CN109438183B - 一种红没药烯的合成方法 - Google Patents
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- XBGUIVFBMBVUEG-UHFFFAOYSA-N 1-methyl-4-(1,5-dimethyl-4-hexenylidene)-1-cyclohexene Chemical compound CC(C)=CCCC(C)=C1CCC(C)=CC1 XBGUIVFBMBVUEG-UHFFFAOYSA-N 0.000 title claims abstract description 41
- YHBUQBJHSRGZNF-HNNXBMFYSA-N alpha-bisabolene Natural products CC(C)=CCC=C(C)[C@@H]1CCC(C)=CC1 YHBUQBJHSRGZNF-HNNXBMFYSA-N 0.000 title claims abstract description 18
- 229930003493 bisabolene Natural products 0.000 title claims abstract description 17
- 238000001308 synthesis method Methods 0.000 title abstract description 5
- WTRAORJBWZMQIV-UHFFFAOYSA-N gamma-bisabolene Natural products CC(C)CCCC(C)=C1CCC(C)=CC1 WTRAORJBWZMQIV-UHFFFAOYSA-N 0.000 claims abstract description 28
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 23
- PDRRWJFZFIUXLR-UHFFFAOYSA-M CC(C[Mg]Br)=CC Chemical compound CC(C[Mg]Br)=CC PDRRWJFZFIUXLR-UHFFFAOYSA-M 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003377 acid catalyst Substances 0.000 claims abstract description 11
- 239000007818 Grignard reagent Substances 0.000 claims abstract description 8
- -1 Grignard reagent 2-methyl-2 butenyl magnesium bromide Chemical class 0.000 claims abstract description 8
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 6
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 4
- 238000010189 synthetic method Methods 0.000 claims abstract description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 74
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 28
- 238000002360 preparation method Methods 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- LOYZVRIHVZEDMW-UHFFFAOYSA-N 1-bromo-3-methylbut-2-ene Chemical compound CC(C)=CCBr LOYZVRIHVZEDMW-UHFFFAOYSA-N 0.000 claims description 9
- 239000012043 crude product Substances 0.000 claims description 9
- 238000007792 addition Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 239000008346 aqueous phase Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 3
- 239000012074 organic phase Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000010791 quenching Methods 0.000 claims description 3
