2-Bromothiophene → HCID 20041072, compound

HRID 1762462Notes

Reaction equation

HRID 1762462 reaction equation
BrC1SC=CC=1.[Mg].[Cl:8][C:9]1[CH:10]=[C:11]([C:16]2(C#N)[CH2:19][CH2:18][CH2:17]2)[CH:12]=[CH:13][C:14]=1[Cl:15].[S:22]1[CH:26]=[CH:25][CH:24]=[C:23]1[CH:27]=[N:28][Mg]Br>CCOCC>[ClH:8].[Cl:8][C:9]1[CH:10]=[C:11]([C:16]2([NH:28][CH2:27][C:23]3[S:22][CH:26]=[CH:25][CH:24]=3)[CH2:17][CH2:18][CH2:19]2)[CH:12]=[CH:13][C:14]=1[Cl:15]

Participants

6

Reactant 4

HCID 138512-BromothiopheneHCID 5462224Magnesium2×HCID 108571341-(3,4-Dichlorophenyl)-1-cyclobutane-carbonitrileHCID 178419685HCID 178419685, compound

Product 1

HCID 20041072HCID 20041072, compound

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent3×

Conditions

Temperature
20 °C

Procedure

A solution of 2-bromothiophene (32.9 g) in dry ether (50 ml) was added dropwise to a stirred mixture of magnesium turnings (4.85 g) and ether (50 ml) under nitrogen. When all the magnesium had dissolved a solution of 1-(3,4-dichlorophenyl)cyclobutanecarbonitrile (30.6 g) in dry ether (200 ml) was added and the mixture stirred at 20° C. for one hour and then heated under reflux for one hour. A solid formed which is believed to be 1-(3,4-dichlorophenyl)cyclobutyl](thien-2-yl)methaniminylmagnesium bromide and was collected by filtration. The solid was dissolved in ethanol (200 ml) and a solution of sodium borohydride (10 g) in ethanol (500 ml) added and the mixture heated under reflux for four hours. The mixture was cooled and water (200 ml) and then 5N hydrochloric acid added. The ethanol was removed by evaporation and the aqueous solution basified by the addition of 5N sodium hydroxide solution. The aqueous layer was extracted with ether and the extract dried. Hydrogen chloride gas was passed into the ethereal solution to give [1-(3,4-dichlorophenyl)cyclobutyl](thien-2-yl)methylamine hydrochloride (m.p. 238°-242° C.).

Workup

  1. additionwas added
  2. temperatureheated
  3. temperatureunder reflux for one hour
  4. customA solid formed which
  5. filtrationwas collected by filtration
  6. dissolutionThe solid was dissolved in ethanol (200 ml)
  7. additiona solution of sodium borohydride (10 g) in ethanol (500 ml) added
  8. temperaturethe mixture heated
  9. temperatureunder reflux for four hours
  10. temperatureThe mixture was cooled
  11. additionwater (200 ml) and then 5N hydrochloric acid added
  12. customThe ethanol was removed by evaporation
  13. additionthe aqueous solution basified by the addition of 5N sodium hydroxide solution
  14. extractionThe aqueous layer was extracted with ether
  15. customthe extract dried

Sources & evidence

ORD record
ord-98befdcbbc8b4d168956f5357f7f1f7d
Source dataset
uspto-grants-1989_05
Patent number
US04833143

Reaction notes

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