- C70Fullerene Catalyzed Photoinduced Aerobic Oxidation of Benzylamines to Imines and Aldehydes
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C70 fullerene catalyzed photoinduced oxidation of benzylic amines at ambient conditions has been explored here. The developed strategy's main feature includes the additive/oxidant-free conversion of benzylic amine to corresponding imine and aldehydes. The reaction manifests broad substrate scope with excellent function group leniency and is applicable up to the gram scale. Further, symmetrical secondary amines can also be synthesized from benzylic amine in a one-pot two-step process. Various experiments and density functional theory studies revealed that the current reaction involves the generation of reactive oxygen species, single electron transfer reaction, and benzyl radical formation as key steps under photocatalytic conditions.
- Kumar, Inder,Kumar, Rakesh,Gupta, Shiv Shankar,Sharma, Upendra
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supporting information
p. 6449 - 6457
(2021/05/29)
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- One-Pot Direct Oxidation of Primary Amines to Carboxylic Acids through Tandem ortho-Naphthoquinone-Catalyzed and TBHP-Promoted Oxidation Sequence
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Biomimetic oxidation of primary amines to carboxylic acids has been developed where the copper-containing amine oxidase (CuAO)-like o-NQ-catalyzed aerobic oxidation was combined with the aldehyde dehydrogenase (ALDH)-like TBHP-mediated imine oxidation protocol. Notably, the current tandem oxidation strategy provides a new mechanistic insight into the imine intermediate and the seemingly simple TBHP-mediated oxidation pathways of imines. The developed metal-free amine oxidation protocol allows the use of molecular oxygen and TBHP, safe forms of oxidant that may appeal to the industrial application.
- Kim, Hun Young,Oh, Kyungsoo,Si, Tengda
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supporting information
p. 18150 - 18155
(2021/12/09)
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- Catalyst-free photodecarbonylation ofortho-amino benzaldehyde
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It is almost a consensus that decarbonylation of the aldehyde group (-CHO) needs to not only be mediated by transition metal catalysts, but also requires severe reaction conditions (high temperature and long reaction time). In this work, inspired by the “conformational-selectivity-based” design strategy, we broke this consensus and discovered a catalyst-free photodecarbonylation of the aldehyde group. It revealed that decarbonylation can be easily achieved with visible light irradiation by introducing a tertiary amine into theortho-position of the aldehyde group. A diverse array of tertiary amines is tolerated by our photodecarbonylation under mild conditions. Furthermore, the (QM) computations of the mechanism and the experiments on well-designed special substrates revealed that our photodecarbonylation depends on the conformational specificity of the aldehyde group and tertiary amine, and occurs through an unusual [1,4]-H shift and a subsequent [1,3]-H shift.
- Li, Lamei,Wang, Songping,Wei, Wentao,Yan, Ming,Zhou, Jingwei
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supporting information
p. 3421 - 3426
(2020/06/25)
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- Method for synthesizing aromatic aldehyde through iron catalyzed oxidation allyl aromatic compound
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The invention discloses a method for synthesizing aromatic aldehyde through an iron catalyzed oxidation allyl aromatic compound. According to the specific method, under the promotion effect of hydrogen silane, with air or oxygen as the oxidant, the aromatic aldehyde compound is synthesized through the iron catalyzed oxidation allyl aromatic compound, the reaction temperature is 20-150 DEG C, and the time is 0.25-60 h. The method has the advantages that a catalyst source is wide, the price is low and the environment is protected; an oxidant source is wide, the price is low and no waste is generated; the reaction conditions are mild, selectivity is high and the yield is high; a substrate source is wide and stable; a substrate functional group is high in compatibility and a substrate is widein application range; complicated small molecules are compatible and can be well converted into aldehyde. The target product separation yield can reach up to 96% under the optimized reaction conditions.
