CN104496998B - A kind of preparation method of hydrogen spiral shell [1, the 3 dioxolane 2] quinoline of 1 ' benzyl, 2 ' ketone 5 ', 7 ', 8 ' three - Google Patents
A kind of preparation method of hydrogen spiral shell [1, the 3 dioxolane 2] quinoline of 1 ' benzyl, 2 ' ketone 5 ', 7 ', 8 ' three Download PDFInfo
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- CN104496998B CN104496998B CN201410776603.0A CN201410776603A CN104496998B CN 104496998 B CN104496998 B CN 104496998B CN 201410776603 A CN201410776603 A CN 201410776603A CN 104496998 B CN104496998 B CN 104496998B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
- C07D491/10—Spiro-condensed systems
- C07D491/113—Spiro-condensed systems with two or more oxygen atoms as ring hetero atoms in the oxygen-containing ring
Abstract
The present invention provides a kind of ketone 5 ' of 1 ' benzyl 2 ', 7 ', 8 ' three hydrogen spiral shells [1,3 dioxolanes 2] quinoline synthetic method, the ketone 5 ', 7 ' of 1 ' benzyl 2 ', 8 ' three hydrogen spiral shells [1,3 dioxolanes 2] quinoline preparation method with the ketone 3 ', 4 ', 5 ' of 1 ' benzyl 2 ', 7 ', 8 ' pentahydro- spiral shells [1,3 dioxolane 2] quinoline is raw material, passes through dehydrogenation reaction, it is prepared into the ketone 5 ' of 1 ' benzyl 2 ', 7 ', 8 ' three hydrogen spiral shells [1,3 dioxolane 2] quinoline.The synthetic method of the hydrogen spiral shell of 1 ' benzyl, 2 ' ketone 5 ', 7 ', 8 ' three [1, the 3 dioxolane 2] quinoline is simple to operate, and product yield and purity are high, cheap, simple to operate, are adapted to industrialized production.
Description
Technical field
The present invention relates to medicine intermediate technical field, and in particular to and 1 '-benzyl of huperzine intermediate -5 ', 7 ', 8 ' -
Three hydrogen-spiral shell-[1,3- dioxolane -2]-quinoline its preparation method.
Background technology
With alzheimer, disease patient is increasing, has turned into after senile dementia after angiocardiopathy, neoplastic disease and has threatened old
3rd disease of year people's life.The decline of acetylcholine function has important pass with the forfeiture of learning and memory ability
System, therefore, the research emphasis for treating the disease is searching maincenter choline medicine, and acetylcholinesteraseinhibitors inhibitors are still current research
It is at most most widely used.
Second generation acetylcholinesteraseinhibitors inhibitors huperzine, the hydrolysis by acetylcholine esterase inhibition to acetylcholine
Act on and improve outside the acetylcholine concentration between cynapse, neuron can also be produced by anti-oxidation stress and anti-apoptotic approach
Raw protective effect, with unique pharmacology and hypotoxicity, has the medicine of bright prospects in treatment alzheimer disease field.
Either synthesising racemation huperzine or optics huperzine, it is most of be first synthesis 1 '-benzyl -2 ' -one -
5 ', 7 ', 8 '-three hydrogen-spiral shell-[1,3- dioxolane -2]-quinoline.
In the prior art, most of synthesis 1 '-benzyl -2 ' -one -5 ', 7 ', 8 '-three hydrogen-spiral shell-[1,3- dioxolane -2] -
Quinoline is that, using cesium chloride benzene as catalyst, the catalyst is expensive, reclaims difficult, and severe reaction conditions are not suitable for extensive
Production.
The content of the invention
In order to solve the technical problem in the presence of background technology, the invention provides a kind of 1 '-benzyl -2 ' -one -5 ',
The preparation method of 7 ', 8 '-three hydrogen-spiral shell-[1,3- dioxolane -2]-quinoline, this method is with low cost, simple to operate, and product is received
Rate and purity are high, are adapted to industrialized production.
