CN104910116A - Method for preparing 4,4-pyran diethyl dicarboxylate derivative - Google Patents
Method for preparing 4,4-pyran diethyl dicarboxylate derivative Download PDFInfo
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- CN104910116A CN104910116A CN201510255683.XA CN201510255683A CN104910116A CN 104910116 A CN104910116 A CN 104910116A CN 201510255683 A CN201510255683 A CN 201510255683A CN 104910116 A CN104910116 A CN 104910116A
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- alkali
- diethyl malonate
- butoxide
- dimethyl formamide
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D309/08—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D309/08—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D309/10—Oxygen atoms
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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing 4,4-pyran diethyl dicarboxylate and a derivative thereof. According to the invention, diethyl malonate and substituted dichloroethyl ether are adopted as raw materials; cuprous iodide is used for catalyzing; one or a mixture of compounds selected from potassium tert-butoxide, sodium tert-butoxide and sodium tert-pentoxide is adopted as an alkali, and a reaction is carried out; when the reaction is finished, a solvent is removed by reduced-pressure distillation; and reduced-pressure distillation is continued, such that 4,4-pyran diethyl dicarboxylate or the derivative thereof are obtained. The method provided by the invention has never been reported before. The raw materials are easy to obtain, the reaction method is simple and feasible, and the reaction time is short. The method has high application and market values.
Description
Technical field
The present invention relates to the method that one prepares 4,4-pyrans dicarboxylate and derivative thereof, belong to the synthesis field of Other substrate materials.
Background technology
In recent years, the microelectronics of China and the development of dull and stereotyped display industries rapidly, have driven foundation and the development of the relevant supporting enterprise in the industrial chains such as Other substrate materials.Particularly 2009 LED (photodiode) fast development, more effectively promoted the development of photoresist material industry.China photoresist material industrial market is on the basis of original discrete device, IC, LCD (liquid-crystal display), add LED again, add the potential market of photovoltaic, the photoresist material market to China in 2010 more than 2,000,000,000 yuan, will account for more than 10% of international photoresist material market ratio.
Photoresist material, in imaging process, owing to there is certain diffraction, reflection and scattering, reduces the contrast gradient of photoetching offset plate figure, thus reduces the resolving power of figure.Along with exposure the reducing of machining feature size, the reflection of incident light and scattering increasing on the impact improving graphics resolution.In order to improve the performance of exposure system resolving power, people are studying and adding one deck antireflecting coating between exposed photoresist and substrates, obviously can reduce photoresist material surface to the reflection of incident light and scattering, thus improve the resolving power performance of photoresist material.
4,4-pyrans dicarboxylate is the important source material preparing tetrahydropyrans-4-formic acid, and tetrahydropyrans-4-formic acid can be obtained by reacting photoresist material monomer with vinyl compound.The anti-reflecting layer prepared as raw material can reduce photoresist material surface significantly to the reflection of incident light and scattering, improves the resolving power of photoresist material.Similar compound is generally with sodium ethylate, sodium hydride, and salt of wormwood is alkali, adopt the feed way dripping dihalo-ether or drip diethyl malonate, but these synthetic method reaction times longer complicated operations, reaction yield is on the low side shortcomings of Denging, limits the widespread use of this compounds.
Summary of the invention
Technical problem to be solved by this invention is to provide one and prepares 4, the method of 4-pyrans dicarboxylate, the inventive method is different from the method that routine prepares this compounds, the feed way adopted is to diethyl malonate and replaces the DMF solution adding alkali in dichloroethyl ether system, use cuprous iodide catalysis, improve reactive behavior, shorten the reaction times, be easy to suitability for industrialized production.
The technical scheme that the present invention solves the problems of the technologies described above is as follows: one prepares the method for 4,4-pyrans dicarboxylate and derivative thereof, comprising:
In the reactor of nitrogen protection, add diethyl malonate, replace dichloroethyl ether, cuprous iodide and dimethyl formamide; the quality of described dimethyl formamide is 10 times of diethyl malonate quality; stirring is warming up to 100-110 DEG C; drip the dimethyl formamide solution of alkali, reaction 2h terminates, and removes solvent under reduced pressure; continue underpressure distillation again; obtain 4,4-pyrans dicarboxylate and derivative thereof, reaction equation is as follows:
Wherein, R is hydrogen, methoxyl group or ethyl; The dimethyl formamide solution of described alkali is that 1g alkali dissolution is in the dimethyl formamide of 3-5g.
On the basis of technique scheme, the present invention can also do following improvement.
Further, the mol ratio of described diethyl malonate, replacement dichloroethyl ether and alkali is 1:(1-1.1): (2-2.2), the mol ratio of described cuprous iodide and diethyl malonate is (0.5-1): 100.
