ES2381725B2 - PROCEDURE FOR THE CATALYTIC REDUCTION OF ORGANIC SULPHOXIDS. - Google Patents
PROCEDURE FOR THE CATALYTIC REDUCTION OF ORGANIC SULPHOXIDS. Download PDFInfo
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- ES2381725B2 ES2381725B2 ES201001413A ES201001413A ES2381725B2 ES 2381725 B2 ES2381725 B2 ES 2381725B2 ES 201001413 A ES201001413 A ES 201001413A ES 201001413 A ES201001413 A ES 201001413A ES 2381725 B2 ES2381725 B2 ES 2381725B2
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- 238000000034 method Methods 0.000 title claims abstract description 51
- 238000010531 catalytic reduction reaction Methods 0.000 title claims abstract description 19
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 claims abstract description 46
- 150000003462 sulfoxides Chemical group 0.000 claims abstract description 37
- 150000003568 thioethers Chemical group 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 10
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 7
- 239000011733 molybdenum Substances 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 238000006722 reduction reaction Methods 0.000 claims description 28
- ASLHVQCNFUOEEN-UHFFFAOYSA-N dioxomolybdenum;dihydrochloride Chemical compound Cl.Cl.O=[Mo]=O ASLHVQCNFUOEEN-UHFFFAOYSA-N 0.000 claims description 10
- -1 4-pentenyl Chemical group 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 238000006392 deoxygenation reaction Methods 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 3
- 230000000694 effects Effects 0.000 claims 3
- 229910000077 silane Inorganic materials 0.000 claims 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 2
- ILVXOBCQQYKLDS-UHFFFAOYSA-N pyridine N-oxide Chemical class [O-][N+]1=CC=CC=C1 ILVXOBCQQYKLDS-UHFFFAOYSA-N 0.000 claims 2
- 239000000126 substance Substances 0.000 claims 2
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- FSGYTLFCOYYZKG-UHFFFAOYSA-N n,n-dichloroformamide Chemical compound ClN(Cl)C=O FSGYTLFCOYYZKG-UHFFFAOYSA-N 0.000 claims 1
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 claims 1
- 238000010992 reflux Methods 0.000 claims 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 239000007832 Na2SO4 Substances 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 150000002898 organic sulfur compounds Chemical class 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000004611 spectroscopical analysis Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- LOWMYOWHQMKBTM-UHFFFAOYSA-N 1-butylsulfinylbutane Chemical compound CCCCS(=O)CCCC LOWMYOWHQMKBTM-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229930186147 Cephalosporin Natural products 0.000 description 2
- HTIRHQRTDBPHNZ-UHFFFAOYSA-N Dibutyl sulfide Chemical compound CCCCSCCCC HTIRHQRTDBPHNZ-UHFFFAOYSA-N 0.000 description 2
- JJHHIJFTHRNPIK-UHFFFAOYSA-N Diphenyl sulfoxide Chemical compound C=1C=CC=CC=1S(=O)C1=CC=CC=C1 JJHHIJFTHRNPIK-UHFFFAOYSA-N 0.000 description 2
- 101100073357 Streptomyces halstedii sch2 gene Proteins 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229940124587 cephalosporin Drugs 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- ZUBXPSDFPQTKQN-ZCFIWIBFSA-N (6r)-3-hydroxy-5-thia-1-azabicyclo[4.2.0]oct-2-en-8-one Chemical compound S1CC(O)=CN2C(=O)C[C@H]21 ZUBXPSDFPQTKQN-ZCFIWIBFSA-N 0.000 description 1
- HTFTURZHXAWZPC-SSDOTTSWSA-N (6r)-3-methylidene-5-thia-1-azabicyclo[4.2.0]octan-8-one Chemical class C1C(=C)CS[C@@H]2CC(=O)N21 HTFTURZHXAWZPC-SSDOTTSWSA-N 0.000 description 1
- WQADWIOXOXRPLN-UHFFFAOYSA-N 1,3-dithiane Chemical compound C1CSCSC1 WQADWIOXOXRPLN-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 1
- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 238000005842 biochemical reaction Methods 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 125000006412 propinylene group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 150000003461 sulfonyl halides Chemical class 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 150000003582 thiophosphoric acids Chemical class 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
La presente invención se refiere a un procedimiento para la reducción catalítica de compuestos orgánicos que incluyen un grupo funcional sulfóxido a compuestos tipo sulfuro que incluyen un grupo funcional tioéter mediante la utilización de pinacol (2,3-dimetil-2,3-butanodiol) como agente reductor en presencia de un catalizador de molibdeno (VI), en un medio libre de disolventes orgánicos, bajo presión atmosférica y a una temperatura entre 70-90º C, generando como únicos subproductos agua y acetona.The present invention relates to a process for the catalytic reduction of organic compounds that include a sulfoxide functional group to sulfur-like compounds that include a thioether functional group by using pinacol (2,3-dimethyl-2,3-butanediol) as reducing agent in the presence of a molybdenum catalyst (VI), in a medium free of organic solvents, under atmospheric pressure and at a temperature between 70-90 ° C, generating as only by-products water and acetone.
