CA1079304A - Dehydrogenation of hydroxy-cycloaliphatic compounds - Google Patents
Dehydrogenation of hydroxy-cycloaliphatic compoundsInfo
- Publication number
- CA1079304A CA1079304A CA243,915A CA243915A CA1079304A CA 1079304 A CA1079304 A CA 1079304A CA 243915 A CA243915 A CA 243915A CA 1079304 A CA1079304 A CA 1079304A
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- carried out
- catalyst
- iii
- dehydrogenation
- Prior art date
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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
- C07C37/06—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation
- C07C37/07—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation with simultaneous reduction of C=O group in that ring
Abstract
DEHYDROGENATION OF HYDROXY-CYCLOALIPHATIC
COMPOUNDS
Abstract of the Disclosure:
Preparation of 2-hydroxynaphthalenes optionally sub-stituted by aliphatic or aromatic radicals from cycloalkenones or hydroxycycloalkanones by heating them in the presence of a dehydrogenation agent.
COMPOUNDS
Abstract of the Disclosure:
Preparation of 2-hydroxynaphthalenes optionally sub-stituted by aliphatic or aromatic radicals from cycloalkenones or hydroxycycloalkanones by heating them in the presence of a dehydrogenation agent.
Description
HO~ 75/F _06 lO~/93~
The present invention provides a novel process for the preparation of 2-hydroxynaphthalencs by dehydrogenation of the reaction products obtained from cyclohexanones and ~ un-saturated ketones in the Robinson anellation.
Hitherto, the industrial-scale manufacture of 2-hydroxy-naphthalenes consists in reacti.ng naphthalenes with sulfuric acid, neutralizing the naphthalenesulfonic acid, fusiny the naphthalene sulfonate with caustic soda, and liberating the hydroxynaphthalene by means of sulfu.ric acid. The disadvan-tage of this process resides .in the fact that large amounts of salts (Na2SO3, Na2SO~) are inevitably formed which have to be removed from the sewage water with great expenditure.
; Furthermore, it is known to obtain 2-hydroxynaph-thalene by catalytic dehydroyenation of ~-tetralone. However, this lS process yields only 26% of ~-naphthol, apart from 54% of naphthalene.
The present invention provides a novel process for the preparation of 2-hydroxynaphthalencs by dehydrogenation of the reaction products obtained from cyclohexanones and ~ un-saturated ketones in the Robinson anellation.
Hitherto, the industrial-scale manufacture of 2-hydroxy-naphthalenes consists in reacti.ng naphthalenes with sulfuric acid, neutralizing the naphthalenesulfonic acid, fusiny the naphthalene sulfonate with caustic soda, and liberating the hydroxynaphthalene by means of sulfu.ric acid. The disadvan-tage of this process resides .in the fact that large amounts of salts (Na2SO3, Na2SO~) are inevitably formed which have to be removed from the sewage water with great expenditure.
; Furthermore, it is known to obtain 2-hydroxynaph-thalene by catalytic dehydroyenation of ~-tetralone. However, this lS process yields only 26% of ~-naphthol, apart from 54% of naphthalene.
2-hydroxynaphthalenes are important intermediate products : for organic dyestuffs.
There has now been found a process for the preparatio.n of 2-hydroxy-naphthalenes of the formula R R
R ~ OH
R R
wherein the radicals R, being identical or different, are hydrogen, aliphatic or aromatic radicals; adjacent aliphatic radicals R optionally forming together an alicyclic 5- or 6-membered ring, which comprises heatiny cycloalkenones or hydroxycycloalkanones of the formulae II to IV
~ 93~
R ~ ~ ~ 0 R ~ 0 R ~ ~ 0 R R R ~ R
Il III . IV
.. . . .
wherein the radicals R ar6! as defined above, in the presence o~ a dehydrogenating agent.
The compounds o~ formulae II~ III and IV may be obtained in known manner, ~or example ~rom ~t n-unsaturat~d ketones and cyclic ketones such as cyclohexanones, or ~- and B-decalones or thelr enamines or ketimi.ne~.
~ Suitable aliphatio radical~ are straight~chain, branched or cyclic alkyl radicals, pre~erably those having up to 12 carbon atoms. Especially mcthyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, cyclopentyl, cyclohexyl and cy~lo-dodecyl are pre~erred.
