CN111517938A - Synthesis of heptatomic bridged ring derivatives and preparation method thereof - Google Patents
Synthesis of heptatomic bridged ring derivatives and preparation method thereof Download PDFInfo
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- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/82—Ketones containing a keto group bound to a six-membered aromatic ring containing hydroxy groups
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- C07D207/46—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with hetero atoms directly attached to the ring nitrogen atom
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- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
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Abstract
The invention discloses a seven-membered bridged ring derivative shown in formula (I) and a synthesis method thereof, wherein the synthesis method comprises the step of synthesizing the seven-membered bridged ring derivative shown in formula (I) by taking an alkynone compound and 1, 3-indandione as raw materials under the promotion action of alkali. The preparation method has the advantages of simple and easily obtained raw materials, high atom economy, high chemical regioselectivity, simple and convenient post-treatment, good universality, good yield, environmental friendliness and the like. The seven-membered bridged ring derivatives disclosed by the invention are main structural units in a plurality of natural products and drug molecules, most of the seven-membered bridged ring derivatives have stronger biological activity, and have great research value in the aspect of drug synthesis.
Description
Technical Field
The invention belongs to the technical field of organic compound synthesis, and relates to a synthetic method of a base-catalyzed seven-membered bridged ring derivative.
Background
Bridged ring compounds are widely found in natural products and drug molecules. The seven-element bridge ring system is the core skeleton of natural products with obvious activity. Based on these, many researches have been made on the synthesis method of the seven-membered bridged ring compound. Conventional methods for synthesizing seven-membered bridged ring compounds generally include intramolecular cyclization reactions, Ring Closing Metathesis (RCM), and carbon-carbon bond activation reactions. For example: literature (1) Brailsford, j.a., Zhu, l.; lo, m.; shea, k.j.j.org.chem.2007,72,9402.(2) Morehead Jr, a.; grubbs, r.chem.commun.1998,275.(3) Ko, h.m.; dong, g.nat.chem.2014,6,739.
In addition, [4+2] cycloaddition of a seven-membered ring compound (4 π component) with an unsaturated compound (2 π component) is also a direct and efficient method for the synthesis of seven-membered bridged cyclic compounds and has high atom economy. For example, documents (4) Li, p.j.am.chem.soc.2009,131,16628.(5) Uyehara, t.; miyakoshi, s.; kitahara, Y.Bull.chem.Soc.JP.1979,52,2023, but the prior art has the defects of needing Lewis acid catalysis or high-temperature promotion, poor chemical regioselectivity, complicated raw material synthesis, limited substrate and the like. Therefore, the development of more economical and efficient synthetic methods of seven-membered bridged ring compounds with simple reaction conditions and high chemical regioselectivity is still needed.
Disclosure of Invention
The invention aims to provide a seven-membered bridged ring derivative and a synthesis method thereof, wherein the synthesis method is an alkali-promoted, low-cost and environment-friendly synthesis method. The seven-membered bridged ring derivatives provided by the invention are main structural units in a plurality of natural products and drug molecules, most of the seven-membered bridged ring derivatives have stronger biological activity, and have great research value in the aspect of drug synthesis.
The structure of the seven-membered bridged ring derivative not reported in the invention is shown in the formula (I):
wherein the content of the first and second substances,
R1is phenyl, electron-donating substituted phenyl, naphthyl, furyl or pyrrolyl, and the electron-donating group is alkyl or alkoxy;
R2is phenyl, electron-withdrawing or electron-donating substituted phenyl, the electron-withdrawing group is halogen, and the electron-donating group is alkoxy;
preferably, the first and second electrodes are formed of a metal,
R1is phenyl, C1-C10 alkyl substituted phenyl, C1-C10 alkoxy substituted phenyl, naphthyl, furyl or pyrrolyl;
R2is phenyl, halogen substituted phenyl, C1-C10 alkoxy substituted phenyl;
it is further preferred that the first and second liquid crystal compositions,
R1is phenyl, p-methylphenyl, p-methoxyphenyl, 3, 4-dimethoxyphenyl, 3,4, 5-trimethoxyphenyl, α -naphthyl, 2-furyl or 2-pyrrolyl;
R2is phenyl, p-methylphenyl, p-chlorophenyl, p-methoxyphenyl.
