NO156648B - PROCEDURE FOR HYDROXYLATION OF AROMATIC HYDROCARBONES. - Google Patents
PROCEDURE FOR HYDROXYLATION OF AROMATIC HYDROCARBONES. Download PDFInfo
- Publication number
- NO156648B NO156648B NO830926A NO830926A NO156648B NO 156648 B NO156648 B NO 156648B NO 830926 A NO830926 A NO 830926A NO 830926 A NO830926 A NO 830926A NO 156648 B NO156648 B NO 156648B
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- Norway
- Prior art keywords
- acetone
- reaction
- yield
- hydroxylation
- cresol
- Prior art date
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- 238000000034 method Methods 0.000 title claims description 21
- 230000033444 hydroxylation Effects 0.000 title claims description 10
- 238000005805 hydroxylation reaction Methods 0.000 title claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 7
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 6
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 6
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 6
- FZERHIULMFGESH-UHFFFAOYSA-N N-phenylacetamide Chemical compound CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 claims description 6
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 239000010457 zeolite Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000000052 comparative effect Effects 0.000 claims description 4
- 229910021419 crystalline silicon Inorganic materials 0.000 claims description 4
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- 229960001413 acetanilide Drugs 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- 229910052790 beryllium Inorganic materials 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 150000003738 xylenes Chemical class 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims 4
- 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 1
- 229930003836 cresol Natural products 0.000 claims 1
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 8
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 8
- 150000002576 ketones Chemical class 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 229920002994 synthetic fiber Polymers 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229960001867 guaiacol Drugs 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by oxidation reactions introducing directly hydroxy groups on a =CH-group belonging to a six-membered aromatic ring with the aid of other oxidants than molecular oxygen or their mixtures with molecular oxygen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Description
Foreliggende oppfinnelse vedrører en fremgangsmåte for hydroksylering av aromatiske hydrokarboner valgt blant gruppen av fenol, toluen, anisol, xylener, mesitylen, benzen, nitrobenzen, etylbenzen og acetanilid, ved omsetning med hydrogenperoksyd i nærvær av syntetiske zeolitt-katalysatorer bestående av krystallinsk silisiumoksyd modifisert ved at silisiumatomer er utvekslet med og/eller erstattet av elementer valgt blant Cr, Be, Ti, V, Mn, Fe, Co, Zn, Zr, Rh, Ag, Sn, Sb, og B, og det særegne ved fremgangsmåten i henhold til oppfinnelsen er at omsetningen gjennomføres i nærvær av aceton, foretrukket ved tilbake-løpstemperaturen. Disse trekk ved oppfinnelsen fremgår av patentkravet. The present invention relates to a method for the hydroxylation of aromatic hydrocarbons selected from the group of phenol, toluene, anisole, xylenes, mesitylene, benzene, nitrobenzene, ethylbenzene and acetanilide, by reaction with hydrogen peroxide in the presence of synthetic zeolite catalysts consisting of crystalline silicon oxide modified by silicon atoms are exchanged with and/or replaced by elements selected from Cr, Be, Ti, V, Mn, Fe, Co, Zn, Zr, Rh, Ag, Sn, Sb, and B, and the peculiarity of the method according to the invention is that the reaction is carried out in the presence of acetone, preferably at the reflux temperature. These features of the invention appear in the patent claim.
Den direkte hydroksylering av aromatiske hydrokarboner med The direct hydroxylation of aromatic hydrocarbons with
hjelp av hydrogenperoksyd har vært kjent i noen tid og gjennomføres i nærvær av en katalysator generelt valgt fra overgangsmetallene. using hydrogen peroxide has been known for some time and is carried out in the presence of a catalyst generally selected from the transition metals.
Denne reaksjon har imidlertid visse ulemper, inklusive de følgende: - lav selektivitet med hensyn til hydrogenperoksydet pga. dets delvise spaltning pga. metallionene, - lav selektivitet med hensyn til utgangshydrokarbonet pga. koblingsreaksjoner med intermediat-organiske radikaler, - i det spesielle tilfellet med fenol er de dannede difenoler lettere oksyderbare enn selve fenolen og dette resul-terer uunngåelig i betraktelig omdannelsesreduksjon. However, this reaction has certain disadvantages, including the following: - low selectivity with respect to the hydrogen peroxide due to its partial cleavage due to the metal ions, - low selectivity with regard to the starting hydrocarbon due to coupling reactions with intermediate organic radicals, - in the special case of phenol, the diphenols formed are more easily oxidizable than the phenol itself and this inevitably results in a considerable reduction in conversion.
