FR2688507A1 - New derivs. of tetrazolyl-benzene-boronic acids - useful as synthetic intermediates - Google Patents

New derivs. of tetrazolyl-benzene-boronic acids - useful as synthetic intermediates Download PDF

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FR2688507A1
FR2688507A1 FR9203114A FR9203114A FR2688507A1 FR 2688507 A1 FR2688507 A1 FR 2688507A1 FR 9203114 A FR9203114 A FR 9203114A FR 9203114 A FR9203114 A FR 9203114A FR 2688507 A1 FR2688507 A1 FR 2688507A1
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dimethylethyl
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FR2688507B1 (en
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Chekroun Isaac
Bedoya Zurita Manuel
Ruiz Montes Jose
Rossey Guy
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Synthelabo SA
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
    • C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D257/04—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
    • C07F5/02—Boron compounds
    • C07F5/025—Boronic and borinic acid compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
    • C07F5/02—Boron compounds
    • C07F5/05—Cyclic compounds having at least one ring containing boron but no carbon in the ring

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Abstract

The prods. 2-(1-(1,1-dimethylethyl)-1H-tetrazole-5-yl)benzene-boronic acid and 2-(2-(1,1-dimethylethyl)-2H-tetrazole-5-yl)-benzene boronic acid are new. Also claimed are their prepn. and use to obtain cpds. of formula (I). The cpds. are prepared according to the specified reaction scheme. The protected cpd. (3) is reacted with an alkyl-lithium (such as butyl-lithium) in an aprotic solvent (such as THF) at a temp. between -50 deg.C to +20 deg.C: an organo-lithium is obtd. which is reacted with trialkyl borate in a solvent (e.g. THF). An alkyl benzeneboronate is obtd. which is hydrolysed to the acid. USE/ADVANTAGE - The cpds. are used to prepare cpds. with aryl-aryl couplings in the presence of Pd catalysts. The gp. 1,1-dimethylethyl is a very stable protecting gp. in different reaction conditions encountered in organic chemistry.

Description

La présente invention concerne des dérivés de l'acide benzèneboronique répondant à la formule (1)

Figure img00010001

dans laquelle le groupement 1,1-diméthyléthyle est en position 1 ou 2 du cycle tétrazole, leur préparation et leur utilisation dans des couplages aryle-aryle en présence de catalyseurs au palladium.The present invention relates to benzeneboronic acid derivatives corresponding to formula (1)
Figure img00010001

in which the 1,1-dimethylethyl group is in position 1 or 2 of the tetrazole ring, their preparation and their use in aryl-aryl couplings in the presence of palladium catalysts.

Les composés de l'invention sont préparés, à partir du 5-phényltétrazole de formule (2), selon le schéma suivant:

Figure img00010002
The compounds of the invention are prepared, from 5-phenyltetrazole of formula (2), according to the following scheme:
Figure img00010002

On protège le groupe tétrazolyle du 5-phényltétrazole (2) par un groupement 1,1-diméthyléthyle selon la méthode décrite pour un dérivé analogue par J. W. TILLE et coll. J. Med.The tetrazolyl group of 5-phenyltetrazole (2) is protected by a 1,1-dimethylethyl group according to the method described for an analogous derivative by J. W. TILLE et al. J. Med.

Chem. 1991, 34, 1125-1126 et on fait réagir le composé (3) obtenu avec un alkyllithium, tel le butyllithium, dans un solvant aprotique comme le tétrahydrofurane, à une température comprise entre - 500C et + 200C. On obtient un organolithien que l'on fait réagir avec du trialkylborate dans un solvant tel que le tétrahydrofurane. On obtient un benzeneboronate d'alkyle que l'on soumet à une réaction d'hydrolyse. Chem. 1991, 34, 1125-1126 and the compound (3) obtained is reacted with an alkyllithium, such as butyllithium, in an aprotic solvent such as tetrahydrofuran, at a temperature between - 500C and + 200C. An organolithium is obtained which is reacted with trialkylborate in a solvent such as tetrahydrofuran. An alkyl benzeneboronate is obtained which is subjected to a hydrolysis reaction.

Les dérivés de l'acide benzèneboronique ainsi obtenus, sont des solides stables que l'on peut coupler avec des halogénures aromatiques comportant de nombreux substituants tels que par exemple, les groupes carboxamide, carbonyle, carboxyle, cyano, alcoxyle ou nitro. Ces couplages peuvent être réalisés en milieu hydroorganique. The benzeneboronic acid derivatives thus obtained are stable solids which can be coupled with aromatic halides containing numerous substituents such as, for example, carboxamide, carbonyl, carboxyl, cyano, alkoxyl or nitro groups. These couplings can be carried out in a hydroorganic medium.

