CN107033016A - 一种3‑氨基茚酮类化合物的合成方法 - Google Patents
一种3‑氨基茚酮类化合物的合成方法 Download PDFInfo
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- -1 amino indanone class compound Chemical class 0.000 title claims abstract description 27
- 238000010189 synthetic method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 150000002466 imines Chemical class 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 229940071125 manganese acetate Drugs 0.000 claims abstract description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims abstract description 4
- WUJLLKJTIKSMEJ-UHFFFAOYSA-L [Cl-].[Cl-].[Rh+2].CC1C(C)=C(C)C(C)=C1C Chemical compound [Cl-].[Cl-].[Rh+2].CC1C(C)=C(C)C(C)=C1C WUJLLKJTIKSMEJ-UHFFFAOYSA-L 0.000 claims abstract description 3
- 238000012805 post-processing Methods 0.000 claims abstract description 3
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical group OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 claims description 4
- HNXHMCTUYDVMNC-UHFFFAOYSA-N 3-amino-2,3-dihydroinden-1-one Chemical class C1=CC=C2C(N)CC(=O)C2=C1 HNXHMCTUYDVMNC-UHFFFAOYSA-N 0.000 claims description 3
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 3
- 125000005466 alkylenyl group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 229930192474 thiophene Natural products 0.000 claims description 2
- 150000003577 thiophenes Chemical class 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 239000000758 substrate Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 230000009466 transformation Effects 0.000 abstract description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 60
- 150000001875 compounds Chemical class 0.000 description 16
- 238000001228 spectrum Methods 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 8
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 4
- SNWQUNCRDLUDEX-UHFFFAOYSA-N inden-1-one Chemical compound C1=CC=C2C(=O)C=CC2=C1 SNWQUNCRDLUDEX-UHFFFAOYSA-N 0.000 description 4
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- 0 *C(C1=C(*)c2ccccc2C1=O)=O Chemical compound *C(C1=C(*)c2ccccc2C1=O)=O 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 150000001608 tolans Chemical class 0.000 description 2
- UOBYKYZJUGYBDK-UHFFFAOYSA-M 2-naphthoate Chemical compound C1=CC=CC2=CC(C(=O)[O-])=CC=C21 UOBYKYZJUGYBDK-UHFFFAOYSA-M 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- XMADUXVBEOQHDQ-UHFFFAOYSA-N CC1C(=C(C(=C1C)C)C)C.[Rh] Chemical compound CC1C(=C(C(=C1C)C)C)C.[Rh] XMADUXVBEOQHDQ-UHFFFAOYSA-N 0.000 description 1
