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1.
A method for the synthesis of the title compound 3 consisted of an intramolecular cyclization in a stannic chloride catalyzed Friedel-Crafts reaction of N-(2-methylthiophenyl)-5-oxoproline chloride 10 , prepared by chlorination of the corresponding acid 9 obtained by hydrolysis of its ethyl ester 8 . Condensation of 2-methylthioaniline 4 with diethyl bromomalonate 5 afforded diethyl 2-methylthioanilinomalonate 6 which gave 8 either directly by reaction with ethyl acrylate or by alkylation with ethyl β-bromopropionate or ethyl acrylate and cyclization of resulting triethyl 2-(2-methylthio)anilino-2-carboxyglutarate 7 . This method was not convenient because of the poor yield of 3 (14%). On the other hand, cyclization of N-(2-mercaptophenyl)-5-oxoproline 14 with DCC and DMAP provided 3 in 45% yield. Oxidation with m-CPBA of the esters 11 and 8 , demethylation via the Pummerer rearrangement of the respective sulphoxides 12 and 17 with TFAA and oxidation with iodine of resulting N-(2-mercap-tophenyl)-5-oxoproline esters 13 and 18 gave the corresponding disulphides 16 and 19 . Hydrolysis of these latter compounds and reduction of the resulting bis[2-[2-(hydroxycarbonyl)-5-oxo-1-pyrrolidinyl]phenyl] disulphide 15 with sodium dithionite afforded the required 14 . Deprotection of t-butyl ester 13 with TFA at 55° to obtain 14 led to 3 in 42% yield. Finally the Pummerer rearrangement of N-(2-methylsulphinylphenyl)-5-oxo-proline 20 yielded the mixture of 14 and 15 . 相似文献
2.
Cyclization of 4-(1-methylindol-3-yl)-2-butanone and the corresponding 1-benzyl analog in trifluoroacetic acid furnishes 9-methyl- and 9-benzyl-3,4,4a,9a-tetrahydro-2(1H)-carbazolone, respectively. Under the same conditions, 4-(indol-3-yl)-2-butanone gives the dimer, 3-(3-oxo-butyl)-2-[3-(3-oxobutyl)-2-indolinyl] indole. When boron trifluoride etherate is used instead of trifluoroacetic acid, the desired 3,4,4a,9a-tetrahydro-2(1H)-carbazolone is obtained. The determination of the structure of the tetrahydrocarbazolones is described and the stereochemistry of the ring fusion is discussed. 相似文献
3.
Synthesis of 3-Dimethylamino-3a,4,5, 7a-tetrahydro-1H-isoindol-1-ones by Intramolecular Diels-Alder Reaction Thermolysis of N2-acylamidines, the acyl group of which derives from an α,β,γ,δ-unsaturated carboxylic acid ( 2, 5 – 7 ), yields 3-dimethylamino-3a,4,5,7a-tetrahydro-1H-isoindol-1-ones ( 3,8 – 10 , Schemes 1 and 3) in 63–78%. Only the thermodynamically controlled cis-fused ring system is formed. The starting materials are readily available by the reaction of 3-dimethylamino2H-azirines ( 1 and 4 ) and carboxylic acid chlorides. 相似文献
4.
David T. Connor Patricia A. Young Maximillian von Strandtmann 《Journal of heterocyclic chemistry》1978,15(1):115-117
The reaction of 1-methyl-3-(methylsulfinyl)-4(1H)quinolinone ( 1 ) with acetic anhydride and thionyl chloride gave 3-[[(acetyloxy)methyl]thio]]-1-methyl-4(1H)quinolinone ( 2 ) and 3-[(chloromethyl)thio]-1-methyl-4(1H)quinolinone ( 3 ) respectively. 3-(Methylsulfinyl)-4(1H)cinnolinone ( 4 ) gave the corresponding products when treated under similar conditions. Treatment of 8-methoxy-3-(methylsulfinyl)-4H-1-benzopyran-4-one ( 11 ) with acetic anhydride and thionyl chloride gave bis addition vinyl Pummerer products 2,3-bis(acetyloxy)-2,3-dihydro-8-methoxy-3-(methylthio)-4H-1-benzopyran-4-one ( 12 ) and 2,3-dichloro-2,3-dihydro-8-methoxy-3-(methylthio)-4H-1-benzopyran-4-one ( 13 ), respectively. 相似文献
5.
N. A. Ivanova V. A. Akhmetyanova N. P. Akhmetdinova O. V. Shitikova K. Yu. Suponitzky M. S. Miftakhov 《Russian Journal of Organic Chemistry》2014,50(6):810-814
Baeyer-Villiger oxidation of racemic [2 +2 ]-cycloadduct derived from dichloroketene and dimethylfulvene gave 3,3-dichloro-6-(1-methylidene)-3,3a,6,6a-tetrahydro-2H-cyclopenta[b]furan-2-one, and opening of the lactone ring in the latter with (+)-α-methylbenzylamine produced diastereoisomeric amides which can be readily separated by chromatography on silica gel. The subsequent lactonization and reductive dechlorination afforded enantiomeric (?)- and (+)-6-(propan-2-ylidene)-3,3a,6,6a-tetrahydro-2H-cyclopenta[b]-furan-1-ones. 相似文献
6.
Treatment of N‐[2‐(methylsulfanylmethyl)aryl]pyrroles ( 4 ) with phenyliodine(III) bis(trifluoroacetate) containing trifluoroacetic acid resulted in an interrupted Pummerer‐type reaction to give 5H‐pyrrolo[1,2‐a][3,1]benzothiazines ( 5 ) rather than the normal Pummerer‐type products. 相似文献
7.
The title compound ( 3 ), a β-ketosulfoxide prepared by a Claisen-type condensation of ethyl 2-(10-phenothiazino)acetate ( 4 ) with dimsyl carbanion, was subjected to a variety of catalysts in attempts to achieve a Pummerer cyclization to 1,2-dihydro-3-methylthio-2-oxo-3H-pyrido[3,2,1-kl]phenothiazine ( 2 ). Although the Pummerer rearrangement product, 10-(2-oxo-3-hydroxy-3-methylthiopropyl)phenothiazine ( 5 ), could be obtained in excellent yield under mild conditions, neither it nor the β-ketosulfoxide could be successfully cyclized under any of the conditions attempted. Instead, phenothiazine, 2-hyroxy-3-(10-phenothiazinyl)-2-propen-1-al ( 7 ), 3-(10-phenothiazinyl)-1,1-di(methylthio)propan-2-one ( 8 ), 3-(10-phenothiazinyl)-1-methylthiopropan-2-one ( 9 ) and 10-phenothiazinylformamide ( 10 ) were variously obtained. 相似文献
8.
The nucleophilic introduction of chloro- ( 2 ), azido- ( 4 ), (substituted) amino ( 3, 6 ), mercapto ( 10 ) and hydrazino-groups ( 13 ) into 2-aryl-5-hydroxypyridazin-3(2H)-ones [3] is described. The 5-aminopyridazin-3(2H)-one ( 6 ) also reacts with activated malonates 8 [4] to give pyrido[2,3-d]pyridazines 9 . Hydrazino compounds 13 can be treated with aldehydes to yield compounds 14 . Iodine can be introduced into position 4 of 5 -amino -(15 ) and 5-hydroxypyridazin-3(2H)-ones ( 17 ) by electrophilic substitution to afford compounds 18 . 相似文献
9.
The 4,4′,6,6′-tetrasubstituted 2,2′-alkylidene-bisphenols 1 reacted with sulfur monochloride to give 4,10a-(epidithio)-4,4a,10,10a-tetrahydro-1H-5-oxaanthracen-1-ones ( 3 and 4 ). The structure of the products were elucidated by a combination of X-ray crystal-structure analysis and 1H- and 13C-NMR spectroscopy. 相似文献
10.
