CS273921B1 - Method of 2-chloro-1,4-phenylendiamine preparation - Google Patents
Method of 2-chloro-1,4-phenylendiamine preparation Download PDFInfo
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- CS273921B1 CS273921B1 CS230889A CS230889A CS273921B1 CS 273921 B1 CS273921 B1 CS 273921B1 CS 230889 A CS230889 A CS 230889A CS 230889 A CS230889 A CS 230889A CS 273921 B1 CS273921 B1 CS 273921B1
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- CS
- Czechoslovakia
- Prior art keywords
- chloro
- phenylenediamine
- preparation
- nitroaniline
- dichlorobenzene
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- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- MGLZGLAFFOMWPB-UHFFFAOYSA-N 2-chloro-1,4-phenylenediamine Chemical compound NC1=CC=C(N)C(Cl)=C1 MGLZGLAFFOMWPB-UHFFFAOYSA-N 0.000 title claims description 17
- 238000000034 method Methods 0.000 title claims description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 24
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- LOCWBQIWHWIRGN-UHFFFAOYSA-N 2-chloro-4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1Cl LOCWBQIWHWIRGN-UHFFFAOYSA-N 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000006298 dechlorination reaction Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- GQFGHCRXPLROOF-UHFFFAOYSA-N 2-chloro-1,4-phenylenediamine sulfate Chemical compound OS(O)(=O)=O.NC1=CC=C(N)C(Cl)=C1 GQFGHCRXPLROOF-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012458 free base Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
(57)(57)
Příprava 2-chlor-l,4-fenylendiaminu katalytickou hydrogenaci 2-chlor-4-nitroanilinu na platinovém katalyzátoru tak, že reakce se uskutečňuje v prostředí chlorovaného organického rozpouštědla, s výhodou o-dichlorbenzenu, při 50 až 120 °C a tlaku vodíku 2 až 5 MPa.Preparation of 2-chloro-1,4-phenylenediamine by catalytic hydrogenation of 2-chloro-4-nitroaniline on a platinum catalyst such that the reaction is carried out in an environment of chlorinated organic solvent, preferably o-dichlorobenzene, at 50 to 120 ° C and hydrogen pressure 2 up to 5 MPa.
CS 273 921 BlCS 273 921 Bl
273 921273 921
CS 273 921 BlCS 273 921 Bl
Vynález se týká přípravy 2-chlor-l,4-fenylendiaminu katalytickou hydrogenací 2-chlor-4-mitroanilinu na platinovém katalyzátoru naneseném na aktivním uhlí. Reakce se uskutečňuje v chlorovaném organickém rozpouštědle.The present invention relates to the preparation of 2-chloro-1,4-phenylenediamine by catalytic hydrogenation of 2-chloro-4-mitroaniline on a platinum catalyst supported on activated carbon. The reaction is carried out in a chlorinated organic solvent.
Získá se roztok 2-chlor-l,4-fenylendiaminu v rozpouštědle, který lze přímo použít v dalši výrobě. Látka slouží při barvení kožešin nebo při přípravě červených azokondenzačních pigmentů.A solution of 2-chloro-1,4-phenylenediamine in a solvent is obtained which can be used directly in the next production. The substance is used for dyeing of fur or for preparation of red azocondensation pigments.
průmyslové přípravě je poměrně málo informací. V reportové literatuře (FIAT 1313) je zmínka o redukci 2-chlor-4-nitroanilinu v systému železo-voda-elektrolyt. Produkoval se 2-chlor-l,4-fenylendiamin ve formě sulfátu s výtažkem 94 % v závodech I. Cr. Farbenindustrie.Industrial preparation is relatively little information. The report literature (FIAT 1313) mentions the reduction of 2-chloro-4-nitroaniline in the iron-water-electrolyte system. 2-Chloro-1,4-phenylenediamine was produced in the form of sulfate with a yield of 94% in I. Cr. Farbenindustrie.
Více informací se týká laboratorního měřítka. NejstarSÍ údaje volí způsob redukce 2-chlor-4-nitroanilinu cínem v kyselině chlorovodíkové nebo zinkem v kyselině chlorovodíkové. V roce 1933 uveřejňuje A. M. Popov způsob přípravy 2-chlor-l,4-fenylendiaminu z 2-chlor-4-nit.roanilinu katalytickou hydrogenací na niklu při 90 až 96 °C ve vodném prostředí.More information is on laboratory scale. The earliest data are based on a method of reducing 2-chloro-4-nitroaniline with tin in hydrochloric acid or zinc in hydrochloric acid. In 1933, A. M. Popov discloses a process for preparing 2-chloro-1,4-phenylenediamine from 2-chloro-4-nitroaniline by catalytic hydrogenation on nickel at 90 to 96 ° C in an aqueous medium.