- XGGAAWWJUHHFIJ-UHFFFAOYSA-N CCCCOC(C(C(C1=CC(F)=CC=C11)=O)=C1N)=O Chemical compound CCCCOC(C(C(C1=CC(F)=CC=C11)=O)=C1N)=O XGGAAWWJUHHFIJ-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- JRXXLCKWQFKACW-UHFFFAOYSA-N biphenylacetylene Chemical group C1=CC=CC=C1C#CC1=CC=CC=C1 JRXXLCKWQFKACW-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000003923 scrap metal Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
- C07C227/10—Formation of amino groups in compounds containing carboxyl groups with simultaneously increasing the number of carbon atoms in the carbon skeleton
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- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D333/78—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems condensed with rings other than six-membered or with ring systems containing such rings
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- C07F9/40—Esters thereof
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- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
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Abstract
本发明公开了一种3‑氨基茚酮类化合物的合成方法，包括如下步骤：将亚胺类衍生物、烯烃类化合物、二氯化五甲基环戊二烯铑、醋酸锰加入到有机溶剂中，空气条件下加热进行反应，反应完全后，后处理得到所述的3‑氨基茚酮类化合物。该方法通过简单易得的原料一步合成3‑氨基茚酮类化合物，转化效率高，原子经济性好；同时合成方法操作简单，反应收率高，同时底物适应性广。
Description
技术领域
本发明属于有机合成领域，具体涉及一种3-氨基茚酮类化合物的合成方法。
背景技术
茚酮是一类广泛存在于天然产物和药物分子的重要结构，同时在有机发光材料和染料方面也得到广泛应用。传统合成茚酮的方法通常需要底物预官能化，较多的反应步骤和较为苛刻的反应条件，同时传统的这些反应都会不可避免地产生大量的废碱，废酸以及金属废料。寻求发展新的不同方法是非常必要的。
过渡金属催化的C-H键活化是一种最近十几年才发展起来的一种实现原子经济型，减少反应步骤，合成复杂化合物的合成策略。过去几年中通过C-H键活化的方法来实现茚酮化合物的合成已经有所报道。例如，Li课题组报道了首例利用硝酮导向的铑催化的硝酮类化合物和二苯乙炔类化合物合成2，3-二芳基茚酮化合物，随后Shi课题组也报道了利用酰胺作为导向基团，铑催化的和二苯乙炔的反应，我们课题组和Li课题组在2016年又利用酯作为导向基团，钴催化的和二苯乙炔反应构筑茚酮化合物，这些报道都得到同样的2，3-二芳基取代的的茚酮。然而，利用C-H键的方法合成2，3-非芳基取代的茚酮化合物却没有报道，受最近利用亚胺酸酯作为导向基团跟不同反应底物合成多种杂化合物的启发，我们课题组首次发展了一种利用铑催化的亚胺酸酯和一系列吸电子烯烃一步合成2,3-双官能化的茚酮，该方法条件温和，反应适应性广，为合成不对称2,3-双官能化茚酮提供了一种简单有效的方法。
发明内容
本发明提供了一种3-氨基茚酮类化合物的合成方法，该合成方法底物适用性广，反应收率高。
一种3-氨基茚酮类化合物的合成方法，包括如下步骤：将亚胺类衍生物、烯烃类化合物、二氯化五甲基环戊二烯铑、醋酸锰加入到有机溶剂中，空气条件下加热进行反应，反应完全后，后处理得到所述的3-氨基茚酮类化合物；
所述的亚胺类衍生物的结构如式(II)所示：
所述的烯烃类化合物的结构如式(III)所示：
所述的3-氨基茚酮类化合物的结构如式(I)所示：
式(I)～(III)中，R1选自H、C1～C4烷基、三氟甲基、卤素、取代萘基或取代噻吩基；
R2为-COOR3、-CONR4R5或-SO2R6，其中，R3、R4、R5和R6独立地选自C1～C4烷基或苯基。
作为优选，所述的3-氨基茚酮类化合物为式(I-1)-式(I-10)所示化合物中的一种：
作为优选，所述的有机溶剂为三氟乙醇(TFE)。
作为优选，反应温度为60～80℃，反应时间为2～10小时。
同现有技术相比，本发明的有益效果体现在：
(1)本发明通过简单易得的原料一步合成3-氨基茚酮类化合物，转化效率高，原子经济性好；
(2)本发明的合成方法操作简单，反应收率高，同时底物适应性广。
附图说明
图1为实施例1得到的化合物的氢谱和碳谱谱图；
图2为实施例2得到的化合物的氢谱和碳谱谱图；
图3为实施例3得到的化合物的氢谱和碳谱谱图；
图4为实施例4得到的化合物的氢谱和碳谱谱图；
图5为实施例5得到的化合物的氢谱和碳谱谱图；
图6为实施例6得到的化合物的氢谱和碳谱谱图；
