CN104860864A - New synthetizing method of 2-carbonyl-5-alkynyl pyrrole compound - Google Patents

New synthetizing method of 2-carbonyl-5-alkynyl pyrrole compound Download PDF

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CN104860864A
CN104860864A CN201510303733.7A CN201510303733A CN104860864A CN 104860864 A CN104860864 A CN 104860864A CN 201510303733 A CN201510303733 A CN 201510303733A CN 104860864 A CN104860864 A CN 104860864A
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CN104860864B (en
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潘英明
滕青湖
王恒山
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Guangxi Normal University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms

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  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a new synthetizing method of a 2-carbonyl-5-alkynyl pyrrole compound. The new synthetizing method comprises the following steps: sequentially adding 0.5 mmol of acetylene acetone, 0.55 mmol of glycine ester hydrochloride, 0.5 mmol of KOAc, 0.5 mmol of KHCO3 and 2 mL of DMF in a round-bottomed flask to be used as a solvent; heating the solvent to 120 DEG C, carrying out a reaction for 2 hours, and tracking the reaction according to TLC; after the reaction is completely finished, cooling a reactant to a room temperature, pouring the cooled reactant into 10-30 mL of water, performing extraction with 20-30 mL of ethyl acetate, and washing the extracted reactant with a saturated saline solution (10-20 mL) for three times; drying the washed reactant with anhydrous Na2SO4, filtering the dried reactant, and reducing pressure so as to remove the solvent; performing rapid silica gel column chromatography purification (the ratio of the ethyl acetate to ligroin is 1:(20-50) so as to obtain the product. The method has the advantages that raw materials are easy to obtain, the operation is simple, the reaction steps are few, the yield is high, the application scope of substrates is wide, and the application prospect is broad.

