Phthaloyl Dichloride Research Articles

Synthesis and ring‐opening polymerization of macrocyclic aryl ketone oligomers

AbstractA series of macrocyclic aryl ketone oligomers were prepared by the reaction of phthaloyl dichloride or isophthaloyl dichloride with various bridge‐linking electron‐rich aromatic hydrocarbons 3a–d under pseudo‐high dilution conditions in the presence of Lewis base via Friedel–Crafts acylation reaction. Detailed structural characterization of these oligomers confirmed the cyclic nature by a combination of MALDI‐TOF‐MS, GPC, and 1H NMR analyses. These cyclic ketone oligomers have high solubility in organic solvents and the cyclic oligomers derived from phthaloyl dichloride are amorphous. The cyclic ketone oligomers readily undergo anionic ring‐opening polymerization in the melt by using potassium 4,4′‐biphenoxide as the initiator, producing linear, high molecular weight poly(ether ketone)s. Moreover, the isothermal chemorheology of the ring‐opening polymerization of cyclic oligomers 4a and 4b was also investigated. The results show that the shear viscosity of the molten reactive mixture is lower than 10 Pa · S at a constant shear rate of 0.05 rad/sec and increases slowly in the initial stage of ring‐opening polymerization. Copyright © 2009 John Wiley & Sons, Ltd.

A New Class of Tröger’s Base Analogues Bearing Spiro[4.5] Lactone Straps

A protocol for the introduction of spiro[4.5] lactone straps onto the Troger's base scaffold has been developed. The conversion was found to be most efficient when an appropriate carboxylic acid derivative reacted with 5,6,11,12-tetrahydrodibenzo[b,f][1,5]diazocines. Whilst phthaloyl dichloride was the main strap-forming precursor used, other 1,2-unsaturated dicarboxylic acids could be used in the presence of N,N'-dicyclohexylcarbodiimide.

Rapid phthaloylation and succinylation of hemicelluloses by microwave irradiation

AbstractRapid phthaloylation and succinylation of wheat straw hemicelluloses with phthaloyl dichloride (PdC) and succinyl chloride (SC) in N,Ndimethylformamide/ lithium chloride (DMF/LiCl) system using N-bromosuccinimide (NBS) as a catalyst was achieved for only 5 minutes at 50 °C by microwave irradiation. The degree of substitution (DS) ranged between 0.43 and 1.47. The effect of the molar ratios of xylose units in hemicelluloses to phthaloyl dichloride or succinyl chloride on the degree of substitution was investigated. It was found that the reactivity of succinyl chloride was higher as compared to Phthaloyl dichloride under similar experimental conditions. 13C NMR studies revealed that the esterification occurred at the C-3 and C-2 positions in the β-D-xylose units of hemicelluloses, but preferentially at C-3 position. However, it should be noted that microwave irradiation did result in more degradation of the macromolecular hemicelluloses than conventional heating technique as shown by a lower thermal stability of the hemicellulosic derivatives obtained by microwave irradiation than those obtained by conventional heating technique.

A One‐Pot Synthesis of 1,3‐Dihydro‐1,3,3‐tris(perfluoroalkyl)isobenzofuran‐1‐olates and Their Complete NMR Spectroscopic Analysis on the Basis of 1D and 2D Experiments

AbstractA convenient synthesis of the 1,3‐dihydro‐1,3,3‐tris(perfluoroalkyl)isobenzofuran‐1‐ols 3a,b was elaborated starting from commercially available phthaloyl dichloride and trimethyl(perfluoroalkyl)silanes (Me3SiRf) 1a,b (Rf=CF3, C2F5) in the presence of a fluoride source (Schemes 1 and 3). In a reaction analogous to alkyl Grignard reagents, double chloride substitution by two perfluoroalkyl groups and subsequent addition of one perfluoroalkyl group with concomitant ring closure led to this new class of compounds (Scheme 2). The syntheses of the alcohols and some alcoholates, as well as of the corresponding trimethylsilyl ethers are described. A combination of special 1D and 2D NMR experiments allowed the assignment of all atoms of the new compounds. The solid‐state structure of 1,3‐dihydro‐1,3,3‐tris(trifluoromethyl)isobenzofuran‐1‐ol (3a) was elucidated by X‐ray diffraction methods.

Design of reversible multi-electron redox systems using benzochalcogenophenes containing aryl and/or ferrocenyl fragments

2,3-Disubstituted benzo[ b]thiophenes, 1,3-disubstituted benzo[ c]thiophenes, and 1,3-disubstituted benzo[ c]selenophene have been systematically and selectively synthesized from benzo[ b]thiophene or phthaloyl dichloride as a starting material, respectively. Characterization of the molecules was performed by physical and spectroscopic means and X-ray crystallographic analyses. The cyclic voltammograms of the chalcogenophene derivatives containing aryl fragments showed well-defined reversible both anodic and cathodic steps derived from the unusually stable 5π chalcogenophene radical cations and 7π chalcogenophene radical anions. The cyclic voltammograms of the novel chalcogenophene derivatives containing ferrocenyl fragments showed a well-defined reversible cathodic step derived from the unusually stable 7π chalcogenophene radical anions and two distinct reversible anodic steps derived from ferrocenium cations separated from each other by a thiophene-heterocycle. The radical character of several novel 7π chalcogenophene radical anions was measured by ESR spectroscopy.

