- Photochemistry of Bis(sulfonyl)diazomethanes
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The photochemistry of a series of bis(sulfonyl)diazomethanes was investigated in solution and in low temperature matrices. These diazo compounds are of interest as photoacid generators in photoresists for deep UV lithography. Triplet carbenes could be trapped in solution, but attempts to isolate the carbenes in argon matrices at 10 K were unsuccessful, the corresponding sulfenes and other rearranged products being observed under these conditions instead. This is in line with DFT and ab initio calculations, which predict the singlet carbenes to be transition states on the pathway to oxathiirene oxides, which can be looked upon as intramolecularly stabilized carbenes. The triplet carbenes lie energetically above the singlet transition states and so are not expected to have a prolonged lifetime even in low-temperature matrices.
- Sander, Wolfram,Strehl, Anja,Winkler, Michael
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- POSITIVE RESIST COMPOSITION AND PATTERNING PROCESS
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A positive resist composition comprises (A) a resin component which becomes soluble in an alkaline developer under the action of an acid and (B) an acid generator. The resin (A) is a polymer comprising recurring units containing a non-leaving hydroxyl group represented by formula (1) wherein R1 is H, methyl or trifluoromethyl, X is a single bond or methylene, m is 1 or 2, and the hydroxyl group attaches to a secondary carbon atom. The composition is improved in resolution when processed by lithography.
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- Nitrogen-containing organic compound, resist composition and patterning process
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Resist compositions comprising nitrogen-containing organic compounds having a benzimidazole structure and a specific ether chain moiety have an excellent resolution, form precisely configured patterns with minimized roughness of sidewalls and are useful in microfabrication using electron beams or deep-UV light.
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- Sulfonates, polymers, resist compositions and patterning process
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A sulfonate compound having formula (1) is novel wherein R1 to R3 are H, F or C1-20 alkyl or fluoroalkyl, at least one of R1 to R3 contains F. A polymer comprising units derived from the sulfonate compound is used as a base resin to formulate a resist composition which is sensitive to high-energy radiation, maintains high transparency at a wavelength of up to 200 nm, and has improved alkali dissolution contrast and plasma etching resistance
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- Sulfonylation of Organometallic Reagents with Arenesulfonyl Fluorides: A Simple One-Step Synthesis of Sulfones
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Sulfonylation of organometallic reagents was accomplished with arenesulfonyl fluorides to provide a wide variety of alkylaryl- and diaryl sulfones.Organolithium and diorganocopper lithium reagents react smoothly with arenesulfonyl fluorides to give sulfones in high yields.Alkyl Grignard reagents often lead to mixtures of monosulfonylated and disulfonylated products.However, allylmagnesium chloride and phenylmagnesium chloride provide the corresponding sulfones in excellent yields.Organocopper reagents were also found to yield sulfones upon treatment with arenesulfonyl fluorides.By utilizing this methodology, synthetically useful alkyl, (trimethylsilyl)methyl, and allyl sulfones are easily prepared in high yields.
- Frye, Leah L.,Sullivan, Eileen L.,Cusack, Kevin P.,Funaro, John M.
