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Several kinds of fruit and vegetable seed meals were examined as the novel biocatalysts for the synthesis of alkyl and phenylalkyl glycosides, an important group of nonionic surfactants, from d -glucose and primary alcohols. The crude enzymes from prune and black plum seeds displayed comparable or slightly higher catalytic efficiency and better operational stability as compared to those from apple and peach seeds. These alkyl glycosides were synthesized with the yields of 14–78% using prune seed meals. In addition, synthetic yields of alkyl and phenylalkyl glycosides decreased dramatically with the elongation of the chain of the primary alcohols. In the synthesis of octyl β- d -glucopyranoside, the maximal yield of 14% was obtained with prune seed meals. However, in the synthesis of ethyl, propyl and butyl β- d -glucopyranoside with the same catalyst, the yields were 78%, 69% and 53%, respectively, which were much higher than that of octyl β- d -glucopyranoside. Enzymatic synthesis of butyl β- d -glucopyranoside was conducted on a 0.9 g scale, with an average isolated yield of 30% for the first two batches. [ABSTRACT FROM AUTHOR]

We have recently reported that, in the presence of light and a copper catalyst, nitrogen nucleophiles such as carbazoles and primary amides undergo C-N coupling with alkyl halides under mild conditions. In the present study, we establish that photoinduced, copper-catalyzed alkylation can also be applied to C-C bond formation, specifically, that the cyanation of unactivated secondary alkyl chlorides can be achieved at room temperature to afford nitriles, an important class of target molecules. Thus, in the presence of an inexpensive copper catalyst (CuI; no ligand coadditive) and a readily available light source (UVC compact fluorescent light bulb), a wide array of alkyl halides undergo cyanation in good yield. Our initial mechanistic studies are consistent with the hypothesis that an excited state of [Cu(CN)2]- may play a role, via single electron transfer, in this process. This investigation provides a rare example of a transition metal-catalyzed cyanation of an alkyl halide, as well as the first illustrations of photoinduced, copper-catalyzed alkylation with either a carbon nucleophile or a secondary alkyl chloride. [ABSTRACT FROM AUTHOR]

Thionyl chloride is often used to convert alcohols into more reactive alkyl chloride, which can be easily converted to many compounds that are not possible from alcohols directly. One important reaction of alkyl chloride is nucleophilic substitution, which is typically conducted under basic conditions. Sulfur dioxide, the by-product from alcohol-thionyl chloride reactions, often reacts with alkyl chloride to form a sulfonyl acid impurity, resulting in yield loss. Therefore, the alkyl chloride is typically isolated to remove the by-products including sulfur dioxide. However, in our laboratory, the alkyl chloride formed from alcohol and thionyl chloride was found to be a potential mutagenic impurity, and isolation of this compound would require extensive safety measures. As a result, a flow-through process was developed, and the sulfur dioxide was purged using a combination of vacuum degassing and nitrogen gas sweeping. An analytical method that can quickly and accurately quantitate residual levels of sulfur dioxide in the reaction mixture is desired for in-process monitoring. We report here a simple ultraviolet (UV) spectrophotometry method for this measurement. This method takes advantage of the dramatic change in the UV absorbance of sulfur dioxide with respect to pH, which allows for accurate quantitation of sulfur dioxide in the presence of the strong UV-absorbing matrix. Each sample solution was prepared using 2 different diluents: 1) 50 mM ammonium acetate in methanol +1% v/v hydrochloric acid, pH 1.3, and 2) 50 mM ammonium acetate in methanol +1% glacial acetic acid, pH 4.0. The buffer solutions were carefully selected so that the UV absorbance of the sample matrix (excluding sulfur dioxide) at 276 nm remains constant. In the pH 1.3 buffer system, sulfur dioxide shows strong UV absorbance at 276 nm. Therefore, the UV absorbance of sample solution is the sum of sulfur dioxide and sample matrix. While in the pH 4.0 buffer system, sulfur dioxide has negligible UV absorbance at 276 nm, and the UV absorbance is attributed only to sample matrix. Quantitation of sulfur dioxide is achieved by subtracting the UV absorbance of sample solution at pH 4.0 from that at pH 1.3. The method is simple but sensitive, with a limit of quantitation of 80 μg L −1 . The method linearity was demonstrated from 2 mg L −1 to 40 mg L −1 with an R 2 of 0.998, and the spiked recovery ranges from 94% to 105% within the same range. The results are comparable with those obtained using inductively coupled plasma–atomic emission spectrometry (ICP–AES) and gas chromatography–mass spectrometry (GC–MS), suggesting that this method is accurate. [ABSTRACT FROM AUTHOR]

A series of N-alkyl- N, N-dimethyl- N-( o-hydroxymethyl)benzylammonium chlorides surfactants (DHBA- m) were synthesized using o-chloromethylbenzyl alcohol and N-alkyl- N, N-dimethyl tertiary amine as raw materials. The structure of the products was confirmed by FT-IR, H NMR, C NMR and MS. DHBA- m surfactants exhibit low Krafft points and high surface activities. The process of micellization of DHBA- m is spontaneous, exothermic, and entropy-driven. The hydroxymethyl substitution increases hydrophobicity of DHBA- m, thus making micellization more favorable compared with that of N-dodecyl- N, N-dimethyl- N-benzylammonium chlorides (DDBAC- m). The bactericidal activity of DHBA- m is stronger on E. coli than that of DDBAC-12, and DHBA-16 shows strong bactericidal activity on Salmonella, S. aureus, and Streptococcus. [ABSTRACT FROM AUTHOR]

