Succinyl Dichloride Research Articles

PECULIARITIES OF THE BEHAVIOR OF SUCCINYL DICHLORIDE IN FRIEDEL-CRAFTS REACTION WITH THIOPHENES

The reactions of thiophene, 2-methyl-, and 2-bromothiophene with succinyl dichloride in the presence of AlCl 3 , TiCl 4 , and SnCl 4 have been studied. The effect of the acylation conditions, the relative amounts and nature of the Lewis acid on the ratio and yields of the 1,4-di(2-thienyl)-1,4-diones and 4-oxo-4-(2-thienyl)butyric acids formed have been demonstrated. Under the reaction conditions, the formation of 4,4-di(2-thienyl)but-3-enoic acids (the main products in many cases) and also 4,4-di(2-thienyl)-butyrolactones was demonstrated. How to Cite Smirnov, V. I.; Afanas'ev, A. V.; Belen'kii, L. I. Chem. Heterocycl. Compd. 2011 , 46 , 1199. [ Khim. Geterotsikl. Soedin. 2010 , 1485.] For this article in the English edition see DOI 10.1007/s10593-011-0653-z

New Production Processes of Dichlorohydrins from Glycerol Using Acyl Chlorides as Catalysts or Reactants

A new class of catalysts promoting the hydrochlorination of glycerol to obtain selectively 1,3-dichlorohydrin has recently been discovered. These catalysts are acyl chlorides and prove to be much more active and sometimes more selective than the corresponding carboxylic acids, usually employed to promote this reaction. Many different kinetic runs have been performed to compare the performances of acetyl chloride and acetic acid, propanoyl chloride and propionic acid, adipoyl dichloride and adipic acid, succinyl dichloride and succinic acid, and malonyl dichloride and malonic acid, respectively. In all cases, the activity of the acyl chloride proved to be much higher. This behavior has been discussed and explained on the basis of a possible reaction mechanism. The reaction occurs rapidly even if glycerol is contaminated with NaCl. By adding a stoichiometric amount of an acyl chloride to glycerol, the hydrochlorination occurs in a short time, with a high selectivity, without any external supply of HCl, beca...

Quantum chemical study of the electronic structure and reactivity of complexes of 4-oxo-4-(2-thienyl)- and 4-(5-methyl-2-thienyl)-4-oxobutyryl chlorides with aluminum chloride

The geometry and electronic structures of complexes of 4-oxo-4-(2-thienyl)- and 4-oxo-4-(5-methyl-2-thienyl)butyryl chlorides with aluminum chloride, as well as the corresponding carbocations, were studied in terms of the density functional theory (DFT) using the B3LIP/6-311+G(2d,p) method and the semiempirical PM6 method. An analysis of the relative energies of the complexes and cations made it possible to interpret side reactions accompanying the acylation of thiophenes with succinyl dichloride.

Peculiarities of the behavior of succinyl dichloride in Friedel-Crafts reaction with thiophenes*

The reactions of thiophene, 2-methyl-, and 2-bromothiophene with succinyl dichloride in the presence of AlCl 3 , TiCl 4 , and SnCl 4 have been studied. The effect of the acylation conditions, the relative amounts and nature of the Lewis acid on the ratio and yields of the 1,4-di(2-thienyl)-1,4-diones and 4-oxo-4-(2-thienyl)butyric acids formed have been demonstrated. Under the reaction conditions, the formation of 4,4-di(2-thienyl)but-3-enoic acids (the main products in many cases) and also 4,4-di(2-thienyl)-butyrolactones was demonstrated.

Bis(4-nitrophenyl) succinate

The title compound, C16H12N2O8, was prepared by the reaction of succinyl dichloride with 4-nitro­phenol. The mol­ecule is centrosymmetric and the two benzene rings are coplanar.

Thermomechanical film properties and aging of blends of poly(lactic acid) and malonate oligomers

AbstractMalonate oligomers were synthesized as plasticizers for poly(lactic acid) (PLA). Esterification reactions were performed between diethyl bishydroxymethyl malonate (DBM) and either adipoyl dichloride or succinyl dichloride. Two molar masses were obtained within each series. Blending was carried out with PLA and the four oligomers as well as the monomeric unit from the syntheses (DBM). Dynamic mechanical analysis and differential scanning calorimetry were used to investigate the viscoelastic mechanical and thermal film properties of the blends. All the investigated plasticizers reduced the glass‐transition temperature of PLA, and the plasticization effect was better for the plasticizers of low molar mass. However, the amorphous domains of PLA became saturated with plasticizer at a certain concentration, and phase separation occurred. A higher molar mass of the plasticizer caused this saturation to occur at lower plasticizer concentrations. Subsequently, the aging of the blends at the ambient temperature for 4 months induced phase separation in the blends containing DBM, whereas those with an oligomeric plasticizer were stable and remained compatible with PLA within the aging period. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2140–2149, 2004

