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CN113754590B - Preparation method of rosuvastatin calcium intermediate - Google Patents

Preparation method of rosuvastatin calcium intermediate Download PDF

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CN113754590B
CN113754590B CN202111037971.XA CN202111037971A CN113754590B CN 113754590 B CN113754590 B CN 113754590B CN 202111037971 A CN202111037971 A CN 202111037971A CN 113754590 B CN113754590 B CN 113754590B
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methylsulfonyl
fluorophenyl
pyrimidine
isopropyl
methyl
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CN113754590A (en
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王志华
谢太阳
盛绿青
卢荣彬
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Zhejiang Lepu Pharmaceutical Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/32—One oxygen, sulfur or nitrogen atom
    • C07D239/42—One nitrogen atom
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/40—Special temperature treatment, i.e. other than just for template removal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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Abstract

The invention discloses a preparation method of a rosuvastatin calcium intermediate. The method comprises the steps of firstly preparing a Co-Mn bimetallic oxide catalyst, and oxidizing 4- (4-fluorophenyl) -6-isopropyl-2- [ (N-methyl-N-methylsulfonyl) amine ] pyrimidine-5-methanol by hydrogen peroxide under the action of the Co-Mn bimetallic oxide catalyst to obtain (4-fluorophenyl) -6-isopropyl-2- [ (N-methyl-N-methylsulfonyl) amino ] pyrimidine-5-formaldehyde. The invention has simple raw materials, mild reaction conditions and environmental protection, and can be used for industrial mass production.

