Syntheses and Investigation of Some New Polyarylates and Copolyarylates. Part I

By the interfacial condensation of acid chlorides I, II, and III, respectively, with bifunctional phenols (IV-X), soluble or mold-able thermostable polyarylates were obtained. Similarly, copolyarylates were prepared from a mixture of the acid chlorides I + II or I + III. With bisphenol-A (VIII), soluble polymers are usually obtained. Methylene dichloride and/or carbon tetra-chloride-water systems were the best media for interfacial condensations, and the polymers formed showed the highest reduced viscosity values.

Polyester films are useful in many industrial applications because of their broad range of mechanical, optical, and electrical properties. The aromatic polyesters‐polyarylates-dominate the field of industrial polyester films [1].

Polyarylates prepared from dihydric phenols and purely aromatic dicarboxylic acid chlorides are highly heat resistant materials [2], but they are insoluble and nonmoldable [3]. However, by the introduction of ether linkages in the aromatic dicarboxylic acid moiety, soluble and/or moldable polyamides were obtained [4].     

Isoquinoline derivatives VI. Synthesis and pharmacological properties of 4,6,7-substituted 1(2)-arylalkyl-1,2,3,4-tetrahydroisoquinolines and their analogs

The condensation of 6,7-dimethoxy-1,2.3.4-tetrahydroisoquinoline (II) with diphenylacetyl and diphenylpropionyl chlorides gave the corresponding amides (III). Reduction of III with lithium aluminum hydride converted them to tertiary amines IV, which were characterized as their hydrochlorides. The condensation of equimolecular amounts of amines I with the acid chlorides of substituted phenylacetic and diphenylpropionic acids gave amides V. The reduction of amides V with lithium aluminum hydride gave secondary amines VI. The corresponding tetrahydroisoquinolines (VII) were obtained by the cyclization of amides V and subsequent reduction with lithium aluminum hydride, The condensation of 1-diphenylethyl-6,7-dimethoxy-l,2,3,4-tetrahydroisoquinoline with formalin gave VIII. The IR spectra of the synthesized compounds were examined. The effect of these compounds on the arterial blood pressure and the coronary blood flow was studied.See [1] for communication V.Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1683–1687, December, 1971.     

Heterocycles derived from the condensation of 1,3-propanediamine with phthalic acid derivatives

The condensation of phthalic anhydride with 1,3-propanediamine afforded N-(o-carboxybenzoyl)-1,3-propanediamine (I) which by intravolecular cyclization was transformed into 2,3,4,6-b-tetrahydropyrimido[2,1-a]isoindol-6-one (II) rather than the benzodiazonine (III). An intermediate in the condensation is proposed. The reaction of 1,3-propanediamine with dimethyl phthalate also did not afford III, but rather a more complex product, dibenzo[c,l]-1,6,10,15-tetraazacyclooctadecane-5,11,16,22-tetraone (IX). Reaction of 1,3-propanediamine with phthaloyl chloride gave 6,13-propanodibenz[c,h]-1,6-diazecine-5,7,12,14-tetrone (XII). Spectroscopic data of the heterocycles obtained and chemical properties of II are given.     

Synthesis of 1,2,3‐Triazole Substituted Isoxazoles via Copper (I) Catalyzed Cycloaddition

The synthesis of a series of 3,5‐disubstituted isoxazole‐4‐carboxylic esters containing N‐substituted 1,2,3‐triazoles ( V ) starting from various benzaldehydes ( I ) is reported. Benzaldehydes undergo oximation with hydroxylamine hydrosulfate. Later, chlorination followed by condensation with methylacetoacetate and the hydrolysis of the resulting ester afforded respective carboxylic acid ( II ), which on chlorination with PCl₅ gave the corresponding acid chlorides ( III ). The coraboxylic acid chlorides ( III ) on propargylation gave propargylic esters ( IV ) and these on click reaction gave the title compounds ( V ).     

