CN107337631A - It is a kind of based on Oxoindole spiro-compound and its synthetic method of the allyl sulfide ylide as three carbon synthons - Google Patents

It is a kind of based on Oxoindole spiro-compound and its synthetic method of the allyl sulfide ylide as three carbon synthons Download PDF

Info

Publication number
CN107337631A
CN107337631A CN201611025219.2A CN201611025219A CN107337631A CN 107337631 A CN107337631 A CN 107337631A CN 201611025219 A CN201611025219 A CN 201611025219A CN 107337631 A CN107337631 A CN 107337631A
Authority
CN
China
Prior art keywords
compound
ylide
oxoindole
spiro
allyl sulfide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201611025219.2A
Other languages
Chinese (zh)
Inventor
于爱敏
杜艳龙
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tianjin University of Technology
Original Assignee
Tianjin University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tianjin University of Technology filed Critical Tianjin University of Technology
Priority to CN201611025219.2A priority Critical patent/CN107337631A/en
Publication of CN107337631A publication Critical patent/CN107337631A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/96—Spiro-condensed ring systems

Abstract

It is a kind of based on Oxoindole spiro-compound of the allyl sulfide ylide as three carbon synthons, its chemical molecular formula is C21+ mH21+nO6+x, wherein m, n, x is 1 10 integer, and molecule has following structureWherein：R1For methyl, ethyl, acetyl group, methyl ethyl ether, benzyl or two dimethyl dicarbonate butyl；R2For hydroxyl, methoxy or ethoxy；R3For 5 F, 5 Br, 5 Cl, 5 CH3、5‑OCH3、6‑Cl、6‑Br、6‑OCH3、7‑CH3, 7 Cl or 7 Br.It is an advantage of the invention that：This method utilizes the characteristic of cascade reaction, reach the purpose of one-step synthesis target product, it is significant to improve reaction efficiency, save the reaction time, simplify reactions steps, a brand-new method and thinking is provided for trisubstituted five yuan oxidation spiro-compounds, the synthesis to similar compound has certain reference value.

