杀真菌的吡唑、吡唑啉和四氢哒嗪的制作方法

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专利名称:杀真菌的吡唑、吡唑啉和四氢哒嗪的制作方法
专利说明 本发明涉及新的杀真菌剂及其盐和金属配合物;涉及制备它们产品的方法、含有它们的杀真菌组合物和应用它们杀真菌的方法。
控制植物真菌生长的新的杀真菌剂一直为人们所需求。在大多数情况下,人们寻求这样的化合物以选择性地控制有用作物(例如棉花、水稻、玉米、小麦和大豆)的真菌生长,但这样的化合物甚少。在上述的作物中,未抑制的真菌生长可能引起明显的损失,降低农民的收益,同时增加消费者的费用。对于所述目的已有许多产品出售,但人们一直在研究更有效、更价廉和对环境更安全的产品。
已开发和应用了许多杀真菌剂,例如U.S.3,920,646公开了下式化合物作为抗炎剂
Konishi等人(J.Pest.Sci.1990,15,13-22)公开了杀真菌的下式的吡唑基嘧啶化合物
式中R1-R6是氢,烷基,芳基或链烯基。在吡唑环和嘧啶环上烷基取代均增加杀真菌活性。在吡唑环上引入苯基降低杀真菌活性。
本发明涉及包括所有几何和立体异构体的下述式Ⅰ、Ⅱ、Ⅲ、Ⅳ、Ⅴ和Ⅵ化合物及其盐和金属配合物;涉及含有它们的农用组合物和它们作为杀真菌剂的用途
式中
A是2-嘧啶基,2-吡啶基,2-喹啉基,2-喹唑啉基,1-异喹啉基或3-异喹啉基,所述每一个基团均可被R3、R4和R18取代;或是可被R3和R4取代的S-三嗪基;条件是R3、R4和R18只取代杂环的碳原子;
G是可由R3、R4和R18取代的2-喹唑啉基;
E是氢;囟素;C1-C6烷基;可由1至2个甲基取代的C3-C7环烷基;C1-C6囟代烷基;C1-C6烷硫基;C1-C6烷氧基;C1-C6囟代烷氧基;或者可由R5、R6和R7取代的下列基团苯基,苯氧基,苯硫基,苯氨基,苯甲基,2,3-二氢化茚基,四氢化萘基,1-萘基,2-萘基,噻吩基,呋喃基或吡啶基;
n是1,2或3;
R1是氢;囟素;氰基;羟基;C1-C4烷氧基;-OC(=O)R19;-OC(=O)NHR20;C1-C4烷基;C1-C4囟代烷基;C2-C3烷基羰基;C2-C4链烯基;C2-C6烷氧基烷基;C2-C4炔基;C2-C3烷氧基羰基;或可由R8、R9和R10取代的下列基团苯基,苯甲基,1-萘基,2-萘基,噻吩基,呋喃基或吡啶基;
R2是氢,氰基,C1-C4烷基或C1-C4囟代烷基;
R3、R4和R18分别是囟素;氰基;羟基;(C1-C4烷基)3甲硅烷基甲基;可由R21取代的苯基;C1-C6烷基;环丙基;C1-C6囟代烷基;C1-C6烷硫基;C2-C4链烯基;C2-C4炔基;C1-C4烷氧基;C1-C4囟代烷氧基;C2-C4链烯氧基;C2-C4炔氧基;C2-C4烷氧基烷基;NR11R12;或者当R3和R4、R3和R18或R4和R18取代邻位碳原子时,R3和R4、R3和R18或R4和R18可以一起是可由1至2个甲基取代的-(CH2)3-或-(CH2)4-;
R5和R8分别是囟素;氰基;硝基;羟基;羧基;C1-C6烷基;C3-C6环烷基;C1-C6囟代烷基;C1-C4烷硫基;C1-C4烷基亚磺酰基;C1-C4烷基磺酰基;(C1-C4烷基)3甲硅烷基;C2-C5烷基羰基;C2-C4链烯基;C2-C4链烯氧基;C2-C4炔基;C2-C4炔氧基;C1-C4烷氧基;C1-C4囟代烷氧基;C2-C4烷氧基烷基;C2-C5烷氧基羰基;C2-C4烷氧基烷氧基;NR13R14;C(=O)NR15R16;或可被R17取代的苯基,苯氧基或苯硫基;
R6、R7、R9、R10、R17、R21、R22和R24分别是囟素,C1-C4烷基,C1-C4囟代烷基,C1-C4烷氧基或C1-C4囟代烷氧基;
R11、R12、R13、R14、R15和R16分别是氢;C1-C2烷基;或者R11和R12、R13和R14或R15和R16可以与它们相连接的氮原子一起形成吗啉代,吡咯烷基或哌啶子基团;
R19和R25是氢或C1-C3烷基;
R20和R26是C1-C4烷基;或可被R22取代的苯基;
R23是氢,C1-C4烷基,C1-C4囟代烷基,C2-C5烷基羰基,可被R24取代的苯基羰基,C3-C4链烯基,C3-C4炔基,苯环上可被R24取代的苯甲基,C1-C4烷基亚磺酰基,C1-C4烷基磺酰基,可被R24取代的苯基亚磺酰基,可被R24取代的苯基磺酰基,C2-C4烷氧羰基,可被R24取代的苯氧基羰基,C(=O)NR25R26,C(=S)NHR26P(=S)(OR26)2,P(=O)(OR26)2,或S(=O)2NR25R26;
条件是
ⅰ)当E是囟素,C1-C6烷硫基,C1-C6烷氧基,C1-C6囟代烷氧基,苯氧基,苯硫基或苯氨基时,E仅可取代式Ⅰ或Ⅲ化合物;
ⅱ)就式Ⅰ化合物而言,当A是2-吡啶基,n是2,R1和R2是氢时,E不是被1至2个氟、氯、三氟甲基、C1-C4烷基或C1-C4烷氧基取代的苯基,或者E不是噻吩基或呋喃基;
ⅲ)就式Ⅲ化合物而言,E是苯基,苯氧基,苯硫基,苯甲基,1-萘基,2-萘基,噻吩基,呋喃基,吡啶基,上述每一个基团可被R5、R6和R7取代;或者R1是苯基,苯甲基,1-萘基,2-萘基,噻吩基,呋喃基或吡啶基,所述的每一个基团可被R8、R9和R10取代;和R1必须是在4-位;
ⅳ)对于式Ⅲ化合物,R5不是NR13R14;
ⅴ)对于式Ⅰ和Ⅱ化合物,当n是1时,R1和R2不占据吡唑啉环的5-位;
ⅵ)对于式Ⅰ化合物,当A是S-三嗪基时,R3或R4不是氨基;
ⅶ)就式Ⅰ化合物而言,当A是可被R3、R18和R4取代的2-吡啶基和n是1时,E不是可由R5、R6和R7取代的苯氨基;
ⅷ)就式Ⅰ和式Ⅲ化合物而言,当A是2-吡啶基,n是1,R1和R2是氢时,E不是苯基,4-溴苯基,4-甲氧基苯基,4-硝基苯基或4-羟基苯基;
ⅸ)对于式Ⅱ化合物,当n是3时,E不是氢或C1-C5烷基;
ⅹ)对于式Ⅱ化合物,当n是1时,E不是氢;
ⅹⅰ)对于式Ⅰ化合物,当n是1和A是6-甲氧基吡啶基时,E不是4-N,N-二甲氨基苯基;
ⅹⅱ)对于式Ⅱ化合物,当A是2-吡啶基,n是2,R1和R2是氢时,E不是C1-C4烷基或吡啶基。
鉴于最大地杀真菌活性和/或易于合成的原因,优选的化合物是
1.下述的式Ⅰ和Ⅴ化合物及其金属配合物,其中
A是2-嘧啶基或2-喹唑啉基,它们可被R3、R4和R18取代;和
R1是氢;羟基;C1-C4烷氧基;C1-C4烷基;C1-C4囟代烷基;C2-C3烷基羰基;C2-C4链烯基;C2-C4炔基;C2-C3烷氧基羰基;或苯基,苯甲基,1-萘基,2-萘基,噻吩基,呋喃基或吡啶基,所述的每一个基团可被R8、R9和R10取代;
R3、R4和R18分别是囟素,C1-C4烷基,环丙基,C1-C4囟代烷基,烯丙基,C2-C3炔基,C1-C4烷氧基或C1-C4囟代烷氧基;R23是氢,C(=O)NHR26或C2-C4烷氧基羰基。
2.下述优选的1的化合物及其金属配合物,其中
A是可被R3、R4和R18取代的2-嘧啶基;
n是1或2;
E是苯基,2,3-二氢茚基,四氢萘基,1-萘基,噻吩基或吡啶基,所述每一个基团可被R5、R6和R7取代;
R1是氢,羟基,C1-C4烷氧基或C1-C4烷基;
R5是囟素,氰基,C1-C4烷基,C1-C4囟代烷基,烯丙基,炔丙基,C1-C4烷氧基,C1-C4囟代烷氧基,可被R17取代的苯基或苯氧基;和
R6、R7、R9、R10和R17分别是H,F,Cl,甲基,三氟甲基,甲氧基或三氟甲氧基。
3.优选的2的化合物及其金属配合物,其中
E是可被R5、R6和R7取代的苯基、2,3-二氢茚基或四氢萘基;和
R2是氢或C1-C4烷基。
就最大的抗真菌活性和/或容易合成而言,特别优选的化合物是
1-(4,6-二甲基-2-嘧啶基)-3-(3,4-二甲基苯基)-1,4,5,6-四氢哒嗪;
1-(4,6-二甲基-2-嘧啶基)-3-(4-乙基苯基)-1,4,5,6-四氢哒嗪;
1-(4,6-二甲基-2-嘧啶基)-1,4,5,6-四氢-3-(4-甲基苯基)哒嗪;
1-(4,6-二甲基-2-嘧啶基)-1,4,5,6-四氢-3-[4-(1-甲基乙基)苯基]哒嗪;
1-(4,6-二甲基-2-嘧啶基)-4-乙基-1,4,5,6-四氢-3-苯基哒嗪;
1-(4,6-二甲基-2-嘧啶基)-1,4,5,6-四氢-4-甲基-3-苯基哒嗪。
本发明还包括控制植物真菌病的方法,该方法包括将有效量的下述式Ⅰ、Ⅱ、Ⅲ、Ⅳ、Ⅴ或Ⅵ化合物或其农业上适宜的盐或其金属配合物施用于欲保护植物所在地,所述式Ⅰ、Ⅱ、Ⅲ、Ⅳ、Ⅴ或Ⅵ化合物是其中
A和G是2-嘧啶基,2-吡啶基,2-喹啉基,2-喹唑啉基,1-异喹啉基或3-异喹啉基,所述每一个基团均可被R3、R4和R18取代;或是可被R3和R4取代的S-三嗪基;条件是R3、R4和R18只取代杂环的碳原子;
E是氢;囟素;C1-C6烷基;可由1至2个甲基取代的C3-C7环烷基;C1-C6囟代烷基;C1-C6烷硫基;C1-C6烷氧基;C1-C6囟代烷氧基;或者可由R5、R6和R7取代的下列基团苯基,苯氧基,苯硫基,苯氨基,苯甲基,2,3-二氢化茚基,四氢化萘基,1-萘基,2-萘基,噻吩基,呋喃基或吡啶基;
n是1,2或3;
R1是氢;囟素;氰基;羟基;C1-C4烷氧基;-OC(=O)R19;-OC(=O)NHR20;C1-C4烷基;C1-C4囟代烷基;C2-C3烷基羰基;C2-C4链烯基;C2-C6烷氧基烷基;C2-C4炔基;C2-C3烷氧基羰基;或可由R8、R9和R10取代的下列基团苯基,苯甲基,1-萘基,2-萘基,噻吩基,呋喃基或吡啶基;
R2是氢,氰基,C1-C4烷基或C1-C4囟代烷基;
R3、R4和R18分别是囟素;氰基;羟基;(C1-C4烷基)3甲硅烷基甲基;可由R21取代的苯基;C1-C6烷基;环丙基;C2-C4囟代烷基;C1-C6烷硫基;C2-C4链烯基;C2-C4炔基;C1-C4烷氧基;C1-C4囟代烷氧基;C2-C4链烯氧基;C2-C4炔氧基;C2-C4烷氧基烷基;NR11R12;或者当R3和R4、R3和R18或R4和R18取代邻位碳原子时,R3和R4、R3和R18或R4和R18可以一起是可由1至2个甲基取代的-(CH2)3-或-(CH2)4-;
R5和R8分别是囟素;氰基;硝基;羟基;羧基;C1-C6烷基;C3-C6环烷基;C1-C6囟代烷基;C1-C4烷硫基;C1-C4烷基亚磺酰基;C1-C4烷基磺酰基;(C1-C4烷基)3甲硅烷基;C2-C5烷基羰基;C2-C4链烯基;C2-C4链烯氧基;C2-C4炔基;C2-C4炔氧基;C1-C4烷氧基;C1-C4囟代烷氧基;C2-C4烷氧基烷基;C2-C5烷氧基羰基;C2-C4烷氧基烷氧基;NR13R14;C(=O)NR15R16;或可被R17取代的苯基,苯氧基或苯硫基;
R6、R7、R9、R10、R17、R21、R22和R24分别是囟素,C1-C4烷基,C1-C4囟代烷基,C1-C4烷氧基或C1-C4囟代烷氧基;
R11、R12、R13、R14、R15和R16分别是氢;C1-C2烷基;或者R11和R12、R13和R14或R15和R16可以与它们相连接的氮原子一起形成吗啉代,吡咯烷基或哌啶子基团;
R19和R25是氢或C1-C3烷基;
R20和R26是C1-C4烷基;或可被R22取代的苯基;
R23是氢,C1-C4烷基,C1-C4囟代烷基,C2-C5烷基羰基,可被R24取代的苯基羰基,C3-C4链烯基,C3-C4炔基,苯环上可被R24取代的苯甲基,C1-C4烷基亚磺酰基,C1-C4烷基磺酰基,可被R24取代的苯基亚磺酰基,可被R24取代的苯基磺酰基,C2-C4烷氧羰基,可被R24取代的苯氧基羰基,C(=O)NR25R26,C(=S)NHR26P(=S)(OR26)2,P(=O)(OR26)2,或S(=O)2NR25R26;
条件是
ⅰ)当E是囟素,C1-C6烷硫基,C1-C6烷氧基,C1-C6囟代烷氧基,苯氧基,苯硫基或苯氨基时,E仅可取代式Ⅰ和Ⅲ化合物;
ⅱ)就式Ⅲ化合物而言,E是苯基,苯氧基,苯硫基,苯氨基,苯甲基,1-萘基,2-萘基,噻吩基,呋喃基,吡啶基,上述每一个基团可被R5、R6和R7取代;或者R1是苯基,苯甲基,1-萘基,2-萘基,噻吩基,呋喃基或吡啶基,所述的每一个基团可被R8、R9和R10取代;和R1必须是在4-位;和
ⅲ)就式Ⅰ化合物而言,当E是氢,n是1,R1是5-甲基和R2是氢时,A不是可被R3和R4取代的S-三嗪基。
就最大的杀真菌活性和/或易于合成而言,优选的方法是
1.利用下述式Ⅰ和Ⅴ化合物及其金属配合物的方法,其中
A和G是2-嘧啶基或2-喹唑啉基,它们可被R3、R4和R18取代;和
R1是氢;羟基;C1-C4烷氧基;C1-C4烷基;C1-C4囟代烷基;C2-C3烷基羰基;C2-C4链烯基;C2-C4炔基;C2-C3烷氧基羰基;或苯基,苯甲基,1-萘基,2-萘基,噻吩基,呋喃基或吡啶基,所述的每一个基团可被R8、R9和R10取代;
R3、R4和R18分别是囟素,C1-C4烷基,环丙基,C1-C4囟代烷基,烯丙基,C2-C3炔基,C1-C4烷氧基或C1-C4囟代烷氧基;和
R23是氢,C(=O)NHR26或C2-C4烷氧基羰基。
2.按优选的1的方法,其中
A是可被R3、R4和R18取代的2-嘧啶基;
n是1或2;
E是苯基,2,3-二氢茚基,四氢萘基,1-萘基,噻吩基或吡啶基,所述每一个基团可被R5、R6和R7取代;
R1是氢,羟基,C1-C4烷氧基或C1-C4烷基;
R5是囟素,氰基,C1-C4烷基,C1-C4囟代烷基,烯丙基,炔丙基,C1-C4烷氧基,C1-C4囟代烷氧基,可被R17取代的苯基或苯氧基;和R6、R7、R9、R10和R17分别是H,F,Cl,甲基,三氟甲基,甲氧基或三氟甲氧基。
3.按优选的2的方法,其中
E是可被R5、R6和R7取代的苯基、2,3-二氢茚基或四氢萘基;和
R2是氢或C1-C4烷基。
就最大的抗真菌活性和/或容易合成而言,特别优选的方法是利用下列化合物
1-(4,6-二甲基-2-嘧啶基)-3-(3,4-二甲基苯基)-1,4,5,6-四氢哒嗪;
1-(4,6-二甲基-2-嘧啶基)-3-(4-乙基苯基)-1,4,5,6-四氢哒嗪;
1-(4,6-二甲基-2-嘧啶基)-1,4,5,6-四氢-3-(4-甲基苯基)哒嗪;
1-(4,6-二甲基-2-嘧啶基)-1,4,5,6-四氢-3-[4-(1-甲基乙基)苯基]哒嗪;
1-(4,6-二甲基-2-嘧啶基)-4-乙基-1,4,5,6-四氢-3-苯基哒嗪;
1-(4,6-二甲基-2-嘧啶基)-1,4,5,6-四氢-4-甲基-3-苯基哒嗪。
合成
通过一种或多种反应式1至14中描述的方法,可制备式Ⅰ化合物,其中E的定义如前所述,但不包括囟素、苯氧基、苯硫基苯氨基、C1-C6烷氧基、C1-C6烷硫基和C1-C6囟代烷氧基,R1和R2的定义如前所述。
如下面的反应式1中所示,用强碱例如异丙基酰胺锂(LDA)使式Ⅰb化合物去质子化,然后加入R2-L(其中L是离去基团,例如Cl,Br,I,OSO2CH3或OSO2C6H4CH3),可制备式Ⅰa化合物。此反应于惰性的非质子溶剂例如四氢呋喃(THF)或二甲氧基乙烷(DME)中在-78℃至100℃进行。
反应式1
如反应式2所示,将肼1与化合物2反应可制备式Ⅰb化合物。反应在约50℃至100℃于低级醇溶剂,例如乙醇或2-丙醇中进行。
反应式2
LG=Cl,NMe2,NMe2·HCl
必要时可加入碱,例如氢氧化钠。按EP293743-A和Naito等人(Chem.Pharm.Bull.1969,17,1467-1468)的教导,用肼的一水合物处理式3化合物可制得肼1。式2化合物可商购到或按下述文献方法制备
Carey,F.A.;Sundberg,R.J.AdvancedOrganicChemistry;plenumNewYork,1983;PartB,pp.58-62
A-X+NH2NH2·H2O→1
3
X=Cl,SH
如下面的反应式3,4和5中所示,将化合物1与α,β-不饱和酮4,5或6反应,可制备式Ⅰc,Ⅰd和Ⅰe化合物。反应在催化量的酸存在下,于低级醇溶剂(如乙醇或2-丙醇)中,在50℃至100℃下进行。式4,5和6化合物是文献中已知的化合物,并可按专业人员熟悉知的方法制得。
反应式3
反应式4
反应式5
如下面的反应式6中所示,按前述制备式Ⅰb化合物的方法,可由式Ⅰg化合物制备式Ⅰf化合物。
反应式6
按下面反应式7所示,反应化合物1和7可制备式Ⅰg化合物。此反应在催化量的酸(如对甲苯磺酸)和干燥剂[如分子筛(3A)]的存在下,于有机溶剂(例如乙醇,2-丙醇,乙腈或N,N-二甲基甲酰胺)中,在25℃至100℃下进行。反应可分两步实施。第一步包括在有机溶剂(如乙酸或乙腈)中由酮7和肼1形成腙。然后分离腙,并将其溶于惰性溶剂如THF中,用氢化钠处理得到Ⅰg。如果采用乙腈为溶剂,可用碳酸钾代替氢化钠作为碱。
反应式7
用Cannon等人(Org.Syn.,Coll.Vol.IV,1963,597-600)描述的普通方法,由酮基酯8和环氧乙烷可制得式7化合物。
X=Cl,Br
按文献方法(例如参见Close;J.Am.Chem.Soc.1957,79,1455),用R取代的4-氯丁酰氯使母体化合物E-H遭受Friedel-Crafts酰化反应,可制得式7a化合物,其中E是可被R5、R6和R7取代的芳香基团,R1是氢、烷基、囟素或囟代烷基。所述方法解释如下。
按Goel等人(Synthesis,1973,538;参见下面的反应式)教导的方法,在氯化锌存在下,将γ-丁酸内酯与亚硫酰氯反应,可制备相应的氯化丁酰氯。
式7a化合物还可按下法制备将γ-丁酸内酯与酯缩合,然后用R1X烷基化,并用盐酸处理烷基化的产物
同样,用同一方法,由相应的酮基酯和环氧乙烷可制得式Ⅰh,Ⅰi,Ⅰj和Ⅰk化合物,如下面的反应式8,9和10中所示。反应中得到的立体异构体可通过色谱法分离。
反应式8
反应式9
反应式10
制备β-酮基酯和环氧乙烷的方法是文献中公知的,并可通过专业人员熟知的方法制备。例如,酮基酯8可按下法制备用碱(如氢化钠)于质子惰性溶剂(如DMF)中处理式9的酮,然后加入碳酸二乙酯。
如反应式11中所示,用丙二酸酯为原料也可制备式Ⅰj和Ⅰk化合物。中间体内酯10和11与酯ECOOR缩合,然后脱羧化反应,并与肼Ⅰ环合,得到Ⅰj和Ⅰk。
如下面的反应式12所示,用前述的R2-L将式Ⅰo化合物烷基化,可制备式Ⅰn化合物。
反应式12
按制备式Ⅰb化合物的方法,如反应式13所示,由化合物1和溴代酮12可制得式Ⅰo化合物。制备式12化合物的方法是专业人员公知的。
反应式13
专业人员知道通过上述的同一方法,由适宜取代的溴代酮可制备式Ⅰp化合物
通过一种或多种反应式14,15和16中所示的方法,可制备式Ⅱ化合物。
如反应式14中所示,将肼13与α,β-不饱和酮14反应,可制备式Ⅱa化合物,式Ⅱ化合物中的一部分。反应在酸催化剂(如盐酸)存在下,于低级醇溶剂(如乙醇或2-丙醇)中在约50℃至100℃下进行。
反应式14
如反应式15中所示,按制备式Ⅱa所述方法,将式13化合物与酮15a或15b反应,可制备式Ⅱb化合物,其中R1和R2取代在不同的碳原子上。
反应式15
如反应式16所示,按上述制备式Ⅱa的方法,由式13化合物和酮16可制得式Ⅱc化合物。用碱如LDA将式Ⅱc去质子化,然后用R2-L烷基化,得到式Ⅱd化合物。
反应式16
由酮17和式18的羰基化合物制备酮14、15a、15b和16的方法是专业人员熟知的。
Z=H,R1,或R2
制备杂芳基羰基化合物17和羰基化合物18的方法是专业人员公知的。
通过上述的制备式Ⅰf至Ⅰp化合物的各种方法,可制备式Ⅱ化合物,其中n=2(Ⅱe)和n=3(Ⅱf)
专业人员可制备适宜的原料酮、环氧化合物、溴代酮和链烯。
如下面的反应式17所示,将吡唑盐19a(例如钠盐)与含活化的离去基团(如囟素)的杂环20于有机溶剂(如THF)中反应,可制备式Ⅲ的吡唑。此方法可制备3-位具有大取代基E的吡唑Ⅲ。
由吡唑19b和有机金属化合物(如氢化钠)可制备盐19a。
反应式17
19aX=Li,Na或K,
19bX=H,
L是离去基团,如Cl,Br,I,MeSO2等。
也可由二羰基化合物制备式Ⅲa的吡唑。如下面反应式18所示,在醇溶剂(如乙醇)和酸存在下,将例如化合物21的酮基醛与杂环肼缩合,得到吡唑的3,4-和4,5-异构体混合物,然后通过色谱法将它们分离。
反应式18
如反应式19所示,按同一方法,二酮22的反应得到吡唑23的异构体混合物,然后用色谱法分离。
反应式19
R=R1或R2
在醇溶剂(如乙醇)中和微量酸催化剂(如盐酸)存在下,加热酮基醛(如化合物21)和肼的混合物,也可制备吡唑24,如反应式20所示
反应式20
在相同条件下,将二酮22与肼反应,可制备吡唑25的异构体混合物,见反应式21
反应式21
制备吡唑的几种其它方法参见文献Kost,A.N.;Grandberg,I.I.,Advan.Heterocycl.Chem.1966,6,347-429。
当A=G时,式Ⅲ化合物也可按下法制备按Evans等人(J.Org.Chem.1979,44,497-501)教导的方法,用过氧化镍(NiO2)或二氧化锰(MnO2)氧化式Ⅰc和Ⅰd化合物,如反应式22所示
反应式22
当A=G时,用过氧化镍氧化化合物Ⅱb,同样可制备式Ⅳ化合物,见反应式23
反应式23
按Kano等人(Synthesis,1980,695)教导的方法,用硼氢化钠/氯化钛(Ⅳ)还原式Ⅰ化合物,可制备式Ⅴa化合物,式Ⅴ化合物的一部分,其中R23是氢。此反应示于反应式24中。专业人员知道式Ⅰ化合物中的某些取代基与还原条件不能共存,因此,此反应中采用保护和去保护技术是必需的。
反应式24
如下面反应式25所示,用适宜的式26的烷化剂处理式Ⅴa化合物,可制备式Ⅴb化合物,其中R27是C1-C4烷基,C1-C4囟代烷基,可取代的苯甲基,C3-C4链烯基或C3-C4炔基。
反应式25
式26化合物中的离去基团X可以是囟素,乙酸酯基或本专业用于烷基化的其它基团。碘和溴是常用的离去基团X。
将式Ⅴa化合物溶于惰性溶剂(如二氯甲烷,四氢呋喃(THF)或苯)中,于0℃至100℃下用式26化合物和碱处理。优选的碱是三乙胺、N,N-二异丙基乙胺和其它叔胺碱。
式Ⅴb产物可按下法分离蒸发溶剂;并将残余物溶于水不混溶的溶剂(如醚)中;分别用稀的无机酸、水和盐水洗;干燥;蒸发溶剂,然后结晶或色谱法分离,得到纯产物。
如反应式26所示,用式27的适宜的酰化剂、亚磺酰化剂、磺酰化剂或磷酸化试剂处理式Ⅴa化合物,可制备式Ⅴc化合物,其中R28是C1-C4烷基亚磺酰基,可被取代的苯基亚磺酰基,C1-C4烷基磺酰基,可被取代的苯基磺酰基,C1-C4烷基羰基,可被取代的苯基羰基,C(=O)NR25R26,P(=S)(OR26)2,P(=O)(OR26)2,或S(O)2NR25R26,
反应式26
反应式26中,式27化合物的离去基团X可以是囟素,乙酸酯或或本专业用于酰化、亚磺酰基化、磺酰基化或磷酸化的其它基团。最常用的离去基团X是氯。在上述情况下,式27化合物可以是酰氯,氯甲酸酯,亚磺酰氯,磺酰氯,氯磷酸酯或氨基甲酰氯。
将式Ⅴa化合物溶于惰性溶剂如二氯甲烷,四氢呋喃(THF)或苯中,并在0℃至100℃下用式27化合物和碱处理,优选的碱是三乙胺,N,N-二异丙基乙胺;和其它叔胺碱。
按下法分离式Ⅴc产物蒸发溶剂;将残余物溶于水不混溶的溶剂如乙醚中;分别用稀无机酸水溶液、水和盐水洗醚液;干燥;蒸发溶剂,然后通过结晶或色谱法分离,得纯产物。
当R23是C(=O)NR25R26和R25是氢或C(=S)NHR26时,用异氰酸酯或异硫氰酸酯处理式Ⅴa化合物,可制备式Ⅴd化合物,如反应式27所示
反应式27
将式Ⅴa化合物溶于惰性溶剂(如甲苯,THF,乙腈或1,2-二氯乙烷)中,于0℃至50℃用异氰酸酯或异硫氰酸酯处理。蒸发溶剂,然后结晶或用色谱法分离,得到式Ⅴd产物。
按制备式Ⅴ化合物的方法,由式Ⅱ化合物同样可制得式Ⅵ化合物。
本发明化合物Ⅰ-Ⅵ的金属配合物包括与铜、锌、铁、镁或锰阳离子的配合物。这些配合物按下法制备将本发明化合物于质子惰性溶剂(如乙醚或四氢呋喃)中与金属盐混合,反应也可在质子溶剂(如甲醇)中进行。配合物可以从溶液中结晶或沉淀出来,或者移去溶剂后结晶。
专业人员知道式Ⅰ、Ⅱ、Ⅴ和Ⅵ可含有两个或多个不对称碳原子。必要时,用本领域公知的标准方法分离得到的立体异构体。
如反应式28所示,在碱存在下,用各种亲核试剂取代式28化合物的甲硫基,可制备式Ⅰ化合物(Ⅰq),其中E是C1-C6烷硫基、C1-C6烷氧基、苯硫基、苯氧基或苯氨基。适宜的亲核试剂是可取代的苯酚、苯硫酚或苯胺,C1-C6烷硫醇,C1-C6烷醇和C1-C6囟代烷醇。
反应式28
Nu=可取代的苯酚、苯硫酚或苯胺,C1-C6烷醇,C1-C6烷硫醇,C1-C6囟代烷醇;
n=1-3。
式28化合物可按下法制备在吡啶中回流状态下用P2S5处理式29的酰肼,然后在碱(如三乙胺)存在下将得到的硫代衍生物用碘甲烷烷基化,见反应式29。
反应式29
在碱(如三乙胺)存在下,用式30化合物处理式3a化合物可制得式29化合物(反应式30)。
反应式30
反应酰氯31,可制备式30化合物(反应式31)。
反应式31
按文献中的标准方法,用囟化剂(例如溴化磷或氯化磷囟化式29化合物,可制备式Ⅰ化合物,其中E是氯和溴(Ⅰr),见反应式32。
反应式32
勿需作进一步的详细说明,溶信专业人员根据上述的说明,便可将本发明利用至最充分的程度。下述优选的具体实施例仅仅是解释本发明,而不是对本发明做任何限制。下述实施例中,除非另有说明,所有的温度均为摄氏度(℃),所有的份数和百分数均是重量份数和重量百分数。
实施例1
2-[3-(2-氯苯基)-4,5-二氢-1H-吡唑-1-基]-4,6-二甲基嘧啶的合成
将多聚甲醛(7.20g,240mmol),1-(2-氯苯基)乙基酮(23.2g,150mmol),二乙胺盐酸盐(14.7g,180mmol)和盐酸(12M,7.2ml)加入180ml乙醇中。加热时该混悬液变成溶液。将该混悬液加热回流4天,然后将其冰浴冷却,于旋转蒸发器中减压蒸发,烧瓶中一出现沉淀便停止蒸发,冰浴冷却混悬液,过滤得13.6g1-(2-氯苯基)-3-(二甲氨基)-1-丙酮盐酸盐,白色固体。
mp 168-170℃.1H NMR(DMSO-d6)δ2.75(s,6H),3.40(t,2H),3.57(t,2H),7.50(m,3H),7.81(d,1H),11.10(bs,1H).
将50%氢氧化钠溶液(1.2ml)加入上述化合物(1.76g,7.09mmol)和4,6-二甲基-2-肼基嘧啶(0.98g,7.09mmol)的2-丙醇(40ml)混悬液中,加热回流7小时,室温下搅拌过夜,除去溶剂,残余物在50ml水和60ml氯仿中分配,分出有机层,水层用氯仿(60ml)提取,合并有机层,用MgSO4干燥,除去溶剂,残余物经闪层析纯化,得0.35g标题化合物,固体。
mp 116-118℃.1H NMR(CDCl3)δ2.40(s,6H),3.47(t,2H),4.21(t,2H),6.47(s,1H),7.40(m,3H),7.89(m,1H).
实施例2
1-(4,6-二甲基-2-嘧啶基)-1,4,5,6-四氢-3-苯基哒嗪的合成
将4-氯-1-苯基-1-丁酮(2.00g,11.0mmol),4,6-二甲基-2-肼基嘧啶(1.50g,10.9mmol)和三乙胺(3ml)加入60ml 2-丙醇中,加热回流过夜,除去溶剂,残余物于75ml 5%碳酸氢钠溶液和75ml乙酸乙酯中分配,分出有机层,用乙酸乙酯(75ml)提取水层,合并有机层,用50ml盐水洗,MgSO4干燥,除去溶剂,残余物经色谱法纯化,得0.58g 1-(4,6-二甲基-2-嘧啶基)-1,4,5,6-四氢-3-苯基哒嗪,固体,m.p.95-97℃。
1H NMR(CDCl3)δ2.11(m,2H),2.42(s,6H),2.71(t,2H),4.10(t,2H),6.50(s,1H),7.30(m,3H),7.90(m,2H).
实施例3
4-甲基-2-(4-甲基-3-苯基-1H-吡唑-1-基)嘧啶的合成
充氮下,将0.35g(8.86mmol)氢化钠用己烷洗,加入40mlTHF,冷却至0℃,滴入1.00g(6.33mmol)4-甲基-3-苯基-1H-吡唑(Matsukawa,T.;Ohta,B.,J.Pharm.Soc.Japn.,1950,70,134)的10ml THF溶液。气体逸出停止后,加入0.85g(6.64mmol)2-氯-4-甲基嘧啶(Moon,M.W.et al.;J.Agric.Food Chem.,1977 25(5),1039-49)的10ml THF溶液,加热回流过夜,加入150ml水,用乙酸乙酯(2×50ml)提取,分别用水和盐水洗有机层,MgSO4干燥,浓缩,得1.6g棕色油。
该油经硅胶柱层析纯化。静置固化成固体,得1.02g固体状标题化合物。
1H NMR(CDCl3)δ2.3(s,3H),2.6(s,3H),7.0(d,1H),7.3-7.5(m,3H),7.8(m,2H),8.4(s,1H),8.6(d,1H).
实施例4
4,6-二甲基-2-(5-甲基-4-苯基-1H-吡唑-1-基)-嘧啶和4,6-二甲基-2-(3-甲基-4-苯基-1H-吡唑-1-基)嘧啶的合成
将3滴浓盐酸加入2.0g(12.3mmol)2-苯基-3-氧代丁醛和1.7g(12.3mmol)2-肼基-4,6-二甲基嘧啶(Graf,H.etal.,EP293743)及100ml甲醇的混合物中,加热回流4小时,减压除去甲醇,得油状物,静置时结晶。将其用己烷研磨,得2.42g吡唑基嘧啶,它是68%4,6-二甲基-2-(5-甲基-4-苯基-1H-吡唑-1-基)嘧啶和32%4,6-二甲基-2-(3-甲基-4-苯基-1H-吡唑-1-基)嘧啶的混合物。
将1.17g上述的吡唑基嘧啶于120ml硅胶柱上层析,用1∶2的乙酸乙酯∶己烷洗脱,首先得到0.160g4,6-二甲基-2-(3-甲基-4-苯基-1H-吡唑-1-基)嘧啶,固体,m.p.123-124.5℃。
1H-NMR
(CDCl3)δ2.56(s,9H),6.92(s,1H),7.3-7.55(m,5H),8.70(s,1H).
