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A sensitive assay has been devised for glutathione- S -arene oxidase transferase using as substrates naphthalene-1,2-oxide or styrene oxide along with [ 35 S]glutathione. Activity of the order of 2–3 nmoles of conjugate formed during a 5-min incubation can be detected. This yields about 2000 cpm above a blank of about 1500 cpm. Transferase activity was found mainly in liver and kidney but was also present in most other tissues of rats. Glutathione- S -arene oxide transferase has been purified 70- to 80-fold from sheep liver 100,000 g supernatants using the conventional procedures. After electrofocusing, enzyme activity separated into two major peaks and two or three minor peaks, ranging in isoelectric point from pH 6.5 to 7.5. Activities assayed with naphthalene-1,2-oxide or styrene oxide as substrates were found to almost parallel each other in all the peaks. The sheep liver transferase required neither metal ions nor cofactors such as FAD, pyridoxal-phosphate and thiamine pyrophosphate. The molecular weight of the transferase has been estimated to be about 40,000. K m values for glutathione, naphthalene-1,2-oxide, and styrene oxide are 1.6, 0.11, and 0.13 m m , respectively. K m values for glutathione decreased with increasing pH, whereas the K m values for naphthalene-1,2-oxide were independent of pH in the range of 6.5–8.

Epoxy resin was cured with diethylaminopropylamine (DEAPA) in amounts ranging from 10% to 50% of stoichiometric amount. The yield strength of resulting thermosets formed by heat curing at 75°C is found to increase with decreasing amount of hardener. This is attributed to a more densely crosslinked structure resulting from increased tertiary amine-initiated epoxide–epoxide chain reaction and decreased primary and secondary amine–epoxide reaction. Infrared analysis and swelling data are also presented. Styrene oxide diluent is found to have a moderate effect on mechanical properties in the range from 10 to 25 parts per hundred (phr).

Mixtures of ring-opened and other products of reactions of acetic or benzoic acids, or ethanol, or phenol with styrene oxide under various conditions can be qualitatively and quantitatively analyzed without isolation of the components by the use of n.m.r. This method, in the case of the ester products, avoids confusing the initial ring-opening result with the results observed after subsequent acyl migrations which readily occur in this type of system.

The metastable ion spectra of ethylene oxide, acetaldehyde, acetaldehyde-d4, propylene oxide, propionaldehyde and trimethylene oxide are presented. They reveal no reason to suppose that electron-impact-induced isomerisation of oxide to aldehyde structure occurs, although many spectral features are common to various members of this set. The spectra of phenylacetaldehyde and styrene oxide are compared, and the more plausible possibility of partial isomerisation in this case is discussed.

Solubilized cytochrome P-450 monooxygenase and epoxide hydrase activities from rat liver microsomes have been separated by column chromatography. The highly active epoxide hydrase fraction is still contaminated with cytochrome P-450, which has very low monooxygenase activity. The highly purified cytochrome P-450 fraction possesses high monooxygenase activity and is essentially devoid of epoxide hydrase activity. Purification factors for the epoxide hydrase through four purification steps are similar with [3H]styrene oxide, [3H]naphthalene oxide, [3H]cyclohexene oxide, and benzene oxide as substrates. Failure of benzene oxide to inhibit hydration of styrene or naphthalene oxide in the most purified preparations in indicative of the presence of at least two hydrases. These purified cytochrome monooxygenase and hydrase preparations represent valuable tools for the study of the intermediacy of arene oxides in drug metabolism. Thus, with naphthalene, only naphthol is formed with the monooxygenase, while both naphthol and the dihydrodiol are formed in the presence of monooxygenase and hydrase. A convenient radiochemical synthesis of [3H]naphthalene 1,2-oxide and assays for the measurement of the hydration of [3H]naphthalene oxide and benzene oxide, based on differential extractions and high-pressure liquid chromatography, respectively, are described.

High molecular weight poly(isobutylene oxide) has been synthesized and characterized. Two novel catalysts were found: (1) a Zn-S composition made by reacting ZnEt2 and H2S in presence of cyclohexylamine and (2) a ternary system consisting of ZnEt2 a metal compound (such as ZnO, ZnS, or Zn titanate), plus cyclohexylamine. Products with reduced specific viscosities of 1.5 to 13 dl/g were easily made. Highest yields were obtained at 110°C, but these products had lower molecular weights than products synthesized at 70°C. The activity of the Nippon-Carbide catalyst was increased two to three times by heating it with a small amount of styrene oxide. High molecular weight poly(isobutylene oxide) appears to have an attractive balance of properties which are in the range of many engineering thermoplastics.

