CN107641076A - A kind of synthetic method of luxuriant and rich with fragrance quinones - Google Patents
A kind of synthetic method of luxuriant and rich with fragrance quinones Download PDFInfo
- Publication number
- CN107641076A CN107641076A CN201610616949.3A CN201610616949A CN107641076A CN 107641076 A CN107641076 A CN 107641076A CN 201610616949 A CN201610616949 A CN 201610616949A CN 107641076 A CN107641076 A CN 107641076A
- Authority
- CN
- China
- Prior art keywords
- solvent
- formulas
- alkene
- neighbour
- alcohol
- 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.)
- Withdrawn
Links
- YYVYAPXYZVYDHN-UHFFFAOYSA-N O=C(c1ccccc1-c1ccccc11)C1=O Chemical compound O=C(c1ccccc1-c1ccccc11)C1=O YYVYAPXYZVYDHN-UHFFFAOYSA-N 0.000 description 2
- ARWRFSCXAQGXSN-UHFFFAOYSA-N CC(C)c(cc1)cc(C2=O)c1-c1ccccc1C2=O Chemical compound CC(C)c(cc1)cc(C2=O)c1-c1ccccc1C2=O ARWRFSCXAQGXSN-UHFFFAOYSA-N 0.000 description 1
Abstract
The present invention provides a kind of method for preparing luxuriant and rich with fragrance quinones, using the alcohol of alkene 1 of 1 adjacent benzene phenyl shown in Formulas I the third 2 as raw material, mixed with salt, oxidant, solvent completely, react 8~24h at 80~120 DEG C, gained reaction solution isolates and purifies the phenanthrenequione and its derivative shown in obtained Formula II；Described salt is trifluoromethanesulfonic acid sodium, sodium carbonate, sodium acid carbonate, sodium sulphate or sodium chloride；The ratio between amount of the alcohol matter of alkene 1 of 1 adjacent benzene phenyl shown in described salt and Formulas I the third 2 is 0.5~2:1.The method course of reaction safety and environmental protection of the present invention, substrate adaptability are good, and reaction condition is simple to operation, are a kind of variation routes for synthesizing the various luxuriant and rich with fragrance quinones containing substituent.
Description
Technical field
The present invention relates to a kind of preparation method of luxuriant and rich with fragrance quinones.
Background technology
Luxuriant and rich with fragrance quinones is a kind of important organic compound, has good bioactivity, is widely used in manufacture medicine
Thing, dyestuff, and be the important intermediate of some important industrial chemicals.Because the purposes of phenanthrenequione is very extensive, at home and abroad
Market prospects are very optimistic.It is more on phenanthrenequione and its pertinent literature of the synthetic route of derivative report at present, mainly have following
Three kinds of methods：1) using phenanthrene as raw material high price salt metal synthetic method (referring to DE, 3305528,1984,08；US Patent,
4510090,1985,04)；2) using phenanthrene as raw material oxidation operation synthetic method (referring to J.Org.Chem, 1993,58,
1593-1595；Tetrahedron,1997,53,7889-7896)；3) with the luxuriant and rich with fragrance nitric acid synthetic method for raw material of 9,10- epoxies
(referring to JP, 60233029,1985).But some oxidants involved by first method are on the high side, some courses of reaction
That " three wastes " bring serious pollution to environment be present；Some oxidants involved by second method prepare it is relatively difficult, and
And Some Drugs toxicity is larger, should not use；The third method formality is more, not easy to operate.
In view of the problem of above method is present, develops the synthetic route that a kind of raw material is cheap, the reaction time is short, simple to operate
Extremely it is necessary to synthesize luxuriant and rich with fragrance quinones.
The content of the invention
For the deficiency and technological difficulties of conventional synthesis phenanthrene quinones method, it is an object of the invention to realize with letter
Single cheap oxidant, and a kind of new method of Material synthesis phenanthrene quinones simple and easy to get.
The technical solution adopted by the present invention is as follows：
Using 1- neighbour's benzene phenyl propyl- 2- alkene -1- alcohol shown in Formulas I as raw material, mixed with salt, oxidant, solvent completely, 80
~120 DEG C of 8~24h of reaction, gained reaction solution isolate and purify the phenanthrenequione and its derivative shown in obtained Formula II；Described salt is three
Fluorine methanesulfonic sodium, sodium carbonate, sodium acid carbonate, sodium sulphate or sodium chloride；1- neighbour's benzene phenyl propyl- 2- shown in described salt and Formulas I
The ratio between amount of alkene -1- alcohol matters is 0.5~2：1；
R in Formulas I1、R2Respectively with R in Formula II1、R2Identical, described R1For H, fluorine-based or chloro；Described R2For H, first
Base, ethyl or isopropyl.
