CN103819345B - A kind of preparation method of 2-aminobiphenyl derivate - Google Patents
A kind of preparation method of 2-aminobiphenyl derivate Download PDFInfo
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- CN103819345B CN103819345B CN201410107417.8A CN201410107417A CN103819345B CN 103819345 B CN103819345 B CN 103819345B CN 201410107417 A CN201410107417 A CN 201410107417A CN 103819345 B CN103819345 B CN 103819345B
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- LNTYYGQVRWRIKV-UHFFFAOYSA-N C[F]c(cc1-c2ccccc2)ccc1N Chemical compound C[F]c(cc1-c2ccccc2)ccc1N LNTYYGQVRWRIKV-UHFFFAOYSA-N 0.000 description 1
- XAMBIJWZVIZZOG-UHFFFAOYSA-N Cc(cc1)ccc1NN Chemical compound Cc(cc1)ccc1NN XAMBIJWZVIZZOG-UHFFFAOYSA-N 0.000 description 1
- HKOOXMFOFWEVGF-UHFFFAOYSA-N NNc1ccccc1 Chemical compound NNc1ccccc1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 1
- KRZCOLNOCZKSDF-UHFFFAOYSA-N Nc(cc1)ccc1F Chemical compound Nc(cc1)ccc1F KRZCOLNOCZKSDF-UHFFFAOYSA-N 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Nc1ccccc1 Chemical compound Nc1ccccc1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- JPBWZIPCMDZOPM-UHFFFAOYSA-N Nc1ccccc1-c(cc1)ccc1Cl Chemical compound Nc1ccccc1-c(cc1)ccc1Cl JPBWZIPCMDZOPM-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a kind of preparation method of 2-aminobiphenyl derivate, be specially and anils, phenylhydrazine derivant and phthalocyanine metal complex compound catalyzer are dissolved in solvent, react at 20-80 DEG C, obtain 2-aminobiphenyl derivate.The present invention uses anils for initiator, and raw material is easy to get, kind is a lot; The product types utilizing method of the present invention to obtain is various, not only directly can use, but also may be used for other and further react; Meanwhile, reaction conditions gentleness of the present invention, operation and last handling process are simple, and reaction process is catalysis, and greatly reduce the consumption of reagent and react generation and the discharge of refuse, productive rate is higher, is suitable for scale production.
Description
Technical field
The invention belongs to the preparing technical field of organic compound, be specifically related to a kind of preparation method of 2-aminobiphenyl derivate.
Background technology
2-aminobiphenyl derivate is the very important compound of a class, and it is all widely used in medicine, dyestuff and agricultural chemicals.Such as, 2-amino-4 '-chlordiphenyl can be used for the synthesis of sterilant boscalid amine Boscalid, amino-3 ' 4 ' 5 of 2-'-trifluoro-biphenyl can be used for the synthesis of pyrazole amide series bactericidal agent Xemium, and 2-amino-4-fluoro-3 ', 4 '-DCBP can be used for the synthesis of sterilant Bixafen.
The following method can synthesizing 2-aminobiphenyl derivate is had in prior art:
A. the people such as Wetzel discloses under titanous chloride exists, utilize the method for diazonium salt and anils Reactive Synthesis 2-aminobiphenyl derivate (see A. Wetzel, V. Ehrhardt, M. R. Heinrich Angew. Chem. Int. Ed. 2008,47,9130-9133), its synthetic route is as follows:
The raw materials used diazonium salt of the method, due to poor stability, is not easily stored, and needs in situ preparation onsite application, and reacts wayward, and productive rate is unstable, limits its industrial applications.
The people such as Hannelore Jasch disclose under Manganse Dioxide exists, utilize the method for phenylhydrazine and anils Reactive Synthesis 2-aminobiphenyl derivate (see Hannelore Jasch, Julia Scheumann, Markus R. Heinrich, J. Org. Chem. 2012,77,10,699 10706), its synthetic route is as follows:
Aforesaid method needs add greatly excessive anils and Manganse Dioxide just can obtain product, and resource utilization is too low, not only makes preparation cost high, and unfavorable to environment.
Therefore, the method developing the synthesis 2-aminobiphenyl derivate that wide application range of substrates is general, product yield is high, production cost is low, preparation process is simply controlled, be suitable for suitability for industrialized production is very important.
