CS232775B1

CS232775B1 - Process for producing 3-methyl-4-nitroenol

Info

Publication number: CS232775B1
Application number: CS517682A
Authority: CS
Inventors: Peter Hauskrecht; Jan Bena; Frantisek Rajnoha; Karol Fancovic; Jan Vanek
Original assignee: Peter Hauskrecht; Jan Bena; Frantisek Rajnoha; Karol Fancovic; Jan Vanek
Priority date: 1982-07-07
Filing date: 1982-07-07
Publication date: 1985-02-14

Abstract

Účelom vynálezu je výroba 3-metyl-4-nitrofenůlu pri čiastočnej recyklácii matečnej minerálnej kyseliny. 3-metyl-4-nitrofenol sa připravuje z 3-metylfenolu nitrozáciou a následnou oxidáciou nitrózoderivátu na 3-metyl-4-nitrofenol. Matečná kyselina sa použije na přípravu kyseliny pre dalšiu nitrozáciu. V recyklujúcej kyselině sa zníži obsah kyseliny dusičnej denitráciou. Vynález najde uplatnenie pri výrobě 3- -metyl-4-nitrofenolu, ktorý sa používá ako medziprodukt pri výrobě pesticidov.The purpose of the invention is the production of 3-methyl-4-nitrophenol with partial recycling of the parent mineral acid. 3-Methyl-4-nitrophenol is prepared from 3-methylphenol by nitrosation and subsequent oxidation of the nitroso derivative to 3-methyl-4-nitrophenol. The mother acid is used to prepare the acid for further nitrosation. The nitric acid content in the recycle acid is reduced by denitration. The invention finds application in the production of 3-methyl-4-nitrophenol, which is used as an intermediate in the production of pesticides.

Description

Vynález sa týká výroby 3-metyl-4-nitrofemolu používaného ako medziprodukt pre prí, právu organofosfátových insekticídov, najma, O,O-dimetyl-O- (3-metyl-4-nitrof enyl j -tiofosfátu.The invention relates to the preparation of 3-methyl-4-nitrophemol used as an intermediate for the preparation of organophosphate insecticides, in particular O, O-dimethyl-O- (3-methyl-4-nitrophenyl) thiophosphate.

Najčastejšie sa 3-metyl-4-nitrofenol připravuje dvojstupňové nitrozáciou 3-metylfenolu a oxidáciou 3-mstýl-4-nitrózofenolu kyselinou dusičnou. Pri nitrizácii s HNO3 vznikajú okrem želaného 3-metyl-4-nitrofenolu aj ďalšie izoméry znižujúce výťažok. Známa je příprava 3-meíyl-4-nitrofenolu reakciou metatoluidínu s dusitanom sodným v přítomnosti kyseliny sírovej. Ďalej sa 3-metyl-4-nitrofenol připravuje nitrozáciou 3-metylfenolu s kyselinou dusitou a následnou oxidáciou 3-metyl-4-nitrózofenolu na 3-metyl fenol v prostředí kyseliny sírovej (Bridge Morgan, J. Am. Chem. Soc. 20, 766, /1898/, v prostředí koncentrovanej kyseliny sírovej (US pat. l,'50.2, 849). Oxidácia 3-metyl-4-nitrózofenolu sa uskutočňuje kyselinou dusičnou (Koelsch, J. Am. Chem. Soc. BS, 2019, 1944), (csl. pat. 140 179) a (CSSR AO 149 726). Oxidácia 3-metyl-4-nitrózofenolu peroxidom vodíka v alkalickom prostředí je popísaná v Travagli, Chem. Abstr. 45, 7594 e /1951/).Most commonly, 3-methyl-4-nitrophenol is prepared by two-step nitrosation of 3-methylphenol and oxidation of 3-methyl-4-nitrosophenol with nitric acid. In addition to the desired 3-methyl-4-nitrophenol, nitrization with HNO3 also yields other isomers which reduce the yield. It is known to prepare 3-methyl-4-nitrophenol by reacting metatoluidine with sodium nitrite in the presence of sulfuric acid. Further, 3-methyl-4-nitrophenol is prepared by nitrosating 3-methylphenol with nitrous acid and then oxidizing 3-methyl-4-nitrosophenol to 3-methyl phenol in sulfuric acid (Bridge Morgan, J. Am. Chem. Soc. 20, 766, (1898), in concentrated sulfuric acid (US Pat. 1, 50, 2, 849) The oxidation of 3-methyl-4-nitrosophenol is carried out with nitric acid (Koelsch, J. Am. Chem. Soc. BS, 2019, 1944), (csl. Pat. 140 179) and (CSSR AO 149 726) The oxidation of 3-methyl-4-nitrosophenol with hydrogen peroxide in an alkaline medium is described in Travagli, Chem. Abstr. 45, 7594 e (1951).

