Allyl Chloride Research Articles

Technological Aspects of Highly Selective Synthesis of Allyloxyalcohols—New, Greener, Productive Methods

Allyl ethers bearing free hydroxyl groups of CH2=CH-CH-O-A-OH type (hydroxyalkyl allyl ethers, allyloxyalcohols) are valuable chemicals in many environmentally friendly industrial applications. The development of technologically attractive methods for their production is necessary. The two pathways (L-L PTC and non-catalytic solvent-free conditions) were optimized for the highly selective and yield synthesis of 4-allyloxybutan-1-ol. Improvements in the PTC method (50% NaOH(aq), the equimolar ratio of NaOH to diol, cyclohexane as solvent) with a new highly selective and effective PT catalyst, i.e., Me(n-Oct)3N+Br− (0.3 mol%), resulted in 88% yield and 98% selectivity of 4-allyloxybutan-1-ol with minimal formation of allyl chloride hydrolysis by-products (<1%). In turn, application of non-catalytic solvent-free conditions and the change in the key substrate with an excess of diol and use of solid NaOH solely led to a mono-O-allylation product with an excellent yield of 99% in a relatively short reaction time (3.5 h), with trace amounts of by-products (<0.1%). This sustainable method is perfectly suitable for the synthesis on a larger scale (3 moles of the key substrate) and for the full O-allylation process.

Reactivity of short radicals at the initial stages of radical polymerization of allyl chloride: Chain growth versus addition to fullerene

AbstractA quantum‐chemical study of the C60 interaction with various radicals generated from monomers in radical polymerization is significant in the fundamental aspects. However, the interactions between fullerene and radicals formed from allyl monomers has been poorly studied. Using the modern density functional theory methods, we performed quantum‐chemical simulation on the C60 interaction with the radicals arising upon the initial stages of the allyl chloride polymerization. We have found that the addition of growth radicals (with 1–4 monomer units) to C60 are more favorable than the chain growth reactions. Herewith, the radicals with 2–4 monomer units are most reactive in the addition reaction. Our quantum‐chemical findings explain the features of the initial stages of the allyl chloride radical polymerization in the presence of C60, namely, the increasing inhibition degree of the radical copolymerization of allyl chloride with methyl methacrylate and increasing induction period of copolymerization with styrene.

Design of MFI Type Aluminum- and Titanium-Containing Zeolites

HZSM-5 (MFI type) of composition (Hx)[Al3+xSi12−xO24] × wH2O and nanocomposites NA/HZSM-5, NA:M/HZSM-5 (NA—nanoscale anatase; M = V, Ni, Ag) with Si/Al = 12, 25, 40, 300 (sp.gr. Pnma or P21/n; z = 8), as well as zeolites [(Ti4+xSi12−xO24] × wH2O (TS) with Si/Ti = 47, 53, 73.5 (sp.gr. Pnma) were studied by XRPD, XAS, FTIR-spectroscopy, BET, XPS, SEM, EDX, TPD, UV–VIS-spectroscopy, UV–DRS, and chemiluminescence methods. The results obtained together with photocatalytic, adsorption, antimicrobial, catalytic properties were analyzed using crystallochemical concepts and literature data. It was shown that NA or NA:M introduction into HZSM-5 leads, respectively, to the photodegradation of MeO dye in the UV region or difenoconazole in the visible range, and contributes to the appearance in the dark of adsorption (almost complete extraction of P(V), As(V), and Se(V) from aquatic environment) and bacteriostatic properties in respect to Staphylococcus epidermidis, Bacillus antracoides, and Escherichia coli for NA:Ag/HZSM-5(40, 300). The presence of titanium ions in NA nanoparticles on the HZSM-5 surface improves the catalytic activity in ethanol and propane (the best performance for NA/HZSM-5(25) and NA/HZSM-5(40), respectively) conversion. Determination of the composition (surface and bulk) and structure (statistical and local) of TS zeolites together with the found correlations made it possible to propose new catalysts in the reactions of propane, ethanol, and allyl chloride conversion.

