CN101898944A - Preparation process of α-bromocinnamaldehyde - Google Patents
Preparation process of α-bromocinnamaldehyde Download PDFInfo
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- CN101898944A CN101898944A CN2010102513352A CN201010251335A CN101898944A CN 101898944 A CN101898944 A CN 101898944A CN 2010102513352 A CN2010102513352 A CN 2010102513352A CN 201010251335 A CN201010251335 A CN 201010251335A CN 101898944 A CN101898944 A CN 101898944A
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- bromocinnamaldehyde
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- cinnamaldehyde
- reaction
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- WQRWNOKNRHCLHV-TWGQIWQCSA-N (z)-2-bromo-3-phenylprop-2-enal Chemical compound O=CC(/Br)=C/C1=CC=CC=C1 WQRWNOKNRHCLHV-TWGQIWQCSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 34
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 24
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 24
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 239000003208 petroleum Substances 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000000706 filtrate Substances 0.000 claims abstract description 10
- 239000002585 base Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229940117916 cinnamic aldehyde Drugs 0.000 claims abstract description 8
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- DVHARADPZCQQHR-UHFFFAOYSA-N 2,3-dibromo-3-phenylpropanal Chemical compound O=CC(Br)C(Br)C1=CC=CC=C1 DVHARADPZCQQHR-UHFFFAOYSA-N 0.000 claims abstract 4
- 239000002253 acid Substances 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- -1 ester compound Chemical class 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims 1
- 150000001340 alkali metals Chemical class 0.000 claims 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 18
- 239000000047 product Substances 0.000 abstract description 15
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 231100000419 toxicity Toxicity 0.000 abstract description 2
- 230000001988 toxicity Effects 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000010792 warming Methods 0.000 description 16
- WPNANGZVPFJPNZ-UHFFFAOYSA-N 2-bromo-3-phenylpropanal Chemical compound O=CC(Br)CC1=CC=CC=C1 WPNANGZVPFJPNZ-UHFFFAOYSA-N 0.000 description 9
- 238000007601 warm air drying Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 239000012065 filter cake Substances 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 239000012044 organic layer Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000003379 elimination reaction Methods 0.000 description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 229940040526 anhydrous sodium acetate Drugs 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-Lutidine Substances CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- 229940043232 butyl acetate Drugs 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 101150101537 Olah gene Proteins 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- AXMVYSVVTMKQSL-UHFFFAOYSA-N UNPD142122 Natural products OC1=CC=C(C=CC=O)C=C1O AXMVYSVVTMKQSL-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-M benzoate Chemical compound [O-]C(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-M 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- XKPJKVVZOOEMPK-UHFFFAOYSA-M lithium;formate Chemical compound [Li+].[O-]C=O XKPJKVVZOOEMPK-UHFFFAOYSA-M 0.000 description 1
- DYUMLJSJISTVPV-UHFFFAOYSA-N phenyl propanoate Chemical compound CCC(=O)OC1=CC=CC=C1 DYUMLJSJISTVPV-UHFFFAOYSA-N 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 235000020995 raw meat Nutrition 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- HFRXJVQOXRXOPP-UHFFFAOYSA-N thionyl bromide Chemical compound BrS(Br)=O HFRXJVQOXRXOPP-UHFFFAOYSA-N 0.000 description 1
- 229940126680 traditional chinese medicines Drugs 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及α-溴代肉桂醛的制备工艺，包括有以下步骤：1)将原料肉桂醛溶解于溶剂中，低温下滴加溴素，待溴素滴加完毕，搅拌15分钟，得到2，3-二溴-3-苯基丙醛溶液；2)按肉桂醛的物质的量1～4倍向步骤1)所得2，3-二溴-3-苯基丙醛溶液中加入弱碱，体系先升温至50±5℃反应(给出时间范围)，然后升温至80±5℃反应(给出时间范围)，然后冷却至室温，过滤，滤液经水洗，浓缩蒸出溶剂，残余物加入石油醚搅拌结晶，过滤，热风干燥，得α-溴代肉桂醛。本发明的方法与现有技术方法比，选用了可回收套用的溶剂，消去反应过程选用价廉低毒的碱，优化了工艺条件，降低了生产成本，产品质量好，收率高，有利于工业化生产。The present invention relates to a preparation process of α-bromocinnamaldehyde, comprising the following steps: 1) dissolving raw material cinnamaldehyde in a solvent, adding bromine dropwise at a low temperature, and stirring for 15 minutes after the bromine addition is completed, to obtain 2, 3-dibromo-3-phenylpropanal solution; 2) add a weak base to step 1) gained 2,3-dibromo-3-phenylpropanal solution by 1 to 4 times the amount of cinnamaldehyde, The system was first heated to 50±5°C for reaction (time range given), then heated to 80±5°C for reaction (time range given), then cooled to room temperature, filtered, the filtrate was washed with water, concentrated and evaporated to remove the solvent, and the residue was added to Stir and crystallize petroleum ether, filter, and dry with hot air to obtain α-bromocinnamaldehyde. Compared with the method of the prior art, the method of the present invention selects a recyclable solvent, eliminates the alkali with low price and toxicity in the reaction process, optimizes the process conditions, reduces the production cost, and has good product quality and high yield, which is beneficial to Industrial production.
