RU2372341C2 - METHOD OF PRODUCING [4N-1,3,5-DITHIAZINE-5(6N)-HYDROXY]-METHANOL, [2-[4N -1,3,5-DITHIAZIN-5 (6N)-YL]ETHOXY]-METHANOL, [2-[4N-1,3,5-DITHIAZIN-5(6N)-YL]BUTOXY]-METHANOL OR DIHYDRO-α-[(HYDROXYMETHOXY)METHYL]-4N-1,3,5-DITHIAZINE-5-ACETIC ACID - Google Patents
METHOD OF PRODUCING [4N-1,3,5-DITHIAZINE-5(6N)-HYDROXY]-METHANOL, [2-[4N -1,3,5-DITHIAZIN-5 (6N)-YL]ETHOXY]-METHANOL, [2-[4N-1,3,5-DITHIAZIN-5(6N)-YL]BUTOXY]-METHANOL OR DIHYDRO-α-[(HYDROXYMETHOXY)METHYL]-4N-1,3,5-DITHIAZINE-5-ACETIC ACID Download PDFInfo
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- RU2372341C2 RU2372341C2 RU2006115740/04A RU2006115740A RU2372341C2 RU 2372341 C2 RU2372341 C2 RU 2372341C2 RU 2006115740/04 A RU2006115740/04 A RU 2006115740/04A RU 2006115740 A RU2006115740 A RU 2006115740A RU 2372341 C2 RU2372341 C2 RU 2372341C2
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- methanol
- dithiazin
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- dithiazine
- hydroxymethoxy
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- 238000000034 method Methods 0.000 title claims abstract description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims description 28
- -1 HYDROXYMETHOXY Chemical class 0.000 title description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 title description 2
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical class [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 title 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 31
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000001414 amino alcohols Chemical class 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- CGZLPAGAIHOFPV-UHFFFAOYSA-N 2-(1,3,5-dithiazinan-5-yl)butoxymethanol Chemical compound OCOCC(CC)N1CSCSC1 CGZLPAGAIHOFPV-UHFFFAOYSA-N 0.000 claims description 20
- WNNHXOUGIUVSAJ-UHFFFAOYSA-N 2-(1,3,5-dithiazinan-5-yl)ethoxymethanol Chemical compound S1CSCN(C1)CCOCO WNNHXOUGIUVSAJ-UHFFFAOYSA-N 0.000 claims description 13
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 10
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 5
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 2
- 239000002594 sorbent Substances 0.000 abstract description 2
- 230000001580 bacterial effect Effects 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract 1
- 239000010970 precious metal Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 12
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N DMSO Substances CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- MHAKNDMCJAVDTK-UHFFFAOYSA-N 1-(1,3,5-dithiazinan-5-yl)ethanol Chemical compound S1CSCN(C1)C(C)O MHAKNDMCJAVDTK-UHFFFAOYSA-N 0.000 description 3
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 3
- WEMREENHLUWMAJ-UHFFFAOYSA-N 1-(1,3,5-oxathiazinan-5-yl)ethanol Chemical compound O1CSCN(C1)C(C)O WEMREENHLUWMAJ-UHFFFAOYSA-N 0.000 description 2
- GXAFNKBVQWVXTO-UHFFFAOYSA-N 4h-1,3,5-dithiazine Chemical class C1SCN=CS1 GXAFNKBVQWVXTO-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ZRKMQKLGEQPLNS-UHFFFAOYSA-N 1-Pentanethiol Chemical class CCCCCS ZRKMQKLGEQPLNS-UHFFFAOYSA-N 0.000 description 1
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 1
- BLFRQYKZFKYQLO-UHFFFAOYSA-N 4-aminobutan-1-ol Chemical compound NCCCCO BLFRQYKZFKYQLO-UHFFFAOYSA-N 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- LXGVMCWMPDUSNJ-UHFFFAOYSA-N OCON1CSCSC1 Chemical compound OCON1CSCSC1 LXGVMCWMPDUSNJ-UHFFFAOYSA-N 0.000 description 1
