CN117466724A - 一种2-戊基-2-环戊烯-1-酮的制备方法 - Google Patents
一种2-戊基-2-环戊烯-1-酮的制备方法 Download PDFInfo
- Publication number
- CN117466724A CN117466724A CN202311211314.1A CN202311211314A CN117466724A CN 117466724 A CN117466724 A CN 117466724A CN 202311211314 A CN202311211314 A CN 202311211314A CN 117466724 A CN117466724 A CN 117466724A
- Authority
- CN
- China
- Prior art keywords
- amyl
- reaction
- methyl
- oxo
- cyclopentanone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- VNWOJVJCRAHBJJ-UHFFFAOYSA-N 2-pentylcyclopentan-1-one Chemical compound CCCCCC1CCCC1=O VNWOJVJCRAHBJJ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000001590 oxidative effect Effects 0.000 claims abstract description 18
- PZBBESSUKAHBHD-UHFFFAOYSA-N methyl 2-oxocyclopentane-1-carboxylate Chemical compound COC(=O)C1CCCC1=O PZBBESSUKAHBHD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000007800 oxidant agent Substances 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims abstract description 13
- YZWKKMVJZFACSU-UHFFFAOYSA-N 1-bromopentane Chemical compound CCCCCBr YZWKKMVJZFACSU-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 239000000706 filtrate Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 8
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000000967 suction filtration Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- JJKWGCAJCPFUPM-UHFFFAOYSA-N 2-methyl-2-pentylcyclopentan-1-one Chemical compound CCCCCC1(C)CCCC1=O JJKWGCAJCPFUPM-UHFFFAOYSA-N 0.000 claims abstract description 3
- 230000000911 decarboxylating effect Effects 0.000 claims abstract description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 3
- 239000011259 mixed solution Substances 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 17
- ILHZVKAXFCDFMT-UHFFFAOYSA-N 2-pentylcyclopent-2-en-1-one Chemical compound CCCCCC1=CCCC1=O ILHZVKAXFCDFMT-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 230000035484 reaction time Effects 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- BRMCOKJTFZKQJK-UHFFFAOYSA-N methyl 2-oxo-1-pentylcyclopentane-1-carboxylate Chemical compound CCCCCC1(C(=O)OC)CCCC1=O BRMCOKJTFZKQJK-UHFFFAOYSA-N 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000002585 base Substances 0.000 claims description 8
