Hydrochloric Acid → HCID 86691913, compound

HRID 714461Notes

Reaction equation

HRID 714461 reaction equation
N[C:2]1[N:7]=[C:6]([S:8][CH2:9][C:10]2[CH:15]=[CH:14][N:13]=[C:12]([C:16]([NH:18][CH3:19])=[O:17])[CH:11]=2)[C:5]([C:20]#[N:21])=[C:4]([C:22]2[CH:27]=[CH:26][C:25]([F:28])=[C:24]([F:29])[CH:23]=2)[C:3]=1[C:30]#[N:31].N(OCCC(C)C)=O.[ClH:40]>C(#N)C.[Cu](Cl)Cl>[Cl:40][C:2]1[N:7]=[C:6]([S:8][CH2:9][C:10]2[CH:15]=[CH:14][N:13]=[C:12]([C:16]([NH:18][CH3:19])=[O:17])[CH:11]=2)[C:5]([C:20]#[N:21])=[C:4]([C:22]2[CH:27]=[CH:26][C:25]([F:28])=[C:24]([F:29])[CH:23]=2)[C:3]=1[C:30]#[N:31]

Participants

6

Reactant 3

HCID 313Hydrochloric AcidHCID 8053Isoamyl Nitrite2×HCID 56592011HCID 56592011, compound

Product 1

HCID 86691913HCID 86691913, compound

Reagents, catalysts & solvents 2

HCID 24014Cupric ChlorideCatalyst2×HCID 6342AcetonitrileSolvent

Conditions

Temperature
65 °C

Procedure

Under argon, 0.86 g (1.97 mmol) of 4-({[6-amino-3,5-dicyano-4-(3,4-difluorophenyl)pyridin-2-yl]sulfanyl}methyl)-N-methylpyridine-2-carboxamide (Example 4), 0.46 g (3.93 mmol) of isopentyl nitrite and 0.53 g (3.93 mmol) of copper(II) chloride were initially charged in 20 ml of acetonitrile and the mixture was stirred at 65° C. overnight. After a reaction time of 3 h, another 0.23 g (1.97 mmol) of isopentyl nitrite and 0.26 g (1.97 mmol) of copper(II) chloride were added to the reaction mixture. After cooling to RT, 3.93 ml of 1N hydrochloric acid were added. The aqueous phase was extracted three times with ethyl acetate. The combined organic phases were dried over sodium sulfate, filtered and evaporated. The residue was purified by preparative HPLC (Chromasil, water/acetonitrile+0.1% trifluoroacetic acid).

Workup

  1. temperatureAfter cooling to RT
  2. extractionThe aqueous phase was extracted three times with ethyl acetate
  3. dry with materialThe combined organic phases were dried over sodium sulfate
  4. filtrationfiltered
  5. customevaporated
  6. customThe residue was purified by preparative HPLC (Chromasil, water/acetonitrile+0.1% trifluoroacetic acid)

Sources & evidence

ORD record
ord-a8bf27e050e24a8aa46f854f406ad753
Source dataset
uspto-grants-2015_11
Patent number
US09187428B2

Reaction notes

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