cas 626-43-7, 3,5-Dichloroaniline | Articles data

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Determination and identification of metabolites of the fungicides Iprodione and Procymidone in compost
The main metabolites formed from Iprodione and Procymidone during the composting process have been isolated and identified by HPLC-DAD-MSD. After addition of the fungicides to the composting pile, we monitored the reaction of the two analytes and the form
Vanni, Adriano,Gamberini, Roberta,Calabria, Adelaide,Nappi, Pina
p. 1431 - 1439
(2000)
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Chemical and Biological Transformation of the Fungicide Vinclozolin
Two mixed bacterial cultures were isolated from a French soil adapted to the dicarboximide fungicide vinclozolin. The vinclozolin was transformed by the mixed bacterial cultures according to two degradation pathways: (a) the formation of 2-[[(3,5-dichlorophenyl)carbamoyl]oxy]-2-methyl-3-butenoic acid and then 3,5-dichloroaniline or (b) the formation of 3′,5′-dichloro-2-hydroxy-2-methylbut-3-enanilide and then 3,5-dichloroaniline. The structure of 2-[[(3,5-dichlorophenyl)-carbamoyl]oxy]-2-methyl-3-butenoic acid was unambiguously established by 1H and 13C 2-D NMR analysis. A bacterial strain isolated from soil that degrades this compound was identified as a strain of Corynebacterium sp. Attempts to obtain pure vinclozolin-degrading strains via 3′,5′-dichloro-2-hydroxy-2-methylbut-3-enanilide were unsuccessful.
Mercadier, Christine,Vega, Danielle,Bastide, Jean
p. 3817 - 3822
(1998)
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High yielding electrophilic amination with lower order and?higher order organocuprates: Application of acetone O-(4-Chlorophenylsulfonyl)oxime in the construction of the C?N bond at room temperature
Electrophilic amination reaction was performed with lower order and?higher order organocuprates using acetone O-(4-Chlorophenylsulfonyl)oxime (1). It was proceeded smoothly at room temperature in the presence of organocuprates to provide the corresponding primary amines in good yields with 10 and 60 min, respectively. The primary amine yields of the electrophilic amination of bromomagnesium organocyanocuprates and dibromomagnesium diorganocyanocuprates were obtained 52–72% and 58–83%, respectively. We observed that higher order organocuprates were more successful than lower order organocuprates in the synthesis of functionalized arylamines by electrophilic amination.
Duran, Serdar,Korkmaz, Adem
p. 2077 - 2087
(2021/05/27)

Cyclic (Alkyl)(amino)carbene Ligand-Promoted Nitro Deoxygenative Hydroboration with Chromium Catalysis: Scope, Mechanism, and Applications
Transition metal catalysis that utilizes N-heterocyclic carbenes as noninnocent ligands in promoting transformations has not been well studied. We report here a cyclic (alkyl)(amino)carbene (CAAC) ligand-promoted nitro deoxygenative hydroboration with cost-effective chromium catalysis. Using 1 mol % of CAAC-Cr precatalyst, the addition of HBpin to nitro scaffolds leads to deoxygenation, allowing for the retention of various reducible functionalities and the compatibility of sensitive groups toward hydroboration, thereby providing a mild, chemoselective, and facile strategy to form anilines, as well as heteroaryl and aliphatic amine derivatives, with broad scope and particularly high turnover numbers (up to 1.8 × 106). Mechanistic studies, based on theoretical calculations, indicate that the CAAC ligand plays an important role in promoting polarity reversal of hydride of HBpin; it serves as an H-shuttle to facilitate deoxygenative hydroboration. The preparation of several commercially available pharmaceuticals by means of this strategy highlights its potential application in medicinal chemistry.
Zhao, Lixing,Hu, Chenyang,Cong, Xuefeng,Deng, Gongda,Liu, Liu Leo,Luo, Meiming,Zeng, Xiaoming
supporting information
p. 1618 - 1629
(2021/01/25)

Mechanochemical synthesis of aromatic sulfonamides
A three-component Pd-catalysed aminosulfonylation reaction of K2S2O5 and amine with aryl bromides or aromatic carboxylic acids was developed. This strategy was developed to utilise mechanical energy and accommodate primary as well as secondary aliphatic and aromatic amines to provide a new shortcut to a wide range of sulfonamides. Studies on the scope and limitations of the reaction indicated its tolerance of a vast range of functional groups and many structural patterns. The reactions were scaled up to gram quantities.
Mkrtchyan, Satenik,Iaroshenko, Viktor O.
supporting information
p. 11029 - 11032
(2021/11/03)

