CN1278243A - 二酯胺加合物 - Google Patents
二酯胺加合物 Download PDFInfo
- Publication number
- CN1278243A CN1278243A CN98810815A CN98810815A CN1278243A CN 1278243 A CN1278243 A CN 1278243A CN 98810815 A CN98810815 A CN 98810815A CN 98810815 A CN98810815 A CN 98810815A CN 1278243 A CN1278243 A CN 1278243A
- Authority
- CN
- China
- Prior art keywords
- formula
- amine adducts
- diester amine
- alkyl
- adducts
- 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.)
- Pending
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- -1 Diester amine Chemical class 0.000 title claims abstract description 43
- 150000001875 compounds Chemical class 0.000 claims abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 239000004753 textile Substances 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 239000000654 additive Substances 0.000 claims abstract description 5
- 238000004061 bleaching Methods 0.000 claims abstract description 4
- 235000013305 food Nutrition 0.000 claims abstract description 4
- 239000000498 cooling water Substances 0.000 claims abstract description 3
- 239000002243 precursor Substances 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 31
- 229910052717 sulfur Inorganic materials 0.000 claims description 26
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 24
- 150000002148 esters Chemical class 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 150000003839 salts Chemical group 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000002657 fibrous material Substances 0.000 claims description 3
- 150000000000 tetracarboxylic acids Chemical class 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 9
- 239000000835 fiber Substances 0.000 abstract description 7
- 229910052742 iron Inorganic materials 0.000 abstract description 6
- 230000003647 oxidation Effects 0.000 abstract description 6
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003599 detergent Substances 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 3
- 239000011777 magnesium Substances 0.000 abstract description 3
- 229910052725 zinc Inorganic materials 0.000 abstract description 3
- 239000011701 zinc Substances 0.000 abstract description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 abstract 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 2
- 150000003863 ammonium salts Chemical class 0.000 abstract 1
- 235000013361 beverage Nutrition 0.000 abstract 1
- 125000004432 carbon atom Chemical group C* 0.000 abstract 1
- 239000012459 cleaning agent Substances 0.000 abstract 1
- 238000003776 cleavage reaction Methods 0.000 abstract 1
- 229910001431 copper ion Inorganic materials 0.000 abstract 1