Generally, the radicals R together do not contain more than 24 carbon atoms. The alkyl radioals may be subst.ituted~
for example by halogen, espec~ally fluorine or chlorine, or by ~ .
pheny}, naph~hyl,:hydroxy, methoxy5 acetoxy9 carbamide or carbo--nitrile, but also by carbalkoxy ha~ing up to 6 carbon atoms, for example carboxymethyl ( -coocH3 3 or carbo~yethyl (_COOC2H5).
~25~ :~ Suitable aromatic radioals are ~or example aryl groups having~from 6~to:1~ carbon a~oms; phen~l or naphthyl being pr~er~ed. :Th.e aryl groups may be ~ubstituted, ~or example by ha~ogen, especially fluorine:or~chlorine, alkyl having up to 29~ 6 carbcn~atom~,~cr~by tri~luoro~ethyl or nitro, but also by ',~5~ 3 -. .
; ~. . .. . , . . : - . ' .` , ~ . , ' , , .
. ~ . . . .
~IOE 751F 006 ~ 3~'~
alkoxy having up to 6 carbon atoms such as methoxy or ethoxy.
Dehydrogenation o~ the cycloalkenones or hydroxyalka~ones is carried out by hea-ting them in the presence of a dehydrogen-ating agent, for example by reaction with sulfur9 selenium, chloranil~ Pd(II) salt~ or by heating them in the presence of a dehydrogenation catalyst/
Suitable dehydrogenation cRtalysts are for example ruthenium~ rhodium, palladium, osmium9 iridium and platinum, but also metals such as copper, silver, gold, iron, cobalt, nickel and chromium~ or mixtures of these elements, as well as also the salts thereo~. Suitable salts are ~or example chlorides, oxides, acetates or carbonates. Preferred elements are palladi~, platinum, ruthenium and copper, or the salts ; thereof.
The catalysts are preferably used on carriers, ~or example on carbon9 aluminum oxide, silicic acid, magnesium oxide, calcium oxide, titanium oxide and asbestos, or a mixture o~
two or more of the cited carriers ~ Palladium o~ carhon is especially recommended. The concentration o~ the catalyst is ~20 advantageously from 0.02 to 20 weight %, relative to the carrier, preferably from 0.1 to 10 weight %.
The process may be carried out in the liquid or gaseous phase, batchwise or continuously~
Operations in the liquid phase are generally carried out at temperatures of from 140 to 350C and under a pressure . su~icient ~or maintaining the liquid phase. Temperatures of ~rom 180 to 250C are preferred/ since these temperatures ensure an e~pecially high selectivity and simultaneously a 29 ~ very rapid course of the dehydrogenation reaction.
.
.
~ - 4 - ~
. . . . .
. .. : ~ .. , - - . - - . .. .. .. . . -: ', ' . ': - ' '' ' ~ ' .: . , .
, , : :, - .. : : ... .
.. . .
k~ _Z~F ~6 10~9~
The reaction pressure in the case of liquid phase operation is generally from 0.5 to 20 atmospheres, but it must be at leas-t su~ficient for maintaining a liquid phase.
It is important to keep low the partial pressure of the nydrogen Iormed during ihe dehydrogenaiion3 so thai ihe equi-librium is shifted in ~avor of the dehydrogerlation and hydro-genation or hydrogenolysis o~ I;he starting compounds and ~inal product~ is prevented. Such a low hydrogen partial pressure may be obtained by flushing the reaction system with an inert gas, ~or example nitrogen or carbon dioxide.
Liquid phase operation may be carried out in the pre~ence o~ a suitable solvent, for example aliphatic ethers, aromatic ethers 9 such as diphenyl ether; hydrocarbons, such as benzene, toluene, ~ylene, pseudo-cumene, naphthalene, biphenyl, tetra-line, decaline; ketones/ such as acetone, diethylketone~ methyl-ethylketone or methylisobu-tylketone; esters, such as cyclo-hexyl propionate or trimethyleneglycol diacetate; but also acid amides, for example dimethyl formamide or N-methyl-pyrro lidone, alcohols, phenols, water or the reaction product it~
self are suitable.
P~e~erred solvents are aliphatic ethers, for example poly-glycol dialkyl ethers, such as di.~ tri- or tetraethyleneglycol dialkyl ethers having generally alkyl groups o~ up to 6 carbon a*oms.
