CN101397258A - Process for preparation of 3,3-diamino-4,4-dihydroxybiphenyl - Google Patents
Process for preparation of 3,3-diamino-4,4-dihydroxybiphenyl Download PDFInfo
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- CN101397258A CN101397258A CNA2008100413437A CN200810041343A CN101397258A CN 101397258 A CN101397258 A CN 101397258A CN A2008100413437 A CNA2008100413437 A CN A2008100413437A CN 200810041343 A CN200810041343 A CN 200810041343A CN 101397258 A CN101397258 A CN 101397258A
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- dihydroxybiphenyl
- diamino
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- palladium
- hydrazine hydrate
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- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title description 3
- RPYXBUGGLSDICQ-UHFFFAOYSA-N 6,6-diamino-4-phenylcyclohexa-2,4-diene-1,1-diol Chemical group C1=CC(O)(O)C(N)(N)C=C1C1=CC=CC=C1 RPYXBUGGLSDICQ-UHFFFAOYSA-N 0.000 title 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 31
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 21
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000012452 mother liquor Substances 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- KZLDGFZCFRXUIB-UHFFFAOYSA-N 2-amino-4-(3-amino-4-hydroxyphenyl)phenol Chemical group C1=C(O)C(N)=CC(C=2C=C(N)C(O)=CC=2)=C1 KZLDGFZCFRXUIB-UHFFFAOYSA-N 0.000 claims abstract description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Substances CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 4
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 3
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 claims description 2
- JDFDHBSESGTDAL-UHFFFAOYSA-N 3-methoxypropan-1-ol Chemical compound COCCCO JDFDHBSESGTDAL-UHFFFAOYSA-N 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 238000007670 refining Methods 0.000 abstract description 2
- NTXCSKZBHUKPQU-UHFFFAOYSA-N 4-(4-hydroxy-3-nitrophenyl)-2-nitrophenol Chemical group C1=C([N+]([O-])=O)C(O)=CC=C1C1=CC=C(O)C([N+]([O-])=O)=C1 NTXCSKZBHUKPQU-UHFFFAOYSA-N 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- YVNRUPSDZZZUQJ-UHFFFAOYSA-N [O].NC1=CC=CC=C1 Chemical compound [O].NC1=CC=CC=C1 YVNRUPSDZZZUQJ-UHFFFAOYSA-N 0.000 description 9
- 239000011810 insulating material Substances 0.000 description 9
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- 239000004642 Polyimide Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000003141 primary amines Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- WBODDOZXDKQEFS-UHFFFAOYSA-N 1,2,3,4-tetramethyl-5-phenylbenzene Chemical group CC1=C(C)C(C)=CC(C=2C=CC=CC=2)=C1C WBODDOZXDKQEFS-UHFFFAOYSA-N 0.000 description 2
- -1 alkyl substituent aromatic diamine Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 230000003460 anti-nuclear Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000008359 benzonitriles Chemical class 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- IMHDGJOMLMDPJN-UHFFFAOYSA-N dihydroxybiphenyl Natural products OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002577 polybenzoxazole Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及一种3，3′－二氨基－4，4′－二羟基联苯的制备方法，包括：3，3′－二硝基－4，4′－二羟基联苯，在钯/炭、水合肼溶液和有机溶剂体系中于70℃～150℃温度范围内反应1～5小时后，过滤，冷却母液，析出产物，过滤，真空干燥，得3，3′－二氨基－4，4′－二羟基联苯。本发明操作简单，无需后续的精制提纯工艺，耗时少，所得产品收率高，纯度达99％以上，适用于工业化生产。
The present invention relates to a preparation method of 3,3'-diamino-4,4'-dihydroxybiphenyl, comprising: 3,3'-dinitro-4,4'-dihydroxybiphenyl, in palladium/ Carbon, hydrazine hydrate solution and organic solvent are reacted in the temperature range of 70°C to 150°C for 1 to 5 hours, filtered, cooled mother liquor, precipitated product, filtered, and vacuum dried to obtain 3,3'-diamino-4, 4′-Dihydroxybiphenyl. The invention is simple in operation, does not need a subsequent refining and purification process, takes less time, has a high yield of a product with a purity of over 99%, and is suitable for industrial production.
Description
Technical field
The invention belongs to the preparation field of phenolic hydroxy group aromatic dicarboxylic primary amine, particularly relate to a kind of 3,3 '-diamino-4, the preparation method of 4 '-dihydroxybiphenyl.
Background technology
The heteroaromatic polymkeric substance has outstanding thermostability, anti-nuclear radiation, flame retardant resistance, organic solvent resistance and good high cryogenic mechanics performance and electric property, has obtained widespread use in space flight and aviation, electronics microelectronics, automobile boats and ships, electric contour performance field.
