Reaction #64608

Reaction equation

triethylamine

triethylamine

6-benzyloxy-4-methoxymethyl-1,2,3,4-tetrahydro-β-carboline-3-carboxylic acid isopropyl ester

tert-butyl hypochlorite

→

6-benzyloxy-4-methoxymethyl-β-carboline-3-carboxylic acid isopropyl ester

Yield 35.0%

Solvents

methylene chloride

methylene chloride

Conditions

Workup

1. 1
   workup.STIRRINGagitated for 2 hours at room temperature
2. 2
   ConcentrationSubsequently, the mixture is concentrated to one-half
3. 3
   Extractionextracted once
4. 4
   workup.STIRRINGby shaking with dilute ammonia solution
5. 5
   OtherThe organic phase is dried
6. 6
   Filtrationfiltered
7. 7
   Concentrationconcentrated
8. 8
   OtherThe residue is chromatographed over silica gel with methylene chloride
9. 9
   OtherRecrystallization from ethyl acetate

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.

Source