FR2717480A1 - New bis(phosphane oxide(s)) and macro:cyclic bis(phosphane(s)) - Google Patents
New bis(phosphane oxide(s)) and macro:cyclic bis(phosphane(s)) Download PDFInfo
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- FR2717480A1 FR2717480A1 FR9403313A FR9403313A FR2717480A1 FR 2717480 A1 FR2717480 A1 FR 2717480A1 FR 9403313 A FR9403313 A FR 9403313A FR 9403313 A FR9403313 A FR 9403313A FR 2717480 A1 FR2717480 A1 FR 2717480A1
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- 0 CC(C)C(C=C(Cc1cc(*)cc(CC(C2=O)=CC(*)=CC2=C2)c1O*)C1=O)=CC1=Cc1cc(*)cc2c1O* Chemical compound CC(C)C(C=C(Cc1cc(*)cc(CC(C2=O)=CC(*)=CC2=C2)c1O*)C1=O)=CC1=Cc1cc(*)cc2c1O* 0.000 description 7
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- B01J31/2457—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring with more than one complexing phosphine-P atom comprising aliphatic or saturated rings, e.g. Xantphos
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Abstract
Description
Procédé de préparation de bis(oxyd-s de phoaphane) et bis(phosphanes) macrocycliqueo. Process for the preparation of bis (phoaphane oxides) and macrocyclic bis (phosphanes).
La présente invention a pour objet un procédé de préparation de bis(oxydes de phosphane) de formule générale
dans laquelle - R1, R2, R3 et Rs, qui peuvent être identiques ou différents, représentent un atome d'hydrogène ou un groupe hydrocarboné, substitué ou non substitué, saturé ou insaturé, linéaire, ramifié, cyclique ou aromatique, de 1 à 28 atomes de carbone, comprenant éventuellement dans son squelette un ou plusieurs atomes choisis parmi les atomes d'oxygène, de soufre, d'azote, de phosphore et de silicium, ou encore SO3Ml/v avec M symbolisant un métal et v étant la valence du métal M; - RS, R6, R7 et R6 qui peuvent être identiques ou différents, représentent un atome d'hydrogène ou un groupe hydrocarboné, substitué ou non substitué, saturé ou insaturé, linéaire, ramifié, cyclique ou aromatique, de 1 à 28 atomes de carbone, comprenant éventuellement dans son squelette un ou plusieurs atomes choisis parmi les atomes d'oxygène, de soufre, d'azote, de phosphore et de silicium, et - Y, faisant la jonction entre O et P, représente un groupe hydrocarboné, substitué ou non substitué, saturé ou insaturé, linéaire, ramifié, cyclique ou aromatique, de 1à 28 atomes de carbone, comprenant éventuellement dans son squelette un ou plusieurs atomes choisis parmi les atomes d'oxygène, de soufre, d'azote, de phosphore et de silicium, ou
- dans laquelle R1 et R3 forment ensemble avec
un hétérocycle saturé ou insaturé comportant éventuellement d'autres hétéroatomes, et/ou - dans laquelle R2 et R4 forment ensemble avec
un hétérocycle saturé où insaturé comportant éventuellement d'autres hétéroatomes, et/ou - dans laquelle R5 et R6 forment ensemble avec
un hétérocycle saturé ou insaturé comportant éventuellement d'autres hétéroatomes, et/ou - dans laquelle R7 et R8 forment ensemble avec l'atome de phosphore auquel ces deux groupes sont respectivement liés un hétérocycle monocyclique ou bicyclique ayant de 1 à 8 atomes de carbone dans chaque cycle, les composés de formule générale (I) étant utilisables en particulier pour la complexation métallique.The present invention relates to a process for the preparation of bis (phosphane oxides) of general formula
in which - R1, R2, R3 and Rs, which may be identical or different, represent a hydrogen atom or a hydrocarbon group, substituted or unsubstituted, saturated or unsaturated, linear, branched, cyclic or aromatic, from 1 to 28 carbon atoms, optionally comprising in its backbone one or more atoms chosen from the atoms of oxygen, sulfur, nitrogen, phosphorus and silicon, or else SO3Ml / v with M symbolizing a metal and v being the valence of the metal M; - RS, R6, R7 and R6 which may be identical or different, represent a hydrogen atom or a hydrocarbon group, substituted or unsubstituted, saturated or unsaturated, linear, branched, cyclic or aromatic, from 1 to 28 carbon atoms , optionally comprising in its backbone one or more atoms chosen from the atoms of oxygen, sulfur, nitrogen, phosphorus and silicon, and - Y, making the junction between O and P, represents a hydrocarbon group, substituted or unsubstituted, saturated or unsaturated, linear, branched, cyclic or aromatic, from 1 to 28 carbon atoms, optionally comprising in its backbone one or more atoms chosen from the atoms of oxygen, sulfur, nitrogen, phosphorus and silicon, or
- in which R1 and R3 together with
a saturated or unsaturated heterocycle optionally comprising other heteroatoms, and / or - in which R2 and R4 form together with
a saturated or unsaturated heterocycle optionally comprising other heteroatoms, and / or - in which R5 and R6 form together with
a saturated or unsaturated heterocycle optionally comprising other heteroatoms, and / or - in which R7 and R8 form together with the phosphorus atom to which these two groups are respectively attached a monocyclic or bicyclic heterocycle having from 1 to 8 carbon atoms in each cycle, the compounds of general formula (I) being usable in particular for metal complexation.
Dans la formule donnée ci-dessus, lorsque R1, R2,
R3, R4, R5, R6, R7 et/ou R8 sont des groupes hydrocarbonés substitués, les substituants sont choisis avantageusement dans le groupe comprenant les atomes d'halogène et les groupes de formules: -C (O) R9 -C (O) OR10 -C(S)OR -C(O)NR12R13 -C (S)NR12R13 -NR12R13 -pyridile -bipyridyle -PR12R13 -C (OH) R9R10 -C(R9)=N-OH -C(R15)=pRR R14 -C-N -pyrolyle -S03R16 -P(O) (OR12) (OR13) dans lesquelles -R9, Rl0 R, R, R , R14 et R15 qui peuvent être identiques ou différents, représentent un atome d'hydrogène ou un groupe hydrocarboné; -R16 représente un atome d'hydrogène, un groupe hydrocarboné ou
M'l/v avec M' représentant un métal et v étant la valence du métal M'.In the formula given above, when R1, R2,
R3, R4, R5, R6, R7 and / or R8 are substituted hydrocarbon groups, the substituents are advantageously chosen from the group comprising halogen atoms and the groups of formulas: -C (O) R9 -C (O) OR10 -C (S) OR -C (O) NR12R13 -C (S) NR12R13 -NR12R13 -pyridil -bipyridyl -PR12R13 -C (OH) R9R10 -C (R9) = N-OH -C (R15) = pRR R14 -CN -pyrolyl -S03R16 -P (O) (OR12) (OR13) in which -R9, R10 R, R, R, R14 and R15 which may be the same or different, represent a hydrogen atom or a hydrocarbon group; -R16 represents a hydrogen atom, a hydrocarbon group or
M'l / v with M 'representing a metal and v being the valence of the metal M'.
Dans les formules données ci-dessus, les groupes hydrocarbonés ont généralement de 1 à 28 atomes de carbone et ils peuvent être linéaires et ramifiés; les métaux peuvent être n'importe quel métal, mais on préfère généralement les métaux alcalins, alcalino-terreux et les métaux de transition. In the formulas given above, the hydrocarbon groups generally have from 1 to 28 carbon atoms and they can be linear and branched; the metals can be any metal, but the alkali, alkaline earth and transition metals are generally preferred.
Dans le présent texte, le terme groupe 'hydrocarboné' signifie un groupe formé d'un squelette d'atomes de carbone qui peut être linéaire ou ramifié, substitué ou non substitué, saturé ou insaturé, cyclique ou aromatique, constitué de 1 à 28 atomes de carbone, comprenant éventuellement dans son squelette un ou plusieurs atomes choisis parmi les atomes d'oxygène, de soufre, d'azote, de phosphore ou de silicium, intercalés dans le squelette carboné ou greffés sur ce dernier. In the present text, the term 'hydrocarbon' group means a group formed by a skeleton of carbon atoms which may be linear or branched, substituted or unsubstituted, saturated or unsaturated, cyclic or aromatic, consisting of 1 to 28 atoms. of carbon, optionally comprising in its backbone one or more atoms chosen from the atoms of oxygen, sulfur, nitrogen, phosphorus or silicon, intercalated in the carbon skeleton or grafted onto the latter.
A titre d'exemple, ces groupes hydrocarbonés peuvent être des groupes alkyle ou alcoxy, des groupes cyclo-alkyles, des groupes benzyliques, des groupes aromatiques comme les groupes phényle, naphtyle; anisyle, pyridyle, bi-pyridyle, ... By way of example, these hydrocarbon groups can be alkyl or alkoxy groups, cyclo-alkyl groups, benzyl groups, aromatic groups such as phenyl or naphthyl groups; anisyl, pyridyl, bi-pyridyl, ...
On peut aussi utiliser des groupes insaturés comportant une ou plusieurs insaturations éthyléniques et/ou acétyléniques. It is also possible to use unsaturated groups comprising one or more ethylenic and / or acetylenic unsaturations.
Dans ces chaînes hydrocarbonées, les groupes alkyle ou alcoxy jouant le rôle de substituant ont de préférence de 1 à 28 atomes de carbone, et ils peuvent être linéaires ou ramifiés. In these hydrocarbon chains, the alkyl or alkoxy groups acting as a substituent preferably have from 1 to 28 carbon atoms, and they can be linear or branched.
Selon l'invention, le procédé de préparation d'un composé de type (I), se caractérise en ce qu'il comprend la réaction d'un di-anion avec deux équivalents d'un oxyde de phosphane fonctionnel. Le di-anion est obtenu par abstraction des deux protons des groupes hydroxyles portés par les atomes de carbone numéro 26 et 28 d'un diol de formule générale
dans laquelle R1, R2, R3, R4, R5 et R6 ont les significations données ci-dessus.According to the invention, the process for preparing a compound of type (I) is characterized in that it comprises the reaction of a di-anion with two equivalents of a functional phosphane oxide. The di-anion is obtained by abstraction of the two protons of the hydroxyl groups carried by the carbon atoms number 26 and 28 of a diol of general formula
wherein R1, R2, R3, R4, R5 and R6 have the meanings given above.
Les numéros 26 et "28' correspondent à l'indexation définie pour les composés communément appelés calixE4]arènes, par C. D.The numbers 26 and "28 'correspond to the indexing defined for the compounds commonly called calixE4] arenes, by C. D.
Gutsche dans Topics in Current Chemistry 123, Springer Verlag,
Berlin, page 3.Gutsche in Topics in Current Chemistry 123, Springer Verlag,
Berlin, page 3.
L'oxyde de phosphane fonctionnel a la formule générale dans laquelle
-R7 et RS ont les significations données ci-dessus; -X, représente un atome ou groupe partant, et -Y, lié à X et P, représente un groupe hydrocarboné, substitué ou non substitué, saturé ou insaturé, linéaire, ramifié, cyclique ou aromatique, de 1 à 28 atomes de carbone, comprenant éventuellement dans son squelette un ou plusieurs atomes choisis parmi les atomes d'oxygène, de soufre, d'azote, de phosphore et de silicium. Functional phosphane oxide has the general formula where
-R7 and RS have the meanings given above; -X, represents an atom or leaving group, and -Y, bonded to X and P, represents a hydrocarbon group, substituted or unsubstituted, saturated or unsaturated, linear, branched, cyclic or aromatic, from 1 to 28 carbon atoms, optionally comprising in its backbone one or more atoms chosen from oxygen, sulfur, nitrogen, phosphorus and silicon.
Par atome ou groupe partant, on entend la partie d'une molécule substrat qui, après clivage, est remplacée par le réactif d'attaque. Cette notion, bien connue des chimistes organiciens, est définie par exemple par J. March dans Advanced Organic Chemistzy, 3rd Ed., John Wiley, New York, 1985, pages 179 et 315. Des exemples de groupes partants sont C1, Br, I, ptoluènesulfonate, p-bromobenzènesulfonate, p nitrobenzènesulfonate, méthanesulfonate, trifluorométhanesulfonate, alkylesulfonate, arylesulfonate
Avec le procédé décrit ci-dessus, on obtient le composé de type (I) en échangeant chacun des atomes d'hydrogène des groupes hydroxyles portés par les atomes de carbone numéro 26 et 28 du diol (II) par le groupe YP(O)R7Re. By atom or leaving group is meant the part of a substrate molecule which, after cleavage, is replaced by the attack reagent. This notion, well known to organic chemists, is defined for example by J. March in Advanced Organic Chemistzy, 3rd Ed., John Wiley, New York, 1985, pages 179 and 315. Examples of leaving groups are C1, Br, I , ptoluenesulfonate, p-bromobenzenesulfonate, p nitrobenzenesulfonate, methanesulfonate, trifluoromethanesulfonate, alkylsulfonate, arylesulfonate
With the process described above, the compound of type (I) is obtained by exchanging each of the hydrogen atoms of the hydroxyl groups carried by the carbon atoms number 26 and 28 of the diol (II) with the group YP (O) R7Re.
Cette réaction de diphosphorylation d'un diol dé rivé du pentacyclo [19 .3 .1. l3,7.l9,13.115,19]octaosa- 1(25) ,3,5,'7(28),9,l1,13(27),15,17,l9(26),21,23-dodécaène-26,28- diol n'a pas été décrite dans la littérature. This diphosphorylation reaction of a diol derived from pentacyclo [19 .3 .1. 13,7,19,13,115,19] octaosa- 1 (25), 3,5, '7 (28), 9, 11,13 (27), 15,17, 19 (26), 21,23-dodecaene -26,28- diol has not been described in the literature.