Some reactions of 5-methyl-11H-isoindolo[2,1-α] benzimidazolium salts

5-Methyl-11H-isoindolo[2,1-α]benzirnidazolium halide (IV), obtained by direct quaternization of the precursor III, underwent facile condensation reactions at its 11-methylene group similar to those of 11H-isoindolo[1,2-b]benzothiazolium cation II. Although the treatment of II with alkali regenerated its precursor I, treatment of IV with alkali caused ring opening to a phthalimidine. Attempted thermal cyclization of 2-(alkylaminophenyl)phthalimidines, e.g., VII, resulted in dealkylation to produce III.     

Synthesis of some substituted pyrido[1,2-a]pyrimidin-4-ones and 1,8-naphthyridines

The substituted 4H-pyrido[1, 2-a]pyrimidin-4-ones (I) were obtained by the condensation of substituted 2-aminopyridines with δ-ketocarboxylic esters in PPA. Some of the derivatives I were transformed into the corresponding 1, 8-naphthyridines II and III.     

Preparation and properties of polyamides from 2,8-phenoxathiin-bis-(γ-ketobutyric acid), 2,7-thianthrene-bis(γ-ketobutyric acid), and aromatic diamines

Aromatic-aliphatic polyamides containing phenoxathiin and thianthrene heterocyclic units were prepared by the direct polycondensation of 2,8-phenoxathiin-bis(γ-ketobutyric acid) ( I ) or 2,7-thianthrene-bis(γ-ketobutyric acid) (II) with various aromatic diamines in a triphenylphosphite-pyridine system. Prior to polymer synthesis two model diamides were prepared by condensing γ-keto acid I or II with p-toluidine. The model diamides and polyamides were characterized by spectral methods and elemental analysis. The polyamides, obtained in 56–90% yields, had inherent viscosities in the 0.82–1.1 dL/g range in concentrated H₂SO₄ at 30°C. The effect of heterocyclic units on polymer properties, such as solubility, crystallinity, and thermal stability has been discussed.     

Ein neuer zugang zu indeno[1,2-b]pyridinen

A new synthesis of 5H-indeno[1,2-6]pyridines [IV] starting from 4-cyanobutyrophenones [I] or their cyclization products, the 6-phenyl-3,4-dihydropyridin-2-ones [II], is reported. The condensation of I or II in polyphosphoric acid with aromatic or heteroaromatic aldehydes [III] yields 1,2,3,4-tetrahydro-5H-indeno[1,2-b]pyridin-2-ones [IV]. 2,3,4,4a,5,9b-Hexahydro-1H-indeno[1,2-b]pyridines [X, XI] which were previously difficult to obtain can now be easily synthesized from compounds IV.     

Synthesis of 3,4-Dihydrophthalazin-1(2H)-one by Zinc Reduction of Phthalazin-1(2H)-one

3,4-Dihydrophthalazin-1(2H)-one (II) was first prepared by H.Sund ¹⁾, by electrochemical reduction of phthalazin-1(2H)-one (I) (phthalazone). In the recent years we have described new syntheses of II, through easily hydrolyzable mono- or diacetyl- derivatives, namely condensation of 2-bromomethylbenzoylchloride with N,N'-diacetylhydrazine ²⁾ catalytic reduction of I in acetic acid ²⁾ or of 2-acetylphthalazone in acetic anhydride ³⁾ The reduction of I with zinc is known to proceed with ring contraction and formation of N-aminophthalimidine (III)⁴⁾ (zinc and sodium hydroxide at about 100[ddot]C) or of phthalimidine (IV) ⁵⁾ (zinc and hydrochloric acid under unspecified conditions).

