CN109651310A - A kind of N- furanonyl arylsulfonyl hydrazine derivative and its preparation method and application - Google Patents

A kind of N- furanonyl arylsulfonyl hydrazine derivative and its preparation method and application Download PDF

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CN109651310A
CN109651310A CN201811597466.9A CN201811597466A CN109651310A CN 109651310 A CN109651310 A CN 109651310A CN 201811597466 A CN201811597466 A CN 201811597466A CN 109651310 A CN109651310 A CN 109651310A
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furanonyl
arylsulfonyl hydrazine
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汪朝阳
杨凯
罗时荷
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South China Normal University
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Abstract

The invention discloses a kind of N- furanonyl arylsulfonyl hydrazine derivative and its preparation method and application, the general structures of the N- furanonyl arylsulfonyl hydrazine derivative are as follows:Wherein, R1For C1~C6Alkyl, 6- chlorine hexyl, phenyl, benzyl, one of xenyl, R2It is Cl or Br for one of H, methyl, methoxyl group, trifluoromethyl, X.Preparation method is simple, and the C-N coupling reaction of arylsulfonyl hydrazine and 5- oxyl -3,4- dihalo- -2 (5H) furanone is carried out under the action of 4-dimethylaminopyridine and tetrabutylammonium iodide.The present invention has synthesized a kind of completely new N- furanonyl arylsulfonyl hydrazine derivative with bioactivity such as antitumor, antibacterials.Synthetic method of the invention has many advantages, such as that simple and easy, reaction time is short, raw material is easy to get, wide application range of substrates, yield are high.

