CN102584610B - Bisphenol 2 (m-amino p-hydroxy phenyl) ether hydrochloride and preparation method and application thereof - Google Patents

Abstract

The invention discloses bisphenol 2 (m-amino p-hydroxy phenyl) ether hydrochloride such as 2,2-2(4-(3-amino-4-hydroxy phenoxy)phenyl) propane hydrochloride and a preparation method and an application of the bisphenol 2 (m-amino p-hydroxy phenyl) ether hydrochloride. The preparation method comprises the steps: nitrating p-hydroxy halogen benzene to obtain m-nitro p-hydroxy halogen benzene, protecting hydroxyl by benzyl, coupling the hydroxyl with a bisphenol agent to obtain ether, removing benzyl by means of hydrogenation and reduction and reducing nitryl into amino, and finally using hydrochloric acid to perform salifying to obtain the bisphenol 2 (m-amino p-hydroxy phenyl) ether hydrochloride. The compound provided by the invention is particularly suitable for the preparation of soluble polybenzoxazol, and the prepared polybenzoxazol has the characteristics of high strength and solubility in the common organic solvent, the defects of insolubility and difficulty in processing of the existing polybenzoxazol polymer are overcome, and the bisphenol 2 (m-amino p-hydroxy phenyl) ether hydrochloride can also be used for the preparation of polyamide and polyimide.

Description

Bis-phenol two (an amino p-hydroxybenzene) ether hydrochloride and its production and use

Technical field

The invention belongs to monomer of benzoxazole base polymer and preparation method thereof, relate to bis-phenol two (an amino p-hydroxybenzene) ether hydrochloride and its production and use.Bis-phenol two provided by the invention (an amino p-hydroxybenzene) ether hydrochloride is specially adapted to synthetic polybenzoxazole, also can be used for the preparation of polymeric amide and polyimide.

Background technology

Since last century the eighties, benzoxazole base polymer, owing to showing good mechanics, thermal property and chemical stability, has caused extensive attention and research.Wherein the most representative polyparaphenylene Ben Bing bis-oxazole (PBO) is a kind of high strength the polymkeric substance with superior heat resistance flame retardant properties.Its tensile strength can reach 5.8GPa, and modulus can reach 300GPa, and heat decomposition temperature reaches 650 ℃, and LOI reaches 68.But because PBO molecule is rigid rod-like molecules, degree of crystallinity is high and plane of crystal is smooth, cause it not melt insoluble and intermiscibility is poor, limited greatly its range of application.In order to improve these shortcomings of PBO, expand its application, people have carried out a large amount of research, mainly comprise the PBO monomer that pbo fiber is carried out to surface modification and design synthesizing new, such as introducing side-chain radical or use special monomer to form side chain in monomer, or in monomer, introduce flexible group as saturated carbon chains, ehter bond etc.

As in patent CN 1660776A, synthesized not containing the diamino bis-phenol of fragrant ehter bond, in patent CN 101362700A, also synthesized similar compound simultaneously.In these compounds, contain saturated carbon chains or sulfuryl group, can improve the kindliness of polybenzoxazole molecule.But mention the polybenzoxazole being prepared by monomer whose in CN 101362700A, be dissolved in hardly organic solvent, solvability is not improved significantly.

In patent US 2004/0049081, synthesized and contained the diamino dihydroxy compound of fragrant ehter bond for the monomer of polybenzoxazole.The monomer of this structure, owing to containing the groups such as fragrant ehter bond and saturated carbon chains simultaneously, has further improved the molecular flexibility of polybenzoxazole.But its raw material is difficult for preparation to hydroxyl fluorobenzene between nitro, expensive, be difficult to promote practical.

In addition, in patent CN101263180A, the polybenzoxazole that has synthesized solubility, in itself and CN 1660776A the difference of polybenzoxazole with 1,4-cyclohexane cyclohexanedimethanodibasic has replaced terephthalic acid, the kindliness of hexanaphthene group has improved the solvability of polymkeric substance, has kept again good performance simultaneously.But the price of 1,4 cyclohexanedicarboxylic acid is up to more than 50000 yuan/ton, is the more than 5 times of price (8000～10000 yuan/ton) of terephthalic acid, and its cost is significantly improved, and practicality is poor.

Summary of the invention

Object of the present invention is intended to overcome above-mentioned deficiency of the prior art, and functional, the practical bis-phenol of a kind of quality product two (an amino p-hydroxybenzene) ether hydrochloride and its production and use is provided.

Content of the present invention is: 2,2-bis-(4-(3-amino-4-hydroxy phenoxy group) phenyl) propane hydrochloride salt, is characterized in that this compound has the chemical structural formula of formula I:

（Ⅰ）

Described in content of the present invention 2,2-bis-(4-(3-amino-4-hydroxy phenoxy group) phenyl) preparation method of propane hydrochloride salt, is characterized in that comprising the following steps:

Step I: between preparation, nitro is to hydroxyl halobenzene:

To add in reactor A hydroxyl halobenzene, and add methylene dichloride to dissolve, be wherein 1:1～5 to hydroxyl halobenzene mmole (mmol) number with the ratio of methylene dichloride milliliter (ml) number; Agitation condition borehole cooling to 0～10 ℃, drip 65% concentrated nitric acid, to hydroxyl halobenzene mmole (mmol) number, are wherein 1:1～1.5 with the ratio of nitric acid mmole (mmol) number; After nitric acid finishes, stir 2～6 hours at 0～10 ℃, after reaction finishes, the washing of use methylene dichloride 1～3 volume multiple 2～3 times, uses solvent orange 2 A recrystallization, dry, makes a nitro to hydroxyl halobenzene;

Describedly to hydroxyl halobenzene structure, be:

In formula, X is: Cl, Br or I;

Reaction formula is:

To nitro between hydroxyl halobenzene to hydroxyl halobenzene

Described recrystallization solvent A is: water, and alcohol is methyl alcohol, ethanol, Virahol, and halohydrocarbon is methylene dichloride, chloroform, ethylene dichloride, and ester is ethyl acetate, butylacetate; Ether is ether, tertiary butyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF), and nitrile is one or more the mixture in acetonitrile, propionitrile;

Step II: between preparation, nitro is to benzyloxy halobenzene:

Under agitation condition, nitro between step I gained is added in reactor B hydroxyl halobenzene and solvent B, in the middle of it, nitro is 1:1～5 to hydroxyl halobenzene mmole (mmol) number with the ratio of solvent B milliliter (ml) number; After a nitro dissolves completely to hydroxyl halobenzene, then add halo benzyl, alkali and catalyst A, in the middle of it, nitro is 1:1～2 to hydroxyl halobenzene mmole (mmol) number with the ratio of halo benzyl mmole (mmol) number; Between nitro to hydroxyl halobenzene mmole (mmol) number, be 1:1～5 with the ratios of alkali mmole (mmol) number; Between nitro to hydroxyl halobenzene mmole (mmol) number, be 1:0.01～0.1 with the ratios of catalyst A mmole (mmol) number; Being heated to 40～100 ℃ stirs 2～8 hours, after reaction finishes, steaming desolventizes B, adds the water of solvent B total amount 0.5～2 volume multiple, and a nitro is 1:0.5～2 to hydroxyl halobenzene mmole (mmol) number with the ratio of water milliliter (ml) number, stir 0.5～2 hour, suction filtration, solids, with after the water washing of solvent B total amount 1～3 volume multiple 2～3 times, is used solvent C recrystallization, dry, make a nitro to benzyloxy halobenzene;

Described nitro to the chemical structural formula of hydroxyl halobenzene is:

In formula, X is: Cl, Br or I;

Reaction formula is:

Between nitro to nitro between hydroxyl halobenzene halo benzyl to benzyloxy halobenzene

Wherein X is: Cl, Br or I; X' is: Cl, Br or I;

Described catalyst A is selected from iodine and salt compounded of iodine, is sodium iodide or potassiumiodide;

Described alkali is selected from alkali or its salt of weak acid that alkalies and alkaline earth generates, and is sodium hydroxide, potassium hydroxide, hydrated barta, sodium carbonate, salt of wormwood or sodium-acetate;

Described solvent B is: ether is ether, tertiary butyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF), ketone is acetone, butanone, and nitrile is acetonitrile, propionitrile, and acid amides is N, the mixture of one or more in dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone;

Described recrystallization solvent C is: water, and alcohol is methyl alcohol, ethanol, Virahol, and halohydrocarbon is methylene dichloride, chloroform, ethylene dichloride, and ester is ethyl acetate, butylacetate; Ether is ether, tertiary butyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF), and nitrile is one or more the mixture in acetonitrile, propionitrile;

Step III: preparation 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) propane:

Between step II is made, nitro adds in reactor C benzyloxy halobenzene and solvent D, then adds dihydroxyphenyl propane, alkali and catalyst B, and in the middle of it, nitro is 1:1～5 to benzyloxy halobenzene mmole (mmol) number with the ratio of solvent D milliliter (ml) number; Between nitro to benzyloxy halobenzene mmole (mmol) number, be 1:0.2～0.5 with the ratios of dihydroxyphenyl propane mmole (mmol) number; Between nitro to benzyloxy halobenzene mmole (mmol) number, be 1:1～5 with the ratios of alkali mmole (mmol) number; Between nitro to benzyloxy halobenzene mmole (mmol) number, be 1:0.1～1 with the ratios of catalyst B mmole (mmol) number; At nitrogen (N ₂) be heated to 120～180 ℃ under atmosphere and stir 10～48 hours, after reaction finishes, the water that adds solvent D total amount 5～10 volume multiples, suction filtration, solids is with after the water washing of solvent D total amount 1～3 volume multiple 2～3 times, with solvent E recrystallization, make 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) propane;

Reaction formula is:

Between nitro to benzyloxy halobenzene dihydroxyphenyl propane

2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) propane

Wherein X is: Cl, Br or I;

Described catalyst B is selected from elemental copper and cuprous salt, is cuprous chloride, cuprous bromide or cuprous iodide;

Described alkali is selected from alkali or its salt of weak acid that alkalies and alkaline earth generates, and is any in sodium hydroxide, potassium hydroxide, hydrated barta, sodium carbonate, salt of wormwood, sodium-acetate;

Described solvent D is: acid amides is that DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone, sulfoxide are any in methyl-sulphoxide;

Described recrystallization solvent E: water, alcohol is methyl alcohol, ethanol, Virahol, and halohydrocarbon is methylene dichloride, chloroform, ethylene dichloride, and ester is ethyl acetate, butylacetate; Ether is ether, tertiary butyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF), and nitrile is one or more the mixture in acetonitrile, propionitrile;

Step IV: preparation 2,2-bis-(4-(3-amino-4-hydroxy phenoxy group) phenyl) propane hydrochloride salt;

Step III is made 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) propane adds in reactor D with solvent F dissolving, wherein 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) propane mmole (mmol) number is 1:10～15 with the ratios of solvent F milliliter (ml) number; Adding again catalyzer C, 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) ratio of propane quality gram (g) and catalyzer C quality gram (g) is 1:0.01～0.1; Hydrogen (H at 1～10bar pressure ₂) under atmosphere, in 25～50 ℃, stir 10～24 hours, after reaction finishes, filtration catalizer C, steaming desolventizes F, with the 2～12mol/L aqueous hydrochloric acid recrystallization that contains massfraction 1% tindichloride, 100 ℃ of vacuum-drying 24h of gained solid, make 2,2-bis-(4-(3-amino-4-hydroxy phenoxy group) phenyl) propane hydrochloride salt;

Reaction formula is:

2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) propane

Structure formula I

Described solvent F: alcohol is methyl alcohol, ethanol, Virahol, ether is one or more the mixture in ether, tetrahydrofuran (THF);

Described catalyzer C is the platinum family precious metal being loaded on carrier, and platinum family precious metal is palladium, platinum or rhodium, and carrier is gac, aluminum oxide or silicon oxide.

This compound 2,2-bis-(4-(3-amino-4-hydroxy phenoxy group) phenyl) essential characteristic of propane hydrochloride salt: white powder, structural characterization is as follows: infrared spectra (KBr, cm ^-1) 3374,2947,1632,1593,1526,1463,1429,1280,1263,1235,1182,1167,1149,1073,1032,967,911,864,831,819,755; Ultimate analysis (%): theoretical value: C:62.92, H:5.48, N:5.43; Measured value: C:62.86, H:5.43, N:5.37; ¹hNMR:(D ₂o, 400MHz, ppm) 7.30(8H); 6.63(4H); 6.14(2H); 1.73(6H); ESI-MS:m/z (M+1) 443.3.

Another content of the present invention is: 4,4 '-bis-(3-amino-4-hydroxy phenoxy group) sulfobenzide hydrochloride, is characterized in that this compound has the chemical structural formula of formula II:

（Ⅱ）

The preparation method of 4,4 '-bis-(3-amino-4-hydroxy phenoxy group) described in another content of the present invention sulfobenzide hydrochloride, is characterized in that comprising the following steps:

Step I: between preparation, nitro is to hydroxyl halobenzene:

To add in reactor A hydroxyl halobenzene, and add methylene dichloride to dissolve, be wherein 1:1～5 to hydroxyl halobenzene mmole (mmol) number with the ratio of methylene dichloride milliliter (ml) number; Agitation condition borehole cooling to 0～10 ℃, drip 65% concentrated nitric acid, to hydroxyl halobenzene mmole (mmol) number, are wherein 1:1～1.5 with the ratio of nitric acid mmole (mmol) number; After nitric acid finishes, stir 2～6 hours at 0～10 ℃, after reaction finishes, the washing of use methylene dichloride 1～3 volume multiple 2～3 times, uses solvent orange 2 A recrystallization, dry, makes a nitro to hydroxyl halobenzene;

Describedly to hydroxyl halobenzene structure, be:

In formula, X is: Cl, Br or I;

Reaction formula is:

To nitro between hydroxyl halobenzene to hydroxyl halobenzene

Described recrystallization solvent A is: water, and alcohol is methyl alcohol, ethanol, Virahol, and halohydrocarbon is methylene dichloride, chloroform, ethylene dichloride, and ester is ethyl acetate, butylacetate; Ether is ether, tertiary butyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF), and nitrile is one or more the mixture in acetonitrile, propionitrile;

Step II: between preparation, nitro is to benzyloxy halobenzene:

Under agitation condition, nitro between step I gained is added in reactor B hydroxyl halobenzene and solvent B, in the middle of it, nitro is 1:1～5 to hydroxyl halobenzene mmole (mmol) number with the ratio of solvent B milliliter (ml) number; After a nitro dissolves completely to hydroxyl halobenzene, then add halo benzyl, alkali and catalyst A, in the middle of it, nitro is 1:1～2 to hydroxyl halobenzene mmole (mmol) number with the ratio of halo benzyl mmole (mmol) number; Between nitro to hydroxyl halobenzene mmole (mmol) number, be 1:1～5 with the ratios of alkali mmole (mmol) number; Between nitro to hydroxyl halobenzene mmole (mmol) number, be 1:0.01～0.1 with the ratios of catalyst A mmole (mmol) number; Being heated to 40～100 ℃ stirs 2～8 hours, after reaction finishes, steaming desolventizes B, adds the water of solvent B total amount 0.5～2 volume multiple, and a nitro is 1:0.5～2 to hydroxyl halobenzene mmole (mmol) number with the ratio of water milliliter (ml) number, stir 0.5～2 hour, suction filtration, solids, with after the water washing of solvent B total amount 1～3 volume multiple 2～3 times, is used solvent C recrystallization, dry, make a nitro to benzyloxy halobenzene;

Described nitro to the chemical structural formula of hydroxyl halobenzene is:

In formula, X is: Cl, Br or I;

Reaction formula is:

Between nitro to nitro between hydroxyl halobenzene halo benzyl to benzyloxy halobenzene

Wherein X is: Cl, Br or I; X' is: Cl, Br or I;

Described catalyst A is selected from iodine and salt compounded of iodine, is sodium iodide or potassiumiodide;

Described alkali is selected from alkali or its salt of weak acid that alkalies and alkaline earth generates, and is sodium hydroxide, potassium hydroxide, hydrated barta, sodium carbonate, salt of wormwood or sodium-acetate;

Described solvent B is: ether is ether, tertiary butyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF), ketone is acetone, butanone, and nitrile is acetonitrile, propionitrile, and acid amides is N, the mixture of one or more in dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone;

Described recrystallization solvent C is: water, and alcohol is methyl alcohol, ethanol, Virahol, and halohydrocarbon is methylene dichloride, chloroform, ethylene dichloride, and ester is ethyl acetate, butylacetate; Ether is ether, tertiary butyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF), and nitrile is one or more the mixture in acetonitrile, propionitrile;

Step III: preparation 4,4 '-bis-(3-nitro-4-benzyloxy phenoxy group) sulfobenzide:

Nitro between step II gained is added in reactor C benzyloxy halobenzene and solvent D, add again bisphenol S, alkali and catalyst B, in the middle of it, nitro is 1:1～5 to benzyloxy halobenzene mmole (mmol) number with the ratio of solvent D milliliter (ml) number, between nitro to benzyloxy halobenzene mmole (mmol) number, be 1:0.2～0.5 with the ratios of bisphenol S mmole (mmol) number, between nitro to benzyloxy halobenzene mmole (mmol) number, be 1:1～5 with the ratios of alkali mmole (mmol) number, between nitro to benzyloxy halobenzene mmole (mmol) number, be 1:0.1～1 with the ratios of catalyst B mmole (mmol) number, nitrogen (N ₂) be heated to 120～180 ℃ under atmosphere and stir 10～48 hours, after reaction finishes, the water that adds solvent D total amount 5～10 volume multiples, suction filtration, solids is with after the water washing of solvent D total amount 1～3 volume multiple 2～3 times, with solvent E recrystallization, make 4,4 '-bis-(3-nitro-4-benzyloxy phenoxy group) sulfobenzide,

Reaction formula is:

Between nitro to benzyloxy halobenzene bisphenol S

4,4 '-bis-(3-nitro-4-benzyloxy phenoxy group) sulfobenzide

Described catalyst B is selected from elemental copper and cuprous salt, is cuprous chloride, cuprous bromide or cuprous iodide;

Described alkali is selected from alkali or its salt of weak acid that alkalies and alkaline earth generates, and is any in sodium hydroxide, potassium hydroxide, hydrated barta, sodium carbonate, salt of wormwood, sodium-acetate;

Described solvent D is: acid amides is DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone; Sulfoxide is any in methyl-sulphoxide;

Described recrystallization solvent E is: water, alcohol is methyl alcohol, ethanol, Virahol, halohydrocarbon is methylene dichloride, chloroform, ethylene dichloride, ester is ethyl acetate, butylacetate, ether is ether, tertiary butyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF), and nitrile is one or more the mixture in acetonitrile, propionitrile;

Step IV: preparation 4,4 '-bis-(3-amino-4-hydroxy phenoxy group) sulfobenzide hydrochloride:

By step III gained 4,4 '-bis-(3-nitro-4-benzyloxy phenoxy group) sulfobenzide adds in reactor D with solvent F dissolving, wherein 4,4 '-bis-(3-nitro-4-benzyloxy phenoxy group) sulfobenzide mmole (mmol) number is 1:10～15 with the ratio of solvent F milliliter (ml) number; Add catalyzer C, 4,4 '-bis-(3-nitro-4-benzyloxy phenoxy group) sulfobenzide quality gram (g) is 1:0.01～0.1 with the ratio of catalyzer C quality gram (g) again; Hydrogen (the H of 1～10bar pressure ₂) under atmosphere, 25～50 ℃ are stirred 10～24 hours; After reaction finishes, filtration catalizer C, steams and desolventizes F, with the 2～12mol/L aqueous hydrochloric acid recrystallization that contains massfraction 1% tindichloride, 100 ℃ of vacuum-drying 24h of gained solid, make 4,4 '-bis-(3-amino-4-hydroxy phenoxy group) sulfobenzide hydrochloride;

Reaction formula is:

4,4 '-bis-(3-nitro-4-benzyloxy phenoxy group) sulfobenzide

Structure formula II

Described solvent F is: alcohol is methyl alcohol, ethanol, Virahol, and ether is one or more the mixture in ether, tetrahydrofuran (THF);

Described catalyzer C is the platinum family precious metal being loaded on carrier, and platinum family precious metal is palladium, platinum or rhodium; Carrier is gac, aluminum oxide or silicon oxide.

The essential characteristic of this compound 4,4 '-bis-(3-amino-4-hydroxy phenoxy group) sulfobenzide hydrochloride: white powder, structural characterization is as follows: infrared spectra (KBr, cm ^-1) 3372,3061,1597,1516,1445,1381,1314,1287,1255,1218,1143,1101,1069,934,859,818,772,723,694,657; Ultimate analysis (%): theoretical value: C:53.64, H:4.13, N:5.21; Measured value: C:53.53, H:4.08, N:5.14; ¹hNMR:(D ₂o, 400MHz, ppm) 8.12(4H); 7.54(4H); 6.64(4H); 6.15(2H); ESI-MS:m/z (M+1) 465.1.

Another content of the present invention is: 4,4 '-(3-amino-4-hydroxy phenoxy group) ditane hydrochloride, is characterized in that this compound has the chemical structural formula of formula III:

（Ⅲ）

The preparation method of described 4,4 '-(3-amino-4-hydroxy phenoxy group) ditane hydrochloride, is characterized in that comprising the following steps:

Step I: between preparation, nitro is to hydroxyl halobenzene:

To add in reactor A hydroxyl halobenzene, and add methylene dichloride to dissolve, be wherein 1:1～5 to hydroxyl halobenzene mmole (mmol) number with the ratio of methylene dichloride milliliter (ml) number; Agitation condition borehole cooling to 0～10 ℃, drip 65% concentrated nitric acid, to hydroxyl halobenzene mmole (mmol) number, are wherein 1:1～1.5 with the ratio of nitric acid mmole (mmol) number; After nitric acid finishes, stir 2～6 hours at 0～10 ℃, after reaction finishes, the washing of use methylene dichloride 1～3 volume multiple 2～3 times, uses solvent orange 2 A recrystallization, dry, makes a nitro to hydroxyl halobenzene;

Describedly to hydroxyl halobenzene structure, be:

In formula, X is: Cl, Br or I;

Reaction formula is:

To nitro between hydroxyl halobenzene to hydroxyl halobenzene

Described recrystallization solvent A is: water, and alcohol is methyl alcohol, ethanol, Virahol, and halohydrocarbon is methylene dichloride, chloroform, ethylene dichloride, and ester is ethyl acetate, butylacetate; Ether is ether, tertiary butyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF), and nitrile is one or more the mixture in acetonitrile, propionitrile;

Step II: between preparation, nitro is to benzyloxy halobenzene:

Under agitation condition, nitro between step I gained is added in reactor B hydroxyl halobenzene and solvent B, in the middle of it, nitro is 1:1～5 to hydroxyl halobenzene mmole (mmol) number with the ratio of solvent B milliliter (ml) number; After a nitro dissolves completely to hydroxyl halobenzene, then add halo benzyl, alkali and catalyst A, in the middle of it, nitro is 1:1～2 to hydroxyl halobenzene mmole (mmol) number with the ratio of halo benzyl mmole (mmol) number; Between nitro to hydroxyl halobenzene mmole (mmol) number, be 1:1～5 with the ratios of alkali mmole (mmol) number; Between nitro to hydroxyl halobenzene mmole (mmol) number, be 1:0.01～0.1 with the ratios of catalyst A mmole (mmol) number; Being heated to 40～100 ℃ stirs 2～8 hours, after reaction finishes, steaming desolventizes B, adds the water of solvent B total amount 0.5～2 volume multiple, and a nitro is 1:0.5～2 to hydroxyl halobenzene mmole (mmol) number with the ratio of water milliliter (ml) number, stir 0.5～2 hour, suction filtration, solids, with after the water washing of solvent B total amount 1～3 volume multiple 2～3 times, is used solvent C recrystallization, dry, make a nitro to benzyloxy halobenzene;

Described nitro to the chemical structural formula of hydroxyl halobenzene is:

In formula, X is: Cl, Br or I;

Reaction formula is:

Between nitro to nitro between hydroxyl halobenzene halo benzyl to benzyloxy halobenzene

Wherein X is: Cl, Br or I; X' is: Cl, Br or I;

Described catalyst A is selected from iodine and salt compounded of iodine, is sodium iodide or potassiumiodide;

Described alkali is selected from alkali or its salt of weak acid that alkalies and alkaline earth generates, and is sodium hydroxide, potassium hydroxide, hydrated barta, sodium carbonate, salt of wormwood or sodium-acetate;

Described solvent B is: ether is ether, tertiary butyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF), ketone is acetone, butanone, and nitrile is acetonitrile, propionitrile, and acid amides is N, the mixture of one or more in dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone;

Described recrystallization solvent C is: water, and alcohol is methyl alcohol, ethanol, Virahol, and halohydrocarbon is methylene dichloride, chloroform, ethylene dichloride, and ester is ethyl acetate, butylacetate; Ether is ether, tertiary butyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF), and nitrile is one or more the mixture in acetonitrile, propionitrile;

Step III: preparation 4,4 '-(3-nitro-4-benzyloxy phenoxy group) ditane:

Nitro between step II gained is added in reactor C benzyloxy halobenzene and solvent D, then add Bisphenol F, alkali and catalyst B, in the middle of it, nitro is 1:1～5 to benzyloxy halobenzene mmole (mmol) number with the ratio of solvent D milliliter (ml) number; Between nitro to benzyloxy halobenzene mmole (mmol) number, be 1:0.2～0.5 with the ratios of Bisphenol F mmole (mmol) number; Between nitro to benzyloxy halobenzene mmole (mmol) number, be 1:1～5 with the ratios of alkali mmole (mmol) number; Between nitro to the ratio of benzyloxy halobenzene mmole (mmol) and catalyst B mmole (mmol) number, be 1:0.1～1; Nitrogen (N ₂) be heated to 120～180 ℃ under atmosphere and stir 10～48 hours, after reaction finishes, the water that adds solvent D total amount 5～10 volume multiples, suction filtration, solids is with after the water washing of solvent D total amount 1～3 volume multiple 2～3 times, with solvent E recrystallization, make 4,4 '-(3-nitro-4-benzyloxy phenoxy group) ditane;

Reaction formula is:

Between nitro to benzyloxy halobenzene Bisphenol F

4,4 '-(3-nitro-4-benzyloxy phenoxy group) ditane

In formula, X is: Cl, Br or I;

Described catalyst B is selected from elemental copper and cuprous salt, is cuprous chloride, cuprous bromide or cuprous iodide;

Described alkali is selected from alkali or its salt of weak acid that alkalies and alkaline earth generates, and is any in sodium hydroxide, potassium hydroxide, hydrated barta, sodium carbonate, salt of wormwood, sodium-acetate;

Described solvent D is: acid amides is DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone, and sulfoxide is any in methyl-sulphoxide;

Described recrystallization solvent E is: water, and alcohol is methyl alcohol, ethanol, Virahol, and halohydrocarbon is methylene dichloride, chloroform, ethylene dichloride, and ester is ethyl acetate, butylacetate; Ether is ether, tertiary butyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF), and nitrile is one or more the mixture in acetonitrile, propionitrile;

Step IV: preparation 4,4 '-(3-amino-4-hydroxy phenoxy group) ditane hydrochloride:

Step III is made 4,4 '-(3-nitro-4-benzyloxy phenoxy group) ditane adds in reactor D with solvent F dissolving, wherein 4,4 '-(3-nitro-4-benzyloxy phenoxy group) ditane mmole (mmol) number is 1:10～15 with the ratio of solvent F milliliter (ml) number; Add catalyzer C, 4,4 '-(3-nitro-4-benzyloxy phenoxy group) ditane quality gram (g) is 1:0.01～0.1 with the ratio of catalyzer C quality gram (g) again; Hydrogen (the H of 1～10bar pressure ₂) under atmosphere, 25～50 ℃ are stirred 10～24 hours; After reaction finishes, filtration catalizer C, steams and desolventizes F, with the 2～12mol/L aqueous hydrochloric acid recrystallization that contains massfraction 1% tindichloride, 100 ℃ of vacuum-drying 24h of gained solid, make 4,4 '-(3-amino-4-hydroxy phenoxy group) ditane hydrochloride;

Reaction formula is:

4,4 '-(3-nitro-4-benzyloxy phenoxy group) ditane

Structure formula III

Described solvent F is: alcohol is methyl alcohol, ethanol, Virahol, and ether is one or more the mixture in ether, tetrahydrofuran (THF);

Described catalyzer C is selected from the platinum family precious metal being loaded on carrier, and platinum family precious metal is palladium, platinum or rhodium, and carrier is gac, aluminum oxide or silicon oxide.

The essential characteristic of this compound 4,4 '-(3-amino-4-hydroxy phenoxy group) ditane hydrochloride: white powder, structural characterization is as follows: infrared spectra (KBr, cm ^-1) 3352,2921,1617,1585,1519,1467,1422,1263,1226,1161,1137,1049,1013,965,924,861,817,737; Ultimate analysis (%): theoretical value: C:61.61, H:4.96, N:5.75; Measured value: C:61.55, H:4.87, N:5.70; ¹hNMR:(D ₂o, 400MHz, ppm) 7.24(8H); 6.66(4H); 6.16(2H); 3.96(2H); ESI-MS:m/z (M+1) 414.2.

Another content of the present invention is: 2,2-bis-(4-(3-amino-4-hydroxy phenoxy group) phenyl) HFC-236fa hydrochloride, is characterized in that this compound has the chemical structural formula of formula IV:

（Ⅳ）

Described 2,2-bis-(4-(3-amino-4-hydroxy phenoxy group) phenyl) preparation method of HFC-236fa hydrochloride, is characterized in that comprising the following steps:

Step I: between preparation, nitro is to hydroxyl halobenzene:

To add in reactor A hydroxyl halobenzene, and add methylene dichloride to dissolve, be wherein 1:1～5 to hydroxyl halobenzene mmole (mmol) number with the ratio of methylene dichloride milliliter (ml) number; Agitation condition borehole cooling to 0～10 ℃, drip 65% concentrated nitric acid, to hydroxyl halobenzene mmole (mmol) number, are wherein 1:1～1.5 with the ratio of nitric acid mmole (mmol) number; After nitric acid finishes, stir 2～6 hours at 0～10 ℃, after reaction finishes, the washing of use methylene dichloride 1～3 volume multiple 2～3 times, uses solvent orange 2 A recrystallization, dry, makes a nitro to hydroxyl halobenzene;

Describedly to hydroxyl halobenzene structure, be:

In formula, X is: Cl, Br or I;

Reaction formula is:

To nitro between hydroxyl halobenzene to hydroxyl halobenzene

Described recrystallization solvent A is: water, and alcohol is methyl alcohol, ethanol, Virahol, and halohydrocarbon is methylene dichloride, chloroform, ethylene dichloride, and ester is ethyl acetate, butylacetate; Ether is ether, tertiary butyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF), and nitrile is one or more the mixture in acetonitrile, propionitrile;

Step II: between preparation, nitro is to benzyloxy halobenzene:

Under agitation condition, nitro between step I gained is added in reactor B hydroxyl halobenzene and solvent B, in the middle of it, nitro is 1:1～5 to hydroxyl halobenzene mmole (mmol) number with the ratio of solvent B milliliter (ml) number; After a nitro dissolves completely to hydroxyl halobenzene, then add halo benzyl, alkali and catalyst A, in the middle of it, nitro is 1:1～2 to hydroxyl halobenzene mmole (mmol) number with the ratio of halo benzyl mmole (mmol) number; Between nitro to hydroxyl halobenzene mmole (mmol) number, be 1:1～5 with the ratios of alkali mmole (mmol) number; Between nitro to hydroxyl halobenzene mmole (mmol) number, be 1:0.01～0.1 with the ratios of catalyst A mmole (mmol) number; Being heated to 40～100 ℃ stirs 2～8 hours, after reaction finishes, steaming desolventizes B, adds the water of solvent B total amount 0.5～2 volume multiple, and a nitro is 1:0.5～2 to hydroxyl halobenzene mmole (mmol) number with the ratio of water milliliter (ml) number, stir 0.5～2 hour, suction filtration, solids, with after the water washing of solvent B total amount 1～3 volume multiple 2～3 times, is used solvent C recrystallization, dry, make a nitro to benzyloxy halobenzene;

Described nitro to the chemical structural formula of hydroxyl halobenzene is:

In formula, X is: Cl, Br or I;

Reaction formula is:

Between nitro to nitro between hydroxyl halobenzene halo benzyl to benzyloxy halobenzene

Wherein X is: Cl, Br or I; X' is: Cl, Br or I;

Described catalyst A is selected from iodine and salt compounded of iodine, is sodium iodide or potassiumiodide;

Described alkali is selected from alkali or its salt of weak acid that alkalies and alkaline earth generates, and is sodium hydroxide, potassium hydroxide, hydrated barta, sodium carbonate, salt of wormwood or sodium-acetate;

Described solvent B is: ether is ether, tertiary butyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF), ketone is acetone, butanone, and nitrile is acetonitrile, propionitrile, and acid amides is N, the mixture of one or more in dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone;

Described recrystallization solvent C is: water, and alcohol is methyl alcohol, ethanol, Virahol, and halohydrocarbon is methylene dichloride, chloroform, ethylene dichloride, and ester is ethyl acetate, butylacetate; Ether is ether, tertiary butyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF), and nitrile is one or more the mixture in acetonitrile, propionitrile;

Step III: preparation 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) HFC-236fa:

