CS268748B1 - Method of 2-ethylaniline production - Google Patents
Method of 2-ethylaniline production Download PDFInfo
- Publication number
- CS268748B1 CS268748B1 CS886096A CS609688A CS268748B1 CS 268748 B1 CS268748 B1 CS 268748B1 CS 886096 A CS886096 A CS 886096A CS 609688 A CS609688 A CS 609688A CS 268748 B1 CS268748 B1 CS 268748B1
- Authority
- CS
- Czechoslovakia
- Prior art keywords
- ethylaniline
- production
- ethylnitrobenzene
- purity
- hydrazine
- Prior art date
Links
- MLPVBIWIRCKMJV-UHFFFAOYSA-N 2-ethylaniline Chemical compound CCC1=CC=CC=C1N MLPVBIWIRCKMJV-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- 238000000034 method Methods 0.000 title description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000009835 boiling Methods 0.000 claims abstract description 4
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 6
- 239000007868 Raney catalyst Substances 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 4
- PXWYZLWEKCMTEZ-UHFFFAOYSA-N 1-ethyl-2-nitrobenzene Chemical compound CCC1=CC=CC=C1[N+]([O-])=O PXWYZLWEKCMTEZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 7
- 239000011541 reaction mixture Substances 0.000 abstract description 3
- 239000013543 active substance Substances 0.000 abstract description 2
- 150000001412 amines Chemical class 0.000 abstract description 2
- -1 2-ethylnitrobenzene hydrazine Chemical compound 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 229910052759 nickel Inorganic materials 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- IXQGCWUGDFDQMF-UHFFFAOYSA-N 2-Ethylphenol Chemical compound CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 244000309464 bull Species 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052742 iron Inorganic materials 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
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
2-ethylanilin je důležitý meziprodukt výroby biologicky aktivních látek. Tento amin se jednoduSe vyrábí tak, že se 2-ethylnitrobenzen redukuje hydrazinem v ethanolu v přítomnosti katalytického množství Raneyova niklu v rozmezí teplot 40 C až teplota varu reakční směei.2-ethylaniline is an important intermediate biologically active substances. This amine is simply produced by reducing the 2-ethylnitrobenzene hydrazine in ethanol in the presence catalytic amount of Raney of nickel in the temperature range of 40 ° C to temperature boiling reaction mixture.
Description
CS 268748 B1 1CS 268748 B1 1
Vynález se týká způsobu výroby 2-ethylanilinu. Tato sloučenina je známá, a předsta-vuje důležitý meziprodukt výroby biologicky aktivních látek. V literatuře je popsána řada způsobů přípravy 2-ethylanilinu. Tento amin je přístup-ný z 2-ethylnltrobenzenu redukcí cínem nebo železem v kyselém prostředí (Cline, Reid: J. Amer. Chem. Soc. 49, 3150 (1927); Bull. Soc. Chim. France /3/ 11. 208; DDR Pat. 89848)nebo hydrogenací na platině nebo Raneyově niklu (Vavon Mitchovitch: Bull. Soc. Chim.France /4/ 45 962; Birch, Dean, Fidler, Lowry: J. Amer, Chem Soc. 71, 1362 (1949), neboelektrochemickou redukcí za kontrolovaného potenciálu na Cu(Hg) katodě (Pesheva: Farma-cija (Sofia) Ji, 18 (1983)). 2-Ethylanilin se dále vyrábí podle patentové literaturybuá alkylaeí anilinu ethylenem v přítomnosti katalysátorů za vysokých teplot a tlaků(U.S. Pat. 3649693 a 3862233), nebo reakcí 2-ethylfenolu s amoniakem za vysokých teplotv přítomnosti kovů (např. Ru, Rh, Pt, Pd) na vhodných nosičích (Eur. Pat. Appl. EP 53696a 53819)· Nevýhody postupů spočívají převážně v technologické náročnosti procesů, použí-vání vysokých teplot, ale i někdy v nízkých výtěžcích.The present invention relates to a process for the preparation of 2-ethylaniline. This compound is known and represents an important intermediate in the production of biologically active substances. A number of methods for preparing 2-ethylaniline are described in the literature. This amine is accessible from 2-ethylntrobenzene by reduction with tin or iron in an acid medium (Cline, Reid: J. Amer. Chem. Soc. 49, 3150 (1927); Bull. Or DDR Pat. No. 89848) or by hydrogenation on platinum or Raney nickel (Vavon Mitchovitch: Bull. Soc. Chim. or by electrochemical reduction under controlled potential on Cu (Hg) cathode (Pesheva: Farm-cija (Sofia) Ji, 18 (1983)). (US Pat. No. 3649693 and 3862233), or by reacting 2-ethylphenol with ammonia at high temperatures in the presence of metals (e.g., Ru, Rh, Pt, Pd) on suitable carriers (Eur. Pat. Appl. predominantly in the technological demands of processes, the use of high temperatures, but sometimes sometimes in low yields ch.
