<b>Nucleophilic Displacement Reactions of Polyhalogenated Cyclopentadienes and Cyclopentenes. I</b>

McBee, E. T.; Crain, D. L.; Crain, Ronald Dee; Belohlav, L.; Braendlin, H. P.

doi:10.1021/ja00877a028

Cited by 30 publications

(6 citation statements)

References 1 publication

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“…The reactivity of the allylic chlorine atoms in hexachloroc~~clopentacliene and the ease of their displacement by nucleophiles had been previously denlonstrated b) other worliers (1,2). Recently, JIcBee and co-wor1;ers (3) de~nonstrated this type of reaction with secollclary amines.…”

Section: Condensation O F Hexachlorocyclopentadiene With Dieti-ianolamentioning

confidence: 97%

Condensation of Hexachlorocyclopentadiene With Diethanolamine

Kamal¹,

Wicklatz²

1964

Can. J. Chem.

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Recently, Franzus and Hudson (3), and Russell and co-workers (4) reported an extensive study of 1,3-dibroinocyclohexanes and 1,3-and 1,4-dichlorocyclohexanes. Acidic treatment, with either hydrobromic acid or hydrochloric acid of 1,4-(or 1,3-) cyclohexanediols yielded cis-trans mixtures of dihalogen-substituted cyclohexanes.The bulk of our product (FI), when isolated and recrystallized from ethanol, melts a t 102-103", in agreement with trans-l,4-dichlorocyclohexane prepared by Russell and co-workers by a similar procedure. Proton magnetic resonance spectra show a peak a t T = 5.9 (Russell et al. T = 5.82), due to the methine protons in 1,4-dichlorocyclohexane, the C-1 and C-4 protons being predominantly diaxial. Proton magnetic resonance spectra of F 4 showed presence of trans-1,4-dichlorocyclohexane (T = 5.9) and a pealc a t T = 5.67, consistent with the signal due to methine protons of trans-1,3-dichlorocyclohexane (4). The reaction between 1,4-cyclohexanediol and hydrochloric acid uTas then followed up in the manner described below.A series of Carius tubes each containing 0.98 moles of the diol and 4.1 moles of hydrochloric acid were sealed and heated a t 80-90'. At regular intervals one tube was cooled, and the reaction nlixture worked up as described a t the beginning of the note. The isolated products were then analyzed by n.1n.r. (30y0 carbon tetrachloride solution, int. TJIS). In addition to unreacted material, 4-cl~lorocyclohexanol, 1,4-dichloroc~~clol~exane, peaks a t T = 4.45 and T = 2.9 appeared. The T = 4.45 pealc is consistent with formation of l,4-cyclohexadiene and the T = 2.9 peal; is consistent with formation of aromatic byproducts. Presence of 1,3-dichlorocyclohexane in our F4 fraction can thus be explained as due to the random addition of hydrochloric acid across the double bonds in 1,4-cyclohexadiene.1. L. I\T. O\\.ES and P. .-I. Ronlxs.

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Section: Condensation O F Hexachlorocyclopentadiene With Dieti-ianolamentioning

confidence: 97%

Condensation of Hexachlorocyclopentadiene With Diethanolamine

Kamal¹,

Wicklatz²

1964

Can. J. Chem.

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“…It is suspected that it is the extremely reactive diether (3), which is seldom isolated under basic conditions due to the vinylic fluorine (6). However, a 3-phenoxide (4) derivative, resulting from an outward elimination (7) could conceivably be formed, because of a competitive reaction path between the electronically favored inward elimination (1) us.…”

Section: Stockel: 12-dichlorohexafluorocyclopentenementioning

confidence: 99%

“…However, the latter route is very much less influential in the cyclopentene system than in the cyclohexene system. The diether structure is also preferred because its retention time on the g. gives comparable bands as fgr 1 with bands at 6.02 (C==C stretch), 6.28 (phenyl), 7.88,8.38, and 8.80 p (for CF, and C-0-C).…”

Section: Stockel: 12-dichlorohexafluorocyclopentenementioning

confidence: 99%

Reaction of 1,2-Dichlorohexafluorocyclopentene with Phenol and p-Nitrothiophenol

Stockel¹

1975

Can. J. Chem.

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The reaction of phenol with 1,2-dichlorohexafluorocyclopentene gave two major components. These have been identified as 1-chloro-2-phenoxy-3,3,4,4,5,5-hexafluorocyclopentene (1) and l-chloro-3,3,4,4-tetrafluoro-2,5,5triphenoxycyclopentene (2). A third component was detected by g.c. and assumed to be 3.Withp-nitrothiophenol as the reactant only 1,2-bis(p-nitrophenylthio)-3,3,4,4,5,5-hexafluorocyclopentene (4) was isolated in excellent yields.

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“…The fluid characteristics of these two types of ethers are compared, including the effects of ring size.IN UCLEOPHILIC displacement of halogens in alicydic perhalo-olefins by alkoxide ions yields two types of ethers, depending upon the nature of the vinylic halogen in the olefin. Most of the reported work (6,7,8,10,11,12,14,15) relates to the reactions of the perhalocyclobutene…”

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confidence: 99%

Polyfluoroalkyl ethers of alicyclic fluoroolefins

Gash¹

1969

J. Chem. Eng. Data

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The base-catalyzed addition of polyfluoroalkanols to perhalo-alicydic olefins yields stable polyfluoroalicydic ethers. Two series of diand triethers are obtained, depending on the identity of the vinylic halogens in the four-, five-, and six-membered ring alicydic olefins. Evidence is cited for the presence of double bond isomers only in the fiveand six-membered ring diethers. All of the diethers (but not the triethers) readily undergo chlorine addition to yield stable a-chloroethers. The fluid characteristics of these two types of ethers are compared, including the effects of ring size.IN UCLEOPHILIC displacement of halogens in alicydic perhalo-olefins by alkoxide ions yields two types of ethers, depending upon the nature of the vinylic halogen in the olefin. Most of the reported work (6,7,8,10,11,12,14,15) relates to the reactions of the perhalocyclobutene

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Nucleophilic Displacement Reactions of Polyhalogenated Cyclopentadienes and Cyclopentenes. I

Cited by 30 publications

References 1 publication

Condensation of Hexachlorocyclopentadiene With Diethanolamine

Condensation of Hexachlorocyclopentadiene With Diethanolamine

Reaction of 1,2-Dichlorohexafluorocyclopentene with Phenol and p-Nitrothiophenol

Polyfluoroalkyl ethers of alicyclic fluoroolefins

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