CN1106798A - 吡咯类的烷氧甲基化 - Google Patents

吡咯类的烷氧甲基化 Download PDF

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CN1106798A
CN1106798A CN94113271A CN94113271A CN1106798A CN 1106798 A CN1106798 A CN 1106798A CN 94113271 A CN94113271 A CN 94113271A CN 94113271 A CN94113271 A CN 94113271A CN 1106798 A CN1106798 A CN 1106798A
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R·F·德纳
J·M·巴顿
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Abstract

本发明提供经合适的吡咯前体相继地与二烷氧 基甲烷、Vilsmeier试剂和一种叔胺反应，使能在各种 吡咯化合物的环氮原子上引入烷氧甲基的一种安全 和有效的方法。产物1-(烷氧甲基)-吡咯作为杀昆 虫剂、杀螨剂、杀线虫剂和杀软体动物剂是有用的。

Description

吡咯腈、硝基吡咯、芳基吡咯、双芳基吡咯、硫代烷基吡咯、烷磺酰基吡咯、烷基亚磺酰基吡咯、硫代羧酰胺吡咯和杂芳基吡咯化合物及其衍生物是用于动、植物科学的高效杀昆虫剂、杀螨剂、杀线虫剂、杀软体动物剂和endecticidal剂。一般来说，上述在吡咯环的氮原子上有烷氧甲基取代的吡咯衍生物比其母核吡咯化合物更有效。
在吡咯的氮上烷氧甲基化生成N-（烷氧甲基）吡咯一般是在强碱如氢化钠〔i.e.J.Muchowski，et  al，Journal  of  Organic  Chemistry，49（1），p.203（1984）〕或叔丁醇钾（i.e.U.S.5，010，098）的存在下，经合适的吡咯与α-卤代甲醚缩合而达到。但是，由于α-卤代甲醚的严重致癌性，它在商业或小规模实验性工厂规模的生产上的使用是不合要求的。而且，大规模使用强碱如金属氢化物或叔丁氧化物是费钱和有害的。
人们知道用烷基醛和Vilsmeier试剂，得到苯酚羟基的烷氧甲醚，如U.S.4，500，738所描述的方法。但是，当应用于吡咯的环氮原子时，此方法是不成功的，无反应发生。
因此，本发明的一个目的是提供无须分开制备和处理α-卤代甲醚即可制取N-（烷氧甲基）吡咯的安全、有效的方法。
本发明的另一个目的是提供一种无须使用诸如金属氢化物或金属叔丁氧化物之类的强碱的吡咯烷氧甲基化方法。
本发明的进一步目的是提供各种重要的杀虫吡咯化合物的N-烷氧甲基衍生物的易得来源。本发明的更进一步的目的和特征从下面的描述中将更为明了。
本发明提供制备1-（烷氧甲基）吡咯化合物的安全有效方法，该方法包括在可任选的升高的温度下，在非质子传递溶剂中将1-H-吡咯化合物与二烷氧甲烷、二甲基甲酰胺和磷酰氯反应，生成反应混合物，并用一种叔胺处理反应混合物。
用本发明的方法可高产、高效地并大大减少对环境和人的危害性地制备各种杀虫用1-（烷氧甲基）吡咯化合物，如吡咯腈、硝基吡咯、芳基吡咯、双芳基吡咯、硫代烷基吡咯、烷磺酰基吡咯、烷基亚磺酰基吡咯、羧酰胺吡咯、硫代羧酰胺吡咯、杂芳基吡咯等。
吡咯化合物表现出很多有用的生物学特性，如杀细菌、杀真菌、杀螨虫、杀昆虫、杀软体动物和杀线虫性质。安全有效的将吡咯环上的氮衍生化的方法可大大地发展吡咯技术的医学和农业上的应用。特别是，表现农业杀虫性质的吡咯的烷氧甲基化有引起这些性质增强的倾向。然而，在吡咯环氮上的烷氧甲基化技术上至今所知的方法导致使用α-卤代甲醚（致癌）和/或诸如金属氢化物或金属烷氧化物（有害、价贵）之类强碱的使用和处理。
