1,5-Dipolare Elektrocyclisierung von Acyl-substituierten ‘Thiocarbonyl-yliden’ zu 1,3-Oxathiolen

1,5-Dipolar Electrocyclization of Acyl-Substituted ‘Thiocarbonyl-ylides’ to 1,3-Oxathioles The reaction of α-diazoketones 15a, b with 4,4-disubstituted 1,3-thiazole-5(4H)-thiones 6 (Scheme 3), adamantanethione ( 17 ), 2,2,4,4-tetramethyl-3-thioxocyclobutanone ( 19 ; Scheme 4), and thiobenzophenone ( 22 ; Scheme 5), respectively, at 50–90° gave the corresponding 1,3-oxathiole derivatives as the sole products in high yields. This reaction opens a convenient access to this type of five-membered heterocycles. The structures of three of the products, namely 16c, 16f , and 20b , were established by X-ray crystallography. The key-step of the proposed reaction mechanism is a 1,5-dipolar electrocyclization of an acyl-substituted ‘thiocarbonyl-ylide’ (cf. Scheme 6). The analogous reaction of 15a, b with 9H-xanthen-9-thione ( 24a ) and 9H-thioxanthen-9-thione ( 24b ) yielded α,β-unsaturated ketones of type 25 (Scheme 5). The structures of 25a and 25c were also established by X-ray crystallography. The formation of 25 proceeds via a 1,3-dipolar electrocyclization to a thiirane intermediate (Scheme 6) and desulfurization. From the reaction of 15a with 24b in THF at 50°, the intermediate 26 (Scheme 5) was isolated. In the crude mixtures of the reactions of 15a with 17 and 19 , a minor product containing a CHO group was observed by IR and NMR spectroscopy. In the case of 19 , this side product could be isolated and was characterized by X-ray crystallography to be 21 (Scheme 4). It was shown that 21 is formed – in relatively low yield – from 20a . Formally, the transformation is an oxidative cleavage of the C?C bond, but the reaction mechanism is still not known.     

Diazo-Transfer Reaction with Diphenyl Phosphorazidate

Diphenyl phosphorazidate (DPPA) was used as the azide source in a one-pot synthesis of 2,2-disubstituted 3-amino-2H-azirines 1 (Scheme 1). The reaction with lithium enolates of amides of type 2 , bearing two substituents at C(2), proceeded smoothly in THF at 0°; keteniminium azides C and azidoenamines D are likely intermediates. Under analogous reaction conditions, DPPA and amides of type 3 with only one substituent at C(2) gave 2-diazoamides 5 in fair-to-good yield (Scheme 2). The corresponding 2-diazo derivatives 6–8 were formed in low yield by treatment of the lithium enolates of N,N-dimethyl-2-phenylacetamide, methyl 2-phenylacetate, and benzyl phenyl ketone, respectively, with DPPA. Thermolysis of 2-diazo-N-methyl-N-phenylcarboxamides 5a and 5b yielded 3-substituted 1,3-dihydro-N-methyl-2H-indol-2-ones 9a and 9b , respectively (Scheme 3). The diazo compounds 5–8 reacted with 1,3-thiazole-5 (4H)-thiones 10 and thiobenzophenone ( 13 ) to give 6-oxa-1,9-dithia-3-azaspiro[4.4]nona-2,7-dienes 11 (Scheme 4) and thiirane-2-carboxylic acid derivatives 14 (Scheme 5), respectively. In analogy to previously described reactions, a mechanism via 1,3-dipolar cycloaddition, leading to 2,5-dihydro-1,3,4-thiadiazoles, and elimination of N₂ to give the ‘thiocarbonyl ylides’ of type H or K is proposed. These dipolar intermediates with a conjugated C?O group then undergo either a 1,5-dipolar electrocyclization to give spirohetrocycles 11 or a 1,3-dipolar electrocyclization to thiiranes 14 .     

Bildung von 5,6-Dihydro-1,3(4H)-thiazin-4-carbonsäure-estern aus 4-Allyl-1,3-thiazol-5(4H)-onen

Formation of Methyl 5,6-Dihydro-l, 3(4H)-thiazine-4-carboxyiates from 4-Allyl-l, 3-thiazol-5(4H)-ones . The reaction of N-[1-(N, N-dimethylthiocarbamoyl)-1-methyl-3-butenyl]benzamid ( 1 ) with HCl or TsOH in MeCN or toluene yields a mixture of 4-allyl-4-methyl-2-phenyl-1,3-thiazol-5(4H)-one ( 5a ) and allyl 4-methyl-2-phenyl-1,3-thiazol-2-yl sulfide ( 11 ; Scheme 3). Most probably, the corresponding 1,3-oxazol-5(4H)-thiones B are intermediates in this reaction. With HCl in MeOH, 1 is transformed into methyl 5,6-dihydro-4,6-dimethyl-2-phenyl-1,3(4H)-thiazine-4-carboxylate ( 12a ). The same product 12a is formed on treatment of the 1,3-thiazol-5(4H)-one 5a with HCl in MeOH (Scheme 4). It is shown that the latter reaction type is common for 4-allyl-substituted 1,3-thiazol-5(4H)-ones.     

Synthese von 4-Benzylthio- und 4-(Arylthio)-1,3-oxazol-5(2H)-onen

Synthesis of 4-(Benzylthio)-and 4-(Arylthio)-1,3-oxazole-5(2H)-ones Following a known procedure, 4-(benzylthio)-1,3-oxazol-5(2H)-one ( 4a ) was synthesized starting from sodium cyanodithioformate ( 1 ) and cyclohexanone (Scheme 1). The structure of the intermediate 4-(benzylthio)-1,3-thiazol-5(2H)-one ( 3a ) was established by X-ray crystallography. An alternative route was developed for the synthesis of 4-(arylthio)-1,3-oxazol-5(2H)-ones which are not accessible by the former reaction. Treatment of ethyl cyanoformate ( 5 ) with a thiophenol in the presence of catalytic amounts of Et₂NH and TiCl₄, followed by addition of a ketone and BF₃.Et₂O in a one-pot-reaction, gave 4f–i in low-to-fair yields (Scheme 3). Both synthetic pathways-complementary as for benzyl–S and aryl-S derivatives–seem to be limited with respect to variation of substituents of the ketone.     

Über den Anteil sigmatroper 1, 5-Wanderung von Kohlenwasserstoffgruppen bei der thermolytischen Skelettisomerisierung 5,5-disubstituierter 1, 3-Cyclohexadiene

On the Extent of Sigmatropic 1, 5-Migration of Hydrocarbon Groups in the Thermolytic Skeletal Rearrangement of 5,5-Disubstituted 1,3-Cyclohexadienes The uncatalyzed skeletal isomerization of 5, 5-disubstituted 1, 3-cyclohexadienes was investigated with the aim to establish the extent to which sigmatropic 1,5-shifts of hydrocarbon groups are participating in these reactions. Gas phase pyrolysis of 5,5-diethyl-1,3-cyclohexadiene ( 7 ) at 460° followed by chloranil aromatization yields only 4% of 1,3-diethylbenzene resulting from 7 through a 1, 5-ethyl migration in the primary reaction step. 2, 3-Dimethylethylbenzene (56%) and 1, 4-diethylbenzene (4%) are obtained as other C₁₀-compounds. This shows that isomerization proceeds mainly through a sequence of electrocyclic and 1, 7-shift reactions. Ethylbenzene (24%) and other aromatic C₈- and C₉-hydrocarbons are formed to a considerable extent, indicating that C, C-bond cleavage is a major competing process and that the 1, 3-diethylbenzene found is the result of a radical recombination reaction and not of a concerted sigmatropic shift of the ethyl group. 5-Methyl-5-phenyl-1, 3-cyclohexadiene ( 12 ) yields 3-methylbiphenyl ( 14 ) and biphenyl upon thermolysis and aromatization. Through ¹³C-substitution of the methyl group in 12 it is shown that in solution at 300° skeletal isomerization proceeds through electrocyclic and 1, 7-H-shift reactions exclusively. In the gas phase at 500° 4% of the isomerization product is formed by a 1, 5-shift of a substitutent, presumably of the methyl group, through a dissociative mechanism. Thermolysis of 5, 5-diphenyl-1, 3-cyclohexadiene ( 22 ) at 560° in the gas phase leads to 1, 1-diphenyl-1, 3, 5-hexatriene ( 23 ) and 1-vinyl-4-phenyl-1, 2-dihydronaphthalene ( 24 ) through electrocyclic reaction steps. In addition a small amount of m-terphenyl is obtained at high conversion of 22 . This indicates that sigmatropic 1,5-phenyl migration can participate in product formation only at high temperature and in the absence of other irreversible pathways to stable products.     

Umsetzung von Diazoessigsäure-ethylester mit 1,3-Thiazol-5(4H)-thionen

Reaction of Ethyl Diazoacetate with 1,3-Thiazole-5(4H)-thiones Reaction of ethyl diazoacetate ( 2a ) and 1,3-thiazole-5(4H)-thiones 1a,b in Et₂O at room temperature leads to a complex mixture of the products 5–9 (Scheme 2). Without solvent, 1a and 2a react to give 10a in addition to 5a–9a . In Et₂O in the presence of aniline, reaction of 1a,b with 2a affords the ethyl 1,3,4-thiadiazole-2-carboxylate 10a and 10b , respectively, as major products. The structures of the unexpected products 6a, 7a , and 10a have been established by X-ray crystallography. Ethyl 4H-1,3-thiazine-carboxylate 8b was transformed into ethyl 7H-thieno[2,3-e][1,3]thiazine-carboxylate 11 (Scheme 3) by treatment with aqueous NaOH or during chromatography. The structure of the latter has also been established by X-ray crystallography. In the presence of thiols and alcohols, the reaction of 1a and 2a yields mainly adducts of type 12 (Scheme 4), compounds 5a,7a , and 9a being by-products (Table 1). Reaction mechanisms for the formation of the isolated products are delineated in Schemes 4–7: the primary cycloadduct 3 of the diazo compound and the C?S bond of 1 undergoes a base-catalyzed ring opening of the 1,3-thiazole-ring to give 10 . In the absence of a base, elimination of N₂ yields the thiocarbonyl ylide A ′, which is trapped by nucleophiles to give 12 . Trapping of A ′, by H₂O yields 1,3-thiazole-5(4H)-one 9 and ethyl mercaptoacetate, which is also a trapping agent for A ′, yielding the diester 7 . The formation of products 6 and 8 can be explained again via trapping of thiocarbonyl ylide A ′, either by thiirane C (Scheme 6) or by 2a (Scheme 7). The latter adduct F yields 8 via a Demjanoff-Tiffeneau-type ring expansion of a 1,3-thiazole to give the 1,3-thiazine.     

Umlagerungsreaktionen von (2′-Propinyl)cyclohexadienolen und -semibenzolen

Rearrangements of (2′-Propinyl)cyclohexadienols and -semibenzenes The acid-catalyzed dienol-benzene rearrangement of 3- and 5-methyl-substituted (2′-propinyl)cyclohexadienols has been investigated. Treatment of the dienols with CF₃COOH in CCl₄ yields allenyl- and (2′-propinyl)benzenes via [3,4]- and [1,2]-sigmatropic rearrangements, respectively. The reaction with H₂SO₄ in Et₂O leeds to a mixture of allenyl-, 2′-propinyl-, 3′-butinyl- and (2′,3′-butadienyl)benzenes (Scheme 3). The latter are products of a thermal semibenzene-benzene rearrangement (cf. Scheme 9). The corresponding semibenzenes have been prepared by dehydration of the cyclohexadienols with H₂SO₄ or POCl₃ (Schemes 6 and 7). Under acidic conditions, the p-(2′-propinyl)semibenzenes 33–35 (Scheme 8) undergo [3,4]- and [1,2]-sigmatropic rearrangements to give again allenyl- and (2′-propinyl)benzenes, whereas the thermal rearrangements to the 3′-butinyl- and (2′,3′-butadienyl)benzenes (Scheme 9) involves a radical mechanism. In contrast, the o-(2′-propinyl)semibenzene b (Scheme 7) leads to (2′,3′-butadienyl)benzene 32 via a thermal [3,3]-sigmatropic rearrangement.     

Does the HO2 radical react with ketones?

The possible reactions of HO₂ with five ketones were studied using a flow tube reactor equipped with a laser magnetic resonance detector. We did not observe reactive loss of HO₂ in any of the five reactions. We place upper limits of <8 × 10⁻¹⁶, <7 × 10⁻¹⁶, <5 × 10⁻¹⁶, <4 × 10⁻¹⁶, and <9 × 10⁻¹⁶ (in units of cm³; molecule⁻¹ S⁻¹) at 298 K for the reactions of HO₂ with CH₃COCH₃, CH₃COC₂H₅, CH₃COC₃H₇, C₂H₅COC₂H₅, and CH₃COC₄H₉, respectively, to give products other than an adduct. We conclude that their reactions with HO₂ are unlikely to be important loss processes for ketones in the atmosphere. © 2000 John Wiley & Sons, Inc. Int J Chem Kinet 32: 573–580, 2000     

Polarographisches Verhalten organischer Verbindungen, die zwei elektronegative Gruppen tragen

Zusammenfassung Der Einfluß der Wechselwirkung von zwei elektronegativen Gruppen R¹ und R² an einem gegebenen molekularen Gerüst auf den Verlauf der polarographischen Kurven, der von dem Charakter dieser Gruppen abhängt, wird diskutiert. Unter den besprochenen Beispielen werden vor allem Benzolverbindungen, die in para-Stellung zwei Gruppen wie CN, SO₂CH₃, SO₂NH₂, COCH₃, COC₆H₅, CHO oder COOH tragen, hervorgehoben.

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Summary Mutual effects of two electronegative groups, R₁ and R₂, on a given molecular frame affect the course of polarographic curves. The shape of the resulting curve depends on the type of mutual interaction of these groups. Among the examples described attention is paid particularly to those benzene derivatives that bear in para-position two groups such as CN, SO₂CH₃, SO₂NH₂, COCH₃, COC₆H, CHO, or COOH.

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Herrn Prof. Dr. M. von Stackelberg zum 70. Geburtstag gewidmet.     

Improved synthesis of cyclic and polymeric phosphazenes based on facile chlorine substitution with phenols promoted by cesium carbonate

In this report we describe a very convenient synthetic method for the preparation in high yields and purity of cyclic [N₃P₃(OCH₂CF₃)₆] and [N₃P₃(OC₆H₄R)₆] (R = Br, CN, CHO, COC₆H₅, COCH₃, H, OCH₃), and polymeric [NP(OC₆H₄R)₂]_n (R = Br, CHO, COC₆H₅, H, Bu^t) phosphazenes from the direct reaction of the trimer [N₃P₃Cl₆] or the high polymer [NPCl₂]_n and the alcohol HO CH₂CF₃ or the para-substituted phenols HO C₆H₄R, using Cs₂CO₃ as proton abstractor and acetone or tetrahydrofuran as solvent.     

Die durch Silberionen katalysierte Umlagerung von Propargyl-phenyläther

It is known that propargyl-phenylethers rearrange at about 200° to 2 H-chromenes [1–4]. It is shown that this rearrangement occurs in benzene or chloroform at lower temperatures (20–80°) in the presence of silver-tetrafluoroborate (or-trifluoracetate). The ethers examined are presented in Scheme 1. Thus in chloroform at 61° in the presence of AgBF₄, phenyl-propargylether ( 3 ) yields 2 H-chromene ( 13 ). With 0.78 molar equivalents AgBF₄ in benzene at 80° the same ether 3 yields a 3:1 mixture of 2-methyl-cumaron ( 14 ) and 2 H-chromene ( 13 ). From 1′-methylpropargyl-phenylether ( 4 ) and 2′-butinyl-3,5-dimethylphenylether ( 5 ) under similar conditions the corresponding chromenes 16 and 17 resp. are obtained. Rearrangement of propargyl- and 2′-butinyl-1-methyl-2-naphthylether ( 6 and 7 resp.) in benzene at 80° in the presence of AgBF₄ gives the corresponding allenyl-naphthalenones 18 and 19 resp. Treatment of propargyl- and 2′-butinyl-mesityl-ether ( 8 and 9 resp.), and propargyl- and l′-methylpropargyl- 2 , 6 -dimethyl-phenylether ( 10 and 11 resp.) in benzene at 80° with AgRF, yields as the only product the corresponding 3 -allenyl-phenols 21 , 22 , 24 and 25 (Scheme 3). It is shown that in the presence of μ-dichlor-dirhodiuni (1)-tetracarbonyl in benzene a t 80° the ether 4 rearranges to 2-methyl-2H-chromene (16). However with this catalyst the predominant reaction is a cleavage to phenol. No reaction was observed when ethers 3 and 12 , (Scheme 7 ) were treated with the tris-(trimethylsily1)-ester of vanadic acid in benzene a t 80° (see also [8]). By analogy with the known mechanism for thc silver catalysis of the reversible propargylesterl/allenylester rearrangement [S], the silver (1)ion is assumed to form a pre-equilibrium π-complex with the C, C-triplebond of the substrate. This complex then undergoes a [3s, 3s]-sigmatropic rearrangement (Scheme 2). In the case of the others 6 , 7 and 12 the resulting allenyldienones were isolated. The 2,G-dimethyl substituted ethers 8 , 9 , 10 and 11 resp. first give the usual allenyl- dienones (Scheme 3). These then undergo a novel silver catalysed dienon-phenol-rearrangement (Sclzenzu4) to give the 3-allenylphenols 21 , 22 , 24 and 25 . Thc others 3 , 4 and 5 with free ortho positions presumably rearrange first to the non-isolated 2-allenyl-phenols 15 , 42 and 43 resp.(Scheme 7). These then rearrange, either thermally or by silver (1)ion catalysis to the 2H-chromenes 13 , 16 and 17 resp. The rate of the rearrangement of 2-allenylphenol ( 15 ) to 13 at room temperature in benzene or chloroform is approximately doubled when silver ions are present as catalyst.     

氧化腈与丙炔1,3-偶极环加成反应中区域选择性的理论研究

用密度泛函(DFT)B3LYP/6-311＋＋G**方法研究了氧化腈(RCNO, R＝F, NO₂, OCH₃, OH, COOCH₃, CHO, CONH₂, H, CH₃)与丙炔的1,3-偶极环加成反应, 并且计算了不同温度下的反应速率常数, 讨论了氧化腈上不同取代基R的取代效应和温度对反应区域选择性的影响. 结果显示, 氧化腈与富电子亲偶极体——炔烃反应, 5-取代反应占优势; 氧化腈上取代基R为强吸电子基团时或在较高温度下, 有利于4-取代反应的进行.     

Eine überraschende Ringerweiterung von 3-(Dimethylamino)-2,2-dimethyl-2H-azirin zu 4,5-Dihydropyridin-2(3H)-on-Derivaten

An Unexpected Ring Enlargement of 3-(Dimethylamino)-2,2-dimethyl-2H-azirine to 4,5-Dihydropyridin-2(3H)-one Derivatives The reaction of 3-(dimethylamino)-2,2-dimethyl-2H-azirine ( 1a ) and 4,4-disubstituted 2-(trifluoromethyl)-1,3-oxazol-5(4H)-ones 7 in MeCN at 70° afforded 5-(dimethylamino)-3,6-dihydropyrazin-2(1H)-ones 10 (Scheme 4), whereas no reaction could be observed between 1a and 2-allyl-4-phenyl-2-(trifluoromethyl)-1,3-oxazol-5(2H)-one ( 8a ) or 4,4-dibenzyl-2-phenyl-1,3-oxazol-5(4H)-one ( 9 ). The formation of 10 is rationalized by a mechanism via nucleophilic attack of 1a onto 7 . The failure of a reaction with 9 shows that only activated 1,3-oxazol-5(4H)-ones bearing electron-withdrawing substituents do react as electrophiles with 1a . The amino-azirine 1a and 2,4-disubstituted 1,3-oxazol-5(4H)-ones 2b – e in refluxing MeCN undergo a novel ring enlargement to 4,5-dihydropyridin-2(3H)-ones 11 (Scheme 5). Several side products were observed in these reactions. Two different reaction mechanisms for the formation of 11 are proposed: either 1a undergoes a nucleophilic addition onto the open-chain ketene tautomer of 2 (Scheme 6), or 2 reacts as CH-acidic compound (Scheme 7).     

Radikalische Cyclisierungen von Alkenyl-substituierten 4,5-Dihydro-1,3-thiazol-5-thiolen

Radical Cyclizations of Alkenyl-Substituted 4,5-Dihydro-1,3-thiazole-5-thiols Heating of 5-alkenyl- or 5-alkinyl-4,5-dihydro-1,3-thiazole-5-thiols of type 5 in the presence of a radical initiator gave dithiaspirobicycles in fair-to-excellent yield (Scheme 3). Under analogous conditions, the 4,5-dihydro-4-vinyl-1,3-thiazole-5-thiol 5d underwent a cyclization to give the annellated dithiabicycle 7 (Scheme 4). In this reaction, a minor product 8 was formed by an unknown reaction mechanism. The structure of 8 was established by X-ray crystallography. The starting 1,3-thiazole-5-thiols 5 have been synthesized by carbophilic alkylation of me C?S group of 1,3-thiazole-5(4H)-thiones with Grignard-reagents or alkylcuprates. The thiazolethiones were obtained by the reaction of 3-amino-2H-azirines with thiobenzoic acid followed by sulfurization and cyclization. The 4-benzyl derivative 1b was thermally rearranged via 1,3-benzyl migration to yield the benzyl (1,3-thiazol-5-yl) sulfide 11 (Scheme 5).     

[(1,3-Dioxolan-2-yliden)methyl]phosphonate und -phosphinate als (einfache) Synthone in der Heterocyclensynthese

[(1,3-Dioxolan-2-ylidene)methyl]phosphonates and -phosphinates as [simple] Synthons in Heterocyclic Synthesis The readily available [(1,3-dioxolane-2-ylidene)methyl]phosphonates and -phosphinates 2a–f (Scheme 1) can be transformed with amines to aliphatic ketene N,O-and N,N-acetales (see Scheme 2, 2a → 3–7 ). Alkanediamines yield with 2a–f the imidazolidines 8a–f and the hexahydropyrimidines 9a–d (Scheme 3). the oxazolidine derivatives 10a–e and the thiazolidine 11 are accessible under special reaction conditions starting from 2a, b (Scheme 4). Hydrazines react with the CN-group-containing ketene O,O-acetals 2a–c to the pyrazoles 12a–g , whereof 12a, d, e can be cyclized to pyrazolo[1,5-a]pyrimidines 13a–d (Scheme 5). Amidines as starting materials transform 2a–c in an analogous way to the pyrimidine derivatives 14a–c (Scheme 6).     

Photoinduced superoxide radical anion and singlet oxygen generation in the presence of novel selenadiazoloquinolones (an EPR Study)

Novel 7‐substituted 6‐oxo‐6,9‐dihydro[1,2,5]selenadiazolo[3,4‐h]quinoline ( SeQ(1–6) ) and 8‐substituted 9‐oxo‐6,9‐dihydro[1,2,5]selenadiazolo[3,4‐f ]quinoline derivatives ( SeQN(1–5) ) with R₇, R₈ = H, COOC₂H₅, COOCH₃, COOH, COCH₃ or CN were synthesized and their spectral characteristics were obtained by UV/Vis spectroscopy. Ultraviolet A photoexcitation of the selenadiazoloquinolones in dimethylsulfoxide or acetonitrile resulted in the formation of paramagnetic species coupled with molecular oxygen activation generating the superoxide radical anion or singlet oxygen, evidenced by electron paramagnetic resonance spectroscopy. The cytotoxic/photocytotoxic impact of selenadiazoloquinolones on murine and human cancer cell lines was demonstrated using the derivative SeQ5 (with R₇ = COCH₃).     

Electronic structure of ferrocence derivatives studied by He(I) photoelectron spectroscopy and CNDO /2 method

The effect of substituents in the Cp ligands on the electronic structure has been studied for the 1,1′-disubstituted ferrocenes Fe(CpX)₂, with X = C₂H₅, OCH₃, CN, COCH₃, COOCH₃, OOCCH₃, CH₂C₆H₅, or C₆H₅, by UV photoelectron spectroscopy and by CNDO /2 calculations. The energy gap between the ²E_2g and ²AT_1g ion states, 0.36 eV in the parent ferrocene, is affected only by the COCH₃ and COOCH₃ substituents, which lower it to 0.22 and 0.28 eV, respectively. Splitting of e_1u(π) level due to the lowering of the symmetry is the only effect observed in the photoelectron spectra. There is a strong conjugation between the phenyl and cyclopentadienyl β-orbitals in 1,1′-diphenylferrocene. The changes in the a_1g(d) ionization energy calculated by the ΔSCF method using CNDO /2 total energies are in a good agreement with the experimental data.     

