CN109331875A - 一种双核镁金属催化剂及其制备方法和应用 - Google Patents
一种双核镁金属催化剂及其制备方法和应用 Download PDFInfo
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- 239000011777 magnesium Substances 0.000 title claims abstract description 23
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 16
- 239000003863 metallic catalyst Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- PKZJLOCLABXVMC-UHFFFAOYSA-N 2-Methoxybenzaldehyde Chemical compound COC1=CC=CC=C1C=O PKZJLOCLABXVMC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000006880 cross-coupling reaction Methods 0.000 claims abstract description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006423 Tishchenko reaction Methods 0.000 claims abstract description 8
- 239000000284 extract Substances 0.000 claims abstract description 8
- 239000005457 ice water Substances 0.000 claims abstract description 7
- 239000013078 crystal Substances 0.000 claims abstract description 6
- KJJBSBKRXUVBMX-UHFFFAOYSA-N magnesium;butane Chemical compound [Mg+2].CCC[CH2-].CCC[CH2-] KJJBSBKRXUVBMX-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- 239000003446 ligand Substances 0.000 claims abstract description 4
- RSUCYDXEFFBUSN-UHFFFAOYSA-N n-tert-butylmethanimine Chemical compound CC(C)(C)N=C RSUCYDXEFFBUSN-UHFFFAOYSA-N 0.000 claims abstract description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 3
- 230000002269 spontaneous effect Effects 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 21
- 238000000034 method Methods 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 20
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000012043 crude product Substances 0.000 description 5
- 239000002024 ethyl acetate extract Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- AVPYQKSLYISFPO-UHFFFAOYSA-N 4-chlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C=C1 AVPYQKSLYISFPO-UHFFFAOYSA-N 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- -1 ester compounds Chemical class 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 241000208340 Araliaceae Species 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 150000002895 organic esters Chemical class 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229940065287 selenium compound Drugs 0.000 description 1
- 150000003343 selenium compounds Chemical class 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/44—Preparation of carboxylic acid esters by oxidation-reduction of aldehydes, e.g. Tishchenko reaction
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
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- C07F3/02—Magnesium compounds
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
