CN105801422A - Preparation method of o-nitrobenzol - Google Patents
Preparation method of o-nitrobenzol Download PDFInfo
- Publication number
- CN105801422A CN105801422A CN201610229777.4A CN201610229777A CN105801422A CN 105801422 A CN105801422 A CN 105801422A CN 201610229777 A CN201610229777 A CN 201610229777A CN 105801422 A CN105801422 A CN 105801422A
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- Prior art keywords
- benzoquinone
- ethane
- bis
- reaction
- methanol
- 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.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 title abstract 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 45
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 238000006722 reduction reaction Methods 0.000 claims abstract description 11
- 239000006227 byproduct Substances 0.000 claims abstract description 10
- 239000000047 product Substances 0.000 claims abstract description 10
- 238000004821 distillation Methods 0.000 claims abstract description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 4
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 15
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 12
- 238000004064 recycling Methods 0.000 claims description 6
- -1 boron Sodium hydride Chemical compound 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 6
- YBOZRPPSBVIHGJ-UHFFFAOYSA-N 1-nitro-2-[2-(2-nitrophenyl)ethyl]benzene Chemical compound [O-][N+](=O)C1=CC=CC=C1CCC1=CC=CC=C1[N+]([O-])=O YBOZRPPSBVIHGJ-UHFFFAOYSA-N 0.000 abstract 3
- BWRBVBFLFQKBPT-UHFFFAOYSA-N (2-nitrophenyl)methanol Chemical compound OCC1=CC=CC=C1[N+]([O-])=O BWRBVBFLFQKBPT-UHFFFAOYSA-N 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- CMWKITSNTDAEDT-UHFFFAOYSA-N 2-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=CC=C1C=O CMWKITSNTDAEDT-UHFFFAOYSA-N 0.000 description 2
- JKTYGPATCNUWKN-UHFFFAOYSA-N 4-nitrobenzyl alcohol Chemical compound OCC1=CC=C([N+]([O-])=O)C=C1 JKTYGPATCNUWKN-UHFFFAOYSA-N 0.000 description 2
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- ZWWCURLKEXEFQT-UHFFFAOYSA-N dinitrogen pentaoxide Chemical compound [O-][N+](=O)O[N+]([O-])=O ZWWCURLKEXEFQT-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- HYIMSNHJOBLJNT-UHFFFAOYSA-N nifedipine Chemical compound COC(=O)C1=C(C)NC(C)=C(C(=O)OC)C1C1=CC=CC=C1[N+]([O-])=O HYIMSNHJOBLJNT-UHFFFAOYSA-N 0.000 description 2
- 229960001597 nifedipine Drugs 0.000 description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical group [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 0 *Cc(cccc1)c1[N+]([O-])=O Chemical compound *Cc(cccc1)c1[N+]([O-])=O 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- CDMGNVWZXRKJNS-UHFFFAOYSA-N 2-benzylphenol Chemical compound OC1=CC=CC=C1CC1=CC=CC=C1 CDMGNVWZXRKJNS-UHFFFAOYSA-N 0.000 description 1
- 206010002383 Angina Pectoris Diseases 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 208000035126 Facies Diseases 0.000 description 1
- 206010020772 Hypertension Diseases 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- WBOHXLDSPBIPTP-UHFFFAOYSA-N N,N-dimethyl-1,8-naphthyridin-4-amine Chemical compound CN(C1=CC=NC2=NC=CC=C12)C WBOHXLDSPBIPTP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- BVJSGOYEEDZAGW-UHFFFAOYSA-N [chloro(nitro)methyl]benzene Chemical group [O-][N+](=O)C(Cl)C1=CC=CC=C1 BVJSGOYEEDZAGW-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 208000029078 coronary artery disease Diseases 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 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 preparation method of o-nitrobenzol, which takes 1, 2-bis (o-nitrophenyl) ethane (13) as a raw material to react with benzoquinone; after the reaction is finished, evaporating excessive benzoquinone and a byproduct hydroquinone; adding methanol into the residue for dissolving, and then adding sodium borohydride for reduction; after the reduction reaction, the solvent methanol is recovered, and 160-165 ℃/15mmHg target product o-nitrobenzyl alcohol is collected by distillation. The method for preparing the o-nitrobenzol by directly reacting the raw material 1, 2-bis (o-nitrophenyl) ethane with benzoquinone has a symmetrical structure, is simple, can recycle byproducts, and has great industrial value.
Description
Technical field
The present invention relates to a kind of pharmaceutical-chemical intermediate, be specifically related to the preparation method of a kind of nitro alcohol.
