CN101134741A - Catalyst for selective oxidation of protection monosaccharide primary hydroxy group - Google Patents
Catalyst for selective oxidation of protection monosaccharide primary hydroxy group Download PDFInfo
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Abstract
The present invention relates to selective oxidation catalyst and process capable of protecting primary hydroxyl group in monosaccharide. It is found that using 4-alkoxyl group or acryloxy substituted 2, 2, 6, 6-tetramethyl piperidino-N-oxide as catalyst in the reaction of the protected monosaccharide and hypohaloid solution can oxidize the protected primary hydroxyl group in monosaccharide selectively into carboxyl group without need of auxiliary oxidant and with yield as high as 95 %.
Description
Technical field:
The present invention relates to a kind of catalyzer of protecting the monosaccharide primary hydroxy group selective oxidation, the invention still further relates to a kind of method of protecting the monosaccharide primary hydroxy group selective oxidation.
Background technology:
Monose is a polyol, only the primary hydroxyl in its structure is carried out selective oxidation and becomes the monose thuja acid, has great importance, because of it is synthetic many important intermediate with physiologically active substance.
The Catalyst And Method of the primary hydroxyl in the selective oxidation monose material of now having reported has following several:
1.GB670929 make oxygenant with nitric acid and Sodium Nitrite, a large amount of nitric acid of this method consumption, yield is low, and by product is many, can produce a large amount of nitrogen peroxide (i.e. industry alleged " Huanglong "), and environment is caused great pollution.
2.US2592249 US2683150 is to be oxygenant with the nitrogen dioxide gas, but nitrogen dioxide gas operation inconvenience equally also causes serious pollution to environment.
3.US2845439 and US2627520 is in the presence of precious metal, is oxygenant with oxygen, this method need use metals such as expensive platinum, palladium to make catalyzer.
4. with 2,2,6,6-tetramethyl piperidine-N-oxide compound (TEMPO) is as catalyzer, as:
1) TEMPO+ clorox+Sodium Bromide is seen Tetrahedron Lett.34,1181-1184,1993 and WO9507303;
2) TEMPO+ clorox+hydrogen peroxide is seen WO0134657;
3) the TEMPO+ clorox is seen P.L.Bragd:J.Mol.Cata.A:Chem, 170, and 35-42,2001
Above-mentioned with some need use secondary oxidizer in the method for TEMPO, can produce some problems: as adding impurity such as can introducing Br in Sodium Bromide, the product; Hydrogen peroxide is easy to blast in aftertreatment, very high to the security requirement of operation; The pH scope of its reaction generation is narrower in addition, and reaction conditions is comparatively harsh.And the aforesaid method reaction yield is lower.
Summary of the invention:
Final purpose of the present invention provides the method to protection monose matter selective oxidation of primary hydroxyl of a kind of convenience, economy.Directly purpose is to find a kind of new catalyzer, and finds only reaction conditions, makes this selective oxidation reaction more effective and economical.
For reaching the foregoing invention purpose; the contriver passes through molecular designing; synthetic and screened a series of TEMPO derivative, and use it for the selective catalytic oxidation test of monosaccharide primary hydroxy group respectively, finally find out compound of Formula I: 4-alkoxyl group or acyloxy replace-2; 2; 6,6-tetramethyl piperidine-N-oxide compound, this type of new compound can be separately as catalyzer; do not need the just alternative oxidation protection monosaccharide primary hydroxy group of secondary oxidizer to become carboxyl, and reaction yield can reach more than 95%.
Formula I
Among the formula I: R is selected from chain-like alkyl, cycloalkyl or acyl group, preferred tertiary butyl, sec.-propyl, cyclohexyl, propionyl, butyryl radicals or pentanoyl, preferred tertiary butyl, sec.-propyl, cyclohexyl, butyryl radicals.
The invention provides a kind of method of new protection monose matter selective oxidation of primary hydroxyl:
With the compound of Formula I is catalyzer, and protection monose material and 1%～20% (W/W) the hypohalite solution for the treatment of oxidation is reacted; The consumption of compound of Formula I is 0.1%～5.0% (W/W) of protection monose.