Room-temperature copper-catalyzed electrophilic amination of arylcadmium iodides with ketoximes
We started our study by preparation two ketoximes. Later, there were studies to reveal these ketoximes' effects in the electrophilic amination reaction with organocadmium reagents. Primarily, it was observed that arylcadmium iodides could not be reacted with ketoximes at room temperature in the absence of a catalyst. CuCN was a suitable catalyst for this electrophilic amination reaction of arylcadmium iodides and allowed the preparation of functionalized aniline derivatives in good yields under mild reaction conditions. We obtained the results indicated that the yield of primary arylamines was strongly dependent on the steric and electronic effects of organocadmium reagent and amination agent. In the case of both amination reagents, meta-substituted arylamines were obtained in higher yields than para-substituted arylamines. We observed that acetone O-(4-chlorophenylsulfonyl)oxime, 1, as an aminating agent, was more successful than acetone O-(2-Naphthylsulfonyl)oxime, 2, in the synthesis of functionalized arylamines by electrophilic amination of corresponding aryl cadmium iodides. In this method, there is no cadmium release to the environment.
Korkmaz, Adem
p. 3119 - 3125
(2021/05/10)

Hydrogenation of nitroarenes to anilines in a flow reactor using polystyrene supported rhodium in a catalyst-cartridge (Cart-Rh@PS)
The present methodology described the chemo-selective hydrogenation of various nitroarenes in a flow reactor under polystyrene supported rhodium in a catalyst-cartridge (Cart-Rh@PS) as a heterogeneous nano-catalyst. The polystyrene supported Rh (Rh@PS) nanoparticles (NPs) were prepared by following our earlier reported protocol and packed inside the catalyst-cartridge (Cat-Cart) to obtain Cart-Rh@PS, which is compatible with ThalesNano's H-Cube Pro flow system. The advantages of the prepacked catalyst Cart-Rh@PS are as follows: no need for catalyst activation up to 12 runs, negligible metal leaching detected by ICP-AES analysis and significantly less back pressure generated under the flow conditions. The same catalyst, Cart-Rh@PS, was also effective up to a 1 gram scale for the reduction of nitroarenes and reusable for successive runs. The hydrogenation in the flow reactor is a greener approach for the reduction of nitroarenes to their corresponding anilines in high yields.
Sharma, Saurabh,Yamini,Das, Pralay
supporting information
p. 1764 - 1769
(2019/01/28)

meta-Nitration of Arenes Bearing ortho/para Directing Group(s) Using C?H Borylation
Herein, we report the meta-nitration of arenes bearing ortho/para directing group(s) using the iridium-catalyzed C?H borylation reaction followed by a newly developed copper(II)-catalyzed transformation of the crude aryl pinacol boronate esters into the corresponding nitroarenes in a one-pot fashion. This protocol allows the synthesis of meta-nitrated arenes that are tedious to prepare or require multistep synthesis using the existing methods. The reaction tolerates a wide array of ortho/para-directing groups, such as ?F, ?Cl, ?Br, ?CH3, ?Et, ?iPr ?OCH3, and ?OCF3. It also provides regioselective access to the nitro derivatives of π-electron-deficient heterocycles, such as pyridine and quinoline derivatives. The application of this method is demonstrated in the late-stage modification of complex molecules and also in the gram-scale preparation of an intermediate en route to the FDA-approved drug Nilotinib. Finally, we have shown that the nitro product obtained by this strategy can also be directly converted to the aniline or hindered amine through Baran's amination protocol.
Li, Xuejing,Deng, Xingwang,Coyne, Anthony G.,Srinivasan, Rajavel
supporting information
p. 8018 - 8023
(2019/05/29)

A 3, 5 - dichloroaniline synthetic method (by machine translation)
The invention discloses a 3, 5 - dichloroaniline synthetic method, in order to 1, 3, 5 - trichlorobenzene as raw materials, in the organic solvent, the addition of a base, ammonia solution or ammonium salt as the Ammon, the transition metal catalyst and under the action of the ligand, coupled reactions, to obtain the product 3, 5 - dichloroaniline. The method of the invention, and is simple, low cost, simple synthesis steps, only one step reaction can be by the 1, 3, 5 - trichlorobenzene direct coupling with ammonia to obtain the product 3, 5 - dichloroaniline, few by-products, three wastes, environmental protection, the updating process of the product, for reducing the 3, 5 - dichloroaniline and its synthesis of derivatives cost is of great significance. (by machine translation)
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Paragraph 0035-0050

(2017/07/19)