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Paragraph 0090-0092; 0150
(2019/06/27)
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- Purple acid phosphatase inhibitors as leads for osteoporosis chemotherapeutics
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Purple acid phosphatases (PAPs) are metalloenzymes that catalyse the hydrolysis of phosphate esters under acidic conditions. Their active site contains a Fe(III)Fe(II) metal centre in mammals and a Fe(III)Zn(II) or Fe(III)Mn(II) metal centre in plants. In humans, elevated PAP levels in serum strongly correlate with the progression of osteoporosis and metabolic bone malignancies, which make PAP a target suitable for the development of chemotherapeutics to combat bone ailments. Due to difficulties in obtaining the human enzyme, the corresponding enzymes from red kidney bean and pig have been used previously to develop specific PAP inhibitors. Here, existing lead compounds were further elaborated to create a series of inhibitors with Ki values as low as ~30 μM. The inhibition constants of these compounds were of comparable magnitude for pig and red kidney bean PAPs, indicating that relevant binding interactions are conserved. The crystal structure of red kidney bean PAP in complex with the most potent inhibitor in this series, compound 4f, was solved to 2.40 ? resolution. This inhibitor coordinates directly to the binuclear metal centre in the active site as expected based on its competitive mode of inhibition. Docking simulations predict that this compound binds to human PAP in a similar mode. This study presents the first example of a PAP structure in complex with an inhibitor that is of relevance to the development of anti-osteoporotic chemotherapeutics.
- Hussein, Waleed M.,Feder, Daniel,Schenk, Gerhard,Guddat, Luke W.,McGeary, Ross P.
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p. 462 - 479
(2018/08/21)
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- Fungal biofilm inhibition by piperazine-sulphonamide linked Schiff bases: Design, synthesis, and biological evaluation
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We report the synthesis of some new piperazine-sulphonamide linked Schiff bases as fungal biofilm inhibitors with antibacterial and antifungal potential. The biofilm inhibition result of Candida albicans proposed that the compounds 6b (IC50 = 32.1 μM) and 6j (IC50 = 31.4 μM) showed higher inhibitory activity than the standard fluconazole (IC50 = 40 μM). Compound 6d (MIC = 26.1 μg/mL) with a chloro group at the para position was found to be the most active antibacterial agent of the series against Bacillus subtilis when compared with the standard ciprofloxacin (MIC = 50 μg/mL). Compound 6j (MIC = 39.6 μg/mL) with an OH? group at the ortho position showed more potent antifungal activity as compared to that of the standard fluconazole (IC50 = 50 μM) against C. albicans. Thus, the synthesized compounds 6a–k were found to be potent biofilm inhibitors as well as active antibacterial and antifungal agents. The molecular docking study of the synthesized compounds against the secreted aspartyl protease (SAP5) enzyme of C. albicans exhibited good binding properties. The in silico ADME properties of the synthesized compounds were also analyzed and showed their potential to be developed as potential oral drug candidates.
- Patil, Rajendra H.,Kalam Khan, Firoz A.,Jadhav, Kaivalya,Damale, Manoj,Akber Ansari, Siddique,Alkahtani, Hamad M.,Ali Khan, Azmat,Shinde, Shantanu D.,Patil, Rajesh,Sangshetti, Jaiprakash N.
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- Synthesis of 5-arylisoxazole-3-carboxylates derived from salicylaldehyde
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A procedure has been developed for the synthesis of 5-arylisoxazole-3-carboxylates on the basis of phenols and oximes derived from salicylaldehyde. Selective reduction of 4-(2-ethoxybenzylideneaminophenyl) 5-arylisoxazole-3-carboxylates afforded the corresponding amines.
- Petkevich, S. K.,Dikusar, E. A.,Potkin, V. I.,Mikhei, I. V.
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- Solid supported Ru(0) nanoparticles: An efficient ligand-free heterogeneous catalyst for aerobic oxidation of benzylic and allylic alcohol to carbonyl
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Polymer immobilized stable, spherical ruthenium nanoparticles were prepared, characterized, and acted as a heterogeneous catalyst for the selective benzylic and allylic alcohol oxidation into the corresponding carbonyls using molecular oxygen. The solid supported Ru(0) (SS-Ru) as a heterogeneous catalyst exhibits good reusability and easy separation from the reaction mixture by filtration.
