Study of internal rotation of the vinyl group in 1-, vinylpyridones by the AM-1 method

By the AM-1 method in the semirigid model approximation, the potential energy of internal rotation of the vinyl group has been calculated for 1-vinyl-2-pyridone, 1-vinyl-6-methyl-2-pyridone, and 1-vinyl-4-pyridone. The potential energy of internal rotation in the first and third of these molecules has two minima corresponding to torsion angles around the N-C bond approximately 0 and 180°, separated by barriers to internal rotation 3.99 and 2.94 kcal/mole, respectively. For the 1-vinyl-2-pyridone, the energy minimum at =180°, the s-cis(O) conformation, is 1.83 kcal/mole above the first minimum. For the 1-vinyl-6-methyl-2-pyridone, the torsion angles 0 and 180° correspond to energy maxima; the energy minima occur at 35° and 140°. In the harmonic oscillator approximation, the intervals of torsional vibrations of the vinyl group in these comopunds have been estimated. Data from the AM-1 calculation are in qualitative agreement with the available¹H and¹³C NMR data on the structure of 1-vinyl-2-pyridone, 1-vinyl-5-methyl-2-pyridone, and 1-vinyl-4-pyridone.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1367–1372, June, 1991.     

Zur Struktur der Tetrahydro-4-phenylspiro([1]benzopyran-2,4′(1′H)-pyrimidin)-2′(3′H)-one bzw.-thione Über Heterocyclen, 49. Mitt

The structures of tetrahydro-4-phenylspiro([1]benzopyran-2,4(1H)-pyrimidin)-2(3H)-ones and-thiones4 a, b resp., are proved by synthesis. 3-(2-methoxy-3,5-dimethylphenyl)-3-phenylpropionic acid11 b is prepared from 3,4-dihydro-6,8-dimethyl-4-phenylcoumarin10. The lithium salt of11 b reacts with isobutenyl-lithium to 1-(2-methoxy-3,5-dimethylphenyl)-5-methyl-1-phenyl-4-hexen-3-on12 a. 12 a is transferred with urea in acid medium and NH₄CNS resp. in a mixture of dihydro-6-[2-(2-methoxy-3,5-dimethylphenyl)-2-phenyläthyl]-4,4-dimethyl-2(1H)-pyrimidinone and-thione13 a, b and tetrahydro-6-[2-(2-methoxy-3,5-dimethylphenyl)-2-phenyläthyliden]-4,4-dimethyl-2(1H)-pyrimidinone and-thione14 a, b resp.14 b leads to13 a, b with H₂O₂. Heating of13 a, 14 a and14 b resp. with pyridin-HCl leads to the spiro compounds4 a, b.     

Über 1H-2,1,5-Benzothiadiazocine, 1. Mitt.

Zusammenfassung Beim Umsetzen von 2-Aminobenzophenonen mit -Chloräthansulfochlorid erhält man die entsprechenden 2-Vinylsulfonyl-aminobenzophenone, die durch Behandeln mit NH₃ in absol. Äthanol zu 3,4-Dihydro-6-phenyl-1H-2,1,5-benzothiadiazocin-2,2-dioxiden als ersten Vertretern eines neuen heterocyclischen Ringsystems cyclisiert wurden. Das unterschiedliche Verhalten des 2-Aminobenzophenons und des 5-Chlor-2-aminobenzophenons bei der Reaktion mit -Chloräthansulfochlorid in Gegenwart von Triäthylamin wird diskutiert.

---

The reaction of 2-aminobenzophenones with -chloromethanesulfonylchloride yields the corresponding 2-vinylsulfonylaminobenzophenones, which are converted to 3,4-dihydro-6-phenyl-1H-2,1,5-benzothiadiazocine-2,2-dioxides by reaction with NH₃ in absolute ethanol. The latter are representatives of a new heterocyclic ringsystem. The different behavior of 2-aminobenzophenone and 5-chloro-2-aminobenzophenone in the reaction with -chloroethane sulfonylchloride in the presence of triethylamine is discussed.

---

---

Herrn Prof.L. Schmid mit besten Wünschen zum 70. Geburtstag gewidmet.