Le groupement 1,1-diméthyléthyle est un groupement protecteur particulièrement stable dans différentes conditions réactionnelles rencontrées en chimie organique. Son utilisation comme groupement protecteur de la fonction tétrazolyle, autorise l'emploi des composés de l'invention et des produits en résultant, dans différentes réactions de transformation chimique.The 1,1-dimethylethyl group is a particularly stable protective group under various reaction conditions encountered in organic chemistry. Its use as a protecting group for the tetrazolyl function allows the use of the compounds of the invention and of the products resulting therefrom, in various chemical transformation reactions.

L'exemple suivant illustre la préparation d'un composé selon l'invention.The following example illustrates the preparation of a compound according to the invention.

Les analyses confirment la structure des produits obtenus.The analyzes confirm the structure of the products obtained.

Exemple acide 2-F 2- (1, 1-dimethylethyl)-21?-ttrazol-5-ylJbenzene- boronique.Example 2-F 2- (1,1-dimethylethyl) -21? -Ttrazol-5-ylJbenzene-boronic acid.

1. 2-(1,1-diméthyléthyl)-5-phényl-2N-tétrazole. 1. 2- (1,1-Dimethylethyl) -5-phenyl-2N-tetrazole.

Dans un ballon de 500 ml, on introduit 30 g de 5-phényltétrazole et 210 ml d'acide trifluoroacétique. A la suspension obtenue, on ajoute 10 ml d'acide sulfurique concentré et 33,6 g de 1,1-diméthyléthanol. On laisse le mélange réactionnel, sous agitation, pendant 48 heures puis on le verse sur 750 ml d'acétate d'éthyle. On lave la solution avec 2 fois 200 ml d'eau puis avec de la soude à 10 % jusqu'à pH alcalin et à nouveau avec 2 fois 200 ml d'eau. Après séchage de la phase organique et évaporation sous vide, on obtient 36,15 g de produit sous forme d'huile.30 g of 5-phenyltetrazole and 210 ml of trifluoroacetic acid are introduced into a 500 ml flask. To the suspension obtained, 10 ml of concentrated sulfuric acid and 33.6 g of 1,1-dimethylethanol are added. The reaction mixture is left under stirring for 48 hours and then poured onto 750 ml of ethyl acetate. The solution is washed with 2 times 200 ml of water then with 10% sodium hydroxide until alkaline pH and again with 2 times 200 ml of water. After drying the organic phase and evaporation under vacuum, 36.15 g of product are obtained in the form of an oil.

Ce produit a les mêmes caractéristiques que celui décrit par
R. A. HENRY, J. Heterocyclic Chem., 1976, 13, 391-392.This product has the same characteristics as that described by
RA HENRY, J. Heterocyclic Chem., 1976, 13, 391-392.

2. acide 2-t2-(1,1-diméthyléthyl)-2H-tétrazol-5-yll- benzèneboronique.2. 2-t2- (1,1-dimethylethyl) -2H-tetrazol-5-yll-benzeneboronic acid.

Dans un ballon tricol de 250 ml, sous azote, on introduit 5 g de 2-(1,1-diméthyléthyl)-5-phényl-2H-tétrazole et 40 ml de tétrahydrofurane anhydre. A cette solution, refroidie à - 500C, on ajoute goutte à goutte 20 ml d'une solution 2,5 M de n-butyllithium dans l'hexane. On agite la solution pendant 30 min à la température ambiante puis pendant 30 min à 500C. 5 g of 2- (1,1-dimethylethyl) -5-phenyl-2H-tetrazole and 40 ml of anhydrous tetrahydrofuran are introduced into a 250 ml three-necked flask under nitrogen. To this solution, cooled to −500 ° C., 20 ml of a 2.5 M solution of n-butyllithium in hexane are added dropwise. The solution is stirred for 30 min at room temperature and then for 30 min at 500C.

