CN102131763B - 不饱和α,ω-二羧酸和/或不饱和α,ω-二羧酸二酯的制备方法 - Google Patents
不饱和α,ω-二羧酸和/或不饱和α,ω-二羧酸二酯的制备方法 Download PDFInfo
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- CN102131763B CN102131763B CN200980132264.XA CN200980132264A CN102131763B CN 102131763 B CN102131763 B CN 102131763B CN 200980132264 A CN200980132264 A CN 200980132264A CN 102131763 B CN102131763 B CN 102131763B
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- unsaturated
- omega
- acid
- carboxylic acid
- dicarboxylic acid
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- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- -1 dicarboxylic acid diesters Chemical class 0.000 title claims description 24
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- 238000000034 method Methods 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 150000001735 carboxylic acids Chemical class 0.000 claims description 32
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- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 4
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 2
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- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 2
- 230000006750 UV protection Effects 0.000 claims 1
- 235000003642 hunger Nutrition 0.000 claims 1
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- 239000000047 product Substances 0.000 description 5
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- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 4
- 229960004488 linolenic acid Drugs 0.000 description 4
- 150000004702 methyl esters Chemical class 0.000 description 4
- 230000003711 photoprotective effect Effects 0.000 description 4
- BITHHVVYSMSWAG-KTKRTIGZSA-N (11Z)-icos-11-enoic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCC(O)=O BITHHVVYSMSWAG-KTKRTIGZSA-N 0.000 description 3
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
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- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 3
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- 125000004417 unsaturated alkyl group Chemical group 0.000 description 3
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- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 2
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- SECPZKHBENQXJG-FPLPWBNLSA-N palmitoleic acid Chemical compound CCCCCC\C=C/CCCCCCCC(O)=O SECPZKHBENQXJG-FPLPWBNLSA-N 0.000 description 2
- CNVZJPUDSLNTQU-SEYXRHQNSA-N petroselinic acid Chemical compound CCCCCCCCCCC\C=C/CCCCC(O)=O CNVZJPUDSLNTQU-SEYXRHQNSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
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- 239000002600 sunflower oil Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GWHCXVQVJPWHRF-KTKRTIGZSA-N (15Z)-tetracosenoic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCCCC(O)=O GWHCXVQVJPWHRF-KTKRTIGZSA-N 0.000 description 1
