Reaction of 1,1,2-trifluoro-2-hexafluoro-2′-(heptafluoropropoxy)-propoxyethylene with amines or alcohols

Fürin, G. G.; Pressman, Luiza S; Pokrovsky, L. M.; Krysin, A. P.; Chi, Ki‐Whan

doi:10.1016/s0022-1139(00)00290-6

Cited by 20 publications

(7 citation statements)

References 12 publications

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“…Also, the 13 C NMR spectra revealed a coupling between the carbon and the fluorine at the C2 position, characterized by J values of between 233.1 and 234.2 Hz ( 13 C NMR, CDCl 3 ). These results are in good accordance with 13 C NMR data (CDCl 3 ) reported in the literature for compounds bearing similar structural subunits 22b. 23…”

Section: Resultssupporting

confidence: 92%

Synthesis of 2‐Hydroxy‐1,4‐oxazin‐3‐ones through Ring Transformation of 3‐Hydroxy‐4‐(1,2‐dihydroxyethyl)‐β‐lactams and a Study of Their Reactivity

Piens

Mollet

Goossens

et al. 2013

Chemistry A European J

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The reactivity of 3-hydroxy-4-(1,2-dihydroxyethyl)-β-lactams with regard to the oxidant sodium periodate was evaluated, unexpectedly resulting in the exclusive formation of new 2-hydroxy-1,4-oxazin-3-ones through a C3C4 bond cleavage of the intermediate 4-formyl-3-hydroxy-β-lactams followed by a ring expansion. This peculiar transformation stands in sharp contrast with the known NaIO(4)-mediated oxidation of 3-alkoxy- and 3-phenoxy-4-(1,2-dihydroxyethyl)-β-lactams, which exclusively leads to the corresponding 4-formyl-β-lactams without a subsequent ring enlargement. In addition, this new class of functionalized oxazin-3-ones was further evaluated for its potential use as building blocks in the synthesis of a variety of differently substituted oxazin-3-ones, morpholin-3-ones and pyrazinones. Furthermore, additional insights into the mechanism and the factors governing this new ring-expansion reaction were provided by means of density functional theory calculations.

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Section: Resultssupporting

confidence: 92%

Synthesis of 2‐Hydroxy‐1,4‐oxazin‐3‐ones through Ring Transformation of 3‐Hydroxy‐4‐(1,2‐dihydroxyethyl)‐β‐lactams and a Study of Their Reactivity

Piens

Mollet

Goossens

et al. 2013

Chemistry A European J

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“…The combined organic layers were washed with water (2 50 mL), dried over MgSO 4 , filtered over a pad of silica gel, and concentrated under vacuum affording the product mixture (Z)/(E)-3 as an oily yellow solid (484 mg, 75%). 1 H NMR (300 MHz, CDCl 3 ) d 7.51-7.43 (m), 7.02 (d, J = 8.9 Hz), 6.95 (d, J = 8.9); 19 F NMR (283 MHz, CDCl 3 ) d -121.7 (s, (Z)-CF CF, 2F), -127.8 (s, (E)-CF CF, 2F); GC-EIMS (70 eV) m/z (% relative intensity) (Z)-3: 408, 406, 404 (M + , 10, 19, 11), 235, 233 (25,26), 207, 205 (19,19), 185, 183 (17,17), 157, 155 (86, 91), 76, (89), 75 (89), 74 (24), 50 (100); (E)-3: 408, 406, 404 (M + , 10, 18, 9), 235, 233 (25,23), 207, 205 (18,20), 185, 183 (17,16), 176, 175 (9,11), 157, 155 (82, 85), 76 (85), 75 (88), 50 (100).…”

