- Facile preparation and synthetic applications of LiCH2C(CF3)2Oli
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Bromohydrin BrCH2C(CF3)2OH readily reacts with two equivalents of n-BuLi at - 78 °C to produce the corresponding dilithium derivative LiCH2C(CF3)2OLi in high yield. This dilithiated derivative reacts selectively, acting as a C-nucleophile, with a variety of electrophiles such as R2PCl, carbonyl compounds, and epoxides, to give electron-deficient phosphines R2PCH2C(CF3)2OH, 1,3- and 1,4-diols, correspondingly.
- Grushin, Vladimir V.,Marshall, William J.,Halliday, Gary A.,Davidson, Fredric,Petrov, Viacheslav A.
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- The cross-aldol reaction of hexafluoroacetone (HFA) with ketones catalyzed by an acid
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The cross-aldol reactions of hexafluoroacetone (HFA) and ketones using an acid catalyst are reported. When concentrated sulfuric acid was employed as the catalyst, HFA reacted regioselectively with various ketones at 50-100 °C to give the aldol adducts (6) in good yields. The reaction is initiated by an acid-catalyzed transformation of the ketone into the corresponding enol that reacts with HFA. The obtained adducts (6) can be reduced with hydrogen under a Ru/C catalyst to lead to the corresponding fluorine-containing diols (13).
- Komata, Takeo,Matsunaga, Kei,Hirotsu, Yoshiki,Akiba, Shinya,Ogura, Katsuyuki
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p. 902 - 909
(2008/03/14)
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- 1,1-Bis(trifluoromethyl)butadiene-1,3-A new fluorinated building block
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Although 1,1-bis(trifluoromethyl)butadiene-1,3 (1) reacts with dimethylamine with selective formation of 1,4-adduct [trans-(CF3)2CHCH{double bond, long}CHCH2N(CH3)2], halogenation of 1 proceeds with predominant formation (>92%) of 1,2-adducts (CF3)2C{double bond, long}CHCHXCH2X (X = Cl or Br). Electrophilic conjugated addition of "ClF" or "BrF" to 1 proceeds exclusively with the formation of 1,2-adducts (CF3)2C{double bond, long}CHCHFCH2X (major) and (CF3)2C{double bond, long}CHCHXCH2F (X = Cl or Br). Difluorocarbene adds selectively to {single bond}CH{double bond, long}CH2 moiety of 1 forming thermally stable vinylcyclopropane. In Diels-Alder reaction with linear or cyclic dienes (butadienes, cyclopentadiene, cyclohexadiene-1,3) and quadricyclane compound 1 behaves as dienophile providing for the reaction electron-deficient {single bond}CH{double bond, long}CH2 bond. The relative rate of cycloaddition of 1 and other fluoroolefins to quadricyclane, measured by high temperature NMR, indicates that (CF3)2C{double bond, long}CH{single bond} acts as very strong electron-withdrawing substituent. Synthetic utility of products based on 1 was also demonstrated.
- Petrov, Viacheslav A.
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p. 529 - 538
(2008/09/17)
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- NEW HEXAFLUOROALCOHOL-BASED MONOMERS AND PROCESSES OF PREPARATION THEREOF
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The present invention relates to compounds of formula (I): wherein R1 is H, or a C1-C10 linear, branched or cyclic alkyl group which is unsubstituted or substituted with fluorine; R2 is an alicyclic group having 5 to 20 carbon atoms which is unsubstituted or substituted with fluorine; and R3 represents a C1-C10 linear or branched alkylène which is unsubstituted or substituted with fluorine. Processes for preparing such compounds are also disclosed. The compounds of the present invention can be used as monomers in the fields of photolithography and semiconductor fabrication.
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Page/Page column 14-15
(2008/06/13)
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- Fluorinated vinyl ethers, copolymers thereof, and use in lithographic photoresist compositions
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Fluorinated vinyl ethers are provided having the structure of formula (I) the structure of formula (I) wherein at least one of X and Y is a fluorine atom, and L, R1, R2, R3, R4 are as defined herein. Also provided are copolymers prepared by radical polymerization of (I) and a second monomer that may not be fluorinated. The polymers are useful in lithographic photoresist compositions, particularly chemical amplification resists. In a preferred embodiment, the polymers are substantially transparent to deep ultraviolet (DUV) radiation, and are thus useful in DUV lithographic photoresist compositions. A method for using the composition to generate resist images on a substrate is also provided, i.e., in the manufacture of integrated circuits or the like.
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Page/Page column 12-13
(2008/06/13)
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- Processes for producing fluorine-containing 2,4-diols and their derivatives
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A process for producing a fluorine-containing 2,4-diol represented by the formula [4], wherein R1 represents a hydrogen atom or an acyclic or cyclic alkyl group having a carbon atom number of 1 to 7; R2 represents an acyclic or cyclic alkyl group having a carbon atom number of 1 to 7, a phenyl group, or a substituted phenyl group; and R1 and R2 are optionally bonded to each other to form a ring, includes reducing a hydroxy ketone represented by the formula [3], wherein R1 and R2 are defined as above, by hydrogen in the presence of a ruthenium catalyst.
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Page/Page column 9
(2008/06/13)
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- Process for producing alpha-substituted acrylic acid esters
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A process for producing an α-substituted acrylic acid ester represented by the formula [1], wherein each of R1 and R2 is independently a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, or perfluoroethyl group, includes reacting an α-substituted acrylic acid anhydride represented by the formula [7], with 1,1-bis(trifluoromethyl)-1,3-diol represented by the formula [2].
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Page/Page column 4
(2008/06/13)
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- Precursors to fluoroalkanol-containing olefin monomers and associated methods of synthesis and use
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The invention provides alkene fluoroalkanol and fluorinated polyol precursors to fluoroalkanol-substituted α,β-unsaturated esters. The fluoroalkanol-substituted α,β-unsaturated esters are olefins that can be readily polymerized to provide fluoroalkanol-substituted polymers useful in lithographic photoresist compositions. Also provided are methods for synthesizing the alkene fluoroalkanol and fluorinated polyol precursors.
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Page/Page column 13
(2008/06/13)
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- Precursors to fluoroalkanol-containing olefin monomers, and associated methods of synthesis and use
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The invention provides alkene fluoroalkanol and fluorinated polyol precursors to fluoroalkanol-substituted αβ-unsaturated esters. The fluoroalkanol-substituted αβ-unsaturated esters are olefins that can be readily polymerized to provide fluoroalkanol-substituted polymers useful in lithographic photoresist compositions. Also provided are methods for synthesizing the alkene fluoroalkanol and fluorinated polyol precursors.
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Page/Page column 13
(2008/06/13)
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