2-乙基己醇,4-二甲氨基苯甲酸乙酯置于titanium(Iv) Oxide Bis(2,4-Pentanedionate)体系中,用 Xylene 用作溶剂,化学反应 30.23H,以98%的收率获得对二甲氨基苯甲酸异辛酯 参考文献:Nucleophilic Acyl Substitutions Of Esters With Protic Nucleophiles Mediated By Amphoteric,Oxotitanium,And Vanadyl Species 标题:Nucleophilic Acyl Substitutions Of Esters With Protic Nucleophiles Mediated By Amphoteric,Oxotitanium,And Vanadyl Species 摘要:[graphics]A Diverse Array Of Oxometallic Species Were Examined As Catalysts In Nucleophilic Acyl Substitution (Nas) Reactions Of Methyl (Or Ethyl) Esters With Protic Nucleophiles. Among Them,Oxotitanium Acetylacetonate (Tio(Acac)(2)) And Vanadyl Chloride (Vocl2-(Thf)(X)) Served As The Most Efficient And Water-Tolerant Catalysts. Transesterifications Of Methyl And/or Ethyl Esters With Functionalized (Including Acid-Or Base-Sensitive) 1Degrees And 2Degrees Alcohols Can Be Carried Out Chemoselectively In Refluxed Toluene Or Xylene In A 1:1 Substrate Stoichiometry Using 1 Mol % Catalyst Loading. The Resultant Products Were Furnished In 85-100% Yields By Simple Aqueous Workup To Remove Water-Soluble Catalysts. The New Nas Protocol Is Also Amenable To Amines And Thiols In 74-91% Yields,Albeit With Higher Loading (2.5 Equiv) Of Protic Nucleophiles. Representative Examples Of Commercial Interests Such As Padimate 0 And Antioxidant Additives For Plastics Were Also Examined To Demonstrate Their Practical Applications. A 1:1 Adduct Between Tio(Acac)2 And A Given 1-octadecanol Was Identified As (C18H37O)(2)Ti(Acac)(2) And Was Responsible For Its Subsequent Nas Of Methyl Esters. Doi:10.1021/jo0484878
专利号:US-5977301-A 优先权日:1992-09-24 标题 :Synthesis of N-substituted oligomers 发明人:ZUCKERMAN RONALD N; KERR JANICE M; KENT STEPHEN B H; MOOS WALTER H; SIMON REYNA J; GOFF DANE A 权利人:CHIRON CORP 摘要:A solid-phase method for the synthesis of N-substituted oligomers, such as poly (N-substituted glycines) (referred to herein as poly NSGs) is used to obtain oligomers, such as poly NSGs of potential therapeutic interest which poly NSGs can have a wide variety of side-chain substituents. Each N-substituted glycine monomer is assembled from two 'sub-monomers' directly on the solid support. Each cycle of monomer addition consists of two steps: (1) acylation of a secondary amine bound to the support with an acylating agent comprising a leaving group capable of nucleophilic displacement by -NH2, such as a haloacetic acid, and (2) introduction of the side-chain by nucleophilic displacement of the leaving group, such as halogen (as a resin-bound alpha -haloacetamide) with a sufficient amount of a second sub-monomer comprising an -NH2 group, such as a primary amine, alkoxyamine, semicarbazide, acyl hydrazide, carbazate or the like. Repetition of the two step cycle of acylation and displacement gives the desired oligomers. The efficient synthesis of a wide variety of oligomeric NSGs using automated synthesis technology of the present method makes these oligomers attractive candidates for the generation and rapid screening of diverse peptidomimetic libraries. The oligomers of the invention, such as N-substituted glycines (i.e. poly NSGs) disclosed here provide a new class of peptide-like compounds not found in nature, but which are synthetically accessible and have been shown to possess significant biological activity and proteolytic stability.
