EP1631539A1 - Difluormethylen substituierte allylester, deren herstellungsverfahren und deren verwendung - Google Patents

Difluormethylen substituierte allylester, deren herstellungsverfahren und deren verwendung

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Publication number
EP1631539A1
EP1631539A1 EP03799615A EP03799615A EP1631539A1 EP 1631539 A1 EP1631539 A1 EP 1631539A1 EP 03799615 A EP03799615 A EP 03799615A EP 03799615 A EP03799615 A EP 03799615A EP 1631539 A1 EP1631539 A1 EP 1631539A1
Authority
EP
European Patent Office
Prior art keywords
advantageously
base
formula
equal
hydrogen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP03799615A
Other languages
English (en)
French (fr)
Inventor
Laurent Saint-Jalmes
Nicolas Roques
Jean-Marie Bernard
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shasun Pharma Solutions Ltd
Original Assignee
Rhodia Chimie SAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rhodia Chimie SAS filed Critical Rhodia Chimie SAS
Publication of EP1631539A1 publication Critical patent/EP1631539A1/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D207/08—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon radicals, substituted by hetero atoms, attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/297—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/007—Esters of unsaturated alcohols having the esterified hydroxy group bound to an acyclic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
    • C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/08—Compounds containing oxirane rings with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals

Definitions

  • the subject of the present invention is compounds forming an allyl ester substituted with a difluoromethylene group.
  • heterocycles in particular nitrogen-containing and in particular 5-membered, have become relatively frequent when they carry groups (-CF 2 ).
  • -CF 2 groups
  • one of the aims of the present invention is to provide a family of precursors for these nitrogen heterocycles.
  • the use of these precursors should be easy, should not require many steps.
  • Another object of the present invention is to provide a process for the synthesis of said precursors.
  • Another object of the present invention is to provide a technique for using these precursors.
  • R f is a radical carrying a perfluoromethylene group which group ensures the bond with the rest of the molecule: *> R 1 and R 3> which may be the same or different, are chosen from hydrogen and the radicals alcohols or aryls; ⁇ is an electron-withdrawing group such that ⁇ -OH is an acid whose pKa (in water) is at most equal to 8, advantageously 6, preferably 5.
  • the ⁇ -OH group constitutes an acid whose pKa is at least equal to 1, advantageously to 2.
  • the ⁇ -O "group does not constitute a good group therefore, both for use as a precursor of cycloaddition and for its synthesis.
  • R, and R 3 do not clutter the molecule too much, so it is advisable to avoid that Ri and / or R 3 are attached to the double bond by a tertiary or even secondary carbon.
  • At least one of Ri and R 3 is a light alkyl (light, that is to say at most 4 carbons) or better still, hydrogen.
  • R is hydrogen; it is also preferred that R 3 is hydrogen; and it is even more preferred that R 1 and R 3 are hydrogen.
  • R f is of formula (II)
  • the X similar (that is to say that they are identical) or different, represent a chlorine, a fluorine or a radical of formula C n F 2n + ⁇ with n integer at most equal to 5, preferably to 2, with the condition that the Xs of the methylene group carrying the open bond are not chlorine and that at least one of them is a fluorine atom, advantageously the Xs of methylene carrying the open bond are either fluorine atoms or else a fluorine atom and a radical of formula C n F 2n + ⁇ (such radicals are indeed considered to be electronically close to fluorine atoms),
  • - GEA is a hydrocarbon or electro-attractor group (that is to say that the Hammett constant ⁇ p (sigma p) is> 0, advantageously at least equal à, 0,2), preferably inert, advantageously, when p is equal to 1, an electron-withdrawing group (cf. preceding lines); - p is a positive integer, that is, it cannot understand the value 0.
  • GEA is advantageously fluorine especially when p is less than or equal to 2.
  • the X's are advantageously all fluors, especially when p is less than or equal to 2.
  • GEA electron-withdrawing group
  • p represents an integer advantageously at most equal to 4, preferably to 2;
  • GEA advantageously represents an electron-withdrawing group the possible functions of which are inert under the conditions of the reaction, advantageously fluorine or a perfluorinated residue of formula C n F 2n + ⁇ , with n integer at most equal to 8, advantageously 5,