还洗脱出0.782g两种标题化合物的混合物(70∶30);最后得到0.175g4,6-二甲基-2-(5-甲基-4-苯基-1H-吡唑-1-基)嘧啶,固体,m.p.93.5-94℃。
1H-NMR(CDCl3)δ2.58(s,6H),2.75(s,3H),6.98(s,1H),7.3-7.45(m,5H),7.85(s,1H).
实施例5
3-(4-氯苯基)-1,4,5,6-四氢-1-[4-甲基-6-三氟甲基)-2-嘧啶基]哒嗪的合成
将4-氯-1-(4-氯苯基)-1-丁酮(690mg,3.16mmol),4-甲基-6-三氟甲基-2-肼基嘧啶(500mg,2.87mmol),丁磺酸(5滴)和3
分子筛(一勺)加入14ml无水乙腈中,室温下搅拌过夜,用二氟甲烷稀释,过滤,滤液用饱和的碳酸氢钠溶液洗,干燥(Na2SO4),过滤,浓缩,残余物通过硅胶柱,用30%乙酸乙酯/己烷洗脱,滤液浓缩,溶于14ml无水THF中,加入氢化钠(130mg,60%分散体,3.16mmol),于25℃搅拌10分钟,加入饱和的氯化铵溶液和乙醚。分出醚层,用饱和氯化钠溶液洗,Na2SO4干燥,过滤,浓缩,残余物经色谱法纯化,得580mg标题化合物,固体
mp 150-152℃.1H NMR(CDCl3)δ2.1(m,2H),2.6(s,3H),2.7(m,2H),4.1(m,2H),6.9(s,1H),7.4(m,2H),7.8(m,2H).
实施例6
3-(3,4-二甲基苯基)-1-(4,6-二甲基-2-嘧啶基)-1,4,5,6-四氢哒嗪的合成
将4,6-二甲基-2-肼基嘧啶(500mg,3.62mmol)溶于7.2ml乙酸中,充氮和搅拌下加入4-氯-1-(3,4-二甲基苯基)-1-丁酮(763mg,3.62mmol),于25℃下搅拌过夜,除去乙酸,残余物溶于稀碳酸氢钠溶液中,用二氯甲烷提取两次,用MgSO干燥,浓缩,得中间体腙,棕色油性固体(1.21g),将部分固体(200mg,0.6mmol)溶于3ml无水THF中,充氮下搅拌,分3部分加入氢化钠(29mg,60%分散体,0.72mmol),25分钟后加入2滴水。用20ml水稀释,用二氯甲烷(4×5ml)提取,并用10ml乙酸乙酯提取。合并有机提取液,用MgSO4干燥,浓缩,残留物经色谱法纯化,得115mg(两步收率65%)标题化合物,固体
mp 119-120℃.1H NMR(CDCl3)δ2.1(m,2H),2.27(s,3H),2.30(s,3H),2.42(s,6H),2.7(t,2H),4.1(dd,2H),6.49(s,1H),7.1(d,1H),7.55(dd,1H),7.7(d,1H).
实施例7
2-[3-(3,4-二甲基苯基)-5,6-二氯-1(4H)-哒嗪基]-4-甲基喹唑啉的合成
将2-肼基-4-甲基喹唑啉(500mg,3.34mmol)溶于18ml无水乙腈中,充氮下,加入4-氯-1-(3,4-二甲基苯基)-1-丁酮(770mg,3.67mmol)、丁磺酸(5滴)和3A分子筛(1勺),于25℃搅拌过夜,加入过量的碳酸钾,搅拌过周末,加入二氯甲烷和水,分出有机层,用饱和氯化钠溶液洗,Na2SO4干燥,浓缩,残留物经色谱法纯化,得670mg(62%)标题化合物,黄色固体
mp 159-161℃.1H NMR(CDCl3)δ2.18(m,2H),2.29(s,3H),2.33(s,3H),2.75(t,2H),2.93(s,3H),4.2(m,2H),7.15(d,1H),7.3(m,1H),7.6-7.8(m,4H),7.9(d,1H)
实施例8
2-[3-(4-氯苯基)-5,6-二氢-1(4H)-哒嗪基]-4-甲基喹唑啉的合成
将2-肼基-4-甲基喹唑啉(300mg,2.0mmol)溶于15ml无水乙腈中,充氮下加入4-氯-1-(4-氯苯基)-1-丁酮(0.48g,2.2mmol)和丁磺酸(3滴),于25℃搅拌过夜,过滤,用己烷洗固体,得0.35g(53%)标题化合物
mp 248-252℃.1H NMR(CDCl3)δ2.22(m,2H),2.9(t,2H),2.99(s,3H),4.3(m,2H),7.5(m,4H),7.95(d,2H),8.45(d,2H).
实施例9
3-(3,4-二甲基苯基)-1-(4,6-二甲基-2-嘧啶基)六氢哒嗪的合成
于0℃,将1-(4,6-二甲基-2-嘧啶基)-3-(3,4-二甲基苯基)-1,4,5,6-四氢哒嗪(0.30g,1.02mmol)的无水1,2-二甲氧基乙烷(5ml)溶液滴入氯化钛(IV)(1.5mmol,1.5ml)、硼氢化钠(3.06mmol,0.12g)和10ml 1,2-二甲氧基乙烷的混合物中,升温至室温,并搅拌16小时,用水终止反应,用饱和碳酸氢钠水溶液碱化反应液,用二氯甲烷提取3次,合并有机层,用盐水洗,Na2SO4干燥,浓缩,于硅胶柱上闪层析,得210mg目标产物,油状物
1H NMR(CDCl3)δ7.25(s,1H),7.17(m,2H),6.4(bs,1H),6.22(s,1H),4.8(m,1H),3.7(m,1H),3.2(m,1H),2.28(s,3H),2.27(s,9H),1.9(m,2H),1.8(m,1H),1.7(m,1H).
实施例10
3-(4-氯苯基)-1-(4,6-二甲基-2-嘧啶基)-1,4,5,6-四氢哒嗪与氯化锌的配合物的合成
将3-(4-氯苯基)-1-(4,6-二甲基-2-嘧啶基)-1,4,5,6-四氢哒嗪(302mg,1.00mmol)溶于5ml乙醚和5ml四氢呋喃中,室温下,用1.0ml 1.0M ZnCl2的乙醚溶液处理,加ZnCl2乙醚液的同时,有白色结晶性沉淀生成,室温下搅拌18小时,真空浓缩,得0.46g白色结晶性固体,m.p.231-232℃。将其于二氯甲烷中结晶,得白色针状结晶
1H NMR(CDCl3,400MHz)7.78(d,8.5Hz,2H);7.52(d,8.5Hz,2H);6.71(s,1H);4.31-4.25(m,2H);2.92(t,6.4Hz,2H);2.66(s,3H);2.48(s,3H);2.26-2.16(m,2H).
实施例11
3-(4-氯苯基)-1-(4,6-二甲基-2-嘧啶基)-1,4,5,6-四氢哒嗪与氯化铜(II)的配合物的合成
将401mg(1.33mmol)3-(4-氯苯基)-1-(4,6-二甲基-2-嘧啶基)-1,4,5,6-四氢哒嗪的四氢呋喃(8ml)溶液用179mg无水CuCl的无水甲醇(4ml)溶液处理,反应混合物立即呈深橄榄绿色,室温下搅拌18小时,真空浓缩,残留物用乙醚研磨几次,每次用真空浓缩,共得0.55g自由流动的绿宝石绿固体,m.p.135-138℃。于二氯甲烷中结晶,得绿宝石绿棱晶体。
本发明化合物的实例示于表1-35中,专业人员知道这些化合物很容易被转变成它们的酸加成盐。表1-35化合物举例说明最宽的方法权利要求的界限。表中所列的某些化合物超出了本发明化合物权利要求的范围。表1-35中采用下列缩写
t-叔MeO-甲氧基
s-仲i-PrO-异丙氧基
n-正EtS-乙硫基
i-异sec-BuS-仲丁硫基
c-环CN-氰基
Me-甲基TMS-三甲基甲硅烷基
Et-乙基Ac-乙酰基
Pr-丙基MeS(O)-甲亚磺酰基
Bu-丁基MeS(O)-甲磺酰基
Pent-戊基di-二
Hex-己基naphthalenyl-萘基
Ph-苯基Furanyl-呋喃基
Bzl-苄基thienyl-噻吩基
i-Pr-异丙基pieridino-哌啶子基
t-Bu-叔丁基pyridyl-吡啶基
n-Bu-正丁基indanyl-2,3-茚基
c-Pr-环丙基ph-S-苯硫基
c-Hex-环己基ph-O-苯氧基
sec-Bu-仲丁基
表1
R7=H;R3=Me;R4=Me
R1R5R6R1R5R6
HHHHH4-F
HFHHF4-F
HClHHCl4-F
HMeHHMe4-F
H CF3CH2O H H CF3CH2O 4-F
H CF3H H CF34-F
HMeOHHMeO4-F
HH4-ClMeHH
MeF5-FMeFH
MeCl5-ClMeClH
MeMe4-FMeMeH
Me CF3CH2O 4-F Me CF3CH2O H
Me CF34-F Me CF3H
MeMeO4-FMeMeOH
H H 3-CF3Et H H
HF6-FEtFH
HCl6-ClEtClH
HMe6-MeEtMeH
R7=H;R3=Me;R4=Me
R1R5R6R1R5R6
H CF3CH2O 6-Me Et CF3CH2O H
H CF36-Me Et CF3H
HMeO6-MeOEtMeOH
HH4-Bri-PrHH
MeF6-Fi-PrFH
MeCl6-Cli-PrClH
MeMe6-Mei-PrMeH
n-Pr CF3CH2O H i-Pr CF3CH2O H
t-Bu CF3H i-Pr CF3H
sec-BuMeOHi-PrMeOH
H HCF2O H H HCF2O 6-HCF2O
HBrHHIH
Ht-BuOHHEtOH
H H 4-NMe2Me H 4-NEt2
HH4-piperidinoMeH4-吡咯烷基
R7=H;R3=Me;R4=H
R1R5R6R1R5R6
HHHHH4-F
HFHHF4-F
HClHHCl4-F
HMeHHMe4-F
H CF3CH2O H H CF3CH2O 4-F
H CF3H H CF34-F
HMeOHHMeO4-F
HH4-ClMeHH
MeF5-FMeFH
MeCl5-ClMeClH
MeMe4-FMeMeH
R7=H;R3=Me;R4=H
R1R5R6R1R5R6
Me CF3CH2O 4-F Me CF3CH2O H
Me CF34-F Me CF3H
MeMeO4-FMeMeOH
H H 3-CF3Et H H
HF6-FEtFH
HCl6-ClEtClH
HMe6-MeEtMeH
H CF3CH2O 6-Me Et CF3CH2O H
H CF36-Me Et CF3H
HMeO6-MeOEtMeOH
HH4-Bri-PrHH
MeF6-Fi-PrFH
MeCl6-Cli-PrClH
MeMe6-Mei-PrMeH
n-Pr CF3CH2O H i-Pr CF3CH2O H
t-Bu CF3H i-Pr CF3H
sec-BuMeOHi-PrMeOH
H NO26-Cl Me CN 6-CN
H Br 6-Br Me MeS(O)24-F
H HCF2O 4-MeO Me i-Pr H
R7=H;R3=H;R4=H
R1R5R6R1R5R6
HHHHH4-F
HFHHF4-F
HClHHCl4-F
HMeHHMe4-F
H CF3CH2O H H CF3CH2O 4-F
H CF3H H CF34-F
R7=H;R3=H;R4=H
R1R5R6R1R5R6
HMeOHHMeO4-F
HH4-ClMeHH
MeF5-FMeFH
MeCl5-ClMeClH
MeMe4-FMeMeH
Me CF3CH2O 4-F Me CF3CH2O H
Me CF34-F Me CF3H
MeMeO4-FMeMeOH
H H 3-CF3Et H H
HF6-FEtFH
HCl6-ClEtClH
HMe6-MeEtMeH
H CF3CH2O 6-Me Et CF3CH2O H
H CF36-Me Et CF3H
HMeO6-MeOEtMeOH
HH4-Bri-PrHH
MeF6-Fi-PrFH
MeCl6-Cli-PrClH
MeMe6-Mei-PrMeH
n-Pr CF3CH2O H i-Pr CF3CH2O H
t-Bu CF3H i-Pr CF3H
sec-BuMeOHi-PrMeOH
Met-BuHHTMS6-Me
Mei-PrOHHTMS4-F
Me CF3CF2CF2H H TMS 5-CF3
R1=H;R3和R4是Me R1,R3和R4=Me
R5R6R7R5R6R7
H4-Cl5-ClCl4-Cl6-Cl
H4-F6-sec-BuCl4-Cl6-MeO
H4-Et5-ICl3-Me4-Cl
R1=H;R3和R4是Me R1,R3和R4=Me
R5R6R7R5R6R7
H 3-F 6-CF3CH2O Cl 3-CF35-CF3
H 4-Me 6-CF3CF2Cl 4-MeO 5-t-BuO
H4-Br6-n-BuOCl3-n-Bu4-Me
Me4-Me6-MeTMSHH
Me4-F6-MeTMSH4-F
Me4-t-Bu6-t-BuTMSH6-Me
Me 4-CF36-Cl TMS H 6-MeO
Me3-Me5-BrTMSH6-Cl
Me 5-i-Pr 6-MeO TMS H 6-HCF2O
t-Bu6-t-BuHBr6-BrH
t-Bu 4-t-BuO H NMe2H H
t-BuHHCONHEtHH
CF3(CH2)3O H H CN H H
CF3(CF2)2H H 4-F-Ph H H
(CF3)2CH H H 2-MePh H H
sec-BuS H H NO26-Me H
MeS6-MeSH4-Me-PhOHH
EtS4-FHPhSHH
MeS(O) H H CO2H 3-MeO H
i-Prs(O) H H CO2H H H
t-BuS(O)2H H HC≡C H H
MeS(O)2H H MeC≡C H H
CH2=CH H H MeC≡CCH2O 4-F H
CH2=C(CH3)CH2H H t-BuO H H
CH2=CHCH2O H H n-PrO H H
MeOCH2CH2H H EtO 5-EtO H
MeO2C H H Ac H H
MeOCH2O H H sec-BuCO H H
R4=Me;R6和R7和H R1,R6和R7和H
R1R3R5R3R4R5
Hc-PrHc-Prc-PrH
Hc-PrFc-Prc-PrF
Hc-PrClc-Prc-PrCl
Hc-PrMec-Prc-PrMe
H c-Pr CF3CH2O c-Pr CH3C≡C CF3CH2O
H c-Pr CF3c-Pr CH3C≡C CF3
H c-Pr MeO c-Pr CH3C≡C MeO
Me MeC≡C H c-Pr CF3H
Me MeC≡C F c-Pr CF3F
Me MeC≡C Cl c-Pr CF3Cl
Me MeC≡C Me c-Pr CH3OCH2Me
Me MeC≡C CF3CH2O c-Pr CF3CH2O CF3CH2O
Me Cl CF3c-Pr MeS CF3
Me CF2Cl MeO c-Pr CH2=C(Et) MeO
i-Pr CF3H c-Pr CH2=CHCH2H
i-Prsec-BuFc-Prt-BuOF
i-Pr CF3Cl c-Pr HCF2O Cl
i-Pr CF3Me c-Pr CH2=CHCH2O Me
i-Pr CF3CF3CH2O c-Pr MeC≡CCH2O CF3CH2O
i-Pr Et CF3c-Pr NMe2CF3
i-PrMeOMeOc-PrNHEtMeO
Etc-PrHClClH
EtMeC≡CFClClF
Et CH2F Cl Cl Cl Cl
Et CF3CH2O Me Cl Cl Me
Et i-Pr CF3CH2O CH3C≡C Cl CF3CH2O
Et n-Bu CF3CH3C≡C F CF3
Et HC≡CCH2O MeO CH3C≡C CH3OCH2MeO
t-Bu Br Cl OCF3sec-Bu Cl
Ph CF3(CF2)3Me OCF3Br Me
Bzl sec-BuS CF3CH2O OCF3i-Pr CF3CH2O
Me NH2H NH2NH2H
Me NMe2H NMe2NMe2H
Me 4-NEt2H Me NH2H
Me 4-piperidino H Me NEt2H
表2
R1,R2,和R3和H; R1和R2和H;R3=4-Me;
R4=Me R4=Me
EE
1-naphthalenyl1-naphthalenyl
2-furanyl2-furanyl
2-naphthalenyl2-naphthalenyl
3-thienyl3-thienyl
2,5-di-Me-3-furanyl2,5-diMe-3-furanyl
2,5-di-Me-3-thienyl2,5-diMe-3-thienyl
4-Me-pho-4-Me-pho-
2-Cl-pho-2-Cl-pho-
2,6-二甲基苯氧基2,6-diMe-Pho-
3-Me-PhS-4-CN-PhS-
PhNH-4-Me-PhNH-
BzlCl
Etn-hex
sec-BuMe
c-prc-hex
顺式-2-甲基环庚烷基 CF3CH2CH2
sec-BuS-n-BuO
CF3CH2O Cl(CH2)5O
5-Me-2-thienyl4-Me-3-furanyl
5-Me-2-pyridyl2-Me-3-pyridyl
R1,R2和R3和H;R4=Me R1和R2和H;R3=4-Me;
R4=Me
EE
4-pyridyl4-Cl-3-pyridyl
2-indanyl2-indanyl
2-四氢-naphthalenyl2-四氢-naphthalenyl
R1,R2,R3和R4和H R1和R4和Me;R3=4-Me;
R2=H
EE
1-naphthalenyl1-naphthalenyl
2-furanyl2-furanyl
3-thienyl3-thienyl
3-pyridyl3-pyridyl
R3=4-Me;R4=Me R3=H;R4=Me
R1R2E R1R2E
H5-MePhH5-EtPh
H5-i-Pr2-Me-PhH5-sec-Bu2-Me-Ph
H 5-n-Bu 2-Cl-Ph H 5-CF3(CF2)32-Cl-Ph
H5-CN2-MeO-PhH5-t-Bu2-MeO-Ph
H 5-CF32-CF3CH2O-Ph H 5-FCH22-CF3CH2O-Ph
H 5-CF3CH21-naphthalenyl H 5-n-Pr 1-naphthalenyl
i-Pr5-MePhMe4-MePh
i-Pr5-Me2-Me-PhMe4-Me2-Me-Ph
R3=4-Me;R4=Me
R1R2E
i-Pr5-Me2-Cl-Ph
i-Pr5-Me2-MeO-Ph
i-Pr 5-Me 2-CF3CH2O-Ph
ClHPh
FH2-Me-Ph
CF3CF2H 2-Cl-Ph
CH2=CHCH2H 2-MeO-Ph
CO2Me H 2-CF3CH2O-Ph
2-Me-PhHMe
BzlHPh
2-naphthalenylHn-Bu
3-thienyl H CF3CF2
3-pyridylHMe
CN5-MePh
t-Bu5-Me2-Me-Ph
ClCH25-Me 2-Cl-Ph
Et5-Me2-MeO-Ph
n-Pr 5-Me 2-CF3CH2O-Ph
Me 4-Me 2-CF3-Ph
i-Pr 4-Me 2-CF3-Ph
CF34-CF32-CF3-Ph
Me4-Me2-TMS-Ph
H5-OHPh
H5-MeO4-Me-Ph
H5-OC(O)Me4-Cl-Ph
H5-OC(O)NHMePh
R3=H;R4=Me
R1R2E
Me4-Me2-Cl-Ph
Me4-Me2-MeO-Ph
Me 4-Me 2-CF3CH2O-Ph
BrHPh
CNH2-Me-Ph
AcH2-Cl-Ph
CH3C≡CCH2H 2-MeO-Ph
CO2Et H 2-CF3CH2O-Ph
4-Cl-PhHPh
5-Me-3-furylHi-Pr
EtCOH2-Cl-Ph
2-furyl 4-Me CF3
Ph5-MeMe
CN4-MePh
t-Bu4-Me2-Me-Ph
FCH24-Me 2-Cl-Ph
Et4-Me2-MeO-Ph
Cl(CH2)44-Me 2-CF3CH2O-Ph
Me 4-Me 2-CF3-Ph
i-Pr 5-CN 2-CF3-Ph
CF35-Me 2-CF3-Ph
i-Pr4-Me2-TMS-Ph
H5-OHPh
H5-MeO4-Me-Ph
H5-OC(O)Me4-Cl-Ph
H5-OC(O)NHEtPh
表3
R7=H;R3=H;R4=H;Y=CH
R1R5R6R1R5R6
HHHHH4-F
HFHHF4-F
HClHHCl4-F
HMeHHMe4-F
H CF3CH2O H H CF3CH2O 4-F
H CF3H H CF34-F
HMeOHHMeO4-F
HH4-ClMeHH
MeF5-FMeFH
MeCl5-ClMeClH
MeMe4-FMeMeH
Me CF3CH2O 4-F Me CF3CH2O H
Me CF34-F Me CF3H
MeMeO4-FMeMeOH
H H 3-CF3Et H H
HF6-FEtFH
HCl6-ClEtClH
R7=H;R3=H;R4=H;Y=CH
R1R5R6R1R5R6
HMe6-MeEtMeH
H CF3CH2O 6-Me Et CF3CH2O H
H CF36-Me Et CF3H
HMeO6-MeOEtMeOH
HH4-Bri-PrHH
MeF6-Fi-PrFH
MeCl6-Cli-PrClH
MeMe6-Mei-PrMeH
n-Pr CF3CH2O H i-Pr CF3CH2O H
t-Bu CF3H i-Pr CF3H
sec-BuMeOHi-PrMeOH
H HCF2O H H HCF2O 6-HCF2O
HBrHHIH
Ht-BuOHHEtOH
R7=H;R3=H;R4=Me;Y=CH
R1R5R6R1R5R6
HHHHH4-F
HFHHF4-F
HClHHCl4-F
HMeHHMe4-F
H CF3CH2O H H CF3CH2O 4-F
H CF3H H CF34-F
HMeOHHMeO4-F
HH4-ClMeHH
MeF5-FMeFH
MeCl5-ClMeClH
MeMe4-FMeMeH
Me CF3CH2O 4-F Me CF3CH2O H
Me CF34-F Me CF3H
R7=H;R3=H;R4=Me;Y=CH
R1R5R6R1R5R6
MeMeO4-FMeMeOH
H H 3-CF3Et H H
HF6-FEtFH
HCl6-ClEtClH
HMe6-MeEtMeH
H CF3CH2O 6-Me Et CF3CH2O H
H CF36-Me Et CF3H
HMeO6-MeOEtMeOH
HH4-Bri-PrHH
MeF6-Fi-PrFH
MeCl6-Cli-PrClH
MeMe6-Mei-PrMeH
n-Pr CF3CH2O H i-Pr CF3CH2O H
t-Bu CF3H i-Pr CF3H
sec-BuMeOHi-PrMeOH
H HCF2O H H HCF2O 6-HCF2O
HBrHHIH
Ht-BuOHHEtOH
R7=H;R3=4-Me;R4=Me;Y=N
R1R5R6R1R5R6
HHHHH4-F
HFHHF4-F
HClHHCl4-F
HMeHHMe4-F
H CF3CH2O H H CF3CH2O 4-F
H CF3H H CF34-F
HMeOHHMeO4-F
HH4-ClMeHH
MeF5-FMeFH
MeCl5-ClMeClH
MeMe4-FMeMeH
R7=H;R3=4-Me;R4=Me;Y=N
R1R5R6R1R5R6
Me CF3CH2O 4-F Me CF3CH2O H
Me CF34-F Me CF3H
MeMeO4-FMeMeOH
H H 3-CF3Et H H
HF6-FEtFH
HCl6-ClEtClH
HMe6-MeEtMeH
H CF3CH2O 6-Me Et CF3CH2O H
H CF36-Me Et CF3H
HMeO6-MeOEtMeOH
HH4-Bri-PrHH
MeF6-Fi-PrFH
MeCl6-Cli-PrClH
MeMe6-Mei-PrMeH
n-Pr CF3CH2O H i-Pr CF3CH2O H
t-Bu CF3H i-Pr CF3H
sec-BuMeOHi-PrMeOH
H HCF2O H H HCF2O 6-HCF2O
HBrHHBrH
Ht-BuOHHt-BuOH
R4=Me;R6和R7和H R1,R6,和R7和H;Y=N
Y=CH
R1R3R5R3R4R5
H4-c-PrH4-c-Prc-PrH
H4-c-PrF4-c-Prc-PrF
H4-c-PrCl4-c-Prc-PrCl
H4-c-PrMe4-c-Prc-PrMe
H 4-c-Pr CF3CH2O 4-c-Pr CH3C≡C CF3CH2O
H 4-c-Pr CF34-c-Pr CH3C≡C CF3
H 4-c-Pr MeO 4-c-Pr CH3C≡C MeO
R4=Me;R6和R7和H R1,R6,和R7和H;Y=N
Y=CH
R1R3R5R3R4R5
Me 4-MeC≡C H 4-c-Pr CF3H
Me 4-MeC≡C F 4-c-Pr CF3F
Me 4-MeC≡C Cl 4-c-Pr CF3Cl
Me 4-MeC≡C Me 4-c-Pr CH3OCH2Me
Me 4-MeC≡C CF3CH2O 4-c-Pr CF3CH2O CF3CH2O
Me 5-Cl CF34-c-Pr MeS CF3
Me 4-CF2Cl MeO 4-c-Pr CH2=C(Et) MeO
i-Pr 5-CF3H 4-c-Pr CH2=CHCH2H
i-Pr4-sec-BuF4-c-Prt-BuOF
i-Pr 4-CF3Cl 4-c-Pr HCF2O Cl
i-Pr 4-CF3Me 4-c-Pr CH2=CHCH2O Me
i-Pr 4-CF3CF3CH2O 4-c-Pr MeC≡CCH2O CF3CH2O
i-Pr 5-Et CF34-c-Pr NMe2CF3
i-Pr4-MeOMeO4-c-PrNHEtMeO
Et4-c-PrH4-ClClH
Et3-MeC≡CF4-ClClF
Et 4-CH2F Cl 4-Cl Cl Cl
Et 4-CF3CH2O Me 4-Cl Cl Me
Et 4-i-Pr CF3CH2O 4-CH3C≡C Cl CF3CH2O
Et 4-n-Bu CF34-CH3C≡C F CF3
Et 4-HC≡CCH2O MeO 4-CH3C≡C CH3OCH2MeO
t-Bu 3-Br Cl 4-OCF3sec-Bu Cl
Ph 4-CF3(CF2)3Me 4-OCF3Br Me
Bzl 4-sec-BuS CF3CH2O 4-OCF3i-Pr CF3CH2O
表4
R1,R2,和R3=H; R1和R2=H;R3=4-Me;
R4=Me;Y=CH R4=Me;Y=N
EE
1-naphthalenyl1-naphthalenyl
2-furanyl2-furanyl
2-naphthalenyl2-naphthalenyl
3-thienyl3-thienyl
2,5-di-Me-3-furanyl2,5-diMe-3-furanyl
2,5-di-Me-3-thienyl2,5-diMe-3-thienyl
4-Me-pho-4-Me-pho-
2-Cl-pho-2-Cl-pho-
2,6-二甲基苯氧基2,6-diMe-Pho-
3-Me-PhS-4-CN-PhS-
PhNH-4-Me-PhNH-
BzlCl
Etn-hex
sec-BuMe
c-prc-Hex
顺式-2-甲基环庚烷基 CF3CH2CH2
sec-BuS-n-BuO
CF3CH2O Cl(CH2)5O
5-Me-2-thienyl4- Me-3-furanyl
5-Me-2-pyridyl2- Me-3-pyridyl
R1,R2,R3和R4和H; R1和R4和Me;R3=4-Me;
Y=CH R2=H;Y=N
EE
4-pyridyl4-Cl-3-pyridyl
2-indanyl2-indanyl
2-四氢-naphthalenyl2-四氢naphthalenyl
R1,R2,R3和R4和H; R1和R4和Me;R3=4-Me;
Y=CH R2=H;Y=N
EE
1-naphthalenyl1-naphthalenyl
2-furanyl2-furanyl
3-thienyl3-thienyl
3-pyridyl3-pyridyl
表5
R2=H;R3=Me;R4=Me;R7=H;R18=H
R1R5R6R1R5R6
HHHMe4-EtH
H 4-NMe2H Me 4-i-Pr H
H4-MeHMe4-ClH
H4-EtHMe4-MeOH
H4-n-PrHMe4-EtOH
H 4-i-Pr H Me 4-CF3H
H4-n-BuHEtHH
H 4-sec-Bu H H 3-NMe2H
H4-i-BuHH3-MeH
H4-t-BuHH3-EtH
H4-ClHH3-n-PrH
H4-BrHH3-i-PrH
H4-FHH3-n-BuH
H4-OHHH3-ClH
H4-MeOHH3-BrH
H4-EtOHH3-FH
H 4-CF3H H 3-OH H
H 4-CF3CH2O H H 3-MeO H
MeHHH3-EtOH
Me 4-Me H H 3-CF3H
R2=H;R3=Me;R4=Me;R7=H;R18=H
R1R5R6R1R5R6
H 3-CF3CH2O H H 2-Me 5-Me
Me3-MeHH3-Me4-Me
Me3-EtHH2-Et4-Et
Me3-i-PrHH2-Et5-Et
Me3-ClHH3-Et4-Et
Me3-MeOHH2-Me5-t-Bu
Me3-EtOHH2-Cl4-Cl
Me 3-CF3H H 2-Cl 5-Cl
Et3-MeHEt3-MeOH
Et3-EtHEt3-EtOH
Et 3-i-Pr H Et CF3H
Et3-ClHMe2-Me4-Me
Et4-MeHMe2-Me5-Me
Et4-EtHMe3-Me4-Me
Et4-i-PrHMe2-Et4-Et
Et4-ClHMe2-Et5-Et
Et4-MeOHMe3-Et4-Et
Et4-EtOHMe2-Me5-t-Bu
Et 4-CF3H Et 2-Me 4-Me
H2-MeHEt2-Me5-Me
H2-EtHEt3-Me4-Me
H2-ClHEt2-Et4-Et
H2-FHEt2-Et5-Et
H2-OHHEt3-Et4-Et
Me2-MeHH4-PhH
Me2-ClHH4-PhOH
Me2-FHH4-c-HexH
Et2-MeHH4-HexH
Et2-ClHH4-n-AmylH
Et2-FHMe4-PhH
H2-Me4-MeMe4-PhOH
R2=H;R3=Me;R4=Me;R7=H;R18=H
R1R5R6R1R5R6
Me 4-c-Hex H H 3-NH2H
Me 4-Hex H H 4-NH2H
Me 4-n-Amyl H Me 3-NH2H
H 3-Cl 4-Cl Me 4-NH2H
Me 2-Cl 4-Cl Et 3-NH2H
Me 2-Cl 5-Cl Et 4-NH2H
Me 3-Cl 4-Cl n-Pr 4-NMe2H
Et2-Cl4-Cln-Pr4-MeH
Et2-Cl5-Cln-Pr4-EtH
Et3-Cl4-Cln-Pr4-n-PrH
H2-MeO4-MeOn-Pr4-ClH
H3-MeO5-MeOn-Pr4-FH
H3-MeO4-MeOn-Pr4-BrH
Me2-MeO4-MeOn-Pr4-MeOH
Me3-MeO5-MeOn-Pr4-EtOH
Me 3-MeO 4-MeO n-Pr 4-CF3H
Et 2-MeO 4-MeO n-Pr 4-CF3CH2O H
Et 3-MeO 5-MeO n-Pr 3-NMe2H
Et3-MeO4-MeOn-Pr3-MeH
H3-Br5-Brn-Pr3-EtH
Me3-Br5-Brn-Pr3-n-PrH
Et3-Br5-Brn-Pr3-ClH
H3-Me5-Men-Pr3-FH
Me3-Me5-Men-Pr3-BrH
Et3-Me5-Men-Pr3-MeOH
H3-Cl4-MeOn-Pr3-EtOH
Me 3-Cl 4-MeO n-Pr 3-CF3H
Et 3-Cl 4-MeO n-Pr 3-CF3CH2O H
Me 4-NMe2H n-Pr 3-Me 4-Me
Me 3-NMe2H n-Pr 3-Me 5-Me
Et 4-NMe2H n-Pr 3-Cl 4-Cl
Et 3-NMe2H n-Pr 3-MeO 4-MeO
R2=H;R3=Me;R4=Me;R7=H;R18=H
R1R5R6R1R5R6
n-Pr3-MeO5-MeOi-Pr4-MeOH
n-PrHHi-Pr4-EtOH
n-Bu H H i-Pr 4-CF3H
n-Bu 4-Me H i-Pr 4-CF3CH2O H
n-Bu4-EtHi-Pr3-Me4-Me
n-Bu4-n-PrHi-Pr3-Me5-Me
n-Bu4-i-PrHi-Pr3-Cl4-Cl
n-Bu4-ClHi-Pr3-MeO4-MeO
n-Bu4-FHi-Pr3-MeO5-MeO
n-Bu4-BrHH4-TMSH
n-Bu4-MeOHH4-IH
n-Bu4-EtOHH4-t-BuOH
n-Bu 4-CF3H H 4-CF3(CH2)3O H
n-Bu 4-CF3CH2O H H 4-CF3(CF2)2H
n-Bu 3-Me H H 4-(CF3)2CH H
n-Bu 3-Et H H 4-CH3CHClCH H
n-Bu3-n-PrHMe4-TMSH
n-Bu3-ClHMe4-IH
n-Bu3-FHMe4-t-BuOH
n-Bu 3-MeO H Me 4-CF3(CH2)3O H
n-Bu3-EtOHH4-MeSH
n-Bu 3-CF3H H 4-EtS H
n-Bu 3-CF3CH2O H H 4-MeS(O) H
i-PrHHH4-i-PrS(O)H
i-Pr 4-Me H H 4-MeS(O)2H
i-Pr 4-Et H H 4-CH2=CH H
i-Pr 4-n-Pr H H 4-CH2=C(CH3)CH2) H
i-Pr 4-i-Pr H H 4-CH2=CHCH2O H
i-Pr 4-Cl H H 4-MeOCH2CH2H
i-Pr 4-F H H 4-MeOCH2O H
i-Pr4-BrH
R2=H;R3=Me;R4=c-Pr;R7=H;R18=H
R1R5R6R1R5R6
HHHH3-ClH
H 4-NMe2H H 3-Br H
H4-MeHH3-FH
H4-EtHH3-OHH
H4-n-PrHH3-MeOH
H4-i-PrHH3-EtOH
H 4-n-Bu H H 3-CF3H
H 4-sec-Bu H H 3-CF3CH2O H
H4-i-BuHMe3-MeH
H4-t-BuHMe3-EtH
H4-ClHMe3-i-PrH
H4-BrHMe3-ClH
H4-FHMe3-MeOH
H4-OHHMe3-EtOH
H 4-MeO H Me 3-CF3H
H4-EtOHEt3-MeH
H 4-CF3H Et 3-Et H
H 4-CF3CH2O H Et 3-i-Pr H
MeHHEt3-ClH
Me4-MeHEt4-MeH
Me4-EtHEt4-EtH
Me4-i-PrHEt4-i-PrH
Me4-ClHEt4-ClH
Me4-MeOHEt4-MeOH
Me4-EtOHEt4-EtOH
Me 4-CF3H Et 4-CF3H
EtHHH2-MeH
H 3-NMe2H H 2-Et H
H3-MeHH2-ClH
H3-EtHH2-FH
H3-n-PrHH2-OHH
H3-i-PrHMe2-MeH
R2=H;R3=Me;R4=c-Pr;R7=H;R18=H
R1R5R6R1R5R6
H3-n-BuHMe2-ClH
Me2-FHH4-HexH
Et2-MeHH4-n-AmylH
Et2-ClHMe4-PhH
Et2-FHMe4-PhOH
H2-Me4-MeMe4-c-HexH
H2-Me5-MeMe4-HexH
H3-Me4-MeMe4-n-AmylH
H2-Et4-EtH3-Cl4-Cl
H2-Et5-EtMe2-Cl4-Cl
H3-Et4-EtMe2-Cl5-Cl
H2-Me5-t-BuMe3-Cl4-Cl
H2-Cl4-ClEt2-Cl4-Cl
H2-Cl5-ClEt2-Cl5-Cl
Et3-MeOHEt3-Cl4-Cl
Et3-EtOHH2-MeO4-MeO
Et 3-CF3H H 3-MeO 5-MeO
Me2-Me4-MeH3-MeO4-MeO
Me2-Me5-MeMe2-MeO4-MeO
Me3-Me4-MeMe3-MeO5-MeO
Me2-Et4-EtMe3-MeO4-MeO
Me2-Et5-EtEt2-MeO4-MeO
Me3-Et4-EtEt3-MeO5-MeO
Me2-Me5-t-BuEt3-MeO4-MeO
Et2-Me4-MeH3-Br5-Br
Et2-Me5-MeMe3-Br5-Br
Et3-Me4-MeEt3-Br5-Br
Et2-Et4-EtH3-Me5-Me
Et2-Et5-EtMe3-Me5-Me
Et3-Et4-EtEt3-Me5-Me
H4-PhHH3-Cl4-MeO
H4-PhOHMe3-Cl4-MeO
H4-c-HexHEt3-Cl4-MeO
Me 4-NMe2H n-Pr 3-Me 5-Me
R2=H;R3=Me;R4=c-Pr;R7=H;R18=H
R1R5R6R1R5R6
Me 3-NMe2H n-Pr 3-Cl 4-Cl
Et 4-NMe2H n-Pr 3-MeO 4-MeO
Et 3-NMe2H n-Pr 3-MeO 5-MeO