An efficient alkylation method of functionalized alkyl halides under mild nickel-catalyzed C( sp3)C( sp2) Suzuki cross-coupling conditions is described. The features of this approach are excellent functional group compatibility, low cost nickel catalyst, and the use of a mild base. This is also the first successful example of the nickel-catalyzed direct 2,2-difluoroethylation or 2,2,2-trifluoroethylation of aryl-/heteroarylboronic acids. [ABSTRACT FROM AUTHOR]

The potential of hydrophobically-modified poly(vinyl pyrrolidone) as a shear-responsive, self-associative hydrogel for ophthalmic applications is demonstrated. Hydrophobic modification was achieved via random copolymerization of N-vinylpyrrolidone with N-vinylformamide, the latter of which can be hydrolyzed to expose a desired degree of reactive amine groups permitting grafting of alkyl chlorides of varying alkyl chain lengths. The resulting materials formed highly shear-responsive physical hydrogels, exhibiting tunable shear thinning over 4–5 decades of viscosity from infinite shear to zero shear conditions that facilitates lubrication upon blinking and/or facile injection or drop-based delivery to the anterior or posterior segments of the eye. Viscosity changes due to self-association over time can also be tuned by changing the length of the hydrophobe, with C 18 -grafted materials exhibiting prolonged thickening over several weeks to form extremely stiff hydrogels and shorter grafts equilibrating significantly faster but forming weaker gels. The hydrogels remained transparent even at very high polymer concentrations (20 wt%) and are demonstrated to facilitate controlled release of a model drug (doxorubicin). The polymers exhibit minimal cytotoxicity in vitro to human corneal epithelial cells and retinal pigment epithelial cells, particularly when lower molecular weight backbone polymers were used. In vivo assessments in rabbits indicated no significant conjunctival edema or redness, secretion, corneal opacity, or iris involvement upon anterior application. Following intravitreal injection in rat eyes, no opacification of the lens, cornea or vitreous, nor any morphological or functional change to the posterior segment was observed. Examination of wholemount tissues and histology demonstrated no adverse effect from the injection or deposition of material. As such, these shear-thinning materials offer potential for drug delivery in both the anterior and posterior segments or as a vitreal replacement that can be easily administered or removed. [ABSTRACT FROM AUTHOR]

[Figure not available: see fulltext.] In the current study, five novel perimidinium chlorides were synthesized in good yields by reaction of 1-(3-methylbenzyl)perimidine with five different alkyl chlorides under microwave irradiation in 30 minutes. Synthesized compounds were characterized by IR, H, C NMR spectroscopic methods and elemental analyses. Performance of in situ formed catalytic system which consist of the perimidinium salts and Pd(OAc) was investigated for Heck and Suzuki reactions in aqueous media, and desired products were obtained in good yields. [ABSTRACT FROM AUTHOR]

A simple and cost-effective one-pot parallel synthesis approach to sulfides, sulfoxides, and sulfones from thiourea was elaborated. The method combines two procedures optimized to the parallel synthesis conditions: alkylation of thiourea with alkyl chlorides and mono or full oxidation of in situ generated sulfides with H2O2 or H2O2-(NH4)2MoO4. The experimental set up required commonly used lab equipment: conventional oven and ultrasonic bath; the work up includes filtration or extraction with chloroform. The method was evaluated on an 81 member library of drug-like sulfides, sulfoxides, and sulfones yielding the compounds on a 30-300 mg scale. A small-scale synthesis of 2-(benzhydrylsulfinyl)acetamide (modafinil) utilizing our approach resulted in similar efficiency to the published procedures. [ABSTRACT FROM AUTHOR]

Four cationic surfactants of quaternary hexammonium silane chloride based on hexamethylenetetramine and alkyl chloride were synthesized. The chemical structures of the prepared cationic surfactants were elucidated using Fourier transform infrared (FT-IR) spectroscopy and mass spectrometry analysis. The surface and thermodynamic properties of the prepared surfactants were also studied. The performance of these cationic surfactants as microfouling agents against two strains of Gram-negative bacteria, namely, Pseudomonas aeruginosa and Escherichia coli, and two strains of Gram-positive bacteria, namely, Staphylococcus aureus and Bacillus subtilis, were evaluated as antimicrobial agents. The results showed that the maximum antimicrobial activity was detected for N-hexamethylenetetramine- N-ethyl silane ammonium trichloride (Ah). The maximum and minimum antimicrobial activities were 73 and 60 % against S. aureus and E. coli, respectively, at a concentration of 5 mg/l, pH 7, and 37 °C. [ABSTRACT FROM AUTHOR]

A cobalt-N-heterocyclic carbene catalytic system promotes pyridine-directed olefinic C-H alkylation reactions using a variety of primary and secondary alkyl chlorides under mild conditions. Radical clock experiments suggest that the reaction involves single-electron transfer from the cobalt intermediate to the alkyl chloride. [ABSTRACT FROM AUTHOR]

[Display omitted] • Barbier reaction was reported as a convenient reaction tool in covalent modification of poly(vinyl chloride). • Tailorable functionalization was achieved under magnesium mediated conditions. The development of efficient synthetic methodologies for chemical functionalization and modification of existing polymers to improve or diversify the physicochemical and mechanical properties is an ongoing quest in macromolecular science. This is especially true for the generation of polymeric materials out of commercial/commodity polymers via structural tailoring since these polymers are produced in vast quantities and are structurally diverse. In this study, we report on benign chemical modification of an important commercial polymer, poly(vinyl chloride) (PVC) via Barbier reaction. The methodology is based on the employment of magnesium metal to generate nucleophilic alkyl-magnesium chloride groups on polymer backbone and addition of these nucleophilic centers to electrophilic carbonyl groups. The synthetic procedure can be implemented in a one-pot fashion by utilizing commonly available aldehyde or epoxide bearing compounds along with elemental magnesium. The Barbier addition of PVC backbone generated alkyl-magnesium chloride groups on the model aldehyde substrates with different structures were achieved with > 84 % functionalization degrees. It was shown that the functionalization degrees can easily be regulated by the simple alteration of employed magnesium ratio to backbone present alkyl chloride groups. Functionalization studies were investigated via 1H NMR, FT-IR and SEC analyses as well as contact angle measurements. Considering the wide industrial/ research utilization of poly(vinyl chloride) together with commercial availability, abundant reactive alkyl chloride bonds in backbone chains of this polymer offer easy to implement structural tailoring via proposed organometallic Barbier reaction. [ABSTRACT FROM AUTHOR]

