- Synthesis of 4-substituted-1,2-dihydroquinolines by means of gold-catalyzed intramolecular hydroarylation reaction of n-ethoxycarbonyl-n-propargylanilines
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An alternative Au(I)-catalyzed synthetic route to functionalized 1,2-dihydroquinolines is reported. This novel approach is based on the use of N-ethoxycarbonyl protected-Npropargylanilines as building blocks that rapidly undergo the IMHA reaction affording the 6-endo cyclization product in good to high yields. In the presence of N-ethoxycarbonyl-N-propargyl-metasubstituted anilines, the regiodivergent cyclization at the ortho-/para-position is achieved by the means of catalyst fine tuning.
- Arcadi, Antonio,Calcaterra, Andrea,Fabrizi, Giancarlo,Fochetti, Andrea,Goggiamani, Antonella,Iazzetti, Antonia,Marrone, Federico,Marsicano, Vincenzo,Mazzoccanti, Giulia,Serraiocco, Andrea
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supporting information
(2021/06/21)
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- Synthesis of Acetaminophen Analogues Containing α-Amino Acids and Fatty Acids for Inhibiting Hepatotoxicity
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Acetaminophen is a popular antipyretic analgesic medicine that has weaker anti-inflammatory properties and lower incidence of side effects than nonsteroidal anti-inflammatory drugs (NSAIDs). However, acetaminophen causes hepatotoxicity due to the reactive metabolite N -acetyl- p -benzoquinone imine (NAPQI). We have obtained acetaminophen analogues in 57-99percent yields by using aniline derivatives with protected α-amino acids and fatty acids via the corresponding mixed carbonic carboxylic anhydrides in aqueous MeCN. We have also succeeded in synthesizing AM404 analogues in 76-97percent yields, which are expected to be promising candidates for reducing hepatotoxicity.
- Imai, Nobuyuki,Jung, Seunghee,Kawashima, Yuya,Noguchi, Takuya
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p. 3686 - 3696
(2019/09/30)
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- Teaching Old Compounds New Tricks: DDQ-Photocatalyzed C?H Amination of Arenes with Carbamates, Urea, and N-Heterocycles
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The C?H amination of benzene derivatives was achieved using DDQ as photocatalyst and BocNH2 as the amine source under aerobic conditions and visible light irradiation. Electron-deficient and electron-rich benzenes react as substrates with moderate to good product yields. The amine scope of the reaction comprises Boc-amine, carbamates, pyrazoles, sulfonimides and urea. Preliminary mechanistic investigations indicate arene oxidation by the triplet of DDQ to radical cations with different electrophilicity and a charge transfer complex between the amine and DDQ as intermediate of the reaction.
- Das, Somnath,Natarajan, Palani,K?nig, Burkhard
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supporting information
p. 18161 - 18165
(2017/12/28)
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- BMIm HCO3: an ionic liquid with carboxylating properties. Synthesis of carbamate esters from amines
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1-Butyl-3-methylimidazolium hydrogen carbonate (BMIm HCO3) was used as an ionic liquid with carboxylating properties able to convert, in the presence of an alkyl halide, amines into the corresponding carbamate esters. Moderate to good yields of
- Di Nicola,Arcadi,Rossi
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supporting information
p. 9895 - 9898
(2016/12/07)
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- One-pot preparation of carbamoyl benzotriazoles and their applications in the preparation of ureas, hydrazinecarboxamides and carbamic esters
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Carbamoyl benzotriazoles were conveniently synthesized in one-pot from carboxylic acids, diphenyl phosphorazidate (DPPA) and 1H-benzotriazole (BtH). The reactivity and applications of carbamoyl benzotriazoles were also explored. Carbamoyl benzotriazoles react smoothly with amino acids, hydrazines and alcohols, thus providing facile access to the corresponding ureas, hydrazinecarboxamides and carbamic esters, respectively, in good to excellent yields.
- Mao, Hui,Liu, Huili,Tu, Yawei,Zhong, Zhiyun,Lv, Xin,Wang, Xiaoxia
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- Convenient synthesis of acetaminophen analogues containing α-amino acids and fatty acids via their mixed carbonic carboxylic anhydrides in aqueous organic solvent
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Acetaminophen analogues containing α-amino acid and fatty acids were easily synthesized in 77-99% yields from the corresponding mixed carbonic carboxylic anhydrides of α-amino acid and fatty acids using aniline derivatives in aqueous MeCN.