Especially advantageous are polyglycol dimethyl and di-ethyl ethers. The polyglycol dialkyl ethers have the advantage o~ boiling under atmospheric pressure in the pre~erred temper-ature range of from 180 to 260C, which is extremely fa~orable 29 ~or the process of the in~ention, since it allows operating - 5 ~
:: :
. . .
.
. . .
ilOE 75/F _06 1~93~
without pressure an~ since the dehydrogenation ~ith reElux in the preferred temperat~lre range proceeds most rapidly and wi-th high selectivity.
The efficiency of the process is increased by vigorous agitation of the reaction mixture as long as it is in contact with the catalyst.
It is very advantageous -to operate in the presence of hydrogen accepting substances, that is, substances which bind the hydrogen immediately after its formation, thus cnsuring that the dehydrogena-tion reaction proceeds under relatively gentle conditions. Suitable hydrogen accep-tors are unsaturated compounds such as styrene, ~- and ~-methylstyrene, s-tilhene, anthracene, acenaphthylene, crotonic acid, maleic acid, fumaric and cinnamic acid as well as the alkyl esters of these acids with alcohols having up to 6 car~on atoms/ butene-diol, butine-diol and thir acetates and propionates, mesityl oxide, benzal-acetone or maleic acid anhydride. Also nitro compounds, for example nitrobenzene, p-nitrotoluene or o-nitrophenol are appro-priate.
The process of the invention is generally carried out in the presence of a fixed bed catalyst or a catalyst being main-: tained in suspension in the reaction solution by vigorous agi-- tation.
In the case of using a fixed bed catalyst, the particle 25~ size of the catal~st is advantageously from 0.5 to 10 mm, pre-ferably from 2 to 5 mm.
In the case where a`catalyst on a carrier suspended in the reaction. medium i9 used, a particle size of the catalyst of ~:~ from O.Ol to 5 mm, preferably from 0.05 to 1 mm, is recommended.
.. , : . . : . . ........................................ ..
~, : , .; , 10~930~
Depending on the nature of the liquid and the catalyst, the suspension ~ontains generally from 0.~ to 40 parts by weight o~ catalyst on carrier per 100 parts by weight o~ the l~quid.
A ratio of from 1 to 30 parts by weight of catalyst on carrier pe~ 100 p~rts by weight ~ s~l~rPnt ~s pre~P red.
When the process is carried out in the gaseous phase, a carrier gas such as nitrogen, C02, or hydrogen or a hydrogen acceptor such as ethylene or propylene, or highly volatile æolvents, ~or example alcohols, ethers, acetic acid or acetone~
ma~ be added to the starting material be~ore the vaporization.
Water is mo~t advantageous, slnce it~ presence increases con-siderably the se~tivity of 2-hydroxy-naphthalene ~ormation~
be~ause it prevents ~ormation of naphthalene~
In the liquid as well as in the gaseous phase~ the ternper-ature and the residence time necessary for dehydrogenation may vary within a wide range, depending on the starting materials and ~he kind o~ cntalyst used. Generally~ operations are carried out at temperatures of ~rom 160 to 450C, preferably ~rom 200 to 350C, continuously or batchwise, under reduced or normal pressure, although higher pressures are allowed~ for example 20 atmospheres~ on condition that the H2 partial pres--sure is kept low.
The following exampl~s illustrate the in~ention.
E X A M P L E S:
m e starting materials for Examples 1 to 5 have been pre-pared according to the method described ln Organic Syntheses, ; Vol. 459 pp. 130 - 83, and identified according ko the data in-, ~
dicated by ~.L. Augustine et al. in Chem. Ind. (London~, 1963 29 pp. 490j491.
. ~ .
~ - 7 ---, : . ~ . ........ .
~ ; . ~" .' ' '. ' HOE 75~ 006 ~ 3 E X A M P L E 1:
In a three~-necked flask having a capacity o~ 100 ml and provided with thermometer, reflux condenser and gas colleotor vessel, 50 ml of diethyleneglyool diethyl ether, 1 g of de-hydrogenation catalyst (0.1 g Pd on 0.9 g active carbon and 4.8 g (0.032 mol) of a mixture composed of about 80 % of (9~-octalone-27 10 % of~9 (1)-octalone-2 an~ 10 % of 9-hydroxydecalone-2 were heated for 5 hours at 190C7 which caused the development of 2.1 l o~ gasO A~ter suction~filtra-tion of the catalyst~ the gas chromatography analysis o~ the filtrate yielded 3.9 g o~ B-naphthol (85 mol %) and 0.5 g of naphthalene (12 mol ~).
