The preparation of a stable 8-oxatricyclo[4,3,0,07,9]nona-2,4-diene and an evaluation of its potential as a source for the photochemical generation of oxiren

1981 ◽  
Vol 34 (4) ◽  
pp. 855 ◽  
Author(s):  
RN Warrener ◽  
RA Russell ◽  
RYS Tan
Keyword(s):  
Hydrogen Peroxide ◽  
Double Bond ◽  
Photochemical Reaction ◽  
Ring Opening ◽  
Thermal Conditions ◽  
Ring System ◽  
Crystalline Solid ◽  
Mercuric Oxide ◽  
Azo Compound ◽  
Photochemical Generation

The synthesis of 2-methyl-3,4,5-triphenyl-8-oxatricyclo[4,3,0,07,9]nona-2,4-diene (14) is described, the first stable member of this ring system. Preparation of (14) was achieved by reacting dibenzyl diazenedicarboxylate with 2-methyl-3,4,5-triphenylbicyclo[4,2,0]octa-2,4,7-triene (29) to form the adduct (30a), which was selectively epoxidized at the cyclobutenyl double bond with 3-chloroperbenzoic to yield the epoxide (32a). Removal of the benzyl groups (H2/Pd) from the hydrazo bridge of (32a), followed by oxidation (red mercuric oxide or hydrogen peroxide) yielded the putative azo compound (33) which spontaneously lost dinitrogen, even at -78�, to yield (14) as a crystalline solid, m.p. 128�. While (14) has the potential to undergo 1,2-photoaromatization to yield oxiren (4a), this is not realized and ring-opening to the cyclic epoxide (34) is the major photochemical reaction observed under various ultraviolet irradiation conditions. Isomerization of (14) into (34) also occurs under thermal conditions. The 1H n.m.r, spectra of (14) as well as its trapping with dienophiles is discussed.

scholarly journals Non-Isocyanate Polyurethane (NIPU) based on Rubber Seed Oil Synthesized via Low-Pressured Carbonization Reaction

2021 ◽  
Vol 50 (8) ◽  
pp. 2407-2417
Author(s):  
R.A. Hambali ◽  
M.A. Faiza ◽  
A. Zuliahani
Keyword(s):  
Hydrogen Peroxide ◽  
Double Bond ◽  
Formic Acid ◽  
Ring Opening ◽  
Seed Oil ◽  
Epoxide Ring ◽  
Rubber Seed Oil ◽  
Rubber Seed ◽  
Ring Opening Reaction ◽  
Epoxidation Reaction

Epoxidised rubber seed oil (ERSO) was successfully synthesized into non-isocyanate polyurethane via carboxylation method whereas peroxoformic acid was formed by in-situ reaction for epoxidation. The effects of temperature and ratio of hydrogen peroxide and formic acid to rubber seed oil carboxylation were studied. The optimum temperature for the epoxidation reaction was found at 50 °C to avoid ring opening reaction of epoxy whilst the optimum ratio of hydrogen peroxide and formic acid is equal molar of double bond: formic acid at 1:2 and 1:1, respectively. At a lower concentration of hydrogen peroxide and formic acid, the oxirane ring was stable due to the lower hydrolysis (oxirane cleavage) of an epoxide. The effect of using low content of formic acid tends to minimize unwanted epoxide ring opening to occur and make the epoxidation rate increased with increasing of oxirane number. Fourier transform infrared (FTIR) spectral displayed the presence of an epoxy functional group at 822 cm-1 and the disappearance of double bond peak at 3011 cm-1 corresponding to epoxidised oil and carbonyl group confirmed the epoxidation reaction had taken place. 1H-NMR was used to confirm the formation of carboxylate functionality after the reaction of epoxy at δ 4.83 and 4.61 ppm. In conclusion, ERSO has great potential to be used as a precursor in producing environmentally friendly non-isocyanate polyurethane.

Resolving the Mystery of Ring Opening in the Synthesis of Benzo[d][1, 3]oxazin-4-one and Quinazolin-4(3H)-one

2019 ◽  
Vol 16 (11) ◽  
pp. 898-905
Author(s):  
Harun Patel ◽  
Rahul Pawara ◽  
Sanjay Surana
Keyword(s):  
Characteristic Feature ◽  
Ring Opening ◽  
Biological Activities ◽  
Heterocyclic Ring ◽  
Ring System ◽  
Time Saving ◽  
Fusion Strategy ◽  
Good Template ◽  
Lead Generation

Quinazoline is the six-membered heterocyclic ring system reported for its versatile biological activities. This characteristic feature of quinazoline makes it a good template for a lead generation library. Ring opening is one of the major concerns in the synthesis of quinazolin-4(3H)-one that results in diamide formation. Here, alternative fusion strategy is reported, which is a time-saving and costeffective method to overcome the ring opening problem associated with the synthesis of benzo[ d][1,3]oxazin-4-one and quinazolin-4(3H)-one.

