CN108676012A - A kind of preparation method of imines coumarin kind compound - Google Patents

A kind of preparation method of imines coumarin kind compound Download PDF

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CN108676012A
CN108676012A CN201810862995.0A CN201810862995A CN108676012A CN 108676012 A CN108676012 A CN 108676012A CN 201810862995 A CN201810862995 A CN 201810862995A CN 108676012 A CN108676012 A CN 108676012A
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preparation
reaction
imines
rhodium
alkyl
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赵应伟
陈展
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Huaqiao University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pyrane Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

The invention discloses a kind of preparation method of imines coumarin kind compound, reaction equation is as follows：The present invention overcomes raw materials in conventional method to be not easy to obtain, has the shortcomings that danger.Because being one pot of three component reaction, reaction efficiency is high, while this reacting middle catalyst dosage is low, substantially increases the application prospect of the reaction industrially.

Description

A kind of preparation method of imines coumarin kind compound
Technical field
The invention belongs to catalytic synthetic techniques fields, and in particular to a kind of preparation method of imines coumarin kind compound.
Background technology
Cumarin and its derivative are a kind of heterocyclic compounds with important biomolecule activity and material applications.Imines tonka-bean Element is an important branch of this kind of compound, be widely used in drug matrices, fluorescence indicator, fluorescence probe, laser dye, The application fields such as pH sensors.For example, a kind of molecule containing imines tonka bean camphor structure is a kind of tyrosine protein kinase inhibition Agent (J.Med.Chem.1993,36,425-432) and dynamin GTP enzyme inhibitors (J.Med.Chem.2010,53,4094- 4102)；Imines coumarin kind compound is also successfully used for the identification of the amino acid containing mercapto as fluorescence probe (Chem.Asian.J., 2015,10,422-426) is in addition alternatively arranged as very sensitive zinc ion probe (J.Am.Chem.Soc.2007,129,13447-13454).
The prior synthesizing method of imines cumarin molecule is the condensation reaction by salicylide and cyano compound (in such as 103641820 A of state patent CN).Another method be by the salicylide (or salicylonitrile) of copper catalysis, alkynes, Azido compound three components coupling cyclization (Org.Lett., 2006,8,4517-4520；CN 106146447 A).This The shortcomings that a little methods is that substrate is not easy to obtain, and in addition to use the dangerous azido compound of tool, it is often more important that, cumarin The substitution of No. 4 positions of skeleton is difficult to obtain.Therefore, a kind of reaction of efficient synthesizing imine cumarin molecule is before very having application Scape.
Invention content
The purpose of the present invention is to provide a kind of preparation methods of imines coumarin kind compound.
Technical scheme is as follows：
A kind of preparation method of imines coumarin kind compound, reaction equation are as follows：
Wherein, reaction atmosphere is air, and reaction temperature is 60~120 DEG C, and the reaction time is 2~12h, R1For hydrogen, alkyl, Aryl and ring, halogen, alkoxy, alkylthio group, amide groups, cyano, formoxyl, formyloxy or trifluoromethyl, and R1Not take Generation, monosubstituted, disubstituted or three substitutions, R2For methyl, ethyl or isopropyl, R3For hydrogen, alkyl or aryl, R4For hydrogen, alkyl or Aryl, R5For alkyl or aryl sulfonyl；Above-mentioned rhodium catalyst is that dichloro (pentamethylcyclopentadiene base) closes rhodium (III) dimer Or dichloro (pentamethylcyclopentadiene base) closes the mixture of rhodium (III) dimer and the silver salt of four times of amounts, above-mentioned oxidant is two Valence mantoquita.
In a preferred embodiment of the invention, the anion of the silver salt is trifluoromethanesulfonic acid root, hexafluoro-antimonic acid Root or bis-trifluoromethylsulfoandimide anion.
In a preferred embodiment of the invention, the cupric salt is copper acetate, copper sulphate, copper trifluoromethanesulfcomposite Or copper oxide.