- 230000000171 quenching effect Effects 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 239000002904 solvent Substances 0.000 abstract description 6
- 125000003995 gamma-bisabolene group Chemical group 0.000 abstract description 4
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000010306 acid treatment Methods 0.000 abstract description 2
- 230000009471 action Effects 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 2
- 230000005012 migration Effects 0.000 abstract description 2
- 238000013508 migration Methods 0.000 abstract description 2
- 238000005935 nucleophilic addition reaction Methods 0.000 abstract description 2
- 230000007062 hydrolysis Effects 0.000 abstract 1
- 230000005588 protonation Effects 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 239000003205 fragrance Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- WTVHAMTYZJGJLJ-UHFFFAOYSA-N (+)-(4S,8R)-8-epi-beta-bisabolol Natural products CC(C)=CCCC(C)C1(O)CCC(C)=CC1 WTVHAMTYZJGJLJ-UHFFFAOYSA-N 0.000 description 2
- RGZSQWQPBWRIAQ-CABCVRRESA-N (-)-alpha-Bisabolol Chemical compound CC(C)=CCC[C@](C)(O)[C@H]1CCC(C)=CC1 RGZSQWQPBWRIAQ-CABCVRRESA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- ZTYHGIAOVUPAAH-UHFFFAOYSA-N 2-(4-methyl-1-cyclohex-3-enyl)propan-1-ol Chemical compound OCC(C)C1CCC(C)=CC1 ZTYHGIAOVUPAAH-UHFFFAOYSA-N 0.000 description 2
- AMKGKYQBASDDJB-UHFFFAOYSA-N 9$l^{2}-borabicyclo[3.3.1]nonane Chemical compound C1CCC2CCCC1[B]2 AMKGKYQBASDDJB-UHFFFAOYSA-N 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- RGZSQWQPBWRIAQ-LSDHHAIUSA-N alpha-Bisabolol Natural products CC(C)=CCC[C@@](C)(O)[C@@H]1CCC(C)=CC1 RGZSQWQPBWRIAQ-LSDHHAIUSA-N 0.000 description 2
- HHGZABIIYIWLGA-UHFFFAOYSA-N bisabolol Natural products CC1CCC(C(C)(O)CCC=C(C)C)CC1 HHGZABIIYIWLGA-UHFFFAOYSA-N 0.000 description 2
- 229940036350 bisabolol Drugs 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229960001922 sodium perborate Drugs 0.000 description 2
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 2
