Pyridine → HCID 19767417, compound

HRID 1979892Notes

Reaction equation

HRID 1979892 reaction equation
[CH3:1][O:2][C:3]1[C:12]2[C:11]([CH3:14])([CH3:13])[CH2:10][CH2:9][C:8]([CH3:16])([CH3:15])[C:7]=2[CH:6]=[C:5]([CH3:17])[C:4]=1[CH:18]=O.Cl.NO.[N:23]1C=CC=CC=1.C1(C)C=CC=CC=1>O.CCCCCC.C(OCC)(=O)C>[CH3:1][O:2][C:3]1[C:12]2[C:11]([CH3:14])([CH3:13])[CH2:10][CH2:9][C:8]([CH3:16])([CH3:15])[C:7]=2[CH:6]=[C:5]([CH3:17])[C:4]=1[C:18]#[N:23]

Participants

7

Reactant 4

HCID 1049PyridineHCID 1140TolueneHCID 1747662-Naphthalenecarboxaldehyde, 5,6,7,8-tetrahydro-1-methoxy-3,5,5,8,8-pentamethyl-HCID 443297Hydroxyamine hydrochloride

Product 1

HCID 19767417HCID 19767417, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 21226206Ethyl acetate hexaneSolvent

Procedure

A mixture 1-methoxy-3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalene-2-carboxaldehyde (67.95 g, 0.261 mol), hydroxylamine hydrochloride (19.10 g, 0.275 mol), pyridine (21 mL) and toluene (260 mL) was heated at reflux, with removal of water via a Dean-Stark trap, for 20 h. The mixture was cooled and hexane/ethyl acetate (8:1, 100 mL) and water (250 mL) was added. The layers were separated and the aqueous layer extracted with hexane/ethyl acetate (8:1, 2×50 mL). The combined organic extracts were washed with water (2×100 mL), 2N hydrochloric acid (2×100 mL), and brine (100 mL). Evaporation of solvents and crystallization from hexane provided 1-methoxy-3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalene-2-carbonitrile (1), (56.17 g), mp 71°-73° C., GLC purity 99%+. 1H-NMR (CDCl3) δ 1.25 and 1.36 (12H, 2s), 1.62 (4H, s), 2.43 (3H, s), 4.07 (3H, s), 6.92 (1H, s); IR (CHCl3) νmax 2950, 2200, 1600, 1540, 1460 cm-1. MS (m/e) 257, 242, 200; UV νmax (ethanol) 224 (ε=2100), 247 (ε=2800), 289 (ε=840) nm.

Workup

  1. temperatureThe mixture was cooled
  2. customThe layers were separated
  3. extractionthe aqueous layer extracted with hexane/ethyl acetate (8:1, 2×50 mL)
  4. washThe combined organic extracts were washed with water (2×100 mL), 2N hydrochloric acid (2×100 mL), and brine (100 mL)
  5. customEvaporation of solvents and crystallization from hexane

Sources & evidence

ORD record
ord-5e8cb5bb388c4ef2bad0715c903f3655
Source dataset
uspto-grants-1984_11
Patent number
US04483786

Reaction notes

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