CN113244951B - 介孔分子筛负载的催化剂及其应用 - Google Patents

介孔分子筛负载的催化剂及其应用 Download PDF

Info

Publication number
CN113244951B
CN113244951B CN202110206143.8A CN202110206143A CN113244951B CN 113244951 B CN113244951 B CN 113244951B CN 202110206143 A CN202110206143 A CN 202110206143A CN 113244951 B CN113244951 B CN 113244951B
Authority
CN
China
Prior art keywords
catalyst
formula
molecular sieve
mcm
mesoporous molecular
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202110206143.8A
Other languages
English (en)
Other versions
CN113244951A (zh
Inventor
赵丹丹
张羽杰
付译瑶
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tianjin University of Commerce
Original Assignee
Tianjin University of Commerce
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tianjin University of Commerce filed Critical Tianjin University of Commerce
Priority to CN202110206143.8A priority Critical patent/CN113244951B/zh
Publication of CN113244951A publication Critical patent/CN113244951A/zh
Application granted granted Critical
Publication of CN113244951B publication Critical patent/CN113244951B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0237—Amines
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0254—Nitrogen containing compounds on mineral substrates
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0271—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0231
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B53/00—Asymmetric syntheses
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C227/02—Formation of carboxyl groups in compounds containing amino groups, e.g. by oxidation of amino alcohols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/07—Optical isomers
    • 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

Landscapes

  • 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)

Abstract

本发明公开了一种介孔分子筛MCM‑41负载的手性冠醚催化剂及其应用。本发明的催化剂，其结构如式(I)所示。所述催化剂式(I)可高对映选择性制备非天然氨基酸，催化剂催化对映选择性高，分离纯化简单，可反复循环利用。

