Synthesis and Properties of Fluorinated Ethers with Fluorobenzene Rings

Chen, Jianguo; Kirchmeier, Robert L.; Shreeve, Jean’ne M.

doi:10.1021/ic950962k

Cited by 4 publications

(5 citation statements)

References 18 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Quantities of volatile materials were determined by PVT measurements assuming ideal gas behavior. A Bruker 300 MHz AMX nuclear magnetic resonance spectrometer was used to record 1 H, 13 C, and 19 F NMR spectra at 300.1, 282.4, and 75. F nuclei].…”

Section: Methodsmentioning

confidence: 99%

“…Among these methods, nucleophilic substitution of fluoroalkenes, which involves addition followed by b-elimination in the presence of a base, is a well-established strategy. Substitutions of fluoroaromatic, [13] fluoroheterocyclic, [14] fluoroalkene, [2][3][4][5][6][7][8][9][10]12] and, more recently, fluorinated fullerenes [15] are being used to carefully design compounds with desired physical and chemical properties. This enables their use in diverse applications, [4,16] such as blood substitutes, agrochemicals, electric insulators, liquid-crystalline materials, conducting polymers, the construction of super hydrophobic surfaces, and so forth.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Azoles as Reactive Nucleophiles with Cyclic Perfluoroalkenes

Garg

Twamley

Zhang

et al. 2009

Chemistry A European J

View full text Add to dashboard Cite

Di- and multiazole-substituted fluorocyclic products (2-13) were readily synthesized in good to high yields. These were synthesized by nucleophilic substitution reactions of perfluorocycloalkenes with azoles (i.e., imidazole, triazole) involving simple reaction procedures. Interestingly, these azoles were later found to be reactive not only with the vinylic, but also with the allylic fluorine atoms. This resulted in the substitution of up to six azoles on the fluorinated rings. Stoichiometry plays a key role in determining the degree of substitution. For comparison, the analogous reactions of N-substituted 1-(trimethylsilyl)-imidazole and 1-(trimethylsilyl)-1,2,4-triazole were also investigated. All of the new compounds were fully characterized by elemental, spectral ((19)F, (1)H, (13)C NMR), and thermal differential scanning calorimetry (DSC) analyses.

show abstract

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Azoles as Reactive Nucleophiles with Cyclic Perfluoroalkenes

Garg

Twamley

Zhang

et al. 2009

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…The utilization of silyl ethers (siloxanes) as transfer agents provides a powerful preparative pathway for the synthesis of new or heretofore difficultly accessible per- and polyfluorinated compounds. − These transfer reactions that ordinarily occur under relatively mild conditions, compared to those required when the analogous metalated compounds (alkoxy or aryloxy) are employed, are catalyzed by the presence of fluoride ion.…”

Section: Introductionmentioning

confidence: 99%

“…We and others used this methodology to explore the reactivity of mono- and disiloxy per- and polyfluorinated derivatives with a large number of halogenated compounds in order to prepare a variety of new perfluoro and polyfluoro ethers. − Also studied was the behavior of perfluorinated aromatic siloxanes, e.g. , C 6 F 5 OSiMe 3 , 3,6,7,9,10 1,4-(Me 3 SiO) 2 C 6 F 4 , 1,4-[Me 3 SiOC(CF 3 ) 2 ] 2 C 6 F 4 , toward a range of electrophiles.…”

Section: Introductionmentioning

confidence: 99%

Studies on the Reactivity of Tetrafluoro- and Pentafluorophenyl Trimethylsilyl Ether with Pentafluorobenzenes. Chemistry and X-ray Structural Investigations of Polyfluorodiphenyl Ethers

