CN114478576A - Synthetic method of spiroheterocyclic compound - Google Patents

Synthetic method of spiroheterocyclic compound Download PDF

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CN114478576A
CN114478576A CN202210157582.9A CN202210157582A CN114478576A CN 114478576 A CN114478576 A CN 114478576A CN 202210157582 A CN202210157582 A CN 202210157582A CN 114478576 A CN114478576 A CN 114478576A
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silver
spiroheterocyclic
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杨西发
李祥
樊良鑫
安世恒
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Henan Agricultural University
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
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Abstract

The invention provides a synthesis method of a spiro-heterocyclic compound, which is used for solving the technical problems of complex substrate synthesis, limited functional group, inadequately mild reaction conditions, difficult industrialization in the later period and other practical defects in the synthesis of the existing spiro-heterocyclic compound, and comprises the following specific steps: adding a 3-aryl benzoxazine compound, a diazo compound, a catalyst and an additive into a solvent, reacting under the protection of inert atmosphere, and purifying after the reaction is finished to obtain the spiroheterocyclic compound. The invention provides a simple and effective synthesis method for the construction of a complex spiro ring, and the method has the characteristics of mild reaction conditions, simple operation, atom economy, economic steps, strong functional group tolerance, good yield and the like; the obtained product has wide industrial application prospect, and provides a new idea and a new method for the fields of medicine, natural product synthesis, luminescent materials and the like.

Description

Synthetic method of spiroheterocyclic compound
Technical Field
The invention belongs to the technical field of organic synthetic chemistry, and particularly relates to a synthetic method of a spiroheterocyclic compound.
Background
The C-H bond is a basic structural unit for forming an organic compound, widely exists in petrochemical industry, biomass, natural products, medicines, organic functional materials and the like, and development of simple, efficient and high-selectivity C-H bond functionalization is an important direction for researches of chemists all the time, and the fundamental reason is that: by reducing the synthesis steps of the compound, the cost is saved, the atom economy of synthesis conversion is improved, and the harm to the environment is relieved. Therefore, it is desirable to construct complex cyclic compounds using the C-H bond activation strategy. The high-efficiency functionalization of C-H bonds is an important research content of organic synthetic chemistry and one of the most challenging leading research fields, has important significance for chemical basic research and development of fields such as medicine, chemical industry, environment, energy, materials and the like, and is known as 'chemical holy cup' (Acta Chim. Sinica 2015,73,1223) by students.
Spirocycles, i.e., a special ring system in which two rings share one carbon atom, tend to have a strong rigidity and good stability in the skeleton. Also, we have readily found that the presence of a spiro backbone is often seen among biologically active natural products and biologically active molecules, and that this type of backbone is often the core backbone of many drug molecules (bioorg. Med. chem. Lett.1999,9,2921; chem. Rev.2007,107, 1011; nat. chem.2018,9, 1). In addition, the spiro skeleton also shows excellent catalytic performance and optical performance in the asymmetric catalytic field (Acc.chem.Res.2018,41,581) and the photoelectric material field (chem.Rev.,2016,116,14675; org.Electron.,2018,61, 376). In view of this, the efficient synthesis of the skeleton is always the focus of attention of synthetic chemists, and most of scientists at home and abroad realize the construction of a variety of spiro molecules by means of various synthesis methods, and especially under the promotion of a transition metal catalyst, the synthesis of the spiro skeleton takes a new step. The existing synthesis means often needs to perform pre-functionalization on a substrate (introduce halogen, a guide group and the like), so that the difficulty of the substrate in synthesis is increased, and the later removal of the guide group also limits the further development of the reaction. Meanwhile, the substrate used by the existing synthesis means generally needs multi-step synthesis, and the diversity of the obtained frameworks is limited. In addition, for complex spiro rings containing multiple ring systems, ring-by-ring construction is generally required, and the process economy is low. Therefore, the aim of synthesizing cumin by chemists is always to explore a simple and efficient synthesis means.
Disclosure of Invention
The invention provides a synthesis method of a spiro [4.5] heterocyclic compound, which adopts a simple and easily-obtained 3-arylbenzoxazine compound and a diazo compound as reactants, completes the fracture and recombination of a plurality of chemical bonds in one-step chemical transformation through a series strategy of [4+2] and [3+3] under the catalysis of cyclopentadienyl rhodium complex, prepares a spiro [5.5] heterocyclic skeleton containing a quaternary carbon center, and realizes the purposes of simple and easily-obtained reaction raw materials, mild reaction conditions and simple operation.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a synthesis method of spiro-heterocyclic compounds takes 3-aryl benzoxazine compounds and diazo compounds as raw materials, and synthesizes novel spiro-heterocyclic compounds under the promotion of catalysts, wherein the reaction formula is as follows:
Figure BDA0003513395460000021
wherein R is any one of H, Me, F, Cl and Br; r1Any one of Me, Pr and Ph; r2Is Me, Et,iAny one of Pr; ar is Me, OMe, F, Cl, Br, Ph, CF3Any one of the substituted benzene rings.
The synthesis method of the spiro-heterocyclic compound comprises the following specific steps: adding a 3-aryl benzoxazine compound, a diazo compound, a catalyst and an additive into a solvent, reacting under the protection of inert atmosphere, and purifying after the reaction is finished to obtain the spiroheterocyclic compound.
The catalyst comprises a rhodium catalyst and a silver salt; the molar ratio of rhodium catalyst to silver salt is 1: (2-4); the rhodium catalyst is dichloro (pentamethylcyclopentadienyl) rhodium dimer ([ Cp & RhCl)2]2) Pentamethylcyclopentadienyl rhodium acetate (CpRh (OAc))2) Or bis (hexafluoroantimonic acid) triethylenenitrile (pentamethylcyclopentadienyl) rhodium (CpRh (CH)3CN)3(SbF6)2) Any one of the above; the silver salt is silver hexafluoroantimonate (AgSbF)6) Bis (trifluoromethanesulfonyl) imide silver (AgNTf)2) Silver tetrafluoroborate (AgBF)4) Silver trifluoromethanesulfonate (AgOTf), silver sulfate (Ag)2SO4) And silver acetate (AgOAc) and silver trifluoroacetate (AgTFA).