Reaction of optically active styrene oxide with triethyl α-phosphonopropionate gives 2-phenyl-1-methylcyclopropanecarboxylate in optically active form. When the −CO 2 Et group is transformed into −CH 3 , the product has but one asymmetric centre originating from styrene oxide. Based on the intramolecular S 2 mechanism of the formation of the cyclopropane ring, the absolute configuration of the title compound is suggested.

Tributyltin diethylamide, Bu3SnNEt2, reacts with epoxides such as 1-butene oxide, styrene oxide and cyclohexene oxide in the presence of a small quantity of LiNET2 causing aminostannylation to tributyl(2-diethylamino-alkoxy)tin derivatives, R-CH(OSnBu3),-CH2-NEt2. The structure of these compounds is deduced from NMR measurements of products of hydrolysis and by preparation from sodium diethylamino-alcoholates and tributyltin chloride. In the monomeric compounds pentacoordinated tin atoms are discussed.

Intrinsic viscosity and light scattering data are reported for fractions of the poly(styrene oxide) and for fractions of a commercial sample of poly(ethylene oxide). A few results obtained for fractions of the poly( t -butyl ethylene oxide) are also included. The following intrinsic viscosity/molecular weight relationships are obtained: [η] ( benzene at 25°C )=3.97×10 −4 M 0.686 v [η] ( toluence at 25°C )=6.79×10 −5 M 0.766 v Estimates of the unperturbed dimensions of these polymers yield values of ( r 2 0 M ) 1 2 of 0·93 A for poly(ethylene oxide) and of 0·64 A for poly(styrene oxide).

The copolymerization of styrene with substituted ethylene oxides catalyzed by boron trifluoride - diethyl ether has been investigated. In all cases, rather low-molecular-weight copolymers were obtained. The copolymerization reactivity of the substituted ethylene oxides with styrene varied with the substituents, in the order of: isobutene oxide>propylene oxide>styrene oxide>epichlorohydrin. This has been explained in terms of cross-propagation or the reaction of the growing oxide cation with styrene. The styrene unit content of the copolymer of styrene and epichlorohydrin increases with an increase in the solvent polarity and with an increase in the temperature. It has been concluded from the experimental results that the copolymerizability of alkylene oxide toward styrene is increased by the introduction of electron-releasing substituents into the oxide and by the use of a polar solvent at a moderate temperature.

1. The activation energy of the formation of styrene oxide in the coupled oxidation of styrene and acetaldehyde in benzene at 70–100° and a pressure of 50 atm was determined. 2. The parallel formation of styrene oxide, benzaldehyde, and phenylacetaldehyde in the coupled oxidation of styrene and acetaldehyde was established. 3. Benzaldehyde is a precursor of styrene oxide in the oxidation of styrene by oxygen, and the rate of epoxidation of styrene by benzoyl peroxide radicals is far lower than that by acetyl peroxide radicals.

The reaction is studied between epoxides and trialkylaluminium compounds containing a hydrogen atom in position β with respect to the metal atom. These organometallic compounds which are generally known to be capable of adding on to epoxides are shown to be equally suitable for reducing them. The ratio addition/reduction is largely dependent on the epoxide considered. To our knowledge, magnesium compounds have not been observed to undergo a similar reaction. A detailed study of the reaction of triisobutylaluminium with styrene oxide has been carried out. This establishes essentially that the ratio addition/reduction is independent of the time of contact of the reactants, the ratio of reactants, the temperature and the substituent carried by the aromatic part of the epoxide. A mechanism is suggested to account for the observed phenomena. This involves two molecules of the aluminium compound and an epoxide molecule, reacting via the formation of a cationic carbon compound and i-Bu − 4 Al.

