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EP0000165B1 - Procédé de préparation d'alcool 2-hydroxybenzylique pur et d'alcool 4-hydrobenzylique pur, ou d'un mélange de ces deux alcools - Google Patents

Procédé de préparation d'alcool 2-hydroxybenzylique pur et d'alcool 4-hydrobenzylique pur, ou d'un mélange de ces deux alcools Download PDF

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Publication number
EP0000165B1
EP0000165B1 EP78100188A EP78100188A EP0000165B1 EP 0000165 B1 EP0000165 B1 EP 0000165B1 EP 78100188 A EP78100188 A EP 78100188A EP 78100188 A EP78100188 A EP 78100188A EP 0000165 B1 EP0000165 B1 EP 0000165B1
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EP
European Patent Office
Prior art keywords
hydroxybenzyl alcohol
water
extraction
phenol
extraction stage
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
Application number
EP78100188A
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German (de)
English (en)
Other versions
EP0000165A1 (fr
Inventor
Kurt Dr. Bauer
Alfred Krempel
Reiner Dr. Mölleken
Karlfried Dr. Wedemeyer
Helmut Dr. Fiege
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Haarmann and Reimer GmbH
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Haarmann and Reimer GmbH
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Filing date
Publication date
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Publication of EP0000165A1 publication Critical patent/EP0000165A1/fr
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Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
    • C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
    • C07C37/72—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by liquid-liquid treatment
    • 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
    • C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
    • C07C37/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones

Definitions

  • the invention relates to a process for the preparation of pure 2-hydroxybenzyl alcohol, pure 4-hydroxybenzyl alcohol or a mixture of both hydroxybenzyl alcohols.
  • 2- and 4-hydroxybenzyl alcohol are the primary products; depending on the catalyst used, more or less predominantly 2-hydroxybenzyl alcohol. Due to their high reactivity, however, the hydroxybenzyl alcohols react with the formaldehyde in the reaction mixture to give 2,6- and 2,4-dihydroxymethylphenol and 2,4,6-trihydroxymethylphenoi, and with phenol to give 2,2'-, 2, 4'- and 4,4'-dihydroxy-diphenylmethane. In addition, they condense with themselves to form dihydroxybenzyl ethers, which in turn, if the reaction of phenol with formaldehyde is carried out at higher temperatures, are converted into dihydroxydiphenylmethanes by condensation.
  • British Patent 751 845 describes the preparation of 2-hydroxybenzyl alcohol (saligenin) by reacting phenol with formaldehyde in the presence of basic catalysts and extracting the reaction product obtained with benzene.
  • 2-hydroxybenzyl alcohol is only obtained in a yield of 50% based on the phenol converted.
  • British patent specification 774 696 describes the pure preparation of 2-hydroxybenzyl alcohol from phenol-formaldehyde reaction products by fractional crystallization; a yield of pure 2-hydroxybenzyl alcohol of 21% based on the formaldehyde used is stated for the process.
  • 2- and 4-hydroxybenzyl alcohol can be prepared in high purity and in excellent yields in a simple, economical manner, which can also be carried out on an industrial scale, if phenol is reacted with formaldehyde in the presence of basic catalysts and the reaction product obtained, if appropriate after removing a portion of the unreacted phenol, subject to an at least 2-stage countercurrent extraction in a solvent system water / water-immiscible or limitedly miscible organic solvent, in which either phenol and dihydroxydiphenyl-methane in the first extraction stage and 2-hydroxybenzyl alcohol in the second extraction stage or the mixture of 2- and 4-hydroxybenzyl alcohol and, if only 2-hydroxybenzyl alcohol was extracted in the second extraction stage, optionally 4-hydroxybenzyl alcohol is separated off in a third extraction stage or polyhydroxymethylp in the first extraction stage henols, in the second extraction stage 4-hydroxybenzyl alcohol or the mixture of 2- and 4-hydroxybenzyl alcohol and, if only 4-hydroxybenzyl alcohol
  • 2- and 4-hydroxybenzyl alcohol can be isolated on an industrial scale in a practically quantitative yield from the reaction mixtures obtained in the reaction of phenol with formaldehyde. Since the yields of hydroxybenzyl alcohols in the reaction of phenol with formaldehyde are about 70 to 90%, based on the formaldehyde used, the process according to the invention opens up a way of producing pure hydroxybenzyl alcohols in a total yield of 70 to 85% based on the formaldehyde used on an industrial scale .
  • paraformaldehyde has also proven to be advantageous. It can keep the water content of the reaction mixture below 5%. This leads to an increase in the conversion and an increase in the reaction rates and the removal of the excess phenol is facilitated.
  • Alkaline and alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide or barium hydroxide, alkali phenolates, furthermore oxides and salts of organic acids such as acetic acid, formic acid and lactic acid, divalent metals such as magnesium oxide, zinc oxide, lead oxide, zinc acetate, magnesium acetate etc. come as basic catalysts Question.
  • Basic nitrogen compounds e.g. Ammonium salts and amines such as triethanolamine and hexamethylenetetramine. The selection of the catalyst depends essentially on the desired composition of the reaction product.
  • the reaction temperature can vary between 25 and 120 ° C. In general, it has proven advantageous in the process according to the invention to carry out the reaction of phenol with formaldehyde at temperatures from 40 to 90 ° C.
  • reaction of phenol with formaldehyde can be carried out continuously and batchwise.
  • the reaction mixture obtained in the reaction of phenol with formaldehyde can be subjected to countercurrent extraction without further pretreatment, in particular if the reaction was carried out without a large excess of phenol.
  • Larger excess of phenol for example 5 to 15 moles of phenol per mole of paraformaldehyde, it has proven advantageous to remove enough phenol from the reaction mixture before the countercurrent extraction that the amount of phenol in the product to be extracted is only 50% by weight or less.
  • the phenol can be removed by distillation and / or freezing. It has proven to be advantageous only to subject the reaction mixture remaining after the freezing out of the main amount of phenol to a continuous vacuum distillation, for example in a falling film evaporator. Unreacted formaldehyde, water and other phenol are also recovered. The recovered phenol can be used again for the reaction with formaldehyde.
  • the separation of the hydroxybenzyl alcohols from the remaining reaction mixture is carried out by countercurrent extraction in a water / water-immiscible or limited miscible organic solvent system.
  • Suitable organic solvents for the water / water-immiscible or limited miscible organic solvent system especially alkyl aromatics with 7 or 8 carbon atoms, such as toluene, o-, m- and p-xylene and ethylbenzene, have cyclic hydrocarbons 6 to 8 carbon atoms, such as cyclohexane, cycloheptane and cyclooctane, aliphatic, 6 to 8 carbon atoms, such as di-n-propyl ether, di-n-butyl ether and di-isopropyl ether, and mixtures of these solvents.
