CN106397149A - Preparation method of pentafluorobenzaldehyde - Google Patents
Preparation method of pentafluorobenzaldehyde Download PDFInfo
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- CN106397149A CN106397149A CN201610736829.7A CN201610736829A CN106397149A CN 106397149 A CN106397149 A CN 106397149A CN 201610736829 A CN201610736829 A CN 201610736829A CN 106397149 A CN106397149 A CN 106397149A
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- pentafluorobenzaldehyde
- phenyl
- preparation
- water
- formic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/44—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reduction and hydrolysis of nitriles
Abstract
The invention relates to a preparation method of pentafluorobenzaldehyde, and belongs to the field of fine chemical product preparation. According to the preparation method, catalyst Ni-Al alloy, pentafluorobenzonitrile, and formic acid are subjected to reaction in water to prepare pentafluorobenzaldehyde. Ni-Al alloy is adopted, formic acid and water are taken as reducing agents, and pentafluorobenzaldehyde is prepared via reduction of pentafluorobenzonitrile. The preparation method is capable of realizing direction reduction of pentafluorobenzonitrile into pentafluorobenzaldehyde, so that reaction steps are reduced, generation of waste is reduced, production cost is reduced, and environmental pollution is reduced.
Description
Technical field
The present invention relates to a kind of preparation method of pentafluorobenzaldehyde, belong to fine chemical product preparation field.
Background technology
Pentafluorobenzaldehyde is a kind of important pesticide, medicine intermediate, and domestic and international public technology has following several reports.
Document《Highly fluorinated Analogues of Pharmacologically Active
Compounds》N.B.Chapman, J.Chem.Soc., 1967, describe by phenyl-pentafluoride nitrile, anhydrous stannous chloride prepares five fluorine
The method of benzaldehyde, due to needing to use ether and hydrogen chloride gas, is difficult expanding production.
Patent US20040110990 domestic for CN03127891 propose a kind of water, acid, nickeliferous and aluminum catalyst with
And the method in the presence of hydrogen, substituted cyanophenyl catalysis being reduced to the benzaldehyde of replacement.The method needs autoclave to be hydrogenated with, and leads to
The production capacity that production is amplified by factory is low, and the perishable kettle of acid used, higher to equipment requirements.
Document Journal of Chemical Society C P1343-1348 1971 see this document of page 1348 show by
Phenyl-pentafluoride nitrile can prepare pentafluorobenzaldehyde, and existing problems are that Ni-Al alloy consumes too greatly, and need to first pass through sodium hydroxide
It is processed into Raney's nickel, yield is also than relatively low.
Remaining document major part was also produced pentafluorobenzaldehyde originally using pentafluorobenzoic acid derivant, and phenyl-pentafluoride first
Acid derivative is typically prepared by sulphuric acid hydrolysis by phenyl-pentafluoride nitrile, can produce a large amount of spent acid, abraum salt is difficult to process.
Content of the invention
For above-mentioned technical problem, the present invention provides a kind of preparation method of pentafluorobenzaldehyde, and the method is by phenyl-pentafluoride nitrile
It is directly reduced to pentafluorobenzaldehyde, decreases reactions steps, decrease the generation of waste, be beneficial to reduce production cost, reduce
Environmental pollution.
The preparation method of pentafluorobenzaldehyde, the method is to make catalyst nickel alumin(i)um alloy, phenyl-pentafluoride nitrile, and formic acid reacts in water
Prepare pentafluorobenzaldehyde.
With nickel alumin(i)um alloy, formic acid and water, as reducing agent, phenyl-pentafluoride nitrile are reduced into phenyl-pentafluoride first to the method for the invention
Aldehyde.
The preparation method of the further preferably described pentafluorobenzaldehyde of the present invention is：By phenyl-pentafluoride nitrile, formic acid, water is placed in reaction
In kettle, it is warming up to 60～105 DEG C, add nickel alumin(i)um alloy powder, 60～105 DEG C of insulation 30～120min, cooling, filter, extraction,
Rectification, obtains pentafluorobenzaldehyde.
Further, by phenyl-pentafluoride nitrile, formic acid, water is placed in reactor, is warming up to 60～105 DEG C, adds nickel alumin(i)um alloy
Powder, 60～105 DEG C of insulation 30～120min, it is cooled to room temperature, filters, after filtrate dilute, add dichloromethane extraction,
Rectification after desolvation, obtains pentafluorobenzaldehyde.
In technique scheme, preferably nickel alumin(i)um alloy powder is dividedly in some parts to reaction system.
In technique scheme, preferably described reaction temperature is 85～95 DEG C, and temperature retention time is 60～90min.
Further, the preparation method of pentafluorobenzaldehyde of the present invention is being provided with the anti-of condensing units and agitating device
Answer in device and carry out.
In all technical schemes of preparation method of pentafluorobenzaldehyde of the present invention, all preferably described reaction is in inert atmosphere
Under carry out, preferably carry out under nitrogen protection.
In all technical schemes of preparation method of pentafluorobenzaldehyde of the present invention, all preferably described nickel alumin(i)um alloy is nickel aluminum
Alloy powder, commercially available, further, it is preferable to the granularity of nickel alumin(i)um alloy powder is 100～300 mesh.