Mit Hilfe des stark basischen Ionenaustauschers Amberlite IRA 400 in der OH-Form lassen sich Epoxyd-Reaktionen mit Mercaptanen katalysieren. Der Vorteil dieser Methode besteht darin, das die Reaktion bei ca. 60°C durchgefuhrt werden kann. Die Umsetzung von Styroloxyd mit Thioglykolsaure-athylester fuhrte unter Athanol-Abspaltung zur Bildung von 2-Phenyl-thioxanon-(6). Durch Synthese bzw. Abbau wird der sterische Verlauf der Reaktion von Mercaptanen mit 10,11-Epoxy-undecansaure-methylester und Styroloxyd aufgeklart. Epoxy- and Epithio-Compounds in the Field of Fats III With the help of the strong basic ionexchanger Amberlite IRA 400 in the OH-form the epoxyd-reactions with mercaptans can be catalyzed. The advantage of this method is based upon the fact that the reaction can be carried out at about 60°C. The reaction of styrene oxide with thioglycolic acid ethylester led to the formation of 2-phenyl-thioxanone-(6). Through synthesis respectively analysis the steric pattern of the reaction of mercaptans with the methylester of 10,11-epoxy-undecanoic acid and styrene oxide is explained.

p-Vinylphenyl methyl sulfide prepared by the reduction of p- (methylmercapto) acetophenone using lithium aluminium hydride with subsequent dehydration with the aid of potassium hydrogen sulfate could be bulk-polymerized in the presence of an initiator, 2, 2'-azobisisobutyronitrile. The linear sulfide-type polymer so formed was treated with dimethyl sulfate to obtain a water-soluble sulfonium-type derivative. A water insoluble sulfonium-type polymer was prepared in a similar manner from a p-vinylphenyl methyl sulfide-divinylbenzene copolymer.The sulfonium-type polymers were readily converted into polymer S-ylides in dry dimethyl sulf oxide containing potassium tirt-butoxide. The ylide reacted as a nucleophile with benzaldehyde to give styrene oxide.A cross-linked sulfoxide-type polymer, a polystyrene derivative, containing pendant sulf oxide groups was prepared by the oxidation of p-vinylbenzyl methyl sulfide-divinylbenzene copolymer with hydrogen peroxide.An analogous polymer S-ylide could also be prepared from sodium hydride and an oxosulfonium-type polymer, which had been prepared from a sulfoxide-type polymer and methyl iodide. It was noted that styrene oxide could also be obtained from such a polymer S-ylide and benzaldehyde.

The reaction between olefins, N-chloroacetamide or 1,3-dibromo-5,5-dimethylhydantoin, and hydrogen peroxide affords β-halohydroperoxides in good yields. These compounds react extremely rapidly in basic solution to give products which depend upon their structure. The 3-halo-2,3-dimethyl-2-butyl hydroperoxides form 2,3-dimethyl-3-hydroperoxy-1-butene and from the 2-halo-1,2-dimethylcyclohexyl hydroperoxides 1-methyl-2-methylene-cyclohexyl hydroperoxide is obtained. No allylic hydroperoxide can be detected from the reaction between base and 3-bromo-2-methyl-2-butyl hydroperoxide. Mainly cleavage products, acetone and acetaldehyde, are formed together with some 2,3-epoxy-2-methylbutane. The reaction between base and 2-bromo-1-phenylethyl hydroperoxide gives styrene oxide, benzoic acid, and some benzaldehyde. From trans-2-bromocyclohexyl hydroperoxide, trans-2-bromocyclohexanol, cyclohexene oxide, and some trans-1,2-cyclohexanediol are obtained upon reaction with base. No evidence for the formation of the allylic hydroperoxide was obtained.

The reaction of benzamide with thionyl chloride in the presence of pyridine gave N-sulfinylbenzamide and N,N′-dibenzoylsulfurdiimide. It has been found that N-sulfinylbenzamide reacted with styrene oxide in the presence of tetraethylammonium bromide to give 4-oxo-5-benzoyl-2,6-diphenyl-1,4,3,5-oxathiadiazepine as the main product, accompanied by lesser quantities of two N-benzoyl-phenylaminoethanols, 2,5-diphenyloxazoline, benzonitrile, and benzamide. The pathways for the formation of the products are suggested.

