CN105622438A - Synthetic method for tyramine hydrochloride - Google Patents
Synthetic method for tyramine hydrochloride Download PDFInfo
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- CN105622438A CN105622438A CN201610111210.7A CN201610111210A CN105622438A CN 105622438 A CN105622438 A CN 105622438A CN 201610111210 A CN201610111210 A CN 201610111210A CN 105622438 A CN105622438 A CN 105622438A
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- synthetic method
- copper powder
- gac
- hydrochloride
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- ASTZQWXFTIFTEE-UHFFFAOYSA-N I/N=[I]/N1CC1 Chemical compound I/N=[I]/N1CC1 ASTZQWXFTIFTEE-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The invention discloses a synthetic method for tyramine hydrochloride. The synthetic method includes the steps that phenol is used as a raw material and reacts with aminoacetonitrile to generate p-hydroxy phenylaminoethanol, p-hydroxy phenylaminoethanol is subjected to catalytic reduction to obtain tyramine hydrochloride, activated carbon and copper powder are used as a composite catalyst, and the mass ratio of the activated carbon to the copper powder is (3-5):1. As the activated carbon and copper powder composite catalyst is added, the ratio of the dosage of the catalyst to the substrate weight can be reduced to (0.1-0.2):1. The catalytic efficiency is improved remarkably, the number of times of continuously using the catalyst can be increased to be 10 or more, the total yield of the reactions is increased, and the synthetic method has high economic benefits.
Description
Technical field:
The present invention relates to the synthetic method of a kind of Hydrphenacetamine Hydrochloride, the method is taking gac and copper powder as composite catalyst.
Background technology:
Tyrasamine (Tyramine) has another name called Uteramin (molecular weight 137.18, CAS 51-67-2), is white or off-white color solid. Tyrasamine is a kind of compound separated from ergotine and rotten animal tissues at first. Owing to this compound has the pharmacological action such as raising blood pressure and excited uterus, it is synthesized again by people with manual method, it is applied to biochemical reagents, organic chemical industry and medicine intermediate, can be used as treatment migraine and the medicine of diagnosis pheochromocytoma, at present mainly for the preparation of blood lipid-lowering medicine bezafibrate.
In prior art, tyrasamine synthetic route mainly contains 4:
Route one: being that raw material obtains tyrasamine through nitrated, reduction, diazotization, reduction taking benzyl cyanide, this route steps is loaded down with trivial details, and total recovery is low.
Route two: be that raw material and propanedioic acid reaction generate p-methoxycinnamic acid taking aubepine, then obtain Hydrphenacetamine Hydrochloride through reduction, chlorination, ammonification, rearrangement, demethylation. Although respectively step receipts rate is all higher for this route, but reactions steps is more, uses the stronger raw materials of corrodibility such as more sulfur oxychloride, ammoniacal liquor, concentrated hydrochloric acid in reaction process, environmental pollution is bigger.
Route three: take tyrosine as the pyrolysis decarboxylation route of raw material. The product that this route obtains is difficult to purify, and temperature of reaction height, reaches 245 DEG C, and equipment requirements is higher.
Route four: be that raw material first obtains hydroxy-beta-nitrostyrolene with Nitromethane 99Min. condensation taking p-Hydroxybenzaldehyde, then adopt 5% palladium carbon reduction to obtain tyrasamine. The palladium carbon consumption that reduction in this route uses is too big, and wherein the consumption of 5% palladium carbon is 1: 1 (m/m) with the ratio of the charging capacity to hydroxy-beta-nitrostyrolene, owing to palladium carbon price is higher, and character is active, easy spontaneous combustion, consumption too conference make cost higher, poor stability.
Route five: take phenol as starting raw material, first generate parahydroxyacet-ophenone amine with aminoacetonitriles reaction, then catalytic reduction obtains Hydrphenacetamine Hydrochloride, time m (substrate): m (catalyzer)=1: 0.09 ideal, catalysis receipts rate is about 80%, catalytic efficiency is lower, and catalyzer can be applied mechanically about 5 times continuously, and product yield is on the low side.
The current tyrasamine of China mainly relies on import, and price is higher, therefore urgently needs to develop the synthesis route that cost is lower, be applicable to suitability for industrialized production on market.
