The Birch Reduction - Dialkylation Reaction of Aromatic Carboxylic Acids. Identification of NaNH2 as the Base Responsible for the Second Alkylation

The Birch reduction-alkylation of 3,5-dimethoxybenzoic acid with excesses Na and EtBr gives 1,4-diethyl-3,5-dimethoxy-2, 5-cyclohexadiene carboxylic acid, 3. The responsible for the alkylation at C-4 has been identified as NaNH₂, generated in Situ.     

Selective side-chain oxidation of peralkylated pyrromethene?BF2 complexes

Treatment with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) oxidized 2,6-diethyl-1,3,5,7,8-pentamethylpyrromethene–BF₂ complex 1 , 13,14-trimethyl-2, 3, 4, 5,9,10,11,12-octahydroindomethene–BF₂ complex 5 , and 1,3,5,7,8-pentamethyl-1,2,3,5,6,7-hexahydropyromethene–BF₂ complex 8 to the weakly fluorescent 3-formyl, 5-oxo, and 8-formyl derivatives 4 , 6 , and 9 , respectively. The dye 1 was oxidized by lead tetraacetate to 1,7,8-trimethyl-2,6-diethyl-3,5-diacetoxymethylpyrromethene–BF₂ complex 12 [λ_f (ethanol) 538 nm, Φ 0.62, λ_las (ethanol) 555–570 nm]. Catalytic reduction (Pd/C) converted the aldehyde 4 to 2,6-diethyl-3-hydroxymethyl-1,5,7,8-tetramethylpyrromethene–BF₂ complex 10 [λ_f (ethanol) 537 nm, Φ 0.70, λ_las (ethanol) 547–575 nm].     

Relationship between reduction potentials and electron affinities of fullerenes and their derivatives

A linear relationship was found between the first reduction potentials (E°_red) and electron affinities (EA) for fullerenes C₆₀ and C₇₀, their hydro- and fluoro-derivatives, and aromatic hydrocarbons: E°_red = –3.04 + 0.81·EA. This equation was used to estimate the unknown values of EA = 2.45 eV for C₆₀H₂, 2.47 eV for C₇₀H₂, –0.15 eV for C₇₀H_36—38, –0.41 eV for C₇₀H_44—46, and E°_red = –1.74—–1.91 V (vs. Fc^0/+) for C₆₀H₁₈.     

Organometallic derivatives of 2,6-di-tert-butylphenols as specific inhibitors of methyl oleate oxidation

2,6-Di-tert-butylphenols containing the Pt—SnCl₃ and Pt—GeCl₃ groups in the para position exert a dual effect on the oxidation of methyl oleate by molecular oxygen. Initially, these compounds act as antioxidants producing the corresponding phenoxyl radicals whose decomposition is accompanied by elimination of SnCl₂ and GeCl₂, which are oxidation promoters.     

Methylthiomethylierung von Anilinen und Phenolen, 3. Mitt.: Darstellung von N-Aryl-S,S-dialkylsulfimiden

Zusammenfassung Aus Anilinen, die im aromatischen Ring mit CH₃, CH₃SCH₂, CH₃O, Cl, Br oder NO₂ substituiert sind, und Sulfoxiden wird in Anwesenheit von P₄O₁₀ und Triäthylamin eine Reihe von N-Aryl-S,S-dialkylsulfimiden erhalten. Diese Reihe umfaßt Verbindungen mit CH₃-, C₂H₅- und –(CH₂)₄-Gruppen am Schwefelatom. Das Sulfimid aus Mesidin lagert sich—formal analog zu einerSommelet—Hauser-Umlagerung—zum 2,4,6-Trimethyl-2-methylthiomethylcyclohexa-3,5-dien-1-imin um.

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Methylthiomethylation of anilines and phenols, III: Preparation of N-aryl-S,S-dialkylsulfimides

The synthesis of a number of N-aryl-S,S-dialkylsulfimides by reaction of anilines with sulfoxides in presence of P₄O₁₀ and triethylamine is given. This series includes compounds with CH₃-, CH₃SCH₂-, CH₃O-, Cl-, Br- and nitro-groups attached to the aromatic nucleus, resp., and with CH₃-, C₂H₅-or–(CH₂)₄-groups on the sulfur atom. The sulfimide obtained from mesidine is rearranged in formal analogy to aSommelet-Hauser rearrangement to 2.4.6-trimethyl-2-methylthio-methylcyclohexa-3.5-dien-1-imine.

