ES2393951B1 - DERIVATIVES OF RENT GALATES AS ANTIOXIDANTS AND SURFACTANTS - Google Patents
DERIVATIVES OF RENT GALATES AS ANTIOXIDANTS AND SURFACTANTS Download PDFInfo
- Publication number
- ES2393951B1 ES2393951B1 ES201130985A ES201130985A ES2393951B1 ES 2393951 B1 ES2393951 B1 ES 2393951B1 ES 201130985 A ES201130985 A ES 201130985A ES 201130985 A ES201130985 A ES 201130985A ES 2393951 B1 ES2393951 B1 ES 2393951B1
- Authority
- ES
- Spain
- Prior art keywords
- compound
- general formula
- gallate
- dihydroxybenzoate
- alkyl
- 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.)
- Expired - Fee Related
Links
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 36
- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 30
- 150000001875 compounds Chemical class 0.000 claims abstract description 95
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 73
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000000839 emulsion Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 6
- 125000000304 alkynyl group Chemical group 0.000 claims abstract description 4
- 150000003839 salts Chemical class 0.000 claims abstract description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 7
- JUUBCHWRXWPFFH-UHFFFAOYSA-N Hydroxytyrosol Chemical compound OCCC1=CC=C(O)C(O)=C1 JUUBCHWRXWPFFH-UHFFFAOYSA-N 0.000 claims description 33
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical class OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 33
- 235000013305 food Nutrition 0.000 claims description 17
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 235000003248 hydroxytyrosol Nutrition 0.000 claims description 15
- 229940095066 hydroxytyrosol Drugs 0.000 claims description 15
- -1 acyl gallate Chemical compound 0.000 claims description 14
- 229940071221 dihydroxybenzoate Drugs 0.000 claims description 14
- 230000003078 antioxidant effect Effects 0.000 claims description 13
- 125000002347 octyl 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])[H] 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000010511 deprotection reaction Methods 0.000 claims description 12
- 229920006395 saturated elastomer Polymers 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 9
- 239000008103 glucose Substances 0.000 claims description 9
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- AEMOLEFTQBMNLQ-AQKNRBDQSA-N D-glucopyranuronic acid Chemical compound OC1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@H]1O AEMOLEFTQBMNLQ-AQKNRBDQSA-N 0.000 claims description 7
- IAJILQKETJEXLJ-UHFFFAOYSA-N Galacturonsaeure Natural products O=CC(O)C(O)C(O)C(O)C(O)=O IAJILQKETJEXLJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003905 agrochemical Substances 0.000 claims description 7
- 239000002537 cosmetic Substances 0.000 claims description 7
- 229940097043 glucuronic acid Drugs 0.000 claims description 7
- DQHJNOHLEKVUHU-UHFFFAOYSA-N hexyl 3,4,5-trihydroxybenzoate Chemical compound CCCCCCOC(=O)C1=CC(O)=C(O)C(O)=C1 DQHJNOHLEKVUHU-UHFFFAOYSA-N 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 6
- 125000004036 acetal group Chemical group 0.000 claims description 5
- 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 claims description 5
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical group O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- HEWZVZIVELJPQZ-UHFFFAOYSA-N 2,2-dimethoxypropane Chemical compound COC(C)(C)OC HEWZVZIVELJPQZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000348 glycosyl donor Substances 0.000 claims description 4
- 150000002772 monosaccharides Chemical class 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- UPQQXPKAYZYUKO-UHFFFAOYSA-N 2,2,2-trichloroacetamide Chemical compound OC(=N)C(Cl)(Cl)Cl UPQQXPKAYZYUKO-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 125000000913 palmityl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000006239 protecting group Chemical group 0.000 claims description 3
- 239000003599 detergent Substances 0.000 claims description 2
- 239000008194 pharmaceutical composition Substances 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims 5
- 244000155688 Abutilon pannosum Species 0.000 claims 3
- 230000001077 hypotensive effect Effects 0.000 claims 3
- 125000003132 pyranosyl group Chemical group 0.000 claims 3
- CJDRUOGAGYHKKD-XMTJACRCSA-N (+)-Ajmaline Natural products O[C@H]1[C@@H](CC)[C@@H]2[C@@H]3[C@H](O)[C@@]45[C@@H](N(C)c6c4cccc6)[C@@H](N1[C@H]3C5)C2 CJDRUOGAGYHKKD-XMTJACRCSA-N 0.000 claims 2
- 241000940612 Medina Species 0.000 claims 2
- 241000282320 Panthera leo Species 0.000 claims 2
- 235000009330 Terminalia Nutrition 0.000 claims 2
- 241001534869 Terminalia Species 0.000 claims 2
- 229940013317 fish oils Drugs 0.000 claims 2
- 229930182478 glucoside Natural products 0.000 claims 2
- 150000008131 glucosides Chemical class 0.000 claims 2
- 125000002367 glucuronosyl group Chemical group 0.000 claims 2
- 229930182470 glycoside Natural products 0.000 claims 2
- 150000002338 glycosides Chemical class 0.000 claims 2
- 125000000623 heterocyclic group Chemical group 0.000 claims 2
- 238000002955 isolation Methods 0.000 claims 2
- HSMJRIUFXFAZSY-UHFFFAOYSA-N methylenedinitramine Chemical compound [O-][N+](=O)NCN[N+]([O-])=O HSMJRIUFXFAZSY-UHFFFAOYSA-N 0.000 claims 2
- 229930014626 natural product Natural products 0.000 claims 2
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical group OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 claims 1
- 241000196324 Embryophyta Species 0.000 claims 1
- 102220547770 Inducible T-cell costimulator_A23L_mutation Human genes 0.000 claims 1
- 244000071109 Terminalia arjuna Species 0.000 claims 1
- 235000000538 Terminalia arjuna Nutrition 0.000 claims 1
- 150000001241 acetals Chemical group 0.000 claims 1
- 150000001298 alcohols Chemical class 0.000 claims 1
- 235000014113 dietary fatty acids Nutrition 0.000 claims 1
- 239000000284 extract Substances 0.000 claims 1
- 229930195729 fatty acid Natural products 0.000 claims 1
- 239000000194 fatty acid Substances 0.000 claims 1
- 239000000399 hydroalcoholic extract Substances 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 235000006708 antioxidants Nutrition 0.000 description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 238000002376 fluorescence recovery after photobleaching Methods 0.000 description 9
- 150000002430 hydrocarbons Chemical group 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 229940074391 gallic acid Drugs 0.000 description 8
- 235000004515 gallic acid Nutrition 0.000 description 8
- 125000003147 glycosyl group Chemical group 0.000 description 7
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 7
- NRPKURNSADTHLJ-UHFFFAOYSA-N octyl gallate Chemical compound CCCCCCCCOC(=O)C1=CC(O)=C(O)C(O)=C1 NRPKURNSADTHLJ-UHFFFAOYSA-N 0.000 description 7
- RPWFJAMTCNSJKK-UHFFFAOYSA-N Dodecyl gallate Chemical compound CCCCCCCCCCCCOC(=O)C1=CC(O)=C(O)C(O)=C1 RPWFJAMTCNSJKK-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- XOPOEBVTQYAOSV-UHFFFAOYSA-N butyl 3,4,5-trihydroxybenzoate Chemical compound CCCCOC(=O)C1=CC(O)=C(O)C(O)=C1 XOPOEBVTQYAOSV-UHFFFAOYSA-N 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- AOTRKUOCGUXQCY-UHFFFAOYSA-N decyl 3,4,5-trihydroxybenzoate Chemical compound CCCCCCCCCCOC(=O)C1=CC(O)=C(O)C(O)=C1 AOTRKUOCGUXQCY-UHFFFAOYSA-N 0.000 description 6
- 235000010387 octyl gallate Nutrition 0.000 description 6
- 239000000574 octyl gallate Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- MGJZITXUQXWAKY-UHFFFAOYSA-N diphenyl-(2,4,6-trinitrophenyl)iminoazanium Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1N=[N+](C=1C=CC=CC=1)C1=CC=CC=C1 MGJZITXUQXWAKY-UHFFFAOYSA-N 0.000 description 4
- 235000010386 dodecyl gallate Nutrition 0.000 description 4
- 239000000555 dodecyl gallate Substances 0.000 description 4
- 229940080643 dodecyl gallate Drugs 0.000 description 4
- BRNPAEUKZMBRLQ-UHFFFAOYSA-N octadecyl 3,4,5-trihydroxybenzoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C1=CC(O)=C(O)C(O)=C1 BRNPAEUKZMBRLQ-UHFFFAOYSA-N 0.000 description 4
- 150000003214 pyranose derivatives Chemical group 0.000 description 4
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229920001213 Polysorbate 20 Polymers 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- WPMWEFXCIYCJSA-UHFFFAOYSA-N Tetraethylene glycol monododecyl ether Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCO WPMWEFXCIYCJSA-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- CGWVAQMLSHXXQE-GASJEMHNSA-N [(3r,4s,5s,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] 2,2,2-trichloroethanimidate Chemical compound OC[C@H]1OC(OC(=N)C(Cl)(Cl)Cl)[C@H](O)[C@@H](O)[C@@H]1O CGWVAQMLSHXXQE-GASJEMHNSA-N 0.000 description 3
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- GTIPOIHUAWNHMQ-UHFFFAOYSA-N decyl 2-hydroxyacetate Chemical compound CCCCCCCCCCOC(=O)CO GTIPOIHUAWNHMQ-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 239000000386 donor Substances 0.000 description 3
- HHEAADYXPMHMCT-UHFFFAOYSA-N dpph Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1[N]N(C=1C=CC=CC=1)C1=CC=CC=C1 HHEAADYXPMHMCT-UHFFFAOYSA-N 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 238000003818 flash chromatography Methods 0.000 description 3
- TYCUSKFOGZNIBO-UHFFFAOYSA-N hexadecyl 3,4,5-trihydroxybenzoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C1=CC(O)=C(O)C(O)=C1 TYCUSKFOGZNIBO-UHFFFAOYSA-N 0.000 description 3
- 239000000693 micelle Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 3
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- XYJQBHCHAZPWHA-UHFFFAOYSA-N CC(C)C([CH2-])=O Chemical compound CC(C)C([CH2-])=O XYJQBHCHAZPWHA-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000011786 L-ascorbyl-6-palmitate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ZTHYODDOHIVTJV-UHFFFAOYSA-N Propyl gallate Chemical compound CCCOC(=O)C1=CC(O)=C(O)C(O)=C1 ZTHYODDOHIVTJV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000006071 cream Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 125000005640 glucopyranosyl group Chemical group 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000006210 lotion Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 239000000825 pharmaceutical preparation Substances 0.000 description 2
- 229940127557 pharmaceutical product Drugs 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 125000004079 stearyl 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])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])[H] 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000037072 sun protection Effects 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 125000001544 thienyl group Chemical group 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- JPYHXSWNADKGBI-GASJEMHNSA-N (3r,4s,5s,6r)-2-chloro-6-(hydroxymethyl)oxane-3,4,5-triol Chemical compound OC[C@H]1OC(Cl)[C@H](O)[C@@H](O)[C@@H]1O JPYHXSWNADKGBI-GASJEMHNSA-N 0.000 description 1
