- Mechanistically optimized intramolecular catalysis in the hydrolysis of esters. Global changes involved in molecular reactivity
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The hydrolysis of the 2′,2′,2′-trifluoroethyl monoester of 1,8-naphthalic acid (1) proceeds via the monoanion with the intermediate formation of the corresponding anhydride. The rate constant for the formation of 1,8-naphthalic anhydride (2) is ca 2500 times faster than its rate of hydrolysis. The isotope effect in the plateau region and theoretical calculations at the PM3 level suggest that elimination of the alkoxide is the rate-limiting step for the reaction. Accordingly, decomposition of the isopropyl monoester of naphthalic acid proceeds 104 times slower than the spontaneous decomposition of 1. The remarkably high rate of monoester decomposition derives from the special configuration of the substrates and important contributions that arise from relief of torsional strain, which clearly includes electron redistribution due to the decrease in steric hindrance to resonance and the fact that proximity obviates solvation.
- Yunes, Santiago F.,Gesser, Jose C.,Chaimovich, Hernan,Nome, Faruk
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Read Online
- Reactions of hydroxyl radicals and ozone with acenaphthene and acenaphthylene
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Acenaphthene and acenaphthylene are polycyclic aromatic hydrocarbons (PAHs) emitted into the atmosphere from a variety of incomplete combustion sources such as diesel exhaust. Both PAHs are present in the gas phase under typical atmospheric conditions and
- Reisen, Fabienne,Arey, Janet
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Read Online
- Degradation of acenaphthylene and anthracene by chemically modified laccase from Trametes versicolor
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We are studying the chemically modified laccase from Trametes versicolor for use in the in vitro oxidation of two polycyclic aromatic hydrocarbons (PAHs), acenaphthylene and anthracene, in combination with 2,2′-azino-bis- (3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) as a redox mediator. The results indicate that the maleic anhydride modified laccase (MA-Lac) improved the stability of laccase to temperature, pH and storage time compared with the free enzyme. After incubation for 72 h, the MA-Lac-ABTS system oxidized acenaphthylene and anthracene to more than 70% from the reaction mixture. This journal is the Partner Organisations 2014.
- Liu, Yulong,Hua, Xiufu
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Read Online
- Naphthalimide-polyamine conjugate as well as preparation method and application thereof
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The invention discloses a naphthalimide-polyamine conjugate, which has a structural general formula as shown in I, a novel skeleton, high efficiency, low toxicity and good inhibitory activity for tumor cells. The invention also discloses a preparation method of the conjugate. Firstly, 3-amino groups with toxic and side effects of amonafide are removed, a phenylpyrazole structure fragment is introduced to the naphthalimide parent naphthalene ring, and a naphthalimide side chain with a polyamine chain is modified, acetyltransferase in vivo is prevented from acetylating the amino groups on the naphthalene ring of amonafideand, and toxic and side effects are reduced; and further by introducing a low-toxicity phenyl pyrazole active structure fragment, the naphthalimide polyamine conjugate witha novel skeleton, high efficiency and low toxicity is synthesized; and secondly, quinazoline with low toxicity is introduced to replace hydrogen atoms of amonafide 3-amino, so that the naphthalimide polyamine conjugate with anti-tumor activity and low toxicity is obtained. The invention also discloses an application of the conjugate in preparation of antitumor drugs, and good development potentialis realized.
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Paragraph 0030; 0108-0110; 0112
(2021/02/10)
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- A Pt(IV)-based mononitro-naphthalimide conjugate with minimized side-effects targeting DNA damage response via a dual-DNA-damage approach to overcome cisplatin resistance
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Platinum(Pt)(II) drugs and new Pt(IV) agents behave the dysregulation of apoptosis as the result of DNA damage repair and thus, are less effective in the treatment of resistant tumors. Herein, mononitro-naphthalimide Pt(IV) complex 10b with minimized side-effects was reported targeting DNA damage response via a dual-DNA-damage approach to overcome cisplatin resistance. 10b displayed remarkably evaluated antitumor (70.10percent) activities in vivo compared to that of cisplatin (52.88percent). The highest fold increase (FI) (5.08) for A549cisR cells and the lowest (0.72) for A549 indicated 10b preferentially accumulated in resistant cell lines. The possible molecular mechanism indicates that 10b targets resistant cells in a totally different way from the existing Pt drugs. The cell accumulation and the Pt levels in genomic DNA from 10b is almost 5 folds higher than that of cisplatin and oxaliplatin, indicating the naphthalimide moiety in 10b exhibits preferentially DNA damage. Using 5′-dGMP as a DNA model, the DNA-binding properties of 10b (1 mM) with 5′-dGMP (3 mM) in the presence of ascorbic acid (5 mM) deduced that 10b was generated by the combination of cisplatin with 5′-dGMP after reduction by ascorbic acid. Moreover, 10b promoted the expression of p53 gene and protein more effectively than cisplatin, leading to the increased anticancer activity. The up-regulated γH2A.X and down-regulated RAD51 indicates that 10b not only induced severe DNA damage but also inhibited the DNA damage repair, thus resulting in its higher cytotoxicity in comparison to that of cisplatin. Their preferential accumulation in cancer cells (SMMC-7721) compared to the matched normal cells (HL-7702 cells) demonstrated that they were potentially safe for clinical therapeutic use. In addition, the higher therapeutic indices of 10b for 4T1 cells in vivo indicated that naphthalimide-Pt(IV) conjugates behaved a vital function in the treatment of breast cancer. For the first time, our study implies a significant strategy for Pt drugs to treat resistance cancer targeting DNA damage repair via dual DNA damage mechanism in a totally new field.