Background technology
Nitro alcohol is important organic synthesis, medicine intermediate, can synthesize treatment coronary disease through nitro alcohol
Sick angina drug nifedipine and hypertension agents nifedipine etc..Main preparation methods is as follows:
1, with ortho-methylnitrobenzene as raw material, the substitution reaction first issuing raw free radical with bromine in the catalysis of peroxide prepares adjacent nitre
Bromide benzyl, then hydrolysis obtains nitro alcohol in the basic conditions, its synthetic route is as follows:
Intermediate product neighbour's nitro bromobenzyl that the method first step generates has stronger corrosivity, has higher requirement to equipment,
And yield is relatively low, document is reported as 70%.
2, in United States Patent (USP) US4994568 A1 and US4260627 A1, with adjacent nitrochloroformate as raw material, with 4-
Dimethylamino naphthyridine reaction prepares containing crude mixture, extracts organic facies, and vacuum drying obtains nitro alcohol, and it synthesizes road
Line is as follows:
。
3, with 1-Formyl-2-nitrobenzene as raw material, reduction reaction is occurred to obtain adjacent nitre in oxolane with boron trifluoride diethyl etherate
Base benzyl alcohol, its synthetic route is as follows:
The method route is simple, and yield is high, however it is necessary that and carries out at low temperatures, and raw material is costly.
4, with benzyl phenol as raw material, dichloromethane and dinitrogen pentoxide generation oxidation reaction obtain nitro alcohol and to nitre
Base benzyl alcohol, its synthetic route is as follows:
The method obtains the mixture of nitro alcohol and p nitrobenzyl alcohol, is not readily separated purification, is not suitable for industry metaplasia
Produce.
5, with p nitrobenzyl alcohol as raw material, under conditions of heating, react 2h with phosphotungstic acid, prepare ortho-nitrophenyl first
Alcohol, its synthetic route is as follows:
The method obtains product ultimate yield and is about 86%, but course of reaction needs heating, and energy consumption is bigger.
Summary of the invention
It is an object of the invention to: the preparation method of a kind of nitro alcohol is provided,
The raw material 1 of symmetrical structure, 2-bis-(O-Nitrophenylfluorone) ethane and benzoquinone direct reaction is utilized to prepare nitro alcohol,
Method is succinct, and by-product can recycle, great industrial value.
The technical solution of the present invention is: with 1, and 2-bis-(O-Nitrophenylfluorone) ethane is raw material, reacts with benzoquinone；Reaction
After end, steam benzoquinone and the by-product hydroquinone of excess；In residue, add methanol dissolve, add sodium borohydride also
Former reaction；After reduction reaction, recycling design methanol, 160-165 DEG C/15mmHg target product ortho-nitrophenyl first is collected in distillation
Alcohol；Its reaction equation is as follows:
。
It specifically comprise the following steps that 1, the benzoquinone of 2-bis-(O-Nitrophenylfluorone) ethane and its 5-10 times of mole, in
120-150 DEG C is reacted 4-8 hour；After reaction terminates, the benzoquinone of recovered under reduced pressure excess and by-product hydroquinone；In residue
Adding 1, the methanol of 3 times of weight of 2-bis-(O-Nitrophenylfluorone) ethane dissolves, and adds 1, and 2-bis-(O-Nitrophenylfluorone) ethane etc. rubs
15 DEG C of reduction reactions of sodium borohydride of your amount；After reduction reaction, recycling design methanol, 160-165 DEG C/15mmHg is collected in distillation
Target product nitro alcohol.
The invention have the advantage that raw material 1,2-bis-(O-Nitrophenylfluorone) ethane is raw material condensation preparation by adjacent nitro benzyl chloride,
The benzoquinone of excess and by-product hydroquinone can be to be utilized respectively after recovered under reduced pressure, separation, and concise in technology, industrial value is high.
Detailed description of the invention
Further illustrate the technical solution of the present invention below in conjunction with specific embodiment, these embodiments it is not intended that
It it is the restriction to technical scheme.
The analytical tool used in embodiment and equipment: gas chromatography mass spectrometry, MS5973N-GC6890N(U.S. Agilent is public
Department)；Nuclear magnetic resonance analyser, AVANCE DMX II I 500M(TMS internal standard, Bruker company)；High performance liquid chromatograph: Agilent
Technologies 1200 Series。
Embodiment 1: 136 grams of 1,2-bis-(O-Nitrophenylfluorone) ethane (0.50mol), 324 grams of benzoquinone (3.0mol) are added
In four mouthfuls of reaction bulbs of 1000 milliliters, after heating and melting, stirring and react 6 hours in 135-140 DEG C, high performance liquid chromatography is followed the tracks of
Detection；After reaction, the benzoquinone of water pump recovered under reduced pressure excess and by-product hydroquinone；408 grams of methanol are added molten in residue
Solve, add 19 grams of sodium borohydrides (0.5 mole), in 15 DEG C of stirring reactions 2 hours；After reduction reaction, recycling design methanol,
160-165 DEG C/15mmHg product 145.4 grams is collected in distillation, for target product nitro alcohol, liquid content 94.9%, yield
90.2%；Light yellow crystal 125.2 grams, mp70～72 DEG C, liquid content 99.2%, total recovery 81.1% is obtained with re crystallization from toluene.
