CN116730922A - 一种吡唑磺酰肼衍生物、制备方法及其应用 - Google Patents
一种吡唑磺酰肼衍生物、制备方法及其应用 Download PDFInfo
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- CCCGEKHKTPTUHJ-UHFFFAOYSA-N N-[9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-3-(difluoromethyl)-1-methylpyrazole-4-carboxamide Chemical compound FC(F)C1=NN(C)C=C1C(=O)NC1=CC=CC2=C1C1CCC2C1=C(Cl)Cl CCCGEKHKTPTUHJ-UHFFFAOYSA-N 0.000 description 1
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- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
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- C07D231/18—One oxygen or sulfur atom
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- A01N51/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds having the sequences of atoms O—N—S, X—O—S, N—N—S, O—N—N or O-halogen, regardless of the number of bonds each atom has and with no atom of these sequences forming part of a heterocyclic ring
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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Abstract
本发明属于杀菌剂领域,公开了一种吡唑磺酰肼衍生物、制备方法及其应用,该衍生物的结构如式(I)所示:
Description
技术领域
本发明涉及农药领域,具体来说涉及一种吡唑磺酰肼衍生物,同时涉及该衍生物的制备方法,还涉及该衍生物在防治植物病原微生物方面的应用。
背景技术
吡唑酰胺类杀菌剂是近年来国内外研究开发的一系列新型SDH抑制剂,这类杀菌剂抗真菌活性非常突出,且具有广谱、低毒等优点,当前已有多种吡唑酰胺类杀菌剂实现了商品化或正处于推广应用阶段,其中包括吡噻菌胺(penthiopyrad)、氟唑菌酰胺(fluxapyroxad)、苯并烯氟菌唑(benzovindiflupyr)、氟唑菌酰羟胺(pydiflumetofen)、氟苯醚酰胺(flubeneteram)等品种。这些SDHI类杀菌剂的分子结构具有相同的吡唑甲酰胺这一活性结构单元,易导致交互抗性的产生,设计和创制具有独特分子结构的新型SDHI类杀菌剂是克服抗药性问题的手段之一,具有十分重要的意义。
肼基是农药化合物的重要结构单元,在杀虫剂、除草剂及杀菌剂的研究与应用领域均受到人们的广泛关注。近年来,人们在杀菌剂创制研究方面常常将肼基引入到目标化合物分子结构中,发现不少化合物对真菌具有显著的抑制活性。这些具有抑制真菌活性的化合物基本都属于碳酰肼,包括单酰肼和双酰肼两种类型。而有关磺酰肼类化合物具有农药生物活性的报道比较少见。本发明将吡唑基团通过磺酰肼结构片段与苯基有机结合,设计并合成了一种吡唑磺酰肼衍生物,发现对植物病原真菌具有显著的抑制作用。
发明内容
本发明的目的在于,提供一种吡唑磺酰肼衍生物。
本发明的另一目的在于提供一种吡唑磺酰肼衍生物的制备方法。
本发明的第3个目的在于提供上述衍生物的用途。
本发明的第一方面提供了一种具有通式(I)所示结构的吡唑磺酰肼衍生物,
在式(I)中,所述各个基团具有如下所述的定义:
R1选自H、C1~C6烷基、C3~C6环烷基;
R2选自H、C1~C6烷基、C3~C6环烷基、含1~3个卤素的C1~C6烷基;
R3选自H、卤素、C1~C6烷基;
R4选自1~4个下列基团:H、卤素、C1~C6烷基、含1~3个卤素的C1~C6烷基、C1~C6烷氧基、硝基;
以上基团的定义中提及的卤素选自F、Cl、Br、I;
以上基团的定义中R1、R2、R3不同时为H。
在式(I)中,所述各个基团具有如下所述的优选定义:
R1选自H、C1~C3烷基;
R2选自H、C1~C3烷基、含2~3个F的C1~C3烷基;
R3选自H、C1~C3烷基;
R4选自1~3个下列基团:H、F、Cl;
以上基团的定义中R1、R2、R3不同时为H。
在式(I)中,所述各个基团具有如下所述的进一步优选定义;
R1选自H、CH3;
R2选自H、CH3、CF3;
R3选自H、CH3;
R4选自1~2个下列基团:H、F、Cl;
以上基团的定义中R1、R2、R3不同时为H。
在式(I)中,所述各个基团具有如下所述的特别优选定义:
1-甲基-N-苯基-1H-吡唑-4-磺酰肼(I-1)、
N′-(2-氟苯基)-1-甲基-1H-吡唑-4-磺酰肼(I-2)、
N′-(3-氟苯基)-1-甲基-1H-吡唑-4-磺酰肼(I-3)、
N′-(4-氟苯基)-1-甲基-1H-吡唑-4-磺酰肼(I-4)、
