Facile Synthesis of Sulfonyl Chlorides/Bromides from Sulfonyl Hydrazides

A simple and rapid method for efficient synthesis of sulfonyl chlorides/bromides from sulfonyl hydrazide with NXS (X = Cl or Br) and late-stage conversion to several other functional groups was described. A variety of nucleophiles could be engaged in this transformation, thus permitting the synthesis of complex sulfonamides and sulfonates. In most cases, these reactions are highly selective, simple, and clean, affording products at excellent yields.     

N－烷基吡咯烷酮的合成

Ｎ－烷基吡咯烷酮的合成王锡臣，张颂培，祝钧（北京轻工业学院化工系北京１０００３７）关键词烷基吡咯烷酮，固－液相转移催化，合成Ｎ－烷基吡咯烷酮可用作香波增稠剂，染发烫发调理剂，啤酒、葡萄酒中多酚洁净化剂和洗涤去渍剂等［１］，其合成一般采用吡咯烷酮Ｎ－烷...     

Multicomponent Reaction for Synthesis of N-Arylsulfonyl Pyrazoles

A synthesis of functionalized N-arylsulfonyl pyrazoles from the multicomponent reaction of arylsulfonyl hydrazones and dialkyl acetylenedicarboxylates in the presence nucleophilic compounds such as pyridine, isoquinoline, or triphenylphosphine, in good yields, is described.

[Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications® for the following free supplemental resources: Full experimental and spectral details.]     

One-Pot Synthesis of Highly Functionalized Stable Ketenimines by Three-Component Reaction of Cyclohexyl Isocyanide,Dialkyl Acetylenedicarboxylates,and Benzoyl Hydrazones

The adduct produced in the reaction between cyclohexyl isocyanide and dialkyl acetylenedicarboxylates was trapped by benzoyl hydrazones to afford highly functionalized ketenimines in good yields. The reaction is characterized by mild conditions, high selectivity, and tolerance to various functional groups.     

Synthesis of Dialkyl Phosphorylsuccinates from the Reaction of Thiouracil Derivatives with Dialkyl Acetylenedicarboxylates in the Presence of Trialkylphosphites

Abstract

Dialkyl-2-(dialkoxyphosphonyl)-3-(1,6-dihydro-6-oxo-4-propylpyrimidin-2-ylthio) succinates and dialkyl-2-(dialkoxyphosphonyl)-3-(1,6-dihydro-6-oxopyrimidin-2-ylthio) succinates were synthesized in moderate to high yields using a novel, facile, and one-pot condensation of dialkyl acetylenedicarboxylates, trialkylphosphites, and thiouracil derivatives.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.

GRAPHICAL ABSTRACT      

Novel Thiochromanone Derivatives Containing a Sulfonyl Hydrazone Moiety: Design,Synthesis, and Bioactivity Evaluation

A series of novel thiochromanone derivatives containing a sulfonyl hydrazone moiety were designed and synthesized. Their structures were determined by ¹H-NMR, ¹³C-NMR, and HRMS. Bioassay results showed that most of the target compounds revealed moderate to good antibacterial activities against Xanthomonas oryzae pv. oryzae, Xanthomonas oryzae pv. oryzicolaby, and Xanthomonas axonopodis pv. citri. Compound 4i had the best inhibitory activity against Xanthomonas oryzae pv. oryzae, Xanthomonas oryzae pv. oryzicolaby, and Xanthomonas axonopodis pv. citri, with the EC₅₀ values of 8.67, 12.65, and 10.62 μg/mL, which were superior to those of Bismerthiazol and Thiodiazole-copper. Meanwhile, bioassay results showed that all of the target compounds proved to have lower antifungal activities against Sclerotinia sclerotiorum, Fusarium oxysporum, Gibberella zeae, Rhizoctonia solani, Verticillium dahlia, and Botrytis cinerea than those of Carbendazim.     

Synthesis of 2,2'-Quinocyanines with Long N-Alkyl Substituents

2,2'-Quinocyanines with long alkyl substituents on one or both nitrogen atoms have been synthesized. ¹H NMR spectroscopy has been used to study the processes occurring during the alkylation of the starting quinoline bases.     

Synthesis of Novel Saccharide Hydrazones

Synthesis of important heterocyclic hydrazine derivatives N-aminopyrrolidine, N-aminopiperidine, and N-aminoazepane from hydrazine hydrate and dihalogenides were examined and optimized. These heterocyclic hydrazine derivatives were used in condensation reactions with six different monosaccharides to form corresponding hydrazones. Biological evaluations of these novel compounds, which are simple acyclic nucleoside analogs, were done. L-Arabinose N-aminoazepane hydrazone showed minor anti-HIV activity, giving a starting point for further structural modifications.     