Synthesis of γ‐(2,4‐Dioxobut‐1‐ylidene)butenolides by Reaction of Masked 1,3‐Dicarbonyl Dianions with Maleic Anhydrides and Phthaloyl Dichloride.

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Synthesis, structure, and both cathodic and anodic reversible redox reactions of benzochalcogenophenes containing ferrocene units

2,3-Diferrocenylbenzo[ b]thiophene and 1,3-diferrocenylbenzo[ c]thiophene have been systematically and selectively synthesized from benzo[ b]thiophene and phthaloyl dichloride, respectively. Characterization of the molecules was performed by physical and spectroscopic means and X-ray crystallographic analyses. The cyclic voltammograms of the novel thiophene derivatives containing ferrocene fragments showed a well-defined reversible cathodic step derived from the unusually stable thiophene radical anions and two distinct reversible anodic steps derived from ferrocenium cations separated from each other by a thiophene heterocycle. 1,3-Diferrocenylbenzo[ c]selenophene was also synthesized in a similar manner for formation of 1,3-diferrocenylbenzo[ c]thiophene by the use of bis(dimethylaluminum) selenide as a selenating reagent.

Synthesis of γ-(2,4-Dioxobut-1-ylidene)butenolides by Reaction of Masked 1,3-Dicarbonyl Dianions with Maleic Anhydrides and Phthaloyl Dichloride

γ-(2,4-Dioxobut-1-ylidene)butenolides were prepared with very good regioselectivity by reaction of (2,4-dioxobutylidene)triphenylphosphoranes with maleic anhydrides. The reaction of 1,3-bis-silyl enol ethers with phthaloyl dichloride afforded benzo-annulated γ-(2,4-dioxobut-1-ylidene)butenolides; the formation of these products can be explained by formation of iso-phthaloyl dichloride and attack of the bis-silyl enol ether onto the latter.

Electroreduction of (1S,2S)-2-amino-1-(4-nitrophenyl)-propane-1,3-diol derivatives. Behaviour of electrogenerated species and applications to organic synthesis

Hydroxylamines electrogenerated from (1S,2S)-2-amino-1-(4-nitrophenyl)-propane-1,3-diol derivatives (derivatives of p-nitrophenylserinol) are unstable in methanol–acetate buffer and practically stable in acetonitrile–aqueous acetate buffer. This latter medium was used to carry out subsequent reactions in situ involving the triacetylated p-hydroxylaminophenylserinol and various reagents. An azoxy compound was the major product isolated after reaction with maleic or phthalic anhydrides. In contrast, a benzoxazine dione was normally obtained with phthaloyl dichloride and a N-sulphonylated hydroxylamine was produced with p-toluenesulphonyl chloride.

Reactions of N‐(Perfluorophenyl)carbonimidoyl Dichloride with Aromatic Acids and Their Derivatives in the Presence of AlCl3. Formation of 2‐(Perfluorophenyl)isoindoline‐1,3‐dione and Its Derivatives.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Reactions of N-(Perfluorophenyl)carbonimidoyl Dichloride with Aromatic Acids and Their Derivatives in the Presence of AlCl3. Formation of 2-(Perfluorophenyl)isoindoline-1,3-dione and Its Derivatives

Reactions of N-(perfluorophenyl)carbonimidoyl dichloride with benzoic acid, benzoyl chloride, ethyl benzoate, and also with phthalic acid, phthaloyl dichloride, and phthalic anhydride in the presence of AlCl3 at 170°C afford2-(perfluorophenyl)isoindoline-1,3-dione. With benzoic acid and benzoyl chloride form also 2-(perfluorophenyl)-3-[(perfluorophenyl)imino]isoindolin-1-one. In reactions with compounds of the benzene series arise also derivatives of arylimidoyl chlorides and amide type compounds containing a CONHC6F5 moiety.

Synthesis of N,N′‐Bis(2‐thiazolinyl)‐, N,N′‐Bis(2‐thiazolyl)‐, and N,N′‐Bis(2‐pyrimidinyl)‐benzene Dicarboxamides.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Synthesis of Macrocyclic Arylene Ketone Oligomers Containing the Phthaloyl Moiety by Friedel–Crafts Acylation Reaction

Abstract Two kinds of macrocyclic arylene ketone oligomers have been synthesized in high yield from phthaloyl dichloride and various bridge-linking electron-rich aromatic hydrocarbons via the modified Friedel–Crafts acylation reaction. The presence of a Lewis base in this reaction is demonstrated to be advantageous for forming macrocycle oligomers. These resultant oligomers can undergo melt ring-opening polymerization to give polymers with high Tg and excellent thermal stability.

