Clark, Robert L.; Pessolano, Arsenio A. published the artcile< Synthesis of some substituted benzimidazolinones>, Name: (9Z,12Z)-Methyl octadeca-9,12-dienoate, the main research area is .
The appropriate aromatic ο-diamine in aqueous HCl treated with COCl2 until the precipitate formation was complete, filtered, and the precipitate with H2O gave the corresponding substituted 2-benzimidazolinone (I) (substituents and m.p. given): 4-Me, 302-3° (MeOH); 4,7-di-Me, 337° (AcOH); 5-Et, 264-5° (EtOH); 4-Et, 261-2° (EtOH); 5-Pr, 239-41° (aqueous EtOH); 5-iso-Pr, 270-2° (EtOH); 5-Bu, 250° (aqueous EtOH); 5-EtMeCH, 253-4° (aqueous EtOH); 5-Me3C, 310° (aqueous EtOH); 5-EtMe2C, 284-5° (aqueous EtOH); 5-MePrCH, 217-18° (EtOAc); 5-C6H13, 250-2° (EtOAc); 5-Ac, 296-7° (aqueous EtOH); 5-HO, 307-9° (aqueous EtOH); 5-MeO, 256-7° (EtOH); 5-F, 303° (aqueous EtOH); 4-iso-Pr, 7-Br, 245-9° (aqueous EtOH); 5-Br, 336-7° (AcOH); 4-Cl, 335-6° (aqueous EtOH); 1-Et, 5-Me, 115° (aqueous EtOH); 1-Ph, 206-7° (EtOH); 1,5-di-Me, 197-9° (aqueous EtOH); 1-Et, 117-18° (Et2O-petr. ether); 4,5-CH:CHCH:CH, above 345° (HCONMe2-Et2O). The appropriate aromatic ο-diamine (1.0 mole) (or its HCl salt) and 1.1 moles urea heated at 140° or higher during 15 min., cooled, dissolved in 2.5N NaOH, filtered, acidified with concentrated HCl, and the base-acid treatment repeated or the precipitate recrystallized gave the corresponding I (same data given): 5,6-di-Me, above 345° (AcOH); 5-Ph, 350° (AcOH); 5,6-di-MeO, 268° (dioxane); 4,6-di-Cl, above 340° (aqueous dioxane); 5,6-di-Cl, 345° (reprecipitated); 4,5,6-tri-Cl, 342° (reprecipitated). The appropriate nitro compound in EtOH hydrogenated at 40 lb. over 5% Pd-C, filtered, and evaporated (or treated with dry HCl) gave the corresponding amino analog (m.p. given): 5-amino-1,3-dimethylbenzimidazolone-0.5-H2O.HCl, 310° (MeOH-Et2O); 5-aminobenzimidazolone-HCl, above 340° (EtOH-Et2O). The following substituted ο-phenylenediamines (substituent and m.p. given): 4-Et.2HCl, 308° (EtOH-Et2O); 3-Et.HCl, 258° (EtOH); 4-Pr.2HCl, 206-10° (EtOH-Et2O); 4-iso-Pr.2HCl, 267° (aqueous EtOH); 4-Bu.2HCl, 235° (EtOH); 4-EtMeCH.2HCl, 249-51° (EtOH-Et2O); 4-MePrCH.2HCl, 214-17° (EtOH); 4-Ac.HCl, 280-7° (aqueous EtOH); 4-MeO.2HCl, 227° (EtOH-Et2O); 4,5-di-MeO.HCl, 230-50° (aqueous MeOH); 4,2-Me(H2N)C6H3NHEt.2HCl, 178-80° (EtOH); ο-H2NC6H4NHEt.HCl, 188-93° (EtOH-Et2O). SnCl2.2H2O (100 g.) in 180 cc. concentrated HCl treated portionwise with stirring with 30 g. 4,2-Ph(O2N)C6H3NH2 below 40°, stirred 2 hrs., kept at room temperature overnight, added below 10° to 350 g. NaOH in about 800 cc. cold H2O, filtered after 3 hrs., and the residue reprecipitated from 700 cc. hot EtOH with H2O gave 20 g. 3,4-(H2N)2C6H3Ph, m. 102-3°. 