- 230000002255 enzymatic effect Effects 0.000 abstract 1
- 229910001425 magnesium ion Inorganic materials 0.000 abstract 1
- 230000007017 scission Effects 0.000 abstract 1
- 239000003381 stabilizer Substances 0.000 abstract 1
- VKZRWSNIWNFCIQ-WDSKDSINSA-N (2s)-2-[2-[[(1s)-1,2-dicarboxyethyl]amino]ethylamino]butanedioic acid Chemical compound OC(=O)C[C@@H](C(O)=O)NCCN[C@H](C(O)=O)CC(O)=O VKZRWSNIWNFCIQ-WDSKDSINSA-N 0.000 description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 239000011541 reaction mixture Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000000047 product Substances 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 6
- 239000000123 paper Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 241000894006 Bacteria Species 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 150000005690 diesters Chemical class 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 235000019198 oils Nutrition 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 229920001817 Agar Polymers 0.000 description 4
- 239000008272 agar Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- WOFPPJOZXUTRAU-UHFFFAOYSA-N 2-Ethyl-1-hexanol Natural products CCCCC(O)CCC WOFPPJOZXUTRAU-UHFFFAOYSA-N 0.000 description 3
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 241000186245 Corynebacterium xerosis Species 0.000 description 3
- 230000001580 bacterial effect Effects 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 229960004756 ethanol Drugs 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-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
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000001888 Peptone Substances 0.000 description 2
- 108010080698 Peptones Proteins 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229940024606 amino acid Drugs 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- 239000005018 casein Substances 0.000 description 2
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 2
- 235000021240 caseins Nutrition 0.000 description 2
- 239000012230 colorless oil Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 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 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 238000011534 incubation Methods 0.000 description 2
- 230000000968 intestinal effect Effects 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 235000013336 milk Nutrition 0.000 description 2
- 239000008267 milk Substances 0.000 description 2
- 210000004080 milk Anatomy 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 235000019319 peptone Nutrition 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000002453 shampoo Substances 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical class CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- ILPBINAXDRFYPL-UHFFFAOYSA-N 2-octene Chemical compound CCCCCC=CC ILPBINAXDRFYPL-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
