CN111153931A - 一种2-吡啶甲烷亚胺锡（ii）化合物及其制备方法和应用 - Google Patents
一种2-吡啶甲烷亚胺锡（ii）化合物及其制备方法和应用 Download PDFInfo
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- -1 2-pyridine methane imine tin (II) compound Chemical class 0.000 title claims abstract description 44
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title abstract description 19
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 50
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 32
- BDNKZNFMNDZQMI-UHFFFAOYSA-N 1,3-diisopropylcarbodiimide Chemical compound CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 claims abstract description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 20
- 239000000706 filtrate Substances 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000013078 crystal Substances 0.000 claims abstract description 9
- FFNVQNRYTPFDDP-UHFFFAOYSA-N 2-cyanopyridine Chemical compound N#CC1=CC=CC=N1 FFNVQNRYTPFDDP-UHFFFAOYSA-N 0.000 claims abstract description 8
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000001376 precipitating effect Effects 0.000 claims abstract description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 3
- 239000003054 catalyst Substances 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 24
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 12
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 3
- IATQLXZUDMWFGV-UHFFFAOYSA-N 2,6-di(propan-2-yl)-n-trimethylsilylaniline Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N[Si](C)(C)C IATQLXZUDMWFGV-UHFFFAOYSA-N 0.000 claims 1
- XGIUDIMNNMKGDE-UHFFFAOYSA-N bis(trimethylsilyl)azanide Chemical compound C[Si](C)(C)[N-][Si](C)(C)C XGIUDIMNNMKGDE-UHFFFAOYSA-N 0.000 claims 1
- IPJPAQIHUIKFLV-UHFFFAOYSA-N n-trimethylsilylaniline Chemical group C[Si](C)(C)NC1=CC=CC=C1 IPJPAQIHUIKFLV-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 150000001875 compounds Chemical class 0.000 abstract description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 27
- 239000000047 product Substances 0.000 description 21