Along with the information electronic product towards high performance, lightweight, slimming, the development that becomes more meticulous, the insulating material of flexible copper-clad plate (FCCL) is had higher requirement, high strength heat-resisting, low-k and low-dielectric loss etc. as the needs height.Therefore, polyimide material enjoys favor in the FCCL field.
3,3 '-diamino-4,4 '-dihydroxybiphenyl are one of important source material of synthetic hydroxyl polyimide resin, and therefore, it not only can be applicable to the FCCL field, but also can be applicable to the photo-sensistive polyimide material.In addition, 3,3 '-diamino-4,4 '-dihydroxybiphenyl also are the important raw and processed materials of synthetic polybenzoxazole resin.
3,3 '-diamino-4,4 '-dihydroxybiphenyl are one of a kind of important aromatic dicarboxylic primary amine.The preparation method of aromatic dicarboxylic primary amine has many patents, bibliographical information:
Chinese patent CN1485315A, disclose a kind of 3,4 '-preparation method of diaminodiphenyl oxide;
Chinese patent CN1425644A, disclose a kind of 2, the preparation method of two [4-(4-amino-benzene oxygen) phenyl] propane of 2-;
Japanese Patent JP63-126848, disclose a kind of 4,4 '-two (3-amino-benzene oxygen)-3,3 ', 5,5 '-preparation method of tetramethyl biphenyl;
Japanese Patent JP62-248635, disclose a kind of 4,4 '-preparation method of two (3-amino-benzene oxygen) biphenyl;
U.S. Pat 4377525, disclose a kind of 1, the preparation method of two (3-amino-benzene oxygen) benzene of 3-;
U.S. Pat 4064107, disclose a kind of 4,4 '-preparation method of two (4-amino-benzene oxygen) phenyl ether;
Chinese patent CN1919829A discloses a kind of preparation method of alkyl substituent aromatic diamine;
Chinese patent CN101134730A, disclose a kind of 4,4 '-diamino-4 "-preparation method of hydroxy benzophenone alkane;
Chinese patent CN101157623A, disclose a kind of 1, the preparation method of two (4-amino-benzene oxygen) benzene of 4-;
Chinese patent CN101117324A, disclose a kind of 2, the preparation method of two (4-amino-benzene oxygen) cyanobenzenes of 6-;
Chinese patent CN101100446A, disclose a kind of 2, the preparation method of two [3-amino-4-(4-cyano-benzene oxygen) phenyl] propane of 2-;
Chinese patent CN101130502A, disclose a kind of 2, two [3-amino-4-(4-nitrophenoxy) phenyl]-1,1,1,3,3 of 2-, the preparation method of 3-HFC-236fa;
Chinese patent CN101186579A, disclose a kind of 4,4 '-two (4-amino-benzene oxygen)-3,3 ', 5,5 '-preparation method of tetramethyl biphenyl;
It is a kind of 1 that people such as Yu Xinhai [insulating material communication, 1999,32 (5): 1-4] disclose, the preparation method of two (3-amino-benzene oxygen) benzene of 3-, simultaneously, the also synthetic series of heat plastic polyimide that obtained.
That people such as Yu Xinhai [insulating material, 2001,34 (4): 13-16] disclose is a kind of 3,3 '-preparation method of diaminodiphenyl oxide;
It is a kind of 2 that people such as Yu Xinhai [insulating material, 2001,34 (6): 3-6] disclose, the preparation method of two [4-(3-amino-benzene oxygen) phenyl] propane of 2-;
It is a kind of 2 that people such as Yu Xinhai [insulating material, 2002,35 (4): 3-7] disclose, the preparation method of two [4-(4-amino-benzene oxygen) phenyl] propane of 2-;
It is a kind of 2 that Yu Xinhai [New Chemical Materials, 2003,31 (10): 24-27] discloses, two [4-(4-amino-benzene oxygen) phenyl]-1,1,1,3,3 of 2-, the preparation method of 3-HFC-236fa;
That people such as Yu Xinhai [insulating material, 2006,39 (5): 1-3,6] disclose is a kind of 4,4 '-preparation method of two (3-amino-benzene oxygen) benzophenone;
It is a kind of 1 that people such as Yu Xinhai [insulating material, 2006,39 (3): 1-4,8] disclose, the preparation method of two (4-amino-benzene oxygen) benzene of 3-;
It is a kind of 2 that people such as Yu Xinhai [insulating material, 2007,40 (4): 1-5,8] disclose, two (the 3-amino-4-hydroxy phenyl)-1,1,1,3,3 of 2-, the preparation method of 3-HFC-236fa;
That people such as Yu Xinhai [insulating material, 2008,41 (2): 10-14] disclose is a kind of 4,4 '-preparation method of two (4-amino-benzene oxygen) biphenyl.
