Synthesis of Some Naphthothiadiazolophanes. Derivatives of 4,10,14-Ethenylylidene-7H-[1,2,3]thiadiazolo[5,4-e]azacyclotridecine and 4,11,15-Ethenylylidene[1,2,3]thiadiazolo[5,4-f]azacyclotetradecine

1989 ◽  
Vol 42 (11) ◽  
pp. 1951 ◽  
Author(s):  
JB Bremner ◽  
W Jaturonrusmee
Keyword(s):  
Potassium Carbonate ◽  
Cyanogen Bromide ◽  
Diels Alder ◽  
Reaction Products ◽  
Analogous Structure ◽  
Derivatives Of

Reaction of 7,8-dimethoxy-1,2,4,5,1lb, 11c-hexahydrobenzo [de]pyrrolo[3,2,1-ij][1,2,3]thiadiazolo[4,5-g]quinoline (3a) and 8,9-dimethoxy-2,3,5,6,12b,12c-hexahydro-1H-[1,2,3]thiadiazolo-[5',4':3,4]naphtho[2,1,8-ijalquinoline (3b) with cyanogen bromide in the presence of potassium carbonate gave the naphthothiadiazolophanes 12,13-dimethoxy-5,6,8,9-tetrahydro-4,10,14- ethenylylidene-7H-[1,2,3]thiadiazolo[5,4-e]azacyclotridecine-7-carbonitrile (4a) and 13,14-di-methoxy-6,7,9,10-tetrahydro-4,11,15-ethenylylidene[1,2,3]thiadiazolo[5,4-f]azacyclotetradecine-8(5H)-carbonltrile (4b) in 39 and 89% yield respectively;7-(2-bromoethyl)-1,2-dimethoxy-5,6,6a,7-tetrahydro-4H-benzo[de][1,2,3]thiadiazolo[4,5-g]quinoline-6-car bonitrile (5a) was also obtained in 40% yield from the former reaction. Products of analogous structure resulted from (3a,b) when methyl chloroformate was used In place of cyanogen bromide. Attempted Diels-Alder reactions of (4b,c) with some powerful dienophiles were unsuccessful.

Cyanogen-Bromide-Mediated and Methyl-Chloroformate-Mediated Synthesis of Some [3]Benzazonino[8,7,6-abc]Carbazole, [3]Benzazecino[9,8,7-abc]Carbazole, Naphth[1,8,7-def]Azonine and Naphth[1,8,7-def]Azecine Derivatives

1986 ◽  
Vol 39 (1) ◽  
pp. 1 ◽  
Author(s):  
JB Bremner ◽  
KN Winzenberg
Keyword(s):  
Magnesium Oxide ◽  
Potassium Carbonate ◽  
Cyanogen Bromide ◽  
Reaction Products ◽  
Analogous Structure ◽  
Lithium Tetrahydroaluminate ◽  
Elimination Reactions

Reaction of 7,8-dimethoxy-1,4,5,9,13c,13d-hexahydro-2H-indolo [3′,2′:4,5] indolo [1,7,6-aji] isoquinoline (4a) and 8,9-dimethoxy- 1,2,3,5,6,10,14c,14d-octahydro-indolo[3′,2′:3,4] naphtho [2,1,8-ija] quinolizine (4b) with cyanogen bromide in the presence of potassium carbonate afforded the elimination products 7,8-dimethoxy-1,2,3,4,5,9- hexahydro [3] benzazonino [8,7,6-abc]carbazole-3-carbonitrile (5a) and 8,9-dimethoxy-2,3,4,5,6,10-hexahydro-1H-[3] benzazecino [9,8,7-abc]carbazole-4-carbonitrile (5b) in 4% and 88% yield respectively; 7- (2-bromo)ethyl-1,2-dimethoxy-4,5,6,6a,7,12-hexahydroisoquino[8,1-ab ]carbazole-6-carbonitrile (6a) was also isolated in 20% yield from the former reaction. Products of analogous structure were also obtained from (4a,b) when methyl chloroformate was used in place of cyanogen bromide. Reaction of (4b) with cyanogen bromide in the presence of water and magnesium oxide afforded the solvolysis product 14d-hydroxy-8,9-dimethoxy-2,3,4,5,6,10,14d,14d-octahydro-1H-[3] benzazecino [9,8,7- abc ]carbazole-4-carbonitrile (8b) together with (5b). Similarly application of this reaction to 8,9-dimethoxy-2,3,5,6,11a,11b-hexahydro-1H-naphtho[2,1,8-ija] quinolizine (1b) afforded both the corresponding solvolysis and elimination products; (4a) and 7,8- dimethoxy-1,2,4,5,10a,10b-hexahydronaphtho[1,8,7-ghi] indolizine (1a), however, gave only solvolysis products. Solvolysis and elimination products were also isolated when (1b) and (4b) were subjected to cyanogen -bromide-mediated methanolysis reactions. Acid-catalysed elimination reactions of the alcohol solvolysis products are described along with reaction of some of the elimination products with lithium tetrahydroaluminate.