  • the alkyl aromatics with 7 to 8 ' C atoms have proven particularly useful. The remaining reaction products of the reaction mixture remain in the aqueous phase.
  • aliphatic ethers having 6 to 8 carbon atoms - but using a larger volume ratio V L / V w than in the first extraction stage - or with aliphatic, 5 to 6 carbon atoms ketones, such as diethyl ketone, ethyl propyl ketone, ethyl isopropyl ketone, methyl butyl ketone and methyl iso-butyl ketone.
  • the aliphatic 6 to 8 carbon atoms are preferably used.
  • the 4-hydroxybenzyl alcohol remaining after the extraction of the 2-hydroxybenzyl alcohol in the aqueous phase in addition to the polyhydroxy-methylphenols can optionally be used in a third extraction step, e.g. with the abovementioned 5 to 6 carbon atoms aliphatic ketones - but using a larger volume ratio VJVw than in the second extraction stage - or with aliphatic alcohols with 4 to 8 carbon atoms such as butanol (1 butanol (2) , Pentanol (1), pentanol (2), 3-methylbutanol (1), hexanol (1), heptanol (1), heptanol (2).
  • the aliphatic, Ketones containing 5 to 6 carbon atoms e.g. with the abovementioned 5 to 6 carbon atoms aliphatic ketones - but using a larger volume ratio VJVw than in the second extraction stage - or with aliphatic alcohols with 4 to 8 carbon atoms such as
  • the aqueous phase obtained in the first extraction stage is advantageously extracted with the above-mentioned aliphatic ketones having 5 to 6 carbon atoms - but using a larger volume ratio V L / V w as in the extraction of the 2-hydroxybenzyl alcohol - or 4 to 8 carbon atoms containing alcohols.
  • the 5 to 6 carbon atoms-containing aliphatic ketones are preferably used.
  • the organic phase then contains the mixture of 2- and 4-hydroxybenzyl alcohol, while the more polar polyhydroxymethylphenols remain in the aqueous phase, from which they can, if desired, be isolated in a subsequent extraction.
  • reaction mixture to be separated contains no or only little phenol, for example because of the molar ratios used in the reaction, it may be advantageous to isolate the reaction components in reverse order, that is to say in the first extraction stage polyhydroxymethylphenols, in the second extraction stage 4-hydroxybenzyl alcohol or the mixture to separate 2-hydroxybenzyl alcohol from 2- and 4-hydroxybenzyl alcohol and, if only 4-hydroxybenzyl alcohol was extracted in the second stage, in the third extraction stage. Since in this procedure the compounds to be separated are always obtained in the aqueous phase, it is expedient to select organic solvents of such polarity for this countercurrent extraction that a change in the volume ratio V L / V W is sufficient to achieve the distribution equilibrium for the individual compounds in one to change their separation sufficiently. Such solvents can then be used in all two or three extraction stages. It is only necessary to change the volume ratio V L / V W in the individual extraction stages and it will avoided that the reaction components remaining in the organic phase must be converted into a different organic solvent for each extraction stage.
  • Organic solvents of this polarity are e.g. the above-mentioned aliphatic, 5 to 6 carbon atoms ketones, especially methyl isobutyl ketone.
  • reaction mixture to be separated is extracted in the first extraction stage using a relatively large volume ratio VJVw; the polyhydroxymethylphenols pass into the aqueous phase, while the hydroxybenzyl alcohols remain together with the dihydroxydiphenylmethanes and any phenol present in the organic phase.
  • organic solvents can also be used for the individual extraction stages in addition to the organic solvents or solvent mixtures mentioned by way of example if these also have sufficient capacity for the compounds to be separated in addition to sufficient selectivity.
  • the countercurrent extraction according to the invention can be carried out batchwise or continuously. In general, it has proven useful if the volume ratio V JV w in the water / water-immiscible or limited miscible organic solvent system is approximately 0.05 to 20. Continuous countercurrent extraction generally requires maintaining volume ratios of approximately 0.05 to 20 for technical reasons.
  • reaction mixtures are obtained in the reaction of phenol with formaldehyde, which essentially contain 2-hydroxybenzyl alcohol and only small amounts of 4-hydroxybenzyl alcohol, it may be expedient for economic reasons not to separate the 4-hydroxybenzyl alcohol as described in a separate extraction stage, but together with it discard the polyhydroxymethylphenols.
  • the 2- and 4-hydroxybenzyl alcohols obtained in the organic phase or the mixture of both compounds are isolated by distilling off the solvent. If, on the other hand, they occur in the aqueous phase, they must first be extracted from it with an organic solvent and then isolated from this as described.
  • the countercurrent extraction to be used according to the invention can be carried out in extraction devices known per se, e.g. in columns without stirrers, such as extraction spray towers or extraction towers with or without packing, or in columns with stirrers such as Scheibel columns or RDC columns (Rotating Disc Contactor) or in extraction centrifuges.
  • stirring devices known per se, e.g. in columns without stirrers, such as extraction spray towers or extraction towers with or without packing, or in columns with stirrers such as Scheibel columns or RDC columns (Rotating Disc Contactor) or in extraction centrifuges.
