Methyl chloroformate → 2-Cyclopentyl-4-(4-methylpent-1-ynyl)-5-nitrophenyl methyl carbonate

HRID 471940ノート

反応式

HRID 471940 の反応式
[C:1](=[O:20])([O:18][CH3:19])[O:2][C:3]1[CH:8]=[C:7]([N+:9]([O-:11])=[O:10])[C:6](Br)=[CH:5][C:4]=1[CH:13]1[CH2:17][CH2:16][CH2:15][CH2:14]1.[CH3:21][CH:22]([CH3:26])[CH2:23][C:24]#[CH:25].ClC(OC)=O>C(OCC)(=O)C.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu]I.C(N(CC)CC)C.CN(C=O)C>[C:1](=[O:20])([O:18][CH3:19])[O:2][C:3]1[CH:8]=[C:7]([N+:9]([O-:11])=[O:10])[C:6]([C:25]#[C:24][CH2:23][CH:22]([CH3:26])[CH3:21])=[CH:5][C:4]=1[CH:13]1[CH2:17][CH2:16][CH2:15][CH2:14]1

参加物

9

反応物 3

HCID 6586Methyl chloroformateHCID 1389484-Methyl-1-pentyneHCID 59394953HCID 59394953、化合物

生成物 1

HCID 593950772-Cyclopentyl-4-(4-methylpent-1-ynyl)-5-nitrophenyl methyl carbonate収率 75%

試薬・触媒・溶媒 5

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 178418476HCID 178418476、化合物触媒HCID 6228Dimethylformamide溶媒HCID 8471Triethylamine溶媒2 回HCID 8857Ethyl Acetate溶媒

実験手順

To 4-bromo-2-cyclopentyl-5-nitrophenyl methyl carbonate (100 mg, 0.29 mmol), Pd(PPh3)2Cl2 (4 mg, 0.006 mmol), and CuI (1 mg, 0.006 mmol) was added DMF (600 μL), triethylamine (750 μL), and 4-methylpent-1-yne (72 mg, 103 μL, 0.87 mmol). The reaction mixture was stirred under N2 atmosphere for 20 min, resulting in product formation with partial loss of the carbonate group. The reaction was diluted with ethyl acetate, washed with 50% saturated sodium bicarbonate solution (2×20 mL), water, and brine. The solution was dried over Na2SO4 and filtered through a plug of silica. The filtrate was treated with triethylamine (29 mg, 40 μL, 0.29 mmol) and then dropwise with methyl chloroformate (14 mg, 11 μL, 0.14 mmol). The reaction mixture was stirred for 10 min, and was then dried down, diluted with ethyl acetate, washed with 50% saturated sodium bicarbonate solution (2×20 mL), water, 0.5 M HCl, and brine. The solution was dried over Na2SO4, filtered, and concentrated in vacuo to provide 2-cyclopentyl-4-(4-methylpent-1-ynyl)-5-nitrophenyl methyl carbonate as an orange oil (75 mg, 75% yield). 1H NMR (400.0 MHz, DMSO-d6) δ 8.05 (s, 1H), 7.77 (s, 1H), 4.00 (s, 3H), 3.25-3.18 (m, 1H), 2.46 (d, J=6.3 Hz, 2H), 2.00-1.88 (m, 3H), 1.79-1.75 (m, 2H), 1.73-1.55 (m, 4H), 1.06 (d, J=6.6 Hz, 6H).

後処理

  1. customresulting in product formation with partial loss of the carbonate group
  2. washwashed with 50% saturated sodium bicarbonate solution (2×20 mL), water, and brine
  3. dry with materialThe solution was dried over Na2SO4
  4. filtrationfiltered through a plug of silica
  5. stirringThe reaction mixture was stirred for 10 min
  6. customwas then dried down
  7. additiondiluted with ethyl acetate
  8. washwashed with 50% saturated sodium bicarbonate solution (2×20 mL), water, 0.5 M HCl, and brine
  9. dry with materialThe solution was dried over Na2SO4
  10. filtrationfiltered
  11. concentrationconcentrated in vacuo

出典と根拠

ORDレコード
ord-086daa04476349c59ba898b6639bd02f
出典データセット
uspto-grants-2014_01
特許番号
US08633189B2

反応ノート

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