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The animation of chloromethylated polystyrene (CMPS) and benzyl chloride with diethyl amine, diethanolamine, and di-n-butylamine was investigated kinetically in N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), or dioxane. The apparent second-order rate constant decreased as the amination proceeded in the amination of CMPS with diethylamine and di-n-butylamine in DMF as well as in dioxane. Although a similar deceleration was also observed in the amination of CMPS with diethanolamine in DMF and DMSO, acceleration was observed during the course of the amination in dioxane. It is assumed that the deceleration and the acceleration are due to the steric obstruction and to the formation of a hydrogen bond by the neighboring groups in the transition state respectively. The intrinsic rate constants of the amination of CMPS were almost the same as those of benzyl chloride. The rate of the amination with diethanolamine was lower than that of the amination with diethylamine because of the inductive effect of t...

The reaction of benzothiazol-2-yltrimethylsilane with trichlorogermane yields 2-trimethylsilylbenzothiazoliumtrichlorogermanate (VI), from which the monomeric benzothiazoledichlorogermylene (IX) is obtained under elimination of trimethylchlorosilane. The constituttion of IX is confirmed by ′H NMR, IR and Mass spectra. The germaniumnitrogen bond in IX is shown to be very reactive: it is easily cleaved by boron trichloride and hydrogen chloride; exchange reactiion take place with aromatic nitrogen bases. A carbene analogous insertion into the carbonhalogen bond occurs with benzyl chloride.

An investigation has been made on the change in the physico-chemical properties of aqueous solutions of branched and linear polyethyleneimine (a high mol. wt catalyst for hydrolysis of nitrophenyl esters) occurring on its being alkylated by benzyl chloride. The first result of alkylation is benzyldiethylamine fragments in PEI. Provided that the degree of conversion is below 0–3, the reaction is second order. Then the rate constant decreases, probably due to a decrease in the steric factor. Alkylation diminishes pKa's of nitrogen atoms of PEI. Accumulation of benzyl groups in PEI results in a marked contraction of its macromolecules in aqueous solutions and enhances the sorption ability with respect to n-nitroanilides. The free energy of sorption is −4 · 1 to − 5·5 kcal/mole.

Die Alkylierung von Diathyl- und Diisopropylestern 1a,1b,2a,2b3a und 3b der 2-Furyl-, 2-Thienyl- und 2-Pyridylmethylphosphonsaure mit Alkylhalogeniden in flussigem Ammoniak und in Gegenwart von Natriumamid fuhrt beim Reaktantenverhaltnis 1:1:1 zu den Monoalkylderivaten 4a,4b,5a,5b,7a,7b,8a,8b,10a,10b, 11a,11b,12a und 12b in 87-98proz. Ausbeuten. Beim Reaktantenverhaltnis 1 : 2.5 : 2.5 werden mit Butylbromid die entsprechenden Dibutylderivate 14a,14b,17b,20a und 20b in 89-95proz. Ausbeuten erhalten. Isopropylbromid liefert nur das Monoisopropylderivat von la in 91 proz. Ausbeute. Mit Benzylchlorid werden beim Reaktantenverhaltnis 1 : 1 : 1 neben den Monobenzylderivaten 6a,b und 9b auch die Dibenzylderivate von 1a,b und 2b in geringen Ausbeuten gebildet. Die Alkylierung der Monobutylderivate von 1a,1b,2b,3a und 3b fuhrt zu den Alkylbutylderivaten 13a,13b,15a,15b,16b,18b,19a,19b,21a und 21b in 85 -94proz. Ausbeuten. Der Einflus der heteroaromatischen Ringe auf die Reaktionsfahigkeit von Carbanionen der Phosphonate 1a, 1b, 2a, 2b, 3a und 3b wird diskutiert. Alkylation of Esters of 2-Furyl-, 2-Thienyl- and 2-Pyridylmethylphosphonic Acid with Alkyl Halides in Liquid Ammonia Alkylation of the diethyl and diisopropyl esters 1a, 1b, 2a, 2b, 3a, 3b of 2-furyl-, 2-thienyl-, and 2-pyridylmethylphosphonic acid with alkyl halides in liquid ammonia and in the presence of sodium amide gives the corresponding monoalkyl derivatives 4a, 4b, 5a, 5b, 7a, 7b, 8a, 8b, 10a, 10b, 11 a, 11 b, 12a, and 12b (yields 87-97%), when the reactants are used in a ratio of 1 : 1 : 1. With butyl bromide and a reactant ratio of 1 :2.5 :2.5 the corresponding dibutyl derivatives 14a,14b,17b,20a, and 20b (yields 89-95%) are obtained; with isopropyl bromide, however, only the monoisopropyl derivative of 1a is formed in 91 % yield. With benzyl chloride in a reactant ratio of 1:1:1 some dibenzyl derivatives of 1a,1b, and 2b are formed along with the monobenzylated products 6a,6b, and 9b. Alkylation of the monobutyl derivatives of 1a,1b,2b,3a, and 3b gives the corresponding alkyl butyl derivatives 13a,13b,15a,15b,16b,18b,19a,19b,21a, and 21b in 85-94% yields. The influence of the hetero- aromatic ring on the reactivity of the carbanions of the phosphonates 1a,1b,2a,2b,3a, and 3b is discussed.

