Bis(trimethylsilyl)carbodiimide → N-(6-(phenylethynyl)-2',4',5',6'-tetrahydrospiro[chroman-2,3'-pyran]-4-ylidene)cyanamide

HRID 1408831Notes

Reaction equation

HRID 1408831 reaction equation
[C:1]1([C:7]#[C:8][C:9]2[CH:10]=[C:11]3[C:21](=[CH:22][CH:23]=2)[O:20][C:14]2([CH2:19][CH2:18][CH2:17][O:16][CH2:15]2)[CH2:13][C:12]3=O)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.C[Si]([N:29]=[C:30]=[N:31][Si](C)(C)C)(C)C>C(Cl)Cl.Cl[Ti](Cl)(Cl)Cl>[C:1]1([C:7]#[C:8][C:9]2[CH:10]=[C:11]3[C:21](=[CH:22][CH:23]=2)[O:20][C:14]2([CH2:19][CH2:18][CH2:17][O:16][CH2:15]2)[CH2:13][C:12]3=[N:31][C:30]#[N:29])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1

Participants

5

Reactant 2

HCID 70473Bis(trimethylsilyl)carbodiimideHCID 584246946-(Phenylethynyl)-2',4',5',6'-tetrahydrospiro[chroman-2,3'-pyran]-4-one

Product 1

HCID 58424611N-(6-(phenylethynyl)-2',4',5',6'-tetrahydrospiro[chroman-2,3'-pyran]-4-ylidene)cyanamideYield 121.2%

Reagents, catalysts & solvents 2

HCID 24193Titanium TetrachlorideCatalystHCID 6344DichloromethaneSolvent

Procedure

To a solution of 6-(phenylethynyl)-2′,4′,5′,6′-tetrahydrospiro[chroman-2,3′-pyran]-4-one (86 mg, 0.27 mmol) in anhydrous DCM (10 mL) under N2 atmosphere was added 1 M TiCl4 (in DCM, 0.54 mL, 0.54 mmol) dropwise within 15 min at room temperature. It was stirred another 1 h after the addition. To this mixture was added Bis-trimethylsilylcarbodiimide (0.16 mL, 0.427 mmol) dropwise. The resulting mixture was stirred 80 h. The reaction mixture was quenched with ice-water (15 g), and stirred for 30 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 112 mg the crude desired product as light yellow solid, which was used for next step without further purification. MS ESI+ve m/z 343 (M+H)+.

Workup

  1. additionafter the addition
  2. stirringThe resulting mixture was stirred 80 h
  3. customThe reaction mixture was quenched with ice-water (15 g)
  4. stirringstirred for 30 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-b9c3136ad7b44cb38e592b0147ae7d29
Source dataset
uspto-grants-2014_12
Patent number
US08921359B2

Reaction notes

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