Methanol → Bis [4-(vinyloxy)butyl]trimethyl-1,6-hexanediylbiscarbamate

HRID 1983220Notes

Reaction equation

HRID 1983220 reaction equation
[CH3:1][CH:2]([CH2:9][CH2:10][CH2:11][CH2:12][N:13]=[C:14]=[O:15])[C:3]([CH3:8])([CH3:7])[N:4]=[C:5]=[O:6].[O:16]1[CH2:20][CH2:19][CH2:18][CH2:17]1.[CH:21]([O:23][CH2:24][CH2:25][CH2:26][CH2:27][OH:28])=[CH2:22].[N-]=[C:30]=[O:31].[CH3:32]O>C([O-])(=O)CCCCCCCCCCC.C([O-])(=O)CCCCCCCCCCC.C([Sn+2]CCCC)CCC>[CH3:1][CH:2]([CH2:9][CH2:10][CH2:11][CH2:12][NH:13][C:14](=[O:15])[O:16][CH2:20][CH2:19][CH2:18][CH2:17][O:31][CH:30]=[CH2:32])[C:3]([CH3:7])([CH3:8])[NH:4][C:5](=[O:6])[O:28][CH2:27][CH2:26][CH2:25][CH2:24][O:23][CH:21]=[CH2:22]

Participants

7

Reactant 5

HCID 887MethanolHCID 8028TetrahydrofuranHCID 873291,4-Butanediol monovinyl etherHCID 105034IsocyanateHCID 3033881Trimethylhexa-1,6-diyl diisocyanate

Product 1

HCID 87462387Bis [4-(vinyloxy)butyl]trimethyl-1,6-hexanediylbiscarbamateYield 89%

Reagents, catalysts & solvents 1

HCID 9809426Di-n-butyldilauryltinCatalyst

Procedure

To a 2 liter three neck flask equipped with a stopper, dropping funnel, stir bar, and reflux condenser was added trimethyl-1,6-diisocyanatohexane (mixture of 2,2,4- and 2,4,4-isomers, 118.7 grams, 0.57 mol, obtained from Sigma-Aldrich, Milwaukee, Wis.), dibutyltin dilaurate (3.56 grams, 5.6 mmol, obtained from Sigma-Aldrich) and anhydrous tetrahydrofuran (1 liter). 1,4-Butanediol vinyl ether (133.2 grams, 1.2 mol, obtained from Sigma-Aldrich) was added slowly dropwise to the stirring solution via the addition funnel. The reaction mixture was brought to reflux and was kept at this temperature until deemed complete by infrared spectroscopy (about 5 hours, confirmed by the disappearance of the isocyanate peak at 2200 cm−1). When the reaction was complete, methanol (500 milliliters) was added to quench any residual isocyanate and the solution was stirred for 0.5 hour. The solvent was stripped in vacuo and the residual oil was triturated with hexane (3×500 milliliters), dissolved in methylene chloride (1 liter), washed with water (1×750 milliliters), dried over anhydrous magnesium sulfate, filtered, and concentrated in vacuo to afford 221 grams of a pale yellow oil (89 percent yield). The product was believed to be a mixture of compounds of the formulae

Workup

  1. temperaturereflux condenser
  2. temperatureto reflux
  3. customabout 5 hours
  4. customto quench any residual isocyanate
  5. stirringthe solution was stirred for 0.5 hour
  6. customthe residual oil was triturated with hexane (3×500 milliliters)
  7. dissolutiondissolved in methylene chloride (1 liter)
  8. washwashed with water (1×750 milliliters)
  9. dry with materialdried over anhydrous magnesium sulfate
  10. filtrationfiltered
  11. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-2a30802d6fec45498b4272a168e68a5a
Source dataset
uspto-grants-2009_06
Patent number
US07541406B2

Reaction notes

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