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1. The reactions of mixed chlorophosphines, containing one functional group, withα,β-unsaturated acids or their amides lead to the formation of bifunctional tertiary phosphine oxides. 2. The hydrolysis of ethyl-bis-(β-cyanoethyl)phosphine oxide gave ethyl-bis-(β-carboxyethyl)phosphine oxide.

A general method to synthesise optically-active silicon compounds is described. monofunctional chiral organosilanes of known absolute configuration are obtained, with high stereospecificity, by coupling the asymmetric bifunctional organosilicon compounds Ph-α-Np()MenOSiH (I), Ph-α-Np()MenOSiCl (II) and Ph-α-Np()MenOSiOMe (III) with saturated, vinylic or arylic organometallic reagents (M = Li,Mg). When two ligands of different reactivity such as (H and OMen) or (Cl and OMen) are bonded to silicon, the more polarisable functional group is always replaced. The stereochemistry of these reactions is analogous to that observed for monofunctional organosilanes. The menthoxyl group of (I) is sustituted with retention of configuration. In the case of the chlorosilane (II), only the function SiCl reacts with inversion of configuration. For the dialkoxysilane (III), the substitution of the less bulky methoxyl group proceeds with retention of configuration.

A spin-labelled ligand is defined as a molecule with two functional groups, one of which provides a Lewis base site suitable for complexing to a metal ion. The second functional group comprises a site bearing an unpaired electron. The possible utility of such compounds in coordination chemistry has been explored. The spin density distribution in 4-pyridyl-t-butyl nitroxide provides information on the relative electron accepting abilities of different metal ions in various ligand environments. A method for measuring the rates of very rapid ligand exchange reactions is also suggested.

It is shown that the antioxidant 3,5-di-tert-butyl-4-hydroxybenzyl acrylate, may be grafted to the surface of polymer artefacts. The antioxidant activity of the resulting “efficiently dispersed” antioxidant is very much higher than that of low molecular weight antioxidants containing the same functional group. Even after extraction with an effective solvent for the antioxidant-monomer and derived polymer, the oxidative stability of the polymer films is very much greater than that of polymer containing the antioxidant-monomer or antioxidant-polymer incorporated by a conventional melt technique without extraction. Optimum activity is believed to be associated with the formation of frequent short chain grafts in the surface of the polymer and is achieved by the use of a polymerization photo-activator such as benzophenone which also terminates kinetic chains. Surface grafted antioxidants are also found to be effective u.v. stabilizers for polypropylene in contrast to the normal ineffectiveness of chain terminating antioxidants incorporated into the polymer by conventional techniques.

Several forms of cation exchange resins with different crosslinkages have bsen subjected to 60Co γ-radiation, in wet or dry state and the effects of such variables as adsorbed ionic species, crosslinkage of the resin, and the water content in the resin on radiation damage to organic resin have been examined in their relation to γ-radiation dose. The result showed that radiation caused marked changes in the chemical and physical properties of the resin, and phenomena such as de-crosslinking, loss of strong-acid capacity, formation of a functional group composed of a weak-acid exchange group were observed. The degree of such degradation phenomena was not affected by adsorbed ions when their valency states were kept unchanged during irradiation, but when the adsorbed ions were reduced during exposure, the extent of degradation was found inhibited to a significant extent. It may be concluded from the results that the decomposition of the cation exchange resin is mainly initiated by reaction with the resin pro...

The use of bromoacetyl derivatives in the determination of structure-function relationships in proteins is reviewed. Specific attention is paid to the advantages of the bromoacetyl functional group in the design and synthesis of active-site-directed reagents. Modification studies on staphylococcal nuclease and myeloma protein 315C are discussed in detail. Reagents containing the bromoacetyl group at prescribed distances from the binding center of the affinity label are described. Information gained from these studies gives insight into the spatial orientation of the amino acid side chains near the active sites of proteins.