The catalyst consists of dichloro (pentamethylcyclopentadienyl) rhodium dimer and silver hexafluoroantimonate, and the molar ratio of the dichloro (pentamethylcyclopentadienyl) rhodium dimer to the silver hexafluoroantimonate is 1: 4.
the additive is any one of trimesoyl benzoic acid, pivalic acid, acetic acid, benzoic acid, proline, adamantane formic acid, zinc acetate, sodium carbonate, potassium acetate and potassium carbonate.
The solvent is any one of dichloroethane, dichloromethane, methanol, acetonitrile, 1, 4-dioxane and toluene.
The 3-aryl benzoxazine compound: diazo compound: catalyst: the molar ratio of the additive is 1: 2.2: 0.02-0.04: 0.08-0.16.
The concentration of the reaction system in the solvent is 0.05M-0.2M.
The inert atmosphere is a nitrogen atmosphere.
The reaction temperature is 30-90 ℃, and the reaction time is 0.5-6 h.
The reaction mode of this reaction is shown in FIG. 35. Firstly, obtaining a pentabasic rhodium hetero intermediate A under the co-catalysis of rhodium and silver by a substrate 1a, then coordinating a diazo reagent with the intermediate A to obtain a rhodium carbene intermediate B, then carrying out carbene migration and insertion to obtain an intermediate C, then carrying out metal elimination to obtain an intermediate compound D, carrying out enol isomerization on the compound D, wherein enol hydroxyl attacks an imine bond to obtain an intermediate E, carrying out the interaction between the intermediate E and a metal rhodium catalyst again to obtain an intermediate F, carrying out the same quick interconversion on the intermediate F into the enol intermediate G, carrying out further nucleophilic attack on the intermediate G to obtain an intermediate H, and finally carrying out further addition-elimination reaction on the intermediate H to obtain a final target compound 4 aa.
The invention has the beneficial effects that: the invention creatively selects simple and easily obtained oxazine compounds and diazo compounds as reactants, realizes the construction of a novel spiro [5.5] heterocyclic skeleton containing a quaternary carbon center in one step by a series strategy of [4+2] and [3+3] under the catalysis of cyclopentadienyl rhodium complexes, provides a simple and effective synthetic method for the construction of a complex spiro, and has the characteristics of mild reaction conditions, simple operation, atom economy, economic steps, strong functional group tolerance, good yield and the like. The obtained product has wide industrial application prospect, and provides a new idea and a new method for the fields of medicine, natural product synthesis, luminescent materials and the like.
Drawings
FIG. 1 is nuclear magnetism of compound 4aa1H, spectrogram; FIG. 2 Nuclear magnetism of Compound 4aa13And C, spectrum.
FIG. 3 nuclear magnetism of Compound 4ba1H, spectrogram; FIG. 4 nuclear magnetism of Compound 4ba13And C, spectrum.
FIG. 5 shows nuclear magnetism of Compound 4ca1H, spectrogram; FIG. 6 shows nuclear magnetism of Compound 4ca13And C, spectrum.
FIG. 7 shows NMR spectra for Compound 4da1H, spectrogram; FIG. 8 nuclear magnetism of Compound 4da13And C, spectrum.
FIG. 9 is nuclear magnetism of Compound 4ea1H, spectrogram; FIG. 10 is nuclear magnetism of Compound 4ea13And C, spectrum.
FIG. 11 is nuclear magnetism of compound 4fa1H, spectrogram; FIG. 12 nuclear magnetism of compound 4fa13And C, spectrum.
FIG. 13 nuclear magnetism of Compound 4ga1H, spectrogram; FIG. 14 is of Compound 4gaNuclear magnetism13And C, spectrum.
FIG. 15 is nuclear magnetism of compound 4ha1H, spectrogram; FIG. 16 is nuclear magnetism of compound 4ha13And C, spectrum.
FIG. 17 is nuclear magnetism of Compound 4ia1H, spectrogram; FIG. 18 is nuclear magnetism of Compound 4ia13And C, spectrum.
FIG. 19 NMR of Compound 4ja1H, spectrogram; FIG. 20 Nuclear magnetism of Compound 4ja13And C, spectrum.
FIG. 21 nuclear magnetism of Compound 4ka1H, spectrogram; FIG. 22 is nuclear magnetism of Compound 4ka13And C, spectrum.
FIG. 23 is nuclear magnetism of compound 4la1H, spectrogram; FIG. 24 is nuclear magnetism of compound 4la13And C, spectrum.
FIG. 25 nuclear magnetism of Compound 4ma1H, spectrogram; FIG. 26 nuclear magnetism of Compound 4ma13And C, spectrum.
FIG. 27 Nuclear magnetism of Compound 4na1H, spectrogram; FIG. 28 is nuclear magnetism of compound 4na13And C, spectrum.
FIG. 29 is nuclear magnetism of Compound 4ab1H, spectrogram; FIG. 30 NMR of Compound 4ab13And C, spectrum.
FIG. 31 nuclear magnetism of Compound 4ac1H, spectrogram; FIG. 32 NMR of Compound 4ac13And C, spectrum.
FIG. 33 NMR of Compound 4ad1H, spectrogram; FIG. 34 NMR of Compound 4ad13And C, spectrum.
FIG. 35 is a reaction scheme of the synthetic pathway.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
Figure BDA0003513395460000041
Under the condition of nitrogen, 3-aryl benzoxazine compound 1a (0.20mmol), diazo compound 2a (0.44mmol), [ Cp + RhCl2]2(4mol％)，AgSbF6(16 mol%), MesCOOH (0.4mmol) and solvent DCE (2.0mL) were added into a 10mL sealed tube, reacted in a 30 ℃ reaction block for 30min, after the reaction was completed, the solvent was removed under reduced pressure, and the desired product, 8, 14-dimethyl-6H-benzo [5,6 ], was isolated by silica gel column][1,4]Oxazines [3,4-a ]]Pyran [4,3,2-ij ]]Isoquinoline-9, 13-dicarboxylic acid diethyl ester (4aa), and all eluents are petroleum ether, ethyl acetate and dichloromethane which are prepared according to the ratio of 30:1: 1.
