Авторы

  • Г. Рахматова
    Karshi State Technical University

DOI:

https://doi.org/10.71337/inlibrary.uz.imjrd.113750

Аннотация

 Condensation reactions of sulfur bicyclic organic compounds with circaethyl ether were studied. as a result of the reaction, it was found that compounds of the acetylthiochroman series react with circaethyl ether in the same way as aliphatic and aromatic ketones, and as a result of the reaction, the corresponding thiochromanoylacetones are formed with good yield.


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INTERNATIONAL MULTIDISCIPLINARY JOURNAL FOR

RESEARCH & DEVELOPMENT

SJIF 2019: 5.222 2020: 5.552 2021: 5.637 2022:5.479 2023:6.563 2024: 7,805

eISSN :2394-6334 https://www.ijmrd.in/index.php/imjrd Volume 12, issue 06 (2025)

119

CONDENSATION REACTIONS OF HETEROCYCLIC SULFUR COMPOUNDS

G.B.Raxmatova

Karshi State Technical University, Department of Natural Sciences

rakhmatova

85guzal@mail.ru

Abstract:

Condensation reactions of sulfur bicyclic organic compounds with circaethyl ether

were studied. as a result of the reaction, it was found that compounds of the acetylthiochroman

series react with circaethyl ether in the same way as aliphatic and aromatic ketones, and as a result

of the reaction, the corresponding thiochromanoylacetones are formed with good yield.

Keywords:

thiochroman,

acylthiochroman,

circaethyl

ether,

diketone,

sodium

thiochromanoylacetone, filtrate, desiccator, electron donor, electron acceptor, carbonyl group,

ketone, absolute ether, charge, reagent.

It is known that the condensation reactions of complex esters with ketones lead to the formation

of β-diketones. Most ketones can readily undergo enol tautomerization in the presence of bases or

acids if they have hydrogen atoms on the α-carbon atom relative to the keto group. For diketones

and ketones, the amount of enols in equilibrium is stabilized by the additional unsaturation groups

in their enol form. The amount of enols formed from ketones strongly depends on the structure of

the ketone and the nature of the solvent used.

It was found that the appearance of β-diketones in the enol form is higher in solution than in the

keto form. A similar pattern is observed in β-diketones of the 1-thiochroman series.

O

CH

3

- C - CH

2

- C

O

CH

3

- C - CH- C

O

O

CH

3

- C - CH- C

Î Í

Î Í

S

S

S

The resulting compounds are crystalline substances, soluble in organic solvents, but insoluble in

water. The mechanism of the condensation reaction of ketones of the acetylthiochroman type with

circaethyl ether can be expressed in the following order:

- C - CH

2

H

O

(1)

C

2

H

5

O

-C

2

H

5

OH

- C - CH

2

O

(2)

CH

3

COOC

2

H

5

- C - CH

2

- C - CH

3

O

O

OC

2

H

5

(3)

(4)

-C

2

H

5

O

- C - CH - C - CH

3

O

O

H

(5)

C

2

H

5

O

-C

2

H

5

OH

- C = CH - C - CH

3

O

O (6)

R

R

R

R

R

where: R= thiochromene molecule.
The catalyst (ethylate anion) removes a proton from ketone (1), which is a methylene component.

The resulting highly reactive carbanion (2) attacks the partially positively charged carbon atom of

ethyl ether (3) of acetic acid, which is a carbonyl component. As a result, anion (4) is formed, and

thiochromanoylacetone (5) is obtained due to the separation of the ethylate ion. This compound

exists as the enolate form (6) in alkaline media. The reaction mixture is acidified to isolate


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thiochromanoylacetones:

R

R

R

- C = CH - C - CH

3

O

O (6)

Na

CH

3

COOH

-CH

3

COONa

-C = CH -C - CH

3

OH

O

-C - CH

2

-C - CH

3

O

O

(7)

The structure of the synthesized compounds was determined using IR- and PMR-spectra, and the

composition was determined using the method of elemental combustion analysis. Monitoring the

progress of the reaction and determining the purity of the obtained substances was carried out

using the thin-layer chromatographic method on the "Silufol" plate.

In the PMR-spectrum of 2-Methyl-1-thiaindanoylacetone (I), the protons of the methyl group in

the sixth position are singlet at 1.27 m.u. show their signals in , the signals of methylene group

protons are 2.13 m.u. in the form of a complex multiplet. and 2.32 m.u. give their signals, while

the signals of protons in the aromatic ring are 8.28 m.u. and 8.32 m.u. appears. The characteristic

aspect of the spectrum of this substance lies in the presence of a strong internal molecular

hydrogen bond in compounds with this structure. As the acidity of β-diketones in the form of enol

increases, the shift of the signals of the hydroxyl group shows a shift towards the dark region. A

similar appearance is shown by the enol-form molecule of 1-thiochroman β-diketones in the

complex multiplet form of the proton in the hydroxyl group at 2.08 m.u. manifestation and the

signals of the proton in the SN group of α-carbon atom are 7.12 m.u. can be seen in their

manifestations.