N′-(2-氯苯基)-1-甲基-1H-吡唑-4-磺酰肼(I-5)、
N′-(3-氯苯基)-1-甲基-1H-吡唑-4-磺酰肼(I-6)、
N′-(4-氯苯基)-1-甲基-1H-吡唑-4-磺酰肼(I-7)、
N′-(2,4-二氯苯基)-1-甲基-1H-吡唑-4-磺酰肼(I-8)、
N′-(4-溴苯基)-1-甲基-1H-吡唑-4-磺酰肼(I-9)、
3,5-二甲基-N′-苯基-1H-吡唑-4-磺酰肼(I-10)、
N′-(2-氟苯基)-3,5-二甲基-1H-吡唑-4-磺酰肼(I-11)、
N′-(4-氟苯基)-3,5-二甲基-1H-吡唑-4-磺酰肼(I-12)、
N′-(2-氯苯基)-3,5-二甲基-1H-吡唑-4-磺酰肼(I-13)、
N′-(3-氯苯基)-3,5-二甲基-1H-吡唑-4-磺酰肼(I-14)、
N′-(2,4-二氯苯基)-3,5-二甲基-1H-吡唑-4-磺酰肼(I-15)、
N′-(2-氟苯基)-1,3-二甲基-1H-吡唑-4-磺酰肼(I-16)、
N′-(3-氟苯基)-1,3-二甲基-1H-吡唑-4-磺酰肼(I-17)、
N′-(2-氯苯基)-1,3-二甲基-1H-吡唑-4-磺酰肼(I-18)、
N′-(3-氯苯基)-1,3-二甲基-1H-吡唑-4-磺酰肼(I-19)、
N′-(2,4-二氯苯基)-1,3-二甲基-1H-吡唑-4-磺酰肼(I-20)、
N′-(2-氟苯基)-1,3,5-三甲基-1H-吡唑-4-磺酰肼(I-21)、
N′-(2-氯苯基)-1,3,5-三甲基-1H-吡唑-4-磺酰肼(I-22)、
N′-(2,4-二氯苯基)-1,3,5-三甲基-1H-吡唑-4-磺酰肼(I-23)、
N′-(2-氯苯基)-3-(三氟甲基)-1H-吡唑-4-磺酰肼(I-24)、
N′-(2,4-二氯苯基)-3-(三氟甲基)-1H-吡唑-4-磺酰肼(I-25)、
N′-(3-氟苯基)-1-甲基-3-(三氟甲基)-1H-吡唑-4-磺酰肼(I-26)、
N′-(2,4-二氯苯基)-1-甲基-3-(三氟甲基)-1H-吡唑-4-磺酰肼(I-27)、
N′-(4-溴苯基)-1-甲基-3-(三氟甲基)-1H-吡唑-4-磺酰肼(1-28)、
5-甲基-N′-苯基-3-(三氟甲基)-1H-吡唑-4-磺酰肼(I-29)、
N′-(2-氟苯基)-5-甲基-3-(三氟甲基)-1H-吡唑-4-磺酰肼(1-30)、
N′-(3-氟苯基)-5-甲基-3-(三氟甲基)-1H-吡唑-4-磺酰肼(I-31)、
N′-(2-氯苯基)-5-甲基-3-(三氟甲基)-1H-吡唑-4-磺酰肼(I-32)、
N′-(3-氯苯基)-5-甲基-3-(三氟甲基)-1H-吡唑-4-磺酰肼(I-33)、
N′-(4-氯苯基)-5-甲基-3-(三氟甲基)-1H-吡唑-4-磺酰肼(I-34)、
N′-(2,4-二氯苯基)-5-甲基-3-(三氟甲基)-1H-吡唑-4-磺酰肼(1-35)、
N′-(4-溴苯基)-5-甲基-3-(三氟甲基)-1H-吡唑-4-磺酰肼(I-36)。
本发明的第二个方面提供了如通式(A)所示的一种吡唑磺酰肼衍生物(I)的制备方法,在吡啶(Pyridine)存在下,以二氯甲烷(DCM)为溶剂,取代吡唑磺酰氯(II)与取代苯肼(III)反应,生成一种吡唑磺酰肼衍生物(I):
其中在上述各结构式中:
R1、R2、R3、R4均具有如前所述的相应基团的定义。
本发明的第三个方面提供了式(I)所示的一种吡唑磺酰肼衍生物的应用,该类衍生物对植物病原真菌具有显著的抑制活性,可应用于防治植物真菌性病害。
本发明式(I)的一种吡唑磺酰肼衍生物适合于抑制水稻纹枯病菌、小麦赤霉病菌、番茄灰霉病菌、番茄早疫病菌,适合用于防治水稻纹枯病、小麦赤霉病、番茄灰霉病、番茄早疫病。
有益效果:
本发明与现有技术相比,具有明显的有益效果,从以上技术方案可知;本发明通过磺酰肼结构片段将吡唑基团与苯基结合,设计合成了一系列吡唑磺酰肼类衍生物(I),其分子结构具有新颖性;将该类化合物应用于抗植物病原真菌方面的研究,发现此类化合物对植物病原真菌拥有突出的抑制活性,体现出本技术方案的显著进步;其中部分化合物对水稻纹枯病菌、小麦赤霉病菌、番茄灰霉病菌、番茄早疫病菌的抑制活性超过对照药剂氟唑菌酰胺或啶酰菌胺,体现了明显的应用性。
具体实施方式
实施例一;1-甲基-N′-苯基-1H-吡唑-4-磺酰肼(I-1)的合成:
称取化合物II-1(1.00g,5.54mmol)于50mL单口瓶内,加入20mL二氯甲烷做溶剂,用冰盐浴控制温度在0℃以下,搅拌,用注射器缓慢加入0.83mL吡啶,称取苯肼(0.66g,6.09mmol),溶于5mL二氯甲烷,缓慢滴加,反应过夜,反应结束后减压蒸馏除去溶剂,用乙酸乙酯+石油醚(V/V=2∶1)的混和液作为洗脱液进行硅胶柱层析分离,得到白色固体1.24g,即化合物I-1。
化合物I-1~I-36按照实施例一的方法依次合成。所合成的吡唑磺酰肼衍生物(I-1~I-36)的分子结构均通过核磁共振谱(1H NMR)和高分辨质谱(HR-MS)进行了确证,化合物I-1~I-36的名称、结构式、物理参数如下所示:
1-甲基-N′-苯基-1H-吡唑-4-磺酰肼(I-1)
白色粉末;产率88.7%;m.p.143.1-144.5℃;1H NMR(400MHz,DMSO-d6)δ:9.25(s,1H),8.27(s,1H),7.75(s,1H),7.63(s,1H),7.11(t,J=7.8Hz,2H),6.83(d,J=7.9Hz,2H),6.70(t,J=7.3Hz,1H),3.88(s,3H);m/z calcd for C10H13N4O2S([M+H]+)253.0754,found253.0756.