Product structure is verified:1H NMR (CDCl3, 500 MHz) δ (ppm): 4.97 (s, 2H),7.47 (m,
1H), 7.67 (m, 1H), 7.73−7.47(m, 1H), 8.1 (dd, J = 8.0, 1 Hz, 1H)；13C NMR
(CDCl3, 125MHz) δ (ppm): 62.5, 124.9, 128.48, 129.9, 134.1, 136.8。
Embodiment 2～8: the preparation condition experiment of 1-Formyl-2-nitrobenzene
136 grams of 1,2-bis-(O-Nitrophenylfluorone) ethane (0.50mol), a certain amount of benzoquinone are joined four mouthfuls of 1000 milliliters instead
Answer in bottle, after heating and melting, stir and react in uniform temperature, high performance liquid chromatography tracing detection；After reaction, water pump recovered under reduced pressure
The benzoquinone of excess and by-product hydroquinone；In residue, add 408 grams of methanol dissolve, add 19 grams of sodium borohydrides (0.5
Mole), in 15 DEG C of stirring reactions 2 hours；After reduction reaction, recycling design methanol, 160-165 DEG C/15mmHg is collected in distillation
Product, liquid phase analysis content, calculated yield, result such as following table.
。
Claims (2)
1. the preparation method of nitro alcohol, is characterized in that: with 1, and 2-bis-(O-Nitrophenylfluorone) ethane is raw material, anti-with benzoquinone
Should；After reaction terminates, steam benzoquinone and the by-product hydroquinone of excess；In residue, add methanol dissolve, add boron
Sodium hydride reduces；After reduction reaction, recycling design methanol, 160-165 DEG C/15mmHg target product ortho-nitrophenyl is collected in distillation
Methanol；Its reaction equation is as follows:
。
The preparation method of nitro alcohol the most according to claim 1, it is characterized in that it specifically comprises the following steps that 1,
2-bis-(O-Nitrophenylfluorone) ethane and the benzoquinone of its 5-10 times of mole, react 4-8 hour in 120-150 DEG C；After reaction terminates,
The benzoquinone of recovered under reduced pressure excess and by-product hydroquinone；3 times of weights of 1,2-bis-(O-Nitrophenylfluorone) ethane are added in residue
The methanol of amount dissolves, and adds 1,15 DEG C of reduction reactions of the sodium borohydride of 2-bis-(O-Nitrophenylfluorone) ethane equimolar amounts；Reduction
After reaction, recycling design methanol, 160-165 DEG C/15mmHg target product nitro alcohol is collected in distillation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610229777.4A CN105801422A (en) | 2016-04-14 | 2016-04-14 | Preparation method of o-nitrobenzol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610229777.4A CN105801422A (en) | 2016-04-14 | 2016-04-14 | Preparation method of o-nitrobenzol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105801422A true CN105801422A (en) | 2016-07-27 |
Family
ID=56459277
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610229777.4A Pending CN105801422A (en) | 2016-04-14 | 2016-04-14 | Preparation method of o-nitrobenzol |
Country Status (1)
| Country | Link |
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| CN (1) | CN105801422A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1819984A (en) * | 2003-08-27 | 2006-08-16 | 庵原化学工业株式会社 | Production of aromatic aldehyde |
| CN102070596A (en) * | 2011-01-22 | 2011-05-25 | 浙江大学 | Preparation method for dihydrosafrole |
| CN105152947A (en) * | 2015-09-09 | 2015-12-16 | 江苏正大清江制药有限公司 | Preparation method of 2-amino-3,5-dibromobenzaldehyde |
-
2016
- 2016-04-14 CN CN201610229777.4A patent/CN105801422A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1819984A (en) * | 2003-08-27 | 2006-08-16 | 庵原化学工业株式会社 | Production of aromatic aldehyde |
| CN102070596A (en) * | 2011-01-22 | 2011-05-25 | 浙江大学 | Preparation method for dihydrosafrole |
| CN105152947A (en) * | 2015-09-09 | 2015-12-16 | 江苏正大清江制药有限公司 | Preparation method of 2-amino-3,5-dibromobenzaldehyde |
Non-Patent Citations (2)
| Title |
|---|
| LIPENG ZHOU ET AL.: "Electronic Effect of Substituent of Quinones on their Catalytic Performance in Hydrocarbons Oxidation", 《CATALYSIS LETTERS》 * |
| QIAOHONG ZHANG ET AL.: "Efficient metal-free aerobic oxidation of aromatic hydrocarbons utilizing aryl-tetrahalogenated N-hydroxyphthalimides and 1,4-diamino-2,3-dichloroanthraquinone", 《JOURNAL OF CHEMICAL TECHNOLOGY AND BIOTECHNOLOGY》 * |
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