CN101429122B - 二氢茉莉酮酸甲酯合成中的一种脱羧方法 - Google Patents
二氢茉莉酮酸甲酯合成中的一种脱羧方法 Download PDFInfo
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- CN101429122B CN101429122B CN2008102445818A CN200810244581A CN101429122B CN 101429122 B CN101429122 B CN 101429122B CN 2008102445818 A CN2008102445818 A CN 2008102445818A CN 200810244581 A CN200810244581 A CN 200810244581A CN 101429122 B CN101429122 B CN 101429122B
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- methyl dihydrojasmonate
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- KVWWIYGFBYDJQC-UHFFFAOYSA-N methyl dihydrojasmonate Chemical compound CCCCCC1C(CC(=O)OC)CCC1=O KVWWIYGFBYDJQC-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000006114 decarboxylation reaction Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims abstract description 10
- 230000015572 biosynthetic process Effects 0.000 title 1
- 238000003786 synthesis reaction Methods 0.000 title 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims abstract description 12
- ILHZVKAXFCDFMT-UHFFFAOYSA-N 2-pentylcyclopent-2-en-1-one Chemical compound CCCCCC1=CCCC1=O ILHZVKAXFCDFMT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- ZIYVHBGGAOATLY-UHFFFAOYSA-N methylmalonic acid Chemical compound OC(=O)C(C)C(O)=O ZIYVHBGGAOATLY-UHFFFAOYSA-N 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 5
- 240000002853 Nelumbo nucifera Species 0.000 claims description 5
- 235000006508 Nelumbo nucifera Nutrition 0.000 claims description 5
- 238000007865 diluting Methods 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 5
- 239000012074 organic phase Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229960000583 acetic acid Drugs 0.000 claims description 4
- 239000012362 glacial acetic acid Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims 1
- 238000010992 reflux Methods 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- BEPAFCGSDWSTEL-UHFFFAOYSA-N dimethyl malonate Chemical compound COC(=O)CC(=O)OC BEPAFCGSDWSTEL-UHFFFAOYSA-N 0.000 abstract 3
- 238000007259 addition reaction Methods 0.000 abstract 1
- 238000005859 coupling reaction Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 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 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- YCIXWYOBMVNGTB-UHFFFAOYSA-N 3-methyl-2-pentylcyclopent-2-en-1-one Chemical compound CCCCCC1=C(C)CCC1=O YCIXWYOBMVNGTB-UHFFFAOYSA-N 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- 235000010254 Jasminum officinale Nutrition 0.000 description 1
- 240000005385 Jasminum sambac Species 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical group O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- -1 keto-acid methyl ester Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N pentanal Chemical compound CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了二氢茉莉酮酸甲酯合成中的一种脱羧方法，2-戊基环戊烯酮与丙二酸二甲酯在甲醇溶液中甲醇钠催化下进行加成和脱羧的藕合反应，得到二氢茉莉酮酸甲酯；其中，丙二酸二甲酯与2-戊基环戊烯酮摩尔比为1.2∶1，甲醇钠的投料量为丙二酸二甲酯摩尔量的1.1倍，反应温度60-70℃，回流反应20-25小时。本发明的方法反应条件温和，操作方便提高产率及顺体含量，改善产品香气品质，反应安全、环保，易于工业化生产。
Description
技术领域
本发明涉及一种香料化合物的合成，具体地说是二氢茉莉酮酸甲酯合成中的一种脱羧方法。