- DOUMFZQKYFQNTF-WUTVXBCWSA-N (R)-rosmarinic acid Chemical class C([C@H](C(=O)O)OC(=O)\C=C\C=1C=C(O)C(O)=CC=1)C1=CC=C(O)C(O)=C1 DOUMFZQKYFQNTF-WUTVXBCWSA-N 0.000 description 1
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 1
- NQBXMEBFYHFAIU-UHFFFAOYSA-N 2-(3,4-dihydroxyphenyl)ethyl decanoate Chemical compound CCCCCCCCCC(=O)OCCC1=CC=C(O)C(O)=C1 NQBXMEBFYHFAIU-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- QAQJMLQRFWZOBN-LAUBAEHRSA-N L-ascorbyl-6-palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](O)[C@H]1OC(=O)C(O)=C1O QAQJMLQRFWZOBN-LAUBAEHRSA-N 0.000 description 1
- 235000000072 L-ascorbyl-6-palmitate Nutrition 0.000 description 1
- 230000002292 Radical scavenging effect Effects 0.000 description 1
- IBUZGVQIKARDAF-RQICVUQASA-N [(2r,3r,4s,5r)-3,4,5-triacetyloxy-6-(2,2,2-trichloroethanimidoyl)oxyoxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@H]1OC(OC(=N)C(Cl)(Cl)Cl)[C@H](OC(C)=O)[C@@H](OC(C)=O)[C@@H]1OC(C)=O IBUZGVQIKARDAF-RQICVUQASA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010385 ascorbyl palmitate Nutrition 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- CBDBLXUJRXZQMK-UHFFFAOYSA-N butyl 3,4-dihydroxybenzoate Chemical compound CCCCOC(=O)C1=CC=C(O)C(O)=C1 CBDBLXUJRXZQMK-UHFFFAOYSA-N 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229920006184 cellulose methylcellulose Polymers 0.000 description 1
- 239000011153 ceramic matrix composite Substances 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000012710 chemistry, manufacturing and control Methods 0.000 description 1
- CWVRJTMFETXNAD-JUHZACGLSA-N chlorogenic acid Chemical class O[C@@H]1[C@H](O)C[C@@](O)(C(O)=O)C[C@H]1OC(=O)\C=C\C1=CC=C(O)C(O)=C1 CWVRJTMFETXNAD-JUHZACGLSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 235000015872 dietary supplement Nutrition 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 235000013376 functional food Nutrition 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000002417 nutraceutical Substances 0.000 description 1
- 235000021436 nutraceutical agent Nutrition 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 235000010388 propyl gallate Nutrition 0.000 description 1
- 239000000473 propyl gallate Substances 0.000 description 1
- 229940075579 propyl gallate Drugs 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229930003799 tocopherol Natural products 0.000 description 1
- 239000011732 tocopherol Substances 0.000 description 1
- 150000003611 tocopherol derivatives Chemical class 0.000 description 1
- 235000019149 tocopherols Nutrition 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- FTVLMFQEYACZNP-UHFFFAOYSA-N trimethylsilyl trifluoromethanesulfonate Chemical compound C[Si](C)(C)OS(=O)(=O)C(F)(F)F FTVLMFQEYACZNP-UHFFFAOYSA-N 0.000 description 1
- QUEDXNHFTDJVIY-UHFFFAOYSA-N γ-tocopherol Chemical class OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1 QUEDXNHFTDJVIY-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
- C07H15/20—Carbocyclic rings
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23B—PRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
- A23B2/00—Preservation of foods or foodstuffs, in general
- A23B2/70—Preservation of foods or foodstuffs, in general by treatment with chemicals
- A23B2/725—Preservation of foods or foodstuffs, in general by treatment with chemicals in the form of liquids or solids
- A23B2/729—Organic compounds; Microorganisms; Enzymes
- A23B2/742—Organic compounds containing oxygen
- A23B2/754—Organic compounds containing oxygen containing carboxyl groups
- A23B2/758—Carboxylic acid esters
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/06—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite
- A61K47/08—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite containing oxygen, e.g. ethers, acetals, ketones, quinones, aldehydes, peroxides
- A61K47/10—Alcohols; Phenols; Salts thereof, e.g. glycerol; Polyethylene glycols [PEG]; Poloxamers; PEG/POE alkyl ethers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D309/08—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members 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
- C07D309/10—Oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
- C11D3/223—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin oxidised
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- Pharmacology & Pharmacy (AREA)
- Polymers & Plastics (AREA)
- Animal Behavior & Ethology (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Emergency Medicine (AREA)
- Saccharide Compounds (AREA)
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Abstract
Derivados de galatos de alquilo como antioxidantes y surfactantes.#Compuesto de fórmula general (I) o una de sus sales, donde: R{sub,1} representa a CH{sub,2}OH o COOH y R{sub,2} representa una cadena hidrocarbonada C{sub,4}-C{sub,22} lineal o ramificada, donde la cadena hidrocarbonada puede opcionalmente presentar una o varias insaturaciones elegidas independientemente entre insaturaciones de tipo alquenilo o alquinilo; siempre que, cuando R{sub,1} representa CH{sub,2}OH y R{sub,2} representa una cadena hidrocarbonada lineal o ramificada, opcionalmente con una o varias insaturaciones alquenilo, la longitud de la cadena hidrocarbonada es C{sub,4}-C{sub,12}. Su procedimiento de obtención y su uso como surfactante y oxidante, en particular como parte de una composición en forma de emulsión.Derivatives of alkyl gallates as antioxidants and surfactants. # Compound of general formula (I) or one of its salts, where: R {sub, 1} represents CH {sub, 2} OH or COOH and R {sub, 2} represents a linear or branched C {sub, 4} -C {sub, 22} hydrocarbon chain, where the hydrocarbon chain may optionally have one or more unsaturations independently selected from alkenyl or alkynyl unsaturations; provided that, when R {sub, 1} represents CH {sub, 2} OH and R {sub, 2} represents a linear or branched hydrocarbon chain, optionally with one or more alkenyl unsaturations, the length of the hydrocarbon chain is C { sub, 4} -C {sub, 12}. Its process of obtaining and its use as a surfactant and oxidant, in particular as part of an emulsion composition.
Description
Derivados de galatos de alquilo como antioxidantes y surfactantes. Derivatives of alkyl gallates as antioxidants and surfactants.
5 La presente invención se refiere a un grupo de compuestos derivados de galatos de alquilo con propiedades antioxidantes y surfactantes, a su procedimiento de obtención y a su uso como antioxidante en composiciones alimentarias, cosméticas y farmacéuticas, preferentemente en forma de emulsión. The present invention relates to a group of compounds derived from alkyl gallates with antioxidant and surfactant properties, their method of production and their use as an antioxidant in food, cosmetic and pharmaceutical compositions, preferably in the form of emulsion.
ESTADO DE LA TÉCNICA ANTERIOR STATE OF THE PREVIOUS TECHNIQUE
10 Los antioxidantes son compuestos capaces de retardar o prevenir la oxidación de otras moléculas o materiales. La oxidación es un proceso que deteriora el estado de todo tipo de materiales. Por esta razón los antioxidantes se usan principalmente como conservantes de alimentos y cosméticos, así como en otros procesos tales como en la prevención de la degradación del caucho y la gasolina. 10 Antioxidants are compounds capable of retarding or preventing the oxidation of other molecules or materials. Oxidation is a process that deteriorates the state of all types of materials. For this reason antioxidants are mainly used as food and cosmetic preservatives, as well as in other processes such as in the prevention of degradation of rubber and gasoline.
15 En el caso de los alimentos, las emulsiones son especialmente sensibles a la oxidación. Los antioxidantes que se vienen utilizando para conservar las emulsiones son los tocoferoles y derivados de tocoferol (EP1634502), el ácido ascórbico y el ascorbil palmitato, el butil-hidroxi-anisol (BHA) y el butil-hidroxi-tolueno (BHT) y algunos galatos de alquilo como el galato de propilo, galato de octilo y galato de dodecilo (US6261541). 15 In the case of food, emulsions are especially sensitive to oxidation. The antioxidants that are being used to preserve emulsions are tocopherols and tocopherol derivatives (EP1634502), ascorbic acid and ascorbyl palmitate, butyl hydroxy-anisole (BHA) and butyl-hydroxy-toluene (BHT) and some alkyl gallates such as propyl gallate, octyl gallate and dodecyl gallate (US6261541).
20 Una serie de derivados de galatos de alquilo se describieron como agentes blaqueantes de la piel y antioxidantes donde el grupo alquilo podía ser de longitud C1-C18 e incluir alguna insaturación y alguno de los grupos hidroxilos podían estar sustituidos por un monosacárido (US7282520B2, JP2004075815 y JP2000319116). 20 A series of derivatives of alkyl gallates were described as skin blasting agents and antioxidants where the alkyl group could be of C1-C18 length and include some unsaturation and some of the hydroxyl groups could be substituted by a monosaccharide (US7282520B2, JP2004075815 and JP2000319116).
25 Recientemente se han descrito un nuevo tipo de compuestos, los fenoles lipídicos, que están demostrando gran efectividad como antioxidantes en emulsiones. Es el caso de los ésteres de ácido clorogénico (Laguerre y col. J. Agric. Food Chem. 2010, 2869), los ésteres del ácido rosmarínico (Laguerre y col. J. Agric. Food Chem. 2009, 11335) y los ésteres de hidroxitirosol (Medina y col. J. Agric. Food Chem. 2009, 9773), donde precisamente los derivados modificados con cadenas alquílicas de tamaño medio (C8-C12) son los antioxidantes más eficaces. 25 A new type of compound, lipid phenols, has recently been described, which is proving highly effective as antioxidants in emulsions. This is the case of chlorogenic acid esters (Laguerre et al. J. Agric. Food Chem. 2010, 2869), rosmarinic acid esters (Laguerre et al. J. Agric. Food Chem. 2009, 11335) and esters hydroxytyrosol (Medina et al. J. Agric. Food Chem. 2009, 9773), where precisely modified derivatives with medium-sized alkyl chains (C8-C12) are the most effective antioxidants.
30 Adicionalmente, se ha demostrado para el caso de los ésteres de hidroxitirosol que los antioxidantes más eficaces, el octanoato de hidroxitirosol y el decanoato de hidroxitirosol además también son los mejores surfactantes de la serie de derivados alquílicos (Lucas y col. J. Agric. Food Chem. 2010, 9778). In addition, it has been demonstrated in the case of hydroxytyrosol esters that the most effective antioxidants, hydroxytyrosol octanoate and hydroxytyrosol decanoate are also the best surfactants in the series of alkyl derivatives (Lucas et al. J. Agric. Food Chem. 2010, 9778).