Description
Technical field
The present invention relates to the preparation technology of alpha-bromo-cinnamaldehyde.
Background technology
Alpha-bromo-cinnamaldehyde is a kind of broad-spectrum high efficacy antimildew disinfectant, all be widely used in leather, weaving, food and daily necessities industry, be that raw material synthesizing fungicide alpha-bromo-cinnamaldehyde is the most direct reaction scheme at present with the phenylacrolein, this route comprises bromine addition and cancellation two-step reaction, the bromine adduct need not to separate usually, directly carries out elimination reaction and obtains product.To the report alpha-bromo-cinnamaldehyde of this reaction the earliest by people such as Zinko at J.Organomet, 17:1815 (1884) reports its synthetic method, it is solvent that this synthetic route adopts Glacial acetic acid, the elimination reaction process is used highly basic salt of wormwood, and the reaction system viscosity is big when amplifying production, and reaction is evenly difficult, last handling process need use in a large amount of alkali and the solvent Glacial acetic acid, generate a large amount of by product acetate, and the alpha-bromo-cinnamaldehyde color that this method obtains is darker, influences quality product.Simultaneously, Lu Yujing mentions the method for using yellow soda ash to replace salt of wormwood in Chinese patent open file CN1086214A, still can't solve the big and irretrievable problem of Glacial acetic acid of reactant viscosity.And Sun Mingkun etc. are in fine chemistry industry, 7:5 (1990) has reported the method for tetracol phenixin as solvent of using, in this method, the bromine addition reaction uses tetracol phenixin to be solvent, the elimination reaction process uses 2, and the 4-lutidine is done alkali, because 2, the 4-lutidine costs an arm and a leg, and this method is unfavorable for the large-scale production process cost control.In addition, people such as Olah have reported the another kind of method of alpha-bromo-cinnamaldehyde at J.Prakt.Chem. (1981), and it is bromizating agent that this method adopts thionyl bromide, and this bromizating agent price is expensive, and toxicity is big, is unfavorable for suitability for industrialized production equally.
Summary of the invention
The problem that the present invention is directed to above-mentioned prior art existence proposes a kind of preparation technology of alpha-bromo-cinnamaldehyde, solved the unfavorable factor that exists in original preparation process, select raw material cheap and easy to get, safety and low toxicity for use, improve reaction conditions, reduced production cost, simplify the operation course, improve the quality of products, more help suitability for industrialized production.
The present invention for the solution that problem adopts of the above-mentioned proposition of solution is: the preparation technology of alpha-bromo-cinnamaldehyde is characterized in that including following steps:
1) the raw meat cinnamic aldehyde is dissolved in the solvent, slowly drips the bromine of equimolar amount under the low temperature, treat that bromine dropwises, keep and stirred 15 minutes, obtain 2,3-two bromo-3-phenylpropionaldehyde solution;
2) press 1～4 times of the amount of substance of phenylacrolein to step 1) gained 2, add weak base in the 3-two bromo-3-phenylpropionaldehyde solution, system is warming up to 50 ± 5 ℃ of reactions (providing time range) earlier, is warming up to 80 ± 5 ℃ of reactions (providing time range) then, be cooled to room temperature then, filter, filtrate concentrates and steams solvent through washing, resistates adds the petroleum ether and stirring crystallization, filter, warm air drying gets alpha-bromo-cinnamaldehyde.
Press such scheme, the described solvent of step 1) is a general formula R
1COOR
2Ester cpds, wherein: R
1Represent hydrogen, C
1～C
4Alkyl, phenyl, R
2Represent C
1～C
4Alkyl, phenyl.
Press such scheme, the consumption of the described solvent of step 1) is 2～10 times of volume mass ratios of phenylacrolein.
Press such scheme, the consumption of the described solvent of step 1) is 3～5 times of volume mass ratios of phenylacrolein.
Press such scheme, the described low temperature of step 1) is-30～30 ℃.
Press such scheme, the described low temperature of step 1) is preferably-5～5 ℃.
Press such scheme, step 2) described weak base is any one or multiple mixing in the alkali-metal salt of weak acid, and base wherein is lithium, sodium or potassium, and the weak acid root is C
1～C
4Carboxylic acid, bicarbonate radical, hydrogen phosphate or benzoate anion.
Press such scheme, step 2) 1～2 times of the described weak base consumption amount of substance that is phenylacrolein.
