Cyanocarbon Chemistry. IX.<sup>1</sup> Heterocyclic Compounds from Dicyanoketene Acetals

Middleton, W. J.; Engelhardt, V. A.

doi:10.1021/ja01544a059

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“…can be prepared in reactions of dicyanoketene acetals with certain N-bases [34]. Therefore the synthesis of heterocycles starting from 1 as described by Saalfrank & Ackermann [9] [lo] is not characteristic for vinyl-diazonium ions, but is rather an additional example for the reactivity of certain ketene acetals.…”

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confidence: 99%

Reactions of Alkenediazonium Salts. Part 1. 2,2‐Diethoxyethene‐diazonium hexachloroantimonate: A diazonium, a carbenium or an oxonium salt?

Szele¹,

Tencer²,

Zollinger³

1983

Helvetica Chimica Acta

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SummaryReactions of the title compound 1 with various nucleophiles have been studied. The salt behaves like an alkylating agent towards ethers, alcohols and water forming ethyl diazoacetate (2), which reacts further with excess of the nucleophile. A solvent cage mechanism accounting for the observed products is proposed. Thermal decomposition in inert solvents leads to the alkylation of the counter-ion, i.e. formation of chloroethane, and in anisole, alkylation and chlorination of the solvent are also observed.With a standard coupling component, 2-naphtholate ion, no azo coupling reaction of 1 is observed, but instead 14-methyl-14H-dibenzo [a,j]xanthene (17) is formed. The products of the reaction with diethylamine are diethylcyanoformamide (18) and ethyl diethylcarbamate (19). None of the chemistry of salt 1 is explained by the intervention of vinyl cations expected to be formed in a heterolytic dediazoniation. The predominant pathways seem to involve reactions of an oxonium salt (alkylating properties) or, in the case of diethylamine, a carbenium salt (primary nucleophilic attack on the p-C-atom of 1).The free energy barrier to C=C rotation in 1 is estimated to be 75 to 77 kJ/mol (18.0 to 18.5 kcal/mol), a value which falls between those expected for a double and a single bond.Introduction. -In the context of our investigations on the dediazoniation mechanism of aromatic diazonium ions'), comparisons with the reactivity of vinyldiazonium ions are interesting. Owing to their electronic similarity vinyldiazonium ions might be reagents for the formation of vinyl cations.The unsubstituted vinyldiazonium ion, H,C=CH-N,+, is not yet known. Therefore a theoretical study on the vinyldiazonium ion in the gas phase and in aqueous solution is a worthwhile undertaking. With others, we recently made such a study [2] for the gas phase by ab initio (STO-3G and 4-31G), and for solution by CND0/2 methods. This investigation is a continuation of previous theoretical

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confidence: 99%

Reactions of Alkenediazonium Salts. Part 1. 2,2‐Diethoxyethene‐diazonium hexachloroantimonate: A diazonium, a carbenium or an oxonium salt?

Szele¹,

Tencer²,

Zollinger³

1983

Helvetica Chimica Acta

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“…The compound was obtained in 87% yield as a yellow solid, mp 170–180°C. IR (KBr): 3330, 3225, 2922, 2856, 2214, 1627, 1530, 1384, 980 cm −1 ; 1 H NMR (500 MHz, DMSO‐ d 6 ): δ 2.58 (s, 3H, SCH 3 ), 7.41–7.47 (m, 3H, ArH), 8.25–8.29 (m, 2H, ArH); 13 C NMR (125 MHz, DMSO‐ d 6 ): δ 12.5, 82.8, 115.1, 128.9, 128.9, 132.1, 136.6, 163.1, 163.1, 173.1; HRMS (TOF ES + ): m / z calcd for C 12 H 11 N 4 S [(M+H) + ], 243.0699; found, 243.0703 [22].…”

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confidence: 99%

Microwave‐Assisted Solvent‐Free Synthesis of Highly Functionalized Pyrimidine Derivatives

Yan

Niu

Chen

et al. 2012

Journal of Heterocyclic Chem

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“…Then we synthesized monomethoxypyrimidines, which are important in pyrimidine chemistry not only due to their high biological activity [6,7] but also their chemical properties, which are reminiscent of iminoethers. They can act as intermediates in the synthesis of polyfunctional pyrimidine derivatives [8 -10].…”

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Synthesis and antitumor activity of new 5-(4-alkoxybenzyl)pyrimidines

et al. 2008

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Cyanocarbon Chemistry. IX.¹ Heterocyclic Compounds from Dicyanoketene Acetals

Cited by 50 publications

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Reactions of Alkenediazonium Salts. Part 1. 2,2‐Diethoxyethene‐diazonium hexachloroantimonate: A diazonium, a carbenium or an oxonium salt?

Reactions of Alkenediazonium Salts. Part 1. 2,2‐Diethoxyethene‐diazonium hexachloroantimonate: A diazonium, a carbenium or an oxonium salt?

Microwave‐Assisted Solvent‐Free Synthesis of Highly Functionalized Pyrimidine Derivatives

Synthesis and antitumor activity of new 5-(4-alkoxybenzyl)pyrimidines

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Cyanocarbon Chemistry. IX.1 Heterocyclic Compounds from Dicyanoketene Acetals

Cited by 50 publications

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Reactions of Alkenediazonium Salts. Part 1. 2,2‐Diethoxyethene‐diazonium hexachloroantimonate: A diazonium, a carbenium or an oxonium salt?

Reactions of Alkenediazonium Salts. Part 1. 2,2‐Diethoxyethene‐diazonium hexachloroantimonate: A diazonium, a carbenium or an oxonium salt?

Microwave‐Assisted Solvent‐Free Synthesis of Highly Functionalized Pyrimidine Derivatives

Synthesis and antitumor activity of new 5-(4-alkoxybenzyl)pyrimidines

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Cyanocarbon Chemistry. IX.¹ Heterocyclic Compounds from Dicyanoketene Acetals