Description

It is a kind of based on Oxoindole spirocyclization of the allyl sulfide ylide as three carbon synthons Compound and its synthetic method
Technical field
It is more particularly to a kind of to be synthesized based on allyl sulfide ylide as three carbon the invention belongs to technical field of organic synthesis The Oxoindole spiro-compound and its synthetic method of son.
Background technology
Sulfur ylide is the nucleopilic reagent with leaving group, can be with shorts of electricity such as attack aldehyde, ketone, imines and electron deficient olefins The experimental data of sub- reagent, many physics and chemistry shows that the key between the carbon atom in sulfur ylide and sulphur atom has part The property of double bond.In general, according to its stability or activity it is different in ylide can be divided into active, semi-stability and stably The class of sulfur ylide three, the sulfur ylide of wherein alkyl, aryl and vinyl is unstable, and contains carbonyl, cyano group, nitro and sulphur The sulfur ylide of acyl group can be stabilized.Therefore sulfur ylide has playing a very important role in organic synthesis.In relatively early stage Research in, sulfur ylide is mainly used in the small ring compounds such as synthesizing epoxy ethane, aziridine and cyclopropane, recently Nian Lai, this kind of reagent are also widely used in the synthesis of non-ternary compound, including tetrahydrofuran, nafoxidine and some more For complexity and in ring, volution compound.
The Domino cyclizations that sulfur ylide participates in have great importance in organic synthesis, can easily conform to the principle of simplicity Single raw material is set out, and efficiently builds multiple chemical bonds, organic molecule of the synthesis with structure diversity and complexity, and sulphur leaf is stood The Domino cyclizations that moral participates in widely are paid close attention to by region of chemistry.Apply in recent years cyclization synthesis of ternary ring, five yuan Good development is achieved on ring, hexatomic ring and polynary and cyclics.
Currently, the competition of the protection of world's novel technique and technological innovation, this brings to the research of synthesis new drug Huge opportunities and challenges.Spiro-compound occupies critical role with its unique structure and property in new drug is synthesized, especially It is Oxoindole spiro-compound, and Oxoindole spirane structure has been increasingly becoming one kind because it has extensive bioactivity Important quasi-medicated property skeleton, is widely present in natural products and bioactive molecule, such as kounidine (Gelsemine) is one The common alkaloid of class, there is good bioactivity, helical curve inhibin (Spirotryprostains) A and B is in lactation Good anti-G2/M cells transfer activity is shown in animal tsFT210 cells, therefore, develops simple efficient synthetic method structure The Oxoindole spiro-compound storehouse for building complexity has become one of research direction of chemist extensive concern.Due to the modern times Organic chemistry is by the puzzlement of intermediate product separating-purifying and protective group, deprotection strategy etc., and cascade reaction goes out Now to overcome many problems of the above to provide opportunity, and shown in synthesizing with optically active natural products and complicated molecule His huge advantage.In recent years, by organic cascade reaction strategy asymmetric syntheses Oxoindole volution compound by The extensive concern of numerous researchers, numerous studies are reported, and respectively from C (3) position, unsaturation oxoindole derivative is satisfied With oxoindole derivative, the unsubstituted oxoindole derivative in C (3) position and the major class initiation material of non-oxide indole derivatives four Set out, carry out a series of related research work.
The synthesis of the organic compound containing complicated functional group such as natural products and drug molecule containing five, hexatomic ring usually needs Multistep reaction is wanted to realize, pilot process also relates to cumbersome separation and purification operations.And participated in by sulfur ylide Domino cyclizations can realize the five, synthesis of hexa-atomic cycle compound, and such new methodology of organic synthesis can equally be reduced Reactions steps, the Separation ＆ Purification for avoiding intermediate in course of reaction, reduce cost and reduce environmental pollution.Thus on The synthesis five of sulfur ylide participation, the Domino cyclizations of hexatomic ring have become the inexorable trend of scientific research development.