现已发现，在无强金属碱存在下，可使1-H-吡咯化合物在吡咯环上的氮上烷氧甲基化，得到高产量的1-（烷氧甲基）吡咯产物而无须分离或处理致癌性中间体，该方法系在非质子传递溶剂中将1-H-吡咯化合物与二-（C1-C6烷氧）甲烷和Vilsmeier试剂反应，生成反应混合物，随后连续加入一种叔胺到反应混合物中，生成所需要的1-（C1-C6烷氧甲基）吡咯化合物。
令人吃惊的是，向1-H-吡咯化合物、二-（C1-C6烷氧）甲烷和Vilsmeier试剂在非质子传递溶剂中的混合物随后持续地加入一种叔胺，使1-H-吡咯化合物极好地转变成相应的1-（C1-C6烷氧甲基）吡咯产物。
在本发明的一个实施方案中，式Ⅰ吡咯化合物
Figure 941132714_IMG6
其中
W为CN、NO2、S（O）nCR或
Figure 941132714_IMG7
X为氢、卤素、CN、NO2、S（O）mCR3、C1-C4卤代烷基、Q、或可任意地被1个或1个以上卤素、NO2、CN、C1-C4烷基、C1-C4卤代烷基、C1-C4烷氧基或C1-C4卤代烷氧基取代的苯基;
Y为氢、卤素、C1-C4卤代烷基或可任意地被1个或1个以上卤素、NO2、CN、C1-C4烷基、C1-C4卤代烷基、C1-C4烷氧基或C1-C4卤代烷氧基取代的苯基;
Z为氢、卤素或C1-C4卤代烷基;
n和m各自独立地为整数0、1或2;
R和R3各自独立地为整数C1-C6卤代烷基;
R1-R2各自独立地为整数C1-C4烷基、C1-C4卤代烷基或可任意地被1个或1个以上卤素、NO2、CN、C1-C4烷基、C1-C4卤代烷基、C1-C4烷氧基或C1-C4卤代烷氧基取代的苯基;
Q为
Figure 941132714_IMG8
R4、R5和R6各自独立地为氢、卤素、NO2、CHO或R5和R6可与它们所连的原子联在一起形成一个环，其中R5、R6以如下结构表示：
Figure 941132714_IMG9
R7、R8、R9和R10各自独立地为氢、卤素、CN或NO2;及
A和A1各自独立地为O或S
可安全有效地转化为式Ⅱ的1-（C1-C6烷氧甲基）吡咯化合物
其中W、X、Y和Z如上面对式Ⅰ所描述的，R11为C1-C6烷基。
在实际的实践中，将大致化学计算量的1-H-吡咯化合物、二-（C1-C6烷氧）甲烷、二甲基甲酰胺和磷酰氯在非质子传递溶剂中的混合物于0°-150℃（较好为20°-60℃）下搅拌约0.25-2.0小时;然后用约1-2摩尔当量叔（3°）胺于0-150℃（较好为0-60℃）下搅拌处理，直至反应完全，用水淬灭反应，得所需的1-（C1-C6烷氧甲基）吡咯产物。用如一个实施例中那样的1-H-吡咯化合物，反应如流程Ⅰ所示，其中DMF为二甲基甲酰胺，R11为C1-C6烷基。
流程Ⅰ
Figure 941132714_IMG11
虽然化学计算量的1-H-吡咯、二-（C1-C6烷氧）基甲烷、二甲基甲酰胺和磷酰氯是合适的，但以略过量的Vilsmeier试剂（DMF和POCl3）（约1.0-1.5摩尔当量）为好，约1.0-2.0摩尔当量二-（C1-C6烷氧）甲烷为好。化学计算是以所用的起始1-H-吡咯化合物为基准的。
适宜用于本发明方法的非质子传递溶剂是芳香烃、卤代芳香烃、脂族腈、醚等。较佳的非质子传递溶剂为甲苯、二甲苯、卤代苯和乙腈。
反应速率随温度升高而加快，但过高温度是不利的，会导致副反应和降低产量。适于本发明方法的温度在约0°-150℃的范围内，较佳为约20°-60°。
适用于本发明方法的叔胺包括现有技术中已知的任何三取代的胺，如三烷基胺、二烷基芳胺、三芳基胺等，较佳为三烷基胺，更佳为三乙胺。
令人注目的是，本发明的方法用于制备1-H-吡咯化合物的1-烷氧甲基衍生物。较佳的1-H-吡咯化合物是W、X、Y和Z定义如上的式Ⅰ化合物。更佳的式Ⅰ化合物为这样的化合物，其中W为CN或NO2;X为氢、卤素或C1-C4卤代烷基;Y为氢、卤素或C1-C4卤代烷基;及Z为卤素、C1-C4卤代烷基或可被11个或1个以上卤素或C1-C4卤代烷基任意取代的苯基。
