Hydrochloric Acid → HCID 54508553, compound

HRID 265209Notes

Reaction equation

HRID 265209 reaction equation
[F:1][C:2]1[C:9]([O:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH3:18])=[CH:8][CH:7]=[CH:6][C:3]=1[CH:4]=O.[Br-].[F:20][C:21]1[C:46]([O:47][CH2:48][CH2:49][CH2:50][CH2:51][CH2:52][CH2:53][CH2:54][CH3:55])=[CH:45][CH:44]=[CH:43][C:22]=1[CH2:23][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[H-].[H-].[H-].[H-].[Li+].[Al+3].FC(O)C1C=CC=C(OCCCCCCCC)C=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.BrBr.FC1C(OCCCCCCCC)=CC=CC=1CBr.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CC(C)([O-])C.[K+].Cl>C1COCC1.C1(C)C=CC=CC=1.O>[F:1][C:2]1[C:9]([O:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH3:18])=[CH:8][CH:7]=[CH:6][C:3]=1[CH:4]=[CH:23][C:22]1[CH:43]=[CH:44][CH:45]=[C:46]([O:47][CH2:48][CH2:49][CH2:50][CH2:51][CH2:52][CH2:53][CH2:54][CH3:55])[C:21]=1[F:20]

Participants

13

Reactant 9

HCID 313Hydrochloric AcidHCID 11776TriphenylphosphineHCID 15219970HCID 15219970, compound2×HCID 190337812-Fluoro-3-octyloxybenzyl bromideHCID 19033783HCID 19033783, compoundHCID 21226445Aluminium lithium hydrideHCID 23665647Potassium tert-butoxideHCID 44191054Bromine triphenylphosphineHCID 54042522HCID 54042522, compound

Product 1

HCID 54508553HCID 54508553, compound

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 1140TolueneSolventHCID 8028TetrahydrofuranSolvent3×

Procedure

A solution of 2.5 g of 2-fluoro-3-octyloxybenzaldehyde (prepared by reacting 2-octyloxyfluorobenzene with lithium diisopropylamide followed by reaction with N,N-dimethylformamide) in 50 ml of THF is added dropwise at 20° C. to a fully reacted mixture of 5.6 g of 2-fluoro-3-octyloxybenzyltriphenylphosphoniumbromide (prepared by the reaction sequence: reaction of 2-fluoro-3-octyloxybenzaldehyde with LiAlH4 in THF to give fluoro-3-octyloxybenzyl alcohol, reaction of the latter with triphenylphosphine/Br2 to give 2-fluoro-3-octyloxybenzyl bromide and reaction of the latter with triphenylphosphine in toluene) and 1.2 g of potassium tert-butoxide in 100 ml of THF. When the reaction is complete, the mixture is adjusted to pH 5 using HCl, 500 ml of H2O are added, and the mixture is extracted three times with 100 ml of diethyl ether in each case. Chromatography on silica gel using dichloromethane/heptane 1:1 gives 1,2-bis(2-fluoro-3-octyloxyphenyl)ethene as an E/Z-mixture. The latter is dissolved in cyclohexane, 4 mol % of iodine are added, and the mixture is exposed to UV light for 8 hours at 25° C. in a quartz apparatus. Chromatography on SiO2 using dichloromethane and recrystallization from acetonitrile give 1.2 g of 1,8-difluoro-2,7-dioctyloxyphenanthrene as colorless crystals.

Workup

  1. customprepared by the reaction sequence
  2. customto give
  3. customto give
  4. additionare added
  5. extractionthe mixture is extracted three times with 100 ml of diethyl ether in each case

Sources & evidence

ORD record
ord-9c2dc07ff3df4f9e9d427809f42eff4f
Source dataset
uspto-grants-1997_07
Patent number
US05648021

Reaction notes

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