CN1309701C - Method for producing alpha-(5-dihydroacenaphthenyl)ethylamine hydrochloride - Google Patents
Method for producing alpha-(5-dihydroacenaphthenyl)ethylamine hydrochloride Download PDFInfo
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- CN1309701C CN1309701C CNB021371687A CN02137168A CN1309701C CN 1309701 C CN1309701 C CN 1309701C CN B021371687 A CNB021371687 A CN B021371687A CN 02137168 A CN02137168 A CN 02137168A CN 1309701 C CN1309701 C CN 1309701C
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- dihydro
- acenaphthene
- ethylamine hydrochloride
- acenaphthylene base
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Abstract
The present invention discloses a method for preparing alpha-(5-dihydro acenaphthenyl)ethylamine hydrochloride. 5-acetyl dihydro acenaphthene as raw material reacts with an aminating reagent and a reducing agent in alcohol solvent to obtain alpha-(5-dihydro acenaphthenyl)ethylamine, and then, the alpha-(5-dihydro acenaphthenyl)ethylamine is acidified by hydrochloric acid to obtain the target product of the present invention. The purity of the alpha-(5-dihydro acenaphthenyl)ethylamine hydrochloride prepared by the preparing method reaches more than 98%, the productive rate is from 40% to 50%, and the melting point is from 235.5 to 237.5 DEG C. Compared with the prior art, the method has the advantages of reaction under ordinary pressure, safe and convenient operation, operational environment improvement, low toxicity of used raw material and stable product quality, and is suitable for industrialized production.
Description
Technical field
The present invention relates to the preparation method of a kind of α-(5-dihydro-acenaphthylene base) ethylamine hydrochloride.
Background technology
α-(5-dihydro-acenaphthylene base) ethylamine hydrochloride is a kind of important organic synthesis intermediate, can be used as the intermediate of synthesis of chiral stationary phase especially, has very to use widely in the fractionation field of chipal compounds, and its structural formula is as follows:
At present, existing many patents and bibliographical information the preparation method of α-(5-dihydro-acenaphthylene base) ethylamine compounds, as U.S. Pat 2,996,545 disclose a kind of method for preparing α-(Alpha-Naphthyl) ethamine with methyl-Alpha-Naphthyl ketone through high pressure amination reduction.In autoclave, methyl-Alpha-Naphthyl ketone, liquefied ammonia are dissolved in the methanol solution, add Raney Ni catalyzer, at 175-200 ℃, 500kg/cm
2Under the above high pressure hydrogenation reaction 3-4 hour, make α-(Alpha-Naphthyl) ethamine.The method of this patent report, is synthesized in autoclave as solvent with highly toxic methyl alcohol, complex operation, and have suitable danger, industrial prospect is undesirable;
" chemical journal " (1988,46,784-790) reported with methyl-Alpha-Naphthyl ketone by the synthetic α of Blicke method-acetonaphthone oxime; α-acetonaphthone oxime under T1 type Raney Ni catalyzer, at 90-100 ℃, 80-100kg/cm
2Following hydrogenation, preparation α-(Alpha-Naphthyl) ethamine.This method need be carried out two-step reaction, high pressure, and complex operation, dangerous, industrial prospect is undesirable;
J.Org.Chem. (1992; Vol.57No.14; 3854-3860) disclosed a kind of cyclic ketones compound under nitrogen protection; with the ammonium acetate is amination reagent, and sodium cyanoborohydride is a reductive agent, and Virahol is a solvent; at 95-100 ℃; under the pressurized conditions, vigorous stirring 24 hours gets corresponding aminated compounds.In this preparation method, need compressive reaction under nitrogen protection, in 24 hours reaction times, by product is more in the products therefrom, the value of not applying.
Summary of the invention
The technical problem that the present invention solves provides the preparation method of a kind of α-(5-dihydro-acenaphthylene base) ethylamine hydrochloride, to overcome the shortcoming that needs reaction under high pressure, dangerous big, complex operation in the prior art.
Technical conceive of the present invention is such: with 5-ethanoyl acenaphthene is raw material, in the alcohols reaction solvent, reacts with amination reagent and reductive agent, obtains α-(5-dihydro-acenaphthylene base) ethamine, carries out the salt acidifying then, promptly obtains target product of the present invention.