And (3) product data characterization: brown liquid, 88% yield. As shown in figures 1 and 2 of the drawings,1H NMR(400MHz,CDCl3)δ7.47(dd,J＝8.0,1.0Hz,1H),7.30(t,J＝8.0Hz,1H),7.18–7.06(m,3H),6.97–6.88(m,2H),4.55(d,J＝11.4Hz,1H),4.37–4.31(ddt,J＝9.4,7.1,3.7Hz,4H),4.16(d,J＝11.4Hz,1H),2.14(s,3H),2.09(s,3H),1.37(t,J＝7.1Hz,6H).13C NMR(101MHz,CDCl3)δ168.5,166.6,160.2,149.3,143.7,130.2,128.2,128.1,126.9,125.5,121.6,121.5,119.9,116.7,115.0,109.0,105.7,86.2,64.1,60.9,60.8,19.5,19.3,14.4.HRMS[M+H]+calculated for C26H26NO6 +＝448.1755,found:448.1758.
example 2
Figure BDA0003513395460000042
Under the condition of nitrogen, 3-aryl benzoxazine compound 1b (0.20mmol), diazo compound 2a (0.44mmol), [ Cp + RhCl2]2(2mol％)，AgSbF6(8mol percent), MesCOOH (0.4mmol) and a solvent DCE (2.0mL) are added into a 10mL sealed tube and reacted for 1H in a 40-degree reaction module, the solvent is removed under reduced pressure after the reaction is finished, and the target product, 4-bromo-8, 14-dimethyl-6H-benzo [ 5], is obtained by silica gel column separation,6][1,4]Oxazines [3,4-a ]]Pyran [4,3,2-ij ]]Isoquinoline-9, 13-dicarboxylic acid diethyl ester (4ba), and all eluents are petroleum ether, ethyl acetate and dichloromethane which are prepared according to the ratio of 30:1: 1.
And (3) product data characterization: white solid, 88% yield. Melting range: 127 ℃ and 128 ℃. As shown in figures 3 and 4 of the drawings,1H NMR(400MHz,CDCl3)δ7.48(d,J＝7.9Hz,1H),7.43(dd,J＝8.0,1.2Hz,1H),7.32(t,J＝8.0Hz,1H),7.14(d,J＝7.9Hz,1H),7.06(dd,J＝8.0,1.2Hz,1H),6.83(t,J＝8.0Hz,1H),4.71(d,J＝11.4Hz,1H),4.39–4.30(m,4H),4.24(d,J＝11.4Hz,1H),2.12(s,3H),2.09(s,3H),1.38–1.35(m,6H).13C NMR(101MHz,CDCl3)δ168.2,166.4,159.7,146.1,142.9,130.4,130.3,128.1,127.9,127.3,126.7,121.8,121.6,120.4,114.9,110.3,109.2,106.4,85.8,64.9,60.9,60.8,19.3,19.2,14.4,14.4.HRMS[M+H]+calculated for C26H25BrNO6 +＝526.0860,found:526.0861.
example 3
Figure BDA0003513395460000051
Under the condition of nitrogen, 3-aryl benzoxazine compound 1c (0.20mmol), diazo compound 2a (0.44mmol), [ Cp + RhCl2]2(3mol％)，AgSbF6(12 mol%), MesCOOH (0.4mmol) and solvent DCE (2.0mL) were added into a 10mL sealed tube, reacted in a 40 ℃ reaction block for 30min, after the reaction was completed, the solvent was removed under reduced pressure, and the desired product, 3-fluoro-8, 14-dimethyl-6H-benzo [5,6 ] was isolated by silica gel column][1,4]Oxazines [3,4-a ]]Pyran [4,3,2-ij ]]Isoquinoline-9, 13-dicarboxylic acid diethyl ester (4ca), and all eluents are petroleum ether, ethyl acetate and dichloromethane which are prepared according to the ratio of 30:1: 1.
And (3) product data characterization: white solid, 73% yield. Melting range: 180 ℃ and 181 ℃. As shown in figures 5 and 6 of the drawings,1H NMR(400MHz,CDCl3)δ7.47(d,J＝7.9Hz,1H),7.30(t,J＝8.0Hz,1H),7.13(d,J＝7.9Hz,1H),7.03(dd,J＝8.5,6.1Hz,1H),6.67(dd,J＝13.2,5.7Hz,2H),4.52(d,J＝11.4Hz,1H),4.43–4.27(m,4H),4.15(d,J＝11.5Hz,1H),2.10(s,3H),2.10(s,3H),1.38–1.35(m,6H).13C NMR(101MHz,CDCl3)δ168.3,166.5,161.1(d,J＝244.8Hz),159.8,150.2,150.0,143.5,130.3,128.7(d,J＝10.0Hz),128.1,121.8(d,J＝3.0Hz),121.7,121.5,114.7,109.0,107.1(d,J＝23.0Hz),105.9,103.9(d,J＝26.0Hz),86.1,64.0,60.9,60.8,19.3,19.3,14.4,14.4.HRMS[M+H]+calculated for C26H25FNO6 +＝466.1660,found:466.1661
example 4
Figure BDA0003513395460000061
Under the condition of nitrogen, 3-aryl benzoxazine compound 1d (0.20mmol), diazo compound 2a (0.44mmol), [ Cp + RhCl2]2(4mol％)，AgSbF6(16 mol%), MesCOOH (0.4mmol) and solvent DCE (2.0mL) were added in a 10mL sealed tube, reacted for 2H in a 40 ℃ reaction block, after the reaction was completed, the solvent was removed under reduced pressure, and the desired product, 3-chloro-8, 14-dimethyl-6H-benzo [5,6 ] was isolated by silica gel column][1,4]Oxazines [3,4-a ]]Pyran [4,3,2-ij ]]Isoquinoline-9, 13-dicarboxylic acid diethyl ester (4da), and all eluents are petroleum ether, ethyl acetate and dichloromethane which are prepared according to the ratio of 30:1: 1.
