ES2981841B2 - Procedure for the reduction of nitroaromatic compounds using y-terpinene as a reducing agent - Google Patents
Procedure for the reduction of nitroaromatic compounds using y-terpinene as a reducing agent Download PDFInfo
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- ES2981841B2 ES2981841B2 ES202330202A ES202330202A ES2981841B2 ES 2981841 B2 ES2981841 B2 ES 2981841B2 ES 202330202 A ES202330202 A ES 202330202A ES 202330202 A ES202330202 A ES 202330202A ES 2981841 B2 ES2981841 B2 ES 2981841B2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
- C07C13/02—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
- C07C13/16—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with a six-membered ring
- C07C13/23—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with a six-membered ring with a cyclohexadiene ring
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Description
DESCRIPCIÓNDESCRIPTION
Procedimiento de reducción de compuestos nitroaromáticos empleando Y-terpineno como agente reductorProcedure for the reduction of nitroaromatic compounds using Y-terpinene as a reducing agent
La presente invención se refiere a un procedimiento de reducción de compuestos nitroaromáticos empleando Y-terpineno como agente reductor. The present invention relates to a process for reducing nitroaromatic compounds using Y-terpinene as a reducing agent.
Más concretamente, la invención proporciona un procedimiento de reducción catalítica de compuestos nitroaromáticos, que incluyen un grupo funcional nitro, R1-NO2, de fórmula general 1, a compuestos orgánicos de tipo amina, R1-NH2, de fórmula general 2, que contienen un grupo funcional amino, donde como agente reductor se emplea Y-terpineno (1-isopropil-4-metil-1,4-ciclohexadieno) More specifically, the invention provides a process for the catalytic reduction of nitroaromatic compounds, which include a nitro functional group, R1-NO2, of general formula 1, to amine type organic compounds, R1-NH2, of general formula 2, which contain an amino functional group, where Y-terpinene (1-isopropyl-4-methyl-1,4-cyclohexadiene) is used as the reducing agent.
siendo R1 un grupo arilo o heteroarilo, sustituido o no sustituido, y [cat] un catalizador de dioxomolibdeno (VI). where R1 is a substituted or unsubstituted aryl or heteroaryl group, and [cat] is a dioxomolybdenum (VI) catalyst.
Los nitrocompuestos aromáticos tienen pocos usos directos; sin embargo, las aminas aromáticas resultantes de la reducción de dichos nitrocompuestos se pueden convertir en una amplia gama de productos (Burke y Danheiser, Handbook of Reagents for Organic Synthesis Oxidizing and Reducing Agents, Wiley, (1999), pp.458-461; Li et al., An Effective Strategy for Discovering Novel Chemical Inhibitors of Human Cyclophilin A: Focused Library Design, Virtual Screening, Chemical Synthesis and Bioassay, Journal of Combinatorial Chemistry, 8 (2006), pp. 326-337, 2006) con aplicaciones tan diversas como: colorantes, productos farmacéuticos, materias primas para la formación de diversos grupos funcionales. Aromatic nitro compounds have few direct uses; however, aromatic amines resulting from the reduction of such nitro compounds can be converted into a wide range of products (Burke and Danheiser, Handbook of Reagents for Organic Synthesis Oxidizing and Reducing Agents, Wiley, (1999), pp. 458-461; Li et al., An Effective Strategy for Discovering Novel Chemical Inhibitors of Human Cyclophilin A: Focused Library Design, Virtual Screening, Chemical Synthesis and Bioassay, Journal of Combinatorial Chemistry, 8 (2006), pp. 326-337, 2006) with applications as diverse as: dyes, pharmaceuticals, raw materials for the formation of various functional groups.