A new and efficient method for the chlorodehydration of alcohols utilizing TCCA/DMF is described. Various alcohols can be converted smoothly into their corresponding alkyl chlorides in high yields under mild conditions with short reaction times. [ABSTRACT FROM PUBLISHER]

A novel phenol-linked bis(imidazolium) salt, HLCl (L = O-4-C(CH)-CH-2,6-di[CH{C(NCHCHNAr)}], Ar = 2,6-diisopropylphenyl, 1), was designed and used to prepare an ionic iron(III) complex [HL][FeCl] ( 2). Complex 2 was a highly efficient catalyst for aryl Grignard cross-coupling of alkyl chlorides bearing β-hydrogens. Furthermore, complex 2 was reusable and could be reused in at least eight times without significant loss in catalytic activity. [ABSTRACT FROM AUTHOR]

The first total synthesis of N-methylwelwitindolinone B isothiocyanate is reported. The route features several key steps, including a regio- and diastereoselective chlorinative oxabicycle ring-opening reaction to introduce the challenging alkyl chloride motif. [ABSTRACT FROM AUTHOR]

The alkylation of the starting pseudooctahedral dichlorido imido hydridotris(3,5-dimethylpyrazolyl)borate niobium and tantalum(V) compounds [MTp*Cl2(NtBu)] (M = Nb,Ta; Tp* = BH(3,5-Me2C3HN2)3) with MgClR in different conditions led to new alkyl chlorido imido derivatives [MTp*ClR(NtBu)] (M = Nb/Ta, R = CH2CH3 1a/1b, CH2Ph 2a/2b, CH2tBu 3a/3b, CH2SiMe3 4a/4b, CH2CMe2Ph 5a/5b), whereas the dimethyl derivatives [MTp*Me2(NtBu)] (M = Nb 6a, Ta 6b) could be isolated as unitary species when the reaction was carried out using 2 equivalents of the magnesium reagent MgClMe. However, the chlorido methyl [MTp*ClMe(NtBu)] (M = Nb 7a, Ta 7b) complexes were obtained by heating at 50 °C the dichlorido and dimethyl imido complexes mixtures in a 1 : 1 ratio. All of the complexes were studied by multinuclear magnetic resonance spectroscopy and the molecular structures of 1b, 2a/b, 3a/b, 4a and 5a/b were determined by X-ray diffraction methods. In the solid state the complexes 1b, 4a and 5a exhibit only a gauche-anti conformation and the complexes 2a/b, 3a/b and 5b exhibit only a gauche-syn conformation of the alkyl substituents, whereas both conformational states, which do not show mutual exchange in the NMR time scale, were observed for 3a/b in a benzene-d6 solution. The 15N chemical shifts of the complexes 1-7 are discussed. [ABSTRACT FROM AUTHOR]

The adsorption enthalpies, ΔH, of a series of alkyl chlorides in acidic (H-FAU) zeolite have been investigated using density functional theory (DFT) and molecular mechanics methods. Two models were employed to simulate the zeolite cluster, each containing one Brønsted acid site. The first model, corresponding to the formula Al(OH)(OH)(SiOH), forms a 12-membered ring (12T) constructed from 11 Si tetrahedral atoms and one Al atom in the windows of the twelve O atoms and has been fully optimized at the B3LYP/6-31+G(d,p) level of theory. The second model is represented by the more realistic cluster of 84 tetrahedral units (84T) and has been examined with the help of the ONIOM2 approach using the two layered schemes B3LYP/6-31+G(d,p):UFF and M06-2X/6-31+G(d,p):UFF in two series of calculations. The latter series using the newly developed M06-2X functional by Truhlar and coworkers (Zhao et al., J Chem Phys 123:161103, ; Zhao and Truhlar, Theor Chem Acc 120:215, ), is expected to make a more reliable and realistic estimation of the effect of the dispersion forces which are quite important in this type of systems. The calculated structural variations and adsorption enthalpies of the van der Waals 1:1 adsorption complex assumingly formed, are shown to exhibit an impressive dependence both on the size of the zeolite cluster model and on the theoretical method employed, particularly the M06-2X functional. Indeed, the M06-2X calculations bring out most clearly the important role and the significant contribution of the dispersion forces to the adsorption enthalpies of a series of the alkyl chlorides on acidic zeolite leading to ΔH values higher by more than 30 % compared to the B3LYP results. Finally, the present calculations reconfirm the dependence of the interaction energy on the size and the branching of the alkyl radical. [ABSTRACT FROM AUTHOR]

Indiumchloride catalyzed alkylative rearrangement of propargylicacetates into α-alkyl-α,β-unsaturated carbonyl compoundshas been achieved. Propargylic acetates functioned as α-acylvinylanion equivalents to react with carbocations generated from alkylchlorides. Other alkyl electrophiles such as alcohols and acetateswere also applicable. [ABSTRACT FROM AUTHOR]

A general and conceptually novel method for preparing polychloro-substituted pyrrolidin-2-ones and indeno[2,1- c]pyrrol-3(3a H)-ones is established by visible-light-facilitated 5- exo-trig cyclization of 1,6-dienes with alkyl chlorides through selectively splitting the C(sp3)-H bond adjacent to the chloride atom to form an alkyl radical. [ABSTRACT FROM AUTHOR]