DESCRIPCIÓN DE LA INVENCIÓN DESCRIPTION OF THE INVENTION
35 La presente invención proporciona un grupo de compuestos derivados de galatos de alquilo que debido a sus propiedades antioxidantes y surfactantes, pueden ser usados como antioxidantes en emulsiones y por lo tanto tener aplicación en productos alimentarios, agroquímicos, cosméticos, de higiene personal o en productos farmacéuticos. The present invention provides a group of compounds derived from alkyl gallates that due to their antioxidant and surfactant properties, can be used as antioxidants in emulsions and therefore have application in food, agrochemical, cosmetic, personal hygiene products or products Pharmacists
40 En un primer aspecto, la presente invención se refiere a un compuesto de fórmula general (I) In a first aspect, the present invention relates to a compound of general formula (I)
OH OH
o una de sus sales, donde: or one of its salts, where:
R1 representa a CH2OH o COOH y R2 representa una cadena hidrocarbonada C4-C22 lineal o ramificada, donde la R1 represents CH2OH or COOH and R2 represents a linear or branched C4-C22 hydrocarbon chain, where the
45 cadena hidrocarbonada puede opcionalmente presentar una o varias insaturaciones elegidas independientemente entre insaturaciones de tipo alquenilo o alquinilo; The hydrocarbon chain may optionally have one or more unsaturations independently selected from alkenyl or alkynyl type unsaturations;
siempre que, cuando R1 representa CH2OH y R2 representa una cadena hidrocarbonada lineal o ramificada, opcionalmente con una o varias insaturaciones alquenilo, la longitud de la cadena hidrocarbonada es C4-C12. provided that when R1 represents CH2OH and R2 represents a linear or branched hydrocarbon chain, optionally with one or more alkenyl unsaturations, the length of the hydrocarbon chain is C4-C12.
En una realización preferida de los compuestos de fórmula general (I), el anillo de piranosa es una glucosa. In a preferred embodiment of the compounds of general formula (I), the pyranose ring is a glucose.
En otra realización preferida de la presente invención, el anillo de piranosa del compuesto de fórmula general (I) representa un ácido glucurónico. In another preferred embodiment of the present invention, the pyranose ring of the compound of general formula (I) represents a glucuronic acid.
En otra realización preferida adicional, el compuesto de fórmula (I) de la presente invención se caracteriza porque la unión del monosacárido, preferentemente glucosa o ácido glucurónico, al anillo fenólico puede ser alfa o beta. Preferentemente, dicha unión es beta. In another additional preferred embodiment, the compound of formula (I) of the present invention is characterized in that the binding of the monosaccharide, preferably glucose or glucuronic acid, to the phenolic ring can be alpha or beta. Preferably, said binding is beta.
En los compuestos de fórmula general (I), R2 es una cadena hidrocarbonada que puede ser lineal o ramificada. Además, esta cadena hidrocarbonada puede ser una cadena saturada, monoinsaturada o poliinsaturada. Así mismo, las insaturaciones pueden ser de tipo alquenilo, alquinilo o de ambos. Preferentemente, R2 es una cadena hidrocarbonada saturada. In the compounds of general formula (I), R2 is a hydrocarbon chain that can be linear or branched. In addition, this hydrocarbon chain can be a saturated, monounsaturated or polyunsaturated chain. Also, the unsaturations can be alkenyl, alkynyl or both. Preferably, R2 is a saturated hydrocarbon chain.
En otra realización preferida adicional, el compuesto de fórmula (I) se caracteriza porque cuando R1 = CH2OH y el anillo de piranosa representa glucosa, R2 representa una cadena hidrocarbonada C4-C12 lineal, siendo preferente que R2 sea una cadena hidrocarbonada C4-C12 lineal y saturada. In another additional preferred embodiment, the compound of formula (I) is characterized in that when R1 = CH2OH and the pyranose ring represents glucose, R2 represents a linear C4-C12 hydrocarbon chain, with R2 being preferably a linear C4-C12 hydrocarbon chain and saturated.
De forma más preferente, el compuesto de fórmula (I) se caracteriza porque la unión de la glucosa con el anillo fenólico tiene estereoquímica beta y R2 representa una cadena hidrocarbonada C4-C12 lineal, siendo preferente que R2 sea una cadena hidrocarbonada C4-C12 lineal y saturada. More preferably, the compound of formula (I) is characterized in that the union of glucose with the phenolic ring has beta stereochemistry and R2 represents a linear C4-C12 hydrocarbon chain, with R2 being preferably a linear C4-C12 hydrocarbon chain and saturated.
De forma aún más preferente, el compuesto de fórmula (I) de la presente invención, cuando R1 es glucosa, se elige entre el grupo que consiste en: Even more preferably, the compound of formula (I) of the present invention, when R1 is glucose, is selected from the group consisting of:
3-O-(�-D-glucopiranosil)-4,5-dihidroxibenzoato de butilo, 3-O-(�-D-glucopiranosil)-4,5-dihidroxibenzoato de hexilo, 3-O-(�-D-glucopiranosil)-4,5-dihidroxibenzoato de octilo, 3-O-(�-D-glucopiranosil)-4,5-dihidroxibenzoato de decilo, y 3-O-(�-D-glucopiranosil)-4,5-dihidroxibenzoato de dodecilo. Butyl 3-O- (�-D-glucopyranosyl) -4,5-dihydroxybenzoate, Hexyl 3-O- (�-D-glucopyranosyl) -4,5-dihydroxybenzoate, Octyl 3-O- (�-D-glucopyranosyl) -4,5-dihydroxybenzoate, Decyl 3-O- (�-D-glucopyranosyl) -4,5-dihydroxybenzoate, and Dodecyl 3-O- (�-D-glucopyranosyl) -4,5-dihydroxybenzoate.
De forma especialmente preferente, el compuesto de fórmula (I) de la presente invención, cuando R1 es glucosa, se elige entre el grupo que consiste en: Particularly preferably, the compound of formula (I) of the present invention, when R1 is glucose, is selected from the group consisting of:
3-O-(�-D-glucopiranosil)-4,5-dihidroxibenzoato de hexilo, 3-O-(�-D-glucopiranosil)-4,5-dihidroxibenzoato de octilo, y 3-O-(�-D-glucopiranosil)-4,5-dihidroxibenzoato de decilo. Hexyl 3-O- (�-D-glucopyranosyl) -4,5-dihydroxybenzoate, Octyl 3-O- (�-D-glucopyranosyl) -4,5-dihydroxybenzoate, and Decyl 3-O- (�-D-glucopyranosyl) -4,5-dihydroxybenzoate.
En otra realización preferida adicional, el compuesto de fórmula (I) se caracteriza porque cuando R1 = COOH y el anillo de piranosa representa ácido glucurónico, R2 representa una cadena hidrocarbonada C4-C22 lineal, siendo preferente que R2 es una cadena hidrocarbonada C4-C22 lineal y saturada. In another further preferred embodiment, the compound of formula (I) is characterized in that when R1 = COOH and the pyranose ring represents glucuronic acid, R2 represents a linear C4-C22 hydrocarbon chain, with R2 being preferably a C4-C22 hydrocarbon chain linear and saturated.
De forma aún más preferente R2 es una cadena hidrocarbonada C8-C16 lineal y saturada. Even more preferably R2 is a linear and saturated C8-C16 hydrocarbon chain.
De forma especialmente preferente, el compuesto de fórmula (I) se caracteriza porque la unión del ácido glucurónico con el anillo fenólico tiene estereoquímica beta y R2 representa una cadena hidrocarbonada C4-C22 lineal. Preferentemente, R2 es una cadena hidrocarbonada C4-C22 lineal y saturada. Especially preferably, the compound of formula (I) is characterized in that the union of glucuronic acid with the phenolic ring has beta stereochemistry and R2 represents a linear C4-C22 hydrocarbon chain. Preferably, R2 is a linear and saturated C4-C22 hydrocarbon chain.
De forma aún más preferente, R2 es una cadena hidrocarbonada C8-C16 lineal y saturada. Even more preferably, R2 is a linear and saturated C8-C16 hydrocarbon chain.
De forma especialmente preferente, el compuesto de fórmula (I) de la presente invención, cuando R1 es ácido glucurónico, se elige entre el grupo que consiste en: Especially preferably, the compound of formula (I) of the present invention, when R 1 is glucuronic acid, is selected from the group consisting of:
3-O-(�-D-glucurunopiranosil)-4,5-dihidroxibenzoato de octilo, y 3-O-(�-D-glucurunopiranosil)-4,5-dihidroxibenzoato de hexadecilo Octyl 3-O- (�-D-glucurunopyranosyl) -4,5-dihydroxybenzoate, and Hexadecyl 3-O- (�-D-glucurunopyranosyl) -4,5-dihydroxybenzoate
Un segundo aspecto de la presente invención se refiere al procedimiento de obtención del compuesto de fórmula general (I) de la invención, que comprende las siguientes etapas: A second aspect of the present invention relates to the process for obtaining the compound of general formula (I) of the invention, which comprises the following steps:
- a. to.
- protección mediante un grupo acetal de dos grupos fenólicos contiguos del correspondiente galato de acilo (II), donde R2 tiene el mismo significado que en el compuesto de fórmula (I) para obtener el derivado (III); protection by means of an acetal group of two contiguous phenolic groups of the corresponding acyl gallate (II), where R2 has the same meaning as in the compound of formula (I) to obtain the derivative (III);
- b. b.
- reacción de (III) con el donador de glicosilo (IV), donde R1 representa a CH2OH o COOH y X representa a un grupo saliente para dar el derivado (V); reaction of (III) with the glycosyl donor (IV), where R 1 represents CH 2 OH or COOH and X represents a leaving group to give the derivative (V);
- c. C.
- desprotección del grupo acetal del derivado (V) para obtener (VI); deprotection of the acetal group of the derivative (V) to obtain (VI);
- d. d.
- desprotección del resto de grupos protectores del derivado (VI) para obtener el compuesto de fórmula general (I), deprotection of the other protecting groups of the derivative (VI) to obtain the compound of general formula (I),
donde el orden de las etapas de desprotección c y d se puede invertir. where the order of the deprotection stages c and d can be reversed.
El procedimiento de la invención se puede observar en el siguiente esquema: The process of the invention can be observed in the following scheme:
R1O X R1O X
OH O O(IV) HO OH HO O OAc R1OO OAcO OAc OH O O (IV) HO OH HO O OAc R1OO OAcO OAc
AcO OAc AcO OAc
O OR2 O OR2 OAc (V) O OR2(II) (III) OR OR2 OR OR2 OAc (V) OR OR2 (II) (III)
OH OH R1O O OH OH R1O O
OHOH R1OO OHOH R1OO
AcO HO OAc OH AcO HO OAc OH
(I) (I)
OAc OH (VI) O OR2 O OR2 OAc OH (VI) OR OR2 OR OR2
En una realización preferida, el compuesto (III) se prepara por reacción de (II) con un dimetil acetónido y un ácido en un disolvente orgánico para formar el grupo dimetil acetal. Preferentemente, el dimetil acetónido puede ser acetona In a preferred embodiment, the compound (III) is prepared by reacting (II) with a dimethyl acetonide and an acid in an organic solvent to form the dimethyl acetal group. Preferably, the dimethyl acetonide can be acetone
- o dimetoxipropano y en una realización más preferida puede ser dimetoxipropano. Preferentemente, el ácido puede ser ácido canforsulfónico, ácido toluensulfónico, ácido acético, ácido fosfórico o ácido cítrico y en una realización más preferida puede ser ácido canforsulfónico. Preferentemente, el disolvente puede ser cloroformo, diclorometano, tetrahidrofurano o éter etílico y en una realización más preferida puede ser cloroformo. or dimethoxypropane and in a more preferred embodiment it may be dimethoxypropane. Preferably, the acid may be camphorsulfonic acid, toluenesulfonic acid, acetic acid, phosphoric acid or citric acid and in a more preferred embodiment it may be camphorsulfonic acid. Preferably, the solvent may be chloroform, dichloromethane, tetrahydrofuran or ethyl ether and in a more preferred embodiment it may be chloroform.
