Ammonia → 9-(prop-2-yn-1-yl)-9H-carbazole

HRID 1703768Notes

Reaction equation

HRID 1703768 reaction equation
C(=O)=O.[CH3:4][C:5]([CH3:7])=O.[CH:8]1[C:20]2[NH:19][C:18]3[C:13](=[CH:14][CH:15]=[CH:16][CH:17]=3)[C:12]=2[CH:11]=[CH:10][CH:9]=1.[NH2-].[Na+].N.BrCC#C>>[CH:5]1[C:7]2[N:19]([CH2:20][C:8]#[CH:9])[C:18]3[C:13](=[CH:14][CH:15]=[CH:16][CH:17]=3)[C:12]=2[CH:11]=[CH:10][CH:4]=1

Participants

6

Reactant 5

HCID 222Ammonia2×HCID 6854CarbazoleHCID 7842Propargyl bromideHCID 24533Sodium amideHCID 18522661Acetone cardice

Product 1

HCID 2844439-(prop-2-yn-1-yl)-9H-carbazole

Conditions

Temperature
33 °C

Procedure

A 3,000 ml. 3-necked, round bottom flask was fitted with mechanical stirrer, addition funnel, Dry Ice/acetone reflux condenser and means for providing nitrogen atmosphere. To the flask was added 75 g (0.45 mole) of carbazole, 20 g (0.50 mole) of sodium amide, and 1500 ml of liquid ammonia. After stirring vigorously at 31 33° C for about 2.5 hr, 75 g (0.63 mole) of 3-bromo-1-propyne was added dropwise over a period of 1 hr to the reaction mixture at -55° C. After the addition, striring was continued for an additional 5 hrs, and the ammonia was allowed to evaporate overnight. The residue in the reaction flask was extracted with hexane four times. In each extraction, 3,000 ml of hexane was used and the hexane mixture was stirred vigorously with a mechanical stirrer for about 5 hrs at room temperature. Removal of the solvent from each fraction gave the desired product: fraction #1 =24 g (m.p. 94°-100° C); fraction #2 =21 g (m.p. 103°-106° C); fraction #3 =25 g (m.p. 104°-106° C); and fraction 190 4 =17 g (m.p. 100°-106° C). The combined crystals (87 g, 94% yield) were recrystallized from hexane at a concentration of 7 g per 100 ml of hexane, giving 60 g of plate-like crystals, m.p. 104°-107° C. IR (KBr pellet) in cm-1 : 3250 (C≡CH), 2120 (C≡C), 1620 +1590 (C=C), 1480 (CH2), 1450 +1320 (C--N), 740 +720 (Ar), 680 +660 (C ≡CH).

Workup

  1. custom3-necked, round bottom flask was fitted with mechanical stirrer, addition funnel
  2. customfor providing nitrogen atmosphere
  3. additionAfter the addition, striring
  4. waitwas continued for an additional 5 hrs
  5. customto evaporate overnight
  6. extractionThe residue in the reaction flask was extracted with hexane four times
  7. extractionIn each extraction, 3,000 ml of hexane
  8. stirringthe hexane mixture was stirred vigorously with a mechanical stirrer for about 5 hrs at room temperature
  9. customRemoval of the solvent from each fraction

Sources & evidence

ORD record
ord-4412905d6f21453a8a3b55d932e8a13b
Source dataset
uspto-grants-1978_11
Patent number
US04125534

Reaction notes

Loading…