WO1998034943A1 - Surfactant amines and glycosides - Google Patents
Surfactant amines and glycosides Download PDFInfo
- Publication number
- WO1998034943A1 WO1998034943A1 PCT/NL1998/000077 NL9800077W WO9834943A1 WO 1998034943 A1 WO1998034943 A1 WO 1998034943A1 NL 9800077 W NL9800077 W NL 9800077W WO 9834943 A1 WO9834943 A1 WO 9834943A1
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- Prior art keywords
- group
- alkyl
- chor
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- formula
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- 150000001412 amines Chemical class 0.000 title claims abstract description 15
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 10
- 229930182470 glycoside Natural products 0.000 title claims description 25
- 150000002338 glycosides Chemical class 0.000 title claims description 19
- -1 pyrrolidino, piperidino Chemical group 0.000 claims abstract description 55
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 31
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 28
- 235000000346 sugar Nutrition 0.000 claims abstract description 25
- 239000001257 hydrogen Substances 0.000 claims abstract description 23
- 125000002252 acyl group Chemical group 0.000 claims abstract description 22
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 17
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 9
- 125000001841 imino group Chemical group [H]N=* 0.000 claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 7
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims abstract description 7
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 6
- 125000000304 alkynyl group Chemical group 0.000 claims abstract description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 3
- 239000003599 detergent Substances 0.000 claims abstract description 3
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims abstract description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract 2
- 239000000203 mixture Substances 0.000 claims description 19
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 18
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 7
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims description 6
- 150000003333 secondary alcohols Chemical class 0.000 claims description 6
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 5
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 150000004820 halides Chemical class 0.000 claims description 5
- 125000002519 galactosyl group Chemical group C1([C@H](O)[C@@H](O)[C@@H](O)[C@H](O1)CO)* 0.000 claims description 4
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims description 4
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 150000002923 oximes Chemical class 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 125000005843 halogen group Chemical group 0.000 claims 3
- 125000003282 alkyl amino group Chemical group 0.000 claims 2
- 125000005115 alkyl carbamoyl group Chemical group 0.000 claims 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 2
- 125000006701 (C1-C7) alkyl group Chemical group 0.000 claims 1
- 229930194542 Keto Natural products 0.000 claims 1
- 125000003545 alkoxy group Chemical group 0.000 claims 1
- 239000000010 aprotic solvent Substances 0.000 claims 1
- 239000003638 chemical reducing agent Substances 0.000 claims 1
- 230000001804 emulsifying effect Effects 0.000 claims 1
- 125000004043 oxo group Chemical group O=* 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 14
- 239000003995 emulsifying agent Substances 0.000 abstract description 3
- 150000002431 hydrogen Chemical class 0.000 abstract description 3
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 45
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 42
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 239000002253 acid Substances 0.000 description 13
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 9
- 239000008101 lactose Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 description 7
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 229930182830 galactose Natural products 0.000 description 7
- 239000012074 organic phase Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 229930182474 N-glycoside Natural products 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 6
- 239000002808 molecular sieve Substances 0.000 description 6
- 150000003335 secondary amines Chemical class 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- JDXBXORQIMKXEI-UHFFFAOYSA-N methyl 12-aminooctadecanoate Chemical compound CCCCCCC(N)CCCCCCCCCCC(=O)OC JDXBXORQIMKXEI-UHFFFAOYSA-N 0.000 description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 230000003595 spectral effect Effects 0.000 description 5
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 4
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 4
- OFOWUDSDZLONKT-UHFFFAOYSA-N 12-oxo-octadecanoic acid Chemical compound CCCCCCC(=O)CCCCCCCCCCC(O)=O OFOWUDSDZLONKT-UHFFFAOYSA-N 0.000 description 4
- 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 description 4
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 4
- 238000004566 IR spectroscopy Methods 0.000 description 4
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 4
- 229910006069 SO3H Inorganic materials 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 150000002341 glycosylamines Chemical class 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical compound [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 4
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 3
- CYAYKKUWALRRPA-RGDJUOJXSA-N [(2r,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-bromooxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@H]1O[C@H](Br)[C@H](OC(C)=O)[C@@H](OC(C)=O)[C@@H]1OC(C)=O CYAYKKUWALRRPA-RGDJUOJXSA-N 0.000 description 3
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 150000002016 disaccharides Chemical class 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- 150000002692 maltoses Chemical class 0.000 description 3
- NGYIMTKLQULBOO-UHFFFAOYSA-L mercury dibromide Chemical compound Br[Hg]Br NGYIMTKLQULBOO-UHFFFAOYSA-L 0.000 description 3
- 150000002772 monosaccharides Chemical class 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 238000006268 reductive amination reaction Methods 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- YUQFYQHUZOPVPH-UHFFFAOYSA-N 12-amino-octadecanoic acid Chemical compound CCCCCCC(N)CCCCCCCCCCC(O)=O YUQFYQHUZOPVPH-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- NPDSHTNEKLQQIJ-UHFFFAOYSA-N 9-hydroxyoctadeca-10,12-dienoic acid Chemical compound CCCCCC=CC=CC(O)CCCCCCCC(O)=O NPDSHTNEKLQQIJ-UHFFFAOYSA-N 0.000 description 2
- RKHXDCVAPIMDMG-UHFFFAOYSA-N 9-hydroxyoctadecanoic acid Chemical compound CCCCCCCCCC(O)CCCCCCCC(O)=O RKHXDCVAPIMDMG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229910004727 OSO3H Inorganic materials 0.000 description 2
- LPTITAGPBXDDGR-UHFFFAOYSA-N Penta-Ac-Mannose Natural products CC(=O)OCC1OC(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C1OC(C)=O LPTITAGPBXDDGR-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000010933 acylation Effects 0.000 description 2
- 238000005917 acylation reaction Methods 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 125000005529 alkyleneoxy group Chemical group 0.000 description 2
- 238000005576 amination reaction Methods 0.000 description 2
- 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 2
- LPTITAGPBXDDGR-IBEHDNSVSA-N beta-d-glucose pentaacetate Chemical compound CC(=O)OC[C@H]1O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](OC(C)=O)[C@@H]1OC(C)=O LPTITAGPBXDDGR-IBEHDNSVSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000031709 bromination Effects 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229960001031 glucose Drugs 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 150000002632 lipids Chemical group 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- RVWOWEQKPMPWMQ-UHFFFAOYSA-N methyl 12-hydroxyoctadecanoate Chemical compound CCCCCCC(O)CCCCCCCCCCC(=O)OC RVWOWEQKPMPWMQ-UHFFFAOYSA-N 0.000 description 2
- XVSPEBNRFAFNAV-UHFFFAOYSA-N methyl 12-oxooctadecanoate Chemical compound CCCCCCC(=O)CCCCCCCCCCC(=O)OC XVSPEBNRFAFNAV-UHFFFAOYSA-N 0.000 description 2
- NNUFZSSGONRIJT-UHFFFAOYSA-N methyl 9-oxooctadecanoate Chemical compound CCCCCCCCCC(=O)CCCCCCCC(=O)OC NNUFZSSGONRIJT-UHFFFAOYSA-N 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- ZPVFWPFBNIEHGJ-UHFFFAOYSA-N n-hexyl methyl ketone Natural products CCCCCCC(C)=O ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 0.000 description 2
- 229940038384 octadecane Drugs 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920001542 oligosaccharide Polymers 0.000 description 2
- 150000002482 oligosaccharides Chemical class 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000006146 oximation reaction Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- WBHHMMIMDMUBKC-QJWNTBNXSA-N ricinoleic acid Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(O)=O WBHHMMIMDMUBKC-QJWNTBNXSA-N 0.000 description 2
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 150000008163 sugars Chemical class 0.000 description 2
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ZBQKPDHUDKSCRS-UHFFFAOYSA-N $l^{1}-oxidanyl acetate Chemical group CC(=O)O[O] ZBQKPDHUDKSCRS-UHFFFAOYSA-N 0.000 description 1
- DKXNBNKWCZZMJT-QMRWEYQWSA-N (2s,3r,4r,5r)-2,3,5,6-tetrahydroxy-4-[(2s,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxyhexanal Chemical compound O=C[C@@H](O)[C@@H](O)[C@@H]([C@H](O)CO)O[C@@H]1O[C@H](CO)[C@H](O)[C@H](O)[C@H]1O DKXNBNKWCZZMJT-QMRWEYQWSA-N 0.000 description 1
- LGQKSQQRKHFMLI-SJYYZXOBSA-N (2s,3r,4s,5r)-2-[(3r,4r,5r,6r)-4,5,6-trihydroxyoxan-3-yl]oxyoxane-3,4,5-triol Chemical compound O[C@@H]1[C@@H](O)[C@H](O)CO[C@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O)OC1 LGQKSQQRKHFMLI-SJYYZXOBSA-N 0.000 description 1
- ATYSZLKTHMZHJA-UXLSSDPBSA-N (3R,4R,5S,6R)-6-(hydroxymethyl)-2-[(3R,4S,5R,6R)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]-5-[(2S,3R,4S,5R,6R)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxyoxane-2,3,4-triol Chemical compound C1([C@H](O)[C@@H](O)[C@@H](O)[C@H](O1)CO)C1(O)[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@@H](O)[C@H](O2)CO)[C@H](O1)CO ATYSZLKTHMZHJA-UXLSSDPBSA-N 0.000 description 1
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- 125000000075 primary alcohol group Chemical group 0.000 description 1
- XOPPYWGGTZVUFP-DLWPFLMGSA-N primeverose Chemical compound O=C[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO[C@@H]1OC[C@@H](O)[C@H](O)[C@H]1O XOPPYWGGTZVUFP-DLWPFLMGSA-N 0.000 description 1
- QYNRIDLOTGRNML-UHFFFAOYSA-N primeverose Natural products OC1C(O)C(O)COC1OCC1C(O)C(O)C(O)C(O)O1 QYNRIDLOTGRNML-UHFFFAOYSA-N 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 238000009717 reactive processing Methods 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229940100890 silver compound Drugs 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- PZDOWFGHCNHPQD-VNNZMYODSA-N sophorose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](C=O)O[C@@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O PZDOWFGHCNHPQD-VNNZMYODSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 150000004043 trisaccharides Chemical class 0.000 description 1
- FYGDTMLNYKFZSV-BYLHFPJWSA-N β-1,4-galactotrioside Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@H](CO)O[C@@H](O[C@@H]2[C@@H](O[C@@H](O)[C@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O FYGDTMLNYKFZSV-BYLHFPJWSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/56—Glucosides; Mucilage; Saponins
-
- 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
- C07H15/02—Acyclic radicals, not substituted by cyclic structures
- C07H15/04—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical
- C07H15/10—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical containing unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C229/06—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton
- C07C229/10—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
- C07C229/12—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings to carbon atoms of acyclic carbon skeletons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/89—Carboxylic acid amides having nitrogen atoms of carboxamide groups quaternised
-
- 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
- C07H15/02—Acyclic radicals, not substituted by cyclic structures
- C07H15/04—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H3/00—Compounds containing only hydrogen atoms and saccharide radicals having only carbon, hydrogen, and oxygen atoms
- C07H3/06—Oligosaccharides, i.e. having three to five saccharide radicals attached to each other by glycosidic linkages
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/18—Quaternary ammonium compounds
Definitions
- the invention relates to novel surface-active secondary amine compounds and glycosides.
