CA1055963A - Process for the manufacture of resorcinol - Google Patents
Process for the manufacture of resorcinolInfo
- Publication number
- CA1055963A CA1055963A CA232,790A CA232790A CA1055963A CA 1055963 A CA1055963 A CA 1055963A CA 232790 A CA232790 A CA 232790A CA 1055963 A CA1055963 A CA 1055963A
- Authority
- CA
- Canada
- Prior art keywords
- catalyst
- cyclohexane
- dione
- weight
- resorcinol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
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
-
- 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
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/64—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of functional groups containing oxygen only in singly bound form
-
- 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
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/65—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
PROCESS FOR THE MANUFACTURE OF RESORCINOL
Abstract of the Disclosure:
The present invention is related to a process for the manufacture of resorcinols by catalytic dehydrogenation of cyclohexane diones-(1,3) in the liquid phase by means of a dehydrogenating mixture consisting of a solvent and of a catalyst containing a noble metal of the eighth subgroup of the periodical system.
Abstract of the Disclosure:
The present invention is related to a process for the manufacture of resorcinols by catalytic dehydrogenation of cyclohexane diones-(1,3) in the liquid phase by means of a dehydrogenating mixture consisting of a solvent and of a catalyst containing a noble metal of the eighth subgroup of the periodical system.
Description
Resorcinl is essentially used as synthetic resin component of resorcinol-aldehyde-resins for the rubber and wood glue industries. Substituted resorcinols are employed as coupling components of dyestuffs, e.g. for diazo pr~nting. The manu-facture on a technical scale is carried out, for example, by having benzene react with S03, subsequent alcali fusion of the neutralized benzene disulfonic acid with caustic soda and by acidification of the thus produced resorcinol disodium salt with sulfuric acid. This process has the drawback that large quantities of salt (Na2S04) are formed at rates which surpass by several times the quantities of resorcinol which are pro- -duced by the same process so that the waste waters are sub~ect to considerable contamination.
It is also known that resorcinol may be produced by de-hydrogenation of cyclohexane-dione in the presence of a paliadium catalyst. This method being described by British Patent 1 188 387, is handicapped by small yields in resorcinol of only 26 %, calculated on the quantity of cyclohexane-dione-(1,3) charged.
Cyclohexane-diones-(1,3) are accessible meanwhile according to German Offenlegungsschrift 2 245 270 by cyclization of 4-oxocarboxylic acid esters at excellent yield rates.
A process for the manufacture of resorcinols, having the formula
It is also known that resorcinol may be produced by de-hydrogenation of cyclohexane-dione in the presence of a paliadium catalyst. This method being described by British Patent 1 188 387, is handicapped by small yields in resorcinol of only 26 %, calculated on the quantity of cyclohexane-dione-(1,3) charged.
Cyclohexane-diones-(1,3) are accessible meanwhile according to German Offenlegungsschrift 2 245 270 by cyclization of 4-oxocarboxylic acid esters at excellent yield rates.
A process for the manufacture of resorcinols, having the formula
2~ R-R4~R2 HO ~ H
R~
~9 ~
has now been found wherein the radicals Rl to R4 may be identical or different and represent hydrogen, straight-chain, branched or cyclic alkyl groups which may as well carry sub-stituents, or aryl groups which may also carry substituents, which comprises that cyclohexane diones-(1,3) of formuia R H
R4~R2H
Rl ~
wherein Rl to R4 have the above mentioned meaning are added to a dehydrogenation mixture composed of a solvent and of a catalyst containing a noble metal of the eighth subgroup of the periodical system under a pressure of from 0.5 to 20 atmos-pheres and at a temperature of from 160 to 350C in such a way that the concentration in cyclohexane-dione which is to be dehydro-genated does not surpass 30%, calculated on the weight of the liquid phase.
Especially suitable straight-chain, branched or cyclic alkyl groups are those having up to 12 carbon atoms such as for example methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, cyclopentyl, cyclohexyl, cyclododecyl. Alkyl groups with a double bond are also suitable, e.g. the allyl group.
The alkyl radicals may furthermore be substituted for example by halogens, especially fluorine and chlorine, or by a phenyl, naphthyl, amino, hydroxy, keto, carboxy, carbamide or nitrile group, but as well by a carbalkoxy group having up to 6 carbon atoms such as carboxymethyl (-COOCH3) or by carboxy-10559f~3 ethyl (-COOC2H5).