Glucose promoted facile reduction of azides to amines under aqueous alkaline conditions
A quick and efficient method for the reduction of azides to amines in water using d-glucose and KOH as green reagents is reported. The protocol is simple, inexpensive, scalable, and can be applied to different aromatic, heteroaromatic and sulphonyl azides. A high level of chemoselectivity is observed for azide reduction in the presence of other reducible functionalities like cyano, nitro, ether, ketone, amide and acid. The reaction gets completed in a short time (5-20 minutes), and furnishes the amines in high yield (85-99%). Unlike conventional hydrogenations, this reduction protocol does not require any metal catalyst, elaborate experimental setup or use of high-pressure equipment.
Chandna, Nisha,Kaur, Fatehjeet,Kumar, Shobhna,Jain, Nidhi
supporting information
p. 4268 - 4271
(2017/09/29)

Chemoselective transfer hydrogenation of nitroarenes by highly dispersed Ni-Co BMNPs
Highly dispread Ni-Co bimetallic nanoparticles (Ni-Co BMNPs) are synthesized and applied as an efficient catalyst in the chemoselective transfer hydrogenation of nitroarenes (CTH) using hydrazine hydrate as the hydrogen donor. The BMNPs can efficiently catalyze the reduction reaction without any additives under mild conditions with high TOF. Significantly higher activity is achieved when compared with corresponding single-component catalysts, optimal composition of the Ni-Co BMNPs was screened which was proved to be crucial in both the selectivity and yields. Excellent performance of Ni-Co BMNPs can be ascribed to the improved dispersion of active sites on the BMNPs surface (compared with Ni NPs) and the electron transfer from cobalt to nickel.
Zhang, Jia-Wei,Lu, Guo-Ping,Cai, Chun
p. 25 - 29
(2016/06/13)

Aryl C-N bond formation by electrophilic amination of diarylcadmium reagents with O-substituted ketoximes
Diorganocadmium reagents cannot react with ketoxime at room temperature. CuCN catalysis allows diarylcadmium reagents to react with ketoxime and to give corresponding arylamines in good to high yields at room temperature. According to the electronic effects of the substituent attached to the aromatic ring, functionalized diarylcadmium reagents show meta-para selectivity in their amination reactions. Also compared to diarylzinc reagents, diarylcadmium reagents react with O-substituted ketoxime under milder reaction conditions and they form corresponding arylamines in higher yields. CuCN cannot help dialkyl-, dicycloalky-, and dibenzylcadmium reagents to react with ketoxime. Our Aryl C-N bond formation method does not include cadmium excretion into the environment.
Da?kapan, Tahir,Korkmaz, Adem
supporting information
p. 813 - 817
(2016/07/06)

USE OF THERMALLY-TREATED SUPPORTED COBALT CATALYSTS COMPRISING A POLYCYCLIC AROMATIC STRUCTURE CONSISTING OF NITROGEN LIGANDS FOR HYROGENATING AROMATIC NITRO COMPOUNDS
The invention relates to the use of thermally-treated supported cobalt catalysts for hydrogenating aromatic nitro compounds, the cobalt catalysts having been prepared by in situ immobilization of a cobalt-amine complex on an inorganic porous support and subsequent pyrolysis, and, in the cobalt-amine complex used, cobalt being present bonded to an aromatic or heterocyclic nitrogen ligand L, the nitrogen ligand being selected so as to form a polyaromatic structure with the cobalt atom.
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Paragraph 0031; 0032

(2015/11/16)

Iridium-catalyzed transfer hydrogenation of nitroarenes to anilines
A simple and general homogeneous catalyst system composed of commercially available [Ir(cod)Cl]2 and 1,10-phenanthroline has been developed for the selective transfer hydrogenation of nitroarenes to anilines. It utilized the readily accessible 2-propanol as a hydrogen donor and had wide substrate scope. A careful mechanistic investigation through real-time detection and a series of controlled experiments with possible intermediates was also carried out, which showed that the transformation proceeds via both phenylhydroxylamine and azobenzene intermediates and the reduction of hydrazobenzene leading to aniline might be the rate-determining step.
Chen, Shujie,Lu, Guoping,Cai, Chun
p. 5360 - 5365
(2015/07/07)

Alkaline hydrolysis of vinclozolin: Effect of humic acids aggregates in water
The influence of natural organic substances as humate colloidal aggregates in water solutions upon the chemical stability of vinclozolin has been investigated in basic media. A large inhibition (9 times-fold) has been observed and it has been rationalized in terms of a micellar pseudophase model. The observed behaviour could increase significantly the half-life of this fungicide. Moreover, these experimental results have been compared with the corresponding ones of other substances in these natural colloidal aggregates.
Morales,Cid,Mejuto
p. 13 - 17
(2015/03/14)

