IL43738A - Process for the production of 3-halophenols and 3,5-dihalophenols - Google Patents

Process for the production of 3-halophenols and 3,5-dihalophenols

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Publication number
IL43738A
IL43738A IL43738A IL4373873A IL43738A IL 43738 A IL43738 A IL 43738A IL 43738 A IL43738 A IL 43738A IL 4373873 A IL4373873 A IL 4373873A IL 43738 A IL43738 A IL 43738A
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Israel
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catalyst
halogen
sulphur
reaction
carried out
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IL43738A
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IL43738A0 (en
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Bayer Ag
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Priority claimed from DE19722259433 external-priority patent/DE2259433A1/en
Priority claimed from DE2344926A external-priority patent/DE2344926C3/en
Priority claimed from DE19732344925 external-priority patent/DE2344925C3/en
Application filed by Bayer Ag filed Critical Bayer Ag
Publication of IL43738A0 publication Critical patent/IL43738A0/en
Publication of IL43738A publication Critical patent/IL43738A/en

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    • 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
    • C07C41/24—Preparation of ethers by reactions not forming ether-oxygen bonds by elimination of halogens, e.g. elimination of HCl
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/043—Sulfides with iron group metals or platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/20—Sulfiding
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • 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
    • 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
    • C07C37/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Description

A process for ;the production of 3-halophenols and 3»5-dihalophenols AKTIEHGESELLSCHAFT O- 41833 3-halogen-phenols and 3, 5-dihalogen-phenols by the partial, selective dehalogenation of higher-halogenated phenols using catalytic hydrogenation .
Conventional methods of producing 3-halogen- and 3,5- dihalogen-phenols are complicated and are expensive in terms of both labour and costs to carry out in practice. Thus, in processes based on the halogenation of a nitrobenzene, the resulting 3-halogen-l-nitrobenzene has to be catalytically reduced into the corresponding aniline, followed by diazotisation and boiling to form the 3-halogen-phenol (cf. Beilsteins Handbuch .der organijs.ciien_-Cheir £,--Ji^h^dJ;ior^_ypl^_ YI, . page^JL85) . » .
In the alkaline hydrolysis of suitable dihalogen' and trihalogen benzenes to form the corresponding 3-halogen- and 3, 5-dihalogen-phenols, the dihalogen and trihalogen benzenes used as starting materials have to be used in a purity which is extremely difficult to obtain (cf. Chemischer Informationsdienst, 1971, B-24-232).
Furthermore, it is already known that individual halogenated phenols can be subjected to catalytic hydro enation. Hydrogenation catalysts, for. example^ Ra eyL.n_i_c.kel_(cf. Houben-Key-l-,— Methoden der Organischen Chemie, 4th Edition, Vol. V/4, page 772) or palladium (Indian J. Chem. 2, 29½ (196½), Vol. 86, 501 (1953), are used for this purpose.
However,—a selectivey—partial~"dehalogenation is unknown in the catalytic hydrogenation of polychlorophenols.
Le A 14 609-I-E 1 For example, the hydrogenation of pentachlorophenol with Raney nickel results in the formation of phenol through complete dehalogenation (Bull. 1963. No. 11, page 2 k2) . ' The hydrogenation of .polychlorophenols in the gas phase on activated alumina impregnated with copper (i) chloride to form phenol mixtures of different chlorine content (DAS 1,109,70 is neither complete nor specific.
Surprisingly, it has now been found that 3-halogen- and 3 , 5-dihalogen-phenols of the general formula in which X represents halogen, c c n o R , R , R and R independently of one another have the same of halogen and the group R 1 — - R," .Tr-CH2-; provided that - 5 6 8 at least one of the radicals R , R and R represents 7 ~ hydrogen whilst the radical R can also represent a hydroxy group andf^in^Ke^case of "3, 5-dihalogen-phenols, exiusively represents a halogen atom can__be__selectively obtained without difficulty from higher-halogenated compounds by reacting a halogen compound corresponding to the general formula - la - in which X represents halogen^ R 1 , R2 , R3 and R4 independently of one another represent hydrogen, halogen, alkyl, cycloalkyl, aralkyl optionally substituted as specified hereinafter, aryl optionally substituted as specified hereinafter, alkoxy, cycloalkoxy, aryloxy optionally substituted as specified hereinafter, alkylthio, cycloalkylthio or a group R R,'; -CH2- wherein R' and R" are the same or different and each represents an alkyl or cycloalkyl group, or R* and R" together with the nitrogen atom to which they are attached form a saturated azacyclic ring; 1 2 4 provided that at least one of the radicals R , R or R ... 3 represents a halogen atom whilst the radical R can also represent a hydroxy group and, in the case of 3,5- dihalogen"phenoj,s7 -exG-U-sAvely---?epresents-- - halogen- om — R represents OH, or R together with R1 can represent the radical - 0 - CHg - 0 - CH2 -, - o the phenol oxygen atom standing for R, in which case X, R JLJ and R independently of one another represent hydrogen, 146Ό9-Ι-Ε 2 halogen or an alkyl radical and at least one of the radicals X or R^ and at least one of the radicals R or R represents a halogen atom, with hydrogen at an elevated temperature and pressure in the presence of a sulphide or polysulphide of one or more of the metals Fe, Co, Ni, optionally applied to a support, or of a mixture of these metal sulphides or polysulphides as catalyst or in the presence of ai- catalyst-containing— ne—or -more-noble— metals of Group VIII of the Periodic System in the form of thei metals, oxides or sulfides and sulphur and/or sulphur compounds (as hereinafter specified) , optionally applied to a support.
The halogen atoms represented by the radicals X and R1 4 to R may be fluorine, chlorine/ bromine, iodine, preferably chlorine and bromine.
Suitable alkyl radicals and alkyl moieties in alkoxy and 1 4 alkylthio R to R are linear or branched alkyl radicals or moieties having up to 12 carbon atoms and preferably with up to 6 carbon atoms. The methyl, ethyl, propyl, isopropyl and tert. -butyl radicals and moieties are mentioned as specific examples.
Preferred cycloalkyl radicals and cycloalkyl moieties in cyclo¾lkoxy and cycloalkylthio are those having 5 or 6 carbon atoms in the ring.
In the context of this specification the term "optionally substituted" refers to the following substituents: halogen (fluorine, chlorine, bromine or iodine~)~rpreferabl chlorine and bromine; the hydroxy group; linear or branche alkyl radicals having up to 12 carbon atoms and preferably having up to 6 carbon atoms; cycloaliphatic radicals, preferably with 5 or 6 carbon atoms in the ring; and aryl radicals, especially the phenyl radical.
The benzyl radical and optionally substituted benzyl In the hydrogenation of polyhalogen phenols with dialkyl amino methyl radicals, dialkylamine is split off in addition to the partial and selective dehalogenation. It is possible in this way to obtain the corresponding methyl-m-halogen phenols.
