Hydrochloric Acid → Tetrahydropyranyl ether

HRID 1703991ノート

反応式

HRID 1703991 の反応式
CS(C)=[O:3].[CH2:5]([Li])[CH2:6][CH2:7]C.Cl[CH2:11][C:12]([O-:14])=[O:13].[Li+].Cl.C[CH2:18][CH2:19][CH2:20][CH2:21][CH3:22]>O.CN(C)C=O.O1CCCC1>[O:13]1[CH2:7][CH2:6][CH2:5][CH2:11][CH:12]1[O:14][CH:18]1[CH2:19][CH2:20][CH2:21][CH2:22][O:3]1

参加物

9

反応物 5

HCID 313Hydrochloric AcidHCID 679Dimethyl SulfoxideHCID 8058HexaneHCID 23695591Lithium chloroacetateHCID 178418339Butyllithium

生成物 1

HCID 263182Tetrahydropyranyl ether

試薬・触媒・溶媒 3

HCID 962Water溶媒HCID 6228Dimethylformamide溶媒HCID 8028Tetrahydrofuran溶媒

反応条件

温度
10 °C

実験手順

Refer to Chart E. There is first prepared the bis-tetrahydropyran-2-yl ether of the title compound. A solution of the formula-XLI 3,3aβ,4,5,6,6aβ-hexahydro-5α-hydroxy-2ξ-(2'-hydroxyethyl-4β-(3'α-hydroxy-trans-1-octenyl)-2H-cyclopenta[b]furan, 3',5-bistetrahydropyran-2-yl ether (Example 5, 0.80 g.) in 10 ml. of dimethyl sulfoxide and 5 ml. of tetrahydrofuran is treated at about 0-5° C. with 1.1 ml. of 1.6 M n-butyllithium in hexane added dropwise over a one-minute period. Thereafter the mixture is stirred at about 10° C. for 5 min., followed by additions of 8 ml. of dimethylformamide and 0.35 g. of lithium chloroacetate. The mixture is stirred at about 25° C. for 22 hr., then diluted with 125 ml. of ice and water containing 3 ml. of concentrated hydrochloric acid. The resulting mixture is extracted with dichloromethane and the organic phase is washed with cold water and brine, and concentrated. The residue containing the acid form of the formula-LIII bistetrahydropyran-2-yl ether, is converted to the methyl ester in diethyl ether by reaction with diazomethane. After 3 min., the excess diazomethane is destroyed with acetic acid and the mixture is washed with dilute potassium hydroxide solution and brine, dried, and concentrated to yield the formula-LIII bistetrahydropyran-2-yl ether of the title compound, as mixed isomers.

後処理

  1. stirringThe mixture is stirred at about 25° C. for 22 hr
  2. addition, then diluted with 125 ml
  3. extractionThe resulting mixture is extracted with dichloromethane
  4. washthe organic phase is washed with cold water and brine
  5. concentrationconcentrated
  6. additionThe residue containing the acid form of the formula-LIII bistetrahydropyran-2-yl ether
  7. customis converted to the methyl ester in diethyl ether by reaction with diazomethane
  8. waitAfter 3 min.
  9. customthe excess diazomethane is destroyed with acetic acid
  10. washthe mixture is washed with dilute potassium hydroxide solution and brine
  11. customdried
  12. concentrationconcentrated

出典と根拠

ORDレコード
ord-e3293ae72e7e47b2b1852da4eb525900
出典データセット
uspto-grants-1978_11
特許番号
US04125713

反応ノート

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