2-Methyl-5-(2-nitro-phenylamino)-thiazole-4-carbonitrile → 2-methyl-4H-3-thia-1,4,9-triazabenzo[f]azulene-10-ylamine hydrochloride

HRID 131350Notes

Reaction equation

HRID 131350 reaction equation
[CH3:1][C:2]1[S:3][C:4]([NH:9][C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=2[N+:16]([O-])=O)=[C:5]([C:7]#[N:8])[N:6]=1.O.[Sn](Cl)[Cl:21]>C(O)(C)C.Cl>[ClH:21].[CH3:1][C:2]1[S:3][C:4]2[NH:9][C:10]3[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=3[N:16]=[C:7]([NH2:8])[C:5]=2[N:6]=1

Participants

5

Reactant 2

HCID 210935062-Methyl-5-(2-nitro-phenylamino)-thiazole-4-carbonitrileHCID 43835034Tin dichloride dihydrate

Product 1

HCID 1357977452-methyl-4H-3-thia-1,4,9-triazabenzo[f]azulene-10-ylamine hydrochlorideYield 99.3%

Reagents, catalysts & solvents 2

HCID 313Hydrochloric AcidSolventHCID 3776IsopropanolSolvent

Conditions

Temperature
65 °C

Procedure

Combine a suspension of 2-methyl-5-(2-nitroanilino)thiazole-4-nitrile (36 g, 138.5 mmol) in isopropanol (400 ml) in a 2.0 liter 3-necked RB flask equipped with a reflux condenser, thermometer, magnetic stirrer bar and heat with stirring to 65° C. (orange solution). Add tin (II) chloride hydrate (78.7 g, 415.4 mmol) in hydrochloric acid (400 ml; 5M) and heat the resulting solution at reflux. After 2.5 h., cool the reaction to 15° C., filter the suspension, wash with isopropanol/water (2:1) and dry at 50° C. under reduced pressure to leave a yellow solid (36.7 g). Evaporate the filtrate to around 200 mL to form a yellow slurry. Filter the slurry again and dry at 50° C. under reduced pressure to leave a yellow solid (10 g). Combine the solid and suspend in 1 N HCl (700 mL) and heat to reflux for 20 min, cool to 15° C. Filter the resulting yellow slurry and dry at 50° C. under reduced pressure to leave a yellow solid (32.4 g, 88%): mass spectrum (m/e): 231 (M+1); 1HNMR(300 MHz, DMSO-d6, ppm): δ 2.5(s, 3H), 6.78(dd, 1H), 6.85(dd, 1H), 6.98(t, 1H), 7.02(t, 1H), 8.80(s, 1H), 9.10(s, 1H), 9.98(s, 1H), 10.78(s, 1H). 13CNMR(75 MHz, DMSO, ppm): δ 19.6, 120.1, 120.8, 123.6, 125.8, 127.8, 129.2, 137.6, 154.4, 159.3, 160.4. Formula C11H11N4S.

Workup

  1. customequipped with a reflux condenser
  2. temperaturethermometer, magnetic stirrer bar and heat
  3. temperatureat reflux
  4. temperaturecool
  5. customthe reaction to 15° C.
  6. filtrationfilter the suspension
  7. washwash with isopropanol/water (2:1)
  8. customdry at 50° C. under reduced pressure

Sources & evidence

ORD record
ord-73df586f714242a7b796fb6ea7f5f9b1
Source dataset
uspto-grants-2008_06
Patent number
US07384934B2

Reaction notes

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