Description

A kind of N- furanonyl arylsulfonyl hydrazine derivative and its preparation method and application
Technical field
The present invention relates to a kind of N- furanonyl arylsulfonyl hydrazine derivatives and its preparation method and application, belong to chemistry Synthesis technical field.
Background technique
Since many arylsulfonyl hydrazine class compounds all have the bioactivity such as antitumor, antibacterial, so containing arylsulfonyl Hydrazine structural unit is got more and more attention in the design and synthesis of drug molecule.However, the arylsulfonyl hydrazine reported at present is raw Object bioactive molecule is usually the structure that 2- N replace, such as:
[bibliography: Kamal A, Khan M N A, Reddy K S, et al.Bioorg Med Chem, 2007,15 (2), 1004- 1013；Arkinstall S,Halazy S,Church D,et al.Pharmaceutically active sulfonyl hydrazide derivatives,EP1088822,2001-04-04]。
2 (5H)-furanone structure units are widely present in natural products, these natural products have mostly it is antitumor, The bioactivity such as antibacterial [bibliography: 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, at present There is no the noval chemical compounds for combining arylsulfonyl hydrazine structural unit and 2 (5H)-furanone structure units to synthesize report.
Summary of the invention
The purpose of the present invention is to provide a kind of N- furanonyl arylsulfonyl hydrazine derivative and preparation method thereof and answer With.
The technical solution used in the present invention is:
A kind of N- furanonyl arylsulfonyl hydrazine derivative, general structure are as follows:
Wherein, R1For C1~C6Alkyl, 6- chlorine hexyl, phenyl, benzyl, one of xenyl, R2For H, methyl, methoxyl group, trifluoro One of methyl, X are Cl or Br.
Preferably, a kind of N- furanonyl arylsulfonyl hydrazine derivative, general structure are as follows:
Wherein, R1For C1~C6Alkyl, 6- chlorine hexyl, phenyl, benzyl, one of xenyl, R2For H, methyl, first One of oxygroup, trifluoromethyl, X are Cl or Br.
Preferably, the R2For H or methyl.
The preparation method of above-mentioned N- furanonyl arylsulfonyl hydrazine derivative, comprising the following steps: in 4- dimethylamino Under the action of pyridine and tetrabutylammonium iodide, the C-N of arylsulfonyl hydrazine and 5- oxyl -3,4- dihalo- -2 (5H) furanone is carried out Coupling reaction to get arrive N- furanonyl arylsulfonyl hydrazine derivative.
Preferably, the C-N coupling reaction carries out at room temperature.
Preferably, the time of the C-N coupling reaction is 10~60min.
Note: C1~C6Alkyl include straight chained alkyl, branched alkyl and naphthenic base.
The beneficial effects of the present invention are: the present invention synthesized it is a kind of completely new with bioactivity such as antitumor, antibacterials N- furanonyl arylsulfonyl hydrazine derivative.Synthetic method of the invention is with simple and easy, reaction time is short, raw material is easy , wide application range of substrates, high yield the advantages that.
Detailed description of the invention
Fig. 1 is the X-ray single crystal diffraction figure of the N- furanonyl arylsulfonyl hydrazine derivative 1 of embodiment 1.
Specific embodiment
The present invention will be further explained combined with specific embodiments below and explanation.
Embodiment 1:
N- furanonyl arylsulfonyl hydrazine derivative 1:
The preparation method is as follows: by bromo- 2 (the 5H)-furanone of 5- methoxyl group -3,4- two of 0.50mmol (0.136g), 0.60mmol (0.112g) to the 4-dimethylaminopyridine (DMAP) of Methyl benzenesulfonyl hydrazine, 1.0mmol (0.122g), Tetrabutylammonium iodide (the n-Bu of 0.015mmol (0.005g)4NI), the water of the methylene chloride of 2.5mL and 0.5mL are uniformly mixed, Reaction 30min is stirred at room temperature, is diluted after reaction with the water of 15mL, then is extracted with methylene chloride (15mL × 3), liquid separation, has Machine layer is dry with anhydrous sodium sulfate, and decompression is spin-dried for, and crude product column separation obtains the N- furanonyl arylsulfonyl hydrazine of 0.155g Analog derivative 1 (white solid, yield 82%, 135.4~136.9 DEG C of fusing point).
The relevant characterization data of N- furanonyl arylsulfonyl hydrazine derivative 1 are as follows:
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；
X-ray single crystal diffraction figure is as shown in Figure 1；
Nuclear magnetic resonance spectroscopy, carbon-13 nmr spectra, high resolution mass spectrum and X-ray single crystal diffraction characterization result show N- furan Mutter ketone group arylsulfonyl hydrazine derivative 1 structure with expection it is consistent.
Embodiment 2:
N- furanonyl arylsulfonyl hydrazine derivative 2:
The preparation method is as follows: by two bromo- 2 (5H)-furans of 5- (6- chlorine hexyloxy) -3,4- of 0.50mmol (0.187g) Ketone, 0.60mmol (0.112g) to the 4-dimethylaminopyridine (DMAP) of Methyl benzenesulfonyl hydrazine, 1.0mmol (0.122g), Tetrabutylammonium iodide (the n-Bu of 0.015mmol (0.005g)4NI), the water of the methylene chloride of 2.5mL and 0.5mL are uniformly mixed, Reaction 30min is stirred at room temperature, is diluted after reaction with the water of 15mL, then is extracted with methylene chloride (15mL × 3), liquid separation, has Machine layer is dry with anhydrous sodium sulfate, and decompression is spin-dried for, and crude product column separation obtains the N- furanonyl arylsulfonyl hydrazine of 202mg Analog derivative 2 (colorless oil, yield 84%).
The relevant characterization data of N- furanonyl arylsulfonyl hydrazine derivative 2 are as follows:
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；