Technical scheme：
1 '-the benzyl -2 ' -one -5 ', the preparation method of 7 ', 8 '-three hydrogen-spiral shell-[1,3- dioxolane -2]-quinoline, including
Following steps：
In a nitrogen environment, by 1 '-benzyl -2 ' -one -3 ', 4 ', 5 ', 7 ', 8 '-pentahydro--spiral shell-[1,3- dioxolane -2] -
Quinoline, tetrachloroquinone (or chloro- 5, the 6- dicyano benzoquinone DDQ of 2,3- bis-) are added in toluene, are stirred, in 40-110 DEG C of bar
2-10h is reacted under part, distilled water is then added, 3-7h is reacted under the conditions of 25-65 DEG C, room temperature is cooled to, ethyl acetate is used
Extraction, concentration, both 1 '-benzyl -2 ' -one -5 ', 7 ', 8 '-three hydrogen-spiral shell-[1,3- dioxolane -2]-quinoline；1 '-the benzyl
Base -2 ' -one -3 ', 4 ', 5 ', 7 ', 8 '-pentahydro--spiral shell-[1,3- dioxolane -2]-quinoline, tetrachloroquinone, toluene, distilled water
Mol ratio is 1:1-2:28-56:100-300.
Above-mentioned method optimum condition is：In a nitrogen environment, by 1 '-benzyl -2 ' -one -3 ', 4 ', 5 ', 7 ', 8 '-five
Hydrogen-spiral shell-[1,3- dioxolane -2]-quinoline, tetrachloroquinone (or chloro- 5, the 6- dicyano benzoquinone DDQ of 2,3- bis-) are added to toluene
In, stir, 6h is reacted under the conditions of 80 DEG C, distilled water is then added, react 5h under the conditions of 60 DEG C, be cooled to room
Temperature, is extracted with ethyl acetate, concentration, both 1 '-benzyl -2 ' -one -5 ', 7 ', 8 '-three hydrogen-spiral shell-[1,3- dioxolane -2]-quinoline
Quinoline；1 '-the benzyl -2 ' -one -3 ', 4 ', 5 ', 7 ', 8 '-pentahydro--spiral shell-[1,3- dioxolane -2]-quinoline, tetrachloroquinone, first
Benzene, the mol ratio of distilled water are 1:1.2:37.8:180.
The technique effect of the present invention：
1 '-the benzyl -2 ' -one -5 ', the preparation method of 7 ', 8 '-three hydrogen-spiral shell-[1,3- dioxolane -2]-quinoline, operation
Simply, product yield and purity are high, and the compound is important huperzine intermediate, are adapted to industrialized production.
Embodiment
1 '-benzyl -2 ' -one -5 ', the synthetic method of 7 ', 8 '-three hydrogen-spiral shell-[1,3- dioxolane -2]-quinoline is as follows：
Embodiment 1
Under nitrogen protection, by 1 '-benzyl -2 ' -one -3 ', 4 ', 5 ', 7 ', 8 '-pentahydro--spiral shell-[1,3- dioxolane -2] -
In quinoline 30.0g, tetrachloroquinone 68.9g, addition 400mL toluene, stirring, 80 DEG C are reacted 6 hours, are added and are steamed into reaction solution
Distilled water 325mL, 65 DEG C are reacted 3 hours, are cooled to room temperature, ethyl acetate extraction, concentration, be prepared into described 1 '-benzyl -5 ',
7 ', 8 '-three hydrogen-spiral shell-[1,3- dioxolane -2]-quinoline, yield：61.3%；Purity：96.3%.Wherein：1 '-benzyl -2 ' -
Ketone -3 ', 4 ', 5 ', 7 ', 8 '-pentahydro--spiral shell-[1,3- dioxolane -2]-quinoline and tetrachloroquinone, toluene, the mol ratio of distilled water
For 1:1.2:37.8:180.
