151436-92-9Relevant articles and documents
Cyclopropane formation via a simple barbier reaction in DMF
Oudeyer, Sylvain,Aaziz, Akima,Léonel, Eric,Paugam, Jean Paul,Nédélec, Jean-Yves
, p. 485 - 488 (2003)
Cyclopropanes are prepared in good yields via magnesium activation of polyhalomethyl compounds (dichlorodiphenylmethane, methyl trichloroacetate, α,α,α-trichlorotoluene, benzal chloride, benzal bromide) in the presence of activated olefins in DMF.
Nickel-Catalyzed Favorskii-Type Rearrangement of Cyclobutanone Oxime Esters to Cyclopropanecarbonitriles
Fang, Ping,Mei, Tian-Sheng,Shuai, Bin
supporting information, p. 1637 - 1641 (2021/10/02)
A nickel-catalyzed base-promoted rearrangement of cyclobutanone oxime esters to cyclopropanecarbonitriles was developed. The ring opening of cyclobutanone oxime esters occurs at the sterically less hindered side. A base-promoted nickelacyclobutane intermediate, formed in situ, is assumed to be involved in the formation of the product.
Preparation method of cibenzoline succinate midbody
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Paragraph 0015; 0016; 0017; 0018, (2017/12/09)
The invention discloses a preparation method of a cibenzoline succinate midbody, relates to a preparation method of the cibenzoline succinate midbody 1-cyanogroup-2,2-diphenyl cyclopropane and belongs to the field of drug chemical synthesis. The preparation method comprises the following steps that an oxidation reaction is generated with benzophenone hydrazone as a raw material and hydrogen peroxide as an oxidizing agent under the presence of a phase transfer catalyst, then diphenyldiazomethane is obtained and directly reacts with acrylonitrile without purification in the reaction system, and the midbody 1-cyanogroup-2,2-diphenyl cyclopropane is obtained. According to the method, the recovery rate is high, operation is easy and convenient, discharging of three wastes is reduced, the production cost of cibenzoline succinate is reduced remarkably, and the method is quite beneficial for industrialized production.
Towards nitrile-substituted cyclopropanes-a slow-release protocol for safe and scalable applications of diazo acetonitrile
Hock, Katharina J.,Spitzner, Robin,Koenigs, Rene M.
supporting information, p. 2118 - 2122 (2017/07/24)
Diazo acetonitrile has long been neglected despite its high value in organic synthesis due to a high risk of explosions. Herein, we report our efforts towards the transient and safe generation of this diazo compound, its applications in iron catalyzed cyclopropanation and cyclopropenation reactions and the gram-scale synthesis of cyclopropyl nitriles.
New synthesis of multisubstituted cyanocyclopropanes by the intramolecular SN2 alkylation and 1,3-CC insertion reaction of magnesium carbenoids as the key reactions
Saitoh, Hideki,Watanabe, Tatsuya,Kimura, Tsutomu,Kato, Yuichi,Satoh, Tsuyoshi
scheme or table, p. 2481 - 2495 (2012/05/05)
Addition reaction of 1-chlorovinyl p-tolyl sulfoxides derived from ketones and aldehydes with lithium α-cyano carbanions gave nitrile adducts in high to quantitative yields. Treatment of the nitrile adducts derived from acetonitrile with excess i-PrMgCl in THF resulted in the formation of cyanocyclopropanes via the intramolecular SN2 alkylation of the generated magnesium carbenoids. The intermediate of this reaction was proved to be a cyclopropylmagnesium chloride and was reactive with electrophiles to give multisubstituted cyanocyclopropanes. On the other hand, the reaction of the nitrile adducts derived from arylacetonitriles with i-PrMgCl resulted in the formation of 2-arylcyanocyclopropanes by the 1,3-carbon-carbon (1,3-CC) insertion reaction of the generated magnesium carbenoid intermediates. This reaction was found to proceed in a highly stereospecific manner. The key reactions, intramolecular SN2 alkylation and 1,3-CC insertion reaction of the magnesium carbenoids, are the first examples for the reaction of the magnesium carbenoids bearing a nitrile functional group.
Novel process for the synthesis of class I antiarrhythmic agent (±)-cibenzoline and its analogs
Gholap, Atul R.,Paul, Vincent,Srinivasan, Kumar V.