The compounds corresponding to the above general formula are known and are readily obtainable. The following are mentioned as examples of compounds which can be used for the process according to the invention: 2,3-, 2,5-, 3,4-dihalogenphenols; 2,3,4-, 2,3,6-, 2,4,5-, 2,3,5- and 3, 4, 5-trihalogenphenols; 2,3,4,6-, 2,3,4,5-, Le A 14 609-I-E k 2,3,5,6-tetrahalogen phenols, pentachlorophenol , 2-bromo-3- chlorophenol, 3-bromo-4-chlorophenol , 3-bromo-2-chlorophenol| 2-bromo-5-chlorophenol, 5-bromo-2-chlorophenol , 4-bromo-3- chlorophenol , 4-bromo-2,5-dichlorophenol, 4-chloro-2,3,6- tribromophenol , »6-dichioro-o- cresol, 2,4,5,6-tetrachloro-m-cresol,- 2,4,5,6-tetrabromo-m- cresol, 2,5-dibromo-£-cresol, 2,5-dichloro-£-cresol, 2,3,5,6-tetrachloro-p_-cresol, 6-chloro-2,5-dibromo-£-cresol , 2,3,6-tribormo-£-cresol , 2,3,5, 6-tetrabromo-£-cresol , 2 , 5-dichlbro-! [3,4]-xylenol , 2,5^ 6-tribromo- [3 , ]-xylenol , 4-chloro-3-bromo- [2,6 ]-xylenol , 3 , 4-dibromo- [2,6]-xylenol , 3, 5-dibromo-4-chloro- [2, 6 ]-xylenol , 3,4, 5-tribromo- [2,6]-xylenol, · 3,4,6-tribromo- [2,5 ]-xylenol, 2, 5-dichloro-4-ethyl-phenol , 2, 5-dichloro-4-propylphenol , 2, 5-dichloro-4-tert. -butyl phenol, tetrachloro resorcinol, 2,4;6-trichloro-2-benzylphenol, 2, 21-dihydroxy-3 , , 6, 31 ,5' ,6f-hexachloro diphenylmethane, 3.4.5-trichloro-2-hydroxy .biphenyl , 4,4" -dihydroxy^joctachloro-biphenyl, 3,4-dichloro^guaiacol , 3,6-dichloro^uaiacol, 4,5-dichloro guaiacol, 5,6-dichloro guaiacol, 3,4,6-triehloro— guaiacol, 3,4,5-trichloro^guaiacol, 3,4,5,6-tetrachloro —-guaiacol, 4,5-dichloro-3-methoxyphenol, 5,6-dichloro-3-inethoxy-phenol, 2,5-dichloro-3-methoxyphenol, 4, 5,6-trichloro-3-methoxyphenol^ 2,4i5,6-tetrachloro-3-methoxyphenol, 2,3-dichloro-4-methoxyphenol , 2, 5-dichloro-4-methoxyphenol , 2.3.6-trichl6ro-4-methoxyphenol , 2,3, 5-trichloro-4-methoxy-phenol, 2,3,5,6-tetrachloro-4-methoxyphenol, 4, -dichloro-2-phenoxyphenol, 3,4,5,6-tetrachloro-2-phenoxy phenol, 2,4,5,6-tetrachloro-3-phenoxyphenol , 2,5-dichloro-4-phenoxyphenol, 2, 3 , 5,6-tetrachloro-4-phenoxyphenol , 2, 5-dichloro-4-methyl-mexcaptophenol ,. 2,4,5, -tetrachloro-4-methylmercaptophenol , 2-(dimethylamino methyl )-3,6-dichlorophenol , 4-(dimethylamino l -2 - ichloro hen l 2- - - trichloro henol , 2,4-bis-(dimethylamino methyl)-3 , 6-dichloro- phenol, 2t ¼-bis-(dipiperidyl amino methyl )-3 ,6 -dichloro-1 , 3-benzodioxan, 5,8-dichloro-l , 3-benzodioxan, ^ 5,7, 8-trichloro-l , 3- enzodioxan, 5 » 6-dichloro-8-me thy1-1 , 3-beizodioxan and 5 , 8-dichloro-6-methyl-l , 3-benzodioxan.
The catalysts which can be used for the process according to the invention consist a) of the metals Fe, Co, Ni in the form of their sulphides and polysulphides and b) of noble metals of Group VIII of the Periodic System of Elements which are known per se as hydrogenation catalysts (cf.K.A. Hoffmann and U.R. Hoffmann, Anorranische Chemie, 12th Edition, Braunschweig 1948, page 380) in the form of their metals, oxides and sulphides" and sulphur and/or sulphur compounds (as hereinafter specified). Ruthenium, rhodium, palladium, osmium, iridium and platinum, for example, are mentioned as examples of the Group VIII noble metals which can be used in the form of their metals, oxides, and sulphides; palladium and platinum are preferably used.
The catalysts can of course also be applied to supporting materials. Any supporting materials known per se can be used for this purpose, providing they are inert with respect to bases and water. Examples of suitable supporting materials incJ ude BaSO^ , Ca^CPO^^ and carbon. Active carbon is preferably used as the supporting material.
The catalysts a) can be prepared in different ways : polysulphides of iron, cobalt or nickel to be separately prepared. Water soluble salts of iron, cobalt or nickel, for or' ^ example the halides, nitrates / sulphates , and sulphide or ( polysulphide ions, for example in the form of hydrogen sulphide or a water-soluble sulphide or polysulphide can be individually added to the reaction mixture at the beginning of the reaction.
However, it can also be advantageous, for example in cases where aprotic solvents such as toluene and benzene are used, to prepare the iron, cobalt. or nickel sulphide or polysulphide catalyst in a separate process. To this end, the water-soluble salts of iron, cobalt or nickel, for example the halides, nitrates, sulphates, are precipitated by the addition of sulphide or polysulphide ions, for example by introducing hydrogen sulphide or by adding a water-soluble sulphide or polysulphide in aqueous solution. They may even be precipitated on to a support. If necessary, the catalyst subsequently filtered off can even be dried before it is used in an aprotic solvent.
This method of preparation can generally be carried out with any water-soluble salts of iron, cobalt and nickel, for example halides, nitrates, sulphates, salts or organic acids such as oxalates or acetates. However, it is preferred to use readily accessible salts such as chlorides, nitrates and sulphate The quantity in which the catalyst a) is used is by no means a critical parameter in the process according to the invention. It can be varied within wide limits. In general, the catalyst is used in a quantity of from 0.5 to 20% by weight and preferably in a quantity of from 1 to 10% by weight, based on the starting material. In cases where it is applied to a support, the catalyst is used in a correspondingly larger quantity, generally amounting to from about 5 to 30% by weight In the context of this specification, the sulphur compounds contained in the catalysts according to b) are inorganic or organic sulphur compounds. They can be either f soluble or substantially or completely insoluble i_n water and solvents. In general , - however , it is preferred to use substantially insoluble or completely insoluble sulphur compounds Examples of suitable inorganic sulphur compounds include monosulphides and polysulphides , thiosulphates and thiocyanates ; the cations can generally be selected as required.
Preferred inorganic sulphur compounds include monosulphides and polysulphides, for example water soluble monosulphides and polysulphides such as sodium sulphide and potassium sulphide, and substantially insoluble monosulphides and polysulphides such s.i calcium sulphide, manganese sulphide, iron sulphide, cobalt sulphide, nickel sulphide, copper sulphide, silver sulphide, cadmium sulphide, antimony sulphide and lead sulphide.
Thioalcohols , thiophenols, thioaldehydes and thioketones are mentioned as examples of organic sulphur compounds. It is of course also possible to use the corresponding anions and salts such as sodium th~ oethylate ami silver thioethylate.
It is also possible to use organic sulphur compounds which are not included in the above-mentioned groups, such as carbon disulphide and thiourea.
The ratio of sulphur and/or sulphur compound to the Group VIII noble, metal is generally 0.5 to 30, preferably 1 to 15 and more particularly 2 to 5 mols of sulphur and/or sulphur compound per mol of noble metal, oxide or sulphide.
The catalysts b) can of course also be applied to supporting materials. Any supporting materials known pe se are suitable for this purpose, providing they are inert with respect to bases and water. Examples of supporting materials such as these include carbon. Active carbon is preferably used as the supporting material.
The catalysts b) can be prepared in different ways: In general, it is not necessary to combine the noble metal, oxide or sulphide and the sulphur and/or sulphur compound before they are used in the process according to the invention, instead they can be individually added to the reaction mixture before the beginning of the reaction. It can be advantageous, especially in cases where the process according to the invention is carried out continually, to arrange the noble metal, oxide or sulphide as a fixed bed or fluidised-bed catalyst in the reaction zone and continuously to add sulphur and/or a sulphur compound- with the starting material and/or hydrogen or separately.
However, _ it can_als be advantageous to add sulphur and/or a sulphur compound to the noble metal, oxide or sulphide before use and, optionally, intimately to mix the components with one another. However, it can also be advantageous to suspend the noble metal, oxide or sulphide, optionally applied to a support, in an aqueous solution of a corresponding water-soluble metal salt and to precipitate the sulphur compound, for example the metal sulphide, polysulphide or mercaptide, on the noble metal, oxide or sulphide, optionally applied to a support, by the addition of sulphide or polysulphide ions, for example by introducing hydrogen sulphide or by adding a water-soluble sulphide or by adding an organic compound containing the mercapto group.
In general, this method of preparation can be carried out with any water-soluble metal salts, for example halides, nitrates, sulphates, salts of organic acids such as oxalates and acetates. However, it is preferred to use readily accessible salts such as chlorides, nitrates and sulphates.