En una realización preferida, el compuesto (V) se prepara por reacción de (III) con un dador de glicosilo (IV) en presencia de un catalizador y en un disolvente orgánico. El sustituyente X es un grupo saliente habitual en química orgánica tal como, por ejemplo, Cl, F, SPh, ONHCCl3. Preferentemente, el dador de glucosilo (IV) puede ser el tricloroacetimidato de 2,3,4,6-O-tetraacetil glucopiranosilo, el cloruro de 2,3,4,6-O-tetraacetil glucopiranosilo, el fluoruro de 2,3,4,6-O-tetraacetil glucopiranosilo, el tiofenilo de 2,3,4,6-O-tetraacetil glucopiranosilo, el cloruro de 2,3,4,6-O-tetraacetil glucurunopiranosilo, el fluoruro de 2,3,4,6-O-tetraacetil glucurunopiranosilo, el tiofenilo de 2,3,4,6-O-tetraacetil glucurunopiranosilo y en una realización más preferida puede ser el tricloroacetimidato de 2,3,4,6-O-tetraacetil glucopiranosilo (Schmidt, R. R.; Kinzy, W. Adv. Carbohydr. Chem. Biochem. 1994, 50, 21–123) In a preferred embodiment, the compound (V) is prepared by reacting (III) with a glycosyl donor (IV) in the presence of a catalyst and in an organic solvent. The substituent X is a common leaving group in organic chemistry such as, for example, Cl, F, SPh, ONHCCl3. Preferably, the glycosyl (IV) donor may be 2,3,4,6-O-tetraacetyl glucopyranosyl trichloroacetimidate, 2,3,4,6-O-tetraacetyl glucopyranosyl chloride, 2,3, fluoride, 4,6-O-tetraacetyl glucopyranosyl, thiophenyl 2,3,4,6-O-tetraacetyl glucopyranosyl, 2,3,4,6-O-tetraacetyl glucurunopyranosyl chloride, 2,3,4 fluoride, 6-O-tetraacetyl glucurunopyranosyl, thiophenyl of 2,3,4,6-O-tetraacetyl glucurunopyranosyl and in a more preferred embodiment may be 2,3,4,6-O-tetraacetyl glucopyranosyl trichloroacetimidate (Schmidt, RR; Kinzy, W. Adv. Carbohydr. Chem. Biochem. 1994, 50, 21–123)
- o el tricloroacetimidato de 2,3,4-O-triacetil glucurunopiranosilo (Lucas y col. Carbohydrate Res. 2009, 344, 1340). El catalizador puede ser preferentemente trifluoro boro eterato, ácido tríflico o triflato de trimetilsililo y en una realización más preferida puede ser trifluoro boro eterato. El disolvente orgánico puede ser diclorometano, cloroformo, tetrahidrofurano o éter etílico y en una realización más preferida puede ser diclorometano. or 2,3,4-O-triacetyl glucurunopyranosyl trichloroacetimidate (Lucas et al. Carbohydrate Res. 2009, 344, 1340). The catalyst may preferably be trifluoro boron etherate, triflic acid or trimethylsilyl triflate and in a more preferred embodiment it may be trifluoro boron etherate. The organic solvent may be dichloromethane, chloroform, tetrahydrofuran or ethyl ether and in a more preferred embodiment it may be dichloromethane.
En una realización preferida, el compuesto (VI) se obtiene por tratamiento del compuesto (V) con un ácido fuerte. Preferentemente, el ácido puede ser ácido trifluoroacético, ácido perclórico, ácido clorhídrico, ácido sulfúrico o ácido bromhídrico y en una realización más preferida puede ser ácido trifluoroacético. In a preferred embodiment, the compound (VI) is obtained by treating the compound (V) with a strong acid. Preferably, the acid may be trifluoroacetic acid, perchloric acid, hydrochloric acid, sulfuric acid or hydrobromic acid and in a more preferred embodiment it may be trifluoroacetic acid.
En una realización preferida, el compuesto (I) se obtiene por tratamiento del compuesto (VI) con medio básico en un disolvente orgánico protonado. Preferentemente, el medio básico puede ser carbonato sódico, carbonato potásico, o hidróxido de amonio y en una realización más preferida puede ser carbonato sódico. Preferentemente, el disolvente puede ser metanol, etanol, tert-butanol y en una realización más preferida puede ser metanol. De forma especialmente preferente, la desprotección del compuesto (VI) para obtener el compuesto (I) tiene lugar con carbonato sódico en metanol. In a preferred embodiment, the compound (I) is obtained by treating the compound (VI) with basic medium in a protonated organic solvent. Preferably, the basic medium may be sodium carbonate, potassium carbonate, or ammonium hydroxide and in a more preferred embodiment it may be sodium carbonate. Preferably, the solvent may be methanol, ethanol, tert-butanol and in a more preferred embodiment it may be methanol. Especially preferably, the deprotection of the compound (VI) to obtain the compound (I) takes place with sodium carbonate in methanol.
En una realización especialmente preferida, el procedimiento de obtención del compuesto de fórmula general (I) de la invención, comprende las siguientes etapas: In a particularly preferred embodiment, the process for obtaining the compound of general formula (I) of the invention comprises the following steps:
- a. to.
- protección mediante un dimetil acetal de dos grupos fenólicos contiguos del correspondiente galato de acilo (II), donde R2 tiene el mismo significado que en el compuesto de fórmula (I) para obtener el derivado (III); protection by a dimethyl acetal of two contiguous phenolic groups of the corresponding acyl gallate (II), wherein R2 has the same meaning as in the compound of formula (I) to obtain the derivative (III);
- b. b.
- reacción de (III) con el donador de glicosilo (IV) elegido entre el grupo que consiste en tricloroacetimidato de 2,3,4,6-tetra-O-acetil-D-glucopiranosilo y tricloroacetimidato de 2,3,4-tri-O-acetil-D-glucurunopiranosilo; reaction of (III) with the glycosyl (IV) donor selected from the group consisting of 2,3,4,6-tetra-O-acetyl-D-glucopyranosyl trichloroacetimidate and 2,3,4-tri- trichloroacetimidate O-acetyl-D-glucurunopyranosyl;
- c. C.
- desprotección del grupo acetal del derivado (V) para obtener el compuesto de fórmula general (VI) mediante tratamiento con un ácido fuerte; deprotection of the acetal group of the derivative (V) to obtain the compound of general formula (VI) by treatment with a strong acid;
- d. d.
- desprotección del resto de grupos protectores del derivado (VI) para obtener (I) con una base en un disolvente orgánico protonado; deprotection of the other protecting groups of the derivative (VI) to obtain (I) with a base in a protonated organic solvent;
donde el orden de las etapas de desprotección c y d se puede invertir. where the order of the deprotection stages c and d can be reversed.
Un tercer aspecto de la presente invención se refiere al uso de los compuestos de fórmula general (I) de la invención como antioxidantes en productos alimentarios, agroquímicos, cosméticos, de higiene personal o en productos farmacéuticos. A third aspect of the present invention relates to the use of the compounds of general formula (I) of the invention as antioxidants in food products, agrochemicals, cosmetics, personal hygiene or pharmaceutical products.
En otra realización preferida, la presente invención se refiere al uso de los compuestos de fórmula (I) descritos anteriormente como surfactantes, en particular en productos alimentarios, agroquímicos, cosméticos-dermatológicos, de higiene personal o farmacéuticos. In another preferred embodiment, the present invention relates to the use of the compounds of formula (I) described above as surfactants, in particular in food, agrochemical, cosmetic-dermatological, personal hygiene or pharmaceutical products.
Debido al carácter anfifílico de estos derivados de galatos de alquilo, los compuestos de fórmula (I) descritos en la presente invención poseen propiedades surfactantes, además de antioxidantes, lo que los convierte en aditivos muy útiles para ser usados en productos de las industrias agroquímica, alimentaria, cosmética-dermatológica y farmacéutica. Due to the amphiphilic character of these alkyl gallate derivatives, the compounds of formula (I) described in the present invention possess surfactant properties, in addition to antioxidants, which makes them very useful additives for use in products of the agrochemical industries, food, cosmetic-dermatological and pharmaceutical.
Los compuestos de la presente invención son adecuados para usarse como antioxidantes o/y surfactantes en preparaciones alimenticias, en particular como parte de una composición en forma de emulsión, tales como, pero sin limitarse a, alimentos en general, complementos alimenticios, alimentos funcionales o nutracéuticos. Asimismo se pueden usar en productos cosméticos o dermatológicos tales como, pero sin limitarse a, productos de higiene personal (jabón, champú gel, desodorante, cremas, lociones etc.) o productos para el bronceado y para la protección solar que pueden presentarse en forma de aceite, loción, gel, spray o crema. The compounds of the present invention are suitable for use as antioxidants or / and surfactants in food preparations, in particular as part of an emulsion composition, such as, but not limited to, foods in general, food supplements, functional foods or nutraceuticals They can also be used in cosmetic or dermatological products such as, but not limited to, personal hygiene products (soap, gel shampoo, deodorant, creams, lotions etc.) or tanning and sun protection products that can be presented in the form of oil, lotion, gel, spray or cream.
Los compuestos de la presente invención son adecuados también como antioxidantes o/y surfactantes en productos agroquímicos tales como, pero sin limitarse a, herbicidas, pesticidas o insecticidas. The compounds of the present invention are also suitable as antioxidants or / and surfactants in agrochemicals such as, but not limited to, herbicides, pesticides or insecticides.
A lo largo de la descripción y las reivindicaciones la palabra "comprende" y sus variantes no pretenden excluir otras características técnicas, aditivos, componentes o pasos. Para los expertos en la materia, otros objetos, ventajas y características de la invención se desprenderán en parte de la descripción y en parte de la práctica de la invención. Los siguientes ejemplos y gráficas se proporcionan a modo de ilustración, y no se pretende que sean limitativos de la presente invención. Throughout the description and the claims the word "comprises" and its variants are not intended to exclude other technical characteristics, additives, components or steps. For those skilled in the art, other objects, advantages and features of the invention will be derived partly from the description and partly from the practice of the invention. The following examples and graphs are provided by way of illustration, and are not intended to be limiting of the present invention.
