CS215470B1 - Method of reduction of aromatic nitrosubstances - Google Patents
Method of reduction of aromatic nitrosubstances Download PDFInfo
- Publication number
- CS215470B1 CS215470B1 CS937480A CS937480A CS215470B1 CS 215470 B1 CS215470 B1 CS 215470B1 CS 937480 A CS937480 A CS 937480A CS 937480 A CS937480 A CS 937480A CS 215470 B1 CS215470 B1 CS 215470B1
- Authority
- CS
- Czechoslovakia
- Prior art keywords
- reduction
- aromatic
- methoxy
- methyl
- hydrazine hydrate
- Prior art date
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- 230000009467 reduction Effects 0.000 title claims description 13
- 238000000034 method Methods 0.000 title claims description 10
- 125000003118 aryl group Chemical group 0.000 title 1
- -1 aromatic nitro compounds Chemical class 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 150000002828 nitro derivatives Chemical class 0.000 claims description 3
- 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 6
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- BSFHJMGROOFSRA-UHFFFAOYSA-N 1,4-dimethyl-2-nitrobenzene Chemical group CC1=CC=C(C)C([N+]([O-])=O)=C1 BSFHJMGROOFSRA-UHFFFAOYSA-N 0.000 description 1
- NWPKEYHUZKMWKJ-UHFFFAOYSA-N 1-ethoxy-4-nitrobenzene Chemical compound CCOC1=CC=C([N+]([O-])=O)C=C1 NWPKEYHUZKMWKJ-UHFFFAOYSA-N 0.000 description 1
- PLAZTCDQAHEYBI-UHFFFAOYSA-N 2-nitrotoluene Chemical compound CC1=CC=CC=C1[N+]([O-])=O PLAZTCDQAHEYBI-UHFFFAOYSA-N 0.000 description 1
- QZYHIOPPLUPUJF-UHFFFAOYSA-N 3-nitrotoluene Chemical compound CC1=CC=CC([N+]([O-])=O)=C1 QZYHIOPPLUPUJF-UHFFFAOYSA-N 0.000 description 1
- ZPTVNYMJQHSSEA-UHFFFAOYSA-N 4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1 ZPTVNYMJQHSSEA-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Vynález se týká způsobu redukce aromatických nitrolátek obecného vzorce I, NOgThe invention relates to a process for the reduction of aromatic nitro compounds of the general formula I, NOg
kde X značí jeden ze substituentů metyl, etyl, metoxy nebo etoxy, a dále obecného vzorce II,wherein X is one of methyl, ethyl, methoxy or ethoxy, and of formula II,
kde X a Y značí substituent metyl nebo metoxy, hydrazinhydrátem. Této redukce je možno použít při syntéze mnoha barvářských polotovarů.wherein X and Y are methyl or methoxy, hydrazine hydrate. This reduction can be used in the synthesis of many dyeing products.
Dosud publikované způsoby redukce aromatických nitrolátek hydrazinhydrátem jsou prováděny v roztoku organických rozpouštědel za katalýzy Raney niklem, palladiem, platinou, železem nebo mědí při teplotách v rozmezí 20 °C až bodu varu použitého rozpouštědla. Nevýhodou těchto způsobů je používání nákladných katalyzátorů v případě platinových kovů a hlavně přítomnost organických rozpouštědel se všemi negativními důsledky. Z ostatních používaných redukcí je redukce vodíkem málo vhodná k použití při nízkotonážních výrobách obvyklých u barvářských polotovarů a často používaná klasická Běchampovská redukce je příliš pracná.Hitherto published methods for reducing aromatic nitro compounds by hydrazine hydrate are carried out in organic solvent solution under Raney catalysis with nickel, palladium, platinum, iron or copper at temperatures ranging from 20 ° C to the boiling point of the solvent used. The disadvantage of these processes is the use of expensive catalysts in the case of platinum metals and especially the presence of organic solvents with all the negative consequences. Of the other reductions used, hydrogen reduction is poorly suited for use in low tonnage products customary in dyeing semi-finished products, and the frequently used Bechampian reduction is too laborious.
Tyto nevýhody odstraňuje způsob redukce aromatických nitrolátek obecného vzorce I,These disadvantages are overcome by the method of reducing the aromatic nitro compounds of formula I,
kde X značí jeden ze substituentů metyl, etyl, metoxy nebo etoxy, a dále obecného vzorce II, kde X a Y značí substituent metyl nebo metoxy,; i hydrazinhydrátem za katalýzy Raney niklem, železem nebo mědí, spočívající v tom, že redukce se provádí v tavenině výchozí nitrolátky při teplotě 100 až 120 °C, s výhodou při 105 až 110 °C.wherein X is one of methyl, ethyl, methoxy or ethoxy, and of formula II wherein X and Y are methyl or methoxy; Hydrazine hydrate under Raney catalysis with nickel, iron or copper, characterized in that the reduction is carried out in the melt of the starting nitro compound at a temperature of 100 to 120 ° C, preferably at 105 to 110 ° C.
