- One-pot biotransformation of glycerol into serinol catalysed by biocatalytic composites made of whole cells and immobilised enzymes
-
Biocatalytic cascades afford the development of economically sustainable and green processes. Herein we examined the unprecedented coupling of co-immobilisedGluconobacter oxydansand an isolated transaminase to synthesise serinol from glycerol. Through this approach, we manufactured up to 36 mM serinol, the highest titer ever reported for a non-fermentative biosynthesis. More importantly, similar productivities are obtained starting from the industrial by-product crude glycerol, demonstrating the possibilities of this hybrid heterogenenous biocatalyst for valorising bio-based raw materials.
- Ripoll, Magdalena,Velasco-Lozano, Susana,Jackson, Erienne,Diamanti, Eleftheria,Betancor, Lorena,López-Gallego, Fernando
-
supporting information
p. 1140 - 1146
(2021/02/26)
-
- Novel method for producing 2-amino-1, 3-propylene glycol by JIT method
-
The invention belongs to the field of fine chemical engineering, and relates to a novel method for producing 2-amino-1, 3-propylene glycol by a JIT method, the novel method is composed of a catalytic chlorination reaction and a catalytic amination reaction, glycerol is chlorinated by hydrogen chloride under the catalysis of zinc chloride to obtain 2-chloro-1, 3-propylene glycol, and the 2-chloro-1, 3-propylene glycol is subjected to a catalytic reaction by urotropin to obtain 2-chloro-1, 3-propylene glycol.
- -
-
Paragraph 0048-0051
(2021/11/26)
-
- 2-amino-1, 3-propanediol synthesis process
-
The invention discloses a 2-amino-1, 3-propanediol synthesis process. In a homogeneous system, nitromethane reacts with formalin in a methanol/water system by the aid of catalytic activity of organicalkali triethylamine catalysts to generate an intermediate product mainly comprising 2-nitro-1, 3-propanediol, the intermediate product is not separated in the homogeneous system, Raney nickel catalysts are directly added to perform catalytic hydrogenation reduction reaction and generate mixed mother solution taking 2-amino-1, 3-propanediol as a main product, and the mother solution is separated,concentrated, distilled, recrystallized, purified, separated and dried to obtain a finished product. Separation steps are simplified, the process is low in production equipment requirement, simple andconvenient in operation, less in wastewater discharge amount, low in cost and more suitable for industrial large-scale production and application, and the recycling rate of Raney nickels is effectively increased in the post-treatment process.
- -
-
Paragraph 0007; 0017; 0018
(2019/04/06)
-
- A non-noble metal continuous hydrogenation reduction method of preparing serinol
-
The invention belongs to the field of organic synthesis reaction, discloses a non-noble metal continuous hydrogenation reduction preparation of serinol method, characterized in that comprises the following steps: malonic acid dimethyl ester asia through nitration and reduction, preparation to obtain 2 - amino - 1, 3 - malonic acid dimethyl ester; comprising the 2 - amino - 1, 3 - malonic acid dimethyl ester, the reaction catalyst, non-homogeneous metal supported catalyst raw materials into the reactor for oxidation-reduction reaction, to obtain a mixed solution, in the prepared mixed solution in reaction adds the hydrogen, to obtain the product 2 - amino - 1, 3 - propylene glycol. The invention relates the ordinary non-homogeneous metal copper zinc-based alloy ternary to four ternary catalyst, greatly improves the reaction yield, reduce the reaction pressure, improves the safety of the reaction, the production cost is reduced, to a clean, high-efficiency, safety, environmental protection, continuous new hydrogenation process technology.
- -
-
Paragraph 0036; 0040-0068
(2019/04/10)
-
- Serinol synthesis of new technology
-
The invention relates to a serinol preparation method, and belongs to the technical field of serinol preparation through a reduction reaction, wherein serinol is an important intermediate of a non-ionic X-ray contrast agent iopamidol. According to the present invention, nitromethane and paraformaldehyde are adopted as raw materials, hydrogen is adopted as a reduction agent, and palladium/charcoal is adopted as a catalyst to prepare the serinol; and the method has characteristics of mature process, simple equipment and high serinol yield, and is suitable for industrial production.