But 3,3 '-diamino-4, the simple and yield of the technology of 4 '-dihydroxybiphenyl, the preparation method that purity is high also do not have report.
Summary of the invention
The purpose of this invention is to provide a kind of 3,3 '-diamino-4, the preparation method of 4 '-dihydroxybiphenyl, this method technology is simple, need not follow-up refining purifying technique, consuming time few, the three wastes are few, the purity of product and yield height, are applicable to suitability for industrialized production.
Chemical equation of the present invention is as follows:
Of the present invention a kind of 3,3 '-diamino-4, the preparation method of 4 '-dihydroxybiphenyl comprises the following steps:
3,3 '-dinitrobenzene-4,4 '-dihydroxybiphenyl, in palladium/charcoal, hydrazine hydrate solution and organic solvent system in 70 ℃～150 ℃ temperature range internal reactions after 1～5 hour, filtered while hot, the cooling mother liquor is separated out the white crystal product, filters, dry, obtain 3 of white, 3 '-diamino-4,4 '-dihydroxybiphenyl crystal.
Described palladium/charcoal is that the palladium mass percent is palladium/charcoal of 1%～15%.
Described hydrazine hydrate solution is that mass percent concentration is 60%～85% hydrazine hydrate solution.
Described organic solvent is methyl alcohol, ethanol, Virahol, n-propyl alcohol, propyl carbinol, isopropylcarbinol, ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,4-dioxane, 2-methyl cellosolve, cellosolvo, 2-methyl cellosolve, 3-methoxypropanol, 2-oxyethyl group propyl alcohol, 3-oxyethyl group propyl alcohol, N-ethyl-2-pyrrolidone, N-N-methyl-2-2-pyrrolidone N-, dimethyl sulfoxide (DMSO), N, one or more mixtures in dinethylformamide, the N,N-dimethylacetamide.
Described 3,3 '-dinitrobenzene-4, the weight ratio of 4 '-dihydroxybiphenyl and palladium/charcoal is 100:1～20.
Described 3,3 '-dinitrobenzene-4, the mol ratio of 4 '-dihydroxybiphenyl and hydrazine hydrate is 1:10～30.
Described 3,3 '-dinitrobenzene-4, the weightmeasurement ratio of 4 '-dihydroxybiphenyl and organic solvent are 1 gram: 15 milliliters～100 milliliters.
Beneficial effect of the present invention:
(1) the present invention is preparation 3,3 '-diamino-4, the commercial run of 4 '-dihydroxybiphenyl;
(2) three wastes are few, and are environmentally friendly;
(3) consuming time few, obviously energy-saving and cost-reducing;
(4) industrial chemicals convenient sources simple to operate, related, kind is few;
(5) product yield and purity are all very high, and purity reaches more than 99%.
Description of drawings
Fig. 1 is 3,3 '-diamino-4, the molecular structure of 4 '-dihydroxybiphenyl;
Fig. 2 is 3,3 '-diamino-4, the differential scanning calorimeter of 4 '-dihydroxybiphenyl crystallized product (DSC) scanning spectra.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
With 27.6 gram (0.1 moles) 3,3 '-dinitrobenzene-4,4 '-dihydroxybiphenyl, 0.3 gram palladium mass percent are that 15% palladium/charcoal and 480ml ethylene glycol add in the reaction flask, stir, heat temperature raising to 60 ℃, begin to drip mass concentration and be 60% hydrazine hydrate solution, totally 160.0 grams (solution weight).After hydrazine hydrate is added dropwise to complete, in 70 ℃-150 ℃ temperature range, continued stirring reaction 1 hour, cold slightly, filtered while hot, cooling mother liquor, separate out the white crystals product, filter, vacuum-drying obtains 3 of 19.5 gram whites, 3 '-diamino-4,4 '-dihydroxybiphenyl crystal, fusing point are 334.4 ℃ (seeing accompanying drawing 2), and purity is 99.8%, according to 3 of reality acquisition, 3 '-diamino-4, the amount of 4 '-dihydroxybiphenyl and theoretical amount (21.6 gram) calculate 3,3 '-diamino-4, the yield of 4 '-dihydroxybiphenyl are 90.2%.