The content of the invention
The purpose of the present invention is problem be present for above-mentioned, there is provided one kind is synthesized based on allyl sulfide ylide as three carbon The Oxoindole spiro-compound and its synthetic method of son, this method utilize the characteristic of cascade reaction, save intermediate link, reach The purpose of one-step synthesis target product, reaction efficiency is significantly improved, the reaction time is saved, simplifies reactions steps, is taken for three Five yuan of oxidation spiro-compounds in generation provide a brand-new method and thinking, and the synthesis to similar compound has certain Reference value.
Technical scheme：
It is a kind of to be led to based on Oxoindole spiro-compound of the allyl sulfide ylide as three carbon synthons, its chemical molecular Formula is C21+mH21+nO6+x, wherein m, n, x is 1-10 integer, and molecule has following structure
Wherein：R1For methyl, ethyl, acetyl group, methyl ethyl ether, benzyl or two dimethyl dicarbonate butyl；R2For hydroxyl, first Epoxide or ethyoxyl；R3For 5-F, 5-Br, 5-Cl, 5-CH3、5-OCH3、6-Cl、6-Br、6-OCH3、7-CH3, 7-Cl or 7-Br.
A kind of synthesis side based on Oxoindole spiro-compound of the allyl sulfide ylide as three carbon synthons Method, synthetic route are as follows：
Synthesis step is as follows：
1) preparation of C (3) unsaturated Oxoindole
Under argon gas protection, R will be carried1,R3The isatin of two kinds of substituents, dry toluene and with R2The phosphine leaf of substituent Vertical moral mixing, the amount ratio of the isatin, dry toluene and phosphonium ylide is 1mol (1eq)：10mL：1.5mol (1.5eq), adds Heat is reacted four hours to 85 DEG C, after TLC detection reactions completely, solution is spin-dried for, column chromatography for separation, is obtained C (3) unsaturated oxygen Change indoles；
2) preparation of allyl sulfide ylide
By ethyl crotonate, CCl4Solvent, N- bromo-succinimides and azodiisobutyronitrile are added in reactor and mixed, Ethyl crotonate, CCl4, N- bromo-succinimides and azodiisobutyronitrile amount ratio be 10.4g (0.1mol)：200mL： 1.2eq：500mg, 6h is heated to reflux, reaction terminates rear ice bath cooling, filtering, and revolving removes CCl4, column chromatography for separation, obtain Bromo crotonate light yellow liquid；Bromo crotonate is mixed with acetone solvent, then adds dimethyl sulphide, bromo The amount ratio of ethyl crotonate, acetone and dimethyl sulphide is 3.7g (0.02mol)：15mL：5.6mol (3.3eq.), is stirred at room temperature 12h, filter, washed with acetone, obtain white solid, allyl sulfide ylide is made；
3) synthesis of Oxoindole spiro-compound
Under argon gas protection, the unsaturated Isatine derivatives of C (3), allyl sulfide ylide, acetonitrile and cesium carbonate are added anti- Answer in device and mix, the unsaturated Isatine derivatives of C (3), allyl sulfide ylide, the amount ratio of acetonitrile and cesium carbonate are 1mmol (1.0eq.)：1.5mmol(1.5eq.)：1mL：2.5mmol (2.5eq.), 80 degree are heated to, react 1h, be spin-dried for removing solvent, Column chromatography for separation, obtain Oxoindole spiro-compound.
Used silica gel post is effective length 25cm, internal diameter 26mm, 200-300 mesh SILVER REAGENT silicon in the column chromatography for separation Glue, solvent are the mixed liquor of ethyl acetate and petroleum ether, and the volume ratio of ethyl acetate and petroleum ether is 1 in mixed liquor:3.
It is an advantage of the invention that：This method utilizes the characteristic of cascade reaction, saves intermediate link, reaches one-step synthesis target The purpose of product, reaction efficiency is significantly improved, the reaction time is saved, simplifies reactions steps, for trisubstituted five yuan oxidations Spiro-compound provides a brand-new method and thinking, and the synthesis to similar compound has certain reference value.
Brief description of the drawings
Fig. 1 is the single crystal diffraction figure of the compound in embodiment 1.
Fig. 2 is the one-dimensional carbon nuclear magnetic spectrogram of the compound in embodiment 1, and abscissa is chemical shift, and ordinate is signal Intensity.
