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We report here our synthetic approach to acetylenic esters of six different steroids. The use of flash vacuum pyrolysis (FVP) is a very appealing tool for the acetylenic moiety to efficiently cyclize and rearrange which allows access to medicinally and pharmaceutically valuable products. Each substrate was subjected to FVP. The products were analyzed, identified and characterized. Acetylenic esters of aromatic steroids resulted in 2 H -cyclohepta[ b ]furan-2-one, and 2 H -chromen-2-one derivatives, while aliphatic esters afforded unsaturated polycyclic hydrocarbons via elimination of propiolic acid. [Display omitted] • Acetylenic aromatic steroid esters react via carbene insertion reactions. • FVP of steroid esters provides direct access to prepare interesting fused steroid derivatives. • Acetylenic aliphatic steroid esters undergo elimination reaction via six-membered transition state. [ABSTRACT FROM AUTHOR]

Synthesis and flash vacuum pyrolysis (FVP) of acetylenic esters and ethers of paracetamol and aspirin and their analogues were performed. The products were analyzed, identified, and characterized. Acetylenic esters and ethers of paracetamol resulted in benzofuran, and cyclohepta[ b ]pyrrol-2(1 H)-one. Aspirin and its derivatives produced chromenones, xanthones, indenones, chromenes, and other heterocyclic compounds. [Display omitted] • Synthesis and FVP of aspirinderivatives. • Synthesis and FVP of paracetamol derivatives and analogues. • Valuable routes for synthesis of xanthones and chromenones by FVP. [ABSTRACT FROM AUTHOR]

1-aryl-1,2,3-triazole-4-carboxylate esters 1 - 13 , − 4-carboxamides 14–16 , ethyl 1-aryl-5-methyl/phenyl-1,2,3-triazole carboxylates 17–21 , − 4-carboxamides 22–24 , and 1,4,5-triphenyltriazole 25 have been synthesized via click reactions. Flash vacuum pyrolysis (FVP) for each triazole has been investigated. FVP of triazole-4-carboxylates gave mainly 4-hydroxyquinolin-2(1 H)-one and indole derivatives, while FVP of triazole-4-carboxamides gave indole and urea derivatives. In addition, unanticipated novel products were also isolated. All products were identified, analyzed, and fully characterized. • FVP reaction for twenty-five triazole derivatives were performed. • Indoles and quinolones are the major products from FVP of triazoles at 500–650 ºC. • Methyl triazole-4-carboxylates generate two quinolones isomers. • FVP of 5-substituted triazoles provides two positional isomers of indoles. [ABSTRACT FROM AUTHOR]

Flash vacuum pyrolysis (FVP) of aryl propargyl ether 9 produces 2-methylbenzofuran 21 , 2 H -chromene indanone 22 and benzocyclobutene 23. o -chloro- and bromo-aryl propargyl ethers 10 & 11 resulted mainly in methylbenzofurans 25 , 26 & 29 and 2 H -chromene derivative 27. On the other hand, FVP of arylpropargyl ethers with an active substituent at the ortho position of the aryl group 12 - 15 & 20 has resulted in interesting, unexpected products. All products were analyzed, fully characterized, and identified. Mechanisms are proposed for most of these FVP reactions. [Display omitted] • FVP reaction for twelve aryl propargyl ethers were performed. • Reaction products were analyzed, characterized, and identified. • Non-ortho substituted aryl ethers chose Claisen-rearrangement leading to 2-indanones and benzocyclobutene. • An active function group at the ortho position interacts with carbene intermediates to form interesting unexpected products. [ABSTRACT FROM AUTHOR]

Abstract: Thermolysis of benzoin benzene-p-sulfonylhydrazone I in nitrogen atmosphere at 200°C leads to the formation of numerous products among which the following were identified: ammonia, benzoic acid, benzophenone, benzil, aniline, diphenyl acetylene, deoxybenzoin, N-benzylbenzamide, diphenyldisulfide, diphenylthiosulfone, S-phenylthiobenzoate, benzenesulfonamide, 2-phenylindole, 2,3,4,5-tetraphenylfuran, 2,4,5-triphenylimidazole, and 2,4,5-triphenyloxazole. Similarly, thermolysis of I in the presence of isoquinoline as a radical trap under the same conditions gave 1-phenylisoquioline in addition to the previously mentioned products. Analogous results were also obtained for thermolysis of benzoin toluene-p-sulfonylhydrazone II. The formation of such products which implies the homolysis of different bonds in the benzoin derivatives followed by reaction of the so formed radicals. [Copyright &y& Elsevier]

• Synthetic application of FVP of acetylenic amides for 1-azazzulene-2-ones and unsaturated lactams. • Two independent process are involved: retro-ene reaction and carbene intermediate. • Alkyne functionality provides antiproliferative activity. Flash vacuum pyrolysis (FVP) of twelve acetylenic amides was investigated. Products of pyrolysis were analyzed, characterized, and mechanisms for their thermal behavior were suggested. The mechanistic approach was determined by the nature of the substituents at the nitrogen of the amide moiety. This study provides a synthetically useful application for the synthesis of 1-azaazulen-2-ones and other unsaturated lactams via FVP of acetylenic amides. The biological activity of selected substrates and their pyrolysis products against MDA-MB-231 breast cancer cells was assessed. [ABSTRACT FROM AUTHOR]

• Acetylenic esters of β -hydrogen pyrolyse by a retero-ene reaction. • Acetylenic esters of no β -hydrogen pyrolyse via carbene intermediate. Products from flash vacuum pyrolysis of eleven acetylenic esters are reported in this study. The mechanism of their pyrolysis is proposed based on the products isolated. These reveal a combination of two main mechanistic approaches. Esters with β -hydrogens favor a retro-ene reaction via a six-membered transition state, the absence of such β -hydrogen leads to a carbene intermediate followed by insertion and cyclization. [ABSTRACT FROM AUTHOR]

• FVP of aminobenzo- and naphthofurans give formylbenzo- and naphthonitriles. • Absence of amino group renders cleavage of furan ring more difficult. • Substituted phenoxy and naphthoxy carbenes isomerize to benzaldehyde and naphthocarboaldehyde derivatives. Benzo- and naphthofuran carboxylates 1, 2 and carboxamides 3 , 4 were synthesized and pyrolysed by flash vacuum pyrolysis at 550 and 650 °C/10−2 mmHg. 2-Formylbenzonitrile 7 from benzofurans and 2-formylnaphthonitrile 14 from naphthofurans were isolated and identified as major products. The mechanism suggested for these pyrolytic reactions involves elimination of alcohol and amine from carboxylates 1, 2 and carboxamides 3 , 4 respectively, followed by extrusion of CO to form phenoxy and naphthoxycarbenes that leads to 7 and 14 respectively. [ABSTRACT FROM AUTHOR]