EP3571188A1 - Verfahren zur herstellung von thiolactonen, mit diesem verfahren gewonnene thiolactone und verwendungen davon - Google Patents

Verfahren zur herstellung von thiolactonen, mit diesem verfahren gewonnene thiolactone und verwendungen davon

Info

Publication number
EP3571188A1
EP3571188A1 EP18704047.2A EP18704047A EP3571188A1 EP 3571188 A1 EP3571188 A1 EP 3571188A1 EP 18704047 A EP18704047 A EP 18704047A EP 3571188 A1 EP3571188 A1 EP 3571188A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
aryl
hydrogen atom
radical
group
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Withdrawn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
EP18704047.2A
Other languages
English (en)
French (fr)
Inventor
Olivier COUTELIER
Mathias Destarac
Marvin LANGLAIS
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.)
Centre National de la Recherche Scientifique CNRS
Universite Toulouse III Paul Sabatier
Original Assignee
Centre National de la Recherche Scientifique CNRS
Universite Toulouse III Paul Sabatier
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 Centre National de la Recherche Scientifique CNRS, Universite Toulouse III Paul Sabatier filed Critical Centre National de la Recherche Scientifique CNRS
Publication of EP3571188A1 publication Critical patent/EP3571188A1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D333/30—Hetero atoms other than halogen
    • C07D333/32—Oxygen atoms