The effect of specific functional group modification of wool on the binding of a number of metal ions (individually) from aqueous solutions was studied. The metal ion uptake profiles for the different modified keratin polymers show that a degree of specificity of binding is imparted by the various modifications in terms of changes in capacities or rates of metal ion uptakes. The changes of uptake depend on both the particular ion and the particular protein modification involved. The results show the potential usefulness of the keratin derivatives for removal of toxic and industrial metal ions from water and contribute to interpretation of metal ions interactions with native wool and proteins in general. Treatments of woven wool with aqueous solutions of certain metal salts impart flame and insect resistance to the fabric.

The differential enthalpy of evaporation from solution (AH???) is reported the following functional groups: CH2, OH, O , C O, CHO, OC(O)H, and OC(O)CH3. These values are reported on seventy-five liquid phases using fifty solutes. The functional groupAH values for the liquid phases have been used to rank the selectivity of the liquid phase towards each functional group.

The chemical synthesis of ppGpp (guanosine 3′,5′-dipyrophosphate) is described. The synthesis started from guanosine 3′,5′-diphosphate. The acidlabile ethoxyethyl group was used to protect the 2′-OH functional group. The pyrophosphate linkages were built up simultaneously according to the anionexchange method and the protecting group was removed by dilute aqueous acetic acid. In an analogous manner the isomeric non-natural ppGpp (guanosine 2′,5′-dipyrophosphate) and uridine 2′(3′),5′-dipyrophosphate were synthesized as well.

Wahrend acyclische Acylimine und cyclische Acylimoniumsalze ohne substituent am Kohlen stoffatom der Funktionsgruppe (4a aud 4b) metallorganisch Verbindungen an der Cn-Doppelbindung addieren, reagiert 1-Oxo-2,3-diphenyl-1H-isoindol-2-ium-Salze 4c addieren Phenylmagnesiumbromid an der Co-Doppeldbindung, Methylmagnesiumjodid hingegen an der CN-Doppelbindung. Das deutet auf sterische Faktoren. Die Umsetzung des 3-Chlor-3-phenyl-1-isoindolinous (9) mit Phenylmagnesiumbromid entspricht der der salze 4c. Acylimines, III. The Reaction of Acylimonium Salts with Grignard Reagents Organometallic compounds add to the CN-double bond to acyclic acylimines and cyclic acylimonium salts without substituent to the carbon atom of the functional group (4a and 4n). 1-Oxo-2,3-diphenyl-1H-isoinodol-2-ium hexachloroantiomonate (4d) does not react with phenylmagnesium bromide, and 1-oxo-3-phenyl-1H-isoindol-2-ium salts 4c add phenylmagnesium bromide at the CO- and methylmagnesium iodide at the CN-double bond These results show that the reaction is strongly influenced by steric factors. The reaction of 4c and that of 9 with phenylmagnesium bromide yield the same products, indicating that 1-hydroxy-1,3-diphenyl-1H-isonidol (8) is an intermediate in both reactions.

Heptafluorobutyrylation and trimethylsilylation have been found with several carbamates and urethanes to result in the formation of unexpected products. Among the functional group transformations are conversion to the corresponding heptafluorobutyramide and trimethylsilyl ether. An on-column conversion of a trimethylsilylated carbamate to the corresponding isocyanate has been studied with respect to rate of trimethylsilylation and column temperature. By judicious choice of conditions the carbamate, its trimethylsilyl derivative, and the corresponding isocyanate can be chromatographed, allowing for an additional dimension of selective detection with a mass spectrometer.

Thermal antioxidants were incorporated into polyethylene as solutions in the silane coupling agent N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane. Substantial improvements in retained concentration and induction time were observed for commercial phenolic and amine-type antioxidants on prolonged oven aging in thin polyethylene films. As an alternative to solution formation, a stabilizer was bonded directly to silicon as the organic functional group in a silane coupling agent, resulting in improved dispersion and induction time. Improvements in antioxidant retention and induction time appear to correlate with compatibility of the silane–polyethylene system.

