Methyl chloroformate → HCID 9834021, compound

Temperature

-70 °C

11.8 g (0.048 M) of N-(3-trimethylsilylprop-2-ynyl)benzenecarboximidate in 20 ml of tetrahydrofuran is added to lithium diisopropylamide, prepared from 4.9 g (6.78 ml, 0.048 M) of diisopropylamide in 60 ml of tetrahydrofuran and 23.6 ml of a 2.05 M solution of n-butyllithium at -70° C. after which 9.5 g (0.042 M) of N-(3-bromopropyl)benzylimine is added, and the mixture is stirred at -70° C. for 51/2 hours. To the reaction mixture is added 23.6 ml of a 2.05 M solution of n-butyllithium followed by the addition of 4.5 g (3.67 ml, 0.048 M) of methyl chloroformate. After 30 minutes at -78° C. the mixture is treated with brine, and the reaction product is isolated by ether extraction. The ether extract is evaporated and 300 ml of 3 N HCl is added to the resulting residue and the mixture is refluxed for 7 hours. On cooling the mixture is washed well with methylene chloride, made alkaline and washed again. The aqueous solution is acidified and concentrated to dryness. The residue is triturated with ethanol, filtered and the ethanol evaporated. The residue is dissolved in water, the pH adjusted to 6, and the solution is applied to a column of Amberlite 120 H+, eluting with 1 M NH4OH which affords, upon recrystallization from ethanol-water, α-ethynyl-α,δ-diaminovaleric acid, M.P. 168-169 (dec.).

1. additionis added
2. extractionThe ether extract
3. customis evaporated
4. addition300 ml of 3 N HCl is added to the resulting residue
5. temperaturethe mixture is refluxed for 7 hours
6. temperatureOn cooling the mixture
7. washis washed well with methylene chloride
8. washwashed again
9. concentrationconcentrated to dryness
10. customThe residue is triturated with ethanol
11. filtrationfiltered
12. customthe ethanol evaporated
13. dissolutionThe residue is dissolved in water
14. washeluting with 1 M NH4OH which

ORD record

ord-01d2177e8ee4431393d7a775a9adbdfa

Source dataset

uspto-grants-1982_06

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US04336054