Section: (Z)-and (E)-12-bis(4-bromophenoxy)-12-difluoroethene ((Z)/(e...mentioning

confidence: 99%

Synthesis of internal fluorinated alkenes via facile aryloxylation of substituted phenols with aryl trifluorovinyl ethers

et al. 2011

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Nucleophilic addition-elimination of ortho- or para-substituted phenols to aryl trifluorovinyl ethers (TFVEs) in N,N-dimethylformamide was studied. Using sodium hydride as a base afforded vinyl substitution products R-Ar-O-CF=CF-O-Ar-R', where R or R' = H, Br, OMe, tert-Bu, or Ph. The vinyl substitution products produced mixtures of (Z)/(E)-isomers and this isomer ratio was influenced by substitution with more sterically encumbered phenol nucleophiles. Reactions using caesium carbonate afforded addition products R-Ar-O-CHFCF(2)-O-Ar-R' whereas upon dehydrofluorination using sodium hydride produced vinyl substitution products. The preparation of vinyl substituted and addition products proceeded in overall good isolated yields and were elucidated using (1)H and (19)F NMR, GC-MS, and X-ray analysis. Vinyl substituted products were inert to UV light and chemical reactivity using common polymerization promoters. Thermal activation of the (Z)/(E)-fluoroolefin (-CF=CF-) was observed at an onset of 310 °C in nitrogen using differential scanning calorimetry (DSC) producing insoluble network material. The synthesis, characterization, and mechanism for stereoselectivity are discussed.

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“…Subsequent column chromatographic separation removed unreacted decafluorobiphenyl and the disubstituted compound to give the monosubstituted compound 3 in 31% yield. The precursors 6c and 6d , on the other hand, required a two-step synthesis; the first stage was a monosubstitution reaction of 1 with 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-heptadecafluoro-12-iodododecane ( 4 ) , or perfluoro(5-methyl-3,6-dioxanon-1-ene) ( 5 ) in the presence of K 2 CO 3 as a base. The reaction between 1 and 4 was a nucleophilic substitution reaction, while the reaction of 1 and 5 was an addition reaction , of OH groups to the trifluorovinyl ether moiety in 5 .…”

Section: Resultsmentioning

confidence: 99%

Cross-Linkable Molecular Glasses: Low Dielectric Constant Materials Patternable in Hydrofluoroethers

Murotani

Lee

Chatzichristidi

et al. 2009

ACS Appl. Mater. Interfaces

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We report a new approach to solution-processable low-dielectric-constant (low-k) materials including photolithographic patterning of these materials in chemically benign and environmentally friendly solvents. A series of semiperfluorinated molecular glasses with styrenic substituents were successfully synthesized. These small molecular materials were thermally stable up to 400 °C and also exhibited an amorphous nature, which is essential to forming uniform films. Differential scanning calorimetry studies revealed that a cross-linking reaction occurred in the presence of acid, resulting in the formation of robust polymeric films. Atomic force microscopy images of the cross-linked films showed uniform and pinhole-free surface properties. Dielectric constants determined by a capacitance measurement were 2.6-2.8 (100 kHz) at ambient conditions, which are comparable to other polymeric low-k materials. The incorporation of semiperfluorinated substituents was effective in decreasing the dielectric constant; in particular, the fluorinated alkyl ether structure proved best. In addition, the fluorinated substituents contributed to good solubility in hydrofluoroether (HFE) solvents, which enabled the successful photolithographic patterning of those materials in HFEs down to a submicrometer scale.

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Reaction of 1,1,2-trifluoro-2-hexafluoro-2′-(heptafluoropropoxy)-propoxyethylene with amines or alcohols

Cited by 20 publications

References 12 publications

Synthesis of 2‐Hydroxy‐1,4‐oxazin‐3‐ones through Ring Transformation of 3‐Hydroxy‐4‐(1,2‐dihydroxyethyl)‐β‐lactams and a Study of Their Reactivity

Synthesis of 2‐Hydroxy‐1,4‐oxazin‐3‐ones through Ring Transformation of 3‐Hydroxy‐4‐(1,2‐dihydroxyethyl)‐β‐lactams and a Study of Their Reactivity

Synthesis of internal fluorinated alkenes via facile aryloxylation of substituted phenols with aryl trifluorovinyl ethers

Cross-Linkable Molecular Glasses: Low Dielectric Constant Materials Patternable in Hydrofluoroethers

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