CN102304051A - Method for preparing 5-nitro vanillin - Google Patents
Method for preparing 5-nitro vanillin Download PDFInfo
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- CN102304051A CN102304051A CN201110206498A CN201110206498A CN102304051A CN 102304051 A CN102304051 A CN 102304051A CN 201110206498 A CN201110206498 A CN 201110206498A CN 201110206498 A CN201110206498 A CN 201110206498A CN 102304051 A CN102304051 A CN 102304051A
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Abstract
The invention discloses a method for preparing 5-nitro vanillin. The method comprises the following specific steps of: dissolving vanillin and ceric ammonium nitrate in 5-90% by volume of acetic acid according to the weight ratio of the vanillin to the ceric ammonium nitrate of 1:(0.6-1.6), adding polyethylene glycol-400 as a phase transfer catalyst according to the mol ratio of the polyethylene glycol-400 to the vanillin of 1:1.25, reacting at 20-60 DEG C for 1.0-2.5 h under magnetic stirring, tracking by TLC (Thin Layer Chromatography), wherein a developing agent includes ethyl acetate and petroleum ether in the ratio of 1:1, and stopping stirring after a reactant is completely converted into a product; and pouring a mixture into proper ice water, separating out yellow solid, and obtaining the 5-nitro vanillin product by filtering, washing, drying and re-crystallizing. According to the method disclosed by the invention, the green chemical product, namely ceric ammonium nitrate, is used as a nitration reagent; the polyethylene glycol-400 is used as the phase transfer catalyst; and the method has the advantages of short reaction time, few by-products, simplicity and convenience for operation and low production cost.
Description
Technical field
The present invention relates to the preparation method of compound, be specifically related to a kind of preparation method of 5-nitro vanillin food grade,1000.000000ine mesh.
Background technology
5-nitro vanillin food grade,1000.000000ine mesh, systematic name are 3-methoxyl group-4-hydroxyl--5 nitrobenzaldehydes.Be mainly used in medicine and field of perfumery; Can be used for 3; 5-two replaces the synthetic of pyrocatechol catechol-O-methyltransferase (COMT-I) suppressor factor tolcapone (tolcapone); Or as the synthetic biosynthetic precursor of rifamycinoid antibiotics (3-hydroxyl methoxyl group rifomycin, 3-hydroxyl rifomycin).5-nitro vanillin food grade,1000.000000ine mesh preparation method mainly is through the vanillin food grade,1000.000000ine mesh nitrofication process, is raw material with the vanillin food grade,1000.000000ine mesh promptly, and nitric acid is nitrating agent, in organic solvent, obtains.But this method is big with the acid amount, and the spent acid wastewater flow rate is big, is unfavorable for environment protection.Simultaneously, because the strong oxidizing property of nitric acid also makes side reaction increase, the product separation complex process.
Summary of the invention
The objective of the invention is to: a kind of preparation method of 5-nitro vanillin food grade,1000.000000ine mesh is provided, selects for use ceric ammonium nitrate (CAN) as nitrating agent, easy and simple to handle, the reaction times is short, and productive rate is higher.
Technical solution of the present invention is: this preparation method select for use ceric ammonium nitrate and vanillin food grade,1000.000000ine mesh react 5-nitro vanillin food grade,1000.000000ine mesh, wherein, ceric ammonium nitrate is a nitrating agent, acetic acid is solvent, polyoxyethylene glycol-400 is a phase-transfer catalyst.
Among the preparation method of 5-nitro vanillin food grade,1000.000000ine mesh of the present invention, preparing method's reaction equation is following:
Among the preparation method of 5-nitro vanillin food grade,1000.000000ine mesh of the present invention; Concrete preparation process is following: vanillin food grade,1000.000000ine mesh is 1: 0.6～1.6 with the ratio of the amount of substance of ceric ammonium nitrate; Being dissolved in the acetic acid of volume(tric)fraction 5%～90%, is that 1:1.25 adds polyoxyethylene glycol-400 as phase-transfer catalyst according to the mol ratio with vanillin food grade,1000.000000ine mesh
,Under magnetic agitation, in 20～60 ℃, reaction 1.0～2.5h, followed the tracks of developping agent: ETHYLE ACETATE by TLC: sherwood oil=1: 1 stops to stir when reactant is converted into product fully; Mixture is poured in an amount of frozen water, had the xanchromatic solid to separate out, suction filtration, washing, drying, recrystallization obtains the product of 5-nitro vanillin food grade,1000.000000ine mesh.
