Dicarboxylic Acid Dichlorides Research Articles

Polylactones, 67

AbstractSummary: Spirocyclic initiators were prepared by condensation of Ge(OEt)4 and tetra(ethylene glycol), TEG, or PEG‐2000 ($\overline M _{\rm n}$ = 2 000 Da). These spirocycles were used as initiators for the ring‐expansion polymerization of L‐lactide in chlorobenzene at 120 °C. The resulting cyclic block copolymers were reacted in situ with aliphatic dicarboxylic acid dichlorides (ADADs) or with hexamethylene diisocyanate (HMDI) to achieve chain extension. The reaction conditions were optimized via model reactions. The isolated Ge‐free multiblock copolymers were characterized by viscosity and by 1H NMR measurements. In selected cases SEC measurements and MALDI‐TOF mass spectrometry were conducted. The mass spectra revealed small amounts of cyclic oligo‐ and polylactides, whereas the high molecular weight multiblock copolymers did not “fly”.Structure of spirocyclic Ge‐initiator used here.imageStructure of spirocyclic Ge‐initiator used here.

Efficient Synthesis of New Sulfur Macrocyclic Diamides

Some new sulfur macrocyclic diamides and tetraamides were obtained via a simple and convenient method. This method consists of reacting a dicarboxylic acid dichloride with the appropriate diamine in dichloromethane. The cyclization does not require high dilution technique or template effect and the expected dilactams were obtained in high yields.

Macrocycles 27: Cyclic aliphatic polyesters of isosorbide

AbstractNumerous polycondensations of isosorbide and suberoyl chloride or other aliphatic dicarboxylic acid dichlorides were performed with pyridine as a catalyst and HCl acceptor. The reaction conditions were varied to optimize both the molecular weight and the fraction of cyclic oligo‐ and polyesters. Furthermore, we attempted to obtain the cyclic monomer by catalyzed back‐biting degradation of the molten cyclic polyesters above 220 °C in vacuo. The polyesters were characterized by viscosity and size exclusion chromatographic measurements as well as matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry. In selected cases, mixtures of linear and cyclic polyesters were treated with a hot solution of partially methylated β‐cyclodextrin in methanol. This treatment allowed for a selective extraction of the linear chains up to approximately 5000 Da. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3414–3424, 2003

Syntheses of biodegradable (multi) block copolymers, star‐shaped polyesters and networks via ring‐expansion polymerization

AbstractNumerous cyclic dibutyltin alkoxides were prepared by condensation of Bu2Sn(OMe)2 with various short or long α,ω‐diols. Insertion of lactones or lactide into the SnO bonds resulted in ring‐expansion polymerizations which allowed a control of the ring size (chain length) via the monomer initiator ratio. When the cyclic initiators were derived from a long α,ω‐diol, such as poly(tetrahydrofuran)diols or polysiloxane diols, the resulting cyclic polylactones were necessarily cyclic triblock copolymers. The high nucleophilicity of the Sn‐O bond enabled ring‐opening polycondensations with dicarboxylic acid dichlorides yielding multiblock copolyesters. Condensations with monocarboxylic acids yielded functionalized A‐B‐A triblock copolymers. Polycondensation with trifunctional acid chlorides yielded biodegradable networks. Hydroxyethylated pentaerythritol condensed with Bu2Sn(OMe)2 yielded a spirocyclic initiator. Ring‐expansion polymerization with lactones followed by acylation with carboxylic acid chlorides produces star‐shaped polylactones having functional endgroups. Biodegradable networks were also obtained when bisstannylenated α‐glucose methyl glycoside was used as initiator for ϵ‐caprolactone, and when the resulting spirocyclic polylactone was polycondensed with sebacoyl chloride. Copyright © 2003 John Wiley & Sons, Ltd.

ChemInform Abstract: Unexpected Ring Size Effect of the Annulation Reaction of Heterocyclic Secondary Enamines with Dicarboxylic Acid Dichlorides.

