ES2551245B2 - Procedure for the reduction of sulfoxides using a supported thiol as a reducing agent - Google Patents
Procedure for the reduction of sulfoxides using a supported thiol as a reducing agent Download PDFInfo
- Publication number
- ES2551245B2 ES2551245B2 ES201400381A ES201400381A ES2551245B2 ES 2551245 B2 ES2551245 B2 ES 2551245B2 ES 201400381 A ES201400381 A ES 201400381A ES 201400381 A ES201400381 A ES 201400381A ES 2551245 B2 ES2551245 B2 ES 2551245B2
- Authority
- ES
- Spain
- Prior art keywords
- procedure
- organic
- catalytic reduction
- reduction
- substituted
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 150000003462 sulfoxides Chemical class 0.000 title claims abstract description 25
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 title claims description 43
- 150000003573 thiols Chemical class 0.000 title 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 19
- -1 3-mercaptopropyl Chemical group 0.000 claims abstract description 18
- 238000010531 catalytic reduction reaction Methods 0.000 claims abstract description 17
- 239000000741 silica gel Substances 0.000 claims abstract description 17
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000006722 reduction reaction Methods 0.000 claims description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 150000003568 thioethers Chemical class 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 4
- 229910052721 tungsten Inorganic materials 0.000 abstract description 2
- 125000000101 thioether group Chemical group 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- NRXWFTYEJYEOGW-UHFFFAOYSA-N 1-methyl-4-(4-methylphenyl)sulfanylbenzene Chemical compound C1=CC(C)=CC=C1SC1=CC=C(C)C=C1 NRXWFTYEJYEOGW-UHFFFAOYSA-N 0.000 description 4
- MJWNJEJCQHNDNM-UHFFFAOYSA-N 1-methyl-4-(4-methylphenyl)sulfinylbenzene Chemical compound C1=CC(C)=CC=C1S(=O)C1=CC=C(C)C=C1 MJWNJEJCQHNDNM-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 150000002898 organic sulfur compounds Chemical class 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229930186147 Cephalosporin Natural products 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 229940124587 cephalosporin Drugs 0.000 description 2
- 239000012320 chlorinating reagent Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- 238000005406 washing Methods 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
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000006362 organocatalysis Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000003447 supported reagent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002351 wastewater Substances 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
La presente invención se refiere al uso de gel de sílice funcionalizado con 3-mercaptopropilo como agente reductor para la reducción catalítica de compuestos orgánicos que incluyen un grupo funcional sulfóxido a compuestos tipo sulfuro en presencia de un catalizador de molibdeno (VI), en un disolvente orgánico o en un medio libre de disolventes orgánicos, bajo presión atmosférica y a una temperatura entre 130-190°C o, alternativamente, por irradiación en un horno microondas monomodo a una potencia máxima de 270 W y a una temperatura comprendida entre 130ºC y 140ºC.The present invention relates to the use of 3-mercaptopropyl functionalized silica gel as a reducing agent for the catalytic reduction of organic compounds that include a sulfoxide functional group to sulfide type compounds in the presence of a molybdenum (VI) catalyst, in a solvent. organic or in a medium free of organic solvents, under atmospheric pressure and at a temperature between 130-190 ° C or, alternatively, by irradiation in a single-mode microwave oven at a maximum power of 270 W and at a temperature between 130 ° C and 140 ° C.
Description
55
1010
15fifteen
20twenty
2525
3030
PROCEDIMIENTO PARA LA REDUCCION DE SULFOXIDOS EMPLEANDO UN TIOL SOPORTADO COMO AGENTE REDUCTORPROCEDURE FOR REDUCING SULFOXIDES USING A SUPPORTED THOLE AS A REDUCING AGENT
DESCRIPCIONDESCRIPTION
OBJETO DE LA INVENCIONOBJECT OF THE INVENTION
La presente invention se refiere a un procedimiento para la reduction de sulfoxidos organicos.The present invention relates to a process for the reduction of organic sulfoxides.
