CN1216534A - 杂环取代的新颖苯衍生物和除草剂 - Google Patents
杂环取代的新颖苯衍生物和除草剂 Download PDFInfo
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Abstract
一种用通式(Ⅰ)表示的化合物:式中R1是卤原子、C1-6烷基、C1-6烷氧基等,R2为卤原子、C1-6烷基磺酰基等,n为0或1等,Het是含有1-4个用碳原子键合的N、O或S原子且被R7和R8取代的饱和或不饱和的五员杂环,R3为氢原子等,R4为氢原子、C1-6烷基等,R5为C1-6烷基等,R6为可取代的苯基,X是SO2、CH2CO或亚甲基。本发明的化合物具有优良的除草活性。含有它们的组合物适用作除草剂。
Description
技术领域:
本发明涉及一种在吡唑环的4位上被苯甲酰基取代的新颖吡唑衍生物和除草剂。
背景技术:
(Z=杂环基)
本发明的目的是提供一种适于以工业规模方便地合成的除草剂。这种除草剂能在较低剂量下肯定有效,并且非常安全,而且它对作物具有较高的选择性。
发明的公开:
本发明涉及用通式[Ⅰ]表示的苯甲酰基部分的3位被一个杂环取代的4-苯甲酰基吡唑化合物以及含有吡唑环上烯醇羟基被保护的化合物作为活性组分的除草剂。
就是说,本发明涉及一种用结构式[Ⅰ]表示的化合物或含有这种化合物的除草剂:(其中R1是卤原子、C1-6烷基、C1-6烷氧基、硝基、氰基、C1-6卤代烷基、C1-6卤代烷氧基、C1-6烷硫基、C1-6烷基亚磺酰基、或C1-6烷基磺酰基。
R2是卤原子、硝基、氰基、C1-6烷基、C1-6烷氧基、C1-6卤代烷基、C1-6卤代烷氧基、C1-6烷硫基、C1-6烷基亚磺酰基、或C1-6烷基磺酰基。
R3是卤原子、C1-6烷基、C1-6烷氧基、硝基、氰基、C1-6卤代烷基、C1-6烷硫基、C1-6烷基亚磺酰基、或C1-6烷基磺酰基。n为0、1或2,当n等于2时,用R3表示的基团可以相同或不同。
Het是含有1-3个N、O或S原子且被R7和R8取代的饱和或不饱和的五员杂环,它的碳原子部分与苯环键合。
R4是氢原子或C1-6烷基,
R5是氢原子、C1-6烷基、C2-6链烯基或C2-6链炔基。
R6是C1-6烷基、C3-8环烷基或苯基(它可以被C1-6烷基、C1-6烷氧基、C1-6卤代烷基、C1-6卤代烷氧基、硝基或卤原子取代)。
X是SO2、(CH2)mCO、C1-6可被烷基取代的亚烷基或一个单键,m为0、1、2或3)。
下面,将详细叙述本发明。
本发明涉及一种用上述结构式[Ⅰ]表示的吡唑化合物以及含有这些化合物作为有效组分的除草剂:在结构式[Ⅰ]中,R1是卤原子(如氟、氯或溴)、C1-6烷基(如甲基、乙基、丙基、异丙基、丁基和叔丁基)、C1-6烷氧基(甲氧基、乙氧基、丙氧基、异丙氧基、丁氧基或叔丁氧基)、硝基、氰基、C1-6卤代烷基(如三氟甲基和三氟乙基)、C1-6卤代烷氧基(如三氟甲氧基)、C1-6烷硫基(甲硫基、乙硫基、丙硫基或异丙硫基)、C1- 6烷基亚磺酰基(如甲基亚磺酰基、乙基亚磺酰基、丙基亚磺酰基和异丙基亚磺酰基)、或C1-6烷基磺酰基(如甲基磺酰基、乙基磺酰基、丙基磺酰基和异丙基磺酰基)。
R2是卤原子(如氟、氯或溴)、硝基、氰基、C1-6烷基(如甲基、乙基、丙基、异丙基、丁基和叔丁基)、C1-6烷氧基(甲氧基、乙氧基、丙氧基、异丙氧基、丁氧基或叔丁氧基)、C1-6卤代烷基(如三氟甲基和三氟乙基)、C1-6卤代烷氧基(如三氟甲氧基或三氯甲氧基)、C1-6烷硫基(甲硫基、乙硫基、丙硫基或异丙硫基)、C1-6烷基亚磺酰基(如甲基亚磺酰基、乙基亚磺酰基、丙基亚磺酰基和异丙基亚磺酰基)、或C1-6烷基磺酰基(如甲基磺酰基、乙基磺酰基、丙基磺酰基和异丙基磺酰基)。
R3是卤原子(如氟、氯或溴)、C1-6烷基(如甲基、乙基、丙基、异丙基、丁基和叔丁基)、C1-6烷氧基(甲氧基、乙氧基、丙氧基、异丙氧基、丁氧基或叔丁氧基)、硝基、氰基、C1-6卤代烷基(如三氟甲基和三氟乙基)、C1-6烷硫基(甲硫基、乙硫基、丙硫基或异丙硫基)、C1-6烷基亚磺酰基(如甲基亚磺酰基、乙基亚磺酰基、丙基亚磺酰基和异丙基亚磺酰基)、或C1-6烷基磺酰基(如甲基磺酰基、乙基磺酰基、丙基磺酰基和异丙基磺酰基)。
Het是含有1-4个N、O或S原子且可能被R7和R8取代的饱和或不饱和的五员杂环,该杂环的碳原子部分与苯环键合。
Het的例子包括2-呋喃基、3-呋喃基、4-呋喃基、5-呋喃基、2-噻吩基、3-噻吩基、4-噻吩基、5-噻吩基、2-吡咯基、3-吡咯基、4-吡咯基、2-咪唑基、4-咪唑基、5-咪唑基、3-吡唑基、4-吡唑基、5-吡唑基、1,3-噁唑-2-基、1,3-噁唑-4-基、1,3-噁唑-5-基、1,2-异噁唑-3-基、1,2-异噁唑-4-基、1,2-异噁唑-5-基、1,3-噻唑-2-基、1,3-噻唑-4-基、1,3-噻唑-5-基、1,2-异噻唑-3-基、1,2-异噻唑-4-基、1,2-异噻唑-5-基、1,2,4-噁二唑-3-基、1,2,4-噁二唑-5-基、1,3,4-噁二唑-2-基、1,3,4-噁二唑-5-基、1,2,4-噻二唑-3-基、1,2,4-噻二唑-5-基、1,3,4-噻二唑-2-基、1,3,4-噻二唑-5-基、1,2,4-三唑-3-基和1,2,4-三唑-5-基。
另外,每个杂环可在任选的部位有R7和R8,R7和R8分别是卤原子(如氟、氯或溴)、C1-6烷基(如甲基或乙基)、C1-6烷氧基(如甲氧基或乙氧基)或C1-6卤代烷基(如三氟甲基)。
在上述通式中,R7和R8各自分别为氢原子、C1-6烷基(如甲基、乙基、丙基、异丙基、丁基或叔丁基)、C1-6烷氧基(如甲氧基、乙氧基或丙氧基)、卤原子(如氟、氯或溴)或C1-6卤代烷基(如三氟甲基)。
另外,R4是氢原子或C1-6烷基(如甲基、乙基、丙基、异丙基、丁基、异丁基和叔丁基)、C1-6卤代烷基(如三氟甲基)、羟基C1-6烷基(如羟甲基、1-羟乙基、2-羟乙基或羟丙基)、C1-6烷氧基C1-6烷基(如甲氧基甲基、乙氧基甲基、丙氧基甲基、异丙氧基甲基、甲氧基乙基、乙氧基乙基、乙氧基丙基、甲氧基丙基、乙氧基丙基、丁氧基甲基、叔丁氧基甲基或叔丁氧基乙基)。
R5是氢原子、C1-6烷基(如甲基、乙基、丙基、异丙基、丁基、异丁基和叔丁基)、C2-6链烯基(如乙烯基、丙烯基、巴豆基、烯丙基)或C2-6链炔基(如乙炔基或炔丙基)。
R6是C1-6烷基(如甲基、乙基、丙基、异丙基、丁基、异丁基和叔丁基)、C3-C8环烷基(如环丙基、环丁基、环戊基和环己基)或苯基(可被C1-6烷基,如甲基、乙基、丙基、异丙基、丁基、异丁基和叔丁基)、C1-6烷氧基(甲氧基、乙氧基、丙氧基、异丙氧基、丁氧基或叔丁氧基)、C1-6卤代烷基(如三氟甲基、三氯甲基、氟甲基、氯甲基、二氟甲基、二氯甲基、三氟乙基或五氟乙基)、C1-6卤代烷氧基(如三氟甲氧基)、硝基或卤原子(如氟、氯或溴)取代)。
X是SO2、(CH2)mCO(m为0、1、2或3)或C1-6可被烷基(如甲基或乙基)取代的亚烷基(如亚甲基、亚乙基或亚丙基)或一个单键。
XR6优选的实例包括CH2Ar、CH2COAr或SO2Ar(式中Ar是苯基,其中苯环的任选部位可被C1-6烷基(如甲基、乙基、丙基、异丙基、丁基、异丁基和叔丁基)、C1-6烷氧基(如甲氧基、乙氧基、丙氧基、异丙氧基、丁氧基或叔丁氧基)、C1-6卤代烷基(如三氟甲基、三氯甲基、氟甲基、氯甲基、二氟甲基、二氯甲基、三氟乙基或五氟乙基)取代的苯基)或卤原子(如氟、氯或溴)。更优选的实例包括可有取代基的CH2Ar基团。
化合物的制备方法
化合物[Ⅳa]和[Ⅳb]可分别在1摩尔或过量的碱存在下通过化合物[Ⅶ]和[Ⅴa](Q如上所述)的反应制得。化合物[Ⅶ]和[Ⅴa]的用量分别为1摩尔,或一种化合物的用量过量。可用于上述反应中的碱的实例是碱金属氢氧化物(如KOH和NaOH)、碱金属碳酸盐(如碳酸钠和碳酸钾)、碱土金属氢氧化物(如氢氧化钙和氢氧化镁)、碱土金属碳酸盐(如碳酸钙)、三(C1-6烷基)胺(如三乙胺和二异丙基乙胺)、有机碱(如吡啶)和磷酸钠等。
而且,可用于上述反应的溶剂实例是水、二氯甲烷、氯仿、甲苯、乙酸乙酯、二甲基甲酰胺(DMF)、四氢呋喃(THF)、二甲氧基乙烷(DMB)、乙腈等。
将上述的反应混合物在0℃至50℃温度范围内搅拌,直至所述反应完全为止。另外,所述反应可通过采用相转移剂(如季铵盐)在两相体系中进行。
而且,结构式[Ⅳa]和[Ⅳb]的化合物也可通过在脱水缩合剂(debydrocondesing agent)(如二环己基碳化二亚胺(DCC))的存在下化合物[Ⅶ]与[Ⅴb]的反应制得。可用来与DCC等反应中的溶剂实例包括二氯甲烷、氯仿、甲苯、乙酸乙酯、二甲基甲酰胺、THF、二甲氧基乙烷、乙腈和叔戊醇。反应混合物在-10℃至50℃的温度范围内顺利进行。反应混合物可根据常规方法进行处理。
可将化合物[Ⅳa]和[Ⅳb]作为混合物用于下列的转变反应。该转变反应可在氰基化合物和弱碱存在下进行。就是说,1摩尔化合物[Ⅳa]和化合物[Ⅳb]与1-4摩尔(较佳的为1-2摩尔)的碱和0.01-1.0摩尔(较佳的为0.05-0.2摩尔)的氰基化合物反应来制得用[Ⅰa]表示的化合物。这里可用的碱可采用上述碱的任何一个。此外,氰基化合物的实例包括氰化钾、氰化钠、丙酮氰醇、氰化氢和含有氰化钾的聚合物。如果在反应体系中加入少量相转移催化剂如冠醚,反应可在较短时间内完成。反应温度低于80℃,最好在室温至40℃范围内。可用的溶剂的实例是1,2-二氯乙烷、甲苯、乙腈、二氯甲烷、乙酸乙酯、二甲基甲酰胺、甲基异丙基酮、THF和二甲氧基乙烷。
另外,该转变反应也可在碱(如碳酸钾、碳酸钠、三乙胺或吡啶)的存在下在惰性溶剂中进行。反应中碱的用量按化合物[Ⅳa]和[Ⅳb]计为0.5-2.0摩尔,反应中可用的溶剂包括THF、二噁烷、叔戊醇和叔丁醇。反应温度在室温至所用溶剂沸点的温度范围内。
另外,化合物[Ⅰa]也可通过在不分离化合物[Ⅳa]和[Ⅳb]的条件下同时用碱和脱水缩合剂(如DCC)来制得。可用碱的实例是碳酸钾、碳酸钠、三乙胺和吡啶。碱的用量按化合物[Ⅶ]计在0.5-2.0摩尔范围内。另外,可用于该反应的溶剂的实例是THF、二噁烷、叔戊醇、叔丁醇等,反应温度在室温至所用溶剂沸点的温度范围内。
化合物[Ⅰ]可通过在碱的存在下化合物[Ⅰa]与R8X-L(L为卤素)的反应制得。可用于本反应的碱的实例包括碱金属氢氧化物(如KOH和NaOH)、碱金属碳酸盐(如碳酸钠和碳酸钾)、碱土金属氢氧化物(如氢氧化钙)、碱土金属碳酸盐(如碳酸钙)、三(C1-6烷基)胺(如三乙胺和二异丙基乙胺)、有机碱(如吡啶)和磷酸钠等。可用溶剂的实例包括二氯甲烷、氯仿、甲苯、乙酸乙酯、二甲基甲酰胺、THF、二甲氧基乙烷和乙腈。该反应在0℃至溶剂的沸点间某一温度进行。另外,化合物[Ⅰ]也可通过使用相转移催化剂(如季铵盐)在水和上述溶剂中非水溶性溶剂的两相体系中进行的反应制得。
其中R1和R2如上所述,R9是氢原子或低级烷基,W是卤原子。
醛化合物(3)可根据已知的方法从甲苯衍生物(1)制得,该方法例如包括在光或自由基反应引发剂(如过氧苯甲酰)的存在下,使与卤化剂(如卤素(如氯和溴)、N-溴代琥珀酰亚胺(NBS)和N-氯代琥珀酰亚胺(NCS))反应来制得苄基卤化物衍生物(2),然后根据J.Am.Chem.Soc.,Vol.71,p.1767(1949)中所述的方法对其进行处理制备醛化合物(3)。更具体地,醛化合物(3)可通过在醇溶剂(如甲醇和乙醇)中和在0℃至所用溶剂沸点的温度范围内苄基卤化物衍生物(2)与硝基烷(如2-硝基丙烷)的碱金属盐的反应来制得。
下面,羧酸化合物(4)可通过高锰酸钾等的氧化反应从甲苯衍生物(1)制得,或是它可用已知的方法(如琼斯试剂、铬酸、高锰酸钾等的另一种氧化反应)由醛化合物(3)制得。
醛肟化合物(5)可在碱的存在下通过醛(3)与盐酸羟胺或硫酸羟胺的反应制得。另外,该醛肟化合物(5)可与脱水剂(如乙酸酐、五氧化磷或亚硫酰氯)来制备氰基化合物(6)。
接下来,酮化合物(8)例如通过应用有机反应、第15卷、第254页所述的诺葛耳反应制备硝基烯烃物质(7),用活性铁-水体系、氢化锂铝等还原该硝基烯烃物质(7),然后进行水解而制得。
酰基化合物(10)可通过使醛(3)与格氏试剂反应来制备醇物质(9),然后用氧化剂(如活化的二氧化锰、铬酸等)来氧化醇化合物(9)而制得。
乙烯基酮化合物(24)可用文献中已知的方法制得,即在水中使醛化合物(3)与甲基酮(21)在催化剂的存在下和在0-50℃的温度下反应1-50小时,制得醛醇化合物(23),然后在合适的溶剂中和催化剂的存在下使这种化合物脱水。可用于制备醛醇化合物(23)的反应中的催化剂实例是金属氢氧化物(如氢氧化钠和氢氧化钡)和有机碱(如哌啶和吡啶)。
另外,可用于上述脱水反应的催化剂的实例是酸,例如浓硫酸和对-甲苯磺酸。此外,用于所述脱水反应的溶剂的实例是烃(如苯和甲苯)和卤代烃(如二氯甲烷和氯仿)。
乙烯基酮化合物(24)也可通过醛化合物(3)与正膦(22)(rhosphorane)化合物在合适的溶剂中、室温至所用溶剂沸点的温度范围内反应10分钟-30小时来制得。
(式中R1、R2和R9如上所述,R13、R14和R15分别是低级烷基。)
首先,羧酸化合物(4)与氯化剂(如光气、亚硫酰氯和草酰氯)在惰性溶剂(诸如苯或甲苯之类的烃,或诸如二氯甲烷或氯仿之类的卤代烃)中反应,制得结羰酰氯化合物(11)中间体。
接着,用已知的方法制备酰胺化合物(12)和酰肼化合物(13)。在该方法中用碳酰氯化合物(11)处理氨或肼。另外,通过碳酰氯化合物(11)与将镁的醇化合物作用于β-酮酯化合物(14)上制得的镁盐反应可制得β-二酮化合物(15)。
(式中R1、R2和R9如下所述,R16相应于上述的R7或R8)。
用结构式(17)表示的噁唑可通过在合适的溶剂中、在室温至所选溶剂的沸点的温度范围内以及在碱的存在下使醛化合物(3)与异腈化合物(16)反应1-30小时而制得。
该反应中所用的碱的实例是碳酸盐(如碳酸氢钠和碳酸钾)、碱金属氢氧化物(如氢氧化钠和氢氧化钾)、金属醇化物(如甲醇钠和乙醇钠)和有机碱(如三乙胺和1,8-二氮杂双环[5.4.0]十一碳-7-烯(DBU))。
(式中R1、R2和R9如上所述,R17相应于上述的R7或R8)。
用结构式(20)表示的噻唑化合物可由酰胺化合物(12)经过硫代酰胺化合物(18)制得。这就是说,硫代酰胺化合物(18)可通过在溶剂中或无溶剂的条件下在室温至所选溶剂的沸点的温度范围内使酰胺化合物(12)与五硫化磷或Lawesson’试剂反应制得。该反应中可用的溶剂的实例包括烃(如苯和甲苯)和醚(如二噁烷)。
然后在合适的溶剂中,在室温至所选溶剂的沸点的温度范围内和加入碱或不加入碱的条件下使所得的硫代酰胺化合物(18)与α-卤代酮(19)反应1-30小时,制得噻唑化合物(20)。
可用于该反应中的碱的实例包括碳酸盐(如碳酸氢钠和碳酸钾)、碱金属氢氧化物(如氢氧化钠和氢氧化钾)、金属醇化物(如甲醇钠和乙醇钠)和有机碱(如三乙胺和1,8-二氮杂双环[5.4.0]十一碳-7-烯(DBU))。另外,该反应中所用的溶剂的实例是醇(如甲醇、乙醇和异丙醇)、烃(如苯和甲苯)、卤代烃(如二氯甲烷和氯仿)、酮类(如丙酮和丁酮)、酯类(如乙酸甲酯和乙酸乙酯)、醚类(如四氢呋喃和二噁烷)、腈类(如乙腈)、二甲基甲酰胺。
(式中的、R2、R9和R18如上所述,R19是氢原子或C1-6烷基)。
异噁唑化合物(26a)可通过如下方法制得:即首先在0℃-所用溶剂沸点的温度下使乙烯基酮化合物(24)和羟胺在合适的溶剂中反应0.5-5小时,获得肟化合物(25),然后进行闭环反应和氧化反应。在该反应中,可使用羟胺的硫酸盐或盐酸盐,可不进行中和就直接使用,然而,这些羟胺盐也可在用合适的碱中和后再使用。中和所用的碱的实例是碳酸盐(如碳酸氢钠和碳酸钾)、碱金属氢氧化物(如氢氧化钠和氢氧化钾)、羧酸盐(如乙酸钠)、金属醇化物(如甲醇钠和乙醇钠)和有机碱(如三乙胺和吡啶)。
另外,该反应中所用的溶剂的实例是醇(如甲醇、乙醇和异丙醇)、烃(如苯和甲苯)、卤代烃(如二氯甲烷和氯仿)、醚(如THF和二噁烷)、腈(如乙腈)、DMF、吡啶、乙酸、水和上述两种或多种溶剂组成的混合溶剂。在上述闭环氧化反应中,可采用碘-碘化钾、N-溴代琥珀酰亚胺或钯催化剂,它们可分别根据J.Amer.chem.Soc.,P.94(1972),J.Heterocycl.Chem.,Vol.14,p.1289(1977)和TetrahedronLett.p.5075(1977)中所述的方法来制备。
吡唑化合物(28a)可分两步由乙烯基酮化合物(24)制得。即在0℃至所用溶剂沸点的温度下使乙烯基酮化合物(24)和取代的肼在合适的溶剂中反应0.5-5小时,制得二氢吡唑化合物(27)。该反应中所用的溶剂的实例是醇(如甲醇、乙醇和异丙醇)、烃(如苯和甲苯)、卤代烃(如二氯甲烷和氯仿)、醚(如THF和二噁烷)、腈(如乙腈)、DMF、吡啶、乙酸、水和上述两种或多种溶剂组成的混合溶剂。
接着,可通过在室温至所用溶剂沸点的温度下使二氢吡唑化合物(27)与氧化剂(如活化的二氧化锰、二氰二氯苯醌(DDQ)、过氧化镍或NBS)在合适的溶剂中反应制得吡唑化合物(28a)。该反应中所用的溶剂的实例包括烃(如苯和甲苯)和卤代烃(如氯仿和四氯化碳)。
(式中R1、R2、R9如上所述,R20和R21分别相应于上述的R7或R8,R22相应于上述的R5)。
用结构式(26b)表示的异噁唑化合物和用结构式(28b)表示的吡唑化合物也可分别通过使β-二酮化合物(15)与羟胺和取代肼反应来制得。两种反应都可在合适的溶剂中在0℃至所用溶剂沸点的温度范围内进行以制备所需的化合物。在该反应中,也可用酸如硫酸或对-甲苯磺酸来作为催化剂。该反应中所用的溶剂的实例包括醇(如甲醇、乙醇和异丙醇)、烃(如苯和甲苯)、卤代烃(如二氯甲烷和氯仿)、醚(如THF和二噁烷)、腈(如乙腈)、DMF、吡啶、乙酸、水和上述两种或多种溶剂组成的混合溶剂。
(式中R1、R2和R9如上所述,R23和R24相应于上述的R7或R8)。
用结构式(31)表示的异噁唑化合物可通过在-10至50℃的温度下使乙醛肟化合物(5)与卤化剂(如氯、溴、N-氯代琥珀酰亚胺(NCS)或NBS)在,溶剂(诸如苯或甲苯之类的烃、诸如二氯甲烷或氯仿之类的卤代烃、THF或二噁烷之类的醚、乙腈之类的腈或DMF)中反应,进一步与三乙胺之类的有机碱或碳酸盐(如碳酸氢钠或碳酸钾)之类的碱反应,制得氧化腈化合物(29),然后使该氧化腈化合物与乙酸乙烯酯(30)在室温至所选溶剂的沸点的温度范围内进行反应而制得。另外,异噁唑化合物(31)可通过在乙酸乙烯酯的存在下使上述卤化物与上述碱反应而制得。
(式中R1、R2和R9如上所述,R25相应于上述的R7)。
噁二唑化合物(34)可通过偕胺肟化合物(31)制得。偕胺肟化合物(31)可通过在合适的溶剂中和在室温至所选溶剂的沸点的温度范围内使腈化合物(6)与羟胺反应而制得。通过用合适的碱中和可以使用羟胺的硫酸盐或盐酸盐。中和所用的碱的实例包括碳酸盐(如碳酸氢钠和碳酸钾)、碱金属氢氧化物(如氢氧化钠和氢氧化钾)、羧酸盐(如乙酸钠)、金属醇化物(如甲醇钠和乙醇钠)和有机碱(如三乙胺和吡啶)。
该反应中所用的溶剂的实例包括醇(如甲醇、乙醇和异丙醇)、烃(如苯和甲苯)、卤代烃(如二氯甲烷和氯仿)、醚(如THF和二噁烷)、腈(如乙腈)、DMF、吡啶、乙酸、水和上述两种或多种溶剂组成的混合溶剂。
然后在合适碱的存在下,在合适的溶剂中和在-15℃至所选溶剂的沸点的温度范围内使所得的偕胺肟化合物(31)与酸酐(32)或酰氯(33)反应1-30小时,制备噁二唑化合物(34)。
该反应中所用的碱的实例包括碳酸盐(如碳酸氢钠和碳酸钾)、碱金属氢氧化物(如氢氧化钠和氢氧化钾)和有机碱(如三乙胺、吡啶和1,8-二氮杂双环[5.4.0]十一碳-7-烯(DBU))。
(式中R1、R2和R9如上所述,R26相应于上述的R7,R27是低级烷基)。
酰肼化合物(13)与原酸酯(35)或亚氨酸酯(imidate)(36)在合适的溶剂中和在-15℃至所选溶剂的沸点的温度范围内反应1-30小时,制备噁二唑化合物(37)。该反应中所用的溶剂的实例包括烃(如苯和甲苯)、卤代烃(如二氯甲烷和氯仿)、醚(如THF和二噁烷)、腈(如乙腈)、DMF和吡啶。
(式中R1、R2和R9如上所述,R28、R29和R31相应于上述的R7或R8,R30是低级烷基)。
用结构式(40)表示的异噁唑化合物可由酮化合物(8)经二甲氨基次甲基(methylidene)化合物(39)制得。即异噁唑化合物可通过在不加溶剂的条件下或在合适的溶剂中和在室温至200℃或所选溶剂的沸点的温度范围内使酮化合物(8)与二甲基酰氨基缩醛(38)反应而制得。可用于该反应的溶剂的实例包括烃,如甲苯和二甲苯。
接着使所得的二甲氨基次甲基化合物(39)与羟胺反应制备异噁唑化合物(40),条件如制备异噁唑化合物(26b)时一样。
(式中R1、R2、R9和R30如下所述,R32相应于上述的R7,R33相应于上述的R5)。
用结构式(44)表示的噁二唑可由酰胺化合物(12)经脒(43)制得。即这种脒化合物(43)可通过在无溶剂的条件下或在一种合适的溶剂中和在0至200℃或所选溶剂的沸点的温度范围内使酰胺化合物(12)与二甲基酰氨基缩醛(42)反应而制得。该反应中所用的溶剂的实例包括烃,如甲苯和二甲苯。接着,按与制备异噁唑化合物(26b)时相同的方法由所得的脒化合物(43)和羟胺制备噁二唑化合物(44)。
另外,用结构式(45)表示的三唑化合物也可通过按与制备吡唑化合物(28b)时相同的方法使脒化合物(43)与取代的肼反应而制得。
另外,用通式(26-3)表示的异噁唑化合物可通过在碱的存在下使用结构式(26-1)表示的4-Cl化合物与用R′SH表示的硫醇反应来制得用结构式(26-2)表示的4-SR′化合物,然后将其氧化而制得。
(式中R1、R9和Het如上所述,R′为C1-6烷基)。
该反应中所用的碱的实例包括碱金属氢氧化物(如氢氧化钠和氢氧化钾)、金属醇化物(如甲醇钠和乙醇钠)、碳酸盐(如碳酸钠和碳酸钾)、氢化物(如氢化钠)和有机碱(如三乙胺、二异丙基乙基胺和二氮杂双环[5.4.0]十一碳-7-烯(DBU)和吡啶)。另外,该反应中所用的溶剂的实例包括醇(如甲醇和乙醇)、醚(如四氢呋喃(THF)和1,2-二甲氧基乙烷(DME))、酰胺(N,N-二甲基甲酰胺(DMF)和N,N-二甲基乙酰胺(DMA))、DMSO、乙腈、苯、甲苯和二甲苯。接下来的氧化反应可在惰性溶剂(如水、乙酸之类的有机酸或卤代烃(如二氯甲烷、氯仿或四氯化碳))中用氧化剂(如过酸(如过氧化氢、过乙酸、过苯甲酸或间氯过苯甲酸)或次氯酸(如次氯酸钠或次氯酸钾))进行。该反应在室温至所选溶剂的沸点的温度范围内顺利进行。
本发明的化合物以及各种中间体可通过在反应完成后用常规的后处理方法制得。
本发明化合物和各种中间体的结构已用IR、NMR和MS测定。
本发明的最佳实施方式:
以下将参照实施例、制备实施例和对比例来更详细地描述本发明的化合物。
实施例1
制备4-[2,4-二氯-3-(3-甲基-1,2-异噁唑-5-基)苯甲酰基]-1,3-二甲基-5-(4-甲基苯磺酰氧基)吡唑(化合物Ⅰ-16)
将1.5克4-[2,4-二氯-3-(3-甲基-1,2-异噁唑-5-基)苯甲酰基]-1,3-二甲基-5-羟基吡唑溶解在100毫升二氯甲烷中,加入含0.75克碳酸钾的50毫升水,然后加入1.5克对甲苯磺酰氯。再加入0.15克氯化苄基三乙铵后,在室温下搅拌过夜。从反应溶液中分离出所得的有机相,用饱和氯化钠溶液洗涤,然后用无水硫酸镁干燥,减压下蒸掉溶剂。所得的残余物用硅胶柱色谱纯化后得到1.4克所需化合物结晶,熔点为160-161℃。
实施例2
将0.60克4-[2,4-二氯-3-(3-甲基-1,2-异噁唑-5-基)苯甲酰基]-5-羟基-1-甲基吡唑溶解在100毫升DMF中,加入0.30克碳酸钾,然后加入0.34克苄基溴。在室温下搅拌过夜后,将反应溶液倒入100毫升冰水中,然后用100毫升氯仿萃取。所得的有机相用饱和氯化钠溶液洗涤,然后用无水硫酸镁干燥,蒸掉溶剂。所得的残余物用硅胶柱色谱纯化后得到0.1克所需化合物粉末。
1H-NMR的数据是表10中的NMR-2。
实施例3
将0.20克4-[2,4-二氯-3-(3-甲基-1,2-异噁唑-5-基)苯甲酰基]-5-羟基-1-甲基吡唑溶解在3毫升DMF中,加入0.10克碳酸钾,然后加入0.14克苯甲酰甲基溴。在室温下搅拌3小时后,将反应溶液倒入60毫升冰水中,然后用60毫升氯仿萃取。所得的有机层用饱和氯化钠溶液洗涤,然后用无水硫酸镁干燥,蒸掉溶剂。所得的残余物用硅胶柱色谱纯化后得到0.2克所需化合物粉末。
1H-NMR的数据是表10中的NMR-5。
实施例4
将0.40克4-[2,4-二氯-3-(1,2-异噁唑-3-基)苯甲酰基]-1-乙基-5-羟基吡唑溶解在5毫升DMF中,加入0.20克碳酸钾,然后加入0.23克苄基溴。在室温下搅拌4小时后,将反应溶液倒入50毫升冰水中,然后用70毫升乙醚萃取。所得的有机层用饱和碳酸氢钠水溶液洗涤,然后用饱和氯化钠溶液洗涤,然后用无水硫酸镁干燥,蒸掉溶剂。将所得的残余物溶解在氯仿中,加入正己烷。过滤收集沉淀的结晶,得到0.36克所需的化合物,熔点为124-127℃。
可按上述方法制得的本发明化合物的实例总结于表1-9中。另外,将1H-NMR光谱数据总结于表10中。
No. | R1 | R2 | R4 | R5 | R7 | R8 | X | R6 | 物理值熔点℃ |
Ⅰ-1 | Cl | Cl | H | CH3 | H | H | SO2 | 4-Me-Ph | |
Ⅰ-2 | Cl | Cl | H | C2H5 | H | H | SO2 | 4-Me-Ph | |
Ⅰ-3 | Cl | Cl | H | iPr | H | H | SO2 | 4-Me-Ph | |
Ⅰ-4 | Cl | Cl | CH3 | CH3 | H | H | SO2 | 4-Me-Ph | |
Ⅰ-5 | Cl | Cl | H | CH3 | H | H | CH2 | Ph | |
Ⅰ-6 | Cl | Cl | H | C2H5 | H | H | CH2 | Ph | |
Ⅰ-7 | Cl | Cl | H | iPr | H | H | CH2 | Ph | |
Ⅰ-8 | Cl | Cl | CH3 | CH3 | CH3 | H | CH2 | 2-Me-Ph | |
Ⅰ-9 | Cl | Cl | H | CH3 | H | H | CH2CO | Ph | |
Ⅰ-10 | Cl | Cl | H | C2H5 | H | H | CH2CO | Ph | |
Ⅰ-11 | Cl | Cl | H | iPr | H | H | CH2CO | Ph | |
Ⅰ-12 | Cl | Cl | CH3 | CH3 | CH3 | H | CH2CO | 3-Me-Ph | |
Ⅰ-13 | Cl | Cl | H | CH3 | CH3 | H | SO2 | 4-Me-Ph | [154-159] |
Ⅰ-14 | Cl | Cl | H | C2H5 | CH3 | H | SO2 | 4-Me-Ph | 粉末(NMR-1) |
Ⅰ-15 | Cl | Cl | H | iPr | CH3 | H | SO2 | 4-Me-Ph | |
Ⅰ-16 | Cl | Cl | CH3 | CH3 | CH3 | H | SO2 | 4-Me-Ph | [160-161] |
Ⅰ-17 | Cl | Cl | H | CH3 | CH3 | H | CH2 | Ph | [111-112.5](NMR-2) |
Ⅰ-18 | Cl | Cl | H | C2H3 | CH3 | H | CH2 | Ph | [78.5-80](NMR-3) |
表1(续)
No. | R1 | R2 | R4 | R5 | R7 | R8 | X | R6 | 物理值熔点℃ |
Ⅰ-19 | Cl | Cl | H | iPr | CH3 | H | CH2 | Ph | |
Ⅰ-20 | Cl | Cl | CH3 | CH3 | CH3 | H | CH2 | Ph | [125-127](NMR-4) |
Ⅰ-21 | Cl | Cl | H | CH3 | CH3 | H | CH2CO | Ph | 粉末(NMR-5) |
Ⅰ-22 | Cl | Cl | H | C2H5 | CH3 | H | CH2CO | Ph | |
Ⅰ-23 | Cl | Cl | H | iPr | CH3 | H | CH2CO | Ph | |
Ⅰ-24 | Cl | Cl | CH3 | CH3 | CH3 | H | CH2CO | Ph | |
Ⅰ-25 | Cl | Cl | H | CH3 | H | CH3 | SO2 | 4-Me-Ph | |
Ⅰ-26 | Cl | Cl | H | C2H5 | H | CH3 | SO2 | 4-Me-Ph | |
Ⅰ-27 | Cl | Cl | H | iPr | H | CH3 | SO2 | 4-Me-Ph | |
Ⅰ-28 | Cl | Cl | CH3 | CH3 | H | CH3 | SO2 | 4-Me-Ph | |
Ⅰ-29 | Cl | Cl | H | CH3 | H | CH3 | CH2 | Ph | |
Ⅰ-30 | Cl | Cl | H | C2H5 | H | CH3 | CH2 | Ph | |
Ⅰ-31 | Cl | Cl | H | iPr | H | CH3 | CH2 | Ph | |
Ⅰ-32 | Cl | Cl | CH3 | CH3 | CH3 | CH3 | CH2 | Ph | |
Ⅰ-33 | Cl | Cl | H | CH3 | H | CH3 | CH2CO | Ph | |
Ⅰ-34 | Cl | Cl | H | C2H5 | H | CH3 | CH2CO | Ph | |
Ⅰ-35 | Cl | Cl | H | iPr | H | CH3 | CH2CO | Ph | |
Ⅰ-36 | Cl | Cl | CH3 | CH3 | CH3 | CH3 | CH2CO | Ph | |
Ⅰ-37 | Cl | Cl | H | CH3 | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅰ-38 | Cl | Cl | H | C2H5 | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅰ-39 | Cl | Cl | H | iPr | CH3 | CH3 | SO2 | 4-Me-Ph |
表1(续)
No. | R1 | R2 | R4 | R5 | R7 | R8 | X | R6 | 物理值熔点℃ |