图7为实施例7得到的化合物的氢谱和碳谱谱图；
图8为实施例8得到的化合物的氢谱和碳谱谱图；
图9为实施例9得到的化合物的氢谱和碳谱谱图；
图10为实施例10得到的化合物的氢谱和碳谱谱图；
图11为实施例11得到的化合物的氢谱和碳谱谱图；其中，氢谱在400MHz核磁仪器上进行测试。碳谱在100MHz核磁仪器上进行测试。测试条件均为室温下使用四甲基硅烷作内标，样品用氘代二甲基亚砜溶解。
具体实施方式
下面结合具体实施例对本发明做进一步的描述，以下具体实施例都是本发明的最优实施方式。
实施例1～11
按照表1的原料配比在试管中加入亚胺(0.2mmol)、烯烃类化合物(0.4mmol)、二氯化五甲基环戊二烯铑(0.02mmol)、醋酸锰(0.2mmol)、和有机溶剂1ml，混合搅拌均匀，按照表2的反应条件反应完成后，冷却，抽滤，硅胶拌样，经过柱层析纯化得到相应的3-氨基茚酮化合物(Ⅰ)，反应过程如下式所示：
表1 实施例1～11的原料配比
表2 实施例1～11的反应条件和反应结果
表1和表2中，T为反应温度，t为反应时间，n-Bu为正丁基，2-naphthyl为2-取代萘基，CF3为三氟甲基，Ph为苯基，2-thiophene为2-取代噻吩。
实施例1～10制备得到部分化合物的结构确认数据：
butyl 3-amino-1-oxo-1H-indene-2-carboxylate(I-1)
Yield:(40.2mg,82％)；Yellow solid；m.p:166.2-167.0℃.1H NMR(DMSO,400MHz)δ9.66(s,1H),9.03(s,1H),7.99-7.97(m,1H),7.60-7.58(m,2H),7.47-7.45(m,1H),4.14(t,J＝6.8Hz,2H),1.64-1.59(m,2H),1.43-1.37(m,2H),0.92(t,J＝7.6Hz,3H).13C NMR(DMSO,100MHz)δ186.2,170.6,165.1,135.6,135.2,132.9,131.8,121.1,120.8,93.4,62.0,30.6, 18.7,13.6.HRMS(EI-TOF)calcd for C14H15NO3[M+Na+]:268.0950,found:268.0953.
butyl 3-amino-6-methyl-1-oxo-1H-indene-2-carboxylate(I-2)
Yield:(40.4 mg,78％)；Yellow solid；m.p:207.6-208.6℃.1H NMR(DMSO,400MHz)δ9.60(s,1H),8.99(s,1H),7.85(d,J＝7.6 Hz,1H),7.37(d,J＝8 Hz,1H),7.29(s,1H),4.14(t,J＝6.8 Hz,2H),2.39(s,3H),1.66-1.59(m,2H),1.45-1.36(m,2H),0.92(t,J＝7.6 Hz,3H).13C NMR(DMSO,100MHz)δ186.3,170.8,165.1,143.3,136.0,132.5,131.9,121.6,121.0,93.3,61.9,30.6,21.3,18.7,13.6.HRMS(EI-TOF)calcd forC15H17NO3[M+Na+]:282.1106,found:282.1113.
butyl 3-amino-6-fluoro-1-oxo-1H-indene-2-carboxylate
Yield:(35.8 mg,68％)；Yellow solid；m.p:222.8-223.8 ℃.1H NMR(DMSO,400MHz)δ9.71(s,1H),9.07(s,1H),7.97(dd,J1＝8.4 Hz,J2＝4.8Hz,1H),7.38-7.32(m,1H),7.20(dd,J1＝7.6 Hz,J2＝2.4 Hz,1H),4.08(t,J＝6.8 Hz,2H),1.59-1.52(m,2H),1.38-1.29(m,2H),0.86(t,J＝7.6 Hz,3H).13CNMR(DMSO,100 MHz)δ184.2,169.9,164.8,165.4(d,J1C-F＝250.1 Hz),139.1(d,J3C-F＝8.1 Hz),131.0(d,J4C-F＝2.7 Hz),123.5(d,J3C-F＝9.1 Hz),117.9(d,J2C-F＝23.4 Hz),108.9(d,J2C-F＝24.4 Hz),94.1(d,J4C-F＝2.7 Hz),62.1,30.5,18.7,13.6.HRMS(EI-TOF)calcd forC14H14FNO3[M+Na+]:286.0855,found:286.0861.
butyl 3-amino-1-oxo-6-(trifluoromethyl)-1H-indene-2-carboxylate(I-4)
Yield:(37.6 mg,60％)；Yellow solid；m.p:229.6-231.5℃.1H NMR(DMSO,400MHz)δ9.93(s,1H),9.24(s,1H),8.25(d,J＝7.6 Hz,1H),8.07(d,J＝7.6 Hz,1H),7.71(s,1H),4.21(t,J＝6.4 Hz,2H),1.71-1.64(m,2H),1.49-1.40(m,2H),0.97(t,J＝7.6 Hz,3H).13C NMR(DMSO,100 MHz)δ184.3,169.1,164.8,139.1,136.4,132.6(q,JCF3-C＝32.5Hz),129.3(q,JCF3-C＝3.6 Hz),125.0,122.3,122.0,117.0(d,JCF3-C＝3.6 Hz),94.8,62.3,30.5,18.7,13.6.HRMS(EI-TOF)calcd for C15H14F3NO3[M+Na+]:336.0823,found:336.0827.