A facile method for the stereoselective synthesis of trans-2,3-dihydrobenzofurans from ortho-quinone methides in situ generated from readily available 2-alkyl-substituted phenols using silver oxide-mediated oxidation has been developed. Additionally, the 2,3-dihydrobenzofurans can be further transformed into the aromatized 2,3-disubstituted benzofurans in the presence of DDQ. [ABSTRACT FROM AUTHOR]

[Display omitted] • Using TPCC quenching method to study the polymerization kinetics of a-diimine nickel catalyst. • The ability of different alkylaluminum cocatalysts to activate a-diimine nickel catalyst was compared. • The effect of temperature on the activation ability of AlEtCl2 on a-diimine nickel catalyst was analyzed. • Proposed the possibility of enhancing the thermal stability of a-diimine nickel catalyst through cocatalyst. 2-thiophenecarbonyl chloride (TPCC) quenching method was used into the study of alkylaluminum activation behavior on α-diimine nickel catalysts. The influence of alkylaluminum structure (AlEt 2 Cl, Al 2 Et 3 Cl 3 , AlEtCl 2 and modified methylaluminoxane (MMAO)) and polymerization temperature on the kinetic factors (active center concentration [C*] and chain propagation rate constant k p) of ethylene polymerization catalyzed by the system was systematically studied. It was found that, compared with MMAO, alkyl aluminum chloride could better activate catalyst and produced more active centers in the polymerization system, but the value of k p was lower than MMAO. Unexpectedly, as the polymerization temperature increased, [C*] in the polymerization system with AlEtCl 2 as cocatalyst gradually increased, and k p decreased. But the change of [C*] and k p of the polymerization system with MMAO as cocatalyst was opposite. It was proposed that cocatalyst is one of the factors affecting the thermal stability of catalyst. [ABSTRACT FROM AUTHOR]

Keywords: Chloroalkanes; Cross-Coupling; Photocatalysis; Reaction Mechanisms; Synthetic Methods EN Chloroalkanes Cross-Coupling Photocatalysis Reaction Mechanisms Synthetic Methods 1 1 1 05/11/22 20220516 NES 220516 B Photocatalysis b The photoredox activation of inert chloroalkanes for cross-coupling reactions with olefins is presented by Julio Lloret-Fillol et al. in their Research Article (e202114365). Chloroalkanes, Cross-Coupling, Photocatalysis, Reaction Mechanisms, Synthetic Methods Frontispiece: Photoredox Activation of Inert Alkyl Chlorides for the Reductive Cross-Coupling with Aromatic Alkenes. [Extracted from the article]

[Display omitted] • Ti(III) cationic complexes were first used to catalyze ethylene polymerization. • Activity in the presence of Et 2 AlCl/Bu 2 Mg up to 4.6 tonn kgPE/mol Ti h⋅atm. • Activity largely depends on the Ti/Al molar ratio. • UHMWPE samples were processed into high-strength and high-modulus oriented films. Complex cations with a vacant coordination site are considered as the most plausible catalytically active centers of metallocene and post-metallocene polymerization catalysts. For the first time we demonstrated that cationic titanium (III) complexes stabilized with crown ether can be used as pre-catalysts for ethylene polymerization. In the presence of alkyl aluminum chlorides and MgBu 2 as cocatalysts, these complexes catalyze ethylene polymerization to produce Ultra High Molecular Weight Polyethylene (UHMWPE) with productivity up to 4650 kg PE /mol Ti h⋅atm and molecular weight up to 1.8·106 Da. UHMWPE powders were processed by the solid-phase method with subsequent orientation drawing into high-strength (1.4–2.1 GPa) and high-modulus (91–118 GPa) films. [ABSTRACT FROM AUTHOR]

Alkyl aryl ketones were prepared on a gram scale by the nickel-catalyzed reductive coupling of alkyl iodides with aroyl chlorides. When scaled up 30-fold, this reaction shows a comparable coupling efficiency to the previously reported reaction performed under smallscale conditions. The mild and convenient reaction conditions show excellent tolerance to a range of functional groups and provide the ketones in good to excellent yields [ABSTRACT FROM AUTHOR]

We report here cobalt-N-heterocyclic carbene catalytic systems for the ortho alkylation of aromatic imines with alkyl chlorides and bromides, which allows the introduction of a variety of primary and secondary alkyl groups at room temperature. The stereochemical outcomes of the reaction of secondary alkyl halides suggest that the present reaction involves single-electron transfer from a cobalt species to the alkyl halide to generate the corresponding alkyl radical. A cycloalkylated product obtained by this method can be transformed into unique spirocycles through manipulation of the directing and cycloalkyl groups. [ABSTRACT FROM AUTHOR]

Highly efficient arylations of β-chloro ketones and their ester and amide derivatives were achieved by means of domino dehydrochlorination/Rh(I)-catalyzed conjugate addition. In situ generated vinyl ketones and their analogues were identified as the reaction intermediates. The present synthetic protocol provides a concise route to (chiral) β-aryl ketones, esters, and amides. [ABSTRACT FROM AUTHOR]

Two bimetallic cryptates (containing Cu and Co), which have previously been shown to react with and activate atmospheric CO2, were tethered to modified mesoporous SiO2 and their activities in promoting the CO2+H2 reaction has been analysed. The cryptates were tethered to C3H6Cl-modified SBA-15 through a condensation reaction between surface alkyl chlorides and 2° amines of the ligands, which released HCl and formed 3° amine linkages. The materials were characterised using BET, thermogravimetric analysis, FTIR and elemental analysis and their activities in promoting the CO2+H2 reaction was tested under batch reactor conditions. Co ions appear to selectively populate the medal sites of the tethered ligands whereas Cu ions appear to deposit on the surface as Cu(BF4)2 salts. The composite materials generate CO and CH4 from the CO2+H2 mixtures. Co-containing catalysts are more effective than their Cu analogues in promoting the reaction. [ABSTRACT FROM AUTHOR]

