CN106986774A - A kind of preparation method of 2 nitrobiphenyl - Google Patents
A kind of preparation method of 2 nitrobiphenyl Download PDFInfo
- Publication number
- CN106986774A CN106986774A CN201710330220.4A CN201710330220A CN106986774A CN 106986774 A CN106986774 A CN 106986774A CN 201710330220 A CN201710330220 A CN 201710330220A CN 106986774 A CN106986774 A CN 106986774A
- Authority
- CN
- China
- Prior art keywords
- preparation
- reaction
- nitro biphenyl
- nitrobiphenyl
- copper powder
- 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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- YOJKKXRJMXIKSR-UHFFFAOYSA-N 1-nitro-2-phenylbenzene Chemical group [O-][N+](=O)C1=CC=CC=C1C1=CC=CC=C1 YOJKKXRJMXIKSR-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- -1 nitrobenzene NITRODIAZONIUM Chemical compound 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- 238000005292 vacuum distillation Methods 0.000 claims abstract description 5
- 238000006887 Ullmann reaction Methods 0.000 claims abstract description 4
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims 1
- 150000002829 nitrogen Chemical class 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 238000012805 post-processing Methods 0.000 abstract description 2
- 238000010189 synthetic method Methods 0.000 abstract description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 235000010338 boric acid Nutrition 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- FRBUNLLUASHNDJ-UHFFFAOYSA-N (2-nitrophenyl)hydrazine Chemical class NNC1=CC=CC=C1[N+]([O-])=O FRBUNLLUASHNDJ-UHFFFAOYSA-N 0.000 description 1
- FWUHUNUOUDQTFG-UHFFFAOYSA-N (3,4,5-trifluorophenoxy)boronic acid Chemical class OB(O)OC1=CC(F)=C(F)C(F)=C1 FWUHUNUOUDQTFG-UHFFFAOYSA-N 0.000 description 1
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical class [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- ZOQCZTRFTARYGJ-UHFFFAOYSA-N chlorooxy(phenyl)borinic acid Chemical compound ClOB(O)C1=CC=CC=C1 ZOQCZTRFTARYGJ-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- LXNAVEXFUKBNMK-UHFFFAOYSA-N palladium(II) acetate Substances [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of preparation method of 2 nitrobiphenyl; it is related to technical field of organic synthesis; reaction raw materials are used as using 2 nitrobenzene NITRODIAZONIUM FLUOROBORATEs and chlorobenzene; copper powder is used as catalyst; ullmann reaction occurs for backflow under nitrogen protection; reaction is filtered to remove insoluble matter after terminating, and the nitrobiphenyl of product 2 is made through vacuum distillation.2 nitrobiphenyl purity can reach more than 98% made from synthetic method of the present invention, and yield reaches more than 75%, simplify post-processing operation on the basis of low preparation cost, it is ensured that product purity.
Description
Technical field：
The present invention relates to technical field of organic synthesis, and in particular to a kind of preparation method of 2 nitro biphenyl.
Background technology：
2 nitro biphenyl as function dough biphenyl compound, in agricultural chemicals and medical synthesis field, with important
Value.The analog of presently disclosed 2 nitro biphenyl, generally passes through precious metal palladium, cobalt, Huo Zhetong using boric acid as substrate
Cross reaction under high pressure to prepare, such as：
1st, patent CN201410692141, using palladium diacetate as catalyst, use to chlorophenylboronic acid and 2- nitrophenyl hydrazines for
Raw material, is prepared for 2 nitro biphenyl class compound.
2nd, patent CN201410785170, using palladium as catalyst, the nitre replaced using 3,4,5- trifluoro phenyl boric acids and ortho position
Base benzene is raw material, is prepared for 2 nitro biphenyl class compound.
3rd, document [Catalysis Communications, 2016, Vol.82, p24-28], [Journal of the
American Chemical Society,2016,Vol.138,p6392-5]、[Advanced Synthesis and
Catlysis, 2010, Vol.352, p3089-97], deliver and be coupled by suzuki, by 2- chloronitrobenzenes and the benzene of substitution
Boric acid is under noble metal catalyst, the method that coupling prepares 2 nitro biphenyl class compound.
The content of the invention：
The technical problems to be solved by the invention are that providing one kind prepares that cost is low, isolate and purify simple to operate and product
The preparation method of the high 2 nitro biphenyl of purity.
The technical problems to be solved by the invention are realized using following technical scheme：
A kind of preparation method of 2 nitro biphenyl, reaction raw materials, copper are used as using 2- nitrobenzene NITRODIAZONIUM FLUOROBORATE and chlorobenzene
As catalyst, under nitrogen protection backflow ullmann reaction occurs for powder, and reaction is filtered to remove insoluble matter after terminating, and through decompression
Product 2 nitro biphenyl is made in distillation.
The mol ratio of the 2- nitrobenzene NITRODIAZONIUM FLUOROBORATE, chlorobenzene and copper powder is 1:5-10:0.03-0.05.
The reaction time is 5-8h.
The copper powder mesh number is 100-200 mesh.
