CS221004B1 - Method of making the 2-methyl-4-chlorphenoles - Google Patents
Method of making the 2-methyl-4-chlorphenoles Download PDFInfo
- Publication number
- CS221004B1 CS221004B1 CS700781A CS700781A CS221004B1 CS 221004 B1 CS221004 B1 CS 221004B1 CS 700781 A CS700781 A CS 700781A CS 700781 A CS700781 A CS 700781A CS 221004 B1 CS221004 B1 CS 221004B1
- Authority
- CS
- Czechoslovakia
- Prior art keywords
- methyl
- chlorophenol
- cresol
- reaction mixture
- mother liquor
- Prior art date
Links
- 238000004519 manufacturing process Methods 0.000 title description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 28
- RHPUJHQBPORFGV-UHFFFAOYSA-N 4-chloro-2-methylphenol Chemical compound CC1=CC(Cl)=CC=C1O RHPUJHQBPORFGV-UHFFFAOYSA-N 0.000 claims description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 238000005660 chlorination reaction Methods 0.000 claims description 9
- 239000011541 reaction mixture Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 5
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 5
- 239000012452 mother liquor Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- -1 2-methyl-4-chlorophenyl Chemical group 0.000 description 1
- OQNJYFSATOQHSM-UHFFFAOYSA-N 6-chloro-3-hydroxy-2-methylbenzoic acid Chemical class CC1=C(O)C=CC(Cl)=C1C(O)=O OQNJYFSATOQHSM-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910006024 SO2Cl2 Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Vynález možno využit pri príprave 2-metyl-4-chlórfenoIu, ako organického medziproduktu, ako i pri výrobě chemikálií vysokej čistoty.The invention can be used in the preparation of 2-methyl-4-chlorophenyl as an organic intermediate as well as in the production of high purity chemicals.
Vynálezom je sposob výroby 2-metyl-4-chlórfenolu chloráciou o-krezolu pomocou SO2CI2 za použitia ZnCh ako katalyzátora.The present invention is a process for the preparation of 2-methyl-4-chlorophenol by chlorination of o-cresol with SO 2 Cl 2 using ZnCl 2 as a catalyst.
2-metyl-4-chlórfenol sa používá ako medziprodukt pri róznych organických syntézách resp. ako čistá chemikália pri analytickom stanovovaní chlórkrezolátov.2-Methyl-4-chlorophenol is used as an intermediate in various organic syntheses, respectively. as a pure chemical in the analytical determination of chlorocresolates.
Pódia dosial známých postupov sa 2-metyl-4-chlórfenol připravuje chloráciou o-krezolu. Například Sah. A; J. Am. Chem. Soc. 63 (3164) 1941 uvádza jeho přípravu chlóráciou o-krezolu, za použitia SO2CI2 ako chloračného média, pričom sa získává produkt v 81,5 % výtažku.According to known processes, 2-methyl-4-chlorophenol is prepared by chlorination of o-cresol. Sah. A; J. Am. Chem. Soc. 63 (3164) 1941 discloses its preparation by chlorination of o-cresol using SO 2 Cl 2 as the chlorinating medium to give the product in 81.5% yield.
Podl'a US patentu 2 777 002 (1957) sa 2-metyl-4-chlórfenol připravuje chloráciou 0-krezolu za použitia SO2CI2 ako chloračného média a FeCb ako katalyzátora. Proces chlorácie podl'a uvedeného patentu prebieha 17 hodin pri teplote +15 °C pri náběhu a 35 až 40 °C pri doreagovaní, pričom po destilaci! sa získal produkt 81,7 % výtažku. Množsvo katalyzátora nepresiahlo 1,5% hmotnosti nasadeného fenolu.According to U.S. Patent 2,777,002 (1957), 2-methyl-4-chlorophenol is prepared by chlorination of O-cresol using SO 2 Cl 2 as the chlorination medium and FeCl 3 as the catalyst. The chlorination process of this patent is carried out for 17 hours at a temperature of + 15 ° C on the inlet and 35 to 40 ° C in the post-distillation. 81.7% yield. The amount of catalyst did not exceed 1.5% by weight of the phenol employed.
Zistili šme, že 2-metyl-4-chlórfenol vysokej čistoty možno vyrobit’ chloráciou o-krezolu prostredníctvom SO2CI2 za katalytického posobenia ZnCÍ2.We also found that 2-methyl-4-chlorophenol of high purity can be produced by chlorination of o-cresol with SO2Cl2 with catalytic ZnCl2.
