CN106928137A - A kind of method of Graphene palladium copper catalysis synthesis MK chirality alcohol intermediate - Google Patents

A kind of method of Graphene palladium copper catalysis synthesis MK chirality alcohol intermediate Download PDF

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CN106928137A
CN106928137A CN201710100475.1A CN201710100475A CN106928137A CN 106928137 A CN106928137 A CN 106928137A CN 201710100475 A CN201710100475 A CN 201710100475A CN 106928137 A CN106928137 A CN 106928137A
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palladium
phenyl
graphene
vinyl
alcohol intermediate
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郑庚修
高令峰
韩歆雨
付凯
王秋芬
冯雪
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University of Jinan
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/18—Halogen atoms or nitro radicals
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8926—Copper and noble metals
    • 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

The invention discloses a kind of novel graphite alkene palladium copper and the method for chiral diphosphine ligand composite catalyzing synthesis MK chirality alcohol intermediate [S (E)] 2 [3 [3 [2 (quinolyl of 7 chlorine 2) vinyl] phenyl] 3 hydroxypropyls] methyl benzoate, the method is using high activity Graphene palladium copper and chiral diphosphine ligand composite catalyst, catalysis borane reduction ketone carbonyl, the method chiral selectivity is good, it is simple to operate, catalyst is easily isolated recovery, yield is up to 82.1%, ee values preferably 99.5%, it is adaptable to industrialized production.