Ved å gjennomføre reaksjonen mellom et aromatisk hydrokarbon og hydrogenperoksyd er det også kjent å anvende et surt alumino-silikat som er blitt underkastet doping eller delvis modifisert ved hjelp av sjeldne jordartmetaller (US-patentskrift 3.580.956). By carrying out the reaction between an aromatic hydrocarbon and hydrogen peroxide, it is also known to use an acidic aluminosilicate which has been subjected to doping or partially modified by means of rare earth metals (US patent 3,580,956).
Selv om det forbedrer yteevnen ved de nevnte systemer, vil imidlertid ikke bruken av dette katalytiske material full-stendig eliminere dannelse av betraktelige mengder av unyttige biprodukter, og disse påvirker negativt de ende-lige resultater og lønnsomheten av hele prosenten. Although it improves the performance of the mentioned systems, the use of this catalytic material will not completely eliminate the formation of considerable amounts of useless by-products, and these negatively affect the final results and the profitability of the whole percentage.
Det er fra den norske patentansøkning nr. 81.3025 også kjent at det er mulig å binde hydroksylgrupper til aromatiske kjerner ved å omsette det angjeldende aromatiske hydrokarbon med hydrogenperoksyd, uten noen av de nevnte ulemper, ved gjennomføring av reaksjonen i nærvær av syntetiske zeolitter inneholdende enten erstattede eller utvekslede heteroatomer. It is also known from the Norwegian patent application no. 81.3025 that it is possible to bind hydroxyl groups to aromatic nuclei by reacting the aromatic hydrocarbon in question with hydrogen peroxide, without any of the aforementioned disadvantages, when carrying out the reaction in the presence of synthetic zeolites containing either substituted or exchanged heteroatoms.
Zeolittmaterialer som kan anvendes ved fremgangsmåten i henhold til den nevnte patentansøkning kan velges f.eks. Zeolite materials that can be used in the method according to the aforementioned patent application can be chosen, e.g.
fra den som er beskrevet i den norske patentansøkning nr. 79.2059. from the one described in the Norwegian patent application no. 79.2059.
Den sistnevnte ansøkning beskriver et syntetisk material bestående av krystallinsk silisiumoksyd modifisert ved nærvær av elementer som går inn i det krystallinske silisium-oksydgitter for å erstatte noen silisiumatomer. The latter application describes a synthetic material consisting of crystalline silicon oxide modified by the presence of elements that enter the crystalline silicon oxide lattice to replace some silicon atoms.
De modifiserende elementer velges fra Cr, Be, Ti, V, Mn, Fe, Co, Zn, Rh, Ag, Sn, Sb, B.'The modifying elements are selected from Cr, Be, Ti, V, Mn, Fe, Co, Zn, Rh, Ag, Sn, Sb, B.'
Den nevnte patentansøkning vedrører også fremgangsmåter for fremstilling av disse syntetiske materialer og det vises til denne ansøkning for mulige ytterligere detaljer og for en bedre forståelse av strukturen av selve materi-alet. The aforementioned patent application also relates to methods for the production of these synthetic materials and reference is made to this application for possible further details and for a better understanding of the structure of the material itself.
I forbindelse med hydroksyleringsprosessen som er gjen-stand for den nevnte norske patentansøkning nr. 81,3025 In connection with the hydroxylation process which is the subject of the aforementioned Norwegian patent application no. 81,3025
er det viktig å legge vekt på den store fordel med å gjen-nomføre prosessen som skyldes bruken av av syntetiske it is important to emphasize the great advantage of carrying out the process due to the use of synthetics
zeolitter, idet denne fordel består i muligheten av å sty-re reaksjonen mot dannelse av et produkt snarere enn et annet ved enkelt valg av en bestemt modifisert zeolitt. zeolites, as this advantage consists in the possibility of directing the reaction towards the formation of one product rather than another by simply choosing a particular modified zeolite.
