ES2586248T3 - Proceso de síntesis de arilaminas - Google Patents
Proceso de síntesis de arilaminas Download PDFInfo
- Publication number
- ES2586248T3 ES2586248T3 ES08840252.4T ES08840252T ES2586248T3 ES 2586248 T3 ES2586248 T3 ES 2586248T3 ES 08840252 T ES08840252 T ES 08840252T ES 2586248 T3 ES2586248 T3 ES 2586248T3
- Authority
- ES
- Spain
- Prior art keywords
- dmf
- acac
- reaction
- aromatic
- diketone
- 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
- 238000000034 method Methods 0.000 title abstract description 6
- 150000004982 aromatic amines Chemical class 0.000 title abstract description 4
- 230000015572 biosynthetic process Effects 0.000 title description 4
- 238000003786 synthesis reaction Methods 0.000 title description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 11
- 239000003446 ligand Substances 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 229910021529 ammonia Inorganic materials 0.000 abstract description 4
- 125000003118 aryl group Chemical group 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 150000001491 aromatic compounds Chemical group 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 150000004696 coordination complex Chemical class 0.000 abstract 1
- 238000000605 extraction Methods 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000002955 isolation Methods 0.000 abstract 1
- 239000003960 organic solvent Substances 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- 239000012429 reaction media Substances 0.000 abstract 1
- 239000011541 reaction mixture Substances 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 38
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- ZKXWKVVCCTZOLD-FDGPNNRMSA-N copper;(z)-4-hydroxypent-3-en-2-one Chemical compound [Cu].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O ZKXWKVVCCTZOLD-FDGPNNRMSA-N 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 8
- 239000010949 copper Substances 0.000 description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 description 6
- 235000011152 sodium sulphate Nutrition 0.000 description 6
- 229910000024 caesium carbonate Inorganic materials 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 150000001879 copper Chemical class 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 3
- PKJBWOWQJHHAHG-UHFFFAOYSA-N 1-bromo-4-phenylbenzene Chemical group C1=CC(Br)=CC=C1C1=CC=CC=C1 PKJBWOWQJHHAHG-UHFFFAOYSA-N 0.000 description 3
- YRAJNWYBUCUFBD-UHFFFAOYSA-N 2,2,6,6-tetramethylheptane-3,5-dione Chemical compound CC(C)(C)C(=O)CC(=O)C(C)(C)C YRAJNWYBUCUFBD-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 239000007832 Na2SO4 Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- DPZNOMCNRMUKPS-UHFFFAOYSA-N 1,3-Dimethoxybenzene Chemical compound COC1=CC=CC(OC)=C1 DPZNOMCNRMUKPS-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 238000005576 amination reaction Methods 0.000 description 2
- 150000001502 aryl halides Chemical group 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- NCBZRJODKRCREW-UHFFFAOYSA-N m-anisidine Chemical compound COC1=CC=CC(N)=C1 NCBZRJODKRCREW-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- PLDWAJLZAAHOGG-UHFFFAOYSA-N 1-bromo-3-methoxybenzene Chemical compound COC1=CC=CC(Br)=C1 PLDWAJLZAAHOGG-UHFFFAOYSA-N 0.000 description 1
- GSOHKPVFCOWKPU-UHFFFAOYSA-N 3-methylpentane-2,4-dione Chemical compound CC(=O)C(C)C(C)=O GSOHKPVFCOWKPU-UHFFFAOYSA-N 0.000 description 1
- YBAZINRZQSAIAY-UHFFFAOYSA-N 4-aminobenzonitrile Chemical compound NC1=CC=C(C#N)C=C1 YBAZINRZQSAIAY-UHFFFAOYSA-N 0.000 description 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 1
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
- C07C209/10—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/22—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of other functional groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
- C07C211/45—Monoamines
- C07C211/46—Aniline
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
- C07C211/58—Naphthylamines; N-substituted derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/72—Nitrogen atoms
- C07D213/73—Unsubstituted amino or imino radicals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Pyridine Compounds (AREA)
Abstract
Procedimiento de preparación de arilaminas de fórmula R0-(NH2)m, donde R0 representa un aromático y m se encuentra entre 1 y 3; dicho procedimiento comprende las siguientes etapas: a) preparación de un medio de reacción que comprenda: 1) un compuesto aromático que lleve al menos un grupo saliente de la fórmula R0-Ym en la que R0 es un radical aromático e Y representa un átomo de halógeno, encontrándose m entre 1 y 3; 2) una solución acuosa de amoniaco; 3) un sistema catalizador que comprenda un complejo de complejo de metal/ligando seleccionado de Fe/ß-dicetona y/o Cu/ß-dicetona; 4) una base; y 5) un disolvente orgánico polar aprótico; b) el calentamiento de dicha mezcla de reacción a una temperatura de entre 20 °C y 200 °C; c) la implementación de la reacción; y d) la extracción y el aislamiento de la arilamina R0-(NH2)m formada.