Description

A kind of method of Graphene palladium copper catalysis synthesis MK chirality alcohol intermediate
Technical field
The invention belongs to medical chemistry synthesis field, and in particular to a kind of synthetic method of MK intermediate.
Background technology
Menglusitena (Montrlukast Sodium) it is chemical entitled：2- (1- ((1 (R)-(3- (2- (the chloro- 2- quinolines of 7- Quinoline base)-(E)-vinyl) phenyl) -3- (2- (propyl group of 2- hydroxyls -2) phenyl)-rosickyite base) methyl) cyclopropyl) sodium acetate, use Make Zhichuan agent, anti-allergic agent etc..Exploitation is synthesized by Canadian Merk-Frosst companies first.
Investigation patent and periodicals and magazines find, in the route methods of synthesis MK, synthesize the chirality of S- configurations Propyl alcohol intermediate is all mostly important work, either by the control of chiral catalyst, or by other chiral reagents Fractionation obtain single chiral product, can all have very big limitation.In terms of chiral ligand and metallic catalyst, mainly pass through Ru, Rh, Ir, Pd are combined the chiral catalyst for obtaining with chiral nitrogen-containing ligands, greatest problem and limitation that such catalyst is present It is that metallic catalyst relative price is too high, and there is larger heavy metal toxicity, it is necessary to is separated by strict heavy metal. Secondly, reuse cannot be reclaimed after such homogeneous catalyst reaction, causes the relatively costly of whole method, made in amplification scale There is huge limitation with aspect.Separated using chiral selectors more than traditional synthetic process, but half product It is the propyl alcohol of R configurations, causes and greatly waste and work-loss costs.
As coupling reaction is furtherd investigate, the industrialization of coupling reaction is quoted to be become more and more extensively, Stoltz in 2004 Group reports using the chiral propyl alcohol raw material 7a of S configurations, by the bromine of 3 of raw material 7a on Adv. Synth. Catal. It is coupled with the double bond on 2- vinyl -7- chloroquinolines, so that quinoline ring and the chiral propyl alcohol efficient coupling of raw material.In this piece In article, author have also been developed a kind of method of new synthesis S configuration Montelukast propyl alcohol intermediates, mainly by such as figure three Thinking, the raw alcohol for being complexed chiral catalyst selective oxidation R configurations by palladium is converted into ketone carbonyl, so as to S configurations Alcohol retain separates, then by ketone carbonyl be reduced into alcohol after re-use, chiral alcohol can be obtained with efficient.So Chiral separation method go out value higher in terms of the chiral raw material recovery of high price.Reaction equation is shown below.
2001, Hashiguchi groups reported using the restoring method of Ru chiral catalysts on JOC magazines, can 8a ketone carbonyls are reduced into alcohol, yield is 68%, product propyl alcohol ee values can reach 92%.But this catalyst needs high rhodium And chiral ligand, the synthesis cost of catalyst and the synthesis difficulty of chiral ligand are all than larger, and product alcohol ee values also compare Low, it is impossible to reach the requirement that medicine is used, the presence of chiral impurity is influenceed also than larger on follow-up reaction.Reaction is such as following formula institute Show.
Either most traditional linear synthetic route method, chiral alcohol is obtained in the fractionation by chiral selectors, also It is that molecular framework is built by coupling reaction, and using the catalysis selection fractionation of chiral catalyst, can clearly sees, hand Property alcohol synthesis be committed step in MK synthesis, the fast synthesis of chiral raw polyol is most important.Find research The synthetically prepared MK intermediate chirality alcohol intermediate right and wrong of the method for synthesis of chiral alcohol intermediate, more quickness and high efficiency Often important basic research direction, is also beneficial to create bigger economic society value.
The content of the invention
Present invention mainly solves technical problem, be to provide a kind of chiral alcohol intermediate [S- (E)] -2- of MK The novel graphite alkene palladium copper of [3- [3- [2- (the chloro- 2- quinolyls of 7-) vinyl] phenyl] -3- hydroxypropyls] methyl benzoate is urged Agent and the synthetic method of biphosphine ligand catalysis reduction.Specifically related to：
1st, a kind of Graphene palladium copper and chiral diphosphine ligand composite catalyzing synthesis MK chirality alcohol intermediate（II）[S- (E)] the method for -2- [3- [3- [2- (the chloro- 2- quinolyls of 7-) vinyl] phenyl] -3- hydroxypropyls] methyl benzoate, uses Borine and BY3Reducing agent, using the graphene-supported palladium copper nanometer of high activity and chiral diphosphine ligand composite catalyst reduction synthesis MK chirality alcohol intermediate（II）, the reaction equation as shown in formula.