Embodiment 2
Under nitrogen protection, by 1 '-benzyl -2 ' -one -3 ', 4 ', 5 ', 7 ', 8 '-pentahydro--spiral shell-[1,3- dioxolane -2] -
In quinoline 30.0g, tetrachloroquinone 57.4g, addition 300mL toluene, stirring, 40 DEG C are reacted 10 hours, are added into reaction solution
Distilled water 180mL, 25 DEG C are reacted 7 hours, are cooled to room temperature, ethyl acetate extraction, concentration, be prepared into described 1 '-benzyl-
5 ', 7 ', 8 '-three hydrogen-spiral shell-[1,3- dioxolane -2]-quinoline, yield：41.8%；Purity：95.8%.Wherein：1 '-benzyl-
2 ' -one -3 ', 4 ', 5 ', 7 ', 8 '-pentahydro--spiral shell-[1,3- dioxolane -2]-quinoline and tetrachloroquinone, toluene, distilled water rubs
You are than being 1:1:28.3:100.
Embodiment 3
Under nitrogen protection, by 1 '-benzyl -2 ' -one -3 ', 4 ', 5 ', 7 ', 8 '-pentahydro--spiral shell-[1,3- dioxolane -2] -
In quinoline 30.0g, tetrachloroquinone 114.8g, addition 600mL toluene, stirring, 60 DEG C are reacted 8 hours, are added into reaction solution
Distilled water 540mL, 35 DEG C are reacted 6 hours, are cooled to room temperature, ethyl acetate extraction, concentration, be prepared into described 1 '-benzyl-
2 ' -one -5 ', 7 ', 8 '-three hydrogen-spiral shell-[1,3- dioxolane -2]-quinoline, yield：46.2%；Purity：96.7%.Wherein：1′-
Benzyl -2 ' -one -3 ', 4 ', 5 ', 7 ', 8 '-pentahydro--spiral shell-[1,3- dioxolane -2]-quinoline and tetrachloroquinone, toluene, distilled water
Mol ratio be 1:1:56.6:300.
Embodiment 4
Under nitrogen protection, by 1 '-benzyl -2 ' -one -3 ', 4 ', 5 ', 7 ', 8 '-pentahydro--spiral shell-[1,3- dioxolane -2] -
In quinoline 30.0g, tetrachloroquinone 57.4g, addition 500mL toluene, stirring, 110 DEG C are reacted 2 hours, are added into reaction solution
Distilled water, 55 DEG C are reacted 5 hours, are cooled to room temperature, ethyl acetate extraction, concentration, be prepared into described 1 '-benzyl -2 ' -one -
5 ', 7 ', 8 '-three hydrogen-spiral shell-[1,3- dioxolane -2]-quinoline, yield：51.7%；Purity：95.6%.Wherein：1 '-benzyl-
2 ' -one -3 ', 4 ', 5 ', 7 ', 8 '-pentahydro--spiral shell-[1,3- dioxolane -2]-quinoline and tetrachloroquinone, toluene, distilled water rub
You are than being 1:1:28.3:180.
Embodiment 5
Under nitrogen protection, by 1 '-benzyl -2 ' -one -3 ', 4 ', 5 ', 7 ', 8 '-pentahydro--spiral shell-[1,3- dioxolane -2] -
In quinoline 30.0g, DDQ 27.2g, addition 400mL toluene, stirring, 80 DEG C are reacted 6 hours, into reaction solution
Add distilled water, 65 DEG C are reacted 3 hours, are cooled to room temperature, ethyl acetate extraction, concentration, be prepared into described 1 '-benzyl -2 ' -
Ketone -5 ', 7 ', 8 '-three hydrogen-spiral shell-[1,3- dioxolane -2]-quinoline, yield：61.9%；Purity：96.7%.Wherein：1 '-benzyl
Base -2 ' -one -3 ', 4 ', 5 ', 7 ', 8 '-pentahydro--spiral shell-[1,3- dioxolane -2]-quinoline and tetrachloroquinone, toluene, distilled water
Mol ratio is 1:1.2:37.8:180.
In order to determine the optimum material proportion and optimised process step of the present invention, inventor has carried out substantial amounts of laboratory
Development test, various test situations are as follows：
1st, influence of the reaction temperature to product yield
Ith, influence of the reaction temperature (reaction temperature not plus before distilled water) to product yield
According to 1 '-benzyl -2 ' -one -3 ', 4 ', 5 ', 7 ', 8 '-pentahydro--spiral shell-[1,3- dioxolane -2]-quinoline and tetrachloro
Benzoquinones, toluene, the mol ratio of water are 1:1.2:37.8:180, respectively 25,40,60,80,100,110 DEG C of reactions 6 hours, plus
After water, 60 DEG C are reacted 5 hours, and 1 '-benzyl -2 ' -one -5 shown in formula I ', 7 ', 8 '-three hydrogen-spiral shell-[1,3- dioxolane -
2]-quinoline, calculates its yield.Result of the test is shown in Table 1.