Heterogenized cobalt oxide catalysts for nitroarene reduction by pyrolysis of molecularly defined complexes
Molecularly well-defined homogeneous catalysts are known for a wide variety of chemical transformations. The effect of small changes in molecular structure can be studied in detail and used to optimize many processes. However, many industrial processes require heterogeneous catalysts because of their stability, ease of separation and recyclability, but these are more difficult to control on a molecular level. Here, we describe the conversion of homogeneous cobalt complexes into heterogeneous cobalt oxide catalysts via immobilization and pyrolysis on activated carbon. The catalysts thus produced are useful for the industrially important reduction of nitroarenes to anilines. The ligand indirectly controls the selectivity and activity of the recyclable catalyst and catalyst optimization can be performed at the level of the solution-phase precursor before conversion into the active heterogeneous catalyst.
Westerhaus, Felix A.,Jagadeesh, Rajenahally V.,Wienhoefer, Gerrit,Pohl, Marga-Martina,Radnik, Joerg,Surkus, Annette-Enrica,Rabeah, Jabor,Junge, Kathrin,Junge, Henrik,Nielsen, Martin,Brueckner, Angelika,Beller, Matthias
p. 537 - 543
(2013/07/19)

Ultraviolet degradation of procymidone - Structural characterization by gas chromatography coupled with mass spectrometry and potential toxicity of photoproducts using in silico tests
RATIONALE Procymidone is a dicarboximide fungicide mainly used for vineyard protection but also for different crops. The structural elucidation of by-products arising from the UV-visible photodegradation of procymidone has been investigated by gas chromatography coupled with mass spectrometry. The potential toxicities of photoproducts were estimated by in silico tests. METHODS Aqueous solutions of procymidone were irradiated for up to 90 min in a self-made reactor equipped with a mercury lamp. Analyses were carried out on a gas chromatograph coupled with an ion trap mass spectrometer operated in electron ionization and methanol positive chemical ionization. Multistage collision-induced dissociation (CID) experiments were performed to establish dissociation pathways of ions. Toxicities of byproducts were estimated using the QSAR T.E.S.T. program. RESULTS Sixteen photoproducts were investigated. Chemical structures were proposed mainly based on the interpretation of multistage CID experiments, but also on their relative retention times and kinetics data. These structures enabled photodegradation pathways to be suggested. Only three photoproducts remain present after 90 min of irradiation. Among them, 3,5-dichloroaniline presents a predicted rat LD50 toxicity about ten times greater than that of procymidone. CONCLUSIONS 3,5-Dichloroaniline is the only photoproduct reported in previous articles. Eight by-products among the sixteen characterized might be as toxic, if not more, than procymidone itself considering the QSAR-predicted rat LD50. Copyright 2013 John Wiley & Sons, Ltd. Copyright
Rifai, Ahmad,Souissi, Yasmine,Genty, Christophe,Clavaguera, Carine,Bourcier, Sophie,Jaber, Farouk,Bouchonnet, Stéphane
p. 1505 - 1516
(2013/07/27)

Mild and highly selective palladium-catalyzed monoarylation of ammonia enabled by the use of bulky biarylphosphine ligands and palladacycle precatalysts
A method for the Pd-catalyzed arylation of ammonia with a wide range of aryl and heteroaryl halides, including challenging five-membered heterocyclic substrates, is described. Excellent selectivity for monoarylation of ammonia to primary arylamines was achieved under mild conditions or at rt by the use of bulky biarylphosphine ligands (L6, L7, and L4) as well as their corresponding aminobiphenyl palladacycle precatalysts (3a, 3b, and 3c). As this process requires neither the use of a glovebox nor high pressures of ammonia, it should be widely applicable.
Cheung, Chi Wai,Surry, David S.,Buchwald, Stephen L.
supporting information
p. 3734 - 3737
(2013/08/23)

Highly selective hydrogenation of halonitroaromatics to aromatic haloamines by ligand modified Ni-based catalysts
Ligand modification of Ni-based catalysts by coordination of dicyandiamide to Ni metal leads to enhanced selectivity for the selective hydrogenation of halonitroaromatics. The selectivity of above 99.9% to aromatic haloamines can be achieved at the conversion of 100%. The results of H2-TPD and FT-IR experiments show that Ni-H+ species possessing the properties of Lewis acid site on the surface of Raney Ni could be responsible for the hydrodehalogenation. When Raney Ni was treated by dicyandiamide, Ni -H+ species interacted with N atom from the dicyandiamide. This interaction was stable even at reaction temperature, which reduced the possibility to form the intermediate state of ArCl?H+Ni -. And then CCl bond could not be polarized and activated. The hydrodechlorination process was suppressed effectively.
Lu, Chun Shan,Lv, Jing Hui,Ma, Lei,Zhang, Qun Feng,Feng, Feng,Li, Xiao Nian
experimental part
p. 545 - 548
(2012/06/16)