专利号:EP-0671928-B1 优先权日:1992-09-24 标题 :Synthesis of n-substituted oligomers 发明人:ZUCKERMANN RONALD N; KERR JANICE M; KENT STEPHEN BRIAN HENRY; MOOS WALTER H; SIMON REYNA J; GOFF DANE A 权利人:CHIRON CORP 摘要:Poly N-substituted Glycines (poly NSGs), wherein the substituents bear purine or pyrimidine bases (R<9>) every second glycine: In addition, a solid phase method for the synthesis of N-substituted oligomers of more general structures is disclosed.The poly NSGs obtainable by this method can have a wide variety of side-chain substituents. Each N-substituted glycine monomer is assembled from two 'sub-monomers' directly on the solid support. Each cycle of monomer addition consists of two steps: (1) acylation of a secondary amine bound to the support with an acylating agent comprising a leaving group capable of nucleophilic displacement by -NH2, such as a haloacetic acid, and (2) introduction of the side-chain by nucleophilic displacement of the leaving group, such as halogen (as a resin-bound alpha -haloacetamide) with a sufficient amount of a second sub-monomer comprising an -NH2 group, such as a primary amine, alkoxyamine, semicarbazide, acyl hydrazide, carbazate or the like. Repetition of the two step cycle of acylation and displacement gives the desired oligomers. The efficient synthesis of a wide variety of oligomeric NSGs using the automated synthesis technology of the present method makes these oligomers attractive candidates for the generation and rapid screening of diverse peptidomimetic libraries. The oligomers of the invention, such as N-substituted glycines (i.e. poly NSGs) disclosed here provide a new class of peptide-like compounds not found in nature, but which are synthetically accessible and have been shown to possess significant biological activity and proteolytic stability.
专利号:US-5877278-A 优先权日:1992-09-24 标题:Synthesis of N-substituted oligomers 发明人:ZUCKERMANN RONALD N; GOFF DANE A; NG SIMON; SPEAR KERRY; SCOTT BARBARA O; SIGMUND AARON C; GOLDSMITH RICHARD A; MARLOWE CHARLES K; PEI YAZHONG; RICHTER LUTZ; SIMON REYNA 权利人:CHIRON CORP 摘要:A solid-phase method for the synthesis of N-substituted oligomers, such as poly (N-substituted glycines) (referred to herein as poly NSGs) is used to obtain oligomers, such as poly NSGs of potential therapeutic interest which poly NSGs can have a wide variety of side-chain substituents. Each N-substituted glycine monomer is assembled from two 'sub-monomers' directly on the solid support. Each cycle of monomer addition consists of two steps: (1) acylation of a secondary amine bound to the support with an acylating agent comprising a leaving group capable of nucleophilic displacement by -NH2, such as a haloacetic acid, and (2) introduction of the side-chain by nucleophilic displacement of the leaving group, such as halogen (as a solid support-bound alpha -haloacetamide) with a sufficient amount of a second sub-monomer comprising an -NH2 group, such as a primary amine, alkoxyamine, semicarbazide, acyl hydrazide, carbazate or the like. Repetition of the two step cycle of acylation and displacement gives the desired oligomers. The efficient synthesis of a wide variety of oligomeric NSGs using automated synthesis technology of the present method makes these oligomers attractive candidates for the generation and rapid screening of diverse peptidomimetic libraries. The oligomers of the invention, such as N-substituted glycines (i.e. poly NSGs) disclosed here provide a new class of peptide-like compounds not found in nature, but which are synthetically accessible and have been shown to possess significant biological activity and proteolytic stability. Combinatorial libraries of cyclic compounds are disclosed wherein the cyclic compounds are comprised of at least one ring structure derived from cyclization of a peptoid backbone. The diversity of product compounds is generated by the sequential addition of substituted submonomers. The combinatorial library includes 10 or more, preferably 100 or more, and more preferably 1,000 or more distinct and different compounds. The library includes each of the product compounds in retrievable and analyzable amounts and preferably includes at least one biologically active compound. Methods of synthesizing the combinatorial libraries and assay devices produced using the libraries are disclosed as is methodology for screening for and obtaining biologically active cyclic organic compounds.