Thioalcohols such as thioethanol, thiophenols and thio-and dithio-carboxylic acids are mentioned as examples of organic compounds containing the mercapto group. It is, of course, also possible to use their water-soluble salts, such as their alkali salts.
In general, it is best to use nonvolatile and/or insoluble sulphur compounds especially insoluble sulphides, for preparing the catalyst used^ in the process according to the invention. In this way, the catalysts retain their activity and selectivity over pro/onged periods, even when they are repeatedly used in tne process according to the invention and even in cases where the process according to the invention is carried out continuously, and give consistently high yields of 3-halogen- and 3,5-dihalogen-phenol.
In cases where volatile and/or soluble sulphur compounds are used in the preparation of the catalyst, the catalyst may show a drop in its activity and selectivity after a while in cases where it is re-used in a new batch or when the process according to the invention is carried out continuously. For this reason, it can be advantageous to add more sulphur and/or sulphur compound to an already used catalyst before it is re-used. In cases where the process according to the invention is carried out continuously, it is advantageous in this case to add small quantities of sulphur and/or sulphur compound continuously as just described.
The qyantity in which the catalyst b) is used is by no means a critical parameter in the process according to the invention. It can be varied within wide limits. of from 0.1 to 2% by weight, based on the starting material used. In cases where the catalyst is applied to a support, it is used in a correspondingly larger quantity, generally in a quantity of from 1 to 20% by weight, based on the starting material.
The catalysts retain their activity o er prolonged periods', even when tht y are repeatedly used in ..he process according to the invention and even when the process according to the invention is carried out cont nuously.
The process according to the invention is generally carried out at a temperature of from about 100 to about 350° and preferably at temperatures of from about 180 to 330°.
On account of the vapour pressure, if any, of the compounds to be hydrogenated and .he catalyst used^ at these temperatures, it is best to work at elevated pressure, In general, the process i carried out under a hydrogen pressure of from about 20 to 250 atms., preferably under a hydrogen pressure of from 40 to 220 atms and more particularly under a hydrogen pressure of from 50 to 200 atms.
The reaction time is generally go^ erned by the reaction temperature to the extent that, with increased reaction temperature and reaction velocity, a shorter reaction time is . equired for the same conversion. On account of this depen nc f it is generally not possible to state the reaction time, although, even f the necessary reaction time is exceeded, there is no danger of undesirable dehalogenation of the halogen atom meta to the hydroxy group.
In general, the process according to the invention is cfc'-ried out in solution. It is possible for this purpose to υ e any solvents that are inert under the reaction conditions, referably water, monohydric and polyhydric alcohols, The process according to the invention is illustrated by the following reaction equation for the dehalogenation of 2,4,5-trichlorophenol into 3-chlorophenol : Since hydrogen halide is evolved during the reaction according to the invention, it is generally best to add a base as hydrogen halide acceptor to the starting mixture before the beginning of the reaction. The bases normally used as hydrogen halide acceptors can be employed for this purpose. It is preferred to use tertiary amines, anilines and pyridine, also the hydroxides, carbonates, bicarbonates and acetates of the alkali metals, especially sodium and potassium, and of the alkaline earth metals, especially calcium hydroxide. The quantity in which the base is used is generally selected so that one equivalent of base is used per halogen atom of the starting compound which is not in the 3- or 5-position to the hydroxy group. However, it is also possible to use an excess of base over and above this ratio.
In general, the process is carried out by introducing the starting material, solvent and hydrogen halide acceptor into an autoclave, adding the catalyst and, after the autoclave has been closed, flushing out the air present in it with nitrogen. The nitrogen is then flushed out with hydrogen, the autoclave placed under the hydrogen pressure selected and completion of the reaction, the 3-halogen- or 3, 5-d halogen-phenol is dissolved or kept in solution as phenolate by the addition of alkali hydroxide and the catalyst separated off, for example by filtration. The catalyst-free solution is worked up by methods known per se. for example by acidification with a mineral acid, for example concentrated hydrochloric acid, extracting the 3-halogen- or 3,5-dihalogen-phenol by shaking with an organic solvent, for example methylene chloride, and subsequently working up the organic phase, for example by fractional distillation.
The process according to the invention can be carried out both in batches and continuously. It can be particularly advantageous to carry out the process according to the invention continuously. The layout required for this purpose in terms of apparatus to enable the process to.be carried out as a fixed-bed or fluidised-bed catalyst process, is known per se from the prior art, as is the continuous introduction of the starting and auxiliary materials required and the continuous isolation of the reaction product from the reaction mixture (c . for example German Patent Specification No. ^8,784).
The surprising advantage of the process according to the invention is that it enables corresponding higher-halogenated phenols to be selectivity dehalogenated into 3-halogen- and 3,5-dihalogen-phenol without difficulty by catalytic hydrogenatio Another advantage of the process according to the invention is that it is also possible to use as starting material mixtures in which there is no halogen in the 3- or 5-position to the hydroxy group. In the process according to the invention, these compounds are dehalogenated into phenol which is readily separated off by distillation. By contrast, separation of the corresponding halogen phenols from the compounds corresponding to the above general formula in which R represents OH is both com licated and time-consumin cf. for exam le DAS No The 3-haiogen- and 3,5-dihalogen-phenols which can be obtained by the process according to the invention correspond to thc> general formula: in which X represents halogen, R5 , R6 , R7 and R8 independently of one another have the 1 2 3 4 same meanings as R , R , R and R herein with the exception of halogen and the group R^-N~CH2~' provided 6 8 that at least one of the radicals R , R and .R represent 7 hydrogen whilst the radical R can also represent a hydroxy group and, in the case of 3 , 5-dihalogen-phenols , exclusively represents a halogen atom.
The following ure mentioned as examples of halogcn-phenolsj which can be /obtained as products of the process according to the invention. 3-bromophcnol, 3-chlorophenol , 3, 5-dichloro- phenol, 5»chloro-o-cresol, 5-chloro-m-crqsol , , 3-chloro-j)-crcsol, 3, 5-dichloro-£-cresol , 3- romo-j-cresol , 3, 5-dibromo-ji-crcsol . 5-chloro-5 , 'i-xylenol , 5-bromo-3# 4-xylcno I 3-bromo-2, 6-xy1eno1 , 3, 5-dibroaio-2, 6-xy1eno1 , 3-bromo-2, 5-xy1eno 3-chloro-¾-ethylphenol, 3-chloro--¾-propylphenol , 3-chloro-4-tert. -butylphenol , 5-chlororesorcinol , 3-chloro-2-benzyl^phenol 2,2' -dihydroxy-6 , 61-dichlorojiiiphenyl methane , 4-chloro-2-hydroxy-biphenyl , 4,4'-dihydroxy-2 , 6 , 2 ' , 6 '-tetrachlorobiphenyl , 3-chloro-guaiacol , 5-chloroguaiacol , 3 , 5-dichloroguaiacol , 5-chloro-3-methoxyphenol, 3-chloro-4-methoxy-p¾enoJ., 3, 5-dichlor 4-methoxy-phenol , 3-chloro-2-phenoxyphenol , 5-chloro-2-phenoxy-phenol , 3 , 5-dichloro-2-phenoxyphenol , 5-chloro-3-phenoxyphenol , products and are used in particular in the production of plant- { protection agents (German Patent Specifications No. 921,870, 1,116, 656, 814.152 ) . T EXAMPLES A) Preparations of the catalysts according to a) EXAMPLES 1 to 5 ^ g of active carbon were introduced into 200 ml of water. The quantity specified in Table I of an Fe, Co or Ni salt or of a mixture of these salts, dissolved in 30 ml of water, was initially run in with stirring. The metal sulphide or polysulphide was then precipitated by the dropwxse addition of Na^S or NagS^, dissolved in 30 ml of water, in the quantity specified in Table I. On completion of the addition, stirring was continued for another 30 minutes at 80°C. The catalyst was then filtered off under suction and washed with water until free from sulphide.
If the catalyst is intended to be used in aprotic solvents, it is dried for about 12 hours at 80°C/250 Torr.
Table I.