- -
-
Page/Page column 4-7
(2018/04/01)
-
- Method for preparing polyamine by direct ammoniation of polyhydroxy compound
-
A method for preparing polyamine by direct ammoniation of a polyhydroxy compound is disclosed. By using a polyhydroxy compound, ammonia gas or liquefied ammonia as a raw material and using a carrier-loaded liquid-phase reduced transition metal as a catalyst, an ammoniation reaction of the polyhydroxy compound under mild conditions is realized. The catalyst has high selectivity of polyamine. The catalyst can be recovered and recycled.
- -
-
Paragraph 0046; 0047; 0061; 0062
(2016/10/24)
-
- Characterization of a novel amine transaminase from Halomonas elongata
-
Chiral amines are indispensable building blocks in the production of biologically active compounds. They are fundamental for the pharmaceutical industry, both as active molecules themselves and as chiral auxiliaries in asymmetric synthesis; however, the available synthetic strategies often present disadvantages. ω-Transaminases (ω-TAs) appear as an attractive alternative by driving the stereoselective amination of prochiral ketones. HEWT is a novel amine transaminase from the moderate halophilic bacterium, Halomonas elongata DSM 2581, which is highly (S)-selective, being able to fully convert (S)-1-phenylethylamine to acetophenone and showing no activity with the corresponding (R)-1-phenylethylamine. HEWT has a broad substrate scope, active with a range of amino donors and acceptors, and naturally accepts isopropylamine (IPA) as amino donor in asymmetric synthesis providing a 41% conversion of pyruvate in 24 h at 37°C starting with 1:1 molar ratio between the reagents. HEWT also accepts ortho-xylylenediamine as amino donor in for amine synthesis, in particular, with benzaldehyde yielding high conversions between 90 and 95%. The enzyme is also tolerant to the presence of cosolvents up to 20% making it a promising candidate for industrial applications.
- Cerioli, Lorenzo,Planchestainer, Matteo,Cassidy, Jennifer,Tessaro, Davide,Paradisi, Francesca
-
p. 141 - 150
(2015/09/01)
-
- Insight into the mechanism of hydrogenation of amino acids to amino alcohols catalyzed by a heterogeneous MoOx-modified Rh catalyst
-
Hydrogenation of amino acids to amino alcohols is a promising utilization of natural amino acids. We found that MoOx-modified Rh/SiO2 (Rh-MoOx/SiO2) is an efficient heterogeneous catalyst for the reaction at low temperature (323 K) and the addition of a small amount of MoOx drastically increases the activity and selectivity. Here, we report the catalytic potential of Rh-MoOx/SiO2 and the results of kinetic and spectroscopic studies to elucidate the reaction mechanism of Rh-MoOx/SiO2 catalyzed hydrogenation of amino acids to amino alcohols. Rh-MoOx/SiO2 is superior to previously reported catalysts in terms of activity and substrate scope. This reaction proceeds by direct formation of an aldehyde intermediate from the carboxylic acid moiety, which is different from the reported reaction mechanism. This mechanism can be attributed to the reactive hydride species and substrate adsorption caused by MoOx modification of Rh metal, which results in high activity, selectivity, and enantioselectivity.
- Tamura, Masazumi,Tamura, Riku,Takeda, Yasuyuki,Nakagawa, Yoshinao,Tomishige, Keiichi
-
p. 3097 - 3107
(2015/02/05)
-
- Catalytic hydrogenation of amino acids to amino alcohols with complete retention of configuration
-
Rh-MoOx/SiO2 is an effective heterogeneous catalyst for selective hydrogenation of amino acids to amino alcohols in a water solvent. MoOx modification of Rh drastically enhanced the activity and improved the selectivity and ee. Various amino alcohols were obtained in high yields (90-94%) with complete retention of configuration. This journal is the Partner Organisations 2014.
- Tamura, Masazumi,Tamura, Riku,Takeda, Yasuyuki,Nakagawa, Yoshinao,Tomishige, Keiichi
-
p. 6656 - 6659
(2014/06/10)
-
- Process for production of serinol and its bis-adduct
-
An improved method for the production of 2-amino-1,3-propanediol (serinol) and its bis-adduct, 2,2′-iminobis-1,3-propanediol, from dihydroxyacetone and ammonia in the presence of a hydrogenation catalyst such as Raney nickel, followed by separation using an acidic ion-exchange resin.