A review of the literature indicates compelling evidence that: (1) loss of ROH from esters requires protonation of the alkoxy oxygen; (2) the (symmetry forbidden) [1,3] hydrogen migration from protonated carbonyl to alkoxy oxygen does not occur in the mass spectra of esters; (3) hydrogen abstraction in esters occurs almost exclusively to the carbonyl oxygen. Mechanisms are proposed which account for all examples of ROH loss from esters. Alkanol loss from molecular ions in esters requires the presence of a second functional group to act as an intramolecular catalyst, either as a general acid in transferring a proton to the alkoxy oxygen, or as a general base in assisting the [1,3] carbonyl oxygen to alkoxy oxygen proton transfer. Loss of ROH from fragment ions requires proton transfer from an atom α to the positive charge to the alkoxy oxygen. These mechanisms are generalized to include a wide class of bifunctional esters and a selection of natural products.

The role and trends in the development of chromatographic methods for the functional group analysis of organic compounds are discussed. Attention is concentrated on the analytical possibilities of using chemical reactions of the test compounds together with gas-chromatographic separation (chemical-chromatographic method). The bibliography includes 192 references.

Graft Copolymerization onto Cellulose Derivatives. IV. Graft Copolymerization of Styrene and Styrene—Methyl Methacrylate onto Cellulosic Materials Containing Carbonyl and Carboxyl Groups

1. The vulcanization system based on nitrosophenols (quinone monoximes) is not primarily based on the formation of a urethane group. Evidence is presented that the crosslink consists of carbon—carbon, carbon—sulfur, and urea groups. Urea groups can be identified in reaction products which also contain the free phenol group of the nitrosophenol (oxime); urethane groups are identified in products which also contain quinone groups. 2. The presence of zinc dithiocarbamate is conducive to the formation of the amino group which is the functional group on which the crosslinking reaction with diisocyanate is based. The dithiocarbamate also acts as a sulfur donor. The dialkyl amino group of the dithiocarbamate is bound into the network. 3. Nitroso compounds which have no tautomeric oxime structures show no vulcanization in combination with free diisocyanate. 4. The level of vulcanization of various substituted phenols, when used in combination with a diisocyanate precursor, is dependent on their thermal decomposition termperatures, but such a dependence is not apparent when these compounds are used in combination with free diisocyanate. 5. A reaction mechanism is suggested for the vulcanization with oximes and diisocyanates which does not require the splitting of their adducts into their components but instead into ionic fragments. This mechanism explains why monoximes lead to vulcanization whereas nitroso compounds do not. 6. Attempts to effect premature vulcanization should be directed towards delaying the formation of the diisocyanate/oxime adduct since it provides the vulcanization-active intermediates. Towards this goal it has been shown that a diisocyanate precursor can be applied but then a thermally stable nitroso compound (oxime) is required. 7. Tautomerism between O-derivatives of oximes, nitrones, and oxaziridines can be assumed to provide a working hypothesis for the discovery of new N-O-containing crosslinking agents for unsaturated polymers.

The gas-liquid chromatographic characteristics of 4 kinds of Δ4-stenol (Δ4-cholestenol, 4-methyl-Δ4-cholestenol, 6α-methyl-Δ4-cholestenol, 6β-methyl-Δ4-cholestenol) and also their acetoxy, trifluoracetoxy and trimethylsiloxy (TMS) derivatives have been studied. The Δ4-stenols and their derivatives gave two peaks (a and b) which have retention times significantly shorter than would be expected from comparison to other sterols. On the TMS derivatives, the third peak (c) which is less volatile component was also observed. Peak a, b and c were respectively identified to Δ2, 4-diene, Δ3, 5-diene and the original TMS derivative by means of preparative GLC, UV, IR and gas chromatography-mass spectrometry. These results suggested that the Δ4-stenols and their derivatives underwent a thermal elimination reaction of functional group at c-3, and yielded unsaturated hydrocarbons (a and b). The structure of resulting hydrocarbons was not affected by the nature of a methyl group in proximity to the Δ4-bond.