N′-(2-氟苯基)-1-甲基-1H-吡唑-4-磺酰肼(I-2)
白色粉末;产率78.5%;m.p.156.9-158.1℃;1H NMR(400MHz,DMSO-d6)δ:9.34(s,1H),8.28(s,1H),7.75(s,1H),7.73(s,1H),7.11(t,J=7.9Hz,1H),7.02(dt,J=16.2,8.2Hz,2H),6.77-6.69(m,1H),3.88(s,3H);HR-MS(ESI):m/z calcd for C10H12FN4O2S([M+H]+)271.0660,found 271.0669.
N′-(3-氟苯基)-1-甲基-1H-吡唑-4-磺酰肼(I-3)
白色粉末;产率87.1%;m.p.180.5-181.7.3℃;1H NMR(400MHz,DMSO-d6)δ:9.37(s,1H),8.30(s,1H),7.95(s,1H),7.76(s,1H),7.12(dd,J=15.0,8.0Hz,1H),6.66-6.61(m,1H),6.58(dd,J=11.8,2.1Hz,1H),6.47(td,,J=8.5,2.2Hz,1H),3.89(s,3H);HR-MS(ESI):m/z calcd for C10H12FN4O2S([M+H]+)271.0660,found 271.0660.
N′-(4-氟苯基)-1-甲基-1H-吡唑-4-磺酰肼(I-4)
白色粉末;产率69.5%;m.p.151.7-153.3℃;1H NMR(400MHz,DMSO-d6)δ:9.29(s,1H),8.28(s,1H),7.75(s,1H),7.61(s,1H),6.96(t,J=8.9Hz,2H),6.87-6.80(m,2H),3.89(s,3H);HR-MS(ESI):m/z calcd for C10H12FN4O2S([M+H]+)271.0660,found 271.0670.
N′-(2-氯苯基)-1-甲基-1H-吡唑-4-磺酰肼(I-5)
白色粉末;产率78.5%;m.p.153.2-154.5℃;1H NMR(400MHz,DMSO-d6)δ:9.33(s,1H),8.30(s,1H),7.76(s,1H),7.32(s,1H),7.25(d,J=7.8Hz,1H),7.16(qd,J=8.2,4.5Hz,2H),6.81-6.73(m,1H),3.89(s,3H);HR-MS(ESI):m/z calcd for C10H12ClN4O2S([M+H]+)287.0364,found 287.0378.
N′-(3-氯苯基)-1-甲基-1H-吡唑-4-磺酰肼(I-6)
白色粉末;产率89.4%;m.p.168.0-169.2℃;1H NMR(400MHz,DMSO-d6)δ:9.41(s,1H),8.31(s,1H),7.97(s,1H),7.76(s,1H),7.12(t,J=8.0Hz,1H),6.83(t,J=1.9Hz,1H),6.74(ddd,J=9.1,8.0,1.5Hz,2H),3.89(s,3H);HR-MS(ESI):m/z calcd for C10H12ClN4O2S([M+H]+)287.0364,found 287.0378.
N′-(4-氯苯基)-1-甲基-1H-吡唑-4-磺酰肼(I-7)
白色粉末;产率79.9%;m.p.156.7-157.9℃;1H NMR(400MHz,DMSO-d6)δ:9.36(s,1H),8.29(s,1H),7.84(s,1H),7.75(s,1H),7.15(d,J=8.8Hz,2H),6.83(d,J=8.8Hz,2H),3.89(s,3H);HR-MS(ESI):m/z calcd for C10H12ClN4O2S([M+H]+)287.0364,found287.0365.
N′-(2,4-二氯苯基)-1-甲基-1H-吡唑-4-磺酰肼(I-8)
棕黄色粉末;产率90.3%;m.p.175.7-176.5℃;1H NMR(400MHz,DMSO-d6)δ:9.43(s,1H),8.30(s,1H),7.76(s,1H),7.62(s,1H),7.40(d,J=2.3Hz,1H),7.25(dd,J=8.9,2.2Hz,1H),7.14(d,J=8.9Hz,1H),3.89(s,3H);HR-MS(ESI):m/z calcd forC10H11Cl2N4O2S([M+H]+)320.9974,found 320.9983.