Fast pyrolysis of polyurethanes and polyisocyanurate with and without flame retardant: Compounds of interest for chemical recycling

To date, the recycling of polyurethane (PU) and polyisocyanurate (PIR) waste still poses a significant problem. Within this contribution, the thermal degradation of high-resilient ether PU, semirigid PU, rigid PU, and (PIR) with and without TCPP flame retardant was studied at different temperatures to identify and quantify the main products. For this, a tandem micropyrolyzer coupled to GC × GC with FID and ToF-MS detectors was used, and the yield volatiles, light gases, and residue was quantified. The volatile pyrolysis vapours obtained from pyrolyzing high-resilient ether PU and semirigid PU at 600 °C were very similar, and the main products obtained were ethylene and propylene (combined yield of ~13 wt%), ~16 wt% of various oxygenates, and 4–6 wt% organic nitrogen compounds. The oxygenates included mostly poly-ether type compounds with varying molecular weight, and these are attributed to the decomposition of the polyol chains forming the soft segments of the polymer. The main semi-volatile nitrogen compound was 4,4′-methylenedianiline, attributed to the decomposition of the hard segments in the PU structure synthesized from MDI. The pyrolysis vapours from rigid PU contained several ether-type compounds and high yields of heteroatom-free monoaromatics—in particular styrene. The PIRs were more difficult to decompose and volatilize than the PUs, resulting in ~20 wt% higher residue yields. The charring propensity was even higher in the absence of a flame retardant in the formulation. Pyrolysis of TCPP-containing PIR produced Cl-containing pyrolysis vapours such as allyl chlorides. While the yield of H2O was comparable for the different PUs and PIR, pyrolysis of PIR produced higher yields of CO2 and less CO compared to the different PUs. The use of catalysts can help to convert PU waste pyrolysis vapours more efficiently to desirable chemicals.

Epoxidation of Allyl Chloride in the Presence of Tungsten Oxo–Peroxo Heteropoly Compounds of P(V), As(V), and Si(IV) Under Phase-Transfer Catalysis Conditions

Epoxidation of Allyl Chloride in the Presence of Tungsten Oxo–Peroxo Heteropoly Compounds of P(V), As(V), and Si(IV) Under Phase-Transfer Catalysis Conditions

Preparation of anatase-free hierarchical titanosilicalite-1 in favor of allyl chloride epoxidation

The exploration of highly efficient titanium silicalite-1 (TS-1) zeolite based on small crystal size and controllable coordination state of Ti species is of great importance in promoting the industrial application of TS-1. Herein, hierarchical small-crystal TS-1 free of anatase has been hydrothermally prepared via a glycine-assisted strategy in a tetrapropylammonium bromide (TPABr)-ethanolamine system. Under the synergistic effect of the glycine and seed, a 1 μm in sized microporous TS-1 zeolite was prepared with all Ti species existed in the form of framework Ti. By density functional theory (DFT) calculations, it was found that the self-condensation of Ti(OH)4 to TiO2 could be hindered in the presence of glycine. Furthermore, the TS-1 zeolite was alkaline etched to prepare hierarchical TS-1 free of anatase. The desilication could be slowed down and the framework Ti was basically preserved, when the glycine was present during post-synthesis treatment. The resultant hierarchical TS-1 exhibited a superior catalytic performance in the epoxidation of allyl chloride, that the H2O2 conversion and H2O2 utilization reached 99.3% and 99.7%, respectively. This preparation could simultaneously control over crystal size and coordination state of Ti species and also provide a practical strategy for exploring highly efficient zeolite catalyst.