The invention also provides a synthetic method of the seven-membered bridged ring derivative, in a solvent, reacting raw materials of an alkynone compound and 1, 3-indandione under the action of alkali to obtain the seven-membered bridged ring derivative; the reaction process is shown as the formula (II):
wherein the content of the first and second substances,
R1is phenyl, electron-donating substituted phenyl, naphthyl, furyl or pyrrolyl, and the electron-donating group is alkyl or alkoxy;
R2is phenyl, electron-withdrawing or electron-donating substituted phenyl, the electron-withdrawing group is halogen, and the electron-donating group is alkoxy;
preferably, the first and second electrodes are formed of a metal,
R1is phenyl, C1-C10 alkyl substituted phenyl, C1-C10 alkoxy substituted phenyl, naphthyl, furyl or pyrrolyl;
R2is phenyl, halogen substituted phenyl, C1-C10 alkoxy substituted phenyl;
it is further preferred that the first and second liquid crystal compositions,
R1is phenyl, p-methylphenyl, p-methoxyphenyl, 3, 4-dimethoxyphenyl, 3,4, 5-trimethoxyphenyl, α -naphthyl, 2-furyl or 2-pyrrolyl;
R2is phenyl, p-methylphenyl, p-chlorophenyl, p-methoxyphenyl.
Wherein the base is a catalyst selected from DABCO, NaOH and K2CO3、Cs2CO3And the like.
Wherein the solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide or dimethyl sulfoxide.
Wherein the molar ratio of the alkynone compound to the 1, 3-indandione to the alkali is 2.2: 1: 3.
wherein the temperature of the reaction is 110 ℃.
Wherein the reaction time is 3 hours.
The invention is preferably carried out under nitrogen protection.
In one embodiment, the synthesis method of the heptatomic bridged ring derivative is as follows: under the protection of nitrogen, in a solvent, reacting raw materials of an alkynone compound and 1, 3-indandione under the action of alkali to obtain the seven-membered bridged ring derivative; the reaction process is shown as the formula (II'):
wherein R is1、R2Is as defined in formula (II).
The invention has the beneficial effects that: the preparation method has the advantages of simple and easily obtained raw materials, high atom economy, high chemical regioselectivity, simple and convenient post-treatment, good universality, good yield (58-98%), environmental friendliness and the like. The seven-membered bridged ring derivatives provided by the invention are main structural units in a plurality of natural products and drug molecules, most of the seven-membered bridged ring derivatives have stronger biological activity, and have great research value in the aspect of drug synthesis.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples. The procedures, conditions, implementation methods and the like for carrying out the present invention are general knowledge and well-known attempts in the art, except for those specifically mentioned below, and the present invention is not particularly limited thereto.
Example 1: synthesis of IA
The alkynone, the alkali and the solvent are respectively selected from 1, 3-diphenyl-2-propargyl-1-ketone and K2CO3N, N-Dimethylformamide (DMF), the dosages of the raw materials are 0.44mmol of alkynone 1, 3-diphenyl-2-propargyl-1-ketone, 0.2mmol of 1, 3-indandione and K2CO30.6mmol and 5mL of solvent are reacted at 110 ℃ for 3 hours to obtain the target product, namely the formula (IA), yellow solid, and the isolation yield is 64%. mp 167-169 ℃.
Nuclear magnetic data:
1H NMR(400MHz,CDCl3,TMS):4.68(s,1H),5.23(s,1H),7.10-7.15(m,10H),7.26-7.33(m,6H),7.37-7.49(m,6H),7.60(d,J＝7.8Hz,1H),8.38(d,J＝7.8Hz,1H)；13C NMR(100MHz,CDCl3):69.23,77.91,123.73,127.44,128.02,128.53,128.70,128.82,128.86,129.53,131.27,133.64,133.71,136.71,137.06,138.13,145.41,146.53,187.70,197.54.
high resolution mass spectral data: HRMS (ESI) calcd for C39H27O4[M+H]+:559.1904；found559.1913.
