AU2018100392A4 - Medicine intermediates o-aminobiphenyl synthesis method - Google Patents
Medicine intermediates o-aminobiphenyl synthesis method Download PDFInfo
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- AU2018100392A4 AU2018100392A4 AU2018100392A AU2018100392A AU2018100392A4 AU 2018100392 A4 AU2018100392 A4 AU 2018100392A4 AU 2018100392 A AU2018100392 A AU 2018100392A AU 2018100392 A AU2018100392 A AU 2018100392A AU 2018100392 A4 AU2018100392 A4 AU 2018100392A4
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- Australia
- Prior art keywords
- solution
- aminobiphenyl
- washed
- mass fraction
- dimethylamine
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- Ceased
Links
- SCSIOHKHCVWXMX-MYODQMKGSA-N CC/C=C(\C=C/C)/c(cccc1)c1[N+]([O-])=O Chemical compound CC/C=C(\C=C/C)/c(cccc1)c1[N+]([O-])=O SCSIOHKHCVWXMX-MYODQMKGSA-N 0.000 description 1
- VRXJWXCJKVUSPM-UHFFFAOYSA-N CC1C=CC=CC1Br Chemical compound CC1C=CC=CC1Br VRXJWXCJKVUSPM-UHFFFAOYSA-N 0.000 description 1
- IQHSUWDZVBJPJR-ZCFIWIBFSA-N C[C@H](CC=C1)C(C=O)=C1Br Chemical compound C[C@H](CC=C1)C(C=O)=C1Br IQHSUWDZVBJPJR-ZCFIWIBFSA-N 0.000 description 1
- TWBPWBPGNQWFSJ-UHFFFAOYSA-N Nc1ccccc1-c1ccccc1 Chemical compound Nc1ccccc1-c1ccccc1 TWBPWBPGNQWFSJ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/84—Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/86—Separation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Abstract Medicine intermediates o-aminobiphenyl synthesis method, comprises the following steps: the reaction vessel were added 3 mol o-nitrobiphenyl and 4-5 mol 5 2-bromotoluene, 0.5 g p-chloromethylstyrene, raised the solution temperature to 50-55 'C, refluxed for 80-110 min, reduced solution temperature to 10-16 C, standing for layered, the solution was separated and the aqueous layer was extracted with dimethylamine solution, the extract was dried with anhydrous calcium sulfate, the anhydrous calcium sulfate was removed by filtration, after recovering dimethylamine, 10 the remaining solution was distilled under reduced pressure to collect 110-120 'C, washed with sodium bromide solution, washed with methylene chloride solution, washed with trifluoroacetic acid solution, dehydrated with dehydrating agent to obtain o-aminobiphenyl.
Description
FIELD OF THE INVENTION
The present invention relates to medicine intermediates o-aminobiphenyl 5 synthesis method.
GENERAL BACKGROUND
O-aminobiphenyl is mainly used as pharmaceutical intermediates, organic synthesis of raw materials, however, most of the existing synthetic methods are using stannous chloride as reactants, it is complicated and the final yield is not very high. Therefore, it is necessary to propose a new synthetic method for further improving the quality and yield of the product and reducing the byproduct content, it has important economic significance.
SUMMARY
The purpose of the present invention is to provide medicine intermediates o-aminobiphenyl synthesis method, comprises the following steps:
(i) the reaction vessel were added 3 mol o-nitrobiphenyl and 4-5 mol 2-bro mo toluene, 0.5 g p-chloromethylstyrene, raised the solution temperature to
50-55 °C, refluxed for 80-110 min, reduced solution temperature to 10-16°C, standing for layered, the solution was separated and the aqueous layer was extracted with dimethylamine solution, the extract was dried with anhydrous calcium sulfate, the anhydrous calcium sulfate was removed by filtration, after recovering dimethylamine, the remaining solution was distilled under reduced pressure to collect 110-120°C, washed with sodium bromide solution, washed with methylene chloride solution, washed with trifluoroacetic acid solution, dehydrated with dehydrating agent to obtain o-aminobiphenyl; wherein, the dimethylamine solution in step (i) has a mass fraction of 50 to 55%, the pressure at which the vacuum distillation described in step (i) is 0.7 to 0.8 kPa, the mass fraction of the sodium bromide solution in step (i) is 10-16%, the mass fraction of the dichloromethane solution in step (i) is 60-65%, the mass fraction of the trifluoroaeetic acid solution in step (i) is 70 to 77%, and the dehydrating agent described in step (i) is any one of solid sodium hydroxide and phosphorus pentoxide.
2018100392 28 Mar 2018
Advantage of the present invention is that: reducing intermediate links reaction, decreasing the reaction time and improving the reaction yield.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
The following examples with reference to specific embodiments of the present invention are further illustrated:
medicine intermediates o-aminobiphenyl synthesis method.
Embodiment 1
3 mol o-nitrobenzene, 4 mol 2-bromotoluene, 0.5 g p-chloromethylstyrene were added to the reaction vessel, the temperature of the solution was raised to 50 °C and refluxed for 80 min, the solution temperature was reduced to 10 °C, standing for layered, the solution was separated and the aqueous layer was extracted with dimethylamine solution with a mass fraction of 50%, the extract was dehydrated with anhydrous calcium sulfate, filtered to remove anhydrous calcium sulfate, after recovering dimethylamine, the remaining solution was heated at a pressure of 0.7 kPa to collect 110 °C fraction, washed with sodium bromide solution with a mass fraction of 10%, washed with dichloromethane solution with a mass fraction of 60%, washed with trifluoroaeetic acid solution with a mass fraction of 70%, dehydrated with solid sodium hydroxide dehydrating agent, got the finished o-amino biphenyl 446.16g, yield
2018100392 28 Mar 2018 of 88%.