N′-(4-溴苯基)-1-甲基-1H-吡唑-4-磺酰肼(I-9)
白色粉末;产率84.3%;m.p.169.8-170.5℃;1H NMR(400MHz,DMSO-d6)δ:9.35(s,1H),8.29(s,1H),7.86(s,1H),7.75(s,1H),7.27(d,J=8.8Hz,2H),6.79(d,J=8.8Hz,2H),3.89(s,3H);HR-MS(ESI):m/z calcd for C10H12BrN4O2S([M+H]+)330.9859,found330.9882.
3,5-二甲基-N′-苯基-1H-吡唑-4-磺酰肼(I-10)
白色粉末;产率89.8%;m.p.141.2-142.4℃;1H NMR(400MHz,DMSO-d6)δ:12.85(s,1H),9.07(d,J=1.1Hz,1H),7.59(s,1H),7.07(t,J=7.9Hz,2H),6.77(d,J=7.7Hz,2H),6.65(t,J=7.3Hz,1H),2.28(s,6H);HR-MS(ESI):m/z calcd for C10H15N4O2S([M+H]+)267.0910,found 267.0919.
N′-(2-氟苯基)-3,5-二甲基-1H-吡唑-4-磺酰肼(I-11)
棕黄色粉末;产率59.7%;m.p.172.9-173.5℃;1H NMR(400MHz,DMSO-d6)δ:12.82(s,1H),9.13(s,1H),7.65(s,1H),7.00(ddd,J=17.6,14.5,7.2Hz,3H),6.76-6.57(m,1H),2.27(s,6H);HR-MS(ESI):m/z calcd for C10H1M4O2S([M+H]+)285.0816,found 285.0829.
N′-(4-氟苯基)-3,5-二甲基-1H-吡唑-4-磺酰肼(I-12)
白色粉末;产率78.3%;m.p.157.4-158.3℃;IR(KBr,cm-1)v:3325,3214,1509,1413,1319,1195,1108,825,702,643;1H NMR(400MHz,DMSO-d6)δ:9.12(s,1H),7.56(s,1H),6.97-6.88(m,2H),6.81-6.73(m,2H),2.27(s,6H);HR-MS(ESI):m/z calcd forC10H14FN4O2S([M+H]+)285.0816,found 285.0832.
N′-(2-氯苯基)-3,5-二甲基-IH-吡唑-4-磺酰肼(I-13)
白色粉末;产率68.9%;m.p.159.6-160.3℃;1H NMR(400MHz,DMSO-d6)δ:12.84(s,1H),9.14(d,J=1.0Hz,1H),7.30(s,1H),7.24(dd,J=7.9,1.2Hz,1H),7.13(dd,J=11.3,4.1Hz,1H),7.06(dd,J=8.2,1.4Hz,1H),6.73(td,J=7.8,1.6Hz,1H),2.28(s,6H);HR-MS(ESI):m/z calcd for C10H14ClN4O2S([M+H]+)301.0521,found 301.0536.
N′-(3-氯苯基)-3,5-二甲基-1H-吡唑-4-磺酰肼(I-14)
白色粉末;产率54.9%;m.p.161.8-162.9℃;1H NMR(400MHz,DMSO-d6)δ:12.94(s,1H),9.21(s,1H),7.94(s,1H),7.08(t,J=8.0Hz,1H),6.78(d,J=1.9Hz,1H),6.73-6.62(m,2H),2.27(s,6H);HR-MS(ESI):m/z calcd for C10H14ClN4O2S([M+H]+)301.0521,found301.0537.
N′-(2,4-二氯苯基)-3,5-二甲基-1H-吡唑-4-磺酰肼(I-15)
白色粉末;产率85.1%;m.p.173.2-174.5℃;1H NMR(400MHz,DMSO-d6)δ:9.24(s,1H),7.57(s,1H),7.37(d,J=2.4Hz,1H),7.21(dd,J=8.9,2.3Hz,1H),7.06(d,J=8.9Hz,1H),2.27(s,6H);HR-MS(ESI):m/z calcd for C10H13Cl2N4O2S([M+H]+)335.0131,found335.0155.
N′-(2-氟苯基)-1,3-二甲基-1H-吡唑-4-磺酰肼(I-16)
淡黄色粉末;产率58.7%;m.p.160.1-161.3℃;1H NMR(400MHz,DMSO-d6)δ:9.28(s,1H),8.14(s,1H),7.76(s,1H),7.05(ddd,J=20.5,16.4,8.3Hz,3H),6.72(dd,J=11.8,6.5Hz,1H),3.78(s,3H),2.29(s,3H);HR-MS(ESI):m/z calcd for C10H14FN4O2S([M+H]+)285.0816,found 285.0834.
N′-(3-氟苯基)-1,3-二甲基-1H-吡唑-4-磺酰肼(I-17)
白色粉末;产率54.5%;m.p.157.9-158.6℃;1H NMR(400MHz,DMSO-d6)δ:9.31(s,1H),8.15(s,1H),7.95(s,1H),7.11(dd,J=15.0,8.1Hz,1H),6.61(dd,J=8.2,1.4Hz,1H),6.55(dt,J=11.9,2.2Hz,1H),6.46(td,J=8.3,2.3Hz,1H),3.78(s,3H),2.28(s,3H);HR-MS(ESI):m/z calcd for C10H14FN4O2S([M+H]+)285.0816,found 285.0835.
