Ammonia → HCID 178483395, compound

HRID 552927Notes

Reaction equation

HRID 552927 reaction equation
[CH3:1][N:2]([CH3:16])[CH2:3][CH2:4][CH2:5][C:6]1[C:14]2[C:9](=[CH:10][CH:11]=[C:12]([NH2:15])[CH:13]=2)[NH:8][CH:7]=1.I.CS[C:20]([C:22]1[S:23][CH:24]=[CH:25][CH:26]=1)=[NH:21].N.Cl>C(O)C.CO.ClCCl.CCOCC>[CH3:16][N:2]([CH3:1])[CH2:3][CH2:4][CH2:5][C:6]1[C:14]2[C:9](=[CH:10][CH:11]=[C:12]([NH:15][C:20]([C:22]3[S:23][CH:24]=[CH:25][CH:26]=3)=[NH:21])[CH:13]=2)[NH:8][CH:7]=1

Participants

9

Reactant 4

HCID 222AmmoniaHCID 313Hydrochloric AcidHCID 57474451HCID 57474451, compoundHCID 66704664Methyl thiophene-2-carbimidothioate hydroiodide

Product 1

HCID 178483395HCID 178483395, compound

Reagents, catalysts & solvents 4

HCID 702EthanolSolventHCID 887MethanolSolvent2×HCID 3283Diethyl EtherSolvent2×HCID 6344DichloromethaneSolvent

Procedure

To an argon purged round bottom flask containing 55 (340 mg, 1.56 mmol) was added thiophene-2-carboximidothioic acid methyl ester hydroiodide (669 mg, 2.35 mmol). The two were suspended in absolute ethanol (10 mL) and stirred at room temperature for 16 hours. TLC (10% 2M ammonia in methanol, 90% dichloromethane) revealed all amine had reacted. The reaction was diluted with ether (80 mL) and the fluffy yellow precipitate collected by vacuum filtration. The precipitate was washed with ether (50 mL) and became an oil on the fritted filter. Ethanol was used to wash the product through the filter into a round bottom flask (50 mL). The flask was fitted with a stir bar and DOWEX-66 (5.5 g) was added. The reaction was stirred for 2 hours. The reaction was filtered and the filtrate concentrated to afford a yellow foam. The product was purified by silica gel column chromatography (5-10% 2M ammonia in methanol, 95-90% dichloromethane) to afford a yellow oil. The oil was taken up in methanol (5 mL) and stirred during the addition of 1M hydrogen chloride in ether (3 mL). After stirring for 2 hours the reaction was concentrated on the rotary evaporator. The resulting yellow foam was dried further on the high vacuum line. Yield: 347 mg of yellow foam, compound 56, 1H NMR (DMSO) δ 11.44 (br s, 1H), 11.26 (s, 1H), 10.62 (bs, 1H), 9.66 (bs, 1H), 8.61 (bs, 1H), 8.18-8.17 (d, 2H, J=4.2 Hz), 7.65 (s, 1H), 7.54-7.51 (d, J=8.7 Hz, 1H), 7.41-7.36 (q 2H, J=4.5 Hz), 7.13-7.09 (dd, J=1.2, 8.7 Hz, 1H), 3.10-3.04 (t J=7.5, 2H), 2.79-2.74 (t, J=7.5 Hz, 2H), 2.72 (s, 6H), 2.05 (m, 2H). ESI-MS m/z (%): 327 (M+, 100).

Workup

  1. customhad reacted
  2. filtrationthe fluffy yellow precipitate collected by vacuum filtration
  3. washThe precipitate was washed with ether (50 mL)
  4. washto wash the product through the
  5. filtrationfilter into a round bottom flask (50 mL)
  6. customThe flask was fitted with a stir bar
  7. additionDOWEX-66 (5.5 g) was added
  8. stirringThe reaction was stirred for 2 hours
  9. filtrationThe reaction was filtered
  10. concentrationthe filtrate concentrated
  11. customto afford a yellow foam
  12. customThe product was purified by silica gel column chromatography (5-10% 2M ammonia in methanol, 95-90% dichloromethane)
  13. customto afford a yellow oil
  14. stirringAfter stirring for 2 hours the reaction
  15. concentrationwas concentrated on the rotary evaporator
  16. customThe resulting yellow foam was dried further on the high vacuum line

Sources & evidence

ORD record
ord-f92f6aa412ef4cce8edd00e72ebf1d74
Source dataset
uspto-grants-2011_05
Patent number
US07951940B2

Reaction notes

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