Patent Application
20190202849
The present invention relates to the field of thiolactones.
More particularly, the present invention relates to a process for preparing substituted thiolactones of formula (I), novel substituted thiolactones of formula (I′) able to be obtained by carrying out this process, the use of substituted thiolactones of formula (I) or of formula (I′) for the preparation of polymers or for surface functionalization or polymer functionalization.
Thiolactones are heterocyclic compounds analogous to lactones, in which an oxygen atom is replaced by a sulfur atom. The sulfur atom is located in the ring and is adjacent to a carbonyl group. The heterocycle of thiolactones may be substituted by at least one chemical group, in particular by an alkyl or aryl group.
Several processes for synthesizing thiolactones have already been proposed.
F. Korte et al. (Chem. Ber., 1961, 94, 1966), for example, proposed either carrying out thermal cyclization of a mercaptocarboxylic acid bearing an alkyl substituent, or directly substituting a thiolactone with an alkyl radical in the presence of an alkyl halide group (R—X) and lithium dialkylamide (LiNR′2). These two synthesis routes may be represented by the following reaction scheme (1):
According to this synthesis route, only the final step of thermal cyclization is general, with the preceding steps leading to the mercaptocarboxylic acid and the reagents used being specific to the type of R group that it is desired to introduce to the heterocycle. Moreover, these two synthesis routes do not make it possible to introduce substituents other than alkyl groups.
A more recent synthesis process makes it possible to obtain thiolactones having alkyl or aryl groups (J.-J. Filippi et al., Tet. Lett., 2006, 47, 6067). This process is based on a process of catalytic isomerization of a thionolactone to a thiolactone in the presence of boron trifluoride (BF3) and diethyl ether (Et2O) in an organic solvent such as toluene at reflux, according to the following reaction scheme (2):
However, this process uses a catalyst of Lewis acid type (boron trifluoride) and cannot be readily used for the synthesis of thiolactones bearing substituents other than alkyl or phenyl groups, such as complex organic functions and/or those that are incompatible with this type of catalyst. Moreover, the isolated thiolactone yields are often low. Finally, this process requires the synthesis of starting thionolactones from the corresponding lactones.
There is therefore a need for a process which makes it possible to synthesize thiolactones substituted by various functional groups in a flexible and simple manner, and according to a process which is both efficient and economical.
Therefore, the first subject of the present invention is a process for preparing substituted thiolactones of the following formula (I):
wherein:
in which the symbol # is the point of attachment of said group to R6 and in which Y has the same meaning as that chosen for the radical Y of the formula (I), OH; P(O)(OR7)(OR7′) in which the radicals R7 and R7′, which are identical or different, represent a hydrogen atom or an alkyl radical; CnF2n+1 in which n is an integer ranging from 1 to 20; SiR8p(OR9)3-p, in which the radicals R8 and R9, which are identical or different, represent a hydrogen atom or an alkyl radical and p is an integer equal to 0, 1 or 2; BF3M+, in which M=K or Na; B(OR10)2, in which the two radicals R10, which are identical or different, represent a hydrogen atom, an alkyl radical or form a carbon-based ring with the two oxygen atoms to which they are bonded; OR11, in which R11 represents a hydrogen atom or an alkyl, aryl or aralkyl radical; O(C═O)R12, in which R12 represents a hydrogen atom or an alkyl, aryl or aralkyl radical; O(C═O)OR13, in which R13 represents a hydrogen atom or an alkyl, aryl or aralkyl radical; N+R14R14′R14″A−, in which the radicals R14, R14′ and R14″, which are identical or different, represent a hydrogen atom or an alkyl, aryl or aralkyl radical and A represents a chlorine or bromine atom; NR15′(C═O)R15, in which the radicals R15 and R15′, which are identical or different, represent a hydrogen atom or an alkyl or aryl radical or are connected together and form a ring such as a pyrrolidone or caprolactam ring; NR16′(C═O)OR16, in which R16 et R16′, which are identical or different, represent a hydrogen atom or an alkyl, aryl or aralkyl radical; CN; a halogen atom chosen from Cl, F, and Br; NCS; OCH2-epoxy; COOR17, in which R17 represents a hydrogen atom, an alkyl, aryl or aralkyl radical; CONR18R18′, in which R18 and R18′, which are identical or different, represent a hydrogen atom or an alkyl or aryl radical; SO2R19, in which R19 represents an alkyl or aryl radical; azide N3 and alkyne,
it being understood that:
1) when A1=A2=H and e=0, then W represents a hydrogen atom and Z1 represents a group selected from the groups alkyl; aryl; P(O)(OR7)(OR7′), in which the radicals R7 and R7′, which are identical or different, represent a hydrogen atom or an alkyl radical; CnF2n+1 in which n is an integer ranging from 1 to 20; SiR8p(OR9)3-p, in which the radicals R8 and R9, which are identical or different, represent a hydrogen atom or an alkyl radical and p is an integer equal to 0, 1 or 2; BF3M+, in which M=K or Na; B(OR10)2, in which the two radicals R10, which are identical or different, represent a hydrogen atom, an alkyl radical or form a carbon-based ring with the two oxygen atoms to which they are bonded; OR11, in which R11 represents a hydrogen atom or an alkyl, aryl or aralkyl radical; O(C═O)R12, in which R12 represents a hydrogen atom or an alkyl, aryl or aralkyl radical; O(C═O)OR13, in which R13 represents a hydrogen atom or an alkyl, aryl or aralkyl radical; N+R14R14′R14″A−, in which the radicals R14, R14′ and R14″, which are identical or different, represent a hydrogen atom or an alkyl, aryl or aralkyl radical and A represents a chlorine or bromine atom; NR15′(C═O)R15, in which the radicals R15 and R15′, which are identical or different, represent a hydrogen atom or an alkyl or aryl radical or are connected together and form a ring such as a pyrrolidone or caprolactam ring; NR16′(C═O)OR16, in which R16 and R16′, which are identical or different, represent a hydrogen atom or an alkyl, aryl or aralkyl radical; CN; a halogen atom chosen from Cl, F, and Br; NCS; OCH2-epoxy; COOR17, in which R17 represents a hydrogen atom, an alkyl, aryl or aralkyl radical; CONR18R18′, in which R18 and R18′, which are identical or different, represent a hydrogen atom or an alkyl or aryl radical; SO2R19, in which R19 represents an alkyl or aryl radical; azide N3 and alkyne; and a thiolactone ring of formula
in which the symbol # is the point of attachment of the thiolactone ring to L and in which Y has the same meaning as that chosen for the radical Y of the formula (I),
2) when A1=A2=H, m=1 and e=0, then W represents a hydrogen atom and Z1 may also represent a hydrogen atom;
3) when A1=A2=H, e=1 and m=0, then Z1 and W are identical and represent —CH2— or CO;
4) when A1=A2=H, e=1, m=1 and T=CH2 then Z1=W=—CH2,
5) when A1=A2=F, e=0 and m=0, then W represents a fluorine atom and Z1=F or represents a linear or branched chain OCqF2q+1 in which q is an integer ranging from 1 to 5, [OCF2CF(CF3)]rOC3F7, with r=an integer ranging from 0 to 20, OC2F4SO2F, OCF2CF(CF3)OC2F4SO2F, or OCF2CF(CF3)OC2F4CO2CH3;
6) when A1=A2=F, e=1 and m=0, then W=Z1=CF2 and T=(CF2)s, with s=an integer ranging from 1 to 5; and
7) when A1=H, A2=F, and e=m=0, then W represents a hydrogen atom and Z1=F or CnF2n+1, in which n is an integer ranging from 1 to 20;
said process 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:
wherein:
with a monomer comprising at least one ethylenic unsaturation of the following formula (III):
wherein:
it being understood that:
1) when A1=A2=H and e=0, then W represents a hydrogen atom and Z2 represents a group selected from the groups alkyl; aryl; P(O)(OR7)(OR7′), in which the radicals R7 and R7′, which are identical or different, represent a hydrogen atom or an alkyl radical; CnF2n+1, in which n is an integer ranging from 1 to 20; SiR8p(OR9)3-p, in which the radicals R8 and R9, which are identical or different, represent a hydrogen atom or an alkyl radical and p is an integer equal to 0, 1 or 2; BF3M+, in which M=K or Na; B(OR10)2, in which the two radicals R10, which are identical or different, represent a hydrogen atom, an alkyl radical or form a carbon-based ring with the two oxygen atoms to which they are bonded; OR11, in which R11 represents a hydrogen atom or an alkyl, aryl or aralkyl radical; O(C═O)R12, in which R12 represents a hydrogen atom or an alkyl, aryl or aralkyl radical; O(C═O)OR13, in which R13 represents a hydrogen atom or an alkyl, aryl or aralkyl radical; N+R14R14′R14″A−, in which the radicals R14, R14′ and R14″, which are identical or different, represent a hydrogen atom or an alkyl, aryl or aralkyl radical and A represents a chlorine or bromine atom; NR15′(C═O)R15, in which the radicals R15 and R15′, which are identical or different, represent a hydrogen atom or an alkyl or aryl radical or are connected together and form a ring such as a pyrrolidone or caprolactam ring; NR16′(C═O)OR16, in which R16 and R16′, which are identical or different, represent a hydrogen atom or an alkyl, aryl or aralkyl radical; CN; a halogen atom chosen from Cl, F, and Br; NCS; OCH2-epoxy; COOR17, in which R17 represents a hydrogen atom, an alkyl, aryl or aralkyl radical; CONR18R18′, in which R18 and R18′, which are identical or different, represent a hydrogen atom or an alkyl or aryl radical; SO2R19, in which R19 represents an alkyl or aryl radical; azide N3, alkyne and C2H3 (i.e. CH═CH2);
2) when A1=A2=H, m=1 and e=0, then W represents a hydrogen atom and Z2 may also represent a hydrogen atom,
3) when A1=A2=H, e=1 and m=0, then Z2 and W are identical and represent —CH2— or CO;
4) when A1=A2=H, e=1, m=1 and T=CH2, then Z2=W=—CH2,
5) when A1=A2=F, e=0 and m=0, then W represents a fluorine atom and Z2=F or represents a linear or branched chain OCqF2q+1 in which q is an integer ranging from 1 to 5, [OCF2CF(CF3)]rOC3F7, with r=an integer ranging from 0 to 20, OC2F4SO2F, OCF2CF(CF3)OC2F4SO2F, or OCF2CF(CF3)OC2F4CO2CH3; and
6) when A1=A2=F, e=1 and m=0, then W=Z2=CF2 and T=(CF2)s, with s=an integer ranging from 1 to 5;
7) when A1=H, A2=F, and e=m=0, then W represents a hydrogen atom and Z2=F or CnH2n+1, in which n is an integer ranging from 1 to 20;
to form a monoadduct of the following formula (IV):
wherein:
it being understood that:
1) when A1=A2=H and e=0, then W represents a hydrogen atom and Z3 represents a group selected from the groups alkyl; aryl; P(O)(OR7)(OR7′), in which the radicals R7 and R7′, which are identical or different, represent a hydrogen atom or an alkyl radical; CnF2n+1, in which n is an integer ranging from 1 to 20; SiR8p(OR9)3-p, in which the radicals R8 and R9, which are identical or different, represent a hydrogen atom or an alkyl radical and p is an integer equal to 0, 1 or 2; BF3M+, in which M=K or Na; B(OR10)2, in which the two radicals R10, which are identical or different, represent a hydrogen atom, an alkyl radical or form a carbon-based ring with the two oxygen atoms to which they are bonded; OR11, in which R11 represents a hydrogen atom or an alkyl, aryl or aralkyl radical; O(C═O)R12, in which R12 represents a hydrogen atom or an alkyl, aryl or aralkyl radical; O(C═O)OR13, in which R13 represents a hydrogen atom or an alkyl, aryl or aralkyl radical; N+R14R14′R14″A−, in which the radicals R14, R14′ and R14″, which are identical or different, represent a hydrogen atom or an alkyl, aryl or aralkyl radical and A represents a chlorine or bromine atom; NR15′(C═O)R15, in which the radicals R15 and R15′, which are identical or different, represent a hydrogen atom or an alkyl or aryl radical or are connected together and form a ring such as a pyrrolidone or caprolactam ring; NR16′(C═O)OR16, in which R16 and R16′, which are identical or different, represent a hydrogen atom or an alkyl, aryl or aralkyl radical; CN; a halogen atom chosen from Cl, F, and Br; NCS; OCH2-epoxy; COOR17, in which R17 represents a hydrogen atom, an alkyl, aryl or aralkyl radical; CONR18R18′, in which R18 and R18′, which are identical or different, represent a hydrogen atom or an alkyl or aryl radical; SO2R19, in which R19 represents an alkyl or aryl radical; azide N3, alkyne, and a group of the following formula (V):
in which the symbol # is the point of attachment of the group of formula (V) to L and R1, R2, R3, R4, R5 and Y respectively have the same meaning as that chosen for R1, R2, R3, R4, R5 and Y in the formula (IV),
2) when A1=A2=H, m=1 and e=0, then W represents a hydrogen atom and Z3 may also represent a hydrogen atom,
3) when A1=A2=H, e=1 and m=0, then Z3 and W are identical and represent —CH2— or CO;
4) when A1=A2=H, e=1, m=1 and T=CH2, then Z3=W=—CH2,
5) when A1=A2=F, e=0 and m=0, then W represents a fluorine atom and Z3=F or represents a linear or branched chain OCqF2q+1 in which q is an integer ranging from 1 to 5, [OCF2CF(CF3)]rOC3F7, with r=an integer ranging from 0 to 20, OC2F4SO2F, OCF2CF(CF3)OC2F4SO2F, or OCF2CF(CF3)OC2F4CO2CH3; and
6) when A1=A2=F, e=1 and m=0, then W=Z3=CF2 and T=(CF2)s, with s=an integer ranging from 1 to 5;
7) when A1=H, A2=F, and e=m=0, then W represents a hydrogen atom and Z3=F or CnF2n+1, in which n is an integer ranging from 1 to 20;
then
2) a step of thermolysis of the monoadduct of formula (IV) obtained above in the preceding step, to form a corresponding substituted thiolactone of formula (I).
