CN102967683B - High-performance liquid chromatography method for methyl(3R)-3-(tert-butyldimethylsilyloxy)-5-oxo-6-triphenylphos phoranylidenehexanoate - Google Patents
High-performance liquid chromatography method for methyl(3R)-3-(tert-butyldimethylsilyloxy)-5-oxo-6-triphenylphos phoranylidenehexanoate Download PDFInfo
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- CN102967683B CN102967683B CN201210462620.8A CN201210462620A CN102967683B CN 102967683 B CN102967683 B CN 102967683B CN 201210462620 A CN201210462620 A CN 201210462620A CN 102967683 B CN102967683 B CN 102967683B
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Abstract
The invention discloses a high-performance liquid chromatography method for methyl(3R)-3-(tert-butyldimethylsilyloxy)-5-oxo-6-triphenylphos phoranylidenehexanoate, which comprises the following steps: (1) preparing methyl(3R)-3-(tert-butyldimethylsilyloxy)-5-oxo-6-triphenylphos phoranylidenehexanoate serving as a raw material into a sample solution with a concentration of 0.1-1 mg/mL; (2) adding 2-50 mu L of the sample solution into a liquid chromatograph; and (3) carrying out gradient elution by adopting a reversed phase column and taking methanol and buffer salt with a pH value of 2-7 as mobile phases, wherein the flow rate of the gradient elution is 0.5-1.5 ml/min, and the detection wavelength is 210-260 nm. The method disclosed by the invention solves the interference with methyl(3R)-3-(tert-butyldimethylsilyloxy)-5-oxo-6-triphenylphos phoranylidenehexanoate, caused by unknown impurities, and has the advantages of simpleness in operation, good repeatability and high specificity.
Description
Technical field
The present invention relates to a kind of high efficiency liquid phase chromatographic analysis method, specifically refer to the high efficiency liquid phase chromatographic analysis method of one (the 3R)-tert-butyl group two silyloxies-5-oxo-6-triphenylphosphine alkene methyl caproate.
Background technology
(3R)-the tert-butyl group two silyloxies-5-oxo-6-triphenylphosphine alkene methyl caproate is the crucial main material of synthesizing rosuvastatin spit of fland calcium, and its structural formula is as follows:
(3R) the quality of-tert-butyl group two silyloxies-5-oxo-6-triphenylphosphine alkene methyl caproate directly affects the quality of its synthetic rosuvastain calcium, and then the curative effect of medicine is produced to larger impact.In order to ensure the quality of synthetic rosuvastain calcium, need to set up the content of fairly perfect method detection (3R)-tert-butyl group two silyloxies-5-oxo-6-triphenylphosphine alkene methyl caproate.Have no at present disclosed about (3R) – tert-butyl group two silyloxies-5-oxygen for the content of – 6 – triphenylphosphine alkene methyl caproates and the detection method of related substance.Having carried out detailed research by the actual degradation material occurring in the raw material to (3R)-tert-butyl group two silyloxies-5-oxo-6-triphenylphosphine alkene methyl caproate and product finds: because degradation material is many, physicochemical property differs greatly, cause each impurity to show and differ greatly in chromatographic column, adopt the elution process of existing degree such as grade to be difficult to each impurity to separate preferably, and general liquid phase analysis method lack control to (3R)-tert-butyl group two silyloxies-5-oxo-6-triphenylphosphine alkene methyl caproate catabolite.
Summary of the invention
Object of the present invention is mainly to solve the interference of unknown impuritie to (3R)-tert-butyl group two silyloxies-5-oxo-6-triphenylphosphine alkene methyl caproate, and general liquid phase analysis method lacks the shortcoming of control to (3R)-tert-butyl group two silyloxies-5-oxo-6-triphenylphosphine alkene methyl caproate catabolite, provide a kind of high efficiency liquid phase chromatographic analysis method of (3R)-tert-butyl group two silyloxies-5-oxo-6-triphenylphosphine alkene methyl caproate.
The present invention is achieved through the following technical solutions:
A kind of high efficiency liquid phase chromatographic analysis method of (3R)-tert-butyl group two silyloxies-5-oxo-6-triphenylphosphine alkene methyl caproate, is characterized in that, is mainly made up of following steps:
(1) get (3R)-tert-butyl group two silyloxies-5-oxo-6-triphenylphosphine alkene methyl caproate raw material, make the sample solution that concentration is 0.1～1mg/mL;
(2) choose in the sample solution injection liquid chromatography of 2 μ L～50 μ L;
(3) adopt reverse-phase chromatographic column, the buffer salt taking methyl alcohol and pH value as 2～7 carries out gradient elution as mobile phase, and the flow velocity of this gradient elution is that 0.5ml/min～1.5ml/min, detection wavelength are 210nm～260nm.