Method of the present invention comprises the steps:
(1) α-(5-dihydro-acenaphthylene base) ethamine is synthetic: with reaction 5-15 hour under the condition of normal pressure, 80-85 ℃ of 5-ethanoyl acenaphthene, amination reagent, reductive agent and alcohols reaction solvent, collect α-(5-dihydro-acenaphthylene base) ethamine from reaction product;
According to the present invention, preferably adopt extraction agent from reaction product, to collect α-(5-dihydro-acenaphthylene base) ethamine, said extraction agent is one or more in ether, methylene dichloride, the tetrahydrofuran (THF), and the consumption of extraction agent is a 5-ethanoyl acenaphthene: extraction agent=1.0: 10.0-15.0 (mass ratio);
Said amination reagent is an ammonium salt, a kind of in commonly used ammonium acetate, ammonium chloride or the ammonium sulfate;
Said reductive agent is a kind of in sodium cyanoborohydride, sodium borohydride or the lithium aluminium hydride;
Said alcohols reaction solvent is C
2～C
4Unit alcohol, one or more in Virahol, propyl alcohol, butanols or the ethanol preferably;
Ratio of components is a 5-ethanoyl acenaphthene: reductive agent: amination reagent=1.0: 3.0-4.0: 10.0-20.0 (mol ratio), the consumption of reaction solvent are 5-ethanoyl acenaphthene: reaction solvent=1.0: 10.0-20.0 (mass ratio);
(2) salt acidifying: in α-(5-dihydro-acenaphthylene base) ethamine that step (1) is collected, feed the exsiccant hydrogen chloride gas, collect the white solid of separating out, be the said α of the present invention-(5-dihydro-acenaphthylene base) ethylamine hydrochloride.
According to the present invention, the mixed solvent that can preferably adopt ethanol, ether and normal hexane to form carries out recrystallization to α-(5-dihydro-acenaphthylene base) ethylamine hydrochloride of collecting.
The consumption of mixed solvent is α-(5-dihydro-acenaphthylene base) ethylamine hydrochloride: mixed solvent=1.0: 5.0-10.0 (mass ratio).
Mixed solvent of the present invention is by ethanol: ether: normal hexane=5-10: 2: 3 volume ratio is prepared.
Reaction formula of the present invention is as follows:
Behind α-(5-dihydro-acenaphthylene base) the ethylamine hydrochloride recrystallization that obtains with preparation method of the present invention, purity reaches more than 98%, and productive rate is 40%-50%, and fusing point is 235.5-237.5 ℃.
Raw material 5-ethanoyl acenaphthene used in the present invention is according to J.Chem.Soc., PerkinTrans.2, and 1996, the 2125-2131 reported method prepares.
The present invention is reflected under the normal pressure and carries out compared with prior art, simple and safe operation, and operating environment improves, and used starting material toxicity reduces, and constant product quality is suitable for suitability for industrialized production.
Embodiment
Below by embodiment the invention will be further described the present invention, but embodiment does not limit protection scope of the present invention.
Embodiment 1
In the reactor that has heating, stirring, thermometer, reflux condensing tube, add 5-ethanoyl acenaphthene 38g (0.191mol) respectively; sodium cyanoborohydride 45g (0.716mol) and ammonium acetate 225g (2.92mol); its mol ratio is 1.0: 3.75: 15.3; add Virahol 800ml again; stirring at room, heating gradually, temperature of reaction is controlled at 80-85 ℃; reacted 5 hours, and obtained α-(5-dihydro-acenaphthylene base) ethamine.After reaction solution steamed the solvent Virahol with rotatory evaporator, be cooled to room temperature, add 300ml water, 300ml ether, tell the ether layer after stirring, leaving standstill, water is used the 300ml extracted with diethyl ether once again, tell the ether layer, secondary ether is also laminated, uses anhydrous magnesium sulfate drying, filters, filtrate feeds the exsiccant hydrogen chloride gas, separates out a large amount of white solid product α-(5-dihydro-acenaphthylene base) ethylamine hydrochloride.Filter, use ether drip washing, the mixed solvent 154g that adds ethanol, ether and normal hexane carries out recrystallization, obtains the 22g product, productive rate 48.3%, and purity is 98.7%, fusing point is 235.7-237.3 ℃.
Embodiment 2
In the reactor that has heating, stirring, thermometer, reflux condensing tube, add 5-ethanoyl acenaphthene 38g (0.191mol), sodium cyanoborohydride 36g (0.573mol), ammonium acetate 147g (1.91mol) respectively; its mol ratio is 1.0: 3.0: 10.0; add Virahol 800ml again; stirring at room; heating; temperature of reaction is controlled at 80-85 ℃, and the reaction times is 15 hours, obtains α-(5-dihydro-acenaphthylene base) ethamine.Other processing step, material proportion and reaction parameter are all with embodiment 1.The productive rate 41.3% of product, purity are 98.3%, and fusing point is 235.4-237.0 ℃.
