CN102675382B - Preparation method of 3-O-benzyl-1,2-O-isopropylidene-6-oxy-alpha-D-glucofuranoside-6-phenyl dithoorthoester - Google Patents
Preparation method of 3-O-benzyl-1,2-O-isopropylidene-6-oxy-alpha-D-glucofuranoside-6-phenyl dithoorthoester Download PDFInfo
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- CN102675382B CN102675382B CN201210173405.6A CN201210173405A CN102675382B CN 102675382 B CN102675382 B CN 102675382B CN 201210173405 A CN201210173405 A CN 201210173405A CN 102675382 B CN102675382 B CN 102675382B
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Abstract
The invention relates to a preparation method of 3-O-benzyl-1,2-O-isopropylidene-6-oxy-alpha-D-glucofuranoside-6-phenyl dithoorthoester. The 3-O-benzyl-1,2-O-isopropylidene-6-oxy-alpha-D- glucofuranoside-6-phenyl dithoorthoester is mainly prepared from the following components in parts by weight: 35-40 parts of 3-O-benzyl-1,2-O-isopropylidene-6-oxy-alpha-D-glucofuranoside-tetrahydrofuran solution, 5-10 parts of n-butyl lithium and 15-20 parts of trithiophenyl methane-tetrahydrofuran solution. According to the preparation method, the n-butyl lithium does not invalidate, the temperature requirement is not high, the reaction operation is simple, and economy and practicability are realized.
Description
Technical field
The present invention relates to the preparation method of glucofuranose anhydride phenyl thio-orthoester, be specifically related to 3-O-benzyl-1, the preparation method of 2-O-isopropylidene-6-oxygen-α-D-glucofuranose acid anhydride-6-phenyl thio-orthoester.
Background technology
Preparation 3-O-benzyl-1, in the prior art of 2-O-isopropylidene-6-oxygen-α-D-glucofuranose acid anhydride-6-phenyl thio-orthoester, WO2011/014793 A2 discloses a kind of 3-O-benzyl-1, the method of 2-O-isopropylidene-6-oxygen-α-D-glucofuranose acid anhydride-6-phenyl thio-orthoester, first three thioanisoles are dissolved in tetrahydrofuran (THF), then be cooled to below-80 DEG C, temperature required harsher, then drip n-Butyl Lithium, and reaction is violent after dropping n-Butyl Lithium, be not easy to control, and n-Butyl Lithium is very active, even if rate of addition is very slow, also easy and airborne reaction of moisture, cause losing efficacy.CN102250357A, CN102311547A, CN1644548A etc. disclosed phenyl thio reaction, but raw material is all not easy to make, and the reaction process time is long, also not easy to operate.
Summary of the invention
In order to overcome above-mentioned defect, the object of this invention is to provide a kind ofly react controlled, temperature requirement is not high, simple to operate, 3-O-benzyl-1 of economic environmental protection, the preparation method of 2-O-isopropylidene-6-oxygen-α-D-glucofuranose acid anhydride-6-phenyl thio-orthoester.
In 3-O-of the present invention benzyl-1, in the preparation method of 2-O-isopropylidene-6-oxygen-α-D-glucofuranose acid anhydride-6-phenyl thio-orthoester, described 3-O-benzyl-1,2-O-isopropylidene-6-oxygen-α-D-glucofuranose acid anhydride-6-phenyl thio-orthoester, is mainly prepared from by each composition of following weight parts:
3-O-benzyl-1 of 35～40 parts, 2-O-isopropylidene-6-oxygen-α-D-glucofuranose acid anhydride-tetrahydrofuran solution, the n-Butyl Lithium of 5～10 parts, the three thioanisoles-tetrahydrofuran solution of 15～20 parts.
Wherein, described 3-O-benzyl-1,3-O-benzyl-1 in 2-O-isopropylidene-6-oxygen-α-D-glucofuranose acid anhydride-tetrahydrofuran solution, the weight percentage of 2-O-isopropylidene-6-oxygen-α-D-glucofuranose acid anhydride is 10%～20%.
In addition, in described three thioanisoles-tetrahydrofuran solution, the weight percentage of three thioanisoles is 35%～45%.