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Macrocycles. 19. Cyclization in the Nematic Phase? Polyesters Derived from Hydroquinone 4-Hydroxybenzoate and Aliphatic Dicarboxylic Acids

Silylated hydroquinone 4-hydroxybenzoate (HHB) was polycondensed with aliphatic dicarboxylic acid dichlorides (ADADs) in bulk at temperature up to 240 °C. These polycondensations proceeded in the nematic phase, and both transesterification and backbiting degradation were avoided as evidenced by 1 H NMR spectroscopy. The nematic LC phases were characterized by optical microscopy and DSC measurements. The MALDI-TOF mass spectra revealed the formation ofeven-membered cycles (in addition to linear oligomers), whereas odd-membered cycles were almost absent. When the reaction mixture was slightly diluted with 1-chloronaphthalene, so that the polycondensation proceeded in the isotropic phase, odd-membered cycles with a predominance of the cyclic trimer were found. When free HHB was polycondensed with ADADs in 1-chloronaphthalene at 220 °C in 1,2-dichlorobenzene at 190 °C or in the presence of pyridine at 5-10 °C, again odd-membered cycles were found. Obviously, the nematic phase enforces a parallel alignment of polyester chains with strong electronic interaction of neighboring mesogens, so that cyclization can only occur in the case of even-membered chains via hairpin conformations of the aliphatic spacers.

Unexpected ring size effect of the annulation reaction of heterocyclic secondary enamines with dicarboxylic acid dichlorides

Heterocyclic enamines are versatile ambident nucleophilic reagents able to react with both aliphatic and aromatic dicarboxylic acid dichlorides in diverse manners. The reaction outcome was strongly dependent upon the heterocyclic structure of the enamines and the nature of the diacid dichlorides employed.

A preliminary study on polyhydrazides incorporating furan moieties

Solution and interfacial polycondensation of difuranic dihydrazides with aromatic or aliphatic dicarboxylic acid dichlorides led to the corresponding polyhydrazides which were characterized in terms of structure and average chain length. Their conversion to the corresponding polyoxadiazoles was also examined. Model compounds were prepared to facilitate the synthesis and the characterization of the polymers.

Macrocycles. 17. The Role of Cyclization in Kinetically Controlled Polycondensations. 2. Polyamides

Two series of kinetically controlled polycondensations were conducted yielding polyamides of aliphatic dicarboxylic acids. First, the bis(trimethylsilyl) derivatives of 1,3-diaminobenzene, 4,4‘-diaminodiphenylmethane, 1,12-diamino-4,9-dioxadodecane, and 1,12-diaminododecane were polycondensed with dicarboxylic acid dichlorides in N-methylpyrrodidone below 0 °C. After optimization of the reaction conditions mainly cyclic polyamides were detectable in the MALDI−TOF mass spectra (up to 13 000 Da) of the semiaromatic polyamides in contrast to the Carothers−Flory theory. In the case of silylated aliphatic diamines, side reactions of the acid chlorides prevented a complete conversion of the amino groups, so that the reaction products mainly consisted of cycles and linear chains having two amino end groups. Second, normal interfacial polycondensations were performed either with 1,6-diaminohexane and adipoyl chloride or with 1,12-diaminododecane and decane-1,10-dicarbonyl chloride. When the loss of acid chloride ...

New polymer syntheses. CIX. Biodegradable, alternating copolyesters of terephthalic acid, aliphatic dicarboxylic acids, and alkane diols

AbstractCopolyesters with an alternating sequence of terephthalic acid and aliphatic dicarboxylic acids were prepared with three different methods. First, dicarboxylic acid dichlorides were reacted with bis(2‐hydroxyethyl)terephthalate (BHET) in refluxing 1,2‐dichlorobenzene. Second, the same monomers were polycondensed at 0–20 °C in the presence of pyridine. Third, dicarboxylic acid dichlorides and silylated BHET were polycondensed in bulk. Only this third method gave satisfactory molecular weights. Matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry revealed that the copolyesters prepared by the pyridine and silyl methods might have contained considerable fractions of cyclic oligoesters and polyesters despite the absence of transesterification and backbiting processes. The alternating sequences and thermal properties were characterized with 1H NMR spectroscopy and differential scanning calorimetry measurements, respectively. In agreement with the alternating sequence, all copolyesters proved to be crystalline, but the crystallization was extremely slow [slower than that of poly(ethylene terephthalate)]. A second series of alternating copolyesters was prepared by the polycondensation of silylated bis(4‐hydroxybut‐ yl)terephthalate with various aliphatic dicarboxylic acid dichlorides. The resulting copolyesters showed significantly higher rates of crystallization, and the melting temperatures were higher than those of the BHET‐based copolyesters. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3371–3382, 2001

Annulation of heterocyclic secondary enamines with dicarboxylic acid dichlorides, an unexpected ring size effect

Under very mild conditions heterocyclic secondary enamines react efficiently with malonyl chloride to produce hydroxylated 2-pyridinone-fused heterocycles. The reactions of enamines with oxalyl chloride, however, afford varied products depending upon the heterocyclic structure of the enamine. Whilst a C-acylated enamine and a lactam-fused heterocycle were obtained from the reaction of the five- and seven-membered heterocyclic enamines, respectively, the six-membered heterocyclic enamine gave 2-oxo-5,6,7,8-tetrahydro-2 H-pyrido[3,2- b]pyran. The reaction mechanisms are discussed.

Macrocycles. 15. The Role of Cyclization in Kinetically Controlled Polycondensations. 1. Polyester Syntheses

Various diols were polycondensed with dicarboxylic dichlorides in the presence of pyridine or γ-picoline. Aliphatic dicarboxylic acid dichlorides were reacted with 1,4-butanediol, catechol resorcin...

ChemInform Abstract: Reactions of Grignard Reagents with Bis- and Monophosphonium Ions in situ Generated from Bu3P and Dicarboxylic Acid Dichlorides or ω-Ethoxycarbonyl Alkanoyl Chlorides as a Novel Method to Obtain Diketones and Ketoesters.

ChemInform Abstract: Reactions of Grignard Reagents with Bis- and Monophosphonium Ions in situ Generated from Bu3P and Dicarboxylic Acid Dichlorides or ω-Ethoxycarbonyl Alkanoyl Chlorides as a Novel Method to Obtain Diketones and Ketoesters.

LC-polyimide 38. Smectic poly(ester-imide)s of N, N-bis(4-hydroxy-phenyl)biphenyl-3,3′,4,4′-tetracarboxylic imide having long aliphatic spacers. Part I

A new monomer ( 7) was prepared by alkylation of N, N,-bis(4-hydroxyphenyl)biphenyl-3,3′,4,4′-tetracarboxylic imide with 11-bromoundecanol. This imide diol ( 7) did not form a LC-phase, but showed two reversible first-order transitions in the solid state. It was polycondensed with various aliphatic dicarboxylic acid dichlorides in 1-chloronaphthalene. The phases and phase transitions of the resulting poly(ester-imide)s were characterized by optical microscopy, DSC measurements and X-ray measurements at variable temperature. All poly(ester-imide)s formed a crystalline smectic phase in the solid state. In the case of short spacers enantiotropic smectic-A phase were observed which vanished in the case of long spacers.

Metal Complexes of Biologically Important Ligands, CXXV [1]. Palladium(II) and Platinum(II) Complexes of Quinine Derivatives and in vitro Tests

Several quinine substituted derivatives at the C(9)-O position (1 - 7) have been obtained from quinine and N-protected glycine chloride, chlorocarbonyl ferrocene, phenylisocyanate, dicarboxylic acid dichlorides or trimesinic trichloride. From these only the glycine derivative 1 showed significant antimalarial activity in in vitro tests against Plasmodium falciparum isolates. The quinine derivatives were used as ligands and from chloro bridged palladium and platinum complexes Cl(R3P)M(μ-Cl)2M(PR3)Cl (M = Pd, Pt) di-, tri-, tetra- and hexametallic compounds 8-21 with coordination both of the aliphatic and aromatic N-atoms were synthesized. Protection of the tertiary N atom by protonation gave the quinoline complexes 22-25. Using a stoichiometric ratio metal/ligand = 1/1 it could be shown that the coordination of metal ions at the quinoline N-atom is by far preferred. A titanium(IV) complex 36 is formulated as [Ti(quinine)3Cl]Cl3 with quinine as a zwitterionic ligand

Efficient Synthesis of a Range of Benzosubstituted Macrocyclic Diamides

Some new macrocyclic dibenzotetraoxadiamides, tribenzotetraoxadimides, tribenzopentaoxadiamide, tribenzohexaoxadiamide, and tetrabenzoheptaoxadiamide 15-22 have been prepared. These compounds were obtained in the macrocyclization step by reacting the diamines 6 and 7 with appropriate dicarboxylic acid dichlorides 8-14. The cyclization does not require high dilution techniques or template effect and provides the expected dilactams in high yields ranging from 63% to 81%.

Reactions of grignard reagents with bis- or mono-phosphonium ions in situ generated from Bu3P and dicarboxylic acid dichlorides or omega-ethoxycarbonyl alkanoyl chlorides as a novel method to obtain diketones and ketoesters.

Reactions of Grignard reagents with bis-phosphonium or mono-phosphonium ions in situ generated from BusP and ClCO(CH2)nCOCl (5) or ClCO(CH2)nCO2Et (13) as a tool for preparation of symmetrical diketones or ketoesters were examined. Addition of Bu3P (2.0 eq) to a THF solution of 5 (n=2) at -40 degrees C followed by addition of n-BuMgCl (2.0 eq) gave the corresponding diketone in good yield. When a mixture of BusP and the Grignard reagent (2.0 eq each) was added to the dichloride solution at the same temperature, a better result was obtained. The latter method not with PhMgBr but with n-BuMgCl or MeMgBr was shown to be useful for preparation of symmetrical alkanediones and keto alkanoates from various 5 (n=2-6) and 13 (n=2 or 3), respectively. For synthesis of alpha-diketones or alpha-ketoesters, only PhMgBr entered the reaction, although the yields were not satisfactory. Addition of a mixture of Bu3P (2.0 eq), MeMgBr (1.0 eq) and BuMgCl (1.0 eq) to a THF solution of 5 (n=4) at -40 degrees C afforded a mixture of 2,7-undecanedione and the corresponding two symmetrical diketones, with the yield of the unsymmetrical diketone being 36%.

Synthesis of Novel α,ω-Type 1-Glucosamide and 1-Galactosamide Bolaamphiphiles

A new family of bolaamphiphiles in which two glucosylamine or galactosylamine moieties are linked via a β-N-glycosidic bond to an α,ω-dicarboxylic acid has been described. The 1-D-glucosamide and 1-D-galactosamide bolaamphiphiles were obtained in good yield by the condensation of the dicarboxylic acid dichloride with the corresponding 1-aldopyranosylamine.

Macrocyclic polymerization ‐ a new approach to molecular engineering

Abstract2,2‐Dibutyl‐2‐stanna‐1,3‐dioxacycloalkanes were used as cyclic initiators for the ring‐opening polymerization of various lactons. This method exclusively yielded series of macrocyclic polylactones without any competition with linear polymers. Under optimized reaction conditions these macrocyclic polymerizations obey the pattern of “living polymerizations”. The living chain ends allow the syntheses of macrocyclic blockcopolymers. The macrocyclic polylactones react with carboxylic acid chlorides by ring‐opening yielding telechelic oligo or polylactones. Furthermore, the tin containing macrocyclic polylactones can be used as difunctional “monomers” for polycondensations with dicarboxylic acid dichlorides.

New Polymer Syntheses. 89. Thermosetting Cholesteric Oligoesters Having Propargyl Endgroups

Three series of cholesteric oligoesters containing propargyl endgroups were prepared by polycondensations of three different dicarboxylic acid dichlorides with mixtures of diols and monofunctional propargyl derivatives in pyridine. These three series are based on terephthaloylchloride, naphthalene-2,6-dicarbonylchloride, and biphenyl-4,4′-dicarbonylchloride. tert-Butylhydroquinone, phenylhydroquinone, and isosorbide were the diols, and propargyl alcohol, 4-propargylthiophenol, and 6-propargyloxynaphthaloyl chloride served as chain stoppers. All isolated oligoesters were thermotropic, but only a few of them were capable of forming a Grandjean texture upon shearing of the cholesteric melt. The thermal crosslinking of the propargyl endgroups was monitored by an exothermic process in the DSC measurements. The lowest cure temperatures (200–240°C) were observed for the 6-propargyloxy-2-naphthoic acid endgroups. Thermal crosslinking in the cholesteric phase was observed for four samples.