Nevýhodou daných postupov je spotřeba velkého množstva minsrálnych kyselin, predovšetkým kyseliny sírovej. Po oddělení 3-metyl-4-nitrofenolu sa zrisdené minerálně kyseliny odvádzajú do odpadových vod.A disadvantage of these processes is the consumption of large amounts of minsral acids, especially sulfuric acid. After separation of the 3-methyl-4-nitrophenol, the precipitated mineral acids are discharged to waste water.

Vyššie uvedené nedostatky sú odstránené sposobom výroby 3-metyl-4-nitrofenolu, podstata ktorého spočívá v tom, že sa nitrózuje s NaNCk v prostředí kyseliny sírovej a vzniknutý 3-metyl-4-nitrózofenol sa oxiduje kyselinou dusičnou na 3-metyl-4-nitrofenol, ktorý sa od matečného roztoku oděli.The above-mentioned drawbacks are overcome by the process of producing 3-methyl-4-nitrophenol, which consists in nitrosating with NaNCk in sulfuric acid and oxidizing the resulting 3-methyl-4-nitrosophenol to 3-methyl-4- nitrophenol separated from the mother liquor.

Na přípravu kyseliny sírovej sa použije matečná kyselina sírová z predchádzajúcej nitrozácie a nitráeie v množstve 5 až 50 % hmot. z celkového množstva potrebnej kyseliny sírovej, s výhodou so zníženým obsahom kyseliny dusičnej. Zníženie obsahu kyseliny dusičnej sa dosiahne Paulingovým prístrojom, alebo přídavkem močoviny. Výsledná koncentrácia kyseliny dusičnej je max. 0,2 % hmot. a 3-metyl-4-nitrofenolu max. 100 mg/1.For the preparation of sulfuric acid, the parent sulfuric acid from the previous nitrosation and nitration is used in an amount of 5 to 50% by weight. % of the total amount of sulfuric acid required, preferably with a reduced nitric acid content. Reduction of nitric acid content is achieved by Pauling apparatus or by addition of urea. The final concentration of nitric acid is max. and 3-methyl-4-nitrophenol max 100 mg / L.

Výhodou sposobu podlá vynálezu je až o 50 % menšia spotřeba kyseliny sírovej pri výrobě 3-metyl-4-nitrózofenolu, například v porovnaní s CSSR AO 149 726. Použitie kyseliny sírovej je obmedzené výslednou koncentráciou kyseliny sírovej použitej na nitrozáciu a možnosťou kryštalizácie hydrogénsíranu sodného z nej. Po odfiltrovaní 3-metyl-4-nitrofenolu sa odpadná kyselina sírová ďalej nevyužívá a odchádza do kanalizácie. Vynález zlepšuje ekonomiku procesu a zlepšuje kvalitu odpadných vod, pričom ich množstvo a kvalita je na jednotku produkcie lepšia ako dosial.An advantage of the process according to the invention is up to 50% less consumption of sulfuric acid in the production of 3-methyl-4-nitrosophenol, for example compared to CSSR AO 149 726. The use of sulfuric acid is limited by the resulting concentration of sulfuric acid used for nitrosation and nej. After filtering off the 3-methyl-4-nitrophenol, the waste sulfuric acid is no longer used and is discharged into the sewer. The invention improves the economy of the process and improves the quality of the wastewater, the quantity and quality of which are better than the production units per unit of production.

