Pentachlorophenol → HCID 54166524, compound

HRID 329253Notes

Reaction equation

HRID 329253 reaction equation
[C:1]([CH2:20][CH2:21][C:22]([OH:24])=[S:23])([C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[Cl:25][C:26]1[C:31](O)=[C:30]([Cl:33])[C:29]([Cl:34])=[C:28]([Cl:35])[C:27]=1[Cl:36].C1(N=C=NC2CCCCC2)CCCCC1>O1CCCC1>[Cl:25][C:26]1[C:31]([O:24][C:22](=[S:23])[CH2:21][CH2:20][C:1]([C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)([C:14]2[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=2)[C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=2)=[C:30]([Cl:33])[C:29]([Cl:34])=[C:28]([Cl:35])[C:27]=1[Cl:36]

Participants

5

Reactant 3

HCID 992PentachlorophenolHCID 10868DicyclohexylcarbodiimideHCID 178526179HCID 178526179, compound2×

Product 1

HCID 54166524HCID 54166524, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

In a preferred embodiment of the preparation of the above first tetrapeptide hydrazide, the activated ester of 3-tritylthiopropionic acid, preferably the pentachlorophenyl ester, is prepared by combining substantially equimolar amounts of 3-tritylthiopropionic acid, pentachlorophenol and dicyclohexylcarbodiimide in an inert organic solvent, preferably tetrahydrofuran, at about 0° to 10° C. The mixture is stirred at about 0° to 10° C for about 1 hour and then at about 20° to 30° C for about 1 hour. The mixture is cooled to about 0° C, filtered and the filtrate evaporated. The residue is crystallized to obtain 3-tritylthiopropionic acid pentachlorophenyl ester. A solution of said last-named compound and a substantially equimolar amount of the tetrapeptide of formula H-Lys(Boc)-Asn-Phe-Phe-OMe acetate, prepared as described by H. U. Immer et al., cited above, in an inert organic solvent, preferably dimethylformamide or tetrahydrofuran, is treated with a substantially equimolar amount of an organic base, preferably triethylamine, at about 20° to 30° C. The mixture is stirred for 2 to 3 days at about 20° to 30° C and the solvent evaporated under reduced pressure. The residue is triturated with cold dilute aqueous citric acid and water, dried, and crystallized to give the tetrapeptide of formula Trt--SCH2CH2CO--Lys(Boc)--Asn--Phe--Phe--OMe. Said last-named compound is dissolved in an inert organic solvent, for example, methanol, ethanol, or preferably dimethylformamide. The solution is treated with an excess of hydrazine hydrate, for example 15 to 30 molar equivalents. The reaction mixture is kept at about 20° to 30° C for about 20 to 30 hours and evaporated under reduced pressure. The residue is triturated with cold water and dried to give said tetrapeptide hydrazide of formula (2, R = H) Trt--SCH2CH2CO--Lys(Boc)--Asn--Phe--Phe--NHNH2.

Workup

  1. customat about 0° to 10° C
  2. waitat about 20° to 30° C for about 1 hour
  3. filtrationfiltered
  4. customthe filtrate evaporated
  5. customThe residue is crystallized

Sources & evidence

ORD record
ord-ebde7add68db4044aac8fa98f0f69ea1
Source dataset
uspto-grants-1977_04
Patent number
US04020157

Reaction notes

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