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 239000002699 waste material Substances 0.000 abstract description 4
- 239000007787 solid Substances 0.000 abstract description 2
- 239000011949 solid catalyst Substances 0.000 abstract description 2
- -1 2-oxo-1-amyl methyl Chemical group 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- KVWWIYGFBYDJQC-UHFFFAOYSA-N methyl dihydrojasmonate Chemical compound CCCCCC1C(CC(=O)OC)CCC1=O KVWWIYGFBYDJQC-UHFFFAOYSA-N 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- 238000005292 vacuum distillation Methods 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- BWZVCCNYKMEVEX-UHFFFAOYSA-N 2,4,6-Trimethylpyridine Chemical compound CC1=CC(C)=NC(C)=C1 BWZVCCNYKMEVEX-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- OHCMANJUZNNOQW-UHFFFAOYSA-N 2,4,4-trimethylcyclohexene-1-carbaldehyde Chemical compound CC1=C(C=O)CCC(C)(C)C1 OHCMANJUZNNOQW-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000020176 deacylation Effects 0.000 description 1
- 238000005947 deacylation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- JHZPNBKZPAWCJD-UHFFFAOYSA-N ethyl 2-oxocyclopentane-1-carboxylate Chemical compound CCOC(=O)C1CCCC1=O JHZPNBKZPAWCJD-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/65—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
-
- 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
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/673—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton
- C07C45/676—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton by elimination of carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated
Abstract
本发明公开了一种2‑戊基‑2‑环戊烯‑1‑酮的制备方法,包括如下步骤:搅拌条件下,在溶剂二甲基亚砜和碱的混合溶液中,先后滴加2‑氧代环戊烷羧酸甲酯和溴戊烷进行反应,反应结束后,反应液抽滤,滤液经减压精馏得到2‑氧代‑1‑戊基环戊烷甲酸甲酯;在碱的水溶液中加入2‑氧代‑1‑戊基环戊烷甲酸甲酯,脱羧水解,分液,水洗,干燥得到2‑戊基‑环戊酮;在溶剂中加入催化剂二苯基膦和氧化剂2,3‑二氯‑5,6‑二氰基‑1,4‑苯醌,滴加2‑戊基‑环戊酮,氧化得到2‑戊基‑2‑环戊烯‑1‑酮。本发明总收率与现有的合成路线相比,收率较高,避免了传统路线收率低的问题,反应后处理后可将固体催化剂和溶剂回收利用,且反应后处理简单,避免了传统路线易产生大量废固废液的问题。
Description
技术领域
本发明属于化学有机合成技术领域,具体涉及一种2-戊基-2-环戊烯-1-酮的制备方法。
背景技术
二氢茉莉酮酸甲酯是最为流行,深受调香师欢迎的合成香料,而2-戊基-2-环戊烯-1-酮则是合成二氢茉莉酮酸甲酯等香料的重要中间体。其分子式为 C10H16O,相对分子质量为152.12。2-戊基-2-环戊烯-1-酮的分子结构式为:
现有的制备2-戊基-2-环戊烯-1-酮的包括如下几种:
方法(1)以丁二烯与乙酰乙酸乙酯在钯催化下得到链状乙酰乙酸乙酯类化合物,该化合物经过选择性加氢、脱酰、水解、酰氯化、环化等过程最后得到产物2-戊基-2-环戊烯酮。其反应方程式如下所示:
不过该路线的缺点是路线较长,反应收率低,只有不到50%,且使用的金属催化剂价格昂贵。
