CN103204826B - One prepares the method for 3,7-dibromo thiodiphenylamine - Google Patents
One prepares the method for 3,7-dibromo thiodiphenylamine Download PDFInfo
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- CN103204826B CN103204826B CN201310128151.0A CN201310128151A CN103204826B CN 103204826 B CN103204826 B CN 103204826B CN 201310128151 A CN201310128151 A CN 201310128151A CN 103204826 B CN103204826 B CN 103204826B
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- Prior art keywords
- thiodiphenylamine
- dibromo
- hydrogen peroxide
- add
- mass concentration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000000034 method Methods 0.000 title claims abstract description 10
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims abstract description 36
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 32
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims abstract description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001953 recrystallisation Methods 0.000 claims abstract description 14
- 239000012153 distilled water Substances 0.000 claims abstract description 11
- 238000013019 agitation Methods 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000035484 reaction time Effects 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000012065 filter cake Substances 0.000 abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229950000688 phenothiazine Drugs 0.000 description 2
- 150000002990 phenothiazines Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Abstract
The invention provides the method that one prepares 3,7-dibromo thiodiphenylamine, first in reactor, add thiodiphenylamine, distilled water and hydrogen peroxide, then under agitation add Hydrogen bromide, stirred at ambient temperature backflow 0.5 ~ 1.5h, obtains turbid solution; After decompress filter, filter cake acetone recrystallization can obtain 3,7-dibromo thiodiphenylamine.The present invention is using hydrogen peroxide as oxygenant, and adopt " treating different things alike " legal system for 3,7-dibromo thiodiphenylamine, raw material of the present invention is easy to get, the reaction times is short, through recrystallization the higher target compound of productive rate.
Description
Technical field
The invention belongs to the field of chemical synthesis, particularly one prepares the method for 3,7-dibromo thiodiphenylamine.
Background technology
Since thiodiphenylamine synthesis in 1883, due to the structure that itself is special, thiodiphenylamine and derivative thereof has been made to have many-sided application, as pharmacology, sensitive materials etc.Be easy to introduce different substituting groups with 10-position at 3-, 7-of its structure, the phenothiazine derivative that stuctures and properties is more optimized can be formed.Because scientists is to the continuous research and development of electroluminescent organic material in recent years, the preparation technology of 3,7-position substituted phenothiazine is more and more efficient, optimization.
By Hsin-hunglin etc. at DyesandPigments, Volume83,2009, in the Spectroscopicinvestigationsofvinyl-substituted10H-phenot hiazine Research Literature delivered in pp.230-236, introduce and adopt thiodiphenylamine and N-bromo imide to be reaction raw materials, tetrahydrofuran (THF), as solvent, reacts under condition of ice bath, 3,7-dibromo thiodiphenylamine are synthesized.Although the method has successfully synthesized target compound, long reaction time, last handling process is complicated, and its synthesis technique need perfect further.
Summary of the invention
The invention provides that a kind of reaction times is short, productive rate is high and the method for 3,7-dibromo thiodiphenylamine is simply prepared in aftertreatment.
In order to achieve the above object, the technical solution used in the present invention comprises the following steps:
1) in reactor, add thiodiphenylamine, water and hydrogen peroxide, then under agitation add Hydrogen bromide, stirred at ambient temperature 0.5 ~ 1.5h, obtains turbid solution; Wherein, the H in thiodiphenylamine, hydrogen peroxide
2o
2and the mol ratio of HBr in Hydrogen bromide is 1:2:(2.1 ~ 2.5);
2) by turbid solution decompress filter, filter cake, through recrystallization, obtains 3,7-dibromo thiodiphenylamine.
Described step 1) in the thiodiphenylamine of every mole add the water of 3mL.
Described step 1) in the water that adds be distilled water.
Described step 1) in the mass concentration of hydrogen peroxide be 30%.
Described step 1) in hydrobromic mass concentration be 48%.
Described step 1) in Hydrogen bromide be adopt the mode dropwise dripped to add.
Described step 2) in filter cake dry before carrying out recrystallization.
Described step 2) in the solvent that adopts of recrystallization be acetone.