Description

The new synthetic method of 2-carbonyl-5-alkynyl azole compounds
Technical field
The present invention relates to chemosynthesis, specifically the new synthetic method of 2-carbonyl-5-alkynyl azole compounds.
Background technology
Pyrroles and derivative thereof are important heterogeneous ring compounds, and a large amount of is applied to organic synthesis, functional material and medicine.Pyrroles is the female ring " GB 1428272 (1973) " of antalgica tolmetin.2-carbonyl pyrrolidine is important intermediate in complete synthesis natural product, complete synthesis " J.Org.Chem.2014,79,529. " of such as sheet spiral shell element.In addition, azole compounds can also construct the heterogeneous ring compound of many rings, such as, construct indolone " Synlett 2009,2010 ".2-carboxylicesters pyrroles also has antimitotic and cytostatic effect " Biorg.Med.Chem.2006,14,4627 ".Organic chemists are never interrupted for the research of the method for efficient synthesis azole compounds all the time.Classical synthetic method has Hantzsch to react " A.Hantzsch, Ber., 1890,23,1474 " and Paal – Knorr react " J.Am.Chem.Soc., 2000,122,3801 ", the cycloaddition method of many metal catalytics is also had to be in the news " Angew.Chem., Int.Ed.2013,52,6953 ", the cycloisomerization of functionalization intermediate.Although report so many method synthesis pyrroles, have not yet to see and utilize the report that diine acetone and glycinate are Material synthesis pyrrole derivative.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of new synthetic method and their application of 2-carbonyl-5-alkynyl azole compounds.
The technical scheme realizing the object of the invention is:
A new synthetic method for 2-carbonyl-5-alkynyl azole compounds, comprises the steps:
(1) in round-bottomed flask, 0.5mmol 1,0.55mmol 2,0.5mmol KOAc is added successively, 0.5mmol KHCO 3, 2mL DMF is as solvent;
(2) be heated to 120 DEG C of reactions 2h, TLC and follow the tracks of reaction;
(3) question response completely after, cool to room temperature, pours into reactant in 10 ~ 30mL water, and with 20 ~ 30mL extraction into ethyl acetate, washs three times with saturated aqueous common salt (10 ~ 20mL);
(4) anhydrous Na is used 2sO 4drying, filters, removal of solvent under reduced pressure;
(5) product is obtained through Flash silica column chromatography purification (ethyl acetate/petroleum ether=1:20 ~ 50).
Its synthesis general formula is as follows:
In formula:
1 is diine acetone, and 2 is glycine ester hydrochloride, and 3 for having the polysubstituted pyrrole of acetylene bond;
R 1for phenyl, 4-aminomethyl phenyl, 4-ethylphenyl, 4-p-methoxy-phenyl, 4-amyl group phenyl, 4-fluorophenyl
R 2for phenyl, 4-aminomethyl phenyl, 4-ethylphenyl, 4-p-methoxy-phenyl, 4-amyl group phenyl, 4-fluorophenyl
R 3for alkoxyl group.
Advantage of the present invention is: raw material is easy to get, simple to operate, and productive rate is considerable, has good application prospect.
Embodiment
Embodiment 1:
The preparation of 2-carboxyethyl-3-phenyl-5-(2-phenylacetylene base) pyrroles
1 is added successively, 5 – phenylbenzene-Isosorbide-5-Nitrae-diine-propione 0.5mmol (0.115g), utamic acid carbethoxy hydrochloride 0.55mmol (0.0757g), KOAc 0.5mmol (0.0491g), KHCO in round-bottomed flask 30.5mmol (0.05g), solvent DMF 2mL, be heated to 120 DEG C of reactions 2h, TLC and follow the tracks of reaction.After question response is complete, cool to room temperature, pours into reactant in 10 ~ 30mL water, and with 20 ~ 30mL extraction into ethyl acetate, washs three times, finally use anhydrous Na with saturated aqueous common salt (10 ~ 20mL) 2sO 4drying, filters, removal of solvent under reduced pressure, obtains yellow solid 3aa, productive rate 85% through Flash silica column chromatography purification (ethyl acetate/petroleum ether=1:20 ~ 50).
Characterization of The Products:
1H NMR(400MHz,CDCl 3)δ9.88(s,1H),7.64–7.60(m,2H),7.58–7.54(m,2H),7.44–7.39(m,2H),7.38–7.31(m,5H),6.74(d,J＝2.9Hz,1H),4.46–4.35(m,2H),1.44(t,J＝7.1Hz,4H).
13C NMR(100MHz,CDCl 3)δ161.0,136.0,131.4,130.6,129.0,128.3,128.1,128.0,125.0,124.4,123.7,111.9,92.5,83.7,61.0,14.4.
Embodiment 2:
The preparation of 2-carboxyethyl-3-(4-aminomethyl phenyl)-5-(2-is to methylbenzene ethynyl) pyrroles
1,5-, bis-p-methylphenyls-Isosorbide-5-Nitrae-diine-propione 0.5mmol (0.1421g), utamic acid carbethoxy hydrochloride 0.55mmol (0.0757g), KOAc 0.5mmol (0.0491g), KHCO 30.5mmol (0.05g), solvent DMF 2mL, be heated to 120 DEG C of reactions 2h, TLC and follow the tracks of reaction.After question response is complete, cool to room temperature, pours into reactant in 10 ~ 30mL water, and with 20 ~ 30mL extraction into ethyl acetate, washs three times, finally use anhydrous Na with saturated aqueous common salt (10 ~ 20mL) 2sO 4drying, filters, removal of solvent under reduced pressure, obtains yellow solid 3ba, productive rate 86% through Flash silica column chromatography purification (ethyl acetate/petroleum ether=1:20 ~ 50).
Characterization of The Products:
1H NMR(400MHz,CDCl 3)δ9.49(s,1H),7.48(s,1H),7.45(d,J＝4.3Hz,2H),7.43(s,1H),7.23(d,J＝8.0Hz,3H),7.16(d,J＝8.0Hz,3H),6.67(d,J＝2.9Hz,1H),4.40(q,J＝7.1Hz,3H),2.38(s,3H),2.37(s,2H),1.43(t,J＝7.1Hz,4H).
13C NMR(100MHz,CDCl 3)δ160.9,138.2,138.1,136.0,131.3,129.7,129.1,127.8,124.7,123.9,120.7,112.1,111.4,92.7,83.0,60.8,21.5,21.2,14.5.
Embodiment 3:
The preparation of 2-carboxyethyl-3-(4-ethylphenyl)-5-(2-p-ethyl-phenylacetylene base)
1,5-bis-couples ethylphenyl-Isosorbide-5-Nitrae-diine-propione 0.5mmol (0.1431g), utamic acid carbethoxy hydrochloride 0.55mmol (0.0757g), KOAc 0.5mmol (0.0491g), KHCO 30.5mmol (0.05g), solvent DMF 2mL, be heated to 120 DEG C of reactions 2h, TLC and follow the tracks of reaction.After question response is complete, cool to room temperature, pours into reactant in 10 ~ 30mL water, and with 20 ~ 30mL extraction into ethyl acetate, washs three times, finally use anhydrous Na with saturated aqueous common salt (10 ~ 20mL) 2sO 4drying, filters, removal of solvent under reduced pressure, obtains yellow solid 3ca, productive rate 89% through Flash silica column chromatography purification (ethyl acetate/petroleum ether=1:20 ~ 50).
Characterization of The Products:
1H NMR(400MHz,CDCl 3)δ9.74(s,1H),7.53(d,J＝8.1Hz,2H),7.48(d,J＝8.0Hz,2H),7.25(d,J＝8.1Hz,2H),7.19(d,J＝8.0Hz,2H),6.69(d,J＝2.7Hz,1H),4.41(q,J＝7.1Hz,2H),2.68(q,J＝7.3Hz,4H),1.44(t,J＝7.1Hz,3H),δ1.26(td,J＝7.5,1.4Hz,6H).
13C NMR(100MHz,CDCl 3)δ161.0,144.44,144.35,136.2,131.4,128.5,128.2,127.8,125.0,124.1,121.0,112.2,111.5,92.7,83.1,60.8,28.8,28.6,15.4,15.3,14.5.
Embodiment 4:
The preparation of 2-carboxyethyl-3-(4-amyl group phenyl)-5-(2-is to amylbenzene ethynyl)
1,5-, bis-couples of amyl group phenyl-Isosorbide-5-Nitrae-diine-propione 0.5mmol (0.1853g), utamic acid carbethoxy hydrochloride 0.55mmol (0.0757g), KOAc 0.5mmol (0.0491g), KHCO 30.5mmol (0.05g), solvent DMF 2mL, be heated to 120 DEG C of reactions 2h, TLC and follow the tracks of reaction.After question response is complete, cool to room temperature, pours into reactant in 10 ~ 30mL water, and with 20 ~ 30mL extraction into ethyl acetate, washs three times, finally use anhydrous Na with saturated aqueous common salt (10 ~ 20mL) 2sO 4drying, filters, removal of solvent under reduced pressure, obtains yellow solid 3ea, productive rate 87% through Flash silica column chromatography purification (ethyl acetate/petroleum ether=1:20 ~ 50).
Characterization of The Products:
1H NMR(400MHz,CDCl 3)δ9.87(s,1H),7.54(d,J＝8.0Hz,2H),7.48(d,J＝8.0Hz,2H),7.23(d,J＝8.0Hz,2H),7.18(d,J＝8.0Hz,2H),6.69(d,J＝2.7Hz,1H),4.40(q,J＝7.1Hz,2H),2.63(t,J＝7.7Hz,4H),1.64(dt,J＝14.4,7.4Hz,4H),1.44(t,J＝7.1Hz,3H),1.35(d,J＝3.2Hz,6H),0.92(t,J＝6.7Hz,6H).