ŽnCl2 sa přidává v množstve 0,1 až 5 % hmot., vtahované na hmotnost' o-krezolu. Pridávanie SO2CI2 do o-krezolu sa uskutočňuje pri teplotách 20 až 65 °C, z výhodou 40 až 65 °C, pričom prekročenie teploty 65 °C sa nedoporučuje.ZnCl2 is added in an amount of 0.1 to 5% by weight, based on the weight of o-cresol. The addition of SO 2 Cl 2 to o-cresol is carried out at temperatures of 20 to 65 ° C, preferably 40 to 65 ° C, and exceeding 65 ° C is not recommended.
Pridávanie SO2CI2 do o-krezolu sa uskutočňuje počas intenzívneho miešania tak, aby nedošlo k prekročeniu teploty 65 °C.The addition of SO 2 Cl 2 to o-cresol is carried out with vigorous stirring so as not to exceed 65 ° C.
Molárny poměr o-krezolu a SO2CI2 je 1 ku 1 až 1,3.The molar ratio of o-cresol to SO 2 Cl 2 is 1 to 1 to 1.3.
Po ukončení pridávania reakčná zmes doreagováva počas 10 až 64 min. Na vytesnenie reakčných plynov (SO2, HClj sa reakčná zmes vyhřeje na teplotu 100 až 110 °C. Reakčná zmes sa potom podrobí rektifikácií za zníženého tlaku, napr. pri teplote 95 °C/ /1,33 kPa sa oddělí predná frakcia a pri teplote 96 až 100 °C/1,33 kPa sa odoberie frakcia čistého 2-metyl-4-chlórfenolu. Získaný 2-metyl-4-chlórfenol sa krystalizuje zaužívaným technickým postupom z petroléteru. Filtrát po kryštalizácii 2-metyl-4-chlórfenolu sa opatovne dá použit 2- až lOkrát na kryštalizáciu 2-metyl-4-chlórfenolu.After the addition was complete, the reaction mixture was allowed to react for 10 to 64 min. To displace the reaction gases (SO2, HCl), the reaction mixture is heated to a temperature of 100 to 110 [deg.] C. The reaction mixture is then subjected to rectification under reduced pressure, e.g. at 95 [deg.] C./33 mm Hg. A fraction of pure 2-methyl-4-chlorophenol is collected at 96-100 ° C / 50 psi, and the 2-methyl-4-chlorophenol obtained is crystallized from petroleum ether according to conventional techniques. used 2 to 10 times to crystallize 2-methyl-4-chlorophenol.
Po opakované] kryštalizácii z petroléteru sa získá 2-metyl-4-chlórfenol chromatografickej čistoty.After repeated crystallization from petroleum ether, 2-methyl-4-chlorophenol of chromatographic purity is obtained.
Výhodou postupu je, že sa skrátila reakčná doba chlorácie pri dosiahnutí vysokej výťažnosti a selektivity procesu.The advantage of the process is that the chlorination reaction time is shortened while achieving high process yield and selectivity.
Možnost využitia predmetu vynálezu je pri výrobě 2-metyl-4-chlórfenolu ako východzej suroviny pri výrobě niektorých organických zlúčenín (MCPA), resp. pri výrobě 2-metyl-4-chlórfenolu používaného ako standard pre plynovú chromatografiu.The object of the present invention is to produce 2-methyl-4-chlorophenol as a starting material in the production of certain organic compounds (MCPA), respectively. in the manufacture of 2-methyl-4-chlorophenol used as a standard for gas chromatography.