The process for preparing the substituted thiolactones of formula (I) in accordance with the invention may be represented by the following reaction scheme (3):
By virtue of the process in accordance with the present invention, and as described above, it is now possible to simply and quickly, and with a good yield, obtain thiolactones substituted by various organic groups.
According to a first particularly advantageous embodiment form, the process of the invention leads to the formation of a dithiolactone of formula (Ia), in which A1, A2, L, m and Y have the same meaning as in formula (I) and W=H, said dithiolactone being obtained according to the reaction scheme (4a)
in which
According to another particularly advantageous embodiment form, the process of the invention leads to the formation of a dithiolactone of formula (Ib), in which A1, A2 and Y have the same definition as in formula (I), m=0, W and Z1=CO, e=1, T=NR6, in which R6 has the same meaning as that chosen for the radical R6 of formula (I), said dithiolactone being obtained according to the following reaction scheme (4b):
in which the monomer comprising an ethylenic unsaturation of general formula (IIIb) corresponds to a monomer of formula (III) in which A1 and A2 have the same meaning as in formula (I), m=0, Z2=W=CO, e=1 and T=NR6 with R6=the same meaning as that chosen for the radical R6 of formula (I), and
According to the invention, the thiolactones of formula (I) in which A1 and A2 represent a hydrogen atom are preferred.
The nature of the linker arm L is not critical. The linker arm L may especially be an optionally fluorinated or perfluorinated hydrocarbon-based chain, in particular optionally fluorinated or perfluorinated linear alkylene, which may be interrupted by one or more heteroatoms, preferably by one or more oxygen atoms and preferentially at least one oxygen atom is in the penultimate position, said optionally fluorinated or perfluorinated hydrocarbon-based chain having from 1 to 100 carbon atoms, preferentially from 1 to 12 carbon atoms, and even more preferentially from 1 to 3 carbon atoms.
According to a particularly preferred embodiment form of the invention, the linker arm L is a linear alkylene chain having from 1 to 8 carbon atoms.
The alkyl radicals mentioned for R1, R2, R3, R4, R5, R6, Y and the radicals Z (Z1, Z2 and Z3) may be linear, branched, substituted or unsubstituted and comprise from 1 to 12 carbon atoms. They are preferably chosen from methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, neo-pentyl, tert-pentyl, hexyl, n-octyl, iso-octyl, 2-ethyl-1-hexyl, 2,2,4-trimethylpentyl, nonyl, decyl, dodecyl and benzyl radicals. Among such radicals, methyl, ethyl, n-propyl, iso-propyl and n-butyl radicals are most particularly preferred.
For the purposes of the present invention, an acyl group denotes a group of formula —C(═O)-D, in which D denotes a hydrogen atom or a linear or branched, saturated or unsaturated hydrocarbon-based chain comprising from 1 to 12 carbon atoms. Among such acyl groups mentioned for R1, R2, R3, R4, R5, R6, Z1, Z2 and Z3, mention may especially be made of formyl, acetyl, propanoyl pivaloyl groups.
For the purposes of the invention, aryl group is intended to mean a monocyclic or polycyclic aromatic hydrocarbon-based group that is optionally monosubstituted or polysubstituted. By way of aryl radical mentioned for R1, R2, R3, R4, R5, R6, Z1, Z2 and Z3, mention may in particular be made of naphthyl, anthranyl, phenanthryl, o-tolyl, p-tolyl, xylyl, ethylphenyl, mesityl and phenyl groups. Among such groups, the phenyl group is particularly preferred.
For the purposes of the present invention, the cycloalkyl group is a saturated cyclic group comprising from 3 to 10 carbon atoms. Among such cycloalkyl groups mentioned for R1, R2, R3, R4, R5 and R6, mention may in particular be made of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl groups.
Still for the purposes of the present invention, a heterocycloalkyl group is a saturated cyclic group comprising from 3 to 9 carbon atoms and at least one heteroatom chosen from N, O, P, Si and S. Among such heterocycloalkyl groups mentioned for R1, R2, R3, R4, R5 and R6, mention may in particular be made of oxacyclopropanyl, azacyclopropanyl, thiacyclopropanyl, tetrahydrofuranyl, pyrrolidinyl, tetrahydrothiophenyl, tetrahydropyranyl, piperidinyl, piperazinyl and thiacyclohexane groups.
For the purposes of the present invention, a heterocycloaryl group is a monocyclic or polycyclic aromatic group comprising from 5 to 6 carbon atoms and at least one heteroatom chosen from N, O, P, Si and S. Among such heterocycloaryl groups mentioned for R1, R2, R3, R4, R5 and R6, mention may in particular be made of furanyl, thiophenyl, pyrrolyl, pyridinyl, pyranyl, oxazinyl, thazinyl, pyrimidinyl, piperazinyl and thiinyl groups.
In a particular embodiment, R1, R2, R3 and R4, which are identical or different, represent a hydrogen atom or an alkyl group, of course with the proviso, as indicated above, that at least one of the groups R1 and R3 is other than a hydrogen atom.
According to a particularly preferred embodiment form of the invention, R1 (respectively R3) is an alkyl group, especially a methyl group, and R3 (respectively R1) is a hydrogen atom.
Preferably, at least one of the groups R2 and R4 is other than a hydrogen atom.
Further preferably, R2 (respectively R4) is an alkyl group, especially a methyl group, and R4 (respectively R2) is a hydrogen atom or an alkyl group, especially a methyl group.
Finally, according to the present invention, polymer chain is intended to mean any linked sequence of monomer units obtained by a radical polymerization process controlled by reversible addition-fragmentation (RAFT/MADIX process as described, for example, by Moad, G. et al., Aust. J. Chem., 2012, 65(8), 985-1076) or atom transfer (ATRP process, i.e. Atom Transfer Radical Polymerization as described, for example, by Matyjaszewski, K., Chem. Rev., 2001, 101(9), 2921-2990), carried out such that the terminal monomer unit connected respectively to the sulfur atom of the thiocarbonylthio group (RAFT/MADIX), or halogen (Cl, Br) group for ATRP, is of acrylate type, for example methyl acrylate, or acrylamido, such as N-isopropylacrylamide.
For the purposes of the present invention, in the compounds of formula (I), (III) or (IIIa) and (IV) or (IVa), when e=0 then T is absent and W and, respectively, Z1, Z2 and Z3 are not connected.
The process in accordance with the invention is preferably carried out for preparing substituted thiolactones of formula (I) as defined above, in which:
According to a particularly preferred embodiment form of the invention, R5 is an alkyl group, especially a methyl group.
The process in accordance with the invention is preferably carried out to prepare thiolactones of formula (I) in which e=0, m=1 and Z1 is other than a hydrogen atom.
According to a particularly advantageous embodiment form, the process of the invention leads to the formation of a thiolactone of formula (I) chosen from:
When they are not commercially available, the xanthates of formula (II) may be obtained according to a process analogous to that used in international application WO 2004/024681 and consisting in:
a) in a first step, reacting, in an organic solvent, an alcohol of following formula (VI):
in which the radicals R1, R2, R3 and R4 have the same meaning as in the compounds of formula (II) above
with carbon disulfide in the presence of a base to obtain a salt of following formula (VII):
in which the radicals R1, R2, R3 and R4 have the same meaning as in the xanthate of formula (II) above, and J+ is a cation chosen from alkali metals, such as a K+ or Na+ cation, then
b) in a second step, reacting the compound of formula (VII) obtained above in the preceding step with a compound of following formula (VIII):
in which R5 and X have the same meaning as in the xanthate of formula (II) above, to obtain a corresponding xanthate of formula (II).
The first step a) of preparing a compound of formula (VII) is preferably carried out at room temperature in an organic solvent such as tetrahydrofuran and using a strong base, preferably potassium hydroxide. The duration of step a) is generally from approximately 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 an ice bath, since the reaction of addition of the compound of formula (VIII) is highly exothermic.
Once the addition of the compound of formula (VIII) has finished, the reaction is preferably carried out at room temperature for a duration of approximately 2 to 4 hours. When the reaction has finished, the xanthate of formula (II) thus obtained is filtered, then the filtrate is preferably concentrated under vacuum. The xanthate of formula (II) may subsequently be used in the process in accordance with the present invention without additional purification.
According to a first embodiment of the invention, the xanthate of formula (II) is O-1,2-dimethylpropyl S-methoxycarbonylmethyl xanthate (XA1) or O-1,2-dimethylpropyl S-(1-methoxycarbonyl)ethyl xanthate (XA2).
According to a second embodiment of the invention, the xanthate of formula (II) is as defined in the invention [i.e. with R1, R2, R3, R4, Y, X and R5 as defined in the invention], excluding the xanthates of the first embodiment above.
Step 1) of preparing the monoadduct of formula (IV) of the process in accordance with the invention may 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 preferentially in an organic solvent. The organic solvent of use during this step 1) is thus preferably chosen from toluene, tetrahydrofuran (THF), ethyl acetate and 1,4-dioxane. Among such organic solvents, toluene is particularly preferred.
For the purposes of the present invention, radical initiator is intended to mean a chemical entity capable of forming free radicals, that is to say a chemical entity having one or more unpaired electrons in its outer shell.