And (3) product data characterization: white solid, 84% yield. Melting range: 201 ℃ and 202 ℃. As shown in figures 7 and 8 of the drawings,1H NMR(400MHz,CDCl3)δ7.48(d,J＝7.8Hz,1H),7.30(t,J＝8.0Hz,1H),7.12(d,J＝7.5Hz,1H),7.01(d,J＝8.4Hz,1H),6.95–6.91(m,2H),4.54(d,J＝11.4Hz,1H),4.40–4.28(m,4H),4.14(d,J＝11.4Hz,1H),2.11(s,3H),2.11(s,3H),1.39–1.35(m,6H).13C NMR(101MHz,CDCl3)δ168.3,166.5,159.9,149.8,143.0,131.9,130.3,128.7,128.2,128.0,124.3,121.8,121.6,120.2,116.9,114.7,109.1,106.2,86.0,64.1,61.0,60.9,19.3,19.3,14.4.HRMS[M+H]+calculated for C26H25ClNO6 +＝482,1365,found:482.1364.
example 5
Figure BDA0003513395460000062
Under the condition of nitrogen, 3-aryl benzoxazine compound 1e (0.20mmol), diazo compound 2a (0.44mmol), [ Cp + RhCl2]2(2mol％)，AgSbF6(8 mol%), MesCOOH (0.4mmol) and solvent DCE (2.0mL) were added to a 10mL sealed tube, reacted in a 30 ℃ reaction block for 0.5H, after the reaction was complete, the solvent was removed under reduced pressure, and the desired product, 3-bromo-8, 14-dimethyl-6H-benzo [5,6 ] -was isolated on a silica gel column][1,4]Oxazines [3,4-a ]]Pyran [4,3,2-ij ]]Isoquinoline-9, 13-dicarboxylic acid diethyl ester (4ea), and all eluents are petroleum ether, ethyl acetate and dichloromethane which are prepared according to the ratio of 30:1: 1.
And (3) product data characterization: white solid, 81% yield. Melting range: 195 ℃ and 196 ℃. As shown in figures 9 and 10 of the drawings,1H NMR(400MHz,CDCl3)δ7.47(d,J＝7.4Hz,1H),7.30(t,J＝8.0Hz,1H),7.16–7.03(m,3H),6.95(d,J＝8.5Hz,1H),4.54(d,J＝11.4Hz,1H),4.45–4.25(m,4H),4.13(d,J＝11.4Hz,1H),2.11(s,3H),2.11(s,3H),1.39–1.35(m,6H).13C NMR(101MHz,CDCl3)δ168.3,166.5,159.9,149.9,142.9,130.3,129.0,128.2,128.0,124.8,123.1,121.8,121.6,119.8,119.5,114.7,109.1,106.2,86.0,64.1,61.0,60.9,19.3,19.3,14.4.HRMS[M+H]+calculated for C26H25BrNO6 +＝526.0860,found:526.0858.
example 6
Figure BDA0003513395460000071
Under the condition of nitrogen, 3-aryl benzoxazine compound 1f (0.20mmol), diazo compound 2a (0.44mmol), [ Cp + RhCl2]2(4mol％)，AgSbF6(16 mol%), MesCOOH (0.4mmol) and solvent DCE (2.0mL) were added to a 10mL sealed tube, reacted in a 30 ℃ reaction block for 0.5H, after the reaction was complete, the solvent was removed under reduced pressure, and the desired product, 3,8, 14-trimethyl-6H-benzo [5,6 ] was isolated on a silica gel column][1,4]Oxazines [3,4 ]-a]Pyran [4,3,2-ij ]]Isoquinoline-9, 13-dicarboxylic acid diethyl ester (4fa), and all eluents are petroleum ether, ethyl acetate and dichloromethane which are prepared according to the ratio of 30:1: 1.
And (3) product data characterization: white solid, 87% yield. Melting range: 178 ℃ and 182 ℃. As shown in figures 11 and 12 of the drawings,1H NMR(400MHz,CDCl3)δ7.46(d,J＝7.9Hz,1H),7.29(t,J＝8.0Hz,1H),7.13(d,J＝7.9Hz,1H),6.96(d,J＝7.9Hz,1H),6.73(d,J＝7.7Hz,2H),4.52(d,J＝11.4Hz,1H),4.41–4.28(m,4H),4.13(d,J＝11.4Hz,1H),2.33(s,3H),2.14(s,3H),2.10(s,3H),1.38–1.35(m,6H).13C NMR(101MHz,CDCl3)δ168.5,166.6,160.2,148.8,144.0,136.9,130.1,128.3,128.2,127.6,122.9,121.5,121.4,120.8,117.0,114.9,108.9,105.3,86.3,64.0,60.8,60.7,21.2,19.4,19.3,14.4.HRMS[M+H]+calculated for C27H28NO6 +＝462.1911,found:462.1913.
example 7
Figure BDA0003513395460000072
Under the nitrogen condition, 1g (0.20mmol) of 3-aryl benzoxazine compound, 2a (0.44mmol) of diazo compound, [ Cp + RhCl2]2(4mol％)，AgSbF6(16 mol%), MesCOOH (0.4mmol) and solvent DCE (2.0mL) were added into a 10mL sealed tube, reacted in a 50 ℃ reaction block for 2H, after the reaction was completed, the solvent was removed under reduced pressure, and the desired product, 2-chloro-8, 14-dimethyl-6H-benzo [5,6 ] was isolated by silica gel column][1,4]Oxazines [3,4-a ]]Pyran [4,3,2-ij ]]Isoquinoline-9, 13-dicarboxylic acid diethyl ester (4ga), and all eluents are petroleum ether, ethyl acetate and dichloromethane which are prepared according to the ratio of 30:1: 1.