  • Sieve plate pulsation columns or RDC columns have proven to be particularly advantageous for continuous countercurrent extraction.
  • the extraction temperature for the individual extraction stages can vary within wide limits. For practical reasons, temperatures from 20 to 70 ° C., preferably from 50 to 60 ° C., are generally used. For practical and economic reasons, the extractions are generally carried out under normal pressure or, when using particularly low-boiling extractants, under excess pressure.
  • the compounds produced by the process according to the invention are important intermediates for the production of organic compounds.
  • 2-hydroxybenzyl alcohol is an important starting material for the production of salicylaldehyde
  • 4-hydroxybenzyl alcohol is an important starting material for the production of 4-hydroxybenzaldehyde, anis alcohol and anis aldehyde.
  • the reaction mixture obtained in this way had the following composition:
  • composition of the obtained reaction mixture was purified by high pressure liquid chromatography or - after conversion of the components of the reaction mixture in their trimethylsilyl derivatives by N-methyl-N-trimethylsilyl-acetamide - b e by gas chromatography - right.
  • the conversion based on paraformaldehyde used, was about 98%.
  • the formaldehyde conversion was determined polarographically.
  • the reaction mixture was subjected to countercurrent extraction in the form of 10% and 20% solutions in distilled water.
  • the reaction mixture obtained in this way had the following composition:
  • the reaction mixture was subjected to countercurrent extraction in the form of a 15% solution in distilled water.
  • the potassium hydroxide contained in the mother liquor was neutralized with acetic acid.
  • the bottom product as such and in the form of 20 or 25% solutions in distilled water was subjected to the countercurrent distribution.
  • the reaction mixture was subjected to countercurrent extraction in the form of a 20% solution in distilled water.
  • Example 1 of the 25% aqueous solution of the bottom product obtained in Example 1 c) was extracted in a 14-stage extraction apparatus using a Craig distribution (see Houben-Weyl, Methods of Organic Chemistry, Volume I / 1, '1958, page 257 and ff .) subjected.
  • the solution to be extracted was placed in element 1 of the apparatus and extracted with toluene at a temperature of 60 ° C. using a volume ratio V L / V W of 1.05 / 1.
  • the data show that the separation of phenol and dihydroxydiphenylmethanes from the hydroxybenzyl alcohols and the di- and polyhydroxymethylphenols is achieved in the first extraction stage of the process according to the invention.
  • Aqueous solutions with solids contents between 10 and 25% of the reaction mixtures obtained according to Examples 1 a) to d) were extracted using various organic solvents at temperatures between 25 and 60 ° C. in extraction apparatus according to Craig.
  • column 1 shows the amount of aqueous solution used, the solids content and the composition of the solid according to Examples 1 a) to d), in Column 2 the solvents and amounts of solvent used for the extraction, and the temperature, in Column 3 the number of extraction stages, in columns 4 and 5 the content of the solvent or raffinate phases of phenol and dihydroxydiphenylmethanes (A), 2-hydroxybenzyl alcohol (B) and 4-hydroxybenzyl alcohol and di- and polyhydroxymethylphenols (C) as well as those for Determination of the content used fractions (fractions obtained) listed. The fractions not listed were discarded.
  • the amounts of solvent relate to one extraction stage.
  • the data show that in the first extraction stage of the process according to the invention, phenol and dihydroxydiphenylmethanes are separated from the hydroxybenzyl alcohols and the di- and polyhydroxymethylphenols.
  • the aqueous solution obtained in fractions 1-15 of the raffinate phase in Example 12 was concentrated to a solids content of 1.5% by weight by azeotropically distilling off the water.
  • 0.1 l of the concentrated solution were placed in element 1 of an extraction apparatus comprising 86 stages and subjected to a Craig distribution at 55 ° C. with various organic solvents.
  • column 1 shows the solvents and amounts of solvent used, and in columns 2 and 3 the 2-hydroxybenzyl alcohol (B), 4-hydroxybenzyl alcohol (D), 2,6-dihydroxymethylphenol (E ) and 2,4-dihydroxymethylphenol and polyhydroxymethylphenols (F) as well as the fractions used to determine the content. The fractions not listed were discarded.
  • the amounts of solvent each relate to an extraction stage.
  • the mixture (Feed I) was introduced into the middle of a glass sieve tray column (column 1; overall length: 5.50 m; inner diameter: 50 mm; plate spacing: 50 mm; number of practical trays: 90).
  • the column was passed through a jacket heating to 60 ° C and maintained at a pressure of 0.4 bar with nitrogen.
  • the solvent phase was continuously freed from the solvent in a falling film and thin film evaporator in vacuo.
  • the 6.284 kg raffinate phase produced per hour was first passed through a toluene stripper in order to remove the dissolved toluene azeotropically.
  • the 6.250 kg of toluene-free aqueous solution (feed 11) obtained during the distillation were metered into the middle of a second sieve plate column (column 2; total length: 9 m; inner diameter: 72.5 mm; plate spacing: 100 mm).
  • Column 2 was kept at 55 ° C. by jacket heating and at an excess pressure of 0.65 bar by means of nitrogen.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (6)