C-Nucleosides and related compounds. VI. Carbocyclic analogues of C-nucleosides: synthesis and derivatives of some useful intermediates

1976 ◽  
Vol 54 (6) ◽  
pp. 849-860 ◽  
Author(s):  
George Just ◽  
Grant Reader ◽  
Bernadette Chalard-Faure
Keyword(s):  
Acrylic Acid ◽  
Wittig Reaction ◽  
Diels Alder ◽  
Reaction Products ◽  
Free Aldehyde ◽  
Derivatives Of ◽  
Related Compounds ◽  
Alder Adduct

The Diels–Alder adduct of cyclopentadiene and β-bromo acrylic acid 1 was converted to D,L-exo-6,7-(dihydroxy-di-O-isopropylidene)-2-hydroxy-3-oxabicyclo[3.2.1]octane (9) in an eight-step sequence and a 24% yield based on 1. Alternatively, the hemiacetal 9 was obtained in five steps and 22% yield from norbornadiene through the intermediate lactone 11. The thiosemicarbazone and semicarbazone of 9 were prepared. The synthesis of the free aldehyde 13 as well as that of the Wittig reaction products 12 and 19 are described.

Synthesis and Isomerization of Adducts of Azodicarbonyl Compounds and Cyclopentadiene

1972 ◽  
Vol 50 (3) ◽  
pp. 371-380 ◽  
Author(s):  
J. A. Campbell ◽  
Donald Mackay ◽  
T. D. Sauer
Keyword(s):  
Thermal Isomerization ◽  
Diels Alder ◽  
Derivatives Of

The synthesis of a range of bicyclic Diels–Alder adducts (structures b) of cyclopentadiene with symmetrical and unsymmetrical azodicarbonyl compounds is described. Thermal isomerization of these adducts to the bicyclic 1,3,4-oxadiazines (structures c and d) is especially rapid with bulky acyl groups. In unsymmetrical adducts with acyl groups of markedly different size, the larger group dictates completely the direction of isomerization. Adducts with two different aroyl groups give both isomers.Spectroscopic properties of the adducts, the oxadiazines and the dihydro derivatives of the oxadiazines are described.

Cycloadditionen, XXII [1]. Synthese und thermische Reaktion von S-(Alkyl/Aryl)- 2.3-butadienthiosäure-estern / Cycloadditions, XXII [1]. Synthesis and Thermal Reaction of S-(Alkyl/Aryl)-2,3-butadienethioates

1994 ◽  
Vol 49 (4) ◽  
pp. 542-550 ◽  
Author(s):  
Gerhard Himbert ◽  
Dieter Fink
Keyword(s):  
Alder Reaction ◽  
Thermal Reaction ◽  
Diels Alder ◽  
Alkyl Aryl ◽  
Diels Alder Reaction ◽  
Ester Moiety ◽  
Derivatives Of

While the S-alkyl- or S-phenyl-2,3-butadienethioates 4 a-c are synthesized via the usual “Wittig ylide way”, the corresponding 2-methyl-2,3-butadienethioates 9 a-d and the 2-methyl-4.4-diphenyl-2,3-butadienethioates 9 e,f are obtained by condensation of the allenic acids 7 a,b with the thiols and thiophenols 8 in the presence of dicyclohexylcarbodiimide (DCC) and a catalytic am ount of 4-dimethylaminopyridine (DMAP). In contrast to N- or O-phenyl 2,3- butadienamides or -esters, resp., the phenyl derivatives of 4 and 9 do not undergo the intram olecular Diels-Alder reaction, but by heating, all representatives of 4 only decompose, while 9 a-d and 9 e,f rearrange to 3-alkyl(aryl)thio-2-cyclobuten-1-ones 12a-d and to 3-arylthio- 1-naphthols 14a, b, resp. Heating of the cyclobutenone 12d in the presence of N-methylaniline furnishes the 2-butenanilide 16. On reacting 1-phenylthio-1-propyne 17 with diphenylketene 18, the diphenylacetate 19 is isolated, where the naphthol derivative 14a represents the ester moiety.

Nitrosocarbonyl Carbohydrate Derivatives: Hetero Diels–Alder and Ene Reaction Products for Useful Organic Synthesis

Synthesis ◽  
2020 ◽  
Author(s):  
Paolo Quadrelli ◽  
Marco Corti ◽  
Marco Leusciatti ◽  
Mattia Moiola ◽  
Mariella Mella
Keyword(s):  
Organic Synthesis ◽  
Tertiary Amine ◽  
Diels Alder ◽  
Mild Oxidation ◽  
Reaction Products ◽  
Ene Reaction ◽  
Nitrile Oxides

AbstractThe generation and trapping of two new nitrosocarbonyl intermediates bearing carbohydrate-based chiral substituents is achieved by the mild oxidation of the corresponding nitrile oxides with tertiary amine N-oxides. Their capture with suitable dienes and alkenes afforded the corresponding hetero Diels–Alder cycloadducts and ene adducts from fair to excellent yields. The entire methodology looks highly promising by the easy conversion of aldoximes into hydroxymoyl halides, widening the access to nitrosocarbonyls, versatile tools in organic synthesis.

Sign in / Sign up

Export Citation Format

Share Document