Ⅰ-40 | Cl | Cl | CH3 | CH3 | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅰ-41 | F | Cl | H | CH3 | CH3 | CH3 | CH2 | Ph | |
Ⅰ-42 | F | Cl | H | C2H5 | CH3 | CH3 | CH2 | Ph | |
Ⅰ-43 | Cl | Cl | H | iPr | CH3 | CH3 | CH2 | Ph | |
Ⅰ-44 | Cl | Cl | CH3 | CH3 | CH3 | CH3 | CH2 | Ph | |
Ⅰ-45 | Cl | Cl | H | CH3 | CH3 | CH3 | CH2CO | Ph | |
Ⅰ-46 | Cl | Cl | H | C2H5 | CH3 | CH3 | CH2CO | Ph | |
Ⅰ-47 | Cl | Cl | H | iPr | CH3 | CH3 | CH2CO | Ph | |
Ⅰ-48 | Cl | Cl | CH3 | CH3 | CH3 | CH3 | CH2CO | Ph | |
Ⅰ-49 | Cl | Cl | H | tBu | CH3 | H | CH2 | Ph | NMR-6 |
Ⅰ-50 | Cl | Cl | H | tBu | CH3 | H | CH2 | Ph | |
Ⅰ-51 | Cl | Cl | CH3 | tBu | CH3 | H | SO2 | 4-Me-Ph | |
Ⅰ-52 | Cl | Cl | CH3 | tBu | CH3 | H | SO2 | 4-Me-Ph | |
Ⅰ-53 | Cl | Cl | CH3 | tBu | CH3 | H | CH2CO | Ph | |
Ⅰ-54 | Cl | Cl | CH3 | tBu | CH3 | H | CH2CO | Ph | |
Ⅰ-55 | Cl | SO2CH3 | H | CH3 | H | H | SO2 | 4-Me-Ph | |
Ⅰ-56 | Cl | SO2CH3 | H | C2H5 | H | H | SO2 | 4-Me-Ph | |
Ⅰ-57 | Cl | SO2CH3 | H | iPr | H | H | SO2 | 4-Me-Ph | |
Ⅰ-58 | Cl | SO2CH3 | CH3 | CH3 | H | H | SO2 | 4-Me-Ph | |
Ⅰ-59 | F | SO2CH3 | H | CH3 | H | H | CH2 | Ph | |
Ⅰ-60 | F | SO2CH3 | H | C2H5 | H | H | CH2 | Ph | |
Ⅰ-61 | Cl | SO2CH3 | H | iPr | H | H | CH2 | Ph | |
Ⅰ-62 | Cl | SO2CH3 | CH3 | CH3 | CH3 | H | CH2 | Ph |
表1(续)
No. | R1 | R2 | R4 | R5 | R7 | R8 | X | R6 | 物理值熔点℃ |
Ⅰ-63 | Cl | SO2CH3 | H | CH3 | H | H | CH2CO | Ph | |
Ⅰ-64 | Cl | SO2CH3 | H | C2H5 | H | H | CH2CO | Ph | |
Ⅰ-65 | Cl | SO2CH3 | H | iPr | H | H | CH2CO | Ph | |
Ⅰ-66 | Cl | SO2CH3 | CH3 | CH3 | CH3 | H | CH2CO | Ph | |
Ⅰ-67 | F | SO2CH3 | H | CH3 | CH3 | H | SO2 | 4-Me-Ph | |
Ⅰ-68 | F | SO2CH3 | H | C2H5 | CH3 | H | SO2 | 4-Me-Ph | |
Ⅰ-69 | Cl | SO2CH3 | H | iPr | CH3 | H | SO2 | 4-Me-Ph | |
Ⅰ-70 | Cl | SO2CH3 | CH3 | CH3 | CH3 | H | SO2 | 4-Me-Ph | |
Ⅰ-71 | Cl | SO2CH3 | H | CH3 | CH3 | H | CH2 | Ph | [152-154] |
Ⅰ-72 | Cl | SO2CH3 | H | C2H5 | CH3 | H | CH2 | Ph | [133-135] |
Ⅰ-73 | Cl | SO2CH3 | H | iPr | CH3 | H | CH2 | Ph | |
Ⅰ-74 | Cl | SO2CH3 | CH3 | CH3 | CH3 | H | CH2 | Ph | [190-193] |
Ⅰ-75 | Cl | SO2CH3 | H | CH3 | CH3 | H | CH2CO | Ph | |
Ⅰ-76 | Cl | SO2CH3 | H | C2H5 | CH3 | H | CH2CO | Ph | |
Ⅰ-77 | Cl | SO2CH3 | H | iPr | CH3 | H | CH2CO | Ph | |
Ⅰ-78 | Cl | SO2CH3 | CH3 | CH3 | CH3 | H | CH2CO | Ph | |
Ⅰ-79 | CH3 | SO2CH3 | H | CH3 | CH3 | H | SO2 | 4-Me-Ph | |
Ⅰ-80 | CH3 | SO2CH3 | H | C2H5 | CH3 | H | SO2 | 4-Me-Ph | |
Ⅰ-81 | CF3 | SO2CH3 | H | CH3 | CH3 | H | CH2 | Ph | |
Ⅰ-82 | CF3 | SO2CH3 | H | C2H5 | CH3 | H | CH2 | Ph | |
Ⅰ-83 | Cl | SO2CH3 | H | CH3 | H | CH3 | SO2 | 4-Me-Ph | |
Ⅰ-84 | Cl | SO2CH3 | H | C2H5 | H | CH3 | SO2 | 4-Me-Ph | |
Ⅰ-85 | Cl | SO2CH3 | H | iPr | H | CH3 | SO2 | 4-Me-Ph |
表1(续)
No. | R1 | R2 | R4 | R5 | R7 | R8 | X | R6 | 物理值 |
Ⅰ-86 | Cl | SO2CH3 | CH3 | CH3 | H | CH3 | SO2 | 4-Me-Ph | |
Ⅰ-87 | Cl | SO2CH3 | H | CH3 | H | CH3 | CH2 | Ph | |
Ⅰ-88 | Cl | SO2CH3 | H | C2H5 | H | CH3 | CH2 | Ph | |
Ⅰ-89 | Cl | SO2CH3 | H | iPr | H | CH3 | CH2 | Ph | |
Ⅰ-90 | Cl | SO2CH3 | CH3 | CH3 | CH3 | CH3 | CH2 | Ph | |
Ⅰ-91 | Cl | SO2CH3 | H | CH3 | H | CH3 | CH2CO | Ph | |
Ⅰ-92 | Cl | SO2CH3 | H | C2H5 | H | CH3 | CH2CO | Ph | |
Ⅰ-93 | Cl | SO2CH3 | H | iPr | H | CH3 | CH2CO | Ph | |
Ⅰ-94 | Cl | SO2CH3 | CH3 | CH3 | CH3 | CH3 | CH2CO | Ph | |
Ⅰ-95 | Cl | SO2CH3 | H | CH3 | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅰ-96 | Cl | SO2CH3 | H | C2H5 | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅰ-97 | Cl | SO2CH3 | H | iPr | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅰ-98 | Cl | SO2CH3 | CH3 | CH3 | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅰ-99 | Cl | SO2CH3 | H | CH3 | CH3 | CH3 | CH2 | Ph | |
Ⅰ-100 | Cl | SO2CH3 | H | C2H5 | CH3 | CH3 | CH2 | Ph | |
Ⅰ-101 | Cl | SO2CH3 | H | iPr | CH3 | CH3 | CH2 | Ph | |
Ⅰ-102 | Cl | SO2CH3 | CH3 | CH3 | CH3 | CH3 | CH2 | Ph | |
Ⅰ-103 | Cl | SO2CH3 | H | CH3 | CH3 | CH3 | CH2CO | Ph | |
Ⅰ-104 | Cl | SO2CH3 | H | C2H5 | CH3 | CH3 | CH2CO | Ph | |
Ⅰ-105 | Cl | SO2CH3 | H | iPr | CH3 | CH3 | CH2CO | Ph | |
Ⅰ-106 | Cl | SO2CH3 | CH3 | CH3 | CH3 | CH3 | CH2CO | Ph | |
Ⅰ-107 | Cl | SO2CH3 | H | tBu | CH3 | H | CH2 | Ph | |
Ⅰ-108 | Cl | SO2CH3 | H | tBu | H | CH3 | CH2 | Ph | |
Ⅰ-109 | Cl | SO2CH3 | H | tBu | CH3 | H | SO2 | 4-Me-Ph |
表1(续)
No. | R1 | R2 | R4 | R5 | R7 | R8 | X | R6 | 物理值熔点℃ |
Ⅰ-110 | Cl | SO2CH3 | H | tBu | H | CH3 | SO2 | 4-Me-Ph | |
Ⅰ-111 | Cl | SO2CH3 | H | tBu | CH3 | H | CH2CO | Ph | |
Ⅰ-112 | Cl | SO2CH3 | H | tBu | CH3 | CH3 | CH2CO | Ph | |
Ⅰ-113 | Cl | SO2CH3 | CH3 | tBu | CH3 | H | CH2CO | Ph | |
Ⅰ-114 | Cl | SO2CH3 | CH3 | tBu | H | H | CH2CO | Ph | |
Ⅰ-115 | CH3 | SO2CH3 | H | CH3 | CH3 | H | CH2 | Ph | [113-116] |
Ⅰ-116 | Cl | SO2CH3 | H | C2H5 | CH3 | H | CH2 | 4-CF3-Ph | NMR-6 |
Ⅰ-117 | Cl | Cl | CH3 | CH3 | CH3 | H | CH2 | 4-NO2-Ph | NMR-7 |
Ⅰ-118 | Cl | Cl | H | C2H5 | CH3 | H | CH2 | 2,6-Cl2-Ph | NMR-8 |
Ⅰ-119 | Cl | Cl | H | C2H5 | CH3 | H | CH(CH3) | Ph | NMR-9 |
Ⅰ-120 | CH3 | SO2CH3 | CH3 | CH3 | CH3 | H | CH2 | Ph | [186-188] |
Ⅰ-12l | CH3 | SO2CH3 | H | C2H5 | CH3 | H | CH2 | Ph | NMR-10 |
Ⅰ-122 | Cl | Cl | H | CH3 | CH3 | H | bond | Ph | NMR-11 |
Ⅰ-123 | Cl | SO2CH3 | H | CH3 | CH3 | H | bond | C2H5 | NMR-12 |
Ⅰ-124 | Cl | Cl | CH3 | CH3 | CH3 | H | bond | CH3 | [142-143] |
Ⅰ-125 | Cl | SO2CH3 | H | CH3 | CH3 | H | SO2 | 4-CH3-Ph | [155-157] |
Ⅰ-126 | Cl | OCH3 | H | CH3 | CH3 | H | CH2 | Ph | [102-103] |
Ⅰ-127 | H | SO2CH3 | H | CH3 | i-Pr | H | CH2 | Ph | NRM-13 |
Ⅰ-128 | Cl | SO2CH3 | C2H5 | CH3 | CH3 | H | CH2 | Ph | [178-182] |
Ⅰ-129 | OCH3 | Cl | H | CH3 | CH3 | H | CH2 | Ph | NMR-14 |
Ⅰ-130 | Cl | Cl | CH3 | C2H5 | CH3 | H | CH2 | Ph | [109-110] |
Ⅰ-13l | Cl | SO2CH3 | H | CH3 | CH3 | H | CH2 | 4-OCH3-Ph | NMR-15 |
Ⅰ-132 | Cl | SO2CH3 | H | CH3 | CH3 | H | CH2 | 4-CF3-Ph | [125-126] |
表1(续)
*:c-Hex表示环己基。
No. | R1 | R2 | R4 | R5 | R7 | R8 | X | R6 | 物理值熔点℃ |
Ⅰ-133 | CH3 | Cl | H | CH3 | CH3 | H | CH2 | Ph | [79-81] |
Ⅰ-134 | Cl | CH3 | H | CH3 | CH3 | H | CH2 | Ph | NMR-16 |
Ⅰ-135 | Cl | Cl | H | CH3 | CH3 | H | CO | C2H5 | [122-123] |
Ⅰ-136 | Cl | Cl | H | CH3 | CH3 | H | bond | CH3 | [85-87] |
Ⅰ-137 | OCH3 | SO2CH3 | H | C2H5 | CH3 | H | CH2 | Ph | NMR-17 |
Ⅰ-138 | OCH3 | SO2CH3 | H | CH3 | CH3 | H | CH2 | Ph | NMR-18 |
Ⅰ-139 | Cl | Cl | H | CH3 | CH3 | H | CH2 | 3-Cl-Ph | [95-97] |
Ⅰ-140 | Cl | SO2CH3 | H | CH3 | CH3 | H | CH2 | 3-Cl-Ph | [195-196] |
Ⅰ-141 | Cl | Cl | H | CH3 | CH3 | H | CH2 | 4-Cl-Ph | [134-135] |
Ⅰ-142 | Cl | SO2CH3 | H | CH3 | CH3 | H | CH2 | 4-Cl-Ph | [200-201] |
Ⅰ-143 | Cl | Cl | H | CH3 | CH3 | H | CH2 | 3-CH3-Ph | NMR-20 |
Ⅰ-144 | Cl | SO2CH3 | H | CH3 | CH3 | H | CH2 | 3-CH3-Ph | NMR-21 |
Ⅰ-145 | Cl | Cl | H | CH3 | CH3 | H | CH2 | 4-CH3-Ph | NMR-22 |
Ⅰ-146 | Cl | SO2CH3 | H | CH3 | CH3 | H | CH2 | 4-CH3-Ph | [179-181] |
Ⅰ-147 | Cl | Cl | H | CH3 | CH3 | H | CH2 | c-Hex* | NMR-23 |
Ⅰ-148 | Cl | SO2CH3 | H | CH3 | CH3 | H | CH2 | c-Hex* | NMR-24 |
Ⅰ-149 | Cl | Cl | H | CH3 | CH3 | H | bond | i--Pr | NMR-25 |
Ⅰ-150 | Cl | SO2CH3 | H | CH3 | CH3 | H | bond | i--Pr | [170-175] |
Ⅰ-151 | Cl | Cl | H | CH3 | CH3 | H | CO | 4-Cl-Ph | [148-149] |
Ⅰ-152 | Cl | SO2CH3 | H | CH3 | CH3 | H | CO | 4-Cl-Ph | NMR-26 |
Ⅰ-153 | Cl | Cl | H | CH3 | CH3 | H | CH2CO | Ph | |
Ⅰ-154 | Cl | SO2CH3 | H | CH3 | CH3 | H | CH2CO | Ph | [211-212] |
Ⅰ-155 | Cl | Cl | H | H | CH3 | H | CH2 | Ph | |
Ⅰ-156 | Cl | SO2CH3 | H | H | CH3 | H | CH2 | Ph |
表1(续)
No. | R1 | R2 | R4 | R5 | R7 | R8 | X | R6 | 物理值熔点℃ |
Ⅰ-157 | Cl | Cl | H | CH3 | CH3 | H | CH2CH2 | Ph | |
Ⅰ-158 | Cl | SO2CH3 | H | CH3 | CH3 | H | CH2CH2 | Ph | |
Ⅰ-159 | Cl | Cl | H | C2H5 | CH3 | H | CH2CH2 | Ph | |
Ⅰ-160 | Cl | SO2CH3 | H | C2H5 | CH3 | H | CH2CH2 | Ph | |
Ⅰ-161 | Cl | Cl | CH3 | CH3 | CH3 | H | CH2CH2 | Ph | |
Ⅰ-162 | Cl | SO2CH3 | CH3 | CH3 | CH3 | H | CH2CH2 | Ph | |
Ⅰ-163 | CH3 | Cl | H | CH3 | CH3 | H | CH2CH2 | Ph | |
Ⅰ-164 | CH3 | SO2CH3 | H | CH3 | CH3 | H | CH2CH2 | Ph | |
Ⅰ-165 | CH3 | Cl | H | C2H5 | CH3 | H | CH2CH2 | Ph | |
Ⅰ-166 | CH3 | SO2CH3 | H | C2H5 | CH3 | H | CH2CH2 | Ph | |
Ⅰ-167 | CH3 | Cl | CH3 | CH3 | CH3 | H | CH2CH2 | Ph | |
Ⅰ-168 | CH3 | SO2CH3 | CH3 | CH3 | CH3 | H | CH2CH2 | Ph | |
Ⅰ-169 | CH3 | Cl | H | CH3 | CH3 | H | CH2CH2CO | Ph | |
Ⅰ-170 | CH3 | SO2CH3 | H | CH3 | CH3 | H | CH2CH2CO | Ph | |
Ⅰ-171 | CH3 | Cl | H | C2H5 | CH3 | H | CH2CH2CO | Ph | |
Ⅰ-172 | CH3 | SO2CH3 | H | C2H5 | CH3 | H | CH2CH2CO | Ph | |
Ⅰ-173 | Cl | Cl | CH3 | CH3 | CH3 | H | (CH2)3 | Ph | |
Ⅰ-174 | Cl | SO2CH3 | CH3 | CH3 | CH3 | H | (CH2)3 | Ph | |
Ⅰ-175 | Cl | Cl | CH3 | CH3 | CH3 | H | (CH2)5 | Ph | |
Ⅰ-176 | Cl | SO2CH3 | CH3 | CH3 | CH3 | H | (CH2)5 | Ph | |
Ⅰ-177 | Cl | SO2CH3 | CH3 | CH3 | CH3 | H | (CH2)5CO | Ph |
表2
No. | R1 | R2 | R4 | R5 | R7 | R8 | X | R6 | 物理值 |
Ⅱ-1 | Cl | Cl | H | CH3 | H | CH3 | SO2 | 4-Me-Ph | |
Ⅱ-2 | Cl | Cl | H | C2H5 | H | CH3 | SO2 | 4-Me-Ph | |
Ⅱ-3 | Cl | Cl | H | iPr | H | CH3 | SO2 | 4-Me-Ph | |
Ⅱ-4 | Cl | Cl | CH3 | CH3 | H | CH3 | SO2 | 4-Me-Ph | |
Ⅱ-5 | Cl | Cl | H | CH3 | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅱ-6 | Cl | Cl | H | C2H5 | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅱ-7 | Cl | Cl | H | iPr | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅱ-8 | Cl | Cl | CH3 | CH3 | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅱ-9 | Cl | Cl | H | tBu | H | CH3 | SO2 | 4-Me-Ph | |
Ⅱ-10 | Cl | Cl | H | tBu | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅱ-11 | Cl | Cl | CH3 | tBu | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅱ-12 | Cl | Cl | H | CH3 | H | CH3 | CH2 | Ph | |
Ⅱ-13 | Cl | Cl | H | C2H5 | H | CH3 | CH2 | Ph | |
Ⅱ-14 | Cl | Cl | H | iPr | H | CH3 | CH2 | Ph | |
Ⅱ-15 | Cl | Cl | CH3 | CH3 | H | CH3 | CH2 | Ph | |
Ⅱ-16 | Cl | Cl | H | CH3 | CH3 | CH3 | CH2 | Ph | 粉末(NMR-27) |
表2(续)
No. | R1 | R2 | R4 | R5 | R7 | R8 | X | R6 | 物理值 |
Ⅱ-17 | Cl | Cl | H | C2H5 | CH3 | CH3 | CH2 | Ph | |
Ⅱ-18 | Cl | Cl | H | iPr | CH3 | CH3 | CH2 | Ph | |
Ⅱ-19 | Cl | Cl | CH3 | CH3 | CH3 | CH3 | CH2 | Ph | |
Ⅱ-20 | Cl | Cl | H | tBu | H | CH3 | CH2 | Ph | |
Ⅱ-21 | Cl | Cl | H | tBu | CH3 | CH3 | CH2 | Ph | |
Ⅱ-22 | Cl | Cl | CH3 | tBu | CH3 | CH3 | CH2 | Ph | |
Ⅱ-23 | Cl | Cl | H | CH3 | H | CH3 | CH2CO | Ph | |
Ⅱ-24 | Cl | Cl | H | C2H5 | H | CH3 | CH2CO | Ph | |
Ⅱ-25 | Cl | Cl | H | iPr | H | CH3 | CH2CO | Ph | |
Ⅱ-26 | Cl | Cl | CH3 | CH3 | H | CH3 | CH2CO | Ph | |
Ⅱ-27 | Cl | Cl | H | CH3 | CH3 | CH3 | CH2CO | Ph | |
Ⅱ-28 | Cl | Cl | H | C2H5 | CH3 | CH3 | CH2CO | Ph | |
Ⅱ-29 | Cl | Cl | H | iPr | CH3 | CH3 | CH2CO | Ph | |
Ⅱ-30 | Cl | Cl | CH3 | CH3 | CH3 | CH3 | CH2CO | Ph | |
Ⅱ-31 | Cl | Cl | H | tBu | H | CH3 | CH2CO | Ph | |
Ⅱ-32 | Cl | Cl | H | tBu | CH3 | CH3 | CH2CO | Ph | |
Ⅱ-33 | Cl | Cl | CH3 | tBu | CH3 | CH3 | CH2CO | Ph | |
Ⅱ-34 | Cl | Cl | H | CH3 | CH3 | C2H5 | SO2 | 4-Me-Ph | |
Ⅱ-35 | Cl | Cl | H | C2H5 | CH3 | C2H5 | SO2 | 4-Me-Ph | |
Ⅱ-36 | Cl | Cl | H | CH3 | H | C2H5 | CH2 | Ph | |
Ⅱ-37 | Cl | Cl | H | C2H5 | H | C2H5 | CH2 | Ph | |
Ⅱ-38 | Cl | Cl | H | CH3 | CH3 | C2H5 | CH2CO | Ph | |
Ⅱ-39 | Cl | Cl | H | C2H5 | CH3 | C2H5 | CH2CO | Ph |
表2(续)
No. | R1 | R2 | R4 | R5 | R7 | R8 | X | R6 | 物理值熔点℃ |
Ⅱ-4O | Cl | SO2CH3 | H | CH3 | H | CH3 | SO2 | 4-Me-Ph | |
Ⅱ-41 | Cl | SO2CH3 | H | C2H5 | H | CH3 | SO2 | 4-Me-Ph | |
Ⅱ-42 | Cl | SO2CH3 | H | iPr | H | CH3 | SO2 | 4-Me-Ph | |
Ⅱ-43 | Cl | SO2CH3 | CH3 | CH3 | H | CH3 | SO2 | 4-Me-Ph | |
Ⅱ-44 | Cl | SO2CH3 | H | CH3 | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅱ-45 | Cl | SO2CH3 | H | C2H5 | CH3 | CH3 | SO2 | 3-Me-Ph | |
Ⅱ-46 | Cl | SO2CH3 | H | iPr | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅱ-47 | Cl | SO2CH3 | CH3 | CH3 | CH3 | CH3 | SO2 | 3-Me-Ph | |
Ⅱ-48 | Cl | SO2CH3 | CH3 | tBu | H | CH3 | SO2 | 4-Me-Ph | |
Ⅱ-49 | Cl | SO2CH3 | CH3 | tBu | CH3 | CH3 | SO2 | 3-Me-Ph | |
Ⅱ-50 | Cl | SO2CH3 | CH3 | tBu | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅱ-51 | Cl | SO2CH3 | H | CH3 | H | CH3 | CH2 | Ph | |
Ⅱ-52 | Cl | SO2CH3 | H | C2H5 | H | CH3 | CH2 | Ph | |
Ⅱ-53 | Cl | SO2CH3 | H | iPr | H | CH3 | CH2 | Ph | |
Ⅱ-54 | Cl | SO2CH3 | CH3 | CH3 | H | CH3 | CH2 | Ph | |
Ⅱ-55 | Cl | SO2CH3 | H | CH3 | CH3 | CH3 | CH2 | Ph | [111-113] |
Ⅱ-56 | Cl | SO2CH3 | H | C2H5 | CH3 | CH3 | CH2 | Ph | |
Ⅱ-57 | Cl | SO2CH3 | H | iPr | CH3 | CH3 | CH2 | Ph | |
Ⅱ-58 | Cl | SO2CH3 | CH3 | CH3 | CH3 | CH3 | CH2 | Ph | |
Ⅱ-59 | Cl | SO2CH3 | H | tBu | H | CH3 | CH2 | Ph | |
Ⅱ-60 | Cl | SO2CH3 | H | tBu | CH3 | CH3 | CH2 | Ph | |
Ⅱ-61 | Cl | SO2CH3 | CH3 | tBu | CH3 | CH3 | CH2 | Ph |
表2(续)
No. | R1 | R2 | R4 | R5 | R7 | R8 | X | R6 | 物理值熔点℃ |
Ⅱ-62 | Cl | SO2CH3 | H | CH3 | H | CH3 | CH2CO | Ph | |
Ⅱ-63 | Cl | SO2CH3 | H | C2H5 | H | CH3 | CH2CO | Ph | |
Ⅱ-64 | Cl | SO2CH3 | H | iPr | H | CH3 | CH2CO | Ph | |
Ⅱ-65 | Cl | SO2CH3 | CH3 | CH3 | H | CH3 | CH2CO | Ph | |
Ⅱ-66 | Cl | SO2CH3 | H | CH3 | CH3 | CH3 | CH2CO | Ph | |
Ⅱ-67 | Cl | SO2CH3 | H | C2H5 | CH3 | CH3 | CH2CO | Ph | |
Ⅱ-68 | Cl | SO2CH3 | H | iPr | CH3 | CH3 | CH2CO | Ph | |
Ⅱ-69 | Cl | SO2CH3 | CH3 | CH3 | CH3 | CH3 | CH2CO | Ph | |
Ⅱ-70 | Cl | SO2CH3 | H | tBu | H | CH3 | CH2CO | Ph | |
Ⅱ-71 | Cl | SO2CH3 | H | tBu | CH3 | CH3 | CH2CO | Ph | |
Ⅱ-72 | Cl | SO2CH3 | CH3 | tBu | CH3 | CH3 | CH2CO | Ph | |
Ⅱ-73 | Cl | SO2CH3 | H | CH3 | CH3 | C2H5 | SO2 | 4-Me-Ph | |
Ⅱ-74 | Cl | SO2CH3 | H | C2H5 | CH3 | C2H5 | SO2 | 4-Me-Ph | |