F.eks. i tilfellet med fenolhydroksylering anvendes et porøst krystallinsk syntetisk material dannet fra silisi-um og titanoksyder, og bruken av et slikt material mulig-gjør oppnåelse av en blanding av hydrokinon og pyrokatekol i forhold libeller mer. E.g. in the case of phenol hydroxylation, a porous crystalline synthetic material formed from silicon and titanium oxides is used, and the use of such a material makes it possible to obtain a mixture of hydroquinone and pyrocatechol in more equal proportions.
Slike krystallinske syntetiske materialer er hvilke som helst av de materialer som er kjent fra den norske patent-ansøkning nr. 80.3859. Such crystalline synthetic materials are any of the materials known from Norwegian patent application no. 80.3859.
Reaksjonen mellom deta aromatiske hydrokarbon og hydrogenperoksyd gjennomføres ved en temperatur mellom 80 og 120°c i nærvær av hydrokarbonet enten alene eller med et løsnings-middel valgt fra vann, metanol, eddiksyre, isopropanol eller acetonitril. The reaction between the aromatic hydrocarbon and hydrogen peroxide is carried out at a temperature between 80 and 120°c in the presence of the hydrocarbon either alone or with a solvent selected from water, methanol, acetic acid, isopropanol or acetonitrile.
Hydrokarbonsubstrater som kan behandles ved den foreliggende oppfinnelse er fenol, toluen, anisol, xylener, mesitylen, benzen, nitrobenzen, etylbenzen,og acetanilid, og ved å gjennomføre reaksjonen av angjeldende hydrokarbon i nærvær av aceton, kan man anvende meget høye tilførselstakter og oppnå ytterst høye utbytter. Hydrocarbon substrates that can be treated by the present invention are phenol, toluene, anisole, xylenes, mesitylene, benzene, nitrobenzene, ethylbenzene, and acetanilide, and by carrying out the reaction of the hydrocarbon in question in the presence of acetone, very high feed rates can be used and extremely high yields.
Mengden av tunge biprodukter er meget liten. The amount of heavy by-products is very small.
Reaksjonen gjennomføres foretrukket ved tilbakeløpstempe-ratur. The reaction is preferably carried out at reflux temperature.
Arbeidsbetingelsene vil fremgå fra de illustrerende eksempler og sammenlikningseksempler som er gitt i det følgende, hvori følgende definisjoner anvendes: The working conditions will appear from the illustrative examples and comparative examples given below, in which the following definitions are used:
I det etterfølgende er "katalysatoren" et titanium-silikalitt fremstilt i samsvar med eksempel 1 i norsk patentansøkning 80.3859. In what follows, the "catalyst" is a titanium silicalite produced in accordance with example 1 in Norwegian patent application 80.3859.
EKSEMPEL 1 EXAMPLE 1
50 g fenol, 39 g aceton, og 2,5 g katalysator innføres i en 250 cc kolbe. Når systemet oppnår en temperatur på 50 g of phenol, 39 g of acetone, and 2.5 g of catalyst are introduced into a 250 cc flask. When the system reaches a temperature of
80°C tilsettes 10 cc 36% vekt/volum ^ 2°2' Følgende resultater oppnås etter 2 timers reaksjon: 80°C add 10 cc 36% weight/volume ^ 2°2' The following results are obtained after 2 hours of reaction:
EKSEMPEL 2 EXAMPLE 2
Metoden i eksempel 1 følges, men det tilsettes 15 cc 36* vekt/volum ^C^. Følgende resultater oppnås etter 2 timer: The method in example 1 is followed, but 15 cc 36* weight/volume ^C^ is added. The following results are achieved after 2 hours:
EKSEMPEL 3 EXAMPLE 3
Metoden i eksempel 2 følges, men det tilsettes 20 cc 36% vekt/volum f^C^. The method in example 2 is followed, but 20 cc of 36% weight/volume f^C^ are added.
Følgende resultater oppnås etter 2 timer: The following results are achieved after 2 hours:
EKSEMPEL 4 EXAMPLE 4
Metoden i eksempel 3 følges, men det tilsettes 25 cc 36* <H>2<0>2. The method in example 3 is followed, but 25 cc of 36* <H>2<0>2 are added.
