4-Toluenesulfonyl chloride → HCID 178419512, Verbindung

HRID 325282

Reaktionsgleichung

Reaktionsgleichung von HRID 325282
[NH2:1][C@@H:2]([C:7]([NH:9][CH2:10][C:11]([NH:13][C@H:14]([C:22]([NH:24][C:25]1[CH:33]=[CH:32][C:28]([N+:29]([O-:31])=[O:30])=[CH:27][CH:26]=1)=[O:23])[CH2:15][CH2:16][CH2:17][NH:18][C:19](=[NH:21])[NH2:20])=[O:12])=[O:8])[CH2:3][CH:4]([CH3:6])[CH3:5].[S:34](Cl)([C:37]1[CH:43]=[CH:42][C:40]([CH3:41])=[CH:39][CH:38]=1)(=[O:36])=[O:35].N(CC)(CC)CC.[BrH:52].N(CC)(CC)CC.Cl>CN(C=O)C.CCN(CC)CC>[NH:1]([S:34]([C:37]1[CH:43]=[CH:42][C:40]([CH3:41])=[CH:39][CH:38]=1)(=[O:36])=[O:35])[C@@H:2]([C:7]([NH:9][CH2:10][C:11]([NH:13][C@H:14]([C:22]([NH:24][C:25]1[CH:26]=[CH:27][C:28]([N+:29]([O-:31])=[O:30])=[CH:32][CH:33]=1)=[O:23])[CH2:15][CH2:16][CH2:17][NH:18][C:19](=[NH:20])[NH2:21])=[O:12])=[O:8])[CH2:3][CH:4]([CH3:5])[CH3:6].[BrH:52]

Komponenten

7

Edukt 4

HCID 73974-Toluenesulfonyl chlorideHCID 11130Triethylamine hydrochlorideHCID 2734074Triethylammonium bromideHCID 178446030HCID 178446030, Verbindung

Produkt 1

HCID 178419512HCID 178419512, Verbindung

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 6228DimethylformamideLösungsmittelHCID 8471TriethylamineLösungsmittel

Versuchsvorschrift

6.26 g (10 mM) of 2HBr.H-D-Leu-Gly-Arg-pNA (prepared according to Example 7f, see Table 3) were dissolved in 30 ml of distilled DMF. The solution was cooled to -15°, and first 2.80 ml (20 mM) of Et3N and immediately afterwards 1.91 g (10 mM) of tosyl chloride were added, while stirring, in the absence of humidity. After a reaction time of about 2 to 3 hours at -15°, the reaction mixture was allowed to further react overnight at room temperature. The reaction mixture was again cooled to -15°. The precipitated mixture of Et3N.HBr and Et3N.HCl was removed by filtration and washed with a small amount of cold DMF. The filtrate and the washing solution were combined and concentrated to dryness in vacuo at 50°. The residue was dissolved in 75 ml of 50% AcOH. The solution was purified on a column of "Sephadex" G-15 equilibrated with 50% AcOH. The main fraction of the AcOH eluate which was split by treatment with trypsin with release of p-nitroaniline was concentrated to dryness in vacuo at 40°. The residue was dissolved in 100 ml of MeOH, and the solution was again concentrated to dryness. The residue was dried in a vacuum desiccator at 60° over P2O5 to obtain 6.65 g (95.0% of the theory) of amorphous compound Tos-D-Leu-Gly-Arg-pNA.HBr which was homogeneous in the SS as shown by TLC. Elementary analysis and calculation from the empirical formula C27H39N8SO7Br gave the following values: C=46.85% (46.35%), H=5.66% (5.62%), N=16.28% (16.02%), S=4.43% (4.58%) and Br=11.22% (11.42%).

Aufarbeitung

  1. temperatureThe solution was cooled to -15°
  2. customAfter a reaction time of about 2 to 3 hours
  3. customat -15°
  4. customto further react overnight at room temperature
  5. temperatureThe reaction mixture was again cooled to -15°
  6. customwas removed by filtration
  7. washwashed with a small amount of cold DMF
  8. concentrationconcentrated to dryness in vacuo at 50°
  9. dissolutionThe residue was dissolved in 75 ml of 50% AcOH
  10. customThe solution was purified on a column of "Sephadex" G-15
  11. customThe main fraction of the AcOH eluate which was split by treatment with trypsin with release of p-nitroaniline
  12. concentrationwas concentrated to dryness in vacuo at 40°
  13. dissolutionThe residue was dissolved in 100 ml of MeOH
  14. concentrationthe solution was again concentrated to dryness
  15. dry with materialThe residue was dried in a vacuum desiccator at 60° over P2O5

Quellen und Nachweise

ORD-Eintrag
ord-5488d639101d4b6989e33348850745c2
Quelldatensatz
uspto-grants-1984_04
Patentnummer
US04440678

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