Definitions

  • the present invention relates to the field of thiolactones.
  • the present invention relates to a process for the preparation of substituted thiolactones of formula (I), substituted thiolactones of formula ( ⁇ ) obtainable by the implementation of this method, the use of substituted thiolactones of formula (I) or of formula ( ⁇ ) for the preparation of polymers or for the functionalization of particles, flat surfaces or polymers.
  • Thiolactones are heterocyclic compounds analogous to lactones, in which an oxygen atom is replaced by a sulfur atom.
  • the sulfur atom is in the ring and is adjacent to a carbonyl group.
  • the heterocycle of the thiolactones may be substituted with at least one chemical group, in particular with an alkyl or aryl group.
  • R Alkyl
  • a more recent synthetic method provides access to thiolactones having alkyl or aryl groups (Filippi et al., Tet Lett, 2006, 47, 6067-6070).
  • This process is based on a catalytic isomerization process of a thionolactone to a thiolactone in the presence of boron trifluoride (BF 3 ) and diethyl ether (Et 2 O) in an organic solvent such as toluene under reflux according to following reaction scheme (2):
  • R alkyl, phenyl
  • this process utilizes a Lewis acid type catalyst (eg, boron trifluoride) and can not be readily used for the synthesis of thiolactones bearing substituents other than alkyl or phenyl moieties, such as complex organic functions and / or or incompatible with this type of catalyst.
  • a Lewis acid type catalyst eg, boron trifluoride
  • isolated yields of thiolactones are often low.
  • this process requires the synthesis of the starting thionolactones from the corresponding lactones.
  • the subject of the present invention is therefore a process for the preparation of substituted thiolactones of formula (I) below: in which :
  • R 1 , R 2 , R 3 and R 4 which may be identical or different, represent a hydrogen atom or a group chosen from alkyl, acyl, aryl, heteroaryl, saturated or unsaturated cycloalkyl and saturated or unsaturated heterocycloalkyl groups; radicals R 1 , R 2 , R 3 and R 4 may also together form a saturated or unsaturated cycloalkyl or heterocycloalkyl group or an aryl or heteroaryl group; and
  • R 5 - R 6 and R 7 identical or different, are:
  • R 5 is different from the other two groups R 6 and R 7 , R 6 and R 7 have the same definition as in alternative (a), and R 5 is a thiolactone radical of the following formula:
  • R 1 , R 2 , R 3 , and R 4 have the same meaning as in formula (I) above, R 6 and R 7 have the same definition as in alternative (a), Z represents a divalent group chosen from a carbonyl group, a carbonate group, an alkylene group and an arylene group, and the # sign represents the attachment point of the thiolactone radical to the -CR 6 R 7 CH 2 -thiolactone radical of the compound of formula (I );
  • said method being characterized in that it comprises at least the following steps: 1) a step during which, in the presence of a radical initiator, a xanthate of the following formula (II) is reacted:
  • R 21 , R 22 , R 23 and R 24 which may be identical or different, represent a hydrogen atom or a group chosen from alkyl, acyl, aryl, heteroaryl, alkene, alkyne, saturated or unsaturated cycloalkyl and saturated heterocycloalkyl groups; or unsaturated 1 , the radicals R 21 , R 22 , R 23 and R 24 may also together form a saturated or unsaturated cycloalkyl or heterocycloalkyl group or an aryl or heteroaryl group; and
  • R 5a , R 6 and R 7 identical or different, are:
  • (a ') selected from hydrogen, cyano (CN), alkyl, acyl, aryl, heteroaryl, aralkyl, saturated or unsaturated cycloalkyl, saturated heterocycloalkyl or unsaturated and a phthalimido group, said alkyl, acyl, aryl, heteroaryl, aralkyl, saturated or unsaturated cycloalkyl, saturated or unsaturated heterocycloalkyl and phthalimido groups which may be substituted with a group X selected from the following groups: P (0) (OR 8 ) (OR 8 ) in which the radicals R 8 and R 8 ' , which may be identical or different, represent a hydrogen atom or an alkyl radical; C n F 2 n + i wherein n is an integer from 1 to 20; SiR 9 p (OR 10 ) 3 -p in which the radicals R 9 and R 10 , which may be identical or different, represent a hydrogen atom or an alkyl radical