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Als 1. Mitt. soll gelten:P. Claus, Mh. Chem.99, 1034 (1968).

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2. Mitt.:P. Claus undW. Vycudilik, Tetrahedron Letters1968, 3607.     

Chemistry of condensed thiophenes. III. Acetylation of triphenyleno [1,12-bcd]thiophene

Friedel-Crafts reaction of triphenyleno[1,12-bcd]thiophene (2) by means of aluminum chloride, nitrobenzene, and a limited excess of acetyl chloride yielded 3-acetyl-2 (78%) and 3,5-diacetyl-2 (7%). Use of a large excess of acetyl chloride gave yields of 42% and 22%, respectively. Wolff-Kishner reduction of the acetyl compounds produced 3-ethyl-2 (15%) and 3,5-diethyl-2 (8%). Structures were assigned largely on the basis of ¹H nmr and ultraviolet absorption spectra of the products.     

Pyrolysis and photolysis processes of pyran and thiopyran derivatives

Summary Pyrolysis and photolysis of 2-amino-3,5-dicyano-6-phenyl-4H-pyran (1) afford HNCO, acrylonitrile, cinnamonitrile, and 2-hydroxy-3,5-dicyano-6-phenylpyridine. Pyrolysis of 2-carboxyimino-3,5-dicyano-6-phenyl-4H-pyran (2) gives HCN, acrylonitrile, cinnamonitrile and 2-hydroxy-3,5-dicyano-6-phenylpyridine. Furthermore, both pyrolysis and photolysis of 2,6-diamino-3,5-dicyanothiopyran (3a) gives rise to HNCS, acrylonitrile and 6-amino-3,5-dicyano-6-mercaptopyridin. Moreover, comparative studies of pyrolysis and photolysis of 2,6-dicyano-4-arylthiopyran derivatives3b–d revealed similar results. The similarity of products obtained from pyrolysis and photolysis and the mechanistic implications of these data are discussed.

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Pyrolyse- und Photolyseprozesse von Pyran- und Thiopyranderivaten

Zusammenfassung Pyrolyse und Photolyse von 2-Amino-3,5-dicyano-6-phenyl-4H-pyran (1) ergeben HNCO, Acrylnitril, Zimtsäurenitril und 2-Hydroxy-3,5-dicyano-6-phenyl pyridin. Durch Pyrolyse von 2-Carboximino-3,5-dicyano-6-phenyl-4H-pyran (2) entstehen HCN, Acrylnitril, Zimtsäurenitril und 2-Hydroxy-3,5-dicyano-6-phenylpyridin. Weiters resultieren sowohl Photolyse als auch Pyrolyse von 2,6-Diamino-3,5-dicyanithiopyran (3a) in der Bildung von HNCS, Acrylnitril und 6-Amino-3,5-dicyano-6-mercaptopyridin. Vergleichende Untersuchungen zur Pyrolyse und Photolyse von 2,6-Dicyano-4-arylthiopyranderivaten (3b–d) lieferten vergleichbare Ergebnisse. Die Ähnlichkeit der Resultate von Pyrolyse und Photolyse sowie die sich daraus ergebenden mechanistischen Implikationen werden diskutiert.

     

Investigation of the compositions and structures of the components of lactone C12H22O2 — the side product of the condensation of n-butyl alcohol

It was established by gas-liquid chromatography (GLC) that lactone C₁₂H₂₂O₂ consists of three components. Two components, which are its isomers, were isolated by rectification and also by means of preparative GLC. A racemic mixture of optical isomers of 2,4-diethyl-3-n-propylpentanedioic acid was isolated from the products of potassium permanganate oxidation of the salts of the hydroxy acids obtained from the isolated lactone isomers in one case, whereas the meso form of this acid was isolated in another case. On the basis of this, it was concluded that one lactone isomer, constituting 60–70% of the mixture, is 2,4_trans-diethyl-3_cis-n-propyl-5-pentanolide or 2,4_trans-diethyl-3_trans-n-propyl-5-pentanolide, and the other isomer, constituting 20–30% of the mixture, is 2,4_cis-diethyl-3_cis-n-propyl-5-pentanolide or 2,4_cis-diethyl-3-_trans-n-Propyl-5-Pentanolide.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1174–1179, September, 1975.     