Described protection monose material comprises allose first glycosides, allose second glycosides, allose third glycosides, different third glycosides of allose; glucose first glycosides, glucose second glycosides, glucose third glycosides, different third glycosides of glucose; altrose first glycosides, altrose second glycosides, altrose third glycosides, different third glycosides of altrose; seminose first glycosides, seminose second glycosides, seminose third glycosides, different third glycosides of seminose; gulose first glycosides, gulose second glycosides, gulose third glycosides, different third glycosides of gulose; semi-lactosi first glycosides, semi-lactosi second glycosides, semi-lactosi third glycosides, different third glycosides of semi-lactosi.
Described hypohalite comprises hypochlorite, hypobromite, preferred clorox or sodium hypobromite.
The present invention compared with prior art has the following advantages:
1. need not secondary oxidizer
Not only saved raw material but also stopped the chance of introducing impurity in the product.
2. reaction conditions is loose
Need under acidic conditions, not react, under the environment of pH4-10, all can carry out.
3. cost is low
Catalyzer is directly used in catalyzed reaction, and reactions steps is few, and speed of response is fast, saves manpower, is particularly suitable for plant-scale big production.
4. efficient height
Reaction yield can reach more than 95%.
Embodiment:
The invention will be further described below in conjunction with embodiment, can make this area professional and technical personnel understand the present invention more all sidedly, but not limit the present invention in any way.
Embodiment 1 4-tert.-butoxy-2,2,6, the preparation of 6-tetramethyl piperidine-N-oxide compound
Under 0 ℃, in the there-necked flask of 1L, add the 300ml methylene dichloride, the 60ml pyridine, 30g4-hydroxyl-2,2,6,6-tetramethyl piperidine-N-oxide compound drips the 66g Tosyl chloride then and is dissolved in solution in the methylene dichloride of 200ml, reacts 180 minutes.Dropwise 5 0g sodium tert-butoxide is dissolved in solution in the methylene dichloride of 200ml, stirring reaction 120 minutes in this solution again.After reaction is finished, wash reaction solution with water three times, the organic layer anhydrous sodium sulfate drying, the evaporate to dryness methylene dichloride adds the 100ml normal hexane, and freezing and crystallizing filters and obtains 4-tert.-butoxy-2,2,6, the red crystals 34g of 6-tetramethyl piperidine-N-oxide compound.
1H NMR (CDCl
3, 300MHz, δ) 1.22 (s, 9H) 1.73 (s, 12H) 1.95-2.20 (m, 4H) 2.83 (m, 1H); Ultimate analysis: C, 68.36; H, 11.43; N, 6.07; O, 14.03; This catalyzer of ESI-MS:found:228.1965 (calu:228.1964) is directly used in catalyzed reaction.
Embodiment 2 4-isopropoxies-2,2,6, the preparation of 6-tetramethyl piperidine-N-oxide compound
Under 0 ℃, in the there-necked flask of 1L, add the 300ml methylene dichloride, the 60ml pyridine, 30g4-hydroxyl-2,2,6,6-tetramethyl piperidine-N-oxide compound drips the 66g Tosyl chloride then and is dissolved in solution in the methylene dichloride of 200ml, reacts 180 minutes.Drip the 46.5g sodium isopropylate again in this solution and be dissolved in solution in the methylene dichloride of 200ml, stirring reaction 120 minutes.After reaction is finished, wash reaction solution with water three times, the organic layer anhydrous sodium sulfate drying, the evaporate to dryness methylene dichloride adds the 100ml normal hexane, and freezing and crystallizing filters and obtains 4-isopropoxy-2,2,6, the red crystals 28g of 6-tetramethyl piperidine-N-oxide compound.
