CS224843B1 - Method of preparation of 2,4,4 trimethylpentan-3-one - Google Patents
Method of preparation of 2,4,4 trimethylpentan-3-one Download PDFInfo
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- CS224843B1 CS224843B1 CS293082A CS293082A CS224843B1 CS 224843 B1 CS224843 B1 CS 224843B1 CS 293082 A CS293082 A CS 293082A CS 293082 A CS293082 A CS 293082A CS 224843 B1 CS224843 B1 CS 224843B1
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- Czechoslovakia
- Prior art keywords
- sulfuric acid
- trimethylpentane
- oxide
- trimethylpentan
- preparation
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 8
- OVCHQRXVZXVQNQ-UHFFFAOYSA-N 2,2,4-trimethylpentan-3-one Chemical compound CC(C)C(=O)C(C)(C)C OVCHQRXVZXVQNQ-UHFFFAOYSA-N 0.000 title claims description 7
- 238000002360 preparation method Methods 0.000 title claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000006317 isomerization reaction Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- WDKALHWKBIWSNZ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-en-3-ol Chemical compound CC(=C)C(O)C(C)(C)C WDKALHWKBIWSNZ-UHFFFAOYSA-N 0.000 description 1
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical compound CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000002051 biphasic effect Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
Vynález sa týká spósobu přípravy 2,4,4-triraetylpeatán3-onu,The present invention relates to a process for the preparation of 2,4,4-triraethylpeatan-3-one,
Podlá PV 7270 jo možné připravit’ 2,4,4-trimetylpeatán3-on vo výtažku 8,7 % izomerizáciou 2* 4»4-trimetylpentán<»2,3oxidu v prostředí přebytku 3,0 %-ného vodného roztoku kyseliny sírověj pri 90 °C, pričom hlavným produktem sú kte^noly.According to PV 7270, 2,4,4-trimethylpeatan-3-one can be prepared in 8.7% yield by isomerization of 2 * 4, 4-trimethylpentane <2.3 2,3 in an excess of 3.0% aqueous sulfuric acid at 90%. ° C, the major product being those.
Podstata spósobu přípravy 2,4,4-trimetylpentán-3-ónu izomerizáciou 2,4,4-trimetylpentán-2,3-oxidu za katalytického účinku kyseliny sírovej podlá vynálezu spočívá v tom, že sa kyselina sírová nanesie na silikágél, pričom molový poměr 2,4,4trimetylpentán-2,3-oxidu ku kyselino sírovej je 15 : 1 až 320:The process for the preparation of 2,4,4-trimethylpentan-3-one by isomerization of 2,4,4-trimethylpentan-2,3-oxide under the catalytic action of sulfuric acid according to the invention is characterized in that sulfuric acid is applied to the silica, the molar ratio 2,4,4-trimethylpentane-2,3-oxide to sulfuric acid is 15: 1 to 320:
s výhodou 15 ; 1 až 40 : 1 a izomerizácia prebieha pri teploto 10 až 50°C za miešania v přítomnosti uhlovodíkového rozpúšťadla s výhodou cyklohexánu do 100 %-nej konvorzie 2,4,4-trimetylpentán-2,3-oxidu.preferably 15; 1-40: 1 and the isomerization is carried out at a temperature of 10 to 50 ° C with stirring in the presence of a hydrocarbon solvent, preferably cyclohexane, to 100% conversion of 2,4,4-trimethylpentane-2,3-oxide.
Katalyzátor, ktorým je kyselina sírová na silikagéli, možno po oddestilování opátovné použiť pre cíalšiu reakciu.The catalyst, which is sulfuric acid on silica gel, can be reused for further reaction after distillation.
Kyselina sírová je v reakčnej sústav© prakticky nerozpustná a tvoří kvapalnú dvojfázovú sústavu, pričom jej časť ulpieva na stěnách reakčnej nádoby v závislosti na intenzito a spósobe miešania. Napriek tomu sú výtažky pri použití kyseliny sírovej priaznivó, dosahujú 77,5 % teorie 2,4,4-trimetylpentán3-onu.Sulfuric acid is practically insoluble in the reaction system 8 and forms a liquid biphasic system, a part of which adheres to the walls of the reaction vessel depending on the intensity and manner of mixing. Nevertheless, the yields using sulfuric acid are favorable, reaching 77.5% of the 2,4,4-trimethylpentan-3-one theory.
Zvýšenie výtažku na 83,1 % teorie je možno dosiahnúť v případe viazania kyseliny sírovej na vhodný nosič, napr. silikagél.An increase in yield to 83.1% of theory can be achieved in the case of binding of sulfuric acid to a suitable carrier, e.g. silica.
