Diethyl Pyrocarbonate → (S)(-)-Ethyl N-(3,4-dihydro-2-naphthoyl)prolinate

HRID 2057729

反応式

HRID 2057729 の反応式
[CH:1]1[C:10]2[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=2)[CH2:4][CH2:3][C:2]=1[C:11]([OH:13])=O.[NH:14]1[CH2:23][CH2:22][CH2:21][C@H:15]1[C:16]([O:18][CH2:19][CH3:20])=[O:17].CCOC(OC(OCC)=O)=O.C(N(CC)CC)C>C(OCC)(=O)C.CN(C=O)C>[CH:1]1[C:10]2[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=2)[CH2:4][CH2:3][C:2]=1[C:11]([N:14]1[CH2:23][CH2:22][CH2:21][C@H:15]1[C:16]([O:18][CH2:19][CH3:20])=[O:17])=[O:13]

参加物

7

反応物 4

HCID 3051Diethyl PyrocarbonateHCID 8471TriethylamineHCID 79888L-Proline, ethyl esterHCID 5822833,4-Dihydronaphthalene-2-carboxylic acid

生成物 1

HCID 12743978(S)(-)-Ethyl N-(3,4-dihydro-2-naphthoyl)prolinate収率 92.7%

試薬・触媒・溶媒 2

HCID 6228Dimethylformamide溶媒3 回HCID 8857Ethyl Acetate溶媒

実験手順

To a DMF solution (60 ml) containing 3,4-dihydro-2-naphthoic acid (9a, 7.12 g, 40.0 mmole), and (S)(-)-ethyl prolinate (6.41 g, 44.8 mmole), a DMF solution (60 ml) containing DEPC (7.17 g, 44.0 mmole) and a DMF solution (60 ml) containing triethylamine (4.05 g, 40.0 mmole) are dropwise added at 0° C. in 5 minutes. The resultant mixture is stirred at 0° C. for 2 hours and then at room temperature for 2 days. The reaction mixture is diluted with ethyl acetate (1.8 liters), and the ethyl acetate solution is washed with 5% hydrochloric acid (130 ml×2), water (130 ml×2), a saturated aqueous solution of sodium chloride (130 ml×2), a saturated aqueous solution of sodium hydrogen carbonate (130 ml×2) and water (130 ml×2) in order and then dried over anhydrous magnesium sulfate. After filtration and evaporation, a crude product (10a) is obtained as a yellow caramel (13.9 g, 116%), which is purified by column chromatography (silica gel, 300 g; solvent, ether) to obtain an almost pure product (10a) as colorless needles (11.1 g, 91%). M.P. 55°-57° C. Recrystallization from ether-hexane affords an analytical sample as colorless needles melting at 56°-57° C. [α]D20 -18.6° (c=1.03, ethanol). IRνmaxNujol cm-1 : 1750 (ester), 1650 (C=C), 1610 (CON), NMR (in CDCl3): 1.27 (3H, t, J=7 Hz, CO2CH2CH3), 1.64-2.40 (4H, m, NCH2CH2CH2), 2.40-3.20 (4H, m, CH2CH2C=), 3.72 (2H, t, J=6 Hz, N--CH2), 4.16 (2H, q, J= 7 Hz, CO2CH2CH3), 4.58 (1H, t, J=6 Hz, NCHCO2), 6.77 (1H, s, CH=C), 7.12 (4H, s, aromatic proton).

後処理

  1. additionare dropwise added at 0° C. in 5 minutes
  2. washthe ethyl acetate solution is washed with 5% hydrochloric acid (130 ml×2), water (130 ml×2)
  3. dry with materiala saturated aqueous solution of sodium chloride (130 ml×2), a saturated aqueous solution of sodium hydrogen carbonate (130 ml×2) and water (130 ml×2) in order and then dried over anhydrous magnesium sulfate
  4. filtrationAfter filtration and evaporation
  5. customa crude product (10a) is obtained as a yellow caramel (13.9 g, 116%), which
  6. customis purified by column chromatography (silica gel, 300 g; solvent, ether)

出典と根拠

ORDレコード
ord-6f88768ad6db4b258ca04fef0184dc11
出典データセット
uspto-grants-1980_07
特許番号
US04212828

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