Nitro between step II gained is added in reactor C benzyloxy halobenzene and solvent D, then add bisphenol AF, alkali and catalyst B, in the middle of it, nitro is 1:1～5 to benzyloxy halobenzene mmole (mmol) number with the ratio of solvent D milliliter (ml) number; Between nitro to benzyloxy halobenzene mmole (mmol) number, be 1:0.2～0.5 with the ratios of bisphenol AF mmole (mmol) number; Between nitro to benzyloxy halobenzene mmole (mmol) number, be 1:1～5 with the ratios of alkali mmole (mmol) number; Between nitro to benzyloxy halobenzene mmole (mmol) number, be 1:0.1～1 with the ratios of catalyst B mmole (mmol) number; Nitrogen (N ₂) be heated to 120～180 ℃ under atmosphere and stir 10～48 hours, after reaction finishes, the water that adds solvent D total amount 5～10 volume multiples, suction filtration, solids is with after the water washing of solvent D total amount 1～3 volume multiple 2～3 times, with solvent E recrystallization, make 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) HFC-236fa;

Reaction formula is:

Between nitro to benzyloxy halobenzene bisphenol AF

2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) HFC-236fa

In formula, X is: Cl, Br or I;

Described catalyst B is selected from elemental copper and cuprous salt, is cuprous chloride, cuprous bromide or cuprous iodide;

Described alkali is selected from alkali or its salt of weak acid that alkalies and alkaline earth generates, and is any in sodium hydroxide, potassium hydroxide, hydrated barta, sodium carbonate, salt of wormwood, sodium-acetate;

Described solvent D is: acid amides is DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone, and sulfoxide is any in methyl-sulphoxide;

Described recrystallization solvent E is: water, alcohol is methyl alcohol, ethanol, Virahol, halohydrocarbon is methylene dichloride, chloroform, ethylene dichloride, ester is ethyl acetate, butylacetate, ether is ether, tertiary butyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF), and nitrile is one or more the mixture in acetonitrile, propionitrile;

Step IV: preparation 2,2-bis-(4-(3-amino-4-hydroxy phenoxy group) phenyl) HFC-236fa hydrochloride:

Step III is made 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) HFC-236fa adds in reactor D with solvent F dissolving, wherein 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) HFC-236fa mmole (mmol) number is 1:10～15 with the ratios of solvent F milliliter (ml) number; Adding again catalyzer C, 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) ratio of HFC-236fa quality gram (g) and catalyzer C quality gram (g) is 1:0.01～0.1; Hydrogen (H at 1～10bar pressure ₂) under atmosphere, in 25～50 ℃, stir 10～24 hours, after reaction finishes, filtration catalizer C, steaming desolventizes F, with the 2～12mol/L aqueous hydrochloric acid recrystallization that contains massfraction 1% tindichloride, 100 ℃ of vacuum-drying 24h of gained solid, make 2,2-bis-(4-(3-amino-4-hydroxy phenoxy group) phenyl) HFC-236fa hydrochloride;

Reaction formula is:

2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) HFC-236fa

Structure formula IV

Described solvent F is: alcohol is methyl alcohol, ethanol, Virahol, and ether is one or more the mixture in ether, tetrahydrofuran (THF);

Described catalyzer C is selected from the platinum family precious metal being loaded on carrier, and platinum family precious metal is palladium, platinum or rhodium, and suitable carrier is gac, aluminum oxide or silicon oxide.

This compound 2,2-bis-(4-(3-amino-4-hydroxy phenoxy group) phenyl) essential characteristic of HFC-236fa hydrochloride: white powder, structural characterization is as follows: infrared spectra (KBr, cm ^-1) 3407,3105,1625,1517,1321,1303,1248,1212,1180,982,967,875,809,740,718; Ultimate analysis (%): theoretical value: C:52.02, H:3.56, N:4.49; Measured value: C:51.93, H:3.51, N:4.45; ¹hNMR:(D ₂o, 400MHz, ppm) 7.29(8H); 6.66(4H); 6.16(2H); ESI-MS:m/z (M+1) 551.1.

Bis-phenol two (an amino p-hydroxybenzene) ether hydrochloride (being the compound of said structure formula I, II, III or IV) that adopts the present invention to make is applicable to prepare soluble poly benzo oxazole.During application:

Bis-phenol two (an amino p-hydroxybenzene) ether hydrochloride and disodium terephthalate reactant salt generate after bis-phenol two (an amino p-hydroxybenzene) ether terephthalate, in polyphosphoric acid, can polycondensation generate soluble poly benzo oxazole, reaction formula is:

Bis-phenol two (an amino p-hydroxybenzene) ether hydrochloride disodium terephthalate salt

Bis-phenol two (an amino p-hydroxybenzene) ether terephthalate

Soluble poly benzo oxazole

In formula, R is:

,

,

or

.

The fiber yarn fiber number that the novel polyphenyl Bing oxazole processing of being prepared by bis-phenol two (an amino p-hydroxybenzene) ether hydrochloride obtains is about 5.47dtex, intensity can reach 26.72CN/dtex, modulus can reach 583.3CN/dtex, second-order transition temperature is about 275 ℃, and in nitrogen, 10% thermal weight loss temperature is about 450 ℃.Be dissolvable in water the organic solvents such as dimethyl formamide simultaneously, be easy to be processed as variant production.

Compared with prior art, the present invention has following feature and beneficial effect:

(1) compound provided by the invention is for the preparation of soluble poly benzo oxazole; In the monomer of benzoxazole base polymer, introduce the groups such as ehter bond, increased the molecular flexibility of benzoxazole base polymer, maintain certain intensity and stable on heating solvability that increases polybenzoxazole simultaneously, make it be easy to machine-shaping;

(2) adopt the present invention, will be to the nitrated nitro that obtains of hydroxyl halobenzene to hydroxyl halobenzene, use benzyl protection hydroxyl, then become ether with the coupling of bis-phenol reagent, by hydro-reduction, remove benzyl again and by nitroreduction for amino, finally with hydrochloric acid salify, make bis-phenol two (an amino p-hydroxybenzene) ether hydrochloride (monomer); Four step synthetic methods of this monomer from cheapness to hydroxyl halobenzene, can obtain this monomer with good yield, compare on raw materials cost and have great advantage with the route of US 2004/0049081, cost of the present invention is low;

(3) the present invention compares with CN101263180A, there is similar mechanics and thermal property, but due in CN101263180A raw materials used 1, the price of 4-cyclohexane cyclohexanedimethanodibasic is up to more than 50000 yuan/ton, the more than 5 times of price (8000～10000 yuan/ton) of the present invention's terephthalic acid used, even if add the cost (approximately 13000 yuan/ton) of para-chlorophenol, the present invention compares with CN101263180A and on cost, still has greater advantage, and cost of the present invention is low, commercial effect is obvious;

(4) product preparation process of the present invention is simple, and operation is easy, and easily operation, practical.

Embodiment

Embodiment given below intends so that the invention will be further described; but can not be interpreted as it is limiting the scope of the invention; some nonessential improvement and adjustment that person skilled in art makes the present invention according to the content of the invention described above, still belong to protection scope of the present invention.

Embodiment 1:

Step I: between preparation, nitro is to hydroxyl halobenzene (embodiment 1)

Synthesizing of embodiment 1:3-nitro-4-hydroxyl base chlorobenzene

To hydroxychlorobenzene 152.62g(1.188mol) be placed in reaction flask, add 1500ml methylene dichloride to dissolve, under stirring, be cooled to 0 ℃, drip 126.74g concentrated nitric acid (65%, 1.308mol), control temperature lower than 5 ℃, dropwise rear temperature control and stir 3 hours lower than 5 ℃.1500ml washing twice, adds 500ml methyl alcohol, steams except methylene dichloride, and suction filtration makes pure 3-nitro-4-hydroxyl base chlorobenzene 180.51g, yellow powder, yield 87.6%.

Structural characterization is as follows: infrared spectra (KBr, cm ^-1) 3421,3064,1537,1473,1335,1291,1222,818; Ultimate analysis (%): theoretical value: C:41.52, H:2.32, N:8.07; Measured value: C:41.57, H:2.30, N:8.12; ¹hNMR:(CDCl ₃, 400MHz, ppm) and 10.48(1H); 8.11(1H); 7.54(1H); 7.14(1H); ESI-MS:m/z (M+1) 173.0.

Step II: between preparation, nitro is to benzyloxy halobenzene (embodiment 2)

Synthesizing of embodiment 2:3-nitro-4-benzyloxy chlorobenzene

3-nitro-4-hydroxychlorobenzene 126.34g(0.726mol) be placed in reaction flask, add 1000ml acetonitrile.After dissolving, then add 124.58g(0.903mol under stirring) salt of wormwood and 92.46g benzyl chlorine (0.730mol) and 10.39g potassiumiodide (0.0626mol), reflux 2 hours.Cooling rear steaming, except acetonitrile, adds 1000ml water, stirs 45min, suction filtration, and 1000ml washing twice, obtains thick product.Thick product ethyl alcohol recrystallization, makes pure 3-nitro-4-benzyloxy chlorobenzene 178.24g, yellow crystals, yield 93.0%.

Structural characterization is as follows: infrared spectra (KBr, cm ^-1) 3092,3029,2866,1611,1567,1529,1481,1454,1342,1301,1264,1225,1132,1018,859,814,747,706; Ultimate analysis (%): theoretical value: C:59.22, H:3.82, N:5.31; Measured value: C:59.27, H:3.78, N:5.35; ¹hNMR:(CDCl ₃, 400MHz, ppm) and 8.25(1H); 7.76(1H); 7.43(5H); 7.20(1H); 5.15(2H); ESI-MS:m/z (M+1) 264.1.

Step III: prepare bis-phenol two (nitro is to benzyloxy phenyl) ether (embodiment 3～6)

Embodiment 3:2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) propane is synthetic

By 3-nitro-4-benzyloxy chlorobenzene 30.90g(0.117mol), dihydroxyphenyl propane 13.33 g(0.0585mol), salt of wormwood 17.14g(0.124mol), cuprous chloride 1.17g(0.0118mol) be placed in reaction flask, add 150ml N-Methyl pyrrolidone.Under nitrogen protection, stir, and be heated to 150 ℃ of reactions 18 hours.After cooling, pour in 1200ml water, suction filtration after stirring 10min, with 400ml washing twice, obtains thick product.Ethyl acetate and normal hexane mixed solvent recrystallization for thick product, make pure 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) propane 28.61g, yellow powder, yield 71.6%.

Structural characterization is as follows: infrared spectra (KBr, cm ^-1) 3074,2820,1568,1534,1471,1361,1255,1139,1016,852,803,759,714; Ultimate analysis (%): theoretical value: C:72.13, H:5.02, N:4.10; Measured value: C:72.21, H:5.08, N:3.97; ¹hNMR:(CDCl ₃, 400MHz, ppm) and 7.84(2H); 7.71(2H); 7.36(20H); 5.15(4H); 1.74(6H); ESI-MS:m/z (M+1) 683.2.

Embodiment 4:4,4 '-bis-(3-nitro-4-benzyloxy phenoxy group) sulfobenzide synthetic:

By 3-nitro-4-benzyloxy chlorobenzene 63.56g(0.241mol), bisphenol S 30.08g(0.120mol), salt of wormwood 33.92g(0.246mol), cuprous chloride 3.23g(0.0326mol) be placed in reaction flask, add 270ml N-Methyl pyrrolidone.Under nitrogen protection, stir, and be heated to 170 ℃ of reactions 18 hours.After cooling, pour in 2500ml water, suction filtration after stirring 10min, with 700ml washing twice, obtains thick product.Thick product methylene dichloride and ethyl acetate mixed solvent recrystallization, make pure 4,4 '-bis-(3-nitro-4-benzyloxy phenoxy group) sulfobenzide 53.75g, yellow powder, yield 63.5%.

Structural characterization is as follows: infrared spectra (KBr, cm ^-1) 3110,2872,1625,1543,1412,1348,1335,1309,1155,1102,1031,858,763,724,681,619,584; Ultimate analysis (%): theoretical value: C:64.77, H:4.00, N:3.98, S:4.55; Measured value: C:64.81, H:4.06, N:3.92, S:4.47; ¹hNMR:(CDCl ₃, 400MHz, ppm) and 8.14(4H); 7.84(2H); 7.71(2H); 7.48(12H); 7.21(2H); 5.17(4H); ESI-MS:m/z (M+1) 705.2.

Embodiment 5:4,4 '-(3-nitro-4-benzyloxy phenoxy group) ditane synthetic:

By 3-nitro-4-benzyloxy chlorobenzene 40.17g(0.152mol), 4,4 '-dioxydiphenyl methane 15.08g(0.0754mol), salt of wormwood 24.48g(0.177mol), cuprous chloride 1.85g(0.0187mol) be placed in reaction flask, add 170ml N-Methyl pyrrolidone.Under nitrogen protection, stir, and be heated to 150 ℃ of reactions 18 hours.After cooling, pour in 1500ml water, suction filtration after stirring 10min, with 400ml washing twice, obtains thick product.Thick product ethyl acetate and normal hexane mixed solvent recrystallization, make 4,4 '-(3-nitro-4-benzyloxy phenoxy group) pure ditane 40.32g, yellow powder, yield 81.8%.

Structural characterization is as follows: infrared spectra (KBr, cm ^-1) 3110,2872,1612,1531,1327,1104,879,846,813,735,722,701,514; Ultimate analysis (%): theoretical value: C:71.55, H:4.62, N:4.28; Measured value: C:71.61, H:4.73, N:4.22; ¹hNMR:(CDCl ₃, 400MHz, ppm) and 7.84(2H); 7.71(6H); 7.43(10H); 7.24(10H); 5.17(4H); 3.97(2H); ESI-MS:m/z (M+1) 655.2.

Embodiment 6:2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) HFC-236fa is synthetic:

By 3-nitro-4-benzyloxy chlorobenzene 40.50g(0.153mol), 2,2-bis-(4-hydroxy phenyl) HFC-236fa 25.63g(0.0763mol), salt of wormwood 22.47g(0.163mol), cuprous chloride 1.76g(0.0178mol) be placed in reaction flask, add 170ml N-Methyl pyrrolidone.Under nitrogen protection, stir, and be heated to 150 ℃ of reactions 18 hours.After cooling, pour in 1500ml water, suction filtration after stirring 10min, with 400ml washing twice, obtains thick product.Ethyl acetate and normal hexane mixed solvent recrystallization for thick product, make pure 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) HFC-236fa 47.33g, yellow powder, yield 78.5%.

Structural characterization is as follows: infrared spectra (KBr, cm ^-1) 3081,2906,1615,1501,1352,1328,1304,1241,1195,1165,1127,1029,954,917,833,729,691; Ultimate analysis (%): theoretical value: C:62.28, H:3.57, N:3.54; Measured value: C:62.31, H:3.64, N:3.52; ¹hNMR:(CDCl ₃, 400MHz, ppm) and 7.83(2H); 7.73(2H); 7.33(20H); 5.16(4H); ESI-MS:m/z (M+1) 791.2.

Step IV: prepare bis-phenol two (an amino p-hydroxybenzene) ether hydrochloride (embodiment 7～10)

Embodiment 7:2,2-bis-(4-(3-amino-4-hydroxy phenoxy group) phenyl) propane hydrochloride salt is synthetic:

2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) propane 48.30g(0.071mol) be placed in reaction flask, add 800ml tetrahydrofuran (THF) to dissolve.Add 2.79g10%Pd/C, vacuumize replacing hydrogen, maintenance hydrogen pressure is 1bar, stirs 24 hours at 25 ℃.Suction filtration is removed Pd/C, steams except tetrahydrofuran (THF).With the 6mol/L hydrochloric acid recrystallization that contains massfraction 1% tindichloride, 100 ℃ of vacuum-drying 24h of gained solid, obtain pure 2,2-bis-(4-(3-amino-4-hydroxy phenoxy group) phenyl) propane hydrochloride salt 35.07g, yield 96.3%.

This compound 2,2-bis-(4-(3-amino-4-hydroxy phenoxy group) phenyl) essential characteristic of propane hydrochloride salt: white powder, structural characterization is as follows: infrared spectra (KBr, cm ^-1) 3374,2947,1632,1593,1526,1463,1429,1280,1263,1235,1182,1167,1149,1073,1032,967,911,864,831,819,755; Ultimate analysis (%): theoretical value: C:62.92, H:5.48, N:5.43; Measured value: C:62.86, H:5.43, N:5.37; ¹hNMR:(D ₂o, 400MHz, ppm) 7.30(8H); 6.63(4H); 6.14(2H); 1.73(6H); ESI-MS:m/z (M+1) 443.3.

Embodiment 8:4,4 '-bis-(3-amino-4-hydroxy phenoxy group) sulfobenzide hydrochloride synthetic:

4,4 '-bis-(3-nitro-4-benzyloxy phenoxy group) sulfobenzide 40.85g(0.0579mol) be placed in reaction flask, add 700ml tetrahydrofuran (THF) to dissolve.Add 2.06g10%Pd/C, vacuumize replacing hydrogen, maintenance hydrogen pressure is 1bar, stirs 24 hours at 25 ℃.Suction filtration is removed Pd/C, steams except tetrahydrofuran (THF).With the 6mol/L hydrochloric acid recrystallization that contains massfraction 1% tindichloride, 100 ℃ of vacuum-drying 24h of gained solid, obtain pure 4,4 '-bis-(3-amino-4-hydroxy phenoxy group) sulfobenzide hydrochloride 29.28g, yield 94.1%.

