CN102584610A - Bisphenol 2 (m-amino p-hydroxy phenyl) ether hydrochloride and preparation method and application thereof - Google Patents
Bisphenol 2 (m-amino p-hydroxy phenyl) ether hydrochloride and preparation method and application thereof Download PDFInfo
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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
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.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 the last century the eighties, the benzoxazole base polymer has caused extensive attention and research owing to show good mechanics, thermal property and chemicalstability.Wherein the most representative polyparaphenylene Ben Bing Er oxazole (PBO) is a kind of HS and 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 the PBO molecule is rigid rod-like molecules, percent crystallinity height and plane of crystal are smooth, cause it not melt insoluble and intermiscibility is poor, have limited its range of application greatly.In order to improve these shortcomings of PBO; Enlarge its application; People have carried out a large amount of research; Mainly comprise the PBO monomer that pbo fiber is carried out surface-treated and design synthesizing new, such as in monomer, introducing side-chain radical or use special monomer to form side chain, or in monomer, introduce flexible group such as saturated carbon chains, ehter bond etc.
As in patent CN 1660776A, synthesized the diamino-bis-phenol that does not contain fragrant ehter bond, in patent CN 101362700A, also synthesized similar compounds simultaneously.Contain saturated carbon chains or sulfuryl group in these compounds, can improve the kindliness of polybenzoxazole molecule.Be dissolved in organic solvent hardly but in CN 101362700A, mention the polybenzoxazole that is prepared by monomer whose, solvability is not improved significantly.
In patent US 2004/0049081, synthesized the monomer that the diamino-dihydroxy compound that contains fragrant ehter bond is used for polybenzoxazole.The monomer of this structure has further improved the molecular flexibility of polybenzoxazole owing to contain groups such as fragrant ehter bond and saturated carbon chains simultaneously.But its raw material is difficult for preparation to hydroxyl fluorobenzene between nitro, costs an arm and a leg, and is difficult to promote practical.
In addition; In patent CN101263180A; In the polybenzoxazole that has synthesized solubility, itself and CN 1660776A the difference of polybenzoxazole with replaced terephthalic acid with 1,4 cyclohexanedicarboxylic acid; The kindliness of hexanaphthene group has improved the solvability of polymkeric substance, has kept good performance simultaneously again.But the price of 1,4 cyclohexanedicarboxylic acid is more than 5 times of price (8000～10000 yuan/ton) of terephthalic acid up to more than 50000 yuan/ton, and its cost is significantly improved, and practicality is relatively poor.
Summary of the invention
The object of the 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 is provided.
Content of the present invention is: 2, and 2-two (4-(3-amino-4-hydroxy phenoxy) phenyl) propane hydrochloride salt is characterized in that this compound has the chemical structural formula of formula I:
（Ⅰ）
Content of the present invention is said 2, and the preparation method of 2-two (4-(3-amino-4-hydroxy phenoxy) phenyl) propane hydrochloride salt is characterized in that comprising the following steps:
The step I: nitro is to the hydroxyl halobenzene between preparation:
To add in the reactor A the hydroxyl halobenzene, and add the methylene dichloride dissolving, wherein the ratio to hydroxyl halobenzene mmole (mmol) number and methylene dichloride milliliter (ml) number is 1:1～5; Be cooled to 0～10 ℃ under the agitation condition, drip 65% concentrated nitric acid, wherein the ratio to hydroxyl halobenzene mmole (mmol) number and nitric acid mmole (mmol) number is 1:1～1.5; Nitric acid finishes the back and stirred 2～6 hours down at 0～10 ℃, after reaction finishes, with the washing of methylene dichloride 1～3 volume multiple 2～3 times, uses the solvent orange 2 A recrystallization, and drying makes a nitro to the hydroxyl halobenzene;
Saidly be to hydroxyl halobenzene structure:
X is in the formula: Cl, Br or I;
Reaction formula is:
To nitro between the hydroxyl halobenzene to the hydroxyl halobenzene
Said recrystallization solvent A is: water, and alcohol is methyl alcohol, ethanol, Virahol, and halohydrocarbon is methylene dichloride, chloroform, ethylene dichloride, and ester is ETHYLE ACETATE, butylacetate; Ether is ether, uncle's butyl ether, ethylene glycol diethyl ether, THF, and nitrile is one or more the mixture in acetonitrile, the propionitrile;
The step II: nitro is to the benzyloxy halobenzene between preparation:
Under agitation condition, nitro between step I gained is added in the reactor B hydroxyl halobenzene and solvent B, wherein between nitro be 1:1～5 to the ratios of hydroxyl halobenzene mmole (mmol) number and solvent B milliliter (ml) number; After treating that a nitro dissolves the hydroxyl halobenzene fully, add halo benzyl, alkali and catalyst A again, wherein between nitro be 1:1～2 to the ratios of hydroxyl halobenzene mmole (mmol) number and halo benzyl mmole (mmol) number; Between nitro be 1:1～5 to the ratios of hydroxyl halobenzene mmole (mmol) number and alkali mmole (mmol) number; Between nitro be 1:0.01～0.1 to the ratios of hydroxyl halobenzene mmole (mmol) number and catalyst A mmole (mmol) number; Be heated to 40～100 ℃ and stirred 2～8 hours, after reaction finished, steaming desolventized B; The water that adds solvent B total amount 0.5～2 volume multiple, a nitro is 1:0.5～2 to the ratio of hydroxyl halobenzene mmole (mmol) number and water milliliter (ml) number, stirs 0.5～2 hour; Suction filtration, solids with the water washing of solvent B total amount 1～3 volume multiple 2～3 times after, use the solvent C recrystallization; Drying makes a nitro to the benzyloxy halobenzene;
Said nitro to the chemical structural formula of hydroxyl halobenzene is:
X is in the formula: Cl, Br or I;
Reaction formula is:
Between nitro to nitro between hydroxyl halobenzene halo benzyl to the benzyloxy halobenzene
Wherein X is: Cl, Br or I; X' is: Cl, Br or I;
Said catalyst A is selected from iodine and salt compounded of iodine, is Soiodin or potassiumiodide;
Said alkali is selected from alkali or its salt of weak acid that alkalies and alkaline earth generates, and is sodium hydroxide, Pottasium Hydroxide, hydrated barta, yellow soda ash, salt of wormwood or sodium-acetate;
Said solvent B is: ether is ether, uncle's butyl ether, ethylene glycol diethyl ether, THF; Ketone is acetone, butanone, and nitrile is acetonitrile, propionitrile, and acid amides is N; The mixture of one or more in dinethylformamide, DMAC N,N, the N-Methyl pyrrolidone;
Said recrystallization solvent C is: water, and alcohol is methyl alcohol, ethanol, Virahol, and halohydrocarbon is methylene dichloride, chloroform, ethylene dichloride, and ester is ETHYLE ACETATE, butylacetate; Ether is ether, uncle's butyl ether, ethylene glycol diethyl ether, THF, and nitrile is one or more the mixture in acetonitrile, the propionitrile;
The step III: preparation 2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) propane:
With the step II make between nitro benzyloxy halobenzene and solvent D are added among the reactor drum C, add dihydroxyphenyl propane, alkali and catalyst B again, wherein between nitro be 1:1～5 to the ratios of benzyloxy halobenzene mmole (mmol) number and solvent D milliliter (ml) number; Between nitro be 1:0.2～0.5 to the ratios of benzyloxy halobenzene mmole (mmol) number and dihydroxyphenyl propane mmole (mmol) number; Between nitro be 1:1～5 to the ratios of benzyloxy halobenzene mmole (mmol) number and alkali mmole (mmol) number; Between nitro be 1:0.1～1 to the ratios of benzyloxy halobenzene mmole (mmol) number and catalyst B mmole (mmol) number; At nitrogen (N
2) be heated to 120～180 ℃ under the atmosphere and stirred 10～48 hours; After reaction finishes, add the water of solvent D total amount 5～10 volume multiples, suction filtration; Solids with the water washing of solvent D total amount 1～3 volume multiple 2～3 times after; With solvent E recrystallization, make 2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) propane;
Reaction formula is:
Between nitro to benzyloxy halobenzene dihydroxyphenyl propane
2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) propane
Wherein X is: Cl, Br or I;
Said catalyst B is selected from elemental copper and cuprous salt, is cuprous chloride, cuprous bromide or cuprous iodide;
Said alkali is selected from alkali or its salt of weak acid that alkalies and alkaline earth generates, and is in sodium hydroxide, Pottasium Hydroxide, hydrated barta, yellow soda ash, salt of wormwood, the sodium-acetate any;
Said solvent D is: acid amides is N, and dinethylformamide, DMAC N,N, N-Methyl pyrrolidone, sulfoxide are any in the methyl-sulphoxide;
Said recrystallization solvent E: water, alcohol is methyl alcohol, ethanol, Virahol, and halohydrocarbon is methylene dichloride, chloroform, ethylene dichloride, and ester is ETHYLE ACETATE, butylacetate; Ether is ether, uncle's butyl ether, ethylene glycol diethyl ether, THF, and nitrile is one or more the mixture in acetonitrile, the propionitrile;
Step IV: preparation 2,2-two (4-(3-amino-4-hydroxy phenoxy) phenyl) propane hydrochloride salt;
With the step III make 2; Dissolve with solvent F among 2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) the propane adding reactor drum D; Wherein 2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) propane mmole (mmol) number is 1:10～15 with the ratios of solvent F milliliter (ml) number; Add catalyzer C again, 2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) propane quality gram (g) is 1:0.01～0.1 with the ratio of catalyzer C quality gram (g); Hydrogen (H at 1～10bar pressure
2) under the atmosphere, stirred 10～24 hours in 25～50 ℃, 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-two (4-(3-amino-4-hydroxy phenoxy) phenyl) propane hydrochloride salt;
Reaction formula is:
2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) propane
The structure formula I
Said solvent F: alcohol is methyl alcohol, ethanol, Virahol, and ether is one or more the mixture in ether, the THF;
Said catalyzer C is the platinum family precious metal that is stated from the carrier, and the platinum family precious metal is palladium, platinum or rhodium, and carrier is gac, aluminum oxide or silicon oxide.
This compound 2, the essential characteristic of 2-two (4-(3-amino-4-hydroxy phenoxy) phenyl) propane hydrochloride salt: white powder, structural characterization is following: ir 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 '-two (3-amino-4-hydroxy phenoxy) sulfobenzide hydrochloride is characterized in that this compound has the chemical structural formula of formula II:
（Ⅱ）
The preparation method of 4,4 '-two (3-amino-4-hydroxy phenoxy) described in another content of the present invention sulfobenzide hydrochloride is characterized in that comprising the following steps:
The step I: nitro is to the hydroxyl halobenzene between preparation:
To add in the reactor A the hydroxyl halobenzene, and add the methylene dichloride dissolving, wherein the ratio to hydroxyl halobenzene mmole (mmol) number and methylene dichloride milliliter (ml) number is 1:1～5; Be cooled to 0～10 ℃ under the agitation condition, drip 65% concentrated nitric acid, wherein the ratio to hydroxyl halobenzene mmole (mmol) number and nitric acid mmole (mmol) number is 1:1～1.5; Nitric acid finishes the back and stirred 2～6 hours down at 0～10 ℃, after reaction finishes, with the washing of methylene dichloride 1～3 volume multiple 2～3 times, uses the solvent orange 2 A recrystallization, and drying makes a nitro to the hydroxyl halobenzene;
Saidly be to hydroxyl halobenzene structure:
X is in the formula: Cl, Br or I;
Reaction formula is:
To nitro between the hydroxyl halobenzene to the hydroxyl halobenzene
Said recrystallization solvent A is: water, and alcohol is methyl alcohol, ethanol, Virahol, and halohydrocarbon is methylene dichloride, chloroform, ethylene dichloride, and ester is ETHYLE ACETATE, butylacetate; Ether is ether, uncle's butyl ether, ethylene glycol diethyl ether, THF, and nitrile is one or more the mixture in acetonitrile, the propionitrile;
The step II: nitro is to the benzyloxy halobenzene between preparation:
Under agitation condition, nitro between step I gained is added in the reactor B hydroxyl halobenzene and solvent B, wherein between nitro be 1:1～5 to the ratios of hydroxyl halobenzene mmole (mmol) number and solvent B milliliter (ml) number; After treating that a nitro dissolves the hydroxyl halobenzene fully, add halo benzyl, alkali and catalyst A again, wherein between nitro be 1:1～2 to the ratios of hydroxyl halobenzene mmole (mmol) number and halo benzyl mmole (mmol) number; Between nitro be 1:1～5 to the ratios of hydroxyl halobenzene mmole (mmol) number and alkali mmole (mmol) number; Between nitro be 1:0.01～0.1 to the ratios of hydroxyl halobenzene mmole (mmol) number and catalyst A mmole (mmol) number; Be heated to 40～100 ℃ and stirred 2～8 hours, after reaction finished, steaming desolventized B; The water that adds solvent B total amount 0.5～2 volume multiple, a nitro is 1:0.5～2 to the ratio of hydroxyl halobenzene mmole (mmol) number and water milliliter (ml) number, stirs 0.5～2 hour; Suction filtration, solids with the water washing of solvent B total amount 1～3 volume multiple 2～3 times after, use the solvent C recrystallization; Drying makes a nitro to the benzyloxy halobenzene;
Said nitro to the chemical structural formula of hydroxyl halobenzene is:
X is in the formula: Cl, Br or I;
Reaction formula is:
Between nitro to nitro between hydroxyl halobenzene halo benzyl to the benzyloxy halobenzene
Wherein X is: Cl, Br or I; X' is: Cl, Br or I;
Said catalyst A is selected from iodine and salt compounded of iodine, is Soiodin or potassiumiodide;
Said alkali is selected from alkali or its salt of weak acid that alkalies and alkaline earth generates, and is sodium hydroxide, Pottasium Hydroxide, hydrated barta, yellow soda ash, salt of wormwood or sodium-acetate;
Said solvent B is: ether is ether, uncle's butyl ether, ethylene glycol diethyl ether, THF; Ketone is acetone, butanone, and nitrile is acetonitrile, propionitrile, and acid amides is N; The mixture of one or more in dinethylformamide, DMAC N,N, the N-Methyl pyrrolidone;
Said recrystallization solvent C is: water, and alcohol is methyl alcohol, ethanol, Virahol, and halohydrocarbon is methylene dichloride, chloroform, ethylene dichloride, and ester is ETHYLE ACETATE, butylacetate; Ether is ether, uncle's butyl ether, ethylene glycol diethyl ether, THF, and nitrile is one or more the mixture in acetonitrile, the propionitrile;
Step III: preparation 4,4 '-two (3-nitro-4-benzyloxy phenoxy) sulfobenzide:
Nitro between step II gained is added among the reactor drum C benzyloxy halobenzene and solvent D; Add bisphenol S, alkali and catalyst B again; Nitro is 1:1～5 to the ratio of benzyloxy halobenzene mmole (mmol) number and solvent D milliliter (ml) number wherein; Between nitro be 1:0.2～0.5 to the ratios of benzyloxy halobenzene mmole (mmol) number and bisphenol S mmole (mmol) number; Between nitro be 1:1～5 to the ratios of benzyloxy halobenzene mmole (mmol) number and alkali mmole (mmol) number, a nitro is 1:0.1～1 to the ratios of benzyloxy halobenzene mmole (mmol) number and catalyst B mmole (mmol) number, nitrogen (N
2) be heated to 120～180 ℃ under the atmosphere and stirred 10～48 hours; After reaction finishes, add the water of solvent D total amount 5～10 volume multiples, suction filtration; Solids with the water washing of solvent D total amount 1～3 volume multiple 2～3 times after; With solvent E recrystallization, make 4,4 '-two (3-nitro-4-benzyloxy phenoxy) sulfobenzide;
Reaction formula is:
Between nitro to benzyloxy halobenzene bisphenol S
4,4 '-two (3-nitro-4-benzyloxy phenoxy) sulfobenzide
Said catalyst B is selected from elemental copper and cuprous salt, is cuprous chloride, cuprous bromide or cuprous iodide;
Said alkali is selected from alkali or its salt of weak acid that alkalies and alkaline earth generates, and is in sodium hydroxide, Pottasium Hydroxide, hydrated barta, yellow soda ash, salt of wormwood, the sodium-acetate any;