V roce 1970 patentovala firma CLAYTON ANILINE (evropský patent č. 805) postup na hydrogenací chlorovaných arylaminů za přítomnosti thiofenu jako inhibitoru dechlorace. Oako katalyzátor je preferována platina na aktivním uhlí (1 % Pt) ve formě 50 '-i pasty. Firma DU PONT (britský patent 859251) připravila 2-chlor-l,4-fenylendiamin z odpovídající nitrolátky o teplotě tání 58,5 až 61 °C katalytickou hydrogenací na platinovém katalyzátoru ve vodném prostředí při 90 až 95 °C.In 1970, CLAYTON ANILINE (European Patent No. 805) patented a process for the hydrogenation of chlorinated arylamines in the presence of thiophene as a dechlorination inhibitor. Oako catalyst is preferred platinum on activated carbon (1% Pt) in the form of a 50'-paste. DU PONT (British patent 859251) prepared 2-chloro-1,4-phenylenediamine from the corresponding nitro compound having a melting point of 58.5 to 61 ° C by catalytic hydrogenation on a platinum catalyst in an aqueous medium at 90 to 95 ° C.
Společnou nevýhodou všech postupů je problém odstranění vody z reakčni směsi. Odpaření vody s následnou destilaci volné báze není bezpečné. Podle údaje P. E. Frankenberga (Chem. Eng. News 60, 97 /1982) je 2-chlor-l,4-fenylendiamin tepelně nestabilní a během destilace je možnú exploze. Vzhledem k vysoké rozpustnosti 2-chlor-l,4-fenylendiaminu ve vodě (11,5 % při 20 °C) je nutné zpracovávat i matečné louhy po izolaci produktu odpařením, což znamená spotřebu energie.A common disadvantage of all processes is the problem of removing water from the reaction mixture. Evaporation of water followed by distillation of the free base is not safe. According to P. E. Frankenberg (Chem. Eng. News 60, 97/1982), 2-chloro-1,4-phenylenediamine is thermally unstable and an explosion is possible during distillation. Due to the high solubility of 2-chloro-1,4-phenylenediamine in water (11.5% at 20 ° C), it is also necessary to treat the mother liquors after product isolation by evaporation, which means energy consumption.
Izolace ve formě sulfátu 2-chlor-l,4-fenylendiaminu je sice možná (rozpustnost ve vodě 2,8 % při 20 °C), ale po usušení se problém přesunuje do následující výroby, kde je potřebaamin ve formě volné báze.Isolation in the form of 2-chloro-1,4-phenylenediamine sulphate is possible (water solubility 2.8% at 20 ° C), but after drying, the problem is transferred to the following production, where the free amine is needed.
Nyní bylo objeveno, že lze 2-chlor-l,4-fenylendiamin připravit přímo v chlorovaném organickém rozpouštědle s výhodou v o-dichlorbenzenu a po oddělení a odstavení vody destilačně se nechá roztok 2-chlor-l,4-fenylendiaminu přímo použít ve výrobě organických pigmentů. Vynález je založen na skutečnosti, že při podmínkách hydrogenace na platinovém katalyzátoru nedochází k dechloraci rozpouštědla. Plynovou chromatografií byly zjištěny jen stopy níže chlorovaných látek.It has now been discovered that 2-chloro-1,4-phenylenediamine can be prepared directly in a chlorinated organic solvent, preferably o-dichlorobenzene, and after separation and removal of the water by distillation, the 2-chloro-1,4-phenylenediamine solution can be used directly in the production organic pigments. The invention is based on the fact that under hydrogenation conditions on a platinum catalyst there is no dechlorination of the solvent. Only traces of lower chlorinated substances were found by gas chromatography.
Jako suroviny lze použít-2-chlor-4-nitroanilin ve formě vodné pasty (30 až 80 % sušiny) nebo v suchém stavu.As raw materials, 2-chloro-4-nitroaniline can be used in the form of an aqueous paste (30-80% dry matter) or in the dry state.
iand
Z chlorovaných rozpouštědel je preferován o-dichlorbenzen, ev. chlorbenzen, a to jak v čisté formě, tak v technické kvalitě s přítomností p- a m-dichlorbenzenu.Of the chlorinated solvents, o-dichlorobenzene, resp. chlorobenzene, both in pure form and in technical quality, in the presence of p- and m-dichlorobenzene.
AAND
Katalyzátorem je platina nanesená na aktivním uhlí v koncentraci 1 % Pt ve formě 50 % vodné pasty.The catalyst is platinum deposited on activated carbon at a concentration of 1% Pt in the form of a 50% aqueous paste.
CS 273 921 BlCS 273 921 Bl
Rezultuje 4 až B-% roztok 2-chlor-l,4-fenylendiaminu v rozpouštědle. Obsah báze ve vodné vrstvě se pohybuje v rozmezí 4 až 9 %. Výtěžek procesu je 93 až 94% 2-chlor-l,4-fenylendiaminu vztaženo na nasazený 2-chlor-4-nitroanilin..5 až 6 % báze odchází v oddělené vodné vrstvě. Zahuštěním roztoku je možno izolovat 2-chlor-l,4-fenylendiamin ve formě 60 až 70 % pasty.This resulted in a 4 to B-solution of 2-chloro-1,4-phenylenediamine in a solvent. The base content of the aqueous layer is between 4 and 9%. The yield of the process is 93-94% of 2-chloro-1,4-phenylenediamine based on the 2-chloro-4-nitroaniline used. 5-6% of the base leaves in a separate aqueous layer. By concentrating the solution, 2-chloro-1,4-phenylenediamine can be isolated as a 60-70% paste.