Fig. 3 is the one-dimensional hydrogen nuclear magnetic spectrogram of the compound in embodiment 2, and abscissa is chemical shift, and ordinate is signal Intensity.
Fig. 4 is the one-dimensional hydrogen nuclear magnetic spectrogram of the compound in embodiment 3, and abscissa is chemical shift, and ordinate is signal Intensity.
Fig. 5 is the one-dimensional carbon nuclear magnetic spectrogram of the compound in embodiment 4, and abscissa is chemical shift, and ordinate is signal Intensity.
Embodiment
Embodiment 1：
It is a kind of to be based on Oxoindole spiro-compound of the allyl sulfide ylide as three carbon synthons, its chemical formula C24H25NO9, there is following structural formula：
Its synthesis step is as follows：
1) preparation of C (3) unsaturated Oxoindole
Under argon gas protection, R will be carried1,R3The isatin of two kinds of substituents, dry toluene and with R2The phosphine leaf of substituent Vertical moral mixing, the amount ratio of the isatin, dry toluene and phosphonium ylide is 1mol (1eq)：10mL：1.5mol (1.5eq), adds Heat is reacted four hours to 85 DEG C, after TLC detection reactions completely, solution is spin-dried for, column chromatography for separation, is obtained C (3) unsaturated oxygen Change indoles；
2) preparation of allyl sulfide ylide
By ethyl crotonate, CCl4Solvent, N- bromo-succinimides and azodiisobutyronitrile are added in reactor and mixed, Ethyl crotonate, CCl4, N- bromo-succinimides and azodiisobutyronitrile amount ratio be 10.4g (0.1mol)：200mL： 1.2eq：500mg, 6h is heated to reflux, reaction terminates rear ice bath cooling, filtering, and revolving removes CCl4, column chromatography for separation, obtain Bromo crotonate light yellow liquid；Bromo crotonate is mixed with acetone solvent, then adds dimethyl sulphide, bromo The amount ratio of ethyl crotonate, acetone and dimethyl sulphide is 3.7g (0.02mol)：15mL：5.6mol (3.3eq.), is stirred at room temperature 12h, filter, washed with acetone, obtain white solid, allyl sulfide ylide is made；
3) under argon gas protection, C (3) unsaturated Isatine derivatives of 5-OMe substitutions are sequentially added into 25mL reaction tubes 1a 1mmol (1.0eq.), allyl sulfide ylide 1.5mmol, (1.5eq.), acetonitrile 1mL and cesium carbonate 2.5mmol (2.5eq.), 80 DEG C are heated to, react 1h, TLC detection reactions are complete, are spin-dried for removing solvent, column chromatography for separation, used silica gel post For effective length 25cm, internal diameter 26mm, the 200-300 mesh SILVER REAGENT silica gel of Shanghai Sheng Ya companies production, solvent is acetic acid second The mixed liquor of ester and petroleum ether, the volume ratio of ethyl acetate and petroleum ether is 1 in mixed liquor:3, obtain target product, yield 87%.
Fig. 1 is the single crystal diffraction figure of the compound in embodiment 1.
Fig. 2 is the one-dimensional carbon nuclear magnetic spectrogram of the compound in embodiment 1, and abscissa is chemical shift, and ordinate is signal Intensity.
1H NMR (400MHz, Chloroform-d) δ=8.05 (d, J=8.9Hz, 1H), 6.95 (q, J=2.5Hz, 1H), 6.77 (dd, J=8.9,2.8Hz, 1H), 6.61 (d, J=2.7Hz, 1H), 5.56-5.49 (m, 1H), 4.71 (s, 1H), 3.91 (q, J=7.1Hz, 2H), 3.75 (s, 3H), 3.72 (s, 3H), 3.42 (s, 3H), 3.23 (ddd, J=19.2,2.8, 1.7Hz, 1H), 2.88 (dt, J=19.1,2.7Hz, 1H), 2.72 (s, 3H), 1.11 (t, J=7.1Hz, 3H) ppm；13C NMR (101MHz,CDCl3) δ=182.04,170.99,169.97,166.77,163.97,156.81,141.85,134.26, 133.80,131.98,116.99,113.04,110.03,93.14,59.52,57.10,56.75,55.39,51.61,45.47, 26.13,14.12,1.00ppm；ESI-HRMS:calcd.For C24H25NO9S+H 472.1608,found 472.1610.
Embodiment 2：
It is a kind of to be based on Oxoindole spiro-compound of the allyl sulfide ylide as three carbon synthons, its chemical formula C25H27NO9, and there is following structural formula：
Its synthesis step is as follows：
1) it is, 2) same as Example 1；
3) under argon gas protection, C (3) unsaturated Isatine derivatives of 5-OMe substitutions are sequentially added into 25mL reaction tubes 1b (1mmol, 1.0eq.), allyl sulfide ylide (1.5mmol, 1.5eq.), acetonitrile 1mL, cesium carbonate (2.5mmol, 2.5eq.), 80 degree are heated to, reacts 1.5h, TLC detection reactions are complete, are spin-dried for removing solvent, column chromatography for separation, used silica gel Post is effective length 25cm, internal diameter 26mm, the 200-300 mesh SILVER REAGENT silica gel of Shanghai Sheng Ya companies production, and solvent is acetic acid The mixed liquor of ethyl ester and petroleum ether, the volume ratio of ethyl acetate and petroleum ether is 1 in mixed liquor:3, obtain target product, yield 79%.