A topological approach to the LIS simulation process of compounds bearing the carbonyl functional group is reported. The Lanthanide was always found to complex in the less hindered position, along the sp 2 lone-pair orbital of the O atom. The relevance to chemistry of such an approach is that only chemical significant positions are considered as feasible sites of complexation of the Lanthanide with the substrate, disregarding all other positions. More important, the results obtained have thrown some light on the factors that may influence the equilibria of conformationally mobile systems, in the presence of LSR. The reliability of the method employed has been tested in several disparate carbonyl derivatives.

Polyamides were prepared from linear, aliphatic dicarboxylic acids of six to twelve carbon atoms with 1,4-cyclohexanebis(methylamine), 1,4-cyclohexanebis (ethylamine), p-xylylenediamine, and p-phenylenebis(ethylamine). Melting points, glass transition temperatures, densities, and moisture regains were compared for the polymers to determine the relative effect of the cyclohexylene and phenylene linkages. While polyamides containing the trans-cyclohexylene group possessed higher glass transition temperatures than their aromatic counterparts, melting behavior was not as consistent. The odd-even rule, which states that polyamides with an even number of methylene linkages between the ring and the functional group melt higher than those with an odd number of such linkages, was violated in the cycloaliphatic systems. The Tg of ring-containing polyamide fibers was not dependent solely upon ring concentration, but was influenced by the molecular fit of the ringed intermediate in the polymer chains. Molecular fit appears to affect the Tg and melting point of alicyclic polyamides to a greater extent than the aromatic analogs. Differences in Tg, both within and among the polymer series, was not explained by either density or the degree of crystallinity.

Durch Umsetzung von (-)β-Pinen (1) mit Triisobutylaluminium (2), anschliesende Oxidation mit Sauerstoff und Hydrolyse erhalt man neben (-)-trans-Myrtanol (6) als Neben-produkt trans-Pinan-1, 10-diol (9), das als erstes Pinanderivat eine funktionelle Gruppe am C1-Bruckenkopfatom besitzt. Das Diol 9 kann leicht in (-)-trans-Pinan-1-ol (11) uber-gefuhrt werden. (-)-(1R,2R,5S)-trans-Pinane-1,10-diol and (+)-(1R,2S,5S)-trans-Pinan-1-ol, Two Pinane Derivatives Containing a Functional Group at the Bridgehead Treatment of (-)-P-pinene (1) with triisobutylaluminium (2) followed by oxidation with oxygen and hydrolysis yields (-)-trans-myrtanol (6) and the by-product trans-pinane-1, 10-diol (9). The latter, which is the first pinane derivative found to contain a functional group at the C1 bridgehead, may be easily converted into (-)-trans-pinan-1-ol (11).

四種の縮合反応, すなわちAGF+AG→AGMAG+H2O (i)AGF+U→AGMU+H2O (ii)UF+U→UMU+H2O (iii)UF+AG→UMAG+H2O (iv)を pH3～7 の範囲で動力学的に検討した。ここで AG と U はそれぞれアセトグアナミンと尿素であり, AGF と U はそれぞれモノメチロールアセトグアナミンとモノメチロール尿素, そして M はメチレン結合を表わしている。反応 (i)～(iv) は2次反応速度式に従い, 速度は [H3O+]にほぼ比例していた。アミノ基の反応性は AG の方が U より大きかったが, AGF と UF のメチロール基の反応性はほぼ同程度であった。そしてメチレン化反応においては, アミノ基の性質の方がメチロール基の性質よりも支配的であることを知った。反応(i)～(iv)に対する活性化エネルギーとして次のような値を得た。

A gas-chromatographic procedure for the microdetermination of carboxyl groups by decarboxylation is described. The sample is heated in the presence of quinoline and cupric carbonate in a closed vessel; the carbon dioxide formed is then driven into the gas chromatograph. The peak-height on the chromatogram varies linearly with the amount of carboxylic acid in the sample. The method is rapid, simple, and accurate.