- Li, Linrong,Li, Yingguang,Liu, Hanfang,Ma, Jing,Niu, Jie,Xie, Songqiang,Yue, Kexin
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- Tetravalent platinum naphthalimide complex, preparation method and application thereof
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The invention belongs to the technical field of medicinal chemistry, and particularly relates to a tetravalent platinum naphthalimide complex, a preparation method and application thereof. The tetravalent platinum naphthalimide complex has good anti-tumor activity, which is better than that of cis-platinum and oxaliplatin, and the tetravalent platinum naphthalimide complex has better stability than bivalent platinum like cis-platinum, carboplatin and oxaliplatin. According to the invention, the naphthalimide modified tetravalent platinum has good targeting performance on tumor cells, high selectivity on tumor cells is improved, and different from a classic divalent platinum drug, the complex provided by the invention regulates and controls subcellular organelles and cell nucleus functionsto reverse drug resistance by targeting a tumor high polyamine microenvironment, and relieves immunosuppression of T cells around tumors at the same time. The complex provided by the invention also solves the problems of poor solubility, tedious clinical compatibility, poor patient immunity in clinical application of chemotherapeutic drugs and the like of previous bivalent platinum antitumor drugs, and has good fat solubility and water solubility.
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Paragraph 0079; 0092-0095; 0099-0102; 0106-0109; 0113-0116
(2020/07/21)
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- A 3, 9 - perylene dicarboxylic acid preparation method
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The invention discloses a 3, 9 - perylene dicarboxylic acid of preparation method, specific step is ice-acetic acid in a solvent, in the dihydro e is obtained under the action of the sodium dichromate of 1, 8 - naphthalenedicarboxylic anhydride; 1, 8 - naphthalenedicarboxylic anhydride in saturated ammonia under the action of the acylation to obtain the 1, 8 - naphthalene asia amide; 1, 8 - naphthalene asia amide in potassium hydroxide and anhydrous sodium acetate manufacturing of the alkaline environment in the alkaline environment in C - C under high-temperature conditions obtained by coupling the 3, 4, 9, 10 - perylenetetracarboxylic acid diimide; 3, 4, 9, 10 - perylenetetracarboxylic acid diimide in under the action of the strong acid is converted into the 3, 4, 9, 10 - [...]; 3, 4, 9, 10 - [...] in microwave reactor in alkaline hydrolysis by the decarboxylation of 3, 9 - perylene dicarboxylic acid. The invention synthetic process more economic, environmental protection, high-efficient and simple.
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Paragraph 0018; 0019; 0020
(2019/03/23)
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- The Remarkable Effect of Halogen Substitution on the Membrane Transport of Fluorescent Molecules in Living Cells
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Small-molecule-based fluorescent probes have become important tools in biology for sensing and imaging applications. However, the biological applications of many of the fluorescent molecules are hampered by low cellular uptake and high toxicity. In this paper, we show for the first time that the introduction of halogen atoms enhances the cellular uptake of fluorescent molecules and the nature of halogen atoms plays a crucial role in the plasma membrane transport in mammalian cells. The remarkably higher uptake of iodinated compounds compared to that of their chloro or bromo analogues suggests that the strong halogen bonding ability of iodine atoms may play an important role in the membrane transport. This study provides a novel strategy for the transport of fluorescent molecules across the plasma membrane in living cells.
- Ungati, Harinarayana,Govindaraj, Vijayakumar,Mugesh, Govindasamy
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supporting information
p. 8989 - 8993
(2018/07/25)
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- Preparation method and application of novel perylene acid medicinal molecule with antineoplastic activity
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The invention discloses a preparation method and application of a novel perylene acid medicinal molecule with antineoplastic activity, and belongs to the technical field of pharmaceutical synthesis. The novel perylene acid medicinal molecule with antineoplastic activity is characterized by having the structural formula as shown in the description. The invention also provides a preparation method of the novel perylene medicinal molecule with the antineoplastic activity. The prepared perylene medicinal molecule has higher inhibiting activity for human cervical carcinoma Hela cells, human breastcancer MDA-MB-231 cells and human liver cancer HepG2 cells, and has the potential of becoming an antineoplastic medicament.