Ⅱ-75 | Cl | SO2CH3 | H | CH3 | H | C2H5 | CH2 | Ph | |
Ⅱ-76 | Cl | SO2CH3 | H | C2H5 | H | C2H5 | CH2 | Ph | |
Ⅱ-77 | Cl | SO2CH3 | H | CH3 | CH3 | C2H5 | CH2CO | Ph | |
Ⅱ-78 | Cl | SO2CH3 | H | C2H5 | CH3 | C2H5 | CH2CO | Ph | |
Ⅱ-79 | Cl | SO2CH3 | H | tBu | H | C2H5 | CH2CO | Ph | |
Ⅱ-80 | Cl | SO2CH3 | H | tBu | CH3 | C2H5 | CH2CO | Ph | |
Ⅱ-81 | Cl | SO2CH3 | CH3 | tBu | CH3 | C2H5 | CH2CO | Ph |
No. | R1 | R2 | R4 | R5 | R7 | R8 | X | R6 | 物理值 |
Ⅲ-1 | Cl | Cl | H | CH3 | H | H | SO2 | 4-Me-Ph | |
Ⅲ-2 | Cl | Cl | H | C2H5 | H | H | SO2 | 4-Me-Ph | |
Ⅲ-3 | Cl | Cl | H | iPr | H | H | SO2 | 4-Me-Ph | |
Ⅲ-4 | Cl | Cl | CH3 | CH3 | H | H | SO2 | 4-Me-Ph | |
Ⅲ-5 | Cl | Cl | H | CH3 | H | H | CH2 | Ph | |
Ⅲ-6 | Cl | Cl | H | C2H5 | H | H | CH2 | Ph | NMR-28 |
Ⅲ-7 | Cl | Cl | H | iPr | H | H | CH2 | Ph | |
Ⅲ-8 | Cl | Cl | CH3 | CH3 | CH3 | H | CH2 | Ph | |
Ⅲ-9 | Cl | Cl | H | CH3 | H | H | CH2CO | Ph | |
Ⅲ-10 | Cl | Cl | H | C2H5 | H | H | CH2CO | Ph | |
Ⅲ-11 | Cl | Cl | H | iPr | H | H | CH2CO | Ph | |
Ⅲ-12 | Cl | Cl | CH3 | CH3 | CH3 | H | CH2CO | Ph | |
Ⅲ-13 | Cl | Cl | H | CH3 | CH3 | H | SO2 | 4-Me-Ph | |
Ⅲ-14 | Cl | Cl | H | C2H5 | CH3 | H | SO2 | 4-Me-Ph | |
Ⅲ-15 | Cl | Cl | H | iPr | CH3 | H | SO2 | 4-Me-Ph | |
Ⅲ-16 | Cl | Cl | CH3 | CH3 | CH3 | H | SO2 | 4-Me-Ph |
表3(续)
No. | R1 | R2 | R4 | R5 | R9 | R10 | X | R6 | 物理值 |
Ⅲ-17 | Cl | Cl | H | CH3 | CH3 | H | CH2 | Ph | |
Ⅲ-18 | Cl | Cl | H | C2H5 | CH3 | H | CH2 | Ph | |
Ⅲ-19 | Cl | Cl | H | iPr | CH3 | H | CH2 | Ph | |
Ⅲ-20 | Cl | Cl | CH3 | CH3 | CH3 | H | CH2 | Ph | |
Ⅲ-21 | Cl | Cl | H | CH3 | CH3 | H | CH2CO | Ph | |
Ⅲ-22 | Cl | Cl | H | C2H5 | CH3 | H | CH2CO | Ph | |
Ⅲ-19 | Cl | Cl | H | iPr | CH3 | H | CH2CO | Ph | |
Ⅲ-20 | Cl | Cl | CH3 | CH3 | CH3 | H | CH2CO | Ph | |
Ⅲ-21 | Cl | Cl | H | CH3 | H | CH3 | SO2 | 4-Me-Ph | |
Ⅲ-22 | Cl | Cl | H | C2H5 | H | CH3 | SO2 | 4-Me-Ph | |
Ⅲ-23 | Cl | Cl | H | iPr | H | CH3 | SO2 | 4-Me-Ph | |
Ⅲ-24 | Cl | Cl | CH3 | CH3 | H | CH3 | SO2 | 4-Me-Ph | |
Ⅲ-25 | Cl | Cl | H | CH3 | H | CH3 | CH2 | Ph | |
Ⅲ-26 | Cl | Cl | H | C2H5 | H | CH3 | CH2 | Ph | |
Ⅲ-27 | Cl | Cl | H | iPr | H | CH3 | CH2 | Ph | |
Ⅲ-28 | Cl | Cl | CH3 | CH3 | CH3 | CH3 | CH2 | Ph | |
Ⅲ-29 | Cl | Cl | H | CH3 | H | CH3 | CH2CO | Ph | |
Ⅲ-30 | Cl | Cl | H | C2H5 | H | CH3 | CH2CO | Ph | |
Ⅲ-31 | Cl | Cl | H | iPr | H | CH3 | CH2CO | Ph | |
Ⅲ-32 | Cl | Cl | CH3 | CH3 | CH3 | CH3 | CH2CO | Ph |
表3(续)
No. | R1 | R2 | R4 | R5 | R9 | R10 | X | R6 | 物理值 |
Ⅲ-33 | Cl | Cl | H | CH3 | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅲ-34 | Cl | Cl | H | C2H5 | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅲ-35 | Cl | Cl | H | iPr | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅲ-36 | Cl | Cl | CH3 | CH3 | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅲ-37 | Cl | Cl | H | CH3 | CH3 | CH3 | CH2 | Ph | |
Ⅲ-38 | Cl | Cl | H | C2H5 | CH3 | CH3 | CH2 | Ph | |
Ⅲ-39 | Cl | Cl | H | iPr | CH3 | CH3 | CH2 | Ph | |
Ⅲ-40 | Cl | Cl | CH3 | CH3 | CH3 | CH3 | CH2 | Ph | |
Ⅲ-41 | Cl | Cl | H | CH3 | CH3 | CH3 | CH2CO | Ph | |
Ⅲ-42 | Cl | Cl | H | C2H5 | CH3 | CH3 | CH2CO | Ph | |
Ⅲ-43 | Cl | Cl | H | iPr | CH3 | CH3 | CH2CO | Ph | |
Ⅲ-44 | Cl | Cl | CH3 | CH3 | CH3 | CH3 | CH2CO | Ph | |
Ⅲ-45 | Cl | Cl | H | tBu | CH3 | H | CH2 | Ph | |
Ⅲ-46 | Cl | Cl | H | tBu | CH3 | H | CH2 | Ph | |
Ⅲ-47 | Cl | Cl | CH3 | tBu | CH3 | H | SO2 | 4-Me-Ph | |
Ⅲ-48 | Cl | Cl | CH3 | tBu | CH3 | H | SO2 | 4-Me-Ph | |
Ⅲ-49 | Cl | Cl | CH3 | tBu | CH3 | H | CH2CO | Ph | |
Ⅲ-50 | Cl | Cl | CH3 | tBu | CH3 | H | CH2CO | Ph |
表3(续)
No. | R1 | R2 | R4 | R5 | R9 | R10 | X | R6 | 物理值熔点℃ |
Ⅲ-51 | Cl | SO2CH3 | H | CH3 | H | H | SO2 | 4-Me-Ph | |
Ⅲ-52 | Cl | SO2CH3 | H | C2H5 | H | H | SO2 | 4-Me-Ph | |
Ⅲ-53 | Cl | SO2CH3 | H | iPr | H | H | SO2 | 4-Me-Ph | |
Ⅲ-54 | Cl | SO2CH3 | CH3 | CH3 | H | H | SO2 | 4-Me-Ph | |
Ⅲ-55 | Cl | SO2CH3 | H | CH3 | H | H | CH2 | Ph | |
Ⅲ-56 | Cl | SO2CH3 | H | C2H5 | H | H | CH2 | Ph | |
Ⅲ-57 | Cl | SO2CH3 | H | iPr | H | H | CH2 | Ph | |
Ⅲ-58 | Cl | SO2CH3 | CH3 | CH3 | CH3 | H | CH2 | Ph | |
Ⅲ-59 | Cl | SO2CH3 | H | CH3 | H | H | CH2CO | Ph | |
Ⅲ-60 | Cl | SO2CH3 | H | C2H5 | H | H | CH2CO | Ph | |
Ⅲ-61 | Cl | SO2CH3 | H | iPr | H | H | CH2CO | Ph | |
Ⅲ-62 | Cl | SO2CH3 | CH3 | CH3 | CH3 | H | CH2CO | Ph | |
Ⅲ-63 | Cl | SO2CH3 | H | CH3 | CH3 | H | SO2 | 4-Me-Ph | |
Ⅲ-64 | Cl | SO2CH3 | H | C2H5 | CH3 | H | SO2 | 4-Me-Ph | |
Ⅲ-65 | Cl | SO2CH3 | H | iPr | CH3 | H | SO2 | 4-Me-Ph | |
Ⅲ-66 | Cl | SO2CH3 | CH3 | CH3 | CH3 | H | SO2 | 4-Me-Ph | |
Ⅲ-67 | Cl | SO2CH3 | H | CH3 | CH3 | H | CH2 | Ph | |
Ⅲ-68 | Cl | SO2CH3 | H | C2H5 | CH3 | H | CH2 | Ph | |
Ⅲ-69 | Cl | SO2CH3 | H | iPr | CH3 | H | CH2 | Ph | |
Ⅲ-70 | Cl | SO2CH3 | CH3 | CH3 | CH3 | H | CH2 | Ph |
表3(续)
No. | R1 | R2 | R4 | R5 | R9 | R10 | X | R6 | 物理值 |
Ⅲ-7l | Cl | SO2CH3 | H | CH3 | CH3 | H | CH2CO | Ph | |
Ⅲ-72 | Cl | SO2CH3 | H | C2H5 | CH3 | H | CH2CO | Ph | |
Ⅲ-73 | Cl | SO2CH3 | H | iPr | CH3 | H | CH2CO | Ph | |
Ⅲ-74 | Cl | SO2CH3 | CH3 | CH3 | CH3 | H | CH2CO | Ph | |
Ⅲ-75 | CH3 | SO2CH3 | H | CH3 | CH3 | H | SO2 | 4-Me-Ph | |
Ⅲ-76 | CH3 | SO2CH3 | H | C2H5 | CH3 | H | SO2 | 4-Me-Ph | |
Ⅲ-77 | CH3 | SO2CH3 | H | CH3 | CH3 | H | CH2 | Ph | |
Ⅲ-78 | CH3 | SO2CH3 | H | C2H5 | CH3 | H | CH2 | Ph | |
Ⅲ-79 | Cl | SO2CH3 | H | CH3 | H | CH3 | SO2 | 4-Me-Ph | |
Ⅲ-80 | Cl | SO2CH3 | H | C2H5 | H | CH3 | SO2 | 4-Me-Ph | |
Ⅲ-81 | Cl | SO2CH3 | H | iPr | H | CH3 | SO2 | 4-Me-Ph | |
Ⅲ-82 | Cl | SO2CH3 | CH3 | CH3 | H | CH3 | SO2 | 4-Me-Ph | |
Ⅲ-83 | Cl | SO2CH3 | H | CH3 | H | CH3 | CH2 | Ph | |
Ⅲ-84 | Cl | SO2CH3 | H | C2H5 | H | CH3 | CH2 | Ph | |
Ⅲ-85 | Cl | SO2CH3 | H | iPr | H | CH3 | CH2 | Ph | |
Ⅲ-86 | Cl | SO2CH3 | CH3 | CH3 | CH3 | CH3 | CH2 | Ph | |
Ⅲ-87 | Cl | SO2CH3 | H | CH3 | H | CH3 | CH2CO | Ph | |
Ⅲ-88 | Cl | SO2CH3 | H | C2H5 | H | CH3 | CH2CO | Ph | |
Ⅲ-89 | Cl | SO2CH3 | H | iPr | H | CH3 | CH2CO | Ph | |
Ⅲ-90 | Cl | SO2CH3 | CH3 | CH3 | CH3 | CH3 | CH2CO | Ph | |
Ⅲ-91 | Cl | SO2CH3 | H | CH3 | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅲ-92 | Cl | SO2CH3 | H | C2H5 | CH3 | CH3 | SO2 | 4-Me-Ph |
表3(续)
No. | R1 | R2 | R4 | R5 | R9 | R10 | X | R6 | 物理值 |
Ⅲ-93 | Cl | SO2CH3 | H | iPr | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅲ-94 | Cl | SO2CH3 | CH3 | CH3 | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅲ-95 | Cl | SO2CH3 | H | CH3 | CH3 | CH3 | CH2 | Ph | |
Ⅲ-96 | Cl | SO2CH3 | H | C2H5 | CH3 | CH3 | CH2 | Ph | |
Ⅲ-97 | Cl | SO2CH3 | H | iPr | CH3 | CH3 | CH2 | Ph | |
Ⅲ-98 | Cl | SO2CH3 | CH3 | CH3 | CH3 | CH3 | CH2 | Ph | |
Ⅲ-99 | Cl | SO2CH3 | H | CH3 | CH3 | CH3 | CH2CO | Ph | |
Ⅲ-l00 | Cl | SO2CH3 | H | C2H5 | CH3 | CH3 | CH2CO | Ph | |
Ⅲ-101 | Cl | SO2CH3 | H | iPr | CH3 | CH3 | CH2CO | Ph | |
Ⅲ-102 | Cl | SO2CH3 | CH3 | CH3 | CH3 | CH3 | CH2CO | Ph | |
Ⅲ-103 | Cl | SO2CH3 | H | tBu | CH3 | H | CH2 | Ph | |
Ⅲ-104 | Cl | SO2CH3 | H | tBu | H | CH3 | CH2 | Ph | |
Ⅲ-105 | Cl | SO2CH3 | H | tBu | CH3 | H | SO2 | 4-Me-Ph | |
Ⅲ-106 | Cl | SO2CH3 | H | tBu | H | CH3 | SO2 | 4-Me-Ph | |
Ⅲ-107 | Cl | SO2CH3 | H | tBu | CH3 | H | CH2CO | Ph | |
Ⅲ-108 | Cl | SO2CH3 | H | tBu | CH3 | CH3 | CH2CO | Ph | |
Ⅲ-109 | Cl | SO2CH3 | CH3 | tBu | CH3 | H | CH2CO | Ph | |
Ⅲ-110 | Cl | SO2CH3 | CH3 | tBu | H | H | CH2CO | Ph |
表4
No. | R1 | R2 | R4 | R5 | R7 | R8 | X | R6 | 物理值熔点℃ |
Ⅳ-1 | Cl | Cl | H | CH3 | H | H | SO2 | 4-Me-Ph | |
Ⅳ-2 | Cl | Cl | H | C2H5 | H | H | SO2 | 4-Me-Ph | |
Ⅳ-3 | Cl | Cl | H | iPr | H | H | SO2 | 4-Me-Ph | |
Ⅳ-4 | Cl | Cl | CH3 | CH3 | H | H | SO2 | 4-Me-Ph | |
Ⅳ-5 | Cl | Cl | H | CH3 | H | H | CH2 | Ph | |
Ⅳ-6 | Cl | Cl | H | C2H5 | H | H | CH2 | Ph | [124-127] |
Ⅳ-7 | Cl | Cl | H | iPr | H | H | CH2 | Ph | |
Ⅳ-8 | Cl | Cl | CH3 | CH3 | CH3 | H | CH2 | Ph | |
Ⅳ-9 | Cl | Cl | H | CH3 | H | H | CH2CO | Ph | [149-151] |
Ⅳ-10 | Cl | Cl | H | C2H5 | H | H | CH2CO | Ph | |
Ⅳ-11 | Cl | Cl | H | iPr | H | H | CH2CO | Ph | |
Ⅳ-12 | Cl | Cl | CH3 | CH3 | CH3 | H | CH2CO | Ph | |
Ⅳ-13 | Cl | Cl | H | CH3 | CH3 | H | SO2 | 4-Me-Ph | |
Ⅳ-14 | Cl | Cl | H | C2H5 | CH3 | H | SO2 | 4-Me-Ph | |
Ⅳ-15 | Cl | Cl | H | iPr | CH3 | H | SO2 | 4-Me-Ph | |
Ⅳ-16 | Cl | Cl | CH3 | CH3 | CH3 | H | SO2 | 4-Me-Ph |
表4(续)
No. | R1 | R2 | R4 | R5 | R7 | R8 | X | R6 | 物理值熔点℃ |
Ⅳ-17 | Cl | Cl | H | CH3 | CH3 | H | CH2 | Ph | [121-123] |
Ⅳ-18 | Cl | Cl | H | C2H5 | CH3 | H | CH2 | Ph | |
Ⅳ-19 | Cl | Cl | H | iPr | CH3 | H | CH2 | Ph | |
Ⅳ-20 | Cl | Cl | CH3 | CH3 | CH3 | H | CH2 | Ph | |
Ⅳ-21 | Cl | Cl | H | CH3 | CH3 | H | CH2CO | Ph | |
Ⅳ-22 | Cl | Cl | H | C2H5 | CH3 | H | CH2CO | Ph | |
Ⅳ-19 | Cl | Cl | H | iPr | CH3 | H | CH2CO | Ph | |
Ⅳ-20 | Cl | Cl | CH3 | CH3 | CH3 | H | CH2CO | Ph | |
Ⅳ-21 | Cl | Cl | H | CH3 | H | CH3 | SO2 | 4-Me-Ph | |
Ⅳ-22 | Cl | Cl | H | C2H5 | H | CH3 | SO2 | 4-Me-Ph | |
Ⅳ-23 | Cl | Cl | H | iPr | H | CH3 | SO2 | 4-Me-Ph | |
Ⅳ-24 | Cl | Cl | CH3 | CH3 | H | CH3 | SO2 | 4-Me-Ph | |
Ⅳ-25 | Cl | Cl | H | CH3 | H | CH3 | CH2 | Ph | |
Ⅳ-26 | Cl | Cl | H | C2H5 | H | CH3 | CH2 | Ph | |
Ⅳ-27 | Cl | Cl | H | iPr | H | CH3 | CH2 | Ph | |
Ⅳ-28 | Cl | Cl | CH3 | CH3 | CH3 | CH3 | CH2 | Ph | |
Ⅳ-29 | Cl | Cl | H | CH3 | H | CH3 | CH2CO | Ph | |
Ⅳ-30 | Cl | Cl | H | C2H5 | H | CH3 | CH2CO | Ph | |
Ⅳ-31 | Cl | Cl | H | iPr | H | CH3 | CH2CO | Ph | |
Ⅳ-32 | Cl | Cl | CH3 | CH3 | CH3 | CH3 | CH2CO | Ph |
表4(续)
No. | R1 | R2 | R4 | R5 | R7 | R8 | X | R6 | 物理值熔点℃ |
Ⅳ-33 | Cl | Cl | H | CH3 | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅳ-34 | Cl | Cl | H | C2H5 | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅳ-35 | Cl | Cl | H | iPr | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅳ-36 | Cl | Cl | CH3 | CH3 | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅳ-37 | Cl | Cl | H | CH3 | CH3 | CH3 | CH2 | Ph | |
Ⅳ-38 | Cl | Cl | H | C2H5 | CH3 | CH3 | CH2 | Ph | |
Ⅳ-39 | Cl | Cl | H | iPr | CH3 | CH3 | CH2 | Ph | |
Ⅳ-40 | Cl | Cl | CH3 | CH3 | CH3 | CH3 | CH2 | Ph | |
Ⅳ-41 | Cl | Cl | H | CH3 | CH3 | CH3 | CH2CO | Ph | |
Ⅳ-42 | Cl | Cl | H | C2H5 | CH3 | CH3 | CH2CO | Ph | |
Ⅳ-43 | Cl | Cl | H | iPr | CH3 | CH3 | CH2CO | Ph | |
Ⅳ-44 | Cl | Cl | CH3 | CH3 | CH3 | CH3 | CH2CO | Ph | |
Ⅳ-45 | Cl | Cl | H | tBu | CH3 | H | CH2 | Ph | |
Ⅳ-46 | Cl | Cl | H | tBu | CH3 | H | CH2 | Ph | |
Ⅳ-47 | Cl | Cl | CH3 | tBu | CH3 | H | SO2 | 4-Me-Ph | |
Ⅳ-48 | Cl | Cl | CH3 | tBu | CH3 | H | SO2 | 4-Me-Ph | |
Ⅳ-49 | Cl | Cl | CH3 | tBu | CH3 | H | CH2CO | Ph | |
Ⅳ-50 | Cl | Cl | CH3 | tBu | CH3 | H | CH2CO | Ph |
表4(续)
No. | R1 | R2 | R4 | R5 | R7 | R8 | X | R6 | 物理值 |
Ⅳ-51 | Cl | SO2CH3 | H | CH3 | H | H | SO2 | 4-Me-Ph | |
Ⅳ-52 | Cl | SO2CH3 | H | C2H5 | H | H | SO2 | 4-Me-Ph | |
Ⅳ-53 | Cl | SO2CH3 | H | iPr | H | H | SO2 | 4-Me-Ph | |
Ⅳ-54 | Cl | SO2CH3 | CH3 | CH3 | H | H | SO2 | 4-Me-Ph | |
Ⅳ-55 | Cl | SO2CH3 | H | CH3 | H | H | CH2 | Ph | |
Ⅳ-56 | Cl | SO2CH3 | H | C2H5 | H | H | CH2 | Ph | |
Ⅳ-57 | Cl | SO2CH3 | H | iPr | H | H | CH2 | Ph | |
Ⅳ-58 | Cl | SO2CH3 | CH3 | CH3 | CH3 | H | CH2 | Ph | |
Ⅳ-59 | Cl | SO2CH3 | H | CH3 | H | H | CH2CO | Ph | |
Ⅳ-60 | Cl | SO2CH3 | H | C2H5 | H | H | CH2CO | Ph | |
Ⅳ-61 | Cl | SO2CH3 | H | iPr | H | H | CH2CO | Ph | |
Ⅳ-62 | Cl | SO2CH3 | CH3 | CH3 | CH3 | H | CH2CO | Ph | |
Ⅳ-63 | Cl | SO2CH3 | H | CH3 | CH3 | H | SO2 | 4-Me-Ph | |
Ⅳ-64 | Cl | SO2CH3 | H | C2H5 | CH3 | H | SO2 | 4-Me-Ph | |
Ⅳ-65 | Cl | SO2CH3 | H | iPr | CH3 | H | SO2 | 4-Me-Ph | |
Ⅳ-66 | Cl | SO2CH3 | CH3 | CH3 | CH3 | H | SO2 | 4-Me-Ph | |
Ⅳ-67 | Cl | SO2CH3 | H | CH3 | CH3 | H | CH2 | Ph | [159-160] |
Ⅳ-68 | Cl | SO2CH3 | H | C2H5 | CH3 | H | CH2 | Ph | |
Ⅳ-69 | Cl | SO2CH3 | H | iPr | CH3 | H | CH2 | Ph | |
Ⅳ-70 | Cl | SO2CH3 | CH3 | CH3 | CH3 | H | CH2 | Ph |
表4(续)
No. | R1 | R2 | R4 | R5 | R7 | R8 | X | R6 | 物理值 |
Ⅳ-71 | Cl | SO2CH3 | H | CH3 | CH3 | H | CH2CO | Ph | |
Ⅳ-72 | Cl | SO2CH3 | H | C2H5 | CH3 | H | CH2CO | Ph | |
Ⅳ-73 | Cl | SO2CH3 | H | iPr | CH3 | H | CH2CO | Ph | |
Ⅳ-74 | Cl | SO2CH3 | CH3 | CH3 | CH3 | H | CH2CO | Ph | |
Ⅳ-75 | CH3 | SO2CH3 | H | CH3 | CH3 | H | SO2 | 4-Me-Ph | |
Ⅳ-76 | CH3 | SO2CH3 | H | C2H5 | CH3 | H | SO2 | 4-Me-Ph | |
Ⅳ-77 | CH3 | SO2CH3 | H | CH3 | CH3 | H | CH2 | Ph | |
Ⅳ-78 | CH3 | SO2CH3 | H | C2H5 | CH3 | H | CH2 | Ph | |
Ⅳ-79 | Cl | SO2CH3 | H | CH3 | H | CH3 | SO2 | 4-Me-Ph | |
Ⅳ-80 | Cl | SO2CH3 | H | C2H5 | H | CH3 | SO2 | 4-Me-Ph | |
Ⅳ-81 | Cl | SO2CH3 | H | iPr | H | CH3 | SO2 | 4-Me-Ph | |
Ⅳ-82 | Cl | SO2CH3 | CH3 | CH3 | H | CH3 | SO2 | 4-Me-Ph | |
Ⅳ-83 | Cl | SO2CH3 | H | CH3 | H | CH3 | CH2 | Ph | |
Ⅳ-84 | Cl | SO2CH3 | H | C2H5 | H | CH3 | CH2 | Ph | |
Ⅳ-85 | Cl | SO2CH3 | H | iPr | H | CH3 | CH2 | Ph | |
Ⅳ-86 | Cl | SO2CH3 | CH3 | CH3 | CH3 | CH3 | CH2 | Ph | |
Ⅳ-87 | Cl | SO2CH3 | H | CH3 | H | CH3 | CH2CO | Ph | |
Ⅳ-88 | Cl | SO2CH3 | H | C2H5 | H | CH3 | CH2CO | Ph | |
Ⅳ-89 | Cl | SO2CH3 | H | iPr | H | CH3 | CH2CO | Ph | |
Ⅳ-90 | Cl | SO2CH3 | CH3 | CH3 | CH3 | CH3 | CH2CO | Ph | |
Ⅳ-91 | Cl | SO2CH3 | H | CH3 | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅳ-92 | Cl | SO2CH3 | H | C2H5 | CH3 | CH3 | SO2 | 4-Me-Ph |
表4(续)
No. | R1 | R2 | R4 | R5 | R7 | R8 | X | R6 | 物理值 |
Ⅳ-93 | Cl | SO2CH3 | H | iPr | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅳ-94 | Cl | SO2CH3 | CH3 | CH3 | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅳ-95 | Cl | SO2CH3 | H | CH3 | CH3 | CH3 | CH2 | Ph | |