Description

Preparation method of rosuvastatin calcium intermediate
Technical Field
The invention belongs to the field of organic synthesis, relates to a preparation method of a rosuvastatin calcium intermediate, and in particular relates to a preparation method of (4-fluorophenyl) -6-isopropyl-2- [ (N-methyl-N-methylsulfonyl) amino ] pyrimidine-5-formaldehyde.
Background
(4-fluorophenyl) -6-isopropyl-2- [ (N-methyl-N-methylsulfonyl) amino ] pyrimidine-5-carbaldehyde is a key intermediate (Current Organic Chemistry,2010,14,816-845) for the synthesis of rosuvastatin. It can be obtained by oxidizing 4- (4-fluorophenyl) -6-isopropyl-2- [ (N-methyl-N-methylsulfonyl) amine ] pyrimidine-5-methanol, and the reaction process is as follows:
Figure BDA0003248044950000011
numerous attempts have been made in the prior art to find suitable oxidants and catalysts in the course of this reaction, for example:
WO2006017357, US20060004200 discloses the oxidation of 4- (4-fluorophenyl) -6-isopropyl-2- [ (N-methyl-N-methylsulfonyl) amine ] pyrimidine-5-methanol to the target product using sodium hypochlorite as the oxidant, however this method produces a large amount of sodium chloride waste salt, is hazardous and has high treatment cost.
CN1821242, CN1763015 discloses that the above reaction is carried out with pyridine chlorochromate as oxidant, however this method produces very difficult to handle chromium as well as pyridine.
WO2007074391 uses calcium hypochlorite as an oxidant, butA large amount of calcium chloride waste salt is produced. CN1958593 with K 2 Cr 2 O 7 Is an oxidizing agent but also produces chromium salts which are extremely difficult to handle. Jingxi Huagong,23 (2), 192-194;2006 in MnO 2 This process produces a large amount of manganese sludge that is extremely difficult to filter as an oxidizing agent.
WO2008059519 uses pyridine sulfur trioxide as oxidant, and the process has great pollution and more three wastes. Organic Process Research & Development,19 (11), 1548-1553;2015 is catalyzed with copper complex, oxygen oxidation, however, the catalyst copper complex preparation is complex. Chemical Science,11 (16), 4251-4262;2020 also uses complex copper complex as catalyst, TMPO oxidation, and its catalyst copper complex preparation is complex.
Therefore, although a great deal of attempts are made in the prior art, the reaction process which has the advantages of simple raw materials, mild reaction conditions and environmental friendliness and can be used for industrial mass production is not found.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a rosuvastatin calcium intermediate.
The invention provides a preparation method of a rosuvastatin calcium intermediate, which comprises the following steps:
1) Dissolving 4- (4-fluorophenyl) -6-isopropyl-2- [ (N-methyl-N-methylsulfonyl) amine ] pyrimidine-5-methanol in a solvent with the weight ratio of 5-10 times of the raw materials, adding a Co-Mn bimetallic oxide catalyst with the weight ratio of 1-10% of the raw materials, and cooling to-10-0 ℃;
the preparation method of the Co-Mn bimetallic oxide catalyst comprises the following steps:
a) 1 part by weight of SBA-15 powder is weighed, normal hexane is added into the powder, and the mixture is stirred for 2 to 10 hours;
b) Weighing cobalt nitrate hexahydrate and manganese nitrate tetrahydrate according to a molar ratio of 1-5:1, wherein the total weight of the cobalt nitrate hexahydrate and the manganese nitrate tetrahydrate is 5-10% of SBA-15, and dissolving the cobalt nitrate hexahydrate and the manganese nitrate tetrahydrate by deionized water;
c) Dropping the solution prepared in the step B) into the normal hexane solution containing SBA-15 in the step A, stirring for 12-24 hours, filtering, transferring the obtained solid phase into a crucible, putting into a muffle furnace, and raising the temperature to 500-600 ℃ at 2-5 ℃/min to obtain the Co-Mn bimetallic oxide catalyst;
2) Dropwise adding 3-30% hydrogen peroxide into the material in the step 1), wherein the molar ratio of the hydrogen peroxide in the hydrogen peroxide to the raw material 4- (4-fluorophenyl) -6-isopropyl-2- [ (N-methyl-N-methylsulfonyl) amine ] pyrimidine-5-methanol is 1-2:1, and stirring for 3-10 hours at the temperature of 0-30 ℃ to obtain (4-fluorophenyl) -6-isopropyl-2- [ (N-methyl-N-methylsulfonyl) amino ] pyrimidine-5-formaldehyde.
The reaction equation is as follows:
Figure BDA0003248044950000021
preferably, in said step A), n-hexane is used in an amount of 10 to 20 times the weight of SBA-15.
Preferably, in the step B), the dosage of deionized water is 5-10 times of the total weight of cobalt nitrate hexahydrate and manganese nitrate tetrahydrate.
Preferably, in step 1), the solvent is one or more of dichloromethane, tetrahydrofuran or acetonitrile.
Compared with the prior art, the invention adopts hydrogen peroxide as an oxidant, has simple raw materials, does not generate waste salt in the reaction, and is easy for post-treatment; the invention adopts Co-Mn bimetallic oxide as the catalyst, the catalyst is simple and convenient to prepare, the catalytic efficiency is high, and the yield of the whole reaction can reach about 95 percent.
Drawings
FIG. 1 is a transmission electron microscope image of a catalyst; wherein (a) is a cross-section transmission electron microscope of the catalyst, and (b) is a longitudinal section transmission electron microscope of the catalyst.
FIG. 2 is a powder X-ray diffraction pattern of a metal oxide catalyst with a ratio of SBA-15 to Co-Mn of 3:1;
FIG. 3 is a scanning electron microscope image of a catalyst;
fig. 4 is an N2 adsorption-desorption isotherm of the catalyst.
Detailed Description