H 3-NH2H n-Pr H H
H 4-NH2H n-Bu H H
Me 3-NH2H n-Bu 4-Me H
Me 4-NH2H n-Bu 4-Et H
Et 3-NH2H n-Bu 4-n-Pr H
Et 4-NH2H n-Bu 4-i-Pr H
n-Pr 4-NMe2H n-Bu 4-Cl H
n-Pr4-MeHn-Bu4-FH
n-Pr4-EtHn-Bu4-BrH
n-Pr4-n-PrHn-Bu4-MeOH
n-Pr4-ClHn-Bu4-EtOH
n-Pr 4-F H n-Bu 4-CF3H
n-Pr 4-Br H n-Bu 4-CF3CH2O H
n-Pr4-MeOHn-Bu3-MeH
n-Pr4-EtOHn-Bu3-EtH
n-Pr 4-CF3H n-Bu 3-n-Pr H
n-Pr 4-CF3CH2O H n-Bu 3-Cl H
n-Pr 3-NMe2H n-Bu 3-F H
n-Pr3-MeHn-Bu3-MeOH
n-Pr3-EtHn-Bu3-EtOH
n-Pr 3-n-Pr H n-Bu 3-CF3H
n-Pr 3-Cl H n-Bu 3-CF3CH2O H
n-Pr3-FHi-PrHH
n-Pr3-BrHi-Pr4-MeH
n-Pr3-MeOHi-Pr4-EtH
n-Pr3-EtOHi-Pr4-n-PrH
n-Pr 3-CF3H i-Pr 4-i-Pr H
n-Pr 3-CF3CH2O H i-Pr 4-Cl H
n-Pr3-Me4-Mei-Pr4-FH
R2=H;R3=Me;R4=c-Pr;R7=H;R18=H
R1R5R6R1R5R6
i-Pr 4-Br H H CH3CHClCH H
i-Pr4-MeOHMe4-TMSH
i-Pr4-EtOHMe4-IH
i-Pr 4-CF3H Me 4-t-BuO H
i-Pr 4-CF3CH2O H Me 4-CF3(CH2)3O H
i-Pr3-Me4-MeH4-MeSH
i-Pr3-Me5-MeH4-EtSH
i-Pr3-Cl4-ClH4-MeS(O)H
i-Pr3-MeO4-MeOH4-i-PrS(O)H
i-Pr 3-MeO 5-MeO H 4-MeS(O)2H
H 4-TMS H H 4-CH2=CH H
H 4-I H H 4-CH2=C(CH3)CH2) H
H 4-t-BuO H H 4-CH2=CHCH2O H
H 4-CF3(CH2)3O H H 4-MeOCH2CH2H
H 4-CF3(CF2)2H H 4-MeOCH2O H
H 4-(CF3)2CH H
R2=H;R3=Me;R4=Et;R7=H;R18=H
R1R5R6R1R5R6
HHHH4-FH
H 4-NMe2H H 4-OH H
H4-MeHH4-MeOH
H4-EtHH4-EtOH
H 4-n-Pr H H 4-CF3H
H 4-i-Pr H H 4-CF3CH2O H
H4-n-BuHMeHH
H4-sec-BuHMe4-MeH
H4-i-BuHMe4-EtH
H4-t-BuHMe4-i-PrH
H4-ClHMe4-ClH
H4-BrHMe4-MeOH
Me 4-EtO H Et 4-CF3H
R2=H;R3=Me;R4=Et;R7=H;R18=H
R1R5R6R1R5R6
Me 4-CF3H H 2-Me H
EtHHH2-EtH
H 3-NMe2H H 2-Cl H
H3-MeHH2-FH
H3-EtHH2-OHH
H3-n-PrHMe2-MeH
H3-i-PrHMe2-ClH
H3-n-BuHMe2-FH
H3-ClHEt2-MeH
H3-BrHEt2-ClH
H3-FHEt2-FH
H3-OHHH2-Me4-Me
H3-MeOHH2-Me5-Me
H3-EtOHH3-Me4-Me
H 3-CF3H H 2-Et 4-Et
H 3-CF3CH2O H H 2-Et 5-Et
Me3-MeHH3-Et4-Et
Me3-EtHH2-Me5-t-Bu
Me3-i-PrHH2-Cl4-Cl
Me3-ClHH2-Cl5-Cl
Me3-MeOHEt3-MeOH
Me3-EtOHEt3-EtOH
Me 3-CF3H Et CF3H
Et3-MeHMe2-Me4-Me
Et3-EtHMe2-Me5-Me
Et3-i-PrHMe3-Me4-Me
Et3-ClHMe2-Et4-Et
Et4-MeHMe2-Et5-Et
Et4-EtHMe3-Et4-Et
Et4-i-PrHMe2-Me5-t-Bu
Et4-ClHEt2-Me4-Me
Et4-MeOHEt2-Me5-Me
R2=H;R3=Me;R4=Et;R7=H;R18=H
R1R5R6R1R5R6
Et4-EtOHEt3-Me4-Me
Et2-Et4-EtMe3-Me5-Me
Et2-Et5-EtEt3-Me5-Me
Et3-Et4-EtH3-Cl4-MeO
H4-PhHMe3-Cl4-MeO
H4-PhOHEt3-Cl4-MeO
H 4-c-Hex H Me 4-NMe2H
H 4-Hex H Me 3-NMe2H
H 4-n-Amyl H Et 4-NMe2H
Me 4-Ph H Et 3-NMe2H
Me 4-PhO H H 3-NH2H
Me 4-c-Hex H H 4-NH2H
Me 4-Hex H Me 3-NH2H
Me 4-n-戊基 H Me 4-NH2H
H 3-Cl 4-Cl Et 3-NH2H
Me 2-Cl 4-Cl Et 4-NH2H
Me 2-Cl 5-Cl n-Pr 4-NMe2H
Me3-Cl4-Cln-Pr4-MeH
Et2-Cl4-Cln-Pr4-EtH
Et2-Cl5-Cln-Pr4-n-PrH
Et3-Cl4-Cln-Pr4-ClH
H2-MeO4-MeOn-Pr4-FH
H3-MeO5-MeOn-Pr4-BrH
H3-MeO4-MeOn-Pr4-MeOH
Me2-MeO4-MeOn-Pr4-EtOH
Me 3-MeO 5-MeO n-Pr 4-CF3H
Me 3-MeO 4-MeO n-Pr 4-CF3CH2O H
Et 2-MeO 4-MeO n-Pr 3-NMe2H
Et3-MeO5-MeOn-Pr3-MeH
Et3-MeO4-MeOn-Pr3-EtH
H3-Br5-Brn-Pr3-n-PrH
Me3-Br5-Brn-Pr3-ClH
Et3-Br5-Brn-Pr3-FH
H3-Me5-Men-Pr3-BrH
R2=H;R3=Me;R4=Et;R7=H;R18=H
R1R5R6R1R5R6
n-Pr3-MeOHi-Pr4-i-PrH
n-Pr3-EtOHi-Pr4-ClH
n-Pr 3-CF3H i-Pr 4-F H
n-Pr 3-CF3CH2O H i-Pr 4-Br H
n-Pr3-Me4-Mei-Pr4-MeOH
n-Pr3-Me5-Mei-Pr4-EtOH
n-Pr 3-Cl 4-Cl i-Pr 4-CF3H
n-Pr 3-MeO 4-MeO i-Pr 4-CF3CH2O H
n-Pr3-MeO5-MeOi-Pr3-Me4-Me
n-PrHHi-Pr3-Me5-Me
n-BuHHi-Pr3-Cl4-Cl
n-Bu4-MeHi-Pr3-MeO4-MeO
n-Bu4-EtHi-Pr3-MeO5-MeO
n-Bu4-n-PrHH4-TMSH
n-Bu4-i-PrHH4-IH
n-Bu4-ClHH4-t-BuOH
n-Bu 4-F H H 4-CF3(CH2)3O H
n-Bu 4-Br H H 4-CF3(CF2)2H
n-Bu 4-MeO H H 4-(CF3)2CH H
n-Bu 4-EtO H H 4-CH3CHClCH H
n-Bu 4-CF3H Me 4-TMS H
n-Bu 4-CF3CH2O H Me 4-I H
n-Bu3-MeHMe4-t-BuOH
n-Bu 3-Et H Me 4-CF3(CH2)3O H
n-Bu3-n-PrHH4-MeSH
n-Bu3-ClHH4-EtSH
n-Bu3-FHH4-MeS(O)H
n-Bu3-MeOHH4-i-PrS(O)H
n-Bu 3-EtO H H 4-MeS(O)2H
n-Bu 3-CF3H H 4-CH2=CH H
n-Bu 3-CF3CH2O H H 4-CH2=C(CH3)CH2) H
i-Pr H H H 4-CH2=CHCH2O H
i-Pr 4-Me H H 4-MeOCH2CH2H
i-Pr 4-Et H H 4-MeOCH2O H
i-Pr4-n-PrH
R2=H;R3=Et;R4=Et;R7=H;R18=H
R1R5R6R1R5R6
HHHH3-n-BuH
H 4-NMe2H H 3-Cl H
H4-MeHH3-BrH
H4-EtHH3-FH
H4-n-PrHH3-OHH
H4-i-PrHH3-MeOH
H4-n-BuHH3-EtOH
H 4-sec-Bu H H 3-CF3H
H 4-i-Bu H H 3-CF3CH2O H
H4-t-BuHMe3-MeH
H4-ClHMe3-EtH
H4-BrHMe3-i-PrH
H4-FHMe3-ClH
H4-OHHMe3-MeOH
H4-MeOHMe3-EtOH
H 4-EtO H Me 3-CF3H
H 4-CF3H Et 3-Me H
H 4-CF3CH2O H Et 3-Et H
MeHHEt3-i-PrH
Me4-MeHEt3-ClH
Me4-EtHEt4-MeH
Me4-i-PrHEt4-EtH
Me4-ClHEt4-i-PrH
Me4-MeOHEt4-ClH
Me4-EtOHEt4-MeOH
Me 4-CF3H Et 4-EtO H
Et H H Et 4-CF3H
H 3-NMe2H H 2-Me H
H3-MeHH2-EtH
H3-EtHH2-ClH
H3-n-PrHH2-FH
H3-i-PrHH2-OHH
R2=H;R3=Et;R4=Et;R7=H;R18=H
R1R5R6R1R5R6
Me2-MeHH4-PhH
Me2-ClHH4-PhOH
Me2-FHH4-c-HexH
Et2-MeHH4-HexH
Et2-ClHH4-n-戊基H
Et2-FHMe4-PhH
H2-Me4-MeMe4-PhOH
H2-Me5-MeMe4-c-HexH
H3-Me4-MeMe4-HexH
H2-Et4-EtMe4-n-戊基H
H2-Et5-EtH3-Cl4-Cl
H3-Et4-EtMe2-Cl4-Cl
H2-Me5-t-BuMe2-Cl5-Cl
H2-Cl4-ClMe3-Cl4-Cl
H2-Cl5-ClEt2-Cl4-Cl
Et3-MeOHEt2-Cl5-Cl
Et3-EtOHEt3-Cl4-Cl
Et 3-CF3H H 2-MeO 4-MeO
Me2-Me4-MeH3-MeO5-MeO
Me2-Me5-MeH3-MeO4-MeO
Me3-Me4-MeMe2-MeO4-MeO
Me2-Et4-EtMe3-MeO5-MeO
Me2-Et5-EtMe3-MeO4-MeO
Me3-Et4-EtEt2-MeO4-MeO
Me2-Me5-t-BuEt3-MeO5-MeO
Et2-Me4-MeEt3-MeO4-MeO
Et2-Me5-MeH3-Br5-Br
Et3-Me4-MeMe3-Br5-Br
Et2-Et4-EtEt3-Br5-Br
Et2-Et5-EtH3-Me5-Me
Et3-Et4-EtMe3-Me5-Me
R2=H;R3=Et;R4=Et;R7=H;R18=H
R1R5R6R1R5R6
Et3-Me5-Men-Pr3-MeOH
H3-Cl4-MeOn-Pr3-EtOH
Me 3-Cl 4-MeO n-Pr 3-CF3H
Et 3-Cl 4-MeO n-Pr 3-CF3CH2O H
Me 4-NMe2H n-Pr 3-Me 4-Me
Me 3-NMe2H n-Pr 3-Me 5-Me
Et 4-NMe2H n-Pr 3-Cl 4-Cl
Et 3-NMe2H n-Pr 3-MeO 4-MeO
H 3-NH2H n-Pr 3-MeO 5-MeO
H 4-NH2H n-Pr H H
Me 3-NH2H n-Bu H H
Me 4-NH2H n-Bu 4-Me H
Et 3-NH2H n-Bu 4-Et H
Et 4-NH2H n-Bu 4-n-Pr H
n-Pr 4-NMe2H n-Bu 4-i-Pr H
n-Pr4-MeHn-Bu4-ClH
n-Pr4-EtHn-Bu4-FH
n-Pr4-n-PrHn-Bu4-BrH
n-Pr4-ClHn-Bu4-MeOH
n-Pr4-FHn-Bu4-EtOH
n-Pr 4-Br H n-Bu 4-CF3H
n-Pr 4-MeO H n-Bu 4-CF3CH2O H
n-Pr4-EtOHn-Bu3-MeH
n-Pr 4-CF3H n-Bu 3-Et H
n-Pr 4-CF3CH2O H n-Bu 3-n-Pr H
n-Pr 3-NMe2H n-Bu 3-Cl H
n-Pr3-MeHn-Bu3-FH
n-Pr3-EtHn-Bu3-MeOH
n-Pr3-n-PrHn-Bu3-EtOH
n-Pr 3-Cl H n-Bu 3-CF3H
n-Pr 3-F H n-Bu 3-CF3CH2O H
n-Pr3-BrHi-PrHH
R2=H;R3=Et;R4=Et;R7=H;R18=H
R1R5R6R1R5R6
i-Pr 4-Me H H 4-CF3(CH2)3O H
i-Pr 4-Et H H 4-CF3(CF2)2H
i-Pr 4-n-Pr H H 4-(CF3)2CH H
i-Pr 4-i-Pr H H 4-CH3CHClCH H
i-Pr4-ClHMe4-TMSH
i-Pr4-FHMe4-IH
i-Pr4-BrHMe4-t-BuOH
i-Pr 4-MeO H Me 4-CF3(CH2)3O H
i-Pr4-EtOHH4-MeSH
i-Pr 4-CF3H H 4-EtS H
i-Pr 4-CF3CH2O H H 4-MeS(O) H
i-Pr3-Me4-MeH4-i-PrS(O)H
i-Pr 3-Me 5-Me H 4-MeS(O)2H
i-Pr 3-Cl 4-Cl H 4-CH2=CH H
i-Pr 3-MeO 4-MeO H 4-CH2=C(CH3)CH2) H
i-Pr 3-MeO 5-MeO H 4-CH2=CHCH2O H
H 4-TMS H H 4-MeOCH2CH2H
H 4-I H H 4-MeOCH2O H
H4-t-BuOH
R2=H;R3=Me;R4=i-Pr;R7=H;R18=H
R1R5R6R1R5R6
HHHH4-i-BuH
H 4-NMe2H H 4-t-Bu H
H4-MeHH4-ClH
H4-EtHH4-BrH
H4-n-PrHH4-FH
H4-i-PrHH4-OHH
H4-n-BuHH4-MeOH
H4-sec-BuHH4-EtOH
R2=H;R3=Me;R4=i-Pr;R7=H;R18=H
R1R5R6R1R5R6
H 4-CF3H Et 3-Me H
H 4-CF3CH2O H Et 3-Et H
MeHHEt3-i-PrH
Me4-MeHEt3-ClH
Me4-EtHEt4-MeH
Me4-i-PrHEt4-EtH
Me4-ClHEt4-i-PrH
Me4-MeOHEt4-ClH
Me4-EtOHEt4-MeOH
Me 4-CF3H Et 4-EtO H
Et H H Et 4-CF3H
H 3-NMe2H H 2-Me H
H3-MeHH2-EtH
H3-EtHH2-ClH
H3-n-PrHH2-FH
H3-i-PrHH2-OHH
H3-n-BuHMe2-MeH
H3-ClHMe2-ClH
H3-BrHMe2-FH
H3-FHEt2-MeH
H3-OHHEt2-ClH
H3-MeOHEt2-FH
H3-EtOHH2-Me4-Me
H 3-CF3H H 2-Me 5-Me
H 3-CF3CH2O H H 3-Me 4-Me
Me3-MeHH2-Et4-Et
Me3-EtHH2-Et5-Et
Me3-i-PrHH3-Et4-Et
Me3-ClHH2-Me5-t-Bu
Me3-MeOHH2-Cl4-Cl
Me3-EtOHH2-Cl5-Cl
Me 3-CF3H Et 3-MeO H
R2=H;R3=Me;R4=i-Pr;R7=H;R18=H
R1R5R6R1R5R6
Et3-EtOHH2-MeO4-MeO
Et CF3H H 3-MeO 5-MeO
Me2-Me4-MeH3-MeO4-MeO
Me2-Me5-MeMe2-MeO4-MeO
Me3-Me4-MeMe3-MeO5-MeO
Me2-Et4-EtMe3-MeO4-MeO
Me2-Et5-EtEt2-MeO4-MeO
Me3-Et4-EtEt3-MeO5-MeO
Me2-Me5-t-BuEt3-MeO4-MeO
Et2-Me4-MeH3-Br5-Br
Et2-Me5-MeMe3-Br5-Br
Et3-Me4-MeEt3-Br5-Br
Et2-Et4-EtH3-Me5-Me
Et2-Et5-EtMe3-Me5-Me
Et3-Et4-EtEt3-Me5-Me
H4-PhHH3-Cl4-MeO
H4-PhOHMe3-Cl4-MeO
H4-c-HexHEt3-Cl4-MeO
H 4-Hex H Me 4-NMe2H
H 4-n-戊基 H Me 3-NMe2H
Me 4-Ph H Et 4-NMe2H
Me 4-PhO H Et 3-NMe2H
Me 4-c-Hex H H 3-NH2H
Me 4-Hex H H 4-NH2H
Me 4-n-戊基 H Me 3-NH2H
H 3-Cl 4-Cl Me 4-NH2H
Me 2-Cl 4-Cl Et 3-NH2H
Me 2-Cl 5-Cl Et 4-NH2H
Me 3-Cl 4-Cl n-Pr 4-NMe2H
Et2-Cl4-Cln-Pr4-MeH
Et2-Cl5-Cln-Pr4-EtH
Et3-Cl4-Cln-Pr4-n-PrH
R2=H;R3=Me;R4=i-Pr;R7=H;R18=H
R1R5R6R1R5R6
n-Pr4-ClHn-Bu4-MeOH
n-Pr4-FHn-Bu4-EtOH
n-Pr 4-Br H n-Bu 4-CF3H
n-Pr 4-MeO H n-Bu 4-CF3CH2O H
n-Pr4-EtOHn-Bu3-MeH
n-Pr 4-CF3H n-Bu 3-Et H
n-Pr 4-CF3CH2O H n-Bu 3-n-Pr H
n-Pr 3-NMe2H n-Bu 3-Cl H
n-Pr3-MeHn-Bu3-FH
n-Pr3-EtHn-Bu3-MeOH
n-Pr3-n-PrHn-Bu3-EtOH
n-Pr 3-Cl H n-Bu 3-CF3H
n-Pr 3-F H n-Bu 3-CF3CH2O H
n-Pr3-BrHi-PrHH
n-Pr3-MeOHi-Pr4-MeH
n-Pr3-EtOHi-Pr4-EtH
n-Pr 3-CF3H i-Pr 4-n-Pr H
n-Pr 3-CF3CH2O H i-Pr 4-i-Pr H
n-Pr3-Me4-Mei-Pr4-ClH
n-Pr3-Me5-Mei-Pr4-FH
n-Pr3-Cl4-Cli-Pr4-BrH
n-Pr3-MeO4-MeOi-Pr4-MeOH
n-Pr3-MeO5-MeOi-Pr4-EtOH
n-Pr H H i-Pr 4-CF3H
n-Bu H H i-Pr 4-CF3CH2O H
n-Bu4-MeHi-Pr3-Me4-Me
n-Bu4-EtHi-Pr3-Me5-Me
n-Bu4-n-PrHi-Pr3-Cl4-Cl
n-Bu4-i-PrHi-Pr3-MeO4-MeO
n-Bu4-ClHi-Pr3-MeO5-MeO
n-Bu4-FHH4-TMSH
n-Bu4-BrHH4-IH
R2=H;R3=Me;R4=i-Pr;R7=H;R18=H
R1R5R6R1R5R6
H4-t-BuOHH4-EtSH
H 4-CF3(CH2)3O H H 4-MeS(O) H
H 4-CF3(CF2)2H H 4-i-PrS(O) H
H 4-(CF3)2CH H H 4-MeS(O)2H
H 4-CH3CHClCH H H 4-CH2=CH H
Me 4-TMS H H 4-CH2=C(CH3)CH2) H
Me 4-I H H 4-CH2=CHCH2O H
Me 4-t-BuO H H 4-MeOCH2CH2H
Me 4-CF3(CH2)3O H H 4-MeOCH2O H
H4-MeSH
R2=H;R3=Me;R4=H;R7=H;R18=H
R1R5R6R1R5R6
H H H H 4-CF3CH2O H
H 4-NMe2H Me H H
H4-MeHMe4-MeH
H4-EtHMe4-EtH
H4-n-PrHMe4-i-PrH
H4-i-PrHMe4-ClH
H4-n-BuHMe4-MeOH
H4-sec-BuHMe4-EtOH
H 4-i-Bu H Me 4-CF3H
H4-t-BuHEtHH
H 4-Cl H H 3-NMe2H
H4-BrHH3-MeH
H4-FHH3-EtH
H4-OHHH3-n-PrH
H4-MeOHH3-i-PrH
H4-EtOHH3-n-BuH
H 4-CF3H H 3-Cl H
R2=H;R3=Me;R4=H;R7=H;R18=H
R1R5R6R1R5R6
H3-BrHMe2-MeH
H3-FHMe2-ClH
H3-OHHMe2-FH
H3-MeOHEt2-MeH
H3-EtOHEt2-ClH
H 3-CF3H Et 2-F H
H 3-CF3CH2O H H 2-Me 4-Me
Me3-MeHH2-Me5-Me
Me3-EtHH3-Me4-Me
Me3-i-PrHH2-Et4-Et
Me3-ClHH2-Et5-Et
Me3-MeOHH3-Et4-Et
Me3-EtOHH2-Me5-t-Bu
Me 3-CF3H H 2-Cl 4-Cl
Et3-MeHH2-Cl5-Cl
Et3-EtHEt3-MeOH
Et3-i-PrHEt3-EtOH
Et 3-Cl H Et 3-CF3H
Et4-MeHMe2-Me4-Me
Et4-EtHMe2-Me5-Me
Et4-i-PrHMe3-Me4-Me
Et4-ClHMe2-Et4-Et
Et4-MeOHMe2-Et5-Et
Et4-EtOHMe3-Et4-Et
Et 4-CF3H Me 2-Me 5-t-Bu
H2-MeHEt2-Me4-Me
H2-EtHEt2-Me5-Me
H2-ClHEt3-Me4-Me
H2-FHEt2-Et4-Et
H2-OHHEt2-Et5-Et
R2=H;R3=Me;R4=H;R7=H;R18=H
R1R5R6R1R5R6
Et3-Et4-EtH3-Cl4-MeO
H4-PhHMe3-Cl4-MeO
H4-PhOHEt3-Cl4-MeO
H 4-c-Hex H Me 4-NMe2H
H 4-Hex H Me 3-NMe2H
H 4-n-戊基 H Et 4-NMe2H
Me 4-Ph H Et 3-NMe2H
Me 4-PhO H H 3-NH2H
Me 4-c-Hex H H 4-NH2H
Me 4-Hex H Me 3-NH2H
Me 4-n-戊基 H Me 4-NH2H
H 3-Cl 4-Cl Et 3-NH2H
Me 2-Cl 4-Cl Et 4-NH2H
Me 2-Cl 5-Cl n-Pr 4-NMe2H
Me3-Cl4-Cln-Pr4-MeH
Et2-Cl4-Cln-Pr4-EtH
Et2-Cl5-Cln-Pr4-n-PrH
Et3-Cl4-Cln-Pr4-ClH
H2-MeO4-MeOn-Pr4-FH
H3-MeO5-MeOn-Pr4-BrH
H3-MeO4-MeOn-Pr4-MeOH
Me2-MeO4-MeOn-Pr4-EtOH
Me 3-MeO 5-MeO n-Pr 4-CF3H
Me 3-MeO 4-MeO n-Pr 4-CF3CH2O H
Et 2-MeO 4-MeO n-Pr 3-NMe2H
Et3-MeO5-MeOn-Pr3-MeH
Et3-MeO4-MeOn-Pr3-EtH
H3-Br5-Brn-Pr3-n-PrH
Me3-Br5-Brn-Pr3-ClH
Et3-Br5-Brn-Pr3-FH
H3-Me5-Men-Pr3-BrH
Me3-Me5-Men-Pr3-MeOH
R2=H;R3=Me;R4=H;R7=H;R18=H
R1R5R6R1R5R6
Et3-Me5-Men-Pr3-EtOH
n-Pr 3-CF3H i-Pr 4-i-Pr H
n-Pr 3-CF3CH2O H i-Pr 4-Cl H
n-Pr3-Me4-Mei-Pr4-FH
n-Pr3-Me5-Mei-Pr4-BrH
n-Pr3-Cl4-Cli-Pr4-MeOH
n-Pr3-MeO4-MeOi-Pr4-EtOH
n-Pr 3-MeO 5-MeO i-Pr 4-CF3H
n-Pr H H i-Pr 4-CF3CH2O H
n-BuHHi-Pr3-Me4-Me
n-Bu4-MeHi-Pr3-Me5-Me
n-Bu4-EtHi-Pr3-Cl4-Cl
n-Bu4-n-PrHi-Pr3-MeO4-MeO
n-Bu4-i-PrHi-Pr3-MeO5-MeO
n-Bu4-ClHH4-TMSH
n-Bu4-FHH4-IH
n-Bu4-BrHH4-t-BuOH
n-Bu 4-MeO H H 4-CF3(CH2)3O H
n-Bu 4-EtO H n-Bu 4-CF3H
n-Bu 4-CF3H n-Bu 4-CF3CH2O H
n-Bu 4-CF3CH2O H n-Bu 3-Me H
n-Bu3-MeHn-Bu3-EtH
n-Bu3-EtHn-Bu3-n-PrH
n-Bu3-n-PrHn-Bu3-ClH
n-Bu3-ClHn-Bu3-FH
n-Bu3-FHn-Bu3-MeOH
n-Bu3-MeOHn-Bu3-EtOH
n-Bu 3-EtO H n-Bu 3-CF3H
n-Bu 3-CF3H n-Bu 3-CF3CH2O H
n-Bu 3-CF3CH2O H i-Pr H H
i-PrHHi-Pr4-MeH
i-Pr4-MeHi-Pr4-EtH
i-Pr4-EtHi-Pr4-n-PrH
i-Pr4-n-PrHi-Pr4-i-PrH
R2=H;R3=Me;R4=H;R7=H;R18=H
R1R5R6R1R5R6
i-Pr 4-Cl H H 4-(CF3)2CH H
i-Pr 4-F H H 4-CH3CHClCH H
i-Pr4-BrHMe4-TMSH
i-Pr4-MeOHMe4-IH
i-Pr4-EtOHMe4-t-BuOH
i-Pr 4-CF3H Me 4-CF3(CH2)3O H
i-Pr 4-CF3CH2O H H 4-MeS H
i-Pr3-Me4-MeH4-EtSH
i-Pr3-Me5-MeH4-MeS(O)H
i-Pr3-Cl4-ClH4-i-PrS(O)H
i-Pr 3-MeO 4-MeO H 4-MeS(O)2H
i-Pr 3-MeO 5-MeO H 4-CH2=CH H
H 4-TMS H H 4-CH2=C(CH3)CH2) H
H 4-I H H 4-CH2=CHCH2O H
H 4-t-BuO H H 4-MeOCH2CH2H
H 4-CF3(CH2)3O H H 4-MeOCH2O H
H 4-CF3(CF2)2H
R2=H;R3=Me;R4=H;R7=H;R18=H
R1R5R6R1R5R6
HHHH4-BrH
H 4-NMe2H H 4-F H
H4-MeHH4-OHH
H4-EtHH4-MeOH
H4-n-PrHH4-EtOH
H 4-i-Pr H H 4-CF3H
H 4-n-Bu H H 4-CF3CH2O H
H4-sec-BuHMeHH
H4-i-BuHMe4-MeH
H4-t-BuHMe4-EtH
H4-ClHMe4-i-PrH
R2=H;R3=H;R4=H;R7=H;R18=H
R1R5R6R1R5R6
Me4-ClHEt4-i-PrH
Me4-MeOHEt4-ClH
Me4-EtOHEt4-MeOH
Me 4-CF3H Et 4-EtO H
Et H H Et 4-CF3H
H 3-NMe2H H 2-Me H
H3-MeHH2-EtH
H3-EtHH2-ClH
H3-n-PrHH2-FH
H3-i-PrHH2-OHH
H3-n-BuHMe2-MeH
H3-ClHMe2-ClH
H3-BrHMe2-FH
H3-FHEt2-MeH
H3-OHHEt2-ClH
H3-MeOHEt2-FH
H3-EtOHH2-Me4-Me
H 3-CF3H H 2-Me 5-Me
H 3-CF3CH2O H H 3-Me 4-Me
Me3-MeHH2-Et4-Et
Me3-EtHH2-Et5-Et
Me3-i-PrHH3-Et4-Et
Me3-ClHH2-Me5-t-Bu
Me3-MeOHH2-Cl4-Cl
Me3-EtOHH2-Cl5-Cl
Me 3-CF3H Et 3-MeO H
Et3-MeHEt3-EtOH
Et 3-Et H Et 3-CF3H
Et3-i-PrHMe2-Me4-Me
Et3-ClHMe2-Me5-Me
Et4-MeHMe3-Me4-Me
Et4-EtHMe2-Et4-Et
R2=H;R3=H;R4=H;R7=H;R18=H
R1R5R6R1R5R6
Me2-Et5-EtEt2-MeO4-MeO
Me3-Et4-EtEt3-MeO5-MeO
Me2-Me5-t-BuEt3-MeO4-MeO
Et2-Me4-MeH3-Br5-Br
Et2-Me5-MeMe3-Br5-Br
Et3-Me4-MeEt3-Br5-Br
Et2-Et4-EtH3-Me5-Me
Et2-Et5-EtMe3-Me5-Me
Et3-Et4-EtEt3-Me5-Me
H4-PhHH3-Cl4-MeO
H4-PhOHMe3-Cl4-MeO
H4-c-HexHEt3-Cl4-MeO
H 4-Hex H Me 4-NMe2H
H 4-n-戊基 H Me 3-NMe2H
Me 4-Ph H Et 4-NMe2H
Me 4-c-Hex H H 3-NH2H
Me 4-Hex H H 4-NH2H
Me 4-n-戊基 H Me 3-NH2H
H 3-Cl 4-Cl Me 4-NH2H
Me 2-Cl 4-Cl Et 3-NH2H
Me 2-Cl 5-Cl Et 4-NH2H
Me 3-Cl 4-Cl n-Pr 4-NMe2H
Et2-Cl4-Cln-Pr4-MeH
Et2-Cl5-Cln-Pr4-EtH
Et3-Cl4-Cln-Pr4-n-PrH
H2-MeO4-MeOn-Pr4-ClH
H3-MeO5-MeOn-Pr4-FH
H3-MeO4-MeOn-Pr4-BrH
Me2-MeO4-MeOn-Pr4-MeOH
Me3-MeO5-MeOn-Pr4-EtOH
Me 3-MeO 4-MeO n-Pr 4-CF3H
R2=H;R3=H;R4=H;R7=H;R18=H
R1R5R6R1R5R6
n-Pr 4-CF3CH2O H n-Bu 3-n-Pr H
n-Pr 3-NMe2H n-Bu 3-Cl H
n-Pr3-MeHn-Bu3-FH
n-Pr3-EtHn-Bu3-MeOH
n-Pr3-n-PrHn-Bu3-EtOH
n-Pr 3-Cl H n-Bu 3-CF3H
n-Pr 3-F H n-Bu 3-CF3CH2O H
n-Pr3-BrHi-PrHH
n-Pr3-MeOHi-Pr4-MeH
n-Pr3-EtOHi-Pr4-EtH
n-Pr 3-CF3H i-Pr 4-n-Pr H
n-Pr 3-CF3CH2O H i-Pr 4-i-Pr H
n-Pr3-Me4-Mei-Pr4-ClH
n-Pr3-Me5-Mei-Pr4-FH
n-Pr3-Cl4-Cli-Pr4-BrH
n-Pr3-MeO4-MeOi-Pr4-MeOH
n-Pr3-MeO5-MeOi-Pr4-EtOH
n-Pr H H i-Pr 4-CF3H
n-Bu H H i-Pr 4-CF3CH2O H
n-Bu4-MeHi-Pr3-Me4-Me
n-Bu4-EtHi-Pr3-Me5-Me
n-Bu4-n-PrHi-Pr3-Cl4-Cl
n-Bu4-i-PrHi-Pr3-MeO4-MeO
n-Bu4-ClHi-Pr3-MeO5-MeO
n-Bu4-FHH4-TMSH
n-Bu4-BrHH4-IH
n-Bu4-MeOHH4-t-BuOH
n-Bu 4-EtO H H 4-CF3(CH2)3O H
n-Bu 4-CF3H H 4-CF3(CF2)2H
n-Bu 4-CF3CH2O H H 4-(CF3)2CH H
n-Bu 3-Me H H 4-CH3CHClCH H
n-Bu3-EtHMe4-TMSH
R2=H;R3=H;R4=H;R7=H;R18=H
R1R5R6R1R5R6
Me 4-I H H 4-MeS(O)2H
Me 4-t-BuO H H 4-CH2=CH H
Me 4-CF3(CH2)3O H H 4-CH2=C(CH3)CH2) H
H 4-MeS H H 4-CH2=CHCH2O H
H 4-EtS H H 4-MeOCH2CH2H
H 4-MeS(O) H H 4-MeOCH2O H
H4-i-PrS(O)H
R3=H;R4=H;R7=H;R18=H
R1R2R5R6R1R2R5R6
Me4-MeHHMe4-Et4-EtH
Me4-Me4-MeHMe4-Et4-i-PrH
Me4-Me4-ClHMe4-Et3-MeH
Me4-Me4-MeOHMe4-Et3-ClH
Me4-Me4-EtOHMe4-Et3-MeOH
Me4-Me4-EtHMe4-Et3-EtOH
Me4-Me4-i-PrHMe4-Et3-EtH
Me4-Me3-MeHMe4-Et3-i-PrH
Me4-Me3-ClHEt4-EtHH
Me4-Me3-MeOHEt4-Et4-MeH
Me4-Me3-EtOHEt4-Et4-ClH
Me4-Me3-EtHEt4-Et4-MeOH
Me4-Me3-i-PrHEt4-Et4-EtOH
Me4-EtHHEt4-Et4-EtH
Me4-Et4-MeHEt4-Et4-i-PrH
Me4-Et4-ClHMe4-Me3-Me4-Me
Me4-Et4-MeOHMe4-Me3-Me5-Me
Me4-Et4-EtOHMe4-Me3-Cl4-Cl
R3=H;R4=H;R7=H;R18=H
R1R2R5R6R1R2R5R6
Me4-Me3-Cl5-ClH6-OH4-MeH
Me4-Me3-MeO4-MeOH6-OMe3-MeH
Me4-Me3-MeO5-MeOH6-OMe3-Me4-Me
H6-OHHHH6-OEt4-ClH
H6-OMeHHH5-OMe4-FH
H6-OEtHHH5-OMe3-ClH
H6-OC(O)MeHHH5-OMe4-ClH
H5-OHHHH5-Br4-ClH
H5-OMeHHMe6-OHHH
H5-OEtHHMe6-OMeHH
H5-BrHHMe4-n-PrHH
H5-MeHHEt4-n-PrHH
H6-MeHH
R3=Me;R4=H;R7=H;R18=H
R1R2R5R6R1R2R5R6
Me4-MeHHMe4-Et4-MeH
Me4-Me4-MeHMe4-Et4-ClH
Me4-Me4-ClHMe4-Et4-MeOH
Me4-Me4-MeOHMe4-Et4-EtOH
Me4-Me4-EtOHMe4-Et4-EtH
Me4-Me4-EtHMe4-Et4-i-PrH
Me4-Me4-i-PrHMe4-Et3-MeH
Me4-Me3-MeHMe4-Et3-ClH
Me4-Me3-ClHMe4-Et3-MeOH
Me4-Me3-MeOHMe4-Et3-EtOH
Me4-Me3-EtOHMe4-Et3-EtH
Me4-Me3-EtHMe4-Et3-i-PrH
Me4-Me3-i-PrHEt4-EtHH
Me4-EtHHEt4-Et4-MeH
R3=Me;R4=H;R7=H;R18=H
R1R2R5R6R1R2R5R6
Et4-Et4-ClHH5-OEtHH
Et4-Et4-MeOHH5-BrHH
Et4-Et4-EtOHH5-MeHH
Et4-Et4-EtHH6-MeHH
Et4-Et4-i-PrHH6-OH4-MeH
Me4-Me3-Me4-MeH6-OMe3-MeH
Me4-Me3-Me5-MeH6-OMe3-Me4-Me
Me4-Me3-Cl4-ClH6-OEt4-ClH
Me4-Me3-Cl5-ClH5-OMe4-FH
Me4-Me3-MeO4-MeOH5-OMe3-ClH
Me4-Me3-MeO5-MeOH5-OMe4-ClH
H6-OHHHH5-Br4-ClH
H6-OMeHHMe6-OHHH
H6-OEtHHMe6-OMeHH
H6-OC(O)MeHHMe4-n-PrHH
H5-OHHHEt4-n-PrHH
H5-OMeHH
R3=Me;R4=Me;R7=H;R18=H
R1R2R5R6R1R2R5R6
Me4-MeHHMe4-Me3-EtOH
Me4-Me4-MeHMe4-Me3-EtH
Me4-Me4-ClHMe4-Me3-i-PrH
Me4-Me4-MeOHMe4-EtHH
Me4-Me4-EtOHMe4-Et4-MeH
Me4-Me4-EtHMe4-Et4-ClH
