Reactions of Polyfluoro Olefins. III.<sup>1</sup> Preparation of Polyfluoro Ethers<sup>2</sup>

Barr, John T.; Rapp, Karl E.; Pruett, Roy L.; Bahner, Carl Tabb; Gibson, J. Donald; Lafferty, R.H.

doi:10.1021/ja01166a041

Cited by 24 publications

(9 citation statements)

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“…The origin of this decline may be traced to the dominant role played by the Hückel 4n + 2 rule and its experimental "verifications" for n jA l.8 Recent cyclopropenium ion (2) and cyclopropenone (3)9'10 studies have focused on the stabilization of the "aromatic" but highly strained 2tr3C ring system by appropriate electron-donating substituents, particularly heteroatoms.11"14 In a search for alternative substituents which are capable of delocalizing the positive charge of the three-membered ring, we have considered the azulenyl group. The rationale underlying this approach is based on the extra "aromatic" stabilization of 1-azulenylcarbenium ion (4), a variation of the tropylium ion theme.9-15 1-Azulenylcyclopropenium ion (5) may formally be considered as a triapentafulvalene system condensed to tropylium ion (5a). We report straightforward syntheses and various properties of cyclopropenium ion and cyclopropenone totally substituted by guaiazulenyl groups: tri-3-guaiazulenylcyclopropenium perchlorate (6) and di-3-guaiazulenylcyclopropenone (7).…”

Section: Methodsmentioning

confidence: 99%

Fluorinated cyclopropenyl methyl ethers. New stable cyclopropenium cations

Smart¹

1976

J. Org. Chem.

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The first fluorinated cyclopropenyl ethers, 1 -methoxytrifluorocyclopropene, l-methoxy-2-chlorodifluorocyclopropene, and 1,2-dimethoxydifluorocyclopropene, have been synthesized. These ethers are exceedingly reactive and much less stable than homologous polyfluorocycloalkenyl ethers, but they react with antimony pentafluoride to give unusually stable cyclopropenium hexafluoroantimonate salts.The reaction of nucleophiles, especially alkoxides, with perfluoroalkenes and perfluorocycloalkenes (having four, five, and six carbons) has received considerable mechanistic and synthetic attention.1•2 However, similar studies on polyfluorocyclopropenes generally have been limited and often unsuccessful. West and co-workers3 described the synthesis of various fluorinated cyclopropenes where polyhalocyclopropenes were treated with fluoride ion. Sargeant and Krespan4 reported that perfluorocyclopropene reacted, often uncontrollably, with amines to give extensive degradation products. Polyfluorocyclopropenes are reported here to react with methoxide ion to give the first examples of polyfluorocyclopropenyl ethers.

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Section: Methodsmentioning

confidence: 99%

Fluorinated cyclopropenyl methyl ethers. New stable cyclopropenium cations

Smart¹

1976

J. Org. Chem.

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“…Later papers5,6 explained displacements of vinylic halogens by alkoxides in both cyclic and acyclic systems in terms of carbanion intermediates. This interpretation was disputed by Rapp,et al,7,8 who proposed instead an addition-elimination mechanism.…”

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confidence: 99%

“…Hence, the order of leaving groups for carbanions is I > Br > Cl > F > OR > H. (7) Fluorine will not be lost from a gem-difluoro group if there is another 3-halogen which can leave. (8) If a choice must be made between two equivalent leaving moieties, loss will occur so as to give the more stable olefin.…”

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confidence: 99%

Nucleophilic Substitution in Halogenated Cyclobutenes¹

Park¹,

Lacher²,

Dick³

1966

J. Org. Chem.

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“…As me ntio ned before, it had bee n fo und diffic ult to e ffec t the successful cleavage of the e thoxy e ther of he ptaAu oro-p-cresol by c he mical means [141 Howe ve r , the relative in s ta bility of other t-butyl e the rs to both heat a nd acid [16][17][18] s uggested that the tbutyl e ther of hepta flu oro-p -cresol might poss ibl y undergo fac ile clea vage to th e desired c resol. Ind eed , it was fo und th a t by eith er liquid ph ase or vapor pyrol ys is the e ther undergoes clea vage to give heptaflu oro-pcresol a nd iso but ylene.…”