1H NMR (CDCl
3, 300MHz, δ) 1.17 (s, 6H) 1.71 (s, 12H) 1.95-2.20 (m, 4H) 2.83 (m, 1H) 3.20 (m, 1H); Ultimate analysis: C, 67.24; H, 11.30; N, 6.58; O, 14.90; ESI-MS:found:214.1810 (calu:214.1807).This catalyzer is directly used in catalyzed reaction.
Embodiment 3 4-cyclohexyloxies-2,2,6, the preparation of 6-tetramethyl piperidine-N-oxide compound
Under 0 ℃, in the there-necked flask of 1L, add the 300ml methylene dichloride, the 60ml pyridine, 30g4-hydroxyl-2,2,6,6-tetramethyl piperidine-N-oxide compound drips the 66g Tosyl chloride then and is dissolved in solution in the methylene dichloride of 200ml, reacts 180 minutes.In this solution, drip the 200ml dichloromethane solution that contains 52.4g hexamethylene sodium alkoxide, stirring reaction 120 minutes again.After reaction is finished, wash reaction solution with water three times, the organic layer anhydrous sodium sulfate drying, the evaporate to dryness methylene dichloride adds the 100ml normal hexane, and freezing and crystallizing filters and obtains 4-isopropoxy-2,2,6, the red crystals 32g of 6-tetramethyl piperidine-N-oxide compound.
1H NMR (CDCl
3, 300MHz, δ) 1.39-1.46 (m, 8H) 1.71 (s, 12H) 1.73 (m, 2H) 1.95-2.20 (m, 4H) 2.79 (m, 1H) 2.83 (m, 1H); Ultimate analysis: C, 70.81; H, 11.10; N, 5.54; O, 12.57; ESI-MS:found:254.3881 (calu:254.3883).This catalyzer is directly used in catalyzed reaction.
Embodiment 4 4-propionyloxies-2,2,6, the preparation of 6-tetramethyl piperidine N-oxide compound
To add the 500ml methylene dichloride in the 1L there-necked flask of clean dried, add the 127ml pyridine when cooling to below 0 ℃, 172g 4-OH-TEMPO, the 200ml dichloromethane solution of dropping 101ml propionyl chloride dripped off in 2 hours, stirred 30min.Reaction solution is changed in the 2L separating funnel, and dichloromethane layer is given a baby a bath on the third day after its birth time (150ml * 3) with 0.5N HCl, washes with water twice (200ml * 2), and anhydrous sodium sulfate drying filters.35 ℃ of following evaporated under reduced pressure methylene dichloride get the 284g brown liquid, add the 100ml normal hexane, freeze overnight in the refrigerator-freezer.Filter, filter cake divides three washings with 100ml ice normal hexane, gets orange crystal 2 14g.1.14 (t, 3H) 1.16 (s, 12H) 1.78-1.53 (m, 4H) 2.29 (q, 2H) 3.97 (m, 1H); Ultimate analysis: C, 63.12; H, 9.72; N, 6.13; O, 21.04; ESI-MS:found:228.1601 (calu:228.1600).This catalyzer is directly used in catalyzed reaction.
Embodiment 5 4-butyryl acyloxies-2,2,6, the preparation of 6-tetramethyl piperidine N-oxide compound
To add the 500ml methylene dichloride in the 1L there-necked flask of clean dried, add the 127ml pyridine when cooling to below 0 ℃, 172g 4-OH-TEMPO, the 200ml dichloromethane solution of dropping 112ml butyryl chloride dripped off in 2 hours, stirred 30min.Reaction solution is changed in the 2L separating funnel, and dichloromethane layer is given a baby a bath on the third day after its birth time (150ml * 3) with 0.5N HCl, washes with water twice (200ml * 2), and anhydrous sodium sulfate drying filters.35 ℃ of following evaporated under reduced pressure methylene dichloride get the 290g brown liquid, add the 100ml normal hexane, freeze overnight in the refrigerator-freezer.Filter, filter cake divides three washings with 100ml ice normal hexane, gets orange crystal 2 18g.0.96 (t, 3H) 1.16 (s, 12H) 1.72 (m, 2H) 1.78-1.53 (m, 4H) 2.26 (q, 2H) 3.97 (m, 1H); Ultimate analysis: C, 64.44; H, 9.96; N, 5.74; O, 19.83; ESI-MS:found:242.1757 (calu:242.1756).This catalyzer is directly used in catalyzed reaction.