2.
4,8 g of the oxo-cycloaliphatic mixture o~ Example 1 and 1 g of Pd/C catalyst (0.1 g Pd, 0.~ g active carbon ) were heated for 1 hour at 215 - 220C, which caused the development of 2.0 l o~ gas. After cooling, the reaction mixture was digested with ~0 ml of di-ethyleneglycol diethyl ether~ and the catalyst was suction-filtered. The gas chromatography analysis o~ the filtrate yielded 3.2 g of R-naphthol (70 % o~
the theoretical yield~ and O.g g of naphthalene (22 % of the theoretical yieId)~
E X A M ,~ ~ B 3~
In a glass reactor having a diameter of 10 mm and a length of 120 mm, there were 5 ml of catalyst (2.0 weight % o~ Pd on active carbon~ bu~k density 005 g/ml, diameter 0~2~2 mm).
The catal~st temperature was maintained during the reaction . j ,-a~ ~0C by means o~ an electric stove. Before the reaction~
29 ~he catalyst had been actlvated ~or 2 hours at 170C b~ me~ns : 8 -. .
.
- . . . -, . ~ .,,. , ., . . . . . .
, - , .: ~. . . . . ~ .
HOE 7~F 006 ___ _ ~0~
of 0.7 l!h of N2 and 1.4 l/h of H2.
Subsequently, 2.25 g/h of the oxoc;ycloaliphatic mixture described in Example 1, 0 7 l o~ N2 and 1.4 l o~ H2 per hour were forwarded via an evaporator preheated to 350C to the ~boYs cata~yst haYl nv a tempera+l]re of 32QC, The prO~l~C+
collected at the reactor outlet in a cooled collector vessel solidified in the form of white crystals (2.15 g/h3 having a melting point of 106C, which crystals9 according to GLC
~ analysis,consisted o~ 60 % o~ B-naphthol and 35 % of naph~
thalene.
E X A M P L E 4:
The glass reactor described in Example 3 was charged with the catalyst described in the same Example.
After a 2 hour activation by means of 0.7 l/h o~ N2 and 1.4 l/h of H2 at 170C, 1.9 ~/h of the oxo-cycloaliphatic mixture as described in Example 1, and 1.4 1 of H2, 2~0 g of H20 and 0 7 l o~ N2 (all per hour) were forwarded to the catalyst ha~ing a temperature of 285C. The product obtained in the cooled collector vessel was in ~he form of an aqueous crystal pulp which, according to GLC analysis, contained 1.5 g (~2 % o~ the theoretical yield)o~ ~-naphthol and 0.24 g (15 ~ of the theore-tical yield ) of naphthalene.
_A~
0.5 g of 9-hydroxydecalone~2 (melting poi~t 145C) and 0.1 g of catal~Jst (0.01 g of Pd on 0.09 g o~ active carbon) were heat~d ~or 20 minutes at 210C in a~ Erle~eye~ ~lask having a capac$ty o~ 20 ml whereby gas development occurred-~ A~te~ cooling, 10 ml~ of ethanol were added9 the catalyst was 29 separated by ~iltration9 and the filtrate was subjected to thin _ g .,, ;~
~ ~ , , IOE 75/ _006 ~ 3~
layer chromatograph~ on sil:ica gel plates with an ether/hexane 1/1 mixture as solven-t, whereby ~-naphthol was de-tec-ted.
On spraying with a methanolic so].ution of fast blue salt ss and subse~uent treating w:ith ammon:ia vapor, ~-naphthol was showing as a violet spot having a Rf value of 0.51. Color and Rf value are identical to color and Rf value of yenuine ~-naphthol.
' : .
.
~ ' ~
: :
, - 1 0 - '
There has now been found a process for the preparatio.n of 2-hydroxy-naphthalenes of the formula R R
R ~ OH
R R
wherein the radicals R, being identical or different, are hydrogen, aliphatic or aromatic radicals; adjacent aliphatic radicals R optionally forming together an alicyclic 5- or 6-membered ring, which comprises heatiny cycloalkenones or hydroxycycloalkanones of the formulae II to IV
~ 93~
R ~ ~ ~ 0 R ~ 0 R ~ ~ 0 R R R ~ R
Il III . IV
.. . . .
wherein the radicals R ar6! as defined above, in the presence o~ a dehydrogenating agent.