In a preferred embodiment of the invention, the organic solvent is 1,2- dichloroethanes, tertriary amylo alcohol, N, N- bis- Methylformamide, tetrahydrofuran or acetonitrile.
In a preferred embodiment of the invention, the thiocarbamic acid phenolic ester, alkynes, amine, rhodium catalyst, silver The molar ratio of salt and oxidant is 1: 1~1.5: 1~1.5: 0.005~0.025: 0~0.1: 1~1.5.
In a preferred embodiment of the invention, the reaction temperature is 120 DEG C, reaction time 12h.
In a preferred embodiment of the invention, after reaction directly concentration and with column chromatography on a silica gel column Purified, use the mixed liquor of petroleum ether and ethyl acetate as eluant, eluent eluted to get.
It is further preferred that the volume ratio of the eluant, eluent petrochina ether and ethyl acetate is 3~10: 1.
The beneficial effects of the invention are as follows：
1, the present invention overcomes raw materials in conventional method to be not easy to obtain, has the shortcomings that danger.Because being one pot of three component Reaction, so reaction efficiency is high, while this reacting middle catalyst dosage is low, before substantially increasing the application of the reaction industrially Scape.
2, new reaction of the invention can be by changing alkynes structure so that method is difficult to 3, the 4- synthesized bis- before synthesis Substituted imine cumarin expands range for the Structure Selection of this kind of compound.
Description of the drawings
Fig. 1 is imines coumarin kind compound made from the embodiment of the present invention 11H NMR spectras.
Fig. 2 is imines coumarin kind compound made from the embodiment of the present invention 113C NMR spectras.
Fig. 3 is imines coumarin kind compound made from the embodiment of the present invention 21H NMR spectras.
Fig. 4 is imines coumarin kind compound made from the embodiment of the present invention 213C NMR spectras.
Fig. 5 is imines coumarin kind compound made from the embodiment of the present invention 31H NMR spectras.
Fig. 6 is imines coumarin kind compound made from the embodiment of the present invention 313C NMR spectras.
Fig. 7 is imines coumarin kind compound made from the embodiment of the present invention 41H NMR spectras.
Fig. 8 is imines coumarin kind compound made from the embodiment of the present invention 413C NMR spectras.
Fig. 9 is the X-ray single crystal diffraction analysis chart of imines coumarin kind compound made from the embodiment of the present invention 2.
Specific implementation mode
Technical scheme of the present invention is further detailed and is described below by way of specific implementation mode combination attached drawing.
Embodiment 1
The structural formula of imines coumarin kind compound made from the present embodiment is as follows：
By the thio dimethylamino formic acid acid sesamol esters of 0.25mmol, 0.3mmol dibenzenyls, 0.2mmol to toluene sulphur Amide and 0.0025mmol dichloros (pentamethylcyclopentadiene base) close rhodium (III) dimer, 0.01mmol hexafluoros telluric acid silver, 0.25mmol copper acetates are placed in 25mL pressure-resistant seal reaction tubes, are sealed after 1, the 2- dichloroethanes of 1mL is added, at 120 DEG C It is stirred to react in oil bath 12 hours.Resulting material is cooled to room temperature, and after ethyl acetate is added, mixes silica gel concentration, pure with silicagel column Change product, then the eluant, eluent for being successively 10: 1,5: 1,3: 1 with the volume ratio of petroleum ether and ethyl acetate carries out gradient elution, obtains To corresponding imines coumarin kind compound (Z)-N- (7,8-diphenyl-6H- [1,3] dioxolo [4,5-g] chromen- 6-ylidene) -4-methylbenzenesulfonamide, yield 76%.It characterizes as depicted in figs. 1 and 2：1HNMR (500MHz, CDCl3) δ 2.37 (s, 3H), 5.75 (s, 2H), 7.00-7.05 (m, 6H), 7.10-7.12 (m, 3H), 7.15- 7.20 (m, 3H), 7.22-7.23 (m, 2H), 7.80 (s, 1H), 7.82 (s, 1H)；13CNMR (126MHz, CDCl3) δ 21.5, 102.3,106.7,108.9,111.1,127.0,127.4,127.5,128.2,128.7,129.1,130.7,133.0, 135.3,139.6,142.7,144.3,145.1,146.5,147.9,158.2. in addition, X-ray single crystal diffraction analysis chart such as figure Shown in 9.
Embodiment 2
The structural formula of imines coumarin kind compound made from the present embodiment is as follows：