Fig. 3 is the one-dimensional hydrogen nuclear magnetic spectrogram of the compound in embodiment 2, and abscissa is chemical shift, and ordinate is signal Intensity.
1H NMR (400MHz, Chloroform-d) δ=8.07 (d, J=9.0Hz, 1H), 6.96 (d, J=2.4Hz, 1H), 6.78 (dd, J=8.9,2.7Hz, 1H), 6.65 (d, J=2.8Hz, 1H), 5.55 (q, J=2.3Hz, 1H), 4.70 (s, 1H), 3.93 (q, J=7.1Hz, 2H), 3.77 (s, 3H), 3.74 (s, 3H), 3.66 (dd, J=9.7,7.0Hz, 1H), 3.49 (dq, J=9.6,7.0Hz, 1H), 3.27 (dt, J=19.1,2.2Hz, 1H), 2.89 (dt, J=19.1,2.8Hz, 1H), 2.75 (s, 3H), 1.32-1.24 (m, 3H), 1.13 (t, J=7.1Hz, 3H) ppm；13C NMR(101MHz,CDCl3) δ=181.99, 171.02,169.17,166.94,164.10,156.75,141.39,134.48,133.77,132.10,116.90,112.73, 110.45,93.22,63.90,59.44,57.22,56.81,55.52,51.52,45.50,29.31,26.14,14.14, 13.90ppm；ESI-HRMS:calcd.For C25H27NO9+H 486.1764,found 486.1776.
Embodiment 3：
It is a kind of to be based on Oxoindole spiro-compound of the allyl sulfide ylide as three carbon synthons, its chemical formula C24H25NO8, and there is following structural formula：
Its synthesis step is as follows：
1) it is, 2) same as Example 1；
3) argon gas protection under, sequentially added into 25mL reaction tubes the unsaturated Isatine derivatives 1c of C (3) (1mmol, 1.0eq.), allyl sulfide ylide (1.5mmol, 1.5eq.), acetonitrile 1mL, cesium carbonate (2.5mmol, 2.5eq.), are heated to 80 degree, 1.5h is reacted, TLC detection reactions are complete, are spin-dried for removing solvent, column chromatography for separation, used silica gel post is effective length 25cm, internal diameter 26mm, the 200-300 mesh SILVER REAGENT silica gel of Shanghai Sheng Ya companies production, solvent is ethyl acetate and petroleum ether Mixed liquor, the volume ratio of ethyl acetate and petroleum ether is 1 in mixed liquor:3, obtain target product, yield 88%.
1H NMR (400MHz, Chloroform-d) δ=8.26 (d, J=7.7Hz, 1H), 7.36 (dd, J=15.7, 9.9Hz, 1H), 7.11 (td, J=7.6,1.1Hz, 1H), 6.74 (dd, J=7.6,1.3Hz, 1H), 6.09 (d, J=15.7Hz, 1H), 5.14 (d, J=1.1Hz, 1H), 4.64 (s, 3H), 3.99-3.91 (m, 3H), 3.74 (s, 3H), 3.61 (dq, J=9.6, 7.0Hz, 3H), 3.15 (dd, J=9.9,8.2Hz, 1H), 2.75 (d, J=1.3Hz, 3H), 1.48 (t, J=7.0Hz, 3H), 1.09(t,3H)ppm；13C NMR(100MHz,CDCl3) δ=173.65,171.02,166.25,163.85,142.21, 140.49,128.50,127.89,125.30,124.41,124.02,119.53,116.54,116.09,96.16,93.15, 64.56,59.74,51.61,41.96,40.87,37.79,26.71,14.11ppm；ESI-HRMS:calcd.For C24H25NO8 +H 456.1658,found 456.1658.
Fig. 4 is the one-dimensional hydrogen nuclear magnetic spectrogram of the compound in embodiment 3, and abscissa is chemical shift, and ordinate is signal Intensity.
Embodiment 4：
It is a kind of to be based on Oxoindole spiro-compound of the allyl sulfide ylide as three carbon synthons, its chemical formula C17H17NO5, and there is following structural formula：
Its synthesis step is as follows：
1) it is, 2) same as Example 1；
3) argon gas protection under, sequentially added into 25mL reaction tubes the unsaturated Isatine derivatives 1d of C (3) (1mmol, 1.0eq.), allyl sulfide ylide (1.5mmol, 1.5eq.), acetonitrile 1mL, cesium carbonate (2.5mmol, 2.5eq.), are heated to 80 degree, 1.5h is reacted, TLC detection reactions are complete, are spin-dried for removing solvent, column chromatography for separation, used silica gel post is effective length 25cm, internal diameter 26mm, the 200-300 mesh SILVER REAGENT silica gel of Shanghai Sheng Ya companies production, solvent is ethyl acetate and petroleum ether Mixed liquor, the volume ratio of ethyl acetate and petroleum ether is 1 in mixed liquor:3, obtain target product, yield 98%.
Fig. 5 is the one-dimensional hydrogen nuclear magnetic spectrogram of the compound in embodiment 4, and abscissa is chemical shift, and ordinate is signal Intensity.
1H NMR (400MHz, Chloroform-d) δ=8.28 (d, J=7.7Hz, 1H), 7.26 (dd, J=15.7, 9.9Hz, 1H), 7.15 (td, J=7.6,1.1Hz, 1H), 6.79 (dd, J=7.6,1.3Hz, 1H), 6.19 (d, J=15.7Hz, 1H), 5.24 (d, J=1.1Hz, 1H), 4.66 (s, 3H), 3.99-3.91 (m, 3H), 3.71 (s, 3H), 3.62 (dq, J=9.6, 7.0Hz, 3H), 3.12 (dd, J=9.9,8.2Hz, 1H), 2.71 (d, J=1.3Hz, 3H), 1.41 (t, J=7.0Hz, 3H), 1.08(t,3H)ppm；13C NMR(101MHz,CDCl3) δ=174.65,171.08,166.55,163.75,142.31, 140.59,128.51,127.88,125.31,124.42,124.03,119.43,116.57,116.00,96.11,93.11, 64.54,59.70,51.64,41.95,40.86,37.79,26.71,14.21ppm；ESI-HRMS:calcd.For C23H23NO8 +H 442.1502,found 442.1515.