- GB 2237018 discloses the use of methyl 12- and 9-aminooctadecanoate as components of pharmaceutical compositions which modify the lipid structure of cell membranes.
- US patents 2,312,967 and 2,610,212 describe the preparation of 12-amino- octadecanoic acid by reductive amination of 12-oxo-octadecanoic acid.
- Alkyl glycosides having a long aliphatic chain are known from Biermann et al, Starch/St ⁇ rke, 45 (1993) 281-288, Balzer, Tenside Surf. Det. 28 (1991) 419-427, and others. It has been found now that polar derivatives of certain secondary aminoalkyl compounds, as well as certain alkyl glycosides, have a more useful combination of surfactant properties and critical micelle concentration.
- novel secondary amine surfactant derivatives comply with formula 1
- A represents a C ⁇ -C ⁇ alkylene group, in particular a decamethylene group
- R 1 represents hydroxymethyl, carbamoyl, carboxyl or C ⁇ -C alkoxycarbonyl
- R represents a C 5 -C 9 alkyl group, in particular a hexyl group
- R and R each represent hydrogen or a C j - t alkyl group, in particular a methyl group, or R 10 and R 11 together with the nitrogen atom represent a pyrrolidino, piperidino or morpholino group; R can also be absent (neutral amine);
- R represents a C ⁇ - 2Q alkyl, alkenyl, alkynyl, cycloalkyl(alkyl), aralkyl or acyl group, which group may be interrupted by one or more oxygen atoms or imino groups, or a
- R 12 may also represent a group having the formula Sac-(Z-A )n-, wherein
- A represents a C 2 -C 6 alkylene group optionally substituted by hydroxy
- Z represents an oxygen atom or an imino group optionally substituted by a alkyl, hydroxyalkyl or acyl group; n is an integer of 0-4; and
- Sac represents a sugar residue
- These compounds can be cationic and anionic as well as non-ionic or zwitterionic.
- these surface-active amine compounds are 9- and 12-trimethyl- ammonio-, -benzyldimethylammonio-, -(carboxymethyl)dimethylammonio-, -(3- sulphopropyl)dimethylammonio-, -acetyldimethylammonio-, -phosphomethylamino- and - ⁇ -sulphosuccinoylamino-stearic acid and esters thereof, as well as analogues wherein one or more ethyleneimino groups are bound to the amine nitrogen, such as in
- the sugar residue represented by Sac has the formula:
- R 3 , R 4 , R and R each represent hydrogen, a C j -C ⁇ alkyl, alkenyl, aralkyl or acyl group or a C j -03 alkyl or C 2 -C alkanoyl group substituted by a carboxyl, phospho and/or sulpho group;
- R 7 represents hydrogen, a carboxyl group or a group CH 2 OR ;
- R 8 represents hydrogen or together with one of the symbols R and R 6 forms a direct bond; wherein one of the symbols R 3 , R 4 , R 5 and R may also represent a sugar residue [R 6 OCHR 7 -CHOR 5 -CHOR 4 -CHOR 3 -CHR 8 -].
- glycoside derivatives of the amine compounds include 12- and 9-(galactosylamino)stearic acid and 12- and 9-(glucosylamino)stearic acid and esters thereof and the corresponding stearic alcohol derivatives.
- Other possible sugar residues are described below.
- the sugar residue can be a reducing monosaccharide, disaccharide or oligosaccharide.
- Suitable sugars include the monosaccharides glucose (Glc), galactose (Gal), mannose (Man), fructose, xylose (Xyl) and arabinose, the disaccharides maltose (Glc-l ⁇ 4-Glc), isomaltose (Glc-l ⁇ 6-Glc), cellobiose (Glc-l ⁇ 4-Glc), gentio- biose (Glc-l ⁇ 6-Glc), laminaribiose (Glc-l ⁇ 3-Glc), melibiose (Gal-l ⁇ 6-Glc), lactose (Gal-l ⁇ 4-Glc), epilactose (Gal-l ⁇ 4-Man), primeverose (Xyl-1 ⁇ 6-Glu) and xylobiose (Xyl-l ⁇ 4-Xyl) and the corresponding trisaccharides such as maltotriose, galacto
- Di- and higher saccharides wherein the second sugar group is attached to the 2 position of the first sugar are somewhat less useful. Pentasaccharides and higher are also less important. Preference is given to aldoses, in particular non-expensive sugars such as glucose, galactose, lactose and maltose. Examples of groups forming part of the C j -C ⁇ alkyl groups interrupted by one
- oxygen atoms or imino groups represented by R examples include alkyleneoxy or alkyleneimino groups, such as ethyleneoxy, 1,2-propyleneoxy, 2-hydroxy- 1,3-propyleneoxy, 2,2-bis(hydroxy- methyl)- 1,3-propyleneoxy, ethyleneimino, 1,3-propyleneimino, hexamethyleneimino,
- the secondary amines can be prepared from the corresponding unsaturated compounds, halogen compounds, ketones or alcohols.
- a mixture of methyl-9- and -10-aminooctadecanoic acid can be obtained by treatment of methyl oleate with 70% nitric acid and hydrogenation with Raney nickel
- 12-aminooctadecanoic acid can be obtained from 12-oxooctadecanoic acid by reductive amination with ammonia and a catalyst, of, advantageously, by oximation with anhydrous hydroxylamine in methanol followed by hydrogenation, such as illustrated in the examples.
- the same procedure can be followed for the corresponding 1-hydroxy compounds, starting from l-hydroxy-9- or -12-octadecanone, respectively.
- the oximation of oxoalkanoic acids and oxoalkanols is preferably performed using neutral hydroxylamine in a C j -C 3 alcohol, in particular methanol.
- the reduction thereof is preferably performed using mild temperatures, preferably about room temperature (10-30°C) and using hydrogen under a pressure of e.g. 1.5-5 bar in the presence of a transition metal catalyst, especially palladium on carbon.
- a transition metal catalyst especially palladium on carbon.
- the groups R 10 , R 11 and R 12 can be introduced in a manner known per se. If R 10 , R 11 (and R 12 ) are alkyl groups, these can be introduced by reaction of the secondary amine with the corresponding alkyl halide, s ⁇ lphonate, sulphate or the like, such as methyl iodide, diethyl sulphate, butyl bromide. Similarly, groups such as alkenyl (e.g. allyl or octadienyl), alkynyl (e.g. propargyl), benzyl, cycloalkylalkyl, represented by R 12 , can be introduced using the corresponding halide, (methane)sulphonate etc.. Hydroxy- alkyl groups can be introduced using halides or epoxides, such as epichlorohydrine. Acyl groups R such as acetyl are introduced using the appropriate acid anhydride or acid halide.
