Ion-pair formation in aqueous solutions of silver nitrate: A Raman and infrared spectral study

A detailed study of the Raman and infrared spectral line shapes and line parameters of aqueous solutions (both H₂O and D₂O) of AgNO₃ is interpreted in terms of an equilibrium between “free” ions and the ion pair Ag⁺NO ₃ ^? . An association constant of 0.1M ^?1 was obtained from both the 717 cm^?1 and 1047 cm^?1 line intensities. Spectral features suggest a significant degree of covalence in the interaction. A C_s(σ_V) model with Ag⁺ above the plane of NO ₃ ^? is consistent with the data.     

Structure and reactivity of the condensation products of aromatic amines with aliphatic aldehydes

A number of previously undescribed propylidenearylamine dimers have been synthesized by the interaction of propionaldehyde with a series of para-substituted anilines(R=H, CH₃, OCH₃, F, Cl, Br, I) and with-naphthylamine. The structure of the bis-propylidenearylamines has been established by a study of their IR and UV spectra. It has been shown that all the bis-propylidenearylamines, except for bis(propylidene-p-fluoroaniline), have the structure of 2-ethyl-3-methyl-4-arylamino-1, 2, 3, 4-tetrahydroquinolines. The dipole moments of the bis(propylidene-p-R-anilines) have been determined. Comparison of the values obtained with the calculated values indicates that the most favorable molecular conformation of the bispropylidenearylamines is a tetrahydroquinoline half-chain with quasi-equatorial positions for the 4-NHAr and NH groups and an equatorial 3-CH₃ group. In contrast to the bis-ethylideneanilines, we did not succeed in finding other stable conformers for the bis-propylidene derivatives. It has been established that bis (propylidene-p-fluoroaniline) has the 1, 3-bis (p-fluorophenylamino)-2-ethyl-1-hexene structure.For communication VI, see [1].     

PHOTOREACTIVATING ENZYME FROM NEUROSPORA CRASSA*

Abstract— Extracts of Neurospora crassa contain photoreactivating enzyme by the criteria of ability to split thymine-containing dimers and to increase the transforming ability of u.v.-irradiated Hemophilus influenzae DNA. The latter activity is heat-labile and is destroyed by trypsin. The action spectrum of such in vitro photoreactivation is a simple one (with a single maximum at 405 nm in the range 313 to 436 nm), differing from the more complicated in vitro spectra for yeast and Escherichia coli. However, the in vitro Neurospora spectrum coincides closely with the in vivo spectrum for this organism, suggesting that there is little or no “indirect” photoreactivation in Neurospora. It is concluded that the Neurospora photoreactivating enzyme is probably of a different type than those of yeast and Escherichia coli.     

Electrochemical behaviour of mono- and oligonucleotides I. Effects of charge and configuration of adenine mononucleotides on their adsorption at the mercury—solution interface

A systematic study of the adsorption and interfacial behaviour of the adenine mono-nucleotides (5′-AMP, 3′-AMP, cyclic 3′,5′-AMP, 5′-ADP and 5′-ATP) and adenosine for comparison at the HMDE has been carried out at pH 3.4 to 3.5. Thus, the N(1) of the adenine moiety is protonated to a major extent.The adsorption was followed by single sweep voltammetry (measurement of the time integral of the reduction peak of the adsorbed adenine moiety) and by a.c. voltammetry (out-of-phase component of the a.c. response being proportional to the differential double layer capacity). In this paper the situation corresponding to a “dilute” adsorption layer existing at low bulk concentrations is studied for various degrees of coverage. The potential dependence of the coverage is of bell shaped type with an extended maximum region around the potential of electrocapillary maximum (E_ecm) of the blank. For the same bulk concentration the coverage decreases in the series AMP, ADP, ATP, i.e. with increasing negative charge of the nucleotide, and at the same time the potential range of adsorption narrows. Among the monophosphates the coverage decreases in the series 3′-AMP, 5′-AMP, cyclic 3′,5′-AMP. The variations are connected with the varying charge of the mononucleotides and with the possibilities for interactions with adjacent molecules in the adsorption layer.At elevated bulk concentrations above a threshold value a substantial increase in coverage occurs around E_ecm as due to strong interactions between the adsorbed base moieties a rather compact film is formed.     

New method for the synthesis of macrocyclic compounds

A mixture of isomers corresponding to closing of the ring at the 3 and 4 positions of the thiophene ring is formed during intramolecular acylation of 12-(5-methyl-2-thienyl)-lauryl chloride in a homogeneous medium; the reaction proceeds primarily to favor the formation of the isomer with the larger ring (80%). A method for the synthesis of macrocyclic -alkylcycloalkanones by reductive desulfurization of the corresponding bicyclic ketones, which contain thiophene rings, was developed.See Izv. Akad. Nauk SSSR, Ser. Khim., 2228 (1970) for Communication XI.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1467–1472, November, 1970.     