An insoluble polymer support system was used as a unique method of blocking one functional group of a completely symmetrical difunctional compound. The monotetrahydropyranyl and monotrityl ethers of the symmetrical diols, HO—(CH2)n—OH, where n = 2,4,6,8, and 10, were prepared. Reaction conditions for the preparation of the monotetrahydropyranyl ether of 1,10-decanediol were optimized.

1. Among compounds of the homologous series Cl3Ge(CH2)n the compound with chlorine in theβ-position (n=2), unlike compounds with chlorine in theα- andγ-positions (n=1 and 3), is characterized by extreme instability and is prone to β -breakdown, with liberation of ethylene and GeCl4, under the action of alkali or RMgX. 2. The tendency of compounds of the types Cl3MCH2CH2Cl and Cl3MCH=CHC1 to undergoβ-breakdown increases as M is changed in the following order: Si < Ge < Sn < Pb, i.e., in the same order as the degree of σ, σ-conjugation increase in these compounds. 3. It is suggested that the main cause of conjugation in organosilicon and organogermanium compounds is the possibility of the mutual approach between the silicon (germanium) atom and the functional group in theβ-position and also the presence in the silicon (germanium) atom of vacant d-orbitals. These two circumstances lead to powerful interaction between silyl (germyl) andβ-carbofunctional groups. 4. The chemistries of the organic compounds of Si and Ge have many features in common and are substantially different from those of Sn and Pb compounds.

A selective sorption of uranyl ions on organic ion-exchangers containing -OPO(OH)2 or -PO(OH)2 groups from dilute nitric acid solution and the affinity of various divalent cations to these groups in acetate medium were studied. Practical applications of these ion exchangers for the separation are described.

Chloromaleic anhydride was found to copolymerize with divinyl ether to form soluble copolymers of 1:1 composition, devoid of residual unsaturation. A bicyclic structure is proposed in which the polymer backbone consists only of divinyl ether units. The ease with which the copolymers underwent dehydrohalogenation suggests that the hydrogen and chlorine atoms on the anhydride unit are in a trans configuration as a result of a stepwise cycli-zation process. Oxidation of the hydrolyzed, dehydrohalogenated copolymers afforded the corresponding vic-diol copolymers. The absence of a significant decrease in copolymer molecular weight upon periodic acid cleavage of the vic-diol copolymers supported the proposed structure. Functional group analyses and softening points were in accord with the structures of the derived copolymers.

The gas-liquid chromatographic behavior of a group of zearalenones has been investigated through the use of both selective and nonselective stationary phases. Separation of these compounds can be effected using conditions similar to those employed for steroid work, differentiation being accomplished on the basis of molecular weight, unsaturation, functional groups, and stereochemistry. Functional group alteration has been employed to improve separations and the quantitative aspects of analysis. Separation of a pair of epimeric alcohols proved to be especially difficult, requiring the use of several approaches. The contribution of the phenolic group at the 2 position to retention behavior is considerably smaller than that of the 4-phenol, a difference ascribed to the ability of the former to intramolecularly hydrogen bond to the carbonyl group of the lactone. These methods have been employed to identify the major urinary metabolite of one of the compounds of this series in the sheep.

