Methanol → 2-Iodo-3-nitrobenzyl alcohol

HRID 366834

反応式

HRID 366834 の反応式
B.CSC.[I:5][C:6]1[C:14]([N+:15]([O-:17])=[O:16])=[CH:13][CH:12]=[CH:11][C:7]=1[C:8](O)=[O:9].B(OC)(OC)OC.CO>C1COCC1.O>[I:5][C:6]1[C:14]([N+:15]([O-:17])=[O:16])=[CH:13][CH:12]=[CH:11][C:7]=1[CH2:8][OH:9]

参加物

7

反応物 4

HCID 887MethanolHCID 8470Trimethyl borateHCID 2209662-Iodo-3-nitrobenzoic acidHCID 12423031(Dimethyl sulfide)trihydroboron

生成物 1

HCID 540609152-Iodo-3-nitrobenzyl alcohol

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 8028Tetrahydrofuran溶媒

実験手順

Borane-dimethylsulfide (34 mL, 0.34 mmol) was added to a solution of 2-iodo-3-nitrobenzoic acid (43) [P. J. Culhane, Org. Synth. Coll. Vol 1, 1967, 125-127] (82.3 g, 0.28 mol) and trimethyl borate (64 mL, 0.56 mol) in dry THF (400 mL) under nitrogen, and the mixture stirred at reflux for 90 min. The solution was cooled, MeOH then H2O were added, and the mixture was evaporated. Aq NaCl was added to the residue and the mixture was extracted with EtOAc (×3). The extracts were washed with aq NaCl, dried (Na2SO4), and evaporated to give crude 2-iodo-3-nitrobenzyl alcohol (44) as a yellow-orange solid suitable for use in the next step. A sample was filtered through a short column of silica eluting with CH2Cl2 and recrystallized from PhH as pale yellow needles, mp 91-91.5° C. 1H NMR (CDCl3) δ 7.72 (dd, J=7.7, 1.1 Hz, 1 H, H-4 or 6), 7.59 (dd, J=8.1, 1.5 Hz, 1 H, H-4 or 6), 7.50 (t, J=7.8 Hz, 1 H, H-5), 4.78 (s, 2 H, CH2), 2.14 (br s, 1 H, OH). Anal. Calculated for C7H6INO3 : C, 30.1; H, 2.2; N, 5.0. Found: C, 30.4; H, 2.1; N, 4.9%.

後処理

  1. temperatureat reflux for 90 min
  2. temperatureThe solution was cooled
  3. customthe mixture was evaporated
  4. additionAq NaCl was added to the residue
  5. extractionthe mixture was extracted with EtOAc (×3)
  6. washThe extracts were washed with aq NaCl
  7. dry with materialdried (Na2SO4)
  8. customevaporated

出典と根拠

ORDレコード
ord-7af5724141fc45579afb152a524136d9
出典データセット
uspto-grants-2000_10
特許番号
US06130237

関連ノート

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