Secondary alkyl chlorides have been efficiently prepared from secondary alkyl sulfonates under mild and user-friendly conditions. The exchange reaction was generally performed by using benzyltributylammonium chloride in acetone (reflux, 30 min). Yields are excellent from functionalized, base-sensitive and hindered secondary alkyl sulfonates [ABSTRACT FROM AUTHOR]

Abstract: The acyl-Claisen rearrangement of substituted phenylacetyl chlorides and cinnamyl morpholines gives 2,3-syn-diarylpent-4-enamides. Electron-rich cinnamyl morpholines containing alkoxy substituents only reacted with phenylacetyl chlorides; replacement of the phenylacetyl chlorides with alkyl acid chlorides in these reactions gave no rearranged products. Use of the morpholine amides generated in the synthesis of the natural tetrahydrofuran neolignan magnosalicin and tetraphenyl tetrahydrofuran is also reported. [Copyright &y& Elsevier]

We present a building-block approach toward functionalized CB[7] derivatives by the condensation of methylene-bridged glycoluril hexamer 1 and glycoluril bis(cycic ethers) 2 and 12. The CB[7] derivatives Me2CB[7] and CyCB[7] are highly soluble in water (264 mM and 181 mM, respectively). As a result of the high intrinsic solubility of Me2CB[7], it is able to solubilize the insoluble benzimidazole drug albendazole. The reaction of hexamer 1 with glycoluril derivative 12, which bears a primary alkyl chloride group, gives CB[7] derivative 18 in 16% isolated yield. Compound 18 reacts with NaN3 to yield azide-substituted CB[7] 19 in 81% yield, which subsequently undergoes click reaction with propargylammonium chloride (21) to yield CB[7] derivative 20 in 95% yield, which bears a covalently attached triazolyl ammonium group along its equator. The results of NMR spectroscopy (¹H, variable-temperature, and DOSY) and electrospray mass spectrometry establish that 20 undergoes self-assembly to form a cyclic tetrameric assembly (204) in aqueous solution. CB[7] derivatives bearing reactive ftmctional groups (e.g., N3, Cl) are now available for incorporation into more complex functional systems. [ABSTRACT FROM AUTHOR]

Activation of primary aliphatic alcohols with triphosgene and triethylamine mixtures afforded either alkyl chloride or diethylcarbamate products, and the switch in selectivity appeared to be driven by sterics. The reaction conditions to achieve this highly useful transformation were unexceptionally mild and readily tolerated by a wide range of sensitive functionalities. [ABSTRACT FROM AUTHOR]

The unimolecular gas-phase elimination kinetics of 2-methoxy-1-chloroethane, 3-methoxy-1-chloropropane, and 4-methoxyl-1-chloroburane has been studied by using density functional theory (DFT) methods to propose the most reasonable mechanisms of decomposition of the aforementioned compounds. Calculation results of 2-methoxy-1-chloroethane and 3-methoxy-1-chloropropane suggest dehydrochlorination through a concerted nonsynchronous four-centered cyclic transition state (TS) to give the corresponding olefin. In the case of 4-methoxyl-1-chloroburane, in addition to the 1,2-elimination mechanism, the anchimeric assistance by the methoxy group, through a polar five-centered cyclic TS, provides additional pathways to give 4-methoxy-butene, tetrahydrofuran and chloromethane. The bond polarization of the CCl, in the direction of C δ+ ···Cl δ−, is the limiting step of these elimination reactions. The significant increase in rate together with the formation of a cyclic product tetrahydrofuran in the gas-phase elimination of 4-methoxyl-1-chloroburane is attributed to neighboring group participation of the oxygen of the methoxy group in the TS. The theoretical calculations show a good agreement with the reported experimental results. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2011 [ABSTRACT FROM AUTHOR]

This paper reports computations that were done in conjunction with an experimental study, reported in an accompanying paper, involving single pulse shock tube measurements of the thermal decomposition of 2-chloropropane, chlorocyclopentane, and chorocyclohexane. The overall aim of the combined work is to provide a well-defined, self-consistent, and reliable set of rate constants for those species over an extended temperature range for use as reference reactions in comparative rate studies. To provide additional validation of the results for the compounds of direct interest, the dehydrochlorination reactions of the related compounds chloroethane, 1-chloropropane, and 2-chlorobutane are also considered. The present work reviews and summarizes the literature information regarding the molecular properties, thermochemistry, and chemical kinetic data for the above six alkyl chlorides. Quantum chemical methods are used to compute the structure and energies of reactants, products, and transition states and the fundamental nature of these types of reaction (four-centered 'semi-ion pair' transition states) is discussed. The experimental and theoretical results are compared in detail, and uncertainties are assessed. The computations are used, in conjunction with experimentally determined rate constants, to develop Rice-Ramsperger-Kassel-Marcus (RRKM)/Master Equation models and thereby allow extrapolation of the experimental data over an extended range of temperatures. © 2011 Wiley Periodicals, Inc.* Int J Chem Kinet 44: 369-385, 2012 [ABSTRACT FROM AUTHOR]

Abstract: To gain an understanding of the role of an alkyl chloride as a hydrogen bond acceptor, geometries and interaction energies were calculated at the MP2/aug-cc-pVDZ level of theory for complexes between ethyl chloride and representative hydrogen donor groups. The results establish that these donors, which include hydrogen cyanide, methanol, nitrobenzene, pyrrole, acetamide, and N-methylurea, form XCl hydrogen bonds (X=C,N,O) of weak to moderate strength, with ΔE values ranging from −2.8 to −5.3kcal/mol. [ABSTRACT FROM AUTHOR]

