HCID 10669852, compound → HCID 10641075, compound

HRID 2258352Notes

Reaction equation

[CH2:1]([N:4]1[C@H:9]([CH3:10])[CH2:8][N:7]([C@@H:11]([C:19]2[S:20][CH:21]=[C:22](Br)[CH:23]=2)[C:12]2[CH:13]=[C:14]([OH:18])[CH:15]=[CH:16][CH:17]=2)[C@@H:6]([CH3:25])[CH2:5]1)[CH:2]=[CH2:3].C([Li])CCC>>[CH2:1]([N:4]1[C@H:9]([CH3:10])[CH2:8][N:7]([C@@H:11]([C:19]2[S:20][CH:21]=[CH:22][CH:23]=2)[C:12]2[CH:13]=[C:14]([OH:18])[CH:15]=[CH:16][CH:17]=2)[C@@H:6]([CH3:25])[CH2:5]1)[CH:2]=[CH2:3]

Participants

Reactant 2

HCID 10669852HCID 10669852, compound

HCID 178418339Butyllithium

Product 1

HCID 10641075HCID 10641075, compoundYield 77%

Procedure

(-)-3-((R)-((2S,5R)-4-Allyl-2,5-dimethyl-1-piperazinyl)(4-bromo-2-thienyl)methyl)phenol (0.53 g, 1.3 mmol, Example 66) was debrominated with n-butyllithium as in Example 9. The crude product was recrystallized from acetonitrile to give 0.33 g (77%) of (-)-3-((R)-((2S,5R)-4-allyl-2,5-dimethyl-1-piperazinyl)(2-thienyl)methyl)phenol as beige crystals, mp 176°-178° C., [α]D20 =-23.30° (ethyl acetate, c=1.5). HPLC on β-cyclodextrin with methanol:0.1M aqueous ammonium acetate/1:1 gave one peak at tR =8.5 min. Calc. for C20H26BrN2OS 0.25 H2O: C, 69.23; H, 7.70; N, 8.07; S, 9.24. Found: C, 68.86; H, 7.47; N, 8.27; S, 9.06. The product (0.30 g, 0.87 mmol) was treated with ethanolic hydrogen chloride as in Example 42 to give 0.201 g (61%) of the monohydrochloride salt. Calc. for C20H26BrN2OS HCl 0.75 H2O: C, 61.21; H, 7.32: N, 7.12; S, 8.17; Cl, 9.03. Found: C, 61,35; H, 7.01; N,7.30; S, 8.16; Cl, 9.11. [α]D20 =-11.9° (ethanol, c=1.05).

Workup

customThe crude product was recrystallized from acetonitrile

Sources & evidence

ORD record: ord-43a486663dc8493bbd14bc8977fc5f3c
Source dataset: uspto-grants-1997_08
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05658908

Reaction notes

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