Hexamethylenetetramine → HCID 69542107, compound

HRID 724349Notes

Reaction equation

HRID 724349 reaction equation
[CH3:1][CH:2]([CH3:18])[CH2:3][C:4]([C:6]1[S:7][CH:8]=[C:9]([C:11]2[CH:16]=[C:15]([CH3:17])[CH:14]=[CH:13][CH:12]=2)[CH:10]=1)=[O:5].[CH2:19]1N2CN3CN(C2)CN1C3.C(OC(=O)C)(=O)C>>[CH:2]([C:3](=[CH2:19])[C:4]([C:6]1[S:7][CH:8]=[C:9]([C:11]2[CH:16]=[C:15]([CH3:17])[CH:14]=[CH:13][CH:12]=2)[CH:10]=1)=[O:5])([CH3:18])[CH3:1]

Participants

4

Reactant 3

HCID 4101HexamethylenetetramineHCID 7918Acetic AnhydrideHCID 69542112HCID 69542112, compound

Product 1

HCID 69542107HCID 69542107, compoundYield 88.2%

Conditions

Temperature
110 °C

Procedure

3-methyl-1-(5-methyl-4-phenyl-(2-thienyl))butan-1-one (106 g, 0.411 mol), urotropin (161.2 g, 1.15 mol), and acetic anhydride (151.1 g, 1.48 mol) were mixed in a 1 L flask, sparged with nitrogen, and stirred for 24 h at 110° C. The dark mixture was cooled to 70° C. and poured into 700 mL of a 2 N aqueous solution of NaOH. The organic fraction was extracted with 50/50 (v/v) dichloromethane/hexane (3×250 mL), washed with 1 N HCl, saturated aqueous solution of NaHCO3, and dried (MgSO4). Evaporation of solvents gave 98 g of crude product (70% product by GC/MS) used without further purification. 1H-NMR δ (CDCl3): 7.5 (s, 1H), 7.2–7.38 (m, 5H), 5.6 (s, 1H), 5.45 (s, 1H), 2.9 (m, 1H), 2.41 (s, 3H), 1.05 (d, 6H). EIMS: m/z (%) 270 (M+, 65), 255 (100), 237 (11), 201 (89), 171 (11), 129 (38).

Workup

  1. customsparged with nitrogen
  2. temperatureThe dark mixture was cooled to 70° C.
  3. additionpoured into 700 mL of a 2 N aqueous solution of NaOH
  4. extractionThe organic fraction was extracted with 50/50 (v/v) dichloromethane/hexane (3×250 mL)
  5. washwashed with 1 N HCl, saturated aqueous solution of NaHCO3
  6. dry with materialdried (MgSO4)
  7. customEvaporation of solvents

Sources & evidence

ORD record
ord-225e0a7879af447885c5884335227fc1
Source dataset
uspto-grants-2006_11
Patent number
US07141637B2

Reaction notes

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