- CUXYLFPMQMFGPL-UHFFFAOYSA-N (9Z,11E,13E)-9,11,13-Octadecatrienoic acid Natural products CCCCC=CC=CC=CCCCCCCCC(O)=O CUXYLFPMQMFGPL-UHFFFAOYSA-N 0.000 description 1
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- YWWVWXASSLXJHU-UHFFFAOYSA-N 9E-tetradecenoic acid Natural products CCCCC=CCCCCCCCC(O)=O YWWVWXASSLXJHU-UHFFFAOYSA-N 0.000 description 1
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 201000009030 Carcinoma Diseases 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
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- 235000021322 Vaccenic acid Nutrition 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- JAZBEHYOTPTENJ-JLNKQSITSA-N all-cis-5,8,11,14,17-icosapentaenoic acid Chemical compound CC\C=C/C\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O JAZBEHYOTPTENJ-JLNKQSITSA-N 0.000 description 1
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- 235000021342 arachidonic acid Nutrition 0.000 description 1
- 229940114079 arachidonic acid Drugs 0.000 description 1
- PNPBGYBHLCEVMK-UHFFFAOYSA-N benzylidene(dichloro)ruthenium;tricyclohexylphosphanium Chemical compound Cl[Ru](Cl)=CC1=CC=CC=C1.C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1.C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1 PNPBGYBHLCEVMK-UHFFFAOYSA-N 0.000 description 1
- FCDPQMAOJARMTG-UHFFFAOYSA-M benzylidene-[1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene]-dichlororuthenium;tricyclohexylphosphanium Chemical compound C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1.CC1=CC(C)=CC(C)=C1N(CCN1C=2C(=CC(C)=CC=2C)C)C1=[Ru](Cl)(Cl)=CC1=CC=CC=C1 FCDPQMAOJARMTG-UHFFFAOYSA-M 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- KJDZDTDNIULJBE-QXMHVHEDSA-N cetoleic acid Chemical compound CCCCCCCCCC\C=C/CCCCCCCCCC(O)=O KJDZDTDNIULJBE-QXMHVHEDSA-N 0.000 description 1
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- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
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- 238000000605 extraction Methods 0.000 description 1
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- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
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- 235000020778 linoleic acid Nutrition 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
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- 201000001441 melanoma Diseases 0.000 description 1
- 150000002759 monoacylglycerols Chemical class 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000036312 photoerythema Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- RWUZSCCQJHYWDK-UHFFFAOYSA-N ruthenium(2+);tricyclohexylphosphane Chemical compound [Ru+2].C1CCCCC1P(C1CCCCC1)C1CCCCC1 RWUZSCCQJHYWDK-UHFFFAOYSA-N 0.000 description 1
