DE4308562A1 - Process for the preparation of aromatic bromomethyl compounds - Google Patents

Process for the preparation of aromatic bromomethyl compounds

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Publication number
DE4308562A1
DE4308562A1 DE19934308562 DE4308562A DE4308562A1 DE 4308562 A1 DE4308562 A1 DE 4308562A1 DE 19934308562 DE19934308562 DE 19934308562 DE 4308562 A DE4308562 A DE 4308562A DE 4308562 A1 DE4308562 A1 DE 4308562A1
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Prior art keywords
aromatic
radical
bromination
bromomethyl
preparation
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DE19934308562
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German (de)
Inventor
Adalbert Dr Wagner
Heinz-Werner Dr Kleemann
Dieter Dr Regnat
Hans-Jerg Dr Kleiner
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Hoechst AG
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Hoechst AG
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Priority to DE19934308562 priority Critical patent/DE4308562A1/en
Priority to EP93116788A priority patent/EP0595150B1/en
Priority to ES93116788T priority patent/ES2092737T3/en
Priority to DE59303357T priority patent/DE59303357D1/en
Priority to FI934749A priority patent/FI934749A/en
Priority to AU50332/93A priority patent/AU5033293A/en
Priority to NO933904A priority patent/NO933904L/en
Priority to CA002109470A priority patent/CA2109470A1/en
Priority to JP5270087A priority patent/JPH06234667A/en
Priority to HU9303084A priority patent/HU9303084D0/en
Publication of DE4308562A1 publication Critical patent/DE4308562A1/en
Priority to US08/763,877 priority patent/US5750728A/en
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D275/00—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings
    • C07D275/04—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D275/06—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings condensed with carbocyclic rings or ring systems with hetero atoms directly attached to the ring sulfur atom
    • C—CHEMISTRY; METALLURGY
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    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B39/00—Halogenation
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
    • C07C17/14—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms in the side-chain of aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C22/00—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom
    • C07C22/02—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings
    • C07C22/04—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/15—Sulfonamides having sulfur atoms of sulfonamide groups bound to carbon atoms of six-membered aromatic rings
    • C07C311/16—Sulfonamides having sulfur atoms of sulfonamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the sulfonamide groups bound to hydrogen atoms or to an acyclic carbon atom
    • C07C311/18—Sulfonamides having sulfur atoms of sulfonamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the sulfonamide groups bound to hydrogen atoms or to an acyclic carbon atom to an acyclic carbon atom of a hydrocarbon radical substituted by nitrogen atoms, not being part of nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/50—Compounds containing any of the groups, X being a hetero atom, Y being any atom
    • C07C311/52—Y being a hetero atom
    • C07C311/53—X and Y not being nitrogen atoms, e.g. N-sulfonylcarbamic acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/307—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/24—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
    • C07D333/54—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
    • C07D333/60—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
    • C07D333/62—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring
    • C07D333/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
    • C07D333/62—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring
    • C07D333/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C07D333/70—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems

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

Abstract

The present invention relates to a process for the preparation of aromatic bromomethyl compounds in which, starting from an aromatic methyl compound, the bromomethyl compound is obtained by free-radical bromination in the solvent chlorobenzene.

Description

Brommethyl-Derivate haben sich seit langem als wertvolle Zwischenprodukte zur Herstellung von Katalysatoren und Wirkstoffen wie beispielsweise Pflanzenschutzmitteln oder Pharmaka erwiesen. Im allgemeinen werden aromatische Brommethyl-Verbindungen durch radikalische Bromierung gewonnen (siehe z. B. Römpps Chemielexikon, Bd. 1, Seite 521, 8. Aufl. (1979), Franckhsche Verlagshandlung Stuttgart).Bromomethyl derivatives have long been valuable intermediates Manufacture of catalysts and active ingredients such as Pesticides or pharmaceuticals proven. Generally will aromatic bromomethyl compounds by radical bromination won (see e.g. Römpps Chemielexikon, Vol. 1, page 521, 8th ed. (1979), Franckhsche Verlaghandlung Stuttgart).