Having observed that II is transformed into N-aminophthalimidine when heated with hydrazine hydrate ⁶⁾ or sodium hydroxide ²⁾, the zinc reduction of I was reinvestigated with the aim to find out in which cases the intermediate formation of II can be dem-onstratedo     

Synthesis and characterization of fluorine-containing polyamides derived from 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane by direct polycondensation

A fluorine-containing diamine, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (BAPPH) ( II ), was synthesized in two steps on condensation of 2,2-bis(4-hydroxyphenyl)hexafluoropropane with p-chloronitrobenzene in the presence of potassium carbonate, giving 2,2-bis[4-(4-nitrophenoxy)phenyl]hexafluoropropane ( I ), followed by reduction with hydrazine monohydrate/Pd—C. Fluorine-containing polyamides and copolyamides having inherent viscosities 0.41–0.88 dL g⁻¹ were prepared by direct polycondensation of BAPPH with various aromatic diacids or with mixed diacids, by triphenyl phosphite and pyridine in N-methyl-2-pyrrolidinone (NMP). The polyamides were examined by elemental analysis, IR spectra, inherent viscosity, x-ray diffraction, solubility, DSC, and TGA. The diffractogram showed that the polyamides were crystalline except IVb , IVc , IVf , and Vc . Almost all polyamides were soluble in polar aprotic solvents. The polymers obtained from BAPPH lost no mass below 350°C, with 10% loss of mass being recorded above 467°C in nitrogen. These aromatic polyamides had glass transition temperatures in the 221–253°C range. © 1996 John Wiley & Sons, Inc.     

Use of phosphite amides in the synthesis of polyamides

The preparation of polyamides by the phosphite amide procedure was investigated. The yield of amidation was determined in the reaction of diethyl- or o-phenylenephosphite derivatives of piperidine, piperazine, or trans-2,5-dimethylpiperazine with either mono- or dicarboxylic acids. Higher yields were obtained by using diethyl phosphite derivatives; however, for both types of derivatives the yields were never greater than 90%. Only low molecular weight polymers could be obtained under optimum reaction conditions. In the polycondensation of (+)-trans-1,3-cyclohexanedicarboxylic acid or (+)-trans-1,2-cyclohexanedicarboxylic acid with phosphite derivatives of either piperazine or trans-2,5-dimethylpiperazine, the optical rotation of the polymers was lower than the rotation of the corresponding polyamides prepared by the interfacial condensation procedure with dicarboxylic acid chlorides. It was shown that an intermediate mixed anhydride was formed during the amidation reaction. This may account for the observed racemization.     

Aromatic Polyamides of 2,6-Naphthalenedicarboxylic Acid

Wholly aromatic polyamides have been prepared by the interfacial polycondensation of 2,6-naphthalenedicarboxylic acid chloride with m-phenylenediamine. Also, copolyamides with isophthaloyl or terephthaloyl chlorides and the naphthalene diacid chloride were synthesized. The resultant polyamides were amorphous or slightly crystalline as determined by x-ray diffraction, had tensile properties characteristic of hard, strong materials, and were more thermally stable than aromatic polyamides prepared solely from benzene diacid chlorides.     

Bis(trimethylsilyl)amino-halogenoborane und ihre cyclischen Kondensationsprodukte

Zusammenfassung Bis-[bis(trimethylsilyl)amino]-fluorboran (I), Bis-(trimethylsilyl)-amino-dichlorboran (II) und Bis-[bis(trimethylsilyl)-amino]-chlor-boran (III) werden durch Umsetzung von BCl₃ und BF₃ mit NaN(Sime ₃)₂ in Äther dargestellt. Alle Verbindungen lassen sich thermisch unter Abspaltung von Trimethylhalogenosilanen kondensieren. Während II zu B-Trichloro-N-tris(trimethylsilyl)-borazol kondensiert, ergeben I und III überraschend ein viergliedriges B–N-Ringsystem.Phenyl-alkoxy-bis(trimethylsilyl)aminoborane gehen ähnliche Kondensationsreaktionen ein.

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Bis-[bis(trimethylsilyl)amino]-fluoroborane (I), bis(trimethylsilyl)amino-dichloroborane (II) and bis-[bis-(trimethylsilyl)amino-]chloroborane (III) were synthesized by reaction of BF₃ and BCl₃ with sodium-bis(trimethylsilyl)-amide. All compounds undergo thermal condensation under elimination of the corresponding trimethylhalosilane. So II forms B-trichloro-N-tris(trimethylsilyl)-borazene, while I and III unexpectedly yield a fourmembered B–N-ring system. Phenyl-alkoxy-bis-(trimethylsilyl)-aminoboranes condense in a similar way to B-phenyl-N-trimethylsilyl-borazene.