The invention is further illustrated and described below in connection with specific embodiments. The technical features of the embodiments of the invention can be combined correspondingly on the premise of no mutual conflict.
Example 1
10.84 g of SBA-15 powder was weighed, 100 g of n-hexane was added thereto, and stirred for 2 hours; weighing 0.291 cobalt nitrate hexahydrate and 0.251 manganese nitrate tetrahydrate, dissolving the cobalt nitrate hexahydrate and the manganese nitrate tetrahydrate in 2.5 g of deionized water, dripping the prepared solution into an n-hexane solution containing SBA-15, stirring for 12 hours, filtering, transferring the obtained solid phase into a crucible, putting into a muffle furnace, and heating to 500 ℃ at a speed of 2 ℃/min by programming to obtain the Co-Mn bimetallic oxide catalyst.
30 g of 4- (4-fluorophenyl) -6-isopropyl-2- [ (N-methyl-N-methylsulfonyl) amine ] pyrimidine-5-methanol were dissolved in 150 times the weight of the starting material in methylene chloride, and 0.3 g of catalyst was added. Cooled to-10 ℃. 96.3 g of 3% hydrogen peroxide was added dropwise thereto and stirred at 30℃for 3 hours. The catalyst was removed by filtration, the layers were separated, the organic layer was taken and the solvent was recovered to give (4-fluorophenyl) -6-isopropyl-2- [ (N-methyl-N-methylsulfonyl) amino ] pyrimidine-5-carbaldehyde in a yield of 95.1% and a content of 98.3%.
Example 2
17.06 g of SBA-15 powder was weighed, 200 g of n-hexane was added thereto, and stirred for 10 hours; 1.455 g of cobalt nitrate hexahydrate and 0.251 g of manganese nitrate tetrahydrate are weighed, 10 g of deionized water is used for dissolving the cobalt nitrate hexahydrate and the manganese nitrate tetrahydrate, the prepared solution is dripped into an n-hexane solution containing SBA-15, the mixture is stirred for 24 hours, the obtained solid phase is filtered, transferred into a crucible, placed into a muffle furnace, and heated to 600 ℃ at a speed of 5 ℃ per minute by programming, so as to obtain the Co-Mn bimetallic oxide catalyst.
30 g of 4- (4-fluorophenyl) -6-isopropyl-2- [ (N-methyl-N-methylsulfonyl) amine ] pyrimidine-5-methanol were dissolved in 300 g of tetrahydrofuran, 3 g of catalyst. Cooled to 0 ℃. 19.3 g of 30% hydrogen peroxide is added dropwise and stirred for 10 hours at 0 ℃. The catalyst was removed by filtration, the layers were separated, the organic layer was taken and the solvent was recovered to give (4-fluorophenyl) -6-isopropyl-2- [ (N-methyl-N-methylsulfonyl) amino ] pyrimidine-5-carbaldehyde in a yield of 94.5% and a content of 97.3%.
Example 3
10 g of SBA-15 powder was weighed, 150 g of n-hexane was added thereto, and stirred for 5 hours; weighing 0.466 g of cobalt nitrate hexahydrate and 0.134 g of manganese nitrate tetrahydrate, dissolving the cobalt nitrate hexahydrate and the manganese nitrate tetrahydrate with 6.4 g of deionized water, dripping the prepared solution into an n-hexane solution containing SBA-15, stirring for 20 hours, filtering, transferring the obtained solid phase into a crucible, putting into a muffle furnace, and heating to 550 ℃ at a speed of 3 ℃/min by programming to obtain the Co-Mn bimetallic oxide catalyst. Fig. 1 is a transmission electron microscope image of the prepared Co-Mn bimetallic oxide catalyst, and as can be seen from fig. a, the internal structure of a sample can be clearly observed in a TEM image, and the catalyst is obviously a porous structure, and belongs to a mesoporous material. The SBA-15 is shown in the figure b to have regular and orderly structural characteristics, wherein the white part is a silicon wall, the black part is a hole, and the pore channels are arranged along one direction. The method comprises the steps of carrying out a first treatment on the surface of the FIG. 2 is a powder X-ray diffraction chart of SBA-15 powder and a bimetallic oxide catalyst (Co-Mn ratio 3:1) of the present example, from which it can be seen that 2 theta is 19.16 deg., 24.6 deg., 32.88 deg., 34.12 deg., 36.64 deg., 38.04 deg., 42.04 deg., 44.52 deg., characteristic peaks appear, and the main component may be CoMn 2 O 4 And CoMnO 3 The method comprises the steps of carrying out a first treatment on the surface of the Fig. 3 is a scanning electron microscope image of the bimetallic oxide catalyst of the embodiment, which shows a regular short rod-shaped distribution, smooth surface and uniform size, and the appearance may be caused by weak characteristics of inorganic matters generated by hydrogen bonds, adsorption force or coordination bonds and inactive matter surfactants, and the inorganic matters are aggregated under the action of active agent micelles to form short rod-shaped aggregates along with shrinkage and shrinkage aggregation of silicate. The method comprises the steps of carrying out a first treatment on the surface of the Fig. 4 is an N2 adsorption-desorption isotherm of the bimetallic oxide catalyst of the present embodiment, and it can be seen from the figure that the samples all exhibit typical Langmiur type IV adsorption-desorption isotherms, which are typical mesoporous material adsorption types, and the mesoporous size is uniform. .
30 g of 4- (4-fluorophenyl) -6-isopropyl-2- [ (N-methyl-N-methylsulfonyl) amine ] pyrimidine-5-methanol were dissolved in 240 g of acetonitrile, and 0.6 g of catalyst was added. Cooled to-5 ℃. 43.3 g of 10% hydrogen peroxide is added dropwise and stirred for 5 hours at 15 ℃. The catalyst was removed by filtration, the layers were separated, the organic layer was taken and the solvent was recovered to give (4-fluorophenyl) -6-isopropyl-2- [ (N-methyl-N-methylsulfonyl) amino ] pyrimidine-5-carbaldehyde in a yield of 96.5% and a content of 99.3%.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of the invention should be assessed as that of the appended claims.

