CN1172794A - Method for combined preparation of hydroxylamine salt and hypocarbonyl compound - Google Patents
Method for combined preparation of hydroxylamine salt and hypocarbonyl compound Download PDFInfo
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- CN1172794A CN1172794A CN 96122334 CN96122334A CN1172794A CN 1172794 A CN1172794 A CN 1172794A CN 96122334 CN96122334 CN 96122334 CN 96122334 A CN96122334 A CN 96122334A CN 1172794 A CN1172794 A CN 1172794A
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- acid
- dicarbonyl compound
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Abstract
A process for preparing both hydroxylamine salt and hypocarbonyl compound includes such steps as the reaction of carbonyl compound (ArCOCH2Ar') with two or three H on alpha -C on nitrite at -10 -100 deg. C, hydrolysis in acidic solution, and distillation or reduction distillation or extracting, or freezing.
Description
What the present invention relates to is to have the carbonyl compound of two or three hydrogen and nitrous acid ester reaction to generate hydroxylammonium salt and the novel method that connects dicarbonyl compound on alpha-carbon.
Chemicals application manual P
152The report oxammonium hydrochloride is that reacting again with acetone afterwards, hydrolysis produces oxammonium hydrochloride with Sodium Nitrite and Sodium Pyrosulfite, sulfuric acid reaction.Graboyes, Harold et al reports in EP0049638, with (CH
3COCNOHCO
2Et) in acidic aqueous solution, add Paraformaldehyde 96 and be hydrolyzed, generate CH
3COCOCO
2Et.Tong Zunxing is at Zhejiang chemical industry nineteen ninety 22 volumes the 4th phase P
50Report is used CH
3COCNOHCH
3In acidic aqueous solution, add formaldehyde and be hydrolyzed, generate CH
3COCOCH
3Add formaldehyde and all increased impurity.
94105128.5 in number applying for a patent, I have reported a kind of manufacture method that connects dicarbonyl compound; Be used in the carbonyl compound of two or three hydrogen (ArCOCH is arranged on α-carbonyl
2Ar ') generates carbonyl oxime (ArCOCNOHAr ') with nitrous acid (HONO) or nitrous acid ester (RONO) reaction; With the hydrolysis in acidic solution of carbonyl oxime, can add formaldehyde or Paraformaldehyde 96, but bubbling air or O
2Or NO
nGas obtains connecting dicarbonyl compound.But because most dicarbonyl compound that connects easily dissolves in water, so the dicarbonyl compound purity that this method obtains is all not too pure, and the azanol in the solution also all has been wasted.The present invention is exactly on the basis of above-mentioned patent, make carbonyl compound and nitrous acid ester reaction that two or three hydrogen are arranged on alpha-carbon, hydrolysis generates azanol and connects dicarbonyl compound under acidic conditions afterwards, adopt distillation or extraction or refrigerated method at last, obtain azanol respectively and connect dicarbonyl compound, thereby finish the present invention.
Following mask body describes the present invention in detail:
The present invention makes company's dicarbonyl compound and hydroxylammonium salt relates to two-step reaction:
The first step: be used in the carbonyl compound that two or three hydrogen are arranged on the alpha-carbon and carry out the carbonyl oxime that nitrosation reaction generates correspondence.Reaction formula is expressed as follows:
R-can be alkyl or the alkyl with 1-6 carbon atom.
Ar-can be H, OH, and OR has the low alkyl group or the substituted alkyl of 1-6 carbon atom, aryl or substituted aryl, carboxyl or ester group.
Ar '-can be H, OH, OR has the low alkyl group or the substituted alkyl of 1-6 carbon atom, aryl or substituted aryl, carboxyl or ester group.
For example: ArCOCH
2Ar can be acetaldehyde (CH
3CHO), acetone (CH
3COCH
3), propionic aldehyde (CH
3CH
2CHO), methylethylketone (CH
3COCH
2CH
3), acetate (CH
3COOH), methyl phenyl ketone (C
6H
5COCH
3), beta-hydroxy butanone (CH
3COCH
2CH
2OH), methyl aceto acetate (CH
3COCH
2CO
2Et) etc.
The acid that reaction is used can be hydrochloric acid, sulfuric acid, phosphoric acid, Phenylsulfonic acid, acetic acid etc.
Temperature of reaction is advisable at-10～100 ℃ usually.
Embodiment 4. (production of azanol and pyruvic aldehyde)
Get the 500ml four-hole bottle, load onto condenser, thermometer is plugged in electronic stirring, gas duct; Add the 116g propionic aldehyde, 15ml water, 8gH
2SO
4Feed ethyl nitrite, keep 35 ℃ of temperature of reaction, till no longer rising to temperature, continue reaction 1 hour, add 30% sulfuric acid 150ml, continue reaction 2 hours, extraction afterwards adds diethyl ether, extraction liquid boils off ether and gets pyruvic aldehyde, the raffinate condensing crystal obtains oxammonium sulfate, pyruvic aldehyde yield 72%, oxammonium sulfate yield 88%.