While benzyl trichloromethanesulfenate undergoes no rearrangement to sulfoxide even at high temperatures, the corresponding anisyl ester rearranges to p -anisyl trichloromethyl sulfoxide in hexane under mild conditions. Substitution of hexane by chloroform under similar conditions, lead to the formation of p -anisyl chloride and dichlorosulfine as main reaction products. This process is enhanced by the use of more polar solvents and higher temperatures. The conversion of trichloromethanesulfenate to chloride has also been observed with the benzyl and benzhydryl esters on heating in various solvents, though at very differing rates. Both rearrangements are suggested to take place by an ionization mechanism. Depending on the reaction conditions and nature of the substrate, the sulfenate anion can either recombine with the cation to give sulfoxide, or further dissociate to dichlorosulfine and chloride ion, which gives the benzyl chloride. The observation of an S N 1 type mechanism for rearrangement of sulfenates appears to be unique.

The following ethers, of potential value for the synthesis of α- D -galactopyranosides, were prepared: 2- O -benzyl- D -galactose, 2,6-di- O -benzyl- D -galactose, and 2,3-di- O -benzyl- D -galactose. Isopropylidenation of methyl α- D -galactopyranoside in the presence of phosphorus pentaoxide gave its 3,4-, and 4,6- O -isopropylidene derivatives. Treatment of the 3,4-acetal with trityl chloride in pyridine produced the 6-trityl ether, which was benzylated with benzyl chloride and sodium hydride in N,N -dimethylformamide to yield the 2-benzyl ether. Acid hydrolysis of this product gave 2- O -benzyl- D -galactose. Benzylation of methyl 3,4- O -isopropylidene-α- D -galactopyranoside, followed by hydrolysis, gave 2,6-di- O -benzyl- D -galactose. Similarly, 2,3-di- O -benzyl- D -galactose was obtained by acid hydrolysis of methyl 2,3-di- O -benzyl-4,6- O -isopropylidene-α- D -galactopyranoside and of methyl 2,3-di- O -benzyl-4,6- O -benzylidene-β- D -galactopyranoside.

A study was made of quaternization of poly-4-vinylpyridine with benzyl chloride and individual reaction rate constants found: k0=5·8×10−4, k1=k2=1·7×10−4 1./ole· sec.. From constants found by the Monte Carlo method the funnctions of composition distribution of products of quaternization were calculated; these describe satisfactorily the experimental results derived by gel permeation chromatography. The possibility of describing and composition heterogeneity by the same set of constants k0, k1, and k2 enables us t draw conclusions regarding the decisive role of the effect of adjacent units in the reaction studied.