On refroidit la solution obtenue à - 50 C. On l'ajoute à une solution de 6,3 ml de triéthylborate dans 20 ml de tetrahydrofurane anhydre maintenue à - 500C. On laisse le mélange une nuit, sous agitaton, à la température ambiante puis on le verse sur 100 ml d'acide chlorhydrique à 10 %. On extrait le mélange par 350 ml d'acétate d'éthyle. On lave la phase organique avec 100 ml d'eau et on la sèche sur du sulfate de magnésium. Après filtration et évaporation, on recueille un résidu que l'on purifie par chromatographie.The solution obtained is cooled to -50 C. It is added to a solution of 6.3 ml of triethylborate in 20 ml of anhydrous tetrahydrofuran maintained at -500C. The mixture is left overnight, under agitation, at room temperature and then poured onto 100 ml of 10% hydrochloric acid. The mixture is extracted with 350 ml of ethyl acetate. The organic phase is washed with 100 ml of water and dried over magnesium sulfate. After filtration and evaporation, a residue is collected which is purified by chromatography.

On obtient 4,32 g de produit.4.32 g of product are obtained.

Point de fusion = 115-1180C Rendement = 71 %
Les composés selon l'invention peuvent être utilisés pour la synthèse de composés répondant à la formule (I)

Figure img00030001

dans laquelle
X représente soit un groupe (C14)alkyle, soit un groupe formyle, soit un groupe (C13)alcoxy, soit un groupe CH(ORs)2, soit un groupe CH(OH)OR5 où R5 est un atome d'hydrogène ou un groupe (C1~3)alkyle pouvant éventuellement former dans le cas de CH(OR5)2 un cycle 1,3-dioxolane ou 1,3-dioxane, soit un groupe de formule générale
Figure img00040001

dans laquelle
R1 représente soit un groupe (C~7)alkyle droit ou ramifie, soit un groupe (C3-9)alcényle droit ou ramifie, soit un groupe cyclo(C3-7)alkyl(C1-6)alkyle,
R2 représente soit un atome d'hydrogène, soit un groupe (C1-7)alkyle droit ou ramifié, soit un groupe cyclo(C3 7)alkyl(C13)alkyle, soit un groupe aryl(C1~3)alkyle éventuellement substitué sur le noyau, soit un groupe aryloxy(C1~3)alkyle éventuellement substitué sur le noyau, soit un groupe arylthio(C13)alkyle éventuellement substitué sur le noyau, soit un groupe arylsulfonyl(C1-3)alkyle éventuellement substitué sur le noyau, soit un groupe hétéroaryl(C1~3)alkyle éventuellement substitué sur le noyau, composés décrits dans les demandes de brevets français 9116290 et 9102032.Melting point = 115-1180C Yield = 71%
The compounds according to the invention can be used for the synthesis of compounds corresponding to formula (I)
Figure img00030001

in which
X represents either a (C14) alkyl group, or a formyl group, or a (C13) alkoxy group, or a CH (ORs) 2 group, or a CH (OH) OR5 group where R5 is a hydrogen atom or a (C1 ~ 3) alkyl group which may optionally form, in the case of CH (OR5) 2, a 1,3-dioxolane or 1,3-dioxane ring, ie a group of general formula
Figure img00040001

in which
R1 represents either a straight or branched (C ~ 7) alkyl group, or a straight or branched (C3-9) alkenyl group, or a cyclo (C3-7) alkyl (C1-6) alkyl group,
R2 represents either a hydrogen atom, or a (C1-7) straight or branched alkyl group, or a cyclo (C3-7) alkyl (C13) alkyl group, or an aryl (C1 ~ 3) alkyl group optionally substituted on the nucleus, either an aryloxy (C1 ~ 3) alkyl group optionally substituted on the nucleus, or an arylthio (C13) alkyl group optionally substituted on the nucleus, or an arylsulfonyl (C1-3) alkyl group optionally substituted on the nucleus, or a heteroaryl group (C1 ~ 3) alkyl optionally substituted on the nucleus, compounds described in French patent applications 9116290 and 9102032.

Le schéma suivant décrit la synthèse des composés de formule générale (I) à partir des composés de l'invention:

Figure img00040002
The following diagram describes the synthesis of the compounds of general formula (I) from the compounds of the invention:
Figure img00040002

On fait réagir un dérivé de l'acide benzèneboronique de formule générale (1) avec un dérivé bromé de formule générale (4) dans laquelle X est tel que défini ci-dessus, en présence d'une base telle que le carbonate de sodium et d'un catalyseur tel que le palladium tetrakistriphénylphosphine, dans un solvant tel que le toluène.A benzeneboronic acid derivative of general formula (1) is reacted with a brominated derivative of general formula (4) in which X is as defined above, in the presence of a base such as sodium carbonate and a catalyst such as palladium tetrakistriphenylphosphine, in a solvent such as toluene.