Ⅳ-96 | Cl | SO2CH3 | H | C2H5 | CH3 | CH3 | CH2 | Ph | |
Ⅳ-97 | Cl | SO2CH3 | H | iPr | CH3 | CH3 | CH2 | Ph | |
Ⅳ-98 | Cl | SO2CH3 | CH3 | CH3 | CH3 | CH3 | CH2 | Ph | |
Ⅳ-99 | Cl | SO2CH3 | H | CH3 | CH3 | CH3 | CH2CO | Ph | |
Ⅳ-100 | Cl | SO2CH3 | H | C2H5 | CH3 | CH3 | CH2CO | Ph | |
Ⅳ-101 | Cl | SO2CH3 | H | iPr | CH3 | CH3 | CH2CO | Ph | |
Ⅳ-102 | Cl | SO2CH3 | CH3 | CH3 | CH3 | CH3 | CH2CO | Ph | |
Ⅳ-103 | Cl | SO2CH3 | H | tBu | CH3 | H | CH2 | Ph | |
Ⅳ-104 | Cl | SO2CH3 | H | tBu | H | CH3 | CH2 | Ph | |
Ⅳ-105 | Cl | SO2CH3 | H | tBu | CH3 | H | SO2 | 4-Me-Ph | |
Ⅳ-106 | Cl | SO2CH3 | H | tBu | H | CH3 | SO2 | 4-Me-Ph | |
Ⅳ-107 | Cl | SO2CH3 | H | tBu | CH3 | H | CH2CO | Ph | |
Ⅳ-108 | Cl | SO2CH3 | H | tBu | CH3 | CH3 | CH2CO | Ph | |
Ⅳ-109 | Cl | SO2CH3 | CH3 | tBu | CH3 | H | CH2CO | Ph | |
Ⅳ-110 | Cl | SO2CH3 | CH3 | tBu | H | H | CH2CO | Ph |
表5
No. | R1 | R2 | R4 | R5 | R7 | X | R6 | 物理值 |
Ⅴ-1 | Cl | Cl | H | CH3 | H | SO2 | 4-Me-Ph | |
Ⅴ-2 | Cl | Cl | H | C2H5 | H | SO2 | 4-Me-Ph | |
Ⅴ-3 | Cl | Cl | H | Pr | H | SO2 | 4-Me-Ph | |
Ⅴ-4 | Cl | Cl | CH3 | CH3 | H | SO2 | 4-Me-Ph | |
Ⅴ-5 | Cl | Cl | H | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅴ-6 | Cl | Cl | H | C2H5 | CH3 | SO2 | 4-Me-Ph | |
Ⅴ-7 | Cl | Cl | H | iPr | CH3 | SO2 | 4-Me-Ph | |
Ⅴ-8 | Cl | Cl | CH3 | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅴ-9 | Cl | Cl | H | tBu | H | SO2 | 4-Me-Ph | |
Ⅴ-10 | Cl | Cl | H | tBu | CH3 | SO2 | 4-Me-Ph | |
Ⅴ-11 | Cl | Cl | CH3 | tBu | CH3 | SO2 | 4-Me-Ph | |
Ⅴ-12 | Cl | Cl | H | CH3 | H | CH2 | Ph | |
Ⅴ-13 | Cl | Cl | H | C2H5 | H | CH2 | Ph | |
Ⅴ-14 | Cl | Cl | H | Pr | H | CH2 | Ph | |
Ⅴ-15 | Cl | Cl | CH3 | CH3 | H | CH2 | Ph | |
Ⅴ-16 | Cl | Cl | H | CH3 | CH3 | CH2 | Ph |
表5(续)
No. | R1 | R2 | R4 | R5 | R7 | X | R6 | 物理值 |
Ⅴ-17 | Cl | Cl | H | C2H5 | CH3 | CH2 | Ph | |
Ⅴ-18 | Cl | Cl | H | iPr | CH3 | CH2 | Ph | |
Ⅴ-19 | Cl | Cl | CH3 | CH3 | CH3 | CH2 | Ph | |
Ⅴ-20 | Cl | Cl | H | tBu | H | CH2 | Ph | |
Ⅴ-21 | Cl | Cl | H | tBu | CH3 | CH2 | Ph | |
Ⅴ-22 | Cl | Cl | CH3 | tBu | CH3 | CH2CO | Ph | |
Ⅴ-23 | Cl | Cl | H | CH3 | H | CH2CO | Ph | |
Ⅴ-24 | Cl | Cl | H | C2H5 | H | CH2CO | Ph | |
Ⅴ-25 | Cl | Cl | H | iPr | H | CH2CO | Ph | |
Ⅴ-26 | Cl | Cl | CH3 | CH3 | H | CH2CO | Ph | |
Ⅴ-27 | Cl | Cl | H | CH3 | CH3 | CH2CO | Ph | |
Ⅴ-28 | Cl | Cl | H | C2H5 | CH3 | CH2CO | Ph | |
Ⅴ-29 | Cl | Cl | H | iPr | CH3 | CH2CO | Ph | |
Ⅴ-30 | Cl | Cl | CH3 | CH3 | CH3 | CH2CO | Ph | |
Ⅴ-31 | Cl | Cl | H | tBu | H | CH2CO | Ph | |
Ⅴ-32 | Cl | Cl | H | tBu | CH3 | CH2CO | Ph | |
Ⅴ-33 | Cl | Cl | CH3 | tBu | CH3 | CH2CO | Ph | |
Ⅴ-34 | Cl | Cl | H | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅴ-35 | Cl | Cl | H | C2H5 | CH3 | SO2 | 4-Me-Ph | |
Ⅴ-36 | Cl | Cl | H | CH3 | H | CH2 | Ph | |
Ⅴ-37 | Cl | Cl | H | C2H5 | H | CH2 | Ph | |
Ⅴ-38 | Cl | Cl | H | CH3 | CH3 | CH2CO | Ph | |
Ⅴ-39 | Cl | Cl | H | C2H5 | CH3 | CH2CO | Ph |
表5(续)
No. | R1 | R2 | R4 | R5 | R7 | X | R6 | 物理值 |
Ⅴ-40 | Cl | SO2CH3 | H | CH3 | H | SO2 | 4-Me-Ph | |
Ⅴ-41 | Cl | SO2CH3 | H | C2H5 | H | SO2 | 4-Me-Ph | |
Ⅴ-42 | Cl | SO2CH3 | H | iPr | H | SO2 | 4-Me-Ph | |
Ⅴ-43 | Cl | SO2CH3 | CH3 | CH3 | H | SO2 | 4-Me-Ph | |
Ⅴ-44 | Cl | SO2CH3 | H | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅴ-45 | Cl | SO2CH3 | H | C2H5 | CH3 | SO2 | 4-Me-Ph | |
Ⅴ-46 | Cl | SO2CH3 | H | iPr | CH3 | SO2 | 4-Me-Ph | |
Ⅴ-47 | Cl | SO2CH3 | CH3 | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅴ-48 | Cl | SO2CH3 | H | tBu | H | SO2 | 4-Me-Ph | |
Ⅴ-49 | Cl | SO2CH3 | H | tBu | CH3 | SO2 | 4-Me-Ph | |
Ⅴ-50 | Cl | SO2CH3 | CH3 | tBu | CH3 | SO2 | 4-Me-Ph | |
Ⅴ-51 | Cl | SO2CH3 | H | CH3 | H | CH2 | Ph | |
Ⅴ-52 | Cl | SO2CH3 | H | C2H5 | H | CH2 | Ph | |
Ⅴ-53 | Cl | SO2CH3 | H | iPr | H | CH2 | Ph | |
Ⅴ-54 | Cl | SO2CH3 | CH3 | CH3 | H | CH2 | Ph | |
Ⅴ-55 | Cl | SO2CH3 | H | CH3 | CH3 | CH2 | Ph | |
Ⅴ-56 | Cl | SO2CH3 | H | C2H5 | CH3 | CH2 | Ph | |
Ⅴ-57 | Cl | SO2CH3 | H | iPr | CH3 | CH2 | Ph | |
Ⅴ-58 | Cl | SO2CH3 | CH3 | CH3 | CH3 | CH2 | Ph | |
Ⅴ-59 | Cl | SO2CH3 | H | tBu | H | CH2 | Ph | |
Ⅴ-60 | Cl | SO2CH3 | H | tBu | CH3 | CH2 | Ph | |
Ⅴ-61 | Cl | SO2CH3 | CH3 | tBu | CH3 | CH2 | Ph |
表5(续)
No. | R1 | R2 | R4 | R5 | R7 | X | R6 | 物理值 |
Ⅴ-62 | Cl | SO2CH3 | H | CH3 | H | CH2CO | Ph | |
Ⅴ-63 | Cl | SO2CH3 | H | C2H5 | H | CH2CO | Ph | |
Ⅴ-64 | Cl | SO2CH3 | H | iPr | H | CH2CO | Ph | |
Ⅴ-65 | Cl | SO2CH3 | CH3 | CH3 | H | CH2CO | Ph | |
Ⅴ-66 | Cl | SO2CH3 | H | CH3 | CH3 | CH2CO | Ph | |
Ⅴ-67 | Cl | SO2CH3 | H | C2H5 | CH3 | CH2CO | Ph | |
Ⅴ-68 | Cl | SO2CH3 | H | iPr | CH3 | CH2CO | Ph | |
Ⅴ-69 | Cl | SO2CH3 | CH3 | CH3 | CH3 | CH2CO | Ph | |
Ⅴ-70 | Cl | SO2CH3 | H | tBu | H | CH2CO | Ph | |
Ⅴ-71 | Cl | SO2CH3 | H | tBu | CH3 | CH2CO | Ph | |
Ⅴ-72 | Cl | SO2CH3 | CH3 | tBu | CH3 | CH2CO | Ph | |
Ⅴ-73 | Cl | SO2CH3 | H | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅴ-74 | Cl | SO2CH3 | H | C2H5 | CH3 | SO2 | 4-Me-Ph | |
Ⅴ-75 | Cl | SO2CH3 | H | CH3 | H | CH2 | Ph | |
Ⅴ-76 | Cl | SO2CH3 | H | C2H5 | H | CH2 | Ph | |
Ⅴ-77 | Cl | SO2CH3 | H | CH3 | CH3 | CH2CO | Ph | |
Ⅴ-78 | Cl | SO2CH3 | H | C2H5 | CH3 | CH2CO | Ph | |
Ⅴ-79 | Cl | SO2CH3 | H | tBu | H | CH2CO | Ph | |
Ⅴ-80 | Cl | SO2CH3 | H | tBu | CH3 | CH2CO | Ph | |
Ⅴ-81 | Cl | SO2CH3 | CH3 | tBu | CH3 | CH2CO | Ph |
No. | R1 | R2 | R4 | R5 | R7 | R8 | X | R6 | 物理值 |
Ⅵ-1 | Cl | Cl | H | CH3 | H | H | SO2 | 4-Me-Ph | |
Ⅵ-2 | Cl | Cl | H | C2H5 | H | H | SO2 | 4-Me-Ph | |
Ⅵ-3 | Cl | Cl | H | iPr | H | H | SO2 | 4-Me-Ph | |
Ⅵ-4 | Cl | Cl | CH3 | CH3 | H | H | SO2 | 4-Me-Ph | |
Ⅵ-5 | Cl | Cl | H | CH3 | H | H | CH2 | Ph | |
Ⅵ-6 | Cl | Cl | H | C2H5 | H | H | CH2 | Ph | |
Ⅵ-7 | Cl | Cl | H | iPr | H | H | CH2 | Ph | |
Ⅵ-8 | Cl | Cl | CH3 | CH3 | CH3 | H | CH2 | Ph | |
Ⅵ-9 | Cl | Cl | H | CH3 | H | H | CH2CO | Ph | |
Ⅵ-10 | Cl | Cl | H | C2H5 | H | H | CH2CO | Ph | |
Ⅵ-11 | Cl | Cl | H | iPr | H | H | CH2CO | Ph | |
Ⅵ-12 | Cl | Cl | CH3 | CH3 | CH3 | H | CH2CO | Ph | |
Ⅵ-13 | Cl | Cl | H | CH3 | CH3 | H | SO2 | 4-Me-Ph | |
Ⅵ-14 | Cl | Cl | H | C2H5 | CH3 | H | SO2 | 4-Me-Ph | |
Ⅵ-15 | Cl | Cl | H | iPr | CH3 | H | SO2 | 4-Me-Ph | |
Ⅵ-16 | Cl | Cl | CH3 | CH3 | CH3 | H | SO2 | 4-Me-Ph |
表6(续)
No. | R1 | R2 | R4 | R5 | R7 | R8 | X | R6 | 物理值 |
Ⅵ-17 | Cl | Cl | H | CH3 | CH3 | H | CH2 | Ph | |
Ⅵ-18 | Cl | Cl | H | C2H5 | CH3 | H | CH2 | Ph | |
Ⅵ-19 | Cl | Cl | H | iPr | CH3 | H | CH2 | Ph | |
Ⅵ-20 | Cl | Cl | CH3 | CH3 | CH3 | H | CH2 | Ph | |
Ⅵ-21 | Cl | Cl | H | CH3 | CH3 | H | CH2CO | Ph | |
Ⅵ-22 | Cl | Cl | H | C2H5 | CH3 | H | CH2CO | Ph | |
Ⅵ-19 | Cl | Cl | H | iPr | CH3 | H | CH2CO | Ph | |
Ⅵ-20 | Cl | Cl | CH3 | CH3 | CH3 | H | CH2CO | Ph | |
Ⅵ-21 | Cl | Cl | H | CH3 | H | CH3 | SO2 | 4-Me-Ph | |
Ⅵ-22 | Cl | Cl | H | C2H5 | H | CH3 | SO2 | 4-Me-Ph | |
Ⅵ-23 | Cl | Cl | H | iPr | H | CH3 | SO2 | 4-Me-Ph | |
Ⅵ-24 | Cl | Cl | CH3 | CH3 | H | CH3 | SO2 | 4-Me-Ph | |
Ⅵ-25 | Cl | Cl | H | CH3 | H | CH3 | CH2 | Ph | |
Ⅵ-26 | Cl | Cl | H | C2H5 | H | CH3 | CH2 | Ph | |
Ⅵ-27 | Cl | Cl | H | iPr | H | CH3 | CH2 | Ph | |
Ⅵ-28 | Cl | Cl | CH3 | CH3 | CH3 | CH3 | CH2 | Ph | |
Ⅵ-29 | Cl | Cl | H | CH3 | H | CH3 | CH2CO | Ph | |
Ⅵ-30 | Cl | Cl | H | C2H5 | H | CH3 | CH2CO | Ph | |
Ⅵ-31 | Cl | Cl | H | iPr | H | CH3 | CH2CO | Ph | |
Ⅵ-32 | Cl | Cl | CH3 | CH3 | CH3 | CH3 | CH2CO | Ph |
表6(续)
No. | R1 | R2 | R4 | R5 | R7 | R8 | X | R6 | 物理值 |
Ⅵ-33 | Cl | Cl | H | CH3 | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅵ-34 | Cl | Cl | H | C2H5 | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅵ-35 | Cl | Cl | H | iPr | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅵ-36 | Cl | Cl | CH3 | CH3 | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅵ-37 | Cl | Cl | H | CH3 | CH3 | CH3 | CH2 | Ph | |
Ⅵ-38 | Cl | Cl | H | C2H5 | CH3 | CH3 | CH2 | Ph | |
Ⅵ-39 | Cl | Cl | H | iPr | CH3 | CH3 | CH2 | Ph | |
Ⅵ-40 | Cl | Cl | CH3 | CH3 | CH3 | CH3 | CH2 | Ph | |
Ⅵ-41 | Cl | Cl | H | CH3 | CH3 | CH3 | CH2CO | Ph | |
Ⅵ-42 | Cl | Cl | H | C2H5 | CH3 | CH3 | CH2CO | Ph | |
Ⅵ-43 | Cl | Cl | H | iPr | CH3 | CH3 | CH2CO | Ph | |
Ⅵ-44 | Cl | Cl | CH3 | CH3 | CH3 | CH3 | CH2CO | Ph | |
Ⅵ-45 | Cl | Cl | H | tBu | CH3 | H | CH2 | Ph | |
Ⅵ-46 | Cl | Cl | H | tBu | CH3 | H | CH2 | Ph | |
Ⅵ-47 | Cl | Cl | CH3 | tBu | CH3 | H | SO2 | 4-Me-Ph | |
Ⅵ-48 | Cl | Cl | CH3 | tBu | CH3 | H | SO2 | 4-Me-Ph | |
Ⅵ-49 | Cl | Cl | CH3 | tBu | CH3 | H | CH2CO | Ph | |
Ⅵ-50 | Cl | Cl | CH3 | tBu | CH3 | H | CH2CO | Ph |
表6(续)
No. | R1 | R2 | R4 | R5 | R7 | R8 | X | R6 | 物理值 |
Ⅵ-5l | Cl | SO2CH3 | H | CH3 | H | H | SO2 | 4-Me-Ph | |
Ⅵ-52 | Cl | SO2CH3 | H | C2H5 | H | H | SO2 | 4-Me-Ph | |
Ⅵ-53 | Cl | SO2CH3 | H | iPr | H | H | SO2 | 4-Me-Ph | |
Ⅵ-54 | Cl | SO2CH3 | CH3 | CH3 | H | H | SO2 | 4-Me-Ph | |
Ⅵ-55 | Cl | SO2CH3 | H | CH3 | H | H | CH2 | Ph | |
Ⅵ-56 | Cl | SO2CH3 | H | C2H5 | H | H | CH2 | Ph | |
Ⅵ-57 | Cl | SO2CH3 | H | iPr | H | H | CH2 | Ph | |
Ⅵ-58 | Cl | SO2CH3 | CH3 | CH3 | CH3 | H | CH2 | Ph | |
Ⅵ-59 | Cl | SO2CH3 | H | CH3 | H | H | CH2CO | Ph | |
Ⅵ-60 | Cl | SO2CH3 | H | C2H5 | H | H | CH2CO | Ph | |
Ⅵ-61 | Cl | SO2CH3 | H | iPr | H | H | CH2CO | Ph | |
Ⅵ-62 | Cl | SO2CH3 | CH3 | CH3 | CH3 | H | CH2CO | Ph | |
Ⅵ-63 | Cl | SO2CH3 | H | CH3 | CH3 | H | SO2 | 4-Me-Ph | |
Ⅵ-64 | Cl | SO2CH3 | H | C2H5 | CH3 | H | SO2 | 4-Me-Ph | |
Ⅵ-65 | Cl | SO2CH3 | H | iPr | CH3 | H | SO2 | 4-Me-Ph | |
Ⅵ-66 | Cl | SO2CH3 | CH3 | CH3 | CH3 | H | SO2 | 4-Me-Ph | |
Ⅵ-67 | Cl | SO2CH3 | H | CH3 | CH3 | H | CH2 | Ph | |
Ⅵ-68 | Cl | SO2CH3 | H | C2H5 | CH3 | H | CH2 | Ph | |
Ⅵ-69 | Cl | SO2CH3 | H | iPr | CH3 | H | CH2 | Ph | |
Ⅵ-70 | Cl | SO2CH3 | CH3 | CH3 | CH3 | H | CH2 | Ph |
表6(续)
No. | R1 | R2 | R4 | R5 | R7 | R8 | X | R6 | 物理值 |
Ⅵ-71 | Cl | SO2CH3 | H | CH3 | CH3 | H | CH2CO | Ph | |
Ⅵ-72 | Cl | SO2CH3 | H | C2H5 | CH3 | H | CH2CO | Ph | |
Ⅵ-73 | Cl | SO2CH3 | H | iPr | CH3 | H | CH2CO | Ph | |
Ⅵ-74 | Cl | SO2CH3 | CH3 | CH3 | CH3 | H | CH2CO | Ph | |
Ⅵ-75 | CH3 | SO2CH3 | H | CH3 | CH3 | H | SO2 | 4-Me-Ph | |
Ⅵ-76 | CH3 | SO2CH3 | H | C2H5 | CH3 | H | SO2 | 4-Me-Ph | |
Ⅵ-77 | CH3 | SO2CH3 | H | CH3 | CH3 | H | CH2 | Ph | |
Ⅵ-78 | CH3 | SO2CH3 | H | C2H5 | CH3 | H | CH2 | Ph | |
Ⅵ-79 | Cl | SO2CH3 | H | CH3 | H | CH3 | SO2 | 4-Me-Ph | |
Ⅵ-80 | Cl | SO2CH3 | H | C2H5 | H | CH3 | SO2 | 4-Me-Ph | |
Ⅵ-81 | Cl | SO2CH3 | H | iPr | H | CH3 | SO2 | 4-Me-Ph | |
Ⅵ-82 | Cl | SO2CH3 | CH3 | CH3 | H | CH3 | SO2 | 4-Me-Ph | |
Ⅵ-83 | Cl | SO2CH3 | H | CH3 | H | CH3 | CH2 | Ph | |
Ⅵ-84 | Cl | SO2CH3 | H | C2H5 | H | CH3 | CH2 | Ph | |
Ⅵ-85 | Cl | SO2CH3 | H | iPr | H | CH3 | CH2 | Ph | |
Ⅵ-86 | Cl | SO2CH3 | CH3 | CH3 | CH3 | CH3 | CH2 | Ph | |
Ⅵ-87 | Cl | SO2CH3 | H | CH3 | H | CH3 | CH2CO | Ph | |
Ⅵ-88 | Cl | SO2CH3 | H | C2H5 | H | CH3 | CH2CO | Ph | |
Ⅵ-89 | Cl | SO2CH3 | H | iPr | H | CH3 | CH2CO | Ph | |
Ⅵ-90 | Cl | SO2CH3 | CH3 | CH3 | CH3 | CH3 | CH2CO | Ph | |
Ⅵ-91 | Cl | SO2CH3 | H | CH3 | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅵ-92 | Cl | SO2CH3 | H | C2H5 | CH3 | CH3 | SO2 | 4-Me-Ph |
表6(续)
No. | R1 | R2 | R4 | R5 | R7 | R8 | X | R6 | 物理值 |
Ⅵ-93 | Cl | SO2CH3 | H | iPr | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅵ-94 | Cl | SO2CH3 | CH3 | CH3 | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅵ-95 | Cl | SO2CH3 | H | CH3 | CH3 | CH3 | CH2 | Ph | |
Ⅵ-96 | Cl | SO2CH3 | H | C2H5 | CH3 | CH3 | CH2 | Ph | |
Ⅵ-97 | Cl | SO2CH3 | H | iPr | CH3 | CH3 | CH2 | Ph | |
Ⅵ-98 | Cl | SO2CH3 | CH3 | CH3 | CH3 | CH3 | CH2 | Ph | |
Ⅵ-99 | Cl | SO2CH3 | H | CH3 | CH3 | CH3 | CH2CO | Ph | |
Ⅵ-100 | Cl | SO2CH3 | H | C2H5 | CH3 | CH3 | CH2CO | Ph | |
Ⅵ-101 | Cl | SO2CH3 | H | iPr | CH3 | CH3 | CH2CO | Ph | |
Ⅵ-102 | Cl | SO2CH3 | CH3 | CH3 | CH3 | CH3 | CH2CO | Ph | |
Ⅵ-103 | Cl | SO2CH3 | H | tBu | CH3 | H | CH2 | Ph | |
Ⅵ-104 | Cl | SO2CH3 | H | tBu | H | CH3 | CH2 | Ph | |
Ⅵ-105 | Cl | SO2CH3 | H | tBu | CH3 | H | SO2 | 4-Me-Ph | |
Ⅵ-106 | Cl | SO2CH3 | H | tBu | H | CH3 | SO2 | 4-Me-Ph | |
Ⅵ-107 | Cl | SO2CH3 | H | tBu | CH3 | H | CH2CO | Ph | |
Ⅵ-108 | Cl | SO2CH3 | H | tBu | CH3 | CH3 | CH2CO | Ph | |
Ⅵ-109 | Cl | SO2CH3 | CH3 | tBu | CH3 | H | CH2CO | Ph | |
Ⅵ-110 | Cl | SO2CH3 | CH3 | tBu | H | H | CH2CO | Ph |
表7
No. | R1 | R2 | R4 | R5 | R7 | R8 | X | R6 | 物理值 |
Ⅶ-1 | Cl | Cl | H | CH3 | H | H | SO2 | 4-Me-Ph | |
Ⅶ-2 | Cl | Cl | H | C2H5 | H | H | SO2 | 4-Me-Ph | |
Ⅶ-3 | Cl | Cl | H | iPr | H | H | SO2 | 4-Me-Ph | |
Ⅶ-4 | Cl | Cl | CH3 | CH3 | H | H | SO2 | 4-Me-Ph | |
Ⅶ-5 | Cl | Cl | H | CH3 | H | H | CH2 | Ph | |
Ⅶ-6 | Cl | Cl | H | C2H5 | H | H | CH2 | Ph | |
Ⅶ-7 | Cl | Cl | H | iPr | H | H | CH2 | Ph | |
Ⅶ-8 | Cl | Cl | CH3 | CH3 | CH3 | H | CH2 | Ph | |
Ⅶ-9 | Cl | Cl | H | CH3 | H | H | CH2CO | Ph | |
Ⅶ-10 | Cl | Cl | H | C2H5 | H | H | CH2CO | Ph | |
Ⅶ-11 | Cl | Cl | H | iPr | H | H | CH2CO | Ph | |
Ⅶ-12 | Cl | Cl | CH3 | CH3 | CH3 | H | CH2CO | Ph | |
Ⅶ-13 | Cl | Cl | H | CH3 | CH3 | H | SO2 | 4-Me-Ph | |
Ⅶ-14 | Cl | Cl | H | C2H5 | CH3 | H | SO2 | 4-Me-Ph | |
Ⅶ-15 | Cl | Cl | H | iPr | CH3 | H | SO2 | 4-Me-Ph | |
Ⅶ-16 | Cl | Cl | CH3 | CH3 | CH3 | H | SO2 | 4-Me-Ph |
表7(续)
No. | R1 | R2 | R4 | R5 | R7 | R8 | X | R6 | 物理值 |
Ⅶ-17 | Cl | Cl | H | CH3 | CH3 | H | CH2 | Ph | |
Ⅶ-18 | Cl | Cl | H | C2H5 | CH3 | H | CH2 | Ph | |
Ⅶ-19 | Cl | Cl | H | iPr | CH3 | H | CH2 | Ph | |
Ⅶ-20 | Cl | Cl | CH3 | CH3 | CH3 | H | CH2 | Ph | |
Ⅶ-21 | Cl | Cl | H | CH3 | CH3 | H | CH2CO | Ph | |
