Reaction of some nucleophiles with 2,6-di-tert-butylpyrylium perchlorate

1987 ◽  
Vol 52 (5) ◽  
pp. 1305-1314 ◽  
Author(s):  
Stanislav Böhm ◽  
Renata Prantová ◽  
David Šaman ◽  
Petr Trška ◽  
Josef Kuthan
Keyword(s):  
Hydrogen Sulfide ◽  
Sodium Borohydride ◽  
Ammonium Acetate ◽  
Sodium Cyanide ◽  
Pyridine Derivative ◽  
Similar Reaction ◽  
Subsequent Reaction ◽  
Tert Butyl ◽  
Electrophilic Reagents ◽  
Pyran Derivative

The title compound IV reacted with sodium borohydride to give the 4H-pyran VIIa and the dienone VIIIa whereas its reaction with sodium cyanide afforded exclusively the dienone VIIIb. Reaction of the salt IV with tert-butylmagnesium chloride or bromide gave a mixture of the 4H-pyran VIIa and the corresponding 4-tert-butyl derivative V. Upon treatment with hydrogen sulfide and hydrogen chloride, this mixture afforded 2,4,6-tri-tert-butyl-4H-thiopyran XI whereas aromatization with chloranil and subsequent reaction with ammonium acetate resulted in 2,4,6-tri-tert-butylpyridine (X). Analogously, the perchlorate IV reacted with ammonium acetate to give 2,6-di-tert-butylpyridine (VI). Addition of triphenylphosphine and potassium phthalimide to IV afforded exclusively the 4H-pyran derivatives XII and XIII. A similar reaction of nitromethyl anion led to the 4,4'-bis(4H-pyran) derivative XIV. Mechanism of the studied reactions and the reasons for the low reactivity of the sterically hindered pyridine derivative VI with electrophilic reagents are discussed.

Déplacements homolytiques intramoléculaires. 2. Décomposition du perpentène-4 oate de tert-butyle dans les éthers

1984 ◽  
Vol 62 (11) ◽  
pp. 2385-2390 ◽  
Author(s):  
A. Kharrat ◽  
C. Gardrat ◽  
B. Maillard
Keyword(s):  
Double Bond ◽  
Main Product ◽  
Similar Reaction ◽  
Tert Butyl ◽  
Lower Temperature ◽  
Induced Decomposition

The thermolysis of tert-butyl perpent-4-enoate 1 in THF led to several compounds; the main product, 5-(2-tetrahydrofuryl)-4-pentanolide (yield 42%) comes from an induced decomposition of the perester occurring with the addition of 2-tetrahydrofuryl radical to the double bond. A similar reaction was performed at a lower temperature, using butyl perdicarbonate as initiator, but did not define the mechanism (concerted or two-step). The thermolysis of 1 in ethers (THP, oxepane, 1,4-dioxane, dipropyl ether) appears to be a useful synthetic tool: several new γ-lactones have been obtained in this way.

scholarly journals Uses of -diketones for the synthesis of novel heterocyclic compounds and their antitumor evaluations

2020 ◽  
Vol 34 (2) ◽  
pp. 385-405
Author(s):  
R. M. Mohareb ◽  
M. M. Kamel ◽  
Y. R. Milad
Keyword(s):  
Cell Lines ◽  
Ammonium Acetate ◽  
Benzimidazole Derivative ◽  
Ethyl Cyanoacetate ◽  
Pyridine Derivative ◽  
Active Compounds ◽  
Reference Drug ◽  
Thiophene Derivatives ◽  
Active Methylene ◽  
Dihydropyridine Derivatives

The reaction of the 3-oxo-N,3-diphenylpropan-amide (3) with either malononitrile or ethyl cyanoacetate in ammonium acetate gave the 1,2-dihydropyridine derivatives 6a or 6b, respectively. On the other hand, carrying the same reaction in the presence of triethylamine gave the 1,6-dihydropyridine derivatives 7a and 7b, respectively. Moreover, compound 3 reacted with 2-aminoprop-1-ene-1,1,3-tricarbonitrile to give the pyridine derivative 9. Compound 7b reacted with the active methylene derivatives 10a,b and 4a,b to give the naphthyridine derivatives 11a,b and 12a,b; respectively. Compound 3 was also used for the synthesis of thiophene derivatives 13a,b and 16a,b. In addition, the reaction of ethyl benzoylacetate (1) with o-phenylene diamine gave the benzimidazole derivative 18. The reactivity of the latter product towards different reagents was studied to give different products. The cytotoxicity of the newly synthesized products was studied towards some cancer and normal cell lines, in addition toxicity of compounds was measured and docking of the most active compounds was done. Compounds 6b, 7b, 9, 13a, 13b, 16a, 20b, 20c, 24b, 25 and 26b exhibited optimal cytotoxic effect against cancer tested cell lines. These active compounds were evaluated against c-Met kinase using foretinib as the reference drug where all compounds expressed higher activity than the reference drug.                     KEY WORDS: Ethyl benzoylacetate, Pyridine, Benzimidazole, Cytotoxicity   Bull. Chem. Soc. Ethiop. 2020, 34(2), 385-405 DOI: https://dx.doi.org/10.4314/bcse.v34i2.15

