1,5-Dibromopentane → Ethyl 7-bromo-2-methyl-2-phenylheptanoate

HRID 239077

反応式

HRID 239077 の反応式
[Li+].CC([N-]C(C)C)C.[CH2:9]([O:11][C:12](=[O:21])[CH:13]([C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1)[CH3:14])[CH3:10].Br[CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][Br:28].[NH4+].[Cl-]>C1COCC1.CN1C(=O)N(C)CCC1>[Br:28][CH2:27][CH2:26][CH2:25][CH2:24][CH2:23][C:13]([CH3:14])([C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1)[C:12]([O:11][CH2:9][CH3:10])=[O:21]

参加物

7

反応物 4

HCID 81001,5-DibromopentaneHCID 25517Ammonium ChlorideHCID 99643Benzeneacetic acid, alpha-methyl-, ethyl esterHCID 2724682Lithium diisopropylamide

生成物 1

HCID 11313415Ethyl 7-bromo-2-methyl-2-phenylheptanoate収率 58%

試薬・触媒・溶媒 2

HCID 8028Tetrahydrofuran溶媒HCID 816462(1H)-Pyrimidinone, tetrahydro-1,3-dimethyl-溶媒

実験手順

Under N2 atmosphere, a solution of LDA (2.0 M in heptane/THF/ethylbenzene, 1.85 mL, 3.70 mol) was added dropwise to a stirred solution of 202 (660 g, 3.70 mol) in anhydrous THF (6.6 L) over 30 min at −78° C. After 1 h, 1,5-dibromopentane (1390 g, 6.05 mol) was added, followed by the addition of DMPU (660 mL). The reaction mixture was stirred for 1 h, then warmed to room temperature and stirred overnight. The mixture was poured into saturated aqueous NH4Cl solution (24 L) and extracted with ethyl acetate (4×6.7 L). The combined organic layers were washed with brine (9 L), 1 N HCl (6 L), saturated aqueous NaHCO3 solution (6 L), and brine (6 L). The solution was dried over MgSO4 and concentrated in vacuo. The residue was distilled in high vacuo to yield 205h (700g, 58%) as a yellowish oil. Bp 140-145° C./0.3 mmHg. 1H NMR (CDCl3): δ 7.30-7.20 (m, 5 H), 4.09 (m, 2 H), 3.34 (t, 2 H, J=6.9), 2.05-1.80 (m, 4 H), 1.53 (s, 3 H), 1.43-1.14 (m, 4 H), 1.16 (t, 3 H, J=6.6). 13C NMR (CDCl3): δ 176.03, 143.99, 128.33, 126.60, 125.89, 60.68, 50.11, 39.03, 33.75, 32.51, 28.59, 23.93, 22.78, 14.10. HRMS (LSIMS, nba): Calcd for C16H24BrO2 (MH+): 327.0960, found: 327.0952. HPLC: 91.2% pure.

後処理

  1. stirringstirred overnight
  2. extractionextracted with ethyl acetate (4×6.7 L)
  3. washThe combined organic layers were washed with brine (9 L), 1 N HCl (6 L), saturated aqueous NaHCO3 solution (6 L), and brine (6 L)
  4. dry with materialThe solution was dried over MgSO4
  5. concentrationconcentrated in vacuo
  6. distillationThe residue was distilled in high vacuo

出典と根拠

ORDレコード
ord-2e28450e03d84b6b89f1e861a08b4203
出典データセット
uspto-grants-2014_02
特許番号
US08642653B2

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