2-Methyl-2-butene → Ethyl (+/-)-3-[3-carboxy-1-propyl]-5H-dibenzo [a,d]cycloheptene-10-acetate

HRID 613387ノート

反応式

HRID 613387 の反応式
[OH:1][CH2:2][CH2:3][CH2:4][CH2:5][C:6]1[CH:7]=[CH:8][C:9]2[CH:15]=[C:14]([CH2:16][C:17]([O:19][CH2:20][CH3:21])=[O:18])[C:13]3[CH:22]=[CH:23][CH:24]=[CH:25][C:12]=3[CH2:11][C:10]=2[CH:26]=1.[Cl-].CC1(C)CCCC(C)(C)[N+]1=[O:37].CC(=CC)C.[O-]Cl=O.[Na+]>C(Cl)Cl.O.CCOC(C)=O>[C:2]([CH2:3][CH2:4][CH2:5][C:6]1[CH:7]=[CH:8][C:9]2[CH:15]=[C:14]([CH2:16][C:17]([O:19][CH2:20][CH3:21])=[O:18])[C:13]3[CH:22]=[CH:23][CH:24]=[CH:25][C:12]=3[CH2:11][C:10]=2[CH:26]=1)([OH:37])=[O:1]

参加物

8

反応物 4

HCID 105532-Methyl-2-buteneHCID 10954377Piperidinium, 2,2,6,6-tetramethyl-1-oxo-, chlorideHCID 23668197Sodium ChloriteHCID 53688679Ethyl (+/-)-3-[4-hydroxy-1-butyl]-5H-dibenzo[a,d]cycloheptene-10-acetate

生成物 1

HCID 54111116Ethyl (+/-)-3-[3-carboxy-1-propyl]-5H-dibenzo [a,d]cycloheptene-10-acetate

試薬・触媒・溶媒 3

HCID 962Water溶媒HCID 6344Dichloromethane溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
0 °C

実験手順

A solution of ethyl (±)-3-[4-hydroxy-1-butyl]-5H-dibenzo[a,d]cycloheptene-10-acetate (342.4 mg, 0.97 mmole) in anhydrous CH2Cl2 (19 mL) was cooled to 0° C. under argon, and 2,2,6,6-tetramethyloxopiperidinium chloride (J. Org. Chem. 1985, 50, 1332-1334; 260 mg, 1.36 mmole) was added in one portion. The reaction was stirred at 0° C. for 1 hr, then 2-methyl-2-butene (1.2 mL, 11 64 mmole) was added, followed by a cold (0° C.) solution of NaClO2 (0.88 g, 7.76 mmole) and NaH2PO4 (0.90 g, 6.50 mmole) in H2O (26 mL). After 10 min, the reaction was diluted with EtOAc (100 mL) and the layers were separated. The organic layer was washed sequentially with cold 1.0 N HCl (10 mL) and saturated brine (20 mL), dried (MgSO4), and concentrated. Silica gel chromatography (gradient: 1:1 EtOAc/CHCl3 then 9:9:2 EtOAc/CHCl3 /EtOH) gave impure title compound. Rechromatography on silica gel (7:3:0.1 toluene/EtOAc/AcOH) gave the pure title compound (233.7 mg, 66%): TLC (1:1 EtOAc/CHCl3) Rf 0.46; 1H NMR (400 MHz, CDCl3) δ 7.05-7.22 (m, 4 H), 6.92-7.05 (m, 3 H), 4.34 (d, J=15.0 Hz, 1 H), 4.10-4.25 (m, 2 H), 3.80-3.90 (m, 2 H), 3.33 (dd, J=15.1, 4.1 Hz, 1 H), 2.95 (dd, J=15.1, 9.4 Hz, 1 H), 2.48-2.60 (m, 4 H), 2.48-2.60 (m, 4 H), 2.37 (t, J=7.4 Hz, 2 H), 1.87-2.00 (m, 2 H), 1.27 (t, J=7.2 Hz, 3 H); MS (ES) m/e 389 (M+Na)+, 367 (M+H)+.

後処理

  1. waitAfter 10 min
  2. customthe layers were separated
  3. washThe organic layer was washed sequentially with cold 1.0 N HCl (10 mL) and saturated brine (20 mL)
  4. dry with materialdried (MgSO4)
  5. concentrationconcentrated

出典と根拠

ORDレコード
ord-2ba5b790ef13472b8450897a962f97ef
出典データセット
uspto-grants-1999_12
特許番号
US06008213

反応ノート

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