CN104193596B - Trans adjacent hydroxy stibene derivative and its preparation method and application - Google Patents
Trans adjacent hydroxy stibene derivative and its preparation method and application Download PDFInfo
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- CN104193596B CN104193596B CN201410432114.3A CN201410432114A CN104193596B CN 104193596 B CN104193596 B CN 104193596B CN 201410432114 A CN201410432114 A CN 201410432114A CN 104193596 B CN104193596 B CN 104193596B
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- 0 C*(C)C1(C)C=CC(C(F)(F)F)=CC=C1 Chemical compound C*(C)C1(C)C=CC(C(F)(F)F)=CC=C1 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/24—Halogenated derivatives
- C07C39/373—Halogenated derivatives with all hydroxy groups on non-condensed rings and with unsaturation outside the aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/27—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups
- C07C205/35—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C255/53—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and hydroxy groups bound to the carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/205—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic, containing only six-membered aromatic rings as cyclic parts with unsaturation outside the rings
- C07C39/21—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic, containing only six-membered aromatic rings as cyclic parts with unsaturation outside the rings with at least one hydroxy group on a non-condensed ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
Abstract
The invention discloses a kind of trans adjacent hydroxy stibene derivative and its preparation method and application, this preparation method comprises the steps: under rhodium catalyst and acetate existent condition, o-hydroxystyrene compounds and aryl boric acid react in a solvent, after having reacted, obtain described trans adjacent hydroxy stibene derivative through aftertreatment.This preparation method's reaction conditions is gentle, and means are succinctly quick, and yield is higher.With trans-resveratrol in contrast, cell experiment shows that its anti-tumor activity is generally better to the product of gained.
Description
Technical field
The invention belongs to medicinal chemistry art, be specifically related to a kind of preparation method of trans adjacent hydroxy stibene derivative, and the antitumor cell energy for growth of compound is tested.
Background technology
The rare compounds of hexichol second is a class material with biological activity or pharmaceutical use.Especially, there is hydroxyl substituted diphenylamine ethene and show significantly anti-oxidant, antineoplastic characteristic.Trans-resveratrol (resveratrol) is exactly a kind of biological very strong natural product, and it all has obvious restraining effect to Several Kinds of Malignancy cells such as mammary cancer, cancer of the stomach, colorectal carcinoma, prostate cancer, leukemia, ovarian cancer, skin carcinomas.Below for having the hydroxyl diphenylethylene compounds structure representative of pharmaceutical active:
Method mainly Wittig reaction and the Mizoroki-Heck reaction of the synthesis diphenylethylene compounds that the past is conventional.But it is low that they exist yield, along shortcomings such as inverted stereo poor selectivity or the required condition harshnesses of reaction.Will at Pd (OAc) as Heck reaction
2carry out in high temperature inert gas environment under catalysis (TetrahedronLett.2002,43,597), reaction formula is as follows:
Summary of the invention
The invention provides a kind of adjacent hydroxy stibene derivative and its preparation method and application, this preparation method can the trans product of narrow spectrum generation, and reaction yield is high.Meanwhile, cell experiment (Colo-205, MDA-468, HT-29 and MGC80-3) shows that wherein a part of compound has the anti-tumor activity being obviously better than trans-resveratrol.
A kind of trans adjacent hydroxy stibene derivative, structure is as shown in formula I:
In formula I, R
1, R
2be one or more alkyl, halogen, phenyl, hydroxyl, carbalkoxy, alkoxyl group, nitro or cyano group independently;
R
3for H, alkyl or aryl.Cell experiment shows that this class formation has good anti-tumor activity, especially for these cells of Colo-205, MDA-468, HT-29 and MGC80-3.
As preferably, described R
1, R
2be nitro, methyl, methoxyl group, bromine, hydroxyl or cyano group independently.
As further preferred, described trans adjacent hydroxy stibene derivative is selected from the one in following particular compound:
Present invention also offers a kind of preparation method of described trans adjacent hydroxy stibene derivative, it is characterized in that, comprise the steps: under rhodium catalyst and acetate existent condition, o-hydroxystyrene compounds and aryl boric acid react in a solvent, after having reacted, obtain described trans adjacent hydroxy stibene derivative through aftertreatment;
The structure of described o-hydroxystyrene compounds is as shown in formula II:
Described aryl boric acid structure is as shown in formula III:
Wherein, R
1, R
2and R
3definition as mentioned before.