Example No. Catalyst of 10 g of active carbon and-;— 1 4.2 g of CoSO^ . 7 ¾0 2.1 g of Na2S . 3 ¾0 2 4.2 g of CoS0¾ . 7 ¾0 Na„S, from 2.1 g of Na9S . 3 H„0 and 1 * 3 2 2 of S 3 25.2 g of FeSO^ . 7 ¾0 12.0 g of Na2S . 3 ¾0 4 4.2 g of CoSO^ . 7 HgO 8.4 g of FeS0 . 7 ¾0 6.0 g of Na2S . 3^¾0 B) Preparation of the catalysts according to b) Examples 6 to 17 g of an approximately 5 J6 by weight noble metal-active carbon (a 0.005 mol of metal) were introduced into a solution of 3 times the molar quantity of a water-soluble metal salt, based on the quantity of noble metal, in 200 ml of water, followed by heating to a temperature of 80°C with stirring. 2 g of Na2S . 3¾0 (0. 015 mol of S), dissolved in 30 ml of water, were then slowly added dropwise in an inert-gas atmosphere (nitrogen). On completion of the addition, stirring was continued for 30 minutes at 80°C. The catalyst was then filtered' off under suction and washed thoroughly with distilled water until free from sulphide. Individual Examples for the preparation of the catalyst in accordance with the general procedure described above are given in the following Table II in which the Example No. is given in column 1 , the noble metal of the noble metal-active carbon in column 2 and the quantity and type of the aforementioned metal salt in column 3 : Table II Example No. Noble metal Metal salt 6 Pd 4.2 g of FeSO^HgO 7 Pd 4.2 g of CoS0 7¾0 8* Pd 3.6 g of NiCl2.6H20 9 Pd 3.0. g of MnCl2.4H20 Pd 5.7 g of Pb(CH3C00)2.3H20 11 Pd 2.56 g of AgN03 12 Pd 3.75 g of CuS04.5H20 13 Pd 3 g of CdCl2.H20 14 Pt * 4.2 g of FeSO^HgO ' EXAMPLE 16 _ ( s Following the procedure of Example 6, 10 g of an approximately 5 by weight palladium-active carbon (= 0.005 mol of palladium) were-introduced into a solution of 4.2 g of FeSO^ . 7 H20 in 200 ml of water, followed by heating to 80°C with stirring. 2.14 g of N jS^, dissolved in 30 ml of water were added dropwise in an inert-gas atmosphere (nitrogen).
On completion of the addition, stirring was continued for another 30 minutes at a temperature of 80°C. The catalyst was then filtered off under suction and washed--thoroughly—with distilled water until free from sulphide.
EXAMPLES 19 to 26 The following Examples illustrate the preparation of catalysts simply-by^combining the noble metal -and the sulphur or the sulphur compound; the two components can be combined before their addition to the substance to be hydrogenated or its solution or can be combined in this substance or solution. To this end, 10 g batches of an approximately 5 by weight noble metal-active carbon (= 0.005 mol of metal) have added to them the quantities of sulphur and sulphur compound specified in Table III below (corresponding to 0.015 mol of sulphur).
The Example No. the noble metal of the noble metal-active carbon, and the quantity and type of sulphur compound appear as separate headings in the Table.
Table XII EXAMPLE 27 g of an approximately 5 ¾y weight palladium sulphide- active carbon were introduced into a solution of 4.2 g of FeSO^ 71^0 in 200 ml of water, followed by heating to a temperature of 8 C~whiIe~stirring. A solution of "2 g of Na2S * 3H2° in 30 of water was slowly added dropwise in an inert-gas atmosphere (nitrogen). On completion of the addition, stirring was continued for another 30 minutes at 80°C. The catalyst was then filtered off under suction and washed thoroughly with distilled water until free from sulphide.
EXAMPLE 28 g of an approximately 5 hy weight platinum sulphide-active carbon were introduced into a solution of 4.2 g of FeSO^ . 7H20 ih 200 ml of water, and the resulting solution was heated to 80°C with stirring. A solution of 2 g of Na2S . 3H20 in 30 ml of water was slowly added dropwise in an inert-gas atmosphere (nitrogen). On completion of the addition, stirring was continued for another 30 minutes at 80°C. The catalyst was then filtered off under suction and washed thoroughly with distilled water until free from sulphide.
EXAMPLE 29 g of an approximately 5 by weight palladium oxide-active carbon were introduced into a solution of 4.2 g of FeSO^ . 7H20 in 200 ml of water, followed by heating to 80°C with stirring. A solution of 2 g of a2S . 3H2° in 30 of water was slowly added dropwise in an inert-gas atmosphere (nitrogen). On completion of the addition, stirring was continued for 30 minutes at 80°C. The catalyst Was then filtered off under suction and washed thoroughly with distilled water until free from sulphide.
C) Process Examples EXAMPLE 30 81 g of 2,5-dichlorophenol (0.5 mol), 22 g of NaOH (0.55 mol )_ and JJQO^mL of. waker^were^introducfid^i to^a-.0-.7.JLitre capacity hydrogenation autoclave (equipped with a stirring mechanism). 10 g of the catalyst prepared in accordance with Example 1 were then added.
LeA 1 609-I-E - 19 - The autoclave was closed; the air displaced with nitrogen and the nitrogen subsequently flushed out with hydrogen.
The contents of the autoclave were then heated to 250°C and hydrogenated for 60 minutes under a hydrogen pressure of 200 atms On completion of hydrogenation, 30 ml of concentrated sodium hydroxide (approximately 0. 5 mol) were added to the reaction mixture. The reaction mixture was stirred briefly and vigorously and the catalyst filtered off under suction from the liquid reaction mixture. The catalyst was then washed with 300 to ¾00 ml of warm water (approximately 60 to 70°C).
The reaction. solution which accumulated as filtrate was cooled and acidified at room temperature with 70 ml of concentrated hydrochloric acid (approximately 0. 8 mol of HCl). The aqueous mixture was extracted by shaking with approximately 150 ml of methylene chloride in several portions. The organic phases which accumulated were combined and dried over NagSO^.
The solvent (methylene chloride) was then distilled off and the liquid residue distilled at around 100°C/10 mm Hg.
The yield comprised 96 of the theoretical yield.
EXAMPLE 31 The procedure was as described in Example 30, except that the CoS/FeS catalyst prepared in accordance with Example was used as catalyst. The yield amounted to 93 % of the theoretical yield.
Table IV below shows the analyses of the crude products as determined by gas chromatography, and the yields derived therefrom: Table IV Exam le Yield Analysis No. of theoretical fo 3-CP J6 2,5-DCP P 2-CP 96 97.18 - 2.40 0.07 31 93 97.78 - 2.21 The abbreviations used for the results of analysis in Table IV above and in the following Tables have the following meanings : J P = phenol 3-CP = 3-chlorophenol 2-CP 2-chlorophenol 2,5-DCP = 2 , 5-dichlorophenol 2 , 4-DCP = 2 , 4^-dichlorophenol 3 , 4-DCP = 3 , 4-dichlorpphenol 3,5-DCP = 3 , 5-dichlorophenol EXAMPLES 32 to 35 Following the procedure of Example 30, 81 g of a dichloro-phenol mixture (74.4 of 2, -dichlorophenol, 9.1 of 3,4-di^-chlorophenol , 14.9 of 2,4-dichlorophenol ) , 22 g of NaOH and 300 ml of water were hydrogenated under a hydrogen pressure of 200 atms. over the periods and at the temperatures specified in the following Table. Working up was carried out in the same way as described in Example 30. Table V below shows the analysis of the crude products, as determined by gas chromatography, and the yields derived therefrom.
Table V Example Catalyst Time Yield J6 Analysis No. according mins. of theoreto Example tical #2, 5-DCP No . 32 1 45 280 82.5 85.27 0.08 13.89 33 · 2 45 280 83.5 88.07 0.03 11.44 34 3 45 300 66.0 84. 36 - 15.63 5 280 82.5 80.05 0.54 13.60 EXAMPLE 36 Following the procedure of Example 30, 133 g (0. 5 mol) of pentachlorophenol are hydrogenated in a solution of 105 g (l mol) of agCO^ in 220 ml of water over a period of 25 minutes at 260°c/l50 atms. hydrogen pressure using the catalyst prepared in accordance with Example 4. Working up was carried out as described in Example 30.