The control of the temperature of bromine addition is low more, and then product colour is shallow more, and 20 ℃ of the room temperatures products that obtain of reaction down are little yellow, and-15 ℃ the products that obtain of reaction are almost colourless down, for ease of the temperature control of suitability for industrialized production, preferred-5～5 ℃ of reactions.
In the preparation process of compound (I), elimination reaction is carried out under lower temperature earlier, and elevated temperature is complete to elimination reaction again, has avoided reacting play and has caused color dark partially, the problem that yield is on the low side.
Reaction formula of the present invention is as follows:
Method of the present invention and art methods ratio have been selected the recyclable solvent of applying mechanically for use, and the elimination reaction process is selected the alkali of inexpensive low toxicity for use, has optimized processing condition, has reduced production cost, good product quality, and the yield height helps suitability for industrialized production.
Embodiment
Below explain the present invention by specific embodiment, but the present invention is not subjected to the qualification of these embodiment.
The phenylacrolein that the present invention uses provides all the other raw materials to be analytical pure or chemical pure by traditional Chinese medicines group, and melting point compound is measured by RY-1 type MELTING POINT TESTER, and temperature is not proofreaied and correct.
Embodiment 1:
Phenylacrolein 13.2g (0.1mol) is dissolved in the 50ml ethyl acetate, ice bath is cooled to 0 ℃, stir down, slowly drip 16.0g (0.1mol) bromine, added in about 1 hour, bromine finishes to keep and stirred 15 minutes, obtain 2,3-two bromo-3-phenylpropionaldehyde solution, this solution need not to separate, directly add 12.3g (0.15mol) anhydrous sodium acetate, be warming up to 50 ℃ and stirred 30 minutes, be warming up to 80 ℃ of stirrings 3 hours that reflux again, be cooled to room temperature, filter, filtrate is steamed and is desolventized with 2 * 30ml water washing, branch vibration layer, organic layer vacuum concentration, resistates adds the 50ml petroleum ether and stirring and is cooled to room temperature, separates out crystalline particulate.Filter, filter cake 25ml petroleum ether, 45 ℃ of warm air dryings, receive product 18.2g (yield 86.2%), fusing point 70-72 ℃.
Embodiment 2:
Phenylacrolein 13.2g (0.1mo1) is dissolved in the 80ml ethyl acetate, ice bath is cooled to 0 ℃, stir down, slowly drip 16.0g (0.1mol) bromine, added in about 1 hour, bromine finishes to keep and stirred 15 minutes, obtain 2,3-two bromo-3-phenylpropionaldehyde solution, this solution need not to separate, directly add 25.6g (0.18mol) Sodium phosphate dibasic, be warming up to 50 ℃ and stirred 30 minutes, be warming up to 80 ℃ again and stirred 3 hours, be cooled to room temperature, filter, filtrate is steamed and is desolventized with 2 * 30ml water washing, branch vibration layer, organic layer vacuum concentration, resistates adds the 50ml petroleum ether and stirring and is cooled to room temperature, separates out crystalline particulate.Filter, filter cake 25ml petroleum ether, 45 ℃ of warm air dryings, receive product 17.7g (yield 83.9%), fusing point 70-72 ℃.
Embodiment 3
Phenylacrolein 13.2g (0.1mol) is dissolved in the 50ml ethyl formate, ice bath is cooled to 0 ℃, stir down, slowly drip 16.0g (0.1mol) bromine, added in about 1 hour, bromine finishes to keep and stirred 15 minutes, obtain 2,3-two bromo-3-phenylpropionaldehyde solution, this solution need not to separate, directly add 13.1g (0.16mol) anhydrous sodium acetate, be warming up to 50 ℃ and stirred 30 minutes, be warming up to 80 ℃ again and stirred 3 hours, be cooled to room temperature, filter, filtrate is steamed and is desolventized with 2 * 30ml water washing, branch vibration layer, organic layer vacuum concentration, resistates adds the 50ml petroleum ether and stirring and is cooled to room temperature, separates out crystalline particulate.Filter, filter cake 25ml petroleum ether, 45 ℃ of warm air dryings, receive product 15.3g (yield 72.5%), fusing point 70-72 ℃.
Embodiment 4
Phenylacrolein 13.2g (0.1mol) is dissolved in the 50ml butylacetate, ice bath is cooled to 0 ℃, stir down, slowly drip 16.0g (0.1mol) bromine, added in about 1 hour, bromine finishes to keep and stirred 15 minutes, obtain 2,3-two bromo-3-phenylpropionaldehyde solution, this solution need not to separate, directly add 12.6g (0.15mol) sodium bicarbonate, be warming up to 50 ℃ and stirred 30 minutes, be warming up to 80 ℃ of stirrings 3 hours that reflux again, be cooled to room temperature, filter, filtrate is steamed and is desolventized with 2 * 30ml water washing, branch vibration layer, organic layer vacuum concentration, resistates adds the 50ml petroleum ether and stirring and is cooled to room temperature, separates out crystalline particulate.Filter, filter cake 25ml petroleum ether, 45 ℃ of warm air dryings, receive product 16.3g (yield 77.2%), fusing point 70-72 ℃.