In reaction process, Rh (III) first inserts in the C-B key in aryl boric acid, then the C-Rh-O key of ring-type is formed with the hydroxyl effect in o-hydroxystyrene compounds, then vinyl is inserted into C-Rh key generation cationoid reaction, finally reduce elimination, form final trans adjacent hydroxy stibene compounds.
As preferably, described rhodium catalyst is [Cp*RhCl
2]
2or [Cp*Rh (OAc) (CAS:12354-85-7)
2]
2, consumption is 1 ~ 2% of the molar weight of described o-hydroxystyrene compounds, and this kind of rhodium catalyst is good to the suitability of the substrate in the present invention, and catalytic efficiency is high.
As preferably, described acetate is neutralized verdigris, and consumption is 200 ~ 300% of the molar weight of described o-hydroxystyrene compounds.
As preferably, described R
1for alkyl, halogen or alkoxyl group, now, o-hydroxystyrene compounds easily obtains, and the reactive behavior of substrate is higher.
As preferably, described R
2for hydrogen, methyl, methoxyl group, hydroxyl, halogen, now, the activity of reaction is higher.
Described o-hydroxystyrene compounds can be prepared with reference to existing method, specifically can see document (J.Am.Chem.Soc.2014,136,834).
As preferably, described o-hydroxystyrene compounds and the mol ratio of aryl boric acid are 1:1.5 ~ 2.5, and the latter is excessive slightly, are convenient to react carry out more thorough.
As preferably, described solvent is at least one in water, methyl alcohol, ethanol, and these solvents are all polar aprotic solvent, and as further preferably, described solvent is methyl alcohol.
As preferably, the temperature of reaction is 5 ~ 80 DEG C, and temperature of reaction is too high, and aryl boric acid compounds easily divides and depolymerizes, and temperature of reaction is too low, can reduce the transformation efficiency of reactant, and as further preferably, the temperature of reaction is room temperature.
In the present invention, the time of reaction can be monitored by TLC, at room temperature stirs reaction in 0.5-4 hour and can occur completely.
Present invention also offers a kind of described trans adjacent hydroxy stibene derivative and prepare the application in antitumor drug.
As preferably, described antitumor drug is for suppressing colon cancer cell, breast cancer cell or stomach cancer cell.Described trans adjacent hydroxy stibene derivative generally has good restraining effect to the growth of these cancer cells.
Compared with the existing technology, beneficial effect of the present invention is embodied in: reaction substrate is easy to get, easy to operate, and this trans adjacent hydroxy stibene analog derivative yield be obtained by reacting is high, and the required mild condition of reaction, the reaction times is short.
Accompanying drawing explanation
Fig. 1 is the obtained product of embodiment 1
1hNMR spectrogram;
Fig. 2 is the obtained product of embodiment 1
13cNMR spectrogram;
Fig. 3 is the obtained product of embodiment 2
1hNMR spectrogram;
Fig. 4 is the obtained product of embodiment 2
13cNMR spectrogram;
Fig. 5 is the single crystal structure figure of the product that embodiment 1 obtains.
Embodiment
Be described in detail the present invention below in conjunction with specific embodiment, these embodiments, just for explaining technical scheme of the present invention, are not form any restriction to the present invention.
Reactant o-hydroxystyrene compounds used in the present invention can be adopted and be prepared with the following method:
With R
1and R
3all select H to be example, concrete operations are as follows: in three mouthfuls of reaction flasks, add methyl triphenyl phosphonium iodide and potassium tert.-butoxide, vacuumize, argon replaces, squeezes into tetrahydrofuran (THF) with syringe, is put in 0 DEG C of environment and stirs, drip salicylic aldehyde, drip off and be put in stirred at ambient temperature 12h, use saturated ammonium chloride cancellation, decompression rotary evaporation removes tetrahydrofuran (THF), by ether extraction, salt is washed, dry, crosses post (PE/EA) and obtains product.
