- Syntheses of 12-aminododecanoic and 11-aminoundecanoic acids from vernolic acid
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12-Aminododecanoic acid and 11-aminoundecanoic acid, monomer precursors for nylon-12 and nylon-11, respectively, have been synthesized from vernolic (cis-12,13-epoxy-cis-9-octadecenoic) acid via a reaction sequence that includes the formation of 12-oxododecanoic acid oxime. Saponification of vernonia oil, followed by a low-temperature recrystallization at -20°C, gave 51% vernolic acid (97% purity, m.p. 23-25°C). Hydrogenation afforded cis-12,13-epoxystearic acid (m.p. 52-54°C, lit. m.p. 52-54°C), which upon oxidation with periodic acid in tertiary butyl alcohol gave 12-oxododecanoic acid with an isolated yield of 71.0%. Reaction of the oxoacid with hydroxylamine hydrochloride gave 12-oxododecanoic acid oxime, which was catalytically reduced to give 12-aminododecanoic acid with a yield greater than 85% and a melting point of 184-186°C (lit. m.p. 185-187C). 11-Aminoundecanoic acid was prepared from the 12-oxododecanoic acid oxime via a three-step reaction sequence that involved a Beckmann rearrangement, Hofmann degradation, and hydrolysis. Thus, the aldoxime acid was hydrolyzed in the presence of nickel acetate tetrahydrate to give 11-carbamoylundecanoic acid (48% yield, m.p. 129-131°C, lit. m.p. 129-130°C). The amide was then treated with a solution of sodium methoxide and bromine at 70-80°C to give 11-(methoxycarbonylamino)undecanoic acid at 75% yield (m.p. 84-86°C; elemental analysis, calculated for C13H25NO4: C, 60.19; H, 9.73; N, 5.40; O, 24.68%; found C, 60.02; H, 9.81; N, 5.26; O, 24.91%), which upon alkaline hydrolysis and subsequent neutralization gave 11-aminoundecanoic acid at 34% yield (m.p. 189-192°C, lit. m.p. 190°C). Mass spectrometric and 13C nuclear magnetic resonance data of the previously unreported 11-(methoxycarbonylamino)undecanoic acid is provided.
- Ayorinde, Folahan O.,Nana, Erick Y.,Nicely, Pete D.,Woods, Anthony S.,Price, Elvis O.,Nwaonicha, Chukwuma P.
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- TARGET PROTEIN EED DEGRADATION-INDUCING DEGRADUCER, PREPARATION METHOD THEREOF, AND PHARMACEUTICAL COMPOSITION FOR PREVENTING OR TREATING DISEASES RELATED TO EED, EZH2, OR PRC2, COMPRISING SAME AS ACTIVE INGREDIENT
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The present invention relates to a target protein degradation-inducing Degraducer, a preparation method thereof, and a pharmaceutical composition for preventing or treating diseases related to EED, EZH2, or PRC2 comprising same as an active ingredient. A novel compound represented by formula 1, according to the present invention is a Degraducer compound that induces degradation of a target protein, i.e., embryonic ectoderm development (EED) or polycomb repressive complex 2 (PRC2), utilizing cereblon E3 ubiquitin ligase, von Hippel-Lindau tumor suppressor (VHL) E3 ubiquitin ligase, mouse double minute 2 homolog (MDM2) E3 ubiquitin ligase, and cellular inhibitor of apoptosis protein 1 (cIAP) E3 ubiquitin ligase, wherein the compound has an aspect of remarkably achieving target protein degradation-inducing activity through a ubiquitin proteasome system (UPS), and therefore there is a useful effect in that it is possible to provide a pharmaceutical composition for preventing or treating diseases or conditions related to a target protein, and a functional health food composition for preventing or improving same, comprising said compound as an active ingredient.
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- Self-Adjuvanting Cancer Vaccines from Conjugation-Ready Lipid A Analogues and Synthetic Long Peptides
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Self-adjuvanting vaccines, wherein an antigenic peptide is covalently bound to an immunostimulating agent, have been shown to be promising tools for immunotherapy. Synthetic Toll-like receptor (TLR) ligands are ideal adjuvants for covalent linking to peptides or proteins. We here introduce a conjugation-ready TLR4 ligand, CRX-527, a potent powerful lipid A analogue, in the generation of novel conjugate-vaccine modalities. Effective chemistry has been developed for the synthesis of the conjugation-ready ligand as well as the connection of it to the peptide antigen. Different linker systems and connection modes to a model peptide were explored, and in vitro evaluation of the conjugates showed them to be powerful immune-activating agents, significantly more effective than the separate components. Mounting the CRX-527 ligand at the N-terminus of the model peptide antigen delivered a vaccine modality that proved to be potent in activation of dendritic cells, in facilitating antigen presentation, and in initiating specific CD8+ T-cell-mediated killing of antigen-loaded target cells in vivo. Synthetic TLR4 ligands thus show great promise in potentiating the conjugate vaccine platform for application in cancer vaccination.
