CN107474004B - 三氟甲基季碳中心化合物及其制备方法和应用 - Google Patents
三氟甲基季碳中心化合物及其制备方法和应用 Download PDFInfo
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- 241000219144 Abutilon Species 0.000 description 1
- 240000006995 Abutilon theophrasti Species 0.000 description 1
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- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 235000010086 Setaria viridis var. viridis Nutrition 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
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- 238000003556 assay Methods 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
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- 239000011541 reaction mixture Substances 0.000 description 1
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- 239000007858 starting material Substances 0.000 description 1
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- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical compound [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- C07D207/18—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 one double bond between ring members or between a ring member and a non-ring member
- C07D207/22—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 one double bond between ring members or between a ring member and a non-ring member 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
- C07D207/24—Oxygen or sulfur atoms
- C07D207/26—2-Pyrrolidones
- C07D207/273—2-Pyrrolidones 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 other ring carbon atoms
- C07D207/277—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D207/28—2-Pyrrolidone-5- carboxylic acids; Functional derivatives thereof, e.g. esters, nitriles
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/46—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom rings with more than six members
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
- C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D263/10—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
- C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D263/10—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D263/14—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with radicals substituted by oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
- C07D491/04—Ortho-condensed systems
- C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
- C07D491/048—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring the oxygen-containing ring being five-membered
Landscapes
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dentistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
本发明公开了三氟甲基季碳中心化合物及其制备方法和应用。该三氟甲基季碳中心化合物如式3或3’所示。本发明的制备方法简单、反应收率高,得到的三氟甲基季碳中心化合物有较强的生物活性,对玉米锈病、黄瓜霜霉病、小麦白粉病和黄瓜炭疽病具有一定的防治效果。
Description
技术领域
本发明涉及一种三氟甲基季碳中心化合物及其制备方法和应用。
背景技术
由于三氟甲基的独特性质,将三氟甲基引入到分子中通常能增强分子的脂溶性、提高生物利用度和代谢稳定性等,因此,含三氟甲基的化合物被广泛应用于医药、农药、材料等领域。另一方面,季碳中心结构是许多天然产物和药物分子中的常见结构。三氟甲基和季碳中心相结合,即形成三氟甲基季碳中心(TFQC)。这是一种特殊的结构,特征为三氟甲基直接连接在四取代的碳原子上,使分子具有强的刚性和独特的电性。
目前已有的向分子内引入三氟甲基的方法,大多发生在sp2碳上,而合成C(sp3)-CF3键的方法相对较少,构建含三氟甲基季碳中心(TFQC)的方法更是有限。构筑季碳中心要克服较大的位阻,α-三氟甲基碳负离子的脱氟反应给三氟甲基季碳中心的构筑带来更大的挑战。由于α-三氟甲基碳负离子极易发生β-脱氟副反应,该类反应需要非常活泼的亲电试剂,例如活泼卤代物、π-烯丙基钯物种等,这就限制了反应的适用范围。
发明内容
本发明所要解决的技术问题是为了克服现有技术中三氟甲基季碳中心化合物制备困难、反应收率低的缺陷,提供了一种三氟甲基季碳中心化合物及其制备方法和应用。本发明通过从α-三氟甲基卤代物出发,采用引发手段,生成α-三氟甲基自由基,之后发生自由基加成反应构建含三氟甲基的季碳中心化合物。本发明的制备方法简单、反应收率高,得到的三氟甲基季碳中心化合物有较强的生物活性,对玉米锈病、黄瓜霜霉病、小麦白粉病和黄瓜炭疽病具有一定的防治效果。
本发明主要是通过以下技术方案解决上述技术难题的。
本发明提供了一种如式3或3’所示的三氟甲基季碳中心化合物,
其中X为卤素(例如F、Cl、Br或I);m为1、2、3、4或5;
R1为H、取代或未取代的C1~6烷基;
R2为H、取代或未取代的C1~6烷基;
其中,所述的R1较佳地为H、甲基或乙基,更佳地为H或甲基。
其中,所述的R2较佳地为H、甲基或乙基,更佳地为H或甲基。
其中,所述的C1~6烷氧基较佳地为甲氧基、乙氧基、丙氧基或丁氧基,更佳地为OEt、OiPr、OtBu或OnBu。
其中,所述的芳香烃硫基较佳地为SPh。
本发明中,所述的如式3或3’所示的三氟甲基季碳中心化合物进一步优选如下任一化合物:
本发明还提供了所述的如式3或3’所示的三氟甲基季碳中心化合物的制备方法,其包括下述步骤:
有机溶剂中,在催化剂的作用下,化合物1与化合物2或2’反应,即可得到化合物3或3’;
m、X、R1、R2、R3的定义均同上所述。
其中,所述的有机溶剂较佳地为二甲基甲酰胺、苯、甲苯、N-甲基吡咯烷酮和四氯化碳中的一种或多种,更佳地为二甲基甲酰胺。
其中,所述的催化剂较佳地为金属络合物催化剂,更佳地为Ru(bpy)3(PF6)2、fac-Ir(ppy)3、Ir(bpy)2(dtbbpy)(PF6)、Ir(dF(CF3)ppy)2(dtbbpy)(PF6),最佳地为Ir(dF(CF3)ppy)2(dtbbpy)(PF6)。本领域技术人员均清楚上述金属络合物催化剂为本领域常用的光引发催化剂。
其中,所述的反应较佳地为在可见光辐照下进行的反应,更佳地为在荧光辐照下进行的反应。
其中,所述的反应的温度较佳地为15~30℃。
其中,所述的化合物1与所述的化合物2或2’的摩尔比较佳地为1∶(1~10)。
其中,所述的反应的进程可通过本领域常规手段(如TLC或HPLC)进行监测,一般以化合物1消失时作为反应的终点,所述的反应的时间较佳地为1分钟~1小时,更佳地为10分钟~1小时。
其中,所述的反应结束后还可包括后处理过程。所述后处理过程优选包括如下步骤:倒入水和乙酸乙酯中分液,水相用乙酸乙酯萃取,合并有机相,饱和食盐水洗涤,无水硫酸钠干燥,抽滤,柱层析即可。
本发明还提供了所述的如式3或3’所示的三氟甲基季碳中心化合物在制备治疗和/或预防植物疾病的药物中的应用;所述的植物疾病较佳地包括黄瓜霜霉病、小麦白粉病、黄瓜炭疽病、玉米锈病中的一种或多种。
本发明提供了一种如式5所示的三氟甲基季碳中心化合物,
其中X为卤素(例如F、Cl、Br或I);
R1为H、取代或未取代的C1~6烷基;
R2为H、取代或未取代的C1~6烷基;
R4为H、取代或未取代的苯基、取代或未取代的萘基、取代或未取代的蒽基;
R5为H、取代或未取代的苯基、取代或未取代的萘基、取代或未取代的蒽基;
R4与R5不同时为H。
其中,所述的R1较佳地为H、甲基或乙基,更佳地为H或甲基。
其中,所述的R2较佳地为H、甲基或乙基,更佳地为H或甲基。
其中,所述的取代或未取代的苯基较佳地为其中R6为H、C1~6烷基、C1~6烷氧基、C6~10环烷氧基、卤素(例如F、Cl、Br或I)、乙酰氧基或苯基;所述的C1~6烷基较佳地为甲基、乙基、正丙基、异丙基、正丁基、异丁基或叔丁基,所述的C1~6烷氧基较佳地为甲氧基、乙氧基、OiPr、OtBu或OnBu,所述的C6~10环烷氧基较佳地为或
本发明中,所述的如式5所示的三氟甲基季碳中心化合物进一步优选如下任一化合物:
本发明还提供了所述的如式5所示的三氟甲基季碳中心化合物的制备方法,其包括下述步骤:
有机溶剂中,在催化剂的作用下,化合物1与化合物4反应,即可得到化合物5;
X、R1、R2、R4、R5的定义均同上所述。
其中,所述的有机溶剂较佳地为二甲基甲酰胺、苯、甲苯、N-甲基吡咯烷酮和四氯化碳中的一种或多种,更佳地为二甲基甲酰胺。
