CN103193606B - Synthesis method of brominated phenolic compound - Google Patents
Synthesis method of brominated phenolic compound Download PDFInfo
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Abstract
The invention relates to a synthesis method of a brominated phenolic compound, belonging to the technical field of organic synthesis and solving the problems of the existing synthesis method of brominated phenolic compound, such as bad environmental protection property and low reaction efficiency. The synthesis method comprises the steps of: adding a phenol derivative, terpyridyl ruthenium chloride, sodium persulfate, a metal bromide and an organic solvent in a reaction container, stirring the mixture at room temperature under the condition of visible light irradiation to react to obtain reaction liquid, separating and purifying the reaction liquid to obtain the brominated phenolic compound. The synthesis method provided by the invention is simple to operate, a small dose of photocatalyst is used and can be recycled, the selected brominating agent and oxidant are low-toxic and even non-toxic, the reaction yield is high, environmentally-friendly, clean and facile visible light is used for irradiation during reaction, and a common filament lamp, an LED lamp or sunlight is used as a light source. The synthesis method provided by the invention is mainly used for synthesizing brominated phenolic compounds.
Description
Technical field
The invention belongs to organic synthesis field, be specifically related to the synthetic method of bromide phenol compound.
Background technology
Bromide phenol compound is the important organic compound of a class, and on the one hand, bromide phenol compound not only serves as important organic reaction intermediate in organic synthesis, has important application in dyestuff, material, medicine and agricultural chemicals etc. simultaneously in industrial production.On the other hand, scientific research in recent years finds, bromide phenol compound all shows good biological activity in anti-oxidant, anti-inflammatory, antitumor, antimicrobial, antithrombotic and biological food refusal etc., but the content in natural biology is large compared with low, separating difficulty, and the research therefore for the high-efficiency synthesis method of bromide phenol compound is essential.
Synthetic bromide is a lot of for the method for phenolic compound, however existing most synthetic method have adopt a large amount of toxic reagent (as bromine, Lewis acid etc.), produce strongly-acid, poisonous and volatile by product (mainly hydrogen bromide), atom utilization is low, reaction preference is poor and the defect such as severe reaction conditions.Therefore, seek to realize high yield, highly selective, green, simple operations the synthetic method of bromide phenol compound still have broad application prospects.
Summary of the invention
The present invention seeks to the problem that the synthetic method feature of environmental protection is poor and reaction yield is low in order to solve existing bromide phenol compound, and a kind of synthetic method of bromide phenol compound is provided.
The synthetic method of bromide phenol compound of the present invention joins in reaction vessel by phenol analog derivative, Tris(2,2'-bipyridyl) ruthenium (II) chloride, Sodium Persulfate, metal bromide and organic solvent, reaction solution is obtained by reacting as stirring at room temperature under radiation of visible light condition, reaction solution is again through aftertreatment separation and purification, complete the synthesis of bromide phenol compound, reaction expression is as follows:
Wherein Ar represents the aromatic base of non-heterocycle or the aromatic base with substituent non-heterocycle, R
1represent hydrogen base, alkyl, acyl group, alkoxyl group, alkylsulfonyl or silylation, MBr represents metal bromide, and hv represents the visible ray that incandescent light, LED or the sun produce.
The synthetic method of bromide phenol compound of the present invention take phenol analog derivative as substrate, metal bromide is bromizating agent, and Tris(2,2'-bipyridyl) ruthenium (II) chloride is photocatalyst, and Sodium Persulfate is oxygenant, visible ray is light source, carries out reaction to obtain bromide phenol compound under stirring at normal temperature illumination.
The present invention has following advantage in sum:
1, reaction conditions is gentle, and building-up process is carried out at ambient temperature and pressure, and order of addition(of ingredients) can be any, easy and safe to operate, simple.
2, reaction adopts radiation of visible light that is green, that clean, be easy to get, and common incandescent light, LED and sunlight all can be used as light source, for a kind of visible ray reacts, belong to Green Chemistry.
