add isopropyl acetate/I/co/l/40 again.
rnt, after recrystallization with 17.5% hydrochloric acid 8 (l), 5
Crystals precipitate when neutralized with ammonia water in 0% IPA/water. After filtering, washing with water and drying, benzene and n-
Recrystallization was performed using a mixed solvent of hexane to obtain 2,2-bis(:4-(3-aminophenoxy)phenyl)-hexafluoropropane. Yield: 13.67 (yield: 75
%) Colorless crystals mp, 137-139°C Purity 99
．． 2% (by high performance liquid chromatography) HNF Analysis value (%) 62.30 3.89 5.20
End of 21.95) C2? IR as H2ON2Fll
(KBr, CrrL-'): 3480 and 3380
(NH2 group), 1240 (ether bond) Example 6: In a 30 (l ml) glass container, crude 2,2-bis(1-(3-=to0 phenoxy)phenyl]-hexafluoropropane 20
,'i4 (0,035 mol) to 5%Pd/C1,%,
It was charged with 1001 nl of isopropyl alcohol.

When hydrogen is introduced with vigorous stirring at 60-65°C,
After 8 hours, no further absorption occurred and the reaction was complete.

Post-treatment and purification were performed in the same manner as in Example 5.
2,2-bis(4-(3-aminophenoquine)phenyl]-hexafluoropropane was obtained. Yield: 12.7p (
Yield 70%) Colorless crystals mp, 137-1.39°
C purity 99.4% (by high performance liquid chromatography) Example 7 Into a 500 ml glass reaction vessel, 20 y-(0,093 mol) of 4,4'-dihydroxybenzophenone, m
- dinitrobenzene 37.5 P (0.22 mol),
Charge 30 g of potassium carbonate and 350 ml of sulfolane, and react at 160-170°C for 10 hours. After the reaction is completed, the mixture is poured into 2000 ml of water and stirred for 30 minutes. Next, the crystals are separated, washed with water, dried and 4,4'-bis(3-
Brown crystals of -40phenoxy)benzophenone were obtained. Yield: 395L (yield 92%) In a 300 ml glass reaction vessel, add crude 4,4
'-Bis(3-nitrophenoxy)benzophenone 25
P (0.06 mol), activated carbon 2.51, ferric chloride.
hexahydrate 0.255' and methyl cellosolve 130r
nl and stir for 30 minutes at 70-80°C. Next, hydrazine hydrate 1251-(0,
24 mol) was added dropwise over 2 hours, and the mixture was further stirred at 70 to 80°C for 6 hours. After cooling, the catalyst was removed by filtration, and the solvent was distilled off. Next, 131% 35% hydrochloric acid and 6 Qvtl of water were added and dissolved by heating, and 6y- of common salt was added and cooled to precipitate the hydrochloride. After filtering this, it was recrystallized again with 10% saline, and then heated and dissolved in 50% IPA2/water 901, and activated carbon l. was added and filtered, and then neutralized with aqueous ammonia to precipitate crystals.

This was filtered, washed with water, and dried to obtain 4,4'-bis(3-aminophenoxy)penzophenone.

Yield xci, o? (Yield 80%) Colorless crystals mp, 142~] 44°C CHN Analysis value (%) 75.60 5,20 6.99:
*) MS as C2, H2oNto3: 396
(M+), 212 IR (KBr, cm-'): 3470 and 33
70 (NH2 group), l625 (carbonyl group), 12
20 and 1240 (ether bond) Example 8 Into a 500 ml glass sealed container, 4,4'-bis(3-nitrophenoki 7
) 5% P of benzophenone 5051-(0.12 mol)
d/C1i and 250 ml of methyl cellosolve. Hydrogen was introduced at 65-70'C with vigorous stirring, and no further absorption occurred in 9 hours, and the reaction was complete. Workup and purification were carried out in the same manner as in Example 7 to obtain 4,4'-bis(3-aminophenoxy)benzophenone.

Yield 35.5 y- (yield 75%) Colorless crystals mp, 142-144°C Purity 99.
3% (by flat liquid chromatography) Example 9 4,4'-dihydroxydiphenyl sulfone 2 oz (O
, OS mol), m-dinitrobenzene 32.3? (0,
19 mol), potassium carbonate 26.1'i' and N, N
'-Dimethylformamide 150ml was charged from 145~
React at 150°C for 15 hours. After the reaction is complete, 2000 g of water
m1 and stir for 30 minutes. Next, separate the crystals by P,
After washing with water and drying, brown crystals of 4,4'-bis(3-nitrophenoxy)diphenylsulfone were obtained.