其中,所述的催化剂较佳地为金属络合物催化剂,更佳地为Ru(bpy)3(PF6)2、fac-Ir(ppy)3、Ir(ppy)2(dtbbpy)(PF6)、Ir(dF(CF3)ppy)2(dtbbpy)(PF6),最佳地为Ir(ppy)2(dtbbpy)(PF6)。本领域技术人员均清楚上述金属络合物催化剂为本领域常用的光引发催化剂。
其中,所述的反应较佳地为在可见光辐照下进行的反应,更佳地为在荧光辐照下进行的反应。
其中,所述的反应的温度较佳地为15~30℃。
其中,所述的化合物1与所述的化合物4的摩尔比较佳地为1∶(1~10)。
其中,所述的反应的进程可通过本领域常规手段(如TLC或HPLC)进行监测,一般以化合物1消失时作为反应的终点,所述的反应的时间较佳地为1分钟~20小时,更佳地为10小时~20小时。
其中,所述的反应结束后还可包括后处理过程。所述后处理过程优选包括如下步骤:倒入水和乙酸乙酯中分液,水相用乙酸乙酯萃取,合并有机相,饱和食盐水洗涤,无水硫酸钠干燥,抽滤,柱层析即可。
本发明还提供了所述的如式5所示的三氟甲基季碳中心化合物在制备治疗和/或预防植物疾病的药物中的应用;所述的植物疾病较佳地包括黄瓜霜霉病、小麦白粉病、黄瓜炭疽病、玉米锈病中的一种或多种。
本发明提供了一种如式7所示的三氟甲基季碳中心化合物,
其中X为卤素(例如F、Cl、Br或I);
R1为H、取代或未取代的C1~6烷基;
R2为H、取代或未取代的C1~6烷基;
R7为C1~10烷基、 n为1、2、3、4或5,R8为H、C1~6烷基、C1~6烷氧基、C6~10环烷氧基、卤素(例如F、Cl、Br或I)、三氟甲基或氰基;R9为H、C1~6烷基、C1~6烷氧基、C6~10环烷氧基、卤素(例如F、Cl、Br或I)、三氟甲基或氰基。
其中,所述的R1较佳地为H、甲基或乙基,更佳地为H或甲基。
其中,所述的R2较佳地为H、甲基或乙基,更佳地为H或甲基。
其中,所述的C1~10烷基较佳地为C6~10烷基,更佳地为-C8H17。
本发明中,所述的如式7所示的三氟甲基季碳中心化合物进一步优选如下任一化合物:
本发明还提供了所述的如式7所示的三氟甲基季碳中心化合物的制备方法,其包括下述步骤:
有机溶剂中,在催化剂的作用下,化合物1与化合物6反应,即可得到化合物7;
X、R1、R2、R7的定义均同上所述。
其中,所述的有机溶剂较佳地为二甲基甲酰胺、苯、甲苯、N-甲基吡咯烷酮和四氯化碳中的一种或多种,更佳地为二甲基甲酰胺。
其中,所述的催化剂较佳地为金属络合物催化剂,更佳地为Ru(bpy)3(PF6)2、[Ir(bpy)3Cl]2、Ir(bpy)2(dtbbpy)(PF6)、Ir(ppy)2(dtbbpy)(PF6)、Ir(dF(CF3)ppy)2(dtbbpy)(PF6)、fac-Ir(ppy)3,最佳地为fac-Ir(ppy)3。本领域技术人员均清楚上述金属络合物催化剂为本领域常用的光引发催化剂。
其中,所述的反应较佳地为在可见光辐照下进行的反应,更佳地为在荧光辐照下进行的反应。
其中,所述的反应的温度较佳地为15~30℃。
其中,所述的化合物1与所述的化合物6的摩尔比较佳地为1∶(1~10)。
其中,所述的反应的进程可通过本领域常规手段(如TLC或HPLC)进行监测,一般以化合物1消失时作为反应的终点,所述的反应的时间较佳地为1分钟~20小时,更佳地为10小时~20小时。
其中,所述的反应结束后还可包括后处理过程。所述后处理过程优选包括如下步骤:倒入水和乙酸乙酯中分液,水相用乙酸乙酯萃取,合并有机相,饱和食盐水洗涤,无水硫酸钠干燥,抽滤,柱层析即可。
本发明还提供了所述的如式7所示的三氟甲基季碳中心化合物在制备治疗和/或预防植物疾病的药物中的应用;所述的植物疾病较佳地包括黄瓜霜霉病、小麦白粉病、黄瓜炭疽病、玉米锈病中的一种或多种。
本发明提供了一种如式9所示的三氟甲基季碳中心化合物,
其中X为卤素(例如F、Cl、Br或I);
R1为H、取代或未取代的C1~6烷基、苯基、甲苯基或苯甲基;
R2为H、取代或未取代的C1~6烷基、苯基、甲苯基或苯甲基;
其中,所述的R1较佳地为H、甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、苯基、甲苯基或苯甲基。
其中,所述的R2较佳地为H、甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、苯基、甲苯基或苯甲基。
本发明中,所述的如式9所示的三氟甲基季碳中心化合物进一步优选如下任一化合物:
本发明还提供了所述的如式9所示的三氟甲基季碳中心化合物的制备方法,其包括下述步骤:
有机溶剂中,在催化剂的作用下,化合物1与化合物8反应,即可得到化合物9;
X、R1、R2、R10的定义均同上所述。
其中,所述的有机溶剂较佳地为二甲基甲酰胺、二甲基乙酰胺、二甲基亚砜、CH3CN、CH3NO2、N-甲基吡咯烷酮和四氯化碳中的一种或多种,更佳地为二甲基甲酰胺。
其中,所述的催化剂较佳地为金属络合物催化剂,更佳地为Ru(bpy)3Cl2、Ru(bpy)3(PF6)2、[Ir(bpy)3Cl]2、Ir(bpy)2(dtbbpy)(PF6)、Ir(ppy)2(dtbbpy)(PF6)、Ir(dF(CF3)ppy)2(dtbbpy)(PF6)、fac-Ir(ppy)3,最佳地为fac-Ir(ppy)3。本领域技术人员均清楚上述金属络合物催化剂为本领域常用的光引发催化剂。
其中,所述的反应较佳地为在可见光辐照下进行的反应,更佳地为在荧光辐照下进行的反应。
其中,所述的反应的温度较佳地为15~30℃。
其中,所述的化合物1与所述的化合物8的摩尔比较佳地为1∶(1~10)。
其中,所述的反应的进程可通过本领域常规手段(如TLC或HPLC)进行监测,一般以化合物1消失时作为反应的终点,所述的反应的时间较佳地为1分钟~20小时,更佳地为10小时~20小时。
其中,所述的反应结束后还可包括后处理过程。所述后处理过程优选包括如下步骤:倒入水和乙酸乙酯中分液,水相用乙酸乙酯萃取,合并有机相,饱和食盐水洗涤,无水硫酸钠干燥,抽滤,柱层析即可。
本发明还提供了所述的如式9所示的三氟甲基季碳中心化合物在制备治疗和/或预防植物疾病的药物中的应用;所述的植物疾病较佳地包括黄瓜霜霉病、小麦白粉病、黄瓜炭疽病、玉米锈病中的一种或多种。
在符合本领域常识的基础上,上述各优选条件,可任意组合,即得本发明各较佳实例。
本发明所用试剂和原料均市售可得。
本发明的积极进步效果在于:本发明的制备方法简单、反应收率高,得到的三氟甲基季碳中心化合物有较强的生物活性,对玉米锈病、黄瓜霜霉病、小麦白粉病和黄瓜炭疽病具有一定的防治效果。
具体实施方式
下面通过实施例的方式进一步说明本发明,但并不因此将本发明限制在所述的实施例范围之中。下列实施例中未注明具体条件的实验方法,按照常规方法和条件,或按照商品说明书选择。
本发明中,室温是指15~30℃。
在干燥的10mL Schlenk管中加入Ir[dF(CF3)ppy]2(dtbbpy)(PF6)(11.23mg,2mmol%),严格抽换氮气三次,在氮气条件下加入DMF(1mL),底物1(0.5mmol)和富电子烯烃化合物2(1.0mmol),置于24瓦荧光灯照射下室温搅拌反应1小时。体系倒入水(20mL)和乙酸乙酯(20mL)中分液,水相用乙酸乙酯萃取三次(5mL×3),合并有机相,饱和食盐水洗三次(5mL×3),无水硫酸钠干燥,抽滤,硅胶柱层析得到产物。
实施例1
浅黄色液体;分离产率85%;IR(neat)v/cm-1:2979,1759,1722,1435,1378,1280,1195,1096,991,924,799;1H NMR(400MHz,CDCl3)δ1.19-1.27(m,3H),2.29(dd,J=14.4,4.4Hz,0.53H),2.64(t,J=4.8Hz,1H),2.86(dd,J=14.4,7.6Hz,0.47H),3.42-3.68(m,5H),3.82(m,3H),3.86-3.94(m,1H),5.08(dd,J=4.8,2.8Hz,0.47H),5.20(dd,J=6.4,3.6Hz,0.53H);19F NMR(376MHz,CDCl3)δ-70.7(s,1.4F),-70.2(s,1.6F);13C NMR(100MHz,CDCl3)δ15.2,15.3,27.8,28.3,32.9,33.4,43.0,43.5,53.7,53.8,59.3(q,JCF=28Hz),63.3,63.6,87.0,123.0(q,JCF=279Hz),123.3(q,JCF=277Hz),163.7,164.6,165.4,165.6;MS(ESI)m/z(%):362[M+1]+;HRMS(ESI)calcd.for C11H15BrF3NNaO4[M+Na]+:384.0029;found:384.0046.
实施例2
浅黄色液体;分离产率83%;IR(neat)v/cm-1:2974,2928,2856,1760,1723,1435,1327,1279,1143,1089,1030,956,866,801,711;1H NMR(400MHz,CDCl3)δ1.17-1.29(m,6H),2.27(dd,J=14.4,4.4Hz,0.53H),2.59-2.70(m,1H),2.89(dd,J=14.4,6.0Hz,0.47H),3.44-3.66(m,3H),3.74-3.93(m,5H),5.15(dd,J=5.2,2.4Hz,0.47H),5.26(dd,J=6.4,4.4Hz,0.53H);19F NMR(376MHz,CDCl3)δ-70.3(s,1.4F),-69.8(s,1.6F);13C NMR(100MHz,CDCl3)δ22.1,22.4,23.0,23.3,28.2,28.6,29.6,34.5,35.2,42.8,43.3,53.8,59.2(q,JCF=17Hz),70.8,72.0,85.7,86.1,123.0(q,JCF=284Hz),123.4(q,JCF=274Hz),163.5,164.6,165.4,165.7;MS(ESI)m/z(%):378[M+1]+;HRMS(ESI)calcd.for C12H17BrF3NNaO4[M+Na]+:398.0185;found:398.0194.
实施例3
乳白色固体;m.p.55.6-57.9℃;分离产率84%;IR(KBr)v/cm-1:2976,2925,2853,1761,1721,1436,1396,1368,1322,1279,1192,1086,1027,897,745;1H NMR(400MHz,CDCl3)δ1.26-1.28(m,9H),2.23(dd,J=14.4,4.4Hz,0.57H),2.55(d,J=12.0Hz,0.43H),2.70(dd,J=14.0,6.0Hz,0.43H),2.85(dd,J=14.0,6.4Hz,0.57H),3.42-3.63(m,3H),3.71-3.78(m,1H),3.82(s,3H),5.25-5.35(m,1H);19F NMR(376MHz,CDCl3)δ-69.9(s,1.3F),-69.5(s,1.7F);13C NMR(100MHz,CDCl3)δ28.4,28.6,36.6,36.9,42.3,42.8,53.7,59.5(q,JCF=28Hz),74.8,75.0,81.3,81.4,123.0(q,JCF=280Hz),163.4,164.4,166.5;MS(ESI)m/z(%):390[M+1]+;HRMS(ESI)calcd.for C13H19BrF3NNaO4[M+Na]+:412.0342;found:412.0345.