Summary of the invention
The object of this invention is to provide a kind of preparation method of 2-aminobiphenyl derivate.
To achieve the above object of the invention, the technical solution used in the present invention is: a kind of preparation method of 2-aminobiphenyl derivate, comprise the following steps: anils, phenylhydrazine derivant and catalyzer are dissolved in solvent, react at 20 ~ 80 DEG C, obtain 2-aminobiphenyl derivate;
Described anils is as shown in having structure general formula:
Wherein R
1, R
2, R
3selection take one of following scheme:
(1) R
1for nitro, R
2and R
3for hydrogen;
(2) R
2for nitro, R
1and R
3for hydrogen;
(3) R
1and R
2for hydrogen, R
3for hydrogen, methyl, methoxyl group, hydroxyl, fluorine, chlorine, bromine, 4-aminophenyl or nitro;
Described phenylhydrazine derivant is as shown in having structure general formula:
(1) R
4, R
5and R
6for hydrogen;
(2) R
4for methyl or chlorine, R
5and R
6for hydrogen;
(3) R
5for methyl, methoxyl group, fluorine, chlorine or bromine, R
4and R
6for hydrogen;
(4) R
4, R
5and R
6for fluorine;
(5) R
4, R
5for chlorine, R
6for hydrogen;
Described catalyzer is FePC, Cobalt Phthalocyanine, CuPc or manganese phthalocyanine;
Described solvent is selected from: the one in methyl alcohol, ethanol, acetonitrile, acetic acid, chloroform or toluene;
Described 2-aminobiphenyl derivate is as shown in having structure general formula:
。
In technique scheme, described anils is selected from the one in aniline, 4-monomethylaniline, 4-anisidine, 4-fluoroaniline, 4-bromaniline, 4-chloroaniline, PAP, p-diaminodiphenyl, 2-N-methyl-p-nitroaniline, 3-N-methyl-p-nitroaniline and 4-N-methyl-p-nitroaniline; Described phenylhydrazine derivant is selected from the one in phenylhydrazine, 3,4,5-trifluoro phenylhydrazines, 4-procarbazine, 4-methoxyl group phenylhydrazine, 4-fluorine phenylhydrazine, 4-chlorophenyl hydrazine, 4-bromophenyl-hydrazine, 3-procarbazine, 3-chlorophenyl hydrazine, 3,4-dichloro phenyl hydrazines.
In technique scheme, thin-layer chromatography (TLC) is utilized to follow the tracks of reaction until terminate completely.
In technique scheme, in molar ratio, anils: phenylhydrazine derivant: catalyzer is (5 ~ 10): 1: (0.05 ~ 0.2); Be preferably 10: 1: 0.1.
In preferred technical scheme, reaction terminates to carry out column chromatography for separation purification processes to product afterwards.
The reaction process of technique scheme can be expressed as:
Due to the utilization of technique scheme, the present invention compared with prior art has following advantages:
1. the present invention uses anils and phenylhydrazine derivant to be initiator, and raw material is easy to get, shelf-stable, of a great variety, and raw material dosage ratio is reasonable; The product 2-aminobiphenyl derivate type prepared thus is various, not only directly can use, but also may be used for other and further react;
2. preparation method's reaction conditions gentleness disclosed by the invention, operation and last handling process are simple; reaction process is stablized controlled, and catalytic efficiency is high, greatly reduces the consumption of reagent and reacts generation and the discharge of refuse; product yield is high, is suitable for large-scale production.
Embodiment
Below in conjunction with embodiment, the invention will be further described:
The synthesis of embodiment one: 2-phenylaniline
Using aniline, phenylhydrazine as raw material, its reaction formula is as follows:
(1) in reaction flask, aniline 0.47 gram (5 mmol), phenylhydrazine 0.108 gram (1 mmol), FePC 0.057 gram (0.1 mmol) and 10 ml methanol are added, 20 DEG C of reactions;
(2) TLC follows the tracks of reaction until terminate completely;
(3) crude by column chromatography that reaction obtains after terminating is separated (sherwood oil: ethyl acetate=20:1), obtains target product (productive rate 72%).
