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The heterocyclization of hydrazides, prepared from methyl 5-phenyl-2-hydrozinothiazole-4-carboxylate and organic acids or their anhydrides, leads to the production of thiazolo[2,3-c]triazoles which do not undergo rearrangement to the corresponding thiazolo[3, 2-b]triazoles under the action of mineral acids. The 2-trifluoroacetylhydrazine derivative does not cyclize, even under severe conditions.

Esters and amides of 2,2-dichloro-3-(2-furyl)-3-hydroxypropionic acid were prepared by the reaction of furfural with dichloroacetic acid derivatives under the conditions of the Darzens condensation. The structures of the reaction products were confirmed by their1H NMR and IR spectra and chemical transformations.

Cyclization of thiosemicarbazide with methyl 3-chloro-2-oxo-3-phenylpropionate in MeCN results in 5-hydroxy-2-imino-5-methoxycarbonyl-6-phenylperhydro-1,3,4-thiadiazine. The structure of the product has been confirmed using spectral (IR,1H,13C,13C{1H} NMR) methods and chemical transformations.

The methyl ester and N,N-diethylamide of 2-azido-5-phenyl-4-thiazolecarboxylic acid were obtained by the reaction of the corresponding 4-substituted 2-hydrazino-5-phenylthiazole with NaNO2 in acid media. IR and UV spectroscopy were used to show that the compounds synthesized retain azide form in both the crystalline state and in solution. The reaction of azides with dicarbonyl compounds gave derivatives of 2-[5′-methyl-4′-acetyl-or 2-[5′-methyl-4′-ethoxycarbonyl-1′,2′,3′-triazol-1′-yl]-5-phenylthiazole-4-carboxylic acid.

The reaction of methyl 3-phenyl-3-chloro-2-oxopropionate with thiosemicarbazones proceeds via the intermediate formation of methyl [S-(1′-alkylideneisothiosemicarbazidyl)]-3-phenyl-2-oxopropionate hydrochlorides, which then cyclize to novel 4-methoxycarbonyl-5-phenyl-2-substituted thiazoles. Hydrolysis of the intermediate products and the thiazoles obtained therefrom with simultaneous distillation of the carbonyl compound affords 2-hydrazino-4-methoxy-carbonyl-5-phenylthiazole.

It was found that the nature of the SH and OH groups in 2-mercapto- and 2-hydroxyethanolamines plays a decisive role in the reactions between these compounds and methyl 3-phenyl-3-chloro-2-oxopropionate, the products comprising 1,4-thiazine and 1,4-oxazane derivatives, respectively. Some of the reactions of these products were investigated.

The reaction of the title compound with dichloroacetic acid esters in the presence of butyllithium gave esters of 3-thienyl-3-hydroxy-2,2-dichloropropionic acid.

1. According to the data of the IR spectra, solutions of N-(p-methoxyphenyl)amidodichlorophosphate and N-phenylamidodichlorophosphate are characterized by a conformational equilibrium, whereas one steric structure is stabilized for N-(p-bromophenyl)amidodichlorophosphate and N-(p-nitrophenyl)amidodichlorophosphate. 2. It is suggested that forms with shielding of the PO and NH bonds and a skewed mutual arrangement of them participate in the equilibrium. 3. The observed changes in the displacement of the conformational equilibrium as a function of the nature of the substituents in the p-position of the benzene ring are explained by the different degree of conjugation on the nitrogen atom with the phosphorus portion of the molecule.

1. The reaction of diphenylurea with the chlorides of phosphorous and phosphonous esters gives phosphorylated urea derivatives, whereas reaction with the chloride of diethylphosphoric acid leads to tetraethyl pyrophosphate and diphenylcarbodiimide.

1. An investigation was made of the reactions of chloral with certain phosphoramidous ester, acylphosphoramidous esters, mixed anhydrides of acetic acid and dialkyl hydrogen phosphites, cyclic ethylene phosphorochloridite, and diethyl hydroxymethylphosphonate amd also of chloral hydrate with dibutyl phosphorochloridite. 2. As a result of these reactions we prepared and characterized the corresponding phosphoramidic and acylphosphoramidic esters containing a 2,2-dichlorovinyl group, derivatives of 2,2,2-trichloro-1-droxyethylphosphonic acid, and chloral acetyl (diethoxyphosphinyl) methyl acetal.

By the interaction of the mono-N- and di-N-oxides of 2,3-di-(w-bromomethyl)-quinoxallne with trialkyl phosphites there was synthesized a series of esters of phosphinic acid containing mono-N- and di-N-oxidoquinoxalinic radicals; some of their properties were studied.

