Cinnamoyl Chloride Research Articles

Bulky N(,N)-(Di)alkylethane-1,2-diamineplatinum(II) Compounds as Precursors for Generating Unsymmetrically Substituted Platinum(IV) Complexes

Investigations of the influence of bulky groups in the equatorial ligand sphere of platinum(IV) compounds on the complexes' stability and reaction pattern were performed. Four dihydroxidoplatinum(IV) complexes were reacted with anhydrides, cinnamoyl chloride, and n-propyl isocyanate and yielded the symmetric dicarboxylated products or, if steric hindrance was observed, unsymmetrically substituted monocarboxylated analogues. With the aim of raising the steric demand, the following ligands were chosen: N-cyclohexylethane-1,2-diamine, N,N-dimethylethane-1,2-diamine, N,N-diethylethane-1,2-diamine, and N,N-diisopropylethane-1,2-diamine. All of the novel complexes were characterized by electrospray ionization mass spectrometry (ESI-MS), one- and two-dimensional NMR spectroscopy, elemental analysis, and reversed-phase HPLC; complexes B3, C3, C6, and D4 were also analyzed by X-ray diffraction. Additionally, the cytotoxicities of 10 compounds toward the cisplatin-sensitive cell line CH1 and the intrinsically cisplatin-resistant cell lines A549 and SW480 were investigated, and IC50 values down to the nanomolar range were found. To aid in the interpretation of structure-activity relationships, log k(w) values as a measure for the lipophilicity were determined for all of the new complexes, and the rates of reduction of C1, C3, and C4 relative to satraplatin were determined by means of NMR spectroscopy and ESI-MS.

Photo and thermal properties of cinnamoyl Pluronic F-127

Cinnamoyl chloride was covalently attached to the ends of Pluronic F-127 chains. The molar ratio of cinnamoyl groups to Pluronic F-127 of the cinnamoyl Pluronic F-127 (Cin-Plu) was calculated to be about 1:1 on a 1H NMR spectrum. The melting point (around 52 °C) of Cin-Plu was somewhat less than that (around 55 °C) of Pluronic F-127. Furthermore, the melting point of Cin-Plu decreased to around 50 °C on UV irradiation. The micellization temperature of Pluronic F-127 was around 15 °C and it was affected neither by the covalent attachment of cinnamoyl chloride nor the UV irradiation. On the other hand, Pluronic F-127 solution (22% w/v) in distilled water became a gel at around 28 °C and Cin-Plu solution (22% w/v) at around 39 °C. The elevation in the gelation temperature is possibly because the cinnamoyl group interferes with the intermolecular hydrophobic interaction of propylene oxide blocks, a main cause for the gelation. Cin-Plu solution (22% w/v) which had been subjected to UV irradiation (365 nm, 400 W) for 3 h exhibited no gelation temperature but a gradual increase in viscosity when the solution temperature increased from 17 °C to 37 °C, possibly due to the coexistence of dimeric Cin-Plu and monomeric Cin-Plu. © 2013 Society of Chemical Industry

Synthesis and antibacterial evaluation of typharin analog: 6,8-dihydroxy-7-methyl-3-styryl-3,4-dihydroisocoumarin

Synthesis of the 6-hydroxy-7-methyl analog of typharin (8-dihydroxy-3-styryl-3,4-dihydroisocoumarin) isolated from the rhizomes of Typha capensis has been described. Direct condensation of 3,5-dimethoxy-4-methylhomophthalic acid (1) with cinnamoyl chloride at elevated temperature under inert conditions afforded 6,8-dihydroxy-7-methyl-3-styrylisocoumarin (2). Hydrolysis of isocoumarin to keto acid (3) followed by reduction and cyclodehydration of hydroxy acid analog (4) afforded ( ± )-6,8-dimethoxy-3-(4-methoxyphenyl)-3,4-dihydroisocoumarin (5). Demethylation of the latter using anhydrous aluminum chloride/ethane thiol furnished the title isocoumarin (6). Compounds (1–6) were screened for in vitro antibacterial activity against a representative panel of Gram-positive and Gram-negative bacteria using levofloxacin as the reference drug.

