CN101973903A - Method for synthesizing capsaicin homolog - Google Patents
Method for synthesizing capsaicin homolog Download PDFInfo
- Publication number
- CN101973903A CN101973903A CN2010105046268A CN201010504626A CN101973903A CN 101973903 A CN101973903 A CN 101973903A CN 2010105046268 A CN2010105046268 A CN 2010105046268A CN 201010504626 A CN201010504626 A CN 201010504626A CN 101973903 A CN101973903 A CN 101973903A
- Authority
- CN
- China
- Prior art keywords
- beta
- chloride
- nitrostyrene
- capsaicin
- salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 0 *C(NCCc1cc(*)c(*)cc1)=O Chemical compound *C(NCCc1cc(*)c(*)cc1)=O 0.000 description 1
Abstract
The invention relates to a method for chemically synthesizing capsaicin homolog. The structure of capsaicin homolog is shown in the formula (1) in the specification, wherein R1 is alkyl, cycloalkyl or aryl with carbon atom number of 2-20; R2 is -H or -OCH3; and R3 is -H, -OCH3 or -OH. The method comprises the following steps: in the presence of an ammonium acetate catalyst, vanillin, 4-hydroxybenzaldehyde, 3-methoxylbenzaldehyde or 3,4-dimethoxybenzaldehyde reacts with excessive nitromethane in glacial acetic acid under the backflow state; the obtained 4-hydroxyl-3-methoxyl-beta-nitrostyrene, 4-hydroxyl-beta-nitrostyrene, 3-methoxyl-beta-nitrostyrene or 3,4-dimethoxyl-beta-nitrostyrene is reduced by a reducing agent and then is acidized; and the phenethylamine salt obtained through acidizing reacts with alkyl acyl chloride, thus obtaining capsaicin homolog. The method is simple and convenient in preparation process, easily obtained in raw materials and mild in reaction conditions and provides new development space for study of the capsaicin substances. The formula (1) is shown in the specification.
Description
Technical field
The present invention relates to the chemical synthesis process of capsaicin homologue.
Background technology
The fruit of capsicum plant (Capsicum) is one of maximum seasonings of whole world consumption.Contain at least 15 kinds of capsicine materials that can produce pungent in these pepper fruits, be respectively capsicine (N-(4-hydroxyl-3-methoxy-benzyl)-8-methyl-6-nonene acid amides), Dihydrocapsaicin (N-(4-hydroxyl-3-methoxy-benzyl)-8-methyl pelargonamide), capsicine (N-(4-hydroxyl-3-methoxy-benzyl)-7-methyl-5-octene acid amides) falls, Nordihydrocapsaicin I (N-(4-hydroxyl-3-methoxy-benzyl)-7-methyl decoylamide), Nordihydrocapsaicin II (N-(4-hydroxyl-3-methoxy-benzyl)-6-methyl decoylamide), capsicine (N-(4-hydroxyl-3-methoxy-benzyl)-6-methyl-4-heptene acid amides) falls, homocpsaicin I (N-(4-hydroxyl-3-methoxy-benzyl)-9-methyl-7-decene acid amides), Homodihydrocapsaicin I I (N-(4-hydroxyl-3-methoxy-benzyl)-9-methyl decyl amide), homocpsaicin II (N-(4-hydroxyl-3-methoxy-benzyl)-8-methyl-6-decene acid amides), Homodihydrocapsaicin I II (N-(4-hydroxyl-3-methoxy-benzyl)-8-methyl decyl amide), homocpsaicin III (N-(4-hydroxyl-3-methoxy-benzyl)-9-methyl-6-decene acid amides), high homocpsaicin (N-(4-hydroxyl-3-methoxy-benzyl)-10-methyl-8-hendecene acid amides), high homocpsaicin (N-(4-hydroxyl-3-methoxy-benzyl)-11-methyl-9-laurylene acid amides), the blue amine (N-(4-hydroxyl-3-methoxy-benzyl)-decoylamide) of decoyl pod, the blue amine (N-(4-hydroxyl-3-methoxy-benzyl)-pelargonamide) of nonanoyl pod, the blue amine (N-(4-hydroxyl-3-methoxy-benzyl)-decyl amide) of caprinoyl pod.
