CN103214328B - Synthesis method for alpha-bromo-aromatic ketone compounds - Google Patents
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Abstract
The invention relates to a synthesis method for alpha-bromo-aromatic ketone compounds, and aims at solving the problems of pollution to environment, no selectivity and low yield of the existing synthesis method for alpha-bromo-aromatic ketone compounds. The specific method comprises the following steps of: adding a bromination reagent and a photoreaction catalyst in aromatic ethylene oxide compounds; reacting in an organic solvent for 6-12 hours at a room temperature under the irradiation of a visible light; filtering and concentrating; and taking the mixed solution of petroleum ether and alpha-bromo-aromatic ketone in a volume ratio of (10-16):1 as an eluent, and performing silica gel column chromatography purification and separation to obtain the alpha-bromo-aromatic ketone compounds, namely, finishing the synthesis method for the alpha-bromo-aromatic ketone compounds. The synthesis method for the alpha-bromo-aromatic ketone compounds disclosed by the invention is applied to the field of chemical industry.
Description
Technical field
The present invention relates to a kind of synthetic method of alpha-brominated aromatic ketones compound.
Background technology
Alpha-brominated aromatic ketones compound is the important intermediate of the Minute Organic Synthesis chemical such as medicine and agricultural chemicals.Because it has high reaction activity, attracted increasing concern constructing as precursor fragment aspect complicated molecule, people also pay attention to the research of its synthetic method more.
The synthetic method of alpha-brominated aromatic ketones compound is a lot, and wherein most methods is to adopt bromine or hydrogen bromide, as bromide reagent, the alpha-position of corresponding aromatic ketone is carried out to bromo.Yet, the use of such bromide reagent is but restricted day by day, this is due to its toxicity, strong volatility and pungency, to the safety issue in the corrodibility of equipment, production and transportation and produce a large amount of acid waste gas and can produce and pollute greatly and destroy environment, inevitably can threaten the harmonious development of human society, productive rate is only 50% left and right, and can generate monobromo simultaneously and replace and dibromo substitution product, the poor selectivity of reaction.Therefore, use the free of contamination bromide reagent of low toxicity, seek a kind of environmental protection, synthetic method simple to operate and that have an alpha-brominated aromatic ketones compound of selectivity, high yield conforms with people's demand.
Summary of the invention
The present invention will solve the synthetic method of existing alpha-brominated aromatic ketones compound environment is had to the low problem of pollution, poor selectivity and productive rate, and a kind of synthetic method of alpha-brominated aromatic ketones compound is provided.
The synthetic method of a kind of alpha-brominated aromatic ketones compound of the present invention, by following steps, undertaken: in aromatic epoxy ethane compound, add bromide reagent and photoresponse catalyzer, then under radiation of visible light, room temperature reaction 6～12h in organic solvent, then filtering also concentration of reaction solution extremely does, using volume ratio as (10～16): 1 sherwood oil: the mixing solutions of ethyl acetate is as eluent again, carry out purification by silica gel column chromatography separation, obtain alpha-brominated aromatic ketones compound, complete the synthetic method of alpha-brominated aromatic ketones compound, wherein bromide reagent is carbon tetrabromide or metal bromide, photoresponse catalyzer is Tris(2,2'-bipyridyl) ruthenium (II) chloride, wherein the mol ratio of aromatic epoxy ethane compound and bromide reagent is 1: (1.1～1.5), the mol ratio of aromatic epoxy ethane compound and photoresponse catalyzer is 1: (0.01～0.05).
The present invention can react at normal temperatures and pressures, and reaction conditions is gentle, and without strict, except water treatment and protection of inert gas, order of addition(of ingredients) is any, simple to operation.Reaction adopts the visible ray that cleans, is easy to get as energy derive, and the incandescent light of family expenses, LED lamp and sunlight all can be used as light source, cleanliness without any pollution; Carbon tetrabromide or metal bromide that the bromide reagent adopting is low toxicity, cheap and easy to get, be easy to feed in raw material, cocatalyst Sodium Persulfate is cheaply easy to get and is pollution-free; Photocatalyst consumption is few and can recycling.And reaction substrate of the present invention is applied widely, can utilize the high yield of different aromatic epoxy ethane substrate realization responses, such as alkyl, ketone group, ester group and aromatic group etc.Productive rate of the present invention and selectivity are all higher, and partial reaction yield can be up to more than 90%, and generates single bromination product, and the product replacing without dibromo generates; ; Whole reaction safety and environmental protection, cost is low, and economic benefit is high, belongs to green chemistry process.