By the thio dimethylamino formic acid p bromophenol esters of 0.25mmol, 0.3mmol dibenzenyls, 0.2mmol to toluene Sulfonamide and 0.0025mmol dichloros (pentamethylcyclopentadiene base) close rhodium (III) dimer, 0.01mmol hexafluoros telluric acid silver, 0.25mmol copper acetates are placed in 25mL pressure-resistant seal reaction tubes, are sealed after 1, the 2- dichloroethanes of 1mL is added, at 120 DEG C It is stirred to react in oil bath 12 hours.Resulting material is cooled to room temperature, and after ethyl acetate is added, mixes silica gel concentration, pure with silicagel column Change product, then the eluant, eluent for being successively 10: 1,5: 1,3: 1 with the volume ratio of petroleum ether and ethyl acetate carries out gradient elution, obtains To corresponding imines coumarin kind compound (Z)-N- (6-bromo-3,4-diphenyl-2H-chromen-2-ylidene)- 4-methylbenzenesulfonamide, yield 72%.It characterizes as shown in Figure 3 and Figure 4：1H NMR (500MHz, CDCl3) δ 2.38 (s, 3H), 7.02-7.06 (m, 4H), 7.12-7.14 (m, 3H), 7.22 (s, 1H), 7.24 (s, 1H), 7.28- 7.31 (m, 4H) 7.43-7.45 (m, 1H), 7.65-7.67 (m, 1H), 7.81 (s, 1H), 7.82 (s, 1H)；13CNMR (126MHz, CDCl3) δ 21.3,118.3,118.5,122.4,126.9,127.6,127.9,128.5,128.8,129.1,129.2, 129.6,130.1,130.5,133.0,133.4,134.6,139.4,142.9,149.7,151.0,157.8.
Embodiment 3
The structural formula of imines coumarin kind compound made from the present embodiment is as follows：
By the thio dimethylamino formic acid of 0.25mmol to formoxyl phenol ester, 0.3mmol dibenzenyls, 0.2mmol pairs Toluenesulfonamide and 0.0025mmol dichloros (pentamethylcyclopentadiene base) close rhodium (III) dimer, 0.01mmol hexafluoro telluric acids Silver, 0.25mmol copper acetates are placed in 25mL pressure-resistant seal reaction tubes, are sealed after 1, the 2- dichloroethanes of 1mL is added, at 120 DEG C Oil bath in be stirred to react 12 hours.Resulting material is cooled to room temperature, and after ethyl acetate is added, is mixed silica gel concentration, is used silicagel column Purified product, then the eluant, eluent for being successively 10: 1,5: 1,3: 1 with the volume ratio of petroleum ether and ethyl acetate carry out gradient elution, Obtain corresponding imines coumarin kind compound (Z)-N- (6-formyl-3,4-diphenyl-2H-chromen-2- Ylidene) -4-methylbenzenesulfonamide, yield 62%.It characterizes as shown in Figure 5 and Figure 6：1H NMR (500MHz, CDCl3) δ 2.39 (s, 3H), 7.06-7.08 (m, 4H), 7.14-7.16 (m, 3H), 7.23-7.26 (m, 2H), 7.31-7.33 (m, 2H), 7.69 (d, J=8.5Hz, 1H), 7.73 (d, J=1.9Hz, 1H), 7.82 (d, J=8.3Hz, 2H), 8.09 (dd, J1=5.6Hz, J2=1.9Hz, 1H), 9.90 (s, 1H)；13C NMR (126MHz, CDCl3) δ 21.5,118.0, 121.3,126.9,127.7,128.0,128.6,129.0,129.2,129.2,129.7,130.4,130.5,131.9, 132.9,133.3,133.4,139.2,143.1,150.2,155.4,157.5,190.0.
Embodiment 4
The structural formula of imines coumarin kind compound made from the present embodiment is as follows：
By the thio dimethylamino formic acid phenol esters of 0.25mmol, 0.3mmol 4- octynes, 0.2mmol para toluene sulfonamides and 0.0025mmol dichloros (pentamethylcyclopentadiene base) close rhodium (III) dimer, 0.01mmol hexafluoros telluric acid silver, 0.25mmol vinegar Sour copper is placed in 25mL pressure-resistant seal reaction tubes, is sealed after 1, the 2- dichloroethanes of 1mL is added, is stirred in 120 DEG C of oil bath Reaction 12 hours.Resulting material is cooled to room temperature, and after ethyl acetate is added, mixes silica gel concentration, with silicagel column purified product, then according to The secondary eluant, eluent for being 10: 1,5: 1,3: 1 with the volume ratio of petroleum ether and ethyl acetate carries out gradient elution, obtains corresponding imines Coumarin kind compound (Z)-N- (3,4-dipropyl-2H-chromen-2-ylidene) -4- Methylbenzenesulfonamide, yield 61%.It characterizes as shown in Figure 7 and Figure 8：1H NMR (500MHz, CDCl3)δ 1.01 (t, J=7.4Hz, 3H), 1.10 (t, J=7.4Hz, 3H), 1.58-1.62 (m, 4H), 2.42 (s, 3H), 2.64 (t, J= 8.0Hz, 2H), 2.81 (t, J=8.0Hz, 2H), 7.29-7.35 (m, 3H), 7.38-7.40 (m, 1H), 7.49-7.52 (m, 1H), 7.61-7.63 (m, 1H)；13C NMR (126MHz, CDCl3) δ 14.4,14.5,21.5,22.0,23.0,29.5,30.7, 116.9,119.9,124.6,125.3,127.2,127.4,129.1,130.8,139.7,142.8,150.1,151.4, 158.7.
The foregoing is only a preferred embodiment of the present invention, therefore cannot limit the scope of implementation of the present invention according to this, i.e., According to equivalent changes and modifications made by the scope of the claims of the present invention and description, all should still belong in the range of the present invention covers.

