Compounds, viii

Macrocyclic tetraammonium compounds VIII and IX 611 form stable 1 1 inclusion complexes with anionic molecules in aqueous solutions 62). The anions are halides, carbonate, phosphate, AMP, ATP etc. The stability of the inclusion complexes hepends on electrostatic as well as hydrophobic interactions. Whereas the complexes of VIII are dominated by the electfostatic component, the hydrophobic interaction plays the main part in complexes of IX. 

Occurring Acetylene Compounds. VIII. The Synthesis of Methyl n-Dec-2-en-4 6 8-triynoate, an Isomer of the Naturally Occurring Dehydro-matricaria Ester. Acta Chem. Scand. 6, 602 (1952). 

The molecular structures of compounds (VII), (VIII), and (IX) also have much in common (Fig. If, Table 1) all three compounds consist of [TC6Br6(/t3-Br)5]2 anions and M+ cations where M+ = (C4H9)4N+ or [H30(H20)3]+). For compound (IX) such a structure is established indirectly, because compound (VIII) is easy to obtain by adding [(C4H9)4N] + cations both to the solutions of compound (IX) and to those of compound (VII). Besides, compound (IX) possesses chemical and physico-chemical properties similar to those of compounds (VII) and (VIII). 

A unique compound, (VIII), is formed be reacting C6H402BC1 with (C6Hs)2ONSi(CH3)3 or (C6Hs)2C=NLi 47>, compound (VIII)... 

Violland, R., Violland-Duperret, N., Pacheco, H., Trouiller, G., and LeBlanc, A. (1971) Potential psychotropic compounds. VIII. Synthesis and pharmacological activity of 2-aminotetralins related to psychotomimetics. Bull. Chim. Ther., 6 196-202. 

It was to be expected that the imino ether hydrochlorides would be hydrolysed in the animal body to give the corresponding fluoroacetate and ammonium chloride, and the toxicities should be roughly the same as those of the fluoroacetates. The results show this to be the case. The compound (VIII iZ = CH2,CH2F) was expectedly more toxic than the other compounds, as this would be hydrolysed to 2-fluoroethyl fluoroacetate which is known to be twice as toxic as methyl or ethyl fluoroacetate,1 as indicated below. 

A thorough examination of the whole problem was carried out by Gardner and Heath. Using diethyl phosphorochloridate containing 32P, they prepared compound (VIII) thus ... 

It should be noted that the compound alone has no therapeutic effect in malignant tumours. Cases of inoperable carcinoma of the bronchus have been treated2 by a combination of X-ray therapy and compound (VIII). In such cases and also in connexion with malignant tumours of other types, there are indications from preliminary clinical studies, that the intravenous administration of compound (VIII) has a small but useful effect as a clinical radiosensitizer. 

There is only one compound which carries an aldehyde group, so glyceraldehyde-3-P must be compound (viii) and acetone you may already know as a ketone, so compound (ii) is dihydroxyacetone phosphate, DHAP. 

Small-Ring Compounds. VIII. Some Nucleophilic Displacement... 

Isotope Abundances Negative Ions Synthetic Models V. High-Resolution Studies VI. Metastable-Ion Techniques VII. Coupled Gas Chromatography and Mass Spectrometry Inorganic and Organometallic Compounds VIII. Conclusion. ... 

Indenylidene compounds VIII, K, XXI, XXIII, XXVIIIa and XXVIIIb act as atom transfer radical polymerization catalysts for the polymerization of methyl methacrylate and styrene in high yields and with good control (Table 8.7). The catalytic activity can be dramatically improved by transforming the complexes into cationic species by treatment with AgBp4 [61]. 

The dicychc compound (VIII) is also obtained by reacting for a week at 60° a mixture of oxamidedioxime and formic acid containing a catalytic amount of BFg. IX is a by-product isolated from the reaction mixture (44 c). 