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Paragraph 0019; 0020; 0021; 0022; 0023; 0024; 0025-0036
(2019/01/08)
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- Preparation method and application of novel perylene drug molecule with biological activity
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The invention discloses a preparation method and application of a novel perylene drug molecule with the biological activity, and belongs to the technical field of medicine synthesis. According to thekey points of the technical scheme of the preparation method and application of the novel perylene drug molecule, the structural formula of the perylene drug molecule with the biological activity is as shown in the specification, wherein R is O or S. The invention further relates to the preparation method for the novel perylene drug molecule with the biological activity. The perylene drug moleculeprepared through the preparation method has good inhibitory activity on human cervical cancer hHela cells, human breast cancer MDA-MB-231 cells and human liver cancer HepG2 cells, is relatively low in toxicity on human normal cells and has the potential of becoming an anti-tumor drug.
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Paragraph 0019-0021
(2018/12/14)
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- Contraction of π-Conjugated Rings upon Oxidation from Cyclooctatetraene to Benzene via the Tropylium Cation
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We have serendipitously discovered a unique transformation of a cyclooctatetraene derivative 1 into a cycloheptatriene spirolactone 3 upon oxidation, which is the first such transformation reported in 60 years. Product 3 could be reversibly interconverted into the aromatic tropylium cation 3H+ by acid/base treatment, which was accompanied by drastic spectroscopic changes. The resultant cycloheptatriene could be further converted into benzene upon oxidation. We characterized all the key structures by X-ray studies. Eventually, the π-conjugated ring size shrinks from 8 to 7, then finally to 6 upon oxidation, in the direction of the stronger aromatization.
- Tamoto, Akira,Aratani, Naoki,Yamada, Hiroko
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p. 16388 - 16392
(2017/11/21)
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- A novel Schiff-base fluorescent probe based on 1,8-naphthyridine and naphthalimide for Al3+
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A novel Schiff-base, 7-acetamino-4-methyl-1,8-naphthyridine-2-carbaldehyde-(1′,8′-naphthalenedicarbonyl) hydrazone (HL) was designed, synthesized and evaluated as a fluorescent probe. The fluorescence properties of this probe towards various metal ions were investigated by UV–vis and fluorescence spectra in methanol. Test results indicated that the probe had high selectivity towards Al3+ over other commonly coexisting metal ions. Upon addition of Al3+, the fluorescence intensity at 414?nm increased significantly due to the inhibition of the PET process. The binding constant (Ka) of Al3+ binding to HL was calculated to be 5.64?×?104?M?1 from a Benesi-Hildebrand plot, and the detection limit (LOD) of HL for sensing Al3+ was calculated to be 0.13?μM. The binding stoichiometry between HL and Al3+ was determined as 1:1 by the Job's plot. Furthermore, the probe was chemically reversible for Al3+ in methanol by the addition of Na2EDTA solution.
- Yue, Xiao-li,Li, Chao-rui,Yang, Zheng-yin
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p. 167 - 171
(2017/05/29)
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- Synthesis, in vitro evaluation and DNA interaction studies of N-allyl naphthalimide analogues as anticancer agents
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A novel series of 2-allyl-6-substituted-benzo[de]isoquinoline-1,3-diones has been synthesized and evaluated against 60 human tumor cell lines for their in vitro antitumor activities. Compound 6b proved to be the most active member at a single dose concentration of 10 μM and broad spectrum of antitumor activity with GI50, TGI and LC50 values of 84.2 nM, 27.6 μM and 89.3 μM respectively at five dose concentration levels. The DNA binding properties of this compound has been investigated by a UV-Vis and fluorescence spectrophotometer as well as thermal denaturation experiments. Molecular docking studies of compound 6b have also supported the corresponding biological data.
- Verma, Meenakshi,Luxami, Vijay,Paul, Kamaldeep
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p. 41803 - 41813
(2015/05/27)
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- Reduction of 1,2-dicarbonyl compounds and of their N-phenylimine derivatives by sodium cyanide under aprotic conditions
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Some aromatic 1,2-dicarbonyl compounds, i.e. 9,10-phenanthrenequinone, acenaphthenequinone and benzil, and their corresponding N-phenyl monoimines, have been reduced, using dry acetonitrile as the solvent, in the presence of sodium cyanide as a reducing agent. Comparative potentiostatic preparative-scale electrolysis is described.
- Batanero, Belen,Hamrouni, Kaouthar,Barba, Fructuoso,Barba, Isidoro,Boujlel, Khaled,Benkhoud, Mohamed Lamine
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p. 1284 - 1288
(2015/12/12)
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- Synthesis, in vitro evaluation and molecular modelling of naphthalimide analogue as anticancer agents
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A series of amine substituted naphthalimide analogue were synthesized and evaluated for in vitro anti-tumour activities against 60 tumour cell lines at a single dose concentration of 10 μM. These new analogue showed potential anticancer activities against various cancer cell lines. Compound 5d exhibited significant growth inhibition and was evaluated as 60 cell panel at five dose concentration levels. Compound 5d proved to be fivefold more active than standard antitumour drug 5-fluorouracil (5-FU) with MG-MID GI50 and TGI values of 5.05 and 38.71 respectively. ct-DNA binding studies of most active compound 5d revealed strong interacting properties. Molecular docking studies in the active binding site provided complementary theoretical support for the experimental biological data acquired.