Further, the phenanthrenequione shown in preferably described Formula II and its derivative are one of following：
Further, preferably described salt is trifluoromethanesulfonic acid sodium, 1- neighbour's benzene phenyl propyl- 2- shown in described salt and Formulas I
The ratio between amount of alkene -1- alcohol matters is 1:1.The characteristics of salt of the present invention is cheap and easy to get, low toxicity.
Oxidant of the present invention is iodic anhydride；Further, described oxidant and 1- neighbour's benzene benzene shown in Formulas I
The ratio between amount of base propyl- 2- alkene -1- alcohol matters is 1~2：1, preferably 1.5:1.
Further, described solvent is the mixed solution of acetonitrile and water composition；Further, in described solvent acetonitrile with
The volume ratio of water is 1~500：1；Further, the volume ratio of acetonitrile and water is 1.5 in preferably described solvent：1.
Further, the volumetric usage of described solvent is with the material of 1- neighbour's benzene phenyl propyl- 2- alkene -1- alcohol shown in Formulas I
Amount is calculated as 10~15mL/mmol.
Reaction temperature of the present invention is 110 DEG C, and the reaction time is 12 hours.
Further, reaction solution isolation and purification method of the present invention is：After reaction terminates, post is added into gained reaction solution
Chromatographic silica gel, and solvent is removed by being evaporated under reduced pressure, with column chromatographic isolation and purification, with petrol ether/ethyl acetate=20:1 conduct
Eluant, eluent is eluted, and collects the eluent containing target product, and the phenanthrenequione and its derivative shown in Formula II are obtained after removing solvent
Thing.
Further, more specifically, the method for the invention is carried out according to the following steps：
Mix completely, stirred at 110 DEG C anti-by 1- neighbour's benzene phenylallylalcohol shown in Formulas I, with salt, oxidant, solvent
Answer 12 hours, after reaction terminates, column chromatography silica gel is added into gained reaction solution, and solvent is removed by being evaporated under reduced pressure, with post
Chromatography purifies, with petrol ether/ethyl acetate=20:1 is eluted as eluant, eluent, collects the elution containing target product
Liquid, the phenanthrenequione and its derivative shown in Formula II are obtained after removing solvent；
Described salt is trifluoromethanesulfonic acid sodium；1- neighbour's benzene phenyl propyl- 2- alkene -1- alcohol matters shown in described salt and Formulas I
The ratio between amount be 1:1；Described oxidant is iodic anhydride；Described oxidant with 1- neighbour's benzene phenyl propyl- shown in Formulas I
The ratio between amount of 2- alkene -1- alcohol matters is 1.5：1；Described solvent is acetonitrile/water (V：V=1.5：1)；The body of described solvent
Product dosage is calculated as 12.5mL/mmol with the amount of the material of 1- neighbour's benzene phenyl propyl- 2- alkene -1- alcohol shown in Formulas I.
Compared with prior art, the beneficial effects of the invention are as follows：
(1) salt is cheap and easy to get, and toxicity is relatively low；
(2) oxidant is cheap, and environment-friendly；
(3) reaction condition is simple to operation, substrate universality is strong；
Specific implementation method
The present invention is described in further detail with reference to specific embodiment, but protection scope of the present invention is not limited to
This：
Embodiment 1：
By 0.2mmol 1- neighbour benzene phenyl propyl- 2- alkene -1- alcohol, 0.3mmol iodic anhydrides, 0.2mmol trifluoromethanesulfonic acids
Sodium is added in 15mL pressure pipes, adds 2.5mL acetonitrile/waters (V：V=1.5：1) solvent is made.Magnetic force at a temperature of being 110 DEG C
Stir 12h.Then, two spoon column chromatography silica gels (100-200 mesh) are added in reaction solution, and it is molten by being evaporated under reduced pressure removing
Agent, then by column chromatographic isolation and purification, with petrol ether/ethyl acetate volume ratio 20:1 is eluted as eluant, eluent, and collection contains
There is the eluent of target product, pure product is obtained after removing solvent.The material is yellow solid, yield 63%.