Synthesis of N,N′‐bis(2‐Thiazolinyl)‐, N,N′‐bis(2‐Thiazolyl)‐, and N,N′‐bis(2‐Pyrimidinyl)‐Benzene Dicarboxamides

New heteroaromatic benzene dicarboxamides have been synthesized in moderate to good yields by the reactions of 2‐aminothiazoline, 2‐aminothiazole, and 2‐aminopyrimidine with phthaloyl dichloride, isophthaloyl dichloride, and terephthaloyl dichloride in the presence of an organic base. The amides are sparingly soluble in common organic solvents but dissolve readily in dimethyl sulfoxide. Reactions of 2‐aminothiazoline and 2‐aminopyrimidine with phthaloyl dichloride yield a tricyclic compound and an imide, respectively, instead of the expected products.

Polycondensation of Chiral 3,4-Dihydro- N -Substituted Succinimide and Phthalic Acid Dichloride

Polycondensations of (3R,4R)-3,4-dihydro-N-substituted succinimide (DHRSI) and phthaloyl dichloride (x-PA) were carried out to obtain optically active polyesters ([α] D = -11.0° to +206.1°). The GPC curve of poly(DHPhSI/o-PA) by polarimetric detector (α Hg ) showed dextro rotation at a low molecular weight fraction and levo rotation at a high molecular weight fraction. Optical activities were attributed to configurational and/or conformational chirality.

Novel macrocyclic aryl thioether ester oligomers: structure characterization and free-radical ring opening polymerization

Novel macrocyclic aryl thioether ester oligomers have been synthesized in high yield from phthaloyl dichloride and 4,4′-thiodiphenol under pseudo high dilution conditions. The cyclic nature was unambiguously confirmed by a combination of MALDI-TOF MS, gel permeation chromatography and NMR analyses. Single-crystal X-ray diffraction of cyclic ester dimer reveals no severe strain on the cyclic structure. The free-radical ring opening polymerization (ROP) of the macrocyclic oligomers was achieved to give high molecular weight polymers via a transthioetherification reaction. The molecular weight of the polymer resulting from ROP decreases as the conversion of cyclic oligomers increases after a polymerization period of 30 min.

Novel macrocyclic aryl thioether ester oligomers: structure characterization and free-radical ring opening polymerization

Novel macrocyclic aryl thioether ester oligomers have been synthesized in high yield from phthaloyl dichloride and 4,4'-thiodiphenol under pseudo high dilution conditions. The cyclic nature was unambiguously confirmed by a combination of MALDI-TOF MS, gel permeation chromatography and NMR analyses. Single-crystal X-ray diffraction of cyclic ester dimer reveals no severe strain on the cyclic structure. The free-radical ring opening polymerization (ROP) of the macrocyclic oligomers was achieved to give high molecular weight polymers via a transthioetherification reaction. The molecular weight of the polymer resulting from ROP decreases as the conversion of cyclic oligomers increases after a polymerization period of 30 min.

Reactions of 3-Chloro-3-(Dimethylphosphono) Isobenzofuranone and its Derivatives

3-Chloro-3-(dimethylphosphono)isobenzofuranone (I), obtained by the reaction of phthaloyl dichloride with (MeO)3P can be monodemethylated to sodium 3-chloro-3-(methylphosphono)isobenzofuranone (2) by Nal, or hydrolyzed to 3-hydroxy-3-(methyl)phosphonoiso- benzofuranone (3 and 4), depending on the reaction conditions. The 31P nmr spectra of hydroxyphosphonoisobenzofuanones 3 and 4 were found to be pH dependent. Raising the pH of the solutions to 10 caused reversible changes in the spectra of 3 (31P δ = 10.2 ppm) and 4 (31P δ = 8.96 ppm) consistent with opening of the isobenzohranone ring and the formation of orrho-(phosphonoformyl)benzoate anions 5 (31P δ = 0.89 ppm) and 6 (31P δ = 0.19 ppm). Analogous changes were also observed in the 31C nmr spectra of the compounds. 3-Chloro-3 (dimethy1phosphono)-isobenzohra-none (1) reacts rapidly with aliphatic mines and with amino acids at room temperature to give phthalimides in high yields thus providing a new convenient sythetic method to such compounds. Ackowledgment J. K. thanks the Rabin Foundation in Denmark for a generous grant.

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.

Linear polythioesters, XXVI. Products of interfacial polycondenation of bis(4‐mercaptomethylphenyl)methane with some aliphatic and isomeric phthaloyl dichlorides

AbstractNew polythioesters were synthesized by interfacial polycondensation of bis(4‐mercaptomethylphenyl)methane with selected aliphatic and isomeric phthaloyl dichlorides. To determine optimum polycondensation conditions, the influence of the following factors on reduced viscosity and yield were studied: type of organic phase, concentration of hydrogen chloride acceptor (NaOH), concentration of reagents, aqueous/organic phase ratio, rate of acid chloride addition, reaction time and reaction temperature.A thorough examination was carried out only for the polycondensation of dithiol with adipoyl and isophthaloyl dichlorides chosen as model systems. The structures of polythioesters were confirmed by elemental analysis, X‐ray analysis and infrared spectroscopy. Some physicochemical, mechanical and electrical properties were determined. The molecular weights were not measured, because of the low solubility of the obtained polythioesters.