方法( 2 )以α-乙氧羰基环戊酮为起始原料经过1-溴代正戊烷的取代,取代产物使用氯化钠和二甲基亚砜的水溶液脱羧,脱羧的产物用SO2C12的四氯化碳溶液把其烷基取代的碳原子氯代,然后在2,4,6,三甲基吡啶溶液中回流,得到产物2-戊基-2-环戊烯-1-酮。其反应方程式如下:
此路线的选择性不高,且需要用到毒性较大,危险性较高的氯化亚砜,且总收率只有55%左右。
发明内容
针对现有技术中存在的缺陷,本发明的目的在于提供一种2-戊基-2-环戊烯-1-酮的制备方法。
本发明的技术方案如下:
一种2-戊基-2-环戊烯-1-酮的制备方法,包括如下步骤:
1)搅拌条件下,在溶剂二甲基亚砜和碱的混合溶液中,先后滴加2-氧代环戊烷羧酸甲酯和溴戊烷进行反应,反应结束后,反应液抽滤,滤液经减压精馏得到2-氧代-1-戊基环戊烷甲酸甲酯;
2)在碱的水溶液中加入通过步骤1)得到的2-氧代-1-戊基环戊烷甲酸甲酯,脱羧水解,分液,水洗,干燥得到2-戊基-环戊酮;
3)在溶剂中加入催化剂二苯基膦(DPP)和氧化剂2,3-二氯-5,6-二氰基-1,4-苯醌(DDQ),滴加通过步骤2)得到的2-戊基-环戊酮,氧化得到2-戊基-2-环戊烯-1-酮;
4)步骤1)中的碱为碳酸钠、碳酸钾、氢氧化钠、甲醇钠或叔丁醇钠;
5)步骤2)中为氢氧化钠、氢氧化钾、碳酸钠、碳酸钾。
本发明反应方程式如下:
进一步地,步骤4)中所述的溶剂为苯、乙腈、四氢呋喃或二氯甲烷。
进一步地,步骤1)中2-氧代环戊烷羧酸甲酯、溴戊烷和碱的投料摩尔比为1:1~1.5:0.5~1.5,步骤1)的反应温度为30-90℃,原料滴完反应时间为4-12h。
进一步地,步骤2)中2-氧代-1-戊基环戊烷甲酸甲酯和碱的投料摩尔比为1:2~3,步骤2)的反应温度为50~100℃,原料滴完反应时间为4~8h。
进一步地,步骤3)中2-戊基-环戊酮、氧化剂和催化剂的投料摩尔比为1:1~1.5:0.05~0.5,步骤3)的反应温度为30~80℃,原料滴完反应时间为12~24h。
优选地,步骤1)中2-氧代环戊烷羧酸甲酯、溴戊烷和碱的投料摩尔比为1:1.1:1,步骤1)的反应温度为35℃,原料滴加完后反应时间为8h。
优选地,步骤2)中2-氧代-1-戊基环戊烷甲酸甲酯和碱的投料摩尔比为1:2.28,所述反应温度为90℃,原料滴加完后反应时间为6h。
优选地,步骤3)中2-戊基-环戊酮、氧化剂和催化剂的投料摩尔比为1:1.05:0.1,所述反应温度为40℃,原料滴加完后反应时间为16h。
本发明的有益效果如下:
1、本发明反应条件温和,原料廉价易得,操作简单快捷,适合工业化生产。
2、本发明改变了2-戊基-2-环戊烯-1-酮的合成路线,总收率在75%左右,和原先两条合成路线总收率在55%左右相比,收率较高。避免了传统路线收率低的问题。
3、本发明反应后处理后可将固体催化剂和溶剂回收利用,且反应后处理简单,避免了传统路线易产生大量废固废液的问题。
实施方式
下面结合具体实施例对本发明进行进一步描述,但本发明的保护范围并不仅限于此。
实施例1:2-戊基-2-环戊烯-1-酮的合成
在一个500 ml 三口烧瓶中加入磁子,依次加入69.0g碳酸钾、300 mL DMSO,在35℃下搅拌0.5 h后滴加71.0g 2-氧代环戊烷羧酸甲酯,滴加时间为1h,滴完后0.5 h开始滴加83.0g溴戊烷,滴加时间为1h,滴完后继续在35℃下反应8h,将反应液抽滤,滤液减压精馏,压力为138 Pa,回收80℃的馏分(DMSO),并收集到115℃的馏分102.2g,2-氧代-1-戊基环戊烷甲酸甲酯纯度95.2%,收率92.1%。
2-氧代-1-戊基环戊烷甲酸甲酯(无色透明油状液体)
核磁共振氢谱:1H NMR (600 MHz, Chloroform-d) δ 3.55 (s, 3H), 2.42 –2.34 (m, 1H), 2.28 – 2.06 (m, 2H), 1.90 – 1.71 (m, 4H), 1.45 – 1.36 (m, 1H),1.22 – 1.02 (m, 6H), 0.73 (t, J = 7.1 Hz, 3H).
核磁共振碳谱:13C NMR (151 MHz, CDCl3) δ 214.45, 171.34, 60.38, 52.16,37.75, 33.73, 32.53, 31.88, 24.33, 22.18, 19.45, 13.73.
在一个500mL茄形瓶中加入磁子,依次加入氢氧化钠42.0g,水220.0 g,搅拌溶解后加入2-氧代-1-戊基环戊烷甲酸甲酯102.2g(纯度95.2%),升温至90℃,反应时间为6h。反应结束后,分液,取下层有机相,水洗后用无水硫酸钠干燥即可得到2-戊基-环戊酮71.0g,纯度96.1%,收率95.1%。
2-戊基-环戊酮核磁数据(浅黄色透明油状液体):
核磁共振氢谱:1H NMR (600 MHz, Chloroform-d) δ 2.24 – 2.10 (m, 2H),2.05 – 1.88 (m, 3H), 1.74 – 1.63 (m, 2H), 1.45 (qd, J = 10.7, 6.6 Hz, 1H),1.30 – 1.12 (m, 7H), 0.80 (t, J = 7.0 Hz, 3H).
核磁共振碳谱:13C NMR (151 MHz, CDCl3) δ213.42, 49.03, 38.04, 31.70,29.57, 29.51, 27.13, 22.41, 20.67, 13.89.
