Hydrochloric Acid → 1-(N-carbazolyl)-2,4-heptadecadiyne

HRID 1703771Notes

Reaction equation

HRID 1703771 reaction equation
Cl.NO.[CH:4]1[C:16]2[N:15]([CH2:17][C:18]#[CH:19])[C:14]3[C:9](=[CH:10][CH:11]=[CH:12][CH:13]=3)[C:8]=2[CH:7]=[CH:6][CH:5]=1.C(N)C.Br[C:24]#[C:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][CH2:35][CH2:36][CH3:37].[Cl-].[Na+].Cl.[K+].[Br-]>O.CN(C)C=O>[CH:13]1[C:14]2[N:15]([CH2:17][C:18]#[C:19][C:24]#[C:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][CH2:35][CH2:36][CH3:37])[C:16]3[C:8](=[CH:7][CH:6]=[CH:5][CH:4]=3)[C:9]=2[CH:10]=[CH:11][CH:12]=1

Participants

10

Reactant 7

HCID 313Hydrochloric AcidHCID 5234Sodium ChlorideHCID 6341EthylamineHCID 253877Potassium BromideHCID 2844439-(prop-2-yn-1-yl)-9H-carbazoleHCID 443297Hydroxyamine hydrochlorideHCID 140260081-Bromotetradec-1-yne

Product 1

HCID 203343961-(N-carbazolyl)-2,4-heptadecadiyneYield 95%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
37 °C

Procedure

A 250 ml, three-necked, round bottom flask was fitted with mechanical stirrer, addition funnel, reflux condenser, thermometer and means for providing nitrogen atmosphere. To the flask was added 0.5 g of hydroxylamine hydrochloride, 0.25 g of cuprous chloride, 15.0 g (0.073 mole) of 3-(N-carbazolyl) propyne (prepared as in Example 2A), 75 ml of dimethylformamide, 12 ml of water, and 12 ml of 70% ethylamine. The resulting mixture was stirred and heated to 37° C, and 21.9 g (0.080 mole) of 1-bromo-1-tetradecyne (from Example 17A) was added dropwise over a period of 30 min at a temperature of 37° to 52° C. After stirring and heating at 50° to 55° C for an additional 75 min, the reaction mixture was cooled to room temperature and poured into an aqueous solution of 150 ml of sodium chloride containing 5 ml of concentrated HCl. The resulting mixture was extracted four times with 100 ml portions of ether. The combined ethereal layers were washed ten times with 50 ml portions of 0.6 N HCl, twice with 50 ml portions of sodium bicarbonate, dried and concentrated, resulting in 28.0 g (95% yield), of yellow powder, m.p. 53°-58° C. Recrystallization once from methanol gave colorless long needle crystals, m.p. 71°-72° C. I. R. (KBr pellet) in cm-1 : 3060 (Ar H), 2920 + 2850 (CH), 2260 (C≡C), 1620 + 1600 (C=C), 1480 (CH2), 1460 + 1330 (CN), 750 +720 (Ar H).

Workup

  1. customA 250 ml, three-necked, round bottom flask was fitted with mechanical stirrer, addition funnel
  2. temperaturereflux condenser
  3. customfor providing nitrogen atmosphere
  4. stirringAfter stirring
  5. temperatureheating at 50° to 55° C for an additional 75 min
  6. temperaturethe reaction mixture was cooled to room temperature
  7. extractionThe resulting mixture was extracted four times with 100 ml portions of ether
  8. washThe combined ethereal layers were washed ten times with 50 ml portions of 0.6 N HCl
  9. dry with materialtwice with 50 ml portions of sodium bicarbonate, dried
  10. concentrationconcentrated
  11. customresulting in 28.0 g (95% yield), of yellow powder, m.p. 53°-58° C
  12. customRecrystallization once from methanol
  13. customgave colorless long needle crystals, m.p. 71°-72° C

Sources & evidence

ORD record
ord-c8995d63e5b54445bc4237ddadc14f6a
Source dataset
uspto-grants-1978_11
Patent number
US04125534

Reaction notes

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