The reactions of the lithium, sodium, potassium and cesium derivatives of 3-methyl-5-carbomethoxy-pyrazole, of 3-methyl-5-ethyl-pyrazole and of 3-methyl-5-methoxy-methylene-pyrazole with methyl iodide, allyl bromide and benzyl chloride were investigated in 1,2-dimethoxy-ethane solution and at a liquid/solid interface (suspension of the pyrazole in a 1:1 mixture of n-hexane and n-heptane). Comparison of the ratios of the two nitrogen alkylated products formed from the reaction in solution and at the liquid/solid interface, suggests that the latter ratio is determined by the size of the alkali metal cation and by the presence of a coordination centre placed non-symmetrically with respect to the mirror plane passing through the nitrogen-nitrogen bond. It is suggested that a “cation in the way” effect is responsible for the liquid/solid-interface alkylation results.

The reactions of benzyl chloride,p-methyl benzyl chloride,p-chloro benzyl chloride, benzyl bromide andp-nitro benzyl bromide with aromatic and heterocyclic bases have been studied in carbon tetrachloride-phenol mixtures. The reactions of amines and pyridine with benzylchloride andp-methyl benzyl chloride have been extended to solvent mixtures like benzene-phenol, nitrobenzene-phenol, nitro-benzene-ethanol and carbontetrachloride-ethanol mixtures and those of amines and pyridine with benzyl bromide andp-nitrobenzyl-bromide have been extended to DMF-phenol mixtures. The results are discussed in the light of basicity, nucleophilicity, electronic, steric and medium effects.

The amination of chloromethylated polystyrene (CMPS) and benzyl chloride with butylamine isomers and diethylamine was investigated kinetically in dioxane, methyl ethyl ketone (MEK), and N,N-dimethylformamide (DMF). Although the amination of i- and s-butylamine conformed to the ordinary second-order kinetics in all the solvents, deceleration was observed during the course of the amination of CMPS with n-butylamine in MEK as well as in dioxane, with t-butylamine in DMF, and with diethylamine in both dioxane and DMF. The intrinsic rate constants of the amination of CMPS were generally almost the same as those of benzyl chloride. The magnitudes of the rate constants in each solvent were in this order; n-butyl>i-butyl>s-butyl>t-butyl; it was in the order of DMF>>MEK≈dioxane with all the amines investigated. These results were interpreted in terms of both the structures of the amines and the interaction between the amine and the solvent molecules.

The thermal and photochemical reactions of toluene with anhydrous iron(III) chloride in the solid state result in nuclear chlorination. In a homogeneous system, a side-chain reaction occurs under irradiation with light, although no product is obtained in the thermal reaction. The addition of water to the iron(III) chloride–toluene system in the range of the molar ratio of 1–5 changes the course of the photochemical reaction; in the water/iron(III) chloride molar ratios of 1–1.7, 3, and 4–5, the main products are the diphenylmethane-type compound, o- or p-chlorotoluene (o>p), and benzyl chloride respectively. Pyridine as a ligand acts to give benzyl chloride selectively. The Mossbauer data of the FeCl3/nH2O solid show that the arrangement of the Cl− ion around the Fe(III) ion changes upon the addition of water. The thermal and photochemical reactions of p-methoxytoluene with anhydrous iron(III) chloride give 2,2′-dimethoxy-4,4′-dimethylbiphenyl by oxidative aryl coupling. Water inhibits the aryl coupling r...

The absorption spectra and kinetic behavior of the species produced in irradiated ethanol solutions of 1- and 2-chloronaphthalenes, 4-chlorobiphenyl, 1- and 2-bromonaphthalenes, and 2and 4-bromobiphenyls were studied using pulse radiolysis at 100 deg K. The spectra observed are ascribed to the parent negative ions of these halogenated compounds. The negative ions of the chlorinated compounds have long lifetimes and an appreciable part remains even at a few seconds after the pulse. On the other hand, the negative ions of the brominated compounds disappear in a complicated manner within 100 msec. Ethanol solutions of 1,2,3trichlorobenzene and tetrachloroethylene give intense absorptions in the ultraviolet region which may also be ascribed to the negative ions of these solutes. Pulse radiolysis of ethanol solutions of benzyl chloride gives only absorption due to benzyl radicals. The negative ion of benzyl chloride dissociates into a benzyl radical and a chloride ion at 100 deg K. (auth)

Results of electron scavenging experiments for gamma irradiation at 4 K are reviewed. An anomalous increase in the scavenging efficiency at 4 K is discussed. Intermediate anions which have very short lifetimes at usual temperatures are very stable at 4 K. As an example of these anions, the optical absorption spectrum of the benzyl chloride anion is described.