在一个500mL三口烧瓶中加入磁子,依次加入催化剂二苯基膦8.1g、氧化剂2,3-二氯-5,6-二氰基-1,4-苯醌104.4g,苯200mL,搅拌溶解升温至40℃后,开始滴加2-戊基-环戊酮71.0g(纯度96.1%),滴加时间为1h,滴完后再反应16h。反应结束后,旋蒸回收苯,而后再抽滤,滤饼回收氧化剂2,3-二氯-5,6-二氰基-1,4-苯醌,滤液减压精馏,压力为138 Pa,收集到80℃的馏分58.5g,纯度96.0%,收率85.0%。
2-戊基-2-环戊烯-1-酮核磁数据(浅黄色透明油状液体):
核磁共振氢谱:1H NMR (600 MHz, Chloroform-d) δ 7.16 (dq, J = 2.7, 1.3Hz, 1H), 2.41 (dp, J = 6.7, 2.0 Hz, 2H), 2.24 – 2.20 (m, 2H), 2.03 – 1.97 (m,2H), 1.32 (p, J = 7.6 Hz, 2H), 1.19 – 1.10 (m, 4H), 0.73 (t, J = 7.1 Hz, 3H).
核磁共振碳谱:13C NMR (151 MHz, CDCl3) δ 209.63, 157.09, 146.27,34.38, 31.43, 27.27, 26.25, 24.57, 22.25, 13.78.
以2-氧代环戊烷羧酸甲酯为原料,合成2-戊基-2-环戊烯-1-酮的总收率为74.4%。
实施例2:2-戊基-2-环戊烯-1-酮的合成
在一个500 ml 三口烧瓶中加入磁子,依次加入27.0g甲醇钠、300 mL DMSO,在35℃下搅拌0.5 h后滴加71.0g 2-氧代环戊烷羧酸甲酯,滴加时间为1h。滴完后0.5 h开始滴加83.0g溴戊烷,滴加时间为1h。滴完后继续在35℃下反应8h,将反应液抽滤,滤液减压精馏,压力为138 Pa,回收80℃的馏分(DMSO),并收集到115℃的馏分100.5g,纯度95.1%,收率90.2%。
在一个500mL茄形瓶中加入磁子,依次加入氢氧化钾57.6g,水270.0 g,搅拌溶解后加入2-氧代-1-戊基环戊烷甲酸甲酯100.5g,升温至90℃,反应时间为6h。反应结束后,分液,取下层有机相,水洗后用无水硫酸钠干燥即可得到2-戊基-环戊酮69.2g,纯度96%,收率95.7%。
在一个500mL三口烧瓶中加入磁子,依次加入催化剂二苯基膦8.0 g、氧化剂2,3-二氯-5,6-二氰基-1,4-苯醌102.8g,乙腈200mL,搅拌溶解升温至40℃后,开始滴加入2-戊基-环戊酮69.2g, 滴加时间为1h,滴完后再反应16h。反应结束后,旋蒸回收乙腈,而后再抽滤,滤饼回收氧化剂2,3-二氯-5,6-二氰基-1,4-苯醌,滤液减压精馏,压力为138 Pa,收集到80℃的馏分57.1g,纯度96%,收率83.5%。
以2-氧代环戊烷羧酸甲酯为原料,合成2-戊基-2-环戊烯-1-酮的总收率为72.1%。
实施例3:2-戊基-2-环戊烯-1-酮的合成
在一个500 ml 三口烧瓶中加入磁子,依次加入48g.0叔丁醇钠、300 mL DMSO,在35℃下搅拌0.5 h后滴加71.0g 2-氧代环戊烷羧酸甲酯,滴加时间为1h。滴完后0.5 h开始滴加83.0g溴戊烷,滴加时间为1h。滴完后继续在35℃下反应8h,将反应液抽滤,滤液减压精馏,压力为138 Pa,回收80℃的馏分(DMSO),并收集到115℃的馏分103.0g,纯度95.0%,收率92.2%。
在一个1000mL茄形瓶中加入磁子,依次加入碳酸钠111.4g,水440.3 g,搅拌溶解后加入2-氧代-1-戊基环戊烷甲酸甲酯103.0g,升温至90℃,反应时间为6h。反应结束后,分液,取下层有机相,水洗后用无水硫酸钠干燥即可得到2-戊基-环戊酮69.2g,纯度96.0%,收率93.4%。
在一个500mL茄形瓶中加入磁子,依次加入催化剂二苯基膦8.0g、氧化剂2,3-二氯-5,6-二氰基-1,4-苯醌102.6g,200mL四氢呋喃,搅拌溶解升温至40℃后,开始滴加入2-戊基-环戊酮69.2g, 滴加时间为1h,滴完后再反应16h。反应结束后,旋蒸回收四氢呋喃,而后再抽滤,滤饼回收氧化剂2,3-二氯-5,6-二氰基-1,4-苯醌,滤液减压精馏,压力为138Pa,收集到80℃的馏分57.6g,纯度96.2%,收率84.7%。
