N-二茂铁甲酰基-N′-芳(烷)基硫脲的合成及光谱性质研究  

Synthetic and Spectroscopic Studies on N-Ferrocenoyl-N' - Aryl (alkyl) thioureas

作　　者：王积涛[1] 张蕴文[1] 许育明[1] 袁耀锋[1] 高生华[2] 

机构地区：[1]南京大学化学系,天津300071 [2]1992年内蒙古师范大学

出　　处：《高等学校化学学报》1993年第6期801-805,共5页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金;国家教委博士学科点专项基金

摘　　要：合成了二茂铁甲耽墓异硫氛酸始，并可与各种胺类(取代苯胺类，a-茶胺，低分于1的脂肪按，六红毗咬)反应，合成了未见报道的21种含二茂铁甲耽基的硫膝衍生物.本法简便，产物易分离提纯，产率高.二茂铁甲耽基异硫氛酸脂也可在低温(一5一0℃)下与强城性的脂肪胺在水溶液中石应.产物为经牙资夺娇_红夕卜产.讲_牙定磁共版讲确宁了里去构.In this paper, ferrocenoyl isothiocyanate is synthesized for the first time. Without being separated, it reacts with various amines, such as heterocyclic amines, aliphatic amines with lower molecular weight, α-naphthyl amine and aromatic amines containing various substituted groups. Twenty one N-ferrocenoyl-N'-Ary (alkyl) thiourea derivatives have been obtained in good yields. They can be conveniently isolated and purified. At a low temperature ( - 5-0℃ ) , ferrocenoyl-isoth-iocyanate reacts with aqueous solutions of free amines (i. e. 33% ethyl amine, 25% methyl amine) to form corresponding derivatives in fairly good yields. All the compounds have not been reported so far and their structures have been confirmed by elemental analysis, 1H NMR and IR.IR and JH NMR data show that the product exists in enol form and exibits intramolecular hydrogen bonding.-HS (R'=H, comp. 1~15, 18-21)The IR 1663 cm'1 (middle strong band) is generally found, it is lower than the normal carbonyl absorbtion due to ferrocene moiety as the electron donor which enhances the enolation and promotes the formation of intramolecular hydrogen bonding. The frequency coincides with the IR absorption of C=N in enol structure. In the region 3200-2500 cm'1 the IR shows broad band probably due to vibration of O-H; the IR 1146. 5 cm'1 shows strong single band duo to stretching of C-O single bond; in the region 3160-2840 cm'1 IR shows broad band due to the vibration of N-H. All the IR data indicate the structure of N-Ferrocenoyl-N'-Aryl(Alkyl) thioureas in solid state. Tautomers may be at equilibrium.In the ]H NMR spectra the chemical shifts of the mioety -CO-NH-CS- move down to 11. 3-13 ppm(l-15) or 10. 4-10. 72 ppm(18-21). These are due to the de-shielding of intramolecular hydrogen bonding. When R1=H, 'H NMR shift of N-H shows 8. 48-8. 88 ppm singlet, regardless of R2. The 1H NMR 12. 8 ppm indicates no-free hydroxy group due to intramolecular hydrogen bonding. For compound 8, the 12. 8 ppm is found in CDC13 at 25, 60 and 70℃ throughout the temp

关 键 词：胺类 硫脲 加成反应 二茂铁基 

分 类 号：O623.542[理学—有机化学]