CN109651310B - N-furanone aryl sulfonyl hydrazide derivative and preparation method and application thereof - Google Patents

N-furanone aryl sulfonyl hydrazide derivative and preparation method and application thereof Download PDF

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CN109651310B
CN109651310B CN201811597466.9A CN201811597466A CN109651310B CN 109651310 B CN109651310 B CN 109651310B CN 201811597466 A CN201811597466 A CN 201811597466A CN 109651310 B CN109651310 B CN 109651310B
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汪朝阳
杨凯
罗时荷
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Abstract

The invention discloses an N-furanone aryl sulfonyl hydrazide derivative and a preparation method and application thereof, wherein the structural general formula of the N-furanone aryl sulfonyl hydrazide derivative is as follows:
Figure DDA0001921677570000011
wherein R is1Is C1～C6One of alkyl, 6-chlorohexyl, phenyl, benzyl and biphenyl, R2Is one of H, methyl, methoxyl and trifluoromethyl, and X is Cl or Br. The preparation method is simple, and the C-N coupling reaction of aryl sulfonyl hydrazide and 5-oxyl-3, 4-dihalo-2 (5H) furanone is carried out under the action of 4-dimethylamino pyridine and tetrabutylammonium iodide. The invention synthesizes a brand new N-furanone aryl sulfonyl hydrazide derivative with biological activities such as anti-tumor and antibacterial activities. The synthesis method has the advantages of simplicity, easiness in implementation, short reaction period, easiness in obtaining raw materials, wide application range of substrates, high yield and the like.

Description

N-furanone aryl sulfonyl hydrazide derivative and preparation method and application thereof
Technical Field
The invention relates to an N-furanone aryl sulfonyl hydrazide derivative and a preparation method and application thereof, belonging to the technical field of chemical synthesis.
Background
Because many aryl sulfonyl hydrazide compounds have biological activities such as anti-tumor and anti-bacterial activities, aryl sulfonyl hydrazide-containing structural units are increasingly emphasized in the design and synthesis of drug molecules. However, the currently reported bioactive molecules of the arylsulfonylhydrazide class are generally structures substituted by N at the 2-position, such as:
Figure BDA0001921677550000011
[ reference: kamal A, Khan M N A, Reddy K S, et al, Bioorg Med Chem,2007,15(2), 1004-; arkinstall S, Halazy S, Church D, et al pharmaceutical active sulfonyl hydrazide derivatives, EP1088822,2001-04]。
2(5H) -furanone structural units are widely found in natural products, and most of the natural products have biological activities such as anti-tumor and anti-bacterial activities [ references: wu Y-C, Luo S-H, Mei W-J, et al Eur.J.Med.chem.2017,139, 84-94; wei M-X, Zhang J, Ma F-L, et al, Eur, J, Med, chem, 2018,155,165-170 ]. However, no new compound synthesis report combining aryl sulfonyl hydrazide structural units and 2(5H) -furanone structural units is currently available.
Disclosure of Invention
The invention aims to provide an N-furanone aryl sulfonyl hydrazide derivative and a preparation method and application thereof.
The technical scheme adopted by the invention is as follows:
the N-furanone aryl sulfonyl hydrazide derivative has a structural general formula as follows:
Figure BDA0001921677550000012
wherein R is1Is C1～C6One of alkyl, 6-chlorohexyl, phenyl, benzyl and biphenyl of (A), R2Is one of H, methyl, methoxyl and trifluoromethyl, and X is Cl or Br.
Preferably, the N-furanone aryl sulfonyl hydrazide derivative has a structural general formula:
Figure BDA0001921677550000021
wherein R is1Is C1～C6Alkyl, 6-chlorohexyl, phenyl, benzylOne of phenyl and biphenyl, R2Is one of H, methyl, methoxyl and trifluoromethyl, and X is Cl or Br.
Preferably, said R is2Is H or methyl.
