CHROMATO-MASS SPECTRUM ANALYSIS OF (2S)-1-MORPHOLIN-4-YL BUTAN-2-OL

ABSTRACT

Based on chromatograph mass spectrometry analysis, the formation of (2S)-1-morpholin-4-ylbutan-2-ol was identified as a secondary product resulting from the nucleophilic addition of morpholine to vinyl acetate, indicating the occurrence of a side reaction pathway under these experimental conditions. Chromatographic mass spectrometry was performed on an Agilent MSD 5975C-GC7890A chromatograph mass spectrometer. Analysis using other scientific literature showed that (2S)-1-morpholin-4-ylbutan-2-ol was formed. The yield of the product can be increased by reducing N-morpholinobutan-2-one. Compounds containing a morpholine fragment

АННОТАЦИЯ

На основании хромато-масс-спектрометрического анализа было идентифицировано образование (2S)-1-морфолин-4-илбутан-2-ола как вторичного продукта, возникающего в результате нуклеофильного присоединения морфолина к винилацетату, что указывает на возникновение побочного пути реакции в данных экспериментальных условиях. Хромато-масс-спектр был выполнен на приборе хромато-масс-спектрометр Agilent MSD 5975C-GC7890A. Анализ с использованием другой научной литературы показал, что образовался (2S)-1-морфолин-4-илбутан-2-ол. Увеличить выход продукта можно путем восстановления N-морфолинобутан-2-она. Соединения, содержащие фрагмент морфолина, могут быть использованы в качестве лекарств или ингибиторов коррозии.

Keywords: Morpholine, (2S)-1-morpholin-4-ylbutan-2-ol, chromatographic-mass spectrum, N-morpholinobutan-2-one.

Ключевые слова: Морфолин, (2S)-1-морфолин-4-илбутан-2-ол, хромато-масс-спектр, N-морфолинобутан-2-он

Introduction

In the studies [1], the medicinal structure of the morpholine ring and the medicinal chemistry/pharmacological activity of morpholine derivatives were investigated. In the study [2], the inhibition efficiency of new Mannich bases, 3-morpholino-1-phenylpropan-1-one and 3-morpholino-1-phenyl-3-(pyridin-4-yl)propan-1-one, as corrosion inhibitors for N80 steel was investigated with increasing inhibitor concentration. In other studies [3], the analytical methods for the determination of morpholine in peel and pulp fatty acids of morpholine fruits and vegetables were optimized. The reactions of vinyl acetylene with morpholine [4,5], salicylic acid [6], resorcinol [7] and the factors influencing them were studied. The chromatograph mass spectral analysis of the compound formed with phthalic anhydride was investigated [8]. From the analysis of the articles it is evident that the compounds formed by morpholine and vinyl acetyl have been studied in certain directions. In our studies [9] the synthesis of N-morpholinobutanone-2 and its inhibitory properties were studied. It was found that (2S)-1-morpholin-4-ylbutan-2-ol is formed as an adduct in this reaction.

The purpose of the study:

Chromatographic mass spectral analysis of (2s)-1-morpholin-4-yl butan-2-ol

Materials and research methods

The synthesis process was carried out as described in our previous study [9]. In addition to the equipment used for the synthesis, an Agilent MSD 5975C-GC7890A chromatograph mass spectrometer was used.

In our previous [9] studies, the additional formation of (2s)-1-morpholin-4-yl butan-2-ol in the synthesis of N-morpholinobutanone-2 was analyzed by chromatograph mass spectrometry. Chromatograph mass spectrometry analysis - chromatograph mass spectra were obtained on a standard HP-5MS column in liquid phase with control parameters in the range of 0-320 °C and an initial temperature from 50°C to 120 °C. Chromatograph mass spectrum of the synthesized 2s)-1-morpholin-4-yl butan-2-ol revealed the formation of ions corresponding to its molecular weight and the mass of fragment ions formed during its decomposition.

Research results

Based on our previous studies [9], the formation of an intermediate alcohol in the Kucherov reaction was determined based on the reaction mechanism. During the hydration process, the part of the diene form that did not convert to the in form in turn forms an alcohol. The resulting alcohol is also used in a mixture, since it exhibits inhibitory properties with its electron pairs. Based on the mass spectrum analysis of the synthesized alcohol, its structure was confirmed by chromato-mass spectrum. The chromato-mass spectrum of the synthesized (2s)-1-morpholin-4-yl butan-2-ol revealed the formation of ions corresponding to its molecular mass and the mass of fragment ions formed during its decomposition.

Figure 1. Chromatographic-mass spectrum of (2s)-1-morpholin-4-yl butan-2-ol

The chromatographic-mass spectrum of the synthesized (2s)-1-morpholin-4-yl butan-2-ol clearly showed the formation of an ion corresponding to its molecular mass and the mass of the fragment ion resulting from its fragmentation (Figure 1).In this case, the molecular ion peak of (2s)-1-morpholin-4-yl butan-2-ol corresponds to 159.0. Below is the fragmentation scheme of the fragment ions generated from the initial (2s)-1-morpholin-4-yl butan-2-ol molecular ion, as shown in table  1

Table 1.