- YHBUQBJHSRGZNF-UHFFFAOYSA-N trans-α-Bisabolene Chemical compound CC(C)=CCC=C(C)C1CCC(C)=CC1 YHBUQBJHSRGZNF-UHFFFAOYSA-N 0.000 description 2
- XZRVRYFILCSYSP-OAHLLOKOSA-N (-)-beta-bisabolene Chemical compound CC(C)=CCCC(=C)[C@H]1CCC(C)=CC1 XZRVRYFILCSYSP-OAHLLOKOSA-N 0.000 description 1
- FEJUGLKDZJDVFY-UHFFFAOYSA-N 9-borabicyclo[3.3.1]nonane Substances C1CCC2CCCC1B2 FEJUGLKDZJDVFY-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000229182 Ledebouriella seseloides Species 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- XZRVRYFILCSYSP-UHFFFAOYSA-N beta-Bisabolene Natural products CC(C)=CCCC(=C)C1CCC(C)=CC1 XZRVRYFILCSYSP-UHFFFAOYSA-N 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000834 fixative Substances 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930004725 sesquiterpene Natural products 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
- C07C29/40—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing carbon-to-metal bonds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/02—Magnesium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
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- Chemical Kinetics & Catalysis (AREA)
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- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种红没药烯的合成方法,该红没药烯为γ‑红没药烯,首先制备了格式试剂2‑甲基‑2丁烯基溴化镁,2‑甲基‑2丁烯基溴化镁与2‑(4‑甲基‑3‑烯‑1‑环己基)丙醛进行亲核加成反应,加成产物经酸处理,即水解得到了γ‑红没药烯醇,γ‑红没药烯醇在酸催化剂的作用下,醇先质子化,形成一个较好的离去基团H2O,而产生的碳正离子,接着通过氢迁移,形成一个更稳定的叔碳正离子,接着按照查依采夫规则脱去一个β氢原子,即得到了单一的产物γ‑红没药烯;该合成方法步骤简单,采用的溶剂均为常规试剂,适宜工业化生产,为红没药烯的合成提供了一种有效的方法。
Description
技术领域
本发明属于动物香料技术领域,具体涉及一种红没药烯的合成方法。
背景技术
红没药醇又称甜红没药醇、防风根醇,是自然界中存在较多的倍半萜化合物之一,红没药醇香气清淡愉快,是一种稳定性较好的定香剂,该产品在饲料香料目录里,可以用在动物香料诱食上。
现有的红没药烯一般采用从植物中提取的方法制备,得到的红没药烯为α-红没药烯、β-红没药烯和γ-红没药烯的混合物,难以分离得到单一的产物,且提取效率较低,俨然无法满足市场需求,采用有机合成的方法制备单一的红没药烯更是鲜有。
发明内容
本发明的目的在于提供一种红没药烯的合成方法,该合成方法步骤简单,采用的溶剂均为常规试剂,适宜工业化生产,为红没药烯的合成提供了一种有效的方法。
本发明的目的可以通过以下技术方案实现:
一种红没药烯的合成方法,该红没药烯为γ-红没药烯,γ-红没药烯的合成方法,具体包括以下步骤:
步骤一:2-甲基-2丁烯基溴化镁的制备
4-溴-2-甲基-2-丁烯与镁屑在无水甲基叔丁基醚的环境下回流反应得到格式试剂2-甲基-2丁烯基溴化镁的甲基叔丁基醚溶液,反应式如下:
步骤二:γ-红没药烯的合成
反应式如下:
S1、γ-红没药烯醇的制备
