THIAINDAN AND THIOCHROMANE DERIVATIVES BASED ON THE SYNTHESIS OF ORGANIC ALCOHOLS

ABSTRACT

In this article, the chemical properties of the reaction of acylthioamines and acylthiochromans containing a carbonyl group based on organomagnesium compounds with magnesium oxide and absolute ether in the synthesis of tertiary alcohols were studied. As a result of the reaction, 2-methyl-5-(1-methyl-1-oxypropyl)-1-thiaindane was synthesized with a yield of 76%, 2-methyl-5-(1-methyl-1-oxybutyl)-1-thiaindane with a yield of 79%, 2-methyl-5-(1-methyl-1-oxyamyl)-1-thiaindane with a yield of 82%, 6-methyl-7-(1-methyl-1-oxypropyl)-1-thiochroman with a yield of 86%, 6-(1-methyl-1-oxybutyl)-1-thiochroman with a yield of 84%, 6-(1-methyl-1-oxyamyl)-1-thiochroman with a yield of 91%, and 6-(1-ethyl-1-oxyamyl)-1-thiochroman with a yield of 93%. It was shown that compounds with a large number of carbon atoms in the hydrocarbon radical significantly predominate. It was observed that as the molecular mass of the reactant increased, the yield of the reaction product also increased in parallel.

АННОТАЦИЯ

В данной статье изучены химические свойства реакции ацилтиохроманов и ацилтиохроманов с карбонильными группами на основе соединений магния при синтезе третичных спиртов в присутствии порошка магния и абсолютного эфира. В результате реакции вещество 2-метил-5-(1-метил-1-оксипропил)-1-тиаиндан составило 76%, выход 2-Метил-5-(1-метил-1-оксибутил) -1-тиаиндана составило 79%, 2- Выход метил-5-(1-метил-1-оксиамил)-1-тиайндана составил 82%, 6-метил-7-(1-метил-1-оксипропил)- 1-тиохроман выход 86%, выход 6-(1-метил-1-оксибутил)-1-тиохромана 84%, выход 6-(1-метил-1-оксиамил)-1-тиохромана 91%, 6-(1-этил-1 -оксиамил)-1-тиохроман синтезирован с выходом 93%. был показан. Было замечено, что выход продукта реакции увеличивается параллельно с увеличением молекулярной массы реагента.

Keywords: thiochroman, magnesium, organomagnesium, diketone, sodium chromanoylacetone, filtrate, desiccator, electron donor, electron acceptor, carbonyl group, ketone, absolute ether, charge, reagent.

Ключевые слова: тиохроман, магний, органомагний, дикетон, хроманоилацетон натрия, фильтрат, эксикатор, донор электронов, акцептор электронов, карбонильная группа, кетон, абсолютный эфир, заряд, реагент

INTRODUCTION

As we all know, in organomagnesium compounds, the magnesium atom is directly connected to the carbon atom of the organic compound. The electronegativity difference between atoms in this bond is quite large. Therefore, the bond between carbon and magnesium in mixed organomagnesium compounds is strongly polarized. A partial negative charge appears on the carbon atom bonded to magnesium in the molecule. It can be seen that organomagnesium compounds are considered to be nucleophilic reagents and are highly reactive agents for positively charged reactive center compounds. The number of compounds with this type of positively charged center is very large, so it is possible to synthesize representatives of a large number of different classes of organic compounds on the basis of organomagnesium compounds. Below, we studied the chemical properties of these organomagnesium compounds in the synthesis of tertiary alcohols of acylthiamines and acylthiochromans containing a carbonyl group. [1; 54-59 p].

It is known that the reaction of ketones and organomagnesium compounds is one of the main methods of obtaining tertiary alcohols. For this, we conduct a reaction in magnesium powder and absolute ether. [2; 55-58 p].

The synthesis process carried out above can be expressed schematically based on the following chemical formulas:

I  R=CH₃;  R₁= C₂H₅;    II R=CH₃;  R₁= C₃H₇ ;

III  R=CH₃;  R₁= C₄H₉ ; IV R= C₂H₅;  R₁= C₄H₉ ; 

                                                                                                        V  R₁ = C₂H₅;

VI  R=CH₃;  R₁= C₂H₅;    VII  R=CH₃;  R₁= C₃H₇ ;

VIII  R=CH₃;  R₁= C₄H₉ ; IX R= C₂H₅;  R₁= C₄H₉ ; 

X  R= C₂H₅

MATERIALS AND METODS

The reaction was carried out in a water bath slowly heated to a temperature of 25 ⁰C, initially for 10 minutes with constant stirring of the reaction mixture. Then the reaction mixture was kept under stirring at a temperature of 40-45 ⁰C for 2 hours. After that, the purity and individuality of the substance was checked in the benzene:hexane (1:4) system using the Silufol plate. The yield of the product, namely 2-Methyl-5-(1-methyl-1-oxybutyl)-1-thiaindane (II) is 79%. The refractive index was found to be p²⁰_d=1.54840.