The radiation-induced polymerization of propylene oxide in the liquid and solid states was investigated and the polymerization mechanism is discussed. The polymerization was carried out at various temperatures by initiating with γ-rays from Co60 and electrons from a VAN DE GRAAFF accelerator. It was found from these experiments that propylene oxide can polymerize in the presence of styrene oxide in both liquid and solid state, while the polymerization of the pure monomer takes place in neither state. Although in a mixture of styrene oxide and propylene oxide in the liquid state the polymerization of styrene oxide takes place predominantly, the polymerization of propylene oxide can not be neglected at higher concentration of propylene oxide and at low temperatures. On the other hand, polypropylene oxide polymerizes predominantly in a mixture of the two monomers in the solid state. Styrene oxide may play two important roles in the polymerization; the acceleration of initiation reaction and the glassification of propylene oxide in the solid state. Die Polymerisation von Propylenoxid im flussigen und im festen Zustand mittels Co60-γ-Strahlung sowie durch Elektronen aus einem VAN DE GRAAFF-Beschleuniger wurde untersucht. Propylenoxid polymerisiert unter diesen Bedingungen nur in Gegenwart von Styroloxid. Wahrend in einer flussigen Mischung der beiden Monomeren das Styroloxid rascher polymerisiert, erhalt man im festen Zustand uberwiegend Polypropylenoxid. Das Styroloxid bewirkt dabei vermutlich eine Beschleunigung der Startreaktion sowie die Bildung eines glasartigen Polymerisationsmediums.

The betaines Ar3P+·CH2·CH(O–)·Ar′, formed either from methylphosphonium salt and aromatic aldehyde in alcohol–alkoxide or from phosphine and epoxide in alcoholic solution, rearrange to the phosphine oxides Ar2PO·CHAr·CH2Ar′, that aryl group migrating which is most stable as the anion. In Wittig olefin synthesis, similar rearrangements are not generally competitive with olefin formation. The analogous betaine formed from diphenylphosphine and styrene oxide rearranges in a similar way but also, depending on the conditions, gives styrene and products derived from betaine dissociation.

The reaction of p-substituted N-sulfinylanilines with styrene oxide in the presence of tetraethylammonium bromide gave the corresponding 1,2,4,5- and 1,2,4,6-tetraarylpiperazines, whose configurations were established on the basis of the NMR spectral studies. On the other hand, while a similar reaction of p-substituted N-sulfinylphenylhydrazines with the oxide in benzene gave the corresponding diaryl disulfide, diaryl sulfide, and p-substituted biphenyl, the reaction in acetonitrile did not give the biphenyl. The pathways for these reactions are suggested.

High resolution NMR spectra of four epoxides have been observed at 40 Mcps and analyzed. These epoxides are of the type [Complex chemical formula] where R is a phenyl group (styrene oxide), a cyanide group (glycidonitrile), an acetyl group (1,2‐epoxy‐3‐butanone), and a carboxyl group (glycidic acid). For each molecule the spin‐spin coupling constants and nuclear magnetic screening parameters for the A, B, and C protons were derived from the experimentally determined energy levels. The method for obtaining numerical values for the energy levels from the spectra is described fully. ABK and AA′K approximations as well as an iterative ABC method of solution are described and illustrated.Corresponding coupling constants are found to be about the same in all four molecules with JAB=5.8±0.5 cps, JAC=2.2±0.5 cps and JBC=4.6±0.5 cps. However, the variations from molecule to molecule are considerably greater than the estimated precision of ±0.05 cps. The ABX approximation is shown to be inadequate either for the pr...

The addition reaction of various mono-epoxides such as epichlorohydrin, glycidol, allylglycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, propylene oxide, styrene oxide, hexadecene oxide, and vinyl cyclohexene monoepoxide with silk fibroin was investigated in the presence of some salts in different solvents at 30–80°C. Histidine, lysine, arginine, aspartic acid and glutamic acid, serine and tyrosine reacted. The weight gains decreased with increasing solubility parameter of the solvents, reached a minimum value at about 10 or at the solubility parameter of the epoxide, and then increased with the parameter. The salt effects on the epoxide-silk reaction were described partly by the hydration ability or by the acidity of the cations, and also by the basicity or the nucleophilicity of the anions. The substituent effects of the epoxide on the add-ons were elucidated by the modified TAFT equation, (log k − log k0)/σ* = ρp + ρsEs/σ*, where k0 and k are the rate constants for the reaction of a given compound and for the same reaction of one of its derivatives; σ* is the polar substituent constant characteristic of the substituent, Es is the steric substituent constant, and ρp and ρs are the reaction constants as measure of the susceptibility of the reaction to the polar and steric effects of substituents. Die Addition verschiedener Mono-Epoxide, wie Epichlorhydrin, Glycid, Allyl-, Butyl-und Phenylglycidather, Propylenoxid, Styroloxid, Hexadecenoxid und Vinylcyclohexenmonoepoxid an Seidenfibroin wurde in Gegenwart einiger Salze in verschiedenen Losungsmitteln bei 30–80°C untersucht. Es reagierten Histidin, Lysin, Arginin, Asparaginsaure und Glutaminsaure, Serin und Tyrosin. Die Gewichtszunahmen fallen mit steigendem Loslichkeitsparameter der Losungsmittel, erreichen einen Minimalwert bei etwa 10 oder beim Loslichkeitsparameter des Epoxids und steigen dann mit dem Parameter an. Die Salzeffekte gegenuber der Reaktion der Epoxide mit Seide werden teils durch die Fahigkeit zur Hydratisierung oder die Aciditat der Kationen erklart, teils durch die Basizitat oder Nucleophilie der Anionen. Der Einflus der Substitution des Epoxids auf die Additionsreaktion wird durch eine modifizierte TAFTsche Gleichung beschrieben: dabei sind k0 und k die Geschwindigkeitskonstanten fur die Reaktion einer gegebenen Verbindung und fur die gleiche Reaktion eines ihrer Derivate, σ* die polare und Es die sterische Substituentenkonstante; ρp und ρs sind die Reaktionskonstanten als Mas fur die Beeinflussung der Reaktion durch polare und sterische Effekte der Substituenten.