et al. 1997

Self Cite

View full text Add to dashboard Cite

The introduction of tetrafluoro- and pentafluorophenoxy moieties into a variety of pentafluorobenzenes C6F5R (R = CF3, CN, NO2) is accomplished by employing the trimethylsilyl ethers (siloxanes) 4-HC6F4OSiMe3 (1) and C6F5OSiMe3 (2) as transfer agents. Depending on the nature of the electrophile, the stoichiometry of the reaction, and the reaction conditions, polysubstituted polyfluorodiphenyl ethers are obtained. Excess C6F5R results in the formation of the 1,4-monosubstituted benzenes (diphenyl ethers) 4-(4‘-XC6F4O)C6F4R (R = CF3, X = H (3), F (4); R = CN, X = H (5), F (6); R = NO2, X = H (9), F (10)). When R = NO2, the 1,2-substituted isomers are also detected. Additional byproducts that are isolable are the disubstituted benzenes 2,4-(4‘-XC6F4O)2C6F3R (R = CN, X = H (7), F (8); R = NO2, X = H (11), F (12)). Excess 1 or 2, when reacted with C6F5R, results in the formation of the trisubstituted benzenes 2,4,6-(4‘-XC6F4O)3C6F2R (R = CN, X = H (13), F (14); R = NO2, = H (15), F (16)). The hydrolysis of nitrile-containing diphenyl ethers (5, 6, 13, and 14) under acidic conditions results in the substituted benzoic acids 4-(4‘-XC6F4O)C6F4COOH (X = H (17), F (18)) and 2,4,6-(4‘-XC6F4O)3C6F2COOH (X = H (19), F (21)). These acids are decarboxylated to form the respective hydropolyfluoro aromatics (4-HC6F4)2O (23), 4-(C6F5O)C6F4H (24), and 2,4,6-(4‘-XC6F4O)3C6F2H (X = H (20), F (22)). In addition to acid 17, alkaline hydrolysis of 5 gives the α-hydroxy-substituted acid 4-(4‘-HC6F4O)C6F3(2-OH)COOH (25). Alkaline hydrolysis under milder conditions enables the isolation of the amide 4-(4‘-HC6F4O)C6F4CONH2 (26). The compounds 3, 4, 14 − 18, 23, and 26 have been characterized by single-crystal X-ray diffraction analysis. The presence of a hydrogen atom in 3, as well as protection of the reactive 4‘-position with a trifluoromethyl group, gives 4-(4‘-CF3C6F4O)C6F4Li (3a) on reaction with n-butyllithium. In situ reactions between 3a and ketones or acid chlorides result in novel mono- or bis(perfluorodiphenyl ether)-substituted tertiary alcohols 4-(4‘-CF3C6F4O)C6F4C(R)(R‘)OH (R/R‘ = CF3 (27), C6F5 (28), C6H5 (29), C3F7/C8F17 (30), C6F5/CH3 (31)), [4-(4‘-CF3C6F4O)C6F4]2C(R)OH (R = CF3 (32), C3F7 (33), C7F15 (34), i-C3H7 (35)). When R = i-C3H7, the major product is the ester [4-(4‘-CF3C6F4O)C6F4]2C(i-C3H7)OC(O)(i-C3H7) (36). The ketone C3F7(C8F17)CO (37) is synthesized and characterized. Reaction of 3a with hexafluoroglutaryl chloride gives [4-(4‘-CF3C6F4O)C6F4]2C(OH)(CF2)3C(O)C6F4O(4‘‘-C6F4CF3) (38), whereas with dimethyl carbonate or carbonyl fluoride, [4-(4‘-CF3C6F4O)C6F4]2CO (39) as well as small amounts of [4-(4‘-CF3C6F4O)C6F4]3COH (40) and [4-(4‘-CF3C6F4O)C6F4]3COC(O)C4H9 (41) are formed. Residual n-butyllithium cleaves the intermediate 4-(4‘-CF3C6F4O)C6F4COOCH3 to form 4-CF3C6F4C4H9 (42) and 4-HOC6F4COOCH3 (43).

show abstract

“…In previous work, we have found that fluorinated ethers containing fluorobenzene rings exhibited useful thermal properties . To further these studies fluorinated alcohols that contain fluorobenzene rings are prepared using the free radical addition technique mentioned above.…”

Section: Introductionmentioning

confidence: 99%

Insertion of Fluoroalkenes into Activated CH Bonds for the Preparation of Polyfluorinated Sulfanes, Alcohols, and Acyclic and Cyclic Ethers

