NL9200968A - Method for the preparation of a p-hydroxybenzaldehyde - Google Patents
Method for the preparation of a p-hydroxybenzaldehyde Download PDFInfo
- Publication number
- NL9200968A NL9200968A NL9200968A NL9200968A NL9200968A NL 9200968 A NL9200968 A NL 9200968A NL 9200968 A NL9200968 A NL 9200968A NL 9200968 A NL9200968 A NL 9200968A NL 9200968 A NL9200968 A NL 9200968A
- Authority
- NL
- Netherlands
- Prior art keywords
- hydroxybenzaldehyde
- catalyst
- cresol
- process according
- base
- Prior art date
Links
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 4
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 150000002739 metals Chemical class 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001392 phosphorus oxide Inorganic materials 0.000 claims abstract description 5
- 239000007800 oxidant agent Substances 0.000 claims abstract description 4
- 239000010703 silicon Substances 0.000 claims abstract description 4
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims description 2
- 229930003836 cresol Natural products 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 239000002585 base Substances 0.000 claims 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims 1
- 239000002638 heterogeneous catalyst Substances 0.000 abstract description 3
- 239000004411 aluminium Substances 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical class [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- BVJSUAQZOZWCKN-UHFFFAOYSA-N p-hydroxybenzyl alcohol Chemical compound OCC1=CC=C(O)C=C1 BVJSUAQZOZWCKN-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 4
- -1 for example Substances 0.000 description 4
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- IGCQTZQTGKNFLX-UHFFFAOYSA-N 4-[2-[2-(4-hydroxyphenyl)ethoxy]ethyl]phenol Chemical compound C1=CC(O)=CC=C1CCOCCC1=CC=C(O)C=C1 IGCQTZQTGKNFLX-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- AHXXIALEMINDAW-UHFFFAOYSA-N p-hydroxybenzyl methyl ether Natural products COCC1=CC=C(O)C=C1 AHXXIALEMINDAW-UHFFFAOYSA-N 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical class CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical class CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 1
- 150000002931 p-cresols Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/36—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in compounds containing six-membered aromatic rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
WERKWIJZE VOOR DE BEREIDING VAN EEN P-HYDROXYBENZALDEHYDEPROCESS FOR PREPARING A P-HYDROXYBENZALDEHYDE
De uitvinding betreft een werkwijze voor de bereiding van een p-hydroxybenzaldehyde door behandeling met een oxiderend agens van een p-cresol in aanwezigheid van een base, een oplosmiddel en een metaal bevattende katalysator.The invention relates to a process for the preparation of a p-hydroxybenzaldehyde by treatment with an oxidizing agent of a p-cresol in the presence of a base, a solvent and a metal-containing catalyst.
Een dergelijke werkwijze is bekend uit EP-A-12939. In deze publikatie staat beschreven de oxidatie van p-cresol met een cobaltverbinding of metallisch cobalt.Such a method is known from EP-A-12939. This publication describes the oxidation of p-cresol with a cobalt compound or metallic cobalt.
Nadelen van de beschreven werkwijze zijn dat de katalysator in de praktijk slechts moeizaam terugwinbaar is en dat de bereikte opbrengst aan p-hydroxybenzaldehyde relatief laag is. Weliswaar zijn er tevens publikaties bekend waar in getracht wordt de opbrengst aan p-hydroxybenzaldehyde te verhogen door toevoegen van andere verbindingen of cokatalysatoren, echter steeds blijft hieraan het nadeel van de slechte terugwinbaarheid van de katalysator verbonden. Dit is met name van belang aangezien het verlies van de gebruikelijke metaalkatalysatoren een nadelige belasting van het milieu vormen.Disadvantages of the described process are that in practice the catalyst is difficult to recover and that the yield of p-hydroxybenzaldehyde achieved is relatively low. Although there are also known publications which attempt to increase the yield of p-hydroxybenzaldehyde by adding other compounds or cocatalysts, the drawback of the poor recoverability of the catalyst is always associated with this. This is particularly important since the loss of conventional metal catalysts is detrimental to the environment.