En general, los métodos clásicos conocidos de reducción de nitrocompuestos se engloban en dos grupos: In general, the known classical methods of reducing nitro compounds are grouped into two groups:
• por hidrogenación catalítica (Rylander, Hydrogenation Methods, Academic Press, (1985), pp. 3651985; Tafesh y Weigunty 1996), y • by catalytic hydrogenation (Rylander, Hydrogenation Methods, Academic Press, (1985), pp. 365-1985; Tafesh and Weigunty 1996), and
• por reducción química vía la transferencia de hidrógeno proveniente de un donador adecuado (Brieger y Nestick, Catalytic transfer hydrogenation, Chemical Revíews, 74 (1974), pp. 567-580) • by chemical reduction via the transfer of hydrogen from a suitable donor (Brieger and Nestick, Catalytic transfer hydrogenation, Chemical Reviews, 74 (1974), pp. 567-580)
Una revisión de los diferentes métodos para la reducción de nitrocompuestos orgánicos a aminas puede encontrarse, por ejemplo, en Larock, R.C., "Comprehensive Organic Transformations: A Guide to Functional 5 Group Preparation", 2a ed.; Wiley-VCH, Weinheim, 1999, 821-828; Ono, N., "The Nitro Group in Organic Synthesis", Wiley-VCH, New York, 2001; Blaser, H.-U.; Steiner, H.; Studer, M., "Selective Catalytic Hydrogenation of Functionalized Nitroarenes: An Update" Chem. Cat. Chem. 2009, 1,210-221. A review of the different methods for the reduction of organic nitrocompounds to amines can be found, for example, in Larock, R.C., "Comprehensive Organic Transformations: A Guide to Functional 5 Group Preparation", 2nd ed.; Wiley-VCH, Weinheim, 1999, 821-828; Ono, N., "The Nitro Group in Organic Synthesis", Wiley-VCH, New York, 2001; Blaser, H.-U.; Steiner, H.; Studer, M., "Selective Catalytic Hydrogenation of Functionalized Nitroarenes: An Update" Chem. Cat. Chem. 2009, 1,210-221.
En el documento EP3523271 se describe un proceso para la hidrogenación continua de dinitrotolueno a tolilendiamina en una mezcla de reacción líquida que comprende dinitrotolueno en presencia de un catalizador soportado que comprende como componente activo una mezcla de níquel y platino en una relación níquel:platino de 30:70 a 70:30 y opcionalmente uno o más metales adicionales, donde la hidrogenación se realiza en presencia de al menos una sal seleccionada del grupo que consiste en sales de metales alcalinos, metales alcalinotérreos y de tierras raras. EP3523271 describes a process for the continuous hydrogenation of dinitrotoluene to tolylenediamine in a liquid reaction mixture comprising dinitrotoluene in the presence of a supported catalyst comprising as an active component a mixture of nickel and platinum in a nickel:platinum ratio of 30:70 to 70:30 and optionally one or more additional metals, wherein the hydrogenation is carried out in the presence of at least one salt selected from the group consisting of alkali metal, alkaline earth metal and rare earth metal salts.
Entre las desventajas de muchos de estos métodos conocidos de la técnica anterior para reducir compuestos nitroaromáticos a aminas se encuentran unas condiciones de reacción que resultan incompatibles con la presencia de grupos funcionales sensibles en la molécula, por ejemplo, aquellos potencialmente reducibles (carbonilos, nitrilos, enlaces C C insaturados o halógenos). Igualmente, muchos de estos métodos conocidos dan lugar a subproductos difícilmente separables del producto final, siendo necesarias tediosas y costosas etapas de purificación para obtener un producto puro. Among the disadvantages of many of these prior art methods for reducing nitroaromatic compounds to amines are reaction conditions that are incompatible with the presence of sensitive functional groups in the molecule, for example, those potentially reducible (carbonyls, nitriles, unsaturated C-C bonds, or halogens). Likewise, many of these known methods result in byproducts that are difficult to separate from the final product, requiring tedious and costly purification steps to obtain a pure product.
Así, el objeto de la invención es desarrollar un procedimiento para la desoxigenación de compuestos nitroaromáticos que no conlleve las desventajas citadas de los procedimientos conocidos, empleando como agente reductor un producto natural procedente de la biomasa, medioambientalmente benigno, sostenible, de bajo coste, fácilmente accesible, manejable y eliminable del medio de reacción, facilitando la obtención operacionalmente sencilla de aminas con un alto rendimiento y de elevada pureza. Thus, the object of the invention is to develop a process for the deoxygenation of nitroaromatic compounds that does not entail the aforementioned disadvantages of known processes, using as a reducing agent a natural product derived from biomass, environmentally benign, sustainable, low cost, easily accessible, manageable and eliminable from the reaction medium, facilitating the operationally simple obtaining of amines with a high yield and high purity.