Embodiment 2 mol o-nitrobenzene, 4.5 mol 2-bromotoluene, 0.5 g p-chloromethylstyrene were 5 added to the reaction vessel, the temperature of the solution was raised to 52 °C and refluxed for 90 min, the solution temperature was reduced to 13 °C, standing for layered, the solution was separated and the aqueous layer was extracted with dimethylamine solution with a mass fraction of 53%, the extract was dehydrated with anhydrous calcium sulfate, filtered to remove anhydrous calcium sulfate, after recovering dimethylamine, the remaining solution was heated at a pressure of 0.75 kPa to collect 115 °C fraction, washed with sodium bromide solution with a mass fraction of 13%, washed with dichloromethane solution with a mass fraction of 62%, washed with trifluoroacetic acid solution with a mass fraction of 73%, dehydrated with solid sodium hydroxide dehydrating agent, got the finished o-amino biphenyl 461.37g, yield of91%.
Embodiment 3 mol o-nitrobenzene, 5 mol 2-bromotoluene, 0.5 g p-chloromethylstyrene were added to the reaction vessel, the temperature of the solution was raised to 55 °C and refluxed for 110 min, the solution temperature was reduced to 16 °C, standing for layered, the solution was separated and the aqueous layer was extracted with dimethylamine solution with a mass fraction of 55%, the extract was dehydrated with anhydrous calcium sulfate, filtered to remove anhydrous calcium sulfate, after recovering dimethylamine, the remaining solution was heated at a pressure of 0.8 kPa to collect 120 °C fraction, washed with sodium bromide solution with a mass fraction of 16%, washed with dichloro methane solution with a mass fraction of 65%, washed with trifluoroacetic acid solution with a mass fraction of 77%, dehydrated with solid sodium hydroxide dehydrating agent, got the finished o-amino biphenyl 471.51 g, yield of 93%.
2018100392 28 Mar 2018
Claims (3)
- Claims1. Medicine intermediates o-aminobiphenyl synthesis method, comprises the following steps:(i) the reaction vessel were added 3 mol o-nitrobiphenyl and 4-5 mol 5 2-bromotoluene, 0.5 g p-chloromethylstyrene, raised the solution temperature to 50-55 °C, refluxed for 80-110 min, reduced solution temperature to 10-16°C, standing for layered, the solution was separated and the aqueous layer was extracted with dimethylamine solution, the extract was dried with anhydrous calcium sulfate, the anhydrous calcium sulfate was removed by filtration, after recovering dimethylamine,10 the remaining solution was distilled under reduced pressure to collect 110-120°C, washed with sodium bromide solution, washed with methylene chloride solution, washed with trifluoroacetic acid solution, dehydrated with dehydrating agent to obtain o-aminobiphenyl; wherein, the dimethylamine solution in step (i) has a mass fraction of 50 to 55%, the pressure at which the vacuum distillation described in step (i) is 0.715 to 0.8 kPa, the mass fraction of the sodium bromide solution in step (i) is 10-16%, the mass fraction of the dichloromethane solution in step (i) is 60-65%.
- 2. Medicine intermediates o-aminobiphenyl synthesis method according to claim 1 wherein the mass fraction of the trifluoroacetic acid solution in step (i) is 70 to 77%.
- 3. Medicine intermediates o-aminobiphenyl synthesis method according to claim 1 wherein the dehydrating agent described in step (i) is any one of solid sodium hydroxide and phosphorus pentoxide.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710074530.4A CN108409578A (en) | 2017-02-10 | 2017-02-10 | A kind of synthetic method of medicine intermediate o-aminobiphenyl |
| GBGB1705497.4A GB201705497D0 (en) | 2017-02-10 | 2017-04-05 | Medicine intermediates o-aminobiphenyl synthesis method |
| GBGB1705497.4 | 2017-04-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| AU2018100392A4 true AU2018100392A4 (en) | 2018-05-10 |
Family
ID=58682540
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU2018100392A Ceased AU2018100392A4 (en) | 2017-02-10 | 2018-03-28 | Medicine intermediates o-aminobiphenyl synthesis method |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN108409578A (en) |
| AU (1) | AU2018100392A4 (en) |
| GB (1) | GB201705497D0 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114471419A (en) * | 2021-12-28 | 2022-05-13 | 西安近代化学研究所 | Production device and process for preparing 1, 8-p-menthane diamine by one-step method |
-
2017
- 2017-02-10 CN CN201710074530.4A patent/CN108409578A/en active Pending
- 2017-04-05 GB GBGB1705497.4A patent/GB201705497D0/en not_active Ceased
-
2018
- 2018-03-28 AU AU2018100392A patent/AU2018100392A4/en not_active Ceased
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114471419A (en) * | 2021-12-28 | 2022-05-13 | 西安近代化学研究所 | Production device and process for preparing 1, 8-p-menthane diamine by one-step method |
| CN114471419B (en) * | 2021-12-28 | 2024-03-29 | 西安近代化学研究所 | Production device and process for preparing 1, 8-p-menthanediamine by one-step method |
Also Published As
| Publication number | Publication date |
|---|---|
| GB201705497D0 (en) | 2017-05-17 |
| CN108409578A (en) | 2018-08-17 |
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| Date | Code | Title | Description |
|---|---|---|---|
| FGI | Letters patent sealed or granted (innovation patent) | ||
| MK22 | Patent ceased section 143a(d), or expired - non payment of renewal fee or expiry |