The present invention has the following advantages: select for use the green chemical ceric ammonium nitrate as nitrating agent, as phase-transfer catalyst, shortened the reaction times with polyoxyethylene glycol-400, side reaction is few, and is easy and simple to handle, and production cost is low.
Description of drawings
Fig. 1 is the infrared spectrogram of 5-nitro vanillin food grade,1000.000000ine mesh of the present invention.
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of 5-nitro vanillin food grade,1000.000000ine mesh of the present invention.
Embodiment
Further specify technical solution of the present invention below in conjunction with specific embodiment, embodiment can not be interpreted as it is the restriction to technical solution like this.
Embodiment 1:
In the Erlenmeyer flask of 25mL, add 0.152g (1mmol) vanillin food grade,1000.000000ine mesh; Volume(tric)fraction 90% acetic acid of 2mL, 0.50 g (1.25 mmol) polyoxyethylene glycol-400 slowly splashes into the aqueous solution of 0.09 g (0.58mmol) ceric ammonium nitrate under agitation condition; 20 ℃ were reacted 2.5 hours; Followed the tracks of developping agent: ETHYLE ACETATE by TLC: sherwood oil=1: 1 stops to stir when reactant is converted into product fully; Reactant is poured in an amount of frozen water, had the xanchromatic solid to separate out, suction filtration with distilled water wash solids 2-3 time, obtains the thick product of 5-nitro vanillin food grade,1000.000000ine mesh; Weigh: 0.14g, productive rate: 71%; Product is through fusing point test and ir spectra, hydrogen nuclear magnetic resonance spectrum analysis, and is consistent with bibliographical information; Recording fusing point is: m.p: 177.2 ~ 178.6 ℃;
IR: ν
Max(KBr compressing tablet, cm
-1), 3203,3077,2945,2876,1685,1611,1548,1402,1335,1269,1231,1103,1047,916;
1HNMR: (DMSO-d
6, ppm) δ: 3.99 (s, 3H, OCH
3), 7.65 (s, 1H, Ar-H), 8.14 (s, 1H, Ar-H), 9.90 (s, 1H, CHO).
Embodiment 2:
In the Erlenmeyer flask of 100mL, add 0.76g (5mmol) vanillin food grade,1000.000000ine mesh, volume(tric)fraction 90% acetic acid of 10mL, 2.5 g (6.25 mmol) polyoxyethylene glycol-400 slowly splashes into the aqueous solution of 0.76 g (4.9 mmol) ceric ammonium nitrate under agitation condition; 40 ℃ were reacted 1.5 hours, were followed the tracks of developping agent: ETHYLE ACETATE by TLC: sherwood oil=1: 1 stops to stir when reactant is converted into product fully; Reactant is poured in an amount of frozen water, had the xanchromatic solid to separate out, suction filtration with distilled water wash solids 2-3 time, obtains the thick product of 5-nitro vanillin food grade,1000.000000ine mesh; Weigh: 0.68g, productive rate: 69%; Recording fusing point is: m.p: 177.5 ~ 178.6 ℃.
Embodiment 3:
In the round-bottomed flask of 1000mL, add 15.2g (100mmol) vanillin food grade,1000.000000ine mesh; Volume(tric)fraction 90% acetic acid of 200mL, 50.0 g (125 mmol) polyoxyethylene glycol-400 slowly splashes into the aqueous solution of 24.32g (158 mmol) ceric ammonium nitrate under agitation condition; 60 ℃ were reacted 1.0 hours; Followed the tracks of developping agent: ETHYLE ACETATE by TLC: sherwood oil=1: 1 stops to stir when reactant is converted into product fully; Reactant is poured in an amount of frozen water, had the xanchromatic solid to separate out, suction filtration with distilled water wash solids 2-3 time, obtains the thick product of 5-nitro vanillin food grade,1000.000000ine mesh; Weigh: 13.8g, productive rate: 70%.Recording fusing point is: m.p: 177.5 ~ 178.5 ℃.