Synthesis,crystal structure and e.p.r. spectra of one-dimensional manganese(II) 3,5-dinitrobenzoate dihydrate

The crystal structure of catena-diaquatetrakis(₂-3,5-dinitrobenzoato-O,O)manganese(II) has been determined by X-ray diffraction. It consists of a chain with the 3,5-dinitrobenzoate group acting in the syn-anti ₂-O,O-bridging fashion, in which the Mn^II atom is octahedrally coordinated by two aqua ligands [2.162(3) Å] and four carboxy oxygen atoms [Mn—O = 2.114(3) and 2.221(3) Å]. The X-band e.p.r. spectra of this complex show a hyperfine structure due to Mn^II (I = 5/2) with a splitting factor (A) of 97 G at 5 K and 93 G at 19 K, respectively.     

Ring-closing metathesis of 2,2-diallyl derivatives of pyrrolidine and piperidine: a route to azaspiroheterocyclic structures

Transformations of 1-benzyl-2,2-di(2-propenyl)pyrrolidine and 1-benzyl-2,2-di(2-propenyl)piperidine into the corresponding 1-azaspiro[4.n]alkenes via ring-closing metathesis using accessible homogeneous catalytic systems WCl₆—H₂SiPh₂, WOCl₄—H₂SiPh₂, and Ru(=CHPh)(PCy₃)₂Cl₂ (Cy is cyclohexyl) were performed for the first time.     

Formation of 1,2,4-triazoles by the action of angeli's salt on secondary amines and alkylhydrazones

Two years ago we reported [1] the presence of one of the isomeric triazoles C₆H₁₁N₃ — apparently 3,5-dimethyl-1-ethyl-1,2,4-triazole — in the products of the reaction of Angeli's salt with diethylamine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 563–564, April. 1976.     

Syntheses and structures of silver(I) complexes of 4-amino-3,5-dimethyl-4<Emphasis Type="Italic">H</Emphasis>-1,2,4-triazole and 4-amino-3,5-diethyl-4<Emphasis Type="Italic">H</Emphasis>-1,2,4-triazole: role of the substituents

Five silver(I) adducts of 4-amino-3,5-diethyl-4H-1,2,4-triazole (4-NH₂-3,5-Et₂-tz) or 4-amino-3,5-dimethyl-4H-1,2,4-triazole (4-NH₂-3,5-Me₂-tz), namely [Ag₄(4-NH₂-3,5-Et₂-tz)₆](ClO₄)₄ (1), [Ag(4-NH₂-3,5-Et₂-tz)₂] _n ·n(ClO₄) (2), [Ag₄(4-NH₂-3,5-Et₂-tz)₆](CF₃SO₃)₄ (3), [Ag₄(4-NH₂-3,5-Me₂-tz)₆](ClO₄)₄·4H₂O (4) and [Ag₄(4-NH₂-3,5-Me₂-tz)₆](CF₃SO₃)₄·2H₂O (5), have been prepared and structurally characterised by X-ray single crystal diffraction. Two types of Ag₄tz₆ cluster have been observed in the structures of compound 1, 3, 4 and 5, which is rationalised based on the minimisation of the steric repulsions between the substituents on the 3,5-positions of triazole ring. Compound 2 displays an infinite chain structure and may be an intermediate or a minor product in the preparation.     

l,3-Dipolar cycloaddition of unsatu rated ferrocene derivatives with carbonitrileN-oxides

3,5-Disubstituted isoxazolines and isoxazoles have been synthesized using 1,3-dipolar cycloaddition of ferrocene derivatives FcCH=CH₂, FcCOCH=CH₂ and FcCCH with aliphatic and aromatic carbonitrileTV-oxides.Translated fromIzyestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 139–142, January, 1994.     

Eine verbesserte fluorimetrische Bestimmung des Glycerid-Glycerins

Zusammenfassung Glycerid-Glycerin gibt bei der Oxydation mit Perjodat Formaldehyd, der sich fluorimetrisch als 3,5-Diacetyl-1,4-dihydrolutidin bestimmen läßt. Überschüssiges Perjodat liefert hohe Blankwerte. Durch Reduktion mit KJ/Na₂S₂O₃ oder Rhamnose wird die Blankfluoreszenz verringert. Rhamnose beeinflußt im Gegensatz zum Thiosulfat die Fluoreszenz des gebildeten 3,5-Diacetyl-1,4-dihydrolutidins nicht. Der Bestimmungsbereich beträgt 3·10^–10 —3·10^–8 Mol Glycerin.