The preparation method of the N-furanone aryl sulfonyl hydrazide derivative comprises the following steps: under the action of 4-dimethylamino pyridine and tetrabutyl ammonium iodide, the C-N coupling reaction of aryl sulfonyl hydrazide and 5-oxyl-3, 4-dihalo-2 (5H) furanone is carried out to obtain the N-furanone aryl sulfonyl hydrazide derivative.
Preferably, the C-N coupling reaction is carried out at room temperature.
Preferably, the time of the C-N coupling reaction is 10-60 min.
Note: c1～C6The alkyl group of (a) includes straight-chain alkyl groups, branched-chain alkyl groups and cyclic alkyl groups.
The beneficial effects of the invention are: the invention synthesizes a brand new N-furanone aryl sulfonyl hydrazide derivative with biological activities such as anti-tumor and antibacterial activities. The synthesis method has the advantages of simplicity, easiness in operation, short reaction period, easiness in obtaining raw materials, wide application range of substrates, high yield and the like.
Drawings
FIG. 1 is an X-ray single crystal diffraction pattern of N-furanosyl arylsulfonylhydrazide derivative 1 according to example 1.
Detailed Description
The invention will be further explained and illustrated with reference to specific examples.
Example 1:
n-furanone aryl sulfonyl hydrazide derivative 1:
Figure BDA0001921677550000022
the preparation method comprises the following steps: 0.50mmol (0.136g) of 5-methoxy-3, 4-dibromo-2 (5H) -furanone, 0.60mmol (0.112g) of p-methylbenzenesulfonyl hydrazide, 1.0mmol (0.122g) of 4-Dimethylaminopyridine (DMAP), and 0.015mmol (0.005g) of tetrabutylammonium iodide (n-Bu)4NI)2.5mL of dichloromethane and 0.5mL of water are mixed uniformly, the mixture is stirred at room temperature for reaction for 30min, after the reaction is finished, the mixture is diluted by 15mL of water, dichloromethane (15mL multiplied by 3) is used for extraction and liquid separation, an organic layer is dried by anhydrous sodium sulfate, reduced pressure is used for spin drying, and a crude product is subjected to column separation to obtain 0.155g of N-furanone aryl sulfonyl hydrazide derivative 1 (white solid, yield 82%, melting point 135.4-136.9 ℃).
The related characterization data of the N-furanone aryl sulfonyl hydrazide derivative 1 are as follows:
Figure BDA0001921677550000031
1H NMR(600MHz,CDCl3)：2.48(s,3H,CH3-13),3.61(s,3H,OCH3-6),4.46(s,2H,NH2),6.24(s,1H,CH-5),7.41(d,J＝6.0Hz,2H,ArH-9,11),7.85(d,J＝6.0Hz,2H,ArH-8,12)；
13C NMR(150MHz,CDCl3)：21.9(C-13),57.5(C-6),95.3(C-3),101.6(C-5),128.8(C-8,12),130.2(C-9,11),132.3(C-7),146.2(C-10),155.7(C-4),165.9(C-2)；
ESI-HRMS,m/z(％)：Calcd for C12H14BrN2O5S[M+H]+,376.9807,found:376.9819；
the X-ray single crystal diffractogram is shown in FIG. 1;
the characterization results of hydrogen nuclear magnetic resonance spectrum, carbon nuclear magnetic resonance spectrum, high resolution mass spectrum and X-ray single crystal diffraction show that the structure of the N-furanone aryl sulfonyl hydrazide derivative 1 is consistent with the expectation.
Example 2:
n-furanone aryl sulfonyl hydrazide derivative 2:
Figure BDA0001921677550000032
the preparation method comprises the following steps: 0.50mmol (0.187g) of 5- (6-chlorohexyloxy) -3, 4-dibromo-2 (5H) -furanone, 0.60mmol (0.112g) of p-methylbenzenesulfonyl hydrazide, 1.0mmol (0.0 g)122g) of 4-Dimethylaminopyridine (DMAP), 0.015mmol (0.005g) of tetrabutylammonium iodide (n-Bu)4NI), 2.5mL of dichloromethane and 0.5mL of water were mixed well, the mixture was stirred at room temperature for 30min, after completion of the reaction, the mixture was diluted with 15mL of water, extracted with dichloromethane (15 mL. times.3), separated, dried over anhydrous sodium sulfate for the organic layer, and dried under reduced pressure, and the crude product was subjected to column separation to obtain 202mg of N-furanone based arylsulfonylhydrazide derivative 2 (colorless oil, 84% yield).