1. Procédé de production d'alcool 2-hydroxybenzylique pur et d'alcool 4-hydroxybenzylique pur, ou d'un mélange des deux composés par réaction de phénol avec le formaldéhyde en présence d'un catalyseur basique et extraction de la solution aqueuse du mélange réactionnel obtenu avec un solvant organique, éventuellement avec élimination d'une partie du phénol n'ayant pas réagi, procédé qui est caractérisé en ce qu'on soumet le mélange réactionnel contenant des dihydroxydiphénylméthanes, du phénol, de l'alcool 2-hydroxybenzylique, de l'alcool 4-hydroxybenzylique, des dihydroxyméthylphénols et des polyhydroxyméthylphénols à une extraction à contre-courant en au moins deux étapes dans un mélange de solvants formé d'eau et d'un solvant organique non miscible ou partiellement miscible à l'eau, et on conduit l'extraction à contre-courant de façon telle que:
(a) on utilise dans la première étape d'extraction comme solvants organiques non miscibles à l'eau ou partiellement miscibles à l'eau, dés hydrocarbures alkylaromatiques ayant 7 ou 8 atomes de carbone, des hydrocarbures cycliques ayant 6 à 8 atomes de carbone ou des éthers aliphatiques comprenant 6 à 8 atomes de carbone et on utilise un rapport en volume Vsolvant/Veau de manière qu'il se forme une phase organique contenant du phénol et des dihydroxydiphénylméthanes et une phase aqueuse contenant les autres composés, on sépare la phase organique et on soumet la phase aqueuse dans la seconde étape d'extraction à une répartition à contre-courant avec des éthers aliphatiques contenant 6 à 8 atomes de carbone ou des cétones aliphatiques comprenant 5 ou 6- atomes de carbone, de manière qu'il se forme une phase organique qui contient ou bien l'alcool 2-hydroxybenzylique ou bien les alcools 2- et 4-hydroxybenzyliques et une phase aqueuse qui contient les composés restants, on sépare la phase organique et, au cas où l'alcool 2-hydroxybenzylique a été séparé dans la seconde étape d'extraction, on soumet la phase aqueuse dans une troisième étape d'extraction à une répartition à contre-courant avec des cétones aliphatiques ayant 5 ou 6 atomes de carbone ou des alcools aliphatiques ayant 4 à 8 atomes de carbone, de manière qu'il se forme une phase organique contenant l'alcool 4-hydroxybenzylique et une phase aqueuse contenant les polyhydroxyméthylphénols, ou bien
(b) on utilise comme solvants organiques non miscibles à l'eau ou partiellement miscibles à l'eau dans la première étape d'extraction, des cétones aliphatiques ayant 5 ou 6 atomes de carbone et un rapport en volume Vsolvant/Veau choisi de manière qu'il se forme une phase aqueuse contenant les polyhydroxyméthylphénols et une phase organique contenant les autres composés, on sépare la phase aqueuse et on soumet la phase organique dans une seconde étape d'extraction à une répartition à contre-courant avec de l'eau, de manière qu'il se forme une phase aqueuse qui contient ou bien l'alcool 4-hydroxybenzylique ou bien les alcools 4- et 2-hydroxybenzyliques, et une phase organique qui contient les autres composés, on sépare la phase aqueuse et, au cas où l'alcool 4-hydroxybenzylique a seul été extrait dans la seconde étape d'extraction, on soumet la phase organique dans une troisième étape d'extraction à une répartition à contre-courant avec de l'eau, de manière qu'il se forme une phase organique contentant l'alcool 2-hydroxybenzylique et une phase aqueuse contenant les composés restants.
2. Procédé suivant la revendication 1, caractérisé en ce qu'on utilise comme solvant organique dans la variante (a), du toluène dans la première étape d'extraction, de l'éther de diisopropyle dans la deuxième étape d'extraction et de la méthylisobutylcétone dans la troisième étape d'extraction.
3. Procédé suivant les revendications 1 et 2, caractérisé en ce que le rapport en volume V sN a une valeur de 0,05 à 20 dans le système eau/solvant organique non miscible ou partiellement miscible à l'eau utilisé pour l'extraction à contre-courant.
4. Procédé suivant les revendications 1 à 4, caractérisé en ce que l'extraction à contre-courant est conduite à des températures de 20 à 70°C.
5. Procédé suivant les revendications 1 à 4, caractérisé en ce qu'on fait réagir du phénol avec du paraformaldéhyde dans le rapport molaire de 5 à 15:1.
6. Procédé suivant les revendications 1 à 4, caractérisé en ce qu'on fait réagir du phénol avec du paraformaldehyde dans un rapport molaire de 8 à 12:1.
EP78100188A 1977-06-28 1978-06-19 Procédé de préparation d'alcool 2-hydroxybenzylique pur et d'alcool 4-hydrobenzylique pur, ou d'un mélange de ces deux alcools Expired EP0000165B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2729075 1977-06-28
DE19772729075 DE2729075A1 (de) 1977-06-28 1977-06-28 Verfahren zur herstellung von reinem 2-hydroxybenzylalkohol, reinem 4-hydroxybenzylalkohol oder einem gemisch beider hydroxybenzylalkohole