Example 2: synthesis of IB
The alkynone, alkali and solvent are respectively selected from 1- (p-methylphenyl) -3-phenyl-2-propargyl-1-ketone and K2CO3N, N-Dimethylformamide (DMF), the dosages of the raw materials are respectively 0.44mmol of 1- (p-methylphenyl) -3-phenyl-2-propargyl-1-ketone, 0.2mmol of 1, 3-indandione and K2CO30.6mmol and 5mL of solvent are reacted at 110 ℃ for 3 hours to obtain the target product of formula (IB), a yellow solid, and the isolation yield is 71%. mp 114-.
Nuclear magnetic data:
1H NMR(400MHz,CDCl3,TMS):2.23(s,6H),4.54(s,1H),5.22(s,1H),6.93(d,J＝8Hz,4H),7.09-7.16(m,6H),7.30-7.40(m,9H),7.45-7.48(m,1H),7.60(d,J＝7.6Hz,1H),8.37(d,J＝7.8Hz,1H)；13C NMR(100MHz,CDCl3,TMS):21.35,69.05,77.83,123.79,127.54,127.98,128.68,128.73,129.34,129.74,131.20,133.58,134.27,137.21,137.35,144.86,145.66,146.50,187.94,197.11.
high resolution mass spectral data: HRMS (ESI) calcd for C41H31O4[M+H]+:587.2217；found587.2224.
Example 3: synthesis of IC
The alkynone, alkali and solvent are respectively selected from 1- (p-methoxyphenyl) -3-phenyl-2-propargyl-1-one and K2CO3N, N-Dimethylformamide (DMF), the dosages of the raw materials are respectively 0.44mmol of 1- (p-methoxyphenyl) -3-phenyl-2-propargyl-1-ketone, 0.2mmol of 1, 3-indandione and K2CO30.6mmol and 5mL of solvent are reacted at 110 ℃ for 3 hours to obtain the target product, namely the formula (IC), yellow solid, and the isolation yield is 63%. mp 109-.
Nuclear magnetic data:
1H NMR(400MHz,CDCl3,TMS):3.70(s,6H),4.56(s,1H),5.21(s,1H),6.60(d,J＝8.8Hz,4H),7.08-7.17(m,6H),7.32(d,J＝7.4Hz,4H),7.39-7.46(m,6H),7.61(d,J＝7.9Hz,1H),8.37(d,J＝8.0Hz,1H)；13C NMR(100MHz,CDCl3,TMS):55.22,68.94,77.77,113.80,123.81,127.58,127.94,128.67,129.79,131.18,132.07,133.56,136.88,137.29,145.78,146.56,164.23,188.02,195.88.
high resolution mass spectral data: HRMS (ESI) calcd for C41H31O6[M+H]+:619.2115；found619.2119.
Example 4: synthesis of ID
The alkynone, the alkali and the solvent are respectively selected from 1- (3, 4-dimethoxyphenyl) -3-phenyl-2-propargyl-1-ketone and K2CO3N, N-Dimethylformamide (DMF), the dosages of the raw materials are respectively 0.44mmol of 1- (3, 4-dimethoxyphenyl) -3-phenyl-2-propargyl-1-ketone, 0.2mmol of 1, 3-indandione and K2CO30.6mmol and 5mL of solvent, and reacting at 110 ℃ for 3 hours to obtain the target product of formula (ID) as a yellow solid with an isolated yield of 72%. mp 133-.
