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Sulfuric acid magnesium salt (1:1) → 3,5-bis(((tert-butyldimethylsilyl)oxy)methyl)-N-(2-(2-(2-methoxyethoxy)ethoxy)ethyl)-N-(2-methyl-2-(methyldisulfanyl)propyl)aniline

HRID 336325
ノート
印刷プレビュー

反応式

HRID 336325 の反応式
[Si:1]([O:8][CH2:9][C:10]1[CH:11]=[C:12]([CH:24]=[C:25]([CH2:27][O:28][Si:29]([C:32]([CH3:35])([CH3:34])[CH3:33])([CH3:31])[CH3:30])[CH:26]=1)[NH:13][CH2:14][CH2:15][O:16][CH2:17][CH2:18][O:19][CH2:20][CH2:21][O:22][CH3:23])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].[CH3:36][S:37][S:38][C:39]([CH3:43])([CH3:42])[CH:40]=O.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+].S([O-])([O-])(=O)=O.[Mg+2]>ClCCCl.[Cl-].[Zn+2].[Cl-]>[Si:1]([O:8][CH2:9][C:10]1[CH:11]=[C:12]([CH:24]=[C:25]([CH2:27][O:28][Si:29]([C:32]([CH3:35])([CH3:34])[CH3:33])([CH3:30])[CH3:31])[CH:26]=1)[N:13]([CH2:14][CH2:15][O:16][CH2:17][CH2:18][O:19][CH2:20][CH2:21][O:22][CH3:23])[CH2:40][C:39]([CH3:43])([S:38][S:37][CH3:36])[CH3:42])([C:4]([CH3:5])([CH3:7])[CH3:6])([CH3:3])[CH3:2]
参加物実験手順後処理出典と根拠反応ノート

参加物

7

反応物 4

HCID 24083Sulfuric acid magnesium salt (1:1)HCID 1062172-(Methyldithio)isobutyraldehydeHCID 5049666Sodium triacetoxyborohydride2 回HCID 594402243,5-bis((tert-butyldimethylsilyloxy)methyl)-N-(2-(2-(2-methoxyethoxy)ethoxy)ethyl)aniline

生成物 1

HCID 866712843,5-bis(((tert-butyldimethylsilyl)oxy)methyl)-N-(2-(2-(2-methoxyethoxy)ethoxy)ethyl)-N-(2-methyl-2-(methyldisulfanyl)propyl)aniline
収率 41.7%

試薬・触媒・溶媒 2

HCID 3007855Zincchloride触媒HCID 111,2-Dichloroethane溶媒

実験手順

To a solution of 3,5-bis(((tert-butyldimethylsilyl)oxy)methyl)-N-(2-(2-(2-methoxyethoxy)ethoxy)ethyl)aniline (6.7 g, 12.69 mmol) in anhydrous 1,2-dichloroethane (50 ml) was added 2-(methyldithio)isobutyraldehyde (2.74 ml, 19.04 mmol), sodium triacetoxyborohydride (2.8 g, 1 eq), zinc(II) chloride (0.865 g, 6.35 mmol) and magnesium sulfate (2.292 g, 19.04 mmol). The mixture was stirred for five hours at ambient temperature. Sodium triacetoxyborohydride (2.8 g, 1 eq) was added. The reaction continued to stir at ambient temperature for 20 hours. The mixture was filtered through celite rinsing with dichloromethane and concentrated under reduced pressure then extracted with ethyl acetate and water. The organic extracts were washed with brine, dried over magnesium sulfate, filtered, concentrated and purified by combiflash (EtOAc/Hex) to give 3,5-bis(((tert-butyldimethylsilyl)oxy)methyl)-N-(2-(2-(2-methoxyethoxy)ethoxy)ethyl)-N-(2-methyl-2-(methyldisulfanyl)propyl)aniline (3.5 g, 40%). 1H NMR (400 Hz, CDCl3): δ 6.73 (s, 2H), 6.59 (s, 1H), 4.56 (s, 4H), 3.65-3.51 (m, 14H), 3.30 (s, 3H), 2.38 (s, 3H), 1.28 (s, 6H), 0.84 (s, 18H), 0.00 (s, 12H). MS (m/z). found 684.2 (M+Na)+. See FIG. 46.

後処理

  1. stirringto stir at ambient temperature for 20 hours
  2. filtrationThe mixture was filtered
  3. washthrough celite rinsing with dichloromethane
  4. concentrationconcentrated under reduced pressure
  5. extractionthen extracted with ethyl acetate and water
  6. washThe organic extracts were washed with brine
  7. dry with materialdried over magnesium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated
  10. custompurified by combiflash (EtOAc/Hex)

出典と根拠

ORDレコード
ord-3e9dc086e2164c29be9195eabd292e29
出典データセット
uspto-grants-2014_11
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US08889669B2

反応ノート

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