With 27.6 gram (0.1 moles) 3,3 '-dinitrobenzene-4,4 '-dihydroxybiphenyl, 5.5 gram palladium mass percents are that 1% palladium/charcoal, 2500ml ethylene glycol and 260ml ethanol add in the reaction flask, stir, heat temperature raising to 60 ℃, begin to drip mass concentration and be 85% hydrazine hydrate solution, totally 95.0 grams (solution weight).After hydrazine hydrate is added dropwise to complete, in 70 ℃-150 ℃ temperature range, continued stirring reaction 5 hours, cold slightly, filtered while hot, cooling mother liquor, separate out the white crystals product, filter, vacuum-drying obtains 3 of 18.3 gram whites, 3 '-diamino-4,4 '-dihydroxybiphenyl crystal, fusing point are 335.9 ℃, and purity is 99.9%, according to 3 of reality acquisition, 3 '-diamino-4, the amount of 4 '-dihydroxybiphenyl and theoretical amount (21.6 gram) calculate 3,3 '-diamino-4, the yield of 4 '-dihydroxybiphenyl are 84.5%.
Embodiment 3
With 27.6 gram (0.1 moles) 3,3 '-dinitrobenzene-4,4 '-dihydroxybiphenyl, 4.0 gram palladium mass percents are that 5% palladium/charcoal, 500ml ethylene glycol and 500ml 2-methyl cellosolve add in the reaction flask, stir, heat temperature raising to 60 ℃, begin to drip mass concentration and be 80% hydrazine hydrate solution, totally 90.6 grams (solution weight).After hydrazine hydrate is added dropwise to complete, in 70 ℃-150 ℃ temperature range, continued stirring reaction 4 hours, cold slightly, filtered while hot, the cooling mother liquor is separated out the white crystals product, filter, vacuum-drying obtains 3 of 20.0 gram whites, 3 '-diamino-4,4 '-dihydroxybiphenyl crystal, purity is 99.7%, according to 3 of reality acquisition, 3 '-diamino-4, the amount of 4 '-dihydroxybiphenyl and theoretical amount (21.6 gram), calculate 3,3 '-diamino-4, the yield of 4 '-dihydroxybiphenyl are 92.5%.
Embodiment 4
With 27.6 gram (0.1 moles) 3,3 '-dinitrobenzene-4,4 '-dihydroxybiphenyl, 3.0 gram palladium mass percents are 10% palladium/charcoal, 200ml N, N-N,N-DIMETHYLACETAMIDE and 1000ml 1, the 2-propylene glycol adds in the reaction flask, stirs heat temperature raising to 60 ℃, begin to drip mass concentration and be 80% hydrazine hydrate solution, totally 185.0 grams (solution weight).After hydrazine hydrate is added dropwise to complete, in 70 ℃-150 ℃ temperature range, continued stirring reaction 1 hour, cold slightly, filtered while hot, the cooling mother liquor is separated out the white crystals product, filter, vacuum-drying obtains 3 of 19.7 gram whites, 3 '-diamino-4,4 '-dihydroxybiphenyl crystal, purity is 99.8%, according to 3 of reality acquisition, 3 '-diamino-4, the amount of 4 '-dihydroxybiphenyl and theoretical amount (21.6 gram), calculate 3,3 '-diamino-4, the yield of 4 '-dihydroxybiphenyl are 91.0%.
Embodiment 5
With 27.6 gram (0.1 moles) 3,3 '-dinitrobenzene-4,4 '-dihydroxybiphenyl, 3.5 gram palladium mass percents are that 10% palladium/charcoal, 600ml dimethyl sulfoxide (DMSO), 20ml methyl alcohol and 1200ml cellosolvo add in the reaction flask, stir, heat temperature raising to 60 ℃, begin to drip mass concentration and be 85% hydrazine hydrate solution, totally 80.6 grams (solution weight).After hydrazine hydrate is added dropwise to complete, in 70 ℃-150 ℃ temperature range, continued stirring reaction 2 hours, cold slightly, filtered while hot, the cooling mother liquor is separated out the white crystals product, filter, vacuum-drying obtains 3 of 17.8 gram whites, 3 '-diamino-4,4 '-dihydroxybiphenyl crystal, purity is 99.8%, according to 3 of reality acquisition, 3 '-diamino-4, the amount of 4 '-dihydroxybiphenyl and theoretical amount (21.6 gram), calculate 3,3 '-diamino-4, the yield of 4 '-dihydroxybiphenyl are 82.5%.