Description
se lavó con agua. La fase acuosa se extrajo cinco veces con diclorometano. Las fases orgánicas se combinaron, se secaron sobre sulfato de sodio (Na2SO4), y después se concentraron para obtener el producto bruto.
[0110] Este producto en bruto se purificó por cromatografía sobre gel de sílice (ciclohexano eluyente/acetato 5 de etilo, 9:1) para obtener 4-aminobenzonitrilo en forma de sólido.
[0111] En un tubo de Schlenk o en un tubo de Radley (previamente purgado con nitrógeno y rellenado con 10 nitrógeno) se cargó el complejo de cobre/acetilacetonato ([Cu(acac)2]; 52 mg, 0,2 mmol), acetilacetonato (82 µL; 0,8 mmol), 3-bromoanisol (374 mg; 2 mmol) y carbonato de cesio (Cs2CO3, 978 mg, 3,0 mmol).
[0112] Después se añadieron en atmósfera de nitrógeno dimetilformamida (4 ml DMF).y a continuación amoniaco al 28% (en peso) (600 uL). El tubo se selló bajo nitrógeno y la mezcla se calentó a 90 °C y se agitó
15 durante 24 horas. Después de enfriarse a temperatura ambiente, la mezcla se diluyó con diclorometano, y después se lavó con agua. La fase acuosa se extrajo cinco veces con diclorometano. Las fases orgánicas se combinaron, se secaron sobre sulfato de sodio (Na2SO4), y después se concentraron para obtener el producto bruto.
[0113] Este producto en bruto se purificó por cromatografía sobre gel de sílice (ciclohexano/acetato de etilo, 20 9:1) para obtener 3-anisidina, en forma de un aceite.
[0114] Para probar la extensión de la reacción de aminación, se realizaron varias pruebas de acuerdo a los 25 mismos procedimientos descritos anteriormente, a partir de diversos haluros de arilo que llevan sustituyentes bien de tipo aceptor de electrones o donante de electrones.
[0115] Los resultados se muestran en la Tabla 3.
30 --Tabla 3 -Reacciones con diversos precursores aromáticos --
- N.°
- ArX ArNH2 Rendimiento‡ (%)
- D1
- 90
- D2
- 80
- D3
- 93**, 99†,97*
- D4
-
imagen10 imagen11 63
- D5
- 23
- D6
- PhBr PhNH2 78
- D7
- 88
- D8
- 85
- D9
- 65, 79***
- D10
- 90, 98††
- D11
- 92, (82 *and**)
- D12
-
imagen12 imagen13 92, 84**
- D13
-
imagen14 imagen15 41 †††
- D14
-
imagen10 imagen16 84
- D15
- 82
Ejemplo E: Influencia del ligando [0117] Para probar la influencia de la naturaleza de los ligandos en la reacción de aminación, se llevaron a 10 cabo varias pruebas a partir de 4-bromobifenilo en presencia de complejos de cobre con diferentes ligandos. [0118] Los resultados se muestran en la Tabla 4.