Synthesis and Biological Evaluation of Chalcone Derivatives (Mini Review)

Chalcones are the principal precursors for the biosynthesis of flavonoids and isoflavonoids. A three carbon α, β-unsaturated carbonyl system constitutes chalcones. Chalcones are the condensation products of aromatic aldehyde with acetophenones in attendance of catalyst. They go through an assortment of chemical reactions and are found advantageous in synthesis of pyrazoline, isoxazole and a variety of heterocyclic compounds. In synthesizing a range of therapeutic compounds, chalcones impart key role. They have showed worth mentioning therapeutic efficacy for the treatment of various diseases. Chalcone based derivatives have gained heed since they own simple structures, and diverse pharmacological actions. A lot of methods and schemes have been reported for the synthesis of these compounds. Amongst all, Aldol condensation and Claisen-Schmidt condensation still grasp high up position. Other distinguished techniques include Suzuki reaction, Witting reaction, Friedel-Crafts acylation with cinnamoyl chloride, Photo-Fries rearrangement of phenyl cinnamates etc. These inventive techniques utilize various catalysts and reagents including SOCl(2) natural phosphate, lithium nitrate, amino grafted zeolites, zinc oxide, water, Na(2)CO(3), PEG400, silicasulfuric acid, ZrCl(4) and ionic liquid etc. The development of better techniques for the synthesis of α, β- unsaturated carbonyl compounds is still in high demand. In brief, we have explained the methods and catalysts used in the synthesis of chalcones along with their biological activities in a review form to provide information for the development of new-fangled processes targeting better yield, less reaction time and least side effects with utmost pharmacological properties.

Synthesis and structure of N-aryl(phenoxy, benzylidene)acetyl-1,4-benzoquinone monoimines

New N-aryl(phenoxy, benzylidene)acetyl-1,4-benzoquinone monoimines were synthesized by reaction of aminophenols with arylacetyl, phenoxyacetyl, and cinnamoyl chlorides in dimethylformamide-acetic acid (1: 3) in the presence of anhydrous sodium acetate. Structural parameters of the products and their probable biological activity were determined.

Preparation and characterization of UV-sensitive chitosan for UV-cure with poly(ethylene glycol) dimethacrylate

In this study, gel membranes of chitosan-g-poly(ethylene glycol) dimethacrylate (CS-g-PEGDMA) with pH sensitive properties were synthesized without employing any photo-initiator and crosslinker. First, CS was endowed with UV-sensitive property by reaction with cinnamoyl chloride in methanesulfonic acid. The reaction mainly occurred on the hydroxyl groups of the pyranose unit, while most C-2 amino groups were protected. The substitution degree of cinnamoyl group was 0.98, while the protection efficiency of –NH2 was about 80 %. Upon UV-irradiation, initial free radicals were produced only along the cinnamoyl-modified CS chains, which induced the grafting of PEGDMA from the chitosan chains and eventually the crosslinking. Increasing the feeding amount of PEGDMA increased the grafting ratio as well as the crosslinking density. The Tg value decreased from 161 °C for the pure chitosan to about 90 °C for the CS-g-PEGDMA with a grafting ratio of 1.29. Two stages of degradation correspondent to the individual degradation of CS chains and the PEGDMA chains were observed for all CS-g-PEGDMA copolymers, demonstrating their nature of graft copolymers. The tensile mechanical properties of the CS-g-PEGDMA membranes were affected by the two opposing factors: inter-connected soft PEGDMA chains and crosslinking density; and the optimum properties were achieved when the grafting ratio was increased to about 0.80. By combining CS and PEGDMA components, these copolymer membranes thus have the potential to be used as biomedical membranes.