Este objeto se consigue mediante un procedimiento de reducción catalítica de compuestos orgánicos que incluyen un grupo funcional nitro, de fórmula general 1, a compuestos orgánicos de tipo amina, de fórmula general 2, empleando como agente reductor estequiométrico Y-terpineno, un producto natural procedente de la biomasa, medioambientalmente benigno y sostenible, en presencia de un catalizador de dioxomolibdeno(VI), bajo presión atmosférica y con irradiación de microondas. This object is achieved through a catalytic reduction process of organic compounds that include a nitro functional group, of general formula 1, to amine-type organic compounds, of general formula 2, using as a stoichiometric reducing agent Y-terpinene, a natural product derived from biomass, environmentally benign and sustainable, in the presence of a dioxomolybdenum(VI) catalyst, under atmospheric pressure and with microwave irradiation.
siendo R1 un grupo arilo o heteroarilo, sustituido o no sustituido, y [cat] un catalizador de dioxomolibdeno(VI) where R1 is a substituted or unsubstituted aryl or heteroaryl group, and [cat] is a dioxomolybdenum(VI) catalyst
A este respecto, la utilización de Y-terpineno (1-isopropil-4-metil-1,4-ciclohexadieno) como agente reductor, un compuesto natural que constituye uno de los principales componentes de los aceites esenciales procedentes de los cítricos, fácilmente accesible y manejable, genera subproductos fácilmente separables y permite la obtención de aminas de elevada pureza con un alto rendimiento y con un único y sencillo paso de purificación. El procedimiento de la invención tiene además la ventaja de no necesitar una atmósfera inerte ni presiones elevadas para llevar a cabo la reacción de reducción, ya que no implica el manejo y almacenamiento de hidrógeno gas, siendo todos los reactivos sólidos o líquidos y fácilmente manipulables. In this regard, the use of Y-terpinene (1-isopropyl-4-methyl-1,4-cyclohexadiene) as a reducing agent, a natural compound that constitutes one of the main components of essential oils from citrus fruits, easily accessible and manageable, generates easily separable by-products and allows the production of highly pure amines with high yield and with a single, simple purification step. The process of the invention also has the advantage of not requiring an inert atmosphere or high pressures to carry out the reduction reaction, since it does not involve the handling and storage of hydrogen gas, and all the reactants are solid or liquid and easily manipulated.
Así, el procedimiento de la invención proporciona por tanto ventajas desde el punto de vista económico, medioambiental y de seguridad. Thus, the process of the invention provides advantages from an economic, environmental and safety point of view.
En una forma de realización de la invención, la reacción descrita se lleva a cabo en un medio libre de disolventes orgánicos, bajo presión atmosférica y por irradiación en un horno microondas monomodo. In one embodiment of the invention, the described reaction is carried out in a medium free of organic solvents, under atmospheric pressure and by irradiation in a single-mode microwave oven.
Alternativamente, la reacción descrita se lleva a cabo en un disolvente orgánico seleccionado de N,N-dimetilacetamida, N,N-dimetilformamida o 1-metil-2-pirrolidona como disolvente orgánico bajo presión atmosférica y por irradiación en un horno microondas monomodo. Alternatively, the described reaction is carried out in an organic solvent selected from N,N-dimethylacetamide, N,N-dimethylformamide or 1-methyl-2-pyrrolidone as organic solvent under atmospheric pressure and by irradiation in a single-mode microwave oven.
En una forma de realización de la invención, la irradiación con microondas se produce a una potencia máxima de 270 W, a una temperatura de 180 °C, y en un tiempo de reacción de 1 hora. In one embodiment of the invention, microwave irradiation occurs at a maximum power of 270 W, at a temperature of 180 °C, and in a reaction time of 1 hour.