Suitable aryl groups are for example those having from 6 to 14 carbon atoms, preference is given to the phenyl radical and to the naphthyl radical. The aryl groups may also carry 8ub-stituents, e.g. halogen, especially fluorine and chlorine, alkyl æroups having up to 6 carbon atoms, or by trifluoromethyl groups, pentafluoro-ethyl or nitro groups. There may also be considered for example alkoxy groups having up to 6 carbon atoms, such as the methoxy or ethoxy group.
Especially suitable noble metals are palladium, platinum, - ruthenium and rhodium. These catalysts are generally employed on carrier materials such as carbon, aluminum oxide, silicic acid, magnesium oxide, calcium oxide, titanium oxide and asbestos, preference is given to the use of palladium on carbon.
The useful concentration rate of the noble metal varies from 0.02 to 20 %, calculated on the weight of the carrier material, preferably from 0.1 to 10 weight %.
The process may be carried through continuously or dis-continuously, at temperatures from 160 to 350C, preferably from 180 to 260C, since the latter temperatures achieve a particularly high selectivity combined with a very rapid de-hydrogenation.
The reaction pressure varies from 0.5 to 20 atmospheres, being preferably chosen at such a level that it is sufficient for maintaining a liquid phase.
Preference is given to keeping low the partial pressure of the hydrogen which is formed during the dehydrogenation so as to shift the equilibrum in favor of the dehydrogenation and 29 to avoid a hydrogenation or hydrogenolysis of the starting compounds and the fipal products. This low partial pressure of hydrogen may be achieved by purging the reaction system with an lnert gas, such as nitrogen or carbon dioxide.
Suitable solvents are aliphatic ethers, aliphatic esters ~ 5 such as e.g. succinic acid dialkyl ester or propane-diol-; diacetate or butane-diol-diacetate, aromatic ethers such as - diphenyl ether; hydrocarbons such as benzene, toluene, xylene, pseudocumene, naphthalene, biphenyl, tetralene, decalene;
ketones such as acetone, diethylketone, methyl-ethylketone or methylisobutyl ketone. Also suitable are acid amides such as dlmethyl formamide or N-methyl-pyrrolidone, alcohols, phenols -and water. Preferred solvents are aliphatic ethers such as the polyglycol dialkyl ethers, e.g. diethylene glycol dialkyl ether, triethylene glycol dialkyl ether or tetraethylene glycol dialkyl ether having generally alkyl groups with up to 6 carbon atoms.
Special preference is given to the polyglycol dimethyl ethers and polyglycol diethyl ethers. The polyglycol dialkyl ethers have the advantage that they boil under an atmospheric pressure in the preferred temperature range from 180 to 260C - a fact which has a particularly favorable effect on the process, since it allows for operating under normal pressure ~nd slnce the dehydrogenation is carried out with special speed and selectivity under reflux conditions within the preferred temperature range. The efficiency of the process is enhanced ~; by vigorous agitation of the reaction mixture as long as it is contacting the catalyst.
When the reaction is carried out discontinuously, an es-29 pecially ccnvenient embodi~ent is the addition under reflux - `` 1055963 .
conditions of the cyclohexane dione which is dehydrogenated dissolved in an easily volatile solvent such as acetone, iso-propanol, methanol or water to the dehydrogenation mixture consisting of a catalyst suspension and polyglycol ether as $ sol~ent. The solvent for the cyclohexane dione is thereby removed from the reaction mixture by distillation via a des-cending condenser. The hydrogen which is thereby produced contributes additionally to improve the thorough mixing. After completion of the reaction the reaction mixture is filtered off the catalyst and the resorcinal thus produced is obtained in its pure state by distillation of the filtrate.
When the reaction is carried out continuously, a solution of a cyclohexane dione in the same sol~ent which is also employed for the suspension of the catalyst, is introduced continuously via a preheating device into the dehydrogenation reactor, while simultaneously a corresponding quantity of the reaction mixture containing the resorcinol produced is dis-charged. In that case the catalyst is either retained in the reactor by means of a frit, or, after separation e.g. by means of a hydrocyclone, fed back into the reactor. After having separated by distillation the resorcinol produced from the solvent? the latter is re-used for dissolving newly introduced cyclohexane-dione for dehydrogenation.