Nuclear magnetic data:
1H NMR(400MHz,CDCl3,TMS):3.60(s,6H),3.79(s,6H),4.46(s,1H),5.24(s,1H),6.56(d,J＝8.4Hz,2H),7.05-7.18(m,10H),7.33(d,J＝7.4Hz,4H),7.44-7.49(m,2H),7.64(d,J＝7.8Hz,1H),8.38(d,J＝8.0Hz,1H)；13C NMR(100MHz,CDCl3):55.44,55.81,68.70,77.74,110.23,111.25,124.12,124.80,127.68,127.77,128.69,128.75,129.74,131.06,133.75,136.61,137.34,145.78,146.46,148.92,154.01,188.15,195.92.
high resolution mass spectral data: HRMS (ESI) calcd for C43H35O8[M+H]+:679.2326；found679.2321.
Example 5: synthesis of IE
The alkynone, the alkali and the solvent are respectively selected from 1- (3,4, 5-trimethoxyphenyl) -3-phenyl-2-propargyl-1-one and K2CO3N, N-Dimethylformamide (DMF), the dosages of the raw materials are respectively 0.44mmol of 1- (3,4, 5-trimethoxyphenyl) -3-phenyl-2-propargyl-1-ketone, 0.2mmol of 1, 3-indandione and K2CO30.6mmol and 5mL of solvent are reacted at 110 ℃ for 3 hours to obtain the target product, namely the formula (IE), as a yellow solid, and the isolation yield is 62%. mp 171-.
Nuclear magnetic data:
1H NMR(400MHz,CDCl3,TMS):3.53(s,12H),3.78(s,6H),4.39(s,1H),5.25(s,1H),6.74(s,4H),7.15-7.20(m,6H),7.31(d,J＝7.3Hz,4H),7.44-7.47(m,2H),7.67(d,J＝7.3Hz,1H),8.38(d,J＝7.2Hz,1H)；13C NMR(100MHz,CDCl3):55.62,60.69,68.62,77.74,106.73,124.46,127.63,127.72,128.78,128.90,128.93,130.98,131.43,134.03,136.88,137.26,143.14,145.57,146.41,153.07,188.10,196.18.
high resolution mass spectral data: HRMS (ESI) calcd for C45H39O10[M+H]+:739.2538；found739.2553.
Example 6: synthesis of IF
The alkynone, alkali and solvent are respectively selected from 1-naphthalene-3-phenyl-2-propargyl-1-one and K2CO3N, N-Dimethylformamide (DMF), the dosages of the raw materials are 0.44mmol of 1-naphthalene-3-phenyl-2-propargyl-1-ketone, 0.2mmol of 1, 3-indandione and K2CO30.6mmol and 5mL of solvent are reacted at 110 ℃ for 3 hours to obtain the target product, formula (IF), yellow solid, with the isolation yield of 68%. mp 114-.
Nuclear magnetic data:
1H NMR(400MHz,CDCl3,TMS):5.15(s,1H),5.37(s,1H),6.94-7.01(m,6H),7.19(d,J＝7.3Hz,2H),7.25-7.28(m,3H),7.40-7.44(m,2H),7.47-7.52(m,4H),7.56-7.63(m,4H),7.73(d,J＝8.4Hz,4H),8.38(d,J＝8.0Hz,1H),8.87(d,J＝8.7Hz,2H)；13C NMR(100MHz,CDCl3):70.12,78.70,123.92,124.04,125.96,126.65,127.96,128.47,128.51,128.64,128.77,130.98,131.24,131.50,133.63,133.79,133.98,134.54,137.21,139.93,147.25,147.69,187.04,199.03.
high resolution mass spectral data: HRMS (ESI) calcd for C47H31O4[M+H]+:659.2217；found659.2209.
Example 7: synthesis of IG
The alkynone, the alkali and the solvent are respectively selected from 1- (2-furan) -3-phenyl-2-propargyl-1-ketone and K2CO3N, N-Dimethylformamide (DMF), the dosages of the raw materials are respectively 0.44mmol of 1- (2-furan) -3-phenyl-2-propargyl-1-ketone, 0.2mmol of 1, 3-indandione and K2CO30.6mmol and 5mL of solvent are reacted at 110 ℃ for 3 hours to obtain the target product, namely a yellow solid shown in the formula (IG), with the isolated yield of 67%. mp 151-.
