合成路线:1) By reduction of 2-(5-oxo-5H[1]benzopyrano[2,3-b]pyridin-7-yl)propionic acid (I) with NaBH4 in basic water.2) By treating with CO2 the Grignard compound prepared from 7-(1-bromoethyl)-5H[1]benzopyrane[2,3-b]pyridine (II) with Mg in THF.3) By oxidation of 2-(5H[1]benzopyrane[2,3b]pyridin-7-yl)propionaldehyde (III) with silver oxide in basic ethanol.4) By reduction of 2-(5H[1]benzopyrane[2,3-b]pyridin-7-yl)acrylic acid (IV) or 2-(5H[1]benzopyrane[2,3b]pyridin-7-yl)-2-chloropropionic acid (V) with H2 over Raney-Ni in aqueous NaOH.
合成路线:1) By cyclization of 2-[p-(alpha-carboxyethyl)phenoxy]nicotinic acid (XIII) with phosphoric acid at 130-40 C.2) By cyclization of 2-[3-(2-chloronicotinoyl)-4-hydroxyphenyl]propionic acid (XIV) hy means of Cu - Cu2I2 in aqueous NaOH.3) By oxidation of 2-(5-oxo-5H[1]benzopyrano[2,3-b]-pyridin-7-yl)propionaldehyde (XV) with KMnO4 in pyridine-water.
合成路线:The bromination of 7-methyl-5-oxo-5H[1]benzopyrane[2,3-b]pyridine (XVI) with NBS in CCl4 gives 7-bromomethyl-5-oxo-5H[1]benzopyrane[2,3-b] pyridine (XVII),which is treated with NaCN in DMF yielding 7-cyanomethyl-5-oxo-5H[1]benzopyrane[2,3b]pyridine (XVIII).The reaction of (XVIII) with diethyl carbonate (A) by means of sodium ethoxide in ethanol affords ethyl 2-cyano-2-(5-oxo-5H[1]benzopyrane[2,3b]pyridine-7-yl)acetate (XIX),which,without isolation,is methylated with MeI giving ethyl 2-cyano-2-(5-oxo-5H[1]benzopyrane[2,3b]pyridine-7-yl)propionate (XX); finally this product is hydrolyzed and decarboxylated with dry HCl in refluxing acetic acid.An alternative way starting from the cyano derivative (XVIII) is its methylation with NaNH2 and MeI giving 7-(1-cyanoethyl)-5-oxo-5H[1]benzopyrane[2,3-b]pyridine (XXI),which is hydrolyzed with dry HCl in refluxing acetic acid.
参考文献标题:Substituted alkanoic acids and derivatives
文献作者:Nakanishi,M.; Oe,T.; Tsuruda,M.
参考来源:DE 2337052; FR 2193593; GB 1403487; US 3931205
合成路线:1) By cyclization of 2-[p-(alpha-carboxyethyl)phenoxy]nicotinic acid (XIII) with phosphoric acid at 130-40 C.2) By cyclization of 2-[3-(2-chloronicotinoyl)-4-hydroxyphenyl]propionic acid (XIV) hy means of Cu - Cu2I2 in aqueous NaOH.3) By oxidation of 2-(5-oxo-5H[1]benzopyrano[2,3-b]-pyridin-7-yl)propionaldehyde (XV) with KMnO4 in pyridine-water.
参考文献标题:
文献作者:Nakanishi,M.; et al.
参考来源:JP 7505398
合成路线:1) By reduction of 2-(5-oxo-5H[1]benzopyrano[2,3-b]pyridin-7-yl)propionic acid (I) with NaBH4 in basic water.2) By treating with CO2 the Grignard compound prepared from 7-(1-bromoethyl)-5H[1]benzopyrane[2,3-b]pyridine (II) with Mg in THF.3) By oxidation of 2-(5H[1]benzopyrane[2,3b]pyridin-7-yl)propionaldehyde (III) with silver oxide in basic ethanol.4) By reduction of 2-(5H[1]benzopyrane[2,3-b]pyridin-7-yl)acrylic acid (IV) or 2-(5H[1]benzopyrane[2,3b]pyridin-7-yl)-2-chloropropionic acid (V) with H2 over Raney-Ni in aqueous NaOH.