Preferentemente, el catalizador de molibdeno (VI) se selecciona de entre bis-(dimetilformamida)diclorodioxomolibdeno(VI), MoO2Cl2(dmf)2, bis-(dimetilsulfóxido)-diclorodioxomolibdeno(VI), MoO2Ch(dmso)2, en cantidades de un 5 mol%, empleando como ligando quelante del molibdeno 2,2’-bipiridina o 1,10-fenantrolina en la misma cantidad. Preferably, the molybdenum (VI) catalyst is selected from bis-(dimethylformamide)dichlorodioxomolybdenum(VI), MoO2Cl2(dmf)2, bis-(dimethylsulfoxide)-dichlorodioxomolybdenum(VI), MoO2Ch(dmso)2, in quantities of 5 mol%, using as molybdenum chelating ligand 2,2'-bipyridine or 1,10-phenanthroline in the same quantity.
Los únicos subproductos de la reacción obtenidos según el procedimiento de la invención son agua y p-cimeno, lo que permite obtener la amina de forma pura tras filtración a través de gel de sílice. The only reaction by-products obtained according to the process of the invention are water and p-cymene, which allows the amine to be obtained in pure form after filtration through silica gel.
Las aminas obtenidas a partir del procedimiento de la invención tienen una alta pureza, con un rendimiento de entre aproximadamente el 50% y aproximadamente el 90%. The amines obtained from the process of the invention have a high purity, with a yield of between approximately 50% and approximately 90%.
Este nuevo procedimiento destaca por utilizar un agente reductor sostenible, procedente de la biomasa, fácilmente accesible, seguro desde el punto de vista de su manejo, no tóxico, 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. Además, los subproductos generados son igualmente no tóxicos y fácilmente separables de las aminas sintetizadas por filtración. This new process is notable for its use of a sustainable, biomass-derived reducing agent that is easily accessible, safe to handle, and non-toxic. This allows the process of the invention to be carried out without the need for significant protection systems or safety investments. Furthermore, the byproducts generated are also non-toxic and easily separable from the synthesized amines by filtration.
EjemplosExamples
A continuación, se describe más detalladamente la invención en base a ejemplos de realización de la misma. The invention is described in more detail below based on exemplary embodiments.
Ejemplo 1: Reducción de 4-nitrobenzonitriloExample 1: Reduction of 4-nitrobenzonitrile
Una mezcla de 148.1 mg de 4-nitrobenzonitrilo (1 mmol), 1,0 ml de Y-terpineno, 0,1 ml de N,N-dimetilacetamida, 17,3 mg de MoO2Cl2(dmf)2 (5 mol%) y 7,8 mg de 2,2-bipiridina se calentó por irradiación en un horno microondas monomodo a una potencia máxima de 270 W y a una temperatura de 180 °C, en un vial de reacción de 10 ml, durante 1 hora. Transcurrido ese tiempo, se dejó enfriar la mezcla hasta temperatura ambiente y se filtró a través de del de sílice utilizando una mezcla hexano:acetato de etilo 2:1 como eluyente. Se obtuvieron 95,7 mg de 4-aminobenzonitrilo (rendimiento: 81%, pureza >95%). A mixture of 148.1 mg of 4-nitrobenzonitrile (1 mmol), 1.0 ml of Y-terpinene, 0.1 ml of N,N-dimethylacetamide, 17.3 mg of MoO2Cl2(dmf)2 (5 mol%) and 7.8 mg of 2,2-bipyridine was heated by irradiation in a single-mode microwave oven at a maximum power of 270 W and a temperature of 180 °C, in a 10 ml reaction vial, for 1 hour. After that time, the mixture was allowed to cool to room temperature and filtered through a silica gel using a 2:1 hexane:ethyl acetate mixture as eluent. 95.7 mg of 4-aminobenzonitrile was obtained (yield: 81%, purity >95%).
Alternativamente, la misma reacción se llevó a cabo en presencia de 1,0 ml N,N-dimetilacetamida y con 0,8 ml de Y-terpineno, obteniéndose 105,9 mg de 4 aminobenzonitrilo (rendimiento: 90%, pureza >95%). Alternatively, the same reaction was carried out in the presence of 1.0 ml N,N-dimethylacetamide and with 0.8 ml Y-terpinene, obtaining 105.9 mg of 4-aminobenzonitrile (yield: 90%, purity >95%).
