In Situ Formation of Vilsmeier Reagents Mediated by Oxalyl Chloride: a Tool for the Selective Synthesis of <i>N</i>‐Sulfonylformamidines

Gazvoda, Martin; Kočevar, Marijan; Polanc, Slovenko

doi:10.1002/ejoc.201300402

Cited by 32 publications

(20 citation statements)

References 41 publications

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“…Intermediate 4 was obtained through the diazotization of material 2-chloro-5-nitrobenzenamine (1), [21] nucleophilic substitution reaction of 2-chloro-5-nitrophenylsulfonyl chloride (2) and 25% -28% ammonium hydroxide, [22] and reduction of nitro group with Fe/HCl. [27] The synthetic routes towards the target compounds I were summarized in Scheme 1. 2-Chloro-5-diethylaminophenylsulfonamide (II-7) was prepared by a process starting from ethylation of amino group in structure 4 with sodium cyanoborohydride, 40% acetaldehyde aqueous solution and acetic acid in acetonitrile at room temperature, [24] followed by protection of sulfonamide with N,N-dimethylformamide dimethyl acetal (DMF-DMA), [25,26] then the second ethylation at 50 ℃, and finally deprotection with 80% hydrazine hydrate in ethanol.…”

Section: Synthetic Chemistrymentioning

confidence: 99%

Controllable Effect of Structural Modification of Sulfonylurea Herbicides on Soil Degradation

et al. 2016

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The study of soil degradation behaviors of sulfonylurea herbicides in relation to their different structural attributes is utmost important for us to comprehend the development of new eco-friendly herbicides. It is postulated that the structural modification of the chemical structures could influence their degradation rates in soil. Nine devised structures were synthesized to study their herbicidal activity as well as their soil degradation behaviors respectively. The novel compounds I-3-I-7 were characterized by UV, 1 H NMR and 13 C NMR, MS and EA. Bioassays indicated that most of target compounds displayed superior herbicidal activities in comparison with Chlorsulfuron. Soil degradation results further confirmed our previous assumption that the introduction of electron-donating substituents at 5 th position of the benzene ring distinctly increased their degradation rates, among which dimethylamino and diethylamino groups can adjust the degradation rate to a more favorable status.

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Section: Synthetic Chemistrymentioning

confidence: 99%

Controllable Effect of Structural Modification of Sulfonylurea Herbicides on Soil Degradation

et al. 2016

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“…13 C NMR spectroscopic data were recorded with a Bruker Avance DRX 500 (125.7 MHz) spectrometer. 31 (6), 41157 (7) reflections were measured at 173(1) K (for 3a, 5b, 6) and 123(1) K (for 7) with a Bruker Smart Apex II diffractometer operating in the ωand -scan mode. 2686 (3a), 4877 (5b), 5328 (6), 11035 (7) unique reflections [R int = 0.041 (3a), 0.036 (5b), 0.042 (6), 0.095 (7)] were used in further refinement.…”

Section: Methodsmentioning

confidence: 99%

“…The formamidine substituent P-C bonds are not equivalent [P-1-C-1 1.8670(16), P-1-C-10 1.8795(15) Å] and substantially longer than those P-C bonds to the phenyl ring [P-1-C-21 1.8218(16) Å]. (16), P-1-C-10 1.8795(15), P-1-C-21 1.8218 (16), N-1-C-1 1.367 (2), N-2-C-1 1.283 (2), N-3-C-10 1.360 (2), N-4-C-10 1.290(2); C-1-P-1-C-10 101.99 (7), N-1-C-1-N-2 128.29 (15), N-3-C-10-N-4 119.11 (14).…”

Section: Reaction With Phosphorus(iii) Chloridesmentioning

confidence: 99%

C‐Silyl‐N,N‐dialkyl‐N′‐arylformamidines: Synthesis and Reactions with Phosphorus(III) Chlorides

et al. 2016

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A method for the synthesis of new C‐silyl‐N,N‐dialkyl‐N′‐arylformamidines was developed. These derivatives were formed by the deprotonation of N‐(trimethylsilyl)formamidinium salts to give the corresponding N‐trimethylsilyl carbenes followed by a 1,2‐migration of the silyl group. The reactions of C‐silylformamidines with phosphorus(III) chlorides were then studied. The reactions between chlorodiphenylphosphane and the C‐silylformamidines readily afforded C‐phosphanylformamidines in high yields. The reactions of dichlorophosphanes and C‐silylformamidines yielded previously unknown phosphanes that feature two formamidine substituents. In the reaction with phosphorus trichloride, the sterically least encumbered formamidine gave a stable two‐coordinate compound through the formation of an intermediate tris(phosphane). The reactions of the sterically more encumbered formamidines led to the substitution of only two chlorine atoms to give a chlorophosphane or benzazaphosphole. The structures of key compounds were proven by X‐ray crystal structure analyses.

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“…A straightforward, cheap, and very selective route for constructing N ‐sulfonylformamidines 202 from sulfonamides or N ‐acylated sulfonamides 201 using imidoyl chloride mediated by oxalyl chloride under mild reaction conditions was discovered. Treatment between N , N ‐disubstituted formamides 200 and oxalyl chloride produced in situ imidoyl chlorides which undergo acylation with sulfonamides or N ‐acylated sulfonamides 201 to provide the expected N ‐sulfonylformamidines 202 in excellent yields (Scheme ) …”

Section: Preparation Of Imidoyl Chloridesmentioning

confidence: 99%

Oxalyl Chloride: A Versatile Reagent in Organic Transformations

Mohammadkhani

Heravi

2019

ChemistrySelect

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Oxalyl chloride, (COCl)2, as an inexpensive commercially available chemical is one of the most versatile applicable organic reagents in chemical transformations. It is also employed extensively in various chemical industries. It is employed in various chemical transformations such as chlorination, oxidation, reduction, dehydration, decarboxylation, and formylation reactions as well as ring cleavage of epoxides. During the past decades, numerous procedures using (COCl)2 as reagent have been developed and published. However, its importance has largely been overlooked by the absence of a comprehensive review in chemical literature dealing with its application in organic transformations and its utilization in the chemical industry. This Review aims to provide an overview for the applications of oxalyl chloride in organic synthesis, including its physical properties, synthesis, as well as its unique roles as the reagent in organic reactions, covering the literature over the past 103 years (from 1916 to date).

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In Situ Formation of Vilsmeier Reagents Mediated by Oxalyl Chloride: a Tool for the Selective Synthesis of N‐Sulfonylformamidines

Cited by 32 publications

References 41 publications

Controllable Effect of Structural Modification of Sulfonylurea Herbicides on Soil Degradation

Controllable Effect of Structural Modification of Sulfonylurea Herbicides on Soil Degradation

C‐Silyl‐N,N‐dialkyl‐N′‐arylformamidines: Synthesis and Reactions with Phosphorus(III) Chlorides

Oxalyl Chloride: A Versatile Reagent in Organic Transformations

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