- Jung, Seunghee,Tsukuda, Yuki,Kawashima, Rie,Ishiki, Takumi,Matsumoto, Ayaka,Nakaniwa, Aya,Takagi, Miho,Noguchi, Takuya,Imai, Nobuyuki
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p. 5718 - 5720
(2013/09/24)
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- Reaction of organozinc halides with aryl isocyanates
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Reformatsky reagent, benzylzinc bromide or alkylzinc iodides react with aryl isocyanates directly to give corresponding N-substituted carbamates under mild reaction conditions. However, the reaction of allylzinc bromide or propargylzinc bromide with aryl isocyanates produces the corresponding N-substituted amides. The reactions provide alternative methods for the synthesis of N-substituted carbamates or amides.
- Yang, Haoran,Huang, Danfeng,Wang, Ke-Hu,Xu, Changming,Niu, Teng,Hu, Yulai
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supporting information
p. 2588 - 2593
(2013/03/28)
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- Design and synthesis of novel stiripentol analogues as potential anticonvulsants
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A series of stiripentol (STP) analogues namely, 2-[(1E)-1-(1,3-benzodioxol- 5-yl)-4,4-dimethylpent-1-en-3-ylidene]-N-(aryl/H)hydrazinecarboxamides 7a-h, (±)-(5RS)-N-(aryl/H)-(1,3-benzodioxol-5-yl)-3-tert-butyl-4, 5-dihydro-1H-pyrazole-1-carboxamides (±)-8a-h, and (±)-[(5RS)-(1, 3-benzodioxol-5-yl)-3-tert-butyl-4,5-dihydro-1H-pyrazol-1-yl](aryl)methanones (±)-13a-f was synthesized by adopting appropriate synthetic routes and was pharmacologically evaluated in the preliminary anticonvulsant screens. The selected bioactive new chemical entities were subjected to ED50 determination and neurotoxicity evaluation. The most active congeners are 7h in MES screen and (±)-13b in scPTZ screen which displayed ED50 values of 87 and 110 mg/kg, respectively, as compared to that of STP (ED 50 = 277.7 and 115 mg/kg in MES and scPTZ, respectively).
- Aboul-Enein, Mohamed N.,El-Azzouny, Aida A.,Attia, Mohamed I.,Maklad, Yousreya A.,Amin, Kamilia M.,Abdel-Rehim, Mohamed,El-Behairy, Mohammed F.
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experimental part
p. 360 - 369
(2012/03/11)
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- Synthesis of aryl carbamates via copper-catalyzed coupling of aryl halides with potassium cyanate
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Coupling of aryl halides with potassium cyanate takes place at 100-110 °C in alcohols under the catalysis of CuI (cuprous iodide) and 2-(2,6-dimethylphenylamino)-2-oxoacetic acid, affording the corresponding aryl carbamates with great diversity. Copyright
- Yang, Xinye,Zhang, Yihua,Ma, Dawei
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supporting information
p. 2443 - 2446,4
(2020/08/31)
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- Copper-catalyzed coupling of arylboronic acids with potassium cyanate: A new approach to the synthesis of aryl carbamates
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The copper-catalyzed coupling of aromatic boronic acids with potassium cyanate in the presence of an alcohol has been employed for the synthesis of arylcarbamates. This simple and highly efficient approach can be carried out in air at room temperature and, importantly, no base, ligand, or additive is required. Copyright
- Kianmehr, Ebrahim,Baghersad, Mohammad Hadi
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supporting information; experimental part
p. 2599 - 2603
(2011/11/29)
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- Synthesis and antibacterial activity of isothiazolyl oxazolidinones and analogous 3(2H)-isothiazolones
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The synthesis and antibacterial activity of several new 5-((3-oxoisothiazol-2(3H)-yl)methyl)-3-phenyloxazolidin-2-ones 8 and analogous 2-(4-substituted phenyl)-3(2H)-isothiazolones 3 and 4 substituted at 4 and/or 3-positions of the phenyl moiety with different groups of which some have shown to increase the antibacterial activity of both 3-aryl-2-oxazolidinones and 3(2H)-isothiazolones is described. The most active compounds were isothiazolyl oxazolidinones 8a,j with unsubstituted and 8b with 4-F substituted phenyl rings which showed activities higher than analogous 3(2H)-isothiazolones and comparable or superior to linezolid, vancomycin, and ciprofloxacin against some tested microorganisms. The change in position of F and/or the use of larger substituents gave compounds with reduced or no activity. Evaluation of cytotoxicity to mouse fibroblast (NIH/3T3) cells indicated that these compounds exhibit antibacterial activity at non-cytotoxic concentrations.