- GHPHCACQRYSXSS-UHFFFAOYSA-N ruthenium;tricyclohexylphosphane Chemical compound [Ru].C1CCCCC1P(C1CCCCC1)C1CCCCC1 GHPHCACQRYSXSS-UHFFFAOYSA-N 0.000 description 1
- 238000005872 self-metathesis reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
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- UWHZIFQPPBDJPM-BQYQJAHWSA-N trans-vaccenic acid Chemical compound CCCCCC\C=C\CCCCCCCCCC(O)=O UWHZIFQPPBDJPM-BQYQJAHWSA-N 0.000 description 1
- CUXYLFPMQMFGPL-UYWAGRGNSA-N trichosanic acid Natural products CCCCC=C/C=C/C=CCCCCCCCC(=O)O CUXYLFPMQMFGPL-UYWAGRGNSA-N 0.000 description 1
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- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/475—Preparation of carboxylic acid esters by splitting of carbon-to-carbon bonds and redistribution, e.g. disproportionation or migration of groups between different molecules
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
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- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/37—Esters of carboxylic acids
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/593—Dicarboxylic acid esters having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/22—Organic complexes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/24—Phosphines
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- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Veterinary Medicine (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
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- Emergency Medicine (AREA)
- Epidemiology (AREA)
- Birds (AREA)
- Dermatology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Cosmetics (AREA)
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Abstract
本发明涉及使用两种钌络合物催化剂制备不饱和α，ω‑二羧酸和/或α，ω‑二羧酸二酯的方法。根据本发明方法得到的不饱和α，ω‑二羧酸和/或α，ω‑二羧酸二酯特别适合用于防晒用化妆品制剂中。
Description
本发明涉及不饱和α，ω-二羧酸以及α，ω-二羧酸二酯的制备方法，该不饱和α，ω-二羧酸以及α，ω-二羧酸二酯具有在UV-区域、特别是UV-B区域中的改善的吸收性。
对于防晒用制剂，一直存在着改进UV吸收性并由此改进对皮肤和毛发的保护的需求。在此，特别重要的是吸收短波高能UV-B辐射(280-320nm)，因为它不仅会导致光照性红斑、晒斑和皮肤坏死，还会引起皮肤癌(黑色素瘤)。然而，传统的UV光防护过滤物质在配制技术方面向本领域技术人员提出了挑战，此外，还已知有皮肤对UV光防护过滤物质的不耐性。
本发明的目的为提供一种在UV-区域、特别是UV-B区域具有改进吸收性的物质，并且这种物质可以代替已知的UV光防护过滤物质使用或者除已知的UV光防护过滤物质之外补充使用。该物质应当可以与常见的化妆品成份一起配制。
此外，还感兴趣的是得到着色尽可能少的物质，这种物质适于结合进入无色或透明化妆品制剂中。
出人意料地发现：使用本发明方法得到的不饱和α，ω-二羧酸以及α，ω-二羧酸二酯在UV-区域、特别是在UV-B区域中吸收增加。因此，根据本发明方法得到的不饱和α，ω-二羧酸和/或α，ω-二羧酸二酯特别适合于防晒用化妆品制剂。
从不饱和羧酸开始制备不饱和α，ω-二羧酸二酯的方法记载于现有技术中：Ngo等人(JAOCS，Vol 83，No.7，第629-634页，2006)描述了借助所谓第一代和第二代Grubbs催化剂以复分解(Metathese)不饱和羧酸。这种使用第一代Grubbs催化剂的方法记载于US 5,750,815中。J.Mol(Topics in Catalysis，Vo.27，Nos.1-4，第97-104页，2004年2月)以及A.Rybak等人(Green Chem.2007，9，1356-1361)也记载了这类方法。
本发明的主题为不饱和α，ω-二羧酸以及α，ω-二羧酸二酯的制备方法，其中不饱和羧酸和/或不饱和羧酸的酯在催化剂(1)和/或(2)的存在下反应
反应物
作为本发明方法的反应物，合适的是具有14至24个碳原子的单或多不饱和羧酸，其任选为支化的。在此，该羧酸的双键可以以顺式或反式构型存在。
适合作为羧酸的为式R1-COOH的化合物，其中R1为具有13至23个碳原子的单或多不饱和烃基(Alkylrest)。作为多不饱和烃基例如可以提及二、三、四、五或六不饱和烃基。
该R1基团可以为环状或无环的，优选的是该基团R1为无环的。该R1基团可以为支化或非支化的。优选的是具有非支化基团R1的羧酸。特别优选的是具有无环状基团R1的羧酸。