L'exemple ci-dessous illustre la synthèse des composés de formule générale (I) à partir des composés selon l'invention.The example below illustrates the synthesis of the compounds of general formula (I) from the compounds according to the invention.

2'-f2-(1,1-diméthYléthyl)-2N-tétrazol-5-sllE1 1'biphénol]-4- carboxaldéhyde. 2'-f2- (1,1-dimethYlethyl) -2N-tetrazol-5-sllE1 1'biphenol] -4- carboxaldehyde.

Dans un ballon de 50 ml muni d'un réfrigérant, on introduit 1 g d'acide 2-[2-(1,1-diméthyléthyl)-2H-tétrazol-5-yl]ben- zèneboronique, 0,828 g de 4-bromobenzaldéhyde, 0,116 g de palladium dibenzilidèneacétone, 0,22 g de triphénylphosphine, 20 ml de toluène et 4,1 ml d'une solution 2 M de carbonate de sodium. On porte le mélange au reflux pendant 4 heures. On verse la solution dans 20 ml d'une solution saturée de chlorure d'ammonium. On extrait avec de l'acétate d'éthyle. On lave la phase organique avec 20 ml d'eau puis avec 20 ml d'une solution saturée de chlorure de sodium. On la sèche sur du sulfate de magnésium et on évapore sous vide.1 g of 2- [2- (1,1-dimethylethyl) -2H-tetrazol-5-yl] benzeneneboronic acid, 0.828 g of 4-bromobenzaldehyde is introduced into a 50 ml flask equipped with a condenser , 0.116 g of palladium dibenzilideneacetone, 0.22 g of triphenylphosphine, 20 ml of toluene and 4.1 ml of a 2 M solution of sodium carbonate. The mixture is brought to reflux for 4 hours. The solution is poured into 20 ml of a saturated ammonium chloride solution. Extraction is carried out with ethyl acetate. The organic phase is washed with 20 ml of water and then with 20 ml of a saturated sodium chloride solution. It is dried over magnesium sulphate and evaporated under vacuum.

On purifie le résidu par chromatographie sur colonne de gel de silice.The residue is purified by chromatography on a column of silica gel.

On obtient 0,861 g de produit.0.861 g of product is obtained.

Point de fusion = 71-730C Rendement = 70 % Melting point = 71-730C Yield = 70%

Claims (3)