- Adibpour, Neda,Khalaj, Ali,Rajabalian, Saeed
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scheme or table
p. 19 - 24
(2010/03/24)
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- Substituent effect on aniline carbonylation reaction in the presence of the PdCl2/Fe/I2/Py catalytic system
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A study of the effect of substituents in the aromatic ring on the aniline carbonylation reaction in the presence of the PdCl2/Fe/I 2/Py catalytic system, where oxygen or nitrobenzene were used as oxidants, showed that the electronodonor substituents accelerate the aniline carbonylation reaction, when the reaction is conducted in the presence of oxygen. For nitrobenzene used as an oxidant in this reaction substituent was found to have no effect on the carbamate yield. The nitrobenzene reduction is the rate-determining step in the aniline carbonylation process.
- Karpinska,Baran,Skupinska
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p. 1105 - 1116
(2008/09/21)
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- Electrochemically promoted C-N bond formation from amines and CO 2 in ionic liquid BMIm-BF4: Synthesis of carbamates
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A new electrochemical procedure for the synthesis of organic carbamates from amines and carbon dioxide has been developed using selective cathodic reduction of carbon dioxide in CO2-saturated room-temperature ionic liquid BMIm-BF4 solutions containing amines 1a-j, followed by addition of EtI as an alkylating agent. The synthesis was carried out under mild (PCO2 = 1.0 atm, t = 55 °C) and safe conditions, and the use of volatile and toxic solvents and catalysts (according to the growing demand for ecofriendly synthetic methodologies), as well as of any supporting electrolyte (for a very easy workup of the reaction mixture), was avoided. Carbamates 2a-j were isolated in good to high yields.
- Feroci,Orsini,Rossi,Sotgiu,Inesi
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p. 200 - 203
(2007/10/03)
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- A new access to quinazolines from simple anilines
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A new synthetic pathway to quinazolines is described. This new method uses hexamethylenetetramine in TFA and potassium ferricyanide in aqueous ethanolic KOH, starting from simple N-protected anilines. The method affords substituted quinazolines with high
- Chilin, Adriana,Marzaro, Giovanni,Zanatta, Samuele,Barbieri, Vera,Pastorini, Giovanni,Manzini, Paolo,Guiotto, Adriano
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p. 12351 - 12356
(2007/10/03)
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- Synthesis of some heterocycle containing urea derivatives and their anti-viral activity
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Some new isoindol heterocyclic ureas (6a-6i) have been synthesized using N-aminophthalimide (2) and ethyl N-monosubstituted/ethyl N,N-disubstituted carbamate (5a-5i). All the newly synthesized final compounds have been evaluated for their anti-viral activities against a variety of viruses. The compound (6f) with the methoxy substituent showed reasonably better activity as compared to the standard drugs against all the viruses (cf. Tables 1, 2 and 3). Further, all the products (6a-6i) were found to be active against Vesicular stomatitis virus, Coxsackie virus B4 and Respiratory syncytical virus (cf. Table 2) and the compounds (6h) and (6i) displayed better antiviral activity in comparison to Brivudin and (S)-DHPA (cf. Table 3).
- Verma, Majusha,Singh, Krishna N.,Clercq, Erik D.
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- Synthesis and fungicidal activity of some sulphide derivatives of O-ethyl-N-substituted phenylcarbamates
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Monosulphides of O-ethyl-N-substituted phenylcarbamates were prepared by the reaction between O-ethyl-N-substituted phenylcarbamates and sulphur dichloride, while the corresponding disulphides were prepared by the reaction between O-ethyl-N-substituted ph
- Adelowo-Imeokparia,Ojo
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p. 324 - 329
(2007/10/03)
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- Identification and characterization of amino-piperidinequinolones and quinazolinones as MCHr1 antagonists
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Several potent, functionally active MCHr1 antagonists derived from quinolin-2(1H)-ones and quinazoline-2(1H)-ones have been synthesized and evaluated. Pyridylmethyl substitution at the quinolone 1-position results in derivatives with low-nM binding potency and good selectivity with respect to hERG binding.