Analysis of the crude product as determined by gas chromatography and the yield derived therefrom are shown in Table VI below: Table VI Example Catalyst Yield 56 Analysis No. of Example of theore¬ No. tical fo 3, 5^-DCP 5&3-CP #4-CP #2,4-DCP 36 4 80. 5 84.89 3.92 5.6 2.61 EXAMPi. *¾7 -» ' Following the procedure of Example 30, 40 g of tetrachloro-p_-cresol, 26 g of NaHCO^ in 250 ml of water were hydrogenated for 90 minutes at 200°C under a hydrogen pressure of 200 atms.
A CoS/FeS catalyst according to Example 4 was used as the catalyst. ' 29 g of a crude product of which 79 consists of 3, 5-dichloro-£- cresol, corresponding to a yield of 68 of the theoretical.
Melting point 97 to 9B°C (recrystallised from ligroin).
EXAMPLE 38 Following the procedure of Example 30,25 g of tetrachloro-o-cresol, 14. 5 g of soda, 10 g of the CoS catalyst accordin to Example 1 and 100 ml of water were hydrogenated for Ί5 minutes at 230°C under a hydrogen pressure of 200 alms. Working up was carried out in the same way as described in Example 0 , giving 15.5 g of a crude product of which 77 % consisted of 3, 5-dichloro-o-cresol , corresponding to a yield of 67 of the theoretical yield. Melting point: 87 to 89°C (recrystallised from ligroin).
EXAMPLE 39 Following the procedure of Example 30,20 g of 2,3,6-trichloro-4-tert.-butylphenol, k g of NaOH and 5 g of NagCO^ in 150 ml of water were hydrogenated for 60 minutes at 2 0°C/200 atms. hydrogen pressure using 10 g of the CoS catalyst produced in accordance with Example 1. Working up is carried out in the same way as described in Example 30, giving 13. 5 g of a crude product of which 85 consisted of 3-ehloro- -tert butylphenol, corresponding to a yield of 79 of the theoretical yield. Melting point: 65 to 66°C (recrystallised from petroleum ether).
EXAMPLE 40 Following the procedure of Example 30,20 g of tetra-chloro-£-methoxyphenol, 13 g of NaHCO^, 10 g of the CoS/FeS catalyst according to Example k and 240 ml of water were hydrogenated for 60 minutes at 200°C under a hydrogen pressure of 200 atms.
Working up was carried out in the same way as described in Example 30 ,giving 15 g of a crude product of which 92.12 - - - yield of 94 of the theoretical yield. Melting point: 121 to 122°C (recrystallised from chlorobutane ) .
EXAMPLE 40 g (0.087 mol) of , 4'-dihydroxy octachlorobiphenyl were hydrogf nated in a solution of 29 g (0.35 mol) of NaHCO- and 300 ml of water for a period of 40 minutes at 270°C/l50 atms. hydrogen pressure using the CoS/FeS catalyst of Example 4.
Working up was carried out in the same way as described in Example 30. The residue was recrystallised from diisopropyl ether, giving 18.6 g of pure 4, ' -dihydroxy-2, 6 , 2 f , 6 »-tetrachloro biphenyl (65 > of the theoretical yield).
Melting point 186 to 187°C.
EXAMPLE 42 · 60 g of 2,4-bis-(dimethylaminomethyl)-3j6-dichlorophenol, 10 g of a CoS catalyst according to Example 1 and 350 ml of toluene were introduced into a 0.7 litre capacity hydrogenation autoclave (equipped with a stirring mechanism). The autoclave was closed, the air present in it displaced with nitrogen and the nitrogen subsequently flushed out with hydrogen. Thereafter the contents of the autoclave were heated to 200°C and x hydrogenated for 60 minutes under a hydrogen pressure of 200 atms On completion of hydrogenation, the catalyst was filtered off under suction, the toluene solution washed with approximately 300 ml of 2 N HC1 and subsequently dried with Na2S0^. The solvent-was. run. off- and -the residue- distilled, giving _2.5-g_.of._a -crude product of which 84 consisted of 2,4-dimethyl-3-chloro -phenol, corresponding to a yield of 68 of the theoretical yield. Melting point: 67 to 68°C (recrystallised from petroleum ether).
EXAMPLE 3 - 41 g of 2,2'-dihydroxy-3,5,6,3', i,6'-. hexachlorodiphenyl- catalyst according to Example 1 and >00 ml of toluene were introduced into a 0.7 litre capacity hydrogenation The autoclave was closed, the air present in it disp aced witi^ nitrogen and the nitrogen subsequently flushed out with hydrogen. The contents of the autoclave were then heated to 280°C and hydrogenated for 60 minutes at 280°C under a hydrogen pressure of 300 atms. On completion of hydrogenation, the catalyst was filtered off under suction, the toluene solution washed with approximately 300 ml of 2 N HC1 and subsequently d ied with NagSO^. The solvent was distilled off, giving 2k g of a crude product of which 82.17 consisted of 2 , 2 ' -dihydroxy-6 , 6 ' - dichlorodiphenylmethang, corresponding to a yield of 73 of the theoretical yield. Melting point 176 to 178°C (recrystallised from toluene).
EXAMPLE Following the procedure of Example 0,41 g of 2 , 5-di chloro- ½-methylmercaptophenol , 18 g of NaHCO^, 10 g of a CoS ca lyst according to Example 1 and 240 ml of water were hydrogenated for 60 minutes at 200°C under a hydrogen pressure of 200 atms, was carried out in the same way as described in Example 30, giving 26.5 g of a crude product of which 71.3 fo consisted of 3-chloro-4-methylmercaptophenol , correspondin -to a yield of 5½ 1° of the theoretical yield. Melting point: 59 to 60°C (recrystallised from cyclohexane ) .
EXAMPLE 45 Following-' -the^procedure"t>f .Ε*βίπ ϊ¾-437^¾2.^ Βοί^†6«i'8≤.' ^ * trichloro-1, 3-benzodioxane, 15 g of pyridine, 10 g of a CoS catalyst according to Example 1 and 200 ml of toluene were hydrogenated for 60 minutes at 280°C under a hydrogen pressure of 200 atms. Working up was carried out as described in Example 43, giving 8.4 g of a crude product of which 82.9 consisted of 3-chloro-o cresol corres ondin to a ield of of the theoretical yield. Melting point: 84°C (recrystallised from ligroin).
EXAMPLE ^6 Following the procedure of Example 30 , 34.2 g of 4,5-dichloro-2-phenoxyphenol, 10 g of NaHCO^, 10 g of a CoS catalyst according to Example 1 and 300 ml of water were hydrogenated for 90 minutes at 250°C under a hydrogen pressure of 200 atms.
Working up was carried out in the same way as described in Example 30 , giving.24. g of a crude product of which 65 # consisted of 5-chloro-2-phenoxy phenol boiling at 130 to 133°C/ v 1 Torr, and 18 of unreacted 4,5-dichloro-2-phenoxyphenol.
Accordingly, the yield comprised 63.5 and 5 of the theoretical, based on the starting material reacted and used, respectively.
EXAMPLE 47 81 g of 2,5-dichlorophenol (0.5 mol), 22 g of NaOH (0.55 mol) and 240 ml of water were introduced into a 0.7 litre capacity hydrogenation autoclave (equipped with a stirring mechanism). g of the catalyst prepared in accordance with Example 6 were added.
The autoclave was closed, the air present in it was displaced with nitrogen and the nitrogen subsequently flushed out with hydrogen. The contents of the autoclave were then heated to 260°C and hydrogenated for 1 minutes under a hydrogen pressure of about 40 to 60 atms. On completion of hydrogenation, 30 ml of concentrated sodium hydroxide ("0.5 mol) were added to the reaction mixture. The reaction mixture was stirred briefly and vigorously, and the catalyst filtered off from the liquid reaction mixture. The catalyst was washed with 300 to 400 ml of warm water (approximately 60 to 70°C), and can be subsequently re-used. The reaction solution which accumulated as filtrate was cooled and acidified at room temperature with 70 ml of concentrated hydrochloric acid (ΛΌ.8 tool of HCl). The aqueous mixture was extracted by shaking with ahout 150 ml of methylene chloride in several portions. The organic phases which accumulated were combined and dried over Na2S0^.