Datos espectroscópicos: Spectroscopic data:
1H-RMN (300 MHz, DMSO-d6): 5 (ppm): 6,10 (s, 2H), 6,59-6,70 (m, 2H), 7,35-7,43 (m, 2H). 1H-NMR (300 MHz, DMSO-d6): 5 (ppm): 6.10 (s, 2H), 6.59-6.70 (m, 2H), 7.35-7.43 (m, 2H).
13C-RMN (75,4 MHz, DMSO-d6): 5 (ppm): 96,8 (C), 113,6 (2 x CH), 120,7 (C), 133,5 (2 x CH), 153,0 (C). 13C-NMR (75.4 MHz, DMSO-d6): 5 (ppm): 96.8 (C), 113.6 (2 x CH), 120.7 (C), 133.5 (2 x CH), 153.0 (C).
Ejemplo 2: Reducción de 4-nitrobenzofenonaExample 2: Reduction of 4-nitrobenzophenone
Una mezcla de 227,2 mg de 4-nitrobenzofenona (1 mmol), 1,0 ml de Y-terpineno, 0,1 ml de N,N-dimetilacetamida, 17,3 mg de MoO2Cl2(dmf)2 (5 mol%) y 7,8 mg de 2,2’-bipiridina se calentó por irradiación en un horno microondas monomodo a una potencia máxima de 270 W y a una temperatura de 180 °C, en un vial de reacción de 10 ml, durante 1 hora. Transcurrido ese tiempo, se dejó enfriar la mezcla hasta temperatura ambiente y se filtró a través de gel de sílice utilizando una mezcla hexano:acetato de etilo 2:1 como eluyente. Se obtuvieron 158,0 mg de 4-aminobenzofenona (rendimiento: 80%, pureza >95%). A mixture of 227.2 mg of 4-nitrobenzophenone (1 mmol), 1.0 ml of Y-terpinene, 0.1 ml of N,N-dimethylacetamide, 17.3 mg of MoO2Cl2(dmf)2 (5 mol%) and 7.8 mg of 2,2’-bipyridine was heated by irradiation in a single-mode microwave oven at a maximum power of 270 W and a temperature of 180 °C, in a 10 ml reaction vial, for 1 hour. After that time, the mixture was allowed to cool to room temperature and filtered through silica gel using a 2:1 hexane:ethyl acetate mixture as eluent. 158.0 mg of 4-aminobenzophenone was obtained (yield: 80%, purity >95%).
Alternativamente, la misma reacción se llevó a cabo en presencia de 1,0 ml deN,N-dimetilacetamida y con 0,8 ml de Y-terpineno, obteniéndose 169,8 mg de 4-aminobenzofenona (rendimiento 86%, pureza >95%). Alternatively, the same reaction was carried out in the presence of 1.0 ml of N,N-dimethylacetamide and with 0.8 ml of Y-terpinene, obtaining 169.8 mg of 4-aminobenzophenone (yield 86%, purity >95%).
Datos espectroscópicos: Spectroscopic data:
1H-RMN (300 MHz, CDCh): 5 (ppm): 4,22 (bs, 2H), 6,65 (d, J = 8,6 Hz, 2H), 7,40-7,54 (m, 3H), 7,67-7,75 (m, 4H). 1H-NMR (300 MHz, CDCh): 5 (ppm): 4.22 (bs, 2H), 6.65 (d, J = 8.6 Hz, 2H), 7.40-7.54 (m, 3H), 7.67-7.75 (m, 4H).
13C-RMN (75,4 MHz, CDCh): 5 (ppm): 113,7 (2 x CH), 127,1 (C), 128,1 (2 x CH), 129,6 (2 x CH), 131,5 (CH), 133,0 (2 x CH), 138,9 (C), 151,2 (C), 195,5 (C). 13C-NMR (75.4 MHz, CDCh): 5 (ppm): 113.7 (2 x CH), 127.1 (C), 128.1 (2 x CH), 129.6 (2 x CH), 131.5 (CH), 133.0 (2 x CH), 138.9 (C), 151.2 (C), 195.5 (C).