Ausgehend von aromatischen Methyl-Verbindungen lassen sich durch radikalische Bromierung mit Bromierungsagentien, wie z. B. N-Bromsuccinimid oder 1,3-Dibrom-5,5-dimethylhydantoin, gegebenenfalls unter Zusatz eines Radikalstarters, wie beispielsweise Azoisobuttersäurenitril oder Benzoylperoxid, die entsprechenden aromatischen Brommethyl-Verbindungen herstellen. Bei dieser Umsetzung finden im allgemeinen Lösungsmittel wie Tetrachlormethan Verwendung, welche eine hohe Toxizität aufweisen und die darüber hinaus leicht flüchtig sind.Starting from aromatic methyl compounds, radical bromination with bromination agents, such as. B. N-bromosuccinimide or 1,3-dibromo-5,5-dimethylhydantoin, optionally with the addition of a Radical initiators, such as azoisobutyronitrile or benzoyl peroxide, produce the corresponding aromatic bromomethyl compounds. At this reaction generally find solvents such as carbon tetrachloride Use that have high toxicity and beyond are volatile.

Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung von aromatischen Brom-Methyl-Verbindungen der allgemeinen Formel (I)The present invention relates to a method for producing aromatic bromomethyl compounds of the general formula (I)

A(CH2-Br)n (I)A (CH 2 -Br) n (I)

bei dem eine aromatische Verbindung A-CH3, welche eine Methylgruppe enthält, in einer radikalischen Bromierungsreaktion unter Verwendung des Lösungsmittels Chlorbenzol zum Brommethyl-Derivat der Formel (I) umgesetzt wird, wobei n eine ganze Zahl 1, 2 oder 3, vorzugsweise 1 oder 2, bedeutet. in which an aromatic compound A-CH 3 , which contains a methyl group, is reacted in a radical bromination reaction using the solvent chlorobenzene to give the bromomethyl derivative of the formula (I), where n is an integer 1, 2 or 3, preferably 1 or 2 means.

Bei Verwendung von Chlorbenzol als Lösungsmittel kann überraschenderweise eine verbesserte Reaktionsausbeute erhalten werden. Darüberhinaus ergeben sich aufgrund der geringeren Giftigkeit des Lösungsmittels Chlorbenzol verfahrenstechnische Vereinfachungen, was insbesondere bei der Herstellung im Technikums- oder Produktionsmaßstab von Vorteil ist. Aufgrund des hohen Siedepunktes von Chlorbenzol (132°C) kann bei technischen Synthesen je nach Reaktivität des Eduktes in einem größeren Temperaturbereich eine Optimierung der Reaktionsbedingungen durchgeführt werden.Surprisingly, when using chlorobenzene as a solvent an improved reaction yield can be obtained. Furthermore result due to the lower toxicity of the solvent chlorobenzene procedural simplifications, which is particularly true in the manufacture of Technology or production scale is an advantage. Because of the high The boiling point of chlorobenzene (132 ° C) can vary depending on the technical synthesis Reactivity of the educt in a larger temperature range an optimization the reaction conditions are carried out.

Die Erfindung bezieht sich vorzugsweise auf ein Verfahren zur Herstellung von solchen aromatischen Brommethyl-Verbindungen der allgemeinen Formel (1),The invention preferably relates to a method for producing such aromatic bromomethyl compounds of the general formula (1),

A(CH2-Br)n (I)A (CH 2 -Br) n (I)

in denen n eine ganze Zahl 1, 2 oder 3, vorzugsweise 1 oder 2, bedeutet und die Gruppierung A für einen mono-, bi-, tri-, tetra-, penta- oder hexacyclischen Aryl- oder Heteroarylrest steht, der gegebenenfalls einfach, zweifach, dreifach oder vierfach substituiert sein kann.in which n is an integer 1, 2 or 3, preferably 1 or 2, and the grouping A for a mono-, bi-, tri-, tetra-, penta- or hexacyclic Aryl or heteroaryl radical, which is optionally single, double, triple or can be substituted four times.

Die Gruppierung A kann auch durch mehrere -CH3-Gruppen substituiert sein, die je nach eingesetzter Menge an Bromierungsagentien dann in CH2-Br-Gruppen überführt werden.The group A can also be substituted by several —CH 3 groups, which are then converted into CH 2 -Br groups, depending on the amount of bromination agents used.

