CN107824213B - A kind of method that carried heteropoly acid catalyst prepares chronic obstructive pulmonary disease pharmaceutical intermediate - Google Patents

A kind of method that carried heteropoly acid catalyst prepares chronic obstructive pulmonary disease pharmaceutical intermediate Download PDF

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CN107824213B
CN107824213B CN201711250855.XA CN201711250855A CN107824213B CN 107824213 B CN107824213 B CN 107824213B CN 201711250855 A CN201711250855 A CN 201711250855A CN 107824213 B CN107824213 B CN 107824213B
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heteropoly acid
2h
acid crystal
solution
molecular sieve
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CN201711250855.XA
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CN107824213A (en
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李励
赵兴亚
杨志远
于法鹏
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李励
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Abstract

The invention belongs to organic catalysis technical fields, and in particular to a kind of method that carried heteropoly acid catalyst prepares chronic obstructive pulmonary disease pharmaceutical intermediate, the present invention is with Na2WO4.2H2O、NaVO3.2H2O, disodium hydrogen phosphate, manganese acetate and three n-butylmagnesium chloride ammonium of benzyl are that raw material prepares heteropoly acid crystal, then carry out loading to obtain carried heteropoly acid catalyst with MCM-48 molecular sieve;Using carried heteropoly acid crystal as catalyst, catalysis prepares three phenylacetate intermediate of asthmatic medicament Vilantro, solves the disadvantage that alleviate environmental protection pressure, process route is environmentally protective, meets existing industrial requirement using highly basic in prior art.

Description

A kind of method that carried heteropoly acid catalyst prepares chronic obstructive pulmonary disease pharmaceutical intermediate

Original bill application number 2017102260793, the title a kind of preparation method and purposes of heteropoly acid crystal, the applying date 2017.04.08。

Technical field

The invention belongs to organic catalysis technical fields, and in particular to a kind of carried heteropoly acid catalyst prepares chronic obstructive pulmonary disease medicine The method of object intermediate.

Background technique

Heteropoly acid (Polyoxometalates is abbreviated as POMs) is by hetero atom (such as P, Si, Fe, Co) He Duoyuan The oxygen-containing polyacid of one kind that sub (such as Mo, W, V, Nb, Ta) is made up of by certain structure oxygen atom ligand bridging, has very high Catalytic activity, it is a kind of multifunctional novel catalyst, heteropoly acid that it, which not only has acidity, and has oxidation-reduction quality Stability is good, can make homogeneous and heterogeneous reaction, or even can make phase transfer catalyst, no pollution to the environment, is before one kind has greatly The green catalyst on way, it can be used as going back with alkylating aromatic hydrocarbon and dealkylation, esterification, dehydration/combination reaction, oxidation Original reaction and open loop, condensation, addition and etherification reaction etc..Because of the unique acidity of heteropoly acid, " quasi- liquid phase " behavior, multi-functional The advantages that (acid, oxidation, photoelectrocatalysis), is in catalyticing research field by the extensive attention of researchers.

Three phenylacetate of Vilantro (vilanteroltrifenatate, chemistry it is entitled (R)-4-[2-[[6-[2- [(2,6- dichloro benzyl) oxygroup]-ethyoxyl] hexyl] amino] -1- hydroxyethyl] -2- hydroxymethylphenol three Phenylacetate is 2 receptor stimulating agent of New-type long-acting β of GlaxoSmithKline PLC (GSK) company exploitation, for treating chronic obstruction Property tuberculosis and asthma;Having a key intermediate in the preparation process of active constituent is (II), by (I) formula compound in the tertiary fourth of highly basic Under the action of potassium alcoholate cyclization generate, yield is only that 70%(is detailed in US7361787 B2), and solvent for use be DMF, alkaline waste liquor and Solvent is difficult to be recycled, and environmental protection treatment pressure is big.

So developing a kind of novel process, yield is further increased, and solves environmental protection pressure with great economic significance.

Summary of the invention

The purpose of the present invention is overcome in the prior art (R) -4- [2- [[6- [2- [(2,6- dichloro benzyl) oxygroup] - Ethyoxyl] hexyl] amino] -1- hydroxyethyl] -2- hydroxymethylphenol three phenylacetate intermediate (II) preparation Yield is low in the process, the disagreeableness disadvantage of environment, provides a kind of heteropoly acid crystal for catalysis and prepares intermediate (II).

