Bis(trimethylsilyl)carbodiimide → N-(5-(3-cyanophenyl)-2',3',5',6'-tetrahydrospiro[indene-2,4'-pyran]-3(1H)-ylidene)cyanamide

HRID 472959Notes

Reaction equation

HRID 472959 reaction equation
O=[C:2]1[C:10]2([CH2:15][CH2:14][O:13][CH2:12][CH2:11]2)[CH2:9][C:8]2[C:3]1=[CH:4][C:5]([C:16]1[CH:17]=[C:18]([CH:21]=[CH:22][CH:23]=1)[C:19]#[N:20])=[CH:6][CH:7]=2.C[Si]([N:28]=[C:29]=[N:30][Si](C)(C)C)(C)C>C(Cl)Cl.Cl[Ti](Cl)(Cl)Cl>[C:19]([C:18]1[CH:17]=[C:16]([C:5]2[CH:4]=[C:3]3[C:8](=[CH:7][CH:6]=2)[CH2:9][C:10]2([CH2:11][CH2:12][O:13][CH2:14][CH2:15]2)[C:2]3=[N:30][C:29]#[N:28])[CH:23]=[CH:22][CH:21]=1)#[N:20]

Participants

5

Reactant 2

HCID 70473Bis(trimethylsilyl)carbodiimideHCID 665847993-(1-Oxo-1,2',3,3',5',6'-hexahydrospiro[indene-2,4'-pyran]-6-yl)benzonitrile

Product 1

HCID 86652168N-(5-(3-cyanophenyl)-2',3',5',6'-tetrahydrospiro[indene-2,4'-pyran]-3(1H)-ylidene)cyanamideYield 96.7%

Reagents, catalysts & solvents 2

HCID 24193Titanium TetrachlorideCatalystHCID 6344DichloromethaneSolvent

Procedure

To a solution of 3-(1-oxo-1,2′,3,3′,5′,6′-hexahydrospiro[indene-2,4′-pyran]-6-yl)benzonitrile (42 mg, 0.139 mmol) in anhydrous DCM (10 mL) under N2 atmosphere was added 1 M TiCl4 (in DCM, 0.28 mL, 0.28 mmol) dropwise within 15 min at room temperature. It was stirred another 1 h after the addition. To this mixture was added Bis-trimethylsilylcarbodiimide (0.1 mL, 0.427 mmol) dropwise. The resulting mixture was stirred overnight. The reaction mixture was quenched with ice-water (20 g), and stirred for 20 min, then it was transferred to a separating funnel, the separated aqueous phase was extracted 2 times with DCM. The combined organic phases were dried over anhydrous Na2SO4, and filtered, and concentrated to give 44 mg of N-(5-(3-cyanophenyl)-2′,3′,5′,6′-tetrahydrospiro[indene-2,4′-pyran]-3(1H)-ylidene)cyanamide as light brown solid which was used for next step without further purification. MS ESI+ve m/z 328 (M+H)+.

Workup

  1. additionafter the addition
  2. stirringThe resulting mixture was stirred overnight
  3. customThe reaction mixture was quenched with ice-water (20 g)
  4. stirringstirred for 20 min
  5. customit was transferred to a separating funnel
  6. extractionthe separated aqueous phase was extracted 2 times with DCM
  7. dry with materialThe combined organic phases were dried over anhydrous Na2SO4
  8. filtrationfiltered
  9. concentrationconcentrated

Sources & evidence

ORD record
ord-47522a6aed0a459bb13f014c5fab4561
Source dataset
uspto-grants-2014_01
Patent number
US08633212B2

Reaction notes

Loading…