Said solvent D is: acid amides is N, dinethylformamide, DMAC N,N, N-Methyl pyrrolidone; Sulfoxide is any in the methyl-sulphoxide;
Said recrystallization solvent E is: water; Alcohol is methyl alcohol, ethanol, Virahol; Halohydrocarbon is methylene dichloride, chloroform, ethylene dichloride; Ester is ETHYLE ACETATE, butylacetate, and ether is ether, uncle's butyl ether, ethylene glycol diethyl ether, THF, and nitrile is one or more the mixture in acetonitrile, the propionitrile;
Step IV: preparation 4,4 '-two (3-amino-4-hydroxy phenoxy) sulfobenzide hydrochloride:
With step III gained 4; Dissolve with solvent F among 4 '-two (3-nitro-4-benzyloxy phenoxy) sulfobenzide adding reactor drum D; Wherein 4,4 '-two (3-nitro-4-benzyloxy phenoxy) sulfobenzide mmole (mmol) number is 1:10～15 with the ratio of solvent F milliliter (ml) number; Add catalyzer C again, 4,4 '-two (3-nitro-4-benzyloxy phenoxy) sulfobenzide quality gram (g) is 1:0.01～0.1 with the ratio of catalyzer C quality gram (g); Hydrogen (the H of 1～10bar pressure
2) under the atmosphere, 25～50 ℃ were stirred 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 4,4 '-two (3-amino-4-hydroxy phenoxy) sulfobenzide hydrochloride;
Reaction formula is:
4,4 '-two (3-nitro-4-benzyloxy phenoxy) sulfobenzide
The structure formula II
Said solvent F is: alcohol is methyl alcohol, ethanol, Virahol, and ether is one or more the mixture in ether, the THF;
Said catalyzer C is the platinum family precious metal that is stated from the carrier, and the 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 '-two (3-amino-4-hydroxy phenoxy) sulfobenzide hydrochloride: white powder, structural characterization is following: ir 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) ditane hydrochloride is characterized in that this compound has the chemical structural formula of formula III:
（Ⅲ）
The preparation method of said 4,4 '-(3-amino-4-hydroxy phenoxy) ditane hydrochloride is characterized in that comprising the following steps:
The step I: nitro is to the hydroxyl halobenzene between preparation:
To add in the reactor A the hydroxyl halobenzene, and add the methylene dichloride dissolving, wherein the ratio to hydroxyl halobenzene mmole (mmol) number and methylene dichloride milliliter (ml) number is 1:1～5; Be cooled to 0～10 ℃ under the agitation condition, drip 65% concentrated nitric acid, wherein the ratio to hydroxyl halobenzene mmole (mmol) number and nitric acid mmole (mmol) number is 1:1～1.5; Nitric acid finishes the back and stirred 2～6 hours down at 0～10 ℃, after reaction finishes, with the washing of methylene dichloride 1～3 volume multiple 2～3 times, uses the solvent orange 2 A recrystallization, and drying makes a nitro to the hydroxyl halobenzene;
Saidly be to hydroxyl halobenzene structure:
X is in the formula: Cl, Br or I;
Reaction formula is:
To nitro between the hydroxyl halobenzene to the hydroxyl halobenzene
Said recrystallization solvent A is: water, and alcohol is methyl alcohol, ethanol, Virahol, and halohydrocarbon is methylene dichloride, chloroform, ethylene dichloride, and ester is ETHYLE ACETATE, butylacetate; Ether is ether, uncle's butyl ether, ethylene glycol diethyl ether, THF, and nitrile is one or more the mixture in acetonitrile, the propionitrile;
The step II: nitro is to the benzyloxy halobenzene between preparation:
Under agitation condition, nitro between step I gained is added in the reactor B hydroxyl halobenzene and solvent B, wherein between nitro be 1:1～5 to the ratios of hydroxyl halobenzene mmole (mmol) number and solvent B milliliter (ml) number; After treating that a nitro dissolves the hydroxyl halobenzene fully, add halo benzyl, alkali and catalyst A again, wherein between nitro be 1:1～2 to the ratios of hydroxyl halobenzene mmole (mmol) number and halo benzyl mmole (mmol) number; Between nitro be 1:1～5 to the ratios of hydroxyl halobenzene mmole (mmol) number and alkali mmole (mmol) number; Between nitro be 1:0.01～0.1 to the ratios of hydroxyl halobenzene mmole (mmol) number and catalyst A mmole (mmol) number; Be heated to 40～100 ℃ and stirred 2～8 hours, after reaction finished, steaming desolventized B; The water that adds solvent B total amount 0.5～2 volume multiple, a nitro is 1:0.5～2 to the ratio of hydroxyl halobenzene mmole (mmol) number and water milliliter (ml) number, stirs 0.5～2 hour; Suction filtration, solids with the water washing of solvent B total amount 1～3 volume multiple 2～3 times after, use the solvent C recrystallization; Drying makes a nitro to the benzyloxy halobenzene;
Said nitro to the chemical structural formula of hydroxyl halobenzene is:
X is in the formula: Cl, Br or I;
Reaction formula is:
Between nitro to nitro between hydroxyl halobenzene halo benzyl to the benzyloxy halobenzene
Wherein X is: Cl, Br or I; X' is: Cl, Br or I;
Said catalyst A is selected from iodine and salt compounded of iodine, is Soiodin or potassiumiodide;
Said alkali is selected from alkali or its salt of weak acid that alkalies and alkaline earth generates, and is sodium hydroxide, Pottasium Hydroxide, hydrated barta, yellow soda ash, salt of wormwood or sodium-acetate;
Said solvent B is: ether is ether, uncle's butyl ether, ethylene glycol diethyl ether, THF; Ketone is acetone, butanone, and nitrile is acetonitrile, propionitrile, and acid amides is N; The mixture of one or more in dinethylformamide, DMAC N,N, the N-Methyl pyrrolidone;
Said recrystallization solvent C is: water, and alcohol is methyl alcohol, ethanol, Virahol, and halohydrocarbon is methylene dichloride, chloroform, ethylene dichloride, and ester is ETHYLE ACETATE, butylacetate; Ether is ether, uncle's butyl ether, ethylene glycol diethyl ether, THF, and nitrile is one or more the mixture in acetonitrile, the propionitrile;
Step III: preparation 4,4 '-(3-nitro-4-benzyloxy phenoxy) ditane:
Nitro between step II gained is added among the reactor drum C benzyloxy halobenzene and solvent D, adds Bisphenol F, alkali and catalyst B again, wherein between nitro be 1:1～5 to the ratios of benzyloxy halobenzene mmole (mmol) number and solvent D milliliter (ml) number; Between nitro be 1:0.2～0.5 to the ratios of benzyloxy halobenzene mmole (mmol) number and Bisphenol F mmole (mmol) number; Between nitro be 1:1～5 to the ratios of benzyloxy halobenzene mmole (mmol) number and alkali mmole (mmol) number; Between nitro be 1:0.1～1 to the ratio of benzyloxy halobenzene mmole (mmol) and catalyst B mmole (mmol) number; Nitrogen (N
2) be heated to 120～180 ℃ under the atmosphere and stirred 10～48 hours; After reaction finishes, add the water of solvent D total amount 5～10 volume multiples, suction filtration; Solids with the water washing of solvent D total amount 1～3 volume multiple 2～3 times after; With solvent E recrystallization, make 4,4 '-(3-nitro-4-benzyloxy phenoxy) ditane;
Reaction formula is:
Between nitro to benzyloxy halobenzene Bisphenol F
4,4 '-(3-nitro-4-benzyloxy phenoxy) ditane
X is in the formula: Cl, Br or I;
Said catalyst B is selected from elemental copper and cuprous salt, is cuprous chloride, cuprous bromide or cuprous iodide;
Said alkali is selected from alkali or its salt of weak acid that alkalies and alkaline earth generates, and is in sodium hydroxide, Pottasium Hydroxide, hydrated barta, yellow soda ash, salt of wormwood, the sodium-acetate any;
Said solvent D is: acid amides is N, and dinethylformamide, DMAC N,N, N-Methyl pyrrolidone, sulfoxide are any in the methyl-sulphoxide;
Said recrystallization solvent E is: water, and alcohol is methyl alcohol, ethanol, Virahol, and halohydrocarbon is methylene dichloride, chloroform, ethylene dichloride, and ester is ETHYLE ACETATE, butylacetate; Ether is ether, uncle's butyl ether, ethylene glycol diethyl ether, THF, and nitrile is one or more the mixture in acetonitrile, the propionitrile;
Step IV: preparation 4,4 '-(3-amino-4-hydroxy phenoxy) ditane hydrochloride:
With the step III make 4; Dissolve with solvent F among 4 '-(3-nitro-4-benzyloxy phenoxy) the ditane adding reactor drum D; Wherein 4,4 '-(3-nitro-4-benzyloxy phenoxy) ditane mmole (mmol) number is 1:10～15 with the ratio of solvent F milliliter (ml) number; Add catalyzer C again, 4,4 '-(3-nitro-4-benzyloxy phenoxy) ditane quality gram (g) is 1:0.01～0.1 with the ratio of catalyzer C quality gram (g); Hydrogen (the H of 1～10bar pressure
2) under the atmosphere, 25～50 ℃ were stirred 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 4,4 '-(3-amino-4-hydroxy phenoxy) ditane hydrochloride;
Reaction formula is:
4,4 '-(3-nitro-4-benzyloxy phenoxy) ditane
The structure formula III
Said solvent F is: alcohol is methyl alcohol, ethanol, Virahol, and ether is one or more the mixture in ether, the THF;
Said catalyzer C is selected from the platinum family precious metal that is stated from the carrier, and the 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) ditane hydrochloride: white powder, structural characterization is following: ir 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, and 2-two (4-(3-amino-4-hydroxy phenoxy) phenyl) HFC-236fa hydrochloride is characterized in that this compound has the chemical structural formula of formula IV:
（Ⅳ）
Said 2, the preparation method of 2-two (4-(3-amino-4-hydroxy phenoxy) phenyl) HFC-236fa hydrochloride is characterized in that comprising the following steps:
The step I: nitro is to the hydroxyl halobenzene between preparation:
To add in the reactor A the hydroxyl halobenzene, and add the methylene dichloride dissolving, wherein the ratio to hydroxyl halobenzene mmole (mmol) number and methylene dichloride milliliter (ml) number is 1:1～5; Be cooled to 0～10 ℃ under the agitation condition, drip 65% concentrated nitric acid, wherein the ratio to hydroxyl halobenzene mmole (mmol) number and nitric acid mmole (mmol) number is 1:1～1.5; Nitric acid finishes the back and stirred 2～6 hours down at 0～10 ℃, after reaction finishes, with the washing of methylene dichloride 1～3 volume multiple 2～3 times, uses the solvent orange 2 A recrystallization, and drying makes a nitro to the hydroxyl halobenzene;
Saidly be to hydroxyl halobenzene structure:
X is in the formula: Cl, Br or I;
Reaction formula is:
To nitro between the hydroxyl halobenzene to the hydroxyl halobenzene
Said recrystallization solvent A is: water, and alcohol is methyl alcohol, ethanol, Virahol, and halohydrocarbon is methylene dichloride, chloroform, ethylene dichloride, and ester is ETHYLE ACETATE, butylacetate; Ether is ether, uncle's butyl ether, ethylene glycol diethyl ether, THF, and nitrile is one or more the mixture in acetonitrile, the propionitrile;
The step II: nitro is to the benzyloxy halobenzene between preparation:
Under agitation condition, nitro between step I gained is added in the reactor B hydroxyl halobenzene and solvent B, wherein between nitro be 1:1～5 to the ratios of hydroxyl halobenzene mmole (mmol) number and solvent B milliliter (ml) number; After treating that a nitro dissolves the hydroxyl halobenzene fully, add halo benzyl, alkali and catalyst A again, wherein between nitro be 1:1～2 to the ratios of hydroxyl halobenzene mmole (mmol) number and halo benzyl mmole (mmol) number; Between nitro be 1:1～5 to the ratios of hydroxyl halobenzene mmole (mmol) number and alkali mmole (mmol) number; Between nitro be 1:0.01～0.1 to the ratios of hydroxyl halobenzene mmole (mmol) number and catalyst A mmole (mmol) number; Be heated to 40～100 ℃ and stirred 2～8 hours, after reaction finished, steaming desolventized B; The water that adds solvent B total amount 0.5～2 volume multiple, a nitro is 1:0.5～2 to the ratio of hydroxyl halobenzene mmole (mmol) number and water milliliter (ml) number, stirs 0.5～2 hour; Suction filtration, solids with the water washing of solvent B total amount 1～3 volume multiple 2～3 times after, use the solvent C recrystallization; Drying makes a nitro to the benzyloxy halobenzene;
Said nitro to the chemical structural formula of hydroxyl halobenzene is:
X is in the formula: Cl, Br or I;
Reaction formula is:
Between nitro to nitro between hydroxyl halobenzene halo benzyl to the benzyloxy halobenzene
Wherein X is: Cl, Br or I; X' is: Cl, Br or I;
Said catalyst A is selected from iodine and salt compounded of iodine, is Soiodin or potassiumiodide;
Said alkali is selected from alkali or its salt of weak acid that alkalies and alkaline earth generates, and is sodium hydroxide, Pottasium Hydroxide, hydrated barta, yellow soda ash, salt of wormwood or sodium-acetate;
Said solvent B is: ether is ether, uncle's butyl ether, ethylene glycol diethyl ether, THF; Ketone is acetone, butanone, and nitrile is acetonitrile, propionitrile, and acid amides is N; The mixture of one or more in dinethylformamide, DMAC N,N, the N-Methyl pyrrolidone;
Said recrystallization solvent C is: water, and alcohol is methyl alcohol, ethanol, Virahol, and halohydrocarbon is methylene dichloride, chloroform, ethylene dichloride, and ester is ETHYLE ACETATE, butylacetate; Ether is ether, uncle's butyl ether, ethylene glycol diethyl ether, THF, and nitrile is one or more the mixture in acetonitrile, the propionitrile;
The step III: preparation 2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) HFC-236fa:
Nitro between step II gained is added among the reactor drum C benzyloxy halobenzene and solvent D, adds bisphenol AF, alkali and catalyst B again, wherein between nitro be 1:1～5 to the ratios of benzyloxy halobenzene mmole (mmol) number and solvent D milliliter (ml) number; Between nitro be 1:0.2～0.5 to the ratios of benzyloxy halobenzene mmole (mmol) number and bisphenol AF mmole (mmol) number; Between nitro be 1:1～5 to the ratios of benzyloxy halobenzene mmole (mmol) number and alkali mmole (mmol) number; Between nitro be 1:0.1～1 to the ratios of benzyloxy halobenzene mmole (mmol) number and catalyst B mmole (mmol) number; Nitrogen (N
2) be heated to 120～180 ℃ under the atmosphere and stirred 10～48 hours; After reaction finishes, add the water of solvent D total amount 5～10 volume multiples, suction filtration; Solids with the water washing of solvent D total amount 1～3 volume multiple 2～3 times after; With solvent E recrystallization, make 2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) HFC-236fa;
Reaction formula is:
Between nitro to benzyloxy halobenzene bisphenol AF
2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) HFC-236fa
X is in the formula: Cl, Br or I;
Said catalyst B is selected from elemental copper and cuprous salt, is cuprous chloride, cuprous bromide or cuprous iodide;
Said alkali is selected from alkali or its salt of weak acid that alkalies and alkaline earth generates, and is in sodium hydroxide, Pottasium Hydroxide, hydrated barta, yellow soda ash, salt of wormwood, the sodium-acetate any;
Said solvent D is: acid amides is N, and dinethylformamide, DMAC N,N, N-Methyl pyrrolidone, sulfoxide are any in the methyl-sulphoxide;
Said recrystallization solvent E is: water; Alcohol is methyl alcohol, ethanol, Virahol; Halohydrocarbon is methylene dichloride, chloroform, ethylene dichloride; Ester is ETHYLE ACETATE, butylacetate, and ether is ether, uncle's butyl ether, ethylene glycol diethyl ether, THF, and nitrile is one or more the mixture in acetonitrile, the propionitrile;
The step IV: preparation 2,2-two (4-(3-amino-4-hydroxy phenoxy) phenyl) HFC-236fa hydrochloride:
With the step III make 2; Dissolve with solvent F among 2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) the HFC-236fa adding reactor drum D; Wherein 2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) HFC-236fa mmole (mmol) number is 1:10～15 with the ratios of solvent F milliliter (ml) number; Add catalyzer C again, 2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) HFC-236fa quality gram (g) is 1:0.01～0.1 with the ratio of catalyzer C quality gram (g); Hydrogen (H at 1～10bar pressure
2) under the atmosphere, stirred 10～24 hours in 25～50 ℃, 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-two (4-(3-amino-4-hydroxy phenoxy) phenyl) HFC-236fa hydrochloride;
Reaction formula is:
2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) HFC-236fa
The structure formula IV
Said solvent F is: alcohol is methyl alcohol, ethanol, Virahol, and ether is one or more the mixture in ether, the THF;
Said catalyzer C is selected from the platinum family precious metal that is stated from the carrier, and the platinum family precious metal is palladium, platinum or rhodium, and suitable carrier is gac, aluminum oxide or silicon oxide.
