CN105237413B - 一种手性含结晶水苯甘氨醇钴配合物 - Google Patents
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 10
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- GNEPOXWQWFSSOU-UHFFFAOYSA-N dichloro-methyl-phenylsilane Chemical compound C[Si](Cl)(Cl)C1=CC=CC=C1 GNEPOXWQWFSSOU-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000010992 reflux Methods 0.000 claims abstract description 4
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- 238000006243 chemical reaction Methods 0.000 abstract description 20
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- 238000005712 Baylis-Hillman reaction Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract description 2
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- 238000001308 synthesis method Methods 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 7
- QMXOFBXZEKTJIK-UHFFFAOYSA-N Glycinol Natural products C1=C(O)C=C2OCC3(O)C4=CC=C(O)C=C4OC3C2=C1 QMXOFBXZEKTJIK-UHFFFAOYSA-N 0.000 description 6
- 150000001414 amino alcohols Chemical class 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
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- 238000002360 preparation method Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- GSOLWAFGMNOBSY-UHFFFAOYSA-N cobalt Chemical compound [Co][Co][Co][Co][Co][Co][Co][Co] GSOLWAFGMNOBSY-UHFFFAOYSA-N 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- -1 glycinol cobalt complex Chemical class 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
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- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- JAWGVVJVYSANRY-UHFFFAOYSA-N cobalt(3+) Chemical class [Co+3] JAWGVVJVYSANRY-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- CWKVFRNCODQPDB-UHFFFAOYSA-N 1-(2-aminoethylamino)propan-2-ol Chemical compound CC(O)CNCCN CWKVFRNCODQPDB-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- XUEWIQNQPBSCOR-UHFFFAOYSA-N 2-nitro-1-phenylethanol Chemical class [O-][N+](=O)CC(O)C1=CC=CC=C1 XUEWIQNQPBSCOR-UHFFFAOYSA-N 0.000 description 1
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- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 1
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Abstract
一种手性苯甘氨醇钴配合物（I），其化学式如下：（I）该手性苯甘氨醇钴配合物（I）的合成方法，是称取8.9005gL‑苯甘氨醇放入100ml圆底烧瓶中，加入50ml氯苯，搅拌使其溶解，将2.3794gCoCl2·6H2O及5.0Ml 的甲基苯基二氯硅烷加入上述溶液，加热回流48h，旋转出去溶剂，加入石油醚、二氯甲烷配制饱和溶液溶液，静置自然挥发，析出红棕色晶体；该配合物在苯甲醛的亨利反应，腈硅化反应，烯丙基烷基化反应及baylis‑Hillman反应中显示了一定的催化性能，其转化率分别达48%，34%，53%及58%。
Description
一、技术领域
本发明涉及一种新化合物及其制备方法，特别涉及一种钴化合物及其制备方法，确切地说是一种手性含结晶水L-苯甘氨醇钴配合物的制备及合成方法。
二、背景技术
手性氨基醇钴配合物是重要的催化剂和医药化工产品，其作为催化剂在二乙基锌与苯甲醛对映选择性加成反应等反应中有较好的催化效果。【1-6】
参考文献：
1.Asymmetric hydrogenation catalyzed by bis(dimethylglyoximato)cobalt(II)-achiral base complex and chiral amino alcohol conjugatedsystems.Oxidoreductase model with enantioselectivity，Ohgo,Yoshiaki；Natori,Yukikazu；Takeuchi,Seiji；Yoshimura,Juji,Chemistry Letters(1974),(11),1327-30.
2.Synthesis,structure and acid-base properties of cobalt(III)complexes with aminoalcohols tepanenko,O.N.；Reiter,L.G.UkrainskiiKhimicheskii Zhurnal(Russian Edition),(1992),58(12),1047-54.
3.Cobalt(III)mono-and trinuclear complexes with O,N-chelatingaminoalcohols apanadze,T.Sh.；Gulya,A.P.；Novotortsev,V.M.；Ellert,O.G.；Shcherbakov,V.M.；Kokunov,Yu.V.；Bushaev,Yu.A.Koordinatsionnaya Khimiya(1991),17(7),934-40.
4.Magnetic properties of cobalt complexes with amino alcohols,Evreev,V.N.；Bogdanov,A.P.13 Vses.Chugaev.Soveshch.po Khimii Kompleks.Soedin.,1978(1978),137.
5.Synthesis,stereochemistry,and reactions of cobalt(III)complexeswith amino alcohol ligands Okamoto,Martha S.No Corporate Source dataavailable|(1974),146pp.