- 238000007259 addition reaction Methods 0.000 description 12
- 239000007832 Na2SO4 Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- 229910052938 sodium sulfate Inorganic materials 0.000 description 10
- 238000000605 extraction Methods 0.000 description 9
- 230000007062 hydrolysis Effects 0.000 description 9
- 238000006460 hydrolysis reaction Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000003446 ligand Substances 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- YNESATAKKCNGOF-UHFFFAOYSA-N lithium bis(trimethylsilyl)amide Chemical compound [Li+].C[Si](C)(C)[N-][Si](C)(C)C YNESATAKKCNGOF-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910020328 SiSn Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- RPEPFAFJOVVDGR-UHFFFAOYSA-N lithium [2,6-di(propan-2-yl)phenyl]-trimethylsilylazanide Chemical compound C(C)(C)C1=C(C(=CC=C1)C(C)C)[N-][Si](C)(C)C.[Li+] RPEPFAFJOVVDGR-UHFFFAOYSA-N 0.000 description 1
- JZSSNAVPFLMHDJ-UHFFFAOYSA-N lithium phenyl(trimethylsilyl)azanide Chemical compound [Li+].C[Si](C)(C)[N-]c1ccccc1 JZSSNAVPFLMHDJ-UHFFFAOYSA-N 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229910001848 post-transition metal Inorganic materials 0.000 description 1
- UZEMMOMRSHUTOA-UHFFFAOYSA-N pyridin-2-ylmethanimine Chemical compound N=CC1=CC=CC=N1 UZEMMOMRSHUTOA-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/22—Tin compounds
- C07F7/2284—Compounds with one or more Sn-N linkages
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C277/00—Preparation of guanidine or its derivatives, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups
- C07C277/08—Preparation of guanidine or its derivatives, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups of substituted guanidines
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- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
- B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
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Abstract