  • R 21 , R 22 , R 23 and R 24 have the same meaning as in formula (II) above, R 6 and R 7 have the same definition as in the alternative (a '), Z represents a divalent group selected from a carbonyl group, a carbonate group, an alkylene group and an arylene group, and the sign # represents the point of attachment of the xanthate group to the -CR 6 R 7 -xanthate group of the compound of formula (II);
  • R 25 represents a group selected from saturated or unsaturated alkyl, acyl, aryl, heteroaryl, aralkyl, cycloalkyl and saturated or unsaturated heterocycloalkyl groups;
  • Y is an oxygen atom or an NR 26 radical in which R 26 represents a hydrogen atom or an alkyl group, and preferably an oxygen atom;
  • R 1 , R 2 , R 3 and R 4 have the same meaning as in formula (I) above;
  • R 1 , R 2 , R 3 and R 4 have the same meaning as in formula (I) above;
  • R 21 , R 22 , R 23 and R 24 have the same meaning as in formula (II) above; and R 25 has the same meaning as in formula (III) above;
  • R 5b , R 6 and R 7 identical or different, are:
  • (a ) selected from hydrogen, cyano (CN), alkyl, acyl, aryl, heteroaryl, aralkyl, saturated or unsaturated cycloalkyl, saturated heterocycloalkyl or unsaturated and a phthalimido group, said alkyl, acyl, aryl, heteroaryl, aralkyl, saturated or unsaturated cycloalkyl, saturated or unsaturated heterocycloalkyl and phthalimido groups which may be substituted with a group X selected from the following groups: P (0) (OR 8 ) (OR 8 ) in which the radicals R 8 and R 8 ' , which may be identical or different, represent a hydrogen atom or an alkyl radical; C n F 2 n + 1 in which n is an integer ranging from 1 to 20 ; SiR 9 p (oR 10) 3 -p wherein the radicals R 9 and R 10, identical or different, represent a hydrogen atom or an alkyl radical and p is
  • R 1 , R 2 , R 3 , R 4 , R 21 , R 22 , R 23 , R 24 , Y and R 25 have the same meaning as in formula (IV) above
  • R 6 and R 7 have the same definition as in alternative (a ")
  • Z represents a divalent group selected from a carbonyl group, a carbonate group, an alkylene group and an arylene group
  • the sign # represents the anchor point of the mono radical -adducted with the radical - CR 6 R 7 -monoadduct of the compound of formula (IV);
  • the process of the invention makes it possible, during step 2) of thermolysis, to access, in a single simple step, a substituted thiolactone.
  • Thermolysis 2) implements less aggressive conditions than the conditions generally used in the prior art such as acid-base conditions that employ acidic and / or basic reagents in several steps. These acid-base conditions are not desirable because they do not make it possible to obtain substituted thiolactones having fragile chemical groups such as cyano groups; moreover, they very often lead to poor yields by the formation of by-products.
  • R 17 , R 17 , R 18 , R 19 , R 19 ' , R 20 , R 21 , R 22 , R 23 , R 24 and R 25 may be linear or branched, substituted or unsubstituted, and may contain from 1 to 12 carbon atoms, and preferably 1 to 6 carbon atoms. They are preferably chosen from methyl, ethyl, n-propyl, naphthyl, n-butyl, n-butyl, n-butyl, n-butyl, n-butyl, n-butyl, n-butyl, n-pentyl, neo-pentyl, tert-pentyl, hexyl, r?
  • R 20 , R 21 , R 22 , R 23 , R 24 and R 25 may be fluorinated or perfluorinated.
  • D denotes a hydrogen atom or a linear or branched, saturated or unsaturated hydrocarbon-based chain which may contain from 1 to 12 carbon atoms, and preferably 1 to 6 carbon atoms.
  • acyl groups mentioned for R 1 , R 2 , R 3 , R 4 , R 5 , R 5a , R 5b , R 6 , R 7 , R 21 , R 22 , R 23 , R 24 and R 25 mention may especially be made of formyl, acetyl, propanoyl or pivaloyl groups.
  • aryl group means an optionally mono- or polysubstituted monocyclic or polycyclic aromatic hydrocarbon group comprising from 3 to 10 carbon atoms, and preferably from 3 to 6 carbon atoms.
  • aryl radical mentioned for R 1 , R 2 , R 3 , R 4 , R 5 , R 5a , R 5b , R 6 , R 7 , R 12 , R 13 , R 14 , R 15 , R 15 ' , R 15 " , R 16 , R 16 ' , R 17 , R 17' , R 18 , R 19 , R 19 ' , R 20 , R 21 , R 22 , R 23 , R 24 and R 25 , may in particular mention may be made of naphthyl, anthranyl, phenanthryl, o-tolyl, p-tolyl, xylyl, ethylphenyl, mesityl and phenyl
  • the cycloalkyl group is preferably saturated.
  • cycloalkyl groups mentioned for R 1 , R 2 , R 3 , R 4 , R 5 , R 5a , R 5b , R 6 , R 7 , R 21 , R 22 , R 23 , R 24 and R 25 mention may in particular be made of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl groups.
