CN102731446B - 3-(thiazol-2-yl)-ALANINE transition metal complex catalyzed oxidation tetrahydrofuran (THF) prepares the method for gamma-butyrolactone and succinic acid - Google Patents
3-(thiazol-2-yl)-ALANINE transition metal complex catalyzed oxidation tetrahydrofuran (THF) prepares the method for gamma-butyrolactone and succinic acid Download PDFInfo
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- CN102731446B CN102731446B CN201110090964.6A CN201110090964A CN102731446B CN 102731446 B CN102731446 B CN 102731446B CN 201110090964 A CN201110090964 A CN 201110090964A CN 102731446 B CN102731446 B CN 102731446B
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Abstract
Having the present invention relates to 3-(thiazol-2-yl)-ALANINE transition metal complex for catalyzer, is the best catalytic condition of gamma-butyrolactone and succinic acid at catalysis in aerobic condition oxidation tetrahydrofuran (THF).Method comprises the steps: first 3-(thiazol-2-yl)-ALANINE to be mixed with into catalyzer from different transition metal salts, again catalyzer is added in tetrahydrofuran (THF), under different conditions, with atmospheric oxygen or purity oxygen, tetrahydrofuran (THF) is oxidized to as gamma-butyrolactone and succinic acid.
Description
Technical field
The present invention relates to the method that 3-(thiazol-2-yl)-ALANINE transition metal complex catalysis in aerobic condition oxidation tetrahydrofuran (THF) obtains gamma-butyrolactone and succinic acid.
Background technology
The transition metal complex with oxygen carrying capability can form fit key with molecular oxygen, metal ion provides electronics to oxygen molecule, thus activated molecular oxygen, make oxygen molecule have higher oxidation activity, so this metal complexes can be used as catalyst oxidizing reaction.
The α hydroxide of ethers is the important organic oxidizing reaction of a class, and there is a challenging problem as the tetrahydrofuran (THF) of ethers equally---the selectivity oxygenation oxidation of tetrahydrofuran (THF), in recent years, the oxidation research of tetrahydrofuran (THF) is main with O
2, TBHP etc. are oxygen source, and metal complexes is carry out under the condition of catalyzer.
Transition metal complex has a lot of application as the reaction that catalyst is oxidized, and as catalyzed oxidation Trimethylmethane, the alkane such as hexanaphthene are corresponding alcohol, ketone, catalyzed oxidation toluene, and ethylbenzene etc. are corresponding alcohol, ketone, acid.But the catalyzer of bibliographical information mostly is porphyrin, phthalocyanines, and amino acid transition metal complex is the more rare of catalyzer.The present invention is with 3-(thiazol-2-yl)-ALANINE transition metal complex for catalyzer, and catalysis in aerobic condition oxidation tetrahydrofuran (THF) is gamma-butyrolactone and succinic acid; This method has reaction conditions gentleness, simple advantage.
Summary of the invention
The invention provides the method that 3-(thiazol-2-yl)-ALANINE transition metal complex catalyzed oxidation tetrahydrofuran (THF) obtains gamma-butyrolactone, succinic acid, as following step:
1) 3-(thiazol-2-yl)-ALANINE is mixed with into catalyzer from different transition metal salts by a certain percentage respectively;
2) catalyzer is added in refining tetrahydrofuran (THF), under different ratios and temperature condition, with atmospheric oxygen or purity oxygen catalyzed oxidation tetrahydrofuran (THF);
3) product obtained is carried out be separated, purify.
Embodiment
Embodiment 1: accurately take 0.2mmol3-(thiazol-2-yl)-ALANINE, with 0.1mmol nickelous chloride, after mixing, add 15ml tetrahydrofuran (THF), be placed in the airtight large container being filled with pure oxygen, after reaction terminates, after filtering separation, obtain gamma-butyrolactone and succinic acid white solid.
Embodiment 2: accurately take 0.2mmol3-(thiazol-2-yl)-ALANINE, respectively with 0.1mmol cobalt chloride, after mixing, add 15ml tetrahydrofuran (THF), be placed in the airtight large container being filled with pure oxygen, after reaction terminates, after filtering separation, obtain gamma-butyrolactone and succinic acid white solid.
Embodiment 3: accurately take 0.2mmol3-(thiazol-2-yl)-ALANINE, with 0.1mmol manganous acetate, after mixing, add 15ml tetrahydrofuran (THF), be placed in the airtight large container being filled with pure oxygen, after reaction terminates, after filtering separation, obtain gamma-butyrolactone and succinic acid white solid.。
Embodiment 4: take 0.2mmol cobaltous acetate, 3-(thiazol-2-yl)-ALANINE with 0.4mmol, adds 15ml tetrahydrofuran (THF) after mixing, be placed in the airtight large container being filled with pure oxygen, after reaction terminates, after filtering separation, obtain gamma-butyrolactone and succinic acid white solid.
Embodiment 5: take 0.2mmol3-(thiazol-2-yl)-ALANINE, 0.1mmol ironic acetate, add 15ml tetrahydrofuran (THF) after mixing, be placed in the airtight large container being filled with pure oxygen, react at 20 DEG C, after reaction terminates, after filtering separation, obtain succinic acid white solid.
