CN106397149B - The preparation method of pentafluorobenzaldehyde - Google Patents
The preparation method of pentafluorobenzaldehyde Download PDFInfo
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- CN106397149B CN106397149B CN201610736829.7A CN201610736829A CN106397149B CN 106397149 B CN106397149 B CN 106397149B CN 201610736829 A CN201610736829 A CN 201610736829A CN 106397149 B CN106397149 B CN 106397149B
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- pentafluorobenzaldehyde
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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
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Abstract
The present invention relates to a kind of preparation methods of pentafluorobenzaldehyde, belong to fine chemical product preparation field.The preparation method of pentafluorobenzaldehyde, this method are to make catalyst nickel alumin(i)um alloy, and phenyl-pentafluoride nitrile, formic acid reaction in water prepares pentafluorobenzaldehyde.Phenyl-pentafluoride nitrile, as reducing agent, is reduced into pentafluorobenzaldehyde with nickel alumin(i)um alloy, formic acid and water by the present invention.The above method can a step phenyl-pentafluoride nitrile will be directly reduced to pentafluorobenzaldehyde, reduce reaction step, and reduce the generation of waste simultaneously, be beneficial to reduce production cost, reduce environmental pollution.
Description
Technical field
The present invention relates to a kind of preparation methods of pentafluorobenzaldehyde, belong to fine chemical product preparation field.
Background technique
Pentafluorobenzaldehyde is the important pesticide of one kind, 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, it describes by phenyl-pentafluoride nitrile, anhydrous stannous chloride prepares five fluorine
The method of benzaldehyde is not easy expanding production due to needing to use ether and hydrogen chloride gas.
The country patent US20040110990 be CN03127891 propose it is a kind of water, acid, nickeliferous and aluminium catalyst with
And the method that substituted cyanophenyl catalysis is reduced to the benzaldehyde of substitution in the presence of hydrogen.This method needs autoclave to add hydrogen, causes
The production capacity of factory's amplification production is low, and the perishable autoclave body of acid used, relatively high to equipment requirement.
Document Journal of Chemical Society C P1343-1348 1971 see this document of page 1348 show by
Phenyl-pentafluoride nitrile can prepare pentafluorobenzaldehyde, be that the consumption of Ni-Al alloy is too big, and needs to first pass through sodium hydroxide there are problem
It is processed into Raney's nickel, yield is also relatively low.
Remaining document is largely also produced pentafluorobenzaldehyde using pentafluoro benzoic acid derivative originally, and phenyl-pentafluoride first
Acid derivative is usually to be prepared by phenyl-pentafluoride nitrile by sulphuric acid hydrolysis, can generate a large amount of spent acid, abraum salt is difficult to handle.
Summary of the invention
In view of the above technical problems, the present invention provides a kind of preparation method of pentafluorobenzaldehyde, and this method is by phenyl-pentafluoride nitrile
It is directly reduced to pentafluorobenzaldehyde, reduces reaction step, reduces the generation of waste, is beneficial to reduce production cost, reduce
Environmental pollution.
The preparation method of pentafluorobenzaldehyde, this method are to make catalyst nickel alumin(i)um alloy, and phenyl-pentafluoride nitrile, formic acid reacts in water
Prepare pentafluorobenzaldehyde.
Phenyl-pentafluoride nitrile, as reducing agent, is reduced into phenyl-pentafluoride first with nickel alumin(i)um alloy, formic acid and water by 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, 60~105 DEG C are warming up to, nickel alumin(i)um alloy powder is added, 60~105 DEG C of 30~120min of heat preservation cool down, it filters, extraction,
Rectifying obtains pentafluorobenzaldehyde.
Further, by phenyl-pentafluoride nitrile, formic acid, water is placed in reaction kettle, is warming up to 60~105 DEG C, and nickel alumin(i)um alloy is added
Powder, 60~105 DEG C of 30~120min of heat preservation, is cooled to room temperature, filtering, and methylene chloride extraction is added in filtrate after being diluted with water,
Rectifying after removing solvent, obtains pentafluorobenzaldehyde.
In above-mentioned technical proposal, preferably nickel alumin(i)um alloy powder is added portionwise into reaction system.
In above-mentioned technical proposal, the preferably described reaction temperature is 85~95 DEG C, and soaking time is 60~90min.
Further, the preparation method of pentafluorobenzaldehyde of the present invention is being equipped with the anti-of condensing unit and agitating device
It answers in device and carries out.
The preferably described reaction is in inert atmosphere in all technical solutions of the preparation method of pentafluorobenzaldehyde of the present invention
Lower progress, preferably carries out under nitrogen protection.
Preferably the nickel alumin(i)um alloy is nickel aluminium in all technical solutions of the preparation method of pentafluorobenzaldehyde of the present invention
Alloy powder, it is commercially available, further, it is preferable to which the granularity of nickel alumin(i)um alloy powder is 100~300 mesh.
The dosage of the preferred nickel alumin(i)um alloy in all technical solutions of the preparation method of pentafluorobenzaldehyde of the present invention
For 0.2~0.6 times of phenyl-pentafluoride nitrile weight, preferably 0.45 times.
Preferably the dosage of the formic acid is five in all technical solutions of the preparation method of pentafluorobenzaldehyde of the present invention
2~5 times of fluorobenzonitrile weight, preferably 3 times
Preferably the dosage of the water is five fluorine in all technical solutions of the preparation method of pentafluorobenzaldehyde of the present invention
1~2 times of cyanophenyl weight, preferably 1.7 times.
The preferably described reaction is in stirring in all technical solutions of the preparation method of pentafluorobenzaldehyde of the present invention
Lower progress, mixing speed are 300~500r/min.