- 102100038239 Protein Churchill Human genes 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- MNQDKWZEUULFPX-UHFFFAOYSA-M dithiazanine iodide Chemical class [I-].S1C2=CC=CC=C2[N+](CC)=C1C=CC=CC=C1N(CC)C2=CC=CC=C2S1 MNQDKWZEUULFPX-UHFFFAOYSA-M 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Предлагаемое изобретение относится к органической химии, в частности к способу получения [4H-1,3,5-дитиазин-5(6H)-гидрокси]-метанола, [2-[4H-1,3,5-дитиазин-5(6H)-ил]этокси]-метанола, [2-[4H-1,3,5-дитиазин-5(6H)-ил]бутокси]-метанола и дигидро-α-[(гидроксиметокси)метил]-4H-1,3,5-дитиазин-5-ацетик ацида общей формулыThe present invention relates to organic chemistry, in particular to a method for producing [4H-1,3,5-dithiazin-5 (6H) -hydroxy] methanol, [2- [4H-1,3,5-dithiazin-5 (6H ) -yl] ethoxy] methanol, [2- [4H-1,3,5-dithiazin-5 (6H) -yl] butoxy] methanol and dihydro-α - [(hydroxymethoxy) methyl] -4H-1, 3,5-dithiazin-5-acetic acidide of the general formula
где R=OCH2OH (1а);where R = OCH 2 OH (1a);
R=СН2СН2ОСН2ОН (1б);R = CH 2 CH 2 OCH 2 OH (1b);
R=СН(СН2СН3)CH2OCH2OH (1в);R = CH (CH 2 CH 3 ) CH 2 OCH 2 OH (1c);
R=СН2(CH2OCH2OH)СН2СООН (1г).R = CH 2 (CH 2 OCH 2 OH) CH 2 COOH (1 g).
Соединения дитиазинового ряда могут найти применение в качестве селективных сорбентов и экстрагентов, специальных реагентов для подавления жизнедеятельности бактерий в различных средах (от легкой промышленности до нефти), биологически активных веществ по отношению к сульфатредуцирующим бактериям.The compounds of the dithiazine series can be used as selective sorbents and extractants, special reagents for suppressing the activity of bacteria in various media (from light industry to oil), biologically active substances with respect to sulfate-reducing bacteria.
Известен способ (С.Р.Хафизова, В.Р.Ахметова, Л.Ф.Коржова, Т.В.Хакимова, Г.Р.Надыргулова, Р.В.Кунакова, Э.А.Круглов, У.М.Джемилев. Многокомпонентная конденсация алифатических аминов с формальдегидом и сероводородом. Изв. АН. Сер. хим. 2005, 2, 423) получения производных 1,3,5-дитиазина, в частности 2-пергидро(1,3,5-дитиазин-5-ил)-1-этанола (2) и 2-пергидро(1,3,5-оксатиазин-5-ил)-1-этанола (3) взаимодействием этаноламина с сероводородом и формальдегидом по схеме:The known method (S.R. Khafizova, V.R. Akhmetova, L.F. Korzhova, T.V. Khakimova, G.R. Nadyrgulov, R.V. Kunakova, E.A. Kruglov, U.M. Dzhemilev Multicomponent condensation of aliphatic amines with formaldehyde and hydrogen sulfide. Izv. AN Ser. Chem. 2005, 2, 423) for the preparation of 1,3,5-dithiazine derivatives, in particular 2-perhydro (1,3,5-dithiazin-5- il) -1-ethanol (2) and 2-perhydro (1,3,5-oxathiazin-5-yl) -1-ethanol (3) by the interaction of ethanolamine with hydrogen sulfide and formaldehyde according to the scheme:
Известный способ не позволяет получать [4H-1,3,5-дитиазин-5(6H)-гидрокси]-метанол (1а), [2-[4H-1,3,5-дитиазин-5(6H)-ил]этокси]-метанол (1б), [2-[4H-1,3,5-дитиазин-5(6H)-ил]бутокси]-метанол (1в) и дигидро-α-[(гидроксиметокси)метил]-4H-1,3,5-дитиазин-5-ацетик ацид (1г).The known method does not allow to obtain [4H-1,3,5-dithiazin-5 (6H) -hydroxy] -methanol (1a), [2- [4H-1,3,5-dithiazin-5 (6H) -yl] ethoxy] methanol (1b), [2- [4H-1,3,5-dithiazin-5 (6H) -yl] butoxy] methanol (1c) and dihydro-α - [(hydroxymethoxy) methyl] -4H- 1,3,5-dithiazin-5-acetic acid (1g).
