CN104910116B - 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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- CN104910116B CN104910116B CN201510255683.XA CN201510255683A CN104910116B CN 104910116 B CN104910116 B CN 104910116B CN 201510255683 A CN201510255683 A CN 201510255683A CN 104910116 B CN104910116 B CN 104910116B
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- alkali
- diethyl malonate
- butoxide
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- pyrans
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- VHKODMGKTMPVCE-UHFFFAOYSA-N CCOC(C(C1)(CC(OC)OC1OC)C(OCC)=N)=C Chemical compound CCOC(C(C1)(CC(OC)OC1OC)C(OCC)=N)=C VHKODMGKTMPVCE-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
-
- 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
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 kind prepares 4,4- pyrans dicarboxylate and its derivant, belongs to Other substrate materials
Synthesis field.
Background technology
In recent years, Chinese microelectronics and flat board display industry quickly grow, in having driven the industrial chains such as Other substrate materials
Related supporting enterprise foundation and development.Particularly 2009 LED (light emitting diode) fast development, more effectively push away
The development of photoresist industry is moved.Chinese photoresist industrial market is in original discrete device, the base of IC, LCD (liquid crystal display)
On plinth, LED is added again, along with the potential market of photovoltaic, by 2010, Chinese photoresist market will be accounted for more than 2,000,000,000 yuan
More than the 10% of international photoresist market ratio.
Photoresist due to there is certain diffraction, reflection and scattering, reduces the right of photoetching offset plate figure in imaging process
Than degree, so as to reduce the resolution of figure.With the diminution of exposure machining feature size, the reflection and scattering of incident illumination is to carrying
The impact of high graphics resolution is increasing.In order to improve the performance of exposure system resolution, people are being studied in exposure light
Add one layer of ARC between photoresist and substrate, reflection and scattering of the photoresist surface to incident illumination can be significantly reduced,
So as to improve the resolution performance of photoresist.
4,4- pyrans dicarboxylates are the important source materials for preparing Pentamethylene oxide. -4- formic acid, and Pentamethylene oxide. -4- formic acid can
To obtain photoresist monomer with vinyl compound reaction.The anti-reflecting layer prepared as raw material can significantly reduce photoresist
Reflection and scattering of the surface to incident illumination, improve the resolution of photoresist.Similar compound is usually, with Sodium ethylate, to hydrogenate
Sodium, potassium carbonate are alkali, and using Deca dihalo- ether or the feed way of Deca diethyl malonate, but these synthetic methods are anti-
Longer complex operation between seasonable, reaction yield is low to wait shortcomings, limits the extensive application of such compound.
The content of the invention
The technical problem to be solved is to provide the method that one kind prepares 4,4- pyrans dicarboxylates, this
Bright method is different from the conventional method for preparing such compound, and the feed way for adopting is for diethyl malonate and replacement dichloro
The DMF solution of alkali is added in ether system, is catalyzed using Hydro-Giene (Water Science)., is improve reactivity, shortens the response time, it is easy to
Industrialized production.
The technical scheme that the present invention solves above-mentioned technical problem is as follows：One kind prepare 4,4- pyrans dicarboxylate and its
The method of derivant, including：
Diethyl malonate is added in the reactor of nitrogen protection, replaces dichloroether, Hydro-Giene (Water Science). and dimethyl methyl
Amide, the quality of the dimethylformamide are 10 times of diethyl malonate quality, and stirring is warming up to 100-110 DEG C, Deca
The dimethyl formamide solution of alkali, reaction 2h terminate, and remove solvent under reduced pressure, are further continued for vacuum distillation, obtain 4,4- pyrans diformazans
Diethyl phthalate and its derivant, reaction equation are as follows：
Wherein, R is hydrogen, methoxyl group or ethyl；The dimethyl formamide solution of the alkali is 1g alkali dissolutions in the two of 3-5g
In methylformamide.
On the basis of above-mentioned technical proposal, the present invention can also do following improvement.
Further, the mol ratio of the diethyl malonate, replacement dichloroether and alkali is 1:(1-1.1):(2-2.2),
The Hydro-Giene (Water Science). is (0.5-1) with the mol ratio of diethyl malonate：100.
Further, the alkali be sodium tert-butoxide, potassium tert-butoxide, the mixture of one or more in sodium tert-amyl alcohol.
The invention has the beneficial effects as follows：
The present invention provides a kind of method for being catalyzed using Hydro-Giene (Water Science). and preparing 4,4- pyrans dicarboxylates, and its advantage exists
In：
1. 4, the 4- pyrans dicarboxylates that prepared by the present invention, are important industrial chemicals, can apply well
Pharmaceuticals industry and photoresist field.
2. the present invention prepares 4,4- pyrans dicarboxylates, and the response time is shorter, using the DMF solution of Deca alkali plus
Material mode, it is simple to operate, it is easy to industrialized production.
3. the raw material used by the present invention is cheap and easy to get, it is to avoid using the higher dibromo ether of price and diiodo-ethyl ether.
Specific embodiment
Hereinafter the principle and feature of the present invention are described, example is served only for explaining the present invention, is not intended to limit
Determine the scope of the present invention.
