Carbon Disulfide → Diethyl 2-[bis(4-methoxybenzylsulfanyl)methylene]malonate

HRID 1443080

反応式

HRID 1443080 の反応式
[C:1]([O:9][CH2:10][CH3:11])(=[O:8])[CH2:2][C:3]([O:5][CH2:6][CH3:7])=[O:4].[H-].[Na+].[C:14](=[S:16])=[S:15].[CH3:17][O:18][C:19]1[CH:26]=[CH:25][C:22]([CH2:23]Cl)=[CH:21][CH:20]=1>CN(C)C=O.O>[CH3:17][O:18][C:19]1[CH:26]=[CH:25][C:22]([CH2:23][S:15][C:14]([S:16][CH2:23][C:22]2[CH:25]=[CH:26][C:19]([O:18][CH3:17])=[CH:20][CH:21]=2)=[C:2]([C:3]([O:5][CH2:6][CH3:7])=[O:4])[C:1]([O:9][CH2:10][CH3:11])=[O:8])=[CH:21][CH:20]=1

参加物

7

反応物 4

HCID 6348Carbon DisulfideHCID 7761Diethyl Malonate3 回HCID 24758Sodium hydrideHCID 699934-Methyloxybenzyl chloride

生成物 1

HCID 11561985Diethyl 2-[bis(4-methoxybenzylsulfanyl)methylene]malonate

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 6228Dimethylformamide溶媒3 回

反応条件

温度
0 °C

実験手順

A solution of dimethylformamide (50 mL) containing diethyl malonate (12.78 g, 0.08 mol) is added slowly to an ice-cooled suspension of sodium hydride (60% dispersion in mineral oil, 6.53 g, 0.16 mol) in dimethylformamide (500 mL). The rate of addition of diethyl malonate is such as to maintain the temperature of the reaction mixture below 5° C. After the addition of diethyl malonate is complete, the gray reaction mixture continues to stir at 0° C. for 15 min. Carbon disulfide (14.5 mL, 0.24 mol) is then added dropwise to give a red mixture that is allowed to warm to room temperature with stirring for 1 h. A solution of dimethylformamide (25 mL) containing 4-methoxybenzyl chloride (25.00 g, 0.16 mol) is added dropwise to the reaction mixture at room temperature. The resulting orange mixture is allowed to warm to room temperature with stirring for 15 h, diluted with water (500 mL), and extracted with ethyl acetate (4×500 mL). The combined extracts are concentrated under reduced pressure (˜1 L), washed with water (3×150 mL), washed with brine (3×150 mL), dried over magnesium sulfate, and evaporated under reduced pressure to give crude 1. The crude product is purified by flash column chromatography (eluting with ethyl acetate/hexanes=1:4; Rf 0.21) to give 1 as a yellow solid. mp 57-59° C. 1H NMR (CDCl3): δ 1.27 (t, J=7.0 Hz, 3H, CO2CH2CH3), 3.79 (s, 3H, OCH3), 4.07 (s, 2H, SCH2), 4.23 (q, J=7.0 Hz, 2H, CO2CH2CH3), 6.83 (m, 2H, H-3/H-5), 7.20 (m, 2H, H-2/H-6). 13C{1H} NMR (CDCl3): δ 14.0 (CO2CH2CH3), 40.3 (SCH2), 55.3 (OCH3), 61.4 (CO2CH2CH3), 114.1 (aromatic C-3/C-5), 128.1 (═C—CO2CH2CH3 or C—CH2S—), 128.7 (═C—CO2CH2CH3 or C—CH2S—), 130.4 (aromatic C-2/C-6), 155.6 (—CH2S—C═), 159.1 (aromatic C-4, C—OCH3), 163.9 (CO2CH2CH3). LCMS m/z calcd for C24H28O6S2 476 ([M+]). found 477 ([M+H]+). HRMS m/z calcd for C24H28NaO6S2 499.1225 ([M+Na]+). found 499.1230. Anal. Calcd for C24H28O6S2: C, 60.48; H, 5.92; S, 13.46. Found: C, 60.51; H, 5.97; S, 13.19.

後処理

  1. temperaturecooled
  2. temperatureto maintain the temperature of the reaction mixture below 5° C
  3. customto give a red mixture that
  4. temperatureto warm to room temperature
  5. stirringwith stirring for 1 h
  6. additionis added dropwise to the reaction mixture at room temperature
  7. temperatureto warm to room temperature
  8. stirringwith stirring for 15 h
  9. extractionextracted with ethyl acetate (4×500 mL)
  10. concentrationThe combined extracts are concentrated under reduced pressure (˜1 L)
  11. washwashed with water (3×150 mL)
  12. washwashed with brine (3×150 mL)
  13. dry with materialdried over magnesium sulfate
  14. customevaporated under reduced pressure
  15. customto give crude 1
  16. customThe crude product is purified by flash column chromatography (eluting with ethyl acetate/hexanes=1:4; Rf 0.21)

出典と根拠

ORDレコード
ord-c0d80e5198b347ab91fbcccd52ebcd29
出典データセット
uspto-grants-2010_02
特許番号
US07659399B2

関連ノート

読み込み中…