Hydrochloric Acid → (+/-)-(5-Chloro-2,3-dihydronaphtho[1,2-b]furan-2-yl)methyl azide

HRID 13970

反応式

HRID 13970 の反応式
CC1C=CC(S(OCC(O)[CH2:14][C:15]2[CH:24]=[C:23]([Cl:25])[C:22]3[C:17](=[CH:18][CH:19]=[CH:20][CH:21]=3)[C:16]=2[O:26][CH2:27][C:28]2C=CC=CC=2)(=O)=O)=CC=1.Cl.CC1C=CC(S(OCC(O)CC2C=C(Cl)C3C(=CC=CC=3)C=2O)(=O)=O)=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CC(OC(/N=N/C(OC(C)C)=O)=O)C.CC1C=CC(S(OCC2OC3C4C(C(Cl)=CC=3C2)=CC=CC=4)(=O)=O)=CC=1.S(C1C=CC(C)=CC=1)([O-])(=O)=O.[N-:133]=[N+:134]=[N-:135].[Na+]>[Pd].C(O)(C)C>[Cl:25][C:23]1[C:22]2[C:17](=[CH:18][CH:19]=[CH:20][CH:21]=2)[C:16]2[O:26][CH:27]([CH2:28][N:133]=[N+:134]=[N-:135])[CH2:14][C:15]=2[CH:24]=1

参加物

11

反応物 8

HCID 313Hydrochloric AcidHCID 11776TriphenylphosphineHCID 33557Sodium AzideHCID 85570p-ToluenesulfonateHCID 5363146Diisopropyl azodicarboxylateHCID 86598554(+/-)-3-[1-(Benzyloxy)-4-chloro-2-naphthyl]-2-hydroxypropyl 4-methylbenzenesulfonateHCID 86598578(+/-)-3-(4-Chloro-1-hydroxy-2-naphthyl)-2-hydroxypropyl 4-methylbenzenesulfonateHCID 86598579(+/-)-(5-Chloro-2,3-dihydronaphtho[1,2-b]furan-2-yl)methyl 4-methylbenzenesulfonate

生成物 1

HCID 86598577(+/-)-(5-Chloro-2,3-dihydronaphtho[1,2-b]furan-2-yl)methyl azide

試薬・触媒・溶媒 2

HCID 23938Palladium触媒HCID 3776Isopropanol溶媒

実験手順

Treatment of (±)-3-[1-(benzyloxy)-4-chloro-2-naphthyl]-2-hydroxypropyl 4-methylbenzenesulfonate (4.6 g, 9.26 mmol) with palladium on carbon (5 wt. %, 0.50 g) and hydrogen chloride in isopropanol (4.0 M, 4.0 mL) generally according to the procedure described for Intermediate 4 provided (±)-3-(4-chloro-1-hydroxy-2-naphthyl)-2-hydroxypropyl 4-methylbenzenesulfonate. Treatment of the phenyl with triphenylphosphine (3.5 g, 13.3 mmol) followed by diisopropylazodicarboxylate (2.69 g, 13.3 mmol) generally according to the procedure described for Intermediate 5 afforded (±)-(5-chloro-2,3-dihydronaphtho[1,2-b]furan-2-yl)methyl 4-methylbenzenesulfonate as a colorless oil. Treatment of the tosylate with sodium azide (1.1 g, 16.4 mmol) generally according to the procedure described for Intermediate 24 gave (±)-(5-chloro-2,3-dihydronaphtho[1,2-b]furan-2-yl)methyl azide as a pale brown oil. Treatment of the azide with sulfided platinum on carbon (5 wt. %, 0.15 g) generally according to the procedure described for Example 2 provided 1.07 g (43%) of (±)-1-(5-chloro-2,3-dihydronaphtho[1,2-b]furan-2-yl)methanamine as a white solid, hydrochloride salt. mp 269-271° C.; Anal. calcd. for C13H12ClNOHCl.0.8H2O: C, 54.87; H, 5.17; N, 4.92. Found: C, 54.68; H, 4.78; N, 4.79.

出典と根拠

ORDレコード
ord-9df6618c6da74b71bd9dd4492d3a3151
出典データセット
uspto-grants-2010_06
特許番号
US07728155B2

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