Me4-Me4-i-PrHMe4-Et4-MeOH
Me4-Me3-MeHMe4-Et4-EtOH
Me4-Me3-ClHMe4-Et4-EtH
Me4-Me3-MeOHMe4-Et4-i-PrH
R3=Me;R4=Me;R7=H;R18=H
R1R2R5R6R1R2R5R6
Me4-Et3-MeHH6-OEtHH
Me4-Et3-ClHH6-OC(O)MeHH
Me4-Et3-MeOHH5-OHHH
Me4-Et3-EtOHH5-OMeHH
Me4-Et3-EtHH5-OEtHH
Me4-Et3-i-PrHH5-BrHH
Et4-EtHHH5-MeHH
Et4-Et4-MeHH6-MeHH
Et4-Et4-ClHH6-OH4-MeH
Et4-Et4-MeOHH6-OMe3-MeH
Et4-Et4-EtOHH6-OMe3-Me4-Me
Et4-Et4-EtHH6-OEt4-ClH
Et4-Et4-i-PrHH5-OMe4-FH
Me4-Me3-Me4-MeH5-OMe3-ClH
Me4-Me3-Me5-MeH5-OMe4-ClH
Me4-Me3-Cl4-ClH5-Br4-ClH
Me4-Me3-Cl5-ClMe6-OHHH
Me4-Me3-MeO4-MeOMe6-OMeHH
Me4-Me3-MeO5-MeOMe4-n-PrHH
H6-OHHHEt4-n-PrHH
H6-OMeHH
R2=H;R3=Me;R4=Me; R2=H;R3=Me;R4=H;
R18=H R18=H
R1R5R6R7R1R5R6R7
H3-Me4-Me5-MeMe3-Me4-Me5-Me
H3-Br4-Me5-BrMe3-Br4-Me5-Br
H3-Cl4-MeO5-ClMe3-Cl4-MeO5-Cl
H3-MeO4-MeO5-MeOMe3-MeO4-MeO5-MeO
R2=H;R3=Me;R4=Me; R2=H;R3=Me;R4=H;
R18=H R18=H
R1R5R6R7R1R5R6R7
H4-TMSHHMe3-Me4-Me5-Me
Me4-TMSHHMe3-Br4-Me5-Br
Et4-TMSHHMe3-Cl4-Me5-Cl
Et3-Me4-Me5-MeMe3-MeO4-MeO5-MeO
Et3-MeO4-MeO5-MeOH4-TMSHH
H2-Cl5-BrHMe4-TMSHH
Me2-Cl5-BrHEt4-TMSHH
H3-Me4-Me5-MeEt3-Me4-Me5-Me
H3-Br4-Me5-BrEt3-Me4-MeO5-MeO
H3-Cl4-MeO5-ClH2-Cl5-BrH
H3-MeO4-MeO5-MeOMe2-Cl5-BrH
R4=Me;R6,R2,R18和R7R2,R18,R1,R6和R7
=H
R1R3R5R3R4R5
MeMeC≡C4-Mei-PrMeO4-MeO
Me MeC≡C 4-CF3CH2O Et c-Pr H
Me Cl 3-CF3Et MeC≡C 3-F
Me CF2Cl 4-MeO Et CH2F 4-Cl
i-Pr CF3H Et CF3CH2O 4-Me
i-Pr sec-Bu 2-F Et i-Pr 4-CF3CH2O
i-Pr CF33-Cl Et n-Bu 3-CF3
i-Pr CF33-Me Et HC≡CCH2O 4-MeO
i-Pr CF34-CF3CH2O t-Bu Br 4-Cl
i-Pr Et 3-CF3Ph CF3(CF2)34-Me
R4=Me;R6,R2,R18和R7R2,R18,R1,R6和R7
=H
R1R3R5R3R4R5
Bzl 4-sec-BuS 4-CF3CH2O Cl Cl H
H NH24-Me Cl Cl 2-F
4-c-Pr CH3OCH24-Me Cl Cl 3-Cl
4-c-Pr CF3CH2O 4-CF3CH2O Cl Cl 4-Me
4-c-Pr MeS 4-CF3CH3C≡C Cl 4-CF3CH2O
4-c-Pr CH2=C(Et) 4-MeO CH3C≡C F 3-CF3
4-c-Pr CH2=CHCH2H CH3C≡C CH3OCH24-MeO
4-c-Pr t-BuO 4-F OCF3sec-Bu 4-Cl
4-c-Pr HCF2O 2-Cl OCF3Br 4-Me
4-c-Pr CH2=CHCH2O 4-Me OCF3i-Pr 4-CF3CH2O
4-c-Pr MeC≡CCH2O 4-CF3CH2O NH2NH24-Me
4-c-Pr NMe23-CF3NH2NH24-Cl
4-c-PrNHEt4-MeONHMeNHMe4-MeO
R2=H;R4=Me;R6,R18和 R18,R2,R1,R6和R7=H
R7=H
R1R3R5R3R4R5
MeMeC≡CHc-Prc-PrH
MeMeC≡CFc-Prc-Pr4-F
MeMeC≡CClc-Prc-Pr4-Cl
c-Prc-Pr4-Me
c-Pr CH3C≡C 4-CF3CH2O
c-Pr CH3C≡C 3-CF3
c-Pr CH3C≡C 3-MeO
c-Pr CF3H
c-Pr CF32-F
c-Pr CF33-Cl
表6
R1,R2,和R3=H; R1和R2=H;R3=4-Me;
R4=Me R4=Me
EE
1-naphthalenyl1-naphthalenyl
2-furanyl2-furanyl
2-naphthalenyl2-naphthalenyl
3-thienyl3-thienyl
2,5-diMe-3-furanyl2,5-diMe-3-furanyl
2,5-diMe-3-thienyl2,5-diMe-3-thienyl
4-Me-pho-4-Me-pho-
2-Cl-pho-2-Cl-pho-
2,6-二甲基苯氧基2,6-diMe-Pho-
3-Me-PhS-4-CN-PhS-
PhNH-4-Me-PhNH-
BzlCl
Etn-hex
sec-BuMe
c-prc-Hex
顺式-2-甲基环庚烷基 CF3CH2CH2
sec-BuS-n-BuO
CF3CH2O Cl(CH2)5O
5-Me-2-thienyl4- Me-3-furanyl
5-Me-2-pyridyl2- Me-3-pyridyl
R1,R2和R3=H;R4=Me R1和R2=H;R3=4-Me;
R4=Me
EE
4-pyridyl4-Cl-3-pyridyl
2-indanyl2-indanyl
2-tetrahydronaphthalenyl2-tetrahydronaphthalenyl
6-Me-3-pyridyl6-Me-3-pyridyl
2-pyridyl2-pyridyl
R1,R2,R3和R4=H R1和R4=Me;R3=4-Me;
R2=H
EE
1-naphthalenyl1-naphthalenyl
2-furanyl2-furanyl
3-thienyl3-thienyl
3-pyridyl3-pyridyl
R3=4-Me;R4=Me R3=4-Me;R4=Me
R1R2E R1R2E
H5-MePhH5-EtPh
H5-i-Pr2-Me-PhH5-sec-Bu2-Me-Ph
H 5-n-Bu 2-Cl-Ph H 5-CF3(CF2)32-Cl-Ph
H5-CN2-MeO-PhH5-t-Bu2-MeO-Ph
H 5-CF3CF3CH2O-Ph H 5-FCH22-CF3CH2O-Ph
H 6-CF3CH21-naphthalenyl H 6-n-Pr 1-naphthalenyl
i-Pr5-MePhMe4-MePh
i-Pr5-Me2-Me-PhMe4-Me2-Me-Ph
R3=4-Me;R4=Me
R1R2E
i-Pr5-Me2-Cl-Ph
i-Pr5-Me2-MeO-Ph
i-Pr 6-Me 2-CF3CH2O-Ph
ClHPh
FH4-Me-Ph
CF3CF2H 4-Cl-Ph
CH2=CHCH2H 4-MeO-Ph
R3=4-Me;R4=Me
R1R2E
CO2Me H 2-CF3CH2O-Ph
2-Me-PhHMe
BzlHPh
2-naphthalenylHn-Bu
3-thienyl H CF3CF2
3-pyridylHMe
CN5-MePh
t-Bu5-Me2-Me-Ph
ClCH25-Me 2-Cl-Ph
Et5-Me2-MeO-Ph
n-Pr 5-Me 2-CF3CH2O-Ph
Me 4-Me 2-CF3-Ph
i-Pr 4-Me 2-CF3-Ph
CF34-CF32-CF3-Ph
R3=4-Me;R4=Me
R1R2E
Me4-Me2-TMS-Ph
Me4-Me2-Cl-Ph
Me4-Me2-MeO-Ph
Me 4-Me 2-CF3CH2O-Ph
BrHPh
CNH4-Me-Ph
AcH4-Cl-Ph
CH3C≡CCH2H 4-MeO-Ph
R3=4-Me;R4=Me
R1R2E
CO2Et H 2-CF3CH2O-Ph
4-Cl-PhHPh
5-Me-3-furylHi-Pr
EtCOH2-Cl-Ph
2-furyl 4-Me CF3
Ph5-MeMe
CN4-MePh
t-Bu4-Me2-Me-Ph
FCH24-Me 2-Cl-Ph
Et4-Me2-MeO-Ph
Cl(CH2)44-Me 2-CF3CH2O-Ph
Me 4-Me 2-CF3-Ph
i-Pr 5-CN 2-CF3-Ph
CF35-Me 2-CF3-Ph
i-Pr4-Me2-TMS-Ph
表7
R7=H;R3=H;R4=H;Y=CH
R1R5R6R1R5R6
HHHHH4-F
HFHHF4-F
HClHHCl4-F
HMeHHMe4-F
H CF3CH2O H H CF3CH2O 4-F
H CF3H H CF34-F
HMeOHHMeO4-F
HH4-ClMeHH
MeF5-FMeFH
MeCl5-ClMeClH
MeMe4-FMeMeH
Me CF3CH2O 4-F Me CF3CH2O H
Me CF34-F Me CF3H
MeMeO4-FMeMeOH
H H 3-CF3Et H H
HF6-FEtFH
HCl6-ClEtClH
R7=H;R3=H;R4=H;Y=CH
R1R5R6R1R5R6
HMe6-MeEtMeH
H CF3CH2O 6-Me Et CF3CH2O H
H CF36-Me Et CF3H
HMeO6-MeOEtMeOH
HH4-Bri-PrHH
MeF6-Fi-PrFH
MeCl6-Cli-PrClH
MeMe6-Mei-PrMeH
n-Pr CF3CH2O H i-Pr CF3CH2O H
t-Bu CF3H i-Pr CF3H
sec-BuMeOHi-PrMeOH
H HCF2O H H HCF2O 6-HCF2O
HBrHHIH
Ht-BuOHHEtOH
R7=H;R3=H;R4=Me;Y=CH
R1R5R6R1R5R6
HHHHH4-F
HFHHF4-F
HClHHCl4-F
HMeHHMe4-F
H CF3CH2O H H CF3CH2O 4-F
H CF3H H CF34-F
HMeOHHMeO4-F
HH4-ClMeHH
MeF5-FMeFH
MeCl5-ClMeClH
MeMe4-FMeMeH
Me CF3CH2O 4-F Me CF3CH2O H
Me CF34-F Me CF3H
R7=H;R3=H;R4=Me;Y=CH
R1R5R6R1R5R6
MeMeO4-FMeMeOH
H H 3-CF3Et H H
HF6-FEtFH
HCl6-ClEtClH
HMe6-MeEtMeH
H CF3CH2O 6-Me Et CF3CH2O H
H CF36-Me Et CF3H
HMeO6-MeOEtMeOH
HH4-Bri-PrHH
MeF6-Fi-PrFH
MeCl6-Cli-PrClH
MeMe6-Mei-PrMeH
n-Pr CF3CH2O H i-Pr CF3CH2O H
t-Bu CF3H i-Pr CF3H
sec-BuMeOHi-PrMeOH
H HCF2O H H HCF2O 6-HCF2O
HBrHHIH
HtBuOHMeEtOH
R7=H;R3=4-Me;R4=Me;Y=N
R1R5R6R1R5R6
HHHHH4-F
HFHHF4-F
HClHHCl4-F
HMeHHMe4-F
H CF3CH2O H H CF3CH2O 4-F
H CF3H H CF34-F
HMeOHHMeO4-F
HH4-ClMeHH
MeF5-FMeFH
MeCl5-ClMeClH
MeMe4-FMeMeH
R7=H;R3=4-Me;R4=Me;Y=N
R1R5R6R1R5R6
Me CF3CH2O 4-F Me CF3CH2O H
Me CF34-F Me CF3H
MeMeO4-FMeMeOH
H H 3-CF3Et H H
HF6-FEtFH
HCl6-ClEtClH
HMe6-MeEtMeH
H CF3CH2O 6-Me Et CF3CH2O H
H CF36-Me Et CF3H
HMeO6-MeOEtMeOH
HH4-Bri-PrHH
MeF6-Fi-PrFH
MeCl6-Cli-PrClH
MeMe6-Mei-PrMeH
n-Pr CF3CH2O H i-Pr CF3CH2O H
t-Bu CF3H i-Pr CF3H
sec-BuMeOHi-PrMeOH
H HCF2O H H HCF2O 6-HCF2O
HBrHHIH
Ht-BuOHHEtOH
R4=Me;R6和R7=H R1,R6,和R7=H;Y=N
Y=CH
R1R3R5R3R4R5
H4-c-PrH4-c-Prc-PrH
H4-c-PrF4-c-Prc-PrF
H4-c-PrCl4-c-Prc-PrCl
H4-c-PrMe4-c-Prc-PrMe
H 4-c-Pr CF3CH2O 4-c-Pr CH3C≡C CF3CH2O
H 4-c-Pr CF34-c-Pr CH3C≡C CF3
H 4-c-Pr MeO 4-c-Pr CH3C≡C MeO
R4=Me;R6和R7=H R1,R6,和R7=H;Y=N
Y=CH
R1R3R5R3R4R5
Me 4-MeC≡C H 4-c-Pr CF3H
Me 4-MeC≡C F 4-c-Pr CF3F
Me 4-MeC≡C Cl 4-c-Pr CF3Cl
Me 4-MeC≡C Me 4-c-Pr CH3OCH2Me
Me 4-MeC≡C CF3CH2O 4-c-Pr CF3CH2O CF3CH2O
Me 5-Cl CF34-c-Pr MeS CF3
Me 4-CF2Cl MeO 4-c-Pr CH2=C(Et) MeO
i-Pr 5-CF3H 4-c-Pr CH2=CHCH2H
i-Pr4-sec-BuF4-c-Prt-BuOF
i-Pr 4-CF3Cl 4-c-Pr HCF2O Cl
i-Pr 4-CF3Me 4-c-Pr CH2=CHCH2O Me
i-Pr 4-CF3CF3CH2O 4-c-Pr MeC≡CCH2O CF3CH2O
i-Pr 5-Et CF34-c-Pr NMe2CF3
i-Pr4-MeOMeO4-c-PrNHEtMeO
Et4-c-PrH4-ClClH
Et3-MeC≡CF4-ClClF
Et 4-CH2F Cl 4-Cl Cl Cl
Et 4-CF3CH2O Me 4-Cl Cl Me
Et 4-i-Pr CF3CH2O 4-CH3C≡C Cl CF3CH2O
Et 4-n-Bu CF34-CH3C≡C F CF3
Et 4-HC≡CCH2O MeO 4-CH3C≡C CH3OCH2MeO
t-Bu 3-Br Cl 4-OCF3sec-Bu Cl
Ph 4-CF3(CF2)3Me 4-OCF3Br Me
Bzl 4-sec-BuS CF3CH2O 4-OCF3i-Pr CF3CH2O
表8
R1,R2和R3=H; R1和R2=H;R3=4-Me;
R4=Me;Y=CH R4=Me;Y=N
EE
1-naphthalenyl1-naphthalenyl
2-furanyl2-furanyl
2-naphthalenyl2-naphthalenyl
3-thienyl3-thienyl
2,5-di-Me-3-furanyl2,5-diMe-3-furanyl
2,5-di-Me-3-thienyl2,5-diMe-3-thienyl
4-Me-pho-4-Me-pho-
2-Cl-pho-2-Cl-pho-
2,6-二甲基苯氧基2,6-diMe-Pho-
3-Me-PhS-4-CN-PhS-
PhNH-4-Me-PhNH-
BzlCl
Etn-hex
sec-BuMe
c-prc-hex
顺式-2-甲基环庚烷基 CF3CH2CH2
sec-BuS-n-BuO
CF3CH2O Cl(CH2)5O
5-Me-2-thienyl4- Me-3-furanyl
5-Me-2-pyridyl2- Me-3-pyridyl
R1,R2,R3和R4=H; R1和R2=H;R3=4-Me;
Y=CH R4=Me;Y=N
EE
4-pyridyl4-Cl-3-pyridyl
2-indanyl2-indanyl
2-tetrahydronaphthalenyl2-tetrahydronaphthalenyl
R1,R2,R3和R4=H; R1和R4=Me;R3=4-Me;
Y is CH R2=H;Y=N
EE
1-naphthalenyl1-naphthalenyl
2-furanyl2-furanyl
3-thienyl3-thienyl
3-pyridyl3-pyridyl
表9
R7=H;R3=Me;R4=Me
R1R5R6R1R5R6
HHHHH4-F
HFHHF4-F
HClHHCl4-F
HMeHHMe4-F
H CF3CH2O H H CF3CH2O 4-F
H CF3H H CF34-F
HMeOHHMeO4-F
HH4-ClMeHH
MeF5-FMeFH
MeCl5-ClMeClH
MeMe4-FMeMeH
Me CF3CH2O 4-F Me CF3CH2O H
Me CF34-F Me CF3H
MeMeO4-FMeMeOH
H H 3-CF3Et H H
HF6-FEtFH
HCl6-ClEtClH
HMe6-MeEtMeH
R7=H;R3=Me;R4=Me
R1R5R6R1R5R6
H CF3CH2O 6-Me Et CF3CH2O H
H CF36-Me Et CF3H
HMeO6-MeOEtMeOH
HH4-Bri-PrHH
MeF6-Fi-PrFH
MeCl6-Cli-PrClH
MeMe6-Mei-PrMeH
n-Pr CF3CH2O H i-Pr CF3CH2O H
t-Bu CF3H i-Pr CF3H
sec-BuMeOHi-PrMeOH
H HCF2O H H HCF2O 6-HCF2O
HBrHHIH
Ht-BuOHHEtOH
R1=H;R3和R4=Me R1=H;R3和R4=Me
R5R6R7R5R6R7
H4-Cl5-ClCl4-Cl6-Cl
H4-F6-sec-BuCl4-Cl6-MeO
H4-Et5-ICl3-Me4-Cl
H 3-F 6-CF3CH2O Cl 3-CF35-CF3
H 4-Me 6-CF3CF2Cl 4-MeO 5-t-BuO
H4-Br6-n-BuOCl3-n-Bu4-Me
Me4-Me6-MeTMSHH
Me4-F6-MeTMSH4-F
Me4-t-Bu6-t-BuTMSH6-Me
Me 4-CF36-Cl TMS H 6-MeO
Me3-Me5-BrTMSH6-Cl
Me 5-i-Pr 6-MeO TMS H 6-HCF2O
R1=H;R3和R4=Me R1,R3和R4=Me
R5R6R7R5R6R7
t-Bu6-t-BuHBr6-BrH
t-Bu 4-t-BuO H NMe2H H
t-BuHHCONHEtHH
CF3(CH2)3O H H CN H H
CF3(CF2)2H H 4-F-Ph H H
(CF3)2CH H H 2-Me-Ph H H
sec-BuS H H NO26-Me H
MeS6-MeSH4-Me-PhOHH
EtS4-FHPhSHH
MeS(O) H H CO2H 3-MeO H
i-Prs(O) H H CO2H H H
t-BuS(O)2H H HC≡C H H
MeS(O)2H H MeC≡C H H
CH2=CH H H MeC≡CCH2O 4-F H
CH2=C(CH3)CH2H H t-BuO H H
CH2=CHCH2O H H n-PrO H H
MeOCH2CH2H H EtO 5-EtO H
MeO2C H H Ac H H
MeOCH2O H H sec-BuCO H H
R4=Me;R6和R7=H R1,R6和R7=H
R1R3R5R3R4R5
Hc-PrHc-Prc-PrH
Hc-PrFc-Prc-PrF
Hc-PrClc-Prc-PrCl
Hc-PrMec-Prc-PrMe
H c-Pr CF3CH2O c-Pr CH3C≡C CF3CH2O
H c-Pr CF3c-Pr CH3C≡C CF3
R4=Me;R6和R7=H R1,R6和R7=H
R1R3R5R3R4R5
H c-Pr MeO c-Pr CH3C≡C MeO
Me MeC≡C H c-Pr CF3H
Me MeC≡C F c-Pr CF3F
Me MeC≡C Cl c-Pr CF3Cl
Me MeC≡C Me c-Pr CH3OCH2Me
Me MeC≡C CF3CH2O c-Pr CF3CH2O CF3CH2O
Me Cl CF3c-Pr MeS CF3
Me CF2Cl MeO c-Pr CH2=C(Et) MeO
i-Pr CF3H c-Pr CH2=CHCH2H
i-Prsec-BuFc-Prt-BuOF
i-Pr CF3Cl c-Pr HCF2O Cl
i-Pr CF3Me c-Pr CH2=CHCH2O Me
i-Pr CF3CF3CH2O c-Pr MeC≡CCH2O CF3CH2O
i-Pr Et CF3c-Pr NMe2CF3
i-PrMeOMeOc-PrNHEtMeO
Etc-PrHClClH
EtMeC≡CFClClF
Et CH2F Cl Cl Cl Cl
Et CF3CH2O Me Cl Cl Me
Et i-Pr CF3CH2O CH3C≡C Cl CF3CH2O
Et n-Bu CF3CH3C≡C F CF3
Et HC≡CCH2O MeO CH3C≡C CH3OCH2MeO
t-Bu Br Cl OCF3sec-Bu Cl
Ph CF3(CF2)3Me OCF3Br Me
Bzl sec-BuS CF3CH2O OCF3i-Pr CF3CH2O
表10
R7=H;R3=Me;R4=Me
R1R5R6R1R5R6
HHHHH4-F
HFHHF4-F
HClHHCl4-F
HMeHHMe4-F
H CF3CH2O H H CF3CH2O 4-F
H CF3H H CF34-F
HMeOHHMeO4-F
HH4-ClMeHH
MeF5-FMeFH
MeCl5-ClMeClH
MeMe4-FMeMeH
Me CF3CH2O 4-F Me CF3CH2O H
Me CF34-F Me CF3H
MeMeO4-FMeMeOH
H H 3-CF3Et H H
HF6-FEtFH
HCl6-ClEtClH
HMe6-MeEtMeH
R7=H;R3=Me;R4=Me
R1R5R6R1R5R6
H CF3CH2O 6-Me Et CF3CH2O H
H CF36-Me Et CF3H
HMeO6-MeOEtMeOH
HH4-Bri-PrHH
MeF6-Fi-PrFH
MeCl6-Cli-PrClH
MeMe6-Mei-PrMeH
n-Pr CF3CH2O H i-Pr CF3CH2O H
t-Bu CF3H i-Pr CF3H
sec-BuMeOHi-PrMeOH
H HCF2O H H HCF2O 6-HCF2O
HBrHHIH
Ht-BuOHHEtOH
R7=H;R3=Me;R4=H
R1R5R6R1R5R6
HHHHH4-F
HFHHF4-F
HClHHCl4-F
HMeHHMe4-F
H CF3CH2O H H CF3CH2O 4-F
H CF3H H CF34-F
HMeOHHMeO4-F
HH4-ClMeHH
MeF5-FMeFH
MeCl5-ClMeClH
MeMe4-FMeMeH
Me CF3CH2O 4-F Me CF3CH2O H
Me CF34-F Me CF3H
MeMeO4-FMeMeOH
R7=H;R3=Me;R4=H
R1R5R6R1R5R6
H H 3-CF3Et H H
HF6-FEtFH
HCl6-ClEtClH
HMe6-MeEtMeH
H CF3CH2O 6-Me Et CF3CH2O H
H CF36-Me Et CF3H
HMeO6-MeOEtMeOH
HH4-Bri-PrHH
MeF6-Fi-PrFH
MeCl6-Cli-PrClH
MeMe6-Mei-PrMeH
n-Pr CF3CH2O H i-Pr CF3CH2O H
t-Bu CF3H i-Pr CF3H
sec-BuMeOHi-PrMeOH
H HCF2O H H HCF2O 6-HCF2O
HBrHHIH
Ht-BuOHHEtOH
R4=Me;R6和R7=H R1,R6和R7=H
R1R3R5R3R4R5
Hc-PrHc-Prc-PrH
Hc-PrFc-Prc-PrF
Hc-PrClc-Prc-PrCl
Hc-PrMec-Prc-PrMe
H c-Pr CF3CH2O c-Pr CH3C≡C CF3CH2O
H c-Pr CF3c-Pr CH3C≡C CF3
R4=Me;R6和R7=H R1,R6和R7=H
R1R3R5R3R4R5
H c-Pr MeO c-Pr CH3C≡C MeO
Me MeC≡C H c-Pr CF3H
Me MeC≡C F c-Pr CF3F
Me MeC≡C Cl c-Pr CF3Cl
Me MeC≡C Me c-Pr CH3OCH2Me
Me MeC≡C CF3CH2O c-Pr CF3CH2O CF3CH2O
Me Cl CF3c-Pr MeS CF3
Me CF2Cl MeO c-Pr CH2=C(Et) MeO
i-Pr CF3H c-Pr CH2=CHCH2H
i-Prsec-BuFc-Prt-BuOF
i-Pr CF3Cl c-Pr HCF2O Cl
i-Pr CF3Me c-Pr CH2=CHCH2O Me
i-Pr CF3CF3CH2O c-Pr MeC≡CCH2O CF3CH2O
i-Pr Et CF3c-Pr NMe2CF3
i-PrMeOMeOc-PrNHEtMeO
Etc-PrHClClH
EtMeC≡CFClClF
Et CH2F Cl Cl Cl Cl
Et CF3CH2O Me Cl Cl Me
Et i-Pr CF3CH2O CH3C≡C Cl CF3CH2O
Et n-Bu CF3CH3C≡C F CF3
Et HC≡CCH2O MeO CH3C≡C CH3OCH2MeO
t-Bu Br Cl OCF3sec-Bu Cl
Ph CF3(CF2)3Me OCF3Br Me
Bzl sec-BuS CF3CH2O OCF3i-Pr CF3CH2O
表11
R3=4-Me;R4=Me;Y=N R3=H;R4=Me;Y=CH
R1R2E R1R2E
H4-MePhH4-EtPh
H4-i-Pr2-Me-PhH4-sec-Bu2-Me-Ph
H 4-n-Bu 2-Cl-Ph H 4-CF3(CF2)32-Cl-Ph
H4-CN2-MeO-PhH4-t-Bu2-MeO-Ph
H 4-CF32-CF3CH2O-Ph H 4-FCH22-CF3CH2O-Ph
H 4-CF3CH21-naphthalenyl H 4-n-Pr 1-naphthalenyl
i-Pr4-MePhMe5-MePh
i-Pr4-Me2-Me-PhMe5-Me2-Me-Ph
i-Pr4-Me2-Cl-PhMe5-Me2-Cl-Ph
i-Pr4-Me2-MeO-PhMe5-Me2-MeO-Ph
i-Pr 4-Me 2-CF3CH2O-Ph Me 5-Me 2-CF3CH2O-Ph
ClHPhBrHPh
FH2-Me-PhCNH2-Me-Ph
CF3CF2H 2-Cl-Ph Ac H 2-Cl-Ph
R3=4-Me;R4=Me;Y=N R3=H;R4=Me;Y=CH
R1R2E R1R2E
CH2=CHCH2H 2-MeO-Ph CH3C≡CCH2H 2-MeO-Ph
CO2Me H 2-CF3CH2O-Ph CO2Et H 2-CF3CH2O-Ph
2-Me-PhHMe4-Cl-PhHPh
BzlHPh5-Me-3-furylHi-Pr
2-naphthalenylHn-BuEtCOH2-Cl-Ph
3-thienyl H CF3CF22-furyl 5-Me CF3
3-pyridylHMePh4-MeMe
CN4-MePhCN5-MePh
t-Bu4-Me2-Me-Pht-Bu5-Me2-Me-Ph
ClCH24-Me 2-Cl-Ph FCH25-Me 2-Cl-Ph
Et4-Me2-MeO-PhEt5-Me2-MeO-Ph
n-Pr 4-Me 2-CF3CH2O-Ph Cl(CH2)45-Me 2-CF3CH2O-Ph
Me 5-Me 2-CF3-Ph Me 5-Me 2-CF3-Ph
i-Pr 5-Me 2-CF3-Ph i-Pr 4-CN 2-CF3-Ph
CF35-CF32-CF3-Ph CF34-Me 2-CF3-Ph
Me5-Me2-TMS-Phi-Pr5-Me2-TMS-Ph
表12
R7=H;R3=Me;R4=Me;n=1
R1R5R6R1R5R6
HHHHH4-F
HFHHF4-F
HClHHCl4-F
HMeHHMe4-F
H CF3CH2O H H CF3CH2O 4-F
H CF3H H CF34-F
HMeOHHMeO4-F
HH4-ClMeHH
MeF5-FMeFH
MeCl5-ClMeClH
MeMe4-FMeMeH
Me CF3CH2O 4-F Me CF3CH2O H
Me CF34-F Me CF3H
MeMeO4-FMeMeOH
H H 3-CF3Et H H
HF6-FEtFH
HCl6-ClEtClH
HMe6-MeEtMeH
H CF3CH2O 6-Me Et CF3CH2O H
R7=H;R3=Me;R4=Me;n=1
R1R5R6R1R5R6
H CF36-Me Et CF3H
HMeO6-MeOEtMeOH
HH4-Bri-PrHH
MeF6-Fi-PrFH
MeCl6-Cli-PrClH
MeMe6-Mei-PrMeH
n-Pr CF3CH2O H i-Pr CF3CH2O H
t-Bu CF3H i-Pr CF3H
sec-BuMeOHi-PrMeOH
H HCF2O H H i-Pr H
HBrHHIH
Ht-BuOHHEtOH
R7=H;R3=Me;R4=H;n=1
R1R5R6R1R5R6
HHHHH4-F
HFHHF4-F
HClHHCl4-F
HMeHHMe4-F
H CF3CH2O H H CF3CH2O 4-F
H CF3H H CF34-F
HMeOHHMeO4-F
HH4-ClMeHH
MeF5-FMeFH
MeCl5-ClMeClH
MeMe4-FMeMeH
Me CF3CH2O 4-F Me CF3CH2O H
Me CF34-F Me CF3H
MeMeO4-FMeMeOH
R7=H;R3=Me;R4=H;n=1
R1R5R6R1R5R6
H H 3-CF3Et H H
HF6-FEtFH
HCl6-ClEtClH
HMe6-MeEtMeH
H CF3CH2O 6-Me Et CF3CH2O H
H CF36-Me Et CF3H
HMeO6-MeOEtMeOH
HH4-Bri-PrHH
MeF6-Fi-PrFH
MeCl6-Cli-PrClH
MeMe6-Mei-PrMeH
n-Pr CF3CH2O H i-Pr CF3CH2O H
t-Bu CF3H i-Pr CF3H
sec-BuMeOHi-PrMeOH
H NO26-Cl Me CN 6-CN
H Br 6-Br Me MeS(O)24-F
H HCF2O 4-MeO Me i-Pr H
R4=Me;R6和R7=H; R1,R6和R7=H;
n=1n=1
R1R3R5R3R4R5
Hc-PrHc-Prc-PrH
Hc-PrFc-Prc-PrF
Hc-PrClc-Prc-PrCl
Hc-PrMec-Prc-PrMe
H c-Pr CF3CH2O c-Pr CH3C≡C CF3CH2O
H c-Pr CF3c-Pr CH3C≡C CF3
R4=Me;R6和R7=H; R1,R6和R7=H;
n=1n=1
R1R3R5R3R4R5
H c-Pr MeO c-Pr CH3C≡C MeO
Me MeC≡C H c-Pr CF3H
Me MeC≡C F c-Pr CF3F
Me MeC≡C Cl c-Pr CF3Cl
Me MeC≡C Me c-Pr CH3OCH2Me
Me MeC≡C CF3CH2O c-Pr CF3CH2O CF3CH2O
Me Cl CF3c-Pr MeS CF3
Me CF2Cl MeO c-Pr CH2=C(Et) MeO
i-Pr CF3H c-Pr CH2=CHCH2H
i-Prsec-BuFc-Prt-BuOF
i-Pr CF3Cl c-Pr HCF2O Cl
i-Pr CF3Me c-Pr CH2=CHCH2O Me
i-Pr CF3CF3CH2O c-Pr MeC≡CCH2O CF3CH2O
i-Pr Et CF3c-Pr NMe2CF3
i-PrMeOMeOc-PrNHEtMeO
Etc-PrHClClH
EtMeC≡CFClClF
Et CH2F Cl Cl Cl Cl
Et CF3CH2O Me Cl Cl Me
Et i-Pr CF3CH2O CH3C≡C Cl CF3CH2O
Et n-Bu CF3CH3C≡C F CF3
Et HC≡CCH2O MeO CH3C≡C CH3OCH2MeO
t-Bu Br Cl OCF3sec-Bu Cl
Ph CF3(CF2)3Me OCF3Br Me
Bzl sec-BuS CF3CH2O OCF3i-Pr CF3CH2O
表13
R7=H;R3=Me;R4=Me
R1R5R6R1R5R6
HHHHH4-F
HFHHF4-F
HClHHCl4-F
HMeHHMe4-F
H CF3CH2O H H CF3CH2O 4-F
H CF3H H CF34-F
HMeOHHMeO4-F
HH4-ClMeHH
MeF5-FMeFH
MeCl5-ClMeClH
MeMe4-FMeMeH
Me CF3CH2O 4-F Me CF3CH2O H
Me CF34-F Me CF3H
MeMeO4-FMeMeOH
H H 3-CF3Et H H
HF6-FEtFH
HCl6-ClEtClH
HMe6-MeEtMeH
H CF3CH2O 6-Me Et CF3CH2O H
R7=H;R3=Me;R4=Me
R1R5R6R1R5R6
H CF36-Me Et CF3H
HMeO6-MeOEtMeOH
HH4-Bri-PrHH
MeF6-Fi-PrFH
MeCl6-Cli-PrClH
MeMe6-Mei-PrMeH
n-Pr CF3CH2O H i-Pr CF3CH2O H
t-Bu CF3H i-Pr CF3H
sec-BuMeOHi-PrMeOH
H HCF2O H H HCF2O 6-HCF2O
HBrHHIH
Ht-BuOHHEtOH
R7=H;R3=Me;R4=H
R1R5R6R1R5R6
HHHHH4-F
HFHHF4-F
HClHHCl4-F
HMeHHMe4-F
H CF3CH2O H H CF3CH2O 4-F
H CF3H H CF34-F
HMeOHHMeO4-F
HH4-ClMeHH
MeF5-FMeFH
MeCl5-ClMeClH
MeMe4-FMeMeH
Me CF3CH2O 4-F Me CF3CH2O H
Me CF34-F Me CF3H
MeMeO4-FMeMeOH
R7=H;R3=Me;R4=H
R1R5R6R1R5R6
H H 3-CF3Et H H
HF6-FEtFH
HCl6-ClEtClH
HMe6-MeEtMeH
H CF3CH2O 6-Me Et CF3CH2O H
H CF36-Me Et CF3H
HMeO6-MeOEtMeOH
HH4-Bri-PrHH
MeF6-Fi-PrFH
MeCl6-Cli-PrClH
MeMe6-Mei-PrMeH
n-Pr CF3CH2O H i-Pr CF3CH2O H
t-Bu CF3H i-Pr CF3H
sec-BuMeOHi-PrMeOH
H HCF2O H H HCF2O 6-HCF2O
HBrHHIH
Ht-BuOHHEtOH
R4=Me;R6和R7=H; R1,R6和R7=H;
R1R3R5R3R4R5
Hc-PrHc-Prc-PrH
Hc-PrFc-Prc-PrF
Hc-PrClc-Prc-PrCl
Hc-PrMec-Prc-PrMe
H c-Pr CF3CH2O c-Pr CH3C≡C CF3CH2O
H c-Pr CF3c-Pr CH3C≡C CF3
