Brucine → (R)-1',2',3',4'-tetrahydro-2'-hydroxy-5',8'-dimethoxyspiro[1,3-dithiolane-2,4'-naphthalene]-2'-carboxylic acid

HRID 463479

反応式

HRID 463479 の反応式
[OH:1][C:2]1([C:20]([OH:22])=[O:21])[CH2:11][C:10]2([S:15][CH2:14][CH2:13][S:12]2)[C:9]2[C:4](=[C:5]([O:18][CH3:19])[CH:6]=[CH:7][C:8]=2[O:16][CH3:17])[CH2:3]1.COC1C=C2[C@@]34[C@@H]5C[C@H]6C(CN5CC3)=CCO[C@H]3CC(=O)N([C@H]4[C@@H]63)C2=CC=1OC>>[OH:1][C@@:2]1([C:20]([OH:22])=[O:21])[CH2:11][C:10]2([S:15][CH2:14][CH2:13][S:12]2)[C:9]2[C:4](=[C:5]([O:18][CH3:19])[CH:6]=[CH:7][C:8]=2[O:16][CH3:17])[CH2:3]1

参加物

3

反応物 2

HCID 442021BrucineHCID 132641391',2',3',4'-Tetrahydro-2'-hydroxy-5',8'-dimethoxyspiro[1,3-dithiolane-2,4'-naphthalene]-2'-carboxylic acid

生成物 1

HCID 13264140(R)-1',2',3',4'-tetrahydro-2'-hydroxy-5',8'-dimethoxyspiro[1,3-dithiolane-2,4'-naphthalene]-2'-carboxylic acid収率 35.7%

実験手順

A suspension of 3.42 g of rac-1',2',3',4'-tetrahydro-2'-hydroxy-5',8'-dimethoxyspiro[1,3-dithiolane-2,4'-naphthalene]-2'-carboxylic acid [prepared as described in Example 4(iii)] and 4.0 g of brucine was heated under reflux until a clear solution was obtained. After seeding, the solution was left to cool slowly to room temperature. The crystalline precipitate (3.6 g) was collected after 2 days. The precipitate was dissolved in 1500 ml of boiling ethyl acetate, the solution was concentrated to 600 ml and left to cool slowly. The crystalline product [2.7 g [α]D20 =-46.6°, c=0.5% in dimethylformamide] was suspended in 150 ml of ethyl acetate and shaken with three 10 ml portions of 5-M hydrochloric acid and with two 100 ml portions of brine. After drying over magnesium sulphate, the solvent was evaporated to give a colourless oil which was crystallised from diethyl ether to yield 1.22 g of (R)-1',2',3',4'-tetrahydro-2'-hydroxy-5',8'-dimethoxyspiro[1,3-dithiolane-2,4'-naphthalene]-2'-carboxylic acid in the form of colourless crystals of melting point 147° -149° C.; [α]D20 =+13.8°, c=0.5% in dioxan.

後処理

  1. temperaturewas heated
  2. temperatureunder reflux until a clear solution
  3. customwas obtained
  4. waitthe solution was left
  5. customThe crystalline precipitate (3.6 g) was collected after 2 days
  6. dissolutionThe precipitate was dissolved in 1500 ml of boiling ethyl acetate
  7. concentrationthe solution was concentrated to 600 ml
  8. waitleft
  9. temperatureto cool slowly
  10. customThe crystalline product [2.7 g [α]D20 =-46.6°, c=0.5% in dimethylformamide]
  11. dry with materialAfter drying over magnesium sulphate
  12. customthe solvent was evaporated
  13. customto give a colourless oil which
  14. customwas crystallised from diethyl ether

出典と根拠

ORDレコード
ord-e19183ea7c5e45aaafd8d247c4bf1a95
出典データセット
uspto-grants-1985_05
特許番号
US04518784

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