将装有2-甲基-2丁烯基溴化镁的甲基叔丁基醚溶液的反应瓶移至冰盐浴中,维持温度在-5-0℃,逐滴加入含0.2mol的2-(4-甲基-3-烯-1-环己基)丙醛的甲基叔丁基醚溶液,在30min内滴加完毕,滴加完毕后升温至15℃,搅拌反应1h,加入50ml10%的盐酸水溶液,保温搅拌30-60min进行水解反应,加入20ml饱和氯化铵水溶液淬灭反应,用甲基叔丁基醚萃取水相,合并有机相,用无水硫酸钠干燥,旋转蒸发除去甲基叔丁基醚即得γ-红没药烯醇粗品;
S2、γ-红没药烯的制备
向γ-红没药烯醇粗品中加入酸催化剂,在120-125℃下回流反应1h,减压蒸馏,收集馏分,即得到γ-红没药烯。
进一步,步骤一中2-甲基-2丁烯基溴化镁的制备具体为:在500mL三口烧瓶上,配置搅拌器、恒压滴液漏斗和带有CaCl2干燥管的回流冷凝管,向三口烧瓶中加入0.4mo1镁屑,用100mL无水甲基叔丁基醚浸没,边搅拌边滴入含20%的4-溴-2-甲基-2-丁烯甲基叔丁基醚溶液,加入2粒碘,将三口烧瓶放入水浴锅中,水浴温度为40-45℃,回流反应30min,即得格式试剂2-甲基-2丁烯基溴化镁的甲基叔丁基醚溶液。
进一步,所述的20%的4-溴-2-甲基-2-丁烯甲基叔丁基醚溶液由0.2mol1-溴-3甲基-2-丁烯和无水甲基叔丁基醚配制而成。
进一步,步骤二中,所述的2-(4-甲基-3-烯-1-环己基)丙醛的甲基叔丁基醚溶液中2-(4-甲基-3-烯-1-环己基)丙醛与甲基叔丁基醚溶液的体积比为1:5。
进一步,步骤二中,所述的酸催化剂为质量比为SnCl2:75%浓硫酸=1:20的混合物。
进一步,步骤二中,所述酸催化剂的加入量为γ-红没药烯醇粗品总质量的25-30%。
进一步,步骤二中,所述的收集馏分为收集540Pa下110-112℃的馏分。
γ-红没药烯醇脱水的反应机理为:
反应原理反应式如下:
γ-红没药烯醇在酸催化剂的作用下,醇先质子化,形成一个较好的离去基团H2O,而产生的碳正离子,接着通过氢迁移,形成一个更稳定的叔碳正离子,接着按照查依采夫规则脱去一个β氢原子,即得到了单一的产物γ-红没药烯。
本发明的有益效果:
本发明提供了一种红没药烯的合成方法,首先制备了格式试剂2-甲基-2丁烯基溴化镁,2-甲基-2丁烯基溴化镁与2-(4-甲基-3-烯-1-环己基)丙醛进行亲核加成反应,加成产物经酸处理,即水解得到了γ-红没药烯醇,γ-红没药烯醇脱水重排得到了单一的γ-红没药烯;该合成方法步骤简单,采用的溶剂均为常规试剂,适宜工业化生产,为红没药烯的合成提供了一种有效的方法;
另外,在实验过程中,使用乙醚做溶剂会发生着火事故,换做甲基叔丁基醚以后着火事故明显降低;且乙醚在使用时,见光或接触空气易产生过氧化物,存在过氧化物时,溶剂蒸馏温度高于100℃,易发生爆炸危险,甲基叔丁基醚在使用过程中不易产生过氧化物,提高了实验的安全性。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其它实施例,都属于本发明保护的范围。
实施例1
2-(4-甲基-3-烯-1-环己基)丙醛的制备:
反应式如下:
在0℃惰性气氛下,将溶于四氢呋喃的9-BBN(9-硼双环(3,3,1)-壬烷)溶液(162毫升,81毫摩尔)滴加到双戊烯(10.0克,73毫摩尔)中,添加结束后10分钟取出冷却浴,溶液在室温下搅拌3小时,然后将反应混合物冷却至0℃,并在搅拌下缓慢加入溶于150ml水的过硼酸钠(56g,364mmol)溶液,在0℃搅拌2小时后,加入200毫升饱和NH4Cl溶液和200毫升乙醚,析出混合物,水层用200ml乙醚萃取两次,合并有机层,用盐水洗涤,用硫酸镁干燥,真空浓缩,得到黄色油状物,用硅胶柱色谱法用石油醚/乙醚(8/2)纯化,得到9.06g(80%)β,4-二甲基-3-环己烯-1-乙醇;
在0℃下,将PCC(22.5g,104.6mmol)和硅藻土(22.8g)溶解于345mL二氯甲烷中,滴加溶于106mL二氯甲烷中β,4-二甲基-3-环己烯-1-乙醇(7.87g,51mmol)溶液,并在加入后的2h内在室温下搅拌反应,反应结束后,将粗混合物通过硅藻土和硅胶的短垫过滤,用二氯甲烷漂洗,经蒸馏,得到5.70g(收率为74%)2-(4-甲基-3-烯-1-环己基)丙醛;1H NMR(400MHz,CDCl3):δ9.61–9.57(m,1H),5.29(s,1H),2.27–2.18(m,1H),2.03–1.77(m,6H),1.71–1.59(m,1H),1.57(s,3H),1.00(t,J=6.9Hz,3H)。
实施例2
2-甲基-2丁烯基溴化镁的制备:
反应式如下:
4-溴-2-甲基-2-丁烯与镁屑在无水甲基叔丁基醚的环境下回流反应得到格式试剂2-甲基-2丁烯基溴化镁;
