23901-74-8Relevant academic research and scientific papers
Self-Immolative System for Disclosure of Reactive Electrophilic Alkylating Agents: Understanding the Role of the Reporter Group
Chippindale, Ann M.,Gavriel, Alexander G.,Hayes, Wayne,Khurana, Gurjeet S.,Leroux, Flavien,Lewis, Viliyana G.,Russell, Andrew T.,Sambrook, Mark R.
, p. 10263 - 10279 (2021/08/16)
The development of stable, efficient chemoselective self-immolative systems, for use in applications such as sensors, requires the optimization of the reactivity and degradation characteristics of the self-immolative unit. In this paper, we describe the effect that the structure of the reporter group has upon the self-immolative efficacy of a prototype system designed for the disclosure of electrophilic alkylating agents. The amine of the reporter group (a nitroaniline unit) was a constituent part of a carbamate that functioned as the self-immolative unit. The number and position of substituents on the nitroaniline unit were found to play a key role in the rate of self-immolative degradation and release of the reporter group. The position of the nitro substituent (meta- vs para-) and the methyl groups in the ortho-position relative to the carbamate exhibited an influence on the rate of elimination and stability of the self-immolative system. The ortho-methyl substituents imparted a twist on the N-C (aromatic) bond leading to increased resonance of the amine nitrogen's lone pair into the carbonyl moiety and a decrease of the leaving character of the carbamate group; concomitantly, this may also make it a less electron-withdrawing group and lead to less acidification of the eliminated β-hydrogen.
SELF-IMMOLATIVE SYSTEMS
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Page/Page column 22; 23, (2020/05/28)
The present invention is concerned with self-immolative recognition and/or responsive systems for electrophilic compounds, especially alkylating agents, which systems may comprise disclosure or detection of the alkylating agent. The present invention is especially concerned with non-protic triggered self-immolative systems, molecules, and methods, and in particular for detection of non- protic electrophilic agents, and especially alkylating agents, for example alkyl or benzylic halides, which may be found in pesticides or fumigants, or chemical warfare agents.
Self-immolative systems for the disclosure of reactive electrophilic alkylating agents
Acton, Aaron L.,Leroux, Flavien,Feula, Antonio,Melia, Kelly,Sambrook, Mark R.,Hayes, Wayne,Russell, Andrew T.
supporting information, p. 5219 - 5222 (2019/05/07)
In this paper we report the design, synthesis and assessment of the first examples of self-immolative systems triggered by non-acidic electrophilic agents such as methyl, allyl or benzylic halides. These systems provide a visual colorimetric disclosure response upon exposure to these electrophilic reagents under mild, basic conditions without the need for the use of analytical instrumentation.
PHOSPHORORGANISCHE VERBINDUNGEN 105. Synthese chiraler und achiraler ditertiaerer 1-Phosphino-2-Aminoethan-Derivate (=P-CH2-CHR-N=) und einige Anwendungen
Horner, Leopold,Dickerhof, Karlheinz
, p. 331 - 350 (2007/10/02)
Primary amines with an optical active ligand add to vinyl- and propenylphosphonium salts according the reaction schemes (5) and (6), forming compounds of the type E and F.F contains a new asymmetric center in the bridge giving rise to the formation of a mixture of diastereomers, which can be resolved.Phosphonium salts of the type E and F with a benzyl group on the phosphonium center are cleaved reductively by alkali amalgams (Li/Hg; Na/Hg; K/Hg) forming tertiary phosphines with an aminogroup in the β-position.The reductive cleavage with alkali amalgams is superior to the cathodic cleavage.Application: The synthesis of Ni(0)- and Pd(0)-complexes of type J fails.Bis-phosphine complexes of type 21 are formed.The rate of the homogeneous hydrogenation of 1-hexene with Rh(I)-complexes (containing G as a ligand) has an optimum with respect to a Rh/Co-catalyst proportion of 1:2 to 1:1.6.The optical induction of the homogeneous hydrogenation of Z-N-Acylamino-cinnamic acid is lower than 5percent.