Preparation and Application of a Dual Light-Responsive Triblock Terpolymer

Reported are the preparation and application of a triblock terpolymer poly(ethylene oxide)-ONB-poly[2-(perfluorooctyl)ethyl methacrylate]-block-poly(2-cinnamoyloxyethyl methacrylate) (PEO-ONB-PFOEMA-b-PCEMA). Here PEO is water-soluble, PCEMA is photo-cross-linkable, PFOEMA is of low surface tension, and ONB denotes a photocleavable o-nitrobenzyl unit at the junction of the PEO and PFOEMA blocks. To prepare the copolymer, a macroinitiator bearing an ONB unit between PEO and the initiating site was first synthesized. FOEMA and 2-trimethylsilyloxyethyl methacrylate (HEMA-TMS) were then sequentially polymerized by atom transfer radical polymerization (ATRP) to yield the triblock copolymer PEO-ONB-PFOEMA-b-P(HEMA-TMS). Removal of the trimethylsilyl groups from the P(HEMA-TMS) block and cinnamation of the resultant poly(2-hydroxyethyl methacrylate) block with cinnamoyl chloride resulted in the targeted triblock copolymer. PEO-ONB-PFOEMA-b-PCEMA formed micelles in tetrahydrofuran/water at the water volume fracti...

A New Rhodamine-Based “Off-On” Fluorescent Chemosensor for Hg (II) Ion and its Application in Imaging Hg (II) in Living Cells

A novel rhodamine derivative (Rh-C), synthesized by the reaction of rhodamine ethylenediamine and cinnamoyl chloride, was evaluated as a chemoselective Hg(2+) ion sensor. Addition of Hg(2+) to an ethanol aqueous solution of the Rh-C resulted in a color change from colorless to obvious pink color together with distinctive changes in UV-vis absorption spectrum and fluorescence spectrum. However, other common alkali-, alkaline earth-, transition- and rare earth metal ions induced no or minimal spectral changes. The interaction of Hg(2+) and sensor Rh-C was proven to adopt a 1:1 binding stoichiometry and the recognition process is reversible. The chemosensor displayed a linear response to Hg(2+) in the range of 0.4-5 μM with a detection limit of 7.4 × 10(-8) M. The sensor Rh-C was also successfully applied to the imaging of Hg(2+) in HL-7702 cells.

Synthesis and antitumor activity of lapathoside D and its analogs

Phenylpropanoid sucrose esters are important class of plant-derived natural products and have greater potential to be leads for new drugs because of their structural diversity and broad-array of pharmacological and biological activities. Regio- and chemo-selective acylation of 2,1′:4,6-O-di-isopropylidene sucrose 4 with cinnamoyl chloride 5 and p-acetoxycinnamoyl chloride 6 afforded mono-, di-, tri- and tetra- variant PSEs in moderate yields. The first total synthesis of di-substituted PSE, lapathoside D 1′ has been achieved successfully in short and simple synthetic steps from sucrose 3 as an inexpensive starting material. Lapathoside D 1 and a set of selected synthesized PSEs were tested for in vitro cytotoxicity against human cervical epithelioid carcinoma (HeLa) cell lines. Most of the compounds exhibited significant antitumor activity with their IC50 values ranging from 0.05 to 7.63 μM. The primary screening results indicated that PSEs might be valuable source for new potent anticancer drug candidates.

Effects of ethylene as comonomer on the active center distribution of 1-hexene polymerization with MgCl 2-supported Ziegler–Natta catalysts

1-Hexene homopolymerization and 1-hexene–ethylene copolymerization with TiCl 4/MgCl 2–Al(C 2H 5) 3 catalyst were compared to investigate the effect of ethylene on the distribution of active centers. The polymerizations were quenched with cinnamoyl chloride, and the number of active centers ([C*]/[Ti]) was determined by measuring the cinnamoyl group labeled on the propagation chains. Both polymer samples were fractionated into 9–10 fractions according to molecular weight, and [C*]/[Ti] in each fraction was also determined. Adding small amount of ethylene in 1-hexene polymerization markedly increased the number of active centers that produce low molecular weight polymer. This phenomenon agrees with the mechanism suggesting the presence of Ti−CH(CH 3)(CH 2) 3CH 3 type dormant sites and their activation by ethylene. The k p value of the newly emerging active centers in the copolymerization system is much lower than that of the homopolymerization system. In the copolymerization system, the active centers producing polymer chains of the second highest molecular weight and isotacticity show the highest k p value, while those producing polymer of the highest molecular weight and isotacticity show only the second highest k p. On the other hand, the active centers producing polymer with lower–middle chain length show the lowest ethylene incorporation rate. These results disclose differences of catalytic properties between the multiple active center types and correlations between their different kinetic parameters, which may lead to new understanding of the active centers and polymerization mechanism.