In the IR-spectrum of the synthesized thiochromane series β-diketones, broad absorption lines of

the ON group in the form of enol can be seen in the region of 3570-3420 cm

-1

. Also, the

absorption lines belonging to the broad carbonyl group can be observed in the region of 1600 cm

-1

,

and the absorption lines in the region of 1310-1360 cm

-1

indicate that they belong to SN3SO. It

shows the characteristic absorption lines belonging to the methylene group at 1445 cm

-1

, and the

absorption lines at 1100, 1065 and 1010 cm

-1

belong to the S=S double bond in the enol form.

Absorption lines of characteristic vibrations of SN bonds in the benzene ring are observed in the

region of 840 cm

-1

, while absorption lines corresponding to valence vibrations of hydrogen atoms

in the benzene ring can be observed in the region of 930 and 950 cm

-1

. From the obtained results,

it can be said that in these compounds, the lifetime of the structure in the enol form is much better

than in the keto form.

The following table presents the physicochemical data of β-diketones of the thiochromane series.

Thiochromane series β-diketones

physical and chemical data

Table 1

s.n.

percentage

%

Liquefaction

temperature

ºС.

Found,%

Gross formula

Calculated,%

С

Н

С

Н

I

64

41-42

71,85

71,80

6,59

6,54

C

13

H

14

O

2

S

71,61

6,46

II

56

38-39

67,91

67,87

6,58

6,55

C

14

H

16

O

2

S

67,76

6,45

As can be seen from the above data, it was found that in the reaction of 6-acetyl-1-thiochroman

and 6-methyl-7-acetylthiochroman molecules with circaethyl ether, the reactivity of 6-acetyl-1-

thiochroman molecule is slightly higher than that of 6-methyl-7-acetylthiochroman molecule. The


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main reason for this can be attributed to two factors. The first factor is the steric effect of the

methyl group in the 6-position. The second factor can be explained by the influence of electron-

donor and electron-acceptor groups in the aromatic ring. Thus, it was found that semi-aromatic

sulfur-containing bicyclic compounds, like aliphatic and aromatic ketones, are well suited for

complex ether condensation reactions.

REFERENSES:

1. Botirovna, Rakhmatova Guzal, et al. "Study of inspactive properties against corrosion of α-

aminocetones and their products." Austrian Journal of Technical and Natural Sciences 5-6 (2020):

54-59.
2.Guzal, Rakhmatova. "KINETIC PROPERTIES OF BICYCLIC SULFUR ORGANIC

INHIBITORS." Universum: химия и биология 12-2 (90) (2021): 55-58.
3. Рахматова, Гузал Ботировна, Мингникул Жумагулолвич Курбанов, and Миртемир

Тоштемирович Рузибоев. "Синтез и изучение скорости реакции ацилирования 1-

тиаинданов и 1-тиахроманов." Universum: химия и биология 12 (66) (2019): 82-85.
4. Курбанов, Мингникул Жумагулолвич, and Гузал Ботировна Рахматова. "ПРИМЕНЕНИЕ

ТЕМПЕРАТУРНОЙ И КОНЦЕНТРАЦИОННОЙ ЗАВИСИМОСТИ ЭФФЕКТИВНОСТИ

ИНГИБИТОРОВ НА ОСНОВЕ α-АМИНОКЕТОНОВ." Universum: технические науки 11-4

(92) (2021): 44-48.
5. Рахматова, Гузал Ботировна, Мингникул Жумагулолвич Курбанов, and Дилбар

Дусмурадовна

Атакулова.

"БРОМИРОВАНИЯ

АЦИЛПРОИЗВОДНЫХ

1-

ТИАИНДАНОВОГО РЯДА." EUROPE, SCIENCE AND WE EVROPA, V DA A MY

ЕВРОПА, НАУКА И МЫ (2020): 27.
6. Рахматова, Гузал Ботировна, and Искандар Исокович Аллабердиев. "ТЕМПЕРАТУРНАЯ

ЗАВИСИМОСТЬ АНТИКОРРОЗИОННЫХ СВОЙСТВ БИЦИКЛОВЫХ ОРГАНИЧЕСКИХ

СОЕДИНЕНИЙ." The 4th International scientific and practical conference “The world of science

and innovation”(November 11-13, 2020) Cognum Publishing House, London, United Kingdom.