And (3) product data characterization: white solid, 80% yield. Melting range: 151 ℃ and 152 ℃. As shown in figures 13 and 14 of the drawings,1H NMR(400MHz,CDCl3)δ7.48(d,J＝8.0Hz,1H),7.30(t,J＝8.0Hz,1H),7.12–7.08(m,3H),6.85(d,J＝8.6Hz,1H),4.53(d,J＝11.4Hz,1H),4.41–4.26(m,4H),4.12(d,J＝11.4Hz,1H),2.14(s,3H),2.10(s,3H),1.36(t,J＝7.1Hz,6H).13C NMR(101MHz,CDCl3)δ168.2,166.5,159.9,148.0,142.6,130.3,128.1,127.9,127.6,126.8,126.3,124.5,121.8,121.6,117.6,114.7,109.0,106.3,85.9,64.0,61.0,60.8,19.4,19.2,14.4.HRMS[M+H]+calculated for C26H25ClNO6 +＝482.1365,found:482.1366.
example 8
Figure BDA0003513395460000081
Under the nitrogen condition, the 3-aryl benzoxazine compound 1h (0.20mmol), the diazo compound 2a (0.44mmol), [ Cp + RhCl2]2(4mol％)，AgSbF6(16 mol%), MesCOOH (0.4mmol) and solvent DCE (2.0mL) were added into a 10mL sealed tube, reacted in a 50 ℃ reaction block for 2H, after the reaction was completed, the solvent was removed under reduced pressure, and the desired product, 1-fluoro-8, 14-dimethyl-6H-benzo [5,6 ] was isolated by silica gel column][1,4]Oxazines [3,4-a ]]Pyran [4,3,2-ij ]]Isoquinoline-9, 13-dicarboxylic acid diethyl ester (4ha), and all eluents are petroleum ether, ethyl acetate and dichloromethane which are prepared according to the ratio of 30:1: 1.
And (3) product data characterization: white solid, 47% yield. Melting range: 142 ℃ and 143 ℃. As shown in figures 15 and 16 of the drawings,1H NMR(400MHz,CDCl3)δ7.47(d,J＝7.5Hz,1H),7.31(t,J＝8.0Hz,1H),7.16–7.10(m,2H),6.77–6.73(m,2H),4.54(d,J＝11.5Hz,1H),4.41–4.28(m,4H),4.20(d,J＝11.5Hz,1H),2.15(d,J＝2.7Hz,3H),2.09(s,3H),1.37(t,J＝7.1Hz,6H).13C NMR(101MHz,CDCl3)δ168.2,166.6,159.7,157.7(d,J＝248.0Hz),150.9(d,J＝3.6Hz),144.8,130.3,128.1(d,J＝18.8Hz),126.9,126.8,121.8(d,J＝7.5Hz),115.6(d,J＝15.6Hz),115.1,112.2(d,J＝2.9Hz),109.0,107.9,107.7,106.5,85.9,64.2,60.9,60.9,19.3,17.3,17.2,14.4.HRMS[M+H]+calculated for C26H25FNO6 +＝466.1660,found:466.1664.
example 9
Figure BDA0003513395460000082
Under the condition of nitrogen, 3-aryl benzoxazine compound 1i (0.20mmol), diazo compound 2a (0.44mmol), [ Cp + RhCl2]2(3mol％)，AgSbF6(12 mol%), MesCOOH (0.4mmol) and solvent DCE (2.0mL) were added into a 10mL sealed tube, reacted in a 30 ℃ reaction block for 1H, after the reaction was completed, the solvent was removed under reduced pressure, and the desired product, 11-fluoro-8, 14-dimethyl-6H-benzo [5,6 ] was isolated by silica gel column][1,4]Oxazines [3,4-a ]]Pyran [4,3,2-ij ] s]Isoquinoline-9, 13-dicarboxylic acid diethyl ester (4ia), and all eluents are petroleum ether, ethyl acetate and dichloromethane which are prepared according to the ratio of 30:1: 1.
And (3) product data characterization: white solid, 80% yield. Melting range: 132 ℃ and 133 ℃. As shown in figures 17 and 18 of the drawings,1H NMR(400MHz,CDCl3)δ7.30(dd,J＝10.6,2.4Hz,1H),7.19–7.13(m,1H),7.09(dd,J＝7.9,1.4Hz,1H),6.97–6.87(m,3H),4.51(d,J＝11.5Hz,1H),4.43–4.27(m,4H),4.11(d,J＝11.5Hz,1H),2.17(s,3H),2.10(s,3H),1.39–1.35(m,6H).13C NMR(101MHz,CDCl3)δ167.9,166.2,164.2(d,J＝243.7Hz),161.8,149.2,145.4,130.5(d,J＝2.8Hz),130.4(d,J＝3.3Hz),128.0,127.1,125.1,120.0,116.7,110.3(d,J＝2.1Hz),108.8(d,J＝26.3Hz),108.4(d,J＝23.2Hz),108.2,104.8(d,J＝2.3Hz),86.2,64.2,61.0,60.9,19.6,19.6,14.4,14.4.HRMS[M+H]+calculated for C26H25FNO6 +＝466.1660,found:466.1661.
example 10
Figure BDA0003513395460000091
Under the nitrogen condition, 3-aryl benzoxazine compound 1j (0.20mmol), diazo compound 2a (0.44mmol, [ Cp + RhCl ]2]2(2mol％)，AgSbF6(8 mol%), MesCOOH (0.4mmol) and solvent DCE (2.0mL) were added to a 10mL sealed tube, reacted in a 40 ℃ reaction block for 0.5h, after the reaction was complete, the solvent was removed under reduced pressure, and the desired product, 11-chloro-silica gel column, was isolated-8, 14-dimethyl-6H-benzo [5,6 ]][1,4]Oxazines [3,4-a ]]Pyran [4,3,2-ij ]]Isoquinoline-9, 13-dicarboxylic acid diethyl ester (4ja), and all eluents are prepared from petroleum ether, ethyl acetate and dichloromethane according to the ratio of 30:1: 1.