  • the total number of carbons of R f is advantageously between 1 and 15, preferably between 1 and 10.
  • R f has the formula C r F 2r + 1 with r positive integer ranging from 1 to 10, advantageously from 1 to 5, preferably from 1 to 3.
  • the present invention is particularly advantageous for Rf of low molecular weight, that is to say those which are relatively volatile (that is to say corresponding to an R f H whose boiling point under atmospheric pressure is at most equal to 100 ° C).
  • the technique is particularly interesting for Rf having a radical having an odd number of carbons and a particular mention must be made for the Rf in Ci, C 2 and C 3 .
  • the trifluoromethyl, pentafluoroethyl and heptafluoropropyl radicals are among the preferred values of R f .
  • ⁇ represents an acyl, advantageously such that the pKa (measured or reduced to a value in water) is at least equal to approximately 2 (the expression approximately is used here to underline that the number which follows corresponds to a mathematical rounding), advantageously to around 3.
  • ⁇ -OH is an alkanoic acid, advantageously from 1 to 8 carbon atoms, preferably from 2 to 5. Economically, the value of ⁇ equal to acetyl is the most interesting.
  • Another object of the present invention is to provide an easy access route to the molecules mentioned above.
  • ⁇ (xi) represents a halogen leaving group (heavier than fluorine, chlorine or bromine) or pseudohalogen such that ⁇ H has a Hammett constant at least equal to that of trifluoroacetic acid, advantageously at least equal to that mesylic acid) with a base chosen from strong nitrogenous bases whose associated acid has a pKa at least equal to 12 among anionic bases with the condition that when the base is a non-nitrogenous anionic base the latter is present of a solvent or a mixture of polar solvents.
  • the compounds of formula (III) are fragile compounds whose purification is often difficult, or almost impossible, due to the instability, in particular thermal, of the compounds of formula (III), especially when ⁇ represents a halogen forming a good group leaving as bromine or iodine.
  • the chlorine derivative is a little more stable.
  • Z representing a methylene group (optionally substituted but preferably unsubstituted) carrying ⁇ -O- and ⁇ limited here to Cl and Br, or even I (but the sulfonyl iodide is not stable; its existence which could not be transient, has not been demonstrated and cannot be implemented, except to do so in situ).
  • bases can give good results: - non-anionic bases in which a nitrogen doublet is conjugated with a carbon-nitrogen double bond; these bases can be used, either alone in stoichiometric or over-stoichiometric quantities, or can be used in quantitative quantities with another base, preferably more basic than these said non-anionic bases; in particular these bases can be used with the bases below, which they are in principle used in stoichiometric or super-stoichiometric amounts; - Anionic nitrogen bases which give good results, but are generally expensive, and the effect of which is all the better when polar aprotic solvents are used as solvents; - non-nitrogenous anionic bases, advantageously not derived from an alcohol or water (hydroxide ions and alcoholates are respectively to be avoided and preferably to be avoided).
  • a polar solvent the donor index of which is at least equal to 10, advantageously 15, preferably 20.
  • these polar solvents have a dielectric constant ⁇ (epsilon) at least equal to 7.
  • ⁇ epsilon
  • this basicity is relatively low in the sense of the basicity of Bronsted, that is to say that the pKa of the associated acid of said solvent is greater than 5, advantageously 6, more preferably 7.
  • said reaction medium is aprotic and anhydrous.
  • this aprotic and anhydrous medium is such that the strongest acid present in the medium, without taking into account the substrate, has a pKa at least equal to 20, better to 25, advantageously to 30, preferably 35.
  • This constraint aims to avoid parasitic reactions during the tearing of the proton from the substrate by the base; in fact the anions resulting from the tearing of a proton by a base are nucleophiles which can lead to a nucleophilic substitution reaction which is not desired.
