Sulfonyl Esters Research Articles

DFT Calculations of Photoabsorption Spectra in the VUV Region for Design of Photoresist Materials for 157 nm Lithography.

Time-dependent density functional theory (TD-DFT) calculations using the B3LYP hybrid functional were performed to investigate the transparencies of organic molecules and polymers in the vacuum ultraviolet (VUV) region. The calculated photoabsorption spectra obtained from the combination of geometry optimization using the 6-311G(d) basis set and subsequent calculations of transition energies and oscillator strengths using the 6-311++G(d, p) basis set agree well with the experimental spectra. This method is a useful to infer the transparency of polymers in the VUV region, and in particular helpful for design of photoresist materials for F2 lithography (157nm). The transparencies of the model compounds relating to the representative polymer platforms were estimated, and the calculated spectra demonstrate the effectiveness of judicious introduction of -F and -CF3 groups in reducing optical absorption at the wavelength. In addition, the absorption spectra of model compounds having a sulfonyl fluoride (-SO2F) and sulfonyl ester (-SO2OR) groups, which were proposed by the present authors as novel resist platforms, were calculated and compared with the experimental spectra of corresponding homopolymers.

Selective desulfonylation in D-xylofuranose 3,5-disulfonates

A method for the preparation of D-xylofuranose derivatives with a free terminal (C5) alcohol function was developed, starting from monocyclohexylidene-3,5-disulfonyl- or 5-O-sulfonyl-3-O-methyl ester. The regioselective displacement of the C5 sulfonyl ester functionwith acetate ion in dimethylsulfoxide afforded the corresponding 5-O-acetyl-1,2-O-cyclohexylidene-3-O-sulfonyl or 5-O-acetyl-3-O-methyl- -D-xylofuranose. These esters could be readily hydrolysed into the desired 1,2,3-trisubstituted xylofuranose.

2-Methoxy-4-(2-phthalimidinyl)phenylsulfonyl Chloride as a Fluorescent Labeling Reagent for Determination of Phenols in High-Performance Liquid Chromatography and Application for Determination of Urinary Phenol and p-Cresol

Highly sensitive fluorescent labeling reagents, 2-(alkyloxy)-4-(2-phthalimidinyl)phenylsulfonyl chlorides (alkyloxy = methoxy, ethoxy, and propoxy; MPS-Cl, EPS-Cl, and PPS-Cl, respectively), for determination of phenols by high-performance liquid chromatography (HPLC) have been developed. These reagents react with phenols in basic medium to produce the corresponding fluorescent sulfonyl esters. The maximum fluorescence wavelengths of the derivatives were 308 nm for excitation and 410 nm for emission. The peaks due to phenol labeled with MPS-Cl, EPS-Cl, and PPS-Cl eluted at 6.3, 8.8, and 12.8 min, respectively, on a reversed-phase column with isocratic elution of methanol/water (2:1, v/v), and the detection limits (signal-to-noise = 3) of the derivatives were 10, 12, and 17 fmol per injection, respectively. Among these reagents, MPS-Cl was advantageous because its derivatives had shorter retention times and higher sensitivities in HPLC. The efficiency of converting phenol to the fluorescent derivative by MPS-Cl was about 100%. When MPS-Cl was applied to the determination of urinary phenol and p-cresol by HPLC using p-ethylphenol as an internal standard, the derivatives were separated at retention times of 6.3, 8.7, and 12.3 min, respectively, under the HPLC conditions described above. The concentrations of phenol and p-cresol in normal human urine were 11.9–293.5 and 8.2–346.1 nmol/mg creatinine, respectively.

Synthesis and Characterization of Calix[4]arene Functionalized Poly(ethylene glycol) Derivatives

Calix[4]arenes with both ligating and methoxy poly(ethylene glycol) groups appended have been synthesized using several approaches, involving the formation of sulfonyl ester groups on the wide rim, Schiff base derivatives on the narrow rim, and thioether groups on both the wide and narrow rims. These new derivatives have been characterized by a combination of infrared and 1H NMR spectroscopy. Compounds 10 and 11 are insoluble in both water and aqueous poly(ethylene glycol), but the other new compounds are soluble.