Unter Aryl ist vorzugsweise ein (C6-C20)-Arylrest, wie beispielsweise Phenyl, Naphthyl oder Biphenyl, Binaphthyl zu verstehen, insbesondere jedoch Phenyl oder Biphenyl.Aryl is preferably understood to mean a (C 6 -C 20 ) aryl radical, such as, for example, phenyl, naphthyl or biphenyl, binaphthyl, but in particular phenyl or biphenyl.

Bevorzugt wird auch die zweifache Bromierung eines Binaphthylderivats, welches zwei Methylgruppen enthält.The double bromination of a binaphthyl derivative is also preferred, which contains two methyl groups.

Unter Heteroaryl werden bevorzugt (C1-C9)-Heteroarylgruppen verstanden, die sich von Phenyl oder Naphthyl ableiten und in welchen eine oder mehrere CH- Gruppen durch Stickstoff ersetzt sind und/oder in welchen mindestens zwei benachbarte CH-Gruppen unter Bildung eines 5-gliedrigen aromatischen Rings durch ein Schwefelatom, ein Sauerstoffatom oder eine NH-Gruppe ersetzt sind. Bevorzugte Heteroarylgruppen sind folgende Gruppierungen:
Furanyl, Thienyl, Pyrolyl, Imidazolyl, Pyrazolyl, Triazolyl, Tetrazolyl, Oxazolyl, Isoxazolyl, Thiazolyl, Isothiazolyl, Pyridyl, Pyrazinyl, Pyrimidinyl, Pyridazinyl, Indolyl, Indazolyl, Chinolyl, Isochinolyl, Phthalazinyl, Chinoxylinyl, Chinazolinyl, Cinnolinyl, Benzothienyl, Pyridazopyridyl, Pyridazopyrimidinyl, Pyridinothienyl sowie Imidazopyridyl.Heteroaryl is preferably understood to mean (C 1 -C 9 ) heteroaryl groups which are derived from phenyl or naphthyl and in which one or more CH groups have been replaced by nitrogen and / or in which at least two adjacent CH groups have formed a 5 -membered aromatic ring are replaced by a sulfur atom, an oxygen atom or an NH group. Preferred heteroaryl groups are the following groups:
Furanyl, thienyl, pyrolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolyl, indazolyl, quinolyl, isoquinolyl, pyrothazolylyl, phthalazylylyl, phthalazylylyl, phthalazylylyl, phthalazylylyl, phthalazylylyl, phthalazylylyl, phthalazylyl, phthalazylyl, phthalazylyl, phthalazylyl, phthalazylyl Pyridazopyrimidinyl, pyridinothienyl and imidazopyridyl.

Besonders bevorzugt sind als Heteroaromaten Benzothiophen, Pyridazopyridin, Pyridazopyrimidin, Thienyl, Benzothiazol und Pyridinothienyl.Particularly preferred heteroaromatics are benzothiophene, pyridazopyridine, Pyridazopyrimidine, thienyl, benzothiazole and pyridinothienyl.

Als Substituenten kommen im Prinzip alle üblichen Substituenten von aromatischen Systemen in Frage, die selbst nicht radikalisch bromiert sind.In principle, all customary substituents come from aromatic systems that are not themselves radically brominated.

Als Substituenten geeignet sind z. B. Halogen, insbesondere F, Cl, Br; -(CH2)n-COOR1, -CONR2, -SO2NR2, -SO2-R3, Phenyl, Phenyl mono- oder di­ substituiert durch Halogen, -CN, -(C1-C4)-Alkyl, welches durch COOR1 substituiert ist und -(C2-C4)-Alkenyl, welches durch COOR1 substituiert ist.Suitable substituents are, for. B. halogen, in particular F, Cl, Br; - (CH 2 ) n -COOR 1 , -CONR 2 , -SO 2 NR 2 , -SO 2 -R 3 , phenyl, phenyl mono- or di substituted by halogen, -CN, - (C 1 -C 4 ) - Alkyl which is substituted by COOR 1 and - (C 2 -C 4 ) alkenyl which is substituted by COOR 1 .

R1 bedeutet hierbei (C1-C6)-Alkyl oder Wasserstoff;
R² bedeutetR 1 here denotes (C 1 -C 6 ) alkyl or hydrogen;
R² means

R3 bedeutet NHCOOR1; und
n ist eine ganze Zahl von 0 bis 4, vorzugsweise 1 oder 2.R 3 represents NHCOOR 1 ; and
n is an integer from 0 to 4, preferably 1 or 2.

