Dimethyl Sulfide → HCID 11213235, compound

HRID 606638Notes

Reaction equation

HRID 606638 reaction equation
S(C)C.[CH3:4][O:5][C:6]([C@H:8]1[N:12]2[C:13](=[O:36])[C:14]([C:34]#[N:35])=[C:15]([CH2:23][C:24]3[C:33]4[C:28](=[CH:29][CH:30]=[CH:31][CH:32]=4)[CH:27]=[CH:26][CH:25]=3)[C:16]([C:17]3[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=3)=[C:11]2[S:10][CH2:9]1)=[O:7].[OH-].[Na+]>C1COCC1.C(Cl)Cl>[CH3:4][O:5][C:6]([C@H:8]1[N:12]2[C:13](=[O:36])[C:14]([CH2:34][NH2:35])=[C:15]([CH2:23][C:24]3[C:33]4[C:28](=[CH:29][CH:30]=[CH:31][CH:32]=4)[CH:27]=[CH:26][CH:25]=3)[C:16]([C:17]3[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=3)=[C:11]2[S:10][CH2:9]1)=[O:7]

Participants

6

Reactant 3

HCID 1068Dimethyl SulfideHCID 14798Sodium HydroxideHCID 11339937HCID 11339937, compound

Product 1

HCID 11213235HCID 11213235, compoundYield 72%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
100 °C

Procedure

BH3.Me2S (250 μL, 2M in THF, 0.5 mmol) was added dropwise to a solution of 6a (50 mg, 0.11 mmol) in dry THF (4 mL) at rt. The reaction vessel was sealed and heated for 60 s at 100° C. using microwave irradiation. The reaction mixture was cooled to room temperature, diluted with CH2Cl2, poured onto ice-cold aqueous HCl (1M) and agitated. The pH was then adjusted to ˜10 with 2M aqueous NaOH and the aqueous layer was extracted with CH2Cl2. The combined organic layers were dried and concentrated. The crude product was dissolved in MeOH and swirled with Amberlyst 15. The solid phase was transferred to a filtration funnel and washed with MeOH. The product was released by addition of 10% NH3 in MeOH and eluted with MeOH. Concentration of the filtrate gave 7a as a yellow solid (36 mg, 72%): [α]D−44 (c 0.25, CHCl3); IR λ 2958, 2854, 1747, 1631, 1492, 1440, 1259, 1214 cm−1; 1H NMR (400 MHz, CDCl3) δ7.83 (d, J=8.2, 1H), 7.78 (d, J=8.1, 1H), 7.71 (d, J=8.7, 1H), 7.54-7.00 (m, 9H), 5.74 (dd, J=8.6, 2.7, 1H), 4.25-4.11 (m, 2H), 3.96-3.51 (m, 8H), 3.48 (dd, J=11.8, 2.7, 1H); 13C NMR (100 MHz, CDCl3) δ168.1, 161.3, 153.5, 148.9, 135.8, 133.8, 133.6, 131.2, 129.7, 129.3, 128.7 (splitted), 128.5 (splitted), 127.3, 126.3, 125.9, 125.5, 124.4, 123.2, 118.4, 116.6, 64.2, 53.6, 38.0, 33.2, 31.7; HRMS (FAB+) calcd for C27H24N2NaO3S 479.1405, obsd 479.1405.

Workup

  1. customThe reaction vessel was sealed
  2. custommicrowave irradiation
  3. temperatureThe reaction mixture was cooled to room temperature
  4. additionpoured onto ice-cold aqueous HCl (1M)
  5. extractionthe aqueous layer was extracted with CH2Cl2
  6. customThe combined organic layers were dried
  7. concentrationconcentrated
  8. dissolutionThe crude product was dissolved in MeOH
  9. customThe solid phase was transferred to a filtration funnel
  10. washwashed with MeOH
  11. additionThe product was released by addition of 10% NH3 in MeOH
  12. washeluted with MeOH

Sources & evidence

ORD record
ord-78f2d14bc4694e6294048227bef5cd84
Source dataset
uspto-grants-2011_03
Patent number
US07915417B2

Reaction notes

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