Description

介孔分子筛负载的催化剂及其应用
技术领域
本发明涉及催化材料领域，具体地说，涉及一种介孔分子筛负载的催化剂及其应用。
背景技术
手性冠醚催化剂是一种均相催化剂，存在不易从反应体系分离，难以回收利用的缺点，手性冠醚催化剂价格昂贵，应用成本高。
MCM-41分子筛是介孔分子筛中最典型的一种。作为一种介孔分子筛，MCM-41的孔道为有序六边形结构，其孔径可以在2-10nm之间调控，并且具有极高的比表面积(高达1500m2/g)、孔体积(1.3ml/g)以及优良的热稳定性。
发明内容
本发明提供的MCM-41负载的手性冠醚催化剂，结构如式(I)所示：
Figure BDA0002950740220000011
R2与R3连接形成的a环为苯环或环己烷。
本发明还提供了所述式(I)催化剂在催化合成非天然氨基酸中的应用，如为式VII的(R)-氨基酸
Figure BDA0002950740220000012
中，R1为基叔丁基、环己基；式VII可由α-氨基砜与KCN合成制得，如反应式为：
Figure BDA0002950740220000021
本发明所述MCM-41负载的手性冠醚催化剂的制备方法可包括以下步骤：
a.N2保护下，(R)-BINOL衍生物(II)与三乙二醇醚对甲苯磺酸酯(III)在碱存在下缩合制得中间体(IV)；
b.N2保护下，在碱作用下，中间体(IV)与N-Boc-二胺缩合，制得中间体(V)；
c.N2保护下，中间体(V)在HCl作用下脱保护，制得中间体(VI)；
d.N2保护下，中间体(VI)与氯丙基化的介孔分子筛MCM-41-Cl在KI与碱存在下缩合制得MCM-41负载的手性冠醚催化剂式(I)；
其具体合成路线可如下所示：
Figure BDA0002950740220000022
其中R为苯基或环己基，即，步骤b中的N-Boc-二胺化合物分别用N-Boc-邻苯二胺、N-Boc-1，2-环己二胺时，对应的催化剂产物依次为式Ia、Ib,Ia、Ib的所述a环依次为苯环或环己烷。
在上述MCM-41负载的手性冠醚催化剂的制备方法中，所述的步骤a，b和d中的碱可独立选自：Cs2CO3,K2CO3,Na2CO3。
本发明的有益效果主要体现在：MCM-41负载的手性冠醚催化剂为全新的催化剂，所述的催化剂式(I)简单过滤即可以与反应液分离，式(I)回收率≥98％。回收的催化剂式(I)能循环利用，循环使用10次，催化活性不变。催化剂的合成路线简单，收率高，可以催化多种底物的α-氨基砜与KCN不对称反应，制备的非天然氨基酸光学纯度高。
具体实施方式
实施例1
氮气氛围下，将1g介孔分子筛MCM-41于50℃真空干燥过夜。加入30mL二甲苯与4mL3-氯丙基三甲氧基硅烷，室温下超声处理10min，加热回流24h,冷至rt,离心，异丙醇洗涤，50℃真空干燥12h，制得氯丙基化MCM-41(MCM-41-Cl)。
实施例2
取(R)-BINOL衍生物(II)(582mg,1.0mmol)于反应瓶中，置换氮气后加入50mL乙腈，加入研磨过的碳酸钾粉末(166mg,1.2mmol)，加热回流，将三乙二醇醚对甲苯磺酸酯(III)(503mg,1.1mmol)溶于10mL乙腈中，注射加入反应体系。TLC监测，保温反应8小时，减压蒸出乙腈，加水，二氯甲烷萃取，干燥后，硅胶柱层析分离纯化(PE/EA＝4:1)，制得中间体(IV)，收率90％。ESI-MS(m/z):868[M]+；1H NMR(300MHz，CDCl3)δ8.49(s,1H),7.82(d,J＝7.2Hz,2H),7.78(d,J＝8.2Hz,1H),7.73(d,J＝6.9Hz,2H),7.40(m,3H),7.33-7.23(m,3H),7.06(d,J＝8.8Hz,2H),3.97-3.71(m,4H),3.29-3.24(m,8H),3.21(t,J＝4.5Hz,2H),2.57(s,3H),2.43(s,3H)。
实施例3
中间体(V)的制备：
氮气氛围下，将中间体(IV)(1.0mmol)加入50mL乙腈，加入碳酸铯(1.2mmol)，加热回流，再并列加入不同的N-Boc-二胺各1.1mmol(a、N-Boc-邻苯二胺；b、N-Boc-1，2-环己二胺)，反应36h，减压蒸出乙腈，加水，二氯甲烷萃取，干燥后，硅胶柱层析分离纯化(PE/EA＝4:1)，制得各自的中间体(V)。
使用N-Boc-邻苯二胺制得的中间体(Va)为
Figure BDA0002950740220000041
其收率86％。ESI-MS(m/z):905[M+H]+；1H NMR(300MHz，CDCl3)δ8.54(s,1H),8.01(s,1H),7.79(t,J＝8.9Hz,2H),7.77(d,J＝8.2Hz,1H),7.43(t,J＝7.4Hz,2H),7.33-7.27(m,2H),7.18-7.08(m,2H),6.58-6.42(m,4H),4.95(s,1H),4.21(m,2H),3.97-3.71(m,8H),3.30-3.24(m,2H),3.21(t,J＝4.5Hz,2H),2.57(s,3H),1.43(s,9H)。