Die bei der radikalischen Bromierung unter Verwendung des Lösungsmittels Chlorbenzol gewonnenen Brommethyl-Verbindungen werden in der Regel in so hoher Ausbeute gewonnen, daß eine weitergehende Reinigung nicht erforderlich ist. Sie können dann ohne aufwendige Trennverfahren für die weitere Synthese eingesetzt werden. Erforderlichenfalls können Brommethyl-Verbindungen mit besonderer Reinheit durch gängige Methoden, wie beispielsweise Chromatographie, Destillation oder Kristallisation erhalten werden.The radical bromination using the solvent Chlorobenzene-derived bromomethyl compounds are usually found in this way high yield obtained that further cleaning is not required is. They can then be used for further synthesis without complex separation processes be used. If necessary, bromomethyl compounds can be used  special purity through common methods, such as Chromatography, distillation or crystallization can be obtained.

Die Reaktionstemperatur bei dem erfindungsgemäßen Verfahren beträgt (bei Normaldruck) vorzugsweise zwischen Raumtemperatur und Siedetemperatur, insbesondere 60 bis 132°C. Prinzipiell ist die Durchführung der Bromierung auch unter erhöhtem Druck durchführbar.The reaction temperature in the process according to the invention is (at Normal pressure) preferably between room temperature and boiling temperature, especially 60 to 132 ° C. In principle, the bromination is carried out can also be carried out under increased pressure.

Als Bromierungsagentien können übliche bromhaltige Verbindungen eingesetzt werden, als besonders geeignet hat sich N-Bromsuccinimid ergeben. Die Reaktionszeit beträgt zwischen wenigen Minuten und mehreren Stunden, je nach Reaktivität der eingesetzten aromatischen Methyl-Verbindung.Conventional bromine-containing compounds can be used as bromination agents N-bromosuccinimide has been found to be particularly suitable. The Response time is between a few minutes and several hours, depending according to the reactivity of the aromatic methyl compound used.

Die Erfindung wird durch nachfolgendes Beispiel näher erläutert:The invention is explained in more detail by the following example:

Beispielexample Verfahren zur Herstellung von 2,2′-Bis-(brommethyl)-1,1′-binaphthylProcess for the preparation of 2,2'-bis (bromomethyl) -1,1'-binaphthyl

Zu 8,5 g (30 mmol) 2,2-Dimethyl-1,1′-binaphthyl in 100 ml Chlorbenzol gibt man unter Rückfluß bei Siedetemperatur portionsweise ein Gemisch aus 10,7 g (60 mmol) N-Bromsuccinimid und 100 mg Benzoylperoxid. Nach beendeter Zugabe wird noch 1 Stunde bei Siedetemperatur gerührt und das Lösungsmittel verdampft. Der Rückstand wird in 50 ml Ethylacetat aufgenommen und je 1 × mit 10%iger Na2SO3-Lösung, gesättigter Na2CO3 und gesättigter NaCl-Lösung gewaschen. Nach dem Trocknen mit MgSO4 wird eingeengt. Man erhält 13,2 g (100%) gelbes Öl. Aus Toluol kristallisieren 8,6 g farblose Kristalle mit Schmp. 147-149°C. A mixture of 10.7 g (60 mmol) of N-bromosuccinimide and 100 mg of benzoyl peroxide is added in portions to 8.5 g (30 mmol) of 2,2-dimethyl-1,1'-binaphthyl in 100 ml of chlorobenzene at reflux at the boiling point . When the addition is complete, the mixture is stirred at the boiling temperature for 1 hour and the solvent is evaporated. The residue is taken up in 50 ml of ethyl acetate and washed once each with 10% Na 2 SO 3 solution, saturated Na 2 CO 3 and saturated NaCl solution. After drying with MgSO 4 , the mixture is concentrated. 13.2 g (100%) of yellow oil are obtained. 8.6 g of colorless crystals with mp. 147-149 ° C. crystallize from toluene.