Embodiment 6 semi-lactosi second glycosides selective oxidations are semi-lactosi second thuja acid
Under 0 ℃, in the there-necked flask of 20L, add 2000ml water, under agitation add 1000g exsiccant semi-lactosi second glycosides then, 10g 4-butyryl acyloxy-2,2,6,6-tetramethyl piperidine-N-oxide compound, begin to add the hydrochloric acid of 16%NaClO solution and 2N more simultaneously, keep PH between 5～8, temperature remains on 0-30 ℃ always, when adding about 1800ml NaClO solution, stop to add hydrochloric acid, change and add 2N NaOH solution, dropwise up to 6750ml NaClO solution.Adopt the yield 93% of Blumenkrantz analytical semi-lactosi second thuja acid, the selectivity of primary hydroxyl oxidation is more than 95%.
Embodiment 7 glucose second glycosides selective oxidations are glucose second thuja acid
Under 0 ℃, in the there-necked flask of 20L, add 2000ml water, under agitation add 1000g exsiccant glucose second glycosides then, 10g 4-tert.-butoxy-2,2,6,6-tetramethyl piperidine-N-oxide compound, begin to add the hydrochloric acid of 16%NaClO solution and 2N more simultaneously, keep PH between 6～10, temperature remains on 0-30 ℃ always, when adding about 1800ml NaClO solution, stop to add hydrochloric acid, change and add 2N NaOH solution, dropwise up to 6750ml NaClO solution.Adopt the yield 92% of Blumenkrantz analytical glucose second thuja acid, the selectivity of primary hydroxyl oxidation is more than 94%.
Embodiment 8 glucose first glycosides selective oxidations are glucose first thuja acid
Under 0 ℃, in the there-necked flask of 20L, add 2000ml water, under agitation add 1000g exsiccant glucose first glycosides then, 2g 4-isopropoxy-2,2,6,6-tetramethyl piperidine-N-oxide compound, begin to add the hydrochloric acid of 20%NaBrO solution and 2N more simultaneously, keep PH between 4～8, temperature remains on 0-30 ℃ always, when adding about 1850ml NaBrO solution, stop to add hydrochloric acid, change and add 2N NaOH solution, dropwise up to 5400ml NaBrO solution.Adopt the yield 90% of Blumenkrantz analytical glucose first thuja acid, the selectivity of primary hydroxyl oxidation is more than 95%.
Embodiment 9 glucose first glycosides selective oxidations are glucose first thuja acid
Under 0 ℃, in the there-necked flask of 20L, add 2000ml water, under agitation add 1000g exsiccant glucose first glycosides then, 5g 4-acetoxyl group-2,2,6,6-tetramethyl piperidine-N-oxide compound, begin to add the hydrochloric acid of 20%NaBrO solution and 2N more simultaneously, keep PH between 4～8, temperature remains on 0-30 ℃ always, when adding about 1850ml NaBrO solution, stop to add hydrochloric acid, change and add 2N NaOH solution, dropwise up to 5400ml NaBrO solution.Adopt the yield 90% of Blumenkrantz analytical glucose first thuja acid, the selectivity of primary hydroxyl oxidation is more than 95%.
Embodiment 10 allose first glycosides selective oxidations are allose first thuja acid
Under 0 ℃, in the there-necked flask of 20L, add 2000ml water, under agitation add 1000g exsiccant allose first glycosides then, 45g 4-cyclohexyloxy-2,2,6,6-tetramethyl piperidine-N-oxide compound, begin to add the hydrochloric acid of 10%NaClO solution and 2N more simultaneously, keep PH between 6-10, temperature remains on 0-30 ℃ always, when adding about 2900ml NaClO solution, stop to add hydrochloric acid, change and add 2N NaOH solution, dropwise up to 10800ml NaClO solution.Adopt the yield 93% of Blumenkrantz analytical allose first thuja acid, the selectivity of primary hydroxyl oxidation is more than 96%.