The related characterization data of the N-furanone aryl sulfonyl hydrazide derivative 2 are as follows:
Figure BDA0001921677550000041
1H NMR(600MHz,CDCl3)：1.36-1.48(m,4H,CH2-7,8),1.62-1.67(m,2H,CH2-9),1.75-1.80(m,2H,CH2-10),2.48(s,3H,CH3-18),3.54(t,J＝6.0Hz,2H,CH2-11),3.77-3.90(m,2H,OCH2-6),4.27(b,2H,NH2),6.28(s,1H,CH-5),7.41(d,J＝6.0Hz,2H,ArH-14,16),7.85(d,J＝6.0Hz,2H,ArH-13,17)；
13C NMR(150MHz,CDCl3)：21.8(C-18),25.1(C-8),26.5(C-9),29.2(C-7),32.5(C-10),45.1(C-11),70.9(C-6),95.9(C-3),101.0(C-5),128.7(C-14,16),130.2(C-13,17),132.2(C-12),146.1(C-15),155.9(C-4),165.9(C-2)；
ESI-HRMS,m/z(％)：Calcd for C17H23BrClN2O5S[M+H]+,481.0200,found:481.0207；
the characterization results of the hydrogen nuclear magnetic resonance spectrum, the carbon nuclear magnetic resonance spectrum and the high-resolution mass spectrum show that the structure of the N-furanone aryl sulfonyl hydrazide derivative 2 is consistent with the expectation.
Example 3:
n-furanosyl aryl sulfonyl hydrazide derivative 3:
Figure BDA0001921677550000042
the preparation method comprises the following steps: 0.50mmol (0.149g) of 5-isopropoxy-3, 4-dibromo-2 (5H) -furanone, 0.60mmol (0.112g) of p-methylbenzenesulfonyl hydrazide, 1.0mmol (0.122g) of 4-Dimethylaminopyridine (DMAP), and 0.015mmol (0.005g) of tetrabutylammonium iodide (n-Bu)4NI), 2.5mL of dichloromethane and 0.5mL of water were mixed well, the mixture was stirred at room temperature for 30min, after the reaction was completed, the mixture was diluted with 15mL of water, extracted with dichloromethane (15 mL. times.3), separated, dried over anhydrous sodium sulfate for the organic layer, and dried under reduced pressure, and the crude product was subjected to column separation to obtain 151mg of N-furanone aryl sulfonyl hydrazide derivative 3 (colorless oil, yield 75%).
The related characterization data of the N-furanone aryl sulfonyl hydrazide derivative 3 are as follows:
Figure BDA0001921677550000051
1H NMR(600MHz,CDCl3)：1.24(d,J＝6.0Hz,3H,CH3-7),1.28(d,J＝6.0Hz,3H,CH3-8),2.48(s,3H,CH3-15),4.12-4.18(m,1H,OCH-6),4.43(s,2H,NH2),6.31(s,1H,CH-5),7.40(d,J＝6.0Hz,2H,ArH-11,13),7.85(d,J＝6.0Hz,2H,ArH-10,14)；
13C NMR(150MHz,CDCl3)：21.7(C-15),21.9(C-7),23.1(C-8),75.1(C-6),97.2(C-3),100.3(C-5),128.6(C-10,14),130.1(C-11,13),132.1(C-9),146.0(C-12),156.4(C-4),166.0(C-2)；
ESI-HRMS,m/z(％)：Calcd for C14H18BrN2O5S[M+H]+,405.0120,found:405.0126；
the characterization results of the hydrogen nuclear magnetic resonance spectrum, the carbon nuclear magnetic resonance spectrum and the high-resolution mass spectrum show that the structure of the N-furanone aryl sulfonyl hydrazide derivative 3 is consistent with the expectation.