Description
Procedimiento para la reducción catalítica de sulfóxidos orgánicos. Procedure for catalytic reduction of organic sulfoxides.
Objeto de la invención Object of the invention
La presente invención se refiere a un procedimiento para la reducción catalítica de compuestos orgánicos que incluyen un grupo funcional sulfóxido, esto es compuestos de fórmula general R1-S(=O)-R2, siendo R1 yR2 grupos orgánicos, a compuestos orgánicos de tipo sulfuro, R1-S-R2, incluyendo un grupo funcional tioéter. The present invention relates to a process for the catalytic reduction of organic compounds that include a sulfoxide functional group, that is compounds of the general formula R1-S (= O) -R2, R1 and R2 being organic groups, to sulfide type organic compounds , R1-S-R2, including a thioether functional group.
Más concretamente, la invención se refiere a un procedimiento para la reducción catalítica de compuestos orgánicos que incluyen un grupo funcional sulfóxido a compuestos tipo sulfuro que incluyen un grupo funcional tioéter mediante la utilización de pinacol (2,3-dimetil-2,3-butanodiol) como agente reductor en presencia de un catalizador de molibdeno, en un medio libre de disolventes orgánicos, bajo presión atmosféricayauna temperatura entre 70-90ºC. More specifically, the invention relates to a process for the catalytic reduction of organic compounds that include a sulfoxide functional group to sulfide-type compounds that include a thioether functional group by the use of pinacol (2,3-dimethyl-2,3-butanediol ) as a reducing agent in the presence of a molybdenum catalyst, in a medium free of organic solvents, under atmospheric pressure and at a temperature between 70-90 ° C.
Antecedentes de la invención Background of the invention
La reducción de sulfóxidos a sus correspondientes sulfuros constituye una importante reacción de gran utilidad tanto en reacciones bioquímicas como en reacciones de síntesis orgánica. The reduction of sulfoxides to their corresponding sulphides constitutes an important reaction of great utility both in biochemical reactions and in reactions of organic synthesis.
En general, para la reducción de sulfóxidos a sulfuros se han venido utilizando compuestos que contienen azufre, tales como tioles, sulfuro de hidrógeno, ácidos tales como ácidos carboditiónicos o ácidos tiofosfónicos o tiofosfóricos, cloruros tales como cloruro de sulfonilo o de sulfinilo, disulfuros, azufre elemental (S8) y cloruro de tionilo. Sin embargo, estos métodos presentan ciertas desventajas, haciendo necesario el desarrollo de nuevos métodos de reducción con compuestos que contienen azufre. In general, sulfur-containing compounds, such as thiols, hydrogen sulfide, acids such as carbodithionic acids or thiophosphonic or thiophosphoric acids, chlorides such as sulfonyl or sulphonyl chloride, disulfides have been used for the reduction of sulfoxides to sulfides. elemental sulfur (S8) and thionyl chloride. However, these methods have certain disadvantages, making it necessary to develop new reduction methods with sulfur-containing compounds.
Uno de estos nuevos métodos es, por ejemplo, la desoxigenación de sulfóxidos en presencia de 1,3-ditiano utilizando como catalizador N-bromosuccinimida (NBS), 2,4,4,6-tetrabromo-2,5-ciclohexanodiona (TABCO) o Br2 como fuente electrofílica de bromo a temperatura ambiente (r.t.). One of these new methods is, for example, the deoxygenation of sulfoxides in the presence of 1,3-dithian using as catalyst N-bromosuccinimide (NBS), 2,4,4,6-tetrabromo-2,5-cyclohexanedione (TABCO) or Br2 as electrophilic source of bromine at room temperature (rt).
Es también conocida la reducción de sulfóxidos, bajo condiciones homogéneas, con compuestos de fósforo, tales como fosfinas, fosfatos, fosfolanos cíclicos, haluros de fósforo, etc. Por ejemplo, la reducción de sulfóxidos en presencia de fosfitos catalizada por bis(dimetilformamido)diclorodioxomolibdeno (VI) It is also known to reduce sulfoxides, under homogeneous conditions, with phosphorus compounds, such as phosphines, phosphates, cyclic phospholanes, phosphorus halides, etc. For example, the reduction of sulfoxides in the presence of phosphites catalyzed by bis (dimethylformamide) dichlorodioxomolibdenum (VI)
y también la reducción con PPh3/TiCl4 permite obtener los sulfuros correspondientes bajo condiciones suaves. and also the reduction with PPh3 / TiCl4 allows to obtain the corresponding sulfides under mild conditions.