Mas concretamente, la invention se refiere a un procedimiento para la reduction catalitica de compuestos organicos que incluyen un grupo funcional sulfoxido, esto es compuestos de formula general R1-S(=0)-R2, siendo R1 y R2 grupos organicos, a compuestos organicos de tipo sulfuro, R1-S-R2, empleando gel de sflice funcionalizado con 3-mercaptopropilo como agente reductor y un complejo de molibdeno como catalizador.More specifically, the 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 (= 0) -R2, R1 and R2 being organic groups, to organic compounds of the sulfide type, R1-S-R2, using silica gel functionalized with 3-mercaptopropyl as a reducing agent and a molybdenum complex as a catalyst.
ANTECEDENTES DE LA INVENClONBACKGROUND OF THE INVENTION
La reduction de sulfoxidos a sus correspondientes sulfuros constituye una importante reaction de gran utilidad en sintesis organica. Algunos procesos de reduction de sulfoxidos organicos a sulfuros pueden encontrarse, por ejemplo, en "Reduction of oxygenated organosulfur compounds", J. Sulfur Chem., 2008, 29, 53-97.The reduction of sulfoxides to their corresponding sulphides constitutes an important reaction of great utility in organic synthesis. Some processes of reduction of organic sulfoxides to sulfides can be found, for example, in "Reduction of oxygenated organosulfur compounds", J. Sulfur Chem., 2008, 29, 53-97.
La patente EP 0259882, "Process for the reduction of organic sulfur compounds", se refiere a un procedimiento para la reduction de compuestos organicos de azufre, tales como £cidos sulfonicos, haluros de sulfonilo, sulfonatos, sulfdxidos y/o disulfonas, donde el compuesto en fase liquida 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 100 °C a 500 °C.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, sulphonyl halides, sulphonates, sulfodides and / or disulfones, where the The liquid or gas phase compound 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 reduction selectivaES 2156184 (EP 0738729), "Selective reduction procedure
55
1010
15fifteen
20twenty
2525
3030
3535
de sulfoxidos de cefalosporina", describe un procedimiento para la reduccion selectiva de sulfoxidos de cefalosporina de compuestos de 3-hidroxi-cephem y 3- metilen-cepham mediante un tratamiento con un agente de cloracion en presencia de un aceptor de protones o base y de un disolvente esencialmente anhidro, inertes al agente de cloracion, a una temperatura de entre -65 °C y +50 °C.of cephalosporin sulfoxides, "describes a procedure for the selective reduction of cephalosporin sulfoxides of 3-hydroxy-cephem and 3- methylene-cepham compounds by treatment with a chlorinating agent in the presence of a proton or base acceptor and an essentially anhydrous solvent, inert to the chlorinating agent, at a temperature between -65 ° C and +50 ° C.
Sin embargo, estos metodos previos presentan ciertas desventajas, haciendo necesario el desarrollo de nuevos metodos de reduccion de sulfoxidos. Entre las desventajas de muchos de estos metodos conocidos de la tecnica anterior para la reduccion de sulfoxidos a sulfuros se encuentran unas condiciones de reaccion que resultan incompatibles con la presencia de grupos funcionales sensibles en la molecula. Igualmente, muchos de estos metodos conocidos dan lugar a subproductos dificilmente separables del producto final, que hacen necesarias tediosas y costosas etapas de purification para obtener el producto puro. Muchos de los reductores y subproductos, en las reacciones segun los metodos anteriores son toxicos, medioambientalmente problem&ticos y/o de elevado coste.However, these previous methods have certain disadvantages, making it necessary to develop new sulfoxide reduction methods. Among the disadvantages of many of these methods known from the prior art 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 reducers and by-products, in the reactions according to the above methods are toxic, environmentally problematic and / or high cost.