N′-(2-氯苯基)-1,3-二甲基-1H-吡唑-4-磺酰肼(I-18)
棕黄色粉末;产率65.5%;m.p.157.3-158.3℃;1H NMR(400MHz,DMSO-d6)δ:9.28(d,J=1.1Hz,1H),8.15(s,1H),7.40(s,1H),7.25(dd,J=7.9,1.2Hz,1H),7.21-.08(m,2H),6.76(td,J=7.9,1.7Hz,1H),3.78(s,3H),2.29(s,3H);HR-MS(ESI):m/z calcd forC10H14ClN4O2S([M+H]+)301.0521,found 301.0519.
N′-(3-氯苯基)-1,3-二甲基-1H-吡唑-4-磺酰肼(I-19)
白色粉末;产率63.5%;m.p.150.2-151.1℃;1H NMR(400MHz,DMSO-d6)δ:9.32(s,1H),8.14(s,1H),7.95(s,1H),7.11(t,J=8.0Hz,1H),6.81(t,J=1.9Hz,1H),6.72(ddd,J=12.6,8.1,1.2Hz,2H),3.78(s,3H),2.28(s,3H);HR-MS(ESI):m/z calcd forC10H14ClN4O2S([M+H]+)301.0521,found 301.0536.
N′-(2,4-二氯苯基)-1,3-二甲基-1H-吡唑-4-磺酰肼(I-20)
白色粉末;产率54.7%;m.p.155.6-156.4℃;1H NMR(400MHz,DMSO-d6)δ:9.37(s,1H),8.16(s,1H),7.68(s,1H),7.39(d,J=2.3Hz,1H),7.25(dd,J=8.9,2.3Hz,1H),7.12(d,J=8.9Hz,1H),3.79(s,3H),2.28(s,3H);HR-MS(ESI):m/z calcd for C10H13Cl2N4O2S([M+H]+)335.0131,found 335.0139.
N′-(2-氟苯基)-1,3,5-三甲基-1H-吡唑-4-磺酰肼(I-21)
白色粉末;产率47.3%;m.p.158.5-160.3℃;1H NMR(400MHz,DMSO-d6)δ:9.17(d,J=1.2Hz,1H),7.66(s,1H),7.10-6.90(m,3H),6.75-6.65(m,1H),3.65(s,3H),2.34(s,3H),2.23(s,3H);HR-MS(ESI):m/z calcd for C10H16FN4O-2S([M+H]+)299.0973,found299.0977.
N″-(2-氯苯基)-1,3,5-三甲基-1H-吡唑-4-磺酰肼(I-22)
白色粉末;产率58.3%;m.p.187.2-188.3℃;1H NMR(400MHz,DMSO-d6)δ:9.19(s,1H),7.33(s,1H),7.26-7.20(m,1H),7.14(t,J=7.7Hz,1H),7.09-7.03(m,1H),6.77-6.69(m,1H),3.65(s,3H),2.34(s,3H),2.23(s,3H);HR-MS(ESI):m/z calcd for C10H16ClN4O2S([M+H]+)315.0677,found 315.0669.
N″-(2,4-二氯苯基)-1,3,5-三甲基-1H-吡唑-4-磺酰肼(I-23)
白色粉末;产率68.4%;m.p.177.1-178.3℃;1H NMR(400MHz,DMSO-d6)δ:9.28(d,J=1.0Hz,1H),7.62(s,1H),7.38(d。J=2.3Hz,1H),7.22(dd,J=8.9,2.3Hz,1H),7.07(d,J=8.9Hz,1H),3.66(s,3H),2.35(s,3H),2.22(s,3H);HR-MS(ESI):m/z calcd forC10H15Cl2N4O2S([M+H]+)349.0287,found 349.0294.
N′-(2-氯苯基)-3-(三氟甲基)-1H-吡唑-4-磺酰肼(I-24)
棕黄色粉末;产率46.3%;m.p.147.5-148.5℃;1H NMR(400MHz,DMSO-d6)δ:14.26(s,1H),9.64(s,1H),8.55(s,1H),7.70(s,1H),7.25(dd,J=7.9,1.3Hz,1H),7.20-7.13(m,1H),7.08(dd,J=8.2,1.5Hz,1H),6.76(td,J=7.7,1.6Hz,1H);HR-MS(ESI):m/z calcdfor C10H9ClF3N4O2S([M+H]+)341.0081,found 341.0103.
N′-(2,4-二氯苯基)-3-(三氟甲基)-1H-吡唑-4-磺酰肼(I-25)
白色粉末;产率63.3%;m.p.160.3-161.5℃;1H NMR(400MHz,DMSO-d6)δ:14.28(s,1H),9.71(s,1H),8.56(s,1H),7.94(s,1H),7.40(d,J=2.3Hz,1H),7.25(dd,J=8.9,2.2Hz,1H),7.08(d,J=8.9Hz,1H);HR-MS(ESI):m/z calcd for C10H8Cl2F3N4O2S([M+H]+)374.9692,found 374.9710.
