CN100577629C - 一种甲酸肉桂酯的制备方法 - Google Patents
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- BFNMZJQMWPPBKE-UHFFFAOYSA-N 1-oxo-3h-2-benzofuran-4-carbonitrile Chemical compound C1=CC=C(C#N)C2=C1C(=O)OC2 BFNMZJQMWPPBKE-UHFFFAOYSA-N 0.000 title claims description 22
- 239000001623 3-phenylprop-2-enyl formate Substances 0.000 title claims description 22
- 238000000034 method Methods 0.000 title abstract description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 40
- 235000019253 formic acid Nutrition 0.000 claims abstract description 20
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 19
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 14
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- 238000011084 recovery Methods 0.000 claims description 5
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 238000006386 neutralization reaction Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 2
- 244000037364 Cinnamomum aromaticum Species 0.000 abstract 5
- 235000014489 Cinnamomum aromaticum Nutrition 0.000 abstract 5
- 150000002148 esters Chemical class 0.000 abstract 5
- OOCCDEMITAIZTP-UHFFFAOYSA-N allylic benzylic alcohol Natural products OCC=CC1=CC=CC=C1 OOCCDEMITAIZTP-UHFFFAOYSA-N 0.000 abstract 2
- 230000006837 decompression Effects 0.000 abstract 2
- 238000009776 industrial production Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 2
- 235000013599 spices Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 244000144730 Amygdalus persica Species 0.000 description 1
- 235000016623 Fragaria vesca Nutrition 0.000 description 1
- 240000009088 Fragaria x ananassa Species 0.000 description 1
- 235000011363 Fragaria x ananassa Nutrition 0.000 description 1
- 240000008790 Musa x paradisiaca Species 0.000 description 1
- 235000018290 Musa x paradisiaca Nutrition 0.000 description 1
- 235000006040 Prunus persica var persica Nutrition 0.000 description 1
- 235000011034 Rubus glaucus Nutrition 0.000 description 1
- 244000235659 Rubus idaeus Species 0.000 description 1
- 235000009122 Rubus idaeus Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- -1 formic acid phenylallene ester Chemical class 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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Abstract
本发明公开了一种甲酸肉桂酯的制备方法，其步骤是：A、将甲酸溶于有机溶剂中，按甲酸质量比例加入催化剂，搅拌均匀并降温，保温滴加肉桂醇；B、滴加肉桂醇完毕后，经水洗中和得粗制甲酸肉桂酯；C、将粗制甲酸肉桂酯减压在-0.07～-0.1MPa范围内回收溶剂；D、回收溶剂完毕，再在减压-0.097～-0.1MPa条件下，收集甲酸肉桂酯成品。本发明方法简单，操作方便，原料成本低廉，且收率高，对环境也无污染，非常适于工业化生产，生产甲酸肉桂酯的收率可高达78.5%。
Description
技术领域
本发明属于化学领域，更具体涉及一种甲酸肉桂酯的制备方法，其主要作为香料应用于配置草莓、树莓、桃、香蕉和香辛料等型香精。
背景技术
甲酸肉桂酯化学名称为甲酸苯丙烯酯，是一种重要的精细化工中间体，广泛应用于医药、香料等产品的生产中。目前制备甲酸肉桂酯的通用方法主要有：1、甲酸和肉桂醇直接酯化来制备甲酸肉桂酯，使用不同的催化剂(如氯化铵，氯化镁，磷酸，浓硫酸等)对生产的甲酸肉桂酯的收率和产品质量有较大的影响，此种方法合成的甲酸肉桂酯产品收率低，产品质量差。2、由甲酸钠与肉桂基氯在吡啶存在下反应合成甲酸肉桂酯。此合成方法工艺虽然比较简单，但是溶剂的消耗量大，主要原料甲酸钠和肉桂基氯来源有限，而且所用原料及溶剂价格昂贵，从经济角度考虑不划算。
发明内容
本发明的目的是在于提供了一种甲酸肉桂酯的制备方法，该方法用甲酸和肉桂醇，在有机溶剂甲苯或苯为溶剂、以磷酸或甲苯磺酸为催化剂制备甲酸肉桂酯，工艺简单，操作方便，原料易得、成本低廉，且收率高，对环境也无污染，非常适于工业化生产。
为了实现上述目的，本发明采用以下技术方案，其步骤是：
A、将甲酸按质量比为1∶1-1.5的比例溶于有机溶剂中，按甲酸质量的1.5或2或3或4％的比例加入催化剂，搅拌均匀并降温至20或25或30℃，保温温度控制在20或22或25或27或30℃滴加肉桂醇，甲酸与肉桂醇的摩尔比为2-5∶1。
B、滴加肉桂醇的时间为1或2或3小时，温度保持20或22或25或27或30℃反应0.5小时或1小时，肉桂醇滴加完毕经水洗中和得甲酸肉桂酯粗品。