Efficient and highly selective iron-catalyzed reduction of nitroarenes
Pyrolysis of iron-phenanthroline complexes supported on carbon leads to highly selective catalysts for the reduction of structurally diverse nitroarenes to anilines in 90-99% yields. Excellent chemoselectivity for the nitro group reduction is demonstrated.
Jagadeesh, Rajenahally V.,Wienhoefer, Gerrit,Westerhaus, Felix A.,Surkus, Annette-Enrica,Pohl, Marga-Martina,Junge, Henrik,Junge, Kathrin,Beller, Matthias
supporting information; experimental part
p. 10972 - 10974
(2011/10/31)

Orally active aminopyridines as inhibitors of tetrameric fructose-1,6-bisphosphatase
A novel sulfonylureido pyridine series exemplified by compound 19 yielded potent inhibitors of FBPase showing significant glucose reduction and modest glycogen lowering in the acute db/db mouse model for Type-2 diabetes. Our inhibitors occupy the allosteric binding site and also extend into the dyad interface region of tetrameric FBPase.
Hebeisen, Paul,Haap, Wolfgang,Kuhn, Bernd,Mohr, Peter,Wessel, Hans Peter,Zutter, Ulrich,Kirchner, Stephan,Ruf, Armin,Benz, J?rg,Joseph, Catherine,Alvarez-Sánchez, Rubén,Gubler, Marcel,Schott, Brigitte,Benardeau, Agnes,Tozzo, Effie,Kitas, Eric
scheme or table
p. 3237 - 3242
(2011/07/07)

Copper-catalyzed synthesis of azaspirocyclohexadienones from ∝-azido- N -arylamides under an oxygen atmosphere
A copper-catalyzed reaction of ∝-azido-N-arylamides was found to proceed under an oxygen atmosphere to afford azaspirocyclohexadienones. The present transformation is carried out by a sequence of denitrogenative formation of iminyl copper species from ∝-azido-N-arylamides and their imino-cupration with an intramolecular benzene ring on the amido nitrogen followed by consecutive formation of C-O bonds. The preliminary investigation revealed that molecular oxygen is a prerequisite for achieving the present catalytic cyclization and that one of the oxygen atoms of O2 was found to be incorporated into the cyclohexadienone moiety.
Chiba, Shunsuke,Zhang, Line,Lee, Jian-Yuan
supporting information; experimental part
p. 7266 - 7267
(2010/08/05)

PROCESS FOR THE PREPARATION OF SUBSTITUTED HALOGENATED ANILINE
A process for the preparation of substituted halogenated anilines from substituted halogenated 1-chlorobenzenes which comprisesa) reacting a substituted halogenated 1-chlorobenzene selectively with an imine in the presence of a transition metal catalyst complex and a base to form an N-aryl imine; b) hydrolyzing the N-aryl imine; andc) isolating the substituted halogenated aniline.
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Page 5

(2008/06/13)

Analogues of camptothecin, their use as medicaments and the pharmaceutical compositions containing them
A compound of the formula wherein the substituents are defined as in the specification which compounds are useful in the treatment of cancer.
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(2008/06/13)

Allylic amination of unfunctionalyzed olefins by nitroarenes and CO, catalyzed by Ru3(CO)12/Ph-BIAN (Ph-BIAN=bis(phenylimino) acenaphthenequinone): Extension to the synthesis of allylic amines with strongly electron-withdrawing or el
The allylic amination of unfunctionalyzed olefins by nitroarenes under CO pressure, catalyzed by Ru3(CO)12/Ph-BIAN (Ph-BIAN=bis(phenylimino)acenaphthenequinone) has been extended to some substrates with strongly electron-withdrawing
Ragaini, Fabio,Cenini, Sergio,Turra, Fabrizio,Caselli, Alessandro
p. 4989 - 4994
(2007/10/03)

Process for preparing pesticidal intermediates
The invention relates to processes for the preparation of compounds of formula (I) wherein R1and R2each independently represent a halogen atom.
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(2008/06/13)

