Hydrochloric Acid → 8-Triphenylmethoxy-1-octyne

HRID 1605785Notes

Reaction equation

HRID 1605785 reaction equation
Cl[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][O:8][C:9]([C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1)([C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1)[C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1.Cl[CH2:29][CH2:30]CCCCO.C1(C(Cl)(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Li].Cl>O.CCOCC.CS(C)=O>[C:10]1([C:9]([C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=2)([C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=2)[O:8][CH2:7][CH2:6][CH2:5][CH2:4][CH2:3][CH2:2][C:29]#[CH:30])[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1

Participants

9

Reactant 5

HCID 313Hydrochloric AcidHCID 6456Trityl chlorideHCID 748286-Chloro-1-hexanolHCID 3028194LithiumHCID 11955063Benzene, 1,1',1''-[[(6-chlorohexyl)oxy]methylidyne]tris-

Product 1

HCID 203810448-Triphenylmethoxy-1-octyne

Reagents, catalysts & solvents 3

HCID 679Dimethyl SulfoxideSolvent2×HCID 962WaterSolvent2×HCID 3283Diethyl EtherSolvent

Conditions

Temperature
25 °C

Procedure

To a stirred suspension of 68.1 g. (0.18 moles) of 1-chloro-6-triphenylmethoxyhexane, prepared from 1-chloro-6-hydroxyhexane and triphenylmethyl chloride in the manner of Example 277, in 60 ml. of dimethylsulfoxide is added a solution of 19.9 g. (0.216 moles) of lithium acetylideethylenediamine complex in 120 ml. of dimethylsulfoxide during 20 minutes. The temperature is maintained at 25°C. with an ice bath during the addition, after which the mixture is stirred at ambient temperature for 3.5 hours and then at 30°C. for 15 minutes. The mixture is diluted with 100 ml. of ether and treated dropwise with 150 ml. of water with ice bath cooling. The mixture is diluted with 400 ml. of water and 250 ml. of 2:1 ether-pet ether and acidified with 120 ml. of 4N hydrochloric acid in the ice bath. The phases are separated, and the aqueous phase is extracted with 3:1 ether-pet ether. The combined extracts are washed successively with water and saturated sodium chloride solution, dried over magnesium sulfate, and concentrated. Column chromatography of the residue on Florisil affords the subject compound as white crystals, m.p. 43°-45°C. after recrystallization from pet-ether, ν max 3300 (acetylenic hydrogen), 2360 (triple bond), 1600, 1068, and 706 cm-1 (triphenylmethoxy group).

Workup

  1. additionTo a stirred suspension of 68.1 g
  2. waitat 30°C. for 15 minutes
  3. additionThe mixture is diluted with 100 ml
  4. additionThe mixture is diluted with 400 ml
  5. customThe phases are separated
  6. extractionthe aqueous phase is extracted with 3:1 ether-pet ether
  7. washThe combined extracts are washed successively with water and saturated sodium chloride solution
  8. dry with materialdried over magnesium sulfate
  9. concentrationconcentrated

Sources & evidence

ORD record
ord-a5b367a7788f45cfbed84740202943cb
Source dataset
uspto-grants-1976_04
Patent number
US03950406

Reaction notes

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