2020. 1007 p.. 2020.
7. Guzal, Rakhmatova. "GRAVIMETRIC DETERMINATION OF THE INHIBITORY

PROPERTY AGAINST METAL CORROSION OF SUBSTANCES OBTAINED ON THE

BASIS OF THIAINDAN AND THIOCHROMAN Α-AMINO KETONES." Universum:

технические науки 10-7 (103) (2022): 14-17.
8. Guzal, Rakhmatova. "6-ACEETHYL-1-THIOXROMANE AND 7-ACEETHYL-6-METHYL-

1-THIOXROMANE ACETIC ETHER CONDENSATION REACTIONS WITH." Universum:

химия и биология 2.1 (115) (2024): 66-68.
9. Rakhmatova, Guzal. "INDUSTRIAL USE AND EFFECTIVENESS DETERMINATION OF

INHIBITORS BASED ON BISICLIC ORGANIC SULFUR COMPOUNDS." Universum:

технические науки 12-8 (117) (2023): 66-68.
10. Guzal, Rakhmatova. "METHODS OF SOLVING SAMPLE PROBLEMS ON THREE

UNKNOWN MIXTURES IN ORGANIC CHEMISTRY." International Journal of

Pedagogics 3.12 (2023): 43-48.


background image

INTERNATIONAL MULTIDISCIPLINARY JOURNAL FOR

RESEARCH & DEVELOPMENT

SJIF 2019: 5.222 2020: 5.552 2021: 5.637 2022:5.479 2023:6.563 2024: 7,805

eISSN :2394-6334 https://www.ijmrd.in/index.php/imjrd Volume 12, issue 06 (2025)

122

11. Guzal, Rakhmatova. "SYNTHESIS OF BENZO [B] THIOPHENE Α-HALOKETONE

HYDROCHLORIDES." International Journal of Pedagogics 3.12 (2023): 49-53.

Библиографические ссылки

Botirovna, Rakhmatova Guzal, et al. "Study of inspactive properties against corrosion of α-aminocetones and their products." Austrian Journal of Technical and Natural Sciences 5-6 (2020): 54-59.

Guzal, Rakhmatova. "KINETIC PROPERTIES OF BICYCLIC SULFUR ORGANIC INHIBITORS." Universum: химия и биология 12-2 (90) (2021): 55-58.

Рахматова, Гузал Ботировна, Мингникул Жумагулолвич Курбанов, and Миртемир Тоштемирович Рузибоев. "Синтез и изучение скорости реакции ацилирования 1-тиаинданов и 1-тиахроманов." Universum: химия и биология 12 (66) (2019): 82-85.

Курбанов, Мингникул Жумагулолвич, and Гузал Ботировна Рахматова. "ПРИМЕНЕНИЕ ТЕМПЕРАТУРНОЙ И КОНЦЕНТРАЦИОННОЙ ЗАВИСИМОСТИ ЭФФЕКТИВНОСТИ ИНГИБИТОРОВ НА ОСНОВЕ α-АМИНОКЕТОНОВ." Universum: технические науки 11-4 (92) (2021): 44-48.

Рахматова, Гузал Ботировна, Мингникул Жумагулолвич Курбанов, and Дилбар Дусмурадовна Атакулова. "БРОМИРОВАНИЯ АЦИЛПРОИЗВОДНЫХ 1-ТИАИНДАНОВОГО РЯДА." EUROPE, SCIENCE AND WE EVROPA, V DA A MY ЕВРОПА, НАУКА И МЫ (2020): 27.

Рахматова, Гузал Ботировна, and Искандар Исокович Аллабердиев. "ТЕМПЕРАТУРНАЯ ЗАВИСИМОСТЬ АНТИКОРРОЗИОННЫХ СВОЙСТВ БИЦИКЛОВЫХ ОРГАНИЧЕСКИХ СОЕДИНЕНИЙ." The 4th International scientific and practical conference “The world of science and innovation”(November 11-13, 2020) Cognum Publishing House, London, United Kingdom. 2020. 1007 p.. 2020.

Guzal, Rakhmatova. "GRAVIMETRIC DETERMINATION OF THE INHIBITORY PROPERTY AGAINST METAL CORROSION OF SUBSTANCES OBTAINED ON THE BASIS OF THIAINDAN AND THIOCHROMAN Α-AMINO KETONES." Universum: технические науки 10-7 (103) (2022): 14-17.

Guzal, Rakhmatova. "6-ACEETHYL-1-THIOXROMANE AND 7-ACEETHYL-6-METHYL-1-THIOXROMANE ACETIC ETHER CONDENSATION REACTIONS WITH." Universum: химия и биология 2.1 (115) (2024): 66-68.

Rakhmatova, Guzal. "INDUSTRIAL USE AND EFFECTIVENESS DETERMINATION OF INHIBITORS BASED ON BISICLIC ORGANIC SULFUR COMPOUNDS." Universum: технические науки 12-8 (117) (2023): 66-68.

Guzal, Rakhmatova. "METHODS OF SOLVING SAMPLE PROBLEMS ON THREE UNKNOWN MIXTURES IN ORGANIC CHEMISTRY." International Journal of Pedagogics 3.12 (2023): 43-48.

Guzal, Rakhmatova. "SYNTHESIS OF BENZO [B] THIOPHENE Α-HALOKETONE HYDROCHLORIDES." International Journal of Pedagogics 3.12 (2023): 49-53.