2-Mercaptobenzoic Acid → HCID 122436166, compound

HRID 1479114Notes

Reaction equation

HRID 1479114 reaction equation
C1(P(C2C=CC=CC=2)CCCCP(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[CH2:31]([N:34](C)[CH:35]([CH3:62])[CH2:36][O:37][C:38]1[CH:43]=[C:42]([F:44])[CH:41]=[CH:40][C:39]=1[C:45]([N:47]1[CH2:61][C:50]2=[C:51]3[N:56]([N:57]=[C:49]2[CH2:48]1)[C:55]([CH3:58])=[C:54]([Cl:59])[C:53]([CH3:60])=[N:52]3)=[O:46])C=C.SC1C=CC=CC=1C(O)=O>C1COCC1.CC(=O)OCC.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd]>[Cl:59][C:54]1[C:53]([CH3:60])=[N:52][C:51]2[N:56]([N:57]=[C:49]3[CH2:48][N:47]([C:45]([C:39]4[CH:40]=[CH:41][C:42]([F:44])=[CH:43][C:38]=4[O:37][CH2:36][CH:35]([NH:34][CH3:31])[CH3:62])=[O:46])[CH2:61][C:50]3=2)[C:55]=1[CH3:58]

Participants

7

Reactant 3

HCID 54432-Mercaptobenzoic AcidHCID 821241,4-Bis(diphenylphosphino)butaneHCID 89662809HCID 89662809, compound

Product 1

HCID 122436166HCID 122436166, compoundYield 13%

Reagents, catalysts & solvents 3

HCID 6505921(1E,4E)-1,5-diphenylpenta-1,4-dien-3-one; palladiumCatalystHCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

A mixture of Pd(dba)2 (5.2 mg; 0.01 mmol; 0.05 eq.) and 1,4-bis(diphenylphosphino)butane (3.8 mg; 0.01 mmol; 0.05 eq.) in THF (1 mL) was stirred for 10 minutes then added to a solution of {2-[2-(allyl-methyl-amino)-propoxy]-4-fluoro-phenyl}-(6-chloro-5,7-dimethyl-1H,3H-2,4,7a,8-tetraaza-cyclopenta[a]inden-2-yl)-methanone (85 mg; 0.18 mmol; 1 eq.) in THF (3 mL) followed by 2-mercapto-benzoic acid (31 mg; 0.20 mmol; 1.1 eq.) and the reaction mixture was stirred at 60° C. for 2 hours. The solution was diluted with EA, washed with 0.1M NaOH, dried over sodium sulfate and concentrated in vacuo. Purification by mass directed preparative HPLC afforded the title compound (10 mg, 13%) as a yellow solid. 1H NMR (DMSO-d6) δ 8.25 (s, 1H), 7.39 (ddd, J=8.4, 6.8, 3.2 Hz, 1H), 7.11 (dd, J=11.4, 2.3 Hz, 1H), 6.99-6.80 (m, 1H), 4.84 (d, J=8.8 Hz, 2H), 4.55 (d, J=15.8 Hz, 2H), 4.02 (d, J=5.5 Hz, 2H), 2.97-2.86 (m, 1H), 2.84 (s, 1.5H), 2.81 (s, 1.5H), 2.62 (s, 1.5H), 2.56 (s, 1.5H), 2.25 (d, J=1.7 Hz, 3H), 0.96 (dd, J=6.5, 2.4 Hz, 3H). HPLC (max plot) 99.7%, Rt 2.82 min. UPLC/MS: (MS+) 432.3 ([M+H]+).

Workup

  1. stirringthe reaction mixture was stirred at 60° C. for 2 hours
  2. washwashed with 0.1M NaOH
  3. dry with materialdried over sodium sulfate
  4. concentrationconcentrated in vacuo
  5. customPurification by mass

Sources & evidence

ORD record
ord-078b900f7f804967955745cad438329d
Source dataset
uspto-grants-2016_08
Patent number
US09403835B2

Reaction notes

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