Nuclear magnetic data:
1H NMR(400MHz,CDCl3,TMS):4.63(s,1H),5.20(s,1H),6.13(d,J＝3.5Hz,2H),6.24(s,2H),7.17-7.24(m,6H),7.33-7.35(m,6H),7.45(t,J＝6.4Hz,2H),7.68(d,J＝7.4Hz,1H),8.33(d,J＝7.4Hz,1H)；13C NMR(100MHz,CDCl3):69.01,77.46,112.45,121.41,123.68,127.23,127.88,128.82,128.86,128.97,131.11,133.52,137.18,138.99,144.70,146.56,148.18,152.60,183.34,187.82.
high resolution mass spectral data: HRMS (ESI) calcd for C35H23O6[M+H]+:539.1489；found539.1489.
Example 8: synthesis of IH
The alkynone, the alkali and the solvent are respectively selected from 1- (1-p-methylbenzenesulfonyl-1H-2-pyrrole) -3- (p-methylphenyl) -2-propargyl-1-one and K2CO3N, N-Dimethylformamide (DMF), the dosage of the raw materials is 1- (1-p-methylbenzenesulfonyl-1H-2-pyrrole) -3- (p-methylphenyl) -2-propargyl-0.44mmol of 1-ketone, 0.2mmol of 1, 3-indandione, and K2CO30.6mmol and 5mL of solvent are reacted at 110 ℃ for 3 hours to obtain the target product of formula (IH) as a yellow solid, and the isolation yield is 58%. mp132-134 ℃.
Nuclear magnetic data:
1H NMR(400MHz,CDCl3,TMS):2.20(s,6H),2.48(s,6H),4.41(s,1H),5.07(s,1H),5.78-5.82(m,4H),6.86(d,J＝7.9Hz,4H),7.04(d,J＝7.9Hz,4H),7.34-7.42(m,6H),7.52-7.56(m,3H),7.92(d,J＝8.2Hz,4H),8.27(d,J＝7.7Hz,1H)；13C NMR(100MHz,CDCl3):20.87,21.46,68.93,77.54,110.50,124.23,127.26,127.32,127.85,128.64,128.89,129.34,129.62,130.97,131.01,133.40,133.54,134.13,135.89,138.38,138.60,144.46,145.18,146.65,182.88,188.06.
high resolution mass spectral data: HRMS (ESI) calcd for C51H40N2NaO8S2[M+Na]+:895.2118；found895.2117.
Example 9: synthesis of II
The alkynone, alkali and solvent are respectively selected from 1-phenyl-3- (p-methoxyphenyl) -2-propargyl-1-one and K2CO3N, N-Dimethylformamide (DMF), the dosages of the raw materials are respectively 0.44mmol of 1-phenyl-3- (p-methoxyphenyl) -2-propargyl-1-ketone, 0.2mmol of 1, 3-indandione and K2CO30.6mmol and 5mL of solvent are reacted for 3 hours at 110 ℃ to obtain the target product of formula (II) and yellow solid, and the separation yield is 82%. mp 107-.
Nuclear magnetic data:
1H NMR(400MHz,CDCl3,TMS):3.65(s,6H),4.70(s,1H),5.18(s,1H),6.65(d,J＝8.6Hz,4H),7.12(t,J＝7.7Hz,4H),7.23(d,J＝8.5Hz,4H),7.29-7.39(m,3H),7.42-7.46(m,5H),7.58(d,J＝7.8Hz,1H),8.34(d,J＝7.7Hz,1H)；13C NMR(100MHz,CDCl3):55.02,69.59,77.90,114.04,123.57,127.52,128.51,128.62,129.42,129.53,129.55,131.12,133.53,133.61,136.85,137.96,143.94,147.02,160.12,187.94,197.87.
high resolution mass spectral data: HRMS (ESI) calcd for C41H31O6[M+H]+:619.2115；found619.2128.