Příklad 1Example 1

Zmes 485 g 60%-nej kyseliny sírovej a 49 g 3-metylfenolu sa ochladila na 0 °C a npočas jednej hodiny ssa za intenzívneho miešania přidalo 100 g 37%-ného vodného roztoku dusitanu sodného tak, aby teplota nepřekročila 5 ^CC. Po pol hodině miešania sa přidá 320 g 9%-nej kyseliny dusičnej pri teplote 35 až 45 °C po dobu 2 hodin.A mixture of 485 g of 60% sulfuric acid and 49 g of 3-methylphenol was cooled to 0 ° C and 100 g of 37% aqueous sodium nitrite solution was added with vigorous stirring over one hour so that the temperature did not exceed 5 ^° C. 320 g of 9% nitric acid are added at 35-45 ° C for 2 hours.

Zmes sa mieša ešte 1 hodinu, vzniknutý 3-metyl-4-nitrofenol sa odfiltruje a premyje vodou. Získá sa 112 g 3-metyl-4-niti’ofenolu o koncentrácii 52,1 % hmot., ktorý je vhodný na přípravu 3-metyl-4-nitrofenolátu sodného. Odfiltrovaná matečná kvapalina v množstve 816 ml obsahovala 29,1 % hmot. kyseliny sírovej, 1,2 % hmot. kyseliny dusičnej, 6,8 % hmot. kyselého síranu sodného, popritom koncentrácia 3-metyl-4-nitrofenolu bola 1440 mg/1 a 3-metylfenolu 1260 mg/1.After stirring for 1 hour, the resulting 3-methyl-4-nitrophenol was filtered off and washed with water. 112 g of 3-methyl-4-nitro-phenol having a concentration of 52.1% by weight, which is suitable for the preparation of sodium 3-methyl-4-nitrophenolate, are obtained. The filtered mother liquor in an amount of 816 ml contained 29.1 wt. % sulfuric acid, 1.2 wt. % nitric acid, 6.8 wt. sodium sulfate, the concentration of 3-methyl-4-nitrophenol was 1440 mg / l and 3-methylphenol 1260 mg / l, respectively.

Příklad 2 'Postupovalo sa ako v příklade 1 s tým rozdielom, že sa 485 g 60,2 % hmot. kyseliny sírovej připravilo zmiešaním 29,1 % hmotnostných kyseliny sírovej z matečnej kvapaliny z pokusu 1, v ktorej sa znížil obsah 3-metylfenolu, 3-metyl-4-nitrofenolu a kondenzačných a oxidačných produktov čistěním adsorpciou na aktívnom uhlí, pričom obsah 3-metyl-4-nitrofenolu bol 117 mg/1 -a 70 % hmot. kyseliny sírovej získanej pri výrobě koncentrovanej kyseliny dusičnej. Získalo sa 114 g 2-metyl-4-nitrofenolu o koncentrácii.51,4 ·.% hmot. Obsah-3.-metyl-4řnitrofenolu v kyselině ;sírovej 450, odfiltrovaní 3-metyl-4-nitrofenolu bol 1420 mg/1. ..EXAMPLE 2 The procedure of Example 1 was followed except that 485 g of 60.2 wt. of sulfuric acid by mixing 29.1% by weight of sulfuric acid from the mother liquor of Experiment 1, in which the content of 3-methylphenol, 3-methyl-4-nitrophenol and the condensation and oxidation products was reduced by purification by adsorption on activated carbon, -4-nitrophenol was 117 mg / l and 70 wt. sulfuric acid obtained in the manufacture of concentrated nitric acid. 114 g of 2-methyl-4-nitrophenol having a concentration of 51.4% by weight were obtained. The content of 3-methyl-4-nitrophenol in sulfuric acid 450, the filtered 3-methyl-4-nitrophenol was 1420 mg / l. ..