- B01J2231/4288—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using O nucleophiles, e.g. alcohols, carboxylates, esters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/22—Magnesium
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Abstract
本发明提供了一种双核镁金属催化剂及其制备方法和应用。催化剂制备方法：在惰性气体保护和冰水浴条件下，首先用等当量的二正丁基镁与N‑吡咯亚甲基叔丁胺配体进行反应，将所得溶液室温反应2‑3小时后，再向其中逐滴加入1倍量的邻甲氧基苯甲醛，待反应完毕后真空浓缩反应液，用乙醚萃取，萃取液过滤浓缩析出无色透明晶体即可。该催化剂对于交叉偶合Tishchenko反应具有较高选择性和催化活性，且制备方法简便，原料易得，反应条件温和，有很好的工业应用前景。
Description
技术领域
本发明涉及有机金属镁化合物催化剂，具体涉及一种双核镁金属催化剂及其制备方法和应用。
背景技术
有机酯类化合物的合成是有机合成、制药和食物香料工业等领域的一个重要转化过程。其中Tishchenko反应由于不生成任何副产物，原子经济性达100％，成为化学合成有机酯类化合物的重要反应之一。然而，Tishchenko反应始终不能成为大量合成酯类化合物的实用方法，其最大的局限就是它只能用作偶合两分子相同的醛，所生成的酯类化合物种类单一。
尽管，Stephen J.Connon小组已报道了硫醇盐促进的不同芳香醛分子间的高选择性交叉偶合Tishchenko反应，随后，又利用烃基二硒化合物作为催化剂，二丁基镁助催化剂在四氢呋喃溶剂中分子筛存在下，成功实现了两种相同或不同芳香醛的Tishchenko反应，催化活性及选择性均具有很好的表现。北京科技大学党智敏教授通过理论计算进一步证实了Connon提出的硫醇盐促进的不同芳香醛分子间的高选择性交叉偶合Tishchenko反应机理。
但迄今为止，高选择性的交叉偶联Tishchenko反应仅仅在一些有限的、特殊的反应底物醛中取得了成功。总体而言，想要突破底物局限性以及低选择性，达到普遍实用目的，其研究还远远不够深入。因此，开发合成高效、廉价、选择性高的交叉偶合Tishchenko反应催化剂具有重大的实用价值。
发明内容
本发明的目的是提供一种双核镁金属催化剂及其制备方法，该催化剂制备方法简便，原料易得，反应条件温和；该催化剂用于交叉偶合Tishchenko反应具有较高选择性和催化活性，有很好的工业应用前景。
本发明提供的一种双核镁金属催化剂，其结构式为：
本发明提供的双核镁金属催化剂制备反应式如下：
本发明提供的一种双核镁金属催化剂的制备方法，包括如下步骤：
在惰性气体保护和冰水浴条件下，用等当量的二正丁基镁与N-吡咯亚甲基叔丁胺配体进行反应，溶剂为正己烷，自然恢复到室温，搅拌2-3小时后，将所得溶液用冰水浴再次冷却到0℃，逐滴滴加等当量的邻甲氧基苯甲醛，滴加完毕缓慢恢复到室温，继续搅拌6-8小时，真空浓缩反应液，用乙醚萃取，萃取液过滤浓缩至饱和状态，室温放置1-2天，析出无色透明晶体，即为双核镁金属催化剂。
该催化剂可在不同醛类化合物之间实现交叉偶合Tishchenko反应中应用。
与现有技术相比本发明的优点和效果：本发明催化剂制备过程简单，原料易得，反应条件温和；本发明催化剂对交叉偶合Tishchenko反应具有较高的选择性和催化活性，催化过程可以不使用溶剂，绿色环保，有很好的应用前景。
附图说明
图1本发明双核镁金属催化剂的单晶X射线结构图
具体实施方式
以下仅仅为详细说明本发明而给出的具体实施例，这些实施例并非用于限制本发明的保护范围。
实施例1双核镁金属催化剂的制备
在惰性气体保护和冰水浴条件下，向N-吡咯亚甲基叔丁胺配体(0.451g,3mmol)的正己烷溶液中缓慢滴加二正丁基镁溶液(3.00mL,1.0M)，滴加完毕，自然恢复到室温，继续搅拌2小时后，将所得溶液用冰水浴再次冷却到零摄氏度，依次逐滴滴加邻甲氧基苯甲醛(0.408g,3mmol)，滴加完毕缓慢回到室温继续搅拌7小时，真空浓缩反应液，用乙醚萃取，萃取液过滤浓缩至饱和状态，室温放置1-2天，析出无色透明晶体，即为双核镁金属催化剂(以下简称催化剂)，产率63％。
晶体参数：化学式C42H60Mg2N4O4，单斜晶系(Monoclinic)，空间群P 1 2/n1，晶胞参数 α＝90.00°,β＝103.704(3)°,γ＝90.00°,V＝4167.4(6),Z＝4。单晶结构图见图1。
部分键长Mg-O2 1.941(3),Mg-N1 2.079(3),Mg-O1 2.266(3),Mg-N2 2.146(3),O2-C17 1.420(5),N1-C4 1.385(5),N1-C1 1.345(5),O1-C11 1.408(5),O1-C101.442(5),N2-C5 1.288(5),N2-C6 1.491(5),C17-C16 1.520(6),C17-C18 1.578(7),C5-C4 1.424(6),C4-C3 1.396(6),C1-C2 1.393(6),C6-C9 1.537(6),C6-C7 1.512(6),C15-C16 1.394(6),C15-C14 1.385(7),C16-C11 1.395(5),C11-C12 1.378(6),C12-C13 1.397(7),C3-C2 1.382(7),C14-C13 1.389(7),C18-C19 1.466(7),C19-C20 1.551(8),C20-C211.469(9)；键角(°):O2-Mg-N1 130.42(14),O2-Mg-O1 82.51(11),O2-Mg-N2 146.00(13),N1-Mg-O1 94.15(12),N1-Mg-N2 82.17(13),N2-Mg-O1 86.07(12),C17-O2-Mg 129.2(2),C4-N1-Mg 107.5(2),C1-N1-Mg 145.1(3),C1-N1-C4 105.4(4),C11-O1-Mg 122.4(2),C11-O1-C10 116.5(3),C10-O1-Mg1 120.2(2),C5-N2-Mg 108.1(3),C5-N2-C6 121.0(3),C6-N2-Mg 130.8(2),O2-C17-C16 111.6(3),O2-C17-C18 112.7(4),N2-C5-C4 121.4(4),N1-C4-C5 119.3(3),N1-C4-C3 110.2(4),N2-C6-C8 112.2(3),N2-C6-C9 109.1(3),N2-C6-C7105.8(3),C16-C11-O1 116.7(4)。