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- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
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- CKLJMWTZIZZHCS-UWTATZPHSA-N L-Aspartic acid Natural products OC(=O)[C@H](N)CC(O)=O CKLJMWTZIZZHCS-UWTATZPHSA-N 0.000 description 1
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
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- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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- 125000001204 arachidyl 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])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000002960 margaryl 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])[H] 0.000 description 1
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- 125000001421 myristyl 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])[H] 0.000 description 1
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Abstract
本发明公开了式(1)的二酯胺加合物,其中R1、R2、R3、R4彼此独立地是C4-C22烷基、C2-C22烯基或C5-C7环烷基;X1和X2彼此独立地是氢、C1-C4烷基、C2-C4羟基烷基或C2-C4羟基卤代烷基;Y是式(1b)的基团;A1是C2-C3亚烷基或2-羟基-正-亚丙基;X3是氢、C1-C4烷基、C2-C4羟基烷基或C2-C4羟基卤代烷基;(A)是R或S构型中的不对称碳原子,其中如果C1=R,C2=R;C1=S,C2=S;和C1=R,C2=S;m1是1或 2;和n是1-4的整数;P是0或1;该加合物可以是游离碱或铵盐的形式。所述化合物是具有良好配合物形成性质的化合物的前体,因而能够有效结合重金属离子,例如铁、锌、镁或铜离子,和防止在酶或化学断裂后金属引起的氧化。它们有许多用途,例如在食品和饮料中、除锈和脱钙浴中、在用于冷却水循环的液体中、在个人护理产品中用作添加剂、在清洁剂和洗涤剂中和纺织工业中用作漂白稳定剂,还用作有机纤维材料用的柔软处理剂。
Description
本发明涉及二酯胺加合物,这些化合物的制备方法和它们的用途。
本发明的二酯胺加合物具有下式:其中R1、R2、R3、R4彼此独立地是C4-C22烷基、C2-C22烯基或C5-C7环烷基;X1和X2彼此独立地是氢、C1-C4烷基、C2-C4羟基烷基或C2-C4羟基卤代烷基;Y是式(1b)的基团A1是C2-C3亚烷基或2-羟基-正-亚丙基;X3是氢、C1-C4烷基、C2-C4羟基烷基或C2-C4羟基卤代烷基;是R或S构型中的不对称碳原子,其中如果C1=R,C2=R;C1=S,C2=S;和C1=R,C2=S;m1是1或2;和n是1-4的整数;p是0或1;该加合物可以是游离碱、酸、酸式盐或季铵盐形式。
二酯胺加合物是(SS)、(RR)或(RS)构型的立体化学均匀化合物,即可由下式表示的化合物:
C1-C22烷基是直链或支链烷基,例如甲基、乙基、正丙基、异丙基、正丁基、仲丁基、叔丁基、戊基、异戊基或叔戊基、庚基、辛基、异辛基、壬基、癸基、十一烷基、十二烷基、十四烷基、十五烷基、十六烷基、十七烷基或十八烷基或二十烷基。
C2-C22烯基是例如烯丙基、甲代烯丙基、异丙烯基、2-丁烯基、3-丁烯基、异丁烯基、正戊-2,4-二烯基、3-甲基-丁-2-烯基、正辛-2-烯基、正十二碳-2-烯基、异十二碳烯基、正十二碳-2-烯基或正十八碳-4-烯基。
C5-C7环烷基通常是环戊基、环庚基或优选环己基。
C2-C4羟基烷基是例如2-羟基乙基或4-羟基-正丁基。
C2-C4羟基卤代烷基通常是1-氯-2-羟基乙基。
式(1)的优选二酯胺加合物是如下化合物,其中A1是C2-C3亚烷基;m是2;和p是0。
式(1)的尤其优选的二酯胺加合物是如下化合物,其中X1和X2是氢和非常尤其优选如下化合物,其中R1、R2、R3和R4是C4-C22烷基。
对于C1和C2原子是立体化学均匀的新二酯胺加合物(参见式(1))由本身已知的方法通过使下式的氨基二羧酸:与过量的相关醇在气态HCl或亚硫酰氯作用下在一步反应中反应制备。该方法尤其在CA 62,11911g(1965)中公开。相应的二酯胺加合物可通过使生成的下式的氨基二羧酸酯:与下式的二卤素化合物:
(1f)Hal-(A1)m-1Hal
反应转化为式(1)的相应二酯胺加合物。
亚硫酰氯通常在-70-80℃,优选-10-30℃的温度范围中滴加。在反应的另一过程中,温度上升最高到200℃,优选的温度范围是40-80℃。
亚硫酰氯通常过量使用。原则上亚硫酰氯还可用气态氯化氢代替。