  • the cycloalkyl groups mentioned for R 1 , R 2 , R 3 , R 4 , R 5 , R 5a , R 5b , R 6 , R 7 , R 21 , R 22 , R 23 , R 24 and R 25 may be fluorinated or perfluorinated.
  • a heterocycloalkyl group is a cyclic group comprising from 3 to 10 carbon atoms, and preferably from 3 to 6 carbon atoms, and at least one heteroatom chosen from N, O, P, Si and S.
  • the heterocycloalkyl group is preferably saturated.
  • heterocycloalkyl groups mentioned for R 1 , R 2 , R 3 , R 4 , R 5 , R 5a , R 5b , R 6 , R 7 , R 21 , R 22 , R 23 , R 24 and R 25 , mention may in particular be made of oxacyclopropanyl, azacyclopropanyl, thiacyclopropanyl, tetrahydrofuranyl, pyrrolidinyl, tetrahydrothiophenyl, tetrahydropyranyl, piperidinyl, piperazinyl or thiacyclohexane groups.
  • the heterocycloalkyl groups mentioned for R 1 , R 2 , R 3 , R 4 , R 5 , R 5a , R 5b , R 6 , R 7 , R 21 , R 22 'R 23 , R 24 and R 25 may be fluorinated or perfluorinated.
  • a heteroaryl group is a monocyclic or polycyclic aromatic group, optionally mono or polysubstituted, comprising from 3 to 10 carbon atoms, and preferably from 5 to 6 carbon atoms, and at least one chosen heteroatom. among N, O, P, Si and S.
  • heteroaryl groups mentioned for R 1 , R 2 , R 3 , R 4 , R 5 , R 5a , R 5b , R 6 , R 7 , R 21 , R 22 R 23 , R 24 and R 25 may be mentioned in particular furanyl, thiophenyl, pyrrolyl, pyridinyl, pyranyl, oxazinyl, thazinyl, pyrimidinyl, piperazinyl or thiinyl groups.
  • An aralkyl group within the meaning of the present invention, is a group comprising at least one alkyl radical and at least one aryl radical, said alkyl and aryl radicals being linked by a carbon-carbon bond, and said alkyl and aryl radicals having the same definition than that given for the alkyl and aryl radicals above.
  • aralkyl group mention may in particular be made of the benzyl group.
  • An alkylene group within the meaning of the present invention, can be linear or branched, substituted or unsubstituted, and can comprise from 1 to 12 carbon atoms, and preferably from 1 to 6 carbon atoms.
  • An arylene group within the meaning of the present invention may be mono or polysubstituted, and may comprise from 10 to 30 carbon atoms, and preferably from 10 to 20 carbon atoms.
  • the radicals R 5 , R 6 and R 7 are chosen such that the group -CR 5 R 6 R 7 forms a polymer chain P 1 ; according to alternative (b ') for formula (II), the radicals R 5a , R 6 and R 7 are chosen such that the group -CR 5a R 6 R 7 forms a polymer chain P 1 ; and according to alternative (b ") for formula (IV), the radicals R 5b , R 6 and R 7 are chosen such that the group -CR 5b R 6 R 7 forms a polymer chain P 1 .
  • the term polymer chain P 1 for the groups -CR 5 R 6 R 7 , -CR 5a R 6 R 7 , and -CR 5b R 6 R 7 any sequence of monomer units obtained by a reversible addition-fragmentation controlled radical polymerization process (also known as RAFT / MADIX) such as the RAFT / MADIX method described for example by Moad et al. [Aust. J. Chem. , 2012, 65 (8), 985-1076] or by Destarac et al. [ACS Symposium Series, Vol. 854, American Chemical Society, 2003. Matyjaszewski, K., Ed. Advances in Controlled / Living Radical Polymerization, p.
  • RAFT / MADIX reversible addition-fragmentation controlled radical polymerization process
  • the polymer chain P 1 may also result from the transformation of a polymer having at least one -OH or at least one -NH 2 terminal into a suitable xanthate end.
  • the polymer chain P 1 may be chosen from a polydimethylsiloxane, a random or block copolymer based on dimethylsiloxane units, an ethylene polyoxide, a propylene polyoxide, a block copolymer or random block copolymer.
  • ethylene and propylene oxide a poly (butylene oxide), a random or block copolymer based on ethylene oxide and butylene oxide, a polyethylene tetramethylene oxide (poly (tetrahydrofuran)), a polylactide polycaprolactone, polyester, polyethylene, poly (ethylene-co-butylene) (or hydrogenated polybutadiene), polypropylene, oligopeptide, polypeptide, polyamide, polyurethane, polystyrene and polymer synthesized by controlled radical polymerization unsaturated monomers according to techniques known in the state of the art such as ATRP, NMP (well known under the name of "nitroxide mediated polymerization") described for example by Hawker et al.
  • ATRP ATRP
  • NMP well known under the name of "nitroxide mediated polymerization"