实施例4
浅黄色液体;分离产率80%;IR(neat)v/cm-1:2960,2931,2874,1762,1723,1453,1435,1365,1326,1278,1197,1097,1074;isomer a:1H NMR(400MHz,CDCl3)δ0.94(t,J=6.8Hz,3H),1.35-1.44(m,2H),1.56-1.63(m,2H),2.30(dd,J=14.0,4.0Hz,1H),2.86(dd,J=14.4,6.4Hz,1H),3.44-3.68(m,5H),3.84(s,3H),3.87-3.91(m,1H),5.21(dd,J=6.0,3.6Hz,1H);19F NMR(376MHz,CDCl3)δ-69.8(s);13C NMR(100MHz,CDCl3)δ13.7,19.2,27.8,31.7,33.2,42.0,53.7,59.3(q,JCF=28Hz),67.8,87.1,123.6(q,JCF=280Hz),163.7,165.5;isomer b:1H NMR(400MHz,CDCl3)δ:0.93(t,J=6.8Hz,3H),1.32-1.42(m,2H),1.53-1.60(m,2H),2.60-2.69(m,2H),3.47-3.50(m,3H),3.56-3.61(m,2H);3.84(s,3H),3.87-3.94(m,1H),5.08-5.10(m,1H);19F NMR(376MHz,CDCl3)δ:-70.3(s);13C NMR(100MHz,CDCl3)δ:13.7,18.8,28.3,31.6,32.7,43.5,53.8,59.0(q,JCF=27Hz),67.5,87.1,123.3(q,JCF=280Hz),164.7,165.3;MS(ESI)m/z(%):390,392[M+1]+;HRMS(ESI)calcd.forC13H20BrF3NO4[M+1]+:390.0522;found:390.0522.
实施例5
浅黄色液体;分离产率71%;IR(neat)v/cm-1:2935,2858,1759,1720,1452,1436,1364,1436,1364,1325,1279,1195,1091,1026,980,925,713;1H NMR(400MHz,CDCl3)δ1.20-1.45(m,5H),1.51-1.58(m,1H),1.68-1.95(m,4H),2.27(dd,J=14.0,4.4Hz,0.42H),2.60-2.69(m,1H),2.88(dd,J=14.4,6.4Hz,0.58H),3.41-3.54(m,2H),3.56-3.66(m,2H),3.83(s,3H),3.85-3.91(m,1H),5.18(dd,J=4.2,2.8Hz,0.42H),5.29(dd,J=6.0,4.2Hz,0.58H);19F NMR(376MHz,CDCl3)δ-70.3(s,1.3F),-69.8(s,1.7F);13C NMR(100MHz,CDCl3)δ23.6,23.8,25.2,27.9,28.3,31.9,32.2,33.0,33.3,34.6,35.2,42.8,43.2,53.6,58.8-59.9(m),76.3,77.5,85.5,85.9,122.9(q,JCF=279Hz),123.3(q,JCF=280Hz),163.4,164.5,165.3,165.5;MS(ESI)m/z(%):418[M+1]+;HRMS(ESI)calcd.for C15H21BrF3NO4Na[M+Na]+:438.0498;found:438.0517.
实施例6
浅黄色液体;分离产率52%;IR(neat)v/cm-1:3058,2957,2860,1761,1717,1583,1474,1438,1413,1298,1252,1193,1093,1060,876,805,751,694,605;1H NMR(400MHz,CDCl3)δ:2.40(dd,J=14.4,7.2Hz,0.57H),2.79(dd,J=14.8,4.8Hz,0.43H),2.91-2.98(m,1H),3.41-3.46(m,1H),3.52-3.60(m,1H),3.71(s,1.39H),3.82(s,1.71H),3.91-3.97(m,1H),4.12-4.22(m,1H),5.10-5.17(m,1H),7.34-7.41(m,4H),7.43-7.46(m,1H);19F NMR(376MHz,CDCl3)δ-70.3(s,1.3F),-70.1(s,1.7F);13C NMR(100MHz,CDCl3)δ27.2,27.5,32.5,33.2,42.9,43.3,53.7,59.3(m),64.5,65.6,123.4(q,JCF=281Hz),122.8(q,JCF=280Hz),129.3,129.6,134.7,134.9,164.1,164.3,165.1;MS(ESI)m/z(%):428[M+1]+;HRMS(ESI)calcd.for C15H15BrF3NO3SNa[M+Na]+:447.9800;found:447.9814.
实施例7
浅黄色液体;分离产率73%;IR(neat)v/cm-1:2960,2892,1754,1716,1442,1372,1301,1251,1197,1087,1032,978,935,863;1H NMR(400MHz,CDCl3)δ1.67-1.71(m,1H),2.04-2.27(m,2H),3.27-3.36(m,1H),3.49-3.55(m,1H),3.57-3.66(m,1H),3.68-3.79(m,2H),3.84(s,1.70H),3.85(s,1.30H),3.86-4.02(m,1H),5.64-5.66(m,1H);19F NMR(376MHz,CDCl3)δ-70.1(s,1.3F),-64.0(s,1.7F);13C NMR(100MHz,CDCl3)δ:27.1,27.6,41.0,42.7,43.4,44.0,53.2,53.9,62.8(q,JCF=21Hz),66.5,66.8,91.1,91.6,123.0(q,JCF=281Hz),163.8,165.9;MS(ESI)m/z(%):360,362[M+1]+;HRMS(ESI)calcd.forC11H13BrF3NNaO4[M+Na]+:381.9872;found:381.9889.
实施例8
白色固体;m.p.114.7-118.9℃;分离产率66%;IR(KBr)v/cm-1:2959,1762,1699,1415,1261,1195,1163,1080,1017,879,711,619;isomer a:1H NMR(400MHz,CDCl3)δ2.02-2.15(m,2H),2.32(dd,J=14.4,6.4Hz,1H),2.49(t,J=8.0Hz,2H),2.79(dd.J=14.8,8.0Hz,1H),3.06-3.19(m,2H),3.36-3.42(m,1H),3.46-3.55(m,2H),3.83(s,3H),3.96-4.03(m,1H),6.07(t,J=7.6Hz,1H);19F NMR(376MHz,CDCl3)δ-70.0(s);13C NMR(100MHz,CDCl3)δ17.9,26.4,28.0,31.2,40.9,42.3,53.8,59.3(q,JCF=28Hz),61.9,123.2(q,JCF=287Hz),163.9,165.0,176.3;mixture:1H NMR(400MHz,CDCl3)δ1.98-2.13(m,2H),2.27-2.34(m,0.39H),2.42-2.50(m,2H),2.53-2.59(m,0.61H),2.72-2.81(m,1H),3.04-3.18(m,2H),3.33-3.40(m,1H),3.46-3.47(m,2H),3.78-3.85(m,3H),3.92-4.03(m,1H),5.95-6.07(m,1H);19F NMR(376MHz,CDCl3)δ-70.3(s,2.0F),-70.0(s,1.0F);13C NMR(100MHz,CDCl3)δ17.7,26.4,27.8,28.1,31.0,31.1,40.8,41.1,42.1,53.7,53.8,59.5(q,JCF=28Hz),61.8,61.9,123.2(q,JCF=281Hz),163.8,163.9,164.7,165.5,176.1,176.2;MS(ESI)m/z(%):401,403[M+1]+;HRMS(ESI)calcd.for C13H17BrF3N2O4[M+1]+:401.0318;found:401.0317.Anal.calcd for C13H16BrF3N2O4:C,38.92;H,4.02;N,6.98;Found:C,39.20;H,4.07;N,6.99.
实施例9
白色固体;m.p.98.5-100.3℃;分离产率51%;IR(KBr)v/cm-1:2933,2859,1762,1720,1655,1436,1415,1352,1307,1278,1259,1193,1095,1045,973;1H NMR(400MHz,CDCl3)δ1.41-1.68(m,3H),1.75-1.92(m,3H),2.11-2.20(m,0.50H),2.44-2.51(m,0.50H),2.55-2.94(m,2H),2.73-2.84(m,1H),3.01-3.10(m,1H),3.12-3.35(m,2H),3.39-3.55(m,2H),3.81-3.89(m,3H),3.94-4.04(m,1H),6.43-6.57(m,1H);19F NMR(376MHz,CDCl3)δ-70.1(1.5F),-69.9(s,1.5F);13C NMR(100MHz,CDCl3)δ:23.2,26.2,28.9,29.2,29.3,29.6,37.5,41.3,41.8,42.2,53.7,53.9,58.8-60.2(m),63.7,64.3,123.1(q,JCF=279Hz),123.3(q,JCF=281Hz),164.1,164.2,164.8,165.9,177.3;MS(ESI)m/z(%):429[M+1]+;HRMS(ESI)calcd.for C15H20BrF3N2O4Na[M+Na]+:451.0451;found:451.0437.Anal.calcd forC15H20BrF3N2O4:C,41.97;H,4.70;N,6.53;Found:C,42.28;H,4.74;N,6.48.
实施例10
白色固体;m.p.57.4-59.2℃;分离产率88%;IR(KBr)v/cm-1:3053,2957,2919,2849,1763,1722,1625,1598,1485,1451,1410,1325,1267,1195,1072,751,724;1H NMR(400MHz,CDCl3)δ2.85-2.96(m,1H),2.99-3.10(m,1H),3.18-3.36(m,2H),3.59-3.68(m,1H),3.96-3.98(m,3H),4.00-4.10(m,1H),6.70-6.80(m,1H),7.25-7.33(m,2H),7.42(dd,J=16.0,8.0Hz,1H),7.48-7.56(m,3H),8.10(t,J=8.0Hz,2H);19F NMR(376MHz,CDCl3)δ-69.6(s,1.4F),-68.8(s,1.6F);13C NMR(100MHz,CDCl3)δ27.6,27.9,30.8,31.1,42.3,42.5,54.0,54.2,60.3(m),67.0,67.4,108.4,110.7,111.3,120.7,120.77,120.82,120.9,121.0,123.3(q,JCF=280Hz),123.5,123.7(q,JCF=281Hz),124.7,124.9,126.50,126.56,126.59,126.7,136.7,136.9,140.0,163.8,164.0,165.0,165.5;MS(ESI)m/z(%):485[M+1]+;HRMS(ESI)calcd.for C21H18BrF3N2O3Na[M+Na]+:505.0345;found:505.0321.
