- Application to photoreactive materials of photochemical generation of superbases with high efficiency based on photodecarboxylation reactions
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A thin film of polystyrene containing 4c was spin-coated on a CaF2 plate and irradiated with 365 nm light. The absorption band arising from the carboxylate of 4c at 1372 cm-1 in the FTIR spectrum decreased after UV irradiation. Radical UV curing materials that are well established in the marketplace have drawbacks because of high volume shrinkage and oxygen inhibition. The anionically cured film showed high transparency and no volume shrinkage, in contrast to a conventional radical UV curing system, which showed large volume shrinkage. This is probably due to relatively low quantum yields for photobase generation and weaker basicity of photo-generated bases, leading to low photosensitivity of photoreactive materials sensitized with photobase generators. Furthermore, many of the photobase generators reported are generally prepared via several synthetic steps.
- Arimitsu, Koji,Endo, Ryosuke
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p. 4461 - 4463
(2014/01/06)
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- RESIST COMPOSITION CONTAINING NOVEL SULFONIUM COMPOUND, PATTERN-FORMING METHOD USING THE RESIST COMPOSITION, AND NOVEL SULFONIUM COMPOUND
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A resist composition includes (A) a compound represented by the following formula (I): wherein each of R1 to R13 independently represents a hydrogen atom or a substituent, provided that at least one of R1 to R13 is a substituent containing an alcoholic hydroxyl group; Z represents a single bond or a divalent linking group; and X? represents an anion containing a proton acceptor functional group.
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- Nucleophilicities and carbon basicities of DBU and DBN
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The nucleophilicity and Lewis basicity of DBU and DBN toward C sp2 centers have been measured: nucleophilicities increase in the series DMAP DBU DBN DABCO while Lewis basicities are DABCO DMAP DBU DBN. The Royal Society of Chemistry
- Baidya,Mayr, Herbert
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p. 1792 - 1794
(2008/12/22)
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- An Efficient Synthesis of Bicyclic Amidines by Intramolecular Cyclization
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A real step-saver! In a one-step procedure for the synthesis of bicyclic amidines, the azido group is used directly as the nucleophile in the ring-forming reaction. Many functionalized and chiral bicyclic amidines were synthesized in good yield under mild reaction conditions.
- Kumagai, Naoya,Matsunaga, Shigeki,Shibasaki, Masakatsu
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p. 478 - 482
(2007/10/03)
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- Bicyclic amidines, process for their preparation, and their use as catalyst
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The process for the preparation of bicyclic amidines of the general formula: STR1 wherein A is selected from the group consisting of --CR1 R2 --CR3 R4 --CR5 R6 --, --CR1 R2 --CR3 R4 --CR5 R6 --CR7 R8 -- and --CR1 R2 --CR3 R4 --CR5 R6 --CR7 R8 --CR9 R10 --, wherein the substituents in A are in each case numbered starting from the nitrogen atom, and B is selected from the group consisting of --CR11 R12 --CR13 R14 --, --CR11 R12 --CR15 R16 --CR13 R14 -- and --CR11 R12 --CR15 R16 --CR17 R18 --CR13 R14 --, and R1, R2 and R11 to R14 are, in each case independently of one another, hydrogen, C1 -C4 -alkyl, aryl, or are C1 -C4 -alkyl which is substituted with hydroxyl, amino, C1 -C4 -alkylamino or mercapto, and R3 to R10 and R15 to R18 are, in each case independently of one another, hydrogen, C1 -C4 -alkyl, aryl, hydroxyl, amino, C1 -C4 -alkylamino or mercapto, or are C1 -C4 -alkyl which is substituted with hydroxyl, amino, C1 -C4 -alkylamino or mercapto. The process includes heating (reacting) a lactone of the general formula: STR2 wherein A is as defined above, to at least 150° C. together with an at least equimolar quantity of an amine of the general formula: wherein B is as defined above. The resultant reaction mixture is subjected, without isolating an intermediate, to a fractional distillation.
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- Preparation of bidentate ligands
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A process is disclosed for preparing biaryl, bidentate ligands comprising: (1) contacting a biaryl compound having the structural formula: STR1 with a proton abstracting agent under conditions suitable to form a biaryl dianion, which is then (2) contacted with a Group V compound of the formula: STR2 where X' is halogen or a suitable leaving group.
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- Process for producing quaternary salts
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A process for producing quaternary salts of high purity is disclosed, comprising reacting a tertiary amine or phosphine with a carbonic acid diester to form a corresponding quaternary carbonate and further mixing it with an acid to perform decarboxylation. The quaternary salts thus obtained are useful compounds which can be used in wide fields as various catalysts, electrolytes, additives, medicaments, etc.
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- Process for the acrylamidoacylation of alcohols
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The present invention provides a dramatically improved process for the preparation of acrylamide and methacrylamide functional monomers, oligomers, and polymers that avoids the use of acidic catalysts which can cause undesired side reactions. The present invention process involves reacting an alkenyl azlactone with a hydroxy functional compound in the presence of a catalytic amount of either a bicyclic amidine or a trivalent phosphorus compound. These efficient basic catalysts provide unexpectedly increased reaction rates under mild conditions.
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