Dicarboxylic Acid Dichlorides Research Articles

Dimerization enhances cytotoxicity and tumor/non-tumor cell selectivity of juglone

<span lang="DE">The study investigates the biological activity of spaced juglone dimers derived from the reaction of juglone with dicarboxylic acid dichlorides of varying chain lengths. It builds upon the observation that dimeric structures can exhibit enhanced biological activity compared to their monomeric counterparts. The cytotoxic effects of the synthesized compounds were assessed against a range of human cancer cell lines and non-malignant fibroblasts. Results indicate that the cytotoxicity varied depending on the length of the spacer, with specific dimers showing significantly improved activity. Furthermore, these compounds demonstrated a higher selectivity towards cancer cell lines than non-malignant fibroblasts, suggesting potential for targeted anticancer therapy</span><span lang="EN-US">. </span>

Free Volume and Permeability of Mixed Matrix Membranes Made from a Terbutil-M-terphenyl Polyamide and a Porous Polymer Network.

A set of thermally rearranged mixed matrix membranes (TR-MMMs) was manufactured and tested for gas separation. These membranes were obtained through the thermal treatment of a precursor MMM with a microporous polymer network and an o-hydroxypolyamide,(HPA) created through a reaction of 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane (APAF) and 5′-terbutil-m-terfenilo-3,3″-dicarboxylic acid dichloride (tBTmCl). This HPA was blended with different percentages of a porous polymer network (PPN) filler, which produced gas separation MMMs with enhanced gas permeability but with decreased selectivity. The thermal treatment of these MMMs gave membranes with excellent gas separation properties that did not show the selectivity decreasing trend. It was observed that the use of the PPN load brought about a small decrease in the initial mass losses, which were lower for increasing PPN loads. Regarding the glass transition temperature, it was observed that the use of the filler translated to a slightly lower Tg value. When these MMMs and TR-MMMs were compared with the analogous materials created from the isomeric 5′-terbutil-m-terfenilo-4,4″-dicarboxylic acid dichloride (tBTpCl), the permeability was lower for that of tBTmCl, compared with the one from tBTpCl, although selectivity was quite similar. This fact could be attributed to a lower rigidity as roughly confirmed by the segmental length of the polymer chain as studied by WAXS. A model for FFV calculation was proposed and its predictions compared with those evaluated from density measurements assuming a matrix-filler interaction or ideal independence. It turns out that permeability as a function of FFV for TR-MMMs follows an interaction trend, while those not thermally treated follow the non-interaction trend until relatively high PPN loads were reached.

Synthesis and characterization of novel fluorinated polyamides bearing tetraphenyl imidazole moieties

1,2-Bis(4-aminophenyl)-4,5-bis(4-trifluoromethylphenyl)-1H-imidazole, as a new asymmetric aromatic diamine, was synthesized and used for preparation of novel fluorinated polyamides (PAs) containing tetraphenyl imidazole moieties in the main chain by low-temperature polycondensation of the diamine with various aromatic dicarboxylic acid dichlorides. The resulting PAs were amorphous and their weight-average and number-average molecular weight were in the range of 22,500–34,600 and 12,600–16,800 g/mol, respectively. These PAs exhibited low moisture uptake of 0.97–2.15%, and good thermal stability with 10% weight loss temperatures of 445–453 °C and char yields of 57–61% at 800 °C in nitrogen. All obtained PAs showed good flame retardancy with limited oxygen index value of 39.9–41.9, and were readily soluble in a variety of organic solvents such as N,N-dimethyl acetamide, N-methyl-2-pyrrolidinone, dimethylsulfoxide, pyridine, tetrahydrofuran and acetone at room temperature, and formed low-colored and flexible thin films via solution casting. They also exhibited strong UV–vis absorption in the range of 290–320 nm in solution and in films, and their films exhibited high optical transparency with a cutoff wavelength in the 328–365 nm range.