C、粗品再减压-0.07--0.1Mpa，温度控制在110或115或120℃条件下回收溶剂，溶剂回收完。
D、溶剂回收完毕后，再在减压-0.097--0.1Mpa条件下，温度控制在148或152或156或160或164或170℃收集甲酸肉桂酯成品。
所述的有机溶剂甲苯或苯；
所述的催化剂是浓度为85-98％的磷酸或对甲苯磺酸。
本发明与现有技术相比，具有以下优点和效果：方法易行，工艺简单，生产成本低，无污染，产品质量稳定可靠，原料易得，非常适宜于工业化生产，生产甲酸肉桂酯收率可高达78.5％(以肉桂醇计)。
具体实施方式
实施例1
将88g(1.91mol)甲酸溶于88g(110ml)甲苯中，加入1.32g的85％磷酸或对甲苯磺酸，搅拌均匀，保持温度在20或22或25或27或30℃滴加肉桂醇127g(0.948mol)，滴加时间为1或2或3小时，滴加完毕，继续保持在20或22或25或27或30℃反应0.5或1小时，水洗中和并在-0.07Mpa下加热回收有机溶剂到110或115或120℃。溶剂回收完毕，再减压至-0.097Mpa，收集165-169℃馏分得甲酸肉桂酯111.6g，收率72.05％。产品纯度达95.6％。
实施例2
将88g(1.91mol)甲酸溶于105.6g(132ml)苯中，加入1.8g的88％磷酸或对甲苯磺酸，搅拌均匀，保持温度在20或21或24或26或30℃滴加肉桂醇85g(0.637mol)，滴加时间为1或2或3小时，滴加完毕，继续保持在20或23或26或28或30℃反应0.5或1小时，水洗中和并在-0.08Mpa下加热回收有机溶剂到110或114或120℃。溶剂回收完毕，再减压至-0.098Mpa，收集160-163℃馏分得甲酸肉桂酯78.5g，收率76.4％。产品纯度达95.2％。
实施例3
将88g(1.91mol)甲酸溶于118.8g(148.5ml)苯中，加入2.7g的92％磷酸或对甲苯磺酸，搅拌均匀，保持温度在20或23或26或29或30℃滴加肉桂醇64g(0.477mol)，滴加时间为1或2或3小时，滴加完毕，继续保持在20或21或24或26或30℃反应0.5或1小时，水洗中和并在-0.09Mpa下加热回收有机溶剂到110或115或120℃。溶剂回收完毕，再减压至-0.099Mpa，收集155-158℃馏分得甲酸肉桂酯61g，收率78.8％。产品纯度达96.2％。
实施例4
将88g(1.91mol)甲酸溶于132g(165ml)甲苯中，加入3.5g的98％磷酸或对甲苯磺酸，搅拌均匀，保持温度在20或22或25或27或30℃滴加肉桂醇51.2g(0.382mol)，滴加时间为1或2或3小时，滴加完毕，继续保持在20或22或25或27或30℃反应0.5或1小时，水洗中和并在-0.098Mpa下加热回收有机溶剂到110或115或120℃。溶剂回收完毕，再减压至-0.1Mpa，收集148-152℃馏分得甲酸肉桂酯24.4g，收率75.8％。产品纯度达95.9％。
Claims (1)
1、一种甲酸肉桂酯的制备方法，其步骤是：
A、将甲酸按质量比为1∶1-1.5的比例溶于有机溶剂中，按甲酸质量的1.5-4％的比例加入催化剂，搅拌均匀并降温至20-30℃，保温温度控制在20-30℃滴加肉桂醇，甲酸与肉桂醇的摩尔比为2-5∶1；
B、滴加肉桂醇的时间为1-3小时，温度保持20-30℃反应0.5或1小时，经水洗中和得甲酸肉桂酯制品；
C、将甲酸肉桂酯制品减压-0.07～-0.1Mpa，温度控制在110-120℃条件下回收溶剂；
D、回收溶剂完毕，再在减压-0.097--0.1Mpa条件下，温度控制在148-170℃收集甲酸肉桂酯成品；
所述的有机溶剂为甲苯或苯；
所述的催化剂为85-98％浓度的磷酸或对甲苯磺酸。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810047359A CN100577629C (zh) | 2008-04-17 | 2008-04-17 | 一种甲酸肉桂酯的制备方法 |
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| CN200810047359A CN100577629C (zh) | 2008-04-17 | 2008-04-17 | 一种甲酸肉桂酯的制备方法 |
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| Publication Number | Publication Date |
|---|---|
| CN101260041A CN101260041A (zh) | 2008-09-10 |
| CN100577629C true CN100577629C (zh) | 2010-01-06 |
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| CN200810047359A Expired - Fee Related CN100577629C (zh) | 2008-04-17 | 2008-04-17 | 一种甲酸肉桂酯的制备方法 |
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- 2008-04-17 CN CN200810047359A patent/CN100577629C/zh not_active Expired - Fee Related
Non-Patent Citations (4)
| Title |
|---|
| acetylation and formylation of alcohols in the presence ofsilica sulfuric acid. farhad shirini, et al.phosphorus, sulfur and silicon and the related elements,Vol.178 No.7. 2003 |
| acetylation and formylation of alcohols in the presence ofsilica sulfuric acid. farhad shirini, et al.phosphorus, sulfur and silicon and the related elements,Vol.178 No.7. 2003 * |
| selective formylation of alcohols in the presence of phenolswith chloral. ram N. ram.tetrahedron,No.58. 2002 |
| selective formylation of alcohols in the presence of phenolswith chloral. ram N. ram.tetrahedron,No.58. 2002 * |
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| CN101260041A (zh) | 2008-09-10 |
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