Reactions of 4-Pyrones with Azomethine Ylides as a Chemo­selective Method for the Construction of Multisubstituted Pyrano[2,3-c]pyrrolidines

Synthesis ◽  
2021 ◽  
Author(s):  
Dmitrii L. Obydennov ◽  
Vyacheslav D. Steben’kov ◽  
Konstantin L. Obydennov ◽  
Sergey A. Usachev ◽  
Vladimir S. Moshkin ◽  
...  
Keyword(s):  
Double Bond ◽  
Ring Opening ◽  
Azomethine Ylides ◽  
Azomethine Ylide ◽  
Dipolar Cycloaddition ◽  
Computational Studies ◽  
Carbon Double Bond ◽  
Reactivity Indexes ◽  
Reaction Proceeds

Abstract4-Pyrones bearing electron-donating and electron-withdrawing groups react with nonstabilized azomethine ylides to form pyrano[2,3-c]pyrrolidines in moderate to good yields. The reaction proceeds chemoselectively as a 1,3-dipolar cycloaddition of the azomethine ylide at the carbon–carbon double bond of the pyrone activated by the electron-withdrawing substituent. The reactivity of 4-pyrones toward azomethine ylides was rationalized by computational studies with the use of reactivity indexes. The pyrano[2,3-c]pyrrolidine moiety could be modified, for example by a ring-opening transformation under the action of hydrazine to provide pyrazolyl-substituted pyrrolidines.

scholarly journals Stereoselective total syntheses of (±)-sinularene and (±)-5-epi-sinularene: a general intramolecular Diels–Alder approach to tricyclic sesquiterpenes

1985 ◽  
Vol 63 (4) ◽  
pp. 993-995 ◽  
Author(s):  
Kazimierz Antczak ◽  
John F. Kingston ◽  
Alex G. Fallis
Keyword(s):  
Double Bond ◽  
Methyl Ester ◽  
Total Synthesis ◽  
Ring System ◽  
Diels Alder ◽  
Exocyclic Double Bond ◽  
Total Syntheses ◽  
Methyl Group ◽  
Secondary Hydroxyl ◽  
Selective Hydrogenolysis

Stereoselective total synthesis of (±)-sinularene and (±)-5-epi-sinularene are described. The sequence employs a "blocked" cyclopentadiene in which the cyclopropane unit also serves as a latent methyl group. Thus intramolecular [4 + 2] cycloaddition of the substituted methyl spiro[2.4]hepta-4,6-dien-1-yl)-2-pentenoate 11 affords 5-benzyloxy-6-isopropyl-8-carbomethoxytetracyclo[5.4.01,7.02,4.02,9]undec-10-ene (12) which after selective hydrogenolysis generates the tricyclo[4.4.01,6.02,8]decane (sinularene) ring system. Removal of the secondary hydroxyl function (Ph3P/CCl4/CH3CN; H2/Pd/C), reduction of the methyl ester (LiAlH4), and introduction of the exocyclic double bond (acetate pyrolysis, 550 °C) completes the synthesis of (±)-sinularene in 14 steps from cyclopentadiene. A parallel series of reactions employing the isopropyl epimer of 12 affords (±)-5-epi-sinularene.

A novel rearrangement: the ring opening of a cyclic azo compound to a diazoalkane

1963 ◽  
Vol 4 (21) ◽  
pp. 1405-1408 ◽  
Author(s):  
C.G. Overberger ◽  
Jean-Pierre Anselme
Keyword(s):  
Ring Opening ◽  
Azo Compound

scholarly journals Preparation of 2-phospholene oxides by the isomerization of 3-phospholene oxides

2020 ◽  
Vol 16 ◽  
pp. 818-832 ◽  
Author(s):  
Péter Bagi ◽  
Réka Herbay ◽  
Nikolett Péczka ◽  
Zoltán Mucsi ◽  
István Timári ◽  
...  
Keyword(s):  
Double Bond ◽  
Quantum Chemical Calculations ◽  
Quantum Chemical ◽  
Methanesulfonic Acid ◽  
Thermal Conditions ◽  
Double Bond Migration ◽  
Bond Rearrangement ◽  
Migration Pathways

A series of 1-substituted-3-methyl-2-phospholene oxides was prepared from the corresponding 3-phospholene oxides by double bond rearrangement. The 2-phospholene oxides could be obtained by heating the 3-phospholene oxides in methanesulfonic acid, or via the formation of cyclic chlorophosphonium salts. Whereas mixtures of the 2- and 3-phospholene oxides formed, when the isomerization of 3-phospholene oxides was attempted under thermal conditions, or in the presence of a base. The mechanisms of the various double bond migration pathways were elucidated by quantum chemical calculations.

Synthesis of nitropolychlorinated dibenzo-p-dioxins (NPCDDs) and their photochemical reaction with nucleophiles

1995 ◽  
Vol 73 (6) ◽  
pp. 826-834 ◽  
Author(s):  
Simona G. Merica ◽  
Nigel J. Bunce
Keyword(s):  
Excited State ◽  
Quantum Yield ◽  
Linear Relationship ◽  
Nitro Group ◽  
Photochemical Reaction ◽  
Ring Opening ◽  
Sodium Ethoxide ◽  
Chemical Yield ◽  
Triplet Excited State ◽  
High Chemical

A series of nitropolychlorodibenzo-p-dioxins (NPCDDs) was synthesized by condensation between catechols and 2,6-dinitrohalobenzene derivatives. In the presence of sodium ethoxide in anhydrous ethanol, these underwent photochemical SN2Ar* substitutions meta to the nitro group in high chemical yield and moderate quantum yield. Both ring-opening and chloride replacement reactions were observed. The reactions involved the triplet excited state of the NPCDD, and showed a linear relationship between Φ−1 and [nucleophile]−1. Analogous reactions with KCN in methanol showed similar behaviour, but the products could not be isolated. Keywords: photosubstitution, SN2Ar*, dibenzo-p-dioxins.

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