在反应完成后,如果需要,以结晶化合物的形式分离出四酯的盐酸盐,随后重结晶。
反应使用醇组分作为溶剂(高度过量)。
起始化合物可以是含水四羧酸,例如含水量约20%的EDDS。
氨基二羧酸的单酯可用通常已知的方法通过使羧酸与相应的醇反应高收率地获得。
式(1a)、(1b)和(1c)化合物的混合物通过首先用醇酯化马来酸酐成相应的二酯,随后使2摩尔各自的二酯与二胺反应得到。
对于许多应用,还可以用式(1a)、(1b)和(1c)的立体异构体的混合物代替立体化学均匀产物,所述混合物也以上述方法得到。
式(1)的立体化学均匀化合物和下式的二酯胺加合物:是具有明显配合物形成性质的化合物的前体。在生理条件下,酯基团可通过酯酶断裂。在OH-或H+离子存在下在含水介质中进行化学水解。得到其中R1=R2=R3=R4=H的化合物,例如N,N’-乙二胺二琥珀酸(EDDS)。该化合物因而能够有效结合重金属离子,例如铁、锌、镁或铜离子,并防止金属引发的氧化。
与游离酸或酸的盐(R1=R2=R3=R4=H)相反,式(1)化合物易溶于有机溶剂、脂肪和油中,因此获得了新的应用领域。所述化合物因此适合用作易受氧化和易于变质或变腐败的食品和饮料的添加剂。易于氧化的食品尤其是含有烯属双键的化合物或组合物。
由于其配合物形成性质,新二酯胺加合物还可用于除去不需要的钙沉积、锅垢和铁锈。它们通常在碱性除锈和脱钙浴中用于该用途。
此外,新化合物用作冷却水循环中的液体中的添加剂以防止和溶解钙沉积。
新加合物还用于个人护理产品,例如乳膏、洗液、身体护理产品,例如除臭剂、皂或洗发剂和软膏,以防止氧化、腐败、混浊等。
它尤其可以在头发上获得柔软处理效果。
此外,新二酯胺加合物在洗涤剂中或纺织品或纸漂白中用作例如过硼酸钠的漂白稳定剂。在洗涤剂配方中,在水和纺织品和纸材料中存在痕量重金属,例如铁、铜或镁,它们催化过硼酸钠以及洗涤剂中存在的其它漂白剂降解。新化合物结合这些金属离子,防止在相应的洗涤剂贮存以及洗涤液中漂白体系的不合适的降解。因此改善了漂白体系的有效性,防止了纤维损坏。此外,其它敏感的洗涤剂组分,例如酶、荧光增白剂和香料被有利地保护避免氧化降解。
新加合物还可用于清洁剂和洗涤剂中以除去金属离子和用作防腐剂。在液体清洁配方中,新化合物可以基于配方的总重量按重量计0.05-15%的浓度有利地使用。
新二酯胺加合物还可有利地用于纺织工业以除去在生产和在染色天然和合成纤维过程中的痕量重金属。它们避免了在纺织材料上的成斑和成条纹染色、差的润湿能力和不均匀染色。
新的式(1)二酯胺加合物还非常适合用作有机纤维材料,例如纸或,尤其是纺织纤维材料的柔软处理剂。在疏松纤维、纱线,尤其在天然纤维素,例如棉花或聚丙烯腈的机织或针织品的情况下获得了尤其良好的柔软处理效果。这些加合物还可用于柔软处理合成聚酰胺或再生纤维素的纤维材料。在0.1-1%,优选0.2-0.6%的纤维涂层中已获得了良好的柔软处理效果。
纤维的处理通过优选用含水制剂,例如用这些加合物的水溶液或乳状液处理纤维材料、将加合物施用于纤维随后干燥进行。这方便地使用基于要整理的纤维材料重量的0.5-5%,优选1-3%的约20%乳状液或溶液。含水制剂还可通过工业中通常使用的浸渍法施用于纤维(例如轧染法或耗尽法)。在有机溶剂中的溶液通常经喷洒使用。
同样它可通过喷洒或浸渍过程用新加合物处理纸幅。也获得了很好和柔顺的柔软处理。
式(1)的新二酯胺加合物还可用作纺织品,尤其是聚酯织物的抗静电剂。
在造纸工业中,新化合物可用于除去重金属/铁离子。铁在纸上的沉积在纤维素的氧化、催化降解开始时导致形成所谓的热斑。
新二酯胺加合物还适合用作有机合成的催化剂,例如用于链烷烃的空气氧化或加氢甲酰基化烯烃形成醇。
新二酯胺加合物可以任何所需的形式使用,例如粉末、颗粒、浆状、液体制剂、片、胶囊、丸剂、悬浮液或凝胶。
如果新加合物用作例如身体护理产品,则基于组合物的总重量该产品含有按重量计0.01-15,优选0.5-10%的式(1)或(2)的二酯胺加合物和化妆品相容的助剂。
根据现存身体护理产品的形式,除二酯胺加合物外,它还含有其它组分,例如螯合剂、着色剂、芳香油、增稠剂或稠度调节剂、润肤剂、UV吸收剂、皮肤保护剂、抗氧化剂、改善机械性能的添加剂,例如二羧酸和/或C14-C22脂肪酸的铝、锌、钙、镁盐。
由于其在油和醇中的良好溶解性,新二酯胺加合物可加入相应配方中,无任何困难。
例如皂具有如下组成:
按重量计0.01-5%式(1)或(2)化合物,
按重量计0.3-1%二氧化钛,
按重量计1-10%硬脂酸,
和100%皂基,例如动物油脂肪酸和椰子油脂肪酸或甘油的钠盐。
例如洗发剂具有如下组成:
按重量计0.01-5%式(1)或(2)化合物,
按重量计12.0%月桂基醚-2-硫酸钠,
按重量计4.0%椰油酰氨基丙基甜菜碱,
按重量计3.0%氯化钠,和
至100%的水。
例如除臭剂具有如下组成:
按重量计0.01-5%式(1)或(2)化合物,
按重量计60%乙醇,
按重量计0.3%芳香油,和
至100%的水。
如下非限制性实施例更详细地说明本发明。使用的SS-DDS具有约20%的含水量。实施例1:[S,S]-乙二胺二琥珀酸四乙酯
将乙醇(300g,6.5mol)和[S,S]-乙二胺二琥珀酸(21.92g,0.075mol)放置在容器中,在-5-5℃滴加亚硫酰氯(53.0g,0.45mol)。将反应混合物缓慢加热至室温,在室温下搅拌24小时。随后再加热12小时至60℃。悬浮液首先转化为溶液,在一定时间后,以白色结晶的形式分离四酯的盐酸盐。悬浮液用l00ml乙醇稀释,在60℃下在旋转蒸发器中浓缩。
将白色残余物悬浮在100g冰/氨溶液(25%)的1∶1混合物中。水相用甲基叔丁基醚(300ml)提取两次。合并有机相,随后用水洗涤至中性,用硫酸钠干燥。真空(60℃)除去溶剂,得到式(101)的轻微污染的四酯,为无色液体形式。
混合物可用柱色谱法(硅胶G60,乙酸乙酯/石油醚[40/60]8∶2)纯化。
收率:20.4g,理论值的67%
1H NMR(200MHz,CDCl3,TMS):δ=1.15-1.25(m,CH3,6H),2.0(s,NH,1H),2.52-2.85(m,
NCCH2COO and CH2N,4H),3.6(t,NCH,1H),4.07-4.25-(m,CH2CH3,4H).