The cytotoxicity of 33 organic solvents was determined using Ehrlich-Landschutz diploid (ELD) ascites tumour cells during short-time in vitro incubations. Among the organic solvents studied, tetralin, crotonic aldehyde, formaldehyde, and acrolein were highly toxic to ELD cells. Benzyl chloride, carbon tetrachloride, methyl ethyl ketone, and 1,1,1,2-tetrachloroethane were found to be moderately toxic. Tumour cells treated with crotonic aldehyde were reinoculated into mice. The growth capacity of the inoculated population was shown to be dependent on the frequency of surviving cells after treatment with the organic solvents indicating that true cell mortality was studied.

( h 1 -Benzyl) ( h 5 -cyclopentadienyl)dicarbonyliron, I, ( h 1 -benzyl) ( h 5 -cyclopentadienyl)tricarbonylmolybdenum, II, and its tungsten analog, III, have been prepared, along with linear and crosslinked polystyrenes with I, II, and III as pendant moieties, by the reaction of the corresponding metal carbonyl anions with benzyl chloride. The thermal decomposition of I neat, in decane, or in benzene at 140° gave first order carboniron bond homolysis and h 5 -cyclopentadienyldicarbonyl] dimer, XI, its monobenzylated analog (C 6 H 5 CH 2 C 5 H 4 )(C 5 H 5 )Fe 2 (CO) 4 , XII, dibenzyl, and tar. The mole ratio of XI/XII varied between 8–12. Neat decomposition of polymers containing bound I was slow at 140° but in solution decomposition proceeded to give XI, and polymer-bound dimer XIV at 160° was detected. Similarly, thermal decomposition of II gave (C 5 H 5 ) 2 Mo 2 (CO) 6 , XV, and its benzylated analogs (C 6 H 5 CH 2 C 5 H 4 ) (C 5 H 5 )Mo 2 (CO) 6 , XVI, and (C 6 H 5 CH 2 C 5 H 4 ) 2 Mo 2 (CO) 6 , XVII, while decomposition of III gave (C 5 H 5 ) 2 W 2 (CO) 6 ,XVIII, (C 6 H 5 CH 2 C 5 H 4 ) (C 5 H 5 )W 2 (CO) 6 ,XIX and (C 6 H 5 CH 2 C 5 H 4 ) 2 W 2 (CO) 6 , XX. In these cases benzyl migration to Cp rings predominates even in solution. Solution decompositions also generated dibenzyl except in cumene where toluene was formed. For the decompositions of II and III the results suggest the migrating benzyl groups never become separated from the developing dimer and might “ride up” to attack the endo side of the Cp rings. Both linear and crosslinked polymers with pendant units of II and III composed very slowly neat in the solid phase, faster in solution, and in both modes dimers XV and XVIII formed in addition to polymer-bound benzylated analogs of XVI and XIX. Crosslinked polymers were prepared with dimers XI, XV, and XVIII dispersed throughout.

Although the apparent second-order rate constant of the amination of chloromethylated polystyrene with n-butylamine or with 2-aminobutanol decreased or increased, respectively, during the course of the amination in dioxane, as has been reported previously, both animations as well as the aminations of benzyl chloride have been found to conform to the ordinary second-order kinetics in DMF and DMSO. The viscometric measurements have indicated that the viscosity of the reaction mixture decreased during the amination with n-butylamine and increased slightly during the amination with 2-aminobutanol, but no relation between the kinetic behavior and the viscometric changes in the reaction mixtures could be found. The magnitude of the rate constants was comparable to that of the amination of benzyl chloride, and it increased with an increase in the dielectric constant of the solvents in this order: dioxane<

The reactions between benzyl chloride and various bases as well as p-nitrobenzyl chloride and various bases have been studied in nitrobenzene-ethanol mixtures. The reaction is total second order as found earlier.