3, the photocatalyst consumption adopted in synthetic method is few and can recycle and reuse, the bromizating agent selected and oxygenant all belong to be easy to get, the cheap and mineral compound that low toxicity is even nontoxic, reaction cost is low.
4, reaction substrate phenol analog derivative is applied widely, and the substituting group on aryl can be different functional group, such as acyl group, alkoxyl group, alkylsulfonyl and silane group etc., simultaneously substituting group can be one, two even multiple.
5, the productive rate of reaction and selectivity all higher, when the aromatic ring of especially phenol derivatives being connected with the strong group of electron supplying capacity, reaction yield can up to 100%.Single bromination product of bromide phenol compound is more single, and when the substituting group on aromatic ring on reaction raw materials is Isosorbide-5-Nitrae replacement, selectivity can up to 100%.
Embodiment
Embodiment one: the synthetic method of present embodiment bromide phenol compound joins in reaction vessel by phenol analog derivative, Tris(2,2'-bipyridyl) ruthenium (II) chloride, Sodium Persulfate, metal bromide and organic solvent, reaction solution is obtained by reacting as stirring at room temperature under radiation of visible light condition, reaction solution is again through aftertreatment separation and purification, complete the synthesis of bromide phenol compound, reaction expression is as follows:
Wherein Ar represents the aromatic base of non-heterocycle or the aromatic base with substituent non-heterocycle, R
1represent hydrogen base, alkyl, acyl group, alkoxyl group, alkylsulfonyl or silylation, MBr represents metal bromide, and hv represents the visible ray that incandescent light, LED or the sun produce.
The raw materials used metal bromide of present embodiment, Tris(2,2'-bipyridyl) ruthenium (II) chloride, Sodium Persulfate and organic solvent all can be commercially available.
The metal bromide that above-mentioned synthetic method adopts is Potassium Bromide, lithiumbromide, Sodium Bromide, magnesium bromide or Calcium Bromide;
Above-mentioned synthetic method reactant phenol analog derivative and metal bromide are when single bromine substitution reaction, and molar ratio is 1:1, and when two bromine substitution reactions, molar ratio is 1:2;
The organic solvent that above-mentioned synthetic method adopts is acetonitrile, methyl alcohol, DMF, methylene dichloride or dimethyl sulfoxide (DMSO), and the consumption of organic solvent is the organic solvent that every mmole phenol analog derivative drips 1 ~ 2mL.
Last handling process described in above-mentioned synthetic method: filter, extract, concentrate and purifying, wherein concentrated employing air distillation or underpressure distillation concentrate; Purifying adopts thin-layer chromatography, column chromatography, preparative chromatography, underpressure distillation or the mode purifying bromide phenol compound product of recrystallization.
Present embodiment, when round-bottomed flask selected by reaction vessel, selects the rubber plug with needle tubing to clog round-bottomed flask, and wherein needle tubing is used for reaction system to communicate with outside air, thus prevents the volatilization of solvent.React as under radiation of visible light condition under stirring at room temperature, monitor the disappearance of reaction raw materials spot by TLC and indicate reaction end, obtain reaction solution.
The position that in the middle of the bromide phenol compound adopting present embodiment synthetic method to obtain, bromine replaces has regularity; such as: for single substituent phenol analog derivative; in single bromine substitution product, bromine atoms is preferentially in the contraposition of phenolic hydroxyl group, and in dibromo substitution product, bromine atoms is in ortho position and the contraposition of phenolic hydroxyl group; For 1,2 dibasic phenol analog derivative, single bromine replaces the contraposition being only in phenolic hydroxyl group; For 1,3 dibasic phenol analog derivative, single bromine replaces the contraposition or the ortho position that are only in phenolic hydroxyl group, and two replace the ortho position and the contraposition that are in phenolic hydroxyl group; For 1,4 dibasic phenol analog derivative, single bromine replaces the ortho position being only in phenolic hydroxyl group; When being greater than 2 and position difference for the substituting group number on phenol analog derivative phenyl ring or naphthalene nucleus, have above-mentioned regularity equally, the chemical structure of product bromide phenol compound can be predicted.
