Sodium Chloride → 5-(-4-Chlorophenoxy)-4-methoxymethyl-beta-carboline-3-carboxylic acid ethyl ester

HRID 2166365Notes

Reaction equation

HRID 2166365 reaction equation
[CH2:1]([O:3][C:4]([C:6]1[N:7]=[CH:8][C:9]2[NH:10][C:11]3[C:16]([C:17]=2[C:18]=1[CH2:19][O:20][CH3:21])=[C:15]([O:22][C:23]1[CH:28]=[CH:27][C:26](N)=[CH:25][CH:24]=1)[CH:14]=[CH:13][CH:12]=3)=[O:5])[CH3:2].N([O-])=O.[Na+].S([O-])([O-])(=O)=O.[Na+].[Na+].[Cl-:41].[Na+]>O.Cl.S([O-])([O-])(=O)=O.[Cu+2]>[CH2:1]([O:3][C:4]([C:6]1[N:7]=[CH:8][C:9]2[NH:10][C:11]3[C:16]([C:17]=2[C:18]=1[CH2:19][O:20][CH3:21])=[C:15]([O:22][C:23]1[CH:28]=[CH:27][C:26]([Cl:41])=[CH:25][CH:24]=1)[CH:14]=[CH:13][CH:12]=3)=[O:5])[CH3:2]

Participants

8

Reactant 4

HCID 5234Sodium ChlorideHCID 24436Sodium SulfateHCID 138000665(-4-Aminophenoxy)-4-methoxymethyl-beta-carboline-3-carboxylic acid ethyl esterHCID 23668193Sodium Nitrite

Product 1

HCID 138000755-(-4-Chlorophenoxy)-4-methoxymethyl-beta-carboline-3-carboxylic acid ethyl esterYield 63.5%

Reagents, catalysts & solvents 3

HCID 24462Copper SulfateCatalystHCID 313Hydrochloric AcidSolvent2×HCID 962WaterSolvent5×

Conditions

Temperature
0 °C

Procedure

195 mg 5-(4-aminophenoxy)-4-methoxymethyl-beta-carboline-3-carboxylic acid ethyl ester is suspended in a mixture of 2 ml of water and 2 ml of concentrated hydrochloric acid and, after cooling to 0° C., is mixed drop by drop with a solution of 35 mg of sodium nitrite in 0.5 ml of water. After the addition is completed, it is stirred for 45 minutes at 0° C., whereby a bright yellow solution results. To this is added at 0° C. drop by drop a solution which was previously prepared by addition of 69 mg of sodium sulfate in 0.5 ml of water to 250 mg of copper(II) sulfate, 5 H2O and 87 mg of sodium chloride in 1 ml of water, suctioning off of the precipitate and dissolution in 0.5 ml of concentrated hydrochloric acid. After the addition is completed, a yellow precipitation has occurred and the mixture is then heated to the end of the development of gas on the steam bath. Then it is diluted with water, alkalized with ammonia solution and extracted with ethyl acetate. After evaporation of the organic phase, it is chromatographed over silica gel with methylene chloride: ethanol=10:1 as eluant. 130 mg (55% of theory) of 5-(-4-chlorophenoxy)-4-methoxymethyl-beta-carboline-3-carboxylic acid ethyl ester with a melting point of 207° C. is obtained.

Workup

  1. additionAfter the addition
  2. customwhereby a bright yellow solution results
  3. additionTo this is added at 0° C. drop by drop a solution which
  4. additionAfter the addition
  5. customa yellow precipitation
  6. temperaturethe mixture is then heated to the end of the development of gas on the steam bath
  7. additionThen it is diluted with water
  8. extractionextracted with ethyl acetate
  9. customAfter evaporation of the organic phase, it
  10. customis chromatographed over silica gel with methylene chloride

Sources & evidence

ORD record
ord-a42fd7a5c4684e7984f96111b88de06f
Source dataset
uspto-grants-1990_07
Patent number
US04945090

Reaction notes

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