Ⅶ-22 | Cl | Cl | H | C2H5 | CH3 | H | CH2CO | Ph | |
Ⅶ-19 | Cl | Cl | H | iPr | CH3 | H | CH2CO | Ph | |
Ⅶ-20 | Cl | Cl | CH3 | CH3 | CH3 | H | CH2CO | Ph | |
Ⅶ-21 | Cl | Cl | H | CH3 | H | CH3 | SO2 | 4-Me-Ph | |
Ⅶ-22 | Cl | Cl | H | C2H5 | H | CH3 | SO2 | 4-Me-Ph | |
Ⅶ-23 | Cl | Cl | H | iPr | H | CH3 | SO2 | 4-Me-Ph | |
Ⅶ-24 | Cl | Cl | CH3 | CH3 | H | CH3 | SO2 | 4-Me-Ph | |
Ⅶ-25 | Cl | Cl | H | CH3 | H | CH3 | CH2 | Ph | |
Ⅶ-26 | Cl | Cl | H | C2H5 | H | CH3 | CH2 | Ph | |
Ⅶ-27 | Cl | Cl | H | iPr | H | CH3 | CH2 | Ph | |
Ⅶ-28 | Cl | Cl | CH3 | CH3 | CH3 | CH3 | CH2 | Ph | |
Ⅶ-29 | Cl | Cl | H | CH3 | H | CH3 | CH2CO | Ph | |
Ⅶ-30 | Cl | Cl | H | C2H5 | H | CH3 | CH2CO | Ph | |
Ⅶ-31 | Cl | Cl | H | iPr | H | CH3 | CH2CO | Ph | |
Ⅶ-32 | Cl | Cl | CH3 | CH3 | CH3 | CH3 | CH2CO | Ph |
表7(续)
No. | R1 | R2 | R4 | R5 | R7 | R8 | X | R6 | 物理值 |
Ⅶ-33 | Cl | Cl | H | CH3 | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅶ-34 | Cl | Cl | H | C2H5 | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅶ-35 | Cl | Cl | H | iPr | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅶ-36 | Cl | Cl | CH3 | CH3 | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅶ-37 | Cl | Cl | H | CH3 | CH3 | CH3 | CH2 | Ph | |
Ⅶ-38 | Cl | Cl | H | C2H5 | CH3 | CH3 | CH2 | Ph | |
Ⅶ-39 | Cl | Cl | H | iPr | CH3 | CH3 | CH2 | Ph | |
Ⅶ-40 | Cl | Cl | CH3 | CH3 | CH3 | CH3 | CH2 | Ph | |
Ⅶ-41 | Cl | Cl | H | CH3 | CH3 | CH3 | CH2CO | Ph | |
Ⅶ-42 | Cl | Cl | H | C2H5 | CH3 | CH3 | CH2CO | Ph | |
Ⅶ-43 | Cl | Cl | H | iPr | CH3 | CH3 | CH2CO | Ph | |
Ⅶ-44 | Cl | Cl | CH3 | CH3 | CH3 | CH3 | CH2CO | Ph | |
Ⅶ-45 | Cl | Cl | H | tBu | CH3 | H | CH2 | Ph | |
Ⅶ-46 | Cl | Cl | H | tBu | CH3 | H | CH2 | Ph | |
Ⅶ-47 | Cl | Cl | CH3 | tBu | CH3 | H | SO2 | 4-Me-Ph | |
Ⅶ-48 | Cl | Cl | CH3 | tBu | CH3 | H | SO2 | 4-Me-Ph | |
Ⅶ-49 | Cl | Cl | CH3 | tBu | CH3 | H | CH2CO | Ph | |
Ⅶ-50 | Cl | Cl | CH3 | tBu | CH3 | H | CH2CO | Ph |
表7(续)
No. | R1 | R2 | R4 | R5 | R7 | R8 | X | R6 | 物理值 |
Ⅶ-51 | Cl | SO2CH3 | H | CH3 | H | H | SO2 | 4-Me-Ph | |
Ⅶ-52 | Cl | SO2CH3 | H | C2H5 | H | H | SO2 | 4-Me-Ph | |
Ⅶ-53 | Cl | SO2CH3 | H | iPr | H | H | SO2 | 4-Me-Ph | |
Ⅶ-54 | Cl | SO2CH3 | CH3 | CH3 | H | H | SO2 | 4-Me-Ph | |
Ⅶ-55 | Cl | SO2CH3 | H | CH3 | H | H | CH2 | Ph | |
Ⅶ-56 | Cl | SO2CH3 | H | C2H5 | H | H | CH2 | Ph | |
Ⅶ-57 | Cl | SO2CH3 | H | iPr | H | H | CH2 | Ph | |
Ⅶ-58 | Cl | SO2CH3 | CH3 | CH3 | CH3 | H | CH2 | Ph | |
Ⅶ-59 | Cl | SO2CH3 | H | CH3 | H | H | CH2CO | Ph | |
Ⅶ-60 | Cl | SO2CH3 | H | C2H5 | H | H | CH2CO | Ph | |
Ⅶ-61 | Cl | SO2CH3 | H | iPr | H | H | CH2CO | Ph | |
Ⅶ-62 | Cl | SO2CH3 | CH3 | CH3 | CH3 | H | CH2CO | Ph | |
Ⅶ-63 | Cl | SO2CH3 | H | CH3 | CH3 | H | SO2 | 4-Me-Ph | |
Ⅶ-64 | Cl | SO2CH3 | H | C2H5 | CH3 | H | SO2 | 4-Me-Ph | |
Ⅶ-65 | Cl | SO2CH3 | H | iPr | CH3 | H | SO2 | 4-Me-Ph | |
Ⅶ-66 | Cl | SO2CH3 | CH3 | CH3 | CH3 | H | SO2 | 4-Me-Ph | |
Ⅶ-67 | Cl | SO2CH3 | H | CH3 | CH3 | H | CH2 | Ph | |
Ⅶ-68 | Cl | SO2CH3 | H | C2H5 | CH3 | H | CH2 | Ph | |
Ⅶ-69 | Cl | SO2CH3 | H | iPr | CH3 | H | CH2 | Ph | |
Ⅶ-70 | Cl | SO2CH3 | CH3 | CH3 | CH3 | H | CH2 | Ph |
表7(续)
No. | R1 | R2 | R4 | R5 | R7 | R8 | X | R6 | 物理值 |
Ⅶ-71 | Cl | SO2CH3 | H | CH3 | CH3 | H | CH2CO | Ph | |
Ⅶ-72 | Cl | SO2CH3 | H | C2H3 | CH3 | H | CH2CO | Ph | |
Ⅶ-73 | Cl | SO2CH3 | H | iPr | CH3 | H | CH2CO | Ph | |
Ⅶ-74 | Cl | SO2CH3 | CH3 | CH3 | CH3 | H | CH2CO | Ph | |
Ⅶ-75 | CH3 | SO2CH3 | H | CH3 | CH3 | H | SO2 | 4-Me-Ph | |
Ⅶ-76 | CH3 | SO2CH3 | H | C2H5 | CH3 | H | SO2 | 4-Me-Ph | |
Ⅶ-77 | CH3 | SO2CH3 | H | CH3 | CH3 | H | CH2 | Ph | |
Ⅶ-78 | CH3 | SO2CH3 | H | C2H5 | CH3 | H | CH2 | Ph | |
Ⅶ-79 | Cl | SO2CH3 | H | CH3 | H | CH3 | SO2 | 4-Me-Ph | |
Ⅶ-80 | Cl | SO2CH3 | H | C2H5 | H | CH3 | SO2 | 4-Me-Ph | |
Ⅶ-81 | Cl | SO2CH3 | H | iPr | H | CH3 | SO2 | 4-Me-Ph | |
Ⅶ-82 | Cl | SO2CH3 | CH3 | CH3 | H | CH3 | SO2 | 4-Me-Ph | |
Ⅶ-83 | Cl | SO2CH3 | H | CH3 | H | CH3 | CH2 | Ph | |
Ⅶ-84 | Cl | SO2CH3 | H | C2H5 | H | CH3 | CH2 | Ph | |
Ⅶ-85 | Cl | SO2CH3 | H | iPr | H | CH3 | CH2 | Ph | |
Ⅶ-86 | Cl | SO2CH3 | CH3 | CH3 | CH3 | CH3 | CH2 | Ph | |
Ⅶ-87 | Cl | SO2CH3 | H | CH3 | H | CH3 | CH2CO | Ph | |
Ⅶ-88 | Cl | SO2CH3 | H | C2H5 | H | CH3 | CH2CO | Ph | |
Ⅶ-89 | Cl | SO2CH3 | H | iPr | H | CH3 | CH2CO | Ph | |
Ⅶ-90 | Cl | SO2CH3 | CH3 | CH3 | CH3 | CH3 | CH2CO | Ph | |
Ⅶ-91 | Cl | SO2CH3 | H | CH3 | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅶ-92 | Cl | SO2CH3 | H | C2H5 | CH3 | CH3 | SO2 | 4-Me-Ph |
表7(续)
No. | R1 | R2 | R4 | R5 | R7 | R8 | X | R6 | 物理值 |
Ⅶ-93 | Cl | SO2CH3 | H | iPr | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅶ-94 | Cl | SO2CH3 | CH3 | CH3 | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅶ-95 | Cl | SO2CH3 | H | CH3 | CH3 | CH3 | CH2 | Ph | |
Ⅶ-96 | Cl | SO2CH3 | H | C2H5 | CH3 | CH3 | CH2 | Ph | |
Ⅶ-97 | Cl | SO2CH3 | H | iPr | CH3 | CH3 | CH2 | Ph | |
Ⅶ-98 | Cl | SO2CH3 | CH3 | CH3 | CH3 | CH3 | CH2 | Ph | |
Ⅶ-99 | Cl | SO2CH3 | H | CH3 | CH3 | CH3 | CH2CO | Ph | |
Ⅶ-100 | Cl | SO2CH3 | H | C2H5 | CH3 | CH3 | CH2CO | Ph | |
Ⅶ-101 | Cl | SO2CH3 | H | iPr | CH3 | CH3 | CH2CO | Ph | |
Ⅶ-102 | Cl | SO2CH3 | CH3 | CH3 | CH3 | CH3 | CH2CO | Ph | |
Ⅶ-103 | Cl | SO2CH3 | H | tBu | CH3 | H | CH2 | Ph | |
Ⅶ-104 | Cl | SO2CH3 | H | tBu | H | CH3 | CH2 | Ph | |
Ⅶ-105 | Cl | SO2CH3 | H | tBu | CH3 | H | SO2 | 4-Me-Ph | |
Ⅶ-106 | Cl | SO2CH3 | H | tBu | H | CH3 | SO2 | 4-Me-Ph | |
Ⅶ-107 | Cl | SO2CH3 | H | tBu | CH3 | H | CH2CO | Ph | |
Ⅶ-108 | Cl | SO2CH3 | H | tBu | CH3 | CH3 | CH2CO | Ph | |
Ⅶ-109 | Cl | SO2CH3 | CH3 | tBu | CH3 | H | CH2CO | Ph | |
Ⅶ-110 | Cl | SO2CH3 | CH3 | tBu | H | H | CH2CO | Ph |
表8
No. | R1 | R2 | R4 | R5 | R7 | R8 | X | R6 | 物理值 |
Ⅷ-1 | Cl | Cl | H | CH3 | H | H | SO2 | 4-Me-Ph | |
Ⅷ-2 | Cl | Cl | H | C2H5 | H | H | SO2 | 4-Me-Ph | |
Ⅷ-3 | Cl | Cl | H | iPr | H | H | SO2 | 4-Me-Ph | |
Ⅷ-4 | Cl | Cl | CH3 | CH3 | H | H | SO2 | 4-Me-Ph | |
Ⅷ-5 | Cl | Cl | H | CH3 | H | H | CH2 | Ph | |
Ⅷ-6 | Cl | Cl | H | C2H5 | H | H | CH2 | Ph | |
Ⅷ-7 | Cl | Cl | H | iPr | H | H | CH2 | Ph | |
Ⅷ-8 | Cl | Cl | CH3 | CH3 | CH3 | H | CH2 | Ph | |
Ⅷ-9 | Cl | Cl | H | CH3 | H | H | CH2CO | Ph | |
Ⅷ-10 | Cl | Cl | H | C2H5 | H | H | CH2CO | Ph | |
Ⅷ-11 | Cl | Cl | H | iPr | H | H | CH2CO | Ph | |
Ⅷ-12 | Cl | Cl | CH3 | CH3 | CH3 | H | CH2CO | Ph | |
Ⅷ-13 | Cl | Cl | H | CH3 | C2H5 | H | CH2CO | Ph | |
Ⅷ-14 | Cl | Cl | H | C2H5 | C2H5 | H | CH2CO | Ph | |
Ⅷ-15 | Cl | Cl | H | iPr | C2H5 | H | CH2 | Ph | |
Ⅷ-16 | Cl | Cl | CH3 | CH3 | C2H5 | H | CH2 | Ph |
表8(续)
No. | R1 | R2 | R4 | R3 | R7 | R8 | X | R6 | 物理值 |
Ⅷ-51 | Cl | SO2CH3 | H | CH3 | H | H | SO2 | 4-Me-Ph | |
Ⅷ-52 | Cl | SO2CH3 | H | C2H5 | H | H | SO2 | 4-Me-Ph | |
Ⅷ-53 | Cl | SO2CH3 | H | iPr | H | H | SO2 | 4-Me-Ph | |
Ⅷ-54 | Cl | SO2CH3 | CH3 | CH3 | H | H | SO2 | 4-Me-Ph | |
Ⅷ-55 | Cl | SO2CH3 | H | CH3 | H | H | CH2 | Ph | |
Ⅷ-56 | Cl | SO2CH3 | H | C2H5 | H | H | CH2 | Ph | |
Ⅷ-57 | Cl | SO2CH3 | H | iPr | H | H | CH2 | Ph | |
Ⅷ-58 | Cl | SO2CH3 | CH3 | CH3 | CH3 | CH3 | CH2 | Ph | |
Ⅷ-59 | Cl | SO2CH3 | H | CH3 | H | H | CH2CO | Ph | |
Ⅷ-60 | Cl | SO2CH3 | H | C2H5 | H | H | CH2CO | Ph | |
Ⅷ-61 | Cl | SO2CH3 | H | iPr | H | H | CH2CO | Ph | |
Ⅷ-62 | Cl | SO2CH3 | CH3 | CH3 | CH3 | CH3 | CH2CO | Ph | |
Ⅷ-63 | Cl | SO2CH3 | H | CH3 | CH3 | H | CH2CO | Ph | |
Ⅷ-64 | Cl | SO2CH3 | H | C2H5 | CH3 | H | CH2CO | Ph | |
Ⅷ-65 | Cl | SO2CH3 | H | iPr | CH3 | H | SO2 | 4-Me-Ph | |
Ⅷ-66 | Cl | SO2CH3 | CH3 | CH3 | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅷ-67 | Cl | SO2CH3 | H | CH3 | CH3 | CH3 | CH2 | Ph | |
Ⅷ-68 | Cl | SO2CH3 | H | C2H5 | CH3 | CH3 | CH2 | Ph | |
Ⅷ-69 | Cl | SO2CH3 | H | iPr | CH3 | CH3 | CH2CO | Ph | |
Ⅷ-70 | Cl | SO2CH3 | CH3 | CH3 | CH3 | CH3 | CH2CO | Ph |
表9
No. | R1 | R2 | R4 | R5 | R7 | X | R6 | 物理值 |
Ⅸ-1 | Cl | Cl | H | CH3 | H | SO2 | 4-Me-Ph | |
Ⅸ-2 | Cl | Cl | H | C2H5 | H | SO2 | 4-Me-Ph | |
Ⅸ-3 | Cl | Cl | H | iPr | H | SO2 | 4-Me-Ph | |
Ⅸ-4 | Cl | Cl | CH3 | CH3 | H | SO2 | 4-Me-Ph | |
Ⅸ-5 | Cl | Cl | H | CH3 | CH3 | CH2 | Ph | |
Ⅸ-6 | Cl | Cl | H | C2H5 | CH3 | CH2 | Ph | |
Ⅸ-7 | Cl | Cl | H | iPr | CH3 | CH2 | Ph | |
Ⅸ-8 | Cl | Cl | CH3 | CH3 | CH3 | CH2 | Ph | |
Ⅸ-9 | Cl | Cl | H | tBu | H | CH2CO | Ph | |
Ⅸ-10 | Cl | Cl | H | tBu | CH3 | CH2CO | Ph | |
Ⅸ-11 | Cl | Cl | CH3 | tBu | CH3 | CH2CO | Ph | |
Ⅸ-12 | Cl | Cl | H | CH3 | H | CH2CO | Ph | |
Ⅸ-13 | Cl | Cl | H | C2H5 | H | CH2CO | Ph | |
Ⅸ-14 | Cl | Cl | H | iPr | H | CH2CO | Ph | |
Ⅸ-15 | Cl | Cl | CH3 | CH3 | H | CH2 | Ph | |
Ⅸ-16 | Cl | Cl | H | CH3 | CH3 | CH2 | Ph |
表9(续)
No. | R1 | R2 | R4 | R5 | R7 | X | R6 | 物理值 |
Ⅸ-17 | Cl | Cl | H | C2H5 | CH3 | SO2 | 4-Me-Ph | |
Ⅸ-18 | Cl | Cl | H | iPr | CH3 | SO2 | 4-Me-Ph | |
Ⅸ-19 | Cl | Cl | CH3 | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅸ-20 | Cl | Cl | H | tBu | H | SO2 | 4-Me-Ph | |
Ⅸ-21 | Cl | Cl | H | tBu | CH3 | CH2 | Ph | |
Ⅸ-22 | Cl | Cl | CH3 | tBu | CH3 | CH2 | Ph | |
Ⅸ-23 | Cl | Cl | H | CH3 | H | CH2 | Ph | |
Ⅸ-24 | Cl | Cl | H | C2H5 | H | CH2 | Ph | |
Ⅸ-25 | Cl | Cl | H | iPr | H | CH2CO | Ph | |
Ⅸ-26 | Cl | Cl | CH3 | CH3 | H | CH2CO | Ph | |
Ⅸ-27 | Cl | Cl | H | CH3 | CH3 | CH2CO | Ph | |
Ⅸ-28 | Cl | Cl | H | C2H5 | CH3 | CH2CO | Ph | |
Ⅸ-29 | Cl | Cl | H | iPr | CH3 | CH2CO | Ph | |
Ⅸ-30 | Cl | Cl | CH3 | CH3 | CH3 | CH2CO | Ph | |
Ⅸ-31 | Cl | Cl | H | tBu | CH3 | SO2 | 4-Me-Ph | |
Ⅸ-32 | Cl | Cl | H | tBu | CH3 | SO2 | 4-Me-Ph | |
Ⅸ-33 | Cl | Cl | CH3 | tBu | CH3 | CH2 | Ph | |
Ⅸ-34 | Cl | Cl | H | CH3 | CH3 | CH2 | Ph | |
Ⅸ-35 | Cl | Cl | H | C2H5 | CH3 | CH2CO | Ph | |
Ⅸ-36 | Cl | Cl | H | CH3 | H | CH2CO | Ph | |
Ⅸ-37 | Cl | Cl | H | C2H5 | H | CH2CO | Ph | |
Ⅸ-38 | Cl | Cl | H | CH3 | C2H5 | CH2CO | Ph | |
Ⅸ-39 | Cl | Cl | H | C2H5 | C2H5 | CH2CO | Ph |
表9(续)
No. | R1 | R2 | R4 | R5 | R7 | X | R6 | 物理值 |
Ⅸ-40 | Cl | SO2CH3 | H | CH3 | H | SO2 | 4-Me-Ph | |
Ⅸ-41 | Cl | SO2CH3 | H | C2H5 | H | SO2 | 4-Me-Ph | |
Ⅸ-42 | Cl | SO2CH3 | H | iPr | H | SO2 | 4-Me-Ph | |
Ⅸ-43 | Cl | SO2CH3 | CH3 | CH3 | H | SO2 | 4-Me-Ph | |
Ⅸ-44 | Cl | SO2CH3 | H | CH3 | CH3 | CH2 | Ph | |
Ⅸ-45 | Cl | SO2CH3 | H | C2H5 | CH3 | CH2 | Ph | |
Ⅸ-46 | Cl | SO2CH3 | H | iPr | CH3 | CH2 | Ph | |
Ⅸ-47 | Cl | SO2CH3 | CH3 | CH3 | CH3 | CH2 | Ph | |
Ⅸ-48 | Cl | SO2CH3 | H | tBu | H | CH2CO | Ph | |
Ⅸ-49 | Cl | SO2CH3 | H | tBu | CH3 | CH2CO | Ph | |
Ⅸ-50 | Cl | SO2CH3 | CH3 | tBu | CH3 | CH2CO | Ph | |
Ⅸ-51 | Cl | SO2CH3 | H | CH3 | H | CH2CO | Ph | |
Ⅸ-52 | Cl | SO2CH3 | H | C2H5 | H | CH2CO | Ph | |
Ⅸ-53 | Cl | SO2CH3 | H | iPr | H | CH2CO | Ph | |
Ⅸ-54 | Cl | SO2CH3 | CH3 | CH3 | H | CH2 | Ph | |
Ⅸ-55 | Cl | SO2CH3 | H | CH3 | CH3 | CH2 | Ph | |
Ⅸ-56 | Cl | SO2CH3 | H | C2H5 | CH3 | CH2 | Ph | |
Ⅸ-57 | Cl | SO2CH3 | H | iPr | CH3 | CH2 | Ph | |
Ⅸ-58 | Cl | SO2CH3 | CH3 | CH3 | CH3 | SO2 | 4-Me-Ph | |
Ⅸ-59 | Cl | SO2CH3 | H | tBu | H | SO2 | 4-Me-Ph | |
Ⅸ-60 | Cl | SO2CH3 | H | tBu | CH3 | SO2 | 4-Me-Ph | |
Ⅸ-61 | Cl | SO2CH3 | CH3 | tBu | CH3 | SO2 | 4-Me-Ph |
表10
NMR-No.(Compound No.) | 1H-NMR(CDCl3,δppm) |
NMR-1(1-14) | 1.48(3H,t),2.41(3H,s),2.56(3H,S),4.15(2H,q),6.28(1H,s),7.34(1H,d),7.38(2H,d),7.44(1H,d),7.63(1H,s),7.83(2H,d) |
NMR-2(1-17) | 2.42(3H,s),3.53(3H,s),5.57(2H,s),6.34(1H,s),7.34(1H,s),7.31-7.45(6H,m),7.51(1H,d) |
NMR-3(1-18) | 1.23(3H,t),2.43(3H,s),3.90(2H,q),5.58(2H,s),6.34(1H,s),7.23-7.58(8H,m) |
NMR-4(1-20) | 2.11(3H,s),2.39(3H,s),3.41(3H,s),5.02(2H,s),6.23(1H,s),7.11-7.51(7H,m) |
NMR-5(1-21) | 2.39(3H,s),3.90(3H,s),6.14(2H,s),6.29(1H,s),7.26(1H,s),7.32-7.65(6H,m),7.88(1H,m) |
NMR-6(1-49) | 1.55(9H,s),2.41(3H,s),5.53(2H,s),6.31(1H,s),7.28(1H,s),7.35-7.55(7H,m) |
NMR-7(1-116) | 1.32(3H,t),2.45(3H,s),3.09(3H,s),3.99(2H,dd),5.70(2H,s),6.50(1H,s),7.31(1H,s),7.57(2H,d),7.67(4H,m),8.26(2H,d) |
NMR-8(1-117) | 2.06(3H,s),2.42(3H,s),3.01(3H,s),5.25(2H,s),6.28(1H,s),7.32-7.51(4H,m),8.25(2H,d) |
NMR-9(1-118) | 1.24(3H,t),2.43(3H,s),3.90(2H,dd),5.90(2H,s),6.34(1H,s),7.30(2H,d),7.37-7.40(3H,m),7.47(2H,d),7.52(2H,d) |
NMR-10(1-119) | 1.19(3H,t),1.79(3H,d),2.43(3H,s),3.86(2H,dd),6.15(1H,dd),6.33(1H,s),7.27-7.36(7H,m),7,49(1H,d) |
NMR-11(1-121) | 1.28(3H,t),2.17(3H,s),2.43(3H,s),2.96(3H,s),3.94(2H,q),5.58(2H,s),6.42(1H,s),7.39(5H,s),7.60(1H,d),8.17(1H,d) |
NMR-12(1-122) | 2.39(3H,s),3.70(3H,s),6.20(1H,s),6.62(2H,d),7.03-7.24(5H,m),7.96(1H,s) |
NMR-13(1-123) | 1.42(3H,t),2.43(3H,s),3.08(3H,s),3.71(3H,s),4.62(2H,dd),6.49(1H,s),7.29(1H,s),7.65(1H,s),8.24(1H,d) |
NMR-14(1-127) | 1.38(6H,d),3.16(1H,m),3.23(3H,s),3.59(3H,s),5.46(2H,s),6.66(1H,s),7.33-7.39(5H,m),7.57(1H,s),7.99-8.04(1H,s),8.37(1H,s) |
NMR-15(1-129) | 2.41(3H,s),3.52(3H,s),3.58(3H,s),5.51(2H,s),6.35(1H,s),7.31(1H,d),7.36(5H,s),7.40(1H,d),7.44(1H,s) |
表10(续)
NMR-No.(Compound No.) | 1H-NMR(CDCl3,δppm) |
NMR-16(1-131) | 2.43(3H,s),3.07(3H,s),3.50(3H,s),3.81(3H,s),5.52(2H,s),6.48(1H,s),6.87(2H,d),7.28(3H,m),7.65(1H,d),8.24(1H,d) |
NMR-17(1-134) | 2.19(3H,s),2.41(3H,s),3.56(3H,s),5.54(2H,s),6.25(1H,s),7.32(1H,s),7.35(1H,d),7.37(5H,s),7.40(1H,d) |
NMR-18(1-137) | 1.22(3H,m),2.41(3H,s),3.12(3H,s),3.60(3H,s),3.90(2H,m),5.56(2H,s),6.48(1H,s),7.38(6H,m),7.62(1H,m),8.05(1H,m) |
NMR-19(1-138) | 2.42(3H,s),3.12(3H,s),3.54(3H,s),3.59(3H,s),5.56(2H,s),6.46(1H,s),7.39(6H,m),.7.62(1H,m),8.05(1H,m) |
NMR-20(1-143) | 2.30(3H,s),2.38(3H,s),3.50(3H,s),5.49(2H,s),6.30(1H,s),7.10-7.50(7H,m) |