Estos y otros procesos de reducción de sulfóxidos orgánicos a sulfuros pueden encontrarse, por ejemplo, en Firouzabadi, Habib y Jamalian, Arezu (2008), “Reduction of oxygenated organosulfur compounds”, Journal of Sulfur Chemistry, 29: 1, 53-97. These and other processes for reducing organic sulphides to sulphides can be found, for example, in Firouzabadi, Habib and Jamalian, Arezu (2008), "Reduction of oxygenated organosulfur compounds", Journal of Sulfur Chemistry, 29: 1, 53-97.
La patente EP 0259882, “Process for the reduction of organic sulfur compounds”, se refiere a un procedimiento para la reducción de compuestos orgánicos de azufre, tales como ácidos sulfónicos, haluros de sulfonilo, sulfonatos, sulfóxidos y/o disulfonas, donde el compuesto en fase líquida o gaseosa se hace reaccionar con un hidrocarburo en presencia de un 1 a un 50% en peso de carbono elemental, con respecto al hidrocarburo, a una temperatura de 100ºC a 500ºC. EP 0259882, "Process for the reduction of organic sulfur compounds", refers to a process for the reduction of organic sulfur compounds, such as sulfonic acids, sulfonyl halides, sulphonates, sulfoxides and / or disulfones, where the compound in the liquid or gas phase, it is reacted with a hydrocarbon in the presence of 1 to 50% by weight of elemental carbon, with respect to the hydrocarbon, at a temperature of 100 ° C to 500 ° C.
La ES 2156184 (EP 0738729), “Procedimiento de reducción selectiva de sulfóxidos de cefalosporina”, describe un procedimiento para la reducción selectiva de sulfóxidos de cefalosporina de compuestos de 3-hidroxi-cephem y 3-metilen-cepham mediante un tratamiento con un agente de cloración en presencia de un aceptor de protones o base y de un disolvente esencialmente anhidro, inertes al agente de cloración, a una temperatura de entre -65ºC y +50ºC. ES 2156184 (EP 0738729), "Selective reduction procedure for cephalosporin sulfoxides", describes a method for the selective reduction of cephalosporin sulfoxides of 3-hydroxy-cephem and 3-methylene-cepham compounds by treatment with an agent of chlorination in the presence of a proton or base acceptor and an essentially anhydrous solvent, inert to the chlorination agent, at a temperature between -65 ° C and + 50 ° C.
Entre las desventajas de muchos de estos métodos conocidos de la técnica anterior para la reducción de sulfóxidos a sulfuros se encuentran unas condiciones de reacción que resultan incompatibles con la presencia de grupos funcionales sensibles en la molécula. Igualmente, muchos de estos métodos conocidos dan lugar a subproductos difícilmente separables del producto final, que hacen necesarias tediosas y costosas etapas de purificación para obtener el producto puro. Muchos de los subproductos, reductores y disolventes empleados en las reacciones según los métodos anteriores son tóxicos y medioambientalmente problemáticos. Among the disadvantages of many of these known prior art methods for the reduction of sulfoxides to sulphides are reaction conditions that are incompatible with the presence of sensitive functional groups in the molecule. Likewise, many of these known methods give rise to by-products that are difficult to separate from the final product, which make tedious and expensive purification steps necessary to obtain the pure product. Many of the by-products, reducers and solvents used in the reactions according to the above methods are toxic and environmentally problematic.
El objeto de la presente invención es, por tanto, proporcionar un procedimiento para la reducción catalítica de compuestos orgánicos que incluyen un grupo funcional sulfóxido, esto es compuestos de fórmula general (1), siendo R1 yR2 grupos orgánicos, a compuestos orgánicos de tipo sulfuro (2), R1-S-R2, incluyendo un grupo funcional tioéter que no presente las desventajas de los procedimientos anteriormente mencionados. The object of the present invention is therefore to provide a process for the catalytic reduction of organic compounds that include a sulfoxide functional group, that is compounds of general formula (1), R1 and R2 being organic groups, to sulfide type organic compounds (2), R1-S-R2, including a thioether functional group that does not have the disadvantages of the aforementioned procedures.
