POTASSIUM DERIVATIVES OF FLUORENE AS INTERMEDIATES IN THE PREPARATION OF C9-SUBSTITUTED FLUORENES: III. THE INFLUENCE OF SOLVENT AND METAL IN THE FORMATION OF C9-SUBSTITUTED FLUORENES FROM 9-FLUORENYL METALS

1961 ◽  
Vol 39 (4) ◽  
pp. 799-807 ◽  
Author(s):  
G. W. H. Scherf ◽  
R. K. Brown
Keyword(s):  
Methyl Iodide ◽  
Benzyl Chloride ◽  
Room Temperature ◽  
Organometallic Compounds ◽  
Lithium Compound ◽  
Hydrocarbon Solvents ◽  
Derivatives Of ◽  
Ether Solvents ◽  
Potassium Compound ◽  
Influence Of Solvent

Equimolar quantities of 9-fluorenyl-potassium, -sodium, or -lithium and alkyl or aralkyl halides at room temperature in ether solvents yielded a mixture of unchanged fluorene, C9-monosubstituted fluorene, and C9-disubstituted fluorene. The amount of disubstitution never exceeded that of unchanged fluorene, and was found to be maximum (∼35%) for the potassium compound in 1,2-dimethoxyethane, somewhat less for the sodium analogue, and small (∼5%) for the lithium compound. In hydrocarbon solvents such as hexane, 9-fluorenylpotassium gave only 7% of C9-disubstituted fluorene. The lithium compound, upon reaction with methyl iodide or ethyl iodide gave, along with unreacted fluorene, only C9-monosubstituted fluorene. But reaction of 9-fluorenyllithium with benzyl chloride in hexane gave a small quantity (∼5%) of disubstituted fluorene as well as the monosubstituted product.The results are explained in terms of (a) the solubilities of the organometallic compounds in ether and hydrocarbon solvents, (b) the polarity of the metal carbon bond, and (c) the acidity of the hydrogen on C9 of fluorene.

Organophosphorus chemistry. IV. Synthesis and reactions of 2-Ethoxy-6-oxo-1,2-azaphosphinane 2-oxide

1984 ◽  
Vol 37 (8) ◽  
pp. 1631 ◽  
Author(s):  
DG Hewitt ◽  
MW Teese
Keyword(s):  
Methyl Iodide ◽  
Benzyl Chloride ◽  
Allyl Bromide ◽  
Organometallic Reagents ◽  
Organophosphorus Chemistry ◽  
Derivatives Of

2-Ethoxy-6-oxo-1,2-azaphosphinane 2-oxide (3) has been prepared by cyclocondensation of ethyl 4-(P-amino-P-ethoxyphosphinoyl)butanoate (17). N-Alkylated derivatives of (3) were prepared by cyclocondensation of (17) in the presence of methyl iodide, allyl bromide and benzyl chloride. These derivatives reacted with organometallic reagents and bases to yield acyclic products.

Syntheses of 1, 2, and 9-methyl derivatives of 4,9-dihydro-3-methyl-4-oxo-1H(2H)-pyrazolo[3,4-b]quinoline and their antiviral activity

1985 ◽  
Vol 50 (5) ◽  
pp. 1057-1063 ◽  
Author(s):  
Stanislav Rádl ◽  
Viktor Zikán ◽  
František Šmejkal
Keyword(s):  
Influenza Virus ◽  
Antiviral Activity ◽  
Methyl Iodide ◽  
Room Temperature ◽  
Encephalomyocarditis Virus ◽  
Methyl Derivative ◽  
Sodium Salts ◽  
Methyl Derivatives ◽  
Derivatives Of

The paper describes syntheses of 4,9-dihydro-3-methyl-4-oxo-1H(2H)-pyrazolo[3,4-b]quinoline (Ia), its 1-methyl derivative (Ib), 2-methyl derivative (IIa), 9-methyl derivative (Ic), 1,9-dimethyl derivative (Id) and 2,9-dimethyl derivative (IIb). Sodium salts of compounds Ia, Ib, Ic and IIa were methylated with methyl iodide in dimethylformamide at room temperature, compounds Id and IIb were demethylated with pyridine hydrochloride. The compounds prepared were tested for antiviral activity in vivo in mice against influenza virus A2-Hongkong and the Encephalomyocarditis virus.

Development of the room temperature protocol based on room temperature ionic liquids and surfactant ionic liquids for the synthesis of derivatives of 2-amino-thiazoles and thermo-physical analysis of the synthesized derivatives using TGA-DSC.