Les anions utilisés comme produit de départ dans le procédé de l'invention, répondent par exemple à la formule suivante
dans laquelle R, R2, R3, R4, R5 et R6 ont les significations données ci-dessus.The anions used as starting material in the process of the invention correspond, for example, to the following formula
in which R, R2, R3, R4, R5 and R6 have the meanings given above.
La réaction de l'anion de formule (IV) avec l'oxyde de phosphane de formule (III), correspond au schéma suivant
qui conduit aux dérivés de formule (I) dans laquelle R-', R2, R3,
R4, R5, R6, R7, R5 et Y ont les significations données ci-dessus.The reaction of the anion of formula (IV) with the phosphane oxide of formula (III) corresponds to the following scheme
which leads to the derivatives of formula (I) in which R- ', R2, R3,
R4, R5, R6, R7, R5 and Y have the meanings given above.
Avantageusement les groupes X utilisés dans ce mode de mise en oeuvre du procédé de l'invention sont des tosylates, c'est-à-dire que X dans la formule (III) est un groupe OSO2(p C6H4CH3)
De même lorsque dans l'anion de formule (IV) décrit ci-dessus R1 et R3 forment avec
un hétérocycle saturé ou insaturé comportant éventuellement d'autres hétéroatomes, ces hétéroatomes peuvent être des atomes d'azote, d'oxygène, de soufre, de phosphore ou de silicium.Advantageously, the X groups used in this embodiment of the process of the invention are tosylates, that is to say that X in formula (III) is an OSO2 group (p C6H4CH3)
Likewise when in the anion of formula (IV) described above R1 and R3 form with
a saturated or unsaturated heterocycle optionally comprising other heteroatoms, these heteroatoms can be nitrogen, oxygen, sulfur, phosphorus or silicon atoms.
Lorsque dans l'anion de formule (IV) décrit cidessus R2 et R4 forment avec
un hétérocycle saturé ou insaturé comportant éventuellement d'autres hétéroatomes, ces hétéroatomes peuvent être des atomes d'azote, d'oxygène, de soufre, de phosphore ou de silicium.When in the anion of formula (IV) described above R2 and R4 form with
a saturated or unsaturated heterocycle optionally comprising other heteroatoms, these heteroatoms can be nitrogen, oxygen, sulfur, phosphorus or silicon atoms.
Lorsque dans l'anion de formule (IV) décrit cidessus R' et R6 forment avec
un hétérocycle saturé ou insaturé comportant éventuellement d'autres hétéroatomes, ces hétéroatomes peuvent être des atomes d'azote, d'oxygène, de soufre, de phosphore ou de silicium.When in the anion of formula (IV) described above R 'and R6 form with
a saturated or unsaturated heterocycle optionally comprising other heteroatoms, these heteroatoms can be nitrogen, oxygen, sulfur, phosphorus or silicon atoms.
La stoechiométrie utilisée pour réaliser la réaction conduisant au composé de formule (I) est généralement de 2 équivalents du composé X-Y-P(o)R7R6 pour un équivalent de dianion de départ. Mais on peut également utiliser une stoechiométrie supérieure à cette valeur. The stoichiometry used to carry out the reaction leading to the compound of formula (I) is generally 2 equivalents of the compound X-Y-P (o) R7R6 for one equivalent of the starting dianion. However, it is also possible to use a stoichiometry greater than this value.
On peut aussi avantageusement remplacer dans l'équation conduisant au composé de formule (I), les deux équivalents du composé X-Y-P(o)R7R3 par un seul équivalent d'un composé comportant deux groupes X-Y-P(O)R8-, liés entre eux par un groupe hydrocarboné E, ce qui revient à utiliser un composé de formule générale
dans laquelle -X, Y et R5 ont les significations données ci-dessus, et -E est groupe hydrocarboné, substitué ou non substitué, saturé ou insaturé, linéaire, ramifié, cyclique ou aromatique, de 1 à 28 atomes de carbone, comprenant éventuellement dans son squelette un ou plusieurs atomes choisis parmi les atomes d'oxygène, de soufre, d'azote, de phosphore et de silicium.It is also possible to advantageously replace in the equation leading to the compound of formula (I), the two equivalents of the compound XYP (o) R7R3 by a single equivalent of a compound comprising two groups XYP (O) R8-, linked together by a hydrocarbon-based group E, which amounts to using a compound of general formula
in which -X, Y and R5 have the meanings given above, and -E is a hydrocarbon group, substituted or unsubstituted, saturated or unsaturated, linear, branched, cyclic or aromatic, from 1 to 28 carbon atoms, optionally comprising in its backbone one or more atoms chosen from oxygen, sulfur, nitrogen, phosphorus and silicon.
On obtient alors, après réaction, un composé de formule générale
dans laquelle R1, R2, R3. R4, R5, R6, R8, Y et E ont les significations données ci-dessus.One then obtains, after reaction, a compound of general formula
where R1, R2, R3. R4, R5, R6, R8, Y and E have the meanings given above.
Cette formule n'est, bien entendu, qu'un cas particulier des composés de formule générale (I), dans lequel les deux groupes
R7 liés aux atomes de phosphore sont remplacés par un groupe unique, E, assura. la jonction entre les deux atomes de phosphore.This formula is, of course, only a particular case of the compounds of general formula (I), in which the two groups
R7 attached to phosphorus atoms are replaced by a single group, E, assura. the junction between the two phosphorus atoms.
Pour mettre en oeuvre le procédé de l'invention, on prépare l'anion de formule générale IV, par réaction d'un diol de formule générale II, avec une base pour arracher les atomes d'hydrogène des fonctions OH portées par les atomes de carbone 26 et 28 et former le di-anion. To carry out the process of the invention, the anion of general formula IV is prepared by reacting a diol of general formula II with a base to remove the hydrogen atoms from the OH functions carried by the atoms of carbon 26 and 28 and form the di-anion.
Les bases utilisées sont choisies en fonction du diol de départ. Pour cette réaction, on peut opérer à la température ambiante, à des températures inférieures, allant par exemple jusqu'à -78 OC, ou à des températures supérieures, par exemple au reflux, selon la nature de la base utilisée. The bases used are chosen according to the starting diol. For this reaction, it is possible to operate at room temperature, at lower temperatures, ranging for example down to -78 ° C., or at higher temperatures, for example at reflux, depending on the nature of the base used.
Généralement on réalise cette réaction dans un solvant organique inerte tel que le tétrahydrofuranne ou l'éther éthylique.Generally, this reaction is carried out in an inert organic solvent such as tetrahydrofuran or ethyl ether.
A titre d'exemple de bases susceptibles d'être utilisées, on peut citer les amidures tels que les amidures de lithium, de sodium ou de potassium; les organolithiens tels que n-BuLi, t-BuLi, ou PhLi; les composés organoalcalins formés par réaction de butyllithium avec un silazane; les alcoolates, par exemple t-BuONa, t-BuOK, MeONa; les phénolates alcalins; les hydrures de métaux alcalins, tels que l'hydrure de sodium et l'hydrure de potassium; les amines organiques, par exemple le 1,8-diazabicyclo[5.4.0]undec-7-ène ou le 1,8bis(diméthylamino)naphta-lène et les bases minérales telles que par exemple LiOH, NaOH, Na2CO3, K2CO3, Li2CO3, Ca(OH)2, Cs2CO3, et les hydroxydes ou les carbonates de métaux de transition comme Ag2CO3 ou CuCO3.Cu(OH)2. By way of example of bases which can be used, mention may be made of amides such as lithium, sodium or potassium amides; organoliths such as n-BuLi, t-BuLi, or PhLi; organoalkali compounds formed by reaction of butyllithium with a silazane; alcoholates, for example t-BuONa, t-BuOK, MeONa; alkaline phenolates; alkali metal hydrides, such as sodium hydride and potassium hydride; organic amines, for example 1,8-diazabicyclo [5.4.0] undec-7-ene or 1,8bis (dimethylamino) naphthalene and mineral bases such as for example LiOH, NaOH, Na2CO3, K2CO3, Li2CO3 , Ca (OH) 2, Cs2CO3, and hydroxides or carbonates of transition metals such as Ag2CO3 or CuCO3.Cu (OH) 2.
Pour cette réaction, le ccntre-cation de la base utilisée peut être un cation de métal alcalin, de métal alcalinoterreux ou de métal de transition. For this reaction, the ccntre-cation of the base used can be an alkali metal, alkaline earth metal or transition metal cation.
Pour la réaction de préparation de l'anion, on utilise au moins deux équivalents de base par équivalent de diol de formule (il), mais on peut utiliser une stoechiométrie supérieure à 2. For the reaction for preparing the anion, at least two equivalents of base are used per equivalent of diol of formula (II), but a stoichiometry greater than 2 can be used.
A titre d'exemple, le diol de départ répond à la formule suivante
dans laquelle R5 et R6 sont des groupes hydrocarbonés tels que ceux définis ci-dessus.By way of example, the starting diol corresponds to the following formula
wherein R5 and R6 are hydrocarbon groups such as those defined above.
Ces diois sont des produits du commerce ou peuvent être préparés par des procédés classiques à partir de calix[4]arènes simples. These diois are commercial products or can be prepared by conventional methods from simple calix [4] arenes.
Les oxydes de phosphine (III) utilisés également comme produit de départ dans le procédé de l'invention, sont des produits qui peuvent être préparés par des procédés classiques tels que ceux décrits par W. Wegener, Z. Chem., 11(1971)262. The phosphine (III) oxides, also used as starting material in the process of the invention, are products which can be prepared by conventional processes such as those described by W. Wegener, Z. Chem., 11 (1971) 262.
Selon une variante de l'invention, le procédé décrit ci-dessus peut être mis en oeuvre pour obtenir un bis(phosphane) après l'étape de réaction de l'anion avec l'oxyde de phosphane fonctionnel, en réalisant une étape de double réduction. Cette étape correspond au schéma réactionnel suivant
On obtient ainsi un produit de formule (V), dans laquelle
R1, R2, R3 R4 R5, R6, R7, R8, R9 et Y ont les significations données ci-dessus.There is thus obtained a product of formula (V), in which
R1, R2, R3 R4 R5, R6, R7, R8, R9 and Y have the meanings given above.
Cette réaction de réduction peut être effectuée au moyens d'agents réducteurs appropriés, en opérant généralement dans un solvant organique inerte et sous atmosphère contrôlée. This reduction reaction can be carried out by means of suitable reducing agents, generally operating in an inert organic solvent and under a controlled atmosphere.
Les agents réducteurs appropriés sont par exemple le phényle silane, le trichlorosilane, ou le tributylephosphane. Suitable reducing agents are, for example, phenyl silane, trichlorosilane, or tributylephosphane.
A titre de solvants organiques susceptibles d'être utilisé, on peut citer le toluène, le benzène. As organic solvents which may be used, mention may be made of toluene and benzene.
Les produits obtenus par le procédé de l'invention peuvent être sous 'une quelconque des formes dites "cone", 'cone partiel", 1,3-alternée', "1,2-alternée". Ces conformations ont été définies, par exemple dans M. Iqbal, T. The products obtained by the process of the invention can be in any of the so-called “cone”, “partial cone”, 1,3-alternate ”,“ 1,2-alternate ”forms. These conformations have been defined by example in M. Iqbal, T.
Mangiafico, C. D. Gutsche, Tetrahedron, 1987, vol.43, No 21, pp
4917-4930.Mangiafico, CD Gutsche, Tetrahedron, 1987, vol. 43, No 21, pp
4917-4930.
L'invention a également pour objet les nouveaux dérivés phosphinés obtenus par ce procédé. A subject of the invention is also the novel phosphine derivatives obtained by this process.
Ces dérivés répondent à la formule
dans laquelle
-R1, R2 R3 R4, R5, R6, R7, R8 et Y ont les significations
données ci-dessus.in which
-R1, R2 R3 R4, R5, R6, R7, R8 and Y have the meanings
data above.
A titre d'exemple de tels dérivés, on peut citer ceux répondant aux formules
dans lesquelles
Rl, R2, R3, R4, R7, Ra et R9 ont les significations données ci-dessus.
in which
R1, R2, R3, R4, R7, Ra and R9 have the meanings given above.
Les dérivés de formule (I) décrits ci-dessus peuvent être utilisés comme extractants pour l'extraction des actinides et des lanthanides, par exemple dans des procédés d'extraction tels que ceux décrits dans US-A-4 548 790 et 4 922 012. Cette propriété est liée à la présence de groupes phosphoryles, bien connus pour complexer de tels éléments (voir par exemple R. Babecki, A. W. G. Platt, J. Fawcett, J. Chem. The derivatives of formula (I) described above can be used as extractants for the extraction of actinides and lanthanides, for example in extraction processes such as those described in US-A-4,548,790 and 4,922,012 This property is linked to the presence of phosphoryl groups, well known to complex such elements (see for example R. Babecki, AWG Platt, J. Fawcett, J. Chem.
Soc. Dalton Trans. 1992) pp 675-681).Soc. Dalton Trans. 1992) pp 675-681).
L'aptitude des groupes phosphoryles à complexer des lanthanides rend aussi les ligands de formule générale (I) à la préparation de complexes métalliques luminescents. The ability of the phosphoryl groups to complex lanthanides also makes the ligands of general formula (I) suitable for the preparation of luminescent metal complexes.