The essential characteristic of this compound 4,4 '-bis-(3-amino-4-hydroxy phenoxy group) sulfobenzide hydrochloride: white powder, structural characterization is as follows: infrared spectra (KBr, cm ^-1) 3372,3061,1597,1516,1445,1381,1314,1287,1255,1218,1143,1101,1069,934,859,818,772,723,694,657; Ultimate analysis (%): theoretical value: C:53.64, H:4.13, N:5.21; Measured value: C:53.53, H:4.08, N:5.14; ¹hNMR:(D ₂o, 400MHz, ppm) 8.12(4H); 7.54(4H); 6.64(4H); 6.15(2H); ESI-MS:m/z (M+1) 465.1.

Embodiment 9:4,4 '-(3-amino-4-hydroxy phenoxy group) ditane hydrochloride synthetic:

4,4 '-(3-nitro-4-benzyloxy phenoxy group) ditane 40.32g(0.0617mol) be placed in reaction flask, add 800ml tetrahydrofuran (THF) to dissolve.Add 2.23g10%Pd/C, vacuumize replacing hydrogen, maintenance hydrogen pressure is 1bar, stirs 24 hours at 25 ℃.Suction filtration is removed Pd/C, steams except tetrahydrofuran (THF).With the 6mol/L hydrochloric acid recrystallization that contains massfraction 1% tindichloride, 100 ℃ of vacuum-drying 24h of gained solid, obtain 4,4 '-(3-amino-4-hydroxy phenoxy group) pure ditane hydrochloride 28.70g, yield 95.5%.

The essential characteristic of this compound 4,4 '-(3-amino-4-hydroxy phenoxy group) ditane hydrochloride: white powder, structural characterization is as follows: infrared spectra (KBr, cm ^-1) 3352,2921,1617,1585,1519,1467,1422,1263,1226,1161,1137,1049,1013,965,924,861,817,737; Ultimate analysis (%): theoretical value: C:61.61, H:4.96, N:5.75; Measured value: C:61.55, H:4.87, N:5.70; ¹hNMR:(D ₂o, 400MHz, ppm) 7.24(8H); 6.66(4H); 6.16(2H); 3.96(2H); ESI-MS:m/z (M+1) 414.2.

Embodiment 10:2,2-bis-(4-(3-amino-4-hydroxy phenoxy group) phenyl) HFC-236fa hydrochloride is synthetic:

2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) HFC-236fa 47.33g(0.0599mol) be placed in reaction flask, add 600ml tetrahydrofuran (THF) to dissolve.Add 2.37g10%Pd/C, vacuumize replacing hydrogen, maintenance hydrogen pressure is 1bar, stirs 24 hours at 25 ℃.Suction filtration is removed Pd/C, steams except tetrahydrofuran (THF).With the 6mol/L hydrochloric acid recrystallization that contains massfraction 1% tindichloride, 100 ℃ of vacuum-drying 24h of gained solid, obtain pure 2,2-bis-(4-(3-amino-4-hydroxy phenoxy group) phenyl) HFC-236fa hydrochloride 28.68g, yield 87.0%.

This compound 2,2-bis-(4-(3-amino-4-hydroxy phenoxy group) phenyl) essential characteristic of HFC-236fa hydrochloride: white powder, structural characterization is as follows: infrared spectra (KBr, cm ^-1) 3407,3105,1625,1517,1321,1303,1248,1212,1180,982,967,875,809,740,718; Ultimate analysis (%): theoretical value: C:52.02, H:3.56, N:4.49; Measured value: C:51.93, H:3.51, N:4.45; ¹hNMR:(D ₂o, 400MHz, ppm) 7.29(8H); 6.66(4H); 6.16(2H); ESI-MS:m/z (M+1) 551.1.

Embodiment 11: the preparation of polybenzoxazole:

Bis-phenol two (an amino p-hydroxybenzene) ether hydrochloride is soluble in water, adds and is dissolved with equimolar disodium terephthalate salt, stirs a moment, separates out a large amount of white solids, and filtration drying, obtains bis-phenol two (an amino p-hydroxybenzene) ether to dibenzoate.

Bis-phenol two (an amino p-hydroxybenzene) ether is to adding polyphosphoric acid and Vanadium Pentoxide in FLAKES in dibenzoate, making phosphorus pentoxide content in polyphosphoric acid is 85%, and starting monomer content is 14%.Under nitrogen atmosphere, stir, 120 ℃ 4 hours, 150 ℃ 8 hours, 180 ℃ 4 hours, obtain polybenzoxazole stoste.

After using G3 sand core funnel to filter stoste, with the spinning top dry-jet wet spinning spinning of aperture 0.25mm, through washing with after being dried, obtain polybenzoxazole fibers.Its data are as follows:

Table 1. gained polybenzoxazole fibers Mechanical Data:

note: table 1 Literature value is from CN1709942A, and its polybenzoxazole polymkeric substance is different from the unit of the present patent application.

Table 2. gained polybenzoxazole fibers calorifics data:

note: (1) table 2 Literature value is from the embodiment 9 in CN101362700A; (2) dissolubility test solvent for use comprises dimethyl formamide, N-Methyl pyrrolidone, methyl-sulphoxide, not mentioned tested solvent species in document CN101362700A.

From table 1 and table 2, prepared polybenzoxazole reduces compared with the literature amplitude little on mechanics and thermal property, compare (approximately 280 ℃ of second-order transition temperatures) with document CN101263180A comparatively approaching, although the more traditional polybenzoxazole of its performance is low, but still belong to high strength heat resistant fiber, can in intensity and thermotolerance, meet the requirement of most special applications.The prepared polybenzoxazole of the present invention simultaneously dissolves in organic solvent, is more easy to follow-up machine-shaping, thereby can produces the goods of fiber, film and other type of various different sizes.

Embodiment 12:

2,2-bis-(4-(3-amino-4-hydroxy phenoxy group) phenyl) preparation method of propane hydrochloride salt, comprises the following steps:

Step I: between preparation, nitro is to hydroxyl halobenzene:

To add in reactor A hydroxyl halobenzene, and add methylene dichloride to dissolve, be wherein 1:1～5 to hydroxyl halobenzene mmole number with the ratio of methylene dichloride milliliter number; Agitation condition borehole cooling to 0～10 ℃, drip 65% concentrated nitric acid, to hydroxyl halogen (halogen is Cl, Br or I) benzene mmole number, are wherein 1:1～1.5 with the ratio of nitric acid mmole number; After nitric acid finishes, at 0～10 ℃, stir 2～6 hours, after reaction finishes, with methylene dichloride 1～3 volume multiple washing 2～3 times, use solvent orange 2 A recrystallization, dry, make a nitro to hydroxyl halobenzene;

Described recrystallization solvent A is: water, and alcohol is methyl alcohol, ethanol, Virahol, and halohydrocarbon is methylene dichloride, chloroform, ethylene dichloride, and ester is ethyl acetate, butylacetate; Ether is ether, tertiary butyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF), and nitrile is one or more the mixture in acetonitrile, propionitrile;

Step II: between preparation, nitro is to benzyloxy halobenzene:

Under agitation condition, nitro between step I gained is added in reactor B hydroxyl halobenzene and solvent B, in the middle of it, nitro is 1:1～5 to hydroxyl halobenzene mmole number with the ratio of solvent B milliliter number; After a nitro dissolves completely to hydroxyl halogen (halogen is Cl, Br or I) benzene, then add halo benzyl, alkali and catalyst A, in the middle of it, nitro is 1:1～2 to hydroxyl halobenzene mmole number with the ratio of halo benzyl mmole number; Between nitro to hydroxyl halobenzene mmole number, be 1:1～5 with the ratio of alkali mmole number; Between nitro to hydroxyl halobenzene mmole number, be 1:0.01～0.1 with the ratio of catalyzer mmole number; Being heated to 40～100 ℃ stirs 2～8 hours, after reaction finishes, steaming desolventizes B, adds the water of solvent B total amount 0.5～2 volume multiple, and a nitro is 1:0.5～2 to hydroxyl halobenzene mmole number with the ratio of water milliliter number, stir 0.5～2 hour, suction filtration, solids, with after the water washing of solvent B total amount 1～3 volume multiple 2～3 times, is used solvent C recrystallization, dry, make a nitro to benzyloxy halobenzene;

Described catalyst A is selected from iodine and salt compounded of iodine, is sodium iodide or potassiumiodide;

Described alkali is selected from alkali or its salt of weak acid that alkalies and alkaline earth generates, and is sodium hydroxide, potassium hydroxide, hydrated barta, sodium carbonate, salt of wormwood or sodium-acetate;

Described solvent B is: ether is ether, tertiary butyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF), ketone is acetone, butanone, and nitrile is acetonitrile, propionitrile, and acid amides is N, the mixture of one or more in dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone;

Described recrystallization solvent C is: water, and alcohol is methyl alcohol, ethanol, Virahol, and halohydrocarbon is methylene dichloride, chloroform, ethylene dichloride, and ester is ethyl acetate, butylacetate; Ether is ether, tertiary butyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF), and nitrile is one or more the mixture in acetonitrile, propionitrile;

Step III: preparation 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) propane:

Between step II is made, nitro adds in reactor C benzyloxy halobenzene and solvent D, then adds dihydroxyphenyl propane, alkali and catalyst B, and in the middle of it, nitro is 1:1～5 to benzyloxy halobenzene mmole number with the ratio of solvent D milliliter number; Between nitro to benzyloxy halobenzene mmole number, be 1:0.2～0.5 with the ratio of dihydroxyphenyl propane mmole number; Between nitro to benzyloxy halobenzene mmole number, be 1:1～5 with the ratio of alkali mmole number; Between nitro to benzyloxy halobenzene mmole number, be 1:0.1～1 with the ratio of catalyst B mmole number; At nitrogen (N ₂) be heated to 120～180 ℃ under atmosphere and stir 10～48 hours, after reaction finishes, the water that adds solvent D total amount 5～10 volume multiples, suction filtration, solids is with after the water washing of solvent D total amount 1～3 volume multiple 2～3 times, with solvent E recrystallization, make 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) propane;

Described catalyst B is selected from elemental copper and cuprous salt, is cuprous chloride, cuprous bromide or cuprous iodide;

Described alkali is selected from alkali or its salt of weak acid that alkalies and alkaline earth generates, and is any in sodium hydroxide, potassium hydroxide, hydrated barta, sodium carbonate, salt of wormwood, sodium-acetate;

Described solvent D is: acid amides is that DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone, sulfoxide are any in methyl-sulphoxide;

Described recrystallization solvent E: water, alcohol is methyl alcohol, ethanol, Virahol, and halohydrocarbon is methylene dichloride, chloroform, ethylene dichloride, and ester is ethyl acetate, butylacetate; Ether is ether, tertiary butyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF), and nitrile is one or more the mixture in acetonitrile, propionitrile;

Step IV: preparation 2,2-bis-(4-(3-amino-4-hydroxy phenoxy group) phenyl) propane hydrochloride salt:

Step III is made 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) propane adds in reactor D with solvent F dissolving, wherein 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) propane mmole number is 1:10～15 with the ratio of solvent F milliliter number; Adding again catalyzer C, 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) propane quality grams is 1:0.01～0.1 with the ratio of catalyzer C quality grams; Hydrogen (H at 1～10bar pressure ₂) under atmosphere, in 25～50 ℃, stir 10～24 hours, after reaction finishes, filtration catalizer C, steaming desolventizes F, with the 2～12mol/L aqueous hydrochloric acid recrystallization that contains massfraction 1% tindichloride, 100 ℃ of vacuum-drying 24h of gained solid, make 2,2-bis-(4-(3-amino-4-hydroxy phenoxy group) phenyl) propane hydrochloride salt;

Described solvent F: alcohol is methyl alcohol, ethanol, Virahol, ether is one or more the mixture in ether, tetrahydrofuran (THF);

Described catalyzer C is the platinum family precious metal being loaded on carrier, and platinum family precious metal is palladium, platinum or rhodium, and carrier is gac, aluminum oxide or silicon oxide.

This compound 2,2-bis-(4-(3-amino-4-hydroxy phenoxy group) phenyl) essential characteristic of propane hydrochloride salt: white powder, structural characterization is as follows: infrared spectra (KBr, cm ^-1) 3374,2947,1632,1593,1526,1463,1429,1280,1263,1235,1182,1167,1149,1073,1032,967,911,864,831,819,755; Ultimate analysis (%): theoretical value: C:62.92, H:5.48, N:5.43; Measured value: C:62.86, H:5.43, N:5.37; ¹hNMR:(D ₂o, 400MHz, ppm) 7.30(8H); 6.63(4H); 6.14(2H); 1.73(6H); ESI-MS:m/z (M+1) 443.3.

Embodiment 13:

2,2-bis-(4-(3-amino-4-hydroxy phenoxy group) phenyl) preparation method of propane hydrochloride salt, comprises the following steps:

Step I: between preparation, nitro is to hydroxyl halobenzene:

To add in reactor A hydroxyl halobenzene, and add methylene dichloride to dissolve, be wherein 1:3 to hydroxyl halobenzene mmole number with the ratio of methylene dichloride milliliter number; Agitation condition borehole cooling to 0～10 ℃, drip 65% concentrated nitric acid, to hydroxyl halogen (halogen is Cl, Br or I) benzene mmole number, are wherein 1:1.2 with the ratio of nitric acid mmole number; After nitric acid finishes, at 0～10 ℃, stir 4 hours, after reaction finishes, with methylene dichloride 2 volume multiple washing 3 times, use solvent orange 2 A recrystallization, dry, make a nitro to hydroxyl halobenzene;

Step II: between preparation, nitro is to benzyloxy halobenzene:

Under agitation condition, nitro between step I gained is added in reactor B hydroxyl halobenzene and solvent B, in the middle of it, nitro is 1:3 to hydroxyl halobenzene mmole number with the ratio of solvent B milliliter number; After a nitro dissolves completely to hydroxyl halogen (halogen is Cl, Br or I) benzene, then add halo benzyl, alkali and catalyst A, in the middle of it, nitro is 1:1.5 to hydroxyl halobenzene mmole number with the ratio of halo benzyl mmole number; Between nitro to hydroxyl halobenzene mmole number, be 1:3 with the ratio of alkali mmole number; Between nitro to hydroxyl halobenzene mmole number, be 1:0.05 with the ratio of catalyst A mmole number; Being heated to 40～100 ℃ stirs 4 hours, after reaction finishes, steaming desolventizes B, adds the water of solvent B total amount 1 volume multiple, and a nitro is 1:1.5 to hydroxyl halobenzene mmole number with the ratio of water milliliter number, stir 1 hour, suction filtration, solids, with after the water washing of solvent B total amount 2 volume multiples 2 times, is used solvent C recrystallization, dry, make a nitro to benzyloxy halobenzene;

Step III: preparation 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) propane:

Between step II is made, nitro adds in reactor C benzyloxy halobenzene and solvent D, then adds dihydroxyphenyl propane, alkali and catalyst B, and in the middle of it, nitro is 1:3 to benzyloxy halobenzene mmole number with the ratio of solvent D milliliter number; Between nitro to benzyloxy halobenzene mmole number, be 1:0.4 with the ratio of dihydroxyphenyl propane mmole number; Between nitro to benzyloxy halobenzene mmole number, be 1:3 with the ratio of alkali mmole number; Between nitro to benzyloxy halobenzene mmole number, be 1:0.5 with the ratio of catalyst B mmole number; At nitrogen (N ₂) be heated to 120～180 ℃ under atmosphere and stir 29 hours, after reaction finishes, the water that adds solvent D total amount 7 volume multiples, suction filtration, solids is with after the water washing of solvent D total amount 2 volume multiples 3 times, with solvent E recrystallization, make 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) propane;

Step IV: preparation 2,2-bis-(4-(3-amino-4-hydroxy phenoxy group) phenyl) propane hydrochloride salt:

Step III is made 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) propane adds in reactor D with solvent F dissolving, wherein 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) propane mmole number is 1:13 with the ratio of solvent F milliliter number; Adding again catalyzer C, 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) propane quality grams is 1:0.05 with the ratio of catalyzer C quality grams; Hydrogen (H at 1～10bar pressure ₂) under atmosphere, in 25～50 ℃, stir 17 hours, after reaction finishes, filtration catalizer C, steaming desolventizes F, with the 2～12mol/L aqueous hydrochloric acid recrystallization that contains massfraction 1% tindichloride, 100 ℃ of vacuum-drying 24h of gained solid, make 2,2-bis-(4-(3-amino-4-hydroxy phenoxy group) phenyl) propane hydrochloride salt;

The other the same as in Example 12, omits.