Phase-Transfer-Catalyzed Michaelis-Becker Synthesis of Dialkyl Methyl Phosphonates

A liquid–liquid phase-transfer-catalyzed (PTC) Michaelis-Becker reaction was adopted in the preparation of dialkyl methyl phosphonate (R = Me, iPr, nBu, and iBu). This was performed by the reaction of an appropriate dialkyl hydrogen phosphonate with methyl iodide in the presence of benzyl triethyl ammonium chloride and sodium hydroxide as PTC and base, respectively. A liquid–liquid two-phase system (H₂O/CH₂Cl₂) introduced a suitable situation for the preparation of dialkyl methyl phosphonates with bulky alkyl groups (R = iPr, nBu, and iBu), but with R = Me, the hydrolysis of dimethyl hydrogen phosphonate (reagent) reduced the yield to 22%. In this case, a solid–liquid PTC-free system was successfully applied and yield of over 80% was obtained.     

磺酰氯合成方法研究进展

综述了磺酰氯的合成方法,主要包括氯磺酸直接氯磺化,由磺酸氯化、含硫化合物氧化并氯化、由氨基化合物经重氮化并氯磺化、由卤代物间接氯磺化和饱和烷烃直接氯磺化等,并对各种合成方法的要点和适用范围等进行了评述.     

A Facile,One-Pot Synthesis of Azoic Compounds and Anthraquinone Derivatives Containing Dialkyl Phosphoryl Moieties in Multicomponent Reactions

Protonation of the reactive 1:1 intermediates produced in the reactions between triphenylphosphine and dialkyl acetylenedicarboxylates by 1-amino-anthraquinone or 1,5-diphenylcarbazone as a core dye leads to vinyl phosphonium salts, which undergo Michael addition with conjugate base of NH compounds to produce stable phosphorus ylides as novel dyes in fairly good yields. These ylides can exist in two geometrical isomers (Z) and (E) for 3, because the negative charge of the ylide moiety of these compounds are strongly conjugated with the adjacent carbonyl group. Rotation around the carbon–carbon double bond is slow in the (Z) and (E) geometrical isomers on the NMR time scale at ambient temperature. These compounds are assigned by their IR, ¹H, ¹³C NMR spectral data as well as their mass spectroscopic data.     

Microwave Irradiation Technique for Synthesis of Dialkyl Dithiophosphoric Acids

Microwave heating technique was applied to the preparation of dialkyl dithiophosphoric acids from the reaction of alcohol with phosphorus pentasulphide. A microwave oven (CEM-MDS 2000) was utilized to determine the preparation conditions for the best yield of dialkyl dithiophosphoric acids under atmospheric pressure at various times and power. Six different (C 4 -C 9 ) chain-length of dialkyl dithiophosphoric acids were studied. All experiments were performed in an open Teflon (poly-tetrafluoroethylene) vessel. The results obtained showed that the reaction of dialkyl dithiophosphoric acids can be achieved more rapidly using microwave heating than using conventional procedures.     

The Synthesis and Properties of Some Fluorinated Dialkyl Phosphoramidates

The synthesis and physical properties of the first fluorinated dialkyl phosphoramidates of structure (RCH 2 O) 2 P(O)NHCH 2 R F , where R = CH 3 , CF 3 or CCl 3 and R F = CF 3 or C 2 F 5 , are described. They were obtained by treatment of the respective dialkyl phosphorochloridates with trifluoroethylamine or pentafluoropropylamine in ether in the presence of triethylamine.     

The Synthesis of Aromatic Hydrazones as Nitrogen-Containing Prostaglandin Congeners

Severalnitrogen-containingprostaglandincongeners,suchasAHl9437[I]andSQ29548II',werereportedt0beexhibitingpotentactivitiesontissuesclassifiedascontainingTX-sensitivereceptors(TP).Theseledustopreparetheimp0rtantintermediatesIIIbyusingsubstitutedanilinesthroughthenucle0philicoxiranering0peningreacti0n0f2,3-ep0xylbicyclo[3.2.O]hept-6-one'.Inthisarticle,wereport0nthesynthesis0faromatichydraz0nesIVasnitrogen-c0ntainingprostaglandinc0ngenersfromdifferentar0matichydrazinesandIIItosearchforTP-r…     

An Approach to Disulfide Synthesis Promoted by Sulfonyl Chloride in Sodium Bicarbonate Aqueous Media

A mild and efficient protocol for the synthesis of disulfides in aqueous media using mercaptans promoted by sulfonyl chloride is reported. This reaction offers the advantages of mild reaction conditions, short reaction time, high yields, and simple operation.     

Chemoselective entry to 5-mercaptotriazoles by condensation of acetylenic esters with triphenylphosphine

A new kind of 1,2,4-triazol derivatives containing ylide moiety were designed and synthesized. The reaction is performed by condensation of dialkyl acetylenedicarboxylate with 5-aryl-2H-1,2,4-triazol-3-thiol in the presence of Ph₃P. In these cases, the reactions take place on the sulfur atom in good to excellent yields via a chemoselective manner.     

The Mechanism of Thionyl Chloride Reaction with Dialkyl Alkylphosphonothionate Using 31 P NMR

Based on 31 P NMR studies of thionyl chloride reaction with dialkyl alkylphosphonothionates, a method for preparation of alkylphosphonic dichloride has been investigated. A mechanism via intermediacy of ester chloride is suggested.