CN101284779B - Preparation method of (E)-4-(beta-bromovinyl)phenol ester - Google Patents
Preparation method of (E)-4-(beta-bromovinyl)phenol ester Download PDFInfo
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- CN101284779B CN101284779B CN2008100385634A CN200810038563A CN101284779B CN 101284779 B CN101284779 B CN 101284779B CN 2008100385634 A CN2008100385634 A CN 2008100385634A CN 200810038563 A CN200810038563 A CN 200810038563A CN 101284779 B CN101284779 B CN 101284779B
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Abstract
The invention belongs to the technology field of drug intermediate and high molecular material monomer synthesis, in particular to a method for preparing (E)-4-(Beta-vinyl bromide) phenol ester. Benzene solvent, (E)-4-(Beta-vinyl bromide) carbolic acid, carboxylic acid and dimethylaminopyridine are respectively added into a flask, magnetic stirring is performed for 5 to 20 minutes at room temperature, then N,N'- carbodicyclo hexylimide is added for reaction at room temperature, and the reaction is finished after 2 to 24 hours. The benzene solvent is steamed off through pressure reduction, column chromatographic separation purification is performed to the residue by adopting ethyl acetate/benzinum purificatum as the eluate to obtain the required product, wherein, the mol ratio of the benzene solvent to the (E)-4-(Beta-vinyl bromide) carbolic acid is 50 to 200:1, the mol ratio of the carboxylic acid (RCO2H) to the (E)-4-(Beta-vinyl bromide) carbolic acid is 1 to 1.5:1, the mol ratio of the dimethylaminopyridine (DMAP) to the (E)-4-(Beta-vinyl bromide) carbolic acid is 0.1 to 1.5:1, and the mol ratio of the N,N'- carbodicyclo hexylimide (DCC) to the (E)-4-(Beta-vinyl bromide) carbolic acid is 1 to 1.2:1. The (E)-4-(Beta-vinyl bromide) phenol ester synthesized through the method takes the ester structure and the monobrom ethylene units as the reaction active groups, which can be used for the development of medicines, pesticides, natural products with biological activities, high molecular materials and functional materials.
Description
Technical field
The invention belongs to pharmaceutical intermediate, macromolecular material monomer synthesis technical field, be specifically related to the preparation method of a kind of (E)-4-(beta-bromovinyl) phenol ester.
Background technology
β-haloolefin and derivative thereof are the very useful synthetic intermediates of a class, it can pass through excessive metalcatalyzing linked reactions such as Stille, Suzuki, Heck, Sonogashira, Buchwald and form carbon-to-carbon, carbon-heterodesmic, thereby Stereoselective synthesizes olefin(e) compound, thereby has a wide range of applications in medicine, agricultural chemicals, natural product, polymer and functional materials etc. are synthetic.In the last few years, along with the fast development of Organometallic Chemistry and the quickening of medicament research and development paces, the β-haloolefin particularly purposes of β-bromstyrol derivative was increasingly extensive.
Three-dimensional single-minded (E)-β-bromstyrol and derivative thereof are stereoselective synthetic important organic synthesis intermediates with substituted olefine
[1], also be the precursor of important synthetic alkynes
[2]By various organo-metallic linked reactions, they also are widely used in the synthetic of natural product and antibacterials.
The classical main synthetic method of (E)-β-bromstyrol comprises:
(1) be raw material with 1,1 dibromide
Abbas
[3]Deng discovery, be solvent with DMF, with the O of Hirao, O '-dimethyl phosphine acid esters/triethylamine system optionally reduces 1, and 1-two bromo-2-vinylbenzene obtain three-dimensional single-minded (E)-bromstyrol under 70 ℃, be shown below:
R＝alkyl，aryl，alkenyl，heterocylic
Limitation such as the method for the synthetic E-β-bromstyrol of Abbas exists the reaction times to grow, phosphoric acid ester is excessive, productive rate is lower.The inventor
[4]Use microwave induced method to obtain satisfied result.From 1,1-two bromo-1-alkene set out, and use (C
2H
5O)
2P (O) H/EtONa/EtOH system, microwave irradiation is 1min only, can obtain the E-β-bromstyrol series matter of high yield (90-99%) and selectivity (E:94-99.5%), is shown below:
(2) metal-halogen replacement(metathesis)reaction
Petasis etc.