This compound 2, the essential characteristic of 2-two (4-(3-amino-4-hydroxy phenoxy) phenyl) HFC-236fa hydrochloride: white powder, structural characterization is following: ir 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 preparation soluble poly benzoxazole.During application:
Bis-phenol two (an amino p-hydroxybenzene) ether hydrochloride and after the disodium terephthalate reactant salt generates bis-phenol two (an amino p-hydroxybenzene) ether terephthalate, but polycondensation generates the soluble poly benzoxazole in polyphosphoric acid, reaction formula is:
Bis-phenol two (an amino p-hydroxybenzene) ether hydrochloride disodium terephthalate salt
Bis-phenol two (an amino p-hydroxybenzene) ether terephthalate
The soluble poly benzoxazole
Where R is:
?,
,?
?, or?
.
Process the fiber yarn fiber number that obtains by the novel polyphenyl Bing oxazole of bis-phenol two (an amino p-hydroxybenzene) ether hydrochloride preparation and be about 5.47dtex; Intensity can reach 26.72CN/dtex; Modulus can reach 583.3CN/dtex; Second-order transition temperature is about 275 ℃, and 10% thermal weight loss temperature is about 450 ℃ in the nitrogen.Be dissolvable in water organic solvents such as N simultaneously, be easy to be processed as variant prodn.
Compared with prior art, the present invention has following characteristics and beneficial effect:
(1) compound provided by the invention is used to prepare the soluble poly benzoxazole; In the monomer of benzoxazole base polymer, introduce groups such as ehter bond, increased the molecular flexibility of benzoxazole base polymer, keeping certain intensity and the 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 the hydroxyl halobenzene; Use the benzyl protection hydroxyl; Become ether with the coupling of bis-phenol reagent then, remove benzyl through hydro-reduction again and with nitroreduction for amino, make bis-phenol two (an amino p-hydroxybenzene) ether hydrochloride (monomer) with the hydrochloric acid salify at last; These monomeric four step synthetic methods from cheapness to the hydroxyl halobenzene, can obtain this monomer with yield preferably, compare on raw materials cost with the route of US 2004/0049081 and have great advantage, cost of the present invention is low;
(3) the present invention compares with CN101263180A; Have similar mechanics and thermal property, but since among the CN101263180A price of raw materials used 1,4 cyclohexanedicarboxylic acid up to more than 50000 yuan/ton; Be more than 5 times of price (8000～10000 yuan/ton) of the used terephthalic acid of the present invention; Even add the cost (about 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 operation is practical easily.
Embodiment
Embodiment given below intends so that the present invention is described further; But can not be interpreted as it is restriction to protection domain of the present invention; The technician in this field to some nonessential improvement and adjustment that the present invention makes, still belongs to protection scope of the present invention according to the content of the invention described above.
Embodiment 1:
The step I: nitro is to hydroxyl halobenzene (embodiment 1) between preparation
Synthesizing of embodiment 1:3-nitro-4-hydroxyl base chlorobenzene
Hydroxyl chlorobenzene 152.62g (1.188mol) is placed reaction flask, add the dissolving of 1500ml methylene dichloride, be cooled to 0 ℃ under stirring; Drip 126.74g concentrated nitric acid (65%; 1.308mol), controlled temperature is lower than 5 ℃, dropwises the back temperature control and is lower than 5 ℃ of stirrings 3 hours.1500ml washing twice adds 500ml methyl alcohol, steams and removes methylene dichloride, and suction filtration makes purified 3-nitro-4-hydroxyl base chlorobenzene 180.51g, yellow powder, yield 87.6%.
Structural characterization is following: ir 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) 10.48 (1H); 8.11 (1H); 7.54 (1H); 7.14 (1H); ESI-MS:m/z (M+1) 173.0.
The step II: nitro is to benzyloxy halobenzene (embodiment 2) between preparation
Synthesizing of embodiment 2:3-nitro-4-benzyloxy chlorobenzene
3-nitro-4-hydroxyl chlorobenzene 126.34g (0.726mol) places reaction flask, adds the 1000ml acetonitrile.After the dissolving, restir adds 124.58g (0.903mol) salt of wormwood and 92.46g benzyl chlorine (0.730mol) and 10.39g potassiumiodide (0.0626mol), reflux 2 hours down.The steaming of cooling back removes acetonitrile, adds 1000ml water, stirs 45min, suction filtration, and 1000ml washing twice gets thick product.Thick product is used ethyl alcohol recrystallization, makes purified 3-nitro-4-benzyloxy chlorobenzene 178.24g, yellow crystals, yield 93.0%.
Structural characterization is following: ir 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) 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: preparation bis-phenol two (nitro is to the benzyloxy phenyl) ether (embodiment 3～6)
Embodiment 3:2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) propane synthetic
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) are placed reaction flask, add the 150ml N-Methyl pyrrolidone.Nitrogen protection is stirred down, and is heated to 150 ℃ of reactions 18 hours.Pour into after the cooling in the 1200ml water, suction filtration behind the stirring 10min with 400ml washing twice, gets thick product.Thick product is with ETHYLE ACETATE and normal hexane mixed solvent recrystallization, make purified 2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) propane 28.61g, yellow powder, yield 71.6%.
Structural characterization is following: ir 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) 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 '-two (3-nitro-4-benzyloxy phenoxy) sulfobenzide synthetic:
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) are placed reaction flask, add the 270ml N-Methyl pyrrolidone.Nitrogen protection is stirred down, and is heated to 170 ℃ of reactions 18 hours.Pour into after the cooling in the 2500ml water, suction filtration behind the stirring 10min with 700ml washing twice, gets thick product.Thick product promptly makes purified 4,4 '-two (3-nitro-4-benzyloxy phenoxy) sulfobenzide 53.75g, yellow powder, yield 63.5% with methylene dichloride and ETHYLE ACETATE mixed solvent recrystallization.
Structural characterization is following: ir 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) 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) ditane synthetic:
With 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) place reaction flask, add the 170ml N-Methyl pyrrolidone.Nitrogen protection is stirred down, and is heated to 150 ℃ of reactions 18 hours.Pour into after the cooling in the 1500ml water, suction filtration behind the stirring 10min with 400ml washing twice, gets thick product.Thick product makes purified 4,4 '-(3-nitro-4-benzyloxy phenoxy) ditane 40.32g, yellow powder, yield 81.8% with ETHYLE ACETATE and normal hexane mixed solvent recrystallization.
Structural characterization is following: ir 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) 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-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) HFC-236fa synthetic:
With 3-nitro-4-benzyloxy chlorobenzene 40.50g (0.153mol), 2; 2-two (4-hydroxy phenyl) HFC-236fa 25.63g (0.0763mol), salt of wormwood 22.47g (0.163mol), cuprous chloride 1.76g (0.0178mol) place reaction flask, add the 170ml N-Methyl pyrrolidone.Nitrogen protection is stirred down, and is heated to 150 ℃ of reactions 18 hours.Pour into after the cooling in the 1500ml water, suction filtration behind the stirring 10min with 400ml washing twice, gets thick product.Thick product is with ETHYLE ACETATE and normal hexane mixed solvent recrystallization, make purified 2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) HFC-236fa 47.33g, yellow powder, yield 78.5%.
Structural characterization is following: ir 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) 7.83 (2H); 7.73 (2H); 7.33 (20H); 5.16 (4H); ESI-MS:m/z (M+1) 791.2.
Step IV: preparation bis-phenol two (an amino p-hydroxybenzene) ether hydrochloride (embodiment 7～10)
Embodiment 7:2,2-two (4-(3-amino-4-hydroxy phenoxy) phenyl) propane hydrochloride salt synthetic:
2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) propane 48.30g (0.071mol) places reaction flask, adds the dissolving of 800ml THF.Add 2.79g10%Pd/C, vacuumize displacement hydrogen, the maintenance hydrogen pressure is 1bar, and 25 ℃ were stirred 24 hours down.Suction filtration is removed Pd/C, steams and removes THF.With containing the 6mol/L hydrochloric acid recrystallization of massfraction 1% tindichloride, 100 ℃ of vacuum-drying 24h of gained solid, purified 2,2-two (4-(3-amino-4-hydroxy phenoxy) phenyl) propane hydrochloride salt 35.07g, yield 96.3%.
This compound 2, the essential characteristic of 2-two (4-(3-amino-4-hydroxy phenoxy) phenyl) propane hydrochloride salt: white powder, structural characterization is following: ir 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 '-two (3-amino-4-hydroxy phenoxy) sulfobenzide hydrochloride synthetic:
4,4 '-two (3-nitro-4-benzyloxy phenoxy) sulfobenzide 40.85g (0.0579mol) places reaction flask, adds the dissolving of 700ml THF.Add 2.06g10%Pd/C, vacuumize displacement hydrogen, the maintenance hydrogen pressure is 1bar, and 25 ℃ were stirred 24 hours down.Suction filtration is removed Pd/C, steams and removes THF.With the 6mol/L hydrochloric acid recrystallization that contains massfraction 1% tindichloride, 100 ℃ of vacuum-drying 24h of gained solid get purified 4,4 '-two (3-amino-4-hydroxy phenoxy) sulfobenzide hydrochloride 29.28g, yield 94.1%.
The essential characteristic of this compound 4,4 '-two (3-amino-4-hydroxy phenoxy) sulfobenzide hydrochloride: white powder, structural characterization is following: ir 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) ditane hydrochloride synthetic:
4,4 '-(3-nitro-4-benzyloxy phenoxy) ditane 40.32g (0.0617mol) places reaction flask, adds the dissolving of 800ml THF.Add 2.23g10%Pd/C, vacuumize displacement hydrogen, the maintenance hydrogen pressure is 1bar, and 25 ℃ were stirred 24 hours down.Suction filtration is removed Pd/C, steams and removes THF.With the 6mol/L hydrochloric acid recrystallization that contains massfraction 1% tindichloride, 100 ℃ of vacuum-drying 24h of gained solid get purified 4,4 '-(3-amino-4-hydroxy phenoxy) ditane hydrochloride 28.70g, yield 95.5%.
The essential characteristic of this compound 4,4 '-(3-amino-4-hydroxy phenoxy) ditane hydrochloride: white powder, structural characterization is following: ir 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-two (4-(3-amino-4-hydroxy phenoxy) phenyl) HFC-236fa hydrochloride synthetic:
2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) HFC-236fa 47.33g (0.0599mol) places reaction flask, adds the dissolving of 600ml THF.Add 2.37g10%Pd/C, vacuumize displacement hydrogen, the maintenance hydrogen pressure is 1bar, and 25 ℃ were stirred 24 hours down.Suction filtration is removed Pd/C, steams and removes THF.With containing the 6mol/L hydrochloric acid recrystallization of massfraction 1% tindichloride, 100 ℃ of vacuum-drying 24h of gained solid, purified 2,2-two (4-(3-amino-4-hydroxy phenoxy) phenyl) HFC-236fa hydrochloride 28.68g, yield 87.0%.
This compound 2, the essential characteristic of 2-two (4-(3-amino-4-hydroxy phenoxy) phenyl) HFC-236fa hydrochloride: white powder, structural characterization is following: ir 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 to be dissolved with equimolar disodium terephthalate salt, stirs a moment, separates out a large amount of white solids, and filtration drying gets 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 the dibenzoate, make that phosphorus pentoxide content is 85% in the polyphosphoric acid, and starting monomer content is 14%.Nitrogen atmosphere stirs down, 120 ℃ 4 hours, 150 ℃ 8 hours, 180 ℃ 4 hours, polybenzoxazole stoste.
Stoste is filtered the spinning top dry-jet wet spinning spinning of back with aperture 0.25mm with the G3 sand core funnel, after washing and drying, obtain polybenzoxazole fibers.Its data are following:
Table 1. gained polybenzoxazole fibers mechanics data:
annotates: literature value is from CN1709942A in the table 1, and its polybenzoxazole polymkeric substance is different with the unit of application of the present invention.
