Preparation and properties of alkyl 3-bromopropionimidate hydrochlorides

Schroeder, J. P.; Schroeder, D. C.; Hardin, J.A.; Marshall, Janet K.

doi:10.1021/jo01263a024

Cited by 5 publications

(3 citation statements)

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“…All ring-closing reactions gave yields of 25− 52%, and the yields of the substitution reactions from 5a−d to AOxCnSAc (n = 3−6) were 55 task was the synthesis of the molecules in the series with n = 2, as all of the derivatives, starting from the ω-bromo cyanides to the oxazole thioacetates, are very prone to elimination reactions forming the respective vinyl derivatives. To avoid the application of 3-bromopropionimidate hydrochloride, which already has been reported to be very sensitive, 48 the thioacetate group was introduced in the molecule already before performing all of the other steps. This was possible by addition of thioacetic acid to acrylonitrile.…”

Section: Resultsmentioning

confidence: 99%

Reestablishing Odd–Even Effects in Anthracene-Derived Monolayers by Introduction of a Pseudo-C_2v Symmetry

et al. 2019

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A series of anthracene [2,3-d]oxazolyl-2-alkylthioacetates (AOxCn-SAc) with n = 2−6 methylene groups in the alkyl chain were designed and synthesized to investigate the influence of the substitution along the long axis of the molecule on the structural behavior of the respective self-assembled monolayers (SAMs) on Au(111). While in previous work anthracene-terminated alkanethiols, in which the alkyl group was attached to the off-axis 2-position of the acene, showed an exceptionally small influence of the number of methylene groups (n) in the aliphatic linker, the new system exhibits a strong dependence of almost all monolayer properties on the length of the aliphatic linker, with the parity of n being the decisive parameter. These so-called odd−even effects are a result of the bond angle at the anchoring S atom as well as the all-trans conformation of the alkyl linkers, which in particular affect the packing density and the orientation of the aromatic part. Thus, using a variety of complementary experimental techniques, distinct odd−even variation of molecular inclination (by 10−11°) and the packing density (by 20%) were found, with the packing density of the odd-numbered systems being even as high as the ones of the well-established alkanethiolate systems. The high quality and well-defined character of these SAMs, along with a low band gap of only 3.0 eV, make them relevant for application in organic and molecular electronics.

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Section: Resultsmentioning

confidence: 99%

Reestablishing Odd–Even Effects in Anthracene-Derived Monolayers by Introduction of a Pseudo-C_2v Symmetry

et al. 2019

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“…Methanesulfonic acid (10 drops) was added. Solid m-chloroperbenzoic acid (450 g, 85% litre, 2.21 mol) was added, first in small batches (10)(11)(12)(13)(14)(15)(16)(17)(18)(19)(20) g), and then in increasingly larger amounts, at a rate just sufficient to maintain gentle refluxing of the chloroform. More methanesulfonic acid (10 drops) was added carefully after each 100 g of the peracid was added.…”

Section: Methodsmentioning

confidence: 99%

Synthesis of peristylane and the acs-(Cs)-C14-tetraquinane, C14-pentaquinane, and norperistylane systems

Eaton¹,

Mueller²,

Carlson³

et al. 1977

J. Am. Chem. Soc.

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“…In our original communication on the alcoholysis of amides (5), we postulated that acidic hydrolysis of the acyclic orthoester 24 was the leading pathway to yield the observed esters (Scheme 5). Conversely, there are numerous reported examples of hydrolysis of O-alkyliminium ethers such as 23 under acidic (25)(26)(27)(28)(29)(30)(31) or basic conditions (32)(33)(34)(35)(36)(37)(38)(39). In an effort to identify which of these two intermediates was formed, we decided to monitor the alcoholysis of 1-pyridylimidoyl triflate 6 with ethanol-d 6 by 1 H NMR (Fig.…”

Section: General Mechanisms For the Amide Activation Process And Convmentioning

confidence: 99%

Spectroscopic studies of the electrophilic activation of amides with triflic anhydride and pyridine

Charette¹,

Grenon²

2001

Can. J. Chem.

148

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The reaction of amides with trifluoromethanesulfonic (triflic) anhydride in the presence of pyridine was thoroughly investigated by NMR spectroscopic techniques. Different pyridinium intermediates were generated from secondary amides, tertiary amides with enolizable protons, and tertiary amides lacking enolizable protons. It was found that the actual triflating reagent is N-(trifluoromethylsulfonyl)pyridinium triflate 11 which is formed by the initial reaction of triflic anhydride with pyridine. The alcoholysis of these intermediates yields O-alkyliminium ethers which can then be easily hydrolyzed under mild acidic conditions to the corresponding esters.Résumé : La réaction entre un amide et l'anhydride trifluorométhanesulfonique (triflique) en présence de pyridine a été examinée minutieusement à l'aide de nombreuses techniques de spectroscopie RMN. Des intermédiaires pyridiniums différents ont été générés à partir d'amides secondaires, d'amides tertiaires avec des protons énolisables et d'amides tertiaires ne possédant pas de protons énolisables. Nous avons aussi démontré que le triflate de N-(trifluorométhylsulfonyl)pyridinium 11, formé lors de la réaction initiale entre l'anhydride triflique et la pyridine, est le véritable agent de triflation. L'alcoolyse de ces intermédiaires donne des éthers O-alkyliminiums qui peuvent être facilement hydrolysés dans des conditions légèrement acides aux esters correspondants. Charette and Grenon 1695Scheme 1. Functional group interconversion involving amides as starting materials.Scheme 2. Postulated intermediates formed in the reaction of amides with triflic anhydride.

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Preparation and properties of alkyl 3-bromopropionimidate hydrochlorides

Cited by 5 publications

References 1 publication

Reestablishing Odd–Even Effects in Anthracene-Derived Monolayers by Introduction of a Pseudo-C_2v Symmetry

Reestablishing Odd–Even Effects in Anthracene-Derived Monolayers by Introduction of a Pseudo-C_2v Symmetry

Synthesis of peristylane and the acs-(Cs)-C14-tetraquinane, C14-pentaquinane, and norperistylane systems

Spectroscopic studies of the electrophilic activation of amides with triflic anhydride and pyridine

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Preparation and properties of alkyl 3-bromopropionimidate hydrochlorides

Cited by 5 publications

References 1 publication

Reestablishing Odd–Even Effects in Anthracene-Derived Monolayers by Introduction of a Pseudo-C2v Symmetry

Reestablishing Odd–Even Effects in Anthracene-Derived Monolayers by Introduction of a Pseudo-C2v Symmetry

Synthesis of peristylane and the acs-(Cs)-C14-tetraquinane, C14-pentaquinane, and norperistylane systems

Spectroscopic studies of the electrophilic activation of amides with triflic anhydride and pyridine

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Product

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Reestablishing Odd–Even Effects in Anthracene-Derived Monolayers by Introduction of a Pseudo-C_2v Symmetry

Reestablishing Odd–Even Effects in Anthracene-Derived Monolayers by Introduction of a Pseudo-C_2v Symmetry