1. A study was made of the reaction of the acid chlorides of acetic, benzoic, ethylcarbonic and N-diethylaminosulfenic acids with the diethyl ester of methylurethanphosphorous acid. In all cases the reaction proceeds by the scheme of the Arbuzov rearrangement, with the formation of the corresponding phosphonic acid derivatives. 2. The action of aqueous ammonia solution on the N-methylamide of ethylcarbonic and O-ethylbenzoylphosphonic acids at room temperature results in cleavage of the P-C and P-N bonds, and benzamide, the ammonium salt of ethylphosphorous acid and methylurethan are formed. 3. The reaction of sulfur or selenium with the N-methylamide of ethylcarbonic and diethylphosphorous acids gave the N-methylamide s of the corresponding acids, namely of ethylcarbonic and diethylthiophos-phoric acids, and of ethylcarbonic and diethylselenophosphoric acids.

1. A study was made of the reaction of the chlorides of acetic, ethylcarbonic, and N-diethylaminosulfenic acids with some amidoesters of urethanephosphorous acid. Depending on the nature of the acid chloride, its reaction with the amidoesters proceeds at either one or two reaction centers. 2. Some N-disubstituted amidoesters of urethanephosphorous acid were synthesized.

1. The amides of dialkylphosphoric acids are formed when the dichloromethyleneamidophosphates are treated with water in the presence of triethylamine; isocyanatophosphoric acid esters are formed when the same dichlorides are treated with formamide. 2. The corresponding N-phosphorylated iminocarbamic acids are apparently formed as intermediate products when formamide, methylformamide or water is reacted with the acid chlorides of the N-phosphorylated iminocarbamic acids, which then rearrange to the N-phosphorylated ureas.

1. A study was made of the reaction of the acid chlorides of acetic, butyric and isobutyric acids with the amide of diethylphosphoric acid, and of the acid chloride of diethylphosphoric acid with the amides of acetic, butyric and benzoic acids and with formanilide. 2. With the amide of diethylphosphoric acid the reaction proceeds with the formation of acylamidophosphates, while with the amides of acetic, butyric and benzoic acids and with formanilide the reaction goes with the formation of the ethyl ester of pyrophosphoric acid and the corresponding cyanides or phenyl isocyanide.

1. From the IR spectra of diethylcyanomethylphosphine oxide and diphenylcyanomethylphosphine oxide it follows that the equilibrium of two conformers is characteristic for the solutions of these compounds. A noticeable association of the molecules is manifested under high concentration conditions. 2. The dipole moments of the gauche conformers of the studied molecules, which contain polar P=O and C≡N groupings, are much lower than those calculated by the vector scheme due to coulomb interaction.

1. N-(Sulfenechloro)ethylamide of diethylphosphoric acid (N-sulfenechloride),\(\begin{gathered} (C_2 H_5 O)_2 P - N - S - Cl \hfill \\ \mathop {||}\limits_O \mathop |\limits_{C_2 H_5 } \hfill \\ \end{gathered} \), was prepared by the action of sulfuryl chloride on bis(N-ethylamide of diethylphosphoric acid) N,N'-disulfide. 2. The reactions of the N sulfenechloride with dimethyl- and diethylamine, aniline, and ethyl, isopropyl, and isobutyl alcohols were investigated. As a result of the reactions that were carried out, di-N-substituted amides of diethylphosphoric acid were obtained.

1. The action of acetyl chloride, benzoyl chloride, and ethyl chlorocarbonate on esters of phosphoramidous acids with one and two diethylamide groups forms products of the Arbuzov rearrangement, and, where an ester of tetraethylphosphorodiamidous acid was used, an ester of phosphoroamidochloridous acid and a substituted amide of the corresponding carboxylic acid. 2. Under the action of N-diethylaminosulphenyl chloride, esters of phosphoramidous acids undergo rearrangement into the corresponding derivatives of acids of pentavalent phosphorus (Arbuzov reaction).

Die Einwirkung von Saurechloriden wie Acetyl- oder Benzoyl-chlorid bzw. Chlorkohlensaureester (II) auf Methylurethan-phosphorigsaure-diathylester (I) bei Zimmertemperatur fuhrt ohne Temperaturerhohung unter Umlagerung und Abspaltung von Athylchlorid zu den N-Carbathoxy-N-methylamiden (III) (Ausbeute 62 - 71%).

1. The acid chlorides of N-dialkoxyphosphosphorylated iminodialkylcarbamic acids form unstable intramolecular condensation products, which decompose into the cyanodialkylamine and metaphosphoric acid ester. 2. When reacted with acetic anhydride the dichloromethylenamides of dialkylphosphoric acids form the esters of isocyanatophosphoric acid.