Titanosilicalites (MFI-type): Composition, statistical and local structure, catalytic properties

This article presents the results of a study of three commercial titanosilicalites (TS-1, TS-1N, TS-1G) with general formula [(TixSi12-x)O24] × wH2O (MFI-type) using the X-ray study (XRPD), IR spectroscopy (FT-IR), X-ray absorption spectroscopy (EXAFS/XANES), differential scanning calorimetry (DSC), Brunauer–Emmett–Teller method (BET), UV-VIS spectroscopy. It was established that the samples contain amorphous oxygenous titanium-containing formations, which does not allow the use of quantitative elemental methods of analysis to determine the content of titanium ions in the framework. The full-profile Rietveld method was used to determine the silicate modules (Si/Ti = 53 for TS-1, Si/Ti~47 for TS-1N and TS-1G) and the coordination numbers of titanium: CNTi~5.0, CNTi = 4.5, CNTi>5.0, respectively in the structures of TS-1, TS-1N, TS-1G. The distribution of Ti4+ ions over the sites of the MFI-type structure with the orthorhombic symmetry (space group Pnma, z = 8) were found: T2, T6, T10 for TS-1, T8, T10, T5 (unlikely) for TS-1N (Т10 double positions in sinusoidal channels) and Т2, Т10, Т12, Т9 (unlikely) for TS-1G (Т10 and Т12 double positions in sinusoidal channels). The best indicators of the allyl chloride epoxidation in the epichlorohydrin process at 30 °C were achieved for TS-1N and TS-1G. A higher yield of acetaldehyde was found on the TS-1(75) sample (TS-1 sample annealed at 75 °C for 2 h) at 290 °C (non-oxidative ethanol conversion), and ethylene - on the TS-1G(500) sample (TS-1G annealed at 500 °C for 2 h) at 700 °C (propane conversion). The revealed correlations between the catalytic parameters and the characteristics of the samples studied were discussed.

A Novel Family of [1,4]Thiazino[2,3,4-ij]quinolin-4-ium Derivatives: Regioselective Synthesis Based on Unsaturated Heteroatom and Heterocyclic Compounds and Antibacterial Activity.

A novel family of [1,4]thiazino[2,3,4-ij]quinolin-4-ium derivatives was synthesized by annulation reactions of 8-quinolinesulfenyl chloride with unsaturated heteroatom and heterocyclic compounds. It was found that the reactions with 4-pentenoic and 5-hexenoic acids, allyl chloride and bromide, allyl cyanate and vinyl heterocyclic compounds (N-vinyl pyrrolidin-2-one and 1-vinylimidazole) proceeded in a regioselective mode but with the opposite regiochemistry. The reactions with vinyl heterocyclic compounds included electrophilic addition of the sulfur atom of 8-quinolinesulfenyl chloride to the β-carbon atom of the vinyl group. In the case of other substrates, the annulation proceeded with the attachment of the sulfur atom to the α-carbon atom of the vinyl group. The antibacterial activity of novel water-soluble compounds against Enterococcus durans, Bacillus subtilis and Escherichia coli was evaluated. Compounds with high antibacterial activity were found.

Peculiar Properties of Spontaneous Methacrylate Derivatives Polymerization with Haloidallyl Compounds

The reaction of spontaneous polymerization in the system of N, N-diethylaminoethyl methacrylate with allyl chloride and bromide, orthophosphoric acid in ethanol and dimethyl sulfoxide solutions is considered. Spontaneous polymerization proceeds, consisting of two stages: the quaternization reaction and the polymerization reaction. It was shown that the accompanying reaction of quaternization, spontaneous polymerization, takes place both in a mixture of reagents and in the presence of a solvent, in other words, and by mixing an unsaturated amine and an alkyl halide.

Indium‐mediated allylation of carbonyl compounds in deep eutectic solvents

This study describes, for the first time, the in situ generation of indium organometallic reagents in environmentally friendly deep eutectic solvents (DESs). The allylation process of different carbonyl compounds is achieved mediated by indium metal and using cheap allyl chloride derivatives. The unique DES properties allow to perform the reaction at room temperature and under air, obtaining yields ranging from 45% to 99%. It is possible to recycle the reaction medium for at least four consecutive cycles without much decrease of the observed results. Also, a linear correlation between the yield of the reaction and the density of the DESs is observed.