Example 4:
n-furanone aryl sulfonyl hydrazide derivative 4:
Figure BDA0001921677550000052
the preparation method comprises the following steps: 0.50mmol (0.173g) of 5-benzyloxy-3, 4-dibromo-2 (5H) -furanone, 0.60mmol (0.112g) of p-methylbenzenesulfonyl hydrazide, 1.0mmol (0.122g) of 4-Dimethylaminopyridine (DMAP), and 0.015mmol (0.005g) of tetrabutylammonium iodide (n-Bu)4NI), 2.5mL of dichloromethane and 0.5mL of water are mixed uniformly, the mixture is stirred at room temperature for reaction for 30min, after the reaction is finished, the mixture is diluted by 15mL of water, dichloromethane (15mL multiplied by 3) is used for extraction and liquid separation, an organic layer is dried by anhydrous sodium sulfate and is dried by decompression, and a crude product is subjected to column separation to obtain 181mg of N-furanone aryl sulfonyl hydrazide derivative 4 (colorless wax, yield 80%).
The related characterization data of the N-furanone aryl sulfonyl hydrazide derivative 4 are as follows:
Figure BDA0001921677550000061
1H NMR(600MHz,CDCl3)：2.41(s,3H,CH3-19),4.31(b,2H,NH2),4.77-4.94(dd,J1＝12.0Hz,J2＝12.0Hz,2H,OCH2-6),6.43(s,1H,CH-5),7.20(d,J＝6.0Hz,2H,ArH-8,12),7.32-7.36(m,5H,ArH-9,10,11,15,17),7.76(d,J＝6.0Hz,2H,ArH-14,18)；
13C NMR(150MHz,CDCl3)：21.8(C-19),72.9(C-6),95.3(C-3),100.2(C-5),128.6(C-10),128.7(C-8,12),128.8(C-14,18),128.9(C-9,11),130.0(C-15,17),132.0(C-13),135.5(C-7),146.0(C-16),155.7(C-4),166.0(C-2)；
ESI-HRMS,m/z(％)：Calcd for C18H18BrN2O5S[M+H]+,453.0120,found:453.0115；
the characterization results of the hydrogen nuclear magnetic resonance spectrum, the carbon nuclear magnetic resonance spectrum and the high-resolution mass spectrum show that the structure of the N-furanone aryl sulfonyl hydrazide derivative 4 is consistent with the expectation.
Example 5:
n-furanone aryl sulfonyl hydrazide derivative 5:
Figure BDA0001921677550000062
the preparation method comprises the following steps: 0.50mmol (0.166g) of 5-phenoxy-3, 4-dibromo-2 (5H) -furanone, 0.60mmol (0.112g) of p-methylbenzenesulfonyl hydrazide, 1.0mmol (0.122g) of 4-Dimethylaminopyridine (DMAP), and 0.015mmol (0.005g) of tetrabutylammonium iodide (n-Bu)4NI), 2.5mL of dichloromethane and 0.5mL of water were mixed uniformly, the mixture was stirred at room temperature for 30min, after the reaction was completed, the mixture was diluted with 15mL of water, extracted with dichloromethane (15 mL. times.3), separated, dried the organic layer over anhydrous sodium sulfate, dried under reduced pressure, and the crude product was subjected to column separation to obtain 166mg of N-furanosylarylsulfonylhydrazide derivative 5 (colorless wax, yield 76%).