- Alkyl or alkanoyl groups substituted by a carboxyl, phospho and/or sulpho group as R 12 include alkyl and alkanoyl groups substituted by one or more acid groups -COOH, -PO(R 9 )(OH), -PO(OR 9 )(OH), -OPO(R 9 )(OH), -OPO(OR 9 )(OH), -SO 3 H or -OSO3H, while the group -PO(R 9 )(OH), -PO(OR 9 )(OH), -SO 3 H can also be directly bound to the nitrogen atom.
- R represents a hydrogen atom or a C j -Cy hydrocarbon group, such as methyl, ethyl, allyl, butyl, phenyl, cyclohexyl or benzyl.
- the acid groups can of course be present in ionised form, and in particular as part of zwitter- ions.
- These compounds can be prepared for example by reaction of the amine, for example: a haloacetic acid resulting in a carboxymethyl derivative; acrylonitrile followed by saponification resulting in a carboxyethyl derivative; a halomethylphosphonic acid resulting in a phosphonomethyl derivative; formaldehyde and an alkylphosphinic acid resulting in an ethylphosphinicomethyl) derivative; hydroxymethylsulphonic acid resulting in a sulphomethyl derivative; chloroethanesulphonic acid resulting in a sulpho- ethyl derivative; ethyleneoxide and chlorosulphonic acid resulting in a sulphatoethyl derivative; chlorosulphonic acid or chlorophosphonic acid resulting in an sulphato or phosphato derivative; succinic anhydride resulting in a succinoyl derivative; or maleic anhydride and sulphite resulting in a ⁇ -sulphosuccino
- the invention also relates to novel glycosides complying with formula 2,
- the sugar residue Sac of the glycoside can be a reducing monosaccharide, disaccharide or oligosaccharide as described above.
- the glycosides according to the invention are obtained from a secondary alcohol or a secondary amine.
- the secondary alcohol or the secondary amine which, together with the sugar, forms the surface-active glycoside according to the invention, contains at least 9, in particular 12-24 carbon atoms, the hydroxyl group and the amino group, respectively, being located at a distance of at least 4 atoms from the chain ends, such as in 9-octadecanol.
- the secondary alcohol can optionally contain a second, secondary hydroxyl group.
- the secondary alcohol contains a carboxyl-derived function such as an alkyl ester, an amide or a mono- or di-alkylamide.
- one of the two groups R 13 and R in the formulae 1 and 2 is preferably substituted in the manner as indicated, especially by carboxyl or alkoxycarbonyl.
- suitable hydroxy carboxylic acids are 10-hydroxy ⁇ almitic acid, 9-hydroxystearic acid, 12-hydroxystearic acid, ricinoleic acid (12-hydroxyoleic acid) and dimo ⁇ hecolic acid (9-hydroxy-10,12-octadecadienoic acid).
- saturated acids such as the amino- and hydroxystearic acids.
- Starting materials that are most suitable are the alkyl esters and dialkylamides of the hydroxy acids.
- alkyl means C 1 -C -alkyl, in particular methyl and ethyl.
- the esters and amides can be reduced afterwards to alcohols and amines, respectively, if desired.
- the secondary amine can optionally also contain a hydroxyl group.
- suitable amines are 9- and 12-amino-octadecanoic esters and amides and 9- and 12- amino-octadecanol.
- the alcohols and amines can optionally contain one or more alkyleneoxy or alkyleneimino groups between the aliphatic residue and the sugar residue, as described above.
- novel alkyl glycosides can be prepared for example using the Koenigs- Knorr synthesis (Adv. Carbohydr. Chem. Biochem., 34 (1977) 243), starting with a glycosyl halide and the secondary alcohol in the presence of a heavy metal compound such as a silver or mercury compound, in particular a mercury(II) halide with a cata- lytically active amount of iodide ions in an anhydrous solvent such as dichloromethane and a water-binding agent such as molecular sieves.
- a heavy metal compound such as a silver or mercury compound, in particular a mercury(II) halide with a cata- lytically active amount of iodide ions in an anhydrous solvent such as dichloromethane and a water-binding agent such as molecular sieves.
- the other hydroxyl groups of the glycoside should be protected as an ester (for example an acetate) or ether (for example a benz
- the process starts with an imidate ester of the sugar, in particular a trichloroacetic imidate, obtained by reaction of the sugar with trichloroacetonitrile (scc Angew. Chem., Int. Ed. Engl, 25 (1986) 212; Adv. Carbohydr. Chem. Biochem., 50 (1994) 21).
- imidate ester of the sugar in particular a trichloroacetic imidate
- the novel alkyl glycosides can be obtained in an advantageous manner by reaction of the glycosyl halide with a hindered amine, such as triethylamine or diisopropylamine, in a polar aprotic solvent such as acetonitrile, propiononitrile, tetrahydrofuran, nitromethane or dimethylformamide, in the presence of a water-binding agent. Yield in the order of 50% can be obtained in this way.
- any protecting groups such as acetate groups or benzyl groups can be removed, if desired, by hydrolysis or reduction, in a manner known per se.
- the amine can react with the sugar as such, producing a glycosylamine.
- this glycosylamine is reduced to the more stabile glycitylamine, the direct bond between R 8 and R 5 /R 6 in formula 2 being hydrogenated.
- the reduction can for example be performed with sodium borohydride or with hydrogen and a metal catalyst, such as nickel, palladium, platinum, ruthenium or another group VIII metal, optionally on a support such as carbon.
- the amination and reduction can be carried out in distinct steps. However, higher yields are obtained, when the reductive amination is carried out in a single step, preferably with hydrogen and a catalyst.
- Solvents to be used include, for example, water, an alcohol or an alcohol-water mixture. It was found that if a slightly less than equivalent amount of alkylamine with respect to sugar is used, the sugar is not reduced and thus the product can be further processed in a more simple manner.
- the alkyl glycosylamine can also, advantageously, be acylated, resulting in more stabile derivatives, which moreover have useful surfactant properties; in formula 2, Z represents acylimino for these derivatives.
- the acylation can be effected by treating the alkylglycosylamine with a C j -C 3 carboxylic acid anhydride or halide in a suitable solvent, preferably with a base.
- the amination of the sugar and the acylation can also be performed by "reactive processing” (see e.g. Tomasik et al., Starch/St ⁇ rke 47 (1995), 96-99, and Narkrugsa et al. Starch/St ⁇ rke 44 (1992), 81-90), i.e. without or with low levels of solvents with mechanical agitation, for example in an extruder.
- one or more of the primary alcohol groups in the alkyl glycosides or alkyl glycosylamines can be converted to a carboxylic acid group, for example by oxidation with hypochlorite in the presence of 2,2,6,6-tetramethylpiperidine-l-oxyl (TEMPO), or by oxidation with oxygen and a transition metal catalyst.
- TEMPO 2,2,6,6-tetramethylpiperidine-l-oxyl
- a further aspect of the invention pertains to surfactant glycosyl amines and glycosides bearing an alkyl group or alkanoyl group having 1-4 carbon atoms substituted by one or more acid groups -COOH, -PO(R 9 )(OH), -PO(OR 9 )(OH), -OPO(R 9 )(OH), -OPO(OR 9 )(OH), -SO 3 H or -OSO 3 H on one or more of the oxygen- (and, if applicable, nitrogen) atoms, while the group -PO(R 9 )(OH), -PO(OR 9 )(OH), -SO 3 H can also be directly bound to an oxygen atom.
- R represents hydrogen or a hydrocarbon group as defined above.
- the invention also relates to the use of the derivatives described above as an emulsifier in foodstuffs, as a detergent as an am emulsifier in washing compositions, dish-washing compositions, body care compositions, cosmetics, shampoos, or as a dis- persant for e.g. pesticides etc.
- Methyl 12-(hydroxyimino)-octadecarioate (example 1) (3.27 g) was hydrogenated during 48 hours in methanol (100 ml) with 10% palladium on activated coal (200 mg), at room temperature and 2.1-2.8 bar of hydrogen pressure. Then the catalyst was removed from the reaction mixture by filtration over Celite . The Celite layer was washed with a total of 150 ml warm (50°C) methanol, and the filtrate was evaporated to dryness. The residue was redissolved in 30 ml hot methanol and this solution was added to 120 ml of distilled water.
- Methyl 12-aminooctadecanoate was extracted from the aqueous methanol phase with a total of 150 ml of hexane.
- the organic phase was dried (MgSO 4 ), filtered, and the solvent was evaporated, yielding the title product (3.0 g, 95%).
- Example 6 Methyl 9-aminooctadecanoate The methods as described in example 5 were used starting with the 9-oxime of example 2. Yield: 3.0 g (96%). 1H (3.150 s, 1H, H-9) and 13 C NMR, FT-IR, MS spectral and analysis data are in accordance with the structure.
