Dimethylformamide → 3,3'-Bis(3-Dimethylamino-2-methylpropoxy)Benzil

HRID 1580944Notes

Reaction equation

HRID 1580944 reaction equation
[Tl].[Tl].[OH:3][C:4]1[CH:5]=[C:6]([C:10]([C:12]([C:14]2[CH:19]=[CH:18][CH:17]=[C:16]([OH:20])[CH:15]=2)=[O:13])=[O:11])[CH:7]=[CH:8][CH:9]=1.[CH3:21][N:22]([CH3:28])[CH2:23][CH:24]([CH3:27])[CH2:25]Cl.C1[C:38]2[C:33](=[CH:34]C=CC=2)[CH:32]=CC=1S(O)(=O)=O.[CH3:43][N:44](C)[CH:45]=O>C1(C)C=CC=CC=1.C(O)C>[CH3:21][N:22]([CH3:28])[CH2:23][CH:24]([CH3:27])[CH2:25][O:3][C:4]1[CH:5]=[C:6]([C:10]([C:12]([C:14]2[CH:19]=[CH:18][CH:17]=[C:16]([O:20][CH2:32][CH:33]([CH3:38])[CH2:34][N:44]([CH3:45])[CH3:43])[CH:15]=2)=[O:13])=[O:11])[CH:7]=[CH:8][CH:9]=1

Participants

7

Reactant 4

HCID 6228DimethylformamideHCID 84202-Naphthalenesulfonic acidHCID 909063-Chloro-2-methylpropyl(dimethyl)amineHCID 867330203,3'-Dihydroxybenzil dithallium salt

Product 1

HCID 215322763,3'-Bis(3-Dimethylamino-2-methylpropoxy)Benzil

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 1140TolueneSolvent2×

Procedure

To a dry, stirred suspension of 3,3'-dihydroxybenzil dithallium salt (20 g.) in toluene (250 ml.) and N,N-dimethylformamide (250 ml.) was added dropwise 104 ml. of a solution containing 48 g. of 3-dimethylamino-2-methylpropyl chloride in 500 ml. of toluene. The mixture was stirred and heated under reflux overnight. The resulting heavy white precipitate was removed and washed with toluene. The toluene solution and washings were evaporated to a syrup which was subjected to further evaporation using an oil pump vacuum. The syrup was dissolved in chloroform and applied to a column (48 × 5.2 cm) of a "dry column grade" alumina (Woelm) prepacked in chloroform. Elution was with chloroform and 500 ml. fractions (1 and 2) and 250 ml. (3-6) fractions were collected. Fractions 3-6 were pooled and evaporated to give 10.00 g. of syrup. To 7.55 g. of this material in ethanol (150 ml.) was added naphthalene-2-sulfonic acid (7.72 g.). The solution was warmed and decolorized. Evaporation and addition of seeds and ether gave the title product (9.88 g.) as the bis(2-naphthalenesulfonate) salt; m.p. 162-164°. Recrystallization with decolorization gave pure product; m.p. 164-166°.

Workup

  1. additionwas added dropwise 104 ml
  2. additionof a solution containing 48 g
  3. stirringThe mixture was stirred
  4. temperatureheated
  5. temperatureunder reflux overnight
  6. customThe resulting heavy white precipitate was removed
  7. washwashed with toluene
  8. customThe toluene solution and washings were evaporated to a syrup which
  9. customwas subjected to further evaporation
  10. dissolutionThe syrup was dissolved in chloroform
  11. customdry column grade" alumina (Woelm)
  12. washElution
  13. custom(3-6) fractions were collected
  14. customevaporated
  15. customto give 10.00 g
  16. temperatureThe solution was warmed
  17. customEvaporation and addition of seeds and ether

Sources & evidence

ORD record
ord-89f15f8b1034403888ca0c2cf309d5d7
Source dataset
uspto-grants-1976_01
Patent number
US03935191

Reaction notes

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