The related characterization data of the N-furanone aryl sulfonyl hydrazide derivative 5 are as follows:
Figure BDA0001921677550000071
1H NMR(600MHz,CDCl3)：2.45(s,3H,CH3-18),4.49(b,2H,NH2),6.82(s,1H,CH-5),7.08(d,J＝6.0Hz,2H,ArH-7,11),7.13(t,J＝6.0Hz,1H,ArH-9),7.32-7.36(m,4H,ArH-8,10,14,16),7.83(d,J＝6.0Hz,ArH-13,17)；
13C NMR(150MHz,CDCl3)：21.8(C-18),96.4(C-3),98.5(C-5),117.2(C-7,11),124.3(C-9),128.8(C-8,10),129.9(C-13,17),130.2(C-14,16),132.1(C-12),146.3(C-15),155.6(C-6),155.9(C-4),165.5(C-2)；
ESI-HRMS,m/z(％)：Calcd for C17H16BrN2O5S[M+H]+,438.9963,found:438.9963；
the characterization results of the hydrogen nuclear magnetic resonance spectrum, the carbon nuclear magnetic resonance spectrum and the high-resolution mass spectrum show that the structure of the N-furanone aryl sulfonyl hydrazide derivative 5 is consistent with the expectation.
Example 6:
n-furanone aryl sulfonyl hydrazide derivative 6:
Figure BDA0001921677550000072
the preparation method comprises the following steps: 0.50mmol (0.204g) of 5- (4-phenyl-phenoxy) -3, 4-dibromo-2 (5H) -furanone, 0.60mmol (0.112g) of p-methylbenzenesulfonyl hydrazide, 1.0mmol (0.122g) of 4-Dimethylaminopyridine (DMAP), 0.015mmol (0.005g) of tetrabutylammonium iodide (n-Bu)4NI), 2.5mL of dichloromethane and 0.5mL of water are mixed uniformly, the mixture is stirred at room temperature for reaction for 30min, after the reaction is finished, the mixture is diluted by 15mL of water, dichloromethane (15mL multiplied by 3) is used for extraction and liquid separation, an organic layer is dried by anhydrous sodium sulfate and is dried by decompression and spin-drying, and a crude product is subjected to column separation to obtain 180mg of N-furanone aryl sulfonyl hydrazide derivative 6 (white solid, the yield is 70 percent, and the melting point is 142.4-143.9 ℃).
The related characterization data of the N-furanone aryl sulfonyl hydrazide derivative 6 are as follows:
Figure BDA0001921677550000081
1H NMR(600MHz,CDCl3)：2.47(s,3H,CH3-24),4.47(b,2H,NH2),6.87(s,1H,CH-5),7.16(d,J＝6.0Hz,2H,ArH-7,11),7.34(t,J＝6.0Hz,1H,ArH-15),7.39(d,J＝6.0Hz,2H,ArH-20,22),7.42-7.44(m,2H,ArH-14,16),7.54-7.57(m,4H,ArH-7,8,13,17),7.86(d,J＝6.0Hz,2H,ArH-19,23)；
13C NMR(150MHz,CDCl3)：21.9(C-24),96.6(C-3),98.7(C-5),117.7(C-7,11),127.1(C-13,17),127.4(C-15),128.7(C-19,23),129.0(C-14,16,20,22),130.3(C-8,10),132.2(C-9),137.6(C-18),140.4(C-21),146.4(C-12),155.4(C-6),155.5(C-4),165.5(C-2)；
ESI-HRMS,m/z(％)：Calcd for C23H20BrN2O5S[M+H]+,515.0276,found:515.0273；
the characterization results of the hydrogen nuclear magnetic resonance spectrum, the carbon nuclear magnetic resonance spectrum and the high-resolution mass spectrum show that the structure of the N-furanone aryl sulfonyl hydrazide derivative 6 is consistent with the expectation.
