Reaction #159986

Reaction equation

[[[(1,1-dimethylethoxy)carbonyl]amino]-(methylthio)methylene]-carbamic acid, 1,1-dimethylethyl ester

thiomorpholine

Et3N

methanethiol

→

(tert-Butoxycarbonylimino-thiomorpholin-4-yl-methyl)-carbamic acid tert-butyl ester

Solvents

DMF

EtOAc

Conditions

Workup

1. 1
   Filtrationfiltered through a pad of diatomaceous earth
2. 2
   ConcentrationThe filtrate was concentrated
3. 3
   workup.ADDITIONdiluted with water and EtOAc
4. 4
   Filtrationfiltered again through a pad of diatomaceous earth
5. 5
   OtherThe filtrate aqueous layer was separated
6. 6
   Extractionextracted with EtOAc (2×)
7. 7
   WashThe combined organic layers were washed with water
8. 8
   Dryingaq. NaCl, dried
9. 9
   Concentrationconcentrated
10. 10
    OtherThe solid was triturated with 20% Et2O/40-60° C. petrol
11. 11
    FiltrationThe solid was filtered off
12. 12
    Washwas washed with 20% Et2O/40-60° C. petrol
13. 13
    Otherfollowed by 40-60° C.
14. 14
    OtherThe solid was dried under vacuum
15. 15
    Otherto give 21.2 g (85%) as a white solid

Procedure

A solution of [[[(1,1-dimethylethoxy)carbonyl]amino]-(methylthio)methylene]-carbamic acid, 1,1-dimethylethyl ester [CAS 107819-90-9] (21 g, 0.0723 mol) in DMF (450 mL) was treated sequentially with thiomorpholine (7 mL, 0.0723 mol), mercury chloride (19.6 g, 0.0723 mol), and Et3N (30 mL, 0.22 mol) and the reaction mixture was stirred for 18 h. The mixture was diluted with EtOAc and filtered through a pad of diatomaceous earth. The filtrate was concentrated, diluted with water and EtOAc and filtered again through a pad of diatomaceous earth. The filtrate aqueous layer was separated and extracted with EtOAc (2×). The combined organic layers were washed with water, then satd. aq. NaCl, dried, and concentrated. The solid was triturated with 20% Et2O/40-60° C. petrol. The solid was filtered off and was washed with 20% Et2O/40-60° C. petrol followed by 40-60° C. petrol. The solid was dried under vacuum to give 21.2 g (85%) as a white solid. Note: The reaction was performed with a trap for gaseous loss of methanethiol.

Source