Fluorometric Determination of Phenol andp-Cresol in Urine by Precolumn High-Performance Liquid Chromatography Using 4-(N-Phthalimidinyl)benzenesulfonyl Chloride

A sensitive HPLC method for simultaneous determination of phenol andp-cresol in urine was developed. After acid hydrolysis of urine was conducted, phenol andp-cresol were extracted with diisopropyl ether and derivatized with 4-(N-phthalimidinyl)benzenesulfonyl chloride to give fluorescent sulfonyl esters. The labeling reactions were completed at 75°C for 10 min. The fluorescent derivatives were separated on a reversed-phase column by a gradient elution with acetonitrile–water and detected by fluorescence measurement of excitation at 300 nm and emission at 410 nm. The detection limits (signal-to-noise ratio = 3) for phenol andp-cresol were 0.17 and 0.25 pmol per injection, respectively. The within-day and day-to-day relative standard deviations were 2.31–3.76 and 4.36%, respectively, for phenol and 1.99–4.56 and 3.71%, respectively, forp-cresol. The concentrations (means) of phenol andp-cresol in normal human urine were 67.3 and 167.9 nmol/mg creatinine, respectively.

Sulfonyl esters 7. The second and third sequences in the Trithioorthoformate Reaction

A previous report has established the intermediacy of a sulfide-sulfonate ester in the one-pot conversion of an aryl mercaptan and a sulfonate ester into the corresponding trithioorthoformate. This report describes evidence for the sequential intermediacy of a bissulfide-sulfonate ester and a dithiosulfène in the conversion of the sulfide-sulfonate ester into the trithioorthoformate. A new sulfonate ester is shown to give the highest yield of trithioorthoformate. Key words: single electron transfer, sulfonate esters, sulfenes.

Soft drugs. XX. Design, synthesis, and evaluation of ultra-short acting beta-blockers.

A new type of ultra-short acting beta-blocker which might prove advantageous in treating acute arrhythmias was designed, synthesized and investigated. Based on the soft drug "inactive metabolite approach," the inactive phenylacetic acid metabolite of both metoprolol and atenolol was reactivated by esterification with sulfur-containing aliphatic alcohols. Since the sulfur-containing moieties are labile to the ubiquitous esterases, the new compounds should be inactivated by a one step enzymatic cleavage back to the inactive phenylacetic acid derivative. Pharmacological and pharmacokinetic profiles of the new compounds were evaluated in rats and rabbits. Isoproterenol-induced tachycardia was inhibited with short-term infusion of each compound. This tachycardia blocking effect rapidly disappeared upon termination of infusion, while beta-blocking activity was 2-4-fold longer after comparable doses of the short-acting beta-blocker, esmolol. The rapid recovery from the beta-receptor blockade is believed due to fast hydrolysis of the soft drugs in the body. This is supported from in vitro results showing the t1/2 of esmolol is about 10-fold longer than the new soft drugs in rat, rabbit, dog and human blood. Hydrolysis studies in phosphate buffered solutions indicated that the esters are labile to base-catalyzed hydrolysis. However, the relative t1/2 values measured in biological media compared to phosphate buffered solution clearly support rapid enzymatic cleavage of the soft drugs. Interestingly, one of the soft beta-blockers, the sulfonyl ester derivative, showed a unique property of exhibiting good beta-receptor blocking activity without significant hypotensive action.

Sulfonyl Esters. V. A Preparation of Dichloromethyl Sulfones

α-Sulfonyl methyl esters have been chlorinated in the presence of base. Chlorination proceeds with accompanying demethoxycarbonylation to furnish dichloromethyl sulfones in good yields.

Nucleophilic substitutions of 1-alkenylcyclopropyl esters and 1-alkynylcyclopropyl chlorides catalyzed by palladium(0)

