Ammonia → HCID 44549405, compound

HRID 2238434Notes

Reaction equation

HRID 2238434 reaction equation
[Cl:1][CH2:2][CH:3]1[C:11]2[C:10]3[CH:12]=[C:13]([S:16]([CH3:19])(=[O:18])=[O:17])[CH:14]=[CH:15][C:9]=3[CH:8]=[CH:7][C:6]=2[N:5](C(OC(C)(C)C)=O)[CH2:4]1.[N+:27]([O-])([O-:29])=[O:28].[K+].N>OS(O)(=O)=O>[Cl:1][CH2:2][CH:3]1[C:11]2[C:10]3[CH:12]=[C:13]([S:16]([CH3:19])(=[O:18])=[O:17])[CH:14]=[CH:15][C:9]=3[C:8]([N+:27]([O-:29])=[O:28])=[CH:7][C:6]=2[NH:5][CH2:4]1

Participants

5

Reactant 3

HCID 222AmmoniaHCID 24434Potassium NitrateHCID 44550495HCID 44550495, compound

Product 1

HCID 44549405HCID 44549405, compoundYield 69%

Reagents, catalysts & solvents 1

HCID 1118Sulfuric AcidSolvent2×

Procedure

Powdered 205 (350 mg, 0.88 mmol) was added to stirred conc. H2SO4 (4 mL) at 0° C. and the mixture was warmed to room temperature for 20 min. The resulting solution of amine was cooled to −5° C. and treated dropwise with a solution of KNO3 (98 mg, 0.97 mmol) in conc. H2SO4 (1 mL). The mixture was stirred at 0° C. for a further 5 min, then poured into ice/water and neutralized with dilute aqueous NH3. The resulting solid was filtered off, dissolved in CH2Cl2, and the solution was filtered through a column of silica gel and evaporated to dryness. Recrystallization from CH2Cl2/i-Pr2O followed by EtOAc gave 1-(chloromethyl)-8-(methylsulfonyl)-5-nitro-1,2-dihydro-3H-benzo[e]indole (206) (207 mg, 69%) as a red solid: mp 193-194° C.; 1H NMR [(CD3)2SO] δ 8.34 (d, J=1.5 Hz, 1H), 8.31 (d, J=9.1 Hz, 1H), 7.82 (s, 1H), 7.76 (dd, J=9.1, 1.9 Hz, 1H), 6.62 (br s, 1H), 4.37-4.28 (m, 1H), 3.93 (dd, J=11.1, 4.1 Hz, 1H), 3.87 (td, J=9.8, 2.3 Hz, 1H), 3.80-3.70 (1, 2H), 3.33 (s, 3H). Anal. (C14H13ClN2O4S) C, Ht N. The structure of 206 was confirmed by x-ray crystallography see FIG. 1.

Workup

  1. filtrationThe resulting solid was filtered off
  2. dissolutiondissolved in CH2Cl2
  3. filtrationthe solution was filtered through a column of silica gel
  4. customevaporated to dryness
  5. customRecrystallization from CH2Cl2/i-Pr2O

Sources & evidence

ORD record
ord-4054b3c25862436ca1557ca17e52743e
Source dataset
uspto-grants-2010_05
Patent number
US07718688B2

Reaction notes

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