" fine-chemical intermediate " that volume the 4th phase August the 39th in 2009 publishes discloses one section " synthetic route of tyrasamine and novel process " by name, and author is Chen Wei, Pan Yi, Tao Yong, they propose the new synthetic route that take phenol as starting raw material, and step is simple, and cost is lower, there is industrial applications prospect, be the present invention closest to prior art, but the catalytic efficiency of its catalyst copper powder is lower, copper powder catalyst usage quantity is higher, and total recovery is only 57%, economic benefit is lower.
Summary of the invention:
Technical problem solved by the invention:
The present invention provides the synthetic method of a kind of Hydrphenacetamine Hydrochloride, and the method is taking gac and copper powder as composite catalyst. Composite catalyst usage quantity and substrate weight ratio can narrow down to 0.1-0.2:1, and catalytic efficiency significantly improves, and catalyzer is applied mechanically number of times continuously and can be brought up to more than 10 times; Catalyzed reaction can improve overall yield of reaction, has higher economic benefit.
The present invention provides following technical scheme:
The synthetic method of a kind of Hydrphenacetamine Hydrochloride, take phenol as raw material, phenol and aminoacetonitriles reaction being generated parahydroxyacet-ophenone amine, then parahydroxyacet-ophenone amine catalytic reduction is obtained Hydrphenacetamine Hydrochloride, used catalyst is the composite catalyst that gac and copper powder are formed.
Preferably, in described composite catalyst, the mass ratio of gac and copper powder is 3-5:1.
Preferably, in described composite catalyst, the mass ratio of gac and copper powder is 4.5:1.
Preferably, in described composite catalyst, the mass ratio of gac and copper powder is 4.0:1.
Preferably, described gac is wood activated charcoal or active fruit shell carbon.
Preferably, described gac is particulate state.
Preferably, described catalyst quality: substrate quality is 0.1-0.2:1.
Gac is the solid carbonaceous of a kind of black porous. Shanghai Xi Tan Environmental Protection Technology Co., Ltd by coal by pulverize, shaping or with uniform coal grain through charing, activation produce. Main component is carbon, and containing elements such as a small amount of oxygen, hydrogen, sulphur, nitrogen, chlorine. The specific surface area of normal activated carbon is at 500-1700m2Between/g. There is very strong absorption property, it is a kind of industrial adsorbents that purposes is extremely wide.
Active fruit shell carbon, mainly taking shell and wood chip as raw material, through charing, activation, refining processes. There is the features such as specific surface area is big, intensity height, granularity are even, hole joint structure is flourishing, absorption property is strong. And can free chlorine in active adsorption water, phenol, sulphur, oil, colloid, pesticide residue and other organic contaminations and organic solvent recovery etc. It is applicable to pharmacy, petrochemical complex, sugaring, beverage, drinks purification industry, to aspects such as the decolouring of organism solvent, refining, purification and sewage disposals. Active fruit shell carbon is widely used in tap water, the deep purifying life of industrial water and waste water, industrial purification of water quality and Gas Phase Adsorption, such as power plant, petrochemical industry, refinery, food-drink, sugaring alcoholic, medicine, electronics, breed fish, the process of the industry purification of water quality such as sea-freight, can free chlorine in active adsorption water, phenol, sulphur and other organic pollutant, particularly the precursor of mutagen (THM), reaches purification and impurity removal and removes peculiar smell. Also can be used for industrial tail gas purification, gas sweetening, oil catalytic reforming, the absorption of gas delivery, transformation, dry air, food fresh keeping, smoke mask, solution matchmaker's carrier, industrial solvent filtration, decolouring, purification etc. The separation of various gas, purification, purification; Organic solvent reclaims; The decolouring of sugaring, monosodium glutamate, medicine, drinks, beverage, deodorizing, refining; Noble metal refines; Catalyzer in chemical industry and support of the catalyst. Product has more decolouring, purification, removal of impurities, deodorizing, goes the functions such as peculiar smell, carrier, purification, recovery.
Wood activated charcoal is taking high-quality timber as raw material, profile is powder shape, refine through high temperature carbonization, activation and working procedures and become wood activated charcoal, having specific surface area big, active high, micropore is flourishing, decolorizing ability is strong, the features such as pore texture is bigger, pore texture is big, can have compared with bigger various materials, impurity such as the colors in adsorptive liquid. Be mainly used in food, drinks, oils, beverage, dyestuff, chemical industry, tap water purification, sewage disposal, various purposes is decoloured to fall COD, medicinal carbon etc.