According to an aspect of the present invention, the present invention provides a kind of preparation methods of heteropoly acid crystal, including following step It is rapid:

1) by Na2WO4.2H2O、NaVO3.2H2O stirring and dissolving soluble in water obtains the first solution;

2) the aqueous solution stirring and dissolving of disodium hydrogen phosphate and manganese acetate is obtained into the second solution;

3) the first solution is added drop-wise in the second solution and is stirred, it is then acid that third is molten to strong acid with sulphur acid for adjusting pH Liquid;

4) third solution is warming up to 60-65 DEG C, and the aqueous solution that three n-butylmagnesium chloride ammonium of benzyl is then added dropwise is stirred to react 1- 2h obtains the 4th muddy solution;

5) potassium acetate is added into the 4th solution and adjusts pH to faintly acid, a large amount of black solids are precipitated;

6) filtering, filter cake successively use purified water, ethanol washing, dry at 40-45 DEG C;

7) obtained solid is recrystallized with isopropyl acetate after drying, and obtains heteropoly acid crystal.

In the preparation method of heteropoly acid crystal of the present invention, further technical solution is the Na2WO4.2H2O with NaVO3.2H2The dosage molar ratio of O is 1:1, Na2WO4.2H2The dosage molar ratio of O and disodium hydrogen phosphate is 1:3-4; Na2WO4.2H2The dosage molar ratio of O and manganese acetate is 1:1.1-1.5;Na2WO4.2H2O rubs with three n-butylmagnesium chloride ammonium of benzyl You are than being 1:4.1-4.5;

In the preparation method of heteropoly acid crystal of the present invention, further technical solution is that the highly acid pH is 2.2-3.0; The faintly acid pH is 4.1-5.2.

According to another aspect of the present invention, heteropoly acid crystal prepared by the present invention can be used for being catalyzed (I) formula structural generation The reaction of asthmatic medicament Vilantro three phenylacetate intermediate (II) formula structure, reaction equation are as follows:

Specifically, reaction step are as follows:

1) raw material of (I) formula structure is dissolved in based organic solvent, it is small that catalyst heteropoly acid crystal reaction 3-5 is added When;

2) starting material left 1% of high performance liquid chromatography detection (I) formula structure is hereinafter, stopping reaction, is cooled to room temperature;Then Heteropoly acid crystal is removed using filtering with microporous membrane, obtains (II) formula compound after filtrate concentration.

Preferably, the based organic solvent is ethyl acetate, isopropyl acetate or Ethyl formate;

Preferably, the reaction temperature of reaction 3-5 hours is 10-15 DEG C;

Preferably, the heteropoly acid crystal dosage is the 0.2-10%, more preferably 3-4% of the raw material weight of (I) formula structure.

The present invention provides a kind of catalyst of heteropoly acid crystal to prepare asthmatic medicament Vilantro triphen second for catalysis Hydrochlorate intermediate, i.e. (II) formula compound;Compared with prior art, the present invention has the advantage that

1) heteropoly acid crystal catalyst preparation of the present invention is simple, without harsh reaction condition;

2) heteropoly acid crystal catalyst of the present invention prepares three phenylacetate intermediate of asthmatic medicament Vilantro for catalysis, That is (II) formula compound ratio transformation and selectivity is high, provides product yield, yield is up to 85% or more;

3) heteropoly acid crystal catalyst of the present invention can be separated by simple filtration from reaction system, and can be returned Receipts are applied, and production cost is reduced;

4) heteropoly acid crystal catalyst of the present invention solves the disadvantage that alleviate environmental protection using highly basic in (II) formula compound Pressure, process route is environmentally protective, meets existing industrial requirement.

Detailed description of the invention

Fig. 1 is the TEM phenogram of heteropoly acid crystal prepared by embodiment 1;

Fig. 2 is the SEM phenogram of heteropoly acid crystal prepared by embodiment 1.

Specific embodiment

In order to make the objectives, technical solutions and advantages of the present invention clearer, With reference to embodiment, to this Invention is further described.It should be understood that these descriptions are merely illustrative, and it is not intended to limit the scope of the invention.