Influence of the reaction temperature of table 1 to product yield
From table 1, the purity and yield of 5 hours products therefroms of 60-100 DEG C of reaction are higher, wherein 80 DEG C of reactions 5 are small
When products therefrom purity and yield highest.
IIth, influence of the reaction temperature (plus reaction temperature after distilled water) to product yield
According to 1 '-benzyl -2 ' -one -3 ', 4 ', 5 ', 7 ', 8 '-pentahydro--spiral shell-[1,3- dioxolane -2]-quinoline and tetrachloro
Benzoquinones, toluene, the mol ratio of water are 1:1.2:37.8:180, reacted 6 hours at 80 DEG C, after adding water, respectively 20,30,40,
50th, 60,70 DEG C of reactions 5 hours, 1 '-benzyl -2 ' -one -5 shown in formula I ', 7 ', 8 '-three hydrogen-spiral shell-[1,3- dioxy five
Ring -2]-quinoline, calculate its yield.Result of the test is shown in Table 2.
Influence of the reaction temperature of table 2 to product yield
From table 2, the purity and yield of 5 hours products therefroms of 40-70 DEG C of reaction are higher, wherein 60 DEG C of reactions 5 are small
When products therefrom purity and yield highest.
2nd, the influence of reaction time product yield
Ith, influence of the reaction time (reaction time not plus before distilled water) to product yield
According to 1 '-benzyl -2 ' -one -3 ', 4 ', 5 ', 7 ', 8 '-pentahydro--spiral shell-[1,3- dioxolane -2]-quinoline and tetrachloro
Benzoquinones, toluene, the mol ratio of water are 1:1.2:37.8:180, react 3 at 80 DEG C respectively, 4,5,6,7,8 hours, after adding water, 60
DEG C reaction 5 hours, 1 '-benzyl -2 ' -one -5 shown in formula I ', 7 ', 8 '-three hydrogen-spiral shell-[1,3- dioxolane -2]-quinoline
Quinoline, calculates its yield.Result of the test is shown in Table 3.
Influence of the reaction time of table 3 to product yield
From table, 3,80 DEG C are reacted 5-8 hours, and the purity and yield of products therefrom are higher, and the wherein reaction time is 6
During hour, the purity and yield highest of products therefrom,.
IIth, influence of the reaction time (plus reaction time after distilled water) to product yield
According to 1 '-benzyl -2 ' -one -3 ', 4 ', 5 ', 7 ', 8 '-pentahydro--spiral shell-[1,3- dioxolane -2]-quinoline and tetrachloro
Benzoquinones, toluene, the mol ratio of water are 1:1.2:37.8:180,80 DEG C react 6 hours, after adding water, respectively 60 DEG C reaction 3,4,
5th, 6,7,8 hours, 1 '-benzyl -2 ' -one -5 shown in formula I ', 7 ', 8 '-three hydrogen-spiral shell-[1,3- dioxolane -2]-quinoline
Quinoline, calculates its yield.Result of the test is shown in Table 4.
Influence of the reaction time of table 4 to product yield
From table 4, after adding water, 60 DEG C are reacted 4-8 hours, and the purity and yield of products therefrom are higher, wherein reacting
When time is 5 hours, the purity and yield highest of products therefrom, the extension reaction time influence not on the purity and yield of product
Greatly.
Compbined test 1 and 2,25-110 DEG C is reacted 3-8 hours before present invention selection adds water, 20-70 DEG C of reaction 3-8 after adding water
Hour, after preferably select add water before 60-100 DEG C react 5-8 hour, after adding water 40-70 DEG C reaction 4-8 hours, most preferably add water
First 80 DEG C are reacted 6 hours, and 60 DEG C are reacted 5 hours after adding water.