---

A-1060 Wien VI, Getreidemarkt 9.     

7-Azaindole derivatives

A study is made of new synthetic routes, based on accessible 3-formyl-7-azaindoles, to 3-substituted 7-azaindole. 2-Phenyl-4-(1-phenyl-4-methyl-7-azaindolyl-3-rnethylene)-1, 3-oxazol-5-one is synthesized, and it is converted to 1-phenyl-4-methyl-7-azatryptophane, 1-phenyl-4-methyl-7-azaindolyl-3-acetic acid,1-phenyl-3-(,-dihydroxypropyl)-4-methyl-7-azaindole, and 1-phenyl-4-methyl-7-azaindolyl-3-pyrotartaric acid.For Part XVIII see [1].     

Synthesis,structure and the e.s.r. spectrum of the mixed-valence molybdovandate Na2(NH4)4[(VIVVV8Mo)O28] · 10H2O

The mixed-valence molybdovanadate compound Na₂(NH₄)₄[V^IVV^V ₈Mo)O₂₈] · 10H₂O [Vanadata(6-)tetradeca--oxotetra-₃-oxodi-₆-oxoheptaoxo(oxomolybdate) nonatetrammonium disodium, decahydrate] has been synthesized from sodium molybdate(VI) dihydrate and sodium metavanadate dihydrate in aqueous solution by adding NH₂OH · HCl. The molecular structure has been determined by X-ray diffraction and is based on the isopolydecavanadate structure. The molybdate atom is crystallographically disordered over 6MO₆ octahedral sites. The e.s.r. spectrum clearly indicates that one vanadium atom has the oxidation number +4.     

Über Dihydro-6-methyl- bzw.-6-styryl-4-phenyl-2(1H)-pyrimidinone (-thione) sowie Hexahydro-5-benzoyl- bzw.-cinnamoyl-4,7-diphenyl-2(1H)-chinazolinone (-thione)

Zusammenfassung Dihydro-6-methyl-4-phenyl-2 (1H)-pyrimidinone (-thione) (1) reagieren als -Methylalkenylharnstoffe bzw.-thioharnstoffe mit Säuren zu Hexahydro-4,4-methylendi-2(1H)-pyrimidinonen (-thionen) (3), mit Phenolen zu Tetrahydro-6-hydroxyphenyl-2(1H)-pyrimidinonen (-thionen) (2), mit Benzaldehyd zu 6-Styrylverbindungen (1 d, e, g) und mit ,-ungesättigten Ketonen zu Tetrahydro-2(1H)-chinazolinonen (7). Aus 1,5-Diphenyl-1,4-pentadien-3-on und Harnstoffen, Thioharnstoffen bzw. Ammonrhodanid entstehen Diphenyl-1,3,7,9-tetraazaspiro-5,5-undecan-2,8-dione (9) bzw. Hexahydrotriphenyl-6-cinnamoyl-2(1H)-chinazolinthione (10). Hexahydro-6-benzoyl-bzw.-6-cinnamoyl-2(1H)-chinazolinone (-thione) (10) bilden sich allgemein bei Einwirkung von ,-ungesättigten Ketonen auf Dihydro-4-phenyl-6-styryl-2(1H)-pyrimidinone (-thione) (1 d, e, g).

---

Heterocycles, XXVII: Dihydro-6-methyl-(or-6-styryl-)-4-phenyl-2(1H)-pyrimidinones (-thiones); Hexahydro-5-benzoyl-(or-cinnamoyl-)-4,7-diphenyl-2(1H)-quinazolinones (-thiones)