By the investigation of the solvent effects in the reaction of benzyl chloride and tin powder, it was elucidated that dibenzyltin dichloride was formed at first, and the conversion into tribenzyltin chloride occurred in polar solvents. In water, bis(dibenzylchlorotin) oxide was an intermediate in the conversion. Catalytic effects in the reaction was also studied.

パラ置換シアン化ベンジル存在下においてアゾビスイソブチロニトリルを開始剤として60℃でスチレンおよびメタクリル酸メチルの重合を行ない,パラ置換シアン化ベンジルの連鎖移動定数を決定した。スチレンおよびメタクリル酸メチルの重合において,置換シアン化ベンジルの連鎖移動定数はハメット式(logCx/CH=ρσ)にはしたがわず,改良ハメット式(logCx/CH=ρσ+γER)に対して直線関係が得られ,スチレンの場合はρ=0.24,γ=1.O,メタクリル酸メチルの場合はρ=-1.0,γ=0.8が得られることから,置換シアン化ベンジルの連鎖移動反応性に対してはシアン化ベンジルの置換基の極性と共鳴の両因子が寄与していると考えられる。連鎖移動定数の値から,メスロビアンの式にしたがって置換シアン化ベンジルのQtr,etrを計算した。メスロビアンのetrとハメットのσとの間には直線関係が成立する。

The photochemical substitution of ferrocene in several halogenated hydrocarbon–ethanol solutions was investigated. Ethoxycarbonyl, formyl, ethoxymethyl, benzyl and allyl groups were photochemically introduced into ferrocene in 25–53% yields by the UV-irradiation of ferrocene in carbon tetrachloride–, chloroform–, dichloromethane–, benzyl chloride–, and allyl bromide–ethanol solutions, respectively. The reactions proceeded effectively by the excitation of the charge transfer complexes formed between ferrocene and halogenated hydrocarbons.

When allylbenzene was treated with the same moles of sodium amide and benzyl chloride in liquid ammonia, one or two benzyl radicals were introduced into allylbenzene to produce 3,4-diphenyl-1-butene and 3-benzyl-1-butene. The reaction is similar to the well-known reaction of benzyl cyanide and benzyl chloride in liquid ammonia and that of 2-phenyl-1-ethanol and benzyl chloride in benzene. Two forms of 2,3-diphenylpropionic acid were isolated and their I. R. spectra were measured. Different curves were obtained in KBr disks, while the identical curves were obtained carbon tetrachloride solution. Infrared absorption spectra were measured by Professor Kinumaki and his associates of this Institute and the elementary analyses were performed in the laboratory of Shionogi and Company, Ltd., to whom the writers are deeply indebted.

The kinetics of the solvolysis of benzyl chloride, under catalysis by mercuric chloride, has been examined in a few compositions of aqueous ethanol. Some measurements in the absence of catalyst have also been carried out. The Arrhenius parameters have been determined for both the normal and catalysed reactions as also the effect of added chloride ions on the rates of the reactions. The results have been discussed in terms of the Hughes-Ingold theory of nucleophilic aliphatic substitution.

The presence of alkali metal iodides accelerated the reaction of benzyl chloride with alkali cellulose. The alkali metal iodide was added to the mercerizing alkali used to activate the cotton yarn. The degree of benzylation observed with iodide present was 74% to 110% greater than with iodide absent. A D.S. of 0.7 could readily be obtained within a reaction period of thirty minutes at 115°C. The breaking strength retention at this D.S. was 93% to 119%, based on unmercerized, untreated yarn. Other salts tended to retard benzylation. Borax and neutralized boric acid were ineffective as catalysts, contrary to previous reports. Catalysis by iodide salts is considered to be due to the in situ formation of benzyl iodide from benzyl chloride within the cellulose fibers, the organic iodide being a more active alkylating agent than the chloride. Hydrotropic effects of the alkali iodides appear to be of secondary importance in the catalysis.

