Solution and flash vacuum pyrolyses of .beta.-(3,5-disubstituted-phenyl)ethanesulfonyl azides. Sultam, pyrindine, and azepine formation

Abramovitch, R. A.; Holcomb, William D.; THOMPSON, W. M.; Wake, Shigeo

doi:10.1021/jo00200a022

Cited by 12 publications

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“…The required 4-phenoxybutyl bromide ( 3b ) was commercially available while 4-bromo-1-(4-benzyloxyphenyl)butane ( 3a ) was synthesized in five steps from 4-phenoxybutyl bromide and 4-anisaldehyde following our disclosed procedures 12. Bromides 3a and 3b were heated with sodium sulfite using reaction conditions shown in Table 1, and the crude sodium sulfonates 4a and 4b were treated with thionyl chloride in the presence of catalytic amounts of DMF, under standard conditions,12,46,49 to give the respective sulfonyl chlorides 5a and 5b . As seen in Table 1, heating of 3a and sodium sulfite in refluxing water for 36 hours led to sulfonyl chloride 5a in 18% isolated yield (entry 1).…”

Section: Resultsmentioning

confidence: 99%

“…Non oxidative approaches for the synthesis of alkyl sulfonyl chlorides involve: (a) formation of Grignard or organolithium reagents from alkyl halides and subsequent addition to sulfuryl chloride;18,43,44 and (b) refluxing of bromides with sodium or ammonium sulfite in water45–49 to give the corresponding sulfonates that upon treatment with a chlorinating agent45–51 (e.g. SOCl 2 /DMF, POCl 3 , PCl 5 , cyanuric chloride etc.)…”

Section: Introductionmentioning

confidence: 99%

“…While seeking to improve the method which employs sodium sulfite in refluxing water,45–47,49 we found that use of microwave irradiation remarkably decreases the time required for the conversion of bromides to sodium sulfonates and enhances the yield of the respective sulfonyl chlorides. Optimal conditions involve microwave heating (160°C) of bromide and sodium sulfite in a mixture of THF:EtOH:H 2 O for 15 min.…”

Section: Introductionmentioning

confidence: 99%

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Microwave-assisted synthesis of sodium sulfonates precursors of sulfonyl chlorides and fluorides

Alapafuja

Nikas

Shukla

et al. 2009

Tetrahedron Letters

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Microwave-assisted synthesis of sodium sulfonates precursors of sulfonyl chlorides and fluorides

Alapafuja

Nikas

Shukla

et al. 2009

Tetrahedron Letters

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ChemInform Abstract: SOLUTION AND FLASH VACUUM PYROLYSES OF β‐(3,5‐DISUBSTITUTED‐PHENYL)ETHANESULFONYL AZIDES. SULTAM, PYRINDINE, AND AZEPINE FORMATION

Abramovitch¹,

Holcomb²,

THOMPSON³

et al. 1985

Chemischer Informationsdienst

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I. Photochemical nitration of methoxybenzenes from charge‐transfer complexes with tetranitromethane

Sankararaman

Kochi

1986

Recl. Trav. Chim. Pays‐Bas

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278 S . Sankararaman et al. / Photochemical nitration of methoxybenzenes Deaminations (general procedure)Deaminations in carboxylic acids were performed with 1 mmol of .-A solution of I mmol of the amine (or amine hydrochloride) in 30 ml of water was adjusted to pH 3.5 (glass electrode) with dilute perchloric acid. A conc. aqueous solution of sodium nitrite (0.25 g) and dilute perchloric acid were then added concurrently, maintaining a pH of 3.5. Stirring was continued for 24 h at room temperature. The solution was saturated with sodium chloride and extracted with ether. The extracts were dried over MgSO, and treated with 0.1 gof lithium aluminium hydride (1 h reflux) to remove alkyl nitrites. Excess LiAlH, was hydrolyzed; the precipitate was filtered off and washed with ether. The combined filtrate and washings were dried over MgSO,, concentrated and analyzed by GC. Where appropriate, the alcohols were isolated by prep. GC and acylated with N-(trifluoroacety1)-(S)-propyl chlorideI4 (2-butanol) or with (S)-2-acetoxypropionyl chloride15 (10,14) in order to allow estimation of their enantiomeric purities by GC.amine (or amine hydrochloride) and 0.25 g of sodium nitrite in 2.5 ml of acid (24 h at room temp.). The reaction mixture was stirred with 100 ml of saturated aqueous NaHCO,, followed by extraction with ether. (Complete removal of 2-ethylhexanoic acid required several extractions with NaHCO,). The combined organic solutions were dried over MgSO,, concentrated and analyzed by GC. Peaks were assigned with the aid of authentic compounds; (crude) samples of the esters were obtained from the appropriate alcohols and acid chlorides. The ester and alcohol fractions (order of elution) were separated by HPLC with ether/hexane (I/]). Hydrolysis of the esters with 0.5 g of potassium hydroxide in 2 ml of methanol at reflux was monitored by GC. The alcohols were recovered by partitioning between water and ether. For the estimation of enantiomeric purities, diastereomeric esters were prepared and analyzed by GC (as above).Recl. Trav. Chim. Pays-Bas 105, 278-285 (1986) Abstract. The direct irradiation of the charge-transfer (CT) absorption band of the 1/1 electron donor-acceptor complexes of dimethoxybenzenes with tetranitromethane leads to aromatic nitration with a high quantum yield. The analogous methoxytoluenes under the same photochemical conditions are converted in equally high yields to products of aromatic trinitromethylation. This dichotomy with different methoxybenzenes (ArH) is discussed within the context ofthe common reactive intermediates derived from the CT excitation of the complex. The subsequent interactions of the geminate fragments, i.e., [ArH ' , C(NO,), -, NO,], by radical-pair and ion-pair annihilation represent a unifying mechanism for the CT photochemistry leading to aromatic nitration and trinitromethylation.

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Solution and flash vacuum pyrolyses of .beta.-(3,5-disubstituted-phenyl)ethanesulfonyl azides. Sultam, pyrindine, and azepine formation

Cited by 12 publications

References 1 publication

Microwave-assisted synthesis of sodium sulfonates precursors of sulfonyl chlorides and fluorides

Microwave-assisted synthesis of sodium sulfonates precursors of sulfonyl chlorides and fluorides

ChemInform Abstract: SOLUTION AND FLASH VACUUM PYROLYSES OF β‐(3,5‐DISUBSTITUTED‐PHENYL)ETHANESULFONYL AZIDES. SULTAM, PYRINDINE, AND AZEPINE FORMATION

I. Photochemical nitration of methoxybenzenes from charge‐transfer complexes with tetranitromethane

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