Novel Route to Control Interfacial Properties of Glass Fiber-Reinforced Polystyrene Composites via a Photo-Cross-Linkable Block Copolymer Coupling Agent

A diblock copolymer of polystyrene–block–poly(2-hydroxyethyl acrylate) (PS-b-PHEA) was synthesized via atom transfer radical polymerization (ATRP) and reacted with cinnamoyl chloride in triethylamine to yield PS-b-(PCEA-co-PHEA) copolymer with photo-cross-linkable poly(2-cinnamoylethyl acrylate) (PCEA) moieties. Then the triblock copolymer of polystyrene–block–poly(2-cinnamoylethyl acrylate-co-2-hydroxyethyl acrylate)–block–poly(γ-methacryloxypropyltrimethoxysilane) (PS-b-(PCEA-co-PHEA)-b-PMPS) was synthesized viaATRP from PS-b-(PCEA-co-PHEA) copolymer. Using as-prepared triblock copolymer as a macromolecular coupling agent to modify glass fibers, via microbond tests, the interfacial bond strength between pretreated glass fiber and polystyrene was compared before and after copolymer photo-crosslinking. The partially crosslinked block copolymer coupling agent greatly improved the interfacial adhesion of glass fiber-reinforced polystyrene.

Acylation of Ferrocene with Adamantoyl Chloride and Cinnamoyl Chloride

Liquid phase acylation of ferrocene with adamantoyl and cinnamoyl chloride was studied over different structural types of zeolites. The effect of the zeolite structure and acidity, and the influence of the reaction conditions on the ferrocene conversion and selectivity was investigated. The highest ferrocene conversions were achieved over zeolite Beta with Si/Al ratio 12.5 (cinnamoyl chloride 63.5%, adamantoyl chloride 45.9%). It was observed that with decreasing concentration of active sites in zeolite Beta the ferrocene conversion decreases. In addition, it was found that there is an optimum molar ratio of ferrocene to acylating agent, the ferrocene conversion increased with increasing temperature and amount of catalyst. The most important finding is that acylation of ferrocene with adamantoyl and cinnamoyl chloride leads exclusively to monoacylated products, most probably due to a deactivation of the cyclopentadiene rings after the attachment of the first acyl group.

Stereocontrolled Photodimerization with Congested 1,8-Bis(4′-anilino)naphthalene Templates

Suzuki cross-coupling of a 1,8-dihalonaphthalene with 4-methoxy-3-methylphenylboronic acid or 4-acetamidophenylboronic acid and subsequent functional group transformation gave 1,8-bis(3'-methyl-4'-anilino)naphthalene, 16, and 1,8-bis(4'-anilino)naphthalene, 21, in 65% and 90% overall yield, respectively. These congested compounds exhibit two cofacial aniline rings that favor a proximate, parallel arrangement of covalently attached cinnamoyl units suitable for stereoselective photodimerization. The [2 + 2]cycloaddition was found to proceed with high yield and exclusive formation of cis,trans,cis-cyclobutane-1,2-dicarboxylic acids. Amide formation with cinnamoyl chloride and template 21 followed by photochemical dimerization and acidic hydrolysis gave β-truxinic acid, 10, in 69% overall yield. Coupling of 21 and (E)-3-(3,4-dimethylphenyl)acrylic acid in the presence of EDC, UV irradiation, and cleavage gave cis,trans,cis-3,4-bis(3,4-dimethylphenyl)cyclobutane-1,2-dicarboxylic acid, 26, in 60% yield. In both cases, the template was quantitatively recovered.