Así, el procedimiento para la reducción de sulfóxidos de la presente invención se basa en la utilización de pinacol, como agente reductor, un compuesto fácilmente accesible y manejable; genera subproductos fácilmente separables y medioambientalmente inocuos y permite la obtención de sulfuros de elevada pureza con un alto rendimiento sin necesidad de costosos procedimientos de separación cromatográficos. El procedimiento de la invención tiene además la ventaja de no necesitar una atmósfera inerte ni disolventes orgánicos para llevar a cabo la reacción de reducción. Thus, the process for the reduction of sulfoxides of the present invention is based on the use of pinacol, as a reducing agent, an easily accessible and manageable compound; It generates easily separable and environmentally safe by-products and allows high purity sulphides to be obtained with high performance without the need for expensive chromatographic separation procedures. The process of the invention also has the advantage of not needing an inert atmosphere or organic solvents to carry out the reduction reaction.
Descripción de la invención Description of the invention
A la vista de lo anteriormente enunciado, la presente invención se refiere a un procedimiento para la reducción catalítica de compuestos orgánicos de fórmula (1) que incluyen un grupo funcional sulfóxido a compuestos tipo sulfuro, de fórmula (2), que incluyen un grupo funcional tioéter, mediante la utilización de pinacol (2,3-dimetil-2,3-butanodiol) como agente reductor, utilizando como catalizador de reacción un catalizador de molibdeno (VI), In view of the foregoing, the present invention relates to a process for the catalytic reduction of organic compounds of formula (1) that include a sulfoxide functional group to sulfide type compounds, of formula (2), which include a functional group thioether, by using pinacol (2,3-dimethyl-2,3-butanediol) as a reducing agent, using a molybdenum catalyst (VI) as the reaction catalyst,
donde: where:
R1 representa un grupo alquilo lineal o ramificado, saturado o insaturado, sustituido o no sustituido; o un grupo arilo sustituido o no sustituido; R1 represents a linear or branched, saturated or unsaturated, substituted or unsubstituted alkyl group; or a substituted or unsubstituted aryl group;
R2 representa un grupo alquilo lineal o ramificado, saturado o insaturado, sustituido o no sustituido; o un grupo arilo sustituido o no sustituido; y R2 represents a linear or branched, saturated or unsaturated, substituted or unsubstituted alkyl group; or a substituted or unsubstituted aryl group; Y
[cat.] representa un catalizador de Mo (VI). [cat.] represents a catalyst of Mo (VI).
Exposición detallada de la invención Detailed statement of the invention
La presente invención se refiere a un procedimiento para la reducción catalítica de compuestos orgánicos que incluyen un grupo funcional sulfóxido de fórmula (1) a compuestos tipo sulfuro que incluyen un grupo funcional tioéter The present invention relates to a process for the catalytic reduction of organic compounds that include a sulfoxide functional group of formula (1) to sulfide type compounds that include a thioether functional group
(2) mediante la utilización de pinacol (2,3-dimetil-2,3-butanodiol) como agente reductor, utilizando como catalizador de reacción un catalizador de molibdeno (VI), (2) by using pinacol (2,3-dimethyl-2,3-butanediol) as a reducing agent, using a molybdenum catalyst (VI) as the reaction catalyst,
donde where
R1 en la fórmula (1) y (2) representa un grupo alquilo lineal o ramificado, saturado o insaturado, sustituido o no sustituido; o un grupo arilo sustituido o no sustituido; R1 in formula (1) and (2) represents a linear or branched, saturated or unsaturated, substituted or unsubstituted alkyl group; or a substituted or unsubstituted aryl group;
R2 en la fórmula (1) y (2) representa un grupo alquilo lineal o ramificado, saturado o insaturado, sustituido o no sustituido; o un grupo arilo sustituido o no sustituido; y R2 in formula (1) and (2) represents a linear or branched, saturated or unsaturated, substituted or unsubstituted alkyl group; or a substituted or unsubstituted aryl group; Y
[cat.] representa un catalizador de Mo (VI) [cat.] represents a catalyst of Mo (VI)
desarrollándose la reacción a presión atmosférica, a una temperatura de entre 70ºC y 90ºC y en un medio libre de disolventes orgánicos. the reaction proceeding at atmospheric pressure, at a temperature between 70 ° C and 90 ° C and in a medium free of organic solvents.
Preferentemente R1 yR2 se seleccionan, independientemente uno de otro, de entre grupos alquilo saturados tales como grupos metilo, etilo, butilo, 1-metilpropilo, sustituidos o no sustituidos; grupos alquilo monoinsaturados alquenilo o alquinilo tales como 4-pentenilo o 4-pentinilo, sustituidos o no sustituidos; grupos arilo tales como fenilo no sustituido o sustituido; grupos carbonilo sustituidos o no sustituidos, o grupos éster sustituidos o no sustituidos. Preferably R1 and R2 are independently selected from each other from saturated alkyl groups such as methyl, ethyl, butyl, 1-methylpropyl, substituted or unsubstituted groups; alkenyl or alkynyl monounsaturated alkyl groups such as 4-pentenyl or 4-pentinyl, substituted or unsubstituted; aryl groups such as unsubstituted or substituted phenyl; substituted or unsubstituted carbonyl groups, or substituted or unsubstituted ester groups.