Synthesis, reactivity, crystal and molecular structure of [5,14-dihydro-7,16-bis(2-oxo-3 H-furan-5-yl)-6,8,15,17-tetramethyldibenzo[b,i][1,4,8,11]tetraazacyclotetradecinato(2-)-κ 4N]nickel(II)

The reaction of the Ni(II) complex of 5,14-dihydro-6,8,15,17-tetramethyldibenzo[b,i][1,4,8,11]tetraazacyclotetradecine with succinyl dichloride leads to di- and monosubstituted derivatives bearing β,γ-unsaturated-γ-lactonic rings at the meso positions of the macrocycle. An aminolytic cleavage of these lactonic substituents gives rise to open-chain pendant groups containing the corresponding amide functions. A range of new complexes have been synthesized in this way with use of primary and secondary aliphatic and heterocyclic amines. The new products have been characterized by elemental analyses, 1H, 13C NMR, IR and ESI-MS spectral data. Single crystal X-ray studies revealed that the saddle-shaped molecules of [5,14-dihydro-7,16-bis(2-oxo-3 H-furan-5-yl)-6,8,15,17-tetramethyldibenzo[b,i][1,4,8,11]tetraazacyclotetradecinato(2-)-κ 4N]nickel(II) act as receptors with molecules of toluene forming 1:1 supramolecular complexes.

Activated cyanide

Addition of cis-Na[Fe 2(CN)Cp 2(μ-CO) 2CO] ( 1) to a twenty-fold excess of phthaloyl dichloride (succinyl dichloride, glutaryl dichloride) leads to the μ-phthalimidocarbyne ( 3) (μ-succinimidocarbyne ( 9), μ-glutarimidocarbyne ( 10)) [Fe 2Cp 2(μ-CO)(CO) 2]A (A = Cl ( a), PF 6 ( b), BPh 4 ( c)) complexes which are studied by IR, NMR ( 1H, 13C), MS (pos-FAB) and X-ray ( 3b,3c,10b). The C-N bonds in the N,N-diacylated cyano bridges are highly elongated ( 1.30 A ̊ ) in comparison with the CN triple bond in the cyanide precursor. Their facile cleavage in subsequent 1:1 reactions with a second [Fe 2(CN)Cp 2(μ-CO) 2CO] − anion to give the tetraferrioazaallenium system [Fe 2Cp 2-( μ-CO) (CO) 2[ μ 4-C N C]Fe 2Cp 2( μ-CO)(CO) 2] + prove 3 to be the long sought after ‘activated cyanide’ - intermediate in the synthesis of this compound from 1 and phthaloyl dichloride (2:1). In the reaction of 10b with 1, the tetrairon complex Fe 2Cp 2(CO) 3-( μ 4-CNC (= O) (CH 2) 3C(=O)NC)Fe 2Cp 2(CO) 3 ( 7) forms as a byproduct along with tetraferrioazaallenium, while the short-chain derivative Fe 2Cp 2(CO) 3( μ 4-CNC(=O)-C(=O)NC0Fe 2Cp 2(CO) 3 ( 8) is obtained from stoichiometric reaction of 1 with oxalyl dichloride.

Biodegradable polymers based on renewable resources: Polyesters composed of 1,4 : 3,6-dianhydrohexitol and aliphatic dicarboxylic acid units

A series of polyesters was synthesized by the bulk polycondensations of the respective combinations of three stereoisomeric 1,4 : 3,6-dianhydrohexitols [1,4 : 3,6-dianhydro-D-glucitol (1), 1,4 : 3,6-dianhydro-D-mannitol (2), and 1,4 : 3,6-dianhydro-L-iditol (3)] with succinyl dichloride (4a), glutaryl dichloride (4b), adipoyl dichloride (4c), and sebacoyl dichloride (4d). Biodegradability of these polyesters was investigated by three different methods, i.e., degradation in an activated sludge, soil burial degradation, and enzymatic degradation. Although polyesters (7b–7d) based on 3 and polyester 6a derived from 2 and 4a were crystalline and scarcely biodegraded, all the other amorphous polyesters were more or less biodegradable. Biodegradability of the polyesters was found to vary significantly depending on their molecular structures. Soil burial degradation of polyesters in the soil that was treated with antibiotics, together with electron scanning microscopic observation, showed that polyesters 5b and 5c prepared from 1 and 4b or 4c were degraded by both bacteria and filamentous fungi, whereas polyester 5d from 1 and 4d was degraded primarily by filamentous fungi. © 1996 John Wiley & Sons, Inc.

