Tert-Butylamine → HCID 9865086, compound

HRID 1416441Notes

Reaction equation

HRID 1416441 reaction equation
Br[C:2]1[N:6]([C@@H:7]2[C@@H:11]([OH:12])[C@@H:10]([OH:13])[C@H:9]([CH2:14][OH:15])[CH2:8]2)[C:5]2[CH:16]=[C:17]([Cl:21])[C:18]([Cl:20])=[CH:19][C:4]=2[N:3]=1.[C:22]([NH2:26])([CH3:25])([CH3:24])[CH3:23]>C(O)C>[C:22]([NH:26][C:2]1[N:6]([C@@H:7]2[C@@H:11]([OH:12])[C@@H:10]([OH:13])[C@H:9]([CH2:14][OH:15])[CH2:8]2)[C:5]2[CH:16]=[C:17]([Cl:21])[C:18]([Cl:20])=[CH:19][C:4]=2[N:3]=1)([CH3:25])([CH3:24])[CH3:23]

Participants

4

Reactant 2

HCID 6385Tert-ButylamineHCID 9800858HCID 9800858, compound

Product 1

HCID 9865086HCID 9865086, compoundYield 61%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Conditions

Temperature
148 °C

Procedure

A solution of (1R, 2S, 3S, 5S)-5-(2-bromo-5,6-dichloro-1H-benzimidazol-1-yl)-3-(hydroxymethyl)-1,2-cyclopentanediol (500 mg, 1.26 mmole) was stirred in tert-butylamine (Aldrich, 98%, 20 mL) in a Parr bomb maintained at 148 ° C. (oil bath) for 48 hours. The bomb was cooled and the resulting pale yellow solution diluted with ethanol containing 1 N sodium hydroxide (1.2 mL). Volatiles were evaporated in vacuo and the residue was chromatographed on silica gel. Title compound was eluted with 10% methanol-chloroform as a colorless oil. The oil was dissolved in absolute ethanol, concentrated to an oil, and triturated with water (3 mL) to give (1R, 2S, 3S, 5S)-5-[2-(tert-butylamino)-5,6-dichloro-1H-benzimidazol-1-yl]-3-(hydroxymethyl)-1,2-cyclopentanediol as white powder (303 mg, 61%), m.p.: collapses to glass at 116-150° C.; 1H-NMR(DMSO-d6) δ: 7.63 and 7.43 (both s, 2, aromatic CH), 6.15 (s, 1, NH), 5.08 (t, J=4.3 Hz, 1, OH), 4.85 (d,J=7.4 Hz, 1, OH), 4.71 (d, J=3.8 Hz, 1, OH), 4.7-4.5 (m, 1, NCH), 4.45-4.3 (m, 1, OCH), 3.80 (m, 1, OCH), 3.7-3.4 (m, 2, OCH2), 2.2-1.85 (m, 3, CH2 and CH of cyclopentane), 1.47 (s, 9, 3 CH3); mass spectrum (CI): 388(M+1); [α]20 589-4.0°, [α]20 578-4.3°, [α]20 546-6.0°, [α 20 436-22.6°, [α]20 365-82.1° (c=0.420, methanol). [See Examples 25-28, 30 and 31]

Workup

  1. temperatureThe bomb was cooled
  2. customVolatiles were evaporated in vacuo
  3. customthe residue was chromatographed on silica gel
  4. washTitle compound was eluted with 10% methanol-chloroform as a colorless oil
  5. dissolutionThe oil was dissolved in absolute ethanol
  6. concentrationconcentrated to an oil
  7. customtriturated with water (3 mL)

Sources & evidence

ORD record
ord-d3a25aa580574ffe8a1fe60fd23fa480
Source dataset
uspto-grants-1999_06
Patent number
US05912356

Reaction notes

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