Les dérivés de formule (V) décrits ci-dessus peuvent être utilisés comme complexants pour les métaux de transition. Cette propriété est liée à l'aptitude des atomes de phosphore trivalents à se coordiner à un tel métal (voir, par exemple, W. Lewason dans The Chemiscry of Organophosphorus Compounds, ed. F. r. Hartley, Wiley, Chichester, 1990, vol.l, pp.567-641). Ainsi, il est connu que des complexes diphosphanes de métaux de transition peuvent, par exemple, servir de catalyseurs d'hydrogénation d'alcènes et/ou d'hydroformylation d'alcènes (G. W. Parshall, S. D. Tttel, dans Homogeneous
Catalysis, seconde édition, 1992, John Wiley, New York).The derivatives of formula (V) described above can be used as complexing agents for transition metals. This property is related to the ability of trivalent phosphorus atoms to coordinate with such a metal (see, for example, W. Lewason in The Chemiscry of Organophosphorus Compounds, ed. F. r. Hartley, Wiley, Chichester, 1990, vol.l, pp. 567-641). Thus, it is known that transition metal diphosphane complexes can, for example, serve as catalysts for hydrogenation of alkenes and / or hydroformylation of alkenes (GW Parshall, SD Tttel, in Homogeneous
Catalysis, second edition, 1992, John Wiley, New York).
L'invention a également pour objet des complexes de métaux de transition utilisant un ligand de formule (V) décrit ci-dessus qui répondent à la formule suivante
dans laquelle -R1, R2, R3, R4, R5, R6, R7, R8 et Y ont les significations données ci-dessus; -M" est un métal du groupe Ni, Pd, Pt, et -A et A', identiques ou différents, représentent un atome ou groupe mono-anionique.A subject of the invention is also transition metal complexes using a ligand of formula (V) described above which correspond to the following formula
wherein -R1, R2, R3, R4, R5, R6, R7, R8 and Y have the meanings given above; -M "is a metal from the group Ni, Pd, Pt, and -A and A ', which are identical or different, represent a mono-anionic atom or group.
A titre d'exemple d'atome ou groupe monoanionique, on peut citer C1, Br, I, CN, SCN, Calo4, BF4, CF3S03, BPh4, PF6. As an example of a monoanionic atom or group, mention may be made of C1, Br, I, CN, SCN, Calo4, BF4, CF3S03, BPh4, PF6.
De tels complexes peuvent trouver des applications en catalyse homogène. Such complexes can find applications in homogeneous catalysis.
L'invention a également pour objet des complexes de métaux de transition utilisant un ligand de formule (V) décrit ci-dessus qui répondent à la formule suivante
dans laquelle -R1, R2, R3, R4, R, R6, R7, R8, Y et A ont les significations données ci-dessus; -M''' est un métal du groupe Co, Rh, Ir -L et L', identiques ou différents, formant éventuellement ensemble une seule entité chimique, sont des entités donneur de deux électrons pouvant se coordiner au métal M'''.A subject of the invention is also transition metal complexes using a ligand of formula (V) described above which correspond to the following formula
wherein -R1, R2, R3, R4, R, R6, R7, R8, Y and A have the meanings given above; -M '''is a metal of the Co group, Rh, Ir -L and L', identical or different, possibly forming together a single chemical entity, are donor entities of two electrons which can coordinate with the metal M '''.
A titre d'exemple de coordinat donneur de deux électrons, L ou L', on peut citer l'éthène, le méthanol, l'acétone, le monoxyde de carbone. A titre d'exemple d'entité chimique où L est lié à L' en formant ainsi une seule entité chimique, on peut citer les diènes tel que, par exemple, le 1,5cyclooctadiène, le norbornadiène, 12 cycîooctatétraène. By way of example of ligand donor of two electrons, L or L ', mention may be made of ethene, methanol, acetone and carbon monoxide. As an example of a chemical entity where L is linked to L ', thus forming a single chemical entity, there may be mentioned dienes such as, for example, 1,5cyclooctadiene, norbornadiene, 12 cyciooctatetraene.
De tels complexes peuvent trouver des applications en catalyse homogène, telles que par exemple l'hydrogénation d'alcènes et en particulier, lorsque le coordinat de formule (I) est chiral, l'hydrogénation asymétrique d'alcènes. Such complexes can find applications in homogeneous catalysis, such as for example the hydrogenation of alkenes and in particular, when the ligand of formula (I) is chiral, the asymmetric hydrogenation of alkenes.
D'autres caractéristiques et avantages de l'invention apparaîtront mieux à la lecture des exemples suivants donnés bien entendu à titre illustratif. Dans la partie qui suit, la molécule de formule
sera désignée, pour raison de commodité, par p-tertbutylcalix[4]arène.Other characteristics and advantages of the invention will emerge more clearly on reading the following examples, which are of course given by way of illustration. In the following part, the molecule of formula
will be referred to, for convenience, as p-tertbutylcalix [4] arene.
Exemple 1. Synthèse du 5,11,17,23-tetra-tert-butyl- a5, 27-bis(dléthylcarbamoylmdthoxy)-26,28-dihydroxyca- lix[4]arène. Example 1. Synthesis of 5,11,17,23-tetra-tert-butyl-α5,27-bis (dlethylcarbamoylmdthoxy) -26,28-dihydroxycalix [4] arene.
On fait réagir, à température ambiante, une suspension de p-te~c-butylcalix[4]arène (15,000 g, 23,11 mmol) dans l'acétone (60C ml) avec K2CO3 (3,514 g, 25,43 mmol) pendant 12 heures. Après addition de 2-bromo-N,N-diéthylacétamide (9,400 g, 48,44 mmol), on porte le mélange à reflux pendant 15 h. La solution est refroidie, filtrée, et le filtrat évaporé à sec. Le résidu est ensuite dissous dans CH2C12 (300 ml) et la solution ainsi obtenue est traitée d'abord avec 200 ml d'une solution aqueuse saturée de NH4C1, puis avec 200 ml d'eau. La phase organique est séchee sur MgSO4, puis filtrée. Après évaporation à sec du filtrat, e résidu est recristallisé dans un mélange CH2Cl2-EtOH, ce qu conduit au produit, sous forme de solide blanc (R = 0,69, ~H2Cl2/MeOH 94:6, v/v). Rendement: 15,004 g, 74%. P.F.: 235 OC, décomp. . Analyse centésimale expérimentale:
C, 76,89; H, 9,19; N, 3,21. Analyse centésimale théorique pour C56H78N206 (Mr=875,26): C, 76,85; H, 8,98; N, 3,20. MS (CI), m/z
(%) : 874 (79) [M+]. IR(KBr): v = 1651F (C=O) cm-l. 1H RMN
(CDCl3): 6 1,06 (s, 18H, But), 1,16 (s, 18H, But), 1,17 (t, 6H, N(CH2CH3)2, 3J = 7,1 Hz), 1,27 (t, 6H, N(CH2CH3)2, 3J = 7,1 Hz), 3,27 et 4,48 (syst. AB, 8H, ArCH2Ar, J(AB) = 13,1 Hz), 3,47 (q, 8H, M(CH2CH3)2, 3J = 7,1 Hz), 4,83 (s, 4H, OCH2CONEt2), 6,88 (s, 8H, m-ArH), 7,82 (s, 2H, ArOH). 13C(1H) RMN (CDCl3) : S 12,97 et 14,28 (2s, N(CH2CH3)n), 31,19 et 31,54 (2s, C(CH3)3), 31,93 (s,
ArCH2Ar), 33,65 et 33,91 (2s, C(CH3)3), 40,11 et 41,11 (2s,
N(CH2CH3)2), 73,50 (s, OCH2CONEt2), 124,77 et 125,55 (2s, CH arom.), 127,68, 133,37, 140,96, 146,62, 150,03 et 152,20 (6s, Cquat arom.), 167,88 (s, C=O). A suspension of p-te ~ c-butylcalix [4] arene (15,000 g, 23.11 mmol) in acetone (60C ml) is reacted at room temperature with K2CO3 (3.514 g, 25.43 mmol) for 12 hours. After addition of 2-bromo-N, N-diethylacetamide (9.400 g, 48.44 mmol), the mixture is refluxed for 15 h. The solution is cooled, filtered, and the filtrate evaporated to dryness. The residue is then dissolved in CH2Cl2 (300 ml) and the solution thus obtained is treated first with 200 ml of a saturated aqueous solution of NH4Cl, then with 200 ml of water. The organic phase is dried over MgSO4, then filtered. After evaporating the filtrate to dryness, the residue is recrystallized from a CH2Cl2-EtOH mixture, which results in the product, in the form of a white solid (Y = 0.69, ~ H2Cl2 / MeOH 94: 6, v / v). Yield: 15.004 g, 74%. PF: 235 OC, decomp. . Experimental centesimal analysis:
C, 76.89; H, 9.19; N, 3.21. Theoretical percent analysis for C56H78N2O6 (Mr = 875.26): C, 76.85; H, 8.98; N, 3.20. MS (CI), m / z
(%): 874 (79) [M +]. IR (KBr): v = 1651F (C = O) cm-1. 1H NMR
(CDCl3): 6 1.06 (s, 18H, But), 1.16 (s, 18H, But), 1.17 (t, 6H, N (CH2CH3) 2, 3J = 7.1Hz), 1 , 27 (t, 6H, N (CH2CH3) 2, 3J = 7.1 Hz), 3.27 and 4.48 (syst. AB, 8H, ArCH2Ar, J (AB) = 13.1 Hz), 3, 47 (q, 8H, M (CH2CH3) 2, 3J = 7.1Hz), 4.83 (s, 4H, OCH2CONEt2), 6.88 (s, 8H, m-ArH), 7.82 (s, 2H, ArOH). 13C (1H) NMR (CDCl3): S 12.97 and 14.28 (2s, N (CH2CH3) n), 31.19 and 31.54 (2s, C (CH3) 3), 31.93 (s,
ArCH2Ar), 33.65 and 33.91 (2s, C (CH3) 3), 40.11 and 41.11 (2s,
N (CH2CH3) 2), 73.50 (s, OCH2CONEt2), 124.77 and 125.55 (2s, CH arom.), 127.68, 133.37, 140.96, 146.62, 150.03 and 152.20 (6s, Cquat arom.), 167.88 (s, C = O).
Exemple 2. Synthèse du 5,11,17,23-tetra-tert-butyl 25,27-bis(diNthylcarbamoylmfithoxy)-26,28-bls(diphinyl- phosphinoylméthoxy)calix[4]arène (cône).Example 2. Synthesis of 5,11,17,23-tetra-tert-butyl 25,27-bis (diNthylcarbamoylmfithoxy) -26,28-bls (diphinyl-phosphinoylmethoxy) calix [4] arene (cone).
On porte à reflux pendant une heure un mélange de 5,11,17,23-tetra-tert-butyl-25,27-bis(diéthylcarbamoylméthoxy)- 26,28-dihydroxycalix[4]arène (5,00 g, 5,71 mmol), préparé selon l'exemple 1, et de BuOMa (1,237 g, 12,87 mmol), dans un mélange de tétrahydrofuranne (THF)-diméthylformamide (DMF) (9:1, v/v)
(170 ml). Puis on ajoute Ph2P(O)CH2OTs (4,856 g, 12,56 mmol) (Ts = p-SO2C6H4-CH3) et porte la solution à reflux pendant 20 h.A mixture of 5,11,17,23-tetra-tert-butyl-25,27-bis (diethylcarbamoylmethoxy) - 26,28-dihydroxycalix [4] arene (5.00 g, 5, 71 mmol), prepared according to Example 1, and BuOMa (1.237 g, 12.87 mmol), in a mixture of tetrahydrofuran (THF) -dimethylformamide (DMF) (9: 1, v / v)
(170 ml). Then Ph2P (O) CH2OTs (4.856 g, 12.56 mmol) (Ts = p-SO2C6H4-CH3) are added and the solution is refluxed for 20 h.
Après filtration, les solvants sont évaporés sous vide. Le résidu est dissous dans CH2Cl2 (150 ml) et la solution ainsi obtenue est traitée avec une solution aqueuse saturée de NH4Cl
(150 ml), puis avec de l'eau (100 ml). La phase organique est s é c h é e s u r MgSO4, puis concentrée à env. 20 ml. Après avoir refroidi la solution à env. 5 Ot, on ajoute, sous agitation, de l'acétone, ce qui provoque la précipitation du produit sous forme de microcristaux blancs (Rf = 0,26, CH2Cl2/MeOH 74:26, v/v).After filtration, the solvents are evaporated off under vacuum. The residue is dissolved in CH2Cl2 (150 ml) and the solution thus obtained is treated with a saturated aqueous solution of NH4Cl
(150 ml), then with water (100 ml). The organic phase is dried over MgSO4, then concentrated to approx. 20 ml. After cooling the solution to approx. Ot, acetone is added with stirring causing the product to precipitate as white microcrystals (Rf = 0.26, CH2Cl2 / MeOH 74:26, v / v).