N′-(3-氟苯基)-1-甲基-3-(三氟甲基)-1H-吡唑-4-磺酰肼(I-26)
白色粉末;产率57.3%;m.p.146.4-147.3℃;1H NMR(400MHz,DMSO-d6)δ:9.71(s,1H),8.52(s,1H),8.12(s,1H),7.13(dd,J=15.0,8.0Hz,1H),6.59(d,J=8.2Hz,1H),6.56-6.46(m,2H),3.94(s,3H);HR-MS(ESI):m/z calcd for C11H11F4N4O2S([M+H]+)339.0533,found 339.0551.
N′-(2,4-二氯苯基)-1-甲基-3-(三氟甲基)-1H-吡唑-4-磺酰肼(I-27)
灰色粉末;产率48.3%;m.p.142.5-143.8℃;1H NMR(400MHz,DMSO-d6)δ:9.74(s,1H),8.53(s,1H),7.95(s,1H),7.40(d,J=2.3Hz,1H),7.27(dd,J=8.9,2.2Hz,1H),7.10(d,J=8.9Hz,1H),3.95(s,3H);HR-MS(ESI):m/z calcd for C11H10Cl2F3N4O2S([M+H]+)388.9848,found 388.9864.
N’-(4-溴苯基)-1-甲基-3-(三氟甲基)-1H-吡唑-4-磺酰肼(I-28)
灰色粉末;产率57.3%;m.p.140.9-141.8℃;1H NMR(400MHz,DMSO-d6)δ:9.66(s,1H),8.51(s,1H),8.00(s,1H),7.28(d,J=8.7Hz,2H),6.75(d,J=8.7Hz,2H),3.95(s,3H);HR-MS(ESI):m/z calcd for C11H11BrF3N4O2S([M+H]+)398.9733,found 398.9746.
5-甲基-N′-苯基-3-(三氟甲基)-1H-吡唑-4-磺酰肼(I-29)
灰白色粉末;产率87.3%;m.p.150.9-151.6℃;1H NMR(400MHz,DMSO-d6)δ:13.94(s,1H),9.43(s,1H),7.77(s,1H),7.08(t,J=7.9Hz,2H),6.74(d,J=7.7Hz,2H),6.67(t,J=7.3Hz,1H),2.37(s,3H);HR-MS(ESI):m/z calcd for C11H12F3N4O2S([M+H]+)321.0628,found 321.0648.
N′-(2-氟苯基)-5-甲基3-(三氟甲基)-1H-吡唑-4-磺酰肼(I-30)
棕黄色粉末;产率84.9%;m.p.152.5-153.6℃;1H NMR(400MHz,DMSO-d6)δ:13.95(s,1H),9.49(s,1H),7.89(s,1H),7.08-6.93(m,3H),6.75-6.65(m,1H),2.39(s,3H);HR-MS(ESI):m/z calcd for C11H11F4N4O2S([M+H]+)339.0533,found 339.0559.
N′-(3-氟苯基)-5-甲基-3-(三氟甲基)-1H-吡唑-4-磺酰肼(I-31)
白色粉末;产率88.3%;m.p.168.5-169.6℃;1H NMR(400MHz,DMSO-d6)δ:13.99(s,1H),9.55(s,1H),8.09(s,1H),7.10(dd,J=15.0,7.8Hz,1H),6.55(d,J=8.4Hz,1H),6.46(dd,J=15.2,6.8Hz,2H),2.38(s,3H);HR-MS(ESI):m/z calcd for C11H11F4N4O2S([M+H]+)339.0533,found 339.0558.
N′-(2-氯苯基)-5-甲基-3-(三氟甲基)-1H-吡唑-4-磺酰肼(I-32)
白色粉末;产率77.3%;m.p.155.5-156.3℃;1H NMR(400MHz,DMSO-d6)δ:13.93(s,1H),9.49(s,1H),7.68(s,1H),7.24(d,J=7.8Hz,1H),7.13(t,J=7.7Hz,1H),7.04(d,J=8.0Hz,1H),6.74(t,J=7.5Hz,1H),2.40(s,3H);HR-MS(ESI):m/z calcd forC11H11ClF3N4O2S([M+H]+)355.0238,found 355.0260.
N″-(3-氯苯基)-5-甲基3-(三氟甲基)-1H-吡唑-4-磺酰肼(I-33)
白色粉末;产率89.3%;m.p.155.7-156.9℃;1H NMR(400MHz,DMSO-d6)δ:14.01(s,1H),9.57(s,1H),8.10(s,1H),7.10(t,J=8.0Hz,1H),6.73(d,J=1.9Hz,1H),6.68(dd,J=12.3,4.5Hz,2H),2.38(s,3H);HR-MS(ESI):m/z calcd for C11H11ClF3N4O2S([M+H]+)355.0238,found 355.0262.
N′-(4-氯苯基)-5-甲基-3-(三氟甲基)-1H-吡唑-4-磺酰肼(I-34)
白色粉末;产率78.3%;m.p.157.7-159.3℃;1H NMR(400MHz,DMSO-d6)δ:14.00(s,1H),9.52(s,1H),7.96(s,1H),7.19-7.07(m,2H),6.87-6.63(m,2H),2.37(s,3H);HR-MS(ESI):m/z calcd for C11H11ClF3N4O2S([M+H]+)355.0238,found 355.0263.