Biodegradable polymers based on renewable resources: Polyesters composed of 1,4 : 3,6‐dianhydrohexitol and aliphatic dicarboxylic acid units

A series of polyesters was synthesized by the bulk polycondensations of the respective combinations of three stereoisomeric 1,4 : 3,6-dianhydrohexitols [1,4 : 3,6-dianhydro-D-glucitol (1), 1,4 : 3,6-dianhydro-D-mannitol (2), and 1,4 : 3,6-dianhydro-L-iditol (3)] with succinyl dichloride (4a), glutaryl dichloride (4b), adipoyl dichloride (4c), and sebacoyl dichloride (4d). Biodegradability of these polyesters was investigated by three different methods, i.e., degradation in an activated sludge, soil burial degradation, and enzymatic degradation. Although polyesters (7b–7d) based on 3 and polyester 6a derived from 2 and 4a were crystalline and scarcely biodegraded, all the other amorphous polyesters were more or less biodegradable. Biodegradability of the polyesters was found to vary significantly depending on their molecular structures. Soil burial degradation of polyesters in the soil that was treated with antibiotics, together with electron scanning microscopic observation, showed that polyesters 5b and 5c prepared from 1 and 4b or 4c were degraded by both bacteria and filamentous fungi, whereas polyester 5d from 1 and 4d was degraded primarily by filamentous fungi. © 1996 John Wiley & Sons, Inc.

Synthesis and degradabilities of polyesters from 1,4:3,6‐dianhydrohexitols and aliphatic dicarboxylic acids

AbstractSix different polyesters (6a–6c and 7a–7c) were prepared by the bulk polycondensations of the respective combinations of 1,4:3,6‐dianhydro‐D‐glucitol (3) and 1,4:3,6‐dianhydro‐D‐mannitol (4) with succinyl dichloride (5a), glutaryl dichloride (5b), and adipoyl dichloride (5c) at 140–180°C. Polyesters having number average molecular weights up to 2.6 ×104 were obtained in high yields. Only polyester 7a based on 4 and 5a was partially crystalline, whereas all the other polyesters were amorphous. Thin films of these polyesters except that of 7a were spontancously hydrolyzed in a neutral phosphate buffer solution at 50°C, whereas they were reluctant to be hydrolyzed at 27°C. The polyesters were more or less degraded at 27°C by treatment with an activated sludge or by prolonged burial in soil. © 1995 John Wiley & Sons, Inc.

Side chain liquid crystalline polymers containing siloxane spacer: 7. Syntheses and properties of polyimides and polyamides containing a mesogenic side chain connected with a disiloxane linkage

Preparations of polyimides and polyamides containing a mesogenic group in the side chain connected with a siloxane bond in the spacer component were carried out. A 3,5-diaminobenzyloxy-type monomer having a mesogen consisting of a p'-substituted biphenyl benzoate group was prepared by means of hydrosilylation of 1-[3-43,5-dinitrobenzyloxy)propyl]-1,1,3,3-tetramethyldisiloxane with a mesogenic allyloxy compound, followed by catalytic reduction of the two nitro groups. The polyimides were synthesized by polycondensation of the diamine monomers with 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), followed by chemical imidization. The polyamides were also synthesized by polycondensation of the diamine monomers with dicarboxylic dichloride compounds, i.e., terephthaloyl dichloride, oxalyl dichloride, malonyl dichlonride, succinyl dichloride, glutaryI dichloride, adipoyl dichloride, pimeloyI dichloride and azelaoyl dichloride. The structural effects on the thermal properties of the polymers were investigated. The obtained polyamides having an aliphatic group in the main chain exhibited an enantiotropic smectic mesophase at around 100-150C, while no mesophase was observed for the polyimides and a polyamide having an aromatic backbone.

Radical graft polymerization from carbon whisker initiated by peroxyester groups introduced onto the surface

The radical graft polymerization of vinyl monomers onto carbon whiskers, i.e. vapor grown carbon fibers, initiated by tert-butyl peroxyester groups that are introduced onto the surface was investigated. The introduction of tert-butyl peroxyester groups onto the carbon whisker surface was achieved by the reaction of acyl chloride groups on the surface with tert-butyl hydroperoxide. The carbon whisker having acyl chloride groups was prepared by the following three methods: (1) reaction of surface carboxyl groups with thionyl chloride, (2) reaction of surface phenolic hydroxyl groups with succinyl dichloride, and (3) reaction of surface phenolic hydroxyl groups with phthaloyl dichloride. The carbon whiskers having tert-butyl peroxyester groups prepared from these three methods were abbreviated as CW-POE 1, 2, and 3, respectively. The peroxyester group content of CW-POE 1, 2, and 3 was determined to be 0.06, 0.05, and 0.17 mmol/g, respectively. It was found that the radical polymerization of vinyl monomers su...