Rendement : 5,509 g, 74%. P.F. > 277 OC. Analyse centésimale expérimentale: C, 75,73; H, 7,81; N, 2,05. Analyse centésimale théorique pour C82H100N2O8P2 (Mr = 1303,66): C, 75,55; H, 7,73;
N, 2,15. MS (CI), m/z (%): 1302 (10) [M+]. IR(KBr):V = 1658F (C=O) cm-1. 1H RMN (CDCl3) : 6 0,30 (s, 18H, But), 0,41 (t, 6H, N(CH2CH3)2, 3J = 7,9 Hz), 0,72 (t, 6H, N(CH2CH3)2, 3J = 8,2 Hz), 0,75 (s, 18H, But), 2,64 èt 4,81 (syst. AB, 8H, ArCH2Ar, J(AB) = 14,7 Hz), 3,05 (q, 4H, N(CH2CH3)2, 3J = 8,2 Hz), 3,21 (q, 4H, N(CH2CH3)2, 3J = 7,9 Hz), 4,64 (s, 4H, OCH2CONEt2), 6,13 (s, 4H,
OCH2P(O)Ph2), 6,64 (s, 4H, m-ArH), 6,91 (s, 4H, m-ArH), 7,587,80 et 8,22-8,33 (m, 20H, P(O)Ph2). 13C(1H) RMN (CDCl3): # 12,90 et 14,65 (2s, N(CH CH3)2), 31,00 et 31,55 (2s, C(CH3)3), 32,27 (s, ArCH2Ar), 33,43 et 33,83 (2s, C(CH3)3), 40,21 et 41,65 (s, N(cH2CH3)2), 69,14 d, OCH2P(O)Ph2, J(PC) = 69,3 Hz), 72,10 (s,
OCH2CONEt2), 124,48, 124.63, 127.74, 127,97, 130,47, 130,89 et 131,07 (CH arom.), 32,30-153,03 (Cquat arom.), 167,94 (s, C=O). Yield: 5.509 g, 74%. PF> 277 OC. Experimental percentage analysis: C, 75.73; H, 7.81; N, 2.05. Theoretical Percent Analysis for C82H100N2O8P2 (Mr = 1303.66): C, 75.55; H, 7.73;
N, 2.15. MS (CI), m / z (%): 1302 (10) [M +]. IR (KBr): V = 1658F (C = O) cm-1. 1H NMR (CDCl3): 6 0.30 (s, 18H, But), 0.41 (t, 6H, N (CH2CH3) 2, 3J = 7.9Hz), 0.72 (t, 6H, N ( CH2CH3) 2, 3J = 8.2 Hz), 0.75 (s, 18H, But), 2.64 and 4.81 (syst. AB, 8H, ArCH2Ar, J (AB) = 14.7 Hz), 3.05 (q, 4H, N (CH2CH3) 2, 3J = 8.2Hz), 3.21 (q, 4H, N (CH2CH3) 2, 3J = 7.9Hz), 4.64 (s, 4H, OCH2CONEt2), 6.13 (s, 4H,
OCH2P (O) Ph2), 6.64 (s, 4H, m-ArH), 6.91 (s, 4H, m-ArH), 7,587.80 and 8.22-8.33 (m, 20H, P (O) Ph2). 13C (1H) NMR (CDCl3): # 12.90 and 14.65 (2s, N (CH CH3) 2), 31.00 and 31.55 (2s, C (CH3) 3), 32.27 (s , ArCH2Ar), 33.43 and 33.83 (2s, C (CH3) 3), 40.21 and 41.65 (s, N (cH2CH3) 2), 69.14 d, OCH2P (O) Ph2, J (PC) = 69.3 Hz), 72.10 (s,
OCH2CONEt2), 124.48, 124.63, 127.74, 127.97, 130.47, 130.89 and 131.07 (CH arom.), 32.30-153.03 (Cquat arom.), 167.94 (s , C = O).
P(H) RMN (CH2Cl2/C6D6) : a + 23,7 (s, P(O)Ph2). P (H) NMR (CH2Cl2 / C6D6): a + 23.7 (s, P (O) Ph2).
Exemple 3. Synthèse du 5,11,17,23-tetra-tert-butyl25 , 2 7 - b i s (d i é t h y l c a r b a m o y l m é t h o x y) - 26 , 28 - bis(diphénylphosnhinométhoxy)calix[4]arène (cône).Example 3. Synthesis of 5,11,17,23-tetra-tert-butyl25,2 7 - b i s (d i é t h y l c a r b a m o y l m é t h o x y) - 26, 28 - bis (diphenylphosnhinomethoxy) calix [4] arene (cone).
Un mélange de 5,11,17,23-tetra-tert-butyl-25,27 bis(diéthylarbamoylméthoxy)-26,28- bis(diphénylphosphinoylméthoxy)calix[4]arène, préparé selon l'exemple 2 (3,000 g, 2,30 mmol), et de phénylsilane (5.000 g, èn. 5,7 ml, 46,20 mmol) est chauffé dans le toluène (40 ml) à reflux pendant une semaine. Après évaporation du solvant, le résidu est dissous dans CH2C12 (env. 10 ml) . L'addition d'éthanol (40 ml), sous agitation vigoureuse, à la solution préalablement refroidie à env. 5 C, provoque la précipitation du produit sous forme de poudre blanche (Rf = 0,49 CH2Cl2/MeOH 9:1, v/v). Rendement : 2,700 g, 92%. P.F. 275-278 OC. Analyse centésimale expérimentale: C, 77.40; H, 8.11; N, 2.15. Analyse centésimale théorique pour C82H100N2O6P2 (Mr = 1271,67): C, 77,45; H, 7,93; N, 2,20. MS (CI), m/z (%): 1333 (6) [M02 + 1270 (17) [M+]. IR(KBr) : v = 1652F (C=O) cm-1. 1H RMN (CDCl3) 6 0,83 (s, 18H, But), 0,99 (t, 6H, N(CH2CH3)2, 3J = 7,1 Hz), 1,04 (t, 6H, N(CH2CH3)2, 3J = 7,1 Hz), 1,23 (s, 18H, But), 2,91 et 4,43 (syst. AB, 8H, ArCH2Ar, J(AB) = 12,9 Hz), 3,22 (q, 4H, N(CH2CH3)2, 3J = 7,1 Hz), 3,29 (q, 4H, N(CH2CH3)2, 3J = 7,1 Hz), 4,46 (s, 4H, OCH2CoNEt2), 5,68 (d, 4H, OCH2PPh2, 2J(PH) = 2,5
Hz), 6,42 (s, 4H, m-ArH), 6,76 (s, 4H, m-ArH), 7,17-7,23 et 7,41-7,49 (m, 20H, PPh2). C{H} RMN (CDCl3) : a 13,07 et 14,43 (2s, N(CH2CH3)2), 31,08 et 31,58 (2s, C(CH3)3), 32,23 (d,
ArCH2Ar, 5J(PH) = 4,61 Hz), 33,51 et 33,90 (2s, C(CH3)3), 40,02 et 41,34 (2s, N(CH2CH3)2), 72,96 (s, OCH2CONEt2), 73,85 (d,
OCH2PPh2, J(PC) = 8,7 Hz), 124,67, 124,78, 127,82, 127,95, 127,99, 133,31 et 133,69 (CH arom.), 132,01-153,15 (Cquat arom.), 167,56 (s, C=O). P{H} RMN (CH,C12/C6D6) : a - 22,4 (s, PPh2)
Exemple 4. Synthèse du 5,11,17,23-tetra-tert-butyl25,27-diéthoxycarbonylméthoxy-26,29-bis-(diphénylphos- phinoylm8thoxy)calix[4]arène (cône).A mixture of 5,11,17,23-tetra-tert-butyl-25,27 bis (diethylarbamoylmethoxy) -26,28- bis (diphenylphosphinoylmethoxy) calix [4] arene, prepared according to Example 2 (3.000 g, 2 , 30 mmol), and phenylsilane (5,000 g, en. 5.7 ml, 46.20 mmol) is heated in toluene (40 ml) at reflux for one week. After evaporation of the solvent, the residue is dissolved in CH2C12 (approx. 10 ml). The addition of ethanol (40 ml), with vigorous stirring, to the solution previously cooled to approx. 5 C, precipitates the product as a white powder (Rf = 0.49 CH2Cl2 / MeOH 9: 1, v / v). Yield: 2.700 g, 92%. PF 275-278 OC. Experimental percentage analysis: C, 77.40; H, 8.11; N, 2.15. Theoretical percent analysis for C82H100N2O6P2 (Mr = 1271.67): C, 77.45; H, 7.93; N, 2.20. MS (CI), m / z (%): 1333 (6) [MO2 + 1270 (17) [M +]. IR (KBr): v = 1652F (C = O) cm-1. 1H NMR (CDCl3) 6 0.83 (s, 18H, But), 0.99 (t, 6H, N (CH2CH3) 2, 3J = 7.1Hz), 1.04 (t, 6H, N (CH2CH3 ) 2, 3J = 7.1 Hz), 1.23 (s, 18H, But), 2.91 and 4.43 (syst. AB, 8H, ArCH2Ar, J (AB) = 12.9 Hz), 3 , 22 (q, 4H, N (CH2CH3) 2, 3J = 7.1Hz), 3.29 (q, 4H, N (CH2CH3) 2, 3J = 7.1Hz), 4.46 (s, 4H , OCH2CoNEt2), 5.68 (d, 4H, OCH2PPh2, 2J (PH) = 2.5
Hz), 6.42 (s, 4H, m-ArH), 6.76 (s, 4H, m-ArH), 7.17-7.23 and 7.41-7.49 (m, 20H, PPh2 ). C {H} NMR (CDCl3): a 13.07 and 14.43 (2s, N (CH2CH3) 2), 31.08 and 31.58 (2s, C (CH3) 3), 32.23 (d,
ArCH2Ar, 5J (PH) = 4.61 Hz), 33.51 and 33.90 (2s, C (CH3) 3), 40.02 and 41.34 (2s, N (CH2CH3) 2), 72.96 (s, OCH2CONEt2), 73.85 (d,
OCH2PPh2, J (PC) = 8.7Hz), 124.67, 124.78, 127.82, 127.95, 127.99, 133.31 and 133.69 (CH arom.), 132.01- 153.15 (Cquat arom.), 167.56 (s, C = O). P {H} NMR (CH, C12 / C6D6): a - 22.4 (s, PPh2)
Example 4. Synthesis of 5,11,17,23-tetra-tert-butyl25,27-diethoxycarbonylmethoxy-26,29-bis- (diphenylphosphinoylm8thoxy) calix [4] arene (cone).
On chauffe, pendant une heure, une suspension de 5,11,17,23-tetra-tert-butyl-25,27-diéthoxycarbonylméthoxy-26,28- dihydroxycalix[4]arène (cône) (30,300 g, 36,90 mmol) et de
ButONa (8,735 g, 90,89 mmol), dans un mélange THF-DMF (9:1, v/v) (1000 ml) au reflux. Après addition de Ph2P(O)CH2OTs (31,370 g, 81,18 mmol), on maintient encore le mélange sous reflux pendant 60 heures. Après filtration, on évapore les solvants. Le résidu est dissous dans CH,C12 (500 ml) et la solution obtenue traitée avec de l'eau (2 x 300 ml). Lors de cette étape, le pH de la solution aqueuse est ajusté à pH 7, au moyen d'une solution de
HC1 1N. La phase organique est séchée sur MgSO4, filtrée, puis concentrée à env. 50 ml. L'addition, sous agitation, d'acétone à la solution préalablement refroidie (env. 50C) fait apparaître le produit sous forme de précipité blanc (Rf = 0,41 dans
CH2C12/MeOH, 94:6, :/v). Rendement : 36,005 g, 78%. P.F. : 234239 C. Analyse centésimale expérimentale: C, 75,00; H, 7,51.A suspension of 5,11,17,23-tetra-tert-butyl-25,27-diethoxycarbonylmethoxy-26,28-dihydroxycalix [4] arene (cone) (30,300 g, 36.90 mmol) is heated for one hour. ) and of
ButONa (8.735 g, 90.89 mmol), in THF-DMF (9: 1, v / v) (1000 ml) at reflux. After addition of Ph2P (O) CH2OTs (31.370 g, 81.18 mmol), the mixture is still maintained under reflux for 60 hours. After filtration, the solvents are evaporated off. The residue is dissolved in CH, C12 (500 ml) and the resulting solution treated with water (2 x 300 ml). During this step, the pH of the aqueous solution is adjusted to pH 7, using a solution of
HC1 1N. The organic phase is dried over MgSO4, filtered, then concentrated to approx. 50 ml. The addition, with stirring, of acetone to the previously cooled solution (approx. 50 ° C.) reveals the product in the form of a white precipitate (Rf = 0.41 in
CH2Cl2 / MeOH, 94: 6,: / v). Yield: 36.005 g, 78%. MP: 234239 C. Experimental percentage analysis: C, 75.00; H, 7.51.
Analyse centésimale théorique pour C78H90o10P2 (Mr = 1249,53): C, 74,98; H, 7,26. MS (CI), m/z(%) : 1277 (18) [M + NH3 + H+], 1249
(69) [M + H+]. IR (KBr): V = 1753F (C=O) cm-1. 1H RMN (CDCl3): 5 7,84-7,74 et 7,51-7,34 (m, 20H, P(O)Ph2), 6,77 (s, 4H, m-ArH), 6,42 (s, 4H, m-ArH), 5,20 (s, 4H, OCH2P(O)Ph2), 4,63 (s, 4H, OCH2COXEt), 4,69 et 2,96 (syst. AB, 8H, ArCH2Ar, J(AB) = 13,1
Hz), 4,11 (q, 4H, CH2CH3, 3J = 7,1 Hz), 1,23 (t, 6H, CH2CH3, 3J = 7,1 Hz), 1,11 (s, 18H, But), 0,93 (s, 18H, But). 13C(1H) RMN
(CDC13): a 170,86 (s, C=O), 153,04-132,58 (Cquat arom.), 131,35, 131,17, 128,38, 128,15, 125,40 et 124,79 (CH arom.), 71,82 (d,
OCH2P(O)Ph2, J(PC) = 78,6 Hz), 70,94 (s, OCH2CO2Et), 60,12 (s, OCH2CH3), 33,73 et 33,60 (2s, C(CH3)3), 32,03 (s, ArCH2Ar), 31,32 et 31,22 (2s, C(CH3)3), 14,19 (s, OCH2CH3). . 31P(1H) RMN (CH2Cl3/C6D6): 6 + 24,9 (s, P(O)Ph2). Theoretical percent analysis for C78H90o10P2 (Mr = 1249.53): C, 74.98; H, 7.26. MS (CI), m / z (%): 1277 (18) [M + NH3 + H +], 1249
(69) [M + H +]. IR (KBr): V = 1753F (C = O) cm-1. 1H NMR (CDCl3): 7.84-7.74 and 7.51-7.34 (m, 20H, P (O) Ph2), 6.77 (s, 4H, m-ArH), 6.42 (s, 4H, m-ArH), 5.20 (s, 4H, OCH2P (O) Ph2), 4.63 (s, 4H, OCH2COXEt), 4.69 and 2.96 (syst. AB, 8H, ArCH2Ar, J (AB) = 13.1
Hz), 4.11 (q, 4H, CH2CH3, 3J = 7.1 Hz), 1.23 (t, 6H, CH2CH3, 3J = 7.1 Hz), 1.11 (s, 18H, But), 0.93 (s, 18H, But). 13C (1H) NMR
(CDC13): a 170.86 (s, C = O), 153.04-132.58 (Cquat arom.), 131.35, 131.17, 128.38, 128.15, 125.40 and 124 , 79 (CH arom.), 71.82 (d,
OCH2P (O) Ph2, J (PC) = 78.6 Hz), 70.94 (s, OCH2CO2Et), 60.12 (s, OCH2CH3), 33.73 and 33.60 (2s, C (CH3) 3 ), 32.03 (s, ArCH2Ar), 31.32 and 31.22 (2s, C (CH3) 3), 14.19 (s, OCH2CH3). . 31P (1H) NMR (CH2Cl3 / C6D6): 6 + 24.9 (s, P (O) Ph2).