The 1-ethenylcyclopropylsulfonates 2e,f and 2-cyclopropylideneethyl esters 10b,c, readily available from cyclopropanone hemiacetal 1, undergo regioselective Pd(0) catalyzed nucleophilic substitution via the unsymmetric 1,1-dimethylene-{pi}-allyl complex 23. With stabilized anions (enolates of malonic ester, {beta}-dicarbonyl compounds, {beta}-sulfonyl ester, and Schiff bases as well as acetate anion, sulfonamide anion, etc.) the nucleophilic substitution occurs at the terminal vinylic position exclusively, providing cyclopropylideneethyl derivatives as building blocks of high synthetic potential. Competition experiments have disclosed that 1-ethenylcyclopropyl tosylate (2e) and cyclopropylideneethyl acetate (10b) are more reactive than dimethylallyl acetates 19 and 22, respectively. Use of chiral phosphines as ligands in the palladium catalyst can provide optically active methylenecyclopropane derivatives. With phenyl-, methyl-, and even n-butylzinc chloride as nucleophiles, the reaction apparently proceeds with initial transfer of the organic residue to palladium, followed by reductive elimination entailing tertiary substitution on the cyclopropane ring exclusively; the same type of product is obtained with azide and bis(trimethylsilyl)amide. But the site of hydride attack to yield reduction products depends on the hydride source. 1-Alkynylcyclopropyl chlorides 12, 13, and 14 react only with organozinc chlorides (nonstabilized nucleophiles) to provide mixtures of ethenylidenecyclopropanes 65 and alkynylcyclopropanes 66, via the {sigma}-palladium complexes 69 and 70, while chloride 15 undergoes mainly reduction.more » Other transition metal catalysts (Ni, Mo) also induce substitutions, but with poorer regioselectivity. 81 refs., 9 figs., 3 tabs.« less

Sulfonyl esters 3. The formation of sulfone-sulfonates in the reactions of aryl methanesulfonates with sodium hydride

Sodium hydride reductions of aryl methanesulfonates afford dimeric sulfone-sulfonate esters as well as products arising from SO bond rupture. SO bond rupture becomes more competitive as the LUMO energy of the sulfonate ester declines. Exploration of the chemistry of a sulfone-sulfonate ester revealed a complex novel reaction that resulted in the formation of, inter alia, a dichloromethanesulfonate ester and a trichloromethanesulfonate ester. The first successful approaches to the synthesis of the heretofore unknown trichloromethanesulfonates and dichloromethanesulfonates are reported. Key words: sodium hydride reductions, sulfenes, sulfone-sulfonate esters

En route to thromboxane compounds from carbohydrates, I. Synthesis of the unsaturated sugar precursors

AbstractAllyl 4‐C‐[(carboxamido)‐ and (ethoxycarbonyl)methyl]hex‐2‐enopyranosides 18a–c, representing chiral precursors for the carbohydrate‐based construction of the ring systems of thromboxane A2 and B2 were prepared by means of the Claisen‐type rearrangement of the suitably substituted hex‐3‐enopyranosides 7a, b. The latter sugars were synthesized from allyl α‐D‐glucopyraoside (9) by modification of known procedures, including selective O‐benzoylation with 1‐(benzoyloxy)‐1H‐benzotriazole (11), and Tipson‐Cohen sulfonyl ester elimination of the 3,4‐di‐O‐mesylates 16 and 17. Studies on the corresponding methyl glycosides 8a–c showed a reduced stability of the 6‐O‐(tert‐butyldiphenylsilyl) ether group under the Tipson‐Cohen reaction conditions.

Sulfonyl esters. 2. CS cleavage in some substitution reactions of nitrobenzenesulfonates

An attempt to explore aromatic sulfonate esters as agents for the condensation of alcohols with mercaptans revealed an unusual process for sulfonate esters: CS bond rupture. Two mechanistic possibilities for CS bond rupture are explored: (i) radical anion intermediacy via single electron transfer and (ii) nucleophilic aromatic substitution. Both experiments and molecular orbital computations are presented to support the conclusion that nucleophilic aromatic substitutions are occurring. Keywords: sulfonyl esters, nitrobenzenesulfonates, CS bond rupture.

Sulfonyl esters 1: The reduction of tribromophenyl sulfonates with mercaptide anions

2,4,6-Tribromophenyl sulfonates have been shown to undergo unusually efficient reduction by mercaptide anions in hexamethylphosphoramide. The reduction products include the sulfinate anion derived from the sulfonate ester and the disulfide derived from the mercaptide anions.