1996

Self Cite

View full text Add to dashboard Cite

Free radical addition reactions of tetrahydrothiophene, pentamethylene sulfide, and 1,4-thioxane with various cyclic and acyclic per- and polyfluorinated olefins are readily initiated by di-tert-butyl peroxide, providing a convenient route for synthesizing cyclic sulfanes with fluorinated side groups. Tetrahydrothiophene reacts with hexafluoropropene, perfluoroallylbenzene, perfluorocyclobutene, and 1,2-dichlorotetrafluorocyclobutene in the presence of catalytic amounts of the peroxide to give the corresponding addition products CH(2)CH(2)CH(2)SCHCF(2)CHFCF(3) (1), CH(2)CH(2)CH(2)SCHCF(2)CHFCF(2)C(6)F(5) (2), CH(2)CH(2)CH(2)SCHCFCHFCF(2)CF(2) (3), and CH(2)CH(2)CH(2)SCHCClCHClCF(2)CF(2) (4), respectively. Pentamethylene sulfide reacts analogously with hexafluoropropene to give CH(2)CH(2)CH(2)CH(2)SCHCF(2)CHFCF(3) (8). Reaction of 1,4-thioxane with hexafluoropropene or perfluoroallylbenzene gives a mixture of two products, OCH(2)CH(2)SCH(2)CHCF(2)CHFCF(3) (9) and SCH(2)CH(2)OCH(2)CHCF(2)CHFCF(3) (10) or OCH(2)CH(2)SCH(2)CHCF(2)CHFCF(2)C(6)F(5) (11) and SCH(2)CH(2)OCH(2)CHCF(2)CHFCF(2)C(6)F(5) (12), respectively. Fluorinated alcohols C(6)F(5)CF(2)CHFCF(2)C(CH(3))(2)OH (15), C(6)F(5)CF(2)CHFCF(2)CH(CH(3))OH (16), and C(6)F(5)CF(2)CHFCF(2)CH(2)OH (17) are prepared by reacting perfluoroallylbenzene with the corresponding alcohols. When 15 is reacted with pentafluorobenzonitrile in the presence of potassium carbonate, an unexpected cyclic ether 19 is obtained as the major product in addition to C(6)F(5)CF(2)CHFCF(2)C(CH(3))(2)OC(6)F(5)CN (18). Alcohols 15-17 can be cyclized by heating with potassium carbonate to give fluorinated cyclic ethers 19-21. The X-ray crystal structures of acyclic ether 18 and cyclic ether 19 are given. Compound 18 crystallizes in the tetragonal system, space group P4(2)/n, with a = 18.471(0) Å, b = 18.471(0) Å, c = 11.702(0) Å, V = 3992.5(9) Å(3), D(calc) = 1.768 mg/m(3), Z = 8, and R = 0.0617. Compound 19 crystallizes in the triclinic system, space group P&onemacr;, with a = 8.103(3) Å, b = 8.790(3) Å, c = 9.832(3) Å, alpha = 66.25(4) degrees, beta = 72.01(3) degrees, gamma = 80.19(4) degrees, V = 608.7(4) Å(3), D(calc) = 1.845 mg/m(3), Z = 2, and R = 0.0346.

show abstract

Synthesis and Properties of Fluorinated Ethers with Fluorobenzene Rings

Cited by 4 publications

References 18 publications

Azoles as Reactive Nucleophiles with Cyclic Perfluoroalkenes

Azoles as Reactive Nucleophiles with Cyclic Perfluoroalkenes

Studies on the Reactivity of Tetrafluoro- and Pentafluorophenyl Trimethylsilyl Ether with Pentafluorobenzenes. Chemistry and X-ray Structural Investigations of Polyfluorodiphenyl Ethers

Insertion of Fluoroalkenes into Activated CH Bonds for the Preparation of Polyfluorinated Sulfanes, Alcohols, and Acyclic and Cyclic Ethers

Contact Info

Product

Resources

About