CN105001092A - Method for preparing 2,2-di(4-(4-aminophenoxy)phenyl)hexafluoropropane and intermediate body thereof at low temperature - Google Patents

Abstract

The present invention provides a method for preparing a 2,2-di(4-(4-aminophenoxy)phenyl)hexafluoropropane intermediate body at a low temperature. 2,2-di(4-hydroxylphenyl)hexafluoropropane and para-halogenated nitrobenzene are reacted in the presence of a solvent, a catalyst and copper powder to obtain 2,2-di(4-(4-nitrylphenoxy)phenyl)hexafluoropropane. The present invention further provides a method for preparing the 2,2-di(4-(4-aminophenoxy)phenyl)hexafluoropropane at a low temperature. According to the method, a reaction can be carried out at the low temperature and can be realized at 20-40 DEG C; and the reaction time is short and the preparation of the intermediate body can be finished by only 10 hours. By virtue of the method provided by the present invention, the yield of products can be increased and is higher than 79.9%, and the purity of the product is high and is higher than 99.7%; and meanwhile, the production cost is reduced.

Description

A kind of low-temperature growth 2,2-bis-(4-(4-amino-benzene oxygen) phenyl) method of HFC-236fa and intermediate thereof

Technical field

The invention belongs to compound technical, be specifically related to a kind of method of low-temperature growth 2,2-bis-(4-(4-amino-benzene oxygen) phenyl) HFC-236fa and intermediate thereof.

Background technology

2,2-bis-(4-(4-amino-benzene oxygen) phenyl) HFC-236fa (being called for short 4-BDAF), English name 2,2-bis (4-(4-aminophenoxy (-phenyl)-hexa-fluoropropane, molecular formula: C27H20F6N2O2, structural formula is such as formula shown in (I):

4-BDAF is one of main raw material preparing Thin Film Transistor-LCD (TFT-LCD) liquid crystal aligning material, and be widely used in and produce fluorine-containing vulcanization accelerator and thermoplastic resin, all have in WO02100949, WO2004011528, US5504128 and relate to.

The preparation method of existing 4-BDAF mainly contains following several:

Method one: reaction formula is as follows

In US4111906, first by 2, 2-bis-(4-hydroxy phenyl) HFC-236fa and sodium hydroxide are at N, N-N,N-DIMETHYLACETAMIDE and reflux in toluene divide water, preparation 2, the double sodium salt of 2-bis-(4-hydroxy phenyl) HFC-236fa, and then with parachloronitrobenzene in 150 DEG C of reactions 48 hours, reaction solution is poured into water, separate out 2, 2-bis-(4-(4-nitrophenoxy) phenyl) HFC-236fa, by 2, after 2-bis-(4-(4-nitrophenoxy) phenyl) HFC-236fa is purified by ethyl alcohol recrystallization, with iron powder/hydrochloric acid system reduction, obtain target product 4-BDAF.

In this kind of method, temperature of reaction up to 150 DEG C, and the double sodium salt of 2,2-bis-(4-hydroxy phenyl) HFC-236fa and parachloronitrobenzene reaction times reach 48 hours.And during the separation of 2,2-bis-(4-(4-nitrophenoxy) phenyl) HFC-236fa, need to filter out solid in impouring water, produce a large amount of waste water containing N,N-dimethylacetamide, be extremely not suitable for industrial production.

Method two: reaction formula is as follows

In US5043478, and method one is by comparison, and 2; in the preparation process of the double sodium salt of 2-bis-(4-hydroxy phenyl) HFC-236fa, have employed nitrogen protection, sodium hydroxide adds in batches in addition; and then and parachloronitrobenzene in 150 DEG C of reactions, and the reaction times narrowed down to 4 hours.But 2, the aftertreatment of 2-bis-(4-(4-nitrophenoxy) phenyl) HFC-236fa, or reaction solution is poured in the mixed solution of first alcohol and water, separate out 2,2-bis-(4-(4-nitrophenoxy) phenyl) HFC-236fa, by 2, after 2-bis-(4-(4-nitrophenoxy) phenyl) HFC-236fa is purified by ethyl acetate and methanol mixed solvent recrystallization, under Pd/C catalysis, hydrogen reducing, obtains target product 4-BDAF.