The asymmetric-selection polymerization of styrene oxide was investigated by using diethylzinc/menthol system as catalyst. Monomer consumption was found to follow a second order kinetic, whereas developing of the optical rotation of the remaining monomer followed a first order reaction scheme. This phenomenon is accounted for by the assumption that the polymerization consists of rapid initiation followed by slow stepwise growth. Two moles of monomer participate in the polymerization, one of which is polymerized and the other is responsible for activation of the catalyst. The asymmetric ability of the catalyst is arising from the menthoxyl group but not from propylene oxide complexed to the catalyst. Unter Verwendung von Zinkdiathyl/Menthol als Katalysatorgemisch wurde die asymmetrisch induzierte Polymerisation des Styroloxids untersucht. Es wurde gefunden, das der Verbrauch des Monomeren nach einer Reaktion zweiter Ordnung verlauft, wahrend aus der Bestimmung der optischen Drehung des verbleibenden Monomeren ein Reaktionsschema erster Ordnung folgt. Dieses Phanomen wird durch die Annahme erklart, das die Polymerisation aus einer raschen Initiierung besteht, der ein langsames, schrittweises Wachstum folgt. Es nehmen zwei Mol des Monomeren an der Polymerisation teil, von denen das eine polymerisiert, wahrend das zweite den Katalysator aktiviert. Die Eignung des Katalysators zur asymmetrischen Selektion ist auf die Menthoxylgruppe zuruckzufuhren und nicht auf eine Komplexverbindung zwischen Propylenoxid und dem Katalysator.

Potassium methyl pyrrole-2-carboxylate and styrene oxide are shown to yield trans-1-styrylpyrrole-2-carboxylic acid (dry conditions) and 1-(2-hydroxy-2-phenylethyl)pyrrole-2-carboxylic acid (moist conditions). The hydroxy acid yields 1H-3-phenyl-3,4-dihydropyrrolo[2.1-c]-[1.4]oxazin-1-one, on treatment with polyphosphoric acid. Vinyl acids were also obtained from the potassium pyrrole ester and ethylene oxide, propylene oxide, and cis- and trans-stilbene oxide; the latter two compounds yielded stereospecific products. A pyrrolo[2.1-c]-[1.4]benzoxazinone was obtained from cyclohexene oxide. The photo chemical isomerization of the trans-1-styryl acid and the attempted conversion into lactones is described.

スチレン(M1)とp-クロルおよびp-メチルスチレンオキシド(M2)との共重合をアルミニウムイソプロポキシド触媒( 配位アニオン) , ナトリウムフェノキシド触媒( アニオン) および三フッ化ホウ素エチルエーテル錯合体触媒(カチオン)の3 種の触媒を用いて検討した。得られた共重合のモノマー反応性比より,log1/r1とハメットの置換基定数σ との間には大略直線関係が成立し,その勾配は,アルミニウムイソプロポキシド触媒で+0.2,ナトリウムフェノキシド触媒で+1.0,三フッ化ホウ素エチルエーテル錯合体で-0.8となった。アルミニウムイソプロポキシド触媒による共重合で認められた小さな置換基効果は,配位アニオン触媒によるエポキシ化合物の重合が,金属原子上へのモノマーの配位の難易と, アルコラートアニオンの移動によるエポキシ環の開環速度の大小の両方によって支配されると考えると説明がつく。