, p. 2967 - 2982 (2008/12/22)
Synthesis of (±)-cibenzoline and its analogs has been achieved by a simple sequence of reactions. The diaryl cyanoolefin intermediate 3 could be prepared by Knoevenagel condensation of benzophenone with ethylcyanoacetate to form the tetra-substituted olefin intermediate 2 followed by Krapcho deethoxycarbonylation or from β-hydroxynitrile intermediate 2' followed by the elimination of hydroxyl group respectively. The 2,2- diphenylcyclopropanecarbonitrile 4 was synthesized from intermediate 3 by cyclopropanation, which was converted to (±)-2-(2,2-diphenylcyclopropyl)- 2-imidazoline 5 by reaction with ethylenediamine in the presence of a catalytic amount of sulfur. Moreover, the obtained 2-imidazolines were smoothly oxidized to the corresponding imidazoles 6 in good to moderate yields. Copyright Taylor & Francis Group, LLC.
The first enantioenriched metalated nitrile possessing macroscopic configurationat stability
Carlier, Paul R.,Zhang, Yiqun
, p. 1319 - 1322 (2007/12/29)
Figure presented Magnesium - bromine exchange on enantiopure cyclopropyl bromonitrile 5 at -100°C for 1 min followed by a D2O quench gives the deuterionitrile in 81% ee (retention); additional trapping experiments establish t1/2(rac) = 11.4 h at -100°C. These experiments provide the first glimpse into the stereochemical aspects of Mg-Br exchange. The intermediate formed is the first metalated nitrile demonstrated to possess macroscopic configurational stability.
Cyclopropane formation by copper-catalysed indirect electroreductive coupling of activated olefins and activated α,α,α-trichloro or gem-dichloro compounds
Sengmany,Leonel,Paugam,Nedelec
, p. 533 - 537 (2007/10/03)
Cyclopropanes have been prepared in good yields by indirect electroreductive coupling of activated olefins and activated α,α,α-trichloro or gem-dichloro compounds (Cl3CCO2Me, PhCCl3, Ph2CCl2, PhCHCl2). This process, using a copper complex in catalytic amountss is convenient for the reagent couple activated olefin/activated polyhalide, whatever the reduction potential of each reagent relative to each other. The main advantage of our electrochemical process is that it does not require the use of hazardous, toxic, or not easily prepared reagents like diazocompounds or diazirines.
Reactions of tosylhydrazones of benzaldehyde and benzophenone with cyanoalkenes in a basic two-phase system
Jończyk,Wlostowska,Ma?akosza
, p. 2827 - 2832 (2007/10/03)
Reaction of tosylhydrazones 1a,b with cyanoalkenes 3a,b, carried out in the presence of concentrated aq. sodium hydroxide in dioxane, afforded either cyanocyclopropanes 5, 9 or pyrazoles 13, 14 and 16, 17. The process takes place via generation of diazocompounds 2a,b from 1a,b their [3+2] cycloaddition to 3a,b with the formation of unstable pyrazolines 4, further fate of which depends on the structure of R1 and R2 substituents.
REACTIVITY OF THE ACIDS OF TRIVALENT PHOSPHORUS AND THEIR DERIVATIVES. PART III. THE =P-O- IONS IN REACTION WITH ACTIVATED ALKYL BROMIDES. ATTACK ON BROMINE vs ELECTRON TRANSFER
Dembkowski, Leszek,Rachon, Janusz
, p. 251 - 262 (2007/10/02)
The mechanism of reductive debromination in the course of the reaction of sodium dialkyl (diaryl) phosphites as well as the sodium salt of dibenzylphosphine oxide with activated alkyl bromides in THF has been investigated.Probable mechanisms namely SET and X-philic substitution are discussed.The cyclopropyl system was chosen for the study of this reaction.The results of the carried out experiments (unrearranged products, no influence of light) suggest that the cyclopropyl radical intermediate (if it is formed) does not paticipate in the product-determining step ofthe reductive debromination under the action of the =P-O- ions.Key words: Bromocyclopropanes, reductive debromination, dialkyl phosphites, diaryl phosphites, dibenzylphosphine oxide, SET, X-philic substitution.