224 843224 843
Množstvo kyseliny sírovej, silikagélu a jeho zrnenie sa riadi zásadou zachovania sypkosti katalyzátora. Osvědčila sa koncentrácia 50 % hm. kyseliny sírovej na silikagéli zrnenia 0,07 až 0,16 mm. Takto připravený katalyzátor je silné hygroskopický, musí sa rýchlo navazovat’, preniest do vybratej banky a převrstvit rozpúšťadlom. Katalyzátor neulpieva na stěnách banky a pri miešaní je dobré rozptýlený v zmesi. Nedostatečné množstvo katalyzátora má za následok neúměrné predíženie reakčnej doby spolu so vznikom nežiaducioh produktov. Je výhodné reakciu okamžité ukončit po úplnéj konve^zii 2,4,4-trimetylpentán-2,3-oxidu a začat s izoláciou, ktorú nepřítomnost’ 2,4,4trimetylpentán«2,3-oxidu ulahčuje, V případe přípravy váčšieho množstva 2,4,4-trimetylpentán~3-onu je možné do reakčnej sústavy přidávat 2,4,4-trimetylpentán«2,3-oxid po častiach.The amount of sulfuric acid, silica gel and grain size is controlled by the free flow of catalyst. A concentration of 50 wt. of sulfuric acid on silica gel with a particle size of 0.07 to 0.16 mm. The catalyst prepared in this way is strong hygroscopic, it must quickly bind, transfer to a selected flask and overlay with solvent. The catalyst does not adhere to the walls of the flask and is well dispersed in the mixture with stirring. Insufficient amount of catalyst results in a disproportionate increase in the reaction time along with the formation of undesirable products. It is advantageous to terminate the reaction immediately after complete convection of 2,4,4-trimethylpentane-2,3-oxide and to start isolation, which the absence of 2,4,4-trimethylpentane-2,3-oxide facilitates. 2,4,4-trimethylpentan-3-one can be added in portions to the reaction system.
Ako rozpúštadlo možno použit uhlovodíky, potažné ich zmesi, ktoré sú v reakčnom prostredi dostatočné stále /osvědčil sa cyklohexán/, ktoré súčasne slúžia na reguláciu tepelného režimu. Rozpúštadlá ako voda, éter, alkoholy, karboxylové kyseliny znižujú výtažky produktu a extrahujú kyselinu sírovú zo silikagélu. Použitý katalyzátor mierne stmavne, nestratí však póvodnú aktivitu a zachová si póvodnú zrnitost, tvorba živíc, ktorá je příčinou změny zafarbenia katalyzátora závisí na teplote a přítomnosti alkenických nečistót, ktoré polymerizujú na povrchu katalyzátora a sú příčinou zlepovania častíc katalyzátora·The solvent can be hydrocarbons, coated with mixtures thereof, which are still stable in the reaction medium (cyclohexane has proven to be useful) and at the same time serve to regulate the thermal regime. Solvents such as water, ether, alcohols, carboxylic acids reduce product yields and extract sulfuric acid from silica gel. The catalyst used slightly darkens, but does not lose its original activity and retains the original grain size, the formation of resins causing the color change of the catalyst depends on the temperature and the presence of alkene impurities that polymerize on the catalyst surface and cause the catalyst particles to stick.
Příklad 1Example 1
V 250 ml Erlenmayerovej banke s magnetickým miešadlom, ohrevom, teplomerom, spátným chladičom a zariadením na odběr vzoriek sa zmieša 0,9 g 93 %-nej kyseliny sírovej, 60 ml cyklohexánu a 20 g 2,4,4-trimetylpentán-2,3-oxidu pri teplote 10 °C. Za miešania stupně teplota na 40 °C a po 8 minútach reakčná zmes sa neutralizuje vodným roztokom hydrouhličitanu sodného, vysuší sa bezvodým síranom sodným. Analyzuje sa metodou plynovej chromáto224 843 grafie a vyhodnotí metodou priamej kalibrácie.In a 250 ml Erlenmeyer flask with a magnetic stirrer, heating, thermometer, reflux condenser and sampling device, mix 0.9 g of 93% sulfuric acid, 60 ml of cyclohexane and 20 g of 2,4,4-trimethylpentane-2,3 -oxide at 10 ° C. Stirring the temperature to 40 ° C and after 8 minutes the reaction mixture was neutralized with aqueous sodium bicarbonate solution, dried over anhydrous sodium sulfate. It is analyzed by the gas chromate224 843 graph method and evaluated by the direct calibration method.