In addition, preparation method of the present invention, comprises the steps:
(1) in inert gas environment, be less than under the condition of-40 DEG C, in reactor, add n-Butyl Lithium;
(2) then in reactor, splash into three thioanisoles-tetrahydrofuran solution, stir;
(3) continue to add 3-O-benzyl-1 in reactor 2-O-isopropylidene-6-oxygen-α-D-glucofuranose acid anhydride-tetrahydrofuran solution ,-20 DEG C of following reactions 0.5～1.5 hour;
(4) after reaction finishes, rise to room temperature in 2 hours, continue stirring reaction 1.5～2 hours;
(5) cancellation reaction;
(6) extraction, washing organic phase, dry, make 3-O-benzyl-1,2-O-isopropylidene-6-oxygen-α-D-glucofuranose acid anhydride-6-phenyl thio-orthoester.
Wherein, described rare gas element is argon gas or nitrogen.
In addition, the temperature of described step (2) is below-20 DEG C.
In addition, in step (5), add to reaction system the ammonium chloride solution cancellation reaction that the weight percentage of 70～75 weight parts is 25%～30%.
In addition, the extraction agent of described extraction is one or more in ethyl acetate, ethyl formate or methyl acetate.
In addition, in step (6), described by sodium sulfate powder dry organic phase under room temperature.
Reaction structure formula of the present invention is as follows:
In the present invention, it is very violent that n-Butyl Lithium is met water reaction, even can blast, and therefore must guarantee that solvent, the instrument used are dry.In addition, before feeding in raw material, also can adopt the method for logical argon gas after passing into nitrogen, argon gas or first leading to nitrogen that the air in reactor is drained only, but be not limited to this, also can select any other can get rid of the method for the air in reaction environment.In addition, when reaction finishes, can use developping agent for ethyl acetate: the whether in addition reaction raw materials existence of some plate detection that isohexane equals 1: 2, whether complete by some plate detection reaction.And, after reaction finishes, can adopt ethyl acetate to extract reaction solution, and be dried with sodium sulfate, but be not limited to this, also can adopt other ways well known in the art.
Prepare 3-O-benzyl-1 by method of the present invention, 2-O-isopropylidene-6-oxygen-α-D-glucofuranose acid anhydride-6-phenyl thio-orthoester, first the disposable n-Butyl Lithium that adds, be cooled to-40 DEG C, then slowly add the tetrahydrofuran solution of three thioanisoles and the tetrahydrofuran solution of raw material, not only ensure that n-Butyl Lithium can not lose efficacy, and the requirement of temperature not very harsh, make reaction become simple to operate and economical.
Brief description of the drawings
Fig. 1 is 3-O-benzyl-1 that embodiment makes, the hydrogen nuclear magnetic resonance spectrogram of 2-O-isopropylidene-6-oxygen-α-D-glucofuranose acid anhydride-6-phenyl thio-orthoester.
Fig. 2 is 3-O-benzyl-1 that embodiment makes, the carbon-13 nmr spectra figure of 2-O-isopropylidene-6-oxygen-α-D-glucofuranose acid anhydride-6-phenyl thio-orthoester.
Embodiment
Following examples are used for illustrating the present invention, but are not used for limiting the scope of the invention.
Embodiment 1
1. guarantee that reactor is clean and dry.Valve-off.Detect THF moisture content, its moisture content need be less than 0.05%.
2. in reactor, pass into nitrogen, the nitrogen mouth of pipe is placed in reactor bottom, continues 20 minutes, makes Bas Discharged in still.
3. open refrigeration equipment, require temperature to reach-40 DEG C.
4. open stirring, in reactor, add 7Kg n-Butyl Lithium, adition process will be noted protection.
5. the three thioanisole tetrahydrofuran solutions that are 39% by 19.8Kg tri-thioanisole weight percentages are added dropwise in reactor, and whole adition process guarantees that reacting liquid temperature is lower than-20 DEG C.After dropwising, keep temperature to stir half an hour lower than-20 DEG C.
6. by 36.6Kg3-O-benzyl-1,3-O-benzyl-1 that 2-O-isopropylidene-6-oxygen-α-D-glucofuranose acid anhydride weight percentage is 16%, 2-O-isopropylidene-6-oxygen-α-D-glucofuranose acid anhydride tetrahydrofuran solution, slowly adds in reactor, and whole adition process guarantees that temperature is lower than-20 DEG C.After dropwising, keep temperature to stir 1 hour lower than-20 DEG C.