Biogenic Hydrogen Sulfide for Cyanide Regeneration in Solutions during Cupriferous Gold Ores Processing

2017 ◽  
Vol 262 ◽  
pp. 131-134
Author(s):  
Anna A. Faiberg ◽  
Aleksandra N. Mikhailova ◽  
Vladimir E. Dementiev ◽  
Sergey S. Gudkov
Keyword(s):  
Hydrogen Sulfide ◽  
Sodium Cyanide ◽  
Gold Recovery ◽  
Copper Recovery ◽  
Thermophilic Microorganisms ◽  
Copper Cyanide ◽  
Gold Ores ◽  
Hydrometallurgical Processing ◽  
Optimal Approach ◽  
Process Solutions

An optimal approach to the problem of cupriferous gold ores hydrometallurgical processing is the recycling of process solutions after copper recovery and regeneration of cyanide bound in complexes. The study focuses on the copper-cyanide solutions processing technology using biogenic hydrogen sulfide for copper recovery in the form of сhalcocite, and cyanide regeneration. The strains of anaerobic sulfidogenic thermophilic microorganisms Desulfurella acetivorans and Desulfurella Kamchatkensis were used for producing hydrogen sulfide. The studies on copper precipitation and cyanide regeneration were conducted on copper-cyanide process solutions which were obtained during cyanidation of refractory cupriferous gold-bearing flotation concentrates from one of the deposits in the South Ural (Russia). Ten cycles of "Cyanidation-Regeneration" were carried out in total. The copper recovery was 86–96 %; the cyanide regeneration obtained 96 %. On an average 8.9 kg of sodium cyanide and 4.6 kg of copper sulfide were recovered from 1 m3 of solution. The sodium cyanide consumption decreased from 25.0 kg/t to 6.0 kg/t without reducing gold recovery during the CIL (carbon-in-leach) recycling process. The gold recovery was the same 63–68 %.

Synthesis of a Dinuclear μ-(η2-Thioaldehyde)zirconocene Cation Complex

2002 ◽  
Vol 57 (10) ◽  
pp. 1184-1188 ◽  
Author(s):  
Silke Courtenay ◽  
Sarah Smith ◽  
Emily Hollink ◽  
Ulrich Blaschke ◽  
Gerald Kehr ◽  
...  
Keyword(s):  
Similar Reaction ◽  
Subsequent Reaction ◽  
Rapid Elimination ◽  
Cation Complex

Treatment of (butadiene)zirconocene with two molar equivalents of benzylmercaptane results in the formation of Cp2Zr(SCH2Ph)2 (11). Subsequent reaction of 11 with [Cp2ZrCH3+][CH3B(C6F5)3-](12) leads to rapid elimination of methane to yield the dinuclear [μ-(η2-thiobenzaldehyde)(μ-SCH2Ph)(ZrCp2)2+] cation complex 14. A similar reaction is observed upon treatment of Cp2Zr(SC2H5)2 (15) with 12 to yield the thioacetaldehydebridged dinuclear metallocene cation complex Cp2Zr-μ-(η2-MeCHS)-μ-(SEt)ZrCp2 (16).

ChemInform Abstract: Ring Closure Reaction of 4-tert-Butyl-4-penten-1-ol with Electrophilic Reagents.

ChemInform ◽  
2010 ◽  
Vol 30 (28) ◽  
pp. no-no
Author(s):  
M. Lj. Mihailovic ◽  
S. Gojkovic ◽  
S Milosavljevic ◽  
S. Konstantinovic
Keyword(s):  
Ring Closure ◽  
Tert Butyl ◽  
Electrophilic Reagents

scholarly journals tert-Butyl 3-(3-methyl-1-oxidopyridin-1-ium-2-yl)benzoate

IUCrData ◽  
2016 ◽  
Vol 1 (1) ◽  
Author(s):  
Gerhard Laus ◽  
Volker Kahlenberg ◽  
Sven Nerdinger ◽  
Frank Richter ◽  
Herwig Schottenberger
Keyword(s):  
Hydrogen Bonds ◽  
Dihedral Angle ◽  
Title Compound ◽  
Cyclic Dimer ◽  
Pyridine Derivative ◽  
Tert Butyl ◽  
Compound C ◽  
Sheet Structure ◽  
Ring Centroid

In the title compound, C17H19NO3, which was obtained by oxidation of the corresponding pyridine derivative, the dihedral angle between the benzene and the pyridine rings is 68.2 (1)°. In the crystal, C—H...O hydrogen bonds to carboxyl andN-oxide O-atom acceptors gives a cyclic dimer substructure with anR22(18) motif which is extended into a undulating sheet structure lying parallel to (100) through weak C—H...Ooxidehydrogen bonds. Also present are π–π ring interactions [ring centroid separation = 3.561 (2) Å].

