CN100586931C - Method for synthesizing 2,4-diamino[4'-(4-phenylacetylenylphthalimido)]diphenyl ether - Google Patents
Method for synthesizing 2,4-diamino[4'-(4-phenylacetylenylphthalimido)]diphenyl ether Download PDFInfo
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- CN100586931C CN100586931C CN200810050644A CN200810050644A CN100586931C CN 100586931 C CN100586931 C CN 100586931C CN 200810050644 A CN200810050644 A CN 200810050644A CN 200810050644 A CN200810050644 A CN 200810050644A CN 100586931 C CN100586931 C CN 100586931C
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Abstract
The invention belongs to a method of preparing 2, 4-diamino (4<1>-(4-phenylethynyl phthalimido)) diphenyl ether. Paraaminophenol and 4-phenylethynyl anhydride or 4-phenylacetylene phthalandione areprocessed through the cyclodehydration under the high temperature to generate N-(4-hydroxyphenyl)-4<1>-phenylethynyl phthalimide which is an intermediate product; the nucleophilic substitution reaction is performed between the intermediate product and 2, 4-dinitrochlorobenzol to generate 2, 4-binitro (4<1>-(4-phenylethynyl phthalimido)) diphenyl ether which is deoxygenized to obtain the 2, 4-diamino (4<1>-(4-phenylethynyl phthalimido)) diphenyl ether. The solidifying rate of phenylethynyl is proved to get faster when the electron withdrawing ability of a substitutional group thereof is increased. The solidifying of the phenylethynyl in the 2, 4-diamino (4<1>-(4-phenylethynyl phthalimido)) diphenyl ether follows the second order reaction kinetics, the solidifying rate thereof k equals to 0.45; in addition, the phenylethynyl has the same structure with a terminal group, so that the solidifying reaction between the phenylethynyl and the terminal group is simplified.
Description
Technical field
The invention belongs to 2, the synthetic method of 4-diamino [4 '-(4-phenylacetylene base phthalimide group)] phenyl ether.
Background technology
The imide oligopolymer that contains phenylacetylene base has high solidification value, process window can be expanded to high temperature, the processing of advantageous material, resin behind its forming and hardening has high thermo-oxidative stability, high second-order transition temperature, high mechanical property again, and the hydrolytic resistance of resin and high temperature dimensional stability also greatly improve.Oligopolymer is with tackiness agent, and the form of coating and composite matrix resin has important use in fields such as aerospace.Phenylacetylene base being incorporated on the side chain of imide oligopolymer, is on the basis that does not influence other performance, and the cross-linking density when just solidifying by the content that increases phenylacetylene improves the heat resistance performance and the compressive property of material.The researchist of NASA has synthesized the diamine monomer (United States Patent (USP): US.6124035 that some side chains contain phenylacetylene, 5606014), as: 2,4-diamino-4 '-(4-phenylacetylene base-4 '-phenyl) phenyl ether and 3,5-diamino-4 '-the phenylacetylene base benzophenone.The side chain phenylacetylene base be in the terminated phenylacetylene base relatively, its motion is subjected to bigger obstruction, makes its completion of cure that higher temperature or longer set time (Polymer, 46,6968 (2005)) must be arranged.
Summary of the invention
The invention provides a kind of 2, the preparation method of 4-diamino [4 '-(4-phenylacetylene base phthalimide group)] phenyl ether.
This method is a raw material with p-aminophenol and 4-phenylacetylene phthalic anhydride or 4-phenylacetylene phthalic acid, the high temperature cyclodehydration generate intermediate N (4-hydroxy phenyl)-4 '-the phenylacetylene base phthalimide; This product is again with 2, and 4-dinitrochlorobenzene generation nucleophilic substitution reaction generates 2, and 4-dinitrobenzene [4 '-(4-phenylacetylene base phthalimide group)] phenyl ether obtains 2,4-diamino [4 '-(4-phenylacetylene base phthalimide group)] phenyl ether with this product reduction.