Vzorka obsahovala : 77,5 % hm. 2,4,4-trimetylpentán-3-ónuThe sample contained: 77.5 wt. 2,4,4-trimethylpentane-3-one
0,2 % hm. 4,4-dimetyl-2-metylénpentán“0.2% wt. 4,4-dimethyl-2-metylénpentán "
3-onu3-one
19,0 % hm. 2,5-izobutyl-2-izopropyl-$3 dimetyl-l,3-dioxolanu a19.0% wt. 2,5-isobutyl-2-isopropyl-3-dimethyl-1,3-dioxolane a
3,3 % hm· neidentifikovaných látok.3.3% by weight of unidentified substances.
Konverzia 2,4,4-trimetylpentán-2,3-oxidu bola úplná·2,4,4-Trimethylpentane-2,3-oxide conversion was complete ·
Příklad 2Example 2
Postup ako v příklade 1 s tým rozdielom, že násadu tvoří 0,1 g silikagélu s obsahom 48 % hm· kyseliny sírovej, 60 mJ cyklohexánu a 20 g 2,4,4-trxmetýlpentán-2,3-oxxdu pri počiatočnej teplote 20 °C. PO 52 minútach vzorka obsahovala :Procedure as in Example 1, except that the feed is 0.1 g of silica gel containing 48% by weight sulfuric acid, 60 mJ cyclohexane and 20 g of 2,4,4-trimethylpentane-2,3-oxxde at an initial temperature of 20 ° C. After 52 minutes, the sample contained:
43.5 % hm· 2,4,4-trxmetylpentán-2,3-oxidu43.5% (w / w) 2,4,4-trimethylpentane-2,3-oxide
39.6 % hm. 2,4,4-trimetylpentán-3-ónu39.6% wt. 2,4,4-trimethylpentane-3-one
1,0 % hm. 2,5-izobutyl-2-izopropyl-3,3-dxmetyl-l,3-dxoxolánu a 15,9 % hm, neidentifikovaných látok.1.0 wt. 2,5-isobutyl-2-isopropyl-3,3-dimethylmethyl-1,3-dioxolane and 15.9% by weight of unidentified substances.
Příklad 3Example 3
Postup ako v příklade 1 s tým rozdielom, že násadu tvoří 1,0 g silikagélu s obsahom 48 % hm· kyseliny sírovej, 60 ml cyklohexánu a 20 g 2,4,4-trimetylpentán-2,3-oxidu pri počiatočnej teplote 20 °C, ktorá v priebehu 2 minút vystúpila na 40 °C, čím bola reakcia ukončená·Procedure as in Example 1, except that the batch consists of 1.0 g of silica gel containing 48% by weight sulfuric acid, 60 ml of cyclohexane and 20 g of 2,4,4-trimethylpentane-2,3-oxide at an initial temperature of 20 ° C, which rose to 40 ° C in 2 minutes to complete the reaction.
Vzorka obsahovala :The sample contained:
% hm. 2,4,4-trxmetylpentán-3-ónu% wt. 2,4,4-trxmetylpentán-3-one
0,2 % hm, 4,4-dimetyl-2-metylénpentáa-3-olu0.2 wt%, 4,4-dimethyl-2-methylenepentan-3-ol
0,4 % hm. 2,5-izobutyl-2-izopropyl-3,3-dimetyl-l,3-dioxolánu a 16,3 % hm. neidentifikovaných látok.·0.4% wt. 2,5-isobutyl-2-isopropyl-3,3-dimethyl-1,3-dioxolane and 16.3 wt. unidentified substances ·
Konverzia 2,4,4*trimetylpeatán-2,3-oxidu bola úplná·2,4,4 * trimethylpeate-2,3-oxide conversion was complete ·
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS293082A CS224843B1 (en) | 1982-04-26 | 1982-04-26 | Method of preparation of 2,4,4 trimethylpentan-3-one |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS293082A CS224843B1 (en) | 1982-04-26 | 1982-04-26 | Method of preparation of 2,4,4 trimethylpentan-3-one |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CS224843B1 true CS224843B1 (en) | 1984-01-16 |
Family
ID=5367876
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS293082A CS224843B1 (en) | 1982-04-26 | 1982-04-26 | Method of preparation of 2,4,4 trimethylpentan-3-one |
Country Status (1)
| Country | Link |
|---|---|
| CS (1) | CS224843B1 (en) |
-
1982
- 1982-04-26 CS CS293082A patent/CS224843B1/en unknown
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