Coulometric titration of acids in non-aqueous solvents

Coulometric titrations of mineral acids, sulphonic acids, carboxylic acids, enols, imides and phenols have been carried out in t-butanol or in acetone with electrically generated tetrabutylammonium hydroxide. Either a potentiometric titration or a visual indicator end-point may be used. The amount of acid titrated ranges from 10 to 60 muequiv, and the precision and accuracy of the method are excellent.     

Locating the more acidic hydroxyl group on dihydroxy compounds o,o'-dihydroxyazo-dye metal-ion indicators

In o,o'-dihydroxyazo-dye metal-ion indicators, one hydroxyl group is 10(4) times more acidic than the other. The location of the more acidic group has been a mystery. By methylation of the acidic group, reduction of the monomethylated compound, isolation and characterization of the split methoxyamine and hydroxyamine, the location of the acidic group has been established. Indicators examined include Calmagite, Eriochrome Black T, Eriochrome Blue Black R and 4-(2-pyridylazo)resorcinol (PAR).     

The synthesis of cypridina etioluciferamine and the proof of structure of cypridina luciferin

An unambiguous synthesis of Cypridina etioluciferamine was accomplished in order to prove the structure of this important bioluminescent natural product. Several 2-aminopyrazine 1-oxides were synthesized in order to establish a spectroscopic method for determining the placement of substituents on the pyrazine nucleus of Cypridina etioluciferamine. Titanium tetrachloride was used to improve the yields of these compounds; for example, the yield of 2-amino-3-methyl-5-phenylpyrazine 1-oxide (19) from reaction of phenylglyoxal 1-oxime and α-aminopropionitrile was raised from 3% to 51% by the use of titanium tetrachloride. The pyrazine ring proton is found at τ 1·37 (DMSO-d₆). The isomeric 2-amino-3-methyl-6-phenylpyrazine 1-oxide (22) was similarly prepared and its pyrazine ring proton is found at τ 2·18. This large difference (0·81 ppm) in chemical shift was used to determine whether a 2-aminopyrazine 1-oxide was 5- or 6- substituted. Prepared in an analogous fashion were 2-amino-5-(indol-3-yl)-3-methylpyrazine 1-oxide (23) and 2-amino-5-(indol-3-yl)-3-(3-phthalimidopropyl)pyrazine 1-oxide (16). The structures of these compounds were verified by NMR spectroscopy. By treatment with Raney nickel and hydrogen gas, then 100% hydrazine hydrate, 16 was converted to 2-amino-3-(3-aminopropyl)-5-indol-3-ylpyrazine (5), isolated as the dihydrochloride. This compound, with the indole moiety definitely placed at C-5, is identical with Cypridina etioluciferamine dihydrochloride (IR, UV, TLC). These results show that the structures of Cypridina etioluciferamine and luciferin are correct as published.     

Tautomeric equilibrium of 1-β-D-ribofuranosyl-2-keto-4-(n-methoxyamino)pyrimidine

The 1-β-D-ribofuranosides of 2-keto-4-(N-methoxyamino)pyrimidine, 2-keto-4-(N-methyl-N-methoxyamino)pyrimidine, and 2-keto-3-methyl-4-(N-methoxyamino)pyrimidine were synthesized, and their pK_a values were determined by spectrophotometry. The pK_a values of the compounds are evidence that the tautomeric equilibrium between the oxime and hydroxyamine forms of 1-β-D-ribofuranosyl-2-keto-4-(N-methoxyamino)pyrimidine in aqueous solutions is shifted to favor the oxime form (K_T?25).     

Nitration of Durene and Pentamethylbenzene with Nitronium Salts in Nitromethane and Acetonitrile

Nature and proportions of the products formed in the nitrations mentioned in the title are affected by the process of mixing. Pentamethylnitrobenzene, formed initially in the nitration of pentamethylbenzene, is attacked by a nitronium ion at a position meta to the nitro-group. In the σ-complex formed, loss of a proton from a methyl group leads to production of by-products and release of nitrite ions. The nitrous acid formed is protonated, and water is displaced from the nitrous acidium ion by the anion, PF₆^?, giving the nitrosonium ion which forms a 1:1 symmetric molecular complex with pentamethylbenzene. A similar complex is formed in the reaction between durene and nitronium salts. The results are consistent with the view that no σ-bond is formed between the aromatic compound and the nitrosonium ion.