Embodiment two: present embodiment and embodiment one are phenyl or naphthyl unlike the aromatic base of non-heterocycle.Other step and parameter identical with embodiment one.
Embodiment three: present embodiment and embodiment one or two represent the aromatic base with substituent non-heterocycle unlike Ar, and wherein substituting group is one or more in alkyl, alkoxyl group, halogen.Other step and parameter identical with embodiment one or two.
Present embodiment Ar representative is with the aromatic base of substituent non-heterocycle, and substituting group can be one or more identical or different substituting group, when having multiple substituting group, and the separate or Cheng Huan of two adjacent substituting groups.
Embodiment four: one of present embodiment and embodiment one to three are Potassium Bromide, lithiumbromide, Sodium Bromide, magnesium bromide or Calcium Bromide unlike metal bromide.Other step and parameter identical with one of embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four are 0.01 ~ 0.05:1 unlike the mol ratio of Tris(2,2'-bipyridyl) ruthenium (II) chloride and phenol analog derivative.Other step and parameter identical with one of embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to five are 0.01 ~ 0.02:1 unlike the mol ratio of Sodium Persulfate and phenol analog derivative.Other step and parameter identical with one of embodiment one to five.
Embodiment seven: one of present embodiment and embodiment one to six are unlike phenol analog derivative and metal bromide when single bromine substitution reaction, and molar ratio is 1:1, and when two bromine substitution reactions, molar ratio is 1:2.Other step and parameter identical with one of embodiment one to six.
Embodiment eight: one of present embodiment and embodiment one to seven are acetonitrile, methyl alcohol, DMF, methylene dichloride or dimethyl sulfoxide (DMSO) unlike organic solvent.Other step and parameter identical with one of embodiment one to seven.
Embodiment nine: one of present embodiment and embodiment one to eight are the organic solvent that every mmole phenol analog derivative drips 1 ~ 2mL unlike the consumption of organic solvent.Other step and parameter identical with one of embodiment one to eight.
Embodiment ten: one of present embodiment and embodiment one to nine are concentrated by air distillation unlike last handling process, then enriched product are carried out underpressure distillation again after column chromatography for separation.Other step and parameter identical with one of embodiment one to nine.
Embodiment 11: one of present embodiment and embodiment one to ten are concentrated by underpressure distillation unlike last handling process, then enriched product are carried out recrystallization again after TLC separation.Other step and parameter identical with one of embodiment one to ten.
Embodiment 12: one of present embodiment and embodiment one to ten one are the incandescent light of l5W or the LED of 1W unlike visible light source.Other step and parameter identical with one of embodiment one to ten one.
Embodiment one: the present embodiment adds 2Omg (4-p-methoxy-phenyl) trimethylsilyl ethers in lOmL round-bottomed flask, take 24mg Sodium Persulfate again, 4mg Tris(2,2'-bipyridyl) ruthenium (II) chloride and 9mg lithiumbromide, drawing 2mL acetonitrile with syringe joins in round-bottomed flask, cover the rubber plug being inserted with syringe needle, under shining as lW blue led light, stirring at room temperature monitors reaction end by TLC, obtain reaction solution, again with sherwood oil after concentration of reaction solution: ethyl acetate volume ratio is that the eluent of 10:1 carries out column chromatography purification, complete the synthesis of the bromo-4-methoxyphenol of 2-, the structural formula of 2-bromo-4-methoxyphenol is as follows:
The 2-obtained bromo-4-methoxyphenol is light orange liquid, and productive rate is 74%, and its nuclear magnetic data is as follows:
1HNMR(40OMHz，CDCl
3):δ7.0l(d，J=2.88Hz，lH)，6.94(d，J=8.9lHz，lH)，6.78(dd，J=2.91，2.88Hz，lH)，5.23(s，lH)，3.75(s，3H).