The compounds o~ formulae II~ III and IV may be obtained in known manner, ~or example ~rom ~t n-unsaturat~d ketones and cyclic ketones such as cyclohexanones, or ~- and B-decalones or thelr enamines or ketimi.ne~.
~ Suitable aliphatio radical~ are straight~chain, branched or cyclic alkyl radicals, pre~erably those having up to 12 carbon atoms. Especially mcthyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, cyclopentyl, cyclohexyl and cy~lo-dodecyl are pre~erred.
Generally, the radicals R together do not contain more than 24 carbon atoms. The alkyl radioals may be subst.ituted~
for example by halogen, espec~ally fluorine or chlorine, or by ~ .
pheny}, naph~hyl,:hydroxy, methoxy5 acetoxy9 carbamide or carbo--nitrile, but also by carbalkoxy ha~ing up to 6 carbon atoms, for example carboxymethyl ( -coocH3 3 or carbo~yethyl (_COOC2H5).
~25~ :~ Suitable aromatic radioals are ~or example aryl groups having~from 6~to:1~ carbon a~oms; phen~l or naphthyl being pr~er~ed. :Th.e aryl groups may be ~ubstituted, ~or example by ha~ogen, especially fluorine:or~chlorine, alkyl having up to 29~ 6 carbcn~atom~,~cr~by tri~luoro~ethyl or nitro, but also by ',~5~ 3 -. .
; ~. . .. . , . . : - . ' .` , ~ . , ' , , .
. ~ . . . .
~IOE 751F 006 ~ 3~'~
alkoxy having up to 6 carbon atoms such as methoxy or ethoxy.
Dehydrogenation o~ the cycloalkenones or hydroxyalka~ones is carried out by hea-ting them in the presence of a dehydrogen-ating agent, for example by reaction with sulfur9 selenium, chloranil~ Pd(II) salt~ or by heating them in the presence of a dehydrogenation catalyst/
Suitable dehydrogenation cRtalysts are for example ruthenium~ rhodium, palladium, osmium9 iridium and platinum, but also metals such as copper, silver, gold, iron, cobalt, nickel and chromium~ or mixtures of these elements, as well as also the salts thereo~. Suitable salts are ~or example chlorides, oxides, acetates or carbonates. Preferred elements are palladi~, platinum, ruthenium and copper, or the salts ; thereof.
The catalysts are preferably used on carriers, ~or example on carbon9 aluminum oxide, silicic acid, magnesium oxide, calcium oxide, titanium oxide and asbestos, or a mixture o~
two or more of the cited carriers ~ Palladium o~ carhon is especially recommended. The concentration o~ the catalyst is ~20 advantageously from 0.02 to 20 weight %, relative to the carrier, preferably from 0.1 to 10 weight %.
The process may be carried out in the liquid or gaseous phase, batchwise or continuously~
Operations in the liquid phase are generally carried out at temperatures of from 140 to 350C and under a pressure . su~icient ~or maintaining the liquid phase. Temperatures of ~rom 180 to 250C are preferred/ since these temperatures ensure an e~pecially high selectivity and simultaneously a 29 ~ very rapid course of the dehydrogenation reaction.
.
.
~ - 4 - ~
. . . . .
. .. : ~ .. , - - . - - . .. .. .. . . -: ', ' . ': - ' '' ' ~ ' .: . , .
, , : :, - .. : : ... .
.. . .
k~ _Z~F ~6 10~9~
The reaction pressure in the case of liquid phase operation is generally from 0.5 to 20 atmospheres, but it must be at leas-t su~ficient for maintaining a liquid phase.
It is important to keep low the partial pressure of the nydrogen Iormed during ihe dehydrogenaiion3 so thai ihe equi-librium is shifted in ~avor of the dehydrogerlation and hydro-genation or hydrogenolysis o~ I;he starting compounds and ~inal product~ is prevented. Such a low hydrogen partial pressure may be obtained by flushing the reaction system with an inert gas, ~or example nitrogen or carbon dioxide.
Liquid phase operation may be carried out in the pre~ence o~ a suitable solvent, for example aliphatic ethers, aromatic ethers 9 such as diphenyl ether; hydrocarbons, such as benzene, toluene, ~ylene, pseudo-cumene, naphthalene, biphenyl, tetra-line, decaline; ketones/ such as acetone, diethylketone~ methyl-ethylketone or methylisobu-tylketone; esters, such as cyclo-hexyl propionate or trimethyleneglycol diacetate; but also acid amides, for example dimethyl formamide or N-methyl-pyrro lidone, alcohols, phenols, water or the reaction product it~
self are suitable.