Embodiment
Embodiment one: the synthetic method of a kind of alpha-brominated aromatic ketones compound of present embodiment, by following steps, undertaken: in aromatic epoxy ethane compound, add bromide reagent and photoresponse catalyzer, then under radiation of visible light, room temperature reaction 6～12h in organic solvent, then filtering also concentration of reaction solution extremely does, using volume ratio as (10～16): 1 sherwood oil: the mixing solutions of ethyl acetate is as eluent again, carry out purification by silica gel column chromatography separation, obtain alpha-brominated aromatic ketones compound, complete the synthetic method of alpha-brominated aromatic ketones compound, wherein bromide reagent is carbon tetrabromide or metal bromide, photoresponse catalyzer is Tris(2,2'-bipyridyl) ruthenium (II) chloride, wherein the mol ratio of aromatic epoxy ethane compound and bromide reagent is 1: (1.1～1.5), the mol ratio of aromatic epoxy ethane compound and photoresponse catalyzer is 1: (0.01～0.05).
The reaction formula of present embodiment is:
Present embodiment is suitable for all aromatic epoxy ethane compounds.
Present embodiment can be reacted at normal temperatures and pressures, and reaction conditions is gentle, and without strict, except water treatment and protection of inert gas, order of addition(of ingredients) is any, simple to operation.Reaction adopts the visible ray that cleans, is easy to get as energy derive, and the incandescent light of family expenses, LED lamp and sunlight all can be used as light source, cleanliness without any pollution; Carbon tetrabromide or metal bromide that the bromide reagent adopting is low toxicity, cheap and easy to get, be easy to feed in raw material, cocatalyst Sodium Persulfate is cheaply easy to get and is pollution-free; Photocatalyst consumption is few and can recycling.And the reaction substrate of present embodiment is applied widely, can utilize the high yield of different aromatic epoxy ethane substrate realization responses, such as alkyl, ketone group, ester group and aromatic group etc.The productive rate of present embodiment and selectivity are all higher, and partial reaction yield can be up to more than 90%, and generates single bromination product, and the product replacing without dibromo generates; Whole reaction safety and environmental protection, cost is low, and economic benefit is high, belongs to green chemistry process.
Embodiment two: present embodiment is different from embodiment one is that bromide reagent is while being metal bromide, in aromatic epoxy ethane compound, add cocatalyst Sodium Persulfate, wherein the mol ratio of aromatic epoxy ethane compound and Sodium Persulfate is 1: (1～2).Other steps and parameter are identical with embodiment one.
Embodiment three: present embodiment is different from embodiment one or two is that the mol ratio of aromatic epoxy ethane compound and bromide reagent is 1: (1.1～1.2).Other steps and parameter are identical with embodiment one or two.
Embodiment four: present embodiment is different from one of embodiment one to three is that the mol ratio of aromatic epoxy ethane compound and photoresponse catalyzer is 1: (0.02～0.04).Other steps and parameter are identical with one of embodiment one to three.
Embodiment five: what present embodiment was different from one of embodiment one to four is that organic solvent is acetonitrile, methyl alcohol or DMF, consumption is the organic solvent that every mmole aromatic epoxy ethane compound is used 5-10 milliliter.Other steps and parameter are identical with one of embodiment one to four.
Embodiment six: what present embodiment was different from one of embodiment one to five is that visible ray is incandescent light, LED lamp or sunlight.Other steps and parameter are identical with one of embodiment one to five.