butyl 3-amino-6-nitro-1-oxo-1H-indene-2-carboxylate(I-5)
Yield:(38.3 mg,66％)；Yellow solid；m.p:239.2-240.8℃.1H NMR(DMSO,400MHz)δ10.01(s,1H),9.23(s,1H),8.52(d,J＝6.8 Hz,1H),8.28(d,J＝8.0 Hz,1H),8.08(s,1H),4.21(t,J＝6.4 Hz,2H),1.72-1.65(m,2H),1.48-1.41(m,2H),0.98(t,J＝7.2 Hz,3H).13C NMR(DMSO,100 MHz)δ183.4,168.3,164.6,150.5,140.8,136.8,127.6,122.4,115.1,95.9,62.4,30.4,18.7,13.6.HRMS(EI-TOF)calcd for C14H14N2O5[M+Na+]:313.0800,found:313.0806.
butyl 6-amino-4-oxo-4H-cyclopenta[b]thiophene-5-carboxylate(I-6)
Yield:(16.4 mg,30％)；Orangesolid；m.p:176.8-178.0℃.1H NMR(DMSO,400MHz)δ9.88(s,1H),8.95(s,1H),7.84(d,J＝4.8 Hz,1H),7.05(d,J＝4.8 Hz,1H),4.05(t,J＝6.8 Hz,2H),1.56-1.49(m,2H),1.36-1.27(m,2H),0.85(t,J＝7.6 Hz,3H).13C NMR(DMSO,100 MHz)δ182.3,166.4,164.5, 147.2,141.7,137.0,120.1,91.4,61.6,30.7,18.7,13.6.HRMS(EI-TOF)calcdfor C12H13NO3S[M+Na+]:274.0514,found:274.0522.
butyl 3-amino-1-oxo-1H-cyclopenta[a]naphthalene-2-carboxylate(I-7)
Yield:(20.7 mg,35％)；Orangesolid；m.p:206.8-208.9℃.1H NMR(DMSO,400MHz)δ9.76(s,1H),9.10(s,1H),8.91(d,J＝8.0 Hz,1H),8.08(dd,J1＝12.8 Hz,J2＝8.0Hz,2H),7.92(d,J＝8.4 Hz,1H),7.59-7.51(m,2H),4.09(t,J＝6.4 Hz,2H),1.61-1.54(m,2H),1.41-1.32(m,2H),0.88(t,J＝7.2Hz,3H).13C NMR(DMSO,100 MHz)δ188.8,171.0,164.9,136.1,134.7,132.3,128.7,128.5,127.7,127.4,124.1,117.7,91.8,61.9,30.6,18.8,13.7.HRMS(EI-TOF)calcd for C18H17NO3[M+Na+]:318.1106,found:318.1112.
3-amino-N,N-dimethyl-1-oxo-1H-indene-2-carboxamide(I-8)
Yield:(22.5 mg,52％)；Yellow solid；m.p:239.4-241.5℃.1H NMR(DMSO,400MHz)δ9.08(s,1H),8.56(s,1H),7.76-7.75(m,1H),7.44-7.42(m,2H),7.32-7.30(m,1H),2.87(s,6H).13C NMR(DMSO,100 MHz)δ186.3,169.0,136.0,135.3,132.0,131.3,120.3,120.2,98.3,45.5.HRMS(EI-TOF)calcd for C12H12N2O2[M+Na+]:239.0796,found:239.0797.
dimethyl(3-amino-1-oxo-1H-inden-2-yl)phosphonate(I-9)
Yield:(30.4 mg,60％)；Yellow solid；m.p:167.4-168.9℃.1H NMR(DMSO,400MHz)δ9.51(s,1H),8.60(s,1H),8.03-8.01(m,1H),7.65-7.63(m,2H),7.53-7.51(m,1H),3.66(s,3H),3.64(s,3H).13C NMR(DMSO,100MHz)δ189.2,189.1,173.3,173.2,136.7,136.5,135.9,135.8,132.5,131.8,121.0,120.7,84.9,82.9,51.9,51.8.HRMS(EI-TOF)calcd forC11H12NO4P[M+Na+]:276.0402,found:276.0405.