P~e~erred solvents are aliphatic ethers, for example poly-glycol dialkyl ethers, such as di.~ tri- or tetraethyleneglycol dialkyl ethers having generally alkyl groups o~ up to 6 carbon a*oms.
Especially advantageous are polyglycol dimethyl and di-ethyl ethers. The polyglycol dialkyl ethers have the advantage o~ boiling under atmospheric pressure in the pre~erred temper-ature range of from 180 to 260C, which is extremely fa~orable 29 ~or the process of the in~ention, since it allows operating - 5 ~
:: :
. . .
.
. . .
ilOE 75/F _06 1~93~
without pressure an~ since the dehydrogenation ~ith reElux in the preferred temperat~lre range proceeds most rapidly and wi-th high selectivity.
The efficiency of the process is increased by vigorous agitation of the reaction mixture as long as it is in contact with the catalyst.
It is very advantageous -to operate in the presence of hydrogen accepting substances, that is, substances which bind the hydrogen immediately after its formation, thus cnsuring that the dehydrogena-tion reaction proceeds under relatively gentle conditions. Suitable hydrogen accep-tors are unsaturated compounds such as styrene, ~- and ~-methylstyrene, s-tilhene, anthracene, acenaphthylene, crotonic acid, maleic acid, fumaric and cinnamic acid as well as the alkyl esters of these acids with alcohols having up to 6 car~on atoms/ butene-diol, butine-diol and thir acetates and propionates, mesityl oxide, benzal-acetone or maleic acid anhydride. Also nitro compounds, for example nitrobenzene, p-nitrotoluene or o-nitrophenol are appro-priate.
The process of the invention is generally carried out in the presence of a fixed bed catalyst or a catalyst being main-: tained in suspension in the reaction solution by vigorous agi-- tation.
In the case of using a fixed bed catalyst, the particle 25~ size of the catal~st is advantageously from 0.5 to 10 mm, pre-ferably from 2 to 5 mm.
In the case where a`catalyst on a carrier suspended in the reaction. medium i9 used, a particle size of the catalyst of ~:~ from O.Ol to 5 mm, preferably from 0.05 to 1 mm, is recommended.
.. , : . . : . . ........................................ ..
~, : , .; , 10~930~
Depending on the nature of the liquid and the catalyst, the suspension ~ontains generally from 0.~ to 40 parts by weight o~ catalyst on carrier per 100 parts by weight o~ the l~quid.
A ratio of from 1 to 30 parts by weight of catalyst on carrier pe~ 100 p~rts by weight ~ s~l~rPnt ~s pre~P red.
When the process is carried out in the gaseous phase, a carrier gas such as nitrogen, C02, or hydrogen or a hydrogen acceptor such as ethylene or propylene, or highly volatile æolvents, ~or example alcohols, ethers, acetic acid or acetone~
ma~ be added to the starting material be~ore the vaporization.
Water is mo~t advantageous, slnce it~ presence increases con-siderably the se~tivity of 2-hydroxy-naphthalene ~ormation~
be~ause it prevents ~ormation of naphthalene~
In the liquid as well as in the gaseous phase~ the ternper-ature and the residence time necessary for dehydrogenation may vary within a wide range, depending on the starting materials and ~he kind o~ cntalyst used. Generally~ operations are carried out at temperatures of ~rom 160 to 450C, preferably ~rom 200 to 350C, continuously or batchwise, under reduced or normal pressure, although higher pressures are allowed~ for example 20 atmospheres~ on condition that the H2 partial pres--sure is kept low.
The following exampl~s illustrate the in~ention.
E X A M P L E S:
m e starting materials for Examples 1 to 5 have been pre-pared according to the method described ln Organic Syntheses, ; Vol. 459 pp. 130 - 83, and identified according ko the data in-, ~
dicated by ~.L. Augustine et al. in Chem. Ind. (London~, 1963 29 pp. 490j491.
. ~ .
~ - 7 ---, : . ~ . ........ .