Preferably, described step 1) in thiodiphenylamine, H in hydrogen peroxide
2o
2and the mol ratio of HBr in Hydrogen bromide is 1:2:2.3, return time is 1h.
Compared with prior art, beneficial effect of the present invention is: the present invention take hydrogen peroxide as oxygenant, and thiodiphenylamine and Hydrogen bromide are raw material, adopt " treating different things alike " legal system for 3,7-dibromo thiodiphenylamine, and temperature of reaction is room temperature, therefore operating process of the present invention is easy, is easy to control; Meanwhile, reaction only needs 0.5 ~ 1.5h, and therefore the reaction times is short; Raw material of the present invention is easy to get, and cost is low, aftertreatment decompress filter, drying, recrystallization the higher target compound of productive rate, therefore aftertreatment is simple.
Accompanying drawing explanation
Fig. 1 is reaction scheme figure of the present invention;
Embodiment
See Fig. 1, the present invention by thiodiphenylamine, distilled water and mass concentration be 30% hydrogen peroxide add in there-necked flask, then dropwise dripping mass concentration is the Hydrogen bromide of 48%, stirred at ambient temperature reacts, the suspension liquid be obtained by reacting through decompress filter, filtration cakes torrefaction, then recrystallization, namely 3,7-dibromo thiodiphenylamine is obtained.
Below in conjunction with drawings and Examples, the present invention is described in further details.
Embodiment 1:
1) in there-necked flask, the thiodiphenylamine of 0.005mol and the distilled water of 3mL is added, add the hydrogen peroxide that 0.01mol mass concentration is 30% again, then under agitation dropwise dripping 0.0105mol mass concentration is the Hydrogen bromide of 48%, and stirred at ambient temperature 0.5h, obtains turbid solution;
2) by turbid solution decompress filter, filtration cakes torrefaction, then uses acetone recrystallization, namely obtains 3,7-dibromo thiodiphenylamine, and productive rate is 86.9%;
1hNMR (δ ppm, CDCl
3): 7.26-7.68 (m, 6H, Ar-H), 3.59 (s, 1H ,-NH).
Embodiment 2:
1) in there-necked flask, the thiodiphenylamine of 0.005mol and the distilled water of 3mL is added, add the hydrogen peroxide that 0.01mol mass concentration is 30% again, then under agitation dropwise dripping 0.0105mol mass concentration is the Hydrogen bromide of 48%, and stirred at ambient temperature 1h, obtains turbid solution;
2) by turbid solution decompress filter, filtration cakes torrefaction, then uses acetone recrystallization, namely obtains 3,7-dibromo thiodiphenylamine, and productive rate is 87.2%.
Embodiment 3:
1) in there-necked flask, the thiodiphenylamine of 0.005mol and the distilled water of 3mL is added, add the hydrogen peroxide that 0.01mol mass concentration is 30% again, then under agitation dropwise dripping 0.0105mol mass concentration is the Hydrogen bromide of 48%, and stirred at ambient temperature 1.5h, obtains turbid solution;
2) by turbid solution decompress filter, filtration cakes torrefaction, then uses acetone recrystallization, namely obtains 3,7-dibromo thiodiphenylamine, and productive rate is 87.0%.
Embodiment 4:
1) in there-necked flask, the thiodiphenylamine of 0.005mol and the distilled water of 3mL is added, add the hydrogen peroxide that 0.01mol mass concentration is 30% again, then under agitation dropwise dripping 0.0115mol mass concentration is the Hydrogen bromide of 48%, and stirred at ambient temperature 1h, obtains turbid solution;
2) by turbid solution decompress filter, filtration cakes torrefaction, then uses acetone recrystallization, namely obtains 3,7-dibromo thiodiphenylamine, and productive rate is 88.3%.
Embodiment 5:
1) in there-necked flask, the thiodiphenylamine of 0.005mol and the distilled water of 3mL is added, add the hydrogen peroxide that 0.01mol mass concentration is 30% again, then under agitation dropwise dripping 0.0115mol mass concentration is the Hydrogen bromide of 48%, and stirred at ambient temperature 1h, obtains turbid solution;
2) by turbid solution decompress filter, filtration cakes torrefaction, then uses acetone recrystallization, namely obtains 3,7-dibromo thiodiphenylamine, and productive rate is 87.9%.