中间体(Vb)
Figure BDA0002950740220000051
收率91％。ESI-MS(m/z):911[M+H]+；1H NMR(300MHz，CDCl3)δ8.52(s,1H),8.00(s,1H),7.78(t,J＝8.9Hz,2H),7.76(d,J＝8.2Hz,1H),7.42(t,J＝7.4Hz,2H),7.33-7.27(m,2H),7.18-7.07(m,2H),4.22(m,2H),3.97-3.71(m,9H),3.22(t,J＝4.5Hz,2H),3.19(m,1H),2.83-2.72(m,2H),2.57(s,3H),2.01(s,1H),1.78-1.49(m,5H),1.40(s,9H),1.39(m,3H)。
实施例4
中间体(VI)的制备：
氮气氛围下，并列将不同的中间体V(上一实施例制得的Va、Vb)1.0mmol加入到4mL甲醇与12mL二氯甲烷中，加入50mL浓盐酸，室温搅拌24h，加入碳酸氢钠饱和溶液，搅拌，用二氯甲烷萃取，水洗，无水硫酸钠干燥，过滤，减压蒸干，制得各自的中间体(VI)。用Va制得的中间体VIa
Figure BDA0002950740220000052
其收率为90％，1H NMRδ：8.53(s,1H),8.00(s,1H),7.78(t,J＝8.9Hz,2H),7.76(d,J＝8.1Hz,1H),7.43(t,J＝7.3Hz,2H),7.33-7.27(m,2H),7.18-7.08(m,2H),6.57-6.41(m,4H),5.01(s,1H),4.21-4.15(m,2H),3.95-3.70(m,8H),3.57(s,2H),3.22(t,J＝4.8Hz,2H)。
中间体VIb
Figure BDA0002950740220000061
收率为95％，1HNMRδ：8.52(s,1H),8.00(s,1H),7.78(t,J＝8.9Hz,2H),7.76(d,J＝8.2Hz,1H),7.42(t,J＝7.4Hz,2H),7.33-7.27(m,2H),7.17-7.07(m,2H),4.95(s,1H),4.19-4.15(m,2H),3.96-3.70(m,9H),3.21(t,J＝4.5Hz,2H),3.19-3.10(m,1H),2.04(s,2H),1.78-1.49(m,5H),1.39-1.21(m,3H)。
实施例5
催化剂式(I)的制备：
氮气氛围下，将1g MCM-41-Cl加入到50mL乙腈中，加入碳酸钠(1.2mmol)和KI(1.2mmol)，剧烈搅拌，再并列加入中间体(VI)(2.0mmol)的20mL乙腈溶液，加热回流48h，冷却，过滤，水洗，制得MCM-41负载的手性冠醚催化剂式(I)：催化剂式(Ia)负载量为0.95mmol/g,催化剂式(Ib)负载量为0.93mmol/g。
实施例6
N2保护下，将N-Boc-1-苯磺酰基-2，2-二甲基丙胺(1.0mmol)与KCN(1.1mmol)加入到干燥的15mL甲苯中，冷却至0℃，加入107mg式(Ia)，反应60h，过滤，滤饼用水打浆，过滤，重复3次，最后用甲醇洗涤2次，真空干燥，回收式(I)，循环利用。滤液中加入6NHCl，回流反应3h，冷至室温，分层，有机相回收甲苯，水相加热回流3h，冷至室温，乙酸乙酯洗涤，减压浓缩至干，异丙醇重结晶，制得(R)-叔丁基甘氨酸盐酸盐，收率87％，97％ee。1H NMR(300MHz,D2O):δ3.83(s,1H),1.10(s,9H)；ee用HPLC[手性OA-5000柱,250x4.6mm；流动相：2mmol/LCuSO4溶液/乙腈＝90:10；流速:1.0mL/min；254nm]测定，tR＝17.3min(major),tS＝14.5min。
实施例7
N2保护下，将N-Boc-1-苯磺酰基-1-环己基甲胺(1.0mmol)与KCN(1.1mmol)加入到干燥的15mL甲苯中，冷却至0℃，加入113mg式(Ib)，反应60h，过滤，滤饼用水打浆，过滤，重复3次，最后用甲醇洗涤2次，真空干燥，回收式(I)，循环利用。滤液中加入6NHCl，回流反应3h，冷至室温，分层，有机相回收甲苯，水相加热回流3h，冷至室温，乙酸乙酯洗涤，减压浓缩至干，异丙醇重结晶，制得(R)-环己基甘氨酸盐酸盐，收率76％，96％ee。1H NMR(300MHz,D2O):δ3.91(d,J＝4.5Hz,1H),2.00(m.1H),1.77(s,3H),1.66-1.64(m,2H),1.35-1.26(m,5H)；ee用HPLC[手性OA-5000柱,250x4.6mm；流动相：2mmol/L CuSO4溶液/乙腈＝90:10；流速:1.0mL/min；254nm]测定，tR＝53.3min(major),tS＝47.2min。
实施例8
以N-Boc-1-苯磺酰基-2，2-二甲基丙胺与KCN反应为模板，按实施例6操作，考察催化剂式(I)的循环利用次数。结果显示，催化剂循环使用10次，催化活性不变。
表1催化剂式(Ia)的循环利用次数
Figure BDA0002950740220000081