In this kind of method, compare with method one and improve to some extent, also there is larger shortening in the reaction times, but temperature of reaction is still up to 150 DEG C.And during the separation of 2,2-bis-(4-(4-nitrophenoxy) phenyl) HFC-236fa, need in the mixed solution of impouring first alcohol and water, filter out solid, produce a large amount of waste water containing N,N-dimethylacetamide and methyl alcohol, be still not suitable for industrial production.

Method three: reaction formula is as follows

(liquid crystal and the display such as Zhang Jianli, 2009, 3, in method 345-349) adopted, 2, 2-bis-(4-hydroxy phenyl) HFC-236fa and sodium hydroxide are at N, in N-N,N-DIMETHYLACETAMIDE, first 70 ~ 80 DEG C of reaction generations 2, the double sodium salt of 2-bis-(4-hydroxy phenyl) HFC-236fa, then parachloronitrobenzene is dripped in 140 DEG C, 5 hours reaction times, react complete, most N is reclaimed in underpressure distillation, N-N,N-DIMETHYLACETAMIDE, leftover materials are poured into water, separate out 2, 2-bis-(4-(4-nitrophenoxy) phenyl) HFC-236fa, by 2, after the mixed solvent recrystallization of 2-bis-(4-(4-nitrophenoxy) phenyl) HFC-236fa ethanol and toluene, under Pd/C catalysis, hydrogen reducing, obtain target product 4-BDAF.

This kind of method, although reclaimed most of N,N-dimethylacetamide, containing moisture in the N,N-dimethylacetamide of recovery, can not recovery.And temperature of reaction is up to 140 DEG C.And still have the generation of a large amount of waste water, be not suitable for industrial production.

Summary of the invention

Main purpose of the present invention solves the above-mentioned all drawback of 4-BDAF in preparation process, provides a kind of high yield, the easy to operate and method of the low-temperature growth 4-BDAF of environmental protection and intermediate thereof.

By the unremitting effort of contriver, find 2, in the preparation process of 2-bis-(4-(4-nitrophenoxy) phenyl) HFC-236fa, select suitable solvent, deposit in case in catalyst A and copper powder, can react very easily, reaction can be carried out under low temperature, easy to operate control, and product yield and product content are all higher.2,2-bis-(4-(4-nitrophenoxy) phenyl) HFC-236fa that this step operation is produced, can be reduced into 2,2-bis-(4-(4-amido Phenoxyphenyl)) HFC-236fa very easily.

Reaction scheme is as follows:

The invention provides a kind of low-temperature growth 2, the method of 2-bis-(4-(4-amino-benzene oxygen) phenyl) HFC-236fa intermediate, described 2,2-bis-(4-(4-amino-benzene oxygen) phenyl) HFC-236fa intermediate is 2,2-bis-(4-(4-nitrophenoxy) phenyl) HFC-236fa, by 2,2-bis-(4-hydroxy phenyl) HFC-236fa and para-halo oil of mirbane are deposited at solvent, catalyzer and copper powder and are reacted in case, obtain 2,2-bis-(4-(4-nitrophenoxy) phenyl) HFC-236fa;

Wherein, described solvent is selected from N,N-dimethylacetamide, DMF, acetonitrile, dimethyl sulfoxide (DMSO), N, N-diethyl acetamide, N, N-diethylformamide, N-Methyl pyrrolidone, HMPA, the mixture of a kind of in acetone or two kinds;

Described catalyzer is selected from the one or more kinds of mixture in following structure:

Wherein C-1 name is called: N-phenyl-2-pyridine carboxamide;