With 27.6 gram (0.1 moles) 3,3 '-dinitrobenzene-4,4 '-dihydroxybiphenyl, 1.6 gram palladium mass percents are 15% palladium/charcoal, 200ml ethanol, 1200ml2-ethoxy ethanol and 800ml 1, ammediol adds in the reaction flask, stir, heat temperature raising to 60 ℃ begins to drip mass concentration and is 60% hydrazine hydrate solution, totally 90.0 grams (solution weight).After hydrazine hydrate is added dropwise to complete, in 70 ℃-150 ℃ temperature range, continued stirring reaction 5 hours, cold slightly, filtered while hot, the cooling mother liquor is separated out the white crystals product, filter, vacuum-drying obtains 3 of 14.1 gram whites, 3 '-diamino-4,4 '-dihydroxybiphenyl crystal, purity is 99.5%, according to 3 of reality acquisition, 3 '-diamino-4, the amount of 4 '-dihydroxybiphenyl and theoretical amount (21.6 gram), calculate 3,3 '-diamino-4, the yield of 4 '-dihydroxybiphenyl are 65.4%.
Claims (7)
1. one kind 3,3 '-diamino-4, the preparation method of 4 '-dihydroxybiphenyl comprises the following steps:
3,3 '-dinitrobenzene-4,4 '-dihydroxybiphenyl, in palladium/charcoal, hydrazine hydrate solution and organic solvent system in 70 ℃～150 ℃ temperature range internal reactions after 1～5 hour, filter, the cooling mother liquor is separated out product, filters, drying gets 3,3 '-diamino-4,4 '-dihydroxybiphenyl.
2. according to claim 13,3 '-diamino-4, the preparation method of 4 '-dihydroxybiphenyl is characterized in that: described palladium/charcoal is that the palladium mass percent is palladium/charcoal of 1%～15%.
3. according to claim 13,3 '-diamino-4, the preparation method of 4 '-dihydroxybiphenyl is characterized in that: described hydrazine hydrate solution is that mass percent concentration is 60%～85% hydrazine hydrate solution.
4. according to claim 13,3 '-diamino-4, the preparation method of 4 '-dihydroxybiphenyl, it is characterized in that: described organic solvent is a methyl alcohol, ethanol, Virahol, n-propyl alcohol, propyl carbinol, isopropylcarbinol, ethylene glycol, 1, the 2-propylene glycol, 1, ammediol, 1, the 4-dioxane, 2-methyl cellosolve, cellosolvo, 2-methyl cellosolve, the 3-methoxypropanol, 2-oxyethyl group propyl alcohol, 3-oxyethyl group propyl alcohol, the N-ethyl-2-pyrrolidone, the N-N-methyl-2-2-pyrrolidone N-, dimethyl sulfoxide (DMSO), N, dinethylformamide, one or more mixtures in the N,N-dimethylacetamide.
5. according to claim 1 and 23,3 '-diamino-4, the preparation method of 4 '-dihydroxybiphenyl is characterized in that: described 3,3 '-dinitrobenzene-4, the weight ratio of 4 '-dihydroxybiphenyl and palladium/charcoal is 100:1～20.
6. according to claim 1 or 3 described 3,3 '-diamino-4, the preparation method of 4 '-dihydroxybiphenyl is characterized in that: described 3,3 '-dinitrobenzene-4, the mol ratio of 4 '-dihydroxybiphenyl and hydrazine hydrate is 1:10～30.
7. according to claim 1 or 4 described 3,3 '-diamino-4, the preparation method of 4 '-dihydroxybiphenyl is characterized in that: described 3,3 '-dinitrobenzene-4, the weightmeasurement ratio of 4 '-dihydroxybiphenyl and organic solvent are 1 gram: 15 milliliters～100 milliliters.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102584610A (en) * | 2011-12-28 | 2012-07-18 | 四川东材绝缘技术有限公司 | Bisphenol 2 (m-amino p-hydroxy phenyl) ether hydrochloride and preparation method and application thereof |
| CN104177265A (en) * | 2014-07-23 | 2014-12-03 | 金发科技股份有限公司 | 4,6-diamino-resorcinol hydrochloride synthesis method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584610A (en) * | 2011-12-28 | 2012-07-18 | 四川东材绝缘技术有限公司 | Bisphenol 2 (m-amino p-hydroxy phenyl) ether hydrochloride and preparation method and application thereof |
| CN102584610B (en) * | 2011-12-28 | 2014-03-26 | 四川东材绝缘技术有限公司 | Bisphenol 2 (m-amino p-hydroxy phenyl) ether hydrochloride and preparation method and application thereof |
| CN104177265A (en) * | 2014-07-23 | 2014-12-03 | 金发科技股份有限公司 | 4,6-diamino-resorcinol hydrochloride synthesis method |
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