The consumption of all preferably described nickel alumin(i)um alloy in all technical schemes of preparation method of pentafluorobenzaldehyde of the present invention
For 0.2～0.6 times of phenyl-pentafluoride nitrile weight, preferably 0.45 times.
In all technical schemes of preparation method of pentafluorobenzaldehyde of the present invention, the consumption of all preferably described formic acid is five
2～5 times of fluorobenzonitrile weight, preferably 3 times
In all technical schemes of preparation method of pentafluorobenzaldehyde of the present invention, the consumption of all preferably described water is five fluorine
1～2 times of cyanophenyl weight, preferably 1.7 times.
In all technical schemes of preparation method of pentafluorobenzaldehyde of the present invention, all preferably described reaction is in stirring
Under carry out, mixing speed be 300～500r/min.
Beneficial effects of the present invention are：With nickel alumin(i)um alloy, formic acid and water, as reducing agent, phenyl-pentafluoride nitrile are reduced the present invention
Become pentafluorobenzaldehyde.Said method can be directly reduced to pentafluorobenzaldehyde by a step just phenyl-pentafluoride nitrile, decreases reactions steps, and
Decrease the generation of waste simultaneously, be beneficial to reduce production cost, reduce environmental pollution.
Specific embodiment
Following non-limiting examples can make those of ordinary skill in the art that the present invention is more fully understood, but not with
Any mode limits the present invention.
Test method described in following embodiments, if no special instructions, is conventional method；Described reagent and material, such as
No specified otherwise, all commercially obtains.
In following embodiments, the granularity of Nickel Aluminium Alloy Powder used is 200 mesh.
Embodiment 1
To equipped with condenser, mechanical agitation, in the 50L reactor of thermometer boss, add phenyl-pentafluoride nitrile 4.9Kg, formic acid
15Kg, water 8.5Kg, are passed through nitrogen protection, are warmed up to 65 DEG C, Nickel Aluminium Alloy Powder 2.2Kg are divided 8 batches to put in reactor, mistake
Heat release in journey, maintains reflux state.Nickel Aluminium Alloy Powder addition flows back 1 hour after finishing, sampling, vapor detection phenyl-pentafluoride nitrile ＜
0.2%, it is cooled to room temperature, filters, filtrate adds 25Kg water to be extracted with 10Kg dichloromethane, and the water layer separating adds
10Kg dichloromethane extracts once, after extracting the merging of gained organic layer twice, adds 5% sodium bicarbonate aqueous solution, adjusts PH to 6
～7, separate oil reservoir, dichloromethane is reclaimed in air-distillation, the mother solution after distillation carries out rectification, in pressure -0.09Mpa, top temperature 108
DEG C steam product pentafluorobenzaldehyde 3.1Kg (reception pipe needs heat tracing, easily plugging after product solidification), 24～28 DEG C of fusing point, contain
Amount 98.7%, yield 61.5%.
Embodiment 2
To equipped with condenser, mechanical agitation, in the 1L reactor of thermometer boss, add phenyl-pentafluoride nitrile 100g, formic acid
300g, water 170g, are passed through nitrogen protection, are warmed up to 70 DEG C, Nickel Aluminium Alloy Powder 45g is divided 4 batches to put in reactor, during
Heat release, maintains reflux state.Nickel Aluminium Alloy Powder addition flows back 2 hours after finishing, sampling, vapor detection phenyl-pentafluoride nitrile ＜
0.2%, it is cooled to room temperature, filters, filtrate adds 450g water to extract once with 150g dichloromethane, and the water layer separating adds
150g dichloromethane extracts once, after extracting the merging of gained organic layer twice, adds 5% sodium bicarbonate aqueous solution, adjusts PH to 6
～7, separate oil reservoir, dichloromethane is reclaimed in air-distillation, the mother solution after distillation carries out rectification, in pressure -0.09Mpa, top temperature 108
DEG C steam product pentafluorobenzaldehyde 60.5g (reception pipe needs heat tracing, easily plugging after product solidification), 24～28 DEG C of fusing point, contain
Amount 98.9%, yield 59%.
Embodiment 3
To equipped with condenser, mechanical agitation, in the 1L reactor of thermometer boss, add phenyl-pentafluoride nitrile 90g, formic acid 270g,
Water 150g, be passed through nitrogen protection, be warmed up to 90 DEG C, Nickel Aluminium Alloy Powder 40g divided 4 batches to put in reactor, during heat release,
Maintain reflux state.Nickel Aluminium Alloy Powder addition flows back 2 hours after finishing, sampling, vapor detection phenyl-pentafluoride nitrile ＜ 0.2%, fall
Warm to room temperature, filter, filtrate adds 400g water to extract once with 130g dichloromethane, and the water layer separating adds 130g dichloromethane
Alkane extracts once, after extracting the merging of gained organic layer twice, adds 5% sodium bicarbonate aqueous solution, adjusts PH to 6～7, separate oil
Layer, dichloromethane is reclaimed in air-distillation, and the mother solution after distillation carries out rectification, and in pressure -0.09Mpa, 108 DEG C of top temperature steams product
Pentafluorobenzaldehyde 54.3g (reception pipe needs heat tracing, easily plugging after product solidification), 24-28 DEG C of fusing point, content 98.5%, receive
Rate 58.5%.