Daarnaast is uit EP-A-330036 een werkwijze bekend waarbij een onder bepaalde omstandigheden terugwinbare katalysator in de vorm van een chelaat-ligand wordt toegepast. De verkregen opbrengsten aan p-hydroxybenzaldehyde zijn hier echter laag.In addition, EP-A-330036 discloses a method in which a catalyst in the form of a chelate ligand which can be recovered under certain conditions is used. However, the yields of p-hydroxybenzaldehyde obtained here are low.
De uitvinding stelt zich ten doel met een terugwinbare katalysator in genoemde reaktie, hoge opbrengsten aan p-hydroxybenzaldehyde te bereiken.The object of the invention is to achieve high yields of p-hydroxybenzaldehyde with a recoverable catalyst in said reaction.
Dit wordt volgens de uitvinding bereikt door als katalysator een drie-dimensionale microporeuze structuur, bevattende aluminium-, silicium- en/of fosforoxide, welke gemodificeerd is met een of meerdere metalen toe te passen.This is achieved according to the invention by using as a catalyst a three-dimensional microporous structure, containing aluminum, silicon and / or phosphorus oxide, which has been modified with one or more metals.
Gebleken is namelijk dat wanneer de heterogene katalysator volgens de uitvinding werd toegepast een opbrengst aan p-hydroxybenzaldehyde van meer dan 90% berekend t.o.v. de hoeveelheid ingezet p-cresol kan worden gerealiseerd. Bovendien is gebleken dat ook nadat de katalysator 10 maal hergebruikt was, nog steeds een hoge selektiviteit en conversie werd gerealiseerd. Daarnaast is gebleken dat de reaktiesnelheid bij gebruik van de heterogene katalysator volgens de uitvinding hoger was dan wanneer een homogene metaalkatalysator werd toegepast, terwijl tevens veel minder metaal katalysator werd toegepast ten opzichte van de hoeveelheid substraat. Bovendien is gebleken dat ook p-hydroxybenzalalcohol in de werkwijze volgens de uitvinding wordt omgezet tot p-hydroxybenzaldehyde resulterend in een verlaging van de hoeveelheid gevormde p-hydroxybenzylmethylether en een verhoging van de opbrengst aan p-hydroxybenzaldehyde.Namely, it has been found that when the heterogeneous catalyst according to the invention is used, a yield of p-hydroxybenzaldehyde of more than 90% calculated with respect to the amount of p-cresol used can be realized. Moreover, it has been found that even after the catalyst has been reused 10 times, a high selectivity and conversion was still achieved. In addition, it has been found that the reaction rate when using the heterogeneous catalyst according to the invention was higher than when a homogeneous metal catalyst was used, while also much less metal catalyst was used with respect to the amount of substrate. In addition, it has been found that p-hydroxybenzalcohol is also converted to p-hydroxybenzaldehyde in the process of the invention, resulting in a decrease in the amount of p-hydroxybenzyl methyl ether formed and an increase in the yield of p-hydroxybenzaldehyde.
Als uitgangsstoffen worden in de werkwijze volgens de uitvinding p-cresolen toegepast, welke eventueel in de kern gesubstitueerd kunnen zijn met een of meerdere alkylgroepen, alkoxygroepen en/of halogeniden. De alkyl en alkoxygroepen zullen meestal 1-6 C-atomen bevatten.The starting materials used in the process according to the invention are p-cresols, which may optionally be substituted in the core with one or more alkyl groups, alkoxy groups and / or halides. The alkyl and alkoxy groups will usually contain 1-6 C atoms.