Embodiment 6:
1) in there-necked flask, the thiodiphenylamine of 0.005mol and the distilled water of 3mL is added, add the hydrogen peroxide that 0.01mol mass concentration is 30% again, then under agitation dropwise dripping 0.0125mol mass concentration is the Hydrogen bromide of 48%, and stirred at ambient temperature 1h, obtains turbid solution;
2) by turbid solution decompress filter, filtration cakes torrefaction, then uses acetone recrystallization, namely obtains 3,7-dibromo thiodiphenylamine.
Claims (1)
1. prepare the method for 3,7-dibromo thiodiphenylamine for one kind, it is characterized in that, comprise the following steps:
1) in reactor, add the hydrogen peroxide that thiodiphenylamine, distilled water and mass concentration are 30%, then under agitation add in the mode dropwise dripped the Hydrogen bromide that mass concentration is 48%, stirred at ambient temperature 0.5 ~ 1.5h, obtains turbid solution; Wherein, the thiodiphenylamine of every mole adds the distilled water of 3mL, the H in thiodiphenylamine, hydrogen peroxide
2o
2and the mol ratio of HBr in Hydrogen bromide is 1:2:(2.1 ~ 2.5);
2) by turbid solution decompress filter, with acetone recrystallization after filtration cakes torrefaction, 3,7-dibromo thiodiphenylamine is obtained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310128151.0A CN103204826B (en) | 2013-04-12 | 2013-04-12 | One prepares the method for 3,7-dibromo thiodiphenylamine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310128151.0A CN103204826B (en) | 2013-04-12 | 2013-04-12 | One prepares the method for 3,7-dibromo thiodiphenylamine |
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| Publication Number | Publication Date |
|---|---|
| CN103204826A CN103204826A (en) | 2013-07-17 |
| CN103204826B true CN103204826B (en) | 2016-02-10 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310128151.0A Expired - Fee Related CN103204826B (en) | 2013-04-12 | 2013-04-12 | One prepares the method for 3,7-dibromo thiodiphenylamine |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0716069A1 (en) * | 1994-12-07 | 1996-06-12 | Great Lakes Chemical Konstanz GmbH | Process for the preparation of alkyl 4-bromophenyl ethers |
| WO2012125983A1 (en) * | 2011-03-17 | 2012-09-20 | Prosetta Antiviral Inc. | Antiviral treatments |
| CN102958525A (en) * | 2010-04-30 | 2013-03-06 | 普罗斯泰塔抗病毒药物股份有限公司 | Antiviral compounds |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53111081A (en) * | 1977-03-09 | 1978-09-28 | Agency Of Ind Science & Technol | Preparation of bromophenothiazine |
-
2013
- 2013-04-12 CN CN201310128151.0A patent/CN103204826B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0716069A1 (en) * | 1994-12-07 | 1996-06-12 | Great Lakes Chemical Konstanz GmbH | Process for the preparation of alkyl 4-bromophenyl ethers |
| CN102958525A (en) * | 2010-04-30 | 2013-03-06 | 普罗斯泰塔抗病毒药物股份有限公司 | Antiviral compounds |
| WO2012125983A1 (en) * | 2011-03-17 | 2012-09-20 | Prosetta Antiviral Inc. | Antiviral treatments |
Non-Patent Citations (3)
| Title |
|---|
| Quinones—VII: Halogenation and oxidative halogenation of phenols with hydrogen halides/hydrogen peroxide. Synthesis of p-chloranil and p-bromanil;H.LUBBECKE，等;《Tetrahedron》;19781231;第34卷(第10期);第1577-1579页 * |
| simple and efficient chlorimation and bromination of aromatic compounds with aqueous tbhp;Nivrutti B. Barhate，等;《Tetrahedron Letters》;19980827;第39卷(第35期);第6349-6350 * |
| 氢溴酸/双氧水溴代体系的应用及4-甲基二苯甲酮衍生物的合成;龚年华;《中南大学硕士学位论文》;20100531;第1页 * |
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| CN103204826A (en) | 2013-07-17 |
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