Isoamyl Nitrite → Z-Ser-Leu-Ser-OCH3

HRID 1632419Notes

Reaction equation

[NH:1]([C:9]([O:11][CH2:12][C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1)=[O:10])[C@H:2]([C:5]([NH:7]N)=[O:6])[CH2:3][OH:4].Cl.O1CCOCC1.N(OCCC(C)C)=O.[N-]=[N+]=[N-].N[C@H:38]([C:43]([NH:45][C@H:46]([C:49]([O:51][CH3:52])=[O:50])[CH2:47][OH:48])=[O:44])[CH2:39][CH:40]([CH3:42])[CH3:41].Cl>CN(C)C=O.NN.O.C(N(CC)CC)C>[NH:1]([C:9]([O:11][CH2:12][C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1)=[O:10])[C@H:2]([C:5]([NH:7][C@H:38]([C:43]([NH:45][C@H:46]([C:49]([O:51][CH3:52])=[O:50])[CH2:47][OH:48])=[O:44])[CH2:39][CH:40]([CH3:42])[CH3:41])=[O:6])[CH2:3][OH:4]

Participants

Conditions

Temperature: -15 °C

Procedure

3.19 Grams of Z-Ser-NHNH2 was dissolved in 25 ml of dimethylformamide, and 6.30 ml of 6N-hydrochloric acid/dioxane was added to the solution, cooled to -15° C., then 1.69 ml of isoamyl nitrite was added thereto. After the reaction mixture shows a negative reaction in hydrazine-test, 1.76 ml of a cold dimethylformamide solution with 5.29 ml of triethylamine was added drop by drop in small amount to neutralize the reaction mixture. This reaction mixture containing an azide product was added to 20 ml of a cold dimethylformamide solution containing H-Leu-Ser-OCH3.HCl obtained in the above-mentioned step 14(a) and 1.60 ml of triethylamine, and the whole mixture was stirred at -10° to -15° C. for 2 hours, next at 4° C. for 18 hours. Dimethylformamide was removed by distillation under a reduced pressure, the residue obtained was solidified by adding water, reprecipitated from methanol-ethyl acetate to obtain 4.11 g of the desired product.

Workup

additionwas added drop by drop in small amount
customDimethylformamide was removed by distillation under a reduced pressure
customthe residue obtained
customreprecipitated from methanol-ethyl acetate

Sources & evidence

ORD record: ord-a293f166da0540ffa1c432bcd83609e3
Source dataset: uspto-grants-1984_10
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US04474754

Reaction notes

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