NMR-21(1-144) | 2.32(3H,s),2.41(3H,s),3.06(3H,s),3.52(3H,s),5.52(2H,s),6.48(1H,s),7.10-7.30(5H,m).7.63(1H,d),8.21(1H,d) |
NMR-22(1-145) | 2.34(3H,s),2.43(3H,s),3.50(3H,s),5.52(2H,s),6.32(1H,s),7.16(2H,d),7.26(2H,d),7.32(1H,s),7.39(1H,d),7.50(1H,d) |
NMR-23(1-147) | 0.95-1.36(5H,m),1.67-1.90(6H,m),2.41(3H,s),3.69(3H,s),4.25(2H,d),6.31(1H,s),7.35(1H,s),7.45(1H,m),7.50(1H,m) |
NMR-24(1-148) | 1.34(6H,d),2.39(3H,s),3.67(3H,s),5.20(1H,M),6.10(1H,s),7.33(1H,s),7.37-7.50(2H,q) |
NMR-25(1-149) | 0.96-1.37(5H,m),1.68-1.87(6H,m),2.43(3H,s),3.08(3H,s),3.71(3H,s),4.30(2H,d),6.48(1H,s),7.30(1H,s),7.65(1H,m)8.22(1H,m) |
NMR-26(1-152) | 2.44(3H,s),2.87(3H,s),3.77(3H,s),6.36(1H,s),7.53(2H,d),7.61(1H,d),7.86(1H,s),7.96(2H,d),8.08(1H,d) |
NMR-27(11-16) | 2.34(3H,s),3.53(3H,s),3.61(3H,s),5.57(2H,s),6.08(1H,s),7.29(1H,d),7.38(5H,s),7.41(1H,s),7.52(1H,d) |
NMR-28(Ⅲ-6) | 1.21(3H,t),3.88(2H,q),5.57(2H,s),7.35(8H,m),7.50(1H,d),8.05(1H,d) |
(制备实施例)
下面,参阅3-苯甲酰基-5-羟基吡唑(它是本发明化合物的原料化合物)的制备实施例。3-苯甲酰基-5-羟基吡唑也是除草活性化合物。
制备实施例1
将0.34克(0.0022摩尔)1-乙基-5-羟基吡唑盐酸盐和0.46克(0.0045摩尔)三乙胺溶解在20毫升二氯甲烷中,在室温下滴加含0.74克(0.0023摩尔)2-氯-4-甲磺酰基-3-(1,3-噁唑-5-基)苯甲酰氯的5毫升二氯甲烷溶液,然后在室温下搅拌1小时。依次用1N盐酸和饱和氯化钠溶液洗涤所得的反应混合物,然后用硫酸镁干燥,减压蒸掉溶剂。将残余物溶解在20毫升乙腈中,向此溶液中加入0.23克(0.0022摩尔)三乙胺和0.1克(0.0011摩尔)丙酮合氰化氢,然后在室温下搅拌过夜。接着减压蒸去溶剂,将残余物溶解在乙酸乙酯中,依次用1N盐酸和饱和氯化钠溶液洗涤,然后用硫酸镁干燥,减压蒸掉溶剂。用硅胶柱色谱提纯所得的残余物,得到0.10克所需化合物结晶。
制备实施例2
将0.7克(0.0047摩尔)1-乙基-5-羟基吡唑盐酸盐和0.95克(0.0094摩尔)三乙胺溶解在20毫升二氯甲烷中,在室温下滴加含1.58克(0.0047摩尔)2-氯-4-甲磺酰基-3-(3-甲基-1,2-异噁唑-5-基)苯甲酰氯的5毫升二氯甲烷溶液,然后在室温下搅拌1小时。依次用1N盐酸和饱和氯化钠溶液洗涤所得的反应混合物,然后用硫酸镁干燥,减压蒸掉溶剂。将残余物溶解在20毫升乙腈中,向此溶液中加入0.47克(0.0047摩尔)三乙胺和0.1克(0.0011摩尔)丙酮合氰化氢,然后在室温下搅拌过夜。接着减压蒸去溶剂,将残余物溶解在乙酸乙酯中,依次用1N盐酸和饱和氯化钠溶液洗涤,然后用硫酸镁干燥,减压蒸掉溶剂。用硅胶柱色谱提纯所得的残余物,得到0.73克所需化合物结晶,熔点为230-233℃。
制备实施例3
制备4-[2-氯-3-(3-甲基-1,2,4-噁二唑-5-基)-4-甲磺酰基]苯甲酰基-1-乙基-5-羟基吡唑(化合物ⅩⅥ-4)
将0.78克(0.0052摩尔)1-乙基-5-羟基吡唑盐酸盐和1.1克(0.0108摩尔)三乙胺溶解在20毫升二氯甲烷中,在室温下滴加含1.74克(0.0052摩尔)2-氯-4-甲磺酰基-3-(5-甲基-1,2,4-异噁唑-3-基)苯甲酰氯的5毫升二氯甲烷溶液,然后在室温下搅拌1小时。依次用1N盐酸和饱和氯化钠溶液洗涤所得的反应混合物,然后用硫酸镁干燥,减压蒸掉溶剂。将残余物溶解在20毫升乙腈中,向此溶液中加入0.52克(0.0052摩尔)三乙胺和0.1克(0.0011摩尔)丙酮合氰化氢,然后在室温下搅拌过夜。接着减压蒸去溶剂,将残余物溶解在乙酸乙酯中,依次用1N盐酸和饱和氯化钠溶液洗涤,然后用硫酸镁干燥,减压蒸掉溶剂。用硅胶柱色谱提纯所得的残余物,得到0.94克所需化合物结晶,熔点为211-215℃。
制备实施例4
将0.61克(0.0041摩尔)1-乙基-5-羟基吡唑盐酸盐和0.83克(0.0082摩尔)三乙胺溶解在20毫升二氯甲烷中,在室温下滴加含1.37克(0.0041摩尔)2-氯-4-甲磺酰基-3-(5-甲基-1,3,4-噁二唑-2-基)苯甲酰氯的5毫升二氯甲烷溶液,然后在室温下搅拌1小时。依次用1N盐酸和饱和氯化钠溶液洗涤所得的反应混合物,然后用硫酸镁干燥,减压蒸掉溶剂。将残余物溶解在20毫升乙腈中,向此溶液中加入0.41克(0.0041摩尔)三乙胺和0.1克(0.0011摩尔)丙酮合氰化氢,然后在室温下搅拌过夜。接着减压蒸去溶剂,将残余物溶解在乙酸乙酯中,依次用1N盐酸和饱和氯化钠溶液洗涤,然后用硫酸镁干燥,减压蒸掉溶剂。用硅胶柱色谱提纯所得的残余物,得到0.66克所需化合物结晶,熔点为187-190℃。
制备实施例5
将0.65克(0.0043摩尔)1-乙基-5-羟基吡唑盐酸盐和0.9克(0.0089摩尔)三乙胺溶解在20毫升二氯甲烷中,在室温下滴加含1.39克(0.0043摩尔)2-氯-3-(1,2-异噁唑-3-基)-4-甲磺酰基苯甲酰氯的5毫升二氯甲烷溶液,然后在室温下搅拌1小时。依次用1N盐酸和饱和氯化钠溶液洗涤所得的反应混合物,然后用硫酸镁干燥,减压蒸掉溶剂。将残余物溶解在20毫升乙腈中,向此溶液中加入0.44克(0.0043摩尔)三乙胺和0.1克(0.0011摩尔)丙酮合氰化氢,然后在室温下搅拌过夜。接着减压蒸去溶剂,将残余物溶解在乙酸乙酯中,依次用1N盐酸和饱和氯化钠溶液洗涤,然后用硫酸镁干燥,减压蒸掉溶剂。用硅胶柱色谱提纯所得的残余物,得到0.34克所需化合物结晶,熔点为95-97℃。
制备实施例6
将0.47克(0.0031摩尔)1-乙基-5-羟基吡唑盐酸盐和0.63克(0.0062摩尔)三乙胺溶解在20毫升二氯甲烷中,在室温下滴加含1.05克(0.0031摩尔)2-氯-4-甲磺酰基-3-(5-甲基-1,2-异噁唑-3-基)苯甲酰氯的5毫升二氯甲烷溶液,然后在室温下搅拌1小时。依次用1N盐酸和饱和氯化钠溶液洗涤所得的反应混合物,然后用硫酸镁干燥,减压蒸掉溶剂。将残余物溶解在20毫升乙腈中,向此溶液中加入0.31克(0.0031摩尔)三乙胺和0.1克(0.0011摩尔)丙酮合氰化氢,然后在室温下搅拌过夜。接着减压蒸去溶剂,将残余物溶解在乙酸乙酯中,依次用1N盐酸和饱和氯化钠溶液洗涤,然后用硫酸镁干燥,减压蒸掉溶剂。用硅胶柱色谱提纯所得的残余物,得到0.35克所需化合物结晶,熔点为242-245℃。
制备实施例7
在含0.43克5-羟基-1-甲基吡唑盐酸盐的15毫升二氯甲烷中加入0.64克三乙胺,在室温下加入按常规方法由1.00克2-氯-4-甲磺酰基-3-(4-甲基-1,3-噁唑-5-基)苯甲酰酸和亚磺酰氯合成的2-氯-4-甲磺酰基-3-(4-甲基-1,3-异噁唑-5-基)苯甲酰氯,然后在室温下搅拌1小时。依次用1N盐酸和饱和氯化钠溶液洗涤所得的反应混合物,然后用硫酸镁干燥,减压蒸掉溶剂。将残余物溶解在10毫升乙腈中,向此溶液中加入0.24克三乙胺和0.10克丙酮合氰化氢,然后在室温下搅拌过夜。接着减压蒸去溶剂,将残余物溶解在乙酸乙酯中,依次用1N盐酸和饱和氯化钠溶液洗涤,然后用硫酸镁干燥,减压蒸掉溶剂。用硅胶薄层色谱提纯所得的残余物,得到0.30克所需化合物粉末。
制备实施例8
室温下,在15毫升含0.54克1-乙基-5-羟基吡唑盐酸盐的二氯甲烷中加入0.74克三乙胺,并加入按常规方式由1.00克2,4-二氯-3-(4-甲基-1,3-噁唑-5-基)苯甲酸和亚硫酰(二)氯合成的2,4-二氯-3-(4-甲基-1,3-噁唑-5-基)苯甲酰氯,随后在室温下搅拌1.5小时。产生的反应混合物用1N盐酸洗涤,再用饱和氯化钠溶液洗涤,然后用无水硫酸镁干燥,减压下蒸馏除去溶剂。将残留物溶解于10毫升乙腈,在该溶液中加入0.37克三乙胺和0.10克丙酮合氰化氢,随后在室温下搅拌过夜。之后,减压蒸馏除去溶剂,然后将残留物溶解于乙酸乙酯中,用1N盐酸洗涤,再用饱和氯化钠溶液洗涤,然后用无水硫酸镁干燥,之后蒸馏除去溶剂。制得的残留物通过硅胶薄层色谱提纯,获得0.44克所需化合物,该化合物为晶体状,其m.p.为156-158℃。
制备实施例9
将1.27克5-羟基-1-甲基吡唑盐酸盐和1.92克三乙胺溶解于20毫升二氯甲烷,并在室温下在该溶液中滴加10毫升含2.70克2,4-二氯-3-(3-甲基-1,2-异噁唑-5-基)苯甲酰氯的二氯甲烷溶液,随后在室温下搅拌1小时。产生的反应混合物用1N盐酸洗涤,再用饱和氯化钠溶液洗涤,然后用无水硫酸镁干燥,减压下蒸馏除去溶剂。将残留物溶解于20毫升乙腈,在该溶液中加入1.92克三乙胺和0.21克丙酮合氰化氢,随后在室温下搅拌5小时。之后,减压蒸馏除去溶剂,然后将残留物溶解于苯中,然后用碳酸钠水溶液萃取。随后,在产生的水层中加入100毫升氯仿,并用浓盐酸进行酸沉淀。产生的有机层用水洗涤,再用饱和氯化钠溶液洗涤,然后用无水硫酸镁干燥,蒸馏除去溶剂。制得的残留物通过硅胶柱色谱提纯,获得1.40克所需化合物,该化合物为晶体状,其m.p.为219-224℃。
制备实施例10
将6.31克氢氯化5-羟基-1-甲基吡唑盐酸盐和14.15克2-氯-3-(3-甲基-1,2-异噁唑-5-基)-4-甲磺酰基苯甲酰氯溶解于65毫升氯仿,在用冰冷却下滴加9.54克三乙胺,随后在室温下搅拌过夜。产生的反应混合物用稀盐酸、饱和碳酸氢钠溶液洗涤,再用饱和氯化钠溶液洗涤,然后用无水硫酸镁干燥,减压下蒸馏除去溶剂,获得11.65克残留物。将该残留物溶解于70毫升乙腈,在该溶液中加入4.00克三乙胺和0.85克丙酮合氰化氢,随后在室温下搅拌1小时。之后,减压蒸馏除去溶剂,然后将残留物溶解于乙酸乙酯中,用1N乙酸洗涤,再用饱和氯化钠溶液洗涤,然后用无水硫酸镁干燥,蒸馏除去溶剂。制得的残留物通过硅胶柱色谱提纯,获得5.00克所需化合物,该化合物为晶体状,其m.p.为106-108℃(从甲苯中结晶);m.p.为239-241℃(从甲醇中结晶)。
制备实施例11
将4.46克1-乙基-5-羟基吡唑盐酸盐和8.24克2,4-二氯-3-(3-甲基-1,2-异噁唑-5-基)苯甲酰氯溶解于40毫升氯仿中,在冰冷却下滴加6.36克三乙胺,随后在室温下搅拌25分钟。在产生的反应混合物中加入3.64克三乙胺和0.51克丙酮合氰化氢,之后在室温下搅拌过夜。在该反应化合物中再加入水,并用10%氢氧化钠水溶液碱化。
在产生的钠盐水溶液中,加入稀盐酸调节其pH值至4,然后用乙酸乙酯进行萃取。产生的有机层用水洗涤,再用饱和氯化钠溶液洗涤,然后用无水硫酸镁干燥,减压蒸馏除去溶剂。之后,在产生的残留物中加入甲醇,然后通过过滤收集沉淀的晶体,获得4.82克所需化合物,其m.p.为174-178℃。
制备实施例12
室温下,在15毫升含0.87克1-叔丁基-5-羟基吡唑盐酸盐的二氯甲烷中加入0.7克三乙胺,并滴加10毫升含2-氯-3-(3-甲基-1,2-异噁唑-5-基)-4-甲磺酰基苯甲酰氯(按常规方式由1.7克2-氯-3-(3-甲基-1,2-异噁唑-5-基)-4-甲磺酰基苯甲酸和亚硫酰(二)氯合成)的二氯甲烷,随后在室温下搅拌1小时。产生的反应混合物用1N盐酸、1N氢氧化钠水溶液洗涤,再用饱和氯化钠溶液洗涤,然后用无水硫酸镁干燥,减压下蒸馏除去溶剂。将残留物溶解于10毫升乙腈,在该溶液中加入0.6克三乙胺和0.2克丙酮合氰化氢,随后在室温下搅拌1.5小时。之后,减压蒸馏除去溶剂,然后将残留物溶解于苯中,再用碳酸氢钠水溶液萃取。之后在产生的水层中加入氯仿,用浓盐酸进行酸沉淀。产生的有机层用水洗涤,再用饱和氯化钠溶液洗涤。然后用无水硫酸镁干燥,减压蒸馏除去溶剂。之后在制得的残留物中加入甲醇,通过过滤收集沉淀的晶体,获得1.1克所需化合物,其m.p.为215-217℃。
制备实施例13
室温下,在20毫升含1.06克1,3-二甲基-5-羟基吡唑盐酸盐的二氯甲烷中加入0.96克三乙胺,并滴加2.51克2,4-二氯-3-(3-甲基-1,2-异噁唑-5-基)苯甲酰氯,随后在室温下搅拌1小时。产生的反应混合物用1N盐酸、1N氢氧化钠水溶液洗涤,再用饱和氯化钠溶液洗涤,然后用无水硫酸镁干燥,减压下蒸馏除去溶剂。将残留物溶解于20毫升乙腈,在该溶液中加入0.96克三乙胺和0.14克丙酮合氰化氢,随后在室温下搅拌过夜。之后,减压蒸馏除去溶剂,然后将残留物溶解于苯中,再用碳酸钠水溶液萃取。之后在产生的水层中加入氯仿,用浓盐酸进行酸沉淀。产生的有机层用水洗涤,再用饱和氯化钠溶液洗涤。然后用无水硫酸镁干燥,减压蒸馏除去溶剂。制得的残留物经硅胶柱色谱提纯,加入甲醇,然后通过过滤收集沉淀的晶体,获得0.80克所需化合物,其m.p.为140-141℃。
制备实施例14
将1.14克1-乙基-5-羟基吡唑盐酸盐溶解于20毫升二氯甲烷,然后加入1.48克三乙胺。之后,在室温下滴加10毫升含2.3克2,4-二氯-3-(1,2-异噁唑-3-基)苯甲酰氯的二氯甲烷,随后在室温下搅拌1小时。产生的反应混合物用1N盐酸洗涤,再用饱和氯化钠溶液洗涤,然后用无水硫酸镁干燥,减压下蒸馏除去溶剂。将残留物溶解于20毫升乙腈,在该溶液中加入0.71克三乙胺和0.06克丙酮合氰化氢,随后在室温下搅拌过夜。之后,减压蒸馏除去溶剂,然后将残留物溶解于苯中,再用碳酸钠水溶液萃取。之后在产生的水层中加入氯仿,用浓盐酸进行酸沉淀。产生的有机层用水洗涤,再用饱和氯化钠溶液洗涤。然后用无水硫酸镁干燥,减压蒸馏除去溶剂。之后在制得的残留物中加入甲醇,通过过滤收集沉淀的晶体,获得0.5克所需化合物,其m.p.为177-179℃。
制备实施例15
将0.50克5-羟基-1-甲基吡唑盐酸盐溶解于10毫升二氯甲烷,加入0.72克三乙胺。之后,在室温下滴加5毫升含2,4-二氯-3-(1,3-二甲基吡唑-5-基)苯甲酰氯(由0.80克2,4-二氯-3-(1,3-二甲基吡唑-5-基)苯甲酸和2.0克亚硫酰(二)氯合成)二氯甲烷,随后在室温下搅拌30分钟。产生的反应混合物用1N盐酸、饱和碳酸氢钠水溶液洗涤,再用饱和氯化钠溶液洗涤,然后用无水硫酸镁干燥,减压下蒸馏除去溶剂。将残留物溶解于10毫升乙腈,在该溶液中加入0.3克三乙胺和0.04克丙酮合氰化氢,随后在室温下搅拌过夜。之后,减压蒸馏除去溶剂,然后将残留物溶解于苯中,再用50毫升饱和碳酸氢钠水溶液萃取两次。之后在产生的水层中加入100毫升氯仿,用浓盐酸进行酸沉淀。产生的有机层用水洗涤,再用饱和氯化钠溶液洗涤。然后用无水硫酸镁干燥,减压蒸馏除去溶剂。之后通过硅胶柱色谱提纯制得的残留物,获得0.40克所需化合物,其m.p.为126-129℃。
制备实施例16
将0.40克5-羟基-1-甲基吡唑盐酸盐溶解于25毫升二氯甲烷,加入0.60克三乙胺。之后,在室温下滴加入6毫升含0.85克2-氯-3-(1,3-二甲基吡唑-5-基)-4-甲磺酰基苯甲酰氯的二氯甲烷溶液,随后在室温下搅拌30分钟。产生的反应混合物用1N盐酸、饱和碳酸氢钠水溶液洗涤,再用饱和氯化钠溶液洗涤,然后用无水硫酸镁干燥,减压下蒸馏除去溶剂。将残留物溶解于10毫升乙腈,在该溶液中加入0.28克三乙胺和0.03克丙酮合氰化氢,随后在室温下搅拌过夜。之后,减压蒸馏除去溶剂,然后将残留物溶解于苯中,再用40毫升和20毫升饱和碳酸氢钠水溶液萃取两次。之后在产生的水层中加入100毫升氯仿,用浓盐酸进行酸沉淀。产生的有机层用水洗涤,再用饱和氯化钠溶液洗涤,然后用无水硫酸镁干燥,减压蒸馏除去溶剂。之后通过硅胶柱色谱提纯制得的残留物,获得0.30克所需化合物,该化合物为晶体状,其m.p.为232-235℃。
制备实施例17
将0.36克1-乙基羟基吡唑盐酸盐溶解于25毫升二氯甲烷,加入0.50克三乙胺。之后,在室温下滴加5毫升含2,4-二氯-3-(1,5-二甲基吡唑-3-基)苯甲酰氯(由0.60克2,4-二氯-3-(1,5-二甲基吡唑-3-基)苯甲酸和亚磺酰(二)氯合成)的二氯甲烷溶液,随后在室温下搅拌30分钟。产生的反应混合物用1N盐酸、饱和碳酸氢钠水溶液洗涤,再用饱和氯化钠溶液洗涤,然后用无水硫酸镁干燥,减压下蒸馏除去溶剂。将残留物溶解于5毫升乙腈,在该溶液中加入0.22克三乙胺和0.02克丙酮合氰化氢,随后在室温下搅拌过夜。之后,减压蒸馏除去溶剂,然后将残留物溶解于苯中,再用60毫升和40毫升饱和碳酸氢钠水溶液萃取两次。之后在产生的水层中加入100毫升氯仿,用浓盐酸进行酸沉淀。产生的有机层用水洗涤,再用饱和氯化钠溶液洗涤,然后用无水硫酸镁干燥,减压蒸馏除去溶剂。之后通过硅胶柱色谱提纯制得的残留物,获得0.25克所需化合物,其m.p.为77-79℃。
制备实施例18
在15毫升含0.32克1-乙基-5-羟基吡唑盐酸盐的二氯甲烷中加入0.45克三乙胺,并在室温下加入按常规方式由0.69克2-氯-4-甲磺酰基-3-(5-甲基-1,2-异噁唑-4-基)苯甲酸和亚磺酰(二)氯合成的2-氯-4-甲磺酰基-3-(5-甲基-1,2-异噁唑-4-基)苯甲酰氯,随后在室温下搅拌两昼夜。产生的反应混合物用1N盐酸洗涤,再用饱和氯化钠溶液洗涤,然后用无水硫酸镁干燥,减压下蒸馏除去溶剂。将残留物溶解于10毫升乙腈,在该溶液中加入0.11克三乙胺和0.03克丙酮合氰化氢,随后在室温下搅拌过夜。之后,减压蒸馏除去溶剂,然后将残留物溶解于乙酸乙酯,用1N盐酸洗涤,再用饱和氯化钠溶液洗涤,然后用无水硫酸镁干燥,蒸馏除去溶剂。
通过硅胶薄层色谱提纯制得的残留物,获得0.06克粉末状所需化合物。
制备实施例19
在10毫升含0.21克1-乙基-5-羟基吡唑盐酸盐的二氯甲烷中加入0.29克三乙胺,并在室温下加入按常规方式由0.39克2,4-二氯-3-(4-甲基-1,2-异噁唑-5-基)苯甲酸和亚磺酰(二)氯合成的2,4-二氯-3-(4-甲基-1,2-异噁唑-5-基)苯甲酰氯,随后在室温下搅拌过夜。产生的反应混合物用1N盐酸洗涤,再用饱和氯化钠溶液洗涤,然后用无水硫酸镁干燥,减压下蒸馏除去溶剂。将残留物溶解于10毫升乙腈,在该溶液中加入0.14克三乙胺和0.10克丙酮合氰化氢,随后在室温下搅拌过夜。之后,减压蒸馏除去溶剂,然后将残留物溶解于乙酸乙酯,用1N盐酸洗涤,再用饱和氯化钠溶液洗涤,然后用无水硫酸镁干燥,蒸馏除去溶剂。通过硅胶薄层色谱提纯制得的残留物,获得0.14克粉末状所需化合物。
制备实施例20
将0.55克5-羟基-1-甲基吡唑溶盐酸盐解于10毫升二氯甲烷中,加入0.80克三乙胺。之后,在室温下滴加10毫升含2,4-二氯-3-(1,3-二甲基-1,2,4-三唑-5-基)苯甲酰氯(按常规方式由0.90克2,4-二氯-3-(1,3-二甲基-1,2,4-三唑-5-基)苯甲酸和亚磺酰(二)氯合成)的二氯甲烷溶液,随后在室温下搅拌2小时。产生的反应混合物用50毫升5%碳酸钠水溶液萃取两次。在产生的水层中加入100毫升氯仿,然后用浓盐酸进行酸沉淀。产生的有机层用水洗涤,再用饱和氯化钠溶液洗涤,然后用无水硫酸镁干燥,减压下蒸馏除去溶剂。之后,加入甲醇,通过过滤收集残留物、沉淀晶体,获得0.70克所需化合物,其m.p.为235-240℃。
用于按上述制备的本发明化合物的原料化合物的例子列于表11-20,而1H-NMR谱数据列于表21。
表11
No. | R1 | R2 | R4 | R5 | R7 | R8 | 物理值熔点 |
Ⅺ-1 | Cl | Cl | H | CH3 | H | H | 粉末(NMR-29) |
Ⅺ-2 | Cl | SO2CH3 | H | CH3 | H | H | [243-245℃] |
Ⅺ-3 | Cl | Cl | H | C2H5 | H | H | 粉末(NMR-30) |
Ⅺ-4 | Cl | SO2CH3 | H | C2H5 | H | H | 粉末(NMR-31) |
Ⅺ-5 | Cl | Cl | H | C3H7 i | H | H | |
Ⅺ-6 | Cl | SO2CH3 | H | C3H7 i | H | H | |
Ⅺ-7 | Cl | Cl | H | C4H9 t | H | H | |
Ⅺ-8 | Cl | SO2CH3 | H | C4H9 t | H | H | |
Ⅺ-9 | Cl | Cl | CH3 | CH3 | H | H | |
Ⅺ-10 | Cl | SO2CH3 | CH3 | CH3 | H | H | |
Ⅺ-11 | Cl | Cl | CH3 | CH3 | H | H | |
Ⅺ-12 | Cl | SO2CH3 | H | CH3 | CH3 | H | 粉末(NMR-32) |
Ⅺ-13 | Cl | Cl | H | C2H5 | CH3 | H | [156-157℃] |
Ⅺ-14 | Cl | SO2CH3 | H | C2H5 | CH3 | H | [193-194℃] |
Ⅺ-15 | Cl | Cl | CH3 | CH3 | CH3 | H | |
Ⅺ-16 | Cl | SO2CH3 | CH3 | CH3 | CH3 | H | 粉末(NMR-33) |
表12
No. | R1 | R2 | R4 | R5 | R7 | R8 | 物理值熔点 |
Ⅻ-1 | Cl | Cl | H | CH3 | CH3 | H | |
Ⅻ-2 | Cl | SO2CH3 | H | CH3 | CH3 | H | |
Ⅻ-3 | Cl | Cl | H | C2H5 | CH3 | H | |
Ⅻ-4 | Cl | SO2CH3 | H | C2H5 | CH3 | H | |
Ⅻ-5 | Cl | Cl | H | C3H7 i | CH3 | H | |
Ⅻ-6 | Cl | SO2CH3 | H | C3H7 i | CH3 | H | |
Ⅻ-7 | Cl | Cl | H | C4H9 t | CH3 | H | |
Ⅻ-8 | Cl | SO2CH3 | H | C4H9 t | CH3 | H | |
Ⅻ-9 | Cl | Cl | CH3 | CH3 | CH3 | H | |
Ⅻ-10 | Cl | SO2CH3 | CH3 | CH3 | CH3 | H |
表13
No. | R1 | R2 | R4 | R5 | R7 | R8 | 物理值熔点℃ |
ⅩⅢ-1 | Cl | Cl | H | H | H | H | |
ⅩⅢ-2 | Cl | SO2CH3 | H | H | CH3 | H | [140-145] |
ⅩⅢ-3 | Cl | Cl | H | CH3 | H | H | |
ⅩⅢ-4 | Cl | SO2CH3 | H | CH3 | H | H | |
ⅩⅢ-5 | Cl | Cl | H | CH3 | CH3 | H | [219-224] |
ⅩⅢ-6 | Cl | SO2CH3 | H | CH3 | CH3 | H | [106-108] |
ⅩⅢ-7 | Cl | Cl | H | C2H5 | H | H | [125-129] |
ⅩⅢ-8 | Cl | SO2CH3 | H | C2H5 | H | H | 粉末(NMR-34) |
ⅩⅢ-9 | Cl | Cl | H | C2H5 | CH3 | H | [174-178] |
ⅩⅢ-10 | Cl | SO2CH3 | H | C2H5 | CH3 | H | [230-233] |
ⅩⅢ-11 | Cl | Cl | H | C3H7 i | CH3 | H | |
ⅩⅢ-12 | Cl | SO2CH3 | H | C3H7 i | CH3 | H | [216-219] |
ⅩⅢ-13 | Cl | Cl | H | C4H9 t | CH3 | H | |
ⅩⅢ-14 | Cl | SO2CH3 | H | C4H9 t | CH3 | H | [215-217] |
表13(续)
No. | R1 | R2 | R4 | R5 | R7 | R8 | 物理值熔点℃ |
ⅩⅢ-15 | Cl | Cl | CH3 | CH3 | CH3 | H | [140-141] |
ⅩⅢ-16 | Cl | SO2CH3 | CH3 | CH3 | CH3 | H | 粉末(NMR-35) |
ⅩⅢ-17 | Cl | Cl | CH2OCH3 | CH3 | CH3 | H | |
ⅩⅢ-18 | Cl | SO2CH3 | CH2OCH3 | CH3 | CH3 | H | 粉末(NMR-36) |
ⅩⅢ-19 | Cl | Cl | H | CH3 | C2H5 | H | |
ⅩⅢ-20 | Cl | SO2CH3 | H | CH3 | C2H5 | H | 粉末(NMR-37) |
ⅩⅢ-21 | Cl | Cl | H | C2H5 | C2H5 | H | [166-167] |
ⅩⅢ-22 | Cl | SO2CH3 | H | C2H5 | C2H5 | H | 粉末(NMR-38) |
ⅩⅢ-23 | Cl | Cl | CH3 | CH3 | C2H5 | H | 粉末(NMR-39) |
ⅩⅢ-24 | Cl | SO2CH3 | CH3 | CH3 | C2H5 | H | 粉末(NMR-40) |
ⅩⅢ-25 | Cl | Cl | CH3 | CH3 | iPr | H | |
ⅩⅢ-26 | Cl | SO2CH3 | CH3 | CH3 | iPr | H | |
ⅩⅢ-27 | Cl | Cl | H | CH3 | H | CH3 | |
ⅩⅢ-28 | Cl | SO2CH3 | H | CH3 | H | CH3 | |
ⅩⅢ-29 | Cl | Cl | H | C2H5 | H | CH3 | 粉末(NMR-41) |
ⅩⅢ-30 | Cl | SO2CH3 | H | C2H5 | H | CH3 | |
ⅩⅢ-31 | Cl | Cl | CH3 | CH3 | H | CH3 | |
ⅩⅢ-32 | Cl | SO2CH3 | CH3 | CH3 | H | CH3 | |
ⅩⅢ-33 | Cl | Cl | CH3 | C2H5 | H | CH3 | |
ⅩⅢ-34 | Cl | SO2CH3 | CH3 | C2H5 | H | CH3 |
表13(续)
No. | R1 | R2 | R4 | R5 | R7 | R8 | 物理值熔点℃ |
ⅩⅢ-35 | Cl | Cl | CH3 | CH3 | H | C2H5 | |
ⅩⅢ-36 | Cl | SO2CH3 | CH3 | CH3 | H | C2H5 | |
ⅩⅢ-37 | Cl | Cl | H | CH3 | CH3 | CH3 | 粉末(NMR-42) |
ⅩⅢ-38 | Cl | SO2CH3 | H | CH3 | CH3 | CH3 | |
ⅩⅢ-39 | Cl | Cl | H | C2H5 | CH3 | CH3 | 粉末(NMR-43) |
ⅩⅢ-40 | Cl | SO2CH3 | H | C2H5 | CH3 | CH3 | |
ⅩⅢ-41 | Cl | Cl | H | C2H5 | H | C2H5 | |
ⅩⅢ-42 | Cl | SO2CH3 | H | C2H5 | H | C2H5 | |
ⅩⅢ-43 | Cl | Cl | CH3 | C2H5 | H | C2H5 | |
ⅩⅢ-44 | Cl | SO2CH3 | CH3 | C2H5 | H | C2H5 | |
ⅩⅢ-45 | Cl | Cl | CH3 | CH3 | CH3 | CH3 | 粉末(NMR-44) |
ⅩⅢ-46 | Cl | SO2CH3 | CH3 | CH3 | CH3 | CH3 | |
ⅩⅢ-47 | Cl | Cl | H | iPr | CH3 | CH3 | |
ⅩⅢ-48 | Cl | SO2CH3 | H | iPr | CH3 | CH3 | |
ⅩⅢ-49 | Cl | Cl | CH3 | iPr | CH3 | CH3 | |
ⅩⅢ-50 | Cl | SO2CH3 | CH3 | iPr | CH3 | CH3 |
表14
No. | R1 | R2 | R4 | R5 | R7 | 物理值熔点℃ |
ⅩⅣ-1 | Cl | Cl | H | CH3 | CH3 | |
ⅩⅣ-2 | Cl | SO2CH3 | H | CH3 | CH3 | |
ⅩⅣ-3 | Cl | Cl | H | C2H5 | CH3 | |
ⅩⅣ-4 | Cl | SO2CH3 | H | C2H5 | CH3 | [187-190] |
ⅩⅣ-5 | Cl | Cl | H | C3H7 i | CH3 | |
ⅩⅣ-6 | Cl | SO2CH3 | H | C3H7 i | CH3 | |
ⅩⅣ-7 | Cl | Cl | H | C4H9 t | CH3 | |
ⅩⅣ-8 | Cl | SO2CH3 | H | C4H9 t | CH3 | |
ⅩⅣ-9 | Cl | Cl | CH3 | CH3 | CH3 | |
ⅩⅣ-10 | Cl | SO2CH3 | CH3 | CH3 | CH3 |
表15
No. | R1 | R2 | R4 | R5 | R7 | R8 | 物理值(物理性质℃) |
ⅩⅤ-1 | Cl | Cl | H | CH3 | H | H | |
ⅩⅤ-2 | Cl | SO2CH3 | H | CH3 | H | H | |
ⅩⅤ-3 | Cl | Cl | H | CH3 | H | CH3 | |
ⅩⅤ-4 | Cl | SO2CH3 | H | CH3 | H | CH3 | [25-252] |
ⅩⅤ-5 | Cl | Cl | H | C2H5 | H | H | [177-179] |
ⅩⅤ-6 | Cl | SO2CH3 | H | C2H5 | H | H | [95-97] |
ⅩⅤ-7 | Cl | Cl | H | C2H5 | H | CH3 | [223-224] |
