Allyl Cyanide Research Articles

Removal of Nitriles from Synthetic Wastewater by Acrylonitrile Utilizing Bacteria

This study describes the ability of two bacteria strains, isolated from an ABS resin manufacturing wastewater treatment system, to remove high acrylonitrile concentrations. Straight chain aliphatic nitrile compound (propionitrile, allyl cyanide); branch chain aliphatic nitrile compound (isobutyronitrile) and aromatic nitrile compound (benzonitrile) removal by Comamonas testosteroni and Acidovorax sp. was also investigated. The results are: Comamonas testosteroni and Acidovorax sp. can remove acrylonitrile completely up to 1904.8 mg/L within 66.6 h and 1538.5 mg/L within 143.3 h, respectively. Comamonas testosteroni degraded acrylonitrile faster than Acidovorax sp., and accumulated much more acrylic acid in the medium than Acidovorax sp. The addition of acrylamide to the medium was removed by Comamonas testosteroni and Acidovorax sp. Both strains utilized acrylic acid, a metabolic by-product of acrylonitrile, as a carbon source and ammonium nitrogen, a metabolic by-product of acrylonitrile, as a nitrogen source for growth. Comamonas testosteroni and Acidovorax sp. removed propionitrile completely up to 1352.8 mg/L and 975.7 mg/L within 166.9 h, respectively. With isobutyronitrile as a substrate, more than 97.8% could be removed within 169.8 h by Comamonas testosteroni up to 1352.8 mg/L, and by Acidovorax sp. up to 975.7 mg/L. These two strains could remove allyl cyanide completely up to 775 mg/L within 49.1 h and benzonitrile completely up to 442.7 mg/L within 31.1 h. Because Comamonas testosteroni and Acidovorax sp. have good degrading ability for removing nitrile compounds they are expected to play an important role in the treatment of nitrile compounds.

Parallel ligand screening on olefin mixtures in asymmetric hydroformylation reactions.

[reaction: see text] Herein we describe a new protocol for catalyst evaluation in asymmetric hydroformylation reactions where multisubstrate screening is performed in an array of parallel reactors. This method was successfully demonstrated using a mixture of styrene, allyl cyanide, and vinyl acetate. Using this screening methodology, a set of phosphite ligands was evaluated and led to the discovery of a bisphosphite ligand that gave 88% ee and unprecedented >100:1 branched:linear regioselectivity in asymmetric hydroformylation of vinyl acetate.

The polymer electrolyte based on polysiloxane containing both alkyl cyanide and oligo ethylene oxide pendants

The monomers, (3-cyanopropyl) methylsiloxane cyclics (D4CN) and (3-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)propyl) methylsiloxane cyclics (D4TEG) were prepared by a hydrosilylation reaction of 2,4,6,8-tetramethylcyclotetrasiloxane (D4H) with allyl cyanide and tri(ethylene glycol) methyl allyl ether (allyl TEG), respectively, in toluene using a platinum(0)-1,3-divinyl-1,1,3,3-tetramethyl disiloxane complex as the catalyst. The new crosslinkable polymers with alkyl cyanide and ethylene oxide groups as the pendent were synthesized by ring opening polymerization and characterized by GPC and 1H NMR. And then, the crosslinked solid polymer electrolyte was prepared by UV radiation curing. The conductivities of samples were measured by impedance spectroscopy using an indium–tin oxide (ITO) electrode. As the results, the maximum ionic conductivities of the polymer were 1.15 × 10 −5 S cm −1 at 20 °C and 1 × 10 −4 S cm −1 at 60 °C. The electrolyte was stable electrochemically to 5 V versus Li +/Li at room temperature.

Synthesis and application of a new bisphosphite ligand collection for asymmetric hydroformylation of allyl cyanide.