Characterize data：m.p.218-220℃；IR(neat):ν=1673 (C=O) cm-1；1H NMR(CDCl3,
400MHz):8.17-8.15 (m, 2H), 7.99 (d, J=8Hz, 2H), 7.73-7.68 (m, 2H), 7.48-7.44 (m, 2H)；13C
NMR(CDCl3,100MHz):δ180.3,136.0,135.8,131.0,130.5,129.6,124.0.
Embodiment 2：
0.2mmol 1- neighbour benzene phenyl propyl- 2- alkene -1- alcohol, 0.2mmol iodic anhydrides, 0.1mmol sodium carbonate are added
Into 15mL pressure pipes, 2.5mL acetonitrile/waters (V is added：V=1.5：1) solvent is made.The magnetic agitation 12h at a temperature of 120 DEG C.
Then, two spoon column chromatography silica gels (100-200 mesh) are added in reaction solution, and solvent is removed by being evaporated under reduced pressure, then are passed through
Column chromatographic isolation and purification, with petrol ether/ethyl acetate volume ratio 20:1 is eluted as eluant, eluent, and collection contains target product
Eluent, remove solvent after obtain pure product.The material is yellow solid, yield 48%.
Characterize data：m.p.218-220℃；IR(neat):ν=1673 (C=O) cm-1；1H NMR(CDCl3,
400MHz):8.17-8.15 (m, 2H), 7.99 (d, J=8Hz, 2H), 7.73-7.68 (m, 2H), 7.48-7.44 (m, 2H)；13C
NMR(CDCl3,100MHz):δ180.3,136.0,135.8,131.0,130.5,129.6,124.0.
Embodiment 3：
0.2mmol 1- neighbour benzene phenyl propyl- 2- alkene -1- alcohol, 0.4mmol iodic anhydrides, 0.4mmol sodium acid carbonates are added
Enter into 15mL pressure pipes, add 2.5mL acetonitrile/waters (V：V=1.5：1) solvent is made.The magnetic agitation at a temperature of 80 DEG C
12h.Then, two spoon column chromatography silica gels (100-200 mesh) are added in reaction solution, and solvent is removed by being evaporated under reduced pressure, then
By column chromatographic isolation and purification, with petrol ether/ethyl acetate volume ratio 20:1 is eluted as eluant, eluent, and collection contains target
The eluent of product, pure product is obtained after removing solvent.The material is yellow solid, yield 43%.
Characterize data：m.p.218-220℃；IR(neat):ν=1673 (C=O) cm-1；1H NMR(CDCl3,
400MHz):8.17-8.15 (m, 2H), 7.99 (d, J=8Hz, 2H), 7.73-7.68 (m, 2H), 7.48-7.44 (m, 2H)；13C
NMR(CDCl3,100MHz):δ180.3,136.0,135.8,131.0,130.5,129.6,124.0.
Embodiment 4：
0.2mmol 1- neighbour benzene phenyl propyl- 2- alkene -1- alcohol, 0.2mmol iodic anhydrides, 0.2mmol sodium sulphate are added
Into 15mL pressure pipes, 2mL acetonitrile/waters (V is added：V=1：1) solvent is made.The magnetic agitation 8h at a temperature of 120 DEG C.Then,
Two spoon column chromatography silica gels (100-200 mesh) are added in reaction solution, and solvent is removed by being evaporated under reduced pressure, then pass through column chromatography
Isolate and purify, with petrol ether/ethyl acetate volume ratio 20:1 is eluted as eluant, eluent, collects the elution containing target product
Liquid, pure product is obtained after removing solvent.The material is yellow solid, yield 50%.
Characterize data：m.p.218-220℃；IR(neat):ν=1673 (C=O) cm-1；1H NMR(CDCl3,
400MHz):8.17-8.15 (m, 2H), 7.99 (d, J=8Hz, 2H), 7.73-7.68 (m, 2H), 7.48-7.44 (m, 2H)；13C
NMR(CDCl3,100MHz):δ180.3,136.0,135.8,131.0,130.5,129.6,124.0.
Embodiment 5：
0.2mmol 1- neighbour benzene phenyl propyl- 2- alkene -1- alcohol, 0.3mmol iodic anhydrides, 0.2mmol sodium chloride are added
Into 15mL pressure pipes, 3mL acetonitrile/waters (V is added：V=500：1) solvent is made.The magnetic agitation 24h at a temperature of 80 DEG C.So
Afterwards, two spoon column chromatography silica gels (100-200 mesh) are added in reaction solution, and solvent is removed by being evaporated under reduced pressure, then pass through post
Chromatography purifies, with petrol ether/ethyl acetate volume ratio 20:1 is eluted as eluant, eluent, is collected containing target product
Eluent, pure product is obtained after removing solvent.The material is yellow solid, yield 46%.