Het oxiderend agens dat gebruikt wordt in de werkwijze volgens de uitvinding kan ofwel zuurstof zijn of zuurstof bevattend gas dat bijvoorbeeld verdund is met een inert gas, zoals bijvoorbeeld lucht. De druk van het zuurstof of het zuurstofbevattend gas kan binnen wijde grenzen variëren, en is meestal 0.1-10 MPa, bij voorkeur 0.1-2 MPa.The oxidizing agent used in the method of the invention can be either oxygen or oxygen-containing gas, for example, diluted with an inert gas, such as, for example, air. The pressure of the oxygen or the oxygen-containing gas can vary within wide limits, and is usually 0.1-10 MPa, preferably 0.1-2 MPa.
Als katalyatoren worden verbindingen toegepast die in hoofdzaak bestaan uit een driedimensionale, microporeuze raamstructuur bevattende aluminium-, silicium- en/of fosforoxide, welke zijn gemodificeerd met één of meerdere gemakkelijk oxideerbare metalen. Als metalen kunnen hoofdgroepmetalen zoals B, Al, Ga, overgangsmetalen zoals Cu, Cr, Mn, Fe, Co, Ni, W, Mo en zeldzame aarden zoals V,The catalysts used are compounds which mainly consist of a three-dimensional, microporous window structure containing aluminum, silicon and / or phosphorus oxide, which have been modified with one or more easily oxidizable metals. As metals, main group metals such as B, Al, Ga, transition metals such as Cu, Cr, Mn, Fe, Co, Ni, W, Mo and rare earths such as V,
Ce, La, Pr en No worden toegepast. Bij voorkeur wordt Co, Cr of V toegepast.Ce, La, Pr and No are used. Co, Cr or V is preferably used.
Geschikte katalysatoren die kunnen worden toegepast in de werkwijze van de uitvinding zijn bijvoorbeeld de kraakkatalysatoren zoals beschreven in US-A-4310440, US-A-4567029 en US-A-4759919. Deze katalysatorsystemen (MeAPO's) blijken in de praktijk een hoge chemische en thermische stabiliteit te bezitten.Suitable catalysts that can be used in the process of the invention are, for example, the cracking catalysts described in US-A-4310440, US-A-4567029 and US-A-4759919. These catalyst systems (MeAPOs) have been found to have high chemical and thermal stability in practice.
De hoeveelheid toe te passen metaal is niet kritisch. Meestal zal 0,0001-0,05 equivalent metaal worden toegepast berekend t.o.v. de hoeveelheid p-cresol.The amount of metal to be used is not critical. Usually 0.0001-0.05 equivalent metal will be used calculated with respect to the amount of p-cresol.
Als base komen in de werkwijze volgens de uitvinding in aanmerking alle typen basen die een hogere basiciteit hebben dan de p-cresol verbinding. Voorbeelden van dergelijke verbindingen zijn metaalhydroxiden, metaalalkoxiden en metaalamiden. Geschikte voorbeelden van deze verbindingen zijn natriumhydroxide, kaliumhydroxide, natrium(m)ethoxide, kalium(m)ethoxide. De hoeveelheid base die wordt toegepast is niet kritisch en bedraagt meestal meer dan 1 equivalent base berekend t.o.v. de hoeveelheid p-cresol verbinding, bij voorkeur 2,5-3,5 equivalenten base t.o.v. p-cresol.All types of bases which have a higher basicity than the p-cresol compound are suitable as base in the method according to the invention. Examples of such compounds are metal hydroxides, metal alkoxides and metal amides. Suitable examples of these compounds are sodium hydroxide, potassium hydroxide, sodium (m) ethoxide, potassium (m) ethoxide. The amount of base used is not critical and is usually more than 1 equivalent of base calculated relative to the amount of p-cresol compound, preferably 2.5-3.5 equivalents of base relative to p-cresol.
In de werkwijze volgens de uitvinding kunnen allerlei oplosmiddelen worden toegepast die inert zijn in het reactiemengsel en waarin de uitgangsverbindingen oplossen, zoals bijvoorbeeld alcoholen, ethers, aminen, dimethylformamides en dimethylsulfoxiden. Bij voorkeur worden alcoholen in het bijzonder methanol of ethanol toegepast. De beste resultaten worden verkregen wanneer er zo weinig mogelijk water in het reactiemengsel aanwezig is.A variety of solvents which are inert in the reaction mixture and dissolve the starting compounds, such as, for example, alcohols, ethers, amines, dimethyl formamides and dimethyl sulfoxides, can be used in the process according to the invention. Alcohols, in particular methanol or ethanol, are preferably used. The best results are obtained when there is as little water as possible in the reaction mixture.