- Example 9 1 -Hydroxy -9- (trimethylammonio)octadecane
- the product of example 8 is dissolved in dichloromethane and reacted with methyl iodide (6 equivalents) to produce the title product after evaporation.
- Example 10 Methyl 12-(peracetylgalactosylamino)stearate via Koenings -Knorr reaction
- Example 11 Methyl 12-galactosylaminostearate
- the product of the previous example is deacetylated with sodium methoxide in methanol with reflux for 4 h.
- IR (cm -1 ) 3365 (w); 2936 (s); 2359 (s); 2337 (s); 1651 (s); 1447 (s,w); 1354 (s).
- Examples 12-15 1 -0-(ll -Methoxycarbonyl-1 -hexylundecyl) - ⁇ -D-glucose,
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Abstract
Surface-active amines are described having the formula (1): R?10R11R12N+-CHR2-A1-R1¿ wherein A1 represents a C¿7?-C11 alkylene group; R?1¿ represents hydroxymethyl, carbamoyl, carboxyl or (C¿1?-C4alkoxy)carbonyl; R?2¿ represents a C¿5?-C9 alkyl group; R?10 and R11¿ each represent hydrogen or a C¿1?-C4 alkyl group, or R?10 and R11¿ together with the nitrogen atom represent a pyrrolidino, piperidino or morpholino group; R12 represents a C¿1?-C20 alkyl, alkenyl, alkynyl, cycloalkyl(alkyl), aralkyl or acyl group, which group may be interrupted by one or more oxygen atoms or imino groups, a C1-C3alkyl or C2-C3 alkanoyl group substituted by a carboxyl, phospho and/or sulpho group, or a sugar residue; wherein, if R?10¿ represents hydrogen, the nitrogen atom may also be deprotonated. Surfactant alkylglycosides are also described. The compounds can be used as emulsifiers, in detergents and the like.
Description
Surfactant amines and glycosides
The invention relates to novel surface-active secondary amine compounds and glycosides.
GB 2237018 discloses the use of methyl 12- and 9-aminooctadecanoate as components of pharmaceutical compositions which modify the lipid structure of cell membranes. US patents 2,312,967 and 2,610,212 describe the preparation of 12-amino- octadecanoic acid by reductive amination of 12-oxo-octadecanoic acid. Alkyl glycosides having a long aliphatic chain are known from Biermann et al, Starch/Stάrke, 45 (1993) 281-288, Balzer, Tenside Surf. Det. 28 (1991) 419-427, and others. It has been found now that polar derivatives of certain secondary aminoalkyl compounds, as well as certain alkyl glycosides, have a more useful combination of surfactant properties and critical micelle concentration.
The novel secondary amine surfactant derivatives comply with formula 1
R10R11R12N+_CHR2_A1_R1 j wherein
A represents a Cγ-C^ alkylene group, in particular a decamethylene group;
R1 represents hydroxymethyl, carbamoyl, carboxyl or Cγ-C alkoxycarbonyl;
R represents a C5-C9 alkyl group, in particular a hexyl group;
R and R each represent hydrogen or a Cj- t alkyl group, in particular a methyl group, or R10 and R11 together with the nitrogen atom represent a pyrrolidino, piperidino or morpholino group; R can also be absent (neutral amine);
R represents a C^- 2Q alkyl, alkenyl, alkynyl, cycloalkyl(alkyl), aralkyl or acyl group, which group may be interrupted by one or more oxygen atoms or imino groups, or a
Cj-Cg alkyl or C2-C3 alkanoyl group substituted by a carboxyl, phospho and/or sulpho group. The symbol R12 may also represent a group having the formula Sac-(Z-A )n-, wherein
A represents a C2-C6 alkylene group optionally substituted by hydroxy;
Z represents an oxygen atom or an imino group optionally substituted by a
alkyl, hydroxyalkyl or acyl group; n is an integer of 0-4; and
Sac represents a sugar residue.
These compounds can be cationic and anionic as well as non-ionic or zwitterionic.
Examples of these surface-active amine compounds are 9- and 12-trimethyl- ammonio-, -benzyldimethylammonio-, -(carboxymethyl)dimethylammonio-, -(3- sulphopropyl)dimethylammonio-, -acetyldimethylammonio-, -phosphomethylamino- and -β-sulphosuccinoylamino-stearic acid and esters thereof, as well as analogues wherein one or more ethyleneimino groups are bound to the amine nitrogen, such as in
12-[(carboxymethyl)dimethylammonio-ethyleneamino]stearic acid, and corresponding derivatives of other C14-C2 fatty acids, esters, amides and alcohols. The sugar residue represented by Sac has the formula:
R6OCHR7-CHOR5-CHOR4-CHOR3-CHR8- wherein
R3, R4, R and R each represent hydrogen, a Cj-Cγ alkyl, alkenyl, aralkyl or acyl group or a Cj-03 alkyl or C2-C alkanoyl group substituted by a carboxyl, phospho and/or sulpho group; R7 represents hydrogen, a carboxyl group or a group CH2OR ; R8 represents hydrogen or together with one of the symbols R and R6 forms a direct bond; wherein one of the symbols R3, R4, R5 and R may also represent a sugar residue [R6OCHR7-CHOR5-CHOR4-CHOR3-CHR8-].
Examples of the glycoside derivatives of the amine compounds include 12- and 9-(galactosylamino)stearic acid and 12- and 9-(glucosylamino)stearic acid and esters thereof and the corresponding stearic alcohol derivatives. Other possible sugar residues are described below. The sugar residue can be a reducing monosaccharide, disaccharide or oligosaccharide. Suitable sugars include the monosaccharides glucose (Glc), galactose (Gal), mannose (Man), fructose, xylose (Xyl) and arabinose, the disaccharides maltose (Glc-lα→4-Glc), isomaltose (Glc-lα→6-Glc), cellobiose (Glc-lβ→4-Glc), gentio- biose (Glc-lβ→6-Glc), laminaribiose (Glc-lβ→3-Glc), melibiose (Gal-l →6-Glc), lactose (Gal-lβ→4-Glc), epilactose (Gal-lβ→4-Man), primeverose (Xyl-1→6-Glu) and xylobiose (Xyl-lβ→4-Xyl) and the corresponding trisaccharides such as maltotriose, galactosyl-lactose and higher homologues. Di- and higher saccharides wherein the second sugar group is attached to the 2 position of the first sugar, such as kojibiose and sophorose, are somewhat less useful. Pentasaccharides and higher are also less important. Preference is given to aldoses, in particular non-expensive sugars such as glucose, galactose, lactose and maltose.
Examples of groups forming part of the Cj-C^ alkyl groups interrupted by one
19 or more oxygen atoms or imino groups represented by R , and examples of the groups (Z-A2)n, represented by R12, include alkyleneoxy or alkyleneimino groups, such as ethyleneoxy, 1,2-propyleneoxy, 2-hydroxy- 1,3-propyleneoxy, 2,2-bis(hydroxy- methyl)- 1,3-propyleneoxy, ethyleneimino, 1,3-propyleneimino, hexamethyleneimino,
N-hydroxyethyl-ethyleneimino and oligomers thereof.
The secondary amines can be prepared from the corresponding unsaturated compounds, halogen compounds, ketones or alcohols. Thus, a mixture of methyl-9- and -10-aminooctadecanoic acid can be obtained by treatment of methyl oleate with 70% nitric acid and hydrogenation with Raney nickel, and 12-aminooctadecanoic acid can be obtained from 12-oxooctadecanoic acid by reductive amination with ammonia and a catalyst, of, advantageously, by oximation with anhydrous hydroxylamine in methanol followed by hydrogenation, such as illustrated in the examples. The same procedure can be followed for the corresponding 1-hydroxy compounds, starting from l-hydroxy-9- or -12-octadecanone, respectively.
The oximation of oxoalkanoic acids and oxoalkanols is preferably performed using neutral hydroxylamine in a Cj -C3 alcohol, in particular methanol. The reduction thereof is preferably performed using mild temperatures, preferably about room temperature (10-30°C) and using hydrogen under a pressure of e.g. 1.5-5 bar in the presence of a transition metal catalyst, especially palladium on carbon. The same solvent
(e.g. methanol) can be used in the hydrogenation reaction and prior isolation of the oxime is not necessary.
The groups R10, R11 and R12 can be introduced in a manner known per se. If R10, R11 (and R12) are alkyl groups, these can be introduced by reaction of the secondary amine with the corresponding alkyl halide, sύlphonate, sulphate or the like, such as methyl iodide, diethyl sulphate, butyl bromide. Similarly, groups such as alkenyl (e.g. allyl or octadienyl), alkynyl (e.g. propargyl), benzyl, cycloalkylalkyl, represented by R12, can be introduced using the corresponding halide, (methane)sulphonate etc.. Hydroxy- alkyl groups can be introduced using halides or epoxides, such as epichlorohydrine. Acyl groups R such as acetyl are introduced using the appropriate acid anhydride or acid halide.