Følgende resultater oppnås etter 2 timer: The following results are achieved after 2 hours:
EKSEMPEL 5 EXAMPLE 5
Metoden i eksempel 4 følges, men det tilsettes 30 cc 36* H202. The method in example 4 is followed, but 30 cc of 36* H 2 O 2 are added.
Følgende resultater oppnås etter 2 timer: The following results are achieved after 2 hours:
EKSEMPEL 6 EXAMPLE 6
30 cc anisol, 70 cc aceton og 3g katalysator innføres i en 250 cc kolbe utstyrt med en kulekondensator. 30 cc of anisole, 70 cc of acetone and 3 g of catalyst are introduced into a 250 cc flask equipped with a spherical condenser.
Etter oppnåelse av en temperatur på 70°c tilsettes 75 cc 36* H202 i dråper. De følgende resultater oppnås ved avsluttet reaksjon: After reaching a temperature of 70°c, 75 cc of 36* H 2 O 2 are added dropwise. The following results are obtained upon completion of the reaction:
Produktfordeling: hydrokinon monometyleter (HMME) 64*, guaiacol 36*. Product breakdown: hydroquinone monomethyl ether (HMME) 64*, guaiacol 36*.
EKSEMPEL 7 EXAMPLE 7
Metoden i eksempel 6 følges, men det tilsettes 10 cc 36* <H>2<0>2. The method in example 6 is followed, but 10 cc of 36* <H>2<0>2 are added.
Resultatene er som følger: The results are as follows:
En kombinasjon av læren for eksempel i DE-25 14 742 og norsk patentansøkningnr. 813025 kunne ikke føre til den foreliggende oppfinnelse da det tyske dokument viser bruken av et keton (også aveton) ved hydroksylering av fenoliske forbindelser i nærvær av hydrogenperoksyd og en katalysator som er svovelsyre eller en sulfonsyre eller salter av disse syrer. A combination of the teaching, for example, in DE-25 14 742 and Norwegian patent application no. 813025 could not lead to the present invention as the German document shows the use of a ketone (also avetone) in the hydroxylation of phenolic compounds in the presence of hydrogen peroxide and a catalyst which is sulfuric acid or a sulphonic acid or salts of these acids.
Syntesebetingelsene er klart forskjellige fra betingelsene ved den foreliggende oppfinnelse hvor det ikke på noen måte er tilstede svovelsyre sulfonsyre eller salter derav, idet katalysator ved oppfinnelsen er en syntetisk zeolitt. The synthesis conditions are clearly different from the conditions of the present invention where sulfuric acid, sulphonic acid or salts thereof are not present in any way, as the catalyst of the invention is a synthetic zeolite.
Dette utdypes ved en nærmere drøftelse i sammenheng med de etterfølgende eksempler 8A og 9A i henhold til oppfinnelsen og sammenlikningseksempler 8B og 9B. This is elaborated by a closer discussion in connection with the following examples 8A and 9A according to the invention and comparative examples 8B and 9B.
Nærmere drøftelse Further discussion
I det følgende anføres ytterligere eksempler som viser at aceton ved den foreliggende oppfinnelse ikke på noen måte er noen glatt ekvivalent med det metylisobutylketon som anvendes som keton i den norske patentansøkning nr. 81c3025. In the following, further examples are given which show that acetone in the present invention is in no way a smooth equivalent to the methyl isobutyl ketone used as ketone in the Norwegian patent application no. 81c3025.
I eks. 8A i samsvar med oppfinnelsen utgjør E^C^-utbyttet allerede etter en time med 73,9% nesten 74% og vektforholdet mellom tjæreaktige rester/tjæreaktige +difenoler utgjør bare 7,8:100. In ex. 8A in accordance with the invention, the E^C^ yield is already after one hour with 73.9% almost 74% and the weight ratio between tarry residues/tarry +diphenols is only 7.8:100.