The preparation (sodium tert-amyl alcohol is alkali) of 1 4,4- pyrans dicarboxylates of embodiment
To in the 1L there-necked flasks of nitrogen protection, 48.0g (0.3mol) diethyl malonate, 42.6g (0.3mol) two is added
Dichloroethyl ether, 480g are dried DMF, and 0.6g Hydro-Giene (Water Science) .s obtain system for shallow yellow transparent solution.Stirring is warming up to 100 DEG C.Deca
The DMF solution (being formulated by 69.3g sodium tert-amyl alcohols and 277.2gDMF) of sodium tert-amyl alcohol.Backflow 2h, GC track to surplus without raw material
It is remaining, remove solvent under reduced pressure, be further continued for vacuum distillation, obtain 61.5g colourless liquids, yield：89.1%.
1H NMR(CDCl3,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 2 4,4- pyrans dicarboxylates of embodiment
To in the 1L there-necked flasks of nitrogen protection, 48.0g (0.3mol) diethyl malonate, 42.6g (0.3mol) two is added
Dichloroethyl ether, 480g are dried DMF, and 0.6g Hydro-Giene (Water Science) .s obtain system for shallow yellow transparent solution.Stirring is warming up to 100 DEG C.Deca
The DMF solution (being formulated by 60.5g sodium tert-butoxides and 202gDMF) of 60.5g sodium tert-butoxides.Backflow 2h, GC are tracked to without original
Material is remaining, removes solvent under reduced pressure, is further continued for vacuum distillation, obtains 58.0g colourless liquids, yield：84.1%.
1H NMR(CDCl3,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 3 4,4- pyrans dicarboxylates of embodiment
To in the 1L there-necked flasks of nitrogen protection, 48.0g (0.3mol) diethyl malonate, 42.6g (0.3mol) two is added
Dichloroethyl ether, 480g are dried DMF, and 0.6g Hydro-Giene (Water Science) .s obtain system for shallow yellow transparent solution.Stirring is warming up to 100 DEG C.Deca
The DMF solution (being formulated by 71.2g potassium tert-butoxides and 284.8gDMF) of 71.2g potassium tert-butoxides.Backflow 2h, GC track to nothing
Starting material left, removes solvent under reduced pressure, is further continued for vacuum distillation, obtains 59.5g colourless liquids, yield：86.2%.
1H NMR(CDCl3,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 4 2,6- dimethoxy 4,4- pyrans dicarboxylates of embodiment
To in the 1L there-necked flasks of nitrogen protection, addition 48.0g (0.3mol) diethyl malonate, 60.9g (0.3mol) 1,
1- dimethoxy -2,2- dichloroether, 480g are dried DMF, and 0.6g Hydro-Giene (Water Science) .s obtain system for shallow yellow transparent solution.Stir
Mix and be warming up to 100 DEG C, DMF (being formulated by the 71.2g sodium tert-amyl alcohols and 284.8gDMF) solution of Deca 71.2g potassium tert-butoxide.
Backflow 2h, GC are tracked to without starting material left, and decompression steams solvent, is further continued for vacuum distillation, obtains 63.5g colourless liquids, yield：
73.0%.
1H NMR(CDCl3,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 5 2,6- diethyl 4,4- pyrans dicarboxylates of embodiment
To in the 1L there-necked flasks of nitrogen protection, addition 48.0g (0.3mol) diethyl malonate, 59.7g (0.3mol) 1,
1- diethyl -2,2- dichloroether, 480g are dried DMF, and 0.6g Hydro-Giene (Water Science) .s obtain system for shallow yellow transparent solution.Stirring
100 DEG C are warming up to, the DMF solution (being formulated by 71.2g potassium tert-butoxides and 277.2gDMF) of Deca 71.2g potassium tert-butoxide.Return
Stream 2h, GC are tracked to without starting material left, and decompression steams solvent, is further continued for vacuum distillation, obtains 69.7g colourless liquids, yield：
81.2%.
1H NMR(CDCl3,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 presently preferred embodiments of the present invention, not to limit the present invention, all spirit in the present invention and
Within principle, any modification, equivalent substitution and improvements made etc. should be included within the scope of the present invention.
Claims (2)
1. the method that one kind prepares 4,4- pyrans dicarboxylate and its derivant, it is characterised in that include：
Diethyl malonate is added in the reactor of nitrogen protection, replaces dichloroether, Hydro-Giene (Water Science). and dimethylformamide,
The quality of the dimethylformamide is 10 times of diethyl malonate quality, and stirring is warming up to 100-110 DEG C, the two of Deca alkali
Methylformamide solution, reaction 2h terminate, and remove solvent under reduced pressure, are further continued for vacuum distillation, obtain 4,4- pyrans dicarboxylics
Ester and its derivant, reaction equation are as follows：
Wherein, R is hydrogen, methoxyl group or ethyl；The dimethyl formamide solution of the alkali is 1g alkali dissolutions in the dimethyl of 3-5g
In Methanamide, the mol ratio of the diethyl malonate, replacement dichloroether and alkali is 1:(1-1.1):(2-2.2), the iodine
It is (0.5-1) to change the cuprous mol ratio with diethyl malonate：100.
2. method according to claim 1, it is characterised in that the alkali is sodium tert-butoxide, potassium tert-butoxide, in sodium tert-amyl alcohol
The mixture of one or more.
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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 |
|---|
| Novel Heterospirocyclic 3-Amino-2H-azirines as Synthons for Heterocyclic α-Amino Acids;Christoph Strassler等;《HELVETICA CHIMICA ACTA》;19971231;第80卷;第1542页实验部分第2段 * |
| 丙二酸二乙酯的相转移催化烃基化反应研究;谢文林等;《化学试剂》;20011231;第23卷(第3期);第132-133页 * |
| 相转移催化活泼亚甲基的烃基化;曾庆北等;《化学试剂》;19901231;第12卷(第1期);第58-59页 * |
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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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