Table 2. gained polybenzoxazole fibers calorifics data:
Can know by table 1 and table 2; Prepared polybenzoxazole is compared reduction amplitude and little with document on mechanics and thermal property; Compare (about 280 ℃ of second-order transition temperature) with document CN101263180A comparatively approaching; Though the more traditional polybenzoxazole of its performance is low, but still belong to the high strength anti thermal fiber, can on intensity and thermotolerance, satisfy the requirement of most application specific IC.The prepared polybenzoxazole of the present invention simultaneously dissolves in organic solvent, is easy to follow-up machine-shaping more, thereby can produces the goods of fiber, film and other type of various different sizes.
Embodiment 12:
2, the preparation method of 2-two (4-(3-amino-4-hydroxy phenoxy) phenyl) propane hydrochloride salt comprises the following steps:
The step I: nitro is to the hydroxyl halobenzene between preparation:
To add in the reactor A the hydroxyl halobenzene, and add the methylene dichloride dissolving, wherein the ratio to hydroxyl halobenzene mmole number and methylene dichloride milliliter number is 1:1～5; Be cooled to 0～10 ℃ under the agitation condition, drip 65% concentrated nitric acid, wherein the ratio to hydroxyl halogen (halogen is Cl, Br or I) benzene mmole number and nitric acid mmole number is 1:1～1.5; Nitric acid finishes the back and stirred 2～6 hours down at 0～10 ℃, after reaction finishes, with methylene dichloride 1～3 volume multiple washing 2～3 times, uses the solvent orange 2 A recrystallization, and drying makes a nitro to the hydroxyl halobenzene;
Said recrystallization solvent A is: water, and alcohol is methyl alcohol, ethanol, Virahol, and halohydrocarbon is methylene dichloride, chloroform, ethylene dichloride, and ester is ETHYLE ACETATE, butylacetate; Ether is ether, uncle's butyl ether, ethylene glycol diethyl ether, THF, and nitrile is one or more the mixture in acetonitrile, the propionitrile;
The step II: nitro is to the benzyloxy halobenzene between preparation:
Under agitation condition, nitro between step I gained is added in the reactor B hydroxyl halobenzene and solvent B, wherein between nitro be 1:1～5 to the ratio of hydroxyl halobenzene mmole number and solvent B milliliter number; After treating that a nitro dissolves hydroxyl halogen (halogen is Cl, Br or I) benzene fully, add halo benzyl, alkali and catalyst A again, wherein between nitro be 1:1～2 to the ratio of hydroxyl halobenzene mmole number and halo benzyl mmole number; Between nitro be 1:1～5 to the ratio of hydroxyl halobenzene mmole number and alkali mmole number; Between nitro be 1:0.01～0.1 to the ratio of hydroxyl halobenzene mmole number and catalyzer mmole number; Be heated to 40～100 ℃ and stirred 2～8 hours, after reaction finished, steaming desolventized B; The water that adds solvent B total amount 0.5～2 volume multiple, a nitro is 1:0.5～2 to the ratio of hydroxyl halobenzene mmole number and water milliliter number, stirs 0.5～2 hour; Suction filtration, solids with the water washing of solvent B total amount 1～3 volume multiple 2～3 times after, use the solvent C recrystallization; Drying makes a nitro to the benzyloxy halobenzene;
Said catalyst A is selected from iodine and salt compounded of iodine, is Soiodin or potassiumiodide;
Said alkali is selected from alkali or its salt of weak acid that alkalies and alkaline earth generates, and is sodium hydroxide, Pottasium Hydroxide, hydrated barta, yellow soda ash, salt of wormwood or sodium-acetate;
Said solvent B is: ether is ether, uncle's butyl ether, ethylene glycol diethyl ether, THF; Ketone is acetone, butanone, and nitrile is acetonitrile, propionitrile, and acid amides is N; The mixture of one or more in dinethylformamide, DMAC N,N, the N-Methyl pyrrolidone;
Said recrystallization solvent C is: water, and alcohol is methyl alcohol, ethanol, Virahol, and halohydrocarbon is methylene dichloride, chloroform, ethylene dichloride, and ester is ETHYLE ACETATE, butylacetate; Ether is ether, uncle's butyl ether, ethylene glycol diethyl ether, THF, and nitrile is one or more the mixture in acetonitrile, the propionitrile;
The step III: preparation 2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) propane:
With the step II make between nitro benzyloxy halobenzene and solvent D are added among the reactor drum C, add dihydroxyphenyl propane, alkali and catalyst B again, wherein between nitro be 1:1～5 to the ratio of benzyloxy halobenzene mmole number and solvent D milliliter number; Between nitro be 1:0.2～0.5 to the ratio of benzyloxy halobenzene mmole number and dihydroxyphenyl propane mmole number; Between nitro be 1:1～5 to the ratio of benzyloxy halobenzene mmole number and alkali mmole number; Between nitro be 1:0.1～1 to the ratio of benzyloxy halobenzene mmole number and catalyst B mmole number; At nitrogen (N
2) be heated to 120～180 ℃ under the atmosphere and stirred 10～48 hours; After reaction finishes, add the water of solvent D total amount 5～10 volume multiples, suction filtration; Solids with the water washing of solvent D total amount 1～3 volume multiple 2～3 times after; With solvent E recrystallization, make 2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) propane;
Said catalyst B is selected from elemental copper and cuprous salt, is cuprous chloride, cuprous bromide or cuprous iodide;
Said alkali is selected from alkali or its salt of weak acid that alkalies and alkaline earth generates, and is in sodium hydroxide, Pottasium Hydroxide, hydrated barta, yellow soda ash, salt of wormwood, the sodium-acetate any;
Said solvent D is: acid amides is N, and dinethylformamide, DMAC N,N, N-Methyl pyrrolidone, sulfoxide are any in the methyl-sulphoxide;
Said recrystallization solvent E: water, alcohol is methyl alcohol, ethanol, Virahol, and halohydrocarbon is methylene dichloride, chloroform, ethylene dichloride, and ester is ETHYLE ACETATE, butylacetate; Ether is ether, uncle's butyl ether, ethylene glycol diethyl ether, THF, and nitrile is one or more the mixture in acetonitrile, the propionitrile;
The step IV: preparation 2,2-two (4-(3-amino-4-hydroxy phenoxy) phenyl) propane hydrochloride salt:
With the step III make 2; Dissolve with solvent F among 2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) the propane adding reactor drum D; Wherein 2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) propane mmole number is 1:10～15 with the ratio of solvent F milliliter number; Add catalyzer C again, 2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) propane quality gram number is 1:0.01～0.1 with the ratio of catalyzer C quality gram number; Hydrogen (H at 1～10bar pressure
2) under the atmosphere, stirred 10～24 hours in 25～50 ℃, 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-two (4-(3-amino-4-hydroxy phenoxy) phenyl) propane hydrochloride salt;
Said solvent F: alcohol is methyl alcohol, ethanol, Virahol, and ether is one or more the mixture in ether, the THF;
Said catalyzer C is the platinum family precious metal that is stated from the carrier, and the platinum family precious metal is palladium, platinum or rhodium, and carrier is gac, aluminum oxide or silicon oxide.
This compound 2, the essential characteristic of 2-two (4-(3-amino-4-hydroxy phenoxy) phenyl) propane hydrochloride salt: white powder, structural characterization is following: ir 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, the preparation method of 2-two (4-(3-amino-4-hydroxy phenoxy) phenyl) propane hydrochloride salt comprises the following steps:
The step I: nitro is to the hydroxyl halobenzene between preparation:
To add in the reactor A the hydroxyl halobenzene, and add the methylene dichloride dissolving, wherein the ratio to hydroxyl halobenzene mmole number and methylene dichloride milliliter number is 1:3; Be cooled to 0～10 ℃ under the agitation condition, drip 65% concentrated nitric acid, wherein the ratio to hydroxyl halogen (halogen is Cl, Br or I) benzene mmole number and nitric acid mmole number is 1:1.2; Nitric acid finishes the back and stirred 4 hours down at 0～10 ℃, after reaction finishes, with methylene dichloride 2 volume multiples washing 3 times, uses the solvent orange 2 A recrystallization, and drying makes a nitro to the hydroxyl halobenzene;
The step II: nitro is to the benzyloxy halobenzene between preparation:
Under agitation condition, nitro between step I gained is added in the reactor B hydroxyl halobenzene and solvent B, wherein between nitro be 1:3 to the ratio of hydroxyl halobenzene mmole number and solvent B milliliter number; After treating that a nitro dissolves hydroxyl halogen (halogen is Cl, Br or I) benzene fully, add halo benzyl, alkali and catalyst A again, wherein between nitro be 1:1.5 to the ratio of hydroxyl halobenzene mmole number and halo benzyl mmole number; Between nitro be 1:3 to the ratio of hydroxyl halobenzene mmole number and alkali mmole number; Between nitro be 1:0.05 to the ratio of hydroxyl halobenzene mmole number and catalyst A mmole number; Be heated to 40～100 ℃ and stirred 4 hours, after reaction finished, steaming desolventized B; The water that adds solvent B total amount 1 volume multiple, a nitro is 1:1.5 to the ratio of hydroxyl halobenzene mmole number and water milliliter number, stirs 1 hour; Suction filtration, solids with the water washing of solvent B total amount 2 volume multiples 2 times after, use the solvent C recrystallization; Drying makes a nitro to the benzyloxy halobenzene;
The step III: preparation 2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) propane:
With the step II make between nitro benzyloxy halobenzene and solvent D are added among the reactor drum C, add dihydroxyphenyl propane, alkali and catalyst B again, wherein between nitro be 1:3 to the ratio of benzyloxy halobenzene mmole number and solvent D milliliter number; Between nitro be 1:0.4 to the ratio of benzyloxy halobenzene mmole number and dihydroxyphenyl propane mmole number; Between nitro be 1:3 to the ratio of benzyloxy halobenzene mmole number and alkali mmole number; Between nitro be 1:0.5 to the ratio of benzyloxy halobenzene mmole number and catalyst B mmole number; At nitrogen (N
2) be heated to 120～180 ℃ under the atmosphere and stirred 29 hours; After reaction finishes, add the water of solvent D total amount 7 volume multiples, suction filtration; Solids with the water washing of solvent D total amount 2 volume multiples 3 times after; With solvent E recrystallization, make 2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) propane;
The step IV: preparation 2,2-two (4-(3-amino-4-hydroxy phenoxy) phenyl) propane hydrochloride salt:
With the step III make 2; Dissolve with solvent F among 2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) the propane adding reactor drum D; Wherein 2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) propane mmole number is 1:13 with the ratio of solvent F milliliter number; Add catalyzer C again, 2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) propane quality gram number is 1:0.05 with the ratio of catalyzer C quality gram number; Hydrogen (H at 1～10bar pressure
2) under the atmosphere, stirred 17 hours in 25～50 ℃, 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-two (4-(3-amino-4-hydroxy phenoxy) phenyl) propane hydrochloride salt;
Other omits with embodiment 12.
Embodiment 14:
2, the preparation method of 2-two (4-(3-amino-4-hydroxy phenoxy) phenyl) propane hydrochloride salt comprises the following steps:
The step I: nitro is to the hydroxyl halobenzene between preparation:
To add in the reactor A the hydroxyl halobenzene, and add the methylene dichloride dissolving, wherein the ratio to hydroxyl halobenzene mmole number and methylene dichloride milliliter number is 1:1; Be cooled to 0～10 ℃ under the agitation condition, drip 65% concentrated nitric acid, wherein the ratio to hydroxyl halogen (halogen is Cl, Br or I) benzene mmole number and nitric acid mmole number is 1:1; Nitric acid finishes the back and stirred 2 hours down at 0～10 ℃, after reaction finishes, with methylene dichloride 1 volume multiple washing 3 times, uses the solvent orange 2 A recrystallization, and drying makes a nitro to the hydroxyl halobenzene;
The step II: nitro is to the benzyloxy halobenzene between preparation:
Under agitation condition, nitro between step I gained is added in the reactor B hydroxyl halobenzene and solvent B, wherein between nitro be 1:1 to the ratio of hydroxyl halobenzene mmole number and solvent B milliliter number; After treating that a nitro dissolves hydroxyl halogen (halogen is Cl, Br or I) benzene fully, add halo benzyl, alkali and catalyst A again, wherein between nitro be 1:1 to the ratio of hydroxyl halobenzene mmole number and halo benzyl mmole number; Between nitro be 1:1 to the ratio of hydroxyl halobenzene mmole number and alkali mmole number; Between nitro be 1:0.01 to the ratio of hydroxyl halobenzene mmole number and catalyst A mmole number; Be heated to 40～100 ℃ and stirred 2 hours, after reaction finished, steaming desolventized B; The water that adds solvent B total amount 0.5 volume multiple, a nitro is 1:0.5 to the ratio of hydroxyl halobenzene mmole number and water milliliter number, stirs 0.5 hour; Suction filtration, solids with the water washing of solvent B total amount 1 volume multiple 2 times after, use the solvent C recrystallization; Drying makes a nitro to the benzyloxy halobenzene;
The step III: preparation 2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) propane:
With the step II make between nitro benzyloxy halobenzene and solvent D are added among the reactor drum C, add dihydroxyphenyl propane, alkali and catalyst B again, wherein between nitro be 1:1 to the ratio of benzyloxy halobenzene mmole number and solvent D milliliter number; Between nitro be 1:0.2 to the ratio of benzyloxy halobenzene mmole number and dihydroxyphenyl propane mmole number; Between nitro be 1:1 to the ratio of benzyloxy halobenzene mmole number and alkali mmole number; Between nitro be 1:0.1 to the ratio of benzyloxy halobenzene mmole number and catalyst B mmole number; At nitrogen (N
2) be heated to 120～180 ℃ under the atmosphere and stirred 10 hours; After reaction finishes, add the water of solvent D total amount 5 volume multiples, suction filtration; Solids with the water washing of solvent D total amount 1 volume multiple 2 times after; With solvent E recrystallization, make 2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) propane;
The step IV: preparation 2,2-two (4-(3-amino-4-hydroxy phenoxy) phenyl) propane hydrochloride salt:
With the step III make 2; Dissolve with solvent F among 2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) the propane adding reactor drum D; Wherein 2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) propane mmole number is 1:10 with the ratio of solvent F milliliter number; Add catalyzer C again, 2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) propane quality gram number is 1:0.01 with the ratio of catalyzer C quality gram number; Hydrogen (H at 1～10bar pressure
2) under the atmosphere, stirred 10 hours in 25～50 ℃, 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-two (4-(3-amino-4-hydroxy phenoxy) phenyl) propane hydrochloride salt;
Other omits with embodiment 12.
