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№ 12 (126)
декабрь, 2024 г.
ORGANIC CHEMISTRY
THIAINDAN AND THIOCHROMANE DERIVATIVES BASED ON THE SYNTHESIS OF ORGANIC ALCOHOLS
Chinnigul Bobilova
Senior teacher, Karshi Enginerering Economics Institute, Uzbekistan, Karshi
Guzal Rakhmatova
Doctor of philosophy (PhD), Karshi Enginerering Economics Institute, Uzbekistan, Karshi
ПРОИЗВОДНЫЕ ТИАИНДАНА И ТИОХРОМАНА НА ОСНОВЕ СИНТЕЗА ОРГАНИЧЕСКИХ СПИРТОВ
Бобилова Чиннигул Хайитовна
ст. преподаватель Каршинского инженерно-экономического института, Республика Узбекистан, г. Карши
Рахматова Гузал Ботировна
канд. техн. наук,
сотрудник Каршинского инженерно-экономического института,
Республика Узбекистан, г. Карши
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.
Библиографическое описание: Bobilova C., Rakhmatova G. THIAINDAN AND THIOCHROMANE DERIVATIVES BASED ON THE SYNTHESIS OF ORGANIC ALCOHOLS // Universum: химия и биология : электрон. научн. журн. 2024. 12(126). URL: https://7universum.com/ru/nature/archive/item/18824
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; Ri= C2H5; II R=CH3; Ri= C3H7 ; III R=CH3; Ri= C4H9 ; IV R= C2H5; Ri= C4H9 ;
HC
CH3CO
+ RiMgX-CH3
H3C-
-CH3
A-CH3
OH R
COR
+
R1MgX-
-S'
V Ri = C2H5;
Ri
C—R I
OH
VI R=CH3; Ri= C2H5; VII R=CH3; Ri= C3H7 ; VIII R=CH3; Ri= C4H9 ; IX R= C2H5; Ri= C4H9 :
CH3 COCH'
+ RMgX-
3
^-CH3 OH R
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 p20d=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 p20d=1.58500. Also, the yield of 2-methyl-5-(1-methyl-1-oxyamyl)-1-thiaindane (III) is 82%, refractive index p20d=1.53840,
2-methyl-5-(i-ethyl-i- The yield of oxyamyl)-i-thiaindane (IV) is 85%, the refractive index p20d=i.55600, the yield of 2,5-dimethyl-6-(i-methyl-i-oxypropyl)-i-thiaindane (V) is 83%, refractive index p20d=i.60900, the yield of 6-(i-methyl-i-oxypropyl)-i-thiochroman (VI) is 80%, its refractive index p20d= i.59i00, 6-(i-methyl-i- oxybutyl)-i-thiochroman (VII) yield 84%, refractive index p20d=i.56930, 6-(i-methyl-i-oxyamyl)-i-thiochroman (VIII) yield 9i%, refractive index p20d=i ,57540; 6-(i-ethyl-i-oxyamyl)-i-thiochroman (IX) yield 93%, refractive index p20d=i.58290 and 6-methyl-7-(i-methyl-i-oxypropyl)-i-thiochroman It was found that the yield of (X) is 86%, and the refractive index is p20d=i.56700.
During the conducted reaction, one can see such a pattern that among the synthesized substances, it was
S
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
s/n R Ri persentage „20 n J found %. Gross formula Calculated, %.
C H C H
I CH3 C2H5 76 1,5850 70,79 70,55 8,52 8,33 C13H18OS 70,30 8,10
II CH3 C3H7 79 1,5484 71,38 71,29 8,54 8,51 C14H20OS 71,18 8,47
III CH3 C4H9 82 1,5334 72,18 72,14 8,12 9,03 C15H22OS 71,95 8,85
IV C2H5 C4H9 85 1,5560 72,89 72,81 9,33 9,18 C16H24OS 72,72 9,10
V C2H5 83 1,6090 71,56 71,38 8,52 8,50 C14H20OS 71,18 8,47
Table 2.
Thiochromane series of tertiary alcohols physicochemical description
s/n persentage, % n20 n j found, %. Gross formula calculated, %. R Ri
C H C H
VI 80 1,5910 70,75 70,53 8,49 8,30 C13H18OS 70,30 8,10 CH3 C2H5
VII 84 1,5693 71,35 71,27 8,60 8,57 C14H20OS 71,18 8,47 CH3 C3H7
VIII 91 1,5754 72,21 72,16 9,12 9,00 C15H22OS 71,95 8,85 CH3 C4H9
IX 93 1,5829 72,85 72,81 9,26 9,18 C15H22OS 72,72 9,10 C2H5 C4H9
X 86 1,5670 76,33 71,23 8,60 8,53 C14H20OS 71,18 8,47 C2H5
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
Frequency shift.cm-1 Compounds
I II IIII IV V VI VII VIII
In the benzene ring i6i3 i600 i600 i6i0 i600 i600 i6i5 i625
In the benzene ring CH 830 830 825 825 830 8300 830 830
In the benzene ring H ii20 i220 ii20 ii20 ii20 iii5 ii30 ii20
-C-O 9i5 920 9i0 9i5 920 920 9i0 9i5
-C-O-H ii70 ii70 ii60 ii65 ii70 ii70 ii70 ii70
O-H 3435 3430 3430 3440 3440 3430 3475 3465
C-S-C 740 740 740 740 735 750 740 745
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
OH I
PMR-spectrum data R— C— B
A
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
OH I
PMR-spectrum data R— C— B
A
Table 5.
Association number Structural formula Substituents, chemical shift (m.c.)
OH A B
VI OH rTVfC2H5 ^S-/1^ CH3 2,70 1,50 CH3 0,90 CH2 1,60
VII OH rYirfC'H' CH3 2,56 1,49 CH3 0,90 CH2 1,65 (4 proton)
Association number Structural formula Substituents, chemical shift (m.c.)
OH A B
VIII OH ch3 2,95 1,48 CH3 0,88 CH2 1,30 (6 proton)
IX OH Ctrir 2,64 CH3 0,90 CH2 1,61 CH3 0,88 CH2 1,30 (6 proton)
X CH3 2,70 1,50 CH3 0,90 CH2 1,61
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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2. Kamol M. Dovud. Regio-and stereoselective synthesis of bis-spiropyrazoline-5,3'-spiropyrazoline(thiochroman)-4-one derivatives via bis-nitrilimines. Tetrahedron. Volume 61. Issue 22, 30 may, 2005, pages 5229-5233. [In English].
3. Lara Byanchi, Massimo Makagno, Jovanni Petrillo, Fernando Sankassan, Domeniko Spinelli, Cinzia Tavani. Access to 2,3-diaril-4-nitrothiochroman S,S-dioxides from 3-nitrobenzo[b]thiophene. Tetrahedron. Volume 67, Issue 42, 21 October 2011, pages 8160-8169. [In English].
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