Listado de compuestos Compound List
Hidroxitirosol 1 Octanoato de hidroxitirosol 2 Ácido gálico 3 Galato de butilo 4 Galato de hexilo 5 Galato de octilo 6 Galato de decilo 7 Galato de dodecilo 8 Galato de hexadecilo 9 Galato de octadecilo 10 3-O-(D-D-glucopiranosil)-4,5-dihidroxibenzoato de butilo 11 3-O-(D-D-glucopiranosil)-4,5-dihidroxibenzoato de hexilo 12 3-O-(D-D-glucopiranosil)-4,5-dihidroxibenzoato de octilo 13 3-O-(D-D-glucopiranosil)-4,5-dihidroxibenzoato de decilo 14 3-O-(D-D-glucopiranosil)-4,5-dihidroxibenzoato de dodecilo 15 3-O-(D-D-glucopiranosil)-4,5-dihidroxibenzoato de hexadecilo 16 3-O-(D-D-glucopiranosil)-4,5-dihidroxibenzoato de octadecilo 17 3-O-(D-D-glucurunopiranosil)-4,5-dihidroxibenzoato de butilo 18 3-O-(D-D-glucurunopiranosil)-4,5-dihidroxibenzoato de octilo 19 3-O-(D-D-glucurunopiranosil)-4,5-dihidroxibenzoato de hexadecilo 20 Hydroxytyrosol 1 Hydroxytyrosol octactate 2 Gallic acid 3 Butyl gallate 4 Hexyl gallate 5 Octyl gallate 6 Decyl gallate 7 Dodecyl gallate 8 Hexadecyl gallate 9 Octadecyl gallate 10 3-O- (DD-glucopyranosyl) -4.5 butyl 11-O- (DD-glucopyranosyl) -4,5-hexyl hexyl 12 3-O- (DD-glucopyranosyl) -4,5-octyl dihydroxybenzoate 13 3-O- (DD-glucopyranosyl) Decyl 14,5-dihydroxybenzoate 14 3-O- (DD-glucopyranosyl) -4,5-dodecyl dihydroxybenzoate 15 3-O- (DD-glucopyranosyl) -4,5-hexadecyl dihydroxybenzoate 16 3-O- ( Octadecyl DD-glucopyranosyl) -4,5-dihydroxybenzoate 17 3-O- (DD-glucurunopyranosyl) -4,5-butyl dihydroxybenzoate 18 3-O- (octyl DD-glucurunopyranosyl) -4,5-octyl dihydroxybenzoate 19 3 -O- (DD-glucurunopyranosyl) -4,5-hexadecyl dihydroxybenzoate 20
DESCRIPCIÓN DE LAS FIGURAS DESCRIPTION OF THE FIGURES
FIG. 1. Medidas de tensión superficial frente a logaritmo de la concentración de la serie de galatos de alquilo 4-9 (el ácido gálico 3 se incluye como referencia). FIG. 1. Measures of surface tension versus logarithm of the concentration of the series of alkyl gallates 4-9 (gallic acid 3 is included as a reference).
FIG. 2. Medidas de tensión superficial frente a logaritmo de la concentración de la serie de glucosil galatos de alquilo 11-16 (el ácido gálico 3 se incluye como referencia). FIG. 2. Measures of surface tension versus logarithm of the concentration of the 11-16 alkyl glucosyl gallate series (gallic acid 3 is included as a reference).
FIG. 3. Medidas de tensión superficial frente a logaritmo de la concentración de la serie de glucurunosil galatos de alquilo 18-20 (el ácido gálico 3 se incluye como referencia). FIG. 3. Measures of surface tension versus logarithm of the concentration of the glucurunosyl gallate series of alkyl 18-20 (gallic acid 3 is included as a reference).
FIG. 4. Relación entre el logaritmo de la cmc y la longitud de la cadena alquílica de la serie de derivados galatos de alquilo, para aquellos compuestos que muestran propiedades surfactantes. FIG. 4. Relationship between the logarithm of the cmc and the length of the alkyl chain of the series of alkyl gallate derivatives, for those compounds that show surfactant properties.
FIG. 5. Relación entre la tensión superficial a la CMC y la longitud de la cadena alquílica de las series de galatos de alquilo 4-8, glucosil- y glucurunosil galatos de alquilo 11-15 y 18-20, respectivamente. FIG. 5. Relationship between the surface tension at the CMC and the length of the alkyl chain of the series of alkyl gallates 4-8, glucosyl- and glucurunosyl alkyl gallates 11-15 and 18-20, respectively.
EJEMPLOS EXAMPLES
A continuación se ilustrará la invención mediante unos ensayos realizados por los inventores, que pone de manifiesto la efectividad de los compuestos de la invención. The invention will now be illustrated by tests carried out by the inventors, which demonstrates the effectiveness of the compounds of the invention.
EJEMPLO 1.- Síntesis de compuestos de formula general (I). EXAMPLE 1.- Synthesis of compounds of general formula (I).
R1O X R1O X
OH O O(IV) HO OH HO O AcO OH O O (IV) HO OH HO O AcO
OAc R1OO O OAc AcO OAc R1OO OR OAc AcO
OAc OAc
O OR2 O OR2 OAc (V) O OR2(II) (III) OR OR2 OR OR2 OAc (V) OR OR2 (II) (III)
OH OH R1O O OH OH R1O O
OHOH R1OO OHOH R1OO
AcO HO OAc OH AcO HO OAc OH
(I) (I)
OAc OH (VI) O OR2 O OR2 OAc OH (VI) OR OR2 OR OR2
En general, estos compuestos se obtienen a partir de los correspondientes galatos de alquilo (II) que están disponibles comercialmente. La ruta sintética seguida se refleja a continuación: In general, these compounds are obtained from the corresponding alkyl (II) gallates that are commercially available. The synthetic route followed is reflected below:
Procedimiento general para la preparación de los derivados de tipo (III). General procedure for the preparation of derivatives of type (III).
Los galatos de alquilo (II) se disuelven junto con cantidades catalíticas de ácido canforsulfónico en cloroformo seco. A continuación se añade 2,2-dimetoxipropano y la mezcla de reacción se agita a 60ºC durante 16 horas. Se añade trietilamina para neutralizar el medio ácido de la reacción y se evapora el disolvente en un rotavapor. El crudo de la reacción se purifica por cromatografía flash en silica gel utilizando mezclas de acetato de etilo y hexano como eluyentes, que varían en función de la diferente polaridad del grupo alquilo que contiene el compuesto. Los rendimientos de la reacción variaron entre el 40 y 60%. The alkyl (II) gallates are dissolved together with catalytic amounts of camphorsulfonic acid in dry chloroform. Then 2,2-dimethoxypropane is added and the reaction mixture is stirred at 60 ° C for 16 hours. Triethylamine is added to neutralize the acidic reaction medium and the solvent is evaporated in a rotary evaporator. The reaction crude is purified by flash chromatography on silica gel using mixtures of ethyl acetate and hexane as eluents, which vary depending on the different polarity of the alkyl group containing the compound. The yields of the reaction varied between 40 and 60%.
Procedimiento general para la preparación de los derivados de tipo (V). General procedure for the preparation of derivatives of type (V).
Los derivados de galatos de alquilo protegidos (III) (1 eq.) se disuelven junto el dador de glicosilo (IV) que será el tricloroacetimidato de 2,3,4,6-O-tetraacetil glucopiranosilo (1.2-1.5 eq.) o el tricloroacetimidato de 2,3,4-O-triacetil glucurunopiranosilo (1.2-1.5 eq.) en diclorometano seco (1 mL para cada 100 mg de derivado de alquil galato). A continuación se añade trifluoro boro eterato (0.1-0.15 eq.) y la mezcla de reacción se agita a temperatura ambiente durante 30-60 minutos. Se termina la reacción por adición de trietilamina. Se elimina el disolvente en un rotavapor y el crudo de la reacción se purifica por cromatografía flash en silica gel utilizando mezclas de acetato de etilo y hexano como eluyentes, que varían en función de la diferente polaridad del grupo alquilo que contiene el compuesto. Los rendimientos de la reacción variaron entre el 75 y 95%. The derivatives of protected alkyl gallates (III) (1 eq.) Are dissolved together with the glycosyl (IV) donor which will be 2,3,4,6-O-tetraacetyl glucopyranosyl trichloroacetimidate (1.2-1.5 eq.) Or 2,3,4-O-triacetyl glucurunopyranosyl trichloroacetimidate (1.2-1.5 eq.) in dry dichloromethane (1 mL for every 100 mg of alkyl gallate derivative). Trifluoro boron etherate (0.1-0.15 eq.) Is then added and the reaction mixture is stirred at room temperature for 30-60 minutes. The reaction is terminated by the addition of triethylamine. The solvent is removed in a rotary evaporator and the reaction crude is purified by flash chromatography on silica gel using mixtures of ethyl acetate and hexane as eluents, which vary depending on the different polarity of the alkyl group containing the compound. The yields of the reaction varied between 75 and 95%.
Procedimiento general para la preparación de los derivados de tipo (VI). General procedure for the preparation of derivatives of type (VI).
Los derivados protegidos de glicosil galatos de alquilo (V) se disuelven en ácido trifluoroacético puro seco (1 mL para cada 100 mg de derivado de glicosil alquil galato). La mezcla de reacción se agita a temperatura ambiente durante 24 horas. Se elimina el disolvente en un rotavapor y se co-evapora el crudo de reacción 2-3 veces con tolueno. Finalmente, el crudo de la reacción se purifica por cromatografía flash en silica gel utilizando mezclas de acetato de etilo y hexano como eluyentes, que varían en función de la diferente polaridad del grupo alquilo que contiene el compuesto. Los rendimientos de la reacción variaron entre el 65 y 85%. Protected derivatives of alkyl glycosyl gallates (V) are dissolved in dry pure trifluoroacetic acid (1 mL for every 100 mg of glycosyl alkyl gallate derivative). The reaction mixture is stirred at room temperature for 24 hours. The solvent is removed in a rotary evaporator and the reaction crude is co-evaporated 2-3 times with toluene. Finally, the reaction crude is purified by flash chromatography on silica gel using mixtures of ethyl acetate and hexane as eluents, which vary depending on the different polarity of the alkyl group containing the compound. The yields of the reaction varied between 65 and 85%.
Procedimiento general para la preparación de los derivados de tipo (I). General procedure for the preparation of derivatives of type (I).
Los derivados parcialmente protegidos de glicosil galatos de alquilo (VI) se disuelven en metanol (2 mL por cada 100 mg de derivado glicosil alquil galato). Se añade carbonato sódico (0.3 eq por cada eq. de derivado glicosil alquil galato). La mezcla de reacción se agita a temperatura ambiente durante 1 hora y se añade resina ácida amberlita® IR-120 hasta que el pH es neutro. Finalmente, la mezcla de reacción se filtra, se elimina a vacío el disolvente para obtener los compuestos de tipo (I). Los rendimientos de la reacción variaron entre el 90 y 95%. Partially protected derivatives of alkyl glycosyl gallates (VI) are dissolved in methanol (2 mL per 100 mg of glycosyl alkyl gallate derivative). Sodium carbonate (0.3 eq for each eq. Of glycosyl alkyl gallate derivative) is added. The reaction mixture is stirred at room temperature for 1 hour and amberlite® IR-120 acid resin is added until the pH is neutral. Finally, the reaction mixture is filtered, the solvent is removed in vacuo to obtain the compounds of type (I). The yields of the reaction varied between 90 and 95%.
EJEMPLO 2.- Medidas de tensión superficial y parámetros físico-químicos de galatos de alquilo y de los glucosil y glucurunosil galatos de alquilo. EXAMPLE 2.- Measures of surface tension and physical-chemical parameters of alkyl gallates and glucosyl and glucurunosyl alkyl gallates.
