CN1079733A - The synthetic method of a-benzoin oxime - Google Patents
The synthetic method of a-benzoin oxime Download PDFInfo
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- CN1079733A CN1079733A CN 93110944 CN93110944A CN1079733A CN 1079733 A CN1079733 A CN 1079733A CN 93110944 CN93110944 CN 93110944 CN 93110944 A CN93110944 A CN 93110944A CN 1079733 A CN1079733 A CN 1079733A
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- almond oil
- benzoin oxime
- oxammonium hydrochloride
- bitter almond
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Abstract
The present invention is a kind of synthetic a-benzoin oxime (α-BcnzoinOximc), the method that has another name called An Xixiangwo, in the alcoholic solution of oxammonium hydrochloride, add bitter almond oil camphor and carbonate powder, stirring reaction is 5-10 hours under room temperature (5-40 ℃), boils off most of solvent, and remaining mixture under agitation adds hot water, precipitating, get thick product, yield 95-99%, 140-145 ℃ of fusing points after the cooling.Add an amount of benzene in the thick product and reflux half an hour approximately, get the pure product of a-benzoin oxime, 154-155 ℃ of fusing points, overall yield 71-75%.
Technology of the present invention is simple, the productive rate height, and cost is low, and quality is good, is suitable for industrial production.
Description
The present invention relates to the synthetic method of a kind of sequestrant and organic compound intermediate-a-benzoin oxime.
A-benzoin oxime (α-Benzoin Oxime) be An Xixiangwo again, and its molecular structural formula is:
A-benzoin oxime is commonly called as cupron, is to identify and measure the best reagent that copper, molybdenum and tungsten are particularly measured molybdenum.Also can be used as the sequestrant of extraction tantalum, vanadium, tungsten etc., in ore dressing, have important purposes.
A-benzoin oxime also has important purposes in organic synthesis, be the basic raw material of synthetic 1,2-phenylbenzene-2-hydroxyl-ethamine and derivative and other organic compound.
With bitter almond oil camphor and oxammonium hydrochloride is the synthetic a-benzoin oxime of raw material:
Have many scholar's research to synthesize a-benzoin oxime with this reaction, its synthetic method can be divided into two classes:
One, pyridine method:
In the reaction pyridine double as solvent and in and the alkali of oxammonium hydrochloride, be reflected under 0 ℃ and carry out.〔Kaoru Harada，Bull.Chem.Soc.Jpn.57.1040-1045，1984〕。
The shortcoming of this law is that the yield of product is low.Adopt chromatographic separation in the document, productive rate is 58%.As adopting benzene to make solvent recrystallization, productive rate is 23%.
Adopt pyridine to make solvent, the cost height, and also pyridine has a kind of painful stench, pollutes to environment, makes troubles to synthetic work.
Two, aqueous sodium hydroxide solution-Ethanol Method.
Use in the sodium hydroxide before the reaction and the aqueous solution of oxammonium hydrochloride, and bitter almond oil camphor is dissolved in the ethanol, again both are poured into heating reflux reaction in the reactor.The separation of reaction product, pure system adopt recrystallization method.(Windholz Martha ed.The Merck Index.llth ed.Rahway(New Jersey); Merck ﹠amp; Co., Inc., 1988.1104.(day) the chemical industry day .11 of newspaper office 290 commodity chemical, Tokyo: chemical industry day newspaper office, 1990,14670.）。
Free azanol NH
2Therefore OH is a kind of very unstable compounds, adopts in the sodium hydroxide and the aqueous solution of oxammonium hydrochloride, and the way of heating often cause reacting in the decomposition of azanol, make the productive rate of reactor product of this method low and unstable, have only 24～55%.Thus during the method precipitating, the thick product that draws, it is agglomerating to bond, the aftertreatment difficulty.
The objective of the invention is in the hope of reaching simplification technology, to improve the quality of products, improve product yield, reduce cost, reduce the purpose of environmental pollution by improving the deficiencies in the prior art.