Claims (7)
1. the preparation method of pentafluorobenzaldehyde, the method is to make catalyst nickel alumin(i)um alloy, phenyl-pentafluoride nitrile, and formic acid reacts system in water
Standby pentafluorobenzaldehyde.
2. method according to claim 1 it is characterised in that：By phenyl-pentafluoride nitrile, formic acid, water is placed in reactor, heats up
To 60～105 DEG C, add nickel alumin(i)um alloy powder, 60～105 DEG C of insulation 30～120min, cooling, filter, extraction, rectification, obtain five
Fluorobenzaldehyde.
3. method according to claim 1 it is characterised in that：Described nickel alumin(i)um alloy is nickel alumin(i)um alloy powder, and its granularity is
100～300 mesh.
4. the method according to claim 1 or 3 it is characterised in that：The consumption of described nickel alumin(i)um alloy is phenyl-pentafluoride nitrile weight
0.2～0.6 times.
5. method according to claim 1 it is characterised in that：The consumption of described formic acid is the 2～5 of phenyl-pentafluoride nitrile weight
Times.
6. method according to claim 1 it is characterised in that：The consumption of described water is 1～2 times of phenyl-pentafluoride nitrile weight.
7. method according to claim 1 it is characterised in that：Described reaction is carried out under stirring, and mixing speed is
300～500r/min.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0441480A (en) * | 1990-06-08 | 1992-02-12 | Fujirebio Inc | 3-(4-1-imidazolylmethyl)phenyl@)-2-propene-1-ol and production thereof |
| US5124487A (en) * | 1991-08-05 | 1992-06-23 | Occidental Chemical Corporation | Catalytic reduction of nitriles to aldehydes |
| CN1859903A (en) * | 2003-03-04 | 2006-11-08 | 辉瑞产品公司 | Use of EP2 selective receptor agonists in medical treatment |
| CN101684094A (en) * | 2008-09-24 | 2010-03-31 | 中国科学院上海药物研究所 | 3-substituted-1, 8-naphthalimide compound and synthesis method and medical application thereof |
| CN102186847A (en) * | 2008-10-14 | 2011-09-14 | 奥米罗有限公司 | New 2-amidothiadiazole derivatives |
| CN103998443A (en) * | 2011-11-11 | 2014-08-20 | 阿尔米雷尔有限公司 | New cyclohexylamine derivatives having beta2 adrenergic agonist and M3 muscarinic antagonist activities |
| CN104024245A (en) * | 2011-11-11 | 2014-09-03 | 阿尔米雷尔有限公司 | New cyclohexylamine derivatives having beta 2 adrenergic agonist and M3 muscarinic antagonist acticities |
| CN104311376A (en) * | 2014-09-18 | 2015-01-28 | 东南大学 | New method for directly preparing aryl aldehyde from aryl nitrile |
-
2016
- 2016-08-26 CN CN201610736829.7A patent/CN106397149B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0441480A (en) * | 1990-06-08 | 1992-02-12 | Fujirebio Inc | 3-(4-1-imidazolylmethyl)phenyl@)-2-propene-1-ol and production thereof |
| US5124487A (en) * | 1991-08-05 | 1992-06-23 | Occidental Chemical Corporation | Catalytic reduction of nitriles to aldehydes |
| CN1859903A (en) * | 2003-03-04 | 2006-11-08 | 辉瑞产品公司 | Use of EP2 selective receptor agonists in medical treatment |
| CN101684094A (en) * | 2008-09-24 | 2010-03-31 | 中国科学院上海药物研究所 | 3-substituted-1, 8-naphthalimide compound and synthesis method and medical application thereof |
| CN102186847A (en) * | 2008-10-14 | 2011-09-14 | 奥米罗有限公司 | New 2-amidothiadiazole derivatives |
| CN103998443A (en) * | 2011-11-11 | 2014-08-20 | 阿尔米雷尔有限公司 | New cyclohexylamine derivatives having beta2 adrenergic agonist and M3 muscarinic antagonist activities |
| CN104024245A (en) * | 2011-11-11 | 2014-09-03 | 阿尔米雷尔有限公司 | New cyclohexylamine derivatives having beta 2 adrenergic agonist and M3 muscarinic antagonist acticities |
| CN104311376A (en) * | 2014-09-18 | 2015-01-28 | 东南大学 | New method for directly preparing aryl aldehyde from aryl nitrile |
Non-Patent Citations (1)
| Title |
|---|
| 《J.CHEM.SOC.(C)》 * |
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Inventor after: Sun Faming Inventor after: Jiang Dianbao Inventor after: Zhang Hongxue Inventor after: Zhao Yuguo Inventor before: Sun Faming Inventor before: Jiang Dianping Inventor before: Zhang Hongxue Inventor before: Zhao Yuguo |
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