Claims (6)

1. Verfahren zur Herstellung von aromatischen Brommethyl-Verbindungen, bei dem ausgehend von einer aromatischen Methyl-Verbindung durch radikalische Bromierung im Lösungsmittel Chlorbenzol die Brommethyl- Verbindung erhalten wird.1. Process for the preparation of aromatic bromomethyl compounds, starting from an aromatic methyl compound radical bromination in the solvent chlorobenzene the bromomethyl Connection is obtained. 2. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß man ausgehend von einer Verbindung (E) A(CH3)n (E)eine Verbindung der Formel (I) herstellt,A(CH2-Br)n (I)wobei A für einen aromatischen Rest steht, der gegebenenfalls substituiert ist, und n eine ganze Zahl 1, 2 oder 3 bedeutet.2. The method according to claim 1, characterized in that starting from a compound (E) A (CH 3 ) n (E) a compound of formula (I) is prepared, A (CH 2 -Br) n (I) where A represents an aromatic radical which is optionally substituted and n is an integer 1, 2 or 3. 3. Verfahren gemäß Anspruch 2, dadurch gekennzeichnet, daß A für einen mono-, bi-, tri-, tetra-, penta- oder hexacyclischen Aryl- oder Heteroarylrest steht, der gegebenenfalls einfach, zweifach, dreifach oder vierfach substituiert sein kann.3. The method according to claim 2, characterized in that A for a mono-, bi-, tri-, tetra-, penta- or hexacyclic aryl or Heteroaryl residue, which may be single, double, triple or can be substituted four times. 4. Verfahren gemäß Anspruch 3, dadurch gekennzeichnet, daß A für ein Binaphthyl-System steht und n gleich 2 ist.4. The method according to claim 3, characterized in that A for a Binaphthyl system stands and n is 2. 5. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß die radikalische Bromierung unter Verwendung von N-Bromsuccinimid durchgeführt wird.5. The method according to claim 1, characterized in that the radical bromination using N-bromosuccinimide is carried out. 6. Verfahren gemäß Anspruch 5, dadurch gekennzeichnet, daß die Bromierung unter Einsatz eines Radikalbildners erfolgt.6. The method according to claim 5, characterized in that the Bromination is carried out using a radical generator.
DE19934308562 1992-10-29 1993-03-18 Process for the preparation of aromatic bromomethyl compounds Withdrawn DE4308562A1 (en)

Priority Applications (11)

Application Number Priority Date Filing Date Title
DE19934308562 DE4308562A1 (en) 1993-03-18 1993-03-18 Process for the preparation of aromatic bromomethyl compounds
EP93116788A EP0595150B1 (en) 1992-10-29 1993-10-18 Process for the preparation of aromatic bromomethylcompounds
ES93116788T ES2092737T3 (en) 1992-10-29 1993-10-18 PROCEDURE FOR THE PREPARATION OF BROMOMETIL-AROMATIC COMPOUNDS.
DE59303357T DE59303357D1 (en) 1992-10-29 1993-10-18 Process for the preparation of aromatic bromomethyl compounds
AU50332/93A AU5033293A (en) 1992-10-29 1993-10-27 Process for the preparation of aromatic bromomethyl compounds
FI934749A FI934749A (en) 1992-10-29 1993-10-27 For the production of aromatic bromomethylation
NO933904A NO933904L (en) 1992-10-29 1993-10-28 Process for the preparation of aromatic bromomethyl compounds
CA002109470A CA2109470A1 (en) 1992-10-29 1993-10-28 Process for the preparation of aromatic bromomethyl compounds
JP5270087A JPH06234667A (en) 1992-10-29 1993-10-28 Preparation of aromatic bromomethyl compound
HU9303084A HU9303084D0 (en) 1992-10-29 1993-10-29 Process for preparation of aromatic bromo-methyl compounds
US08/763,877 US5750728A (en) 1992-10-29 1996-12-11 Process for the preparation of aromatic bromomethyl compounds

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0675095A1 (en) 1994-03-23 1995-10-04 Hoechst Aktiengesellschaft Process for preparing 2,2'-bis(halogenomethyl)-1,1'-binaphthalene

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0675095A1 (en) 1994-03-23 1995-10-04 Hoechst Aktiengesellschaft Process for preparing 2,2'-bis(halogenomethyl)-1,1'-binaphthalene

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