Dimethylamine → 1-(6-(Dimethylamino)naphthalen-2-yl)ethanone

HRID 1391985Notes

Reaction equation

HRID 1391985 reaction equation
[CH3:1][NH:2][CH3:3].CN(C)P(=O)(N(C)C)N(C)C.C1(C)C=CC=CC=1.[C:22]([C:25]1[CH:34]=[CH:33][C:32]2[C:27](=[CH:28][CH:29]=[C:30]([O:35][CH3:36])[CH:31]=2)[CH:26]=1)(=[O:24])[CH3:23]>O.C(OCC)(=O)C>[C:22]([C:25]1[CH:34]=[CH:33][C:32]2[C:27](=[CH:28][CH:29]=[C:30]([O:35][CH3:36])[CH:31]=2)[CH:26]=1)(=[O:24])[CH3:23].[C:22]([C:25]1[CH:34]=[CH:33][C:32]2[C:27](=[CH:28][CH:29]=[C:30]([N:2]([CH3:3])[CH3:1])[CH:31]=2)[CH:26]=1)(=[O:24])[CH3:23]

Participants

7

Reactant 4

HCID 674DimethylamineHCID 1140TolueneHCID 12679HexamethylphosphoramideHCID 775062-Acetyl-6-methoxynaphthalene

Product 2

HCID 775062-Acetyl-6-methoxynaphthaleneHCID 153339701-(6-(Dimethylamino)naphthalen-2-yl)ethanoneYield 123.8%

Reagents, catalysts & solvents 1

HCID 22728543Water ethylacetateSolvent

Procedure

To a solution of 5.26 g (117 mmol) of dimethylamine in 29 mL of freshly distilled hexamethylphosphoric triamide (HMPT) were added 31 mL of dry toluene and 780 mg (112 mmol) of Li in small pieces. The mixture was stirred under argon at room temperature for 1.5 hours. 2-Acetyl-6-methoxynaphthalene was prepared as described in Arsenijevic et al., Org. Synth. Coll. 1988, 6:34-36, the disclosure of which is incorporated herein by reference. 2-Acetyl-6-methoxynaphthalene (5.57 g, 27.8 mmol) was added in one portion, and stirring was continued for 20 hours. The mixture was cooled in an ice-water bath and poured into a cold water/ethyl acetate mixture (300 mL each). After thorough mixing, the layers were separated, and the water layer was extracted twice with 225 mL of ethyl acetate. Organic extracts were combined, dried, and evaporated to give a yellow solid. Recrystallization from ethanol afforded 3.67 g (64%) of 2-acetyl-6-(dimethylamino)naphthalene (ADMAN) as a yellow solid, melting at 153.5-155° C.: 1H NMR (CDCl3, TMS) δ 2.67 (s, 3H, COCH3), 3.15 (s, 6H, N(CH3)2), 6.87 (d, 1H, H-5), 7.17 (dd, 1H, H-7), 7.63 (d, 1H, H-4), 7.80 (d, 1H, H-8), 7.92 (dd, 1H, H-3), 8.32 (bs, 1H, H-1). J1,3=2.3 Hz, J3,4=8.7 Hz, J5,7=2.4 Hz, J7,8=9.3 Hz. MS (M+) 213: found: 213. Anal. Calcd for C14H15NO: C, 78.84: H, 7.09; N, 6.57. Found C, 78.96; H, 7.10; N, 6.45.

Workup

  1. stirringstirring
  2. waitwas continued for 20 hours
  3. temperatureThe mixture was cooled in an ice-water bath
  4. customAfter thorough mixing, the layers were separated
  5. extractionthe water layer was extracted twice with 225 mL of ethyl acetate
  6. customdried
  7. customevaporated
  8. customto give a yellow solid
  9. customRecrystallization from ethanol

Sources & evidence

ORD record
ord-d4aa01633c3f4f93961bdab7b7c75964
Source dataset
uspto-grants-2008_03
Patent number
US07341709B2

Reaction notes

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