Alkyl or alkanoyl groups substituted by a carboxyl, phospho and/or sulpho group as R12 include alkyl and alkanoyl groups substituted by one or more acid groups -COOH, -PO(R9)(OH), -PO(OR9)(OH), -OPO(R9)(OH), -OPO(OR9)(OH), -SO3H or
-OSO3H, while the group -PO(R9)(OH), -PO(OR9)(OH), -SO3H can also be directly bound to the nitrogen atom. Herein R represents a hydrogen atom or a Cj-Cy hydrocarbon group, such as methyl, ethyl, allyl, butyl, phenyl, cyclohexyl or benzyl. The acid groups can of course be present in ionised form, and in particular as part of zwitter- ions. These compounds can be prepared for example by reaction of the amine, for example: a haloacetic acid resulting in a carboxymethyl derivative; acrylonitrile followed by saponification resulting in a carboxyethyl derivative; a halomethylphosphonic acid resulting in a phosphonomethyl derivative; formaldehyde and an alkylphosphinic acid resulting in an ethylphosphinicomethyl) derivative; hydroxymethylsulphonic acid resulting in a sulphomethyl derivative; chloroethanesulphonic acid resulting in a sulpho- ethyl derivative; ethyleneoxide and chlorosulphonic acid resulting in a sulphatoethyl derivative; chlorosulphonic acid or chlorophosphonic acid resulting in an sulphato or phosphato derivative; succinic anhydride resulting in a succinoyl derivative; or maleic anhydride and sulphite resulting in a β-sulphosuccinoyl derivative. Suitable derivatisation methods for introducing the acid groups have been described for example by Van
Haveren et al, NMR in Biomedicine, 8, 197-205 (1995), and O'Lenick et al, JAOCS, 73, 935-937 (1996).
The invention also relates to novel glycosides complying with formula 2,
Sac-(Z-A2)n-Z-CH(R13R14) 2 wherein the symbols A2, Z, n, Sac and R3 to R8 are as defined above and R13 and R14 are as defined in claim 6. The sugar residue Sac of the glycoside can be a reducing monosaccharide, disaccharide or oligosaccharide as described above.
The glycosides according to the invention are obtained from a secondary alcohol or a secondary amine. The secondary alcohol or the secondary amine which, together with the sugar, forms the surface-active glycoside according to the invention, contains at least 9, in particular 12-24 carbon atoms, the hydroxyl group and the amino group, respectively, being located at a distance of at least 4 atoms from the chain ends, such as in 9-octadecanol. The secondary alcohol can optionally contain a second, secondary hydroxyl group. Preferably, the secondary alcohol contains a carboxyl-derived function such as an alkyl ester, an amide or a mono- or di-alkylamide. Thus, one of the two groups R13 and R in the formulae 1 and 2 is preferably substituted in the manner as indicated, especially by carboxyl or alkoxycarbonyl. Examples of suitable hydroxy carboxylic acids are 10-hydroxyρalmitic acid, 9-hydroxystearic acid, 12-hydroxystearic acid, ricinoleic
acid (12-hydroxyoleic acid) and dimoφhecolic acid (9-hydroxy-10,12-octadecadienoic acid). Most preferred are saturated acids such as the amino- and hydroxystearic acids. Starting materials that are most suitable are the alkyl esters and dialkylamides of the hydroxy acids. In this context, alkyl means C1-C -alkyl, in particular methyl and ethyl. The esters and amides can be reduced afterwards to alcohols and amines, respectively, if desired.
The secondary amine can optionally also contain a hydroxyl group. Examples of suitable amines are 9- and 12-amino-octadecanoic esters and amides and 9- and 12- amino-octadecanol. The alcohols and amines can optionally contain one or more alkyleneoxy or alkyleneimino groups between the aliphatic residue and the sugar residue, as described above.
The novel alkyl glycosides can be prepared for example using the Koenigs- Knorr synthesis (Adv. Carbohydr. Chem. Biochem., 34 (1977) 243), starting with a glycosyl halide and the secondary alcohol in the presence of a heavy metal compound such as a silver or mercury compound, in particular a mercury(II) halide with a cata- lytically active amount of iodide ions in an anhydrous solvent such as dichloromethane and a water-binding agent such as molecular sieves. The other hydroxyl groups of the glycoside should be protected as an ester (for example an acetate) or ether (for example a benzyl ether). In an alternative embodiment, the process starts with an imidate ester of the sugar, in particular a trichloroacetic imidate, obtained by reaction of the sugar with trichloroacetonitrile (scc Angew. Chem., Int. Ed. Engl, 25 (1986) 212; Adv. Carbohydr. Chem. Biochem., 50 (1994) 21). The other hydroxyl groups of the glycoside can be protected herein as well. It has been found that the novel alkyl glycosides can be obtained in an advantageous manner by reaction of the glycosyl halide with a hindered amine, such as triethylamine or diisopropylamine, in a polar aprotic solvent such as acetonitrile, propiononitrile, tetrahydrofuran, nitromethane or dimethylformamide, in the presence of a water-binding agent. Yield in the order of 50% can be obtained in this way. Once the alkyl glycoside has been obtained, any protecting groups such as acetate groups or benzyl groups can be removed, if desired, by hydrolysis or reduction, in a manner known per se.
The amine can react with the sugar as such, producing a glycosylamine. Advantageously, this glycosylamine is reduced to the more stabile glycitylamine, the
direct bond between R8 and R5/R6 in formula 2 being hydrogenated. The reduction can for example be performed with sodium borohydride or with hydrogen and a metal catalyst, such as nickel, palladium, platinum, ruthenium or another group VIII metal, optionally on a support such as carbon. The amination and reduction can be carried out in distinct steps. However, higher yields are obtained, when the reductive amination is carried out in a single step, preferably with hydrogen and a catalyst. Solvents to be used include, for example, water, an alcohol or an alcohol-water mixture. It was found that if a slightly less than equivalent amount of alkylamine with respect to sugar is used, the sugar is not reduced and thus the product can be further processed in a more simple manner.
The alkyl glycosylamine can also, advantageously, be acylated, resulting in more stabile derivatives, which moreover have useful surfactant properties; in formula 2, Z represents acylimino for these derivatives. The acylation can be effected by treating the alkylglycosylamine with a Cj-C3 carboxylic acid anhydride or halide in a suitable solvent, preferably with a base.
The amination of the sugar and the acylation can also be performed by "reactive processing" (see e.g. Tomasik et al., Starch/Stάrke 47 (1995), 96-99, and Narkrugsa et al. Starch/Stάrke 44 (1992), 81-90), i.e. without or with low levels of solvents with mechanical agitation, for example in an extruder. Optionally one or more of the primary alcohol groups in the alkyl glycosides or alkyl glycosylamines can be converted to a carboxylic acid group, for example by oxidation with hypochlorite in the presence of 2,2,6,6-tetramethylpiperidine-l-oxyl (TEMPO), or by oxidation with oxygen and a transition metal catalyst.
A further aspect of the invention pertains to surfactant glycosyl amines and glycosides bearing an alkyl group or alkanoyl group having 1-4 carbon atoms substituted by one or more acid groups -COOH, -PO(R9)(OH), -PO(OR9)(OH), -OPO(R9)(OH), -OPO(OR9)(OH), -SO3H or -OSO3H on one or more of the oxygen- (and, if applicable, nitrogen) atoms, while the group -PO(R9)(OH), -PO(OR9)(OH), -SO3H can also be directly bound to an oxygen atom. R represents hydrogen or a hydrocarbon group as defined above. These compounds can be prepared for example by reaction of a glycitylamine or glycosylamine as describe above with the reagents described above (a haloacetic acid etc.).
The invention also relates to the use of the derivatives described above as an emulsifier in foodstuffs, as a detergent as an am emulsifier in washing compositions,
dish-washing compositions, body care compositions, cosmetics, shampoos, or as a dis- persant for e.g. pesticides etc.
EXAMPLES General Methyl 9-hydroxyoctadecanoic acid was obtained by extraction of Dimorphoteca pluvialis seeds and transesterification and hydrogenation of the dimoφhecolic esters as described by Tassignon et al, Chem. Phys. Lipids 71 (1994) 187-196; Ind. Crops. Prod. 4 (1995) 121-125. 12-Hydroxyoctadecanoic acid is commercially available, but for the formation of the methyl ester an esterification step followed by crystallisation is advantageous. l-Hydroxy-9-octadecanone and l-hydroxy-12-octadecanone were prepared as described by Tassignon et al, Tetrahedron 51 (1995), 11863-11872.