Nutnou podmínkou při tomto způsobu vedení redukce je teplota převyšující bod varu vody, aby · se v průběhu redukce odpařovala jak voda obsažená v redukčním činidle, tak i voda reakční. Z hlediska tepelné bilance je průběh redukce exotermní reakcí a vyžaduje ve větších objemech dobré míchání a chlazení.A prerequisite for this method of conducting the reduction is a temperature above the boiling point of water, so that during the reduction both the water contained in the reducing agent and the reaction water evaporate. In terms of heat balance, the reduction process is an exothermic reaction and requires good mixing and cooling in larger volumes.
Výsledkem redukce je tavenina finální aminolátky ve velmi dobré čistotě s obsahem katalyzátoru, který lze po oddělení znovu použít. Hlavním efektem tohoto způsobu redukce je nepoužití; organických rozpouštědel, protože výchozí nitrolátka sama o sobě vytváří dostatečně vhodné prostředí pro průběh redukce. Nepřítomnost organických rozpouštědel znamená zlevnění výroby ve fázi materiálových nákladů, snižuje spotřebu energií potřebných na oddělování aTegeneraci rozpouštědel a významné je i Snížení nároků na výrobní i zařízení z hlediska bezpečnosti a hygieny práce.The reduction results in a melt of the final amino compound in very good purity with a catalyst content which can be reused after separation. The main effect of this method of reduction is non-use; organic solvents since the starting nitro compound itself creates a sufficiently suitable environment for the reduction process. The absence of organic solvents means cheaper production in the material cost phase, reduces the energy consumption for separation and solvent regeneration, and it is also important to reduce production and equipment requirements in terms of safety and hygiene at work.
Příklady provedení PřikladlEXAMPLE 1
Do 0,5 1 Kellerovy baňky se čtyřmi hrdly bylo předloženo 137 g o-nitrotoluenu, 4 g práškového katalyzátoru, vloženo míchadlo, teploměr, připojen sestupný chladič a dávkovači čerpadlo ná hydrazinhydrát. Po vyhřátí na zvolenou teplotu bylo dávkováno 110 g hydrazinhydrátu po dobu 4 hodin, pokud ukončení vývoje dusíku z reakce neindikovalo konec redukce. Potom bylo nadávkováno ještě navíc cca 6 g hydrazinhydrátu a ponecháno za míchání ještě 1 hodinu. Po zastavení míchadla se nechal 15 minut sedimentovat kataly: zátor a produkt byl poté odtažen. Byl získáni ; výtěžek 94 % th.To a 0.5 L Keller four-necked flask was charged 137 g o-nitrotoluene, 4 g powder catalyst, a stirrer, a thermometer, a downstream condenser connected, and a metering pump for hydrazine hydrate. After heating to the selected temperature, 110 g of hydrazine hydrate was metered in over 4 hours, unless the completion of nitrogen evolution from the reaction indicated the end of the reduction. An additional 6 g of hydrazine hydrate was then metered in and left under stirring for 1 hour. After stopping the stirrer was allowed 15 minutes to settle catalytic: agents, and the product was then retracted. It was obtained; yield 94% th.
Příklady 2-6Examples 2-6
Postup byl shodný s příkladem 1, suroviny, hlavní technologické údaje a výtěžek jsou v následující tabulce:The procedure was identical to that of Example 1, the raw materials, the main process data and the yield being in the following table:
4.....4 .....
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS937480A CS215470B1 (en) | 1980-12-29 | 1980-12-29 | Method of reduction of aromatic nitrosubstances |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS937480A CS215470B1 (en) | 1980-12-29 | 1980-12-29 | Method of reduction of aromatic nitrosubstances |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CS215470B1 true CS215470B1 (en) | 1982-08-27 |
Family
ID=5444272
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS937480A CS215470B1 (en) | 1980-12-29 | 1980-12-29 | Method of reduction of aromatic nitrosubstances |
Country Status (1)
| Country | Link |
|---|---|
| CS (1) | CS215470B1 (en) |
-
1980
- 1980-12-29 CS CS937480A patent/CS215470B1/en unknown
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