Yield: 35.4 y- (yield: 90%) Then, in a 300 ml glass reaction vessel, the crude 4.4'
-bis(3-nitrophenoxy)diphenylsulfo 72
5% (0,055 mol), activated carbon 2.5z, ferric chloride hexahydrate 0.25P and methyl cellosolve 13
Charge 0 ml and stir under reflux for 30 minutes. 70-8
At 0°C, hydrazine aqueous phase 11P (0.22 mol) was added to 2
After dropping over a period of time, the mixture is further stirred at 70 to 80°C for 6 hours. After cooling, the catalyst was removed by filtration, and the solvent was distilled off under reduced pressure. Next, 121 ml of 35% hydrochloric acid and 73 ml of water were added and dissolved by heating, and then 7 ψ of common salt was added and cooled to precipitate the hydrochloride. After filtering this and recrystallizing it again with 10% saline, 100rnl of 50% IPA/water was added and dissolved by heating.
After adding activated carbon ly- and filtering, crystals are precipitated when neutralized with aqueous ammonia. This was filtered, washed with water, dried, and then recrystallized from ethanol to obtain 4,4'-bis(3-aminophenoxy)diphenylsulfone.

Yield Is, sy (yield 79%) Colorless crystal mp, 134-136°CHNS *) IR as C24H2GN204S (KBr,
cm-' ): 3480 and 3380 (NH2 group), 1310 and 1150 (SO2 group), 1230 (ether bond) Example 10 In a 500 ml glass sealed container, crude 4 produced in the same manner as Example 9 was added. .4'-bis(3-nitrophenoxy)diphenylsulfone 50% (0.1 mol) with 5% P
d/C154 and 250 ml of methyl cellosolve. When hydrogen was introduced with vigorous stirring at 60-65°C, no further absorption occurred in 8 hours, and the reaction was completed. Work-up and purification in the same manner as in Example 9 yielded 4.4'- Bis(3-aminophenoxy)diphenylsulfone was obtained.

Yield 32. sy (Yield 69%) Colorless crystals mp, 134-136°C Purity 99.
2% (by high performance liquid chromatography) Patent applicant: Mitsui Toatsu Chemical Co., Ltd. Procedural amendment (voluntary) l) ``- 1, case description
(1985 Patent Application No. 32568
(92'% al(7) 4 v*
a.

Method for producing bis(3-aminophenoxy) compound
a.

3. Person who makes corrections
5) 4'- Ri 4, Amended Symmetrical Specification, page 2, line 122, "bivalence of 0" is changed to -0- of 2
It is corrected as "the basis of valence."

Similarly, on the 3rd page, line 4, the text is corrected to read ``is bis('') and ``is represented by bis(''.

Similarly, rMs on page 23, bottom 1st line: 470 [”)
, 455 (M-CH3)"J rMs:410["
), 395 (M-CH3)” J.

Similarly, on page 25, line 2, "N,N'-cymenformamide" is corrected to "rN,N-dimethylformamide".

Similarly, on page 29, bottom 8th line, "manufactured 4゜-" is changed to [
Corrected as manufactured crude 4.4・-].

Procedural Amendment (Method) June 18, 1985, Indication of the case against Dr. Gakudono Shiga, Director-General of the Intoxication Agency, 1985 Patent Application No. 32568 2, Name of the invention: Process for producing bis(3-aminophenoxy) compound 5. Relationship with the case of the person making the amendment Patent applicant address: 3-2-5-4 Kasumigaseki, Chiyoda-ku, Tokyo Date of amendment order: May 28, 1985 (shipping date) 1) Specification, No. 4 page, lines 8-9 “J, schra
rrm et al., Liebigs, Ann, Ohem,
, J. Justus Liebigs Ann,
Chem, ), correct J.

2) Same (, page 5, lines 7-8 "H, M, Re1l
es et al., J. Polym Sci, Poly
m, Ohem, Bd,, J [Journal Off.
Polymer Science 0. Polymer Chemistry Education (J, Polym, Sci.).