以2-氧代环戊烷羧酸甲酯为原料,合成2-戊基-2-环戊烯-1-酮的总收率为72.9%。
实施例4:2-戊基-2-环戊烯-1-酮的合成
在一个500 ml 三口烧瓶中加入磁子,依次加入20.0g氢氧化钠、300 mL DMSO,在35℃下搅拌0.5 h后滴加71.0g 2-氧代环戊烷羧酸甲酯,滴加时间为1h。滴完后0.5 h开始滴加83.0g溴戊烷,滴加时间为1h。滴完后继续在35℃下反应8h,将反应液抽滤,滤液减压精馏,压力为138 Pa,回收80℃的馏分(DMSO),并收集到115℃的馏分104.3g,纯度95.2%,收率93.5%。
在一个500mL茄形瓶中加入磁子,依次加入碳酸钾147.3g,水580.3 g,搅拌溶解后加入2-氧代-1-戊基环戊烷甲酸甲酯104.3g,升温至90℃,反应时间为6h。反应结束后,分液,取下层有机相,水洗后用无水硫酸钠干燥即可得到2-戊基-环戊酮70.2g,纯度96.0%,收率93.4%。
在一个500mL三口烧瓶中加入磁子,依次加入催化剂二苯基膦8.0g、氧化剂2,3-二氯-5,6-二氰基-1,4-苯醌104.1g,二氯甲烷200mL,搅拌溶解升温至40℃后,开始滴加2-戊基-环戊酮70.2g, 滴加时间为1h,滴完后再反应16h。反应结束后,旋蒸回收二氯甲烷,而后再抽滤,滤饼回收氧化剂2,3-二氯-5,6-二氰基-1,4-苯醌,滤液减压精馏,压力为138 Pa,收集到80℃的馏分57.6g,纯度96.0%,收率83.2%。
以2-氧代环戊烷羧酸甲酯为原料,合成2-戊基-2-环戊烯-1-酮的总收率为72.7%。
Claims (8)
1.一种2-戊基-2-环戊烯-1-酮的制备方法,其特征在于,包括如下步骤:
1)搅拌条件下,在溶剂二甲基亚砜和碱的混合溶液中,先后滴加2-氧代环戊烷羧酸甲酯和溴戊烷进行反应,反应结束后,反应液抽滤,滤液经减压精馏得到2-氧代-1-戊基环戊烷甲酸甲酯;
2)在碱的水溶液中加入通过步骤1)得到的2-氧代-1-戊基环戊烷甲酸甲酯,脱羧水解,分液,水洗,干燥得到2-戊基-环戊酮;
3)在溶剂中加入催化剂二苯基膦和氧化剂2,3-二氯-5,6-二氰基-1,4-苯醌,滴加通过步骤2)得到的2-戊基-环戊酮,氧化得到2-戊基-2-环戊烯-1-酮;
4)步骤1)中的碱为碳酸钠、碳酸钾、氢氧化钠、甲醇钠或叔丁醇钠;
5)步骤2)中为氢氧化钠、氢氧化钾、碳酸钠、碳酸钾。
2.如权利要求1所述的制备方法,其特征在于,步骤4)中所述的溶剂为苯、乙腈、四氢呋喃或二氯甲烷。
3.如权利要求1所述的制备方法,其特征在于,步骤1)中2-氧代环戊烷羧酸甲酯、溴戊烷和碱的投料摩尔比为1:1~1.5:0.5~1.5,步骤1)的反应温度为30-90℃,原料滴加完后反应时间为4-12h。
4.如权利要求1所述的制备方法,其特征在于,步骤2)中2-氧代-1-戊基环戊烷甲酸甲酯和碱的投料摩尔比为1:2~3,步骤2)的反应温度为50~100℃,原料滴加完后反应时间为4~8h。
5.如权利要求1所述的制备方法,其特征在于,步骤3)中2-戊基-环戊酮、氧化剂和催化剂的投料摩尔比为1:1~1.5:0.05~0.5,步骤3)的反应温度为30~80℃,原料滴加完后反应时间为12~24h。
6.如权利要求3所述的制备方法,其特征在于,步骤1)中2-氧代环戊烷羧酸甲酯、溴戊烷和碱的投料摩尔比为1:1.1:1,步骤1)的反应温度为35℃,原料滴加完后反应时间为8h。
7.如权利要求4所述的制备方法,其特征在于,步骤2)中2-氧代-1-戊基环戊烷甲酸甲酯和碱的投料摩尔比为1:2.28,所述反应温度为90℃,原料滴加完后反应时间为6h。
8.如权利要求5所述的制备方法,其特征在于,步骤3)中2-戊基-环戊酮、氧化剂和催化剂的投料摩尔比为1:1.05:0.1,所述反应温度为40℃,原料滴加完后反应时间为16h。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202311211314.1A CN117466724A (zh) | 2023-09-20 | 2023-09-20 | 一种2-戊基-2-环戊烯-1-酮的制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202311211314.1A CN117466724A (zh) | 2023-09-20 | 2023-09-20 | 一种2-戊基-2-环戊烯-1-酮的制备方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN117466724A true CN117466724A (zh) | 2024-01-30 |