N′-(2,4-二氯苯基)-5-甲基-3-(三氟甲基)-1H-吡唑-4-磺酰肼(I-35)
白色粉末;产率78.7%;m.p.176.7-177.1℃;1H NMR(400MHz,DMSO-d6)δ:13.97(s,1H),9.58(s,1H),7.92(s,1H),7.38(d,J=2.4Hz,1H),7.23(dd,J=8.8,2.3Hz,1H),7.05(d,J=8.9Hz,1H),2.40(s,3H);HR-MS(ESI):m/z calcd for C11H10Cl2F3N4O2S([M+H]+)388.9848,found 388.9874.
N′-(4-溴苯基)-5-甲基-3-(三氟甲基)-1H-吡唑-4-磺酰肼(I-36)
棕色粉末;产率57.3%;m.p.148.9-150.2℃;1H NMR(400MHz,DMSO-d6)δ:14.02(s,1H),9.52(s,1H),7.98(s,1H),7.28-7.21(m,2H),6.74-6.66(m,2H),2.37(s,3H);HR-MS(ESI):m/z calcd for C11H11BrF3N4O2S([M+H]+)398.9733,found 398.9761.
实施例二;吡唑磺酰肼衍生物(I-1~I-36)对植物病原真菌的抑制活性
采用菌丝生长速率法测定了一种吡唑磺酰肼衍生物(I-1~I-36)对水稻纹枯病菌(Rhizoctonia solani)、小麦赤霉病菌(Fusarium graminearum)、番茄灰霉病菌(Botrytiscinerea)和番茄早疫病菌(Alternaria solani)的抑制活性。操作步骤如下:称取一定量的化合物溶于一定体积的DMSO中,得到一定浓度的母液;量取一定体积的母液加入到45mL已灭菌的土豆琼脂培养基中,摇匀,得到含有10μg/mL药剂的培养基;将上述培养基均匀倒入3只直径为9厘米的培养皿中,待其凝固后,将直径为5毫米(mm)的菌饼转接至培养基的中心位置;将上述培养皿在25℃下培养,当空白对照(含等量DMSO)的菌落直接约为7.0厘米时,采用十字交叉法测定菌落直径,计算各药剂的平均抑制率。以氟唑菌酰胺和啶酰菌胺为对照药剂。各化合物对各真菌抑制率的计算公式如下:
抑菌率(%)=(空白对照菌落直径-测试药剂菌落直径)÷(空白对照菌落直径-5mm)×100%。
化合物I-1~I-36的抑菌活性测定结果如表1所示。
表1化合物I-1~I-36(10μg/mL)对4种植物病原真菌的抑制活性(%)
表一表明,一种吡唑磺酰肼衍生物(I-1~I-36)在10μg/mL浓度下对水稻纹枯病菌(Rhizoctonia solani)、小麦赤霉病菌(Fusarium graminearum)、番茄灰霉病菌(Botrytiscinerea)和番茄早疫病菌(Alternaria solani)均显示出显著的抑制活性。对水稻纹枯病菌的抑制率间于59.30%~100%,其中化合物I-2、I-3、I-5、I-6、I-8、I-10~I-27、I-30~I-33及I-35的抑制率高于对照药剂氟唑菌酰胺(82.13%)和啶酰菌胺(77.16%)。对小麦赤霉病菌的抑制率间于2.85%~100%,除了化合物I-22、I-27和I-28以外,其他化合物的抑制率均高于对照药剂氟唑菌酰胺(22.88%)和啶酰菌胺(11.49%)。对番茄灰霉病菌的抑制率间于12.04%~90.86%,其中化合物I-11、I-14和I-16的抑制率分别达到90.86%、87.84%及89.59%,高于对照药剂氟唑菌酰胺(78.68%)和啶酰菌胺(86.35%),化合物I-5和I-18的抑制率分别达到80.65%和78.93%,高于对照药剂氟唑菌酰胺(78.68%)。对番茄早疫病菌的抑制率间于24.93%~90.00%,除了化合物I-24、I-26、I-29和I-31以外,其他化合物的抑制率均高于啶酰菌胺(37.86%),其中化合物I-6、I-11、I-13、I-14、I-16、I-18、I-20及I-21的抑制率高于对照药剂氟唑菌酰胺(69.82)。
以上所述,仅是本发明的较佳实施案例而已,并非对本发明作任何形式上的限制,任何未脱离本发明技术方案内容,依据本发明的技术实质对以上实施例所做的任何简单修改、等同变化与修饰,均属于本发明技术方案的范畴。
Claims (9)
1.式(I)所示结构一种吡唑磺酰肼衍生物,
其中,
R1选自H、C1~C6烷基、C3~C6环烷基;
R2选自H、C1~C6烷基、C3~C6环烷基、含1~3个卤素的C1~C6烷基;
R3选自H、卤素、C1~C6烷基;