Por otro lado, el gel de silice funcionalizado con 3-mercaptopropilo se ha empleado fundamentalmente para la elimination de metales de aguas residuales, como en “A new class of hybrid mesoporous materials with functionalized organic monolayers for selective adsorption of heavy metal ions”, Chem. Commun. 2000, 1145-1146; o de medios de reaccion, como en “Methods for removal of residual catalyst from polymers prepared by ring opening metathesis”, J. Polym. Sci., Part A: Polym. Chem. 2010, 5752-5757; como soporte para catalizadores en “Palladium-supported ionic liquid catalyst (Pd-SH-SILC) immobilized on mercaptopropyl silica gel as a chemoselective, reusable and heterogeneous catalyst for catalytic hydrogenation”, Green Chem. 2011, 13, 1133-1137; o en “Heterogeneous organocatalysis for the asymmetric desymetrization of meso-cyclic anhydrides using silica gel-supported bis-cinchona alkaloids” Tetrahedron 2004, 60, 12051-12057; o como precursor de acidos sulfonicos soportados “Sulfonic acid functionalized silica: A remarkably efficient heterogeneous reusable catalyst for a-monobromination of carbonyl compounds using A/-bromosuccinimide”, J. Mol. Catal. A: Chem. 2006, 253, 107-111. Sin embargo, el gel de silice funcionalizado con 3-mercaptopropilo no ha sido utilizadoOn the other hand, the 3-mercaptopropyl functionalized silica gel has been used primarily for the elimination of wastewater metals, as in "A new class of hybrid mesoporous materials with functionalized organic monolayers for selective adsorption of heavy metal ions", Chem Commun. 2000, 1145-1146; or reaction media, as in "Methods for removal of residual catalyst from polymers prepared by ring opening metathesis", J. Polym. Sci., Part A: Polym. Chem. 2010, 5752-5757; as support for catalysts in "Palladium-supported ionic liquid catalyst (Pd-SH-SILC) immobilized on mercaptopropyl silica gel as a chemoselective, reusable and heterogeneous catalyst for catalytic hydrogenation", Green Chem. 2011, 13, 1133-1137; or in "Heterogeneous organocatalysis for the asymmetric desymetrization of meso-cyclic anhydrides using silica gel-supported bis-cinchona alkaloids" Tetrahedron 2004, 60, 12051-12057; or as a precursor of supported sulfonic acids "Sulfonic acid functionalized silica: A remarkably efficient heterogeneous reusable catalyst for a-monobromination of carbonyl compounds using A / -bromosuccinimide", J. Mol. Catal. A: Chem. 2006, 253, 107-111. However, the 3-mercaptopropyl functionalized silica gel has not been used
55
1010
15fifteen
20twenty
2525
3030
hasta el momento como agente reductor.So far as a reducing agent.
El objeto de la presente invencibn es, por tanto, proporcionar un nuevoThe object of the present invention is therefore to provide a new
procedimiento para la reduction catalitica de compuestos organicos que incluyen un grupo funcional sulfoxido, esto es compuestos de formula general (1), siendo R1 y R2 grupos organicos, a compuestos organicos de tipo sulfuro (2), R1-S-R2, empleando un reductor soportado como es el gel de sllice funcionalizado con 3- mercaptopropilo, que no presenta las desventajas de los procedimientos de reduccion anteriormente mencionados.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 organic compounds of sulfide type (2), R1-S-R2, using a supported reducer such as the 3-mercaptopropyl functionalized silica gel, which does not have the disadvantages of the reduction procedures mentioned above.
Asi, el procedimiento para la reduccion de sulfoxidos de la presente invencibn emplea gel de silice funcionalizado con 3-mercaptopropilo, un compuesto muy facilmente accesible y manejable, como agente reductor. Ademas, al tratarse de un reactivo soportado no libera subproductos al medio de reaccibn y puede eliminarse del mismo mediante una simple filtration, permitiendo la obtencion de sulfuros de elevada pureza con un alto rendimiento sin necesidad de costosos procedimientos de separation cromatograficos. El procedimiento de la invencion tiene ademas la ventaja de no necesitar una atmosfera inerte para llevar a cabo la reaccibn de reduccion.Thus, the process for the reduction of sulfoxides of the present invention employs 3-mercaptopropyl functionalized silica gel, a very easily accessible and manageable compound, as a reducing agent. In addition, as it is a supported reagent, it does not release by-products into the reaction medium and can be removed from it by simple filtration, allowing 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 to carry out the reduction reaction.