Uvedené nevýhody odstraňuje způsob výroby 2-ethylanilinu podle.vynálezu, jehož pod-stata spočívá v tom, že se 2-ethylnitrobenzen redukuje hydrazinem v přítomnosti maxi-málně 10% Raneyova niklu jako katalysátorů, v prostředí ethanolu v rozmezí teplot 40 °Caž teplota varu reakční směsi.The above-mentioned disadvantages are eliminated by the process for the preparation of 2-ethylaniline according to the invention, wherein the 2-ethylnitrobenzene is reduced with hydrazine in the presence of a maximum of 10% Raney nickel as catalyst, in an ethanol environment at a temperature of 40 ° to a boiling point reaction mixture.
Průběh redukce se sleduje pomocí TLC, a po ukončeni redukce se směs zpracuje jedno-duše tak, že se katalysátor odfiltruje a rozpouštědlo se odpaří ve vakuu, nebo oddesti-luje za normálního tlaku. Již takto získaný surový 2-ethylanilin má čistotu minimálně98%, a jeho výtěžek přesahuje 90%,teorie. Destilací se zvýěí čistota produktu na mini-málně 99%.The course of the reduction is monitored by TLC, and after completion of the reduction, the mixture is worked up by simple filtration of the catalyst and evaporation of the solvent in vacuo or distillation under normal pressure. The crude 2-ethylaniline thus obtained has a purity of at least 98%, and its yield exceeds 90%, the theory. By distillation, the purity of the product is increased to at least 99%.
Zjistili jsme, že 2-ethylanilin je možno vyrábět ve vysokém výtěžku a čistotě jed-noduchým způsobem, který je technologicky nenáročný a nevyžaduje ani použití drahých ka-talysátorů.We have found that 2-ethylaniline can be produced in high yield and purity in a simple manner, which is not technologically demanding and does not require the use of expensive catalysts.
Redukci je možno provádět i za laboratorní teploty, nebo v nepřítomnosti Ra-Ni zacenu neúměrně delších reakčních časů. Následující příklady pouze ilustrují, avSak nikterak neomezují obecnost způsobuvýroby podle vynálezu. Příklad 1 K roztoku 15,1 g (0,1 mol) 2-ethylnitrobenzenu v 150 ml ethanolu se přidá 12 ml (0,37mol) 80% hydrátu hydrazinu a po zahřátí na 50 °C se přidá 0,2 g Raneyova niklu. Poodeznění silného pěnění se reakční směs zahřívá k varu 2 h. Potom se směs ochladl, kata-lysátor se odfiltruje a rozpouštědlo se odpaří ve vakuu. Získá se 11,52 g (95,1 %) 2-ethylanilinu s čistotou 98,6 % (GLC). Redestilací ve vakuu (teplota varu 96-97°C/l,46kPa) se získá 2-ethylanilin o čistotě 99,6 % ve výtěžku 91,4 % teoretického množství. Příklad 2The reduction can also be carried out at room temperature, or in the absence of Ra-Ni, starting disproportionately longer reaction times. The following examples illustrate, but do not limit, the generality of the process of the invention. EXAMPLE 1 To a solution of 15.1 g (0.1 mol) of 2-ethylnitrobenzene in 150 ml of ethanol was added 12 ml (0.37 mol) of 80% hydrazine hydrate and after heating to 50 DEG C., 0.2 g of Raney nickel was added. After heavy foaming, the reaction mixture was heated to boiling for 2 h. The mixture was cooled, the catalyst was filtered off and the solvent was evaporated in vacuo. There were obtained 11.52 g (95.1%) of 2-ethylaniline with a purity of 98.6% (GLC). Redistillation in vacuo (b.p. 96-97 ° C / 1.46kPa) gave 2-ethylaniline with a purity of 99.6% in a yield of 91.4% of theoretical. Example 2
Postupem podle příkladu 1, s tím rozdílem, že se použije 10% Raneyova niklu a reakce seprovádí při teplotě 40 °C, přičemž průběh redukce se sleduje TLC na silikagelu se získásurový 2-ethylanilin ve výtěžku 94,4 % a s čistotou 98,1 % dle plynové chromatografie.Following the procedure of Example 1, except that 10% Raney nickel is used and the reaction is carried out at 40 ° C, the reduction is monitored by TLC on silica gel, yielding 2-ethylaniline in 94.4% yield and 98.1% purity. by gas chromatography.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS886096A CS268748B1 (en) | 1988-09-12 | 1988-09-12 | Method of 2-ethylaniline production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS886096A CS268748B1 (en) | 1988-09-12 | 1988-09-12 | Method of 2-ethylaniline production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CS609688A1 CS609688A1 (en) | 1989-07-12 |
| CS268748B1 true CS268748B1 (en) | 1990-04-11 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS886096A CS268748B1 (en) | 1988-09-12 | 1988-09-12 | Method of 2-ethylaniline production |
Country Status (1)
| Country | Link |
|---|---|
| CS (1) | CS268748B1 (en) |
-
1988
- 1988-09-12 CS CS886096A patent/CS268748B1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CS609688A1 (en) | 1989-07-12 |
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