[5]With NBS is bromide reagent, ene boric acid is converted into corresponding β-bromstyrol in second cyanogen.Reaction is at room temperature carried out, the condition milder, and it is also convenient to operate, and does not need exogenously added alkali to finish the elimination process, as shown below:
This method needs expensive metal reagent, thereby has limited its application.
(3) with the aromatic aldehyde be raw material
This method is with aromatic aldehyde and CHX
3(X=Cl, Br I) are raw material, finish reaction with organic chromium (II) reagent.With THF is solvent, phenyl aldehyde, CrCl
2And CHBr
3At 25 ℃ of reaction 1.5h, yield is 32%-43%.If use CrCl
2And LiAlH
4Mixture (1.05eq) replaced C rCl
2(6eq) react 1h down, can obtain (E)-β-bromstyrol (70%, 95/5), be shown below at 50 ℃:
X＝Cl，Br
This method will be used heavy metal, and is unfriendly and yield is not high to environment.
(4) be raw material with the substituted cinnamic acid dibromide
The inventor
[6]First microwave reaction is used for this route of synthesis, uses triethylamine/N, the dinethylformamide system is finished α quickly and easily, the decarboxylation debrominate of beta-unsaturated carboxylic acid dibromide, and the solid property selected ground generates 1-bromo-1-alkene.Microwave not only can fast reaction speed, obtains high stereoselectivity and yield, what is more important, this method also is applicable to the aromatic alpha that contains the ortho para nitro functions, β-unsaturated aromatic carboxylic acid and aliphatic alpha, β-unsaturated aromatic carboxylic acid is shown below:
Also find in the research subsequently
[7], change solvent and additive, trans-3-aryl-2 in the AgOAc/AcOH system, 3-dibromo-propionic acid microwave irradiation then can stereoselective synthetic E-β-bromstyrol series compound.Productive rate reach as high as 96% (E:＞97%), be shown below:
(5) Hunsdiecker reaction
Jorgensen etc.
[8]Reported that at first the styracin series matter is at PhIO or PhI (OAc)
2Effect provides Br by NBS down
+The oxidative decarboxylation halogenating reaction.This reaction is with CH
3CN/H
2O is a solvent, can obtain β-bromstyrol series matter that two key configurations keep at 60 ℃ of following 0.5h.According to the electronic effect difference of para-orienting group on the phenyl ring, productive rate is therefrom waited until higher.And the productive rate of Z-meat silicic acid and stereoselectivity are lower than corresponding E-isomer, are shown below:
The inventor
[9]With the synthetic β of microwave method-bromstyrol series matter.Use the lithium acetate of catalytic amount, the N-bromo-succinimide (NBS) of equivalent and (E)-α, β-unsaturated aromatic carboxylic acid is used microwave irradiation 1 minute in acetonitrile-water (92-8) mixed solvent, can finish the decarboxylation bromo and highly-solid selectively ground generation (E)-β-bromstyrol series matter, productive rate all is higher than the report of Sujit Roy etc., is shown below:
Ar＝C
6H
5，4-CH
3C
6H
4，4-CH
3OC
6H
4?et?al.
Reference:
1?Dehli?J?R，Legros?J，Bolm?C.Chem?Commun，2005，8，973。
2?Matveeva?E?D，Erin?A?S，Kurts?A?L.Russ.J.Org.Chem，1997，33，1065。
3?Abbas?S，Hayes?C?J，Worden?S.Tetrahedron?Lett，2000，41，3215。
4?Kuang?C?X，Senboku?H，Tokuda?M.Tetrahedron，2002，58，1491。
5?Petasis?N?A，Zavialov?I?A.Tetrahedron?Lett，1996，37，567。
6?Kuang?C?X，Senboku?H，Tokuda?M.Tetrahedron?Lett，2001，42，3893。
7?Kuang?C?X，Senboku?H，Tokuda?M.Tetrahedron，2005，61，637。
8?Graven?A，Jorgensen?K?A，Dahl?S，et?al.J.Org.Chem，1994，59，3543。
9?Kuang?C?X，Senboku?H，Tokuda?M.Synlett，2000，10，1439。
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of (E)-4-(beta-bromovinyl) phenol ester.