实施例11
无色液体,分离产率84%;IR(neat)v/cm-1:2980,2881,1759,1716,1445,1401,1304,1194,1089,944,760,677;1H NMR(400MHz,CDCl3)δ1.18(t,J=6.8Hz,1.41H),1.24(t,J=7.2Hz,1.59H),1.53(s,3H),1.59(s,3H),2.33(d,J=14.8Hz,0.53H),2.41(dd,J=13.6,4.8Hz,0.47H),2.71(d,J=13.6Hz,0.47H),2.83(dd,J=14.8,6.4Hz,0.53H),3.33(dd,J=10.0,5.6Hz,1H),3.36-3.52(m,2H),3.82-3.83(m,3H),4.48(d,J=10.4Hz,0.47H),4.54(d,J=10.4Hz,0.53H),4.93(d,J=4.4Hz,0.53H),5.05(d,J=6.4Hz,0.47H);19F NMR(376MHz,CDCl3)δ-70.2(s,1.33F),-69.5(s,1.67F);13C NMR(100MHz,CDCl3)δ15.1,31.5,40.2,40.9,53.6,53.8,57.4,58.0,59.2-60.0(m),61.8,62.1,86.0,86.8,123.0(q,JCF=280Hz),123.3(q,JCF=280Hz),164.6,165.6,165.8,165.9;MS(ESI)m/z(%):390[M+1]+;HRMS(ESI)calcd.for C13H20BrF3NO4[M+1]+:390.0522;found:390.0522.
在干燥的10mL Schlenk管中加入Ir(ppy)2(dtbbpy)(PF6)(6.5mg,2mmol%),严格抽换氮气三次,在氮气条件下加入DMF(1mL),底物1(0.5mmol)和芳基烯烃4(1.0mmol),置于24瓦荧光灯照射下室温搅拌反应过夜。体系倒入水(20mL)和乙酸乙酯(20mL)中分液,水相用乙酸乙酯萃取三次(5mL×3),合并有机相,饱和食盐水洗三次(5mL×3),无水硫酸钠干燥,抽滤,硅胶柱层析得到产物。
实施例12
浅黄色液体;分离产率68%;IR(neat)v/cm-1:3024,2958,2924,1759,1713,1615,1515,1434,1279,1193,1097,1063,1021,883,822,733,506;1H NMR(400MHz,CDCl3)δ2.31-2.36(m,3.42H),2.61(dd,J=14.4,7.2Hz,0.58H),2.86-2.96(m,1H),2.99-3.07(m,1H),3.20-3.27(m,1H),3.40-3.52(m,1H),3.84-3.85(m,3H),3.94-4.00(m,1H),4.83-4.91(m,1H),7.12-7.24(m,4H);19F NMR(376MHz,CDCl3)δ-70.1(s,1.5F),-70.0(s,1.5F);13C NMR(100MHz,CDCl3)δ:21.0,27.3,27.4,35.4,35.8,43.0,43.2,53.5,53.6,59.6,59.8(q,JCF=27Hz),60.1,123.3(q,JCF=280Hz),123.8(q,JCF=282Hz),127.0,127.1,129.96,130.02,134.6,135.2,139.0,139.1,165.2,165.3,165.5,166.1;MS(ESI)m/z(%):410[M+1]+;HRMS(ESI)calcd.for C16H18BrF3NO3[M+1]+:408.0417;found:408.0414.
实施例13
白色固体;m.p.49.7-51.6℃;分离产率66%;IR(KBr)v/cm-1:2958,1759,1714,1496,1458,1435,1300,1269,1245,1193,1058,764,702;1H NMR(400MHz,CDCl3)δ2.37(dd,J=14.0,8.8Hz,0.50H),2.66(dd,J=15.2,7.6Hz,0.50H),2.92-3.10(m,2H),3.26-3.32(m,1H),3.46-3.57(m,1H),3.88(s,1.50H),3.91(s,1.50H),4.01-4.08(m,1H),4.91-4.99(m,1H),7.29-7.33(m,2H),7.39-7.47(m,3H);19F NMR(376MHz,CDCl3)δ-70.1(s,1.5F),-70.0(s,1.5F);13C NMR(100MHz,CDCl3)δ27.4,27.5,35.5,35.9,43.2,43.4,53.7,53.8,59.8(q,JCF=25Hz),60.1.60.5,123.4(q,JCF=280Hz),123.9(q,JCF=280Hz),127.20,127.22,129.2,129.3,129.4,129.5,137.9,138.5,165.3,165.4,165.5,166.1;MS(ESI)m/z(%):396[M+1]+;HRMS(ESI)calcd.for C15H16BrF3NO3[M+1]+:394.0260;found:394.0261.
实施例14
浅黄色液体;分离产率56%;IR(neat)v/cm-1:2958,2840,1758,1713,1613,1587,1514,1434,1301,1250,1194,1177,1063,1033,835;1H NMR(400MHz,CDCl3)δ2.37(dd,J=14.4,8.8Hz,0.64H),2.65(dd,J=14.8,8.0Hz,0.36H),2.89-2.97(m,1H),2.99-3.10(m,1H),3.24-3.31(m,1H),3.44-3.55(m,1H),3.83(s,3H),3.89(s,1.09H),3.90(s,1.91H),3.96-4.03(m,1H),4.86-4.94(m,1H),6.95(d,J=8.4Hz,2H),7.20-7.28(m,2H);19F NMR(376MHz,CDCl3)δ-70.1(s,1.9F),-70.0(s,1.1F);13C NMR(100MHz,CDCl3)δ27.4,27.6,35.6,35.9,43.0,43.2,53.6,53.7,55.3,59.4,59.8(q,JCF=28Hz),60.0,114.7,114.8,123.4(q,JCF=279Hz),123.9(q,JCF=281Hz),128.6,129.4,130.1,160.1,160.2,165.2,165.3,165.6,166.2;MS(ESI)m/z(%):426[M+1]+;HRMS(ESI)calcd.for C16H18BrF3NO4[M+1]+:424.0366;found:424.0366.
实施例15
浅黄色液体;分离产率65%;IR(neat)v/cm-1:2963,2906,2870,1759,1706,1512,1435,1413,1268,1188,1109,1061,1018,837,674;1H NMR(400MHz,CDCl3)δ1.33(s,9H),2.38(dd,J=14.0,5.2Hz,0.29H),2.65(dd,J=14.4,7.2Hz,0.71H),2.89-2.97(m,1H),3.03-3.10(m,1H),3.26-3.32(m,1H),3.46-3.57(m,1H),3.87(s,0.89H),3.89(s,2.11H),3.99-4.06(m,1H),4.87-4.96(m,1H),7.18-7.24(m,2H),7.42-7.44(d,J=8.4Hz,2H);19FNMR(376MHz,CDCl3)δ-70.1(s,2.2F),-70.0(s,0.8F);13C NMR(100MHz,CDCl3)δ20.8,27.2,27.3,35.3,35.7,43.1,43.2,53.5,53.6,59.3,59.6(q,JCF=52Hz),59.7,122.5,122.6,123.2(q,JCF=279Hz),123.7(q,JCF=281Hz),128.2,135.2,135.9,150.9,151.0,165.1,165.2,165.9,169.0;MS(ESI)m/z(%):452[M+1]+;HRMS(ESI)calcd.for C19H24BrF3NO3[M+1]+:450.0886;found:450.0883.
实施例16
浅黄色液体;分离产率72%;IR(neat)v/cm-1:2959,1758,1713,1607,1508,1434,1370,1300,1281,1195,1167,1062,1016,912,851,659;1H NMR(400MHz,CDCl3)δ2.32-2.38(m,3.53H),2.64(dd,J=14.4,6.4Hz,0.47H),2.93-3.02(m,1H),3.04-3.10(m,1H),3.27-3.34(m,1H),3.47-3.58(m,1H),3.86(s,1.41H),3.89(s,1.59H),4.02-4.09(m,1H),4.95-5.03(m,1H),7.16-7.18(m,2H),7.30-7.37(m,2H);19F NMR(376MHz,CDCl3)δ-70.1(s,1.6F),-70.0(s,1.4F);13C NMR(100MHz,CDCl3)δ27.4,27.5,31.2,34.7,36.0,43.2,43.4,53.6,53.7,59.8,60.1(q,JCF=20Hz),123.4(q,JCF=279Hz),126.3,126.4,126.9,134.8,135.4,152.3,152.5,165.3,165.5,165.6,166.2;MS(ESI)m/z(%):454[M+1]+;HRMS(ESI)calcd.for C17H18BrF3NO5[M+1]+:452.0315;found:452.0310.
实施例17
白色固体;m.p.100.3-101.5℃;分离产率59%;IR(KBr)v/cm-1:3030,2957,1758,1713,1487,1450,1435,1413,1299,1270,1189,1060,1008,842,765,698,503;1H NMR(400MHz,CDCl3)δ2.43(dd,J=14.0,8.4Hz,0.22H),2.71(dd,J=14.4,7.2Hz,0.78H),2.99-3.05(m,1H),3.09-3.16(m,1H),3.30-3.35(m,1H),3.50-3.55(m,1H),3.90(s,2.43H),3.92(s,0.57H),4.05-4.12(m,1H),4.97-5.05(m,1H),7.34-7.41(m,3H),7.47(t,J=7.6Hz,2H),7.60(d,J=7.2Hz,2H),7.66(d,J=8.4Hz,2H);19F NMR(376MHz,CDCl3)δ-70.0(s,0.7F),-69.9(s,2.3F);13C NMR(100MHz,CDCl3)δ27.4,27.5,35.5,35.9,43.3,43.5,53.7,59.9(q,JCF=14.1Hz),60.3,123.8(q,JCF=281Hz),127.0,127.7,127.8,128.1,128.2,128.9,136.8,137.4,140.0,142.2,142.3,165.3,166.1;MS(ESI)m/z(%):472[M+1]+;HRMS(ESI)calcd.for C21H19BrF3NNaO3[M+Na]+:492.0393;found:492.0381.