DESCRIPCION DE LA INVENCIONDESCRIPTION OF THE INVENTION
A la vista de lo anteriormente enunciado la presente invencion se refiere a un nuevo procedimiento reductor de moleculas organicas. En concreto, se describe un procedimiento para la reduccibn catalitica de sulfoxidos de formula (1) a compuestos sulfuro de formula (2), donde la reaccion de reduccion se Neva a cabo en presencia de gel de silice funcionalizado con 3-mercaptopropilo como agente reductor, y en presencia de un catalizador de molibdeno (VI),In view of the foregoing, the present invention relates to a new process for reducing organic molecules. Specifically, a process for the catalytic reduction of sulfoxides of formula (1) to sulfide compounds of formula (2) is described, where the reduction reaction is carried out in the presence of 3-mercaptopropyl functionalized silica gel as a reducing agent , and in the presence of a molybdenum catalyst (VI),
(1)(one)
(2)(2)
donde:where:
R1 representa un grupo alquilo lineal o ramificado, sustituido o noR1 represents a linear or branched alkyl group, substituted or not
55
1010
15fifteen
20twenty
2525
3030
sustituido; o un grupo arilo sustituido o no sustituido;replaced; or a substituted or unsubstituted aryl group;
R2 representa un grupo alquilo lineal o ramificado, sustituido o no sustituido; o un grupo arilo sustituido o no sustituido; yR2 represents a linear or branched, 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).
EXP0S1C10N DETALLADA DE LA INVENCIONDETAILED EXP0S1C10N OF THE INVENTION
La presente invencibn se refiere a un procedimiento para la reduction catalitica de sulfoxidos organicos de fbrmula (1) a compuestos sulfuro organicos de fbrmula (2), donde la reaccibn de reduccion se lleva a cabo en presencia de gel de silice funcionalizado con 3-mercaptopropilo como agente reductor, y en presencia de un catalizador de molibdeno (VI),The present invention relates to a process for the catalytic reduction of organic sulfoxides of formula (1) to organic sulfide compounds of formula (2), where the reduction reaction is carried out in the presence of 3-mercaptopropyl functionalized silica gel as a reducing agent, and in the presence of a molybdenum (VI) catalyst,
9 [cat.],9 [cat.],
R1 'R2 " R1'S'R2R1 'R2 "R1'S'R2
(D (2)(D (2)
donde:where:
R1 en la fbrmula (1) y (2) representa un grupo alquilo lineal o ramificado, sustituido o no sustituido; o un grupo arilo sustituido o no sustituido;R1 in formula (1) and (2) represents a linear or branched, substituted or unsubstituted alkyl group; or a substituted or unsubstituted aryl group;
R2 en la formula (1) y (2) representa un grupo alquilo lineal o ramificado, sustituido o no sustituido; o un grupo arilo sustituido o no sustituido; yR2 in formula (1) and (2) represents a linear or branched, 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)
El procedimiento de la invencibn se puede llevar a cabo en ausencia de disolvente organico, de manera que el procedimiento se simplifica.The process of the invention can be carried out in the absence of organic solvent, so that the procedure is simplified.
El procedimiento de la invencibn se puede llevar a cabo en presencia de un disolvente orgbnico. En una materializacion preferente el disolvente organico es mesitileno. En otra materializacion preferente el disolvente orgbnico es tolueno.The process of the invention can be carried out in the presence of an organic solvent. In a preferred embodiment, the organic solvent is mesitylene. In another preferred embodiment the organic solvent is toluene.
Preferentemente el procedimiento se Neva a cabo a presion atmosferica y a una temperatura de entre 130 °C y 190 °C. En otra materializacion preferente el procedimiento se Neva a cabo por irradiacibn en un homo microondas monomodo a una potencia maxima de 270 W y a una temperatura comprendida entre 130 °C y 5 140 °C.Preferably the process is carried out at atmospheric pressure and at a temperature between 130 ° C and 190 ° C. In another preferred embodiment, the procedure is carried out by irradiation in a single-mode microwave oven at a maximum power of 270 W and at a temperature between 130 ° C and 5 140 ° C.
Preferentemente R1 y R2 se seleccionan, independientemente uno de otro, de entre grupos alquilo tales como grupos metilo, ciclopropilo, tert-butilo o bencilo, sustituidos o no sustituidos y grupos arilo tales como fenilo no sustituido o 10 sustituido.Preferably R1 and R2 are selected, independently from each other, from alkyl groups such as methyl, cyclopropyl, tert-butyl or benzyl groups, substituted or unsubstituted and aryl groups such as unsubstituted or substituted phenyl.
