CN113666810A - 一种羟基香茅醛的绿色合成方法 - Google Patents
一种羟基香茅醛的绿色合成方法 Download PDFInfo
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- CN113666810A CN113666810A CN202110983274.7A CN202110983274A CN113666810A CN 113666810 A CN113666810 A CN 113666810A CN 202110983274 A CN202110983274 A CN 202110983274A CN 113666810 A CN113666810 A CN 113666810A
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- hydroxycitronellal
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- WPFVBOQKRVRMJB-UHFFFAOYSA-N hydroxycitronellal Chemical compound O=CCC(C)CCCC(C)(C)O WPFVBOQKRVRMJB-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000001308 synthesis method Methods 0.000 title claims abstract description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- UZFMOKQJFYMBGY-UHFFFAOYSA-N 4-hydroxy-TEMPO Chemical compound CC1(C)CC(O)CC(C)(C)N1[O] UZFMOKQJFYMBGY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012043 crude product Substances 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 238000004321 preservation Methods 0.000 claims abstract description 5
- 239000000047 product Substances 0.000 claims abstract description 5
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- -1 hydroxyl citronellol Chemical compound 0.000 claims description 2
- QMVPMAAFGQKVCJ-SNVBAGLBSA-N (R)-(+)-citronellol Natural products OCC[C@H](C)CCC=C(C)C QMVPMAAFGQKVCJ-SNVBAGLBSA-N 0.000 claims 1
- QMVPMAAFGQKVCJ-UHFFFAOYSA-N Citronellol Natural products OCCC(C)CCC=C(C)C QMVPMAAFGQKVCJ-UHFFFAOYSA-N 0.000 claims 1
- JGQFVRIQXUFPAH-UHFFFAOYSA-N beta-citronellol Natural products OCCC(C)CCCC(C)=C JGQFVRIQXUFPAH-UHFFFAOYSA-N 0.000 claims 1
- 235000000484 citronellol Nutrition 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 17
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000002351 wastewater Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- NEHNMFOYXAPHSD-UHFFFAOYSA-N beta-citronellal Natural products O=CCC(C)CCC=C(C)C NEHNMFOYXAPHSD-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 229930003633 citronellal Natural products 0.000 description 3
- 235000000983 citronellal Nutrition 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 239000003205 fragrance Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 235000013599 spices Nutrition 0.000 description 2