Preferentemente, los compuestos de fórmula (1) se seleccionan de entre los siguientes compuestos: Preferably, the compounds of formula (1) are selected from the following compounds:
En una realización preferente del procedimiento de la invención, el catalizador de Mo (VI) utilizado para la reducción de sulfóxidos es bis-(dimetilformamido)diclorodioxomolibdeno, MoO2Cl2(dmf)2, donde dmf = dimetilformamida. In a preferred embodiment of the process of the invention, the Mo (VI) catalyst used for the reduction of sulfoxides is bis- (dimethylformamide) dichlorodioxomolibdene, MoO2Cl2 (dmf) 2, where dmf = dimethylformamide.
Los únicos subproductos de la reacción obtenidos según el procedimiento de la invención, procedentes de la oxidación del pinacol, son agua y acetona, lo que permite obtener el sulfuro de forma pura tras una simple extracción. The only by-products of the reaction obtained according to the process of the invention, from the oxidation of pinacol, are water and acetone, which allows the sulphide to be obtained purely after simple extraction.
La cantidad de catalizador utilizada en el procedimiento de la invención se encuentra en un rango del 0,5 al 3 mol%, mientras que la cantidad de pinacol utilizada en el procedimiento de la invención oscila entre1y4 equivalentes. The amount of catalyst used in the process of the invention is in a range of 0.5 to 3 mol%, while the amount of pinacol used in the process of the invention ranges between 1 and 4 equivalents.
Los productos obtenidos a partir de la aplicación del procedimiento de la invención tienen una alta pureza y el rendimiento del proceso es excelente, variando éste entre aproximadamente el 80% y aproximadamente el 90%. The products obtained from the application of the process of the invention have a high purity and the yield of the process is excellent, this varying between approximately 80% and approximately 90%.
El pinacol utilizado como agente reductor en el presente procedimiento es un reactivo fácilmente accesible y seguro desde el punto de vista de su manejo, lo cual permite llevar a cabo el procedimiento de la invención sin necesidad de importantes sistemas de protección ni de inversiones en cuanto a seguridad se refiere, ya que los subproductos obtenidos son acetona y agua. Pinacol used as a reducing agent in the present process is an easily accessible and safe reagent from the point of view of its handling, which allows to carry out the process of the invention without the need for important protection systems or investments in terms of safety refers, since the by-products obtained are acetone and water.
Ejemplos Examples
El procedimiento de reducción para la reducción catalítica de compuestos orgánicos que incluyen un grupo funcional sulfóxido de fórmula (1) a compuestos tipo sulfuro que incluyen un grupo funcional tioéter (2) mediante la utilización de pinacol (2,3-dimetil-2,3-butanodiol) como agente reductor, utilizando como catalizador de reacción bis (dimetilformamido)-diclorodioxomolibdeno (VI) (MoO2Cl2(dmf)2) de la invención se ilustra además mediante los siguientes ejemplos, los cuales no son limitativos del alcance de la presente invención. The reduction process for the catalytic reduction of organic compounds that include a sulfoxide functional group of formula (1) to sulfur-like compounds that include a thioether functional group (2) by the use of pinacol (2,3-dimethyl-2,3 -butanediol) as a reducing agent, using bis (dimethylformamide) -dichlorodioxomolibdene (VI) (MoO2Cl2 (dmf) 2) reaction catalyst of the invention is further illustrated by the following examples, which are not limiting the scope of the present invention .
Ejemplo 1 Example 1
Reducción de difenilsulfóxido a difenilsulfuro Reduction of diphenylsulfoxide to diphenylsulfide
Una mezcla de 473 mg de pinacol (2 equivalentes), 405 mg de difenilsulfóxido y 14 mg de MoO2Cl2(dmf)2 (2 mol%) se calienta a 90ºC durante 6 h. A continuación, el crudo de reacción se disuelve en 40 ml de dietil éter y la disolución resultante se lava con una disolución acuosa de NaOH 0,5 M (3 x 20 ml). La fase orgánica se seca sobre Na2SO4 anhidro, se filtra y se eliminan los disolventes a presión reducida. Se obtienen 332 mg de difenilsulfuro (rendimiento: 89%) cuyos datos espectroscópicos se recogen a continuación: A mixture of 473 mg of pinacol (2 equivalents), 405 mg of diphenylsulfoxide and 14 mg of MoO2Cl2 (dmf) 2 (2 mol%) is heated at 90 ° C for 6 h. Then, the reaction crude is dissolved in 40 ml of diethyl ether and the resulting solution is washed with an aqueous solution of 0.5 M NaOH (3 x 20 ml). The organic phase is dried over anhydrous Na2SO4, filtered and the solvents are removed under reduced pressure. 332 mg of diphenylsulfide are obtained (yield: 89%) whose spectroscopic data are collected below:
1H-RMN (300 MHz, CDCl3): δ (ppm): 7.42-7.25 (m, 4H, ArH), 7.38-7.34 (m, 4H, ArH), 7.33-7.26 (m, 3H, ArH). 13C-RMN (75,4 MHz, CDCl3): δ (ppm): 135.8 (2 x C), 131.1 (4 x CH), 129.3 (4 x CH), 127.1 (2 x CH). 1 H-NMR (300 MHz, CDCl 3): δ (ppm): 7.42-7.25 (m, 4H, ArH), 7.38-7.34 (m, 4H, ArH), 7.33-7.26 (m, 3H, ArH). 13C-NMR (75.4 MHz, CDCl3): δ (ppm): 135.8 (2 x C), 131.1 (4 x CH), 129.3 (4 x CH), 127.1 (2 x CH).