3rd, influence of the oxidizer to product yield
Respectively according to according to 1 '-benzyl -2 ' -one -3 ', 4 ', 5 ', 7 ', 8 '-pentahydro--spiral shell-[1,3- dioxolane -2]-quinoline
Quinoline is respectively 1 with tetrachloroquinone, toluene, the mol ratio of water:1.0:37.8:180,1:1.1:37.8:180,1:1.2:37.8:
180,1:1.3:37.8:180,1:1.4:37.8:180,1:2.0:37.8:180, reacted 6 hours at 80 DEG C, after adding water 60 DEG C it is anti-
Answer 5 hours, 1 '-benzyl -2 ' -one -5 shown in formula I ', 7 ', 8 '-three hydrogen-spiral shell-[1,3- dioxolane -2]-quinoline, meter
Calculate its yield.Result of the test is shown in Table 5.
Influence of the oxidizer of table 5 to product yield
From table 5,1 '-benzyl -2 ' -one -3 ', 4 ', 5 ', 7 ', 8 '-pentahydro--spiral shell-[1,3- dioxolane -2]-quinoline
Mol ratio with tetrachloroquinone, toluene, water is 1:1.0-1.4:37.8:180, when, the yield and purity of products therefrom are higher,
Wherein 1 '-benzyl -2 ' -one -3 ', 4 ', 5 ', 7 ', 8 '-pentahydro--spiral shell-[1,3- dioxolane -2]-quinoline and tetrachloroquinone, first
Benzene, the mol ratio of water are 1:1.2:37.8:When 180, the equal highest of purity and yield of products therefrom.
4th, influence of the solvent load to product yield
Respectively according to according to 1 '-benzyl -2 ' -one -3 ', 4 ', 5 ', 7 ', 8 '-pentahydro--spiral shell-[1,3- dioxolane -2]-quinoline
Quinoline is respectively 1 with tetrachloroquinone, toluene, the mol ratio of water:1.2:28.3:180,1:1.2:37.8:180,1:1.2:45.3:
180,1:1.2:56.6:180, reacted 6 hours at 80 DEG C, 60 DEG C are reacted 5 hours after adding water, 1 '-benzyl shown in formula I-
2 ' -one -5 ', 7 ', 8 '-three hydrogen-spiral shell-[1,3- dioxolane -2]-quinoline calculate its yield.Result of the test is shown in Table 6.
Influence of the solvent load of table 6 to product yield
From table 6,1 '-benzyl -2 ' -one -3 ', 4 ', 5 ', 7 ', 8 '-pentahydro--spiral shell-[1,3- dioxolane -2]-quinoline
Mol ratio with tetrachloroquinone, toluene, water is 1:1.2:37.8-45.3:When 180, the yield of product is higher, wherein 1 '-benzyl-
2 ' -one -3 ', 4 ', 5 ', 7 ', 8 '-pentahydro--spiral shell-[1,3- dioxolane -2]-quinoline and tetrachloroquinone, toluene, the mol ratio of water
For 1:1.2:37.8:When 180, the purity height of product, yield are also high.
5th, influence of the consumption of water to product yield
Respectively according to according to 1 '-benzyl -2 ' -one -3 ', 4 ', 5 ', 7 ', 8 '-pentahydro--spiral shell-[1,3- dioxolane -2]-quinoline
Quinoline is respectively 1 with tetrachloroquinone, toluene, the mol ratio of water:1.2:37.8:100,1:1.2:37.8:140,1:1.2:37.8:
180,1:1.2:37.8:240,1:1.2:37.8:300, reacted 6 hours at 80 DEG C respectively, 60 DEG C are reacted 5 hours after adding water, system
1 '-benzyl -2 ' -one -5 shown in standby formula I ', 7 ', 8 '-three hydrogen-spiral shell-[1,3- dioxolane -2]-quinoline calculate its yield.Examination
Test and the results are shown in Table 7.