C-2 name is called: N-(4-aminomethyl phenyl)-2-pyridine carboxamide;

C-3 name is called: N-(4-p-methoxy-phenyl)-2-pyridine carboxamide;

C-4 name is called: N-(4-fluorophenyl)-2-pyridine carboxamide;

C-5 name is called: N-(3,5-3,5-dimethylphenyl)-2-pyridine carboxamide;

C-6 name is called: N-(4-carboxyl phenyl)-2-pyridine carboxamide;

C-7 name is called: N-(4-nitrophenyl)-2-pyridine carboxamide;

Solvent, catalyzer all can any two kinds mix with arbitrary proportion.

Preferably, described para-halo oil of mirbane selects parachloronitrobenzene or p-fluoronitrobenzene.

Preferably, the consumption of described catalyzer is 0.5 ~ 4 times of the amount of substance of 2,2-bis-(4-hydroxy phenyl) HFC-236fa; More preferably, the consumption of described catalyzer is 1 ~ 2 times of the amount of substance of 2,2-bis-(4-hydroxy phenyl) HFC-236fa.Select the yield of product during above-mentioned catalyst levels scope and product content high, the highest time in more preferably scope.

Preferably, the consumption of described copper powder is 1 ~ 8 times of the amount of substance of 2,2-bis-(4-hydroxy phenyl) HFC-236fa; Preferably, the consumption of described copper powder is 2 ~ 4 times of the amount of substance of 2,2-bis-(4-hydroxy phenyl) HFC-236fa.Select the yield of product during above-mentioned catalyst levels scope and product content high, the highest time in more preferably scope.

Preferably, the temperature of described reaction is 20 ~ 40 DEG C, preferably 25 ~ 35 DEG C.

Preferably, acetonitrile is contained in described solvent; As more preferably, acetonitrile mass percentage is in a solvent 10% ~ 90%; As optimum, acetonitrile mass percentage is in a solvent 40% ~ 60%.

Preferably, DMF is contained in described solvent; As preferably, DMF mass percentage is in a solvent 10% ~ 90%; As optimum, DMF mass percentage is in a solvent 40% ~ 60%.

Compared to other solvents, acetonitrile and DMF can reach same reaction effect, and these two kinds of solvents are more cheap, are easy to get; Especially acetonitrile, can reclaim very easily.

Further, by 2, 2-bis-(4-hydroxy phenyl) HFC-236fa, para-halo oil of mirbane, solvent, catalyzer, copper powder is disposable to add in reaction vessel, in 20 ~ 40 DEG C of reactions 10 ~ 20 hours, after completion of the reaction, Filtration of catalyst, vacuum distillation recovered solvent, then in residue mother liquor, water and toluene separatory is added, after organic layer drying, be concentrated into dry, and then crystallization obtains 2, 2-bis-(4-(4-nitrophenoxy) phenyl) HFC-236fa crude product, crude product is through recrystallization, obtain 2, 2-bis-(4-(4-nitrophenoxy) phenyl) HFC-236fa fine work.

The present invention also provides a kind of method of low-temperature growth 2,2-bis-(4-(4-amino-benzene oxygen) phenyl) HFC-236fa, and step is as follows:

(1) 2 are prepared according to the arbitrary described method of claim 1-8,2-bis-(4-(4-amino-benzene oxygen) phenyl) HFC-236fa intermediate, i.e. 2,2-bis-(4-(4-nitrophenoxy) phenyl) HFC-236fa;

(2) prepared by step (1) 2,2-bis-(4-(4-nitrophenoxy) phenyl) HFC-236fa adds in ethyl acetate, deposit in case at Pd/C, 2,2-bis-(4-(4-amino-benzene oxygen) phenyl) HFC-236fa is prepared with hydrogen reducing.

Preferably, in step (2), the pressure of reduction reaction is 0.05MPa; As more preferably, the temperature of reduction reaction is 20 ~ 40 DEG C.