     

Synthesis and properties of polyamides with [60]fullerene in the main chain

A novel series of polyamides having [60]fullerene moieties in the main chain were synthesized by a direct polycondensation of [60]fullerenobis(acetic acid) or [60]fullerenobis(acetic acid)/isophthalic acid mixture with a diamine in the presence of triphenyl phosphite and pyridine. Various properties of the polyamides were characterized by means of IR, GPC, TGA, DSC, UV–visible, and photoluminescence. The molecular weight M_w of the [60]fullerene-containing polyamides was observed in the range from about 300,000 to 3,000; upon the changing of the ratio of [60]fullerenobis(acetic acid)/isophthalic acid in the starting mixture, the resulting M_w decreased with increasing the ratio. Most of the thermal and optical properties gradually changed as the ratio changed; the major optical absorption band in visible range exhibited a significant tailing, which shifted toward a longer wavelength, while the photoluminescence spectrum red-shifted with increasing [60]fullerene content. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 3139–3146, 1998     

Synthesis of heterocycles from arylation products of unsaturated compounds: XVIII. 5-Arylfuran-2-carboxylic acids and their application in the synthesis of 1,2,4-thiadiazole, 1,3,4-oxadiazole,and [1,2,4]triazolo[3,4-<Emphasis Type="Italic">b</Emphasis>][1,3,4]thiadiazole derivatives

Arylation of furan-2-carboxylic acid or its methyl ester with arenediazonium chlorides in the presence of copper(II) chloride gave the corresponding 5-arylfuran-2-carboxylic acids or methyl 5-arylfuran-2-carboxylates. 5-Arylfuran-2-carbonyl chlorides reacted with potassium thiocyanate and then with 5-methyl-1,2-oxazol-3-amine to give 5-aryl-N-[3-(2-oxopropyl)-1,2,4-thiadiazol-5-yl]furan-2-carboxamides as a result of recyclization of intermediate isoxazolylthiourea derivatives. The reactions of 5-arylfuran-2-carbonyl chlorides with 5-(2-furyl)-1H-tetrazole involved opening of the tetrazole ring with elimination of nitrogen molecule and led to the formation of 2-(5-arylfuran-2-yl)-5-(2-furyl)-1,3,4-oxadiazoles. 3-Substituted 6-(5-arylfuran-2-yl)-[1,2,4]triazolo[3,4-b][1,3,4]thiadiazoles were obtained by condensation of 5-arylfuran-2-carboxylic acids with 5-substituted 4-amino-4H-1,2,4-triazole-3-thiols in phosphoryl chloride.     

Sur les dérivés de la fluorénone VIII. Difluorénonyl-cétones,difluorényl-cétones et difluorényl-méthanes

By condensation of the chlorides of the four isomeric fluorenecarboxylic acids, respectively of the three 1-, 3- and 4-fluorenonecarboxylic acids with fluorene, followed by reduction of the obtained mono-respectively diketones, the four difluorenylmethanes I, II, III and IV are synthesized. The oxydation of the diketones gives the corresponding triketones. Starting from the chloride of 4-fluorenecarboxylic acid and 1-methylfluorene, a methyl derivative of IV is analogically obtained.     

Synthese der enantiomeren 1,6-Spiro[4.4]nonadiene

Two new syntheses of spiro[4.4]nonane-1, 6-dione (I) are described: one by rearrangement of 1,6-epoxy-bicyclo[4.3.0]-nonane-2-one (IV) with boron trifluoride, the other by an acid catalyzed, intramolecular Claisen condensation of 4-(2-oxocyclopentyl)-butyric acid. Spiro[4.4]-nonane-1,6-dione is converted into trans, trans-spiro[4.4]nonane-1,6-diol which is resolved into enantiomers via the diastereomeric esters with (?)-camphanic acid. (+)-(5S)-Spiro[4.4]nona-1,6-diene (III) is prepared from (1R, 6R)-trans,trans-spiro[4.4]nonane-1,6-diol (II) by pyrolysis of the corresponding bis-4-methylphenyl-thionocarbonate. This modification of the Chugaev reaction is particularly useful with sterically hindered alcohols which cannot be converted into S-me-thylxanthates. The circular dichroism, UV.- and NMR.-spectrum of optically active spiro[4.4]-nonane-1,6-diene are discussed.     