  • At least one of R 21 or R 22 is different from a hydrogen atom.
  • R 21 , R 22 , R 23 and R 24 represent a hydrogen atom or an alkyl group.
  • R 21 (respectively R 22 ) may be an alkyl group, especially a methyl group, and R 22 (respectively R 21 ) may be a hydrogen atom.
  • At least one of R 23 and R 24 is different from a hydrogen atom.
  • R 23 is an alkyl group, especially a methyl group
  • R 24 is a hydrogen atom or an alkyl group, especially a methyl group.
  • the group R 5 is different from a hydrogen atom.
  • R 5 is a cyano group or a phthalimido group.
  • At least one of the groups R 6 or R 7 is a hydrogen atom and advantageously, the two groups R 6 and R 7 are hydrogen atoms.
  • R 25 is an alkyl group, particularly a methyl group.
  • R 1 , R 2 , R 3 and R 4 represent a hydrogen atom or an alkyl group.
  • R 1 (respectively R 2 ) is an alkyl group, especially a methyl group
  • R 2 (respectively R 1 ) is a hydrogen atom
  • At least one of the groups R 3 or R 4 is a hydrogen atom and more preferably the two groups R 3 and R 4 are hydrogen atoms.
  • the group R 26 is preferably a methyl group.
  • the process of the invention leads to the formation of a thiolactone of formula (I) chosen from:
  • the first step a) of preparing a salt of formula (VII) is preferably carried out at room temperature, in particular in an organic solvent such as tetrahydrofuran and in particular using a strong base, preferably potassium hydroxide.
  • the duration of step a) is generally about 20 to 24 hours.
  • the second step b) of preparing a xanthate of formula (II) is preferably carried out in an organic solvent such as acetone and in particular in an ice bath, the addition reaction of the compound of formula (VIII) being highly exothermic.
  • the reaction is preferably carried out at room temperature, in particular for a period of about 2 to 4 hours.
  • the xanthate of formula (II) thus obtained can be filtered, and then the filtrate is preferably concentrated in vacuo.
  • the xanthate of formula (II) can then be engaged in the process according to the present invention without further purification.
  • the xanthate of formula (II) can be obtained by RAFT / MADIX polymerization of monomers or by organic synthesis of a polymer-xanthate according to the reaction scheme ( 4) next:
  • the xanthate of formula (II) is S- (cyanomethyl) -O- (3-methylbutan-2-yl) carbonodithioate (XAl) and S - ((1-3) dioxoisoindolin-2-yl) methyl) -O- (3-methylbutan-2-yl) carbonodithioate (XA2).
  • Step 1) of preparation of the mono-adduct of formula (IV) of the process according to the invention can be carried out without solvent, in water or in an organic solvent. It is preferably carried out in an organic solvent or in water, and even more preferably in an organic solvent.
  • the organic solvent which can be used during this stage 1) is then preferably chosen from toluene, tetrahydrofuran (THF), ethyl acetate and 1,4-dioxane. Among such organic solvents, toluene is particularly preferred.
  • radical initiator a chemical species capable of forming free radicals that is to say a chemical species having one or more unpaired electrons on its outer layer.
  • the radical initiator used in step 1) is preferably chosen from organic peroxides, azo derivatives and redox systems.
  • organic peroxides mention may in particular be made of dilauroyl peroxide (LPO), t-butyl peroxyacetate, t-butyl peroxybenzoate, t-butyl peroxyoctoate, t-butyl peroxydodecanoate, t-butyl peroxyisobutyrate, t-amyl peroxypyvalate, t-butyl peroxypyvalate, di-isopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, dicumyl peroxide, dibenzoyl peroxide, potassium peroxydisulfate, peroxydisulphate. sodium and ammonium peroxydisulfate.
  • LPO dilauroyl peroxide
  • t-butyl peroxyacetate t-butyl peroxybenzoate
  • t-butyl peroxyoctoate t-butyl peroxydodecanoate
  • azo derivatives mention may in particular be made of 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2-cyano-2-butane), dimethyl-2,2'-azobisdimethylisobutyrate, 4 , 4'-azobis- (4-cyanopentanoic acid), 1,1-azobis- (cyclohexanecarbonitrile), 2- (t-butylazo) -2-cyanopropane, 2,2'-azobis- [2-methyl] N - (1, 1) -bis (hydroxymethyl) -2-hydroxyethyl] propanamide, 2,2'-azobis [2-methyl-N-hydroxyethyl] propanamide, 2,2'-azobis- dihydrochloride ( N, N'-dimethyleneisobutyramidine), 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis- (N, N'-dimethyl isobutyramine), 2,2'-azobis