Příklad 1Example 1
Do štvorhrdlovej banky opatrenej miešadlom, teplomerom, spatným chladičom a dávkovacím otvorom sa nasadilo 108,1 g (1 mólj čistého o-krezolu a 4 g ZnCL·. Po premiešaní sa přidává za miešania počas 7 hodin postupné 140 g 96% SO2CI2 (1 mólj, pričom teplota počas pridávania nepřekročila 65 °C. Po ukončení pridávania sa reakč' ná zmes miešala ešte 10 minút, potom sa vyhriala na teplotu 110 °C, {iričom dochádzalo k vytesneniu plynných produktov. Reakčná zmes sa podrobila rektifikácií, a poodobraní prednej frakcie (do 95 °C/l,33kPa) sa začala odoberat frakcia 2-metyl-4-chlórchenolu pri teplote 95 až 100 °C/1,33 kPa. Získaný 2-metyl-4-chlórfenol sa kryštalizoval dvojnásobnou kryštalizáciou z petroléteru. Získalo sa 118 g 2-metyl-4-chlórchenolu, ktorý má teplotu topenia 48,9 °C. Výfažok — 82,7 % teórie.A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a dosing port was charged with 108.1 g (1 mol of pure o-cresol and 4 g of ZnCL2). After the addition was complete, the reaction mixture was stirred for a further 10 minutes, then heated to 110 ° C to displace the gaseous products. The reaction mixture was rectified to collect the front fraction. (up to 95 ° C / 1.33kPa) a 2-methyl-4-chlorochenol fraction was started to be collected at 95-100 ° C / 1.33 kPa. 118 g of 2-methyl-4-chlorochenol having a melting point of 48.9 DEG C. Yield - 82.7% of theory.
Příklad 2Example 2
Do štvorhrdlovej banky opatrenej miešadlom, teplomerom, spatným chladičom a dávkovacím otvorom sa nasadilo 108,1 g (1 mólj čistého o-krezolu, a přidalo sa 0,(8 gramu ZnClz. Po premiešaní sa přidal za miešania počas 7 hodin postupné 140 g 96 % SO2CI2, pričom teplota počas pridávania nepřekročila 65 °C. Po ukončení pridávania sa reakčná zmes miešala ešte 10 minút, potom sa postupné vyhriala na teplotu 108 až 110 stupňov Celsia, pričom dochádzalo k vytesneniu plynných reakčných splodln, ktoré sa zavádzali do vodného roztoku NaOH.A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a dispensing port was charged with 108.1 g (1 mol of pure o-cresol) and 0.1 g of ZnCl2 was added. The reaction mixture was stirred for 10 minutes after completion of the addition, then gradually heated to a temperature of 108 to 110 degrees Celsius to displace the gaseous reaction gases, which were introduced into an aqueous NaOH solution. .
Ďalej sa reakčná zmes podrobila rektifikácií a po odobraní prednej frakcie (do 95 stupňov Celsia/1,33 kPá) sa začala odoberať frakcia 2-metyl-4-chlófenolu při teplote 95 až 100 °C/1,33 kPa. Získaný 2-metyl-4-chlórfenol sa kryštalizoval dvojnásobnou kryštalizáciou s petroléterom. Získalo sa 107 gramov (75 % teórie) 2-metyl-4-chlórfenolu, o teplote topenia 48,9 °C, chromatografickej čistoty.Further, the reaction mixture was rectified and, after withdrawing the front fraction (to 95 degrees Celsius / 1.33 kPa), the 2-methyl-4-chlorophenol fraction was started to be collected at 95-100 ° C / 1.33 kPa. The obtained 2-methyl-4-chlorophenol was crystallized by two crystallizations with petroleum ether. 107 g (75% of theory) of 2-methyl-4-chlorophenol, m.p. 48.9 DEG C., chromatographic purity was obtained.
Příklad 3Example 3
V pokuse sa postupovalo ako v příklade 1, len na prvú kryštalizáciu 2-metyl-4-chlórfenolu sa použil matečný roztok petroléteru z poslednej kryštálizácie z příkladu 2. Získalo sa 117 g (82 % teórie) 2-metyl-4-chlórfenolu o teplote topenia 48,8 °C.The experiment was carried out as in Example 1, except that for the first crystallization of 2-methyl-4-chlorophenol, a petroleum ether mother liquor from the last crystallization of Example 2 was used. 117 g (82% of theory) of 2-methyl-4-chlorophenol were obtained. mp 48.8 ° C.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS700781A CS221004B1 (en) | 1981-09-23 | 1981-09-23 | Method of making the 2-methyl-4-chlorphenoles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS700781A CS221004B1 (en) | 1981-09-23 | 1981-09-23 | Method of making the 2-methyl-4-chlorphenoles |
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| Publication Number | Publication Date |
|---|---|
| CS221004B1 true CS221004B1 (en) | 1983-04-29 |
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| Application Number | Title | Priority Date | Filing Date |
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| CS700781A CS221004B1 (en) | 1981-09-23 | 1981-09-23 | Method of making the 2-methyl-4-chlorphenoles |
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| CS (1) | CS221004B1 (en) |
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1981
- 1981-09-23 CS CS700781A patent/CS221004B1/en unknown
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