13C NMR(100MHz,CDCl 3)δ161.2,143.2,136.4,131.4,129.1,128.5,128.2,125.0,124.1,121.0,112.3,111.6,92.8,83.2,60.9,35.9,35.7,31.5,31.1,31.0,22.6,14.5,14.1.
Embodiment 5:
The preparation of 2-carboxyethyl-3-(4-methoxyl group base phenyl)-5-(2-is to Methoxy-phenylacetylene base)
1,5-di-p-methoxy phenyl-Isosorbide-5-Nitrae-diine-propione 0.5mmol (0.1452g), utamic acid carbethoxy hydrochloride 0.55mmol (0.0757g), KOAc 0.5mmol (0.0491g), KHCO 30.5mmol (0.05g), solvent DMF 2mL, be heated to 120 DEG C of reactions 2h, TLC and follow the tracks of reaction.After question response is complete, cool to room temperature, pours into reactant in 10 ~ 30mL water, and with 20 ~ 30mL extraction into ethyl acetate, washs three times, finally use anhydrous Na with saturated aqueous common salt (10 ~ 20mL) 2sO 4drying, filters, removal of solvent under reduced pressure, obtains yellow solid 3fa, productive rate 88% through Flash silica column chromatography purification (ethyl acetate/petroleum ether=1:20 ~ 50).
Characterization of The Products:
1H NMR(400MHz,CDCl 3)δ9.55(s,1H),7.52(dd,J＝12.4,8.7Hz,4H),6.94(dd,J＝24.7,8.1Hz,4H),6.63(s,1H),4.41(d,J＝6.9Hz,2H),3.86(s,6H),1.45(t,J＝6.7Hz,3H).
13C NMR(100MHz,CDCl 3)δ161.0,159.7,159.5,136.0,132.9,126.3,123.7,123.5,116.0,114.5,114.0,112.4,111.0,92.6,82.4,60.8,55.4,55.3,14.5.
Embodiment 6:
The preparation of 2-carboxyethyl-3-(4-fluorophenyl)-5-(2-is to fluorophenylethynyl)
1,5-bis-couples fluorophenyl-Isosorbide-5-Nitrae-diine-propione 0.5mmol (0.1331g), utamic acid carbethoxy hydrochloride 0.55mmol (0.0757g), KOAc 0.5mmol (0.0491g), KHCO 30.5mmol (0.05g), solvent DMF 2mL, be heated to 120 DEG C of reactions 2h, TLC and follow the tracks of reaction.After question response is complete, cool to room temperature, pours into reactant in 10 ~ 30mL water, and with 20 ~ 30mL extraction into ethyl acetate, washs three times, finally use anhydrous Na with saturated aqueous common salt (10 ~ 20mL) 2sO 4drying, filters, removal of solvent under reduced pressure, obtains dark red solid 3ha, productive rate 73% through Flash silica column chromatography purification (ethyl acetate/petroleum ether=1:20 ~ 50).
Characterization of The Products:
1H NMR(400MHz,CDCl 3)δ9.62(s,1H),7.56(ddd,J＝18.5,8.6,5.3Hz,4H),7.15(t,J＝8.5Hz,2H),7.06(d,J＝8.7Hz,2H),6.67(d,J＝2.7Hz,1H),4.42(q,J＝7.1Hz,2H),1.45(t,J＝7.1Hz,3H).
13C NMR(100MHz,CDCl 3)δ163.9,163.7,161.4,161.2,160.8,135.1,133.4,133.3,126.9,126.8,124.5,119.8,116.3,116.1,115.8,115.6,111.9,111.8,91.6,83.2,61.0,14.5.
Embodiment 7:
The preparation of 2-carboxyethyl-3-propyl group-5-(valerylene base)
4,7-diine-6-hendecanone 0.5mmol (0.0811g), utamic acid carbethoxy hydrochloride 0.55mmol (0.0757g), KOAc 0.5mmol (0.0491g), KHCO 30.5mmol (0.05g), solvent DMF 2mL, be heated to 120 DEG C of reactions 2h, TLC and follow the tracks of reaction.After question response is complete, cool to room temperature, pours into reactant in 10 ~ 30mL water, and with 20 ~ 30mL extraction into ethyl acetate, washs three times, finally use anhydrous Na with saturated aqueous common salt (10 ~ 20mL) 2sO 4drying, filters, removal of solvent under reduced pressure, obtains yellow solid 3ab, productive rate 63% through Flash silica column chromatography purification (ethyl acetate/petroleum ether=1:20 ~ 50).
Characterization of The Products:
1H NMR(400MHz,CDCl 3)δ8.98(s,1H),6.06(t,J＝11.1Hz,1H),4.33(q,J＝7.1Hz,2H),2.53(t,J＝7.5Hz,2H),2.41(t,J＝7.0Hz,2H),1.63(dd,J＝14.6,7.3Hz,4H),1.37(t,J＝7.1Hz,3H),1.05(t,J＝7.4Hz,3H),0.93(t,J＝7.4Hz,3H).
13C NMR(100MHz,CDCl 3)δ160.9,137.4,122.1,112.5,111.9,93.3,83.1,74.8,60.4,29.6,22.3,22.3,21.8,14.4,13.7,13.6.
The invention provides the method for a synthesis 2-carbonyl-5-alkynyl pyrrole derivative, the method raw material is easy to get, simple to operate, and reactions steps is few, and output is high, wide application range of substrates, and application prospect is extensive.

