CN112811970A - Preparation method of 2-alkoxy-2-cyclopentene-1-ketone - Google Patents
Preparation method of 2-alkoxy-2-cyclopentene-1-ketone Download PDFInfo
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- CN112811970A CN112811970A CN202010501159.7A CN202010501159A CN112811970A CN 112811970 A CN112811970 A CN 112811970A CN 202010501159 A CN202010501159 A CN 202010501159A CN 112811970 A CN112811970 A CN 112811970A
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- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B41/00—Formation or introduction of functional groups containing oxygen
- C07B41/04—Formation or introduction of functional groups containing oxygen of ether, acetal or ketal groups
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- 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
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- C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated
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Abstract
The invention discloses a method for preparing 2-alkoxy-2-cyclopentene-1-ketone, which specifically comprises the steps of taking cyclopentanone and fatty alcohol as reaction substrates, and obtaining the 2-alkoxy-2-cyclopentene-1-ketone through a series reaction of iodination, substitution, oxidation and addition elimination in the presence of equivalent iodine and copper salt. The chemical structural general formula of cyclopentanone is
The chemical structural general formula of the alcohol is R2And OH, wherein the copper salt is selected from one of copper acetate, cuprous iodide, elementary copper and copper oxide. The preparation method disclosed by the invention has the advantages of easily available raw materials, wide substrate range, simplicity and convenience in operation, greenness, safety and the like.
Description
Technical Field
The invention relates to a preparation method of 2-alkoxy-2-cyclopentene-1-ketone.
Background
2-alkoxy-2-cyclopenten-1-ones are a very important class of cyclic compounds which can be used as precursors for drug synthesis. The conventional method is generally obtained by reacting 1, 2-cyclopentanedione with an alkoxy reagent in the presence of an acid (Oncogene 2016, 35, 2518; j.med.chem.2009, 52, 5152; eur.j.org.chem.2010, 6354). However, the further application is limited by the defects of narrow substrate range, generally low yield, difficult raw material acquisition, complex operation and the like.
Disclosure of Invention
Aiming at the technical problems, the invention aims to provide the preparation method of the 2-alkoxy-2-cyclopentene-1-ketone, which has the advantages of wider substrate range, higher yield, simpler and more convenient operation, greenness and safety.
The technical scheme adopted by the invention is as follows: cyclopentanone, iodine and ketone salt (in a ratio of 1: 0.5-1.5) are added to a reaction vessel, and then 20-60 mL of aliphatic alcohol is added, followed by reaction at 100 ℃ for 12 hours. After the reaction is finished, filtering, distilling under reduced pressure and carrying out column chromatography to obtain the 2-alkoxy-2-cyclopentene-1-ketone.
The chemical structural general formula of the cyclopentanone is
Wherein R is1Is one of hydrogen, methyl and ethyl.
The chemical structural general formula of the fatty alcohol is R2OH, wherein R2Is one of methyl, ethyl, n-propyl, n-butyl, isobutyl and isopropyl.
The copper salt is selected from one of copper acetate, cuprous iodide, elementary copper and copper oxide.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
1. the raw materials are cheap and easy to obtain, and the economic cost is low;
2. the method does not need anhydrous and anaerobic operation, is simple and practical to operate, and is easy to realize large-scale production;
3. the method has higher yield, is applicable to different fatty alcohols and cyclopentanone, and has wider substrate range;
4. the reaction byproducts in the invention are inorganic salt and water, thus being more green and safe.
Detailed Description
The present invention will be described in further detail with reference to specific examples. Reagents, equipment and methods employed in the present invention are reagents, equipment and methods conventionally commercially available in the art and conventionally used unless otherwise specified.
The first embodiment is as follows:
cyclopentanone (1a, 5mmol), iodine (5mmol), copper oxide (7.5mmol) and ethanol (2a, 60mL) were charged into a reaction flask, followed by heating at 100 ℃ for 12 hours. After the reaction is finished, filtering, distilling under reduced pressure and carrying out column chromatography to obtain a product 3aa, wherein the yield is 76%. A light yellow oily liquid;1H NMR(600MHz，CDCl3)：δ6.39(t，J＝3.1Hz，1H)，3.93(q，J＝7.1Hz，2H)，2.54-2.51(m，2H)，2.44-2.42(m，2H)，1.40(t，J＝7.1Hz，3H)；13C NMR(150MHz，CDCl3)：δ202.6，156.5，127.2，65.4，32.9，21.8，14.2。
example two:
cyclopentanone (1a, 5mmol), iodine (5mmol), copper oxide (7.5mmol) and methanol (2b, 60mL) were charged into a reaction flask, followed by heating at 100 ℃ for 12 hours. After the reaction is finished, filtering, distilling under reduced pressure and carrying out column chromatography to obtain a product 3ab, wherein the yield is 40%. A colorless oily liquid;1H NMR(400MHz，CDCl3)：δ6.41-6.38(m，1H)，3.75-3.73(m，3H)，2.54-2.51(m，2H)，2.47-2.43(m，2H)；13C NMR(100MHz，CDCl3)：δ202.4，157.5，126.9，57.0，33.1，21.8。
example three:
cyclopentanone (1a, 5mmol), iodine (5mmol), copper oxide (7.5mmol) and n-propanol (2c, 60mL) were added to a reaction flask, followed by heating at 100 ℃ for 12 hours. After the reaction is finished, filtering, distilling under reduced pressure and carrying out column chromatography to obtain a product 3ac, wherein the yield is 67%. A light yellow oily liquid;1H NMR(400MHz，CDCl3)：δ6.37(t，J＝3.0Hz，1H)，3.81(t，J＝6.7Hz，2H)，2.54-2.50(m，2H)，2.45-2.42(m，2H)，1.83-1.77(m，2H)，1.00(t，J＝7.4Hz，3H)；13C NMR(100MHz，CDCl3)：δ202.6，156.7，127.2，71.4，33.1，22.0，21.8，10.3；HRMS(ESI)：calcd for C8H12NaO2[M+Na]+163.0730，found 163.0726。
example four:
cyclopentanone (1a, 5mmol), iodine (5mmol), copper oxide (7.5mmol) and n-butanol (2d, 60mL) were charged into a reaction flask, followed by heating at 100 ℃ for 12 hours. After the reaction is finished, filtering, distilling under reduced pressure and carrying out column chromatography to obtain the product 3ad with the yield of 72 percent. A light yellow oily liquid;1H NMR(400MHz，CDCl3)：δ6.37(t，J＝3.0Hz，1H)，3.85(t，J＝6.6Hz，2H)，2.54-2.50(m，2H)，2.45-2.42(m，2H)，1.79-1.71(m，2H)，1.48-1.41(m，2H)，0.94(t，J＝7.4Hz，3H)；13C NMR(100MHz，CDCl3)：δ202.7，156.7，127.3，69.7，33.1，30.7，21.8，19.1，13.7；HRMS(ESI)：calcd for C9H14NaO2[M+Na]+177.0886，found 177.0883。
example five:
cyclopentanone (1a, 5mmol), iodine (5mmol), copper oxide (7.5mmol) and isobutanol (2e, 60mL) were added to a reaction flask, followed by heating at 100 ℃ for 12 hours. After the reaction is finished, the product 3ae can be obtained by filtering, reduced pressure distillation and column chromatography, and the yield is 44%. A light yellow oily liquid;1H NMR(400MHz，CDCl3)：δ6.36(t，J＝3.0Hz，1H)，3.60(d，J＝6.7Hz，2H)，2.53-2.49(m，2H)，2.45-2.42(m，2H)，2.10(hept，J＝6.7Hz，1H)，0.98(d，J＝6.7Hz，6H)；13C NMR(100MHz，CDCl3)：δ202.5，156.9，127.3，76.3，33.1，27.8，21.8，19.2。
example six:
cyclopentanone (1a, 5mmol), iodine (5mmol), copper oxide (7.5mmol) and isopropanol (2f, 60mL) were added to a reaction flask, followed by heating at 100 ℃ for 12 hours. After the reaction is finished, filtering, distilling under reduced pressure and carrying out column chromatography to obtain a product 3af with the yield of 83%. A light yellow oily liquid;1H NMR(400MHz，CDCl3)：δ6.36(t，J＝3.0Hz，1H)，4.31(hept，J＝6.1Hz，1H)，2.55-2.51(m，2H)，2.45-2.41(m，2H)，1.32(d，J＝6.1Hz，6H)；13CNMR(100MHz，CDCl3)：δ203.4，155.3，127.6，72.1，32.9，21.9，21.3；HRMS(ESI)：calcd for C8H12NaO2[M+Na]+163.0730，found 163.0727。
example seven:
3-methylcyclopentanone (1b, 5mmol), iodine (5mmol), copper oxide (7.5mmol) and ethanol (2a, 60mL) were added to a reaction flask, followed by heating at 100 ℃ for 12 hours. After the reaction is finished, the product 3ba can be obtained by filtering, reduced pressure distillation and column chromatography, and the yield is 46%. Light yellow oily liquidA body;1H NMR(600MHz，CDCl3)：δ6.28(d，J＝2.9Hz，1H)，3.94-3.88(m，2H)，2.90-2.84(m，1H)，2.66(dd，J1＝19.1Hz，J2＝6.2Hz，1H)，1.98(dd，J1＝19.1Hz，J2＝1.8Hz，1H)，1.39(t，J＝7.0Hz，3H)，1.18(d，J＝7.0Hz，3H)；13C NMR(150MHz，CDCl3)：δ202.5，155.8，132.8，65.4，41.8，29.1，21.5，14.3；HRMS(ESI)：calcd for C8H12NaO2[M+Na]+163.0730，found 163.0725。
example eight:
3-Ethylcyclopentanone (1c, 5mmol), iodine (5mmol), copper oxide (7.5mmol) and ethanol (2a, 60mL) were added to a reaction flask, followed by heating at 100 ℃ for 12 hours. After the reaction is finished, filtering, distilling under reduced pressure and carrying out column chromatography to obtain a product 3ca with the yield of 59%. A light yellow oily liquid;1H NMR(600MHz，CDCl3)：δ6.33(d，J＝2.8Hz，1H)，3.92(qd，J1＝7.0Hz，J2＝0.8Hz，2H)，2.74-2.68(m，1H)，2.62-2.57(m，1H)，2.06-2.02(m，1H)，1.60-1.51(m，1H)，1.49-1.41(m，1H)，1.39(tt，J1＝7.0Hz，J2＝1.0Hz，3H)，0.97(tt，J1＝7.4Hz，J2＝1.0Hz，3H)；13C NMR(150MHz，CDCl3)：δ202.3，156.0，131.2，65.4，39.7，35.9，28.8，14.2，11.5；HRMS(ESI)：calcd for C9H14NaO2[M+Na]+177.0886，found 177.0878。
example nine:
cyclopentanone (1a, 5mmol), iodine (5mmol), copper oxide (7.5mmol) and ethanol (2a, 40mL) were added to a reaction flask, which was then heated at 100 deg.C for reactionShould be 12 hours. After the reaction is finished, the product 3aa can be obtained by filtering, reduced pressure distillation and column chromatography, and the yield is 73%. A light yellow oily liquid;1H NMR(600MHz，CDCl3)：δ6.39(t，J＝3.1Hz，1H)，3.93(q，J＝7.1Hz，2H)，2.54-2.51(m，2H)，2.44-2.42(m，2H)，1.40(t，J＝7.1Hz，3H)；13C NMR(150MHz，CDCl3)：δ202.6，156.5，127.2，65.4，32.9，21.8，14.2。
example ten:
cyclopentanone (1a, 5mmol), iodine (5mmol), copper oxide (7.5mmol) and ethanol (2a, 20mL) were charged into a reaction flask, followed by heating at 100 ℃ for 12 hours. After the reaction is finished, filtering, distilling under reduced pressure and carrying out column chromatography to obtain a product 3aa, wherein the yield is 69%. A light yellow oily liquid;1H NMR(600MHz，CDCl3)：δ6.39(t，J＝3.1Hz，1H)，3.93(q，J＝7.1Hz，2H)，2.54-2.51(m，2H)，2.44-2.42(m，2H)，1.40(t，J＝7.1Hz，3H)；13C NMR(150MHz，CDCl3)：δ202.6，156.5，127.2，65.4，32.9，21.8，14.2。
example eleven:
cyclopentanone (1a, 5mmol), iodine (5mmol), copper oxide (2.5mmol) and ethanol (2a, 20mL) were charged into a reaction flask, followed by heating at 100 ℃ for 12 hours. After the reaction is finished, filtering, distilling under reduced pressure and carrying out column chromatography to obtain a product 3aa, wherein the yield is 48%. A light yellow oily liquid;1H NMR(600MHz，CDCl3)：δ6.39(t，J＝3.1Hz，1H)，3.93(q，J＝7.1Hz，2H)，2.54-2.51(m，2H)，2.44-2.42(m，2H)，1.40(t，J＝7.1Hz，3H)；13C NMR(150MHz，CDCl3)：δ202.6，156.5，127.2，65.4，32.9，21.8，14.2。
example twelve:
cyclopentanone (1a, 5mmol), iodine (5mmol), copper oxide (5mmol) and ethanol (2a, 20mL) were charged into a reaction flask, followed by heating at 100 ℃ for 12 hours. After the reaction is finished, filtering, distilling under reduced pressure and carrying out column chromatography to obtain a product 3aa, wherein the yield is 47%. A light yellow oily liquid;1H NMR(600MHz，CDCl3)：δ6.39(t，J＝3.1Hz，1H)，3.93(q，J＝7.1Hz，2H)，2.54-2.51(m，2H)，2.44-2.42(m，2H)，1.40(t，J＝7.1Hz，3H)；13C NMR(150MHz，CDCl3)：δ202.6，156.5，127.2，65.4，32.9，21.8，14.2。
example thirteen:
cyclopentanone (1a, 5mmol), iodine (5mmol), copper powder (5mmol) and ethanol (2a, 20mL) were charged into a reaction flask, followed by heating at 100 ℃ for 12 hours. After the reaction is finished, filtering, distilling under reduced pressure and carrying out column chromatography to obtain a product 3aa, wherein the yield is 13%. A light yellow oily liquid;1H NMR(600MHz，CDCl3)：δ6.39(t，J＝3.1Hz，1H)，3.93(q，J＝7.1Hz，2H)，2.54-2.51(m，2H)，2.44-2.42(m，2H)，1.40(t，J＝7.1Hz，3H)；13C NMR(150MHz，CDCl3)：δ202.6，156.5，127.2，65.4，32.9，21.8，14.2。
example fourteen:
cyclopentanone (1a, 5mmol), iodine (5mmol), cuprous iodide (5mmol) and ethanol (2a, 20mL) were added to a reaction flask, followed by heating at 100 ℃ for 12 hours. After the reaction is finished, filtering, distilling under reduced pressure and carrying out column chromatography to obtain a product 3aa, wherein the yield is 24%. Light yellowA colored oily liquid;1H NMR(600MHz，CDCl3)：δ6.39(t，J＝3.1Hz，1H)，3.93(q，J＝7.1Hz，2H)，2.54-2.51(m，2H)，2.44-2.42(m，2H)，1.40(t，J＝7.1Hz，3H)；13C NMR(150MHz，CDCl3)：δ202.6，156.5，127.2，65.4，32.9，21.8，14.2。
example fifteen:
cyclopentanone (1a, 5mmol), iodine (5mmol), copper acetate (5mmol) and ethanol (2a, 20mL) were added to a reaction flask, followed by heating at 100 ℃ for 12 hours. After the reaction is finished, filtering, distilling under reduced pressure and carrying out column chromatography to obtain a product 3aa, wherein the yield is 25%. A light yellow oily liquid;1H NMR(600MHz，CDCl3)：δ6.39(t，J＝3.1Hz，1H)，3.93(q，J＝7.1Hz，2H)，2.54-2.51(m，2H)，2.44-2.42(m，2H)，1.40(t，J＝7.1Hz，3H)；13C NMR(150MHz，CDCl3)：δ202.6，156.5，127.2，65.4，32.9，21.8，14.2。
Claims (5)
1. a preparation method of 2-alkoxy-2-cyclopentene-1-ketone is characterized in that: firstly, cyclopentanone, iodine and ketone salt are added into a reaction container, then 20-60 mL of aliphatic alcohol is added, then the reaction is carried out for 12 hours at the temperature of 100 ℃, and after the reaction is finished, the 2-alkoxy-2-cyclopentene-1-ketone is obtained by filtering, reduced pressure distillation and column chromatography.
2. The process for producing 2-alkoxy-2-cyclopenten-1-one according to claim 1, characterized in that: the chemical structural general formula of the cyclopentanone is
Wherein R is1Is one of hydrogen, methyl and ethyl.
3. The process for producing 2-alkoxy-2-cyclopenten-1-one according to claim 1The method is characterized in that: the chemical structural general formula of the fatty alcohol is R2OH, wherein R2Is one of methyl, ethyl, n-propyl, n-butyl, isobutyl and isopropyl.
4. The process for producing 2-alkoxy-2-cyclopenten-1-one according to claim 1, characterized in that: the copper salt is selected from one of copper acetate, cuprous iodide, elementary copper and copper oxide.
5. The process for producing 2-alkoxy-2-cyclopenten-1-one according to claim 1, characterized in that: the ratio of cyclopentanone, iodine and ketone salt is 1:1: 0.5-1.5.
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| BE560849A (en) * | 1956-09-19 | 1960-05-06 | Merck & Co Inc | CHEMICAL COMPOUNDS AND METHODS FOR THEIR PREPARATION. |
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2020
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| BE560849A (en) * | 1956-09-19 | 1960-05-06 | Merck & Co Inc | CHEMICAL COMPOUNDS AND METHODS FOR THEIR PREPARATION. |
| WO2003070706A1 (en) * | 2002-02-19 | 2003-08-28 | Pharmacia Corporation | Tricyclic pyrazole derivatives for the treatment of inflammation |
| EP1811037A1 (en) * | 2006-01-18 | 2007-07-25 | Chirogate International Inc. | Process for the preparation of optically active cyclopentenones |
| CN103449996A (en) * | 2012-06-01 | 2013-12-18 | 上海阳帆医药科技有限公司 | Preparation method of meptazinol hydrochloride intermediate 3-alkylox-2-cyclohexenyl-1-one |
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