13C NMR(200MHz,CDCl3,TMS):δ=14.48(CH3),14.54(CH3),38.42(CH2),47.52(CH2)。
将[S,S]-EDDS-四乙酯(1.00g,0.00247mol)悬浮在50ml水中,恒温至95℃。使用pH控制器,保持pH恒定在9.5-10(1N-NaOH)。在24小时后,另加入50ml水,在80℃下在旋转蒸发器中混合物被浓缩至约40ml。残余物转移到50ml容量瓶中,用水填充至校准标记,调节至pH=9.5。水解物的旋光摩尔比量是[α]20 D=-14.5。
由L-天冬氨酸和二溴乙烷制备的[S,S]-EDDS-三钠盐溶液的旋光比量是[α]20 D=-15.9(pH=9.5)。
在pH=9.5-10恒温至95℃24小时后[S,S]-EDDS-三钠盐溶液的旋光比量是[α]20 D=-13.8(pH=9.5)。
这些测量结果显示在EDDS结构中不对称碳原子的构型通过上述酯化过程几乎不改变。实施例3:[S,S]-/[R,R]-/[R,S]-乙二胺二琥珀酸四异辛基酯(异构体混合物)
混合马来酸酐(10.1g)、2-乙基-1-己醇(28.7g)和2,6-二(叔丁基)-对-甲酚(0.1g),加热至90℃。2小时后,加入50ml苯和0.6g浓硫酸。通入氮气,共沸蒸馏出苯和水。冷却后,在混合物中加入2.6g粉末碳酸钠,搅拌30分钟。通过过滤除去反应混合物的未溶解组分,在真空下在旋转蒸发器中浓缩滤液,得到38g式(103)的粗二酯。在高真空下蒸馏以理论值90%的收率得到下式的二酯:
元素分析: %C %H
计算值: 70.55 10.66
实验值: 70.7 10.9
在式(103)的二酯(27.24g,0.08mol)中加入l00ml甲苯后,在20-25℃下滴加乙二胺(2.4g,0.04mol,溶解在5ml甲苯中),加热混合物4小时至80℃。在真空下于旋转蒸发器中除去溶剂。残余物用柱色谱法(硅胶60,甲苯/乙酸乙酯7∶3)纯化。
收率:9.0g,理论值的30%(淡黄色液体)
元素分析: %C %H %N
计算值: 68.07 10.88 3.78
将2-乙基-1-己醇(100g,0.77mol)放置在容器中,在-5-5℃下滴加亚硫酰氯(28.4g,0.24mol)。在反应混合物中分批加入[S,S]-乙二胺二琥珀酸(11.689,0.04mol)。将反应混合物缓慢加热至室温,在室温下搅拌12小时。随后再加热混合物24小时至60℃,然后在室温下搅拌48小时。然后在搅拌下将反应混合物加入冰/氨溶液的混合物中,如实施例1中所述处理。为除去2-乙基-1-己醇,在高真空下浓缩有机相。
这得到了轻微污染的相应于式(104)的四酯,淡黄色油状物(21g,理论值的73%)。
产物可用柱色谱法(硅胶G60,乙酸乙酯/石油醚[40/60]1∶1)纯化。
1H NMR(200MHz,CDCl3,TMS):δ=[0.72-0.90(m),1.11-1.27(m),1.40-1.59(m)
烷基,30H],1.91(s,NH,1H),2.49-2.80(m,NCCH2COO和CH2N,4H),3.57(t,NCH,
1H),3.88-4.10(m,CH2O,4H).
13C NMR(200MHz,CDCl3,TMS):δ=11.29,11.47,14.39,23.33,23.74,24.07,24.10,29.27,
29.51,30.53,30.71,38.48,39.06,39.09,47.67,57.83(CH),67.53(CH2),67.72(CH2),
171.40(Cq),174.08(Cq)[S,S]-构型实施例5:[S,S]-乙二胺二琥珀酸四异丙基酯
将异丙醇(150.0g,2.5mol)放置在容器中,在-5-5℃下滴加亚硫酰氯(14.3g,0.12mol)。在反应混合物中分批加入[S,S]-乙二胺二琥珀酸(5.84g,0.02mol)。将反应混合物缓慢加热至室温,随后加热24小时至60℃。在冷却后形成式(105)的四酯盐酸盐的结晶,然后通过过滤收集,用50ml甲基叔丁基醚洗涤。
在将滤饼在冰/氨溶液的混合物中搅拌后,如实施例1中所述处理。在真空下(60℃)除去溶剂得到轻微污染的四酯,为淡黄色油状物形式(收率:1.71g,理论值的19%)。
产物可用柱色谱法(硅胶G60,乙酸乙酯/石油醚[40/60]/乙醇9∶1∶0.5)纯化。
1H NMR(200MHz,CDCl3,TMS):δ=1.15-1.38(m,CH3,12H),1.99(s,NH,1H),2.54-2.85
NCCH2COO和CH2N,4H),3.58(C,NCH,1H),4.93-5.12(m,OCH,2H).