Exemple 5. Synthèse du 5,11,17,23-tetra-tert-butyl- 25, 27 - d i é t h o x y c a r b o n y l m é t h o x y - 26 ,28 - bis(diphénylphosphinométhoxy)calix[4]arène (cône).Example 5. Synthesis of 5,11,17,23-tetra-tert-butyl- 25, 27 - d i é t h o x y c a r b o n y l m é t h o x y - 26, 28 - bis (diphenylphosphinomethoxy) calix [4] arene (cone).
Un mélange de 5,11,17,23-tetra-tert-butyl-25,27diéthoxycarbonylméthoxy-26,28-bis(diphénylphos- phinoylméthoxy)calix[4]arène (cône) (5,000 g, 4,00 mmol), préparé selon l'exemple 4, et de phénylsilane (8,657 g, env. 10 ml, 80,0 mmol) est chauffé dans le toluène (60 ml) à reflux pendant deux jours. Après évaporation du solvant, le résidu obtenu est chromatographié sur gel de silice 60 (25g, 70-230 mesh) avec CH2Cl2 (70 ml) comme éluant. Le produit obtenu est une poudre blanche (Rf = 0,95, CHC12). Rendement : 4,670 g, 96%. La chromatographie sur gel de silice peut avantageusement être évitée si, en fin de réaction, une fois la solution filtrée, puis concentrée, on précipite le produit avec de l'éthanol. P.F. : 220-225 OC. Analyse centésimale expérimentale:
C, 76,89; H, 7,57. Analyse centésimale théorique pour C78H9008P2 (Mr = 1217,53): C, 76,95 H, 7,45. MS (CI), m/z (8): 1217 (14) [M + H+]. IR (KBr): v = 1758F (C=O) cm-1. H RMN (CDC13): 67,52- 7,42 et 7,33-7,28 (m, 20H, PPh2), 6,89 (s, 4H, m-ArH), 6,51 (s, 4H, m-ArH), 4,97 (d, 4H, OCH2PPh2, -J(PH) = 3,1 Hz), 4,61 (s, 4H, OCH2CO2Et), 4,60 et 3,07 (syst. AB, 8H, ArCH2Ar, J(AB) = 13
Hz), 4,16 (q, 4H, C.f,CH3, 3J = 7,1 Hz), 1,27 (t, 6H, CH2CH3, 3J = 7,1 Hz), 1,19 (s, 18H, But), 0,94 (s, 18H, But). C{H} RMN (CDCl3): 6 170,62 (s, C=O), 153,70-132,57 (Cquat arom.), 133,33, 132,98, 128,53, 128,41, 128,27, 125,53 et 124,75 (CH arom.), 76,95 (d, OCH2PPh, J(PC) = 8,6 Hz), 70,75 (s, OCH2CO,Et), 60,25 (s, OCH.CH3), 33,88 et 33,69 (2s, C(CH3)3), 32,23 (s, ArCH2Ar), 31,50 et 31,26 (2s, C(CH3)3), 14,30 (s, OCH2CH3). . 31P(1H) RMN (CH2Cl/C6D6): a - 22,1 (s, PPh2)-
Exemple 6. Synthèse du (R,R)-(-)-5,11,17,23-tetra-tertbutyl-25,27-bis(méthylbenzylcarbamoylméthoxy)-26,28- dihydroxy) calix (4] arène. A mixture of 5,11,17,23-tetra-tert-butyl-25,27diethoxycarbonylmethoxy-26,28-bis (diphenylphosphinoylmethoxy) calix [4] arene (cone) (5,000 g, 4.00 mmol), prepared according to Example 4, and phenylsilane (8.657 g, approx. 10 ml, 80.0 mmol) is heated in toluene (60 ml) at reflux for two days. After evaporation of the solvent, the residue obtained is chromatographed on silica gel 60 (25g, 70-230 mesh) with CH2Cl2 (70 ml) as eluent. The product obtained is a white powder (Rf = 0.95, CHC12). Yield: 4.670 g, 96%. Chromatography on silica gel can advantageously be avoided if, at the end of the reaction, once the solution has been filtered and then concentrated, the product is precipitated with ethanol. PF: 220-225 OC. Experimental centesimal analysis:
C, 76.89; H, 7.57. Theoretical percent analysis for C78H9008P2 (Mr = 1217.53): C, 76.95H, 7.45. MS (CI), m / z (8): 1217 (14) [M + H +]. IR (KBr): v = 1758F (C = O) cm-1. H NMR (CDCl3): 67.52-7.42 and 7.33-7.28 (m, 20H, PPh2), 6.89 (s, 4H, m-ArH), 6.51 (s, 4H, m-ArH), 4.97 (d, 4H, OCH2PPh2, -J (PH) = 3.1 Hz), 4.61 (s, 4H, OCH2CO2Et), 4.60 and 3.07 (syst. AB, 8H, ArCH2Ar, J (AB) = 13
Hz), 4.16 (q, 4H, Cf, CH3, 3J = 7.1 Hz), 1.27 (t, 6H, CH2CH3, 3J = 7.1 Hz), 1.19 (s, 18H, But ), 0.94 (s, 18H, But). C {H} NMR (CDCl3): 6,170.62 (s, C = O), 153.70-132.57 (Cquat arom.), 133.33, 132.98, 128.53, 128.41, 128.27, 125.53 and 124.75 (CH arom.), 76.95 (d, OCH2PPh, J (PC) = 8.6Hz), 70.75 (s, OCH2CO, Et), 60.25 (s, OCH.CH3), 33.88 and 33.69 (2s, C (CH3) 3), 32.23 (s, ArCH2Ar), 31.50 and 31.26 (2s, C (CH3) 3) , 14.30 (s, OCH2CH3). . 31P (1H) NMR (CH2Cl / C6D6): a - 22.1 (s, PPh2) -
Example 6. Synthesis of (R, R) - (-) - 5,11,17,23-tetra-tertbutyl-25,27-bis (methylbenzylcarbamoylmethoxy) -26,28-dihydroxy) calix (4] arene.
On fait réagir pendant 15 heures, à température ambiante, un mélange de p-tert-butylcalix[4]arène (13,000 g, 20,03 mmol) et de K2CO3 (3,040 g, 22,00 mmol) dans de l'acétone anhydre (500 ml). Après avoir ajouté du (R)-(+)-2-bromo-Nméthylbenzylacétamide (10,427 g, 43,065 mmol), le mélange est chauffé sous reflux pendant 24 heures. Après filtration, la solution est évaporée à sec. Le résidu est dissous dans CH2C12
(300 ml) et la solution ainsi obtenue est traitée avec une solution aqueuse saturée de NH4Cl, puis avec de l'eau (200 ml).A mixture of p-tert-butylcalix [4] arene (13,000 g, 20.03 mmol) and K2CO3 (3.040 g, 22.00 mmol) is reacted for 15 hours at room temperature in anhydrous acetone. (500 ml). After adding (R) - (+) - 2-bromo-N-methylbenzylacetamide (10.427 g, 43.065 mmol), the mixture is heated under reflux for 24 hours. After filtration, the solution is evaporated to dryness. The residue is dissolved in CH2C12
(300 ml) and the solution thus obtained is treated with a saturated aqueous solution of NH4Cl, then with water (200 ml).
La phase organique est séchée sur MgSO4, puis filtrée.The organic phase is dried over MgSO4, then filtered.
L'addition d'éthanol provoque la précipitation du produit sous forme de poudre blanche (Rf = 0,63 CH2C12/MeOH 98:2, v/v).The addition of ethanol causes the product to precipitate in the form of a white powder (Rf = 0.63 CH2Cl2 / MeOH 98: 2, v / v).
Rendement : 14,8 g, 76%. P. F. > 2800C. [α]D20 = - 44,80 (c = 2 g/100 ml, toluène). Analyse centésimale expérimentale: C, 79,00;
H, 8,34; N, 2.85. Analyse centésimale théorique pour C64H78N206
(Mr = 971,35) : C, 79,14; H, 8,09; N, 2,88. MS (CI), m/z (%) 970 (97) [M+]. IR(KBr) : v = 3436F (OH), v = 3345m (NH), v = 1686F (C=O) cm1 H RMN (CDCl3) : 5 1,03 (s, 18H, But), 1,30 (s, 18H, But), 1.65 (d, 6H, NHCH(CH3)Ph, 3 = 7,0 Hz), 3,31 et 4,10
(syst. AB, 4H, ArCH2Ar, J(AB) = 13,2 Hz), 3,45 et 4,06 (syst.Yield: 14.8 g, 76%. PF> 2800C. [α] D20 = - 44.80 (c = 2 g / 100 ml, toluene). Experimental percentage analysis: C, 79.00;
H, 8.34; N, 2.85. Theoretical percent analysis for C64H78N206
(Mr = 971.35): C, 79.14; H, 8.09; N, 2.88. MS (CI), m / z (%) 970 (97) [M +]. IR (KBr): v = 3436F (OH), v = 3345m (NH), v = 1686F (C = O) cm1 H NMR (CDCl3): 1.03 (s, 18H, But), 1.30 ( s, 18H, But), 1.65 (d, 6H, NHCH (CH3) Ph, 3 = 7.0Hz), 3.31 and 4.10
(syst. AB, 4H, ArCH2Ar, J (AB) = 13.2 Hz), 3.45 and 4.06 (syst.
AB, 4H, ArCH2Ar, J(AB) = 13,5 Hz), 4,23 et 4,65 (syst. AB, 4H,
OCH2CONHR, J(AB) = 15,3 Hz), 5,18 (dq, syst. AMX3, 2H,
NHCH(CH3)Ph, 3J(AX) 9 3J(AM) = 7 Hz), 6,S8 et 6,90 (syst.AB, 4H, m-ArH, 4J = 2,4 Hz), 7,07 et 7,09 (syst. AB, 4H, m-ArH, 4J = 2,4
Hz), 7,19-7,31 (m, 10H, NHCH(CH3)(C6H@)), 7,53 (s, 2H, ArOH), 9,26 (d, 2H, NH, 3J = 7,5 Hz). C{H} RMN (CDC13) : S 21,20 (s,
NHCH(CH3)Ph, 30,90 et 31,60 (2s, C(CH3)3), 32,10 et 32,32 (2s,
ArCH2Ar), 33,90 et 34,03 (2s, C(CH3)3), 49,42 (s, NHCH(CH3)Ph), 74,87 (s, OCH2COMHR), 125,40, 125,74, 125,88, 126,60, 127,30 et 128,43 (6s, CH arom.), 126,52, 126,75, 132,10, 132,21, 142,84, 143,13, 148,30, 149,16 et 149,46 (9s, Chat arom.), 167,39 (s, C=O). AB, 4H, ArCH2Ar, J (AB) = 13.5Hz), 4.23 and 4.65 (syst. AB, 4H,
OCH2CONHR, J (AB) = 15.3Hz), 5.18 (dq, syst. AMX3, 2H,
NHCH (CH3) Ph, 3J (AX) 9 3J (AM) = 7 Hz), 6, S8 and 6.90 (syst.AB, 4H, m-ArH, 4J = 2.4 Hz), 7.07 and 7.09 (AB syst., 4H, m-ArH, 4J = 2.4
Hz), 7.19-7.31 (m, 10H, NHCH (CH3) (C6H @)), 7.53 (s, 2H, ArOH), 9.26 (d, 2H, NH, 3J = 7, 5 Hz). C {H} NMR (CDCl3): S 21.20 (s,
NHCH (CH3) Ph, 30.90 and 31.60 (2s, C (CH3) 3), 32.10 and 32.32 (2s,
ArCH2Ar), 33.90 and 34.03 (2s, C (CH3) 3), 49.42 (s, NHCH (CH3) Ph), 74.87 (s, OCH2COMHR), 125.40, 125.74, 125.88, 126.60, 127.30 and 128.43 (6s, CH arom.), 126.52, 126.75, 132.10, 132.21, 142.84, 143.13, 148.30 , 149.16 and 149.46 (9s, Chat arom.), 167.39 (s, C = O).
Exemple 7. Synthèse du (R,)-(+)-5,11,17,23-tetra-tert- butyl-a5,27-bis(mAthylbenzylcarbamoylmAthoxy)-26,28- bis(diphénylphosphlnoylméthosy)callsf4]arine. Example 7. Synthesis of (R,) - (+) - 5,11,17,23-tetra-tert-butyl-a5,27-bis (mAthylbenzylcarbamoylmAthoxy) -26,28- bis (diphenylphosphlnoylmethosy) callsf4] arine.