According to the process in accordance with the invention, the radical initiator used during step 1) is preferably chosen from organic peroxides, azo derivatives, redox couples that generate radicals and redox systems.
Among the 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 peroxypivalate, t-butyl peroxypivalate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, dicumyl peroxide, dibenzoyl peroxide, potassium peroxydisulfate, sodium peroxydisulfate and ammonium peroxydisulfate. Among these organic peroxides, LPO is particularly preferred.
Among the 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([N,N′-dimethyleneisobutyramidine) dihydrochloride, 2,2′-azobis(2-amidinopropane) dihydrochloride, 2,2′-azobis(N,N′-dimethylene isobutyramine), 2,2′-azobis(2-methyl-N-[1, bis(hydroxymethyl)-2-hydroxyethyl]propionamide), 2,2′-azobis(2-methyl-N-[1,1-bis(hydroxymethyl)propionamide], 2,2′-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2′-azobis(isobutyramide) dihydrate, 2,2′-azobis(2,2,4-trimethylpentane) and 2,2′-azobis(2-methylpropane).
The redox systems are for example chosen from systems comprising combinations such as:
Among such redox systems, the combination of ammonium persulfate and sodium formaldehyde sulfoxylate is most particularly preferred.
Moreover, during step 1), the radical initiator may be added to the reaction medium all at once or in several goes, that is to say portionwise. According to a preferred embodiment form of the process of the invention, the radical initiator is added to the reaction medium portionwise.
According to a first embodiment of the invention, the monoadduct of formula (IV) as obtained at the end of step 1) is chosen from O-1,2-dimethylpropyl S-(1-(dimethylphosphoryl)-3-(methoxycarbonyl))propyl xanthate (XA1VP), O-1,2-dimethylpropyl S-(1-(diethylphosphoryl)-4-(methoxycarbonyl))pent-2-yl xanthate (XA2AP), O-1,2-dimethylpropyl S-(1-(diethylphosphoryl)-4-(methoxycarbonyl))but-2-yl xanthate (XA3AP), O-1,2-dimethylpropyl S-2-(methoxycarbonyl)non-4-yl xanthate (XA4H), O-1,2-dimethylpropyl S-1-(methoxycarbonyl)oct-3-yl xanthate (XA5H), methyl-5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heptadecafluoro-2-methyl-4-((((3-methylbutan-2-yl)oxy)carbonothioyl)thio)dodecanoate (XA6DF), the monoadduct of example 7 below (XA7MAL) and methyl 5,5,6,6,7,7,8,8,8-nonafluoro-2-methyl-4-((((3-methylbutan-2-yl)oxy)carbonothioyl)thio)octanoate (XA8HF).
According to a second embodiment of the invention, the monoadduct of formula (IV) is as defined in the invention [i.e. with R1, R2, R3, R4, Y, X, R5, Z3, W, T, e, L and m as defined in the invention], excluding the monoadducts of the first embodiment above.
The monomers of formula (III) are preferably chosen from compounds which are monomers that are only slightly, or not at all, polymerizable under the temperature and pressure conditions used during step 1) of the process in accordance with the invention, that is to say which lead to a monoadduct of formula (IV) without a notable presence of diadduct, triadduct, etc. Among such monomers of formula (III), mention may in particular be made of alkenes and allylic compounds.
Among the alkenes of use as monomer of formula (III), mention may in particular be made of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, perfluorohexylethylene and perfluorooctylethylene.
Among allylic compounds of use as monomer of formula (III), mention may in particular be made of allylic alcohol, N-allyl benzamide, ethyl N-allyl carbamate, tert-butyl N-allyl carbamate, 2-allyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 2-allyl-6-methyl-1,3,6,2-dioxazaborocane-4,8-dione, allylboronic acid, diethyl allylphosphonate, allyl phosphonic dichloride, dimethyl allylphosphonate, allyl cyanide, allyl isothiocyanate, allyl glycidyl ether, allyl benzyl ether, allyl phenyl ether, allyl butyl ether, allyl ethyl ether, allyl methylsulfone, allyl phenylsulfone, allyl chloride, allyl bromide and allyl fluoride.
The monomers of formula (III) may also be chosen from polymerizable compounds, in particular from styrene vinyl compounds, acrylic acid and acrylates, and acrylamide and derivatives thereof. In this case the synthesis is not selective but predominantly obtaining the monoadduct may be promoted by using a smaller amount of monomer of formula (III) than the amount of xanthate of formula (II) so as to limit as far as possible the risk of polymerization of the monomer of formula (III). Moreover, the monoadduct of formula (IV) may be isolated by conventional techniques that are within the grasp of those skilled in the art.
Among the vinyl compounds of use as monomer of formula (III), mention may in particular be made of dimethyl vinylphosphonate, diethyl vinylphosphonate, vinylphosphonic acid, N-vinyl monomers such as N-vinylpyrrolidone, N-vinylcaprolactam and N-methyl-N-vinylacetamide, vinylsulfones such as methyl vinylsulfone and phenyl vinylsulfone, vinylsilanes such as vinyltrimethylsilane and vinyltrimethoxysilane, and vinyl esters, such as vinyl acetate, vinyl pivalate, vinyl butyrate, vinyl valerate, vinyl propionate, vinyl benzoate, vinyl neodecanoate and vinyl trifluoroacetate.
Among the styrene compounds of use as monomer of formula (III), mention may in particular be made of styrene, vinylbenzoic acid, 3-chlorostyrene, 2-methylstyrene, p-t-butylstyrene, p-methoxystyrene, p-methylstyrene, p-chloromethylstyrene and vinylphenylboronic acid.
Among the acrylates, mention may in particular be made of methyl acrylate, n-butyl acrylate, t-butyl acrylate and 2-hydroxyethyl acrylate.
Among the acrylamide derivatives, mention may in particular be made of N-isopropylacrylamide, N,N-dimethylacrylamide, N-t-butylacrylamide and N-octylacrylamide.
The monomers of formula (III) are generally commercially available. When they are not commercially available, they may be readily obtained by synthesis routes that are well known to those skilled in the art.
Step 1) of the process in accordance with the invention is generally carried out at a temperature varying from approximately 10 to 140° C., and preferably from approximately 40 to 110° C., and even more preferentially between approximately 65 and 90° C.
The duration of said step 1) generally varies from approximately 3 to 48 hours, and even more preferentially from approximately 4 to 24 hours.
According to a particular and preferred embodiment form of the invention, the monoadduct of formula (IV) obtained at the end of step 1) is purified, for example by silica gel chromatography, before being used in the second step of thermolysis.
Step 2) of thermolysis of the process according to the present invention may be carried out with or without solvent. According to a preferred embodiment form of the invention, the step of thermolysis is carried out without solvent. The thermolysis temperature is generally between 40 and 210° C., preferably between 100 and 200° C. and more particularly between 160 and 190° C.
The step of thermolysis is generally carried out at a temperature sufficient to decompose the monoadduct of formula (IV).
In the present invention, the expression “thermolysis” means a thermal decomposition. This is a chemical decomposition reaction caused by heat. In the present case, the action of the heat leads to the decomposition of the monoadduct of formula (IV), enabling the formation of the thiolactone of formula (I).
In other words, step 2) of the process of the invention does not employ reagents other than the monoadduct of formula (IV) resulting from step 1). Only the action of heat makes it possible to obtain the thiolactones of formula (I).
Surprisingly, the monoadduct of formula (IV) obtained in step 1) has a suitable chemical structure, especially in terms of the definition of the groups R1, R2, R3, R4, R5, L (if m=1), Y, X, W, T (if e=1) and Z3, to enable the formation of a substituted thiolactone of formula (I) by thermolysis. In other words, cyclization to give thiolactone (I) is favoured.
When the step of thermolysis is carried out in a solvent, then said solvent is preferably chosen from high boiling point solvents (that is to say solvents having a boiling point greater than or equal to the thermolysis temperature), such as, for example, 1,2-dichlorobenzene.
Moreover, the step of thermolysis may be carried out at atmospheric pressure or under vacuum, especially in the latter case, to eliminate the volatile by-products which may have formed during the reaction.
According to a particular embodiment, the step of thermolysis is carried out in a closed container (e.g. Schlenk tube) and preferably under vacuum.
According to a particular and preferred embodiment form of the invention, the step of thermolysis is carried out without solvent and under vacuum.
At the end of step 2) of thermolysis, the thiolactone of formula (I) is preferably purified, for example by silica column chromatography.
Some of the substituted thiolactones of formula (I) that are directly obtained by carrying out the preparation process in accordance with the first subject of the invention are novel per se and thus constitute the second subject of the invention.
Therefore, another subject of the present invention is the substituted thiolactones of the following formula (I′):
wherein:
A′1, A′2, Y′, Z1′, L′, m′, T′ and e′ may respectively assume the same meanings as those defined above for A1, A2, Y, Z1, L, m, T and e for the thiolactones of formula (I), with the proviso that:
in so far as such thiolactones are described in the article by Espeel P. et al., European Polymer Journal, 2015, 62, 247-272.
Among the above substituted thiolactones of formula (I′), mention may especially be made of:
The substituted thiolactones of formula (I) that are able to be obtained by carrying out the process in accordance with the present invention and in particular the thiolactones of formula (I′) in accordance with the second subject of the present invention may advantageously be used for the synthesis of polymers or for surface functionalization or polymer functionalization.
Thus, a third subject of the present invention is also the use of at least one substituted thiolactone of formula (I) obtained according to the process as defined according to the first subject of the invention, in particular of at least one substituted thiolactone of formula (I′), for the synthesis of polymers or for the functionalization of planar surfaces of metal, glass or ceramic type, particles or polymers.
Regarding the preparation of polymers, the thiolactones of formula (I) and in particular of formula (I′) may be used in a polymerization reaction comprising at least one step of reacting a thiolactone of formula (I), in particular of formula (I′), with a nucleophilic compound, making it possible to open the thiolactone ring and to obtain a thiol which may subsequently be used in an addition or condensation polymerization process with, for example, a monomer of diacrylate type such as described in the reference by Lei Yu et al, Polym. Chem., 2015, 6, 1527-1532.
Regarding the surface functionalization or polymer functionalization, it is thus possible:
Depending on the nature of the groups Y or Z1 (respectively Y′ and Z1′), it thus becomes possible to provide a material or a polymer with the properties corresponding to the type of groups Y or Z1 (respectively Y′ or Z1′) grafted, for example release properties when the groups Y or Z1 (respectively Y′ or Z1′) are perfluorinated groups. It is also possible to introduce an additional function when the thiol obtained by opening the thiolactone is reacted with a functional compound that reacts with thiols.
The present invention is illustrated by the following embodiment examples, to which, however, it is not limited.
In this example the thiolactone of the following formula was prepared (TL1):
100 g (1.13 mol) of 3-methylbutan-2-ol (Alfa Aesar), 63.65 g of potassium hydroxide (KOH, Sigma-Aldrich) and carbon disulfide (CS2, Sigma-Aldrich) were suspended in 500 ml of tetrahydrofuran (THF, Sigma-Aldrich) at room temperature for 24 hours.
After total dissolution of the KOH, the yellow emulsion was concentrated under reduced pressure then triturated with pentane (Sigma-Aldrich) and finally filtered to obtain 185 g of the expected product XA0 in the form of a yellow solid (185 g, yield 80%).
1H NMR (300.13 MHz, D2O, 298K) δ 5.31 (p, 3JH,H=6.4 Hz, 1H, (CH3)2CHCH(O)CH3); 2.07-1.84 (m, 1H, (CH3)2CHCH(O)CH3); 1.27 (d, 3JH,H=6.4 Hz, 3H, (CH3)2CHCH(O)CH3); 0.96 (d, 3JH,H=6.9 Hz, 6H, (CH3)2CHCH(O)CH3).