Nearly 800 compounds have been studied for ability to inhibit glycolysis of salivary sediment. These compounds possessed aldehyde, ketone and/or carboxyl groups as a part of the organic structure. The compounds were tested mainly at 1% concentration or half-saturation, in water or in 10% propylene glycol. The most active aldehydes were formaldehyde, succinaldehyde, pyruvic aldehyde, mucochloric acid, 5-nitrosalicylaldehyde and m -hydroxybenzaldehyde. Inhibition can be attributed to the aldehyde group of the first three compounds. Nearly all active aldehydes possessed a high degree of specificity. Among ketones there were nine organic structures which were capable of producing inhibition amounting to 50 per cent or more, but only for one substance, dioleyl ketone, could inhibition be attributed definitely to the keto group. Among others, such as pyruvic aldehyde, 2,3-butanedione-2-methoxime, Rose Bengal, 2-(dibutylamino)-ethylphenylketone and 2,4′-dihydroxybenzophenone, the inhibitory action was attributable to some group other than ketone. The three remaining inhibitory chemicals, verbenone, benzoquinone and 2,5-dimethyl para quinone possessed ketone as the sole functional group. Among the eight organic acids showing inhibitory activity, there was a high degree of specificity. One group, bromacetate, mucochlorate and alphabromopropionate, was related to iodoacetate, but all were less inhibitory. Sodium N-lauroylsarcosinate was inhibitory, but few similar structures were available for comparison. The 3,5-di-iodosalicylic acid probably owes its activity to the presence of the two halogens since loss of one of these produces an inactive structure, but 2-butyl-x-chlorophenoxyacetic has activity which is not possessed by closely related compounds. The two substances, 2- cyclo pentene-1-valeric acid and cyclo hexanebutyric acid are the only structures whose activity could apparently be attributed to the carboxyl group.

Evaporative rate analysis, a new tool for the examination of surfaces, has been applied to aluminum, platinum, copper, and gold thereby permitting a study of the effect on surface sites of aging and the interaction of these sites with some commonly used lubricants (e.g., butyl stearate and stearic acid). Residual activity of a surface at any time is determined by the addition of a high boiling volatile C-14 labeled organic material containing a functional group. The degree of retention of this added material is a function of the number and specificity of available sites and the strength of the bonds between the adsorbed species and the surface.

The existence of cationic complex of chlorotetracycline (CT)-metal chelate having 1 : 1 ratio of CT to metal suggested the possibility of formation of a mixed complex combined with other ligands. Preparation and properties of the mixed complexes with penicillin G (PenG) and PenG-metal complexes were studied using Th4+, Fe3+, Co2+, and Cu2+ ions in acid medium. Th (IV), Co (II), and Fe (III) complexes with PenG which have 1 : 1, 2 : 1, and 2 : 1 ratios of PenG to metal, respectively, were isolated by addition of water to a solution of PenG-K and metal salt in methanol. Copper (II) complex was not obtained. Methyl-PenG was used for the determination of the functional group of PenG. Methyl-Pent-Co (II) complex was also formed. Mixed complexes of CT-metal chelates with PenG were prepared from methanolic solution. Both CT-Th(IV)-PenG and CT-Fe(III)-PenG mixed complexes have a 1 : 1 : 1 ratio. Mixed complexes with Co (II) and Cu(II) did not show a definite composition. Desdimethylamino-chlorotetracycline-Th(Iv) chelate formed a mixed complex with PenG. This indicates the formation of mixed complexes through the metal. The mixed comp1exes were soluble in methanol and insoluble in water and ether. Color of the mixed complexes was similar to that of corresponding CT-metal chelates.

Five humic and three fulvic acids were extracted from Argentine Chestnut, Brunizem, Solod and Solonetz soils and analysed by electrometric, spectroscopic and spectrometric methods. There were great similarities in elementary analysis, functional group content, absorption characteristics in the visible region and in the IR, and in the ESR measurements between the humic acids and, similarly, between the fulvic acids. There were distinct differences between the humic and fulvic acids in C, H, N and O content, distribution of oxygen in functional groups, E 4 /E 6 ratios and free radical content.