The solvent (methylene chloride) was then distilled off and the liquid residue distilled at around 100°C/lO mm Hg. 61.5 g of 3-chlorophenol were obtained, corresponding to a yield of 96.4 of the theoretical yield. Analysis by gas chromatography produced the following results: 99.36 J6 of 3-chlorophenol 0.08 56 of 2,5-dichlorophenol 0.55 of phenol.
EXAMPLES 48 to 68 Table VII below shows the results of Examples 48 to 68 which were carried out in the same way as Example 47, except that the hydrogenation time and temperature wer^Varied.
Le A 14609-I-E - 27 - Table VII Example Time gemp. Yield Analysis No. mins. of theore#3CP J62, 5DCP £2-CP tical 48: 30 230 79 82.7 17.0 0.20 0.10 49 i 30 240 85 94. 5 5. 1 0.33 0.08 50 ; 30 250 90 99.2 0.09 0.68 - 51 30 260 90 99.2 0.17 0.65 - 52 60 220 73 79.6 20.1 0.12 0.07 53 60 230 90 98.1 1.2 0.48 0.03 54 60 240 92 98.4 0.39 0.74 - 55 60 250 91 97.9 0.31 1.31 0.43 56 60 260 87 98.8 - 1.24 - 57 120 200 73 82. 3 16.7 0.40 0.49 58- 120 210 91 96.1 2.5 0.23 0.03 9 120 220 92 98.8 0. 59 0.53 0.02 60 120 230 88 96.5 0.07 3.4 - 61 120 240 88 96.2 0.98 1.4 . - 2 120 250 86 97.0 0.02 1.6 0.41 3 120 260 87 97.2 0. 30 2. 5 - 4 240 220 91 98.7 0.10 1.15 - 5 240 230 85 96.9 0. 15 2.9 - 6 240 240 89 96.3 - 3.7 " - 7 240 250 85 94.4 - 5.6 - 8 240 260 76 90.2 - 9.8 - EXAMPLES 69 to 71 Following the procedure of Example 47, 81 g of 2,5- dichlorophenol , 22 g of NaOH and a mixture of 120 ml of water and 120 ml of methanol were hydrogenated for 120 minutes under a hydrogen pressure of 80 to 90 atms. at the temperatures specified in TableVIII below. On completion of hydrogenation and separation of the catalyst, the methanol was distilled off from the reaction solution. The aqueous solution was further worked up in the same way as described in Example 47. The results obtained are set out in the following Table: Table VIII EXAMPLES 72 to 74 81 g of 2, 5-dichlorophenol and 240 ml of water were introduced into a0.7 litre capacity hydrogenation autoclave in the same way as in Example 47, except that different quantities of sodium hydroxide, as specified in Table I below, were added.
Hydrogenation was carried out over a period of 120 minutes at 230°C under a hydrogen pressure of 80 to 90 atms. On completion of h dro enation 0 ml of concentrated sodium h dr added to the reaction mixture, and the reaction mixture stirred briefly and vigorously. Thereafter the catalyst was filtered off under suction from the liquid reaction mixture and washed with 300 to 400 ml of warm water (approximately 60 to 70°C); it can subsequently be re-used.
The reaction solution which accumulated as filtrate was cooled and acidified at room temperature with 70 ml of concentrated hydrochloric acid. The aqueous mixture was extracted by shaking with approximately 150 ml of methylene chloride in several portions. The organic phases which accumulated were combined and dried over a2S0^. The solvent was then distilled off and the residue distilled at around 100°C/10 mm Hg. Table IX .below shows as separate headings the Example No. the quantity of sodium hydroxide used, the yield obtained and its composition according to analysis by gas chromatography.
Table IX ' EXAMPLES 75 to 97 In these Examples, batches of 81 g of 2,5-dichlorophenol and 22 g of NaOH were hydrogenated at 230°C in a mixture of 220 ml of water and 120 ml of glycol. 10 g of a catalyst prepared in accordance with Examples 6 to 29 were used as catalyst in each test. The hydrogenation time selected is specified in the following Table. The aqueous glycol solution results of these Examples are set out in the following Table: Table X Example Catalyst Time Yield g #3-CP #2,5-DC P ; JtP #2-CP No. according mins fo Of to Example theoreNo. tical 75 6 120 89.5 99.1 0. 50 0.38 0.22 76 7 120 88 93.3 0.08 5.14 0.07 77 8 120 65 74,3 5.8 15.0 - 78 9 120 65 74.5 6.2 13.2 6.0 79 10 120 80 84.4 15.2 0. 23 0.10 80 11 70 88 98.1 0.80 0.83 0.07 81 12 120 88 99.1 0.10 0.73 82 13 120 83 90.0 2.0 5.7 0.60 83 14 90 90 98.5 1.53 - - 84 16 120 78 87.0 2.8 9.9 0.21 85 . 17 90 93 96.4 2.5 1.0 0.13 86 18 120 85 99.3 0.5½ 0. 19 - 87 19 120 87 94.8 4.4 0.40 0.10 88 20 120 80 98.0 0.10 1.9 0.03 89 21 120 91 98.4 0.03 1.6 - 90 22 80 93 98.4 0.60 0.70 - 91 : 23 60 89 98.5 0.56 0.25 - 92 ; 24 120 80 90.7 0.46 7.1 0.41 93 ; 25 120 93.5 98.4 0.03 0.5 - 94 1 26 120 90 99.6 0.02 0.35 - 95 \ 27 120 84 92.5 3.6 3.5 0.40 96 28 120 91.5 99.7 0.08 0.2 - 97 29 120 86.5 98.3 trace 1.7 - EXAMPLE 98 98. 7 g (0. 5 mol) of 2,4, 5-trichlorophenol, 22 g (0. 55 mol of NaOH, 40 g (0.4 mol) of NagCO^, 240 ml of water and the catalyst prepared in accordance with Example 6 were introduced into a 0. 7 litre hydrogenation autoclave in the same way as described in Example 47. Hydrogenation was carried out over a period of 2 hours at 230°C under a hydrogen pressure of 60 atms. On completion of hydrogenation, the aqueous solution was worked up as described in Example 47. 57 g of distillate with the following composition were obtained: 2-chlorophenol 0. 01 % phenol 1.23 % 2,5-dichlorophenol 0.02 3-chlorophenol 98.24 % The resulting yield of 3-chlorophenol corresponds to 87 of the theoretical yield: EXAMPLE 99 52 g ( 0. 3 mol) of 2 , 5-dibromophenol, 25 g (0. 3 mol) of NaHCO^, 300 ml of water and 10 g of the catalyst prepared in accordance with Example 15» were introduced into a 0. 7 litre hydrogenation autoclave as described in Example 47. Hydrogenation was carried out over a period of 1 . 5 hours at 190°C under a hydrogen pressure of 150 atms.
On completion of hydrogenation, 30 ml of concentrated sodium hydroxide were added to the reaction mixture which was then stirred briefly and vigorously and subsequently filtered off from the catalyst. The filtrate was cooled and acidified with 70 ml of concentrated hydrochloric acid. This aqueous mixture is extracted by shaking with a total of about 150 ml of methylene chloride in several portions. The organic phases were separated s e o distilled in vacuo at around 110°C/lO mm Hg. 34.0 g of distillate of the following composition were obtained: 2-bromophenol 0.39 phenol 4.31 2 , 5-dibromophenol 0.040 3-bromophenol 95.25 The yield of 3-bromophenol corresponded to 1 of the theoretical yield.