New soluble, transparent and heat-resistant poly(ether amide)s based on 10,10-bis[4-(4-aminophenoxy)-3-methylphenyl]-9(10H)-anthrone

10,10-Bis[4-(4-aminophenoxy)-3-methylphenyl]-9(10 H)-anthrone, as a new aromatic diamine, was synthesized from 9(10 H)-anthrone by three-step procedure. Low-temperature polycondensation of this diamine with various aromatic dicarboxylic acid dichlorides produced a series of new cardo poly(ether amide)s with moderate to high inherent viscosities of 0.86–1.43 dL g−1 while the weight-average and number-average molecular weights were in the range of 48,600–59,800 and 29,800–35,600 g mol−1, respectively. All the polymers were readily soluble in polar solvents such as N, N-dimethylacetamide (DMAc), N, N-dimethylformamide, N-methyl-2-pyrrolidinone, dimethyl sulfoxide, and pyridine, and afforded transparent, flexible, and strong films upon casting from DMAc solvent. These polymers had glass transition temperatures of 254–297°C, 10% weight loss temperatures of 493–505°C, and char yields of 61–64% at 800°C in nitrogen. All polymers were amorphous and their films exhibited tensile strength of 80.7–101.4 MPa, elongation at break of 8.0–12.8%, and tensile modulus of 1.9–2.6 GPa. These polymers had low moisture uptake in the range of 2.13–4.02% and high transparency with an ultraviolet–visible absorption cutoff wavelength in the 322–375 nm range.

Biopolyester prepared using unsaturated betulin (betulinol) extracted from outer birch bark and dicarboxylic acid dichlorides and its thermal-induced crosslinking

Betulin, also called betulinol, with two hydroxyl moieties extracted from white birch bark, and acid dichloride (ClCO(CH2)mCOCl) were successfully polycondensed to give the corresponding aliphatic biopolyester (ABIOS) in the presence of pyridine; in particular, in the case of sebacoyl dichloride (m = 8), derived from sebacic acid contained in castor oil of Ricinus seed, the ABIOS8 was obtained in a fairly high yield of 91%, with Mw = ∼23,800 and Mw/Mn = ∼2.1, even at room temperature. By contrast, the polymerization using other acid dichlorides with short methylene chains, i.e., m = 2, 4, 5, and 7, and long methylene chains, i.e., m = 10, resulted in relatively lower yields with a lower molecular weight, Mw. The ABIOS8 with (CH2)8 showed a high glass transition temperature (Tg ≈ 150 °C) superior to that of polylactic acid (PLA) known as a typical biopolyester. A colorless transparent film of ABIOS8 was easily fabricated by the solvent-casting method using THF or CHCl3 as solvent. Furthermore, the ABIOS8 gradually became insoluble in solvents such as THF when heated to 250 °C even under a nitrogen atmosphere. It was deduced that the CC bond in the isopropenyl moiety (H2CC(CH3)) as the third substituent within the betulin mother molecule in ABIOS8 acted as a thermally induced cross-linker.

Synthesis of Symmetrical Polyamide–Sulfonimides Based on Bis-saccharin Dicarboxylic Acid Dichlorides

Polycondensation of ethylene-bridged bis(saccharincarbonyl chlorides) with aliphatic diamines afforded soluble polyamide–sulfonimides. The effects of the concentration of the initial reactants and reaction temperature on the yield and intrinsic viscosity of the obtained polymers were studied, and optimal conditions for their synthesis were found. According to the DTA and TGA data, the synthesized polymers are characterized by a high heat resistance and can operate at elevated temperature.

Synthesis of fluorine-containing esters of 2,5-furandicarboxylic acid

Fluorinated esters of 2,5-furandicarboxylic acid have been synthesized starting from 2,5-furan dicarboxylic acid dichloride and fluorine-containing diols. The reaction control was performed by means of 1H, 19F NMR, and IR-spectroscopy. Thermal stability, as well as glass transition temperature, and intrinsic viscosity parameters of the obtained oligomers have been determined.