Nuclear magnetic resonance spectroscopy, carbon-13 nmr spectra and high resolution mass spectrum characterization result show N- furanonyl arylsulfonyl hydrazine The structure of analog derivative 2 is consistent with expection.
Embodiment 3:
N- furanonyl arylsulfonyl hydrazine derivative 3:
The preparation method is as follows: by bromo- 2 (the 5H)-furanone of 5- isopropoxy -3,4- two of 0.50mmol (0.149g), 0.60mmol (0.112g) to the 4-dimethylaminopyridine (DMAP) of Methyl benzenesulfonyl hydrazine, 1.0mmol (0.122g), Tetrabutylammonium iodide (the n-Bu of 0.015mmol (0.005g)4NI), the water of the methylene chloride of 2.5mL and 0.5mL are uniformly mixed, Reaction 30min is stirred at room temperature, is diluted after reaction with the water of 15mL, then is extracted with methylene chloride (15mL × 3), liquid separation, has Machine layer is dry with anhydrous sodium sulfate, and decompression is spin-dried for, and crude product column separation obtains the N- furanonyl arylsulfonyl hydrazine of 151mg Analog derivative 3 (colorless oil, yield 75%).
The relevant characterization data of N- furanonyl arylsulfonyl hydrazine derivative 3 are as follows:
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；
Nuclear magnetic resonance spectroscopy, carbon-13 nmr spectra and high resolution mass spectrum characterization result show N- furanonyl arylsulfonyl hydrazine The structure of analog derivative 3 is consistent with expection.
Embodiment 4:
N- furanonyl arylsulfonyl hydrazine derivative 4:
The preparation method is as follows: by bromo- 2 (the 5H)-furanone of 5- benzyloxy -3,4- two of 0.50mmol (0.173g), 0.60mmol (0.112g) to the 4-dimethylaminopyridine (DMAP) of Methyl benzenesulfonyl hydrazine, 1.0mmol (0.122g), Tetrabutylammonium iodide (the n-Bu of 0.015mmol (0.005g)4NI), the water of the methylene chloride of 2.5mL and 0.5mL are uniformly mixed, Reaction 30min is stirred at room temperature, is diluted after reaction with the water of 15mL, then is extracted with methylene chloride (15mL × 3), liquid separation, has Machine layer is dry with anhydrous sodium sulfate, and decompression is spin-dried for, and crude product column separation obtains the N- furanonyl arylsulfonyl hydrazine of 181mg Analog derivative 4 (colorless waxy, yield 80%).
The relevant characterization data of N- furanonyl arylsulfonyl hydrazine derivative 4 are as follows:
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；
Nuclear magnetic resonance spectroscopy, carbon-13 nmr spectra and high resolution mass spectrum characterization result show N- furanonyl arylsulfonyl hydrazine The structure of analog derivative 4 is consistent with expection.
Embodiment 5:
N- furanonyl arylsulfonyl hydrazine derivative 5:
The preparation method is as follows: by bromo- 2 (the 5H)-furanone of 5- phenoxy group -3,4- two of 0.50mmol (0.166g), 0.60mmol (0.112g) to the 4-dimethylaminopyridine (DMAP) of Methyl benzenesulfonyl hydrazine, 1.0mmol (0.122g), Tetrabutylammonium iodide (the n-Bu of 0.015mmol (0.005g)4NI), the water of the methylene chloride of 2.5mL and 0.5mL are uniformly mixed, Reaction 30min is stirred at room temperature, is diluted after reaction with the water of 15mL, then is extracted with methylene chloride (15mL × 3), liquid separation, has Machine layer is dry with anhydrous sodium sulfate, and decompression is spin-dried for, and crude product column separation obtains the N- furanonyl arylsulfonyl hydrazine of 166mg Analog derivative 5 (colorless waxy, yield 76%).
The relevant characterization data of N- furanonyl arylsulfonyl hydrazine derivative 5 are as follows:
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；
Nuclear magnetic resonance spectroscopy, carbon-13 nmr spectra and high resolution mass spectrum characterization result show N- furanonyl arylsulfonyl hydrazine The structure of analog derivative 5 is consistent with expection.
Embodiment 6:
N- furanonyl arylsulfonyl hydrazine derivative 6:
The preparation method is as follows: by two bromo- 2 (5H)-furan of 5- (4- phenyl-phenoxy group) -3,4- of 0.50mmol (0.204g) Mutter ketone, 0.60mmol (0.112g) to the 4-dimethylaminopyridine (DMAP) of Methyl benzenesulfonyl hydrazine, 1.0mmol (0.122g), Tetrabutylammonium iodide (the n-Bu of 0.015mmol (0.005g)4NI), the water of the methylene chloride of 2.5mL and 0.5mL are uniformly mixed, Reaction 30min is stirred at room temperature, is diluted after reaction with the water of 15mL, then is extracted with methylene chloride (15mL × 3), liquid separation, has Machine layer is dry with anhydrous sodium sulfate, and decompression is spin-dried for, and crude product column separation obtains the N- furanonyl arylsulfonyl hydrazine of 180mg Analog derivative 6 (white solid, yield 70%, 142.4~143.9 DEG C of fusing point).
The relevant characterization data of N- furanonyl arylsulfonyl hydrazine derivative 6 are as follows:
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；
Nuclear magnetic resonance spectroscopy, carbon-13 nmr spectra and high resolution mass spectrum characterization result show N- furanonyl arylsulfonyl hydrazine The structure of analog derivative 6 is consistent with expection.
Embodiment 7:
N- furanonyl arylsulfonyl hydrazine derivative 7:
The preparation method is as follows: by bromo- 2 (the 5H)-furanone of 5- isopropoxy -3,4- two of 0.50mmol (0.149g), The benzene sulfonyl hydrazide of 0.60mmol (0.103g), the 4-dimethylaminopyridine (DMAP) of 1.0mmol (0.122g), 0.015mmol Tetrabutylammonium iodide (the n-Bu of (0.005g)4NI), the water of the methylene chloride of 2.5mL and 0.5mL are uniformly mixed, and are stirred at room temperature anti- 30min is answered, is diluted after reaction with the water of 15mL, then is extracted with methylene chloride (15mL × 3), liquid separation, organic layer is with anhydrous Sodium sulphate is dry, and decompression is spin-dried for, and crude product column separation obtains the N- furanonyl arylsulfonyl hydrazine derivative 7 of 164mg (colorless waxy, yield 84%).
