EP3571188A1 - Procédé de préparation de thiolactones, thiolactones obtenues par ledit procédé et utilisations - Google Patents
Procédé de préparation de thiolactones, thiolactones obtenues par ledit procédé et utilisationsInfo
- 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- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims abstract description 52
- 229920000642 polymer Polymers 0.000 claims abstract description 34
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 125
- 125000000217 alkyl group Chemical group 0.000 claims description 118
- -1 or unsaturated Chemical group 0.000 claims description 118
- 125000003118 aryl group Chemical group 0.000 claims description 81
- 150000003254 radicals Chemical class 0.000 claims description 69
- 229920006395 saturated elastomer Polymers 0.000 claims description 47
- 230000008569 process Effects 0.000 claims description 36
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 34
- 125000001072 heteroaryl group Chemical group 0.000 claims description 32
- 150000005840 aryl radicals Chemical class 0.000 claims description 29
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 28
- OROGUZVNAFJPHA-UHFFFAOYSA-N 3-hydroxy-2,4-dimethyl-2H-thiophen-5-one Chemical class CC1SC(=O)C(C)=C1O OROGUZVNAFJPHA-UHFFFAOYSA-N 0.000 claims description 27
- 125000002252 acyl group Chemical group 0.000 claims description 26
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 23
- 239000012991 xanthate Substances 0.000 claims description 23
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 20
- 238000001149 thermolysis Methods 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 18
- 229910052794 bromium Inorganic materials 0.000 claims description 17
- 239000000460 chlorine Substances 0.000 claims description 17
- 229910052801 chlorine Inorganic materials 0.000 claims description 17
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 claims description 17
- 125000005544 phthalimido group Chemical group 0.000 claims description 16
- 230000015572 biosynthetic process Effects 0.000 claims description 14
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 13
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- 150000001345 alkine derivatives Chemical class 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 125000004429 atom Chemical group 0.000 claims description 9
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical group O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004593 Epoxy Substances 0.000 claims description 8
- 150000001540 azides Chemical class 0.000 claims description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 229910052700 potassium Inorganic materials 0.000 claims description 8
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- 125000000732 arylene group Chemical group 0.000 claims description 7
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 125000005587 carbonate group Chemical group 0.000 claims description 6
- 125000006448 cycloalkyl cycloalkyl group Chemical group 0.000 claims description 6
- 238000007306 functionalization reaction Methods 0.000 claims description 6
- LJNVJNBYYLZZQW-UHFFFAOYSA-N 3-(4-methyl-5-oxothiolan-2-yl)propanenitrile Chemical compound CC1CC(SC1=O)CCC#N LJNVJNBYYLZZQW-UHFFFAOYSA-N 0.000 claims description 4
- 150000001451 organic peroxides Chemical class 0.000 claims description 4
- GAHKOSZFAXGYCV-UHFFFAOYSA-N 2-[2-(4-methyl-5-oxothiolan-2-yl)ethyl]isoindole-1,3-dione Chemical compound CC1CC(SC1=O)CCN1C(C2=CC=CC=C2C1=O)=O GAHKOSZFAXGYCV-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 125000004417 unsaturated alkyl group Chemical group 0.000 claims description 2
- 238000004177 carbon cycle Methods 0.000 claims 1
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 26
- 101150065749 Churc1 gene Proteins 0.000 description 21
- 102100038239 Protein Churchill Human genes 0.000 description 21
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 125000004432 carbon atom Chemical group C* 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 6
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 238000004587 chromatography analysis Methods 0.000 description 5
- 238000007363 ring formation reaction Methods 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 4
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 4
- 229920001400 block copolymer Polymers 0.000 description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 4
- PCDWJNVETVCPSE-UHFFFAOYSA-N methyl 2-methylpent-4-enoate Chemical compound COC(=O)C(C)CC=C PCDWJNVETVCPSE-UHFFFAOYSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- 239000012429 reaction media Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 150000003573 thiols Chemical class 0.000 description 4
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 3
- 101710141544 Allatotropin-related peptide Proteins 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 125000004434 sulfur atom Chemical group 0.000 description 3
- MXLMTQWGSQIYOW-UHFFFAOYSA-N 3-methyl-2-butanol Chemical compound CC(C)C(C)O MXLMTQWGSQIYOW-UHFFFAOYSA-N 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 2
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-araboascorbic acid Natural products OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- LKJPYSCBVHEWIU-UHFFFAOYSA-N N-[4-cyano-3-(trifluoromethyl)phenyl]-3-[(4-fluorophenyl)sulfonyl]-2-hydroxy-2-methylpropanamide Chemical compound C=1C=C(C#N)C(C(F)(F)F)=CC=1NC(=O)C(O)(C)CS(=O)(=O)C1=CC=C(F)C=C1 LKJPYSCBVHEWIU-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- HDFRDWFLWVCOGP-UHFFFAOYSA-N carbonothioic O,S-acid Chemical class OC(S)=O HDFRDWFLWVCOGP-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 125000003636 chemical group Chemical group 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000013626 chemical specie Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 235000010350 erythorbic acid Nutrition 0.000 description 2
- 239000004318 erythorbic acid Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 2