3-amino-2-(phenylsulfonyl)-1H-inden-1-one(I-10)
Yield:(26.8 mg,47％)；Yellow solid；m.p:175.8-176.8℃.1H NMR(DMSO,400MHz)δ9.84(s,1H),9.00(s,1H),8.06(d,J＝6.0 Hz,1H),7.97(d,J＝7.2 Hz,2H),7.63-7.60(m,5H),7.45(s,1H).13C NMR(DMSO,100MHz)δ184.4,165.8,143.8,134.9,134.2,133.2,132.6,132.4,129.0,126.1,122.0,121.1,99.3.HRMS(EI-TOF)calcd for C15H11NO3S[M+Na+]:308.0357,found:308.0360。
Claims (4)
1.一种3-氨基茚酮类化合物的合成方法，其特征在于，包括如下步骤：将亚胺类衍生物、烯烃类化合物、二氯化五甲基环戊二烯铑、醋酸锰加入到有机溶剂中，空气条件下加热进行反应，反应完全后，后处理得到所述的3-氨基茚酮类化合物；
所述的亚胺类衍生物的结构如式(II)所示：
所述的烯烃类化合物的结构如式(III)所示：
所述的3-氨基茚酮类化合物的结构如式(I)所示：
式(I)～(III)中，R1选自H、C1～C4烷基、三氟甲基、卤素、取代萘基或取代噻吩基；
R2为-COOR3、-CONR4R5或-SO2R6，其中，R3、R4、R5和R6独立地选自C1～C4烷基或苯基。
2.根据权利要求1所述的3-氨基茚酮类化合物的合成方法，其特征在于，所述的3-氨基茚酮类化合物为式(I-1)-式(I-11)所示化合物中的一种：
3.根据权利要求1所述的3-氨基茚酮类化合物的合成方法，其特征在于，所述的有机溶剂为三氟乙醇(TFE)。
4.根据权利要求1所述的3-氨基茚酮类化合物的合成方法，其特征在于，反应温度为60～80℃，反应时间为2～10小时。
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| CN107586298A (zh) * | 2017-08-14 | 2018-01-16 | 浙江大学 | 一种含氮螺环化合物的合成方法 |
| CN110372519A (zh) * | 2019-06-17 | 2019-10-25 | 浙江大学 | 一种3-氨基茚类化合物的合成方法 |
| CN112939780A (zh) * | 2020-09-15 | 2021-06-11 | 浙江大学 | 一种茚酮类衍生物的合成方法 |
| CN115057808A (zh) * | 2022-06-23 | 2022-09-16 | 温州大学 | 一种z-3-乙烯基取代的异吲哚啉酮类化合物的合成方法 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107586298A (zh) * | 2017-08-14 | 2018-01-16 | 浙江大学 | 一种含氮螺环化合物的合成方法 |
| CN107586298B (zh) * | 2017-08-14 | 2019-10-25 | 浙江大学 | 一种含氮螺环化合物的合成方法 |
| CN110372519A (zh) * | 2019-06-17 | 2019-10-25 | 浙江大学 | 一种3-氨基茚类化合物的合成方法 |
| CN110372519B (zh) * | 2019-06-17 | 2023-04-11 | 浙江大学 | 一种3-氨基茚类化合物的合成方法 |
| CN112939780A (zh) * | 2020-09-15 | 2021-06-11 | 浙江大学 | 一种茚酮类衍生物的合成方法 |
| CN115057808A (zh) * | 2022-06-23 | 2022-09-16 | 温州大学 | 一种z-3-乙烯基取代的异吲哚啉酮类化合物的合成方法 |
| CN115057808B (zh) * | 2022-06-23 | 2023-08-04 | 温州大学 | 一种z-3-乙烯基取代的异吲哚啉酮类化合物的合成方法 |
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