Následující příklady vysvětlují uvedený postup.The following examples explain the procedure.
Příklad 1Example 1
Do 0,5 1 autoklávu se předložilo 385 g o-dichlorbenzenu, 33,3 g 77% vodné pasty 2-chlor-4-nitroanilinu (0,15 mol) a 0,24 g 50% pasty platinového katalyzátoru na aktivním uhlí (1% Pt). Hydrogenace proběhla za míchání při teplotě 75 °C, za tlaku 4 MPa po dobu 2 h. Katalyzátor se separoval filtraci za sníženého tlaku a organická vrstva se oddělila v děličce od horní vodné fáze. Získalo se 398 g organické vrstvy s obsahem 5,2 % hmot. 2-chlor-l,4-fenylendiaminu a 8,6 g vodné vrstvy s obsahem 8,7 % báze.A 0.5 L autoclave was charged with 385 g o-dichlorobenzene, 33.3 g 77% aqueous 2-chloro-4-nitroaniline paste (0.15 mol) and 0.24 g 50% platinum catalyst on carbon % Pt). The hydrogenation was carried out with stirring at 75 ° C, under 4 MPa for 2 h. The catalyst was separated by filtration under reduced pressure and the organic layer was separated in a separator from the upper aqueous phase. 398 g of an organic layer with a 5.2 wt. 2-chloro-1,4-phenylenediamine and 8.6 g of an aqueous layer containing 8.7% base.
Výtěžek činil 96,7 %. Organická fáze obsahovala 0,01 % p-fenylendiaminu, stopy nezreagovaného 2-chlor-4-nitroanilinu a 0,04 % vody.The yield was 96.7%. The organic phase contained 0.01% p-phenylenediamine, traces of unreacted 2-chloro-4-nitroaniline and 0.04% water.
Příklad 2 Do 0,5 1 autoklávu se navážilo 325 g o-dichlorbenzenu, 105 g 77% vodné pasty 2-chlor-4nitroanilinu (0,47 mol) a 0,74 g 50% pasty platinového katalyzátoru (1% Pt) na aktivním uhlí. Reakce se uskutečnila při teplotě 75 °C tlaku vodíku 4 MPa po dobu 2 h. Po skončení reakce se katalyzátor odfiltroval na skleněné fritě. Filtrát se ochladil na 25 °C a ponechal se do druhého dne. Ze suspenze se separovala 50% o-dichl'orbenzenová pasta 2-chlor-l,4-fenylendiaminu o hmotnosti 99 g. Výtěžek 73,9 %, vztaženo na nasazený 2-chlor-4-nitroanilin.Example 2 325 g of o-dichlorobenzene, 105 g of 77% aqueous 2-chloro-4-nitroaniline paste (0.47 mol) and 0.74 g of 50% platinum catalyst paste (1% Pt) were weighed into a 0.5 L autoclave on an active coal. The reaction was carried out at 75 ° C hydrogen pressure of 4 MPa for 2 h. After completion of the reaction, the catalyst was filtered off on a glass frit. The filtrate was cooled to 25 ° C and left until the next day. 50% o-dichlorobenzene paste of 2-chloro-1,4-phenylenediamine weighing 99 g was separated from the slurry. Yield 73.9% based on 2-chloro-4-nitroaniline employed.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS230889A CS273921B1 (en) | 1989-04-14 | 1989-04-14 | Method of 2-chloro-1,4-phenylendiamine preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS230889A CS273921B1 (en) | 1989-04-14 | 1989-04-14 | Method of 2-chloro-1,4-phenylendiamine preparation |
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| Publication Number | Publication Date |
|---|---|
| CS230889A1 CS230889A1 (en) | 1990-08-14 |
| CS273921B1 true CS273921B1 (en) | 1991-04-11 |
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| Application Number | Title | Priority Date | Filing Date |
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| CS230889A CS273921B1 (en) | 1989-04-14 | 1989-04-14 | Method of 2-chloro-1,4-phenylendiamine preparation |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2547264C1 (en) * | 2013-08-07 | 2015-04-10 | Общество с ограниченной ответственностью "Фенил" (ООО "Фенил") | Method of producing chlorine-substituted phenylenediamines |
-
1989
- 1989-04-14 CS CS230889A patent/CS273921B1/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2547264C1 (en) * | 2013-08-07 | 2015-04-10 | Общество с ограниченной ответственностью "Фенил" (ООО "Фенил") | Method of producing chlorine-substituted phenylenediamines |
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| Publication number | Publication date |
|---|---|
| CS230889A1 (en) | 1990-08-14 |
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