Triethylamine → HCID 58966518, compound

HRID 390755Notes

Reaction equation

HRID 390755 reaction equation
[Br:1][C:2]1[CH:26]=[CH:25][C:24]([C:27]([F:30])([F:29])[F:28])=[CH:23][C:3]=1[CH2:4][N:5]([CH2:8][C:9]1[CH:14]=[C:13]([C:15]([F:18])([F:17])[F:16])[CH:12]=[C:11]([C:19]([F:22])([F:21])[F:20])[CH:10]=1)[C:6]#[N:7].C(N(CC)CC)C.C[Si]([N:42]=[N+:43]=[N-:44])(C)C.[OH-].[Na+]>C(OC)(C)(C)C>[Br:1][C:2]1[CH:26]=[CH:25][C:24]([C:27]([F:28])([F:29])[F:30])=[CH:23][C:3]=1[CH2:4][N:5]([CH2:8][C:9]1[CH:10]=[C:11]([C:19]([F:20])([F:21])[F:22])[CH:12]=[C:13]([C:15]([F:18])([F:17])[F:16])[CH:14]=1)[C:6]1[N:42]=[N:43][NH:44][N:7]=1

Participants

6

Reactant 4

HCID 8471TriethylamineHCID 14798Sodium HydroxideHCID 78378Azidotrimethylsilane2×HCID 58966526HCID 58966526, compound

Product 1

HCID 58966518HCID 58966518, compoundYield 99%

Reagents, catalysts & solvents 1

HCID 15413tert-Butyl methyl etherSolvent

Conditions

Temperature
50 °C

Procedure

To the product of step C (909 g, 1.80 mol) in methyl tert-butyl ether (9 L) was added triethylamine (2.5 L, 18 mol) followed by trimethylsilylazide (415 g, 3.60 mol). The resulting mixture was heated to 50° C. for 8 hours. An aliquot was checked by HPLC and starting material was still present. The mixture was cooled and trimethylsilylazide (50 g) was added. The mixture was again heated to 50° C. and stirred 3 hours. After cooling, 1N sodium hydroxide (9 L) was added. The layers were separated (added 150 ml ethanol to facilitate separation). The organics were washed with aqueous 10% citric acid solution (8 L, then 2 L) until washings were acidic. The organics were dried over sodium sulfate, filtered, and concentrated. The resulting solid turned white upon standing (976 g, 99% yield). 1H-NMR (CD3OD)7.47 (m, 3H), 7.64 (d, 8.3 Hz, 1H), 7.44 (d, 2.1 Hz, 1H), 7.38 (dd, 2.1 Hz, 8.3 Hz, 1H), 4.88 (s, 2H), 4.86 (s, 2H). Mass Spec (ESI): M+1=548.0

Workup

  1. temperatureThe mixture was cooled
  2. temperatureThe mixture was again heated to 50° C.
  3. temperatureAfter cooling
  4. customThe layers were separated
  5. addition(added 150 ml ethanol to facilitate separation)
  6. washThe organics were washed with aqueous 10% citric acid solution (8 L
  7. dry with materialThe organics were dried over sodium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated

Sources & evidence

ORD record
ord-29d95c6c290945deb6e26a3d1baee089
Source dataset
uspto-grants-2013_02
Patent number
US08383660B2

Reaction notes

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