Thermal rearrangements of arylaroylaziridines into 2,5-diaryloxazoles

Padwa, Albert; Eisenhardt, William

doi:10.1039/c19680000380

Cited by 14 publications

(12 citation statements)

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“…It is probable that the benzoyl azirine (11) is an intermediate in the various thermal processes.cf. 12 In earlier reports3, 13 correspond to a 2,3-diphenylazirine ion radical, i.e. the molecular ion of V, and that the decomposing form of the [C13Hs]+ ion had the properties of a phenalenyl rather than a fluorenyl cation.…”

Section: Vi) (Vii)mentioning

confidence: 94%

Electron‐impact studies XCV–skeletal rearrangement fragments in the mass spectra of 3,5‐ diphenylisoxazole and 3,5‐ diphenylpyrazole

Aldous

Bowie

1975

Org. Mass Spectrom.

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Section: Vi) (Vii)mentioning

confidence: 94%

Electron‐impact studies XCV–skeletal rearrangement fragments in the mass spectra of 3,5‐ diphenylisoxazole and 3,5‐ diphenylpyrazole

Aldous

Bowie

1975

Org. Mass Spectrom.

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“…Various aziridines are isomerized by the different conditions such as thermal or non-thermal, [1][2][3] acids or nucleophilic reagents [4][5][6][7][8] and/or photochemical [9,10]. The isomerization of the aziridines are strongly influenced by the nature of the substituents present in them Since the spectral data (e.g., 1 H and 13 Cnmr, ir, and elemental analysis) were not conclusive to assign the stereochemistry of the product, X-ray crystallographic analysis was conducted on 3 to verify product structure.…”

Section: Introductionmentioning

confidence: 99%

Regio- and stereo-synthesis, crystal structure and NMR assignments of N-((Z)-1-oxo-1-phenyl-3-(4-chlorophenyl)prop-2-en-2-yl)-4-nitrobenzamide

Samimi

2015

J IRAN CHEM SOC

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and also the conditions employed [11,12]. Although a large variety of 1-Aroylaziridines are known to be readily isomerized into oxazolines under different conditions, [13][14][15][16][17][18] a literature survey reveals that a few examples of the isomerization of the 2-aryl keto-aziridines has been reported up to now [19][20][21][22]. Padwa and co-worker reported a pyrolytic rearrangement of trans-1,3-dibenzoyl-2-phenyl aziridine in xylene by an initial C-C bond cleavage of the aziridine ring to give a 1,3-dipolar intermediate, which rearranges to give 1,4-diphenyl-4-benzoyloxy-2-azabutadiene via a benzoyl migration (Scheme 1) [2].Our interest in the transformation of the aziridine ring [23-28] to oxazoles, thiazoles, alkenes via C-N bond or C-C bond cleavage, motivated our studies in the isomerizaton of 1,2-diaroyl-3-aryl aziridines to the derivatives of N-((Z)-1-oxo-1,3-diphenylprop-2-en-2-yl) benzamide by a C-N bond cleavage in a regioisomeric manner.The present paper describes regio-and stereo-controlled isomerization of 1,2-diaroyl-3-arylaziridines to the corresponding N-((Z)-1-oxo-1,3-diphenylprop-2-en-2-yl) benzamido in the presence of diethyl thiourea in room temperature. Results and discussionWe prepared trans-2-benzoyl-3-(4-chlorophenyl) aziridines (1) via Gabriel-Cromwell procedure [22]. Then 4-nitrobenzoyl chloride were added to a solution of trans-2-benzoyl-3-(4-chlorophenyl) aziridines (1) in the presence of Et 3 N in CH 2 Cl 2 at 0 °C to furnish 2-benzoyl-1-(4-nitrobenzoyl)-3-(4-chlorophenyl) aziridines (2) which was treated with diethyl thiourea in CH 2 Cl 2 . The reaction afforded the desired product (3) (Scheme 2) (95 %). Abstract Regio and stereo-controlled rearrangement of N-4-nitrophenyl-2-benzoyl-3-(4-Cl phenyl) aziridine to N-((Z)-1-oxo-1-phenyl-3-(4-chlorophenyl)prop-2-en-2-yl)-4 nitrobenzamide is described. The studies on the single crystal X-ray diffraction method confirmed the stereochemistry of the product and the proposed mechanism. The product was crystallized in yellow crystal 0.30 × 0.10 × 0.10 mm, a = 10.0267 (5) Å, b = 16.1419 (9) Å, c = 23.9254 (14) Å, V = 3872.3(4) Å 3 , ρ(calcd) = 1.396 mg cm −3 , μ = 0.229 mm −1 , Z = 8, λ = 0.71073 Å, T = 301 K, ω and ϕ scans, 3591 reflections collected (±h, ±k, ±l), [I ≥ 2 σ(I)], 1959 independent (R int = 0.0808) and 1852 observed reflections [I ≥ 2 σ(I)], 267 refined parameters, R = 0.0544, wR 2 = 0.1260, max residual electron density 0.251 (−0.373) e Å −3 , Flack parameter 0.0040 (6).