- 241000167854 Bourreria succulenta Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 241000234435 Lilium Species 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 244000223014 Syzygium aromaticum Species 0.000 description 1
- 235000016639 Syzygium aromaticum Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 235000019693 cherries Nutrition 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010511 deprotection reaction Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
- B01J27/25—Nitrates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0271—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0231
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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Abstract
本发明公开了一种种羟基香茅醛的绿色合成方法,包括以下步骤:(1)将羟基香茅醇、乙腈、Fe(NO3)3•9H2O和4‑OH‑TEMPO在反应器中混合均匀,并升温;(2)向步骤(1)的反应器中持续通氧气,保温反应,反应结束后,反应液经减压回收乙腈后的粗品,粗品经精馏得到羟基香茅醛成品。本发明以羟基香茅醇为原料,基于Fe(NO3)3/4‑OH‑TEMPO催化体系催化分子氧化羟基香茅醇合成羟基香茅醛,本发明催化效率高、反应选择性高、产率高、反应条件温和、生产效率高、工艺简单、工艺成本低,且反应过程无废水产生,绿色环保,适于工业化、规模化生产羟基香茅醛。
Description
技术领域
本发明属于精细化工技术领域,具体涉及一种绿色的羟基香茅醛的合成方法。
背景技术
羟基香茅醛,为无色至淡黄色透明液体,具有甜的花香气味,类似于柔和的玫瑰香气。微溶于水,溶于乙醇等有机溶剂。沸点为263℃,密度0.925-0.933g/mL,折射率为1.4570-1.4610,闪点>100℃。常用作香料,配制丁香、百合等花香型香精,用于化妆品;也用作食用香料的稳定剂,配制柠檬、樱桃、柑橘等食用香精。
目前,合成羟基香茅醛的方法主要有两种路线:(1)香茅醛醛基保护法(如下式所示)。典型的操作是以香茅醛为原料,利用亚硫酸氢钠(或二乙醇胺等)把醛基保护起来,然后在酸性条件下发生水合成反应,最后通过去保护得到羟基香茅醛。该种方法是目前国内主流的生产方法,但在生产过程中采用高浓度硫酸作为水合催化剂,硫酸难以回收利用会产生大量难以处理的高盐废水。
(2)醇脱氢法。美国专利US3940446公开了一种羟基香茅醇催化脱氢制备羟基香茅醛的方法,以自制氧化铜为催化剂,羟基香茅醇半连续进料,280℃、15kpa真空下反应,反应产率88.5%,转化率为55.6%。脱氢法制备羟基香茅醛,反应条件苛刻,反应转化率不高,催化剂易失活,同时羟基香茅醛本身耐酸、碱性及热稳定性较差,很容易引发自缩合等副反应,严重影响反应的产率和后期的产品的香气品质等,且副产物为氢气,收集较困难,存在安全隐患,工业化普及性不高。
发明内容
针对现有技术的不足,本发明的目的在于提供一种羟基香茅醛的绿色合成方法,本发明以羟基香茅醇为原料,基于Fe(NO3)3/4-OH-TEMPO催化体系催化分子氧化羟基香茅醇合成羟基香茅醛,本发明催化效率高、反应选择性高、产率高、反应条件温和、生产效率高、工艺简单、工艺成本低,且反应过程无废水产生,绿色环保,适于工业化、规模化生产羟基香茅醛。
本发明是通过以下技术方案实现的:
一种羟基香茅醛的绿色合成方法,包括以下步骤:
(1)将羟基香茅醇、乙腈、硝酸铁(Fe(NO3)3•9H2O)和4-羟基-2,2,6,6-四甲基哌啶-1-氧自由基(4-OH-TEMPO)在反应器中混合均匀,并升温;
(2)向步骤(1)的反应器中持续通氧气,保温反应,反应结束后,反应液经减压回收乙腈后的粗品,粗品经精馏得到羟基香茅醛成品。
本发明反应方程式为:
进一步的,步骤(1)中升温至30-70℃。
进一步的,步骤(2)中保温反应的温度为30-70℃,时间为2~8h。
进一步的,所述羟基香茅醇、乙腈、Fe(NO3)3•9H2O以及4-OH-TEMPO的摩尔比为比1.0:(3.0-10.0):(0.01-0.06):(0.01-0.04)。
本发明的有益效果为:
本发明以以羟基香茅醇为原料,基于Fe(NO3)3/4-OH-TEMPO催化体系催化分子氧化羟基香茅醇合成羟基香茅醛,本发明使用的Fe(NO3)3/4-OH-TEMPO催化体系,催化效率高、反应选择性高,可达95.6%。本发明工艺简单、生产效率高、成本低,且反应过程无废水产生,绿色环保,适于工业化、规模化生产羟基香茅醛。
具体实施方式
实施例1