Synthetic route of the present invention is as follows:
1) N-(4-hydroxy phenyl)-4 '-phenylacetylene base phthalimide is synthetic:
According to (1: 1)-(1.2: 1) mol ratio, p-aminophenol and 4-phenylacetylene phthalic anhydride or 4-phenylacetylene phthalic acid are joined in the solvent, be heated to 120-160 ℃ then, reacted 6-10 hour, after being cooled to normal temperature, reactant is poured in water or the ethanol, filtered the back solid and wash 3 times with ethanol, drying gets N-(4-hydroxy phenyl)-4 '-phenylacetylene base phthalimide; Described weight of solvent be p-aminophenol, 4-phenylacetylene phthalic anhydride or 4-phenylacetylene phthalic acid weight 4-10 doubly; Described solvent is: Glacial acetic acid, benzene,toluene,xylene, phenol, cresols or P-Chlorophenol;
2) 2,4-dinitrobenzene [4 '-(4-phenylacetylene base phthalimide group)] phenyl ether synthetic:
According to (1: 1)-(1: 1.2) mol ratio, with N-(4-hydroxy phenyl)-4 '-phenylacetylene base phthalimide and 2, the 4-dinitrochlorobenzene joins in the solvent, the weight of this solvent is N-(4-hydroxy phenyl)-4 '-phenylacetylene base phthalimide or 2, the 4-10 of 4-dinitrochlorobenzene doubly, and then catalyzer also joined in this solvent, reaction is 6-10 hour in 80-120 ℃ of following nitrogen, after being cooled to normal temperature, reactant is poured in ethanol or the water, stirred after-filtration, use washing with alcohol, drying gets 2,4-dinitrobenzene [4 '-(4-phenylacetylene base phthalimide group)] phenyl ether; Described solvent is: N, N '-dimethyl formamide, N, N ' N,N-DIMETHYLACETAMIDE, N-N-methyl-2-2-pyrrolidone N-or dimethyl sulfoxide (DMSO); Described catalyzer is: triethylamine, pyridine or Anhydrous potassium carbonate;
3) 2,4-diamino [4 '-(4-phenylacetylene base phthalimide group)] phenyl ether synthetic:
With 2, phenyl ether is dissolved in 4-dinitrobenzene [4 '-(4-phenylacetylene base phthalimide group)] is in the solvent of its 4-10 times weight, in solution, add tin protochloride, the concentrated hydrochloric acid aqueous solution of iron protochloride or zinc chloride, wherein solvent and concentrated hydrochloric acid volume ratio are (1: 2)-(2: 1), tin protochloride, iron protochloride or zinc chloride and 2, the mol ratio of 4-dinitrobenzene [4 '-(4-phenylacetylene base phthalimide group)] phenyl ether is (1: 3)-(1: 15), then at 20-100 ℃, reacted 10-20 hour, reaction is poured reaction solution in the water into after finishing, leave standstill, filter,, wash with weak ammonia then with the dilute hydrochloric acid washing, wash with pure water again, drying gets 2,4-diamino [4 '-(4-phenylacetylene base phthalimide group)] phenyl ether; Described solvent is: N, N '-dimethyl formamide, N, N '-N,N-DIMETHYLACETAMIDE, N-N-methyl-2-2-pyrrolidone N-, dimethyl sulfoxide (DMSO) or dioxane.
Beneficial effect: the present invention successfully synthesizes the diamine monomer that a kind of side chain contains 4-phenylacetylene phthalimide, and its structure is identical with main chain end-capping reagent structure, and curing reaction is each other oversimplified.The solidification rate of scientist verified (Polymer, 41,5109 (2000)) phenylacetylene base accelerates along with the raising of its substituting group electron-withdrawing power simultaneously.2, the curing of phenylacetylene base is followed second order reaction kinetics, its solidification rate k=0.45 in 4-diamino [4 '-(4-phenylacetylene base the phthalimide group)] phenyl ether.
Embodiment
Embodiment 1:
In the 1000mL round-bottomed flask, add 10.91g (0.1mol) p-aminophenol and 24.88g (0.1mol) 4-phenylacetylene phthalic anhydride, add the 600mL Glacial acetic acid, 120 ℃ of reactions of heating are 10 hours under the mechanical stirring, reaction finishes postcooling to normal temperature, reactant is poured in the ethanol into agitation and filtration, solid is washed twice with ethanol, drying obtains yellow solid N-(4-hydroxy phenyl)-4 '-phenylacetylene base phthalimide 31g, yield 93%, fusing point 259-260 ℃.
In the 250mL round-bottomed flask, add 34.00g (0.1mol) N-(4-hydroxy phenyl)-4 '-phenylacetylene base phthalimide and 24.31g (0.12mol) 2; the 4-dinitrochlorobenzene; add anhydrous N-N-methyl-2-2-pyrrolidone N-of 150mL and 10mL triethylamine again; mechanical stirring; 100 ℃ of reacting by heating are 10 hours under nitrogen protection; reaction finishes postcooling to normal temperature; reactant is poured in the ethanol; filter; solid washes twice with ethanol, and drying obtains yellow solid 2,4-dinitrobenzene [4 '-(4-phenylacetylene base phthalimide group)] phenyl ether 46.5g; yield 92%, fusing point 177-178 ℃.