4-(Phenylamino)-[1,4]dioxano[2,3-g]quinazoline derivatives and process for preparing the same
The present invention relates to 4-(phenylamino)-[1,4]dioxano[2,3-g]quinazoline derivatives which inhibit tyrosine kinase of epidermal growth factor receptor (EGFR), and pharmaceutically acceptable salts, hydrates and solvates thereof, and a process for preparing the same. Since 4-(phenylamino)-[1,4]dioxano[2,3-g]quinazoline derivatives of the invention have a high solubility in water and inhibit the activity of EGFR tyrosine kinase and the growth of cancer cells, they can be practically applied in the treatment of overproliferation-associated diseases such as cancer.
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(2008/06/13)

New analogues of camptothecin, their use as medicaments and the pharmaceutical compositions containing them
A compound of the formula wherein the substituents are defined as in the specification which compounds are useful in the treatment of cancer.
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(2008/06/13)

Camptothecin analogues, preparation methods therefor, use thereof as drugs, and pharmaceutical compositions containing said analogues
A camptothecin analog characterized in that the hydroxy lactone of the camptothecin is a β-hydroxy lactone or the corresponding β-hydroxyacid, resulting from the opening of said lactone, or a derivative of said β-hydroxyacid, or a Pharmaceutically acceptable salt thereof, is disclosed. In particular, compounds of formulae (I) and (II) are disclosed. Methods for preparing the compounds of formulae (I) and (II), pharmaceutical compositions containing said containing said compounds, and their use, particularly as topoisomerase inhibitors and antitumoral drugs, are also disclosed.
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(2008/06/13)

Photochemistry of vinclozolin in water and methanol-water solution
The photolysis of the fungicide vinclozolin in aqueous and methanol- water (50+50 by volume) solution has been examined. Irradiation at λ=254nm for 10 minutes resulted in 2 moiety takes place, and one or both the chlorine atoms are replaced by a methoxy group.
Schick,Moza,Hustert,Kettrup
p. 1116 - 1122
(2007/10/03)

Intermediates for producing 5,7-dichloro-4-hydroxyquinoline
An industrially advantageous process for producing 5,7-dichloro-4-hydroxyquinoline (DCHQ) useful as an intermediate for agrohorticultural bactericides. The process comprises (i) hydrolyzing 3-cyano- or 3-ethoxycarbonyl-5,7-dichloro-4-hydroxyquinoline into 5,7-dichloro-3-carboxy-4-hydroxyquinoline (DCQA) in the presence of hydrochloric, sulfuric or phosphoric acid and (ii) decarboxylating the formed DCQA into DCHQ in the presence of sulfuric or phosphoric acid. In particular, this process comprises continuously conducting the hydrolysis of 5,7-dichloro-3-ethoxycarbonyl-4-hydroxyquinoline and the decarboxylation of the hydrolyzate in the presence of sulfuric acid having a specified concentration. The invention also relates to a process for producing DCQA by hydrolyzing 3-cyano- or 3-ethoxycarbonyl-5,7-dichloro-4-hydroxyquinoline in the presence of hydrochloric, sulfuric or phosphoric acid and a process for producing DCHQ by decarboxylating DCQA in the presence of sulfuric or phosphoric acid.
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(2008/06/13)

Iprodione degradation by isolated soil microorganisms
Three bacterial strains were isolated from soils adapted to iprodione and identified as Pseudomonas fluorescens, Pseudomonas sp. and Pseudomonas paucimobilis. The first two strains transformed iprodione to N-(3,5- dichlorophenyl)-2,4-dioxoimidazo-lidine (II) and under restrictive conditions to 3,5-dichlorophenylurea acetic acid (III); the latter subsequently degraded II to III and III to 3,5-dichloroaniline (3,5-D). We constructed bacterial combinations consisting of Pseudomonas paucimobilis plus one of the iprodione degraders and showed that these combinations transformed iprodione into 3,5- D. It is known that 3,5-D was the major metabolite found in adapted soils, suggesting that such a bacterial combination might be responsible for degrading iprodione into 3,5-D in adapted soils. Plasmids could only be isolated in Pseudomonas fluorescens but we did not investigate if one of these was involved in the ability to degrade iprodione.
Mercadier, Christine,Vega, Danielle,Bastide, Jean
p. 207 - 215
(2007/10/03)