- Reintjens, Niels R. M.,Tondini, Elena,De Jong, Ana R.,Meeuwenoord, Nico J.,Chiodo, Fabrizio,Peterse, Evert,Overkleeft, Herman S.,Filippov, Dmitri V.,Van Der Marel, Gijsbert A.,Ossendorp, Ferry,Codée, Jeroen D. C.
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supporting information
p. 11691 - 11706
(2020/11/26)
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- Method of Preparing Aminoundecane Acid and 11-Aminoundecanoic Acid or Structural Isomer Thereof by Hydroformylation Reaction
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The present invention relates to a method for preparing 11-aminoundecanoic acid or structural isomers thereof using a hydroformylation reaction. More particularly, the present invention is an eco-friendly method capable of preparing aminoundecanoic acid used as a monomer of polyamide and structural isomers thereof from an olefinic acid ester obtained through a metathesis reaction of oleic acid by means of hydroformylation, reductive amination reaction, and hydrolysis reaction, and capable of producing various polyamides having different physical properties according to a ratio of each isomer since the ratio of structural isomers can be adjusted according to a ligand.COPYRIGHT KIPO 2021
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Paragraph 0112-0116; 0119-0136
(2020/11/03)
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- CONJUGATED CHEMICAL INDUCERS OF DEGRADATION AND METHODS OF USE
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The subject matter described herein is directed to antibody-CIDE conjugates (Ab-CIDEs), to pharmaceutical compositions containing them, and to their use in treating diseases and conditions where targeted protein degradation is beneficial.
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Page/Page column 438
(2020/05/28)
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- Preparation method of 11-aminoundecanoic acid
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The invention provides a preparation method of 11-aminoundecanoic acid. The method comprises the following steps: 1) dissolving 9-hydroxyl pelargonic acid or 9-hydroxyl pelargonate in a solvent and carrying out selective oxidization in the presence of an oxidant to prepare 9-oxo pelargonic acid or 9-oxo pelargonate; 2) dissolving 9-oxo pelargonic acid or 9-oxo pelargonate and cyanoacetate in a solvent for knoevenagel condensation reaction to obtain a compound as shown in a formula III; 3) continuously carrying out a hydrolysis reaction on the product obtained in the step 2) and carrying out acidification to obtain 2-cyano cyanohendecene-2-diacid; 4) carrying out a selective decarboxylic reaction on the product obtained in the step 3) to obtain a compound as shown in a formula V: 10-cyno-10-ene capric acid; and 5) adding a catalyst into the 10-cyno-10-ene capric acid obtained in the step 4), replacing the mixture with nitrogen and hydrogen successively for a hydrogenation reduction reaction, and refining a coarse product to obtain the 11-aminoundecanoic acid.
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- PROCESS FOR THE CO-PRODUCTION OF LONG CHAIN AMINO ACIDS AND DIBASIC ACIDS
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There is disclosed a process for the co-production of long chain ω-amino acid and long chain dibasic acid, comprising: (1) reacting long chain ketoacid derivative with hydroxylamine or subjecting ketoacid derivative to an ammoximation to yield oxime derivative; (2) subjecting oxime derivative to Beckmann rearrangement to yield a mixture of mixed amide derivatives; (3) hydrolyzing the mixed amide derivatives to produce long chain ω-amino acid and long chain dibasic acid.
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Paragraph 0058-0061
(2019/02/01)
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- Process for producing long chain amino acids and dibasic acids
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There is disclosed a process for the production of long chain amino acid and long chain dibasic acid, comprising: (1) reacting long chain keto fatty acid with hydroxylamine or subjecting keto fatty acid to an ammoximation reaction to yield an oxime fatty acid; (2) subjecting the oxime fatty acid to the Beckmann rearrangement to yield a mixture of two amide fatty acids; (3) hydrolyzing the mixed amide fatty acids to produce long chain amino acid, long chain dibasic acid, short chain alkylamine, and alkanoic acid.
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Page/Page column 9
(2018/09/21)
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- PREPARATION OF AMINO ACIDS AND AMINO ACID DERIVATIVES
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The invention relates to a method for synthesizing amino acids or amino acid derivatives involving cross metathesis of functionalized olefins and a tandem amination-reduction process. Amino acids and amino acid derivatives present many interesting physical and chemical properties finding many uses in the automotive, fuel, electronic, and textile industries.