And (3) product data characterization: white solid, 82% yield. Melting range: 155 ℃ and 156 ℃. As shown in figures 19 and 20 of the drawings,1H NMR(400MHz,CDCl3)δ7.55(d,J＝1.7Hz,1H),7.20–7.14(m,2H),7.09(d,J＝7.8Hz,1H),6.98–6.89(m,2H),4.51(d,J＝11.5Hz,1H),4.43–4.28(m,4H),4.12(d,J＝11.5Hz,1H),2.16(s,3H),2.10(s,3H),1.38(t,J＝7.0Hz,6H).13C NMR(101MHz,CDCl3)δ167.9,166.1,161.6,149.1,145.3,136.6,129.9,129.8,128.0,127.1,125.1,121.5,121.3,120.0,116.8,112.8,108.1,104.6,86.1,64.1,61.1,61.0,19.7,19.6,14.4,14.4.HRMS[M+H]+calculated for C26H25ClNO6 +＝482,1365,found:482.1362.
example 11
Figure BDA0003513395460000101
Under the nitrogen condition, 3-aryl benzoxazine compound 1k (0.20mmol), diazo compound 2a (0.44mmol), [ Cp + RhCl2]2(4mol％)，AgSbF6(16 mol%), MesCOOH (0.4mmol) and solvent DCE (2.0mL) were added to a 10mL sealed tube, reacted in a 30 ℃ reaction block for 0.5H, after the reaction was complete, the solvent was removed under reduced pressure, and the desired product, 11-bromo-8, 14-dimethyl-6H-benzo [5,6 ] was isolated on a silica gel column][1,4]Oxazines [3,4-a ]]Pyran [4,3,2-ij ] s]Isoquinoline-9, 13-dicarboxylic acid diethyl ester (4ka), and all eluents are petroleum ether, ethyl acetate and dichloromethane which are prepared according to the ratio of 30:1: 1.
And (3) product data characterization: yellow solid, 85% yield. Melting range: 150 ℃ to 151 ℃. As shown in figures 21 and 22 of the drawings,1H NMR(400MHz,CDCl3)δ7.71(d,J＝1.4Hz,1H),7.34(d,J＝1.4Hz,1H),7.16(t,J＝7.7Hz,1H),7.09(d,J＝7.8Hz,1H),6.93(dd,J＝12.0,8.1Hz,2H),4.51(d,J＝11.5Hz,1H),4.44–4.27(m,4H),4.12(d,J＝11.5Hz,1H),2.16(s,3H),2.10(s,3H),1.38(t,J＝7.1Hz,6H).13C NMR(101MHz,CDCl3)δ167.8,166.0,161.6,149.1,145.3,130.0,129.9,128.0,127.1,125.1,124.9,124.3,124.2,120.0,116.7,113.2,108.0,104.4,86.1,64.0,61.0,61.0,19.6,19.5,14.4,14.4.HRMS[M+H]+calculated for C26H25BrNO6 +＝526.0860,found:526.0856.
example 12
Figure BDA0003513395460000102
Under the nitrogen condition, 1l (0.20mmol) of 3-aryl benzoxazine compound, 2a (0.44mmol) of diazo compound and [ Cp & RhCl & lt/EN & gt2]2(4mol％)，AgSbF6(16 mol%), MesCOOH (0.4mmol) and solvent DCE (2.0mL) were added to a 10mL sealed tube, reacted in a 30 ℃ reaction block for 0.5H, after the reaction was complete, the solvent was removed under reduced pressure, and the desired product, 11-phenyl-8, 14-dimethyl-6H-benzo [5,6 ] was isolated on a silica gel column][1,4]Oxazines [3,4-a ]]Pyran [4,3,2-ij ]]Isoquinoline-9, 13-dicarboxylic acid diethyl ester (4la), and all eluents are petroleum ether, ethyl acetate and dichloromethane which are prepared according to the ratio of 30:1: 1.
And (3) product data characterization: white solid, 59% yield. Melting range: 156 ℃ and 157 ℃. As shown in figures 23 and 24 of the drawings,1H NMR(400MHz,CDCl3)δ7.73(d,J＝7.5Hz,1H),7.56(d,J＝7.5Hz,2H),7.43(t,J＝7.5Hz,2H),7.39–7.33(m,2H),7.16(t,J＝7.7Hz,1H),7.11(d,J＝7.8Hz,1H),6.94(t,J＝7.8Hz,2H),4.59(d,J＝11.4Hz,1H),4.45–4.28(m,4H),4.19(d,J＝11.4Hz,1H),2.18(s,3H),2.12(s,3H),1.38(t,J＝7.1Hz,6H).13C NMR(101MHz,CDCl3)δ168.4,166.6,160.6,149.3,144.2,143.3,141.4,128.9,128.6,128.1,127.7,127.4,126.9,125.4,120.7,120.5,119.9,116.7,113.9,108.9,105.6,86.3,64.2,60.9,60.8,19.6,19.4,14.5,14.5.HRMS[M+H]+calculated for C32H30NO6 +＝524.2068,found:524.2066.
example 13
Figure BDA0003513395460000111
Under the condition of nitrogen, 1m (0.20mmol) of 3-aryl benzoxazine compound, 2a (0.44mmol) of diazo compound and [ Cp & RhCl & lt/EN & gt2]2(2mol％)，AgSbF6(8 mol%), MesCOOH (0.4mmol) and solvent DCE (2.0mL) were added into a 10mL sealed tube, reacted in a 60 ℃ reaction block for 0.5H, after the reaction was completed, the solvent was removed under reduced pressure, and the desired product, 11-trifluoromethyl-8, 14-dimethyl-6H-benzo [5,6 ] -was isolated by silica gel column][1,4]Oxazines [3,4-a ]]Pyran [4,3,2-ij ]]Isoquinoline-9, 13-dicarboxylic acid diethyl ester (4ma), and all eluents are prepared from petroleum ether, ethyl acetate and dichloromethane according to the ratio of 30:1: 1.
And (3) product data characterization: white solid, 72% yield. Melting range: 79 to 80 ℃. As shown in figures 25 and 26 of the drawings,1H NMR(400MHz,CDCl3)δ7.83(s,1H),7.46(s,1H),7.18(t,J＝7.7Hz,1H),7.10(d,J＝7.6Hz,1H),6.95(dd,J＝11.9,8.0Hz,2H),4.54(d,J＝11.5Hz,1H),4.46–4.26(m,4H),4.15(d,J＝11.5Hz,1H),2.20(s,3H),2.13(s,3H),1.38(t,J＝7.1Hz,6H).13C NMR(101MHz,CDCl3)δ167.8,166.0,162.0,149.1,145.9,132.5(d,J＝31.9Hz),129.2,129.1,128.0,127.3,125.03,124.1(q,J＝266.3Hz),120.1,118.3,118.3(d,J＝3.8Hz),116.8,108.3,104.6,86.1,63.9,61.1,61.1,19.6,19.5,14.3,14.3.HRMS[M+H]+calculated for C27H25F3NO6 +＝516.1628,found:516.1626.
example 14
Figure BDA0003513395460000112
Under the condition of nitrogen, 3-aryl benzoxazine compound 1n (0.20mmol), diazo compound 2a (0.44mmol), [ Cp + RhCl2]2(4mol％)，AgSbF6(16 mol%), MesCOOH (0.4mmol) and solvent DCE (2.0mL) were charged into a 10mL sealed tube, reacted in a 90 ℃ reaction block for 6 hours, after the reaction was completed, the solvent was removed under reduced pressure, and the reaction product was isolated by silica gel column chromatographyTo obtain the target product 11-methoxy-8, 14-dimethyl-6H-benzo [5,6 ]][1,4]Oxazines [3,4-a ]]Pyran [4,3,2-ij ]]Isoquinoline-9, 13-dicarboxylic acid diethyl ester (4na), and all eluents are petroleum ether ethyl acetate and dichloromethane which are prepared according to the ratio of 30:1: 1.