7. in 2 hours, temperature of reaction kettle is risen to room temperature, stirring reaction 2 hours.
8. reacted that in backward reactor, to add 74Kg weight percentage be 27% ammonium chloride solution, vigorous stirring half an hour.
By ethyl acetate to reaction solution extracting twice, consumption is respectively 110Kg and 70Kg.Merge organic phase, water (35Kg) is washed once.Use 5Kg dried over sodium sulfate.Underpressure distillation (temperature be 40 DEG C, pressure for-0.095MPa), leave standstill crystallization, make white 3-O-benzyl-1,2-O-isopropylidene-6-oxygen-α-D-glucofuranose acid anhydride-6-phenyl thio-orthoester crystal, fusing point 110-115 DEG C, optically-active :+5.51 ± 0.13 (c=1.0, CHCl3), productive rate 55%.
From Fig. 1 and Fig. 2:
1H?NMR(400MHz，CDCl
3)：δ＝1.33(s，3H)；1.50(s，3H)；3.18(brs，1H，-OH)，3.62(d，J＝4.0Hz，1H)；4.22(m，2H)；4.48(m，2H)；4.81(dd，J＝J＝3.6，2.40Hz，2H)；6.00(d，J＝4.0，1H)；7.06-7.69(m，20H)ppm.
13C?NMR(100MHz，CDCl
3)：δ＝26.63；27.22；71.82；72.92，?77.21；77.82；80.00；82.00；83.20；104.96；112.29；127.68；127.88；128.41；128.46；12917；131.40；136.63；137.03ppm.
Can be confirmed by hydrogen nuclear magnetic resonance spectrogram and carbon-13 nmr spectra figure, the product making is 3-O-benzyl-1,2-O-isopropylidene-6-oxygen-α-D-glucofuranose acid anhydride-6-phenyl thio-orthoester.
Embodiment 2
1. guarantee that reactor is clean and dry.Valve-off.Detect THF moisture content, its moisture content need be less than 0.05%.
2. in reactor, pass into argon gas, the argon gas mouth of pipe is placed in reactor bottom, continues 20 minutes, makes Bas Discharged in still.
3. open refrigeration equipment, require temperature to reach-40 DEG C.
4. open stirring, in reactor, add 10Kg n-Butyl Lithium, adition process will be noted protection.
5. the three thioanisole tetrahydrofuran solutions that are 35% by 20Kg tri-thioanisole weight percentages are added dropwise in reactor, and whole adition process guarantees that reacting liquid temperature is lower than-20 DEG C.After dropwising, keep temperature to stir half an hour lower than-20 DEG C.
6. by 40Kg 3-O-benzyl-1,3-O-benzyl-1 that 2-O-isopropylidene-6-oxygen-α-D-glucofuranose acid anhydride weight percentage is 20%, 2-O-isopropylidene-6-oxygen-α-D-glucofuranose acid anhydride tetrahydrofuran solution, slowly adds in reactor, and whole adition process guarantees that temperature is lower than-20 DEG C.After dropwising, keep temperature to stir 0.5 hour lower than-20 DEG C.
7. in 2 hours, temperature of reaction kettle is risen to room temperature, stirring reaction 1.5 hours.
8. reacted that in backward reactor, to add 75Kg weight percentage be 25% ammonium chloride solution, vigorous stirring half an hour.
With ethyl formate to reaction solution extracting twice, consumption is respectively 110Kg and 70Kg.Merge organic phase, water (35Kg) is washed once.Use 10Kg dried over sodium sulfate.Underpressure distillation (temperature be 45 DEG C, pressure for-0.090MPa), leaves standstill crystallization, makes white 3-O-benzyl-1,2-O-isopropylidene-6-oxygen-α-D-glucofuranose acid anhydride-6-phenyl thio-orthoester crystal, fusing point 110-115 DEG C, optically-active :+5.51 ± 0.13 (c=1.0, CHCl
3), productive rate 65%.
Identical with embodiment 1, carry out hydrogen spectrum and the test of carbon spectrum spectrogram, result can verify that product is 3-O-benzyl-1,2-O-isopropylidene-6-oxygen-α-D-glucofuranose acid anhydride-6-phenyl thio-orthoester.