Magnetic susceptibilities of organic compounds: Part V - Influence of substituents on diamagnetic susceptibilities of disubstituted and trisubstituted benzenes
The magnetic susceptibilities of a number of triads of isomeric disubstituted benzenes have been determined, choosing the compounds in such a way that the substituents are present in the following combinations: (i) two electron-releasing substituents, (ii) a halogeno and an electron-releasing substituent, (iii) a halogeno and an electron-attracting substituent, and (iv) two halogeno substituents.The data show that for types (i), (ii) and (iv), the ortho isomers have the highest magnetic susceptibilities, the susceptibilities decreasing in the order: ortho > meta > para; for type (iii), the meta-isomers have the highest susceptibilities, the susceptibilities decreasing in the order: meta > para > ortho.The diamagnetic susceptibilities of some isomeric trisubstituted benzenes have also been determined and the data reveal that the susceptibility is the highest where the crowding of substituents is the highest (1,2,3-isomer) and lowest where the substituents are staggered and least crowded (1,3,5-isomer).Another observation made in the case of trisubstituted benzene is the applicability of a principle of additivity of their diamagnetic susceptibilities.
Baliah, V.,Jeyanthy, J. Judith Diana
p. 472 - 476
(2007/10/02)

Sulphinamoylacetates as sulphine precursors. Mechanism of basic hydrolysis and scheme of irreversible inactivation of cinnamoyl alcohol dehydrogenase, an enzyme of the lignification process
t-Butyl N-arylsulphinamoylacetates are hydrolysed in aqueous basic media by an elimination mechanism. It takes place on the conjugate base of the substrate resulting from a fast deprotonation of the activated methylene group. This elimination is first order (E1cB) for compounds where strong electron-withdrawing groups substitute the aromatic ring. For substitution by weaker electron-withdrawing or -donating groups, the elimination is second order, and needs the presence of general acid catalysis. For t-butyl N-(2-hydroxyphenyl)sulphinamoylisobutyrate where this mechanism of elimination is impossible, a BAc2 attack by hydroxide ion at the sulphur atom takes place. From these mechanisms and the results of complexation of zinc(II) cations by sulphinamoylacetates, a possible scheme for the irreversible inactivation of the title zinc metalloenzyme is proposed.
Baltes, Michel,Cazaux, Louis,Gorrichon, Liliane,Maroni, Pierre,Tisnes, Pierre
p. 1473 - 1478
(2007/10/02)

Process for the preparation of meta-halogenoanilines
Process for the preparation of anilines substituted in the meta-position by a halogen atom. An aniline of the formula: STR1 in which: X' and X", R', R" and R"' are a halogen atom, alkyl (C1 -C4) or alkoxy (C1 -C4), one of the symbols X and one of the symbols R necessarily being a halogen and it being possible for one of the symbols X and one of the symbols R to be a hydrogen atom, is subjected to catalytic hydrogenation, in an anhydrous organic liquid phase, namely a chlorobenzene phase, in the presence of a halogen-containing hydracid and of a noble metal from group VIII of the periodic classification.
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(2008/06/13)

Process for the preparation of optionally halogenated anilines
Process for the manufacture of an optionally halogenated aniline of the formula: STR1 in which Y=halogen, R=H, alkyl (C1 -C4) or alkoxy (C1 -C4) and n=0 to 5. Halogenobenzenes of the formula: STR2 in which Y, R and n are as above and X=halogen, are subjected to ammonolysis with aqueous ammonia solution, in the presence of copper and 8-hydroxyquinoline. The process can be used, in particular, for the preparation of 3,5-dichloroaniline.
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(2008/06/13)

Process for preparation of anilines which are m-substituted by chlorine
The invention relates to a process for the preparation of anilines which are m-substituted by chlorine, by selective dehalogenation of more highly chlorinated anilines in an acid medium in the presence of noble metal catalysts and in the presence of optionally substituted phenols. The 3-chloro- or 3,5-dichloroanilines obtainable by the process according to the invention are known intermediate products, and can be used for the preparation of plant protection agents.
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(2008/06/13)

Process for the selective preparation of meta-chloroanilines
Process for the selective preparation of meta-chloroanilines. It is carried out by the hydrodechlorination of polychloroanilines or polychloronitrobenzenes with hydrogen, in the liquid phase, under the action of heat, at atmospheric pressure or under pressure, in the presence of a noble metal, in an anhydrous organic medium and in the presence of a Lewis acid. These meta-chloroanilines are intermediates especially for active plant-protection substances.
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(2008/06/13)

Process for preparation of anilines substituted by chlorine in the meta-position
A process for the dechlorination of aromatic nitro or amino compounds consists in reacting anilines or nitrobenzenes which are polysubstituted by chlorine, with hydrogen, under the action of heat, in the presence of iodide or bromide ions, in the liquid phase and at low pressure. The process makes it possible selectively to obtain anilines which are chlorine-substituted in the meta-position.
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(2008/06/13)

