CN104557489B - A kind of synthetic method of 3-cyclopenta propionic aldehyde - Google Patents
A kind of synthetic method of 3-cyclopenta propionic aldehyde Download PDFInfo
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- CN104557489B CN104557489B CN201410671944.1A CN201410671944A CN104557489B CN 104557489 B CN104557489 B CN 104557489B CN 201410671944 A CN201410671944 A CN 201410671944A CN 104557489 B CN104557489 B CN 104557489B
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- cyclopentyl
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- cyclopentylpropanal
- propanol
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- 238000010189 synthetic method Methods 0.000 title claims abstract description 7
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 title 2
- 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 25
- UWAOHFMOWBQIJH-UHFFFAOYSA-N 3-cyclopentylpropanal Chemical compound O=CCCC1CCCC1 UWAOHFMOWBQIJH-UHFFFAOYSA-N 0.000 claims abstract description 22
- IBMXMCXCSPGCDQ-UHFFFAOYSA-N 3-cyclopentylpropan-1-ol Chemical compound OCCCC1CCCC1 IBMXMCXCSPGCDQ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- 230000003647 oxidation Effects 0.000 abstract description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 229910052763 palladium Inorganic materials 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- LEHBURLTIWGHEM-UHFFFAOYSA-N pyridinium chlorochromate Chemical compound [O-][Cr](Cl)(=O)=O.C1=CC=[NH+]C=C1 LEHBURLTIWGHEM-UHFFFAOYSA-N 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- -1 3-cyclopentyl-1-propylmethyl ether Chemical compound 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 238000006646 Dess-Martin oxidation reaction Methods 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- NKLCNNUWBJBICK-UHFFFAOYSA-N dess–martin periodinane Chemical compound C1=CC=C2I(OC(=O)C)(OC(C)=O)(OC(C)=O)OC(=O)C2=C1 NKLCNNUWBJBICK-UHFFFAOYSA-N 0.000 description 2
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000746 allylic group Chemical group 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- DGQOCLATAPFASR-UHFFFAOYSA-N tetrahydroxy-1,4-benzoquinone Chemical compound OC1=C(O)C(=O)C(O)=C(O)C1=O DGQOCLATAPFASR-UHFFFAOYSA-N 0.000 description 1
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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
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
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- 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
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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
一种3-环戊基丙醛的合成方法是以3-环戊基-1-丙醇为原料经2,3-二氯-5,6-二氰基-1,4-苯醌/钯炭氧化合成3-环戊基丙醛的方法。本发明提供了一种合成3-环戊基丙醛的新方法，其特点是反应条件温和，操作简单，收率较高，成本较低。A kind of synthetic method of 3-cyclopentyl propionaldehyde is to take 3-cyclopentyl-1-propanol as raw material through 2,3-dichloro-5,6-dicyano-1,4-benzoquinone/palladium A method for the synthesis of 3-cyclopentylpropanal by carbon oxidation. The invention provides a new method for synthesizing 3-cyclopentylpropanal, which is characterized by mild reaction conditions, simple operation, high yield and low cost.
Description
技术领域 technical field
本发明涉及一种3-环戊基丙醛的合成方法，尤其是一种以3-环戊基-1-丙醇为原料经2,3-二氯-5,6-二氰基-1,4-苯醌（DDQ）/钯炭氧化合成3-环戊基丙醛的合成方法。 The present invention relates to a kind of synthetic method of 3-cyclopentyl propanal, especially a kind of 3-cyclopentyl-1-propanol as raw material through 2,3-dichloro-5,6-dicyano-1 , Synthetic method of 4-benzoquinone (DDQ)/palladium-carbon oxidation to 3-cyclopentylpropanal.