  • anions are not formed. More generally, it is preferable that the constituents of the reaction mixture are not, in contact with the base used, capable of giving nucleophyte anions. Strong acids (pKa ⁇ 2), or even medium acids (2 ⁇ pKa ⁇ 4.5) do not, strictly speaking, interfere with the reaction because they consume base, giving only anions with little or no nucleophilicity, and therefore little or no parasitic reaction (s). The acids associated with the bases according to the present invention, or resulting from them, obviously do not harm the present invention. This is the reason why the hydroxide ions, or even alcoholates, are not suitable for the processes according to the present invention. Indeed, they lead to molecules which are to be avoided as solvents.
  • the content of labile hydrogen atoms (that is to say those not corresponding to the pKa specified above) is at most equal to 1/3, advantageously 1 / 4, preferably at 10% (in moles), relative to the initial content in that of said base or of said compound of formula (III) which is not in excess.
  • One of the advantages of encryptors is that it makes it possible to at least partially overcome solvents with a high donor index.
  • donor index or donor number: "donor number”
  • donor number the donor index
  • enthalpy 2 - ⁇ H expressed in kilocaloriemol
  • the donor index will be calculated by donor function by multiplying the donor index of each of the solvents by the molar fraction which it represents and by summing these products .
  • anionic nitrogen bases mention should be made of the salts, in particular alkali or noteworthy alkali, of amines, silylated or not, as well as silylamines.
  • the salts giving the best results mention should be made of the salified disilylamines and in particular the salts, in particular alkali or alkaline earth, of hexamethyldisilazane (HMDZ).
  • HMDZ hexamethyldisilazane
  • non-nitrogenous anionic bases mention should be made of non-oxygenated bases such as, for example, alkali or alkaline earth hydrides, and alkane salts such as butyllithium and alkali carbonates. It should be remembered that the bases of this family must be used in the presence of polar solvents.
  • the bases giving the best results are the bases comprising 2 nitrogen atoms conjugated as already mentioned and as detailed below.
  • said base is nitrogenous and not anionic and corresponds to formula (IV): ° - -A-R2
  • A is a metalloid atom in column VB (column of nitrogen, and advantageously the latter) (the periodic classification of the elements used in this application is that of the supplement to the Bulletin of the departments Chimique de France, January 1966, n ° 1).
  • chalcogens advantageously monosubstituted by a monovalent radical R 6 (in which case the chalcogens constitute said metalloid carrying a doublet),
  • the metalloids of column VB are preferably nitrogen, whether for A "or for A 1 .
  • D is chosen from those described above and whose single bond ensuring the link with the rest of the molecule is carried by an atom chosen from sp 2 hybridization carbon atoms substituted by a function or by a bivalent radical R 7 carrying a hydrogen or optionally substituted by a carbon radical R 6 to give a formula of D specified below:
  • the base of formula (IV) comprises a metalloid atom (saturated, that is to say not carrying a double bond), having a resonance (or conjugation) with a bond ⁇ connecting two atoms, at least one of which is a disubstituted and positively charged atom from the column VB; advantageously an organic base comprising a trivalent atom from column VB (column of nitrogen in Mendeleev's table), advantageously nitrogen, an atom whose doublet is directly or indirectly conjugated to a ⁇ bond connecting two atoms, including minus one is an atom from column VB (i.e. A).
  • the radical R is chosen from hydrogen, the values of D and from hydrocarbon radicals, advantageously aryls and especially alkyls.
  • the radical D and this imine function are arranged in such a way that the atoms of nitrogen and of said metalloid are as far apart as possible, in other words and for example, that the nitrogen of the imine function is that of the two atoms linked by the ⁇ bond which is the farthest from the trivalent atom of column V.
  • the imine function is general for all the atoms of column VB linked by the bond ⁇ in the case where the bond ⁇ has a carbon atom and an atom from column V.
  • the previous sequence corresponds to the formula:
  • said trivalent atom of the VB column forms or constitutes a tertiary amine.
  • said organic base comprising a trivalent atom from column VB, the doublet of which is conjugated to a ⁇ bond, constitutes a molecule of the following formula:
  • the potentiation effect of the base is particularly marked when said ⁇ bond connecting two atoms is intracyclic (or a mesomeric form is intracyclic), even when it is intracyclic in an aromatic cycle.