In the natural capsicum bases material, capsicine (46%～69%), Dihydrocapsaicin (21%～40%), Nordihydrocapsaicin (～7%), Homodihydrocapsaicin I (I) (～1%), homocpsaicin (I) (～1%), all the other capsicine materials are trace.Wherein the peppery degree of capsicine is maximum, up to 16,000, and 000 Scoville Heat Unit (SHU); Secondly being Dihydrocapsaicin, is 15,000,000 SHU; Nordihydrocapsaicin, Homodihydrocapsaicin I (I), the peppery degree of homocpsaicin (I) are respectively 9,100,000 SHU, 8,600,000 SHU, 8,6000,000 SHU.
Except natural capsicine material, also have a lot of capsaicin homologues also to have peppery degree.The structural formula of capsaicin homologue is suc as formula (1)
Wherein, R
1Be alkyl, cycloalkyl or the aromatic base of carbonatoms between 2-20; R
2For-H or-OCH
3R
3For-H ,-OCH
3Or-OH.
Organoleptic analysis result to capsicine material and capsaicin homologue shows that peppery degree depends on its molecular characterization to a great extent:
(I) phenyl ring contraposition hydroxyl plays a part very importantly to the peppery degree of capsicine material, and when it was closed or is replaced by other atom or functional group, the peppery degree of capsicine material reduced significantly, even disappears.
When (II) phenyl ring had vicinal hydroxyl groups, the capsicine material also had certain peppery degree, but its peppery degree will be far smaller than the capsicine material that the phenyl ring contraposition has hydroxyl.
(III) in the amide group-exchange of NH-and-CO-position do not have obvious negative effect to the peppery degree of capsicine material, its peppery degree slightly increased.
(IV) amide group, even N atom wherein is not to be the indispensable factor that the capsicine material produces pungent, they just play the effect that strengthens pungent.
(V) have only aliphatic side chain can produce peppery degree, straight chain or ring-shaped fat side chain can.
(VI) C
9-C
11The peppery degree of straight chain amide compound is the highest, and oversize or too short peppery degree all can obviously reduce when aliphatic lateral chain.Such as being longer than twelve carbon atom or being shorter than 6 carbon atoms, just do not have tangible peppery having spent when alkyl group side chain.
The capsicine material has multiple pharmacological effect because of its sharp flavor, as analgesia, anti-inflammatory, treatment frostbite, antipruritic, sterilization, wind-damp dispelling etc.; Be mainly used in refractory diseases such as neural painful, the serious psoriatic of treatment diabetic clinically; In agriculture production, be used as the environment-friendly biological pesticide; In anti-fouling ship paint, be used as driving agent, prevent that marine life from adhering to; Add in the sheath of electric wire, cable, optical cable, can prevent the food erosion injury of mouse, termite; Can also be as making tear bomb and alert with defensive weapon etc.
At present, it is fewer to utilize chemical synthesis process to prepare the research of capsicine and class material thereof.Harumi Kagaetc. has reported the synthetic method [Harumi Kaga, Masakatsu Miura, Kazuhiko Orito.AFacile Procedure for Synthesis of Capsaicin.J.Org.Chem.1989,54,3477-3478] of capsicine; Peter M.Gannett etc. has reported synthetic [the Peter M.Gannett of capsicine material, Donald L.Nagel, Pam J.Reilly, Terence Lawson, Jody Sharpe, Bela Toth.The Capsaicinoids:Their Separation, Synthesis and Mutagenicity.J.Org.Chem.1988,53:1064-1071]; Yang Yan etc. reported capsaicine and capsicum ester synthetic method [Yang Yan, gold immortality, Dong Zhenxiu etc. capsaicine and capsicum ester synthetic. SCI .2007,28 (7): 1310～1312].People such as Zhou Shengze reported capsaicin homologue artificial synthesis (Zhou Shengze, Zhou Xiangfeng, Peng Bixian. the artificial synthesis of capsaicin homologue. the patent No.: 200910087705.0.).But about capsaicin homologue (wherein, the R shown in general formula (1)
1Be alkyl, cycloalkyl or the aromatic base of carbonatoms between 2-20; R
2For-H or-OCH
3R
3For-H ,-OCH
3Or-OH.) chemosynthesis rarely have report.
Summary of the invention
The chemical synthesis process that the purpose of this invention is to provide the easy capsaicin homologue of a kind of preparation technology.