A new convenient synthesis of dibenzo[b,g][1,5]naphthyridine-6,12(5H,11H)dione starting from N-phenylglycine ethyl ester is described. Ester condensation of N-phenylglycine ethyl ester with diethyl oxalate followed by reaction with aniline under acid catalysis gave a mixture of diethyl dianilinomaleate and diethyl dianilinofumarate in 54% yield. Upon heating this mixture in a high-boiling inert solvent, 3-anilino-2-ethoxycarbonyl-4-quinolone was obtained in 72% yield. Final ring closure of the quinolone derivative using polyphosphoric acid gave the epindolidione. 相似文献
11.
The dipolar 1,4-cycloaddition of dichloroketerie to N,N-disubslituled 3-aminomethylene-2,3-dihydro-4-thiochromanones and 3-aminomethylenetelrahydro-4-thiopyranones gave N,N-disubstituted 4-amino-3,3-diehloro-3,4-dihydro-2H,5H-[1]benzolhiopyrano[4,3-b]pyran-2-ones and 4-amino-3,3-dichloro-3,4,7,8-tetrahydro-2H,5H-thiopyrano[4,3-b]pyran-2-ones, respectively, only in the ease of aromatic or strong hindering aliphatic N-substitution. The adducts gave N,N′-disubstituted 4-amino-3-chloro-2H,5H-[1]benzothiopyrano[4,3-b]pyran-2-ones and 4-amino-3-chloro-7,8-dihydro-2H,5H-thiopyrano[4,3-b]pyran-2-ones, respectively, by dehydro-chlorination with DBN. By chromatography on neutral alumina, 3-(2,2-dichloroethylidene)-2,3-dihydro-4-thiochromanone was isolated as an unstable liquid from the reaction between dichloroketerie and 3-diethylaminornethylene-2,3-dihydro-4-thiochromanone. 相似文献
12.
Otohiko Tsuge Taizo Hatta Hisashi Kojima Nobutaka Miyahara Masafumi Sugaya 《Journal of heterocyclic chemistry》1994,31(5):1283-1287
2-Benzoyl- 5 and 2-acetylacenaphthenone 6 , prepared from the corresponding 1-acyl-2-(1-pyrrolidinyl)-acenaphthylenes 2 and 3 , reacted with arylhydrazines 8 under acidic conditions to give the corresponding 1-arylacenaphtho[1,2-d]pyrazoles 9 and 10 . Novel heteropentalene mesomeric betaines, 5,7-dehydro-5H,7H-benzo[b]acenaphtho[1,2-e]-1,3a,6a-triazapentalenes 13 and 14 were prepared by reductive cyclization of 1-(o-nitrophenyl)acenaphtho[1,2-d]pyrazoles 9d and 10d , respectively. 相似文献
13.
Marino Artico Federico Corelli Silvio Massa Giorgio Stefancich 《Journal of heterocyclic chemistry》1982,19(6):1493-1495
A four-step preparation of 1-methyl-5-p-totylpyrrole-2-acetic acid (Tolmetin) is reported starting from 1-methyl-2-p-tolylpyrrole. Formylation of this compound followed by condensation with methyl(methylthio)-methyl sulfoxide furnished 1-(methylsulfinyl)-1-methylthio-2-(1-methyl-5-p-tolyl-2-pyrrolyl)ethylene. Pummerer rearrangement of the latter compound gave ethyl 1-methyl-5-p-tolylpyrrole-2-acetate, which was hydrolyzed in alkaline medium to afford Tolmetin. 相似文献
14.
2-Methyl-5-(5-oxo-1-benzyl-2-pyrrolidinyl)-1,3,4-oxadiazole is easily obtained by dehydration of N-acetyl-1-benzylpyroglutamic acid hydrazide with a methanesulfonic acid/phosphoric anhydride mixture. 相似文献
15.
Pummerer‐type reaction intermediate 2 of α‐(methylthio)‐N‐methoxy‐N‐methyl acetamide (1) has been found to react with 1‐alkenes to afford ene adducts 3 . N‐Methoxy‐N‐methyl‐(E,E)‐2,4‐dienamides were synthesized from the adducts 3b‐f . 相似文献
16.