De temperatuur waarbij de werkwijze volgens de uitvinding wordt uitgevoerd is niet kritisch en zal meestal tussen 0 en 200°C liggen. Bij voorkeur wordt een temperatuur tussen 40 en 70°C in het bijzonder tussen 50 en 60°C aangehouden.The temperature at which the method according to the invention is carried out is not critical and will usually be between 0 and 200 ° C. Preferably, a temperature between 40 and 70 ° C, in particular between 50 and 60 ° C, is maintained.
De uitvinding zal nu worden toegelicht aan de hand van de volgende voorbeelden, zonder evenwel daartoe te worden beperkt.The invention will now be elucidated by means of the following examples, without, however, being limited thereto.
Voorbeeld IExample I
In een gethermostreerde driehalsreaktor van 100 ml die is uitgerust met een magnetische roerder en verbonden is met automatische gasabsorptie meetapparatuur werd 9 gram (83,4 mmol) p-cresol, 1,5 gram CoAPO-11 kat verkregen met de werkwijze als beschreven in voorbeeld 94 van US-A-4567029 met 1% (0,12 mmol) Co, 10 gram (252 mmol) NaOH en 27 ml methanol gevoerd. De apparatuur werd zorgvuldig met zuurstof gespoeld. Vervolgens werd het mengsel onder roeren (1000 rpm) gedurende 10 uur bij een temperatuur van 55°C onder zuurstofatmosfeer (1 atm.) gehouden.In a 100 ml thermostated three-neck reactor equipped with a magnetic stirrer and connected to automatic gas absorption measuring equipment, 9 grams (83.4 mmol) of p-cresol, 1.5 grams of CoAPO-11 cat was obtained by the method described in example 94 of US-A-4567029 with 1% (0.12 mmol) Co, 10 grams (252 mmol) NaOH and 27 ml methanol. The equipment was carefully flushed with oxygen. Then the mixture was kept under stirring (1000 rpm) for 10 hours at a temperature of 55 ° C under oxygen atmosphere (1 atm.).
Het verloop van de reaktie werd met behulp van HPLC gevolgd. 97% cresol was omgezet tot aldehyde (selektiviteit 93%), ether (selektiviteit 3,5%) en alcohol (selektiviteit 1,4%).The course of the reaction was monitored by HPLC. 97% cresol was converted to aldehyde (selectivity 93%), ether (selectivity 3.5%) and alcohol (selectivity 1.4%).
Voorbeeld IIExample II
De stabiliteit van de katalysator werd getest door deze een aantal malen in de reaktie in te zetten. De reaktie werd uitgevoerd als in voorbeeld I, de katalysator werd hergebruikt waarbij de katalysator na de reaktie werd afgefiltreerd, vervolgens met methanol gewassen, en daarna weer ingezet in de volgende reaktie van de cyclus. De resultaten zijn weergegeven in tabel 1.The stability of the catalyst was tested by reacting it several times. The reaction was carried out as in Example 1, the catalyst was reused with the catalyst filtered off after the reaction, then washed with methanol, and then reused in the next cycle reaction. The results are shown in Table 1.
Deze tabel laat duidelijk zien dat de aktiviteit en selektiviteit op een hoog niveau gehandhaafd blijven.This table clearly shows that the activity and selectivity are maintained at a high level.
Uit atomaire absorptie analyse van Co in de oplossing verkregen na filtratie van de katalysator, is tevens gebleken dat de hoeveelheid Co in de oplossing beneden de detektiegrens van de apparatuur lag (< 10 ppm), hetgeen aantoont dat er geen decompositie van de katalysator in oplosbare Co-complexen optrad.Atomic absorption analysis of Co in the solution obtained after filtration of the catalyst has also shown that the amount of Co in the solution was below the detection limit of the equipment (<10 ppm), showing that there is no decomposition of the catalyst in soluble Co-complexes occurred.