Embodiment 11 allose first glycosides selective oxidations are allose first thuja acid
Under 0 ℃, in the there-necked flask of 20L, add 2000ml water, under agitation add 1000g exsiccant allose first glycosides then, 10g 4-propionyloxy-2,2,6,6-tetramethyl piperidine-N-oxide compound, begin to add the hydrochloric acid of 10%NaClO solution and 2N more simultaneously, keep PH between 6-10, temperature remains on 0-30 ℃ always, when adding about 2900ml NaClO solution, stop to add hydrochloric acid, change and add 2N NaOH solution, dropwise up to 10800ml NaClO solution.Adopt the yield 95% of Blumenkrantz analytical allose first thuja acid, the selectivity of primary hydroxyl oxidation is more than 96%.
Embodiment 12 semi-lactosi first glycosides selective oxidations are semi-lactosi first thuja acid
Under 0 ℃, in the there-necked flask of 50L, add 2000ml water, under agitation add 1000g exsiccant semi-lactosi first glycosides then, 20g 4-tert.-butoxy-2,2,6,6-tetramethyl piperidine-N-oxide compound, begin to add the hydrochloric acid of 5%KClO solution and 2N more simultaneously, keep PH between 4-7, temperature remains on 0-30 ℃ always, when adding about 5760ml KClO solution, stop to add hydrochloric acid, change and add 2N NaOH solution, dropwise up to 21600ml KClO solution.Adopt the yield 92% of Blumenkrantz analytical semi-lactosi first thuja acid, the selectivity of primary hydroxyl oxidation is more than 95%.
Embodiment 13 seminose first glycosides selective oxidations are seminose first thuja acid
Under 0 ℃, in the there-necked flask of 20L, add 2000ml water, under agitation add 1000g exsiccant seminose first glycosides then, 15g 4-isopropoxy-2,2,6,6-tetramethyl piperidine-N-oxide compound, begin to add the hydrochloric acid of 16%KBrO solution and 2N more simultaneously, keep PH between 5-9, temperature remains on 0-30 ℃ always, when adding about 1800mlKBrO solution, stop to add hydrochloric acid, change and add 2N NaOH solution, dropwise up to 6750mlKBrO solution.Adopt the yield 93% of Blumenkrantz analytical seminose first thuja acid, the selectivity of primary hydroxyl oxidation is more than 94%.
Embodiment 14 seminose first glycosides selective oxidations are seminose first thuja acid
Under 0 ℃, in the there-necked flask of 20L, add 2000ml water, under agitation add 1000g exsiccant seminose first glycosides then, 15g 4-butyryl acyloxy-2,2,6,6-tetramethyl piperidine-N-oxide compound, begin to add the hydrochloric acid of 16%KBrO solution and 2N more simultaneously, keep PH between 5-9, temperature remains on 0-30 ℃ always, when adding about 1800mlKBrO solution, stop to add hydrochloric acid, change and add 2N NaOH solution, dropwise up to 6750mlKBrO solution.Adopt the yield 93% of Blumenkrantz analytical seminose first thuja acid, the selectivity of primary hydroxyl oxidation is more than 96%.
Claims (9)
1. compound of Formula I
Among the formula I: R is selected from chain-like alkyl, cycloalkyl or acyl group.
2. the described compound of Formula I of claim 1, wherein R is selected from the tertiary butyl, sec.-propyl, cyclohexyl, propionyl, butyryl radicals or pentanoyl.
3. the described compound of Formula I of claim 2, wherein R is selected from the tertiary butyl, sec.-propyl, cyclohexyl, butyryl radicals.
In the claim 1～3 the described compound of Formula I of each claim as the purposes of the catalyzer of protection monosaccharide primary hydroxy group selective oxidation.