Ved sammenlikningseksempel 8B er I^C^-utbyttet etter 1 times reaksjonstid bare 50* og heller ikke etter 2 timers reasjonstid når J^C^-utbyttet med bare 68* den verdi som oppnås ved oppfinnelsen etter bare den halve reaksjonstid. Videre dannes i sammenlikningseksempelet 8B ved arbeidsmåten i henhold til den norske patentansøkning nr.81.3025 myemere tjæreaktige rester som vises ved forholdet mellom tjæreaktige rester/-tjæreaktige rester +difenoler = 40,55: 100. In comparative example 8B, the I^C^ yield after 1 hour's reaction time is only 50*, nor after 2 hours' reaction time does the J^C^ yield with only 68* reach the value obtained by the invention after only half the reaction time. Furthermore, in the comparison example 8B, by the working method according to the Norwegian patent application no. 81.3025, more tar-like residues are formed, which is shown by the ratio between tar-like residues/-tar-like residues + diphenols = 40.55: 100.
Sammenlikningen mellom eksemplene 9A og 9B viser likeledes at arbeidsmåten i henhold til oppfinnelsen i nærvær av aceton fører til et vesentlig høyere f^C^-utbytte enn ved arbeidsmåten i henhold til den norske patentansøkning nr. 81.3025, nemlig 40,55* i forhold til 29,14*. The comparison between examples 9A and 9B likewise shows that the working method according to the invention in the presence of acetone leads to a significantly higher f^C^ yield than with the working method according to the Norwegian patent application no. 81.3025, namely 40.55* in relation to 29.14*.
Disse resultater er absolutt overraskende og er heller ikke indikert eller nærliggende i forhold til den nevnte DE-AS 25 14 742. Ved den der beskrevne fremgangsmåte for fremstilling åv toverdige fenolderivater, som kan gjennom-føres i nærvær av tallrike ketoner, foretrekkes ganske åpenbart metylisobutylketon, betegnet med den systematiske betegnelse 4-metyl-2-pentanon, som vist i eksemplene 2,3, These results are absolutely surprising and are also not indicated or close in relation to the aforementioned DE-AS 25 14 742. In the process described there for the production of divalent phenol derivatives, which can be carried out in the presence of numerous ketones, methyl isobutyl ketone is quite obviously preferred , designated by the systematic designation 4-methyl-2-pentanone, as shown in examples 2,3,
7 til 35, 38,41 til 47 og 49 til 56. Eksempel 1 i den tyske puplikasjon gir ikke den fagkyndige noen henvisning om at det selv ved overføring av arbeidsmåten i henhold til denne publikasjon-hydroksylering av enverdige fenolderivater i nærvær av et keton - til fremgangsmåten i henhold til den norske patentansøkning - hydroksylering av aromatiske hydrokarboner i nærvær av bestemte syntetiske zeolitter - kunne det med aceton som keton oppnås særlig gode resultater, ettersom totalutbyttene av pyrokatekol og .hydrokinon i eksemplene 1 og 2 i DE-AS 25 14 742 bare skiller seg med 0,6*. 7 to 35, 38,41 to 47 and 49 to 56. Example 1 in the German publication does not give the expert any indication that even when transferring the working method according to this publication - hydroxylation of monovalent phenol derivatives in the presence of a ketone - for the method according to the Norwegian patent application - hydroxylation of aromatic hydrocarbons in the presence of certain synthetic zeolites - particularly good results could be achieved with acetone as a ketone, as the total yields of pyrocatechol and .hydroquinone in examples 1 and 2 in DE-AS 25 14 742 only differ by 0.6*.
Fremgangsmåten i henhold til oppfinnelsen kan således ikke enkelt sluttes fra en mulig kombinering av de to publika-sjoner. Det var tvert om nødvendig å arbeide seg frem til en lære i motsetning til læren i den norske patent-ansøkning (hvor det som keton anvendes metylisobutylketon) ved at det anvendes et annet, ganske bestemt keton ved hydroksyleringen av aromatiske hydrokarboner henholdsvis aromatiske forbindelser i nærvær av andre katalysatorer enn dem som anvendes i henhold til den norske patentansøk-ning. The method according to the invention cannot therefore be simply concluded from a possible combination of the two publications. On the contrary, it was necessary to work towards a teaching contrary to the teaching in the Norwegian patent application (where methyl isobutyl ketone is used as the ketone) by using another, quite specific ketone in the hydroxylation of aromatic hydrocarbons or aromatic compounds in the presence of catalysts other than those used in accordance with the Norwegian patent application.
