Stetter, Hermann; Rauscher, Elli published the artcile< Compounds with urotropine structure. XVII. Adamantane-1-carboxylic acid>, Computed Properties of 112-63-0, the main research area is .
A series of reactions of adamantane-1-carboxylic acid (I), its acid chloride (II), and its Et ester (III) was described. [R = 1-adamantyl throughout this abstract]. RBr (12 g.) in 360 cc. concentrated HCl cooled to 10°, treated dropwise with stirring with 50 cc. HCO2H, stirred 4 h., filtered, poured onto ice, and filtered gave 96% I. I (10 g.) and 20 cc. SOCl2 refluxed 0.5 h. and evaporated, the residue treated with 10 cc. C6H6, the C6H6 distilled, and this procedure repeated gave nearly 100% II. II from 3.6 g. I in 25 cc. dry Et2O added dropwise with stirring and cooling to 4.0 g. PhNH2 in 30 cc. dry Et2O, the mixture stirred 0.5 h., evaporated, the residue extracted with dilute HCl and H2O, and recrystallized from aqueous MeOH gave 4.2 g. anilide of I, m. 197°. I (10.0 g.) and 20 cc. Ac2O distilled to 120° vapor temperature, treated again with 10 cc. Ac2O, the distillation repeated, the excess Ac2O removed in vacuo, and the residue cooled gave 6.0 g. anhydride of I, m. 229° (petr. ether). III (10 g.), 25 cc. 80% N2H4.H2O, and 100 cc. (HOCH2CH2)2O refluxed 30-40 h., cooled, diluted with 300 cc. H2O, and filtered gave 8.7 g. hydrazide (IV) of I, m. 156-7° (aqueous MeOH). NaOH (1.35 g.) in 4.0 cc. H2O and 6.1 g. II in 10 cc. dry Et2O added dropwise simultaneously with stirring to 1.44 g. NaOH in 15 cc. H2O and 2.0 g. N2H4.H2SO4, the mixture stirred briefly, and filtered yielded 7.2 g. (NHO2CR)2, m. 255-6° (aqueous MeOH). IV (6.0 g.) in 60 cc. dry C5H5N treated with stirring and cooling during 15 min. with 6.0 g. p-MeC6H4SO2Cl in portions, stirred 2 h. at room temperature, and poured into 400 cc. 2N HCl gave nearly 100% p-MeC6H4SO2NHNHOCR (V), m. 192°. III (22.5 g.) in 50 cc. dry xylene added dropwise with stirring during 2 h. to 5.0 g. Na in 200 cc. dry xylene under N, heated 1 h. with stirring, cooled, treated dropwise with stirring with 10 cc. concentrated H2SO4 in 50 cc. H2O, diluted with H2O, the aqueous phase extracted with xylene, and the combined xylene solutions washed, dried, and evaporated gave 14.5 g. RCOCH(OH)R (VI), m. 223-4° (glacial AcOH). VI (6.5 g.) in THF added with stirring to 0.5 g. LiAlH4 in 100 cc. dry THF, refluxed 0.5 h., and worked up gave 6.2 g. (RCHOH)2 (VII), m. 257-65° (AcOH), apparently a mixture of isomers. V (11.0 g.) in 200 cc. (CH2OH)2 treated at 160-5° with 11 g. Na2CO3, diluted with 200 cc. H2O after 5 min., cooled, extracted with Et2O, the extract worked up, and the distillate, b0.01 130-40°, (2.5 g.) dissolved in EtOH and treated with 2,4-(O2N)2C6H3NHNH2 gave 1.4 g. 2,4-(O2N)2C6H3NHN:CHR (VIII), m. 225°. VII (2.0 g.) in 150 cc. dry C6H6 and 1 cc. glacial AcOH treated with stirring at 60° during 0.5 h. with 4 g. Pb(OAc)4 in small portions, cooled, filtered, evaporated in vacuo, and the residue in EtOH treated with excess 2,4-(O2N)2C6H3NHNH2 gave 2.6 g. VIII, m. 225°. Similarly was prepared H2NCONHN:CHR, m. 226°. VI (5.0 g.) in 80 cc. glacial AcOH and 0.5 g. concentrated H2SO4 treated with stirring with 0.8 g. CrO3 in 10 cc. 70% AcOH at 30-50°, the mixture poured onto ice, extracted with Et2O, and the extract worked up gave (RCO)2, m. 219° (AcOH). VII (1.0 g.) in 10 cc. concentrated H2SO4 kept 2 days at room temperature, poured into iced H2O, and filtered yielded about 90% RCO-CH2R, m. 277-8° (EtOH). CdCl2 (9.7 g.) added with stirring to PhMgBr from 2.5 g. Mg and 16.2 g. PhBr in 100 cc. absolute Et2O, warmed to room temperature, refluxed 1.5 h., the Et2O distilled, the residue treated with 50 cc. dry C6H6, the suspension refluxed 1 h. with stirring, cooled, treated with ice and then 20% H2SO4, the C6H6 layer worked up, and the residue dissolved in a little MeOH and cooled to -78° gave 9.0 g. BzR, m. 55-6°. The Friedel-Crafts reaction with II and C6H6 gave as the only product RPh. BzR (0.5 g.), 0.5 g. NH2OH.HCl, and 2.0 g. KOH in 10 cc. EtOH refluxed 2 h., cooled, diluted with an equal volume of H2O, and filtered gave 100% RPhC:NOH, m. 224° (dioxane). BzR (0.5 g.) in 10 cc. EtOH treated with a solution of 0.5 g. 2,4-(O2N)2C6H3NHNH2, the mixture kept some time, and filtered gave 100% 2,4-(O2N)2C6H3NHN:CRPh, m. 242-4° (EtOAc-EtOH). III (7.0 g.) in 15 cc. dry Et2O added dropwise during 0.5 h. with cooling to PhMgBr from 2.0 g. Mg and 12.5 g. PhBr in 35 cc. dry Et2O, the mixture refluxed 3-4 h. with stirring, cooled, treated with stirring with iced H2O and HCl, worked up in the usual manner, and the sirupy residue digested with a little MeOH gave 5.8 g. Ph2C(OH)R, m. 127-8°, also obtained in 70% yield from 5.0 g. IV with PhMgBr from 2.5 g. Mg and 16.2 g. PhBr in Et2O. Ph2C(OH)R (5.0 g.), 30 cc. SOCl2, and 20 cc. AcCl mixed, refluxed 0.5 h., and evaporated gave 3.8 g. Ph2CClR, m. 150-2° (petr. ether). Ph2CClR (0.5 g.) in 5 cc. dry refluxing THF treated during 10 min. with 3 cc. absolute MeOH, the mixture refluxed 1 h., cooled, and filtered gave 0.45 g. Ph2C(OMe)R, m. 202° (petr. ether).
Chemische Berichte published new progress about 112-63-0. 112-63-0 belongs to class esters-buliding-blocks, and the molecular formula is C19H34O2, Computed Properties of 112-63-0.
Referemce:
Ester – Wikipedia,
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