Embodiment 5. (production of azanol and alpha-chloro dimethyl diketone)
Get the 500ml four-hole bottle, load onto condenser, thermometer is plugged in electronic stirring, and gas duct adds 1-chloro butanone-2 (CH
2ClCOCH
2CH
3) 160g, 30ml hydrochloric acid, 40 ℃ feed ethyl nitrites react no longer rise to temperature till, will go up reaction solution and join in the 80ml hydrochloric acid, 40 ℃ of hydrolysis 3 hours, add chloroform extraction afterwards and go out the alpha-chloro dimethyl diketone, the extraction liquid fractionation by distillation goes out chloroform, obtains the alpha-chloro dimethyl diketone, yield 81%, the raffinate condensing crystal obtains oxammonium hydrochloride yield 77%.
Embodiment 6. (azanol and phenyl oxalic dialdehyde production)
Get the 500ml four-hole bottle, load onto condenser, electronic stirring, plug thermometer, gas duct, add the 120g methyl phenyl ketone, 20ml hydrochloric acid, feed methyl nitrite till 50 ℃ of temperature of reaction no longer raise, add 80ml hydrochloric acid again, reacted 2 hours, feed HCl gas afterwards, freezing, separate out oxammonium hydrochloride, yield 72%, the debris extraction that adds diethyl ether boils off ether and promptly gets the phenyl oxalic dialdehyde, yield 89% after the extraction.
Claims (6)
1. unite manufacturing hydroxylammonium salt (NH for one kind
2OHHM) and connect the method for dicarbonyl compound ArCOCOAr '.Be characterised in that to be used in the carbonyl compound of two or three hydrogen (ArCOCH is arranged on the alpha-carbon
2Ar ') with nitrous acid ester (RONO) oximation reaction takes place and generate corresponding carbonyl oxime (ArCOCNOHAr '), the hydrolysis in acidic aqueous solution of its crude product or elaboration generates hydroxylammonium salt and connects dicarbonyl compound.
HM-can be hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetate, Phenylsulfonic acid etc.
Ar-can be H, OH, OR, the low alkyl group with 1-6 carbon atom or substituted alkyl, aryl or substituted aryl, carboxyl or ester group.
Ar '-can be H, OH, OR, low alkyl group or substituted alkyl with 1-6 carbon atom, aryl or substituted aryl, carboxyl or ester group.
R-can be alkyl or the alkyl with 1-6 carbon atom.
2. described according to claim 1, it is characterized in that the hydroxylammonium salt that generates and connect the dicarbonyl compound aqueous solution isolating hydroxylammonium salt and connecting dicarbonyl compound by distillation or underpressure distillation or steam distillation or protection of inert gas distillation or extraction or method such as freezing.Extraction solvent can be organic solvents such as chloroform, ether, benzene, butanols.
3. described according to claim 1, react in the intermediate carbonyl oxime adding acidic aqueous solution that it is characterized in that generating.
4. described according to claim 1, it is characterized in that adding aqueous acid to the intermediate carbonyl oxime that generates.
5. described according to claim 1, it is characterized in that oximation reaction and hydrolysis reaction are combined into single stepping, promptly when oximation reaction, add the acid of q.s, make the timely hydrolysis of carbonyl oxime of generation generate hydroxylammonium salt and connect dicarbonyl compound.
6. described according to claim 1.3.4.5., temperature of reaction is-10 °～100 ℃, particularly 0～60 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96122334 CN1172794A (en) | 1996-11-04 | 1996-11-04 | Method for combined preparation of hydroxylamine salt and hypocarbonyl compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96122334 CN1172794A (en) | 1996-11-04 | 1996-11-04 | Method for combined preparation of hydroxylamine salt and hypocarbonyl compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1172794A true CN1172794A (en) | 1998-02-11 |
Family
ID=5127269
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 96122334 Pending CN1172794A (en) | 1996-11-04 | 1996-11-04 | Method for combined preparation of hydroxylamine salt and hypocarbonyl compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1172794A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110845323A (en) * | 2019-11-15 | 2020-02-28 | 山东省化工研究院 | Preparation method of hydroxylamine formate |
-
1996
- 1996-11-04 CN CN 96122334 patent/CN1172794A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110845323A (en) * | 2019-11-15 | 2020-02-28 | 山东省化工研究院 | Preparation method of hydroxylamine formate |
| CN110845323B (en) * | 2019-11-15 | 2022-04-26 | 山东省化工研究院 | Preparation method of hydroxylamine formate |
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