R)-2-Chlorobutane (I) forms free radicals (III and IV) which are conformational diasiereomers with different stabilities and populations. This is also true of I s enantiomer II. (S)-2-chlorobutane. which gives free radicals V and VI. The more stable free-radical conformers are IV and V because their CH, s are anrMike. The transition states for Cl abstractions arising from conformations IV and V have lower SH values than the diastereomeric transition states from the more crowded gauc/te-like conformations. Ill and VI. The major product is therefore the meso compound. VIII = IX. 

Alcohol groups are esterified with nitric acid. Further nitrolysis may cause the cleavage of N—C bonds. The experimental data (Wright and Myers [43]) indicate that the cleavage of bond A most probably occurs with the formation of the hypothetical compound (VI). In turn the latter may undergo nitrolysis at position B to form another hypothetical product (VII) [39, 40, 43, 44] and a known compound (VIII) [39, 40, 44], i.e. 

The introduction of a nitro group at the orl/jo-position to the oxygen atom in 4-diazo-1-oxide (IV) increases the stability. Great stability is also demonstrated by the 0- and p-substituted nitro derivatives of 2-diazo-l-oxide (VI and VII). On the other hand, the m-substituted compound (VIII) has a lower stability than compounds (VI) and (VII). Dinitro substituted derivatives, ortho-ortho (V) and orthopara (Ila), are distinguished by a higher stability than the mononitro derivatives of the same oxides (IV) or (VI) and (VII). 

However, when a free amino group is present (Ri) in compounds VIII and IX, the unpaired electrons of the amino nitrogen atom may influence the electronegativity of the carbonyl carbon atom and thereby decrease its tendency to withdraw electrons from the adjacent a-carbon... 

A second and more recent example, the photochemical rearrangement of 4,4-diphenylcyclohexadienone (VIII), was provided by the present author and co-workers (4, 5,14). This compound (VIII) when photolyzed in aqueous dioxane with light of wavelength above 310 mp. was found (4, 5) to afford the bicyclic ketone IX, 2,3-diphenylphenol (X) and an acid whose structure was shown (14) to correspond to XI. Additionally, 3,4-diphenylphenol (XII) was shown (14) to be a minor by-product. Strikingly and reminiscent of the dependence of product distribution on solvent in santonin photolysis, it was found (14) that approximately equal quantities of 3,4-diphenylphenol and 2,3-diphenylphenol (X) were formed when the photolysis was run in 50% aqueous acetic acid. [Control experiments (14) demonstrated that neither 4,4-diphenylcyclohexadienone nor bicyclic ketone IX were reactive in the dark under the aqueous dioxane or aqueous acetic acid reaction conditions, in the presence or absence of acid XI.] Furthermore, the bicyclic ketone IX has been demonstrated to afford 2,3-diphenylphenol (X) and the photoacid XI on photolysis in aqueous dioxane, and consequently this ketone may be formulated as a reaction intermediate in the formation of X and XI from 4,4-diphenylcyclohexadienone (VIII) (4, 5, 14). 

Stelter L, von Sonntag C, Schulte-Frohlinde D (1975a) Radiation chemistry of DNA-model compounds VIII. Dephosphorylation products from reactions of OH radicals with ribose-5-phos-phate in aqueous solution. The effect of oxygen. Z Naturforsch 30b 609-615 Stelter L, von Sonntag C, Schulte-Frohlinde D (1975b) Radiation chemistry of DNA-model compounds, VII. On the formation of 5-deoxy-D-eryffrro-pentos-4-ulose and the identification of 12 further products from y-irradiated aqueous solutions of ribose-5-phosphate. Z Naturforsch 30b 656-657... 