Further, described alkali is the mixture of one or more in sodium tert-butoxide, potassium tert.-butoxide, sodium tert-amyl alcohol.
The invention has the beneficial effects as follows:
The invention provides one utilizes cuprous iodide catalysis to prepare the method for 4,4-pyrans dicarboxylate, and its advantage is:
1. 4, the 4-pyrans dicarboxylates prepared of the present invention, are important industrial chemicals, can be applied in pharmaceutical industries and photoresist material field well.
2. the present invention prepares 4,4-pyrans dicarboxylate, and the reaction times is shorter, adopts the feed way of the DMF solution dripping alkali, simple to operate, is easy to suitability for industrialized production.
3. the cheaper starting materials that the present invention is used is easy to get, and avoids and uses the dibromo ether and diiodo-ethyl ether that price is higher.
Embodiment
Be described principle of the present invention and feature below, example, only for explaining the present invention, is not intended to limit scope of the present invention.
The preparation (sodium tert-amyl alcohol is alkali) of embodiment 14,4-pyrans dicarboxylate
To in the 1L there-necked flask of nitrogen protection, add 48.0g (0.3mol) diethyl malonate, 42.6g (0.3mol) dichloroethyl ether, dry DMF, the 0.6g cuprous iodide of 480g, the system of obtaining is shallow yellow transparent solution.Stirring is warming up to 100 DEG C.Drip sodium tert-amyl alcohol DMF solution (by 69.3g sodium tert-amyl alcohol and 277.2gDMF formulated).Backflow 2h, GC track to without starting material left, remove solvent under reduced pressure, then continue underpressure distillation, obtain 61.5g colourless liquid, yield: 89.1%.
1H NMR(CDCl
3,TMS,500MHz):4.121-4.132(q,4H)，1.842-1.851(m,4H)，1.124-1.138(t,6H)；GC-MS：229(M+)。
The preparation (sodium tert-butoxide is alkali) of embodiment 24,4-pyrans dicarboxylate
To in the 1L there-necked flask of nitrogen protection, add 48.0g (0.3mol) diethyl malonate, 42.6g (0.3mol) dichloroethyl ether, dry DMF, the 0.6g cuprous iodide of 480g, the system of obtaining is shallow yellow transparent solution.Stirring is warming up to 100 DEG C.Drip 60.5g sodium tert-butoxide DMF solution (by 60.5g sodium tert-butoxide and 202gDMF formulated).Backflow 2h, GC track to without starting material left, remove solvent under reduced pressure, then continue underpressure distillation, obtain 58.0g colourless liquid, yield: 84.1%.
1H NMR(CDCl
3,TMS,500MHz):4.121-4.132(q,4H)，1.842-1.851(m,4H)，1.124-1.138(t,6H)；GC-MS：229(M+)。
The preparation (potassium tert.-butoxide is alkali) of embodiment 34,4-pyrans dicarboxylate
To in the 1L there-necked flask of nitrogen protection, add 48.0g (0.3mol) diethyl malonate, 42.6g (0.3mol) dichloroethyl ether, dry DMF, the 0.6g cuprous iodide of 480g, the system of obtaining is shallow yellow transparent solution.Stirring is warming up to 100 DEG C.Drip 71.2g potassium tert.-butoxide DMF solution (by 71.2g potassium tert.-butoxide and 284.8gDMF formulated).Backflow 2h, GC track to without starting material left, remove solvent under reduced pressure, then continue underpressure distillation, obtain 59.5g colourless liquid, yield: 86.2%.
1H NMR(CDCl
3,TMS,500MHz):4.121-4.132(q,4H)，1.842-1.851(m,4H)，1.124-1.138(t,6H)；GC-MS：229(M+)。
The preparation of embodiment 42,6-dimethoxy 4,4-pyrans dicarboxylate
To in the 1L there-necked flask of nitrogen protection, add 48.0g (0.3mol) diethyl malonate, 60.9g (0.3mol) 1; 1-dimethoxy-2,2-dichloroethyl ether, the dry DMF of 480g; 0.6g cuprous iodide, the system of obtaining is shallow yellow transparent solution.Stirring is warming up to 100 DEG C, drip 71.2g potassium tert.-butoxide DMF (by 71.2g sodium tert-amyl alcohol and 284.8gDMF formulated) solution.Backflow 2h, GC track to without starting material left, and decompression steams solvent, then continues underpressure distillation, obtains 63.5g colourless liquid, yield: 73.0%.