Embodiment 14:

2,2-bis-(4-(3-amino-4-hydroxy phenoxy group) phenyl) preparation method of propane hydrochloride salt, comprises the following steps:

Step I: between preparation, nitro is to hydroxyl halobenzene:

To add in reactor A hydroxyl halobenzene, and add methylene dichloride to dissolve, be wherein 1:1 to hydroxyl halobenzene mmole number with the ratio of methylene dichloride milliliter number; Agitation condition borehole cooling to 0～10 ℃, drip 65% concentrated nitric acid, to hydroxyl halogen (halogen is Cl, Br or I) benzene mmole number, are wherein 1:1 with the ratio of nitric acid mmole number; After nitric acid finishes, at 0～10 ℃, stir 2 hours, after reaction finishes, with methylene dichloride 1 volume multiple washing 3 times, use solvent orange 2 A recrystallization, dry, make a nitro to hydroxyl halobenzene;

Step II: between preparation, nitro is to benzyloxy halobenzene:

Under agitation condition, nitro between step I gained is added in reactor B hydroxyl halobenzene and solvent B, in the middle of it, nitro is 1:1 to hydroxyl halobenzene mmole number with the ratio of solvent B milliliter number; After a nitro dissolves completely to hydroxyl halogen (halogen is Cl, Br or I) benzene, then add halo benzyl, alkali and catalyst A, in the middle of it, nitro is 1:1 to hydroxyl halobenzene mmole number with the ratio of halo benzyl mmole number; Between nitro to hydroxyl halobenzene mmole number, be 1:1 with the ratio of alkali mmole number; Between nitro to hydroxyl halobenzene mmole number, be 1:0.01 with the ratio of catalyst A mmole number; Being heated to 40～100 ℃ stirs 2 hours, after reaction finishes, steaming desolventizes B, adds the water of solvent B total amount 0.5 volume multiple, and a nitro is 1:0.5 to hydroxyl halobenzene mmole number with the ratio of water milliliter number, stir 0.5 hour, suction filtration, solids, with after the water washing of solvent B total amount 1 volume multiple 2 times, is used solvent C recrystallization, dry, make a nitro to benzyloxy halobenzene;

Step III: preparation 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) propane:

Between step II is made, nitro adds in reactor C benzyloxy halobenzene and solvent D, then adds dihydroxyphenyl propane, alkali and catalyst B, and in the middle of it, nitro is 1:1 to benzyloxy halobenzene mmole number with the ratio of solvent D milliliter number; Between nitro to benzyloxy halobenzene mmole number, be 1:0.2 with the ratio of dihydroxyphenyl propane mmole number; Between nitro to benzyloxy halobenzene mmole number, be 1:1 with the ratio of alkali mmole number; Between nitro to benzyloxy halobenzene mmole number, be 1:0.1 with the ratio of catalyst B mmole number; At nitrogen (N ₂) be heated to 120～180 ℃ under atmosphere and stir 10 hours, after reaction finishes, the water that adds solvent D total amount 5 volume multiples, suction filtration, solids is with after the water washing of solvent D total amount 1 volume multiple 2 times, with solvent E recrystallization, make 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) propane;

Step IV: preparation 2,2-bis-(4-(3-amino-4-hydroxy phenoxy group) phenyl) propane hydrochloride salt:

Step III is made 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) propane adds in reactor D with solvent F dissolving, wherein 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) propane mmole number is 1:10 with the ratio of solvent F milliliter number; Adding again catalyzer C, 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) propane quality grams is 1:0.01 with the ratio of catalyzer C quality grams; Hydrogen (H at 1～10bar pressure ₂) under atmosphere, in 25～50 ℃, stir 10 hours, after reaction finishes, filtration catalizer C, steaming desolventizes F, with the 2～12mol/L aqueous hydrochloric acid recrystallization that contains massfraction 1% tindichloride, 100 ℃ of vacuum-drying 24h of gained solid, make 2,2-bis-(4-(3-amino-4-hydroxy phenoxy group) phenyl) propane hydrochloride salt;

The other the same as in Example 12, omits.

Embodiment 15:

2,2-bis-(4-(3-amino-4-hydroxy phenoxy group) phenyl) preparation method of propane hydrochloride salt, comprises the following steps:

Step I: between preparation, nitro is to hydroxyl halobenzene:

To add in reactor A hydroxyl halobenzene, and add methylene dichloride to dissolve, be wherein 1:5 to hydroxyl halobenzene mmole number with the ratio of methylene dichloride milliliter number; Agitation condition borehole cooling to 0～10 ℃, drip 65% concentrated nitric acid, to hydroxyl halogen (halogen is Cl, Br or I) benzene mmole number, are wherein 1:1.5 with the ratio of nitric acid mmole number; After nitric acid finishes, at 0～10 ℃, stir 6 hours, after reaction finishes, with methylene dichloride 3 volume multiple washing 2 times, use solvent orange 2 A recrystallization, dry, make a nitro to hydroxyl halobenzene;

Step II: between preparation, nitro is to benzyloxy halobenzene:

Under agitation condition, nitro between step I gained is added in reactor B hydroxyl halobenzene and solvent B, in the middle of it, nitro is 1:5 to hydroxyl halobenzene mmole number with the ratio of solvent B milliliter number; After a nitro dissolves completely to hydroxyl halogen (halogen is Cl, Br or I) benzene, then add halo benzyl, alkali and catalyst A, in the middle of it, nitro is 1:2 to hydroxyl halobenzene mmole number with the ratio of halo benzyl mmole number; Between nitro to hydroxyl halobenzene mmole number, be 1:5 with the ratio of alkali mmole number; Between nitro to hydroxyl halobenzene mmole number, be 1:0.1 with the ratio of catalyzer mmole number; Being heated to 40～100 ℃ stirs 8 hours, after reaction finishes, steaming desolventizes B, adds the water of solvent B total amount 2 volume multiples, and a nitro is 1:2 to hydroxyl halobenzene mmole number with the ratio of water milliliter number, stir 2 hours, suction filtration, solids, with after the water washing of solvent B total amount 3 volume multiples 3 times, is used solvent C recrystallization, dry, make a nitro to benzyloxy halobenzene;

Step III: preparation 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) propane:

Between step II is made, nitro adds in reactor C benzyloxy halobenzene and solvent D, then adds dihydroxyphenyl propane, alkali and catalyst B, and in the middle of it, nitro is 1:5 to benzyloxy halobenzene mmole number with the ratio of solvent D milliliter number; Between nitro to benzyloxy halobenzene mmole number, be 1:0.5 with the ratio of dihydroxyphenyl propane mmole number; Between nitro to benzyloxy halobenzene mmole number, be 1:5 with the ratio of alkali mmole number; Between nitro to benzyloxy halobenzene mmole number, be 1:1 with the ratio of catalyst B mmole number; At nitrogen (N ₂) be heated to 120～180 ℃ under atmosphere and stir 48 hours, after reaction finishes, the water that adds solvent D total amount 5～10 volume multiples, suction filtration, solids is with after the water washing of solvent D total amount 3 volume multiples 3 times, with solvent E recrystallization, make 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) propane;

Step IV: preparation 2,2-bis-(4-(3-amino-4-hydroxy phenoxy group) phenyl) propane hydrochloride salt:

Step III is made 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) propane adds in reactor D with solvent F dissolving, wherein 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) propane mmole number is 1:15 with the ratio of solvent F milliliter number; Adding again catalyzer C, 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) propane quality grams is 1:0.1 with the ratio of catalyzer C quality grams; Hydrogen (H at 1～10bar pressure ₂) under atmosphere, in 25～50 ℃, stir 24 hours, after reaction finishes, filtration catalizer C, steaming desolventizes F, with the 2～12mol/L aqueous hydrochloric acid recrystallization that contains massfraction 1% tindichloride, 100 ℃ of vacuum-drying 24h of gained solid, make 2,2-bis-(4-(3-amino-4-hydroxy phenoxy group) phenyl) propane hydrochloride salt;

The other the same as in Example 12, omits.

Embodiment 16:

The preparation method of 4,4 '-bis-(3-amino-4-hydroxy phenoxy group) sulfobenzide hydrochloride, comprises the following steps:

Step I: between preparation, nitro is to hydroxyl halobenzene: with arbitrary in above-described embodiment, omit;

Step II: between preparation, nitro is to benzyloxy halobenzene: with arbitrary in above-described embodiment, omit;

Step III: preparation 4,4 '-bis-(3-nitro-4-benzyloxy phenoxy group) sulfobenzide:

Nitro between step II gained is added in reactor C benzyloxy halobenzene and solvent D, add again bisphenol S, alkali and catalyst B, in the middle of it, nitro is 1:4 to benzyloxy halobenzene mmole number with the ratio of solvent D milliliter number, between nitro to benzyloxy halobenzene mmole number, be 1:0.4 with the ratio of bisphenol S mmole number, between nitro to benzyloxy halobenzene mmole number, be 1:4 with the ratio of alkali mmole number, between nitro to benzyloxy halobenzene mmole number, be 1:0.6 with the ratio of catalyst B mmole number, nitrogen (N ₂) be heated to 120～180 ℃ under atmosphere and stir 30 hours, after reaction finishes, add the water of solvent D total amount 8 volume multiples, suction filtration, solids is with after the water washing of solvent D total amount 2 volume multiples 3 times, with solvent E recrystallization, make 4,4 '-bis-(3-nitro-4-benzyloxy phenoxy group) sulfobenzide;

Described catalyst B is selected from elemental copper and cuprous salt, is cuprous chloride, cuprous bromide or cuprous iodide;

Described alkali is selected from alkali or its salt of weak acid that alkalies and alkaline earth generates, and is any in sodium hydroxide, potassium hydroxide, hydrated barta, sodium carbonate, salt of wormwood, sodium-acetate;

Described solvent D is: acid amides is DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone; Sulfoxide is any in methyl-sulphoxide;

Described recrystallization solvent E is: water, alcohol is methyl alcohol, ethanol, Virahol, halohydrocarbon is methylene dichloride, chloroform, ethylene dichloride, ester is ethyl acetate, butylacetate, ether is ether, tertiary butyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF), and nitrile is one or more the mixture in acetonitrile, propionitrile;

Step IV: preparation 4,4 '-bis-(3-amino-4-hydroxy phenoxy group) sulfobenzide hydrochloride:

Step III gained 4,4 '-bis-(3-nitro-4-benzyloxy phenoxy group) sulfobenzide is added in reactor D and dissolved with solvent F, and wherein 4,4 '-bis-(3-nitro-4-benzyloxy phenoxy group) sulfobenzide mmole number is 1:13 with the ratio of solvent F milliliter number; Add catalyzer C, 4,4 '-bis-(3-nitro-4-benzyloxy phenoxy group) sulfobenzide quality grams is 1:0.06 with the ratio of catalyzer C quality grams again; Hydrogen (the H of 1～10bar pressure ₂) under atmosphere, 25～50 ℃ are stirred 18 hours; After reaction finishes, filtration catalizer C, steams and desolventizes F, and with the 2～12mol/L aqueous hydrochloric acid recrystallization that contains massfraction 1% tindichloride, 100 ℃ of vacuum-drying 24h of gained solid, obtain 4,4 '-bis-(3-amino-4-hydroxy phenoxy group) sulfobenzide hydrochloride;

Described solvent F is: alcohol is methyl alcohol, ethanol, Virahol, and ether is one or more the mixture in ether, tetrahydrofuran (THF);

Described catalyzer C is the platinum family precious metal being loaded on carrier, and platinum family precious metal is palladium, platinum or rhodium; Carrier is gac, aluminum oxide or silicon oxide.

The essential characteristic of this compound 4,4 '-bis-(3-amino-4-hydroxy phenoxy group) sulfobenzide hydrochloride: white powder, structural characterization is as follows: infrared spectra (KBr, cm ^-1) 3372,3061,1597,1516,1445,1381,1314,1287,1255,1218,1143,1101,1069,934,859,818,772,723,694,657; Ultimate analysis (%): theoretical value: C:53.64, H:4.13, N:5.21; Measured value: C:53.53, H:4.08, N:5.14; ¹hNMR:(D ₂o, 400MHz, ppm) 8.12(4H); 7.54(4H); 6.64(4H); 6.15(2H); ESI-MS:m/z (M+1) 465.1.

Embodiment 17:

The preparation method of 4,4 '-bis-(3-amino-4-hydroxy phenoxy group) sulfobenzide hydrochloride, comprises the following steps:

Step I: between preparation, nitro is to hydroxyl halobenzene: with arbitrary in above-described embodiment, omit;

Step II: between preparation, nitro is to benzyloxy halobenzene: with arbitrary in above-described embodiment, omit;

Step III: preparation 4,4 '-bis-(3-nitro-4-benzyloxy phenoxy group) sulfobenzide:

Nitro between step II gained is added in reactor C benzyloxy halobenzene and solvent D, add again bisphenol S, alkali and catalyst B, in the middle of it, nitro is 1:1 to benzyloxy halobenzene mmole number with the ratio of solvent D milliliter number, between nitro to benzyloxy halobenzene mmole number, be 1:0.2 with the ratio of bisphenol S mmole number, between nitro to benzyloxy halobenzene mmole number, be 1:1 with the ratio of alkali mmole number, between nitro to benzyloxy halobenzene mmole number, be 1:0.1 with the ratio of catalyst B mmole number, nitrogen (N ₂) be heated to 120～180 ℃ under atmosphere and stir 10 hours, after reaction finishes, add the water of solvent D total amount 5 volume multiples, suction filtration, solids is with after the water washing of solvent D total amount 1 volume multiple 2 times, with solvent E recrystallization, make 4,4 '-bis-(3-nitro-4-benzyloxy phenoxy group) sulfobenzide;

Step IV: preparation 4,4 '-bis-(3-amino-4-hydroxy phenoxy group) sulfobenzide hydrochloride:

Step III gained 4,4 '-bis-(3-nitro-4-benzyloxy phenoxy group) sulfobenzide is added in reactor D and dissolved with solvent F, and wherein 4,4 '-bis-(3-nitro-4-benzyloxy phenoxy group) sulfobenzide mmole number is 1:10 with the ratio of solvent F milliliter number; Add catalyzer C, 4,4 '-bis-(3-nitro-4-benzyloxy phenoxy group) sulfobenzide quality grams is 1:0.01 with the ratio of catalyzer C quality grams again; Hydrogen (the H of 1～10bar pressure ₂) under atmosphere, 25～50 ℃ are stirred 10 hours; After reaction finishes, filtration catalizer C, steams and desolventizes F, and with the 2～12mol/L aqueous hydrochloric acid recrystallization that contains massfraction 1% tindichloride, 100 ℃ of vacuum-drying 24h of gained solid, obtain 4,4 '-bis-(3-amino-4-hydroxy phenoxy group) sulfobenzide hydrochloride;

The other the same as in Example 16, omits.

Embodiment 18:

The preparation method of 4,4 '-bis-(3-amino-4-hydroxy phenoxy group) sulfobenzide hydrochloride, comprises the following steps:

Step I: between preparation, nitro is to hydroxyl halobenzene: with arbitrary in above-described embodiment, omit;

Step II: between preparation, nitro is to benzyloxy halobenzene: with arbitrary in above-described embodiment, omit;

Step III: preparation 4,4 '-bis-(3-nitro-4-benzyloxy phenoxy group) sulfobenzide:

Nitro between step II gained is added in reactor C benzyloxy halobenzene and solvent D, add again bisphenol S, alkali and catalyst B, in the middle of it, nitro is 1:5 to benzyloxy halobenzene mmole number with the ratio of solvent D milliliter number, between nitro to benzyloxy halobenzene mmole number, be 1:0.5 with the ratio of bisphenol S mmole number, between nitro to benzyloxy halobenzene mmole number, be 1:5 with the ratio of alkali mmole number, between nitro to benzyloxy halobenzene mmole number, be 1:1 with the ratio of catalyst B mmole number, nitrogen (N ₂) be heated to 120～180 ℃ under atmosphere and stir 48 hours, after reaction finishes, add the water of solvent D total amount 10 volume multiples, suction filtration, solids is with after the water washing of solvent D total amount 3 volume multiples 3 times, with solvent E recrystallization, make 4,4 '-bis-(3-nitro-4-benzyloxy phenoxy group) sulfobenzide;

Step IV: preparation 4,4 '-bis-(3-amino-4-hydroxy phenoxy group) sulfobenzide hydrochloride:

Step III gained 4,4 '-bis-(3-nitro-4-benzyloxy phenoxy group) sulfobenzide is added in reactor D and dissolved with solvent F, and wherein 4,4 '-bis-(3-nitro-4-benzyloxy phenoxy group) sulfobenzide mmole number is 1:15 with the ratio of solvent F milliliter number; Add catalyzer C, 4,4 '-bis-(3-nitro-4-benzyloxy phenoxy group) sulfobenzide quality grams is 1:0.1 with the ratio of catalyzer C quality grams again; Hydrogen (the H of 1～10bar pressure ₂) under atmosphere, 25～50 ℃ are stirred 10～24 hours; After reaction finishes, filtration catalizer C, steams and desolventizes F, and with the 2～12mol/L aqueous hydrochloric acid recrystallization that contains massfraction 1% tindichloride, 100 ℃ of vacuum-drying 24h of gained solid, obtain 4,4 '-bis-(3-amino-4-hydroxy phenoxy group) sulfobenzide hydrochloride;

The other the same as in Example 16, omits.