Family
ID=89624600
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202311211314.1A Pending CN117466724A (zh) | 2023-09-20 | 2023-09-20 | 一种2-戊基-2-环戊烯-1-酮的制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN117466724A (zh) |
-
2023
- 2023-09-20 CN CN202311211314.1A patent/CN117466724A/zh active Pending
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN113735701B (zh) | 一种8-羟基-2,2,14,14-四甲基十五烷二酸的制备方法 | |
CN113896674B (zh) | 一种阿普斯特的合成方法 | |
US20190359583A1 (en) | Process for preparing optically pure (r)-4-n-propyl-dihydrofuran-2(3h)-one | |
CN111170846B (zh) | 一种制备3,3-二甲基-2-氧-丁酸的方法 | |
CN111574444A (zh) | 一种贝达喹啉的制备方法 | |
CN109535120B (zh) | 7-取代-3,4,4,7-四氢环丁烷并香豆素-5-酮的制备方法 | |
CN117466724A (zh) | 一种2-戊基-2-环戊烯-1-酮的制备方法 | |
CN115010592A (zh) | 4-溴邻苯二甲酸的制备方法 | |
CN111269149B (zh) | 一种5-(3,3-二甲基胍基)-2-氧代戊酸的生产工艺 | |
JPS629098B2 (zh) | ||
CN111574384A (zh) | 一种手性1-氨基-2-丙醇的制备方法 | |
EP0990639B1 (en) | Process for producing n-cyclopropylanilines and intermediates used therefor | |
ZA200503239B (en) | Process for production of an acetylenic compound | |
JPH0421674A (ja) | 2―クロロ―5―(アミノメチル)チアゾールの製造方法 | |
CN115304477B (zh) | 一种芳香族羧酸酯的制备方法 | |
JP3563424B2 (ja) | 4h−ピラン−4−オンの製造方法 | |
CN111138315B (zh) | 一种氰烷基取代的醌类化合物及其合成方法 | |
CN113121321B (zh) | 一种a-R烷氧基对氯苄基磷酸单酯的回收及其再利用方法 | |
CN116003360B (zh) | 一种二氧化碳和炔烃合成橙酮类化合物制备方法 | |
CN112441920B (zh) | 一种铜光催化合成9-乙酰氧基-9,10-二氢菲类化合物的方法 | |
JP2586949B2 (ja) | p―又はm―ヒドロキシベンズアルデヒドの製造法 | |
JPH0251418B2 (zh) | ||
CN116063233A (zh) | 一种1h-咪唑-1-乙酸烃酯的制备方法 | |
JPH03271273A (ja) | 2―クロロ―5―(アミノメチル)ピリジンの製造方法 | |
JPS63270650A (ja) | P−(トランス−4−アミノメチルシクロヘキシルカルボニル)フエニルプロピオン酸の製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination |