Sodium Hydroxide → Pyridine, 3-[[(4-chlorobutyl)thio]methyl]-

HRID 1701911Notes

Reaction equation

HRID 1701911 reaction equation
[OH-].[Na+].Cl.Cl.[N:5]1[CH:10]=[CH:9][CH:8]=[C:7]([CH2:11][S:12][C:13](=N)N)[CH:6]=1.BrC[CH2:18][CH2:19][CH2:20][Cl:21]>O>[Cl:21][CH2:20][CH2:19][CH2:18][CH2:13][S:12][CH2:11][C:7]1[CH:6]=[N:5][CH:10]=[CH:9][CH:8]=1

Participants

5

Reactant 3

HCID 14798Sodium Hydroxide2×HCID 813641-Bromo-4-chlorobutaneHCID 13043947HCID 13043947, compound

Product 1

HCID 10443278Pyridine, 3-[[(4-chlorobutyl)thio]methyl]-Yield 70.8%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
70 °C

Procedure

A 10 N aqueous solution of sodium hydroxide (144 cc) is added dropwise, in the course of 25 minutes and whilst keeping the temperature below 12° C., to a solution of 2-(pyrid-3-ylmethyl)-isothiourea dihydrochloride (173 g) in distilled water (330 cc), cooled to 4° C. After heating for 25 minutes at 70° C. and then cooling to 11° C., a 10 N aqueous solution of sodium hydroxide (89 cc) and then 1-bromo-4-chlorobutane (123.5 g) are added, whilst stirring, and stirring is continued for 15 hours at a temperature of about 20° C. The reaction mixture is then extracted four times with methylene chloride (560 cc in total); the organic extracts are combined, washed twice with distilled water (800 cc in total), dried over anhydrous sodium sulphate and filtered. The solution is poured onto neutral silica gel (150 g) contained in a column of diameter 3.7 cm; the column is eluted with methylene chloride (2500 cc). The first fraction (600 cc) is discarded. The second (2500 cc) is concentrated to dryness under reduced pressure (25 mm Hg; 3.4 kPa) without exceeding 30° C. Pyrid-3-ylmethyl 4-chlorobutyl sulphide (110 g) is thus obtained.

Workup

  1. customthe temperature below 12° C.
  2. temperaturecooling to 11° C.
  3. stirringstirring
  4. extractionThe reaction mixture is then extracted four times with methylene chloride (560 cc in total)
  5. washwashed twice with distilled water (800 cc in total)
  6. dry with materialdried over anhydrous sodium sulphate
  7. filtrationfiltered
  8. additionThe solution is poured onto neutral silica gel (150 g)
  9. washthe column is eluted with methylene chloride (2500 cc)
  10. concentrationThe second (2500 cc) is concentrated to dryness under reduced pressure (25 mm Hg; 3.4 kPa)
  11. customwithout exceeding 30° C

Sources & evidence

ORD record
ord-50cf0983c16c4913a13934d982ee910f
Source dataset
uspto-grants-1983_04
Patent number
US04379154

Reaction notes

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