The process according to the in~ention can be carried out with a fixed-bed catalyst or with a catalyst which is main-; tained in suspension by stirring the reaction solution vi-gourously.
When using a fixed-bed catalyst, a dimension of from O.5 29 to 10 mm, preferably from 2 to 5 mm is recommended for the HOE 74lF 22~.
lOS5963 catalyst particles. Larger particles reduce the efficiency of the catalyst, whilst smaller particles may lead to 103ses in catalyst and to blocking of the catalyst bed.
- When the process is carried out with a supported catalyst and suspended in the reaction medium, the size of the catalyst particles varies generally from 0.01 to 5 mm, preferably from 0.05 to 1 mm. The smaller particles represent the drawback of hardly `separating from the reaction solution. The dis-advantage of larger particles is the difficulty to maintain them in suspension and the minor dehydrogenation speed. De-pending on the type of the liquid and of the catalyst, the sus-pension may contain from 0.1 to 40 parts by weight of catalyst on a carrier material - in relation to 100 parts by weight of the liquid. Preferred proportions are from 1 to 30 parts ~5 by weight of supported catalyst per 100 parts by weight of solvent.
The proce~s according to the in~ention has the advantage that dehydrogenation takes places immediately upon introduction of the cyclohexane dione into the dehydrogenation mixture, so -that the rather unstable cyclohexane-dione-(1,3) is converted immediately to the resorcinol being very stable under the dehydrogenation conditions.
The process according to the invention achieves much higher yieldæ in resorcinol by catalytic dehydrogenation of cyclo-hexane-diones-(1,3) than those obtained according to known processes.
The following examples illustrate the invention:
.
-H~E 74/F 224 E X A M P L E S 1 - 8 (cf. table):
- A mixture of 50 ml of solvent and 1 g of- dehydrogenation catalyst is heated to 180 - 220C while agitating and purging with nitrogen, in a 100 ml three-necked flask, equipped with thermometer, agitator, dropping funnel and descending condenser (Claisen - bridge). Subsequently, the cyclohexane-dione in a solvent which is either identical with the solvent used for the catalyst suspension or which boils considerably lower is added ln such a way that the cyclohexane-dione concentration doe~ not surpass 30 weight %, calculated on the weight of the liquid phase. The operation is controlled by a gas meter measuring the quantity of hydrogen which is formed during the reaction. During the addition, the temperature is maintained within the range ~ ~m180 to 230C. After having completed the addition of cyclohexane-dione, the temperature is kept at 220 - 230C for a short while until no more hydrogen is pro-duced. Cooling takes then pla~ce while purging with nitrogen, the catalyst is separated and the filtrate is analyzed by GLC
~ and finally sub~ect to distillation in vacuo. After frac-tionating the solvent (e.g. $n the case of diethylene glycol - diethyl ether the boiling point is 78 - 84C under 15 mm/Hg) the desired resorcinol i8 obtained in its pure state (boiling point 158C under 15 mm/Hg). The solvent may be'recycled.
If methanol'is used as solvent texample 5), which esterifies with cyclohexane-dione to yield 3-methoxy-cyclo-hexanone, resorcinol-monomethyl ether is formed as by-product.
.
-`" 1055963 ~ 0~ ~ ~ o ~ a: I I I
O ~ ~r u~ u o _, o~
~ ~ ~ o .,.~ ~ ~ N ~ 0 'O O
~ S~ ~
a) ~ ln S
-- a . dP
^ o o o o o o o o ~c O ~ ~ ~D ~ ~D ~ CD
~-- . ~ o C~ ~ -. ao o . ~ o o. ~ o~r o o o o c) o E~
~ ~ O c~ ~ u~ I` ~ a~
r~ ~ c~ ,, _, ,, O _I a~ c~ ,1 , ~ ~J o N N N N N ~1 _I N :~
j:l ~ ~ ~-- . .C
m n R ~
_I ~
h dP
~ o o O ~d h u) o ~ ~ o o o U~ al ,1 0-- ~r In ~ 10 10 ~r I
~ I
o ~ e ~ N ~
0 ~ o o o m o li3 o o x a) ~ ~ ~ ~
~D a~ H H Cl E H H ~i a1 0 O O O ~ O ~
~1 l,q _ _I ~
C) ~ O rl ~10 ~ O .C
.a ~I h ~
h Cl O O ^ ~
1 e l ~ ~ 1 O , ~ ~ e ~ 8 ~ O P. ~ z m ,~
o Q~ ~ I
6-- ~ ~ ~:
~ .. ~ e ~ ~
~ ~ .,~ o O ~q ~ ~ Zrl Q.