In order to isolate better (3R)-tert-butyl group two silyloxies-5-oxo-6-triphenylphosphine alkene methyl caproate, in described gradient elution mobile phase specifically arrange as follows:
The initial ratio of methyl alcohol is 40%～50%; When 0～5min, methyl alcohol ratio rises to 55% from 40%; When 5～45min, methyl alcohol ratio is 55%; When 45～55min, methyl alcohol ratio rises to 90% from 55%.
In order to reach the object of better separation, described buffer salt is phosphate buffer.
In addition, described phosphate buffer is ammonium dihydrogen phosphate (ADP) damping fluid or potassium phosphate buffer.
Situation about changing for fear of obstruction instrument, separating effect variation or peak retention time occurs, and described phosphate buffering liquid concentration is 0.005mol/L～0.1mol/L.
Further, described phosphate buffering liquid concentration is 0.005mol/L～0.03mol/L.
For fear of the too high peak type variation that causes main peak of pH, the pH value of described buffer salt is 2.0～5.0.
Preferably, described reverse-phase chromatographic column is anti-phase C18 chromatographic column or anti-phase C8 chromatographic column.
Further, in described reverse-phase chromatographic column, particle internal diameter is 3.5 μ m.
Preferably, the column temperature of described reverse-phase chromatographic column is 20 DEG C～40 DEG C.
The present invention has the following advantages and beneficial effect:
1, by method of the present invention, can analyze all known impurities in (3R)-tert-butyl group two silyloxies-5-oxo-6-triphenylphosphine alkene methyl caproate simultaneously, solve the interference of unknown impuritie to (3R)-tert-butyl group two silyloxies-5-oxo-6-triphenylphosphine alkene methyl caproate, avoid general liquid phase analysis method (3R)-tert-butyl group two silyloxies-5-oxo-6-triphenylphosphine alkene methyl caproate catabolite to be lacked to the shortcoming of control simultaneously.
2, it is that mobile phase carries out gradient elution method and carries out HPLC detection that the present invention adopts buffer salt that methyl alcohol and pH value are 2～7, can effectively control more comprehensively the impurity in (3R)-tert-butyl group two silyloxies-5-oxo-6-triphenylphosphine alkene methyl caproate raw material and product, (3R)-tert-butyl group two silyloxies-5-oxo-6-triphenylphosphine alkene methyl caproate raw material and catabolite are effectively separated simultaneously, make to separate between all impurity and main peak better, and do not have unknown impuritie to disturb main peak, control well the quality of product, and then be that the quality of synthesizing final products Rui Shutating calcium provides safeguard, there is significant progress.
3, the present invention is simple to operate, reproducible, has good specificity by embodiment.
Brief description of the drawings
Fig. 1 is the chromatographic condition figure of embodiment 1.
Fig. 2 is the chromatographic condition figure of embodiment 2.
Fig. 3 is optimum chromatographic condition acid destruction figure.
Fig. 4 is optimum chromatographic condition alkali destruction figure.
Fig. 5 is optimum chromatographic condition Oxidative demage figure.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is further illustrated, but embodiments of the present invention are not limited to this.
Embodiment 1
Instrument and condition that the present embodiment is required are as follows:
High performance liquid chromatograph: Agilent 1260LC, UV detecting device;
Chromatographic column: C18,4.6 × 250mm, 3.5 μ m;
Damping fluid: take 1.4g potassium dihydrogen phosphate and be dissolved in 1L water, adjust pH to 2.2 with phosphoric acid, filter;
Mobile phase: the phosphate buffer of acetonitrile; Flow velocity: 1.2mL/min; Detect wavelength: 220nm; Column temperature: 40 DEG C; Sampling volume: 20 μ L.
The operation steps of the present embodiment is as follows:
(1) get (3R)-tert-butyl group two silyloxies-5-oxo-6-triphenylphosphine alkene methyl caproate sample appropriate, with methyl alcohol, ultrasonic 15min dissolves, being made into concentration is the sample solution of (3R)-tert-butyl group two silyloxies-5-oxo-6-triphenylphosphine alkene methyl caproate of 0.5mg/mL, centrifugal, get supernatant as sample solution.