- Blackburn, Christopher,LaMarche, Matthew J.,Brown, James,Che, Jennifer Lee,Cullis, Courtney A.,Lai, Sujen,Maguire, Martin,Marsilje, Thomas,Geddes, Bradley,Govek, Elizabeth,Kadambi, Vivek,Doherty, Colleen,Dayton, Brian,Brodjian, Sevan,Marsh, Kennan C.,Collins, Christine A.,Kym, Philip R.
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p. 2621 - 2627
(2007/10/03)
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- Synthesis and insecticidal evaluation of propesticides of benzoylphenylureas
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Two series of benzoylphenylurea derivatives were synthesized as candidate propesticides by a nucleophilic addition reaction between 2,6-difluronbenzoyl isocyanate and N-substitutedaniline. The new compounds were identified by 1H NMR spectroscopy, electron ionization-mass spectrometry, and elemental analyses. The bioactivities of the new compounds were evaluated. All of the propesticides reported here were soluble in most organic solvents, and their hydrophobicities were improved obviously. The result of the bioactivities of the new compounds against Oriental armyworm showed that some of the new compounds are good as compared to diflubenzuron and penfluron.
- Chen, Li,Wang, Qingmin,Huang, Runqiu,Mao, Chunhui,Shang, Jian,Bi, Fuchun
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- Microwave promoted solvent-free one-pot synthesis of N,N′- disubstituted urea derivatives
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An efficient one-pot synthesis of N,N′-disubstituted urea derivatives from substituted anilines, ethyl chloroformate and methyl anthranilate or methyl 3-amino-2-butenoate under microwave irradiation is reported.
- Jadhav, Vinod H.,Deshpande, Shubhada S.,Borate, Hanumant B.,Wakharkar, Radhika D.
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p. 205 - 208
(2007/10/03)
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- BENZIMIDAZOLIDINONE DERIVATIVES
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The present invention can provide novel compounds useful as orally administrable growth hormone releaser, more specifically a benzimidazolidinone derivative of formula (1) or a pharmaceutically acceptable salt thereof:(1) wherein R1 is optional
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Page/Page column 31
(2010/02/07)
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- Cyanomethyl anion/carbon dioxide system: An electrogenerated carboxylating reagent. Synthesis of carbamates under mild and safe conditions
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A new carboxylating reagent (-CH2CN/CO2) was obtained by bubbling CO2 in a CH3CN-TEAP (tetraethylammonium perchlorate) solution previously electrolyzed under galvanostatic control. Organic carbamates were isolated from these solutions after addition of amines and an alkylating agent. In this paper, we describe the optimized conditions for the electrochemical synthesis of carbamates from amines and CO2, in mild and safe conditions, without any addition of bases, probases, or catalysts. Carbamates were isolated from primary and secondary aliphatic amines in high to excellent yields and from aromatic amines in moderate yields (dependent on the nucleophilicity of the nitrogen atom).
- Feroci, Marta,Casadei, Maria Antonietta,Orsini, Monica,Palombi, Laura,Inesi, Achille
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p. 1548 - 1551
(2007/10/03)
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- Direct conversion of azides to carbamates and sulfonamides using Fe/NH4Cl: Effect of sonication
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A simple, direct and effective conversion of azides to carbamates and sulfonamides is achieved using Fe/NH4Cl in methanol. The influence of sonication and direct application in solution phase combinatorial chemistry are also studied by developing a 6x4 matrix library. (C) 2000 Elsevier Science Ltd.
- Chandrasekhar,Narsihmulu
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p. 7969 - 7972
(2007/10/03)
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- The reaction of amines with an electrogenerated base. Improved synthesis of arylcarbamic esters
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The electrogenerated base of 2-pyrrolidone reacts with amines and anilines yielding the corresponding alkyl and aryl carbamates, after addition of carbon dioxide and ethyl iodide. Arylcarbamic esters are obtained in very good yields under mild reaction conditions with respect to the methods so far reported. (C) 2000 Elsevier Science Ltd.