The preparation method of (E)-4-(beta-bromovinyl) phenol ester that the present invention proposes, (E)-4-(beta-bromovinyl) phenol ester structural formula is as follows:
Wherein, R is an alkyl or aryl, and concrete synthetic route is as follows:
Concrete preparation process is as follows:
In flask, add solvent benzol, (E)-4-(beta-bromovinyl) phenol, carboxylic acid (RCO respectively
2H), right-Dimethylamino pyridine (DMAP), at room temperature magnetic agitation 5-20 minute, add N then, N '-dicyclohexylcarbodiimide (DCC), under the room temperature reaction 2-24 hour the reaction promptly finish.Pressure reducing and steaming solvent benzol, residue are that leacheate carries out the column chromatography for separation purification with the ethyl acetate/petroleum ether, promptly get desired product; Wherein, solvent benzol with (E)-4-(beta-bromovinyl) phenol mol ratio is 50-200: 1, carboxylic acid (RCO
2H) with (E)-4-(beta-bromovinyl) phenol mol ratio is 1-1.5: 1, right-Dimethylamino pyridine (DMAP) with (E)-4-(beta-bromovinyl) phenol mol ratio is 0.1-1.5: 1, N, N '-dicyclohexylcarbodiimide (DCC) with (E)-4-(beta-bromovinyl) phenol mol ratio is 1-1.2: 1.
Among the present invention, in the described leacheate, the volume ratio of ethyl acetate and sherwood oil is 1: 4-1: 20.
Among the present invention, (E)-preparation method of 4-(beta-bromovinyl) phenol applied for Chinese patent, application number is 200710040775.1.
The present invention is synthetic building block with (E)-4-(beta-bromovinyl) phenol, obtains a series of (E)-4-(beta-bromovinyl) phenol ester functional compounds by esterification.Compare with existing method, the inventive method has economy, quick, high, the good selective of yield.Present method synthetic (E)-4-(beta-bromovinyl) phenol ester is a reaction active groups with ester structure and bromine ethylene unit, can be used for medicine, agricultural chemicals, the development of natural product, polymer and the functional materials of physiologically active is arranged.
Embodiment
Followingly further specify the present invention, but can not limit content of the present invention by embodiment.
Embodiment 1:(E)-preparation of 4-(beta-bromovinyl) phenol
Synthetic route is as follows:
The first step: this acrylic acid preparation of 4-hydroxyl
In the 50mL three-necked bottle of reflux condensing tube, thermometer is housed, add 0.611g (5mmol) 4-hydroxy benzaldehyde, 1.040g (10mmol) propanedioic acid, 10mL pyridine, 3 piperidines, be warming up to 80 ℃, magnetic agitation reaction 6 to 8 hours, TLC follows the tracks of and detects (developping agent is made in ethyl acetate/normal hexane/acetate=10/20/1).Reaction finishes postcooling to room temperature, is being neutralized to pH=2 with the cold hydrochloric acid of 6M, after filtration, frozen water and ethyl acetate washing, P
2O
5Vacuum-drying gets pale yellow powder 0.700g, i.e. (E)-4-(beta-bromovinyl) phenol, yield 92%.
Second step: (E)-the acrylic acid preparation of 3-(4-acetyl phenyl)
In the 25mL egg type bottle of calcium chloride tube is housed, add 0.761g (5mmol) (E)-4-(beta-bromovinyl) phenol, 5mL acetic anhydride, 0.5mL triethylamine, in 70 ℃ of reactions 2 hours, TLC followed the tracks of detection.Reaction adds water 15mL after finishing, and vigorous stirring is 0.5 hour under room temperature, and hepatitis B is decomposed fully, and system is muddy shape.Filter, filter cake is with 20mL water washing 3 times, through P
2O
5Vacuum-drying promptly gets pale yellow powder (E)-3-(4-acetyl phenyl) vinylformic acid 0.907g, yield 88%.