- Verma, Meenakshi,Luxami, Vijay,Paul, Kamaldeep
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p. 352 - 360
(2013/10/01)
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- Oxygen insertion of o-quinone under catalytic hydrogenation conditions
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An oxygen-insertion reaction that transforms an o-quinone and a conjugated α-diketone substrate into an anhydride product or derivative under catalytic hydrogenation conditions is reported. The experiments and computations indicate that the oxygen insertion proceeds via a radical mechanism mediated by an acetoxyl radical.
- Zhang, Da-Li,Zhou, Li-Yan,Quan, Jun-Min,Zhang, Wei,Gu, Lian-Quan,Huang, Zhi-Shu,An, Lin-Kun
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supporting information
p. 1162 - 1165
(2013/04/23)
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- Pd(OAc)2-catalyzed oxidative carbonylation of aromatics: Synthesis of naphthalenecarboxylic acids
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The liquid-phase oxidative carbonylation of aromatics leading to aromatic carboxylic acids is studied to develop new approaches to 2,6- naphthalenedicarboxylic acid (NDA) preparation. It is shown that the catalytic system Pd(OAc)2/K2S2O8 allows the synthesis of naphthalic anhydride (NAn) by direct oxidative carbonylation of naphthalene under mild conditions (25 C, 2 atm CO). The subsequent alkaline hydrolysis of NAn and isomerization of the obtained 1,8-naphthalenedicarboxylic acid salt is known to lead to NDA.
- Elman, Alexander R.
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p. 5527 - 5531
(2013/09/23)
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- Study of photochemistry without light of substituted benzylidine acenaphthenones
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In order to draw a parallel between light induced reactions as well as photochemistry without light (chemiluminescence), the substituted benzylidineacenaphthenones were subjected to dioxetanedione reactions, which are formed in situ by the reaction of 2,4-dimitrophenyloxalate with hydrogen peroxide to provide chrysene derivatives as well as naphthalene 1,8-dicarboxylic acid anhydride and benzoic acid whose structures were determined by IR and 1H NMR spectra.
- Goel, Vijender
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p. 301 - 304
(2013/06/27)
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- An efficient naphthalimide based fluorescent dyad (ANPI) for F- and Hg2+ mimicking OR, XNOR and INHIBIT logic functions
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A fluorescent bischromophoric dyad combining anthracene and naphthalic anhydride units has been synthesized and characterized. The dyad shows a FRET mediated emission signal at ～535 nm when excited at λex. = 380/360 nm, with efficient energy transfer efficiency (ET = 93%) and quantum yield (Φ = 0.155). Upon interaction with F- and Hg 2+ ions selectively, a diminished (switched-Off) FRET signal is observed and the naked-eye sensitive color of the solution changed to dark red with enhanced emission corresponding to an anthracene moiety (switched-On). Job's plot analysis revealed a 1:1 stoichiometry between dyad and F -/AcO- and Hg2+ ions. The output fluorescence signals exhibited by dyad on chemical inputs of F-, AcO- and Hg2+ ions mimicked OR, XNOR and INHIBIT logic functions. A 1H NMR titration experiment suggested deprotonation of -NH proton and "Y-type or tweezer-like" H-bonding interaction in the presence of F- and AcO-, respectively, involving -NH, -CHN- and anthracene ring protons.
- Shahid, Mohammad,Srivastava, Priyanka,Misra, Arvind
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experimental part
p. 1690 - 1700
(2011/10/04)
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- Plants Tolerant to HPPD Inhibitor Herbicides
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The present invention relates to nucleic acid sequences encoding a hydroxyphenylpyruvate dioxygenase (EC 1.13.11.27, abbreviated herein as HPPD) obtained from protists belonging to the family Blepharismidae, as well as the proteins encoded thereby, and to a chimeric gene which comprises such nucleic acid sequence, and to the use of such nucleic acid sequences, proteins or chimeric genes for obtaining plants which are tolerant to HPPD inhibitor herbicides.
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- Plants Tolerant to HPPD Inhibitor Herbicides
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The present invention relates to nucleic acid sequences encoding a hydroxyphenylpyruvate dioxygenase (EC 1.13.11.27, abbreviated herein as HPPD) obtained from Euryarchaeota belonging to the family Picrophilaceae, as well as the proteins encoded thereby, and to a chimeric gene which comprises such nucleic acid sequence, and to the use of such nucleic acid sequences, proteins or chimeric genes for obtaining plants which are tolerant to HPPD inhibitor herbicides.
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- Plants Tolerant to HPPD Inhibitor Herbicides
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The present invention relates to nucleic acid sequences encoding a hydroxyphenylpyruvate dioxygenase (EC 1.13.11.27, abbreviated herein as HPPD) obtained from bacteria belonging to the genus Kordia, as well as the proteins encoded thereby, and to a chimeric gene which comprises such nucleic acid sequence, and to the use of such nucleic acid sequences, proteins or chimeric genes for obtaining plants which are tolerant to HPPD inhibitor herbicides.
