α-Isocyanatoacrylonitriles from Alkylidene- or Arylidenecyanoacetic Acids; Synthesis and Reactions

Jaafar, Ihsan; Francis, G.; Danion-Bougot, R.; Danion, D.

doi:10.1055/s-1994-25405

Cited by 14 publications

(9 citation statements)

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“…Some of the yields in Table are not those of the isocyanates but those for succeeding one‐pot reactions to synthesize carbamates, amines, oxyazolines, and others . Therefore, the reaction times of the experiments include not only those for the formation of the isocyanates but additional periods for the reactions to obtain the final products.…”

Section: Resultsmentioning

confidence: 99%

“…Because it is better to use more than 20 data for the PLS regression to have meaningful results, we gathered 91 papers describing synthesis experiments of the Curtius rearrangement. However, only 16 examples listed in Table included all the experimental data required for the PLS regression. Figure displays all the acyl azides used to generate a model equation between yields, E a values, and experimental conditions.…”

Section: Methods Of Calculationsmentioning

confidence: 99%

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Predicting experimental yields as an index to rank synthesis routes II: application to the Curtius rearrangement

Yoshimura

Okano

Ishikawa

et al. 2011

J of Physical Organic Chem

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Synthesis yields of organic reactions are one of the most important factors in ranking synthesis routes created by synthesis route design systems such as Transform-Oriented Synthesis Planning and Knowledge base-Oriented Synthesis Planning. If it is possible to predict the yields of synthesis reactions before starting experiments, one can easily determine an order of synthesis routes for experimental works. In the present study, the reaction profiles of the Curtius rearrangement with different substituents were calculated to generate an equation predicting experimental yields of this reaction. Reactions followed by the formation of isocyanates were also analyzed to consider the relationship between reaction times and experimental yields. A partial least squares (PLS) regression was used to correlate the experimental yields with the calculated activation energies, E a (calc), together with experimental conditions such as dielectric constants of solvents, reaction times, and reaction temperatures as explanatory variables. Although the PLS regression using all the data gave very poor results, we succeeded in making a model equation with R 2 = 0.887 using a modified data set. However, there is a conflict between the predictability and the interpretability on the reaction time. This discrepancy mainly comes from unnecessarily long reaction times in the experiments for azides with calculated E a values of less than 33 kcal mol -1 . To construct a good model equation for the experimental yields of the Curtius reaction, we have to use data sets obtained from within 90 min of the reaction for the PLS regression.

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Section: Resultsmentioning

confidence: 99%

Section: Methods Of Calculationsmentioning

confidence: 99%

Predicting experimental yields as an index to rank synthesis routes II: application to the Curtius rearrangement

Yoshimura

Okano

Ishikawa

et al. 2011

J of Physical Organic Chem

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“…The mass spectra were determined using MP model MS-5988 and Shimadzu single focusing mass spectrophotometer (70 eV). Compound 1 has been synthesized according to Jaafar et al method [22]. The conduction time of all reactions and the purity of the products were monitored using thin-layer chromatography (TLC) technique.…”

Section: Methodsmentioning

confidence: 99%

“…In continuation of our ongoing program in the synthesis of biologically active heterocyclic systems from simple readily obtainable materials [11][12][13][14][15][16][17][18][19][20][21], the present work investigates the reactivity of high functionality 2-cyano-3-phenyl-2-propenoyl chloride [22] (1) with different mono-and bi-dentate nucleophiles aiming to obtain new derivatives with anticipated biological activities.…”

Section: Introductionmentioning

confidence: 99%

Utility of 2-cyano-3-phenyl-2-propenoyl chloride as Michael’s acceptor in heterocyclic synthesis with mono- and bi-dentate nucleophiles

et al. 2011

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“…et al[171] has reported that hydrazinolysis of 3-(4-methoxyphenyl) and 3-(2'-thienyl)-2-cyano-2-propenoyl chlorides 155a[172][173][174][175][176] and 155b at 0ºC afforded the pyrazolone derivatives 156, bishydrazine 157 and anisylideneazine 158, while, treatment of 155a with benzoylhydrazine afforded the pyrazolone 159, as outlined in Scheme 54. Ar = C6H4-OMe-p = 2electrophilicity of the lactonic carbonyl functionality of benzoxazinone 160 has been investigated [172] via its reaction with some nitrogen and oxygen nucleophiles.…”

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confidence: 99%

The Chemistry of Alkenyl Nitriles and its Utility in Heterocyclic Synthesis

Elgazwy¹

2013

Organic Chem Current Res

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including purines [7,8], pyrimidines [9], pyrazines [10] (some which are widely employed in the fluorescent dye industry [11]), imidazoles [12], biphenylenes [13], porphyrazines (which have great potential in optical sensor technology) [14] and diimines that are used as catalysts [15]. This review highlights the alkenyl nitrile chemistry with the focus on the utility of heterocyclic compounds. The synthesis and chemistry of the highly strained aryl nitrile is also briefly reviewed [16]. Heterocycles are ubiquitous in all kind of compounds of interest, and among all the possible synthetic methods of achieving their introduction into an structure, probably the use of a alkenyl nitrile analogue is the most direct one. The present review deals with the generation and synthetic uses of alkenyl nitriles and aryl nitriles formed in heterocyclic synthesis, and can be considered as an update of our revision published in 2007 on this topical [17]. Therefore, only references published from the second quarter of 2003 until the third quarter of 2010 are included, and the same restrictions to the literature coverage applied. Thus, only heterocycles compounds which are found applicability are considered. As previously, the present review is organized by the type of ring members and subdivided by the type of heterocycles fused compounds, including methods for their preparation and their synthetic uses. New developments in the utilities of some alkenyl nitriles in heterocyclic synthesis are reviewed. General synthetic routes based on the utilization of alkenyl nitriles of active imines are discussed. The major methods and modifications are analyzed [18-21]. In this review, which covers the literature up to date, we describe the new and improved methods for the construction of the skeletons, with a particular emphasis on the four, five and six membered ring of heterocyclic compounds. Some of these procedures have clear technical advantages over older methods in terms of yield and versatility, but do not employ new chemistry in the construction of the ring systems. The

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α-Isocyanatoacrylonitriles from Alkylidene- or Arylidenecyanoacetic Acids; Synthesis and Reactions

Cited by 14 publications

References 0 publications

Predicting experimental yields as an index to rank synthesis routes II: application to the Curtius rearrangement

Predicting experimental yields as an index to rank synthesis routes II: application to the Curtius rearrangement

Utility of 2-cyano-3-phenyl-2-propenoyl chloride as Michael’s acceptor in heterocyclic synthesis with mono- and bi-dentate nucleophiles

The Chemistry of Alkenyl Nitriles and its Utility in Heterocyclic Synthesis

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