4,2-iso-Pr(O2N)C6H3NHAc (17.5 g.) in 125 cc. concentrated HCl heated 3 hrs. on the steam bath, cooled to 50°, treated slowly with stirring with 75 g. SnCl2.2H2O in 30 cc. H2O and 15 cc. concentrated HCl, cooled to room temperature, treated with C, filtered, and treated directly with COCl2 gave 5-isopropylbenzimidazolinone. The appropriate benzimidazolinone refluxed 3 hrs. with 5 parts acid anhydride and cooled gave the corresponding I (substituents and m.p. given): 1-Me, 3-Ac, 120-1° (EtOH); 1-Ph, 3-Ac, 137-8° (EtOH); 1,3-di-Ac, 5-AcNH, 260-1° (aqueous AcOH; 1,3-di-Ac, 5-Me3C, 127-30° (EtOAc-petr. ether); 1,3-di-EtCO, 169-70° (EtOAc); 1,3-di-Ac, 5-Cl, 172-3° (EtOAc); 1,3-di-Ac, 5-NO2, 131-2° (EtOH); 1,3-di-Ac, 5,6-di-Cl, 218-19° (dioxane); 1-Ac, 3-Me, 120-1° (EtOH); 1-Me, 3-AcOCH2, 115-16° (EtOAc). Benzimidazolinone (152 g.) and 365 g. powd. KOH in 2000 cc. Me2CO refluxed with stirring, the mixture treated dropwise with 432 g. MeI in 350 cc. Me2CO, heated 10 min., decanted, the pasty residue extracted 3 times with Me2CO, the extract evaporated, and the crystalline material recrystallized from 450 cc. hot C6H6 by the slow addition of 100 cc. petr. ether gave 122 g. 1,3-dimethylbenzimidazolinone, m. 111-12°; 39 g. 2nd crop. Similarly were prepared the following I (same data given): 1,3-di-(CH2CH:CH2), 53-4° (petr. ether); 1,3-di-(PhCH2), 107-8° (Et2O); 1,3-di-Me, 5-Me3C, 180-1° (aqueous EtOH); 1,3-di-Me, 5-iso-Pr, 142-3° (aqueous EtOH); 1,3-di-(CH2CMe:CH2), 85-6° (Et2O-petr. ether); 1,3,5,6-tetra-Me, 153-4° (EtOAc); 1,3-di-Me, 5-Cl, 163-41° (aqueous EtOH); 1,3,5-tri-Me, 103-5° (Et2O-petr. ether); 1,3-di-Me, 5-MeO, 92-3° (C6H6-petr. ether); 1,3-di-Et, 68-9° (petr. ether); 1,3-di-(PhCH2CH2), 74-5° (Et2O-petr. ether); 1,3-di-Me, 5-Br, 166-7° (EtOH); 1,3-di-Me, 5-EtO, 104-5° (aqueous EtOH); 1,3-di-(BzCH2), 197-8° (aqueous AcOH); 1,3-di-(Me2NCH2CH2).2HClO4, 238° (aqueous EtOH); 1,3-di-(EtO2CCH2), 169-70° (EtOH); 1,3-di-(Et2NCH2CH2), 5-Me3C.2HClO4, 140° (aqueous EtOH); 1,3-di-(Et2NCH2CH2).2HClO4, 142-3° (MeOH); 1,3-di(Et2NCH2CH2), 4,6-di-Me.2HClO4, 201-3° (aqueous EtOH); 1,3-di-(Me2NCHMeCH2.).2HClO4, 229-30° (aqueous EtOH); 1,3-di-(Et2NCH2CH2), 5-MeO.2HClO4, 160-2°; 1,3-di-Me, 5-NO2, 208-9° (EtOAc); 1,3-di-Me, 5-H2NCONH, 350° (aqueous AcOH). The following I (substituents and m.p. given) were prepared by the method of Vaughan and Blodinger (C.A. 50, 8606g): 5-BuCO, 269-71° (aqueous EtOH); 5-iso-BuCO, 268-70° (EtOH); 5-C7H15CO, 246-7° (EtOH); 5-C13H27CO, 229° (EtOH). 