R4选自1~4个下列基团:H、卤素、C1~C6烷基、含1~3个卤素的C1~C6烷基、C1~C6烷氧基、硝基;
以上基团的定义中提及的卤素选自F、Cl、Br、I;
以上基团的定义中R1、R2、R3不同时为H。
2.权利要求1所述的一种吡唑磺酰肼衍生物,其特征在于:
R1选自H、C1~C3烷基;
R2选自H、C1~C3烷基、含2~3个F的C1~C3烷基;
R3选自H、C1~C3烷基;
R4选自1~3个下列基团:H、F、Cl;
以上基团的定义中R1、R2、R3不同时为H。
3.权利要求2所述的一种吡唑磺酰肼衍生物,其特征在于:
R1选自H、CH3;
R2选自H、CH3、CF3;
R3选自H、CH3;
R4选自1~2个下列基团:H、F、Cl;
以上基团的定义中R1、R2、R3不同时为H。
4.利要求3所述的一种吡唑磺酰肼衍生物,其特征在于其为如下所述化合物之一:
1-甲基-N′-苯基-1H-吡唑-4-磺酰肼、
N′-(2-氟苯基)-1-甲基-1H-吡唑-4-磺酰肼、
N′-(3-氟苯基)-1-甲基-1H-吡唑-4-磺酰肼、
N′-(4-氟苯基)-1-甲基-1H-吡唑-4-磺酰肼、
N′-(2-氯苯基)-1-甲基-1H-吡唑-4-磺酰肼、
N′-(3-氯苯基)-1-甲基-1H-吡唑-4-磺酰肼、
N′-(4-氯苯基)-1-甲基-1H-吡唑-4-磺酰肼、
N′-(2,4-二氯苯基)-1-甲基-1H-吡唑-4-磺酰肼、
N′-(4-溴苯基)-1-甲基-1H-吡唑-4-磺酰肼、
3,5-二甲基-N′-苯基-1H-吡唑-4-磺酰肼、
N′-(2-氟苯基)-3,5-二甲基-1H-吡唑-4-磺酰肼、
N′-(4-氟苯基)-3,5-二甲基-1H-吡唑-4-磺酰肼、
N′-(2-氯苯基)-3,5-二甲基-1H-吡唑-4-磺酰肼、
N′-(3-氯苯基)-3,5-二甲基-1H-吡唑-4-磺酰肼、
N′-(2,4-二氯苯基)-3,5-二甲基-1H-吡唑-4-磺酰肼、
N′-(2-氟苯基)-1,3-二甲基-1H-吡唑-4-磺酰肼、
N′-(3-氟苯基)-1,3-二甲基-1H-吡唑-4-磺酰肼、
N′-(2-氯苯基)-1,3-二甲基-1H-吡唑-4-磺酰肼、
N′-(3-氯苯基)-1,3-二甲基-1H-吡唑-4-磺酰肼、
N′-(2,4-二氯苯基)-1,3-二甲基-1H-吡唑-4-磺酰肼、
N′-(2-氟苯基)-1,3,5-三甲基-1H-吡唑-4-磺酰肼、
N′-(2-氯苯基)-1,3,5-三甲基-1H-吡唑-4-磺酰肼、
N′-(2,4-二氯苯基)-1,3,5-三甲基-1H-吡唑-4-磺酰肼、
N′-(2-氯苯基)-3-(三氟甲基)-1H-吡唑-4-磺酰肼、
N′-(2,4-二氯苯基)-3-(三氟甲基)-1H-吡唑-4-磺酰肼、
N′-(3-氟苯基)-1-甲基-3-(三氟甲基)-1H-吡唑-4-磺酰肼、
N′-(2,4-二氯苯基)-1-甲基-3-(三氟甲基)-1H-吡唑-4-磺酰肼、
N′-(4-溴苯基)-1-甲基-3-(三氟甲基)-1H-吡唑-4-磺酰肼、
5-甲基-N′-苯基-3-(三氟甲基)-1H-吡唑-4-磺酰肼、
N′-(2-氟苯基)-5-甲基-3-(三氟甲基)-1H-吡唑-4-磺酰肼、
N′-(3-氟苯基)-5-甲基-3-(三氟甲基)-1H-吡唑-4-磺酰肼、
N′-(2-氯苯基)-5-甲基-3-(三氟甲基)-1H-吡唑-4-磺酰肼、
N′-(3-氯苯基)-5-甲基-3-(三氟甲基)-1H-吡唑-4-磺酰肼、
N′-(4-氯苯基)-5-甲基-3-(三氟甲基)-1H-吡唑-4-磺酰肼、
N′-(2,4-二氯苯基)-5-甲基-3-(三氟甲基)-1H-吡唑-4-磺酰肼、
N′-(4-溴苯基)-5-甲基-3-(三氟甲基)-1H-吡唑-4-磺酰肼。
5.一种制备权利要求1~4中任一项所述的一种吡唑磺酰肼衍生物的方法,其特征在于按通式(A)表示的方法制备:
其中在上述各结构式中:
R1、R2、R3、R4均具有权利要求1~4中任一项所述的含义。
6.权利要求1~4中任一项所述的一种吡唑磺酰肼衍生物在抑制植物病原真菌方面的应用。
7.权利要求1~4中任一项所述的一种吡唑磺酰肼衍生物在防治植物真菌病害方面的应用。
8.根据权利要求6所述的应用,其特征在于权利要求1~4中任一项所述的一种吡唑磺酰肼衍生物在抑制水稻纹枯病菌、小麦赤霉病菌、番茄灰霉病菌、番茄早疫病菌方面的应用。
9.根据权利要求7所述的应用,其特征在于权利要求1~4中任一项所述的一种吡唑磺酰肼衍生物在防治水稻纹枯病、小麦赤霉病、番茄灰霉病、番茄早疫病方面的应用。
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