Example 1: Methyl 12-(hydroxyimino)octadecanoate
Method 1 (using NH2OH.HCl and Et^): 3.1 g (10 mmol) of methyl 12-oxo-octa- decanoate, 1.1 g (11 mmol) Et3N and 0.75 g (11 mmmol) hydroxylamine-hydrochloride were dissolved in 27 ml of MeOH. This reaction mixture was refluxed for 2 hours and then transferred to a separatory funnel, containing 108 ml of water. The aqueous phase was extracted three times with hexane (50 ml). The organic layers were collected, washed with aq. HC1 (0.1N) until neutral pH of the organic phase, dried (MgSO4), filtered, and evaporated to give 3.14 g (9.61 mmol, 96%) of product. Method 2 (using free NH2OH): Prior to the condensation reaction of hydroxylamine and the keto function, 1.1 g (11 mmol) of Et3N and 0.76 g (11 mmol) HONH2.HCl were dissolved in 6 ml of CH2C12. After 30 minutes, diethyl ether (30 ml) was added to the solution and triethylamine.hydrochloride crystals were formed. After filtration, the organic phase was transferred to a second flask in which 3.12 g (10 mmol) of methyl- 12-oxooctadecanoate in 30 ml of MeOH was dissolved. After 2 hours at reflux temperature, the solvents were evaporated and the crude oil was dissolved again in 2 ml of MeOH and 10 ml hexane and washed with two times 10 ml of water. The organic phase was dried (MgSO4) and the organic solvents were evaporated. Yield for the title compound: 3.17 g (96 %). 1H NMR (δ ppm; 400 MHz): 0.879 (t, 3 H, H-18, J18 17 = 6.9 Hz), 1.270-1.400 (m, 18 H, H-4, 5, 6, 7, 8, 9, 15, 16, 17), 1.497 (m, 4 H, H-10,
14), 1.622 (m, 2 H, H-3), 2.165 (t, 4H, H-ll, 13, Jn l0 = 7.7 Hz, J13 14 = 7.7 Hz), 2.280-2.346 (m, 6 H, H-2, 11/13), 3.659 (s, 3 H, CH3O);
13C NMR (δ ppm: 75 MHz): 14.13 (C-18), 22.66 (C-17), 25.71, 26.32, 26.44, 27.52, 27.58, 29.07, 29.16, 29.46, 29.74 and 29.98 (CH2-alkyl), 31.89 and 31.95 (C-10, C-14), 34.07 and 34.13 (C-11, C-13), 51.44 ( CH3O), 161.61 (C=N-OH, anti and syn), 174.30 (C-1); FT-IR (cm-1): 1738.7 (C=O), 1658.5 (C=N-OH); M/e (%): 328 (M++l,0.3), 310 (M+-OH,8), 242 (C13H24O3N,15), 215(6), 199 (C12H2O2, 23), 198 (21), 110 (7), 83 (12), 73 (C3H5O2,100), 70 (15), 57 (35), 56 (12), 43 (58); Anal. Calc.(%) for C, H, N: 69.6, 11.3, 4.3; Found (%): 69.7, 11.2, 4.2.
Example 2: Methyl 9-(hydroxyimino)octadecanoate
The methods of example 1 were followed using methyl 9-oxo-octadecanoate. Yield: 3.17 g (97%). 1H and 13C NMR, FT-IR, MS spectral and analysis data are in accordance with the structure.
Example 3: l -Hydroxy-12-(hydroxyimino)octadecane
Similar reaction conditions were used as in example 1, using l-hydroxy-12- octanone. Yield: 2.79 g (93%). 1H and 13C NMR, FT-IR, MS spectral and analysis data are in accordance with the structure.
Example 4: l -Hydroxy-9-(hydroxyimino)octadecane
Similar reaction conditions were used as in example 1, using l-hydroxy-9- octanone. Yield: 2.83 g (94%). 1H and 13C NMR, FT-IR, MS spectral and analysis data are in accordance with the structure.
Example 5: Methyl 12-aminooctadecanoate
Methyl 12-(hydroxyimino)-octadecarioate (example 1) (3.27 g) was hydrogenated during 48 hours in methanol (100 ml) with 10% palladium on activated coal (200 mg), at room temperature and 2.1-2.8 bar of hydrogen pressure. Then the catalyst was removed from the reaction mixture by filtration over Celite . The Celite layer was washed with a total of 150 ml warm (50°C) methanol, and the filtrate was evaporated to dryness. The residue was redissolved in 30 ml hot methanol and this solution was added to 120 ml of distilled water. Methyl 12-aminooctadecanoate was extracted from the aqueous methanol phase with a total of 150 ml of hexane. The organic phase was dried (MgSO4), filtered, and the solvent was evaporated, yielding the title product (3.0 g, 95%). 1H NMR (δ ppm; 300 MHz): 0.879 (t, 3H, H-18, J18 17 = 6.9 Hz), 1.270-1.400
(m, 18H, H- 4, 5, 6, 7, 8, 9, 15, 16, 17), 1.497 (m, 4H, H-10, 14), 1.624-1.973 (m, 2H, H-3), 2.179 (t, 2H,J2)3 = 7.7 Hz), 2.280-2.346 (m, 4H, 11/13), 3.212 (s, 1H, H-9), 3.663 (s, 3H, CH3O); 13C NMR (δ ppm: 75 MHz): 13.52 (C-18), 22.06 (C-17), 23.34, 24.44, 24.86, 28.49, 28.64 (CH2-alkyl, with overlap), 31.04 and 32.17 (C-10, C-14), 33.58 (C- 11, C-13), 50.96 (CH3O), 52.08 (C-12) 173.65 (C-1); FT-IR (cm-1): 3402.1-3014.2
(NH^, 1746.2 (C=O); M/e (%): 314 (M+, 0.1), 242 (3), 228 (C13H26O2N, 52), 196 (8), 128 (5), 114 (C7H16N,100), 81 (2); Anal. Calc.(%) for C, H, N: 72.7, 12.4, 4.5; Found (%): 72.6, 12.5, 4.4.
Example 6: Methyl 9-aminooctadecanoate The methods as described in example 5 were used starting with the 9-oxime of example 2. Yield: 3.0 g (96%). 1H (3.150 s, 1H, H-9) and 13C NMR, FT-IR, MS spectral and analysis data are in accordance with the structure.
Example 7: l -Hydroxy-12-aminooctadecane
Similar reaction conditions were used as in example 5 using the compound of example 3. Yield: 2.66 g (94%). 1H (3.125 m, 1H, H-9) and 13C NMR, FT-IR, MS spectral and analysis data are in accordance with the structure.
Example 8: 1 -Hydroxy -9-aminooctadecane
Similar reaction conditions were used as in example 5, using the compound of example 4. Yield: 2.75 g (97%). 1H (δ ppm; 300 MHz): 0.879 (t, 3H, H-18, J18 17 = 6.6 Hz), 1.210-1.456 (m, 24H, H-3,4,5,6,7,11, 12,13,14,15,16,17), 1.560 m, 2H, H-2), 2.13
(1-OH, NH^, 2.371 (2*t, 4H, H-8, 10, J8 7 = 7.6 Hz, Jlo n = 7.6 Hz), 3.231 (m, 1H, H-9), 3.621 (t, 2H, H-l, J1>2 = 6.6 Hz); 13C (d ppm; 75 MHz): 13.92 (c-18), 22.78 (C- 17), 25.16, 25.29 25.56, 27.56, 29.00, 29.59, 29.84, 31.50, 32, 31 (CH2-alkyl), 32,12, 33.18 (C-2, 16), 42.12 (C-9, 10), 52.39 (C-9), 62.78 (C-1); FT-IR: (cm-1): 3600-3040 (OH, NH2), 1703.8, 1610.2; M/e (%): 285 (M++l, 3), 268 (M+-NH2, 8), 267 (M+-OH,
4), 157 (C9H19ON, 26), 155 (CιrjH21N, 26), 131 (12), 127 (8), 97 (94), 81 (40), 69 (53), 57 (29), 55 (100); Anal. Calc.(%) for C, H, N: 76.1, 12.4, 4.9; Found (%): 76.0, 12.4, 5.0.
Example 9: 1 -Hydroxy -9- (trimethylammonio)octadecane The product of example 8 is dissolved in dichloromethane and reacted with
methyl iodide (6 equivalents) to produce the title product after evaporation.
Example 10: Methyl 12-(peracetylgalactosylamino)stearate via Koenings -Knorr reaction
In a 250 ml flask (dried at 105°C) 2.47 g (7.9 mmol) of methyl 12-aminostearate (example 5) and 2.85 g (7.9 mmol) of mercury(II) bromide are added to 100 ml dry dichloromethane. About 10 g of molecular sieves (4) are also added and the flask is equipped with a calcium chloride tube. The mixture is cooled at 0°C in an ice bath, and 3.37 g (7.9 mmol) of peracetylgalactosyl bromide is added after 1 h. The mixture is stirred overnight at 0 °C. The molecular sieves and the mercury bromide are filtered off, the residue is washed with 150 ml of dichloromethane. The dichloromethane phase is consecutively washed with 100 ml of saturated sodium bicarbonate solution and 100 ml of brine (twice). After the washings the dichloromethane phase is dried overnight on magnesium sulphate. The magnesium sulphate is filtered off and the dichloromethane layer is evaporated on a rotary film evaporator. Of the crude product (4.96 g), 2.0 g is brought on a silica gel column with 35/65 ethyl acetate/n-hexane as eluent. The yield of methyl 12-(peracetylgalactosyl)stearate is 0.81 g (36%).