And (3) product data characterization: white solid, 69% yield. Melting range: 183 ℃ and 184 ℃. As shown in figures 27 and 28 of the drawings,1H NMR(400MHz,CDCl3)δ7.16–7.08(m,3H),6.94–6.90(m,2H),6.70(d,J＝2.2Hz,1H),4.50(d,J＝11.4Hz,1H),4.09(d,J＝11.4Hz,1H),3.86(s,3H),3.85(s,3H),3.80(s,3H),2.14(s,3H),2.09(s,3H).13C NMR(101MHz,CDCl3)δ168.7,167.0,161.2,161.1,149.1,144.7,129.4,129.3,128.0,126.9,125.3,119.8,116.6,108.4,107.6,107.3,107.2,105.1,86.2,64.3,55.4,51.7,51.6,19.6,19.5.HRMS[M+H]+calculated for C25H24NO7 +＝450.1547,found:450.1546.
example 15
Figure BDA0003513395460000121
Under the condition of nitrogen, 3-aryl benzoxazine compound 1a (0.20mmol), diazo compound 2b (0.44mmol), [ Cp + RhCl2]2(4mol％)，AgSbF6(16 mol%), MesCOOH (0.4mmol) and solvent DCE (2.0mL) were added to a 10mL sealed tube, reacted in a 30 ℃ reaction block for 0.5H, after the reaction was complete, the solvent was removed under reduced pressure, and the desired product, 8, 14-dimethyl-6H-benzo [5,6 ] was isolated on a silica gel column][1,4]Oxazines [3,4-a ]]Pyran [4,3,2-ij ]]Isoquinoline-9, 13-dicarboxylic acid diisopropyl ester (4ab), and all eluents are petroleum ether ethyl acetate and dichloromethane which are prepared according to the ratio of 30:1: 1.
And (3) product data characterization: white solid, 74% yield. Melting range: 138 ℃ and 139 ℃. As shown in figures 29 and 30 of the drawings,1H NMR(400MHz,CDCl3)δ7.17–7.12(m,1H),7.11–7.08(m,2H),6.94–6.90(m,2H),6.71(d,J＝2.3Hz,1H),5.28–5.20(m,2H),4.52(d,J＝11.4Hz,1H),4.12(d,J＝11.4Hz,1H),3.79(s,3H),2.13(s,3H),2.08(s,3H),1.41–1.31(m,12H).13C NMR(101MHz,CDCl3)δ167.9,166.2,161.1,160.4,149.3,143.7,129.6,129.5,128.1,126.8,125.5,119.8,116.6,109.0,107.7,107.1,107.1,105.9,86.2,68.5,68.4,64.4,55.4,22.2,22.2,22.1,22.0,19.5,19.4.HRMS[M+H]+calculated for C29H32NO7 +＝506.2173,found:506.2173.
example 16
Figure BDA0003513395460000122
Under the condition of nitrogen, 3-aryl benzoxazine compound 1a (0.20mmol), diazo compound 2c (0.44mmol), [ Cp + RhCl2]2(4mol％)，AgSbF6(16 mol%), MesCOOH (0.4mmol) and solvent DCE (2.0mL) were charged into a 10mL sealed tube, reacted in a 30 ℃ reaction block for 0.5H, after the reaction was completed, the solvent was removed under reduced pressure, and the desired product, 8, 14-dipropyl-6H-benzo [5,6 ], was isolated by silica gel column][1,4]Oxazines [3,4-a ]]Pyran [4,3,2-ij ]]Isoquinoline-9, 13-dicarboxylic acid dimethyl ester (4ac), and all eluents are petroleum ether ethyl acetate and dichloromethane which are prepared according to the ratio of 30:1: 1.
And (3) product data characterization: yellow solid, 50% yield. As shown in figures 31 and 32 of the drawings,1H NMR(400MHz,CDCl3)δ7.17(dd,J＝12.1,4.6Hz,2H),7.04(d,J＝2.3Hz,1H),6.96–6.87(m,2H),6.70(d,J＝2.3Hz,1H),4.45(d,J＝11.4Hz,1H),4.14(d,J＝11.4Hz,1H),3.85(s,3H),3.84(s,3H),3.79(s,3H),2.71–2.47(m,4H),1.42–1.25(m,4H),0.80(t,J＝7.4Hz,3H),0.73(t,J＝7.3Hz,3H).13C NMR(101MHz,CDCl3)δ168.7,167.2,163.3,161.2,149.8,149.2,129.6,129.3,127.3,127.1,125.7,120.0,116.5,108.4,107.5,107.3,107.1,105.0,86.4,64.5,55.5,51.8,51.7,34.4,31.8,22.4,20.6,14.0,13.9.HRMS[M+H]+calculated for C29H32NO7 +＝506.2173,found:506.2164.
example 17
Figure BDA0003513395460000131
Under the condition of nitrogen, 3-aryl benzoxazine compound 1a (0.20mmol), diazo compound 2d (0.44mmol), [ Cp + RhCl2]2(4mol％)，AgSbF6(16mol percent), MesCOOH (0.4mmol) and a solvent DCE (2.0mL) are added into a 10mL sealed tube and reacted for 5 hours in a 30-DEG reaction module, the solvent is removed under reduced pressure after the reaction is finished, and the target product 8, 14-diphenyl-6H-benzo [5,6 ] is obtained by silica gel column separation][1,4]Oxazines [3,4-a ]]Pyran [4,3,2-ij ]]Isoquinoline-9, 13-dicarboxylic acid diethyl ester (4ad), and all eluents are petroleum ether, ethyl acetate and dichloromethane which are prepared according to the ratio of 30:1: 1.