本发明提供一种2‑吡啶甲烷亚胺锡(II)化合物及其制备方法和应用。该化合物制备步骤：在氮气保护下将氨基锂用乙醚溶解,在丙酮浴条件下加入2‑氰基吡啶,反应过夜；在丙酮浴条件下加入无水SnCl2,慢慢升至室温，反应过夜；静置，过滤，滤液在真空下浓缩，室温下结晶，析出黄色晶体，即得2‑吡啶甲烷亚胺锡(II)化合物；所述的氨基锂、2‑氰基吡啶和SnCl2的摩尔比为1:1:1。本发明化合物可作为催化剂用于催化苯胺和N,N'‑二异丙基碳化二亚胺加成生成胍的反应，有较好的应用前景。
Description
技术领域
本发明涉及N,N二齿金属化合物，具体涉及一种2-吡啶甲烷亚胺锡(II)化合物及其制备方法和应用。
背景技术
作为一种非环戊二烯的氮基配体在稳定主族金属、过渡金属及稀土元素中发挥着越来越重要的作用。2-吡啶甲烷亚胺，作为一种N，N-二齿配体，其立体位阻和电子效应方便可调，其过渡金属或后过渡金属化合物可作为烯烃聚合催化剂并具有中等或较高的催化活性。本发明2-吡啶甲烷亚胺锡(II)化合物结构新颖，能很好地催化苯胺和N,N'-二异丙基碳化二亚胺的加成反应。
发明内容
本发明的目的在于提供一种方法简单、结构新颖、易于合成的2-吡啶甲烷亚胺锡(II) 化合物及其制备方法和应用。
本发明提供的一种2-吡啶甲烷亚胺锡(II)化合物，其化学结构式为：
本发明提供的一种2-吡啶甲烷亚胺锡(II)化合物的制备方法，包括如下步骤:
在氮气保护下将氨基锂用乙醚溶解,在丙酮浴条件下加入2-氰基吡啶,反应过夜；在丙酮浴条件下加入无水SnCl2,慢慢升至室温，反应过夜；静置，过滤，滤液在真空下浓缩，室温下结晶，析出黄色晶体，即得2-吡啶甲烷亚胺锡(II)化合物；所述的氨基锂、2-氰基吡啶和SnCl2的摩尔比为1:1:1。
所述的氨基锂可以为三甲基硅基苯(基)氨基锂、三甲基硅基-2,6二异丙基苯(基)氨基锂或二(三甲基硅基)氨基锂等。
本发明合成的2-吡啶甲烷亚胺锡(II)化合物是一种很好的催化剂，能以高收率催化苯胺和N,N'-二异丙基碳化二亚胺加成生成胍的反应。
与现有技术相比本发明具有如下优点和效果：本发明2-吡啶甲烷亚胺锡(II)化合物采用金属有机方法得到，合成方法简单，化合物结构新颖，反应易于控制得到目标产物，样品纯度高，收率高。本发明2-吡啶甲烷亚胺锡(II)化合物能很好地催化苯胺和N,N'-二异丙基碳化二亚胺的加成反应，是一种良好的反应催化剂。
附图说明
图1 2-吡啶甲烷亚胺锡(II)化合物a的x-射线衍射结构图
图2 2-吡啶甲烷亚胺锡(II)化合物b的x-射线衍射结构图
具体实施方式
实施例1：
2-吡啶甲烷亚胺锡(II)化合物a的制备：在氮气保护下将三甲基硅基-2,6二异丙基苯 (基)氨基锂0.60g(2.36mmol)用乙醚溶解,在丙酮浴条件下加入2-氰基吡啶0.23ml(2.36 mmol),反应过夜；在丙酮浴条件下加入无水SnCl2 0.45g(2.36mmol),慢慢升至室温，反应过夜；静置，过滤，滤液在真空下浓缩，室温下结晶，析出黄色晶体，即得2-吡啶甲烷亚胺锡(II)化合物a 1.07g；产率89.2％。
熔点：92℃(分解)
元素分析：理论值C,49.77；H,5.97；N,8.29％；实测值C,49.80；H,5.93；N,8.25％。
核磁：1H NMR(CDCl3):δ0.44-0.46(t,9H,SiMe3),0.85(s,6H,CH(CH3)2),1.17(s,6H, CH(CH3)2),3.02-3.06(m,2H,CH(CH3)2)，7.01-7.12(m,3H,Ph),7.24(s,H,5-Py),7.57(s,1H, 4-Py),7.71(s,1H,3-Py),8.56(s,1H,6-Py).13C NMR(CDCl3):δ1.81(SiMe3),23.3,24.07 (CH(CH3)2),28.02(CH(CH3)2),122.1(p-CPh),123.7(m-CPh),129.13(o-CPh),126.2,126.9, 136.8,140.4(C-Py),145.48,146.05(Cipso-Ph),149.81(2-Py),157.65(NCN)。
2-吡啶甲烷亚胺锡(II)化合物a的x-射线衍射结构图见图1。
晶体参数：分子式C21H30ClN3SiSn，分子量506.71，晶系Monoclinic，空间群Cc(No.9)，晶胞参数
β＝116.496(13)°,
Z＝4，Dc＝1.312Mg/m3,μ(Mo-Kα)＝1.157mm-1,T＝295(2)K,R1＝0.0266,wR2＝0.0589。
部分键长
与键角[°]:Sn(1)-N(1)2.224(5),Sn(1)-N(2)2.099(5),Sn(1)-Cl(1)2.453(3), C(5)-C(6)1.518(7),C(6)-N(2)1.369(6)；N(1)-Sn(1)-N(2)75.30(19),N(1)-C(5)-C(6)114.5(5), N(2)-C(6)-C(5)114.4(5),Cl(1)-Sn(1)-N(1)88.52(18),Cl(1)-Sn(1)-N(2)93.22(18)。