- Das, Pralay,Aggarwal, Nidhi,Guha, Nitul Ranjan
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supporting information
p. 2924 - 2928
(2013/06/27)
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- Solid-supported Pd(0): An efficient heterogeneous catalyst for aerobic oxidation of benzyl alcohols into aldehydes and ketones
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Solid-supported nano- and microparticles of Pd(0) (SS-Pd) were used as heterogeneous catalysts for aerobic oxidation of benzyl alcohols. Primary and secondary benzyl alcohols gave the corresponding products in good yields. In addition, the catalysts could be reused up to five runs without significant loss of activities.
- Bandna,Aggarwal, Nidhi,Das, Pralay
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supporting information; experimental part
p. 4954 - 4956
(2011/10/08)
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- Electrophilic carbon transfer in gold catalysis: Synthesis of substituted chromones
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Using easily accessible aromatic alkoxy-arylalkynones, we have investigated the gold-catalyzed intramolecular addition of ethers to alkynes, to give easy access to various substituted chromones. This reaction involves the transfer of the ether substituent via a carbodemetallation process. We also noticed a competing isomerization of several starting materials for which we propose a second gold catalyzed mechanism.
- Renault, Jacques,Qian, Zhao,Uriac, Philippe,Gouault, Nicolas
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supporting information; experimental part
p. 2476 - 2479
(2011/05/16)
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- Palladium-catalyzed aerobic alcohol oxidation supported by a new type of α-diimine ligands
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A series of new ionic sulfonated α-diimine ligands were prepared and employed as supporting ligands for the palladium-catalyzed aerobic alcohol oxidation. The electronic properties, rigidity, and steric hindrance of ligands have remarkable influences upon the catalytic activity of the palladium complexes. The best catalytic result could be achieved using ligand 9 with an electron-withdrawing sulfonyl substituent together with bulky groups (iso-propyl in 2,6-positions). This diimine/palladium-catalyzed system is highly efficient for the oxidation of various benzylic alcohols, and showed moderate yields for the secondary aliphatic alcohols and cyclic alcohols.
- Zhou, Jin,Li, Xiaoyan,Sun, Hongjian
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p. 782 - 790
(2008/12/20)
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- A new application of hexamethylenetetramine-bromine supported onto wet alumina as an efficient reagent for cleavage of phenylhydrazones under classical heating and microwave irradiation
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2,4-Dinitrophenylhydrazones were converted to their parent carbonyl compounds using hexamethylenetetramine-bromine complex supported onto wet alumina under classical heating and microwave irradiation.
- Heravi, Majid M.,Sabaghiani, Ali J.,Bakavoli, Mehdi,Ghassemzadeh, Mitra,Bakhtiari, Khadijeh
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p. 123 - 126
(2008/02/11)
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- Competitive formation of β-amino acids, propenoic, and ylidenemalonic acids by the Rodionov reaction from malonic acid, aldehydes, and ammonium acetate in alcoholic medium
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The Rodionov reaction of 49 available aliphatic and aromatic aldehydes with malonic acid and ammonium acetate in alcoholic medium, resulting in formation of β-amino acids, propenoic, and ylidenemalonic acids, was studied. Certain regioselectivity regularities of the reaction were revealed. Among the variety of ketones studied, cyclohexanone is the only whose reaction yields a β-amino acid. Unusual dehydrofluorination of 6-chloro-2-fluorocinnamic acid under the Rodionov reaction was discovered. 2005 Pleiades Publishing, Inc.