Characterize data：m.p.218-220℃；IR(neat):ν=1673 (C=O) cm-1；1H NMR(CDCl3,
400MHz):8.17-8.15 (m, 2H), 7.99 (d, J=8Hz, 2H), 7.73-7.68 (m, 2H), 7.48-7.44 (m, 2H)；13C
NMR(CDCl3,100MHz):δ180.3,136.0,135.8,131.0,130.5,129.6,124.0.
Embodiment 6：
By 0.2mmol 1- neighbour benzene phenyl propyl- 2- alkene -1- alcohol, 0.4mmol iodic anhydrides, 0.2mmol trifluoromethanesulfonic acids
Sodium is added in 15mL pressure pipes, adds 2.5mL acetonitrile/waters (V：V=1：1) solvent is made.Magnetic force stirs at a temperature of 110 DEG C
Mix 12h.Then, two spoon column chromatography silica gels (100-200 mesh) are added in reaction solution, and solvent is removed by being evaporated under reduced pressure,
Again by column chromatographic isolation and purification, with petrol ether/ethyl acetate volume ratio 20:1 is eluted as eluant, eluent, and collection contains mesh
The eluent of product is marked, pure product is obtained after removing solvent.The material is yellow solid, yield 60%.
Characterize data：m.p.218-220℃；IR(neat):ν=1673 (C=O) cm-1；1H NMR(CDCl3,
400MHz):8.17-8.15 (m, 2H), 7.99 (d, J=8Hz, 2H), 7.73-7.68 (m, 2H), 7.48-7.44 (m, 2H)；13C
NMR(CDCl3,100MHz):δ180.3,136.0,135.8,131.0,130.5,129.6,124.0.
Embodiment 7：
By 0.2mmol 1- neighbour benzene phenyl propyl- 2- alkene -1- alcohol, 0.3mmol iodic anhydrides, 0.4mmol trifluoromethanesulfonic acids
Sodium is added in 15mL pressure pipes, adds 2.5mL acetonitrile/waters (V：V=500：1) solvent is made.Magnetic force stirs at a temperature of 110 DEG C
Mix 12h.Then, two spoon column chromatography silica gels (100-200 mesh) are added in reaction solution, and solvent is removed by being evaporated under reduced pressure,
Again by column chromatographic isolation and purification, with petrol ether/ethyl acetate volume ratio 20:1 is eluted as eluant, eluent, and collection contains mesh
The eluent of product is marked, pure product is obtained after removing solvent.The material is yellow solid, yield 49%.
Characterize data：m.p.218-220℃；IR(neat):ν=1673 (C=O) cm-1；1H NMR(CDCl3,
400MHz):8.17-8.15 (m, 2H), 7.99 (d, J=8Hz, 2H), 7.73-7.68 (m, 2H), 7.48-7.44 (m, 2H)；13C
NMR(CDCl3,100MHz): δ180.3,136.0,135.8,131.0,130.5,129.6,124.0.
Embodiment 8：
By 0.2mmol 1- neighbour benzene phenyl propyl- 2- alkene -1- alcohol, 0.4mmol iodic anhydrides, 0.4mmol trifluoromethanesulfonic acids
Sodium is added in 15mL pressure pipes, adds 2.5mL acetonitrile/waters (V：V=1.5：1) solvent is made.Magnetic force stirs at a temperature of 110 DEG C
Mix 12h.Then, two spoon column chromatography silica gels (100-200 mesh) are added in reaction solution, and solvent is removed by being evaporated under reduced pressure,
Again by column chromatographic isolation and purification, with petrol ether/ethyl acetate volume ratio 20:1 is eluted as eluant, eluent, and collection contains mesh
The eluent of product is marked, pure product is obtained after removing solvent.The material is yellow solid, yield 55%.
Characterize data：m.p.218-220℃；IR(neat):ν=1673 (C=O) cm-1；1H NMR(CDCl3,
400MHz):8.17-8.15 (m, 2H), 7.99 (d, J=8Hz, 2H), 7.73-7.68 (m, 2H), 7.48-7.44 (m, 2H)；13C
NMR(CDCl3,100MHz):δ180.3,136.0,135.8,131.0,130.5,129.6,124.0.