13CNMR(lOOMHz，CDCl
3):δ153.83，146.53，116.85，116.33，115.35，109.92，55.99。
Embodiment two: the present embodiment adds 20mg (3-p-methoxy-phenyl) trimethylsilyl ethers in lOmL round-bottomed flask, take 24mg Sodium Persulfate again, 4mg Tris(2,2'-bipyridyl) ruthenium (II) chloride and 9mg lithiumbromide, drawing 2mL acetonitrile with syringe joins in round-bottomed flask, cover the rubber plug being inserted with syringe needle, under shining as lW blue led light, stirring at room temperature monitors reaction end by TLC, obtain reaction solution, again with sherwood oil after concentration of reaction solution: ethyl acetate volume ratio is that the eluent of 10:1 carries out column chromatography purification, complete the synthesis of the bromo-3-methoxyphenol of 4-, the structural formula of 4-bromo-3-methoxyphenol is as follows:
The 4-obtained bromo-3-methoxyphenol is light orange liquid, and productive rate is 96%, and its nuclear magnetic data is as follows:
lHNMR(40OMHz，CDCl
3）:δ7.34(d，J=8.52Hz，lH)，6.60(d，J=2.85Hz，lH)，6.42(dd，J=2.88，2.85Hz，lH)，5.49(s，lH)，3.77(s，3H).
l3CNMR(lOOMHz，CDCl
3):δ156.76，156.13，133.36，108.51，102.27，100.46，56.19。
Embodiment three: the present embodiment adds 2Omg (2-p-methoxy-phenyl) trimethylsilyl ethers in lOmL round-bottomed flask, take 24mg Sodium Persulfate again, 4mg Tris(2,2'-bipyridyl) ruthenium (II) chloride and 9mg lithiumbromide, drawing 2mL acetonitrile with syringe joins in round-bottomed flask, cover the rubber plug being inserted with syringe needle, under shining as lW blue led light, stirring at room temperature monitors reaction end by TLC, obtain reaction solution, again with sherwood oil after concentration of reaction solution: ethyl acetate volume ratio is that the eluent of 10:1 carries out column chromatography purification, complete the synthesis of the bromo-2-methoxyphenol of 4-, the structural formula of 4-bromo-2-methoxyphenol is as follows:
The light orange liquid of the 4-obtained bromo-2-methoxyphenol, productive rate is 92%, and its nuclear magnetic data is as follows:
lHNMR(40OMHz，CDCl
3）:δ7.00-6.97(m，2H)，6.80(d，J=8.24Hz，lH)，5.51(s，lH)，3.88(s，3H).
l3CNMR(lOOMHz，CDCl
3):δ147.23，144.91，124.19，115.75，114.18，111.57，56.16。
Embodiment four: the present embodiment adds 36mg (4-aminomethyl phenyl) trimethylsilyl ethers in lOmL round-bottomed flask, take 48mg Sodium Persulfate again, 4mg Tris(2,2'-bipyridyl) ruthenium (II) chloride and 18mg lithiumbromide, drawing 2mL acetonitrile with syringe joins in round-bottomed flask, cover the rubber plug being inserted with syringe needle, under shining as lW blue led light, stirring at room temperature monitors reaction end by TLC, obtain reaction solution, again with sherwood oil after concentration of reaction solution: ethyl acetate volume ratio is that the eluent of 15:1 carries out column chromatography purification, complete the synthesis of 2-bromo-4-methylphenol, the structural formula of 2-bromo-4-methylphenol is as follows:
The 2-bromo-4-methylphenol obtained is light orange liquid, and productive rate is 90%, and its nuclear magnetic data is as follows:
lHNMR(40OMHz，CDCl
3）:δ7.27(s，lH)，7.0l(d，J=8.25Hz，lH)，6.9O(d，J=8.24Hz，lH)，5.37(s，lH)，2.27(s，lH).