Embodiment 1
In 5mL single port reaction flask, add 60mg (0.3mmol) 5-bromine o-hydroxystyrene (1.0eq), 64mg3,5-dimethylphenyl boronic acid, [Cp*RhCl
2]
23.7mg (2%), CuOAc120mg (2.0eq).Add 3mL methyl alcohol, in stirred at ambient temperature.After about 2h, TLC detection reaction is complete, adds about 500mg silica gel, steams solvent, solidification, solid loading, with sherwood oil and ethyl acetate for eluent carries out pillar layer separation.Obtain product 52mg, yield 86%.Reaction formula is as follows:
Product physical properties and spectral data as follows: white solid; Fusing point: 90-92 DEG C;
1hNMR (CDCl
3, 400MHz), δ: 7.68 (d, J=2.4Hz, 1H), 7.31-7.26 (m, 2H), 7.20 (s, 2H), 7.09 (d, J=16.4Hz, 1H), 6.99 (s, 1H), 6.75 (d, J=8.4Hz, 1H), 5.08 (s, 1H), 2.40 (s, 6H);
13cNMR (CDCl
3, 100MHz), δ: 152.1,138.3,137.0,131.8,131.1,130.0,129.7,127.2.124.7,121.1,117.7,113.5,21.4; IR (KBr) v:3509,3022,2917,1595,1486,1409,1313,1263,1099,966,860,801,688cm
-1; HRMS (EI) (m/z): calcdforC
16h
15brO (M
+), 302.0306; Found, 302.0306. product
1hNMR spectrogram is shown in Fig. 1,
13cNMR spectrogram is shown in Fig. 2, and single crystal structure figure is shown in Fig. 5.
Embodiment 2
In 5mL single port reaction flask, add 30mg (0.2mmol) 4-methoxyl group o-hydroxystyrene (1.0eq), 89mg3,4,5-Three methyl Benzene boric acid, [Cp*RhCl
2]
22.48mg (2%), CuOAc80mg (2.0eq).Add 2mL methyl alcohol, in stirred at ambient temperature.After about 2h, TLC detection reaction is complete, adds about 500mg silica gel, steams solvent, solidification, solid loading, with sherwood oil and ethyl acetate for eluent carries out pillar layer separation.Obtain product 38mg, yield 60%.Reaction formula is as follows:
Product physical properties and spectral data as follows: Oil;
1hNMR (CDCl
3, 400MHz), δ: 7.42 (d, J=8.4Hz, 1H), 7.21 (d, J=16.4Hz, 1H), 6.92 (d, J=16.0Hz, 1H), 6.70 (s, 2H), 6.51 (dd, J
1=8.8Hz, J
2=2.8Hz, 1H), 6.41 (d, J=2.4Hz, 1H), 6.02 (br, s, 1H), 3.88 (s, 6H), 3.87 (s, 3H), 3.76 (s, 3H);
13cNMR (CDCl
3, 100MHz), δ: 160.3,154.5,153.4,137.4,134.1,128.0,127.7,122.7,117.7,106.9,103.4,101.9,61.1,56.2,55.4; IR (KBr) v:3404,2938,2837,1615,1580,1508,1463,1421,1286,1238,1127,1000,960,817,782cm
-1; HRMS (EI) (m/z): calcdforC
18h
20o
5(M
+), 316.1311; Found, 316.1310.
Product
1hNMR spectrogram is shown in Fig. 3,
13cNMR spectrogram is shown in Fig. 4.
Embodiment 3 ~ 23
The preparation method of embodiment 3 ~ 23 is identical with embodiment 1, and difference is two raw materials to replace to other analog structures, and the product structure obtained lists in table 1.
The product structure of embodiment 3 ~ 23
Cellular sensitivity is tested
Experimental principle: MTT analytical method, based on living cells metabolize thing reductive agent MTT tetrazolium bromide, utilizes microplate reader to measure the optical density(OD) OD value at 490nm place, to reflect number of viable cells, thus measures the fragmentation effect of compound on tumor cell.