1H NMR (400 MHz, CDCl
3):
δ7.40-7.49 (m, 4H), 7.30-7.38 (m, 1H), 7.10-7.20 (m, 2H), 6.76-6.89 (m, 2H), 4.08 (br, s, 2H);
13C NMR (75 MHz, CDCl
3):
δ143.0, 139.4, 130.5, 129.1, 128.8, 128.5, 128.0, 127.2, 119.0, 115.9。
The synthesis of embodiment two: 2-amino-5-fluorine biphenyl
Using 4-fluoroaniline, phenylhydrazine as raw material, its reaction formula is as follows:
(1) in reaction flask, 4-fluoroaniline 1.11 grams (10 mmol), phenylhydrazine 0.108 gram (1 mmol), FePC 0.057 gram (0.1 mmol) and 10 milliliters of ethanol are added, 70 DEG C of reactions;
(2) TLC follows the tracks of reaction until terminate completely; The crude by column chromatography obtained after reaction terminates is separated (sherwood oil: ethyl acetate=20:1), obtains target product (productive rate 71%).
1H NMR (400 MHz, CDCl
3):
δ7.34-7.40 (m, 4H), 7.25-7.33 (m, 1H), 6.78-6.87 (m, 2H), 6.73 (dd,
J= 5.6, 9.4 Hz, 1H);
13C NMR (100 MHz, CDCl
3):
δ157.0 (d,
J= 237.9 Hz), 138.2, 137.7, 129.0, 128.9, 127.8, 117.6 (d,
J = 7.8 Hz), 116.8 (d,
J= 22.5 Hz), 114.9 (d,
J= 22.3 Hz)。
The synthesis of embodiment three: 2-amino-5-chlordiphenyl
Using 4-chloroaniline, phenylhydrazine as raw material, its reaction formula is as follows:
4-chloroaniline 0.89 gram (7 mmol), phenylhydrazine 0.108 gram (1 mmol), FePC 0.057 gram (0.1 mmol) and 10 milliliters of acetonitriles are added, 80 DEG C of reactions in reaction flask; TLC follows the tracks of reaction until terminate completely; The crude by column chromatography obtained after reaction terminates is separated (sherwood oil: ethyl acetate=20:1), obtains target product (productive rate 69%).
1H NMR (400 MHz, CDCl
3):
δ7.40-7.47 (m, 4H), 7.33-7.39 (m, 1H), 7.08-7.14 (m, 2H), 6.74 (d,
J= 8.9 Hz, 1H), 4.20 (br, s, 2H);
13C NMR (75 MHz, CDCl
3):
δ141.1, 137.2, 128.9, 127.9, 127.8, 127.1, 126.6, 122.1, 115.6。
The synthesis of embodiment four: 2-amino-5-bromo biphenyl
Using 4-bromaniline, phenylhydrazine as raw material, its reaction formula is as follows:
(1) in reaction flask, 4-bromaniline 1.55 grams (9 mmol), phenylhydrazine 0.108 gram (1 mmol), FePC 0.057 gram (0.1 mmol) and 10 milliliters of acetic acid are added, 50 DEG C of reactions;
(2) TLC follows the tracks of reaction until terminate completely;
(3) crude by column chromatography that reaction obtains after terminating is separated (sherwood oil: ethyl acetate=20:1), obtains target product (productive rate 68%).
1H NMR (400 MHz, CDCl
3):
δ7.29-7.52 (m, 5H), 7.18-7.27 (m, 2H), 6.64 (d,
J= 8.7 Hz, 1H), 3.63 (br, s, 2H);
13C NMR (100 MHz, CDCl
3):
δ142.6, 138.2, 132.8, 131.1, 129.5, 129.0, 128.9, 127.7, 117.1, 110.2。
The synthesis of embodiment five: 2-amino-5-methyl diphenyl
Using 4-monomethylaniline, phenylhydrazine as raw material, its reaction formula is as follows:
(1) in reaction flask, 4-monomethylaniline 1.07 grams (10 mmol), phenylhydrazine 0.108 gram (1 mmol), CuPc 0.058 gram (0.1 mmol) and 10 milliliters of chloroforms are added, 40 DEG C of reactions;
(2) TLC follows the tracks of reaction until terminate completely;
(3) crude by column chromatography that reaction obtains after terminating is separated (sherwood oil: ethyl acetate=20:1), obtains target product (productive rate 81%).