  • the redox systems are for example chosen from systems comprising combinations such as the following combinations:
  • mixtures of an alkali metal persulfate with an arylphosphinic acid such as benzene phosphonic acid or similar compounds.
  • ammonium persulfate and sodium formaldehyde sulfoxylate is particularly preferred.
  • the radical initiator can be added to the reaction medium in one or more times, that is to say in portions.
  • the radical initiator is added to the reaction medium in portions.
  • the mono-adduct of formula (IV) as obtained at the end of step 1) is chosen from methyl-cyano-2-methyl-4 - (( ((3-Methylbutan-2-yl) oxy) carbonothioyl) thio) hexanoate (XA1CN) and methyl 6- (1,3-dioxoisoindolin-2-yl) -2-methyl-4 - ((((3-methylbutan) -2-yl) oxy) carbonothioylthio) hexanoate (XA2PH).
  • the monomers of formula (III) are preferably chosen from compounds which are monomers with little or no polymerization under the conditions of temperature and pressure used during step 1) of the process according to the invention, that is to say that is to say that lead to a mono-adduct of formula (IV) without significant presence of diadduit, triadduit, etc.
  • monomers of formula (III) there may be mentioned in particular methyl methyl-4-pentenoate ( al).
  • Step 1) of the process according to the invention is generally carried out at a temperature ranging from 10 to 140 ° C, and preferably from 40 to 110 ° C, and more preferably between 65 and 90 ° C.
  • the duration of said step 1) generally varies from about 3 to 48 hours, and still more preferably from 4 to about 24 hours.
  • the mono-adduct of formula (IV) obtained at the end of step 1) is purified, for example by chromatography on silica gel, before being engaged. in the second stage of thermolysis.
  • Step 2) of thermolysis of the process according to the present invention can be carried out with or without a solvent. According to a preferred embodiment of the invention, step 2) of thermolysis is carried out without solvent.
  • the temperature of the thermolysis step 2) is generally between about 40 and 210 ° C., preferably between about 100 and 200 ° C. and more particularly between about 160 and 190 ° C.
  • thermolysis step 2) is generally carried out at a temperature sufficient to decompose the mono-adduct of formula (IV).
  • thermolysis means thermal decomposition. It is a reaction of chemical decomposition caused by heat. In this case, the action of heat leads to the decomposition of the mono-adduct of formula (IV), allowing the formation of the thiolactone of formula (I).
  • step 2) of the process of the invention does not use base (s) and / or acid (s), and preferably does not implement other reagents than the mono-adduct of formula (IV) from step 1). In other words, only the action of heat leads to the thiolactones of formula (I).
  • the mono-adduct of formula (IV) obtained in step 1) has a suitable chemical structure, in particular by defining the groups R 1 , R 2 , R 3 , R 4 , R 5b , R 6. , R 7 , R 21 , R 22 , R 23 , R 24 and R 25 , to allow forming a substituted thiolactone of formula (I) by thermolysis. In other words, cyclization to thiolactone (I) is favored.
  • step 2) of thermolysis is carried out in a solvent
  • said solvent is preferably chosen from high-boiling solvents (that is to say having a boiling point greater than or equal to the temperature thermolysis), such as, for example, 1,2-dichlorobenzene.
  • thermolysis step 2) can be carried out at atmospheric pressure or under vacuum, especially in the latter case, to eliminate any volatile by-products that may be formed during the reaction.
  • step 2) of thermolysis is carried out in a closed container (e.g., schlenk tube), and preferably under vacuum.
  • a closed container e.g., schlenk tube
  • step 2) of thermolysis is carried out without solvent and under vacuum.
  • the thiolactone of formula (I) is preferably purified, for example by chromatography on a silica column.
  • R 1 ' , R 2' , R 3 ' and R 4' which may be identical or different, represent a hydrogen atom or a group chosen from alkyl, acyl, aryl, heteroaryl, saturated or unsaturated cycloalkyl and saturated heterocycloalkyl groups; or unsaturated, the radicals R 1 ' , R 2' , R 3 ' and R 4' may also together form a saturated or unsaturated cycloalkyl or heterocycloalkyl group or an aryl or heteroaryl group; and