Preferentemente, los compuestos de formula (1) se seleccionan de entre los siguientes compuestos:Preferably, the compounds of formula (1) are selected from the following compounds:
En una realizacion preferente del procedimiento de la invencion, el catalizador de Mo (VI) es bis-(dimetilformamida) diclorodioxomolibdeno (VI), Mo02CI2(dmf)2, donde dmf = dimetilformamidaIn a preferred embodiment of the process of the invention, the Mo (VI) catalyst is bis- (dimethylformamide) dichlorodioxomolibdene (VI), Mo02CI2 (dmf) 2, where dmf = dimethylformamide
55
1010
15fifteen
20twenty
2525
3030
Preferentemente la cantidad del catalizador esta comprendida en un rango entre 2 mol % al 5 mol %.Preferably the amount of the catalyst is in a range between 2 mol% to 5 mol%.
Preferentemente la cantidad de gel de silice funcionalizado con 3- mercaptopropilo esta comprendida en un rango entre 1,1 equivalentes y 2 equivalentes.Preferably, the amount of silica gel functionalized with 3-mercaptopropyl is in a range between 1.1 equivalents and 2 equivalents.
Los productos obtenidos a partir de la aplicacidn del procedimiento de la invencion se aislan con elevada pureza tras una simple filtracion y el rendimiento del proceso es excelente, variando este entre aproximadamente el 81% y aproximadamente el 95%.The products obtained from the application of the process of the invention are isolated with high purity after a simple filtration and the yield of the process is excellent, this varying between approximately 81% and approximately 95%.
EJEMPLOSEXAMPLES
El procedimiento para la reduccion catalitica de compuestos organicos que incluyen un grupo funcional sulfoxido de formula (1) a compuestos tipo sulfuro (2) mediante la utilization de gel de silice funcionalizado con 3-mercaptopropilo como agente reductor, utilizando como catalizador de reaction bis- (dimetilformamida) diclorodioxomolibdeno (VI) (Mo02Cl2(dmf)2) de la invencion se ilustra ademas mediante los siguientes ejemplos, los cuales no son limitativos del alcance de la presente invencion.The process for the catalytic reduction of organic compounds that include a sulfoxide functional group of formula (1) to sulfide type compounds (2) by the use of 3-mercaptopropyl functionalized silica gel as a reducing agent, using as bis-reaction catalyst (dimethylformamide) dichlorodioxomolibdene (VI) (Mo02Cl2 (dmf) 2) of the invention is further illustrated by the following examples, which are not limiting the scope of the present invention.
Ejemplo 1:Example 1:
Reduccion de di(p-tolil)sulfoxido a di(p-tolil)sulfuro a 130 °CReduction of di (p-tolyl) sulfoxide to di (p-tolyl) sulfide at 130 ° C
++
Mo02CI2(dmf)2 (2 mol%)Mo02CI2 (dmf) 2 (2 mol%)
130 °C tolueno130 ° C toluene
Una mezcla de 914 mg de gel de silice funcionalizado con 3- mercaptopropilo (1.2 mmol/g, 1.1 equivalentes), 230 mg de di(p-tolil)sulf6xido y 7 mg de Mo02CI2(dmf)2 (2 mol%) en tolueno (1 mL) se calento a 130 °C durante 7 h. A continuacion, se dejo enfriar a temperatura ambiente y se filtro para eliminar elA mixture of 914 mg of silica gel functionalized with 3- mercaptopropyl (1.2 mmol / g, 1.1 equivalents), 230 mg of di (p-tolyl) sulfoxide and 7 mg of Mo02CI2 (dmf) 2 (2 mol%) in toluene (1 mL) was heated at 130 ° C for 7 h. Then, it was allowed to cool to room temperature and filtered to remove the
55
1010
15fifteen
20twenty
2525
3030
gel de sflice funcionalizado, lavando con 10 mL de dietil eter. Se eliminaron los disolventes a presion reducida. Se obtuvieron 191 mg de di(p-tolil)sulfuro (rendimiento: 89%) cuyos datos espectroscopicos se recogen a continuacion: 1H-RMN (300 MHz, CDCI3): 5 (ppm): 7.27-7.23 (m, 4H, ArH), 7.14-7.10 (m, 2H, ArH), 2.34 (s, 6H, 2 * CH3).functionalized silica gel, washing with 10 mL of diethyl ether. The solvents were removed under reduced pressure. 191 mg of di (p-tolyl) sulfide were obtained (yield: 89%) whose spectroscopic data are collected below: 1 H-NMR (300 MHz, CDCI3): 5 (ppm): 7.27-7.23 (m, 4H, ArH ), 7.14-7.10 (m, 2H, ArH), 2.34 (s, 6H, 2 * CH3).
