CN114907215A - 一种芳香甲酰胺与烯烃的催化脱羰氢胺化的方法 - Google Patents
一种芳香甲酰胺与烯烃的催化脱羰氢胺化的方法 Download PDFInfo
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- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000005913 hydroamination reaction Methods 0.000 title claims abstract description 18
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 13
- 230000006324 decarbonylation Effects 0.000 title claims abstract description 10
- 238000006606 decarbonylation reaction Methods 0.000 title claims abstract description 10
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 14
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 23
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 18
- 150000001412 amines Chemical class 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 238000004440 column chromatography Methods 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 229910052765 Lutetium Inorganic materials 0.000 claims description 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- -1 rare earth amine Chemical class 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims 1
- 150000003512 tertiary amines Chemical class 0.000 abstract description 4
- 238000007259 addition reaction Methods 0.000 abstract description 3
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- 238000005810 carbonylation reaction Methods 0.000 abstract description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract 1
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract 1
- 230000006315 carbonylation Effects 0.000 abstract 1
- 239000011261 inert gas Substances 0.000 abstract 1
- 238000003541 multi-stage reaction Methods 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 18
- 150000001345 alkine derivatives Chemical class 0.000 description 9
- ZDYNTRMQDURVDM-UHFFFAOYSA-N bis(trimethylsilyl)azanide;lanthanum(3+) Chemical compound [La+3].C[Si](C)(C)[N-][Si](C)(C)C.C[Si](C)(C)[N-][Si](C)(C)C.C[Si](C)(C)[N-][Si](C)(C)C ZDYNTRMQDURVDM-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000006198 deformylation Effects 0.000 description 1
- 238000006344 deformylation reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000003818 flash chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006452 multicomponent reaction Methods 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/60—Preparation of compounds containing amino groups bound to a carbon skeleton by condensation or addition reactions, e.g. Mannich reaction, addition of ammonia or amines to alkenes or to alkynes or addition of compounds containing an active hydrogen atom to Schiff's bases, quinone imines, or aziranes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen 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
- C07D213/72—Nitrogen atoms
- C07D213/74—Amino or imino radicals substituted by hydrocarbon or substituted hydrocarbon radicals
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- 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
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
本发明属于有机化学技术领域,具体为一种芳香甲酰胺与烯烃的催化脱羰氢胺化的方法。本发明是在惰性气体氛围和稀土催化剂存在下,于有机溶剂中,由芳香甲酰胺与末端烯烃反应,形成脱羰氢胺化产物和一氧化碳。已知的甲酰胺与烯烃的加成反应是得到烯烃氢胺羰化产物或氢酰胺化产物,本发明反应与传统的烯烃与甲酰胺的反应模式具有重要的互补性;前期报道的有限数量的已知三级胺与烯烃的氢胺化反应需要有其它反应试剂(如硅氢烷)存在或者是分步反应,反应条件苛刻,并且仅限于与活化烯烃的反应;本发明反应具有条件温和,底物普适性较好,无需添加剂等优点,得到的是反马氏加成的氢胺化产物。
Description
技术领域
本发明属于有机化学技术领域,具体涉及一类芳香甲酰胺与烯烃的催化脱羰氢胺化的方法。
背景技术
胺是自然界中广泛存在的化合物,胺的转化是药物合成中使用频率最高的反应(J.Med.Chem.2016,59,4443-4458)。在各种胺衍生物的合成方法中,烯烃和炔烃的氢胺化反应是最原子经济性的构建C-N键方法。虽然元素周期表中的绝大部分金属被发现具有催化烯烃和炔烃与N-H键加成的潜能,但是这些胺主要限于一级和二级胺(Chem.Rev.2015,115,2596-2697)。对于三级胺的C-N键与烯(炔)烃的氢胺化反应则仅限于少数其它反应试剂(如硅氢烷)参与的多组分反应,反应条件通常较苛刻,原子经济性差(Eur.J.Org.Chem.2007,4600–4604;J.Am.Chem.Soc.2012,134,6571-6574)。因此,发展三级胺的新活化策略及其与烯(炔)烃的新反应模式是富有挑战性和重要应用价值的研究课题。
三级甲酰胺代表一类重要的胺衍生物,稳定性好,价廉易得。虽然有关这类化合物与烯烃和炔烃的加成反应已经有所报道,但仅能得到氢胺羰化反应产物(Chem.Lett.2012,41,298-300;J.Am.Chem.Soc.2013,135,11772-11775)。若想从三级甲酰胺和烯(炔)烃合成氢胺化产物,则需要采用分步法,先去甲酰化,然后再利用分离提纯的脱保护胺与烯(炔)烃进行氢胺化反应。
发明内容
本发明的目的在于提供一种反应条件温和、底物普适性好、操作简便的芳香甲酰胺与烯烃的催化脱羰氢胺化的方法。
本发明提供的芳香甲酰胺与烯烃的催化脱羰氢胺化的方法,具体步骤为:
以芳香甲酰胺(I)和苯乙烯(II)为原料,以商品化或易制备的稀土金属配合物为催化剂,在有机溶剂中,于25-120℃条件下反应3-36小时;反应完成后,经过分离纯化得到对应的胺(III);其反应路线为:
式中,R1,选自H、烷基、卤素或苯基;R2选自烷基;R选自H、烷基或卤素;X=CH、N或P。
本发明中,所述原料苯乙烯(II)与原料甲酰胺(I)用量之比为2-6倍,优选为3-4倍。