Embodiment 15:
2, the preparation method of 2-two (4-(3-amino-4-hydroxy phenoxy) phenyl) propane hydrochloride salt comprises the following steps:
The step I: nitro is to the hydroxyl halobenzene between preparation:
To add in the reactor A the hydroxyl halobenzene, and add the methylene dichloride dissolving, wherein the ratio to hydroxyl halobenzene mmole number and methylene dichloride milliliter number is 1:5; Be cooled to 0～10 ℃ under the agitation condition, drip 65% concentrated nitric acid, wherein the ratio to hydroxyl halogen (halogen is Cl, Br or I) benzene mmole number and nitric acid mmole number is 1:1.5; Nitric acid finishes the back and stirred 6 hours down at 0～10 ℃, after reaction finishes, with methylene dichloride 3 volume multiples washing 2 times, uses the solvent orange 2 A recrystallization, and drying makes a nitro to the hydroxyl halobenzene;
The step II: nitro is to the benzyloxy halobenzene between preparation:
Under agitation condition, nitro between step I gained is added in the reactor B hydroxyl halobenzene and solvent B, wherein between nitro be 1:5 to the ratio of hydroxyl halobenzene mmole number and solvent B milliliter number; After treating that a nitro dissolves hydroxyl halogen (halogen is Cl, Br or I) benzene fully, add halo benzyl, alkali and catalyst A again, wherein between nitro be 1:2 to the ratio of hydroxyl halobenzene mmole number and halo benzyl mmole number; Between nitro be 1:5 to the ratio of hydroxyl halobenzene mmole number and alkali mmole number; Between nitro be 1:0.1 to the ratio of hydroxyl halobenzene mmole number and catalyzer mmole number; Be heated to 40～100 ℃ and stirred 8 hours, after reaction finished, steaming desolventized B; The water that adds solvent B total amount 2 volume multiples, a nitro is 1:2 to the ratio of hydroxyl halobenzene mmole number and water milliliter number, stirs 2 hours; Suction filtration, solids with the water washing of solvent B total amount 3 volume multiples 3 times after, use the solvent C recrystallization; Drying makes a nitro to the benzyloxy halobenzene;
The step III: preparation 2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) propane:
With the step II make between nitro benzyloxy halobenzene and solvent D are added among the reactor drum C, add dihydroxyphenyl propane, alkali and catalyst B again, wherein between nitro be 1:5 to the ratio of benzyloxy halobenzene mmole number and solvent D milliliter number; Between nitro be 1:0.5 to the ratio of benzyloxy halobenzene mmole number and dihydroxyphenyl propane mmole number; Between nitro be 1:5 to the ratio of benzyloxy halobenzene mmole number and alkali mmole number; Between nitro be 1:1 to the ratio of benzyloxy halobenzene mmole number and catalyst B mmole number; At nitrogen (N
2) be heated to 120～180 ℃ under the atmosphere and stirred 48 hours; After reaction finishes, add the water of solvent D total amount 5～10 volume multiples, suction filtration; Solids with the water washing of solvent D total amount 3 volume multiples 3 times after; With solvent E recrystallization, make 2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) propane;
The step IV: preparation 2,2-two (4-(3-amino-4-hydroxy phenoxy) phenyl) propane hydrochloride salt:
With the step III make 2; Dissolve with solvent F among 2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) the propane adding reactor drum D; Wherein 2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) propane mmole number is 1:15 with the ratio of solvent F milliliter number; Add catalyzer C again, 2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) propane quality gram number is 1:0.1 with the ratio of catalyzer C quality gram number; Hydrogen (H at 1～10bar pressure
2) under the atmosphere, stirred 24 hours in 25～50 ℃, 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-two (4-(3-amino-4-hydroxy phenoxy) phenyl) propane hydrochloride salt;
Other omits with embodiment 12.
Embodiment 16:
The preparation method of 4,4 '-two (3-amino-4-hydroxy phenoxy) sulfobenzide hydrochloride comprises the following steps:
The step I: nitro is to the hydroxyl halobenzene between preparation: with arbitrary among the above-mentioned embodiment, omit;
The step II: nitro is to the benzyloxy halobenzene between preparation: with arbitrary among the above-mentioned embodiment, omit;
Step III: preparation 4,4 '-two (3-nitro-4-benzyloxy phenoxy) sulfobenzide:
Nitro between step II gained is added among the reactor drum C benzyloxy halobenzene and solvent D; Add bisphenol S, alkali and catalyst B again; Nitro is 1:4 to the ratio of benzyloxy halobenzene mmole number and solvent D milliliter number wherein, and a nitro is 1:0.4 to the ratio of benzyloxy halobenzene mmole number and bisphenol S mmole number, and a nitro is 1:4 to the ratio of benzyloxy halobenzene mmole number and alkali mmole number; Between nitro be 1:0.6 to the ratio of benzyloxy halobenzene mmole number and catalyst B mmole number, nitrogen (N
2) be heated to 120～180 ℃ under the atmosphere and stirred 30 hours, after reaction finishes, add the water of solvent D total amount 8 volume multiples; Suction filtration, solids with the water washing of solvent D total amount 2 volume multiples 3 times after, with solvent E recrystallization; Make 4,4 '-two (3-nitro-4-benzyloxy phenoxy) sulfobenzide;
Said catalyst B is selected from elemental copper and cuprous salt, is cuprous chloride, cuprous bromide or cuprous iodide;
Said alkali is selected from alkali or its salt of weak acid that alkalies and alkaline earth generates, and is in sodium hydroxide, Pottasium Hydroxide, hydrated barta, yellow soda ash, salt of wormwood, the sodium-acetate any;
Said solvent D is: acid amides is N, dinethylformamide, DMAC N,N, N-Methyl pyrrolidone; Sulfoxide is any in the methyl-sulphoxide;
Said recrystallization solvent E is: water; Alcohol is methyl alcohol, ethanol, Virahol; Halohydrocarbon is methylene dichloride, chloroform, ethylene dichloride; Ester is ETHYLE ACETATE, butylacetate, and ether is ether, uncle's butyl ether, ethylene glycol diethyl ether, THF, and nitrile is one or more the mixture in acetonitrile, the propionitrile;
Step IV: preparation 4,4 '-two (3-amino-4-hydroxy phenoxy) sulfobenzide hydrochloride:
With dissolving with solvent F among step III gained 4,4 '-two (3-nitro-4-benzyloxy phenoxy) the sulfobenzide adding reactor drum D, wherein 4,4 '-two (3-nitro-4-benzyloxy phenoxy) sulfobenzide mmole number is 1:13 with the ratio of solvent F milliliter number; Add catalyzer C again, 4,4 '-two (3-nitro-4-benzyloxy phenoxy) sulfobenzide quality gram number is 1:0.06 with the ratio of catalyzer C quality gram number; Hydrogen (the H of 1～10bar pressure
2) under the atmosphere, 25～50 ℃ were stirred 18 hours; After reaction finishes, filtration catalizer C, steaming 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 get 4,4 '-two (3-amino-4-hydroxy phenoxy) sulfobenzide hydrochloride;
Said solvent F is: alcohol is methyl alcohol, ethanol, Virahol, and ether is one or more the mixture in ether, the THF;
Said catalyzer C is the platinum family precious metal that is stated from the carrier, and the 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 '-two (3-amino-4-hydroxy phenoxy) sulfobenzide hydrochloride: white powder, structural characterization is following: ir 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 '-two (3-amino-4-hydroxy phenoxy) sulfobenzide hydrochloride comprises the following steps:
The step I: nitro is to the hydroxyl halobenzene between preparation: with arbitrary among the above-mentioned embodiment, omit;
The step II: nitro is to the benzyloxy halobenzene between preparation: with arbitrary among the above-mentioned embodiment, omit;
Step III: preparation 4,4 '-two (3-nitro-4-benzyloxy phenoxy) sulfobenzide:
Nitro between step II gained is added among the reactor drum C benzyloxy halobenzene and solvent D; Add bisphenol S, alkali and catalyst B again; Nitro is 1:1 to the ratio of benzyloxy halobenzene mmole number and solvent D milliliter number wherein, and a nitro is 1:0.2 to the ratio of benzyloxy halobenzene mmole number and bisphenol S mmole number, and a nitro is 1:1 to the ratio of benzyloxy halobenzene mmole number and alkali mmole number; Between nitro be 1:0.1 to the ratio of benzyloxy halobenzene mmole number and catalyst B mmole number, nitrogen (N
2) be heated to 120～180 ℃ under the atmosphere and stirred 10 hours, after reaction finishes, add the water of solvent D total amount 5 volume multiples; Suction filtration, solids with the water washing of solvent D total amount 1 volume multiple 2 times after, with solvent E recrystallization; Make 4,4 '-two (3-nitro-4-benzyloxy phenoxy) sulfobenzide;
Step IV: preparation 4,4 '-two (3-amino-4-hydroxy phenoxy) sulfobenzide hydrochloride:
With dissolving with solvent F among step III gained 4,4 '-two (3-nitro-4-benzyloxy phenoxy) the sulfobenzide adding reactor drum D, wherein 4,4 '-two (3-nitro-4-benzyloxy phenoxy) sulfobenzide mmole number is 1:10 with the ratio of solvent F milliliter number; Add catalyzer C again, 4,4 '-two (3-nitro-4-benzyloxy phenoxy) sulfobenzide quality gram number is 1:0.01 with the ratio of catalyzer C quality gram number; Hydrogen (the H of 1～10bar pressure
2) under the atmosphere, 25～50 ℃ were stirred 10 hours; After reaction finishes, filtration catalizer C, steaming 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 get 4,4 '-two (3-amino-4-hydroxy phenoxy) sulfobenzide hydrochloride;
Other omits with embodiment 16.
Embodiment 18:
The preparation method of 4,4 '-two (3-amino-4-hydroxy phenoxy) sulfobenzide hydrochloride comprises the following steps:
The step I: nitro is to the hydroxyl halobenzene between preparation: with arbitrary among the above-mentioned embodiment, omit;
The step II: nitro is to the benzyloxy halobenzene between preparation: with arbitrary among the above-mentioned embodiment, omit;
Step III: preparation 4,4 '-two (3-nitro-4-benzyloxy phenoxy) sulfobenzide:
Nitro between step II gained is added among the reactor drum C benzyloxy halobenzene and solvent D; Add bisphenol S, alkali and catalyst B again; Nitro is 1:5 to the ratio of benzyloxy halobenzene mmole number and solvent D milliliter number wherein, and a nitro is 1:0.5 to the ratio of benzyloxy halobenzene mmole number and bisphenol S mmole number, and a nitro is 1:5 to the ratio of benzyloxy halobenzene mmole number and alkali mmole number; Between nitro be 1:1 to the ratio of benzyloxy halobenzene mmole number and catalyst B mmole number, nitrogen (N
2) be heated to 120～180 ℃ under the atmosphere and stirred 48 hours, after reaction finishes, add the water of solvent D total amount 10 volume multiples; Suction filtration, solids with the water washing of solvent D total amount 3 volume multiples 3 times after, with solvent E recrystallization; Make 4,4 '-two (3-nitro-4-benzyloxy phenoxy) sulfobenzide;
Step IV: preparation 4,4 '-two (3-amino-4-hydroxy phenoxy) sulfobenzide hydrochloride:
With dissolving with solvent F among step III gained 4,4 '-two (3-nitro-4-benzyloxy phenoxy) the sulfobenzide adding reactor drum D, wherein 4,4 '-two (3-nitro-4-benzyloxy phenoxy) sulfobenzide mmole number is 1:15 with the ratio of solvent F milliliter number; Add catalyzer C again, 4,4 '-two (3-nitro-4-benzyloxy phenoxy) sulfobenzide quality gram number is 1:0.1 with the ratio of catalyzer C quality gram number; Hydrogen (the H of 1～10bar pressure
2) under the atmosphere, 25～50 ℃ were stirred 10～24 hours; After reaction finishes, filtration catalizer C, steaming 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 get 4,4 '-two (3-amino-4-hydroxy phenoxy) sulfobenzide hydrochloride;
Other omits with embodiment 16.
Embodiment 19:
The preparation method of 4,4 '-two (3-amino-4-hydroxy phenoxy) sulfobenzide hydrochloride comprises the following steps:
The step I: nitro is to the hydroxyl halobenzene between preparation: with arbitrary among the above-mentioned embodiment, omit;
The step II: nitro is to the benzyloxy halobenzene between preparation: with arbitrary among the above-mentioned embodiment, omit;
Step III: preparation 4,4 '-two (3-nitro-4-benzyloxy phenoxy) sulfobenzide:
Nitro between step II gained is added among the reactor drum C benzyloxy halobenzene and solvent D; Add bisphenol S, alkali and catalyst B again; Nitro is 1:1～5 to the ratio of benzyloxy halobenzene mmole number and solvent D milliliter number wherein; Between nitro be 1:0.2～0.5 to the ratio of benzyloxy halobenzene mmole number and bisphenol S mmole number; Between nitro be 1:1～5 to the ratio of benzyloxy halobenzene mmole number and alkali mmole number, a nitro is 1:0.1～1 to the ratio of benzyloxy halobenzene mmole number and catalyst B mmole number, nitrogen (N
2) be heated to 120～180 ℃ under the atmosphere and stirred 10～48 hours; After reaction finishes, add the water of solvent D total amount 5～10 volume multiples, suction filtration; Solids with the water washing of solvent D total amount 1～3 volume multiple 2～3 times after; With solvent E recrystallization, make 4,4 '-two (3-nitro-4-benzyloxy phenoxy) sulfobenzide;
Step IV: preparation 4,4 '-two (3-amino-4-hydroxy phenoxy) sulfobenzide hydrochloride:
With dissolving with solvent F among step III gained 4,4 '-two (3-nitro-4-benzyloxy phenoxy) the sulfobenzide adding reactor drum D, wherein 4,4 '-two (3-nitro-4-benzyloxy phenoxy) sulfobenzide mmole number is 1:10～15 with the ratio of solvent F milliliter number; Add catalyzer C again, 4,4 '-two (3-nitro-4-benzyloxy phenoxy) sulfobenzide quality gram number is 1:0.01～0.1 with the ratio of catalyzer C quality gram number; Hydrogen (the H of 1～10bar pressure
2) under the atmosphere, 25～50 ℃ were stirred 10～24 hours; After reaction finishes, filtration catalizer C, steaming 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 get 4,4 '-two (3-amino-4-hydroxy phenoxy) sulfobenzide hydrochloride;
Other omits with embodiment 16.