The chemical synthesis process of capsaicin homologue of the present invention, the structural formula of said capsaicin homologue is suc as formula (1)
Formula (1)
Wherein, R
1Be alkyl, cycloalkyl or the aromatic base of carbonatoms between 2-20; R
2For-H or-OCH
3R
3For-H ,-OCH
3Or-OH,
Its chemical synthesis process may further comprise the steps:
1) in the presence of the ammonium acetate catalyzer, with Vanillin, 4-hydroxy benzaldehyde, 3-methoxybenzaldehyde or 3,4-dimethoxy benzaldehyde and excessive Nitromethane 99Min. react under reflux state in Glacial acetic acid, obtain corresponding 4-hydroxyl-3-methoxyl group-beta-nitrostyrene, 4-hydroxy-beta-nitrostyrolene, 3-methoxyl group-beta-nitrostyrene or 3,4-dimethoxy-beta-nitrostyrene.
2) the 4-hydroxyl-3-methoxyl group-beta-nitrostyrene, 4-hydroxy-beta-nitrostyrolene, the 3-methoxyl group-beta-nitrostyrene or 3 that step 1) are obtained, 4-dimethoxy-beta-nitrostyrene reduces with reductive agent, carry out acidifying with acid solution then and obtain corresponding 4-hydroxy 3-methoxybenzene ethylamine salt, 4-hydroxyphenethylamine salt, 3-anisole ethylamine salt or 3,4-dimethoxy-phenylethylamine salt.
3) with 4-hydroxy 3-methoxybenzene ethylamine salt, 4-hydroxyphenethylamine salt, 3-anisole ethylamine salt or 3,4-dimethoxy-phenylethylamine salt and alkyl acyl chloride reaction, 4-hydroxy 3-methoxybenzene ethylamine salt, 4-hydroxyphenethylamine salt, 3-anisole ethylamine salt or 3, the mol ratio of 4-dimethoxy-phenylethylamine salt and alkyl acyl chloride is 1: 1-1: 1.2, obtain the thick product of capsaicin homologue shown in structural formula (1).
Further feature of the present invention is, with the thick product ether dissolution of capsaicin homologue, adds sherwood oil then, carries out recrystallization purifying, and the volume ratio of ether and sherwood oil is 1: 1～1: 10.
Among the present invention, described reductive agent is LiAlH
4Or in the presence of Pd/C, use H
2Reduction.Said acid solution is the aqueous solution of hydrochloric acid, Hydrogen bromide, hydroiodic acid HI, sulfuric acid or nitric acid.
Described alkyl acyl chloride is Acetyl Chloride 98Min., propionyl chloride, butyryl chloride, valeryl chloride, caproyl chloride, oenanthyl chloro, capryl(yl)chloride, pelargonyl chloride, Benzoyl chloride or cyclohexyl acyl chlorides.
The synthetic method of capsaicin homologue disclosed by the invention, its preparation technology is easy, and raw material is easy to get, and the reaction conditions gentleness is for the research of capsicine material provides new development space.
Embodiment
Further specify the present invention below in conjunction with embodiment.
Embodiment 1
(1) 4-hydroxy-beta-nitrostyrolene is synthetic
In the single port flask of 250mL, add 6.1g 4-hydroxy benzaldehyde, 3.2g ammonium acetate, 10mL Nitromethane 99Min. and 25mL Glacial acetic acid, start magnetic stirrer and heating, make its back flow reaction 3h in 120～130 ℃ oil bath.Stop heating, cool to room temperature is poured reaction solution in the frozen water into, separates out the precipitation of reddish yellow, filters, and filter cake obtains xanchromatic powder 5.2g, productive rate 63% with the solution weight crystallization of ethanol/water (volume ratio of ethanol/water is 2/5) three times.