P r í.k La d 3Example 3

Postupovalo ?sa podlá .příkladu ,1 s tým rozdielom, že sa dBS .g.60%^] kyseliny .sírovej připravilo zmiešaním J.23,9 g.kyseliny sírovej o koncentrácii,294 % .hmot. z matečné j kyseliny z pokusu 1,,pričom koncentrácia v nej obsiahnntej .kyseliny dusičnej bola znížená Paulingovým prístrajora ,z, póvodných 1,2 % hmot. na 0,15 °/o hmot., koncentrácia S-metýl-á-nitrofenolu sa znížila na 900 mg/1 a 3-metylfenolu na 830 mg/1 aThe procedure was as described in Example 1, except that dBS 60% sulfuric acid was prepared by mixing J 23.9 g of sulfuric acid at a concentration of 294% w / w. from the parent acid of Experiment 1, wherein the concentration of nitric acid contained therein was reduced by the Pauling treatment, from the original 1.2 wt. to 0.15% w / w, the concentration of S-methyl-α-nitrophenol was reduced to 900 mg / l and 3-methylphenol to 830 mg / l, and

361,1 g kyseliny sírovej o koncentrácii 70^6 percenta hmot. získanej pri výrobě koncentrovanej kyseliny dusičnej, obsahu-júcej 0,2 percenta hmot. kyseliny dusičnej. Získalo sa 117 g 3-metyl-4-nitrofenolu o koncentrácii 51,5 % hmot. Obsah 3-metyl-4-.nitrofenplu v matečnej kyselině sírovej bol 1140 mg/ /liter.361.1 g of sulfuric acid having a concentration of 70% by weight. % obtained by the production of concentrated nitric acid containing 0.2 wt. nitric acid. 117 g of 3-methyl-4-nitrophenol having a concentration of 51.5% by weight were obtained. The content of 3-methyl-4-nitrophenplu in the parent sulfuric acid was 1140 mg / l.

P r í k 1 a d 4Example 1 4

Postupovalo sa podlá příkladu 1 s tým roz232775 dielom, že na přípravu 485 g 60%-nej kyseliny sírovej sa použila matečná kvapalina z příkladu 3 po znížení obsahu kyseliny dusičnej z 1,8 °/o hmot. denitráciou na 0,18 % hmot. Získalo sa 112 g 3-metyl-4-nitrofenolu o koncentrácii 52,4 % hmot. Trojnásobným opakováním tohto postupu sa získalo 110, 119 a 113 g 3-metyl-4-nitrofenolu o koncentrácii 53,4; 51,9 a 52,4 % hmot. Koncentrácia 3-metyl-4-nitrofenolu v kyselině sírovej po odfiltrovaní 3-metyl-4-nitrofenolu bola 790, 740 a 765 mg/1.The procedure of Example 1 was followed with the exception that the mother liquor of Example 3 was used to prepare 485 g of 60% sulfuric acid after reducing the nitric acid content by 1.8% by weight. denitration to 0.18 wt. 112 g of 3-methyl-4-nitrophenol having a concentration of 52.4% by weight were obtained. Repeating this procedure three times gave 110, 119 and 113 g of 53.4 3-methyl-4-nitrophenol; 51.9 and 52.4 wt. The concentration of 3-methyl-4-nitrophenol in sulfuric acid after filtration of 3-methyl-4-nitrophenol was 790, 740 and 765 mg / l.

Příklad 5Example 5

Postupovalo sa podlá příkladu 2 s 'tým rozdielom, že na přípravu 485 g kyseliny sírovej o koncentraci 60 % hmot. sa použila komerčná kyselina sírová o koncentrácii 96 percent hmot. v množstve 224 g a matečná kyselina z pokusu 1 obsahujúca 29,1 % hmot. kyseliny sírovej v množstve 261 g. Získalo· sa 148 g 3-metyl-4-nitrofenolu o koncentrácii 40,2 % hmot. znečistěného krystalickým hydrogénsíranom sodným.The procedure of Example 2 was followed except that for the preparation of 485 g of 60% by weight sulfuric acid. 96% by weight of commercial sulfuric acid was used. in an amount of 224 g and the parent acid of Experiment 1 containing 29.1 wt. of sulfuric acid in an amount of 261 g. 148 g of 3-methyl-4-nitrophenol having a concentration of 40.2% by weight were obtained. contaminated with crystalline sodium bisulfate.