1H-NMR: (δ in ppm; 400 MHz): 0.8834 (H-18, t, J=5.24 Hz), 1.2618-1.5999 (alkyl, m), 1.9889-2.1799 (CH3, m, acetyl), 2.3329 (H-2, t, J=7.5 Hz), 3.4856 (H-12, q, J=22 Hz), 3.6712 (OCH3), s), 3.9319 (H-5', m), 4.1139-4.1873 (H-6',m), 4.4053 (HI', J=7.96 Hz), 5.0202 (H-3', J=5.3 Hz), 5.2023 (H-2', dd, Jab=6.5 Hz; Jac=7.46 Hz), 5.3974 (H-
4', t, J=3.32 Hz).
13C-NMR: (δ in ppm; 400 MHz) 11.09 (C-18, CH3); 20.60, 20.67, 20.82, 21.07 (acetyl, CH3); 22.59, 22.66, 23.69, 24.98, 25.41, 25.68, 26.51, 27.17, 28.95, 29.05, 29.11, 29.19, 29.29, 29.37, 29.70, 31.59, 34.18 (alkyl, CH2) 42.83, ( ); 51.56 (OMe, CH3); 54.61, 57.00 (α and β CH-N); 61.34 (C-6', CH^, 66.19, 67.13 (α and β C-4'); 67.57, 68.16
(α and β C-2'); 68.19, 68.84 (α and β C-3'); 70.65, 71.01 (α and β C-5'); 97.21, 102.08 ( and β C-1*); 169.54, 170.21, 170.29, 170.47 (acetyl, C=O); 174.60 (C-1, C=O). IR (cm-1): 2935 (s,w): 2855 (s,w); 1783 (s,w); 1517 (s); 1455 (s).
Example 11: Methyl 12-galactosylaminostearate The product of the previous example is deacetylated with sodium methoxide in methanol with reflux for 4 h. IR (cm-1): 3365 (w); 2936 (s); 2359 (s); 2337 (s); 1651 (s); 1447 (s,w); 1354 (s).
Examples 12-15: 1 -0-(ll -Methoxycarbonyl-1 -hexylundecyl) -β-D-glucose,
-galactose, -lactose and -maltose
1, 2, 3, 4, 6-Penta - O -acetyl -β -D -glucopyranose
In a porcelain mortar 4 g (48 mmol) of anhydrous sodium acetate and 5 g (27.4 mmol) dry α-D-glucose are milled, the powder mixture is transferred to a round-bottomed flask of 200 ml and 7 g (25 ml, 0.26 mol) of acetic anhydride is added. The mixture is refluxed (120°C) and occasionally shaken until a clear solution is obtained. After another two hours of heating the reaction mixture is poured onto 250 ml of ice. Na 1 The crystals are filtered off after 1 h, washed with cold water and recrystallised from ethanol. Yield 6.2 g (56%). Galactose, lactose and maltose are acetylated in the same way yields of 57%, 76%, and 74%, respectively. 2, 3,4,6- Tetra - O -acetyl -a-D-glucopyranosyl bromide
To a solution of 1,2,3,4,6-penta-O-acetyl-β-D-glucopyranose (3.90 g, 10 mmol) in dichloromethane (9 ml), 33% HBr in glacial acetic acid (9 ml) is added at 0°C. The mixture is stirred until thin layer chromatography (ethyl acetate/dichloromethane: 1/1;
Rf= 0.56) shows that the bromination is completed (Rf= 0.57). The mixture is poured onto ice, taken up in dichloromethane (50 ml), washed with water (50 ml), saturated NaHCO3 solution (50 ml) and again with water (2x 50 ml). The organic phase is dried on MgSO , filtered concentrated. The residue (oil) is dissolved in ether and stored at 4°C. Crystals appear after several hours; yield 3.83 g (93%). The same method is followed for the bromination of galactose, lactose and maltose (yields 93%, 93%, and 95%, respectively).
2,3,4,6-Tetra-O -acetyl- l-O- (11 -methoxycarbonyl-1 -hexylundecyl) -β-D-glucose Method 1: To a mixture of 0.628 g (2 mmol) methyl 12(R)-hydroxyoctadecanoate, 0.72 g (2 mmol) HgBr2 and 6 g molecular sieves' (4A), 0.1 g KI in 24 ml dry dichloromethane is added. The reaction mixture is stirred at room temperature for 1 h. Finally, 0.82 g (2 mmol) of 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl bromide is added. After overnight stirring at 0°C, the mixture is extracted with 150 ml of dichloromethane, and the organic layer is washed twice with 40 ml of an aqueous 5% (w/v) KI solution, then with saturated NaHCO3 (25 ml) and finally twice with water (40 ml). The organic phase is dried on MgSO4, filtered, and evaporated. The residue is purified with column chromatography (Rf = 0.33; ethyl acetate/hexane: 35/65). Yield 0.45 g (35%). The corresponding galactose, lactose and maltose derivatives are prepared in a similar manner; yields 15%-40%.
Method 2: To a mixture of 0.628 g (2 mmol) methyl 12-hydroxy-octadecanoate (in 50 ml acetonitrile) and 6 g molecular sieves (4A), 0.404 g (4 mmol) Et3N is added. The reaction mixture is stirred at room temperature for 1 h. Then 0.82 g (2 mmol) of 2,3,4,6- tetra-O-acetyl-α-D-glucopyranosyl bromide is added and the mixture is refluxed for 24 h. When the mixture does no longer show any reaction, (check with TLC; ethyl acetate/hexane: 35/65; Rf value 0,33), the molecular sieves are filtered off and the filtrate is then concentrated. The residue (oil) is dissolved in ether, the mixture is filtered and the organic phase is purified by column chromatography (Rf = 0.33; ethyl acetate/hexane: 35/65). Yield 0.54 g (42%). The corresponding galactose, lactose and maltose derivatives are prepared following the same method; yields 41-51%. The 1H NMR, 13C NMR and
IR data of these compounds confirm their structure. 1 -0-(ll -Methoxycarbonyl-1 -hexylundecyl) -β-D-glucose
In a 100 ml flask 0.45 g of the acetylated product described above is refluxed in 30 ml of a mixture of methanol and dichloromethane (60/40, v/v). After 10 minutes 1 g of sodium (5 times 0.2 g) is added in a period of 10 minutes. After standing at 82°C for another 15 h the crystals formed were filtered off, washed twice with dichloromethane (30 ml), dissolved in 20 ml of water and washed with dichloromethane (30 ml). 60 ml of methanol was added to the water phase and then the product crystallises. Yield 0.27 g (94%). The corresponding galactose, lactose and maltose derivatives are prepared by the same method; yields 93-97%. The IR data are presented in table 1. The CMC values and surface tensions are presented in table 2.
Examples 16-19: 1 -O- (8 -Methoxycarbonyl-1 -nonylundecyl)-β-D-glucose, -galactose, -lactose and -maltose
These compounds are prepared following the methods of examples 1-4, however starting with methyl 9-hydroxyoctadecanoate in stead of methyl 12-hydroxyoctadecanoate. The
1H NMR, 13C NMR and IR data of the peracetyl compounds confirm their structure. The IR data of the deacetylated compounds are summarised in table 1 and the CMC values and surface tensions are given in table 2.
Example 20: Methyl 12-maltosylstearate Methyl 12-(peracetylmaltosyl)stearate is dissolved in a small amount of methanol. After addition of sodium, the solution is refluxed for 4 hours. The product precipitates and is filtered. Yield: 80.7%.
IR methyl 12-(peracetylmaltosyl)stearate: 3582-2524 (NH); 2926; 1728,5 (C=O); 1612;
1237; 1040 cm -1.