The addition reaction of styrene oxide (StO) with silk fibroin was studied in the presence of various salts in different solvents at 45–75°C. Some water was required to make StO react with silk padded with various salt solutions. The reaction rate increased with the salt concentration and reached a maximum value at a certain concentration of the salt. Padding with solutions of thiosulfate, cyanide, thiocyanate, bicarbonate, or carbonate resulted in high add-ons (to 65 mole/105 g) and low solubilities in HCl and NaOH aqueous solutions. The weight gains increased with the epoxide concentration and reached a constant value at a certain concentration of StO solution in ethanol, while they decreased slightly with epoxide concentration over 10% of StO solution in n-hexane. Histidine, lysine, arginine, tyrosine, and aspartic and glutamic acids were found to react. The reaction rate decreased with increasing solubility parameter of the solvent used, reached a minimum value about at 10 or at the solubility parameter of the epoxide, and then increased with the parameter. The StO–silk reaction may depend on the distribution of StO between aqueous salt and an organic solvent phases, and on the swelling of silk fiber in different aqueous salt solutions or in various organic solvents. The mechanism for this epoxide-silk reaction and the reactivity difference between StO and phenyl glycidyl ether toward silk fibroin are discussed in the light of the observed phenomena.

In this paper the preparation and characterization of polymers of t-butyl ethylene oxide and styrene oxide are described. Mixtures of water and zinc diethyl, having mole ratios approaching unity, were used as catalysts, and dioxan was used as solvent. The poly(t-butyl ethylene oxide) was highly crystalline and had narrow distributions of both molecular weights and degrees of stereoregularity. The poly(styrene oxide) was slightly crystalline, had a wide molecular weight distribution, and contained molecules of widely different degrees of stereoregularity.

ニトロベンゼン中,トリ-n-ブチルアミンおよびナトリウムフェノキシド(C)を触媒とする,スチレンオキシド(E)とフェノール(P)の反応速度および反応次数は反応条件により変化する。ナトリウムフェノキシドを触媒とする反応は-dE/dt=kcPE=k3CPEにしたがう。速度定数k3と反応温度の逆数は直線関係にならない。トリ-n-ブチルアミン触媒の反応は-dE/dt=k1E=(k0+k2C)Eなる式にしたがうが,見かけの速度定数k1にわずかにフェノール濃度の項を含んでいる。フェニルグリシジルエーテル(PGE)等非共役エポキシドの相応する反応との比較から次の結論が得られた。1.2次速度式にしたがう条件下ではスチレンオキシドの反応もPEGの反応に非常に類似した挙動を示し,錯化合物機構が支配的であると考えられる。2.1次速度式にしたがう条件下ではスチレンオキシドの反応は非共役エポキシドとはかなり異なった様相を示し,イオン解離機構を単純に適用することはできないと思われる。

Styrene oxide has been polymerized by the triisobutylaluminum–water catalyst system. Kinetic studies of the effects of varying the monomer, triisobutylaluminum, and water concentrations in benzene solutions have been made. Styrene oxide was consumed in two reactions: an initial fast one producing trimer and a slower reaction forming higher molecular weight polymer.

Relative signs of nuclear magnetic resonance spin- spin coupling constant in styrene oxide by double resonance

The reaction of styrene oxide with organozinc compounds was studied to clarify the polymerization mechanism of styrene oxide. In the reaction with diethylzine ring scission of styrene oxide was observed to occur almost exclusively at the CH(C6H5)O-bond to form ethylzinc monoalkoxide. In the second step zinc dialkoxide was formed by the reaction of the ethylzinc monoalkoxide with styrene oxide and the dialkoxide was found to be active species for the polymerization of styrene oxide. In the reaction of styrene oxide with zinc dialkoxide both α-scission and β-scission occurred. Studies were also made for butadiene monoxide. Die Reaktion des Styroloxids mit organischen Zinkverbindungen wurde untersucht, um den Polymerisationsmechanismus von Styroloxid zu klaren. Bei der Reaktion mit Zinkdiathyl konnte eine Ringaufspaltung des Styroloxids fast ausschlieslich der CH(C6H5)O-Bindung festgestellt werden, wobei ein Zinkatylmonoalkoxid gebildet wird. Beim zweiten Schritt bildet sich Zinkdialkoxid durch Reaktion des Zinkatbylmonoalkoxides mit Styroloxid, wobei das Dialkoxid sich als das aktive Species bei der Polymerisation des Styroloxids herausstellte. Bei der Reaktion des Styroloxids mit Zinkdialkoxid erfolgte sowohl eine α-wie auch β-Spaltung. Das Butadienmonoxid wurde entsprechend untersucht.