R4=Me;R6和R7=H R1,R6和R7=H
R1R3R5R3R4R5
H c-Pr MeO c-Pr CH3C≡C MeO
Me MeC≡C H c-Pr CF3H
Me MeC≡C F c-Pr CF3F
Me MeC≡C Cl c-Pr CF3Cl
Me MeC≡C Me c-Pr CH3OCH2Me
Me MeC≡C CF3CH2O c-Pr CF3CH2O CF3CH2O
Me Cl CF3c-Pr MeS CF3
Me CF2Cl MeO c-Pr CH2=C(Et) MeO
i-Pr CF3H c-Pr CH2=CHCH2H
i-Prsec-BuFc-Prt-BuOF
i-Pr CF3Cl c-Pr HCF2O Cl
i-Pr CF3Me c-Pr CH2=CHCH2O Me
i-Pr CF3CF3CH2O c-Pr MeC≡CCH2O CF3CH2O
i-Pr Et CF3c-Pr NMe2CF3
i-PrMeOMeOc-PrNHEtMeO
Etc-PrHClClH
EtMeC≡CFClClF
Et CH2F Cl Cl Cl Cl
Et CF3CH2O Me Cl Cl Me
Et i-Pr CF3CH2O CH3C≡C Cl CF3CH2O
Et n-Bu CF3CH3C≡C F CF3
Et HC≡CCH2O MeO CH3C≡C CH3OCH2MeO
t-Bu Br Cl OCF3sec-Bu Cl
Ph CF3(CF2)3Me OCF3Br Me
Bzl sec-BuS CF3CH2O OCF3i-Pr CF3CH2O
表14
R3和R4=Me;R10=H
E R8R9E R8R9
HHHHH4-F
HFHHF4-F
HClHHCl4-F
HMeHHMe4-F
H CF3CH2O H H CF3CH2O 4-F
H CF3H H CF34-F
HMeOHHMeO4-F
HH4-ClMeHH
MeF5-FMeFH
MeCl5-ClMeClH
MeMe4-FMeMeH
Me CF3CH2O 4-F Me CF3CH2O H
Me CF34-F Me CF3H
MeMeO4-FMeMeOH
H H 3-CF3Et H H
HF6-FEtFH
HCl6-ClEtClH
HMe6-MeEtMeH
H CF3CH2O 6-Me Et CF3CH2O H
R3和R4=Me;R10=H
E R8R9E R8R9
H CF36-Me Et CF3H
HMeO6-MeOEtMeOH
HH4-Bri-PrHH
MeF6-Fi-PrFH
MeCl6-Cli-PrClH
MeMe6-Mei-PrMeH
n-Pr CF3CH2O H i-Pr CF3CH2O H
t-Bu CF3H i-Pr CF3H
sec-BuMeOHi-PrMeOH
Ph HCF2O H H HCF2O 6-HCF2O
HBrHHIH
Ht-BuOHHEtOH
R3=Me;R4和R10=H
E R8R9E R8R9
HHHHH4-F
HFHHF4-F
HClHHCl4-F
HMeHHMe4-F
H CF3CH2O H H CF3CH2O 4-F
H CF3H H CF34-F
HMeOHHMeO4-F
HH4-ClMeHH
MeF5-FMeFH
MeCl5-ClMeClH
MeMe4-FMeMeH
Me CF3CH2O 4-F Me CF3CH2O H
Me CF34-F Me CF3H
MeMeO4-FMeMeOH
R3=Me;R4和R10=H
E R8R9E R8R9
H H 3-CF3Et H H
HF6-FEtFH
HCl6-ClEtClH
HMe6-MeEtMeH
H CF3CH2O 6-Me Et CF3CH2O H
H CF36-Me Et CF3H
HMeO6-MeOEtMeOH
HH4-Bri-PrHH
MeF6-Fi-PrFH
MeCl6-Cli-PrClH
MeMe6-Mei-PrMeH
n-Pr CF3CH2O H i-Pr CF3CH2O H
t-Bu CF3H i-Pr CF3H
sec-BuMeOHi-PrMeOH
Ph HCF2O 4-MeO H HCF2O 6-HCF2O
HBrHPhIH
Ht-BuOHHEtOH
R4=Me;R9和R10=H R9和R10=H;E=Me
E R3R8R3R4R8
Hc-PrHc-Prc-PrH
Hc-PrFc-Prc-PrF
Hc-PrClc-Prc-PrCl
Hc-PrMec-Prc-PrMe
H c-Pr CF3CH2O c-Pr CH3C≡C CF3CH2O
H c-Pr CF3c-Pr CH3C≡C CF3
R4=Me;R9和R10=H R9和R10=H;E=Me
E R3R8R3R4R8
H c-Pr MeO c-Pr CH3C≡C MeO
Me MeC≡C H c-Pr CF3H
Me MeC≡C F c-Pr CF3F
Me MeC≡C Cl c-Pr CF3Cl
Me MeC≡C Me c-Pr CH3OCH2Me
Me MeC≡C CF3CH2O c-Pr CF3CH2O CF3CH2O
Me Cl CF3c-Pr MeS CF3
Me CF2Cl MeO c-Pr CH2=C(Et) MeO
i-Pr CF3H c-Pr CH2=CHCH2H
i-Prsec-BuFc-Prt-BuOF
i-Pr CF3Cl c-Pr HCF2O Cl
i-Pr CF3Me c-Pr CH2=CHCH2O Me
i-Pr CF3CF3CH2O c-Pr MeC≡CCH2O CF3CH2O
i-Pr Et CF3c-Pr NMe2CF3
i-PrMeOMeOc-PrNHEtMeO
Etc-PrHClClH
EtMeC≡CFClClF
Et CH2F Cl Cl Cl Cl
Et CF3CH2O Me Cl Cl Me
Et i-Pr CF3CH2O CH3C≡C Cl CF3CH2O
Et n-Bu CF3CH3C≡C F CF3
Et HC≡CCH2O MeO CH3C≡C CH3OCH2MeO
t-Bu Br Cl OCF3sec-Bu Cl
Ph CF3(CF2)3Me OCF3Br Me
Bzl sec-BuS CF3CH2O OCF3i-Pr CF3CH2O
表15
R3=Me;R4=Me R3=H;R4=Me
R1R2E R1R2E
HMePhHEtPh
Hi-Pr2-Me-PhHsec-Bu2-Me-Ph
H n-Bu 2-Cl-Ph H CF3(CF2)32-Cl-Ph
HCN2-MeO-PhHt-Bu2-MeO-Ph
H CF3CF3CH2O-Ph H FCH22-CF3CH2O-Ph
H CF3CH21-naphthalenyl H n-Pr 1-naphthalenyl
i-PrMePhMeMePh
i-PrMe2-Me-PhMeMe2-Me-Ph
i-PrMe2-Cl-PhMeMe2-Cl-Ph
i-PrMe2-MeO-PhMeMe2-MeO-Ph
i-Pr Me 2-CF3CH2O-Ph Me Me 2-CF3CH2O-Ph
ClHPhBrHPh
FH2-Me-PhCNH2-Me-Ph
CF3CF2H 2-Cl-Ph Ac H 2-Cl-Ph
R3=Me;R4=Me R3=H;R4=Me
R1R2E R1R2E
CH2=CHCH2H 2-MeO-Ph CH3C≡CCH2H 2-MeO-Ph
CO2Me H 2-CF3CH2O-Ph CO2Et H 2-CF3CH2O-Ph
2-Me-PhHMe4-Cl-PhHPh
BzlHPh5-Me-3-furylHPh
2-naphthalenylHn-BuEtCOHi-Pr
3-thienyl H CF3CF22-furyl H 2-Cl-Ph
3-pyridyl H Me Ph Me CF3
PhMeHPhMeH
2-Me-PhMeH2-Me-PhMeH
2-Cl-PhMeH2-Cl-PhMeH
2-MeO-PhMeH2-MeO-PhMeH
2-CF3CH2O-Ph Me H 2-CF3CH2O-Ph Me H
PhMen-PrPhi-PrMe
Ph Me CF3Ph CF3Me
PhMei-PrPhEtMe
PhMesec-BuPhn-BuMe
表16
R3和R4=Me;Y=N R3=H;R4=Me;Y=CH
R1R2E R1R2E
HMePhHEtPh
Hi-Pr2-Me-PhHsec-Bu2-Me-Ph
H n-Bu 2-Cl-Ph H CF3(CF2)32-Cl-Ph
HCN2-MeO-PhHt-Bu2-MeO-Ph
H CF3CF3CH2O-Ph H FCH22-CF3CH2O-Ph
H CF3CH21-naphthalenyl H n-Pr 1-naphthalenyl
i-PrMePhMeMePh
i-PrMe2-Me-PhMeMe2-Me-Ph
i-PrMe2-Cl-PhMeMe2-Cl-Ph
i-PrMe2-MeO-PhMeMe2-MeO-Ph
i-Pr Me 2-CF3CH2O-Ph Me Me 2-CF3CH2O-Ph
ClHPhBrHPh
FH2-Me-PhCNH2-Me-Ph
CF3CF2H 2-Cl-Ph Ac H 2-Cl-Ph
R3和R4=Me;Y=N R3=H;R4=Me;Y=CH
R1R2E R1R2E
CH2=CHCH2H 2-MeO-Ph CH3C≡CCH2H 2-MeO-Ph
CO2Me H 2-CF3CH2O-Ph CO2Et H 2-CF3CH2O-Ph
2-Me-PhHMe4-Cl-PhHPh
BzlHPh5-Me-3-furylHi-Pr
2-naphthalenylHn-BuEtCOH2-Cl-Ph
3-thienyl H CF3CF22-furyl H CF3
3-pyridylHMePhMeMe
PhMeHPhMeH
2-Me-PhMeH2-Me-PhMeH
2-Cl-PhMeH2-Cl-PhMeH
2-MeO-PhMeH2-MeO-PhMeH
2-CF3CH2O-Ph Me H 2-CF3CH2O-Ph Me H
PhMen-PrPhi-PrMe
Ph Me CF3Ph CF3Me
PhMei-PrPhEtMe
PhMesec-BuPhn-BuMe
表17
R3和R4=Me;R7=H
R1R5R6R1R5R6
HHHHH4-F
HFHHF4-F
HClHHCl4-F
HMeHHMe4-F
H CF3CH2O H H CF3CH2O 4-F
H CF3H H CF34-F
HMeOHHMeO4-F
HH4-ClMeHH
MeF5-FMeFH
MeCl5-ClMeClH
MeMe4-FMeMeH
Me CF3CH2O 4-F Me CF3CH2O H
Me CF34-F Me CF3H
MeMeO4-FMeMeOH
H H 3-CF3Et H H
HF6-FEtFH
HCl6-ClEtClH
HMe6-MeEtMeH
H CF3CH2O 6-Me Et CF3CH2O H
R3和R4=Me;R7=H
R1R5R6R1R5R6
H CF36-Me Et CF3H
HMeO6-MeOEtMeOH
HH4-Bri-PrHH
MeF6-Fi-PrFH
MeCl6-Cli-PrClH
MeMe6-Mei-PrMeH
n-Pr CF3CH2O H i-Pr CF3CH2O H
t-Bu CF3H i-Pr CF3H
sec-BuMeOHi-PrMeOH
H HCF2O H H HCF2O 6-HCF2O
HBrHHIH
Ht-BuOHHEtOH
R3=Me;R4和R7=H
R1R5R6R1R5R6
HHHHH4-F
HFHHF4-F
HClHHCl4-F
HMeHHMe4-F
H CF3CH2O H H CF3CH2O 4-F
H CF3H H CF34-F
HMeOHHMeO4-F
HH4-ClMeHH
MeF5-FMeFH
MeCl5-ClMeClH
MeMe4-FMeMeH
Me CF3CH2O 4-F Me CF3CH2O H
Me CF34-F Me CF3H
MeMeO4-FMeMeOH
R3=Me;R4和R7=H
R1R5R6R1R5R6
H H 3-CF3Et H H
HF6-FEtFH
HCl6-ClEtClH
HMe6-MeEtMeH
H CF3CH2O 6-Me Et CF3CH2O H
H CF36-Me Et CF3H
HMeO6-MeOEtMeOH
HH4-Bri-PrHH
MeF6-Fi-PrFH
MeCl6-Cli-PrClH
MeMe6-Mei-PrMeH
n-Pr CF3CH2O H i-Pr CF3CH2O H
t-Bu CF3H i-Pr CF3H
sec-BuMeOHi-PrMeOH
H HCF2O H H HCF2O 6-HCF2O
HBrHHIH
Ht-BuOHHEtOH
R4=Me;R6和R7=H R1,R6和R7=H
R1R3R5R3R4R5
Hc-PrHc-Prc-PrH
Hc-PrFc-Prc-PrF
Hc-PrClc-Prc-PrCl
Hc-PrMec-Prc-PrMe
H c-Pr CF3CH2O c-Pr CH3C≡C CF3CH2O
H c-Pr CF3c-Pr CH3C≡C CF3
R4=Me;R6和R7=H R1,R6和R7=H
R1R3R5R3R4R5
H c-Pr MeO c-Pr CH3C≡C MeO
Me MeC≡C H c-Pr CF3H
Me MeC≡C F c-Pr CF3F
Me MeC≡C Cl c-Pr CF3Cl
Me MeC≡C Me c-Pr CH3OCH2Me
Me MeC≡C CF3CH2O c-Pr CF3CH2O CF3CH2O
Me Cl CF3c-Pr MeS CF3
Me CF2Cl MeO c-Pr CH2=C(Et) MeO
i-Pr CF3H c-Pr CH2=CHCH2H
i-Prsec-BuFc-Prt-BuOF
i-Pr CF3Cl c-Pr HCF2O Cl
i-Pr CF3Me c-Pr CH2=CHCH2O Me
i-Pr CF3CF3CH2O c-Pr MeC≡CCH2O CF3CH2O
i-Pr Et CF3c-Pr NMe2CF3
i-PrMeOMeOc-PrNHEtMeO
Etc-PrHClClH
EtMeC≡CFClClF
Et CH2F Cl Cl Cl Cl
Et CF3CH2O Me Cl Cl Me
Et i-Pr CF3CH2O CH3C≡C Cl CF3CH2O
Et n-Bu CF3CH3C≡C F CF3
Et HC≡CCH2O MeO CH3C≡C CH3OCH2MeO
t-Bu Br Cl OCF3sec-Bu Cl
Ph CF3(CF2)3Me OCF3Br Me
Bzl sec-BuS CF3CH2O OCF3i-Pr CF3CH2O
表18
R3和R4=Me;Y=N R3=H;R4=Me;Y=CH
R1R2E R1R2E
HMePhHEtPh
Hi-Pr2-Me-PhHsec-Bu2-Me-Ph
H n-Bu 2-Cl-Ph H CF3(CF2)32-Cl-Ph
HCN2-MeO-PhHt-Bu2-MeO-Ph
H CF3CF3CH2O-Ph H FCH22-CF3CH2O-Ph
H CF3CH21-naphthalenyl H n-Pr 1-naphthalenyl
i-PrMePhMeMePh
i-PrMe2-Me-PhMeMe2-Me-Ph
i-PrMe2-Cl-PhMeMe2-Cl-Ph
i-PrMe2-MeO-PhMeMe2-MeO-Ph
i-Pr Me 2-CF3CH2O-Ph Me Me 2-CF3CH2O-Ph
ClHPhBrHPh
FH2-Me-PhCNH2-Me-Ph
CF3CF2H 2-Cl-Ph Ac H 2-Cl-Ph
R3和R4=Me;Y=N R3=H;R4=Me;Y=CH
R1R2E R1R2E
CH2=CHCH2H 2-MeO-Ph CH3C≡CCH2H 2-MeO-Ph
CO2Me H 2-CF3CH2O-Ph CO2Et H 2-CF3CH2O-Ph
2-Me-PhHMe4-Cl-PhHPh
BzlHPh5-Me-3-furylHPh
2-naphthalenylHn-BuEtCOHi-Pr
3-thienyl H CF3CF22-furyl H 2-Cl-Ph
3-pyridyl H Me Ph Me CF3
PhMeHPhMePh
2-Me-PhMeH2-Me-PhMeH
2-Cl-PhMeH2-Cl-PhMeH
2-MeO-PhMeH2-MeO-PhMeH
2-CF3CH2O-Ph Me H 2-CF3CH2O-Ph Me H
PhMen-PrPhi-PrMe
Ph Me CF3Ph CF3Me
PhMei-PrPhEtMe
PhMesec-BuPhn-BuMe
表19
R3=Me R3=Me;R4和R18一起
形成-(CH2)3-
R1R4R18R5R6R7R1R5R6R7
HOHn-BuClHHHClHH
HOHn-PrMeHHHMeHH
HOHEtMeMeHHEtHH
MeOHn-BuClH2-ClMei-PrHH
EtOHn-BuHMeOHEtHMeH
HPhHClHHHClH2-Cl
HPhHMeHHHMeMeH
HPhHMeMeHHEtEtH
MePhHClH2-ClMeMeMeH
EtPhHHMeOHEtMeHH
H TMS-CH2H Cl H H H F H H
H TMS-CH2H Me H H H H Br H
H TMS-CH2H Me Me H H MeO H H
Me TMS-CH2H Cl H 2-Cl Me H MeO H
Et TMS-CH2H H MeO H Et Cl H H
R3=Me R3=Me;R4和R18一起
形成-(CH2)3-
R1R4R18R5R6R7R1R5R6R7
HMeClMeMeHHHClH
H Me Br Cl H H H H CF3H
HMeClClHHHHFH
MeMeBrFHHMeHClH
Et Me Cl CF3H H
R3=Me R3=Me;R4和R18一起形成 -(CH2)4-
R1R5R6R7R1R5R6R7
HClHHHMeOMeOH
HMeHHMeMeOH2-MeO
HEtHHEtFHH
Me i-Pr H H H CF3H H
Et H Me H H CF3CH2O H H
H Cl H 2-Cl H HCF2O H H
HMeMeHMeEtOHH
HEtEtHEtHEtOH
MeMeMeHHHClH
Et Me H H H H CF3H
HMeOHHHHFH
HHMeOHMeHClH
表20
R3=Me R3=Me;R4和R18一起
R1R4R18R5R6R7形成-(CH2)3-
H OH n-Bu Cl H H R1R5R6R7
HOHn-PrMeHHHClHH
HOHEtMeMeHHMeHH
MeOHn-BuClH2-ClHEtHH
EtOHn-BuHMeOHMei-PrHH
HPhHClHHEtHMeH
HPhHMeHHHClH2-Cl
HPhHMeMeHHMeMeH
MePhHClH2-ClHEtEtH
EtPhHHMeOHMeMeMeH
H TMS-CH2H Cl H H Et Me H H
H TMS-CH2H Me H H H F H H
H TMS-CH2H Me Me H H H Br H
Me TMS-CH2H Cl H 2-Cl H MeO H H
Et TMS-CH2H H MeO H Me H MeO H
R3=Me R3=Me;R4和R18一起
形成-(CH2)3-
R1R4R18R5R6R7R1R5R6R7
HMeClMeMeHEtClHH
HMeBrClHHHHClH
H Me Cl Cl H H H H CF3H
MeMeBrFHHHHFH
Et Me Cl CF3H H Me H Cl H
R3=Me R3=Me;R4和R18一起形成 -(CH2)4-
R1R5R6R7R1R5R6R7
HClHHMeEtOHH
HMeHHEtHEtOH
HEtHHHHClH
Me i-Pr H H H H CF3H
EtHMeHHHFH
HClH2-ClHMeOMeOH
HMeMeHMeMeOH2-MeO
HEtEtHEtFHH
Me Me Me H H CF3H H
Et Me H H H CF3CH2O H H
H MeO H H H HCF2O H H
HHMeOHMeHClH
表21
R7=H;R3=Me;R4=6-Me
R1R5R6R1R5R6
HHHHH4-F
HFHHF4-F
HClHHCl4-F
HMeHHMe4-F
H CF3CH2O H H CF3CH2O 4-F
H CF3H H CF34-F
HMeOHHMeO4-F
HH4-ClMeHH
MeF5-FMeFH
MeCl5-ClMeClH
MeMe4-FMeMeH
Me CF3CH2O 4-F Me CF3CH2O H
Me CF34-F Me CF3H
MeMeO4-FMeMeOH
H H 3-CF3Et H H
HF6-FEtFH
HCl6-ClEtClH
HMe6-MeEtMeH
R7=H;R3=Me;R4=6-Me
R1R5R6R1R5R6
H CF3CH2O 6-Me Et CF3CH2O H
H CF36-Me Et CF3H
HMeO6-MeOEtMeOH
HH4-Bri-PrHH
MeF6-Fi-PrFH
MeCl6-Cli-PrClH
MeMe6-Mei-PrMeH
n-Pr CF3CH2O H i-Pr CF3CH2O H
t-Bu CF3H i-Pr CF3H
sec-BuMeOHi-PrMeOH
H HCF2O H H HCF2O 6-HCF2O
HBrHHIH
Ht-BuOHHEtOH
H H 4-NMe2Me H 4-NEt2
HH4-piperidinoMeH4-吡咯烷基
R7=H;R3=Me;R4=H
R1R5R6R1R5R6
HHHHH4-F
HFHHF4-F
HClHHCl4-F
HMeHHMe4-F
H CF3CH2O H H CF3CH2O 4-F
H CF3H H CF34-F
HMeOHHMeO4-F
HH4-ClMeHH
MeF5-FMeFH
MeCl5-ClMeClH
MeMe4-FMeMeH
Me CF3CH2O 4-F Me CF3CH2O H
Me CF34-F Me CF3H
MeMeO4-FMeMeOH
R7=H;R3=Me;R4=H
R1R5R6R1R5R6
H H 3-CF3Et H H
HF6-FEtFH
HCl6-ClEtClH
HMe6-MeEtMeH
H CF3CH2O 6-Me Et CF3CH2O H
H CF36-Me Et CF3H
HMeO6-MeOEtMeOH
HH4-Bri-PrHH
MeF6-Fi-PrFH
MeCl6-Cli-PrClH
MeMe6-Mei-PrMeH
n-Pr CF3CH2O H i-Pr CF3CH2O H
t-Bu CF3H i-Pr CF3H
sec-BuMeOHi-PrMeOH
H NO26-Cl Me CN 6-CN
H Br 6-Br Me MeS(O)24-F
H HCF2O 4-MeO Me i-Pr H
R7=H;R3=H;R4=H
R1R5R6R1R5R6
HHHHH4-F
HFHHF4-F
HClHHCl4-F
HMeHHMe4-F
H CF3CH2O H H CF3CH2O 4-F
H CF3H H CF34-F
HMeOHHMeO4-F
HH4-ClMeHH
HF5-FMeFH
HCl5-ClMeClH
HMe4-FMeMeH
R7=H;R3=H;R4=H
R1R5R6R1R5R6
Me CF3CH2O 4-F Me CF3CH2O H
Me CF34-F Me CF3H
MeMeO4-FMeMeOH
H H 3-CF3Et H H
HF6-FEtFH
HCl6-ClEtClH
HMe6-MeEtMeH
H CF3CH2O 6-Me Et CF3CH2O H
Me CF36-Me Et CF3H
MeMeO6-MeOEtMeOH
HH4-Bri-PrHH
HF6-Fi-PrFH
HCl6-Cli-PrClH
HMe6-Mei-PrMeH
n-Pr CF3CH2O H i-Pr CF3CH2O H
t-Bu CF3H i-Pr CF3H
sec-BuMeOHi-PrMeOH
Met-Bu4-MeOHTMS6-Me
Mei-PrOHHTMS4-F
Me CF3CF2CF2H H TMS 5-CF3
R1=H;R3=Et;R4=H R1,R3=Et;R4=H
R5R6R7R5R6R7
H4-Cl5-ClCl4-Cl6-Cl
H4-F6-sec-BuCl4-Cl6-MeO
H4-Et5-ICl3-Me4-Cl
H 3-F 6-CF3CH2O Cl 3-CF35-CF3
H 4-Me 6-CF3CF2Cl 4-MeO 5-t-BuO
H4-Br6-n-BuOCl3-n-Bu4-Me
R1=H;R3=Et;R4=H R1,R3=Et;R4=H
R5R6R7R5R6R7
Me4-Me6-MeTMSHH
Me4-F6-MeTMSH4-F
Me4-t-Bu6-t-BuTMSH6-Me
Me 4-CF36-Cl TMS H 6-MeO
Me3-Me5-BrTMSH6-Cl
Me 5-i-Pr 6-MeO TMS H 6-HCF2O
t-Bu6-t-BuHBr6-BrH
t-Bu 4-t-BuO H NMe2H H
t-BuHHCONHEtHH
CF3(CH2)3O H H CN H H
CF3(CF2)2H H 4-F-Ph H H
(CF3)2CH H H 2-MePh H H
sec-BuS H H NO26-Me H
MeS6-MeSH4-Me-PhOHH
EtS4-FHPhSHH
MeS(O) H H CO2H 3-MeO H
i-PrS(O) H H CO2H H H
t-BuS(O)2H H HC≡C H H
MeS(O)2H H MeC≡C H H
CH2=CH H H MeC≡CCH2O 4-F H
CH2=C(CH3)CH2H H t-BuO H H
CH2=CHCH2O H H n-PrO H H
MeOCH2CH2H H EtO 5-EtO H
MeO2C H H Ac H H
MeOCH2O H H sec-BuCO H H
表22
R1,R2和R4=H;R3=Me R1和R2=H;R3=Me;R4=6-Me
EE
1-naphthalenyl1-naphthalenyl
2-furanyl2-furanyl
2-naphthalenyl2-naphthalenyl
3-thienyl3-thienyl
2,5-di-Me-3-furanyl2,5-diMe-3-furanyl
2,5-di-Me-3-thienyl2,5-diMe-3-thienyl
4-Me-pho-4-Me-pho-
2-Cl-pho-2-Cl-pho-
2,6-二甲基苯氧基2,6-diMe-Pho-
3-Me-PhS-4-CN-PhS-
PhNH-4-Me-PhNH-
BzlCl
Etn-hex
sec-BuMe
c-prc-hex
顺式-2-甲基环庚烷基 CF3CH2CH2
sec-BuS-n-BuO
CF3CH2O Cl(CH2)5O
5-Me-2-thienyl4- Me-3-furanyl
5-Me-2-pyridyl2- Me-3-pyridyl
R1,R2和R4=H; R1和R2=H;R3=Me;
R3=Me R4=6-Me
EE
2-indanyl2-indanyl
2-四氢naphthalenyl2-四氢naphthalenyl
R1,R2,R3=R4=H R1和R3=Me;R2=R4
=H;
EE
1-naphthalenyl1-naphthalenyl
2-furanyl2-furanyl
3-thienyl3-thienyl
3-pyridyl3-pyridyl
R3=Me;R4=H R3=Et;R4=H
R1R2E R1R2E
H5-MePhH5-EtPh
H5-i-Pr2-Me-PhH5-sec-Bu2-Me-Ph
H 5-n-Bu 2-Cl-Ph H 5-CF3(CF2)32-Cl-Ph
H5-CN2-MeO-PhH5-t-Bu2-MeO-Ph
H 5-CF3CF3CH2O-Ph H 5-FCH22-CF3CH2O-Ph
H 5-CF3CH21-naphthalenyl H 5-n-Pr 1-naphthalenyl
i-Pr5-MePhMe4-MePh
i-Pr5-Me2-Me-PhMe4-Me2-Me-Ph
i-Pr5-Me2-Cl-PhMe4-Me2-Cl-Ph
i-Pr5-Me2-MeO-PhMe4-Me2-MeO-Ph
R3=Me;R4=H
R1R2E
i-Pr 5-Me 2-CF3CH2O-Ph
ClHPh
FH2-Me-Ph
CF3CF2H 2-Cl-Ph
CH2=CHCH2H 2-MeO-Ph
CO2Me H 2-CF3CH2O-Ph
2-Me-PhHMe
BzlHPh
2-naphthalenylHn-Bu
3-thienyl H CF3CF2
3-pyridylHMe
CN5-MePh
t-Bu5-Me2-Me-Ph
ClCH25-Me 2-Cl-Ph
Et5-Me2-MeO-Ph
n-Pr 5-Me 2-CF3CH2O-Ph
Me 4-Me 2-CF3-Ph
i-Pr 4-Me 2-CF3-Ph
CF34-CF32-CF3-Ph
Me4-Me2-TMS-Ph
H5-OHPh
H5-MeO4-Me-Ph
H5-OC(O)Me4-Cl-Ph
H5-OC(O)NHMePh
R3=Me;R4=Me
R1R2E
i-Pr5-Me2-Cl-Ph
i-Pr5-Me2-MeO-Ph
i-Pr 6-Me 2-CF3CH2O-Ph
ClHPh
FH4-Me-Ph
CF3CF2H 4-Cl-Ph
CH2=CHCH2H 4-MeO-Ph
R3=Me;R4=H
R1R2E
CO2Me H 2-CF3CH2O-Ph
2-Me-PhHMe
BzlHPh
2-naphthalenylHn-Bu
3-thienyl H CF3CF2
3-pyridylHMe
CN5-MePh
t-Bu5-Me2-Me-Ph
ClCH25-Me 2-Cl-Ph
Et5-Me2-MeO-Ph
n-Pr 6-Me 2-CF3CH2O-Ph
Me 4-Me 2-CF3-Ph
i-Pr 4-Me 2-CF3-Ph
CF34-CF32-CF3-Ph
R3=Et;R4=H
R1R2E
Me4-Me2-TMS-Ph
Me4-Me2-Cl-Ph
Me4-Me2-MeO-Ph
Me 4-Me 2-CF3CH2O-Ph
BrHPh
CNH4-Me-Ph
AcH4-Cl-Ph
CH3C≡CCH2H 4-MeO-Ph
R3=4-Me;R4=Me
R1R2E
CO2Et H 2-CF3CH2O-Ph
4-Cl-PhHPh
5-Me-3-furylHi-Pr
EtCOH2-Cl-Ph
2-furyl 4-Me CF3
Ph5-MeMe
CN4-MePh
t-Bu4-Me2-Me-Ph
FCH24-Me 2-Cl-Ph
Et4-Me2-MeO-Ph
Cl(CH2)44-Me 2-CF3CH2O-Ph
Me 4-Me 2-CF3-Ph
i-Pr 5-CN 2-CF3-Ph
CF35-Me 2-CF3-Ph
i-Pr4-Me2-TMS-Ph
表23
R7=H;R3=H;R4=Me
R1R5R6R1R5R6
HHHHH4-F
HFHHF4-F
HClHHCl4-F
HMeHHMe4-F
H CF3CH2O H H CF3CH2O 4-F
H CF3H H CF34-F
HMeOHHMeO4-F
HH4-ClMeHH
MeF5-FMeFH
MeCl5-ClMeClH
MeMe4-FMeMeH
Me CF3CH2O 4-F Me CF3CH2O H
Me CF34-F Me CF3H
MeMeO4-FMeMeOH
H H 3-CF3Et H H
HF6-FEtFH
HCl6-ClEtClH
HMe6-MeEtMeH
R7=H;R3=H;R4=Me
R1R5R6R1R5R6
H CF3CH2O 6-Me Et CF3CH2O H
H CF36-Me Et CF3H
HMeO6-MeOEtMeOH
HH4-Bri-PrHH
MeF6-Fi-PrFH
MeCl6-Cli-PrClH
MeMe6-Mei-PrMeH
n-Pr CF3CH2O H i-Pr CF3CH2O H
t-Bu CF3H i-Pr CF3H
sec-BuMeOHi-PrMeOH
H HCF2O H H HCF2O 6-HCF2O
HBrHHIH
Ht-BuOHHEtOH
表24
R3=H;R4=Me;R10=H
E R8R9E R8R9
HHHHH4-F
HFHHF4-F
HClHHCl4-F
HMeHHMe4-F
H CF3CH2O H H CF3CH2O 4-F
H CF3H H CF34-F
HMeOHHMeO4-F
HH4-ClMeHH
MeF5-FMeFH
MeCl5-ClMeClH
MeMe4-FMeMeH
Me CF3CH2O 4-F Me CF3CH2O H
Me CF34-F Me CF3H
MeMeO4-FMeMeOH
H H 3-CF3Et H H
HF6-FEtFH
HCl6-ClEtClH
HMe6-MeEtMeH
R3=H;R4=Me;R10=H
E R8R9E R8R9
H CF3CH2O 6-Me Et CF3CH2O H
H CF36-Me Et CF3H
HMeO6-MeOEtMeOH
HH4-Bri-PrHH
MeF6-Fi-PrFH
MeCl6-Cli-PrClH
MeMe6-Mei-PrMeH
n-Pr CF3CH2O H i-Pr CF3CH2O H
t-Bu CF3H i-Pr CF3H
sec-BuMeOHi-PrMeOH
Ph HCF2O H H HCF2O 6-HCF2O
HBrHPhIH
Ht-BuOHHEtOH
R4=Et;R3和R10=H
E R8R9E R8R9
HHHHH4-F
HFHHF4-F
HClHHCl4-F
HMeHHMe4-F
H CF3CH2O H H CF3CH2O 4-F
H CF3H H CF34-F
HMeOHHMeO4-F
HH4-ClMeHH
MeF5-FMeFH
MeCl5-ClMeClH
MeMe4-FMeMeH
Me CF3CH2O 4-F Me CF3CH2O H
Me CF34-F Me CF3H
MeMeO4-FMeMeOH
R4=Et;R3和R10=H
E R8R9E R8R9
H H 3-CF3Et H H
HF6-FEtFH
HCl6-ClEtClH
HMe6-MeEtMeH
H CF3CH2O 6-Me Et CF3CH2O H
H CF36-Me Et CF3H
HMeO6-MeOEtMeOH
HH4-Bri-PrHH
MeF6-Fi-PrFH
MeCl6-Cli-PrClH
MeMe6-Mei-PrMeH
n-Pr CF3CH2O H i-Pr CF3CH2O H
t-Bu CF3H i-Pr CF3H
sec-BuMeOHi-PrMeOH
Ph HCF2O 4-MeO H HCF2O 6-HCF2O
HBrHPhIH
Ht-BuOHHEtOH
表25
R3=H;R4=Et R3=H;R4=Me
R1R2E R1R2E
HMePhHEtPh
Hi-Pr2-Me-PhHsec-Bu2-Me-Ph
H n-Bu 2-Cl-Ph H CF3(CF2)32-Cl-Ph
HCN2-MeO-PhHt-Bu2-MeO-Ph
H CF3CF3CH2O-Ph H FCH22-CF3CH2O-Ph
H CF3CH21-naphthalenyl H n-Pr 1-naphthalenyl
i-PrMePhMeMePh
i-PrMe2-Me-PhMeMe2-Me-Ph
i-PrMe2-Cl-PhMeMe2-Cl-Ph
i-PrMe2-MeO-PhMeMe2-MeO-Ph
i-Pr Me 2-CF3CH2O-Ph Me Me 2-CF3CH2O-Ph
ClHPhBrHPh
FH2-Me-PhCNH2-Me-Ph
CF3CF2H 2-Cl-Ph Ac H 2-Cl-Ph
R3=H;R4=Et R3=H;R4=Me
R1R2E R1R2E
CH2=CHCH2H 2-MeO-Ph CH3C≡CCH2H 2-MeO-Ph
CO2Me H 2-CF3CH2O-Ph CO2Et H 2-CF3CH2O-Ph
2-Me-PhHMe4-Cl-PhHPh
BzlHPh5-Me-3-furylHPh
2-naphthalenylHn-BuEtCOHi-Pr
3-thienyl H CF3CF22-furyl H 2-Cl-Ph
3-pyridyl H Me Ph Me CF3
PhMeHPhMeH
2-Me-PhMeH2-Me-PhMeH
2-Cl-PhMeH2-Cl-PhMeH
2-MeO-PhMeH2-MeO-PhMeH
2-CF3CH2O-Ph Me H 2-CF3CH2O-Ph Me H
PhMen-PrPhi-PrMe
Ph Me CF3Ph CF3Me
PhMei-PrPhEtMe