- 229940026239 isoascorbic acid Drugs 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- SKOLWUPSYHWYAM-UHFFFAOYSA-L methanethioate Chemical compound [O-]C([S-])=S SKOLWUPSYHWYAM-UHFFFAOYSA-L 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000012705 nitroxide-mediated radical polymerization Methods 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 150000002976 peresters Chemical class 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 125000004193 piperazinyl group Chemical group 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- AYMDJPGTQFHDSA-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-ethoxyethane Chemical compound CCOCCOCCOC=C AYMDJPGTQFHDSA-UHFFFAOYSA-N 0.000 description 1
- YQTCQNIPQMJNTI-UHFFFAOYSA-N 2,2-dimethylpropan-1-one Chemical group CC(C)(C)[C]=O YQTCQNIPQMJNTI-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- LDQYWNUWKVADJV-UHFFFAOYSA-N 2-[(1-amino-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanamide;dihydrate Chemical compound O.O.NC(=O)C(C)(C)N=NC(C)(C)C(N)=O LDQYWNUWKVADJV-UHFFFAOYSA-N 0.000 description 1
- REXUYBKPWIPONM-UHFFFAOYSA-N 2-bromoacetonitrile Chemical compound BrCC#N REXUYBKPWIPONM-UHFFFAOYSA-N 0.000 description 1
- DTELTOREECFDBC-UHFFFAOYSA-N 3-iodobenzoyl chloride Chemical compound ClC(=O)C1=CC=CC(I)=C1 DTELTOREECFDBC-UHFFFAOYSA-N 0.000 description 1
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 1
- SYMSHCCNDCDLPA-UHFFFAOYSA-N 9h-xanthene-2-carboxylic acid Chemical group C1=CC=C2CC3=CC(C(=O)O)=CC=C3OC2=C1 SYMSHCCNDCDLPA-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- ILBULIVEMIMRKD-UHFFFAOYSA-N C(C=C)#N.CC1CCSC1=O Chemical compound C(C=C)#N.CC1CCSC1=O ILBULIVEMIMRKD-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical class O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 101000582929 Homo sapiens Plasmolipin Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 102000015636 Oligopeptides Human genes 0.000 description 1
- 108010038807 Oligopeptides Proteins 0.000 description 1
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 102100030265 Plasmolipin Human genes 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 description 1
- YPWFISCTZQNZAU-UHFFFAOYSA-N Thiane Chemical group C1CCSCC1 YPWFISCTZQNZAU-UHFFFAOYSA-N 0.000 description 1
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 1
- YOOCQBNGNABQHG-UHFFFAOYSA-L [Zn+2].[O-]S[O-] Chemical compound [Zn+2].[O-]S[O-] YOOCQBNGNABQHG-UHFFFAOYSA-L 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000002521 alkyl halide group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 235000019395 ammonium persulphate Nutrition 0.000 description 1
- 125000005427 anthranyl group Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 125000005997 bromomethyl group Chemical group 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- UOCJDOLVGGIYIQ-PBFPGSCMSA-N cefatrizine Chemical group S([C@@H]1[C@@H](C(N1C=1C(O)=O)=O)NC(=O)[C@H](N)C=2C=CC(O)=CC=2)CC=1CSC=1C=NNN=1 UOCJDOLVGGIYIQ-PBFPGSCMSA-N 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- BLCKNMAZFRMCJJ-UHFFFAOYSA-N cyclohexyl cyclohexyloxycarbonyloxy carbonate Chemical compound C1CCCCC1OC(=O)OOC(=O)OC1CCCCC1 BLCKNMAZFRMCJJ-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- GKCPCPKXFGQXGS-UHFFFAOYSA-N ditert-butyldiazene Chemical compound CC(C)(C)N=NC(C)(C)C GKCPCPKXFGQXGS-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- WVFLGSMUPMVNTQ-UHFFFAOYSA-N n-(2-hydroxyethyl)-2-[[1-(2-hydroxyethylamino)-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCO WVFLGSMUPMVNTQ-UHFFFAOYSA-N 0.000 description 1
- BUGISVZCMXHOHO-UHFFFAOYSA-N n-[1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl]-2-[[1-[[1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl]amino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCC(CO)(CO)NC(=O)C(C)(C)N=NC(C)(C)C(=O)NC(CO)(CO)CO BUGISVZCMXHOHO-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- 125000001325 propanoyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 229940080818 propionamide Drugs 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 239000004296 sodium metabisulphite Substances 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 101150035983 str1 gene Proteins 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- JZFHXRUVMKEOFG-UHFFFAOYSA-N tert-butyl dodecaneperoxoate Chemical compound CCCCCCCCCCCC(=O)OOC(C)(C)C JZFHXRUVMKEOFG-UHFFFAOYSA-N 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 1
- 125000003507 tetrahydrothiofenyl group Chemical group 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000002813 thiocarbonyl group Chemical group *C(*)=S 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
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).
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Abstract
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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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 |
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EP3571188A1 true EP3571188A1 (fr) | 2019-11-27 |
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EP18704047.2A Withdrawn EP3571188A1 (fr) | 2017-01-18 | 2018-01-16 | Procédé de préparation de thiolactones, thiolactones obtenues par ledit procédé et utilisations |
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US (1) | US20190359603A1 (fr) |
EP (1) | EP3571188A1 (fr) |
FR (1) | FR3061907A1 (fr) |
WO (1) | WO2018134510A1 (fr) |
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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 (fr) * | 2011-08-31 | 2015-12-09 | Bridgestone Corporation | Polymères fonctionnalisés avec des lactones ou des thiolactones contenant un groupe aminé protégé |
FR3024734B1 (fr) * | 2014-08-08 | 2018-03-02 | Xanchem | Polymere dote de proprietes d'adherence |
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2017
- 2017-01-18 FR FR1750384A patent/FR3061907A1/fr not_active Withdrawn
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2018
- 2018-01-16 EP EP18704047.2A patent/EP3571188A1/fr not_active Withdrawn
- 2018-01-16 WO PCT/FR2018/050099 patent/WO2018134510A1/fr unknown
- 2018-01-16 US US16/477,424 patent/US20190359603A1/en not_active Abandoned
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WO2018134510A1 (fr) | 2018-07-26 |
US20190359603A1 (en) | 2019-11-28 |
FR3061907A1 (fr) | 2018-07-20 |
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