(2) 4-hydroxyphenethylamine hydrochloride is synthetic
Add the 4.8g lithium aluminum hydride in 500mL single port flask, the 300mL anhydrous diethyl ether adds 4.9g 4-hydroxy-beta-nitrostyrolene in cable-styled drawer device, and the extracting reduction reaction was carried out 52 hours, was colourless to extract.Be cooled to room temperature, dropwise add about 80ml deionized water, transfer between pH value of solution value to 5～6 with 1mol/L hydrochloric acid then, a large amount of precipitations are arranged in the solution, filter.Take by weighing 7.5g picric acid, with the least possible hot ethanol dissolving.The nearly boiling of above-mentioned filtrate heating added picric hot ethanol solution then, in 90 ℃ of stirring reactions 1 hour.Standing over night under the room temperature is separated out crystal, filters.This crystal is dissolved in the 150ml boiling water, adds the 40ml concentrated hydrochloric acid, back flow reaction 0.5h, cooling has solid to separate out, and filters, and filtrate is successively with oil of mirbane and ether washing.Filtrate decompression dephlegmate branch obtains the crude product 3.6g of 4-hydroxyphenethylamine hydrochloride, productive rate 70%.With methyl alcohol-ethyl acetate crude product is carried out recrystallization, obtain pure products 3.1g.
(3) N-[2-(4-hydroxy phenyl) ethyl] benzamide synthetic
Take by weighing 1.8g phenylformic acid and 10mL thionyl chloride in the 150ml there-necked flask, heated and stirred under nitrogen protection, back flow reaction 1h.Be cooled to about 50 ℃, unnecessary thionyl chloride is removed in underpressure distillation.Add the 25ml anhydrous diethyl ether after reducing to room temperature.
In the 2.4g saturated solution of sodium bicarbonate, add 2.5g 4-hydroxyphenethylamine hydrochloride, be stirred to hydrochloride homodisperse in solution under the room temperature.Add the Benzoyl chloride diethyl ether solution at leisure, reaction 1h adds the 50ml anhydrous diethyl ether again, continues reaction 0.5h.Leave standstill in separating funnel, branch vibration layer, ether layer with hydrochloric acid, the saturated sodium bicarbonate solution washing of 1mol/L, are used anhydrous sodium sulfate drying successively then.Filter, ether is removed in underpressure distillation, promptly gets crude product 2.4g, productive rate 69%.The crude product ether dissolution adds sherwood oil then, carries out recrystallization purifying, and the volume ratio of ether and sherwood oil is 1: 1.Promptly get pure capsaicin homologue N-[2-(4-hydroxy phenyl) ethyl] benzamide.
Embodiment 2
Synthesizing of (1) 3,4-dimethoxy-beta-nitrostyrene
Add 16.6g 3 in the single port flask of 250mL, 4-dimethoxy benzaldehyde, 10.0g ammonium acetate, 20mL Nitromethane 99Min. and 60mL Glacial acetic acid start magnetic stirrer and heating, make its back flow reaction 2h in 120～130 ℃ oil bath.Stop heating, cool to room temperature is poured reaction solution in the frozen water into, separates out precipitation, filters, and filter cake obtains pressed powder 11.3g, productive rate 54% with the solution weight crystallization of ethanol/water (volume ratio of ethanol/water is 3/5) three times.
Synthesizing of (2) 3,4-dimethoxy-phenylethylamine hydrochlorides
In three mouthfuls of reaction flasks of 250mL, add 8.3g 3 successively, 4-dimethoxy-beta-nitrostyrene, dehydrated alcohol 150mL, concentrated hydrochloric acid 10mL, 10% palladium carbon 5.0g, under the intensive magnetic agitation, normal temperature and pressure hydrogenation reaction 4h.Filtration catalizer, the filtrate decompression distillation removes desolvates, and obtains linen solid, 9.9g, productive rate 91%.With methyl alcohol-ethyl acetate crude product is carried out recrystallization, obtain pure products 7.2g.
(3) N-[2-(3, the 4-Dimethoxyphenyl) ethyl] hexanaphthene acid amides synthetic
Take by weighing 1.4g hexahydrobenzoic acid and 10mLg thionyl chloride in the 150ml there-necked flask, heated and stirred under nitrogen protection, back flow reaction 1h.Be cooled to about 50 ℃, unnecessary thionyl chloride is removed in underpressure distillation.Add the 10ml anhydrous diethyl ether after reducing to room temperature.