13C-RMN (75,4 MHz, CDCI3): 5 (ppm): 137.0 (2 * C), 132.7 (2 * C), 131.2 (4 x CH), 130.0 (4 xCH), 21.2 (2 x CH3).13C-NMR (75.4 MHz, CDCI3): 5 (ppm): 137.0 (2 * C), 132.7 (2 * C), 131.2 (4 x CH), 130.0 (4 xCH), 21.2 (2 x CH3) .
Ejemplo 2:Example 2:
Reduccion de di(p-tolil)sulfoxido a di(p-tolil)sulfuro bajo radiacion microondasReduction of di (p-tolyl) sulfoxide to di (p-tolyl) sulfide under microwave radiation
Mo02Cl2(dmf)2Mo02Cl2 (dmf) 2
^ (2 mol%)^ (2 mol%)
+ (SiV^-^SH ----------------►+ (SiV ^ - ^ SH ---------------- ►
MW, 140 °C toluenoMW, 140 ° C toluene
Una mezcla de 914 mg de gel de sflice funcionalizado con 3- mercaptopropilo (1.2 mmol/g, 1.1 equivalentes), 230 mg de di(p-tolil)sulfoxido y 7 mg de Mo02CI2(dmf)2 (2 mol%) en tolueno (1 mL) se irradio durante 10 minutos a 140 °C (temperatura determinada por un sensor IR situado debajo de la cavidad de reaccidn) y a una potencia maxima de 270 W en un horno microondas monomodo CEM Discover S-Class. A continuacion, se dejo enfriar a temperatura ambiente y se filtro para eliminar el gel de sflice funcionalizado, lavando con 10 mL de dietil eter. Se eliminaron los disolventes a presidn reducida. Se obtuvieron 203 mg de di(p-tolil)sulfuro (rendimiento: 95%) cuyos datos espectroscdpicos se recogen a continuacion:A mixture of 914 mg of silica gel functionalized with 3- mercaptopropyl (1.2 mmol / g, 1.1 equivalents), 230 mg of di (p-tolyl) sulfoxide and 7 mg of Mo02CI2 (dmf) 2 (2 mol%) in toluene (1 mL) was irradiated for 10 minutes at 140 ° C (temperature determined by an IR sensor located below the reaction cavity) and at a maximum power of 270 W in a CEM Discover S-Class single mode microwave oven. Then, it was allowed to cool to room temperature and filtered to remove the functionalized silica gel, washing with 10 mL of diethyl ether. The solvents were removed under reduced pressure. 203 mg of di (p-tolyl) sulfide were obtained (yield: 95%) whose spectroscopic data are collected below:
1H-RMN (300 MHz, CDCI3): 5 (ppm): 7.27-7.23 (m, 4H, ArH), 7.14-7.10 (m, 2H, ArH), 2.34 (s, 6H, 2 x CH3).1H-NMR (300 MHz, CDCI3): 5 (ppm): 7.27-7.23 (m, 4H, ArH), 7.14-7.10 (m, 2H, ArH), 2.34 (s, 6H, 2 x CH3).
13C-RMN (75,4 MHz, CDCI3): 5 (ppm): 137.0 (2 x C), 132.7 (2 x C), 131.2 (4 x CH), 130.0 (4 xCH), 21.2 (2xCH3).13C-NMR (75.4 MHz, CDCI3): 5 (ppm): 137.0 (2 x C), 132.7 (2 x C), 131.2 (4 x CH), 130.0 (4 xCH), 21.2 (2xCH3).