EXAMPLE 100 55 g (0. 15 mol) of 2 , 3 , 6-tribromo-4-chlorophenol, 42 g (0. 5 mol) of NaNCO^ and 300 ml of water were introduced with 10 g of the catalyst prepared in accordance with Example 15 into a 0.7 litre hydrogenation autoclave, and hydrogenated for about 1.5 hours at 200oc/l50 atms. hydrogen pressure as in Example 47. Working up was carried out as described in Example 47 » giving 17 g of distillate with the following composition: phenol 23.2 J6 4-chlorophenol 9.1 3-bromophenol 67.95 EXAMPLE 101 As in Example 47 , 133 g (0.5 mol) of pentachlorophenol were hydrogenated in a solution of 105 g (l mol) of NagCO^ in 220 ml of water over a period of 25 minutes at 260°C/l50 atms. hydrogen pressure using the catalyst prepared in accordance with Example 6. Working up was carried out in the same way as described in Example 47 , giving 67 g of distillate of the following composition: 2-chlorophenol 0.27 # phenol 0.31 2.4-dichlorophenol 0.46 3-chlorophenol 10.94 % 3.5-dichlorophenol 88.02 EXAMPLE 102 As in Example 47 , 59 g (0.33 mol) of 3,4-dichloro-6-methyl- phenol, 15 g (0.375 mol) of NaOH and 300 ml of water were introduced with the catalyst prepared in accordance with Example 6 into a0. 7 litre hydrogenation autoclave, and hydrogenated for 30 minutes at 250°C/lOO atms. hydrogen pressure. Working up was carried out in the same way as described in Example 47 » giving 43 g of distillate with the following composition: 2 cresol 1.41 by weight 3-chloro-6-methylphenol 98.59 by weight The yield of 3-chloro-6-methylphenol corresponded to 90 # of the theoretical yield. M.p. 73 - 74°C (ligroin).
EXAMPLE 103 As in Example 47 , 35.5 g (0.l6 mol) of 2,5-dichloro-4- tert.-butylphenol were hydrogenated with 7.1 g (0.18 mol) of NaOH in 300 ml of water for 30 minutes at 240°C/100 atms. hydrogen pressure on the catalyst prepared in Example 6.
Working up was carried out in the same way as described in Example 47 , giving 25.5 g of distillate with the following composition: 4-tert.-butylphenol 12 3-chloro-4-tert.-butylphenol 83.3 2, 5-dichloro-4-tert.-butylphenol 4.7 The yield of 3-chloro-4-tert.-butylpJienol amounted to 72 of the theoretical yield. M.p. 65 - 66°C (petroleum ether).
Le A 14 609-I-E - 34 - EXAMPLE 1Q4 60 g of 2,4-bis-(dimethylajmino)-3,6-dichlorophenol, 10 g ^ of the catalyst of Example 15 and 300 ml of toluene, were introduced into a 0.7 litre capacity hydrogenation autoclave (equipped with a stirring mechanism). The autoclave was closed, the air present in it is displaced with nitrogen and the nitrogen subsequently flushed out with hydrogen. The contents of the autoclave were then heated to 200°C and hydrogenated for 60 minutes under a hydrogen pressure of 200 atms. On completion of hydrogenation, the catalyst was filtered off under suction, the toluene solution washed with approximately 300 ml of 2 N HC1 and subsequently dried with NagSO^. The solvent was distilled off and the residue distilled, giving 32.5 g of a crude product of which 92.47 consisted of 2,4-dimethyl-3-chlorophenol , corresponding to a yield of 89 of the theoretical yield. Melting pointing 67 to 68°C (petroleum ether).
EXAMPLE 105 As in Example 47, 60 g of 2, 4-bis-(dimeth laminomethy1 )-2,6-dichlorophenol, 10 g of the catalyst of Example 5 and 300 ml of water were hydrogenated for 60 minutes at 150°C under a hydrogen pressure of 200 atms. Working up was carried out as described in Example 47, and gave 24.7 g of crude product, of which 81.39 consisted of 2,4-dimethyl-3-chlorophenol, corresponding to a yield of 59.5 of the theoretical yield.
EXAMPLE 106 As in Example 104,38 g of 2-(dimethylaminomethyl)-3,4,6-trichlorophenol , 12 g of pyridine, 10 g of the catalyst of Example 6 and 300 ml of toluene were hydrogenated for 60 minutes at 250°C under a hydrogen pressure of 200 Working up was carried out as described in Example 104, and gave 16 g of a of crude product, of which 98.08 J6 consisted/ 3-chloro-_-eresol , EXAMPLE 107 \ ■ As in Example 104, 22.5 g of 5,6,8-trichloro-l,3-benzodioxane, 15 g of pyridine, 6.2 g of the catalyst of Example 15 and 200 ml of toluene were hydrogenated for 60 minutes at 280°C under a hydrogen pressure of 200 atms. Working up was carried out as described in Example 104, giving 10 g of a crude product of which 85.37 consisted of 3-chloro- -cresol , corresponding to a yield of 63.5 of the theoretical yield. Melting point 84°C (ligroin).
EXAMPLE 108 As in Example 47 , 20 g of tetrachloro guaiacol, 13 g of NaHCO^, 5 g of the catalyst of Example 15 * and 240 ml of water were hydrogenated for 30 minutes at 200°C under a hydrogen pressure of 200 atms. Working up was carried out as described in Example 47 , and gave 13.5 g of a crude product of which 74 consisted of 3, 5-dichloro guaiacol, corresponding to a yield of 68 of the theoretical yieid,^._Melting- poitttr~59~to"60°C (petroleum ether).
EXAMPLE 1 QQ As in Example 47 , 34 g of 4, -dichloro-2-phenoxyphenol , 9 g of NaHCO^, 10 g of the catalyst of Example 15 and 300 ml of water were hydrogenated for 90 minutes at 230°C under a hydrogen pressure of 200 atms. Working up was carried out as described consisted of in Example 47 , giving 26 g of a crude product of which 84.5 / 5-chloro-2-phenoxyphenol, corresponding to a yield of 74 of the theoretical yield. B.p., : 130 to 133? Le A 14 609-I-E - 36 - EXAMPLE 110 32 g (0.13 mol) of tetrachloro^resorcinol were hydrogenated in a solution of 42 g (0.5 mol) of NaHC03 in 300 ml of water for 1.5 hours at 180°C/150 atms. hydrogen pressure using the catalyst prepared in accordance with Example 15. The reaction solution was concentrated by evaporation to dryness after the catalyst had been filtered off. The solid residue was sublimated and gave 7 g (27 of the theoretical) of pure 5-chloro resorcinol. M.p. 115 - 116°C.
EXAMPLE 111 40 g (0.087 mol) of 4,4,-dihydrox^octachlorobiphenyl were hydrogenated in a solution of 29 g (0.35 mol) of NaHCO^ in 300 ml of water over a period of 10 minutes at 270°C/l50 atms. hydrogen pressure using the catalyst prepared in accordance with Example 6. Working up was carried out as described in Example 47. The residue was recrystallised from diisopropyl ether, and gave 21.5 g of pure 4,4,-dihydroxy-2,2'-6, 6'-tetra- chloroiiphenyl (75 of the theoretical). M.p. 186 - 187°C.
EXAMPLE—112 As in Example 47 , 42 g of 2, 5-dichloro-4-methylmercapto-phenol, 18 g of NaHCO^, 10 g of the catalyst of Example 15 and 240 ml of water were hydrogenated for 75 minutes at 200°C under a hydrogen pressure of 200 atms. Working up was carried out as described in Example 47 , giving 33.2 g of a crude product of which 78.7 consisted of 3-chloro-4-methylmercaptophenol, corresponding to a yield of 67.5 of the theoretical yield.
After recrystallisation from cyclohexane, the 3-chloro-4-methylmercaptophenol melted at 59 to 60°C.
Le A 14 609-1-E - 37 - EXAMPLE 1 1 g As in Example 104,, kl g of 2 , 2 ' -dihydroxy-3 , 5 , 6 , 3 ',5 ' , 6 hexachlorodipheny^jpethane (hexachlorophene), 33 g Of pyridine, 5 g of the catalyst of Example 6 and 300 ml of toluene were hydrogenated for 60 minutes at 230°C under a hydrogen pressure of 299 atms. Working up was carried out as described in Example 104, giving 18 g of a crude product of which 81. 3 consisted of 2 , 2 ' -dihydroxy-6 , 6 ' - dichlorodiphenylmethane > corresponding to a yield of 55 of the theoretical yield.
After recrystallisation from toluene, the 2 , 2 ' -dihydroxy-6 , 6 1 - dichlorodiphenylmethane, meited at 176 to 180°C.