Embodiment 20:
The preparation method of 4,4 '-(3-amino-4-hydroxy phenoxy) ditane hydrochloride comprises the following steps:
The step I: nitro is to the hydroxyl halobenzene between preparation: with arbitrary among the above-mentioned embodiment, omit;
The step II: nitro is to the benzyloxy halobenzene between preparation: with arbitrary among the above-mentioned embodiment, omit;
Step III: preparation 4,4 '-(3-nitro-4-benzyloxy phenoxy) ditane:
Nitro between step II gained is added among the reactor drum C benzyloxy halobenzene and solvent D, adds Bisphenol F, alkali and catalyst B again, wherein between nitro be 1:1～5 to the ratio of benzyloxy halobenzene mmole number and solvent D milliliter number; Between nitro be 1:0.2～0.5 to the ratio of benzyloxy halobenzene mmole number and Bisphenol F mmole number; Between nitro be 1:1～5 to the ratio of benzyloxy halobenzene mmole number and alkali mmole number; Between nitro be 1:0.1～1 to the ratio of benzyloxy halobenzene mmole and catalyst B mmole number; Nitrogen (N
2) be heated to 120～180 ℃ under the atmosphere and stirred 10～48 hours; After reaction finishes, add the water of solvent D total amount 5～10 volume multiples, suction filtration; Solids with the water washing of solvent D total amount 1～3 volume multiple 2～3 times after; With solvent E recrystallization, make 4,4 '-(3-nitro-4-benzyloxy phenoxy) ditane;
Said catalyst B is selected from elemental copper and cuprous salt, is cuprous chloride, cuprous bromide or cuprous iodide;
Said alkali is selected from alkali or its salt of weak acid that alkalies and alkaline earth generates, and is in sodium hydroxide, Pottasium Hydroxide, hydrated barta, yellow soda ash, salt of wormwood, the sodium-acetate any;
Said solvent D is: acid amides is N, and dinethylformamide, DMAC N,N, N-Methyl pyrrolidone, sulfoxide are any in the methyl-sulphoxide;
Said recrystallization solvent E is: water, and alcohol is methyl alcohol, ethanol, Virahol, and halohydrocarbon is methylene dichloride, chloroform, ethylene dichloride, and ester is ETHYLE ACETATE, butylacetate; Ether is ether, uncle's butyl ether, ethylene glycol diethyl ether, THF, and nitrile is one or more the mixture in acetonitrile, the propionitrile;
Step IV: preparation 4,4 '-(3-amino-4-hydroxy phenoxy) ditane hydrochloride:
4,4 '-(3-nitro-4-benzyloxy phenoxy) ditane that the step III is made adds among the reactor drum D and dissolves with solvent F, and wherein 4,4 '-(3-nitro-4-benzyloxy phenoxy) ditane mmole number is 1:10～15 with the ratio of solvent F milliliter number; Add catalyzer C again, 4,4 '-(3-nitro-4-benzyloxy phenoxy) ditane quality gram (g) number is 1:0.01～0.1 with the ratio of catalyzer C quality gram number; Hydrogen (the H of 1～10bar pressure
2) under the atmosphere, 25～50 ℃ were stirred 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 4,4 '-(3-amino-4-hydroxy phenoxy) ditane hydrochloride;
Said solvent F is: alcohol is methyl alcohol, ethanol, Virahol, and ether is one or more the mixture in ether, the THF;
Said catalyzer C is selected from the platinum family precious metal that is stated from the carrier, and the 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) ditane hydrochloride: white powder, structural characterization is following: ir 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) ditane hydrochloride comprises the following steps:
The step I: nitro is to the hydroxyl halobenzene between preparation: with arbitrary among the above-mentioned embodiment, omit;
The step II: nitro is to the benzyloxy halobenzene between preparation: with arbitrary among the above-mentioned embodiment, omit;
Step III: preparation 4,4 '-(3-nitro-4-benzyloxy phenoxy) ditane:
Nitro between step II gained is added among the reactor drum C benzyloxy halobenzene and solvent D, adds Bisphenol F, alkali and catalyst B again, wherein between nitro be 1:3 to the ratio of benzyloxy halobenzene mmole number and solvent D milliliter number; Between nitro be 1:0.35 to the ratio of benzyloxy halobenzene mmole number and Bisphenol F mmole number; Between nitro be 1:3 to the ratio of benzyloxy halobenzene mmole number and alkali mmole number; Between nitro be 1:0.6 to the ratio of benzyloxy halobenzene mmole and catalyst B mmole number; Nitrogen (N
2) be heated to 120～180 ℃ under the atmosphere and stirred 29 hours, after reaction finishes, add the water of solvent D total amount 7 volume multiples; Suction filtration, solids with the water washing of solvent D total amount 2 volume multiples 2 times after, with solvent E recrystallization; Make 4,4 '-(3-nitro-4-benzyloxy phenoxy) ditane;
Step IV: preparation 4,4 '-(3-amino-4-hydroxy phenoxy) ditane hydrochloride:
4,4 '-(3-nitro-4-benzyloxy phenoxy) ditane that the step III is made adds among the reactor drum D and dissolves with solvent F, and wherein 4,4 '-(3-nitro-4-benzyloxy phenoxy) ditane mmole number is 1:12.5 with the ratio of solvent F milliliter number; Add catalyzer C again, 4,4 '-(3-nitro-4-benzyloxy phenoxy) ditane quality gram (g) number is 1:0.06 with the ratio of catalyzer C quality gram number; Hydrogen (the H of 1～10bar pressure
2) under the atmosphere, 25～50 ℃ were stirred 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 4,4 '-(3-amino-4-hydroxy phenoxy) ditane hydrochloride;
Other omits with embodiment 20.
Embodiment 22:
The preparation method of 4,4 '-(3-amino-4-hydroxy phenoxy) ditane hydrochloride comprises the following steps:
The step I: nitro is to the hydroxyl halobenzene between preparation: with arbitrary among the above-mentioned embodiment, omit;
The step II: nitro is to the benzyloxy halobenzene between preparation: with arbitrary among the above-mentioned embodiment, omit;
Step III: preparation 4,4 '-(3-nitro-4-benzyloxy phenoxy) ditane:
Nitro between step II gained is added among the reactor drum C benzyloxy halobenzene and solvent D, adds Bisphenol F, alkali and catalyst B again, wherein between nitro be 1:1 to the ratio of benzyloxy halobenzene mmole number and solvent D milliliter number; Between nitro be 1:0.2 to the ratio of benzyloxy halobenzene mmole number and Bisphenol F mmole number; Between nitro be 1:1 to the ratio of benzyloxy halobenzene mmole number and alkali mmole number; Between nitro be 1:0.1 to the ratio of benzyloxy halobenzene mmole and catalyst B mmole number; Nitrogen (N
2) be heated to 120～180 ℃ under the atmosphere and stirred 10 hours, after reaction finishes, add the water of solvent D total amount 5 volume multiples; Suction filtration, solids with the water washing of solvent D total amount 1 volume multiple 2 times after, with solvent E recrystallization; Make 4,4 '-(3-nitro-4-benzyloxy phenoxy) ditane;
Step IV: preparation 4,4 '-(3-amino-4-hydroxy phenoxy) ditane hydrochloride:
4,4 '-(3-nitro-4-benzyloxy phenoxy) ditane that the step III is made adds among the reactor drum D and dissolves with solvent F, and wherein 4,4 '-(3-nitro-4-benzyloxy phenoxy) ditane mmole number is 1:10 with the ratio of solvent F milliliter number; Add catalyzer C again, 4,4 '-(3-nitro-4-benzyloxy phenoxy) ditane quality gram (g) number is 1:0.01 with the ratio of catalyzer C quality gram number; Hydrogen (the H of 1～10bar pressure
2) under the atmosphere, 25～50 ℃ were stirred 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 4,4 '-(3-amino-4-hydroxy phenoxy) ditane hydrochloride;
Other omits with embodiment 20.
Embodiment 23:
The preparation method of 4,4 '-(3-amino-4-hydroxy phenoxy) ditane hydrochloride comprises the following steps:
The step I: nitro is to the hydroxyl halobenzene between preparation: with arbitrary among the above-mentioned embodiment, omit;
The step II: nitro is to the benzyloxy halobenzene between preparation: with arbitrary among the above-mentioned embodiment, omit;
Step III: preparation 4,4 '-(3-nitro-4-benzyloxy phenoxy) ditane:
Nitro between step II gained is added among the reactor drum C benzyloxy halobenzene and solvent D, adds Bisphenol F, alkali and catalyst B again, wherein between nitro be 1:5 to the ratio of benzyloxy halobenzene mmole number and solvent D milliliter number; Between nitro be 1:0.5 to the ratio of benzyloxy halobenzene mmole number and Bisphenol F mmole number; Between nitro be 1:5 to the ratio of benzyloxy halobenzene mmole number and alkali mmole number; Between nitro be 1:1 to the ratio of benzyloxy halobenzene mmole and catalyst B mmole number; Nitrogen (N
2) be heated to 120～180 ℃ under the atmosphere and stirred 48 hours, after reaction finishes, add the water of solvent D total amount 10 volume multiples; Suction filtration, solids with the water washing of solvent D total amount 3 volume multiples 3 times after, with solvent E recrystallization; Make 4,4 '-(3-nitro-4-benzyloxy phenoxy) ditane;
Step IV: preparation 4,4 '-(3-amino-4-hydroxy phenoxy) ditane hydrochloride:
4,4 '-(3-nitro-4-benzyloxy phenoxy) ditane that the step III is made adds among the reactor drum D and dissolves with solvent F, and wherein 4,4 '-(3-nitro-4-benzyloxy phenoxy) ditane mmole number is 1:15 with the ratio of solvent F milliliter number; Add catalyzer C again, 4,4 '-(3-nitro-4-benzyloxy phenoxy) ditane quality gram (g) number is 1:0.1 with the ratio of catalyzer C quality gram number; Hydrogen (the H of 1～10bar pressure
2) under the atmosphere, 25～50 ℃ were stirred 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 4,4 '-(3-amino-4-hydroxy phenoxy) ditane hydrochloride;
Other omits with embodiment 20.
Embodiment 24:
2, the preparation method of 2-two (4-(3-amino-4-hydroxy phenoxy) phenyl) HFC-236fa hydrochloride comprises the following steps:
The step I: nitro is to the hydroxyl halobenzene between preparation: with arbitrary among the above-mentioned embodiment, omit;
The step II: nitro is to the benzyloxy halobenzene between preparation: with arbitrary among the above-mentioned embodiment, omit;
The step III: preparation 2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) HFC-236fa:
Nitro between step II gained is added among the reactor drum C benzyloxy halobenzene and solvent D, adds bisphenol AF, alkali and catalyst B again, wherein between nitro be 1:1～5 to the ratio of benzyloxy halobenzene mmole number and solvent D milliliter number; Between nitro be 1:0.2～0.5 to the ratio of benzyloxy halobenzene mmole number and bisphenol AF mmole number; Between nitro be 1:1～5 to the ratio of benzyloxy halobenzene mmole number and alkali mmole number; Between nitro be 1:0.1～1 to the ratio of benzyloxy halobenzene mmole number and catalyst B mmole number; Nitrogen (N
2) be heated to 120～180 ℃ under the atmosphere and stirred 10～48 hours; After reaction finishes, add the water of solvent D total amount 5～10 volume multiples, suction filtration; Solids with the water washing of solvent D total amount 1～3 volume multiple 2～3 times after; With solvent E recrystallization, make 2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) HFC-236fa;
Said catalyst B is selected from elemental copper and cuprous salt, is cuprous chloride, cuprous bromide or cuprous iodide;
Said alkali is selected from alkali or its salt of weak acid that alkalies and alkaline earth generates, and is in sodium hydroxide, Pottasium Hydroxide, hydrated barta, yellow soda ash, salt of wormwood, the sodium-acetate any;
Said solvent D is: acid amides is N, and dinethylformamide, DMAC N,N, N-Methyl pyrrolidone, sulfoxide are any in the methyl-sulphoxide;
Said recrystallization solvent E is: water; Alcohol is methyl alcohol, ethanol, Virahol; Halohydrocarbon is methylene dichloride, chloroform, ethylene dichloride; Ester is ETHYLE ACETATE, butylacetate, and ether is ether, uncle's butyl ether, ethylene glycol diethyl ether, THF, and nitrile is one or more the mixture in acetonitrile, the propionitrile;
The step IV: preparation 2,2-two (4-(3-amino-4-hydroxy phenoxy) phenyl) HFC-236fa hydrochloride:
With the step III make 2; Dissolve with solvent F among 2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) the HFC-236fa adding reactor drum D; Wherein 2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) HFC-236fa mmole (mmol) number is 1:10～15 with the ratios of solvent F milliliter (ml) number; Add catalyzer C again, 2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) HFC-236fa quality gram (g) number is 1:0.01～0.1 with the ratio of catalyzer C quality gram (g) number; Hydrogen (H at 1～10bar pressure
2) under the atmosphere, stirred 10～24 hours in 25～50 ℃, 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-two (4-(3-amino-4-hydroxy phenoxy) phenyl) HFC-236fa hydrochloride;
Said solvent F is: alcohol is methyl alcohol, ethanol, Virahol, and ether is one or more the mixture in ether, the THF;
Said catalyzer C is selected from the platinum family precious metal that is stated from the carrier, and the platinum family precious metal is palladium, platinum or rhodium, and suitable carrier is gac, aluminum oxide or silicon oxide.
This compound 2, the essential characteristic of 2-two (4-(3-amino-4-hydroxy phenoxy) phenyl) HFC-236fa hydrochloride: white powder, structural characterization is following: ir 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, the preparation method of 2-two (4-(3-amino-4-hydroxy phenoxy) phenyl) HFC-236fa hydrochloride comprises the following steps:
The step I: nitro is to the hydroxyl halobenzene between preparation: with arbitrary among the above-mentioned embodiment, omit;
The step II: nitro is to the benzyloxy halobenzene between preparation: with arbitrary among the above-mentioned embodiment, omit;
The step III: preparation 2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) HFC-236fa:
Nitro between step II gained is added among the reactor drum C benzyloxy halobenzene and solvent D, adds bisphenol AF, alkali and catalyst B again, wherein between nitro be 1:3 to the ratio of benzyloxy halobenzene mmole number and solvent D milliliter number; Between nitro be 1:0.3 to the ratio of benzyloxy halobenzene mmole number and bisphenol AF mmole number; Between nitro be 1:3 to the ratio of benzyloxy halobenzene mmole number and alkali mmole number; Between nitro be 1:0.6 to the ratio of benzyloxy halobenzene mmole number and catalyst B mmole number; Nitrogen (N
2) be heated to 120～180 ℃ under the atmosphere and stirred 28 hours; After reaction finishes, add the water of solvent D total amount 7 volume multiples, suction filtration; Solids with the water washing of solvent D total amount 2 volume multiples 3 times after; With solvent E recrystallization, make 2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) HFC-236fa;
The step IV: preparation 2,2-two (4-(3-amino-4-hydroxy phenoxy) phenyl) HFC-236fa hydrochloride:
With the step III make 2; Dissolve with solvent F among 2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) the HFC-236fa adding reactor drum D; Wherein 2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) HFC-236fa mmole number is 1:12 with the ratio of solvent F milliliter number; Add catalyzer C again, 2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) HFC-236fa quality gram (g) number is 1:0.05 with the ratio of catalyzer C quality gram (g) number; Hydrogen (H at 1～10bar pressure
2) under the atmosphere, stirred 16 hours in 25～50 ℃, 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-two (4-(3-amino-4-hydroxy phenoxy) phenyl) HFC-236fa hydrochloride;
Other omits with embodiment 24.