l3CNMR(lOOMHz，CDCl
3):δ150.03，132.12，131.41，129.77，115.74，109.83，20.19。
Embodiment five: the present embodiment adds 2Omg (4-chloro-phenyl-) trimethylsilyl ethers in lOmL round-bottomed flask, take 24mg Sodium Persulfate again, 4mg Tris(2,2'-bipyridyl) ruthenium (II) chloride and 9mg lithiumbromide, drawing 2mL acetonitrile with syringe joins in round-bottomed flask, cover the rubber plug being inserted with syringe needle, under shining as lW blue led light, stirring at room temperature monitors reaction end by TLC, obtain reaction solution, again with sherwood oil after concentration of reaction solution: ethyl acetate volume ratio is that the eluent of 20:1 carries out column chromatography purification, complete the synthesis of the bromo-4-chlorophenol of 2-, the structural formula of 2-bromo-4-chlorophenol is as follows:
The 2-obtained bromo-4-chlorophenol is light orange liquid, and productive rate is 37%, and its nuclear magnetic data is as follows:
lHNMR(40OMHz，CDCl
3):δ7.46(d，J=2.06Hz，lH)，7.19(dd，J=2.44，2.43Hz，lH)，6.95(d，J=8.7lHz，lH)，5.58(s，lH).
13CNMR(lOOMHz，CDCl
3):δ151.20，131.59，131.35，129.23，116.89，116.05。
Embodiment six: the present embodiment adds 23mg (2-methoxyl group-3-ethylphenyl) trimethylsilyl ethers in lOmL round-bottomed flask, take 24mg Sodium Persulfate again, 4mg Tris(2,2'-bipyridyl) ruthenium (II) chloride and 9mg lithiumbromide, drawing 2mL acetonitrile with syringe joins in round-bottomed flask, cover the rubber plug being inserted with syringe needle, under shining as lW blue led light, stirring at room temperature monitors reaction end by TLC, obtain reaction solution, again with sherwood oil after concentration of reaction solution: ethyl acetate volume ratio is that the eluent of 20:1 carries out column chromatography purification, complete the synthesis of the bromo-4-ethyl of 2--6-methoxyphenol, the structural formula of 2-bromo-4-ethyl-6-methoxyphenol is as follows:
The 2-obtained bromo-4-ethyl-6-methoxyphenol is light orange liquid, and productive rate is 44%, and its nuclear magnetic data is as follows:
1HNMR(400MHz,cDCl
3):7.09(s,1H),6.71(s,1H),5.48(s,1H),3.87(s,3H),2.70-2.64(m,2H),1.21-1.17(t,J=15.04Hz,3H).
13CNMR(100MHz,CDC1
3):δ146.03,144.27,134.72,118.43,114.36,111.47,56.07,29.11,14.68。
Embodiment seven: the present embodiment adds 22mg2-trimethylsiloxy group naphthalene ether in 10mL round-bottomed flask, take 24m9 Sodium Persulfate again, 4mg Tris(2,2'-bipyridyl) ruthenium (II) chloride and 9mg lithiumbromide, drawing 2mL acetonitrile with note elbow device joins in round-bottomed flask, cover the rubber plug being inserted with syringe needle, under shining as 1W blue led light, stirring at room temperature monitors reaction end by TLC, obtain reaction solution, again with sherwood oil after concentration of reaction solution: ethyl acetate volume ratio is that the eluent of 15:1 carries out column chromatography purification, complete the synthesis of the bromo-beta naphthal of 1-, the structural formula of the bromo-beta naphthal of 1-is as follows:
The bromo-beta naphthal of the 1-obtained is light orange liquid, and productive rate is 96%, and its nuclear magnetic data is as follows:
lHNMR(400MHz，CDCl
3):δ8.23(d，J=8.60Hz，1H)，7.84-7.73(m，3H)，7.597(t，J=15.42Hz，1H)，7.40(t，J=15.05Hz，1H)，7.28(d，J=8.99Hz，1H)，4.04(s，1H).