- -
-
Page/Page column 3-4
(2014/03/21)
-
- An acyclic trialkylamine virtually planar at nitrogen. Some chemical consequences of nitrogen planarity
-
(Figure presented) The synthesis of the exceedingly congested amine tris(1,3-dihydroxy-2-propyl)amine, 9, was achieved in 47- 51% overall yield. The nitrogen atom of 9 is virtually planar; it is 0.082 A out of the plane defined by the three attached carbons. The corresponding out-of-plane measurement is 0.282 A for triisopropylamine and ca. 0.4 A for uncongested trialkylamines. The N-C bonds of 9 are quite short, despite the steric congestion. The conjugate acid of 9 (viz., 9H+) is very strong: pKa = 3.08 (cf. Et3NH+ pKa = 10.7). Comparison with suitable model compounds suggests 9 is less basic than predicted by ca. 1.5 pKa units. The structure of 9H +Cl- was determined by X-ray crystallography. Here too, the nitrogen is severely flattened relative to ordinary ammonium cations. In 9H+Cl-, the proton on the nitrogen of 9H+ forms three intramolecular hydrogen bonds to hydroxyl groups, i.e., a so-called trifurcated hydrogen bond. The NH ... O lengths in 9H+ are slightly shorter than comparable trifurcated hydrogen bonds. Cyclic voltammetry (CV) on 9 finds E1/2ox is 0.88 V, which is consistent with the inductive effect of the 1,3-dihydroxy-2-propyl groups attached to nitrogen. It is also observed that the electrochemical oxidation of 9 is reversible on the CV time scale. The 15N NMR chemical shift of the essentially planar nitrogen atom of 9 is discussed.
- Jie, Yuanping,Livant, Peter,Li, Hui,Yang, Minmin,Zhu, Wei,Cammarata, Vince,Almond, Philip,Sullens, Tyler,Qin, Yu,Bakker, Eric
-
experimental part
p. 4472 - 4479
(2010/10/02)
-
- GLYCEROL DERIVATIVES AND METHODS OF MAKING SAME
-
Symmetrical polyols, polyol esters, polyesters, polyurethanes, triazoles, and polyvinylethers derived from glycerol and methods of making the symmetrical polyols, polyesters, polyurethanes, polyhydroxyvinylethers and triazoles are discussed. Also provided is a method of making serinol.
- -
-
Page/Page column 55
(2009/01/20)
-
- Stereoselective synthesis and anti-inflammatory activities of 6- and 7-membered dioxacycloalkanes
-
A class of 5-trifluoroacetylamino-1,3-dioxacycloalkanes, 5-benzoylamino-1,3-dioxacycloalkanes, and 5-amino-1,3-dioxacycloalkane compounds were stereoselectively synthesized as potential anti-inflammatory drug candidates. The anti-inflammatory activities of these compounds were tested using the xylene-induced mouse ear edema model, from which multiple compounds possessing anti-inflammatory properties which surpass aspirin were identified; these compounds were then compared to establish structure-activity relationships.
- Gu, Keli,Bi, Lanrong,Zhao, Ming,Wang, Chao,Dolan, Cheryl,Kao, Michael C.,Tok, Jeffrey B.-H.,Peng, Shiqi
-
p. 1339 - 1347
(2007/10/03)
-
- Convenient synthesis of 1-(1,3-Dihydroxy-2-propyl)-4-nitroimidazoles
-
The title compounds have been obtained in reaction of 1,4-dinitroimidazoles with 2-amino-1,3-propanedioles in water-methanol solution. 1-(1,3-Dihydroxy-2-propyl)4-nitroimidazoles were transformed into derivatives that can be used for combinatorial oligomer synthesis.