ChemInform Abstract: Asymmetric Michael Additions of Grignard Reagents to Cinnamamides Deriving from N-Alkyl (R)-(-)-2-Aminobutan-1-ol.

Abstract Reaction of cinnamoyl chloride with various N -alkyl derivatives of (R)-(−)-2-aminobutan-1-ol (a readily available reagent) afforded the corresponding cinnamamides. Michael additions of Grignard reagents to the latter, followed by acidic hydrolysis, yielded optically active β-phenylalkanoic acids whose ee most generally were in the range 72–100%.

Perhydrofuro[3,2-c]-, perhydropyrano[3,2-c]-, and 4-ethoxy-2-(5-R-furan-2-yl)tetrahydroquinolines. Synthesis and transformations

Partly hydrogenated 2-[5-methyl(bromo, nitro)furan-2-yl]-substituted furo[3,2-c]quinolines, pyrano-[3,2-c]quinolines, and 4-ethoxyquinolines were synthesized by the imino Diels-Alder (Povarov) reaction. Cycloadditions of these compounds with maleic, citraconic, and dibromomaleic anhydrides, as well as with acryloyl, methacryloyl, and cinnamoyl chlorides led to the formation of substituted epoxyisoindolo[2,1-a]-quinolines and -quinolinecarboxylic acids. Oxidation of the double C=C bond in the adducts, esterification of the carboxy group, and aromatization of the 7-oxabicycloheptene fragment were accomplished.

Metal uptake by chitosan derivatives and structure studies of the polymer metal complexes

Two modified chitosan polymers were obtained by reaction of chitosan with cinnamoyl chloride and cinnamoyl isothiocyanate to produce two new derivatives. The new modified polymers were characterized by elemental and spectral analysis to confirm their structures. Their metal up take capacity was investigated both under competitive and noncompetitive conditions. At pH 5.6, the (ChitoCin and ChitoThioCin) polymers exhibit higher capacity for Cu(II) (0.461–0.572 mmol/g) than the other metal ions used. Where the capacities of the other metal ions are: Fe(III) (0.235–0.341 mmol/g), Cr(III) (0.078–0.099 mmol/g), Co(II) (0.046–0.057 mmol/g) and Ni(II) (0.041–0.053 mmol/g). These results show that the capacity of ChitoThioCin polymer is higher than that of ChitoCin for each metal ion. However, at lower pH the capacities (for Cr(III) pH < 1.8 and Fe(III) pH < 3.1) are higher than other metal ions under investigation. It has been found that the absorption follows the Langmuir isotherm better than that of the Freundlich isotherm. The metal complexes with several metal cations were isolated and their structures with the new chitosan polymers were found to be octahedral and schematic representations of the complexes were given.

Selective Monoacylation of Ferrocene with Bulky Acylating Agents over Mesoporous Sieve AlKIT‐5

Ferrocene acylation with bulky acylating agents (1-adamantoyl, benzoyl, 2-chlorobenzoyl, and cinnamoyl chlorides; and benzoic anhydride) catalyzed by AlKIT-5 mesoporous catalysts was investigated. AlKIT-5 catalysts with varying ratios of Si/Al were synthesized using tetraethoxysilane and aluminum isopropoxide as the structural building blocks and Pluronic F127 as a template under acidic conditions and were characterized in detail by X-ray powder diffraction, magic-angle spinning (MAS) NMR spectroscopy, sorption of nitrogen, energy-dispersive X-ray spectroscopy (EDS), SEM, TEM, and FTIR with pyridine as a probe molecule. The catalytic activity of the prepared AlKIT-5 catalysts in ferrocene acylation was shown to depend on the type of the acylating agent, thus likely reflecting the strength of interactions between the acyl source, the product, and the solid catalysts when the acylation reaction was carried out at 100 degrees C. In all reactions, the AlKIT-5 catalysts afforded exclusively the monoacylated products (100% selectivity) most likely due to deactivation of the second cyclopentadiene ring by attachment of the first acyl group, steric reasons, and some competitive interactions of the monoacylferrocenes with the catalysts. The prepared AlKIT-5 catalysts could be regenerated without any significant loss of the ferrocene conversion.