Publications (2)

Publication Number Publication Date
EP0000165A1 EP0000165A1 (fr) 1979-01-10
EP0000165B1 true EP0000165B1 (fr) 1981-06-03

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EP78100188A Expired EP0000165B1 (fr) 1977-06-28 1978-06-19 Procédé de préparation d'alcool 2-hydroxybenzylique pur et d'alcool 4-hydrobenzylique pur, ou d'un mélange de ces deux alcools

Country Status (5)

Country Link
US (1) US4192959A (fr)
EP (1) EP0000165B1 (fr)
JP (1) JPS6045616B2 (fr)
DE (2) DE2729075A1 (fr)
IT (1) IT1105067B (fr)

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DE2928554A1 (de) * 1979-07-14 1981-01-29 Bayer Ag Verfahren zur herstellung eines gemisches aus 2- und 4-hydroxybenzylalkohol
FR2462409A1 (fr) * 1979-08-03 1981-02-13 Rhone Poulenc Ind Procede de preparation de particules solides de bisphenol-f
US4351962A (en) * 1980-07-11 1982-09-28 Rhone Poulenc Inc. Process for the preparation of hydroxy benzene carboxaldehydes
US4358624A (en) * 1980-12-31 1982-11-09 General Electric Company Fluorinated monophenols and diphenols and method for their preparation
US4374283A (en) * 1981-06-25 1983-02-15 General Electric Company Purification of aqueous effluent streams containing BPA and phenol
FR2508440B1 (fr) * 1981-06-25 1985-11-08 Saint Gobain Isover Procede de preparation d'alcools orthohydroxybenzyliques
DK335086A (da) * 1985-08-05 1987-02-06 Michele Testa Kemiske sammensaetninger og farmaceutiske praeparater til topisk brug indeholdende mindst en af de kemiske sammensaetninger i en terapeutiskvirksom maengde
US5019656A (en) * 1989-03-04 1991-05-28 Mitsubishi Petrochemical Co., Ltd. Process for preparing p-hydroxybenzyl alcohol
EP0485613B1 (fr) * 1990-05-25 1995-12-06 Mitsubishi Chemical Corporation Procede de para-methylolation d'un compose phenolique
EP0480308A1 (fr) * 1990-10-08 1992-04-15 Hoechst Aktiengesellschaft Procédé pour l'enlèvement de résorcinol des précondensats de résorcinol
FR2754533B1 (fr) * 1996-10-14 1998-11-27 Rhodia Chimie Sa Procede de preparation selective d'un acide 2-hydroxybenzoique et d'un 4-hydroxybenzaldehyde et derives
US7070226B2 (en) 2001-04-26 2006-07-04 Litens Automotive Powered opening mechanism and control system
US6719356B2 (en) 2001-04-26 2004-04-13 Litens Automotive Powered opening mechanism and control system
JP4485178B2 (ja) * 2003-12-01 2010-06-16 新日鐵化学株式会社 ビスフェノール類の製造方法
WO2005107848A2 (fr) 2004-04-01 2005-11-17 The General Hospital Corporation Methode de traitement dermatologique a l'aide de chromophores
JP4724073B2 (ja) * 2006-08-17 2011-07-13 富士通株式会社 レジストパターンの形成方法、半導体装置及びその製造方法
EP2540695A1 (fr) * 2010-02-25 2013-01-02 Ube Industries, Ltd. Procédé de production d'alcool méthylique aromatique de pureté élevée, et composition d'alcool méthylique aromatique de pureté élevée ayant une excellente stabilité au stockage
RU2766486C2 (ru) * 2015-02-12 2022-03-15 Икой С.П.А. Устройство и способ разделения и извлечения компонентов сплава, в частности сплава благородных металлов

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GB774696A (en) * 1954-04-30 1957-05-15 Distillers Co Yeast Ltd Process for the production of ortho-methylol phenols
US3931001A (en) * 1974-06-14 1976-01-06 The Dow Chemical Company Pentachlorophenol recovery with methylene chloride
NL7410872A (nl) * 1974-08-14 1976-02-17 Shell Int Research Werkwijze voor het zuiveren van in polyhydroxy- verbindingen aanwezige ruwe bishydroxyarylver- bindingen.

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Publication number Publication date
DE2729075A1 (de) 1979-01-18
JPS5436223A (en) 1979-03-16
JPS6045616B2 (ja) 1985-10-11
EP0000165A1 (fr) 1979-01-10
IT1105067B (it) 1985-10-28
IT7850028A0 (it) 1978-06-26
DE2860743D1 (en) 1981-09-10
US4192959A (en) 1980-03-11

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