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p. 697 - 701
(2007/10/02)
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- 1,2,3-Benzoxathiazole 2,2-Dioxides: Synthesis, Mechanism of Hydrolysis, and Reactions with Nucleophiles
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The rate of base-induced hydrolysis of some five-membered cyclic sulfamates, X-3-(p-tolylsulfonyl)-1,2,3-benzoxathiazole 2,2-dioxides (1a, X = H; 1b, X = 5-Me; 1c, X = 5-t-Bu; 1d, X = 5-Br; 1e, X = 5-Cl; 1f, X = 5-Ac; 1g, X = 5-NO2; 8a, X = 6-NO2) were measured in aqueous acetonitrile.The hydrolyses occurred with cleavage of the endocyclic N-SO2 bond.A Hammett plot using ?m values for 1a-g and ?p for 8a had ρ = +2.20.Activation enthalpies and entropies were measured for 1a and for 3-methyl-1,2,3-benzoxathiazole 2,2-dioxide (10).Volumes of activation weredetermined for 1g and for 8a.The mechanistic profile for hydrolysis resembled that for the saponification of the analogous sultones and cyclic sulfates.These first examples of 1,2,3-benzoxathiazole 2,2-dioxides (1a-g, 8a) were prepared by treating N-(2-hydroxyphenyl)-p-toluenesulfonamides with sulfuryl chloride and triethylamine or by oxidizing the monoxide precursors using m-chloroperbenzoic acid.Treatment of 1a with potassium fluoride gave 1,2,3-benzoxathiazole 2,2-dioxide (9), which was methylated to give 10.Sulfamate 1a was treated with various nucleophilic reagents: phenyllithium, methyllithium, potassium fluoride, methylamine, tert-butylamine, and sodium methoxide.The first three attacked the tosyl sulfur atom and cleaved the exocyclic N-SO2 bond.The amines attacked the endocyclic sulfonyl sulfur atom and cleaved the endocyclic N-SO2 bond.Sodium methoxide attacked both sulfonyl groups.
- Andersen, Kenneth K.,Bray, Diana D.,Chumpradit, Sumalee,Clark, Michael E.,Habgood, Gregory J.,et al.
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p. 6508 - 6516
(2007/10/02)
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- Stibonium and Bismuthonium Ylides. A Comparison with Arsonium and Other Ylides, also including the Crystal Structure of Triphenylarsonium Bis(phenylsulphonyl)methylide and Triphenylarsonium and Triphenylstibonium 4,4-dimethyl-2,6-dioxocyclohexylides
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The spectra, dipole moments, X-ray structures, and chemistry (stability, hydrolysis, reactivity in Wittig reactions) of a number of stibonium ylides are compared with similar properties of their arsonium analogues.There is a close resemblance between the stibonium and arsonium ylides; this is explained in terms of intramolecular interaction between substituent oxygen atoms and the antimony or arsenic atoms.Attempts to prepare stibonium ylides from dichlorotriphenylantimony(V) led always to ylides contaminated with oxybis(triphenylantimony) dichloride.Other oxybis(triphenylantimony) derivatives were obtained from acid hydrolyses of stibonium ylides.Two bismuthonium ylides were also studied.In their case also there appears to be an intramolecular bismuth-oxygen interaction.
- Ferguson, George,Glidewell, Christopher,Gosney, Ian,Lloyd, Douglas,Metcalfe, Shirley,Lumbroso, Henri
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p. 1829 - 1838
(2007/10/02)
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- Syntheses a l'aide de sulfones. XVIII. Utilisation des disulfones-1,1 pour la synthese stereoselective de composes olefiniques
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2-Alkenyl-1,1-disulfones 4 are readily available in excellent yields by condensation of aldehydes with bisaryl or bisalkylsulfonylmethanes in the presence of piperidine acetate and molecular sieves at room temperature.A small amount of the 1-alkenyl isomer is also found when the aldehyde is α-substituted but it can be converted into the 2-alkenyl isomer by base catalysed equilibration.The 2-alkenyl-1,1-disulfones display only E geometry whereas E allylic monosulfones are difficult to isolate in a state of stereochemical purity (about 20percent of the Z isomer at equilibrium (8)).Alkylation is readily performed: treatment of 4 and 6 by sodium hydride in dimethylformamide and then by methyl iodide gives disulfones 5 E and 7 in 78-95percent yields.The alkylation of 4 (R=Et) by butyl iodide gives 70percent of 5 E(R=Et, R'=n-Bu) resulting from alkylation at the α position and 8percent of 3 (R=Et, R'=n-Bu) resulting from alkylation at the γ position.The α isomer is readily purified by crystallization.Reduction of disulfones 4 or 5 by aluminium amalgam leads quantitatively to allylic sulfones 2E or 8E.Olefins 9E are obtained upon total reduction of disulfones 4 or 5 by lithium in ethylamine at -78 deg C but in the case of disulfones 5 the olefins 9E are contaminated by isomers 10E and 10Z.
- Cuvigny, Therese,Penhoat, Catherine Herve Du,Julia, Marc
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