Dimethyl Disulfide → 2-(3,4-Dichlorophenyl)-3,4-dihydro-6-(methylthio)-2h-pyrano[2,3-b]pyridine

HRID 280198

反応式

HRID 280198 の反応式
Br[C:2]1[CH:3]=[C:4]2[CH2:11][CH2:10][CH:9]([C:12]3[CH:17]=[CH:16][C:15]([Cl:18])=[C:14]([Cl:19])[CH:13]=3)[O:8][C:5]2=[N:6][CH:7]=1.C([Li])(C)(C)C.CCCCC.[Li].BrBr.[CH3:33][S:34]SC>C1(C)C=CC=CC=1.CCOCC>[Cl:19][C:14]1[CH:13]=[C:12]([CH:9]2[O:8][C:5]3=[N:6][CH:7]=[C:2]([S:34][CH3:33])[CH:3]=[C:4]3[CH2:11][CH2:10]2)[CH:17]=[CH:16][C:15]=1[Cl:18]

参加物

8

反応物 5

HCID 12232Dimethyl DisulfideHCID 24408BromineHCID 128207Mdl 20646HCID 3028194LithiumHCID 178446069HCID 178446069、化合物

生成物 1

HCID 5149062-(3,4-Dichlorophenyl)-3,4-dihydro-6-(methylthio)-2h-pyrano[2,3-b]pyridine

試薬・触媒・溶媒 2

HCID 1140Toluene溶媒HCID 3283Diethyl Ether溶媒

反応条件

温度
-100 °C

実験手順

A solution of 3.6 g of 6-bromo-2-(3,4-dichlorophenyl)-3,4-dihydro-2H-pyrano[2,3-b]pyridine in a mixture of 50 ml of toluene and 25 ml of anhydrous ether was cooled to -100° C. under nitrogen and 3.8 ml of 2.9M tert-butyllithium/pentane was added dropwise over about 5 minutes while keeping the temperature below -100° C. This gave a deep blue-green mixture containing the lithio intermediate (i.e., lithium replacing the bromine in the starting material). After 20 minutes, 1.8 ml of dimethyldisulfide was added. The mixture was then allowed to warm to 0° C. and it was partitioned between ether and water. The ether layer was washed with aqueous saturated sodium chloride solution, dried over potassium carbonate and concentrated to a yellow oil which solidified on cooling. Column chromatography on silica gel (20% ethyl acetate/hexane) gave pure product which was further recrystallized from hexane/ethyl acetate to give 2-(3,4-dichlorophenyl)-3,4-dihydro-6-(methylthio)-2H-pyrano[2,3-b]pyridine as colorless needles melting at about 109°-111° C.

後処理

  1. customthe temperature below -100° C
  2. customThis gave a deep blue-green mixture
  3. temperatureto warm to 0° C.
  4. customit was partitioned between ether and water
  5. washThe ether layer was washed with aqueous saturated sodium chloride solution
  6. dry with materialdried over potassium carbonate
  7. concentrationconcentrated to a yellow oil which
  8. temperatureon cooling
  9. customColumn chromatography on silica gel (20% ethyl acetate/hexane) gave pure product which
  10. customwas further recrystallized from hexane/ethyl acetate

出典と根拠

ORDレコード
ord-649dde3b72034a189df2afe607193f06
出典データセット
uspto-grants-1986_05
特許番号
US04588733

関連ノート

読み込み中…