PhMesec-BuPhn-BuMe
表26
R2,R4和R7=H;R3=Me
R1R5R6R1R5R6
HHHMe4-MeH
H 4-NMe2H Me 4-Et H
H4-MeHMe4-i-PrH
H4-EtHMe4-ClH
H4-n-PrHMe4-MeOH
H4-i-PrHMe4-EtOH
H 4-n-Bu H Me 4-CF3H
H4-sec-BuHEtHH
H 4-i-Bu H H 3-NMe2H
H4-t-BuHH3-MeH
H4-ClHH3-EtH
H4-BrHH3-n-PrH
H4-FHH3-i-PrH
H4-OHHH3-n-BuH
H4-MeOHH3-ClH
H4-EtOHH3-BrH
H 4-CF3H H 3-F H
H 4-CF3CH2O H H 3-OH H
MeHHH3-MeOH
R2,R4和R7=H;R3=Me
R1R5R6R1R5R6
H3-EtOHH3-Me4-Me
H 3-CF3H H 2-Et 4-Et
H 3-CF3CH2O H H 2-Et 5-Et
Me3-MeHH3-Et4-Et
Me3-EtHH2-Me5-t-Bu
Me3-i-PrHH2-Cl4-Cl
Me3-ClHH2-Cl5-Cl
Me3-MeOHEt3-MeOH
Me3-EtOHEt3-EtOH
Me 3-CF3H Et 3-CF3H
Et3-MeHMe2-Me4-Me
Et3-EtHMe2-Me5-Me
Et3-i-PrHMe3-Me4-Me
Et3-ClHMe2-Et4-Et
Et4-MeHMe2-Et5-Et
Et4-EtHMe3-Et4-Et
Et4-i-PrHMe2-Me5-t-Bu
Et4-ClHEt2-Me4-Me
Et4-MeOHEt2-Me5-Me
Et4-EtOHEt3-Me4-Me
Et 4-CF3H Et 2-Et 4-Et
H2-MeHEt2-Et5-Et
H2-EtHEt3-Et4-Et
H2-ClHH4-PhH
H2-FHH4-PhOH
H2-OHHH4-c-HexH
Me2-MeHH4-HexH
Me2-ClHH4-n-AmylH
Me2-FHMe4-PhH
Et2-MeHMe4-PhOH
Et2-ClHMe4-c-HexH
Et2-FHMe4-HexH
H2-Me4-MeMe4-n-AmylH
H2-Me5-MeMe4-PhH
R2,R4和R7=H;R3=Me
R1R5R6R1R5R6
Me 4-PhO H Et 3-NMe2H
Me 4-c-Hex H H 3-NH2H
Me 4-n-Amyl H H 4-NH2H
Me 3-Cl 4-Cl Me 3-NH2H
Me 2-Cl 4-Cl Me 4-NH2H
Me 2-Cl 5-Cl Et 3-NH2H
Me 3-Cl 4-Cl Et 4-NH2H
Et 2-Cl 4-Cl n-Pr 4-NMe2H
Et2-Cl5-Cln-Pr4-MeH
Et3-Cl4-Cln-Pr4-EtH
H2-MeO4-MeOn-Pr4-n-PrH
H3-MeO5-MeOn-Pr4-ClH
H3-MeO4-MeOn-Pr4-FH
Me2-MeO4-MeOn-Pr4-BrH
Me3-MeO5-MeOn-Pr4-MeOH
Me3-MeO4-MeOn-Pr4-EtOH
Et 2-MeO 4-MeO n-Pr 4-CF3H
Et 3-MeO 5-MeO n-Pr 4-CF3CH2O H
Et 3-MeO 4-MeO n-Pr 3-NMe2H
H3-Br5-Brn-Pr3-MeH
Me3-Br5-Brn-Pr3-EtH
Et3-Br5-Brn-Pr3-n-PrH
H3-Me5-Men-Pr3-ClH
Me3-Me5-Men-Pr3-FH
Et3-Me5-Men-Pr3-BrH
H3-Cl4-MeOn-Pr3-MeOH
Me3-Cl4-MeOn-Pr3-EtOH
Et 3-Cl 4-MeO n-Pr 3-CF3H
Me 4-NMe2H n-Pr 3-CF3CH2O H
Me 3-NMe2H n-Pr 3-Me 4-Me
Et 4-NMe2H n-Pr 3-Me 5-Me
R2,R4和R7=H;R3=Me
R1R5R6R1R5R6
n-Pr3-Cl4-Cli-Pr4-ClH
n-Pr3-MeO4-MeOi-Pr4-FH
n-Pr3-MeO5-MeOi-Pr4-BrH
n-PrHHi-Pr4-MeOH
n-BuHHi-Pr4-EtOH
n-Bu 4-Me H i-Pr 4-CF3H
n-Bu 4-Et H i-Pr 4-CF3CH2O H
n-Bu4-n-PrHi-Pr3-Me4-Me
n-Bu4-i-PrHi-Pr3-Me5-Me
n-Bu4-ClHi-Pr3-Cl4-Cl
n-Bu4-FHi-Pr3-MeO4-MeO
n-Bu4-BrHi-Pr3-MeO5-MeO
n-Bu4-MeOHH4-TMSH
n-Bu4-EtOHH4-IH
n-Bu 4-CF3H H 4-t-BuO H
n-Bu 4-CF3CH2O H H 4-CF3(CH2)3O H
n-Bu 3-Me H H 4-CF3(CF2)2H
n-Bu 3-Et H H 4-(CF3)2CH H
n-Bu 3-n-Pr H H 4-CH3CHClCH H
n-Bu3-ClHMe4-TMSH
n-Bu3-FHMe4-IH
n-Bu3-MeOHMe4-t-BuOH
n-Bu 3-EtO H Me 4-CF3(CH2)3O H
n-Bu 3-CF3H H 4-MeS H
n-Bu 3-CF3CH2O H H 4-EtS H
i-PrHHH4-MeS(O)H
i-Pr4-MeHH4-i-PrS(O)H
i-Pr 4-Et H H 4-MeS(O)2H
i-Pr 4-n-Pr H H 4-CH2=CH H
i-Pr 4-i-Pr H H 4-CH2=C(CH3)CH2H
R2,R4和R7=H,R3=Et
R1R5R6R1R5R6
H 4-CH2=CHCH2O H H 3-Me H
H 4-MeOCH2CH2H H 3-Et H
H 4-MeOCH2O H H 3-n-Pr H
HHHH3-i-PrH
H 4-NMe2H H 3-n-Bu H
H4-MeHH3-ClH
H4-EtHH3-BrH
H4-n-PrHH3-FH
H4-i-PrHH3-OHH
H4-n-BuHH3-MeOH
H4-sec-BuHH3-EtOH
H 4-i-Bu H H 3-CF3H
H 4-t-Bu H H 3-CF3CH2O H
H4-ClHMe3-MeH
H4-BrHMe3-EtH
H4-FHMe3-i-PrH
H4-OHHMe3-ClH
H4-MeOHMe3-MeOH
H4-EtOHMe3-EtOH
H 4-CF3H Me 3-CF3H
H 4-CF3CH2O H Et 3-Me H
MeHHEt3-EtH
Me4-MeHEt3-i-PrH
Me4-EtHEt3-ClH
Me4-i-PrHEt4-MeH
Me4-ClHEt4-EtH
Me4-MeOHEt4-i-PrH
Me4-EtOHEt4-ClH
Me 4-CF3H Et 4-MeO H
EtHHEt4-EtOH
H 3-NMe2H Et 4-CF3H
R2,R4和R7=H;R3=Et
R1R5R6R1R5R6
H2-MeHEt3-Me4-Me
H2-EtHEt2-Et4-Et
H2-ClHEt2-Et5-Et
H2-FHEt3-Et4-Et
H2-OHHH4-PhH
Me2-MeHH4-PhOH
Me2-ClHH4-c-HexH
Me2-FHH4-HexH
Et2-MeHH4-n-戊基H
Et2-ClHMe4-PhH
Et2-FHMe4-PhOH
H2-Me4-MeMe4-c-HexH
H2-Me5-MeMe4-HexH
H3-Me4-MeMe4-n-戊基H
H2-Et4-EtH3-Cl4-Cl
H2-Et5-EtMe2-Cl4-Cl
H3-Et4-EtMe2-Cl5-Cl
H2-Me5-t-BuMe3-Cl4-Cl
H2-Cl4-ClEt2-Cl4-Cl
H2-Cl5-ClEt2-Cl5-Cl
Et3-MeOHEt3-Cl4-Cl
Et3-EtOHH2-MeO4-MeO
Et 3-CF3H H 3-MeO 5-MeO
Me2-Me4-MeH3-MeO4-MeO
Me2-Me5-MeMe2-MeO4-MeO
Me3-Me4-MeMe3-MeO5-MeO
Me2-Et4-EtMe3-MeO4-MeO
Me2-Et5-EtEt2-MeO4-MeO
Me3-Et4-EtEt3-MeO5-MeO
Me2-Me5-t-BuEt3-MeO4-MeO
Et2-Me4-MeH3-Br5-Br
Et2-Me5-MeMe3-Br5-Br
R2,R4和R7=H;R3=Et
R1R5R6R1R5R6
Et3-Br5-Brn-Pr3-n-PrH
H3-Me5-Men-Pr3-ClH
Me3-Me5-Men-Pr3-FH
Et3-Me5-Men-Pr3-BrH
H3-Cl4-MeOn-Pr3-MeOH
Me3-Cl4-MeOn-Pr3-EtOH
Et 3-Cl 4-MeO n-Pr 3-CF3H
Me 4-NMe2H n-Pr 3-CF3CH2O H
Me 3-NMe2H n-Pr 3-Me 4-Me
Et 4-NMe2H n-Pr 3-Me 5-Me
Et 3-NMe2H n-Pr 3-Cl 4-Cl
H 3-NH2H n-Pr 3-MeO 4-MeO
H 4-NH2H n-Pr 3-MeO 5-MeO
Me 3-NH2H n-Pr H H
Me 4-NH2H n-Bu H H
Et 3-NH2H n-Bu 4-Me H
Et 4-NH2H n-Bu 4-Et H
n-Pr 4-NMe2H n-Bu 4-n-Pr H
n-Pr4-MeHn-Bu4-i-PrH
n-Pr4-EtHn-Bu4-ClH
n-Pr4-n-PrHn-Bu4-FH
n-Pr4-ClHn-Bu4-BrH
n-Pr4-FHn-Bu4-MeOH
n-Pr4-BrHn-Bu4-EtOH
n-Pr 4-MeO H n-Bu 4-CF3H
n-Pr 4-EtO H n-Bu 4-CF3CH2O H
n-Pr 4-CF3H n-Bu 3-Me H
n-Pr 4-CF3CH2O H n-Bu 3-Et H
n-Pr 3-NMe2H n-Bu 3-n-Pr H
n-Pr3-MeHn-Bu3-ClH
n-Pr3-EtHn-Bu3-FH
R2,R4和R7=H;R3=Et
R1R5R6R1R5R6
n-Bu3-MeOHH4-TMSH
n-Bu3-EtOHH4-IH
n-Bu 3-CF3H H 4-t-BuO H
n-Bu 3-CF3CH2O H H 4-CF3(CH2)3O H
i-Pr H H H 4-CF3(CF2)2H
i-Pr 4-Me H H 4-(CF3)2CH H
i-Pr 4-Et H H 4-CH3CHClCH H
i-Pr4-n-PrHMe4-TMSH
i-Pr4-i-PrHMe4-IH
i-Pr4-ClHMe4-t-BuOH
i-Pr 4-F H Me 4-CF3(CH2)3O H
i-Pr4-BrHH4-MeSH
i-Pr4-MeOHH4-EtSH
i-Pr4-EtOHH4-MeS(O)H
i-Pr 4-CF3H H 4-i-PrS(O) H
i-Pr 4-CF3CH2O H H 4-MeS(O)2H
i-Pr 3-Me 4-Me H 4-CH2=CH H
i-Pr 3-Me 5-Me H 4-CH2=C(CH3)CH2H
i-Pr 3-Cl 4-Cl H 4-CH2=CHCH2O H
i-Pr 3-MeO 4-MeO H 4-MeOCH2CH2H
i-Pr 3-MeO 5-MeO H 4-MeOCH2O H
R2=H;R3=Me;R4=H R2=H;R3=Et;R4=H;
R1R5R6R7R1R5R6R7
H3-Me4-Me5-MeH3-Me4-Me5-Me
H3-Br4-Me5-BrH3-Br4-Me5-Br
H3-Cl4-MeO5-ClH3-Cl4-MeO5-Cl
H3-MeO4-MeO5-MeOH3-MeO4-MeO5-MeO
R2=H;R3=Me;R4=H R2=H;R3=Et;R4=H;
R1R5R6R7R1R5R6R7
Me3-Me4-Me5-MeMe3-Me4-Me5-Me
Me3-Br4-Me5-BrMe3-Br4-Me5-Br
Me3-Cl4-MeO5-ClMe3-Cl4-Me5-Cl
Me3-MeO6-MeO5-MeOMe3-MeO4-MeO5-MeO
H4-TMSHHH4-TMSHH
Me4-TMSHHMe4-TMSHH
Et4-TMSHHEt4-TMSHH
Et3-Me4-Me5-MeEt3-Me4-Me5-Me
Et3-MeO4-MeO5-MeOEt3-Me4-MeO5-MeO
H2-Cl5-BrHH2-Cl5-BrH
Me2-Cl5-BrHMe2-Cl5-BrH
R3=Me;R4=H;R7=H
R1R2R5R6R1R2R5R6
Me4-MeHHMe4-Me3-MeH
Me4-Me4-MeHMe4-Me3-ClH
Me4-Me4-ClHMe4-Me3-MeOH
Me4-Me4-MeOHMe4-Me3-EtOH
Me4-Me4-EtOHMe4-Me3-EtH
Me4-Me4-EtHMe4-Me3-i-PrH
Me4-Me4-i-PrHMe4-EtHH
R3=Me;R4=H;R7=H
R1R2R5R6R1R2R5R6
Me4-Et4-MeHMe4-Me3-MeO5-MeO
Me4-Et4-ClHH6-OHHH
Me4-Et4-MeOHH6-OMeHH
Me4-Et4-EtOHH6-OEtHH
Me4-Et4-EtHH6-OC(O)MeHH
Me4-Et4-i-PrHH5-OHHH
Me4-Et3-MeHH5-OMeHH
Me4-Et3-ClHH5-OEtHH
Me4-Et3-MeOHH5-BrHH
Me4-Et3-EtOHH5-MeHH
Me4-Et3-EtHH6-MeHH
Me4-Et3-i-PrHH6-OH4-MeH
Et4-EtHHH6-OMe3-MeH
Et4-Et4-MeHH6-OMe3-Me4-Me
Et4-Et4-ClHH6-OEt4-ClH
Et4-Et4-MeOHH5-OMe4-FH
Et4-Et4-EtOHH5-OMe3-ClH
Et4-Et4-EtHH5-OMe4-ClH
Et4-Et4-i-PrHH5-Br4-ClH
Me4-Me3-Me4-MeMe6-OHHH
Me4-Me3-Me5-MeMe6-OMeHH
Me4-Me3-Cl4-ClMe4-n-PrHH
Me4-Me3-Cl5-ClEt4-n-PrHH
Me4-Me3-MeO4-MeO
表27
R1R3R5R6R7R23
HMeHHHH
HMeHHMeH
HMeHHEtH
HMeHHi-PrH
HMeHHClH
HMeHHOMeH
HMeHMeMeH
HMeHEtEtH
HMeHHMeH
HMeHHHC(O)OMe
HMeHHMeC(O)NHPh
HHHHHH
HHHHMeH
HHHHOMeH
HHHHEtC(O)OMe
HHHHClC(O)NHPh
HEtHHHH
HEtHHMeH
MeHHHHH
MeHHHMeH
MeHHHClH
MeHHHOMeH
R1R3R5R6R7R23
EtHHHHH
EtHHHMeH
EtHHHClH
EtHHHOMeH
i-PrHHHMeH
i-PrHHHClH
i-PrHHHOMeH
i-PrHHHHH
MeMeHHHH
MeMeHHMeH
MeMeHHClH
MeMeHHOMeH
EtMeHHMeH
EtMeHHClH
EtMeHHOMeH
i-PrMeHHMeH
i-PrMeHHClH
i-PrMeHHOMeH
HMe2-MeHHH
HMe2-ClHHH
EtMeHHHC(S)NHPh
EtMeHHHS(O)Ph
Et Me H H H S(O)2Me
Et Me H H H S(O)2NMe2
Et Me H H H P(O)(OEt)2
i-Pr Me H H H P(S)(OEt)2
i-PrMeHHHMe
i-Pr Me H H H CH2Ph
表28
R3和R4=Me
R1R5R6R7R23R1R5R6R7R23
HHMeHHMeHn-PrHH
HHEtHHMeHi-PrHH
HHi-PrHHMeHClHH
HHOMeHHMeHOMeHH
HHn-PrHHMe3-MeMeHH
HHClHHMe3-EtEtHH
H3-MeMeHHEtHHHH
H3-EtEtHHEtHMeHH
H2-EtEtHHEtHEtHH
H2-MeMeHHEt3-MeMeHH
H2-MeH5-MeHEtHClHH
H3-ClHHHEtHOMeHH
H3-MeHHHHHMeHC(O)OMe
H 3-CF3H H H H H Et H C(O)OMe
H3-OMeHHHHHi-PrHC(O)OMe
H2-MeHHHH3-MeMeHC(O)OMe
HHHHHMeHMeHC(O)NHPh
MeHHHHMeHEtHC(O)NHMe
MeHMeHHMe3-MeMeHC(O)NHPh
MeHEtHHMeHOMeHMe
R3=Me,R4=H
R1R5R6R7R23R1R5R6R7R23
HHMeHHMeHn-PrHH
HHEtHHMeHi-PrHH
HHi-PrHHMeHClHH
HHOMeHHMeHOMeHH
HHn-PrHHMe3-MeMeHH
HHClHHMe3-EtEtHH
H3-MeMeHHEtHHHH
H3-EtEtHHEtHMeHH
H2-EtEtHHEtHEtHH
H2-MeMeHHEt3-MeMeHH
H2-MeH5-MeHEtHClHH
H3-ClHHHEtHOMeHH
H3-MeHHHHHMeHC(O)OMe
H 3-CF3H H H H H Et H C(O)OMe
H3-OMeHHHHHi-PrHC(O)OMe
H2-MeHHHH3-MeMeHC(O)OMe
HHHHHMeHMeHC(O)NHPh
MeHHHHMeHEtHC(O)NHMe
MeHMeHHMe3-MeMeHC(O)NHPh
MeHEtHHMeHOMeHMe
R3=Me,R4=Et
R1R5R6R7R23R1R5R6R7R23
HHMeHHMeHn-PrHH
HHEtHHMeHi-PrHH
HHi-PrHHMeHClHH
HHOMeHHMeHOMeHH
HHn-PrHHMe3-MeMeHH
HHClHHMe3-EtEtHH
H3-MeMeHHEtHHHH
R3=Me,R4=Et
R1R5R6R7R23R1R5R6R7R23
H3-EtEtHHEtHMeHH
H2-EtEtHHEtHEtHH
H2-MeMeHHEt3-MeMeHH
H2-MeH5-MeHEtHClHH
H3-ClHHHEtHOMeHH
H3-MeHHHHHMeHC(O)OMe
H 3-CF3H H H H H Et H C(O)OMe
H3-OMeHHHHHi-PrHC(O)OMe
H2-MeHHHH3-MeMeHC(O)OMe
HHHHHMeHMeHC(O)NHPh
MeHHHHMeHEtHC(O)NHMe
MeHMeHHMe3-MeMeHC(O)NHPh
MeHEtHHMeHOMeHMe
表29
R1R5R6R23R1R5R6R23
HHHHMeHEtH
HHMeHMeHOMeH
HHEtHMeHClH
HHi-PrHHHH(CO)OMe
H3-MeMeHHHHC(O)NHPh
HHClHHHHMe
MeHHHMeHMeC(O)OMe
MeHMeHMeHEtC(O)NHPh
MeHMeC(O)NHMe
表30
R1R5R6MLmR1R5R6MLm
H H H ZnCl2Et H H MnCl2
H H H CuCl2i-Pr H H ZnCl2
H H H FeCl3i-Pr H H FeCl3
Me H H ZnCl2Me H Me ZnCl2
Me H H CuCl2Me H Me CuCl2
Me H H FeCl3Me H Me FeCl3
Me H H MnCl2i-Pr H Me MnCl2
Me H H MgCl2Et H Me MgCl2
Et H H ZnCl2H Me Me ZnCl2
Et H H CuCl2
表31
MLm=ZnCl2
R1R5R6R7R1R5R6R7
HHMeHMeHHH
HHEtHMeHMeH
HHi-PrHMeHEtH
HHOMeHMeHn-PrH
HHn-PrHMeHi-PrH
HHClHMeHClH
H3-MeMeHMeHOMeH
H3-EtEtHMe3-MeMeH
H2-EtEtHMe3-EtEtH
H2-MeMeHEtHHH
H2-MeH5-MeEtHMeH
H3-ClHHEtHEtH
H3-MeHHEt3-MeMeH
H 3-CF3H H Et H Cl H
H3-OMeHHEtHOMeH
H2-MeHHMe3-ClHH
HHHH
MLm=FeCl3
R1R5R6R7R1R5R6R7
HHMeHMeHHH
HHEtHMeHMeH
HHi-PrHMeHEtH
HHOMeHMeHn-PrH
HHn-PrHMeHi-PrH
HHClHMeHClH
H3-MeMeHMeHOMeH
H3-EtEtHMe3-MeMeH
H2-EtEtHMe3-EtEtH
H2-MeMeHEtHHH
H2-MeH5-MeEtHMeH
H3-ClHHEtHEtH
H3-MeHHEt3-MeMeH
H 3-CF3H H Et H Cl H
H3-OMeHHEtHOMeH
H2-MeHHMe3-ClHH
HHHH
MLm=CuCl2
R1R5R6R7R1R5R6R7
HHMeHMeHHH
HHEtHMeHMeH
HHi-PrHMeHEtH
HHOMeHMeHn-PrH
HHn-PrHMeHi-PrH
HHClHMeHClH
H3-MeMeHMeHOMeH
H3-EtEtHMe3-MeMeH
H2-EtEtHMe3-EtEtH
H2-MeMeHEtHHH
H2-MeH5-MeEtHMeH
H3-ClHHEtHEtH
MLm=CuCl2
R1R5R6R7R1R5R6R7
H3-MeHHEt3-MeMeH
H 3-CF3H H Et H Cl H
H3-OMeHHEtHOMeH
H2-MeHHMe3-ClHH
HHHH
MLm=MnCl2
R1R5R6R7R1R5R6R7
HHMeHHHHH
HHEtHMeHHH
HHi-PrHMeHMeH
HHOMeHMeHEtH
HHn-PrHMeHn-PrH
HHClHMeHi-PrH
H3-MeMeHMeHClH
H3-EtEtHMeHOMeH
H2-EtEtHMe3-MeMeH
H2-MeMeHMe3-EtEtH
H2-MeH5-MeEtHHH
H3-ClHHEtHMeH
H3-MeHHEtHEtH
H 3-CF3H H Et 3-Me Me H
H3-OMeHHEtHClH
H2-MeHHEtHOMeH
MLm=MgCl2
R1R5R6R7R1R5R6R7
HHMeHHHHH
HHEtHMeHHH
HHi-PrHMeHMeH
HHOMeHMeHEtH
HHn-PrHMeHn-PrH
HHClHMeHi-PrH
H3-MeMeHMeHClH
H3-EtEtHMeHOMeH
H2-EtEtHMe3-MeMeH
H2-MeMeHMe3-EtEtH
H2-MeH5-MeEtHHH
H3-ClHHEtHMeH
H3-MeHHEtHEtH
H 3-CF3H H Et 3-Me Me H
H3-OMeHHEtHClH
H2-MeHHEtHOMeH
表32
R1R5R6R7R1R5R6R7
H H H ZnCl2Me H H ZnCl2
H H Me FeCl3Me H Me CuCl2
H H Et CuCl2Me H Et MnCl2
H H i-Pr MnCl2Me H OMe MgCl2
H 3-Me Me MgCl2Me H Cl ZnCl2
H H Cl FeCl3
表33
R1=Me,R5=H,R6=H R1=H,R5=Me,R6=H
R23R23
MeMe
CH2Ph CH2Ph
CH2CH=CH2CH2CH=CH2
CH2C≡CH CH2C≡CH
C(=O)MeC(=O)Me
C(=O)PhC(=O)Ph
C(=O)OMeC(=O)OMe
C(=O)OPhC(=O)OPh
S(=O)MeS(=O)Me
C(=O)PhC(=O)Ph
S(=O)2Me S(=O)2Me
S(=O)2Ph S(=O)2Ph
C(=O)NHMeC(=O)NHMe
C(=O)NHPhC(=O)NHPh
C(=O)NMe2C(=O)NMe2
C(=S)NHMeC(=S)NHMe
C(=S)NHPhC(=S)NHPh
P(=S)(OEt)2P(=S)(OEt)2
P(=O)(OEt)2P(=O)(OEt)2
S(=O)2NEt2S(=O)2NEt2
R1=Me,R5=H,R6=Me R1=H,R5=Me,R6=Me
R23R23
MeMe
CH2Ph CH2Ph
CH2CH=CH2CH2CH=CH2
CH2C≡CH CH2C≡CH
C(=O)MeC(=O)Me
C(=O)PhC(=O)Ph
C(=O)OMeC(=O)OMe
C(=O)OPhC(=O)OPh
S(=O)MeS(=O)Me
C(=O)PhC(=O)Ph
S(=O)2Me S(=O)2Me
S(=O)2Ph S(=O)2Ph
C(=O)NHMeC(=O)NHMe
C(=O)NHPhC(=O)NHPh
C(=O)NMe2C(=O)NMe2
C(=S)NHMeC(=S)NHMe
C(=S)NHPhC(=S)NHPh
P(=S)(OEt)2P(=S)(OEt)2
P(=O)(OEt)2P(=O)(OEt)2
S(=O)2NEt2S(=O)2NEt2
R1=Me,R5=H,R6=OMe R1=Me,R5=Me,R6=Me
R23R23
MeMe
CH2Ph CH2Ph
CH2CH=CH2CH2CH=CH2
CH2C≡CH CH2C≡CH
C(=O)MeC(=O)Me
C(=O)PhC(=O)Ph
C(=O)OMeC(=O)OMe
R1=Me,R5=H,R6=OMe R1=Me,R5=Me,R6=Me
R23R23
C(=O)OPhC(=O)OPh
S(=O)MeS(=O)Me
C(=O)PhC(=O)Ph
S(=O)2Me S(=O)2Me
S(=O)2Ph S(=O)2Ph
C(=O)NHMeC(=O)NHMe
C(=O)NHPhC(=O)NHPh
C(=O)NMe2C(=O)NMe2
C(=S)NHMeC(=S)NHMe
C(=S)NHPhC(=S)NHPh
P(=S)(OEt)2P(=S)(OEt)2
P(=O)(OEt)2P(=O)(OEt)2
S(=O)2NEt2S(=O)2NEt2
R1=H,R5=Cl,R6=H R1=Et,R5=H,R6=H
R23R23
MeMe
CH2Ph CH2Ph
CH2CH=CH2CH2CH=CH2
CH2C≡CH CH2C≡CH
C(=O)MeC(=O)Me
C(=O)PhC(=O)Ph
C(=O)OMeC(=O)OMe
C(=O)OPhC(=O)OPh
S(=O)MeS(=O)Me
C(=O)PhC(=O)Ph
S(=O)2Me S(=O)2Me
S(=O)2Ph S(=O)2Ph
C(=O)NHMeC(=O)NHMe
R1=Et,R5=Cl,R6=H R1=H,R5=H,R6=H
R23R23
C(=O)NHPhC(=O)NHPh
C(=O)NMe2C(=O)NMe2
C(=S)NHMeC(=S)NHMe
C(=S)NHPhC(=S)NHPh
P(=S)(OEt)2P(=S)(OEt)2
P(=O)(OEt)2P(=O)(OEt)2
S(=O)2NEt2
R1=H,R5=H,R6=Me R1=H,R5=H,R6=OMe
R23R23
MeMe
CH2Ph CH2Ph
CH2CH=CH2CH2CH=CH2
CH2C≡CH CH2C≡CH
C(=O)MeC(=O)Me
C(=O)PhC(=O)Ph
C(=O)OMeC(=O)OMe
C(=O)OPhC(=O)OPh
S(=O)MeS(=O)Me
C(=O)PhC(=O)Ph
S(=O)2Me S(=O)2Me
S(=O)2Ph S(=O)2Ph
C(=O)NHMeC(=O)NHMe
C(=O)NHPhC(=O)NHPh
C(=O)NMe2C(=O)NMe2
C(=S)NHMe C(=O)NPh2
C(=S)NHPhC(=S)NHMe
P(=S)(OEt)2C(=S)NHPh
P(=O)(OEt)2P(=S)(OEt)2
S(=O)2NEt2P(=O)(OEt)2
S(=O)2NEt2
表34
R1,R2和R3=H;R4=6-Et R1和R2=H;R3=Me;R4=H
EE
1-naphthalenyl1-naphthalenyl
2-furanyl2-furanyl
2-naphthalenyl2-naphthalenyl
3-thienyl3-thienyl
2,5-di-Me-3-furanyl2,5-diMe-3-furanyl
2,5-di-Me-3-thienyl2,5-diMe-3-thienyl
4-Me-pho-4-Me-pho-
2-Cl-pho-2-Cl-pho-
2,6-二甲基苯氧基2,6-diMe-Pho-
3-Me-PhS-4-CN-PhS-
PhNH-4-Me-PhNH-
BzlCl
Etn-hex
sec-BuMe
c-prc-hex
顺式-2-甲基环庚烷基 CF3CH2CH2
sec-Bu-S-n-BuO
R1,R2和R3=H;R4=6-Et R1和R2=H;R3=Me;R4=H
EE
CF3CH2O Cl(CH2)5O
5-Me-2-thienyl4- Me-3-furanyl
5-Me-2-pyridyl2- Me-3-pyridyl
R1和R3=Me;R2=5-Me; R1和R3=Me;R2和R4=H;
R4=H
EE
5-Me-2-pyridyl2- Me-3-pyridyl
4-pyridyl4-Cl-3-pyridyl
2-indanyl2-indanyl
2-四氢naphthalenyl2-四氢naphthalenyl
6-Me-3-pyridyl6-Me-3-pyridyl
2-pyridyl2-pyridyl
1-naphthalenyl
R1,R2,R3和R4=H 2-furanyl
E3-thienyl
1-naphthalenyl3-pyridyl
2-furanyl
3-thienyl
3-pyridyl
R3=Me;R4=6-Me R3=Me;R4=6-Me
R1R2E R1R2E
H5-MePhH5-EtPh
H5-i-Pr2-Me-PhH5-sec-Bu2-Me-Ph
H 5-n-Bu 2-Cl-Ph H 5-CF3(CF2)32-Cl-Ph
H5-CN2-MeO-PhH5-t-Bu2-MeO-Ph
H 5-CF3CF3CH2O-Ph H 5-FCH22-CF3CH2O-Ph
H 5-CF3CH21-naphthalenyl H 5-n-Pr 1-naphthalenyl
i-Pr5-MePhMe4-MePh
i-Pr5-Me2-Me-PhMe4-Me2-Me-Ph
R3=Me;R4=6-Me
R1R2E
i-Pr5-Me2-Cl-Ph
i-Pr5-Me2-MeO-Ph
i-Pr 6-Me 2-CF3CH2O-Ph
ClHPh
FH4-Me-Ph
CF3CF2H 4-Cl-Ph
CH2=CHCH2H 4-MeO-Ph
R3=Me;R4=H
R1R2E
CO2Me H 2-CF3CH2O-Ph
2-Me-PhHMe
BzlHPh
2-naphthalenylHn-Bu
3-thienyl H CF3CF2
3-pyridylHMe
CN5-MePh
t-Bu5-Me2-Me-Ph
ClCH25-Me 2-Cl-Ph
Et5-Me2-MeO-Ph
n-Pr 5-Me 2-CF3CH2O-Ph
Me 4-Me 2-CF3-Ph
i-Pr 4-Me 2-CF3-Ph
CF34-CF32-CF3-Ph
R3=Et;R4=H
R1R2E
Me4-Me2-TMS-Ph
Me4-Me2-Cl-Ph
Me4-Me2-MeO-Ph
Me 4-Me 2-CF3CH2O-Ph
BrHPh
CNH4-Me-Ph
AcH4-Cl-Ph
CH3C≡CCH2H 4-MeO-Ph
R3=Me;R4=6-Me
R1R2E
CO2Et H 2-CF3CH2O-Ph
4-Cl-PhHPh
5-Me-3-furylHi-Pr
EtCOH2-Cl-Ph
2-furyl 4-Me CF3
Ph5-MeMe
CN4-MePh
t-Bu4-Me2-Me-Ph
FCH24-Me 2-Cl-Ph
Et4-Me2-MeO-Ph
Cl(CH2)44-Me 2-CF3CH2O-Ph
Me 4-Me 2-CF3-Ph
i-Pr 5-CN 2-CF3-Ph
CF35-Me 2-CF3-Ph
i-Pr4-Me2-TMS-Ph
表35
R5和R6=H R5=H,R6=Me R5=H,R6=MeO
R8R8R8
HHH
2-Me2-Me2-Me
2-Cl2-Cl2-Cl
2-Br2-Br2-Br
2-MeO2-MeO2-MeO
3-Me3-Me3-Me
3-Cl3-Cl3-Cl
3-Br3-Br3-Br
3-MeO3-MeO3-MeO
4-Me4-Me4-Me
4-Cl4-Cl4-Cl
4-Br4-Br4-Br
4-MeO4-MeO4-MeO
3-CF33-CF33-CF3
4-CF34-CF34-CF3
R5=3-Me,R6=Me R5=H,R6=Cl R5=2-Me,R6=H
R8R8R8
HHH
2-Me2-Me2-Me
2-Cl2-Cl2-Cl
R5=3-Me,R6=Me R5=H,R6=Cl R5=2-Me,R6=H
R8R8R8
2-Br2-Br2-Br
2-MeO2-MeO2-MeO
3-Me3-Me3-Me
3-Cl3-Cl3-Cl
3-Br3-Br3-Br
3-MeO3-MeO3-MeO
4-Me4-Me4-Me
4-Cl4-Cl4-Cl
4-Br4-Br4-Br
4-MeO4-MeO4-MeO
3-CF33-CF33-CF3
4-CF34-CF34-CF3
制剂
按常规方法可制备式Ⅰ-Ⅵ化合物的有用制剂,它们包括粉剂、粒剂、丸剂、溶液、混悬液、乳化液、可湿粉、可乳化浓缩物等。这些制剂有许多可以直接应用。可喷洒的制剂可扩散于适宜的介质中,以每公顷几升至几百升的喷洒量应用。高浓度组合物主要用作进一步制剂的中间物。所述制剂一般含有约0.1-99%(重量)的活性成分和至少下列一种成分(a)0.1-20%的表面活性剂和(b)约1-99.9%的惰性固体或液体稀释剂。更具体地讲,它们可含有下述成分,其大约比例如下
制剂重量百分数*
活性成分稀释剂表面活性剂
可湿粉20-900-741-10
油混悬液,乳化液,
溶液(包括可乳化浓缩物)3-5040-950-15
水混悬液10-5040-841-20
粉剂1-2570-990-5
粒剂和丸剂0.1-955-99.90-15
高浓度组合物90-990-100-2
*活性成分加上至少一种表面活性剂或稀释剂等于100%(重量)。
当然,根据用途和化合物的物理性质,活性成分存在的浓度可以更低或更高。表面活性剂与活性成分的较高比率有时是理想的,这可以通过将其掺入制剂或通过罐混合而完成。
典型的固体稀释剂参见下述文献Watkinsetal.,“HandbookofInsecticideDustDiluentsandCarriers”,2ndEd.,Dorland
Books,Caldwell,NewJersey。但也可采用开采的或制造的其它固体。对于可湿粉剂,优选的是吸收力较强的稀释剂,而对于粉剂,密度较大的稀释剂是优选的。典型的液体稀释剂和溶剂参见下述文献Marsden,“SolventsGuide”2ndEd.,Interscience,NewYork,1950。就混悬浓缩物而言,溶解度在0.1%之下是优选的;溶液浓缩物最好是稳定的,在0℃不发生相分离。下述文献列出了表面活性剂及其推荐的用途“McCutcheon′sDetergentsandEmulsifiersAnnual”,MCPublishingCorp.,Ridgewood,NewJersey;SiselyandWood,“EncyclopediaofSurfaceActiveAgents”,ChemicalPublishingCo.,Inc.,NewYork,1964。所有制剂可含有少量添加剂以减少起泡、结块、腐蚀及微生物生长等。
制备上述组合物的方法是公知的。简单地将各成分混合可制备溶液。将各成分混合,并通常用锤磨或流能磨研磨可制得细粉的固体组合物。通过湿磨(例如,参见U.S.Patent3,060,084)可制备混悬液。将活性物质喷于预制的粒状载体上或通过凝聚技术可制备粒剂和丸剂,参见下列文献
J.E.Browning,“Agglomeration”,ChemicalEngineering,December4,1967,pp.147ffand“Perry′sChemicalEngineer′sHandbook”,5thEd.,McGraw-Hill,NewYork,1973,pp.8-59ff.