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- Plants Tolerant to HPPD Inhibitor Herbicides
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The present invention relates to nucleic acid sequences encoding a hydroxyphenylpyruvate dioxygenase (EC 1.13.11.27, abbreviated herein as HPPD) obtained from bacteria belonging to the subfamily Synechococcoideae, as well as the proteins encoded thereby, and to a chimeric gene which comprises such nucleic acid sequence, and to the use of such nucleic acid sequences, proteins or chimeric genes for obtaining plants which are tolerant to HPPD inhibitor herbicides.
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- Plants Tolerant to HPPD Inhibitor Herbicides
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The present invention relates to nucleic acid sequences encoding a hydroxyphenylpyruvate dioxygenase (EC 1.13.11.27, abbreviated herein as HPPD) obtained from bacteria belonging to the genus Rhodococcus as well as the proteins encoded thereby, and to a chimeric gene which comprises such nucleic acid sequence, and to the use of such nucleic acid sequences, proteins or chimeric genes for obtaining plants which are tolerant to HPPD inhibitor herbicides.
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- Formation and decomposition of N-alkylnaphthalimides: Experimental evidences and ab initio description of the reaction pathways
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The kinetics of hydrolysis of 1,8-N-butyl-naphthalimide (1,8-NBN) to 1,8-N-butyl-naphthalamide (1,8-NBAmide) and of 2,3-N-butyl-naphthalimide (2,3-NBN) to 2,3-N-butyl-naphthalamide (2,3-NBAmide), as well as the formation of the respective anhydrides from the amides were investigated in a wide acidity range. 1,8-NBN equilibrates with 1,8-NBAmide in mild alkali. Under the same conditions 2,3-NBN quantitatively yields 2,3-NBAmide. Over a wide range of acidities the reactions of the 1,8- and 2,3-N-butyl-naphthalamides (or imides) yield similar products but with widely different rates and at distinct pH's. Anhydride formation in acid was demonstrated for 1,8-NBAmide. The reactions mechanisms were rationalized in the manifold pathways of ab initio calculations. The differences in rates and pH ranges in the reactions of the 1,8- and 2,3-N-butyl-naphthalamides were attributed to differences in the stability of the tetrahedral intermediates in alkali as well as the relative stabilities of the five and six-membered ring intermediates. The rate of carboxylic acid assisted 1,8-N-Butyl-naphthalamide hydrolysis is one of the largest described for amide hydrolysis models. Copyright
- De Barros, Teresa Cristina,Filho, Pedro Berci,Loos, Michel,Politi, Mario Jose,Chaimovich, Hernan,Cuccovia, Iolanda Midea
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experimental part
p. 385 - 397
(2011/11/06)
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- High-yielding synthesis of Weinreb amides via homogeneous catalytic carbonylation of iodoalkenes and iodoarenes
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Iodoarenes (iodobenzene and 2-iodothiophene) and iodoalkenes (1-iodocyclohexene, 1-iodo-4-tert-butylcyclohexene, 1-iodo-2-methylcyclohexene and 1-iodo-1-(1-naphthyl)ethene) were used as substrates in palladium-catalysed aminocarbonylation with N,O-dimethylhydroxylamine. The corresponding Weinreb amides were prepared in high isolated yields (up to 87%) when forcing conditions (40-60 bar of CO, 50 °C) were used. The aminocarbonylation provides the Weinreb amides as pure products in a chemoselective reaction. No formation of ketocarboxamides, due to double CO insertion, except for 2-iodothiophene, was observed even at 60 bar of CO pressure.
- Takács, Attila,Petz, Andrea,Kollár, László
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experimental part
p. 4479 - 4483
(2010/07/06)
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- Facile synthesis of 1,8-naphthalimides in palladium-catalysed aminocarbonylation of 1,8-diiodo-naphthalene
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1,8-Diiodo-naphthalene was aminocarbonylated with various primary and secondary amines in the presence of palladium(0) complexes formed in situ from palladium(II) acetate and triphenylphosphine. In the case of primary amines, depending on the amine to substrate ratio, two types of products have been obtained in highly chemoselective reaction: dicarboxamides and N-substituted imides have been formed at high and low amine to substrate ratio, respectively. The reaction tolerates the ester functionality, so that amino acid esters could serve as N-nucleophiles and in this way, naphthalimides possessing stereogenic centre in the N-substituent could be synthesised.
- Takács, Attila,ács, Péter,Kollár, László
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p. 983 - 987
(2008/09/18)
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- Active substances for increasing the stress defense in plants to abiotic stress, and methods of finding them
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The invention relates to a method of finding compounds which increase the tolerance of plants to abiotic stress factors acting on this plant, such as, for example, temperature (such as chill, frost or heat), water (such as dryness, drought or anoxia), or the chemical load (such as lack of or excess of mineral salts, heavy metals, gaseous noxious substances) by increasing the expression of plant-endogenous proteins, and to the use of these compounds for increasing the tolerance in plants to abiotic stress factors.