A Cyanide‐free Biocatalytic Process for Synthesis of Complementary Enantiomers of 4‐Chloro‐3‐hydroxybutanenitrile From Allyl Chloride

AbstractA biocatalyst used for selective ring scission of (±)‐5‐(chloromethyl)‐4, 5‐dihydroisoxazole to synthesize chiral (R)‐4‐chloro‐3‐hydroxybutanenitrile (90 % ee, 39 % isolated yield) and (S)‐5‐(chloromethyl)‐4, 5‐dihydroisoxazole (99 % ee, 39 % isolated yield) was developed by site‐saturated mutagenesis on aldoxime dehydratase derived from Pseudomonas chlororaphis B23 (OxdA). The positive mutant (OxdA‐L318I, E=68) improved the enantiomeric ratio E by 6‐fold as compared to the wild type enzyme (OxdA‐wild, E=11). The racemic precursor of (±)‐5‐(chloromethyl)‐4, 5‐dihydroisoxazole, used in the reaction, can be synthesized from readily available allyl chloride without utilizing highly toxic cyanide. The enantiopure (S)‐5‐(chloromethyl)‐4, 5‐dihydroisoxazole remaining in the kinetic resolution can be transformed into corresponding chiral (S)‐4‐chloro‐3‐hydroxybutanenitrile without loss of enantiomeric excess by treating it with triethylamine in acetonitrile (99 % ee, 72 % isolated yield) or catalysis of OxdA‐wild enzyme (99 % ee, 88 % isolated yield).

Synthesis of Poly[Allyl Chloride - Co Acrylic Acid] Polymers for Nucleic Track Detection from Alpha Particles

This paper describes the synthesis and development of new polymers for solid state nuclear trak detector of two novel poly Allyl cloride – co Acrylic acid and diethanol amine of polymeric detectors of alpha charged particle tracks. The detectors were irradiated by two radioactive sources, Amercium (Am-240) and Polonium (Po-210) for 5 hours, and traces of alpha particles were seen in the microscope and their diameters were measured. The results showed the density of tracks of alpha particles from (Am-240) and (Po-210) are 295.86, 655.33 respectively, while the average of their diameters are 5.83, 4.78 respectively.

Preparation and characterized study of new molecularly imprinted polymers for determination Cocaine by GC-Mass based on different Functional Monomers

Molecularly imprinted polymers (MIP) Showing high selectivity and affinity with an increasingly increasing analysis is now seen in the predetermined molecule (template) Furthermore, it is difficult to refine imprinted items due to the fact that there are multiple Variables to worry about, Any or all of this could have a likely effect on the chemical, Properties of the imprinted components in morphological and molecular identification, it is a rapidly emerging technique for the preparation of polymers having unique molecular recognition properties for a given compound MIP synthesis is a relatively easy and inexpensive process, either for its analogues or for a single enantiomer. For the selective extraction of COC and BE from urine samples, newly synthesized molecularly imprinted polymer sorbents were proposed in this report. using a functional monomer which To build a monolithic solid-phase micro extraction (SPME) fiber, Styrene and Allyl chloride are used, as well as Ethylene glycol methacrylate (EGDMA) as a suitable cross-linker and Cocaine as a template. A non-imprinted polymer was created by preparing a polymer without selective binding sites (NIP). All of these analytical procedures were utilized to extract, preconcentrate, and selectively determine Cocaine and its derivatives (SPME) with gas chromatography and mass spectrometry (GC/MS). sturdiness, The manufactured fiber's basic and vital role in SPME is due to its stability and durability. The samples were taken from a suspected cocaine abuser who was donated by the medico-legal directorate (Baghdad, Iraq). The analytes were monitored using a (GC MS), UV-vis, Scanning electron microscopy (SEM), and FTIR. The relative standard deviations (RSD percent ) for two patients' repeated studies for three measurements vary from (1.587-4.545) percent (at 20-100 ppm of Cocaine). Cocaine relative recoveries in human urine samples spiked with the drug are in the range of (102-105).