Reduction processes in the fast atom bombardment mass spectrometry of sulfonyl esters of diazonaphthalenones

AbstractOrthoquinone diazides, which are widely used in microlithography, have attracted considerable attention, especially in terms of their application in the production of high‐contrast resists. Previous electron impact mass spectrometric results have confirmed that the primary fragmentation process of these compounds is the elimination of N2 to form an indenoketene ion. This is analogous to the photodecomposition pathway which makes them effective in the lithographic process. Those results also revealed the occurrence of an alternative process, which involves a two‐hydrogen reduction of the intermediate species formed prior to conversion to the ketene. The present study investigates the behaviour of the orthoquinone diazides when there is an abundance of protons available to form the reduction product. Several different types of diazonaphthalenone sulfonyl esters, ranging in complexity from the monosubstituted phenol esters to disubstituted dihydroxybenzophenones, were examined using fast atom bombardment mass spectrometry. Although reduction was the primary process in the hydrogen‐rich matrices, the extent of reduction was characteristic of the particular isomer as well as the matrix used.

Mass spectrometric studies of sulfonyl esters of diazonaphthalenones: Relationship between fragmentation patterns and photolithographic mechanisms

AbstractEsters of 2‐diazonaphthalenone sulfonic acid were examined by mass spectrometry using electron impact and chemical ionization techniques. Charactristic differences in the fragmentation patterns of positional isomers have been observed. In a manner analogous to photo‐induced decompositions, the diazoketo functional groups fragment by elimination of N2 to form an indenoketene ion. An alternative process involves the apparent loss of 26 mass units from the molecular ion. The latter process is explained by evoking the abstraction of two hydrogen atoms following the loss of N2. With deuterium isotope labeling, it has been shown that the hydrogens are abstracted from the surface of the probe tip used for introduction of the samples into the mass spectrometer. It is concluded that an environment rich in hydrogen or proton‐donating properties promotes and enhances the incorporation of the hydrogen atoms and formation of the [M‐26] species at the expense of the ketene moiety, which is an important intermediate in the photoresist process. By extrapolation it may be inferred that the efficiency of the photolithographic process could be influenced by the availability of protons in the photoresist matrix.

Intramolecular rhodium carbenoid insertions into aromatic CH bonds. Preparation of 1-carboalkoxy-1,3-dihydrobenzo[C]thiophene 2,2-dioxides

Rhodium acetate catalyzed decompostion of various α-diazo-β-phenylmethane sulfonyl esters resulted in the formation of the title compounds in 40–50% yields.

Preparation and characterization of p‐toluene sulfonyl ester and amino derivatives of tri‐ and poly(ethylene glycol)

AbstractMethods described in the literature are inadequate for the preparation of pure polyethylene glycol (PEG) tosylate. Therefore an improved method is presented. The hydroxyl groups on PEG can be quantitatively converted into the tosylate and isolated from the reaction medium free from impurities with no chain cleavage or reduction in molecular weight. 1,2‐Di(N‐phenyl 2‐aminoethoxy) ethane, α,ω‐di(N‐phenyl 2‐aminoethyl) poly(oxyethylene), and α,ω‐di(N‐phenyl, N‐benzyl 2‐aminoethyl) poly(oxyethylene) were prepared from the tosylates of tri‐ and poly(ethylene glycol)s and the corresponding primary and secondary aromatic amines.

Cesium fluoride mediated intramolecular conjugate-addition reactions of alpha sulfonyl ester to enones and alpha-chloroenones

Cesium fluoride is a useful catalyst to effect the intramolecular conjugate-addition of alpha-sulfonyl esters to enones; similar reaction with alpha-chloroenones provides fused cyclopropane adducts.

ChemInform Abstract: SYNTHESIS AND BIOLOGICAL ACTIVITY OF POTENTIAL ANTIMETABOLITES OF L‐FUCOSE

AbstractAus L‐Galaktose erhält man mit Aceton, Kupfersulfat und Schwefelsäure das Ketal (I), deren Sulfonate (III) in die ungeschützten Sulfonate (IV) übergeführt werden.

Synthesis and biological activity of potential antimetabolites of L-fucose.

6-Substituted 6-deoxy-L-galactose (L-fucose) derivatives were synthesized as potential antimetabolites of L-fucose. The cytotoxic effects of these compounds were evaluated on P388 leukemia cells in culture. The L-fucose analogues which showed the most potent growth inhibition were the sulfonyl ester, bromo, and iodo derivatives; since these compounds were all capable of alkylation, it is conceivable that their cytotoxic action is a consequence of this property. In agreement with this interpretation, none of the agents synthesized showed specific inhibition of the incorporation of L-[3H]fucose into glycoprotein.