Claims (3)

  1. It is 1. a kind of based on Oxoindole spiro-compound of the allyl sulfide ylide as three carbon synthons, it is characterised in that chemistry General molecular formula is C21+mH21+nO6+x, wherein m, n, x is 1-10 integer, and molecule has following structure
    Wherein：R1For methyl, ethyl, acetyl group, methyl ethyl ether, benzyl or two dimethyl dicarbonate butyl；R2For hydroxyl, methoxyl group Or ethyoxyl；R3For 5-F, 5-Br, 5-Cl, 5-CH3、5-OCH3、6-Cl、6-Br、6-OCH3、7-CH3, 7-Cl or 7-Br.
  2. It is 2. a kind of as claimed in claim 1 based on Oxoindole spiro-compound of the allyl sulfide ylide as three carbon synthons Synthetic method, it is characterised in that synthetic route is as follows：
    Synthesis step is as follows：
    1) preparation of C (3) unsaturated Oxoindole
    Under argon gas protection, R will be carried1,R3The isatin of two kinds of substituents, dry toluene and with R2The phosphonium ylide of substituent Mixing, the amount ratio of the isatin, dry toluene and phosphonium ylide is 1mol (1eq)：10mL：1.5mol (1.5eq), is heated to 85 DEG C, react four hours, after TLC detection reactions completely, solution is spin-dried for, column chromatography for separation, obtain the unsaturated oxidation Yin of C (3) Diindyl；
    2) preparation of allyl sulfide ylide
    By ethyl crotonate, CCl4Solvent, N- bromo-succinimides and azodiisobutyronitrile are added in reactor and mixed, crotons Sour methyl esters, CCl4, N- bromo-succinimides and azodiisobutyronitrile amount ratio be 10.4g (0.1mol)：200mL： 1.2eq：500mg, 6h is heated to reflux, reaction terminates rear ice bath cooling, filtering, and revolving removes CCl4, column chromatography for separation, obtain Bromo crotonate light yellow liquid；Bromo crotonate is mixed with acetone solvent, then adds dimethyl sulphide, bromo The amount ratio of ethyl crotonate, acetone and dimethyl sulphide is 3.7g (0.02mol)：15mL：5.6mol (3.3eq.), is stirred at room temperature 12h, filter, washed with acetone, obtain white solid, allyl sulfide ylide is made；
    3) synthesis of Oxoindole spiro-compound
    Under argon gas protection, the unsaturated Isatine derivatives of C (3), allyl sulfide ylide, acetonitrile and cesium carbonate are added into reactor Middle mixing, the unsaturated Isatine derivatives of C (3), allyl sulfide ylide, the amount ratio of acetonitrile and cesium carbonate are 1mmol (1.0eq.)：1.5mmol(1.5eq.)：1mL：2.5mmol (2.5eq.), 80 degree are heated to, react 1h, be spin-dried for removing solvent, Column chromatography for separation, obtain Oxoindole spiro-compound.
  3. 3. according to claim 2 based on allyl sulfide ylide as the Oxoindole spiro-compound of three carbon synthons Synthetic method, it is characterised in that：Used silica gel post is effective length 25cm, internal diameter 26mm, 200-300 in the column chromatography for separation Mesh SILVER REAGENT silica gel, solvent are the mixed liquor of ethyl acetate and petroleum ether, the volume of ethyl acetate and petroleum ether in mixed liquor Than for 1:3.
CN201611025219.2A 2016-11-22 2016-11-22 It is a kind of based on Oxoindole spiro-compound and its synthetic method of the allyl sulfide ylide as three carbon synthons Pending CN107337631A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201611025219.2A CN107337631A (en) 2016-11-22 2016-11-22 It is a kind of based on Oxoindole spiro-compound and its synthetic method of the allyl sulfide ylide as three carbon synthons