Известен способ (Deutsche Gold- und Silber-Scheideanstalt vormals Roessler. F.P. 1,341,792/1963 (Chem. Abs., 1964, 60, 5528d)) получения производных 1,3,5-дитиазина, в частности 2-пергидро(1,3,5-дитиазин-5-ил)-1-этанола (2), взаимодействием гидросульфида натрия (NaHS) с этаноламином и формальдегидом по схеме:A known method (Deutsche Gold- und Silber-Scheideanstalt vormals Roessler. FP 1,341,792 / 1963 (Chem. Abs., 1964, 60, 5528d)) for the preparation of 1,3,5-dithiazine derivatives, in particular 2-perhydro (1,3, 5-dithiazin-5-yl) -1-ethanol (2), by the interaction of sodium hydrosulfide (NaHS) with ethanolamine and formaldehyde according to the scheme:
Известный способ не позволяет получать [4H-1,3,5-дитиазин-5(6H)-гидрокси]-метанол (1а), [2-[4H-1,3,5-дитиазин-5(6H)-ил]этокси]-метанол (1б), [2-[4H-1,3,5-дитиазин-5(6H)-ил]бутокси]-метанол (1в) и дигидро-α-[(гидроксиметокси)метил]-4H-1,3,5-дитиазин-5-ацетик ацид (1г). Данным способом получен 2-пергидро(1,3,5-дитиазин-5-ил)-1-этанола (2) на основе дорогостоящего и высокочистого гидросульфита натрия, который получают из сероводорода и этилата натрия.The known method does not allow to obtain [4H-1,3,5-dithiazin-5 (6H) -hydroxy] -methanol (1a), [2- [4H-1,3,5-dithiazin-5 (6H) -yl] ethoxy] methanol (1b), [2- [4H-1,3,5-dithiazin-5 (6H) -yl] butoxy] methanol (1c) and dihydro-α - [(hydroxymethoxy) methyl] -4H- 1,3,5-dithiazin-5-acetic acid (1g). In this way, 2-perhydro (1,3,5-dithiazin-5-yl) -1-ethanol (2) was prepared on the basis of expensive and high-purity sodium hydrosulfite, which is obtained from hydrogen sulfide and sodium ethylate.
Таким образом, в литературе отсутствуют сведения о получении [4Н-1,3,5-дитиазин-5(6H)-гидрокси]-метанола (1а), [2-[4H-1,3,5-дитиазин-5(6H)-ил]этокси]-метанола (1б), [2-[4H-1,3,5-дитиазин-5(6H)-ил]бутокси]-метанола (1в) и дигидро-α-[(гидроксиметокси)метил]-4H-1,3,5-дитиазин-5-ацетик ацида(1г).Thus, there is no information in the literature on the preparation of [4H-1,3,5-dithiazin-5 (6H) -hydroxy] methanol (1a), [2- [4H-1,3,5-dithiazin-5 (6H ) -yl] ethoxy] methanol (1b), [2- [4H-1,3,5-dithiazin-5 (6H) -yl] butoxy] methanol (1c) and dihydro-α - [(hydroxymethoxy) methyl ] -4H-1,3,5-dithiazin-5-acetic acidide (1g).