本发明中,所述有机溶剂选自为不与反应物和产物发生反应的常规极性有机溶剂,如DME、DMSO等,具体优选为N,N-二甲基甲酰胺。
本发明中,所用有机溶剂的质量是原料甲酰胺(I)的10-30倍;优选为15-20倍。
进一步地,所述催化剂选自稀土烷基配合物、稀土芳基配合物、稀土胺基配合物;所述稀土金属选自La、Sm、Yb、Lu、Y;优选为La的胺基、烷基和芳基配合物。
进一步,所述的稀土催化剂与原料甲酰胺(I)的摩尔比为0.02-0.2,优选摩尔比为0.05–0.15。
本发明中,反应温度为25-120℃,优选为60–80℃,反应时间一般在3-36小时,优选为12-24小时。
本发明中,所述的分离纯化采用的是柱层析分离纯化法。反应结束后所得反应液蒸出溶剂,经湿法上样进行柱层析分离纯化干燥即得目标产物。淋洗液为石油醚与乙酸乙酯混合物,石油醚与乙酸乙酯的体积比为50:1-20:1,优选为40:1-20:1。
本发明利用稀土金属配合物作为催化剂,首次实现芳香甲酰胺与烯(炔)烃的催化脱羰氢胺化反应。其有益效果主要体现在:
(1)本发明所述的芳香甲酰胺与烯烃的脱羰氢胺化反应是首例三级胺类化合物与烯烃的直接氢胺化反应;
(2)已知的甲酰胺与烯烃的加成反应一般是得到烯烃氢胺羰化产物或氢酰胺化产物,本发明反应与传统的烯烃与甲酰胺的反应模式具有重要的互补性;
(3)三级甲酰胺因稳定性高时常作为有机反应的溶剂,前期报道的有限数量的已知三级胺与烯(炔)烃的氢胺化反应需要有其它反应试剂(如硅氢烷)存在或者是分步反应,反应条件苛刻,并且仅限于与活化烯烃的反应;
(4)本发明反应具有条件温和,底物普适性较好,无需添加剂等优点,得到的是反马氏加成的氢胺化产物,为甲酰胺的C-N键重组提供实用的方法。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚,下面结合具体的实施案例对本发明进一步说明。应该理解为,本发明实施案例的制备方法仅用于说明本发明,而不是对本发明的限制,本发明的保护范围并不仅限于此,在本发明的构思前提下,对本发明制备方法的简单改进都属于本发明要求保护的范围。
实施例1
室温下,在手套箱内,将0.025mmol催化剂La[N(TMS)2]3加入到带四氟乙烯旋塞和磁性搅拌子的25mLSchlenk反应瓶中,加溶剂DMF 3mL,充分搅拌溶解后,加入0.50mmol上式(I)化合,1.50mmol上式(II)化合物。将反应瓶从手套箱取出,放置加热模块上,搅拌升温至60℃,并在该温度下搅拌反应12小时。反应结束后,将混合物倾入乙酸乙酯中,加盐水洗涤,分离出水层,将水层用乙酸乙酯萃取,合并有机层(即合并洗涤后的有机层和萃取得到的有机层),用无水硫酸钠干燥,减压蒸馏除去溶剂,粗产物通过快速柱色谱(石油醚/乙酸乙酯,两者体积比为40:1)提纯,从而得到上式(III),产率为87%。1H NMR(CDCl3,400MHz,ppm):δ7.31-7.15(m,7H),6.75-6.66(m,3H),3.54(t,JH-H=7.5Hz,2H),2.86(s,3H),2.83(t,JH-H=8.1Hz,2H).13C NMR(CDCl3,100MHz,ppm):δ148.92,139.92,129.37,128.90,128.63,126.29,116.28,112.27,54.84,38.55,33.02。
实施例2:除将催化剂由La[N(SiMe3)2]3替换为Sm[N(SiMe3)2]3外,其它反应条件均不变的情况下,重复实施了实施例1。产率为75%。
实施例3:除将催化剂由La[N(SiMe3)2]3替换为Lu[N(SiMe3)2]3外,其它反应条件均不变的情况下,重复实施了实施例1。产率为70%。
实施例4:除将催化剂由La[N(SiMe3)2]3替换为Y[N(SiMe3)2]3外,其它反应条件均不变的情况下,重复实施了实施例1。产率为72%。
实施例5:除将催化剂由La[N(SiMe3)2]3替换为La[CH2SiMe3]3外,其它反应条件均不变的情况下,重复实施了实施例1。产率为80%。
实施例6:除将催化剂由La[N(SiMe3)2]3替换为(C5H5)2LaPh外,其它反应条件均不变的情况下,重复实施了实施例1。产率为79%。
实施例7:除将催化剂用量调整至15mol%外,其它反应条件均不变的情况下,重复实施了实施例1。产率为85%。
实施例8:除将溶剂由DMF替换为DME,反应温度调整至60℃外,其它反应条件均不变的情况下,重复实施了实施例1。产率为67%。
实施例9:除将溶剂由DMF替换为DMSO外,反应温度调整至60℃外,其它反应条件均不变的情况下,重复实施了实施例1。产率为55%。
实施例10:除将反应温度调整至80℃外,其它反应条件均不变的情况下,重复实施了实施例1。产率为83%。
实施例11