Embodiment 9：
By 0.2mmol 1- neighbour benzene phenyl propyl- 2- alkene -1- alcohol, 0.3mmol iodic anhydrides, 0.1mmol trifluoromethanesulfonic acids
Sodium is added in 15mL pressure pipes, adds 2.5mL acetonitrile/waters (V：V=1.5：1) solvent is made.Magnetic force stirs at a temperature of 110 DEG C
Mix 24h.Then, two spoon column chromatography silica gels (100-200 mesh) are added in reaction solution, and solvent is removed by being evaporated under reduced pressure,
Again by column chromatographic isolation and purification, with petrol ether/ethyl acetate volume ratio 20:1 is eluted as eluant, eluent, and collection contains mesh
The eluent of product is marked, pure product is obtained after removing solvent.The material is yellow solid, yield 43%.
Characterize data：m.p.218-220℃；IR(neat):ν=1673 (C=O) cm-1；1H NMR(CDCl3,
400MHz):8.17-8.15 (m, 2H), 7.99 (d, J=8Hz, 2H), 7.73-7.68 (m, 2H), 7.48-7.44 (m, 2H)；13C
NMR(CDCl3,100MHz):δ180.3,136.0,135.8,131.0,130.5,129.6,124.0.
Embodiment 10
By 0.2mmol 1- (2- is to methylphenyl) propyl- 2- alkene -1- alcohol, 0.3mmol iodic anhydrides, 0.2mmol trifluoros
Methanesulfonic sodium is added in 15mL pressure pipes, adds 2.5mL acetonitrile/waters (V：V=1.5：1) solvent is made.At a temperature of 110 DEG C
Magnetic agitation 12h.Then, two spoon column chromatography silica gels (100-200 mesh) are added in reaction solution, and are removed by being evaporated under reduced pressure
Solvent, then by column chromatographic isolation and purification, with petrol ether/ethyl acetate volume ratio 20:1 is eluted as eluant, eluent, is collected
Eluent containing target product, remove solvent after obtain pure product (.The material is yellow solid, yield 65%.
Characterize data：m.p.145-147℃；IR(neat):ν=1672 (C=O) cm-1；1H NMR(CDCl3,
400MHz):8.04-8.02 (m, 1H), 7.83 (d, J=8.4Hz, 2H), 7.75 (d, J=8Hz, 1H), 7.60-7.56 (m,
1H),7.40-7.38(m,1H), 7.34-7.30(m,1H),2.32(s,3H)；13C NMR(CDCl3,100MHz):δ179.4,
179.4,138.9,135.9,135.0,134.9,132.2,129.8,129.7,129.4,128.1,127.3,123.0,
122.7,19.9.
Embodiment 11
By 0.2mmol 1- (2- is to ethylbenzene phenyl) propyl- 2- alkene -1- alcohol, 0.3mmol iodic anhydrides, 0.2mmol trifluoros
Methanesulfonic sodium is added in 15mL pressure pipes, adds 2.5mL acetonitrile/waters (V：V=1.5：1) solvent is made.It is 110 DEG C of temperature
Lower magnetic agitation 12h.Then, two spoon column chromatography silica gels (100-200 mesh) are added in reaction solution, and are removed by being evaporated under reduced pressure
Solvent is removed, then by column chromatographic isolation and purification, with petrol ether/ethyl acetate volume ratio 20:1 is eluted as eluant, eluent, is received
Collect the eluent containing target product, pure product is obtained after removing solvent.The material is yellow solid, yield 68%.
Characterize data：m.p.122-124℃；IR(neat):ν=1671 (C=O) cm-1；1H NMR(CDCl3,
400MHz):8.01-7.97(m,1H),7.84-7.73(m,3H),7.58-7.53(m,1H),7.41-7.39(m,1H),7.32-
7.28 (m, 1H), 2.63-2.57 (m, 2H), 1.19 (t, J=7.6Hz, 3H)；13C NMR(CDCl3,100MHz):δ180.37,
180.36,146.1,136.02,135.95,135.8,133.4,130.9,130.6,130.3,129.5,129.1,124.1,
123.7,28.3,14.9.