- Lebedev,Lebedeva,Sheludyakov,Kovaleva,Ustinova,Kozhevnikov
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p. 1113 - 1124
(2007/10/03)
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- Synthesis of aromatic aldehydes by oxidative hydroxymethylation
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A new high yield method for the synthesis of aromatic aldehydes has been developed. The procedure is based on an acid catalyzed hydroxymethylation of an arene substrate by paraformaldehyde with concurrent selective oxidation of the intermediate aromatic carbinol by 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) to the aldehyde product.
- Branytska, Oiena,Neumann, Ronny
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p. 1575 - 1576
(2007/10/03)
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- Regeneration of carbonyl compounds by cleavage of C=N bonds under mild and completely heterogeneous conditions
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Oximes, hydrazones, semicarbazones and azines are converted to the corresponding carbonyl compounds using a combination of Zr(HSO4) 4 and wet SiO2 in good to high yields under completely heterogeneous conditions.
- Shirini,Zolfigol,Safari,Mohammadpoor-Baltork,Mirjalili
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p. 7463 - 7465
(2007/10/03)
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- Silica sulfuric acid/wet SiO2 as a novel heterogeneous system for cleavage of carbon nitrogen double bonds under mild conditions
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Silica sulfuric acid in the presence of wet SiO2 was caused to react with oximes, hydrazones, semicarbazones, azines, and Schiff-bases. It was observed that it converts them to their corresponding carbonyl compounds in good to excellent yields under mild and heterogeneous conditions.
- Zolfigol, Mohammad Ali,Poor-Baltork, Iraj Mohammad,Mirjalili, Bibi Fatemeh,Shirini, Farhad,Salehzadeh, Sadegh,Keypour, Hassan,Ghorbani-Choghamarani, Arash,Zebarjadian, Mohammad Hassan,Mohammadi, Kamal,Hazar, Azizeh
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p. 2735 - 2743
(2007/10/03)
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- Compositions containing aromatic aldehydes and their use in treatments
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Disclosed are pharmaceutical and cosmetic compositions containing aromatic aldehyde compounds. Some of the disclosed compositions are useful as topical therapeutics for treating inflammatory dermatologic conditions. Some of the compositions are useful in transdermal and other systemic dose forms for treating other inflammatory conditions in mammals.
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- Reactions of 1-(2-alkoxyphenyl)alkaniminyl radicals
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Reactions of 1-(2-alkoxyphenyl)alkaniminyl radicals were studied. Generation of the iminyls 1d and 1e by standard methods in the gas-phase by flash vacuum pyrolysis (FVP) gives rise to 1,3-benzoxazines 18 and 22 by a mechanism which probably involves a 1,6-hydrogen atom translocation. The results showed that the dealkylation is an integral part of the reaction mechanism and not a subsequent reaction of 2-alkoxybenzonitriles.
- Leardini, Rino,McNab, Hamish,Minozzi, Matteo,Nanni, Daniele,Reed, David,Wright, Andrew G.
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p. 2704 - 2710
(2007/10/03)
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- Sol-gel entrapped chromium(VI): A new selective, efficient and recyclable oxidizing system
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The sol-gel entrapment of chromium(VI) within a silica matrix, obtained by oxidation with ozone of the corresponding entrapped chromium(III), was found to be an efficient and recyclable oxidizing system (at least up to 16 times) for benzylic alcohols. No leaching of chromium in solution was observed, which prevented any environmental pollution.
- Gruttadauria, Michelangelo,Liotta, Leonarda F,Noto, Renato,Deganello, Giulio
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p. 5199 - 5201
(2007/10/03)
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- Method for inhibition of HIV related viruses
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Treatment of AIDS, inhibition of the replication of HIV and related viruses thereof, and formulations using thiourea derivative compounds or salts thereof is disclosed. Also disclosed are novel thiourea derivative compounds.
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- Selective reduction with lithium bis- Or tris(dialkylamino)aluminum hydrides. III. Reduction of primary carboxamides to aldehydes by lithium tris(diethylamino)aluminum hydride
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Both aliphatic and aromatic primary carboxamides are reduced readily to the corresponding aldehydes by lithium tris(diethylamino)aluminum hydride in THF at room temperature in yields of 50-90%.