1H NMR (300 MHz, CDCl
3):
δ740-7.46 (m, 4H), 7.30-7.36 (m, 1H), 6.95-7.01 (m, 2H), 6.74 (d,
J= 7.9 Hz, 1H), 2.28 (s, 3H);
13C NMR (100 MHz, CDCl
3):
δ139.7, 139.3, 131.0, 129.1, 129.0, 128.8, 128.5, 127.2, 116.5, 20.5。
The synthesis of embodiment six: 2-amino-5-xenol
Using PAP, phenylhydrazine as raw material, its reaction formula is as follows:
(1) in reaction flask, PAP 1.09 grams (10 mmol), phenylhydrazine 0.108 gram (1 mmol), CuPc 0.029 gram (0.05 mmol) and 10 milliliters of toluene are added, 80 DEG C of reactions;
(2) TLC follows the tracks of reaction until terminate completely;
(3) crude by column chromatography that reaction obtains after terminating is separated (sherwood oil: ethyl acetate=20:1), obtains target product (productive rate 84%).
1H NMR (300 MHz, CDCl
3):
δ7.32-7.42 (m, 4H), 7.25-7.33 (m, 1H), 6.55-6.66 (m, 3H), 4.40 (s, 1H), 3.44(s, 2H);
13C NMR (75 MHz, DMSO-
d 6):
δ149.4, 140.3, 137.4, 129.1, 129.0, 127.5, 127.1, 117.3, 116.8, 115.7。
The synthesis of embodiment seven: 2-amino-5-methoxyl biphenyl
Using 4-anisidine, phenylhydrazine as raw material, its reaction formula is as follows:
(1) in reaction flask, PAP 1.23 grams (10 mmol), phenylhydrazine 0.108 gram (1 mmol), CuPc 0.058 gram (0.1 mmol) and 10 milliliters of acetic acid are added, 20 DEG C of reactions;
(2) TLC follows the tracks of reaction until terminate completely;
(3) crude by column chromatography that reaction obtains after terminating is separated (sherwood oil: ethyl acetate=20:1), obtains target product (productive rate 87%).
1H NMR (400 MHz, CDCl
3):
δ7.32-7.43 (m, 4H), 7.24-7.31 (m, 1H), 6.66-6.80 (m, 3H), 3.71 (s, 3H);
13C NMR (100 MHz, CDCl
3):
δ153.5, 139.1, 135.2, 129.9, 129.1, 128.8, 127.4, 117.9, 115.8, 114.4, 55.8。
Embodiment eight: 2-amino-5-(4-aminophenyl) synthesis of biphenyl
Using p-diaminodiphenyl, phenylhydrazine as raw material, its reaction formula is as follows:
1.84 grams, p-diaminodiphenyl (10 mmol), phenylhydrazine 0.108 gram (1 mmol), CuPc 0.087 gram (0.15 mmol) and 10 milliliters of acetic acid are added, 30 DEG C of reactions in reaction flask; TLC follows the tracks of reaction until terminate completely; The crude by column chromatography obtained after reaction terminates is separated (sherwood oil: ethyl acetate=20:1), obtains target product (productive rate 89%).
1H NMR (300 MHz, DMSO-
d 6):
δ7.42-7.54 (m, 4H), 7.31-7.39 (m, 1H), 7.25 (d,
J= 7.9 Hz, 3H), 7.15 (s, 1H), 6.79 (d,
J= 8.2 Hz, 1H), 6.59 (d,
J= 7.7 Hz, 2H), 5.02 (br, s, 2H), 4.73 (br, s, 2H);
13C NMR (100 MHz, DMSO-
d 6):
δ147.6, 143.6, 140.3, 130.2, 129.2, 129.1, 128.7, 127.6, 127.2, 126.2, 126.5, 125.9, 116.3, 114.8。
The synthesis of embodiment nine: 2-amino-5-nitrobiphenyl
Using 4-N-methyl-p-nitroaniline, phenylhydrazine as raw material, its reaction formula is as follows:
4-N-methyl-p-nitroaniline 1.38 grams (10 mmol), phenylhydrazine 0.108 gram (1 mmol), CuPc 0.116 gram (0.2 mmol) and 10 milliliters of acetonitriles are added, 40 DEG C of reactions in reaction flask; TLC follows the tracks of reaction until terminate completely; The crude by column chromatography obtained after reaction terminates is separated (sherwood oil: ethyl acetate=20:1), obtains target product (productive rate 70%).
