Sulfuric Acid → Chloro-5-[(methylsulfonimidoyl)methyl]pyridine

Temperature

0 °C

To a stirred mixture of 2-chloro-5-[(methylsulfinyl)methyl]pyridine (B) (7.34 g, 39 mmol) and sodium azide (4.04 g, 62 mmol) in chloroform (80 mL) cooled to 0° C. was slowly added sulfuric acid at a rate such that the temperature did not rise above 8° C. After the addition was over, the ice-water bath was removed and the mixture was heated at 55° C. for 2.5 h. The solvent was decanted into a separation funnel and the residue was stirred and dissolved in water. After a few minutes, the aqueous mixture was made basic to pH 8 by slowly adding solid Na2CO3 and then saturated with solid NaCl. The extra salt was removed by filtration (a portion of the filtrate was sucked into trap and was not recovered) and the filtrate was extracted with CH2Cl2 three times. The combined organic layer was dried over Na2SO4, filtered, concentrated and the residue was triturated in CH2Cl2-ether (1:10, v/v) solvent. The white solid was filtered, washed with CH2Cl2-ether (1:10, v/v) and dried to give 2.70 g of -chloro-5-[(methylsulfon-imidoyl)methyl]pyridine (C) in 34% yield as a white solid (m.p. 134.5-136° C.). LC-MS (ELSD): mass calcd for C7H9ClN2OS [M+H]+ 203.67. Found: 203.22.

1. customdid not rise above 8° C
2. additionAfter the addition
3. customwas removed
4. temperaturethe mixture was heated at 55° C. for 2.5 h
5. customThe solvent was decanted into a separation funnel
6. dissolutiondissolved in water
7. waitAfter a few minutes
8. additionby slowly adding solid Na2CO3
9. customThe extra salt was removed by filtration (a portion of the filtrate
10. customwas sucked into trap
11. customwas not recovered) and the filtrate
12. extractionwas extracted with CH2Cl2 three times
13. dry with materialThe combined organic layer was dried over Na2SO4
14. filtrationfiltered
15. concentrationconcentrated
16. customthe residue was triturated in CH2Cl2-ether (1:10
17. filtrationThe white solid was filtered
18. washwashed with CH2Cl2-ether (1:10
19. customv/v) and dried

ORD record

ord-388192b17ffc42419f811a13e90f90d0

Source dataset

uspto-grants-2011_09

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08017788B2