First-order rate constants for the solvolysis of benzyl chloride in a series of aqueous acetone and aqueous dimethylsulfoxide (DMSO) mixtures at 50.100 °C and at various pressures in the range 1–4083 atm are reported. Volume of activation, calculated from the rate/pressure data, is found to exhibit extremum behavior with varying solvent composition in both solvent systems. The activation volumes are dissected into their initial state and transition state contributions by determining the "instantaneous" volumes of solution of benzyl chloride in the solvent systems. The contributions of both the initial state and the transition state to the behavior of the activation volume as a function of solvent composition are discussed.

Polybenzyl, prepared by treating benzyl chloride with stannic chloride in the presence of air at room temperature, is fluorescent. The fluorescence and absorption spectra of this polybenzyl have been determined. From these spectral studies together with the reactions of polybenzyl with butyl lithium and sodium/potassium alloy, it has been established that the most probable fluorescent unit is a benzyl substituted 9 phenyl or 9:10 diphenyl anthracene. A possible mechanism is given for the formation of this fluorescent group via the formation of a carbonium ion of diphenyl methane type.

The reactions between benzyl chloride and cuprous chloride were studied. It was found that good yields of bibenzyl were obtained by the addition of ethylenediamine, diethylenetriamine, triethylenetetramine, acetylacetone and EDTA. Nothing of bibenzyl was observed in the cases of ethanolamine, pyridine, dipyridyl, phenanthroline and triphenylphosphine. These facts, together with the spectral studies of copper complexes can reasonably be explained by the formation of reactive species of the type CuI(en)nCl. The course of the reaction was discussed on the basis of the substituent and medium effects. Radical but not free type mechanisms which include the transient organocopper species were considered. Some additional comments were also made.

A nomographic method is described for the quantitative gas chromatographic analysis of ternary mixtures of benzyl chloride, benzal chloride and benzotrichloride. The nomograph converts percentages of total peak area on the gas chromatogram into weight percentages of the components of the sample. The nomograph is constructed by combining a triangular composition diagram with two binary calibration graphs. The latter graphs have been experimentally determined by gas chromatographic analysis of two series of synthetic binary mixtures. An experimental check shows the method to be accurate to within 1–2 wt. %.

Es wurde der Einflus einiger n-Alkylhalogenide (n-Butylfluorid, n-Butylchlorid und n-Butylbromid) und einiger Benzylhalogenide (Benzylfluorid, Benzylchlorid und Benzylbromid) auf die durch Aluminiumjodid katalysierte Polymerisation des Isobutylens in Heptan studiert. Dabei wurde festgestellt, das das n-Butylfluorid und die Benzylhalogenide die Polymerisationsgeschwindigkeit wesentlich erhohen. Aus der Abhangigkeit der Polymerisationsgeschwindigkeit und der Molekulargewichte der gewonnenen Polymeren von der Konzentration der Alkylhalogenide und des Aluminiumjodids geht hervor, das die Alkylhalogenide nicht als Cokatalysatoren wirken, sondern das die Erhohung der Polymerisationsgeschwindigkeit durch katalytisch aktive Produkte verursacht wird, die durch Halogenaustausch zwischen dem Aluminiumjodid und den Alkylhalogeniden gebildet werden. Die Ergebnisse der vorliegenden Arbeit werden im Zusammenhang mit den Erkenntnissen diskutiert, die uber die Polymerisation des Isobutylens mit den aus zwei FRIEDEL-CRAFTS-Halogeniden bestehenden Katalysatorsystemen gewonnen wurden. An investigation was made on the effect of some n-alkyl halides (n-butyl fluoride, n-butyl chloride, and n-butyl bromide) and some benzyl halides (benzyl fluoride, benzyl chloride, and benzyl bromide) on the polymerization of isobutene in heptane, catalyzed by aluminium iodide. It was found that n-butyl fluoride and benzyl halides raise the rate of polymerization considerably. It was also established, from the dependence of the rate of polymerization and of the molecular weights on the concentration of alkyl halides and aluminium iodide, that alkyl halides do not act as cocatalysts, but that the increase in the rate of polymerization is due to the formation of catalytically active products of halogen exchange between aluminium iodide and alkyl halides. The results are discussed in terms of our present knowledge concerning the polymerization of isobutene with catalytic systems consisting of two FRIEDEL-CRAFTS halides.