13C NMR(200MHz,CDCl3,TMS):δ=22.11(CH3),22.15(CH3),22.21(CH3),38.72(CH2),
将正丁醇(200g,2.7mol)放置在容器中,在-5-5℃下滴加亚硫酰氯(14.3g,0.12mol)。在反应混合物中分批加入[S,S]-乙二胺二琥珀酸(5.84g,0.02mol)。将反应混合物缓慢加热至室温,随后再加热48小时至60℃。悬浮液首先转化为溶液,在一定时间后,分离出四酯的盐酸盐,为白色结晶形式。将混合物冷却至室温,在加入50ml甲基叔丁基醚后,过滤。滤饼用50ml甲基叔丁基醚洗涤,通过抽吸简单干燥。
将滤饼在冰/氨溶液中搅拌后,如实施例1中所述处理,得到式(106)的四酯,为淡黄色液体形式。收率:5.0g(理论值的48.45%)。1H NMR(200MHz,CDCl3,TMS):δ=0.80-0.95(m,CH3,6H),1.22-1.41(m,烷基-CH2,4H),1.48-1.65(m,烷基-CH2,4H),1.94(s,NH,1H),2.59-2.81(m,NCCH2COO和CH2N,4H),3.57(t,NH,1H),3.98-4.16(m,OCH2).13C NMR(200MHz,CDCl3,TMS):δ=13.99(CH3),19.42(CH2),19.61(CH2),30.94(CH2),30.95(CH2),38.44(CH2),47.56(CH2),57.79(CH),64.88(CH2),65.17(CH2),171.26(Cq).173.94(Cq).[S,S]-构型实施例7:[S,S]-乙二胺二琥珀酸四(2-丁基)酯
将2-丁醇(200g,2.7mol)放置在容器中,在-5-5℃下滴加亚硫酰氯(14.3g,0.12mol)。在反应混合物中分批加入[S,S]-乙二胺二琥珀酸(5.84g,0.02mol)。将反应混合物缓慢加热至室温,随后再加热48小时至60℃。混合物随后加热至80℃,在该温度下保持16小时。将透明,无色溶液冷却至2℃,分离出四酯的盐酸盐,为白色结晶形式。混合物在5℃下过滤,产物用50ml甲基叔丁基醚洗涤。
将滤饼在冰/氨溶液中搅拌后,如实施例1所述处理。得到式(107)的四酯,为淡黄色油状物形式,(收率:0.9g,理论值的9%),产物可用柱色谱法(硅胶G60,乙酸乙酯/石油醚[40/60]8∶2)纯化得到无色油状物。
1H NMR(200MHz,CDCl3,TMS):δ=0.88-0.98(m,CH2Cl3,6H),1.10-1.28(m,CHCH3,6H),,1.42-1.68(m,CH2CH3,4H),1.98(s,NH,1H),2.52-2.88(m,NCCH2COO和CH2N,4H),3.60(t,NCH,1H),4.78-4.96(m,CH2N,2H).
13C NMR(200MHz,CDCl3,TMS):δ=10.46(CH3),10.51(CH3),20.17(CH3),20.28(CH3),29.54(CH2),29.56(CH2),39.18(CH2),48.1(CH2),58.53(CH),73.39(CH),73.88(CH),171.30(Cq)174.01(Cq).[S,S]-构型实施例8:[S,S]-乙二胺二琥珀酸四(异丁基)酯
将异丁醇(200g,2.7mol)放置在容器中,在-5-5℃下滴加亚硫酰氯(14.3g,0.12mol)。在反应混合物中分批加入[S,S]-乙二胺二琥珀酸(5.84g,0.02mol)。将反应混合物缓慢加热至室温,随后再加热41小时至60℃。悬浮液首先转化为溶液,在一定时间后,分离出四酯的盐酸盐,为白色结晶形式。将混合物冷却至室温,过滤,滤饼用50ml甲基叔丁基醚洗涤。
将滤饼在冰/氨水溶液中搅拌后,如实施例1中所述处理混合物。得到式(108)的四酯,为淡黄色油状物形式,(收率:6.8g,理论值的66%),产物可用柱色谱法(硅胶G-60,乙酸乙酯/石油醚[40/60]8∶2)纯化得到无色油状物。
1H NMR(200MHz,CDCl3,TMS):δ=0.84-1.01(m,CH3,12H),1.84-2.08(m,NH和
CH3CH,3H),2.55-2.88(m,NCCH2COO和CH2N,4H),3.65(t,NCH,1H),3.84-3.96(m,
OCH2,4H).