实施例2
(1)催化剂的制备同实施例1。
(2)催化苯甲醛与邻溴苯甲醛交叉偶合Tishchenko反应：
在室温下，将苯甲醛(0.212g,2mmol)和邻溴苯甲醛(0.370g,2mmol)沿甁壁缓慢加入到装有催化剂(0.073g,0.10mmol)的Schlenk反应瓶中，控制温度在30℃下搅拌反应4小时后，用5mL水终止反应，乙酸乙酯萃取三次，真空浓缩萃取液，粗产品用硅胶柱色谱分离，得目标产物，白色固体，产率81％。1H NMR(600MHz,CDCl3):δ＝5.48(s,2H),7.24(t,1H),7.35(t,1H),7.48(m,2H),7.59(m,3H),8.13(d,J＝6.4Hz,2H)；13C(150.9MHz,CDCl3):δ＝66.2,123.5,127.6,128.5,129.7,129.8,129.9,132.9,133.2,135.4,166.2。
实施例3
(1)催化剂的制备同实施例1。
(2)催化苯甲醛与邻甲氧基苯甲醛交叉偶合Tishchenko反应：
在室温下，将苯甲醛(0.212g,2mmol)和邻甲氧基苯甲醛(0.272g,2mmol)沿甁壁缓慢加入到装有催化剂(0.073g,0.10mmol)的Schlenk反应瓶中，控制温度在30℃下搅拌反应4小时后，用5mL水终止反应，乙酸乙酯萃取三次，真空浓缩萃取液，粗产品用硅胶柱色谱分离，得目标产物，白色固体，产率79％。M.p.42-44℃.1H(600MHz,CDCl3):δ＝3.89(s,3H),5.45(s,2H),6.94-6.99(m,2H),7.33-7.36(m,1H),7.44-7.47(m,3H),7.58(t,1H),8.11(d,2H)；13C(150.9MHz,CDCl3):δ＝55.2,61.7,110.0,120.2,123.8,127.9,128.9,129.0,129.4,129.7,132.5,157.3,166.2。
实施例4
(1)催化剂的制备同实施例1。
(2)催化对氯苯甲醛与邻甲氧基苯甲醛交叉偶合Tishchenko反应：
在室温下，将对氯苯甲醛(0.281g,2mmol)和邻甲氧基苯甲醛(0.272g,2mmol)沿甁壁缓慢加入到装有催化剂(0.073g,0.10mmol)的Schlenk反应瓶中，控制温度在30℃下搅拌反应4小时后，用5mL水终止反应，乙酸乙酯萃取三次，真空浓缩萃取液，粗产品用硅胶柱色谱分离，得目标产物，白色固体，产率83％。M.p.52-54℃.1H(600MHz,CDCl3):δ＝3.86(s,3H),5.45(s,2H),6.91-7.01(m,2H),7.32-7.44(m,4H),8.02(d,2H)；13C(150.9MHz,CDCl3):δ＝55.0,62.1,110.3,120.1,123.4,128.2,128.3,129.2,129.2,130.9,138.9,157.3,165.4。
实施例5
(1)催化剂的制备同实施例1。
(2)催化对氯苯甲醛与邻溴苯甲醛交叉偶合Tishchenko反应：
在室温下，将对氯苯甲醛(0.281g,2mmol)和邻溴苯甲醛(0.370g,2mmol)沿甁壁缓慢加入到装有催化剂(0.073g,0.10mmol)的Schlenk反应瓶中，控制温度在30℃下搅拌反应4小时后，用5mL水终止反应，乙酸乙酯萃取三次，真空浓缩萃取液，粗产品用硅胶柱色谱分离，得目标产物，淡黄色固体，产率85％。M.p.67-71℃.1H(600MHz,CDCl3):δ＝5.48(s,2H),7.24(t,1H),7.38(t,1H),7.44(d,2H),7.52(dd,1H),7.65(dd,1H),8.07(d,2H).13C(150.9MHz,CDCl3):δ＝66.1,123.6,127.1,127.8,128.5,129.5,129.7,130.7,132.7,134.7,139.3,165.0。
实施例6
(1)催化剂的制备同实施例1。
(2)催化对甲氧基苯甲醛与邻甲氧基苯甲醛交叉偶合Tishchenko反应：
在室温下，将对甲氧基苯甲醛(0.272g,2mmol)和邻甲氧基苯甲醛(0.272g,2mmol)沿甁壁缓慢加入到装有催化剂(0.073g,0.10mmol)的Schlenk反应瓶中，控制温度在30℃下搅拌反应4小时后，用5mL水终止反应，乙酸乙酯萃取三次，真空浓缩萃取液，粗产品用硅胶柱色谱分离，得目标产物，淡黄色油状液体，产率71％。1H(600MHz,CDCl3):δ＝3.87(s,3H),5.41(s,2H),6.93-6.94(m,3H),7.01(t,1H),7.37(t,1H),7.43(d,1H),8.05(d,2H).13C(150.9MHz,CDCl3):δ＝55.0,61.4,110.0,113.1,120.1,122.4,124.2,125.5,128.8,128.9,131.3,157.0,162.9,165.5。
Claims (3)
1.一种双核镁金属催化剂，其特征在于，结构式为：
2.如权利要求1所述的一种双核镁金属催化剂的制备方法，其特征在于，包括如下步骤：
在惰性气体保护和冰水浴条件下，用等当量的二正丁基镁与N-吡咯亚甲基叔丁胺配体进行反应，溶剂为正己烷，自然恢复到室温，搅拌2-3小时后，将所得溶液用冰水浴再次冷却到0℃，逐滴滴加等当量的邻甲氧基苯甲醛，滴加完毕缓慢恢复到室温，继续搅拌6-8小时，真空浓缩反应液，用乙醚萃取，萃取液过滤浓缩至饱和状态，室温放置1-2天，析出无色透明晶体，即为双核镁金属催化剂。
3.如权利要求1所述的双核镁金属催化剂在交叉偶合Tishchenko反应中的应用。
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