_I R
~ ~ e ~ N ~ ~ 10 ~D t` O~ r!) f~ 1l ~
Q) ~d X W. P~ W
~ c~ ~3 ~ z m ~
E X A M P L E 9: ' .
A mixture of 100 ml of diethylene glycol diethyl ether and 1 g of catalyst (0.1 g Pd on 0.9 g of powdery carbon <0.05 mm) is heated to 190C while purging with nitrogen, in a 250 ml three-necked flask, equipped with agitator, thermometer and descending cooling device. Subsequently, a solution of 22 g of 2,6-dimethyl-3-hydroxycyclohexene-(2)-one (prepared from 4-methyl-5-oxo-hepanoic-acid methyl ester according to German Offenlegungsschrift 2 245 270) in 210 ml of isopropanol is added within two hours, the temperature being maintained at 185C. The isopropanol is removed continuously by distillation.
The development of hydrogen stopped after completion of the addition of the cyclohexane-dione. The contents of the reactor were cooled, the catalyst was filtered off and the filtrate distilled in vacuo. After the diethylene glycol diethyl ether (bolling point 72C under 14 mm/Hg) 18.5 g (= 85.3 % of thec!retical yield) of 2,6-dimethyl resorcinol are passing over at the boiling point of 112C under 2 mm/Hg which cristallize in the collector recipient (m.p. 107C from benzene).
-- ~0 --
R~
~9 ~
has now been found wherein the radicals Rl to R4 may be identical or different and represent hydrogen, straight-chain, branched or cyclic alkyl groups which may as well carry sub-stituents, or aryl groups which may also carry substituents, which comprises that cyclohexane diones-(1,3) of formuia R H
R4~R2H
Rl ~
wherein Rl to R4 have the above mentioned meaning are added to a dehydrogenation mixture composed of a solvent and of a catalyst containing a noble metal of the eighth subgroup of the periodical system under a pressure of from 0.5 to 20 atmos-pheres and at a temperature of from 160 to 350C in such a way that the concentration in cyclohexane-dione which is to be dehydro-genated does not surpass 30%, calculated on the weight of the liquid phase.
Especially suitable straight-chain, branched or cyclic alkyl groups are those having up to 12 carbon atoms such as for example methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, cyclopentyl, cyclohexyl, cyclododecyl. Alkyl groups with a double bond are also suitable, e.g. the allyl group.
The alkyl radicals may furthermore be substituted for example by halogens, especially fluorine and chlorine, or by a phenyl, naphthyl, amino, hydroxy, keto, carboxy, carbamide or nitrile group, but as well by a carbalkoxy group having up to 6 carbon atoms such as carboxymethyl (-COOCH3) or by carboxy-10559f~3 ethyl (-COOC2H5).
Suitable aryl groups are for example those having from 6 to 14 carbon atoms, preference is given to the phenyl radical and to the naphthyl radical. The aryl groups may also carry 8ub-stituents, e.g. halogen, especially fluorine and chlorine, alkyl æroups having up to 6 carbon atoms, or by trifluoromethyl groups, pentafluoro-ethyl or nitro groups. There may also be considered for example alkoxy groups having up to 6 carbon atoms, such as the methoxy or ethoxy group.
Especially suitable noble metals are palladium, platinum, - ruthenium and rhodium. These catalysts are generally employed on carrier materials such as carbon, aluminum oxide, silicic acid, magnesium oxide, calcium oxide, titanium oxide and asbestos, preference is given to the use of palladium on carbon.
The useful concentration rate of the noble metal varies from 0.02 to 20 %, calculated on the weight of the carrier material, preferably from 0.1 to 10 weight %.
The process may be carried through continuously or dis-continuously, at temperatures from 160 to 350C, preferably from 180 to 260C, since the latter temperatures achieve a particularly high selectivity combined with a very rapid de-hydrogenation.
The reaction pressure varies from 0.5 to 20 atmospheres, being preferably chosen at such a level that it is sufficient for maintaining a liquid phase.