By the same method above, 2-methyl-5-(1-methyl-1-oxypropyl)-1-thiain (I) was synthesized with 76% yield. Its refractive index was found to be equal to p²⁰_d=1.58500. Also, the yield of 2-methyl-5-(1-methyl-1-oxyamyl)-1-thiaindane (III) is 82%, refractive index p²⁰_d=1.53840, 2-methyl-5-(1-ethyl-1- The yield of oxyamyl)-1-thiaindane (IV) is 85%, the refractive index p²⁰_d=1.55600, the yield of 2,5-dimethyl-6-(1-methyl-1-oxypropyl)-1-thiaindane (V) is 83%, refractive index p²⁰_d=1.60900, the yield of 6-(1-methyl-1-oxypropyl)-1-thiochroman (VI) is 80%, its refractive index p²⁰_d= 1.59100, 6-(1-methyl-1- oxybutyl)-1-thiochroman (VII) yield 84%, refractive index p²⁰_d=1.56930, 6-(1-methyl-1-oxyamyl)-1-thiochroman (VIII) yield 91%, refractive index p²⁰_d=1 ,57540; 6-(1-ethyl-1-oxyamyl)-1-thiochroman (IX) yield 93%, refractive index p²⁰_d=1.58290 and 6-methyl-7-(1-methyl-1-oxypropyl)-1-thiochroman It was found that the yield of (X) is 86%, and the refractive index is p²⁰_d=1.56700.

During the conducted reaction, one can see such a pattern that among the synthesized substances, it was found that the yield of the reactions conducted with the compounds containing the thiochroman fragment is somewhat higher than that of the thiaindan fragment. So, compared to acyltiaindanes, in the reaction of acylthiochromans with organomagnesium compounds, the compounds containing the thiochroman fragment have an advantage, while in terms of organomagnesium compounds, radical compounds with a high number of carbon atoms in the hydrocarbon radical are more superior. All of the resulting compounds are viscous solid-liquid substances, and the following tables provide information on the physicochemical classification and elemental analysis of the obtained compounds.

Table 1.

Thiain is a series of tertiary alcohols physicochemical description

Table 2.

Thiochromane series of tertiary alcohols physicochemical description

The structure of the synthesized compounds was confirmed using IR- and PMR-spectroscopic methods calculated from modern research methods. The progress of the reaction was monitored by thin-layer chromatography. Purity of the obtained substances and its identification was carried out using a "silufol" plate in the benzene-hexane (1:5) system.

Table 3.

Tertiary alcohols such as thiaindan and thiochroman IR-spectra data

REZULTS

When comparing the IR-spectrum of the synthesized compounds with the IR-spectra of acylthiochroman molecules from the original acylthiain, it became clear that the absorption lines in the 1700 cm^-1 region characteristic of the carbonyl group in the IR-spectrum of the original substance are completely absent in the IR-spectra of tertiary alcohols formed. Instead, it was found that new absorption lines characteristic of the ON group appeared in the region of 3400 cm^-1. The table below presents information about the characteristic absorption lines of the frequency shift in the IR spectrum of tertiary alcohols of thiaindan and thiochromane series.

Figure 1. IR spectrum of 6-(1-methyl-1-oxyamyl)-1-thiochroman

The following tables present the data related to the PMR-spectrum of synthesized thiaindan and thiochromane tertiary alcohols expressed as NO-S(A)(V). IR spectra of the obtained substances were obtained in the range of 3600-400 cm^-1 on a VR-20 spectrophotometer. The samples were prepared in the form of tablets compressed in KBr salt. The thickness of the tablet layer was selected depending on the ability of the studied substance to transmit IR radiation. PMR spectra were obtained on an 80 MHz “TESLA-487 C” device with GMDS as the internal standard and operating with CF3COOH, CCl₄ and CD₃OH as solvents. The purity of the products and the course of the reaction were monitored by thin layer chromatography (TLC) on a “Silufol UV-254” plate in a system of various solvents. Iodine vapor and UV light were used as decolorizers. The liquefaction temperature of the obtained substances was determined using a Boethius device.

Tertiary alcohols such as thiain

PMR-spectrum data                                   

Table 4

Note: here R- is considered as a fragment of the thiandane molecule.

As a result of the study of the reaction of obtaining tertiary alcohols based on thiaindan and thiochromane derivatives, it was found that the yield of the reaction product increases in parallel with the increase in the mass of the reactant. This process was especially evident in tertiary alcohols containing a thiochroman fragment compared to a thiaindan fragment. All obtained carbinols of thiaindan and thioxrman series are well soluble in organic solvents, have a characteristic pleasant smell and are bright reddish colored substances.

Thiochromane series of tertiary alcohols

PMR-spectrum data              

Table 5

Note: here R- should be considered as a fragment of thiochromene molecule.

CONCLUSION

Since the PMR-spectra of thiaindan and thiochromane fragment are given in the above paragraphs, their data are not given in these tables.

Thus, in conclusion, it can be said that thiaindan and thiochroman series acyl derivatives behave like aliphatic and aromatic ketones in the reaction with organomagnesium compounds and form the corresponding tertiary alcohols with high yield.

References:

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