Hydrochloric Acid → HCID 68966057, compound

HRID 2116110Notes

Reaction equation

HRID 2116110 reaction equation
CC1C=CC(S(OCC2CC3C(C)=C(Cl)C=C(C(C)C)C=3O2)(=O)=O)=CC=1.[N-]=[N+]=[N-].[Na+].[N:31]([CH2:34][CH:35]1[CH2:39][C:38]2[C:40]([CH3:48])=[C:41]([Cl:47])[CH:42]=[C:43]([CH:44]([CH3:46])[CH3:45])[C:37]=2[O:36]1)=[N+]=[N-].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.Cl>O1CCCC1.C(O)(C)C.O>[Cl:47][C:41]1[CH:42]=[C:43]([CH:44]([CH3:46])[CH3:45])[C:37]2[O:36][CH:35]([CH2:34][NH2:31])[CH2:39][C:38]=2[C:40]=1[CH3:48]

Participants

9

Reactant 5

HCID 313Hydrochloric AcidHCID 11776TriphenylphosphineHCID 33557Sodium AzideHCID 86599068HCID 86599068, compoundHCID 86599183HCID 86599183, compound2×

Product 1

HCID 68966057HCID 68966057, compoundYield 88%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 3776IsopropanolSolventHCID 8028TetrahydrofuranSolvent

Procedure

Treatment of (±)-(5-chloro-7-isopropyl-4-methyl-2,3-dihydro-1-benzofuran-2-yl)methyl 4-methylbenzenesulfonate (6.64 g, 16.8 mmol) with sodium azide (3.28 g, 50.4 mmol) generally according to the procedure described for Intermediate 98 afforded (±)-2-(azidomethyl)-5-chloro-7-isopropyl-4-methyl-2,3-dihydro-1-benzofuran. To a solution of (±)-2-(azidomethyl)-5-chloro-7-isopropyl-4-methyl-2,3-dihydro-1-benzofuran (4.44 g, 16.71 mmol) in tetrahydrofuran (100 mL) was added triphenylphoshine (5.25 g, 20.05 mmol) followed by water (10 mL) and the reaction mixture was allowed to stir at room temperature for 12 h. The solvent was removed in vacuo to provide a crude solid. Purification by flash column chromatography (silica, 10% ammonium hydroxide in methanol:ethyl acetate 1:9) provided a colorless oil. The oil was re-dissolved in isopropanol (5 mL) and hydrogen chloride (20.0 mL, 1.0 N in diethyl ether) was added. The resulting precipitate was filtered, washed (diethyl ether), and dried to afford 4.08 g (88%) of (±)-1-(5-chloro-7-isopropyl-4-methyl-2,3-dihydro-1-benzofuran-2-yl)methanamine as a white solid, hydrochloride salt. mp >225° C. (dec); Anal. calcd. for C13H18ClNOHCl: C, 56.53; H, 6.93; N, 5.07. Found: C, 56.56; H, 6.91; N, 4.94.

Workup

  1. customThe solvent was removed in vacuo
  2. customto provide a crude solid
  3. customPurification by flash column chromatography (silica, 10% ammonium hydroxide in methanol:ethyl acetate 1:9)
  4. customprovided a colorless oil
  5. filtrationThe resulting precipitate was filtered
  6. washwashed (diethyl ether)
  7. customdried

Sources & evidence

ORD record
ord-2ab8a6568c20414391b959fedb47d5b8
Source dataset
uspto-grants-2008_10
Patent number
US07435837B2

Reaction notes

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