Preference is given to keeping low the partial pressure of the hydrogen which is formed during the dehydrogenation so as to shift the equilibrum in favor of the dehydrogenation and 29 to avoid a hydrogenation or hydrogenolysis of the starting compounds and the fipal products. This low partial pressure of hydrogen may be achieved by purging the reaction system with an lnert gas, such as nitrogen or carbon dioxide.
Suitable solvents are aliphatic ethers, aliphatic esters ~ 5 such as e.g. succinic acid dialkyl ester or propane-diol-; diacetate or butane-diol-diacetate, aromatic ethers such as - diphenyl ether; hydrocarbons such as benzene, toluene, xylene, pseudocumene, naphthalene, biphenyl, tetralene, decalene;
ketones such as acetone, diethylketone, methyl-ethylketone or methylisobutyl ketone. Also suitable are acid amides such as dlmethyl formamide or N-methyl-pyrrolidone, alcohols, phenols -and water. Preferred solvents are aliphatic ethers such as the polyglycol dialkyl ethers, e.g. diethylene glycol dialkyl ether, triethylene glycol dialkyl ether or tetraethylene glycol dialkyl ether having generally alkyl groups with up to 6 carbon atoms.
Special preference is given to the polyglycol dimethyl ethers and polyglycol diethyl ethers. The polyglycol dialkyl ethers have the advantage that they boil under an atmospheric pressure in the preferred temperature range from 180 to 260C - a fact which has a particularly favorable effect on the process, since it allows for operating under normal pressure ~nd slnce the dehydrogenation is carried out with special speed and selectivity under reflux conditions within the preferred temperature range. The efficiency of the process is enhanced ~; by vigorous agitation of the reaction mixture as long as it is contacting the catalyst.
When the reaction is carried out discontinuously, an es-29 pecially ccnvenient embodi~ent is the addition under reflux - `` 1055963 .
conditions of the cyclohexane dione which is dehydrogenated dissolved in an easily volatile solvent such as acetone, iso-propanol, methanol or water to the dehydrogenation mixture consisting of a catalyst suspension and polyglycol ether as $ sol~ent. The solvent for the cyclohexane dione is thereby removed from the reaction mixture by distillation via a des-cending condenser. The hydrogen which is thereby produced contributes additionally to improve the thorough mixing. After completion of the reaction the reaction mixture is filtered off the catalyst and the resorcinal thus produced is obtained in its pure state by distillation of the filtrate.
When the reaction is carried out continuously, a solution of a cyclohexane dione in the same sol~ent which is also employed for the suspension of the catalyst, is introduced continuously via a preheating device into the dehydrogenation reactor, while simultaneously a corresponding quantity of the reaction mixture containing the resorcinol produced is dis-charged. In that case the catalyst is either retained in the reactor by means of a frit, or, after separation e.g. by means of a hydrocyclone, fed back into the reactor. After having separated by distillation the resorcinol produced from the solvent? the latter is re-used for dissolving newly introduced cyclohexane-dione for dehydrogenation.
The process according to the in~ention can be carried out with a fixed-bed catalyst or with a catalyst which is main-; tained in suspension by stirring the reaction solution vi-gourously.
When using a fixed-bed catalyst, a dimension of from O.5 29 to 10 mm, preferably from 2 to 5 mm is recommended for the HOE 74lF 22~.
lOS5963 catalyst particles. Larger particles reduce the efficiency of the catalyst, whilst smaller particles may lead to 103ses in catalyst and to blocking of the catalyst bed.
- When the process is carried out with a supported catalyst and suspended in the reaction medium, the size of the catalyst particles varies generally from 0.01 to 5 mm, preferably from 0.05 to 1 mm. The smaller particles represent the drawback of hardly `separating from the reaction solution. The dis-advantage of larger particles is the difficulty to maintain them in suspension and the minor dehydrogenation speed. De-pending on the type of the liquid and of the catalyst, the sus-pension may contain from 0.1 to 40 parts by weight of catalyst on a carrier material - in relation to 100 parts by weight of the liquid. Preferred proportions are from 1 to 30 parts ~5 by weight of supported catalyst per 100 parts by weight of solvent.
The proce~s according to the in~ention has the advantage that dehydrogenation takes places immediately upon introduction of the cyclohexane dione into the dehydrogenation mixture, so -that the rather unstable cyclohexane-dione-(1,3) is converted immediately to the resorcinol being very stable under the dehydrogenation conditions.
