Hydrochloric Acid → HCID 355604, compound

To a stirred solution of 36.8 g (0.124 mole) N-(n-propyl)-3,5,6-trichloropyridyloxyacetamide (Example 2) in 300 ml tetrahydrofuran at room temperature, 27.2 ml (0.272 mole) boranemethyl sulfide were added in three portions (9 ml, 9 ml and 9.2 ml) rapidly through a syringe. The reaction mixture was stirred at its own exotherm, and then at ambient temperature under nitrogen gas overnight. The gel-like mixture was then refluxed under nitrogen gas for two hours. The stirred reaction mixture was then placed in an ice water bath while 60 ml methanol was added dropwise over 1/2 hour resulting in gas (H2) evolution to give a clear solution. The solution was stirred until bubbling (gas evolution) ceased. The reaction mixture was stripped in vacuo to give an oil. The oil was dissolved in 325 ml methylene chloride. To that stirred mixture in an ice bath, 36 ml concentrated hydrochloric acid were added dropwise over 1/2 hour [gas (H2) evolution]. The resulting mixture was stirred at ambient temperature until gas evolution ceased (about 5 hours). Water (250 ml) was added to the reaction mixture; then concentrated sodium hydroxide (50%) was added until the pH of the mixture reached 10 (about 25 ml). Additional water (200 ml) and methylene chloride (200 ml) were added to the reaction mixture. The resulting mixture was stirred until there were 2 clear layers. The organic layer was separated, washed with water (about 250 ml), dried over magnesium sulfate and filtered. The filtrate was stripped in vacuo to give an oily residue. The residue was slurried in with petroleum ether. The petroleum ether mixture was filtered (to remove solids). The filtrate was stripped in vacuo to give 30.3 g of the above-identified product as an oil.

1. customat ambient temperature
2. customovernight
3. temperatureThe gel-like mixture was then refluxed under nitrogen gas for two hours
4. customThe stirred reaction mixture
5. additionwas added dropwise over 1/2 hour
6. customresulting in gas (H2) evolution
7. customto give a clear solution
8. stirringThe solution was stirred
9. customuntil bubbling (gas evolution)
10. customto give an oil
11. stirringTo that stirred mixture in an ice bath
12. stirringThe resulting mixture was stirred at ambient temperature until gas evolution
13. custom(about 5 hours)
14. stirringThe resulting mixture was stirred until there
15. customThe organic layer was separated
16. washwashed with water (about 250 ml)
17. dry with materialdried over magnesium sulfate
18. filtrationfiltered
19. customto give an oily residue
20. filtrationThe petroleum ether mixture was filtered
21. custom(to remove solids)

ORD record

ord-db11d32f25834444a56902efd655a7b7

Source dataset

uspto-grants-1986_04

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US04579856