The 3rd step: (E)-preparation of 4-(beta-bromovinyl) phenylacetate
In 10mL reaction medium (9.5mL acetonitrile+0.5mL water), add 1.031g (5mmol) (E)-3-(4-acetyl phenyl) vinylformic acid, 0.934g (5.25mmol) N-bromo-succinimide, 0.05g (0.5mmol) Lithium Acetate, under 250 watts, carry out microwave reflection 1 minute.TLC follows the tracks of detection, and question response fully back divides three extractions with 200mL acetate acetic ester, and organic layer pressure reducing and steaming acetate acetic ester behind anhydrous sodium sulfate drying gets white powder 1.186g, i.e. (E)-4-(beta-bromovinyl) phenylacetate, yield 96%.
The 4th step: (E)-preparation of 4-(beta-bromovinyl) phenol
With 20mL contain 1.235g (5mmol) (E)-chloroformic solution of 4-(beta-bromovinyl) phenylacetate and the ethanolic soln that 10mL contains 0.68g (10mmol) sodium ethylate mix magnetic agitation reaction 3 minutes.Reaction finishes the back with 100mL chloroform diluting reaction system, adds hydrochloric acid and the vigorous stirring of 100mL2% again.Tell organic layer after leaving standstill, water layer extracts at twice with the 50mL chloroform, and organic layer merges, and promptly gets light brown solid 0.876g through being washed to neutrality, anhydrous sodium sulfate drying, pressure reducing and steaming chloroform successively, i.e. (E)-4-(beta-bromovinyl) phenol, yield 88%.
Embodiment 2:
In the exsiccant round-bottomed flask of 25mL, add 10mL (110mmol) benzene, 199mg (1mmol) (E)-4-(beta-bromovinyl) phenol, 156mg (1.05mmol) styracin, 12mg (0.1mmol) is right-Dimethylamino pyridine (DMAP), at room temperature magnetic agitation adds 206mg (1mmol) N after 8 minutes, N '-dicyclohexylcarbodiimide (DCC) carries out reaction in 24 hours and promptly finishes under the room temperature.Pressure reducing and steaming solvent, residue are with ethyl acetate: sherwood oil=1: 5-1: 9 is that leacheate carries out column chromatography for separation and purifies and promptly get (E)-4-(beta-bromovinyl) phenol laurate 323mg, and yield is 98%.Reaction and product characterization data are as follows:
White?solid；m.p.151.7-151.8℃.
IR(KBr)：1714，1276，1103，935，746cm
-1.
1H?NMR(300MHz，CDCl
3)：δ＝6.63(1H，d，J＝8.1Hz)，6.76(1H，d，J＝8.4Hz)，7.09-7.16(3H，m)，7.35(2H，d，J＝8.4Hz)，7.42-7.45(3H，m)，7.58-7.60(2H，m)，7.88(1H，d，J＝13.8Hz).
13C?NMR(75MHz，CDCl
3)：δ＝106.59，117.03，122.02，127.10，128.31，128.99，130.78，133.61，134.07，136.23，134.07，136.23，146.84，150.64，165.15.
Embodiment 3:
In the exsiccant round-bottomed flask of 25mL, add 12mL (130mmol) benzene, 199mg (1mmol) (E)-4-(beta-bromovinyl) phenol, 165mg (1.1mmol) to aldehyde radical phenol, 61mg (0.5mmol) right-Dimethylamino pyridine (DMAP), at room temperature magnetic agitation adds 227mg (1.1mmol) N after 10 minutes, N '-dicyclohexylcarbodiimide (DCC) carries out reaction in 22 hours and promptly finishes under the room temperature.Pressure reducing and steaming solvent, residue are with ethyl acetate: sherwood oil=1: 6-1: 10 is that leacheate carries out column chromatography for separation and purifies and promptly get (E)-4-(beta-bromovinyl) phenol to aldehyde radical phenol ester 305mg, and yield is 92%.Reaction and product characterization data are as follows:
White?solid；m.p.127.4-131.0℃.
IR(KBr)：1734，1266，1067，935，756cm
-1.
