- Oxidation of cyclohexanone and/or cyclohexanol catalyzed by Dawson-type polyoxometalates using hydrogen peroxide
-
The oxidation of cyclohexanone, cyclohexanol or cyclohexanone/cyclohexanol mixture using as catalyst, Dawson-type polyoxometalates (POMs) of formula, α- and β-K6P2W18O62, α-K6P2Mo6W12O62 and α1-K7P2Mo5VW12O62 and hydrogen peroxide, carried out at 90 °C with a reaction time of 20 h, led to a high number of mono- and di-acids which were identified by GC-MS. Levulinic, 6-hydroxyhexanoic, adipic, glutaric and succinic acids, major products were evaluated by HPLC. Regardless of the substrate nature, all POMs exhibited high catalytic activity with 94–99% of conversion, whereas the formation of the different products is sensitively related to both the composition and symmetry of the POMs and the substrate nature. The main products are adipic acid in the presence of α-K6P2Mo6W12O62 and α1-K7P2Mo5VW12O62, levulinic acid in the presence of α1-K7P2Mo5VW12O62 and β-K6P2W18O62 and 6-hydroxyhexanoic acid in the presence of α- and β-K6P2W18O62. Graphical abstract: High catalytic activity was observed with?α- and?β-K6P2W18O62, α-K6P2Mo6W12O62 and α1-K7P2Mo5VW12O62 Dawson-type for the oxidation of cyclohexanone, cyclohexanol or cyclohexanone/cyclohexanol mixture, in the hydrogen peroxide presence, to several oxygenated products. Adipic, levulinic and 6-hydroxyhexanoic acids are the main products. The peroxo- species formed in situ could be the active sites.[Figure not available: see fulltext.]
- Dermeche, Leila,Idrissou, Yasmina,Mazari, Tassadit,Moudjahed, Mohammed,Rabia, Cherifa
-
-
- A Heterogeneous Pt-ReOx/C Catalyst for Making Renewable Adipates in One Step from Sugar Acids
-
Renewable adipic acid is a value-added chemical for the production of bioderived nylon. Here, the one-step conversion of mucic acid to adipates was achieved in high yield through deoxydehydration (DODH) and catalytic transfer hydrogenation (CTH) by a bifunctional Pt-ReOx/C heterogeneous catalyst with isopropanol as solvent and reductant. The Pt-ReOx/C catalyst is reusable and was regenerated at least five times. The catalyst exhibits a broad substrate scope of various diols. Spectroscopic studies of Pt-ReOx/C revealed ReVII and Pt0 as the relevant species for DODH and CTH, respectively. Isotope labeling experiments support a monohydride mechanism for CTH over Pt. This work demonstrates a reusable bifunctional catalyst for a one-step valorization of sugar acids to a practical monomer, which opens the door to multifunctional catalysis streamlining valorization of biomass-derived molecules.
- Jang, Jun Hee,Ro, Insoo,Christopher, Phillip,Abu-Omar, Mahdi M.
-
-
- Efficient Palladium-Catalyzed Carbonylation of 1,3-Dienes: Selective Synthesis of Adipates and Other Aliphatic Diesters
-
The dicarbonylation of 1,3-butadiene to adipic acid derivatives offers the potential for a more cost-efficient and environmentally benign industrial process. However, the complex reaction network of regioisomeric carbonylation and isomerization pathways, make a selective and direct transformation particularly difficult. Here, we report surprising solvent effects on this palladium-catalysed process in the presence of 1,2-bis-di-tert-butylphosphin-oxylene (dtbpx) ligands, which allow adipate diester formation from 1,3-butadiene, carbon monoxide, and methanol with 97 % selectivity and 100 % atom-economy under scalable conditions. Under optimal conditions a variety of di- and triesters from 1,2- and 1,3-dienes can be obtained in good to excellent yields.
- Yang, Ji,Liu, Jiawang,Ge, Yao,Huang, Weiheng,Ferretti, Francesco,Neumann, Helfried,Jiao, Haijun,Franke, Robert,Jackstell, Ralf,Beller, Matthias
-
supporting information
p. 9527 - 9533
(2021/03/08)
-
- Preparation process and equipment of diisopropyl adipate
-
The invention relates to a preparation process of diisopropyl adipate. The finished product of diisopropyl adipate is obtained through esterification reaction, dealcoholization, distillation, water washing, dehydration and filtration. A homogeneous catalyst selected in the esterification reaction has high catalytic activity and improves the reaction efficiency, then a film evaporator is combined for separation and refining, a catalyst in the product is effectively removed, the product quality is improved, some impurities influencing the product quality are rapidly and effectively removed through warm water washing, and the obtained product is high in purity, can be stored for a long time, and has neglected corrosion to equipment and extremely small pollution to the environment. In addition, the invention also provides equipment for the preparation process of diisopropyl adipate. The equipment comprises a reaction kettle, a condenser, a water segregator, a distillation kettle, a dealcoholization tower, the film evaporator, a washing tank, a dehydrator, a filtering device and a finished product tank.