The process according to the invention achieves much higher yieldæ in resorcinol by catalytic dehydrogenation of cyclo-hexane-diones-(1,3) than those obtained according to known processes.
The following examples illustrate the invention:
.
-H~E 74/F 224 E X A M P L E S 1 - 8 (cf. table):
- A mixture of 50 ml of solvent and 1 g of- dehydrogenation catalyst is heated to 180 - 220C while agitating and purging with nitrogen, in a 100 ml three-necked flask, equipped with thermometer, agitator, dropping funnel and descending condenser (Claisen - bridge). Subsequently, the cyclohexane-dione in a solvent which is either identical with the solvent used for the catalyst suspension or which boils considerably lower is added ln such a way that the cyclohexane-dione concentration doe~ not surpass 30 weight %, calculated on the weight of the liquid phase. The operation is controlled by a gas meter measuring the quantity of hydrogen which is formed during the reaction. During the addition, the temperature is maintained within the range ~ ~m180 to 230C. After having completed the addition of cyclohexane-dione, the temperature is kept at 220 - 230C for a short while until no more hydrogen is pro-duced. Cooling takes then pla~ce while purging with nitrogen, the catalyst is separated and the filtrate is analyzed by GLC
~ and finally sub~ect to distillation in vacuo. After frac-tionating the solvent (e.g. $n the case of diethylene glycol - diethyl ether the boiling point is 78 - 84C under 15 mm/Hg) the desired resorcinol i8 obtained in its pure state (boiling point 158C under 15 mm/Hg). The solvent may be'recycled.
If methanol'is used as solvent texample 5), which esterifies with cyclohexane-dione to yield 3-methoxy-cyclo-hexanone, resorcinol-monomethyl ether is formed as by-product.
.
-`" 1055963 ~ 0~ ~ ~ o ~ a: I I I
O ~ ~r u~ u o _, o~
~ ~ ~ o .,.~ ~ ~ N ~ 0 'O O
~ S~ ~
a) ~ ln S
-- a . dP
^ o o o o o o o o ~c O ~ ~ ~D ~ ~D ~ CD
~-- . ~ o C~ ~ -. ao o . ~ o o. ~ o~r o o o o c) o E~
~ ~ O c~ ~ u~ I` ~ a~
r~ ~ c~ ,, _, ,, O _I a~ c~ ,1 , ~ ~J o N N N N N ~1 _I N :~
j:l ~ ~ ~-- . .C
m n R ~
_I ~
h dP
~ o o O ~d h u) o ~ ~ o o o U~ al ,1 0-- ~r In ~ 10 10 ~r I
~ I
o ~ e ~ N ~
0 ~ o o o m o li3 o o x a) ~ ~ ~ ~
~D a~ H H Cl E H H ~i a1 0 O O O ~ O ~
~1 l,q _ _I ~
C) ~ O rl ~10 ~ O .C
.a ~I h ~
h Cl O O ^ ~
1 e l ~ ~ 1 O , ~ ~ e ~ 8 ~ O P. ~ z m ,~
o Q~ ~ I
6-- ~ ~ ~:
~ .. ~ e ~ ~
~ ~ .,~ o O ~q ~ ~ Zrl Q.
_I R
~ ~ e ~ N ~ ~ 10 ~D t` O~ r!) f~ 1l ~
Q) ~d X W. P~ W
~ c~ ~3 ~ z m ~
E X A M P L E 9: ' .
A mixture of 100 ml of diethylene glycol diethyl ether and 1 g of catalyst (0.1 g Pd on 0.9 g of powdery carbon <0.05 mm) is heated to 190C while purging with nitrogen, in a 250 ml three-necked flask, equipped with agitator, thermometer and descending cooling device. Subsequently, a solution of 22 g of 2,6-dimethyl-3-hydroxycyclohexene-(2)-one (prepared from 4-methyl-5-oxo-hepanoic-acid methyl ester according to German Offenlegungsschrift 2 245 270) in 210 ml of isopropanol is added within two hours, the temperature being maintained at 185C. The isopropanol is removed continuously by distillation.