ⅩⅤ-8 | Cl | SO2CH3 | H | C2H5 | H | CH3 | [242-245] |
ⅩⅤ-9 | Cl | Cl | CH3 | C3H7 i | H | H | |
ⅩⅤ-10 | Cl | SO2CH3 | CH3 | C3H7 i | H | H | |
ⅩⅤ-11 | Cl | Cl | H | C4H9 t | H | H | |
ⅩⅤ-12 | Cl | SO2CH3 | H | C4H9 t | H | H | |
ⅩⅤ-13 | Cl | Cl | CH3 | CH3 | H | H | |
ⅩⅤ-14 | Cl | SO2CH3 | CH3 | CH3 | H | H | |
ⅩⅤ-15 | Cl | Cl | CH3 | CH3 | H | CH3 | |
ⅩⅤ-16 | Cl | SO2CH3 | CH3 | CH3 | H | CH3 | 粉末(NMR-45) |
表16
No. | R1 | R2 | R4 | R5 | R7 | 物理值(物理性质℃) |
ⅩⅥ-1 | Cl | Cl | H | CH3 | CH3 | |
ⅩⅥ-2 | Cl | SO2CH3 | H | CH3 | CH3 | |
ⅩⅥ-3 | Cl | Cl | H | C2H5 | CH3 | [183-185] |
ⅩⅥ-4 | Cl | SO2CH3 | H | C2H5 | CH3 | [211-215] |
ⅩⅥ-5 | Cl | Cl | H | C3H7 i | CH3 | |
ⅩⅥ-6 | Cl | SO2CH3 | H | C3H7 i | CH3 | |
ⅩⅥ-7 | Cl | Cl | H | C4H8 t | CH3 | |
ⅩⅥ-8 | Cl | SO2CH3 | H | C4H9 t | CH3 | |
ⅩⅥ-9 | Cl | Cl | CH3 | CH3 | CH3 | |
ⅩⅥ-10 | Cl | SO2CH3 | CH3 | CH3 | CH3 |
表17
No. | R1 | R2 | R4 | R5 | R7 | R8 | 物理值(物理性质℃) |
ⅩⅦ-1 | Cl | Cl | H | H | CH3 | CH3 | |
ⅩⅦ-2 | Cl | SO2CH3 | H | H | CH3 | CH3 | |
ⅩⅦ-3 | Cl | Cl | H | CH3 | CH3 | H | |
ⅩⅦ-4 | Cl | SO2CH3 | H | CH3 | CH3 | H | |
ⅩⅦ-5 | Cl | Cl | H | CH3 | H | CH3 | |
ⅩⅦ-6 | Cl | SO2CH3 | H | CH3 | H | CH3 | |
ⅩⅦ-7 | Cl | Cl | H | CH3 | H | CH3 | |
ⅩⅦ-8 | Cl | SO2CH3 | H | CH3 | H | CH3 | |
ⅩⅦ-9 | Cl | Cl | H | C2H5 | H | CH3 | |
ⅩⅦ-10 | Cl | SO2CH3 | H | C2H5 | H | CH3 | |
ⅩⅦ-11 | Cl | Cl | H | CH3 | CH3 | CH3 | [126-129] |
ⅩⅦ-12 | Cl | SO2CH3 | H | CH3 | CH3 | CH3 | [232-235] |
ⅩⅦ-13 | Cl | Cl | H | C2H5 | CH3 | CH3 | [148-150] |
ⅩⅦ-14 | Cl | SO2CH3 | H | C2H5 | CH3 | CH3 | [225-227] |
ⅩⅦ-15 | Cl | Cl | CH3 | CH3 | CH3 | CH3 | |
ⅩⅦ-16 | Cl | SO2CH3 | CH3 | CH3 | CH3 | CH3 |
表17(续)
No. | R1 | R2 | R4 | R5 | R7 | R8 | 物理值(物理性质℃) |
ⅩⅦ-17 | Cl | Cl | H | iPr | CH3 | CH3 | |
ⅩⅦ-18 | Cl | SO2CH3 | H | iPr | CH3 | CH3 | |
ⅩⅦ-19 | Cl | Cl | H | tBu | CH3 | CH3 | |
ⅩⅦ-20 | Cl | SO2CH3 | H | tBu | CH3 | CH3 | |
ⅩⅦ-21 | Cl | Cl | H | C2H5 | C2H5 | CH3 | |
ⅩⅦ-22 | Cl | SO2CH3 | H | C2H5 | C2H5 | CH3 | [162-163] |
ⅩⅦ-23 | Cl | Cl | H | C2H5 | C2H5 | CH3 | |
ⅩⅦ-24 | Cl | SO2CH3 | H | C2H5 | C2H5 | CH3 | |
ⅩⅦ-25 | Cl | Cl | H | C2H5 | iPr | CH3 | |
ⅩⅦ-26 | Cl | SO2CH3 | H | C2H5 | iPr | CH3 |
表18
No. | R1 | R2 | R4 | R5 | R7 | R8 | 物理值(物理性质℃) |
ⅩⅧ-l | Cl | Cl | H | CH3 | CH3 | CH3 | |
ⅩⅧ-2 | Cl | SO2CH3 | H | CH3 | CH3 | CH3 | |
ⅩⅧ-3 | Cl | Cl | H | C2H5 | CH3 | CH3 | [77-79] |
ⅩⅧ-4 | Cl | SO2CH3 | H | C2H5 | CH3 | CH3 | |
ⅩⅧ-5 | Cl | Cl | H | C2H5 | CH3 | CH3 | |
ⅩⅧ-6 | Cl | SO2CH3 | H | C2H5 | CH3 | CH3 | |
ⅩⅧ-7 | Cl | Cl | H | iPr | CH3 | CH3 | |
ⅩⅧ-8 | Cl | SO2CH3 | H | iPr | CH3 | CH3 | |
ⅩⅧ-9 | Cl | Cl | CH3 | CH3 | CH3 | CH3 | |
ⅩⅧ-10 | Cl | SO2CH3 | CH3 | CH3 | CH3 | CH3 |
表19
No. | R1 | R2 | R4 | R5 | R7 | R8 | 物理值(物理性质℃) |
ⅩⅨ-1 | Cl | Cl | H | CH3 | CH3 | H | |
ⅩⅨ-2 | Cl | SO2CH3 | H | CH3 | CH3 | H | |
ⅩⅨ-3 | Cl | Cl | H | C2H5 | CH3 | H | |
ⅩⅨ-4 | Cl | SO2CH3 | H | C2H5 | CH3 | H | 粉末(NMR-46) |
ⅩⅨ-5 | Cl | Cl | CH3 | CH3 | CH3 | H | |
ⅩⅨ-6 | Cl | SO2CH3 | CH3 | CH3 | CH3 | H | |
ⅩⅨ-7 | Cl | Cl | H | CH3 | H | CH3 | |
ⅩⅨ-8 | Cl | SO2CH3 | H | CH3 | H | CH3 | |
ⅩⅨ-9 | Cl | Cl | H | CH3 | CH3 | CH3 | |
ⅩⅨ-10 | Cl | SO2CH3 | H | CH3 | CH3 | CH3 |
表20
No. | R1 | R2 | R4 | R5 | R7 | R8 | 物理值(物理性质℃) |
ⅩⅩ-1 | Cl | Cl | H | CH3 | H | CH3 | |
ⅩⅩ-2 | Cl | SO2CH3 | H | CH3 | H | CH3 | |
ⅩⅩ-3 | Cl | Cl | H | C2H5 | H | CH3 | |
ⅩⅩ-4 | Cl | SO2CH3 | H | C2H5 | H | CH3 | |
ⅩⅩ-5 | Cl | Cl | CH3 | CH3 | H | CH3 | |
ⅩⅩ-6 | Cl | SO2CH3 | CH3 | CH3 | H | CH3 | |
ⅩⅩ-7 | Cl | Cl | CH3 | H | CH3 | CH3 | [235-240] |
ⅩⅩ-8 | Cl | SO2CH3 | CH3 | CH3 | CH3 | CH3 | |
ⅩⅩ-9 | Cl | Cl | H | iPr | CH3 | CH3 | |
ⅩⅩ-10 | Cl | SO2CH3 | H | iPr | CH3 | CH3 |
表21
NMR-No.(Compound No.) | 1H-NMR(CDCl3,δppm) |
NMR-29(Ⅺ-1) | 3.73(3H,s),7.22(1H,bs),7.35(1H,s),7.40(1H,s),7.49(1H,d),7.56(1H,d),8.13(1H,s) |
NMR-30(Ⅺ-3) | 1.46(3H,t),4.07(2H,q),7.34(1H,s),7.40(1H,s),7.48(1H,d),7.55(1H,d),8.09(1H,s),8.25(1H,bs), |
NMR-31(Ⅺ-4) | 1.46(3H,t),3.00(3H,s),4.09(2H,q),6.88(1H,bs),7.36(1H,s),7.43(1H,s),7.74(1H,d),8.15(1H,s),8.28(1H,d) |
NMR-32(Ⅺ-12) | 2.17(3H,s),3.04(3H,s),3.76(3H,s),5.60(1H,bs),7.38(1H,s),7.77(1H,d),8.11(1 H,d),8.28(1H,d) |
NMR-33(Ⅺ-16) | 1.77(3H,S),2.14(3H,s),3.02(3H,s),3.65(3H,s),5.08(1H,bs),7.65(1H,d),8.02(1H,s),8.29(1H,d) |
NMR-34(ⅩⅢ-8) | 1.47(3H,t),3.08(3H,s),4.09(2H,q),6.68(1H,d),7.47(1H,s),7.78(1H,d),8.30(1H,d),8.49(1H,d),8.60(1H,bs) |
NMR-35(ⅩⅢ-16) | 1.79(3H,s),2.45(3H,s),3.10(3H,s),3.66(3H,s),6.00(1H,s),6.70(1H,bs),7.64(1H,d),8.28(1H,d), |
NMR-36(ⅩⅢ-18) | 2.43(3H,s),2.94(3H,s),3.06(3H,s),3.69(3H,s),4.01(2H,s),6.48(1H,s),7.67(1H,d),8.25(1H,d) |
NMR-37(ⅩⅢ-20) | 1.37(3H,t),2.84(2H,q),3.07(3H,s),3.73(3H,s),5.45(1H,bs),7.36(1H,s),7.74(1H,d),8.28(1H,d) |
NMR-38(ⅩⅢ-22) | 1.38(3H,t),1.48(3H,t),2.84(2H,q),3.08(3H,s),4.09(2H,q),6.25(1H,bs),6.53(1H,s),7.37(1H,s),7.M(1H,d),8.27(1H,d) |
NMR-39(ⅩⅢ-23) | 1.35(3H,t),1.82(3H,t),2.82(2H,q),3.63(3H,s),5.20(1H,bs),6.36(1H,s),7.35(1H,d),7.55(1H,d) |
NMR-40(ⅩⅢ-24) | 1.37(3H,t),1.78(3H,t),2.83(2H,q),3.08(3H,s),3.64(3H,s),6.52(1H,s),6.55(1H,bs),7.64(1H,d),8.27(1H,d) |
表21(续)
NMR-No.(Compound No.) | 1H-NMR(CDCl3,δppm) |
NMR-41(ⅩⅢ-29) | 1.45(3H,t),2.00(3H,s),4.07(2H,q),7.41(1H,s),7.57(1H, s),8.30(1H,s),9.00(1H,bs) |
NMR-42(ⅩⅢ-37) | 1.90(3H,s),2.34(3H,s),3.71(3H,s),3.80(1H,bs),7.40(1H,s),7.52(1H,d),7.56(1H,d) |
NMR-43(ⅩⅢ-39) | 1.46(3H, t),1.91(3H,s),2.34(3H,s),4.07(2H,q),5.50(1H,bs),7.40(1H,s),7.53(1H,d),7.56(1H,d) |
NMR-44(ⅩⅢ-45) | 1.82(3H,s),1.88(3H,s),2.33(3H,s),3.63(3H,s),5.75(1H,bs),7.37(1H,d),7.55(1H,d), |
NMR-45(ⅩⅤ16) | 1.78(3H,s),2.55(3H,s),3.28(3H,s),3.65(3H,s),4.43(1H,bs),6.21(1H,s),7.60(1H,d),8.27(1H,d) |
NMR-46(ⅩⅨ-4) | 1.47(3H,t),2.37(3H,s),2.86(3H,s),4.08(2H,q),5.32(1H,bs),6.21(1H,s),7.60(1H,d),8.27(1H.d), |
(参考例)
下面描述关于原料苯甲酸类的参考例。
参考例1
将10克(0.04摩尔)3-甲酰-2,4-二氯苯甲酸甲酯、7.9克(0.04摩尔)对甲苯磺酰基甲基胩和16.7克(0.12摩尔)碳酸钾溶解于100毫升甲醇中,然后在回流下加热该溶液15小时。反应完毕后,减压蒸馏除去甲醇,将残留物溶解于水中,再用乙酸乙酯洗涤。产生的水层用浓盐酸酸化,通过过滤收集沉淀的晶体,用水洗涤,然后干燥,获得8.96克3-(1,3-噁唑-5-基)-2,4-二氯苯甲酸。产率=86%,其m.p.为166-167℃。
参考例2
将8.96克(0.034摩尔)3-(1,3-噁唑-5-基)-2,4-二氯苯甲酸和4.8克(0.034摩尔)碳酸钾溶解于20毫升二甲基甲酰胺中,再加入6.6克(0.046摩尔)甲基碘,随后在室温下搅拌2小时。然后将产生的反应混合物倒入冰水中,用乙酸乙酯萃取,用饱和氯化钠溶液洗涤,之后用无水硫酸镁干燥,减压蒸馏除去溶剂,获得9.26克3-(1,3-噁唑-5-基)-2,4-二氯苯甲酸甲酯。产率=98.1%,其m.p.为78-79℃。
将9.26克(0.034摩尔)所获的3-(1,3-噁唑-5-基)-2,4-二氯苯甲酸甲酯和16.6克(0.035摩尔)15%的甲硫醇钠水溶液溶解于20毫升二甲基甲酰胺中,随后在室温下搅拌2小时。将产生的反应混合物倒入冰水中,用乙酸乙酯萃取,用饱和氯化钠溶液洗涤,然后用无水硫酸镁干燥,并减压蒸馏除去溶剂,获得6.65克3-(1,3-噁唑-5-基)-2-氯-4-甲硫基苯甲酸甲酯。产率=69%,其m.p.为98-101℃。
将6.65克(0.023摩尔)所获的3-(1,3-噁唑-5-基)-2-氯-4-甲硫基苯甲酸甲酯溶解于70毫升乙醇中,再加入70毫升1N苛性苏打,随后在室温下搅拌2小时。将反应混合物倒入冰水中,用浓盐酸酸化,通过过滤收集沉淀的晶体,用水洗涤,然后干燥,获得5.85克3-(1,3-噁唑-5-基)-2-氯-4-甲硫基苯甲酸。产率=92.7%。
参考例3
将5.85克(0.022摩尔)3-(1,3-噁唑-5-基)-2-氯-4-甲硫基苯甲酸溶解于20毫升乙酸中,然后在100℃滴加6.4克(0.066摩尔)35%的过氧化氢水溶液。随后在室温下搅拌1小时。然后将产生的反应混合物倒入冰水中,用乙酸乙酯萃取,用饱和氯化钠溶液洗涤。之后用无水硫酸镁干燥乙酸乙酯层,减压蒸馏除去溶剂,获得3.3克3-(1,3-噁唑-5-基)-2-氯-4-甲磺酰基苯甲酸白色晶体。产率=50%,其m.p.为203-204℃。
参考例4
将13.32克(0.053摩尔)3-氨基羰基-2,4-二氯苯甲酸甲酯和3.6克(0.016摩尔)五硫化磷溶解于90毫升的溶剂中,于80℃搅拌该溶液并使之反应过夜。将反应混合物倒入冰水中,用乙酸乙酯萃取,用饱和氯化钠溶液洗涤,然后用无水硫酸镁干,减压蒸馏除去溶剂。之后,制得的残留物通过硅胶柱色谱提纯,获得5.43克3-氨基硫代羰基-2,4-二氯苯甲酸甲酯。产率=38.4%。
将5.43克(0.02摩尔)所获的3-氨基硫代羰基-2,4-二氯苯甲酸甲酯和1.9克(0.02摩尔)氯代丙酮溶解于30毫升甲基乙基酮中,该溶液在回流下加热过夜。将产生的反应混合物倒入冰水中,用乙酸乙酯萃取,用饱和氯化钠溶液洗涤,然后用无水硫酸镁干燥,并减压蒸馏除去溶剂。之后,制得的残留物经硅胶柱色谱提纯,获得1.0克2,4-二氯-3-(4-甲基-1,3-噻唑-2-基)苯甲酸酯。产率=16.2%。
将1.0克(0.033摩尔)所获的2,4-二氯-3-(4-甲基-1,3-噻唑-2-基)苯甲酸酯溶解于10毫升乙醇中,再加入10毫升1N苛性苏打,随后在室温下搅拌过夜。将反应混合物倒入冰水中,用浓盐酸酸化,通过过滤收集沉淀的晶体,用水洗涤,然后干燥,获得0.84克2,4-二氯-3-(4-甲基-1,3-噻唑-2-基)苯甲酸。产率=88.4%,以及物性值。
参考例5
将24.7克(0.1摩尔)3-甲酰基-2,4-二氯苯甲酸甲酯溶解于120毫升丙酮和12毫升水的溶剂中,然后该溶液在冰水中冷却。之后,在20℃或更低温度下,耗时30分钟滴加35毫升1N苛性苏打水溶液,随后室温下搅拌该溶液过夜。将产生的反应混合物倒入冰水中,用浓盐酸酸化,然后用乙酸乙酯萃取。之后,用饱和氯化钠溶液洗涤乙酸乙酯层,用无水硫酸镁干燥,并在减压下浓缩。将制得的残留物溶解于苯中,然后加入催化量的对甲苯磺酸。随后该溶液在回流下加热4小时,期间除去水。使之冷却后,用饱和氯化钠溶液洗涤,用无水硫酸镁干燥。然后减压浓缩。通过硅胶柱色谱提纯制得的残留物,获得15.4克2,4-二氯-3-(3-氧代-1-丁烯基)苯甲酸甲酯,产率=54.8%。
将15.4克(0.056摩尔)所获的2,4-二氯-3-(3-氧代-1-丁烯基)苯甲酸甲酯和15克(0.216摩尔)羟基胺盐酸盐溶解于80毫升乙醇和80毫升吡啶溶剂中,该溶液在回流下加热2小时。将产生的反应混合物倒入冰水中,用乙酸乙酯萃取,用1N盐酸和饱和氯化钠溶液洗涤乙酸乙酯层,然后用无水硫酸镁干燥。减压蒸馏除去溶剂,获得15.9克2,4-二氯-3-(3-羟基亚胺基-1-丁烯基)苯甲酸甲酯。产率=98.2%。
将15.9克(0.052摩尔)所获的2,4-二氯-3-(3-羟基亚胺基-1-丁烯基)苯甲酸甲酯溶解于250毫升四氢呋喃中,再加入160毫升含16.8克(0.2摩尔)碳酸氢钠的水溶液。随后加入在120毫升水中溶解30.1克(0.18摩尔)碘化钾和14克(0.055摩尔)碘获得的水溶液,该溶液在回流下加热4小时,加热时须遮光。将产生的反应混合物倒入冰水中,加入硫氢化钠,随后用乙酸乙酯萃取。制得的有机层用饱和氯化钠洗涤,然后用硫酸镁干燥,减压蒸馏除去溶剂。残留物通过硅胶柱色谱提纯,获得8.8克2,4-二氯-3-(3-甲基-1,2-异噁唑-5-基)苯甲酸甲酯。产率=54.5%,m.p.为84-89℃。
将2.0克(0.0069摩尔)所获的2,4-二氯-3-(3-甲基-1,2-异噁唑-5-基)苯甲酸甲酯溶解在21毫升乙醇中,加入21毫升1N苛性苏打水溶液,随后在室温下搅拌过夜。产生的反应混合物倒入冰水中,然后用浓盐酸酸化。之后,通过过滤收集沉淀的晶体,用水洗涤并干燥后,获得1.86克2,4-二氯-3-(3-甲基-1,2-异噁唑-5-基)苯甲酸。产率=97.9%。m.p.为154-156℃。
参考例6
将8.8克(0.030摩尔)2,4-二氯-3-(3-甲基-1,2-异噁唑-5-基)苯甲酸甲酯和4.2克(0.030摩尔)碳酸钾溶解于20毫升二甲基甲酰胺中,然后加入含1.9克(0.038摩尔甲硫醇和10毫升二甲基甲酰胺的溶液,随后在室温下搅拌过夜。将产生的反应混合物倒入冰水中,用乙酸乙酯萃取,用饱和氯化钠溶液洗涤,然后用硫酸镁干燥,并减压蒸馏除去溶剂。通过硅胶柱色谱提纯残留物,获得7.49克2-氯-3-(3-甲基-1,3-异噁唑-5-基)-4-甲硫基苯甲酸甲酯,产率=82%。
将7.49克(0.025摩尔)所获的2-氯-3-(3-甲基-1,3-异噁唑-5-基)-4-甲硫基苯甲酸甲酯溶解于30毫升氯仿中,加入13克(0.074摩尔)间氯过苯甲酸,随后在室温下搅拌3小时。过滤反应混合物,制得的滤液用1N苛性苏打水溶液洗涤,再用饱和氯化钠洗涤,然后用硫酸镁干燥,并减压蒸馏除去溶剂。残留物经硅胶柱色谱提纯,获得8.19克2-氯-3-(3-甲基-1,3-异噁唑-5-基)-2-氯-4-甲磺酰基苯甲酸甲酯。产率=99%。
将8.19克(0.024摩尔)所获的2-氯-3-(3-甲基-1,2-异噁唑-5-基)-4-甲磺酰基苯甲酸甲酯溶解于75毫升乙醇中,再加入75毫升1N苛性苏打水溶液,随后在室温下搅拌过夜。将产生的反应混合物倒入冰水中,用浓盐酸酸化。之后通过过滤收集沉淀的晶体,用水洗涤,干燥、获得7.49克白色晶体状所需化合物。产率=96%,m.p.为225-228℃。
参考例7
制备2-氯-4-甲磺酰基-3-(5-甲基-1,3,4-噁二唑-2-基)苯甲酸
在10℃或更低温度下将含16.3克(0.061摩尔)3-甲氧羰基-2,6-二氯苯甲酰氯的氯仿溶液滴加到含9.15克(0.183摩尔)水合肼和150毫升氯仿的溶液中,随后在室温下搅拌过夜。反应完毕后,通过过滤除去不溶物,制得的滤液用饱和氯化钠溶液洗涤,用无水硫酸镁干燥。减压蒸馏除去溶剂,获得8.89克白色晶体状的3-甲氧羰基-2,6-二氯苯甲酸酰肼,产率=55.4%。
将8.89克(0.0338摩尔)所获的3-甲氧羰基-2,6-二氯苯甲酸酰肼和4.6克(0.037摩尔)乙酰亚胺酸乙酯盐酸盐(ethylacetoimidate hydrochloride)溶解于170毫升吡啶中,随后在回流下加热5小时。使溶液冷却后,减压蒸馏除去吡啶,然后该溶液溶解于乙酸乙酯中,用1N盐酸溶液、5%碳酸氢钠溶液和饱和氯化钠溶液洗涤,用硫酸镁干燥。减压蒸馏除去溶剂后,制得的残留物用硅胶柱色谱提纯,获得2.63克油状的2,4-二氯-3-(5-甲基-1,3,4-噁二唑-2-基)苯甲酸甲酯。产率=27.1%。
将2.63克(0.0091摩尔)所获的2,4-二氯-3-(5-甲基-1,3,4-噁二唑-2-基)苯甲酸甲酯和1.3克(0.0094摩尔)碳酸钾溶解于20毫升二甲基甲酰胺中,再加入10毫升溶有0.65克(0.013摩尔)甲硫醇的二甲基甲酰胺溶液,随后在室温下搅拌过夜。之后,将产生的反应混合物倒入冰水中,用乙酸乙酯萃取,用饱和氯化钠洗涤,然后用硫酸镁干燥,减压蒸馏除去溶剂。残留物通过硅胶柱色谱提纯,获得2.11克油状2-氯-3-(5-甲基-1,3,4-噁二唑-2-基)-4-甲硫基苯甲酸甲酯。产率=77.3%。
将2.1克(0.0070摩尔)所获的2-氯-3-(5-甲基-1,3,4-噁二唑-2-基)-4-甲硫基苯甲酸甲酯溶解在20毫升氯仿中,加入3.7克(0.021摩尔)间氯过苯甲酸,随后在室温下搅拌3小时。过滤反应混合物,制得的滤液用1N苛性苏打水溶液洗涤,再用饱和氯化钠溶液洗涤,用硫酸镁干燥,减压蒸去溶剂。残留物通过硅胶柱色谱提纯,获得1.52克2-氯-4-甲磺酰基-3-(5-甲基-1,3,4-噁二唑-2-基)苯甲酸甲酯白色结晶。产率=65.2%。
将1.52克(0.0046摩尔)2-氯-4-甲磺酰基-3-(5-甲基-1,3,4-噁二唑-2-基)苯甲酸甲酯溶解在14毫升乙醇中,然后加入14毫升1N苛性苏打,随后在室温下搅拌过夜。之后,将产生的反应混合物倒入冰水中,再用浓盐酸酸化。然后过滤收集沉淀的晶体,用水洗涤,干燥后获得1.3克白色晶体状的所需化合物。产率=90%,其m.p.为201-203℃。
参考例8
将12.1克羟基胺盐酸盐溶解在100毫升甲醇中,在室温下耗时30分钟,在该溶液中滴加20毫升含10.2克碳酸钠的水溶液。之后加入8.4克(0.036摩尔)3-氰基-2,4-二氯苯甲酸甲酯,随后在60℃搅拌3小时。使溶液冷却后,减压蒸馏除去甲醇,然后将产生的残留物溶解在乙酸乙酯中,然后用饱和氯化钠溶液洗涤,减压蒸馏除去溶剂,获得8.55克2,4-二氯-3-(N-羟基咪基)苯甲酸甲酯(methyl2,4-dichloro-3(N-hydroxyamidino)benzoate)。产率=89.1%。
将8.55克(0.032摩尔)所获的2,4-二氯-3-(N-羟基咪基)苯甲酸甲酯和10克(0.098摩尔)乙酸酐溶解于100毫升甲苯中,随后在回流下加热过夜。使溶液冷却后,用水洗涤,用硫酸镁干燥,并减压蒸馏除去溶剂。残留物用硅胶柱色谱提纯,获得3.63克白色晶体状的2,4-二氯-3-(5-甲基-1,2,4-噁二唑-3-基)苯甲酸甲酯。产率=38.9%,m.p.为70-72℃。
将2.75克(0.0095摩尔)所获的2,4-二氯-3-(5-甲基-1,2,4-噁二唑-3-基)苯甲酸甲酯和1.32克(0.0095摩尔)碳酸钾溶解于20毫升二甲基甲酰胺中,再加入10毫升溶有0.7克(0.014摩尔)甲硫醇的二甲基甲酰胺溶液,随后在室温下搅拌过夜。之后,将产生的反应混合物倒入冰水中,用乙酸乙酯萃取,用饱和氯化钠洗涤,然后用硫酸镁干燥,减压蒸馏除去溶剂。残留物通过硅胶柱色谱提纯,获得2.8克白色晶体状2-氯-3-(5-甲基-1,2,4-噁二唑-3-基)-4-甲硫基苯甲酸甲酯。产率=98.5%,m.p.为84-85℃。
将2.8克(0.0084摩尔)所获的2-氯-3-(5-甲基-1,2,4-噁二唑-3-基)-4-甲硫基苯甲酸甲酯溶解在20毫升氯仿中,加入4.95克(0.028摩尔)间氯过苯甲酸,随后在室温下搅拌3小时。过滤反应混合物除去不溶物,制得的滤液用1N苛性苏打水溶液洗涤,再用饱和氯化钠溶液洗涤,用硫酸镁干燥。之后,减压蒸馏除去溶剂,残留物通过硅胶柱色谱提纯,获得2.16克白色晶体状的2-氯-4-甲磺酰基-3-(5-甲基-1,2,4-噁二唑-3-基)苯甲酸甲酯。产率=77.9%,m.p.=118-120℃。
将2.16克(0.0046摩尔)2-氯-4-甲磺酰基-3-(5-甲基-1,2,4-噁二唑-3-基)苯甲酸甲酯溶解在19毫升乙醇中,然后加入19毫升1N苛性苏打溶液,随后在室温下搅拌过夜。之后,将产生的反应混合物倒入冰水中,再用浓盐酸酸化。然后过滤收集沉淀的晶体,用水洗涤,干燥后获得1.65克2-氯-4-甲磺酰基-3-(5-甲基-1,2,4-噁二唑-2-基)苯甲酸甲酯。产率=79.7%,其m.p.为207-210℃。
参考例9
将11.00克(0.0443摩尔)2,4-二氯-3-肟基甲基苯甲酸甲酯溶解在110毫升二甲基甲酰胺中,在10℃或更低温度下耗时1小时在该溶液中滴加110毫升溶有38.17克(0.214摩尔)N-溴琥珀酰亚胺。之后在10℃或更低温度下耗时1小时,在该溶液中滴加110毫升含21.67克(0.214摩尔)三乙胺的二甲基甲酰胺溶液,随后在该温度再搅拌1小时。将产生的反应混合物倒入冰水,立即用二氯甲烷萃取,用冷水洗涤,再用硫酸镁干燥。过滤后,在制得的滤液中加入15.84克(0.184摩尔)乙酸乙烯酯,随后在回流下加热过夜。冷却反应混合物后,减压蒸馏除去溶剂,然后产生的残留物通过硅胶柱色谱提纯,获得13.35克油状的3-(5-乙酰氧基-4,5-二氢-1,2-异噁唑啉-3-基)-2,4-二氯苯甲酸甲酯。
将13.35克(0.0402摩尔)所获的3-(5-乙酰氧基-4,5-二氢-1,2-异噁唑啉-3-基)-2,4-二氯苯甲酸甲酯溶解于30毫升甲醇中,再加入45毫升浓盐酸,随后在回流下加热5天。之后,冷却反应混合物,减压蒸馏除去甲醇。制得的残留物溶解在乙酸乙酯中,用饱和氯化钠溶液洗涤,然后用硫酸镁干燥,减压蒸馏除去溶剂。残留物经硅胶柱色谱提纯,获得7.19克白色晶体状的所需化合物。其m.p.为54-57℃。
参考例10
将2.90克(0.0106摩尔)参考例9中所获的2,4-二氯-3-(1,2-异噁唑-3-基)苯甲酸甲酯和1.46克(0.0106摩尔)碳酸钾溶解在20毫升二甲基甲酰胺中,再加入0.67克(0.016摩尔)甲硫醇溶于2毫升二甲基甲酰胺获得的溶液,随后在室温下搅拌过夜。将产生的反应混合物倒入冰水中,用乙酸乙酯萃取,用饱和氯化钠溶液洗涤,再用硫酸镁干燥。减压蒸馏除去溶剂,将产生的残留物溶解在30毫升氯仿中。再加入5.48克(0.031摩尔)间氯过苯甲酸,随后在室温下搅拌1小时。之后,过滤反应混合物,制得的滤液用1N苛性苏打溶液、饱和氯化钠溶液洗涤,然后用硫酸镁干燥。减压下蒸馏除去溶剂,制得残留物经硅胶柱色谱提纯,获得1.73克油状的所需化合物。
参考例11
制备2-氯-3-(1,2-异噁唑-3-基)-4-甲磺酰基苯甲酸
将1.73克(0.0054摩尔)参考例10中所获的2-氯-3-(1,2-异噁唑-3-基)-4-甲磺酰基苯甲酸甲酯溶解在17毫升乙醇中,并加入1N苛性苏打溶液,随后在室温下搅拌过夜。之后,将产生的反应混合物倒入冰水中,用浓盐酸酸化,通过过滤收集沉淀的晶体。收集的晶体用水洗涤后干燥,获得1.32克晶体状的所需化合物,其m.p.=182-184℃。
参考例12
制备2,4-二氯-3-(5-甲基-1,2-异噁唑-3-基)苯甲酸甲酯
将15.87克(0.0639摩尔)2,4-二氯-3-肟基甲基-苯甲酸甲酯溶解在160毫升二甲基甲酰胺中,在10℃或更低温度下,耗时1小时在上述溶液中滴加将55.00克(0.308摩尔)N-溴琥珀酰亚胺溶解在160毫升二甲基甲酰胺获得的溶液。之后,在10℃或更低温度下耗时1小时滴加另一种将31.3克(0.309摩尔)三乙胺溶解在160毫升二甲基甲酰胺中获得的溶液,随后在该温度下再搅拌1小时。将产生的反应混合物倒入冰水中,迅速用二氯甲烷萃取,用冷水洗涤,再用硫酸镁干燥。过滤后,在制得的滤液中加入21.53克(0.215摩尔)乙酸异丙烯酯,随后在回流下加热过夜。冷却反应混合物,减压蒸馏除去溶剂。制得的残留物经硅胶柱色谱提纯,获得8.57克油状的所需化合物,其m.p.=96-97℃。
参考例13
制备2-氯-4-甲磺酰基-3-(5-甲基-1,2-异噁唑-3-基)苯甲酸甲酯
将8.57克(0.0299摩尔)在参考例12中所获的2,4-二氯-3-(5-甲基-1,2-异噁唑-3-基)苯甲酸甲酯和4.2克(0.03摩尔)碳酸钾溶解在40毫升二甲基甲酰胺中,加入将2.9克(0.06摩尔)甲硫醇溶解在10毫升二甲基甲酰胺获得的溶液,在室温下搅拌过夜。之后,将产生的反应混合物倒入冰水中,用乙酸乙酯萃取,用饱和氯化钠溶液洗涤,再用硫酸镁干燥。减压蒸馏除去溶剂,将制得的残留物溶解在50毫升氯仿中。随后加入15.5克(0.089摩尔)间氯过苯甲酸,在室温下搅拌1小时。然后过滤反应混合物,制得的滤液用1N苛性苏打溶液和饱和氯化钠溶液洗涤,再用硫酸镁干燥。减压蒸馏除去溶剂,制得的残留物经硅胶柱色谱提纯,获得4.41克白色晶体状的所需化合物,其m.p.=135-136℃。
参考例14