Voorbeeld IIIExample III
Op dezelfde manier als in voorbeeld I beschreven werd de oxidatie uitgevoerd onder druk (2 MPa; zuurstof). Na 8 uur was 95% p-cresol omgezet. Daarvan was 95% in p-hydroxybenzaldehyde, 1,2% in p-hydroxybenzylalcohol en 3,7% in p-hydroxybenzylmethylether omgezet.In the same manner as described in Example I, the oxidation was carried out under pressure (2 MPa; oxygen). After 8 hours, 95% p-cresol was converted. 95% of this had been converted into p-hydroxybenzaldehyde, 1.2% into p-hydroxybenzyl alcohol and 3.7% into p-hydroxybenzyl methyl ether.
Voorbeeld IVExample IV
Op dezelfde manier als in voorbeeld I werd nu gebruik makend van 1,0 g van een Cr-bevattende katalysator CAPO-11, als beschreven in voorbeeld 5 van US-A-4759919, p-cresol geoxideerd. Na 16 uur was 97% van het p-cresol omgezet; daarvan was 95,5% omgezet in p-hydroxybenzaldehyde, 1,3% in p-hydroxybenzylalcohol en 1,2% in p-hydroxybenzyl-methylether.In the same manner as in Example 1, p-cresol was now oxidized using 1.0 g of a Cr-containing catalyst CAPO-11 as described in Example 5 of US-A-4759919. After 16 hours, 97% of the p-cresol was converted; 95.5% of this had been converted to p-hydroxybenzaldehyde, 1.3% to p-hydroxybenzyl alcohol and 1.2% to p-hydroxybenzyl methyl ether.
Voorbeeld VExample V
Op dezelfde manier als in voorbeeld I werd een mengsel van 5,0 g (46,3 mmol) p-cresol en 5,2 g (48,1 mmol) m-cresol, 10 g NaOH, 1,0 g CoAPO-11 en 27 ml methanol ingezet. Het mengsel werd gedurende 10 uur bij een temperatuur van 55°C onder zuurstofatmosfeer geroerd (1 atm) .In the same manner as in Example I, a mixture of 5.0 g (46.3 mmol) p-cresol and 5.2 g (48.1 mmol) m-cresol, 10 g NaOH, 1.0 g CoAPO-11 and 27 ml of methanol used. The mixture was stirred (1 atm) at a temperature of 55 ° C for 10 hours under oxygen atmosphere.
Na afkoelen werd de volgende samenstelling van het reactiemengsel gevonden: 0,86 g (7,96 mmol) p-cresol (conversie: 82,8%) 5,2 g (48,1 mmol) m-cresol (conversie: 0) 3,98 g (32,62 mmol) p-hydroxybenzalhyde (selectiviteit: 85,1%) 0,13 g (1/05 mmol) p-hydroxybenzylalcohol (selectiviteit: 2/7%) 0,36 g (2,61 mmol) p-hydroxybenzylmethylethyl (selectiviteit: 6,8%).After cooling, the following composition of the reaction mixture was found: 0.86 g (7.96 mmol) p-cresol (conversion: 82.8%) 5.2 g (48.1 mmol) m-cresol (conversion: 0) 3.98 g (32.62 mmol) p-hydroxybenzalhyde (selectivity: 85.1%) 0.13 g (1/05 mmol) p-hydroxybenzyl alcohol (selectivity: 2/7%) 0.36 g (2.61 mmol) p-hydroxybenzylmethylethyl (selectivity: 6.8%).
0,018 g (0,13 mmol) p-hydroxybenzoëzuur (selectiviteit: 0,3%) .0.018 g (0.13 mmol) p-hydroxybenzoic acid (selectivity: 0.3%).