A series of mono- and bidentate phosphites was prepared with (S)-5,5',6,6'-tetramethyl-3,3'-di-tert-butyl-1,1'-biphenyl-2,2'-dioxy [(S)-BIPHEN] as a chiral auxiliary and screened in the asymmetric hydroformylation of allyl cyanide. These hydroformylation results were compared with those of two existing chiral ligands, Chiraphite and BINAPHOS, whose utility in asymmetric hydroformylation has been previously demonstrated. Bisphosphite 11 with a 2,2'-biphenol bridge was found to be the best overall ligand for asymmetric hydroformylation of allyl cyanide with up to 80% ee and regioselectivities (branch-to-linear ratio, b/l) of 20 with turnover frequency of 625 [h(-)(1)] at 35 degrees C. BINAPHOS gave enantioselectivities up to 77% ee when the reaction was conducted in either acetone or neat but with poor regioselectivity (b/l 2.8) and activities 7 times lower than that of 11. The product of allyl cyanide hydroformylation using (R,R)-11 was subsequently transformed into (R)-2-methyl-4-aminobutanol, a useful chiral building block. Single-crystal X-ray structures of (S,S)-11 and its rhodium complex 19 were determined.

New biphenol-based, fine-tunable monodentate phosphoramidite ligands for catalytic asymmetric transformations.

Monodentate phosphoramidite ligands have been developed based on enantiopure 6,6'-dimethylbiphenols with axial chirality. These chiral ligands are easy to prepare and flexible for modifications. The fine-tuning capability of these ligands plays a significant role in achieving high enantioselectivity in the asymmetric hydroformylation of allyl cyanide and the conjugate addition of diethylzinc to cycloalkenones.

Kinetics, thermodynamics, and effect of BPh3 on competitive C-C and C-H bond activation reactions in the interconversion of allyl cyanide by [Ni(dippe)

Reaction of [(dippe)Ni(micro-H)](2) with allyl cyanide at low temperature quantitatively generates the eta(2)-olefin complex (dippe)Ni(CH(2)=CHCH(2)CN) (1). At ambient temperature or above, the olefin complex is converted to a mixture of C-CN cleavage product (dippe)Ni(eta(3)-allyl)(CN) (3) and the olefin-isomerization products (dippe)Ni(eta(2)-crotonitrile) (cis- and trans-2), which form via C-H activation. The latter are the exclusive products at longer reaction times, indicating that C-CN cleavage is reversible and the crotononitrile complexes 2 are more thermodynamically stable than eta(3)-allyl species 3. The kinetics of this reaction have been followed as a function of temperature, and rate constants have been extracted by modeling of the reaction. The rate constants for C-CN bond formation (the reverse of C-CN cleavage) show a stronger temperature dependence than those for C-CN and C-H activation, making the observed distribution of C-H versus C-CN cleavage products strongly temperature-dependent. The activation parameters for the C-CN formation step are also quite distinct from those of the C-CN and C-H cleavage steps (larger DeltaH(++) and positive DeltaS(++)). Addition of the Lewis acid BPh(3) to 1 at low temperature yields exclusively the C-CN activation product (dippe)Ni(eta(3)-allyl)(CNBPh(3)) (4). Independently prepared (dippe)Ni(crotononitrile-BPh(3)) (cis- and trans-7) does not interconvert with 4, indicating that 4 is the kinetic product of the BPh(3)-mediated reaction. On standing in solution at ambient temperature, 4 decomposes slowly to complex 5, with structure [(dippe)Ni(eta(3)-allyl)(N triple bond C-BPh(3)), while addition of a second equivalent of BPh(3) immediately produces [(dippe)Ni(eta(3)-allyl)](+)[Ph(3)BC triple bond NBPh(3)](-) (6). Comparison of the barriers to pi-sigma allyl interconversion (determined via dynamic (1)H NMR spectroscopy) for all of the eta(3)-allyl complexes reveals that axial cyanide ligands facilitate pi-sigma interconversion by moving into the P(2)Ni square plane when the allyl group is sigma-bound.