  • R 5 ' , R 6' and R 7 ' are defined according to one of two options (i) or (ii):
  • R 5 ' is selected from cyano group and phthalimido group
  • R 6 ' and R 7' which are identical or different, are chosen from a hydrogen atom, an alkyl group, an acyl group, an aryl group, a heteroaryl group, an aralkyl group, a saturated or unsaturated cycloalkyl group and a saturated or unsaturated heterocycloalkyl group, said alkyl, acyl, aryl, heteroaryl, aralkyl, saturated or unsaturated cycloalkyl and saturated or unsaturated heterocycloalkyl groups which may be substituted with a group X selected from the following groups: P (0) (OR 8 ) (OR 8 ' ) in which the radicals R 8 and R 8' , which may be identical or different, represent a hydrogen atom or an alkyl radical; C n F 2 n + i wherein n is an integer from 1 to 20; SiR 9 p (OR 10 ) 3 -p in which the radicals R 9 and R 10 , which may be identical or different,
  • R 5 ' , R 6' and R 7 ' are such that together they form a polymer chain P 1 .
  • R 1 ' , R 2' , R 3 ' and R 4' represent a hydrogen atom or an alkyl group.
  • R 1 ' (respectively R 2' ) is an alkyl group, especially a methyl group, and R 2 ' (respectively R 1' ) is a hydrogen atom.
  • At least one of the groups R 3 ' or R 4' is a hydrogen atom and more preferably both the groups R 3 ' and R 4' are hydrogen atoms.
  • At least one of the groups R 6 ' or R 7' is a hydrogen atom, and more preferably the two groups R 6 ' and R 7' are hydrogen atoms.
  • the substituted thiolactones of formula (I) obtainable by carrying out the process according to the present invention, and in particular the thiolactones of formula ( ⁇ ) according to the second subject of the present invention may advantageously be used to the synthesis of polymers or for the functionalization of particles, flat surfaces of the metal, glass, ceramic or polymer type.
  • the third subject of the present invention is also the use of at least one substituted thiolactone of formula ( ⁇ ), for the synthesis of polymers or for the functionalization of particles, of flat surfaces of metal, glass or ceramic type, or of polymers.
  • the thiolactones of formula (I), and in particular of formula ( ⁇ ) may be engaged in a polymerization reaction comprising at least one reaction step of a thiolactone of formula (I), in particular of formula ( ⁇ ) with a nucleophilic compound which makes it possible to open the thiolactone ring and to obtain a thiol which can then be engaged in an addition or condensation polymerization process with, for example, a diacrylate-type monomer such as described in the reference by Yu et al. [Polym. Chem. , 2015, 6, 1527-1532].
  • grafting substituted thiolactones of formula (I) (respectively of formula ( ⁇ )) on a solid surface or on a polymer in the liquid state, said surface or said polymer comprising chemical functions capable of reacting with one of the groups R 1 , R 2 , R 3 , R 4 , R 5 , R 6 or R 7 (respectively R 1 ' , R 2' , R 3 ' , R 4' , R 5 , R 6 or R 7 ' ) thiolactones of formula (I) (respectively ( ⁇ )), in order to form a covalent bond, or strong interactions of the hydrogen bonding type.
  • a thiolactone comprising a phosphonate group as an X substituent of R 6 or R 7 on a metal surface.
  • this first embodiment after functionalization, the integrity of the thiolactone ring is preserved.
  • the present invention is illustrated by the following exemplary embodiments, to which it is however not limited.
  • Step 1 Preparation of S- (cyanomethyl) -CH3-methylbutan-2-yl carbonodithioate (Xanthate of formula (II);
  • the crude reaction product was purified by chromatography on silica (eluent ethyl acetate / hexane (2: 8, v: v)) to recover the xanthate XA 2 which did not reacted on the one hand, and the mono-adduct XA2PH on the other hand (1.9 g, 91% yield, yellow oil).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
EP18704047.2A 2017-01-18 2018-01-16 Verfahren zur herstellung von thiolactonen, mit diesem verfahren gewonnene thiolactone und verwendungen davon Withdrawn EP3571188A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1750384A FR3061907A1 (fr) 2017-01-18 2017-01-18 Procede de preparation de thiolactones, thiolactones obtenues par ledit procede et utilisations
PCT/FR2018/050099 WO2018134510A1 (fr) 2017-01-18 2018-01-16 Procédé de préparation de thiolactones, thiolactones obtenues par ledit procédé et utilisations