- Feroci, Marta,Inesi, Achille,Rossi, Leucio
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p. 963 - 966
(2007/10/03)
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- A new route to 2-oxazolines, bis-oxazolines, and 2-Imidazoline-5-ones from imidates using solvent-free cycloadditions: Synthesis, chemical properties, and PM3 MO calculations
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The 1,3-dipolar cycloadditions between imidate 1, derived from dimethylaminomalonate and aldehydes 2(a-f), phthalaldehyde 2g, isophthalaldehyde 2h. 4-chlorophenylisocyanate 9a, ethoxycarbonylisothiocyanate 9d as dipolarophiles proceeds regioselectively in
- Lerestif, Jean Michel,Toupet, Loic,Sinbandhit, Sourisak,Tonnard, Francois,Bazureau, Jean Pierre,Hamelin, Jack
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p. 6351 - 6364
(2007/10/03)
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- Method for treating swine dysentery with the derivatives of the antibiotic A82810
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New polyether antibiotic A82810, its acyl and alkyl ester, acyl ester and urethane derivatives, and salts thereof, are useful antibacterial and anticoccidial agents and increase feed-utilization efficiency in animals. Methods of making A82810 by culture of Actinomodura fibrosa sp. nov. NRRL 18348 and synergistic compositions of the A82810 compounds with nicarbazin, 4,4'-dinitrocarbanilide, certain napthalenamine and benzenamine compounds and metichlorpindol are also provided.
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- Ring Cleavage Reaction of 1,3-Oxazine-2,4(3H)-dione Derivatives with Amines
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The reactions of 3,6-dimethyl -1,3-oxazine-2,4(3H)-diones (1a, 1b, and 1c) with various amines were investigated under various conditions.Several reactions products were obtained such as the pyrimidines (3a, 3b, 3c, and 3d), the acetoacetamides (4a, 4b, and 4c), (4-chlorophenyl)urethane (5a), and ethyl acetoacetate (4d) with primary amines, and the acetoacetamides (4e and 4f), the urethanes (5a and 5b), the carboxamides (5c, 5d, 5e, and 5f), and the butenamides (7a, 7b, and 7c) with secondary amines.In the case of 1c with amine, alcohol used as a solvent reacted as a nucleophile to give the urethane (5a or 5b).
- Kinoshita, Toshio,Takeuchi, Kozue,Kondoh, Masaya,Furukawa, Sunao
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p. 2026 - 2029
(2007/10/02)
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- PREPARATION AND PROPERTIES OF 3-ALKYL-i-ARYLNITROSOUREAS AND RELATED COMPOUNDS
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Nitrosation of 3-alkyl-1-arylureas was investigated with sodium nitrite in 99percent formic acid or with isoamyl nitrite in chloroform.The preparation of 3-alkyl-1-aryl-1-nitrosoureas was effectively performed by using isoamyl nitrite in the absence of acids, since the 1-nitrosoureas were isomerized to the 3-nitroso isomers by acids.The carbon-13 nuclear magnetic resonance and infrared spectral properties of the products were examined and their structural features are discussed.It was found that 3-alkyl-1-aryl-1-nitrosoureas decomposed to form alkyl isocyanates and 3-alkyl-1-(2-nitroaryl)ureas in carbon tetrachloride. 1,3-Rearrangement and transnitrosation also took place in this solvent.Keywords - 3-alkyl-1-arylnitrosourea; 3,3-diethyl-1-tolyl-1-nitrosourea; N-nitrosourea; nitrosation; 1,3-rearrangement; isomerization; transnitrosation; nitration
- Tanno, Masayuki,Sueyoshi, Shoko
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p. 1360 - 1371
(2007/10/02)
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- The Kinetics of the Addition of Ethanol to p-Chlorophenyl Isocyanate in Diethyl Ether Solution in the Presence of Covalent Metal Halides
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The effects of the presence of BF3, ZnCl2, SbCl3, PhSnCl3, (Bun)2SnCl2, and (Bun)3SnCl on the kinetics of ethanolysis of p-chlorophenyl isocyanate in diethyl ether solution have been studied at 25 deg C.The covalent halides rapidly f
- Hazzard, Graham,Lammiman, Steven A.,Poon, Nai L.,Satchell, Derek P. N.,Satchell, Rosemary S.
