Water → HCID 178445833, compound

HRID 370677Notes

Reaction equation

HRID 370677 reaction equation
Br[C:2](Br)=[CH:3][C:4]1[CH:9]=[CH:8][C:7]([C@H:10]2[O:15][CH2:14][C@H:13]([CH2:16][CH2:17][CH2:18][CH3:19])[CH2:12][O:11]2)=[CH:6][CH:5]=1.C([Li])CCC.C1(O[C:33]#[N:34])C=CC=CC=1.O>O1CCCC1.CCCCCC>[CH2:16]([C@@H:13]1[CH2:14][O:15][C@@H:10]([C:7]2[CH:8]=[CH:9][C:4]([C:3]#[C:2][C:33]#[N:34])=[CH:5][CH:6]=2)[O:11][CH2:12]1)[CH2:17][CH2:18][CH3:19]

Participants

7

Reactant 4

HCID 962WaterHCID 70740Phenyl cyanateHCID 178418339ButyllithiumHCID 178445832HCID 178445832, compound

Product 1

HCID 178445833HCID 178445833, compoundYield 50%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent

Conditions

Temperature
-78 °C

Procedure

A solution of 3.5 g of trans-2-[p-(2,2-dibromovinyl)phenyl]-5-butyl-1,3-dioxane in 80 ml of absolute tetrahydrofuran was placed at -78° C. in a sulphonation flask under argon gasification and treated within 5 minutes with 13.4 ml of a 1.2N solution of butyl lithium in hexane. After completion of the addition, the mixture was held at -10° C. for 1 hour, then again cooled to -78° C. and treated with 1.2 ml of phenyl cyanate within 5 minutes. The mixture was stirred at -78° C. for a further 30 minutes, then poured into 100 ml of water and extracted three times with 100 ml of diethyl ether each time. The organic phases were washed with 100 ml of water and 100 ml of saturated sodium chloride solution, dried over potassium carbonate and concentrated. Low-pressure chromatography (0.5 bar) of the residue (3.26 g) on silica gel with petroleum ether/ethyl acetate/triethylamine (97:3:0.2) gave 1.18 g (50%) of p-(trans-5-butyl-1,3-dioxan-2-yl)phenylpropiolonitrile (purity 98.7%). A recrystallization from 50 ml of hexane yielded 1.03 g of the nitrile as colourless crystals (purity 99.7%); m.p. (C-N) 54.3° C., cl.p. (N-I) 108.7° C.

Workup

  1. additionAfter completion of the addition
  2. extractionextracted three times with 100 ml of diethyl ether each time
  3. washThe organic phases were washed with 100 ml of water and 100 ml of saturated sodium chloride solution
  4. dry with materialdried over potassium carbonate
  5. concentrationconcentrated

Sources & evidence

ORD record
ord-07a021422f794c6b9eabe695ad0dbd42
Source dataset
uspto-grants-1985_07
Patent number
US04528114

Reaction notes

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