Dihydro-6-methyl-4-phenyl-2(1H)-pyrimidinones (-thiones) (1) react as -methylalkenylureas (-thioureas) with acids to hexahydro-4.4-methylenedi-2(1H)-pyrimidinones (-thiones) (3), with phenols to tetrahydro-6-hydroxyphenyl-2(1H)-pyrimidinones (-thiones) (2), with benzaldehyde to 6-styryl compounds (1 d, e, g) and with ,-unsaturated ketones to tetrahydro-2(1H)-quinazolinones (7).On reacting 1.5-diphenyl-1.4-pentadien-3-one with ureas, thioureas or ammonium thiocyanate, the products formed are diphenyl-1.3.7.9-tetraazaspiro-5.5-undecane-2.8-diones (9) and hexahydrotriphenyl-6-cinnamoyl-2(1H)-quinazolinethiones (10), resp. Hexahydro-6-benzoyl- (or-6-cinnamoyl-)-2(1H)-quinazolinones (-thiones) (10) are formed generally by the action of ,-unsaturated ketones on dihydro-4-phenyl-6-styryl-2(1H)-pyrimidinones (-thiones) (1 d, e, g).

     

Characteristic Features of the Formation of Copper(I) π-Complexes with N-Allyl Derivatives of Piperazinium Sulfamate

The crystals of two copper(I) complexes and piperazinium sulfamate were synthesized by ac electrochemical technique from Cu(NH₂SO₃)₂· xH₂O and N,N-diallylpiperazine, N-allylpiperazine, or piperazine titrated by sulfamic acid in aqueous methanol to pH 4. The crystal structures of the complexes were determined (DARCh diffractometer, MoK radiation, /2 scan mode). The crystal data: [C₃H₅NH(CH₂)₄NHC₃H₅]_0.5[Cu(NH₂SO₃)₂] · H₂O (I), space group P1¯, a = 8.053(1) Å, b = 10.247(2) Å, c = 8.918(2) Å, = 113.03(1)°, = 107.14(2)°, = 95.15(1)°, Z = 2; [NH₂(CH₂)₄NH₂]_0.5NH₂SO₃ (II), space group P2₁/a, a = 8.468(7) Å, b = 5.92(1) Å, c = 10.890(9) Å, = 100.40(9)°, Z = 4; {[C₃H₅NH(CH₂)₄NHC₃H₅][NH₂(CH₂)₄NH₂]}_0.5[Cu(NH₂SO₃)₃] · H₂O (III), space group P1¯, a = 11.729(3) Å, b = 8.266(2) Å, c = 10.611(3) Å, = 82.13(2)°, = 65.73(2)°, = 74.86(2)°, Z = 2. Structure III is a hybrid of elements of structures I and II and contains the -coordinated Cu(I) atom surrounded by three -donor sulfamate nitrogen atoms, which was found for the first time.     

Arrangement and Diffusive Mobility of Extraframework Species in the Hydrated Ammonium Forms of Zeolites Clinoptilolite and Chabazite

The location and diffusive mobility of ammonium ions and water molecules in the channels of the NH₄substituted forms of the natural zeolites clinoptilolite (NH₄)_6.5[Al_6.5Si_29.5O₇₂] · 12.6H₂O and chabazite (NH₄)_9.6Ca_0.6Na_0.3[Al_11.1Si_24.9O₇₂] · 25.8H₂O were studied by Xray diffraction analysis and ¹H NMR spectroscopy. The arrangement of the extraframework subsystem was shown to be largely determined by hydrogen bonds N—H...O(H₂O) of length 2.7–2.9 . The diffusive mobility of the ions was found to correspond to abnormally low energy barriers, similar to those for H₂O diffusion. The activation parameters for the diffusion jumps of the ions and molecules are E(NH₄) = E(H₂O) = 31(2) kJ/mole, ₀(NH₄) = 2 · 10¹¹ sec^-1, ₀(H₂O) = 4 · 10¹² sec^-1 in NH₄chabazite and E(NH₄) = E(H₂O) = 25(1) kJ/mole, ₀(NH₄) = 2 · 10¹⁰ sec^-1, ₀(H₂O) = 3 · 10¹¹ sec^-1 in NH₄clinoptilolite. It is suggested that the development of ion and molecular diffusion is caused by the same defects, whose formation with temperature rise is controlled by Hbond rearrangement.     

The Mannich reaction with 2-methyl-5-vinylpyridine

1,3-Bis(dimethylamino)-2-(5-vinyl-2-pyridyl)propane and 2-(-dimethylaminoethyl)-5-vinylpyridine were prepared by the aminomethylation of 2-methyl-5-vinylpyridine. These Mannich bases have been transformed into 1-dimethylamino-2-(5-vinyl-2-pyridyl)-1-propene and 2,5-divinylpyridine by the decomposition of their quaternary salts.     