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ES201400381A ES2551245B2 (en) | 2014-05-13 | 2014-05-13 | Procedure for the reduction of sulfoxides using a supported thiol as a reducing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ES201400381A ES2551245B2 (en) | 2014-05-13 | 2014-05-13 | Procedure for the reduction of sulfoxides using a supported thiol as a reducing agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| ES2551245A1 ES2551245A1 (en) | 2015-11-17 |
| ES2551245B2 true ES2551245B2 (en) | 2016-03-03 |
Family
ID=54478472
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| ES201400381A Active ES2551245B2 (en) | 2014-05-13 | 2014-05-13 | Procedure for the reduction of sulfoxides using a supported thiol as a reducing agent |
Country Status (1)
| Country | Link |
|---|---|
| ES (1) | ES2551245B2 (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0219292D0 (en) * | 2002-08-19 | 2002-09-25 | Eisai London Res Lab Ltd | Process |
| ES2381725B2 (en) * | 2010-11-04 | 2012-10-11 | Universidad De Burgos | PROCEDURE FOR THE CATALYTIC REDUCTION OF ORGANIC SULPHOXIDS. |
| ES2428621B2 (en) * | 2012-05-03 | 2014-06-25 | Universidad De Burgos | Procedure for catalytic reduction of organic sulphides |
-
2014
- 2014-05-13 ES ES201400381A patent/ES2551245B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| ES2551245A1 (en) | 2015-11-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yamaguchi et al. | Oxidative nucleophilic strategy for synthesis of thiocyanates and trifluoromethyl sulfides from thiols | |
| Xu et al. | Efficient C–S cross coupling catalyzed by Cu2O | |
| Sorribes et al. | Nanolayered cobalt–molybdenum sulphides (Co–Mo–S) catalyse borrowing hydrogen C–S bond formation reactions of thiols or H 2 S with alcohols | |
| Shi et al. | Self‐Catalyzed Oxidation of Sulfides with Hydrogen Peroxide: A Green and Practical Process for the Synthesis of Sulfoxides | |
| Azizi et al. | An atom-economic and odorless thia-Michael addition in a deep eutectic solvent | |
| CN103073463A (en) | Synthetic method of diaryl thioether | |
| Singh et al. | Harnessing the catalytic behaviour of 1, 1, 1, 3, 3, 3-hexafluoro-2-propanol (HFIP): An expeditious synthesis of thioesters | |
| Luo et al. | Xanthate-mediated synthesis of (E)-alkenes by semi-hydrogenation of alkynes using water as the hydrogen donor | |
| Chen et al. | Iodine-promoted 2-arylsulfanylphenol formation using cyclohexanones as phenol source | |
| Ghorbani-Choghamarani et al. | An efficient and new method on the oxidative coupling of thiols under mild and heterogeneous conditions | |
| Lou et al. | Highly efficient synthesis of 2-mercaptobenzothiazole derivatives in water: metal sulfide–disulfide dynamic interchange reaction | |
| Liebeskind et al. | Bioinspired organometallic chemistry | |
| Yadav et al. | An easy access to functionalized allyl dithiocarbamates from Baylis–Hillman adducts in water | |
| Tosi et al. | [MoO3 (2, 2′–bipy)] n catalyzed oxidation of amines and sulfides | |
| ES2551245B2 (en) | Procedure for the reduction of sulfoxides using a supported thiol as a reducing agent | |
| Samanta et al. | Copper (0) nanoparticles immobilized on SBA-15: A versatile recyclable heterogeneous catalyst for solvent and ligand free C–S coupling reaction from diverse substrates | |
| CN108794436A (en) | A kind of synthetic method of 2- thiophenol groups methylfuran class compound | |
| Liu et al. | Novel synthesis of benzothiazole by self-redox tandem reaction of disulfide with aldehyde | |
| Kuroda et al. | Conversion of Alcohols to Alkyl Aryl Sulfides by a New Type of Oxidation–Reduction Condensation Using Phenyl Diphenylphosphinite | |
| Wang et al. | Ag–Cu copromoted direct C2–H bond thiolation of azoles with Bunte salts as sulfur sources | |
| CN111087331A (en) | A kind of method for preparing thioether from unsaturated olefin without transition metal catalysis | |
| CN102167674B (en) | 3-aryl (alkyl) sulfur substituted-1-propylene compound and method of synthesizing same | |
| JP5764771B2 (en) | Azadirs-Alder reaction catalyst and method for producing tetrahydropyridine compound using the same | |
| ES2381725B2 (en) | PROCEDURE FOR THE CATALYTIC REDUCTION OF ORGANIC SULPHOXIDS. | |
| ES2428621B2 (en) | Procedure for catalytic reduction of organic sulphides |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FG2A | Definitive protection |
Ref document number: 2551245 Country of ref document: ES Kind code of ref document: B2 Effective date: 20160303 |