实施例18
白色固体;m.p.101.2-104.4℃;分离产率42%;IR(KBr)v/cm-1:2959,2924,2853,1758,1714,1606,1512,1436,1270,1228,1188,1059,841,549;isomer a(for X-raysingle crystal analysis):1H NMR(400MHz,CDCl3)δ2.61(dd,J=14.8,7.6Hz,1H),2.94-3.04(m,2H),3.24-3.30(m,1H),3.45-3.51(m,1H),3.87(s,3H),3.99-4.05(m,1H),4.93(t,J=7.2Hz,1H),7.11(t,J=8.4Hz,2H),7.28-7.31(m,2H);19F NMR(376MHz,CDCl3)δ-111.9to-111.8(m,1F),-69.7(s,3F);13C NMR(100MHz,CDCl3)δ27.3,35.6,43.4,53.8,60.0,60.1(q,JCF=22Hz),116.4,116.6,123.8(q,JCF=281Hz),129.0,129.1,134.4,161.8,164.2,165.3;mixture:1H NMR(400MHz,CDCl3)δ2.31(dd,J=14.0,8.4Hz,0.48H),2.60(dd,J=14.8,7.2Hz,0.52H),2.90-3.04(m,2H),3.23-3.30(m,1H),3.44-3.57(m,1H),3.85(s,1.56H),3.87(s,1.44H),3.97-4.05(m,1H),4.90-4.98(m,1H),7.08-7.12(m,2H),7.23-7.31(m,2H);19F NMR(376MHz,CDCl3)δ-120.3--120.0(m,0.5F),-111.8--111.7(m,0.5F),-70.1(s,1.5F),-70.0(s,1.5F);13C NMR(100MHz,CDClx)δ27.3,27.4,35.5,35.9,43.2,43.3,53.6,53.7,59.4,59.8,59.8(q,JCF=53Hz),116.3,116.4,116.5,116.6,123.2(q,JCF=279Hz),123.7(q,JCF=281Hz),129.0,129.1,133.65,133.68,134.29,134.32,164.1,164.2,165.2,165.3,165.4,166.0;MS(ESI)m/z(%):414[M+1]+;HRMS(ESI)calcd.for C15H14BrF4NO3Na[M+Na]+:433.9985;found:433.9991.
实施例19
浅黄色液体;分离产率53%;IR(neat)v/cm-1:3030,2958,2925,2852,1755,1598,1493,1435,1413,1274,1092,1073,1021,883,833,785,759,508;1H NMR(400MHz,CDCl3)δ:2.32(dd,J=14.0,8.4Hz,0.48H),2.61(dd,J=14.4,6.8Hz,0.52H),2.93-3.06(m,2H),3.27-3.33(m,1H),3.47-3.59(m,1H),3.88(s,1.56H),3.90(s,1.44H),4.02-4.10(m,1H),4.92-5.01(m,1H),7.22(d,J=8.4Hz,1H),7.28(s,1H),7.40-7.43(m,2H);19F NMR(376MHz,CDCl3)δ-70.1(s,1.4F),-70.0(s,1.6F);13C NMR(100MHz,CDCl3)δ27.4,27.6,35.4,35.9,43.3,43.4,53.8,53.9,59.6,60.0(q,JCF=25Hz),60.0,123.2(q,JCF=276Hz),123.7(q,JCF=289Hz),128.6,129.7,129.8,135.1,135.3,136.5,137.1,165.3,163.4,166.1;MS(ESI)m/z(%):430[M+1]+;HRMS(ESI)calcd.for C15H15BrClF3NO3[M+1]+:427.9870;found:427.9866.
实施例20
乳白色固体;m.p.82.4-85.1℃;分离产率33%;IR(KBr)v/cm-1:3050,2957,2925,1760,1714,1512,1434,1300,1267,1195,1161,1064,797,779;1H NMR(400MHz,CDCl3)δ2.36(dd,J=14.4,7.6Hz,1H),2.93-3.05(m,1H),3.16-3.26(m,1H),3.30-3.35(m,1H),3.58-3.64(m,1H),3.96-3.97(m,3H),4.13-4.28(m,1H),5.95(t,J=7.6Hz,1H),7.33(d,J=7.6Hz,1H),7.44-7.63(m,3H),7.87-7.96(m,2H),8.05(d,J=8.4Hz,1H);19F NMR(376MHz,CDCl3)δ-69.9(s,2.1F),-69.3(s,0.9F);13C NMR(100MHz,CDCl3)δ:27.4,27.9,33.5,35.8,43.2,43.9,53.8,54.9,60.0(q,JCF=28Hz),62.9,121.4,123.3(q,JCF=280Hz),122.4,123.1,125.2,125.8,126.3,126.4,127.2,127.3,129.2,129.3,129.9,130.2,130.4,130.8,130.9,134.0,134.5,165.3,165.5,165.8,166.0;MS(ESI)m/z(%):446[M+1]+;HRMS(ESI)calcd.for C19H17BrF3NO3Na[M+Na]+:466.0236;found:466.0250.
实施例21
乳白色固体;m.p.98.9-103.4℃;分离产率46%;IR(KBr)v/cm-1:3061,2955,2864,1757,1716,1494,1448,1397,1318,1279,1193,1168,1055,758,703;1H NMR(400MHz,CDCl3)δ2.34-2.41(m,1H),2.86-2.93(m,1H),3.26-3.38(m,3H),3.48(s,3H),3.89-3.97(m,1H),7.15-7.17(m,2H),7.21-7.27(m,3H),7.32-7.41(m,5H);19F NMR(376MHz,CDCl3)δ-69.7(s);13C NMR(100MHz,CDCl3)δ25.9,43.1,45.0,53.4,59.4(q,JCF=27Hz),70.2,123.5(q,JCF=280Hz),127.6,128.2,128.3,128.5,128.9,129.0,140.8,140.4,164.9,165.1;MS(ESI)m/z(%):472[M+1]+;HRMS(ESI)calcd.for C21H19BrF3NO3Na[M+Na]+:492.0393;found:492.0375.
在干燥的10mL Schlenk管中加入fac-Ir(ppy)3(6.5mg,2mol%),严格抽换氮气三次,在氮气条件下加入DMF(1mL),底物1(0.5mmol)和普通烯烃6(1.0mmol),置于24瓦荧光灯照射下室温搅拌反应过夜。体系倒入水(20mL)和乙酸乙酯(20mL)中分液,水相用乙酸乙酯萃取三次(5mL×3),合并有机相,饱和食盐水洗三次(5mL×3),无水硫酸钠干燥,抽滤,硅胶柱层析得到产物。
实施例22
无色液体;分离产率50%;IR(neat)v/cm-1:3409,2929,2857,1759,1713,1606,1594,1435,1378,1275,1195,1128,1062,1032,982,925,793,710,528;1H NMR(400MHz,CDCl3)δ0.88(t,J=8.0Hz,3H),1.19-1.41(m,12H),1.62-1.91(m,2H),2.04(dd,J=16.0,8.0Hz,1H),2.36(dd,J=14.0,8.0Hz,1H),2.61-2.68(m,1H),3.37-3.47(m,2H),3.51-3.59(m,1H),3.82-3.83(m,3H),4.00-4.05(m,1H);19F NMR(400MHz,CDCl3)δ-70.15(s,1.49F),-70.14(s,1.51F);13C NMR(400MHz,CDCl3)δ14.1,22.6,24.1,24.4,27.4,27.5,29.1,29.4,29.45,29.5,31.4,31.8,32.2,33.0,33.2,42.9.43.1,53.6,53.7,55.1,55.7,59.5-59.9(m),123.3(q,JCF=279Hz),123.8(q,JCF=281Hz),165.0,165.4,165.8,166.2;MS(ESI)m/z(%):430[M+1]+;HRMS(ESI)calcd.for C17H28BrF3NO3[M+1]+:430.1199;found:430.1197.
实施例23
无色液体;分离产率50%;IR(neat)v/cm-1:3062,2956,2877,1757,1711,1629,1600,1511,1466,1435,1390,1258,1217,1184,1120,1062,1029,840,750,624;1H NMR(400MHz,CDCl3)δ1.81-2.04(m,1H),2.30-2.53(m,1H),2.61-2.66(m,1H),2.76-2.87(m,1H),3.45-3.51(m,3H),3.78-3.83(m,3H),4.07-4.24(m,4H),7.13-7.15(d,J=8.0Hz,2H),7.37(t,J=8.0Hz,1H),7.47(t,J=8.0Hz,1H),7.77(q,J=8.0Hz,3H);19F NMR(400MHz,CDCl3)δ-70.2(s,1.48F),-70.1(s,1.52F);13C NMR(400MHz,CDCl3)δ27.4,31.2,23,32.6,32.8,43.1,43.3,53.5,53.6,53.8,59.6(q,JCF=22Hz),63.6,106.6,118.4,123.3(q,JCF=226Hz),123.7(q,JCF=224Hz),123.9,126.5,126.7,127.6,129.1,129.6,134.3,156.1,165.0,165.4,165.6,166.1;MS(ESI)m/z(%):490[M+1]+;HRMS(ESI)calcd.forC21H22BrF3NO4[M+1]+:488.0679;found:488.0674.
实施例24
无色液体;分离产率43%;IR(neat)v/cm-1:2955,2877,1758,1713,1601,1452,1435,1275,1190,1112,1070,1027,714;1H NMR(400MHz,CDCl3)δ1.39-1.52(m,3H),1.73-1.99(m,3H),2.03(dd,J=16.0,12.0Hz,0.54H),2.36(dd,J=12.0,4.0Hz,0.46H),2.61-2.68(m,1H),3.35-3.44(m,2H),3.46-3.57(m,1H),3.79-3.80(m,3H),3.81-4.06(m,2H),4.33(t,J=8.0Hz,2H),7.42(t,J=8.0Hz,2H),7.54(t,J=8.0Hz,1H),8.00(d,J=8.0Hz,2H);19F NMR(400MHz,CDCl3)δ-70.14(s,1.4F),-70.12(s,1.6F);13C NMR(400MHz,CDCl3)δ20.8,21.0,27.4,27.5,28.5,31.2,32.0,32.6,32.8,42.8,43.1,53.6,53.7,54.9,55.5,59.5(m),64.2,123.2(q,JCF=279Hz),123.7(q,JCF=280Hz),128.4,129.4,130.0,133.0,164.9,165.3,165.6,166.1,166.5;MS(ESI)m/z(%):494[M+1]+;HRMS(ESI)calcd.forC20H24BrF3NO5[M+1]+:494.0784;found:494.0780.
实施例25
无色液体;分离产率47%;IR(neat)v/cm-1:2958,2903,2231,1758,1713,1435,1276,1190,1107,1020,862,768,692;1H NMR(400MHz,CDCl3)δ1.49-1.62(m,1H),1.73-1.86(m,2H),1.93-2.08(m,1.34H),2.39(dd,J=16.0,8.0Hz,0.66H),2.64-2.72(m,1H),3.35-3.57(m,3H),3.79(s,3H),3.89-4.09(m,2H),4.38(t,J=8.0Hz,2H),7.72(d,J=8.0Hz,2H),8.09(d,J=8.0Hz,2H);19F NMR(400MHz,CDCl3)δ-70.06(s,1.6F),-70.05(s,1.4F);13CNMR(400MHz,CDCl3)δ23.3,23.6,27.5,27.6,29.2,29.5,31.0,31.8,42.8,43.1,53.6,53.7,54.5,55.1,59.6(m),64.8,116.5,117.8,123.2(q,JCF=279Hz),123.6(q,JCF=281Hz),130.0,132.2,133.6,164.7,164.8,165.3,165.5,165.9;MS(ESI)m/z(%):507[M+1]+;HRMS(ESI)calcd.for C20H21BrF3N2O5[M+1]+:505.0591;found:505.0578.