Add 14g (0.028mol) 2 in the 1000mL round-bottomed flask, 4-dinitrobenzene [4 '-(4-phenylacetylene base phthalimide group)] phenyl ether and 350mL dioxane are cooled to 10-20 ℃ with solution after the dissolving.With 74g (0.33mol) SnCl
22H
2O is dissolved in the concentrated hydrochloric acid of 226mL, be cooled to about 10 ℃, slowly splash into this hydrochloric acid soln in the dioxane solution, and keep reacting liquid temperature at 10-20 ℃, there is solid to separate out in the dropping process, after being added dropwise to complete, keeps this to be reflected at 20 ℃ and reacted 20 hours down, reaction is poured in the aqueous hydrochloric acid of PH=1 after finishing, filter, solid washes twice with the aqueous hydrochloric acid of PH=1, washes secondary with weak ammonia again, it is inferior to give a baby a bath on the third day after its birth with pure water again, filter, dry back gets solid 2 with the dioxane recrystallization, 4-diamino [4 '-(4-phenylacetylene base phthalimide group)] phenyl ether 11.2g, yield 90%, fusing point 179-180 ℃.
Embodiment 2:
In the 250mL round-bottomed flask, add 10.91g (0.1mol) p-aminophenol and 26.5g (0.1mol) 4-phenylacetylene phthalic acid, add 100mL phenol, be heated to 160 ℃ of reactions 6 hours under the mechanical stirring, reaction finishes postcooling to 80 ℃, and reactant is poured in the 300mL ethanol, leaves standstill filtration, solid is washed twice with ethanol, drying obtains yellow solid N-(4-hydroxy phenyl)-4 '-phenylacetylene base phthalimide 28g, yield 82%, fusing point 259-260 ℃.
In the 250mL round-bottomed flask, add 34.00g (0.1mol) N-(4-hydroxy phenyl)-4 '-phenylacetylene base phthalimide and 24.31g (0.12mol) 2; the 4-dinitrochlorobenzene; add the anhydrous N of 150mL again; the Anhydrous potassium carbonate of N '-dimethyl formamide and 13.80g (0.1mol); mechanical stirring; 80 ℃ of reacting by heating are 10 hours under nitrogen protection; reaction finishes postcooling; reactant is poured in the aqueous hydrochloric acid, filtered, solid is washed twice with ethanol; drying obtains yellow solid 2; 4-dinitrobenzene [4 '-(4-phenylacetylene base phthalimide group)] phenyl ether 40g, yield 80%, fusing point 177-178 ℃.
In the 1000mL round-bottomed flask, add 14g (0.028mol) 2,4-dinitrobenzene [4 '-(4-phenylacetylene base phthalimide group)] phenyl ether and 150mLN, N '-N,N-DIMETHYLACETAMIDE is cooled to 10-20 ℃ with solution after the dissolving.23.52g (0.42mol) iron powder is joined in the concentrated hydrochloric acid of 120mL gradually, after treating that solid dissolves fully, cooling solution is to about 10 ℃, this hydrochloric acid soln is slowly splashed into N, in N '-dimethylacetamide solution, and keep reacting liquid temperature at 10-20 ℃, there is solid to separate out in the dropping process, after being added dropwise to complete, keeps this to be reflected at 20 ℃ and reacted 20 hours down, reaction is poured in the aqueous hydrochloric acid of PH=1 after finishing, filter, solid washes twice with the aqueous hydrochloric acid of PH=1, washes secondary with saturated aqueous sodium carbonate again, it is inferior to give a baby a bath on the third day after its birth with pure water again, filter, dry back gets solid 2 with the dioxane recrystallization, 4-diamino [4 '-(4-phenylacetylene base phthalimide group)] phenyl ether 10.8g, yield 86%, fusing point 179-180 ℃.
Embodiment 3:
In the 250mL round-bottomed flask, add 13.1g (0.12mol) p-aminophenol and 24.88g (0.1mol) 4-phenylacetylene phthalic anhydride, add 80mL cresols, be heated to 160 ℃ of reactions 6 hours under the mechanical stirring, reaction finishes postcooling to 80 ℃, and reactant is poured in the 300mL ethanol, leaves standstill filtration, solid is washed twice with ethanol, drying obtains yellow solid N-(4-hydroxy phenyl)-4 '-phenylacetylene base phthalimide 29.5g, yield 87%, fusing point 259-260 ℃.