Eksempelqrunnlag for det foregående Sample qbase for the preceding
Eksempel 8A i henhold til oppfinnelsen Example 8A according to the invention
I en 250 ml kolbe innføres 50g fenol, 39g aceton og 215g titansilikalitt (i henhold til eks. 1 i DE-OS 30 47 798) som katalysator. Så snart systemet hadde nådd termisk likevekt ble det tilsatt 20 ml 35* ^ 2°2 (vekt/volum>• Etter 1 times reaksjon ble det oppnådd følgende resultater; In a 250 ml flask, 50 g of phenol, 39 g of acetone and 215 g of titanium silicalite (according to example 1 in DE-OS 30 47 798) are introduced as catalyst. As soon as the system had reached thermal equilibrium, 20 ml of 35* ^ 2°2 (weight/volume>• After 1 hour of reaction, the following results were obtained;
Fenolselektivitet 92,96* Phenol selectivity 92.96*
H202-utbytte 73,9* H202 yield 73.9*
Tjæreaktige rester/tjæreaktige rester + difenoler = 7,3:100 samt forhold mellom pyrokatekol/hydrokinon =1. Tarry residues/tarry residues + diphenols = 7.3:100 and ratio between pyrocatechol/hydroquinone =1.
Eksempel 8B, sammenlikningsforsøk i henhold til norsk patentansøknin<g> nr. 81. 3025 Example 8B, comparison test according to Norwegian patent application<g> no. 81. 3025
Det ble arbeidet som i eksempel 8A, men med 30 ml metylisobutylketon i stedet for aceton. Etter 1 times reaksjonstid utgjorde H202-omdannelsen 50*. Etter 2 timers reaksjon ble det oppnådd følgende resultater: The procedure was as in Example 8A, but with 30 ml of methyl isobutyl ketone instead of acetone. After 1 hour's reaction time, the H 2 O 2 conversion amounted to 50*. After 2 hours of reaction, the following results were obtained:
Fenolselektivitet 89,96* Phenol selectivity 89.96*
Pyrokatekol/hydrokinon = 1 Pyrocatechol/hydroquinone = 1
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT20262/82A IT1150699B (en) | 1982-03-19 | 1982-03-19 | PROCEDURE FOR THE OXIDRILATION OF AROMATIC HYDROCARBONS |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| NO830926L NO830926L (en) | 1983-09-20 |
| NO156648B true NO156648B (en) | 1987-07-20 |
| NO156648C NO156648C (en) | 1987-10-28 |
Family
ID=11165238
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO830926A NO156648C (en) | 1982-03-19 | 1983-03-16 | PROCEDURE TE FOR HYDROXYLATION OF AROMATIC HYDERS. |
Country Status (10)
| Country | Link |
|---|---|
| BE (1) | BE896225A (en) |
| CH (1) | CH652114A5 (en) |
| DE (1) | DE3309669A1 (en) |
| DK (1) | DK171933B1 (en) |
| FR (1) | FR2523575B1 (en) |
| GB (1) | GB2116974B (en) |
| IT (1) | IT1150699B (en) |
| NL (1) | NL192876C (en) |
| NO (1) | NO156648C (en) |
| SE (1) | SE461730B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| FR2618143B1 (en) * | 1987-07-17 | 1989-09-22 | Rhone Poulenc Chimie | PHENOL HYDROXYLATION PROCESS |
| FR2622575B1 (en) * | 1987-10-29 | 1990-02-23 | Rhone Poulenc Chimie | PROCESS FOR HYDROXYLATION OF PHENOLS AND PHENOL ETHERS |
| FR2622574B1 (en) * | 1987-10-29 | 1990-02-23 | Rhone Poulenc Chimie | PROCESS FOR HYDROXYLATION OF PHENOLS AND PHENOL ETHERS |
| US5254746A (en) * | 1987-10-29 | 1993-10-19 | Rhone-Poulenc Chimie | Hydroxylation of phenols/phenol ethers |