1-(4′-Alkylaminosulphurylphenyl)-3-methyl-5-pyrazolonyl azo-anthraquinone dyes were prepared in four steps from 1-aminoanthraquinone, as an approach to enhancing the exhaustion levels of disperse dyes on polylactide fibres. Their structures were confirmed from combustion analysis and mass spectrometry, infrared and proton nuclear magnetic resonance spectroscopy. Results from artificial intelligence-based molecular modelling studies showed that increasing alkyl chain length gave an increase in LogP, molecular volume and aplanar shape. Their application to polylactide fibres led to both good per cent exhaustion values and good light fastness ratings. It was also found that the nature of the alkyl chains attached to the phenyl ring had little influence on dye colour, but clearly influenced per cent exhaustion and wash fastness. [ABSTRACT FROM AUTHOR]

A batchwise, multigram preparation of 2-azabicyclo- [2.1.1]hexane hydrochloride (1·HCl) was developed, delivering a total of 195 grams of material. The key synthetic step involves an intramolecular displacement of a primary alkyl chloride with a tert-butylsulfinamide to forge the [2.1.1]-bicyclic ring system. [ABSTRACT FROM AUTHOR]

A readily available copper carbene complex, (IPr)CuOtBu, catalyses the hydroboration of ketones and aldehydes even at very low catalyst loadings (0.1 mol%), in some cases with turnover frequencies exceeding 6000 h−1. Carbonyl reduction occurs selectivitily in the presence of other reducible functional groups including alkenes, nitriles, esters, and alkyl chlorides. [ABSTRACT FROM AUTHOR]

A cyclic glycerophospholipid, in which two glycerols are connected via alkyl chains to form a 64-membered macrocycle, was synthesized. The structural features that differentiate this from our analogous lipids previously reported are two methylene moieties in the alkyl chains, which were incorporated to improve membrane fluidity. Fluorescence recovery after photobleaching revealed that the membranes made from the methylene-containing cyclic lipid demonstrated fluidity at room temperature unlike those of a linear alkyl-chain lipid of equal ring size. [ABSTRACT FROM AUTHOR]

The oxidation of nine primary and secondary alcohols to the corresponding aldehydes and ketones has been carried out under mild conditions and in good yields using the cyclocarbaphosphazenes (R 2 PN)(ClCN) 2 [R 2 P = Cl 2 P( 1 ), Ph 2 P( 2 )] along with dimethylsulfoxide. While both the P═Cl and C─Cl bonds of the carbaphosphazene can in principle bring about the reaction, we observed an increased preference for the C═Cl bonds over the P═Cl bonds in the oxidation of alcohol. Blocking the reactive P site on the heterocyclic ring with the phenyl groups was found to reduce the yields of the oxidized products, while blocking the C- sites with diethylamino groups resulted in no reaction. In addition, along with DMF, the same cyclocarbaphosphazene has been found to be useful for the conversion of alcohols to alkyl chlorides. [ABSTRACT FROM AUTHOR]

Abstract: The photosulfochlorination of n-tetradecane by sulfuryl chloride leads to a reaction mixture containing unreacted n-tetradecane, chloro n-tetradecanes and n-tetradecanesulfonyl chlorides. Direct and simultaneous GC analysis of the mixture of the sulfochlorinated and chlorinated isomers is followed by mass spectrometry identification of all the components either by electron impact (EI-MS) and by negative and positive chemical ionisation (NCI-MS and PCI-MS). With the goal of performing an accurate quantitative GC analysis, and as n-tetradecanesulfonyl chlorides prone to degrade partially into the corresponding chlorides, the former are converted to N,N-diethylsufonamides, more stable thermally, and then analysed by GC/EI-MS and GC/PCI-MS. The chloro n-tetradecanes, sulfonylchlorides and sulfonamides spectra present strong similarities. However, some differences between terminal and internal isomers are noticed and the peculiar behaviour of sulfonamides is emphasized. [Copyright &y& Elsevier]

For the first time it is shown that N-heterocyclic carbenes are suitable ligands for the palladium-catalyzed coupling of alkyl chlorides with aryl Grignard reagents. A variety of simple as well as functionalized primary alkyl chlorides provide the corresponding alkyl benzenes in general in good to very good yield. By comparing the 1,3-dimesitylimidazol-2-ylidene (IMes) palladium(0) naphthoquinone complex with the previously known palladium phosphine catalyst for the model coupling reaction of 1-chlorohexane with phenylmagnesium bromide it is demonstrated that the new catalyst system is superior. [Copyright &y& Elsevier]

A convenient method for the synthesis of the title compounds has been established. Chloralbenzamides were efficiently converted to N-(1-amino-2,2-dichloroethyl)benzamides which were directly transformed to 4-amino-2-aryl-2-oxazolines in fair to good yields by electrochemical reduction in an aprotic medium under constant cathodic potential. The molecular structure of the electrolysis products has been corroborated by X-ray crystallographic analysis of 4-(1-benzyl-3-phenylureido)-2-phenyl-2-oxazoline. [Copyright &y& Elsevier]

Trichloroisocyanuric acid with triphenylphosphine in anhydrous acetonitrile will convert alcohols into alkyl halides. [ABSTRACT FROM AUTHOR]

[Display omitted] • A solvent-free method for the preparation of phosphinates from P(O)-OH compounds with alkyl chlorides is disclosed. • Various phosphinates can be prepared in good to high yields. • The reaction mechanism were studied systematically by 31P NMR spectroscopy. • The reaction can be scaled up. Herein, a new solvent-free synthetic method using P(O)-OH compound and alkyl chloride for phosphinate compounds is disclosed. This transformation proceeds smoothly under the promotion of a lone base and presents the advantages of an easily available raw material source, a simple post treatment process, good functional group tolerance and high reaction efficiency. Good yield was obtained when the reaction was magnified to gram scale, and the molar ratio of P(O)-OH compounds and alkyl chlorides can be decreased to 1:2. This protocol provides a practical method for the preparation of phosphorus derivatives. Furthermore, the reaction mechanism was explored by means of 31P NMR. [ABSTRACT FROM AUTHOR]