反应釜内投入羟基香茅醇 174.0g(1.0mol)、乙腈 174.0g(4.2mol)、Fe(NO3)3•9H2O 20.2g(0.05mol)和4-OH-TEMPO 5.16g(0.03mol),升温至50±2℃,向釜内按通氧气,保持釜内压力为0.05-0.07MPa,保温反应3h后停止通氧,结束反应,减压回收乙腈后,粗品经精馏得到羟基香茅醛成品137.1g,经气相色谱分析,含量为99.2%,产率为78.8%,选择性为95.6%。
实施例2
本实施例按实施例1的方法合成羟基香茅醛,不同的是改通氧气为空气,其余操作不变。
本实施例中,收集得到羟基香茅醛103.7g 经气相色谱分析,含量为99.1%,产率为59.6%,选择性为91.5%。
实施例3
本实施例按实施例1的方法合成羟基香茅醛,不同的是催化剂量减半,即反应釜内投入羟基香茅醇 174.0g(1.0mol)、乙腈 174.0g(4.2mol)、Fe(NO3)3•9H2O 10.1g(0.025mol)和4-OH-TEMPO 2.58g(0.015mol),其余操作不变。
本实施例中,收集得到羟基香茅醛124.6g 经气相色谱分析,含量为99.1%,产率为71.6%,选择性为94.2%。
实施例4
本实施例按实施例1的方法合成羟基香茅醛,不同的是反应温度为70℃,其余操作不变。
本实施例中,收集得到羟基香茅醛110.8g 经气相色谱分析,含量为98.6%,产率为63.7%,选择性为89.3%。
Claims (4)
1.一种羟基香茅醛的绿色合成方法,其特征在于,包括以下步骤:
(1)将羟基香茅醇、乙腈、Fe(NO3)3•9H2O和4-OH-TEMPO在反应器中混合均匀,并升温;
(2)向步骤(1)的反应器中持续通氧气,保温反应,反应结束后,反应液经减压回收乙腈后的粗品,粗品经精馏得到羟基香茅醛成品。
2.根据权利要求1所述的一种羟基香茅醛的绿色合成方法,其特征在于:步骤(1)中升温至30-70℃。
3.根据权利要求1所述的一种羟基香茅醛的绿色合成方法,其特征在于:步骤(2)中保温反应的温度为30-70℃,时间为2~8h。
4.根据权利要求1所述的一种羟基香茅醛的绿色合成方法,其特征在于:所述羟基香茅醇、乙腈、Fe(NO3)3•9H2O以及4-OH-TEMPO的摩尔比为比1.0:(3.0-10.0):(0.01-0.06):(0.01-0.04)。
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---|---|---|---|---|
GB1342862A (en) * | 1971-03-22 | 1974-01-03 | Givaudan & Cie Sa | Process for preparing hydroxycitronellal |
CN101544548A (zh) * | 2008-03-26 | 2009-09-30 | 中国科学院大连化学物理研究所 | 一种氧气氧化醇制备醛或酮的方法 |
CN101709026A (zh) * | 2009-10-20 | 2010-05-19 | 浙江医药股份有限公司维生素厂 | 一种3-甲基-2-丁烯醛的合成方法 |
CN103936709A (zh) * | 2014-05-13 | 2014-07-23 | 李东风 | 一种洋茉莉醛的合成方法 |
CN108892607A (zh) * | 2018-08-14 | 2018-11-27 | 山东新和成药业有限公司 | 一种羟基香茅醛的制备方法 |
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- 2021-08-25 CN CN202110983274.7A patent/CN113666810B/zh active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1342862A (en) * | 1971-03-22 | 1974-01-03 | Givaudan & Cie Sa | Process for preparing hydroxycitronellal |
CN101544548A (zh) * | 2008-03-26 | 2009-09-30 | 中国科学院大连化学物理研究所 | 一种氧气氧化醇制备醛或酮的方法 |
CN101709026A (zh) * | 2009-10-20 | 2010-05-19 | 浙江医药股份有限公司维生素厂 | 一种3-甲基-2-丁烯醛的合成方法 |
CN103936709A (zh) * | 2014-05-13 | 2014-07-23 | 李东风 | 一种洋茉莉醛的合成方法 |
CN108892607A (zh) * | 2018-08-14 | 2018-11-27 | 山东新和成药业有限公司 | 一种羟基香茅醛的制备方法 |
Non-Patent Citations (1)
Title |
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王心亮;梁鑫淼;: "温和条件下Fe(NO_3)_3/4-OH-TEMPO催化需氧氧化醇制备羰基化合物", 催化学报, no. 09, pages 935 - 939 * |
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