Method of the present invention adopts cold operation, and 20 ~ 40 DEG C just can complete reaction, and the reaction times is short, only need the preparation that just can complete intermediate for 10 hours; Method of the present invention can improve product yield, and yield is more than 79.9%, and product purity is high, more than 99.7%; Meanwhile, production cost is reduced.

Accompanying drawing explanation

Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification sheets, together with embodiments of the present invention for explaining the present invention, is not construed as limiting the invention.In the accompanying drawings:

Fig. 1 is the HPLC collection of illustrative plates of 4-BDAF prepared by the embodiment of the present invention 1.

Embodiment

Following embodiment is convenient to understand the present invention better, but does not limit the present invention.Experimental technique in following embodiment, if no special instructions, is ordinary method.Test materials used in following embodiment, if no special instructions, is commercially available.

Embodiment 1

Prepare 1000 milliliters of there-necked flasks, be equipped with mechanical stirring and water distilling apparatus, add 2, 2-bis-(4-hydroxy phenyl) HFC-236fa 33.6g (0.1mol), N, dinethylformamide 300mL, C-1 19.8g (0.1mol), copper powder 6.35g (0.1mol), parachloronitrobenzene 34.66g (0.22mol), under nitrogen protection, in 25 DEG C, react 10 hours, Filtration of catalyst, after most of solvent is reclaimed in mother liquor underpressure distillation, 300 milliliters of toluene and 100 ml water separatory are added in residue mother liquor, product now extracts organic layer, after organic layer dried over mgso, toluene is evaporated to dry, recrystallize can obtain 2, 2-bis-(4-(4-nitrophenoxy) phenyl) HFC-236fa crude product, in washout, solid adds 800 milliliters of ethanol and 200 milliliters of ethyl acetate mixed solvent recrystallizations, obtain 2, 2-bis-(4-(4-nitro phenoxyl phenyl)) HFC-236fa 53.1g.HPLC 99.6%, mp159.6 DEG C; Yield 91.87%.

2,2-bis-(4-(4-nitro phenoxyl phenyl)) HFC-236fa 53.1g is added, ethyl acetate 600 milliliters in stainless steel hydrogenation still, the palladium carbon 8g of 5%, after nitrogen replacement, in 30 DEG C, after control 0.05MPa hydrogen reducing reacts 6 hours, react complete.Stopped reaction, after nitrogen replacement, takes out material, Filtration of catalyst, and concentrating under reduced pressure removing ethyl acetate, obtain solid 5 times of ethyl alcohol recrystallizations, obtain white crystal 42.8g, HPLC 99.8%, mp162.4 DEG C of yield 89.9%, product HPLC spectrogram is shown in Fig. 1.The method applying this spectrogram calculating content is as shown in table 1.

The method that HPLC spectrogram calculates content applied by table 1

Chromatographic-type: fixed wave length chromatogram, 254nm

Peak quantitative: area

Quantitative calculation method: area %

Two-step reaction total recovery 82.6%.

Embodiment 2 to embodiment 29

In embodiment 2-embodiment 29, unlike in preparation 2,2-bis-(4-(4-nitrophenoxy) phenyl) HFC-236fa process, the kind of halogenated nitrobenzene, the kind of solvent, the kind of catalyzer, one or more in the consumption of copper powder; All the other design parameters and consumption and preparation method all identical with embodiment 1, actual conditions is as shown in table 2A and table 2B:

Table 2A embodiment 2-embodiment 19

Table 2B embodiment 20-embodiment 29

Last it is noted that the foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, although with reference to previous embodiment to invention has been detailed description, for a person skilled in the art, it still can be modified to the technical scheme described in foregoing embodiments, or carries out equivalent replacement to wherein portion of techniques feature.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (10)