Предлагается новый способ синтеза [4H-1,3,5-дитиазин-5(6H)-гидрокси]-метанола (1а), [2-[4H-1,3,5-дитиазин-5(6H)-ил]этокси]-метанола (1б), [2-[4H-1,3,5-дитиазин-5(6H)-ил]бутокси]-метанола (1в) и дигидро-α-[(гидроксиметокси)метил]-4H-1,3,5-дитиазин-5-ацетик ацида (1г).A new method for the synthesis of [4H-1,3,5-dithiazin-5 (6H) -hydroxy] methanol (1a), [2- [4H-1,3,5-dithiazin-5 (6H) -yl] ethoxy ] -methanol (1b), [2- [4H-1,3,5-dithiazin-5 (6H) -yl] butoxy] methanol (1c) and dihydro-α - [(hydroxymethoxy) methyl] -4H-1 , 3,5-dithiazin-5-acetic acidide (1g).
Сущность метода заключается во взаимодействии насыщенного сероводородом водного раствора формальдегида (37%) с водным раствором аминоспирта, общей формулы: R-NH2 (где R=OCH2OH (1a); CH2CH2OCH2OH (1б); СН(СН2СН3)CH2OCH2OH (1в); СН2(CH2OCH2OH)СН2СООН (1г)), взятыми в мольном соотношении аминоспирт: формальдегид:сероводород = 1:4:2, при температуре 40°С и перемешивании в течение 3 часов. Образуется [4H-1,3,5-дитиазин-5(6H)-гидрокси]-метанол (1а), ([2-[4H-1,3,5-дитиазин-5(6H)-ил]этокси]-метанол (1б), [2-[4H-1,3,5-дитиазин-5(6H)-ил]бутокси]-метанол (1в) и дигидро-α-[(гидроксиметокси)метил]-4H-1,3,5-дитиазин-5-ацетик ацид (1г)). Реакция протекает по схеме:The essence of the method consists in the interaction of an aqueous solution of formaldehyde saturated with hydrogen sulfide (37%) with an aqueous solution of an amino alcohol of the general formula: R-NH 2 (where R = OCH 2 OH (1a); CH 2 CH 2 OCH 2 OH (1b); CH ( CH 2 CH 3 ) CH 2 OCH 2 OH (1B); CH 2 (CH 2 OCH 2 OH) CH 2 COOH (1 g)), taken in the molar ratio of amino alcohol: formaldehyde: hydrogen sulfide = 1: 4: 2, at a temperature of 40 ° C and stirring for 3 hours. [4H-1,3,5-dithiazin-5 (6H) -hydroxy] methanol (1a), ([2- [4H-1,3,5-dithiazin-5 (6H) -yl] ethoxy] - methanol (1b), [2- [4H-1,3,5-dithiazin-5 (6H) -yl] butoxy] methanol (1c) and dihydro-α - [(hydroxymethoxy) methyl] -4H-1,3 5-dithiazine-5-acetic acid (1g)). The reaction proceeds according to the scheme:
где R=OCH2OH (1а);where R = OCH 2 OH (1a);
R=CH2CH2OCH2OH (1б);R = CH 2 CH 2 OCH 2 OH (1b);
R=СН(СН2СН3)CH2OCH2OH (1в);R = CH (CH 2 CH 3 ) CH 2 OCH 2 OH (1c);
R=СН2(CH2OCH2OH)СН2СООН (1г).R = CH 2 (CH 2 OCH 2 OH) CH 2 COOH (1 g).