合成路线:The reduction of 5-oxo-5H[1]benzopyrane[2,3-b]pyridine (VI) affords 5-hydroxy-5H[1]benzopyrane[2,3-b]pyridine (VII),which is reduced again with refluxing isopropanol and HCl giving 5H[1]benzopyrane[2,3b]pyridine (VIII).This product is chloromethylated with HCHO and HCl in H2SO4 to yield 7-chloromethyl-5H[1]benzopyrane[2,3-b]pyridine (IX),which is treated with KCN in DMF-water to afford 7-cyanomethyl-5H[1]benzopyrane[2,3-b]pyridine (X).The reaction of (X) with diethyl carbonate (A) in ethanol containing sodium ethoxide gives ethyl 2-cyano-2-(5H[1]benzopyrano[2,3-b]pyridine-7-yl)acetate (XI),which,without isolation,is methylated with MeI to ethyl 2-cyano-2-(5H[1]-benzopyrano[2,3-b]pyridin-7-yl)propionate (XII).Finally,(XII) is hydrolyzed and decarboxylated with dry HCl in refluxing acetic acid.
参考文献标题:
文献作者:Nakanishi,M.; et al.
参考来源:JP 7493398
合成路线:The reduction of 5-oxo-5H[1]benzopyrane[2,3-b]pyridine (VI) affords 5-hydroxy-5H[1]benzopyrane[2,3-b]pyridine (VII),which is reduced again with refluxing isopropanol and HCl giving 5H[1]benzopyrane[2,3b]pyridine (VIII).This product is chloromethylated with HCHO and HCl in H2SO4 to yield 7-chloromethyl-5H[1]benzopyrane[2,3-b]pyridine (IX),which is treated with KCN in DMF-water to afford 7-cyanomethyl-5H[1]benzopyrane[2,3-b]pyridine (X).The reaction of (X) with diethyl carbonate (A) in ethanol containing sodium ethoxide gives ethyl 2-cyano-2-(5H[1]benzopyrano[2,3-b]pyridine-7-yl)acetate (XI),which,without isolation,is methylated with MeI to ethyl 2-cyano-2-(5H[1]-benzopyrano[2,3-b]pyridin-7-yl)propionate (XII).Finally,(XII) is hydrolyzed and decarboxylated with dry HCl in refluxing acetic acid.
参考文献标题:Substituted alkanoic acids and derivatives
文献作者:Takanori,O.; et al.
参考来源:DE 2337052; FR 2193593; GB 1403487; US 3931205
合成路线:1) By reduction of 2-(5-oxo-5H[1]benzopyrano[2,3-b]pyridin-7-yl)propionic acid (I) with NaBH4 in basic water.2) By treating with CO2 the Grignard compound prepared from 7-(1-bromoethyl)-5H[1]benzopyrane[2,3-b]pyridine (II) with Mg in THF.3) By oxidation of 2-(5H[1]benzopyrane[2,3b]pyridin-7-yl)propionaldehyde (III) with silver oxide in basic ethanol.4) By reduction of 2-(5H[1]benzopyrane[2,3-b]pyridin-7-yl)acrylic acid (IV) or 2-(5H[1]benzopyrane[2,3b]pyridin-7-yl)-2-chloropropionic acid (V) with H2 over Raney-Ni in aqueous NaOH.
参考文献标题:
文献作者:Tsuruda,M.; et al.
参考来源:JP 7505399
合成路线:The bromination of 7-methyl-5-oxo-5H[1]benzopyrane[2,3-b]pyridine (XVI) with NBS in CCl4 gives 7-bromomethyl-5-oxo-5H[1]benzopyrane[2,3-b] pyridine (XVII),which is treated with NaCN in DMF yielding 7-cyanomethyl-5-oxo-5H[1]benzopyrane[2,3b]pyridine (XVIII).The reaction of (XVIII) with diethyl carbonate (A) by means of sodium ethoxide in ethanol affords ethyl 2-cyano-2-(5-oxo-5H[1]benzopyrane[2,3b]pyridine-7-yl)acetate (XIX),which,without isolation,is methylated with MeI giving ethyl 2-cyano-2-(5-oxo-5H[1]benzopyrane[2,3b]pyridine-7-yl)propionate (XX); finally this product is hydrolyzed and decarboxylated with dry HCl in refluxing acetic acid.An alternative way starting from the cyano derivative (XVIII) is its methylation with NaNH2 and MeI giving 7-(1-cyanoethyl)-5-oxo-5H[1]benzopyrane[2,3-b]pyridine (XXI),which is hydrolyzed with dry HCl in refluxing acetic acid.
参考文献标题:
文献作者:Nakanishi,M.; et al.
参考来源:JP 7535196
产品链接: CAS No. 52549-17-4››