The present invention is such:
Oxammonium hydrochloride is dissolved in the alcohol, adds bitter almond oil camphor powder and carbonate powder then respectively, proportioning raw materials is an oxammonium hydrochloride: bitter almond oil camphor: carbonate=1～2: 1: 1～2(mol ratio).At room temperature stir about 5-10 hour, there is gas to discharge in the whipping process.Reaction is finished, and about 80% alcohol is reclaimed in underpressure distillation.In the mixture of the reaction product of remainder, add the warm water of capacity, can obtain loose in a large number white precipitate after the vigorous stirring.Collect this white precipitate, clean three times, drain, promptly get the product that fusing point is 140-145 ℃ a a-benzoin oxime after the drying, productive rate 95-99% with distilled water is careful.
This product in a certain amount of benzene reflux about half an hour after, can get fusing point is the pure product of 154-155 ℃ a-benzoin oxime, productive rate 71-75%.
The alcohol that is suitable among the present invention is methyl alcohol and ethanol.The carbonate that uses is: yellow soda ash, sodium bicarbonate, saleratus or bicarbonate of ammonia.
Reaction system of the present invention is the solid-liquid two-phase system, use the minimum amount of alcohol to use in should be able to solubilizing reaction oxammonium hydrochloride.
The temperature range of room temperature of the present invention is 5-40 ℃.
In the method for the invention, because azanol is slowly to discharge in the carbonate that is slightly soluble in alcohol and in the process of oxammonium hydrochloride, reaction is at room temperature carried out, and has so just fully reduced the decomposition loss of azanol in reaction process.Thereby improved the productive rate of benzoinoxime significantly, productive rate reaches as high as 99% generally more than 95%, and very stable.The purity of product is higher.Thick product is loose, is easy to aftertreatment.Simultaneously used raw alcohol and carbonate are all inexpensive, and production cost is greatly reduced, and only are equivalent to about 50% of old production method.
By product of the present invention is few, and waste residue and liquid is few, and is very little to environmental hazard.
Method raw material of the present invention is easy to get, and inexpensive, technology is simple, the product yield height, and cost is low, and good product quality is suitable for industrial production.
, be further elaborated method of the present invention below in conjunction with embodiment:
Embodiment one:
In 2 liters of round-bottom reaction flask of magnetic agitation, add 1 liter of methyl alcohol, 104 gram oxammonium hydrochlorides.After treating that oxammonium hydrochloride all dissolves, add bitter almond oil camphor (Benzoin) 212 grams again, sodium bicarbonate 126 grams.Bitter almond oil camphor and sodium bicarbonate are fine powdered.This mixture stirred 8 hours under 25-28 ℃ room temperature, and CO is arranged
2Gas produces.
Underpressure distillation, remove and reclaim about 800 ml methanol after, in the about 4 intensification hot water of the whole impourings of residuum, vigorous stirring produces a large amount of loose white precipitates.Leave standstill, be cooled to the room temperature after-filtration, collect white precipitate.After white precipitate cleaned three times with distilled water, suction filtration was drained as far as possible.The white precipitate that to clean and drain is divided in a ceramic whiteware dish, dry one day after, with infrared lamp oven dry, temperature is no more than 50 ℃ during baking again.
Output: 225 grams, productive rate: 99%.
Fusing point: 139-144 ℃.
225 gram thick products and 1300 milliliters of benzene are put into 3 liters of round-bottom reaction flask, reflux half an hour.The mixture that reflow treatment is crossed leaves standstill, cooling, suction filtration after about five, six hours, collects white small grains shape product.Clean this white product twice with a small amount of benzene, drain, divide in the ceramic whiteware dish and dry.
Output: 160 grams, productive rate: 71.1%
Fusing point: 154-155 ℃
Embodiment two:
Add 16 gram oxammonium hydrochlorides in-500 milliliters of round-bottomed flasks, 250 ml methanol all are dissolved into colourless transparent solution after stirring.Add 30 pulverous bitter almond oil camphors of gram and 18 gram bicarbonate of ammonia again, 8-10 ℃ was stirred 8 hours down, has gas to emit in the whipping process.
