Arsonium Ylides Research Articles

ChemInform Abstract: REACTION OF PHENACYLTRIPHENYLARSONIUM BROMIDE WITH PHENYLHYDRAZINES: SYNTHESIS OF SOME NEW 3‐PHENYL‐1,2‐DIHYDROCINNOLINES THROUGH ARSONIUM YLIDES

Chemischer InformationsdienstVolume 13, Issue 34 Heterocyclic Compounds ChemInform Abstract: REACTION OF PHENACYLTRIPHENYLARSONIUM BROMIDE WITH PHENYLHYDRAZINES: SYNTHESIS OF SOME NEW 3-PHENYL-1,2-DIHYDROCINNOLINES THROUGH ARSONIUM YLIDES R. K. BANSAL, R. K. BANSALSearch for more papers by this authorS. K. SHARMA, S. K. SHARMASearch for more papers by this authorG. BHAGCHANDANI, G. BHAGCHANDANISearch for more papers by this author R. K. BANSAL, R. K. BANSALSearch for more papers by this authorS. K. SHARMA, S. K. SHARMASearch for more papers by this authorG. BHAGCHANDANI, G. BHAGCHANDANISearch for more papers by this author First published: August 24, 1982 https://doi.org/10.1002/chin.198234221Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume13, Issue34August 24, 1982 RelatedInformation

Remarks on the structural evidence of high reactivity of arsonium ylides bearing with an electron-withdrawing substituent

The crystal structures of benzoylmethylene triphenyl-arsorane, -phosphorane and triphenylarsine oxide have been studied so as to well account for the high reactivity of the title compounds.

Tributylarsonium-2,2,3,3,4,4-hexafluorocyclobutane ylide. Preparation and cleavage

F -cyclobutene forms a stable ylide with n -tributylarsine. In contrast to the halogen cleavage of the analogous phosphonium ylide, which gives 1,1-dihaloalkanes, the arsonium ylide reacts with bromine and iodine to give the 1-halo- F -cyclobutenes.

A highly stereoselective synthesis of transepoxides via arsonium ylides

A highly stereoselective synthesis of transepoxides via arsonium ylides

Preparation and Reactions of Some New Fluorinated Keto‐stabilised Arsonium Ylides

Darstellung und Reaktionen einiger neuer fluorierter ketostabilisierter Arsonium‐YlideZwei neue fluorierte ketostabilisierte Triphenylarsoniumsalze 2a, b werden dargestellt, die bei der alkalischen Zersetzung die entsprechenden neuen Arsoniumylide 3a, b ergeben. Bei Zugabe von Perchlorsäure entstehen daraus die Perchlorate 4a, b.Bei der Reaktion der Ylide 3a, b mit aromatischen Aldehyden entstehen in hohen Ausbeuten die Fluorchalcone 5a–e, 6a–c ohne nennenswerte Epoxidbildung. Zwei neue fluorierte Diketoarsoniumylide 7a, b werden durch Acylierung der Monoketoarsoniumylide dargestellt. Die Verbindungen sind durch Elementaranalysen, IR‐ und NMR‐Spektroskopie belegt.

ChemInform Abstract: STUDIES ON BETAINE DECOMPOSITION OF ARSONIUM YLIDES

AbstractDie Benzylbromide (II) führen bei Behandlung mit Triphenylarsin (I) zu Arsoniumbromiden, die auf zwei Wegen ‐ Behandlung mit NaH in Benzol oder Behandlung mit NaOMe in Methanol ‐ die entsprechenden Arsoniumylide (III) liefern.

ChemInform Abstract: TRANSYLIDATION REACTIONS IN ARSONIUM YLIDES

AbstractQuatemisierung von Triphenylarsin mit substituierten Benzylbromiden führt zu den Arsoniumbromiden (I), die bei Behandlung mit NaH in Benzol unter Dehydrohalogenierung die nicht isolierbaren, in Lösung stabilen Ylide (II) liefern.

Betaine Decomposition Studies of Arsonium Ylides Leading to Lactonyl and Lactothionyl Olefination

Abstract The synthetic potential of the Wittig reaction has reached the maximum as a most versatile tool for carbonyl olefination1–4, but our interest in this field arises from a wish to extend this area to some other types of olefination reactions.5,6 Until now it has been well established that olefination, either via phosphonium ylides or arsonium ylides, proceeds via stepwise formation of a betaine type compound and a four membered intermediate. It is the decomposition pattern of the betaines which is mainly responsible for the nature of product formation. We have recently carried out a thorough investigation of the arsonium betaines of carbonyls and exocyclic thiocarbonyls.7,8 However, the decomposition pattern of betaines formed by the nucleophilic attack of these ylides on α-lactonyl and α-lactothionyl systems still remains uninvestigated.