2nd, according to a kind of MK chirality alcohol intermediate [S- (E)] -2- [3- [3- [2- (chloro- 2- of 7- of claim 1 Quinolyl) vinyl] phenyl] -3- hydroxypropyls] methyl benzoate（II）Method and step, reacting liquid temperature is -5 ~ 0oUnder C BH is added dropwise3, 30 ~ 40oC reacts 3 ~ 5 hours, after reaction terminates, in 0-4oUnder C, reaction is quenched with saturated aqueous ammonium chloride.
3rd, a kind of MK chirality alcohol intermediate [S- (E)] -2- [3- [3- [2- (the chloro- 2- quinolyls of 7-) vinyl] Phenyl] -3- hydroxypropyls] methyl benzoate（II）Method, reaction dissolvent be anhydrous DMF, N, N- diformazans Yl acetamide, 1-METHYLPYRROLIDONE, dimethyl sulfoxide；Raw material（I）：Mol ratio=400 of palladium in Graphene palladium copper nano material ~ 500:1, preferably 400 ~ 450:1；Ligand L is 1 with the mol ratio of palladium in Graphene palladium-copper catalyst:0.9 ~ 1.1, preferably 1: 0.9~1.05；Stirring reaction 10 ~ 30 minutes after addition part；Raw ketone（I）：BH3Mol ratio=1:2.0 ~ 2.5, preferably 1: 2.0~2.2；Raw ketone：BY3Mol ratio=1:1.5 ~ 2.0, preferably 1:2.0~2.2.
A kind of MK chirality alcohol intermediate [S- (E)] -2- [3- [3- [2- (the chloro- 2- quinolyls of 7-) vinyl] benzene Base] -3- hydroxypropyls] methyl benzoate（II）Method, the Graphene palladium-copper catalyst being filtrated to get, through water, ethanol wash, 50 oReusable three times after C vacuum drying.
Beneficial effect of the present invention：The method uses heterogeneous Graphene palladium copper nano material combination axial chirality diphosphine ligand Catalysis reduction ketone carbonyl prepares MK propyl alcohol intermediate.The method chiral selectivity is good, simple to operate, and catalyst is easy to Separation and recovery is reused, and yield is up to 82.1%, ee values preferably 99.5%, it is adaptable to industrialized production.
Specific implementation case：
Specific embodiment is as follows：
Specific embodiment 1：[S- (E)] -2- [3- [3- [2- (the chloro- 2- quinolyls of 7-) vinyl] phenyl] -3- hydroxypropyls] benzene The synthesis of methyl formate：
Take addition 590.1mgmethyl (E) -2- (3- (3- (2- (7- in the three neck round bottom flask of 50 milliliters of a drying Chloroquinolin-2-yl) vinyl) phenyl) -3-oxopropyl) benzoate, 20mg is containing the mass fraction of palladium 10% Graphene-supported palladium copper Nano capsule, nitrogen protection is lower to add 10 milliliters of anhydrous DMFs, keeps reaction system N2Protection, under ice-water bath cooling, control reacting liquid temperature is -2 ~ 0oC, in reaction solution add ligand 1 1.4mg (1S, 2S)- N1,N2-bis(1-(2-(di-4-methoxyphenylphosphanyl) phenyl) ethyl) cyclohexane-1,2- Diamine, stirring reaction 20 minutes, then adds 268mg australenes（alpha-pinene）, syringe dropwise addition 0.18mL BBr3, 0.22mL borine tetrahydrofuran solutions are then added dropwise, it is warming up to 35oUnder C, react 3.5 hours to raw ketone（I）Completely also After original reaction disappears.Then it is 0 to be cooled to temperature in reaction solutionoC, is added dropwise saturated aqueous ammonium chloride and reaction is quenched, and is filtered to remove Palladium-copper catalyst, is then extracted at twice with 100mL ethyl acetate, merges organic phase, and organic phase uses saturated brine (3 × 50 again Milliliter) to wash, anhydrous sodium sulfate drying 1 hour, filtering is spin-dried for rear solid through column chromatography for separation, and column chromatography product uses 5mL again Ethyl alcohol recrystallization is to obtain Meng Lusi sodium intermediates（II）[S- (E)] -2- [3- [3- [2- (the chloro- 2- quinolyls of 7-) vinyl] benzene Base] -3- hydroxypropyls] methyl benzoate 474.5mg, yield 79.7%, 99.3%ee.
Specific embodiment 2：[S- (E)] -2- [3- [3- [2- (the chloro- 2- quinolyls of 7-) vinyl] phenyl] -3- hydroxyls third Base] methyl benzoate synthesis：
Take addition 590.1mg methyl (E) -2- (3- (3- (2- (7- in the three neck round bottom flask of 50 milliliters of a drying Chloroquinolin-2-yl) vinyl) phenyl) -3-oxopropyl) benzoate, 20mg is containing the mass fraction of palladium 10% Graphene-supported palladium copper Nano capsule, nitrogen protection is lower to add 10 milliliters of anhydrous DMFs, keeps reaction system N2Protection, under ice-water bath cooling, control reacting liquid temperature is -2 ~ 0oC, in reaction solution add ligand 1 2.4mg (1S, 2S)- N1,N2-bis(1-(2-(di-4-methoxyphenylphosphanyl) phenyl) ethyl) cyclohexane-1,2- Diamine, stirring reaction 20 minutes, then adds 278.2mg australenes（alpha-pinene）, syringe dropwise addition 0.26mL BBr3, 0.32mL borine tetrahydrofuran solutions are then added dropwise, it is warming up to 35oUnder C, react 3.5 hours to raw ketone（I） After complete