Example 7:
n-furanonyl aryl sulfonyl hydrazide derivative 7:
Figure BDA0001921677550000082
the preparation method comprises the following steps: 0.50mmol (0.149g) of 5-isopropoxy-3, 4-dibromo-2 (5H) -furanone, 0.60mmol (0.103g) of benzenesulfonylhydrazide, 1.0mmol (0.122g) of 4-Dimethylaminopyridine (DMAP), and 0.015mmol (0.005g) of tetrabutylammonium iodide (n-Bu)4NI), 2.5mL of dichloromethane and 0.5mL of water were mixed well, the mixture was stirred at room temperature for 30min, after completion of the reaction, the mixture was diluted with 15mL of water, extracted with dichloromethane (15 mL. times.3), separated, dried over anhydrous sodium sulfate for the organic layer, and dried under reduced pressure, and the crude product was subjected to column separation to obtain 164mg of N-furanone aryl sulfonyl hydrazide derivative 7 (colorless wax, 84% yield).
The related characterization data of the N-furanone aryl sulfonyl hydrazide derivative 7 are as follows:
Figure BDA0001921677550000091
1H NMR(600MHz,CDCl3)：1.25(d,J＝6.0Hz,3H,CH3-7),1.29(d,J＝6.0Hz,3H,CH3-8),4.14-4.19(m,1H,OCH-6),4.43(s,2H,NH2),6.32(s,1H,CH-5),7.60-7.64(m,2H,ArH-11,13),7.74(t,J＝6.0Hz,1H,ArH-12),7.99(d,J＝6.0Hz,2H,ArH-10,14)；
13C NMR(150MHz,CDCl3)：22.0(C-7),23.2(C-8),57.3(C-6),97.8(C-3),100.4(C-5),128.7(C-10,14),129.6(C-11,13),134.7(C-12),135.4(C-9),156.4(C-4),165.9(C-2)；
ESI-HRMS,m/z(％)：Calcd for C13H16BrN2O5S[M+H]+,390.9963,found:390.9967；
the characterization results of the hydrogen nuclear magnetic resonance spectrum, the carbon nuclear magnetic resonance spectrum and the high-resolution mass spectrum show that the structure of the N-furanone aryl sulfonyl hydrazide derivative 7 is consistent with the expectation.
Example 8:
n-furanone aryl sulfonyl hydrazide derivative 8:
Figure BDA0001921677550000092
the preparation method comprises the following steps: 0.50mmol (0.105g) of 5-propoxy-3, 4-dichloro-2 (5H) -furanone, 0.60mmol (0.112g) of p-toluenesulfonyl hydrazide, 1.0mmol (0.122g) of 4-Dimethylaminopyridine (DMAP), 0.015mmol (0.005g) of tetrabutylammonium iodide (n-Bu)4NI), 2.5mL of dichloromethane and 0.5mL of water were mixed uniformly, the mixture was stirred at room temperature for 30min, after the reaction was completed, the mixture was diluted with 15mL of water, extracted with dichloromethane (15 mL. times.3), separated, the organic layer was dried over anhydrous sodium sulfate, dried under reduced pressure, and the crude product was subjected to column separation to obtain 155mg of N-furanosylarylsulfonylhydrazide derivative 8 (colorless wax, yield 86%).
The related characterization data of the N-furanone aryl sulfonyl hydrazide derivative 8 are as follows:
Figure BDA0001921677550000093
1H NMR(600MHz,CDCl3)：0.92(t,J＝6.0Hz,3H,CH3-8),1.60-1.66(m,2H,CH2-7),2.47(s,3H,CH3-15),3.71-3.85(m,2H,OCH2-6),4.42(b,2H,NH2),6.24(s,1H,CH-5),7.40(d,J＝6.0Hz,2H,ArH-11,13),7.85(d,J＝6.0Hz,2H,ArH-10,14)；
13C NMR(150MHz,CDCl3)：10.3(C-8),21.7(C-15),22.7(C-7),72.8(C-6),100.1(C-5),107.4(C-3),128.7(C-10,14),130.1(C-11,13),132.2(C-12),146.1(C-9),152.1(C-4),165.5(C-2)；
ESI-HRMS,m/z(％)：Calcd for C14H18ClN2O5S[M+H]+,361.0625,found:361.0630；
the characterization results of the hydrogen nuclear magnetic resonance spectrum, the carbon nuclear magnetic resonance spectrum and the high-resolution mass spectrum show that the structure of the N-furanone aryl sulfonyl hydrazide derivative 8 is consistent with the expectation.