Целевые продукты [4H-1,3,5-дитиазин-5(6H)-гидрокси]-метанол (1а), [2-[4H-1,3,5-дитиазин-5(6H)-ил]этокси]-метанол (1б), [2-[4H-1,3,5-дитиазин-5(6H)-ил]бутокси]-метанол (1в) и дигидро-α-[(гидроксиметокси)метил]-4H-1,3,5-дитиазин-5-ацетик ацид (1г) образуются только лишь с участием гидроксиламина (этаноламина, 2-амино-3-оксипропановой кислоты, 2-бутаноламина), формалина и сероводорода. В присутствии других производных аминоспиртов (например, 4-аминобутанола, 5-аминобутанола), других альдегидов (например, уксусного, пропионового), других меркаптанов (например, этил- или амилмеркаптаны) целевые продукты (1) не образуются. Реакции проводили при температуре 40°С. При более высокой температуре не наблюдается существенного увеличения выхода целевых продуктов, а при меньшей температуре (например, 0°С) снижается скорость реакции.Target Products [4H-1,3,5-dithiazin-5 (6H) -hydroxy] methanol (1a), [2- [4H-1,3,5-dithiazin-5 (6H) -yl] ethoxy] - methanol (1b), [2- [4H-1,3,5-dithiazin-5 (6H) -yl] butoxy] methanol (1c) and dihydro-α - [(hydroxymethoxy) methyl] -4H-1,3 , 5-dithiazine-5-acetic acid (1 g) are formed only with the participation of hydroxylamine (ethanolamine, 2-amino-3-hydroxypropanoic acid, 2-butanolamine), formalin and hydrogen sulfide. In the presence of other derivatives of amino alcohols (e.g., 4-aminobutanol, 5-aminobutanol), other aldehydes (e.g., acetic, propionic), other mercaptans (e.g. ethyl or amyl mercaptans), the desired products (1) are not formed. The reaction was carried out at a temperature of 40 ° C. At a higher temperature, there is no significant increase in the yield of the target products, and at a lower temperature (for example, 0 ° C), the reaction rate decreases.
Изменение соотношения исходных реагентов в сторону увеличения содержания формалина по отношению к аминоспирту не приводит к повышению выхода целевых продуктов (1).A change in the ratio of the starting reagents in the direction of increasing the formalin content with respect to the amino alcohol does not increase the yield of the target products (1).
Существенные отличия предлагаемого способаSignificant differences of the proposed method
В предлагаемом способе в качестве исходных соединений используются гидроксиламин, этаноламин, 2-амино-3-оксипропановая кислота, 2-бутаноламин в реакции с формальдегидом и сероводородом в соотношении 1:4:2, в известном способе в качестве исходного реагента” применяют этаноламин и дорогостоящий, высокочистый гидросульфит натрия (NaHS) (в соотношении исходных реагентов 1:3:2), который, как известно, получают из сероводорода и этилата натрия.In the proposed method, hydroxylamine, ethanolamine, 2-amino-3-hydroxypropanoic acid, 2-butanolamine in the reaction with formaldehyde and hydrogen sulfide in a ratio of 1: 4: 2 are used as starting compounds, in the known method, ethanolamine and an expensive one are used , high-purity sodium hydrosulfite (NaHS) (in the ratio of the starting reagents 1: 3: 2), which is known to be obtained from hydrogen sulfide and sodium ethylate.
Преимущества предлагаемого способаThe advantages of the proposed method
Способ позволяет получать с высокой региоселективностью [4H-1,3,5-дитиазин-5(6H)-гидрокси]-метанол (1а), [2-[4H-1,3,5-дитиазин-5(6H)-ил]этокси]-метанол (1б), [2-[4H-1,3,5-дитиазин-5(6H)-ил]бутокси]-метанол (1в) и дигидро-α-[(гидроксиметокси)метил]-4H-1,3,5-дитиазин-5-ацетик ацид (1г), синтез которых в литературе не описан. Разработанный нами метод отличается простотой проведения эксперимента и не требует применения дорогостоящего и высокоочищенного гидросульфида натрия.The method allows to obtain with high regioselectivity [4H-1,3,5-dithiazin-5 (6H) -hydroxy] -methanol (1a), [2- [4H-1,3,5-dithiazin-5 (6H) -yl ] ethoxy] methanol (1b), [2- [4H-1,3,5-dithiazin-5 (6H) -yl] butoxy] methanol (1c) and dihydro-α - [(hydroxymethoxy) methyl] -4H -1,3,5-dithiazin-5-acetic acid (1 g), the synthesis of which is not described in the literature. The method we developed is notable for the simplicity of the experiment and does not require the use of expensive and highly purified sodium hydrosulfide.