6.Synthesis and properties of isomeric tris(N-[2-hydroxyethyl]ethylenediamine)cobalt(III)and tris(N-[2-hydroxypropyl]ethylenediamine)cobalt(III)chlorides,arpeiskaya,E.I.；Kukushkin,Yu.N.；Trofimov,V.A.；Yakovlev,I.P.,Zhurnal Neorganicheskoi Khimii(1971),16(7),1960-4。
三、发明内容
本发明旨在提供手性五水合六[(S)-苯甘氨醇]氯化钴配合物。所要解决的技术问题是一步合成得到目标产物。
本发明所称的手性钴配合物是由六水合氯化钴与甲基苯基二氯硅烷及L-苯甘氨醇制备的由以下化学式所示的化合物：
化学名称：五水合六[(S)-苯甘氨醇]氯化钴配合物,简称配合物(I)。
该配合物在苯甲醛的亨利反应，腈硅化反应，烯丙基烷基化反应及baylis-Hillman反应中显示了一定的催化性能，其转化率分别达48.3％，34％，53％及58％。
本合成方法包括合成和分离，称取8.9005g(64.9mmol)L-苯甘氨醇放入100ml圆底烧瓶中，加入50ml氯苯，搅拌使其溶解，将2.3794g(31.2mmol)CoCl2·6H2O及5.0Ml的甲基苯基二氯硅烷加入上述溶液，加热回流48h，旋转出去溶剂，加入石油醚、二氯甲烷配制饱和溶液溶液，静置自然挥发，析出红棕色晶体。
合成反应如下：
本合成方法一步得到目标产物，工艺简单，操作方便。
四、附图说明
图1是手性五水合六[(S)-苯甘氨醇]氯化钴配合物的单晶X-衍射图。
五、具体实施方式
手性五水合六[(S)-苯甘氨醇]氯化钴配合物的制备：
称取8.9005g(64.9mmol)L-苯甘氨醇放入100ml圆底烧瓶中，加入50ml氯苯，搅拌使其溶解，将2.3794g(31.2mmol)CoCl2·6H2O及5.0Ml的甲基苯基二氯硅烷加入上述溶液，加热回流48h，旋转出去溶剂，加入石油醚、二氯甲烷配制饱和溶液溶液，静置自然挥发，析出红棕色晶体；元素分析C48H72Cl2Co3N6O11理论值(％)：理论值(％)：C：49.84％；H:6.27％；N:7.26％；实测值(％)：C:49.53％；H:5.82％；N:7.49％；产率为92％；熔点为182-184℃，[a]5 D＝-327.4°(c 0.134,CH3OH),IR(KBr压片，cm-1)：3415,3291,3195,3062,2929,2854,1586,1535,1497,1454,1156,1056,1011,760,699.649,542,504；
化合物的晶体数据：
晶体典型的键长数据：
晶体典型的键角数据
亨利反应应用
2-硝基-1-苯基乙醇
催化剂I(0.148mmol),苯甲醛0.10mL(0.986mmol)及硝基甲烷(0.50mL,9.255mmol)在室温下搅拌6h，用核磁监测，转化率：48％，1H NMR(300MHz,CDCl3)7.28～7.32(m,5H,Ar-H),5.32～5.35(d,J＝9.18Hz,1H,-CH),4.38～4.56(m,2H,-CH2),3.89(br,1H,-OH)。
腈硅化反应应用
2-苯基-2-(三甲硅氧基)丙腈
0.2mmol配合物I,苯甲醛0.1mL,TMSCN 0.3ml(3.3mmol),2mL无水甲醇,相继在30～35℃下加入，30小时后，加入水淬灭经柱层后(石油醚/二氯甲烷：5/1)，得无色油状液体,转化率：34％；1H NMR(300MHz,CDCl3)7.56–7.59(m,0.9Hz,2H),7.31–7.34(m,3H),5.43(s,1H),0.16(s,9H).13C NMR(75MHz,CDCl3)136.1,128.8(x2),126.2(x2),119.1,63.5,-0.39(x3)。
烯丙基烷基化反应应用
取0.20mmol的配合物I(催化用量为20％)于25mL的小烧瓶中，加入2毫升的二氯甲烷溶液，然后，向上述溶液中加入0.1mL的苯甲醛与0.3mL的烯丙基三甲基硅烷，常温搅拌，反应72小时后，进行核磁分析，转化率：53％；1H NMR(300MHz,CDCl3)7.27～7.33(m,5H,Ar-H),5.79～5.80(m,1H),5.12～5.17(m,2H,-CH2),4.71(d，J＝5Hz，1H),2.49～2.50(m,2H)，2.28(s,1H)；
Baylis-Hillman反应应用
取0.20mmol的配合物I(催化用量为20％)于25mL的小烧瓶中，加入2毫升的二氯甲烷溶液，然后，向上述溶液中加入0.1mL的苯甲醛与0.5mL丙烯酸甲酯，常温搅拌，反应72小时后，进行核磁分析，转化率：58％；1HNMR(300MHz,CDCl3)7.20～7.41(m,5H,Ar-H),6.30(s,1H),5.45(s,1H),3.70(s,3H),3.15(s,1H)。
Claims (3)
1.一种手性苯甘氨醇钴配合物(I)，其化学式如下：
2.权利要求1所述的手性苯甘氨醇钴配合物(I)，在293(2)k温度下，在牛津X-射线单晶衍射仪上，用经石墨单色器单色化的MoKα射线以ω-θ扫描方式收集衍射数据，其特征在于晶体属单斜晶系,P2(1)2(1)2(1), α＝90°；β＝90°；γ＝90°。
3.权利要求1所述的手性苯甘氨醇钴配合物(I)的合成方法，本合成方法包括合成和分离，其特征在于：称取8.9005gL-苯甘氨醇放入100ml圆底烧瓶中，加入50ml氯苯，搅拌使其溶解，将2.3794gCoCl2·6H2O及5.0mL的甲基苯基二氯硅烷加入上述溶液，加热回流48h，旋转除去溶剂，加入石油醚、二氯甲烷配制饱和溶液，静置自然挥发，析出红棕色晶体。
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