Claims (8)

1. a kind of preparation method of imines coumarin kind compound, it is characterised in that：Its reaction equation is as follows：
Wherein, reaction atmosphere is air, and reaction temperature is 60~120 DEG C, and the reaction time is 2~12h, R1For hydrogen, alkyl, aryl, And ring, halogen, alkoxy, alkylthio group, amide groups, cyano, formoxyl, formyloxy or trifluoromethyl, and R1It is unsubstituted, single Substitution, disubstituted or three substitutions, R2For methyl, ethyl or isopropyl, R3For hydrogen, alkyl or aryl, R4For hydrogen, alkyl or aryl, R5For alkyl or aryl sulfonyl；Above-mentioned rhodium catalyst is that dichloro (pentamethylcyclopentadiene base) closes rhodium (III) dimer or two Chlorine (pentamethylcyclopentadiene base) closes the mixture of rhodium (III) dimer and the silver salt of four times of amounts, and above-mentioned oxidant is cupric Salt.
2. preparation method as described in claim 1, it is characterised in that：The anion of the silver salt is trifluoromethanesulfonic acid root, six Fluorine metaantimmonic acid root or bis-trifluoromethylsulfoandimide anion.
3. preparation method as described in claim 1, it is characterised in that：The cupric salt is copper acetate, copper sulphate, fluoroform Sulfonic acid copper or copper oxide.
4. preparation method as described in claim 1, it is characterised in that：The organic solvent be 1,2- dichloroethanes, tertriary amylo alcohol, N,N-Dimethylformamide, tetrahydrofuran or acetonitrile.
5. preparation method as described in claim 1, it is characterised in that：The thiocarbamic acid phenolic ester, alkynes, amine, rhodium are urged The molar ratio of agent, silver salt and oxidant is 1: 1~1.5: 1~1.5: 0.005~0.025: 0~0.1: 1~1.5.
6. preparation method as described in claim 1, it is characterised in that：The reaction temperature is 120 DEG C, reaction time 12h.
7. preparation method as described in claim 1, it is characterised in that：It directly concentrates after reaction and with column chromatography in silicon Purified in rubber column gel column, use the mixed liquor of petroleum ether and ethyl acetate as eluant, eluent eluted to get.
8. preparation method as claimed in claim 7, it is characterised in that：The volume of the eluant, eluent petrochina ether and ethyl acetate Than being 3~10: 1.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112442005A (en) * 2020-12-02 2021-03-05 广东湛江海洋医药研究院 N-sulfonyl imine coumarin derivative and preparation method thereof

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112442005A (en) * 2020-12-02 2021-03-05 广东湛江海洋医药研究院 N-sulfonyl imine coumarin derivative and preparation method thereof
CN112442005B (en) * 2020-12-02 2022-07-05 广东湛江海洋医药研究院 N-sulfonyl imine coumarin derivative and preparation method thereof

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