Se realizaron medidas de tensión superficial de los galatos de alquilo y de los derivados glucosil y glucurunosil galatos de alquilo (I) utilizando el método de Wilhelmy en un tensiómetro Krüss K12. Se prepararon muestras a una concentración inicial y posteriormente se hicieron sucesivas diluciones. Las propiedades de agregación en micelas se evidencian a partir de las isotermas de adsorción cuando se representan en una gráfica la tensión superficial frente al logaritmo de la concentración. El perfil típico de un compuesto con propiedades surfactantes consiste en una caída lineal de la tensión superficial cuando aumenta la concentración, seguida de una estabilización de la tensión superficial cuando se alcanza la saturación de la interfase. La intersección de estas dos partes lineales determina la concentración micelar crítica (CMC). Surface tension measurements of the alkyl gallates and of the glucosyl and glucurunosyl alkyl gallate derivatives (I) were performed using the Wilhelmy method on a Krüss K12 tensiometer. Samples were prepared at an initial concentration and subsequently dilutions were made. The aggregation properties in micelles are evidenced from the adsorption isotherms when the surface tension versus the logarithm of the concentration is plotted. The typical profile of a compound with surfactant properties consists of a linear drop in surface tension when the concentration increases, followed by a stabilization of the surface tension when the interface saturation is reached. The intersection of these two linear parts determines the critical micellar concentration (CMC).
Los valores de tensión superficial frente al logaritmo de la concentración para los galatos de alquilo 4-9 se muestran en la Figura 1. Se puede observar que los tres compuestos poseen buenas propiedades surfactantes, el galato de hexilo 5, el galato de octilo 6 y el galato de decilo 7. Mientras tanto los compuestos galato de butilo 4 y galato de dodecilo 8 tienen un perfil de compuesto surfactante pero con muy baja efectividad. The surface tension values versus the logarithm of the concentration for alkyl gallates 4-9 are shown in Figure 1. It can be seen that the three compounds possess good surfactant properties, hexyl gallate 5, octyl gallate 6 and decyl gallate 7. Meanwhile, the butyl gallate 4 and dodecyl 8 gallate compounds have a surfactant profile but with very low effectiveness.
Los valores de tensión superficial frente al logaritmo de la concentración para los glucosil galatos de alquilo 11-16 se muestran en la Figura 2. Se puede observar que hay cinco compuestos que poseen muy buenas propiedades surfactantes, el 3-O-(D-D-glucopiranosil)-4,5-dihidroxibenzoato de butilo 11, el 3-O-(D-D-glucopiranosil)-4,5dihidroxibenzoato de hexilo 12, el 3-O-(D-D-glucopiranosil)-4,5-dihidroxibenzoato de octilo 13, el 3-O-(D-Dglucopiranosil)-4,5-dihidroxibenzoato de decilo 14, el 3-O-(D-D-glucopiranosil)-4,5-dihidroxibenzoato de dodecilo 15. The surface tension values against the logarithm of the concentration for the 11-16 alkyl glucosyl gallates are shown in Figure 2. It can be seen that there are five compounds that have very good surfactant properties, 3-O- (DD-glucopyranosyl ) Butyl -4,5-dihydroxybenzoate 11, 3-O- (DD-glucopyranosyl) -4,5-hexyl dihydroxybenzoate 12, 3-O- (DD-glucopyranosyl) -4,5-octyl dihydroxybenzoate 13, Decyl 3-O- (D-Dglucopyranosyl) -4,5-dihydroxybenzoate 14, 3-O- (DD-glucopyranosyl) -4,5-dodecyl dihydroxybenzoate 15.
Los valores de tensión superficial frente al logaritmo de la concentración para los glucurunosil galatos de alquilo 1820 se muestran en la Figura 3. Se puede observar que hay dos compuestos que poseen muy buenas propiedades surfactantes, 3-O-(D-D-glucurunopiranosil)-4,5-dihidroxibenzoato de octilo 19 y el 3-O-(D-D-glucurunopiranosil)-4,5dihidroxibenzoato de hexadecilo 20. Mientras tanto el compuesto 3-O-(D-D-glucurunopiranosil)-4,5-dihidroxibenzoato de butilo 18 tiene un perfil de compuesto surfactante pero con muy baja efectividad. The surface tension values versus the logarithm of the concentration for 1820 alkyl glucurunosyl gallates are shown in Figure 3. It can be seen that there are two compounds that have very good surfactant properties, 3-O- (DD-glucurunopyranosyl) -4 , Octyl 19-dihydroxybenzoate 19 and 3-O- (DD-glucurunopyranosyl) -4,5-dihydroxybenzoate hexadecyl 20. Meanwhile, the compound 3-O- (DD-glucurunopyranosyl) -4,5-dihydroxybenzoate 18 has a surfactant compound profile but with very low effectiveness.
A continuación se calcularon distintos parámetros físico-químicos para los galatos de alquilo 4-8, los glucosil galatos de alquilo 11-15 y los glucurunosil galatos de alquilo 18-20 que se resumen en la Tabla 1. Además de los valores de CMC, se calcularon también los siguientes datos: la tensión superficial para la CMC (DCMC) relacionada con la eficacia del surfactante, pC20 (correspondiente a -log C20, siendo C20 la concentración necesaria para disminuir en 20 unidades la tensión superficial del agua pura, es decir, 52 mN/m) relacionado con el rendimiento del surfactante, la adsorción máxima de surfactante [max y el área ocupada por molécula en la interfase saturada (A). Los valores de los compuestos 9, 10, 16 y 17 no se incluyen pues no fueron suficientemente solubles o no mostraron perfiles típicos de compuestos surfactantes. Different physical-chemical parameters were then calculated for alkyl 4-8 gallate, 11-15 alkyl glucosyl gallate and 18-20 alkyl glucurunosyl gallate which are summarized in Table 1. In addition to CMC values, The following data were also calculated: the surface tension for the CMC (DCMC) related to the effectiveness of the surfactant, pC20 (corresponding to -log C20, where C20 is the concentration necessary to decrease the surface tension of pure water by 20 units, that is to say , 52 mN / m) related to the performance of the surfactant, the maximum adsorption of surfactant [max and the area occupied per molecule at the saturated interface (A). The values of compounds 9, 10, 16 and 17 are not included as they were not sufficiently soluble or did not show typical profiles of surfactant compounds.
- Compuesto Compound
- PM HL B CMC (mM) Dcmc (mN/m ) C20 (mM) pC20 D (mol/cm2) A (Å2) P.M HL B CMC (mM) Dcmc (mN / m) C20 (mM) pC20 D (mol / cm2) A (Å2)
- Galato de butilo (4) Butyl Gallate (4)
- 226. 2 11.1 0.60 54.0 - - 3.103 x 1010 53.5 226. 2 11.1 0.60 54.0 - - 3,103 x 1010 53.5
- Galato de hexilo (5) Hexyl Gallate (5)
- 264, 4 9,2 0,073 41,1 0,029 4,54 4,712 x 1010 35,3 264, 4 9.2 0.073 41.1 0.029 4.54 4,712 x 1010 35.3
- Galato de octilo (6) Octyl Gallate (6)
- 282. 3 8.9 0.05 42.2 0.016 4.80 6.589 x 1010 25.2 282. 3 8.9 0.05 42.2 0.016 4.80 6,589 x 1010 25.2
- Galato de decilo (7) Decyl Gallate (7)
- 310. 4 8.1 0.017 46.7 0.012 4.92 6.143 x 1010 27.0 310. 4 8.1 0.017 46.7 0.012 4.92 6,143 x 1010 27.0
- Galato de dodecilo (8) Dodecyl Gallate (8)
- 338. 4 7.4 0.0041 64.1 - - 5.172 x 1010 32.1 338. 4 7.4 0.0041 64.1 - - 5,172 x 1010 32.1
- Glc-Galato de butilo (11) Glc-Butyl Gallate (11)
- 388. 4 14.7 2.40 37.5 0.90 3.04 6.066 x 1010 27.4 388. 4 14.7 2.40 37.5 0.90 3.04 6,066 x 1010 27.4
- Glc-Galato de hexilo (12) Glc-Hexyl Gallate (12)
- 416. 4 13.8 1.30 33.5 0.09 4.05 3.024 x 1010 54.9 416. 4 13.8 1.30 33.5 0.09 4.05 3,024 x 1010 54.9
- Glc-Galato de octilo (13) Octyl Glc-Gallate (13)
- 444. 5 12.9 0.50 31.0 0.055 4.26 3.926 x 1010 42.3 444. 5 12.9 0.50 31.0 0.055 4.26 3,926 x 1010 42.3
- Glc-Galato de decilo (14) Glc-Decyl Gallate (14)
- 472. 12.1 0.032 39.5 0.009 5.04 3.994 x 10 41.6 472 12.1 0.032 39.5 0.009 5.04 3,994 x 10 41.6
- 5 5
- 10 10
- Glc-Galato de dodecilo (15) Glc-Dodecyl Galato (15)
- 500. 6 11.5 0.010 44.3 0.004 8 5.32 3.871 x 1010 42.9 500. 6 11.5 0.010 44.3 0.004 8 5.32 3,871 x 1010 42.9
- GlcA-Galato de butilo (18) GlcA-Butyl Gallate (18)
- 401. 3 15.0 2.70 520 0.002 7 2.57 4.554 x 1010 36.4 401. 3 15.0 2.70 520 0.002 7 2.57 4,554 x 1010 36.4
- GlAc-Galato de octilo (19) Octyl GlAc-Gallate (19)
- 457. 4 13.1 0.18 30.0 0.008 5 5.07 2.966 x 1010 56.0 457. 4 13.1 0.18 30.0 0.008 5 5.07 2,966 x 1010 56.0
- GlcA-Galato de hexadecilo(20) GlcA-Hexadecyl Gallate (20)
- 569. 7 10.5 0.10 37.0 0.022 4.66 3.674 x 1010 45.2 569. 7 10.5 0.10 37.0 0.022 4.66 3,674 x 1010 45.2
- Brij 30 ® (éster alquiletoxilado) Brij 30 ® (alkylethoxylated ester)
- 362, 5 9,4 0,0035 30,0 0,002 4 5,62 3,80 x 10-10 44,0 362.5 9.4 0.0035 30.0 0.002 4 5.62 3.80 x 10-10 44.0
- Tween 20 ® (monolaurato de sorbitánpolioxietileno) Tween 20 ® (sorbitan polyoxyethylene monolaurate)
- 1227 16,6 0,0169 35,0 0,002 5 5,61 3,560 x 1010 46,6 1227 16.6 0.0169 35.0 0.002 5 5.61 3,560 x 1010 46.6
Tabla 1: Parámetros de peso molecular (PM), HLB, CMC, tensión superficial, área por molécula, C20, pC20, D y A de los galatos de alquilo 4-10, los glucosil galatos de alquilo 11-15 y los glucurunosil galatos de alquilo 18-20 y de diversos surfactantes no iónicos convencionales. Table 1: Parameters of molecular weight (PM), HLB, CMC, surface tension, area per molecule, C20, pC20, D and A of 4-10 alkyl gallates, 11-15 alkyl glucosyl gallates and glucurunosyl gallates 18-20 alkyl and various conventional non-ionic surfactants.