1. a low-temperature growth 2, the method of 2-bis-(4-(4-amino-benzene oxygen) phenyl) HFC-236fa intermediate, described 2,2-bis-(4-(4-amino-benzene oxygen) phenyl) HFC-236fa intermediate is 2,2-bis-(4-(4-nitrophenoxy) phenyl) HFC-236fa, it is characterized in that: by 2,2-bis-(4-hydroxy phenyl) HFC-236fa and para-halo oil of mirbane are deposited at solvent, catalyzer and copper powder and are reacted in case, obtain 2,2-bis-(4-(4-nitrophenoxy) phenyl) HFC-236fa;

Wherein, described solvent is selected from N,N-dimethylacetamide, DMF, acetonitrile, dimethyl sulfoxide (DMSO), N, N-diethyl acetamide, N, N-diethylformamide, N-Methyl pyrrolidone, HMPA, the mixture of a kind of in acetone or two kinds;

Described catalyzer is selected from the mixture of a kind of in following structure or two kinds:

2. method according to claim 1, is characterized in that: described para-halo oil of mirbane selects parachloronitrobenzene or p-fluoronitrobenzene.

3. method according to claim 1, is characterized in that: the consumption of described catalyzer is 0.5 ~ 4 times of the amount of substance of 2,2-bis-(4-hydroxy phenyl) HFC-236fa; Preferably, the consumption of described catalyzer is 1 ~ 2 times of the amount of substance of 2,2-bis-(4-hydroxy phenyl) HFC-236fa.

4. method according to claim 1, is characterized in that: the consumption of described copper powder is 1 ~ 8 times of the amount of substance of 2,2-bis-(4-hydroxy phenyl) HFC-236fa; Preferably, the consumption of described copper powder is 2 ~ 4 times of the amount of substance of 2,2-bis-(4-hydroxy phenyl) HFC-236fa.

5. method according to claim 1, is characterized in that: the temperature of described reaction is 20 ~ 40 DEG C, preferably 25 ~ 35 DEG C.

6. method according to claim 1, is characterized in that: containing acetonitrile in described solvent; As preferably, acetonitrile mass percentage is in a solvent 10% ~ 90%; As optimum, acetonitrile mass percentage is in a solvent 40% ~ 60%.

7. method according to claim 1, is characterized in that: containing DMF in described solvent; As preferably, DMF mass percentage is in a solvent 10% ~ 90%; As optimum, DMF mass percentage is in a solvent 40% ~ 60%.

8. according to the arbitrary described method of claim 1-7, it is characterized in that: by 2, 2-bis-(4-hydroxy phenyl) HFC-236fa, para-halo oil of mirbane, solvent, catalyzer, copper powder is disposable to add in reaction vessel, in 20 ~ 40 DEG C of reactions 10 ~ 20 hours, after completion of the reaction, Filtration of catalyst, vacuum distillation recovered solvent, then in residue mother liquor, water and toluene separatory is added, after organic layer drying, be concentrated into dry, and then crystallization obtains 2, 2-bis-(4-(4-nitrophenoxy) phenyl) HFC-236fa crude product, crude product is through recrystallization, obtain 2, 2-bis-(4-(4-nitrophenoxy) phenyl) HFC-236fa fine work.

9. the method for low-temperature growth 2,2-bis-(4-(4-amino-benzene oxygen) phenyl) HFC-236fa, is characterized in that: step is as follows:

(1) 2 are prepared according to the arbitrary described method of claim 1-8,2-bis-(4-(4-amino-benzene oxygen) phenyl) HFC-236fa intermediate, i.e. 2,2-bis-(4-(4-nitrophenoxy) phenyl) HFC-236fa;

(2) prepared by step (1) 2,2-bis-(4-(4-nitrophenoxy) phenyl) HFC-236fa adds in ethyl acetate, deposit in case at Pd/C, 2,2-bis-(4-(4-amino-benzene oxygen) phenyl) HFC-236fa is prepared with hydrogen reducing.

10. method according to claim 8, is characterized in that: in step (2), and the pressure of reduction reaction is 0.05MPa; As preferably, the temperature of reduction reaction is 20 ~ 40 DEG C.