N,N,N',N'-Tetramethylethylenediamine → HCID 14498206, compound

HRID 280648Notes

Reaction equation

HRID 280648 reaction equation
[Si:1]([O:8][CH2:9][C:10]1[CH:15]=[C:14]([Cl:16])[CH:13]=[C:12]([Cl:17])[CH:11]=1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].CN(C)CCN(C)C.C([Li])CCC.CCCCCC.[Cl:37][C:38]1[CH:46]=[CH:45][C:41]([C:42](Cl)=[O:43])=[CH:40][CH:39]=1>O1CCCC1>[Si:1]([O:8][CH2:9][C:10]1[CH:15]=[C:14]([Cl:16])[C:13]([C:42]([C:41]2[CH:45]=[CH:46][C:38]([Cl:37])=[CH:39][CH:40]=2)=[O:43])=[C:12]([Cl:17])[CH:11]=1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2]

Participants

7

Reactant 5

HCID 8037N,N,N',N'-TetramethylethylenediamineHCID 8058HexaneHCID 85014-Chlorobenzoyl chlorideHCID 14498205HCID 14498205, compoundHCID 178418339Butyllithium

Product 1

HCID 14498206HCID 14498206, compoundYield 60%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A stirred -55° C. solution of 3,5-dichlorobenzyl t-butyldimethylsilyl ether (1.46 g, 5.00 mmol) and tetramethylethylenediamine (0.755 mL, 0.581 g, 5.01 mmol) in tetrahydrofuran (5 mL) under nitrogen atmosphere was treated dropwise over 10 minutes with a 1.6 M solution of n-butyllithium in hexane (3.3 mL, 5.25 mmol). After 30 minutes at -55° C., a solution of p-chlorobenzoyl chloride (0.875 g, 5.00 mmol) in tetrahydrofuran (1.0 mL) was added over 15 minutes. The resulting mixture was stirred 2 hours at -55° to -30° C. and 1.5 hours at ambient temperature. The reaction was quenched by addition of saturated aqueous ammonium chloride (1.1 mL) and stirred 30 minutes. The mixture was treated with sodium sulfate (1.1 g), stirred 1 hour, and decanted. The residual solid was washed well with diethyl ether. The combined solution and washes were extracted twice with water, once with 10% aqueous citric acid, and once with brine, dried over anhydrous magnesium sulfate, and evaporated under vacuum to provide 1.93 g of crude brown oil. A total of 585 mg of oil was chromatographed on eight 1000μ 20 cm×20 cm silica gel preparative thick layer chromatography plates developed with 5:1 (v/v) hexane-ethyl acetate to provide 356 mg (60%) 4-(t-butyldimethylsilyloxymethyl)-2,4',6-trichlorobenzophenone; NMR (CDCl3): 0.14 s (6H), 0.95 s (9H), 4.72 s (2H), 7.27 s (2H), 7.35 d (J=9Hz, 2H), 7.70 d (J=9Hz, 2H).

Workup

  1. customThe reaction was quenched by addition of saturated aqueous ammonium chloride (1.1 mL)
  2. stirringstirred 30 minutes
  3. additionThe mixture was treated with sodium sulfate (1.1 g)
  4. stirringstirred 1 hour
  5. customdecanted
  6. washThe residual solid was washed well with diethyl ether
  7. extractionThe combined solution and washes were extracted twice with water, once with 10% aqueous citric acid
  8. dry with materialonce with brine, dried over anhydrous magnesium sulfate
  9. customevaporated under vacuum
  10. customto provide 1.93 g of crude brown oil
  11. customA total of 585 mg of oil was chromatographed on eight 1000μ 20 cm×20 cm silica gel preparative thick layer chromatography plates

Sources & evidence

ORD record
ord-7db0ab23c71340d3b0eceed2e3ca7e54
Source dataset
uspto-grants-1986_05
Patent number
US04590201

Reaction notes

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