Add 2.2g 3 in the 1.8g saturated solution of sodium bicarbonate, 4-dimethoxy-phenylethylamine hydrochloride is stirred to hydrochloride homodisperse in solution under the room temperature.Add hexanaphthene acyl chlorides diethyl ether solution at leisure, reaction 0.5h adds the 30ml anhydrous diethyl ether again, continues reaction 0.5h.Leave standstill in separating funnel, branch vibration layer, ether layer with hydrochloric acid, the saturated sodium bicarbonate solution washing of 1mol/L, are used anhydrous sodium sulfate drying successively then.Filter, ether is removed in underpressure distillation, promptly gets crude product 1.7g, productive rate: 59%.The crude product ether dissolution adds sherwood oil then, carries out recrystallization purifying, and the volume ratio of ether and sherwood oil is 1: 5.Obtain pure capsaicin homologue N-[2-(3, the 4-Dimethoxyphenyl) ethyl] hexanaphthene acid amides 1.1g.
Embodiment 3
(1) 4-hydroxyl-3-methoxyl group-beta-nitrostyrene is synthetic
In the single port flask of 250mL, add 18.6g Vanillin, 9.0g ammonium acetate, 19.5mL Nitromethane 99Min. and 53mL Glacial acetic acid, start magnetic stirrer and heating, make its back flow reaction 2h in 120～130 ℃ oil bath.Stop heating, cool to room temperature is poured reaction solution in the frozen water into, separates out the precipitation of reddish yellow, filters, and filter cake obtains xanchromatic powder 11.1g, productive rate 46% with the solution weight crystallization of ethanol/water (volume ratio of ethanol/water is 3/2) three times.
(2) 4-hydroxy 3-methoxybenzene ethylamine hydrochloride is synthetic
Add the 2.4g lithium aluminum hydride in 250mL single port flask, about 200mL anhydrous diethyl ether adds 2.5g 4-hydroxyl-3-methoxyl group-beta-nitrostyrene in cable-styled drawer device, and extractive reaction carried out 60 hours.Be cooled to room temperature, slowly add about 40ml deionized water, transfer between pH value of solution value to 5～6 with 1mol/L hydrochloric acid then, separate out a large amount of precipitations in the solution, heated and boiled, filtered while hot is removed precipitation.Take by weighing 3.2g picric acid, be dissolved in the least possible hot ethanol, join in the above-mentioned hot filtrate stirring reaction 1 hour.Standing over night under the room temperature is separated out the yellow crystal thing, filters.The yellow crystal thing is dissolved in the 90ml boiling water, adds the 18.2ml concentrated hydrochloric acid, separate out a large amount of solids in the process of cooling, filter, filtrate is successively with oil of mirbane and ether washing.Filtrate decompression dephlegmate branch obtains the crude product of 4-hydroxyl-3-methoxyl group-phenylethylamine hydrochloride.With methyl alcohol-ethyl acetate crude product is carried out recrystallization, obtain final product 0.9g, productive rate 38%.
(3) N-[2-(4-hydroxy 3-methoxybenzene base) ethyl] pelargonamide synthetic
Take by weighing 0.9g n-nonanoic acid and 2.3g thionyl chloride in the 150ml there-necked flask, heated and stirred under nitrogen protection, back flow reaction 1h.Be cooled to about 50 ℃, unnecessary thionyl chloride is removed in underpressure distillation.Add the 25ml anhydrous diethyl ether after reducing to room temperature.
In the 1.6g saturated solution of sodium bicarbonate, add 1.0g 4-hydroxy 3-methoxybenzene ethylamine hydrochloride, be stirred to hydrochloride homodisperse in solution under the room temperature.Add the pelargonyl chloride diethyl ether solution at leisure, reaction 0.5h adds the 30ml anhydrous diethyl ether again, continues reaction 0.5h.Leave standstill in separating funnel, branch vibration layer, ether layer with hydrochloric acid, the saturated sodium bicarbonate solution washing of 1mol/L, are used anhydrous sodium sulfate drying successively then.Filter, ether is removed in underpressure distillation, promptly gets crude product 1.1g, productive rate: 73%.。The crude product ether dissolution adds sherwood oil then, carries out recrystallization purifying, and the volume ratio of ether and sherwood oil is 1: 10.Obtain pure capsaicin homologue N-[2-(4-hydroxy 3-methoxybenzene base) ethyl] pelargonamide.