Influence of the water consumption of table 7 to product yield
From table 7,1 '-benzyl -2 ' -one -3 ', 4 ', 5 ', 7 ', 8 '-pentahydro--spiral shell-[1,3- dioxolane -2]-quinoline
Mol ratio with tetrachloroquinone, toluene, water is 1:1.2:37.8-45.3:During 140-300, the yield of product is higher, wherein 1 '-
Benzyl -2 ' -one -3 ', 4 ', 5 ', 7 ', 8 '-pentahydro--spiral shell-[1,3- dioxolane -2]-quinoline and tetrachloroquinone, toluene, water rub
You are than being 1:1.2:37.8:When 180, the purity height of product, yield are also high.
The result of compbined test 3,4,5, present invention selection 1 '-benzyl -2 ' -one -3 ', 4 ', 5 ', 7 ', 8 '-pentahydro--spiral shell -
[1,3- dioxolane -2]-quinoline is 1 with tetrachloroquinone, toluene, water mol ratio:1.0-2.0:28.3-56.6:100-300, it is excellent
It is 1 to select mol ratio:1.0-1.4:37.8-45.3:140-300, optimum mole ratio is 1:1.2:37.8:180.
Claims (2)
1. one kind 1 '-benzyl -2 ' -one -5 ', the preparation method of 7 ', 8 '-three hydrogen-spiral shell-[1,3- dioxolane -2]-quinoline, it is special
Levy and be, comprise the following steps：
In a nitrogen environment, by 1 '-benzyl -2 ' -one -3 ', 4 ', 5 ', 7 ', 8 '-pentahydro--spiral shell-[1,3- dioxolane -2]-quinoline
It is added in toluene, stirs with tetrachloroquinone, 2-10h is reacted under the conditions of 40-110 DEG C, distilled water is then added,
3-7h is reacted under the conditions of 25-65 DEG C, room temperature is cooled to, is extracted with ethyl acetate, concentrate, produce 1 '-benzyl -2 ' -one -5 ',
7 ', 8 '-three hydrogen-spiral shell-[1,3- dioxolane -2]-quinoline；1 '-the benzyl -2 ' -one -3 ', 4 ', 5 ', 7 ', 8 '-pentahydro--spiral shell -
[1,3- dioxolane -2]-quinoline, tetrachloroquinone, toluene, the mol ratio of distilled water are 1:1-2:28-56:100-300.
2. 1 '-benzyl -2 according to claim 1 ' -one -5 ', 7 ', 8 '-three hydrogen-spiral shell-[1,3- dioxolane -2]-quinoline
Preparation method, it is characterised in that optimum condition is：In a nitrogen environment, by 1 '-benzyl -2 ' -one -3 ', 4 ', 5 ', 7 ', 8 ' -
Pentahydro--spiral shell-[1,3- dioxolane -2]-quinoline and tetrachloroquinone are added in toluene, are stirred, and are reacted under the conditions of 80 DEG C
6h, then adds distilled water, reacts 5h under the conditions of 60 DEG C, is cooled to room temperature, is extracted with ethyl acetate, concentration, produces
1 '-benzyl -2 ' -one -5 ', 7 ', 8 '-three hydrogen-spiral shell-[1,3- dioxolane -2]-quinoline；1 '-the benzyl -2 ' -one -3 ', 4 ',
5 ', 7 ', 8 '-pentahydro--spiral shell-[1,3- dioxolane -2]-quinoline, tetrachloroquinone, toluene, the mol ratio of distilled water are 1:1.2:
37.8:180。
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Address after: 710075 Xi'an high tech Zone, Shaanxi hi tech Road, No. 25 Maple Leaf Garden District, block C, No. 157 Applicant after: SHAANXI JIAHE PHYTOCHEM CO., LTD. Address before: 710075 Xi'an high tech Zone, Shaanxi hi tech Road, No. 25 Maple Leaf Garden District, block C, No. 157 Applicant before: Shanxi Jiahe Plant Chemical Co., Ltd. |
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Inventor after: Yang Junren Inventor after: Liu Na Inventor after: Xu Yiwei Inventor after: Wang Chunde Inventor after: Deng Shangyong Inventor after: Guo Wenhua Inventor after: Xiao Jinxia Inventor before: Xu Yiwei Inventor before: Wang Chunde Inventor before: Deng Shangyong Inventor before: Guo Wenhua Inventor before: Xiao Jinxia |