Ammonia → HCID 21424969, compound

HRID 258871Notes

Reaction equation

HRID 258871 reaction equation
N.[Li].[CH3:3][N:4]([C:6]#[C:7][CH3:8])[CH3:5].[Cl:9][C:10]1[CH:11]=[CH:12][C:13]2[S:19][C:18]3[CH:20]=[CH:21][CH:22]=[CH:23][C:17]=3[CH2:16][C:15](=[O:24])[C:14]=2[CH:25]=1.[Cl-].[NH4+]>O.O1CCCC1>[CH3:3][N:4]([CH3:5])[CH2:6][C:7]#[C:8][C:15]1([OH:24])[C:14]2[CH:25]=[C:10]([Cl:9])[CH:11]=[CH:12][C:13]=2[S:19][C:18]2[CH:20]=[CH:21][CH:22]=[CH:23][C:17]=2[CH2:16]1

Participants

8

Reactant 5

HCID 222AmmoniaHCID 25517Ammonium ChlorideHCID 8270558-chlorodibenzo[b,f]thiepin-10(11H)-oneHCID 3028194LithiumHCID 12225915N,N-Dimethylprop-1-yn-1-amine

Product 1

HCID 21424969HCID 21424969, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Procedure

2100 Ml. of liquid ammonia is reacted with some crystalline ferric nitrate and subsequently with 10.4 g. of lithium metal over a 2-hour period. After stirring for 30 minutes, there are added 369 ml. of dimethylamino-1-propyne over a 40-minute period, and the reaction mixture is stirred for an additional 45 minutes. Over a 105-minute period, there is added dropwise a solution of 300 g. of 8-chloro-10,11-dihydro-5H-dibenzo[b,f]thiepin-10-one in 1500 ml. of tetrahydrofuran. The reaction mixture is allowed to stand overnight. The following morning, the reaction mixture is treated with 228 g. of ammonium chloride in 600 ml. of water. The ammonia, thereafter, is evaporated. 900 Ml. of tetrahydrofuran are added, and the mixture is heated at reflux for 2 hours. The reaction mixture is evaporated, diluted with water and extracted with ether. The ether extract is washed with water and extracted three times with aqueous methanesulfonic acid. The unreacted starting ketones can be recovered from the ethereal phase. The aqueous phase is made alkaline with concentrated sodium hydroxide, whereby there is obtained 10-[3-(dimethylamino)-1-propynyl]-8-chloro-10,11-dihydro-dibenzo[b,f]thiepin-10-ol, which is taken up in chloroform. The chloroform phase is washed with water, dried and evaporated, whereby there is obtained the above-named product, which after recrystallization from acetone, has a melting point of 150°-152°.

Workup

  1. additionthere are added 369 ml
  2. stirringthe reaction mixture is stirred for an additional 45 minutes
  3. additionOver a 105-minute period, there is added dropwise a solution of 300 g
  4. waitto stand overnight
  5. additionThe following morning, the reaction mixture is treated with 228 g
  6. customThe ammonia, thereafter, is evaporated
  7. additionof tetrahydrofuran are added
  8. temperaturethe mixture is heated
  9. temperatureat reflux for 2 hours
  10. customThe reaction mixture is evaporated
  11. additiondiluted with water
  12. extractionextracted with ether
  13. extractionThe ether extract
  14. washis washed with water
  15. extractionextracted three times with aqueous methanesulfonic acid
  16. customcan be recovered from the ethereal phase

Sources & evidence

ORD record
ord-8ff8b9771dfc40258b74ae525133581b
Source dataset
uspto-grants-1977_07
Patent number
US04035385

Reaction notes

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