Publications (1)

Publication Number Publication Date
EP3571188A1 true EP3571188A1 (de) 2019-11-27

Family

ID=58547665

Family Applications (1)

Application Number Title Priority Date Filing Date
EP18704047.2A Withdrawn EP3571188A1 (de) 2017-01-18 2018-01-16 Verfahren zur herstellung von thiolactonen, mit diesem verfahren gewonnene thiolactone und verwendungen davon

Country Status (4)

Country Link
US (1) US20190359603A1 (de)
EP (1) EP3571188A1 (de)
FR (1) FR3061907A1 (de)
WO (1) WO2018134510A1 (de)

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2844264B1 (fr) 2002-09-11 2006-10-20 Rhodia Chimie Sa Nouveaux composes comprenant un groupement thiocarbonylsulfanyle utiles pour la synthese de composes alpha-perfluoroalkylamines par voie radicalaire
EP2751142B1 (de) * 2011-08-31 2015-12-09 Bridgestone Corporation Funktionalisierte polymere mit lactonen oder thiolaktonen mit einer geschützten aminogruppe
FR3024734B1 (fr) * 2014-08-08 2018-03-02 Xanchem Polymere dote de proprietes d'adherence

Also Published As

Publication number Publication date
FR3061907A1 (fr) 2018-07-20
US20190359603A1 (en) 2019-11-28
WO2018134510A1 (fr) 2018-07-26

Similar Documents

Publication Publication Date Title
JP4886109B2 (ja) リビング性を有する重合方法およびその方法で製造されるポリマー
EP0991683B1 (de) Verfahren zur herstellung von blockcopolymeren durch kontrollierte radikalische polymerisation
JP3696203B2 (ja) リビングタイプのフリーラジカル重合制御剤、重合方法、これを用いたエマルジョン及びポリマー
AU2007347458B2 (en) Process for transforming the end groups of polymers
EP1527079B1 (de) Alkoxyamine abgeleitet aus beta-phosphorierten nitroxiden
FR2773161A1 (fr) Procede de synthese de polymeres a blocs
WO1999035177A1 (fr) Procede de synthese de polymeres a blocs par polymerisation radicalaire controlee a partir de composes dithiocarbamates
EP1319027B1 (de) Verfahren zur herstellung von blockcopolymeren durch eine kontrollierte radikalpolymerisation in gegenwart von einer disulfidverbindung
JP3299542B2 (ja) 新規な開環モノマー
WO2003082928A1 (en) Control agents for living-type free radical polymerization and methods of polymerizing
EP3571188A1 (de) Verfahren zur herstellung von thiolactonen, mit diesem verfahren gewonnene thiolactone und verwendungen davon
EP3472174B1 (de) Verfahren zur herstellung von substituierten thiolactonen, neue substituierte thiolactone und verwendungen davon
FR3075199A1 (fr) Nouvelles bis-thiolactones substituees symetriques, leur procede de preparation et utilisations
EP1064260A1 (de) Emulsionspolymerisation mit einer verbindung, die gleichzeitig ein tensid und initiator ist
JP2024527035A (ja) チオノラクトン、合成方法、コモノマーとしての並びにポリマーの官能化及び分解のための使用
US7157537B2 (en) α-Halogenated acid esters with polyvalent alcohols as atom transfer radical polymerization initiators
WO2023175121A1 (fr) Procédé de polymérisation par voie radicalaire de thionolactides
JP3673788B2 (ja) ポリスチレン型グラフト高分子及びその製造方法
FR3064637A1 (fr) Procede de synthese de copolymeres brosses ou de gels brosse, nouveaux copolymeres et leurs utilisations
FR2829140A1 (fr) Procede de synthese de polymeres a fonctions thiols

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20190716

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20200806

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20210625

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20211106