The relative masses and intensities of the ions formed upon the chromatographic-mass spectrometry of (2s)-1-morpholin-4-yl butan-2-ol are as follows

After the introduction of (2s)-1-morpholin-4-yl butan-2-ol into the chromato-mass spectrometer, the molecular ion of (2s)-1-morpholin-4-yl butan-2-ol with m/z 159.0 was formed between 4.732 and 4.778 minutes under the selected conditions.

In addition, the spectrum revealed the formation of fragment ions with masses m/z 144, m/z 130, m/z 114, m/z 100, m/z 86, and m/z 70. The emission of the ion m/z 144 was observed as a result of the elimination of the methyl (-CH₃) radical from the (2s)-1-morpholin-4-yl butan-2-ol ion at 4.732 minutes. This peak corresponds to the C₇H₁₆NO₂⁺ ion with m/z 144.

The separation of the m/z 130 ion is observed due to the release of the methylene (-CH₂) radical from the C₇H₁₄NO₂⁺ ion. This peak corresponds to the C₆H₁₂NO₂+ ion with m/z 130.

At the same time, it can be seen that the ion with m/z 100 is formed from the decomposition of the C₆H₁₂NO₂+ ion with the release of the CHOH radical. This peak corresponds to the C₅H₁₀NO⁺ ion with a mass of m/z 100.

In turn, the release of the CH₂ radical from the C₅H₁₀NO⁺ ion at 1.644 minutes resulted in the release of the ion with m/z 86. This peak corresponds to the C₄H₈NO⁺ ion with m/z 86.

Discussion

The obtained analytical results and the mass of the formed fragment ions, when compared with many scientific literatur [10], confirm that the formed product is (2s)-1-morpholin-4-yl butan-2-ol. This shows that in addition to N-morpholinobutanone-2, (2s)-1-morpholin-4-yl butan-2-ol was formed during the synthesis [9]. The yield of (2s)-1-morpholin-4-yl butan-2-ol can be increased by reducing N-morpholinobutanone-2.

Conclusions

In conclusion, it can be said that based on the mass spectrum analysis of the synthesized substance, its identification is once again confirmed. From the obtained chromato-mass spectrum and the studies carried out during the synthesis, it can be said that (2s)-1-morpholin-4-yl butan-2-ol was formed as a reaction product.   Based on the results obtained, the structure of the substance was analyzed using fragment ions formed in the chromato-mass spectrum of 2s)-1-morpholin-4-yl butan-2-ol. Such substances can be used as inhibitors of compounds containing the morpholine fragment given in the introduction to the article, or applied to other areas of research, such as medicine.

References:

1. Kourounakis A. P., Xanthopoulos D., Tzara A. Morpholine as a privileged structure: A review on the medicinal chemistry and pharmacological activity of morpholine containing bioactive molecules //Medicinal Research Reviews. – 2020. – Т. 40. – №. 2. – С. 709-752.
2. Chen Y., Chen Z., Zhuo Y. Newly synthesized morpholinyl Mannich bases as corrosion inhibitors for N80 steel in acid environment //Materials. – 2022. – Т. 15. – №. 12. – С. 4218.
3. An K. et al. Quantification of Morpholine in Peel and Pulp of Apples and Oranges by Gas Chromatography− Mass Spectrometry //Foods. – 2020. – Т. 9. – №. 6. – С. 746.
4. Жумаев Ж. Х., Шарипова Н. У. Влияние растворителей на процесс взаимодействия морфолина с винилацетиленом //Universum: химия и биология. – 2020. – №. 11-2. – С. 4-7.
5. Жумаев Ж. Х., Ахмедов В. Н. Механизм повышение активности катализатора в процессе алленлизации мофолина винилацетиленом //Universum: химия и биология. – 2022. – №. 3-2 (93). – С. 24-27.
6. Рахматов М. С. Влияние катализатора, температуры и растворителя на синтез и выход продукта реакции с виниловым эфиром салициловый кислоты в присутствии винилацетилена //Universum: химия и биология. – 2020. – №. 11-2 (77). – С. 16-20.
7. Bahodirovich O. B. et al. Synthesis of Resorcinol Vinyl Ether in the Mono-position, Influence of the Catalyst, Temperature and Solvent on the Reaction Yield //JournalNX. – 2020. – С. 44-51.
8. Zukhriddin R., Sadullo K. CHROMATOMATIC MASS ANALYSIS OF DIVINYLACETYLENE DERIVATIVE OF PHTHALIC ANHYDRIDE //Universum: технические науки. – 2023. – №. 5-8 (110). – С. 30-33.
9. Жумаев Ж. Х. Синтез N-морфолинбутанона-2 и его ингибирующие свойства //Universum: химия и биология. – 2024. – Т. 2. – №. 5 (119). – С. 20-23.
10. Anderson R. J., Bendell D. J., Groundwater P. W. Organic spectroscopic analysis. – Royal Society of Chemistry, 2004. – Т. 22.