A Short Synthesis of 4‐Amino‐3‐hydroxybutyric Acid (GABOB) via Allyl Cyanide.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Pi–halogen dimer interactions and the inclusion chemistry of a new tetrahalo aryl host

The preparation of 1,4,8,11-tetrabromo-5b[small alpha],6,12b[small alpha],13-tetrahydropentaleno[1,2-b:4,5-b[prime or minute]]diquinoline is described. This is a further member of the tetrahalo aryl host family, and forms crystalline lattice inclusion compounds with many guests. The X-ray structures of the allyl cyanide, 1,2,3-trichloropropane, chlorobenzene, toluene, benzene-water, methyl chloroform and carbon tetrachloride inclusion compounds are described, and compared with that of the solvent-free apohost. Although several different structural types are produced, the recently reported pi-halogen dimer (PHD) interaction plays an important role in all of these, except for that of pure (where the packing energy is the least favourable of the series).

RhCl 3-catalyzed hydroboration of alkenyl nitriles

RhCl 3-promoted hydroboration–oxidation reactions of representative alkenyl nitriles have been carried out. Carbanion of acetonitrile is formed from the carboncarbon heterolytic bond breaking in allyl cyanide during hydroboration. An unexpected process-trimerization of carbanion of acetonitrile has lead to the formation of 4-amino-2,6-dimethylpyrimidine.

Photodissociation of Methacrylonitrile at 193 nm: The CN Radical Product Channel

Photodissociation dynamics of methacrylonitrile (H2CC(CH3)CN) and 2-butenenitrile at 193 nm have been investigated by measuring laser induced fluorescence spectra of CN fragments. From the spectra, internal and translational energy distributions of CN have been obtained. For both molecules, the measured energy distributions are well represented by statistical prior calculations, assuming the CN and allyl radical products rather than the propenyl isomer. Ab initio calculations were performed for the relevant product species and transition states for isomerization and CN elimination. It has been concluded that methacrylonitrile dissociates in the ground electronic state via allyl cyanide formed by CN and H atom migration prior to dissociation. The quantum yield of the CN channel from methacrylonitrile was measured to be 0.012 ± 0.001.

A short synthesis of 4-amino-3-hydroxybutyric acid (GABOB) via allyl cyanide

4-Amino-3-hydroxybutyric acid was synthesized from allyl cyanide in four steps in an overall yield of 38%. Ultrasonically promoted epoxidation of allyl cyanide with m-chloroperoxybenzoic acid giving oxiranylacetonitrile was used as a key step.

A new class of solid polymer electrolyte: synthesis and ionic conductivity of novel polysiloxane containing allyl cyanide groups

A monomer; (3-cyanopropyl)methylsiloxane cyclics, is prepared by a hydrosiliylation reaction of 2,4,6,8-tetramethylcyclotetrasiloxane with allyl cyanide in toluene using a platinum(0)-1,3-divinyl-1,1,3,3-tetramethyl disiloxane complex as the catalyst. The cross-linkable polysiloxane is synthesised by ring-opening polymerisation with (3-cyanopropyl) methylsiloxane cyclics using fuming sulfuric acid. The polymers, abbreviated as D 4D 2- n indicates the number of cyanide groups in the side chain), are characterised by FT-IR and 1 H NMR. The solid polymer electrolyte is prepared by UV irradiation in an Indium–tin oxide cell. The cyanide pendants on the network backbones make the lithium salt easy to dissolve, accelerate the migration of free lithium ions, and can lower the glass transition temperature ( T g) of the electrolyte. The maximum conductivity of the polymer with n=55 is 3.38×10 −5 S cm −1 at room temperature. The temperature dependence of ionic conductivity ( σ) obeys the Vogel–Tammann–Fulcher relationship which implies ionic conductivity ( σ) obeys the Vogel–Tammann–Fulcher relationship which implies a free-volume cation transport mechanism.

Competing ruthenium catalyzed metathesis condensation and isomerization of allylic olefins

Metathesis condensation and isomerization reactions of allylic compounds were examined using Grubbs’ second-generation ruthenium catalyst [Ru ∗]. Allyl alcohol and allyl cyanide undergo metathesis condensation releasing ethylene, with conversions being the highest reported for these substrates. However, competing olefin isomerization rather than metathesis can occur under certain conditions when heteroatoms are present at the allylic position to the olefin.