Umsetzung von Di(tert-butyl)- und Diphenyldiazomethan mit 1,3-Thiazol-5(4H)-thionen: Isolierung und Kristallstruktur des primären Cycloadduktes

Reaction of Di(tert-butyl)- and Diphenyldiazomethane and 1,3-Thiazole-5(4H)-thiones: Isolation and Crystal Structure of the Primary Cycloadduct Reactions of diazo compounds with C?S bonds proceed via the formation of thiocarbonyl ylides, which, under the reaction conditions, undergo either 1,3-dipolar cycloadditions or electrocyclic ring closer to thiiranes (Scheme 1). With the sterically hindered di(tert-butyl)diazomethane ( 2c ), 1,3-thiazole-5(4H)-thiones 1 react to give spirocyclic 2,5-dihydro-1,3,4-thiadiazoles 3 (Scheme 2). These adducts are stable in solution at ?20°, and they could be isolated in crystalline form. The structure of 3c was established by X-ray crystallography. In CDCl₃ solution at room temperature, a cycloreversion occurs, and the adducts of type 3 are in an equilibrium with 1 and 2c . In contrast, the reaction of 1 with diphenyldiazomethane ( 2d ) gave spirocyclic thiiranes 4 as the only product in high yield (Scheme 3). The crystal structure of 4b was also determined by X-ray analysis. The desulfurization of compounds 4 to 4,5-dihydro-5-(diphenylmethylidene)-1,3-thiazoles 5 was achieved by treating 4 with triphenylphosphine in boiling THF. The crystal structure of 5f is shown.     

4-Amino-1,5-dihydro-2H-pyrrol-2-one aus Bortrifluorid-katalysierten Umsetzungen von 3-Amino-2H-azirinen mit Carbonsäure-Derivaten

4-Amino-1,5-dihydro-2H-pyrrol-2-ones from Boron Trifluoride Catalyzed Reactions of 3-Amino-2H-azirines with Carboxylic Acid Derivatives Reaction of 3-amino-2H-azirines 1 with ethyl 2-nitroacetate ( 6a ) in refluxing MeCN affords 4-amino-1,5-dihydro-2H-pyrrol-2-ones 7 and 3,6-diamino-2,5-dihydropyrazines 8 , the dimerization product of 1 (Scheme 2). Thus, 6a reacts with 1 as a CH-acidic compound by C? C bond formation via C-nucleophilic attack of deprotonated 6a onto the amidinium-C-atom of protonated 1 (Scheme 5). The scope of this reaction seems to be rather limited as 1 and 2-substituted 2-nitroacetates do not give any products besides the azirine dimer 8 (see Table 1). Sodium enolates of carboxylic esters and carboxamides 11 react with 1 under BF₃ catalysis to give 4-amino-1,5-dihydro-2H-pyrrol-2-ones 12 in 50–80% yield (Scheme 3, Table 2). In an analogous reaction, 3-amino-2H-pyrrole 13 is formed from 1c and the Li-enolate of acetophenone (Scheme 4). A reaction mechanism for the ring enlargement of 1 involving BF₃ catalysis is proposed in Scheme 6.     

Eine thermische,intramolekulare [2 + 2]-Cycloaddition eines Allenyl-benzols; Synthese von Allenylbenzolen durch säurekatalysierte Dienol-Benzol-Umlagerung

A thermal Intermolecular [2 + 2]-Cycloaddition of an Allenyl-Allyl-Benzene; Synthesis of Allenylbenzenes via Acid-Catalyzed Dienol-Benzene Rearrangement A few years ago, it has been shown that the acid-catalyzed dienol-benzene rearrangement of 2-propinyl-substituted cyclohexadienols is a convenient synthesis for allenyl-substituted benzene derivatives. The cyclohexadienols 20 and 21 were prepared via C-alkylation of the corresponding phenols with 2-propinylbromide (Scheme 3), followed by reduction of the cyclohexadienone 13 and 17 with LiAlH₄. Treatment of 20 and 21 with p-toluenesulfonic acid in ether at ?15°) yielded the desired allenyl benzenes 8 and 9 , respectively, via [3,4]-sigmatropic rearrangements (Scheme 4). The 2-propinylbenzenes 22–24 , formed via [1,2]-sigmatropic shift of the 2-propinylgroup, were found as by-products. Thermolysis of allenyl benzene 8 in decane yielded two bicyclic ( 25 and 26 ) and two tricyclic products ( 27 and 28 ; Scheme 5). For the formation of 25 and 26 , a pericyclic reaction mechanism (Scheme 6) as well as a mechanism via biradical intermediates (Scheme 7) is discussed. A [2 + 2]-cycloaddition of the α,β-allenic and the allylic C,C-double bound of 8 led to the tricyclic products 27 and 28 (Scheme 9). All attempts to realize a [1,7]-sigmatropic H-shift in the allene 9 failed so far, and the starting material underwent a rapid polymerisation.