Studies on Betaine Decomposition of Arsonium Ylides

Abstract Betaine, Arsonium Ylides A systematic study on the nature of decomposition of betaine formed by nucleophilic attack of semistabilized arsonium ylides on thiocarbonyl substrates has been carried out. A series of substituted benzylidenetriphenylarsenanes have been generated from their corresponding salts and condensed with few cyclic thioketones to yield exocyclic olefins as exclusive products. The non-availability of thioepoxides indicates that the mode of decomposition of such type of betaines is quite analogous to the betaine formed by phosphonium ylides. The structure of the products have been assigned by IR and NMR spectral studies.

Transylidation Reactions in Arsonium Ylides

Abstract Some substituted benzylidenetriphenylarsenanes have been generated from their precursors and treated with acid chlorides or acid anhydrides to afford intermediate arsonium salts which in the presence of starting ylides undergo transylidation to give carbonyl stabilized arsonium ylides in fair to good yields. The structures of these stabilized ylides were confirmed on the basis of their spectral data.

Reaction of Arsonium Ylides with Carbonyl Compounds—Effect of Substituents at Arsenic

Alkenes and/or epoxides are formed on reaction of arsonium ylides with aldehydes. The product ratio can be influenced by variation of the substituents. Phosphonium ylides give only alkenes, and sulfonium ylides only epoxides.

Effect of solvent and base on the reactivity of semi-stabilized arsonium ylides

Effect of solvent and base on the reactivity of semi-stabilized arsonium ylides

Studies on ylides: exclusive carbonyl olefination with semistabilized arsonium ylides

The reactions of some semistabilized arsonium ylides with 9-anthrones and 9-anthraldehyde give 9-arylidene-10-hydroanthracenes, 9-arylidene-2-chloro-10-hydroanthracenes and 1-aryl-2-(9-anthryl)ethylenes, respectively. IR and NMR spectral data of the products are reported.

Studies on ylides: generation and reactions of new 2-naphthylmethylenetriphenylarsenanes

Two new semistabilized arsonium ylides have been generated and treated with carbonyl compounds. In reaction with carbonyl compounds, the carbanionic centres of both the ylides attack the carbonyl carbon to form similar cyclic intermediates. These intermediates, however, decompose to give different reaction products. The structures of the products are indicated by IR and NMR spectroscopy.

Some reactions of arsonium ylides involving transylidation

Methylenetriphenylarsenane, a nonstabilized arsonium ylide, has been shown to undergo transylidation on treatment with acyl halides to give carbonyl stabilized acylmethylenetriphenylarsenanes.

Studies on ylides exclusive formation of olefins from carbonyl compounds on treatment with para-bromo- and para-iodo-benzylidenetriphenylarsenanes

Two new semistabilized arsonium ylides, para-bromo- and para-iodo-benzylidenetriphenylarsenane, have been formed, and treated with a range of carbonyl compounds to yield exclusively trans-olefins. In no case was an epoxide obtained.

Studies on ylides formation and reactions of ortho- and meta-Nitrobenzylidenetriphenylarsenanes

Two semi-stabilized arsonium ylides, ortho-nitrobenzylidenetriphenylarsenane and meta-nitrobenzylidenetriphenylarsenane, were prepared and treated with a range of carbonyl compounds to yield trans-olefins. In no case was an epoxide isolated.

Studies on ylides: Carbonyl olefination with (p-nitro benzylidene)triphenylarsenane

(p-Nitrobenzylidene)triphenylarsenane, a semistabilized arsonium ylide has been prepared and reacted with carbonyl compounds to yield olefins as opposed to epoxidation products. Treatment of the ylide with a ranged acyl halides gave new disubstituted arsonium ylides. IR and NMR spectral data for the resulting products are reported.

Preparation and properties of some stable arsonium ylides

Stable crystalline arsonium ylides have been prepared by thermal decomposition of diazo compounds in the presence of triphenylarsine, and by condensation reactions of reactive methylene compounds with triphenylarsine oxide. The spectra of these ylides, and their reactions with benzaldehydes are discussed. Like other stabilised arsonium ylides they give alkenes rather than epoxides in Wittig reactions. They are generally more polar than their phosphonium analogues and also are more reactive in the Wittig reaction. With diphenylcyclopropenone some more reactive arsonium ylides form α-pyrones.

2,3,4-Triphenylcyclopentadienylides

The properties of pyridinium, triphenylphosphonium and triphenylarsonium 2,3,4-triphenylcyclopentadienylides are described and discussed, including their UV spectra, basicities and reactivities towards aldehydes and nitrosobenzene. The phosphonium and arsonium ylides are less basic than the corresponding tetraphenylcyclopentadienylides, yet more reactive towards benzaldehyde. The ylides undergo protonation and acylation at the 5-position and their salts condense at this position with p-dimethylaminobenzaldehyde.