Zwitterionic [(H3NCH2C≡CC≡CCH2NH3)]Cu2Cl4 π-Complex: Template Synthesis and Crystal Structure

Crystals of the [(H₃NCH₂CCCCCH₂NH₃)]Cu₂Cl₄ -complex, formed in the oxidative dimerization of propargylammonium cations, were obtained by ac electrochemical synthesis from CuCl₂ · 2H₂O and propargylammonium chloride ([CCCH₂NH₃]Cl) and studied by X-ray diffraction analysis (DARCh automated diffractometer, MoK radiation, /2 scan mode; 2275 reflections with F 4(F), R = 0.048). Crystals are monoclinic: space group B2/b, a = 19.591(6) Å, b = 7.299(3) Å, c = 8.636(3) Å, = 106.83(3)°, Z = 4. The structure consists of individual [(H₃NCH₂CCCCCH₂NH₃)]Cu₂Cl₄ moietes united through the elongated Cu···Cl contacts (2.827(5) Å) into chains oriented along the [010] direction. The bond of the centrosymmetric propargylammonium dimer is -coordintated by copper(I) atom and is elongated to 1.227(6) Å.     

Decomposition of benzenediazonium fluoborate in esters of α,β-unsaturated acids

Summary It was shown that In contrast to the Meerwein-Koelsch reaction, the decomposition of benzenediazonlum fluoborate In esters of ,-unsaturated acids proceeds by a heterolytlc mechanism with the phenyl attacking the -carbon and the carbalkoxyl group of these esters. The reaction with ethyl crotonate gave -methylatropic acid (after hydrolysis) and a small amount of a dibasic acid, C₁₄H₁₆O₄ (or C₁₄H₁₄O₄). With methyl acrylate it gave atropic acid, phenyl acrylate, and a smaller amount of -methyl--phenylglutaric acid. With methyl methacrylate It formed benzylacrylic acid and the product of further conversions of phenyl methacrylate, namely the keto phenol 2-methyl-5-hydroxyindan-1-one.     

Influence of the temperature on the extraction of some lanthanides with 1-phenyl-3-methyl-4-benzoyl-pyrazolone-5

The extraction of Pr, Gd and Yb with 1-phenyl-3-methyl-4-benzoyl-pyrazolone-5 (HPMBP) diluted in CHCl₃, C₆H₆, and CCl₄ at 288 K, 298 K, 308 K, and 318 K has been investigated. A compound of the typeMe(PMBP)₃HPMBP is formed in the organic phase. The values of the thermodynamic constants as well as of the parameters H°, S° and G° have been determined.

---

Der Temperatureinfluß auf die Extraktion einiger Lanthaniden mit 1-Phenyl-3-methyl-4-benzoyl-5-pyrazolon

Zusammenfassung Es wurde die Extraktion von Pr, Gd und Yb mit 1-Phenyl-3-methyl-4-benzoyl-5-pyrazolon (HPMBP) in CHCl₃, C₆H₆ oder CCl₄ als verdünnendes Lösungsmittel bei 288 K, 298 K, 308 K und 318 K untersucht. Es wird eine Verbindung des TypsMe(PMBP)₃HPMBP in der organischen Phase gebildet. Die thermodynamischen Konstanten und auch die Parameter H°, S° und G° wurden bestimmt.

     

Platinum(II) Diaquadiammine Complexes. Stable Hydrolysis Products by DFT Quantum-Chemical Calculations

The most stable hydrolysis products of cis-[Pt(NH₃)₂(H₂O)₂]^{2 +} were revealed by means of DFT quantum-chemical calculations of this complex and its deprotonated forms with full geometry optimization. The resulting force fields and normal mode vibrations were used to calculate thermodynamic characteristics for possible hydrolysis stages and equilibrium constants for proton-transfer processes in the gas phase and in aqueous solutions. The hydroxo-bridged dimers [Pt(NH₃)₂(-OH)]₂ ^{2 +} with short Pt+++Pt distances are the hydrolysis products of platinum(II) cis-diaquadiamminates in the aqueous medium.     