With gac and copper powder compounded formation composite catalyst, it is possible to effective catalysis 3,5-dinitrobenzene-4-chlorobenzotrifluoride carries out Ullmann linked reaction in toluene, obtains new compound 2,2', 6,6'-tetra-nitro-4,4'-two (trifluoromethyl) biphenyl.
Hydrphenacetamine Hydrochloride is preparation method comprise the following steps:
The first step: synthesis of hydroxy methyl phenyl ketone amine:
By 300mL methylene dichloride, 107g (0.8mol) aluminum trichloride (anhydrous), 37.4g (0.404mol) aminoacetonitriles hydrochloride and 37.6g (0.4mol) phenol add in reaction flask successively, stirring at room temperature 5h. Stopped reaction, reclaim under reduced pressure methylene dichloride, then add water 300mL in reaction flask, agitation and filtration, dry yellow solid, i.e. parahydroxyacet-ophenone amine hydrochlorate, m.p.242-244 DEG C, HPLC detection level purity.
2nd step: synthesis Hydrphenacetamine Hydrochloride:
The 20g (0.11mol) upper step being obtained by reacting is to hydroxyacetophenonum amine hydrochlorate, 12% palladium carbon 1.8g, 30mL concentrated hydrochloric acid and 250mL water drop in hydrogenation tank, start and stir, after vacuum pumps the air in retort, replacing 1 time with nitrogen, vacuum extracts nitrogen again, then leads to vigorous stirring into hydrogen, after room temperature reaction 6-6.5h, emptying, takes out filter, and catalyzer adds to be directly used in retort after being filtered dry and reacts next time. Filtrate decompression concentrates and precipitates out to solid, and frozen water cools, and filters, and acetone is washed, dry white solid, i.e. Hydrphenacetamine Hydrochloride, m.p.266-268 DEG C (decomposition), HPLC detection level purity.
The useful effect of the present invention:
1. the inventive method is that composite catalyst usage quantity and substrate weight ratio can narrow down to 0.1-0.2:1 taking gac and copper powder as composite catalyst, reduces raw materials cost.
2. catalyst efficiency of the present invention significantly improves, and number of times applied mechanically continuously by catalyzer can bring up to more than 10 times, for total recovery substantially without impact.
3. the present invention can improve overall yield of reaction, has higher economic benefit.
Embodiment:
Being described in detail by embodiments of the invention below, the present embodiment is implemented under premised on inventive technique scheme, gives detailed enforcement mode and concrete operating process, but protection scope of the present invention is not limited to following embodiment. The experimental program of unreceipted concrete condition in embodiment, the condition that conveniently condition or manufacturers advise usually is implemented.
Hydrphenacetamine Hydrochloride is preparation method comprise the following steps:
The first step: synthesis of hydroxy methyl phenyl ketone amine:
By 300mL methylene dichloride, 107g (0.8mol) aluminum trichloride (anhydrous), 37.4g (0.404mol) aminoacetonitriles hydrochloride and 37.6g (0.4mol) phenol add in reaction flask successively, stirring at room temperature 5h. Stopped reaction, reclaim under reduced pressure methylene dichloride, then add water 300mL in reaction flask, agitation and filtration, dry yellow solid, i.e. parahydroxyacet-ophenone amine hydrochlorate, m.p.242-244 DEG C, HPLC detection level purity.
2nd step: synthesis Hydrphenacetamine Hydrochloride:
The 20g (0.11mol) upper step being obtained by reacting is to hydroxyacetophenonum amine hydrochlorate, 12% palladium carbon 1.8g, 30mL concentrated hydrochloric acid and 250mL water drop in hydrogenation tank, start and stir, after vacuum pumps the air in retort, replacing 1 time with nitrogen, vacuum extracts nitrogen again, then leads to vigorous stirring into hydrogen, after room temperature reaction 6-6.5h, emptying, takes out filter, and catalyzer adds to be directly used in retort after being filtered dry and reacts next time. Filtrate decompression concentrates and precipitates out to solid, and frozen water cools, and filters, and acetone is washed, dry white solid, i.e. Hydrphenacetamine Hydrochloride, m.p.266-268 DEG C (decomposition), HPLC detection level purity.
In described 2nd step, the compound prescription of catalyzer and the usage quantity of catalyzer are in table one.