The development of hydrogen stopped after completion of the addition of the cyclohexane-dione. The contents of the reactor were cooled, the catalyst was filtered off and the filtrate distilled in vacuo. After the diethylene glycol diethyl ether (bolling point 72C under 14 mm/Hg) 18.5 g (= 85.3 % of thec!retical yield) of 2,6-dimethyl resorcinol are passing over at the boiling point of 112C under 2 mm/Hg which cristallize in the collector recipient (m.p. 107C from benzene).
-- ~0 --
Claims (7)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the preparation of a resorcinol having the formula wherein the radicals R1 to R4 may be identical or different and represent hydrogen, straight-chain, branched or cyclic alkyl groups which may carry substituents, or aryl groups which may carry substituents, in which a cyclohexane dione-(1,3) of the formula wherein R1 to R4 are as defined above, is added to a dehydrogen-ation mixture of (a) a solvent and (b) a catalyst containing a noble metal of the eighth subgroup of the periodical system, under a pressure of from 0.5 to 20 atmospheres and at a temper-ature of from 160 to 350°C, the cyclohexane dione-(1,3) being added so that the concentration of cyclohexane-dione which is to be dehydrogenated does not surpass 30%, calculated on the weight of the liquid phase.
2. A process as claimed in claim 1 in which the sol-vent is selected from the group of diethylene glycol dialkyl-ethers, triethylene glycol dialkyl ethers and tetraethylene glycol dialkyl ethers in which the alkyl groups have up to 6 carbon atoms.
3. A process as claimed in claim 1 in which the re-action is carried out at a temperature in the range of from 180 to 260°C.
4. A process as claimed in claim 1 in which R1 to R4 are selected from the group of methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, cyclopentyl, cyclohexyl, cyclododecyl, allyl, napthyl and phenyl and said groups may carry substituents.
5. A process as claimed in claim 1, claim 2 or claim 3 in which the catalyst is selected from the group of palladium, platinum, ruthenium and rhodium.
6. A process as claimed in claim 1, claim 2 or claim 3 in which the catalyst is supported on a support material and the catalyst is present in an amount of from 0.02 to 20%, calculated on the weight of the support material.
7. A process as claimed in claim 1, claim 2 or claim 3 in which the catalyst is palladium supported on carbon and the palladium is present in an amount of from 0.1 to 10%, calculated on the weight of carbon.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2437983A DE2437983C3 (en) | 1974-08-07 | 1974-08-07 | Process for the production of resorcinols |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1055963A true CA1055963A (en) | 1979-06-05 |
Family
ID=5922641
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA232,790A Expired CA1055963A (en) | 1974-08-07 | 1975-07-31 | Process for the manufacture of resorcinol |
Country Status (11)
| Country | Link |
|---|---|
| JP (1) | JPS5858334B2 (en) |
| BE (1) | BE832223A (en) |
| BR (1) | BR7505061A (en) |
| CA (1) | CA1055963A (en) |
| CH (1) | CH598166A5 (en) |
| DE (1) | DE2437983C3 (en) |
| FR (1) | FR2281347A1 (en) |
| GB (1) | GB1517726A (en) |
| IT (1) | IT1040401B (en) |
| NL (1) | NL7509211A (en) |
| ZA (1) | ZA754863B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2533920C2 (en) * | 1975-07-30 | 1982-12-09 | Hoechst Ag, 6000 Frankfurt | Process for the production of resorcinols |
| NL7612281A (en) * | 1976-11-05 | 1978-05-09 | Stamicarbon | PROCESS FOR THE PREPARATION OF RESORCINOL AND ALKYL-SUBSTITUTED DERIVATIVES THEREOF. |
| DE2825073A1 (en) * | 1978-06-08 | 1979-12-20 | Hoechst Ag | METHOD FOR THE PRODUCTION OF RESORCINES FROM DELTA-KETOCARBONIC ACID ESTERS |
| JPS6287548A (en) * | 1985-10-11 | 1987-04-22 | Sumitomo Chem Co Ltd | Production of 2-acetylresorcin |
