Transpositions thermiques de derives d'α-pinene

Novel thermal transformations of (+)-pin-2-en-9-al 1 and (+)-9-methyl-pin-2-en-9-one 3 by [3,3] sigmatropic mechanism to allyl vinyl ethers 2 and 4 are described. The ether 4 may undergo further rearrangement in an acid-catalysed step to the (-)-2.6-dimethylbicyclo[3.3.1]non-6-en-2ones (5 and 5'). Formation of the bicyclic ketones (+)-5 and 5' of opposite absolute configuration occurs by [3,3] sigmatropic rearrangement of the trimethylsilyl enol ether of 3 and hydrolysis. The proposed mechanism is confirmed by studying the deuterated ketone d₃^?3.     

Mise en évidence d'un désordre statistique dans les structures chalcogénoiodures d'étain et d'antimoine

The crystal structures of Sn₂SbX₂I₃, with X = S or Se, and Sn₃SbSe₂I₅ are characterized by a statistical disorder of part of the [Sb] and [Sb, Sn] sites. All these crystal structures are built up from infinite ribbons (Sn₂X₄)_n of SnX₅ pyramids where X = ((S, Se) and I). The ribbons are weakly linked through Sn … I interactions to give infinite sheets. Between sheets are located [Sb] or [Sb, Sn] atoms in twinned sites.     

Synthese d'aziridine alcool a fonction aziridine secondaire

The reactions of Grignard reagents with α-keto oximes 1 and α-hydroximino alcohols 3, give secondary aziridine alcohols 2 or 4, which with SOCL₂ (or COCl₂)give azabicyclo[3.1.0]oxo-2 oxaisothiazolidine-1, 5 or azabicyclo[3.1.0]carbamate-1,2,3 6. The determination of configuration of 2,4 and 5 was achieved by an NOE study.     

Reaction des nitrones avec les chlorures d'acides: action de chlorures d'aryl-sulfonyles et du chlorure de benzoyle sur des n-oxy (aryl-1 dihydro-3,4 isoquinoleines). Formation d'une isoquinoleine,d'un isocarbostyryle ou d'une indoline selon les conditions

Toluene-p-sulphonyl chloride, p-nitrobenzoyl chloride, and benzoyl chloride react with 1-aryl 3,4-isoquinoline N-oxide depending on the acidity of the medium, the nature of the substituent at C-1, and the nature of the acid chloride, to give an isoquinoline, an isocarbostyril (resulting from migration of the phenyl substituent at C-1), an indoline (resulting from migration of the phenyl moiety incorporated in the heterocycle), or the formation of an O-acyl hydroxamic acid. The maximum selectivity is obtained in an heterogeneous medium and is governed by the intermediate formation of an hydroxylated pseudo-base.     

Indole derivatives. 140. Friedel-Crafts acylation of some 5-substituted 2-(ethoxycarbonyl)indoles by p-nitrobenzoyl chloride

It was shown that Friedel-Crafls acylation of 5-methyl-2-(ethoxycarbonyl)indole by p-nitrobenzoyl chloride occurs predominantly in the 4 and 7 positions, and that of the 5-methoxy derivative occurs in the 4 position.See [1] for Communication 139.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1055–1059, August, 1993.     

Influence de la longueur d'onde sur la photoisomerisation de derives de l'hexatriene-1,3,5

Kinetic studies of photoisomerization of 1-phenyl 6-methyl-cyclohexa-1,3-diene, and of the four isomeric 5-phenylhepta-1,3,5-trienes, have been performed at 313, 254, 228 and 214 nm. Photoreactions of these compounds are dependent on the wavelength of irradiation. Photolysis at short wavelength of Z,E-5-phenylhepta-1, 3,5-triene initiates a new reaction, sigmatropic [1,5] hydrogen migration, forming an ene-allenic compound. Thermal reactivity data for polyenic compounds supports the assigned structures.     

Processus concurrents de photoisomerisation d'hexatrienes polymethyles: effet de longueur d'one

The ground-state conformer composition is shown to play a determining role in the orientation of the photochemical reactions of two hexatrienes. A pronounced wavelength effect is observed for Z-2,6-dimethyl-1,3,5-heptatriene; photocycloaddition leads to a bicyclo[3.1.0]hexene and [1,5] sigmatropic hydrogen migration occurs from an s-cis-s-trans conformation preferentially excited by longer wavelength light, whereas the Z-E interconversion is predominantly observed as a result of excitation of the s-trans-s-trans conformation by shorter wavelength light.     

5,6-二甲氧基-N-[(R)-4-甲氧基-2-(丙烯-2-基)-2,3-二氢苯并呋喃-5-基]-1,1a,2,7b-四氢环丙并[c]苯并吡喃-7b-基甲酰胺的合成与表征

鱼藤酮与氧硫叶立德反应得到关键中间体(5,6-二甲氧基-1,1a,2,7b-四氢环丙并[c]苯并吡喃-7b-基)[(R)-4-羟基-2-(丙烯-2-基)-2,3-二氢苯并呋喃-5-基]甲酮(2),2再通过醚化、肟化、贝克曼重排得到5,6-二甲氧基-N-[(R)-4-甲氧基-2-(丙烯-2-基)-2,3-二氢苯并呋喃-5-基]-1,1a,2,7b-四氢环丙并[c]苯并吡喃-7b-基甲酰胺(5),化合物的结构经1H NMR,MS和元素分析确认,采用单晶X射线衍射法确定化合物5的晶体结构.化合物5属于三斜晶系,P1空间群,晶胞参数:a=0.95772(5)nm,b=1.06591(6)nm,c=1.30112(7)nm,α=111.8460(10)°,β=109.8870(10)°,γ=93.0870°,V=1.13429(11)nm3,Z=2,Dc=1.281 g/cm3,μ(Mo Kα)=0.092 mm-1,F(000)=464.     

Novel stereoconvergent transformation of 1,2a-disubstituted 1,2,2a,8b-tetrahydro-3H-benzo[b]cyclobuta[d]pyran-3-ones to 1,3-disubstituted 1,2,4a,9b-tetrahydrodibenzofuran-4-ols and its application to the second-generation synthesis of (+/-)-linderol A

1,2a-Disubstituted 1,2,2a,8b-tetrahydro-3H-benzo[b]cyclobuta[d]pyran-3-ones bearing an electron-withdrawing group at the 2a-position were treated with two equivalents of dimethylsulfoxonium methylide to give r-1,t-4a,t-9b-1,3-disubstituted 1,2,4a,9b-tetrahydrodibenzofuran-4-ols stereoconvergently regardless of the stereochemistry of the 1-position on the benzocyclobutapyran ring. This methodology was applied to the second-generation synthesis of (+/-)-linderol A, a melanin biosynthesis inhibitory natural product.     

Studies on ketene and its derivatives. LXXXIII. Reaction of diketene with isoquinolinium and pyridinium methylide derivatives

Reaction of isoquinolinium bis(ethoxycarbonyl)methylide (I) with diketene gave diethyl 1-acetyl-2,3-dihydro-2-oxopyrrolo[2,1-α]isoquinoline-3,3-dicarboxylate (VI), which on hydrolysis with dilute hydrochloric acid afforded ethyl 1-acetyl-2-hydroxypyrrolo[2,1-α]isoquinoline-3-carboxylate (IX) and ethyl 3-methylpyrrolo[2,1-α]isoquinoline-3-carboxylate (X). On the other hand, isoquinolinium cyanoethoxycarbonylmethylide (IIa) reacted with diketene to give isoquinolinium cyano(3-ethoxycarbonyloxy-3-butenoyl)methylide (XIIIa) which was isomerized to isoquinolinium cyano(3-ethoxycarbonyloxy-2-butenoyl)methylide (XIII). Similarly, reactions of isoquinolinium cyanomethoxycarbonylmethylide (IIb) and pyridinium cyanoalkoxycarbonyl-methylide (IIIa,b) with diketene gave rise to the corresponding cyano(3-alkoxycarbonyloxy-3-butenoyl)methylides (XIIb, XVIa,b).     

Synthese und thermisches Verhalten von 6,8-Dimethylentricyclo[3.2.1.02,7]oct-3-enen; [3s 3s]-sigmatropische Umlagerungen von 6-Allenyl- und 6-Propargly-1- Methylen-cyclohexa-2,4-dienen in aromatische Kohlenwasserstoffe als Beispiele für konzertierte Semibenzol → Benzol-Umlagerungen

The tricyclic dimethylene hydrocarbons 5 , 6 , 7 , 8 and d₂- 5 , (Scheme 2), which are prepared by Wittig-reaction from the corresponding ketones, are rearranged, by heating, to 4-aryl-but-1-yne derivatives via the unstable 6-allenyl-1-methylene-cyclohexa-2, 4-diene intermediates (e.g. Scheme 14). Using the deuterium-labelled compound d₂- 5 , it was shown that the allenyl moiety, formed by a retro-Diels-Alder reaction (cycloreversion) of the tricyclic dimethylene compound, migrates with complete inversion in the final o-semibenzene-benzene rearrangement (Schemes 11 and 14). Reaction of 6-propargyl-cyclohexa-2, 4-dien-1-ones with triphenylphosphonium methylide gives 6-propargyl-1-methylene-cyclohexa-2 4-dienes, which immediately undergo a [3s, 3s]-rearrangement to form 4-aryl-buta-1, 2-dienes (Scheme 9). In contrast, the rearrangement of the corresponding 4-propargyl-1-methylene-cyclohexa-2, 5- dienes proceeds by a radical mechanism (Schemes 10 and 13).     

Photo-oxygenations de composes aromatiques sensibilisees par des accepteurs d'electron

Photo-oxygenation of aromatic compounds sensitized by electron acceptors, like 9-10 dicyanoanthracene (DCA) is shown to proceed by two distinct mechanisms each one beginning by an electron-transfer step: in the first way superoxide ion [O₂^?] is involved and in the second one singlet oxygen [¹O₂^*] is produced according to an unusual process.     

2-Aza-l, 3-dienes. Partie 6. Observation d′un effet ‘tert-amino’ dans le traitement acide de (pyrrolidin-l-yl)-azadienes

‘tert-Amino Effect’ on Acidic Treatment of (Pyrrolidin-l-yl)azadienes The behaviour of 4-morpholino- and 4-(pyrrolidin-l-yl)-2-aza-1. 3-diene-l, l-dicarbonitriles 3 , and 4 and 10 , respectively, in acidic medium is described. The former gives with HBr/AcOH 3-bromopyrazine-2-carbonitrile 6. On the other hand, pyrrolidin-1-yl derivatives 4 and 10 furnish, by a [1, 5]-H shift, pyrrolo[l, 2]pyrazine structures 5 and 11 , respectively.     

Spectres de vibration et structure d'un cristal d'amidogallate de sodium

Raman spectra (4000-150 cm^?1) of a single crystal of NaGa(NH₂)₄ and infrared spectra (4000-200 cm^?1 ) of a polycrystalline sample have been studied at different temperatures. An assignment of the bands is given. The spectra are discussed assuming S₄ and T_d point group symmetry of the Ga(NH₂)^?₄ ion at low temperature and at room temperature respectively. Metal-ligand and N-H stretching frequencies are compared to those of some other amido metalates.     

Biohydroxylation d'un aza-2 bicyclo [2.2.1] heptane

Biohydroxylation with Beauveria sulfurescens of the 5-exo position of the 2-aza bicyclo [2.2.1] heptane ring system gives rise to a precursor of carbocyclic 2-deoxy nucleosides.     