Stereochemistry of the synthesis of 1,2,3,4-tetrahydrocinnolines from aryldiazenium salts and olefins

It follows from the PMR spectra that the reaction of 1-methyl-, 1-phenyl-, 1-ethyl-,1-phenyl-, and 1,1-diphenyldiazenium salts with cis- and trans-d-styrenes, which leads to the corresponding 3-d-4-phenyl-1,2,3,4-tetrahydrocinnolines, takes place with retention of the configuration in the starting styrenes. It is therefore proposed that this reaction be regarded as a special case of [4⁺_s + 2_s]-cycloaddition.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1658–1661, December, 1977.     

Pyrimidines

The reaction of cyclohexanone with arylidenebisureas (e.g. benzal-bisurea) in an acid medium has given 4, 4-diaryl-2, 2-dioxo-5, 5-trimethylene-6, 6-spirobishexahydropyrimidines (II). The acid hydrolysis of IIa (aryl-C₆H₅) in the presence of 2, 4-dinitrophenylhydrazine leads to the 2, 4-dinitrophenylhydrazone of 2-hydroxy-8-oxo-4-phenyl-5, 6, 7, 8-tetrahydroquinazoline (IV). Compound IV was also obtained by the ozonization of 2-acetoxy-8-benzal-4-phenyl-5, 6, 7, 8-tetrahydroquinazoline (IX) and subsequent decomposition of the ozonide with a solution of 2, 4-dinitrophenylhydrazine. The structure of the compounds obtained was confirmed by means of their IR, UV, and PMR spectra. Corresponding 6, 6-spirobishexahydropyrimidines have also been obtained from 2-methylcyclohexanone, acetone, and methyl ethyl ketone and benzalbisurea.For part XIV, see [1].     

Acid-base properties of 1,2,5-oxadiazoles. 1. Methylfurazans

The basicities of 3-methyl-4-R-furazans (R = H, CH₃, C₂H₅, n-C₃H₇, NH₂ NHAcOCH₃, I, COOH, and NO₂) were investigated by PMR spectroscopy. It is shown that they are weak bases, the protonation of which is described by the H_A acidity function. Relationships between the chemical shifts of the protons of the methyl group and the R ° constants and the p _aBH ^K + and the M ° constants of the substituents were found.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 35–37, January, 1981.     

Über die Umsetzung von 6-Chlor-4-phenyl-3,4-dihydro-1H-2,1,3-benzothiadiazin-2,2-dioxid mit 1,4-Dijodbutan

Zusammenfassung Bei der Umsetzung des Dinatriumsalzes von 6-Chlor-4-phenyl-3,4-dihydro-1H-2,1,3-benzothiadiazin-2,2-dioxid (1) mit 1,4-Dijodbutan inDMF wurde das erwartete 1,3-Butano-derivat nich erhalten.1 wurde einerseits zu 6-Chlor-4-phenyl-1H-2,1,3-benzothiadiazin-2,2-dioxid (4) dehydriert, andrerseits traten je nach Herstellungsweise des Dinatriumsalzes Methylierungsreaktionen ein bzw. es entstanden 6-Chlor-1-(4-jodbutyl)-4-phenyl-3,4-dihydro-1H-2,1,3-benzothiadiazin-2,2-dioxid (7) und 6,6-Dichlor-4,4-diphenyl-3,3,4,4-tetrahydro-3,3-tetramethylenbis(1H-2,1,3-benzothiadiazin)-2,2,2,2-tetroxid (8).