Embodiment 3
1. guarantee that reactor is clean and dry.Valve-off.Detect THF moisture content, its moisture content need be less than 0.05%.
2. in reactor, pass into nitrogen, the nitrogen mouth of pipe is placed in reactor bottom, continues 20 minutes, makes Bas Discharged in still.
3. open refrigeration equipment, require temperature to reach-40 DEG C.
4. open stirring, in reactor, add 5Kg n-Butyl Lithium, adition process will be noted protection.
5. the three thioanisole tetrahydrofuran solutions that are 45% by 15Kg tri-thioanisole weight percentages are added dropwise in reactor, and whole adition process guarantees that reacting liquid temperature is lower than-20 DEG C.After dropwising, keep temperature to stir half an hour lower than-20 DEG C.
6. by 35Kg 3-O-benzyl-1,3-O-benzyl-1 that 2-O-isopropylidene-6-oxygen-α-D-glucofuranose acid anhydride weight percentage is 10%, 2-O-isopropylidene-6-oxygen-α-D-glucofuranose acid anhydride tetrahydrofuran solution, slowly adds in reactor, and whole adition process guarantees that temperature is lower than-20 DEG C.After dropwising, keep temperature to stir 1.5 hours lower than-20 DEG C.
7. in 2 hours, temperature of reaction kettle is risen to room temperature, stirring reaction 2 hours.
8. reacted that in backward reactor, to add 70Kg weight percentage be 30% ammonium chloride solution, vigorous stirring half an hour.
With methyl acetate to reaction solution extracting twice.Merge organic phase, water (35Kg) is washed once.Use 5Kg dried over sodium sulfate.Underpressure distillation (temperature be 50 DEG C, pressure for-0.095MPa), leaves standstill crystallization, makes white 3-O-benzyl-1,2-O-isopropylidene-6-oxygen-α-D-glucofuranose acid anhydride-6-phenyl thio-orthoester crystal, fusing point 110-115 DEG C, optically-active :+5.51 ± 0.13 (c=1.0, CHCl
3), productive rate 58%.
Identical with embodiment 1, carry out hydrogen spectrum and the test of carbon spectrum spectrogram, result can verify that product is 3-O-benzyl-1,2-O-isopropylidene-6-oxygen-α-D-glucofuranose acid anhydride-6-phenyl thio-orthoester.
Embodiment 4
1. guarantee that reactor is clean and dry.Valve-off.Detect THF moisture content, its moisture content need be less than 0.05%.
2. in reactor, pass into argon gas, the argon gas mouth of pipe is placed in reactor bottom, continues 20 minutes, makes Bas Discharged in still.
3. open refrigeration equipment, require temperature to reach-40 DEG C.
4. open stirring, in reactor, add 8Kg n-Butyl Lithium, adition process will be noted protection.
5. the three thioanisole tetrahydrofuran solutions that are 40% by 18Kg tri-thioanisole weight percentages are added dropwise in reactor, and whole adition process guarantees that reacting liquid temperature is lower than-20 DEG C.After dropwising, keep temperature to stir half an hour lower than-20 DEG C.
6. by 38Kg 3-O-benzyl-1,3-O-benzyl-1 that 2-O-isopropylidene-6-oxygen-α-D-glucofuranose acid anhydride weight percentage is 18%, 2-O-isopropylidene-6-oxygen-α-D-glucofuranose acid anhydride tetrahydrofuran solution, slowly adds in reactor, and whole adition process guarantees that temperature is lower than-20 DEG C.After dropwising, keep temperature to stir 1 hour lower than-20 DEG C.
7. in 2 hours, temperature of reaction kettle is risen to room temperature, stirring reaction 2 hours.
8. reacted that in backward reactor, to add 72Kg weight percentage be 27% ammonium chloride solution, vigorous stirring half an hour.