实施例2：
2-吡啶甲烷亚胺锡(II)化合物b的制备：在氮气保护下将二(三甲基硅基)氨基锂0.48 g(2.89mmol)用乙醚溶解,在丙酮浴条件下加入2-氰基吡啶0.28ml(2.89mmol),反应过夜；在丙酮浴条件下加入无水SnCl2 0.55g(2.89mmol),慢慢升至室温，反应过夜；静置，过滤，滤液在真空下浓缩，室温下结晶，析出黄色晶体，即得2-吡啶甲烷亚胺锡(II)化合物b0.687g；产率56.8％。
熔点：98-103℃.
元素分析：理论值C,34.43；H,5.30；N,10.04％；实测值C,34.40；H,5.29；N,10.09％。
核磁：1H NMR(CDCl3):δ-0.065(s,18H,SiMe3),7.36-7.41(m,2H,Py),7.79-7.82(m,1H, 3-Py),8.65(s,1H,6-Py).13C NMR(CDCl3):δ0.86(SiMe3),121.2,124.5,136.7,149.4,157.7 (C-Py),179.9(NCN)。
2-吡啶甲烷亚胺锡(II)化合物b的x-射线衍射结构图见图2。
晶体参数：分子式C12H22ClN3Si2Sn，分子量418.64，晶系Monoclinic，空间群P21/c(No.14)，晶胞参数
β＝91.811(7)°,
Z＝4，Dc＝1.544Mg/m3,μ(Mo-Kα)＝1.692mm-1,T＝295(2)K,R1＝0.0398, wR2＝0.0741。
部分键长
与键角[°]:Sn(1)-N(1)2.120(3),Sn(1)-N(3)2.253(4),Sn(1)-Cl(1)2.549(2), C(4)-C(8)1.530(6),C(4)-N(1)1.363(5)；N(1)-Sn(1)-N(3)74.81(14),N(3)-C(8)-N(4)116.0(4), N(1)-C(4)-C(8)112.9(4),Cl(1)-Sn(1)-N(1)93.83(11),Cl(1)-Sn(1)-N(3)86.76(10)。
实施例3：
步骤1,2-吡啶甲烷亚胺锡(II)化合物a的制备同实施例1。
步骤2,催化加成:催化苯胺和N,N'-二异丙基碳化二亚胺的加成反应:称量0.010g(0.02 mmol)的2-吡啶甲烷亚胺锡(II)化合物a放到30mL的充满氮气的Schlenk瓶中，加入N,N'-二异丙基碳化二亚胺0.62mL(4.00mmol)和苯胺0.36mL(4.00mmol)。在25℃反应5.0min,用0.5mL水进行水解，用30mL二氯甲烷萃取三次(3×10mL)，无水Na2SO4干燥，过滤。滤液抽干，产品用正己烷结晶纯化，得产物胍，收率52.3％。
实施例4：
步骤1,2-吡啶甲烷亚胺锡(II)化合物a的制备同实施例1。
步骤2,催化苯胺和N,N'-二异丙基碳化二亚胺的加成反应:称量0.010g(0.02mmol) 的2-吡啶甲烷亚胺锡(II)化合物a放到30mL的充满氮气的Schlenk瓶中，加入N,N'- 二异丙基碳化二亚胺0.62mL(4.00mmol)和苯胺0.36mL(4.00mmol)。在25℃反应10min,用0.5mL水进行水解，用30mL二氯甲烷萃取三次(3×10mL)，无水Na2SO4干燥，过滤。滤液抽干，产品用正己烷结晶纯化，得产物胍，收率76.4％。
实施例5：
步骤1,2-吡啶甲烷亚胺锡(II)化合物a的制备同实施例1。
步骤2,催化苯胺和N,N'-二异丙基碳化二亚胺的加成反应:称量0.010g(0.02mmol) 的2-吡啶甲烷亚胺锡(II)化合物a放到30mL的充满氮气的Schlenk瓶中，加入N,N'- 二异丙基碳化二亚胺0.62mL(4.00mmol)和苯胺0.36mL(4.00mmol)。在25℃反应15min,用0.5mL水进行水解，用30mL二氯甲烷萃取三次(3×10mL)，无水Na2SO4干燥，过滤。滤液抽干，产品用正己烷结晶纯化，得产物胍，收率88.7％。
实施例6：
步骤1,2-吡啶甲烷亚胺锡(II)化合物a的制备同实施例1。
步骤2,催化苯胺和N,N'-二异丙基碳化二亚胺的加成反应:称量0.010g(0.02mmol) 的2-吡啶甲烷亚胺锡(II)化合物a放到30mL的充满氮气的Schlenk瓶中，加入N,N'- 二异丙基碳化二亚胺0.62mL(4.00mmol)和苯胺0.36mL(4.00mmol)。在25℃反应20min,用0.5mL水进行水解，用30mL二氯甲烷萃取三次(3×10mL)，无水Na2SO4干燥，过滤。滤液抽干，产品用正己烷结晶纯化，得产物胍，收率98.2％。
实施例7：