水ガラスを原料とする多孔性アモルファスシリカの合成

Amorphous porous silica was prepared from silicic acid and dicarboxylic acid dichlorides. Silicic acid was treated with malonyl dichloride, succinyl dichloride, adipoyl dichloride and sebacoyl dichloride in tetrahydrofuran (THF) at room temperature, and resulting powd ers were calcined at 450, 600 and 800 °C for 3 h in the furnace under 0 atomsphere. The specific surface area of amorphous porous silica thus obtained could be controlled between 960 and 149 m2/g at 600 °C by chosing the starting dicarboxylic acid dichloride and calcination temperature.

Observations on Dibutylstannylene as Template for the Assembly of Macrocyclic Oligolactones

AbstractDibutylstannylene‐mediated macrolactonization of methyl 4,6‐O‐benzylidene‐&7alpha;‐D‐glucopyranoside (2) with glutaryl and phthaloyl dichloride yields the respective dilactones 6e and 6f and parallel tetralactones 5e and 5f as well as the antiparallel tetralactone 4e in the case of glutarylation. The reaction with malonyl dichloride yields a negligible amount of the parallel tetralactone 5d and that of fumaryl and isophthaloyl dichloride yields polyesters only, a byproduct in all these reactions. The mechanism of stannylene‐medidted macrolactonization is discussed incorporating data pertaining to known hexa‐ and octalactone formation when succinyl dichloride is used. A correlation between stannylene dimer symmetry and tetralactone constitutional isomer selectivity is introduced.

Surface modification of a biocompatible polymer based on polyurethane for artificial blood vessels

An OH-functionalized poly(carbonate urethane) (PCU) is used for developing a new antithrombogenic surface. Biomolecules like glycine or the fibronectin fragment Gly-Arg-Gly-Asp-Ser (GRGDS) are covalently bound to the PCU surface by succinyl dichloride coupling. The modification steps are controlled by infrared spectroscopy and amino acid analysis. Successfully modified films are tested under stationary cell culture conditions.

ChemInform Abstract: A Mild, Simple, and Convenient Synthesis of Diesters (IV) from Malonyl or Succinyl Dichloride (II) and Alcohols (I) Catalyzed by Potassium Tetracarbonylhydridoferrate, K(HFe(CO)4) (III), as a New Catalyst.

ChemInform Abstract: A Mild, Simple, and Convenient Synthesis of Diesters (IV) from Malonyl or Succinyl Dichloride (II) and Alcohols (I) Catalyzed by Potassium Tetracarbonylhydridoferrate, K(HFe(CO)4) (III), as a New Catalyst.

A Mild, Simple, and Convenient Synthesis of Diesters from Malonyl or Succinyl Dichloride and Alcohols Catalyzed by Potassium Tetracarbonylhydridoferrate, KHFe(CO)4, as a New Catalyst

A large variety of alcohols react with acyl halides of dicarboxylic acids such as malonyl dichloride and succinyl dichloride in the presence of a catalytic amount of tetracarbonylhydridoferrate at room temperature under carbon monoxide or nitrogen to give the corresponding diesters in good yields.

Nucleophilic Reactions of Hydrazido(2–) Complexes of Molybdenum and Tungsten with Succinyl Dichloride and Phenyl Isocyanate

Abstract Nucleophilic attack of the WNNH2 group in the hydrazido(2-) complex [WF(NNH2)(dpe)2][BF4] (dpe=Ph2PCH2CH2PPh2) on succinyl dichloride gives a novel ethanedioylhydrazido(2-) complex, [WF(NNCOCH2CH2CO)(dpe)2][BF4]. X-Ray structural analysis shows that the carbon, nitrogen, and oxygen atoms of the ethanedioylhydrazido(2-) ligand lie nearly in the same plane, indicating sp2 character of the nitrogen atom bearing the two carbonyl groups. Phenyl isocyanate also undergoes nucleophilic attack by the hydrazido(2-) complex [MBr(NNH2)(dpe)2]Br (M=Mo or W) to yield the phenylsemicarbazido(2-) type complex, [MBr(NNHCONHPh)(dpe)2Br. Treatment of the semicarbazido(2-) complex with triethylamine gives a new diazenido complex [MBr(NNCONHPh)(dpe)2].

Conversion of Succinyl Dichloride into γ‐Chlorocaproic Acid

Conversion of Succinyl Dichloride into γ‐Chlorocaproic Acid