Reaction product in the distilled water of the about 0.8 intensification heat of the whole impourings of residuum, obtains a large amount of white precipitates after stirring after about 200 ml methanol are removed and reclaimed in underpressure distillation.
Filter, collect white precipitate, distilled water is given a baby a bath on the third day after its birth inferior, drains, dries, and is dry under infrared lamp at last.
Output: 31 grams, productive rate: 97%
Fusing point: 143-148 ℃
Embodiment three:
Add 52 gram oxammonium hydrochlorides in-1000 milliliters of round-bottomed flasks, 600 ml methanol all are dissolved into colourless transparent solution after stirring.Add 106 gram bitter almond oil camphor powder and 40 gram powdered sodium carbonates again, under 15-18 ℃ of room temperature, stirred 9 hours, have gas to emit.
Reaction is finished, and after about 500 ml methanol are reclaimed in underpressure distillation, in the about 2.5 intensification hot water of the whole impourings of residuum, obtains a large amount of white precipitates after stirring.
Filter, collect white precipitate, distilled water cleans three times, drains, dries, and uses the infrared lamp drying at last.
Output: 111.5 grams, productive rate: 98%
Fusing point: 140-145 ℃
Claims (4)
1, a kind of method by bitter almond oil camphor and the synthetic a-benzoin oxime of oxammonium hydrochloride is characterized in that oxammonium hydrochloride is dissolved in the alcoholic solvent, adds bitter almond oil camphor and carbonate powder respectively, descends stirring reaction 5-10 hour in room temperature (5-40 ℃).
2, according to the described method of claim 1, its raw material amount ratio is an oxammonium hydrochloride: bitter almond oil camphor: carbonate=1～2: 1: 1～2(mol ratio).
3, according to the described method of claim 1, wherein said carbonate is yellow soda ash, salt of wormwood, sodium bicarbonate, saleratus or bicarbonate of ammonia.
4, according to the described method of claim 1, wherein said alcoholic solvent is methyl alcohol or ethanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93110944 CN1082045C (en) | 1993-04-08 | 1993-04-08 | Synthetic method of a-benzoin oxime |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93110944 CN1082045C (en) | 1993-04-08 | 1993-04-08 | Synthetic method of a-benzoin oxime |
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| Publication Number | Publication Date |
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| CN1079733A true CN1079733A (en) | 1993-12-22 |
| CN1082045C CN1082045C (en) | 2002-04-03 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 93110944 Expired - Fee Related CN1082045C (en) | 1993-04-08 | 1993-04-08 | Synthetic method of a-benzoin oxime |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101671267B (en) * | 2009-09-30 | 2012-09-05 | 浙江理工大学 | Method for directly converting addition product of sodium bisulfite of aldehyde or aliphatic methyl ketone into corresponding oxime |
| CN102702023A (en) * | 2012-05-14 | 2012-10-03 | 清华大学 | Synthesis method of trans-alpha-benzoinoxime |
| US9783492B2 (en) * | 2013-04-03 | 2017-10-10 | Zcl Chemicals Limited | Process for the preparation of fluvoxamine maleate |
-
1993
- 1993-04-08 CN CN 93110944 patent/CN1082045C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101671267B (en) * | 2009-09-30 | 2012-09-05 | 浙江理工大学 | Method for directly converting addition product of sodium bisulfite of aldehyde or aliphatic methyl ketone into corresponding oxime |
| CN102702023A (en) * | 2012-05-14 | 2012-10-03 | 清华大学 | Synthesis method of trans-alpha-benzoinoxime |
| US9783492B2 (en) * | 2013-04-03 | 2017-10-10 | Zcl Chemicals Limited | Process for the preparation of fluvoxamine maleate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1082045C (en) | 2002-04-03 |
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