步骤1,2-吡啶甲烷亚胺锡(II)化合物a的制备同实施例1。
步骤2,催化苯胺和N,N'-二异丙基碳化二亚胺的加成反应:称量0.010g(0.02mmol) 的2-吡啶甲烷亚胺锡(II)化合物a放到30mL的充满氮气的Schlenk瓶中，加入N,N'- 二异丙基碳化二亚胺0.62mL(4.00mmol)和苯胺0.36mL(4.00mmol)。在60℃反应0.5min,用0.5mL水进行水解，用30mL二氯甲烷萃取三次(3×10mL)，无水Na2SO4干燥，过滤。滤液抽干，产品用正己烷结晶纯化，得产物胍，收率89.8％。
实施例8：
步骤1,2-吡啶甲烷亚胺锡(II)化合物a的制备同实施例1。
步骤2,催化苯胺和N,N'-二异丙基碳化二亚胺的加成反应:称量0.010g(0.02mmol) 的2-吡啶甲烷亚胺锡(II)化合物a放到30mL的充满氮气的Schlenk瓶中，加入N,N'- 二异丙基碳化二亚胺0.62mL(4.00mmol)和苯胺0.36mL(4.00mmol)。在80℃反应0.5min,用0.5mL水进行水解，用30mL二氯甲烷萃取三次(3×10mL)，无水Na2SO4干燥，过滤。滤液抽干，产品用正己烷结晶纯化，得产物胍，收率98.5％。
实施例9：
步骤1,2-吡啶甲烷亚胺锡(II)化合物b的制备同实施例2。
步骤2,催化苯胺和N,N'-二异丙基碳化二亚胺的加成反应:称量0.008g(0.02mmol) 的2-吡啶甲烷亚胺锡(II)化合物b放到30mL的充满氮气的Schlenk瓶中，加入N,N'- 二异丙基碳化二亚胺0.62mL(4.00mmol)和苯胺0.36mL(4.00mmol)。在25℃反应2.0h,用0.5mL水进行水解，用30mL二氯甲烷萃取三次(3×10mL)，无水Na2SO4干燥，过滤。滤液抽干，产品用正己烷结晶纯化，得产物胍，收率27.9％。
实施例10：
步骤1,2-吡啶甲烷亚胺锡(II)化合物b的制备同实施例2。
步骤2,催化苯胺和N,N'-二异丙基碳化二亚胺的加成反应:称量0.008g(0.02mmol) 的2-吡啶甲烷亚胺锡(II)化合物b放到30mL的充满氮气的Schlenk瓶中，加入N,N'- 二异丙基碳化二亚胺0.62mL(4.00mmol)和苯胺0.36mL(4.00mmol)。在50℃反应0.25h,用0.5mL水进行水解，用30mL二氯甲烷萃取三次(3×10mL)，无水Na2SO4干燥，过滤。滤液抽干，产品用正己烷结晶纯化，得产物胍，收率56.3％。
实施例11：
步骤1,2-吡啶甲烷亚胺锡(II)化合物b的制备同实施例2。
步骤2,催化苯胺和N,N'-二异丙基碳化二亚胺的加成反应:称量0.008g(0.02mmol) 的2-吡啶甲烷亚胺锡(II)化合物b放到30mL的充满氮气的Schlenk瓶中，加入N,N'- 二异丙基碳化二亚胺0.62mL(4.00mmol)和苯胺0.36mL(4.00mmol)。在50℃反应0.5h,用0.5mL水进行水解，用30mL二氯甲烷萃取三次(3×10mL)，无水Na2SO4干燥，过滤。滤液抽干，产品用正己烷结晶纯化，得产物胍，收率89.8％。
实施例12：
步骤1,2-吡啶甲烷亚胺锡(II)化合物b的制备同实施例2。
步骤2,催化苯胺和N,N'-二异丙基碳化二亚胺的加成反应:称量0.008g(0.02mmol) 的2-吡啶甲烷亚胺锡(II)化合物b放到30mL的充满氮气的Schlenk瓶中，加入N,N'- 二异丙基碳化二亚胺0.62mL(4.00mmol)和苯胺0.36mL(4.00mmol)。在50℃反应1.0h,用0.5mL水进行水解，用30mL二氯甲烷萃取三次(3×10mL)，无水Na2SO4干燥，过滤。滤液抽干，产品用正己烷结晶纯化，得产物胍，收率96.2％。
Claims (4)
1.一种2-吡啶甲烷亚胺锡(II)化合物，其特征在于，结构式为：
2.如权利要求1所述的一种2-吡啶甲烷亚胺锡(II)化合物的制备方法，其特征在于包括如下步骤：
在氮气保护下将氨基锂用乙醚溶解,在丙酮浴条件下加入2-氰基吡啶,反应过夜；在丙酮浴条件下加入无水SnCl2,慢慢升至室温，反应过夜；静置，过滤，滤液在真空下浓缩，室温下结晶，析出黄色晶体，即得2-吡啶甲烷亚胺锡(II)化合物；所述的氨基锂、2-氰基吡啶和SnCl2的摩尔比为1:1:1。
3.如权利要求2所述的一种2-吡啶甲烷亚胺锡(II)化合物的制备方法，其特征在于所述的氨基锂为三甲基硅基苯(基)氨基锂、三甲基硅基-2,6二异丙基苯(基)氨基锂或二(三甲基硅基)氨基锂。
4.如权利要求1所述的2-吡啶甲烷亚胺锡(II)化合物作为催化剂在催化苯胺和N,N'-二异丙基碳化二亚胺加成生成胍中的应用。
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