Bis(trimethylsilyl)carbodiimide → N-(5'-bromo-5,6,8,9-tetrahydro-3'H-spiro[benzo[7]annulene-7,2'-benzofuran]-3'-ylidene)cyanamide

HRID 472969Notes

Reaction equation

HRID 472969 reaction equation
[Br:1][C:2]1[CH:3]=[CH:4][C:5]2[O:9][C:8]3([CH2:15][CH2:14][C:13]4[CH:16]=[CH:17][CH:18]=[CH:19][C:12]=4[CH2:11][CH2:10]3)[C:7](=O)[C:6]=2[CH:21]=1.C[Si](C)(C)[N:24]=[C:25]=[N:26][Si](C)(C)C>C(Cl)Cl.Cl[Ti](Cl)(Cl)Cl>[Br:1][C:2]1[CH:3]=[CH:4][C:5]2[O:9][C:8]3([CH2:15][CH2:14][C:13]4[CH:16]=[CH:17][CH:18]=[CH:19][C:12]=4[CH2:11][CH2:10]3)[C:7](=[N:26][C:25]#[N:24])[C:6]=2[CH:21]=1

Participants

5

Reactant 2

HCID 70473Bis(trimethylsilyl)carbodiimideHCID 581970305'-bromo-5,6,8,9-tetrahydro-3'H-spiro[benzo[7]annulene-7,2'-benzofuran]-3'-one

Product 1

HCID 58197813N-(5'-bromo-5,6,8,9-tetrahydro-3'H-spiro[benzo[7]annulene-7,2'-benzofuran]-3'-ylidene)cyanamide

Reagents, catalysts & solvents 2

HCID 24193Titanium TetrachlorideCatalystHCID 6344DichloromethaneSolvent

Procedure

To a solution of 5′-bromo-5,6,8,9-tetrahydro-3′H-spiro[benzo[7]annulene-7,2′-benzofuran]-3′-one (0.1660 g, 0.48 mmol) in CH2Cl2 (5 mL) was added TiCl4 (1.0 M in CH2Cl2, 1.0 mL, 1.0 mmol) dropwise at room temperature. The reaction mixture was turned into orange precipitates in a few minutes. After 1 h, 1,3-bis(trimethylsilyl)carbodiimide (0.30 mL, 1.32 mmol) was added via a syringe. The precipitates were disappeared and the reaction mixture was turned into a red solution. The mixture was stirred at room temperature for 15 h and then quenched with ice, extracted with CH2Cl2, dried over Na2SO4. After the solvent was removed under reduced pressure, the crude product was directly used in the next step without further purification. LC-MS tR=2.27 min in 3 min chromatography, m/z 367, 369 (MH+).

Workup

  1. custominto orange precipitates in a few minutes
  2. customquenched with ice
  3. extractionextracted with CH2Cl2
  4. dry with materialdried over Na2SO4
  5. customAfter the solvent was removed under reduced pressure
  6. customthe crude product was directly used in the next step without further purification
  7. waitLC-MS tR=2.27 min in 3 min chromatography, m/z 367, 369 (MH+)

Sources & evidence

ORD record
ord-aee747c7ff3d4fd0a8164adbb7df7438
Source dataset
uspto-grants-2014_01
Patent number
US08633212B2

Reaction notes

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