Claims (2)

1.介孔材料MCM-41负载的手性冠醚催化剂，其结构如式(I)所示：
Figure FDA0002950740210000011
R2与R3连接形成的a环为苯环或环己烷。
2.根据权利要求1所述的介孔材料MCM-41负载的手性冠醚催化剂在催化合成非天然氨基酸中的应用。
CN202110206143.8A 2021-02-24 2021-02-24 介孔分子筛负载的催化剂及其应用 Active CN113244951B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110206143.8A CN113244951B (zh) 2021-02-24 2021-02-24 介孔分子筛负载的催化剂及其应用

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110206143.8A CN113244951B (zh) 2021-02-24 2021-02-24 介孔分子筛负载的催化剂及其应用

Publications (2)

Publication Number Publication Date
CN113244951A CN113244951A (zh) 2021-08-13
CN113244951B true CN113244951B (zh) 2022-04-12

Family

ID=77180993

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110206143.8A Active CN113244951B (zh) 2021-02-24 2021-02-24 介孔分子筛负载的催化剂及其应用

Country Status (1)

Country Link
CN (1) CN113244951B (zh)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022179557A1 (zh) * 2021-02-24 2022-09-01 周学明 催化剂及其应用
CN117358291B (zh) * 2023-12-08 2024-02-27 山东新和成药业有限公司 一种用于制备氧杂双环十六烯的催化剂及其制备方法和应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6579997B1 (en) * 1999-07-21 2003-06-17 Uab Research Foundation Metallacrown ether catalysts for hydroformylation
CN102153589A (zh) * 2011-02-28 2011-08-17 大连多相触媒有限公司 一种亚胺的不对称加氢催化剂及其合成方法和应用
CN102858757A (zh) * 2010-03-18 2013-01-02 陶氏环球技术有限责任公司 制备二乙烯基芳烃二氧化物的方法
CN104475066A (zh) * 2014-12-08 2015-04-01 云南师范大学 一种适用于氨基酸手性拆分的高效液相色谱分离柱
CN111269132A (zh) * 2020-01-21 2020-06-12 上海师范大学 一种制备手性β-三氟甲基-β-羟基-α-氨基酸及其衍生物的方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100870227B1 (ko) * 2007-07-20 2008-11-24 (주)그린포뮬라 강력한 수소결합 제공기를 갖는 알라닌 라스메이즈 모방키랄 바이나프톨 유도체 및 이 유도체를 이용한 광학 분할및 변환 방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6579997B1 (en) * 1999-07-21 2003-06-17 Uab Research Foundation Metallacrown ether catalysts for hydroformylation
CN102858757A (zh) * 2010-03-18 2013-01-02 陶氏环球技术有限责任公司 制备二乙烯基芳烃二氧化物的方法
CN102153589A (zh) * 2011-02-28 2011-08-17 大连多相触媒有限公司 一种亚胺的不对称加氢催化剂及其合成方法和应用
CN104475066A (zh) * 2014-12-08 2015-04-01 云南师范大学 一种适用于氨基酸手性拆分的高效液相色谱分离柱
CN111269132A (zh) * 2020-01-21 2020-06-12 上海师范大学 一种制备手性β-三氟甲基-β-羟基-α-氨基酸及其衍生物的方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
A study of tetrapeptide enantiomeric separation on crown ether based chiral stationary phases;T. Upmanis等;《Journal of Chromatography A》;20200428;第1622卷;1-9 *
Asymmetric epoxidation catalyzed by novel azacrown ether-type chiral quaternary ammonium salts under phase-transfer catalytic conditions;Kazushige Hori等;《Tetrahedron Letters》;20060313;第47卷;3115-3118 *
手性冠醚的研究进展及一类新型手性冠醚的合成展望;赵龙;《浙江化工》;20151231;第46卷(第9期);27-35 *

Also Published As

Publication number Publication date
CN113244951A (zh) 2021-08-13

Similar Documents

Publication Publication Date Title
CN113244951B (zh) 介孔分子筛负载的催化剂及其应用
CN108947894B (zh) 联芳结构手性n-甲基吡哆醛催化剂及其合成和应用
CN113999142B (zh) 一种手性N-Boc-反式-1,2-环己二胺的制备方法
CN114315917A (zh) 手性二茂铁pnno四齿配体及其在不对称氢化反应中的应用
CN112973789B (zh) 新介孔材料负载的催化剂及其应用
CN107032972B (zh) 具有2’-羟基查尔酮结构Diels-Alder产物的制备方法
CN111468183A (zh) 多氟代三芳基手性螺环磷酸催化剂及其制备方法、用途
CN107715909B (zh) 一种季戊四醇支载的脯氨酸催化剂及其制备方法及应用
EP2330107A2 (en) Improved production method for adefovir dipivoxil
CN112010910B (zh) 手性二茂铁高烯丙基胺类衍生物及其合成方法与应用
CN112675920B (zh) 一类单手性中心催化剂及其制备和催化合成手性醇类化合物和手性α-烯丙醇的方法
CN110437277B (zh) 一种磷酸烯基酯类化合物的合成方法
CN116063355A (zh) 一种手性多齿配体及其在不对称氢化的应用
CN109251227B (zh) 一类包含二茂铁骨架和刚性螺环结构的手性化合物及合成与应用
US6288280B1 (en) Racemization of atropisomeric bis(phosphine oxide) compounds
CN110540516B (zh) 一种1-磺酰甲基-3,4-二氢萘的制备方法
CN108017580B (zh) 一种可见光催化氨基酸脱羧合成1,2,3,4-四氢喹啉类化合物的方法
CN107474017B (zh) 一种不对称烯丙基化反应合成手性n1-烯丙基嘧啶的方法
WO2022179557A1 (zh) 催化剂及其应用
CN114682298B (zh) 一种手性膦酰胺催化剂及其制备方法和应用
CN111662318B (zh) 一种伊洛前列素关键中间体及其制备方法
EP2876108B1 (en) Compounds of chiral aromatic spiroketal diphosphine ligands, preparation methods and uses thereof
CN110586195B (zh) 一种手性催化剂及其制备方法和应用
CN115197161B (zh) Z-构型的烯丙基氨基酸类衍生物、其制备方法及应用
CN114573473B (zh) 一种(R)-α-芳基丙氨酸酯衍生物的制备方法

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
OL01 Intention to license declared