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Paragraph 0232
(2018/04/20)
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- Parallel anti-sense two-step cascade for alcohol amination leading to ω-amino fatty acids and α,ω-diamines
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Running two two-step cascades in parallel anti-sense to transform an alcohol to an amine allowed the conversion of ω-hydroxy fatty acids (ω-HFAs) and α,ω-diols to the corresponding ω-amino fatty acids (ω-AmFAs) and α,ω-diamines, respectively. The network required only two enzymes namely an aldehyde reductase (AHR) and a transaminase (TA). Benzylamine served on the one hand as amine donor and on the other hand after deamination to benzaldehyde also as oxidant. All ω-HFAs tested were efficiently transformed to their corresponding ω-AmFAs using purified enzymes as well as a whole-cell system, separately expressing both the enzymes, with conversions ranging from 80-95%. Additionally, a single-cell co-expressing all enzymes successfully produced the ω-AmFAs as well as the α,ω-diamines with >90% yield. This system was extended by employing a lactonase, enabling the transformation of ?-caprolactone to its corresponding ω-AmFA with >80% conversion.
- Sung, Sihyong,Jeon, Hyunwoo,Sarak, Sharad,Ahsan, Md Murshidul,Patil, Mahesh D.,Kroutil, Wolfgang,Kim, Byung-Gee,Yun, Hyungdon
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supporting information
p. 4591 - 4595
(2018/10/23)
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- A -10 preparation of cavity 11-amino undecanoic acid method
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The invention relates to a process for producing nylon 11 resin by utilizing castor oil, in particular to a method for preparing 11-aminoundecanoic acid by utilizing 10-undecenoic acid. The method comprises the following steps: proportioning 10-undecenoic acid, methylbenzene and benzene to prepare a raw material solution, and generating 11-bromoundecanoic acid by virtue of the additive reaction of the raw material solution with hydrogen bromide in a double-kettle reaction device in the presence of catalyst; ammonolyzing the 11-bromoundecanoic acid by virtue of three different processing ways without the crystallization; adding a phase-transfer catalyst in the ammonolysis reaction to accelerate the ammonolysis reaction; carrying out vacuum filtering after the ammonolysis reaction is completed, wherein a filter cake is a 11-aminoundecanoic acid crude product; adding the crude product into the deionized water, dissolving the crude product by heating the crude product, cooling and crystallizing the crude product, and filtering the crude product to obtain the refined 11-aminoundecanoic acid product.
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Paragraph 0032
(2017/02/09)
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- METHOD OF SYNTHESISING AMINO ACID BY METATHESIS, HYDROLYSIS, THEN HYDROGENATION
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A method of synthesising an amino acid from an unsaturated fatty compound I that includes at least the following steps: cross-metathesis with a short unsaturated compound II, one of compounds I or II comprising a nitrile function and the other of these compounds II or I an ester function, so as to obtain and recover at least one monounsaturated nitrile ester NEU; hydrolysis of the NEU in unsaturated acid nitrile NAU; hydrogenation of the NAU to saturated amino acid AA; and then purification of the AA, if applicable, in particular by crystallisation. Also, a polymer obtained by polymerisation using the amino acid synthesised according to the method.
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Paragraph 0192-0193
(2016/03/05)
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- Microbial synthesis of medium-chain α,ω-dicarboxylic acids and ω-aminocarboxylic acids from renewable long-chain fatty acids
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Biotransformation of long-chain fatty acids into medium-chain α,ω-dicarboxylic acids or ω-aminocarboxylic acids could be achieved with biocatalysts. This study presents the production of α,ω-dicarboxylic acids (e.g., C9, C11, C 12, C13) and ω-aminocarboxylic acids (e.g., C 11, C12, C13) directly from fatty acids (e.g., oleic acid, ricinoleic acid, lesquerolic acid) using recombinant Escherichia coli-based biocatalysts. ω-Hydroxycarboxylic acids, which were produced from oxidative cleavage of fatty acids via enzymatic reactions involving a fatty acid double bond hydratase, an alcohol dehydrogenase, a Baeyer-Villiger monooxygenase and an esterase, were then oxidized to α,ω- dicarboxylic acids by alcohol dehydrogenase (ADH, AlkJ) from Pseudomonas putida GPo1 or converted into ω-aminocarboxylic acids by a serial combination of ADH from P. putida GPo1 and an ω-transaminase of Silicibacter pomeroyi. The double bonds present in the fatty acids such as ricinoleic acid and lesquerolic acid were reduced by E. coli-native enzymes during the biotransformations. This study demonstrates that the industrially relevant building blocks (C9 to C13 saturated α,ω- dicarboxylic acids and ω-aminocarboxylic acids) can be produced from renewable fatty acids using biocatalysis.