Claims (2)

1. a new synthetic method for 2-carbonyl-5-alkynyl azole compounds, is characterized in that: comprise the steps:
(1) in round-bottomed flask, 0.5 mmol is added successively 1, 0.55 mmol 2, 0.5 mmol KOAc, 0.5 mmol KHCO 3, 2 mL DMF are as solvent;
(2) 120 are heated to oc reacts 2 h, and TLC follows the tracks of reaction;
(3) question response completely after, cool to room temperature, pours into reactant in 10 ~ 30 mL water, and with 20 ~ 30 mL extraction into ethyl acetate, washs three times with saturated aqueous common salt (10 ~ 20 mL);
(4) anhydrous Na is used 2sO 4drying, filters, removal of solvent under reduced pressure;
(5) product is obtained through Flash silica column chromatography purification (ethyl acetate/petroleum ether=1:20 ~ 50).
2. synthetic method according to claim 1, is characterized in that: its synthesis general formula is as follows:
In formula:
1 is diine acetone, and 2 is glycine ester hydrochloride, and 3 for having the polysubstituted pyrrole of acetylene bond;
R 1for phenyl, 4-aminomethyl phenyl, 4-ethylphenyl, 4-p-methoxy-phenyl, 4-amyl group phenyl, 4-fluorophenyl
R 2for phenyl, 4-aminomethyl phenyl, 4-ethylphenyl, 4-p-methoxy-phenyl, 4-amyl group phenyl, 4-fluorophenyl
R 3for alkoxyl group.
CN201510303733.7A 2015-06-04 2015-06-04 The synthetic method of the alkynyl azole compounds of 2 carbonyl 5 Expired - Fee Related CN104860864B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114746408A (en) * 2019-12-02 2022-07-12 豪夫迈·罗氏有限公司 Alkynyl- (heteroaryl) -carboxamide HCN1 inhibitors

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CN101798279A (en) * 2010-03-23 2010-08-11 东北师范大学 Method for preparing iron-catalyzed pyrrole and pyrrole cyclic compounds
CN102659658A (en) * 2012-04-01 2012-09-12 东北师范大学 Method for synthesis of highly functionalized pyrrole compound
WO2014100218A1 (en) * 2012-12-21 2014-06-26 Exxonmobil Chemical Patents Inc. Improved synthesis of succinimides and quaternary ammonium ions for use in making molecular sieves
US8901336B2 (en) * 2011-09-06 2014-12-02 University Of Florida Research Foundation, Inc. Catalysts, methods of making catalysts, and methods of use

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101798279A (en) * 2010-03-23 2010-08-11 东北师范大学 Method for preparing iron-catalyzed pyrrole and pyrrole cyclic compounds
US8901336B2 (en) * 2011-09-06 2014-12-02 University Of Florida Research Foundation, Inc. Catalysts, methods of making catalysts, and methods of use
CN102659658A (en) * 2012-04-01 2012-09-12 东北师范大学 Method for synthesis of highly functionalized pyrrole compound
WO2014100218A1 (en) * 2012-12-21 2014-06-26 Exxonmobil Chemical Patents Inc. Improved synthesis of succinimides and quaternary ammonium ions for use in making molecular sieves

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114746408A (en) * 2019-12-02 2022-07-12 豪夫迈·罗氏有限公司 Alkynyl- (heteroaryl) -carboxamide HCN1 inhibitors

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