Revendications 1. L'acide 2-t1-(1,1-diméthyléthyl)-1H-tétrazol-5- yl)benzèneboronique et l'acide 2-2-(l,l-diméthyléthyl)-2H- tétrazol-5-yl)benzèneboronique. Claims 1. 2-t1- (1,1-dimethylethyl) -1H-tetrazol-5-yl) benzeneboronic acid and 2-2- (1,1-dimethylethyl) -2H-tetrazol-5-yl acid ) benzeneboronic. 2. Procédé de préparation des composés selon la revendication 1, procédé caractérisé en ce que l'on protège le groupe tétrazolyle du 5-phényltétrazole par un groupement 1,1-diméthyléthyle, puis on fait réagir le composé obtenu avec un alkyllithium, puis on fait réagir l'organolithien forme avec du trialkylborate et enfin on soumet le benzèneboronate d'alkyle obtenu à une hydrolyse acide pour obtenir un composé selon la revendication 1.2. Process for the preparation of the compounds according to claim 1, process characterized in that the tetrazolyl group is protected from 5-phenyltetrazole by a 1,1-dimethylethyl group, then the compound obtained is reacted with an alkyllithium, then reacts the organolithium formed with trialkylborate and finally the alkyl benzeneboronate obtained is subjected to acid hydrolysis to obtain a compound according to claim 1. 3. Utilisation des composés selon la revendication 1 pour la préparation des composes de formule (I)3. Use of the compounds according to claim 1 for the preparation of the compounds of formula (I)
Figure img00060001
Figure img00060001
 dans laquelle in which X représente soit un groupe (C14)alkyle, soit un groupe formyle, soit un groupe (C13)alcoxy, soit un groupe CH(OR5)2, soit un groupe CH(OH)OR5 où R5 est un atome d'hydrogène ou un groupe (C1~3)alkyle pouvant éventuellement former dans le cas de CH(OR5)2 un cycle 1,3-dioxolane ou 1,3-dioxane, soit un groupe de formule générale X represents either a (C14) alkyl group, or a formyl group, or a (C13) alkoxy group, or a CH (OR5) 2 group, or a CH (OH) OR5 group where R5 is a hydrogen atom or a (C1 ~ 3) alkyl group which may optionally form, in the case of CH (OR5) 2, a 1,3-dioxolane or 1,3-dioxane ring, ie a group of general formula
Figure img00070001
Figure img00070001
 dans laquelle in which R1 représente soit un groupe (C1-7)alkyle droit ou ramifié, soit un groupe (C3-9)alcényle droit ou ramifié, soit un groupe cyclo(C37)alkyl(C1-6)alkyle,R1 represents either a (C1-7) straight or branched alkyl group, or a (C3-9) straight or branched alkenyl group, or a cyclo (C37) alkyl (C1-6) alkyl group, R2 représente soit un atome d'hydrogène, soit un groupe (C1-7)alkyle droit ou ramifié, soit un groupe cyclo(C3-7)alkyl(C1-3)alkyle, soit un groupe aryl(C1~3)alkyle éventuellement substitué sur le noyau, soit un groupe aryloxy(C13)alkyle éventuellement substitué sur le noyau, soit un groupe arylthio(C1-3)alkyle éventuellement substitué sur le noyau, soit un groupe arylsulfonyl(C1-3)alkyle éventuellement substitué sur le noyau, soit un groupe hétéroaryl(C1-3)alkyle éventuellement substitué sur le noyau. R2 represents either a hydrogen atom, or a (C1-7) straight or branched alkyl group, or a cyclo (C3-7) alkyl (C1-3) alkyl group, or an aryl (C1 ~ 3) alkyl group optionally substituted on the nucleus, either an aryloxy (C13) alkyl group optionally substituted on the nucleus, or an arylthio (C1-3) alkyl group optionally substituted on the nucleus, or an arylsulfonyl (C1-3) alkyl group optionally substituted on the nucleus , or a heteroaryl (C1-3) alkyl group optionally substituted on the nucleus.
FR9203114A 1992-03-16 1992-03-16 DERIVATIVES OF TETRAZOLYLBENZENEBORONIC ACID, THEIR PREPARATION AND THEIR USE AS SYNTHESIS INTERMEDIATES. Expired - Fee Related FR2688507B1 (en)

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KR1019930003887A KR930019649A (en) 1992-03-16 1993-03-15 Tetrazolyl Benzene Boronic Acid Derivatives and Processes for the Preparation and Use as Synthetic Intermediates

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0643704A1 (en) * 1991-11-18 1995-03-22 E.I. Du Pont De Nemours And Company Tetrazolylphenylboronic acid intermediates for the synthesis of aii receptor antagonists

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0238272A2 (en) * 1986-03-13 1987-09-23 Btg International Limited Intermediates useful in the production of pesticides
EP0470795A1 (en) * 1990-08-09 1992-02-12 Zeneca Limited Process for the manufacture of nitriles

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0238272A2 (en) * 1986-03-13 1987-09-23 Btg International Limited Intermediates useful in the production of pesticides
EP0470795A1 (en) * 1990-08-09 1992-02-12 Zeneca Limited Process for the manufacture of nitriles

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JOURNAL OF HETEROCYCLIC CHEMISTRY vol. 13, 1975, pages 391 - 392 HENRY, R.A. *
JOURNAL OF MEDICINAL CHEMISTRY vol. 34, no. 3, 1991, pages 1125 - 1136 TILLEY, J.W. ET AL *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0643704A1 (en) * 1991-11-18 1995-03-22 E.I. Du Pont De Nemours And Company Tetrazolylphenylboronic acid intermediates for the synthesis of aii receptor antagonists
EP0643704A4 (en) * 1991-11-18 1995-04-12 E.I. Du Pont De Nemours And Company Tetrazolylphenylboronic acid intermediates for the synthesis of aii receptor antagonists.
EP1384717A2 (en) * 1991-11-18 2004-01-28 E.I. Dupont De Nemours And Company Tetrazolylphenylboronic acid intermediates for the synthesis of A II receptor antagonists
EP1384717A3 (en) * 1991-11-18 2004-02-04 E.I. Dupont De Nemours And Company Tetrazolylphenylboronic acid intermediates for the synthesis of A II receptor antagonists

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