The Morita-Baylis-Hillman (MBH) reaction is the formation of a-methylene-/ -hydroxycarbonyl compounds X by addition of aldehydes IX to a,/ -unsaturated carbonyl compounds VIII, for example vinyl ketones, acrylonitriles or acrylic esters (Scheme 6.58) [143-148]. For the reaction to occur the presence of catalytically active nucleophiles ( Nu , Scheme 6.58) is required. It is now commonly accepted that the MBH reaction is initiated by addition of the catalytically active nucleophile to the enone/enoate VIII. The resulting enolate adds to the aldehyde IX, establishing the new stereogenic center at the aldehydic carbonyl carbon atom. Formation of the product X is completed by proton transfer from the a-position of the carbonyl moiety to the alcoholate oxygen atom with concomitant elimination of the nucleophile. Thus Nu is available for the next catalytic cycle. 

Roberts, J. D. Chambers, V. C. Small-ring compounds. VIII. Some nudeophilic displacement reactions of cydopropyl, cydobutyl, cyclopentyl and cydohexyl p-toluenesulfonates and halides./. Am. Chem. Soc. 1951, 73, 5034— 5040. 

Thus reaction with alkyl halides such as allyl bromide or pro-pargyl bromide allow for the introduction of oleflnlc2. . or acetylenic side groups onto the phosphazene ring VI, while alcohol leads to the formation of hydrido-phosphazene complexes VII. The hydrogen in these compounds can be replaced with halogen to yield the first series of iodor-phosphazene compounds VIII. 

Compound VIII gave 2,4,6-tri-t-butylphenylphosphonic chloride (X) by the reaction with chlorine in carbon tetrachloride followed by hydrolysis in almost quantitative yield. 

Sulfur compound VIII, a carboxytrimethylbenzene sulfonic acid, could have come from an aryl disulfide, a thiol or could be derived from the further oxidation of compound IX, a carboxytrimethyldibenzothiophene-1,1-dioxide. This latter possibility is indicated by the lower concentration of compound IX relative to compound VIII in the oxidation products of coals containing mineral matter. Once again the catalytic effect of the mineral component of coal is indicated. 

Other studies have shown that both the fulvalene titanocene (V), and the cyclopentadiene dititanium compound (VIII) act as homogeneous catalysts for the conversion of ethylene into ethane and buta-1,3-diene. In this case, an intermediate containing Ti-H bonds has also been proposed (72). 

Lukas, I., C. Strusievici, and C. Liteanu. 1967. Vanadate compounds. VIII. Formation of bronzes in the silver vanadate-vanadium oxide system. Z. Anorg. Alg. Chem. 349 92-100. 

A blue hydroxynitroso compound (VIII) is formed as an unstable Intermediate product. 

The successful preparation of isomers IX and X as well as the different reactivities of the chlorine atoms in the two rings of compound VIII and different tendency to hydrolysis shown by the methoxy groups in compound XIII provide further evidence in favour of an unsymmetrical structure of the azoxy group, in accordance with Angeli s view. 

An equilibrium between the isomeric hydroxysulfones, VIII/44 and VIII/45, was observed in the presence of butyllithium. Treatment of VIII/44 with potassium ferf-butoxide gave only the ring enlarged (E)-isomer VIII/46. The ( -configuration of the double bond is the result of the stereoelectronic course of the fragmentation. Under the same reaction conditions the formation of the isomeric VIII/47 from VIII/45 was not observed only compound VIII/46 was isolated. This must happen via thermodynamically controlled epimerization of VIII/45 —> VIII/44. For similar reactions, see ref. [28]. 

The application of the Emde degradation conditions (0.1 N KOH/C2H5OH, H2/Pt) to the quaternary curare alkaloid, mavacurine iodide (VIII/94), led to the so-called e2-dihydromavacurine (VIII/95), a tertiary base, Scheme III/18. Protonation (e.g. HC1/H20) or methylation (CH3I) of VIII/95 led to the trans-annular reaction products, VIII/96 and VIII/97, respectively. The quaternary compound, VIII/96, returns to tertiary VIII/95 (reversible Hofmann elimination) in the presence of base or on tic (silica gel) [55]. 

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