实施例26
无色液体;分离产率42%;IR(neat)v/cm-1:3041,2955,2882,1758,1712,1612,1434,1381,1275,1178,1108,1036,842,755,691;1H NMR(400MHz,CDCl3)δ1.37-1.47(m,2H),1.75-1.93(m,3H),2.00-2.04(m,1H),2.35(s,3H),2.59-2.66(m,1H),3.32-3.39(m,2H),3.42-3.55(m,1H),3.76-3.77(m,4H),3.78-4.03(m,1H),4.29(t,J=8.0Hz,3H),7.19(d,J=8.0Hz,2H),7.86(d,J=8.0Hz,2H);19F NMR(400MHz,CDCl3)δ-70.2(1.5F),-70.1(1.5F);13C NMR(400MHz,CDCl3)δ20.7,21.0,21.6,27.4,27.5,28.5,31.2,32.0,32.5,32.7,42.8,43.0,53.5,53.6,54.9,55.5,59.5(m),64.0,123.2(q,JCF=279Hz),123.7(q,JCF=281Hz),127.3,129.1,129.4,143.7,164.9,165.3,165.6,166.1,166.5ppm;MS(ESI)m/z(%):510[M+1]+;HRMS(ESI)calcd.for C21H26BrF3NO5[M+1]+:508.0941;found:508.0939.
实施例27
无色液体;分离产率32%;IR(neat)v/cm-1:2956,2874,1763,1715,1602,1572,1455,1435,1293,1257,1197,1146,1084,1038,741;1H NMR(400MHz,CDCl3)δ1.39-1.51(m,3H),1.74-2.07(m,3.45H),2.36(dd,J=16.0,8.0Hz,0.55H),2.57(s,3H),2.61-2.68(m,1H),3.36-3.56(m,3H),3.79-3.80(m,3H),3.81-4.06(m,2H),4.30(t,J=8.0Hz,2H),7.22-7.24(m,2H),7.38(t,J=8.0Hz,1H),7.86(d,J=8.0Hz,1H);19F NMR(400MHz,CDCl3)δ-70.14(s,1.3F),-70.13(s,1.7F);13C NMR(400MHz,CDCl3)δ20.8,21.0,21.7,27.4,27.5,28.5,31.2,32.0,32.5,32.7,42.8,43.0,53.5,54.8,55.5,59.6(m),63.9,123.2(q,JCF=279Hz),123.7(q,JCF=280Hz),125.6,129.4,130.1,131.7,132.0,140.0,164.9,165.3,165.6,166.1,167.4;MS(ESI)m/z(%):510[M+1]+;HRMS(ESI)calcd.for C21H26BrF3NO5[M+1]+:508.0941;found:508.0933.
实施例28
无色液体;分离产率41%;IR(neat)v/cm-1:2956,2865,2834,1758,1712,1606,1512,1435,1383,1257,1178,1103,1030,849,772,698,613;1H NMR(400MHz,CDCl3)δ1.35-1.50(m,3H),1.72-2.07(m,3.54H),2.34(dd,J=12.0,8.0Hz,0.66H),2.60-2.67(m,1H),3.32-3.52(m,3H),3.77(s,3H),3.81(s,3H),3.94-4.05(m,2H),4.23-4.32(m,2H),6.88(d,J=8.0Hz,2H),7.93(d,J=8.0Hz,2H);19F NMR(400MHz,CDCl3)δ-70.2(s,1.5F),-70.1(s,1.5F);13C NMR(400MHz,CDCl3)δ20.7,21.0,27.4,27.5,28.6,31.2,32.0,32.5,32.7,42.8,43.0,53.5,53.6,54.9,55.4,55.5,59.5(m),63.9,113.6,122.5,123.2(q,JCF=267Hz),123.7(q,JCF=277Hz),131.4,163.3,164.9,165.3,165.6,166.0,166.2;MS(ESI)m/z(%):526[M+1]+;HRMS(ESI)calcd.for C21H26BrF3NO6[M+1]+:524.0890;found:524.0885.
实施例29
无色液体;分离产率41%;IR(neat)v/cm-1:2954,2867,1758,1713,1586,1434,1393,1278,1177,1103,1035,1008,923,847,755,683;1H NMR(400MHz,CDCl3)δ1.36-1.47(m,3H),1.75-1.93(m,3H),2.02(dd,J=16.0,8.0Hz,0.53H),2.34(dd,J=16.0,8.0Hz,0.47H),2.60-2.67(m,1H),3.35-3.44(m,2H),3.46-3.55(m,1H),3.79(s,3H),3.82-3.88(m,1H),3.97-4.06(m,1H),4.30(t,J=8.0Hz,2H),7.69(dd,J=8.4Hz,2.0Hz,2H),7.77(d,J=8.0Hz,2H);19F NMR(400MHz,CDCl3)δ-70.10(s,1.64F),-70.09(s,1.36F);13C NMR(400MHz,CDCl3)δ20.7,20.9,27.4,27.5,28.5,31.2,32.0,32.5,32.7,42.9,43.1,53.5,53.6,54.9,55.5,59.6(m),64.4,100.7,123.2(q,JCF=223Hz),123.7(q,JCF=225Hz),129.5,130.9,137.7,164.9,165.3,165.5,165.9,166.0;MS(ESI)m/z(%):622[M+1]+;HRMS(ESI)calcd.for C20H23BrIF3NO5[M+1]+:619.9751;found:619.9744.
实施例30
无色液体;分离产率31%;IR(neat)v/cm-1:2956,2920,1759,1713,1594,1435,1322,1296,1277,1193,1169,1073,832,688;1H NMR(400MHz,CDCl3)δ1.80-1.94(m,1H),2.30(s,6H),2.39-2.46(m,1H),2.57-2.62(m,1H),2.73-2.83(m,1H),3.45-3.62(m,3H),3.80(s,1.19H),3.83(s,1.81H),4.04-4.17(m,4H),6.52(s,2H),6.64(s,1H);19F NMR(400MHz,CDCl3)δ-70.2(s,1.23F),-70.1(s,1.77F);13C NMR(400MHz,CDCl3)δ27.4,31.3,32.4,32.8,32.9,43.1,43.3,53.56,53.64,53.8,59.6(m),63.4,112.0,123.1,123.3(q,JCF=279Hz),123.7(q,JCF=281Hz),139.4,158.2,165.0,165.4,165.6,166.2;MS(ESI)m/z(%):466[M+1]+;HRMS(ESI)calcd.for C19H24BrF3NO4[M+1]+:466.0835;found:466.0831.
实施例31
无色液体;分离产率33%;IR(neat)v/cm-1:2959,2863,1758,1711,1598,1435,1358,1276,1291,1283,1097,1035,967,923,816,737,664,555;1H NMR(400MHz,CDCl3)δ1.38-1.48(m,1H),1.52-1.59(m,2H),1.82-1.97(m,1.49H),2.26-2.31(dd,J=12.0,8.0Hz,0.51H),2.43(s,3H),2.56-2.63(m,1H),3.29-3.40(m,2H),3.45-3.54(m,1H),3.80-3.81(m,3H),3.96-4.08(m,3H),7.34(d,J=8.0Hz,2H),7.76(d,J=8.0Hz,2H);19F NMR(400MHz,CDCl3)δ-70.2(s,1.47F),-70.1(1.53F);13C NMR(400MHz,CDCl3)δ21.6,23.6,23.9,27.4,27.4,28.9,29.1,30.8,31.6,42.8,43.0,53.6,53.8,54.3,54.9,59.4(q,JCF=14Hz),69.4,123.2(q,JCF=279Hz),123.6(q,JCF=281Hz),127.8,130.0,145.1,164.9,165.3,165.4,166.0;MS(ESI)m/z(%):530[M+1]+;HRMS(ESI)calcd.for C19H24BrF3NO6S[M+1]+:530.0454;found:530.0450.
实施例32
浅黄色液体;分离产率45%;IR(neat)v/cm-1:3061,2954,2869,1762,1712,1459,1428,1379,1334,1308,1193,1075,996,756,728,704,672;1H NMR(400MHz,CDCl3)δ:1.52-1.66(m,1H),1.80-1.88(m,2H),1.97-2.11(m,1.32H),2.36(dd,J=12.0Hz,4.0Hz,0.68H),2.63-2.71(m,1H),3.31-3.56(m,5H),3.77-3.79(m,3H),3.86-4.03(m,2H),7.28(t,J=8.0Hz,1H),7.39(t,J=8.0Hz,1H),7.73(d,J=8.0Hz,1H),7.83(d,J=8.0Hz,1H);19F NMR(400MHz,CDCl3)δ:-70.10(s,1.4F),-70.05(s,1.6F);13C NMR(400MHz,CDCl3)δ:24.1,24.3,27.4,27.5,31.1,31.6,31.9,32.6,42.8,43.1,53.5,53.6,54.5,55.0,59.6(m),121.0,123.2(q,JCF=280Hz),121.3,123.6(q,JCF=281Hz),126.0,136.1,152.9,164.9,165.3,165.5,165.9;MS(ESI)m/z(%):527[M+1]+;HRMS(ESI)calcd.for C19H21BrF3N2O3S2[M+1]+:525.0124;found:525.0117.Anal.Calcd for C19H20BrF3N2O3S2:C,43.43;H,3.84;N,5.33;Found:C,43.48;H,3.64;N,4.97.