13C NMR{1H} (75.47 MHz, D2O, 298K) δ 232.6 (C═S); 86.3 ((CH3)2CHCH(O)CH3); 32.8 ((CH3)2CHCH(O)CH3); 17.7 ((CH3)2CHCH(O)CH3); 17.6 ((CH3)2CHCH(O)CH3); 15.8 ((CH3)2CHCH(O)CH3) ppm.
0.21 mol (32.12 g) of methyl 2-bromoacetate (Sigma-Aldrich) was added to a suspension of 40.5 g (0.2 mol) of the compound XA0 obtained above in the preceding step 1.1) in 200 ml of acetone (Sigma-Aldrich), in an ice bath. Once the addition had ended, the reaction medium was stirred at room temperature for 3 hours then filtered. The filtrate was concentrated under vacuum in order to obtain the expected product XA1 in the form of a yellow oil (42 g, yield 89%) which will be used in the following step without purification.
14.2 g (60 mmol) of the xanthate XA1 obtained above in the preceding step, 2.72 g (20 mmol) of dimethyl vinylphosphonate and 1.2 g (3 mmol) of dilauroyl peroxide (LPO: radical initiator) were mixed in a Schlenk tube. The mixture was subsequently degassed by 3 operations of freezing under vacuum. After 5 hours of heating at a temperature of 90° C., the crude reaction product was purified by silica chromatography (eluent ethyl acetate/petroleum ether (95:5, v:v) to recover the unreacted xanthate XA1, and with an eluent formed from a mixture of ethyl acetate/dichloromethane (1:4, v:v) to recover the monoadduct XA1VP (3.13 g, yield 42%, yellow oil).
1H NMR (300.13 MHz, CDCl3, 298K) δ 5.53-5.33 (m, 1H, (CH3)2CHCH(O)CH3); 4.31-4.11 (m, 1H, CHP); 3.75-3.65 (m, 6H, O═P(OCH3)2); 3.59 (s, 3H, CO2CH3); 2.56-2.44 (m, 2H, CH2CH2CO2CH3); 2.43-1.87 (m, 2H, CH2CH2CO2CH3); 2.02-1.87 (m, 1H, (CH3)2CHCH(O)CH3); 1.25-1.21 (m, 3H, (CH3)2CHCH(O)CH3); 0.89-0.86 (m, 6H, (CH3)2CHCH(O)CH3).
13C NMR{1H} (75.47 MHz, CDCl3, 298K) δ 211.8-211.5 (C═S); 175.7 (CO2CH3); 87.3; 87.2 ((CH3)2CHCH(O)CH3); 53.9-53.4 (O═P(OCH3)2); 51.7 (CO2CH3); 44.6-42.5 (CHP); 32.7 ((CH3)2CHCH(O)CH3); 31.0-30.8 (CH2CH2CO2CH3); 25.1-24.9 (CH2CH2CO2CH3); 18.0-17.8 ((CH3)2CHCH(O)CH3); 15.7; 15.6 ((CH3)2CHCH(O)CH3).
31P NMR{1H} (121.49 MHz, CDCl3, 298K) δ 26.3; 26.2 ppm.
IR: 1738.5 cm−1 (C═O), 1035.1 cm−1 (C═S).
Molar mass: IC(CH4), MH+:
Found: 373.0916 g/mol
Calculated: 373.0908 g/mol.
3.70 g (10 mmol) of XA1VP obtained above in the preceding step were placed in a sealed Schlenk tube under vacuum and brought to a temperature of 190° C. for 15 minutes. The reaction mixture was subsequently cooled to room temperature and the volatile compounds formed were eliminated under vacuum. The thiolactone TL1 thus obtained in the form of a colourless oil (1.2 g, yield 57%) was subsequently purified on a silica chromatography column (eluent ethyl acetate/dichloromethane: 1:4 (v:v)).
1H NMR (300.13 MHz, CDCl3, 298K) δ 3.87-3.76 (m, 1H, CHP); 3.72-3.57 (m, 6H, O═P(OCH3)2); 2.63-2.33 (m, 2H, CH2CH2CHP); 2.32-2.17 (m, 2H, CH2CH2CHP).
13C NMR{1H} (75.47 MHz, CDCl3, 298K) δ 205.7-205.6 (C═O); 53.2-53.1 (O═P(OCH3)2); 42.3-40.2 (CHP); 39.6-39.5 (CH2CH2CHP); 25.40-25.35 (CH2CH2CHP).
31P NMR{1H} (121.49 MHz, CDCl3, 298K) δ 25.7 ppm.
IR: 1713.9 cm−1 (C═O).
Molar mass: IC(CH4), MH+
Found: 211.0198 g/mol
Calculated: 211.0194 g/mol.
0.21 mol (35.07 g) of methyl 2-bromopropionate (Sigma-Aldrich) was added to a suspension of 40.5 g (0.2 mol) of the compound XA0 obtained above in the preceding step 1.1) of example 1, in 200 ml of acetone (Sigma-Aldrich), in an ice bath. Once the addition had ended, the reaction medium was stirred at room temperature for 3 hours then filtered. The filtrate was concentrated under vacuum in order to obtain the expected product XA2 in the form of a yellow oil (43 g, yield 86%) which will be used in the following step without purification.
1H NMR (300.13 MHz, CDCl3, 298K) δ 5.51 (p, 3JH,H=6.3 Hz, 1H, (CH3)2CHCH(O)CH3); 4.42-4.30 (m, 1H, CH(CH3)CO2CH3); 3.73 (s, 3H, CO2CH3); 2.09-1.88 (m, 1H, (CH3)2CHCH(O)CH3); 1.56-1.52 (m, 3JH,H=7.4 Hz, 3H, CH(CH3)CO2CH3); 1.29-1.25 (m, 3JH,H=6.4 Hz, 3H, (CH3)2CHCH(O)CH3); 1.02-0.91 (m, 6H, (CH3)2CHCH(O)CH3).
13C NMR{1H} (75.47 MHz, CDCl3, 298K) δ 211.4; 211.4 (C═S); 172.0 (CO2CH3); 86.2-86.1 ((CH3)2CHCH(O)CH3); 52.8 (CO2CH3); 46.5 (CH(CH3)CO2CH3); 32.7 ((CH3)2CHCH(O)CH3); 18.2-17.8 ((CH3)2CHCH(O)CH3); 17.0-16.9 (CH(CH3)CO2CH3); 15.8-15.7 ((CH3)2CHCH(O)CH3) ppm.
IR: 1738.5 cm−1 (C═O); 1046.2 cm−1 (C═S)
9.26 g (37 mmol) of the xanthate XA2 obtained above in step 1.1), 5.87 g (33 mmol) of diethyl allylphosphonate (DEAP, Alfa Aesar) and 2 g (5 mmol) of LPO were dissolved in 5 ml of toluene (Sigma-Aldrich). The solution thus obtained was transferred to a Schlenk tube and degassed by 3 successive operations of freezing under vacuum. After 18 hours of heating at 90° C., 10.1 g of crude reaction product were obtained in the form of a yellow oil (yield 79%) which was purified by silica chromatography (eluent ethyl acetate/dichloromethane: 1:4, v:v).
12.7 g of XA2AP were thus obtained (yield 90%).
1H NMR (300.13 MHz, CDCl3, 298K) δ 5.54-5.46 (m, 1H, (CH3)2CHCH(O)CH3); 4.15-4.02 (m, 4H, O═P(OCH2CH3)2); 4.02-3.89 (m, 1H, CHS); 3.62 (s, 3H, CO2CH3); 2.75-1.63 (m, 6H, CH2P, (CH3)2CHCH(O)CH3, CH2CHCO2CH3); 1.32-1.23 (m, 9H, O═P(OCH2CH3)2, CH3CHCO2CH3); 1.17-1.14 (m, 3H, (CH3)2CHCH(O)CH3); 0.92-0.90 (m, 6H, (CH3)2CHCH(O)CH3).
13C NMR{1H} (75.47 MHz, CDCl3, 298K) δ 212.7-215.6 (C═S); 176.2-176.0 (CO2CH3); 85.8-85.7 ((CH3)2CHCH(O)CH3); 62.0-61.8 (O═P(OCH2CH3)2); 51.8 (CO2CH3); 43.8-43.6 (CHS); 37.8-36.6 (CH2P); 37.3-37.1 ((CH3)2CHCH(O)CH3); 33.4-31.1 (CH2CH2CO2CH3); 32.7 (CHCO2CH3); 18.3-17.9 ((CH3)2CHCH(O)CH3); 18.3-17.8 (CH3CHCO2CH3); 16.6-165 (O═P(OCH2CH3)2); 15.9-15.8 ((CH3)2CHCH(O)CH3).
31P NMR{1H} (121.49 MHz, CDCl3, 298K) δ 26.7 ppm.
IR: 1736.9 cm−1 (C═O); 1043.6 cm−1 (C═S)
Molar mass: IC(CH4), MH+
Found: 429.1533 g/mol
Calculated: 429.1534 g/mol.
4.28 g (10 mmol) of XA2AP obtained above in the preceding step were placed in a sealed Schlenk tube under vacuum and brought to a temperature of 190° C. for 15 minutes. The reaction mixture was subsequently cooled to room temperature and the volatile compounds formed were eliminated under vacuum. The thiolactone TL2 thus obtained in the form of a colourless oil (2.4 g, yield 90%) was subsequently purified on a silica chromatography column (eluent ethyl acetate/dichloromethane: 1:4 (v:v)).
1H NMR (300.13 MHz, CDCl3, 298K) δ 4.18-4.05 (m, 4H, O═P(OCH2CH3)2); 4.05-3.90 (m, 1H, CHCH2P); 2.77-2.29 (m, 2H, CH2CH(CH3)); 2.28-2.07 (m, 2H, CHCH2P); 1.62-1.20 (m, 1H, CHCH2P); 1.35-1.29 (m, 6H, O═P(OCH2CH3)2); 1.19-1.14 (m, 3H, CH2CH(CH3)).
13C NMR{1H} (75.47 MHz, CDCl3, 298K) δ 210.0-209.0 (C═O); 62.2-62.1 (O═P(OCH2CH3)2); 48.7-45.4 (CHCH2P); 42.6-42.4 (CH2CH(CH3)); 41.0-40.9 (CH2CH(CH3)); 34.2-31.7 (CHCH2P); 16.6-16.5 (O═P(OCH2CH3)2); 15.2-14.3 (CH2CH(CH3)).
31P NMR{1H} (121.49 MHz, CDCl3, 298K) δ 26.40, 26.36 ppm.
IR: 1700.5 cm−1 (C═O); 1245.7 cm−1 (P═O); 1025.4 cm−1 (P—O)
Molar mass: IC(CH4), MH+
Found: 267.0826 g/mol
Calculated: 267.0820 g/mol.
The monoadduct XA3AP was prepared according to the procedure used above in step 1.2) of example 2 for the preparation of the monoadduct XA2AP, but using 8.74 g (37 mmol) of the xanthate XA1 as prepared above in step 1) of example 1, 5.88 g (33 mmol) of DEAP (Sigma-Aldrich) and 2 g (5 mmol) of LPO.
12.31 g of XA3AP were thus obtained (yield 90%).