Embodiment 12
By 0.2mmol 1- (2- is to ethylbenzene -4- chlorphenyls) propyl- 2- alkene -1- alcohol, 0.3mmol iodic anhydrides,
0.2mmol trifluoromethanesulfonic acid sodium is added in 15mL pressure pipes, adds 2.5mL acetonitrile/waters (V：V=1.5：1) solvent is made.
Magnetic agitation 12h at a temperature of 110 DEG C.Then, two spoon column chromatography silica gels (100-200 mesh) are added in reaction solution, and are passed through
It is evaporated under reduced pressure and removes solvent, then by column chromatographic isolation and purification, with petrol ether/ethyl acetate volume ratio 20:1 enters as eluant, eluent
Row elution, collects the eluent containing target product, and pure product is obtained after removing solvent.The material is yellow solid, yield
66%.
Characterize data：m.p.205-206℃；IR(neat):ν=1673 (C=O) cm-1；1H NMR(CDCl3,
400MHz):8.00 (d, J=8.4Hz, 1H), 7.92 (d, J=1.6Hz, 1H), 7.82 (d, J=1.6Hz, 1H), 7.75 (d, J
=8.4Hz, 1H), 7.48-7.45 (m, 1H), 7.31-7.29 (m, 1H), 2.68-2.62 (m, 2H), 1.21 (t, J=7.6Hz,
3H)；13C NMR(CDCl3,100MHz):δ179.9,179.4,147.0,142.9,137.7,135.9,132.1,131.9,
131.2,129.8,129.3,129.0,124.2,124.0,28.4,14.9.
Embodiment 13
By 0.2mmol 1- (2- is to ethylbenzene -4- fluorophenyls) propyl- 2- alkene -1- alcohol, 0.3mmol iodic anhydrides,
0.2mmol trifluoromethanesulfonic acid sodium is added in 15mL pressure pipes, adds 2.5mL acetonitrile/waters (V：V=1.5：1) solvent is made.
The magnetic agitation 12h at a temperature of 110 DEG C.Then, two spoon column chromatography silica gels (100-200 mesh) are added in reaction solution, and are led to
Cross decompression and solvent is distilled off, then by column chromatographic isolation and purification, with petrol ether/ethyl acetate volume ratio 20:1 is used as eluant, eluent
Eluted, collect the eluent containing target product, pure product is obtained after removing solvent.The material is yellow solid, production
Rate 65%.
Characterize data：Yellow solid,m.p.182-183℃；IR(neat):ν=1668 (C=O) cm-1；1H NMR
(CDCl3,400MHz):8.20-8.16 (m, 1H), 7.98 (d, J=1.6Hz, 1H), 7.78 (d, J=8Hz, 1H), 7.59-
7.53 (m, 2H), 7.12-7.07 (m, 1H), 2.75-2.70 (m, 2H), 1.29 (t, J=7.6Hz, 3H)；13C NMR(CDCl3,
100MHz):δ 180.0,178.8,167.7 (d, J=257Hz), 147.0,139.3 (d, J=9Hz), 135.8,133.7 (d, J
=10Hz), 132.1 (d, J=2Hz), 131.1,129.6,127.4 (d, J=3Hz), 124.2,116.5 (d, J=22Hz),
110.8 (d, J=24Hz), 28.4,14.9.
Embodiment 14
By 0.2mmol 1- (2- is to isopropylbenzene phenyl) propyl- 2- alkene -1- alcohol, 0.3mmol iodic anhydrides, 0.2mmol tri-
Fluorine methanesulfonic sodium is added in 15mL pressure pipes, adds 2.5mL acetonitrile/waters (V：V=1.5：1) solvent is made.Then, in 110
Magnetic agitation 12h at a temperature of DEG C.Then, two spoon column chromatography silica gels (100-200 mesh) are added in reaction solution, and pass through decompression
Solvent is distilled off, then pure product is obtained (with petrol ether/ethyl acetate=20 by pillar layer separation:1 as elution
Agent).The material is yellow solid, yield 69%.