~ ; . ~" .' ' '. ' HOE 75~ 006 ~ 3 E X A M P L E 1:
In a three~-necked flask having a capacity o~ 100 ml and provided with thermometer, reflux condenser and gas colleotor vessel, 50 ml of diethyleneglyool diethyl ether, 1 g of de-hydrogenation catalyst (0.1 g Pd on 0.9 g active carbon and 4.8 g (0.032 mol) of a mixture composed of about 80 % of (9~-octalone-27 10 % of~9 (1)-octalone-2 an~ 10 % of 9-hydroxydecalone-2 were heated for 5 hours at 190C7 which caused the development of 2.1 l o~ gasO A~ter suction~filtra-tion of the catalyst~ the gas chromatography analysis o~ the filtrate yielded 3.9 g o~ B-naphthol (85 mol %) and 0.5 g of naphthalene (12 mol ~).
2.
4,8 g of the oxo-cycloaliphatic mixture o~ Example 1 and 1 g of Pd/C catalyst (0.1 g Pd, 0.~ g active carbon ) were heated for 1 hour at 215 - 220C, which caused the development of 2.0 l o~ gas. After cooling, the reaction mixture was digested with ~0 ml of di-ethyleneglycol diethyl ether~ and the catalyst was suction-filtered. The gas chromatography analysis o~ the filtrate yielded 3.2 g of R-naphthol (70 % o~
the theoretical yield~ and O.g g of naphthalene (22 % of the theoretical yieId)~
E X A M ,~ ~ B 3~
In a glass reactor having a diameter of 10 mm and a length of 120 mm, there were 5 ml of catalyst (2.0 weight % o~ Pd on active carbon~ bu~k density 005 g/ml, diameter 0~2~2 mm).
The catal~st temperature was maintained during the reaction . j ,-a~ ~0C by means o~ an electric stove. Before the reaction~
29 ~he catalyst had been actlvated ~or 2 hours at 170C b~ me~ns : 8 -. .
.
- . . . -, . ~ .,,. , ., . . . . . .
, - , .: ~. . . . . ~ .
HOE 7~F 006 ___ _ ~0~
of 0.7 l!h of N2 and 1.4 l/h of H2.
Subsequently, 2.25 g/h of the oxoc;ycloaliphatic mixture described in Example 1, 0 7 l o~ N2 and 1.4 l o~ H2 per hour were forwarded via an evaporator preheated to 350C to the ~boYs cata~yst haYl nv a tempera+l]re of 32QC, The prO~l~C+
collected at the reactor outlet in a cooled collector vessel solidified in the form of white crystals (2.15 g/h3 having a melting point of 106C, which crystals9 according to GLC
~ analysis,consisted o~ 60 % o~ B-naphthol and 35 % of naph~
thalene.
E X A M P L E 4:
The glass reactor described in Example 3 was charged with the catalyst described in the same Example.
After a 2 hour activation by means of 0.7 l/h o~ N2 and 1.4 l/h of H2 at 170C, 1.9 ~/h of the oxo-cycloaliphatic mixture as described in Example 1, and 1.4 1 of H2, 2~0 g of H20 and 0 7 l o~ N2 (all per hour) were forwarded to the catalyst ha~ing a temperature of 285C. The product obtained in the cooled collector vessel was in ~he form of an aqueous crystal pulp which, according to GLC analysis, contained 1.5 g (~2 % o~ the theoretical yield)o~ ~-naphthol and 0.24 g (15 ~ of the theore-tical yield ) of naphthalene.
_A~
0.5 g of 9-hydroxydecalone~2 (melting poi~t 145C) and 0.1 g of catal~Jst (0.01 g of Pd on 0.09 g o~ active carbon) were heat~d ~or 20 minutes at 210C in a~ Erle~eye~ ~lask having a capac$ty o~ 20 ml whereby gas development occurred-~ A~te~ cooling, 10 ml~ of ethanol were added9 the catalyst was 29 separated by ~iltration9 and the filtrate was subjected to thin _ g .,, ;~
~ ~ , , IOE 75/ _006 ~ 3~
layer chromatograph~ on sil:ica gel plates with an ether/hexane 1/1 mixture as solven-t, whereby ~-naphthol was de-tec-ted.
On spraying with a methanolic so].ution of fast blue salt ss and subse~uent treating w:ith ammon:ia vapor, ~-naphthol was showing as a violet spot having a Rf value of 0.51. Color and Rf value are identical to color and Rf value of yenuine ~-naphthol.
' : .
.
