Triethylamine → Abecarnil

HRID 36330Notes

Reaction equation

HRID 36330 reaction equation
[CH:1]([O:4][C:5]([CH:7]1[CH:19]([CH2:20][O:21][CH3:22])[C:18]2[C:17]3[C:12](=[CH:13][CH:14]=[C:15]([O:23][CH2:24][C:25]4[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=4)[CH:16]=3)[NH:11][C:10]=2[CH2:9][NH:8]1)=[O:6])([CH3:3])[CH3:2].C(N(CC)CC)C.ClOC(C)(C)C>C(Cl)Cl>[CH:1]([O:4][C:5]([C:7]1[N:8]=[CH:9][C:10]2[NH:11][C:12]3[C:17]([C:18]=2[C:19]=1[CH2:20][O:21][CH3:22])=[CH:16][C:15]([O:23][CH2:24][C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1)=[CH:14][CH:13]=3)=[O:6])([CH3:3])[CH3:2]

Participants

5

Reactant 3

HCID 8471Triethylamine2×HCID 521297Tert-Butyl hypochloriteHCID 110800626-Benzyloxy-4-methoxymethyl-1,2,3,4-tetrahydro-beta-carboline-3-carboxylic acid isopropyl ester

Product 1

HCID 65914AbecarnilYield 35%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
-15 °C

Procedure

A solution is prepared from 3.3 g (8.5 mmol) of 6-benzyloxy-4-methoxymethyl-1,2,3,4-tetrahydro-β-carboline-3-carboxylic acid isopropyl ester in 150 ml of methylene chloride, combined under argon with 3.9 ml of triethylamine, and cooled to -15° C. At this temperature, a solution of 3.2 ml (25.6 mmol) of tert-butyl hypochlorite in 50 ml of methylene chloride is added dropwise without delay to this solution. After the adding step is completed, the mixture is stirred for another 10 minutes, combined with 2.6 ml of triethylamine, and agitated for 2 hours at room temperature. Subsequently, the mixture is concentrated to one-half thereof and extracted once by shaking with dilute ammonia solution. The organic phase is dried, filtered, and concentrated. The residue is chromatographed over silica gel with methylene chloride:acetone=4:1 as the eluent. Recrystallization from ethyl acetate gives 1.1 g (35% yield) of 6-benzyloxy-4-methoxymethyl-β-carboline-3-carboxylic acid isopropyl ester, mp 150°-151° C.

Workup

  1. stirringagitated for 2 hours at room temperature
  2. concentrationSubsequently, the mixture is concentrated to one-half
  3. extractionextracted once
  4. stirringby shaking with dilute ammonia solution
  5. customThe organic phase is dried
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe residue is chromatographed over silica gel with methylene chloride
  9. customRecrystallization from ethyl acetate

Sources & evidence

ORD record
ord-3cef612d3cf94e509c18805108718a24
Source dataset
uspto-grants-1995_05
Patent number
US05414002

Reaction notes

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