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- Segregated assemblies in bridged electron-rich and electron-poor π-conjugated moieties
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We report a general strategy for the spontaneous segregation of electron-rich and electron-poor π-conjugated moieties using mutually phobic aliphatic fluorocarbon-hydrocarbon interactions. The Royal Society of Chemistry.
- Benanti, Travis L.,Saejueng, Pranorm,Venkataraman
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p. 692 - 694
(2007/10/03)
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- Use of fourier transform infrared spectroscopy to follow the heterocumulene aided thermal dehydration of phthalic and naphthalic acids
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Fourier transform infrared (FT-IR) spectroscopy has been successfully employed to follow the formation of phthalic anhydride and 1,8-naphthallc anhydride on heating their corresponding acids. The effects of three heterocumulenes, cyanamide, dicyandlamide, and sodium cyanate, on the temperature of formation of the anhydrides were also investigated using this method. It was found that the carbodlimides cyanamide and dicyandiamide dramatically lowered the temperature at which thermal dehydration of the acid led to anhydride formation. It was noted that cyanamide had a stronger catalytic effect than dicyandiamide, presumably due to the electron-withdrawing effect of the amidine group. Sodium cyanate was also found to promote the thermal dehydration of the acids to form the corresponding anhydrides. Under more severe conditions, phthalic acid anhydride formed is seen to react further, leading to the formation of phthalimide. The discrepancy between the products obtained with cyanamide and sodium cyanate leads to the conclusion that, unlike earlier claims, imide formation is not due to the reaction of the anhydride with the urea formed but with sodium cyanate itself. However, only the phthalic anhydride flve-membered ring system is sufficiently reactive towards the CNO- nucleophile to form the imide; the six-membered 1,8-naphthalic anhydride system does not react in this way.
- Rigout, Muriel L. A.,Lewis, David M.
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p. 1405 - 1413
(2008/02/01)
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- Direct oxidative cleavage of α- and β-dicarbonyls and α-hydroxyketones to diesters with KHSO5
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Presented is a methodology to oxidatively cleave α-hydroxyketones and α- or β-diones using the environmentally benign reagent KHSO 5, prepared easily from Oxone, to diesters in one simple transformation. In addition, we undertook a mechanistic study to provide a plausible mechanistic interpretation. These reactions may prove to be valuable alternatives to other related metal-mediated processes.
- Yan, Jun,Travis, Benjamin R.,Borhan, Babak
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p. 9299 - 9302
(2007/10/03)
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- Herbicides comprising benzoylcyclohexanediones and safeners
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Herbicidal compositions are described that comprise active substances from the group of the benzoylcyclohexanediones and also safeners. These herbicidal compositions are especially suitable for use against weed plants in crop plant cultures.
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- Combination of herbicides and safeners
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A herbicidally active composition comprises a mixture of A. a herbicidally effective amount of one or more compounds of the formula (I), ?and B. an antidote-effective amount of one or more compounds of the formulae (II) to (IV),
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- COMBINATIONS OF HERBICIDES AND SAFENERS
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There are described herbicidal compositions which comprise at least one herbicidally active compound of the formula (I) and at least one crop-plant-protecting compound as safener. In this formula (I), V is an optionally substituted radical selected from the group consisting of isoxazol-4-yl, pyrazol-4-yl, cyclohexane-1,3-dion-2-yl and 3-oxopropionitril-2-yl and R9 is nitro, amino, halogen or a carbon-containing radical. The group of the safeners contains, for example, 2,4-D, cyometrinil, dicamba, dymron, fenclorim, flurazole, fluxofenim, lactidichlor, MCPA, mecoprop, MG-191, oxabetrinil, methyl diphenylmethoxyacetate, 1-[4-(N-2-methoxybenzoylsulfamoyl)phenyl]-3-methylurea, 1,8-naphthalaic anhydride, 1-[4-(N-2-methoxybenzoylsulfamoyl)phenyl]-3,3-dimethylurea, 1-[4-(N-4,5-dimethylbenzoylsulfamoyl)phenyl]-3-methylurea, 1-[4-(N-naphthoylsulfamoyl)phenyl]-3,3-dimethylurea, (4-chlorophenoxy)acetic acid, 4-(2,4-dichlorophenoxy)butyric acid, 4-(4-chloro-o-tolyloxy)butyric acid, 4-(4-chlorophenoxy)butyric acid, in each case their acids and esters, N-acylsulfonamides, N-acylsulfamoyl-benzamides, in each case, if appropriate, also in salt form and in each case optionally substituted 1-phenylpyrazoline, 1-phenylpyrazole, 1-phenyl-triazole, 5-phenylisoxazoline and 5-phenylmethylisoxazoline-3-carboxylic esters and 2-(8-quinolinyloxy)acetic acid derivatives.