专利号:US-9920160-B2 优先权日:2014-09-03 标题 :Method for synthesis of polymer containing multiple epoxy groups 发明人:GAO CHAO; ZHENG YAOCHEN; PENG LI; CAI SHENGYING; WENG ZHULIN 权利人:UNIV ZHEJIANG 摘要:A method for a synthesis of a polymer containing multiple epoxy groups includes steps of: under protection of nitrogen or argon, with a photosensitive free radical initiator under an ultraviolet light irradiation, initiating a mixture of a dithiol compound and alkynyl glycidyl ether or other alkynyl-containing compounds to proceed a thiol-yne polymerization, so as to obtain the polymer. The number of the epoxy groups is able to be adjusted through changing a type of a dithiol monomer, a mixing ratio of the dithiol monomer, and a mixing ratio between the alkynyl glycidyl ether and other alkynyl compounds. The present invention has advantages of: fast reaction, convenient process, easy post-processing, a large number of the epoxy groups, and adjustable and controllable content. The obtained polymer has a wide potential application in fields of coating, adhesive, ink, encapsulating material, resin for composite material, additive, high performance material, function material, and so on.
专利号:US-2012003164-A1 优先权日:1998-12-30 标题 :Cosmetic or dermatological composition containing an active agent which stimulates synthesis of the protein hsp 32 in the skin 发明人:NIZARD CARINE; MOREAU MARIELLE; BONTE FREDERIC 权利人:NIZARD CARINE; MOREAU MARIELLE; BONTE FREDERIC; DIOR CHRISTIAN PARFUMS 摘要:A dermatological or cosmetological composition for an external topical administration, included together with pharmaceutically and/or cosmetologically acceptable excipients: at least one UVA-stabilizing and/or UVB-stabilizing screening agent, at least one compound capable of activating the endogenous synthesis of Heat Shock Protein (HSP) 32 or a functional peptide fragment of such a protein, and forskolin or any extract containing it.
专利号:WO-2024260915-A1 优先权日:2023-06-19 标题:Dynamic covalent chemistry of spiropyrans for synthesis of photoswitchable photoinitiators and uses thereof 发明人:GARMSHAUSEN YVES 权利人:XOLO GMBH 摘要:The present invention relates to spiropyrans and process for the manufacture of them. In particular, a method is provided to exchange the indole and salicylaldehyde part of a spiropyran in a reversible reaction. The method is used for the synthesis of dual color photoinitiators with specific substituents and substitution patterns, which result in improved dual color volumetric printing (xolography). Furthermore, a process for locally polymerizing a starting material by dual color photopolymerization is disclosed.
1: Chang KY, Yang CH, Chou HY, Chen KC, Huang YC. Organic ultraviolet filters regulate hyaluronan metabolism in human epidermal keratinocytes through the phosphatidylinositol 3-kinase pathway. Toxicol In Vitro. 2023 Feb;86:105511. doi: 10.1016/j.tiv.2022.105511. Epub 2022 Nov 4. 8(11):4987-4995. doi: 10.1021/acsbiomaterials.2c00680. Epub 2022 Oct 31. 29(13):18605-18616. doi: 10.1007/s11356-021-16970-0. Epub 2021 Oct 25. 69(11):1039-1044. doi: 10.1248/cpb.c21-00398. Epub 2021 Aug 28. 268(Pt B):115894. doi: 10.1016/j.envpol.2020.115894. Epub 2020 Oct 17. 206:111199. doi: 10.1016/j.ecoenv.2020.111199. Epub 2020 Sep 2. 402:123477. doi: 10.1016/j.jhazmat.2020.123477. Epub 2020 Jul 15. 14(7):e0220280. doi: 10.1371/journal.pone.0220280.
合成参考文献
摘要:McHugh PJ, Knowland J; Photochem Photobiol 66(2): 279-81 (1997) 摘要: 摘要:EPA/Office of Pollution Prevention and Toxics; High Production Volume (HPV) Challenge Program. Benzoic acid, 4-(dimethylamino)-, 2-ethylhexyl ester (21245-02-3). Available from, as of October 18, 2013: 摘要:Franke C et al; Chemosphere 29: 1501-14 (1994) 摘要: