The facile (<−50°C) formation of cis-bicyclo[6.1.0]nona-2,4,6-trienes from cyclonona-1,3,5,7-tetraenes: A symmetry - forbidden reaction

The formation of the $\text{cis}$-bicyclo [6.1.0] nona-2,4,6-trienes $\text{4a}$-$\text{c}$ is not due to the sequence $\text{1}$ → $\text{2}$ → $\text{4}$, which would involve the symmetry-forbidden reaction $\text{2}$ → $\text{4}$ even at ?50°C. Rather, reaction of RX at C^4–7 of $\text{5}$, which is formed together with $\text{1}$, leads (probably via $\text{6a}$-$\text{c}$ and $\text{7a}$-$\text{c}$ to $\text{4a}$-$\text{c}$.     

Photochemistry of N-aryl-2(1H)-pyrimidin-2-ones

Irradiation of N-aryl-2(1H)-pyrimidin-2-ones ($\text{3a}$-$\text{c}$) in a mixed benzene-alcohol solution afforded the products initiated by Type I cleavage, 1-(3-alkoxycarbonylamino-2-propene)-N-arylimines ($\text{4a}$-$\text{c}$, $\text{5}$, and $\text{6}$) in 45–51% yields.     

Oxidative decarboxylation of [n.2.2]propellane carboxylic acids with lead tetraacetate. rearrangement approach to bicyclo [n.2.2.]bridgehead alkenes.

Oxidative decarboxylation of [n.2.2]propellane carboxylic acids ($\text{1a}$-$\text{c}$) with lead tetraacetate gave the bicyclic acetates ($\text{2b}$, $\text{c}$) having a bridgehead double bond and/or the tricyclic acetates ($\text{3a}$, $\text{b}$) in good yields. Vapor phase thermolysis of $\text{3a}$ or $\text{3b}$ afforded the bridgehead olefin $\text{2a}$ or $\text{2b}$ quantatively.     

Conjugative cycloaddition of N-chlorosulfonyl isocyanate across vinylcyclopropane system. A new pathway towards macro-heterocycles

trans- -Isopropenyl-4-methylene-spiro[2.x]alkanes ($\text{4a}$ and $\text{4b}$) react at 0°C with CSI to give as major products the trans bicyclic cycloazanondienones ($\text{12a}$-$\text{12b}$) and as the minor products bicyclodihydro-azepinones ($\text{11a}$ and $\text{11b}$), and the respective cis isomer of bicyclic cycloazanondienones ($\text{13a}$ and $\text{13b}$).     

Solid solution formation in chalcopyrite systems of the type AgInX2AgMIIIX2 where M = Al,Ga, and X = S,Se

Previous (1) work on ternary chalcopyrite solid solution formation has shown that the difference in end point axial ratios ($\text{Δc}\text{a}$) is an important factor in determining the extent of mutual solubility. It was concluded that when $\text{Δc}\text{a}\text{> 0.13}$ complete solid solubility will not occur. In this work it is shown that complete solid solution formation in the systems AgAlS₂AgInS₂ ($\text{Δc}\text{a}\text{= 0.111}$), AgGaS₂AgInS₂ ($\text{Δc}\text{a}\text{= 0.11}$) and AgAlSe₂AgInSe₂ ($\text{Δc}\text{a}\text{= 0.112}$) does occur. This shows that the value of $\text{Δc}\text{a}\text{= 0.13}$ as an upper limit for solid solution formation can be approached closely.     

Stereochemical studies — 79 synthesis and kinetic study on the retrodiene decomposition of norbornene-condensed 1,3-oxazin-4-ones

The $\text{cis}$-$\text{cxo}$- amino acid $\text{c}$ with norbornene skeleton was converted into 2-aryvl-$\text{cis}$-$\text{cxo}$-1,3-oxazin-4-ones $\text{5a}$-$\text{d}$. These compounds, similarly to the $\text{diendo}$ isomers $\text{1a}$-$\text{d}$ studied by us earlier, undergo retrodiene decomposition under mild conditions to give 2-aryl-6$\text{2}$-l,3-oxazin-6-ones ($\text{2}$$\text{a}$-$\text{d}$) in 50-60% yield. The ratio of the decomposition rate constants of the tricyclic $\text{diendo}$ and $\text{diexo}$-1,3-oxazin-4-ones, measured in toluene solution, is about 2.     

