Methyl chloroformate → HCID 70533243, compound

HRID 435451Notes

Reaction equation

HRID 435451 reaction equation
C(NC(C)C)(C)C.C([Li])CCC.[C:13]1([C:19]2[C:20]3[O:40][CH2:39][O:38][CH:22]([CH:23]([N:30]=[CH:31][C:32]4[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=4)[C:24]#[C:25][Si:26]([CH3:29])([CH3:28])[CH3:27])[C:21]=3[CH:41]=[CH:42][C:43]=2[C:44]2[CH:49]=[CH:48][CH:47]=[CH:46][CH:45]=2)[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.Cl[C:51]([O:53][CH3:54])=[O:52].[NH4+].[Cl-]>O1CCCC1.O>[C:51]([C:23]([CH:22]1[O:38][CH2:39][O:40][C:20]2[C:19]([C:13]3[CH:14]=[CH:15][CH:16]=[CH:17][CH:18]=3)=[C:43]([C:44]3[CH:49]=[CH:48][CH:47]=[CH:46][CH:45]=3)[CH:42]=[CH:41][C:21]1=2)([N:30]=[CH:31][C:32]1[CH:33]=[CH:34][CH:35]=[CH:36][CH:37]=1)[C:24]#[C:25][Si:26]([CH3:29])([CH3:28])[CH3:27])([O:53][CH3:54])=[O:52]

Participants

8

Reactant 5

HCID 6586Methyl chloroformateHCID 7912DiisopropylamineHCID 25517Ammonium ChlorideHCID 70533072HCID 70533072, compoundHCID 178418339Butyllithium

Product 1

HCID 70533243HCID 70533243, compoundYield 96.6%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent3×

Procedure

To diisopropylamine (700 mg.) in 15 ml. tetrahydrofuran at -78° under N2 was added 3.8 ml. of 1.64 M n-butyllithium dropwise. After 5 minutes, 3-(3,4-diphenylmethylenedioxybenzyl)-1-trimethylsilyl-N-benzylidene-3-aminoprop-1-yne (3.378 g.; 6.74 mmol) in 15 ml. tetrahydrofuran was added dropwise (10 minutes). After an additional 5 minutes, methyl chloroformate (680 mg.) in tetrahydrofuran (10 ml.) was added dropwise (5 minutes). After 40 minutes at -78° the solution was warmed to 0° and the color lightened from deep red to orange. After 10 minutes at 0°, water (5 ml.) was added dropwise followed by 10% aqueous NH4Cl (30 ml.). The layers were separated and the mixture extracted as in the previous example, dried over Na2SO4 and concentrated to dryness to give 3-carbomethoxy-3-(3,4-diphenylmethylenedioxybenzyl)-1-trimethylsilyl-N-benzylidene-3-aminoprop-1-yne (3.645 g.) as an orange foam; Mass spectrum M/e 559, large fragmentation peaks at 287 (base peak) and 272. ##STR13##

Workup

  1. waitAfter an additional 5 minutes
  2. temperatureAfter 40 minutes at -78° the solution was warmed to 0°
  3. waitAfter 10 minutes at 0°
  4. customThe layers were separated
  5. dry with materialdried over Na2SO4
  6. concentrationconcentrated to dryness

Sources & evidence

ORD record
ord-5786311c84534a3e8a7e76dd51a402b6
Source dataset
uspto-grants-1983_08
Patent number
US04401676

Reaction notes

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