2020 ◽  
Vol 10 ◽  
Author(s):  
Chandrakant Sarode ◽  
Sachin Yeole ◽  
Ganesh Chaudhari ◽  
Govinda Waghulde ◽  
Gaurav Gupta
Keyword(s):  
Thermal Analysis ◽  
Heat Capacity ◽  
Ionic Liquids ◽  
Specific Heat ◽  
Specific Heat Capacity ◽  
Room Temperature ◽  
Heat Capacity Data ◽  
General Strategy ◽  
Capacity Data ◽  
Derivatives Of

Aims: To develop an efficient protocol, which involves an elegant exploration of the catalytic potential of both the room temperature and surfactant ionic liquids towards the synthesis of biologically important derivatives of 2-aminothiazole. Objective: Specific heat capacity data as a function of temperature for the synthesized 2- aminothiazole derivatives has been advanced by exploring their thermal profiles. Method: The thermal gravimetry analysis and differential scanning calorimetry techniques are used systematically. Results: The present strategy could prove to be a useful general strategy for researchers working in the field of surfactants and surfactant based ionic liquids towards their exploration in organic synthesis. In addition to that, effect of electronic parameters on the melting temperature of the corresponding 2-aminothiazole has been demonstrated with the help of thermal analysis. Specific heat capacity data as a function of temperature for the synthesized 2-aminothiazole derivatives has also been reported. Conclusion: Melting behavior of the synthesized 2-aminothiazole derivatives is to be described on the basis of electronic effects with the help of thermal analysis. Additionally, the specific heat capacity data can be helpful to the chemists, those are engaged in chemical modelling as well as docking studies. Furthermore, the data also helps to determine valuable thermodynamic parameters such as entropy and enthalpy.

scholarly journals Cat-CrNP as new material with catalytic properties for 2-chloro-2-propen-1-ol and ethylene oligomerizations

2021 ◽  
Vol 11 (1) ◽  
Author(s):  
Jacek Malinowski ◽  
Dagmara Jacewicz ◽  
Artur Sikorski ◽  
Mariusz Urbaniak ◽  
Przemysław Rybiński ◽  
...  
Keyword(s):  
Complex Compound ◽  
Atmospheric Pressure ◽  
Room Temperature ◽  
Organometallic Compounds ◽  
Ethylene Oligomerization ◽  
High Catalytic Activity ◽  
New Material ◽  
Activity Requirement ◽  
Olefin Oligomerization ◽  
Xrd Method

AbstractThe contemporary search for new catalysts for olefin oligomerization and polymerization is based on the study of coordinating compounds and/or organometallic compounds as post-metallocene catalysts. However known catalysts are suffered by many flaws, among others unsatisfactory activity, requirement of high pressure or instability at high temperatures. In this paper, we present a new catalyst i.e. the crystalline complex compound possesing high catalytic activity in the oligomerization of olefins, such as 2-chloro-2-propen-1-ol and ethylene under very mild conditions (room temperature, 0.12 bar for ethylene oligomerization, atmospheric pressure for 2-chloro-2-propen-1-ol oligomerization). New material—Cat-CrNP ([nitrilotriacetato-1,10-phenanthroline]chromium(III) tetrahydrate) has been obtained as crystalline form of the nitrilotriacetate complex compound of chromium(III) with 1,10-phenanthroline and characterized in terms of its crystal structure by the XRD method and by multi-analytical investigations towards its physicochemical propeties The yield of catalytic oligomerization over Cat-CrNP reached to 213.92 g · mmol−1 · h−1· bar−1 and 3232 g · mmol−1 · h−1 · bar−1 for the 2-chloro-2-propen-1-ol and ethylene, respectively. Furthemore, the synthesis of Cat-CrNP is cheap, easy to perform and solvents used during preparation are environmentally friendly.

Unterscheidung von Stickstoff- und Phosphor-Inversion, Rotation um die N-P-Bindung und Ligandenaustausch am Phosphor

1968 ◽  
Vol 23 (6) ◽  
pp. 759-766 ◽  
Author(s):  
D. Imbery ◽  
H. Friebolin
Keyword(s):  
Low Temperatures ◽  
Room Temperature ◽  
Nitrogen Inversion ◽  
Kinetic Processes ◽  
Derivatives Of

A large number of aminophosphines were prepared to study the kinetic processes. It could be shown that at room temperature there is rapid nitrogen-inversion but slow phosphorous-inversion. At higher temperatures ( + 80 °C), a rapid chlorine-exchange takes place with inversion of configuration at phosphorous. At low temperatures ( — 80 °C), rotation around the N-P-bond was slow. A dependence of the barrier of rotation on the size of the substituents could be recognized. It is possible that pπ-dπ-bonding is partially responsible for the relatively high barrier of rotation compared with derivatives of ethane and hydrazine.