Synthesis of Substituted Helicenes by Ir-Catalyzed Annulative Coupling of Biarylcarboxylic Acid Chlorides with Alkynes

Abstract A series of substituted [4] and [5]helicenes were synthesized in moderate to good yields by an Ir-catalyzed annulative coupling of biarylcarboxylic acid chlorides with internal alkynes, which involves facile C-H bond cleavage and decarbonylation. The double annulative coupling of 1,1′:5′,1′′-ternaphthalene-2,2′′-dicarboxylic acid dichloride with 4-octyne was also accomplished to give rise to an S-shaped double helicene. Unexpectedly, a π-extended benzofluoranthene-merged [5]helicene was constructed through the annulative coupling and the successive C(aryl)-C(aryl) bond forming reaction when 1,1′:4′,1′′-ternaphthalene-2,2′′-dicarboxylic acid dichloride was employed as the substrate. The crystal structure and the optical properties of the latter unique product were also investigated.

Synthesis of Chiral Polyamides Containing an (R,R)‐1,2‐Diphenylethylenediamine Monosulfonamide Structure and Their Application to Asymmetric Transfer Hydrogenation Catalysis

AbstractA chiral main‐chain polyamide containing an (R,R)‐1,2‐diphenylethylenediamine monotoluenesulfonamide (TsDPEN) repeating unit was prepared. Polycondensation of dicarboxylic acid dichloride with the chiral bisaniline of N‐tert‐butoxycarbonyl‐protected TsDPEN was successful and afforded a chiral polyamide with a TsDPEN repeating unit as the chiral ligand structure. Treatment of the main‐chain polymer chiral ligand with transition‐metal complexes, such as [IrCl2Cp*]2 (Cp*=η5‐pentamethylcyclopentadienyl), [RhCl2Cp*]2, and [RuCl2(p‐cymene)]2, afforded polymer chiral metal complexes. Asymmetric transfer hydrogenation of a cyclic sulfonamide was efficiently catalyzed by the chiral TsDPEN polymer–metal complex to give an optically active cyclic sulfonylamine with quantitative conversion and high enantioselectivity. The polymer catalyst was easily recovered from the reaction mixture and reused several times without any loss in catalytic activity or enantioselectivity.

Synthesis of C2‐Symmetric Bisphosphine Ligands from Tartaric Acid, and Their Performance in the Pd‐Catalyzed Asymmetric O‐Allylation of a Phenol

AbstractStarting from tartaric acid derived chiral diols or dicarboxylic acid dichlorides with either a 2,2‐dimethyl‐1,3‐dioxolane (Taddol) or a 2,3‐dimethoxy‐2,3‐dimethyl‐1,4‐dioxane (Tatrol) core structure, and BH3‐protected ortho‐phosphanyl phenols, a set of fourteen new C2‐symmetric diphosphine ligands was synthesized. In addition, three related ligands were obtained from ortho‐diphenylphosphino‐anilines. The fully characterized ligands were then tested in the Pd‐catalyzed enantioselective O‐allylation of 4‐methoxyphenol using crotyl methyl carbonate as a reagent. In addition, a pseudo‐intramolecular variant of the reaction, using crotyl 4‐methoxyphenyl carbonate as a substrate, was studied. The so‐called Trost ligand was used as a reference. Although the Trost ligand (3 mol‐%) gave up to 84 % ee, one of the new ligands showed higher activity (50 % ee with 0.075 mol‐%).