- Wengel,Walczak
-
-
- Catalytic Hydrogenation of Chiral α-Amino and α-Hydroxy Esters at Room Temperature with Nishimura Catalyst without Racemization
-
The hydrogenation of carboxylic acid derivatives at room temperature was investigated. With a mixed Rh/Pt oxide (Nishimura catalyst), low to medium activity was observed for various α-amino and α-hydroxy esters. At 100 bar hydrogen pressure and 10% catalysts loading, high yields of the desired amino alcohols and diols were obtained without racemization. The most suitable α-substituents were NH2, NHR, and OH, whereas β-NH2 were less effective. Usually, aromatic rings were also hydrogenated, but with the free bases of amino acids as substrates, some selectivity was observed. No reaction was found for α-NR2, α-OR, and unfunctionalized esters; acids and amides were also not reduced under these conditions. A working hypothesis for the mode of action of the catalyst is presented.
- Studer, Martin,Burkhardt, Stefan,Blaser, Hans-Ulrich
-
p. 802 - 808
(2007/10/03)
-
- Process for the purification of an aminoalcohol
-
The present invention relates to a process for the preparation of 2-amino-1,3-propanediol, having a content of organic impurities lower than 0.1% and inorganic impurities lower than 0.05%, comprising the following steps: a) formation of a 2-amino-1,3-propanediol salt with an acid; b) crystallization of the salt resulting from step a) from an aqueous or a hydro-organic mixture with a solvent selected from the group consisting of an alcohol of general formula R--OH, wherein R is a C1 -C6 straight or branched alkyl chain, and a mono(C1 -C3)alkylether of the (C3 -C7)alkylcellosolve group; c) elution of the free base by using ion exchangers to give an aqueous solution of said base; d) precipitation or crystallization of the solid 2-amino-1,3-propanediol from a solvent as defined in step b).
- -
-
-
- Synthesis and Hydrolytic Lability of α-Phenoxyacetamides Containing Hydroxy Groups in the N-alkyl Residue
-
Secondary and tertiary amides of 3,5-biscarbonyl>phenoxyacetic acid bearing hydroxy groups in positions β (β-OH) and γ (γ-OH) relative to the acetamide nitrogen atom have been synthesized.Such amides easily undergo cleavage of the acetamide bond in water at neutral pH.Hydrolysis rate constant for a series of such amides and protonation constants for the corresponding leaving amines were determined.No simple correlation between the two parameters could be found.A study of the dependence of these parameters on the structural features of the substrates, such as the presence of an N-methyl group and number of β-OH and γ-OH groups, was carried out.All these features lead to enhancement of the amide hydrolysis rate and a synergistic effect is operative when both N-methyl and β-OH groups are contained in the substrate.Presence of a methyl group increases the basicity of amines whereas β-OH and γ-OH groups have the opposite effect.Mechanistic speculations seem to indicate that the abnormal lability of the acetamide bond is due to protic-like catalysis by an intramolecular OH...N hydrogen bond.
- Anelli, Pier Lucio,Brocchetta, Marino,Canipari, Sonia,Losi, Pietro,Manfredi, Giuseppe,et al.
-
p. 135 - 142
(2007/10/03)
-
- Amino Acids and Peptides; 70. Optically Active α-Amino Acids, N-Boc-Aminoaldehydes and α-Amino-β-hydroxy Acids from 2,3-Epoxy Alcohols
-
Trichloroacetimidic esters of 2,3-epoxy alcohols are transformed into oxazolines 5 and dihydrooxazines 6, respectively, depending on the structure of the educts and the catalyst.The five-membered ring compounds 5 are transformed into erythro-α-amino-β-hydroxy acids (60-70percent from epoxy alcohols) via axazolidinones 11, 12, and 13. α-Amino acids and α-substituted α-amino acids 10 as well as the corresponding aldehydes 9 are obtained from the dihydrooxazines 6 (50-60percent from epoxy alcohols).
- Schmidt, Ulrich,Respondek, Mathias,Lieberknecht, Albrecht,Werner, Juergen,Fischer, Peter
-
p. 256 - 261
(2007/10/02)
-
- Process for the preparation of 2-aminopropanediol-1,3(serinol)
-
2-Aminopropanediol-1,3 (serinol) can be prepared by hydrogenation of the alkali salt of 2-nitro-1,3-propanediol with assuredly high yields by maintaining a narrow range of temperatures of extending from 50°-80° C. by use of a cooling device.
- -
-
-