On chauffe sous reflux, pendant une heure, un mélange de (R,R)-(-)-5,11,17,23-tetra-tert-butyl-25,27- bis(méthylbenzylcarbamoylméthoxy)-26,28-(dihydroxy)calix[4]arène (8,000 g, 8,24 mmol), préparé selon l'exemple 6, et de ButONa (1,97 g, 20,50 mmol) dans un mélange THF-DMF (9:1, v/v) (250 ml). Après addition de Ph2P(O)CH2OTs (7,300 g, 18,89 mmol), on maintient le reflux pendant encore 60 heures. Après évaporation des solvants, le résidu est repris dans CH2Cl2 (200 ml) et la solution ainsi obtenue est lavée avec une solution saturée en
NH4Cl (100 ml), puis avec de l'eau (100 ml). La phase organique est séchée sur MgSO4, filtrée, puis concentrée à env. 20 ml.A mixture of (R, R) - (-) - 5,11,17,23-tetra-tert-butyl-25,27- bis (methylbenzylcarbamoylmethoxy) -26,28- ( dihydroxy) calix [4] arene (8,000 g, 8.24 mmol), prepared according to Example 6, and ButONa (1.97 g, 20.50 mmol) in a THF-DMF mixture (9: 1, v / v) (250 ml). After addition of Ph2P (O) CH2OTs (7.300 g, 18.89 mmol), reflux is maintained for a further 60 hours. After evaporation of the solvents, the residue is taken up in CH2Cl2 (200 ml) and the solution thus obtained is washed with a saturated solution in
NH4Cl (100ml), then with water (100ml). The organic phase is dried over MgSO4, filtered, then concentrated to approx. 20 ml.
L'additon d'acétone à la solution refroidie à env. 5 OC provoque la précipitation du produit sous forme de poudre blanche (Rf = 0,45 CH2Cl2/MeOH 92:8, v/v). Rendement : 10,800 g, 95%.The addition of acetone to the solution cooled to approx. 5 OC causes precipitation of the product as a white powder (Rf = 0.45 CH2Cl2 / MeOH 92: 8, v / v). Yield: 10.800 g, 95%.
P.F. > 2800C. [ a].-O = + 48,00 (c = 2 g/100 ml, toluène).M.p.> 2800C. [a] .- O = + 48.00 (c = 2 g / 100 ml, toluene).
Analyse centésimale expérimentale: C, 77,39; H, 7,37; N, 1,99. Experimental percentage analysis: C, 77.39; H, 7.37; N, 1.99.
Analyse centésimale théorique pour CgoHlooN2o8P2(Mr = 1399,76):
C, 77,23; H, 7,20; N, 2,00. MS (CI), m/z (%) : 1398 (5) [M+].Theoretical centesimal analysis for CgoHlooN2o8P2 (Mr = 1399.76):
C, 77.23; H, 7.20; N, 2.00. MS (CI), m / z (%): 1398 (5) [M +].
IR(KBr) : 3259F (NH), 1676F (C=O) cm1. 1H RMN (CDCl3) : 5 0,82 (s, 18H, But), 1,25 (s, 18H, But), 1,44 (d, 6H,
NHCH(CH3)Ph, J = 7,0 Hz), 3,03 et 4,68 (syst. AB, 4H, ArCH2Ar,
J(AB) = 12,8 Hz), 3,19 et 4,78 (syst. AB, 4H, ArCH2Ar, J(AB) = 12,9 Hz), 4,11 et 4,76 (syst. AB, 4H, OCH2CONHR, J(AB) = 12,3
Hz), 4,57 et 4,82 (syst. ABX, 4H, OCHAHBP(O)Ph2, J(AB) = 13,9
Hz, J(AX) = 6,5 Hz, J(BX) = 2,3 Hz), 4,98 (dq, syst. AMX3, 2H, MHCH(CH3)Ph, 3J(AX) = 3J(AM) = 7,6 Hz), 6,39 et 6,45 (syst. AB, 4H, m-ArH, 4J = 2,4 Hz), 6,92 (s, 4H, m-ArH), 6,96-7,56 et 7,68-7,80 (m, 30H, H arom.), 9,30 (d, 2H, NH, 3J = 8,4 Hz).IR (KBr): 3259F (NH), 1676F (C = O) cm1. 1H NMR (CDCl3): 0.82 (s, 18H, But), 1.25 (s, 18H, But), 1.44 (d, 6H,
NHCH (CH3) Ph, J = 7.0Hz), 3.03 and 4.68 (syst. AB, 4H, ArCH2Ar,
J (AB) = 12.8 Hz), 3.19 and 4.78 (syst. AB, 4H, ArCH2Ar, J (AB) = 12.9 Hz), 4.11 and 4.76 (syst. AB, 4H, OCH2CONHR, J (AB) = 12.3
Hz), 4.57 and 4.82 (syst. ABX, 4H, OCHAHBP (O) Ph2, J (AB) = 13.9
Hz, J (AX) = 6.5 Hz, J (BX) = 2.3 Hz), 4.98 (dq, syst. AMX3, 2H, MHCH (CH3) Ph, 3J (AX) = 3J (AM) = 7.6Hz), 6.39 and 6.45 (syst. AB, 4H, m-ArH, 4J = 2.4Hz), 6.92 (s, 4H, m-ArH), 6.96- 7.56 and 7.68-7.80 (m, 30H, H arom.), 9.30 (d, 2H, NH, 3J = 8.4Hz).
3C(lH) RMN (CDCl3) : 5 22,09 (s, NHCH(CH3)Ph), 31,02 et 31,63
(2s, C(CH3)3), 31,99 et 32,16 (2s, ArCH,Ar), 33,54 et 33,91 (2s,
C(CH3)3), 48,15 (s, NHCH(CH3)Ph), 70,90 (s, OCH2CONHR), 72,91
(d, OCH2P(O)Ph2, J(PC) = 83,0 Hz), 124,89-132,05 (CH arom.), 124,96-154,29 (CBa. arom.), 167,06 (s, C=O) . 31P(1H) RMN
(CH2C12/C6D6): 527,12 (s, P(O)Ph2).3C (1H) NMR (CDCl3): 5 22.09 (s, NHCH (CH3) Ph), 31.02 and 31.63
(2s, C (CH3) 3), 31.99 and 32.16 (2s, ArCH, Ar), 33.54 and 33.91 (2s,
C (CH3) 3), 48.15 (s, NHCH (CH3) Ph), 70.90 (s, OCH2CONHR), 72.91
(d, OCH2P (O) Ph2, J (PC) = 83.0 Hz), 124.89-132.05 (CH arom.), 124.96-154.29 (CBa. arom.), 167.06 (s, C = O). 31P (1H) NMR
(CH2Cl2 / C6D6): 527.12 (s, P (O) Ph2).
Exemple 8. Synthèse du (R, R) (R,)-(+)-5,11,17,23-tetra-tort- butyl-25,27-bis(méthylbenzylcarbamoylmAthosy)-26,28- bis(diphénylphosphinométhoxy)calix[4]arène.Example 8. Synthesis of (R, R) (R,) - (+) - 5,11,17,23-tetra-tort- butyl-25,27-bis (methylbenzylcarbamoylmAthosy) -26,28- bis (diphenylphosphinomethoxy) calix [4] arena.
On chauffe pendant un mois un mélange de phénylsilane (9,307 g, env. 11 ml, 86,0 mmol) et de (R,R)-(+) 5, 11,17, 23 - t etra- t ert -buty 1 - 25,27 - bis(méthylbenzylcarbamoylméthoxy)-26,28-(dihydroxy)calix[4]arène
(6,000 g, 4,28 mmol), préparé selon l'exemple 7, dans le toluène
(90 ml) au reflux. Après filtration, la solution est évaporée à sec. Le résidu est dissous dans un minimum de CH2C12. L'addition d'éthanol, sous agitation vigoureuse, à la solution préalablement refroidie provoque la précipitation du produit sous forme de poudre blanche. Rendement : 5,400 g, 92*. P.F.A mixture of phenylsilane (9.307 g, approx. 11 ml, 86.0 mmol) and of (R, R) - (+) 5, 11,17, 23 - t etra- t ert -buty 1 is heated for one month. - 25,27 - bis (methylbenzylcarbamoylmethoxy) -26,28- (dihydroxy) calix [4] arene
(6.000 g, 4.28 mmol), prepared according to Example 7, in toluene
(90 mL) at reflux. After filtration, the solution is evaporated to dryness. The residue is dissolved in a minimum of CH2Cl2. The addition of ethanol, with vigorous stirring, to the previously cooled solution causes the product to precipitate in the form of a white powder. Yield: 5.400 g, 92 *. PF
235-2400C. [a]00 = + 34,60 (c = 2 g/100 ml, toluène). Analyse centésimale expérimentale: C, 79,28; H, 7,65; N, 2,04. Analyse
centésimale théorique pour C90H100N2P2O6 (Mr = 1367,76) : C,
79,03; H, 7,37 N, 2,05. MS (CI), m/z (%) : 1367 (6) [M+].235-2400C. [a] 00 = + 34.60 (c = 2 g / 100 ml, toluene). Experimental percentage analysis: C, 79.28; H, 7.65; N, 2.04. Analysis
theoretical centesimal for C90H100N2P2O6 (Mr = 1367.76): C,
79.03; H, 7.37N, 2.05. MS (CI), m / z (%): 1367 (6) [M +].
IR(KBr) : v = 3329F (NH), 1676F (C=O), 1659F, 1645F cm-1. 1H
RMN (CDCl3) : 5 7,32 (d, 2H, NH, 3J = 7,7 Hz), 7,29-7,17 (m,
30H, H arom.), 6,66 (s, 4H, m-ArH), 6,59 et 6,56 (syst. AB, 4H, m-ArH, 4J = 2,5 Hz), 5,2 (dq, syst. AMX3, 2H, NHCH(CH3)Ph, 3J(AX) = 3J(AM) = 7,5 Hz), 5,04 et 4,93 (syst. ABX, 4H, OCHAH9PPh2 J(AB) = 12,5 Hz, J(AX) = 3,5 Hz, J(BX) = 2,7 Hz), 4,52 (s, 4H, OCH2COMHR), 4,42 et 3,04 (syst. AB, 4H, ArCH2Ar,
J(AB) = 13,1 Hz), 4,39 et 2,97 (syst. AB, 4H, ArCH2Ar, J(AB) = 12,9 Hz), 1,38 (d, iH, NHCH(CH3)Ph, 3J = 7,0 Hz), 1,04 (s, 36H,
But). 13C(1H) RMN (CDCl3) : # 169,17 (s, C=O), 153,41-125,04
(Cquat) 133,22, 133,00, 132,85, 132,64, 128,65, 128,58, 128,43, 128,31, 127,04, 12i,36, 125,53, 125,46 et 125,11 (CH arom.), 76,31 (d, OCH2PPh, J(PC) = 8,8 Hz), 74,33 (s, OCH2CONHR), 48,50 (s, NHCH(CH.)Ph), 33,75 (s, C(CH3)3), 32,04 (s large,
ArCH2Ar), 31,30 (s, C(CH3)3), 21,46 (s, NHCH(CH3)Ph). 31P(lH)
RMN (CH2Cl2/CED6) : S - 20,9 (s, PPh2).IR (KBr): v = 3329F (NH), 1676F (C = O), 1659F, 1645F cm-1. 1 hour
NMR (CDCl3): 7.32 (d, 2H, NH, 3J = 7.7Hz), 7.29-7.17 (m,
30H, H arom.), 6.66 (s, 4H, m-ArH), 6.59 and 6.56 (syst. AB, 4H, m-ArH, 4J = 2.5Hz), 5.2 ( dq, syst. AMX3, 2H, NHCH (CH3) Ph, 3J (AX) = 3J (AM) = 7.5 Hz), 5.04 and 4.93 (syst. ABX, 4H, OCHAH9PPh2 J (AB) = 12.5 Hz, J (AX) = 3.5 Hz, J (BX) = 2.7 Hz), 4.52 (s, 4H, OCH2COMHR), 4.42 and 3.04 (syst. AB, 4H , ArCH2Ar,
J (AB) = 13.1 Hz), 4.39 and 2.97 (syst. AB, 4H, ArCH2Ar, J (AB) = 12.9 Hz), 1.38 (d, iH, NHCH (CH3) Ph, 3J = 7.0Hz), 1.04 (s, 36H,
Goal). 13C (1H) NMR (CDCl3): # 169.17 (s, C = O), 153.41-125.04
(Cquat) 133.22, 133.00, 132.85, 132.64, 128.65, 128.58, 128.43, 128.31, 127.04, 12i, 36, 125.53, 125.46 and 125.11 (CH arom.), 76.31 (d, OCH2PPh, J (PC) = 8.8 Hz), 74.33 (s, OCH2CONHR), 48.50 (s, NHCH (CH.) Ph ), 33.75 (s, C (CH3) 3), 32.04 (br s,
ArCH2Ar), 31.30 (s, C (CH3) 3), 21.46 (s, NHCH (CH3) Ph). 31P (lH)
NMR (CH2Cl2 / CED6): S - 20.9 (s, PPh2).
Exemple 9. Synthèse du cis-P,P-5,11,17,23-tetra-tert- butyl-25,27diéthoxycarbonylméthoxy-26,28 - bis(diphénylphosphinométhoxy)calixf4]arine-1,5-(cyclo- octadiène) rhodium (I) tetrafluoroborate (5). Example 9. Synthesis of cis-P, P-5,11,17,23-tetra-tert-butyl-25,27diethoxycarbonylmethoxy-26,28 - bis (diphenylphosphinomethoxy) calixf4] arine-1,5- (cyclo-octadiene) rhodium (I) tetrafluoroborate (5).