(2) get above-mentioned sample solution 20 μ L sample introductions, using the phosphate buffer liquid of acetonitrile as mobile phase, carry out gradient elution by following condition, main gradient is described below: the concentration of initial acetonitrile is 45%; When 0～5min, the ratio of acetonitrile rises to 55% from 45%; When 5～45min, the ratio of acetonitrile rises to 90% from 55%.
Record chromatogram, this chromatogram of result has a unknown impuritie to be wrapped in main peak, and Fig. 1 is shown in by its typical collection of illustrative plates; Wherein, horizontal ordinate is the time, and ordinate is absorbance.
Embodiment 2
Instrument and condition that the present embodiment is required are as follows:
High performance liquid chromatograph: Agilent 1260LC, UV detecting device;
Chromatographic column: C18,4.6 × 250mm, 3.5 μ m;
Damping fluid: take 1.4g ammonium dihydrogen phosphate (ADP) and be dissolved in 1L water, adjust pH to 2.4 with phosphoric acid, filter;
Mobile phase: the phosphate buffer of methyl alcohol; Flow velocity: 1.0mL/min; Detect wavelength: 220nm; Column temperature: 30 DEG C; Sampling volume: 20 μ L.
The operation steps of the present embodiment is as follows:
(1) get (3R)-tert-butyl group two silyloxies-5-oxo-6-triphenylphosphine alkene methyl caproate sample appropriate, use methyl alcohol ultrasonic dissolution, being made into concentration is the sample solution of (3R)-tert-butyl group two silyloxies-5-oxo-6-triphenylphosphine alkene methyl caproate of 0.5mg/mL, centrifugal, get supernatant as sample solution.
(2) get above-mentioned sample solution 20 μ L sample introductions, using the phosphate buffer liquid of methyl alcohol as mobile phase, carry out gradient elution by following condition, main gradient is described below: the concentration of initial methyl alcohol is 45%; When 0～5min, the ratio of methyl alcohol rises to 55% from 45%; When 5～45min, the ratio of methyl alcohol rises to 90% from 55%.
Record chromatogram, this chromatogram unknown impuritie of result can separate with main peak, and each known impurities and main peak degree of separation are better, and Fig. 2 is shown in by its typical collection of illustrative plates; Wherein, horizontal ordinate Minutes is the time, and ordinate AU is absorbance.
Embodiment 3
Instrument and condition that the present embodiment is required are as follows:
High performance liquid chromatograph: Agilent 1260LC, UV detecting device;
Chromatographic column: C18,4.6 × 250mm, 3.5 μ m;
Damping fluid: take 1.4g ammonium dihydrogen phosphate (ADP) and be dissolved in 1L water, adjust pH to 2.4 with phosphoric acid, filter;
Mobile phase: the phosphate buffer of methyl alcohol; Flow velocity: 1.0mL/min; Detect wavelength: 220nm; Column temperature: 30 DEG C; Sampling volume: 20 μ L.
The operation steps of the present embodiment is as follows:
(1) preparation alkali destroys, acid destroys, the sample of Oxidative demage,
Alkali destroys: get (3R)-tert-butyl group two silyloxies-5-oxo-6-triphenylphosphine alkene methyl caproate sample in right amount to 10mL volumetric flask, add 1N sodium hydroxide solution 2mL, normal temperature is placed half an hour, add the neutralization of 1N hydrochloric acid, be configured to (3R)-tert-butyl group two silyloxies-5-oxo-6-triphenylphosphine alkene methyl caproate sample solution that concentration is 0.5mg/mL by methanol constant volume, after filtration, destroy sample as alkali;
Acid destroys: get (3R)-tert-butyl group two silyloxies-5-oxo-6-triphenylphosphine alkene methyl caproate sample in right amount to 10mL volumetric flask, add 1N hydrochloric acid solution 2mL, 60 DEG C of water-baths 1 hour, add the neutralization of 1N sodium hydroxide solution, be configured to (3R)-tert-butyl group two silyloxies-5-oxo-6-triphenylphosphine alkene methyl caproate sample solution that concentration is 0.5mg/mL by methanol constant volume, after filtration, destroy sample as acid;
Oxidative demage: get (3R)-tert-butyl group two silyloxies-5-oxo-6-triphenylphosphine alkene methyl caproate sample in right amount to 10mL volumetric flask, add 30% hydrogen peroxide 2mL, normal temperature is placed half an hour, be configured to (3R)-tert-butyl group two silyloxies-5-oxo-6-triphenylphosphine alkene methyl caproate sample solution that concentration is 0.5mg/mL by methanol constant volume, after filtration, as Oxidative demage sample.