Embodiment 26:
2, the preparation method of 2-two (4-(3-amino-4-hydroxy phenoxy) phenyl) HFC-236fa hydrochloride comprises the following steps:
The step I: nitro is to the hydroxyl halobenzene between preparation: with arbitrary among the above-mentioned embodiment, omit;
The step II: nitro is to the benzyloxy halobenzene between preparation: with arbitrary among the above-mentioned embodiment, omit;
The step III: preparation 2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) HFC-236fa:
Nitro between step II gained is added among the reactor drum C benzyloxy halobenzene and solvent D, adds bisphenol AF, alkali and catalyst B again, wherein between nitro be 1:1 to the ratio of benzyloxy halobenzene mmole number and solvent D milliliter number; Between nitro be 1:0.2 to the ratio of benzyloxy halobenzene mmole number and bisphenol AF mmole number; Between nitro be 1:1 to the ratio of benzyloxy halobenzene mmole number and alkali mmole number; Between nitro be 1:0.1 to the ratio of benzyloxy halobenzene mmole number and catalyst B mmole number; Nitrogen (N
2) be heated to 120～180 ℃ under the atmosphere and stirred 10 hours; After reaction finishes, add the water of solvent D total amount 5 volume multiples, suction filtration; Solids with the water washing of solvent D total amount 1 volume multiple 2 times after; With solvent E recrystallization, make 2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) HFC-236fa;
The step IV: preparation 2,2-two (4-(3-amino-4-hydroxy phenoxy) phenyl) HFC-236fa hydrochloride:
With the step III make 2; Dissolve with solvent F among 2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) the HFC-236fa adding reactor drum D; Wherein 2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) HFC-236fa mmole number is 1:10 with the ratio of solvent F milliliter number; Add catalyzer C again, 2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) HFC-236fa quality gram (g) number is 1:0.01 with the ratio of catalyzer C quality gram (g) number; Hydrogen (H at 1～10bar pressure
2) under the atmosphere, stirred 10 hours in 25～50 ℃, 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-two (4-(3-amino-4-hydroxy phenoxy) phenyl) HFC-236fa hydrochloride;
Other omits with embodiment 24.
Embodiment 27:
2, the preparation method of 2-two (4-(3-amino-4-hydroxy phenoxy) phenyl) HFC-236fa hydrochloride comprises the following steps:
The step I: nitro is to the hydroxyl halobenzene between preparation: with arbitrary among the above-mentioned embodiment, omit;
The step II: nitro is to the benzyloxy halobenzene between preparation: with arbitrary among the above-mentioned embodiment, omit;
The step III: preparation 2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) HFC-236fa:
Nitro between step II gained is added among the reactor drum C benzyloxy halobenzene and solvent D, adds bisphenol AF, alkali and catalyst B again, wherein between nitro be 1:5 to the ratio of benzyloxy halobenzene mmole number and solvent D milliliter number; Between nitro be 1:0.5 to the ratio of benzyloxy halobenzene mmole number and bisphenol AF mmole number; Between nitro be 1:5 to the ratio of benzyloxy halobenzene mmole number and alkali mmole number; Between nitro be 1:1 to the ratio of benzyloxy halobenzene mmole number and catalyst B mmole number; Nitrogen (N
2) be heated to 120～180 ℃ under the atmosphere and stirred 48 hours; After reaction finishes, add the water of solvent D total amount 10 volume multiples, suction filtration; Solids with the water washing of solvent D total amount 3 volume multiples 3 times after; With solvent E recrystallization, make 2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) HFC-236fa;
The step IV: preparation 2,2-two (4-(3-amino-4-hydroxy phenoxy) phenyl) HFC-236fa hydrochloride:
With the step III make 2; Dissolve with solvent F among 2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) the HFC-236fa adding reactor drum D; Wherein 2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) HFC-236fa mmole number is 1:15 with the ratio of solvent F milliliter number; Add catalyzer C again, 2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) HFC-236fa quality gram (g) number is 1:0.1 with the ratio of catalyzer C quality gram (g) number; Hydrogen (H at 1～10bar pressure
2) under the atmosphere, stirred 24 hours in 25～50 ℃, 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-two (4-(3-amino-4-hydroxy phenoxy) phenyl) HFC-236fa hydrochloride;
Other omits with embodiment 24.
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 preparation soluble poly benzoxazole.
The fiber yarn fiber number that the novel polyphenyl Bing oxazole processing that bis-phenol two (an amino p-hydroxybenzene) ether hydrochloride that is made by the present invention prepares 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 10% thermal weight loss temperature is about 450 ℃ in the nitrogen.Be dissolvable in water organic solvents such as N simultaneously, be easy to be processed as variant prodn.
In the foregoing description: each raw material that is adopted is the commercially available prod.
In the foregoing description: in the percentage that is adopted, do not indicate especially, be the mass percent example; Said mass parts can all be gram or kilogram.
In the foregoing description: 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 narrating of technology contents in content of the present invention and the foregoing description.
The invention is not restricted to the foregoing description, content of the present invention is said all can implement and have said good result.
Claims (9)
1.2 2-two (4-(3-amino-4-hydroxy phenoxy) phenyl) propane hydrochloride salt is characterized in that this compound has the chemical structural formula of formula I:
（Ⅰ）。
2. said 2 by claim 1, the preparation method of 2-two (4-(3-amino-4-hydroxy phenoxy) phenyl) propane hydrochloride salt is characterized in that comprising the following steps:
The step I: nitro is to the hydroxyl halobenzene between preparation:
To add in the reactor A the hydroxyl halobenzene, and add the methylene dichloride dissolving, wherein the ratio to hydroxyl halobenzene mmole number and methylene dichloride milliliter number is 1:1～5; Be cooled to 0～10 ℃ under the agitation condition, drip 65% concentrated nitric acid, wherein the ratio to hydroxyl halobenzene mmole number and nitric acid mmole number is 1:1～1.5; Nitric acid finishes the back and stirred 2～6 hours down at 0～10 ℃, after reaction finishes, with methylene dichloride 1～3 volume multiple washing 2～3 times, uses the solvent orange 2 A recrystallization, and drying makes a nitro to the hydroxyl halobenzene;
Saidly be to hydroxyl halobenzene structure:
X is in the formula: Cl, Br or I;
Said recrystallization solvent A is: the mixture of one or more in water, methyl alcohol, ethanol, Virahol, methylene dichloride, chloroform, ethylene dichloride, ETHYLE ACETATE, butylacetate, ether, uncle's butyl ether, ethylene glycol diethyl ether, THF, acetonitrile, the propionitrile;
The step II: nitro is to the benzyloxy halobenzene between preparation:
Under agitation condition, nitro between step I gained is added in the reactor B hydroxyl halobenzene and solvent B, wherein between nitro be 1:1～5 to the ratio of hydroxyl halobenzene mmole number and solvent B milliliter number; After treating that a nitro dissolves the hydroxyl halobenzene fully, add halo benzyl, alkali and catalyst A again, wherein between nitro be 1:1～2 to the ratio of hydroxyl halobenzene mmole number and halo benzyl mmole number; Between nitro be 1:1～5 to the ratio of hydroxyl halobenzene mmole number and alkali mmole number; Between nitro be 1:0.01～0.1 to the ratio of hydroxyl halobenzene mmole number and catalyst A mmole number; Be heated to 40～100 ℃ and stirred 2～8 hours, after reaction finished, steaming desolventized B; The water that adds solvent B total amount 0.5～2 volume multiple, a nitro is 1:0.5～2 to the ratio of hydroxyl halobenzene mmole number and water milliliter number, stirs 0.5～2 hour; Suction filtration, solids with the water washing of solvent B total amount 1～3 volume multiple 2～3 times after, use the solvent C recrystallization; Drying makes a nitro to the benzyloxy halobenzene;
Said nitro to the chemical structural formula of hydroxyl halobenzene is:
X is in the formula: Cl, Br or I;
Said catalyst A is Soiodin or potassiumiodide;
Said alkali is sodium hydroxide, Pottasium Hydroxide, hydrated barta, yellow soda ash, salt of wormwood or sodium-acetate;
Said solvent B is: ether, uncle's butyl ether, ethylene glycol diethyl ether, THF, acetone, butanone, be acetonitrile, propionitrile, N, the mixture of one or more in dinethylformamide, DMAC N,N, the N-Methyl pyrrolidone;
Said recrystallization solvent C is: the mixture of one or more in water, methyl alcohol, ethanol, Virahol, methylene dichloride, chloroform, ethylene dichloride, ETHYLE ACETATE, butylacetate, ether, uncle's butyl ether, ethylene glycol diethyl ether, THF, acetonitrile, the propionitrile;
The step III: preparation 2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) propane:
With the step II make between nitro benzyloxy halobenzene and solvent D are added among the reactor drum C, add dihydroxyphenyl propane, alkali and catalyst B again, wherein between nitro be 1:1～5 to the ratio of benzyloxy halobenzene mmole number and solvent D milliliter number; Between nitro be 1:0.2～0.5 to the ratio of benzyloxy halobenzene mmole number and dihydroxyphenyl propane mmole number; Between nitro be 1:1～5 to the ratio of benzyloxy halobenzene mmole number and alkali mmole number; Between nitro be 1:0.1～1 to the ratio of benzyloxy halobenzene mmole number and catalyzer mmole number; At nitrogen (N
2) be heated to 120～180 ℃ under the atmosphere and stirred 10～48 hours; After reaction finishes, add the water of solvent D total amount 5～10 volume multiples, suction filtration; Solids with the water washing of solvent D total amount 1～3 volume multiple 2～3 times after; With solvent E recrystallization, make 2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) propane;
Said catalyst B is cuprous chloride, cuprous bromide or cuprous iodide;
Said alkali is any in sodium hydroxide, Pottasium Hydroxide, hydrated barta, yellow soda ash, salt of wormwood, the sodium-acetate;
Said solvent D is: N, any in dinethylformamide, DMAC N,N, N-Methyl pyrrolidone, the methyl-sulphoxide;
Said recrystallization solvent E: the mixture of one or more in water, methyl alcohol, ethanol, Virahol, methylene dichloride, chloroform, ethylene dichloride, ETHYLE ACETATE, butylacetate, ether, uncle's butyl ether, ethylene glycol diethyl ether, THF, acetonitrile, the propionitrile;
Step IV: preparation 2,2-two (4-(3-amino-4-hydroxy phenoxy) phenyl) propane hydrochloride salt;
With the step III make 2; Dissolve with solvent F among 2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) the propane adding reactor drum D; Wherein 2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) propane mmole number is 1:10～15 with the ratio of solvent F milliliter number; Add catalyzer C again, 2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) propane quality gram number is 1:0.01～0.1 with the ratio of catalyzer C quality gram number; Hydrogen (H at 1～10bar pressure
2) under the atmosphere, stirred 10～24 hours in 25～50 ℃, 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; Get 2,2-two (4-(3-amino-4-hydroxy phenoxy) phenyl) propane hydrochloride salt;
Said solvent F:, one or more the mixture in the methyl alcohol, ethanol, Virahol, ether, THF;
Said catalyzer C is the platinum family precious metal that is stated from the carrier, and the platinum family precious metal is palladium, platinum or rhodium, and carrier is gac, aluminum oxide or silicon oxide.
3.4 4 '-two (3-amino-4-hydroxy phenoxy) sulfobenzide hydrochloride is characterized in that this compound has the chemical structural formula of formula II:
（Ⅱ）。
4. by the preparation method of claim 3 said 4,4 '-two (3-amino-4-hydroxy phenoxy) sulfobenzide hydrochloride, it is characterized in that comprising the following steps:
The step I: nitro is to the hydroxyl halobenzene between preparation:
To add in the reactor A the hydroxyl halobenzene, and add the methylene dichloride dissolving, wherein the ratio to hydroxyl halobenzene mmole number and methylene dichloride milliliter number is 1:1～5; Be cooled to 0～10 ℃ under the agitation condition, drip 65% concentrated nitric acid, wherein the ratio to hydroxyl halobenzene mmole number and nitric acid mmole number is 1:1～1.5; Nitric acid finishes the back and stirred 2～6 hours down at 0～10 ℃, after reaction finishes, with methylene dichloride 1～3 volume multiple washing 2～3 times, uses the solvent orange 2 A recrystallization, and drying makes a nitro to the hydroxyl halobenzene;
Saidly be to hydroxyl halobenzene structure:
X is in the formula: Cl, Br or I;
Said recrystallization solvent A is: the mixture of one or more in water, methyl alcohol, ethanol, Virahol, methylene dichloride, chloroform, ethylene dichloride, ETHYLE ACETATE, butylacetate, ether, uncle's butyl ether, ethylene glycol diethyl ether, THF, acetonitrile, the propionitrile;
The step II: nitro is to the benzyloxy halobenzene between preparation:
Under agitation condition, nitro between step I gained is added in the reactor B hydroxyl halobenzene and solvent B, wherein between nitro be 1:1～5 to the ratio of hydroxyl halobenzene mmole number and solvent B milliliter number; After treating that a nitro dissolves the hydroxyl halobenzene fully, add halo benzyl, alkali and catalyst A again, wherein between nitro be 1:1～2 to the ratio of hydroxyl halobenzene mmole number and halo benzyl mmole number; Between nitro be 1:1～5 to the ratio of hydroxyl halobenzene mmole number and alkali mmole number; Between nitro be 1:0.01～0.1 to the ratio of hydroxyl halobenzene mmole number and catalyst A mmole number; Be heated to 40～100 ℃ and stirred 2～8 hours, after reaction finished, steaming desolventized B; The water that adds solvent B total amount 0.5～2 volume multiple, a nitro is 1:0.5～2 to the ratio of hydroxyl halobenzene mmole number and water milliliter number, stirs 0.5～2 hour; Suction filtration, solids with the water washing of solvent B total amount 1～3 volume multiple 2～3 times after, use the solvent C recrystallization; Drying makes a nitro to the benzyloxy halobenzene;
Said nitro to the chemical structural formula of hydroxyl halobenzene is:
X is in the formula: Cl, Br or I;
Said catalyst A is Soiodin or potassiumiodide;
Said alkali is sodium hydroxide, Pottasium Hydroxide, hydrated barta, yellow soda ash, salt of wormwood or sodium-acetate;
Said solvent B is: ether, uncle's butyl ether, ethylene glycol diethyl ether, THF, acetone, butanone, be acetonitrile, propionitrile, N, the mixture of one or more in dinethylformamide, DMAC N,N, the N-Methyl pyrrolidone;
Said recrystallization solvent C is: the mixture of one or more in water, methyl alcohol, ethanol, Virahol, methylene dichloride, chloroform, ethylene dichloride, ETHYLE ACETATE, butylacetate, ether, uncle's butyl ether, ethylene glycol diethyl ether, THF, acetonitrile, the propionitrile;
Step III: preparation 4,4 '-two (3-nitro-4-benzyloxy phenoxy) sulfobenzide:
Nitro between step II gained is added among the reactor drum C benzyloxy halobenzene and solvent D; Add bisphenol S, alkali and catalyst B again; Nitro is 1:1～5 to the ratio of benzyloxy halobenzene mmole number and solvent D milliliter number wherein; Between nitro be 1:0.2～0.5 to the ratio of benzyloxy halobenzene mmole number and bisphenol S mmole number; Between nitro be 1:1～5 to the ratio of benzyloxy halobenzene mmole number and alkali mmole number, a nitro is 1:0.1～1 to the ratio of benzyloxy halobenzene mmole number and catalyst B mmole number, nitrogen (N
2) be heated to 120～180 ℃ under the atmosphere and stirred 10～48 hours; After reaction finishes, add the water of solvent D total amount 5～10 volume multiples, suction filtration; Solids with the water washing of solvent D total amount 1～3 volume multiple 2～3 times after; With solvent E recrystallization, make 4,4 '-two (3-nitro-4-benzyloxy phenoxy) sulfobenzide;
Said catalyst B is cuprous chloride, cuprous bromide or cuprous iodide;
Said alkali is any in sodium hydroxide, Pottasium Hydroxide, hydrated barta, yellow soda ash, salt of wormwood, the sodium-acetate;
Said solvent D is: N, any in dinethylformamide, DMAC N,N, N-Methyl pyrrolidone, the methyl-sulphoxide;
Said recrystallization solvent E is: the mixture of one or more in water, methyl alcohol, ethanol, Virahol, methylene dichloride, chloroform, ethylene dichloride, ETHYLE ACETATE, butylacetate, ether, uncle's butyl ether, ethylene glycol diethyl ether, THF, acetonitrile, the propionitrile;
Step IV: preparation 4,4 '-two (3-amino-4-hydroxy phenoxy) sulfobenzide hydrochloride:
With dissolving with solvent F among step III gained 4,4 '-two (3-nitro-4-benzyloxy phenoxy) the sulfobenzide adding reactor drum D, wherein 4,4 '-two (3-nitro-4-benzyloxy phenoxy) sulfobenzide mmole number is 1:10～15 with the ratio of solvent F milliliter number; Add catalyzer C again, 4,4 '-two (3-nitro-4-benzyloxy phenoxy) sulfobenzide quality gram number is 1:0.01～0.1 with the ratio of catalyzer C quality gram number; Hydrogen (the H of 1～10bar pressure
2) under the atmosphere, 25～50 ℃ were stirred 10～24 hours; After reaction finishes, filtration catalizer C, steaming 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 get 4,4 '-two (3-amino-4-hydroxy phenoxy) sulfobenzide hydrochloride;
Said solvent F is: the mixture of one or more in methyl alcohol, ethanol, Virahol, ether, the THF;
Said catalyzer C is the platinum family precious metal that is stated from the carrier, and the platinum family precious metal is palladium, platinum or rhodium; Carrier is gac, aluminum oxide or silicon oxide.