1H NMR (300.13 MHz, CDCl3, 298K) δ 5.49-5.39 (m, 1H, (CH3)2CHCH(O)CH3); 4.09-3.96 (m, 4H, O═P(OCH2CH3)2); 3.96-3.87 (m, 1H, CHS); 3.55 (s, 3H, CO2CH3); 2.48-1.84 (m, 7H, CH2P, (CH3)2CHCH(O)CH3, CH2CH2CO2CH3); 1.26-1.20 (m, 6H, O═P(OCH2CH3)2); 1.20-1.17 (m, 3H, (CH3)2CHCH(O)CH3); 0.86-0.83 (m, 6H, (CH3)2CHCH(O)CH3).
13C NMR{1H} (75.47 MHz, CDCl3, 298K) δ 212.2 (C═S); 172.8 (CO2CH3); 85.6 ((CH3)2CHCH(O)CH3); 61.9-61.7 (O═P(OCH2CH3)2); 51.5 (CO2CH3); 44.5 (CHS); 32.5 ((CH3)2CHCH(O)CH3); 32.5-30.5 (CH2P); 31.2-31.1 (CH2CH2CO2CH3); 29.1-28.7 (CH2CH2CO2CH3); 18.1-17.8 ((CH3)2CHCH(O)CH3); 16.4-16.3 (O═P(OCH2CH3)2); 15.6 ((CH3)2CHCH(O)CH3).
31P NMR{1H} (121.49 MHz, CDCl3, 298K) δ 26.53; 26.51 ppm.
IR: 1738.8 cm−1 (C═O); 1044.9 cm−1 (C═S)
Molar mass: IC(CH4), MH+
Found: 415.1390 g/mol
Calculated: 415.1378 g/mol.
The thiolactone TL3 was prepared according to the same procedure as that used above in example 2, step 2) for the preparation of the thiolactone TL2, but using 4.14 g (10 mmol) of the monoadduct XA3AP prepared above in the preceding step instead of the monoadduct XA2AP.
2.3 g of TL3 were thus obtained in the form of a colourless oil (yield 91%).
1H NMR (300.13 MHz, CDCl3, 298K) δ 4.15-4.00 (m, 5H, CHCH2P, O═P(OCH2CH3)2); 2.63-2.45 (m, 3H, CH2CH2CO, CH2CH2CO); 2.29-2.08 (m, 2H, CHCH2P); 2.05-1.89 (m, 1H, CH2CH2CO); 1.32-1.25 (m, 6H, O═P(OCH2CH3)2).
13C{1H} 13C NMR{1H} (75.47 MHz, CDCl3, 298K) δ 207.4 (C═O); 62.1-62.0 (O═P(OCH2CH3)2); 44.44-44.39 (CHCH2P); 41.8 (CH2CH2CO); 33.7-31.8 (CHCH2P); 33.4-33.3 (CH2CH2CO); 16.5-16.4 (O═P(OCH2CH3)2).
31P NMR{1H} (121.49 MHz, CDCl3, 298K) δ 26.2 ppm.
IR: 1704.4 cm−1 (C═O); 1250.5 cm−1 (P═O); 1025.2 cm−1 (P—O)
Molar mass: IC(CH4), MH+
Found: 253.0667 g/mol
Calculated: 253.0663 g/mol.
The monoadduct XA4H was prepared according to the same procedure as that used above in step 1.2) of example 2 for the preparation of the monoadduct XA2AP, but using 9.26 g (37 mmol) of the xanthate XA2 prepared in step 1.1) of example 2, 3.24 g (33 mmol) of 1-heptene (Sigma-Aldrich) and 2 g (5 mmol) of LPO.
10.7 g of XA4H were thus obtained (yellow oil; eluent ethyl acetate/petroleum ether (95:5; v:v), in the form of a racemate (yield 92%).
1H NMR (300.13 MHz, CDCl3, 298K) δ 5.59-5.46 (m, 1H, (CH3)2CHCH(O)CH3); 3.78-3.64 (m, 1H, SCHCH2CH(CH3)CO2CH3); 3.64-3.61 (m, 3H, CO2CH3); 2.73-2.54 (m, 1H, SCHCH2CH(CH3)CO2CH3); 2.13-1.87 (m, 2H, SCHCH2CH(CH3)CO2CH3); 1.75-1.47 (m, 3H, (CH3)2CHCH(O)CH3, CH2(CH2)3CH3); 1.47-1.31 (m, 2H, CH2CH2(CH2)2CH3); 1.31-1.18 (m, 7H, CH(CH3)CO2CH3, (CH2)2(CH2)2CH3); 1.18-1.09 (m, 3H, (CH3)2CHCH(O)CH3); 0.97-0.87 (m, 6H, (CH3)2CHCH(O)CH3); 0.87-0.79 (m, 3H, (CH2)4CH3).
13C NMR{1H} (75.47 MHz, CDCl3, 298K) δ 213.8-213.7 (C═S); 176.3-176.3 (CO2CH3); 85.2-85.0 ((CH3)2CHCH(O)CH3); 51.6 (CO2CH3); 49.1-48.6 (SCHCH2CH(CH3)CO2CH3); 38.1-37.5 (SCHCH2CH(CH3)CO2CH3); 37.2-37.1 (SCHCH2CH(CH3)CO2CH3); 35.2-34.7 (CH2(CH2)3CH3); 32.7 ((CH3)2CHCH(O)CH3); 31.6 ((CH2)2CH2CH2CH3); 26.3-26.2 (CH2CH2(CH2)2CH3); 22.4 ((CH2)3CH2CH3); 18.1-17.0 ((CH3)2CHCH(O)CH3); 17.9-17.8 (CH(CH3)CO2CH3); 15.71-15.69 ((CH3)2CHCH(O)CH3); 13.9 (SCH(CH2)4CH3) ppm.
IR: 1738.5 cm−1 (C═O); 1047.2 cm−1 (C═S).
Molar mass: IC(CH4), MH+
Found: 349.1861 g/mol
Calculated: 349.1871 g/mol.
The thiolactone TL4 was prepared according to the same procedure as that used above in example 2, step 2) for the preparation of the thiolactone TL2, but using 3.48 g (10 mmol) of the monoadduct XA4H prepared above in the preceding step instead of the monoadduct XA2AP.
1.73 g of thiolactone TL4 were thus obtained (yield 93%) in the form of a colourless liquid (eluent: ethyl acetate/petroleum ether: 9:1; v:v).
1H NMR (300 MHz, CDCl3, 298K) δ 3.79-3.64 (m, 1H, SCHCH2CH); 2.76-2.46 (m, 2H, SCHCH2CH); 2.20-1.97 (m, 1H, SCHCH2CH); 1.83-1.62 (m, 2H, CH2CH2(CH2)2CH3); 1.55-1.35 (m, 2H, CH2(CH2)3CH3); 1.35-1.21 (m, 4H, (H2)2(CH2)2CH3); 1.20-1.13 (m, 3H, CHCH3); 0.92-0.84 (m, 3H, (CH2)4CH3).
13C NMR{1H} (75.47 MHz, CDCl3, 298K) δ 211.2-210.0 (C═O); 48.92-47.89 (SCHCH2CH); 47.5-456 (SCHCH2CH); 415-39.7 (SCHCH2CH); 36.8-36.5 (CH2(CH2)3CH3); 31.7-31.6 ((CH2)2CH2CH2CH3); 28.2-28.0 (CH2CH2(CH2)2CH3); 22.60-22.56 ((CH2)3CH2CH3); 15.5-14.6 (CHCH3); 14.1 ((CH2)4CH3) ppm.
IR: 1700.9 cm−1 (C═O).
Molar mass: IE
Found: 186.1075 g/mol
Calculated: 186.1078 g/mol.
The monoadduct XA5H was prepared according to the procedure used above in step 1.2) of example 2 for the preparation of the monoadduct XA2AP, but using 8.74 g (37 mmol) of the xanthate XA1 as prepared above in step 1.2) of example 1, 3.24 g (33 mmol) of 1-heptene and 2 g (5 mmol) of LPO.
10 g of thiolactone XA5H were thus obtained in the form of a yellow oil (eluent: ethyl acetate/petroleum ether: 95:5; v:v) in the form of a racemate (yield 90%).
1H NMR (300.13 MHz, CDCl3, 298K) δ 5.53 (p, 3JH,H=6.3 Hz, 1H, (CH3)2CHCH(O)CH3); 3.78-3.66 (m, 1H, SCHCH2CH2CO2CH3); 3.64 (s, 3H, CO2CH3); 2.49-2.36 (m, 2H, SCHCH2CH2CO2CH3); 2.12-1.94 (m, 2H, CH2(CH2)3CH3); 1.93-1.77 (m, 1H, (CH3)2CHCH(O)CH3); 1.69-1.52 (m, 2H, SCHCH2CH2CO2CH3); 1.52-1.33 (m, 2H, CH2CH2(CH2)2CH3); 1.33-1.16 (m, 7H, (CH2)2(CH2)2CH3; (CH3)2CHCH(O)CH3); 0.93 (d, J=6.8 Hz, 6H, (CH3)2CHCH(O)CH3); 0.89-0.79 (m, 3H, (CH2)4CH3).
13C NMR{1H} (75.47 MHz, CDCl3, 298K) δ 214.0-213.9 (C═S); 173.5-173.5 (CO2CH3); 85.4-85.4 ((CH3)2CHCH(O)CH3); 51.7 (CO2CH3); 50.3-50.2 (SCHCH2CH2CO2CH3); 34.6-34.3 (CH2(CH2)3CH3); 32.8 ((CH3)2CHCH(O)CH3); 31.7 ((CH2)2CH2CH2CH3); 31.5-31.4 (SCHCH2CH2CO2CH3); 29.7-29.3 (SCHCH2CH2CO2CH3); 26.6-26.5 (CH2CH2(CH2)2CH3); 22.6 ((CH2)3CH2CH3); 18.3-18.0 ((CH3)2CHCH(O)CH3); 15.8 ((CH3)2CHCH(O)CH3); 14.1 ((CH2)4CH3) ppm.
IR: 1740.9 cm−1 (C═O); 1048.6 cm−1 (C═S).
Molar mass: IC(CH4), MH+
Found: 335.1701 g/mol
Calculated: 335.1715 g/mol
The thiolactone TL5 was prepared according to the same procedure as that used above in example 2, step 2) for the preparation of the thiolactone TL2, but using 3.34 g (10 mmol) of the monoadduct XA5H prepared above in the preceding step instead of the monoadduct XA2AP.
1.55 g of TL5 were thus obtained in the form of a colourless liquid (eluent: ethyl acetate/petroleum ether: 9:1; v:v) (yield 90%).
1H NMR (300.13 MHz, CDCl3, 298K) δ 3.82 (tt, 3JH,H=8.5; 5.8 Hz, 1H, SCHCH2CH2); 2.66-2.44 (m, 2H, SCHCH2CH2); 2.43-1.79 (m, 2H, SCHCH2CH2); 1.79-1.62 (m, 2H, CH2CH2(CH2)2CH3); 1.47-1.33 (m, 2H, CH2(CH2)3CH3); 1.32-1.19 (m, 4H, (CH2)2(CH2)2CH3); 0.86 (t, 3JH,H=7.0 Hz, 3H, (CH2)4CH3).
13C NMR{1H} (75.47 MHz, CDCl3, 298K) δ 208.6 (C═O); 51.4 (SCHCH2CH2); 42.1 (SCHCH2CH2); 36.5 (CH2(CH2)3CH3); 32.3 ((CH2)2CH2CH2CH3); 31.5 (SCHCH2CH2); 28.0 (CH2CH2(CH2)2CH3); 22.5 ((CH2)3CH2CH3); 14.0 ((CH2)4CH3) ppm.
IR: 1704.6 cm−1 (C═O)
Mass: IE
Found: 172.0910 g/mol
Calculated: 172.0922 g/mol.