By ethyl acetate to reaction solution extracting twice, consumption is respectively 110Kg and 70Kg.Merge organic phase, water (35Kg) is washed once.Use 5Kg dried over sodium sulfate.Underpressure distillation (temperature be 40 DEG C, pressure for-0.095MPa), leaves standstill crystallization, makes white 3-O-benzyl-1,2-O-isopropylidene-6-oxygen-α-D-glucofuranose acid anhydride-6-phenyl thio-orthoester crystal, fusing point 110-115 DEG C, optically-active :+5.51 ± 0.13 (c=1.0, CHCl
3), productive rate 60%.Identical with embodiment 1, carry out hydrogen spectrum and the test of carbon spectrum spectrogram, result can verify that product is 3-O-benzyl-1,2-O-isopropylidene-6-oxygen-α-D-glucofuranose acid anhydride-6-phenyl thio-orthoester.
Claims (6)
1.3-O-benzyl-1, the preparation method of 2-O-isopropylidene-6-oxygen-α-D-glucofuranose acid anhydride-6-phenyl thio-orthoester, it is characterized in that, described 3-O-benzyl-1,2-O-isopropylidene-6-oxygen-α-D-glucofuranose acid anhydride-6-phenyl thio-orthoester is mainly prepared from by each composition of following weight parts:
3-O-benzyl-1 of 35～40 parts, 2-O-isopropylidene-6-oxygen-α-D-glucofuranose acid anhydride-tetrahydrofuran solution, the n-Butyl Lithium of 5～10 parts, the three thioanisoles-tetrahydrofuran solution of 15～20 parts;
Described 3-O-benzyl-1,3-O-benzyl-1 in 2-O-isopropylidene-6-oxygen-α-D-glucofuranose acid anhydride-tetrahydrofuran solution, the weight percentage of 2-O-isopropylidene-6-oxygen-α-D-glucofuranose acid anhydride is 10%～20%;
In described three thioanisoles-tetrahydrofuran solution, the weight percentage of three thioanisoles is 35%～45%;
Described 3-O-benzyl-1, the preparation method of 2-O-isopropylidene-6-oxygen-α-D-glucofuranose acid anhydride-6-phenyl thio-orthoester, comprises the steps:
(1) in inert gas environment, be less than under the condition of-40 DEG C, in reactor, add n-Butyl Lithium;
(2) then in reactor, splash into three thioanisoles-tetrahydrofuran solution, stir;
(3) continue to add 3-O-benzyl-1 in reactor 2-O-isopropylidene-6-oxygen-α-D-glucofuranose acid anhydride-tetrahydrofuran solution ,-20 DEG C of following reactions 0.5～1.5 hour;
(4) after reaction finishes, rise to room temperature in 2 hours, continue stirring reaction 1.5～2 hours;
(5) cancellation reaction;
(6) extraction, washing organic phase, dry, make 3-O-benzyl-1,2-O-isopropylidene-6-oxygen-α-D-glucofuranose acid anhydride-6-phenyl thio-orthoester.
2. preparation method according to claim 1, is characterized in that, described rare gas element is argon gas or nitrogen.
3. preparation method according to claim 1, is characterized in that, the temperature of described step (2) is below-20 DEG C.
4. preparation method according to claim 1, is characterized in that, in step (5), adds to reaction system the ammonium chloride solution cancellation reaction that the weight percentage of 70～75 weight parts is 25%～30%.
5. preparation method according to claim 1, is characterized in that, the extraction agent of described extraction is one or more in ethyl acetate, ethyl formate or methyl acetate.
6. preparation method according to claim 1, is characterized in that, in step (6), described by sodium sulfate powder dry organic phase under room temperature.
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Non-Patent Citations (4)
| Title |
|---|
| "Efficient selective preparation of methyl-1,2,4-tri-O-acetyl-3-O-benzyl-β-L-idopyranuronate from methyl 3-O-benzyl-L-iduronate";Anna Dilhas et al.;《Carbohydrate Research》;20031231;第338卷;681-686 * |
| "New accesses to L-iduronyl synthons";A. Lubineau et al.;《Tetrahedron Letters》;20001231;第41卷;307-311 * |
| A. Lubineau et al.."New accesses to L-iduronyl synthons".《Tetrahedron Letters》.2000,第41卷307-311. |
| Anna Dilhas et al.."Efficient selective preparation of methyl-1,2,4-tri-O-acetyl-3-O-benzyl-β-L-idopyranuronate from methyl 3-O-benzyl-L-iduronate".《Carbohydrate Research》.2003,第338卷681-686. |
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