Hydrochloric Acid → Methyl 21-(2-hydroxy-3,4-dimethoxy-6-methylbenzoyl)heneicosanoate

HRID 2412844ノート

反応式

HRID 2412844 の反応式
Cl[C:2]([CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][C:24]([O:26][CH3:27])=[O:25])=[O:3].[Cl-].[Al+3].[Cl-].[Cl-].[CH3:32][O:33][C:34]1[CH:35]=[C:36]([CH3:44])[CH:37]=[C:38]([O:42]C)[C:39]=1[O:40][CH3:41].Cl>ClCCCl>[OH:42][C:38]1[C:39]([O:40][CH3:41])=[C:34]([O:33][CH3:32])[CH:35]=[C:36]([CH3:44])[C:37]=1[C:2]([CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][C:24]([O:26][CH3:27])=[O:25])=[O:3]

参加物

6

反応物 4

HCID 313Hydrochloric AcidHCID 809223,4,5-TrimethoxytolueneHCID 6451240Aluminum(III) Chloride2 回HCID 20431167Methyl 21-chloroformylheneicosanoate

生成物 1

HCID 12824097Methyl 21-(2-hydroxy-3,4-dimethoxy-6-methylbenzoyl)heneicosanoate

試薬・触媒・溶媒 1

HCID 111,2-Dichloroethane溶媒2 回

実験手順

In 60 ml of 1,2-dichloroethane is dissolved 8 g of methyl 21-chloroformylheneicosanoate, followed by addition of 5.5 g of aluminum chloride. The mixture is stirred. Then, under ice-cooling and stirring in a nitrogen stream, a solution of 5.67 g of 3,4,5-trimethoxytoluene in 1,2-dichloroethane (13 ml) is added dropwise. The mixture is stirred for 48 hours, after which 1.3 g of aluminum chloride is added. The mixture is stirred at room temperature for 16 hours and further at 35° C.-38° C. for 40 minutes. To this reaction mixture are added ice-water and 3N-HCl, followed by extraction with chloroform. The extract is washed with water, a saturated aqueous solution of sodium hydrogen carbonate and water in that order. After drying, the solvent is distilled off under reduced pressure and the residue is chromatographed on silica gel. The fractions containing the desired compound are pooled and recrystallized from methanol. The above procedure yields methyl 21-(2-hydroxy-3,4-dimethoxy-6-methylbenzoyl)heneicosanoate as colorless needles. m.p. 73°-74° C. NMR(δ, in deuteriochloroform): 1.24(36H, b, CH2), 2.27(2H,t,CH2COO), 2.42(3H, s, nuclear CH3), 2.86(2H, t,COCH2), 3.64(3H,s,COOCH3), 3.84(3H,s,OCH3), 3.87(3H,s,OCH3), 6.22(1H,s,nuclear H).

後処理

  1. temperatureThen, under ice-cooling
  2. stirringstirring in a nitrogen stream
  3. stirringThe mixture is stirred for 48 hours
  4. stirringThe mixture is stirred at room temperature for 16 hours and further at 35° C.-38° C. for 40 minutes
  5. extractionfollowed by extraction with chloroform
  6. washThe extract is washed with water
  7. customAfter drying
  8. distillationthe solvent is distilled off under reduced pressure
  9. customthe residue is chromatographed on silica gel
  10. additionThe fractions containing the desired compound
  11. customrecrystallized from methanol

出典と根拠

ORDレコード
ord-e5127744d79647438eb032303d2f715e
出典データセット
uspto-grants-1985_01
特許番号
US04495104

反応ノート

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