Se observa en cada una de las series que al aumentar el tamaño de la cadena alquílica disminuye el valor de la CMC. Esto se debe a que el proceso de auto-agregación en micelas es más rápido cuanto más hidrofóbica es la cadena del compuesto para evitar el contacto con las moléculas de agua. También se observa una relación lineal entre el logaritmo de la CMC y el tamaño de la cadena alquílica para la serie de los galatos de alquilo y la serie de los glucosil galatos de alquilo (ver Figura 4). En cambio no se observa este comportamiento lineal en la serie de los glucurunosil galatos de alquilo. It is observed in each of the series that increasing the size of the alkyl chain decreases the value of the CMC. This is because the process of self-aggregation in micelles is faster the more hydrophobic the compound chain is to avoid contact with water molecules. There is also a linear relationship between the CMC logarithm and the size of the alkyl chain for the series of alkyl gallates and the series of alkyl glucosyl gallates (see Figure 4). On the other hand, this linear behavior is not observed in the series of alkyl glucurunosyl gallates.
Es importante destacar que para un valor determinado de tamaño de cadena, las series de los glucosil galatos de alquilo y los glucurunosil galatos de alquilo muestran valores de CMC mayores que para la serie de los galatos de alquilo. Las diferencias disminuyen cuando aumenta la longitud de la cadena alquílica. It is important to note that for a given value of chain size, the series of alkyl glucosyl gallates and alkyl glucurunosyl gallates show higher CMC values than for the series of alkyl gallates. The differences decrease when the length of the alkyl chain increases.
Los mayores valores de CMC obtenidos para los glucosil y glucurunosil galatos de alquilo con respecto a los galatos de alquilo para una misma longitud de cadena alquílica, son debidos al mayor carácter hidrófilo que imparten a las moléculas los grupos polares glucosil y glucurunosil. Dado que el proceso de micelización está directamente relacionado con las hidrofobicidad de las moléculas, es lógico que para estos compuestos menos hidrófobos, la formación de micelas experimente un retraso. The higher CMC values obtained for the glucosyl and glucurunosyl alkyl gallates with respect to the alkyl gallates for the same alkyl chain length are due to the greater hydrophilic character imparted to the molecules by the glucosyl and glucurunosyl polar groups. Since the micellization process is directly related to the hydrophobicity of the molecules, it is logical that for these less hydrophobic compounds, micelle formation experiences a delay.
Por otra parte, el hecho que las diferencias entre las CMC de las distintas series disminuyan a medida que la longitud de la cadena hidrocarbonada aumenta, es una consecuencia lógica de la pérdida de influencia la naturaleza de los grupos hidrófilos ante un incremento progresivo del tamaño de los grupos hidrófobos. On the other hand, the fact that the differences between the CMCs of the different series decrease as the length of the hydrocarbon chain increases, is a logical consequence of the loss of influence the nature of the hydrophilic groups before a progressive increase in the size of hydrophobic groups.
Con respecto a la eficacia de estos compuestos como surfactantes, reflejada por el valor DCMC, se observa que los derivados de la serie de los glucosil galatos de alquilo y los glucurunosil galatos de alquilo muestran valores mucho mejores que para los correspondientes galatos de alquilo. Así por ejemplo, los valores de DCMC para el glucosil galato de hexilo, el glucosil galato de octilo y el glucurunosil galato de octilo (30-33.5 mN/m) son del mismo rango de los que muestran buenos surfactantes de uso común como son el Brij 30 o el Tween 20 (ver sus valores en la Tabla 1). En cambio, los mejores surfactantes de la serie de los galatos de alquilo, como son los de cadena de hexilo, octilo y decilo tienen valores de DCMC entre 40 y 46 mN/m. Estos valores indican que la modificación del azúcar sobre la estructura de galato de alquilo convierte a los nuevos compuestos en mejores surfactantes que los galatos de alquilo. With respect to the efficacy of these compounds as surfactants, reflected by the DCMC value, it is observed that derivatives of the series of alkyl glucosyl gallates and alkyl glucurunosyl gallates show much better values than for the corresponding alkyl gallates. For example, the DCMC values for hexyl glucosyl gallate, octyl glucosyl gallate and octyl glucurunosyl gallate (30-33.5 mN / m) are in the same range as those showing good commonly used surfactants such as Brij 30 or Tween 20 (see their values in Table 1). On the other hand, the best surfactants of the series of alkyl gallates, such as those of hexyl, octyl and decyl chains, have DCMC values between 40 and 46 mN / m. These values indicate that the modification of sugar on the structure of alkyl gallate converts the new compounds into better surfactants than alkyl gallates.
Cuando el valor de DCMC se representa frente al número de carbonos de la cadena alquílica se observa para las tres series de derivados un valor mínimo correspondiente a un tamaño de cadena intermedio, entre 6 y 8 carbonos (ver Figura 5). Se puede ver claramente que la introducción de un monosacárido neutro como la glucosa o de uno cargado como el ácido glucurónico en la cabeza polar de los galatos de alquilo resulta en unos nuevos derivados que poseen mejores propiedades surfactantes que los propios galatos de alquilo y además con propiedades similares a otros surfactantes comerciales (como Brij 30 o el Tween 20). When the DCMC value is represented against the number of carbons in the alkyl chain, a minimum value corresponding to an intermediate chain size, between 6 and 8 carbons, is observed for the three series of derivatives (see Figure 5). It can be clearly seen that the introduction of a neutral monosaccharide such as glucose or a charged one such as glucuronic acid in the polar head of the alkyl gallates results in new derivatives that have better surfactant properties than the alkyl gallates themselves and also with properties similar to other commercial surfactants (such as Brij 30 or Tween 20).
Los resultados obtenidos para los compuestos con 4 carbonos en la cadena sugieren que estos derivados de galato con un número inferior de carbonos tendrán propiedades surfactantes significativamente inferiores a los compuestos de la presente invención. The results obtained for compounds with 4 carbons in the chain suggest that these gallate derivatives with a lower number of carbons will have significantly lower surfactant properties than the compounds of the present invention.
EJEMPLO 3.- Medidas de actividad antioxidante de galatos de alquilo y de los glucosil y glucurunosil galatos de alquilo. EXAMPLE 3.- Measures of antioxidant activity of alkyl gallates and of glucosyl and glucurunosyl alkyl gallates.
Se realizaron medidas de capacidad antioxidante de los galatos de alquilo y de los derivados glucosil y glucurunosil galatos de alquilo (I) utilizando dos métodos distintos, el ensayo de capacidad de captación de radicales DPPH (1,1difenil-2- picrilhidrazilo) y el ensayo de capacidad reductora FRAP (“ferric reducing antioxidant power”, capacidad antioxidante de hierro reducido) (ver Tablas 2 y 3). Las medidas experimentales de valores de DPPH EC50 y de valores FRAP se han realizado siguiendo protocolos descritos previamente (Nenadis y col. J. Am. Oil Chem. Soc. 2002, 79, 1191; Benzie y col. Anal. Biochem. 1996, 239, 70). Se utilizaron como controles el ácido gálico, el hidroxitirosol y el octanoato de hidroxitirosol. Measurements of antioxidant capacity of the alkyl gallates and of the glucosyl and glucurunosyl alkyl (1) glutes derivatives were performed using two different methods, the DPPH radical uptake capacity test (1,1-diphenyl-2-picrylhydrazyl) and the test FRAP reducing capacity (“ferric reducing antioxidant power”, reduced iron antioxidant capacity) (see Tables 2 and 3). Experimental measurements of DPPH EC50 values and FRAP values have been performed following previously described protocols (Nenadis et al. J. Am. Oil Chem. Soc. 2002, 79, 1191; Benzie et al. Anal. Biochem. 1996, 239 , 70). Gallic acid, hydroxytyrosol and hydroxytyrosol octanoate were used as controls.
Los resultados obtenidos en el ensayo de capacidad de captación de radicales DPPH muestran valores muy similares para los galatos de alquilo y el ácido gálico. En el caso de los derivados glucosil y glucurunosil galatos de alquilo (I) este valor disminuye en términos generales, aunque menos para los glucurunosil galatos de alquilo que para los glicosil derivados. La pérdida de un hidroxilo fenólico en los nuevos derivados de tipo (I) parece que afecta negativamente a su capacidad de captación de radicales. The results obtained in the DPPH radical scavenging capacity test show very similar values for alkyl gallates and gallic acid. In the case of the glucosyl and glucurunosyl alkyl (I) alkyl derivatives this value decreases in general terms, although less for alkyl glucurunosyl gallates than for glycosyl derivatives. The loss of a phenolic hydroxyl in the new type (I) derivatives seems to negatively affect its ability to capture radicals.
Los resultados obtenidos en el ensayo de capacidad reductora FRAP muestra que el número de electrones donados disminuye cuando aumenta el tamaño de la cadena alquílica de los galatos de alquilo y de los nuevos derivados de tipo (I). A su vez, los valores de FRAP fueron menores para los compuestos de tipo (I) que para los galatos de alquilo. Sin embargo, es importante destacar que los valores obtenidos de capacidad de captación de radicales y de capacidad reductora para los nuevos derivados, los glucosil y glucurunosil galatos de alquilo (I) parecen ser muy satisfactorios en su conjunto para poder actuar como antioxidantes óptimos en distintas matrices. De hecho, los valores de DPPF y FRAP de los nuevos derivados de tipo (I) son mejores que los descritos para el hidroxitirosol y el octanoato de hidroxitirosol, dos compuestos fenólicos que han mostrado ser excelentes antioxidantes en aceites y emulsiones. The results obtained in the FRAP reductive capacity test show that the number of donated electrons decreases when the size of the alkyl chain of the alkyl gallates and of the new type (I) derivatives increases. In turn, FRAP values were lower for compounds of type (I) than for alkyl gallates. However, it is important to note that the values obtained from the ability to capture radicals and reducing capacity for the new derivatives, the glucosyl and glucurunosyl alkyl gallates (I) seem to be very satisfactory as a whole to be able to act as optimal antioxidants in different matrices In fact, the DPPF and FRAP values of the new type (I) derivatives are better than those described for hydroxytyrosol and hydroxytyrosol octanoate, two phenolic compounds that have proven to be excellent antioxidants in oils and emulsions.
- Compuesto Compound
- DPPH EC50 FRAP DPPH EC50 FRAP
- Hidroxitirosol (1) Hydroxytyrosol (1)
- 0.720 ± 0.000 1.144 ± 0.095 0.720 ± 0.000 1,144 ± 0.095
- Octanoato de hidroxitirosol (2)Ácido gálico (3) Hydroxytyrosol Octanoate (2) Gallic Acid (3)
- 0.686 ± 0.033 0.205 ± 0.001 1.128 ± 0.120 4.411± 0.121 0.686 ± 0.033 0.205 ± 0.001 1,128 ± 0,120 4,411 ± 0.121
- Galato de butilo (4) Butyl Gallate (4)
- 0.227 ± 0.002 2.827± 0.092 0.227 ± 0.002 2,827 ± 0.092
- Galato de hexilo (5) Hexyl Gallate (5)
- 0.253 ± 0.004 2.552± 0.060 0.253 ± 0.004 2,552 ± 0.060
- Galato de octilo (6) Octyl Gallate (6)
- 0.264 ± 0.001 1.643± 0.072 0.264 ± 0.001 1,643 ± 0.072
- Galato de decilo (7) Decyl Gallate (7)
- 0.255 ± 0.001 1.417± 0.089 0.255 ± 0.001 1,417 ± 0.089
- Galato de dodecilo (8) Dodecyl Gallate (8)
- 0.238 ± 0.002 1.565± 0.025 0.238 ± 0.002 1,565 ± 0.025
- Galato de hexadecilo (9) Hexadecyl gallate (9)
- 0.261 ± 0.001 1.136± 0.053 0.261 ± 0.001 1,136 ± 0.053
- Galato de octadecilo (10) Octadecyl gallate (10)
- 0.258 ± 0.001 0.965± 0.082 0.258 ± 0.001 0.965 ± 0.082
Tabla 2: Medida de capacidad de captación de radicales DPPH y de capacidad reductora FRAP de los galatos de alquilo 4-10. Los controles son hidroxitirosol 1, octanoato de hidroxitirosol 2 y ácido gálico 3. Table 2: Measurement of DPPH radical uptake capacity and FRAP reducing capacity of 4-10 alkyl gallates. The controls are hydroxytyrosol 1, hydroxytyrosol octanoate 2 and gallic acid 3.