~ ' ~
: :
, - 1 0 - '
Claims (7)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the preparation of 2-hydroxy-naphtha-lene of the formula wherein the radicals R, being identical or different, are hy-drogen, aliphatic or aromatic radicals; and adjacent aliphatic radicals R may together form an alicyclic 5- or 6-membered ring, in which a cycloalkenone or hydroxycycloalkanone of the formula II, III or IV
II III IV
wherein the radica1s R are as defined above, is heated in the presence of a dehydrogenating agent.
II III IV
wherein the radica1s R are as defined above, is heated in the presence of a dehydrogenating agent.
2. A process as claimed in claim 1 in which the reaction is carried out in the liquid phase at a temperature of from 140 to 350°C and under a pressure of from 0.5 to 20 atmospheres in the presence of a catalyst containing at least one noble metal of the 8th subgroup of the Periodic System.
3. A process as claimed in claim 1 in which the reaction is carried out in the gaseous phase at a temperature of from 160 to 450°C and under a pressure of from 0.5 to 20 atmospheres in the presence of a catalyst containing at least one noble metal of the 8th subgroup of the Periodic System, or cobalt, nickel, copper or chromium.
4. A process as cliamed in cliam 3 in which the compound of the formula II, III, or IV
II III IV
diluted with hydrogen, nitrogen argon, carbon dioxide, ethylene, propylene or water is fed to the catalyst.
II III IV
diluted with hydrogen, nitrogen argon, carbon dioxide, ethylene, propylene or water is fed to the catalyst.
5. A process as claimed in claim 1 or claim 2 in which the reaction is carried out in a solvent selected from the group of aromatic hydrocarbons, alcohols, ethers, esters, ketones, phenols, water and the reaction product itself.
6. A process as claimed in claim 1, claim 2 or claim 3 in which the dehydrogenation is carried in the presence of a hydrogen acceptor.
7. A process as claimed in claim 1, claim 2 or claim 3 in which the reaction is carried out in the presence of solvent selected from the group of triethylene glycol dialkyl ethers and diethyleneglycol dialkyl ethers containing alkyl groups of up to 6 carbon atoms.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19752501770 DE2501770A1 (en) | 1975-01-17 | 1975-01-17 | PROCESS FOR THE PREPARATION OF 2-HYDROXYNAPHTHALINES |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1079304A true CA1079304A (en) | 1980-06-10 |
Family
ID=5936677
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA243,915A Expired CA1079304A (en) | 1975-01-17 | 1976-01-16 | Dehydrogenation of hydroxy-cycloaliphatic compounds |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JPS51125365A (en) |
| BE (1) | BE837691A (en) |
| CA (1) | CA1079304A (en) |
| CH (1) | CH619916A5 (en) |
| DE (1) | DE2501770A1 (en) |
| FR (1) | FR2297825A1 (en) |
| GB (1) | GB1529012A (en) |
| IT (1) | IT1054795B (en) |
| NL (1) | NL7600258A (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1039710A (en) * | 1950-06-27 | 1953-10-09 | Bataafsche Petroleum | Process for the preparation of phenols |
| FR1344298A (en) * | 1962-08-30 | 1963-11-29 | Progil | Manufacture of heavy phenols |
| NO122978B (en) * | 1968-03-08 | 1971-09-13 | Basf Ag |
-
1975
- 1975-01-17 DE DE19752501770 patent/DE2501770A1/en not_active Withdrawn
-
1976
- 1976-01-12 NL NL7600258A patent/NL7600258A/en not_active Application Discontinuation
- 1976-01-14 CH CH40776A patent/CH619916A5/en not_active IP Right Cessation
- 1976-01-15 GB GB157676A patent/GB1529012A/en not_active Expired
- 1976-01-15 IT IT1930976A patent/IT1054795B/en active
- 1976-01-16 CA CA243,915A patent/CA1079304A/en not_active Expired
- 1976-01-16 JP JP328476A patent/JPS51125365A/en active Pending
- 1976-01-19 BE BE163614A patent/BE837691A/en unknown
- 1976-01-19 FR FR7601217A patent/FR2297825A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| CH619916A5 (en) | 1980-10-31 |
| GB1529012A (en) | 1978-10-18 |
| FR2297825A1 (en) | 1976-08-13 |
| DE2501770A1 (en) | 1976-07-22 |
| NL7600258A (en) | 1976-07-20 |
| BE837691A (en) | 1976-07-19 |
| JPS51125365A (en) | 1976-11-01 |
| FR2297825B1 (en) | 1979-06-29 |
| IT1054795B (en) | 1981-11-30 |
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