5-Myristoylbenzimidazolinone (100 g.) in 1500 cc. EtOH hydrogenated 3.5 hrs. at 225° over 10 g. Cu chromite, filtered, extracted with hot dioxane, and the filtered extract cooled gave 65 g. 5-tetradecylbenzimidazolinone, m. 226° with previous softening (AcOH). Similarly were prepared the following I (substituent and m.p. given): 5-Am, 261-4° (aqueous EtOH); 5-iso-Am, 256-9° (aqueous EtOH); 5-C8H17, 240-2° (EtOH). p-AcNHC6H3Ac (47 g.) in 150 cc. AcOH and 50 cc. Ac2O treated with stirring with 23 cc. fuming HNO3 at 40°, stirred 1 hr., poured into 1500 cc. H2O, and the gummy precipitate (45 g.) crystallized from 115 cc. AcOH gave 20 g. 4,3-AcNH(O2N)C6H3Ac, m. 140-1°. In the same manner were prepared the following substituted benzenes (m.p. given): 4,2-Pr(O2N)C6H3NHAc, 135° (aqueous EtOH); 3,2-iso-Pr(O2N)C6H3NHAc, 81-2° (aqueous EtOH); 4,2-EtMe2C(O2N)C6H3NHAc, 53-4° (petr. ether); 4,2-C6H13(O2N)C6H3NHAc, 51-2° (aqueous EtOH); 4,2-F(O2N)C6H3NHAc, 72-3° (aqueous EtOH); 4,5,2-Br(iso-Pr)(O2N)C6H2NHAc, 139-41°. p-MePrCHC6H4NH2 acetylated in the usual manner gave the N-Ac derivative, m. 122-4° (Et2O-petr. ether). Similarly was prepared p-C6H13C6H4NHAc, m. 74-6° (petr. ether). The appropriate acylamine heated 3 hrs. with HCl or with NaOMe by the method of Verkade and Witjens (C.A. 38, 23228) gave the corresponding amine; in this manner was prepared 4,2-Pr(O2N) C6H3NH2, m. 59-60° (aqueous EtOH). By catalytic hydrogenation of the corresponding 6-Br compound was prepared the 5-iso-Pr derivative, m. 232-3° (aqueous EtOH), of benzimidazolinone (II). The 5-NH2 derivative of II in acid treated with KOCN gave the 5-NHCONH2 derivative of II, m. 345° (reprecipitated). II, EtCOCl, and PhNO2 refluxed 4 hrs. gave the 1-EtCO derivative of II, m. 212-13° (EtOH). 1-Me derivative of II refluxed with aqueous CH2O gave the 3-CH2OH derivative, m. 153-4° (EtOH). The 5-Me3C derivative of II was converted by the method of Monti (C.A. 38, 45991 to the 1-xanthyl derivative, m. 253-4° (EtOAc). 1,3-Di-(HO2CCH2) derivative of II, m. 291-2° (EtOH), was prepared by hydrolysis of the di-Et ester. 5,6-Di-NO2 derivative of II reduced and the resulting diamine treated with COCl2 gave the 5,6-(NHCONH) derivative of II.0.5H2O, m. above 340° (EtOH).
Journal of the American Chemical Society published new progress about 112-63-0. 112-63-0 belongs to class esters-buliding-blocks, and the molecular formula is C19H34O2, Name: (9Z,12Z)-Methyl octadeca-9,12-dienoate.
Referemce:
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics