Functional polymers. XLIX. Copolymerization of ω-alkenoates with α-olefins and ethylene

The 2,6-dimethylphenyl ester of 10-undecenoic acid was copolymerized with 1-dodecene, 1-octene, 1-hexene, propylene, and ethylene using coordination initiation systems based on “aluminum-activated” titanium trichloride and dialkylaluminum chlorides. The copolymerizations with higher α-olefins proceeded smoothly and gave copolymers incorporating from 60 to 90% of the 10-undecenoate feed. Copolymerization with propylene gave incorporation of 5 mol % of 2,6-dimethylphenyl 10-undecenoate; with ethylene only 3 mol % of the ω-alkenoate was readily incorporated. All copolymers were characterized by elemental analysis, dilute solution viscosity, and by their IR ¹H- and ¹³C-NMR spectra.     

Functional polymers. XLVII. Synthesis of various derivatives of ω-alkenoates

A number of derivatives of ω-alkenoates were synthesized in preparation for the synthesis of functional polymers based on α-olefins. For the preparation of most of the methyl esters, the regular esterification of ω-alkenoic acids, specifically 10-undecenoic acid with methanol and sulfuric acid as the catalyst, was most effective. For the preparation of the tert-butyl- and 2-ethylhexyl esters of 10-undecenoic acid, the acid chloride route was found to be most convenient, whereas for the preparation of the corresponding esters of 5-hexenoic acid, our method of choice was the synthesis via the imidazolyl derivative of the acid. 2,2,2-Trifluoroethyl 10-undecenoate and the 2,2-dimethyloxazolidine derivative of 10-undecenoic acid were prepared from the acid and 2,2,2-trifluoroethanol or 2-amino-2-methyl-propanol with p-toluene sulfonic acid as the catalyst. Esters of phenol, 2,6-dimethylphenol, and 2,6-diphenylphenol were synthesized from 3-butenoic and 10-undecenoic acid with trifluoroacetic anhydride.     

Functional Polymers. L Terpolymers of 10-Undecenoate Derivatives with Ethylene and Propylene

Terpolymers of 2,6-dimethylphenyl 10-undecenoate with ethylene and propylene have been synthesized. With titanium-based coordination initiator systems, a crystalline terpolymer was obtained which consists of blocks of ethylene and propylene, indicated by two distinct melting transitions. With vanadium-based systems, an amorphous ethylene/ propylene terpolymer was obtained. The crystalline terpolymer was hydrolyzed to the sodium carboxylate salt, which was acidified to give the polymeric carboxylic acid. All polymers were characterized by their infrared,¹H-, and ¹³C-NMR spectra, by differential scanning caiorim-etry, elemental analysis, and dilute-solution viscometry. In addition the polymeric sodium salt was characterized by wide-angle x-ray diffraction.     

Polymeric catalysis: Imidazoles grafted onto poly(vinylamine). I. Synthesis and grafting of imidazolylalkanoic acids

Some ω-(1-imidazolyl) and ω-[4(5)-imidazolyl]alkanoic acids were synthesized and grafted onto poly(vinylamine) with an amide bond. These water-soluble grafts were used to study the kinetics of the esterolysis of activated phenyl esters. The 1-substituted imidazoles were prepared by the reaction of the sodium salt of imidazole with the ethyl ω-bromoalkanoates. The 4(5)-substituted imidazoles were prepared from urocanic acid or 4(5)-hydroxymethylimidazole. The ω-(1-imidazolyl)alkanoic acids were grafted onto poly(vinylamine) via their acyl–guanidine derivatives; the 3-[4(5)-imidazolyl]propanoic acid was grafted with a water-soluble carbodiimide.     

Synthesis and study of block copolycondensates containing polysiloxane and unsaturated polyester blocks in the chain. II. Poly(unsaturated esters-b-siloxanes) with blocks linked by Si?C bonds and poly(butadienes-b-siloxanes)

Poly(unsaturated esters-b-siloxanes) whose blocks are linked by Si? C bonds and poly(butadienes-b-siloxanes) have been obtained by polycondensation of ω,ω′-diepoxy polydimethylsiloxanes and ω,ω′-dicarboxylic poly(unsaturated esters). The reaction between polysiloxanes with Si? H end groups and allylepoxy has been studied; the resulting ω,ω-diepoxy polysiloxanes have the expected structure. The polycondensation of oligomers with, respectively, epoxy and carboxylic end groups has been studied and the optimal conditions established. The samples with Si? C bonds are not affected by hydrolysis in pure water. The poly(siloxanes-b-unsaturated esters) can be cured by UV light.     

酶法拆分(±)-N-(2,6-二甲苯基)-丙氨酸甲酯

用脂肪酶Candida rugosa lipase (CRL)拆分(±)-N-(2,6-二甲苯基)-丙氨酸甲酯, 并进一步优化反应条件. 结果表明, 在加入1 mmol N-(2,6-二甲苯基)-丙氨酸甲酯、100 mL的0.2 mol/L磷酸缓冲液中, CRL拆分该底物的最适反应条件为: pH 6.4, CRL脂酶250 mg, 聚乙二醇(PEG) 2 g, 转速160 r•min^－1, 温度 35 ℃. 其中酶量、温度对转化率影响较大. 反应后分离得R-(＋)-N-(2,6-二甲苯基)-丙氨酸甲酯. 它和酰氯反应可制备一系列旋光性N-酰基丙氨酸类杀菌剂.     

Lokalisierung der Ketogruppe in Inandenin-onen. 160. Mitteilung über Alkaloide

Localization of the keto group in Inandenin-ones . By Schmidt degradation of the spermidine alkaloids inandenine-12-on ( 1 ) and inandenine-13-on ( 2 ) from Oncinotis inandensis followed by hydrolysis, acetylation and esterification four different types of products were obtained: the dicarboxylic diesters 9 and 10 , the ω-amino-carboxylic esters 11 and 12 , the acetylated polyamines 14 and 15 , and the acetylated triaminecarboxylic esters 16 and 17 . By GLC. and mass spectral analysis of these degradation products, and by comparison with synthetic compounds it was possible to confirm the structures 1 and 2 . The same alkaloid mixture ( 1+2 ) was obtained from the leaves of Oncinotis nitida BENTH .     

Flavinyl peptides. I. Synthesis of flavinyl-aromatic amino acids

The syntheses of flavinyl peptides, in which L-tryptophan, L-tyrosine, or L-phenylalanine are attached via peptide linkage to the isoalloxazine system with ω-carboxyalkyl groups in position 3 or 10, are described. Lumiflavin was carboxymethylated by known methods to yield N-3-carboxymethyllumiflavin. Oxidation of 10-ω-hydroxyhexyl-, 10-ω-hydroxypentyl-, 10-ω-hydroxybutyl-, and 10-formylmethylflavins gave the corresponding 10-ω-carboxyalkylflavins. The 10-ω-carboxyethylflavin was obtained by condensation of 2-amino-4,5-dimethyl-N-ω-carboxyethylaniline with alloxan. Activations of the carboxyl group of the flavins were achieved with N,N′-carbonyldiimidazole and p-nitrophenyltrifluoroacetate to form the corresponding acyl imidazoles and p-nitrophenyl esters. 10-Carboxymethylflavin was hydrogenated to form 10-carboxymethyldihydroflavin and activated by carbodiimide. Reaction of the carboxy-activated flavins with the appropriate amino acid methyl esters, followed by air oxidation in the case of dihydroflavin, gave the corresponding flavinyl peptides. Interaction of the flavin with aromatic amino acids results in a broadening of the visible flavin absorption towards the green, without the appearance of discrete new maxima, and in quenching of the flavin fluorescence. The fluorescence efficiency increases with increasing numbers of methylene groups in the flavin side chain. The nonlinear dependency of fluorescence quenching versus number of methylene groups indicates that different types of intramolecular interactions are involved.     

Thianthrene-containing polyimides with monomer formation via nucleophilic aromatic substitution

Thianthrene-2,3,7,8-tetracarboxylic dianhydride was synthesized via nucleophilic aromatic substitution of N-phenyle-4,5-dichlorophthalimide with thiobenzamide, thioacetamide, and sodium sulfide. This monomer was then polymerized with aromatic diamines by the con-ventional low temperature technique in N,N-dimethylacetamide (DMAc) to yield soluble poly(amic acid)s. Polyimides were obtained by thermal cyclization of the poly(amic acid) films. Polymers obtained formed creasable thin films and had excellent thermal stability in air and nitrogen. The bent thianthrene structure limited crystallization and chain packing, as indicated by x-ray analysis. The amorphous thianthrene-containing polyimides were only soluble in H₂SO₄. © 1995 John Wiley & Sons, Inc.     

Synthesis of poly(p‐phenylene sulfide) from bis(4‐bromophenyl) disulfide

Improved reaction conditions for the preparation of poly(p‐phenylene sulfide) (PPS) directly from bis(4‐bromophenyl) disulfide (BBD) have been established. Heating BBD with magnesium metal afforded only a low molecular weight polymer. PPS with a melting temperature around 280 °C was obtained from BBD in the presence of sodium carbonate or zinc metal. The best results were obtained with the addition of a catalytic amount of KI to the zinc–BBD mixture. Polymers prepared by the above methods are semicrystalline and dissolve in 1‐chloronaphthalene and have properties comparable to commercial PPS. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 900–904, 2006     

Functional polymers and sequential copolymers by phase transfer catalysis. 18. Synthesis and characterization of α,ω-bis(2,6-dimethylphenol)–poly(2,6-dimethyl-1,4-phenylene oxide) and α,ω-bis(vinylbenzyl)–poly(2,6-dimethyl-1,4-phenylene oxide) oligomers

A novel and convenient synthetic method for the preparation of α,ω-bis(2,6-dimethylphenol)–poly(2,6-dimethyl-1,4-phenylene oxide) (PPO-2OH) is presented. It is based on the oxidative copolymerization of 2,6-dimethylphenol (DMP) with 2,2′-di(4-hydroxy-3,5-dimethylphenyl propane) (TMBPA) in a mixture of water–methanol or chlorobenzene–methanol. By using a 4/1 mole ratio of DMP to TMBPA and different solvent mixtures, it was possible to obtain bifunctional PPO-2OHs with number average molecular weights between 1000 and 5000. A phase-transfer-catalyzed etherification of PPO-2OH chain ends with a mixture of m- and p-chloromethylstyrene was used to synthesize α,ω-bis(vinylbenzyl)-poly(2,6-dimethyl-1,4-phenylene oxide)s (PPO-2VBs). The thermal polymerization of the PPO-2VBs was studied by differential scanning calorimetry, and has demonstrated a very high thermal reactivity for this new class of reactive oligomers.     

3-Oxo-1,2-benzoisothiazoline-2-acetic acid 1,1-dioxide derivatives. I. Reaction of esters with alkoxides

Reaction of 3-oxo-1,2-benzoisothiazoline-2-acetic acid alkyl esters 1,1-dioxide ( 1a-d ) with alkaline alkoxides was carried out under various conditions. Under mild conditions, o-(N-carboxymethylsulfamyl)benzoic acids dialkyl esters ( 2a-d ) were obtained with good yields. Reaction of 1a-d or 2a-d with sodium alkoxides under drastic conditions afforded 4-hydroxy-2H-1,2-benzothiazine-3-carboxylic acid alkyl esters 1,1-dioxide ( 3a-d ). Transesterification was observed when esters 1b-d were treated with sodium methoxide in methanol. Esters 3a-d were hydrolyzed in concentrated aqueous sodium hydroxide affording the acid 6 . Attempts to recrystallize 6 from water resulted in its decarboxylation to give 2H-1,2-benzothiazine-4-(3H)one 1,1-dioxide (7). Compound 6 could not be obtained by acid hydrolysis of esters 3a-d or by rearrangement of 3-oxo-1,2-benzoisothiazoline-2-acetic acid 1,1-dioxide ( 8 ). Different experimental evidence supports the suggestion that rearrangement took place by ethanolysis of the carboxamide linkage affording the open sulfonamides (fast step) followed by a Dieckmann cyclization (slow step). It was demonstrated that transesterification took place in the open sulfonamides 2 .     

Les β-cétonitriles groupes protecteurs de la fonction amine. Préparation d'amino-alcools

β-Ketonitrile-Derived Protecting Groups of the Amino Function. Synthesis of Amino Alcohols The amino group of natural L -amino acid esters is protected by condensation with 2-oxocyclopentanenitrile ( 1 ) or 2-formyl-2-phenylacetonitrile ( 10 ). Only the ester group of the formed cyanoenamino esters 2 and 11 reacts with nucleophilic reagents such as organometallics (RMgX, RLi), borohydrides, or metal amides, whereas the cyanoenamino group is unchanged (Schemes 1 and 2). Cyanoenamino alcohols obtained by reduction of cyanoenamino esters 2 are hydrolyzed under acidic conditions to amino alcohols with retention of the configuration of the starting amino acid. This sequence of reactions allows to prepare derivatives of L -tyrosinol from (?)-L -tyrosine (see, e.g., Scheme 4). Cyanoenamino esters 11 are readily methylated at the N-atom to give N-methylated cyanoenamino esters (Scheme 3). This property is exploited on the way of a multistep procedure to obtain N-methylated amino alcohols homologous to natural (?)-(1R,2S)-ephedrine.     

One step synthesis of pyrimido[1,2-a][1,8]naphthyridinones,pyrido[1,2-a]pyrimidinones and 1,8-naphthyridinones. Antihypertensive agents. V

The condensation of 2,6-diaminopyridine and 2-acetamido-6-aminopyridine with β-keto esters in polyphosphophoric acid was studied. In this reaction some 1,8-naphthyridinones, pyrido[1,2-a]pyrimidinones and pyrimido[1,2-a][1,8]naphthyridinones variously substituted were obtained.     

Bemerkung zur vorstehenden Notiz [1] von H. REMBOLD

The possible transition state conformations (chair (S), boat (W), and twist (T), respectively cross (K) forms) and methods for their determination in the thermal ortho-CLAISEN rearrangement of allyl aryl ethers are discussed. Crotyl 3,5-dimethylphenyl ether ( 11 ) gives a mixture of 2-(α-methylallyl)-3,5-dimethyl-phenol ( 12 ) and 4-crotyl-3,5-dimethyl-phenol ( 13 ) on heating in N, N-diethylaniline. Values of 3 and 31 were obtained for the ratio of 12 / 13 for trans- 11 and cis- 11 , respectively. It therefore follows that both ethers rearrange steroselectively ( > 90%) by the S or W forms of the activated complex. αMethylallyl 6-alkylphenyl ethers rearrange on heating in various solvents to a mixture of trans-and cis-2-crotyl-6-alkyl-phenols. The amount of the cis-phenols in the rearrangement products decreases with the increasing bulk of the 6-alkyl substituent. This result is only obvious if the chair form of the transition state during the rearrangement of these ethers is highly favoured. trans-Crotyl 2,6-dimethylphenyl ether (trans- 33 ) rearranges highly steroselectively (94%) on heating to trans-4-crotyl-2,6-dimethyl-phenol (trans- 34 ). In the case of the corresponding cis ether 33 , the rapid cis → trans isomerisation of this ether and the cis/trans ratio of the phenol 34 indicate that the reverse rearrangement of the intermediate ortho-dienone to the ether 33 and the further rearrangement to 4-crotyl-2,6-dimethyl-phenol ( 34 ) has little stereoselective character.     

A new route for the preparation of pyrazolo[3,4-c] pyridines

Catalytic reduction of the oximes of 4-phenacyl-3(5)R-pyrazole-4-carboxylic acid esters ( 4a,b ) followed by cyclisalion constitutes a new appraoch to substituted pyrazolo[3,4-c]pyridines. The starting materials 4a,b were prepared by reaction of ω-bromoacetophenone oxime and sodium salts of oxalyl derivatives 2a,b and successive action of hydrazine on the obtained products 3a,b . Structural assignments rested upon correct elemental analysis and spectroscopic evidences.     

Syntheses and reactions of functional polymers. XCIII. Syntheses of polymers containing the N-(4-hydroxy-3-nitrophenyl)succinimide structure in the chain and the use of these activated polymer esters of N-blocked amino acids or peptides

Polymers containing the N-(4-hydroxy-3-nitrophenyl)succinimide residue were designed in order to achieve acyl activation of a reacting carboxylic acid in the solid phase. These polymers were prepared through the following three routes: (a) styrene was allowed to copolymerize with N-(4-hydroxy-3-nitrophenyl)- or N-(4-acetoxy-3-nitrophenyl)maleimide, (b) styrene was copolymerized with N-(4-acetoxyphenyl)maleimide in the presence of divinylbenzene (DVB), and the copolymer obtained was hydrolyzed and nitrated, (c) a copolymer of maleic anhydride and styrene was reacted with p-aminophenol, followed by nitration. The polymers prepared by routes b and c were converted to the activated polymer esters of N-blocked amino acids and peptides by using dicyclohexylcarbodiimide (DCC). The acylated polymers thus obtained were treated with amino acid esters and found to give peptides quantitatively without racemization.     

Lactide polymerization co‐initiated by carbohydrate esters and pyranoses

The polymerization of [S]‐lactide was accomplished using an initiating system comprising an alkyl zinc complex and a series of well defined carbohydrate co‐initiators derived from D ‐glucose, D ‐xylose, and 2‐deoxy‐D ‐ribose. The monosaccharide co‐initiators were aldonate esters and pyranoses, they were all prepared in high yield and had only a single alcohol co‐initiating group; the remaining carbohydrate hydroxyl functionalities were protected as acetyl, benzyl ether and isopropylidene acetal groups. The polymerizations were all well controlled, illustrated by the linear increase in poly(S‐lactide) M_n with percentage conversion of lactide, the increase in poly(S‐lactide) M_n with [lactide]₀‐[lactide]_t/[co‐initiator] and the narrow polydispersity indices of the polylactides. Thus, the novel initiating systems were used to produce poly(S‐lactides) end functionalized with a variety of different aldonate ester and pyranose groups and with degrees of polymerization from 10 to 250. The polyesters were fully characterized, including by NMR spectroscopy, size exclusion chromatography (SEC), matrix‐assisted laser deposorption/ionization (MALDI) mass spectrometry and by static water contact angle measurements. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4350–4362, 2008     

Bio‐based copolymers obtained through miniemulsion copolymerization of methyl esters of acrylated fatty acids and styrene

Polymers based on renewable sources are promising materials, and can find many uses in coatings and adhesive applications. The goal of this work was to synthesize and characterize bio‐based styrene/acrylated fatty acid methyl ester (AFAME) copolymer—poly(styrene‐co‐AFAME) prepared by miniemulsion polymerization. The main strategy adopted was to functionalize the bio‐monomer with acrylic acid that was confirmed by ¹H NMR and FTIR measurements, to allow its free‐radical homo‐ or copolymerization with styrene. Poly(styrene‐co‐AFAME) with different AFAME content were obtained and their composition were evaluated by ¹H NMR. Dynamic light scattering measurements throughout the reactions have indicated a very stable colloidal systems and average particles size ranges 100–150 nm. The structural and physical properties of poly(styrene‐co‐AFAME) were investigated by DTG‐DTA, DSC which displayed a decreasing of glass transition temperature with increase of AFAME content. The results showed in this study have indicated that the poly(styrene‐co‐AFAME) can be used in several fields because their characteristics are totally distinct. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 1422–1432     

Synthesis and characterization of thianthrene-containing poly(benzoxazole)s

New thioether- and thianthrene-containing poly(benzoxazole)s (PBOs) were synthesized from 4,4′-thiobis[3-chlorobenzoic acid] and thianthrene-2,7- and -2,8-dicarbonyl chlorides with commercially available bis-o-aminophenols. Polymers were prepared via solution polycondensation in poly(phosphoric acid) at 90–200°C. Transparent PBO films were cast directly from polymerization mixtures or m-cresol. The films were flexible and tough. Non-fluorinated PBOs were soluble only in strong acids and AlCl₃/NO₂R systems by forming complexes with the benzoxazole heterocycle Glass transition temperatures ranged from 298–450°C, and thermogravimetric analysis showed good thermal stabilities in both air and nitrogen atmospheres. © 1995 John Wiley & Sons, Inc.