The polycondensation reactions of benzyl chloride, α-chloroethylbenzene, and benzhydryl chloride in the presence of SnCl4 or AlCl3 as catalysts have been investigated in the temperature range between +80° and −135°C. Polycondensations of benzyl chloride and α-chloroethylbenzene are quite similar in the reaction kinetics and are thought to occur by the same displacement mechanism. Polycondensation of benzhydryl chloride, however, seems to involve the formation of benzhydryl carbonium ions. At low temperatures linear polymers tend to be formed, in contrast with branched polymers produced at room temperature. Steric effects are found to play a major role in protecting polymers from branching at lower temperatures. Polybenzyl polymers are found to be less linear than poly(-α-methylbenzyl), even when prepared at −135°C.

When 2 mol. of phenyllithium are allowed to react with 1 mol. of lutidine and the mixture is then treated with an excess of benzyl chloride, α-methyl-α′-(dibenzyl-methyl) pyridine (I) is produced along with α-methyl-α′-phenylethylpyridine (VI). The statement of Bergmann and Rosenthal, that α,α′-bis-(phenylethyl)pyridine (II) should be produced in this reaction, is incorrect. When 2 mols. of phenyllithium are allowed to react with 1 mol, of lutidine and the product is treated with an exces of benzoic anhydride, a derivative of lutidine is produced, which, contrary to the opinion of Kloppenburg and Wibaut, is to be considered as the benzoate of the enol form of 2-phenacyl-6-methylpyridine (VIIb). (VIII). By the interaction of 2 mols. of phenyllithium and 2 mols. of The action of 1 mol. of phenyllithium and 1 mol. of benzonitrile on 1 mol. of α,α′-lutidine leads to the formation of 6-methyl-2-phenacylpyridine (VIII). By the interaction of 2 mols of phenyllithium and 2 mols of benzonitrile on 1 mol. of α,α′-lutidine, a complicated reaction takes place with the formation of a compound C21H19N3, to which a tricyclic structure (XI) is ascribed.

The polarographic behavior of trans-stilbene, triphenylethylene, tetraphenylethylene, benzyl chloride and carbon tetrachloride has been studied in tetramethylurea containing tetrabutylammonium bromide. The results obtained indicate that this solvent offers no advantage over dimethylformamide. The high resistance of the solvent made the large scale electrolysis of benzyl chloride difficult to carry out. Products obtained were toluene, n-butane, butenes and tri-n-butylamine. The similarity in structure of tetramethylurea to dimethylformamide suggested an evaluation of this liquid as a solvent for the polarographic studies of organic compounds. Studies in the latter have furnished evidence for the existence of stable anion-free radicals in the reduction of aromatic hydrocarbons, quinones, aromatic ketones and of dihalocarbenes in the reduction of carbon tetrachloride and bromide.

Benzyl chloride vapor has been photolyzed in the presence of ethane or n‐butane at 184.9, 206.2, and 253.7 nm. Pressure, wavelength, and temperature effects on the quantum yields of products were examined. Benzyl chloride was found to photodecompose predominantly to a benzyl radical and a chlorine atom. The chlorine atoms abstract the hydrogen atom from ethane or n‐butane to form ethyl or butyl radicals. The reaction of these radicals with benzyl radicals results in the formation of various products. The quantum yield of the initial photodecomposition of the C–Cl bond in benzyl chloride at 184.9 nm (at zero n‐butane pressure) was obtained to be 0.9. The initial photodecomposition rate constant of benzyl chloride at 184.9 nm has been estimated. The ratio between disproportionation and recombination reaction rate constants of radicals has also been obtained.