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- Catalytic oxidation of acenaphthene and its derivatives in acetic acid
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The chemistry of formation of products of acenaphthene oxidation in the presence of the catalyst containing both manganese and cobalt bromides under batch conditions is discussed. The main reaction products are acenaphthene quinone, acenaphthenol-9, trans-acenaphthylene glycol, naphthalide, and naphthalic anhydride. The sequence of reactions leading to the final products is established. It is shown that the main oxidation product in the presence of the manganese-based catalyst is naphthalic anhydride, and the main product in the presence of the cobalt-based catalyst is acenaphthene quinone. The process and engineering techniques providing for the high overall and fractional yields of the desired products are discussed.
- Bukharkina, Tatiana V.,Grechishkina, Olga S.,Digurov, Nikolai G.,Kon'kov, Ivan I.
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p. 394 - 400
(2013/09/06)
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- Hydrolysis of 1,8- and 2,3-naphthalic anhydrides and the mechanism of cyclization of 1,8-naphthalic acid in aqueous solutions
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Naphthalene-1,8-dicarboxylic acid, 1,8-Acid, cyclizes spontaneously in acidic aqueous solution to naphthalene-1,8-dicarboxylic anhydride, 1,8-An, and here we Present an ab initio study of the reaction pathway. The effect of pH on the hydrolysis of 1,8-An was analysed and compared with the hydrolysis of naphthalene-2,3-dicarboxylic anhydride, 2,3-An, to naphthalene-2,3-dicarboxylic acid, 2,3-Acid. The values of the pKa's of 1,8-Acid and 2,3-Acid were ca. 3.5 and 3.0, for monoanion formation, pKa1, and 5.5 and 5.0 for dianion formation, pKa2, respectively. Fluorimetric titration demonstrated that the diprotonated 2,3-Acid. AH2, was further protonated to yield AH3+. The pH-rate constant profile for 2,3-An hydrolysis showed a water reaction between pH's 1.0 and 6.0 and a base catalysed hydrolysis above pH 7.0. Under no condition was 2,3-An formed from 2,3-Acid. The pH dependent decomposition kinetics of 1,8-An is complex and, below pH 6.0, the pH-rate constant profile was fitted by assuming that both AH2 and AH3+ are in equilibrium with 1,8-An. The values of the equilibrium constants for 1,8-An formation from AH2 and AH3+ were ca. 4 and 100 in dilute and concentrated acid, respectively. Ab initio calculations for a possible reaction pathway connecting the undissociated 1,8-Acid to 1,8-An show a transition state where an intramolecular proton transfer is concerted with oxygen alignment towards the carbonyl centre. The planar intermediate is then dehydrated yielding a complex between water and 1,8-An.
- Barros, Teresa C.,Yunes, Santiago,Menegon, Guilherme,Nome, Faruk,Chaimovich, Hernan,Politi, Mario J.,Dias, Luis G.,Cuccovia, Iolanda M.
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p. 2342 - 2350
(2007/10/03)
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- Safened herbicidal sulfonamide compositions
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The disclosure herein relates to the use of a variety of antidotal compounds to safen crop plants from the phytotoxicity of azolopyrimidine sulfonamide herbicides.
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- Decomposition of acenaphthylene by ultrasonic irradiation
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Polycyclic aromatic hydrocarbons were extracted from a soil sample using ultrasound and dichloromethane-, cyclohexane-, and toluene-water mixtures. It was found that when dichloromethane is used as an extractant, acenaphthylene reacts with the solvent Several chlorinated and oxygenated derivatives were identified. The results show that chlorinated solvents should be avoided because of their sonolytic decomposition. Particularly unsaturated nonaromatic compounds might react with intermediate decomposition radicals of the solvent
- Leonhardt,Stahl
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p. 1228 - 1230
(2007/10/03)
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- Herbicide antidotes as safeners for reducing phytotoxicity resulting from synergistic interaction between herbicides and other pesticides
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The disclosure herein relates to means for combatting the adverse phytotoxic action to crops arising from the interaction of various herbicidal compounds and biocidal compounds, e.g., insecticidal and/or fungicidal compounds. The means employed to reduce said interaction involves the safening action of various antidotal compounds.
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- Safening imidazolinone herbicides
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The disclosure herein relates to the use of certain amides of dichloroacetic acid and other compounds as safener/antidotal compounds to reduce the phytotoxicity to crop plants, especially corn, of imidazolinone-type herbicides alone or in admixture with other co-herbicidal compounds, e.g., α-haloacetamides.
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- Nonlineaphores and polymers incorporating such nonlineaphores
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Nonlinear-optic (NLO) compositions containing functionalized merocyanine dyes, such that the molecules, comprising the NLO-active compositions have a functional group at each end of the molecule and each functional group differing in reactivity, thus permitting stepwise reaction of each functional group, and NLO-active molecules prepared from hemioxonol dyes derviatived with (meth)acrylate or (meth)acrylamide groups, and their uses in devices such as second harmonic generators or polymer integrated optics.