A new method of active center determination for olefin polymerization with supported Ziegler-Natta catalysts

A novel method based on a reaction between the growing polymer chain and cinnamoyl chloride (CC) was developed to determine the number of active centers (Cp) in olefin polymerization with supported Ziegler-Natta catalysts. The reaction of titanium-polymeryl bonds in the active centers of MgCl2/ID/TiCl4-AlR3 type catalysts with CC was very fast at 20∼80 °C. Cinnamoyl labeled polymer chains were formed, which were stable in the reaction system for at least 10 min when the CC/Al molar ratio was > 1. The number of active centers was determined by measuring the number of carbonyl groups in the polymer with the UV-vis method. The Cp values of the 1-hexene polymerization systems with the addition of hydrogen were also measured. Open image in new window

On the Importance of the Aromatic Ring Parameter in Studies of the Solvolyses of Cinnamyl and Cinnamoyl Halides

In solvolysis studies using Grunwald-Winstein plots, dispersions were observed for substrates with aromatic rings at the α-carbon. Several examples for the unimolecular solvolysis of monoaryl benzylic derivatives and related diaryl- or naphthyl- substituted derivatives have now been reported, where the application of the aromatic ring parameter (I) removes this dispersion. A recent claim suggesting the presence of an appreciable nucleophilic component to the I scale, has now been shown, in a review of the solvolysis of highly-hindered alkyl halides, to be unlikely to be correct. Attention is now focused on the application of the hI term for the solvolysis of compounds containing a double bond in the vicinity of any developing carbocation. Available specific rates of solvolysis (plus some new values) at 25°C of cinnamyl chloride, cinnamyl bromide, cinnamoyl chloride, p-chlorocinnamoyl chloride, and p-nitrocinnamoyl chloride are analyzed using the simple and extended (including the hI term) Grunwald-Winstein equations.

ChemInform Abstract: Novel Heterocycles. Synthesis of 2,3-Dihydro-6-methyl-2-phenyl-4H,6H-pyrano[3,2-c] [2,1]benzothiazin-4-one 5,5-Dioxide and Related Compounds.

The reaction of 2-chloro-4-(methylsulfonyl)benzoyl chloride (5) with 1-methyl-1H-2,1-benzothiazin-4-(3H)-one 2,2-dioxide (4) gave the O-benzoyl compound, 1-methyl-2,2-dioxido-1H-2,1-benzothiazin-4-yl 2-chloro-4-(methylsulfonyl)benzoate (6), which rearranged to give the C-benzoyl isomer, [2-chloro-4-(methylsulfonyl)phenyl] (4-hydroxy-1-mefhyl-2,2-dioxido-1H-2,1-benzothiazin-3-yl)methanone (7). The O-cinnamoyl compound 13 that resulted from the addition of 2,4-dichlorocinnamoyl chloride (11) to compound 4 rearranged to give the C-cinnamoyl compound, 3-(2,4-dichlorophenyl)-1-(4-hydroxy-1-methyl-2,2-dioxido-1H-2,1-benzothiazin-3yl)-2-propen-1-one (15). On the other hand, 1-methyl-2,2-dioxido-1H-2,1-benzothiazin-4-yl 3-phenyl-2-propenoate (19) (from cinnamoyl chloride (17) and compound 4) rearranged to give 2,3-dihydro-6-methyl-2-phenyl-4H,6H-pyrano[3,2-c][2,1]benzothiazin-4-one 5,5-dioxide (21), an example of a hitherto unknown ring system. Additional examples of this novel heterocycle were prepared from 1-methyl-7-(trifluoromethyl)-1H-pyrido[2,3-c][1,2]thiazin-4(3H)-one 2,2-dioxide (23) and 1-methyl-1H-thieno[3,2-c][1,2]thiazin-4(3H)-one 2,2-dioxide (8).