The method was developed for synthesis of hard-to-reach phosphorylated aldehides with hidden carbonyl group. As compounds with active methylene group triethyl ethers of phosfonacetic acid and diethoxycianomethyl phosfonate were used at the condensation with bromo- and chloroacetals to produce the corresponding acetals. It was found that in the mentioned phosphonates the alkylation by haloid acetal occurs exceptionally on the carbon atom of active methylene group, not touching the nitrile and ester groups. The hydrolysis of obtained phosphorylated acetals led to preparation of phosphorylated aldehydes. It was found that an application of chlorinated acetals led to decreasing the yield of final products. On the basis of obtained aldehydes the corresponding hydrozones were prepared. The latter in the course of reaction undergoes the conversion occurring on the nitrile and ester groups. The high reaction activity of synthesized phosphorylated acetals was used in the further synthesis of different kind of phosphoroganic compounds. The reaction of phosphorylated aldehydes with hydrazine led to obtaining the nitrogen and phosphor containing organic compounds. The structures of synthesized compounds were studied and proved by IR and NMR spectroscopy methods. Forcitation: Ismailov V.M., Yusubov N.N., Sadykhova N.D., Ibragimova G.G., Mamedov I.A. Alkylation of triethyl ester of phosphonoacetic acid and diethoxycyanomethylphosphonate with haloidacetals and products of their transformation. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2017. V. 60. N 2. P. 13-16.
Acetaldehyddimethyl‐ und diäthylacetal (I) geben mit Pentachlorid bei 8 ‐ 10°C einen kristallinen Komplex, der bei Behandlung mit Schwefeldioxid die β‐Alkoxyvixiylphosphonsäuredichloride (II) liefert.
The high synthetic potential of the functionalized aromatic diketones makes it possible to use them as "multi-side" intermediates, in the synthesis of heterocyclic compounds and potentially biologically active molecules. Friedel-Crafts acylation of aromatic hydrocarbons is the most important method of synthesis of acylaromatic ketones, which allows the introduction of only one carbonyl group into the aromatic ring. The application of the Friedel-Crafts acylation reaction is not so often used to obtain aromatic diketones. Have been investigated the possibilities of synthesis functionalized diketones by the Friedel-Crafts acylation of aromatic hydrocarbons on the basis of 1,4-diacetyl- and 1-acetyl-4-methylhydroquinones in the presence of AlCl3 in dichloroethane. 2,6-diacetyl derivatives of hydroquinone and the products of their hydrolysis were obtained. Have been studied the dependence of the yield of the products on the reaction conditions. The properties of synthesized ketones in the reactions with electrophilic and nucleophilic reagents have also been studied. The reaction of 2,6-diacetylhydroquinone and its esters with hydroxylamine produced dioximes. The reaction of acetylhydroquinone and its derivatives with urea produces the corresponding imine that forms by the nucleophilic addition of urea to the carbonyl group. These ketones with guanidine hydrochloride give the corresponding guanidinium derivatives. Ketones with guanidine hydrochloride give the corresponding guanidinium derivatives, the formation of which refers to the reactions of nucleophilic addition to the carbonyl group. It was shown that this reaction with 1,4-dimethoxybenzene proceeds according to the scheme of electrophilic substitution in the aromatic nucleus, followed by destruction, forming a mixture of nitriles. These ketones are readily nitrated with partial hydrolysis of the methoxy group giving 1-(2-hydroxy-5-metoksi-3-nitrofenil)propan-1-ona. Unconventional electrophilic substitution reaction was observed at the Beckmann rearrangement of the oxime (E)-1-(2-hydroxy-5-methylphenyl)etan-1-one proceeds by sulfonation and hydrolysis of the rearrangement reaction product to form 3-amino-2-hydroxy-5-methylbenzensulfonat. Have been shown the conditions and suggested mechanisms of carried out reactions.
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