Organic thiocyanates. XIX. Thiocyanation of phenol ethers was written by Pohloudek-Fabini, Roland;Luess, K. D.. And the article was included in Archives de Pharmacie (Paris) in 1966.Computed Properties of C11H14N2OS The following contents are mentioned in the article:
Thiocyanation of alkyl phenyl ethers with inorganic thiocyanates and Br gave low yields of thiocyanates because bromination occurred simultaneously. Alkyl aminophenyl ethers yielded mixtures of mono and dithiocyanato derivatives When heated or treated with acids, the o-aminothiocyanato derivatives isomerized to 2-aminobenzothiazoles. Unsubstituted alkyl thiocyanatophenyl ethers were prepared from the corresponding aminophenyl ethers by diazotization and treatment with KSCN, CuSCN, and CoCl2. Phenol ethers (0.1 mole) and 0.3 mole NaSCN or KSCN in AcOH, 100 g. NH4SCN in MeOH, or 0.5 mole NaSCN or KSCN in AcOMe were cooled and treated with 0.2 mole Br in the same solvent (compound used, product(s), m.p., and % yield in AcOH, MeOH, and AcOMe listed): PhOMe, 4-MeOC6H4SCN, 34-5°, 12, 0, -; PhOEt, 4-EtOC6H4SCN, 46-7.5°, 17, 0, -; PhOPr, 4-PrOC6H4SCN, 36-6.5°, 17, 0, -; PhOBu, 4-BuOC6H4SCN, 26-7°, 15, 0, -; o-anisidine, 1,2,5-MeO(H2N)C6H3SCN, 52-3°, 68, 41, 92; 1,2,3,5-MeO(H2N)C6H2(SCN)2, 101-3° and 233° (twice), 28, 56, 0, and 4-methoxy-6-thiocyanato-2-aminobenzothiazole, 233-5° (decomposition), 60, 0, 0; m-anisidine, 1,3,6-MeO(H2N)C6H3SCN, 109-11°, 39, 2, 22, and 1,3,4,6-MeO(H2N)C6H2(SCN)2, 155-7°, 84, 75, 47; p-anisidine, 1,4,3-MeO(H2N)C6H3SCN, 61-2 and 168°, 0, 0, 25, 6-methoxy-2-aminobenzothiazole, 169°, 91, 3, 3, and 6-methoxy-4-thiocyanato-2-aminobenzothiazole, 212-16° (decomposition), 15, 72, 0; o-phenetidine, 1,2,5-EtO(H2N)C6H3SCN, 82-3°, 79, 53, 75, and 1,2,3,5-EtO(H2N)C6H2(SCN)2, 103-6° and 228°, 30, 80, 0; m-phenetidine, 1,3,4,6-EtO(H2N)C6H2(SCN)2, 105-7.5°, 100, 100, 92; p-phenetidine, 1,4,3-EtO(H2N)C6H3SCN, 70-2 and 164°, 0, 0, 31, 6-ethoxy-2-aminobenzothiazole, 164-6, 89, 42, 0, and 6-ethoxy-4-thiocyanato-2-aminobenzothiazole, 206-12° (decomposition), 5, 31, 0; 1,4-PrOC6H4NH2, 6-propoxy-2-aminobenzothiazole, 137-9°, 67, 22, -; 1,4-BuOC6H4NH2, 6-butoxy-2-aminobenzothiazole, 120-1°, 26, 15, -. Thiocyanates prepared by diazotization were (starting material, product, m.p., and % yield listed): o-anisidine, 1,2-MeOC6H4SCN, – (b14 151-2°), 39; m-anisidine, 1,3-MeOC6H4SCN, – (b8 151-2°), 40; p-anisidine, 1,4-MeOC6H4SCN, 33-4°, 29; o-phenetidine, 1,2-EtOC6H4SCN, 23-4° (b7 122-31°), 14; m-phenetidine, 1,3-EtOC6H4SCN, – (b9 138-42°), 42; p-phenetidine, 1,4-EtOC6H4SCN, 44-6°, 17; 1,4-PrOC6H4NH2, 1,4-PrOC6H4NH2, 1,4-PrOC6H4SCN, 34-6° (b6 145°), 20; 1,4-BuOC6H4NH2, 1,4-BuOC6H4SCN, 25-6°, 25; 1,2,5-MeO(H2N)C6H3SCN, 1,2,5-MeOC6H3(SCN)2, 89-93.5°, 29; 1,2,3,5-MeO(H2N)C6H2(SCN)2, 1,2,3,5-MeOC6H2(SCN)3, 129-34°, 59; 1,3,4,6-MeO(H2N)C6H2(SCN)2, 1,3,4,6-MeOC6H2(SCN)3, 114-18.5°, 90 (putative); 1,3,4,6-EtO(H2N)C6H2(SCN)2, 1,3,4,6-EtOC6H2(SCN)3, 115-19°, 100 (putative); 4-methoxy-6-thiocyanato-2-aminobenzothiazole, 4-methoxy-2,6-dithiocyanobenzothiazole, 125-8°, 43; 6-methoxy-2-aminobenzothiazole, 6-methoxy-2-thiocyanobenzothiazole, 86-7°, 30; 6-ethoxy-2-aminobenzothiazole, 6-ethoxy-2-thiocyanatobenzothiazole, 84-8°, 80; 1,2,5-EtO(H2N)C6H3SCN, 1,2,5-EtOC6H3(SCN)2, 52-7°, 80 (putative). This study involved multiple reactions and reactants, such as 6-Butoxybenzo[d]thiazol-2-amine (cas: 14372-65-7Computed Properties of C11H14N2OS).
6-Butoxybenzo[d]thiazol-2-amine (cas: 14372-65-7) belongs to thiazole derivatives. The higher aromaticity of thiazole is due to delocalization of a lone pair of sulfur electrons across the ring, which is evidenced by chemical shifts of ring hydrogen at δ 7.27 and 8.77 ppm (C2 and C4), indicating diamagnetic ring current. Electrophilic attack at nitrogen depends on the presence of electron density at nitrogen as well as the position and nature of substituent linked to the thiazole ring.Computed Properties of C11H14N2OS
Referemce:
Thiazole | C3H3NS – PubChem,
Thiazole | chemical compound | Britannica