Способ поясняется примерамиThe method is illustrated by examples.
ПРИМЕР 1. В стеклянный реактор, снабженный механической мешалкой, обратным холодильником, газоподводящей трубкой и капельной воронкой, при комнатной температуре 40°С помещают 3 моля формалина (37% водный раствор), барботированием насыщают раствор формалина сероводородом в течение 30 мин, прикапывают 1 моль солянокислый гидроксиламин в воде, перемешивают 3 ч. При 40°С выделяют [4H-1,3,5-дитиазин-5(6H)-гидрокси]-метанол (1а) с выходом 56%.EXAMPLE 1. In a glass reactor equipped with a mechanical stirrer, a reflux condenser, a gas supply tube and a dropping funnel, 3 mol of formalin (37% aqueous solution) was placed at room temperature 40 ° C, bubbling saturated formalin solution with hydrogen sulfide for 30 min, dropping 1 mol hydroxylamine hydrochloride in water, stirred for 3 hours. At 40 ° C, [4H-1,3,5-dithiazin-5 (6H) -hydroxy] -methanol (1a) was isolated in 56% yield.
Спектр ЯМР 13С, δ, м.д.: 30.44 т (С2), 57.22 т (С4,6), 89.98 т (С8). 1 H NMR, δ, ppm .: (d 6 -DMSO) 4.50 bs (2H, 2 H), 4.90 bs (4H, H 4,6) 5.19 d (2H, H 8, 3 J 5.4 Hz), 6.99 t (N, OH 3 J 5.4 Hz).
13 C NMR spectrum, δ, ppm: 30.44 t (C 2 ), 57.22 t (C 4.6 ), 89.98 t (C 8 ).
[CHSCH2S]+, 75 (32) [HOCH2ONHCH2]+, 57 (29) [ONCH2CH]+, 46 (76) [CH2S]+, 45 (100) [CHS]+.Mass spectrum, m / z (I Rel ,%): 167 (5) [M] + , 135 (7) [MS] + , 121 (57) [M-SCH 2 ] + , 110 (8) [M -CSCH] + , 91 (10)
[CHSCH 2 S] + , 75 (32) [HOCH 2 ONHCH 2 ] + , 57 (29) [ONCH 2 CH] + , 46 (76) [CH 2 S] + , 45 (100) [CHS] + .
ПРИМЕР 2. Аналогичным способом из этаноламина получают [2-[4Н-1,3,5-дитиазин-5(6H)-ил]этокси]-метанол (1б) с выходом 18%.EXAMPLE 2. [2- [4H-1,3,5-dithiazin-5 (6H) -yl] ethoxy] methanol (1b) was obtained from ethanolamine in a yield of 18%.
Спектр ЯМР 13С, δ, м.д.: 31.52 т (С2), 53.53 т (С7), 57.11 т (С4,6), 63.37 т (С8), 88.44 т (С10). 1 H NMR, δ, ppm .: (d 6 -DMSO) 1.95 m (2H, H 7, 3 J 7.1 Hz), 3.60 m (2H, H 8, 3 J 7.1 Hz), 4.50 brs (2Н, Н 2 ), 4.90 br.s (4Н, Н 4,6 ), 5.19 d (2Н, Н 10 , 3 J 5.4 Hz), 6.99 t (Н, ОН 3 J 5.4 Hz).