  • organic base comprising a saturated metalloid atom, having a resonance with a ⁇ bond can be advantageously chosen from dialkoyiaminopyridines, in particular in the para or ortho position (that is to say in the position 2 of pyridine or 4 see formula above).
  • said base carrying at least 2 trivalent nitrogen is advantageously such that said 2 trivalent nitrogen form a binding system comprising an imine conjugated with the doublet of an amine.
  • Amines which, like DBU (DiazaBicycloUndecene, which has 9 carbon atoms) or DBN (DiazaBicycloNonene which has 7 carbon atoms), form with the imine function a substituted amidine function, advantageously intracyclic with 1 or even 2 rings, constitute also particularly interesting bases for implementing the present invention. Examples of such bases are to be found in diazabicycloalkenes of 6 to 15 carbon atoms:
  • R 6 'and R 6 "have the same value as Rs. It is possible to substitute the free aryl vertices (engaged in an aromatic) or aliphatic (whose attachment point is a sp 3 carbon). But this is of little interest and the disadvantage of weighing down the base.
  • Another object of the present invention is to find a cycloaddition technique capable of working with the compounds of formula (I).
  • one of the main interests of the present invention is to provide easy access to heterocycles by a 3 + 2 type addition, and in particular 1, 3 dipolar cycloadditions.
  • the co-substrate is an organic compound carrying a pentavalent nitrogen itself carrying 2 double bonds (including the donor-acceptor type bonds) of which at least one double bond connects said nitrogen to a carbon.
  • the co-substrates providing the part of 3 atoms correspond to the canonical dipolar forms as follows:
  • b can be a nitrogen, optionally substituted, a and c can be oxygen, nitrogen or carbon, these last two atoms can carry a hydrocarbon radical or a hydrogen.
  • R f is trifluoromethyl
  • Ri and R 3 are hydrogen and ⁇ is chlorine.
  • Test 02JGR910 test in RPAS 100 ml with double envelope, agitation: 4 inclined blades (600 rpm): 2a (10 g at 96% by weight, 38.5 mmol), DMF (35 g), K 2 C0 3 (18 g, 0.130 mol), b)% CPG area
  • the reaction medium is left overnight at room temperature before treatment. After filtration (filtered glass No. 4) and washing of the cake with 10 ml of DMF, the filtrate is poured into 20 ml of water and this aqueous phase is extracted with MTBE (3 * 25 ml). The organic layer is assayed by 19 F NMR with internal standard:
  • 2-chloro-4,4,4-trifluorobutyl acetate is charged into a 250 ml three-necked flask fitted with a condenser, a thermometer, an addition funnel and a magnetic stirrer (3a) (12 g 58.9 mmol) and diisopropyl ether (135 ml 0.95 mol). 1, 8-diazabicyclo [5.4.0] undec-7-ene (8.98 g 59 mmol) is added dropwise over 25 minutes. The reaction medium is heated at 70 ° C for 4 hours. The evolution is followed by CPG injections. At the end of the reaction, a yield of product formed of 77.5% is determined by GC assay with internal standard.
  • the reaction medium is poured into 200 ml of water. Extraction is carried out with 3 times 100 ml of diisopropyl ether and the organic phases, previously grouped together, are dried over magnesium sulfate. After concentration at atmospheric pressure of the diisopropyl ether, 7 g (Yield: 71%) of the trifluorobutenol acetate are isolated by conventional distillation.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
EP03799615A 2002-12-20 2003-12-17 Difluormethylen substituierte allylester, deren herstellungsverfahren und deren verwendung Withdrawn EP1631539A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0216308A FR2849025B1 (fr) 2002-12-20 2002-12-20 Esters d'allyle substitue par un groupe difluoromethylene, leur procede de synthese et leur utilisation
PCT/FR2003/003780 WO2004065347A1 (fr) 2002-12-20 2003-12-17 Esters d'allyle substitue par un groupe difluoromethylene, leur procede de synthese et leur utilisation

Publications (1)

Publication Number Publication Date
EP1631539A1 true EP1631539A1 (de) 2006-03-08

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EP03799615A Withdrawn EP1631539A1 (de) 2002-12-20 2003-12-17 Difluormethylen substituierte allylester, deren herstellungsverfahren und deren verwendung

Country Status (6)

Country Link
US (1) US20060069284A1 (de)
EP (1) EP1631539A1 (de)
JP (1) JP2006511592A (de)
AU (1) AU2003299334A1 (de)
FR (1) FR2849025B1 (de)
WO (1) WO2004065347A1 (de)

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Also Published As

Publication number Publication date
WO2004065347A1 (fr) 2004-08-05
JP2006511592A (ja) 2006-04-06
AU2003299334A1 (en) 2004-08-13
FR2849025B1 (fr) 2005-10-14
FR2849025A1 (fr) 2004-06-25
US20060069284A1 (en) 2006-03-30

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