Embodiment 3
In the reactor that has heating, stirring, thermometer, reflux condensing tube, add 5-ethanoyl acenaphthene 20g (0.102mol), sodium cyanoborohydride 26g (0.408mol), ammonium acetate 157g (2.04mol) respectively; its mol ratio is 1.0: 4.0: 20.0; stir; heating; temperature of reaction is controlled at 80-85 ℃; reaction times is 10 hours, obtains α-(5-dihydro-acenaphthylene base) ethamine.Other processing step, material proportion and reaction parameter are all with embodiment 1.The productive rate 45.6% of product, purity are 98.4%, and fusing point is 235.2-236.9 ℃.
Claims (6)
1. the preparation method of α-(5-dihydro-acenaphthylene base) ethylamine hydrochloride is characterized in that comprising the steps:
(1) 5-ethanoyl acenaphthene, amination reagent, reductive agent and alcohols reaction solvent were reacted 5～15 hours under the condition of normal pressure, 80-85 ℃, produce the thing from reaction and collect α-(5-dihydro-acenaphthylene base) ethamine;
(2) in α-(5-dihydro-acenaphthylene base) ethamine that step (1) is collected, feed the exsiccant hydrogen chloride gas, collect the white solid of separating out, be α-(5-dihydro-acenaphthylene base) ethylamine hydrochloride;
Amination reagent is a kind of in ammonium acetate, ammonium chloride or the ammonium sulfate;
Reductive agent is a kind of in sodium cyanoborohydride, sodium borohydride or the lithium aluminium hydride;
The alcohols reaction solvent is C
2～C
4Unit alcohol.
2. method according to claim 1 is characterized in that the alcohols reaction solvent is one or more in Virahol, propyl alcohol, butanols or the ethanol.
3. method according to claim 1 is characterized in that, takes extraction agent to produce the thing from reaction and collects α-(5-dihydro-acenaphthylene base) ethamine, and said extraction agent is one or more in ether, methylene dichloride, the tetrahydrofuran (THF).
4. method according to claim 3 is characterized in that, the consumption of extraction agent is a 5-ethanoyl acenaphthene: extraction agent=1.0: 10.0-15.0, mass ratio.
5. method according to claim 1, it is characterized in that, the mixed solvent of forming with ethanol, ether and normal hexane carries out recrystallization to the product of step (2), and the consumption of mixed solvent is α-(5-dihydro-acenaphthylene base) ethylamine hydrochloride: mixed solvent=1.0: 5.0-10.0, mass ratio; Mixed solvent is by ethanol: ether: normal hexane=5-10: 2: 3 volume ratio is prepared.
6. according to each described method of claim 1～5, it is characterized in that the ratio of components of step (1) is a 5-ethanoyl acenaphthene: reductive agent: amination reagent=1.0: 3.0-4.0: 10.0-20.0, mol ratio; The consumption of reaction solvent is a 5-ethanoyl acenaphthene: reaction solvent=1.0: 10.0-20.0, mass ratio.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021371687A CN1309701C (en) | 2002-09-26 | 2002-09-26 | Method for producing alpha-(5-dihydroacenaphthenyl)ethylamine hydrochloride |
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|---|---|---|---|
| CNB021371687A CN1309701C (en) | 2002-09-26 | 2002-09-26 | Method for producing alpha-(5-dihydroacenaphthenyl)ethylamine hydrochloride |
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|---|---|
| CN1485314A CN1485314A (en) | 2004-03-31 |
| CN1309701C true CN1309701C (en) | 2007-04-11 |
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| CNB021371687A Expired - Fee Related CN1309701C (en) | 2002-09-26 | 2002-09-26 | Method for producing alpha-(5-dihydroacenaphthenyl)ethylamine hydrochloride |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2996545A (en) * | 1957-08-05 | 1961-08-15 | Chemetron Corp | Optical resolution of alpha-(alpha-naphthyl) ethylamine |
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2002
- 2002-09-26 CN CNB021371687A patent/CN1309701C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2996545A (en) * | 1957-08-05 | 1961-08-15 | Chemetron Corp | Optical resolution of alpha-(alpha-naphthyl) ethylamine |
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