Sodium Chloride → HCID 12245806、化合物

HRID 1066689ノート

反応式

HRID 1066689 の反応式
C([Li])CCC.[OH:6][CH2:7][C@@H:8]1[C@@H:12]([CH2:13][OH:14])[O:11][C:10]([CH3:16])([CH3:15])[O:9]1.[C:17]1([CH3:27])[CH:22]=[CH:21][C:20]([S:23](Cl)(=[O:25])=[O:24])=[CH:19][CH:18]=1.[Cl-].[Na+]>O1CCCC1>[C:17]1([CH3:27])[CH:22]=[CH:21][C:20]([S:23]([O:14][CH2:13][C@@H:12]2[C@@H:8]([CH2:7][OH:6])[O:9][C:10]([CH3:16])([CH3:15])[O:11]2)(=[O:25])=[O:24])=[CH:19][CH:18]=1

参加物

6

反応物 4

HCID 5234Sodium ChlorideHCID 73974-Toluenesulfonyl chlorideHCID 785244(-)-2,3-O-Isopropylidene-D-threitolHCID 178418339Butyllithium

生成物 1

HCID 12245806HCID 12245806、化合物収率 74.6%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒2 回

反応条件

温度
20 °C

実験手順

21.7 mmol of n-butyllithium (1.59 molar in n-hexane, 13.6 ml) were added at -78 C to a solution of (4R,5R)-4,5-bis(hydroxymethyl)-2,2-dimethyl-1,3-dioxolane (3.32 g, 20.5 mmol) in 60 ml of tetrahydrofuran ((4R,5R)-4,5-bis(hydroxymethyl)-2,2-dimethyl-1,3-dioxolane was prepared according to J. Org. Chem. 33 (1968), page 2171). After stirring for 10 minutes, a solution of p-toluenesulfonyl chloride (4 g, 21 mmol) in 20 ml of tetrahydrofuran which was cooled to −78° C. was added. After stirring at −78° C. for 15 minutes, the mixture was warmed to 20° C. and poured into 200 ml of concentrated sodium chloride solution. The organic phase was separated off and the aqueous phase was extracted twice with 50 ml of ethyl acetate. The combined organic phases were dried over anhydrous sodium sulfate and then concentrated. The residue was chromatographed on 400 g of silica gel using ethyl acetate and n-hexane in the weight ratio 60:40 as eluent. 74.6% of (4R,5R)-[5-hydroxymethyl-2,2-dimethyl-1,3-dioxolan-4-yl]methyl p-toluenesulfonate were obtained ([α]D19=+11.80 (c=1.88 in trichloromethane); cf. J. Org. Chem. 55 (1990), page 4417: [α]D21=+11.30 (c=2.70 in trichloromethane)).

後処理

  1. additionwas added
  2. stirringAfter stirring at −78° C. for 15 minutes
  3. customThe organic phase was separated off
  4. extractionthe aqueous phase was extracted twice with 50 ml of ethyl acetate
  5. dry with materialThe combined organic phases were dried over anhydrous sodium sulfate
  6. concentrationconcentrated
  7. customThe residue was chromatographed on 400 g of silica gel

出典と根拠

ORDレコード
ord-bd98d10b040244759efdc2ed1395ca0e
出典データセット
uspto-grants-2001_06
特許番号
US06245328B1

反応ノート

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