Reactivite de lithiens derives d'ethers de la cyanhydrine du benzaldehyde vis-a-vis d'α-enones cycliques

Conjugate addition of reagent 1A to 2-cyclohexenone 3 can be realized in THF-HMPT, so that one-pot conjugate addition—CH₃I enolate trapping, leading to trans 2-methyl 3-benzoylcyclohexanone 17 can be easily performed. From isophorone 4 and Δ¹⁽⁹⁾-2-octalone 5, 1, 4-addition under kinetic control is observed in THF. In the presence of HMPA, the reaction is under thermodynamic control. At low temperatures enolate 19a is in equilibrium with 1A and 4; from 4 at 0° or 5 at ?65° or at 0°, the equilibrium lies on the side of starting materials. No reaction between 1A and 6 takes place in any solvent.The reaction of 1B and isophorone 4 in THF leads to 1, 2-addition under kinetic control and to 1, 4-addition under thermodynamic control. In THF-HMPT, retro-Michael addition is observed. However, 1, 2-addition takes place in THF to 6.The different results are interpreted in terms of interplay of ion-pairing, steric decompression and steric hindrance to 1, 4-addition as well as the possibility of participation of the Li cation for 1, 2-addition.     

Monofluoromethyl‐Substituted Sulfonium Ylides: Electrophilic Monofluoromethylating Reagents with Broad Substrate Scopes

Two electrophilic monofluoromethylating reagents, monofluoromethyl(phenyl)sulfonium bis(carbomethoxy)methylide ( 3 a ) and monofluoromethyl(4‐nitrophenyl)sulfonium bis(carbomethoxy)methylide ( 3 b ), and their reactions under mild conditions with a variety of nucleophiles, such as alcohols and malonate derivatives, sulfonic and carboxylic acids, phenols, amides, and N heteroarenes, are described. Mechanistic studies with deuterated reagents [D₂] 3 a /[D₂] 3 b suggest that these monofluoromethylation reactions proceed through an electrophilic substitution pathway.     

Thiofenchone s‐methylide and its spiro‐1,3,4‐thiadiazoline precursor

Spiro[fenchane‐2,2′‐(1,3,4)‐thiadiazoline] ( 6 ), prepared from thiofenchone and diazomethane, extrudes N₂ (t_1/2 22 min, 46°C, toluene) and furnishes the S‐methylide 7 which, in turn, closes the thiirane ring or else is intercepted by 1,3‐cycloadditions to dipolarophiles (tetracyanoethylene, maleic anhydride, N‐methyl‐1,2,4‐triazoline‐3,5‐dione, aromatic thioketones). When thiocarbonyl S‐methylide 7 is set free in methanol, fenchone S,O‐dimethylacetal is formed as an HX adduct. Catalysis by acetic acid converts 7 to 1‐(methylthio)‐α‐fenchene ( 25 ) by way of a Wagner‐Meerwein rearrangement. The addition of diazomethane to thiocampher leads, via thiadiazoline 12 , to thiocamphor S‐methylide; the latter undergoes a 1,4‐H shift, thus affording 2‐methylthio‐2‐bornene ( 11 ). © 2001 John Wiley & Sons, Inc. Heteroatom Chem 12:136–145, 2001     

Per - bicyclophosphoranylation d'alditols

Reaction of bicyclophosphane $\text{1}$ with glycol $\text{2}$, glycerol $\text{3}$, erythritol $\text{4}$, L(-)arabitol $\text{5}$ and dulcitol $\text{6}$ leads to the corresponding per-alkoxybicyclophosphoranes $\text{2p}$ - $\text{6p}$ which are in tautomeric equilibrium with the phosphates forms $\text{2p}$′ - $\text{6p}$′.The amount of these latters increases regularly from traces to 24%.     

Synthese et transposition thermique d'alcools α-ethyleniques β'-alleniques

Thirteen variously substituted α-ethylenic β'-allenic alcohols (1,5,6-triene-3-ols) have been synthesized by three different methods, for two of which the key step was the reaction of an organo copper reagent with a derivative of a β-hydroxy γ-ethylenic alcohol (1-ene-5-yne-3,7-diol). The[3,3]-sigmatropic rearrangement of these alcohols, following the heating of their solution in diglyme, leads to γ-dienic aldehydes and ketones. The yields are best (60–70%) for tertiary alcohols substituted on carbon 5. Comparisons of the reactivities of these 13 alcohols show that the mechanism of this rearrangement can probably vary, following the substitution from a cyclohexadiyl biradical process to a concerted pathway involving a cyclohexane transition state.