Synthesis and Aggregation Properties of Two‐ and Three‐Armed Nitrogen‐Rich Chelate Ligands: Novel Bis(N‐acylamidines), Tris(N‐acylamidines) and Bis(triazapentadienes) with Flexible or Rigid Spacers

AbstractTwo‐ and three‐armed ligands, like bis(N‐acylamidines) 7 and 9, tris(N‐acylamidines) 8 and bis(1,3,5‐triazapenta‐1,3‐dienes) 10 with different spacers between the ligand moieties, have been easily prepared in moderate‐to‐good yields starting from diamines, triamines or dicarboxylic acid derivatives. Thus, the reaction of diamines and triamines with N‐acylimidates 3 led to bis(N‐acylamidines) 7 and tris(N‐acylamidines) 8, respectively, linked through the amino group. Ligands 9, interconnected through the carbonyl groups, were obtained starting from dicarboxylic acid dichlorides and amidines. Bis(triazapentadienes) 10, linked through carbon atoms, were synthesized from a diamide, which was converted into a bis(N‐imidoylimidate) 17 followed by reactions with deprotonated amines. These compounds show variable aggregation behaviour in the solid state as a result of intra‐ and intermolecular hydrogen bonding. All compounds were thoroughly characterized including by X‐ray diffraction.

Synthesis of New Multibenzo Oxygen–Sulfur Donor Macrocycles Containing Lactams at Room Temperature

Some new oxygen–sulfur, multibenzo macrocyclic ligands containing amide groups have been prepared using the macrocyclization process with the reaction of 2,2′-thiobis-[4-methyl(2-aminophenoxy)phenyl ether] as a symmetrical diamine with appropriate dicarboxylicacid dichlorides in moderate yields. This macrocyclization led to the formation of di- and tetramide macrocycles. These reactions were routinely carried out at ambient temperature in CH2Cl2 as solvent in high dilution without template effect conditions. It is found that sulfur the atom affects the rigidity of the macrocycles and diastereotopicity of nuclei in the ring of these series of macrocyclic compounds.

Synthesis and properties of new poly(arylene thiophenes)

Soluble poly(arylene thiophenes) containing amide bridge bonds and free nitrile groups have been synthesized through polycondensation of new arylene-bis(2-aminothiophene-3-carbonitrile)s with arylene- dicarboxylic acid dichlorides, and their physical and photochemical properties have been studied. Thermostable and acid-resistant poly(thiene pyrimidones) co ntaining main-chain thiophene, arylene, and pyrimidone fragments have been obtained via the isomerization polycyclomerization of the poly(arylene thiophenes).

Synthesis of new macrocyclic lactones and their extraction study

New macrocyclic lactones were synthesized by reaction of 3-bromo-5-(5-tert-butyl-2-hydroxybenzyl)biphenyl-4-ol with appropriate polyethylene glycol-based dicarboxylic acid dichlorides, and their complexes with Mg(ClO4)2·6H2O, Pb(SCN)2, NaClO4·H2O, and KClO4 were prepared. The macrocyclic ligands were evaluated as extractants in the transfer of Li+, Na+, K+, Cu2+, Ni2+, and Hg2+ picrates from aqueous to organic phase.

Multicyclic Polythioesters Derived from Pentaerythritol Tetra(mercaptoacetate)

Dry pentaerythritol tetra(mercaptoacetate), PETMA, was polycondensed with double molar amounts of phthaloyl chloride, isophthaloyl chloride, tetraphthaloyl chloride, adipoyl, suberoyl, sebacoyl and 1,10‐decanedioyl chloride. Pyridine served as HCl‐acceptor and catalyst. The concentration of PETMA was varied between 0.1 mol/L and 0.0125 mol/L. With the aromatic dicarboxylic acid, dichlorides gelation occurred in all experiments. With aliphatic dicarboxylic acid dichlorides (ADADs), soluble multicyclic polythioesters were obtained at concentrations of 0.025 or 0.0125 mol/L. These multicyclic polythioesters were characterized by viscosity measurements,1H‐NMR spectroscopy and MALDI‐TOF mass spectrometry. A few experiments with pentaerythritol tetra(mercaptopropionate) showed a lower cyclization tendency relative to PETMA. Polycondensations of PETMA with α,ω‐dibromoalkanes or tri(ethylene glycol) bistosylate all ended with gelation.