Aliphatische Alkoxy-diazenium-Salze 6 werden im Wasrigen Medium durch Hydroxyl-Ionen in α-Hydroxy-dialkyldiazene 4, umgewandelt. Die Struktur dieser neuen Verbindungsklasse, die trans-Anordnung der Substituenten an der Azogruppe und intramolekulare Wasserstoffbrucke, folgt aus UV- und IR-Spektren. Zum Nachweis der funktionellen Gruppe erhalt man aus den Azo-alkoholen 4 mit Acetanhydrid/Pyridin glatt die Azo-ester 8, wahrend beim Einleiten von HCl-Gas in die atherische Losung von 4 die Hydrochloride 7 der isomeren Saurehydrazide ausfallen. Alkoxydiazenium Salts, VI. Reaction with Hydroxide Ions to trans-α-Hydroxydialkyldiazenes Aliphatic alkoxydiazenium salts 6 are converted to α-hydroxydialkyldiazenes 4 by reaction with hydroxide ion. This new class of compounds is shown by u.v. and i.r. spectra to possess trans-stereochemistry about the azo double bond with intramolecular hydrogen bonding. Further evidence for the functional group is obtained from esterification by acetic anhydride/pyridine to the azoester 8, whilst treatment of an ethereal solution of 4 with HCl gas yields the hydrochloride 7 of the isomeric acid hydrazide.

A recurring problem in polymer chemistry is the dependence of functional group reactivities on the reacted‐or‐unreacted status of neighboring groups. This problem has been attacked by means of a closed‐loop model and an infinite‐chain model. For the latter model, an approximate solution has been developed for the general case, and an exact solution has been shown for the speical case where k1=k2.

The properties of copper chelate compound of 1-hydroxyphenazine, which possesses one oxine-like functional group to form a chelate, as well as the composition of the chelate in solution and its dissociation constant were studied by the spectrophotometric method. 1-Hydroxyphenazine-copper chelate forms a five-membered ring compound in a neutral medium. 1-Hydroxyphenazine di-N-oxide also has a chelating functional group which seems to be a little different from the former compound, and the properties and composition of copper chelate were also investigated. The copper chelate of its di-N-oxide forms a six-membered chelate ring.

Compounds having a semipolar functional group, generally formulated X → Y, i.e. sulfoxide, sulfilimine, sulfonium ylide, pyridine N-oxide, and N-iminopyridinium betaine, were found to react readily with O,O-dialkyl dithiophosphoric acid to afford the corresponding reduction products, sulfide and pyridine.

The presence of α-methylenecyclohexanol grouping in ignavine or des-N-methyl-anhydroignavinol was proved by rearrangement reaction to ketone. Oxidative cleavage of the cyclohexanol ring in des-N-methylanhydroignavinol gave a dicarboxylic and one of the carboxyl groups in this acid was confirmed as tertiary. α-Glycol group which is another functional group in des-N-methylanhydroignavinol was also cleaved by oxidation to give a dicarboxylic acid and the glycol was proved to exist at carbons γ ond δ to the nitrogen.

Except for the benzalmalononitriles, two functional group stretching vibrations occur in the infrared (i.r.) spectra of the beta,beta-difunctional-styrenes with similar functional groups. For geometrically homogeneous compounds with dissimilar functional groups only one absorption band occurs for each functional group. The two bands for similar functional groups have been ascribed to S-cis- and S-trans-conformations of the carbonyl groups with respect to the ethylene and variation in the frequencies of each of these oriented carbonyls to rotation of the functional group or groups out of the plane of the ethylene by steric factors. Frequencies for ethylenic C--H out of plane deformation bands for beta-monofunctional styrenes accorded with those already assigned to this vibration. A similar assignment could not be made for the difunctional analogues. (Author)

The behaviour of some substituted silacyclobutanes with respect to sulfur trioxide and other sulfonating agents (SO 3 /dioxane, trimethylsilyl chlorosulfonate) is studied. The 1,1-dialkylated derivatives of silacyclobutane, 2-methylsilacyclobutane and 3-methylsilacyclobutane as well as the spiranes of the type (CH 2 ) n Si(CH 2 ) 3 ( n = 4 or 5) react with sulfur trioxide to give 4-sila-1,4-butanesultones. On the other hand, the alkoxylated or dialkylaminated derivatives fix SO 3 via the functional group, thus giving silacyclobutanyl sulfates or amidosulfates of the type XSO 2 O(R)Si(CH 2 ) 3 (X = OR′, NR′ 2 ). The sulfonation of 1-methyl-1-phenylsilacyclobutane leads mainly to 1-methyl-1-silacyclobutylbenzenesulfonate, besides the expected sultone. The structure of the insertion products of SO 3 in the SiC, SiN, SiO and SiCl bonds is deduced from their infrared and protonic resonance spectra. Reaction mechanisms, permitting to ascertain the role of the substituents on the mode of insertion of sulfur trioxide and the reactivity of the cyclobutane SiC bond, are considered.

