Formaldehyde → HCID 13755881, compound

HRID 867871Notes

Reaction equation

HRID 867871 reaction equation
[C:1]([C:5]1[CH:6]=[C:7]2[C:12](=[CH:13][CH:14]=1)[CH2:11][CH2:10][C:9]([CH2:15][N:16]1[CH2:21][CH2:20][CH2:19][CH2:18][CH2:17]1)=[CH:8]2)([CH3:4])([CH3:3])[CH3:2].Cl.N1CCCCC1.C(C1C=C2C(CCCC2=[O:43])=CC=1)(C)(C)C.C=O>C(O)C.Cl>[C:1]([C:5]1[CH:6]=[C:7]2[C:12]([CH2:11][CH2:10][CH:9]([CH2:15][N:16]3[CH2:21][CH2:20][CH2:19][CH2:18][CH2:17]3)[C:8]2=[O:43])=[CH:13][CH:14]=1)([CH3:4])([CH3:2])[CH3:3]

Participants

7

Reactant 4

HCID 712FormaldehydeHCID 6045627-tert-Butyl-1-tetraloneHCID 2723721Piperidine, hydrochloride (1:1)HCID 13755887HCID 13755887, compound

Product 1

HCID 13755881HCID 13755881, compoundYield 43%

Reagents, catalysts & solvents 2

HCID 313Hydrochloric AcidCatalystHCID 702EthanolSolvent

Procedure

This Example illustrates the preparation of 6-tert-butyl-3-piperidinomethyl-1,2-dihydronaphthalene (Compound number 4 of Table I). Piperidine hydrochloride (8.9 g, 0.073 mol), 7-tert-butyl-1,2,3,4-tetrahydronaphthalen-1-one (7.0 g, 0.035 mol) and paraformaldehyde (2.2 g, 0.073 mol) were refluxed together in ethanol (150 ml) along with concentrated hydrochloric acid (1 ml) as a catalyst for 16 hours. The reaction mixture was concentrated under reduced pressure and the residue dissolved in water then extracted with diethyl ether. The resulting aqueous solution was neutralized with sodium bicarbonate and extracted with diethyl ether (2×200 ml); the ethereal extracts were dried over magnesium sulphate and concentrated under reduced pressure to give 7-tert-butyl-2-piperidinomethyl-1,2,3,4-tetrahydronaphthalen-1-one (4.5 g, 43% yield) as a buff coloured solid melting at 62°-3°. The 7-tert-butyl-2-piperidinomethyl-1,2,3,4-tetrahydronaphthalen-1-one (4.5 g, 0.015 mol) was dissolved in methanol (100 ml) and sodium borohydride (0.6 g, 0.016 mol) was added portionwise over 30 minutes at room temperature. It was stirred for 3 hours at room temperature then the methanol was evaporated under reduced pressure and the residue treated with water (100 ml) and extracted with ether (2×100 ml) which was washed with brine, dried over magnesium sulphate and evaporated under reduced pressure to give a viscous oil (4.0 g) which crystallised on standing. Separation by column chromatography on silica gel (Merck 60) using a gradient elution of petrol 60°-80° to ethyl acetate gave the alcohol as two isomers:

Workup

  1. concentrationThe reaction mixture was concentrated under reduced pressure
  2. dissolutionthe residue dissolved in water
  3. extractionthen extracted with diethyl ether
  4. extractionextracted with diethyl ether (2×200 ml)
  5. dry with materialthe ethereal extracts were dried over magnesium sulphate
  6. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-80c8ea30fed54fcf96ba72388f55adfd
Source dataset
uspto-grants-1988_10
Patent number
US04777176

Reaction notes

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