Multicyclic Poly(ether ester)s by Polycondensation of Ethoxylated Pentaerythritol with Dicarboxylic Acid Dichlorides

AbstractCommercial ethoxylated pentaerythritol (EPE) was polycondensed with phthaloyl chloride, isophthaloylchloride, terephthaloyl chloride, and sebacoyl chloride. The monomer concentration was varied to find the borderline between soluble multicylic polyesters and gelation. The tendency of gelation increased in the above given order of dicarboxylic acids. Gelation was also favored by a lower content of ethylene oxide units in the EPE. An alternative approach based on the cyclization of EPEs with dibutyltin dimethoxide followed by acylation with dicarboxylic acid dichloride proved to be unsuccessful. The soluble multicycles were characterized by 1H NMR spectroscopy, MALDI‐TOF mass spectrometry, viscosity, and SEC measurements. The DSC measurements confirmed an amorphous character of all polyesters.magnified image

Cyclic and branched functional polyesters derived from 5,5′,6,6′‐tetrahydroxy‐3,3,3′,3′‐tetramethyl spirobisindane and various dicarboxylic acids

AbstractTriethylamine‐promoted polycondensations of 5,5′,6,6′‐tetrahydroxy‐3,3, 3′,3′‐tetramethyl spirobisindane (TTSBI) and α,ω‐alkane dicarboxylic acid dichlorides were performed with equimolar feed ratios. Three different procedures were compared. At a TTSBI concentration of 0.05 mol/L, gelation was avoided, and soluble cyclic polyesters having two OH groups per repeat unit were isolated. These polyesters were characterized with 1H NMR spectroscopy, MALDI‐TOF mass spectrometry, and SEC and DSC measurements. All polycondensations with sebacoyl chloride resulted in gelation, regardless of the procedure. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1699–1706, 2007

Multicyclic Polyesters by Polycondensation of 5,5‘,6,6‘-Tetrahydroxy-3,3,3‘,3‘-tetramethylspirobisindane with Dicarboxylic Acid Dichlorides

5,5‘,6,6‘-Tetrahydroxy-3,3,3‘,3‘-tetramethylspirobisindane (TTSBI) was polycondensed with 2 equiv of sebacoyl chloride or 1,6-hexanediol bischloroformiate. Although the monomer concentration was varied by a factor of 10, partially or totally cross-linked polyesters were obtained in all experiments. Analogous polycondensations of TTSBI were conducted with double molar amounts of α,ω-bis(4-chlorocarbonylphenoxy)alkanes or α,ω-bis(3-chlorocarbonylphenoxy)alkanes. Depending on concentration and structure of the dicarboxylic acid dichlorides, either gels or soluble multicyclic polyesters were obtained and characterized by 1H and 13C NMR spectroscopy, MALDI-TOF, and FAB mass spectrometry. SEC measurements revealed broad molecular weight distributions, and DSC measurements indicated an amorphous character of all multicycles.

Synthesis of strapped zinc chlorophyll derivatives and their complexation with a single axial ligand

Zinc chlorins having a bridged moiety between 3- or 8- and 17-positions were designed as protected chlorophylls at one of π-faces, aiming at the investigation of asymmetric coordination ability towards the central metal. These strapped chlorins were synthesized by the cyclization of the dihydroxylated chlorins with dicarboxylic acid dichlorides under highly diluted conditions. The synthetic zinc chlorins complexed with pyridine as an axial ligand in benzene to form 5-coordinated species. The 1:1 binding constants determined by UV–vis titration method were smaller than those of the corresponding acyclic (unstrapped) compounds.

An access to original 3,3-bis(phospholyl)lactones

The reaction of lithium 3,4-dimethylphospholide with dicarboxylic acid dichlorides yields the original 3,3-bis(3,4-dimethylphospholyl)lactones via an unexpected cyclization reaction. One of the products has been characterized by X-ray crystal structure analysis of its bis(pentacarbonylmolybdenum) complex.