CN1159310C - 2-ethoxycarbonyl-2-methyl trimethylene carbonate and its preparing process - Google Patents
2-ethoxycarbonyl-2-methyl trimethylene carbonate and its preparing process Download PDFInfo
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- CN1159310C CN1159310C CNB021157979A CN02115797A CN1159310C CN 1159310 C CN1159310 C CN 1159310C CN B021157979 A CNB021157979 A CN B021157979A CN 02115797 A CN02115797 A CN 02115797A CN 1159310 C CN1159310 C CN 1159310C
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- ethoxycarbonyl
- trimethylene carbonate
- methyl trimethylene
- present
- methyl
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Abstract
The present invention relates to 2-ethoxycarbonyl-2-methyl trimethylene carbonate. A structural formula is the right formula. The present invention also provides a method for preparing the 2-ethoxycarbonyl-2-methyl trimethylene carbonate. 2, 2-dimethylolpropionic acid carries out esterification and ring closing reaction to prepare novel six-membered ring cyclic carbonate monomer, namely the 2-ethoxycarbonyl-2-methyl trimethylene carbonate. The 2-ethoxycarbonyl-2-methyl trimethylene carbonate is used as a monomer to synthesize biologic degrading/absorption polycarbonate which has good biocompatibility and contains functionalization groups. The present invention is used as raw material to prepare a polymer, and the polymer which is used as biodegradable high molecular material has no poison of the degraded products in vivo. Thus, the present invention has important practical significance on the fields of drug controlled release, tissue engineering, gene therapy, etc.
Description
Technical field
The present invention relates to 2-ethoxycarbonyl-2-methyl trimethylene carbonate and preparation method thereof.
Background technology
Closely for decades, the research of biological medical polymer material has obtained developing rapidly, as biodegradable macromolecular material, because it does not need to take out through surgical operation after implanting, thus at operating sutures, artificial skin, artificial blood vessel, bone is fixing and repair and fields such as drug delivery system obtain more and more widely application.Biological degradable synthesized polymer mainly contains polyester, polyamino acid, poly phosphate, poly-acid anhydrides, poe, polycarbonate etc.Aliphatic acid ester carbonate is the polymer of class biodegradable/absorption, it has biocompatibility, certain elasticity is arranged under the condition in vivo, can be used as bio-medical material at controlled release drug delivery system, there are extensive studies and application in aspects such as material implanted and soft tissue repair material.For obtain side chain contain functionalization biodegradable/the nontoxic biological medical macromolecular materials that absorb, one of important approach is exactly to design and the carbonate monomer of composite structure novelty or modify by side chain.
The Polymer Synthesizing method generally has reactions such as addition polymerization polymerization, isomerization polymerization, cancellation polymerization, polycondensation, cyclopolymerization, ring-opening polymerization, poly-addition, addition polycondensation, at present biodegradable polycarbonate synthetic general adopted ring-opening polymerization, and heat effect is low because it has, polymerization velocity fast, can reach advantage such as higher molecular weight at short notice.The monomer of common aliphatic acid ester carbonate ring-opening polymerization is generally five-ring or six-ring cyclic carbonate, but always more or less have the decarbonation phenomenon to produce during owing to the ring-opening polymerization of five-ring cyclic carbonate, so the synthetic general six-ring cyclic carbonate that adopts of polycarbonate.
But the aliphatic polycarbonate that contains the functionalization side group is significant in practice.The various medicines of bonding form the polymer drug system on functional pendant groups, and may command discharges or continues and discharges; Perhaps bonding bioactive molecules is with biocompatibility and the biological activity of improving material; Can also change degradation rate, physical and mechanical properties, the hydrophilic/hydrophobic performance of polymkeric substance by the introducing of side chain functionalities; Therefore also can come control degradation speed, but the research and the application that contain the aliphatic polycarbonate of functionalization side group have caused the great interest of people by the ratio of control functional group.
Summary of the invention
The purpose of this invention is to provide 2-ethoxycarbonyl-2-methyl trimethylene carbonate and preparation method thereof, but gained 2-ethoxycarbonyl-2-methyl trimethylene carbonate can be used for preparing and has biodegradable/absorption polycarbonate that good biocompatibility contains the functionalization group.
Technical scheme provided by the invention is, the 2-ethoxycarbonyl-2-methyl trimethylene carbonate, and its structural formula is:
The present invention also provides the preparation method of above-mentioned 2-ethoxycarbonyl-2-methyl trimethylene carbonate, promptly from 2, the 2-dimethylol propionic acid sets out, by esterification, it is the 2-ethoxycarbonyl-2-methyl trimethylene carbonate that ring closure reaction has prepared novel six-ring cyclic carbonate monomer, and concrete synthetic route is as follows:
With 2,2-dimethylol propionic acid and ethanol prepare 2-ethoxycarbonyl-2-methyl, ammediol through esterification under acidic conditions (pH＜7); Gained 2-ethoxycarbonyl-2-methyl, ammediol and Vinyl chloroformate are being catalyzer with the triethylamine, and tetrahydrofuran (THF) is a solvent, make the 2-ethoxycarbonyl-2-methyl trimethylene carbonate under-15～5 ℃ the condition, its fusing point is 49-50 ℃, measures through micro-fusing point instrument.The structure of 2-ethoxycarbonyl-2-methyl trimethylene carbonate is through infrared spectra (FT-IR), proton NMR spectrum (
1H NMR) confirms.