In the 250mL round-bottomed flask, add 34.00g (0.1mol) N-(4-hydroxy phenyl)-4 '-phenylacetylene base phthalimide and 24.31g (0.1mol) 2; the 4-dinitrochlorobenzene; add the anhydrous N of 150mL again; the Anhydrous potassium carbonate of N '-N,N-DIMETHYLACETAMIDE and 6.90g (0.05mol); mechanical stirring; 160 ℃ of reacting by heating are 8 hours under nitrogen protection; reaction finishes postcooling; reactant is poured in the aqueous hydrochloric acid, filtered, solid is washed twice with ethanol; drying obtains yellow solid 2; 4-dinitrobenzene [4 '-(4-phenylacetylene base phthalimide group)] phenyl ether 43g, yield 85%, fusing point 177-178 ℃.
Add 14g (0.028mol) 2.4-dinitrobenzene [4 '-(4-phenylacetylene base phthalimide group)] phenyl ether and 150mL N in the 500mL round-bottomed flask, N '-dimethyl formamide is heated to 80 ℃ of dissolving postcooling to 50 ℃.5.46g (0.084mol) zinc powder is joined in the concentrated hydrochloric acid of 100mL gradually, after treating that solid dissolves fully, this hydrochloric acid soln is slowly splashed into N, in N '-dimethyl formamide solution, the temperature of reaction solution little by little raises in the dropping process, keeps this reaction solution 50 ℃ of reactions 15 hours, reaction is poured in the aqueous hydrochloric acid after finishing, filter, solid washes twice with the aqueous hydrochloric acid of PH=1, washes secondary with saturated aqueous sodium carbonate again, it is inferior to give a baby a bath on the third day after its birth with pure water again, filter, dry back gets solid 2 with the dioxane recrystallization, 4-diamino [4 '-(4-phenylacetylene base phthalimide group)] phenyl ether 9.8g, yield 78%, fusing point 179-180 ℃.
Embodiment 4:
In the 1000mL round-bottomed flask, add 21.8g (0.2mol) p-aminophenol and 49.6g (0.2mol) 4-phenylacetylene phthalic anhydride, add 200mLN, N '-N,N-DIMETHYLACETAMIDE and 80mL toluene are heated to 130 ℃ of toluene band water under the mechanical stirring, steam toluene after 6 hours, reacted again 2 hours, and poured in the ethanol after the reactant cooling, filter, solid is washed twice with ethanol, drying obtains yellow solid N-(4-hydroxy phenyl)-4 '-phenylacetylene base phthalimide 60g, yield 88%, fusing point 259-260 ℃.
In the 500mL round-bottomed flask, add 68.00g (0.2mol) N-(4-hydroxy phenyl)-4 '-phenylacetylene base phthalimide and 48.62g (0.24mol) 2; the 4-dinitrochlorobenzene; add the anhydrous N of 300mL again; N '-N,N-DIMETHYLACETAMIDE and 10mL pyridine; mechanical stirring; 120 ℃ of reacting by heating are 12 hours under nitrogen protection; reaction finishes postcooling; reactant is poured in the ethanol, filtered, solid is washed twice with ethanol; drying obtains yellow solid 2; 4-dinitrobenzene [4 '-(4-phenylacetylene base phthalimide group)] phenyl ether 90g, yield 89%, fusing point 177-178 ℃.
In the 1000mL round-bottomed flask, add 28g (0.056mol) 2,4-dinitrobenzene [4 '-(4-phenylacetylene base phthalimide group)] phenyl ether and 500mLN, N '-dimethyl formamide is cooled to 10-20 ℃ with solution after the dissolving, has solid to separate out.With 74g (0.33mol) SnCl
22H
2O is dissolved in the concentrated hydrochloric acid of 250mL, this hydrochloric acid soln is slowly splashed into N, in N '-dimethyl formamide solution, there is solid to separate out in the dropping process, keep this reaction solution 100 ℃ of reactions 10 hours, reaction is poured in the aqueous hydrochloric acid of PH=1 after finishing, filter, solid washes twice with the aqueous hydrochloric acid of PH=1, washes secondary with saturated aqueous sodium carbonate again, it is inferior to give a baby a bath on the third day after its birth with pure water again, filter, dry back gets solid 2 with the dioxane recrystallization, 4-diamino [4 '-(4-phenylacetylene base phthalimide group)] phenyl ether 20g, yield 80%, fusing point 179-180 ℃.