使用以下速记方式描述不饱和羧酸：第一个数字描述羧酸中碳原子的总数，第二个数字描述双键的数目，括号中的数字描述双键相对于羧基的位置。因此，油酸的速记方式为18:1(9)。只要双键以反式构型存在，就以缩写“tr”表示。由此，反油酸的速记方式为18:1(tr9)。
合适的单不饱和羧酸有，例如：肉豆蔻脑酸[14:1(9)；(9Z)-十四碳-9-烯酸]，棕榈油酸[16:1(9)；(9Z)-十六碳-9-烯酸]，岩芹酸[(6Z)-十八碳-6-烯酸]，油酸[18:1(9)；(9Z)-十八碳-9-烯酸]，反油酸[18:1(tr9)；(9E)-十八碳-9-烯酸)]，异油酸[18:1(tr11)；(11E)-十八碳-11-烯酸]，鳕油酸[20:1(9)；(9Z)-二十碳-9-烯酸]，二十烯酸(＝巨头鲸鱼酸)[20:1(11)；(11Z)-二十碳-11-烯酸]，鲸蜡烯酸[22:1(11)；(11Z)-二十二碳-11-烯酸]，芥酸[22:1(13)；(13Z)-二十二碳-13-烯酸]，神经酸[24:1(15)；(15Z)-二十四碳-15-烯酸]。
合适的多不饱和羧酸有例如：亚油酸[18:2(9，12)；(9Z，12Z)-十八碳-9，12-二烯酸]，α-亚麻酸[18:3(9，12，15)；(9Z，12Z，15Z)-十八碳-9，12，15-三烯酸]，γ-亚麻酸[18:3(6，9，12)；(6Z，9Z，12Z)-十八碳-6，9，12-三烯酸]，十八碳三稀酸[18:3(8，10，12)；(8E，10E，12Z)-十八碳-8，10，12-三烯酸]，石榴油酸[18:3(9，11，13)；(9Z，11E，13Z)-十八碳-9，11，13-三烯酸]，α-桐酸[18:3(9，11，13)；(9Z，11E，13E)-十八碳-9，11，13-三烯酸]，花生四烯酸[20:4(5，8，11，14)，(5Z，8Z，11Z，14Z)-二十碳-5，8，11，14-四烯酸]，二十碳五烯酸[20:5(5，8，11，14，17)，(5Z，8Z，11Z，14Z，17Z)-二十碳-5，8，11，14，17-五烯酸]，鱼酸[22:5(7，10，13，16，19)，(7Z，10Z，13Z，16Z，19Z)-二十二碳-7，10，13，16，19-五烯酸]，二十二碳六烯酸[22:6(4，7，10，13，16，19)，(4Z，7Z，10Z，13Z，16Z，19Z)-二十二碳-4，7，10，13，16，19-六烯酸]。
合适作为反应物的还有所述单或多不饱和羧酸的酯。适合作为酯的特别是羧酸与醇R2-OH的酯，其中R2为具有1至8个碳原子的烃基(Alkylrest)。作为合适的基团R2例如有：甲基、乙基、丙基、异丙基、丁基、2-甲基丙基、戊基、2，2-二甲基丙基、2-甲基丁基、3-甲基丁基、己基、1-甲基戊基、2-甲基戊基、3-甲基戊基、4-甲基戊基、1-乙基丁基、2-乙基丁基、庚基和辛基。
此外，适合作为反应物的还有所述单或多不饱和羧酸与甘油的酯(＝甘油酯)。在此，合适的有甘油单酯(＝单酸甘油酯，单酰基甘油)、甘油二酯(＝二酸甘油酯，二酰基甘油)和甘油三酯(＝三酸甘油酯，三酰基甘油)，以及这些不同甘油酯的混合物。
不饱和羧酸以及不饱和羧酸的酯可以单独使用，或者以彼此混合的形式使用。如果使用仅一种不饱和羧酸或仅一种不饱和羧酸的酯，那么会发生称 为自身复分解(Selbstmetathese)的反应。如果使用不同不饱和羧酸或不同不饱和羧酸的酯，那么会发生称为交叉复分解(Kreuz-Metathese)的反应。
在本发明一个优选的实施方式中，使用单不饱和羧酸和/或单不饱和羧酸的酯和/或单不饱和羧酸的混合物或单不饱和羧酸的酯的混合物。
催化剂
本发明的方法在催化剂(1)和/或(2)的存在下进行。
催化剂(1)为结构式如下的化合物：
该催化剂的化学名称为二氯-[1，3-二(基)-2-咪唑烷亚基]-(3-苯基-1H-茚-1-亚基)(三环己基膦)钌(II)，CAS号536724-67-1。其可以例如以名称NeolystTM M2(Umicore公司)购买获得。
催化剂(2)为结构式如下的化合物：
该催化剂的化学名称为[1，3-二(2，4，6-三甲基苯基)-2-咪唑烷亚基]-[2-[[(4-甲基苯基)亚氨基]甲基]-4-硝基苯氧基(phenolyl)]-[3-苯基-1H-茚-1-亚基]氯化钌(II)，CAS号934538-04-2。其可以例如以名称NeolystTM M41(Umicore公 司)购买获得。
本发明催化剂的优选使用浓度小于等于1000ppm、特别在10至1000ppm的范围、优选在20至200ppm的范围。
反应条件
本发明方法可以在0至100℃、优选20至90℃、特别为40至80℃的温度进行。
本方法可以在溶解反应物或催化剂的常见的溶剂中进行，这类溶剂例如可以提及：烃或醇。在本发明优选的实施方式中，该方法可以在无溶剂的条件下进行。
纯化
通过本发明方法得到了不饱和α，ω-二羧酸以及不饱和α，ω-二羧酸二酯以及相应的不饱和烃类。物质混合物的分离可以例如以蒸馏方式、通过分步结晶或通过提取进行。
任选地对如此得到的产物进行氢化处理。
应用
出人意料地发现，根据本发明方法制备的不饱和α，ω-二羧酸以及不饱和α，ω-二羧酸二酯适合用于化妆品制剂中。由于其UV-B吸收性，它们特别适合用于防晒用化妆品制剂。
实施例
实施例1a)
50ml的甲酯混合物(包括92.0％油酸甲酯和2.9％亚油酸甲酯，百分比基于未校准的面积百分比气相色谱法)在200ppm催化剂(1)[CAS号536724-67-1]的存在下于50℃反应1.4小时。反应结束后，得到23.1％的二甲基二酯以及20.2％9-十八碳烯。
实施例1b)
重复实施例1a)，除了反应在40℃进行4小时。产率与实施例1a)相同。
实施例1c)
重复实施例1a)，除了反应在30℃进行7小时。产率与实施例1a)相同。
实施例2)
50ml的甲酯混合物(包括92.0％油酸甲酯和2.9％亚油酸甲酯)在200ppm催化剂(2)[CAS号934538-04-2]的存在下于80℃反应8小时。反应结束后，得到23.3％二甲基二酯以及20.6％9-十八碳烯。
实施例3)
在50ml的2颈圆底烧瓶中称量10g高油酸葵花油甲酯(High OleicSonnenblumen-Methylester，含75至93％的油酸甲酯)，并加入0.2g的钌催化剂NeolystTM M2(Umicore公司)[CAS号：536724-67-1](＝催化剂(1))。然后在氮气保护下，将该烧瓶置入培养皿中，该培养皿填充有水并且位于磁力搅拌器的上方，并在35-40℃搅拌60分钟。在冷却至室温后，通过填充有硅胶60的柱滤出催化剂固体。由此得到了红棕色液体。