The preparation of 2H-1,2,3-benzothiadiazine-1,1-dioxides, 11H-11a-dihydrobenzimidazo[1,2-b] [1,2] benzisothiazole-5,5-dioxides, 6H-dibenzo[c,g] [1,2,5] thiadiazocine-5,5-dioxides and 5H-Dibenzo[c,g] [1,2,6] thiadiazocine-6,6-dioxides

o-Benzoylbenzenesulfonyl chlorides (I) were prepared conveniently from aminobenzophenones by diazotization followed by reaction with sulphur dioxide in the presence of Cu⁺, according to the general method of Meerwein. Reaction of the sulfonyl chlorides with hydrazine led to 4-phenyl-2H-1,2,3-benzothiadiazine-1,1-dioxides (II). The latter compounds could be methylated and acetylated readily in the 2-position. The 2-methyl derivative (III) could be prepared also by reaction of the sulfonyl chloride (Ia) with methylhydrazine. Catalytic hydrogenation of 6-chloro-4-phenyl-2H-1,2,3-benzothiadiazine-1,1-dioxide (IIa) gave the 3,4-dihydro derivative (V). Reaction of the sulfonyl chlorides (I) with o-phenylenediamine followed by cyclodehydration led to 11H-11,11a-dihydrobenzimidazo[1,2-b] [1,2]benzisothiazole-5,5-dioxides (VII). One of the latter compounds (VIIa) in sodium hydroxide solution in the presence of methyl iodide or benzyl chloride was transformed into 6-methyl- and 6-benzyl-5H-dibenzo[c,g] [1,2,6]thiadiazocine-5,5-dioxides (VIII), respectively. 5H-Dibenzo[c,g] [1,2,6] thiadiazocine-6,6-dioxides (XIV) were prepared also by cyclodehydration of 2-amino-2′-benzoylbenzenesulfonanilides (XIII).     

Formation of 6-formyl-7-hydroxy-8-methoxycoumarin and 5,8-dioxopsoralen by reaction of 8-methoxypsoralen with H2O2 and potassium superoxide (KO2) catalyzed by halogenated or perhalogenated 5,10,15,20-tetraarylporphyrinatoiron(III) chlorides

The oxidation of 8-methoxypsoralen (2) with hydrogen peroxide and potassium superoxide catalyzed by 5,10,15,20-(2,4,6-trimethylphenyl)porphyrinatoiron(III) chlorides [Me12TPPFe(III)Cl] (1a) and 5,10,15,20-(2,6-dichlorophenyl)porphyrinatoiron(III) chlorides [Cl8TPPFe(III)Cl] (1b) in dichloromethane gives 6-formyl-7-hydroxy-8-methoxycoumarin (3) in moderate yields, whereas the oxidation of (2) with H2O2 catalyzed by 5,10,15,20-(2,6-dichlorophenyl)-beta-octahaloporphyrinatoiron(III) chlorides [Cl8betaX8TPPFe(III)Cl] (X=Cl, Br) (1c, 1d) gives specifically 5,8-dioxopsoralen (4) in moderate yields.     

Synthesis of 1,2,3,4-tetrahydroquinazoline derivatives as potential alpha-adrenergic blocking agents

The synthesis of N,N′-bis[6-(1,2,3,4-tetrahydro-3-quinazolidyl)hexyl]cystamine (I) and 3-(6-aminohexyl)-1,2,3,4-tetrahydroquinazoline (II) are described. Compound I is obtained by condensation of o-nitrobenzoyl chloride with 3-(6-aminohexyl)-1,3-thiazolidine (III) followed by dimerization, reduction and formation of tetrahydroquinazoline ring. A similar method was used for preparation of compound II. These compounds and some synthesis intermediates are potential alpha-adrenergic blockers.