On March 23, 2017, Watanabe, Atsushi; Sato, Yuuki; Ogura, Keiji; Tatsumi, Yoshiyuki published a patent.Synthetic Route of 25813-24-5 The title of the patent was Preparation of biaryl derivatives as antifungal agents and medicine containing them. And the patent contained the following:
Biaryl derivatives represented by general formula I (ring A, X1, X2, X3, Y, Z, R2a, R3, and Q are defined below) or salts thereof having excellent antifungal activity against Trichophyton, which is a major causative organism of superficial mycoses. Ring A, X1, X2, X3, Y, Z, Q, and R3 are defined as [ring A = each (un)substituted Ph or 5- or 6-membered heteroaryl each optionally fused to form (un)substituted condensed ring; Q = CH2, CF2, S(O), SO2, C(O), NH, or S; X1, X2, X3 = CR1 or N; Y = CH or N; Z = CR2b or N; R1 = H, halo, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy, or C1-6 haloalkoxy; R3 = H, halo, or each (un)substituted C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy, C1-6 haloalkoxy, C3-7 cycloalkyl, C2-6 alkenyl, C2-6 alkynyl, or aralkyl]. R2a and R2b are defined as [R2a, R2b = H, halo, HO, cyano, formyl, pentafluorosulfanyl, Q1, or each (un)substituted C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy, C1-6 haloalkoxy, C1-4 alkoxy-C1-4 alkyl, C1-4 alkoxy-C1-4 haloalkyl, C1-6 alkyl carbonyl, C1-6 alkoxycarbonyl, C1-6 alkylcarbonyloxy, C3-7 cycloalkyl, heterocycloalkyl, heterocycloalkyloxy, C2-6 alkenyl, C2-6 alkenyloxy, C2-6 alkenyl-C1-6 alkyl, C2-6 alkenyl-C1-6 alkoxy, C2-6 alkenyloxy-C1-4 alkoxy, C2-6 alkenyloxy-C1-4 haloalkyl, C2-6 alkenyloxy-C1-4 haloalkoxy, C2-6 alkynyl, C2-6 alkynyloxy, C2-6 alkynyl-C1-6 alkyl, C2-6 alkynyl-C1-6 alkoxy, C2-6 alkynyloxy-C1-4 alkyl, C2-6 alkynyloxy-C1-4 alkoxy, C2-6 alkynyloxy-C1-4 haloalkyl, C2-6 alkynyloxy-C1-4 haloalkoxy, NH2, C1-6 alkylthio, C1-6 haloalkylthio; ring B = each (un)substituted carbocyclic or heterocyclic ring; L = a single bond, (CH2)p, O(CH2)p, (CH2)pO, (CH2)pO(CH2)q, NRc(CH2)p , (CH2)pNRc, or (CH2)pNRc(CH2)q; p, q = 1, 2, or 3; one or a plural number of H atoms of each (CH2)p or (CH2)q is optionally substituted with halo, C1-4 alkyl, or C3-7 cycloalkyl; Rc = H or C1-6 alkyl; when Z = CR2b, R2a and R2b together with the carbon atoms to which they are bonded form each (un)substituted carbocyclic or heterocyclic ring]. The biaryl derivatives I include arylpyridine or heterocyclylpyridine derivatives, e.g. 3-phenyl-2-[(pyridin-3-yl)oxy]pyridine, 2-[(pyridin-3-yl)oxy]-3,3′-bipyridine, 5-[2-[(pyridin-3-yl)oxy]pyridin-3-yl]isoquinoline, 8-[2-[(pyridin-3-yl)oxy]pyridin-3-yl]quinoline, 3-(2,3-dihydrobenzofuran-7-yl)-2-[(pyridin-3-yl)oxy]pyridine, 5-[2-[(pyridin-3-yl)oxy]pyridin-3-yl]quinoxaline, and 3-(chroman-8-yl)-2-[(pyridin-3-yl)oxy]pyridine derivatives Thus, etherification of 3-bromo-2-chloropyridine with 6-(trifluoromethyl)pyridin-3-ol in the presence of Cs2CO3 in DMSO with stirring at 120° for 18 h gave 76% 3-[(3-bromopyridin-2-yl)oxy]-6-(trifluoromethyl)pyridine (II). Coupling of II with 2-methoxyphenylboronic acid in the presence of bis[di-tert-butyl(4-dimethylaminophenyl)phosphine]palladium(II) and Cs2CO3 in aqueous dioxane solution with stirring at 120° for 30 min under microwave irradiation gave 76% 3-(2-methoxyphenyl)-2-[[6-(trifluoromethyl)pyridin-3-yl]oxy]pyridine (III). III showed min. inhibitory concentration of ≤0.1 μg/mL against Trichophyton mentagrophytes and T. rubrum. The experimental process involved the reaction of 3,5-Dibromo-4-methoxypyridine(cas: 25813-24-5).Synthetic Route of 25813-24-5
The Article related to bipyridine phenylpyridine pyridylquinoline pyrimidinylpyridine heterocyclylpyridine preparation antifungal, biaryl preparation antifungal agent, Heterocyclic Compounds (One Hetero Atom): Pyridines and other aspects.Synthetic Route of 25813-24-5