背景技术 Background technique
3-环戊基丙醛是化工中间体，也可用来制备药物，它的应用逐渐增多。3-环戊基丙醛的合成方法报道较少。US2011166191报道采用3-环戊基-1-丙醇为原料在DMSO和草酰氯的氧化下生成3-环戊基丙醛，收率89%。该方法的不足是需要-78℃的低温反应，反应条件苛刻。US2010/0234345报道采用3-环戊基-1-丙醇为原料在戴斯-马丁氧化剂的氧化下生成3-环戊基丙醛，收率73%。戴斯-马丁氧化剂价格较贵，氧化产物成本较高。WO99/32475文献采用了氯铬酸吡啶鎓（PCC）氧化3-环戊基-1-丙醇为3-环戊基丙醛，收率为70%。该方法的不足是PCC易造成环境污染。J.Org.Chem.,1996,60,8267-8269报道用HOF·CH3CN氧化裂解3-环戊基-1-丙甲醚得到3-环戊基丙醛，收率太低（15%）。 3-Cyclopentylpropanal is a chemical intermediate and can also be used to prepare medicines, and its application is gradually increasing. The synthesis method of 3-cyclopentylpropanal is less reported. US2011166191 reported that 3-cyclopentyl-1-propanol was used as a raw material to generate 3-cyclopentylpropanal under the oxidation of DMSO and oxalyl chloride, with a yield of 89%. The disadvantage of this method is that the low temperature reaction at -78°C is required, and the reaction conditions are harsh. US2010/0234345 reported using 3-cyclopentyl-1-propanol as a raw material to generate 3-cyclopentylpropanal under the oxidation of Dess-Martin oxidant, with a yield of 73%. Dess-Martin oxidizers are more expensive, and the cost of oxidation products is higher. WO99/32475 document uses pyridinium chlorochromate (PCC) to oxidize 3-cyclopentyl-1-propanol to 3-cyclopentyl propanal, and the yield is 70%. The disadvantage of this method is that PCC is easy to cause environmental pollution. J.Org.Chem., 1996,60,8267-8269 reported that 3-cyclopentyl-1-propylmethyl ether was oxidatively cracked with HOF CH 3 CN to obtain 3-cyclopentyl propionaldehyde, and the yield was too low (15% ).
发明内容 Contents of the invention
本发明的目的在于提供一种反应条件温和、操作简单、收率较高、成本较低的3-环戊基丙醛合成方法。 The object of the present invention is to provide a kind of 3-cyclopentyl propanal synthesis method with mild reaction conditions, simple operation, higher yield and lower cost.
DDQ作为氧化剂易氧化烯丙位的醇为醛。由于它不会进一步把醛氧化为酸且选择性好而广泛应用于烯丙醇制备醛的反应中，但较难氧化脂肪族醇。为了提高DDQ氧化脂肪族醇的活性，本发明通过在DDQ中加入钯炭协同氧化3-环戊基-1-丙醇得到较高收率的3-环戊基丙醛。 As an oxidizing agent, DDQ easily oxidizes the alcohols at the allylic position to aldehydes. Because it will not further oxidize aldehyde to acid and has good selectivity, it is widely used in the reaction of allyl alcohol to aldehyde, but it is difficult to oxidize aliphatic alcohol. In order to improve the activity of DDQ in oxidizing aliphatic alcohols, the present invention obtains 3-cyclopentylpropanal with a higher yield by adding palladium carbon into DDQ to synergistically oxidize 3-cyclopentyl-1-propanol.
本发明的上述目的是通过以下技术方案实现的： Above-mentioned purpose of the present invention is achieved through the following technical solutions:
一种3-环戊基丙醛的合成方法，其所述方法是按以下方案实现的： A kind of synthetic method of 3-cyclopentylpropanal, its described method is realized according to the following scheme:
将3-环戊基-1-丙醇、甲醇、钯炭、DDQ按照质量比例为W:W:W:W=6.7:52.7:1:6.7依次投料,反应至原料消耗毕，处理反应液得到3-环戊基丙醛，收率80%。 3-cyclopentyl-1-propanol, methanol, palladium carbon, and DDQ are fed sequentially according to the mass ratio of W:W:W:W=6.7:52.7:1:6.7, react until the raw materials are consumed, and process the reaction solution to obtain 3-cyclopentyl propanal, yield 80%.
本发明的优点在于： The advantages of the present invention are:
（1）反应条件温和。常压操作，没有太低或太高的温度。 (1) The reaction conditions are mild. Normal pressure operation, no too low or too high temperature.
（2）成本较低。本发明所用的氧化剂DDQ，氧化反应后变为2,3-二氯-5,6-二氰基-1,4-氢醌，只要用矿物酸或其它价廉的氧化剂氧化即可把2,3-二氯-5,6-二氰基-1,4-氢醌又转变成2,3-二氯-5,6-二氰基-1,4-苯醌。钯炭可重复使用。本发明较易实现工业化生产。 (2) The cost is lower. The oxidizing agent DDQ used in the present invention becomes 2,3-dichloro-5,6-dicyano-1,4-hydroquinone after the oxidation reaction, and 2, 3-Dichloro-5,6-dicyano-1,4-hydroquinone is converted into 2,3-dichloro-5,6-dicyano-1,4-benzoquinone. Palladium on charcoal is reusable. The invention is easier to realize industrialized production.