| EP0331422A3 (en) * | 1988-03-02 | 1991-02-06 | Mitsui Petrochemical Industries, Ltd. | Method of preparing 2-acylresorcinols |
| JPH0558931A (en) * | 1991-08-30 | 1993-03-09 | Sumitomo Chem Co Ltd | Production of 2-methylresorsinol and 2-methyl-1,3-cyclohexanedione |
| US20040249225A1 (en) | 2001-10-24 | 2004-12-09 | Tatsuya Hirata | Method an system for recovery of catalysts and process and unit for production of perfluoroalkyl iodide telomers |
| US7294748B2 (en) * | 2004-10-19 | 2007-11-13 | Wake Forest University Health Sciences | Sulfenic acid-reactive compounds and their methods of synthesis |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3865884A (en) * | 1970-05-11 | 1975-02-11 | Canadian Thermo Images Ltd | Preparation of orcinol |
| GB1188387A (en) * | 1967-05-31 | 1970-04-15 | British Oxygen Co Ltd | Preparation of Resorcinol |
| NL7102722A (en) * | 1970-03-04 | 1971-09-07 | ||
| US3953526A (en) * | 1972-09-22 | 1976-04-27 | Atlantic Richfield Company | Synthesis of hydroquinone |
-
1974
- 1974-08-07 DE DE2437983A patent/DE2437983C3/en not_active Expired
-
1975
- 1975-07-29 ZA ZA00754863A patent/ZA754863B/en unknown
- 1975-07-31 CA CA232,790A patent/CA1055963A/en not_active Expired
- 1975-08-01 NL NL7509211A patent/NL7509211A/en not_active Application Discontinuation
- 1975-08-04 CH CH1013875A patent/CH598166A5/xx not_active IP Right Cessation
- 1975-08-05 IT IT26152/75A patent/IT1040401B/en active
- 1975-08-06 JP JP50095089A patent/JPS5858334B2/en not_active Expired
- 1975-08-07 GB GB33075/75A patent/GB1517726A/en not_active Expired
- 1975-08-07 BR BR7505061*A patent/BR7505061A/en unknown
- 1975-08-07 BE BE159024A patent/BE832223A/en not_active IP Right Cessation
- 1975-08-07 FR FR7524644A patent/FR2281347A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5141332A (en) | 1976-04-07 |
| BE832223A (en) | 1976-02-09 |
| DE2437983C3 (en) | 1982-04-01 |
| BR7505061A (en) | 1976-08-03 |
| GB1517726A (en) | 1978-07-12 |
| NL7509211A (en) | 1976-02-10 |
| CH598166A5 (en) | 1978-04-28 |
| FR2281347B1 (en) | 1978-10-27 |
| DE2437983B2 (en) | 1981-05-21 |
| JPS5858334B2 (en) | 1983-12-24 |
| IT1040401B (en) | 1979-12-20 |
| ZA754863B (en) | 1976-09-29 |
| DE2437983A1 (en) | 1976-02-26 |
| FR2281347A1 (en) | 1976-03-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3329722A (en) | Production of 3-hydroxy-2, 2, 4, 4-tetraalkyl-cyclobutanones | |
| AU604961B2 (en) | A process for the production of ether carboxylic acids | |
| CA1055963A (en) | Process for the manufacture of resorcinol | |
| US4160113A (en) | Process for the manufacture of resorcinol | |
| Okubo et al. | The Anodic Oxidation of Esters | |
| US3124614A (en) | Preparation of z-substituteb | |
| US1787205A (en) | Production of alcohols | |
| US2524096A (en) | Process for preparing beta-phenyl ethyl alcohol | |
| US4024196A (en) | Process for the manufacture of hydroquinone | |
| US2174242A (en) | Aminoglycols | |
| US2947784A (en) | Preparation of n, n-dibutyl aniline | |
| US2560950A (en) | Production of o-cresol derivatives | |
| US3794668A (en) | Vapor phase oxidation of phenols | |
| US3217041A (en) | Preparation of olefinic oxygencontaining compounds | |
| US4855516A (en) | Method of manufacturing 2-propyn-1-ol | |
| US3692848A (en) | Production of alkenediols | |
| US2748173A (en) | Process for preparing monochlorohydroquinone | |
| US3607874A (en) | Production of n-methylpiperazine | |
| KR930003935B1 (en) | Process for the preparation of 2,2 dimethyl propane-1,3-diol | |
| US3663626A (en) | Hydrogenation of arylaldehydes | |
| US2784221A (en) | Method of converting aldehydes into acids | |
| US4124643A (en) | Preparation of 3-fluorosalicylaldehyde | |
| US3663628A (en) | Catalysts for producing acetylenic alcohols | |
| JPH02231488A (en) | Production of acetals | |
| US4060563A (en) | Process for preparing 2-allyl phenol |