Ammonium Hydroxide → HCID 22735970, compound

HRID 51000Notes

Reaction equation

HRID 51000 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([N+]([O-])=O)[C:3]=1[S:11][CH2:12][CH2:13][CH2:14][Cl:15].O.O.[Sn](Cl)Cl.[OH-].[NH4+:22]>C(O)C.Cl>[Br:1][C:2]1([NH2:22])[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]1[S:11][CH2:12][CH2:13][CH2:14][Cl:15]

Participants

6

Reactant 3

HCID 14923Ammonium HydroxideHCID 61436Stannous chloride dihydrate2×HCID 22735512(2-Bromo-6-nitrophenyl)(3-chloropropyl)sulfane

Product 1

HCID 22735970HCID 22735970, compoundYield 93.2%

Reagents, catalysts & solvents 2

HCID 313Hydrochloric AcidSolvent2×HCID 702EthanolSolvent

Conditions

Temperature
0 °C

Procedure

1-Bromo-2-[(3-chloropropyl)thio]-3-nitrobenzene (6.78 g, 21.9 mmol) was dissolved in ethyl alcohol (125 mL) and cooled in an ice bath to 0° C. Tin (II) chloride dihydrate (7.4 g, 32.8 mmol) was dissolved in concentrated hydrochloric acid (25 mL) and then added to the first solution over 20 minutes. The reaction was then allowed to warm to room temperature and stirred over night. Reaction mixture was cooled to 0° C. in an ice bath and another (1.5 eq, 7.4 g) of tin (II) chloride dihydrate in concentrated hydrochloric acid (25 mL) was added. This was stirred at 0° C. for 30 minutes and then allowed to warm to room temperature and stirred until loss of starting material. Reaction was then basified to pH 12 with ammonium hydroxide and then filtered. The filtrate was then concentrated to a aqueous slurry, the slurry was then diluted with water (100 mL) and extracted with ethyl acetate (3×300 mL). Organic extracts were dried over magnesium sulfate and filtered. The filtrate was concentrated to give 1-bromo-2-[(3-chloropropyl)thio]-benzenamine (5.7 g, 93.2%). 1H NMR (CDCl3, 300 MHz): δ7.02-60.87 (m, 2H), 6.65 (dd, 1H, J=7.7, 1.9 Hz), 4.63 (s-broad, 2H), 3.68 (t, 2H, J=6.4 Hz), 2.92 (t, 2H, J=6.95 Hz), 2.04-1.95 (m, 2H) ppm.

Workup

  1. additionadded to the first solution over 20 minutes
  2. temperatureto warm to room temperature
  3. customReaction mixture
  4. temperaturewas cooled to 0° C. in an ice bath
  5. stirringThis was stirred at 0° C. for 30 minutes
  6. temperatureto warm to room temperature
  7. stirringstirred until loss of starting material
  8. customReaction
  9. filtrationfiltered
  10. concentrationThe filtrate was then concentrated to a aqueous slurry
  11. additionthe slurry was then diluted with water (100 mL)
  12. extractionextracted with ethyl acetate (3×300 mL)
  13. dry with materialOrganic extracts were dried over magnesium sulfate
  14. filtrationfiltered
  15. concentrationThe filtrate was concentrated

Sources & evidence

ORD record
ord-8b48e054603c43f6bd92cbc610758894
Source dataset
uspto-grants-2004_03
Patent number
US06713471B1

Reaction notes

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