按照实施例1所述方法,0.50mmol上式(I)化合物与1.50mmol上式(II)化合物在0.025mmol催化剂La[N(TMS)2]3存在下于DMF(3mL)中加热(60℃)反应,得到上式(III),产率为94%。1H NMR(CDCl3,400MHz,ppm):δ7.35(t,JH-H=7.2Hz,2H),7.30–7.17(m,5H),6.67(d,JH-H=9.1Hz,2H),3.59(t,JH-H=7.9Hz,2H),2.89(s,3H),2.87(t,JH-H=7.4Hz,2H).13C NMR(CDCl3,100MHz,ppm):δ147.43,139.54,129.02,128.79,128.58,126.31,121.00,113.29,54.83,38.66,32.86。
实施例12
按照实施例1所述方法,0.50mmol上式(I)化合物与1.50mmol上式(II)化合物在0.025mmol催化剂La[N(TMS)2]3存在下于DMF(3mL)中加热(60℃)反应,得到上式(III),产率为77%。1H NMR(CDCl3,400MHz,ppm):δ7.40-7.36(m,4H),7.30(d,JH-H=7.2Hz,3H),6.80(d,JH-H=8.8Hz,2H),3.62(t,JH-H=8.3Hz,2H),2.97(s,3H),2.93(t,JH-H=7.4Hz,2H),1.40(s,9H).13C NMR(CDCl3,100MHz,ppm):δ146.76,140.05,138.92,128.87,128.58,126.21,126.11,112.06,55.06,38.54,33.82,33.13,31.67。
实施例13
按照实施例1所述方法,0.5mmol上式(I)化合物与1.50mmol上式(II)化合物在0.025mmol催化剂La[N(TMS)2]3存在下于DMF(3mL)中加热(60℃)反应,得到上式(III),产率为75%。1H NMR(CDCl3,400MHz,ppm):δ8.17(s,1H),7.97(s,1H),7.36–7.11(m,6H),6.98(d,JH-H=8.3Hz,1H),3.59(t,JH-H=7.5Hz,2H),2.90(s,3H),2.86(t,JH-H=7.6Hz,2H).13C NMR(CDCl3,100MHz,ppm):δ139.07,136.94,134.22,128.75,128.60,126.40,118.57,54.22,38.16,32.81。
实施例14
按照实施例1所述方法,0.5mmol上式(I)化合物与1.50mmol上式(II)化合物在0.025mmol催化剂La[N(TMS)2]3存在下于DMF(3mL)中加热(60℃)反应,得到上式(III),产率为72%。1H NMR(CDCl3,400MHz,ppm):δ7.43-7.21(m,7H),6.82(d,JH-H=8.1Hz,2H),6.75(t,JH-H=7.2Hz,1H),3.56(t,JH-H=8.0Hz,2H),3.37(q,J=7.0Hz,2H),2.93(t,JH-H=7.7Hz,2H),1.18(t,JH-H=7.0Hz,3H).13C NMR(CDCl3,100MHz,ppm):δ147.34,139.78,129.43,128.83,128.56,126.26,116.11,112.24,52.64,45.45,33.81,12.37。
实施例15
按照实施例1所述方法,0.5mmol上式(I)化合物与1.50mmol上式(II)化合物在0.025mmol催化剂La[N(TMS)2]3存在下于DMF(3mL)中加热(60℃)反应,得到上式(III),产率为57%。1H NMR(CDCl3,400MHz,ppm):δ7.34–7.24(m,2H),7.14(s,4H),6.83–6.70(m,3H),3.57(t,JH-H=7.9Hz,2H),2.93(s,3H),2.85(t,JH-H=7.7Hz,2H),2.37(s,3H).13C NMR(CDCl3,100MHz,ppm):δ148.78,136.63,135.65,129.24,129.19,128.64,116.14,112.17,54.86,38.47,32.38,21.03。
实施例16
按照实施例1所述方法,0.5mmol上式(I)化合物与1.50mmol上式(II)化合物在0.025mmol催化剂La[N(TMS)2]3存在下于DMF(3mL)中加热(60℃)反应,得到上式(III),产率为88%。1H NMR(CDCl3,400MHz,ppm):δ7.44(d,JH-H=8.2Hz,2H),7.29(t,JH-H=7.5Hz,2H),7.10(d,JH-H=8.1Hz,2H),6.75(d,JH-H=7.2Hz,3H),3.57(t,JH-H=7.5Hz,2H),2.89(s,3H),2.84(t,JH-H=7.5Hz,2H).13C NMR(CDCl3,100MHz,ppm):δ148.66,138.80,131.56,130.57,129.30,120.00,116.35,112.18,54.56,38.62,32.44。