背景技术
二氢茉莉酮酸甲酯是目前最为流行、深受调香师欢迎的合成香料，具有优雅柔和的茉莉花香韵和舒适的柠檬样果香气息，整个香气轻盈飘逸留香持久，调香效果好，广泛用于化妆品香精和皂用香精配方中，能使香精产生优雅、圆和、逼真的天然样花香感，二氢茉莉酮酸甲酯已成为耗量最大和最成功的人工合成香料之一。
二氢茉莉酮酸甲酯的合成路线有很多，以环戊酮与正戊醛经缩合、异构化、Michael加成、高温脱羧等反应这条路线应用最广，脱羧温度有时高达200℃以上，会发生断键、炭化等，严重影响产品收率及香气品质，有部分顺式-二氢茉莉酮酸甲酯继续脱羧转化为二氢茉莉酮。
发明内容
本发明的目的是：提供一种二氢茉莉酮酸甲酯合成中的脱羧方法，该方法反应条件温和，操作方便，提高产率及顺体含量，改善产品香气品质，反应安全、环保，易于工业化生产。
本发明的技术解决方案是：2-戊基环戊烯酮与丙二酸二甲酯在甲醇溶液中甲醇钠催化下进行加成和脱羧的藕合反应，得到二氢茉莉酮酸甲酯，其中，丙二酸二甲酯与2-戊基环戊烯酮摩尔比为1.2∶1，甲醇钠的投料量为丙二酸二甲酯摩尔量的1.1倍，反应温度60-70℃，回流反应20-25小时。
本发明的二氢茉莉酮酸甲酯合成中的一种脱羧方法中，加成和脱羧的藕合反应结束后，冰浴降温，滴加经预冷的冰乙醇使固体全部溶解，回收甲醇，残留物加入蒸馏水稀释，特丁基甲醚萃取，分层，有机相经水洗、无水MgSO4干燥，蒸馏得二氢茉莉酮酸甲酯。
本发明采用加成和脱羧的藕合反应，节约反应步骤，产率高，反应温度低。
具体实施方式
下面结合具体的实例，进一步详细地描述本发明。应理解，这些实施例只是为了举例说明本发明，而非以任何方式限制本发明的范围。
实施例1
将900ml无水甲醇、35克甲醇钠、80克丙二酸二甲酯投入2000ml三口烧瓶，加热至60℃，回流保温1小时，再加入75克2-戊基环戊烯酮，继续保持回流约20小时，随着反应时间的增加析出的橙色晶体不断增加；反应结束后，冰浴冷至0℃，滴加45克经预冷的冰乙酸，摇动烧瓶，使固体全部溶解，回收出850ml甲醇，残留物加入600ml蒸馏水稀释，特丁基甲醚萃取，分层有机相经水洗、无水MgSO4干燥，蒸馏得100.9克二氢茉莉酮酸甲酯，二氢茉莉酮酸甲酯含量为98.3％，反应收率89.9％。
实施例2
将900ml无水甲醇、35克甲醇钠、80克丙二酸二甲酯投入2000ml三口烧瓶，加热至65℃，回流保温1.5小时，再加入75克2-戊基环戊烯酮，保持回流约22小时，随着反应时间的增加析出的橙色晶体也不断增加，反应结束后，冰浴冷至0℃，滴加51克经预冷的冰乙酸，摇动烧瓶，使固体全部溶解，回收出830ml甲醇，残留物加入620ml蒸馏水稀释，特丁基甲醚萃取，分层有机相经水洗、无水MgSO4干燥，蒸馏得102.2克二氢茉莉酮酸甲酯，二氢茉莉酮酸甲酯含量为98.6％，反应收率91.1％。
实施例3
将900ml无水甲醇、35克甲醇钠、80克丙二酸二甲酯投入2000ml三口烧瓶，加热至70℃，回流保温1.5小时，再加入75克2-戊基环戊烯酮，保持回流约25小时，随着反应时间的增加析出的橙色晶体也不断增加，反应结束后，冰浴冷至0℃，滴加51克经预冷的冰乙酸，摇动烧瓶，使固体全部溶解，回收出830ml甲醇，残留物加入620ml蒸馏水稀释，特丁基甲醚萃取，分层有机相经水洗、无水MgSO4干燥，蒸馏得103.2克二氢茉莉酮酸甲酯，二氢茉莉酮酸甲酯含量为98.5％，反应收率92.2％。
Claims (2)
1.二氢茉莉酮酸甲酯合成中的一种脱羧方法，其特征在于：2-戊基环戊烯酮与丙二酸二甲酯在甲醇溶液中甲醇钠催化下进行加成和脱羧的藕合反应，得到二氢茉莉酮酸甲酯；其中，丙二酸二甲酯与2-戊基环戊烯酮摩尔比为1.2∶1，甲醇钠的投料量为丙二酸二甲酯摩尔量的1.1倍，反应温度60-70℃，回流反应20-25小时。
2.根据权利要求1所述的二氢茉莉酮酸甲酯合成中的一种脱羧方法，其特征在于：加成和脱羧的藕合反应结束后，冰浴降温，滴加经预冷的冰乙酸使固体全部溶解，回收甲醇，残留物加入蒸馏水稀释，特丁基甲醚萃取，分层有机相经水洗、无水MgSO4干燥，蒸馏得二氢茉莉酮酸甲酯。
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| WO2023216615A1 (zh) | 2022-05-11 | 2023-11-16 | 浙江新化化工股份有限公司 | 一种3-(3-氧-2-戊基)环戊基丙二酸二甲酯的合成方法及催化剂 |
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| CN109516905A (zh) * | 2018-11-28 | 2019-03-26 | 盐城市春竹香料有限公司 | 低成本二氢茉莉酮的制备方法 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1577287A2 (en) * | 2004-03-15 | 2005-09-21 | Kao Corporation | Cycloalkanone composition |
| CN101234956A (zh) * | 2008-02-29 | 2008-08-06 | 北京化工大学 | 顺式-二氢茉莉酮酸甲酯合成中一种酮醛缩合方法 |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1577287A2 (en) * | 2004-03-15 | 2005-09-21 | Kao Corporation | Cycloalkanone composition |
| CN101234956A (zh) * | 2008-02-29 | 2008-08-06 | 北京化工大学 | 顺式-二氢茉莉酮酸甲酯合成中一种酮醛缩合方法 |
Non-Patent Citations (3)
| Title |
|---|
| Jiro Tsuji et al.A New Synthetic Method for Methyl Dihydrojasmonate from a Butadiene Telomer.《BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN》.1979,第52卷(第1期),216-217. * |
| Uzi Ravid et al.New Synthesis in Dihydrojasmone Series.《The Journal of Organic Chemistry》.1974,第39卷(第17期),2637-2639. * |
| 周景尧等.二氢茉莉酮酸甲酯的简便合成方法.《有机化学》.1985,(第6期),490-493. * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023216615A1 (zh) | 2022-05-11 | 2023-11-16 | 浙江新化化工股份有限公司 | 一种3-(3-氧-2-戊基)环戊基丙二酸二甲酯的合成方法及催化剂 |
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