新型含咪唑啉2,4-二酮的磷酰胺类化合物的合成和生物活性  

Synthesis and Biological Activity of Novel Phosphoramide with Hydantoin

作　　者：王进敏[1] 徐志红[1,2] 韩金涛[1] 董宏波[1] 刘斌[1] 王明安[1] 

机构地区：[1]中国农业大学应用化学系,北京100193 [2]长江大学农学院,荆州434205

出　　处：《有机化学》2013年第10期2186-2195,共10页Chinese Journal of Organic Chemistry

基　　金：“十二五”科技支撑计划(No.2011BAE06B03);国家自然科学基金(No.20772150);南开大学元素有机化学国家重点实验室开放基金(Nos.0902,201003)资助项目~~

摘　　要：在合成含咪唑啉2,4-二酮磷酸酯和磷酰胺酯类化合物的基础上,将5-[4-氨基-苯(苄)基]-2,4-咪唑啉二酮中间体与O,O-二烷(芳)基硫代磷酰氯反应合成得到了38个结构新颖的O,O-二烷(芳)基-5-[4-氨基-苯(苄)基]-2,4-咪唑啉二酮硫代磷酰胺类化合物,其结构通过1H NMR,31P NMR,IR,元素分析和X射线衍射表征.化合物9b:C14H20N3O3PS21/3H2O,Mr=379.43,三斜晶系,P-1空间群,a=0.82092(5)nm,b=1.79810(14)nm,c=2.0153(2)nm,α=72.289(8)°,β=79.355(7)°,γ=77.288(6)°,V=2.7421(4)nm3,Dc=1.379 g/cm3,Z=6,F(000)=1196,μ(Mo Kα)=0.397 mm-1,S=1.031,final R=0.0426,wR=0.0797.初步生物测定结果表明化合物O,O-二甲基-5-(4-氨基苯基)-2,4-咪唑啉二酮硫代磷酰胺(7a),O-乙基-O-苯基-5-(4-氨基苄基)-2-硫代-2,4-咪唑啉二酮硫代磷酰胺(9n)和O,O-二甲基-5-(3-氨基苯基)-2-硫代-2,4-咪唑啉二酮硫代磷酰胺(11a)在100μg/mL浓度下对油菜的抑制率分别为75.4%,80.5%,81.7%,其中11个化合物对蚜虫的LD50值在182.41~368.52μg/mL之间,表现了良好的杀虫活性.Based on the synthesis of phosphates and phosphorylamidates with hydantoin, thirty and eight new O,O-dialkyl- （aryl）-5-[4-aminophenyl（benzyl）]-2,4-imidazolidinedione thiophosphoramide derivatives with hydantoin were synthesized by the reaction of O,O-dialkyl（aryl） thiophosphoryl chloride with 5-（4-aminophenyl）- and 5-（4-aminobenzyl）-2,4-imidazolidine- dione intermediates, and their structures were confirmed by ~H NMR, 3~p NMR, IR, elemental analysis and X-ray diffraction. 9b： C14H20N303PSE＇l/3H2O, Mr=379.43, triclinic, space group P-l, a=0.82092（5） nm, b= 1.79810（14） nm, c=2.0153（2） nm, a=72.289（8）~, fl=79.355（7）~, ~,=77.288（6）~, V----2.7421（4） nm3, De-----1.379 g/cm3, Z=6, F（000）= 1196,/^（Mo Kct）= 0.397 mm-1, S=1.031, final R=0.0426, wR----0.0797. The preliminary bioassay showed that O,O-dimethyl-5-（4-amino- phenyl）-2,4-imidazolidinedione thiophosphoramide （7a）, O-ethyl-O-phenyl-5-（4-aminobenzyl）- 2,4-imidazolidine-dione thio-phosphoramide （9n） and O,O-dimethyl-5-（3-aminophenyl）-2-thio-2,4-imidazolidinedione thiophosphoramide （lla） have inhibitory rates 75.4%, 80.5% and 81.7% against Brasica campestris at the concentration of 100 ~tg/mL, while eleven com- pounds showed excellent insecticidal activities against Myzus Persicae with the LD50 data in the range of 182.41~368.52 i.tg/mL, respectively.

关 键 词：咪唑啉 2 4-二酮 硫代磷酰胺 腺苷酸琥珀酸合成酶 生物活性 

分 类 号：TQ457.2[化学工程—农药化工]