| FR2643633B1 (en) * | 1989-02-28 | 1991-05-10 | Rhone Poulenc Chimie | PROCESS FOR HYDROXYLATION OF PHENOLS AND PHENOL ETHERS |
| EP0466545A1 (en) * | 1990-06-29 | 1992-01-15 | Rhone-Poulenc Chimie | Zeolites based on silica and oxides of tetravalent elements, method for their synthesis and their use |
| FR2666333B1 (en) * | 1990-08-31 | 1994-04-08 | Rhone Poulenc Chimie | PROCESS FOR HYDROXYLATION OF PHENOLS AND PHENOL ETHERS. |
| EP0473509A3 (en) * | 1990-08-29 | 1992-03-18 | Rhone-Poulenc Chimie | Method for preparation of zeolites based on silica and, possibly, oxides of tetravalent elements |
| DE4138155A1 (en) | 1991-11-21 | 1993-05-27 | Basf Ag | METHOD FOR PRODUCING ESSENTIALLY ALKALIFIED TITANICILICATE CRYSTALS WITH ZEOLITE STRUCTURE |
| US5426244A (en) * | 1991-12-20 | 1995-06-20 | Mitsubishi Gas Chemical Company, Inc. | Method for preparing dihydric phenols |
| DE4214174A1 (en) * | 1992-04-30 | 1993-11-04 | Basf Ag | METHOD FOR PRODUCING N-HYDROXYAZOLES |
| FR2693457B1 (en) * | 1992-07-10 | 1994-09-02 | Rhone Poulenc Chimie | Process for the hydroxylation of phenolic compounds. |
| US5233097A (en) * | 1992-10-15 | 1993-08-03 | Uop | Oxidation of aromatics to hydroxyaromatics using aluminosilicates containing framework titanium |
| HU214200B (en) * | 1992-12-03 | 1998-01-28 | Leuna-Katalysatoren Gmbh. | Oxydation catalysts and methods of producing them and their use |
| DE4419195A1 (en) * | 1993-07-12 | 1995-01-19 | Degussa | Structured catalyst consisting of microporous oxides of silicon, aluminum and titanium |
| RU2058286C1 (en) * | 1994-04-12 | 1996-04-20 | Институт катализа им.Г.К.Борескова СО РАН | Method for production of phenol or its derivatives |
| RU2074164C1 (en) * | 1994-04-12 | 1997-02-27 | Институт катализа им.Г.К.Борескова СО РАН | Method of producing phenol and derivatives thereof |
| US5712402A (en) | 1994-08-22 | 1998-01-27 | Board Of Trustees Operating Michigan State University | Catalytic applications of mesoporous metallosilicate molecular sieves and methods for their preparation |
| DE19607577A1 (en) * | 1996-02-29 | 1997-09-04 | Basf Ag | Mesh catalyst based on titanium or vanadium zeolites and inert mesh fabrics to accelerate oxidation reactions |
| US5874646A (en) * | 1996-08-07 | 1999-02-23 | Solutia Inc. | Preparation of phenol or phenol derivatives |
| US5892132A (en) * | 1996-08-08 | 1999-04-06 | Solutia Inc. | Transport hydroxylation reactor |
| US5874647A (en) * | 1996-08-20 | 1999-02-23 | Solutia Inc. | Benzene hydroxylation catalyst stability by acid treatment |
| US5808167A (en) * | 1996-08-20 | 1998-09-15 | Solutia Inc. | Selective introduction of active sites for hydroxylation of benzene |
| DK0929507T3 (en) | 1996-10-07 | 2003-03-24 | Solutia Inc | Process for hydroxylation of benzene |
| US6156938A (en) * | 1997-04-03 | 2000-12-05 | Solutia, Inc. | Process for making phenol or phenol derivatives |
| CN1278808A (en) * | 1997-11-14 | 2001-01-03 | 杜邦药品公司 | Process for the selective oxidation of organic compounds |
| EP1044196A2 (en) * | 1997-11-24 | 2000-10-18 | E.I. Du Pont De Nemours And Company | Process for the selective oxidation of organic compounds |