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p. 1029 - 1034
(2007/10/02)
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- Process for the preparation of N,O-disubstituted urethanes useful for the preparation of isocyanates
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A process for the preparation of N,O-disubstituted urethanes. Urea or polyurets, primary amines and alcohols are reacted at 120°-350° C. in the presence of N-substituted urethanes and/or N-mono- or N,N'-disubstituted ureas or polyureas. In a preferred embodiment, the reactants further include catalysts known to be useful in esterification of carboxylic acids. The urethanes produced in accordance with this process are particularly useful as starting materials for preparation of isocyanates.
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- UEBER DIE Si-N-BINDUNG. XLII. BESTIMMUNG DER AKTIVIERUNGSPARAMETER FUER DIE HYDROLYSE VON TRIMETHYLSILYLURETHANEN DES TYPS Me3Si(p-XC6H4)NCOOEt
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Hydrolysis reactions of silylurethanes Me3Si(p-XC6H4)NCOOEt with X = Cl, H or Me in aqueous buffer solutions, with pH values of 2.33, 3.80, and 9.38 and at temperatures of 20, 30, and 40 deg C were studied.The catalytic rate constants for the acid- and base-catalysed reactions and for the "non-catalysed" reaction k(H3O+), k(OH-), and k0 were evaluated from the pseudo first-order rate constants kexp, determined by UV spectroscopy.Activation parameters were obtained by means of the Arrhenius or Eyring equation from the dependence of rate constants of the temperature.From ρ values and activation parameters we assume for the acid and general base-catalysed reactions a SN2-Si mechanism with more or less clear d-participation at the silicon atom and for the OH--catalysed reaction a SN2-Si mechanism.
- Haenig, K.,Grosse-Ruyken, H.,Ruehlmann, K.
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p. 143 - 150
(2007/10/02)
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- UEBER DIE Si-N-BINDUNG. XLI. KINETISCHE UNTERSUCHUNGEN ZUR HYDROLYSE VON TRIMETHYLSILYLURETHANEN DES TYPS Me3Si(p-XC6H4)NCOOEt
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Hydrolysis reactions of silylurethanes Me3Si(p-XC6H4)NCOOEt (I) with X=Cl, H or Me in aqueous buffer solutions, with pH values from 1.94 to 10.00 were studied.The catalytic rate constants for the acid and base catalysed reactions and for the "non-catalysed" reaction k(H3O+), k(CH3COO-), k(H2PO-4), k(HPO2-4), k(NH3), k(OH-) and k0 were evaluated from the pseudo first-order rate constants kexp determined by UV spectroscopy.The Broensted coefficients for the base-catalysed reactions were obtained from the catalytic rate constants found and the known constants of dissociation K(HB+).The ρ values of the reactions could be derived from the ? constants given by Jaffe.The kinetical results obtained are interpreted mechanistically and are believed to also have model character for other nucleophilic substitution reactions with silicon compounds.
- Grosse-Ryuken, H.,Haenig, K.,Wagner, S.,Ruehlmann, K.,Schlapa, J.
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- PLATINUM COMPLEX CATALYZED REDUCTIVE N-CARBONYLATION OF NITROARENES TO THE CARBAMATES.
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The platinum catalyst combined with triphenylphosphine, tin(IV) chloride, and triethylamine showed high activity for the reductive N-carbonylation of nitroarene in ethanol at 180 degree C under carbon monoxide of 60 kg cm** minus **2. From nitrobenzene, ethyl phenylcarbamate was obtained in 83% yield. Iron(III) chloride, aluminum chloride and titanium(IV) chloride could be used as Lewis acids in place of tin(IV) chloride. Various nitroarenes were transformed into corresponding carbamate in moderate to excellent yields with the platinum catalyst.
- Watanabe,Tsuji,Takeuchi,Suzuki
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p. 3343 - 3348
(2007/10/02)
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- Preparation of aromatic urethanes
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This invention relates to an improved process for the preparation of urethanes by the reaction of aromatic nitro compounds with alcohols and carbon monoxides in the presence of catalyst systems containing sulphur and/or selenium and/or compounds of these elements.
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