Vapour-phase infrared spectroscopy has been used to study the behaviour of a wide range of thioalkyl compounds when refluxed with constant-boiling hydriodic acid. A very wide range of reactivity has been observed. Unusually labile compounds exist which react quantitatively in less than 3 hr ; the kinetics of the decomposition of such compounds must be investigated individually, since over-production of methyl iodide can occur. Many thiomethyl compounds, however, do not yield methyl iodide, and others react very slowly, giving variable non-quantitative yields of methyl iodide after reflux for 16–20 hr. It is therefore concluded that the mere extension of Zeisel reaction conditions for prolonged reflux periods does not usefully provide a general method for the functional group analysis of thioalkyl compounds.

Dicyclohexylcarbodiimide (DCCD) inhibits the membrane ATPase of Streptococcus fecalis indirectly through a reaction with another membrane component as yet unidentified. Whether or not DCCD reacts covalenly to produce this inhibition is also not known. We have now found that several other carbodiimide compounds differing greatly from DCCD in structure and water solubility are also inhibitory. However, the hydrophobic carbodiimides were more potent by many orders of magnitude. Since structurally diverse carbodiimides could inhibit the membrane-bound ATPase we conclude that the inhibition results from a covalent reaction. The relatively high potency of the hydrophobic carbodiimides indicates that the reactive site is located within a non-polar region of the membrane. It is suggested that hydrophobic carbodiimides such as DCCD, by partitioning in the lipid phase of the membrane can reach a local concentration sufficiently high to react covalently with a membrane protein functional group.

Adsorption of organic molecules on esterified silica gel. I. Heat of adsorption as a key to a model of adsorption Silica gel was dehydrated at high temperatures and the remaining silanol groups were esterified with polyethylene glycol 200. Good stationary phases for gas chromatography were obtained by this method, differing in the surface density of the surface-bonded alcohol molecules. Heats of adsorption of different organic molecules were determined by gas chromatographic methods. A linear relationship between heat of adsorption and surface density of the esterified alcohol molecules was found. From these data a model for the adsorption mechanism was assumed: Generally the strength of the surface field of the silica gel determines the adsorption. This field is more or less weakened depending on the size and surface density of the esterified alcohol molecules. The nature of the alcohol affects the adsorption only if it contains a polar functional group in the ω-positiom which differs essentially from the silanol groups.

The reaction of NCA's with some amino acids having a nucleophilic functional group on the side chain was studied in a heterogeneous reaction medium (acetonitrile-water). Glutamic acid and aspartic acid, having a free carboxyl group on the side chain, were successfully used to synthesize oligopeptides without interactions of the γ- and β-carboxyl group with NCA's. Two products were obtained by the reaction of NCA with L-lysine, which contains a free amino group on the side chain. e-Protected lysine was used to prepare α-peptides as a nucleophile in the reaction. No racemization was observed in the synthesis of peptides by the NCA method in the heterogeneous solvent system. Oligopeptides with some polar side chains were synthesized by the NCA method.

The functional group of sterol sulfonates is eliminated under the conditions usually used for steroid separations, and the products depend upon the structure of the original compound. For example, 2-cholestene is formed from cholestanyl methanesulfonate and p-toluenesulfonate. The products from cholesteryl methanesulfonate are 3,5-cholestadiene, 3,5-cyclo-6-cholestene and an unidentified cholestadiene (probably 2,4- or 2,5-cholestadiene); the i-steroid reaction presumably occurs in the gas phase in this instance. Derivatives from primary alcohols and rom phenols (estrone) were found to be stable under ordinary gas chromatographic conditions.