1H NMR (300 MHz, CDCl
3):
δ8.00-8.11 (m, 2H), 7.46-7.53 (m, 2H), 7.38-7.46 (m, 3H), 6.72 (d,
J= 9.1 Hz, 1H), 4.50 (br, s, 2H);
13C NMR (75 MHz, CDCl
3):
δ149.8, 139.1, 136.9, 129.3, 128.8, 128.3, 126.6, 126.3, 125.1, 114.0。
The synthesis of embodiment ten: 2-amino-4-nitrobiphenyl
Using 3-N-methyl-p-nitroaniline, phenylhydrazine as raw material, its reaction formula is as follows:
3-N-methyl-p-nitroaniline 0.69 gram (5 mmol), phenylhydrazine 0.108 gram (1 mmol), CuPc 0.116 gram (0.2 mmol) and 10 milliliters of acetic acid are added, 50 DEG C of reactions in reaction flask; TLC follows the tracks of reaction until terminate completely; The crude by column chromatography obtained after reaction terminates is separated (sherwood oil: ethyl acetate=20:1), obtains target product (productive rate 67%).
1H NMR (300 MHz, CDCl
3):
δ7.63 (d,
J= 8.3 Hz, 1H), 7.59 (s, 1H), 7.46-7.52 (m, 2H), 7.38-7.46 (m, 3H), 7.22 (d,
J= 8.3 Hz, 1H), 4.09 (br, s, 2H);
13C NMR (75 MHz, CDCl
3):
δ148.1, 144.5, 137.4, 133.4, 131.0, 129.2, 128.6, 128.4, 113.1, 109.6。
Embodiment 11: 2-amino-5-methoxyl group-4 ' synthesis of-methyl diphenyl
Using 4-anisidine, 4-procarbazine as raw material, its reaction formula is as follows:
4-anisidine 1.02 grams (8 mmol), 4-procarbazine 0.122 gram (1 mmol), Cobalt Phthalocyanine 0.086 gram (0.15 mmol) and 10 milliliters of acetonitriles are added, 60 DEG C of reactions in reaction flask; TLC follows the tracks of reaction until terminate completely; The crude by column chromatography obtained after reaction terminates is separated (sherwood oil: ethyl acetate=20:1), obtains target product (productive rate 86%).
1H NMR (300 MHz, CDCl
3):
δ7.35 (d,
J = 7.7 Hz, 2H), 7.25 (d,
J = 7.3 Hz, 2H), 6.63-6.85 (m, 3H), 3.76 (s, 3H), 2.40 (s, 3H);
13C NMR (100 MHz, CDCl
3):
δ153.8, 137.2, 136.0, 130.3, 129.5, 129.0, 118.2, 115.8, 114.1, 55.8, 21.2。
Embodiment 12: 2-amino-5-methoxyl group-4 ' synthesis of-chlordiphenyl
Using 4-anisidine, 4-chlorophenyl hydrazine as raw material, its reaction formula is as follows:
4-anisidine 1.23 grams (10 mmol), 4-chlorophenyl hydrazine 0.142 gram (1 mmol), Cobalt Phthalocyanine 0.057 gram (0.1 mmol) and 10 milliliters of acetic acid are added, 70 DEG C of reactions in reaction flask; TLC follows the tracks of reaction until terminate completely; The crude by column chromatography obtained after reaction terminates is separated (sherwood oil: ethyl acetate=20:1), obtains target product (productive rate 90%).
1H NMR (300 MHz, CDCl
3):
δ7.34-7.46 (m, 4H), 6.78-6.91 (m, 2H), 6.72 (s, 1H), 5.23 (br, s, 2H), 3.78 (s, 3H);
13C NMR (100 MHz, CDCl
3):
δ153.1, 137.8, 136.4, 133.3, 130.4, 129.0, 127.8, 117.4, 115.7, 114.7, 55.8。
The synthesis of the chloro-4 '-chlordiphenyl of embodiment 13: 2-amino-5-
Using 4-chloroaniline, 4-chlorophenyl hydrazine as raw material, its reaction formula is as follows:
(1) in reaction flask, 4-chloroaniline 1.27 grams (10 mmol), 4-chlorophenyl hydrazine 0.142 gram (1 mmol), Cobalt Phthalocyanine 0.057 gram (0.1 mmol) and 10 milliliters of ethanol are added, 80 DEG C of reactions;
(2) TLC follows the tracks of reaction until terminate completely;
(3) crude by column chromatography that reaction obtains after terminating is separated (sherwood oil: ethyl acetate=20:1), obtains target product (productive rate 91%).