Example 9:
n-furanone aryl sulfonyl hydrazide derivative 9:
Figure BDA0001921677550000101
the preparation method comprises the following steps: 0.50mmol (0.125g) of 5-cyclohexyloxy-3, 4-dichloro-2 (5H) -furanone, 0.60mmol (0.112g) of p-toluenesulfonyl hydrazide, 1.0mmol (0.122g) of 4-Dimethylaminopyridine (DMAP), 0.015mmol (0.005g) of tetrabutylammonium iodide (n-Bu)4NI), 2.5mL of dichloromethane and 0.5mL of water were mixed well, the mixture was stirred at room temperature for 30min, after completion of the reaction, the mixture was diluted with 15mL of water, extracted with dichloromethane (15 mL. times.3), separated, dried over anhydrous sodium sulfate for the organic layer, and dried under reduced pressure, and the crude product was subjected to column separation to obtain 156mg of N-furanone aryl sulfonyl hydrazide derivative 9 (colorless wax, yield 78%).
The related characterization data of the N-furanone aryl sulfonyl hydrazide derivative 9 are as follows:
Figure BDA0001921677550000102
1H NMR(600MHz,CDCl3)：1.17-1.55(m,6H,CH2-8,9,10),1.70-1.77(m,2H,CH2-7),1.94-1.99(m,2H,CH2-11),2.48(s,3H,CH3-17),3.82-3.86(m,1H,OCH-6),4.36(b,2H,NH2),6.33(s,1H,CH-5),7.40(d,J＝6.0Hz,2H,ArH-14,16),7.85(d,J＝6.0Hz,2H,ArH-13,17)；
13C NMR(150MHz,CDCl3)：21.9(C-18),24.0(C-8),24.1(C-10),25.4(C-9),32.0(C-7),33.3(C-11),80.7(C-6),99.4(C-5),108.8(C-3),128.8(C-13,17),130.2(C-14,16),132.3(C-15),146.1(C-12),152.7(C-4),165.6(C-2)；
ESI-HRMS,m/z(％)：Calcd for C17H22ClN2O5S[M+H]+,401.0938,found:401.0945；
the characterization results of the hydrogen nuclear magnetic resonance spectrum, the carbon nuclear magnetic resonance spectrum and the high-resolution mass spectrum show that the structure of the N-furanone aryl sulfonyl hydrazide derivative 9 is consistent with the expectation.
Example 10:
n-furanonyl arylsulfonylhydrazide derivatives 10:
Figure BDA0001921677550000111
the preparation method comprises the following steps: 0.50mmol (0.091g) of 5-methoxy-3, 4-dichloro-2 (5H) -furanone, 0.60mmol (0.103g) of benzenesulfonylhydrazide, 1.0mmol (0.122g) of 4-Dimethylaminopyridine (DMAP), 0.015mmol (0.005g) of tetrabutylammonium iodide (n-Bu)4NI), 2.5mL of dichloromethane and 0.5mL of water were mixed well, the mixture was stirred at room temperature for 30min, after the reaction was completed, the mixture was diluted with 15mL of water, extracted with dichloromethane (15 mL. times.3), separated, dried over anhydrous sodium sulfate for the organic layer, and dried under reduced pressure, and the crude product was subjected to column separation to obtain 130mg of N-furanone aryl sulfonyl hydrazide derivative 10 (colorless wax, yield 82%).