The application of the long-known Friedel-Crafts reaction to rubber hydrocarbons led to a new type of condensation products which may be called provisionally aral cyclorubbers (“benzylidene rubbers”), since their benzylidene groups are probably condensed with the polyprene skeleton to cyclic systems. It would not have been foreseen without further work that rubber would form this type of condensation product with aral halides in the presence of aluminum chloride, since on the one hand benzyl chloride is known to form, by the action of aluminum chloride in the Friedel-Crafts reaction, an amorphous, apparently high molecular hydrocarbon of the empirical composition (C7H6)x, and on the other hand rubber in solution is transformed by the metal chlorides, especially aluminum chloride, into amorphous polycyclorubbers. Under definite conditions of condensation with aluminum chloride aral groups are combined with the skeleton of the rubber hydrocarbon with the formation of white to yellowish amorphous bodies which contain, in addition to a small proportion of organically combined chlorine, only carbon and hydrogen, and are therefore to be regarded as hydrocarbons. In their physical and chemical properties these substances resemble the already known amorphous substance of the empirical formula (C7H6)x, which doubtless is polybenzylidene, probably hexabenzylidene.

Among the aryl-aliphatic nitriles subject to alkylation, phenylacetonitrile is especially reactive and its methylene hydrogens are readily replaced by one or two alkyl groups. The benzylation of this substance is most commonly performed with benzyl chloride in the presence of finely powdered sodium amide in an inert solvent. The preliminary communication from this laboratory reported several examples of benzylation of phenylacetonitrile and related nitriles (I) by means of benzyl alcohol and sodium. (Chart 1). The present paper is concerned with the detailed study of the reaction and additional comments about the mechanism.

Rates of solvolysis of benzyl chloride and of substituted benzyl chlorides have been measured in an acetone-water mixture (acetone mole fraction 0.147) at pressures ranging from atmospheric to 1 kbar. Pressure studies have also been made for p-methyl benzyl chloride in various acetone-water mixtures. Measurements have also been made of the partial molar volumes of the reactants. The plots of log k against pressure are fitted to a second-degree polynomial in P, and values of ΔV‡ and (δΔV//δP)T are obtained. The ΔV‡ values are all negative, having values ranging from −18 to −24 cc/mole. The results are interpreted on the view that the mechanisms are SN2(1), i.e. are towards the SN1 end of the SN2 spectrum of behavior. The ΔV‡ values steadily become more negative in the series pCH3, H, pCl, pNO2, and this is interpreted in terms of the greater spreading of positive charge in the pCH3 case and in terms of greater SN2(2) character in the pNO2 case. The ΔV‡ values go through a minimum as the solvent composition is varied, a result that is related to the existence of a corresponding maximum in the partial molar volumes of the reactant. The (δΔV‡/δP)T values show a negative correlation with ΔV‡, suggesting, as expected, that the more compact activated complexes are the least compressible.

The first order rate constants for the solvolysis of benzyl chloride in a series of mixtures of methyl, ethyl, i-propyl, and t-butyl alcohols with water are reported at 40.05 and 60.50 °C. The ΔH* and ΔS* values are calculated using these rate constants and those previously reported at 50.25 °C (1, 2). The dependence of these parameters on solvent composition is discussed.

A wide variety of organochlorine compounds has been tested in a tapping torque cutting test at 15 mg atoms chlorine per 100 g blend in liquid paraffin. The relative effectiveness of the blends was compared with that given by the same fluids in the four-ball extreme pressure test. A representative number of the fluids was tested in another cutting test, the drill life test. In general, good correlation between these tests was found. The tightness of the curl of the swarf obtained from the tapping test was seen to be characteristic of the activity of the test fluid. Examination of the outer surface of the swarf using the scanning electron microscope showed scoring marks when pure carbon tetrachloride was used as the cutting fluid. These marks were not observed when cutting with any of the liquid paraffin blends. A five-fold increase in concentration of the additive gave a rank order of the blends in the tapping test similar to that found at the lower concentration. The chemical reactivity towards steel of certain of the blends was found and the bond dissociation energies of those organochlorine compounds where data were available were calculated. The reactivity and the carbon-chlorine bond strength correlated well with the cutting efficiency and EP activity of the fluids. The cutting results can be explained in terms of the ability of the blends to form a low shear chloride film on the rake face-chip interface. This function appeared to be controlled by the carbon-chlorine bond strength in the additive, which in increasing order was found to be benzyl chloride