Le A 14 609-I-E - 38 -

Claims (19)

43738/2 What ve claim is;
1. A process for the production of 3-halogen- and 3,5- dihalogen-phenols of the general formula in which X represents halogen, 5 6 7 8 R , R , R and R independently of one another have the 1 2 3 4 . same meanings as R , R , R and R herein with the R' exception of halogen and the group -^ ^CHj-; provided 5 6 8 that at least one of the radicals R , R and R represents 7 hydrogen whilst the radical R can also represent a hydrox group and, in the case of 3 , 5-dihalogen-phenols , exclusive represents a halogen atom wherein a halogen compound corresponding to the general formula: in which X represents halogen; 1 2 3 4 R , R , R and R independently of one another represent hydrogen, halogen, alkyl, cycloalkyl, aralkyl optionally substituted as specified hereinbefore,aryl optionally substituted as specified hereinbefore, alkoxy, cycloalkoxy, and R" are the same or different and each represents an alkyl or cycloalkyl group, Or R' and R" together with the nitrogen atom to which they are attached form a saturated azacyclic ring; provided that at least one of' the radicals 1 2 4 3 R ' R or R represents a halogen atom, whilst the radical R can also represent a hydroxy group and, in the case of 3,5- dihalogen-phenols , exclusively represents a halogen atom; R represents OH; 2 or R together with R can represent the radical - 0 - CH2 - 0 - CH2 -, the phenol oxygen atom standing f°r R» in which case X, 9 "5 k R , R and R independently of one another represent hydrogen, halogen or an alkyl radical and at least one 3 of the radicals X or R and at least one of the radicals 2 k - R or R represents a halogen atom, is reacted with hydrogen at an elevated temperature and pressure in the presence of a catalyst comprising a sulphide or polysulphide of Fe, Co or Ni or of a mixture of these metal sulphides or polysulphides optionally applied to a sup jort or in the presence of a catalyst containing one or mor< noble metals of Group VIII of the Periodic System and sulphur and/or sulphur compounds (as hereinbefore specified) , optionally . applied to a support.
2. A process as claimed in Claim 1, wherein the catalyst is the sulphide of one or more of the metals Fe, Co and Ni.
3. A process as claimed in Claim 1, wherein the catalyst is the polysulphide of one or more of the metals Fe, Co and
Ni. k , A process as claimed in Claim 1, wherein the catalyst is a mixture of the sulphides and polysulphides of one or more of the metals Fe, Co and Ni.
5. A process as claimed in Claim 1, wherein the noble metals of Group VIII of the Periodic System are used in the form of their metals, oxides or sulphides.
6. A process as claimed in Claim 1 or 5, wherein the reaction takes place in the presence of the elements palladium and/or platinum.
7. A process as claimed in any of Claims 1 and or 5 to 6, wherei the reaction takes place in the presence of palladium-active carbon and iron-(ll)-sulphide.
8. A process as claimed in any of claims 1 and 5 to 7 wherein the catalyst is used in a quantity of 0.1 to 2 by weight based on the starting material.
9. A process as claimed in any of claims 1 and 5 to Θ wherein the ratio of sulphur and/or sulphur compound to the Group VIII noble metal or compound is 0.5 to 30 mols of sulphur and/or sulphur compound per mol of the noble metal or compound thereof. Ie A H 609-I-E - 40 - ,ο
10. A process as claimed in claim 9» wherein 2 to 5 mols of sulphur and/or sulphur compound are used per mol of noble metal or compound thereof.
11. A process as claimed in any of Claims 1 to 10, wherein the catalyst is supported on a carrier.
12. A process as claimed in any of claims 1 to 11, wherein the reaction is carried out at a temperature of from 100 to 350°C.
13. A process as claimed in claim 12, wherein the reaction is carried out at a temperature of from 180°C to 330°C.
14. A process as claimed in any of claims 1 to 13» wherein the reaction is carried out under a hydrogen pressure of from 20 to 250 atms.
15. A process as claimed in claim 14, wherein the reaction is carried out under a hydrogen pressure of from 50 to 200 atms.
16. A process as claimed in any of claims 1 to 15» wherein the reaction is carried out in solution.
17. A process as claimed in any of Claims 1 to 7» wherein 4 , 41-dihydroxy octachlorodiphenyl is used as starting material for the production of 4 , 4 f-dihydroxy-2 , 6, 21 ,6'- tetrachloro diphenyl.
18. A process as claimed in claim 1 , substantially as herein described with reference to any of the specific Examples.
19* A 3-halogen-and/or 3 , 5-dihalogen phenol when prepared by the process claimed in any of claims 1 to 18.
IL43738A 1972-12-05 1973-12-03 Process for the production of 3-halophenols and 3,5-dihalophenols IL43738A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19722259433 DE2259433A1 (en) 1972-12-05 1972-12-05 3-Halo- and 3,5-dihalo-phenols prodn. - by selective partial dehalogenation of higher phenols
DE2344926A DE2344926C3 (en) 1973-09-06 1973-09-06 Process for the preparation of 3-halophenols or 3,5-dihalophenols
DE19732344925 DE2344925C3 (en) 1973-09-06 1973-09-06 Process for the preparation of 3-halophenols and 3,5-dihalophenols

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IL43738A0 IL43738A0 (en) 1974-03-14
IL43738A true IL43738A (en) 1977-03-31

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JP (1) JPS5745727B2 (en)
AT (1) AT329023B (en)
CA (1) CA1023766A (en)
CH (1) CH592592A5 (en)
DK (1) DK143226C (en)
ES (1) ES421137A1 (en)
FR (1) FR2209738B1 (en)
GB (1) GB1419603A (en)
IE (1) IE38873B1 (en)
IL (1) IL43738A (en)
IT (1) IT1000182B (en)
LU (1) LU68921A1 (en)
NL (1) NL7316527A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2443152C3 (en) * 1974-09-10 1981-05-21 Bayer Ag, 5090 Leverkusen Process for the preparation of phenols meta-substituted by halogen
DE2607349A1 (en) * 1976-02-24 1977-08-25 Bayer Ag MICROBICIDAL META-CHLOROPHENOLS
US4215229A (en) * 1978-06-15 1980-07-29 Koppers Company, Inc. Process for alkylating phenolic compounds to produce ortho- and para-monoalkylated phenols and 2,4- and 2,6-dialkylated phenols
SU877836A1 (en) * 1978-11-23 1984-01-30 Предприятие П/Я Р-6913 Catalyst for dealkylating alkyl benzoates with steam
FR2496639A1 (en) * 1980-12-24 1982-06-25 Rhone Poulenc Ind PROCESS FOR THE PREPARATION OF METACHLORIC PHENOLS
FR2496641A1 (en) * 1980-12-24 1982-06-25 Rhone Poulenc Ind PROCESS FOR THE PREPARATION OF METACHLORIC PHENOLS
FR2496640A1 (en) * 1980-12-24 1982-06-25 Rhone Poulenc Ind PROCESS FOR THE PREPARATION OF METACHLORIC PHENOLS
JPS60115543A (en) * 1983-11-26 1985-06-22 Dai Ichi Kogyo Seiyaku Co Ltd Brominated p-phenylphenol
FR2645531B1 (en) * 1989-04-07 1991-06-07 Atochem PROCESS AND CATALYST FOR DEHALOGENATION OF ALPHAHALOGENIC CARBOXYLIC ACIDS
FR2647032B1 (en) * 1989-04-07 1993-12-10 Atochem PROCESS AND CATALYST FOR DEHALOGENATION OF ALPHAHALOGENIC CARBOXYLIC ACIDS

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LU68921A1 (en) 1974-02-11
AT329023B (en) 1976-04-26
NL7316527A (en) 1974-06-07
IE38873B1 (en) 1978-06-21
JPS5745727B2 (en) 1982-09-29
FR2209738B1 (en) 1977-08-05
IE38873L (en) 1974-06-05
ATA1009773A (en) 1975-07-15
GB1419603A (en) 1975-12-31
FR2209738A1 (en) 1974-07-05
DK143226B (en) 1981-07-27
CA1023766A (en) 1978-01-03
DK143226C (en) 1981-12-07
IT1000182B (en) 1976-03-30
CH592592A5 (en) 1977-10-31
ES421137A1 (en) 1976-07-01
IL43738A0 (en) 1974-03-14
JPS4993330A (en) 1974-09-05

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