Embodiment 19:

The preparation method of 4,4 '-bis-(3-amino-4-hydroxy phenoxy group) sulfobenzide hydrochloride, comprises the following steps:

Step I: between preparation, nitro is to hydroxyl halobenzene: with arbitrary in above-described embodiment, omit;

Step II: between preparation, nitro is to benzyloxy halobenzene: with arbitrary in above-described embodiment, omit;

Step III: preparation 4,4 '-bis-(3-nitro-4-benzyloxy phenoxy group) sulfobenzide:

Nitro between step II gained is added in reactor C benzyloxy halobenzene and solvent D, add again bisphenol S, alkali and catalyst B, in the middle of it, nitro is 1:1～5 to benzyloxy halobenzene mmole number with the ratio of solvent D milliliter number, between nitro to benzyloxy halobenzene mmole number, be 1:0.2～0.5 with the ratio of bisphenol S mmole number, between nitro to benzyloxy halobenzene mmole number, be 1:1～5 with the ratio of alkali mmole number, between nitro to benzyloxy halobenzene mmole number, be 1:0.1～1 with the ratio of catalyst B mmole number, nitrogen (N ₂) be heated to 120～180 ℃ under atmosphere and stir 10～48 hours, after reaction finishes, the water that adds solvent D total amount 5～10 volume multiples, suction filtration, solids is with after the water washing of solvent D total amount 1～3 volume multiple 2～3 times, with solvent E recrystallization, make 4,4 '-bis-(3-nitro-4-benzyloxy phenoxy group) sulfobenzide;

Step IV: preparation 4,4 '-bis-(3-amino-4-hydroxy phenoxy group) sulfobenzide hydrochloride:

Step III gained 4,4 '-bis-(3-nitro-4-benzyloxy phenoxy group) sulfobenzide is added in reactor D and dissolved with solvent F, and wherein 4,4 '-bis-(3-nitro-4-benzyloxy phenoxy group) sulfobenzide mmole number is 1:10～15 with the ratio of solvent F milliliter number; Add catalyzer C, 4,4 '-bis-(3-nitro-4-benzyloxy phenoxy group) sulfobenzide quality grams is 1:0.01～0.1 with the ratio of catalyzer C quality grams again; Hydrogen (the H of 1～10bar pressure ₂) under atmosphere, 25～50 ℃ are stirred 10～24 hours; After reaction finishes, filtration catalizer C, steams and desolventizes F, and with the 2～12mol/L aqueous hydrochloric acid recrystallization that contains massfraction 1% tindichloride, 100 ℃ of vacuum-drying 24h of gained solid, obtain 4,4 '-bis-(3-amino-4-hydroxy phenoxy group) sulfobenzide hydrochloride;

The other the same as in Example 16, omits.

Embodiment 20:

The preparation method of 4,4 '-(3-amino-4-hydroxy phenoxy group) ditane hydrochloride, comprises the following steps:

Step I: between preparation, nitro is to hydroxyl halobenzene: with arbitrary in above-described embodiment, omit;

Step II: between preparation, nitro is to benzyloxy halobenzene: with arbitrary in above-described embodiment, omit;

Step III: preparation 4,4 '-(3-nitro-4-benzyloxy phenoxy group) ditane:

Nitro between step II gained is added in reactor C benzyloxy halobenzene and solvent D, then add Bisphenol F, alkali and catalyst B, in the middle of it, nitro is 1:1～5 to benzyloxy halobenzene mmole number with the ratio of solvent D milliliter number; Between nitro to benzyloxy halobenzene mmole number, be 1:0.2～0.5 with the ratio of Bisphenol F mmole number; Between nitro to benzyloxy halobenzene mmole number, be 1:1～5 with the ratio of alkali mmole number; Between nitro to benzyloxy halobenzene mmole, be 1:0.1～1 with the ratio of catalyst B mmole number; Nitrogen (N ₂) be heated to 120～180 ℃ under atmosphere and stir 10～48 hours, after reaction finishes, the water that adds solvent D total amount 5～10 volume multiples, suction filtration, solids is with after the water washing of solvent D total amount 1～3 volume multiple 2～3 times, with solvent E recrystallization, make 4,4 '-(3-nitro-4-benzyloxy phenoxy group) ditane;

Described catalyst B is selected from elemental copper and cuprous salt, is cuprous chloride, cuprous bromide or cuprous iodide;

Described alkali is selected from alkali or its salt of weak acid that alkalies and alkaline earth generates, and is any in sodium hydroxide, potassium hydroxide, hydrated barta, sodium carbonate, salt of wormwood, sodium-acetate;

Described solvent D is: acid amides is DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone, and sulfoxide is any in methyl-sulphoxide;

Described recrystallization solvent E is: water, and alcohol is methyl alcohol, ethanol, Virahol, and halohydrocarbon is methylene dichloride, chloroform, ethylene dichloride, and ester is ethyl acetate, butylacetate; Ether is ether, tertiary butyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF), and nitrile is one or more the mixture in acetonitrile, propionitrile;

Step IV: preparation 4,4 '-(3-amino-4-hydroxy phenoxy group) ditane hydrochloride:

4,4 '-(3-nitro-4-benzyloxy phenoxy group) ditane that step III is made adds in reactor D uses solvent F to dissolve, and wherein 4,4 '-(3-nitro-4-benzyloxy phenoxy group) ditane mmole number is 1:10～15 with the ratio of solvent F milliliter number; Add catalyzer C, 4,4 '-(3-nitro-4-benzyloxy phenoxy group) ditane quality gram (g) number is 1:0.01～0.1 with the ratio of catalyzer C quality grams again; Hydrogen (the H of 1～10bar pressure ₂) under atmosphere, 25～50 ℃ are stirred 10～24 hours; After reaction finishes, filtration catalizer C, steams and desolventizes F, with the 2～12mol/L aqueous hydrochloric acid recrystallization that contains massfraction 1% tindichloride, 100 ℃ of vacuum-drying 24h of gained solid, make 4,4 '-(3-amino-4-hydroxy phenoxy group) ditane hydrochloride;

Described solvent F is: alcohol is methyl alcohol, ethanol, Virahol, and ether is one or more the mixture in ether, tetrahydrofuran (THF);

Described catalyzer C is selected from the platinum family precious metal being loaded on carrier, and platinum family precious metal is palladium, platinum or rhodium, and carrier is gac, aluminum oxide or silicon oxide.

The essential characteristic of this compound 4,4 '-(3-amino-4-hydroxy phenoxy group) ditane hydrochloride: white powder, structural characterization is as follows: infrared spectra (KBr, cm ^-1) 3352,2921,1617,1585,1519,1467,1422,1263,1226,1161,1137,1049,1013,965,924,861,817,737; Ultimate analysis (%): theoretical value: C:61.61, H:4.96, N:5.75; Measured value: C:61.55, H:4.87, N:5.70; ¹hNMR:(D ₂o, 400MHz, ppm) 7.24(8H); 6.66(4H); 6.16(2H); 3.96(2H); ESI-MS:m/z (M+1) 414.2.

Embodiment 21:

The preparation method of 4,4 '-(3-amino-4-hydroxy phenoxy group) ditane hydrochloride, comprises the following steps:

Step I: between preparation, nitro is to hydroxyl halobenzene: with arbitrary in above-described embodiment, omit;

Step II: between preparation, nitro is to benzyloxy halobenzene: with arbitrary in above-described embodiment, omit;

Step III: preparation 4,4 '-(3-nitro-4-benzyloxy phenoxy group) ditane:

Nitro between step II gained is added in reactor C benzyloxy halobenzene and solvent D, then add Bisphenol F, alkali and catalyst B, in the middle of it, nitro is 1:3 to benzyloxy halobenzene mmole number with the ratio of solvent D milliliter number; Between nitro to benzyloxy halobenzene mmole number, be 1:0.35 with the ratio of Bisphenol F mmole number; Between nitro to benzyloxy halobenzene mmole number, be 1:3 with the ratio of alkali mmole number; Between nitro to benzyloxy halobenzene mmole, be 1:0.6 with the ratio of catalyst B mmole number; Nitrogen (N ₂) be heated to 120～180 ℃ under atmosphere and stir 29 hours, after reaction finishes, add the water of solvent D total amount 7 volume multiples, suction filtration, solids is with after the water washing of solvent D total amount 2 volume multiples 2 times, with solvent E recrystallization, make 4,4 '-(3-nitro-4-benzyloxy phenoxy group) ditane;

Step IV: preparation 4,4 '-(3-amino-4-hydroxy phenoxy group) ditane hydrochloride:

4,4 '-(3-nitro-4-benzyloxy phenoxy group) ditane that step III is made adds in reactor D uses solvent F to dissolve, and wherein 4,4 '-(3-nitro-4-benzyloxy phenoxy group) ditane mmole number is 1:12.5 with the ratio of solvent F milliliter number; Add catalyzer C, 4,4 '-(3-nitro-4-benzyloxy phenoxy group) ditane quality gram (g) number is 1:0.06 with the ratio of catalyzer C quality grams again; Hydrogen (the H of 1～10bar pressure ₂) under atmosphere, 25～50 ℃ are stirred 16 hours; After reaction finishes, filtration catalizer C, steams and desolventizes F, with the 2～12mol/L aqueous hydrochloric acid recrystallization that contains massfraction 1% tindichloride, 100 ℃ of vacuum-drying 24h of gained solid, make 4,4 '-(3-amino-4-hydroxy phenoxy group) ditane hydrochloride;

The other the same as in Example 20, omits.

Embodiment 22:

The preparation method of 4,4 '-(3-amino-4-hydroxy phenoxy group) ditane hydrochloride, comprises the following steps:

Step I: between preparation, nitro is to hydroxyl halobenzene: with arbitrary in above-described embodiment, omit;

Step II: between preparation, nitro is to benzyloxy halobenzene: with arbitrary in above-described embodiment, omit;

Step III: preparation 4,4 '-(3-nitro-4-benzyloxy phenoxy group) ditane:

Nitro between step II gained is added in reactor C benzyloxy halobenzene and solvent D, then add Bisphenol F, alkali and catalyst B, in the middle of it, nitro is 1:1 to benzyloxy halobenzene mmole number with the ratio of solvent D milliliter number; Between nitro to benzyloxy halobenzene mmole number, be 1:0.2 with the ratio of Bisphenol F mmole number; Between nitro to benzyloxy halobenzene mmole number, be 1:1 with the ratio of alkali mmole number; Between nitro to benzyloxy halobenzene mmole, be 1:0.1 with the ratio of catalyst B mmole number; Nitrogen (N ₂) be heated to 120～180 ℃ under atmosphere and stir 10 hours, after reaction finishes, add the water of solvent D total amount 5 volume multiples, suction filtration, solids is with after the water washing of solvent D total amount 1 volume multiple 2 times, with solvent E recrystallization, make 4,4 '-(3-nitro-4-benzyloxy phenoxy group) ditane;

Step IV: preparation 4,4 '-(3-amino-4-hydroxy phenoxy group) ditane hydrochloride:

4,4 '-(3-nitro-4-benzyloxy phenoxy group) ditane that step III is made adds in reactor D uses solvent F to dissolve, and wherein 4,4 '-(3-nitro-4-benzyloxy phenoxy group) ditane mmole number is 1:10 with the ratio of solvent F milliliter number; Add catalyzer C, 4,4 '-(3-nitro-4-benzyloxy phenoxy group) ditane quality gram (g) number is 1:0.01 with the ratio of catalyzer C quality grams again; Hydrogen (the H of 1～10bar pressure ₂) under atmosphere, 25～50 ℃ are stirred 10 hours; After reaction finishes, filtration catalizer C, steams and desolventizes F, with the 2～12mol/L aqueous hydrochloric acid recrystallization that contains massfraction 1% tindichloride, 100 ℃ of vacuum-drying 24h of gained solid, make 4,4 '-(3-amino-4-hydroxy phenoxy group) ditane hydrochloride;

The other the same as in Example 20, omits.

Embodiment 23:

The preparation method of 4,4 '-(3-amino-4-hydroxy phenoxy group) ditane hydrochloride, comprises the following steps:

Step I: between preparation, nitro is to hydroxyl halobenzene: with arbitrary in above-described embodiment, omit;

Step II: between preparation, nitro is to benzyloxy halobenzene: with arbitrary in above-described embodiment, omit;

Step III: preparation 4,4 '-(3-nitro-4-benzyloxy phenoxy group) ditane:

Nitro between step II gained is added in reactor C benzyloxy halobenzene and solvent D, then add Bisphenol F, alkali and catalyst B, in the middle of it, nitro is 1:5 to benzyloxy halobenzene mmole number with the ratio of solvent D milliliter number; Between nitro to benzyloxy halobenzene mmole number, be 1:0.5 with the ratio of Bisphenol F mmole number; Between nitro to benzyloxy halobenzene mmole number, be 1:5 with the ratio of alkali mmole number; Between nitro to benzyloxy halobenzene mmole, be 1:1 with the ratio of catalyst B mmole number; Nitrogen (N ₂) be heated to 120～180 ℃ under atmosphere and stir 48 hours, after reaction finishes, add the water of solvent D total amount 10 volume multiples, suction filtration, solids is with after the water washing of solvent D total amount 3 volume multiples 3 times, with solvent E recrystallization, make 4,4 '-(3-nitro-4-benzyloxy phenoxy group) ditane;

Step IV: preparation 4,4 '-(3-amino-4-hydroxy phenoxy group) ditane hydrochloride:

4,4 '-(3-nitro-4-benzyloxy phenoxy group) ditane that step III is made adds in reactor D uses solvent F to dissolve, and wherein 4,4 '-(3-nitro-4-benzyloxy phenoxy group) ditane mmole number is 1:15 with the ratio of solvent F milliliter number; Add catalyzer C, 4,4 '-(3-nitro-4-benzyloxy phenoxy group) ditane quality gram (g) number is 1:0.1 with the ratio of catalyzer C quality grams again; Hydrogen (the H of 1～10bar pressure ₂) under atmosphere, 25～50 ℃ are stirred 24 hours; After reaction finishes, filtration catalizer C, steams and desolventizes F, with the 2～12mol/L aqueous hydrochloric acid recrystallization that contains massfraction 1% tindichloride, 100 ℃ of vacuum-drying 24h of gained solid, make 4,4 '-(3-amino-4-hydroxy phenoxy group) ditane hydrochloride;

The other the same as in Example 20, omits.

Embodiment 24:

2,2-bis-(4-(3-amino-4-hydroxy phenoxy group) phenyl) preparation method of HFC-236fa hydrochloride, comprises the following steps:

Step I: between preparation, nitro is to hydroxyl halobenzene: with arbitrary in above-described embodiment, omit;

Step II: between preparation, nitro is to benzyloxy halobenzene: with arbitrary in above-described embodiment, omit;

Step III: preparation 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) HFC-236fa:

Nitro between step II gained is added in reactor C benzyloxy halobenzene and solvent D, then add bisphenol AF, alkali and catalyst B, in the middle of it, nitro is 1:1～5 to benzyloxy halobenzene mmole number with the ratio of solvent D milliliter number; Between nitro to benzyloxy halobenzene mmole number, be 1:0.2～0.5 with the ratio of bisphenol AF mmole number; Between nitro to benzyloxy halobenzene mmole number, be 1:1～5 with the ratio of alkali mmole number; Between nitro to benzyloxy halobenzene mmole number, be 1:0.1～1 with the ratio of catalyst B mmole number; Nitrogen (N ₂) be heated to 120～180 ℃ under atmosphere and stir 10～48 hours, after reaction finishes, the water that adds solvent D total amount 5～10 volume multiples, suction filtration, solids is with after the water washing of solvent D total amount 1～3 volume multiple 2～3 times, with solvent E recrystallization, make 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) HFC-236fa;

Described catalyst B is selected from elemental copper and cuprous salt, is cuprous chloride, cuprous bromide or cuprous iodide;

Described alkali is selected from alkali or its salt of weak acid that alkalies and alkaline earth generates, and is any in sodium hydroxide, potassium hydroxide, hydrated barta, sodium carbonate, salt of wormwood, sodium-acetate;

Described solvent D is: acid amides is DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone, and sulfoxide is any in methyl-sulphoxide;

Described recrystallization solvent E is: water, alcohol is methyl alcohol, ethanol, Virahol, halohydrocarbon is methylene dichloride, chloroform, ethylene dichloride, ester is ethyl acetate, butylacetate, ether is ether, tertiary butyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF), and nitrile is one or more the mixture in acetonitrile, propionitrile;

Step IV: preparation 2,2-bis-(4-(3-amino-4-hydroxy phenoxy group) phenyl) HFC-236fa hydrochloride:

Step III is made 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) HFC-236fa adds in reactor D with solvent F dissolving, wherein 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) HFC-236fa mmole (mmol) number is 1:10～15 with the ratios of solvent F milliliter (ml) number; Adding again catalyzer C, 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) HFC-236fa quality gram (g) is counted and the ratio of catalyzer C quality gram (g) number is 1:0.01～0.1; Hydrogen (H at 1～10bar pressure ₂) under atmosphere, in 25～50 ℃, stir 10～24 hours, after reaction finishes, filtration catalizer C, steaming desolventizes F, with the 2～12mol/L aqueous hydrochloric acid recrystallization that contains massfraction 1% tindichloride, 100 ℃ of vacuum-drying 24h of gained solid, make 2,2-bis-(4-(3-amino-4-hydroxy phenoxy group) phenyl) HFC-236fa hydrochloride;

Described solvent F is: alcohol is methyl alcohol, ethanol, Virahol, and ether is one or more the mixture in ether, tetrahydrofuran (THF);

Described catalyzer C is selected from the platinum family precious metal being loaded on carrier, and platinum family precious metal is palladium, platinum or rhodium, and suitable carrier is gac, aluminum oxide or silicon oxide.