The relevant characterization data of N- furanonyl arylsulfonyl hydrazine derivative 7 are as follows:
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；
Nuclear magnetic resonance spectroscopy, carbon-13 nmr spectra and high resolution mass spectrum characterization result show N- furanonyl arylsulfonyl hydrazine The structure of analog derivative 7 is consistent with expection.
Embodiment 8:
N- furanonyl arylsulfonyl hydrazine derivative 8:
The preparation method is as follows: by chloro- 2 (the 5H)-furanone of 5- propoxyl group -3,4- two of 0.50mmol (0.105g), The unifor of 0.60mmol (0.112g), 1.0mmol (0.122g) 4-dimethylaminopyridine (DMAP), Tetrabutylammonium iodide (the n-Bu of 0.015mmol (0.005g)4NI), the water of the methylene chloride of 2.5mL and 0.5mL are uniformly mixed, Reaction 30min is stirred at room temperature, is diluted after reaction with the water of 15mL, then is extracted with methylene chloride (15mL × 3), liquid separation, has Machine layer is dry with anhydrous sodium sulfate, and decompression is spin-dried for, and crude product column separation obtains the N- furanonyl arylsulfonyl hydrazine of 155mg Analog derivative 8 (colorless waxy, yield 86%).
The relevant characterization data of N- furanonyl arylsulfonyl hydrazine derivative 8 are as follows:
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；
Nuclear magnetic resonance spectroscopy, carbon-13 nmr spectra and high resolution mass spectrum characterization result show N- furanonyl arylsulfonyl hydrazine The structure of analog derivative 8 is consistent with expection.
Embodiment 9:
N- furanonyl arylsulfonyl hydrazine derivative 9:
The preparation method is as follows: by chloro- 2 (the 5H)-furanone of 5- cyclohexyloxy -3,4- two of 0.50mmol (0.125g), The unifor of 0.60mmol (0.112g), 1.0mmol (0.122g) 4-dimethylaminopyridine (DMAP), Tetrabutylammonium iodide (the n-Bu of 0.015mmol (0.005g)4NI), the water of the methylene chloride of 2.5mL and 0.5mL are uniformly mixed, Reaction 30min is stirred at room temperature, is diluted after reaction with the water of 15mL, then is extracted with methylene chloride (15mL × 3), liquid separation, has Machine layer is dry with anhydrous sodium sulfate, and decompression is spin-dried for, and crude product column separation obtains the N- furanonyl arylsulfonyl hydrazine of 156mg Analog derivative 9 (colorless waxy, yield 78%).
The relevant characterization data of N- furanonyl arylsulfonyl hydrazine derivative 9 are as follows:
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；
Nuclear magnetic resonance spectroscopy, carbon-13 nmr spectra and high resolution mass spectrum characterization result show N- furanonyl arylsulfonyl hydrazine The structure of analog derivative 9 is consistent with expection.
Embodiment 10:
N- furanonyl arylsulfonyl hydrazine derivative 10:
The preparation method is as follows: by chloro- 2 (the 5H)-furanone of 5- methoxyl group -3,4- two of 0.50mmol (0.091g), The benzene sulfonyl hydrazide of 0.60mmol (0.103g), the 4-dimethylaminopyridine (DMAP) of 1.0mmol (0.122g), 0.015mmol Tetrabutylammonium iodide (the n-Bu of (0.005g)4NI), the water of the methylene chloride of 2.5mL and 0.5mL are uniformly mixed, and are stirred at room temperature anti- 30min is answered, is diluted after reaction with the water of 15mL, then is extracted with methylene chloride (15mL × 3), liquid separation, organic layer is with anhydrous Sodium sulphate is dry, and decompression is spin-dried for, and crude product column separation obtains the N- furanonyl arylsulfonyl hydrazine derivative 10 of 130mg (colorless waxy, yield 82%).
The relevant characterization data of N- furanonyl arylsulfonyl hydrazine derivative 10 are as follows:
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；
Nuclear magnetic resonance spectroscopy, carbon-13 nmr spectra and high resolution mass spectrum characterization result show N- furanonyl arylsulfonyl hydrazine The structure of analog derivative 10 is consistent with expection.
Embodiment 11:
N- furanonyl arylsulfonyl hydrazine derivative 11:
The preparation method is as follows: by chloro- 2 (the 5H)-furanone of 5- phenoxy group -3,4- two of 0.50mmol (0.122g), The benzene sulfonyl hydrazide of 0.60mmol (0.103g), the 4-dimethylaminopyridine (DMAP) of 1.0mmol (0.122g), 0.015mmol Tetrabutylammonium iodide (the n-Bu of (0.005g)4NI), the water of the methylene chloride of 2.5mL and 0.5mL are uniformly mixed, and are stirred at room temperature anti- 30min is answered, is diluted after reaction with the water of 15mL, then is extracted with methylene chloride (15mL × 3), liquid separation, organic layer is with anhydrous Sodium sulphate is dry, and decompression is spin-dried for, and crude product column separation obtains the N- furanonyl arylsulfonyl hydrazine derivative 11 of 139mg (white solid, yield 73%, 129.4~130.8 DEG C of fusing point).
The relevant characterization data of N- furanonyl arylsulfonyl hydrazine derivative 11 are as follows:
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；
Nuclear magnetic resonance spectroscopy, carbon-13 nmr spectra and high resolution mass spectrum characterization result show N- furanonyl arylsulfonyl hydrazine The structure of analog derivative 11 is consistent with expection.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention, It should be equivalent substitute mode, be included within the scope of the present invention.