By following verification experimental verification beneficial effect of the present invention:
Test 1, a kind of synthetic method of alpha-brominated aromatic ketones compound, by following steps, undertaken: in reaction flask, add 45.3mg2-(4-p-methoxy-phenyl)-3-phenyl ethylene oxide, 99.5mg carbon tetrabromide and 7.5mg Tris(2,2'-bipyridyl) ruthenium (II) chloride catalyzer, then with syringe, drawing 2mL acetonitrile joins in reaction flask, the rubber plug that is inserted with syringe needle is beyond the Great Wall placed under radiation of visible light, room temperature reaction 7h, then filtering also concentration of reaction solution extremely does, the sherwood oil that the volume ratio of usining is again 10: 1: the mixing solutions of ethyl acetate is as eluent, carry out purification by silica gel column chromatography separation, obtain the bromo-2-of 2-(4-p-methoxy-phenyl)-1-methyl phenyl ketone, complete the synthetic method of alpha-brominated aromatic ketones compound.Wherein the structural formula of the bromo-2-of 2-(4-p-methoxy-phenyl)-1-methyl phenyl ketone is:
This tests the bromo-2-of synthetic 2-(4-p-methoxy-phenyl)-1-methyl phenyl ketone is light yellow solid, and productive rate is 92%, and its nuclear magnetic data is:
1h NMR (400MHz, CDCl
3): δ 7.98 (d, J=7.8Hz, 2H), 7.56 (t, J=7.4Hz, 1H), 7.49-7.42 (m, 4H), 6.89 (d, J=8.7Hz, 2H), 6.40 (s, 1H), 3.80 (s, 3H).
13c NMR (100MHz, CDCl
3): δ 191.2,160.3, and 134.3,133.7,130.6,129.2,128.9,127.9,114.6,55.4,51.4.
Test 2, a kind of synthetic method of alpha-brominated aromatic ketones compound, by following steps, undertaken: in reaction flask, add 32.8mg2-(4-p-methoxy-phenyl)-3-methyl oxirane, 26mg lithiumbromide, 90mg Sodium Persulfate and 7.5mg Tris(2,2'-bipyridyl) ruthenium (II) chloride catalyzer, then with syringe, drawing 2mL acetonitrile joins in reaction flask, the rubber plug that is inserted with syringe needle is beyond the Great Wall placed under radiation of visible light, room temperature reaction 8h, then filtering also concentration of reaction solution extremely does, the sherwood oil that the volume ratio of usining is again 16: 1: the mixing solutions of ethyl acetate is as eluent, carry out purification by silica gel column chromatography separation, obtain the bromo-1-of 1-(4-p-methoxy-phenyl)-2-acetone, complete the synthetic method of alpha-brominated aromatic ketones compound, wherein the structural formula of the bromo-1-of 1-(4-p-methoxy-phenyl)-2-acetone is:
This tests the bromo-1-of synthetic 1-(4-p-methoxy-phenyl)-2-acetone is white solid, and productive rate is 88%, and its nuclear magnetic data is: 1HNMR (400MHz, CDCl3): δ 7.35 (d, J=8.7Hz, 2H), 6.89 (d, J=8.7Hz, 2H), 5.43 (s, 1H), 3.80 (s, 3H), 2.29 (s, 3H) .13C NMR (100MHz, CDCl3): δ 199.3,160.3,130.2,127.2,114.6,56.4,55.5,26.4.
Test 3, a kind of synthetic method of alpha-brominated aromatic ketones compound, by following steps, undertaken: in reaction flask, add 44.4mg3-(4-p-methoxy-phenyl) oxyethane-2-carboxylic acid, ethyl ester, 99.5mg carbon tetrabromide and 7.5mg Tris(2,2'-bipyridyl) ruthenium (II) chloride catalyzer, then with syringe, drawing 2mL acetonitrile joins in reaction flask, the rubber plug that is inserted with syringe needle is beyond the Great Wall placed under radiation of visible light, room temperature reaction 9h, then filtering also concentration of reaction solution extremely does, the sherwood oil that the volume ratio of usining is again 16: 1: the mixing solutions of ethyl acetate is as eluent, carry out purification by silica gel column chromatography separation, obtain the bromo-3-of 3-(4-p-methoxy-phenyl)-Pyruvic Acid Ethyl ester, complete the synthetic method of alpha-brominated aromatic ketones compound, wherein the structural formula of the bromo-3-of 3-(4-p-methoxy-phenyl)-Pyruvic Acid Ethyl ester is:
This tests the bromo-3-of synthetic 3-(4-p-methoxy-phenyl)-Pyruvic Acid Ethyl ester is weak yellow liquid, and productive rate is 67%, and its nuclear magnetic data is: 1HNMR (400MHz, CDCl3): δ 7.39 (d, J=8.7Hz, 2H), 6.90 (d, J=8.7Hz, 2H), 6.22 (s, 1H), 4.32 (qd, J=7.2,3.7Hz, 2H), 3.81 (s, 3H), 1.33 (t, J=7.2Hz, 3H) .13C NMR (100MHz, CDCl3): δ 184.0,160.7,160.3,131.2,125.0,114.6,63.3,55.5,50.1,14.0.