Embodiment 4
(1) 3-methoxyl group-beta-nitrostyrene is synthetic
In the single port flask of 250mL, add 6.8g 3-methoxybenzaldehyde, 5.2g ammonium acetate, 15mL Nitromethane 99Min. and 25mL Glacial acetic acid, start magnetic stirrer and heating, make its back flow reaction 2h in 120～130 ℃ oil bath.Stop heating, cool to room temperature is poured reaction solution in the frozen water into, separates out a large amount of precipitations, filters, and filter cake obtains pressed powder 4.4g, productive rate 49% with the solution weight crystallization of ethanol/water (volume ratio of ethanol/water is 3/7) three times.
(2) 3-anisole ethylamine hydrochloride is synthetic
In three mouthfuls of reaction flasks of 250mL, add 3.6g 3-methoxyl group-beta-nitrostyrene, dehydrated alcohol 50mL, concentrated hydrochloric acid 5mL, 10% palladium carbon 1.2g successively, under the intensive magnetic agitation, normal temperature and pressure hydrogenation reaction 6h.Filtration catalizer, the filtrate decompression distillation removes desolvates, and obtains linen solid, 3.3g, productive rate 89%.With methyl alcohol-ethyl acetate crude product is carried out recrystallization, obtain pure products 2.7g.
(3) N-[2-(3-p-methoxy-phenyl) ethyl] ethanamide synthetic
Take by weighing 0.7g acetic acid and 8mL thionyl chloride in the 150ml there-necked flask, heated and stirred under nitrogen protection, back flow reaction 1h.Be cooled to about 50 ℃, unnecessary thionyl chloride is removed in underpressure distillation.Add the 10ml anhydrous diethyl ether after reducing to room temperature.
In the 1.7g saturated solution of sodium bicarbonate, add 1.9g 3-anisole ethylamine hydrochloride, be stirred to hydrochloride homodisperse in solution under the room temperature.Add the Acetyl Chloride 98Min. diethyl ether solution at leisure, reaction 0.5h adds the 30ml anhydrous diethyl ether again, continues reaction 0.5h.Leave standstill in separating funnel, branch vibration layer, ether layer with hydrochloric acid, the saturated sodium bicarbonate solution washing of 1mol/L, are used anhydrous sodium sulfate drying successively then.Filter, ether is removed in underpressure distillation, promptly gets crude product 1.2g, productive rate: 65%.。The crude product ether dissolution adds sherwood oil then, carries out recrystallization purifying, and the volume ratio of ether and sherwood oil is 1: 8.Obtain pure capsaicin homologue N-[2-(3-p-methoxy-phenyl) ethyl] ethanamide.
Above-mentioned embodiment is used for the present invention that explains, rather than limits the invention, and in the protection domain of spirit of the present invention and claim, any modification and change to the present invention makes all fall into protection scope of the present invention.For example, in the above-mentioned example, with alkyl acyl chloride be Acetyl Chloride 98Min., pelargonyl chloride, cyclohexyl acyl chlorides, Benzoyl chloride, wherein the C atomicity in propionyl chloride, butyryl chloride, valeryl chloride, caproyl chloride, oenanthyl chloro, the capryl(yl)chloride alkyl chain obviously also is applicable to the present invention between Acetyl Chloride 98Min. and pelargonyl chloride.
Claims (5)
1. the chemical synthesis process of capsaicin homologue, the structural formula of said capsaicin homologue is suc as formula (1)
Wherein, R
1Be alkyl, cycloalkyl or the aromatic base of carbonatoms between 2-20; R
2For-H or-OCH
3R
3For-H ,-OCH
3Or-OH,
Its chemical synthesis process may further comprise the steps:
1) in the presence of the ammonium acetate catalyzer, with Vanillin, 4-hydroxy benzaldehyde, 3-methoxybenzaldehyde or 3,4-dimethoxy benzaldehyde and excessive Nitromethane 99Min. react under reflux state in Glacial acetic acid, obtain corresponding 4-hydroxyl-3-methoxyl group-beta-nitrostyrene, 4-hydroxy-beta-nitrostyrolene, 3-methoxyl group-beta-nitrostyrene or 3,4-dimethoxy-beta-nitrostyrene.