The beneficial effects of the invention are as follows：
(1) using excessive chlorobenzene simultaneously as reaction raw materials and reaction dissolvent, without adding other reaction dissolvents, reduce
The independent reclaimer operation of reaction dissolvent, reaction terminate after only need vacuum distillation chlorobenzene can using unreacted chlorobenzene and as react
The chlorobenzene of solvent is reclaimed in the lump, it is to avoid the waste of raw material and directly pollution of the discharge to environment；
(2) using copper powder as catalyst, 2 nitro biphenyl is prepared through ullmann reaction, different from through suzuki coupling reactions
The method for preparing 2 nitro biphenyl, it is to avoid the use of palladium class noble metal catalyst, is urged using copper powder cheap and easy to get as reaction
Agent, significantly reduces the use cost of catalyst, so that suitable for industrialized production；
(3) more than 98% can be reached by 2 nitro biphenyl purity made from herein described synthetic method, and yield reaches
To more than 75%, post-processing operation is simplified on the basis of low preparation cost, it is ensured that product purity.
Embodiment：
In order that the technical means, the inventive features, the objects and the advantages of the present invention are easy to understand, tie below
Specific embodiment is closed, the present invention is expanded on further.
Embodiment 1
Chlorobenzene (10mol, 1125.6g) is put into reactor as solvent, add 2- nitros NITRODIAZONIUM FLUOROBORATE (1mol,
236.92g), a certain amount of 100 mesh copper powder (0.05mol, 3.18g), system is begun to warm up after carrying out nitrogen displacement, back flow reaction
8h, cooling is filtered to remove insoluble matter, and filtrate carries out vacuum distillation, obtains product 2 nitro biphenyl, purity 98.8%, yield
75.8%.
Embodiment 2
Chlorobenzene (5mol, 562.8g) is put into reactor as solvent, add 2- nitros NITRODIAZONIUM FLUOROBORATE (1mol,
236.92g), a certain amount of 200 mesh copper powder (0.05mol, 3.18g), system is begun to warm up after carrying out nitrogen displacement, back flow reaction
5h, cooling is filtered to remove insoluble matter, and filtrate carries out vacuum distillation, obtains product 2 nitro biphenyl, purity 98.5%, yield
76.1%.
The general principle and principal character and advantages of the present invention of the present invention has been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the simply explanation described in above-described embodiment and specification is originally
The principle of invention, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (4)
1. a kind of preparation method of 2 nitro biphenyl, it is characterised in that：Using 2- nitrobenzene NITRODIAZONIUM FLUOROBORATE and chlorobenzene as anti-
Raw material is answered, as catalyst, under nitrogen protection backflow ullmann reaction occurs for copper powder, and reaction is filtered to remove insoluble after terminating
Thing, and product 2 nitro biphenyl is made through vacuum distillation.
2. the preparation method of 2 nitro biphenyl according to claim 1, it is characterised in that：The 2- nitrobenzene fluoboric acid weight
The mol ratio of nitrogen salt, chlorobenzene and copper powder is 1:5-10:0.03-0.05.
3. the preparation method of 2 nitro biphenyl according to claim 1, it is characterised in that：The reaction time is 5-8h.
4. the preparation method of 2 nitro biphenyl according to claim 1, it is characterised in that：The copper powder mesh number is 100-
200 mesh.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710330220.4A CN106986774B (en) | 2017-05-11 | 2017-05-11 | A kind of preparation method of 2 nitro biphenyl |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710330220.4A CN106986774B (en) | 2017-05-11 | 2017-05-11 | A kind of preparation method of 2 nitro biphenyl |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106986774A true CN106986774A (en) | 2017-07-28 |
| CN106986774B CN106986774B (en) | 2019-01-22 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710330220.4A Active CN106986774B (en) | 2017-05-11 | 2017-05-11 | A kind of preparation method of 2 nitro biphenyl |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106986774B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104529786A (en) * | 2014-12-16 | 2015-04-22 | 上海生农生化制品有限公司 | Method for synthesizing 3,4,5-trifluoro-2'-nitrobiphenyl |
-
2017
- 2017-05-11 CN CN201710330220.4A patent/CN106986774B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104529786A (en) * | 2014-12-16 | 2015-04-22 | 上海生农生化制品有限公司 | Method for synthesizing 3,4,5-trifluoro-2'-nitrobiphenyl |
Non-Patent Citations (2)
| Title |
|---|
| DONG-FANG JIANG，ET AL.: ""A General, Regiospecific Synthetic Route to Perfluoroalkylated Arenes via Arenediazonium Salts with RFCu(CH3CN) Complexes"", 《EUR. J. ORG. CHEM.》 * |
| LONGFEI GENG，ET AL.: ""Highly efficient palladium catalysts supported on nitrogen contained polymers for Suzuki-Miyaura reaction"", 《CATALYSIS COMMUNICATIONS》 * |
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| Publication number | Publication date |
|---|---|
| CN106986774B (en) | 2019-01-22 |
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| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A preparation method of 2-nitrobiphenyl Granted publication date: 20190122 Pledgee: Bengbu financing guarantee Group Co.,Ltd. Pledgor: CHINA SYNCHEM TECHNOLOGY Co.,Ltd. Registration number: Y2024980010170 |
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| PE01 | Entry into force of the registration of the contract for pledge of patent right |