13C NMR(200MHz,CDCl3,TMS):δ=18.39(CH3),26.99,27.03,37.43(CH2),46.61(CH2),
56.80(CH),70.15(CH2),70.41(CH2),170.24(Cq),172.92(Cq)[S,S]-构型实施例9:微生物试验培养基:酪蛋白大豆粉胨琼脂(Merck)酪蛋白大豆粉胨肉汤(Merck)试验用细菌:金黄色葡萄球菌ATCC 9144干燥棒状杆菌ATCC 373大肠杆菌NCTC 8196细菌悬浮液的制备:
将试验细菌在37℃在Caso-Broth(5ml试管)中培养过夜(约18小时)。采用螺旋计数(spiralometer)方法测定培养过夜的细菌数,细菌数必须在108-109KBE/ml之间。
用0.85%氯化钠溶液,pH7.2稀释培养物至约107KBE/ml。基层:
在陪替氏培养皿中加入约18ml无菌营养琼脂,使其固化。顶层:
将3.5ml在0.85%氯化钠中的细菌稀释液用移液管加入在水浴中冷却至47℃的500ml静止液体琼脂中,使其均匀。
将6ml细菌感染的琼脂均匀分布在固化的基层上。干燥后,在4℃贮存约24小时,将培养皿备用于试验。液滴数量:
将100微升式(104)四酯在无水乙醇中的1%溶液用移液管加入培养皿中心,在室温下干燥约30分钟(物质达到约20-30mm的区域)。琼脂扩散试验结果:
琼脂培养皿在37℃培养48小时后,估计液滴区域中试验物质的生长。
试验样品 | 金黄色葡萄球菌ATCC 9144 | 干燥棒状杆菌ATCC373 | 大肠杆菌NCTC8196 |
无水乙醇(对照) | 无抑制 | 无抑制 | 无抑制 |
[S,S]-乙二胺二琥珀酸四(异辛基)酯,1%乙醇溶液 | 无抑制 | 抑制 | 无抑制 |
乙二胺二琥珀酸四(异辛基)酯(异构体混合物),1.0%乙醇溶液 | 无抑制 | 抑制 | 无抑制 |
发现对干燥棒状杆菌ATCC 373的选择性抑制。
Claims (11)
2.根据权利要求1的二酯胺加合物,其中在式(1)中
A1是C2-C3亚烷基;
m是2;和
p是0。
3.根据权利要求1或2的二酯胺加合物,其中X1和X2是氢。
4.根据权利要求1-3的任何一项的二酯胺加合物,其中R1、R2、R3和R4是C4-C22烷基。
7. 根据权利要求6的用途,其包括在食品和饮料中、在除锈和脱钙浴中使用式(2)化合物,在用于冷却水循环的液体中、在个人护理产品中用作添加剂、在清洁剂和洗涤剂中和在纺织和造纸工业中用作漂白稳定剂。
8.根据权利要求6的用途,其包括在体用护理产品中使用式(2)化合物。
9. 根据权利要求8的用途,其包括在除臭剂中使用式(2)化合物。
10.一种体用护理产品,其含有按重量计0.01-15%的式(1)或(2)的二酯胺加合物。
11.式(1)的二酯胺加合物作为有机纤维材料的柔软处理剂的用途。
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Publication number | Publication date |
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US6369268B1 (en) | 2002-04-09 |
NZ504290A (en) | 2002-08-28 |
WO1999024392A1 (en) | 1999-05-20 |
RU2189972C2 (ru) | 2002-09-27 |
IL135545A0 (en) | 2001-05-20 |
AU751838B2 (en) | 2002-08-29 |
KR20010031809A (ko) | 2001-04-16 |
BR9813987A (pt) | 2000-09-26 |
PL340309A1 (en) | 2001-01-29 |
AU2047899A (en) | 1999-05-31 |
EP1028939A1 (en) | 2000-08-23 |
JP2001522827A (ja) | 2001-11-20 |
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