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201611025219.2A CN107337631A (en) 2016-11-22 2016-11-22 It is a kind of based on Oxoindole spiro-compound and its synthetic method of the allyl sulfide ylide as three carbon synthons

Publications (1)

Publication Number Publication Date
CN107337631A true CN107337631A (en) 2017-11-10

Family

ID=60223124

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201611025219.2A Pending CN107337631A (en) 2016-11-22 2016-11-22 It is a kind of based on Oxoindole spiro-compound and its synthetic method of the allyl sulfide ylide as three carbon synthons

Country Status (1)

Country Link
CN (1) CN107337631A (en)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016023217A1 (en) * 2014-08-15 2016-02-18 安润医药科技（苏州）有限公司 Quinazoline derivative, preparation method therefor, and pharmaceutical composition and application thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016023217A1 (en) * 2014-08-15 2016-02-18 安润医药科技（苏州）有限公司 Quinazoline derivative, preparation method therefor, and pharmaceutical composition and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
FANGRUI ZHONG ET AL.: "Highly Enantioselective [3+2] Annulation of Morita-Baylis-Hillman Adducts Mediated by l-Threonine-Derived Phosphines: Synthesis of 3-Spirocyclopentene-2-oxindoles having Two Contiguous Quaternary Centers", 《ANGEW.CHEM.INT.ED.》 *
QING-GANG WANG ET AL.: "Tandem Michael Addition/Ylide Epoxidation for the Synthesis of Highly Functionalized Cyclohexadiene Epoxide Derivatives", 《J.AM.CHEM.SOC.》 *

Similar Documents

Publication Publication Date Title
CN106543070A (en) Carbazole amide-type room temperature phosphorimetry molecule that N replaces and its preparation method and application
CN106928128A (en) A kind of Novel alkyl free radical and preparation method thereof
CN114380675A (en) Method for synthesizing aryl phenol by reaction of halogenated aromatic hydrocarbon and phenol compound induced by visible light
CN106380446B (en) Synthesis method of quinoline-2 formate derivative
CN106117216B (en) A kind of method of atmospheric synthesis 6H- iso-indoles [2,1-a] indoles -6- ketone compounds
CN109705001B (en) Method for preparing 3-sulfonyl-1, 2-dihydronaphthalene compound by photocatalysis
CN112500339B (en) Synthesis method of 8-acylquinoline derivative
CN105669441A (en) Preparation method of alpha-acyloxyketone compound
CN106831531B (en) A kind of Isatine derivatives and its synthetic method
CN112552285A (en) Synthesis method of 4- (2,2, 2-trichloroethyl) -beta-lactam derivative
CN107337631A (en) It is a kind of based on Oxoindole spiro-compound and its synthetic method of the allyl sulfide ylide as three carbon synthons
CN115093372B (en) Synthesis method of imidazole derivative
CN108276334B (en) Preparation method of acridone and derivatives thereof
CN113651788B (en) 3-aminoalkylchromone compound and preparation method thereof
CN115772157A (en) Preparation method of 2-alkoxy indole compound
CN105384715B (en) A kind of bromo- 4- phenyl coumarin series compound preparation method of 3- of 7- substitution
CN111777543B (en) Method for preparing N-phenylcarbazole through copper-catalyzed bromobenzene and carbazole C-N coupling
CN109369678B (en) Synthetic method of natural product isomer (-) -6-epi-Poranteridine
CN104193667A (en) Synthesis method of divergently oriented azacycles
CN110156730A (en) A kind of synthetic method of chiral tricyclic benzofuran compounds
CN112920191B (en) Arylethynyl oxindole oxirane as well as preparation method and application thereof
CN111087402A (en) Method for asymmetrically synthesizing Epicocin G alkaloid of ETP natural product
CN107663165A (en) The new method that a kind of C H bond activations of the positions of indoles C 3 are efficiently esterified
CN108794396A (en) The method for oxidation of 4- oxo -2,3- compound in category of dihydro quinolines
CN113968819B (en) Synthesis method of polysubstituted pyrazole compound

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20171110