Plant-derived biomolecules in fermented cabbage.

The formation of plant-derived biomolecules during sauerkraut fermentation was studied. Cabbage was fermented with a starter culture, and the results were compared to the results of spontaneous fermentation. The concentration of flavonoids and glucosinolates was analyzed by HPLC, and that of the glucosinolate breakdown products, by GC-MS. Of the 20 different flavonoids tested, only kaempferol was found (0.9 mg/ kg FW, fresh weight). The content of kaempferol remained constant in the cabbage fiber matrix over the fermentation process. The nitrite concentration was below the detection limit in both fermentations. The total glucosinolate content in the raw material was 3.71 micro mol/g DW, dry weight. Glucosinolates were totally decomposed in both fermentations during two weeks, and different types of breakdown products were formed. Isothiocyanates, indole-3-carbinol, goitrin, allyl cyanide, and nitriles were determined in the fermented cabbage. Isothiocyanates and allyl cyanide were the predominant breakdown products in both fermentations. Sulforaphane nitrile and goitrin were found only in small quantities in the end products.

Tetra-σ attachment of allyl cyanide onSi(111)−7×7

The investigation of allyl cyanide adsorption on $\mathrm{Si}(111)\ensuremath{-}7\ifmmode\times\else\texttimes\fi{}7$ using high-resolution electron-energy-loss spectroscopy (HREELS), x-ray photoelectron spectroscopy (XPS), and ultraviolet photoelectron spectroscopy (UPS) reveals a tetra-\ensuremath{\sigma} binding mode through two $[2+2]$-like cycloaddition reactions. The HREELS spectra of chemisorbed monolayer show the absence of $\mathrm{C}=\mathrm{C},$ $\mathrm{C}\ensuremath{\equiv}\mathrm{N},$ and $\mathrm{C}{(sp}^{2})---\mathrm{H}$ stretching modes coupled with the appearance of $\mathrm{C}=\mathrm{N}$ stretching mode at \ensuremath{\sim}1590 ${\mathrm{cm}}^{\mathrm{\ensuremath{-}}1}$, demonstrating that both the $\mathrm{C}=\mathrm{C}$ and $\mathrm{C}\ensuremath{\equiv}\mathrm{N}$ of allyl cyanide directly participate in binding with the surface to form $\mathrm{C}\mathrm{---}\mathrm{C}$ and $\mathrm{C}\mathrm{=}\mathrm{N}$ bonds, respectively. This binding configuration was further confirmed in our XPS and UPS studies. The imine-containing skeleton formed on the surface can possibly be employed as a molecular template for a further modification of Si surfaces and syntheses in vacuum.

The role of Pi-conjugation in attachment of organic molecules to the silicon (0 0 1) surface

We have investigated the role of conjugation in attachment of multifunctional organic molecules to the Si(0 0 1) surface. The model molecules we have chosen are acrylonitrile (CH 2CHCN) and allyl cyanide (CH 2CHCH 2CN) due to the electron-withdrawing nature of the cyano group. X-ray photoelectron spectroscopy shows that significant difference in primary binding configuration exists. Infrared spectroscopy establishes that acrylonitrile attaches to the Si(0 0 1) surface primarily through a mechanism involving the cyano group, leading to a novel keteneimine structure that is evidenced by characteristic strong infrared absorbance at 1985 cm −1. Allyl cyanide adsorbs in a way that principally utilizes the vinyl portion of the molecule, leading mainly to alkane infrared absorbance below 3000 cm −1. These results show that conjugation can play an important role in controlling product distribution when attaching multifunctional organic molecules to the Si(0 0 1) surface.