The invention has the benefit that the present invention with nickel alumin(i)um alloy, formic acid and water as reducing agent, phenyl-pentafluoride nitrile is restored
At pentafluorobenzaldehyde.The above method can a step phenyl-pentafluoride nitrile will be directly reduced to pentafluorobenzaldehyde, reduce reaction step, and
The generation for reducing waste simultaneously is beneficial to reduce production cost, reduce environmental pollution.
Specific embodiment
Following non-limiting embodiments can with a person of ordinary skill in the art will more fully understand the present invention, but not with
Any mode limits the present invention.
Test method described in following embodiments is unless otherwise specified conventional method；The reagent and material, such as
Without specified otherwise, commercially obtain.
The granularity of Nickel Aluminium Alloy Powder used is 200 mesh in following embodiments.
Embodiment 1
To condenser is equipped with, phenyl-pentafluoride nitrile 4.9Kg, formic acid are added in the 50L reaction kettle of thermometer boss for mechanical stirring
15Kg, water 8.5Kg, is passed through nitrogen protection, is warming up to 65 DEG C, Nickel Aluminium Alloy Powder 2.2Kg points 8 batches is put into reaction kettle, mistake
Heat release in journey, maintains reflux state.Nickel Aluminium Alloy Powder flows back 1 hour after being added, and samples, vapor detection phenyl-pentafluoride nitrile <
0.2%, it is cooled to room temperature, is filtered, filtrate is added 25Kg water and is extracted with 10Kg methylene chloride, and the water layer separated adds
The extraction of 10Kg methylene chloride is primary, after extracting gained organic layer merging twice, 5% sodium bicarbonate aqueous solution is added, adjusts PH to 6
~7, oil reservoir is separated, methylene chloride is recycled in air-distillation, and the mother liquor after distillation carries out rectifying, in pressure -0.09Mpa, top temperature 108
Product pentafluorobenzaldehyde 3.1Kg (reception pipe needs heat tracing, is easy plugging after product solidification) DEG C is steamed, 24~28 DEG C of fusing point, is contained
Amount 98.7%, yield 61.5%.
Embodiment 2
To condenser is equipped with, phenyl-pentafluoride nitrile 100g, formic acid are added in the 1L reaction kettle of thermometer boss for mechanical stirring
300g, water 170g, is passed through nitrogen protection, is warming up to 70 DEG C, Nickel Aluminium Alloy Powder 45g points 4 batches is put into reaction kettle, in the process
Heat release maintains reflux state.Nickel Aluminium Alloy Powder flows back 2 hours after being added, and samples, vapor detection phenyl-pentafluoride nitrile <
0.2%, it is cooled to room temperature, is filtered, 450g water is added in filtrate and the extraction of 150g methylene chloride is primary, and the water layer separated adds
The extraction of 150g methylene chloride is primary, after extracting gained organic layer merging twice, 5% sodium bicarbonate aqueous solution is added, adjusts PH to 6
~7, oil reservoir is separated, methylene chloride is recycled in air-distillation, and the mother liquor after distillation carries out rectifying, in pressure -0.09Mpa, top temperature 108
Product pentafluorobenzaldehyde 60.5g (reception pipe needs heat tracing, is easy plugging after product solidification) DEG C is steamed, 24~28 DEG C of fusing point, is contained
Amount 98.9%, yield 59%.
Embodiment 3
To condenser is equipped with, phenyl-pentafluoride nitrile 90g, formic acid 270g are added in the 1L reaction kettle of thermometer boss for mechanical stirring,
Water 150g, is passed through nitrogen protection, is warming up to 90 DEG C, Nickel Aluminium Alloy Powder 40g points 4 batches is put into reaction kettle, heat release in the process,
Maintain reflux state.Nickel Aluminium Alloy Powder flows back 2 hours after being added, and samples, vapor detection phenyl-pentafluoride nitrile < 0.2%, drop
It warms to room temperature, filters, 400g water is added in filtrate and the extraction of 130g methylene chloride is primary, and the water layer separated adds 130g dichloromethane
Alkane extraction is primary, after extracting gained organic layer merging twice, 5% sodium bicarbonate aqueous solution is added, adjusts PH to 6~7, separates oil
Methylene chloride is recycled in layer, air-distillation, and the mother liquor after distillation carries out rectifying, and in pressure -0.09Mpa, 108 DEG C of top temperature steams product
Pentafluorobenzaldehyde 54.3g (reception pipe needs heat tracing, is easy plugging after product solidification), 24-28 DEG C of fusing point, content 98.5% is received
Rate 58.5%.
Claims (4)
1. the preparation method of pentafluorobenzaldehyde, this method is by phenyl-pentafluoride nitrile, formic acid, and water is placed in reaction kettle, is passed through nitrogen guarantor
Shield is warming up to 60~105 DEG C, and nickel alumin(i)um alloy powder is added, and reflux heat preservation 1-2 hours cools down, filters, and extraction, rectifying obtains five
Fluorobenzaldehyde, wherein the dosage of the nickel alumin(i)um alloy is 0.2~0.6 times of phenyl-pentafluoride nitrile weight, the nickel alumin(i)um alloy is nickel aluminium
Alloy powder, granularity are 100 ~ 300 mesh.
2. according to the method described in claim 1, it is characterized by: the dosage of the formic acid is the 2~5 of phenyl-pentafluoride nitrile weight
Times.
3. according to the method described in claim 1, it is characterized by: the dosage of the water is 1~2 times of phenyl-pentafluoride nitrile weight.
4. according to the method described in claim 1, mixing speed is it is characterized by: the reaction carries out under stirring
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.M.Birchall等.Polyfluoroarenes. Part ⅩⅦ. Some Reactions of Pentafluorobenzonitrile.《J.Chem.Soc.(C)》.1971, |
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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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