Section: Synthesis Of 2356-tetrafluoro-4-trifluoromethylphenol (Hementioning

confidence: 99%

Synthesis of poly-p-oxyperfluorobenzylene and related polymers. A novel synthesis of the monomer 2,3,5,6-tetrafluoro-4-trifluoromethylphenol

Antonucci¹,

Wall²

1967

J. RES. NATL. BUR. STAN. SECT. A.

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The sy nth esis and polymerization of 2,3,5,6-tetraAuoro-4-triA uoromethylphenol (he ptaAuoro-pcres ol) is desc ribed. Th e polymer , po ly-p-oxype rAu orobenzyle ne (polyperAuoro-p-benzy le ne oxide), is probab ly formed thro ugh the perAuoro -p-quinon e me th id e inte rm e di ate obtaine d by the intramol ec ular loss of e ithe r hydroge n Au oride or a me tal Au orid e. Th e polymer has a s tru c ture a nal ogo us to th at reported for the polymer d erive d from p-triAuoro me thy lphe no l und e r s imil ar co nditi ons.[n th e co urse of th e syn th es is of th e monom er, he ptafluoro-p-c reso l, a novel s yntheti c me thod was dis co vered. Th e sy nthes is cons ists in the prior preparation of I -t-but oxy-2,3,5,6-tetrafluoro -4-triAu orom e thylbenze ne and its s ubsequ e nt th ermal d eco mposition into th e isobutyl ene and the des ire d cresol. S imil arly, N-t-butyl-2,3,5,6-tet raAuoro-4-triAu orome th ylaniline und ergoes a s imil ar liquid phase pyrolys is into isobutyle ne and 2,3,5,6-tetraAuoro-4-triAu oromet hylaniline. However, during the course of thi s pyrolys is, prac ti ca ll y a ll of the ani line undergoes po lymerization with the concomitant los s of hydrogen Au orid e. T he polymer is form e d by th e same mec hani s m operative in the thermal po lymerization of p-heptafluorocresol exce pt th a t additional quantiti es of hydrogen Auoride ca n be elimin ated from th e -NHCF, -segme nts of the polymer c hain the re by introd uc ing -N = CF -units into the polymer bac kbone .Other t-b utyl derivatives were sy nthes ized and th e ir thermal deco mposition studied. Several poss ibl e mec hani s ms for the deco mpos ition of these t-butyl co mpo und s a re considered _ Key Words: I -t-Butoxy-2,3,5,6-te traAu oro-4-triAuorom e th ylbe nzen e , perAuoro-p-quinon e met hid e, po lyme rization, poly-p-oxyperAuorobenzy le ne, pyrolysis, 2,3,5,6-tetrafluoro-4-triAu orome thylph enol.

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Reactions of Polyfluoro Olefins. III.¹ Preparation of Polyfluoro Ethers²

Cited by 24 publications

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Fluorinated cyclopropenyl methyl ethers. New stable cyclopropenium cations

Fluorinated cyclopropenyl methyl ethers. New stable cyclopropenium cations

Nucleophilic Substitution in Halogenated Cyclobutenes¹

Synthesis of poly-p-oxyperfluorobenzylene and related polymers. A novel synthesis of the monomer 2,3,5,6-tetrafluoro-4-trifluoromethylphenol

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Reactions of Polyfluoro Olefins. III.1 Preparation of Polyfluoro Ethers2

Cited by 24 publications

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Fluorinated cyclopropenyl methyl ethers. New stable cyclopropenium cations

Fluorinated cyclopropenyl methyl ethers. New stable cyclopropenium cations

Nucleophilic Substitution in Halogenated Cyclobutenes1

Synthesis of poly-p-oxyperfluorobenzylene and related polymers. A novel synthesis of the monomer 2,3,5,6-tetrafluoro-4-trifluoromethylphenol

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Reactions of Polyfluoro Olefins. III.¹ Preparation of Polyfluoro Ethers²

Nucleophilic Substitution in Halogenated Cyclobutenes¹