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- Safening herbicidal benzoic acid derivatives
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The disclosure herein relates to the use of certain amdies of dichloroacetic acid and other compounds as safener/antidotal compounds to reduce the phytotoxicity to crop plants, especially corn, of benzoic acid-type herbicides alone or in admixture with other co-herbicidal compounds, e.g., α-haloacetamides.
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- Synthesis of 3-Vinyl-1,2,4-trioxolanes by a Cycloaddition of Carbonyl Oxides with α,β-Unsaturated Carbonyl Compounds
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The cycloaddition of a carbonyl oxide, generated by the ozonolysis of a vinyl ether, to an α,β-unsaturated aldehyde gave the 3-vinyl-1,2,4-trioxolane (α-vinyl ozonide) in moderate yield.In contrast, α,β-unsaturated ketones showed a very poor reactivity with carbonyl oxides.Benzylidenecyclohexanones were exceptions, from which the corresponding 3-vinyl-1,2,4-trioxolanes were obtained in excellent yields.Reaction of the 3-vinyl-1,2,4-trioxolanes with ozone led to the formation of the corresponding diozonides.
- Mori, Mitsuyuki,Tabuchi, Toshihiko,Nojima, Masatomo,Kusabayashi, Shigekazu
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p. 1649 - 1652
(2007/10/02)
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- Ozonolysis of Vinyl Ethers in the Presence of α-Diketones and α-Keto Esters
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Ozonolysis of vinyl ethers in the presence of α-diketones provided two types of products, i.e., a Baeyer-Villiger oxidation product and 3-acyl-1,2,4-trioxolane.The evidence suggests that the latter product is labile and, therefore, the former one might be produced by decomposition of the latter.In contrast, 1,2,4-trioxolane-3-carboxylates were stable.As a result, ozonolysis of vinyl ethers in the presence of α-keto esters yielded the expected ozonides in high yield.
- Tabuchi, Toshihiko,Nojima, Masatomo
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p. 6591 - 6595
(2007/10/02)
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- Safening herbicidal benzoic acid derivatives
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The disclosure herein relates to the use of certain amides of dichloroacetic acid and other compounds as safener/antidotal compounds to reduce the phytotoxicity to crop plants, especially corn, of benzoic acid-type herbicides alone or in admixture with other co-herbicidal compounds, e.g., α-haloacet-amides.
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- peri-Diketones with the Ring System of Cyclo-octanaphthalene
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peri-Diketones of naphthalene having an eight-membered ring are obtained by oxidative cleavage of cyclopentacenaphthylenes prepared from acenaphthylene-1,2-dione.Cyclo-octanaphthalenes with two peri β-keto ester ketone carbonyl groups exist as mono-enols.The parent 9,10-dihydrocyclo-octanaphthalene-7,11(8H)-dione is a stable though reactive diketone, reduced to a pinacol with exceptional ease and forming stable adducts with water or methanol.
- Jackson, David A.,Lacy, Philip H.,Smith, Donald C. C.
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p. 215 - 220
(2007/10/02)
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- Preparation and Catalytic Hydrogenation of Spiro and Sprio
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Wittig monoolefination of acenaphthylene-1,2-quinone (1) with ethyl (triphenylphosphoranylidene)acetate yields the o-quinomethane derivative 2 which by 1,3-dipolar cycloaddition reactions with aromatic nitrile oxides affords regioselectively the spiro 3 and 4.Reaction between 1 and benzonitrile oxide gives the spiro 5 which by treatment with ethyl(triphenylphosphoranylidene)acetate gives compound 6.Reaction between 6 and benzonitrile oxide gives regioselectively the diastereomeric dispiro compounds 7 and 7'.Catalytic hydrogenation of the spiro compounds 6,7, and 7' over 10percent Pd/C results in the cleavage of the dioxazole ring while cleavage of the isoxazole ring of compound 3 is achieved either by reduction over Raney nickel or by treatment with sodium ethoxide.Reduction of products prepared according Scheme 1 affords the acenaphthylene derivatives 8,9 and 12-15.
- Lefkaditis, Demetrios A.,Argyropoulos, Nicolaos G.,Nicolaides, Demetrios N.
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p. 1863 - 1871
(2007/10/02)
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- 1,2-DERIVATIVES OF ACENAPHTHYLENE. III. SYNTHESIS OF Z-1,2-DIBROMO-1,2-DIHYDROACENAPHTYLENE
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The cis-addition of bromine to acenaphthylene was discovered.Z-1,2-dibromo-1,2-dihydroacenaphthylene was isolated in the form of two crystalline modifications, i.e., needles and plates.The new isomer isomerizes to the E-1,2-dibromide and like the latter is converted into 1-bromoacenaphthylene, naphtalic anhydride, and the monoacetate of cis-acenaphthene-1,2-diol.
- Anikin, V. F.,Levandovskaya, T. I.,Ganin, Yu. G.
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p. 563 - 566
(2007/10/02)
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