Pathways for the Decomposition of Alkylaryltriazenes in Aqueous Solution
Primary alkylaryltriazenes give solvent-equilibrated alkenediazonium ions and anilines in aqueous solution at 25 deg C by two processes.The first, an A-SE2(N) reaction, involves immobilisation of a molecule of catalysing acid, and a transition state in which the proton is essentially completely transferred and little breakage of the N-N bond has occurred.The structure of this transition state varies with the strength of the catalysing acid and the pKa of the liberated aniline in a way interpretable in terms of a More O'Ferrall-Jencks diagram.The second process is the departure of aniline anion without acid assistance.The first process is governed by positive, the second by negative, βlg values.
Jones, Caroline C.,Kelly, Migel A.,Sinnott, Michael L.,Smith, Paul J.,Tzotzos, George T.
p. 1655 - 1664
(2007/10/02)

Effect of Aryl Substituents on the Kinetics of Inactivation of Glycosidases by Glycosylmethylaryltriazenes: Examination of the 'Suicide' Nature of these Inactivations
The inactivation of the Mg2+-free form of the lacZ-β-galactosidase of Escherichia coli at 25.0 deg C by various β-D-galactopyranosylmethylaryltriazenes resembles the spontaneous, rather than the acid-catalysed decomposition of alkylaryltriazenes in that both the maximum first-order rate constant, and the second-order rate constant, are governed by a negative βlg value at pH 7.0 and at pH 8.0.Less extensive data with the β-xylosidase of Penicillium wortmanni and β-D-xylopyranosylmethylaryltriazenes give a similar result.Although the decomposition of the 2-(β-D-galactopyranosyl)ethyl compounds in aqueous solution is 5-10 fold faster than their lower homologues, β-galactosidase inactivation is 3-13 slower. β-D-Galactopyranosylmethyl-p-nitrophenyltriazene does not inactivate the lectin, RCA ricin.
Sinnott, Michael L.,Tzotzos, George T.,Marshall, Susan E.
p. 1665 - 1670
(2007/10/02)

Process for preparing 3-chloro- and 3,5-dichloro-anilines
Analines, meta-substituted by chlorine are prepared by reacting chloro-anilines having the formula STR1 wherein X1 and X2 are the same or different and represent chlorine, hydrogen or optionally substituted alkyl, aryl, aralkyl, alkoxy or aralkoxy, with one of the radicals X1 or X2 representing chlorine when 3-chloroanilines are being prepared and X1 and X2 representing chlorine when 3,5-dichloroanilines are being prepared and R1, R2 and R3 are the same or different and represent chlorine, hydrogen or optionally substituted alkyl, aryl, aralkyl, alkoxy or aralkoxy, with at least one of the radicals R1, R2 or R3 representing chlorine with hydrogen in solution in a neutral or acid medium in the presence of noble metals which are in the elementary form or in the form of compounds and are optionally applied to supports, and in the presence of sulfur or sulfur compounds at elevated temperatures and under pressure.
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(2008/06/13)

Process for producing 3,5-dichloroaniline from 1-bromo-2,4-dichlorobenzene
3,5-Dichloroaniline is advantageously produced by reacting 1-bromo-2,4-dichlorobenzene with a metal amide in liquid ammonia at a molar ratio of 1-bromo-2,4-dichlorobenzene to the metal amide of 1 : 2 to 7. The 3,5-dichloroaniline is useful as an intermediate for various agricultural chemicals, dyes and medicines.
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(2008/06/13)

Antimicrobial composition and method containing N-(3,5-dihalophenyl)-imide compounds
Novel N-(3,5-dihalophenyl)imide compounds, which exhibit a strong antimicrobial activity against microorganisms including phytopathogenic fungi, parasites of industrial products and pathogenic microorganisms, represented by the formula, STR1 wherein X and X' each represent halogens and A represents a substituted ethylene such as chloroethylene, C1 - C4 alkylthioethylene, C1 - C2 alkyl-ethylene or 1,2-di-C1 - C2 -alkyl-ethylene, a cyclopropylene such as 1,3-dimethylcyclopropylene, trimethylene, a cyclohexylene-1,2-, cyclohexenylene-1,2-, cyclohexadienylene-1,2- or o-phenylene. The N-(3,5-dihalophenyl)imide compounds can be obtained by any of methods which produce imide compounds or reaction of an N-(3,5-dihalophenyl)maleimide compound with a mercaptan, a hydrogen halide, phosphorus chloride or thionylchloride.
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(2008/06/13)