A study of polytypism in AgIn5Se8 by combined electron microscopy techniques

Three different polytypes are found to exist in AgIn₅Se₈. They have been studied by means of conventional electron microscopy and diffraction as well as by high-resolution microscopy. The three different structures have tetragonal symmetry and can be derived from each other by means of periodic antiphase boundaries; they correspond to $\text{c}\text{a}\text{= 4,}\text{c}\text{a}\text{= 2}$, and $\text{c}\text{a}\text{= 1}$, respectively. Regions of $\text{c}\text{a}\text{= 4}$ often occur as microsyntactic intergrowths into $\text{c}\text{a}\text{= 2}$ areas, and a large number of nonperiodic antiphase boundaries also occur. After fast cooling from above T_c a transition state characterized by the presence of diffuse intensity has been observed and analyzed.     

Nucleosides, 45.-Assignment of glycosylation sites in o-hexopyranosyl-ribonucleosides by 13C-NMR

Evidence is presented that glycosylation of a ribose-OH group in nucleosides results in a significant downfield shift for the appended ¹³C nucleus and smaller upfield displacements for the adjacent carbons, providing an efficient tool for differentiating between 2′-$\text{o}$-, 3′-$\text{o}$- and 5′-$\text{o}$-glycosyl-ribonucleosides. Therewith, the products formed on enzymatic galactosylation of uridine, inosine, and adenosine are unequivocally assigned β(1→3)-glycosidic linkages ($\text{3a}$ – $\text{3c}$).     

Photocyclization of n-[ω-(cycloalken-1-yl)alkyl]-and n-[ω-(inden-3-yl)alkyl]phthalimides : Synthesis of spiro-nitrogen multicyclic systems

Photolysis of the N-[ω-(cycloalken-1-yl)alkyl]phthalimides 6b-$\text{e}$ in each case gave a pair of stereoisomers of spiro-nitrogen multicyclic systems (9b-$\text{e}$) in moderate yields, whose stereochemistry was determined by means of chemical and spectroscopic analyses. Similarly, in N-[ω-(inden-3-yl)alkyl]-phthalimides (8), spiro-nitrogen macrocycles up to 13-membered 13a-$\text{c}$ were obtained in good yields     

Studies on nucleosides and nucleotides. X. desulfurization of 2′,3′-0-Isopropylidene-2-thiouridines by dibenzoyldiazene

The reaction of dibenzoyldiazene with 2′,3′-0-isopropylidene derivatives of 2-thioridine, 5-methyl-2-thiouridine, and 5-methoxycarbonylmethyl-2-thio-uridine afforded the corresponding desulfurized products, $\text{3a}$-$\text{3c}$.     

Biomimetic synthesis of bacterial c50 carotenoids decaprenoxanthin and c.p. 450

Alkylation of the distal double bond of pseudoionone $\text{4}$ has been carried out with isoprene epoxide (ZnCl₂ /MeNO₂ ) leading directly to α-$\text{cis 10 a}$, α-$\text{trans}$$\text{10b}$ and γ $\text{10c}$ hydroxyprenylionones. The α-$\text{cis}$ and γ-isomers have been converted in few steps into the C₅₀ carotenoids decaprenoxanthin $\text{1}$ and C.p. 450 $\text{3}$ respectively.     

3-methylthio-1,2-dithiolylium salts : Reaction with 4-hydroxy-6-methyl-2H-pyran-2-one and 4-hydroxycoumarin

The reaction of 4- and 5-aryl-3-methylthio-1,2-dithiolylium iodides with 4-hydroxy-6-methyl-2$\text{H}$-pyran-2-one and 4-hydroxycoumarin has been studied. 4-Substituted salts yielded 3-aryl-7-methyl-2-thioxo-2$\text{H}$,5$\text{H}$-pyrano [3,2-c]pyran-5-ones and 3-aryl-2-thioxo-2H,5H-pyrano[3,2-c]benzo[e]pyran-5-ones, respectively, whereas 5-substituted salts gave rise to 3-(5′-aryl-1′,2′-dithiol-3′-ylidene)-6-methyl-2$\text{H}$-pyran-2,4-diones and 3-(5′-aryl-1′,2′-dithiol-3′-ylidene)-2$\text{H}$-benzo [b]-pyran-2,4-diones.     

The syntheses of polycyclic molecules containing b-carboline units by the photochemically induced ring closure of enamides

The syntheses of 5-methyl-5,8,9,14-tetrahydroindolo(2,3-$\text{c}$)indolo (2,3-$\text{g}$) quinolizin-6-one and 15-methyl-7,8,13,15-tetrahydroindolo ( 3,2-$\text{c}$) indolo(2,3-$\text{g}$)quinolizin-5-one from the photochemical cyclisation of i-methylene-2-(N-`methylindole-2'-carbonyl) 1,2,3,4-tetrahydro-B-carboline and 1-methylene-2- (N-`methylindole-3' carbonyl) 1,2,3,4,-tetrahydro-B-carboline are described. Attempts to prepare indolo(2,3-$\text{c}$)isoquinolines from the photochemical cyclisation of 2-benzamidoindoles were unsuccessful.     