Table one: the compound prescription of embodiment catalyzer and the usage quantity of catalyzer
The catalyst formulation of different embodiment and addition, on the impact of reaction yield in the 2nd step synthesis Hydrphenacetamine Hydrochloride, have been studied applying mechanically number of times simultaneously. Experimental result is in table two.
Table two: embodiment method is for the impact of Hydrphenacetamine Hydrochloride receipts rate
Time the weight ratio of catalyzer and substrate is 0.05:1, receipts rate is lower, and when the weight ratio of catalyzer and substrate is 0.3:1 time, receipts rate improves obvious not, is unfavorable for the raising of economic benefit.
Time gac weight and copper powder weight ratio are 4.5:1 and 4.0:1, catalytic efficiency is higher, and receipts rate is higher.
When applying mechanically number of times 15 times in experiment, receipts rate is substantially not influenced.
Above content is only the better embodiment of the present invention, for the those of ordinary skill of this area, according to the thought of the present invention, all will change in specific embodiments and applications, and this description should not be construed as limitation of the present invention.
Claims (7)
1. the synthetic method of a Hydrphenacetamine Hydrochloride, it is characterized in that: take phenol as raw material, phenol and aminoacetonitriles reaction are generated parahydroxyacet-ophenone amine, then parahydroxyacet-ophenone amine catalytic reduction is obtained Hydrphenacetamine Hydrochloride, taking gac and copper powder as composite catalyst.
2. the synthetic method of a kind of Hydrphenacetamine Hydrochloride according to claim 1, it is characterised in that: in described composite catalyst, the mass ratio of gac and copper powder is 3-5:1.
3. the synthetic method of a kind of Hydrphenacetamine Hydrochloride according to claim 1, it is characterised in that: in described composite catalyst, the mass ratio of gac and copper powder is 4.5:1.
4. the synthetic method of a kind of Hydrphenacetamine Hydrochloride according to claim 1, it is characterised in that: in described composite catalyst, the mass ratio of gac and copper powder is 4.0:1.
5. according to the synthetic method of a kind of Hydrphenacetamine Hydrochloride one of Claims 1-4 Suo Shu, it is characterised in that: described gac is wood activated charcoal or active fruit shell carbon.
6. according to the synthetic method of a kind of Hydrphenacetamine Hydrochloride one of Claims 1-4 Suo Shu, it is characterised in that: described gac is particulate state.
7. according to the synthetic method of a kind of Hydrphenacetamine Hydrochloride one of Claims 1-4 Suo Shu, it is characterised in that: the quality of described catalyzer and the quality of substrate are 0.1-0.2:1.
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| CN201610111210.7A CN105622438A (en) | 2016-03-01 | 2016-03-01 | Synthetic method for tyramine hydrochloride |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116063192A (en) * | 2021-11-04 | 2023-05-05 | 武汉武药制药有限公司 | Synthesis method of dopamine hydrochloride |
| CN116082173A (en) * | 2021-11-08 | 2023-05-09 | 武汉武药制药有限公司 | Preparation method of dopamine hydrochloride |
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| CN102381991A (en) * | 2011-10-22 | 2012-03-21 | 杭州福斯特药业有限公司 | Method for synthesizing DL-Octopamine hydrochloride |
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2016
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Patent Citations (5)
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| EP1314716A1 (en) * | 2001-11-23 | 2003-05-28 | Sigma Coatings B.V. | Amine phenolic compounds and their use as hardener and/or accelerators in epoxy coatings |
| CN101092373A (en) * | 2006-06-20 | 2007-12-26 | 上海药明康德新药开发有限公司 | Method for synthesizing optically active derivative of 5 - aryl - (S) - N - boc - alpha amino pentanoic acid |
| CN102381991A (en) * | 2011-10-22 | 2012-03-21 | 杭州福斯特药业有限公司 | Method for synthesizing DL-Octopamine hydrochloride |
| CN102584677A (en) * | 2012-02-07 | 2012-07-18 | 安徽金鼎医药有限公司 | Method for preparing gliclazide |
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Non-Patent Citations (1)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116063192A (en) * | 2021-11-04 | 2023-05-05 | 武汉武药制药有限公司 | Synthesis method of dopamine hydrochloride |
| CN116082173A (en) * | 2021-11-08 | 2023-05-09 | 武汉武药制药有限公司 | Preparation method of dopamine hydrochloride |
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