Ejemplo 3: Reducción de 4-nitrocinamato de etiloExample 3: Reduction of ethyl 4-nitrocinnamate
Una mezcla de 221,2 mg de 4-nitrocinamato de etilo (1 mmol), 1,0 ml de Y-terpineno, 17,3 mg de MoO2Ch(dmf)2 (5 mol%) y 7,8 mg de 2,2’-bipiridina se calentó por irradiación en un horno microondas monomodo a una potencia máxima de 270 W y a una temperatura de 180 °C, en un vial de reacción de 10 ml, durante 1 hora. Transcurrido ese tiempo, se dejó enfriar la mezcla hasta temperatura ambiente y se filtró a través de sílice utilizando una mezcla hexano:acetato de etilo 2:1 como eluyente. Se obtuvieron 151,1 mg de 4 aminocinamato de etilo (rendimiento: 79%, pureza >95%). A mixture of 221.2 mg of ethyl 4-nitrocinnamate (1 mmol), 1.0 mL of Y-terpinene, 17.3 mg of MoO2Ch(dmf)2 (5 mol%) and 7.8 mg of 2,2’-bipyridine was heated by irradiation in a single-mode microwave oven at a maximum power of 270 W and a temperature of 180 °C, in a 10 mL reaction vial, for 1 h. After that time, the mixture was allowed to cool to room temperature and filtered through silica using a 2:1 hexane:ethyl acetate mixture as eluent. 151.1 mg of ethyl 4-aminocinnamate was obtained (yield: 79%, purity >95%).
Alternativamente, la misma reacción se llevó a cabo en presencia de 1,0 ml deN,N-dimetilacetamida y con 0,8 ml de Y-terpineno, obteniéndose 128,0 mg de 4-aminocinamato de etilo (rendimiento: 67%, pureza >95%). Alternatively, the same reaction was carried out in the presence of 1.0 ml of N,N-dimethylacetamide and with 0.8 ml of Y-terpinene, obtaining 128.0 mg of ethyl 4-aminocinnamate (yield: 67%, purity >95%).
Datos espectroscópicos: Spectroscopic data:
1H-RMN (300 MHz, CDCh): 5 (ppm): 1,30 (t, J = 7,1 Hz, 3H), 4,05 (bs, 2H), 4,22 (q, J = 7,1 Hz, 2H), 6,21 (d, J = 15,8 Hz, 1H), 6,57-6,63 (m, 2H), 7,27-7,33 (m, 2H), 7,58 (d, J = 16,3 Hz, 1H). 1H-NMR (300 MHz, CDCh): 5 (ppm): 1.30 (t, J = 7.1 Hz, 3H), 4.05 (bs, 2H), 4.22 (q, J = 7.1 Hz, 2H), 6.21 (d, J = 15.8 Hz, 1H), 6.57-6.63 (m, 2H), 7.27-7.33 (m, 2H), 7.58 (d, J = 16.3 Hz, 1H).
13C-RMN (75,4 MHz, CDCh): 5 (ppm): 14,3 (CH3), 60,1 (CH2), 113,4 (CH), 114,7 (2 x CH), 124,4 (C), 129,8 (2 x CH), 145,0 (CH), 149,0 (C), 167,8 (C). 13C-NMR (75.4 MHz, CDCh): 5 (ppm): 14.3 (CH3), 60.1 (CH2), 113.4 (CH), 114.7 (2 x CH), 124.4 (C), 129.8 (2 x CH), 145.0 (CH), 149.0 (C), 167.8 (C).
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| DE3717881A1 (en) * | 1987-05-27 | 1988-12-08 | Basf Ag | CATALYTIC TRANSFER HYDRATION WITH AROMATIC NITRO COMPOUNDS AS A HYDROGEN ACCEPTOR |
| ES2392998B2 (en) * | 2011-05-30 | 2013-07-17 | Universidad De Burgos | PROCEDURE FOR CATALYTIC REDUCTION OF NITROAROMATIC COMPOUNDS. |
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