[Display omitted] • Hydrophilic and granulated CTS/HMO was prepared for Li+ adsorption. • A novel two-step cross-linking strategy using ECH was developed. • High thermal and chemical stability was obtained. • Li+ was successfully recovered from high-temperature geothermal water. Adsorption is one of the most promising methods for lithium recovery from aqueous solutions. Herein, eco-friendly chitosan (CTS) was used to prepare granulated H 4 Mn 5 O 12 (HMO) ion-sieve for lithium adsorption from aqueous solutions. It was found that the hydroxyl and amino groups in CTS can react with the epoxy group and alkyl chloride in epichlorohydrin (ECH) under acidic and alkaline conditions, respectively. This unique property resulted in the adequate cross-linking of CTS and the uniform distribution of HMO in the CTS matrix by a novel two-step cross-linking strategy with ECH as the cross-linking agent. Especially when the superfine hydrogen-type rather than lithium-type ion-sieve was coated by this method at a mass ratio of CTS/HMO = 1:1, the material exhibited high thermal and chemical stability. The dissolution loss of Mn was no more than 1.15% in 0.25 mol·L−1 HCl even after 24 h continuous stirring, and it still maintained good thermal stability at 433 K. When the material was used for Li+ (25.78 mg·L−1) recovery from geothermal water which is characterized by high temperature, the adsorption capacity reached 11.4 mg·g−1 with a recovery rate of 88.42% at a solid-to-liquid ratio of 4 g·L−1. Because chitosan is widely applied for the preparation of various adsorption materials, the cross-linking strategy developed in this work provides a new idea for the preparation of chitosan-based composite materials with high stability and adsorption properties. [ABSTRACT FROM AUTHOR]

Enamides are a unique structural moiety in organic chemistry, present in numerous natural products and countless synthetic derivatives. In this report, we wish to disclose our recent work on the development of a novel, metal-free method to access trans -γ-chloro-enamides from the union of acrolein with secondary amides under mildly dehydrative conditions. Subsequent S N 2 displacement of the primary alkyl chloride with a variety of nucleophiles allowed access to a number of trans -γ-functionalized-enamides. In addition to a concise substrate study, two of these derivatives were further reacted to form novel triazole products, as well as di- and trienamide-containing materials. [Display omitted] [ABSTRACT FROM AUTHOR]

β-hydroxynitrates (HN) are a major class of products formed during OH and NO3 initiated oxidation of terpenes. Their production contributes significantly to secondary organic aerosol (SOA) formation and NOx sequestration. However, studying the condensed phase reactions of this important class of molecules has been hindered by the lack of commercially available authentic standards. The goal of this work was to examine the influence of water concentration and solvent identity on product yields of a tertiary HN derived from 3-carene prepared in house. To assess the role of water on conversion chemistry, bulk-phase reactions were conducted in DMSO-d6, a non-nucleophilic solvent, with a gradient of water concentrations, and analyzed with 1H NMR. Product identifications were made by comparison with authentic standards prepared in house. Four major products were identified, including an unexpected diol produced from carbocation rearrangement, diol diastereomers, and trans-3-carene oxide, with varying yields as a function of water concentration. Product yields were also measured in two protic, nucleophilic solvents, MeOD-d4 and EtOD-d6. Finally, reactions with added chloride formed alkyl chloride products in yields approaching 30%. These results are among the first to highlight the complexities of nucleophilic reactions of hydroxynitrates in bulk, mixed aqueous/organic media and to identify new, unexpected products. [ABSTRACT FROM AUTHOR]

• Removal of 1-chlorooctane reached 99% over Al 2 O 3 -9.5 at 150 °C. • 1-Chlorooctane was converted into 1-octanol and Cl− on porous oxides at 150 °C. • The Lewis acid amount on the adsorbent governs its dechlorination performance. Al 2 O 3 , TiO 2 , ZrO 2 and SiO 2 were used for adsorptive dechlorination of model oil at different temperatures. The results showed that chlorine removal over the four mesoporous oxides sharply increased with increasing the temperature from 20 °C to 150 °C. GC–MS and ion chromatography analysis showed that 1-chlorooctane was converted into 1-octanol and chloride ion at the temperature higher than 120 °C, which were then adsorbed on the adsorbent. Precipitation pH had a significant impact on the dechlorination performance of Al 2 O 3. Among various porous oxides, Al 2 O 3 -9.5 precipitated at pH 9.5 exhibited the highest dechlorination performance, over which the chlorine removal reached 99% after adsorption for 3 h at 150 °C. The characterization results indicated that various porous oxides contained only Lewis acid, and the dechlorination performance of the adsorbent basically increased with the increase of its total Lewis acid amount. The dechlorination efficiency for different organochlorine compounds followed the order: straight chain alkyl chlorides > chlorinated cycloalkanes > aromatic hydrocarbons. Al 2 O 3 -9.5 showed good regenerability, and the dechlorination performance of Al 2 O 3 -9.5 had only a slight decrease after six consecutive dechlorination-regeneration cycles, due to slight loss of its Lewis acid amount and surface area. [ABSTRACT FROM AUTHOR]