The monoadduct XA6DF was prepared according to the procedure used above in step 1.2) of example 2 for the preparation of the monoadduct XA2AP, but using 3.09 g (1.23×10−2 mol) of xanthate XA2 as prepared above in step 1.1) of example 2, 5 g (1.12×10−2 mol) of 1H,1H,2H-perfluoro-1-decene (Aldrich), 0.67 g of LPO, and a reaction solvent composed of 4 ml of toluene and 3 ml of trifluorotoluene.
The monoadduct XA6DF obtained in the form of a viscous yellow oil was purified by silica chromatography (eluent hexane/ethyl acetate: 9:1, v:v).
3.2 g of XA6DF were thus obtained (yield 41%).
1H NMR (300.13 MHz, CDCl3, 298K): δ (ppm) 5.58-5.47 (s, 1H, (CH3)2CHCH(O)CH3); 4.87-4.67 (m, 1H, SCHCH2CH(CH3)); 3.70-3.68 (m, 3H, CO2CH3); 2.92-2.68 (1H, m, SCHCH2CH(CH3)); 2.14-1.92 (m, 1H, (CH3)2CHCH(O)CH3); 1.58-1.53 (m, 2H, SCHCH2CH(CH3)); 1.32-1.20 (m, 6H; (CH3)2CHCH(O)CH3 et SCHCH2CH(CH3)); 0.97-0.93 (m, 6H, (CH3)2CHCH(O)CH3).
13C NMR{1H} (75.47 MHz, CDCl3, 298K): δ (ppm) 209.33 (C═S); 175.54 (CO2CH3); 129.01-115.52 (CH(CF2)7CF3); 87.48 ((CH3)2CHCH(O)CH3); 52.71-51.79 (CO2CH3); 46.50 (CH(CF2)3CF3); 36.48 (SCHCH2CH(CH3)); 32.71 ((CH3)2CHCH(O)CH3); 18.30-15.44 ((CH3)2CHCH(O)CH3 et (SCHCH2CH(CH3)).
NMR 19F{1H} (282.38 MHz, CDCl3, 298K): δ (ppm) −80.83 (CH(CF2—CF2—CF2—CF2—CF2—CF2—CF2—CF3)); −105.65-−116.25 (CH(CF2—CF2—CF2—CF2—CF2—CF2—CF2—CF3)); −118.87-−119.33 (CH(CF2—CF2—CF2—CF2—CF2—CF2—CF2—CF3)); −121.69-−121.91 (CH(CF2—CF2—CF2—CF2—CF2—CF2—CF2—CF3)); −122.72 (CH(CF2—CF2—CF2—CF2—CF2—CF2—CF2—CF3)); −126.16 (CH(CF2—CF2—CF2—CF2—CF2—CF2—CF2—CF3)).
2 g (2.87 mmol) of XA6DF obtained above in the preceding step were placed in a sealed Schlenk tube under vacuum and brought to a temperature of 190° C. for 48 hours. The reaction mixture was subsequently cooled to room temperature and the volatile compounds formed were eliminated under vacuum. The thiolactone TL6 thus obtained in the form of a yellow oil was subsequently purified on a silica chromatography column (eluent ethyl acetate/hexane: 1:1 (v:v)).
0.8 g of TL6 were thus obtained in the form of a white powder (yield 52%).
1H NMR (300.13 MHz, CDCl3, 298K): δ (ppm) 4.49-4.36 (m, 1H, CHCF2); 2.75-2.59 (m, 2H, C(O)CH(CH3)CH2CH); 1.99-1.87 (q, 1H, C(O)CH(CH3)CH2CH); 1.26-1.23 (d, 3H, C(O)CH(CH3)).
NMR 19F{1H} (282.38 MHz, CDCl3, 298K): δ (ppm) −81.03 (CH(CF2—CF2—CF2—CF2—CF2—CF2—CF2—CF3)); −112.13-−119.71 (CH(CF2—CF2—CF2—CF2—CF2—CF2—CF2—CF3)); −121.08 (CH(CF2—CF2—CF2—CF2—CF2—CF2—CF2—CF3)); −121.96 (CH(CF2—CF2—CF2—CF2—CF2—CF2—CF2—CF3)); −122.86 (CH(CF2—CF2—CF2—CF2—CF2—CF2—CF2—CF3)); −126.29 (CH(CF2—CF2—CF2—CF2—CF2—CF2—CF2—CF3)).
The monoadduct XA7MAL was prepared according to the procedure used above in step 1.2) of example 2 for the preparation of the monoadduct XA2AP, but using 4.77 g (1.91×10−2 mol) of the xanthate XA2 as prepared above in step 1.1) of example 2, 3 g (1.73×10−2 mol) of N-phenylmaleimide (Aldrich) and 1.03 g of LPO.
The monoadduct XA7MAL obtained in the form of a viscous yellow oil was purified by silica chromatography (eluent hexane/ethyl acetate: 7:3, v:v).
4.9 g of XA7MAL were thus obtained (yield 68%).
1H NMR (300.13 MHz, CDCl3, 298K): δ (ppm) 7.47-7.30 (m, 5H, N—C6H5); 5.57-5.48 (s, 1H, (CH3)2CHCH(O)CH3); 5.22-4.07 (m, 1H, SCH(CO)CH); 3.76-3.66 (m, 3H, CO2CH3); 3.55-3.21 (m, 2H, SCH(CO)CH(CO)CH(CH3)); 2.07-1.92 (1H, (CH3)2CHCH(O)CH3); 1.56-1.39 (m, 3H, CH(CO)CH(CH3)); 1.39-1.26 (m, 3H, (CH3)2CHCH(O)CH3); 0.98-0.92 (m, 3H, (CH3)2CHCH(O)CH3).
13C NMR{1H} (75.47 MHz, CDCl3, 298K): δ (ppm) 209.77 (C═S); 175.59-171.71 (C(O)NC(O) et CO2CH3); 131.38-126.36 (N—C6H5); 87.27 ((CH3)2CHCH(O)CH3); 52.42 CO2CH3); 50.47-46.87 (SCH(CO)CH(CO)CH(CH3)); 39.71-38.99 (SCH(CO)CH(CO)CH(CH3)); 32.82 ((CH3)2CHCH(O)CH3); 18.34-17.84 ((CH3)2CHCH(O)CH3); 15.81-15.21 (SCH(CO)CH(CO)CH(CH3)).
1 g (2.36 mmol) of XA7MAL obtained above in the preceding step was placed in a sealed Schlenk tube under vacuum and brought to a temperature of 190° C. for 48 hours. The reaction mixture was subsequently cooled to room temperature and the volatile compounds formed were eliminated under vacuum. The thiolactone TL7 thus obtained in the form of a yellow oil was subsequently purified on a silica chromatography column (eluent ethyl acetate/hexane: 1:1 (v:v)).
0.4 g of TL7 were thus obtained (yield 65%).
1H NMR (300.13 MHz, CDCl3, 298K): δ (ppm) 7.55-7.30 (m, 5H, N—C6H5); 4.86-4.75 (s, 1H, SCH(CO)CH); 3.46-3.44 (m, 1H, CH(CH3)CHC(O)); 3.34-3.25 (m, 1H, C(O)CH(CH3)); 1.49-1.47 (d, 3H, C(O)CH(CH3)).
13C NMR{1H} (75.47 MHz, CDCl3, 298K): δ (ppm) 205.25 (SC═O); 174.5-173.49 (C(O)NC(O)); 129.21-126.39 (N—C6H5) 49.54 (SCH(CO)); 49.03 (C(O)CH(CH3)); 46.81 (C(O)CH(CH3)CH(CO); 18.41 (C(O)CH(CH3)CH2).
The monoadduct XA8HF was prepared according to the procedure used above in step 1.2) of example 2 for the preparation of the monoadduct XA2AP, but using 4.47 g (1.78×10−2 mol) of the xanthate XA2 as prepared above in step 1.1) of example 2, 4 g (1.62×10−2 mol) of 1H,1H,2H-perfluoro-1-hexene (Aldrich) and 0.969 g of LPO.
The monoadduct XA8HF obtained in the form of a viscous yellow oil was purified by silica chromatography (eluent hexane/ethyl acetate: 9:1, v:v).
3.73 g of XA8HF were thus obtained (yield 46%).
1H NMR (300.13 MHz, CDCl3, 298K): δ (ppm) 5.59-5.48 (s, 1H, (CH3)2CHCH(O)CH3); 4.92-4.66 (m, 1H, SCHCH2CH(CH3)); 3.73-3.67 (m, 3H, CO2CH3); 2.91-2.61 (1H, m, SCHCH2CH(CH3)); 2.16-1.88 (m, 1H, (CH3)2CHCH(O)CH3); 1.60-1.52 (m, 2H, SCHCH2CH(CH3)); 1.32-1.20 (m, 6H, (CH3)2CHCH(O)CH3 et SCHCH2CH(CH3)); 0.96-0.92 (m, 6H, (CH3)2CHCH(O)CH3).
13C NMR{1H} (75.47 MHz, CDCl3, 298K): δ (ppm) 209.30 (C═S); 175.35 (CO2CH3); 129.01-127.51 (CH(CF2)3CF3); 87.49 ((CH3)2CHCH(O)CH3); 52.70-51.91 (CO2CH3); 46.48 CH(CF2)3CF3); 36.46 (SCHCH2CH(CH3)), 32.64 ((CH3)2CHCH(O)CH3); 18.32-14.08 ((CH3)2CHCH(O)CH3 et (SCHCH2CH(CH3)).
NMR 19F{1H} (282.38 MHz, CDCl3, 298K): δ (ppm) −80.80 (CH(CF2—CF2—CF2—CF3)), −105.96-−116.42 (CH(CF2—CF2—CF2—CF3)), −119.86-−120.36 (CH(CF2—CF2—CF2—CF3)), −125.60-−126.30 (CH(CF2—CF2—CF2—CF3)).
2 g (4.03 mmol) of XA8HF obtained above in the preceding step were placed in a sealed Schlenk tube under vacuum and brought to a temperature of 190° C. for 48 hours. The reaction mixture was subsequently cooled to room temperature and the volatile compounds formed were eliminated under vacuum. The thiolactone TL8 thus obtained in the form of a colourless oil was subsequently purified on a silica chromatography column (eluent ethyl acetate/hexane: 5:95 (v:v)).
0.8 g of TL8 were thus obtained in the form of a white powder (yield 52%).
1H NMR (300.13 MHz, CDCl3, 298K): δ (ppm) 4.49-4.36 (m, 1H, CHCF2); 2.75-2.59 (m, 2H, C(O)CH(CH3)CH2CH); 1.99-1.87 (q, 1H, C(O)CH(CH3)CH2CH); 1.26-1.23 (d, 3H, C(O)CH(CH3)).
NMR 19F{1H} (282.38 MHz, CDCl3, 298K): δ (ppm) −81.03 (CH(CF2—CF2—CF2—CF2—CF2—CF2—CF2—CF3)); −112.13-−119.71 (CH(CF2—CF2—CF2—CF2—CF2—CF2—CF2—CF3)); −121.08 (CH(CF2—CF2—CF2—CF2—CF2—CF2—CF2—CF3)); −121.96 (CH(CF2—CF2—CF2—CF2—CF2—CF2—CF2—CF3)); −122.86 (CH(CF2—CF2—CF2—CF2—CF2—CF2—CF2—CF3)); −126.29 (CH(CF2—CF2—CF2—CF2—CF2—CF2—CF2—CF3)).