1H NMR (CDCl
3, 400 MHz):
δ7.42 (d,
J= 8.0 Hz, 2H), 7.36 (d,
J= 7.6 Hz, 2H ), 7.12 (d,
J= 8.5 Hz, 1H), 7.07 (s, 1H), 6.69 (d,
J= 8.4 Hz, 1H), 3.83 (br, 2H);
13C NMR (75 MHz, CDCl
3):
δ141.8, 136.6, 133.6, 130.3, 129.8, 129.2, 128.5, 127.7, 123.4, 116.9.
The synthesis of the bromo-4 '-fluorine biphenyl of embodiment 14: 2-amino-5-
Using 4-bromaniline, 4-fluorine phenylhydrazine as raw material, its reaction formula is as follows:
(1) in reaction flask, 4-bromaniline 1.71 grams (10 mmol), 4-fluorine phenylhydrazine 0.126 gram (1 mmol), FePC 0.057 gram (0.1 mmol) and 10 milliliters of chloroforms are added, 60 DEG C of reactions;
(2) TLC follows the tracks of reaction until terminate completely;
(3) crude by column chromatography that reaction obtains after terminating is separated (sherwood oil: ethyl acetate=20:1), obtains target product (productive rate 93%).
1H NMR (CDCl
3, 400 MHz):
δ7.36-7.40 (m, 2H), 7.19-7.24 (m, 2H), 7.11-7.15(m, 2H), 6.63 (d,
J= 8.43 Hz, 1H), 3.65 (br, 2H);
13C NMR (75 MHz, CDCl
3):
δ162.7 (d,
J= 242.97 Hz), 143.1, 133.2, 131.6, 131.1, 131.0, 128.7, 117.5, 116.3 (d,
J= 21.39 Hz), 110.6.
The synthesis of the iodo-3 '-chlordiphenyl of embodiment 15: 2-amino-5-
Using 4-Iodoaniline, 3-chlorophenyl hydrazine as raw material, its reaction formula is as follows:
(1) in reaction flask, 4-Iodoaniline 2.19 grams (10 mmol), 3-chlorophenyl hydrazine 0.142 gram (1 mmol), Cobalt Phthalocyanine 0.057 gram (0.1 mmol) and 10 milliliters of ethanol are added, 40 DEG C of reactions;
(2) TLC follows the tracks of reaction until terminate completely;
(3) crude by column chromatography that reaction obtains after terminating is separated (sherwood oil: ethyl acetate=20:1), obtains target product (productive rate 83%).
1H NMR (400 MHz, CDCl
3):
δ7.46 (s, 1H), 7.35-7.40 (m, 2H), 7.30-7.35 (m, 1H), 6.79 (dd,
J= 8.7, 2.7 Hz, 1H), 6.72-6.76 (m, 1H), 6.70 (d,
J= 2.7 Hz, 1H);
13C NMR (100 MHz, CDCl
3):
δ153.0, 141.2, 136.6, 134.6, 130.1, 129.2, 127.5, 127.3, 117.4, 115.5, 95.0。
Embodiment 16: 2-amino-5-methoxyl group-3 ' synthesis of-methyl diphenyl
Using 4-anisidine, 3-procarbazine as raw material, its reaction formula is as follows:
(1) in reaction flask, 4-anisidine 1.23 grams (10 mmol), 3-procarbazine 0.122 gram (1 mmol), CuPc 0.058 gram (0.1 mmol) and 10 ml methanol are added, 50 DEG C of reactions;
(2) TLC follows the tracks of reaction until terminate completely;
(3) crude by column chromatography that reaction obtains after terminating is separated (sherwood oil: ethyl acetate=20:1), obtains target product (productive rate 82%).