IR methyl 12-maltosylstearate: 3309 (OH); 2925; 2853; 1604; 1444; 1315; 1049 cm -l
TABLE 1 FT-IR data for the compounds of examples 12-19
Sugar side chain IR (cm-1) residue position glucosyl 12- 3641-3030 (OH); 2788; 2700 1080 galactosyl 12- 3683-3095 (OH); 2801; 2701 1102 lactosyl 12- 3680-3080 (OH); 2802; 2713 1132 maltosyl 12- 3640-3085 (OH); 2803; 2715 1141 glucosyl 9- 3651-3072 (OH); 2809; 2708 1081 galactosyl 9- 3672-3042 (OH); 2819; 2712 1041 lactosyl 9- 3700-3080 (OH); 2820; 2717 1125 maltosyl 9- 3680-3071 (OH); 2821; 2714
1105
TABLE 2 Critical micelle concentrations (CMC) and surface tensions in Milli-Q water of the compounds of examples 12-19
Compound CMC (mol/1) YCMC (mN/m)
Methyl 12-glucosyl-stearate 3.0 x 10-3 32.8
Methyl 9-glucosyl-stearate 2.8 x 10-3 32.2
Methyl 12-galactosyl-stearate 1.2 x 10-3 34.5
Methyl 9-galactosyl-stearate 8.3 x 10-4 33.6
Methyl 12-lactosyl-stearate 5.2 x 10-3 36.8
Methyl 9-lactosyl-stearate 3.1 x 10-3 36.1
Methyl 12-maltosyl-stearate 6.1 x 10-3 38.1
Methyl 9-maltosyl-stearate 4.8 x 10-3 37.2
Claims
1. A surfactant amine compound having formula 1,
R10R11R12N+_CHR2_A1_R1 j wherein
A1 represents a Cy-C^ alkylene group;
R represents hydroxymethyl, carbamoyl, carboxyl or ( ^^ alkoxy)carbonyl;
R2 represents a C5-C9 alkyl group;
R and R11 each represent hydrogen or a Cj- ^ alkyl group, or R and R together with the nitrogen atom represent a pyrrolidino, piperidino or moφholino group;
R12 represents a CJ-C^Q alkyl, alkenyl, alkynyl, cycloalkyl(alkyl), aralkyl or acyl group, which group may be interrupted by one or more oxygen atoms or imino groups, a Cj-03 alkyl or C2-C3 alkanoyl group substituted by a carboxyl, phospho and/or sulpho group, or a group having the formula Sac-(Z-A )n-;
A represents a C2-C6 alkylene group optionally substituted by hydroxy;
Z represents an oxygen atom or an imino group optionally substituted by a CJ-CJ alkyl, hydroxyalkyl or acyl group; n is an integer of 0-4;
Sac represents a sugar residue; wherein, if R10 represents hydrogen, the nitrogen atom may also be deprotonated.
2. An amine compound according to claim 1, wherein A represents a decamethylene group and R2 represents a hexyl group.
3. An amine compound according to claim 1 or 2, wherein R and/or R represent a methyl group.
4. An amine compound according to any one of claims 1-3, wherein Sac represents a sugar residue having the formula R6OCHR7-CHOR5-CHOR4-CHOR3-CHR8- wherein
R3, R4, R5 and R6 each represent hydrogen, a C1-C7 alkyl, alkenyl, aralkyl or acyl group or a Cj-C8 alkyl or C2-C3 alkanoyl group substituted by a carboxyl, phospho and/or sulpho group;
R represents hydrogen, a carboxyl group or a group CH2OR ; R8 represents hydrogen or together with one of the symbols R5 and R6 forms a direct bond; wherein one of the symbols R3, R4, R5 and R6 may also represent a sugar residue
[R6OCHR7-CHOR5-CHOR4-CHOR3-CHR8-]; and Sac is preferably glucosyl or galactosyl.
5. A process for preparing a surfactant amino compound according to any one of claims 1-5, wherein R may also represent hydrogen, comprising reacting a keto compound having the formula R -CO-A1-R1, wherein A1, R1 and R2 are as defined in claim 1, with hydroxylamine, and hydrogenating the oxime obtained, followed, if desired, by reacting the amine obtained with one or halides having the formulae R10X, RnX and R12X, wherein X represents a halogen atom.
6. A surface active glycoside having formula 2,
R6OCHR7-CHOR5-CHOR4-CHOR3-CHR8-(Z-A2)n-Z-CH(R13R14) 2
wherein
R3, R4, R5 and R6 each represent hydrogen, a C^Cy alkyl, alkenyl, aralkyl or acyl group or a Cy-C^- alkyl or C2-C3 alkanoyl group substituted by a carboxyl, phospho and/or sulpho group; R represents hydrogen, a carboxyl group or a group CH2OR ; R8 represents hydrogen or together with one of the symbols R5 and R6 forms a direct bond; wherein one of the symbols R3, R4, R5 and R6 may also represent a sugar residue
[R6OCHR7-CHOR5-CHOR4-CHOR3-CHR8-]; R13 and R14 each represent a C4-C15 alkyl or alkenyl group optionally substituted by hydroxy, alkoxycarbonyl, amino, (di)alkylamino, carbamoyl or (di)alkylcarbamoyl; A2 represents a C2-C6 alkylene group optionally substituted by hydroxy; Z represents an oxygen atom or an imino group optionally substituted by a Cj-C8 alkyl, hydroxyalkyl or acyl group; n is an integer of 0-4.
7. A glycoside according to claim 6, wherein R represents an C7-C alkyl group substituted by hydroxy or alkoxycarbonyl and R14 represents a C5-C9 alkyl group;
8. A glycoside according to claim 6 or 7, wherein R3, R4, R5 and R6 each represent hydrogen, wherein one of the symbols R4, R and R6 may also represent a glucosyl or galactosyl group, and R8 may also form a direct bond with one the symbols R5 and R6.
9. A glycoside according to claim 8, which is a ╬▓-glucoside or ╬▓-galactoside.
10. A glycoside according to any one of claims 6-9, wherein Z represents an oxygen atom; n equals 0 and
R8 together with one of the symbols R and R forms a direct bond.
11. A process for preparing a glycoside according to any one of claims 6-10, comprising reacting a glycosyl halide having the formula 3,
R6OCHR7-CHOR5-CHOR4-CHOR3-CHR8-X 3 wherein R3, R4, R5 and R each represent hydrogen, a Cj-C7 alkyl, alkenyl, aralkyl or acyl group; R represents hydrogen or a group CH2OR ;
R8, together with one of the symbols R5 and R , forms a direct bond; wherein one of the symbols R3, R4, R5 and R6 may also represent an alkylated or acylated sugar residue, X is a halogen atom, with a secondary alcohol or a amine having formula 4,
HZ-(A2-Z)-CHR13R14 4 wherein
R13 and R14 each represent a C4-C15 alkyl or alkenyl group optionally substituted by alkoxycarbonyl, carbamoyl or (di)alkylcarbamoyl, a secondary carbon atom of which being optionally substituted by hydroxy or amino or (di)alkylamino,
A2, Z and n are as defined in claim 6, in a manner known per se, optionally followed by substituting alkyl and acyl groups of R3 to R6 by hydrogen atoms by reduction or hydrolysis, and optionally reducing an alkoxycarbonyl or carbamoyl group in R .
12. A process for preparing a glycoside according to any one of claims 5-10, comprising reacting a glycosyl halide having formula 3,
R6OCHR7-CHOR5-CHOR4-CHOR3-CHR8-X 3 wherein
R3, R4, R5, R6, R7 and R8 are as defined in claim 6,
X is a halogen atom, wwiitthh aa sseeccoonnddaarryy aallceohol having formula 4, wherein R and R are as defined in claim 6, in the presence of a hindered amine in an aprotic solvent, optionally followed by substituting alkyl and acyl groups of R to R by hydrogen atoms by reduction or hydrolysis, and optionally reducing an alkoxycarbonyl or carbamoyl group in R13.
13. A process according to claim 11 or 12, wherein R3 is an acetyl group.
14. A process according to any one of claims 11-13, wherein Z represents oxygen and n equals 0.
15. A process for preparing a glycoside according to any one of claims 6-10, comprising reacting a glycose having formula 3,
R6OCHR7-CHOR5-CHOR4-CHOR3-CHR8-X 3
wherein
R3, R4, R5, R6, and R7 are as defined in claim 1 R8 and X together form an optionally acetalised oxo group, with an amine having formula 4,
HZ-(A2-Z)n-CHR13R14 4 wherein
R13, R14, A2 and n are as defined in claim 1 and Z represents an imino group, optionally in the presence of a reducing agent.
16. A detergent and/or emulsifying composition containing a surface-active compound according to any one of claims 1-10.
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US10570167B2 (en) | 2016-12-22 | 2020-02-25 | Calithera Biosciences, Inc. | Ectonucleotidase inhibitors and methods of use thereof |
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US10472364B2 (en) | 2016-09-09 | 2019-11-12 | Calithera Biosciences, Inc. | Ectonucleotidase inhibitors and methods of use thereof |
US11208414B2 (en) | 2016-09-09 | 2021-12-28 | Calithera Biosciences, Inc. | Ectonucleotidase inhibitors and methods of use thereof |
US10570167B2 (en) | 2016-12-22 | 2020-02-25 | Calithera Biosciences, Inc. | Ectonucleotidase inhibitors and methods of use thereof |
US11034715B2 (en) | 2016-12-22 | 2021-06-15 | Calithera Biosciences, Inc. | Ectonucleotidase inhibitors and methods of use thereof |
US11078228B2 (en) | 2018-06-21 | 2021-08-03 | Calithera Biosciences, Inc. | Ectonucleotidase inhibitors and methods of use thereof |
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