Claims (8)

1. a kind of N- furanonyl arylsulfonyl hydrazine derivative, it is characterised in that: its general structure are as follows:
Wherein, R1For C1~C6Alkyl, 6- chlorine hexyl, phenyl, benzyl, one of xenyl, R2For H, methyl, methoxyl group, One of trifluoromethyl, X are Cl or Br.
2. N- furanonyl arylsulfonyl hydrazine derivative according to claim 1, it is characterised in that: its general structure Are as follows:
Wherein, R1For C1~C6Alkyl, 6- chlorine hexyl, phenyl, benzyl, one of xenyl, R2For H, methyl, methoxyl group, One of trifluoromethyl, X are Cl or Br.
3. N- furanonyl arylsulfonyl hydrazine derivative according to claim 1 or 2, it is characterised in that: the R2For H Or methyl.
4. the preparation method of N- furanonyl arylsulfonyl hydrazine derivative described in any one of claims 1 to 3, special Sign is: the following steps are included: carrying out arylsulfonyl hydrazine and 5- under the action of 4-dimethylaminopyridine and tetrabutylammonium iodide The C-N coupling reaction of oxyl -3,4- dihalo- -2 (5H) furanone to get arrive N- furanonyl arylsulfonyl hydrazine derivative.
5. the preparation method according to claim 4, it is characterised in that: the C-N coupling reaction carries out at room temperature.
6. preparation method according to claim 4 or 5, it is characterised in that: the time of the C-N coupling reaction be 10~ 60min。
7. N- furanonyl arylsulfonyl hydrazine derivative described in any one of claims 1 to 3 is preparing antineoplastic Application in object.
8. N- furanonyl arylsulfonyl hydrazine derivative described in any one of claims 1 to 3 is in preparation antibacterials In application.
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CN115594995A (en) * 2022-08-11 2023-01-13 赵子龙（Cn） Preparation method of filler for coating

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CN115594995A (en) * 2022-08-11 2023-01-13 赵子龙（Cn） Preparation method of filler for coating

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