reduction reaction disappears.Then it is 0 to be cooled to temperature in reaction solutionoC, is added dropwise saturated aqueous ammonium chloride and reaction, mistake is quenched Palladium-copper catalyst is filtered, is then extracted at twice with 100mL ethyl acetate, merge organic phase, organic phase uses saturated brine again (3 × 50 milliliters) washings, anhydrous sodium sulfate drying 1 hour, filtering is spin-dried for rear solid through column chromatography for separation, column chromatography product It is again to obtain Meng Lusi sodium intermediates with 5mL ethyl alcohol recrystallizations（II）[S- (E)] -2- [3- [3- [2- (the chloro- 2- quinolyls of 7-) second Alkenyl] phenyl] -3- hydroxypropyls] methyl benzoate 364.5mg, yield 82.1%, 99.5%ee.
Specific embodiment 3, [S- (E)] -2- [3- [3- [2- (the chloro- 2- quinolyls of 7-) vinyl] phenyl] -3- hydroxyls third Base] methyl benzoate synthesis：
Take addition 974.2mg methyl (E) -2- (3- (3- (2- (7- in the three neck round bottom flask of 100 milliliters of a drying Chloroquinolin-2-yl) vinyl) phenyl) -3-oxopropyl) benzoate, 30mg is containing the mass fraction of palladium 10% Graphene-supported palladium copper Nano capsule, nitrogen protection is lower to add 30 milliliters of anhydrous DMFs, keeps reaction system N2Protection, under ice-water bath cooling, control reacting liquid temperature is -2 ~ 0oC, in reaction solution add ligand 1 9.2mg (1S, 2S)- N1,N2-bis(1-(2-(di-4-methoxyphenylphosphanyl) phenyl) ethyl) cyclohexane-1,2- Diamine, stirring reaction 20 minutes, then adds 428.5mg australenes（alpha-pinene）, syringe dropwise addition 0.31mL BBr3, 0.35mL borine tetrahydrofuran solutions are then added dropwise, it is warming up to 35oUnder C, react 3.8 hours to raw ketone（I） After complete reduction reaction disappears.Then it is 0 to be cooled to temperature in reaction solutionoC, is added dropwise saturated aqueous ammonium chloride and reaction, mistake is quenched Palladium-copper catalyst is filtered, is then extracted at twice with 100mL ethyl acetate, merge organic phase, organic phase uses saturated brine again (3 × 80 milliliters) washings, anhydrous sodium sulfate drying 1 hour, filtering is spin-dried for rear solid through column chromatography for separation, column chromatography product It is again to obtain Meng Lusi sodium intermediates with 5mL ethyl alcohol recrystallizations（II）[S- (E)] -2- [3- [3- [2- (the chloro- 2- quinolyls of 7-) second Alkenyl] phenyl] -3- hydroxypropyls] methyl benzoate 364.5mg, yield 79.7%, 99.4%ee.
Embodiment 4：Reuse Graphene palladium-copper catalyst and prepare [S- (E)] -2- [3- [3- [2- (chloro- 2- quinoline of 7- Base) vinyl] phenyl] -3- hydroxypropyls] methyl benzoate synthesis：
Take addition 595.1mg methyl (E) -2- (3- (3- (2- (7- in the three neck round bottom flask of 50 milliliters of a drying Chloroquinolin-2-yl) vinyl) phenyl) -3-oxopropyl) benzoate, 20mg suction filtrations reclaim Graphene bear Palladium copper Nano capsule is carried, nitrogen protection is lower to add 10 milliliters of anhydrous DMFs, keeps the N of reaction system2Protection, Under ice-water bath cooling, control reacting liquid temperature is -2 ~ 0oC, to addition ligand 1 1.4mg (1S, 2S)-N in reaction solution1,N2-bis (1- (2- (di-4-methoxyphenylphosphanyl) phenyl) ethyl) cyclohexane-1,2-diamine, Stirring reaction 20 minutes, then adds 268mg australenes（alpha-pinene）, syringe dropwise addition 0.18mL BBr3, so 0.22mL borine tetrahydrofuran solutions are added dropwise afterwards, 35 are warming up tooUnder C, react 3.5 hours to raw ketone（I）Complete reduction reaction After disappearance.Then it is 0 to be cooled to temperature in reaction solutionoC, is added dropwise saturated aqueous ammonium chloride and reaction is quenched, and is filtered to remove Graphene Palladium-copper catalyst, the Graphene palladium-copper catalyst of recovery is reusable after ethanol, washing.Filtrate uses 100mL ethyl acetate Extract at twice, merge organic phase, organic phase is washed with saturated brine (3 × 50 milliliters) again, and anhydrous sodium sulfate drying 1 is small When, filtering is spin-dried for rear solid through column chromatography for separation, and column chromatography product is again to obtain in the middle of Meng Lusi sodium with 5mL ethyl alcohol recrystallizations Body（II）[S- (E)] -2- [3- [3- [2- (the chloro- 2- quinolyls of 7-) vinyl] phenyl] -3- hydroxypropyls] methyl benzoate 474.5mg, yield 79.7%, 99.3%ee.
Although above-mentioned be described to specific embodiment of the invention in conjunction with the embodiments, not the present invention is implemented The restriction of mode.For one of ordinary skill in the art, on the basis of technical scheme, those skilled in the art are not Need the various modifications made by paying creative work or deformation still within protection scope of the present invention.