[0116] Los rendimientos son rendimientos aislados. A menos que se indique lo contrario la 2,4-pentanodiona se utiliza como ligando. † con 3-metil-2,4-pentanodiona o 2,2,6,6-tetrametil-3,5-heptanodiona utilizadas como ligandos. * Reacción llevada a cabo a 70 °C. ** La reacción llevada a cabo a 60 °C *** Tiempo de reacción 36 h. ††
5 Realizado con tetrametil-3,5-heptanodiona ††† Formación del producto de doble sustitución para-aminoanilina 42%.
--La Tabla 4 -reacciones en presencia de complejos de cobre con diferentes ligandos --
- N.°
- Ligandos L Rendimiento‡ (%) Selectivitdad†
- E1
- 76 92
- E2
- 24 92
- E3
-
imagen17 7 -
- E4
- 29 91
- E5
-
imagen18 35 99
- E6
-
imagen19 79 99
- E7
-
imagen20 7 -
- E8
- 0 -
- Se utilizaron ‡ L (0.6 eq) y NH3 comercial acuosa al 28% (5 eq). Rendimiento determinado utilizando 1,3dimetoxibenceno como estándar. Selectividad †/C-C de acoplamiento de entre L y 4-bromobifenilo.
Ejemplo F: Influencia de la fuente de cobre y de los disolventes
5 [0119] Para probar la influencia de la fuente de cobre y los disolventes, se llevaron a cabo varias pruebas a partir de 4-bromobifenilo de Cu(acac)2 en presencia de diversas sales de cobre y diversos disolventes.
--Tabla 5 -Reacciones en presencia de diversas sales de cobre y disolventes
- [Cu], 0.1 eq.
- Ligando 1 (eq.) disolvente Rendimiento [a] [%]
- F1
- - 0.6 DMF 0
- F2
- Cul - DMF 0[b]
- F3
- Cul 0.6 DMF 2[c]
- F4
- Cul 0.6 DMF 76
- F5
- Cu 0.6 DMF 68
- F6
- CuO 0.6 DMF 79
- F7
- Cu(OAc)2 0.6 DMF 73
- F8
- Cu2O 0.6 DMF 63
- F9
- Cu(acac)2 - DMF 23
- F10
- Cu(acac)2 0.4 DMF 76
- F11
- Cu(acac)2 0.4 DMSO 18
- F12
- Cu(acac)2 0.4 CH3CN 34
- F13
- Cu(acac)2 0.4 NMP 50
- F14
- Cu(acac)2 0.4 H2O 0
- F15
- Cu(acac)2 0.4 DMF 6[d]
- F16
- Cu(acac)2 0.4 DMF 45[e]
- F17
- Cu(acac)2 0.4 DMF 45[f]
- F18
- Cu(acac)2 0.4 DMF 93[g] , 20[h]
- [a] Rendimiento determinado utilizando benceno 1,3-dimetoxi como patrón interno. [b] A pesar de obtener resultados a 140 °C. [c] Sin base. [d] DMF pre-saturado con gas amoniaco. [e] Adición de 0.5 eq. de NBu4 +Br-. [f] Se utilizó K2CO3 en lugar de Cs2CO3. [g] Tiempo de reacción 24 h. [h] Tiempo de reacción 24 h, se utilizó un 3% de Cu(acac)2.
Ejemplo G: Síntesis de anilina catalizada por hierro
5 [0120] En un tubo de Schlenk o un tubo de Radley (previamente purgado con nitrógeno y rellenado con nitrógeno) se cargó el complejo de hierro/acetilacetonato ([Fe(acac)3]; 70 mg, 0,2 mmol), 2,2,6,6-tetrametil-3,5heptanodiona (166 µL, 0,8 mmol), yodobenceno (204 mg; 1 mmol) y carbonato de cesio (Cs2CO3, 489 mg; 1,5 mmol) .
10 [0121] Después se añadió en atmósfera de nitrógeno dimetilformamida (2 ml DMF) y luego amoniaco al 28% (en peso) (300 uL). El tubo se selló bajo nitrógeno y la mezcla se calentó a 140°C y se agitó durante 24 horas. Después de enfriarse a temperatura ambiente, la mezcla se diluyó con diclorometano, y después se lavó con agua. La fase acuosa se extrajo cinco veces con diclorometano. Las fases orgánicas se combinaron, se secaron sobre
15 sulfato de sodio (Na2SO4), y después se concentraron para obtener el producto bruto.