实施例4)比较例：
在50ml的2颈圆底烧瓶中称量10g高油酸葵花油甲酯(含75至93％的油酸甲酯)，并加入0.2g的钌催化剂二氯(3-甲基-2-亚丁烯基)二(三环己基膦)钌(II)[从Aldrich公司购买得到，目录号576881，CAS号194659-03-5]。然后在氮气保护下，将该烧瓶置入培养皿中，该培养皿填充有水并且位于磁力搅拌器的上方，并在35-40℃搅拌60分钟。在冷却至室温后，通过填充有硅胶60的柱滤出催化剂固体。由此得到了红棕色液体。
UV-吸收：
测量根据实施例3得到的产物以及根据实施例4得到的产物的UV-B吸收。出人意料的是，与根据现有技术制备的产物(实施例4)相比，根据实施例3得到的产物在240至280nm的区域显示更高的吸收。
Claims (13)
1.不饱和α,ω-二羧酸和/或α,ω-二羧酸二酯的制备方法，其中不饱和羧酸和/或不饱和羧酸的酯在催化剂(1)和/或(2)的存在下反应
其中所述催化剂的用量为20至200ppm。
2.根据权利要求1的方法，其特征在于，使用的是不饱和C14至C24羧酸。
3.根据权利要求1的方法，其特征在于，使用的是不饱和羧酸的酯，其中所述不饱和羧酸为C14至C24羧酸。
4.根据权利要求3的方法，其特征在于，作为酯使用的是C1至C8醇与不饱和羧酸的酯。
5.根据权利要求3的方法，其特征在于，作为酯使用的是甘油与不饱和羧酸的酯。
6.根据权利要求5的方法，其特征在于，所述甘油与不饱和羧酸的酯选自甘油单酯、甘油二酯和甘油三酯。
7.根据前述权利要求中任一项的方法，其特征在于，使用单不饱和羧酸。
8.根据权利要求1的方法，其特征在于，所述反应在0至100℃进行。
9.根据权利要求1的方法，其特征在于，所述反应在20至90℃进行。
10.根据权利要求1的方法，其特征在于，所述反应在40至80℃进行。
11.根据前述权利要求1的方法，其特征在于，在无溶剂的条件下进行。
12.根据前述权利要求1的方法，其特征在于，所述不饱和α,ω-二羧酸和/或α,ω-二羧酸二酯以及不饱和烃通过蒸馏进行分离。
13.根据权利要求1至12中任一项的方法得到的不饱和α,ω-二羧酸和/或α,ω-二羧酸二酯的用途，用作紫外光防护过滤物质。
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| WO2012143067A1 (de) | 2011-04-20 | 2012-10-26 | Cognis Ip Management Gmbh | Verfahren zur herstellung ungesättigter verbindungen |
| GB201204715D0 (en) * | 2012-03-18 | 2012-05-02 | Croda Int Plc | Metathesis of olefins using ruthenium-based catalytic complexes |
| BR112014031995A2 (pt) * | 2012-06-26 | 2017-06-27 | Basf Se | processo de preparação de compostos insaturados |
| EP3209486B9 (en) | 2014-10-21 | 2024-08-28 | Stratasys Ltd. | Three-dimensional inkjet printing using ring-opening metathesis polymerization |
| WO2017134672A2 (en) | 2016-02-05 | 2017-08-10 | Stratasys Ltd. | Three-dimensional inkjet printing using polyamide-forming materials |
| WO2017134676A1 (en) | 2016-02-05 | 2017-08-10 | Stratasys Ltd. | Digitally-controlled three-dimensional printing using ring- opening metathesis polymerization |
| WO2017134673A1 (en) | 2016-02-07 | 2017-08-10 | Stratasys Ltd. | Three-dimensional printing combining ring-opening metathesis polymerization and free radical polymerization |
| WO2017187434A1 (en) | 2016-04-26 | 2017-11-02 | Stratasys Ltd. | Three-dimensional inkjet printing using ring-opening metathesis polymerization |
| DE102016010503A1 (de) | 2016-08-30 | 2018-03-01 | Baden-Württemberg Stiftung Ggmbh | Ketten-Vervielfachung ungesättigter Fettsäuren |
| CN110818564A (zh) * | 2019-11-21 | 2020-02-21 | 石河子大学 | 一种利用不饱和脂肪酸酯制备高碳二元酸酯的方法 |
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| CN102131763A (zh) | 2011-07-20 |
| EP2157076A1 (de) | 2010-02-24 |
| WO2010020368A1 (de) | 2010-02-25 |
| EP2313361A1 (de) | 2011-04-27 |
| KR20110044234A (ko) | 2011-04-28 |
| US20110171147A1 (en) | 2011-07-14 |
| JP5653919B2 (ja) | 2015-01-14 |
| BRPI0917520A2 (pt) | 2015-11-17 |
| JP2012500237A (ja) | 2012-01-05 |
| BRPI0917520B1 (pt) | 2016-12-13 |
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