Claims (4)

1. a kind of Graphene palladium copper synthesizes MK chirality alcohol intermediate with chiral diphosphine ligand composite catalyzing（II）[S- (E)] the method for -2- [3- [3- [2- (the chloro- 2- quinolyls of 7-) vinyl] phenyl] -3- hydroxypropyls] methyl benzoate, it is special Levy and be, using borine and BY3Make reducing agent, answered using the graphene-supported palladium copper nano-particle of high activity and chiral diphosphine ligand Close catalyst reduction raw material（I）Synthesis MK chirality alcohol intermediate（II）, reaction equation is as follows：
。
2. according to a kind of MK chirality alcohol intermediate [S- (E)] -2- [3- [3- [2- (chloro- 2- quinoline of 7- of claim 1 Base) vinyl] phenyl] -3- hydroxypropyls] methyl benzoate（II）Method and step, it is characterised in that BH3Dropping liquid temperature It is -5 ~ 0oC, 30 ~ 40 after completion of droppingoC reacts 3 ~ 5 hours, after reaction terminates, in 0-4oIt is water-soluble with saturated ammonium chloride under C Liquid is quenched reaction.
3. according to a kind of MK chirality alcohol intermediate [S- (E)] -2- [3- [3- [2- (chloro- 2- quinoline of 7- of claim 1 Base) vinyl] phenyl] -3- hydroxypropyls] methyl benzoate（II）Method, reaction dissolvent be anhydrous N, N- dimethyl formyls Amine, anhydrous DMA, dry N-methylpyrrolidone, anhydrous dimethyl sulfoxide；Raw material（I）：Graphene palladium copper is received Mol ratio=400 ~ 500 of palladium in rice material:1, ligand L is 1 with the mol ratio of palladium in Graphene palladium-copper catalyst:0.9 ~ 1.1, Stirring reaction 10 ~ 30 minutes after addition part；Raw material（I）：BH3：BY3Mol ratio=1:2.0~2.5:1.5~2.0.
4. a kind of MK chirality alcohol intermediate [S- (E)] -2- [3- [3- [2- (chloro- 2- of 7- according to claim 1 Quinolyl) vinyl] phenyl] -3- hydroxypropyls] methyl benzoate（II）Method, the Graphene palladium copper catalysis being filtrated to get Agent, washs, 50 through water, ethanoloReusable three times after C vacuum drying.
CN201710100475.1A 2017-02-23 2017-02-23 A kind of method of Graphene palladium copper catalysis synthesis MK chirality alcohol intermediate Pending CN106928137A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101028604A (en) * 2006-03-01 2007-09-05 中国科学院大连化学物理研究所 Multi-phase chiral metal catalyst and its production
WO2008157658A1 (en) * 2007-06-21 2008-12-24 Protia Llc Deuterium-enriched montelukast
CN103554016B (en) * 2013-08-23 2015-09-23 南通正达农化有限公司 A kind of complete processing of non-hormone antiphlogiston intermediate
CN105294545A (en) * 2015-11-23 2016-02-03 中山奕安泰医药科技有限公司 Method for preparing montelukast nano chiral alcohol intermediate

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101028604A (en) * 2006-03-01 2007-09-05 中国科学院大连化学物理研究所 Multi-phase chiral metal catalyst and its production
WO2008157658A1 (en) * 2007-06-21 2008-12-24 Protia Llc Deuterium-enriched montelukast
CN103554016B (en) * 2013-08-23 2015-09-23 南通正达农化有限公司 A kind of complete processing of non-hormone antiphlogiston intermediate
CN105294545A (en) * 2015-11-23 2016-02-03 中山奕安泰医药科技有限公司 Method for preparing montelukast nano chiral alcohol intermediate

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
董建霞 等: "手性双膦配体在不对称催化氢化反应中的最新进展", 《化工时代》 *
马静静: "石墨烯负载钯铜纳米催化剂的制备及其催化性能的研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 *

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Application publication date: 20170707