---

Reaction of 6-chloro-4-phenyl-3,4-dihydro-1H-2,1,3-benzothiadiazine-2,2-dioxide with 1,4-Diiodobutane. (Cyclic and bicyclic sulfamides III)

On reaction of the disodium salt of 6-chloro-4-phenyl-3,4-dihydro-1H-2,1,3-benzothiadiazine-2,2-dioxide (1) with 1,4-diiodobutane inDMF the expected 1,3-butano derivative was not obtained. On the one hand1 was dehydrogenated to give 6-chloro-4-phenyl-1H-2,1,3-benzothiadiazine-2,2-dioxide (4), on the other hand according to the method of preparation of the disodium salt either methylation reactions occured or 6-chloro-1-(4-iodobutyl)-4-phenyl-3,4-dihydro-1H-2,1,3-benzothiadiazine-2,2-dioxide (7) and 6,6-dichloro-4,4-diphenyl-3,3,4,4-tetrahydro-3,3-tetramethylenebis(1H-2,1,3-benzothiadiazine)-2,2,2,2-tetroxide (8) were formed.

---

---

Herrn Prof. Dr.H. Nowotny gewidmet.     

Spectroscopic study of the electron-donor properties of 1-vinyl- and 1-ethylazoles

The thermodynamic parameters of the reaction of 1-vinyl- and 1-ethylazoles with phenol (K _as,-H, and -S) were calculated for 11 complexes with the aid of ER spectroscopy. The investigated compounds are arranged in the following order with respect to their basicities on the basis of their K _as and pK _a values: 1-ethylimidazole, 2-methyl-1-vinylimidazole, 1-ethylbenzimidazole, 1-vinylimidazole, 1-vinylbenzimidazole, 1-ethylpyrazole, l-ethyl-l,2,4-triazole 3,5-methyl-1-vinylpyrazole, 1-vinyl-1,2,4-triazole, 1-ethylbenzotriazole, 1-vinylbenzotriazole, and 1-vinylpyrazole. The hypsochromic shifts of the bands and the change in the extinction coefficient in the electronic absorption spectra of imidazoles and benzimidazoles in HCl solution as compared with ethanol solutions are determined by the increase in the conjugation system of the azoles rather than by their basicities.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 828–833, June, 1976.     

Oxidation of 1,3-Dioxacycloalkanes with Complexes of Potassium Chlorochromate and Chlorodiperoxochromate with 15-Crown-5, Catalyzed with 2,2,5,5-Tetramethyl- 4-phenyl-3-oxo-3λ5-imidazolin-1-yloxyl

2,2,5,5-Tetramethyl-4-phenyl-3-oxo-3⁵-imidazolin-1-yloxyl catalyzes oxidation of 2-isopropyl-1,3-dioxolane, 2-phenyl-1,3-dioxolane, 2-phenyl-4-chloromethyl-1,3-dioxolane, and 2-phenyl-1,3-dioxane with 15-crown-5 complexes of potassium chlorodiperoxochromate (KCrO₅Cl·2C₁₀H₂₀O₅) and potassium chlorochromate (KCrO₃Cl·2C₁₀H₂₀O₅). 2-Isopropyl-1,3-dioxolane is oxidized to the corresponding monoester in quantitative yield, and the 2-phenyl derivatives yield benzaldehyde. The spiro ketal, 2,2-pentamethylene-4-methyl-1,3-dioxane, is decomposed to cyclohexanone.     

Structure of the 18-Crown-6 Complex with Ammonium Hexafluorosilicate and Water

The crystalline host–guest type complex [(18-crown-6NH₄)₂][SiF₆]4H₂Ohas been obtained as the result of the interaction of SiF₄2NH₃ with 18-crown-6 (18C6) in an aqueous medium. Crystal data: monoclinic, space groupC 2 c, a=26.541(2), b=8.363(2), c=20.469(2) Å, = 122.43(1)°and Z=4. The final R-value is 0.070 for 3253 reflections with I 2(I).The crystals consist of the complex [NH₄18C6]⁺ cations, [SiF₆]^2-anions and water molecules. The ammonium cation is hydrogen bonded by three of its H-atoms to the crown ether oxygen atoms with N(1) O separations2.923(5)–2.940(5) Å and by the fourth H-atom to the fluorine atom of thehexafluorosilicate anion, the N(1)F(4) distance being 2.797(6) Å.The conformation of the macrocycle and the hydrogen-bond geometry in thecomplex cation closely resemble those in related adducts between 18-crown-6and ammonium salts. All crystal components are connected via a system of hydrogen bonds into a ribbon along the b axis in the unit cell.