Hydrochloric Acid → HCID 18319507, compound

HRID 1699386Notes

Reaction equation

HRID 1699386 reaction equation
[N+]([O-])([O-])=O.[Na+].N[C:7]1[C:17]2[O:16][CH2:15][CH2:14][C:13]([C:18]([O:20][CH2:21][CH3:22])=[O:19])=[CH:12][C:11]=2[CH:10]=[CH:9][CH:8]=1.[ClH:23].[S:24](=[O:26])=[O:25]>O.[Cu](Cl)Cl.C(O)(=O)C>[Cl:23][S:24]([C:7]1[C:17]2[O:16][CH2:15][CH2:14][C:13]([C:18]([O:20][CH2:21][CH3:22])=[O:19])=[CH:12][C:11]=2[CH:10]=[CH:9][CH:8]=1)(=[O:26])=[O:25]

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 1119Sulfur DioxideHCID 24268Sodium NitrateHCID 18319514HCID 18319514, compound

Product 1

HCID 18319507HCID 18319507, compound

Reagents, catalysts & solvents 3

HCID 24014Cupric ChlorideCatalystHCID 176Acetic AcidSolvent2×HCID 962WaterSolvent

Conditions

Temperature
-10 °C

Procedure

A solution of sodium nitrate (800 mg) in water (3 ml) was added to a suspension of ethyl 9-amino-2,3-dihydro-1-benzoxepin-4-carboxylate (2.56 g) in a mixture of conc. hydrochloric acid (18 ml) and acetic acid (12.5 ml) under sodium chloride—ice bath cooling, and the mixture was stirred at the same temperature for 50 minutes. On the other hand, sulfur dioxide gas was introduced to acetic acid (40 ml) at room temperature, and the solution was cooled to −10° C. under stirring. To this was added copper(II) chloride (545 mg), followed by addition of the diazonium salt solution dropwise. After the addition was completed, the mixture was stirred at room temperature for 16 hours. The reaction mixture was poured into ice-water, and extracted with ethyl acetate (×3). The combined extracts were successively washed with water, saturated aqueous sodium bicarbonate and brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give ethyl 9-chlorosulfonyl-2,3-dihydro-1-benzoxepin-4-carboxylate (0.72 g) as an oil.

Workup

  1. temperaturecooling
  2. stirringunder stirring
  3. additionAfter the addition
  4. stirringthe mixture was stirred at room temperature for 16 hours
  5. extractionextracted with ethyl acetate (×3)
  6. washThe combined extracts were successively washed with water, saturated aqueous sodium bicarbonate and brine
  7. dry with materialdried over anhydrous magnesium sulfate
  8. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-ff8ce3dcf5b1486bb790c6f6d73f46bb
Source dataset
uspto-grants-2002_02
Patent number
US06346527B1

Reaction notes

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