Characterize data：Yellow solid,m.p.127-128℃；IR(neat):ν=1671 (C=O) cm-1；1H NMR
(CDCl3,400MHz):8.15 (d, J=2Hz, 1H), 8.11-8.09 (m, 1H), 7.92-7.86 (m, 2H), 7.73-7.70 (m,
1H),7.67-7.63(m,1H),7.41-7.37(m,1H),1.37(s,9H)；13C NMR(CDCl3,100MHz):δ180.5,
180.5,153.1,135.97,135.95,133.4,133.2,130.7,130.3,129.1,127.1,124.0,123.8,
34.9,30.9。
Claims (10)
1. a kind of synthetic method of luxuriant and rich with fragrance quinones, it is characterised in that described method is carried out as follows：
Using 1- neighbour's benzene phenyl propyl- 2- alkene -1- alcohol shown in Formulas I as raw material, mixed with salt, oxidant, solvent completely, 80~
120 DEG C of 8~24h of reaction, gained reaction solution isolate and purify the phenanthrenequione and its derivative shown in obtained Formula II；Described salt is trifluoro
Methanesulfonic sodium, sodium carbonate, sodium acid carbonate, sodium sulphate or sodium chloride；1- neighbour benzene phenyl propyl- 2- alkene shown in described salt and Formulas I-
The ratio between amount of 1- alcohol matters is 0.5~2:1；
R in Formulas I1、R2Respectively with R in Formula II1、R2Identical, described R1For H, fluorine-based or chloro；Described R2For H, methyl, second
Base or isopropyl.
2. the method as described in claim 1, it is characterised in that 1- neighbour's benzene phenyl propyl- 2- alkene -1- shown in described salt and Formulas I
The ratio between amount of alcohol matter is 1:1.
3. the method as described in claim 1, it is characterised in that described oxidant is iodic anhydride.
4. the method as described in claim 1, it is characterised in that 1- neighbour's benzene phenyl propyl- 2- shown in described oxidant and Formulas I
The ratio between amount of alkene -1- alcohol matters is 1~2：1.
5. the method as described in claim 1, it is characterised in that described solvent is the mixed solution of acetonitrile and water composition.
6. method as claimed in claim 4, it is characterised in that the volume ratio of acetonitrile and water is 1~500 in described solvent：1.
7. the method as described in claim 1, it is characterised in that the volumetric usage of described solvent is with 1- neighbour's benzene benzene shown in Formulas I
The amount of the material of base propyl- 2- alkene -1- alcohol is calculated as 10~15mL/mmol.
8. according to the method for claim 1, it is characterised in that described reaction temperature is 110 DEG C, and the reaction time is 12 small
When.
9. method according to claims 1 to 8, it is characterised in that the reaction solution isolation and purification method is：Reaction terminates
Afterwards, column chromatography silica gel is added into gained reaction solution, and solvent is removed by being evaporated under reduced pressure, with column chromatographic isolation and purification, with stone
Oily ether/ethyl acetate=20:1 is eluted as eluant, eluent, collects the eluent containing target product, is obtained after removing solvent
Phenanthrenequione and its derivative shown in Formula II.
10. the method as described in claim 1, it is characterised in that methods described is carried out according to the following steps：
Mixed completely by 1- neighbour's benzene phenylallylalcohol shown in Formulas I, with salt, oxidant, solvent, the stirring reaction 12 at 110 DEG C
Hour, after reaction terminates, column chromatography silica gel is added into gained reaction solution, and solvent is removed by being evaporated under reduced pressure, with column chromatography
Isolate and purify, with petrol ether/ethyl acetate=20:1 is eluted as eluant, eluent, collects the eluent containing target product,
The phenanthrenequione and its derivative shown in Formula II are obtained after removing solvent；
Described salt is trifluoromethanesulfonic acid sodium；The amount of 1- neighbour's benzene phenyl propyl- 2- alkene -1- alcohol matters shown in described salt and Formulas I
The ratio between be 1:1；Described oxidant is iodic anhydride；Described oxidant with 1- neighbour's benzene phenyl propyl- 2- shown in Formulas I
The ratio between amount of alkene -1- alcohol matters is 1.5：1；Described solvent is acetonitrile/water (V：V=1.5：1)；The volume of described solvent is used
Amount is calculated as 12.5 mL/mmol with the amount of the material of 1- neighbour's benzene phenyl propyl- 2- alkene -1- alcohol shown in Formulas I.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610616949.3A CN107641076A (en) | 2016-07-29 | 2016-07-29 | A kind of synthetic method of luxuriant and rich with fragrance quinones |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610616949.3A CN107641076A (en) | 2016-07-29 | 2016-07-29 | A kind of synthetic method of luxuriant and rich with fragrance quinones |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107641076A true CN107641076A (en) | 2018-01-30 |