[0122] Este producto en bruto se purificó por cromatografía sobre gel de sílice (ciclohexano eluyente/acetato de etilo, 9: 1) para obtener anilina (20% -30%), en forma de aceite.
20 [0123] La presente invención proporciona un procedimiento general de aplicación fácil, económica y eficaz para convertir haluros de arilo en derivados de anilina, comprendiendo dicho proceso una sola etapa. Los buenos rendimientos y selectividades, combinados con una variedad de sustituyentes posibles, hace que este proceso resulte bastante rentable y susceptible de aplicación industrial, en particular en el campo de la síntesis orgánica.
25 [0124] El coste relativamente bajo tanto de amoniaco como del cobre catalítico hace que el proceso de la presente invención resulte fácilmente adaptable y rentable para la producción de aminas de arilo (derivados de
Claims (1)
-
imagen1 imagen2
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0706827 | 2007-09-28 | ||
| FR0706827A FR2921656B1 (fr) | 2007-09-28 | 2007-09-28 | Procede de synthese d'arylamines |
| PCT/FR2008/051701 WO2009050366A2 (fr) | 2007-09-28 | 2008-09-24 | Procede de synthese d'arylamines |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| ES2586248T3 true ES2586248T3 (es) | 2016-10-13 |
Family
ID=39386359
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| ES08840252.4T Active ES2586248T3 (es) | 2007-09-28 | 2008-09-24 | Proceso de síntesis de arilaminas |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US8399680B2 (es) |
| EP (1) | EP2197829B1 (es) |
| ES (1) | ES2586248T3 (es) |
| FR (1) | FR2921656B1 (es) |
| WO (1) | WO2009050366A2 (es) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101745680B1 (ko) * | 2010-08-24 | 2017-06-09 | 에스케이케미칼 주식회사 | 파라-페닐렌 디아민의 제조 방법 |
| CN105985258B (zh) * | 2015-01-29 | 2019-08-02 | 上海彩迩文生化科技有限公司 | 一种苯甲酰胺化合物的制备方法及其中间体 |
| CN109456150A (zh) * | 2018-10-25 | 2019-03-12 | 浙江林江化工股份有限公司 | 一种3,4,5-三氟苯酚的合成方法 |
| FR3113287B1 (fr) * | 2020-08-07 | 2023-06-23 | Phv Pharma | Procédé industriel de synthèse de l’imiquimod à partir de la quinolèine-2,4-diol applicable à son utilisation pharmaceutique |
| CN116854603A (zh) * | 2023-07-07 | 2023-10-10 | 沈阳感光化工研究院有限公司 | 一种医药中间体化合物2-氨基-4-溴-5-氯苯甲酸制备方法 |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1840760A (en) * | 1926-08-26 | 1932-01-12 | Dow Chemical Co | Process of making aromatic amino compounds |
| DE586879C (de) * | 1932-01-21 | 1933-10-27 | Chem Fab Von Heyden Akt Ges | Verfahren zur Darstellung von basische Gruppen enthaltenden Pyridinabkoemmlingen |
| US2455932A (en) * | 1944-11-25 | 1948-12-14 | Standard Oil Co | Process of making aryl amines |
| US3975439A (en) | 1973-07-26 | 1976-08-17 | E. I. Du Pont De Nemours And Company | Preparation and amination of iodoaniline |
| IL100537A0 (en) * | 1991-12-27 | 1992-09-06 | Chemagis Ltd | A process for the preparation of n-alkyl-3,4-dialkyloxyanilines and derivatives thereof |
