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 1754892Notes

Reaction equation

HRID 1754892 reaction equation
[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]

Participants

7

Reactant 4

HCID 24083Sulfuric acid magnesium salt (1:1)HCID 1062172-(Methyldithio)isobutyraldehydeHCID 5049666Sodium triacetoxyborohydride2×HCID 59440224HCID 59440224, compound

Product 1

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

Reagents, catalysts & solvents 2

HCID 3007855ZincchlorideCatalystHCID 111,2-DichloroethaneSolvent

Procedure

To a solution of 3,5-bis(((tert-butyldimethylsilyl)oxy)methyl)-N-(2-(2-(2-methoxyethoxyl)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-methoxyethoxyl)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.

Workup

  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)

Sources & evidence

ORD record
ord-5557964f049c41eca2e39a86309e033b
Source dataset
uspto-grants-2015_10
Patent number
US09169272B2

Reaction notes

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