Příklad 6Example 6

Postupovalo sa podfa příkladu 2 s tým rozdielom, že na přípravu 485 g kyseliny sírovej o koncentrácii 60 % hmot. sa použila odpadná kyselina sírová odpadajúca pri premývaní 3-metyl-4-nitrofenolu vodou o zložení 5,1 % hmot. kyseliny sírovej; 0,1 % hmot. kyseliny dusičnej, obsahujúca 540 mg/1 3-metyl-4-nitrofenolu. Získalo sa 114 g 3-metyl-4-nitrofenolu o koncentrácii 51,6 % hmot.The procedure of Example 2 was followed except that for the preparation of 485 g of 60% by weight sulfuric acid. Waste sulfuric acid was used, which was washed off with 3% methyl-4-nitrophenol with 5.1 wt. sulfuric acid; 0.1 wt. nitric acid containing 540 mg / L of 3-methyl-4-nitrophenol. 114 g of 3-methyl-4-nitrophenol having a concentration of 51.6% by weight were obtained.

Příklad 7Example 7

Postupovalo sa podfa příkladu 3 s týrh rozdielom, že sa 485 g 60 % kyseliny sírovej připravilo zmiešaním 123,9 g kyseliny sírovej o koncentrácii 29,1 % hmot. z matečnej kyseliny z pokusu 1, pričom koncentrácia v nej obsiahnutej kyseliny dusičnej bola znížená prídavkom 2 g močoviny z povodných 1,2 °/o hmot. na 0,18 % hmot., koncantrácia 3-metyl-4-nitrofenolu sa znížila na 975 mg/1 a 3-metylfenolu na 907 mg/1, a 361,1 gramov kyseliny sírovej o koncentrácii 70,6 percenta hmot. získanej pri výrobě koncentrovanej kyseliny dusičnej, obsahujúcej 0,2 percenta hmot. kyseliny dusičnej. Získalo sa 112 g 3-metyl-4-nitrofenolu o koncentráciiThe procedure of Example 3 was followed except that 485 g of 60% sulfuric acid was prepared by mixing 123.9 g of 29.1% sulfuric acid. from the parent acid of Experiment 1, the concentration of nitric acid contained therein was reduced by the addition of 2 g of urea from floods of 1.2% by weight. The concentration of 3-methyl-4-nitrophenol was reduced to 975 mg / l and 3-methylphenol to 907 mg / l, and 361.1 grams of 70.6 percent by weight sulfuric acid. % obtained in the manufacture of concentrated nitric acid containing 0.2 wt. nitric acid. 112 g of 3-methyl-4-nitrophenol were obtained at a concentration

52,1 % hmot. Obsah 3-metyl-4-.nitrofenolu v matečnej kyselině sírovej bol 1195 mg/1.52.1 wt. The content of 3-methyl-4-nitrophenol in the parent sulfuric acid was 1195 mg / l.

Vynález je možné použit pri výrobě 3-metýl-4-nitrofenolu, kde spotřeba kyseliny sírovej pri recyklácii je o 18 až 50 % nižšia ako pri klasickom postupe. Vzhladom k tomu, že v kyselině sírovej recykluje aj 3-metyl-4-nitrofenol a 3-metylfenol, je výťažok přibližné o 1 % vyšší. V kyselině sírovej, ktorá odpadla pri výrobě 3-metyl-4-nitrofenolu, stupa obsah NaHSO4, ktorý vysoluje 3-metyl-4-nitrofenol, takže jeho obsáh v nej klesá zhruba o 40 %. Týmto vzniká váčšia možnost využitia H2SO4 odpadajúcej pri výrobě 3-metyl-4-nitrofenolu vzhfadom k nižšiemu obsahu 3-metyl-4-nitrofenolu v nej. V případe výroby čistejšieho 3-metyl-4-nitrofenolu sa v recyklovanej H2SO4 móže obsah doprevádzajúcich polykondenzačných, oxidačných a iných nečistot znižovať čistěním, například adsorpciou na aktívnom uhlí.The invention can be used in the production of 3-methyl-4-nitrophenol, where the consumption of sulfuric acid in recycling is 18 to 50% lower than in the conventional process. Since 3-methyl-4-nitrophenol and 3-methylphenol are also recycled in sulfuric acid, the yield is approximately 1% higher. In the sulfuric acid which has been dropped in the production of 3-methyl-4-nitrophenol, the content of NaHSO4, which salts out 3-methyl-4-nitrophenol, is increased so that its content decreases by about 40%. This gives rise to a greater potential for the use of H2SO4, which is lost in the production of 3-methyl-4-nitrophenol, due to the lower 3-methyl-4-nitrophenol content. In the case of the production of purer 3-methyl-4-nitrophenol in recycled H2SO4, the content of accompanying polycondensation, oxidation and other impurities may be reduced by purification, for example by adsorption on activated carbon.