Synthesis of Chemical Precursors <i>via</i> the Catalytic Hydrogenation of 2-Chloropropene

Allyl chloride, which is a cross-linking agent for synthetic resins and a synthetic intermediate that is used as an alkylating agent for pharmaceuticals, is often utilized and synthesized at production sites related organochlorides. In the synthesis process of allyl chloride, however, 2-chloropropene (2-PEN) is produced as the by-product and that is a problem because it essentially has no practical use. In this study, it was investigated about the hydrogenation of 2-PEN to 2-chloropropane (2-PAN) and propylene, which are precursors for various chemical products. The commercially available palladium catalysts such as OleMax 201, OleMax 301, OleMax 600, and HyFlex 500 were used for 2-PEN hydrogenation. The maximum yield of 2-PAN (10.6 %) was detected at 348 K, P(H2) = 13.5 kPa and P(2-PEN) = 8.8 kPa, on OleMax 600 (0.5 g), while the maximum yield of propylene (26.0 %) was realized under the same reaction conditions, with the exception of using at P(H2) = 7.9 kPa on HyFlex 500 (0.5 g). The selective formation of propylene such as 8.9, 100, and 8.9 % for the conversion of 2-PEN, the selectivity of propylene, and the yield of propylene, respectively, was realized on OleMax 201. The selective formation of 2-PAN, however, was not observed on all catalysts. Palladium loading strongly influenced the catalytic activity, but had none on either the specific surface area, or basic and acidic properties.

Pathway Bifurcations in the Activation of Allylic Halides by Palladium and Their Influence on the Dynamics of η1 and η3 Allyl Intermediates.

Transition-metal-catalyzed allylic substitution often exhibits complex product selectivity patterns, which have been primarily attributed to π ↔ σ ↔ π isomerization of the η1 and η3 allyl intermediates. Product selectivity may be even further complicated if η1- and η3-allyls share a single transition state (TS), leading to their formation resulting in a post-transition-state bifurcation (PTSB). In this work, density functional theory calculations using ab initio molecular dynamics (AIMD) have been carried out that support the presence of a PTSB in Pd-catalyzed allylic halide activation directly influencing product selectivity. The AIMD results initiated from the TS predict the η1-allyl to be favored in the gas phase and a low dielectric (ε < 2.5) for trialkylphosphines, while the selectivity shifts toward the η3-allyl in higher dielectrics. The minimum energy path is also predicted to shift in product preference, consistent with the dynamics predictions. The bifurcation in allylic chloride activation is predicted to largely favor the η3-allyl at any solvent polarity. A PTSB was also discovered to be present in Ni and Pt allylic activation but with less bifurcation. These results offer a unique view into the mechanism of metal-catalyzed allylic substitution.

Cu(I)-Catalyzed 1,2-Alkynyl-propargylation and -benzylation of Benzyne Derivatives.

We report here a three-component, Cu(I)-catalyzed hexadehydro-Diels-Alder (HDDA) benzyne 1,2-difunctionalization reaction. This protocol allowed the introduction of two different carbon-based substituents onto the in situ-generated benzyne. These substituents were terminal monoynes or diynes partnered with propargylic, benzylic, or allylic chlorides. An example of a sequential HDDA reaction is demonstrated using the product of a 1,3-diyne and a propargylic halide, itself a newly created HDDA precursor.

Estimation of Trimethoprim by using a New Selective Electrodes dependent on Molecularly Imprinted Polymers