The relevant characterization data of the N-furanone aryl sulfonyl hydrazide derivative 10 are as follows:
Figure BDA0001921677550000112
1H NMR(600MHz,CDCl3)：3.61(s,3H,OCH3-6),4.51(s,2H,NH2),6.22(s,1H,CH-5),7.61-7.63(m,2H,ArH-9,11),7.74(t,J＝6.0Hz,1H,ArH-10),7.98(d,J＝6.0Hz,2H,ArH-8,12)；
13C NMR(150MHz,CDCl3)：57.5(C-6),100.5(C-5),106.8(C-3),128.6(C-8,12),129.5(C-9,11),134.7(C-10),135.3(C-7),151.9(C-4),165.4(C-2)；
ESI-HRMS,m/z(％)：Calcd for C11H12ClN2O5S[M+H]+,319.0155,found:319.0164；
the characterization results of the hydrogen nuclear magnetic resonance spectrum, the carbon nuclear magnetic resonance spectrum and the high-resolution mass spectrum show that the structure of the N-furanone aryl sulfonyl hydrazide derivative 10 is consistent with the expectation.
Example 11:
n-furanone aryl sulfonyl hydrazide derivative 11:
Figure BDA0001921677550000121
the preparation method comprises the following steps: 0.50mmol (0.122g) of 5-phenoxy-3, 4-dichloro-2 (5H) -furanone, 0.60mmol (0.103g) of benzenesulfonylhydrazide, 1.0mmol (0.122g) of 4-Dimethylaminopyridine (DMAP), 0.015mmol (0.005g) of tetrabutylammonium iodide (n-Bu)4NI), 2.5mL of dichloromethane and 0.5mL of water are mixed uniformly, the mixture is stirred at room temperature for reaction for 30min, after the reaction is finished, the mixture is diluted by 15mL of water, dichloromethane (15mL multiplied by 3) is used for extraction and liquid separation, an organic layer is dried by anhydrous sodium sulfate, reduced pressure is adopted for spin-drying, and a crude product is subjected to column separation to obtain 139mg of N-furanone aryl sulfonyl hydrazide derivative 11 (white solid, the yield is 73 percent, and the melting point is 129.4-130.8 ℃).
The related characterization data of the N-furanone aryl sulfonyl hydrazide derivative 11 are as follows:
Figure BDA0001921677550000122
1H NMR(600MHz,CDCl3)：4.49(s,2H,NH2),6.81(s,1H,CH-5),7.06(d,J＝6.0Hz,2H,ArH-7,11),7.14(t,J＝6.0Hz,1H,ArH-9),7.33-7.35(m,2H,ArH-8,10),7.58-7.60(m,2H,ArH-14,16),7.73(t,J＝6.0Hz,1H,ArH-15),7.97(d,J＝6.0Hz,2H,ArH-13,17)；
13C NMR(150MHz,CDCl3)：97.5(C-5),108.4(C-3),117.3(C-7,11),124.4(C-9),128.8(C-13,17),129.7(C-14,16),130.0(C-8,10),134.9(C-15),135.3(C-12),151.7(C-6),155.9(C-4),164.9(C-2)；
ESI-HRMS,m/z(％)：Calcd for C16H14ClN2O5S[M+H]+,381.0312,found:381.0316；
the characterization results of the hydrogen nuclear magnetic resonance spectrum, the carbon nuclear magnetic resonance spectrum and the high-resolution mass spectrum show that the structure of the N-furanone aryl sulfonyl hydrazide derivative 11 is consistent with the expectation.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (3)

1. A preparation method of N-furanone aryl sulfonyl hydrazide derivatives is characterized by comprising the following steps: the method comprises the following steps: under the action of 4-dimethylamino pyridine and tetrabutylammonium iodide, performing C-N coupling reaction of aryl sulfonyl hydrazide and 5-oxyl-3, 4-dihalo-2 (5H) furanone to obtain an N-furanone aryl sulfonyl hydrazide derivative;
the structural general formula of the N-furanone aryl sulfonyl hydrazide derivative is as follows:
Figure FDA0003597694790000011
wherein R is1Is C1～C6One of alkyl, 6-chlorohexyl, phenyl, benzyl and biphenyl, R2Is one of H, methyl, methoxyl and trifluoromethyl, and X is Cl or Br.
2. The production method according to claim 1, characterized in that: the C-N coupling reaction is carried out at room temperature.
3. The production method according to claim 1 or 2, characterized in that: the time of the C-N coupling reaction is 10-60 min.
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