Test 4, a kind of synthetic method of alpha-brominated aromatic ketones compound, by following steps, undertaken: in reaction flask, add 54.2mg2-(4-p-methoxy-phenyl)-3-(4-nitrophenyl) oxyethane, 26mg lithiumbromide, 90mg Sodium Persulfate and 7.5mg Tris(2,2'-bipyridyl) ruthenium (II) chloride catalyzer, then with syringe, drawing 2mL acetonitrile joins in reaction flask, the rubber plug that is inserted with syringe needle is beyond the Great Wall placed under radiation of visible light, room temperature reaction 8h, then filtering also concentration of reaction solution extremely does, the sherwood oil that the volume ratio of usining is again 10: 1: the mixing solutions of ethyl acetate is as eluent, carry out purification by silica gel column chromatography separation, obtain the bromo-2-of 2-(4-p-methoxy-phenyl)-1-(4-nitrophenyl) ethyl ketone, complete the synthetic method of alpha-brominated aromatic ketones compound, wherein the structural formula of the bromo-2-of 2-(4-p-methoxy-phenyl)-1-(4-nitrophenyl) ethyl ketone is:
This tests the bromo-2-of synthetic 2-(4-p-methoxy-phenyl)-1-(4-nitrophenyl) ethyl ketone is weak yellow liquid, and productive rate is 72%, and its nuclear magnetic data is: 1HNMR (400MHz, CDCl3): δ 8.27 (d, J=8.7Hz, 2H), 8.12 (d, J=8.7Hz, 2H), 7.44 (d, J=8.6Hz, 2H), 6.90 (d, J=8.6Hz, 2H), 6.33 (s, 1H), 3.80 (s, 3H) .13CNMR (100MHz, CDCl3): δ 189.8,160.6,150.5,139.1,130.7,130.3,126.7,124.0,114.8,55.5,51.1.
Test 5, a kind of synthetic method of alpha-brominated aromatic ketones compound, by following steps, undertaken: in reaction flask, add 61.0mg2-(4-bromo phenyl)-3-(4-p-methoxy-phenyl) oxyethane, 99.5mg carbon tetrabromide and 7.5mg Tris(2,2'-bipyridyl) ruthenium (II) chloride catalyzer, then with syringe, drawing 2mL acetonitrile joins in reaction flask, the rubber plug that is inserted with syringe needle is beyond the Great Wall placed under radiation of visible light, room temperature reaction 10h, then filtering also concentration of reaction solution extremely does, the sherwood oil that the volume ratio of usining is again 12: 1: the mixing solutions of ethyl acetate is as eluent, carry out purification by silica gel column chromatography separation, obtain the bromo-1-of 2-(4-bromo phenyl)-2-(4-p-methoxy-phenyl) ethyl ketone, complete the synthetic method of alpha-brominated aromatic ketones compound, wherein the structural formula of the bromo-1-of 2-(4-bromo phenyl)-2-(4-p-methoxy-phenyl) ethyl ketone is:
This tests the bromo-1-of synthetic 2-(4-bromo phenyl)-2-(4-p-methoxy-phenyl) ethyl ketone is faint yellow solid, and productive rate is 86%, and its nuclear magnetic data is:
1h NMR (400MHz, CDCl
3): δ 7.83 (d, J=8.6Hz, 2H), 7.56 (d, J=8.6Hz, 2H), 7.43 (d, J=8.7Hz, 2H), 6.88 (d, J=8.7Hz, 2H), 6.32 (s, 1H), 3.78 (s, 3H).