将4.35克(0.0132摩尔)在参考例13中所获的2-氯-4-甲磺酰基-3-(5-甲基-1,2-异噁唑-3-基)苯甲酸甲酯溶解在40毫升乙醇中,并加入40毫升苛性苏打溶液,随后在室温下搅拌过夜。之后,将产生的反应混合物倒入冰水中,用浓盐酸酸化,通过过滤收集沉淀的晶体。收集的晶体用水洗涤,后干燥,获得3.79克白色晶体状的所需化合物,其m.p.=189-190℃。
参考例15
将26.61克含28%甲醇钠的甲醇溶液加入到100毫升甲醇中,在冰冷却下在25℃滴加12.29克2-硝基丙烷。再加入41.16克3-溴甲基-2,4-二氯苯甲酸甲酯,随后在加热和回流下搅拌30分钟。冷却后,减压下浓缩反应溶液,将制得的残留物溶解在1000毫升乙酸乙酯中,然后在冰冷却下用1%氢氧化钠溶液洗涤。有机层用水洗涤,再用饱和氯化钠溶液洗涤,然后用无水硫酸镁干燥。减压蒸馏除去溶剂,制得的晶体用苯、再用正己烷洗涤,获得22.00克晶体状所需的2,4-二氯-3-甲酰基苯甲酸甲酯,其m.p.=103-104℃。
参考例16
将1.04克2,4-二氯-3-甲酰基苯甲酸甲酯溶解在5毫升乙醇中,然后加入10毫升1N氢氧化钠溶液,随后在室温下搅拌17小时。之后,将反应溶液倒入40毫升冰水中,用浓盐酸酸化。之后,通过过滤收集沉淀的晶体,干燥后获得0.75克晶体状2,4-二氯-3-甲酰基苯甲酸,其m.p.=188-190℃。
参考例17
将24.2克2,4-二氯-3-甲酰基苯甲酸甲酯溶解在350毫升丙酮中,滴加55毫升根据E.R.H.Jones等人在J.Chem.Soc.,P.2548(1953)中所述的方法制备的Jones试剂,滴加时温度保持在10-15℃。在10℃或更低温度下,搅拌该溶液1.5小时后,在其中加入50毫升异丙醇和20克碳酸氢钠,随后搅拌30分钟。之后通过过滤除去不溶物,并浓缩制得的滤液。然后加入300毫升水,用300毫升乙酸乙酯萃取。制得的有机层用饱和氯化钠溶液洗涤,然后用无水硫酸镁干燥。减压蒸馏除去溶剂,获得25.0克晶体状所需的2,6-二氯-3-甲氧基羰基苯甲酸。
参考例18
将2.47克2,4-二氯-3-甲酰基苯甲酸甲酯溶解在20毫升干THF中,在-70℃缓慢滴加4.0毫升溴化甲基镁-乙醚溶液(3.0摩尔/升)。滴加完毕后,除去冷却浴,使溶液温度自发回升,同时搅拌该溶液1小时。将反应混合物倒入冰水,用稀盐酸酸化,然后用乙醚萃取。制得的有机层用水和饱和氯化钠溶液洗涤,然后用无水硫酸镁干燥。减压蒸馏浓缩溶剂,获得2.42克油状的2,4-二氯-3-(1-羟乙基)苯甲酸甲酯。随后将2.42克2,4-二氯-3-(1-羟乙基)苯甲酸甲酯溶解在10毫升苯中,再加入4克二氧化锰,随后在加热和回流下搅拌1小时。再加入3克二氧化锰,在加热和回流下搅拌1小时。反应溶液冷却至室温,过滤除去不溶物。减压蒸馏制得的滤液,除去溶剂,获得1.75克所需的2,4-二氯-3-(1-氧代乙基)苯甲酸甲酯。
参考例19
将25.72克2,4-二氯-3-甲酰基苯甲酸甲酯溶解在100毫升甲苯中,加入39.0克硝基乙烷和1.5克正丁胺,随后在回流下反应21小时。将反应溶液倒入冰水,用乙酸乙酯萃取,用1N盐酸和饱和氯化钠溶液洗涤,然后用硫酸镁干燥。减压蒸馏除去溶剂,获得34.9克2,4-二氯-3-(2-硝基-1-丙烯基)苯甲酸甲酯。随后将30.1克未经提纯的该产物加到120毫升甲苯和360毫升水的混合溶剂中,然后加入20.8克铁粉和0.4克三氯化铁。之后,在80℃滴加104克浓盐酸。滴加完毕,在回流下反应1小时。冷却该反应溶液,加入乙酸乙酯,并通过过滤除去不溶物。制得的有机层用水和饱和氯化钠溶液洗涤,再用无水硫酸镁干燥。减压蒸馏浓缩溶剂,制得的残留物经硅胶柱色谱提纯,获得19.53克2,4-二氯-3-(2-氧代丙基)苯甲酸甲酯。
参考例20
制备2,4-二氯-3-(2-氧代-1-二甲氨基次甲基丙基)苯甲酸甲酯
17.09克2,4-二氯-3-(2-氧代丙基)苯甲酸甲酯和60毫升N,N-二甲基甲酰胺基二甲缩醛的混合物在回流下加热22小时。减压下浓缩该反应溶液,残留物经硅胶柱色谱提纯,获得5.61克2,4-二氯-3-(2-氧代-1-二甲氨基次甲基丙基)苯甲酸甲酯。
参考例21
将4.10克2,4-二氯-3-(2-氧代-1-二甲氨基次甲基丙基)苯甲酸甲酯加到20毫升二噁烷和10毫升水的混合物中,加入0.90克羟胺盐酸盐,随后在室温下搅拌17小时。将反应溶液倒入冰水,用乙酸乙酯萃取,用饱和氯化钠溶液洗涤,然后用无水硫酸镁干燥。减压蒸馏除去溶剂,制得的残留物经硅胶柱色谱提纯,获得1.8克肟的异构体混合物。将该肟物质溶解在甲苯中,加入0.5克对甲苯磺酸,随后在加热和回流下搅拌30分钟。冷却后,溶液用水和饱和氯化钠溶液洗涤,然后用无水硫酸镁干燥。减压蒸馏浓缩该溶液,获得1.42克所需的2,4-二氯-3-(5-甲基异噁唑-4-基)苯甲酸甲酯。
参考例22
将1.42克2,4-二氯-3-(5-甲基异噁唑-4-基)苯甲酸甲酯溶解在20毫升DMF中,然后加入0.70克碳酸钾。再滴加含0.35克甲硫醇的DMF溶液。在室温下搅拌17小时后,将该溶液倒入冰水,用乙酸乙酯萃取。制得的有机层用水和饱和氯化钠溶液洗涤,然后用无水硫酸镁干燥。减压蒸馏浓缩溶剂,获得1.17克2-氯-3-(5-甲基异噁唑-4-基)-4-甲硫基苯甲酸甲酯。
参考例23
制备2-氯-4-甲磺酰基-3-(5-甲基异噁唑-4-基)苯甲酸甲酯
将1.17克2-氯-3-(5-甲基异噁唑-4-基)-4-甲硫基苯甲酸甲酯溶解在20毫升氯仿中,然后在室温下加入2.10克间氯过苯甲酸,随后在室温下搅拌74小时。该溶液用饱和碳酸氢钠溶液洗涤三次,再用饱和氯化钠溶液洗涤,然后用无水硫酸镁干燥。减压蒸馏浓缩溶剂,制得的残留物经硅胶柱色谱提纯后,获得0.84克晶体状所需的2-氯-4-甲磺酰基-3-(5-甲基异噁唑-4-基)苯甲酸甲酯。
m.p.=137-142℃。
参考例24
将0.84克2-氯-4-甲磺酰基-3-(5-甲基异噁唑-4-基)苯甲酸甲酯溶解在20毫升二噁烷中,加入10毫升浓盐酸,随后在加热和回流下搅拌16小时。冷却后,蒸馏除去二噁烷,然后用乙酸乙酯萃取,制得的有机层用饱和氯化钠溶液洗涤,然后用无水硫酸镁干燥。减压蒸馏浓缩溶剂,制得的残留物经硅胶柱色谱提纯后,获得0.69克晶体状所需的2-氯-4-甲磺酰基-3-(5-甲基异噁唑-4-基)苯甲酸。
参考例25
将13.32克甲基丙二酸二甲酯溶解在150毫升甲苯中,再加入10.43克乙醇镁,随后在加热和回流下搅拌2小时。反应溶液冷却后,减压下低沸点组分与甲苯一起蒸馏除去,制得的残留物溶解在200毫升甲苯中。室温下在该溶液中加入24.40克3-甲氧基羰基-2,6-二氯苯甲酰氯,该溶液在室温下搅拌1小时,并在加热和回流下搅拌4.5小时。冷却反应溶液,并且将它倒入冰水,用浓盐酸酸化,然后萃取。萃取的有机层用饱和氯化钠溶液洗涤,然后用无水硫酸镁干燥。减压蒸馏浓缩溶剂,获得34.3克晶体状2,4-二氯-3-(3,3-二甲氧基羰基-1-氧代丙基)苯甲酸甲酯。
将该产物加到40毫升水、由8毫升浓硫酸制备的稀硫酸和63毫升乙酸的混合物中,随后在加热和回流下搅拌12.5小时。冷却后,将该反应溶液倒入冰水中,用乙酸乙酯萃取,用水和饱和氯化钠溶液洗涤,再用无水硫酸镁干燥。减压蒸馏除去溶解,将残留物溶解在DMF中。之后,根据常规的甲基碘法,在碳酸钾存在下进行酯化,获得19.31克3-苯基乙基酮物质(纯度=50%)。然后,将14.29克该粗产品加到60毫升N,N-二甲基甲酰氨基二甲缩醛中,随后在加热和回流下搅拌23.5小时。冷却后,在减压下蒸馏除去低沸点组分,制得的残留物经硅胶柱色谱提纯获得7.75克所需的2,4-二氯-3-(2-二甲氨基次甲基-1-氧代丙氧基)苯甲酸甲酯。
m.p.=127.5-128℃。
参考例26
制备2,4-二氯-3-(4-甲基异噁二唑-5-基)苯甲酸甲酯
将7.57克2,4-二氯-3-(2-二甲氨基次甲基-1-氧代丙基)苯甲酸甲酯溶解在30毫升二噁烷和16毫升水的混合物中,加入1.70克羟胺盐酸盐,随后在室温下搅拌17小时。减压蒸馏除去溶剂,制得的残留物溶解在乙酸乙酯中,用饱和氯化钠溶液洗涤,然后用无水硫酸镁干燥,减压蒸馏蒸去溶剂,将制得的肟化合物粗品溶于30毫升甲苯。然后加入0.5克对甲苯磺酸,在加热回流下搅拌14.5小时。冷却后,反应溶液用水和饱和氯化钠溶液洗涤,用无水硫酸镁干燥。减压浓缩溶剂,制得的残留物经硅胶柱色谱提纯,获得0.83克所需的2,4-二氯-3-(4-甲基异噁唑-5-基)苯甲酸甲酯。
参考例27
制备2,4-二氯-3-(4-甲基异噁唑-5-基)苯甲酸
将0.83克2,4-二氯-3-(4-甲基异噁唑-5-基)苯甲酸甲酯溶解在20毫升二噁烷中,再加入5毫升浓盐酸,随后在加热和回流下搅拌15.5小时。冷却后,蒸去二噁烷,用乙酸乙酯萃取。制得的有机层用饱和氯化钠溶液洗涤,然后用无水硫酸镁干燥。减压蒸馏浓缩溶剂,制得的残留物经硅胶柱色谱提纯,获得0.48克所需的2,4-二氯-3-(4-甲基异噁唑-5-基)苯甲酸结晶。
m.p.=248-252℃。
参考例28
将1.65克乙醇镁悬浮在30毫升甲苯中,在60-70℃滴加2.28克乙酰乙酸叔丁酯。加热和回流2小时后,该溶液冷却至室温,再滴加8.85克2,6-二氯-3-甲氧基羰基苯甲酰氯,随后在室温下搅拌2小时,再在50-100℃搅拌3小时。反应混合物冷却至室温后,在该反应混合物中加入稀盐酸,随后用乙酸乙酯萃取。用5%的碳酸钠溶液对有机层进行碱萃取。之后在水层加入氯仿,用稀盐酸进行酸沉淀,随后萃取。制得的有机层用饱和氯化钠溶液洗涤,然后用无水硫酸镁干燥。减压蒸馏浓缩溶剂,获得2.80克2-(2,6-二氯-3-甲氧基羰基苯甲酰)乙酰乙酸叔丁酯。之后,在该产物中加入45毫升甲苯,再加入0.2克对甲苯磺酸水合物,随后在加热和回流下搅拌6小时。反应溶液冷却后,加入200毫升乙酸乙酯,然后用200毫升水洗涤两次。制得的有机层用饱和氯化钠溶液洗涤,再用无水硫酸镁干燥。减压蒸馏浓缩溶剂,获得2.10克2,6-二氯-3-甲氧基羰基苯甲酰丙酮。
参考例29
制备2,4-二氯-3-(1,3-二甲基吡唑-5-基)苯甲酸
将2.10克2,6-二氯-3-甲氧基羰基苯甲酰丙酮溶解在10毫升乙醇中,加入0.34克甲基肼,随后在室温下搅拌3天。反应溶液浓缩后,制得的残留物经硅胶柱色谱提纯,获得1.75克2,4-二氯-3-(1,3-二甲基吡唑-5-基)苯甲酸的甲酯和乙酯的混合物。之后,将1.75克该酯混合物溶解在20毫升乙醇中,再加入20毫升1N氢氧化钠溶液,随后在室温下搅拌17小时。将产生的反应溶液倒入60毫升冰水中,再用浓盐酸酸化。过滤收集沉淀的晶体,干燥后获得1.50克晶体状所需的2,4-二氯-3-(1,3-二甲基吡唑-5-基)苯甲酸。
m.p.=204-208℃。
参考例30
制备2,4-二氯-3-(1,5-二甲基吡唑-3-基)苯甲酸甲酯
将11.2克2,4-二氯-3-(3-氧代-1-丁烯基)苯甲酸甲酯溶解在40毫升乙醇中,加入1.89克甲基肼,随后在室温下搅拌过夜。之后,加入0.38克甲基肼,该溶液在室温下搅拌2小时。浓缩该反应溶液,然后经硅胶柱色谱提纯,获得0.80克所需的2,4-二氯-3-(1,5-二甲基吡唑-3-基)苯甲酸甲酯和10.0克2,4-二氯-3-(4,5-二氢-1,3-二甲基吡唑-5-基)苯甲酸甲酯。
参考例31
将0.70克2,4-二氯-3-(1,5-二甲基吡唑-3-基)苯甲酸甲酯溶解在7毫升乙醇中,加入5毫升氢氧化钠溶液,随后在室温下搅拌17小时。制得的反应溶液倒入20毫升冰水中,然后用浓盐酸酸化。过滤收集沉淀的晶体,干燥后获得0.60克晶体状所需的2,4-二氯-3-(1,5-二甲基吡唑-3-基)苯甲酸。
m.p.=222-225℃。
参考例32
将6.0克2,4-二氯-3-(4,5-二氢-1,3-二甲基吡唑-5-基)苯甲酸甲酯溶解在50毫升苯中,加入9.1克2,3-二氢-5,6-二氰基苯醌(DDQ),随后在加热和回流下搅拌6小时。冷却后,过滤除去不溶物,制得的滤液用1N氢氧化钠溶液和水洗涤两次,再用饱和氯化钠溶液洗涤,然后用无水硫酸镁干燥。减压蒸馏浓缩溶剂,制得的残留物经硅胶柱色谱提纯,获得1.20克所需的2,4-二氯-3-(1,3-二甲基吡唑-5-基)苯甲酸甲酯。
参考例33
将26.61克含28%甲醇钠的甲醇溶液加到100毫升甲醇中,水冷却下在25℃加入12.29克2-硝基正丙烷。再加入41.16克3-溴甲基-2,4-二氯苯甲酸甲酯,随后在加热和回流下搅拌30分钟。冷却反应溶液,并在减压下蒸馏浓缩,制得的残留物溶剂在1000毫升乙酸乙酯中,在冰冷却下用1%氢氧化钠溶液洗涤。制得的有机层用水,再用饱和氯化钠溶液洗涤,然后用无水硫酸镁干燥。减压蒸馏浓缩溶剂,获得的晶体用苯,再用正己烷洗涤,获得22.00克晶体状所需的2,4-二氯-3-甲酰苯甲酸甲酯。
[除草剂]
本发明的化合物可提供高的除草活性,甚至是在包括耕种条件下的土壤处理或叶片处理的应用中,它们可对各类农田害杂草如看麦娘、苍耳、藜、野燕麦有效。本发明的这些化合物包括能选择性作用于作物如玉米、小麦、大麦、大豆和棉花的化合物。
另外,本发明的化合物包括为有用的植物如农作物、观赏植物、果树等提供植物生长调节活性(如生长控制作用)的化合物。
此外,本发明的化合物特别对杂草(如稗、Cyperus difformis、Sagittariatrifolia和灯心草)有良好的除草效果,它们包括那些对稻谷植物有选择性的化合物。
而且,本发明的化合物可用来抑制果园、草坪、铁路通道、空地等中的杂草。
本发明的除草剂组合物含有一种或多种本发明的化合物作为活性组分。在实际应用中,本发明的化合物无须加入其他任何组分而可以纯的形式使用,为了将本发明的化合物用作农用化学品,本发明的化合物可以常规用作农用化学品的配方形式(即可润湿的粉末、颗粒、粉末、可乳化的浓缩物、水溶性粉末、悬浮体或可流动配方)使用。在以固体药剂应用的情况下,作为添加剂和载体可采用植物加工制得的植物粉末(如豆粉和麦粉)、矿物细粉(如硅藻土、磷灰石、石膏、滑石、膨润土、叶蜡石和粘土)、有机和无机化合物(如苯甲酸钠、脲和芒硝)。在打算采用液体型试药的情况下,可采用溶剂,例如石油馏分(如煤油、二甲苯和溶剂轻油、环己烷、环己酮、二甲基甲酰胺、二甲基亚砜、醇、丙酮、三氯乙烷、甲基异丁基酮、矿物油、植物油和水。为了使配方处于均匀稳定的状态,如果需要,可加入表面活性剂。
活性组分在本发明的除草剂组合物中的浓度根据上述药剂的形式来确定,但是例如,在可润湿粉末例子中,它在5-90%范围内,以10-85%为佳;在乳剂例子中,它在3-70%范围内,以5-60%为佳;在颗粒例子中,它在0.01-50%范围内,以0.05-40%为佳。
由此获得的可润湿粉末或乳剂可用水稀释至预定浓度,以获得悬浮液或乳剂,颗粒可在杂草发芽前或发芽后直接喷洒在土壤上或是与土壤混合。实际上,在施用本发明的除草剂时,待施用的活性组分的合适的量为0.1克/公顷或更多。
另外,本发明的除草剂可与任何已知的杀真菌剂、杀虫剂、杀螨剂、其它除草剂、植物生长调节剂和肥料混合使用。特别是,当本发明的除草剂与其它除草剂混合时,本发明的除草剂的量可以减少。另外,采用本发明的除草剂可减少劳动力,预计本发明混合试剂的协同效果可有更高的效果。在这种情况下,也可以使本发明的除草剂与多种已知的除草剂结合施用。
适于与本发明除草剂混合的制剂实例包括含有N-酰苯胺的除草剂(如吡氟草胺和敌稗)、含有氯代N-乙酰苯胺的除草剂(如甲草胺和丙草胺)、含有芳氧基链烷酸的除草剂(如2,4-D和2,4-DB)、含有芳氧基苯氧基链烷酸的除草剂(如禾草灵-甲基和噻唑禾草录-乙基)、含有芳基羧酸的除草剂(如麦草畏和pyrithiobac-sodium)、含有咪唑啉酮的除草剂(如灭草喹和咪草烟)、含有脲的除草剂(如敌草隆和异丙隆)、含有氨基甲酸酯的除草剂(如氯苯胺灵和苯敌草)、含有硫代氨基甲酸酯的除草剂(杀草丹和扑草灭)、含有二硝基苯胺的除草剂(如氟乐灵和二甲戊乐灵)、含有二苯基醚的除草剂(如三氟羧草醚-钠和氟黄胺草醚)、含有磺酰脲的除草剂(如苄嘧黄隆-甲基和烟嘧黄隆)、含有三嗪酮(triazinone)的除草剂(如嗪草酮和苯嗪草酮)、含有三嗪的除草剂(如莠去津和氰草津(cyanazine))、含有三唑嘧啶的除草剂(如flumetsulam)、含有腈的除草剂(如溴苯腈和敌草腈)、含有哒嗪酮的除草剂(如杀草敏和达草灰)、含有磷酸的除草剂(如草甘膦和草胺膦)、含有季铵盐的除草剂(如对草快和双苯唑快)、环状酰亚胺的除草剂(如flumiclorac-pentyl和fluthiacet-methyl)、其它除草剂(如isoxaben、乙呋草黄、恶草灵、二氯喹啉酸、异噁草酮、sulcotrione、环庚草醚、氟硫草定、吡唑特、哒草特、胺草唑、噻草平、呋草黄)、和含有环己二酮的除草剂(如稀禾定和肟草酮)。而且,在这些活性组分的组合中可加入植物油或油的浓缩物。
实施例
[除草剂]
将在下文中描述本发明的一些除草剂组合物的配方实例,然而,活性组分化合物、添加剂和加料比不应局限于这些实施例描述的范围内,它们可在较广的范围内改变。在配方实施例中,“份”指“重量份数”。
实施例5
可润湿粉末
本发明化合物 20份
白炭 20份
硅藻土 52份
烷基硫酸钠 8份
均匀混合这些材料,然后细磨获得含有20%有效组分的可润湿粉末。
实施例6
乳剂
本发明化合物 20份
二甲苯 55份
二甲基甲酰胺 15份
聚氧乙烯苯基醚 10份
均匀混合并溶解这些材料,获得含有20%有效组分的乳剂。
实施例7
颗粒
本发明化合物 5份
滑石 40份
粘土 38份
膨润土 10份
烷基硫酸钠 7份
均匀混合这些材料,细磨、造粒,获得直径为0.5-1.0mm、含有5%有效组分的颗粒。
[本发明效果]
下文将描述关于本发明除草剂效果的试验实施例。
根据下列评价标准来评价除草效果,由每一除草指数表示除草效果。
评价标准:
除草率% 除草指数
0% 0
20-29% 2
40-49% 4
60-69% 6
80-89% 8
100% 10
测试实施例1
叶片施用试验
在大小为200厘米2的盆中填入土壤,将绒状叶、藜、苍耳、看麦娘、燕麦、玉米和小麦的种子分别种入盆中。在用土壤覆盖种子后,使种子在温室内生长。当各植物长至高度为5-15厘米时,将实施例6中所述的含有样品化合物的乳剂的稀释水溶液用小的喷嘴喷洒在杂草的苗上,使得每个盆内每种活性组分的施用量为250克/公顷。3周后,检查各化合物样品的除草效果和对作物的有害作用,结果列于表22中。
表22
化合物 | 剂量克/公顷 | 绒状叶 | 藜 | 苍耳 | 看麦娘 | 燕麦 | 玉米 | 小麦 |
Ⅰ-67 | 250 | 10 | 10 | 10 | 10 | 6 | 0 | 2 |
Ⅰ-115 | 250 | 10 | 10 | 10 | 10 | 9 | 2 | 0 |
Ⅰ-116 | 250 | 9 | 9 | 10 | 10 | 9 | 0 | 0 |
Ⅰ-117 | 250 | 9 | 9 | 9 | 8 | 5 | 0 | - |
Ⅰ-118 | 250 | 9 | 10 | 9 | 10 | 6 | 0 | - |
Ⅰ-121 | 250 | 10 | 10 | 10 | 10 | 10 | 0 | - |
Ⅰ-123 | 250 | 8 | 10 | 6 | 8 | 0 | 0 | 0 |
Ⅰ-126 | 250 | 9 | 10 | 10 | 10 | 8 | 0 | - |
Ⅰ-128 | 250 | 7 | 9 | 8 | 10 | 10 | 0 | 0 |
Ⅰ-130 | 250 | 8 | 10 | 10 | 6 | 6 | 1 | - |
Ⅲ-6 | 250 | 7 | 10 | 10 | 10 | 6 | 0 | 0 |
Ⅳ-5 | 250 | 10 | 8 | 6 | 10 | 6 | - | 0 |
Ⅳ-17 | 250 | 10 | 10 | 10 | 10 | 5 | - | 0 |
Ⅳ-67 | 250 | 9 | 10 | 10 | 10 | 0 | 0 | 0 |
测试实施例2
稻茎叶处理试验
在表面积为100厘米2的盆中填入稻田土,仔细刻线后,将稗、灯心草、鸭舌草的种子分别种入盆中,然后种植两叶阶段的稻。使该稻在温室中生长,当各种杂草长至1-1.5叶阶段时,灌入水,使水深达3厘米。之后,滴加实施例5中所述的含有样品化合物的可润湿粉末的稀释水溶液,使得活性组分的施用量为63克/公顷。3周后,检查各化合物样品的除草效果和对作物的有害作用,结果列于表23中。
表23
化合物 | 剂量克/公顷 | 稗 | 灯心草 | 鸭舌草 | 种植的稻 |
Ⅰ-115 | 63 | 10 | 7 | 8 | 0 |
Ⅰ-116 | 63 | 10 | 7 | 9 | 1 |
Ⅰ-117 | 63 | 8 | 6 | 7 | 0 |
Ⅰ-118 | 63 | 10 | 8 | 7 | 0 |
Ⅰ-119 | 63 | 10 | 8 | 7 | 0 |
Ⅰ-120 | 63 | 10 | 6 | 8 | 0 |
Ⅰ-121 | 63 | 10 | 8 | 8 | 1 |
Ⅰ-129 | 63 | 10 | 6 | 7 | 0 |
Ⅰ-135 | 63 | 10 | 8 | 8 | 1 |
Ⅲ-6 | 63 | 10 | 6 | 8 | 0 |
Ⅳ-5 | 63 | 10 | 8 | 8 | 1 |
Ⅳ-17 | 63 | 10 | 8 | 6 | 0 |
Ⅳ-67 | 63 | 9 | 8 | 8 | 0 |
工业用途
如上所述,本发明的化合物具有优良的除草活性和对于作物的选择性,包含这些化合物的组合物可优选用作除草剂。
Claims (3)
1.一种用通式[Ⅰ]表示的化合物:式中R1、R2和R3相同或不同,它们表示卤原子、C1-6烷基、C1-6烷氧基、硝基、氰基、C1-6卤代烷基、C1-6卤代烷氧基、C1-6烷硫基、C1-6烷基亚磺酰基、或C1-6烷基磺酰基,n为0、1或2,当n等于2时,用R3表示的基团可以相同或不同;
Het是含有1-3个N、O或S原子且被R7和R8取代的饱和或不饱和的五员杂环,它们通过碳原子部分与苯环键合;
R4是氢原子、C1-6烷基、C1-6卤代烷基、羟基C1-6烷基或C1-6烷氧基C1-6烷基;
R5是氢原子、C1-6烷基、C2-6链烯基或C2-6链炔基;
R6是C1-6烷基、C3-8环烷基或苯基,它可被C1-6烷基、C1-6烷氧基、C1-6卤代烷基、C1-6卤代烷氧基、硝基或卤原子取代;
X是SO2、(CH2)mCO、可被烷基取代的C1-6亚烷基或一个单键,m为0、1、2或3。
2.如权利要求1所述的化合物,其特征在于Het是选自用如下结构式表示的一个基团:式中R7和R8各自表示氢原子、C1-6烷基、C1-6烷氧基、卤原子或C1-6卤代烷基。
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JP13117096 | 1996-04-26 | ||
JP131170/96 | 1996-04-26 | ||
JP31715496 | 1996-11-13 | ||
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CN102329277A (zh) * | 2011-10-24 | 2012-01-25 | 海南霞迪药业有限公司 | 一种制备帕瑞昔布的方法 |
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JP4131337B2 (ja) * | 1996-03-26 | 2008-08-13 | 日本曹達株式会社 | 3―(イソオキサゾール―5―イル)置換安息香酸誘導体およびその製造法 |
EP0900795B1 (en) * | 1996-04-26 | 2004-04-21 | Nippon Soda Co., Ltd. | Benzene derivatives substituted by heterocycles and herbicides |
WO1998028981A1 (fr) * | 1996-12-27 | 1998-07-09 | Nippon Soda Co., Ltd. | Composition herbicide |
KR20050111648A (ko) | 1997-01-17 | 2005-11-25 | 바스프 악티엔게젤샤프트 | 3-헤테로시클릴로 치환된 벤조일 유도체 |
US6165944A (en) * | 1997-01-17 | 2000-12-26 | Basf Aktiengesellschaft | 4-(3-heterocyclyl-1-benzoyl) pyrazoles and their use as herbicides |
AU9068598A (en) * | 1997-08-07 | 1999-03-16 | Basf Aktiengesellschaft | Heterocyclic substituted 4-benzoyl-pyrazole as herbicides |
WO1999021852A1 (fr) * | 1997-10-27 | 1999-05-06 | Nippon Soda Co., Ltd. | Nouveaux derives de benzoylpyrazole et herbicides |
AU9650598A (en) * | 1997-10-30 | 1999-05-24 | Nippon Soda Co., Ltd. | Novel benzoylpyrazole compounds, intermediates, and herbicides |
US6245716B1 (en) | 1998-04-22 | 2001-06-12 | Nippon Soda Co., Ltd. | Benzoylpyrazole compounds and herbicide |
ATE552249T1 (de) * | 1998-05-11 | 2012-04-15 | Basf Se | Verfahren zur herstellung von isoxazolin-3-yl- acylbenzolen |
WO2000003993A1 (fr) * | 1998-07-16 | 2000-01-27 | Ishihara Sangyo Kaisha Ltd. | Composes de type pyrazole, procede de production de ces composes et herbicides contenant lesdits composes |
ATE249456T1 (de) * | 1998-12-04 | 2003-09-15 | Basf Ag | 3-(heterocyclyl)-substituierte benzoylpyrazole |
DE19914140A1 (de) | 1999-03-27 | 2000-09-28 | Bayer Ag | Substituierte Benzoylpyrazole |
DE19946853A1 (de) | 1999-09-30 | 2001-04-05 | Bayer Ag | Substituierte Arylketone |
PL362683A1 (en) | 2000-01-17 | 2004-11-02 | Bayer Aktiengesellschaft | Substituted aryl ketones |
HUE055434T2 (hu) * | 2003-04-11 | 2021-11-29 | Ptc Therapeutics Inc | 1,2,4-Oxadiazol-benzoesav vegyület és alkalmazása nonszensz szupresszióra és betegség kezelésére |
US8101641B2 (en) | 2006-09-25 | 2012-01-24 | Ptc Therapeutics, Inc. | Hydroxylated 1,2,4-oxadiazole benzoic acid compounds and compositions thereof |
CA3174516A1 (en) | 2014-03-06 | 2015-09-11 | Ptc Therapeutics, Inc. | Pharmaceutical compositions and salts of a 1,2,4-oxadiazole benzoic acid |
BR112018008838A8 (pt) | 2015-10-30 | 2019-02-26 | Ptc Therapeutics Inc | método para tratar, prevenir, melhorar ou administrar uma doença epiléptica |
US20230150953A1 (en) | 2020-04-07 | 2023-05-18 | Bayer Aktiengesellschaft | Substituted isophthalic acid diamides |
WO2021204669A1 (de) | 2020-04-07 | 2021-10-14 | Bayer Aktiengesellschaft | Substituierte isophtalsäurediamide |
WO2021204665A1 (de) | 2020-04-07 | 2021-10-14 | Bayer Aktiengesellschaft | Substituierte isophtalsäurediamide |
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IL85659A (en) * | 1987-03-17 | 1992-03-29 | Nissan Chemical Ind Ltd | 4-benzoylpyrazole derivatives,method for their preparation and herbicidal compositions containing them |
GEP20002093B (en) * | 1995-02-24 | 2000-05-10 | Basf Ag | Pyrazol-4-yl-Benzoyl Derivatives and Herbicides Containing Them |
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- 1997-04-24 WO PCT/JP1997/001423 patent/WO1997041105A1/ja not_active Application Discontinuation
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