5. the described purposes of claim 4, described protection monose comprises allose first glycosides, allose second glycosides; allose third glycosides, different third glycosides of allose, altrose first glycosides; altrose second glycosides, altrose third glycosides, different third glycosides of altrose; glucose first glycosides, glucose second glycosides, glucose third glycosides; different third glycosides of glucose, seminose first glycosides, seminose second glycosides; seminose third glycosides; different third glycosides of seminose, gulose first glycosides, gulose second glycosides; gulose third glycosides; different third glycosides of gulose, semi-lactosi first glycosides, semi-lactosi second glycosides; semi-lactosi third glycosides, different third glycosides of semi-lactosi.
6. method of protecting the monosaccharide primary hydroxy group selective oxidation, it is characterized in that with the described compound of Formula I of each claim of claim 1～3 be catalyzer, protection monose material and 1%～20% (W/W) the hypohalite solution for the treatment of oxidation is reacted; The consumption of compound of Formula I is 0.1%～5.0% (W/W) of protection monose.
7. the method for the described protection monosaccharide primary hydroxy group of claim 6 selective oxidation, described protection monose comprises glucose first glycosides, glucose second glycosides; glucose third glycosides, different third glycosides of glucose, allose first glycosides; allose second glycosides, allose third glycosides, different third glycosides of allose; altrose first glycosides, altrose second glycosides, altrose third glycosides; different third glycosides of altrose, seminose first glycosides, seminose second glycosides; seminose third glycosides; different third glycosides of seminose, gulose first glycosides, gulose second glycosides; gulose third glycosides; different third glycosides of gulose, semi-lactosi first glycosides, semi-lactosi second glycosides; semi-lactosi third glycosides, different third glycosides of semi-lactosi.
8. the method for the described protection monosaccharide primary hydroxy group of claim 6 selective oxidation, described hypohalite is selected from hypochlorite, hypobromite.
9. the method for the described protection monosaccharide primary hydroxy group of claim 8 selective oxidation, described hypohalite is clorox or sodium hypobromite.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009067847A1 (en) * | 2007-11-28 | 2009-06-04 | Chongqing Shengkai Science & Technology Co., Ltd. | Catalyst and method for selectively oxidizing primary hydroxy of protected monosaccharide |
| WO2009111915A1 (en) * | 2008-03-12 | 2009-09-17 | Chongqing Shengkai Science & Technology Co., Ltd. | Bromide-free tempo-mediated oxidation of the primary alcohol in carbohydrate under two-phase conditions |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4219459A1 (en) * | 1992-06-13 | 1993-12-16 | Huels Chemische Werke Ag | Process for the preparation of 2,2,6,6-tetramethylpiperidine-N-oxyl and its derivatives substituted in the 4-position |
| US7084196B2 (en) * | 2001-03-20 | 2006-08-01 | Ciba Specialty Chemicals Corporation | Flame retardant compositions |
-
2006
- 2006-11-08 CN CNB2006101143722A patent/CN100460392C/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009067847A1 (en) * | 2007-11-28 | 2009-06-04 | Chongqing Shengkai Science & Technology Co., Ltd. | Catalyst and method for selectively oxidizing primary hydroxy of protected monosaccharide |
| WO2009111915A1 (en) * | 2008-03-12 | 2009-09-17 | Chongqing Shengkai Science & Technology Co., Ltd. | Bromide-free tempo-mediated oxidation of the primary alcohol in carbohydrate under two-phase conditions |
| CN101952237A (en) * | 2008-03-12 | 2011-01-19 | 重庆华邦制药股份有限公司 | Bromide-free TEMPO-mediated oxidation of the primary alcohol in carbohydrate under two-phase conditions |
| CN101952237B (en) * | 2008-03-12 | 2014-01-08 | 重庆华邦制药有限公司 | Bromide-free TEMPO-mediated oxidation of the primary alcohol in carbohydrate under two-phase conditions |
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