2) the 4-hydroxyl-3-methoxyl group-beta-nitrostyrene, 4-hydroxy-beta-nitrostyrolene, the 3-methoxyl group-beta-nitrostyrene or 3 that step 1) are obtained, 4-dimethoxy-beta-nitrostyrene reduces with reductive agent, carry out acidifying with acid solution then and obtain corresponding 4-hydroxy 3-methoxybenzene ethylamine salt, 4-hydroxyphenethylamine salt, 3-anisole ethylamine salt or 3,4-dimethoxy-phenylethylamine salt.
3) with 4-hydroxy 3-methoxybenzene ethylamine salt, 4-hydroxyphenethylamine salt, 3-anisole ethylamine salt or 3,4-dimethoxy-phenylethylamine salt and alkyl acyl chloride reaction, 4-hydroxy 3-methoxybenzene ethylamine salt, 4-hydroxyphenethylamine salt, 3-anisole ethylamine salt or 3, the mol ratio of 4-dimethoxy-phenylethylamine salt and alkyl acyl chloride is 1: 1-1: 1.2, obtain the thick product of capsaicin homologue shown in structural formula (1).
2. the chemical synthesis process of capsaicin homologue according to claim 1 is characterized in that the thick product ether dissolution of capsaicin homologue is added sherwood oil then, carries out recrystallization purifying, and the volume ratio of ether and sherwood oil is 1: 1～1: 10.
3. the chemical synthesis process of capsaicin homologue according to claim 1 is characterized in that described reductive agent is LiAlH
4Or in the presence of Pd/C, use H
2Reduction.
4. the chemical synthesis process of capsaicin homologue according to claim 1 is characterized in that said acid solution is the aqueous solution of hydrochloric acid, Hydrogen bromide, hydroiodic acid HI, sulfuric acid or nitric acid.
5. the chemical synthesis process of capsaicin homologue according to claim 1 is characterized in that described alkyl acyl chloride is Acetyl Chloride 98Min., propionyl chloride, butyryl chloride, valeryl chloride, caproyl chloride, oenanthyl chloro, capryl(yl)chloride, pelargonyl chloride, Benzoyl chloride or cyclohexyl acyl chlorides.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105046268A CN101973903A (en) | 2010-10-12 | 2010-10-12 | Method for synthesizing capsaicin homolog |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105046268A CN101973903A (en) | 2010-10-12 | 2010-10-12 | Method for synthesizing capsaicin homolog |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101973903A true CN101973903A (en) | 2011-02-16 |
Family
ID=43573821
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010105046268A Pending CN101973903A (en) | 2010-10-12 | 2010-10-12 | Method for synthesizing capsaicin homolog |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101973903A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103497108A (en) * | 2013-09-22 | 2014-01-08 | 中北大学 | Synthesis method of p-hydroxy-beta-nitrostyrene |
| CN105777561A (en) * | 2016-03-23 | 2016-07-20 | 叶芳 | Tyramine compound and preparation method thereof |
| CN108586259A (en) * | 2018-07-09 | 2018-09-28 | 上海华堇生物技术有限责任公司 | A kind of new preparation process of 2- methoxyl groups-beta-nitrostyrene |
| CN108623462A (en) * | 2018-06-19 | 2018-10-09 | 上海华堇生物技术有限责任公司 | A kind of new preparation process of 4- hydroxy-betas-nitrostyrolene |
| CN108658778A (en) * | 2018-06-19 | 2018-10-16 | 上海华堇生物技术有限责任公司 | A kind of new preparation process of 3,4- dimethoxys-beta-nitrostyrene |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0132114A1 (en) * | 1983-07-14 | 1985-01-23 | The Procter & Gamble Company | Novel compounds and compositions useful for producing analgesia |
| GB2168976A (en) * | 1984-12-20 | 1986-07-02 | Procter & Gamble | Amides and compositions thereof having anti-inflammatory activity |
| CN1526699A (en) * | 2003-09-22 | 2004-09-08 | 朱松年 | Synthesis of n-nonanoic vanilloylamine |
| CN101607938A (en) * | 2008-06-17 | 2009-12-23 | 中国人民解放军第二军医大学 | A kind of novel isoquinoline anti-tumor compound and preparation method thereof |
