p-Toluenesulfonic acid → Pentanoic acid, 5-(triphenylphosphoranylidene)-

HRID 371800Notes

Reaction equation

HRID 371800 reaction equation
O1C=CCCC1.O1C=CCC1.C(OCC)=C.C1(C)C=CC(S(O)(=O)=O)=CC=1.[H-].C([Al+]CC(C)C)C(C)C.[H-].[Na+].[Br-].[C:41]([CH2:44][CH2:45][CH2:46][CH2:47][P+:48]([C:61]1[CH:66]=[CH:65][CH:64]=[CH:63][CH:62]=1)([C:55]1[CH:60]=[CH:59][CH:58]=[CH:57][CH:56]=1)[C:49]1[CH:54]=[CH:53][CH:52]=[CH:51][CH:50]=1)([OH:43])=[O:42]>C1(C)C=CC=CC=1.CS(C)=O.C(Cl)Cl>[C:41]([CH2:44][CH2:45][CH2:46][CH:47]=[P:48]([C:61]1[CH:66]=[CH:65][CH:64]=[CH:63][CH:62]=1)([C:49]1[CH:50]=[CH:51][CH:52]=[CH:53][CH:54]=1)[C:55]1[CH:60]=[CH:59][CH:58]=[CH:57][CH:56]=1)([OH:43])=[O:42]

Participants

11

Reactant 7

HCID 6101p-Toluenesulfonic acidHCID 8023Ethyl vinyl etherHCID 80803,4-dihydro-2H-pyranHCID 24758Sodium hydrideHCID 709342,3-DihydrofuranHCID 161236(4-Carboxybutyl)triphenylphosphonium bromideHCID 21225700Diisobutylaluminumhydride

Product 1

HCID 10882972Pentanoic acid, 5-(triphenylphosphoranylidene)-

Reagents, catalysts & solvents 3

HCID 679Dimethyl SulfoxideSolventHCID 1140TolueneSolventHCID 6344DichloromethaneSolvent

Procedure

Compounds of formula XX may be prepared by hydrolysis under alkaline conditions of compounds of formula XIX. Compounds of formula XXI may be obtained by the acetylation of compounds of formula XX under mild conditions and may be converted into compounds of formula XXII by reaction with a dihydropyran, dihydrofuran or ethyl vinyl ether in an inert solvent, e.g. methylene chloride, in the presence of a condensing agent, e.g. p-toluenesulphonic acid. Compounds of formula XXIII may be prepared by reducing compounds of formula XXII with diisobutylaluminium hydride in toluene for about 15 minutes at -60° C. Dimsyl anion, previously prepared from sodium hydride and dimethyl sulphoxide, is reacted with (4-carboxybutyl)triphenylphosphonium bromide to form (4-carboxybutylidene)triphenylphosphorane. To that compound is added a compound of formula XXIII and the mixture in dimethyl sulphoxide is made to react for 2 hours at room temperature to yield a compound of formula XVA.

Workup

  1. customfor about 15 minutes
  2. customat -60° C

Sources & evidence

ORD record
ord-53a1f769b2bc4003aaa135c08bdc3ae0
Source dataset
uspto-grants-1978_05
Patent number
US04087620

Reaction notes

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