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“…Examination of the orbital symmetry controlled generation of azomethine ylides from aziridines and exploration of their synthetic potential via 1,3-dipolar cycloaddition to a wide variety of multiple and heteromultiple bonds has recently proved extremely fruitful (1)(2)(3)(4)(5)(6)(7)(8)(9)(10)(11)(12)(13)(14)(15)(16)(17)(18). The isoelectronic carbonyl ylides which are of equal importance have not received as much attention (19)(20)(21)(22)(23)(24)(25)(26)(27)(28)(29).…”

Section: Introductionmentioning

confidence: 99%

Reactions of Carbonyl Ylides

Lown¹,

Matsumoto²

1971

Can. J. Chem.

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2,3-Diphenylindenone oxide 1 undergoes thermal 1,3-dipolar cycloadditions via a carbonyl ylide with symmetrical olefinic dipolarophiles to give (i) with cis addends mixtures of endo and exo adducts in which endo adducts generally predominate in agreement with results obtained with l-cyclohexyl-6-(cyclohexylimino)-la-phenylindano[l,2-b]aziridine and (ii) with trans addends adducts in which the 2-exo-3-endo product predominates. The pyrilium oxide 4is efficiently trapped with benzyne. 1,3-Diphenylisobenzofuran reacts with cis-addends to give endo-exo mixtures in which the endo adducts generally predominate. 2-Acetyl-5,5-pentamethylene-2-phenyl-A3-l,3,4-oxadiazoline undergoes regiospecific cycloaddition via a carbonyl ylide with unsymmetrical olefinic dipolarophiles in accordance with substituent electronic effects, and with 1,4-naphthoquinone a previously postulated type of intermediate adduct is isolated. L'oxyde de diphenylindenone-2,3 1 peut reagir pour donner des cycloadditions dipolaires-1,3 thermiques, par l'intermediaire d'une ylure de carbonyle possedant des dipolarophiles olefiniques symetriques. On obtient ainsi (i) avec des melanges endo et exo des produits cis, des produits d'addition oh la forme endo predomine habituellement, en accord avec les resultats obtenus avec le cyclohexyl-1 (cyclohexylimino)-6 phenylindano-la aziridine[l,2-b] et (ii) avec les produits trans, des produits d'addition oh la forme exo-2-endo-3 predomine. L'oxyde de pyrilium 4 peut &tre recueilli efficacement dans le benzene. Le diphCnylisobenzofuranne reagit avec les produits cis pour donner des melanges endo-exo, oil les produits d'addition endo prkdominent generalement. Le 2-acetyl-5,5 pentamethylene-2 phenyl-A3-1,3,4-oxadiazoline peut reagir pour donner des cycloadditions rtgiospecifiques, via une ylure de carbonylepossedant des dipolarophiles olefiniques non-symetriques, selon les effets dlectroniques du substituant; avec la naphthoquinone-1,4, on isole un produit d'addition intermediaire postule precedemment.

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Thermal rearrangements of arylaroylaziridines into 2,5-diaryloxazoles

Cited by 14 publications

References 0 publications

Electron‐impact studies XCV–skeletal rearrangement fragments in the mass spectra of 3,5‐ diphenylisoxazole and 3,5‐ diphenylpyrazole

Electron‐impact studies XCV–skeletal rearrangement fragments in the mass spectra of 3,5‐ diphenylisoxazole and 3,5‐ diphenylpyrazole

Regio- and stereo-synthesis, crystal structure and NMR assignments of N-((Z)-1-oxo-1-phenyl-3-(4-chlorophenyl)prop-2-en-2-yl)-4-nitrobenzamide

Reactions of Carbonyl Ylides

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