Embodiment 6: take 0.2mmol3-(thiazol-2-yl)-ALANINE, 0.1mmol cadmium acetate, add 15ml tetrahydrofuran (THF) after mixing, be placed in the airtight large container being filled with pure oxygen, react at 30 DEG C, after reaction terminates, after filtering separation, obtain succinic acid white solid.
Embodiment 7: take 0.2mmol3-(thiazol-2-yl)-ALANINE, 0.1mmol cobaltous acetate, add 15ml tetrahydrofuran (THF) after mixing, be placed in the airtight large container being filled with pure oxygen, react at 40 DEG C, after reaction terminates, after filtering separation, obtain succinic acid white solid.
Embodiment 8: take 0.2mmol3-(thiazol-2-yl)-ALANINE, 0.1mmol venus crystals, add 15ml tetrahydrofuran (THF) after mixing, be placed in the airtight large container being filled with pure oxygen, react at 50 DEG C, after reaction terminates, after filtering separation, obtain succinic acid white solid.
Claims (1)
1. 3-(thiazol-2-yl)-ALANINE transition metal complex catalysis in aerobic condition oxidation tetrahydrofuran (THF) obtains a method for gamma-butyrolactone and succinic acid, it is characterized in that the general formula of described amino acid transition metal complex is ML
py
q,
In general formula:
1) M is transition metal ion, is selected from cobalt, copper, nickel, manganese, iron or chromium ion;
2) L is 3-(thiazol-2-yl)-ALANINE, and structure is as follows:
3) Y is the negatively charged ion of transition metal salt, is selected from acetate, nitrate radical, sulfate radical, chlorion or perchlorate;
4) p value is the part number with transition metal ion M coordination, and p is selected from 1,2 or 3; Q is selected from 1 or 2.
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| CN201110090964.6A CN102731446B (en) | 2011-04-12 | 2011-04-12 | 3-(thiazol-2-yl)-ALANINE transition metal complex catalyzed oxidation tetrahydrofuran (THF) prepares the method for gamma-butyrolactone and succinic acid |
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| CN201110090964.6A CN102731446B (en) | 2011-04-12 | 2011-04-12 | 3-(thiazol-2-yl)-ALANINE transition metal complex catalyzed oxidation tetrahydrofuran (THF) prepares the method for gamma-butyrolactone and succinic acid |
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| CN102731446A CN102731446A (en) | 2012-10-17 |
| CN102731446B true CN102731446B (en) | 2016-04-06 |
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Citations (6)
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| US4410501A (en) * | 1979-12-21 | 1983-10-18 | Snamprogetti S.P.A. | Preparation of porous crystalline synthetic material comprised of silicon and titanium oxides |
| WO1995001188A1 (en) * | 1993-07-02 | 1995-01-12 | Rhomed Incorporated | Polyvalent peptide pharmaceutical applications |
| US5683793A (en) * | 1996-06-03 | 1997-11-04 | Xerox Corporation | Ink jet transparencies |
| WO2004033391A1 (en) * | 2002-10-08 | 2004-04-22 | Helsinki University Of Technology | Method for catalytic oxygenation of cyclic ethers with homo and hetero metallic mo/ru complexes and molecular oxygen |
| CN101643426A (en) * | 2008-08-04 | 2010-02-10 | 新疆大学 | Solid-phase synthesis method of transition metal complex of polyamine and use thereof in oxygen absorption |
| CN101903010A (en) * | 2007-12-19 | 2010-12-01 | 雅芳产品公司 | Topical compositions comprising non-proteogenic amino acids and methods of treating skin |
-
2011
- 2011-04-12 CN CN201110090964.6A patent/CN102731446B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4410501A (en) * | 1979-12-21 | 1983-10-18 | Snamprogetti S.P.A. | Preparation of porous crystalline synthetic material comprised of silicon and titanium oxides |
| WO1995001188A1 (en) * | 1993-07-02 | 1995-01-12 | Rhomed Incorporated | Polyvalent peptide pharmaceutical applications |
| US5683793A (en) * | 1996-06-03 | 1997-11-04 | Xerox Corporation | Ink jet transparencies |
| WO2004033391A1 (en) * | 2002-10-08 | 2004-04-22 | Helsinki University Of Technology | Method for catalytic oxygenation of cyclic ethers with homo and hetero metallic mo/ru complexes and molecular oxygen |
| CN101903010A (en) * | 2007-12-19 | 2010-12-01 | 雅芳产品公司 | Topical compositions comprising non-proteogenic amino acids and methods of treating skin |
| CN101643426A (en) * | 2008-08-04 | 2010-02-10 | 新疆大学 | Solid-phase synthesis method of transition metal complex of polyamine and use thereof in oxygen absorption |
Non-Patent Citations (2)
| Title |
|---|
| Thermodynamics of Oxygen Binding in Natural and Synthetic Dioxygen Complexes;ERIC C. NIEDERHOFFER, JAMES H. TIMMONS, and ARTHUR E. MARTELL;《Chem. Rev.》;19840430;第84卷(第2期);第137-203页 * |
| 催化氧化合成己二酸的清洁方法;任水英等;《化学进展》;20090424;第21卷(第4期);第663-671页 * |
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