Correct it as polym, Ohem, Ed, ), j.

Similarly to No. 3, page 5, lines 8 to 9, "J, Rin, Beck.
5J, org, ahem, , J.
Off Org = Yuri Chemistry (J, Org,
chem, )! Correct it with J.

Null Off Polymer Science 6. Polymer chemistry editorial * y (J, Polym, Sc
i.

Correct Polym, Ohem, Ed.), J.

5) Similarly, f-, r, FL on page 5, lines 11-12
.

Beck, Tetrahedron J is corrected as "Tetrahedron (Tetr3-hedron) J.

6) Similarly, from page 5, bottom line 1 to page 6, line 1, “N, Kornblum et al., J, Or9.0hem
, , J is corrected as [Journal of Organic Chemist IJ-(J, Org, Ohem, ), J.

7) Similarly, on page 6, line 10, “p, Montan
ari et al., ahem, & xnd, J. Chemistry Aft.

・Industry (ahem, & Ird, ),”
I am corrected.

Written amendment to the above procedure (spontaneous) August 3, 1985 Michibe Uga, Commissioner of the Patent Office1, Indication of the case Patent Application No. 32568 of 19852, Title of the invention: Bis(3-aminophenoxy) compound Manufacturing method 3, relationship with the case of the person making the amendment Patent applicant address: 3-2-5-4 Kasumigaseki, Chiyoda-ku, Tokyo;
Column 5 of “Detailed Description of the Invention” of the specification to be amended, contents of the amendment, f) t-, i 1) Next in the description, page 32, line 13: Example 11
Add.

"Example 11 4.4I-dihydroxydiphenylsulfi)" 218
F (1 mol) 1m-dinitrobenzene 4'03 f (
2.4 mol), 331 g (2.4 mol) of potassium carbonate and 2.51 g of N,N-dimethylformamide! was charged and reacted at 145 to 150°C for 20 hours. After the reaction is completed, it is cooled and filtered, and the solvent of Solution F is distilled off under reduced pressure. After cooling to 65°C, 800 methanol was charged and stirred for 1 hour.

The crystals were washed individually with methanol and then dried to obtain crystals of 4,4-his(3-nitrophenoxy)diphenyl sulfide. Yield 4299C yield 92.3%).

Then, the crude product 428y (0,
93 moles), activated carbon 22.6 g, ferric chloride hexahydrate 0.9 f and methyl cellosolve 1.51! Charge the
Stir under reflux for 30 minutes. After 155.2 g (3.1 mol) of hydrazine monohydrate was added dropwise over 2 hours at 110 to 115°C, the mixture was further stirred under reflux for 3.5 hours. After cooling, filter to remove the catalyst.

The solvent was concentrated under reduced pressure.

Next, 205% of 35% hydrochloric acid and 1120% of water. After adding 480 g of isopropyl alcohol and dissolving it by heating, 20 f of activated carbon is charged and hot filtered.

Add 112 g of common salt and crystallize by cooling. After the hydrochloride crystals are separated by furnace, they are neutralized with aqueous ammonia to obtain the desired 4,4'
-bis(3-aminophenoxy)diphenyl sulfide was obtained. Yield 265fC Yield 66%) Colorless crystals mp
, 112.4-113.4℃ (corr,) CHNS Elemental analysis Calculated value (to) 71.97 5.03
7.00 8.01* MS (FD) as C2, H2oN20□S: 400 (M IR (KBr, cm-'): 3390 and 3300
(NH, group).

1220 (ether bond) j that's all

Claims (1)

[Claims] 1) General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, X is a divalent hydrocarbon group having 1 to 10 carbon atoms, or -C( CF_3)_2-, -CO-, -S-, -
It represents a divalent group of SO-, -SO_2- or -O-. Moreover, X may be directly bonded with a single bond. General formula (II) obtained by condensing 4,4'-bisphenols represented by ) and m-dinitrobenzene in an aprotic polar solvent in the presence of a base ▲Mathematical formulas, chemical formulas, tables, etc. are available▼ (II) (In the formula, X has the same meaning as in general formula (I))
A bis(3-nitrophenoxy) compound represented by
General formula (III) characterized by subsequent reduction ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) (In the formula, X has the same meaning as in general formula (I))
A method for producing a bis(3-aminophenoxy) compound represented by