| CN101717346A (en) * | 2009-06-24 | 2010-06-02 | 周圣泽 | Artificial synthesis method of capsaicin homologue |
-
2010
- 2010-10-12 CN CN2010105046268A patent/CN101973903A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0132114A1 (en) * | 1983-07-14 | 1985-01-23 | The Procter & Gamble Company | Novel compounds and compositions useful for producing analgesia |
| GB2168976A (en) * | 1984-12-20 | 1986-07-02 | Procter & Gamble | Amides and compositions thereof having anti-inflammatory activity |
| CN1526699A (en) * | 2003-09-22 | 2004-09-08 | 朱松年 | Synthesis of n-nonanoic vanilloylamine |
| CN101607938A (en) * | 2008-06-17 | 2009-12-23 | 中国人民解放军第二军医大学 | A kind of novel isoquinoline anti-tumor compound and preparation method thereof |
| CN101717346A (en) * | 2009-06-24 | 2010-06-02 | 周圣泽 | Artificial synthesis method of capsaicin homologue |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103497108A (en) * | 2013-09-22 | 2014-01-08 | 中北大学 | Synthesis method of p-hydroxy-beta-nitrostyrene |
| CN103497108B (en) * | 2013-09-22 | 2015-06-10 | 中北大学 | Synthesis method of p-hydroxy-beta-nitrostyrene |
| CN105777561A (en) * | 2016-03-23 | 2016-07-20 | 叶芳 | Tyramine compound and preparation method thereof |
| CN108623462A (en) * | 2018-06-19 | 2018-10-09 | 上海华堇生物技术有限责任公司 | A kind of new preparation process of 4- hydroxy-betas-nitrostyrolene |
| CN108658778A (en) * | 2018-06-19 | 2018-10-16 | 上海华堇生物技术有限责任公司 | A kind of new preparation process of 3,4- dimethoxys-beta-nitrostyrene |
| CN108586259A (en) * | 2018-07-09 | 2018-09-28 | 上海华堇生物技术有限责任公司 | A kind of new preparation process of 2- methoxyl groups-beta-nitrostyrene |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101973903A (en) | Method for synthesizing capsaicin homolog | |
| CN102001958A (en) | Method for synthesizing N-(3,4-dimethoxybenzyl)amide capsaicine homologous compounds | |
| CN101921205B (en) | Preparation method of agomelatine I crystal form | |
| CN103396364A (en) | N-alkyloxy-N-2-[1-(4-halogenated phenyl)-3-pyrazolyloxymethyl]phenylalkyl carbamate | |
| CN105085395B (en) | Shellfish reaches the preparation method of quinoline | |
| CN103601735B (en) | A kind of method of mosictin of purifying | |
| CN105085396B (en) | For preparing shellfish up to intermediate of quinoline and its preparation method and application | |
| CN101671292B (en) | Synthetic method of fexofenadine hydrochloride | |
| CA2724716C (en) | Process for preparation of .alpha.-hydroxycarboxylic acid amides | |
| CN102584626A (en) | Synthetic method of (ethoxymethylene)-malononitrile | |
| CN110713443A (en) | Process for preparing malononitrile oxime ether compounds and intermediate compounds | |
| CN105272925A (en) | Preparation method of paddy field herbicide pyriminobac-methyl | |
| CN102336710A (en) | Method for synthesizing edaravone derivative | |
| CN107963976A (en) | A kind of preparation method of phenyl ethyl amine compounds intermediate | |
| CN103333103B (en) | Method for preparing flupirtine maleate by one-pot method | |
| CN103193712B (en) | A kind of preparation method of N-BETA-Alanyl-L-histidine | |
| CN105418445A (en) | Preparation method for high-purity dihydrocapsaicin monomer | |
| CN104926682A (en) | P-chlorophenylu hydrazine hydrochloride preparation method | |
| JP6287290B2 (en) | Method for producing trans-1,2-diaminocyclohexane | |
| CN105523939B (en) | A kind of preparation method of lenalidomide intermediate | |
| CN104817476B (en) | Method for preparing unnatural amino acid | |
| CN104557857A (en) | Method for purifying pomalidomide | |
| CN103664661B (en) | Prepare the method for 1-[2-amino (p-p-methoxy-phenyl) ethyl] hexalin | |
| CN103319373B (en) | The preparation method of 1 [2 amino 1 (4 benzyloxy-phenyl) ethyl] hexamethylene alkanol and related intermediate | |
| CN107739315A (en) | The processing method of 3-acetylaminoaniline hydrochloride mother liquor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20110216 |