1H?NMR(300MHz，CDCl
3)：δ＝6.79(1H，d，J＝13.7Hz)，7.13(1H，d，J＝13.7Hz)，7.21(2H，d，J＝8.7Hz)，7.39(2H，d，J＝8.7Hz)，8.04(2H，d，J＝8.3Hz)，8.37(2H，d，J＝8.3Hz)，10.16(1H，s).
13C?NMR(75MHz，CDCl
3)：δ＝106.96，121.32，121.92，127.23，129.61，130.75，134.08，136.08，139.65，150.47，191.38.
Embodiment 4:
In the exsiccant round-bottomed flask of 25mL, add 15mL (160mmol) benzene, 199mg (1mmol) (E)-4-(beta-bromovinyl) phenol, 148mg (1.2mmol) nicotinic acid, 128mg (1.05mmol) is right-Dimethylamino pyridine (DMAP), at room temperature magnetic agitation adds 206mg (1mmol) N after 12 minutes, N '-dicyclohexylcarbodiimide (DCC) carries out reaction in 15 hours and promptly finishes under the room temperature.Pressure reducing and steaming solvent, residue are with ethyl acetate: sherwood oil=1: 4-1: 6 is that leacheate carries out column chromatography for separation and purifies and promptly get (E)-4-(beta-bromovinyl) phenol nicotinate 295mg, and yield is 97%.Reaction and product characterization data are as follows:
Light?yellow?solid；m.p.126.2-126.9℃.
IR(KBr)：1734，935，777cm
-1.
1H?NMR(300MHz，CDCl
3)：δ＝6.79(1H，d，J＝14.3Hz)，7.13(1H，d，J＝14.3Hz)，7.21(2H，d，J＝8.1Hz)，7.38(2H，d，J＝8.1Hz)，7.46-7.50(1H，t)，8.45(1H，d，J＝8.1Hz)，8.87(1H，d，J＝5.1Hz)，9.40(1H，s).
13C?NMR(75MHz，CDCl
3)：δ＝107.02，121.95，123.50，125.40，127.23，134.07，136.06，137.63，150.26，151.29，154.02，163.65。
Claims (2)
1. the preparation method of (E)-4-(beta-bromovinyl) phenol ester is characterized in that (E)-4-(beta-bromovinyl) phenol ester structural formula is as follows:
Concrete steps are as follows:
In flask, add solvent benzol, (E)-4-(beta-bromovinyl) phenol, carboxylic acid RCO respectively
2H, right-Dimethylamino pyridine, at room temperature magnetic agitation 5-20 minute, add N then, N '-dicyclohexylcarbodiimide, reaction reaction in 2-24 hour is promptly finished under the room temperature; Pressure reducing and steaming solvent benzol, residue are that leacheate carries out the column chromatography for separation purification with the ethyl acetate/petroleum ether, promptly get desired product; Wherein, solvent benzol with (E)-4-(beta-bromovinyl) phenol mol ratio is 50-200: 1, carboxylic acid RCO
2H with (E)-4-(beta-bromovinyl) phenol mol ratio is 1-1.5: 1, right-Dimethylamino pyridine with (E)-4-(beta-bromovinyl) phenol mol ratio is 0.1-1.5: 1, N, N '-dicyclohexylcarbodiimide with (E)-4-(beta-bromovinyl) phenol mol ratio is 1-1.2: 1; R is an alkyl or aryl.
2. the preparation method of (E)-4-according to claim 1 (beta-bromovinyl) phenol ester is characterized in that in the described leacheate that the volume ratio of ethyl acetate and sherwood oil is 1: 4-1: 20.
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| CN101070359A (en) * | 2007-05-17 | 2007-11-14 | 同济大学 | Method for preparing trans-4-(beta-bromoethyl) phenoxy-benzylic resin (I) |
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Non-Patent Citations (6)
| Title |
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| Chengfeng Ye et al..Structure-Dependent Oxidative Bromination of Unsaturated C-C Bonds Mediated by Selectfluor.J.Org.Chem.69 (24).2004,69((24)),8561-8563. |
| Chengfeng Ye et al..Structure-Dependent Oxidative Bromination of Unsaturated C-C Bonds Mediated by Selectfluor.J.Org.Chem.69 (24).2004,69((24)),8561-8563. * |
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