Claims (3)

1. The preparation method of the rosuvastatin calcium intermediate is characterized by comprising the following steps of:
1) Dissolving 4- (4-fluorophenyl) -6-isopropyl-2- [ (N-methyl-N-methylsulfonyl) amine ] pyrimidine-5-methanol in a solvent with the weight ratio of 5-10 times of the raw materials, adding a Co-Mn bimetallic oxide catalyst with the weight ratio of 1-10% of the raw materials, and cooling to-10-0 ℃; the solvent is one or more of dichloromethane, tetrahydrofuran or acetonitrile;
the preparation method of the Co-Mn bimetallic oxide catalyst comprises the following steps:
a) 1 part by weight of SBA-15 powder is weighed, normal hexane is added into the powder, and the mixture is stirred for 2 to 10 hours;
b) Weighing cobalt nitrate hexahydrate and manganese nitrate tetrahydrate according to a molar ratio of 1-5:1, wherein the total weight of the cobalt nitrate hexahydrate and the manganese nitrate tetrahydrate is 5-10% of SBA-15, and dissolving the cobalt nitrate hexahydrate and the manganese nitrate tetrahydrate by deionized water;
c) Dropping the solution prepared in the step B) into the normal hexane solution containing SBA-15 in the step A, stirring for 12-24 hours, filtering, transferring the obtained solid phase into a crucible, putting into a muffle furnace, and raising the temperature to 500-600 ℃ at 2-5 ℃/min to obtain the Co-Mn bimetallic oxide catalyst;
2) Dropwise adding 3-30% hydrogen peroxide into the material in the step 1), wherein the molar ratio of the hydrogen peroxide in the hydrogen peroxide to 4- (4-fluorophenyl) -6-isopropyl-2- [ (N-methyl-N-methylsulfonyl) amine ] pyrimidine-5-methanol is 1-2:1, and stirring for 3-10 hours at the temperature of 0-30 ℃ to obtain (4-fluorophenyl) -6-isopropyl-2- [ (N-methyl-N-methylsulfonyl) amino ] pyrimidine-5-formaldehyde.
2. The process for the preparation of rosuvastatin calcium intermediate according to claim 1, characterized in that in said step a), n-hexane is used in an amount of 10-20 times by weight of SBA-15.
3. The process for preparing rosuvastatin calcium intermediate according to claim 1, wherein in said step B), the amount of deionized water is 5 to 10 times of the total weight of cobalt nitrate hexahydrate and manganese nitrate tetrahydrate.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050222415A1 (en) * 2002-05-21 2005-10-06 Yatendra Kumar Process for the preparation of rosuvastatin
US20080091014A1 (en) * 2005-01-19 2008-04-17 Anhui Quingyun Pharmaceutical And Chemical Co., Ltd. Synthetic Method and Intermediates of Rosuvastatin Calcium and Preparation Methods of Intermediates
CN113004209A (en) * 2021-03-08 2021-06-22 合肥市梓熤科技贸易有限公司 Synthetic method of rosuvastatin calcium intermediate

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006017357A1 (en) * 2004-07-13 2006-02-16 Teva Pharmaceutical Industries Ltd. A process for the preparation of rosuvastatin involving a tempo-mediated oxidation step
CN107983397A (en) * 2017-12-06 2018-05-04 上海应用技术大学 A kind of cobalt manganese bimetallic catalyst aoxidized for cyclohexane selectivity, preparation method and application

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050222415A1 (en) * 2002-05-21 2005-10-06 Yatendra Kumar Process for the preparation of rosuvastatin
US20080091014A1 (en) * 2005-01-19 2008-04-17 Anhui Quingyun Pharmaceutical And Chemical Co., Ltd. Synthetic Method and Intermediates of Rosuvastatin Calcium and Preparation Methods of Intermediates
CN113004209A (en) * 2021-03-08 2021-06-22 合肥市梓熤科技贸易有限公司 Synthetic method of rosuvastatin calcium intermediate

Non-Patent Citations (1)

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Title
瑞舒伐他汀钙的合成工艺改进;李泽标 等;精细化工中间体;第46卷(第06期);第50-52、55页 *

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