| US20010047013A1 (en) * | 2000-03-10 | 2001-11-29 | Fengrui Lang | Process for the preparation of arylamines |
| WO2003006420A1 (en) | 2001-07-12 | 2003-01-23 | Yale University | Catalytic method to convert aryl compounds to aryl amines |
| FR2840608B1 (fr) | 2002-06-11 | 2005-07-01 | Seranalis | Procede de preparation de 1,3,5-triaminobenzene et son hydrolyse en phloroglucinol de haute purete |
| CN100341846C (zh) | 2002-12-12 | 2007-10-10 | 厦门市先端科技有限公司 | 苯胺、苯酚及其衍生物的制备方法 |
| CN1984872A (zh) | 2004-07-16 | 2007-06-20 | 帝斯曼知识产权资产管理有限公司 | 制备（杂）芳胺的方法 |
| CN101437808A (zh) | 2006-03-21 | 2009-05-20 | 耶鲁大学 | 由芳香化合物与氨或金属酰胺反应合成芳基胺的方法 |
-
2007
- 2007-09-28 FR FR0706827A patent/FR2921656B1/fr not_active Expired - Fee Related
-
2008
- 2008-09-24 EP EP08840252.4A patent/EP2197829B1/fr not_active Not-in-force
- 2008-09-24 WO PCT/FR2008/051701 patent/WO2009050366A2/fr not_active Ceased
- 2008-09-24 US US12/680,606 patent/US8399680B2/en not_active Expired - Fee Related
- 2008-09-24 ES ES08840252.4T patent/ES2586248T3/es active Active
Also Published As
| Publication number | Publication date |
|---|---|
| EP2197829B1 (fr) | 2016-05-04 |
| WO2009050366A3 (fr) | 2009-06-11 |
| US20100298571A1 (en) | 2010-11-25 |
| FR2921656A1 (fr) | 2009-04-03 |
| WO2009050366A2 (fr) | 2009-04-23 |
| FR2921656B1 (fr) | 2012-11-02 |
| EP2197829A2 (fr) | 2010-06-23 |
| US8399680B2 (en) | 2013-03-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| ES2586248T3 (es) | Proceso de síntesis de arilaminas | |
| Gogoi et al. | Unique copper–salen complex: an efficient catalyst for N-arylations of anilines and imidazoles at room temperature | |
| ES2657676T3 (es) | Proceso para la preparación de derivados de l-alanina protegidos | |
| TW201302770A (zh) | 萘二醯亞胺和相關組合物的甲錫烷基衍生物及方法 | |
| CN107892704B (zh) | 多齿双核环金属配合物及包含该配合物的器件 | |
| CN103408445A (zh) | 一种芳胺类衍生物及其制备方法 | |
| CN110105305B (zh) | 过渡金属催化的c-h活化/环合合成1,2-苯并噻嗪衍生物的绿色合成方法 | |
| CN101570490A (zh) | 铜催化取代二苯胺的合成方法 | |
| ES2259128T3 (es) | Complejos de cobre y su uso. | |
| JP2001515879A (ja) | アリールオリゴアミン類の調製法 | |
| CN108774189B (zh) | 一种噁嗪苯醚衍生物及其制备方法 | |
| CN102617466A (zh) | 一类“上-下”不对称型叔丁基螺二芴化合物 | |
| CN103464207B (zh) | 一种稀土配合物催化剂,其制备方法、用途以及应用方法 | |
| BR102012000721B1 (pt) | Processo para preparar 1-(6-metilpiridin-3-il)-2-[4-(metilsulfonil)fenil]etanona, um intermediário de etoricoxib , uso de um catalisador de paládio e uso de um ligante xantphos | |
| CN104031088B (zh) | 一种α-氨基烷基膦化物的合成方法 | |
| JP2017165722A (ja) | 非対称ビス（１，２−ジアリールアミノ）ベンゼン類及びその製造方法 | |
| CN112469690B (zh) | 制造芳基胺的方法 | |
| CN102516171A (zh) | N-烷基-4-芳醛腙肼基-1,8-萘酰亚胺化合物及其制备方法 | |
| CN107868089B (zh) | 一种5,12-二氢-5-苯基吲哚并[3,2-a]咔唑的合成方法 | |
| CN102219739A (zh) | 氮杂蒽类化合物及其合成方法 | |
| CN104356170B (zh) | 钌铱异核环金属化合物及其制备方法和应用 | |
| ES2558260A1 (es) | Procedimiento de obtención de derivados de PDI | |
| JP2009298773A (ja) | 芳香族アミン化合物の製造方法 | |
| US2229099A (en) | Amino-aijxoxy-i | |
| CN107501234B (zh) | 一种二苯并噻吩类化合物及其制备方法 |