Water → HCID 3067724, compound

HRID 1388542Notes

Reaction equation

HRID 1388542 reaction equation
[CH:1]1[C:11]2[CH2:10][S:9][C:8]3[CH:12]=[CH:13][CH:14]=[CH:15][C:7]=3[S:6][C:5]=2[CH:4]=[CH:3][CH:2]=1.C([Li])CCC.O.[CH3:22][N:23]([CH3:27])[CH2:24][CH2:25]Cl>CCOCC.CCCCCC>[CH3:22][N:23]([CH3:27])[CH2:24][CH2:25][CH:10]1[S:9][C:8]2[CH:12]=[CH:13][CH:14]=[CH:15][C:7]=2[S:6][C:5]2[CH:4]=[CH:3][CH:2]=[CH:1][C:11]1=2

Participants

7

Reactant 4

HCID 962WaterHCID 79012-Chloro-N,N-dimethylethylamineHCID 12920939HCID 12920939, compoundHCID 178418339Butyllithium

Product 1

HCID 3067724HCID 3067724, compound

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8058HexaneSolvent

Procedure

A solution of 3.40 g of 11H-dibenzo(b,e)-1,4-dithiepin (K. Sindelar, M. Protiva and M. Hrubantova, Czech. 202.239) in 50 ml of ether was treated dropwise over 20 minutes of 15% n-butyllithium solution in hexane in a nitrogen atmosphere. The mixture was stirred for 30 minutes at room temperature and then treated with external cooling with ice and water and with 10 ml of 2-dimethylaminoethyl chloride, added dropwise. Then, the mixture was stirred for another 2 hours at room temperature. It was then washed with water and the basic product extracted into a mild excess of 1:1 dilute hydrochloric acid. The acid aqueous layer was separated, made alkaline with aqueous ammonia and the base extracted with ether. The extract was dried with potassium carbonate and evaporated. The remaining oily base was dissolved in 7 ml of acetone and treated with a solution of 1.81 g of oxalic acid in 5 ml of acetone. The crystalline hydrogen oxalate (5.31 g) separated, was filtered with suction and purified by recrystallization from aqueous ethanol, m.p. 195°-197° C.

Workup

  1. additiontreated
  2. additionadded dropwise
  3. stirringThen, the mixture was stirred for another 2 hours at room temperature
  4. washIt was then washed with water
  5. extractionthe basic product extracted into a mild excess of 1:1 dilute hydrochloric acid
  6. customThe acid aqueous layer was separated
  7. extractionthe base extracted with ether
  8. dry with materialThe extract was dried with potassium carbonate
  9. customevaporated
  10. dissolutionThe remaining oily base was dissolved in 7 ml of acetone
  11. additiontreated with a solution of 1.81 g of oxalic acid in 5 ml of acetone
  12. customThe crystalline hydrogen oxalate (5.31 g) separated
  13. filtrationwas filtered with suction
  14. custompurified by recrystallization from aqueous ethanol, m.p. 195°-197° C.

Sources & evidence

ORD record
ord-b2fa22119dd64e6eb04bb2750e8ea6fe
Source dataset
uspto-grants-1984_02
Patent number
US04431808

Reaction notes

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