用本发明方法获得的较佳的式Ⅱ产物为那些化合物，其中R11为C1-C6烷基;W为CN或NO2;X为卤素或C1-C4卤代烷基;Y为卤素或C1-C4卤代烷基;及Z为可被1个或1个以上卤素或C1-C4卤代烷基任意取代的苯基。更佳的式Ⅱ化合物为那些化合物，其中R11为C1-C3烷基（特别是C2H5）;W为CN;X为卤素;Y为CF3;及Z为可被1个氯原子或溴原子任意取代的苯基。
为了提出更清楚的对本发明的理解，将下面的实施例阐述如下。这些实施例仅仅是说明性的，无论如何不能理解为对本发明范围和基本原则的限制。
术语HPLC和1HNMR分别表示高效液相色谱和质子核磁共振。
实施例1
4-溴-2-对氯苯基-1-乙氧甲基-5-三氟甲基吡咯-3-腈的制备
Figure 941132714_IMG12
在氮气中将搅拌下的4-溴-2-对氯苯基-5-三氟甲基吡咯-3-腈（17.4克，0.05摩尔）、二乙氧基甲烷（10.4克，0.10摩尔）和二甲基甲酰胺（DMF）（4.6克，0.0625摩尔）在甲苯中的混合物分批用磷酰氯（9.6克，0.0625摩尔）于35°-45℃下处理10分钟，45°-53℃加热约0.5小时，冷却至35℃，于35°-45℃历时2小时用三乙胺（7.25克，0.0715摩尔）滴加处理。用水处理反应混合物，共沸蒸馏除去甲苯。留下的残渣用水处理，过滤，滤饼在60℃真空干燥，得标题产物，20.8克，经HPLC分析鉴定，纯度92.7%，得率94.6%。
基本上用同样的方法，用下面的溶剂代替甲苯，得到如下得率的标题产物。
溶剂    得率（%）
乙腈    94.7
二甲苯    96.4
氯苯    93.6
实施例2
4-溴-1-正丁氧甲基-2-对氯苯基-5-三氟甲基吡咯-3-腈的制备
Figure 941132714_IMG13
将搅拌下的4-溴-2-对氯苯基-5-三氟甲基吡咯-3-腈（17.4克，0.05摩尔）、二正丁氧基甲烷（12.0g，0.075摩尔）和二甲基甲酰胺（DMF）（4.6克，0.063摩尔）在二甲苯中的混合物在氮气中用磷酰氯（9.6克，0.063摩尔）于30°-37℃下分批处理10分钟，45-50℃加热0.75小时，冷却至35℃，历时0.25小时用三乙胺（8.1克，0.08摩尔）滴加处理，于45°-50℃下再加热0.75小时。然后将反应混合物冷却至25℃，用水和外加的二甲苯处理，搅拌0.5小时。进行相分离，有机相真空浓缩，得浅棕色固体标题产物，经1HNMR和质谱分析，mp52.0℃-53.5℃，20.6g，得率94.6%。
实施例3
4-溴-2-对氯苯基-1-甲氧甲基-5-三氟甲基吡咯-3-腈的制备
Figure 941132714_IMG14
基本上用实施例2中所述同样的方法，用二甲氧基甲烷替换二正丁氧基甲烷，得标题产物，得率66%，用1HNMR和质谱分析鉴定。
实施例4
2-对氯苯基-1-乙氧基甲基-5-三氟甲基吡咯-3-腈的制备
在氮气中将搅拌下的-2-对氯苯基-5-三氟甲基吡咯-3-腈（13.5克，0.05摩尔）、二乙氧甲烷（7.8g，0.075摩尔）和二甲基甲酰胺（DMF）（5.5克，0.075摩尔）在乙腈中的混合物用磷酰氯（11.5克，0.075摩尔）于39°-45℃处理0.25小时，39-45℃加热0.75小时，于45°-55℃下历时0.5小时用三乙胺（10.1克，0.10摩尔）滴加处理。将反应混合物用水稀释，25℃下搅拌16小时，真空浓缩，得粗产品。将此粗物质在回流温度下与甲苯和稀NaOH水溶液的混合物一起搅拌，冷却至室温。进行相分离，有机相真空浓缩，得固体标题产物，经质谱分析鉴定，mp83-84.5℃，13.1g，得率80%。