Pi-halogen dimers and V-shaped tetrahalo aryl inclusion hosts

1,4,8,11-Tetrabromo-5bα,6,12bα,13-tetrahydropentaleno[1,2-b:4,5-b′]diquinoline 6 has been synthesised and found to be an efficient lattice inclusion host for a range of small solvent molecules. The compound is a new example of the tetrahalo aryl host family, a group of molecules characterised by having a combination of inclined aromatic planes and halogen substitution at their extremities. The X-ray structures of (6)·(carbon tetrachloride) and (6)2·(allyl cyanide) are presented and discussed in crystal engineering terms. Both structures contain a common motif (the pi-halogen dimer) where two inversion-related host molecules pack such that one bromine atom from each is situated in the cleft of its V-shaped partner. This efficient packing motif provides a combination of π⋯Br and OFF (offset face–face) interactions within one supramolecular building block.

Glucosinolate breakdown products as insect fumigants and their effect on carbon dioxide emission of insects

BackgroundGlucosinolate breakdown products are volatile, therefore good candidates for insect fumigants. However, although they are insecticidal, the mode of action of such natural products is not clear. We studied the insecticidal effect of these compounds as fumigants, and monitored the production of carbon dioxide by the insects as a probe to the understanding of their mode of action.ResultsThe fumigation 24-h LC50 against the house fly (Musca domestica L.) of allyl thiocyanate, allyl isothiocyanate, allyl cyanide, and l-cyano-2-hydroxy-3-butene was 0.1, 0.13, 3.66, and 6.2 μg cm-3, respectively; they were 0.55, 1.57, 2.8, and > 19.60 μg cm-3, respectively, against the lesser grain borer (Rhyzopertha dominica Fabricius). The fumigation toxicity of some of the glucosinolate products was very close to or better than that of the commercial insect fumigants such as chloropicrin (LC50: 0.08 and 1.3 μg cm-3 against M. domestica and R. dominica, respectively) and dichlorovos (LC50: < 0.02 and 0.29 μg cm-3 against M. domestica and R. dominica, respectively) in our laboratory tests. Significantly increased CO2 expiration was found in insects exposed to the vapor of allyl isothiocyanate, allyl thiocyanate and allyl isocyanate. Allyl isothiocyanate was also found to increase the CO2 expiration of the American cockroach (Periplaneta americana L.).ConclusionsGlucosinolate breakdown products have potential as biodegradable and safe insect fumigants. They may act on the insect respiratory system in their mode of action.

Determination of isothiocyanates and related compounds in mustard extract and horseradish extract used as natural food additives

Amounts of isothiocyanates and related compounds in a mustard extract and a horseradish extract for food additive use were determined by GC, after confirmation of the identity of GC peaks by GC/MS. Amounts of allyl isothiocyanate, which included that of allyl thiocyanate, because most of the allyl thiocyanate detected in the sample was assumed to have been formed from allyl isothiocyanate during GC analysis, were 97.6% and 85.4%, in the mustard extract and the horseradish extract, respectively. Total amounts of the identified isothiocyanates in the mustard extract and the horseradish extract were 98.5% and 95.4%, respectively. Allyl cyanide, a degradation product of allyl isothiocyanate, was found in the mustard extract and the horseradish extract at the levels of 0.57% and 1.73%, respectively. beta-Phenylethyl cyanide, a possible degradation product of beta-phenylethyl isothiocyanate, and allyl sulfides were found in the horseradish extract, at the levels of 0.13% and 0.46%, respectively. Allylamine, which is another degradation product of allyl isothiocyanate, was determined after acetylation, and was found in the mustard extract and the horseradish extract at the levels of 8 micrograms/g and 67 micrograms/g, respectively.

Photodissociation of allyl cyanide at 193 nm

Photodissociation dynamics of allyl cyanide at 193 nm has been investigated by measuring laser-induced fluorescence spectra of CN fragments. From the spectra, rotational and vibrational energy distributions of CN have been obtained. The measured average rotational energy is 1080, 900 and 760 cm −1 for v ″=0,1,2, respectively, and the fraction of the vibrational population is 0.70/0.24/0.06 for v ″=0/1/2. The measured distributions are well represented by statistical prior calculations, from which the detailed dissociation dynamics is discussed.