Sulfur Linkage in Vulcanized Rubber. Reaction of Methyl Iodide with Sulfur Compounds

1949 ◽  
Vol 22 (1) ◽  
pp. 1-7
Author(s):  
M. L. Selker
Keyword(s):  
Methyl Iodide ◽  
Room Temperature ◽  
Sulfur Compounds ◽  
Point Of View ◽  
Secondary Reaction ◽  
Reaction Products ◽  
Sulfide Sulfur ◽  
Vulcanized Rubber ◽  
Allyl Sulfide

Abstract The work described here is an extension of the study of the reaction of methyl iodide with sulfur compounds originally begun with the purpose of using such data in determining the sulfur linkage in vulcanized rubber. A previous paper dealt with the reactions of methyl iodide with propanethiol, propyl sulfide, propyl disulfide, allyl sulfide, and thiophene. This article adds to the list, n-butyl methallyl sulfide, allyl disulfide, allyl tetrasulfide, n-propyl tetrasulfide, and trithiane. The removal of combined sulfur from vulcanized rubber as trimethylsulfonium iodide on treatment with methyl iodide at room temperature was persuasive evidence of the presence of sulfide sulfur linked to allylic type residues. The evidence offered, however, did not constitute exclusive proof because it was not known whether still other types of sulfur linkage would also yield trimethylsulfonium iodide. To shed more light on this question, the sulfur linkages most likely to occur in vulcanizates—the allyl-alkyl monosulfide, diallyl and dialkyl di- and polysulfide—were investigated. The trithiane reaction is of interest mostly from the point of view of the reaction of overcured stocks or secondary reaction products stemming from the original polysulfides. The reactions were carried out using the method described in a previous paper.

The Chemical Evolution of a Nitrogenase Model, 20 Alkyl Molybdates(VI) and the Mechanism of Hydrocarbon Production by Nitrogenase [1]

1982 ◽  
Vol 37 (3) ◽  
pp. 380-385 ◽  
Author(s):  
G. N. Schrauzer ◽  
Laura A. Hughes ◽  
Norman Strampach
Keyword(s):  
Aqueous Solution ◽  
Alkaline Hydrolysis ◽  
Room Temperature ◽  
Bond Cleavage ◽  
Model Compounds ◽  
Hydrocarbon Production ◽  
Acidic Solutions ◽  
Reducing Conditions ◽  
Hydrolysis Of ◽  
Derivatives Of

Abstract Colorless alkylmolybdates(VI) of composition R-MoO3-are generated in aqueous solutions by the alkaline hydrolysis of complexes R-Mo(Bpy)(0)2Br(Bpy = 2,2′-bipyridyl, R = CH3 and higher alkyl). At room temperature in alkaline aqueous solution, the new organometallic derivatives of oxomolybdate(VI) are remarkably resistant against Mo-C bond hydrolysis. Decomposition occurs more rapidly on heating, affording unrearranged alkanes according to the eq.: R-MoO3- + OH-→RH + Mo04=. In acidic solutions, the methylmolybdate(VI) species decomposes with the formation of a mixture of methane and ethane while higher alkylmolybdates carrying hydrogen in the β-position relative to molybdenum undergo Mo-C bond heterolysis by way of β-elimina-tion: R-CH2CH2-MoO3 → Mo+4 (aq) + H+ + R-CH = CH2. The Mo-C bond of alkylmolybdates is resistant to oxidants but is very sensitive to cleavage under reducing conditions. Reductive Mo-C bond cleavage occurs particularly rapidly in the presence of thiols and reduced ferredoxin model compounds. The latter reactions simulate the terminal steps of hydrocarbon producing reactions of nitrogenase with alternate substrates such as CN-, R-CN or R-NC, confirming previous mechanistic conclusions concerning the mechanism of nitrogenase action.

Reaction of Trivalent Organophosphorus Compounds with Selenium

1978 ◽  
Vol 33 (9) ◽  
pp. 1040-1046 ◽  
Author(s):  
Maria Konieczny ◽  
George Sosnovsky
Keyword(s):  
Room Temperature ◽  
Organophosphorus Compounds ◽  
Phosphorus Compounds ◽  
Trivalent Phosphorus ◽  
Derivatives Of

Selenium derivatives of pentavalent organophosphorus compounds 9, 10, 11 (Ṙ = 2,2,6,6- tetramethyl-1-oxyl-4-piperidyl), 12 and 13 were prepared in 79-99%yields via the reaction of the corresponding trivalent phosphorus compounds 14, 15, 16, 17, 18 with blackselenium in benzene at room temperature in 20 hours.

scholarly journals Nucleofugal behavior of a β-shielded α-cyanovinyl carbanion

2018 ◽  
Vol 14 ◽  
pp. 3018-3024
Author(s):  
Rudolf Knorr ◽  
Barbara Schmidt
Keyword(s):  
Michael Addition ◽  
Carbonyl Compounds ◽  
Room Temperature ◽  
Experimental Conditions ◽  
Metal Free ◽  
Metal Derivatives ◽  
Carbonyl Addition ◽  
Derivatives Of

Sterically well-shielded against unsolicited Michael addition and polymerization reactions, α-metalated α-(1,1,3,3-tetramethylindan-2-ylidene)acetonitriles added reversibly to three small aldehydes and two bulky ketones at room temperature. Experimental conditions were determined for transfer of the nucleofugal title carbanion unit between different carbonyl compounds. These readily occurring retro-additions via C–C(O) bond fission may also be used to generate different metal derivatives of the nucleofugal anions as equilibrium components. Fluoride-catalyzed, metal-free desilylation admitted carbonyl addition but blocked the retro-addition.

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