具体为:在500mL三口烧瓶上,配置搅拌器、恒压滴液漏斗和带有CaCl2干燥管的回流冷凝管,向三口烧瓶中置人,9.6g(0.4mo1)镁屑,用100mL无水甲基叔丁基醚浸没,边搅拌边滴入20%的4-溴-2-甲基-2-丁烯甲基叔丁基醚溶液(由0.2mol1-溴-3甲基-2-丁烯和无水甲基叔丁基醚配制而成),加入2粒碘,将三口烧瓶放入水浴锅中,水浴温度为40-45℃,回流反应30min,即得格式试剂2-甲基-2丁烯基溴化镁的甲基叔丁基醚溶液。
实施例3
一种红没药烯的合成方法,所述的红没药烯为γ-红没药烯,γ-红没药烯的合成方法,具体包括以下步骤:
反应式如下:
S1、γ-红没药烯醇的制备
将装有2-甲基-2丁烯基溴化镁的甲基叔丁基醚溶液的反应瓶移至冰盐浴中,维持温度在-5-0℃,逐滴加入含0.2mol的2-(4-甲基-3-烯-1-环己基)丙醛的甲基叔丁基醚溶液,在30min内滴加完毕,滴加完毕后升温至15℃,搅拌反应1h,加入50ml10%的盐酸水溶液,保温搅拌30-60min进行水解反应,加入20ml饱和氯化铵水溶液淬灭反应,用甲基叔丁基醚萃取水相,合并有机相,用无水硫酸钠干燥,旋转蒸发除去甲基叔丁基醚即得γ-红没药烯醇粗品;收率为93.5%;
所述的2-(4-甲基-3-烯-1-环己基)丙醛与甲基叔丁基醚溶液的体积比为1:5;
S2、γ-红没药烯的制备
向γ-红没药烯醇粗品中加入酸催化剂,在120-125℃下回流反应1h,减压蒸馏,收集540Pa下110-112℃的馏分,即得到γ-红没药烯;收率为88.5%;所得γ-红没药烯的质谱结果为:HRMS m/z(ESI+)calcd for C15H24([M+H]+),205.3935,found 205.1956;1H NMR(400MHz,CDCl3):δ(ppm)5.25(m,2H),2.68(d,2H),2.27(t,8H),1.87(s,9H),1.71(s,3H);
由于烯烃上的H在5.25处只有2个H,由此可知,得到的红没药烯为γ-红没药烯;
所述的酸催化剂为质量比为SnCl2:75%浓硫酸=1:20的混合物,所述酸催化剂的加入量为γ-红没药烯醇粗品总质量的25%。
以上内容仅仅是对本发明的构思所作的举例和说明,所属本技术领域的技术人员对所描述的具体实施例做各种各样的修改或补充或采用类似的方式替代,只要不偏离发明的构思或者超越本权利要求书所定义的范围,均应属于本发明的保护范围。
Claims (6)
1.一种红没药烯的合成方法,其特征在于:该红没药烯为γ-红没药烯,γ-红没药烯的合成方法,具体包括以下步骤:
步骤一:2-甲基-2丁烯基溴化镁的制备
4-溴-2-甲基-2-丁烯与镁屑在无水甲基叔丁基醚的环境下回流反应得到格式试剂2-甲基-2丁烯基溴化镁的甲基叔丁基醚溶液,反应式如下:
步骤二:γ-红没药烯的合成
反应式如下:
S1、γ-红没药烯醇的制备
将装有2-甲基-2丁烯基溴化镁的甲基叔丁基醚溶液的反应瓶移至冰盐浴中,维持温度在-5-0℃,逐滴加入含0.2mol的2-(4-甲基-3-烯-1-环己基)丙醛的甲基叔丁基醚溶液,在30min内滴加完毕,滴加完毕后升温至15℃,搅拌反应1h,加入50ml 10%的盐酸水溶液,保温搅拌30-60min进行水解反应,加入20ml饱和氯化铵水溶液淬灭反应,用甲基叔丁基醚萃取水相,合并有机相,用无水硫酸钠干燥,旋转蒸发除去甲基叔丁基醚即得γ-红没药烯醇粗品;
S2、γ-红没药烯的制备
向γ-红没药烯醇粗品中加入酸催化剂,在120-125℃下回流反应1h,减压蒸馏,收集馏分,即得到γ-红没药烯;所述的酸催化剂为质量比为SnCl2:75%浓硫酸=1:20的混合物。
2.根据权利要求1所述的一种红没药烯的合成方法,其特征在于:步骤一中2-甲基-2丁烯基溴化镁的制备具体为:在500mL三口烧瓶上,配置搅拌器、恒压滴液漏斗和带有CaCl2干燥管的回流冷凝管,向三口烧瓶中加入0.4mo1镁屑,用100mL无水甲基叔丁基醚浸没,边搅拌边滴入含20%的4-溴-2-甲基-2-丁烯甲基叔丁基醚溶液,加入2粒碘,将三口烧瓶放入水浴锅中,水浴温度为40-45℃,回流反应30min,即得格式试剂2-甲基-2丁烯基溴化镁的甲基叔丁基醚溶液。
3.根据权利要求2所述的一种红没药烯的合成方法,其特征在于:所述的20%的4-溴-2-甲基-2-丁烯甲基叔丁基醚溶液由0.2mol 1-溴-3甲基-2-丁烯和无水甲基叔丁基醚配制而成。
4.根据权利要求1所述的一种红没药烯的合成方法,其特征在于:步骤二中,所述的2-(4-甲基-3-烯-1-环己基)丙醛的甲基叔丁基醚溶液中2-(4-甲基-3-烯-1-环己基)丙醛与甲基叔丁基醚溶液的体积比为1:5。
5.根据权利要求1所述的一种红没药烯的合成方法,其特征在于:步骤二中,所述酸催化剂的加入量为γ-红没药烯醇粗品总质量的25-30%。
6.根据权利要求1所述的一种红没药烯的合成方法,其特征在于:步骤二中,所述的收集馏分为收集540Pa下110-112℃的馏分。
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