关于制剂技术的其它信息,可参见下述文献例如
U.S.Patent3,235,361;
U.S.Patent3,309,192;
U.S.Patent2,891,855;and
G.C.Klingman,“WeedControlasaScience”,JohnWiley&Sons,Inc.,NewYork,1961,pp.81-96;and
J.D.Fryeretal.,“WeedControlHandbook”,5thEd.,BlackwellScientificPublications,Oxford,1968,pp.101-103.
下述制剂实施例中,除非另有说明,所有的份数都是重量份数。
实施例A
可湿粉剂
1-(4,6-二甲基-2-嘧啶基)
-1,4,5,6-四氢-3-苯基哒嗪50%
烷基萘磺酸钠2%
木素磺酸钠5%
硅藻土43%
将各成分混合,先锤磨,然后气磨成粒径小于10μ的微粒,混合后包装。
实施例B
粒剂
油状活性成分5%
硅镁土颗粒(过美国筛20-40目;0.84-0.42mm)95%
在双锥混合器中将油状活性成分喷于硅镁土颗粒表面,将颗粒干燥,包装。
实施例C
油混悬液
1-(4,6-二甲基-2-嘧啶基)
-1,4,5,6-四氢-3-苯基哒嗪25%
聚氧乙烯山梨醇六油酸酯5%
高级脂肪烃油70%
将各成分于沙磨机中碾磨至粒径小于5μ为止,得到的稠的混悬液可以直接应用,但最好是用油稀释或于水中乳化后应用。
实施例D
可湿粉剂
1-(4,6-二甲基-2-嘧啶基)
-1,4,5,6-四氢-3-苯基哒嗪50%
烷基萘磺酸钠4%
木素磺酸钠4%
低粘度甲基纤维素3%
硅镁土69%
将各成分充分混合,在锤磨中碾磨至粒径小于100μ后,再混合,过美国50目的筛(孔径0.33mm),然后包装。
实施例E
低浓度颗粒
1-(4,6-二甲基-嘧啶基)
-1,4,5,6-四氢-3-苯基哒嗪1%
二氯甲烷9%
硅镁土颗粒(过美国筛20-40目)90%
将活性成分溶于溶剂中,在双锥混合机中,将该溶液喷于去尘的颗粒上。溶液喷完之后,让混合机转动一短时间,产品温和地干燥,除去溶剂,包装颗粒。
实施例F
水混悬液
1-(4,6-二甲基-2-嘧啶基)
-1,4,5,6-四氢-3-苯基哒嗪10%
聚丙烯酸增稠剂0.3%
十二烷基酚聚乙二醇醚5.0%
磷酸氢二钠1%
磷酸二氢钠0.5%
聚乙烯醇1.0%
水82.2%
将各成分混合,并于匀化器中一起研磨,得到所有的颗粒基本上均小于5μ的颗粒。
实施例G
溶液
1-(4,6-二甲基-2-嘧啶基)
-1,4,5,6-四氢-3-苯基哒嗪5%
水95%
将化合物的盐直接加入水中,同时搅拌,得到溶液,然后包装供使用。
实施例H
低浓度颗粒剂
1-(4,6-二甲基-2-嘧啶基)
-1,4,5,6-四氢-3-苯基哒嗪0.1%
硅镁土颗粒(U.S.S.20-40目)99.9%
将活性成分溶于溶剂中,在双锥混合机中将该溶液喷于去尘的颗粒上,喷完溶液后加温使溶剂挥发,然后冷却,包装。
实施例I
乳化浓缩物
1-(4,6-二甲基-2-嘧啶基)
-1,4,5,6-四氢-3-苯基哒嗪35%
多醇羧酸酯和油溶的石油磺酸盐混合物6%
二甲苯59%
将各成分混合,并搅拌得到溶液。此产品可用油稀释或用水乳化。
实施例J
可乳化浓缩物
1-(4,6-二甲基-2-嘧啶基)
-1,4,5,6-四氢-3-苯基哒嗪20%
氯苯74%
山梨醇单硬脂酸酯及其聚氧乙烯缩合物6%
将各成分混合并搅拌得到溶液,该溶液应用时可在水中乳化。
本发明化合物用作植物疾病的控制剂。它们能控制由担子菌纲、子囊菌纲和卵菌纲的广谱真菌植物病原体引起的病害。它们能有效地控制广泛的植物病害,特别是观赏植物、蔬菜、田间植物、谷物和水果农作物的叶病原体。这些病原体包括苹果黑星菌,球座尾孢,落花生尾孢,菾菜生尾孢,Pseudocercosporellaherpotrichoides,禾白粉菌,葡萄钩丝壳,苹果白粉病菌,隐匿柄锈菌,禾柄锈菌,咖啡驼孢锈菌,条形柄锈菌,落花生柄锈菌,Pyriculariaoryzae,致病疫霉,葡萄生单轴霉,烟草霜霉,石巴假霜霉,瓜果腐霉,灰葡萄孢,Moniliniafructicola,Alternariabrassicae,Septorianodorum,及与上述病原体密切相关的其它种类病原体。本发明化合物还可以控制种子病原体。
本发明化合物可与各种杀真菌剂、杀细菌剂、杀螨剂或其它生物活性化合物混合,以便用最小的时间、精力和材料消费达到期望的结果。上述类型的适宜试剂是专业人员熟知的,其中的某些试剂列举如下
杀真菌剂
2-苯并咪唑氨基甲酸甲酯(carbendazim)
四甲基二硫化秋兰姆(thiuram)
正十二烷基胍乙酸盐(dodine)
亚乙基双二硫代氨基甲酸锰(maneb)
1,4-二氯-2,5-二甲氧基苯(Chloroneb)
1-(丁基氨甲酰基)-2-苯并咪唑氨甲酸甲酯(benomyl)
2-氰基-N-乙基氨甲酰基-2-甲氧基亚氨基乙酰胺(cymoxanil)
N-三氯甲基硫代四氢化邻苯二甲酰胺(captan)
N-三氯甲基硫代四氢化邻苯二甲酰亚胺(folpet)
4,4′-(邻亚苯基)双(3-硫代脲基甲酸)二甲酯(thiophanate-methyl)
2-(噻唑-4-基)苯并咪唑(thiabendazole)
三(O-乙基磷酸)铝(phosethylaluminum)
四氯异邻苯二甲腈(chlorothalonil)
2,6-二氯-4-硝基苯胺(dichloran)
N-(2,6-二甲基苯基)-N-(甲氧基乙酰基)氨基丙酸甲酯(metalaxyl)
顺式-N-[(1,1,2,2-四氯乙基)硫基]环己-4-烯-1,2-二甲酰基亚胺(captafol)
3-(3,5-二氯苯基)-N-(1-甲基乙基)-2,4-二氧-1-咪唑烷甲酰胺(iprodione)
3-(3,5-二氯苯基)-5-乙烯基-5-甲基-2,4-!唑烷二酮(vinclozolin)
春日霉素
O-乙基-S,S-二苯基二硫代磷酸酯(edifenphos)
4-(3-(4-(1,1-二甲基乙基)苯基)-2-甲基)丙基-2,6-二甲基吗啉(fenpropimorph)
4-(3-(4-(1,1-二甲基乙基)苯基)-2-甲基)丙基哌啶(fenpropidine)
1-(4-氯苯氧基)-3,3-二甲基-1-1H-1,2,4-三唑-1-基)丁酮(triadimefon)
2-(4-氯苯基)-2-(1H-1,2,4-三唑-1-基甲基)己腈(myclobutanil)
1-[2-(4-氯苯基)乙基]-1-(1,1-二甲基乙基)-1-(1H-1,2,4-三唑-1-基)乙醇(tebuconazol)
3-氯-4-[4-甲基-2-(1H-1,2,4-三唑)-1-基甲基)-1,3-二氯戊环-2-基]苯基-4-氯苯基醚(difenoconazole)
1-[2-(2,4-二氯苯基)戊基]-1H-1,2,4-三唑(penconazole)
2,4′-二氯-1-(1H-1,2,4-三唑-1-基甲基)二苯甲基醇(flutriafol)
1-[[[双(4-氟苯基)]甲基甲硅烷基]-甲基]-1H-1,2,4-三唑(flusilazole)
N-丙基-N-[2-(2,4,6-三氟苯氧基)乙基]咪唑-1-甲酰胺(prochloraz)
1-[2-(2,4-二氯苯基)-4-丙基-1,3-二氧戊环-2-基甲基]-1H-1,2,4-三唑(propiconazole)
1-(2-氯苯基)-1-(4-氯苯基)-1-(5-嘧啶)甲醇(fenarimol)
1-(4-氯苯氧基)-3,3-二甲基-1-(1H-1,2,4-三唑-1-基)丁-2-醇(triadimenol)
1-(2,4-二氯苯基)-4,4-二甲基-2-(1H-1,2,4-三唑-1-基)戊-3-醇(diclobutrazol)
氯氧化铜
N-(2,6-二甲基苯基)-N-(2-呋喃羰基)-DL-丙氨酸甲酯(furalaxyl)
1-(4-氨基-1,2-二氢-2-氧嘧啶-1-基)-4-[(S)-
3-氨基-5-(1-甲基胍基)正戊酰氨基]-1,2,3,4-四去氧-β-D-赤型-己-2-烯吡喃糖醛酸(blasticidin-S)
6-(3,5-二氯-4-甲基苯基)-3(2H)-哒嗪酮(diclomezine)
O-乙基-S,S-二苯基-二硫代磷酸酯(edifenphos)
1,3-二硫戊环-2-亚基丙二酸二异丙酯(isoprothiolane)
O,O-二异丙基-S-苄基硫代磷酸酯(iprobenfos)
3′-异丙氧基-2-甲基-N-苯甲酰基胺(mepronil)
甲基砷酸铁(铁铵盐)(neo-asozin)
N-[(4-氯苯基)甲基]-N-环戊基-N′-苯基脲(pencycuron)
3-烯丙氧基-1,2-苯并异噻唑-1,1-二氧化物(probenazole)
1,2,5,6-四氢吡咯并[3,2,1-ij]喹啉-4-酮(pyroquilon)
α,α,α-三氟-邻-N-对甲基苯甲酰基苯胺(flutolanil)
5-甲基-1,2,4-三唑(3,4-b)苯并噻唑(tricyclazole)
4,5,6,7-四氯-2-苯并[C]呋喃酮(四氯苯并呋喃酮)
1L-(1,3,4/2,6)-2,3-二羟基-6-羟甲基-4-[(1S,4R,5S,6S)-4,5,6-三羟基-3-羟甲基环己-2-烯基氨基]环己基-β-D-吡喃葡萄糖苷(validamycin)
α,α,α-三氟-3′-异丙氧基-2-N-对甲基苯甲酰基苯胺(flutolanil)
杀细菌剂
三碱基硫酸铜
链霉素硫酸盐
土霉素
杀螨剂
千里光酸2-钟丁基-4,6-二硝基苯基酯(binapacryl)
6-甲基-1,3-二硫戊环并[2,3-B]喹啉-2-酮(oxythi-quinox)
2,2,2-三氟-1,1-双(4-氯苯基)乙醇(dicofol)
双(五氯-2,4-环戊二烯-1-基)(dienochlor)
三环己基锡氢氧化物(cyhexatin)
六双(2-甲基-2-苯丙基)二锡噁烷(fenbutinoxid)
杀线虫剂
2-[二乙氧基氧膦基亚氨基]-1,3-二噻烷(fosthietan)
S-甲基-1-(二甲基氨甲酰基)-N-(甲基氨甲酰氧基)-硫代亚氨基甲基醚(oxamyl)
S-甲基-1-氨甲酰基-N-(甲基氨甲酰氧基)-硫代亚氨基甲基醚
N-异丙基氨基磷酸O-乙基-O′-[4-(甲硫基)-间甲苯基]二酯(fenamiphos)
杀昆虫剂
3-羟基-N-甲基巴豆酰胺(二甲基磷酸)酯(monocrotophos)
甲基氨基甲酸2,3-二氢-2,2-二甲基-7-苯并呋喃酯
(carbofuran)
O-[2,4,5-三氟-α-(氯甲基)苄基]磷酸O′,O′-二甲基酯(tetrachlorvinphos)
2-巯基琥珀酸二乙酯,与硫羰磷酸形成的S-酯,二甲基酯(malathion)
硫代磷酸O,O-二甲基,O-对硝基苯基酯(methylparathion)
甲基氨甲酸α-萘基酯(carbaryl)
N-[[(甲氨基)羰基]氧基]乙亚氨基硫代酸甲酯(methomyl)
N′-(4-氯-邻甲基苯基)-N,N-二甲基甲脒(chlordimeform)
O,O-二乙基-O-(2-异丙基-4-甲基-6-嘧啶基)-硫代磷酸酯(diazinon)
八氯莰烯(toxaphene)
O-乙基O-对硝基苯基苯基硫代磷酸酯(EPN)
4-氯-α-(1-甲基乙基)苯乙酸氰基-(3-苯氧基苯基)-甲基酯(fenvalerate)
3-(2,2-二氯乙烯基)-2,2-二甲基环丙烷基甲酸(3-苯氧基苯基)甲基酯(permethrin)
N,N′-[硫代双(N-甲基亚氨基)羰基氧基]-双[乙亚氨基硫代酸]二甲基酯(thiodicarb)
硫代硫醇磷酸O-乙基-O-[4-(甲硫基)苯基]-S-正丙基酯(sulprofos)
3-(2,2-二氯乙烯基)-2,2-二甲基环丙烷基甲酸α-氰基-3-苯氧基苄基酯(cypermethrin)
4-(二氟甲氧基)-α-(甲基乙基)苯乙酸氰基(3-苯氧基苯基)甲基酯(flucythrinate)
O,O-二乙基-O-(3,5,6-三氟-2-吡啶基)硫代磷酸酯(chlorpyrifos)
O,O-二甲基-S-[(4-氧-1,2,3-苯并三嗪-3(4H)-基甲基]-二硫代磷酸酯(azinphos-methyl)
二甲氨基甲酸5,6-二甲基-2-二甲氨基-4-嘧啶基酯(pirimicarb)
S-(N-甲酰基-N-甲基氨甲酰甲基)-O,O-二甲基二硫代磷酸酯(formothion)
S-2-(乙硫基乙基)-O,O-二甲基硫代磷酸酯(demeton-S-methyl)
(1R,3R)-3-(2,2-二溴乙烯基)-2,2-二甲基环丙烷甲酸(5)-α-氰基-3-苯氧基苄基酯(deltamethrin)
N-(2-氯-4-三氟甲基苯基)丙氨酸氰基(3-苯氧基苯基)甲基酯(fluvalinate)。
应用方法
控制病害一般按下法进行在感染病害前或感染病害后,将有效量的本发明化合物施用于植物的要保护的部分(例如根,茎,叶,果实,种子,块茎或球茎,或施用于要保护的植物生长的介质(如土壤或沙)中。本发明化合物也可施用于种子以保护种子和秧苗。
本发明化合物施用的比率受环境的许多因素影响,因此应根据实际应用的条件而确定。当以少于1g/ha至5000g/ha比率的活性成分处理时,一般可保护叶。用0.1-20kg/ha的浓度处理植物生长的土壤,可保护植物免遭病害。当每公斤种子用0.1-10g的活性化合物处理后一般可保护种子和秧苗。根据下述的试验A-F评价本发明化合物
对病害控制的效力。
试验A
将试验化合物溶于丙酮中,最终浓度为3%(体积),然后以200ppm的浓度混悬于纯化水中,水中含有250ppm表面活性剂Trem014(多元醇酯)。将该混悬液按量喷洒于小麦秧苗上。第二天用Erysiphegraminisf.sp.tritici的孢子粉尘(小麦粉霉致病剂)接种该小麦秧苗,并于20℃的生长室孵化7天,之后评价病害等级。
试验B
将试验化合物溶于丙酮中,最终浓度为3%(体积),然后以200ppm的浓度混悬于纯化水中,水中含有250ppm表面活性剂Trem014(多元醇酯)。将该混悬液按量喷洒于小麦秧苗上。第二天用Pucciniarecondita的孢子混悬液(小麦叶锈病致病剂)接种该小麦秧苗并在饱和气氛中于20℃孵化24小时,然后移至20℃的生长室孵化6天,之后评价病害等级。
试验C
将试验化合物溶于丙酮中,最终浓度为3%(体积),然后以200ppm的浓度混悬于纯化水中,水中含有250ppm表面活性剂Trem014(多元醇酯)。将该混悬液按量喷洒于水稻秧苗上。第二天用Pyriculariaoryzae的孢子混悬液(水稻稻瘟病致病剂)接种该水稻秧苗,在饱和的环境中于27℃孵化24小时,然后移至30℃的生长室孵
化5天,之后评价病害等级。
试验D
将试验化合物溶于丙酮中,最终浓度为3%(体积),然后以200ppm的浓度混悬于纯化水中,水中含有250ppm表面活性剂Trem014(多元醇酯)。将该混悬液按量喷洒于西红柿秧苗上。第二天用Phytophthorainfestans的孢子混悬液(土豆和西红柿晚疫病致病剂)接种该秧苗,并于20℃的饱和环境中孵化24小时,然后移至20℃生长室5天,之后评价病害等级。
试验E
将试验化合物溶于丙酮中,最终浓度为3%(体积),然后以200ppm的浓度混悬于纯化水中,水中含有250ppm表面活性剂Trem014(多元醇酯)。将该混悬液按量喷洒于葡萄秧苗上。第二天用Plasmoparaviticola的孢子混悬液(葡萄绒霉致病剂)接种该秧苗并于饱和环境中20℃孵化24小时,然后移至20℃的生长室孵化6天,再于20℃饱和环境中孵化24小时,之后评价病害等级。
试验F
将试验化合物溶于丙酮中,最终浓度为3%(体积),然后以200ppm的浓度混悬于纯化水中,水中含有250ppm表面活性剂Trem014(多元醇酯)。将该混悬液按量喷洒于黄瓜秧苗上。第二天用Botrytiscinerea的孢子混悬液(许多作物灰霉的致病剂)接种该秧
苗,并在20℃的饱和环境中孵化48小时,然后移至20℃的生长室孵化5天,之后评价病害等级。
在下列索引表A至O中,化合物为油状物和胶状物的1H NMR数据列于索引表O中,其单位为ppm(以四甲基甲硅烷为内标),降非另有说明,样品溶于CDCl3中测定。另外,除采用前述缩写外,还采用下列缩写
CMPD-化合物brs-宽单峰
S-单峰t-三峰
d-双峰q-四峰
dd-双双峰m-多峰
Dec-分解
索引表A
CMPD.
NO. R1R2R3E mp(℃)a
1HMeMePh油
2MeHHPh79-81
3bPh H H Me 114-121
4PhHMeMe123-124.5
5PhMeMeH93.5-94
117 H H CF3Ph 124-127
148HHMe2-pyridyl140-146
b.65%化合物加上35%3-甲基-4-苯基-1H-吡唑。
索引表B
CMPD.
NO. R1R2R3R4R18E mp(℃)a
6HHMeMeHPh127-129
7MeHHMeHPh油
8 H H H Me H 3-CF3-Ph 125-130
9HHHMeH1-naphthalenyl119-126
10HHMeMeH4-Cl-Ph138-143
11HHMeMeH4-F-Ph155-160
12HHMeMeH2-Cl-Ph116-118
13HHHMeHPh142-144
14HHHMeH4-Cl-Ph179-181
15HHHMeH4-F-Ph158-165
16MeHMeMeHPh油
17 H H Me Me H 3-CF3-Ph 122-127
18HHMeMeH1-naphthalenyl199-202
20HHHHH1-naphthalenyl152-158
21HHHMeH2-Cl-Ph油
22HHHMeH2-Me-Ph100-105
23HHMeMeH2-Me-Ph105-109
24HHHHH4-F-Ph169-171
CMPD.
NO. R1R2R3R4R18E mp(℃)a
25HHHHHPh149-151
26HHMeMeH2-furanyl139-141
27HHHMeH2-furanyl152(Dec)
29HHHHH2-furanyl175(Dec)
30EtHHMeHPh油
31EtHMeMeHPh153-155
32HHMeMeH2-naphthalenyl134-137
33HHHMeH2-naphthalenyl182-184
34HHHMeH3-thienyl90-95
35HHMeMeH3-thienyl150-152
36i-PrHMeMeHPh168-170
37i-PrHHMeHPh95-103
38HHMeMeH2,5-di-Me-129-131
3-thienyl
39HHHMeH2,5-di-Me-118-122
3-furanyl
40HHHMeH2,5-dimethyl-119-124
3-thienyl
41HHMeMeH2,5-di-Me-111-113
3-furanyl
47HHMeMeH2-Br-Ph85-92
48HHMeMeH2-i-PrO-Ph115-120
49HHMeMeH2,5-di-MeO-Ph154-156
50HHMeMeH2,4-diCl-Ph103-109
51HHMeMeH3-Me-2-thienyl138-140
52HHMeMeH3-F-Ph139-141
53HHMeMeH2-芴基179-183
CMPD.
NO. R1R2R3R4R18E mp(℃)a
54HHMeMeH2-MeO-Ph142-150
55HHMeMeH3-Cl-Ph144-149
56HHMeMeH4-Me-Ph89-92
57PhHMeMeHPh167-170
58HHMeMeH4-Ph-Ph220
61HHMeMeH2,4,6-tri-Me-Ph110-150
62HPhMeMeHPh179-181
63HHMeMeH3-Me-Ph129-131
64HHMeMeHt-Bu129-131
65HHMeMeH2-pyridyl96-105
(85%纯)
70HHMeMeH4-n-Pr-Ph90-95
71HHMeMeH3,4-di-Me-Ph145-148
72HHMeMeH4-Et-Ph106-112
73HHMeMeH4-c-hex-Ph164-167
74HHMeMeH2,4,5-tri-Me-Ph150-152
75HHMeMeH2,4-di-Me-Ph109-112
76HHMeMeH2,6-di-MeO-Ph109-125
77HHMeMeH2,5-di-Me-Ph141-143
78HHMeMeH6-Me-2-naphthalenyl186-189
114 H H Me CF3H 4-Cl-Ph 173-175
115 H H Me CF3H Ph 151-152
116 H H Me CF3H 4-Me-Ph 胶
118HHMePhH4-Cl-Ph110-113
119HHMec-PrH4-Cl-Ph167-169
120HHMeOHn-Bu4-Cl-Ph228-231
索引表C
CMPD.
NO. R1R2R3R4R18E mp(℃)a
42HHMeMeHPh94-97
43HHMeMeH4-F-Ph90-95
44bH H H Me H Ph 油
45HHHMeH4-F-Ph134-136
46HHMeMeH4-Br-Ph161-164
59HHMeMeH4-OH-Ph>220℃
60HHMeMeH4-t-Bu105-115℃
79HHMeMeH4-Me-Ph102-104
80HHMeMeH4-Cl-Ph146-149
81HHMeMeH4-MeO-Ph91-94
82HHMeMeH3,4-di-Me-Ph120-121
86HHMeMeH4-n-Pr-Ph103-106
87HHMeMeH4-i-Pr-Ph90-93
88HHMeMeH4-s-Bu-Ph74-77
89HHMeMeH4-Et-Ph66-71
90HHMeMeH2,4-di-Me-Ph91-93
91HHMeMeH4-n-Bu-Ph55-58
b化合物与4-氯丁酰基苯酮的比率为5∶1。
CMPD.
NO. R1R2R3R4R18E mp(℃)a
92HOHMeMeHPh153-155
93HHMeMeH4-C-hex-Ph139-141
94HHMeMeH2-Me-Ph90-92
95HHMeEtH3,4-di-Me-Ph106-110
96HHMeMeH4-i-Bu-Ph76-79
97HHMeMeH2-四氢-162-164
naphthalenyl
98HHMeMeH4-Ph-Ph169-171
99HHMeMeH2-indanyl140-142
100HHMeMeH4-Hex-Ph胶
101HHMeMeH3,4-di-Et-Ph75-80
102HHMeMeH4-n-pent-Ph60-63
103HHMeMeH4-PhO152-154
104HHMeMeH3-Me-4-Et-Ph(50%)103-106
&3-Et-4-Me-Ph(50%)
105MeHMeMeHPh109-111
106EtHMeMeHPh112-114
107HHMeMeH2,5-di-Me-Ph胶
108HHMeMeH4-(1-(2-Cl-胶
pr))-Ph
109HHMeMeH3-Cl-Ph98-100
110HHMeMeH2-thienyl160-162
111HHMeMeH3,4,5-tri-Me-Ph154-156
112HHMeMeH2,5-di-Et-Ph胶
90%(纯)
113HMeOMeMeHPh104-108
121HHMeMeCl3,4-di-Me-Ph169-173
CMPD.