在干燥的10mL Schlenk管中加入fac-Ir(ppy)3(6.5mg,2mol%),严格抽换氮气三次,在氮气条件下加入DMF(1mL),底物1(0.5mmol)和芳基炔8(1.0mmol),置于24瓦荧光灯照射下室温搅拌反应过夜。体系倒入水(20mL)和乙酸乙酯(20mL)中分液,水相用乙酸乙酯萃取三次(5mL×3),合并有机相,饱和食盐水洗三次(5mL×3),无水硫酸钠干燥,抽滤,硅胶柱层析得到产物。
实施例33
浅黄色液体;分离产率59%;IR(neat)v/cm-1:3067,2956,2916,2882,1762,1666,1437,1276,1229,1182,1105,1031,925;1H NMR(400MHz,CDCl3)δ:3.48-3.54(m,2H),3.55(s,3H),3.86-3.91(m,2H),6.61(s,1H),7.30-7.39(m,5H);19F NMR(376MHz,CDCl3)δ-67.8(s);13C NMR(100MHz,CDCl3)δ53.6,54.1,60.3(q,JCF=27Hz),67.9,121.9,122.4(q,JCF=264Hz),127.7,128.8,128.9,129.1,137.1,158.7,163.5;MS(ESI)m/z(%):394[M+1]+;HRMS(ESI)calcd.for C15H14BrF3NO3[M+1]+:392.0104;found:392.0102.
实施例34
无色液体;分离产率64%;IR(neat)v/cm-1:3072,2957,2908,2899,1762,1667,1599,1505,1439,1354,1319,1257,1186,1104,1032,936,842;1H NMR(400MHz,CDCl3)δ3.55-3.60(m,5H),3.91-3.99(m,2H),6.61(s,1H),7.02(t,J=8.8Hz,2H),7.36-7.40(m,2H);19F NMR(376MHz,CDCl3)δ-110.7(m,1F),-67.8(s,3F);13C NMR(100MHz,CDCl3)δ53.6,54.2,60.4(q,JCF=27Hz),68.1,114.7,114.9,122.4(q,JCF=274Hz),122.7,127.6,131.1,131.2,158.8,161.5,163.5,164.0;MS(ESI)m/z(%):412[M+1]+;HRMS(ESI)calcd.forC15H13BrF4NO3[M+1]+410.0009;found 410.0007.
实施例35
浅黄色液体;分离产率64%;IR(neat)v/cm-1:3084,2956,2912,2890,1759,1667,1564,1436,1354,1254,1192,1109,1032,929;1H NMR(400MHz,CDCl3)δ3.47-3.54(m,2H),3.59(s,3H),3.89-4.01(m,2H),6.61(s,1H),6.95-7.07(m,1H),7.23-7.30(m,2H),7.34(s,1H);19F NMR(376MHz,CDCl3)δ-67.8(s);13C NMR(100MHz,CDCl3)δ53.6,54.2,60.3(q,JCF=22Hz),68.1,123.0,123.3(q,JCF=227Hz),126.7,127.2,128.9,129.15,129.18,133.5,138.7,158.6,163.3;MS(ESI)m/z(%):428[M+1]+;HRMS(ESI)calcd.for C15H13BrClF3NO3[M+1]+:425.9714;found:425.9705.
实施例36
白色固体;熔点:115.2-117.5℃:分离产率52%;IR(neat)v/cm-1:3084,3037,2954,2877,1758,1666,1486,1435,1255,1187,1104,1031,836;1H NMR(400MHz,CDCl3)δ2.46-3.56(m,2H),3.60(s,3H),3.87-3.93(m,2H),6.63(s,1H),7.36-7.40(m,2H),7.44-7.47(m,4H)7.56-7.59(m,4H);19F NMR(376MHz,CDCl3)δ-67.7(s);13C NMR(100MHz,CDCl3)δ:53.7,54.2,60.4(q,JCF=27Hz),68.0,122.1,122.4(q,JCF=284Hz),126.3,127.0,127.9,128.6,129.0,129.5,137.0,139.9,141.9,158.7,163.6;MS(ESI)m/z(%):470[M+1]+;HRMS(ESI)calcd.for C21H18BrF3NO3[M+1]+:468.0417;found:468.0411.
实施例37
浅黄色液体;分离产率33%;IR(neat)v/cm-1:2955,2933,2843,1757,1701,1603,1508,1435,1257,1173,1113,1031,840;1H NMR(400MHz,CDCl3)δ3.36-3.39(m,2H),3.46(s,3H),3.50-3.62(m,2H),3.80(s,3H),6.50(s,1H),6.84(d,J=8.8Hz,2H),7.23(d,J=8.8Hz,2H);19F NMR(376MHz,CDCl3)δ-67.8(s);13C NMR(100MHz,CDCl3)δ31.1,41.8,53.6,55.3,64.8(q,JCF=25Hz),113.5,122.5(q,JCF=284Hz),122.6,129.1,129.6,130.1,160.2,161.8,165.2;MS(ESI)m/z(%):422[M+1]+;HRMS(ESI)calcd.for C16H16BrF3NO4[M+1]+:422.0209;found:422.0203.
实施例38
浅黄色液体;分离产率62%;IR(neat)v/cm-1:3075,2959,2907,2877,1760,1667,1484,1437,1327,1255,1167,1136,1073,1033,701;1H NMR(400MHz,CDCl3)δ3.51(t,J=9.2Hz,2H),3.55(s,3H),3.87-4.00(m,2H),6.67(s,1H),7.48(t,J=8.0Hz,1H),7.58(d,J=8.0Hz,2H),7.67(s,1H);19F NMR(376MHz,CDCl3)δ-67.8(s,3F),-62.8(s,3F);13C NMR(100MHz,CDCl3)δ53.6,54.1,60.4(q,JCF=27Hz),68.1,122.3(q,JCF=284Hz),123.4,123.6(q,JCF=271Hz),125.8,126.5,128.5,130.2,130.5,132.3,137.9,158.6,163.3;MS(ESI)m/z(%):462[M+1]+;HRMS(ESI)calcd.for C16H13BrF6NO3[M+1]+:459.9978;found:459.9972.
实施例39
浅黄色固体;熔点:77.8-79.3℃:分离产率65%;IR(neat)v/cm-1:2962,2899,2869,1759,1666,1436,1364,1267,1202,1112,1032,926,827;1H NMR(400MHz,CDCl3)δ1.30(s,9H),3.42-3.52(m,2H),3.57(s,3H),3.81-3.91(m,2H),6.58(s,1H),7.31(d,J=8.4Hz,2H),7.34(d,J=8.8Hz,2H);19F NMR(376MHz,CDCl3)δ-67.8(s);13C NMR(100MHz,CDCl3)δ31.0,34.6,53.5,54.0,60.3(q,JCF=28Hz),67.7,121.6,122.4(q,JCF=284Hz),124.5,128.7,129.1,134.1,152.2,158.5,163.6;MS(ESI)m/z(%):450[M+1]+;HRMS(ESI)calcd.for C19H22BrF3NO3[M+1]+:448.0730;found:448.0724.
实施例40
浅黄色液体;分离产率43%;IR(neat)v/cm-1:3075,2955,2916,2877,1758,1666,1584,1483,1436,1353,1104,1086,1032,1012,821;1H NMR(400MHz,CDCl3)δ3.42-3.54(m,2H),3.55(s,3H),3.86-3.96(m,2H),6.57(s,1H),7.22(d,J=8.8Hz,2H),7.43(d,J=8.4Hz,2H);19F NMR(376MHz,CDCl3)δ-67.8(s);13C NMR(100MHz,CDCl3)δ53.7,54.2,60.3(q,JCF=27Hz),68.1,122.3(q,JCF=274Hz),122.7,123.4,127.3,130.6,130.9,136.0,158.6,163.4;MS(ESI)m/z(%):472[M+1]+;HRMS(ESI)calcd.for C15H13Br2F3NO3[M+1]+469.9209,found 469.9205.
实施例41
浅黄色液体;分离产率44%;IR(neat)v/cm-1:3088,2956,2920,2886,1759,1666,1591,1487,1436,1354,1256,1189,1104,1032,927,826;1H NMR(400MHz,CDCl3)δ3.42-3.52(m,2H),3.54(s,3H),3.86-3.97(m,2H),6.58(s,1H),7.24-7.30(m,4H);19F NMR(376MHz,CDCl3)δ-67.8(s);13C NMR(100MHz,CDCl3)δ53.6,54.1,60.3(q,JCF=27Hz),68.0,122.3(q,JCF=284Hz),122.7,127.2,127.9,130.4,136.1,136.5,158.6,163.4;MS(ESI)m/z(%):428[M+1]+;HRMS(ESI)calcd.for C15H13BrClF3NO3[M+1]+:425.9714,found:425.9706.
实施例42
无色液体;分离产率67%;IR(neat)v/cm-1:3325,2936,2864,1757,1665,1436,1352,1253,1145,1092,1031,928,891,827;1H NMR(400MHz,CDCl3)δ1.52-1.58(m,2H),1.62-1.68(m,2H),1.98-2.06(m,2H),2.08-2.25(m,2H),3.80(s,3H),3.95(t,J=9.6Hz,2H),4.36(t,J=9.6Hz,2H),5.94(s,1H),6.26(s,1H);19F NMR(376MHz,CDCl3)δ-68.0(s);13C NMR(100MHz,CDCl3)δ21.3,22.1,25.1,26.1,53.6,54.4,59.7(q,JCF=27Hz),68.6,119.9,122.5(q,JCF=284Hz),130.8,133.8,134.5,160.4,163.9;MS(ESI)m/z(%):398[M+1]+;HRMS(ESI)calcd.for C15H18BrF3NO3[M+1]+:396.0417;found:396.0412.
实施例43
浅黄色液体;分离产率63%;IR(neat)v/cm-1:3063,3028,2955,1759,1666,1603,1490,1472,1436,1351,1272,1189,1103,1031,948,864,700;1H NMR(400MHz,CDCl3)δ2.51(m,1H),3.01(dt,J=14.4,5.2Hz,1H),3.40(s,1.51H),3.44(s,1.49H),3.76-3.80(m,2H),4.03-4.11(m,1H),6.56(s,0.51H),6.69(s,0.49H),7.11-7.24(m,4H),7.28-7.42(m,6H);19F NMR(376MHz,CDCl3)δ-67.8(s,1.5F),-67.7(s,1.5F);13C NMR(100MHz,CDCl3)δ40.4,40.6,53.2,53.3,60.2(m),67.0,67.1,71.9,72.4,122.1,122.2,122.3(q,JCF=284Hz),122.5(q,JCF=284Hz),126.5,127.79,127.82,128.4,128.6,128.8,128.9,129.0,129.1,129.13,129.16,129.3,136.9,137.0,137.09,137.11,158.3,158.7,136.27,163.33;MS(ESI)m/z(%):484[M+1]+;HRMS(ESI)calcd.for C22H20BrF3NO3[M+1]+:482.0573,found:482.0566.
