Ammonia → Methyl 1-butyl-2-methoxy-1,4-dihydronaphthalene-1-carboxylate

HRID 2224962ノート

反応式

HRID 2224962 の反応式
[CH3:1][O:2][C:3]1[CH:12]=[CH:11][C:10]2[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=2)[C:4]=1[C:13]([O:15][CH3:16])=[O:14].C(O)(C)(C)C.N.[K].[CH2:24](I)[CH2:25][CH2:26][CH3:27]>O1CCCC1>[CH2:24]([C:4]1([C:13]([O:15][CH3:16])=[O:14])[C:5]2[C:10](=[CH:9][CH:8]=[CH:7][CH:6]=2)[CH2:11][CH:12]=[C:3]1[O:2][CH3:1])[CH2:25][CH2:26][CH3:27]

参加物

7

反応物 5

HCID 222AmmoniaHCID 6386tert-ButanolHCID 10962Butyl iodideHCID 604022Methyl 2-methoxy-1-naphthoateHCID 5462222Potassium

生成物 1

HCID 68840565Methyl 1-butyl-2-methoxy-1,4-dihydronaphthalene-1-carboxylate

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

実験手順

To a stirred solution of methyl 2-methoxynaphthoate (3.25 g, 15 mmol) and tert-butyl alcohol (1.48 ml, 15 mmol) in tetrahydrofuran (10 mL) at −78° C. was added liquid ammonia (60 mL). Potassium metal (2.9 g, 75 mmol) was added in small pieces until the solution stayed dark blue for 30 min. Butyl iodide (5.47 mL, 48 mmol) was added dropwise (the blue coloration disappeared about half-way through addition) and stirring was continued for 1 hour at −78° C. The solution was allowed to warm to room temperature and purged with nitrogen to remove excess ammonia. To the resulting slurry a solution of saturated sodium bicarbonate (100 mL) was added, and the solution was extracted with ether (3×50 mL). The combined organic phases were washed with 10% Na2S2O3 (aq), dried (Na2SO4), and concentrated in vacuo. Column chromatography on silica (20% ethyl acetate/hexane) gave the title compound. This oil was trituated with hexane to afford a white solid (3.2 g, 77.6%). 1H NMR (300 MHz, CDCl3): δ ppm 0.63 (m, 1 H), 0.76 (t, J=7.35 Hz, 3 H), 0.99 (m, 1 H), 1.18 (m, 2 H), 2.04 (m, 1 H), 2.26 (m, 1 H), 3.55 (d, J=3.68 Hz, 2 H), 3.61 (s, 3 H), 3.63 (s, 3 H), 5.05 (t, J=3.68 Hz, 1 H), 7.16 (m, 4 H); MS (ESI) m/z 275.1 (M+H)+.

後処理

  1. additiondisappeared about half-way through addition) and
  2. waitwas continued for 1 hour at −78° C
  3. custompurged with nitrogen
  4. customto remove excess ammonia
  5. additionTo the resulting slurry a solution of saturated sodium bicarbonate (100 mL) was added
  6. extractionthe solution was extracted with ether (3×50 mL)
  7. washThe combined organic phases were washed with 10% Na2S2O3 (aq)
  8. dry with materialdried (Na2SO4)
  9. concentrationconcentrated in vacuo

出典と根拠

ORDレコード
ord-d950e5d464bf48799fae032b47325b71
出典データセット
uspto-grants-2008_05
特許番号
US07378414B2

反応ノート

読み込み中…