- Compuesto Compound
- DPPH EC50 FRAP DPPH EC50 FRAP
- Glc-galato de butilo (11) Glc-Butyl Gallate (11)
- 0.479 ± 0.000 2.436± 0.078 0.479 ± 0.000 2,436 ± 0.078
- Glc-galato de hexilo (12) Glc-Hexyl Gallate (12)
- 0.458 ± 0.001 1.863± 0.025 0.458 ± 0.001 1.863 ± 0.025
- Glc- galato de octilo (13) Octyl Glylate (13)
- 0.614 ± 0.009 1.388± 0.111 0.614 ± 0.009 1,388 ± 0.111
- Glc- galato de decilo (14) Decyl glycolate (14)
- 0.496 ± 0.004 1.496± 0.087 0.496 ± 0.004 1,496 ± 0.087
- Glc- galato de dodecilo (15) Dodecyl Glylate (15)
- 0.490 ± 0.009 1.144± 0.063 0.490 ± 0.009 1,144 ± 0.063
- Glc- galato de hexadecilo (16) Hexadecyl glyclate (16)
- 0.674 ± 0.006 0.250± 0.056 0.674 ± 0.006 0.250 ± 0.056
- Glc- galato de octadecilo (17) Octadecyl Glylate (17)
- 0.500 ± 0.002 0.232± 0.048 0.500 ± 0.002 0.232 ± 0.048
- GlcA- galato de butilo (18) GlcA-butyl gallate (18)
- 0.590 ± 0.0101 3.785± 0.10 0.590 ± 0.0101 3,785 ± 0.10
- GlcA- galato de octilo (19) GlcA- octyl gallate (19)
- 0.661 ± 0.0026 1.252± 0.075 0.661 ± 0.0026 1,252 ± 0.075
- GlcA- galato de hexadecilo (20) GlcA- hexadecyl gallate (20)
- 0.466 ± 0.0134 0.224± 0.062 0.466 ± 0.0134 0.224 ± 0.062
Tabla 3: Medida de capacidad de captación de radicales DPPH y de capacidad reductora FRAP de los glucosil galatos de alquilo 11-17 y glucurunosil galatos de alquilo 18-20. Table 3: Measurement of DPPH radical uptake capacity and FRAP reducing capacity of 11-17 alkyl glucosyl gallates and 18-20 alkyl glucurunosyl gallates.
En conclusión, estos datos revelan que tanto los galatos de alquilo como los nuevos derivados glucosil y glucurunosil galatos de alquilo (I) se comportan como buenos o muy buenos surfactantes y muy buenos antioxidantes. De esta manera se los puede considerar como antioxidantes surfactantes. Estos resultados abren las puertas a potenciales nuevas aplicaciones de estos antioxidantes surfactantes, por ejemplo, en las industrias alimentaria, agroquímica, farmacéutica, de detergentes, de higiene personal o de protección solar. In conclusion, these data reveal that both the alkyl gallates and the new glucosyl and glucurunosyl alkyl (I) glutes derivatives behave as good or very good surfactants and very good antioxidants. In this way they can be considered as surfactant antioxidants. These results open the door to potential new applications of these surfactant antioxidants, for example, in the food, agrochemical, pharmaceutical, detergent, personal hygiene or sun protection industries.
Claims (20)
- 2.2.
- Compuesto de fórmula general (I) según la reivindicación 1, caracterizado porque el anillo de piranosa es una glucosa. Compound of general formula (I) according to claim 1, characterized in that the pyranose ring is a glucose.
- 3.3.
- Compuesto de fórmula general (I) según la reivindicación 1, caracterizado porque el anillo de piranosa es un ácido glucurónico. Compound of general formula (I) according to claim 1, characterized in that the pyranose ring is a glucuronic acid.
- Categoría Category
- 56 Documentos citados Reivindicaciones afectadas 56 Documents cited Claims Affected
- A TO
- Ali, S. et al. “Mutiniside, new antioxidantphenolic glucoside from Abutilon muticum” Journal of Asian Natural Products Research, 2009, Vol.11, N. 5, Páginas 457-64. Ver Resumen y Figura 1. 1-24 Ali, S. et al. “Mutiniside, new antioxidantphenolic glucoside from Abutilon muticum” Journal of Asian Natural Products Research, 2009, Vol. 11, N. 5, Pages 457-64. See Summary and Figure 1. 1-24
- A TO
- US 7282520 B2 (LION CORPORATION) 16/10/2007. Ver columna 1, líneas 1-10 y 50-57; columna 2, líneas 1-27; ejemplos 31 y 35. 1-24 US 7282520 B2 (LION CORPORATION) 10/16/2007. See column 1, lines 1-10 and 50-57; column 2, lines 1-27; Examples 31 and 35. 1-24
- A TO
- SIDDIQUI, A. et al. “Isolation of phytoconstituentand hypotensive activity of Terminalia arjunabark”. Indian Journal of Heterocyclic Chemistry, 2004, Vol.14, N. 2, páginas 115-118. Ver Resumen. Base de datos de HCAPLUS [Recuperado el 21/08/2012]. STN International, Columbus, OHIO (EEUU). 1-24 SIDDIQUI, A. et al. "Isolation of phytoconstituentand hypotensive activity of Terminalia arjunabark." Indian Journal of Heterocyclic Chemistry, 2004, Vol. 14, N. 2, pages 115-118. See Summary. HCAPLUS Database [Retrieved on 08/21/2012]. STN International, Columbus, OHIO (USA). 1-24
- A TO
- MEDINA, I. et al. “Effect of Lipophilization of Hydroxytyrosol on Its Antioxidant Activity in Fish Oils and Fish Oil-in-Water Emulsions”.Journal of Agricultural Food Chemistry, 2009, Vol. 57, N. 20, páginas 9773–9779. Ver Resumen; Figura 1. 1-24 MEDINA, I. et al. “Effect of Lipophilization of Hydroxytyrosol on Its Antioxidant Activity in Fish Oils and Fish Oil-in-Water Emulsions.” Journal of Agricultural Food Chemistry, 2009, Vol. 57, N. 20, pages 9773–9779. See Summary; Figure 1. 1-24
- Categoría de los documentos citados X: de particular relevancia Y: de particular relevancia combinado con otro/s de la misma categoría A: refleja el estado de la técnica O: referido a divulgación no escrita P: publicado entre la fecha de prioridad y la de presentación de la solicitud E: documento anterior, pero publicado después de la fecha de presentación de la solicitud Category of the documents cited X: of particular relevance Y: of particular relevance combined with other / s of the same category A: reflects the state of the art O: refers to unwritten disclosure P: published between the priority date and the date of priority submission of the application E: previous document, but published after the date of submission of the application
- El presente informe ha sido realizado • para todas las reivindicaciones • para las reivindicaciones nº: This report has been prepared • for all claims • for claims no:
- Fecha de realización del informe 28.08.2012 Date of realization of the report 28.08.2012
- Examinador N. Martín Laso Página 1/4 Examiner N. Martín Laso Page 1/4
- Novedad (Art. 6.1 LP 11/1986) Novelty (Art. 6.1 LP 11/1986)
- Reivindicaciones Reivindicaciones 1-24 SI NO Claims Claims 1-24 IF NOT
- Actividad inventiva (Art. 8.1 LP11/1986) Inventive activity (Art. 8.1 LP11 / 1986)
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- Documento Document
- Número Publicación o Identificación Fecha Publicación Publication or Identification Number publication date
- D01 D01
- Ali, S. et al. “Mutiniside, new antioxidantphenolic glucoside from Abutilon muticum”.Journal of Asian Natural Products Research, 2009, Vol.11, N. 5, páginas 457-64. 2009 Ali, S. et al. “Mutiniside, new antioxidantphenolic glucoside from Abutilon muticum.” Journal of Asian Natural Products Research, 2009, Vol. 11, N. 5, pages 457-64. 2009
- D02 D02
- US 7282520 B2 (LION CORPORATION) 16.10.2007 US 7282520 B2 (LION CORPORATION) 16.10.2007
- D03 D03
- SIDDIQUI, A. et al. “Isolation of phytoconstituentand hypotensive activity of Terminalia arjunabark”. Indian Journal of Heterocyclic Chemistry, 2004, Vol.14, N. 2, páginas 115-118. Ver Resumen. Base de datos de HCAPLUS [Recuperado el 21/08/2012].STN International, Columbus, OHIO (EEUU). 2004 SIDDIQUI, A. et al. "Isolation of phytoconstituentand hypotensive activity of Terminalia arjunabark." Indian Journal of Heterocyclic Chemistry, 2004, Vol. 14, N. 2, pages 115-118. See Summary. HCAPLUS Database [Retrieved on 08/21/2012] .STN International, Columbus, OHIO (USA). 2004
- D04 D04
- MEDINA, I. et al. “Effect of Lipophilization of Hydroxytyrosol on Its Antioxidant Activity in Fish Oils and Fish Oil-in-Water Emulsions”. Journal of Agricultural Food Chemistry, 2009, Vol. 57, N. 20, páginas 9773–9779. 10.06.2009 MEDINA, I. et al. "Effect of Lipophilization of Hydroxytyrosol on Its Antioxidant Activity in Fish Oils and Fish Oil-in-Water Emulsions." Journal of Agricultural Food Chemistry, 2009, Vol. 57, N. 20, pages 9773–9779. 06.10.2009
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ES201130985A ES2393951B1 (en) | 2011-06-14 | 2011-06-14 | DERIVATIVES OF RENT GALATES AS ANTIOXIDANTS AND SURFACTANTS |
| PCT/ES2012/070435 WO2012172143A2 (en) | 2011-06-14 | 2012-06-13 | Alkyl gallate derivatives as antioxidants and surfactants |
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| ES201130985A ES2393951B1 (en) | 2011-06-14 | 2011-06-14 | DERIVATIVES OF RENT GALATES AS ANTIOXIDANTS AND SURFACTANTS |
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| DE60221869T2 (en) * | 2001-09-19 | 2008-05-08 | Lion Corp. | TOPICAL PREPARATION CONTAINING GALLOIC ACID DERIVATIVES |
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| WO2012172143A2 (en) | 2012-12-20 |
| WO2012172143A3 (en) | 2013-04-11 |
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