实施例44
浅黄色液体;分离产率43%;IR(neat)v/cm-1:3071,3032,2968,2916,1755,1664,1493,1436,1352,1273,1236,1174,1104,1030,775,700;1H NMR(400MHz,CDCl3)δ3.44(s,1.51H),3.46(s,1.49H),3.94(t,J=8.4Hz,0.51H),4.04(t,J=8.4Hz,0.51H),4.23(t,J=8.8Hz,0.49H),4.29(t,J=9.6Hz,0.49H),4.83-4.91(m,1H),6.59(s,0.51H),6.81(s,0.49H),7.13-7.19(m,2H),7.28-7.44(m,8H);19F NMR(376MHz,CDCl3)δ-67.64(s,1.5F),-67.59(s,1.5F);13C NMR(100MHz,CDCl3)δ53.3,53.4,60.6(m),69.2,69.4,75.3,75.8,122.0,122.1,122.3(q,JCF=284Hz),122.7(q,JCF=284Hz),126.4,126.6,127.8,127.9,128.7,128.9,129.1,129.17,129.20,137.0,141.0,141.1,159.3,160.0,163.3;MS(ESI)m/z(%):468[M+1]+;HRMS(ESI)calcd.for C21H18BrF3NO3[M+1]+:468.0417,found:468.0412.
实施例45
浅黄色液体;分离产率53%;IR(neat)v/cm-1:3066,2970,2932,2899,1758,1665,1490,1463,1444,1367,1351,1289,1210,1172,1104,1031,919,871,767,701;1H NMR(400MHz,CDCl3)δ1.20(s,6H),3.27(s,3H),3.78(q,J=8.4Hz,2H),6.65(s,1H),7.31-7.39(m,5H);19F NMR(376MHz,CDCl3)δ:-68.0(s);13C NMR(100MHz,CDCl3)δ27.4,27.5,53.0,60.1(q,JCF=27Hz),67.8,79.5,122.5(q,JCF=284Hz),122.6,127.9,128.5,129.0,129.2,137.3,157.1,163.3;MS(ESI)m/z(%):422[M+1]+;HRMS(ESI)calcd.for C17H18BrF3NO3[M+1]+:420.0417,found:420.0406.
实施例46
无色液体;分离产率56%;IR(neat)v/cm-1:3066,2957,2872,1760,1663,1589,1490,1469,1436,1368,1256,1174,1105,1031,939,864,766,700;1H NMR(400MHz,CDCl3)δ0.86-0.91(m,6H),1.12-1.20(m,1H),1.47-1.52(m,1H),1.60-1.67(m,1H),3.40(s,1.49H),3.43(s,1.51H),3.66(q,J=8.0Hz,1H),3.78-3.87(m,1H),3.95-4.00(m,1H),6.56(s,0.51H),6.69(s,0.49H),7.30-7.41(m,5H);19F NMR(376MHz,CDCl3)δ-67.9(s,1.4F),-67.8(s,1.6F);13C NMR(100MHz,CDCl3)δ22.3,22.4,22.8,22.9,25.1,25.2,44.3,44.4,53.2,60.2(m),64.6,64.8,73.4,73.6,122.3(q,JCF=284Hz),122.3,122.4,122.6(q,JCF=284Hz),127.7,127.8,128.5,128.6,128.9,129.00,129.04,129.1,137.2,157.5,157.9,163.4;MS(ESI)m/z(%):450[M+1]+;HRMS(ESI)calcd.for C19H22BrF3NO3[M+1]+:448.0730,found:448.0717.
实施例47
浅黄色液体;分离产率31%;IR(neat)v/cm-1:3058,2960,2908,2869,1761,1668,1436,1350,1252,1173,1104,1030,947,767,700;1H NMR(400MHz,CDCl3)δ0.82(dd,J=6.8,3.6Hz,3H),0.87(t,J=6.8Hz,3H),1.68-1.79(m,1H),3.34(s,1.51H),3.39(s,1.49H),3.61-3.72(m,1H),3.79-3.90(m,2H),6.55(s,0.49H),6.73(s,0.51H),7.30-7.34(m,4H),7.39-7.41(m,1H);19F NMR(376MHz,CDCl3)δ-67.81(s,1.5F),-67.78(s,1.5F);13C NMR(100MHz,CDCl3)δ17.3,17.5,18.3,18.4,31.8,32.0,53.1,60.2(m),70.1,70.6,71.6,71.7,122.3(q,JCF=284Hz),122.3,122.5,122.6(q,JCF=284Hz),127.7,127.8,128.4,128.6,128.9,129.0,129.1,137.09,137.14,157.7,158.2,163.4,163.5;MS(ESI)m/z(%):436[M+1]+;HRMS(ESI)calcd.for C18H20BrF3NO3[M+1]+:434.0573,found:434.0566.
实施例48
浅黄色液体;分离产率53%;IR(neat)v/cm-1:3066,2962,2903,2878,1761,1668,1489,1436,1351,1255,1185,1105,1031,941,864,766,700;1H NMR(400MHz,CDCl3)δ0.75(t,J=6.4Hz,3H),0.88(dt,J=7.2,3.2Hz,3H),1.06-1.17(m,1.51H),1.25-1.41(m,1.49H),3.36(s,1.49H),3.40(s,1.51H),3.71-3.90(m,3H),6.54(s,0.49H),6.73(s,0.51H),7.28-7.37(m,4H),7.40-7.42(m,1H);19F NMR(376MHz,CDCl3)δ-67.8(s);13C NMR(100MHz,CDCl3)δ11.5,13.5,13.7,25.9,38.0,38.2,53.1,60.1(m),69.4,70.0,70.1,70.3,122.3(m),122.6(q,JCF=284Hz),127.7,127.8,128.4,128.6,128.9,128.99,129.04,129.06,137.0,137.1,157.5,158.0,163.3,163.4ppm;MS(ESI)m/z(%):450[M+1]+;HRMS(ESI)calcd.for C19H22BrF3NO3[M+1]+:448.0730,found:448.0720.
生物活性测试
对上述合成的产物,委托沈阳中化农药化工研发有限公司对其杀菌、杀虫以及除草的生物活性进行了测试。经过对黄瓜霜霉病、黄瓜炭疽病、小麦白粉病、玉米锈病、小菜蛾、粘虫、桃蚜、朱砂叶螨、百日草、苘麻、金狗尾和稗草的测试,发现化合物3i对小麦白粉病和玉米锈病具有一定的防治效果,化合物7a对黄瓜霜霉病、小麦白粉病和黄瓜炭疽病具有一定的防治效果。具体情况如下:
1杀菌活性结果
测试结果表明,化合物3i对小麦白粉病和玉米锈病具有一定的防治效果,化合物7a对黄瓜霜霉病、小麦白粉病和黄瓜炭疽病具有一定的防治效果,其它化合物在试验剂量下,活性不明显,结果见表1。
表1 杀菌活性活性测试结果
2杀虫活性结果
测试结果表明,在试验剂量下,3g等5个化合物对小菜蛾、粘虫、桃蚜和朱砂叶螨的活性不明显,结果见表2。
表2 杀虫活性活性测试结果
3除草活性结果
测试结果表明,在试验剂量下,3g等5个化合物对百日草、苘麻、金狗尾和稗草的活性不明显,结果见表3。
表3 除草活性活性测试结果
Claims (8)
2.如权利要求1所述的制备方法,其特征在于,所述的有机溶剂为二甲基甲酰胺、苯、甲苯、N-甲基吡咯烷酮和四氯化碳中的一种或多种;
和/或,所述的反应的温度为15~30℃;
和/或,所述的化合物1与所述的化合物2的摩尔比为1:(1~10);
和/或,所述的反应的时间为1分钟~1小时。
3.如权利要求2所述的制备方法,其特征在于,所述的有机溶剂为二甲基甲酰胺;
和/或,所述的反应的时间为10分钟~1小时。
4.如权利要求1所述的制备方法,其特征在于,所述的催化剂为Ir(dF(CF3)ppy)2(dtbbpy)(PF6)。
6.如权利要求5所述的制备方法,其特征在于,
所述的有机溶剂为二甲基甲酰胺、苯、甲苯、N-甲基吡咯烷酮和四氯化碳中的一种或多种;
和/或,所述的反应的温度为15~30℃;
和/或,所述的化合物1与所述的化合物6的摩尔比为1:(1~10);
和/或,所述的反应的时间为1分钟~20小时。
7.如权利要求6所述的制备方法,其特征在于,所述的有机溶剂为二甲基甲酰胺;
和/或,所述的反应的时间为10小时~20小时。
8.如权利要求5所述的制备方法,其特征在于,所述的催化剂为fac-Ir(ppy)3。
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Citations (3)
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WO2005044813A1 (en) * | 2003-11-11 | 2005-05-19 | Shenyang Research Institute Of Chemical Industry | Benzopyrone compounds, preparation method and use thereof |
WO2005080344A1 (fr) * | 2004-02-20 | 2005-09-01 | Shenyang Research Institute Of Chemical Industry | Compose d'azole substitue et preparation et application correspondantes |
CN101133022A (zh) * | 2004-07-12 | 2008-02-27 | 拜尔农作物科学股份公司 | 用作杀真菌剂和杀虫剂的取代的2-吡咯烷酮衍生物 |
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WO2005044813A1 (en) * | 2003-11-11 | 2005-05-19 | Shenyang Research Institute Of Chemical Industry | Benzopyrone compounds, preparation method and use thereof |
WO2005080344A1 (fr) * | 2004-02-20 | 2005-09-01 | Shenyang Research Institute Of Chemical Industry | Compose d'azole substitue et preparation et application correspondantes |
CN101133022A (zh) * | 2004-07-12 | 2008-02-27 | 拜尔农作物科学股份公司 | 用作杀真菌剂和杀虫剂的取代的2-吡咯烷酮衍生物 |
Non-Patent Citations (2)
Title |
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创制杀菌剂烯肟菌酯生物活性及应用( Ⅱ) ———小麦白粉病;司乃国等;《农药》;20031130;第42卷(第11期);39-40 * |
嘧啶类杀菌剂的研究进展;任玮静等;《农药》;20130131;第52卷(第1期);1-7 * |
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