Dichloromethane → HCID 20452304, compound

HRID 1462976Notes

Reaction equation

HRID 1462976 reaction equation
O[C:2]1[CH:11]=[C:10]2[C:5]([CH2:6][CH2:7][NH:8][CH:9]2[CH2:12][C:13]2[CH:18]=[CH:17][C:16]([O:19][CH3:20])=[C:15]([OH:21])[CH:14]=2)=[CH:4][C:3]=1[O:22][CH3:23].[C:24](=[O:27])(O)[O-].[Na+].[CH2:29](Br)[CH:30]=[CH2:31].F[C:34](F)(F)C(O)=O.C(Cl)[Cl:41]>O=[V].Cl.Cl.Cl.C(O)C>[ClH:41].[CH2:29]([N:8]1[CH:9]2[C:10]3=[C:11]([C:2]([O:27][CH3:24])=[C:3]([O:22][CH3:23])[CH:4]=[C:5]3[CH2:6][CH2:7]1)[C:18]1[CH:17]=[C:16]([O:19][CH3:20])[C:15]([O:21][CH3:34])=[CH:14][C:13]=1[CH2:12]2)[CH:30]=[CH2:31]

Participants

8

Reactant 5

HCID 6344Dichloromethane2×HCID 6422Trifluoroacetic acidHCID 7841Allyl bromideHCID 44376613168-51-9HCID 516892Sodium Bicarbonate

Product 1

HCID 20452304HCID 20452304, compound

Reagents, catalysts & solvents 2

HCID 24410Vanadium trichloride oxideCatalystHCID 702EthanolSolvent

Procedure

8.0 g. (25.37 mmol) (+)-7-Hydroxy-1-(3-hydroxy-4-methoxybenzyl)-6-methoxy-1,2,3,4-tetrahydroisoquinoline (J. Org. Chem., 45, 592/1980) in 150 ml. ethanol are mixed with 5.10 g. (60.7 mmol) sodium bicarbonate and 2.19 ml. (3.07 g.) allyl bromide in a manner analogous to that described in Example 1. The N-allylation product (8.0 g., 22.5 mmol, yellowish foam) obtained after appropriate working up is reacted at -10° C. in a mixture of 70 ml. trifluoroacetic acid and 70 ml. methylene chloride with 3.2 ml. (5.89 g., 33.98 mmol) vanadium oxytrichloride in 35 ml. anhydrous methylene chloride in a manner analogous to that described in Example 1. The crude product obtained (8 g., crystallisation from chloroform/diethyl ether; m.p. 159°-165° C.) is O-methylated in a manner analogous to that described in Example 1 with 115 ml. of a 1N solution of phenyltrimethylammonium hydroxide in methanol in 400 ml. of a mixture of toluene and dimethylformamide (9:1 v/v). The crude product obtained after appropriate working up is, after chromatographic purification on silica gel with chloroform as elution agent, converted with ethanolic hydrochloric acid into the crystalline hydrochloride. There is obtained (-)-6-allyl-5,6,6a,7-tetrahydro-1,2,9,10-tetramethoxy-4H-dibenzo(de,g)quinoline hydrochloride; m.p. 210°-217° C.

Workup

  1. customThe N-allylation product (8.0 g., 22.5 mmol, yellowish foam) obtained
  2. customafter appropriate working up is reacted at -10° C. in a mixture of 70 ml
  3. customThe crude product obtained
  4. custom(8 g., crystallisation from chloroform/diethyl ether; m.p. 159°-165° C.)
  5. additionof a mixture of toluene and dimethylformamide (9:1 v/v)
  6. customThe crude product obtained
  7. customafter chromatographic purification on silica gel with chloroform
  8. washas elution agent

Sources & evidence

ORD record
ord-d9ed27e345c14a6eb7cc38bc0d8700cd
Source dataset
uspto-grants-1984_07
Patent number
US04461895

Reaction notes

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