NO. R1R2R3R4R18E mp(℃)a
122 H H Me CF3H 4-Cl-Ph 150-152
123HHMec-PrH4-Cl-Ph123-126
124HHMeMeBr3,4-di-Me-Ph175-179
125HHMec-PrH4-Me-Ph胶
126HHMeOHn-Bu4-Cl-Ph171-181
127HHMeMeH3,4-di-Me-Ph胶
128HHMeOHn-Bu3,4-di-Me-Ph140-155
129HHMei-BuH3,4-di-Me-Ph油
130HHMei-BuH4-Cl-Ph136-141
131 H H Me CH2CH2CH24-Cl-Ph 181-184
132HHMeEtH4-Cl-Ph95-98
133HHMec-PrH4-i-Pr-Ph95-99
134HHMei-PrH4-Cl-Ph96-98
135HHMec-PrH4-Et-Ph胶
136HHMeMeOH4-Cl-Ph139-143
137HHMei-PrH3,4-di-Me-Ph油
138HHMec-PrH4-n-Pr-Ph128-132
139HHMePhH4-Cl-Ph油
70%
140HHMeC-PrH4-MeO-Ph油
141HHMeMeOH3,4-di-Me-Ph145-148
CMPD.
NO. R1R2R3R4R18E mp(℃)a
142HHMeMeMe4-Cl-Ph161-169
143HHMeEtH4-Et-Ph油
144HHMeEtH4-i-Pr-Ph油
145HHMeEtH4-MeO-Ph油
146HHMeEtH4-Me-Ph油
147HHMei-BuH4-Me-Ph油
159HHMeMeH2,4-diEt-Ph48-51
160HHMeMeH2-Me-4-t-Bu-Ph130-133,
85%
161HHMeMeH3-Me-Ph128-130
162 H H Me Me H 3-CF3-Ph 86-88
163 H H Me TMS-CH2H 3,4-diMe-Ph 油
164HHEtEtH4-Cl-Ph111-114
165HHEtEtH3,4-diMe-Ph油
166HHMei-PrH4-i-Pr-Ph油
167HHEti-PrH4-Ph-Ph胶
168HHMei-PrH4-OMe-Ph油
169 H H Me NMe2H 3,4-diMe-Ph 油
170HHEtEtH4-OMe-Ph油
171HHMei-PrH4-Et-Ph胶
172HHEtEtH4-i-Pr-Ph油
索引表D
CMPD.
NO. R3R4R18E mp(℃)
19HHHPh74-79
28HHH2-furanyl91-93
66MeMeCNPh>240
67 Me CF3H Ph 215-219
68MeHHPh120-121
69MeHH1-naphthalenyl85-90
索引表E
CMPD.
NO. R3R4R18E mp(℃)
83 Me CF3H Ph 75-81
84 Me CF3H 4-t-Bu-Ph 84-90
85MeHH4-Me-Ph82-86
索引表F
CMPD.
NO.Emp(℃)
1524-Cl-Ph171-180
索引表G
CMPD.
NO.Emp(℃)
1533,4-di-Me-Ph159-161
1544-Cl-Ph248-252
1554-i-Pr-Ph136-142
1734-MeO-Ph150-152
索引表H
CMPD.
NO. R3R4E mp(℃)a
156ClCl4-Cl-Ph181-185
157MeCl3,4-di-Me-Ph油
索引表I
CMPD.
NO. R1R2R3R4X E mp(℃)
150HHHHCHPh77-78
索引表J
CMPD.
NO. R1R2R3R4X E mp(℃)a
149HHMeMeNPh油
索引表K
CMPD.
NO. R3R4X E mp(℃)
151MeMeNPh134-135
索引表L
CMPD.
NO. R3R4X E mp(℃)
158MeMeNPh97-98
索引表M
CMPD.
NO. R3R4R23E mp(℃)a
174MeMeH3,4-diMe-Ph油
索引表N
CMPD.
NO. MLnR1R2mp(℃)
175 ZnCl2H Cl 231-232
176 FeCl3H Cl 172-173
177 CuCl2H Cl 135-138
178 CuCl2CH3CH3132-133.5
179 FeCl3CH3CH3150-151
180 MnCl2CH3CH3232-233
181 ZnCl2CH3CH3250-251
182 MgCl2CH3CH3100-101
索引表O
CMPD.
NO.1H NMR Dataa
12.56(s,6H),2.72(s,3H),6.58(s,1H),6.95(s,1H)
71.34(d,3H),2.46(s,3H),6.57(d,1H),8.33(d,1H)
161.4(d,3H),2.4(s,6H),4.0(dd,1H),4.2(dd,1H),
6.4(s,1H)
212.5(s,3H),3.5(t,2H),4.2(t,2H),6.6(d,1H),
8.3(d,1H)
300.93(t,3H),2.4(s,3H),6.50(d,1H),8.28(d,1H)
442.11(m,2H),2.46(s,3H),2.72(t,2H),4.8(t,2H),
6.60(d,1H),7.8(d,2H),7.8(d,2H),8.40(d,1H)
1167.75(d,2H),7.2(d,2H),6.8(s,1H),4.2(t,2H),
3.35(t,2H),2.6(s,3H),2.4(s,3H)
1000.88(t,2H),1.29(m,6H),1.61(m,2H),2.15(m,
2H),2.42(s,6H),2.62(t,2H),2.70(t,2H),
4.09(t,2H),6.50(s,1H),7.18(d,2H),7.78(d,2H)
1072.1(m,2H),2.32(s,3H),2.38(s,6H),2.47(s,3H),
2.59(t,2H),4.10(t,2H),6.47(s,1H),7.05(d,
1H),7.16(d,1H),7.21(s,1H)
1081.48(d,3H),2.10(m,2H),2.41(s,6H),2.69(t,
2H),2.95(dd,1H),3.10(dd,1H),4.08(t,2H),
4.1(m,1H),6.50(s,1H),7.20(d,2H),7.81(d,2H)
1121.2(t,3H),1.27(t,3H),2.11(m,2H),2.36(s,6H),
2.60(m,4H),2.80(q,2H),4.10(t,2H),6.46(s,
1H),7.09(d,1H),7.16(s,1H),7.17(d,1H)
CMPD.
NO.1H NMR Dataa
1257.8(d,2H),7.4(d,2H),6.4(s,1H),4.0(m,2H),
2.67(t,2H),2.42(s,3H),2.35(s,3H),2.1(m,2H),
1.9(m,1H),1.1(m,2H),1.0(m,2H)
1277.68(s,1H),7.55(m,1H),7.15(d,1H),6.46(s,
1H),4.01(m,2H),2.67(t,2H),2.42(s,3H),
2.27(2s,6H),2.15(m,2H),1.90(m,1H),1.14(m,
2H),1.00(m,2H)
1297.7(s,1H),7.55(m,1H),7.1(d,1H),6.45(s,1H),
4.1(m,2H),2.70(t,2H),2.50(d,2H),2.45(s,3H),
2.29(s,3H),2.27(s,3H),2.0-2.2(m,3H),0.95(m,
6H)
1357.76(d,2H),7.22(d,2H),6.47(s,1H),4.0(m,2H),
2.67(m,4H),2.41(s,3H),2.1(m,2H),1.9(m,1H),
1.24(t,3H),1.1(m,2H),0.95(m,2H)
1377.7(s,1H),7.59(m,2H),7.10(d,1H),6.50(s,1H),
4.1(m,2H),2.9(m,1H),2.7(t,2H),2.45(s,3H),
2.30(s,3H),2.27(s,3H),2.1(m,2H),1.28(d,6H)
1398.1(m,2H),7.85(m,2H),7.85(d,2H),7.47(m,3H),
7.36(d,2H),7.11(s,1H),4.2(m,2H),2.7(t,2H),
2.56(s,3H),2.15(m,2H)
1407.8(d,2H),6.9(d,2H),6.46(s,1H),4.05(m,2H),
3.81(s,3H),2.65(t,2H),2.41(s,3H),2.1(m,2H),
1.9(m,1H),1.1(m,2H),0.95(m,2H)
1437.78(d,2H),7.2(d,2H),6.5(s,1H),4.05(m,2H),
2.7(m,6H),2.44(s,3H),2.15(m,2H),1.30(t,3H),
1.24(t,3H)
CMPD.
NO.1H NMR Dataa
1447.79(d,2H),7.22(d,2H),6.50(s,1H),4.05(m,
2H),2.9(m,1H),2.69(m,4H),2.43(s,3H),2.05(m,
2H),1.3(t,3H),1.27(d,6H)
1457.8(d,2H),6.9(d,2H),6.5(s,1H),4.1(m,2H),
3.83(s,3H),2.68(m,4H),2.43(s,3H),2.1(m,2H),
1.30(t,3H)
1467.76(d,2H),7.17(d,2H),6.5(s,1H),4.10(m,2H),
2.68(m,4H),2.43(s,3H),2.36(s,3H),2.10(m,
2H),1.30(t,3H)
1477.75(d,2H),7.15(d,2H),6.5(s,1H),4.1(m,2H),
2.9(m,1H),2.7(t,2H),2.45(s,3H),2.36(s,3H),
2.1(m,2H),1.28(d,6H)
1492.60(s,6H),6.99(s,1H),7.32(m,2H),7.46(t,
2H),7.84(d,2H),8.01(d,1H)
1572.05(s,3H),2.1(m,2H),2.32(s,6H),3.04(t,2H),
4.20(t,2H),7.23(d,1H),7.33(m,3H)
1637.75(m,1H),7.6(m,1H),7.1(m,1H),6.5(s,1H),
4.1(m,2H),2.7(m,2H),2.44(s,5H),2.3(s,3H),
2.27(s,3H),2.1(m,2H),0.15(s,9H)
1657.7(s,1H),7.55(d,1H),7.1(d,1H),6.51(s,1H),
4.1(m,2H),2.70(m,6H),2.30(s,3H),2.27(s,3H),
2.1(m,2H),1.32(t,6H)
1667.8(d,2H),7.2(d,2H),6.5(s,1H),4.1(m,2H),
2.9(m,2H),2.7(t,2H),2.45(s,3H),2.1(m,2H),
1.27(m,12H)
CMPD.
NO.1H NMR Dataa
1677.95(d,2H),7.62(m,2H),7.44(m,2H),7.30(m,
1H),6.52(m,1H),4.10(m,2H),2.9(m,1H),2.73(t,
2H),2.47(s,3H),2.15(m,2H),1.29(d,6H)
1687.82(d,2H),6.90(d,2H),6.49(s,1H),4.09(m,
2H),3.83(s,3H),2.90(m,1H),2.68(m,2H),
2.45(s,3H),2.10(m,2H),1.28(d,6H)
1697.7(s,1H),7.58(m,1H),7.10(d,1H),5.85(s,1H),
4.05(m,2H),3.12(s,6H),2.65(t,2H),2.34(s,
3H),2.29(s,3H),2.26(s,3H),2.10(m,2H)
1707.82(d,2H),6.90(d,2H),6.50(s,1H),4.10(m,
2H),3.83(s,3H),2.7(m,6H),2.1(m,2H),1.31(t,
6H)
1717.8(d,2H),7.2(d,2H),6.5(s,1H),4.1(m,2H),
2.9(m,1H),2.7(m,4H),2.45(s,3H),2.1(m,2H),
1.28(d,6H),1.24(t,3H)
1727.79(d,2H),7.22(d,2H),6.50(s,1H),4.1(m,2H),
2.9(m,1H),2.7(m,6H),2.1(m,2H),1.3(m,12H)
1747.25(s,1H),7.17(m,2H),6.4(brS,1H),6.22(s,
1H),4.8(m,1H),3.7(m,1H),3.2(m,1H),2.38(s,
3H),2.27(s,9H),1.9(m,2H),1.8(m,1H),1.7(m,
1H)
试验A至F的结果列于下表1中,其中等级100表示100%控制病害;0表示不能控制病害(与喷洒载体的对照组比较)。NT表示未做试验。表中Cmpd表示化合物;Test表示试验。
表1
CmpdTestTestTestTestTestTest
No.ABCDEF
197NT970NT0
2 95 97 14 25 47*0
30NT240NT0
4809670NT67
598100240NT81
661897917996
7919927000
87453029906
90146703745
106166014260
11616202190
12818767368089
13799703400
1461901621046
15687304200
169810001910089
1782001900
1801400110
196314003745
2001400114
218662046370
22866200114
CmpdTestTestTestTestTestTest
No.ABCDEF
23956297461194
24840026480
257349047480
265649047660
275649026480
2827000240
2927002600
3098978862730
3190979509294
3283921844150
33241600390
34241618761000
35546218761510
3683988822960
37548174921000
3857658404297
39065025190
4028654747920
410212301946
42969960993582
43578961823589
448810016684994
45948984453869
46605810009198
6158899709648
629193820370
632053797610097
643721304700
65305400018
663700000
678600000
CmpdTestTestTestTestTestTest
No.ABCDEF
6802182100
6911011000
7075617675920
71324139479298
72598629265847
7304100150
7411016000
754102927510
766027759200
77524696844294
782192006
7989100100479198
8091100100259198
81669899977548
82819897479788
83250104600
8446004600
85200200210
869910099010097
879910099259982
889999972510046
89971009909397
9098100100468694
919810097010046
927193960090
9338080850
948041021200
95919890636390
9694999009269
97851009009990
986667900410
99889991010099
CmpdTestTestTestTestTestTest
No.ABCDEF
100632843NT928
101959886NT10094
102859682NT1000
103728690NT430
10498100992310099
1059910099649278
10699100100010096
1071009299821003
1089810099709289
10984100995310098
11046675772068
111 71*44*86*NT 77*NT
1129910099579981
113958497378367
11445270581000
115189705800
1167666073420
11701200190
118611202200
1198661250190
1200240000
1215212920420
122012022420
12371129562920
124410250190
1256284780970
126000000
127549801000
1280240000
129836493239710
130612572NT750
CmpdTestTestTestTestTestTest
No.ABCDEF
131616693NT9799
13210010099NT10099
1331009991010088
13491529109293
135968580010088
136892632010088
137986791010093
1380651403962
1392665140140
140979692010096
1412950003
14246679637099
143989998376496
1449810096576468
1459810099579194
1469710093849299
1479510099749292
14974790000
15002404300
151 31**0**0**NT 0**NT
1525522190370
15386939009195
154806784129398
155730830750
156084100830
157100211200
1587611100632190
CmpdTestTestTestTestTestTest
No.ABCDEF
159 96*85*90*NT 28*79
160008000
1619910099749199
1629810099424193
1639210097847596
164 82*64 89*17 66*97
165 31*85 93 17 88 38*
166 92*8*35*16 20*64
16753000180
168839996409299
16985023859146
170989699417399
171 0***11***4***NT NT NT
17298989081000
173539361169999
17499100987310093
175 31*8*89*40 45*99
176 42*8*82*73 27*99
177 36*93 86*96 84*99
178336184929698
179859899749198
1809510099749699
18185100100749699
1829110099749694
*=喷洒浓度为40ppm.
**=喷洒浓度为20ppm.
***=喷洒浓度为10ppm.
权利要求
1、选自式Ⅰ、Ⅱ、Ⅲ、Ⅳ、Ⅴ或Ⅵ的杀真菌化合物,其中包括其所有的几何异构体和立体异构体及它们的盐和金属配合物,式Ⅰ、Ⅱ、Ⅲ、Ⅳ、Ⅴ、和Ⅵ分别是
式中
A是2-嘧啶基,2-吡啶基,2-喹啉基,2-喹唑啉基,1-异喹啉基或3-异喹啉基,所述每一个基团均可被R3、R4和R18取代;或是可被R3和R4取代的S-三嗪基;条件是R3、R4和R18只取代杂环的碳原子;
G是可由R3、R4和R18取代的2-喹唑啉基;
E是氢;囟素;C1-C6烷基;可由1至2个甲基取代的C3-C7环烷基;C1-C6囟代烷基;C1-C6烷硫基;C1-C6烷氧基;C1-C6囟代烷氧基;或者可由R5、R6和R7取代的下列基团苯基,苯氧基,苯硫基,苯氨基,苯甲基,2,3-二氢化茚基,四氢化萘基,1-萘基,2-萘基,噻吩基,呋喃基或吡啶基;
n是1,2或3;
R1是氢;囟素;氰基;羟基;C1-C4烷氧基;-OC(=O)R19;
-OC(=O)NHR20;C1-C4烷基;C1-C4囟代烷基;C2-C3烷基羰基;C2-C6链烯基;C2-C6烷氧基烷基;C2-C4炔基;C2-C3烷氧基羰基;或可由R8、R9和R10取代的下列基团苯基,苯甲基,1-萘基,2-萘基,噻吩基,呋喃基或吡啶基;
R2是氢,氰基,C1-C4烷基或C1-C4囟代烷基;
R3、R4和R18分别是囟素;氰基;羟基;(C1-C4烷基)3甲硅烷基甲基;可由R21取代的苯基;C1-C6烷基;环丙基;C1-C6囟代烷基;C1-C6烷硫基;C2-C4链烯基;C2-C4炔基;C1-C4烷氧基;C1-C4囟代烷氧基;C2-C4链烯氧基;C2-C4炔氧基;C2-C4烷氧基烷基;NR11R12;或者当R3和R4、R3和R18或R4和R18取代邻位碳原子时,R3和R4、R3和R18或R4和R18可以一起是可由1至2个甲基取代的-(CH2)3-或-(CH2)4-;
R5和R8分别是囟素;氰基;硝基;羟基;羧基;C1-C6烷基;C3-C6环烷基;C1-C6囟代烷基;C1-C4烷硫基;C1-C4烷基亚磺酰基;C1-C4烷基磺酰基;(C1-C4烷基)3甲硅烷基;C2-C5烷基羰基;C2-C4链烯基;C2-C4链烯氧基;C2-C4炔基;C2-C4炔氧基;C1-C4烷氧基;C1-C4囟代烷氧基;C2-C4烷氧基烷基;C2-C5烷氧羰基;C2-C4烷氧基烷氧基;NR13R14;C(=0)NR15R16;或可被R17取代的苯基,苯氧基或苯硫基;
R6、R7、R9、R10、R17、R21、R22和R24分别是囟素,C1-C4烷基,C1-C4囟代烷基2、C1-C4烷氧基或C1-C4囟代烷氧基;
R11、R12、R13、R14、R15和R16分别是氢;C1-C2烷基;或者R11和R12、R13和R14或R15和R16可以与它们相连接的氮原子一起形成吗啉代,吡咯烷基或哌啶子基团;
R19和R25是氢或C1-C3烷基;
R20和R26是C1-C4烷基;或可被R22取代的苯基;
R23是氢,C1-C4烷基,C1-C4囟代烷基,C2-C5烷基羰基,可被R24取代的苯基羰基,C3-C4链烯基,C3-C4炔基,苯环上可被R24取代的苯甲基,C1-C4烷基亚磺酰基,C1-C4烷基磺酰基,可被R24取代的苯基亚磺酰基,C2-C4烷氧羰基,可被R24取代的苯氧基羰基,C(=O)NR25R26,
C(=S)NHR26P(=S)(OR26)2,P(=O)(OR26)2,或S(=O)2NR25R26;
条件是
i)当E是囟素,C1-C6烷硫基,C1-C6烷氧基,C1-C6囟代烷氧基,苯氧基,苯硫基或苯氨基时,E仅可取代式Ⅰ或Ⅲ化合物;
ii)就式Ⅰ化合物而言,当A是2-吡啶基,n是2,R1和R2是氢时,E不是被1至2个氟、氯、三氟甲基、C1-C4烷基或C1-C4烷氧基取代的苯基,或者E不是噻吩基或呋喃基;
iii)就式Ⅲ化合物而言,E是苯基,苯氧基,苯硫基,苯甲基,1-萘基,2-萘基,噻吩基,呋喃基,吡啶基,上述每一个基团可被R5、R6和R7取代;或者R1是苯基,苯甲基,1-萘基,2-萘基,噻吩基,呋喃基或吡啶基,所述的每一个基团可被R8、R9和R10取代;和R1必须是在4-位;
iv)对于式Ⅲ化合物,R5不是NR13R14;
v)对于式Ⅰ和Ⅱ化合物,当n是1时,R1和R2不占据吡唑啉环的5-位;
vi)对于式Ⅰ化合物,当A是S-三嗪基时,R3或R4不是氨基;
vii)就式Ⅰ化合物而言,当A是可被R3、R18和R4取代的2-吡啶基和n是1时,E不是可由R5、R6和R7取代的苯氨基;
viii)就式Ⅰ和式Ⅲ化合物而言,当A是2-吡啶基,n是1,R1和R2是氢时,E不是苯基,4-溴苯基,4-甲氧基苯基,4-硝基苯基或4-羟基苯基;
ix)对于式Ⅱ化合物,当n是3时,E不是氢或C1-C5烷基;
X)对于式Ⅱ化合物,当n是1时,E不是氢;
xi)对于式Ⅰ化合物,当n是1和A是6-甲氧基吡啶基时,E不是4-N,N-二甲氨基苯基;
xii)对于式Ⅱ化合物,当A是2-吡啶基,n是2,R1和R2是氢时,E不是C1-C4烷基或吡啶基。
2、选自式Ⅰ或Ⅱ的杀真菌化合物,其中包括其所有的几何异构体和立体异构体,及它们的盐和金属配合物,式Ⅰ和Ⅱ为
式中
A是2-嘧啶基,2-吡啶基,所述每一个基团均可被R3和R4取代;或是可被R3和R4取代的S-三嗪基;条件是R3和R4只取代杂环的碳原子;
E是氢;囟素;C1-C6烷基;可由1至2个甲基取代的C3-C7环烷基;C1-C6囟代烷基;C1-C6烷硫基;C1-C6烷氧基;C1-C6囟代烷氧基;或者可由R5、R6和R7取代的下列基团苯基,苯氧基,苯硫基,苯氨基,苯甲基,1-萘基,2-萘基,噻吩基,呋喃基或吡啶基;
n是1,2或3;
R1是氢;囟素;氰基;C1-C4烷基;C1-C4囟代烷基;C2-C3烷基羰基;C2-C4链烯基;C2-C6烷氧基烷基;C2-C4炔基;C2-C3烷氧基羰基;或可由R8、R9和R10取代的下列基团苯基,苯甲基,1-萘基,2-萘基,噻吩基,呋喃基或吡啶基;
R2是氢,氰基,C1-C4烷基或C1-C4囟代烷基;
R3和R4分别是囟素;氰基;C1-C4烷基;环丙基;C1-C4囟代烷基;C1-C4烷硫基;C2-C4链烯基;C2-C4炔基;C1-C4烷氧基;C1-C4囟代烷氧基;C2-C4链烯氧基;C2-C4炔氧基;C2-C4烷氧基烷基或NR11R12;
R5和R8分别是囟素;氰基;硝基;羟基;羧基;C1-C4烷基;C1-C4囟代烷基;C1-C4烷硫基;C1-C4烷基亚磺酰基;C1-C4烷基磺酰基;(C1-C4烷基)3甲硅烷基;C2-C5烷基羰基;C2-C4链烯基;C2-C4链烯氧基;C2-C4炔基;C2-C4炔氧基;C1-C4烷氧基;C1-C4囟代烷氧基;C2-C4烷氧基烷基;C2-C5烷氧基羰基;C2-C4烷氧基烷氧基;NR13R14;C(=O)NR15R16;或可被R17取代的苯基,苯氧基或苯硫基;
R6、R7、R9、R10和R17分别是囟素,C1-C4烷基,C1-C4囟代烷基,C1-C4烷氧基或C1-C4囟代烷氧基;
R11、R12、R13、R14、R15和R16分别是氢或C1-C2烷基;
条件是
ⅰ)当E是囟素,C1-C6烷硫基,C1-C6烷氧基,C1-C6囟代烷氧基,苯氧基,苯硫基或苯氨基时,E仅可取代式Ⅰ化合物;
ⅱ)就式Ⅰ化合物而言,当A是2-吡啶基,n是2,R1和R2是氢时,E不是被1至2个氟、氯、三氟甲基、C1-C4烷基或C1-C4烷氧基取代的苯基,或者E不是噻吩基或呋喃基;
ⅲ)对于式Ⅰ和Ⅱ化合物,当n是1时,R1和R2不占据吡唑啉环的5-位;
ⅳ)对于式Ⅰ化合物,当A是S-三嗪基时,R3或R4不是氨基;
ⅴ)就式Ⅰ化合物而言,当A是可被R3、R18和R4取代的2-吡啶基和n是1时,E不是可由R5、R6和R7取代的苯氨基;
ⅵ)就式Ⅰ化合物而言,当A是2-吡啶基,n是1,R1和R2是氢时,E不是苯基,4-溴苯基,4-甲氧基苯基,4-硝基苯基或4-羟基苯基;
ⅶ)对于式Ⅱ化合物,当n是3时,E不是氢或C1-C5烷基;
ⅷ)对于式Ⅱ化合物,当n是1时,E不是氢;
ⅸ)对于式Ⅰ化合物,当n是1和A是6-甲氧基吡啶基时,E不是4-N,N-二甲氨基苯基;
ⅹ)对于式Ⅱ化合物,当A是2-吡啶基,n是2,R1和R2是氢时,E不是C1-C4烷基或吡啶基。
3、权利要求1的式Ⅰ和Ⅴ化合物及其金属配合物,其中
A是2-嘧啶基或2-喹唑啉基,它们可被R3、R4和R18取代;和
R1是氢;羟基;C1-C4烷氧基;C1-C4烷基;C1-C4囟代烷基;C2-C3烷基羰基;C2-C4链烯基;C2-C4炔基;C2-C3烷氧基羰基;或苯基,苯甲基,1-萘基,2-萘基,噻吩基,呋喃基或吡啶基,所述的每一个基团可被R8、R9和R10取代;
R3、R4和R18分别是囟素,C1-C4烷基,环丙基,C1-C4囟代烷基,烯丙基,C2-C3炔基,C1-C4烷氧基或C1-C4囟代烷氧基;
R23是氢,C(=O)NHR26或C2-C4烷氧基羰基。
4、权利要求3的化合物及其金属配合物,其中
A是可被R3、R4和R18取代的2-嘧啶基;
n是1或2;
E是苯基,2,3-二氢茚基,四氢萘基,1-萘基,噻吩基或吡啶基,所述每一个基团可被R5、R6和R7取代;
R1是氢,羟基,C1-C4烷氧基或C1-C4烷基;
R5是囟素,氰基,C1-C4烷基,C1-C4囟代烷基,烯丙基,炔丙基,C1-C4烷氧基,C1-C4囟代烷氧基,可被R17取代的苯基或苯氧基;和
R6、R7、R9、R10和R17分别是H,F,Cl,甲基,三氟甲基,甲氧基或三氟甲氧基。
5、权利要求4的化合物及其金属配合物,其中
E是可被R5、R6或R7取代的苯基、2,3-二氢茚基或四氢萘基;和
R2是氢或C1-C4烷基。
6、权利要求1的化合物,它们选自下述化合物
1-(4,6-二甲基-2-嘧啶基)-3-(3,4-二甲基苯基)-1,4,5,6-四氢哒嗪;
1-(4,6-二甲基-2-嘧啶基)-3-(4-乙基苯基)-1,4,5,6-四氢哒嗪;
1-(4,6-二甲基-2-嘧啶基)-1,4,5,6-四氢-3-(4-甲基苯基)哒嗪;
1-(4,6-二甲基-2-嘧啶基)-1,4,5,6-四氢-3-[4-(1-甲基乙基)苯基]哒嗪;
1-(4,6-二甲基-2-嘧啶基)-4-乙基-1,4,5,6-四氢-3-苯基哒嗪;
1-(4,6-二甲基-2-嘧啶基)-1,4,5,6-四氢-4-甲基-3-苯基哒嗪。
7、杀真菌组合物,它包括杀真菌剂有效量的权利要求1、2、3、4、5或6的化合物和惰性稀释剂或表面活性剂。
8、控制植物真菌病害的方法,它包括将有效量的式Ⅰ、Ⅱ、Ⅲ、Ⅳ、Ⅴ或Ⅵ化合物或它们的农业上适宜的盐或其金属配合物施用于要保护的部位,式Ⅰ、Ⅱ、Ⅲ、Ⅳ、Ⅴ和Ⅵ为
式中
A和G是2-嘧啶基,2-吡啶基,2-喹啉基,2-喹唑啉基,1-异喹啉基或3-异喹啉基,所述每一个基团均可被R3、R4和R18取代;或是可被R3和R4取代的S-三嗪基;条件是R3、R4和R18只取代杂环的碳原子;
E是氢;囟素;C1-C6烷基;可由1至2个甲基取代的C3-C7环烷基;C1-C6囟代烷基;C1-C6烷硫基;C1-C6烷氧基;C1-C6囟代烷氧基;或者可由R5、R6和R7取代的下列基团苯基,苯氧基,苯硫基,苯氨基,苯甲基,2,3-二氢化茚基,四氢化萘基,1-萘基,2-萘基,噻吩基,呋喃基或吡啶基;
n是1,2或3;
R1是氢;囟素;氰基;羟基;C1-C4烷氧基;-OC(=O)R19;-OC(=O)NHR20;C1-C4烷基;C1-C4囟代烷基;C2-C3烷基羰基;C2-C4链烯基;C2-C6烷氧基烷基;C2-C4炔基;C2-C3烷氧基羰基;或可由R8、R9和R10取代的下列基团苯基,苯甲基,1-萘基,2-萘基,噻吩基,呋喃基或吡啶基;
R2是氢,氰基,C1-C4烷基或C1-C4囟代烷基;
R3、R4和R18分别是囟素;氰基;羟基;(C1-C4烷基)3甲硅烷基甲基;可由R21取代的苯基;C1-C6烷基;环丙基;C1-C6囟代烷基;C1-C6烷硫基;C2-C4链烯基;C2-C4炔基;C1-C4烷氧基;C1-C4囟代烷氧基;C2-C4链烯氧基;C2-C4炔氧基;C2-C4烷氧基烷基;NR11R12;或者当R3和R4、R3和R18或R4和R18取代邻位碳原子时,R3和R4、R3和R18或R4和R18可以一起是可由1至2个甲基取代的-(CH2)3-或-(CH2)4-;
R5和R8分别是囟素;氰基;硝基;羟基;羧基;C1-C6烷基;C3-C6环烷基;C1-C6囟代烷基;C1-C4烷硫基;C1-C4烷基亚磺酰基;C1-C4烷基磺酰基;(C1-C4烷基)3甲硅烷基;C2-C5烷基羰基;C2-C4链烯基;C2-C4链烯基氧基;C2-C4炔基;C2-C4炔氧基;C1-C4烷氧基;C1-C4囟代烷氧基;C2-C4烷氧基烷基;C2-C5烷氧基羰基;C2-C4烷氧基烷氧基;NR13R14;C(=O)NR15R16;或可被R17取代的苯基,苯氧基或苯硫基;
R6、R7、R9、R10、R17、R21、R22和R24分别是囟素,C1-C4烷基,C1-C4囟代烷基,C1-C4烷氧基或C1-C4囟代烷氧基;
R11、R12、R13、R14、R15和R16分别是氢;C1-C2烷基;或者R11和R12、R13和R14或R15和R16可以与它们相连接的氮原子一起形成吗啉代,吡咯烷基或哌啶子基团;
R19和R25是氢或C1-C3烷基;
R20和R26是C1-C4烷基;或可被R22取代的苯基;
R23是氢,C1-C4烷基,C1-C4囟代烷基,C2-C5烷基羰基,可被R24取代的苯基羰基,C3-C4链烯基,C3-C4炔基,苯环上可被R24取代的苯甲基,C1-C4烷基亚磺酰基,C1-C4烷基磺酰基,可被R24取代的苯基亚磺酰基,可被R24取代的苯基磺酰基,C2-C4烷氧羰基,可被R24取代的苯氧基羰基,C(=O)NR25R26,C(=S)NHR26P(=S)(OR26)2,P(=O)(OR26)2,或S(=O)2NR25R26;
条件是
ⅰ)当E是囟素,C1-C6烷硫基,C1-C6烷氧基,C1-C6囟代烷氧基,苯氧基,苯硫基或苯氨基时,E仅可取代式Ⅰ和Ⅲ化合物;
ⅱ)就式Ⅲ化合物而言,E是苯基,苯氧基,苯硫基,苯氨基,苯甲基,1-萘基,2-萘基,噻吩基,呋喃基,吡啶基,上述每一个基团可被R5、R6和R7取代;或者R1是苯基,苯甲基,1-萘基,2-萘基,噻吩基,呋喃基或吡啶基,所述的每一个基团可被R8、R9和R10取代;和R1必须是在4-位;和
ⅲ)就式Ⅰ化合物而言,当E是氢,n是1,R1是5-甲基和R2是氢时,A不是可被R3和R4取代的S-三嗪基。
9、权利要求8的方法应用式Ⅰ和Ⅴ的化合物及其金属配合物,其中A和G是2-嘧啶基或2-喹唑啉基,它们可被R3、R4和R18取代;和R1是氢;羟基;C1-C4烷氧基;C1-C4烷基;C1-C4囟代烷基;C2-C3烷基羰基;C2-C4链烯基;C2-C4炔基;C2-C3烷氧基羰基;或苯基,苯甲基,1-萘基,2-萘基,噻吩基,呋喃基或吡啶基,所述的每一个基团可被R8、R9和R10取代;
R3、R4和R18分别是囟素,C1-C4烷基,环丙基,C1-C4囟代烷基,烯丙基,C2-C3炔基,C1-C4烷氧基或C1-C4囟代烷氧基;和
R23是氢,C(=O)NHR26或C2-C4烷氧基羰基。
10、权利要求9的方法,其中
A是可被R3、R4和R18取代的2-嘧啶基;
n是1或2;
E是苯基,2,3-二氢茚基,四氢萘基,1-萘基,噻吩基或吡啶基,所述每一个基团可被R5、R6和R7取代;
R1是氢,羟基,C1-C4烷氧基或C1-C4烷基;
R5是囟素,氰基,C1-C4烷基,C1-C4囟代烷基,烯丙基,炔丙基,C1-C4烷氧基,C1-C4囟代烷氧基,可被R17取代的苯基或苯氧基;和
R6、R7、R9、R10和R17分别是H,F,Cl,甲基,三氟甲基,甲氧基或三氟甲氧基;
及上述化合物的金属配合物。
11、权利要求10的方法,其中
E是可被R5、R6和R7取代的苯基、2,3-二氢茚基或四氢萘基;和
R2是氢或C1-C4烷基。
12、权利要求11的方法,其中化合物选自下述化合物
1-(4,6-二甲基-2-嘧啶基)-3-(3,4-二甲基苯基)-1,4,5,6-四氢哒嗪;
1-(4,6-二甲基-2-嘧啶基)-3-(4-乙基苯基)-1,4,5,6-四氢哒嗪;
1-(4,6-二甲基-2-嘧啶基)-1,4,5,6-四氢-3-(4-甲基苯基)哒嗪;
1-(4,6-二甲基-2-嘧啶基)-1,4,5,6-四氢-3-[4-(1-甲基乙基)苯基]哒嗪;
1-(4,6-二甲基-2-嘧啶基)-4-乙基-1,4,5,6-四氢-3-苯基哒嗪;
1-(4,6-二甲基-2-嘧啶基)-1,4,5,6-四氢-4-甲基-3-苯基哒嗪。
全文摘要
本发明涉及式I—IV化合物及其所有的几何异构体和立体异构体、农业上适宜的盐和金属配合物;涉及含有它们的农用组合物及其作为杀真菌剂的用途。
文档编号A01N43/66GK1066069SQ9210308
公开日1992年11月11日 申请日期1992年4月22日 优先权日1991年4月24日
发明者张仁裕, M·A·哈纳根, T·P·塞尔比, D·A·弗雷泽 申请人:纳幕尔杜邦公司
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