This compound 2,2-bis-(4-(3-amino-4-hydroxy phenoxy group) phenyl) essential characteristic of HFC-236fa hydrochloride: white powder, structural characterization is as follows: infrared spectra (KBr, cm ^-1) 3407,3105,1625,1517,1321,1303,1248,1212,1180,982,967,875,809,740,718; Ultimate analysis (%): theoretical value: C:52.02, H:3.56, N:4.49; Measured value: C:51.93, H:3.51, N:4.45; ¹hNMR:(D ₂o, 400MHz, ppm) 7.29(8H); 6.66(4H); 6.16(2H); ESI-MS:m/z (M+1) 551.1.

Embodiment 25:

2,2-bis-(4-(3-amino-4-hydroxy phenoxy group) phenyl) preparation method of HFC-236fa hydrochloride, comprises the following steps:

Step I: between preparation, nitro is to hydroxyl halobenzene: with arbitrary in above-described embodiment, omit;

Step II: between preparation, nitro is to benzyloxy halobenzene: with arbitrary in above-described embodiment, omit;

Step III: preparation 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) HFC-236fa:

Nitro between step II gained is added in reactor C benzyloxy halobenzene and solvent D, then add bisphenol AF, alkali and catalyst B, in the middle of it, nitro is 1:3 to benzyloxy halobenzene mmole number with the ratio of solvent D milliliter number; Between nitro to benzyloxy halobenzene mmole number, be 1:0.3 with the ratio of bisphenol AF mmole number; Between nitro to benzyloxy halobenzene mmole number, be 1:3 with the ratio of alkali mmole number; Between nitro to benzyloxy halobenzene mmole number, be 1:0.6 with the ratio of catalyst B mmole number; Nitrogen (N ₂) be heated to 120～180 ℃ under atmosphere and stir 28 hours, after reaction finishes, the water that adds solvent D total amount 7 volume multiples, suction filtration, solids is with after the water washing of solvent D total amount 2 volume multiples 3 times, with solvent E recrystallization, make 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) HFC-236fa;

Step IV: preparation 2,2-bis-(4-(3-amino-4-hydroxy phenoxy group) phenyl) HFC-236fa hydrochloride:

Step III is made 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) HFC-236fa adds in reactor D with solvent F dissolving, wherein 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) HFC-236fa mmole number is 1:12 with the ratio of solvent F milliliter number; Adding again catalyzer C, 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) HFC-236fa quality gram (g) is counted and the ratio of catalyzer C quality gram (g) number is 1:0.05; Hydrogen (H at 1～10bar pressure ₂) under atmosphere, in 25～50 ℃, stir 16 hours, after reaction finishes, filtration catalizer C, steaming desolventizes F, with the 2～12mol/L aqueous hydrochloric acid recrystallization that contains massfraction 1% tindichloride, 100 ℃ of vacuum-drying 24h of gained solid, make 2,2-bis-(4-(3-amino-4-hydroxy phenoxy group) phenyl) HFC-236fa hydrochloride;

The other the same as in Example 24, omits.

Embodiment 26:

2,2-bis-(4-(3-amino-4-hydroxy phenoxy group) phenyl) preparation method of HFC-236fa hydrochloride, comprises the following steps:

Step I: between preparation, nitro is to hydroxyl halobenzene: with arbitrary in above-described embodiment, omit;

Step II: between preparation, nitro is to benzyloxy halobenzene: with arbitrary in above-described embodiment, omit;

Step III: preparation 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) HFC-236fa:

Nitro between step II gained is added in reactor C benzyloxy halobenzene and solvent D, then add bisphenol AF, alkali and catalyst B, in the middle of it, nitro is 1:1 to benzyloxy halobenzene mmole number with the ratio of solvent D milliliter number; Between nitro to benzyloxy halobenzene mmole number, be 1:0.2 with the ratio of bisphenol AF mmole number; Between nitro to benzyloxy halobenzene mmole number, be 1:1 with the ratio of alkali mmole number; Between nitro to benzyloxy halobenzene mmole number, be 1:0.1 with the ratio of catalyst B mmole number; Nitrogen (N ₂) be heated to 120～180 ℃ under atmosphere and stir 10 hours, after reaction finishes, the water that adds solvent D total amount 5 volume multiples, suction filtration, solids is with after the water washing of solvent D total amount 1 volume multiple 2 times, with solvent E recrystallization, make 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) HFC-236fa;

Step IV: preparation 2,2-bis-(4-(3-amino-4-hydroxy phenoxy group) phenyl) HFC-236fa hydrochloride:

Step III is made 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) HFC-236fa adds in reactor D with solvent F dissolving, wherein 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) HFC-236fa mmole number is 1:10 with the ratio of solvent F milliliter number; Adding again catalyzer C, 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) HFC-236fa quality gram (g) is counted and the ratio of catalyzer C quality gram (g) number is 1:0.01; Hydrogen (H at 1～10bar pressure ₂) under atmosphere, in 25～50 ℃, stir 10 hours, after reaction finishes, filtration catalizer C, steaming desolventizes F, with the 2～12mol/L aqueous hydrochloric acid recrystallization that contains massfraction 1% tindichloride, 100 ℃ of vacuum-drying 24h of gained solid, make 2,2-bis-(4-(3-amino-4-hydroxy phenoxy group) phenyl) HFC-236fa hydrochloride;

The other the same as in Example 24, omits.

Embodiment 27:

2,2-bis-(4-(3-amino-4-hydroxy phenoxy group) phenyl) preparation method of HFC-236fa hydrochloride, comprises the following steps:

Step I: between preparation, nitro is to hydroxyl halobenzene: with arbitrary in above-described embodiment, omit;

Step II: between preparation, nitro is to benzyloxy halobenzene: with arbitrary in above-described embodiment, omit;

Step III: preparation 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) HFC-236fa:

Nitro between step II gained is added in reactor C benzyloxy halobenzene and solvent D, then add bisphenol AF, alkali and catalyst B, in the middle of it, nitro is 1:5 to benzyloxy halobenzene mmole number with the ratio of solvent D milliliter number; Between nitro to benzyloxy halobenzene mmole number, be 1:0.5 with the ratio of bisphenol AF mmole number; Between nitro to benzyloxy halobenzene mmole number, be 1:5 with the ratio of alkali mmole number; Between nitro to benzyloxy halobenzene mmole number, be 1:1 with the ratio of catalyst B mmole number; Nitrogen (N ₂) be heated to 120～180 ℃ under atmosphere and stir 48 hours, after reaction finishes, the water that adds solvent D total amount 10 volume multiples, suction filtration, solids is with after the water washing of solvent D total amount 3 volume multiples 3 times, with solvent E recrystallization, make 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) HFC-236fa;

Step IV: preparation 2,2-bis-(4-(3-amino-4-hydroxy phenoxy group) phenyl) HFC-236fa hydrochloride:

Step III is made 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) HFC-236fa adds in reactor D with solvent F dissolving, wherein 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) HFC-236fa mmole number is 1:15 with the ratio of solvent F milliliter number; Adding again catalyzer C, 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) HFC-236fa quality gram (g) is counted and the ratio of catalyzer C quality gram (g) number is 1:0.1; Hydrogen (H at 1～10bar pressure ₂) under atmosphere, in 25～50 ℃, stir 24 hours, after reaction finishes, filtration catalizer C, steaming desolventizes F, with the 2～12mol/L aqueous hydrochloric acid recrystallization that contains massfraction 1% tindichloride, 100 ℃ of vacuum-drying 24h of gained solid, make 2,2-bis-(4-(3-amino-4-hydroxy phenoxy group) phenyl) HFC-236fa hydrochloride;

The other the same as in Example 24, omits.

Bis-phenol two (an amino p-hydroxybenzene) ether hydrochloride (being the compound of said structure formula I, II, III or IV) that adopts the present invention to make is applicable to prepare soluble poly benzo oxazole.

The fiber yarn fiber number that novel polyphenyl Bing oxazole processing prepared by the bis-phenol two being made by the present invention (an amino p-hydroxybenzene) ether hydrochloride obtains is about 5.47dtex, intensity can reach 26.72CN/dtex, modulus can reach 583.3CN/dtex, second-order transition temperature is about 275 ℃, and in nitrogen, 10% thermal weight loss temperature is about 450 ℃.Be dissolvable in water the organic solvents such as dimethyl formamide simultaneously, be easy to be processed as variant production.

In above-described embodiment: each raw material adopting is commercially available prod.

In above-described embodiment: in the percentage adopting, do not indicate especially, be mass percent example; Described mass parts can be all gram or kilogram.

In above-described embodiment: the processing parameter in each step (temperature, time, concentration etc.) and each amounts of components numerical value etc. are scope, and any point is all applicable.

The not concrete same prior art of technology contents of narrating in content of the present invention and above-described embodiment.

The invention is not restricted to above-described embodiment, all can implement and have described good result described in content of the present invention.

Claims (4)

1.2,2-bis-(4-(3-amino-4-hydroxy phenoxy group) phenyl) preparation method of propane hydrochloride salt, is characterized in that comprising the following steps:

Step I: between preparation, nitro is to hydroxyl halobenzene:

To add in reactor A hydroxyl halobenzene, and add methylene dichloride to dissolve, be wherein 1:1～5 to hydroxyl halobenzene mmole number with the ratio of methylene dichloride milliliter number; Agitation condition borehole cooling to 0～10 ℃, drip 65% concentrated nitric acid, to hydroxyl halobenzene mmole number, are wherein 1:1～1.5 with the ratio of nitric acid mmole number; After nitric acid finishes, at 0～10 ℃, stir 2～6 hours, after reaction finishes, with methylene dichloride 1～3 volume multiple washing 2～3 times, use solvent orange 2 A recrystallization, dry, make a nitro to hydroxyl halobenzene;

Describedly to hydroxyl halobenzene structure, be:

In formula, X is: Cl, Br or I;

Described recrystallization solvent A is: the mixture of one or more in water, methyl alcohol, ethanol, Virahol, methylene dichloride, chloroform, ethylene dichloride, ethyl acetate, butylacetate, ether, tertiary butyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF), acetonitrile, propionitrile;

Step II: between preparation, nitro is to benzyloxy halobenzene:

Under agitation condition, nitro between step I gained is added in reactor B hydroxyl halobenzene and solvent B, in the middle of it, nitro is 1:1～5 to hydroxyl halobenzene mmole number with the ratio of solvent B milliliter number; After a nitro dissolves completely to hydroxyl halobenzene, then add halo benzyl, alkali and catalyst A, in the middle of it, nitro is 1:1～2 to hydroxyl halobenzene mmole number with the ratio of halo benzyl mmole number; Between nitro to hydroxyl halobenzene mmole number, be 1:1～5 with the ratio of alkali mmole number; Between nitro to hydroxyl halobenzene mmole number, be 1:0.01～0.1 with the ratio of catalyst A mmole number; Being heated to 40～100 ℃ stirs 2～8 hours, after reaction finishes, steaming desolventizes B, adds the water of solvent B total amount 0.5～2 volume multiple, and a nitro is 1:0.5～2 to hydroxyl halobenzene mmole number with the ratio of water milliliter number, stir 0.5～2 hour, suction filtration, solids, with after the water washing of solvent B total amount 1～3 volume multiple 2～3 times, is used solvent C recrystallization, dry, make a nitro to benzyloxy halobenzene;

Described nitro to the chemical structural formula of hydroxyl halobenzene is:

In formula, X is: Cl, Br or I;

Described catalyst A is sodium iodide or potassiumiodide;

Described alkali is sodium hydroxide, potassium hydroxide, hydrated barta, sodium carbonate, salt of wormwood or sodium-acetate;

Described solvent B is: the mixture of one or more in ether, tertiary butyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF), acetone, butanone, acetonitrile, propionitrile, DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone;

Described recrystallization solvent C is: the mixture of one or more in water, methyl alcohol, ethanol, Virahol, methylene dichloride, chloroform, ethylene dichloride, ethyl acetate, butylacetate, ether, tertiary butyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF), acetonitrile, propionitrile;

Step III: preparation 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) propane:

Between step II is made, nitro adds in reactor C benzyloxy halobenzene and solvent D, then adds dihydroxyphenyl propane, alkali and catalyst B, and in the middle of it, nitro is 1:1～5 to benzyloxy halobenzene mmole number with the ratio of solvent D milliliter number; Between nitro to benzyloxy halobenzene mmole number, be 1:0.2～0.5 with the ratio of dihydroxyphenyl propane mmole number; Between nitro to benzyloxy halobenzene mmole number, be 1:1～5 with the ratio of alkali mmole number; Between nitro to benzyloxy halobenzene mmole number, be 1:0.1～1 with the ratio of catalyzer mmole number; At nitrogen (N ₂) be heated to 120～180 ℃ under atmosphere and stir 10～48 hours, after reaction finishes, the water that adds solvent D total amount 5～10 volume multiples, suction filtration, solids is with after the water washing of solvent D total amount 1～3 volume multiple 2～3 times, with solvent E recrystallization, make 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) propane;

Described catalyst B is cuprous chloride, cuprous bromide or cuprous iodide;

Described alkali is any in sodium hydroxide, potassium hydroxide, hydrated barta, sodium carbonate, salt of wormwood, sodium-acetate;

Described solvent D is: any in DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone, methyl-sulphoxide;

Described recrystallization solvent E: the mixture of one or more in water, methyl alcohol, ethanol, Virahol, methylene dichloride, chloroform, ethylene dichloride, ethyl acetate, butylacetate, ether, tertiary butyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF), acetonitrile, propionitrile;

Step IV: preparation 2,2-bis-(4-(3-amino-4-hydroxy phenoxy group) phenyl) propane hydrochloride salt;

Step III is made 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) propane adds in reactor D with solvent F dissolving, wherein 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) propane mmole number is 1:10～15 with the ratio of solvent F milliliter number; Adding again catalyzer C, 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) propane quality grams is 1:0.01～0.1 with the ratio of catalyzer C quality grams; Hydrogen (H at 1～10bar pressure ₂) under atmosphere, in 25～50 ℃, stir 10～24 hours, after reaction finishes, filtration catalizer C, steaming desolventizes F, with the 2～12mol/L aqueous hydrochloric acid recrystallization that contains massfraction 1% tindichloride, 100 ℃ of vacuum-drying 24h of gained solid, obtain 2,2-bis-(4-(3-amino-4-hydroxy phenoxy group) phenyl) propane hydrochloride salt;

Described solvent F:, one or more the mixture in methyl alcohol, ethanol, Virahol, ether, tetrahydrofuran (THF);

Described catalyzer C is the platinum family precious metal being loaded on carrier, and platinum family precious metal is palladium, platinum or rhodium, and carrier is gac, aluminum oxide or silicon oxide.