Ejemplo 2 Example 2
Reducción de dibutilsulfóxido a dibutilsulfuro Reduction of dibutyl sulfoxide to dibutyl sulphide
Una mezcla de 473 mg de pinacol (2 equivalentes), 325 mg de dibutilsulfóxido y 14 mg de MoO2Cl2(dmf)2 (2 mol%) se calienta a 90ºC durante 6 h. A continuación, el crudo de reacción se disuelve en 40 ml de dietil éter y la disolución resultante se lava agua (3 x 20 ml). La fase orgánica se seca sobre Na2SO4 anhidro, se filtra y se eliminan los disolventes a presión reducida. Se obtienen 231 mg de dibutilsulfuro (rendimiento: 79%) cuyos datos espectroscópicos se recogen a continuación: A mixture of 473 mg of pinacol (2 equivalents), 325 mg of dibutyl sulfoxide and 14 mg of MoO2Cl2 (dmf) 2 (2 mol%) is heated at 90 ° C for 6 h. Then, the reaction crude is dissolved in 40 ml of diethyl ether and the resulting solution is washed with water (3 x 20 ml). The organic phase is dried over anhydrous Na2SO4, filtered and the solvents are removed under reduced pressure. 231 mg of dibutyl sulphide are obtained (yield: 79%) whose spectroscopic data are collected below:
1H-RMN (300 MHz, CDCl3): δ (ppm): 2.46 (t, J = 7.3 Hz, 4H, 2 x SCH2), 1.60-1.51 (m, 4H,2xSCH2CH2), 1.441H-NMR (300 MHz, CDCl3): δ (ppm): 2.46 (t, J = 7.3 Hz, 4H, 2 x SCH2), 1.60-1.51 (m, 4H, 2xSCH2CH2), 1.44
1.34(m, 4H,2xCH2CH3), 0.87 (t, J =7.2 Hz, 6H,2xCH3). 1.34 (m, 4H, 2xCH2CH3), 0.87 (t, J = 7.2 Hz, 6H, 2xCH3).
13C-RMN (75,4 MHz, CDCl3): δ (ppm): 31.8 (2 x CH2), 31.7 (2 x CH2), 22.0 (2 x CH2), 13.6 (2 x CH3) 13C-NMR (75.4 MHz, CDCl3): δ (ppm): 31.8 (2 x CH2), 31.7 (2 x CH2), 22.0 (2 x CH2), 13.6 (2 x CH3)
Ejemplo 3 Example 3
Reducción de ácido fenil pent-4-in-1-il sulfóxido a fenil pent-4-in-1-il sulfuro Reduction of phenyl pent-4-in-1-yl sulfoxide to phenyl pent-4-in-1-yl sulfide
Una mezcla de 473 mg de pinacol (2 equivalentes), 385 mg de ácido fenil pent-4-in-1-il sulfóxido y 14 mg de MoO2Cl2(dmf)2 (2 mol%) se calienta a 90ºC durante 4 h. A continuación, el crudo de reacción se disuelve en 40 ml de dietil éter y la disolución resultante se lava con una disolución acuosa de NaOH 0,5 M (3 x 20 ml). La fase orgánica se seca sobre Na2SO4 anhidro, se filtra y se eliminan los disolventes a presión reducida. Se obtienen 321 mg de fenil pent-4-in-1-il sulfuro (rendimiento: 91%) cuyos datos espectroscópicos se recogen a continuación: A mixture of 473 mg of pinacol (2 equivalents), 385 mg of phenyl pent-4-in-1-yl sulfoxide acid and 14 mg of MoO2Cl2 (dmf) 2 (2 mol%) is heated at 90 ° C for 4 h. Then, the reaction crude is dissolved in 40 ml of diethyl ether and the resulting solution is washed with an aqueous solution of 0.5 M NaOH (3 x 20 ml). The organic phase is dried over anhydrous Na2SO4, filtered and the solvents are removed under reduced pressure. 321 mg of phenyl pent-4-in-1-yl sulfide are obtained (yield: 91%) whose spectroscopic data are collected below:
1H-RMN (300 MHz, CDCl3): δ (ppm): 7.41-7.29 (m, 4H, ArH), 7.25-7.18 (m, 1H, ArH), 3.07 (at, J = 7.1 Hz, 2H, SCH2(CH2)2), 2.38 (td, J = 6.9 y 2.7 Hz, 2H, CH2C≡CH), 2.03 (t, J = 2.7 Hz, 1H, C≡CH), 1.88 (aq, J = 7.1 Hz, 2H, S (CH2)2CH2). 1H-NMR (300 MHz, CDCl3): δ (ppm): 7.41-7.29 (m, 4H, ArH), 7.25-7.18 (m, 1H, ArH), 3.07 (at, J = 7.1 Hz, 2H, SCH2 ( CH2) 2), 2.38 (td, J = 6.9 and 2.7 Hz, 2H, CH2C≡CH), 2.03 (t, J = 2.7 Hz, 1H, C≡CH), 1.88 (aq, J = 7.1 Hz, 2H, S (CH2) 2CH2).
13C-RMN (75,4 MHz, CDCl3): δ (ppm): 136.1 (C), 129.2 (2 x CH), 128.9 (2 x CH), 126.0 (CH), 83.3 (C), 69.2 (CH), 32.3 (CH2), 27.7 (CH2), 17.4 (CH2). 13C-NMR (75.4 MHz, CDCl3): δ (ppm): 136.1 (C), 129.2 (2 x CH), 128.9 (2 x CH), 126.0 (CH), 83.3 (C), 69.2 (CH) , 32.3 (CH2), 27.7 (CH2), 17.4 (CH2).
Claims (10)
- 2. 2.
- Procedimiento para la reducción catalítica de sulfóxidos orgánicos según la reivindicación 1, caracterizado porque R1 yR2 se seleccionan, independientemente uno de otro, de entre grupos metilo, etilo, butilo, 1-metilpropilo, sustituidos o no sustituidos; 4-pentenilo o 4-pentinilo, sustituidos o no sustituidos; fenilo no sustituido o sustituido; carbonilo sustituido o no sustituido o éster sustituido o no sustituido. Process for the catalytic reduction of organic sulfoxides according to claim 1, characterized in that R1 and R2 are independently selected from each other from among methyl, ethyl, butyl, 1-methylpropyl groups, substituted or unsubstituted; 4-pentenyl or 4-pentinyl, substituted or unsubstituted; unsubstituted or substituted phenyl; substituted or unsubstituted carbonyl or substituted or unsubstituted ester.
- 3. 3.
- Procedimiento para la reducción catalítica de sulfóxidos orgánicos según la reivindicación 1, caracterizado porque los compuestos de fórmula (1) se seleccionan de entre: Process for catalytic reduction of organic sulfoxides according to claim 1, characterized in that the compounds of formula (1) are selected from:
- 4. Four.
- Procedimiento para la reducción catalítica de sulfóxidos orgánicos según la reivindicación 1, caracterizado porque el catalizador de Mo (VI) empleado en la reacción de reducción es bis(dicloroformamido)-diclorodioxomolibdeno, MoO2Cl2(dmf)2, donde dmf dimetilformamida. Process for the catalytic reduction of organic sulfoxides according to claim 1, characterized in that the catalyst of Mo (VI) used in the reduction reaction is bis (dichloroformamide) -dichlorodioxomolibdene, MoO2Cl2 (dmf) 2, where dmf dimethylformamide.
- 5. 5.
- Procedimiento para la reducción catalítica de sulfóxidos orgánicos según la reivindicación 1, caracterizado porque la reacción de reducción se lleva a cabo a presión atmosférica. Process for the catalytic reduction of organic sulfoxides according to claim 1, characterized in that the reduction reaction is carried out at atmospheric pressure.
- 6. 6.
- Procedimiento para la reducción catalítica de sulfóxidos orgánicos según la reivindicación 1, caracterizado porque la reacción de reducción se lleva a cabo a una temperatura de entre 70ºC y 90ºC. Process for the catalytic reduction of organic sulfoxides according to claim 1, characterized in that the reduction reaction is carried out at a temperature between 70 ° C and 90 ° C.
- 7. 7.