- Cha, Jin Soon,Lee, Jae Cheol,Lee, Heung Soo,Lee, Sung Eun,Kim, Jong Mi,Kwon, Oh Oun,Min, Soo Jin
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p. 6903 - 6904
(2007/10/02)
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- Process for nucleophilic fluoroalkylation of aldehydes
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Aryl difluoromethyl sulfone adds to alkehydes under phase transfer conditions to give novel substituted alcohols of the general formula wherein R is an aryl, cycloaliphatic, sec- or tert-aliphatic, or heterocyclic group and Ar is an aryl group. The substituted alcohols of formula I are of particular utility as intermediates in the synthesis of a variety of useful end products. For example, the products of formula I may be utilized in desulfonylation reactions, oxidation reactions and fluorination reactions.
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- OXIDATIVE DEAMINATION OF BENZYLIC AMINES INDUCED BY PHENYL DICHLOROPHOSPHATE
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Treatment of benzylic amines with phenyl dichlorophosphate and dimethyl sulfoxide followed by sequential addition of triethylamine and oxalic acid gave rise to the corresponding carbonyl compounds.
- Liu, Hsing-Jang,Nyangulu, James M.
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p. 3407 - 3412
(2007/10/02)
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- The Baeyer-Villiger Oxidation of Aromatic Aldehydes and Ketones with Hydrogen Peroxide Catalyzed by Selenium Compounds
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A series of organoselenium compounds was investigated as activators of hydrogen peroxide in the Baeyer-Villiger oxidation.As a result, a convenient and cheap method for transformation of aromatic aldehydes, having polycondensed ring systems or electron-donating substituents, and polymethoxy derivatives of acetophenone, into phenols was elaborated.This method utilizes hydrogen peroxide activated by areneseleninic acids, as oxidizing agent.
- Syper, Ludwik
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p. 167 - 172
(2007/10/02)
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- 3-(substituted phenyl)phthalides
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Process comprises the combination of the three steps of condensing 3-N(R)2 -4-X-benzoic acid with an aromatic or heterocyclic aldehyde, Y-CHO, under acidic conditions to produce 3-Y-5-X-6-N(R)2 phthalide (II), condensing said phthalide with a compound of the formula Z-H under alkaline or acid conditions to produce 2-(α-Y-α-Z)methyl-4-X-5-N(R)2 benzoic acid (III), and oxidizing said benzoic acid to produce 3-Y-3-Z-5-X-6-N(R)2 phthalide (I) where: R is hydrogen, non-tertiary alkyl of one to four carbon atoms, benzyl or substituted benzyl; X is hydrogen or halo; Y is 4-R1 -3-R2 -2-R1 -phenyl, 1-R5 -2-R6 -5/6-R4 -3-indolyl, 9-R7 -3-carbazolyl, 9-julolidinyl, 3,4-dioxymethylenephenyl, 2-thienyl, 1-R8 -2-pyrrolyl, or 4-pyridinyl; and Z is 4-R1 -3-R2 -2-R1 -phenyl, 1-R5 -2-R6 -5/6-R4 -3-indolyl or 1-R8 -2-pyrrolyl which are useful as colorless precursor color formers in carbonless duplicating and in thermal marking systems. The intermediates, 3-Y-5-X-6-N(R)2 phthalides (II) and 2-(α-Y-α-Z)methyl-4-X-5-N(R)2 benzoic acids (III) also have utility as colorless precursor color formers in carbonless duplicating and thermal marking systems.
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- Novel compounds, processes and marking systems
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Mono and bis substituted (arylsulfonyl)alkanes useful as color formers, particularly in carbonless duplicating and thermal marking systems, are prepared by the interaction of the appropriate aldehyde or dialdehyde with the appropriate aryl or heterocyclic moiety and the appropriate phenylsulfinic acid in the presence of a catalyst.
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