• We investigated mechanisms of formation of 1,1-diarylalkanes in enantioselective Ni-catalyzed reductive cross-coupling system. • For the reactant (S)-R 2 to get the products (R, S)-P, the favored way is Path C where the NiI catalyst initially combined with alkyl chloride. • For the reactant (R)-R 2 to get the products (R, S)-P, the favored way is Path A or B where NiI or Ni° catalyst initially combined with aryl bromide. • The formation of (R)-P is dominant over the product (S)-P. The detail mechanisms of enantioselective Ni-catalyzed reductive coupling of 5-bromide-2-methoxypyridine (R 1) and (1-chloropropyl) benzene (R 2) to form 1,1-diarylalkanes (R, S)-P were studied using Density Functional Theory calculations. The overall catalytic cycles include the following basic steps: the oxidative addition, reduction, radical production, radical addition, reductive elimination and the catalyst regeneration. Our calculated results show that the favored way from the reactant (S)-R 2 to get the products (R, S)-P is Path C (the NiI catalyst initially combined with alkyl chloride) where the energy barrier of the rate-determining step is the oxidative addition step with 9.1 kcal/mol (of TS 1b), but the favored path starting from the reactant (R)-R 2 to get the products (R, S)-P is Path A (the NiI catalyst initially combined with aryl bromide) or Path B (the Ni° catalyst initially combined with the aryl bromide) where the energy barrier of the rate-determining step is the radical production step with 12.7 kcal/mol (of (R)-TS 2 ). Our calculated results also indicate that the formation of (R)-P is dominant over the product (S)-P, which meets the experimental results. The ligand effects have also been studied. [Display omitted] [ABSTRACT FROM AUTHOR]

• Concentration of electroactive Al 2 Cl 7 - species from ionic liquids was determined. • Diffusion coefficients of Al-species were determined using CV and CA methods. • Average nuclii radius during nucleation were obtained at various applied potentials. • Number density of nucleation and grain sizes are comparable with the literature. In this study, aluminum was electrodeposited from ionic liquids comprising a melt of alkyl imidazolium chlorides and aluminum chloride (AlCl 3). The ionic liquids utilized in this study were 1-ethyl-3-methyl-imidazolium chloride (EMIC)-AlCl 3 , 1-butyl-3-methylimidazolium chloride (BMIC)-AlCl 3 , and 1-hexyl-3-methyl-imidazolium chloride (HMIC)-AlCl 3 at the AlCl 3 mole fraction of 0.667 (molar ratio of 1:2). The electrochemical behavior of chloroaluminate species in the three ionic liquids was investigated by cyclic voltammetry (CV) and chronoamperometry (CA) techniques at different temperatures. The cyclic voltammograms indicated that the reduction of Al 2 Cl 7 − species to metallic aluminum followed a diffusion-controlled phenomenon. Moreover, even at a less negative applied potential, the higher current density was obtained for EMIC-AlCl 3 ionic liquid. That indicates that EMIC-AlCl 3 favors less energy consumption during the electrodeposition. The chronoamperometric analysis revealed that the onset of aluminum deposition from such ionic liquids proceeds via a three-dimensional instantaneous nucleation process. The concentrations of Al 2 Cl 7 − ions in the ionic liquids were calculated based on the thermodynamic data, which were 2520, 2271, and 2035 mol m−3 for EMIC-AlCl 3 , BMIC-AlCl 3 , and HMIC-AlCl 3 , respectively. The diffusion coefficient (D) values of Al 2 Cl 7 − species in such ionic liquids were also calculated at various temperatures. The D values determined from the CA technique at 363 K are 2.16 × 10−11, 1.03 × 10−11, and 0.87 × 10−11 m2 s−1 for EMIC-AlCl 3 , BMIC-AlCl 3 , and HMIC-AlCl 3 , respectively. In addition, the D value increased as temperature increased and decreased as the hydrocarbon group in the ionic liquid increased. The calculated grain sizes of nucleation range from 2 to 4 μm for these ionic liquids and are in good agreement with experimental data obtained from SEM micrographs. [ABSTRACT FROM AUTHOR]

[Display omitted] • New ionic liquid (IL) containing AlCl 3 catalysts were synthesized and used in PAO production. • The catalytic efficiency of IL/AlCl 3 catalysts was tuned by the proper choice of alkyl chloride in IL composition. • By proper selection of IL, uniformly structured PAOs with low KV and SCB, but higher VI values were achieved. • In the employed catalytic system, the loading of corrosive AlCl 3 was halved. • The achievements open a new area in PAO production for further optimization of IL systems to reach low viscosity PAOs. A new class of ionic liquid (IL) containing AlCl 3 catalysts was synthesized from 1-methylimidazole, and different alkyl chlorides, including: 1-butyl chloride, cyclohexyl chloride and benzyl chloride, named as IL-But/AlCl 3 , IL-CH/AlCl 3 and IL-Benz/AlCl 3 , respectively. The as-synthesized catalysts were employed along with half dosage of AlCl 3 in the 1-decene oligomerization to related polyalphaolefins (PAOs), as a less-toxic alternative to the conventional, corrosive and toxic AlCl 3 and BF 3 catalysts. Besides aiming to achieve new, safer and cost-effective catalyst, the microstructure-flow properties of the synthesized oils were studied by using various techniques. Results revealed that the catalytic efficiency of IL/AlCl 3 catalysts can be tuned by the proper choice of alkyl chloride. IL-Benz/AlCl 3 and IL-CH/AlCl 3 yielded more uniformly structured PAOs with low molecular weight, kinematic viscosity (KV), and short chain branching, but, higher viscosity index (VI) values. However, IL-CH/AlCl 3 resulted PAO whose characteristic was very close to the one obtained by neat AlCl 3. Synthesized from greener IL/AlCl 3 system, in which the loading of AlCl 3 as catalyst is halved, together with enabling to control PAO microstructure by proper selection of IL ligand are substantial achievements of the suggested catalytic systems. [ABSTRACT FROM AUTHOR]