Embodiment 5:
In the 500mL round-bottomed flask, add 21.8g (0.2mol) p-aminophenol and 49.6g (0.2mol) 4-phenylacetylene phthalic anhydride, add 150mL phenol, be heated to 140 ℃ of reactions 8 hours under the mechanical stirring, reaction finishes postcooling to 60 ℃, and reactant is poured in the 350mL ethanol, leaves standstill filtration, solid is washed twice with ethanol, drying obtains yellow solid N-(4-hydroxy phenyl)-4 '-phenylacetylene base phthalimide 61g, yield 90%, fusing point 259-260 ℃.
In the 500mL round-bottomed flask, add 68.00g (0.2mol) N-(4-hydroxy phenyl)-4 '-phenylacetylene base phthalimide and 48.6g (0.24mol) 2; the 4-dinitrochlorobenzene; the Anhydrous potassium carbonate that adds anhydrous N-N-methyl-2-2-pyrrolidone N-of 300mL and 27.6g (0.2mol) again; mechanical stirring; 120 ℃ of heating are sent out and were answered 10 hours under nitrogen protection; reaction finishes postcooling; reactant is poured in the aqueous hydrochloric acid; filter; solid washes twice with ethanol, and drying obtains yellow solid 2,4-dinitrobenzene [4 '-(4-phenylacetylene base phthalimide group)] phenyl ether 89g; yield 88%, fusing point 177-178 ℃.
Add 14g (0.028mol) 2 in the 500mL round-bottomed flask, 4-dinitrobenzene [4 '-(4-phenylacetylene base phthalimide group)] phenyl ether and 150mL dimethyl sulfoxide (DMSO) are heated to 80 ℃ of dissolving postcooling to 50 ℃.With 37.6g (0.168mol) SnCl
22H
2O is dissolved in the concentrated hydrochloric acid of 300mL, slowly splash into this hydrochloric acid soln in the dimethyl sulphoxide solution, the temperature of reaction solution little by little raises in the dropping process, keep this reaction solution at room temperature to react 15 hours, reaction is poured in the aqueous hydrochloric acid after finishing, filter, solid is washed twice with the aqueous hydrochloric acid of PH=1, wash secondary with saturated aqueous sodium carbonate again, it is inferior to give a baby a bath on the third day after its birth with pure water again, filters, dry back gets solid 2 with the dioxane recrystallization, 4-diamino [4 '-(4-phenylacetylene base phthalimide group)] phenyl ether 9.8g, yield 78%, fusing point 179-180 ℃.
Embodiment 6:
In the 1000mL round-bottomed flask, add 21.8g (0.2mol) p-aminophenol and 49.6g (0.2mol) 4-phenylacetylene phthalic anhydride, add the 400mL Glacial acetic acid, reflux is 12 hours under the mechanical stirring, reaction finishes postcooling, and reactant is poured in the ethanol, filters, solid is washed twice with ethanol, drying obtains yellow solid N-(4-hydroxy phenyl)-4 '-phenylacetylene base phthalimide 60g, yield 88%, fusing point 259-260 ℃.
In the 500mL round-bottomed flask, add 68.00g (0.2mol) N-(4-hydroxy phenyl)-4 '-phenylacetylene base phthalimide and 48.6g (0.24mol) 2; the 4-dinitrochlorobenzene; the Anhydrous potassium carbonate that adds 300mL anhydrous dimethyl sulphoxide and 13.8g (0.1mol) again; mechanical stirring; 120 ℃ of reacting by heating are 10 hours under nitrogen protection; reaction finishes postcooling; reactant is poured in the aqueous hydrochloric acid; filter; solid washes twice with ethanol, and drying obtains yellow solid 2,4-dinitrobenzene [4 '-(4-phenylacetylene base phthalimide group)] phenyl ether 89g; yield 90%, fusing point 177-178 ℃.