Embodiment

One, heteropoly acid crystal is prepared

By 10g Na2WO4.2H2O and NaVO3.2H2O(and Na2WO4.2H2O equimolar amounts) be dissolved in 100ml water stir it is molten Then disodium hydrogen phosphate (Na is added dropwise in solution into system2WO4.2H23.5 times of O mole) and manganese acetate (Na2WO4.2H2O moles 1.2 times of amount) aqueous solution stirring, with sulphur acid for adjusting pH to 2.2-3.0 after completion of dropwise addition;Reaction solution is warming up to 60-65 DEG C, so Three n-butylmagnesium chloride ammonium (Na of benzyl is added dropwise afterwards2WO4.2H24.2 times of O mole) aqueous solution be stirred to react 1-2h obtain it is muddy molten Liquid;Potassium acetate is added and adjusts pH to 4.1-5.2, a large amount of black solids are precipitated;Filtering, filter cake successively use purified water, ethyl alcohol to wash It washs, is dried at 40-45 DEG C;Obtained solid is recrystallized with isopropyl acetate after drying, obtains heteropoly acid crystal, and heteropoly acid crystal uses Transmission electron microscope (TEM) phenogram is as shown in Figure 1, heteropoly acid crystal uses scanning electron microscope (SEM) such as Fig. 2 institute Show.

Two, catalysis preparation three phenylacetate intermediate of Vilantro, i.e. (II) formula compound, reaction equation are as follows:

It takes (I) formula raw material 5g to be added in 40ml ethyl acetate to stir, 0.05 10-15 DEG C of heteropoly acid crystal is then added 3-5h is reacted, HPLC detects reaction solution, reacts when (I) formula raw material no longer declines stopping, being cooled to room temperature;Use aperture for 0.2 The miillpore filter of micron is filtered, and removes heteropoly acid crystal, and washing, liquid separation are concentrated to give product.

Embodiment 2

1 reaction process of reference implementation example, using heteropoly acid crystal obtained by above-mentioned preparation as catalyst, with 10g(I) formula is original Material, has investigated reaction dissolvent (being 7 times of weight of substrate), reaction temperature, heteropoly acid crystal dosage (with raw material i.e. (I) formula knot Calculated on the basis of structure) influence to the conversion ratio and product (II) formula yield and its purity of (I) formula compound, as a result such as 1 institute of table Show:

The catalytic effect of 1 differential responses condition of table

Note: yield refers to (separation weight X purity)/theoretical percentage that must be measured;Purity refers to the HPLC for isolating product Purity, area percentage.

The above result shows that the raw material high conversion rate in esters solvent;The raw material selectivity under 10-15 DEG C of reaction temperature Height, product purity are high;Heteropoly acid crystal dosage is not easy excessively, more than 15% or more, selectively to begin to decline.

Embodiment 3

Using ethyl acetate as solvent, reaction temperature is 10-15 DEG C, catalyst amount 2%wt, in reference implementation example 1 (II) The preparation section of formula compound investigates catalyst and applies the influence to reaction, as a result such as table 2:

2 heteropoly acid crystal of table applies influence of the number to reaction

Note: reaction solution purity refers to the purity of the reaction solution after reaction of detection, rather than post-processing obtains crude product Purity;The heteropoly acid crystal rate of recovery filtered after referring to reaction and dry gained heteropoly acid crystal with react before the weight percent that feeds intake Than.

The above result shows that catalyst of the present invention use three times rear raw material conversion ratio and product selectivity it is not bright Aobvious decline;But it is easy to be lost in heteropoly acid crystal reaction process of the present invention.The phenomenon that overcome heteropoly acid crystal to be lost, application People attempts to take molecular sieve carried heteropoly acid crystal.

The specific method is as follows for molecular sieve carried heteropoly acid crystal: the embodiment of the present invention 1 is prepared gained heteropoly acid crystal It is added in the water of 100 times of weight, the MCM-48 molecular sieve (on the basis of heteropoly acid crystal) of 10 times of weight is then added, then sulphur Acid for adjusting pH is to 3.5, and calcining 1h obtains molecular sieve carried heteropoly acid crystal under nitrogen atmosphere at 130 DEG C after dipping filters afterwards for 24 hours, Being used to be catalyzed reaction for the molecular sieve carried heteropoly acid crystal of gained, (heteropoly acid crystal load amount is calculated with 9.1%wt, i.e., theoretical Content;Heteropoly acid crystal dosage is the 3%wt of substrate dosage in reaction), the results are shown in Table 3:

The molecular sieve carried heteropoly acid crystal of table 3 applies influence of the number to reaction

The heteropoly acid crystal rate of recovery/100% Conversion ratio Reaction solution purity First use N/A 100 96.8 Secondary use 96% 99 96.2 It uses three times 95% 99 96.6

The above result shows that the conversion ratio of raw material and product selectivity do not change after load, and overcome heteropoly acid crystalline substance The problem of bulk diffusion.