The following were successively introduced into a 25 ml round-bottomed flask: bis(3-aminopropyl)-poly(dimethylsiloxane) (2500 g·mol−1, 500 mg, 2×10−4 mol, Aldrich), TL4 (52.1 mg, 2.8×10−4 mol) and benzyl acrylate (45.4 mg, 2.8×10−4 mol, Aldrich). The reaction mixture was stirred for 20 hours at 50° C. 1H NMR analysis and MALDI-TOF analysis showed total functionalization of the bis(3-aminopropyl)-poly(dimethylsiloxane).
The following were successively introduced into a 25 ml round-bottomed flask: methoxypolyethylene glycol amine (2000 g·mol−1, 200 mg, 1×10−4 mol, Aldrich), TL4 (16.7 mg, 9×10−5 mol) and benzyl acrylate (14.6 mg, 9×10−5 mol, Aldrich). The reaction mixture was stirred for 20 hours at 60° C. 1H NMR analysis and MALDI-TOF analysis showed total functionalization of the methoxypolyethylene glycol amine.
The following were successively introduced into a 25 ml round-bottomed flask: bis(3-aminopropyl)-poly(dimethylsiloxane) (2500 g·mol−1, 500 mg, 2×10−4 mol, Aldrich), TL2 (74.5 mg, 2.8×104 mol) and benzyl acrylate (45.4 mg, 2.8×10−4 mol, Aldrich). The reaction mixture was stirred for 20 hours at 50° C. 1H NMR analysis showed total functionalization of the bis(3-aminopropyl)-poly(dimethylsiloxane).
The following were successively introduced into a 25 ml round-bottomed flask: methoxypolyethylene glycol amine (2000 g·mol−1, 200 mg, 1×10−4 mol, Aldrich), TL2 (23.9 mg, 9×10−5 mol) and benzyl acrylate (14.6 mg, 9×10−5 mol, Aldrich). The reaction mixture was stirred for 20 hours at 60° C. 1H NMR analysis showed total functionalization of the methoxypolyethylene glycol amine.
The following were successively introduced into a 25 ml round-bottomed flask: bis(3-aminopropyl)-poly(dimethylsiloxane) (2500 g·mol−1, 500 mg, 2.0×10−4 mol, Aldrich), TL2 (74.5 mg, 2.8×10−4 mol) and poly(ethylene glycol) diacrylate (575 g·mol−1, 80.5 mg, 1.4×10−4 mol, Aldrich). The reaction mixture was stirred for 20 hours at 50° C. H and 31P NMR analysis showed total consumption of the monomers, and size exclusion chromatography confirmed the formation of the polymer. Mn(PS)=8100 g·mol−1 Mw(PS)=14 500 g·mol−1.
The monoadduct XA23OD was prepared according to the procedure used above in step 1.2) of example 2 for the preparation of the monoadduct XA2AP, but using 4.77 g (1.90×10−2 mol) of xanthate XA2 as prepared in step 1.2) of example 2, 1 g (0.90×10−2 mol) of 1,7-octadiene (Aldrich), 0.54 g of LPO, and a reaction solvent composed of 2 ml of toluene.
The monoadduct XA23OD obtained in the form of a viscous yellow oil was purified by silica chromatography (eluent hexane/ethyl acetate: 95:5, v:v).
2.49 g of XA23OD were thus obtained (yield 45%).
1H NMR (300.13 MHz, CDCl3, 298K): δ (ppm) 5.47-5.46 (s, 2H, (CH3)2CHCH(O)CH3); 3.77-3.78 (m, 2H, SCHCH2CH(CH3)); 3.66-3.64 (m, 6H, CO2CH3); 2.73-2.61 (2H, m, SCHCH2CH(CH3)); 2.15-1.91 (m, 4H, SCHCH2CH(CH3)); 1.73-1.49 (m, 6H, (CH3)2CHCH(O)CH3 et SCH(CH2CH2)CH2CH(CH3)); 1.49-1.34 (m, 4H, SCH(CH2CH2)CH2CH(CH3)); 1.28-1.23 (d, 3H, SCHCH2CH(CH3)); 1.17-1.15 (d, 3H, (CH3)2CHCH(O)CH3); 0.94-0.92 (m, 6H, (CH3)2CHCH(O)CH3).
2.49 g (4.1 mmol) of XA23OD obtained above in the preceding step were placed in a sealed Schlenk tube under vacuum and brought to a temperature of 190° C. for 48 hours. The reaction mixture was subsequently cooled to room temperature and the volatile compounds formed were eliminated under vacuum. The thiolactone TL9 thus obtained in the form of a yellow oil was subsequently purified on a silica chromatography column (eluent ethyl acetate/hexane: 8:2 (v:v)).
0.877 g of TL23 were thus obtained in the form of a white powder (yield 75%).
1H NMR (300.13 MHz, CDCl3, 298K): δ (ppm) 3.78-3.62 (m, 2H, CHS); 2.75-2.43 (m, 2H, C(O)CH(CH3)CH2CH); 2.20-1.99 (m, 2H, C(O)CH(CH3)CH2CH); 1.84-1.63 (m, 4H, CH2CH2CH2); 1.56-1.38 (m, 5H, CHCH2CH2, CHCH2CH2); 1.17-1.13 (m, 6H, CH3).
13C NMR{1H} (282.38 MHz, CDCl3, 298K): δ (ppm) 210.74-209.61 (C═O); 48.78-45.42 ((CH3)CHCH2CH2CHS); 41.30-39.48 ((CH3)CHCH2CH2CHS); 36.59-36.13 (CHCH2CH2CH2); 28.26-27.94 (CHCH2CH2CH2); 15.38-14.45 (CH3).
0.21 mol (35.07 g) of methyl 2-bromopropionate (Sigma-Aldrich) was added to a suspension of 40.5 g (0.2 mol) of the compound XA0 obtained above in the preceding step 1.1) of example 1, in 200 ml of acetone (Sigma-Aldrich), in an ice bath (highly exothermic reaction). Once the addition had ended, the reaction medium was stirred at room temperature for 3 hours then filtered. The filtrate was concentrated under vacuum in order to obtain the expected product XA2 in the form of a yellow oil (43 g, yield 86%) which will be used in the following step without purification.
1H NMR (300.13 MHz, CDCl3, 298K) δ 5.51 (p, 3JH,H=6.3 Hz, 1H, (CH3)2CHCH(O)CH3); 4.42-4.30 (m, 1H, CH(CH3)CO2CH3); 3.73 (s, 3H, CO2CH3); 2.09-1.88 (m, 1H, (CH3)2CHCH(O)CH3); 1.56-1.52 (m, 3JH,H=7.4 Hz, 3H, CH(CH3)CO2CH3); 1.29-1.25 (m, 3JH,H=6.4 Hz, 3H, (CH3)2CHCH(O)CH3); 1.02-0.91 (m, 6H, (CH3)2CHCH(O)CH3).
13C NMR{1H} (75.47 MHz, CDCl3, 298K) δ 211.4; 211.4 (C═S); 172.0 (CO2CH3); 86.2-86.1 ((CH3)2CHCH(O)CH3); 52.8 (CO2CH3); 46.5 (CH(CH3)CO2CH3); 32.7 ((CH3)2CHCH(O)CH3); 18.2-17.8 ((CH3)2CHCH(O)CH3); 17.0-16.9 (CH(CH3)CO2CH3); 15.8-15.7 ((CH3)2CHCH(O)CH3) ppm.
IR: 1738.5 cm−1 (C═O); 1046.2 cm−1 (C═S)
The xanthate XA2HN was prepared according to the same procedure as that used above in step 1.2) of example 2 for the preparation of the xanthate XA2AP, but using 5.01 g (20 mmol) of the xanthate XA2 prepared in the preceding step, 3.05 g (18 mmol) of undecene-1-ol (Sigma-Aldrich) and 1 g (26 mmol) of LPO.
5.8 g of XA2HN were thus obtained (yellow oil; eluent hexane/ethyl acetate (7:3; v:v), in the form of a racemate (yield 77%).
1H NMR (300.13 MHz, CDCl3, 298K) δ=5.57-5.48 (m, 1H, (CH3)2CHCH(O)CH3); 3.75-3.71 (m, 1H, SCHCH2CH(CH3)CO2CH3); 3.66-3.64 (m, 3H, CO2CH3); 3.62,-3.57 (t, 2H, CH2(CH2)6CH2CH2OH); 2.72-2.65 (m, 1H, SCHCH2CH(CH3)CO2CH3); 2.12-1.91 (m, 2H, SCHCH2CH(CH3)CO2CH3); 1.80 (s, 1H, OH); 1.73-1.48 (m, 5H, (CH3)2CHCH(O)CH3; CH2(CH2)6CH2CH2OH); 1.38-1.24 (m, 15H, CH(CH3)CO2CH3; CH2(CH2)6CH2CH2OH); 1.17-1.15 (m, 3H, (CH3)2CHCH(O)CH3); 0.94-0.92 (m, 6H, (CH3)2CHCH(O)CH3).
13C NMR{1H} (75.47 MHz, CDCl3, 298K) δ=213.80-213.70 (C═S); 176.65 (CO2CH3); 85.40 ((CH3)2CHCH(O)CH3); 62.90 (CH2(CH2)6CH2CH2OH); 51.58 (CO2CH3); 49.14-48.59 (SCHCH2CH(CH3)CO2CH3); 38.16-37.54 (SCHCH2CH(CH3)CO2CH3); 37.50-37.13 (SCHCH2CH(CH3)CO2CH3); 32.70-32.69 ((CH3)2CHCH(O)CH3; CH2(CH2)6CH2CH2OH); 29.48-25.72 (CH2(CH2)6CH2CH2OH); 18.25-18.23 ((CH3)2CHCH(O)CH3); 17.02-15.79 ((CH3)2CHCH(O)CH3); CH(CH3)CO2CH3).
The thiolactone TL24 was prepared according to the same procedure as that used above in example 2, step 3) for the preparation of the thiolactone TL2, but using 3.4 g (8 mmol) of the xanthate XA2HN prepared above in the preceding step instead of the xanthate XA2AP.
1.89 g of thiolactone TL24 were thus obtained (yield 91%) in the form of a colourless liquid (eluent: hexane/ethyl acetate: 5:5; v:v).
1H NMR (300 MHz, CDCl3, 298K) δ=3.74-3.63 (m, 1H, SCHCH2CH); 3.58-3.53 (t, 2H, SCHCH2(CH2)6CH2CH2OH); 2.72-2.43 (m, 1.5H, C(O)CH(CH3)CH2); 2.24 (s, 1H, OH); 2.15-1.95 (m, 1H, SCHCH2CH); 1.74-1.60 (m, 2H, CH2(CH2)6CH2CH2OH); 1.52-1.42 (m, 2.5H, SCHCH2CH, CH2(CH2)6CH2CH2OH); 1.37-1.20 (m, 12H, CH2(CH2)6CH2CH2OH); 1.12-1.09 (m, 3H, C(O)CH(CH3)CH2).
13C NMR{1H} (75.47 MHz, CDCl3, 298K) δ=211.34-210.18 (C═O); 62.78 (CH2(CH2)6CH2CH2OH); 48.81-45.50 (SCHCH2CH, C(O)CH(CH3)CH2); 41.37-39.52 (SCHCH2(CH2)6CH2CH2OH); 36.71-36.36 (C(O)CH(CH3)CH2); 32.70 (SCHCH2(CH2)6CH2CH2OH); 29.45-25.73 (SCHCH2(CH2)6CH2CH2OH); 15.38-14.42 (C(O)CH(CH3)CH2).