The six-ring cyclic carbonate that the present invention has synthesized a kind of novel structure first is the 2-ethoxycarbonyl-2-methyl trimethylene carbonate.With the 2-ethoxycarbonyl-2-methyl trimethylene carbonate is but that monomer can synthesize and has good biocompatibility and contain the biodegradable/absorption polycarbonate of functionalization group-poly-(2-ethoxycarbonyl-2-methyl trimethylene carbonate).Because the existence of this polymer lateral chain functional group, thereby can form the polymer drug system by the various medicines of bonding, may command discharges or continues and discharges, perhaps bonding bioactive molecules, with biocompatibility and the biological activity of improving material, can also change degradation rate, physical and mechanical properties, the hydrophilic/hydrophobic performance of polymkeric substance by the introducing of side chain functionalities, and can come control degradation speed by the ratio of control functional group.And it is nontoxic as the polymkeric substance that raw material makes as the product of biodegradable macromolecular material degradation in vivo with the present invention.Therefore in fields such as medicine sustained release, organizational project, gene therapies very important practice significance is arranged.
Embodiment
Below in conjunction with specific examples technical scheme of the present invention is described further:
Embodiment one:
The 2-ethoxycarbonyl-2-methyl, the preparation of ammediol: with 20.2 grams 2,2-dimethylol propionic acid and 150 milliliters of dehydrated alcohols add in 250 milliliters of round-bottomed flasks, with 3.0 grams, 732 type cation exchange resin as catalyst, 8.0 gram 3A type molecular sieves are added in the apparatus,Soxhlet's, heated and stirred refluxed 72 hours, filter, steam solvent, dry that light yellow oily liquid 22.7 restrains productive rate 93.4%, infrared spectra 1721cm
-1(-COO-).
Embodiment two:
The preparation of 2-ethoxycarbonyl-2-methyl trimethylene carbonate: with 11.4 gram 2-ethoxycarbonyl-2-methyls, ammediol is dissolved in 600 milliliters of tetrahydrofuran (THF)s, add 16 milliliters of Vinyl chloroformates again, stir down at 0 ℃, drip 26 milliliters of triethylamines in 30 minutes, at room temperature stirred then 2 hours, leach triethylamine hydrochloride, filtrate concentrates, add anhydrous diethyl ether and make it precipitation, thick product is with toluene/sherwood oil recrystallization three times, white crystal 2-ethoxycarbonyl-2-methyl trimethylene carbonate 6.8 grams, productive rate 49.6%, infrared spectra 1731cm
-1(-COO-), 1759cm
-1(-OCOO-), proton NMR spectrum (
1H NMR): (CDCl
3, ppm) 4.64-4.72,4.18-4.24 (CH
2, 6H), 1.24-1.36 (CH
3, 6H).
Claims (2)
1.2-ethoxycarbonyl-2-methyl trimethylene carbonate, its structural formula is:
2. the preparation method of the described 2-ethoxycarbonyl-2-methyl trimethylene carbonate of claim 1 is characterized in that:
With 2,2-dimethylol propionic acid and ethanol prepare 2-ethoxycarbonyl-2-methyl, ammediol through esterification under acidic conditions; Gained 2-ethoxycarbonyl-2-methyl, ammediol and Vinyl chloroformate are being catalyzer with the triethylamine, tetrahydrofuran (THF) is a solvent, makes the 2-ethoxycarbonyl-2-methyl trimethylene carbonate under-15～5 ℃ the condition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021157979A CN1159310C (en) | 2002-04-30 | 2002-04-30 | 2-ethoxycarbonyl-2-methyl trimethylene carbonate and its preparing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021157979A CN1159310C (en) | 2002-04-30 | 2002-04-30 | 2-ethoxycarbonyl-2-methyl trimethylene carbonate and its preparing process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1381452A CN1381452A (en) | 2002-11-27 |
| CN1159310C true CN1159310C (en) | 2004-07-28 |
Family
ID=4743875
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021157979A Expired - Fee Related CN1159310C (en) | 2002-04-30 | 2002-04-30 | 2-ethoxycarbonyl-2-methyl trimethylene carbonate and its preparing process |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101941962B (en) * | 2010-08-03 | 2012-09-26 | 武汉大学 | 2-(2-bromoisobutyacylamino) trimethylene carbonate and preparation method and applications thereof |
| CN106518852A (en) * | 2016-10-26 | 2017-03-22 | 中国地质大学（武汉） | 2-methyl-2-(5-fluorouracil)carbonyltrimethylene carbonate as well as preparation method and application thereof |
| CN106543153A (en) * | 2016-10-26 | 2017-03-29 | 中国地质大学（武汉） | 2 imidazoles carbonyl, 2 methyl trimethylene carbonate and its production and use |
| CN110452214B (en) * | 2019-07-10 | 2022-06-28 | 天津大学 | Cyclic carbonate monomer capable of initiating ATRP polymerization, and preparation method and application thereof |
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2002
- 2002-04-30 CN CNB021157979A patent/CN1159310C/en not_active Expired - Fee Related
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| Publication number | Publication date |
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| CN1381452A (en) | 2002-11-27 |
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