The absolute configuration of (−)-trans-1,2-cyclopropanedicarboxylic acid was established as 1R:2R by a direct chemical correlation with known (−)-(1R:2R)-trans-1,2-dimethylcyclopropane. Ozonolysis of (+)-trans-2-phenylcyclopropanecarboxylic acid yielded (+)-trans-1,2-cyclopropanedicarboxylic acid which shows that (+)-trans-2-phenylcyclopropanecarboxylic has the 1S:2S configuration. The significance of these results to the Wittig reaction involving optically active styrene oxide and phosphonoacetates will be discussed.

Nitro-compounds were found to be suitable as cocatalysts for the polymerization of alkylene oxides, such as ethylene oxide, propylene oxide, styrene oxide, allylglycidyl ether, and phenylglycidyl ether when they were used with dialkylzinc or trialkylaluminum catalysts. The nitromethane/diethylzine system exhibits a high catalytic activity to give a polymer of extraordinary high intrinsic viscosity as high as 32 dl/g for ethylene oxide. The system requires heat-treatment at 100°C for activation, but the resulting catalyst is heat-stable. During heat-treatment nitromethane reacts with dialkylzine evolving ethane gas to give a zinc-oxygen linkage together with zinc methazonate. Gas analysis, IR, and NMR studies confirm that the catalyst contains a zinc-oxygen linkage in addition to the ethyl-zinc bond responsible for catalyst activity. The catalyst resembles the diethylzinc/water system, but the catalyst is more heat-stable and has a longer life-time in the polymerization due to the lack of mobile hydrogen in the cocatalyst. Nitro-Verbindungen erwiesen sich in Verbindung mit Dialkylzink- oder Trialkylaluminium-Katalysatoren als wirksame Cokatalysatoren fur die Polymerisation von Alkylenoxiden wie Athylenoxid, Propylenoxid, Styroloxid, Allylglycidylather und Phenylglycidylather. Das System Dialkylzink/Nitromethan zeigt eine hohe katalytische Aktivitat und liefert ein Polymeres mit auserordentlich hoher Viskositatszahl, die z. B. bei Polyathylenoxid 32 dl/g betragt. Zur Aktivierung dieses Systems ist eine Warmebehandlung bei 100°C erforderlich, der entstehende Katalysator ist jedoch temperaturstabil. Wahrend der Warmebehandlung reagiert Nitromethan mit Diathylzink unter Entwicklung gasformigen athans, Ausbildung einer Zink-Sauerstoff-Bindung und Entstehung von Zinkmethazonat. Gasanalyse, IR- und NMR-spektroskopische Untersuchungen zeigen, das der Katalysator zusatzlich zu der fur die katalytische Aktivitat verantwortlichen athyl-Zink-Bindung eine Zink-Sauerstoff-Bindung besitzt. Der Katalysator ahnelt dem System Diathylzink/Wasser, besitzt jedoch grosere Temperaturstabilitat und auf Grund des Fehlens eines beweglichen Wasserstoffs im Cokatalysator eine langere Lebensdauer wahrend der Polymerisation.

Proton spin-lattice relaxation times (T1) within the temperature range −155° to +175°C are reported for fractions of the poly(tBEO) and the poly(styrene oxide). Two T1 minima were observed (at 30 Mc/s for each polymer: 102°C and −112°C for poly(tBEO); 127°C and −130°C for poly(styrene oxide). The high temperature minima are associated with chain backbone motions, the low temperature minima with side group motions. Activation energies for both processes are derived and compared.