Embodiment 5
Phenylacrolein 13.2g (0.1mol) is dissolved in the 50ml butylacetate, ice bath is cooled to 0 ℃, stir down, slowly drip 16.0g (0.1mol) bromine, added in about 1 hour, bromine finishes to keep and stirred 15 minutes, obtain 2,3-two bromo-3-phenylpropionaldehyde solution, this solution need not to separate, directly add 8.2g (0.1mol) anhydrous sodium acetate, 4.2g (0.05mol) sodium bicarbonate, be warming up to 50 ℃ and stirred 30 minutes, be warming up to 80 ℃ again and stirred 3 hours, be cooled to room temperature, filter, filtrate is steamed and is desolventized with 2 * 30ml water washing, branch vibration layer, organic layer vacuum concentration, resistates adds the 50ml petroleum ether and stirring and is cooled to room temperature, separates out crystalline particulate.Filter, filter cake 25ml petroleum ether, 45 ℃ of warm air dryings, receive product 17.4g (yield 82.5%), fusing point 70-72 ℃.
Embodiment 6
Phenylacrolein 13.2g (0.1mol) is dissolved in the 50ml ethyl benzoate, ice bath is cooled to 0 ℃, stir down, slowly drip 16.0g (0.1mol) bromine, added in about 1 hour, bromine finishes to keep and stirred 15 minutes, obtain 2,3-two bromo-3-phenylpropionaldehyde solution, this solution need not to separate, directly add 24.0g (0.15mol) Sodium Benzoate, be warming up to 50 ℃ and stirred 30 minutes, be warming up to 80 ℃ again and stirred 3 hours, be cooled to room temperature, filter, filtrate is steamed and is desolventized with 2 * 30ml water washing, branch vibration layer, organic layer vacuum concentration, resistates adds the 50ml petroleum ether and stirring and is cooled to room temperature, separates out crystalline particulate.Filter, filter cake 25ml petroleum ether, 45 ℃ of warm air dryings, receive product 15.8g (yield 74.9%), fusing point 70-72 ℃.
Embodiment 7
Phenylacrolein 13.2g (0.1mol) is dissolved in the 50ml phenylpropionate, ice bath is cooled to 0 ℃, stir down, slowly drip 16.0g (0.1mol) bromine, added in about 1 hour, bromine finishes to keep and stirred 15 minutes, obtain 2,3-two bromo-3-phenylpropionaldehyde solution, this solution need not to separate, directly add 11.4g (0.15mol) lithium formate, be warming up to 50 ℃ and stirred 30 minutes, be warming up to 80 ℃ again and stirred 3 hours, be cooled to room temperature, filter, filtrate is steamed and is desolventized with 2 * 30ml water washing, branch vibration layer, organic layer vacuum concentration, resistates adds the 50ml petroleum ether and stirring and is cooled to room temperature, separates out crystalline particulate.Filter, filter cake 25ml petroleum ether, 45 ℃ of warm air dryings, receive product 14.6g (yield 69.2%), fusing point 70-72 ℃.
The above only is preferred embodiment of the present invention, thus all according to described feature of the present patent application claim and method, be included in the present patent application claim.(annotate: present patent application is by the subsidy of state natural sciences fund 20902071)
Claims (9)
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1086204A (en) * | 1992-10-30 | 1994-05-04 | 青岛海洋大学 | A kind of synthetic method of alpha-bromo-cinnamaldehyde |
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2010
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1086204A (en) * | 1992-10-30 | 1994-05-04 | 青岛海洋大学 | A kind of synthetic method of alpha-bromo-cinnamaldehyde |
Non-Patent Citations (6)
| Title |
|---|
| 《精细化工》 19901231 孙明昆等 alpha-溴代肉桂醛的合成 5-6,30 1-9 第7卷, * |
| 《食品与机械》 19951231 肖凯军等 alpha-溴代肉桂醛的合成抗菌性及应用 26-28 1-9 , 第5期 * |
| 孙明昆等: "α-溴代肉桂醛的合成", 《精细化工》 * |
| 李光才: "杀菌剂_溴代肉桂醛的合成", 《青岛化工学院学报》 * |
| 田孟超等: "防霉剂2-溴代肉桂醛的合成新工艺研究", 《河南科学》 * |
| 肖凯军等: "α-溴代肉桂醛的合成抗菌性及应用", 《食品与机械》 * |
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