Claims (10)

1、1-烷氧甲基吡咯化合物的制备方法，其特征在于：在任选的升高的温度下，在非质子传递溶剂的存在下，将1-H-吡咯化合物与二烷氧基甲烷、二甲基甲酰胺和磷酰氯反应，形成反应混合物，将反应混合物用一种叔胺处理。
2、如权利要求1所述的方法，其中1-H-吡咯化合物为式Ⅰ化合物
Figure 941132714_IMG1
其中
W为CN、NO2、S（O）nCR或
X为氢、卤素、CN、NO2、S（O）mCR3、C1-C4卤代烷基、Q、或可任意地被1个或1个以上卤素、NO2、CN、C1-C4烷基、C1-C4卤代烷基、C1-C4烷氧基或C1-C4卤代烷氧基取代的苯基;
Y为氢、卤素、C1-C4卤代烷基或可任意地被1个或1个以上卤素、NO2、CN、C1-C4烷基、C1-C4卤代烷基、C1-C4烷氧基或C1-C4卤代烷氧基取代的苯基;
Z为氢、卤素或C1-C4卤代烷基;
n和m各自独立地为整数0、1或2;
R和R3各自独立地为整数C1-C6卤代烷基;
R1-R2各自独立地为整数C1-C4烷基、C1-C4卤代烷基或可任意地被1个或1个以上卤素、NO2、CN、C1-C4烷基、C1-C4卤代烷基、C1-C4烷氧基或C1-C4卤代烷氧基取代的苯基;
Q为
R4、R5和R6各自独立地为氢、卤素、NO2、CHO或R5和R6可与它们所连的原子联在一起形成一个环，其中R5、R6以如下结构表示：
Figure 941132714_IMG4
R7、R8、R9和R10各自独立地为氢、卤素、CN或NO2;及
A和A1各自独立地为O或S。
3、按权利要求2所述的方法，其中
W为CN或NO2;
X为卤素、C1-C4卤代烷基或可被1个或1个以上卤素或C1-C4卤代烷基任意取代的苯基;
Y为氢、卤素或C1-C4卤代烷基;及
Z为氢、卤素或C1-C4卤代烷基。
4、按权利要求1所述的方法，其中非质子传递溶剂为芳香烃或脂族腈。
5、按权利要求4所述的方法，其中溶剂为甲苯、二甲苯或乙腈。
6、按权利要求1所述的方法，其中叔胺为三（C1-C6烷基）胺。
7、按权利要求6所述的方法，其中胺为三乙胺。
8、如权利要求1所述的方法，其中1-烷氧甲基吡咯化合物为1-（C1-C6烷氧甲基）吡咯化合物，二烷氧甲烷为二-（C1-C6烷氧基）甲烷。
9、按权利要求8所述的方法，其中二-（C1-C6烷氧基）甲烷为二乙氧基甲烷。
10、如权利要求9所述的方法，其中1-H-吡咯化合物具有如下结构。
Figure 941132714_IMG5
CN94113271A 1993-12-29 1994-12-22 吡咯类的烷氧甲基化 Expired - Fee Related CN1055464C (zh)

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CN109006823A (zh) * 2018-09-11 2018-12-18 江苏省血吸虫病防治研究所 2-芳基取代吡咯类化合物在杀钉螺药物中的应用
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CN110382462A (zh) * 2017-03-13 2019-10-25 巴斯夫农业公司 在dipea碱存在下生产芳基吡咯化合物
CN109006824A (zh) * 2018-09-11 2018-12-18 江苏省血吸虫病防治研究所 2-芳基取代吡咯类化合物在杀双脐螺药物中的应用
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