John R. Beswick W. David Cotterill Muhammad Iqbal Robert Livingstone 《Journal of heterocyclic chemistry》1993,30(3):623-626
Reaction between some naphtho[2,1-b]pyrans and 1,1-diphenylethene affords 9,9-diphenyl-1,9,10,10a-tetrahydro-2H-phenaleno[1,9-bc]pyrans. 相似文献
17.
Cong Zhang Christian Ludin Marcel K. Eberle Helen Stoeckli-Evans Reinhart Keese 《Helvetica chimica acta》1998,81(1):174-181
(S)-5,5,5,5′,5′,5′-Hexafluoroleucine ((S)- 13 ) of 81 % ee is prepared from hexafluoroacetone ( l ) and ethyl bromopyruvate (= ethyl 2-oxopropanoate) in 7 steps with an overall yield of 18% (Schemes 1 and 2). Key step in this sequence is the highly enantioselective reduction of the carbonyl group in α-keto ester 4 either by bakers' yeast (91 % ee) or by ‘catecholborane’ 6 utilizing an oxazaborolidine catalyst, yielding hydroxy ester (R)- 5 with 99% ee. The absolute configuration was determined by X-ray analysis of the HCl adduct (S,R)- 9b of (2S)-N-[(R)- l-phenylethyl]-5,5,5,5′,5′,5′-hexafluoroleucine ethyl ester. 相似文献
18.
G. S. Walker P. E. Fagemess K. A. Farley S. A. Mizsak 《Journal of heterocyclic chemistry》1997,34(1):295-299
The 1H and 13C nmr spectral assignments of [7bR]-N-[2-[(4,5,8,8a-tetrahydro-7-methyl-4-oxocyclo-propa[c]pyrrolo[3,2-e]indol-2(1H)-ylcarbonyl]-1H-indol-5-yl]-2-benzofurancarboxamide (Adozelesin) (1) are described. Complete and unambiguous assignments of the hydrogen and carbon spectra were made using a combination of conventional homonuclear and gradient-selected inverse-detected heteronuclear nmr experiments: double quantum filtered 1H-1H correlation spectroscopy (COSY), gradient-selected heteronuclear single quantum coherence spectroscopy (gs-HSQC), and gradient-selected heteronuclear multiple bond coherence spectroscopy (gs-HMBC). The enhanced sensitivity of these experiments allowed a smaller sample concentration and shorter spectral collection times for a full nmr analysis of this compound. The nmr data corroborates the published structure of this compound. 相似文献
19.
Airat M. Gimazetdinov Salavat S. Gataullin Ivan S. Bushmarinov Mansur S. Miftakhov 《Tetrahedron》2012,68(29):5754-5758
Diastereomeric amides produced via the cleavage of easily available (±)-7,7-dichloro-4-exo-trimethylsilylbicyclo[3.2.0]hept-2-en-6-one by treatment with (+)-α-methylbenzylamine were transformed into bicyclic lactam-aminals, which can easily be separated by column chromatography on SiO2. The latter products lead to enantiomeric (3a,6a)-4-hydroxy-3,3a,4,6a-tetrahydro-1H-cyclopenta[c]furan-1-ones after the removal of the chiral auxiliary and epoxidation. 相似文献
20.
Harry L. Yale 《Journal of heterocyclic chemistry》1978,15(2):331-332
13-Ethoxy-7-(trifluoromethyl)-11H-11,5-(epoxymethano)dibenzo[b,e][1,4]thiazepine ( 3 ) was formed following the Pummerer Rearrangement of 7-(trifluoromethyl)dibenzo[b,e] [1,4]-thiazepine-5(11H)carboxaldehyde 10-oxide ( 1 ), when the work-up involved the use of diethyl ether that contained ethanol as a normal ingredient, i.e., the grade of that solvent employed in anesthesia. 相似文献