1H NMR (400 MHz, CDCl
3):
δ7.25 (t,
J= 7.5 Hz, 1H), 7.18-7.21 (m, 2H), 7.09 (d,
J= 7.6 Hz, 1H), 6.68-6.72 (m, 2H), 6.65-6.67 (m, 1H), 3.70 (s, 3H), 2.32 (s, 3H);
13C NMR (100 MHz, CDCl
3):
δ153.4, 139.1, 138.5, 137.0, 129.8, 128.7, 128.2, 126.1, 117.8, 115.7, 114.3, 55.8, 21.5。
Embodiment 17: 2-amino-3 ', the synthesis of 4 ', 5 '-trifluoro-biphenyl
With aniline, 3,4,5-trifluoro phenylhydrazines as raw material, its reaction formula is as follows:
(1) in reaction flask, aniline 0.93 gram (10 mmol), 3,4,5-trifluoro phenylhydrazine 0.162 gram (1 mmol), manganese phthalocyanine 0.057 gram (0.1 mmol) and 10 milliliters of toluene are added, 30 DEG C of reactions;
(2) TLC follows the tracks of reaction until terminate completely;
(3) crude by column chromatography that reaction obtains after terminating is separated (sherwood oil: ethyl acetate=20:1), obtains target product (productive rate 71%).
1H NMR (400 MHz, CDCl
3):
δ7.54 (d,
J= 7.6 Hz, 1H), 7.00-7.35 (m, 3H), 6.55-6.95 (m, 2H), 6.27 (br, s, 2H)。
Embodiment 18: 2-amino-4 ' synthesis of-chlordiphenyl
Using aniline, 4-chlorophenyl hydrazine as raw material, its reaction formula is as follows:
Aniline 0.93 gram (10 mmol), 4-chlorophenyl hydrazine 0.142 gram (1 mmol), manganese phthalocyanine 0.057 gram (0.1 mmol) and 10 milliliters of acetonitriles are added, 60 DEG C of reactions in reaction flask; TLC follows the tracks of reaction until terminate completely; The crude by column chromatography obtained after reaction terminates is separated (sherwood oil: ethyl acetate=20:1), obtains target product (productive rate 85%).
1H NMR (300 MHz, CDCl
3):
δ7.76 (d,
J= 7.6 Hz, 2H), 7.45-7.65 (m, 3H), 7.06-6.25 (m, 1H), 6.60-6.95 (m, 2H), 6.24 (br, s, 2H)。
Claims (4)
1. a preparation method for 2-aminobiphenyl derivate, is characterized in that, comprises the following steps: be dissolved in solvent by anils, phenylhydrazine derivant and catalyzer, reacts at 20 ~ 80 DEG C, obtains 2-aminobiphenyl derivate; In molar ratio, anils: phenylhydrazine derivant: catalyzer is (5 ~ 10): 1: (0.05 ~ 0.2);
Described anils is as shown in having structure general formula:
Wherein R
1, R
2, R
3selection take one of following scheme:
(1) R
1for nitro, R
2and R
3for hydrogen;
(2) R
2for nitro, R
1and R
3for hydrogen;
(3) R
1and R
2for hydrogen, R
3for hydrogen, methyl, methoxyl group, hydroxyl, fluorine, chlorine, bromine, 4-aminophenyl or nitro;
Described phenylhydrazine derivant is as shown in having structure general formula:
Wherein R
4, R
5, R
6selection take one of following scheme:
(1) R
4, R
5and R
6for hydrogen;
(2) R
4for methyl or chlorine, R
5and R
6for hydrogen;
(3) R
5for methyl, methoxyl group, fluorine, chlorine or bromine, R
4and R
6for hydrogen;
(4) R
4, R
5and R
6for fluorine;
(5) R
4, R
5for chlorine, R
6for hydrogen;
Described catalyzer is FePC, Cobalt Phthalocyanine, CuPc or manganese phthalocyanine;
Described solvent is selected from: the one in methyl alcohol, ethanol, acetonitrile, acetic acid, chloroform or toluene;
Described 2-aminobiphenyl derivate is as shown in having structure general formula:
。
2. the preparation method of 2-aminobiphenyl derivate according to claim 1, is characterized in that: utilize thin-layer chromatography to follow the tracks of reaction until terminate completely.
3. the preparation method of 2-aminobiphenyl derivate according to claim 1, is characterized in that: in molar ratio, anils: phenylhydrazine derivant: catalyzer is 10: 1: 0.1.
4. the preparation method of 2-aminobiphenyl derivate according to claim 1, is characterized in that: reaction terminates to carry out column chromatography for separation purification processes to product afterwards.
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