具体实施方式 detailed description
下面对本发明的具体实施方式作进一步的说明。 Specific embodiments of the present invention will be further described below.
实施本发明所提供的一种3-环戊基-1-丙醛的合成方法。它是以DDQ、钯炭为氧化剂把3-环戊基-1-丙醇氧化为3-环戊基丙醛。将3-环戊基-1-丙醇、甲醇、钯炭、DDQ按照质量比例为W:W:W:W=6.7:52.7:1:6.7依次投料,反应至原料消耗毕，处理反应液得到3-环戊基丙醛，收率80%。 Implement a kind of synthetic method of 3-cyclopentyl-1-propanal provided by the present invention. It oxidizes 3-cyclopentyl-1-propanol to 3-cyclopentylpropanal with DDQ and palladium carbon as oxidants. 3-cyclopentyl-1-propanol, methanol, palladium carbon, and DDQ are fed sequentially according to the mass ratio of W:W:W:W=6.7:52.7:1:6.7, react until the raw materials are consumed, and process the reaction solution to obtain 3-cyclopentyl propanal, yield 80%.
下面通过具体实施例对本发明的具体实施方式作出进一步的说明。 The specific embodiment of the present invention will be further described below through specific examples.
实施例1Example 1
将20.0g3-环戊基-1-丙醇、200mL甲醇、2.0g钯炭放入反应瓶中，室温搅拌下分批加入54gDDQ。加毕，室温下反应6h，然后回流反应24h至原料3-环戊基-1-丙醇消耗完毕。过滤，减压浓缩反应液除去甲醇，再加入环己烷，过滤，减压蒸馏得15.8g3-环戊基丙醛，收率80%。 Put 20.0g of 3-cyclopentyl-1-propanol, 200mL of methanol, and 2.0g of palladium carbon into the reaction flask, and add 54g of DDQ in batches under stirring at room temperature. After the addition, react at room temperature for 6h, then reflux for 24h until the raw material 3-cyclopentyl-1-propanol is consumed. Filter, concentrate the reaction solution under reduced pressure to remove methanol, then add cyclohexane, filter, and distill under reduced pressure to obtain 15.8 g of 3-cyclopentylpropionaldehyde, with a yield of 80%.
实施例2Example 2
将20.0g3-环戊基-1-丙醇、200mL甲醇、2.0g钯炭放入反应瓶中，室温搅拌下分批加入54gDDQ。加毕，室温下反应6h，然后在250W下微波反应30min。冷却，过滤，减压浓缩反应液除去甲醇，再加入环己烷，冷却，过滤，减压蒸馏得15.4g3-环戊基丙醛，收率78%。 Put 20.0g of 3-cyclopentyl-1-propanol, 200mL of methanol, and 2.0g of palladium carbon into the reaction flask, and add 54g of DDQ in batches under stirring at room temperature. After the addition is complete, react at room temperature for 6 h, then microwave at 250 W for 30 min. Cool, filter, and concentrate the reaction solution under reduced pressure to remove methanol, then add cyclohexane, cool, filter, and distill under reduced pressure to obtain 15.4 g of 3-cyclopentylpropionaldehyde, with a yield of 78%.
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Citations (3)
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|---|---|---|---|---|
| US6051586A (en) * | 1997-12-19 | 2000-04-18 | Bayer Corporation | Sulfonamide substituted chroman derivatives useful as beta 3 adrenoreceptor agonists |
| CN1254344A (en) * | 1997-05-02 | 2000-05-24 | 美国家用产品公司 | Estrogenic 10-Noradnrost-17-one derivatives with aromatic B-ring |
| CN101765593A (en) * | 2007-04-17 | 2010-06-30 | 雅培制药有限公司 | 2-iminoisothiazole derivatives as cannabinoid receptor ligands |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1254344A (en) * | 1997-05-02 | 2000-05-24 | 美国家用产品公司 | Estrogenic 10-Noradnrost-17-one derivatives with aromatic B-ring |
| US6051586A (en) * | 1997-12-19 | 2000-04-18 | Bayer Corporation | Sulfonamide substituted chroman derivatives useful as beta 3 adrenoreceptor agonists |
| CN101765593A (en) * | 2007-04-17 | 2010-06-30 | 雅培制药有限公司 | 2-iminoisothiazole derivatives as cannabinoid receptor ligands |
Non-Patent Citations (1)
| Title |
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| 羰基化法合成碳酸二苯酯技术进展;贾艳秋等;《化学工业与工程技术》;20030630;第24卷(第3期);第11-14页 * |
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