Ethyl chloroformate → HCID 13731034, compound

HRID 2290660Notes

Reaction equation

HRID 2290660 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[C:5]([CH:7]=[CH:8][C:9]=1[O:10][CH3:11])[NH2:6].[OH-].[Na+].Cl[C:15]([O:17][CH2:18][CH3:19])=[O:16]>C(Cl)Cl>[CH3:1][O:2][C:3]1[CH:4]=[C:5]([NH:6][C:15]([O:17][CH2:18][CH3:19])=[O:16])[CH:7]=[CH:8][C:9]=1[O:10][CH3:11]

Participants

5

Reactant 3

HCID 10928Ethyl chloroformateHCID 14798Sodium HydroxideHCID 227703,4-Dimethoxyaniline

Product 1

HCID 13731034HCID 13731034, compoundYield 84%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
12 °C

Procedure

A solution of 919 g (6 mol) of 3,4-dimethoxyaniline in 5 L of methylene chloride was treated with 3.3 L of 2N sodium hydroxide. The reaction mixture was cooled to 12° C. and 603 mL (6.3 mol) of ethyl chloroformate was added at a rate to keep the temperature between 25°-30° C. The reaction mixture was stirred at room temperature for 2 hr and the layers were separated. The aqueous layer was extracted with 3×1500 mL of methylene chloride and the combined organic layers were dried over sodium sulfate and treated with Darco*. Evaporation gave an oil to which 3 L of ethyl acetate and 1 L of hexanes were added to crystallize the product. After cooling at 4° C. for 3 hr, the product was filtered and washed with 3×1 L of hexanes. Drying under vacuum gave 1133 g (84%) of the product, mp 75°-78° C. NMR (CDCl3) δ 1.30 (t, 3H, J=7 Hz, OCH2 --CH3), 3.83 (s, 6H, OCH3), 4.18 (q, 2H, J=7 Hz, OCH2 --CH3), 6.58 (br s, 1H, NH ), 6.70 (m, 2H, ArH), 7.12 (m, 1H, ArH).

Workup

  1. custombetween 25°-30° C
  2. customthe layers were separated
  3. extractionThe aqueous layer was extracted with 3×1500 mL of methylene chloride
  4. dry with materialthe combined organic layers were dried over sodium sulfate
  5. additiontreated with Darco*
  6. customEvaporation
  7. customgave an oil to which 3 L of ethyl acetate and 1 L of hexanes
  8. additionwere added
  9. customto crystallize the product
  10. temperatureAfter cooling at 4° C. for 3 hr
  11. filtrationthe product was filtered
  12. washwashed with 3×1 L of hexanes
  13. customDrying under vacuum

Sources & evidence

ORD record
ord-b44a496fd9304186be851f4e33001702
Source dataset
uspto-grants-1986_10
Patent number
US04617417

Reaction notes

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