Experimental procedure:
(1) collect logarithmic phase cell, adjustment concentration of cell suspension, every hole adds 100 μ L, and bed board makes cell density to be measured be 1000-10000/hole (the aseptic PBS of marginal pore fills);
(2) 96 orifice plates are placed on 5%CO
2, hatch in 37 DEG C of incubators, be paved with at the bottom of hole to cell monolayer, add the medicine (i.e. the compound of contrast Resveratrol and embodiment 1 ~ 23) of concentration gradient.In principle, after cell attachment, get final product dosing, or two hours, or time half a day, this experiment at bed board evening before that day, dosing in morning next day.A general 5-7 gradient, every hole 5 μ L, if 3-5 parallel hole;
(3) 5%CO
2, hatch 16-48 hour for 37 DEG C, observe under inverted microscope;
(4) every hole adds 20 μ LMTT solution (5mg/ml, i.e. 0.5%MTT), continues to cultivate 4h.If medicine and MTT can react, can first centrifugal after discard nutrient solution, carefully with PBS rush 2-3 all over after, then add the nutrient solution containing MTT;
(5) stop cultivating, carefully suck nutrient solution in hole;
(6) every hole adds 150 μ L dimethyl sulfoxide (DMSO), puts low-speed oscillation 10min on shaking table, crystallisate is fully dissolved.Enzyme-linked immunosorbent assay instrument measures the light absorption value in each hole at 490nm place.The result obtained is as shown in table 2.
Table 2 compound structure and activity gather
In table 2, "---" represents active suitable with Resveratrol, or lower than Resveratrol.
Claims (7)
1. the preparation method of a trans adjacent hydroxy stibene derivative, it is characterized in that, comprise the steps: under rhodium catalyst and acetate existent condition, o-hydroxystyrene compounds and aryl boric acid react in a solvent, after having reacted, obtain described trans adjacent hydroxy stibene derivative through aftertreatment;
The structure of described o-hydroxystyrene compounds is as shown in formula II:
Described aryl boric acid structure is as shown in formula III:
The structure of described trans adjacent hydroxy stibene derivative is as shown in formula I:
In formula I, R
1, R
2be one or more alkyl, halogen, phenyl, hydroxyl, carbalkoxy, alkoxyl group, nitro or cyano group independently;
R
3for H, alkyl or aryl.
2. the preparation method of trans adjacent hydroxy stibene derivative according to claim 1, is characterized in that, described R
1, R
2be nitro, methyl, methoxyl group, bromine, hydroxyl or cyano group independently.
3. the preparation method of trans adjacent hydroxy stibene derivative according to claim 1 and 2, it is characterized in that, described rhodium catalyst is [Cp*RhCl
2]
2or [Cp*Rh (OAc)
2]
2, consumption is 1 ~ 2% of the molar weight of described o-hydroxystyrene compounds.
4. the preparation method of trans adjacent hydroxy stibene derivative according to claim 1 and 2, it is characterized in that, described acetate is neutralized verdigris, and consumption is 200 ~ 300% of the molar weight of described o-hydroxystyrene compounds.
5. the preparation method of trans adjacent hydroxy stibene derivative according to claim 1 and 2, is characterized in that, described o-hydroxystyrene compounds and the mol ratio of aryl boric acid are 1:1.5 ~ 2.5.
6. the preparation method of trans adjacent hydroxy stibene derivative according to claim 1 and 2, it is characterized in that, described solvent is at least one in water, methyl alcohol, ethanol.
7. the preparation method of trans adjacent hydroxy stibene derivative according to claim 1 and 2, is characterized in that, the temperature of reaction is 5 ~ 80 DEG C.
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| KR101935793B1 (en) * | 2016-09-30 | 2019-01-08 | (주)나노믹스 | Stilbene derivatives and preparation method thereof |
| KR20180036522A (en) | 2016-09-30 | 2018-04-09 | (주)나노믹스 | Stilbene derivatives and preparation method thereof |
| CN110683930B (en) * | 2019-10-28 | 2022-03-22 | 玉林师范学院 | Synthesis method of trans-stilbene |
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| CN103417518A (en) * | 2013-09-06 | 2013-12-04 | 四川大学 | Application of oxidized resveratrol for preparing tumor treatment drugs |
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| CN103417518A (en) * | 2013-09-06 | 2013-12-04 | 四川大学 | Application of oxidized resveratrol for preparing tumor treatment drugs |
Non-Patent Citations (2)
| Title |
|---|
| Synthesis and biological evaluation of novel (E) stilbene-based antitumor agents;Rene Csuk, et al.;《European Journal of Medicinal Chemistry》;20120618;第54卷;第669-678页 * |
| Two new diphenylethylenes from Arundina graminifolia and their cytotoxicity;Yin-Ke Li, et al.;《Korean Chem. Soc.》;20131231;第34卷(第11期);第3257-3260页 * |
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