4-Toluenesulfonyl chloride → HCID 13799189, compound

HRID 2413716Notes

Reaction equation

HRID 2413716 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][CH2:23][C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1)[CH:14]=[CH:13][CH:12]=3)=[O:5])[CH3:2].CN(C1C=CC=CN=1)C.[S:39](Cl)([C:42]1[CH:48]=[CH:47][C:45]([CH3:46])=[CH:44][CH:43]=1)(=[O:41])=[O:40].C(=O)([O-])O.[Na+]>ClCCl.C(N(CC)CC)C>[CH2:1]([O:3][C:4]([C:6]1[N:7]=[CH:8][C:9]2[N:10]([S:39]([C:42]3[CH:48]=[CH:47][C:45]([CH3:46])=[CH:44][CH:43]=3)(=[O:41])=[O:40])[C:11]3[C:16]([C:17]=2[C:18]=1[CH2:19][O:20][CH3:21])=[C:15]([O:22][CH2:23][C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1)[CH:14]=[CH:13][CH:12]=3)=[O:5])[CH3:2]

Participants

7

Reactant 4

HCID 73974-Toluenesulfonyl chlorideHCID 218852-DimethylaminopyridineHCID 123700ZK 91296HCID 516892Sodium Bicarbonate

Product 1

HCID 13799189HCID 13799189, compoundYield 73.5%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8471TriethylamineSolvent

Conditions

Temperature
0 °C

Procedure

3.9 g of 5-benzyloxy-4-methoxymethyl-beta-carboline-3-carboxylic acid ethyl ester is dissolved in 70 ml of dichloromethane with 1.84 ml of triethylamine and 0.54 g of dimethylaminopyridine. The solution is cooled to 0° C. and then mixed by portions with 2.54 g of tosyl chloride. After stirring for 2 hours at room temperature and standing overnight, it is shaken out three times with sodium hydrogen carbonate solution, the organic phase is concentrated and recrystallized from acetic acid. 4 g of 5-benzyloxy-4-methoxymethyl-9-tosyl-beta-carboline-3-carboxylic acid ethyl ester with a melting point of 149°-150° C. is obtained. This 4 g is dissolved in 40 ml of tetrahydrofuran under argon and mixed at room temperature with 17 ml of a 1.7 molar solution of calcium diisopropoxy aluminum hydride in tetrahydrofuran (Capal); after refluxing for one hour, 17 ml of Capal is added once more and refluxing is continued for 2 hours. After cooling, it is mixed with 2N sodium hydroxide solution and shaken out with acetic acid. The organic phase is concentrated and 3.1 g of 5-benzyloxy-4-methoxymethyl-9-tosyl-3-hydroxymethyl-beta-carboline is obtained, which is suspended in 57 ml of toluene and mixed with 1 ml of azodicarboxylic acid ester. After refluxing for 12 hours, it is concentrated and chromatographed over silica gel with cyclohexane:acetic acid=1:1 as eluant, 1.8 g of 5-benzyloxy-4-methoxymethyl-9-tosyl-beta-carboline-3-carbaldehyde with a melting point of 125°-127° C. is obtained.

Workup

  1. waitstanding overnight
  2. concentrationthe organic phase is concentrated
  3. customrecrystallized from acetic acid

Sources & evidence

ORD record
ord-dc5b497f59b14d368246e05196d8c401
Source dataset
uspto-grants-1988_01
Patent number
US04719210

Reaction notes

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