| DE19939416A1 (en) | 1999-08-20 | 2001-02-22 | Basf Ag | Production of zeolite, e.g. titanium zeolite, useful as catalyst (support), sorbent, pigment or filler for plastics, involves crystallizing solid from precursor(s) and direct drying of reaction mixture |
| US6437197B1 (en) * | 2000-04-27 | 2002-08-20 | Shell Oil Company | Process for catalytic hydroxylation of aromatic hydrocarbons |
| JP2005060384A (en) * | 2003-07-30 | 2005-03-10 | Ube Ind Ltd | Manufacturing method of phenol compound |
| AU2003304661A1 (en) * | 2003-12-31 | 2005-07-21 | Council Of Scientific And Industrial Research | Process for conversion of phenol to hydroquinone and quinones |
| MX2007010066A (en) | 2005-02-17 | 2007-11-07 | Monsanto Technology Llc | Transition metal-containing catalysts and catalyst combinations including transition metal-containing catalysts and processes for their preparation and use as oxidation catalysts. |
| FR2987046B1 (en) * | 2012-02-17 | 2014-03-21 | Rhodia Operations | HYDROXYLATION PROCESS FOR AROMATIC COMPOUNDS, HYDROXYLATION CATALYST AND PROCESS FOR PREPARING THE SAME |
| TWI471299B (en) | 2012-10-04 | 2015-02-01 | China Petrochemical Dev Corp Taipei Taiwan | Hydroxylation of phenol |
| CN105523898B (en) * | 2014-09-29 | 2019-03-22 | 中国石油化工股份有限公司 | A kind of method of oxidation of phenol |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1448358A (en) * | 1974-04-04 | 1976-09-08 | Ube Industries | Process for preparint dihydric phenol derivatives |
| US4013727A (en) * | 1974-11-07 | 1977-03-22 | Ube Industries, Ltd. | Process for preparing hydroxyphenyl ethers |
| IT1195029B (en) * | 1980-09-09 | 1988-09-28 | Anic Spa | PROCEDURE FOR THE OXIDRILATION OF AROMATIC HYDROCARBONS |
-
1982
- 1982-03-19 IT IT20262/82A patent/IT1150699B/en active
-
1983
- 1983-03-16 NO NO830926A patent/NO156648C/en not_active IP Right Cessation
- 1983-03-16 GB GB08307296A patent/GB2116974B/en not_active Expired
- 1983-03-16 CH CH1454/83A patent/CH652114A5/en not_active IP Right Cessation
- 1983-03-17 NL NL8300962A patent/NL192876C/en not_active IP Right Cessation
- 1983-03-17 DE DE19833309669 patent/DE3309669A1/en active Granted
- 1983-03-17 DK DK123783A patent/DK171933B1/en not_active IP Right Cessation
- 1983-03-18 FR FR8304502A patent/FR2523575B1/en not_active Expired
- 1983-03-18 SE SE8301492A patent/SE461730B/en not_active IP Right Cessation
- 1983-03-21 BE BE0/210368A patent/BE896225A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| NO156648C (en) | 1987-10-28 |
| DK123783A (en) | 1983-09-20 |
| FR2523575B1 (en) | 1986-10-10 |
| GB8307296D0 (en) | 1983-04-20 |
| NL8300962A (en) | 1983-10-17 |
| BE896225A (en) | 1983-09-21 |
| FR2523575A1 (en) | 1983-09-23 |
| CH652114A5 (en) | 1985-10-31 |
| SE461730B (en) | 1990-03-19 |
| IT1150699B (en) | 1986-12-17 |
| NL192876C (en) | 1998-04-02 |
| DK123783D0 (en) | 1983-03-17 |
| DE3309669A1 (en) | 1983-09-29 |
| NL192876B (en) | 1997-12-01 |
| GB2116974B (en) | 1985-10-02 |
| SE8301492D0 (en) | 1983-03-18 |
| IT8220262A1 (en) | 1983-09-19 |
| SE8301492L (en) | 1983-09-20 |
| GB2116974A (en) | 1983-10-05 |
| IT8220262A0 (en) | 1982-03-19 |
| DE3309669C2 (en) | 1990-10-25 |
| NO830926L (en) | 1983-09-20 |
| DK171933B1 (en) | 1997-08-18 |
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