Add 14g (0.028mol) 2 in the 500mL round-bottomed flask, 4-dinitrobenzene [4 '-(4-phenylacetylene base phthalimide group)] phenyl ether and 200mL N-N-methyl-2-2-pyrrolidone N-are after the heating for dissolving.With 62.7g (0.28mol) SnCl
22H
2O is dissolved in the concentrated hydrochloric acid of 100mL, this hydrochloric acid soln is slowly splashed in the N-N-methyl-2-2-pyrrolidone N-solution, the temperature of reaction solution little by little raises in the dropping process, keep this reaction solution 50 ℃ of reactions 20 hours, reaction is poured in the aqueous hydrochloric acid after finishing, filter, solid is washed twice with the aqueous hydrochloric acid of PH=1, wash secondary with saturated aqueous sodium carbonate again, it is inferior to give a baby a bath on the third day after its birth with pure water again, filters, dry back gets solid 2 with the dioxane recrystallization, 4-diamino [4 '-(4-phenylacetylene base phthalimide group)] phenyl ether 9.8g, yield 78%, fusing point 179-180 ℃.
Claims (1)
1,2, the synthetic method of 4-diamino [4 '-(4-phenylacetylene base phthalimide group)] phenyl ether is characterized in that synthesis step and condition are as follows:
1) N-(4-hydroxy phenyl)-4 '-phenylacetylene base phthalimide is synthetic:
According to 1: 1-1.2: 1 mol ratio, p-aminophenol and 4-phenylacetylene phthalic anhydride or 4-phenylacetylene phthalic acid are joined in the solvent, be heated to 120-160 ℃ then, reacted 6-10 hour, after being cooled to normal temperature, reactant is poured in water or the ethanol, filtered the back solid and wash 3 times with ethanol, drying gets N-(4-hydroxy phenyl)-4 '-phenylacetylene base phthalimide; Described weight of solvent be p-aminophenol, 4-phenylacetylene phthalic anhydride or 4-phenylacetylene phthalic acid weight 4-10 doubly; Described solvent is: Glacial acetic acid, benzene,toluene,xylene, phenol, cresols or P-Chlorophenol;
2) 2,4-dinitrobenzene [4 '-(4-phenylacetylene base phthalimide group)] phenyl ether synthetic:
According to 1: 1-1: 1.2 mol ratios, with N-(4-hydroxy phenyl)-4 '-phenylacetylene base phthalimide and 2, the 4-dinitrochlorobenzene joins in the solvent, the weight of this solvent is N-(4-hydroxy phenyl)-4 '-phenylacetylene base phthalimide or 2, the 4-10 of 4-dinitrochlorobenzene doubly, and then catalyzer also joined in this solvent, reaction is 6-10 hour in 80-120 ℃ of following nitrogen, after being cooled to normal temperature, reactant is poured in ethanol or the water, stirred after-filtration, use washing with alcohol, drying gets 2,4-dinitrobenzene [4 '-(4-phenylacetylene base phthalimide group)] phenyl ether; Described solvent is: N, N '-dimethyl formamide, N, N '-N,N-DIMETHYLACETAMIDE, N-N-methyl-2-2-pyrrolidone N-or dimethyl sulfoxide (DMSO); Described catalyzer is: triethylamine, pyridine or Anhydrous potassium carbonate;
3) 2,4-diamino [4 '-(4-phenylacetylene base phthalimide group)] phenyl ether synthetic:
With 2, phenyl ether is dissolved in 4-dinitrobenzene [4 '-(4-phenylacetylene base phthalimide group)] is in the solvent of its 4-10 times weight, in solution, add tin protochloride, the concentrated hydrochloric acid aqueous solution of iron protochloride or zinc chloride, wherein solvent and concentrated hydrochloric acid volume ratio are 1: 2-2: 1, tin protochloride, iron protochloride or zinc chloride and 2, the mol ratio of 4-dinitrobenzene [4 '-(4-phenylacetylene base phthalimide group)] phenyl ether is 1: 3-1: 15, then at 20-100 ℃, reacted 10-20 hour, reaction is poured reaction solution in the water into after finishing, leave standstill, filter,, wash with weak ammonia then with the dilute hydrochloric acid washing, wash with pure water again, drying gets 2,4-diamino [4 '-(4-phenylacetylene base phthalimide group)] phenyl ether; Described solvent is: N, N '-dimethyl formamide, N, N '-N,N-DIMETHYLACETAMIDE, N-N-methyl-2-2-pyrrolidone N-, dimethyl sulfoxide (DMSO) or dioxane.
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| CN101916521A (en) * | 2010-08-30 | 2010-12-15 | 中国人民解放军第四军医大学 | Modeling method of osteoporosis centrum in vitro model and mating perfusion fixator |
| CN101916521B (en) * | 2010-08-30 | 2011-08-31 | 中国人民解放军第四军医大学 | Modeling method of osteoporosis centrum in vitro model and mating perfusion fixator |
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