1H NMR(CDCl
3,TMS,500MHz):4.953-4.971(m,2H),4.122-4.132(m,4H),3.242(s,6H),2.312-2.563(m,4H),1.304-1.322(m,6H)；GC-MS：289(M+)。
The preparation of embodiment 52,6-diethyl 4,4-pyrans dicarboxylate
To in the 1L there-necked flask of nitrogen protection, add 48.0g (0.3mol) diethyl malonate, 59.7g (0.3mol) 1,1-diethyl-2,2-dichloroethyl ether, dry DMF, the 0.6g cuprous iodide of 480g, the system of obtaining is shallow yellow transparent solution.Stirring is warming up to 100 DEG C, drip 71.2g potassium tert.-butoxide DMF solution (by 71.2g potassium tert.-butoxide and 277.2gDMF formulated).Backflow 2h, GC track to without starting material left, and decompression steams solvent, then continues underpressure distillation, obtains 69.7g colourless liquid, yield: 81.2%.
1H NMR(CDCl
3,TMS,500MHz):4.125-4.143(m,4H),3.591-3.599(m,2H),2.132-2.382(m,4H),1.462-1.471(m,4H),1.304-1.384(m,6H)；0.961-0971(m，6H)；GC-MS：285(M+)。
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (3)
1. prepare the method for 4,4-pyrans dicarboxylate and derivative thereof for one kind, it is characterized in that, comprising:
In the reactor of nitrogen protection, add diethyl malonate, replace dichloroethyl ether, cuprous iodide and dimethyl formamide; the quality of described dimethyl formamide is 10 times of diethyl malonate quality; stirring is warming up to 100-110 DEG C; drip the dimethyl formamide solution of alkali, reaction 2h terminates, and removes solvent under reduced pressure; continue underpressure distillation again; obtain 4,4-pyrans dicarboxylate and derivative thereof, reaction equation is as follows:
Wherein, R is hydrogen, methoxyl group or ethyl; The dimethyl formamide solution of described alkali is that 1g alkali dissolution is in the dimethyl formamide of 3-5g.
2. method according to claim 1, it is characterized in that, the mol ratio of described diethyl malonate, replacement dichloroethyl ether and alkali is 1:(1-1.1): (2-2.2), the mol ratio of described cuprous iodide and diethyl malonate is (0.5-1): 100.
3. method according to claim 1 and 2, is characterized in that, described alkali is the mixture of one or more in sodium tert-butoxide, potassium tert.-butoxide, sodium tert-amyl alcohol.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040220214A1 (en) * | 1997-06-30 | 2004-11-04 | Targacept, Inc. | Pharmaceutical compositions and methods for effecting dopamine release |
| CN101417945A (en) * | 2008-10-23 | 2009-04-29 | 浙江工业大学 | Method for preparing 4-bromo-2,3,5,6-3-fluorophenylacetic acid |
| CN101743246A (en) * | 2007-05-25 | 2010-06-16 | F2G有限公司 | 2-oxo-2- (2-phenyl-5,6,7,8-tetrahydro-indolizin-3-yl) -acetamide derivatives and related compounds as antifungal agents |
| CN102105170A (en) * | 2008-05-29 | 2011-06-22 | F2G有限公司 | Antifungal combination therapy |
-
2015
- 2015-05-19 CN CN201510255683.XA patent/CN104910116B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040220214A1 (en) * | 1997-06-30 | 2004-11-04 | Targacept, Inc. | Pharmaceutical compositions and methods for effecting dopamine release |
| CN101743246A (en) * | 2007-05-25 | 2010-06-16 | F2G有限公司 | 2-oxo-2- (2-phenyl-5,6,7,8-tetrahydro-indolizin-3-yl) -acetamide derivatives and related compounds as antifungal agents |
| CN102105170A (en) * | 2008-05-29 | 2011-06-22 | F2G有限公司 | Antifungal combination therapy |
| CN101417945A (en) * | 2008-10-23 | 2009-04-29 | 浙江工业大学 | Method for preparing 4-bromo-2,3,5,6-3-fluorophenylacetic acid |
Non-Patent Citations (3)
| Title |
|---|
| CHRISTOPH STRASSLER等: "Novel Heterospirocyclic 3-Amino-2H-azirines as Synthons for Heterocyclic α-Amino Acids", 《HELVETICA CHIMICA ACTA》 * |
| 曾庆北等: "相转移催化活泼亚甲基的烃基化", 《化学试剂》 * |
| 谢文林等: "丙二酸二乙酯的相转移催化烃基化反应研究", 《化学试剂》 * |
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Denomination of invention: A method for preparing diethyl 4,4-pyranodicate derivatives Effective date of registration: 20211202 Granted publication date: 20170322 Pledgee: Yantai Branch of China Merchants Bank Co.,Ltd. Pledgor: VALIANT Co.,Ltd. Registration number: Y2021980013807 |
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Date of cancellation: 20220823 Granted publication date: 20170322 Pledgee: Yantai Branch of China Merchants Bank Co.,Ltd. Pledgor: VALIANT Co.,Ltd. Registration number: Y2021980013807 |
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