0.21 mol (35.07 g) of methyl 2-bromopropionate (Sigma-Aldrich) was added to a suspension of 40.5 g (0.2 mol) of the compound XA0 obtained above in the preceding step 1.1) of example 1, in 200 ml of acetone (Sigma-Aldrich), in an ice bath (highly exothermic reaction). Once the addition had ended, the reaction medium was stirred at room temperature for 3 hours then filtered. The filtrate was concentrated under vacuum in order to obtain the expected product XA2 in the form of a yellow oil (43 g, yield 86%) which will be used in the following step without purification.
1H NMR (300.13 MHz, CDCl3, 298K) δ 5.51 (p, 3JH,H=6.3 Hz, 1H, (CH3)2CHCH(O)CH3); 4.42-4.30 (m, 1H, CH(CH3)CO2CH3); 3.73 (s, 3H, CO2CH3); 2.09-1.88 (m, 1H, (CH3)2CHCH(O)CH3); 1.56-1.52 (m, 3JH,H=7.4 Hz, 3H, CH(CH3)CO2CH3); 1.29-1.25 (m, 3JH,H=6.4 Hz, 3H, (CH3)2CHCH(O)CH3); 1.02-0.91 (m, 6H, (CH3)2CHCH(O)CH3).
13C NMR{1H} (75.47 MHz, CDCl3, 298K) δ 211.4; 211.4 (C═S); 172.0 (CO2CH3); 86.2-86.1 ((CH3)2CHCH(O)CH3); 52.8 (CO2CH3); 46.5 (CH(CH3)CO2CH3); 32.7 ((CH3)2CHCH(O)CH3); 18.2-17.8 ((CH3)2CHCH(O)CH3); 17.0-16.9 (CH(CH3)CO2CH3); 15.8-15.7 ((CH3)2CHCH(O)CH3) ppm.
IR: 1738.5 cm−1 (C═O); 1046.2 cm−1 (C═S)
The xanthate XA2BN was prepared according to the same procedure as that used above in step 1.2) of example 2 for the preparation of the xanthate XA2AP, but using 1.01 g (4 mmol) of the xanthate XA2 prepared in the preceding step, 0.86 g (3.7 mmol) of bromo-11-undecene (Alfa-Aesar) and 0.22 g (0.5 mmol) of LPO.
1.41 g of XA2BN were thus obtained (yellow oil; eluent hexane/ethyl acetate (95:5; v:v), in the form of a racemate (yield 80%).
1H NMR (300.13 MHz, CDCl3, 298K) δ=5.59-5.52 (m, 1H, (CH3)2CHCH(O)CH3); 3.78-3.77 (m, 1H, SCHCH2CH(CH3)CO2CH3); 3.66-3.64 (m, 3H, CO2CH3); 3.41-3.36 (t, 2H, CH2(CH2)6CH2CH2Br); 2.70-2.63 (m, 1H, SCHCH2CH(CH3)CO2CH3); 2.08-1.91 (m, 2H, SCHCH2CH(CH3)CO2CH3); 1.73-1.48 (m, 5H, (CH3)2CHCH(O)CH3; CH2(CH2)6CH2CH2Br); 1.38-1.24 (m, 15H, CH(CH3)CO2CH3, CH2(CH2)6CH2CH2Br); 1.17-1.15 (m, 3H, (CH3)2CHCH(O)CH3); 0.94-0.92 (m, 6H, (CH3)2CHCH(O)CH3).
13C NMR{1H} (75.47 MHz, CDCl3, 298K) δ=213.80-213.70 (C═S); 176.65 (CO2CH3); 85.40 ((CH3)2CHCH(O)CH3); 51.58 (CO2CH3); 49.14-48.59 (SCHCH2CH(CH3)CO2CH3); 38.16-37.54 (SCHCH2CH(CH3)CO2CH3); 37.50-37.13 (SCHCH2CH(CH3)CO2CH3); 34.90 (CH2(CH2)6CH2CH2Br); 32.70-32.69 ((CH3)2CHCH(O)CH3; CH2(CH2)6CH2CH2Br); 29.48-25.72 (CH2(CH2)6CH2CH2Br); 18.25-18.23 ((CH3)2CHCH(O)CH3); 17.02-15.79 ((CH3)2CHCH(O)CH3); CH(CH3)CO2CH3).
The thiolactone TL25 was prepared according to the same procedure as that used above in example 2, step 3) for the preparation of the thiolactone TL2, but using 0.59 g (1.2 mmol) of the xanthate XA2BN prepared above in the preceding step instead of the xanthate XA2AP.
0.202 g of thiolactone TL25 were thus obtained (yield 52%) in the form of a colourless liquid (eluent: hexane/ethyl acetate: 9:1; v:v).
1H NMR (300 MHz, CDCl3, 298K) δ=3.79-3.66 (m, 1H, SCHCH2CH); 3.42-3.38 (t, 2H, SCHCH2(CH2)6CH2CH2Br); 2.74-2.49 (m, 1.5H, C(O)CH(CH3)CH2); 2.18-2.02 (m, 1H, SCHCH2CH); 1.89-1.59 (m, 4H, CH2(CH2)6CH2CH2Br); 1.37-1.20 (m, 13H, CH2(CH2)6CH2CH2Br); 1.12-1.09 (m, 3H, C(O)CH(CH3)CH2).
13C NMR{1H} (75.47 MHz, CDCl3, 298K) δ=211.05-209.91 (C═O); 48.82-45.0 (SCHCH2CH, C(O)CH(CH3)CH2); 41.40 (CH2(CH2)6CH2CH2Br); 39.56-39.52 (SCHCH2(CH2)6CH2CH2Br); 36.76-36.40 (C(O)CH(CH3)CH2); 32.70 (SCHCH2(CH2)6CH2CH2Br); 29.45-25.73 (SCHCH2(CH2)6CH2CH2Br); 15.38-14.42 (C(O)CH(CH3)CH2).
The monoadduct XA2ED was prepared according to the procedure used above in step 1.2) of example 2 for the preparation of the monoadduct XA2AP, but using 8.01 g (3.2×10−2 mol) of xanthate XA2 as prepared in step 1.2) of example 2, 1.25 g (1.5×10−2 mol) of 1,5-hexadiene (Aldrich), 1.77 g of LPO, and a reaction solvent composed of 6 ml of toluene.
The monoadduct XA2ED obtained in the form of a viscous yellow oil was purified by silica chromatography (eluent hexane/ethyl acetate: 95:5, v:v).
3.79 g of XA2ED were thus obtained (yield 73%).
1H NMR (300.13 MHz, CDCl3, 298K): δ (ppm) 5.47-5.46 (s, 2H, (CH3)2CHCH(O)CH3); 3.77-3.78 (m, 2H, SCHCH2CH(CH3)); 3.66-3.64 (m, 6H, CO2CH3); 2.73-2.61 (2H, m, SCHCH2CH(CH3)); 2.15-1.91 (m, 4H, SCHCH2CH(CH3)); 1.73-1.49 (m, 6H, (CH3)2CHCH(O)CH3 et SCH(CH2CH2)CH2CH(CH3)); 1.28-1.23 (d, 3H, SCHCH2CH(CH3)); 1.17-1.15 (d, 3H, (CH3)2CHCH(O)CH3); 0.94-0.92 (m, 6H, (CH3)2CHCH(O)CH3).
3.36 g (5.7 mmol) of XA2ED obtained above in the preceding step were placed in a sealed Schlenk tube under vacuum and brought to a temperature of 190° C. for 48 hours. The reaction mixture was subsequently cooled to room temperature and the volatile compounds formed were eliminated under vacuum. The thiolactone TL26 thus obtained in the form of a yellow oil was subsequently purified on a silica chromatography column (eluent ethyl acetate/hexane: 6:4 (v:v)).
1.2 g of TL26 were thus obtained in the form of a white powder (yield 84%).
1H NMR (300.13 MHz, CDCl3, 298K): δ (ppm) 3.78-3.62 (m, 2H, CHS); 2.75-2.43 (m, 2H, C(O)CH(CH3)CH2CH); 2.20-1.99 (m, 2H, C(O)CH(CH3)CH2CH); 1.56-1.38 (m, 5H, CHCH2CH2, CHCH2CH2); 1.17-1.13 (m, 6H, CH3).
13C NMR{1H} (282.38 MHz, CDCl3, 298K): δ (ppm) 210.74-209.61 (C═O); 48.78-45.42 ((CH3)CHCH2CH2CHS); 41.30-39.48 ((CH3)CHCH2CH2CHS); 36.59-36.13 (CHCH2CH2CH2); 15.38-14.45 (CH3).
The monoadduct XA2HD was prepared according to the procedure used above in step 1.2) of example 2 for the preparation of the monoadduct XA2AP, but using 9.07 g (3.6×10−2 mol) of xanthate XA2 as prepared in step 1.2) of example 2, 2.38 g (1.5×10−2 mol) of 1,9-decadiene (Aldrich), 2.03 g of LPO, and a reaction solvent composed of 7 ml of toluene.
The monoadduct XA2HD obtained in the form of a viscous yellow oil was purified by silica chromatography (eluent hexane/ethyl acetate: 90:10, v:v). 7.37 g of XA2HD were thus obtained (yield 68%).
1H NMR (300.13 MHz, CDCl3, 298K): δ (ppm) 5.58-5.49 (s, 2H, (CH3)2CHCH(O)CH3); 3.77-3.78 (m, 2H, SCHCH2CH(CH3)); 3.66-3.64 (m, 6H, CO2CH3); 2.73-2.61 (2H, m, SCHCH2CH(CH3)); 2.15-1.91 (m, 4H, SCHCH2CH(CH3)); 1.73-1.28 (m, 14H, (CH3)2CHCH(O)CH3 et SCH(CH2CH2CH2CH2CH2CH2)CHSH) et (CH3)2CHCH(O)CH3); 1.28-1.23 (d, 3H, SCHCH2CH(CH3)); 1.17-1.15 (d, 3H, (CH3)2CHCH(O)CH3); 0.94-0.92 (m, 6H, (CH3)2CHCH(O)CH3).
6.56 g (10.2 mmol) of XA2HD obtained above in the preceding step were placed in a sealed Schlenk tube under vacuum and brought to a temperature of 190° C. for 48 hours. The reaction mixture was subsequently cooled to room temperature and the volatile compounds formed were eliminated under vacuum. The thiolactone TL27 thus obtained in the form of a yellow oil was subsequently purified on a silica chromatography column (eluent ethyl acetate/hexane: 7:3 (v:v)).
2.48 g of TL27 were thus obtained in the form of a white powder (yield 77%).
1H NMR (300.13 MHz, CDCl3, 298K): δ (ppm) 3.78-3.62 (m, 2H, CHS); 2.75-2.43 (m, 2H, C(O)CH(CH3)CH2CH); 2.20-1.99 (m, 2H, C(O)CH(CH3)CH2CH); 1.78-1.64 (m, 4H, SCH(CH2CH2CH2CH2CH2CH2)CHSH) 1.53-1.38 (m, 9H, CHCH2CH2, SCH(CH2CH2CH2CH2CH2CH2)CHSH); 1.17-1.13 (m, 6H, CH3).
13C NMR{1H} (282.38 MHz, CDCl3, 298K): δ (ppm) 210.74-209.61 (C═O); 48.78-45.42 ((CH3)CHCH2CHS); 41.30-39.48 ((CH3)CHCH2CHS); 36.71-36.36 (SCH(CH2CH2CH2CH2CH2CH2)CHSH); 28.34-28.16 (SCH(CH2CH2CH2CH2CH2CH2)CHCHSH); 15.38-14.45 (CH3).
| Number | Date | Country | Kind |
|---|---|---|---|
| 1655781 | Jun 2016 | FR | national |
| 1660808 | Nov 2016 | FR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/FR2017/051637 | 6/20/2017 | WO | 00 |