Claims

232775, using a mother liquor of Example 3 to prepare 485 g of 60% sulfuric acid after reducing the nitric acid content of 1.8% by weight. denitration to 0.18 wt. 112 g of 3-methyl-4-nitrophenyl was obtained with a concentration of 52.4% by weight. Repeating this procedure three times yielded 110, 119 and 113 g of 3-methyl-4-nitrophenol at a concentration of 53.4; 51.9 and 52.4 wt. Concentration of 3-methyl-4-nitrophenol in sulfuric acid after filtration of 3-methyl-4-nitrophenolbola 790, 740 and 765 mg / l. EXAMPLE 5 The procedure of Example 2 was followed with the difference that for the preparation of 485 g of 60% by weight sulfuric acid. sulfuric acid at a concentration of 96 percent by weight was used. 224 g and a mother acid of experiment 1 containing 29.1% sulfuric acid at 261 g. 148 g of 3-methyl-4-nitrophenol having a concentration of 40.2% by weight were obtained. contaminated with sodium bicarbonate. Example 6 Example 2 was followed, with the difference that for the preparation of 485 g of sulfuric acid at a concentration of 60 wt. the waste sulfuric acid used in the washing of 3-methyl-4-nitrophenol with water having a composition of 5.1% by weight was used. sulfuric acid; 0.1% by weight of nitric acid containing 540 mg / l of 3-methyl-4-nitrophenol. 114 g of 3-methyl-4-nitrophenol having a concentration of 51.6% by weight were obtained. EXAMPLE 7 Example 3 was followed with the difference that 485 g of 60% sulfuric acid was prepared by mixing 123.9 g of acidic acid at a concentration of 29.1% by weight. from the fatty acid of Experiment 1 wherein the concentration of nitric acid contained therein was reduced by the addition of 2 g of urea from an aqueous 1.2% by weight. to 0.18% by weight, the concen- tration of 3-methyl-4-nitrophenol was reduced to 975 mg / l and 3-methylphenol to 907 mg / l, and 361.1 g of sulfuric acid at 70.6 percent by weight. obtained in the manufacture of concentrated nitric acid containing 0.2% by weight of the product. nitric acid. 112 g of 3-methyl-4-nitrophenol having a concentration of 52.1% by weight were obtained. The content of 3-methyl-4-nitrophenol in mother sulfuric acid was 1195 mg / l. The invention can be used in the production of 3-methyl-4-nitrophenol, where the consumption of acidic acid by recycling is 18 to 50% lower than in the conventional process. Since 3-methyl-4-nitrophenol and 3-methylphenol are also recycled in sulfuric acid, the yield is approximately 1% higher. In sulfuric acid, which fell off in the production of 3-methyl-4-nitrophenol, the NaHSO4 content, which salts out 3-methyl-4-nitrophenol, is about 40%. This results in the possibility of using H 2 SO 4 in the production of 3-methyl-4-nitrophenol with respect to the lower content of 3-methyl-4-nitrophenol therein. the contents of the accompanying polycondensation, oxidation and other impurities can be reduced by purification, for example by adsorption on activated carbon. SUMMARY The process for the production of 3-methyl-4-nitrophenol by nitrosation of 3-methylphenol in an acidic medium followed by oxidation of the resulting 3-methyl-4-nitrosophenol with dilute acid-amide to 3-methyl-4-nitrophenol, which is separated from the parent acids, characterized by for the preparation of sulfuric acid, the parent acid of the above EMBODIMENT is used to nitrosate and oxidize in an amount of 5 to 50% by weight. of the total amount of sulfuric acid required - preferably with a reduced nitric acid content obtained by means of a Pauling apparatus, or by the addition of urea to a maximum of 0.2% by weight, and also with a reduced content of 3-me- teric acid; 4-nitrophenol max. 1000 mg / l.