Base catalysed rearrangement of 2-methyl-3,3-bisalkylthioacrylophenones to 2-alkylthiomethyl-3-alkylthioacrylophenones via mobile keto allyl intermediates

The title compounds ($\text{1a}$-$\text{e}$) undergo facile base catalysed rearrangement to give $\text{5a}$-$\text{e}$. A mechanism involving thioallylic rearrangement of intermediates, 2-bisalkylthiomethyl acrylophenones, ($\text{3a}$-$\text{e}$) has been proposed.     

Synthesis of 12-layer modification of hexagonal BaFeO3 under high oxygen pressure

The modification of hexagonal BaFeO_2.85 with a = 5.700 Å and C = 28.03 Å has been synthesized at high oxygen pressure. The $\text{c}\text{a}$ ratio of 4.917 indicates that it has 12-layer sequence according to the general equation $\text{c}\text{a}\text{= 0.4107}\text{n}$. From Mossbauer spectra at 300 K, it is revealed that there are two different valance states of iron, the isomer shifts are 0.03 mm/sec for Fe⁴⁺ and 0.37 mm/sec for Fe⁴⁺, respectively.     

Reactions of β-substituted amines-IV: Kinetics and stereochemistry of the thermal to (r) 3-chloro-1-ethylpiperidine,and the stereo-chemical course of their reactions with nucleophiles

The rate of the thermal rearrangement of (S) 2 chloromethyl-1-ethylpyrrolidine [(S)-1a] to (R)-3-chloro-1-ethylpiperidine [(R) 2a] has been examined at three temperatures in benzene by PMR and polarimetry. The rearrangement was shown to be completely stereospecific and to obey a simple first order rate law. The calculated E_a ΔH3 and ΔS3 were 22 ± 2 $\text{kcal}\text{mole}$ (25°), 21 ± 2.5 $\text{kcal}\text{mole}$ (25°) and - 10 ± 2 e.u. (0°K) respectively. The effect of solvents having differing dielectric constants was also studied. A transition state 9'a and an ion pair intermediate 3a are suggested for the rearrangement. The stereochemical course of the reactions of (S)-1a, (R)-2a and (S)-2a with hydroxide and methoxide ions have been shown to be 100% stereospecific with an uncertainty of about 1%. The absolute configurations of all optically active reactants and products [(S)- and (R)-4a, (S)-4b (R)- and (S)-5a, (R)-5b, (S,S')-6a, (S,R')-7a and (R,R')-8a] were established by chemical correlations with known compounds or by ORD and chemical inference. The ring opening of both the primary and secondary aziridinium ion positions of 1-azonia-1-ethylbicyclo [3.1.0]hexane [(S)-3a] by nucleophiles proceeds entirely by S_N2 processes. The conversion of (R)-1-ethyl-3-hydroxypiperidine [(R)-5a] to (S)-2a. HCl with thionyl chloride in chloroform proceeds by inversion with 4.8% racemization, whereas the thermal rearrangement of (S)-1a to (R)-2a occurs with complete retention of absolute configuration.     

A convenient synthesis of flindersine,atanine and their analogues

A new synthesis of the pyranoquinolone alkaloids flindersine ($\text{8a}$), 8-methoxyflindersine ($\text{8c}$), N-methylflindersine ($\text{9a}$), zanthobunglanine ($\text{9c}$) oricine ($\text{9d}$) and veprisine ($\text{9e}$) and the prenylquinolone alkaloids atanine ($\text{13a}$), preskimmianine ($\text{13e}$) N-methylatanine ($\text{14a}$), O-methylglycosolone ($\text{14c}$) and N-methylpreskimmianine ($\text{14e}$) is described.     

Die bildung von anellierten und überbrückten produkten bei der intramolekularen cycloaddition von carbonyl-yliden synthese eines “inside-outside”-bicyclo[13.2.1]octadekans

Intramolecular cycloaddition reactions of carbonyl ylides with ester-activated CC-bonds are studied. Whereas the annelated adducts $\text{7}$/$\text{8}$ are formed in the case of $\text{4a}$-$\text{c}$ (n=1, 3, 5) as starting materials, thermolysis of $\text{4d}$ (n=10) leads predominately to the bridged compound $\text{9d}$.