Although embodiments of the present invention are described in detail, it should be understood that, without departing from of the invention In the case where spirit and scope, embodiments of the present invention can be made with various changes, replacement and change.

Claims (4)

1. a kind of preparation method of molecular sieve carried heteropoly acid crystal, it is characterised in that: the following steps are included: by heteropoly acid crystalline substance Body is added in the water of 100 times of weight, the MCM-48 molecular sieve of 10 times of weight is then added, then sulphur acid for adjusting pH to 3.5, dipping For 24 hours, it filters, calcining 1h obtains molecular sieve carried heteropoly acid crystal under nitrogen atmosphere at 130 DEG C;
The heteropoly acid crystal prepares gained by following preparation method:
By Na2WO4.2H2O、NaVO3.2H2O stirring and dissolving soluble in water obtains the first solution;
The aqueous solution stirring and dissolving of disodium hydrogen phosphate and manganese acetate is obtained into the second solution;
First solution is added drop-wise in the second solution and is stirred, then obtains third solution to strong acid is acid with sulphur acid for adjusting pH;
Third solution is warming up to 60-65 DEG C, then be added dropwise three n-butylmagnesium chloride ammonium of benzyl aqueous solution be stirred to react 1-2h obtain it is muddy The 4th turbid solution;
Potassium acetate is added into the 4th solution and adjusts pH to faintly acid, a large amount of black solids are precipitated;
Filtering, filter cake successively use purified water, ethanol washing, dry at 40-45 DEG C;
Obtained solid is recrystallized with isopropyl acetate after drying, obtains heteropoly acid crystal.
2. preparation method according to claim 1, it is characterised in that: the heteropoly acid crystal is specific the preparation method comprises the following steps: will 10g Na2WO4.2H2O and NaVO3.2H2O is dissolved in stirring and dissolving in 100ml water, and disodium hydrogen phosphate and vinegar are then added dropwise into system The aqueous solution of sour manganese stirs, with sulphur acid for adjusting pH to 2.2-3.0 after completion of dropwise addition;Reaction solution is warming up to 60-65 DEG C, is then added dropwise The aqueous solution of three n-butylmagnesium chloride ammonium of benzyl is stirred to react 1-2h and obtains turbid solution;Potassium acetate is added and adjusts pH to 4.1-5.2, analysis A large amount of black solids out;Filtering, filter cake successively use purified water, ethanol washing, dry at 40-45 DEG C;Obtained solid after drying It is recrystallized with isopropyl acetate, obtains heteropoly acid crystal;The NaVO3.2H2O dosage and Na2WO4.2H2O equimolar amounts, the phosphorus Sour disodium hydrogen mole dosage is Na2WO4.2H23.5 times of O mole, the manganese acetate mole dosage are Na2WO4.2H2O moles 1.2 times of amount, the three n-butylmagnesium chloride ammonium mole dosage of benzyl are Na2WO4.2H24.2 times of O mole.
3. a kind of purposes of molecular sieve carried heteropoly acid crystal, the molecular sieve carried heteropoly acid crystal is by claim 1 Or 2 preparation method preparation, it is characterised in that: the molecular sieve carried heteropoly acid crystal is for being catalyzed (I) formula structure system Standby asthmatic medicament Vilantro three phenylacetate intermediate (II) formula compound, reaction equation are as follows:
4. purposes according to claim 3, it is characterised in that: the molecular sieve carried heteropoly acid crystal is for being catalyzed (I) formula structure prepares asthmatic medicament Vilantro three phenylacetate intermediate (II) formula compound, specific steps are as follows:
The raw material of (I) formula structure is dissolved in based organic solvent, it is small that molecular sieve carried heteropoly acid crystal reaction 3-5 is added When;
The starting material left 1% of high performance liquid chromatography detection (I) formula structure is hereinafter, stopping reaction, is cooled to room temperature;Then using micro- Hole membrane filtration removes molecular sieve carried heteropoly acid crystal, obtains (II) formula compound after filtrate washing, liquid separation concentration.
CN201711250855.XA 2017-04-08 2017-04-08 A kind of method that carried heteropoly acid catalyst prepares chronic obstructive pulmonary disease pharmaceutical intermediate CN107824213B (en)

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