5.4 4 '-(3-amino-4-hydroxy phenoxy) ditane hydrochloride is characterized in that this compound has the chemical structural formula of formula III:
（Ⅲ）。
6. by the preparation method of said 4,4 '-(3-amino-4-hydroxy phenoxy) the ditane hydrochloride of claim 5, it is characterized in that comprising the following steps:
The step I: nitro is to the hydroxyl halobenzene between preparation:
To add in the reactor A the hydroxyl halobenzene, and add the methylene dichloride dissolving, wherein the ratio to hydroxyl halobenzene mmole number and methylene dichloride milliliter number is 1:1～5; Be cooled to 0～10 ℃ under the agitation condition, drip 65% concentrated nitric acid, wherein the ratio to hydroxyl halobenzene mmole number and nitric acid mmole number is 1:1～1.5; Nitric acid finishes the back and stirred 2～6 hours down at 0～10 ℃, after reaction finishes, with methylene dichloride 1～3 volume multiple washing 2～3 times, uses the solvent orange 2 A recrystallization, and drying makes a nitro to the hydroxyl halobenzene;
Saidly be to hydroxyl halobenzene structure:
X is in the formula: Cl, Br or I;
Said recrystallization solvent A is: the mixture of one or more in water, methyl alcohol, ethanol, Virahol, methylene dichloride, chloroform, ethylene dichloride, ETHYLE ACETATE, butylacetate, ether, uncle's butyl ether, ethylene glycol diethyl ether, THF, acetonitrile, the propionitrile;
The step II: nitro is to the benzyloxy halobenzene between preparation:
Under agitation condition, nitro between step I gained is added in the reactor B hydroxyl halobenzene and solvent B, wherein between nitro be 1:1～5 to the ratio of hydroxyl halobenzene mmole number and solvent B milliliter number; After treating that a nitro dissolves the hydroxyl halobenzene fully, add halo benzyl, alkali and catalyst A again, wherein between nitro be 1:1～2 to the ratio of hydroxyl halobenzene mmole number and halo benzyl mmole number; Between nitro be 1:1～5 to the ratio of hydroxyl halobenzene mmole number and alkali mmole number; Between nitro be 1:0.01～0.1 to the ratio of hydroxyl halobenzene mmole number and catalyst A mmole number; Be heated to 40～100 ℃ and stirred 2～8 hours, after reaction finished, steaming desolventized B; The water that adds solvent B total amount 0.5～2 volume multiple, a nitro is 1:0.5～2 to the ratio of hydroxyl halobenzene mmole number and water milliliter number, stirs 0.5～2 hour; Suction filtration, solids with the water washing of solvent B total amount 1～3 volume multiple 2～3 times after, use the solvent C recrystallization; Drying makes a nitro to the benzyloxy halobenzene;
Said nitro to the chemical structural formula of hydroxyl halobenzene is:
X is in the formula: Cl, Br or I;
Said catalyst A is Soiodin or potassiumiodide;
Said alkali is sodium hydroxide, Pottasium Hydroxide, hydrated barta, yellow soda ash, salt of wormwood or sodium-acetate;
Said solvent B is: ether, uncle's butyl ether, ethylene glycol diethyl ether, THF, acetone, butanone, be acetonitrile, propionitrile, N, the mixture of one or more in dinethylformamide, DMAC N,N, the N-Methyl pyrrolidone;
Said recrystallization solvent C is: the mixture of one or more in water, methyl alcohol, ethanol, Virahol, methylene dichloride, chloroform, ethylene dichloride, ETHYLE ACETATE, butylacetate, ether, uncle's butyl ether, ethylene glycol diethyl ether, THF, acetonitrile, the propionitrile;
Step III: preparation 4,4 '-(3-nitro-4-benzyloxy phenoxy) ditane:
Nitro between step II gained is added among the reactor drum C benzyloxy halobenzene and solvent D, adds Bisphenol F, alkali and catalyst B again, wherein between nitro be 1:1～5 to the ratio of benzyloxy halobenzene mmole number and solvent D milliliter number; Between nitro be 1:0.2～0.5 to the ratio of benzyloxy halobenzene mmole number and Bisphenol F mmole number; Between nitro be 1:1～5 to the ratio of benzyloxy halobenzene mmole number and alkali mmole number; Between nitro be 1:0.1～1 to the ratio of benzyloxy halobenzene mmole and catalyst B mmole number; Nitrogen (N
2) be heated to 120～180 ℃ under the atmosphere and stirred 10～48 hours; After reaction finishes, add the water of solvent D total amount 5～10 volume multiples, suction filtration; Solids with the water washing of solvent D total amount 1～3 volume multiple 2～3 times after; With solvent E recrystallization, make 4,4 '-(3-nitro-4-benzyloxy phenoxy) ditane;
Said catalyst B is cuprous chloride, cuprous bromide or cuprous iodide;
Said alkali is any in sodium hydroxide, Pottasium Hydroxide, hydrated barta, yellow soda ash, salt of wormwood, the sodium-acetate;
Said solvent D is: N, any in dinethylformamide, DMAC N,N, N-Methyl pyrrolidone, the methyl-sulphoxide;
Said recrystallization solvent E is: the mixture of one or more in water, methyl alcohol, ethanol, Virahol, methylene dichloride, chloroform, ethylene dichloride, ETHYLE ACETATE, butylacetate, ether, uncle's butyl ether, ethylene glycol diethyl ether, THF, acetonitrile, the propionitrile;
Step IV: preparation 4,4 '-(3-amino-4-hydroxy phenoxy) ditane hydrochloride:
4,4 '-(3-nitro-4-benzyloxy phenoxy) ditane that the step III is made adds among the reactor drum D and dissolves with solvent F, and wherein 4,4 '-(3-nitro-4-benzyloxy phenoxy) ditane mmole number is 1:10～15 with the ratio of solvent F milliliter number; Add catalyzer C again, 4,4 '-(3-nitro-4-benzyloxy phenoxy) ditane quality gram number is 1:0.01～0.1 with the ratio of catalyzer C quality gram number; Hydrogen (the H of 1～10bar pressure
2) under the atmosphere, 25～50 ℃ were stirred 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 4,4 '-(3-amino-4-hydroxy phenoxy) ditane hydrochloride;
Said solvent F is: the mixture of one or more in methyl alcohol, ethanol, Virahol, ether, the THF;
Said catalyzer C is selected from the platinum family precious metal that is stated from the carrier, and the platinum family precious metal is palladium, platinum or rhodium, and carrier is gac, aluminum oxide or silicon oxide.
7.2 2-two (4-(3-amino-4-hydroxy phenoxy) phenyl) HFC-236fa hydrochloride is characterized in that this compound has the chemical structural formula of formula IV:
（Ⅳ）。
8. said 2 by claim 7, the preparation method of 2-two (4-(3-amino-4-hydroxy phenoxy) phenyl) HFC-236fa hydrochloride is characterized in that comprising the following steps:
The step I: nitro is to the hydroxyl halobenzene between preparation:
To add in the reactor A the hydroxyl halobenzene, and add the methylene dichloride dissolving, wherein the ratio to hydroxyl halobenzene mmole number and methylene dichloride milliliter number is 1:1～5; Be cooled to 0～10 ℃ under the agitation condition, drip 65% concentrated nitric acid, wherein the ratio to hydroxyl halobenzene mmole number and nitric acid mmole number is 1:1～1.5; Nitric acid finishes the back and stirred 2～6 hours down at 0～10 ℃, after reaction finishes, with methylene dichloride 1～3 volume multiple washing 2～3 times, uses the solvent orange 2 A recrystallization, and drying makes a nitro to the hydroxyl halobenzene;
Saidly be to hydroxyl halobenzene structure:
X is in the formula: Cl, Br or I;
Said recrystallization solvent A is: the mixture of one or more in water, methyl alcohol, ethanol, Virahol, methylene dichloride, chloroform, ethylene dichloride, ETHYLE ACETATE, butylacetate, ether, uncle's butyl ether, ethylene glycol diethyl ether, THF, acetonitrile, the propionitrile;
The step II: nitro is to the benzyloxy halobenzene between preparation:
Under agitation condition, nitro between step I gained is added in the reactor B hydroxyl halobenzene and solvent B, wherein between nitro be 1:1～5 to the ratio of hydroxyl halobenzene mmole number and solvent B milliliter number; After treating that a nitro dissolves the hydroxyl halobenzene fully, add halo benzyl, alkali and catalyst A again, wherein between nitro be 1:1～2 to the ratio of hydroxyl halobenzene mmole number and halo benzyl mmole number; Between nitro be 1:1～5 to the ratio of hydroxyl halobenzene mmole number and alkali mmole number; Between nitro be 1:0.01～0.1 to the ratio of hydroxyl halobenzene mmole number and catalyst A mmole number; Be heated to 40～100 ℃ and stirred 2～8 hours, after reaction finished, steaming desolventized B; The water that adds solvent B total amount 0.5～2 volume multiple, a nitro is 1:0.5～2 to the ratio of hydroxyl halobenzene mmole number and water milliliter number, stirs 0.5～2 hour; Suction filtration, solids with the water washing of solvent B total amount 1～3 volume multiple 2～3 times after, use the solvent C recrystallization; Drying makes a nitro to the benzyloxy halobenzene;
Said nitro to the chemical structural formula of hydroxyl halobenzene is:
X is in the formula: Cl, Br or I;
Said catalyst A is Soiodin or potassiumiodide;
Said alkali is sodium hydroxide, Pottasium Hydroxide, hydrated barta, yellow soda ash, salt of wormwood or sodium-acetate;
Said solvent B is: ether, uncle's butyl ether, ethylene glycol diethyl ether, THF, acetone, butanone, be acetonitrile, propionitrile, N, the mixture of one or more in dinethylformamide, DMAC N,N, the N-Methyl pyrrolidone;
Said recrystallization solvent C is: the mixture of one or more in water, methyl alcohol, ethanol, Virahol, methylene dichloride, chloroform, ethylene dichloride, ETHYLE ACETATE, butylacetate, ether, uncle's butyl ether, ethylene glycol diethyl ether, THF, acetonitrile, the propionitrile;
The step III: preparation 2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) HFC-236fa:
Nitro between step II gained is added among the reactor drum C benzyloxy halobenzene and solvent D, adds bisphenol AF, alkali and catalyst B again, wherein between nitro be 1:1～5 to the ratio of benzyloxy halobenzene mmole number and solvent D milliliter (ml) number; Between nitro be 1:0.2～0.5 to the ratios of benzyloxy halobenzene mmole (mmol) number and bisphenol AF mmole number; Between nitro be 1:1～5 to the ratio of benzyloxy halobenzene mmole number and alkali mmole number; Between nitro be 1:0.1～1 to the ratio of benzyloxy halobenzene mmole number and catalyst B mmole number; Nitrogen (N
2) be heated to 120～180 ℃ under the atmosphere and stirred 10～48 hours; After reaction finishes, add the water of solvent D total amount 5～10 volume multiples, suction filtration; Solids with the water washing of solvent D total amount 1～3 volume multiple 2～3 times after; With solvent E recrystallization, make 2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) HFC-236fa;
Said catalyst B is cuprous chloride, cuprous bromide or cuprous iodide;
Said alkali is any in sodium hydroxide, Pottasium Hydroxide, hydrated barta, yellow soda ash, salt of wormwood, the sodium-acetate;
Said solvent D is: N, any in dinethylformamide, DMAC N,N, N-Methyl pyrrolidone, the methyl-sulphoxide;
Said recrystallization solvent E is: the mixture of one or more in water, methyl alcohol, ethanol, Virahol, methylene dichloride, chloroform, ethylene dichloride, ETHYLE ACETATE, butylacetate, ether, uncle's butyl ether, ethylene glycol diethyl ether, THF, acetonitrile, the propionitrile;
The step IV: preparation 2,2-two (4-(3-amino-4-hydroxy phenoxy) phenyl) HFC-236fa hydrochloride:
With the step III make 2; Dissolve with solvent F among 2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) the HFC-236fa adding reactor drum D; Wherein 2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) HFC-236fa mmole number is 1:10～15 with the ratio of solvent F milliliter number; Add catalyzer C again, 2,2-two (4-(3-nitro-4-benzyloxy phenoxy) phenyl) HFC-236fa quality gram number is 1:0.01～0.1 with the ratio of catalyzer C quality gram number; Hydrogen (H at 1～10bar pressure
2) under the atmosphere, stirred 10～24 hours in 25～50 ℃, 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-two (4-(3-amino-4-hydroxy phenoxy) phenyl) HFC-236fa hydrochloride;
Said solvent F is:, one or more the mixture in the methyl alcohol, ethanol, Virahol, ether, THF;
Said catalyzer C is selected from the platinum family precious metal that is stated from the carrier, and the platinum family precious metal is palladium, platinum or rhodium, and suitable carrier is gac, aluminum oxide or silicon oxide.
9. by claim 1,3,5 or 7 said bis-phenols two (an amino p-hydroxybenzene) ether hydrochloride, it is characterized in that: be applicable to preparation soluble poly benzoxazole.
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