The C-X Bond Formation Research Based On Dimethyl-Dithiocarbamic Acid Phenyl Ester

N-containing organic compounds and S-containing organic compounds play a very important role in natural products,since these N/S-containing compounds are universal in natural products and show important pharmacological activity and physiological activity in medicine,pesticides,et al.The primary amines or secondary amines are mainly chosen as the nitrogen source to synthesize the N-containig compounds through the N-H bond cleavage.Thiophenol or aryl sulfur compounds are usually the sulfur source to get S-containing organic compounds.This thesis studied the C-N/C-S formation reations based on dithiocarbamate,mainly are the following 4 sections.1.The NaH promoted C-N bond formation reaction was studied by using the substituted arylanlilines and dithiocarbamates as starting materials,a series of1,1-dimethyl-3-aryl-thioureas were synthesized in the presence of NaH.The protocol,which let the reactions undergo in a smooth,rapid way(3.5-5 hours)and then give the corresponding arylthioureas in good yields(67%~92%).The method could also be applied in the anilines containing halogen atoms at the ortho position,which could be transformed to benzothiazoles.2.The copper catalyzed C-S bond formation reaction starting from arylthioureas and iodinated benzenes was studied.To our delight,the coupling site is not the desired N site,but the unexpected S site which is from the isomerized isothiourea.A series of aryl isothioureas could be synthesized with good isolation yield(63%~88%),the protocol is easy to handle and shows very good expanding to the substrates.3.The copper catalyzed C-S bond formation reaction starting from arylthioureas and pheylboric acids was studied.Again,he coupling site is not the desired N site,but the unexpected S site which is from the isomerized isothiourea.A series of aryl isothioureas could be synthesized with good isolation yield(72%~89%).The protocol can be performed in water,conducted easily and effectively,showing very good universality to the substrates.4.Starting from arylthioureas and benzoyl chloride compounds,the C-N bond formation reaction with catalyst-free and ligand free was investigated.A series of substituted amides were synthesized with in the presence of K2CO3/DMAC system.The protocol,which let the reactions undergo in a smooth,rapid way(5-7 hours)and then give the corresponding arylthioureas in good yields(70%~86%).The method The protocol is easy to handle,showing economic and environmentally green properties,offering a new approach for the synthesis of substituted aryl amides.