Synthesis of cedranoid sesquiterpenes. V. The biotols

1988 ◽  
Vol 66 (11) ◽  
pp. 2805-2815 ◽  
Author(s):  
Peter Yates ◽  
Rupinder S. Grewal ◽  
Peter C. Hayes ◽  
Jeffery F. Sawyer
Keyword(s):  
Hydrogen Chloride ◽  
Hydrogen Fluoride ◽  
Sodium Borohydride ◽  
Lithium Aluminum Hydride ◽  
Aluminum Hydride ◽  
Butyl Alcohol ◽  
Lithium Aluminum ◽  
Tert Butyl ◽  
Tert Butyl Alcohol ◽  
Cerium Trichloride

Reduction of dimethyl 3-hydroxy-4,4,8-trimethyl-6-oxo-cis-bicyclo[3.3.0]octa-2,7-diene-1,2-dicarboxylate (8) with lithium and ammonia gives dimethyl 3-hydroxy-4,4,exo-8-trimethyl-6-oxo-cis-bicyclo[3.3.0]oct-2-ene-1,2-dicarboxylate (9), which on acetylation, reduction with sodium borohydride, and methanolysis gives dimethyl 3,exo-6-dihydroxy-4,4,exo-8-trimethyl-cis-bicyclo[3.3.0]oct-2-ene-1,2-dicarboxylate (12). This on 2-decarbomethoxylation followed by treatment with lithium acetylide in the presence of cerium trichloride gives methyl 3-ethynyl-3,exo-6-dihydroxy-4,4,exo-8-trimethyl-cis-bicyclo[3.3.0]octane-1-carboxylate (21), which on hydration, diacetylation, and treatment with tri-n-butyltin hydride and azoisobutyronitrile is converted to methyl exo-6-acetoxy-3-acetyl-4,4,exo-8-trimethyl-cis-bicyclo[3.3.0]octane-1-carboxylate (31). Methanolysis of 31. tert-butyldimethylsilylation, and reaction with potassium tert-butoxide in tert-butyl alcohol gives exo-4-tert-butyldimethylsilyloxy-exo-2,6,6-trimethyl[5.3.11,5]undecane-8,10-dione (35). This on treatment with lithium aluminum hydride followed by oxidation and hydrogenation provides the corresponding 10-deoxo compound, 39. Reaction of this with methyllithium, dehydration, and desilylation with hydrogen fluoride in acetonitrile gives a mixture of (±)-α-biotol (1) and (±)-β-biotol (2); desilylation with hydrogen chloride in methanol gives solely (±)-1.

Synthesis of 3,5-dicyano-4-phenyl-2,6-bis(4-p-terphenylyl)-1,4-dihydropyridine. An attempt at extending the Hantzsch synthesis

1985 ◽  
Vol 50 (9) ◽  
pp. 1962-1970 ◽  
Author(s):  
Štefan Marchalín ◽  
Josef Kuthan
Keyword(s):  
Molecular Structure ◽  
Acetic Acid ◽  
Ammonium Acetate ◽  
Spectral Characteristics ◽  
Pyridine Derivative ◽  
Hantzsch Synthesis ◽  
Benzylidene Derivative ◽  
Dihydropyridine Derivatives

The 3-oxopropanenitrile IIIc, prepared from 4-acetyl-p-terphenyl (IV) by the sequence IV → V → VI → IIIc, reacts with benzaldehyde and ammonium acetate in acetic acid to give the Hantzsch 1,4-dihydropyridine VIIc and the corresponding pyridine derivative VIIIc. The alternative cyclocondensation of benzylidene derivative IIc and 3-oxopropanenitrile IIIc in the presence of ammonium acetate exclusively gives the pyridine derivative VIIIc. Rate of thermal and oxidative aromatizations of the 1,4-dihydropyridine derivatives, VIIa → VIIc → VIIIa → VIIIc, decreases in the order VIIc > VIIb > VIIa. Mechanism of these transformations and spectral characteristics of compounds VIIc and VIIIc are discussed with regard to their molecular structure.

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