Claims (1)
1. the preparation method of 5-nitro vanillin food grade,1000.000000ine mesh, this preparation method select for use ceric ammonium nitrate and vanillin food grade,1000.000000ine mesh react 5-nitro vanillin food grade,1000.000000ine mesh, wherein, ceric ammonium nitrate is a nitrating agent, acetic acid is solvent, polyoxyethylene glycol-400 is a phase-transfer catalyst; The concrete steps that it is characterized in that this preparation method are following: vanillin food grade,1000.000000ine mesh is 1: 0.6～1.6 with the ratio of the amount of substance of ceric ammonium nitrate; Being dissolved in the acetic acid of volume(tric)fraction 5%～90%, is that 1:1.25 adds polyoxyethylene glycol-400 as phase-transfer catalyst according to the mol ratio with vanillin food grade,1000.000000ine mesh
,Under magnetic agitation, in 20～60 ℃, reaction 1.0～2.5h, followed the tracks of developping agent: ETHYLE ACETATE by TLC: sherwood oil=1: 1 stops to stir when reactant is converted into product fully; Mixture is poured in an amount of frozen water, had the xanchromatic solid to separate out, suction filtration, washing, drying, recrystallization obtains the product of 5-nitro vanillin food grade,1000.000000ine mesh.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103130681A (en) * | 2013-03-19 | 2013-06-05 | 上海奥博生物医药技术有限公司 | Novel method for preparing entacapone |
| CN107652184A (en) * | 2017-09-26 | 2018-02-02 | 连云港市工业投资集团有限公司 | The method that nitrogen dioxide nitrification vanillic aldehyde prepares 5 nitro vanillins |
Citations (4)
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|---|---|---|---|---|
| CN1558894A (en) * | 2001-07-25 | 2004-12-29 | Method for the nitration of phenolic compounds | |
| CN100999473A (en) * | 2006-12-19 | 2007-07-18 | 浙江工业大学 | 5-nitro coffeic acid phenylglycollic ester and its preparation and use |
| CN101020640A (en) * | 2007-03-15 | 2007-08-22 | 淮阴师范学院 | Prepn process of 3-nitro salicylaldehyde |
| CN101462963A (en) * | 2008-12-30 | 2009-06-24 | 淮阴师范学院 | Preparation of 2,4,6-trinitroresorcinol |
-
2011
- 2011-07-22 CN CN201110206498A patent/CN102304051A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1558894A (en) * | 2001-07-25 | 2004-12-29 | Method for the nitration of phenolic compounds | |
| CN100999473A (en) * | 2006-12-19 | 2007-07-18 | 浙江工业大学 | 5-nitro coffeic acid phenylglycollic ester and its preparation and use |
| CN101020640A (en) * | 2007-03-15 | 2007-08-22 | 淮阴师范学院 | Prepn process of 3-nitro salicylaldehyde |
| CN101462963A (en) * | 2008-12-30 | 2009-06-24 | 淮阴师范学院 | Preparation of 2,4,6-trinitroresorcinol |
Non-Patent Citations (4)
| Title |
|---|
| J. L. GRENIER等: "Synthesis and physico-chemical properties of nitrocaffeic acids", 《J. PHYS. ORG. CHEM.》 * |
| LÁSZLÓ E. KISS等: "Discovery of a long-acting, peripherally selective inhibitor of catechol-O-methyltransferase", 《J. MED. CHEM.》 * |
| 朱惠琴: "5-硝基水杨酸的制备", 《中国医药工业杂志》 * |
| 朱惠琴等: "合成1-硝基-2-萘酚的一种新方法", 《化学试剂》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103130681A (en) * | 2013-03-19 | 2013-06-05 | 上海奥博生物医药技术有限公司 | Novel method for preparing entacapone |
| CN107652184A (en) * | 2017-09-26 | 2018-02-02 | 连云港市工业投资集团有限公司 | The method that nitrogen dioxide nitrification vanillic aldehyde prepares 5 nitro vanillins |
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Application publication date: 20120104 |