Example 10: synthesis of IJ
The alkynone, alkali and solvent are respectively selected from 1-phenyl-3- (p-chlorophenyl) -2-propargyl-1-one and K2CO3N, N-Dimethylformamide (DMF), the dosages of the raw materials are respectively 0.44mmol of 1-phenyl-3- (p-chlorophenyl) -2-propargyl-1-ketone, 0.2mmol of 1, 3-indandione and K2CO30.6mmol and 5mL of solvent are reacted for 3 hours at 110 ℃ to obtain the target product, namely the formula (IJ) and yellow solid, and the separation yield is 98%. mp 209-.
Nuclear magnetic data:
1H NMR(400MHz,CDCl3,TMS):4.57(s,1H),5.08(s,1H),7.11-7.17(m,8H),7.21-7.27(m,4H),7.35-7.42(m,7H),7.49(t,J＝7.5Hz,1H),7.57(d,J＝7.9Hz,1H),8.38(d,J＝7.8Hz,1H)；13C NMR(100MHz,CDCl3):68.86,77.86,123.91,127.26,128.73,129.03,129.30,129.53,131.40,133.85,134.09,135.08,135.39,136.43,136.50,146.10,187.42,197.20.
high resolution mass spectral data: HRMS (ESI) calcd for C39H24Cl2NaO4[M+Na]+:649.0944；found649.0945.
The protection of the present invention is not limited to the above embodiments. Variations and advantages that may occur to those skilled in the art may be incorporated into the invention without departing from the spirit and scope of the inventive concept, and the scope of the appended claims is intended to be protected.
Claims (10)
1. A seven-membered bridged ring derivative is characterized by having a structure shown in formula (I):
wherein the content of the first and second substances,
R1is phenyl, electron-donating substituted phenyl, naphthyl, furyl or pyrrolyl, and the electron-donating group is alkyl or alkoxy;
R2is phenyl, electron-withdrawing or electron-donating substituted phenyl, the electron-withdrawing group is halogen, and the electron-donating group is alkoxy.
2. The seven-membered bridged ring derivative of claim 1, wherein R is1Is phenyl, C1-C10 alkyl substituted phenyl, C1-C10 alkoxy substituted phenyl, naphthyl, furyl or pyrrolyl; r2Is phenyl, halogen substituted phenyl, C1-C10 alkoxy substituted phenyl.
3. The seven-membered bridged ring derivative of claim 1, wherein R is1Is phenyl, p-methylphenyl, p-methoxyphenyl, 3, 4-dimethoxyphenyl, 3,4, 5-trimethoxyphenyl, α -naphthyl, 2-furyl, 2-pyrrolyl R2Is phenyl, p-methylphenyl, p-chlorophenyl, p-methoxyphenyl.
4. A synthetic method of a seven-membered bridged ring derivative is characterized in that in a solvent, raw materials of an alkynone compound and 1, 3-indandione react under the action of alkali to obtain the seven-membered bridged ring derivative shown in a formula (I); the reaction process is shown as the formula (II):
wherein the content of the first and second substances,
R1is phenyl, electron-donating substituted phenyl, naphthyl, furyl or pyrrolyl, and the electron-donating group is alkyl or alkoxy;
R2is phenyl, electron-withdrawing or electron-donating substituted phenyl, the electron-withdrawing group is halogen, and the electron-donating group is alkoxy.
5. The synthetic method of claim 4 wherein R is1Is phenyl, C1-C10 alkyl substituted phenyl, C1-C10 alkoxy substituted phenyl, naphthyl, furyl or pyrrolyl; r2Is phenyl, halogen substituted phenyl, C1-C10 alkoxy substituted phenyl.
6. The synthesis method of claim 4, wherein the base is a catalyst selected from DABCO, NaOH, K2CO3、Cs2CO3One or more of them.
7. The method of claim 4, wherein the solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, or dimethylsulfoxide.
8. A synthesis process according to claim 4, characterized in that the molar ratio of the alkynone compound, 1, 3-indandione and base is 2.2: 1: 3.
9. the method of synthesis according to claim 4, wherein the temperature of the reaction is 110 ℃.
10. The method of synthesis according to claim 4, wherein the reaction time is 3 hours.
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