On ajoute goutte à goutte une solution de AgBF4 (0,040 g, 0,21 mmol) dans THF (1 ml) à une solution de [RhC1(1,5-cyclooctadiène)]2 (0,050 g, 0,10 mmol) dans CH2Cl2 (2 ml). La solution est filtrée sur celite et additionnée à une solution de 5,11,17, 23-tetra-tert-butyl-25,27- diéthoxycarbonylméthoxy -26,28- bis(diphénylphosphinométhoxy)calix[4]arè (0,255 g, 0,21 mmol), préparé selon l'exemple 5, dans CH2Cî2 (15 ml). Après 2 heures, la solution est concentrée à env. 2 ml. Le produit est précipité par addition d'éther éthylique. Il se présente sous la forme d'une poudre jaune. Rendement : 0,130 g, 86%). P.F. : 220 C (décomp.). Analyse centésimale expérimentale: C, 67,28; H, 6,72. A solution of AgBF4 (0.040 g, 0.21 mmol) in THF (1 ml) is added dropwise to a solution of [RhC1 (1,5-cyclooctadiene)] 2 (0.050 g, 0.10 mmol) in CH2Cl2. (2 ml). The solution is filtered through celite and added to a solution of 5,11,17, 23-tetra-tert-butyl-25,27- diethoxycarbonylmethoxy -26,28- bis (diphenylphosphinomethoxy) calix [4] arè (0.255 g, 0 , 21 mmol), prepared according to Example 5, in CH2Cl2 (15 mL). After 2 hours the solution is concentrated to approx. 2 ml. The product is precipitated by adding ethyl ether. It comes in the form of a yellow powder. Yield: 0.130 g, 86%). M.P .: 220 C (decomp.). Experimental percentage analysis: C, 67.28; H, 6.72.
Analyse centésimale théorique pour C86H102BF4O8P2Rh#0,25 CH2Cl2 (M = 1515,43 + 21,23): C, 67,35 H, 6,74 %. MS (FAB), m/z (%): 1443 (40) [(M - BF4 + O)+], 1427 (11) [(M - BF4)+]. IR (nujol): v = 1743 F et 1715 F cm-l (C=O). 1H RMN (CDCl3): 58,17-8,03 et 7,76-7,32 (m, 20H, PPh2), 6,94 (s, 4H, m-ArH), 6,42 (s, 4H,
ArH), 5,64 (signal large, 4H, OCH2PPh2), 4,32 (signal large, 4H,
HC=CH du cyclooct.), 4,31 (q, 4H, CH2CH2, 3J = 7,1 Hz), 4,06 et 2,92 (syst. AB, 8H, ArCH2Ar, J(AB) = 13,5 Hz), 3,77 (s, 4H,
OCH2CO2Et), 2,38 (m, 4H, CH2 du cyclooct.), 2,13 (m, 4H, CH2 du cyclooct.), 1,37 (t, 6H, CH2CH3, 3J = 7,2 Hz), 1,28 (s, 18H,
But), 0,76 (s, 18H, But). 13C1H) RMN (CDCl3, 297 K): 5 170,47 et 169,34 (2s, C=O), 154,70-125,01 (C arom.), 100,12 et 98,31 (2 s larges, CH=CH du cyclooct.), 72,70-70,27 (m, signaux non résolus dus à OCH2PPh2 et OCH2CO2Et), 61,08 et 60,56 (2s, OCH2CH3), 33,85, 33,65 et 33,42 (3 s, C(CH3)3), 31,51 et 30,97 (C(CH3)3), 30,30 et 29,99 (2 s, CH2 du cyclo-oct.), 14,28 et 14,13 (2s, OCH2CH2); les signaux ArCH2 sont masqués par ceux de C(CH3)3.Theoretical percent analysis for C86H102BF4O8P2Rh # 0.25 CH2Cl2 (M = 1515.43 + 21.23): C, 67.35H, 6.74%. MS (FAB), m / z (%): 1443 (40) [(M - BF4 + O) +], 1427 (11) [(M - BF4) +]. IR (nujol): v = 1743 F and 1715 F cm-1 (C = O). 1H NMR (CDCl3): 58.17-8.03 and 7.76-7.32 (m, 20H, PPh2), 6.94 (s, 4H, m-ArH), 6.42 (s, 4H,
ArH), 5.64 (broad signal, 4H, OCH2PPh2), 4.32 (broad signal, 4H,
HC = CH from cyclooct.), 4.31 (q, 4H, CH2CH2, 3J = 7.1 Hz), 4.06 and 2.92 (syst. AB, 8H, ArCH2Ar, J (AB) = 13.5 Hz), 3.77 (s, 4H,
OCH2CO2Et), 2.38 (m, 4H, CH2 from cyclooct.), 2.13 (m, 4H, CH2 from cyclooct.), 1.37 (t, 6H, CH2CH3, 3J = 7.2Hz), 1 , 28 (s, 18H,
Goal), 0.76 (s, 18H, Goal). 13C1H) NMR (CDCl3, 297K): 5,170.47 and 169.34 (2s, C = O), 154.70-125.01 (C arom.), 100.12 and 98.31 (2s broad , CH = CH from cyclooct.), 72.70-70.27 (m, unresolved signals due to OCH2PPh2 and OCH2CO2Et), 61.08 and 60.56 (2s, OCH2CH3), 33.85, 33.65 and 33.42 (3 s, C (CH3) 3), 31.51 and 30.97 (C (CH3) 3), 30.30 and 29.99 (2 s, CH2 from cyclo-oct.), 14, 28 and 14.13 (2s, OCH2CH2); the ArCH2 signals are masked by those of C (CH3) 3.
3lPtlH} RMN (CH,C12/C^D6): 6 18,8 (d, PPh., J(PRh) = 141,0 Hz). 31Pt1H} NMR (CH, C12 / C CD6): 6 18.8 (d, PPh., J (PRh) = 141.0 Hz).
Exemple 10. Synthèse du cçs-P,P-5,11,17,23-tQtra-tert- butyl-25,27-diéthoxycarbonylméthoxy-26,28- bis(diphénylphosphinométhoxy)calix[4]arène-1,5- (cyclooctadiène) iridium (I) hexafluoroantimonate.Example 10. Synthesis of ccs-P, P-5,11,17,23-tQtra-tert-butyl-25,27-diethoxycarbonylmethoxy-26,28-bis (diphenylphosphinomethoxy) calix [4] arene-1,5- ( cyclooctadiene) iridium (I) hexafluoroantimonate.
On ajoute goutte à goutte une solution de AgSbF6
(0,0975 g, 0,278 mmol) dans THF (1 ml) à une solution de [IrCl(1,5-cyclooctadiène)]2 (0,0935 g, 0,139 mmol) dans CH2Cl2 (3 ml). La solution orange est filtrée sur celite et additionnée à une solution de 5,11,17,23-tetra-tert-butyl-25,27-diéthoxycar- bonylméthoxy-26,28-bis(diphénylphosphinométhoxy)calix[4]arène (0,356 g, 0,292 mmol), préparé selon l'exemple 5, dans CH2Cî2 (15 ml). Après une heure, la solution rouge sang est concentrée à env. 3 ml. Le produit, de couleur rose, est précipité par addition d'éther éthylique. Rendement : 0,450 g, 92%. P.F. : 257 C (decomp.). Analyse centésimale expérimentale: C, 58,72; H, 6,02. Analyse cencésimale théorique pour Cs6H102F6TrOsP2 (Mr = 1753.67): C, 58,90 H, 5,86. MS (FAB), m/z (%) : 1517 (48) [(M - SbF6)+]. IR(nujol) : V 1750 (C=O) cm l. 1H RMN (CDC13) : # 8,05 et 7,63 (m, 20H, PPh2), 6,96 (s, 4H, m-ArH), 6,44 (s, 4H, m-ArH), 5,82 (s, 4H, OCH2PPh2), 4,30 (q, 4H, CH2CH3, = 7,1
Hz), 4,08 et 2,93 (syst. AB, 8H, ArCH2Ar, J(AB) = 13,5 Hz), 3,96 (signal large, 4H, HC=CH du cyclooct.), 3,77 (s, 4H,
OCH2CO2Et), 2,2 et ,84 (m, 8H, CH2 du cyclooct.), 1,36 (t, 6H, CH2CH3, 3J = 7,1 Hz), 1,29 (s, 18H, But), 0,78 (s, 18H, But).A solution of AgSbF6 is added dropwise
(0.0975g, 0.278mmol) in THF (1ml) to a solution of [IrCl (1,5-cyclooctadiene)] 2 (0.0935g, 0.139mmol) in CH2Cl2 (3ml). The orange solution is filtered through celite and added to a solution of 5,11,17,23-tetra-tert-butyl-25,27-diethoxycarbonylmethoxy-26,28-bis (diphenylphosphinomethoxy) calix [4] arene (0,356 g, 0.292 mmol), prepared according to Example 5, in CH2Cl2 (15 mL). After one hour, the blood red solution is concentrated to approx. 3 ml. The product, which is pink in color, is precipitated by adding ethyl ether. Yield: 0.450 g, 92%. Mp: 257 C (decomp.). Experimental percentage analysis: C, 58.72; H, 6.02. Theoretical cencesimal analysis for Cs6H102F6TrOsP2 (Mr = 1753.67): C, 58.90H, 5.86. MS (FAB), m / z (%): 1517 (48) [(M - SbF6) +]. IR (nujol): V 1750 (C = O) cm l. 1H NMR (CDCl3): # 8.05 and 7.63 (m, 20H, PPh2), 6.96 (s, 4H, m-ArH), 6.44 (s, 4H, m-ArH), 5, 82 (s, 4H, OCH2PPh2), 4.30 (q, 4H, CH2CH3, = 7.1
Hz), 4.08 and 2.93 (syst. AB, 8H, ArCH2Ar, J (AB) = 13.5 Hz), 3.96 (broad signal, 4H, HC = CH from cyclooct.), 3.77 (s, 4H,
OCH2CO2Et), 2.2 and, 84 (m, 8H, CH2 from cyclooct.), 1.36 (t, 6H, CH2CH3, 3J = 7.1Hz), 1.29 (s, 18H, But), 0 , 78 (s, 18H, Goal).
-3C(1H) RMN (CDC1 : 6 169,29 (s, C=O), 149,95-129,82 (Cquat arom.), 134,92, 124,61, 128,82, 126,54 et 125,03 (CH arom.), 87,64 (s large, CH=CH du cyclooct.), 73,14 (m, syst. AXX',
OCH2PPh2), 72,11 (s, OCH2CO2Et), 61,12 (s, OCH2CH3), 33,86 et 33,68 (2s, C(CH3)3), 31,50 et 30,97 (2s, C(CH3)3), 30,68 (s, CH2 du cyclooct.), 30,:8 (s, ArCH2Ar), 14,22 (s, OCH2CH3). 31p(lH)
RMN (CDC13) : S + 1:,28 (s, PPh2).-3C (1H) NMR (CDCl: 6,169.29 (s, C = O), 149.95-129.82 (Cquat arom.), 134.92, 124.61, 128.82, 126.54 and 125.03 (CH arom.), 87.64 (broad s, CH = CH of cyclooct.), 73.14 (m, syst. AXX ',
OCH2PPh2), 72.11 (s, OCH2CO2Et), 61.12 (s, OCH2CH3), 33.86 and 33.68 (2s, C (CH3) 3), 31.50 and 30.97 (2s, C ( CH3) 3), 30.68 (s, cyclooct CH2), 30,: 8 (s, ArCH2Ar), 14.22 (s, OCH2CH3). 31p (lH)
NMR (CDCl3): S + 1:, 28 (s, PPh2).
Exemple 11. Synthèse du cds-dichloro, 5,11,17,23-tetratert-butyl-25,27-diéthoxycarbonylméthoxy-26,28- bis(diphénylphosphinométhoxy)calix[4]arène platine (II). Example 11. Synthesis of cds-dichloro, 5,11,17,23-tetratert-butyl-25,27-diethoxycarbonylmethoxy-26,28-bis (diphenylphosphinomethoxy) calix [4] arene platinum (II).
On ajoute goutte à goutte une solution de 5,11,17,23-tetra-tert-butyl-25,27-diéthoxycarbonylméthoxy-26,28- bis(diphénylphosphinométhoxy)calix[4]arène (cône) (0,354 g, 0,29 mmol), préparé selon l'exemple 5, dans THF (20 ml) à une solution de PtCl2(PhCN) (0,132 g, 0,28 mmol) dans THF (30 ml). A solution of 5,11,17,23-tetra-tert-butyl-25,27-diethoxycarbonylmethoxy-26,28-bis (diphenylphosphinomethoxy) calix [4] arene (cone) (0.354 g, 0, 29 mmol), prepared according to Example 5, in THF (20 ml) to a solution of PtCl2 (PhCN) (0.132 g, 0.28 mmol) in THF (30 ml).
Après une heure, la solution est concentrée à env. 5 ml. Par addition d'éther éthylique, le produit précipite sous forme de poudre blanche. Rendement : 0,378 g, 91%. P.F. : 275-280 OC. After one hour, the solution is concentrated to approx. 5 ml. On addition of ethyl ether, the product precipitates in the form of a white powder. Yield: 0.378 g, 91%. M.P .: 275-280 OC.