13 C NMR spectrum, δ, ppm: 31.52 t (C 2 ), 53.53 t (C 7 ), 57.11 t (C 4.6 ), 63.37 t (C 8 ), 88.44 t (C 10 ).
ПРИМЕР 3. Аналогичным способом из 2-бутаноламина получают [2-[4H-1,3,5-дитиазин-5(6H)-ил]бутокси]-метанол (1в) с выходом 52%.EXAMPLE 3. In a similar manner from 2-butanolamine receive [2- [4H-1,3,5-dithiazin-5 (6H) -yl] butoxy] methanol (1B) with a yield of 52%.
На 4, Не 6, 2J=11.5). 1 H NMR spectrum (δ, ppm): 0.82-95 t (3H, H 9 ), 1.30-1.60 m (2H, H 8 ), 3.06 t (1H, H 7 ), 3.35 t (1H, OH) ), 3.92 s (2H, H 12), 3.94 d (2H, H 10), 4.02 s (2H, H 2), 4.33 d (2H, H e 4, H and 6, 2 J = 11.5), 4.47 d (2H,
N a 4 , H e 6 , 2 J = 11.5).
[М-CH2OCH2OH3]+; 130 (8) [M-HSCH2SCH3]+; 116 (7) [M-CH2SCH2SCH]+; 84 (46) [СН2СН(СН2СН3)NCH]+; 70 (46) [CH2CH(CH2CH3)N]+; 45 (38) [CHS]+; 42 (100) [СНСН2СН3]+.Mass spectrum, m / z (I rel (%)): 223 (7) [M] + , 162 (20)
[M-CH 2 OCH 2 OH 3 ] + ; 130 (8) [M-HSCH 2 SCH 3 ] + ; 116 (7) [M-CH 2 SCH 2 SCH] + ; 84 (46) [CH 2 CH (CH 2 CH 3 ) NCH] + ; 70 (46) [CH 2 CH (CH 2 CH 3 ) N] + ; 45 (38) [CHS] + ; 42 (100) [CHCH 2 CH 3 ] + .
ПРИМЕР 4. Аналогичным способом из 2-амино-3-оксипропановой кислоты получают дигидро-α-[(гидроксиметокси)метил]-4H-1,3,5-дитиазин-5-ацетик ацид (1г) с выходом 64%.EXAMPLE 4. In a similar manner from 2-amino-3-hydroxypropanoic acid, dihydro-α - [(hydroxymethoxy) methyl] -4H-1,3,5-dithiazin-5-acetic acid (1 g) is obtained in 64% yield.
Н2,4,6,7,8), 4.25 уш.с (2Н, Н10). 1 H NMR spectrum (δ, ppm, d 6 -DMSO, J / Hz): 3.20-3.80 m (9H,
H, 2,4,6,7,8 ), 4.25 br.s (2H, H 10 ).