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An improved fluorimetric determination of glycerid-glycerol

Summary Oxidation of glycerid-glycerol with periodate results in liberation of formaldehyde, which is detected fluorimetrically as 3,5-diacetyl-1,4-dihydrolutidine. Excess of periodate gives high blank values. This fluorescence is reduced through KI/Na₂S₂O₃ or rhamnose. In contrast to sodium thiosulfate rhamnose shows no effect on the 3,5-diacetyl-1,4-dihydrolutidine formed. The method here described permits determination of glycerol within a range of 3·10^–10—3·10^–8mol.

     

Photochemical and thermal transformations of diazo derivatives of 1-aryloxy- and 1-arylthio-2-aminoanthraquinones

In the photochemical and thermal decomposition of diazonium derivatives of 1-aryloxy- and 1-arylthio-2-aminoanthraquinones in CH ₃ COOH and dioxane, high yields of intramolecular arylation products — anthra-[2, 1-d]-4-tert-butylbenzo-[b]-furan-and anthra-[2, 1-d]-4-tert-butylbenzo-[b]-thiophene-8,13-diones — are formed. It was established that 2-azo derivatives of 1-aryloxy- and 1-acyloxyanthraquinones synthesized on the basis of the diazonium salts are stable under photolysis conditions.Novosibirsk Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk 630090. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 3, pp. 582–585, March, 1992.     

Azaindole derivatives

The peculiarities of the Fischer cyclization of the 4-pyridylhydrazones of propionaldehyde and methyl ethyl ketone, the formation of 3-methyl- and 2,3-dimethyl-5-azaindoles, 4aminopyridine, 4-ethylaminopyridine, and 1-(4-pyridyl)-3,5-diethyl-5-methylpyrazoline under these reaction conditions, and the effect of various catalysts on the direction of the process and the yields of products were examined.See [1] for communication XXXIX.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 652–655, May, 1972.     

Reversed-Phase Liquid Chromatographic Separation, on Cellulose Chiral Stationary Phases, of the Stereoisomers of Methoxytetra-hydronaphthalene Derivatives, New Agonist and Antagonist Ligands for Melatonin Receptors

A stereoselective high-performance liquid chromatographic method has been established for chiral separation of melatoninergic derivatives with one or two chiral centers, new agonist and antagonist ligands for melatonin receptors. Reversed-phase separations were performed on cellulose-based chiral stationary phases—tris-3,5-dimethylphenylcarbamate (Chiralcel OD-RH) or tris-methylbenzoate (Chiralcel OJ-R). Water–modifier (methanol or acetonitrile) mixtures in different proportions were used as mobile phases. The effects of organic mobile-phase modifier concentration, temperature, and compound structure were examined. Baseline separation (R_S > 1.5) was readily obtained for many of the compounds.     

Vibrational spectra,structures, and conformations of conjugated azomethines — 3-imidazoline derivatives

The possibility of the use of the ratios of the intensities of the v _C=N bands in the Raman spectra of the compounds to establish the conformations of the conjugated C=N bonds was demonstrated in the case of conjugated azomethines — derivatives of 2,2,5,5-tetramethyl-3-imidazoline and — 3-imidazoline 3-oxide.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 792–797, June, 1987.     

New N-nitrosoamines. 2. Transformations of tetrahydro-1,3-oxazines into nitrates of N-nitrosoamino alcohols

The reactions of HNO₃ with tetrahydro-1,3-oxazines 1a—c produced by aminomethylation of diketopiperazine, isatin, and succinimide, respectively, afforded nitrates of amino alcohols [RCH₂NH₂(CH₂)₃ONO₂]⁺NO₃ ^– (4a—c) whose subsequent N-nitrosation (NaNO₂, AcOH) gave nitrates of N-nitrosoamino alcohols RCH₂N(NO)(CH₂)₃ONO₂ (5a—c). The structures of compound 5b,c were established by X-ray diffraction analysis.     

A new plant growth regulator of microbial origin

A new plant growth regulator — an inhibitor of the germination of mustard seeds — has been isolated from a culture filtrate of a phytopathogenic fungus of the genusPhoma. The methyl and trimethylsilyl derivatives of this compound have been obtained. Its empirical formula — C₁₆H₂₂O₅ — has been determined. On the basis of the results of IR and NMR spectroscopy and mass spectrometry, the compound isolated has been assigned the structure of 3,5-dihydroxy-2-octanoylphenylacetic acid.All-Union Scientific-Research Institute of Applied Molecular Biology and Genetics. V. I. Lenin Academy of Agricultural Sciences, Moscow. Translated from Khimiya Prirodnykh Soedinenii No. 3, pp. 387–391, May–June, 1985.