(2) in order to investigate the specificity of the inventive method, by the sample solution sample introduction respectively of alkali destruction, acid destruction, Oxidative demage, using the phosphate buffer of methyl alcohol as organic phase, sample introduction 20 μ L, carry out gradient elution by following condition, main gradient is described below: the concentration of initial methyl alcohol is 45%; When 0～5min, the ratio of methyl alcohol rises to 55% from 45%; When 5～45min, the ratio of methyl alcohol rises to 90% from 55%.
Record chromatogram, wherein, Fig. 3 is the chromatogram of the sample solution after acid destroys, and Fig. 4 is the chromatogram of the sample solution after alkali destroys, and Fig. 5 is the chromatogram of the sample solution after Oxidative demage; Horizontal ordinate Minutes is the time, and ordinate AU is absorbance.Result shows: after this chromatogram main peak, unknown impuritie can separate with main peak, and each known impurities and main peak degree of separation are better, and then proves that method specificity of the present invention is better.
As mentioned above, just can realize preferably the present invention.
Claims (6)
1. a high efficiency liquid phase chromatographic analysis method for (3R)-tert-butyl group two silyloxies-5-oxo-6-triphenylphosphine alkene methyl caproate, is characterized in that, is mainly made up of following steps:
(1) get (3R)-tert-butyl group two silyloxies-5-oxo-6-triphenylphosphine alkene methyl caproate raw material, make the sample solution that concentration is 0.1～1mg/mL;
(2) choose in the sample solution injection liquid chromatography of 2 μ L～50 μ L;
(3) adopt reverse-phase chromatographic column, the buffer salt taking methyl alcohol and pH value as 2～7 carries out gradient elution as mobile phase, and the flow velocity of this gradient elution is that 0.5ml/min～1.5ml/min, detection wavelength are 210nm～260nm;
Wherein, in described gradient elution mobile phase specifically arrange as follows:
When 0～5min, methyl alcohol ratio rises to 55% from 40%; When 5～45min, methyl alcohol ratio is 55%; When 45～55min, methyl alcohol ratio rises to 90% from 55%;
Described buffer salt is ammonium dihydrogen phosphate (ADP) damping fluid or potassium phosphate buffer;
The concentration of described ammonium dihydrogen phosphate (ADP) damping fluid or potassium phosphate buffer is 0.005mol/L～0.1mol/L.
2. the high efficiency liquid phase chromatographic analysis method of one according to claim 1 (the 3R)-tert-butyl group two silyloxies-5-oxo-6-triphenylphosphine alkene methyl caproate, it is characterized in that, the concentration of described ammonium dihydrogen phosphate (ADP) damping fluid or potassium phosphate buffer is 0.005mol/L～0.03mol/L.
3. the high efficiency liquid phase chromatographic analysis method of one according to claim 1 (the 3R)-tert-butyl group two silyloxies-5-oxo-6-triphenylphosphine alkene methyl caproate, is characterized in that, the pH value of described buffer salt is 2.0～5.0.
4. the high efficiency liquid phase chromatographic analysis method of one according to claim 1 (the 3R)-tert-butyl group two silyloxies-5-oxo-6-triphenylphosphine alkene methyl caproate, it is characterized in that, described reverse-phase chromatographic column is anti-phase C18 chromatographic column or anti-phase C8 chromatographic column.
5. the high efficiency liquid phase chromatographic analysis method of one according to claim 4 (the 3R)-tert-butyl group two silyloxies-5-oxo-6-triphenylphosphine alkene methyl caproate, is characterized in that, in described reverse-phase chromatographic column, particle internal diameter is 3.5 μ m.
6. according to the high efficiency liquid phase chromatographic analysis method of one (the 3R)-tert-butyl group two silyloxies-5-oxo-6-triphenylphosphine alkene methyl caproate described in claim 1～5 any one, it is characterized in that, the column temperature of described reverse-phase chromatographic column is 20 DEG C～40 DEG C.
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| CN114397386A (en) * | 2021-12-30 | 2022-04-26 | 苏州正济医药研究有限公司 | Method for determining 3R-3-tert-butyldimethylsiloxy-5-oxo-6-triphenylphosphine alkene methyl hexanoate isomer |
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| CN101532990B (en) * | 2008-03-10 | 2012-12-19 | 北京德众万全医药科技有限公司 | Method for determining optical isomer of rosuvastatin calcium by using HPLC method |
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