Trimethoprim-MIPs were prepared by using (TMP) as the template as well as allylchloride (AYC) or allylbromide (AYB) as monomer, used (TMPTA) tri methylol propane tri acrylate or ethylene glycol di methyl acrylate (EGDMA) as cross-linker and initiator used (BP) benzyl peroxide. By using different plasticizers (di butyl Phthalate (DBPH), Nitrobenzene (NB), oleic acid (OA) and paraffin) for TMP-MIP1 and (Di butyl sebecate (DBS), Di methyl acrylate (DMA), Tributylphosphate(TBP) and Tris(ethylhexyl phosphate (TEHP) ) for TMP-MIP2. Membranes of MIPs were prepared in PVC matrix. The characterizations of each electrode were determined The Slope range from (55.591 - 40.509) mV/decade, Limit of Detection (1 X 10 -5 - 5 X 10 -6) and Linearity range of electrodes MIPs from (1 X 10 -5 - 1 X 10 -1). Stable Signe of electrode pH from (3-9) and study the selectivity with additives of drugs synthesis (Glucose, Calcium stearate, sodium benzoate and benzoic acid) demonstrate strong selectivity.

Selective hydrosilylation of allyl chloride with trichlorosilane

The transition-metal-catalysed hydrosilylation reaction of alkenes is one of the most important catalytic reactions in the silicon industry. In this field, intensive studies have been thus far performed in the development of base-metal catalysts due to increased emphasis on environmental sustainability. However, one big drawback remains to be overcome in this field: the limited functional group compatibility of the currently available Pt hydrosilylation catalysts in the silicon industry. This is a serious issue in the production of trichloro(3-chloropropyl)silane, which is industrially synthesized on the order of several thousand tons per year as a key intermediate to access various silane coupling agents. In the present study, an efficient hydrosilylation reaction of allyl chloride with trichlorosilane is achieved using the Rh(I) catalyst [RhCl(dppbzF)]2 (dppbzF = 1,2-bis(diphenylphosphino)-3,4,5,6-tetrafluorobenzene) to selectively form trichloro(3-chloropropyl)silane. The catalyst enables drastically improved efficiency (turnover number, TON, 140,000) and selectivity (>99%) to be achieved compared to conventional Pt catalysts.

Effects of π*−σ* coupling on dissociative-electron-attachment angular distributions in vinyl, allyl, and benzyl chloride and in chlorobenzene

We report on a velocity map imaging study of ${\mathrm{Cl}}^{\ensuremath{-}}$ anions resulting from the dissociative electron attachment to four unsaturated chlorohydrocarbons. In all four molecules, this process is mediated by the formation of the lowest shape resonance. The choice of the molecules was motivated by the different character of this resonance. In the planar compounds chlorobenzene and vinyl chloride, it is a ${\ensuremath{\pi}}^{*}$ resonance, which is not dissociative along the C-Cl bond without distortion of the planar geometry. In the nonplanar compounds benzyl chloride and allyl chloride, the shape resonance has a mixed ${\ensuremath{\pi}}^{*}\text{\ensuremath{-}}{\ensuremath{\sigma}}^{*}$ character and is directly dissociative without the need for any additional distortion. Our motivation was to find out whether the dissociation-allowing nuclear motion has a common imprint in the resulting fragment angular distributions. In spite of the expected similarities between the two classes of compounds, the resulting images are quite different for all four molecules. We interpret the results, especially the imprints of the bending dynamics, with the aid of a single-electronic-state model in the axial recoil approximation.

Cu2O Nanocatalysts Immobilized on p(SBMA) for Synergistic CO2 Activation to Afford Esters and Heterocycles at Ambient Pressure

Herein, we report a chemoselective insertion of CO2 into unsaturated alkyne substrates under ambient conditions, which is achieved over poly (sulfobetain methacrylate) (p(SBMA)) supported Cu2O nanocatalyst (Cu2O/p(SBMA)) and a series of 3a,4-dihydronaphtho[2,3-c]furan-1(3H)-ones, can be obtained in excellent yields. Cu2O/p(SBMA) presents high performance for environment pressure activation and interpolation of CO2 into unsaturated alkyne substrates. This provides an attainable and competent catalyst for interpolation of CO2 into aryl alkynes, and binding allylic chlorides through SN2 mechanism in order to produce efficient ester and lactone heterocycles that are supposed to have favorable utilizations. All in all, these findings signify practical methods of hybrid catalyst development for detailed alterations, including CO2 employment in a green and sustainable manner.