13CNMR(100MHz，CDCl
3):δ153.79，133.16，129.86，128.97，128.05，127.75，126.16，124.34，113.68，108.73，57.09。
Embodiment eight: the present embodiment adds 20mg (3-p-methoxy-phenyl) trimethylsilyl ethers in 10mL round-bottomed flask, take 24mg Sodium Persulfate again, 4mg Tris(2,2'-bipyridyl) ruthenium (II) chloride and 18mg lithiumbromide, drawing 2mL acetonitrile with syringe joins in round-bottomed flask, cover the rubber plug being inserted with syringe needle, under shining as lW blue led light, stirring at room temperature monitors reaction end by TLC, obtain reaction solution, again with sherwood oil after concentration of reaction solution: ethyl acetate volume ratio is that the eluent of 10:1 carries out column chromatography purification, complete 2, the synthesis of the bromo-5-methoxyphenol of 4-bis-, 2, the structural formula of 4-bis-bromo-5-methoxyphenol is as follows:
Obtain 2,4-bis-bromo-5-methoxyphenols are faint yellow solid, and productive rate is 95%, and its nuclear magnetic data is as follows:
lHNMR(400MHz，CDCl
3):δ7.58(s，1H)，6.62(s，1H)，5.50(s，1H)，3.85(s，3H).
13CNMR(100MHz，CDCl
3):δ160.61，153.01，131.96，108.45，101.68，100.90，55.55。
Claims (7)
1. the synthetic method of a bromide phenol compound, it is characterized in that the synthetic method of bromide phenol compound joins in reaction vessel by phenol analog derivative, Tris(2,2'-bipyridyl) ruthenium (II) chloride, Sodium Persulfate, metal bromide and organic solvent, under radiation of visible light condition, stirring at room temperature is obtained by reacting reaction solution, reaction solution is again through aftertreatment separation and purification, complete the synthesis of bromide phenol compound, reaction expression is as follows:
Wherein Ar represents the aromatic base of non-heterocycle or the aromatic base with substituent non-heterocycle, R
1represent silylation, MBr represents metal bromide, and hv represents the visible ray that incandescent light, LED or the sun produce, and described organic solvent is acetonitrile, methyl alcohol, DMF, methylene dichloride or dimethyl sulfoxide (DMSO); When Ar represents the aromatic base with substituent non-heterocycle, substituting group is wherein one or more in alkyl, alkoxyl group, halogen;
Described metal bromide is Potassium Bromide, lithiumbromide, Sodium Bromide, magnesium bromide or Calcium Bromide.
2. the synthetic method of a kind of bromide phenol compound according to claim 1, is characterized in that the aromatic base of non-heterocycle is phenyl or naphthyl.
3. the synthetic method of a kind of bromide phenol compound according to claim 1, is characterized in that the mol ratio of Tris(2,2'-bipyridyl) ruthenium (II) chloride and phenol analog derivative is 0.01 ~ 0.05:1.
4. the synthetic method of a kind of bromide phenol compound according to claim 1, is characterized in that the mol ratio of Sodium Persulfate and phenol analog derivative is 0.01 ~ 0.02:1.
5. the synthetic method of a kind of bromide phenol compound according to claim 1, it is characterized in that phenol analog derivative and metal bromide are when single bromine substitution reaction, molar ratio is 1:1.
6. the synthetic method of a kind of bromide phenol compound according to claim 1, is characterized in that the consumption of organic solvent is the organic solvent that every mmole phenol analog derivative adds 1 ~ 2mL.
7. the synthetic method of a kind of bromide phenol compound according to claim 1, is characterized in that visible light source is the incandescent light of 15W or the LED of 1W.
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| Visible Light Photoredox Catalysis with Transition Metal Complexes:Applications in Organic Synthesis;Christopher K. Prier et al.,;《Chem. Rev.》;20130319;第113卷;5322−5363 * |
| Visible-light promoted bimetallic catalysis;Akiko Inagakia et al.,;《Coordination Chemistry Reviews》;20091112;第254卷;1220–1239 * |
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