Analyse centésimale expérimentale: C, 63,18; H, 6,09. Analyse centésimale théorique pour C7sHgoCl2OÔP2Pt (Mr = 1483,53): C, 63,15 H, 6,11. MS (FAB), m/z (%): 1447 (8) [(M - C1)+], 1411 (24) [(M - Cl - HCl)+]. IR (KBr) : v = 1757F et 1732F cm1
(C=o). 1H RMN (CDCl:, 378 K): 6 7,58-7,10 (20H, PPh2), 6,86 (s, 4H, m-ArH), 6,12 (s, 4H, m-ArH), 5,37 (signal large, 4H, OCH2PPh2), 4,17 (s, 4H, OCH2CO2Et), 4,07 (q, 4H, CH2CH3, 3J = 7,0
Hz), 3,91 et 2,65 (syst. AB, 8H, ArCH2Ar, J(AB) = 13 Hz), 1,30 (s, 18H, But), 1,18 (t, 6H, CH2CH3, 3J = 7,1 Hz), 0,78 (s, 18H,
But). l3C(lH) RMN (CDCl3, 345 K): 5 169,70 (s, C=O), 154,62124,43 (C arom.), 73,45 (m, OCH2PPh2), 70,23 (s, OCH2CO2Et), 60,29 (s, OCH2CH3), 33,76 et 33,29 (2s, C(CH3)3), 31,88 (s,
ArCH2Ar), 31,40 et 30,91 (2s, C(CH3)3), 14,03 (s, OCH2CH3).Experimental percentage analysis: C, 63.18; H, 6.09. Theoretical Percent Analysis for C7sHgoCl2OOP2Pt (Mr = 1483.53): C, 63.15H, 6.11. MS (FAB), m / z (%): 1447 (8) [(M - C1) +], 1411 (24) [(M - Cl - HCl) +]. IR (KBr): v = 1757F and 1732F cm1
(C = o). 1H NMR (CDCl :.378K): 6 7.58-7.10 (20H, PPh2), 6.86 (s, 4H, m-ArH), 6.12 (s, 4H, m-ArH), 5.37 (broad signal, 4H, OCH2PPh2), 4.17 (s, 4H, OCH2CO2Et), 4.07 (q, 4H, CH2CH3, 3J = 7.0
Hz), 3.91 and 2.65 (syst. AB, 8H, ArCH2Ar, J (AB) = 13 Hz), 1.30 (s, 18H, But), 1.18 (t, 6H, CH2CH3, 3J = 7.1Hz), 0.78 (s, 18H,
Goal). 13C (1H) NMR (CDCl3, 345K): 5,169.70 (s, C = O), 154.62124.43 (C arom.), 73.45 (m, OCH2PPh2), 70.23 (s, OCH2CO2Et), 60.29 (s, OCH2CH3), 33.76 and 33.29 (2s, C (CH3) 3), 31.88 (s,
ArCH2Ar), 31.40 and 30.91 (2s, C (CH3) 3), 14.03 (s, OCH2CH3).
31P(1H} RMN (CH2Cl2/C6D6) : 5 7,7 (signal large avec satellites
Pt, PPh2, J(PPt) = 3536 Hz). 31P (1H} NMR (CH2Cl2 / C6D6): 5.77 (wide signal with satellites
Pt, PPh2, J (PPt) = 3536 Hz).
Exemple 12. Synthèse du cls-dichloro, cis-dicarbonyl, trans-P,P-5,11,17,23-tetra-tert-butyl-25,27diéthoxycarbonylméthoxy-26,28- bis(diphénylphosphinométhoxy)calix[4]arène ruthénium
(II).Example 12. Synthesis of cs-dichloro, cis-dicarbonyl, trans-P, P-5,11,17,23-tetra-tert-butyl-25,27diethoxycarbonylmethoxy-26,28-bis (diphenylphosphinomethoxy) calix [4] arene ruthenium
(II).
On fait passer un courant de monoxyde de carbone pendant 20 minutes dans une solution de trichlorure de ruthénium commercial (0,080 g, env. 0,33 mmol) dans du 2-éthoxyéthanol (20 ml) au reflux. On ajoute alors du 5,11,17,23-tetra-tert-butyl- 2 5 , 27 - di é t ho xy c a r bon y 1 mé t ho xy - 26 , 28 - bis(diphénylphosphinométhoxy)calix[4]arène (cône) (0,406 g, 0,33 mmol), préparé selon l'exemple 5, tout en maintenant la température à env. 120 OC pendant encore 2 minutes. La solution est ensuite ramenée progressivement à température ambiante, en conservant le flux de CO. On évapore le solvant et recristallise le résidu dans un .mélange CH2Cl2/pentane. Le produit précipite sous forme de microcristaux blancs. Rendement : 0.401 g, 84%. A stream of carbon monoxide is passed for 20 minutes through a solution of commercial ruthenium trichloride (0.080 g, ca. 0.33 mmol) in 2-ethoxyethanol (20 ml) at reflux. Then 5,11,17,23-tetra-tert-butyl- 2 5, 27 - di é t ho xy is added because good y 1 met ho xy - 26, 28 - bis (diphenylphosphinomethoxy) calix [4] arene (cone) (0.406 g, 0.33 mmol), prepared according to Example 5, while maintaining the temperature at approx. 120 OC for another 2 minutes. The solution is then gradually brought back to room temperature, while maintaining the flow of CO. The solvent is evaporated off and the residue recrystallized from a CH2Cl2 / pentane mixture. The product precipitates in the form of white microcrystals. Yield: 0.401 g, 84%.
P.F. > 270 OC. Analyse centésimale expérimentale: C, 63,83; H, 6,40. Analyse centésimale théorique pour C80H90Cl2O10P2Ru#CH2Cl2 (Mr = 1445,53 + 84,:3):C, 63,57 H, 6,06. MS (FAB), m/z (%): 1381 (7) [M - Cl - CO + H+]. IR (KBr) (cm~l): v = 2053F et 1990F (C-O); v = 1758F et 1733F (C=O). IR (nujol): v = 2052F, 1988F (C-O); v = 1748F et 1719F cm-1 (C=O). 1H RMN (CDC13): # 7,88-7,36 (m, 20H, PPh2), 6,85 (s, 4H, m-ArH), 5,98 (s, 4H, m-ArH), 5,89 (signal large, 4H, OCH2PPh2), 4,27 (s large, 4H, OCH2CO2Et), 4,20 (q, 4H, CHCH" 3J = 7,2 Hz), 4,07 et 2,73 (4 signaux larges, syst. AB , 8H, ArCH2Ar, J(AB) = 13 Hz), 1,25 (s, 18H,
But), 1,20 (t, 6H, CH2CH3, 3J = 7,2 Hz), 0,70 (s, 18H, But).PF> 270 OC. Experimental percentage analysis: C, 63.83; H, 6.40. Theoretical Percent Analysis for C80H90Cl2O10P2Ru # CH2Cl2 (Mr = 1445.53 + 84,: 3): C, 63.57H, 6.06. MS (FAB), m / z (%): 1381 (7) [M - Cl - CO + H +]. IR (KBr) (cm ~ 1): v = 2053F and 1990F (CO); v = 1758F and 1733F (C = O). IR (nujol): v = 2052F, 1988F (CO); v = 1748F and 1719F cm-1 (C = O). 1H NMR (CDCl3): # 7.88-7.36 (m, 20H, PPh2), 6.85 (s, 4H, m-ArH), 5.98 (s, 4H, m-ArH), 5, 89 (broad signal, 4H, OCH2PPh2), 4.27 (broad s, 4H, OCH2CO2Et), 4.20 (q, 4H, CHCH "3J = 7.2 Hz), 4.07 and 2.73 (4 signals broad, syst. AB, 8H, ArCH2Ar, J (AB) = 13 Hz), 1.25 (s, 18H,
But), 1.20 (t, 6H, CH2CH3, 3J = 7.2Hz), 0.70 (s, 18H, But).
C{H} RMN (CDCl3, 330 K): 5 192,39 (t, C=O J(PC) = 9,5 Hz), 170,03 (s, C=O), 1=4,71, 153,27, 144,75, 143,51, 134,63, 128,62 et 127,72 (Cquat arcm.), 133,17, 130,38, 128,11, 125,97 et 124,29 (CH arom.), 71,09 (signal large, OCH2PPh2), 70,34 tus, OCH2CO.Et), 60,47 (s, OCH2CH3), 33,76 et 33,24 (2s, C(CH3)3), 32,09 (s, ArCH2Ar,, 31,44 et 30,94 (2s, C(CH3)3), 14,17 (s,
OCH2CH3). 3lP{lH) RMN (CH2Cl2/C6D6): 6 + 18,8 (s, PPh). C {H} NMR (CDCl3, 330K): 5,192.39 (t, C = OJ (PC) = 9.5Hz), 170.03 (s, C = O), 1 = 4.71, 153 , 27, 144.75, 143.51, 134.63, 128.62 and 127.72 (Cquat arcm.), 133.17, 130.38, 128.11, 125.97 and 124.29 (CH arom .), 71.09 (broad signal, OCH2PPh2), 70.34 tus, OCH2CO.Et), 60.47 (s, OCH2CH3), 33.76 and 33.24 (2s, C (CH3) 3), 32 , 09 (s, ArCH2Ar ,, 31.44 and 30.94 (2s, C (CH3) 3), 14.17 (s,
OCH2CH3). 31P (1H) NMR (CH2Cl2 / C6D6): 6 + 18.8 (s, PPh).
Exemple 13. synthèse du trichlorure de 5,11,17,23tetra-tert-butyl-25,27-diéthoxycarbonylméthoxy-26,28- bis(diphénylphosphinoylméthoxy)calix[4]arène Terbium (III)
On dissout du trichlorure de terbiumshexahydrate (0,134 g, 0,35 mmol) dans un mélange d'éthanol (10 ml) et de triéthyle orthoformiate (1 ml, 0,891 g, 6,0 mmol). Après 3 h de chauffage sous reflux, on ajoute à la solution du 5,11,17,23tetra-tert-butyl-25,27-diéthoxycarbonylméthoxy-26,28- bis(diphénylphosphinoylméthoxy)calix[4]arène (0,480 g, 0,38 mmol), préparé selon l'exemple 5, et on maintient encore durant 6 heures le chauffage sous reflux. Après retour à la température ambiante, le complexe du terbium est séparé par centrifugation, puis séché sous vide. Rendement : 0,490 g, 90%. P.F. > 270 OC. Example 13. Synthesis of 5,11,17,23tetra-tert-butyl-25,27-diethoxycarbonylmethoxy-26,28-bis (diphenylphosphinoylmethoxy) trichloride calix [4] arene Terbium (III)
Terbiumshexahydrate trichloride (0.134 g, 0.35 mmol) is dissolved in a mixture of ethanol (10 ml) and triethyl orthoformate (1 ml, 0.891 g, 6.0 mmol). After heating for 3 hours under reflux, 5,11,17,23tetra-tert-butyl-25,27-diethoxycarbonylmethoxy-26,28-bis (diphenylphosphinoylmethoxy) calix [4] arene (0.480 g, 0 , 38 mmol), prepared according to Example 5, and heating under reflux is still maintained for 6 hours. After returning to ambient temperature, the terbium complex is separated by centrifugation, then dried under vacuum. Yield: 0.490 g, 90%. PF> 270 OC.
Analyse centésimale expérimentale: C, 61,95; H, 6,23. Analyse centésimale théorique pour C78HgoCl3OloP2Tb (Mr = 1514,81) : C, 61,85 H, 5,99. IR (KBr) : v 1747F (C=O) .Experimental percentage analysis: C, 61.95; H, 6.23. Theoretical percent analysis for C78HgoCl3OloP2Tb (Mr = 1514.81): C, 61.85H, 5.99. IR (KBr): v 1747F (C = O).
3 P(1H) RMN
(CH2Cl2/C6D6): 5 - 28,8 (s large, P(O)Ph2). 3 P (1H) NMR
(CH2Cl2 / C6D6): 5 - 28.8 (br s, P (O) Ph2).
Claims (26)
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996023800A1 (en) * | 1995-02-01 | 1996-08-08 | Commissariat A L'energie Atomique | Calixarene derivatives, preparation method therefor and use thereof for removing actinides and lanthanides |
| WO2010021863A1 (en) * | 2008-08-19 | 2010-02-25 | Dow Technology Investments Llc | Hydroformylation process using a symmetric bisphosphite ligand for improved control over product isomers |
| US8741173B2 (en) | 2010-10-05 | 2014-06-03 | Dow Technology Investments Llc | Hydroformylation process |
| JP2016128485A (en) * | 2009-10-22 | 2016-07-14 | ザ リージェンツ オブ ザ ユニバーシティ オブ カリフォルニア | Calixarene-bound iridium-containing metal colloids |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02229198A (en) * | 1989-02-28 | 1990-09-11 | Kanebo Ltd | Calxarene derivative |
-
1994
- 1994-03-17 FR FR9403313A patent/FR2717480B1/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02229198A (en) * | 1989-02-28 | 1990-09-11 | Kanebo Ltd | Calxarene derivative |
Non-Patent Citations (1)
| Title |
|---|
| CHEMICAL ABSTRACTS, vol. 114, no. 15, 15 April 1991, Columbus, Ohio, US; abstract no. 143712, KONDO Y ET AL: "Calixarene derivatives having phosphonic acid group" * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996023800A1 (en) * | 1995-02-01 | 1996-08-08 | Commissariat A L'energie Atomique | Calixarene derivatives, preparation method therefor and use thereof for removing actinides and lanthanides |
| US5866087A (en) * | 1995-02-01 | 1999-02-02 | Commissariat A L'energie Atomique | Calixarene derivatives, their preparation process and their use for extracting actinides and lanthanides |
| WO2010021863A1 (en) * | 2008-08-19 | 2010-02-25 | Dow Technology Investments Llc | Hydroformylation process using a symmetric bisphosphite ligand for improved control over product isomers |
| US8507731B2 (en) | 2008-08-19 | 2013-08-13 | Dow Technology Investments Llc | Hydroformylation process using a symmetric bisphosphite ligand for improved control over product isomers |
| CN102123978B (en) * | 2008-08-19 | 2014-03-19 | 陶氏技术投资有限公司 | Hydroformylation process using a symmetric bisphosphite ligand for improved control over product isomers |
| JP2016128485A (en) * | 2009-10-22 | 2016-07-14 | ザ リージェンツ オブ ザ ユニバーシティ オブ カリフォルニア | Calixarene-bound iridium-containing metal colloids |
| EP2490806A4 (en) * | 2009-10-22 | 2017-10-18 | The Regents of The University of California | Calixarene-bound iridium-containing metal colloids |
| US8741173B2 (en) | 2010-10-05 | 2014-06-03 | Dow Technology Investments Llc | Hydroformylation process |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2717480B1 (en) | 1996-08-23 |
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