- Song, Ji-Won,Lee, Jung-Hoo,Bornscheuer, Uwe T.,Park, Jin-Byung
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p. 1782 - 1788
(2014/06/09)
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- Process for Producing Nitrile-Fatty Acid Compounds
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The invention relates to a process for synthesizing a nitrile-fatty acid (heminitrile) from unsaturated fatty acids, in the form of an acid or a simple ester or a “complex” ester of triglyceride type, which is first of all converted into an unsaturated fatty nitrile which is subjected to oxidative cleavage using H2O2 as oxidizing agent. This process can be used for preparing polyamide monomers, such as ω-amino acids or diamines or diacids equivalent to said heminitrile and for obtaining polyamides from raw materials which are of natural origin and from a renewable source.
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Paragraph 0201
(2014/02/15)
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- PROCESS FOR THE AMMONOLYSIS OF 11-BROMOUNDECANOIC ACID
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The invention relates to a process for the ammonolysis of 11-aminoundecanoic acid, carried out under conditions that make it possible to limit secondary reactions that produce impurities, especially secondary amine type reactions, while considerably reducing the reaction time. According to the invention, the process comprises the following steps: i) a step of dispersing 11-bromoundecanoic acid, molten or non-molten, in an aqueous solution of ammonia, and ii) an ammonolysis step comprising the reaction of 11-bromoundecanoic acid with excess ammonia water under conditions whereby the reaction medium is stirred and heated gradually so as to obtain 11-aminoundecanoc acid with total consumption of the 11-bromoundecanoic acid.
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Page/Page column 3
(2011/10/19)
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- NMR Detection of Simultaneous Formation of [2]- and [3]Pseudorotaxanes in Aqueous Solution between α-Cyclodextrin and Linear Aliphatic α,ω-Amino acids, an α,ω-Diamine and an α,ω-Diacid of Similar Length, and Comparison with the Solid-State Structures
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The interactions of 11-aminoundecanoic acid (1), 12-aminododecanoic acid (2), 1,12-diaminododecane (3), and 1,13-tridecanoic diacid (4) with α-cyclodextrin (αCD) were studied in aqueous solution by NMR spectroscopy. The association modes were established with titration and continuous variation plots, variable temperature NMR spectra, and dipolar interactions as recorded in 2D ROESY spectra. The studies were carried out at pH 7.3 and 13.6. These long, linear bifunctional molecules were found to form simultaneously [2]- and [3]pseudorotaxanes with αCD in the aqueous solution. At the higher pH the 1:1 adducts were present at concentrations higher than at the neutral pH. The longer guests formed complexes enriched in the 2:1 constituent at both pH values. There were clear indications that the [2]pseudorotaxanes are present in two isomeric forms. The presence of isomers also in the [3]pseudorotaxanes was not ruled out. Various exchange rate regimes were observed; clearly in neutral solutions the formation of the 1:1 complexes was fast in the NMR time scale, whereas the threading of a second αCD ring was a slower process. In the solid state, the adduct of αCD/2 had the structure of a [3]pseudorotaxane, in accordance with previously solved crystal structures of αCD/3 and βCD/4. The species in solution, in contrast with those present in the solid state, are therefore of varying nature, and thus the frequently and conveniently assumed 1:1 stoichiometry in similar systems is an oversimplification of the real situation.
- Eliadou, Kyriaki,Yannakopoulou, Konstantina,Rontoyianni, Aliki,Mavridis, Irene M.
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p. 6217 - 6226
(2007/10/03)
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- Solid state polycondensation within cyclodextrin channels leading to watersoluble polyamide rotaxanes
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α,ω-Aminocarboxylic acids form microcrystalline inclusion compounds with α-cyclodextrin. In these inclusion compounds cyclodextrins build up channel structures, in which the α,ω-aminocarboxylic acids can be polycondensed at 200-240°C. As the resulting pol
- Wenz, Gerhard,Steinbrunn, Marc Boris,Landfester, Katharina
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p. 15575 - 15592
(2007/10/03)
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- Disazo dyestuffs
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Disazo dyestuffs have been found which, in the form of the free acid, correspond to the formula (I) STR1 represents H or an optionally substituted aliphatic or aromatic radical and R1 to R6 and A have the meaning given in the description, which are outstandingly suitable for inkjet printing.
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- Synthesis and Physicochemical Properties of Schiff Bases of Amino Acids with Salicylaldehyde
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A series of the Schiff bases of α- and ω-amino acids with salicylaldehyde was synthesized.The physicochemical properties of the substances obtained, including the fluorescent characteristics, were examined, and the hydrolysis constants at pH 6.0, 7.0, and 8.0 were determined.Key words: amino acids, hydroxybenzaldehyde, Schiff bases, fluorescence, hydrolysis constant
- Lurie, E. Yu.,Mosina, E. M.,Efremova, A. A.,Kaplun, A. P.,Shvets, V. I.
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p. 520 - 523
(2007/10/03)
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