And (3) product data characterization: white solid, 49% yield. Melting range: 186 ℃ and 187 ℃. As shown in figures 33 and 34 of the drawings,1H NMR(400MHz,CDCl3)δ7.52–7.45(m,2H),7.39–7.17(m,7H),7.12(d,J＝1.7Hz,1H),7.07(t,J＝7.6Hz,1H),6.98(dt,J＝15.2,7.8Hz,2H),6.73(d,J＝7.8Hz,1H),6.39(t,J＝7.6Hz,1H),6.16(d,J＝8.0Hz,1H),4.87(d,J＝11.4Hz,1H),4.47(d,J＝11.4Hz,1H),4.14–3.95(m,2H),3.87(s,3H),3.86–3.73(m,2H),0.92(t,J＝7.1Hz,3H),0.76(t,J＝7.1Hz,3H).13C NMR(101MHz,CDCl3)δ167.6,167.5,161.7,157.9,148.9,146.7,134.7,133.9,130.6,130.4,130.2,129.8,129.5,129.3,128.6,128.1，128.1,128.0,127.7,126.0,125.3,119.7,116.0,109.4,107.8,107.1,107.0,106.8,87.1,64.5,61.0,60.6,55.6,13.6,13.6.HRMS[M+H]+calculated for C37H32NO7 +＝602.2173,found:602.2173.
the above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

1. A method for synthesizing a spiroheterocyclic compound, characterized in that: a3-aryl benzoxazine compound and a diazo compound are used as raw materials, and a novel spiro-heterocyclic compound is synthesized under the promotion of a catalyst, wherein the reaction formula is as follows:
Figure FDA0003513395450000011
wherein R is any one of H, Me, F, Cl and Br; r is1Any one of Me, Pr and Ph; r2Is Me, Et,iAny one of Pr; ar is Me, OMe, F, Cl, Br, Ph, CF3Any one of the substituted benzene rings.
2. A synthesis method of spiro-heterocyclic compounds according to claim 1, characterized by comprising the specific steps of: adding a 3-aryl benzoxazine compound, a diazo compound, a catalyst and an additive into a solvent, reacting under the protection of inert atmosphere, and purifying after the reaction is finished to obtain the spiroheterocyclic compound.
3. A method of synthesizing a spiroheterocyclic compound according to claim 2, characterized in that: the catalyst comprises a rhodium catalyst and a silver salt; the molar ratio of rhodium catalyst to silver salt is 1: (2-4); the rhodium catalyst is dichloro (pentamethylcyclopentadienyl) rhodium dimer, pentamethylcyclopentadienyl rhodium acetate or bis (hexafluoroantimonic acid) triethylenenitrile (pentamethylcyclopentadienyl) rhodium; the silver salt is silver hexafluoroantimonate, silver bistrifluoromethanesulfonylimide, silver tetrafluoroborate, silver trifluoromethanesulfonate, silver sulfate, silver acetate and silver trifluoroacetate.
4. A method of synthesizing a spiroheterocyclic compound according to claim 3, characterized in that: the catalyst consists of dichloro (pentamethyl cyclopentadienyl) rhodium dimer and silver hexafluoroantimonate; the molar ratio of dichloro (pentamethylcyclopentadienyl) rhodium dimer to silver hexafluoroantimonate was 1: 4.
5. a method of synthesizing a spiroheterocyclic compound according to claim 2, characterized in that: the additive is any one of trimesobenzoic acid (MesCOOH), pivalic acid, acetic acid, benzoic acid, proline, adamantanecarboxylic acid, zinc acetate, sodium carbonate, potassium acetate and potassium carbonate.
6. A method of synthesizing a spiroheterocyclic compound according to claim 2, characterized in that: the solvent is any one of dichloroethane, dichloromethane, methanol, acetonitrile, 1, 4-dioxane and toluene.
7. A method of synthesizing a spiroheterocyclic compound according to claim 2, characterized in that: the 3-aryl benzoxazine compound: diazo compound: catalyst: the molar ratio of the additive is 1: 2.2: 0.02-0.04: 0.08-0.16.
8. A method of synthesizing a spiroheterocyclic compound according to claim 2, characterized in that: the concentration of the reaction system in the solvent is 0.05M-0.2M.
9. A method of synthesizing a spiroheterocyclic compound according to claim 2, characterized in that: the inert atmosphere is nitrogen atmosphere.
10. A method of synthesizing a spiroheterocyclic compound according to claim 2, characterized in that: the reaction temperature is 30-90 ℃, and the reaction time is 0.5-6 h.
CN202210157582.9A 2022-02-17 2022-02-21 Synthetic method of spiroheterocyclic compound Pending CN114478576A (en)

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Publication number Priority date Publication date Assignee Title
CN114957284A (en) * 2022-06-07 2022-08-30 中国科学院生态环境研究中心 High-efficiency synthesis method and application of natural product Lycibararine
CN116768916A (en) * 2023-06-20 2023-09-19 河南农业大学 Coumarin compound containing spiropyran structure and synthetic method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JING JING ZHANG ET AL.: ""Synthesis of spiropyrans via the Rh(III)-catalyzed annulation of 3-aryl-2H-benzo[b][1,4]oxazines with diazo ketoesters"", 《CHEM. COMMUN.》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114957284A (en) * 2022-06-07 2022-08-30 中国科学院生态环境研究中心 High-efficiency synthesis method and application of natural product Lycibararine
CN114957284B (en) * 2022-06-07 2023-06-09 中国科学院生态环境研究中心 Efficient synthesis method and application of natural product Lycibarbitine
CN116768916A (en) * 2023-06-20 2023-09-19 河南农业大学 Coumarin compound containing spiropyran structure and synthetic method and application thereof
CN116768916B (en) * 2023-06-20 2024-04-26 河南农业大学 Coumarin compound containing spiropyran structure and synthetic method and application thereof

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