The preparation method of 2.4,4 '-bis-(3-amino-4-hydroxy phenoxy group) sulfobenzide hydrochloride, is characterized in that comprising the following steps:

Step I: between preparation, nitro is to hydroxyl halobenzene:

To add in reactor A hydroxyl halobenzene, and add methylene dichloride to dissolve, be wherein 1:1～5 to hydroxyl halobenzene mmole number with the ratio of methylene dichloride milliliter number; Agitation condition borehole cooling to 0～10 ℃, drip 65% concentrated nitric acid, to hydroxyl halobenzene mmole number, are wherein 1:1～1.5 with the ratio of nitric acid mmole number; After nitric acid finishes, at 0～10 ℃, stir 2～6 hours, after reaction finishes, with methylene dichloride 1～3 volume multiple washing 2～3 times, use solvent orange 2 A recrystallization, dry, make a nitro to hydroxyl halobenzene;

Describedly to hydroxyl halobenzene structure, be:

In formula, X is: Cl, Br or I;

Described recrystallization solvent A is: the mixture of one or more in water, methyl alcohol, ethanol, Virahol, methylene dichloride, chloroform, ethylene dichloride, ethyl acetate, butylacetate, ether, tertiary butyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF), acetonitrile, propionitrile;

Step II: between preparation, nitro is to benzyloxy halobenzene:

Under agitation condition, nitro between step I gained is added in reactor B hydroxyl halobenzene and solvent B, in the middle of it, nitro is 1:1～5 to hydroxyl halobenzene mmole number with the ratio of solvent B milliliter number; After a nitro dissolves completely to hydroxyl halobenzene, then add halo benzyl, alkali and catalyst A, in the middle of it, nitro is 1:1～2 to hydroxyl halobenzene mmole number with the ratio of halo benzyl mmole number; Between nitro to hydroxyl halobenzene mmole number, be 1:1～5 with the ratio of alkali mmole number; Between nitro to hydroxyl halobenzene mmole number, be 1:0.01～0.1 with the ratio of catalyst A mmole number; Being heated to 40～100 ℃ stirs 2～8 hours, after reaction finishes, steaming desolventizes B, adds the water of solvent B total amount 0.5～2 volume multiple, and a nitro is 1:0.5～2 to hydroxyl halobenzene mmole number with the ratio of water milliliter number, stir 0.5～2 hour, suction filtration, solids, with after the water washing of solvent B total amount 1～3 volume multiple 2～3 times, is used solvent C recrystallization, dry, make a nitro to benzyloxy halobenzene;

Described nitro to the chemical structural formula of hydroxyl halobenzene is:

In formula, X is: Cl, Br or I;

Described catalyst A is sodium iodide or potassiumiodide;

Described alkali is sodium hydroxide, potassium hydroxide, hydrated barta, sodium carbonate, salt of wormwood or sodium-acetate;

Described solvent B is: the mixture of one or more in ether, tertiary butyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF), acetone, butanone, acetonitrile, propionitrile, DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone;

Described recrystallization solvent C is: the mixture of one or more in water, methyl alcohol, ethanol, Virahol, methylene dichloride, chloroform, ethylene dichloride, ethyl acetate, butylacetate, ether, tertiary butyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF), acetonitrile, propionitrile;

Step III: preparation 4,4 '-bis-(3-nitro-4-benzyloxy phenoxy group) sulfobenzide:

Nitro between step II gained is added in reactor C benzyloxy halobenzene and solvent D, add again bisphenol S, alkali and catalyst B, in the middle of it, nitro is 1:1～5 to benzyloxy halobenzene mmole number with the ratio of solvent D milliliter number, between nitro to benzyloxy halobenzene mmole number, be 1:0.2～0.5 with the ratio of bisphenol S mmole number, between nitro to benzyloxy halobenzene mmole number, be 1:1～5 with the ratio of alkali mmole number, between nitro to benzyloxy halobenzene mmole number, be 1:0.1～1 with the ratio of catalyst B mmole number, nitrogen (N ₂) be heated to 120～180 ℃ under atmosphere and stir 10～48 hours, after reaction finishes, the water that adds solvent D total amount 5～10 volume multiples, suction filtration, solids is with after the water washing of solvent D total amount 1～3 volume multiple 2～3 times, with solvent E recrystallization, make 4,4 '-bis-(3-nitro-4-benzyloxy phenoxy group) sulfobenzide;

Described catalyst B is cuprous chloride, cuprous bromide or cuprous iodide;

Described alkali is any in sodium hydroxide, potassium hydroxide, hydrated barta, sodium carbonate, salt of wormwood, sodium-acetate;

Described solvent D is: any in DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone, methyl-sulphoxide;

Described recrystallization solvent E is: the mixture of one or more in water, methyl alcohol, ethanol, Virahol, methylene dichloride, chloroform, ethylene dichloride, ethyl acetate, butylacetate, ether, tertiary butyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF), acetonitrile, propionitrile;

Step IV: preparation 4,4 '-bis-(3-amino-4-hydroxy phenoxy group) sulfobenzide hydrochloride:

Step III gained 4,4 '-bis-(3-nitro-4-benzyloxy phenoxy group) sulfobenzide is added in reactor D and dissolved with solvent F, and wherein 4,4 '-bis-(3-nitro-4-benzyloxy phenoxy group) sulfobenzide mmole number is 1:10～15 with the ratio of solvent F milliliter number; Add catalyzer C, 4,4 '-bis-(3-nitro-4-benzyloxy phenoxy group) sulfobenzide quality grams is 1:0.01～0.1 with the ratio of catalyzer C quality grams again; Hydrogen (the H of 1～10bar pressure ₂) under atmosphere, 25～50 ℃ are stirred 10～24 hours; After reaction finishes, filtration catalizer C, steams and desolventizes F, and with the 2～12mol/L aqueous hydrochloric acid recrystallization that contains massfraction 1% tindichloride, 100 ℃ of vacuum-drying 24h of gained solid, obtain 4,4 '-bis-(3-amino-4-hydroxy phenoxy group) sulfobenzide hydrochloride;

Described solvent F is: the mixture of one or more in methyl alcohol, ethanol, Virahol, ether, tetrahydrofuran (THF);

Described catalyzer C is the platinum family precious metal being loaded on carrier, and platinum family precious metal is palladium, platinum or rhodium; Carrier is gac, aluminum oxide or silicon oxide.

The preparation method of 3.4,4 '-(3-amino-4-hydroxy phenoxy group) ditane hydrochloride, is characterized in that comprising the following steps:

Step I: between preparation, nitro is to hydroxyl halobenzene:

To add in reactor A hydroxyl halobenzene, and add methylene dichloride to dissolve, be wherein 1:1～5 to hydroxyl halobenzene mmole number with the ratio of methylene dichloride milliliter number; Agitation condition borehole cooling to 0～10 ℃, drip 65% concentrated nitric acid, to hydroxyl halobenzene mmole number, are wherein 1:1～1.5 with the ratio of nitric acid mmole number; After nitric acid finishes, at 0～10 ℃, stir 2～6 hours, after reaction finishes, with methylene dichloride 1～3 volume multiple washing 2～3 times, use solvent orange 2 A recrystallization, dry, make a nitro to hydroxyl halobenzene;

Describedly to hydroxyl halobenzene structure, be:

In formula, X is: Cl, Br or I;

Described recrystallization solvent A is: the mixture of one or more in water, methyl alcohol, ethanol, Virahol, methylene dichloride, chloroform, ethylene dichloride, ethyl acetate, butylacetate, ether, tertiary butyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF), acetonitrile, propionitrile;

Step II: between preparation, nitro is to benzyloxy halobenzene:

Under agitation condition, nitro between step I gained is added in reactor B hydroxyl halobenzene and solvent B, in the middle of it, nitro is 1:1～5 to hydroxyl halobenzene mmole number with the ratio of solvent B milliliter number; After a nitro dissolves completely to hydroxyl halobenzene, then add halo benzyl, alkali and catalyst A, in the middle of it, nitro is 1:1～2 to hydroxyl halobenzene mmole number with the ratio of halo benzyl mmole number; Between nitro to hydroxyl halobenzene mmole number, be 1:1～5 with the ratio of alkali mmole number; Between nitro to hydroxyl halobenzene mmole number, be 1:0.01～0.1 with the ratio of catalyst A mmole number; Being heated to 40～100 ℃ stirs 2～8 hours, after reaction finishes, steaming desolventizes B, adds the water of solvent B total amount 0.5～2 volume multiple, and a nitro is 1:0.5～2 to hydroxyl halobenzene mmole number with the ratio of water milliliter number, stir 0.5～2 hour, suction filtration, solids, with after the water washing of solvent B total amount 1～3 volume multiple 2～3 times, is used solvent C recrystallization, dry, make a nitro to benzyloxy halobenzene;

Described nitro to the chemical structural formula of hydroxyl halobenzene is:

In formula, X is: Cl, Br or I;

Described catalyst A is sodium iodide or potassiumiodide;

Described alkali is sodium hydroxide, potassium hydroxide, hydrated barta, sodium carbonate, salt of wormwood or sodium-acetate;

Described solvent B is: the mixture of one or more in ether, tertiary butyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF), acetone, butanone, acetonitrile, propionitrile, DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone;

Described recrystallization solvent C is: the mixture of one or more in water, methyl alcohol, ethanol, Virahol, methylene dichloride, chloroform, ethylene dichloride, ethyl acetate, butylacetate, ether, tertiary butyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF), acetonitrile, propionitrile;

Step III: preparation 4,4 '-(3-nitro-4-benzyloxy phenoxy group) ditane:

Nitro between step II gained is added in reactor C benzyloxy halobenzene and solvent D, then add Bisphenol F, alkali and catalyst B, in the middle of it, nitro is 1:1～5 to benzyloxy halobenzene mmole number with the ratio of solvent D milliliter number; Between nitro to benzyloxy halobenzene mmole number, be 1:0.2～0.5 with the ratio of Bisphenol F mmole number; Between nitro to benzyloxy halobenzene mmole number, be 1:1～5 with the ratio of alkali mmole number; Between nitro to benzyloxy halobenzene mmole, be 1:0.1～1 with the ratio of catalyst B mmole number; Nitrogen (N ₂) be heated to 120～180 ℃ under atmosphere and stir 10～48 hours, after reaction finishes, the water that adds solvent D total amount 5～10 volume multiples, suction filtration, solids is with after the water washing of solvent D total amount 1～3 volume multiple 2～3 times, with solvent E recrystallization, make 4,4 '-(3-nitro-4-benzyloxy phenoxy group) ditane;

Described catalyst B is cuprous chloride, cuprous bromide or cuprous iodide;

Described alkali is any in sodium hydroxide, potassium hydroxide, hydrated barta, sodium carbonate, salt of wormwood, sodium-acetate;

Described solvent D is: any in DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone, methyl-sulphoxide;

Described recrystallization solvent E is: the mixture of one or more in water, methyl alcohol, ethanol, Virahol, methylene dichloride, chloroform, ethylene dichloride, ethyl acetate, butylacetate, ether, tertiary butyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF), acetonitrile, propionitrile;

Step IV: preparation 4,4 '-(3-amino-4-hydroxy phenoxy group) ditane hydrochloride:

4,4 '-(3-nitro-4-benzyloxy phenoxy group) ditane that step III is made adds in reactor D uses solvent F to dissolve, and wherein 4,4 '-(3-nitro-4-benzyloxy phenoxy group) ditane mmole number is 1:10～15 with the ratio of solvent F milliliter number; Add catalyzer C, 4,4 '-(3-nitro-4-benzyloxy phenoxy group) ditane quality grams is 1:0.01～0.1 with the ratio of catalyzer C quality grams again; Hydrogen (the H of 1～10bar pressure ₂) under atmosphere, 25～50 ℃ are stirred 10～24 hours; After reaction finishes, filtration catalizer C, steams and desolventizes F, with the 2～12mol/L aqueous hydrochloric acid recrystallization that contains massfraction 1% tindichloride, 100 ℃ of vacuum-drying 24h of gained solid, make 4,4 '-(3-amino-4-hydroxy phenoxy group) ditane hydrochloride;

Described solvent F is: the mixture of one or more in methyl alcohol, ethanol, Virahol, ether, tetrahydrofuran (THF);

Described catalyzer C is selected from the platinum family precious metal being loaded on carrier, and platinum family precious metal is palladium, platinum or rhodium, and carrier is gac, aluminum oxide or silicon oxide.

4. described in 2,2-bis-(4-(3-amino-4-hydroxy phenoxy group) phenyl) preparation method of HFC-236fa hydrochloride, is characterized in that comprising the following steps:

Step I: between preparation, nitro is to hydroxyl halobenzene:

To add in reactor A hydroxyl halobenzene, and add methylene dichloride to dissolve, be wherein 1:1～5 to hydroxyl halobenzene mmole number with the ratio of methylene dichloride milliliter number; Agitation condition borehole cooling to 0～10 ℃, drip 65% concentrated nitric acid, to hydroxyl halobenzene mmole number, are wherein 1:1～1.5 with the ratio of nitric acid mmole number; After nitric acid finishes, at 0～10 ℃, stir 2～6 hours, after reaction finishes, with methylene dichloride 1～3 volume multiple washing 2～3 times, use solvent orange 2 A recrystallization, dry, make a nitro to hydroxyl halobenzene;

Describedly to hydroxyl halobenzene structure, be:

In formula, X is: Cl, Br or I;

Described recrystallization solvent A is: the mixture of one or more in water, methyl alcohol, ethanol, Virahol, methylene dichloride, chloroform, ethylene dichloride, ethyl acetate, butylacetate, ether, tertiary butyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF), acetonitrile, propionitrile;

Step II: between preparation, nitro is to benzyloxy halobenzene:

Under agitation condition, nitro between step I gained is added in reactor B hydroxyl halobenzene and solvent B, in the middle of it, nitro is 1:1～5 to hydroxyl halobenzene mmole number with the ratio of solvent B milliliter number; After a nitro dissolves completely to hydroxyl halobenzene, then add halo benzyl, alkali and catalyst A, in the middle of it, nitro is 1:1～2 to hydroxyl halobenzene mmole number with the ratio of halo benzyl mmole number; Between nitro to hydroxyl halobenzene mmole number, be 1:1～5 with the ratio of alkali mmole number; Between nitro to hydroxyl halobenzene mmole number, be 1:0.01～0.1 with the ratio of catalyst A mmole number; Being heated to 40～100 ℃ stirs 2～8 hours, after reaction finishes, steaming desolventizes B, adds the water of solvent B total amount 0.5～2 volume multiple, and a nitro is 1:0.5～2 to hydroxyl halobenzene mmole number with the ratio of water milliliter number, stir 0.5～2 hour, suction filtration, solids, with after the water washing of solvent B total amount 1～3 volume multiple 2～3 times, is used solvent C recrystallization, dry, make a nitro to benzyloxy halobenzene;

Described nitro to the chemical structural formula of hydroxyl halobenzene is:

In formula, X is: Cl, Br or I;

Described catalyst A is sodium iodide or potassiumiodide;

Described alkali is sodium hydroxide, potassium hydroxide, hydrated barta, sodium carbonate, salt of wormwood or sodium-acetate;

Described solvent B is: the mixture of one or more in ether, tertiary butyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF), acetone, butanone, acetonitrile, propionitrile, DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone;

Described recrystallization solvent C is: the mixture of one or more in water, methyl alcohol, ethanol, Virahol, methylene dichloride, chloroform, ethylene dichloride, ethyl acetate, butylacetate, ether, tertiary butyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF), acetonitrile, propionitrile;

Step III: preparation 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) HFC-236fa:

Nitro between step II gained is added in reactor C benzyloxy halobenzene and solvent D, then add bisphenol AF, alkali and catalyst B, in the middle of it, nitro is 1:1～5 to the ratio of benzyloxy halobenzene mmole number and solvent D milliliter (ml) number; Between nitro to benzyloxy halobenzene mmole (mmol) number, be 1:0.2～0.5 with the ratio of bisphenol AF mmole number; Between nitro to benzyloxy halobenzene mmole number, be 1:1～5 with the ratio of alkali mmole number; Between nitro to benzyloxy halobenzene mmole number, be 1:0.1～1 with the ratio of catalyst B mmole number; Nitrogen (N ₂) be heated to 120～180 ℃ under atmosphere and stir 10～48 hours, after reaction finishes, the water that adds solvent D total amount 5～10 volume multiples, suction filtration, solids is with after the water washing of solvent D total amount 1～3 volume multiple 2～3 times, with solvent E recrystallization, make 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) HFC-236fa;

Described catalyst B is cuprous chloride, cuprous bromide or cuprous iodide;

Described alkali is any in sodium hydroxide, potassium hydroxide, hydrated barta, sodium carbonate, salt of wormwood, sodium-acetate;

Described solvent D is: any in DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone, methyl-sulphoxide;

Described recrystallization solvent E is: the mixture of one or more in water, methyl alcohol, ethanol, Virahol, methylene dichloride, chloroform, ethylene dichloride, ethyl acetate, butylacetate, ether, tertiary butyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF), acetonitrile, propionitrile;

Step IV: preparation 2,2-bis-(4-(3-amino-4-hydroxy phenoxy group) phenyl) HFC-236fa hydrochloride:

Step III is made 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) HFC-236fa adds in reactor D with solvent F dissolving, wherein 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) HFC-236fa mmole number is 1:10～15 with the ratio of solvent F milliliter number; Adding again catalyzer C, 2,2-bis-(4-(3-nitro-4-benzyloxy phenoxy group) phenyl) HFC-236fa quality grams is 1:0.01～0.1 with the ratio of catalyzer C quality grams; Hydrogen (H at 1～10bar pressure ₂) under atmosphere, in 25～50 ℃, stir 10～24 hours, after reaction finishes, filtration catalizer C, steaming desolventizes F, with the 2～12mol/L aqueous hydrochloric acid recrystallization that contains massfraction 1% tindichloride, 100 ℃ of vacuum-drying 24h of gained solid, make 2,2-bis-(4-(3-amino-4-hydroxy phenoxy group) phenyl) HFC-236fa hydrochloride;

Described solvent F is:, one or more the mixture in methyl alcohol, ethanol, Virahol, ether, tetrahydrofuran (THF);

Described catalyzer C is selected from the platinum family precious metal being loaded on carrier, and platinum family precious metal is palladium, platinum or rhodium, and suitable carrier is gac, aluminum oxide or silicon oxide.