Family
ID=61109018
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610616949.3A Withdrawn CN107641076A (en) | 2016-07-29 | 2016-07-29 | A kind of synthetic method of luxuriant and rich with fragrance quinones |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107641076A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115650839A (en) * | 2022-10-26 | 2023-01-31 | 辽宁科技学院 | Refining method of phenanthrenequinone |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3305528A1 (en) * | 1983-02-18 | 1984-08-23 | Rütgerswerke AG, 6000 Frankfurt | METHOD FOR PRODUCING PHENANTHRENE CHINONE |
| EP2128121A4 (en) * | 2007-03-08 | 2012-07-04 | Panasonic Corp | Phenanthrenequinone compound, electrode active material, and electrical storage device |
| CN105367399A (en) * | 2014-08-29 | 2016-03-02 | 浙江工业大学 | Preparing method of 9,10-phenanthraquinone compound |
-
2016
- 2016-07-29 CN CN201610616949.3A patent/CN107641076A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3305528A1 (en) * | 1983-02-18 | 1984-08-23 | Rütgerswerke AG, 6000 Frankfurt | METHOD FOR PRODUCING PHENANTHRENE CHINONE |
| EP2128121A4 (en) * | 2007-03-08 | 2012-07-04 | Panasonic Corp | Phenanthrenequinone compound, electrode active material, and electrical storage device |
| CN105367399A (en) * | 2014-08-29 | 2016-03-02 | 浙江工业大学 | Preparing method of 9,10-phenanthraquinone compound |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115650839A (en) * | 2022-10-26 | 2023-01-31 | 辽宁科技学院 | Refining method of phenanthrenequinone |
| CN115650839B (en) * | 2022-10-26 | 2023-07-14 | 辽宁科技学院 | Method for refining phenanthrenequinone |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109232310A (en) | A kind of trifluoroacetyl group replaces hydazone derivative and its synthetic method | |
| CN104072347B (en) | 4-alkoxyl-1, the preparation method of 1,1-tri-fluoro-3-butene-2-one | |
| CN105732619B (en) | A kind of synthetic method of 5,6,7,8 tetrahydropyridines simultaneously [2,3 d] pyrimidines | |
| CN104892614A (en) | Synthesis method of 6H-isoindolo[2, 1-alpha]indol-6-one derivative | |
| CN105367399B (en) | A kind of preparation method of 9,10 luxuriant and rich with fragrance quinones | |
| CN107641076A (en) | A kind of synthetic method of luxuriant and rich with fragrance quinones | |
| CN102617455A (en) | Preparation method of pyridoxal or pyridoxal hydrochloride | |
| CN106117225A (en) | The synthetic method of benzophenanthrene decane epoxide bridging isobutyltrimethylmethane. phenyl porphyrin metal Zn coordination compound | |
| CN103435477B (en) | A kind of method of synthesizing paraethoxybenxoic acid | |
| CN113651788B (en) | 3-aminoalkylchromone compound and preparation method thereof | |
| CN106243073B (en) | A kind of 2-H 1-benzopyran derivatives and its synthetic method | |
| CN104262122A (en) | Method for synthesizing 1,4-butene diketone compound | |
| CN107663149A (en) | A kind of preparation method of phenanthrenequione and its derivative | |
| CN104327025B (en) | A kind of preparation method of 4-arylnaphthalene lactone derivative | |
| CN107641101A (en) | A kind of preparation method of phenanthridines ketone compounds | |
| CN106117220A (en) | The synthetic method of benzophenanthrene dodecyloxy bridging isobutyltrimethylmethane. phenyl porphyrin metal Zn coordination compound | |
| CN106083690A (en) | A kind of preparation method of polysubstituted 3 methylene indolones | |
| Araki et al. | Allylgallation of cyclopropenes. Crystal structure of a novel cyclopropylgallium compound prepared by allylgallation of hydroxy-bearing cyclopropene | |
| CN106349073B (en) | A kind of synthetic method of phenacylidene malonic acid ester type compound | |
| CN106316819B (en) | A kind of synthetic method of 2- substitution -1,4-naphthoquinone class compound | |
| CN104926628B (en) | A kind of synthetic method of benzil analog derivative | |
| CN107778146A (en) | A kind of synthetic method of ether compound | |
| CN105367396B (en) | A kind of synthetic method of naphthane ketone compounds | |
| CN109422631A (en) | A kind of synthetic method of indanone compounds | |
| CN108409672A (en) | A kind of method that mantoquita catalyzes and synthesizes polysubstituted pyrimidine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20180130 |
|
| WW01 | Invention patent application withdrawn after publication |