Reactions of various monoepoxides and diepoxides with diethylaminoethyl (DEAE) cellulose in the absence and presence of external catalysts have been studied. In the absence of additional catalysts, many epoxides which did not react with the unmodified cotton reacted with DEAE-cotton. Others, which reacted with unmodified cotton in the presence of external bases, imparted different properties when catalyzed by the builtin tertiary amino groups of DEAE-cotton. For example, epichlorohydrin reacted with DEAE-cotton to produce a fabric with excellent conditioned recovery, good wet recovery, and strong-base anion exchange properties. The same epoxide imparted only wet crease recovery to cotton when the reaction was catalyzed by external bases. Phenyl glycidyl ether and styrene oxide reacted with DEAE-cotton to produce a fabric with twentyfold improvement in resistance to flex abrasion. With 8% aqueous NaOH as an external catalyst, the DEAE-cotton displayed greater reactivity with all epoxides than did the unmodified fabric. DEAE-cotton–diepoxide reactions with added base catalyst generally resulted in a decrease in the conditioned recovery angle and an increase in the wet recovery angle. When Zn(BF4)2 was used as an additional catalyst, again the DEAE fabrics displayed the greater reactivity toward the monoepoxides; but the unmodified cotton was more reactive toward the diepoxides than was the DEAE-cotton. The Zn (BF4)2–monoepoxide-treated DEAE fabrics had higher wet recovery angles but lower dry recovery angles than the corresponding epoxide-finished control cottons. Butadiene diepoxide was the only diepoxide investigated which imparted higher dry recovery angles to the DEAE-cotton than to the unmodified cotton control in the presence of Zn(BF4)2. Tertiary amino groups in DEAE-cottons act as an internal catalyst for the opening of the oxirane rings, direct the site for reaction in the absence of additional catalysts, and react with some epoxides to form quaternary nitrogen groups.

The reactions of olefin oxides with cobalt hydrocarbonyl have been studied. The effect of the reaction conditions on the nature of the reaction, especially that of propylene oxide, has been examined in detail. Propylene oxide gave only the products with β-hydroxy-n-butyryl structure under these reaction conditions: temperature, 25∼45°C; atmosphere; nitrogen or carbon monoxide; and mole ratio of propylene oxide, 1.4∼6.2. The inhibitory effect of a nitrogen atmosphere on the formation of carbonylated products (ester and aldehyde) has been observed ; under nitrogen, some side reaction was highly promoted, and the formation of carbonylated products was thereby prevented. The reactions of ethylene oxide, cyclohexene oxide, styrene oxide and epichlorohydrin have also been studied. In the reactions of styrene oxide, the mole ratio of styrene oxide had a significant effect on the nature of the reaction; at a relatively small mole ratio, the reduction gave, mainly two isomeric alcohols, but as the mole ratio incre...

Styrene oxide was deoxygenated to styrene in 83% yield by zinc metal and zinc chloride in aqueous ether. Under the same reaction conditions phenyl glycidyl ether gave only 2.8% of phenyl allyl ether, and propylene oxide did not give propylene. Effects of the reaction variables on the deoxygenation of styrene oxide were investigated. The yield of styrene was varied with metal halide in anhydrous THF in the following order; ZnI2>ZnCl2∼ZnBr2>AlCl3>SnCl4>FeCl3>NaI>>MgBr2. Styrene was formed from styrene oxide by zinc metal and zinc chloride in ca. 50% yield in THF, acetone, acetic acid, and aqueous ethanol, but not in anhydrous benzene. The yield of styrene increased almost proportionally with the increase of the molar ratio of zinc chloride to styrene oxide up to 1:1. 2-Phenyl-2-chloroethanol gave styrene when treated with zinc metal in the presence or absence of zinc chloride, but 1-phenyl-2-chloroethanol did not. Possible reaction paths of the deoxygenation of styrene oxide by zinc metal and metal halide w...

The reaction of styrene oxide with potassium starch alkoxide in dimethyl sulphoxide has been studied. No graft polymerization occurred, even under drastic conditions, and the reaction was found to stop at the initiation stage, as seen from the non-disappearance of the monomer with time (gas chromatography) and from examination of the products of reaction, which on acid hydrolysis yielded phenyl hydroxyethyl ether of glucose. On the other hand, homopolymerization of styrene oxide catalysed by potassium naphthalene in dimethyl sulphoxide was successful, suggesting that the failure to obtain graft polymers of styrene oxide on starch is due to steric hindrance from the starch skeleton.

A kinetic study of the polymerization of several monosubstituted ethylene oxides by the diethylzinc-water system is described. The results are discussed in terms of possible mechanisms, and it is concluded that steric factors probably play a dominant role in determining the rate of polymerization. The polymerization of styrene oxide appears to be of a rather different character from that of the alkyl substituted ethylene oxides.