- Procedimiento para la reducción catalítica de sulfóxidos orgánicos según la reivindicación 1, caracterizado porque la reacción de reducción se lleva a cabo en un medio libre de disolventes orgánicos. Process for the catalytic reduction of organic sulfoxides according to claim 1, characterized in that the reduction reaction is carried out in a medium free of organic solvents.
- 8. 8.
- Procedimiento para la reducción catalítica de sulfóxidos orgánicos según la reivindicación 1, caracterizado porque la cantidad de catalizador utilizada en la reacción de reducción se encuentra en un rango de 0,5 a 3 mol%. Process for the catalytic reduction of organic sulfoxides according to claim 1, characterized in that the amount of catalyst used in the reduction reaction is in a range of 0.5 to 3 mol%.
- 9. 9.
- Procedimiento para la reducción catalítica de sulfóxidos orgánicos según la reivindicación 1, caracterizado porque la cantidad de pinacol utilizada en la reacción de reducción es de1a4 equivalentes. Process for catalytic reduction of organic sulfoxides according to claim 1, characterized in that the amount of pinacol used in the reduction reaction is equivalent to 1.4.
- Categoría Category
- Documentos citados Reivindicaciones afectadas Documents cited Claims Affected
- A TO
- B WOO YOO et al., Bulletin of Korean Chemical Society 2007, vol 28, número 2, páginas 171-172. 1-9 B WOO YOO et al., Bulletin of Korean Chemical Society 2007, vol 28, number 2, pages 171-172. 1-9
- "A facile and efficient deoxygenation of sulfoxides with Mo(CO)6", esquema 1, tabla1. "A facile and efficient deoxygenation of sulfoxides with Mo (CO) 6", scheme 1, table 1.
- A TO
- A FERNANDES et al., Tetrahedron 2006, volumen 62, páginas 9650-9654. "A novel method for 1-9 A FERNANDES et al., Tetrahedron 2006, volume 62, pages 9650-9654. "A novel method for 1-9
- the reduction of sulfoxides and pyridine N-oxides with the system silane / MoO2Cl2", esquema 1, the reduction of sulfoxides and pyridine N-oxides with the system silane / MoO2Cl2 ", scheme 1,
- tabla 2. table 2.
- A TO
- WO 2004016569 A1 (EISAI) 26.02.2004 1-9 WO 2004016569 A1 (EISAI) 26.02.2004 1-9
- Categoría de los documentos citados X: de particular relevancia Y: de particular relevancia combinado con otro/s de la misma categoría A: refleja el estado de la técnica O: referido a divulgación no escrita P: publicado entre la fecha de prioridad y la de presentación de la solicitud E: documento anterior, pero publicado después de la fecha de presentación de la solicitud Category of the documents cited X: of particular relevance Y: of particular relevance combined with other / s of the same category A: reflects the state of the art O: refers to unwritten disclosure P: published between the priority date and the date of priority submission of the application E: previous document, but published after the date of submission of the application
- El presente informe ha sido realizado • para todas las reivindicaciones • para las reivindicaciones nº: This report has been prepared • for all claims • for claims no:
- Fecha de realización del informe 06.06.2011 Date of realization of the report 06.06.2011
- Examinador M. P. Fernández Fernández Página 1/4 Examiner M. P. Fernández Fernández Page 1/4
- Novedad (Art. 6.1 LP 11/1986) Novelty (Art. 6.1 LP 11/1986)
- Reivindicaciones Reivindicaciones 1-9 SI NO Claims Claims 1-9 IF NOT
- Actividad inventiva (Art. 8.1 LP11/1986) Inventive activity (Art. 8.1 LP11 / 1986)
- Reivindicaciones Reivindicaciones 1-9 SI NO Claims Claims 1-9 IF NOT
- Documento Document
- Número Publicación o Identificación Fecha Publicación Publication or Identification Number publication date
- D01 D01
- B WOO YOO et al, Bulletin of Korean Chemical Society 2007, vol 28, número 2, páginas 171-172. "A facile and efficient deoxygenation of sulfoxides with Mo(CO)6", esquema 1, tabla1. 2007 B WOO YOO et al, Bulletin of Korean Chemical Society 2007, vol 28, number 2, pages 171-172. "A facile and efficient deoxygenation of sulfoxides with Mo (CO) 6", scheme 1, table 1. 2007
- D02 D02
- A FERNANDES et al, Tetrahedron 2006, volumen 62, páginas 9650-9654. "A novel method for the reduction of sulfoxides and pyridine N-oxides with the system silane / MoO2Cl2", esquema 1, tabla 2. 2006 A FERNANDES et al, Tetrahedron 2006, volume 62, pages 9650-9654. "A novel method for the reduction of sulfoxides and pyridine N-oxides with the system silane / MoO2Cl2", scheme 1, table 2. 2006
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