Ethanol → HCID 54471273, compound

HRID 1457506Notes

Reaction equation

HRID 1457506 reaction equation
C1(=O)[N:5]([CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][N:11]([CH2:46][C:47]([S:50][C:51]([C:64]2[CH:69]=[CH:68][CH:67]=[CH:66][CH:65]=2)([C:58]2[CH:63]=[CH:62][CH:61]=[CH:60][CH:59]=2)[C:52]2[CH:57]=[CH:56][CH:55]=[CH:54][CH:53]=2)([CH3:49])[CH3:48])[CH2:12][CH2:13][N:14]([C:39]([O:41][C:42]([CH3:45])([CH3:44])[CH3:43])=[O:40])[CH2:15][C:16]([CH3:38])([S:18][C:19]([C:32]2[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=2)([C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)[CH3:17])C(=O)C2=CC=CC=C12.C(O)C.O.O.NN>C1COCC1>[C:42]([O:41][C:39]([N:14]([CH2:15][C:16]([CH3:38])([S:18][C:19]([C:20]1[CH:21]=[CH:22][CH:23]=[CH:24][CH:25]=1)([C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1)[C:32]1[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1)[CH3:17])[CH2:13][CH2:12][N:11]([CH2:46][C:47]([S:50][C:51]([C:64]1[CH:65]=[CH:66][CH:67]=[CH:68][CH:69]=1)([C:58]1[CH:59]=[CH:60][CH:61]=[CH:62][CH:63]=1)[C:52]1[CH:53]=[CH:54][CH:55]=[CH:56][CH:57]=1)([CH3:49])[CH3:48])[CH2:10][CH2:9][CH2:8][CH2:7][CH2:6][NH2:5])=[O:40])([CH3:43])([CH3:44])[CH3:45]

Participants

6

Reactant 4

HCID 702EthanolHCID 962Water2×HCID 24654Hydrazine hydrate (1:1)HCID 54551369HCID 54551369, compound

Product 1

HCID 54471273HCID 54471273, compoundYield 68%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A 250 mL single-necked round-bottomed flask, equipped with stir bar and reflux condenser, was charged with 9-phthalimido-N1 -(t-butoxycarbonyl)-N1, N4 -bis[2-methyl-2-(triphenylmethylthio)propyl ]-1,4-diazanonane (5.50 g, 5.319.43 mmol) in 25 mL of THF. To this was added 100 mL ethanol and 5 mL water. The addition of water caused the starting material to precipitate out of solution. Hydrazine hydrate (1.2 mL, 24.7 mmol, 466 mole %) was added, and the reaction heated at reflux for two days. The reaction mixture was concentrated and partitioned between 100 mL each of water and 0.25M K2CO3. The organic layer was separated and washed once with brine (75 mL), dried over Na2SO4 and concentrated to a solid foam. Purification of the crude product by low-pressure liquid chromatography (100 g SiO2, CHCl3 →5% methanol in CHCl3, the column pre-treated with 200 mL 2% triethylamine in CHCl3) afforded 3.27 g of pure N1 -(t-butoxycarbonyl)-N1,N4 -bis [2-methyl-2-(triphenylmethylthio)propyl ]-1,4,10-triazadecane as a yellow foam (68% yield). Chemical analysis of the purified product confirmed its identity as follows:

Workup

  1. customA 250 mL single-necked round-bottomed flask, equipped
  2. temperaturereflux condenser
  3. customto precipitate out of solution
  4. temperaturethe reaction heated
  5. temperatureat reflux for two days
  6. concentrationThe reaction mixture was concentrated
  7. custompartitioned between 100 mL each of water and 0.25M K2CO3
  8. customThe organic layer was separated
  9. washwashed once with brine (75 mL)
  10. dry with materialdried over Na2SO4
  11. concentrationconcentrated to a solid foam
  12. customPurification of the crude product by low-pressure liquid chromatography (100 g SiO2, CHCl3
  13. additionthe column pre-treated with 200 mL 2% triethylamine in CHCl3)

Sources & evidence

ORD record
ord-6b54a1b9c39742f5a03b6775c05264da
Source dataset
uspto-grants-1998_12
Patent number
US05849261

Reaction notes

Loading…