实施例17
按照实施例1所述方法,0.5mmol上式(I)化合物与1.50mmol上式(II)化合物在0.025mmol催化剂La[N(TMS)2]3存在下于DMF(3mL)中加热(60℃)反应,得到上式(III),产率为70%。1H NMR(CDCl3,400MHz,ppm):δ8.61(d,JH-H=4.7Hz,1H),7.61(t,JH-H=7.5Hz,1H),7.29(d,JH-H=7.4Hz,2H),7.16(d,JH-H=7.6Hz,2H),6.79(d,JH-H=8.1Hz,2H),6.74(t,JH-H=7.2Hz,1H),3.78(t,JH-H=7.4Hz,3H),3.07(t,JH-H=7.4Hz,3H),2.92(s,3H).13C NMR(CDCl3,100MHz,ppm):δ159.88,149.44,148.83,136.42,129.23,123.57,121.32,116.21,112.23,52.96,38.33,35.27。
Claims (8)
2.根据权利要求1所述的方法,其特征在于,所述原料苯乙烯(II)与原料甲酰胺(I)用量之比为2-6倍。
3.根据权利要求2所述的方法,其特征在于,所述有机溶剂选自N,N-二甲基甲酰胺、DME、DMSO。
4.根据权利要求3所述的方法,其特征在于,所用有机溶剂的质量是原料甲酰胺(I)的10-30倍。
5.根据权利要求1所述的方法,其特征在于,所述催化剂选自稀土烷基配合物、稀土芳基配合物、稀土胺基配合物;所述稀土金属选自La、Sm、Yb、Lu、Y。
6.根据权利要求5所述的方法,其特征在于,所述稀土金属配合物催化剂与原料甲酰胺(I)的摩尔比为0.02 – 0.2。
7.根据权利要求1所述的方法,其特征在于,反应温度为60-80℃,反应时间12 -24小时。
8.根据权利要求1所述的方法,其特征在于,所述的分离纯化采用柱层析分离纯化法;即在反应结束后,将所得反应液蒸出溶剂,经湿法上样进行柱层析分离纯化、干燥即得目标产物;所用淋洗液为石油醚与乙酸乙酯混合物,石油醚与乙酸乙酯的体积比为50:1 -20:1。
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102755906A (zh) * | 2012-07-17 | 2012-10-31 | 苏州大学 | 一种氨基芳氧基稀土金属-锂胺化物作为催化剂的应用 |
CN110624542A (zh) * | 2019-09-27 | 2019-12-31 | 北京化工大学 | 一种催化烯烃和胺反马氏氢胺化反应的方法 |
CN113387886A (zh) * | 2021-05-11 | 2021-09-14 | 复旦大学 | 一种2-胺基二苯并[c,e]吖庚因化合物及其合成方法 |
CN113754689A (zh) * | 2021-08-03 | 2021-12-07 | 南京大学 | 一种镍催化的烯烃不对称氢胺化方法 |
CN114249639A (zh) * | 2021-12-02 | 2022-03-29 | 复旦大学 | 一种高效高选择性催化聚丙烯酮(酯)降解环化的方法 |
-
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102755906A (zh) * | 2012-07-17 | 2012-10-31 | 苏州大学 | 一种氨基芳氧基稀土金属-锂胺化物作为催化剂的应用 |
CN110624542A (zh) * | 2019-09-27 | 2019-12-31 | 北京化工大学 | 一种催化烯烃和胺反马氏氢胺化反应的方法 |
CN113387886A (zh) * | 2021-05-11 | 2021-09-14 | 复旦大学 | 一种2-胺基二苯并[c,e]吖庚因化合物及其合成方法 |
CN113754689A (zh) * | 2021-08-03 | 2021-12-07 | 南京大学 | 一种镍催化的烯烃不对称氢胺化方法 |
CN114249639A (zh) * | 2021-12-02 | 2022-03-29 | 复旦大学 | 一种高效高选择性催化聚丙烯酮(酯)降解环化的方法 |
Non-Patent Citations (1)
Title |
---|
周锡庚: "稀土催化的二级胺及其衍生物的新转化反应", 第十届全国无机化学学术会议, pages 1 * |
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