13cNMR (100MHz, CDCl
3): δ 190.2,160.4,133.0,132.2,130.7,130.6,129.0,127.5,114.6,55.4,51.2.
Test 6, a kind of synthetic method of alpha-brominated aromatic ketones compound, by following steps, undertaken: in reaction flask, add 72.1mg (2-benzyloxy phenyl) (3-(4-p-methoxy-phenyl) oxyethane-2-yl) ketone, 26mg lithiumbromide, 90mg Sodium Persulfate and 7.5mg Tris(2,2'-bipyridyl) ruthenium (II) chloride catalyzer, then add with syringe and draw 2mL methyl alcohol in reaction flask, the rubber plug that is inserted with syringe needle is beyond the Great Wall placed under radiation of visible light, room temperature reaction 11h, then filtering also concentration of reaction solution extremely does, the sherwood oil that the volume ratio of usining is again 16: 1: the mixing solutions of ethyl acetate is as eluent, carry out purification by silica gel column chromatography separation, obtain the bromo-1-of 3-(2-benzyloxy phenyl)-3-(4-p-methoxy-phenyl) propane-1, 2-diketone, complete the synthetic method of alpha-brominated aromatic ketones compound, the bromo-1-of 3-(2-benzyloxy phenyl)-3-(4-p-methoxy-phenyl) propane-1 wherein, the structural formula of 2-diketone is:
This tests the bromo-1-of synthetic 3-(2-benzyloxy phenyl)-3-(4-p-methoxy-phenyl) propane-1, 2-diketone is weak yellow liquid, productive rate is 68%, its nuclear magnetic data is: 1H NMR (400MHz, CDCl3): δ 7.89 (d, J=7.8Hz, 1H), 7.55 (t, J=7.8Hz, 1H), 7.48-7.39 (m, 5H), 7.19 (d, J=8.6Hz, 2H), 7.08 (t, J=7.5Hz, 1H), 7.01 (d, J=8.5Hz, 1H), 6.79 (d, J=8.6Hz, 2H), 5.72 (s, 1H), 5.14 (d, J=2.7Hz, 2H), 3.77 (s, 3H) .13CNMR (100MHz, CDCl3): δ 193.0, 192.5, 1602, 159.4, 136.5, 135.3, 131.1, 129.0, 128.7, 128.3, 127.1, 122.9, 121.6, 114.3, 113.3, 71.4, 55.4, 51.3.
Test 7, a kind of synthetic method of alpha-brominated aromatic ketones compound, by following steps, undertaken: in 57.7mg (4-chloro phenyl) (3-(4-p-methoxy-phenyl) oxyethane-2-yl) ketone, add 26mg lithiumbromide, 90mg Sodium Persulfate and 7.5mg Tris(2,2'-bipyridyl) ruthenium (II) chloride catalyzer, then with syringe, draw 2mLN, dinethylformamide joins in reaction flask, the rubber plug that is inserted with syringe needle is beyond the Great Wall placed under radiation of visible light, room temperature reaction 10h, then filtering also concentration of reaction solution extremely does, the sherwood oil that the volume ratio of usining is again 10: 1: the mixing solutions of ethyl acetate is as eluent, carry out purification by silica gel column chromatography separation, obtain the bromo-1-of 3-(4-chloro phenyl)-3-(4-p-methoxy-phenyl) propane-1, 2-diketone, complete the synthetic method of alpha-brominated aromatic ketones compound, the bromo-1-of 3-(4-chloro phenyl)-3-(4-p-methoxy-phenyl) propane-1 wherein, the structural formula of 2-diketone is:
This tests the bromo-1-of synthetic 3-(4-chloro phenyl)-3-(4-p-methoxy-phenyl) propane-1, and 2-diketone is faint yellow solid, and productive rate is 75%, its nuclear magnetic data is: 1H NMR (400MHz, CDCl3): δ 7.97 (d, J=8.5Hz, 2H), 7.48 (d, J=8.2Hz, 2H), 6.91 (d, J=9.5Hz, 2H), 6.37 (s, 1H), 3.82 (s, 3H) .13C NMR (100MHz, CDCl3): δ 189.9,189.4,160.8,141.9,131.8,131.4,130.7,129.5,124.8,114.6,55.5,49.8.