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL9200968A NL9200968A (en) | 1992-06-03 | 1992-06-03 | Method for the preparation of a p-hydroxybenzaldehyde |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL9200968 | 1992-06-03 | ||
| NL9200968A NL9200968A (en) | 1992-06-03 | 1992-06-03 | Method for the preparation of a p-hydroxybenzaldehyde |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| NL9200968A true NL9200968A (en) | 1994-01-03 |
Family
ID=19860870
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NL9200968A NL9200968A (en) | 1992-06-03 | 1992-06-03 | Method for the preparation of a p-hydroxybenzaldehyde |
Country Status (1)
| Country | Link |
|---|---|
| NL (1) | NL9200968A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5773664A (en) * | 1995-02-01 | 1998-06-30 | Bayer Aktiengesellschaft | Process for the recovery of 4-hydroxybenzaldehyde from reaction mixtures containing same |
-
1992
- 1992-06-03 NL NL9200968A patent/NL9200968A/en not_active Application Discontinuation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5773664A (en) * | 1995-02-01 | 1998-06-30 | Bayer Aktiengesellschaft | Process for the recovery of 4-hydroxybenzaldehyde from reaction mixtures containing same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3247262A (en) | Process for making polyphenols | |
| US4254060A (en) | Process for producing an aliphatic amine | |
| EP0012939B1 (en) | Process for the production of 4-hydroxybenzaldehyde derivatives | |
| CA1075253A (en) | Oxidative coupling of alkylphenols catalyzed by metal complexes of diimino acid | |
| US4195189A (en) | Preparation of biphenols by the oxidative coupling of alkylphenols | |
| US4100205A (en) | Oxidative coupling of alkylphenols or 1-naphthols catalyzed by metal complexes of aminoketo compounds | |
| US6680385B2 (en) | Catalytic preparation of aryl methyl ketones using a molecular oxygen-containing gas as the oxidant | |
| GB2055829A (en) | Preparation of carboxylic acids from aldehydes | |
| NL9200968A (en) | Method for the preparation of a p-hydroxybenzaldehyde | |
| US4098830A (en) | Oxidative coupling of alkylphenols or 1-naphthols catalyzed by metal complexes of dicarboxylic acid compounds | |
| US4361709A (en) | Process for the production of o-alkylated phenols | |
| KR19990045384A (en) | Method of Oxidizing An Aromatic Compound into a Hydroxyaromatic Compound | |
| JPS62198641A (en) | Production of carboxylic acid salt | |
| US4471140A (en) | Preparation of aromatic aldehydes | |
| US4100203A (en) | Oxidative coupling of alkylphenols or 1-naphthols catalyzed by metal complexes of an oxime of a keto or aldehyde compound | |
| EP0467063B1 (en) | Process for the preparation of aryl-substituted propionic acid esters | |
| US4097461A (en) | Oxidative coupling of alkylphenols or 1-naphthols catalyzed by metal complexes of diketo compounds | |
| US4100204A (en) | Oxidative coupling of alkylphenols or 1-naphthols catalyzed by metal complexes of a hydroxy- or keto-acid compound | |
| US4100206A (en) | Oxidative coupling of alkylphenols or 1-naphthols catalyzed by metal complexes of keto alcohol compounds | |
| US3703541A (en) | Process for the production of 3-hydroxy-2,2,4-trimethylpentyl isobutyrate | |
| US5101031A (en) | Preparation of 2,4,5-triamino-6-hydroxypyrimidine by catalytic hydrogenation of 2,4-diamino-6-hydroxy-5-nitroso-pyrimidine | |
| EP0074272B1 (en) | Process for the preparation of hydroxybenzaldehydes | |
| CA1065296A (en) | Oxidative coupling of phenols and naphthols | |
| US5352824A (en) | Process for the preparation of alkoxyalkanoic acids | |
| JPH0899933A (en) | Method for producing methacrylic acid ester |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A1B | A search report has been drawn up | ||
| BI | The patent application has been withdrawn |