Claims (1)
где R=OCH2OH;
R=CH2CH2OCH2OH;
R=СН(СН2СН3)CH2OCH2OH;
R=СН2(CH2OCH2OH)СН2СООН,
отличающийся тем, что насыщенный сероводородом водный раствор формальдегида взаимодействует с водным раствором аминоспирта общей формулы R-NH2 (где R=OCH2OH; CH2CH2OCH2OH; СН(СН2СН3)CH2OCH2OH; СН2(CH2OCH2OH)СН2СООН), в мольном соотношении аминоспирт:формальдегид:сероводород, равном 1:4:2, при температуре 40°С и перемешивании в течение 3 ч. The method of obtaining [4H-1,3,5-dithiazin-5 (6H) -hydroxy] methanol, [2- [4H-1,3,5-dithiazin-5 (6H) -yl] ethoxy] methanol, [ 2- [4H-1,3,5-dithiazin-5 (6H) -yl] butoxy] methanol or dihydro-α - [(hydroxymethoxy) methyl] -4H-1,3,5-dithiazin-5-acetic acid general formula
where R = OCH 2 OH;
R = CH 2 CH 2 OCH 2 OH;
R = CH (CH 2 CH 3 ) CH 2 OCH 2 OH;
R = CH 2 (CH 2 OCH 2 OH) CH 2 COOH,
characterized in that the aqueous solution of formaldehyde saturated with hydrogen sulfide interacts with an aqueous solution of an amino alcohol of the general formula R-NH 2 (where R = OCH 2 OH; CH 2 CH 2 OCH 2 OH; CH (CH 2 CH 3 ) CH 2 OCH 2 OH; CH 2 (CH 2 OCH 2 OH) CH 2 COOH), in the molar ratio of amino alcohol: formaldehyde: hydrogen sulfide, equal to 1: 4: 2, at a temperature of 40 ° C and stirring for 3 hours
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| RU2006115740/04A RU2372341C2 (en) | 2006-05-06 | 2006-05-06 | METHOD OF PRODUCING [4N-1,3,5-DITHIAZINE-5(6N)-HYDROXY]-METHANOL, [2-[4N -1,3,5-DITHIAZIN-5 (6N)-YL]ETHOXY]-METHANOL, [2-[4N-1,3,5-DITHIAZIN-5(6N)-YL]BUTOXY]-METHANOL OR DIHYDRO-α-[(HYDROXYMETHOXY)METHYL]-4N-1,3,5-DITHIAZINE-5-ACETIC ACID |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2951149B1 (en) | 2013-01-30 | 2018-10-10 | Ecolab USA Inc. | Hydrogen sulfide scavengers |
| US10538710B2 (en) | 2017-07-13 | 2020-01-21 | Ecolab Usa Inc. | Hydrogen sulfide scavengers |
| US10584286B2 (en) | 2015-09-08 | 2020-03-10 | Ecolab Usa Inc. | Hydrogen sulfide scavengers |
| US11085002B2 (en) | 2015-04-22 | 2021-08-10 | Championx Usa Inc. | Development of a novel high temperature stable scavenger for removal of hydrogen sulfide |
| US11499108B2 (en) | 2019-01-23 | 2022-11-15 | Championx Usa Inc. | Complete removal of solids during hydrogen sulfide scavenging operations using a scavenger and a Michael acceptor |
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| RU2425039C2 (en) * | 2009-01-28 | 2011-07-27 | Учреждение Российской Академии Наук Институт Нефтехимии И Катализа Ран | Method for selective production of 2-, 3- and 4-(1,3,5-dithiazinan-5-yl)thiophenols |
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| С.Р.Хафизова и др. Изв. АН Сер. Хим. 2005, 2, 423. * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2951149B1 (en) | 2013-01-30 | 2018-10-10 | Ecolab USA Inc. | Hydrogen sulfide scavengers |
| US10703710B2 (en) | 2013-01-30 | 2020-07-07 | Ecolab Usa Inc. | Hydrogen sulfide scavengers |
| US11339118B2 (en) | 2013-01-30 | 2022-05-24 | Ecolab Usa Inc. | Hydrogen sulfide scavengers |
| US11085002B2 (en) | 2015-04-22 | 2021-08-10 | Championx Usa Inc. | Development of a novel high temperature stable scavenger for removal of hydrogen sulfide |
| US10584286B2 (en) | 2015-09-08 | 2020-03-10 | Ecolab Usa Inc. | Hydrogen sulfide scavengers |
| US10538710B2 (en) | 2017-07-13 | 2020-01-21 | Ecolab Usa Inc. | Hydrogen sulfide scavengers |
| US11499108B2 (en) | 2019-01-23 | 2022-11-15 | Championx Usa Inc. | Complete removal of solids during hydrogen sulfide scavenging operations using a scavenger and a Michael acceptor |
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