From test 1～test 7, this test reaction conditions is gentle, and without strict, except water treatment and protection of inert gas, order of addition(of ingredients) is any, simple to operation.Reaction adopts the visible ray that cleans, is easy to get as energy derive, and the incandescent light of family expenses, LED lamp and sunlight all can be used as light source, cleanliness without any pollution; Carbon tetrabromide or metal bromide that the bromide reagent adopting is low toxicity, cheap and easy to get, be easy to feed in raw material, cocatalyst Sodium Persulfate is cheaply easy to get and is pollution-free; Photocatalyst consumption is few and can recycling.And the reaction substrate of this test is applied widely, can utilize the high yield of different aromatic epoxy ethane substrate realization responses, such as alkyl, ketone group, ester group and aromatic group etc.The productive rate of this test and selectivity are all higher, and partial reaction yield can be up to more than 90%, and generates single bromination product, and the product replacing without dibromo generates; ; Whole reaction safety and environmental protection, cost is low, and economic benefit is high, belongs to green chemistry process.
Claims (6)
1. the synthetic method of an alpha-brominated aromatic ketones compound, the synthetic method that it is characterized in that alpha-brominated aromatic ketones compound is undertaken by following steps: in aromatic epoxy ethane compound, add bromide reagent and photoresponse catalyzer, then under radiation of visible light, at organic solvent, it is acetonitrile, methyl alcohol or N, room temperature reaction 6～12h in dinethylformamide, then filtering also concentration of reaction solution extremely does, using mixing solutions as eluent again, carry out purification by silica gel column chromatography separation, obtain alpha-brominated aromatic ketones compound, complete the synthetic method of alpha-brominated aromatic ketones compound, wherein bromide reagent is carbon tetrabromide, photoresponse catalyzer is Tris(2,2'-bipyridyl) ruthenium (II) chloride, mixing solutions is by sherwood oil: ethyl acetate is (10～16) by volume: 1 ratio mixes, wherein the mol ratio of aromatic epoxy ethane compound and bromide reagent is 1:(1.1～1.5), the mol ratio of aromatic epoxy ethane compound and photoresponse catalyzer is 1:(0.01～0.05), above-mentioned aromatic epoxy ethane compound is 2-(4-p-methoxy-phenyl)-3-phenyl ethylene oxide, 2-(4-p-methoxy-phenyl)-3-methyl oxirane, 3-(4-p-methoxy-phenyl) oxyethane-2-carboxylic acid, ethyl ester, 2-(4-p-methoxy-phenyl)-3-(4-nitrophenyl) oxyethane, 2-(4-bromo phenyl)-3-(4-p-methoxy-phenyl) oxyethane, (2-benzyloxy phenyl) (3-(4-p-methoxy-phenyl) oxyethane-2-yl) ketone, (4-chloro phenyl) (3-(4-p-methoxy-phenyl) oxyethane-2-yl) ketone.
2. the synthetic method of a kind of alpha-brominated aromatic ketones compound according to claim 1, it is characterized in that bromide reagent is metal bromide lithiumbromide, in aromatic epoxy ethane compound, add cocatalyst Sodium Persulfate, wherein the mol ratio of aromatic epoxy ethane compound and Sodium Persulfate is 1:(1～2).
3. the synthetic method of a kind of alpha-brominated aromatic ketones compound according to claim 1, the mol ratio that it is characterized in that aromatic epoxy ethane compound and bromide reagent is 1:(1.1～1.2).
4. the synthetic method of a kind of alpha-brominated aromatic ketones compound according to claim 1, the mol ratio that it is characterized in that aromatic epoxy ethane compound and photoresponse catalyzer is 1:(0.02～0.04).
5. the synthetic method of a kind of alpha-brominated aromatic ketones compound according to claim 1, it is characterized in that organic solvent is acetonitrile, methyl alcohol or N, dinethylformamide, consumption is the organic solvent that every mmole aromatic epoxy ethane compound is used 5-10 milliliter.
6. the synthetic method of a kind of alpha-brominated aromatic ketones compound according to claim 1, is characterized in that visible light source is incandescent light or LED lamp or sunlight.
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