- -
-
Paragraph 0078-0119
(2021/07/01)
-
- Direct synthesis of adipic acid esters via palladium-catalyzed carbonylation of 1,3-dienes
-
The direct carbonylation of 1,3-butadiene offers the potential for a more cost-efficient and environmentally benign route to industrially important adipic acid derivatives. However, owing to the complex reaction network of regioisomeric carbonylation and isomerization pathways, a selective practical catalyst for this process has thus far proven elusive. Here, we report the design of a pyridyl-substituted bidentate phosphine ligand (HeMaRaphos) that, upon coordination to palladium, catalyzes adipate diester formation from 1,3-butadiene, carbon monoxide, and butanol with 97% selectivity and 100% atom-economy under industrially viable and scalable conditions (turnover number > 60,000). This catalyst system also affords access to a variety of other di- and triesters from 1,2- and 1,3-dienes.
- Yang, Ji,Liu, Jiawang,Neumann, Helfried,Franke, Robert,Jackstell, Ralf,Beller, Matthias
-
p. 1514 - 1517
(2020/01/08)
-
- Metal-free transesterification catalyzed by tetramethylammonium methyl carbonate
-
Environmentally benign metal-free tetramethylammonium methyl carbonate is effective as a catalyst for the chemoselective, scalable, and reusable transesterification of various esters and alcohols in common organic solvents. In situ-generated highly active species, tetramethylammonium alkoxides, can greatly avoid self-decomposition at ≤110 °C, and are reusable. In particular, chelating substrates, such as amino alcohols, diols, triols, sugar derivatives, alkaloids, α-amino acid esters, etc., which deactivate conventional metal salt catalysts, can be used. A 100 gram scale biodiesel production was also demonstrated.
- Hatano, Manabu,Tabata, Yuji,Yoshida, Yurika,Toh, Kohei,Yamashita, Kenji,Ogura, Yoshihiro,Ishihara, Kazuaki
-
supporting information
p. 1193 - 1198
(2018/03/27)
-
- Desymmetrizing Hydroformylation of Dihydromuconic Acid Diesters: Application to the Synthesis of (±)-Vindeburnol
-
The desymmetrizing hydroformylation of internal alkenes derived from dihydromuconic acid is described. The study of this reaction afforded easy access to polyfunction aldehydes. After the evaluation of the reactivity of the dimethyl ester derivative with various primary amines, this methodology was used to design a rapid synthesis of (±)-vindeburnol from tryptamine in only two steps.
- Salacz, Laura,Charpentier, Cyrille,Suffert, Jean,Girard, Nicolas
-
p. 2257 - 2262
(2017/02/26)
-
- CYCLOHEXANE OXIDATION PROCESS BYPRODUCT DERIVATIVES AND METHODS FOR USING THE SAME
-
Disclosed are ester compositions, solvents, cleaning formulations, curing agents, reactive diluent solvents, controlled acid function release agents, polyol monomers, drilling mud and methods of making and using the same. Disclosed compositions include: a) about 10 to 60 weight percent methyl hydroxycaproate; b) about 20 to 80 weight percent dimethyl adipate; c) about 1 to 15 wt % of dimethyl glutarate; d) about 0.1 to 5 wt % of dimethyl succinate; e) about 0.1 to 7 wt % of at least one cyclohexanediol; and f) less than about 20 wt% oligomeric esters.
- -
-
Page/Page column 50-51
(2010/08/05)
-
- SKIN EXTERNAL PREPARATIONS AND COSMETICS
-
An object of the present invention is to provide skin external preparations and cosmetics which contain a branched acyl carnitine and have excellent formulation stability. A skin external preparation of the present invention includes a carnitine derivative represented by the following Formula (1) and/or a carnitine derivative salt represented by the following Formula (2), and an amphoteric surfactant. In Formula (1), R1 and R2 are each independently a C1-18 optionally branched, saturated or unsaturated aliphatic hydrocarbon group. In Formula (2), R1 and R2 are the same as in Formula (1), X? is a specific anion and Y+ is a specific cation.
- -
-
-
- Synergism of microwaves and immobilized enzyme catalysis in synthesis of adipic acid esters in nonaqueous media
-
Low-energy microwave irradiation leads to enhancement by a factor of up to 2.63 in comparison with conventional heating in immobilized lipase-catalyzed esterification of adipic acid with various alcohols and this effect is due to the greater frequency of collision, without any change in activation energy of the two modes of heating. Copyright Taylor & Francis, Inc.
- Yadav, Ganapati D.,Lathi, Piyush S.
-
p. 1699 - 1705
(2007/10/03)
-
- Direct oxidative cleavage of α- and β-dicarbonyls and α-hydroxyketones to diesters with KHSO5
-
Presented is a methodology to oxidatively cleave α-hydroxyketones and α- or β-diones using the environmentally benign reagent KHSO 5, prepared easily from Oxone, to diesters in one simple transformation. In addition, we undertook a mechanistic study to provide a plausible mechanistic interpretation. These reactions may prove to be valuable alternatives to other related metal-mediated processes.
- Yan, Jun,Travis, Benjamin R.,Borhan, Babak
-
p. 9299 - 9302
(2007/10/03)
-
- Na2CO3/SOCl2: A mild and convenient reagent for the preparation of isopropyl carboxylates
-
Na2CO3/SOCl2 has been used for esterification of aliphatic and aromatic acids with isopropanol. This esterification method is compatible with a wide assortment of functional groups.
- Kazemi, Foad,Kiasat, Ali Reza,Mombaini, Began
-
p. 1187 - 1191
(2007/10/03)
-
- Monohydric alcohol derived urethanes and their use in cosmetic formulations
-
The present invention relates to a dimeric urethane compounds derived from monohydric alcohols, generally fatty alcohols, and a diisocyanate according to the following reaction scheme: wherein R1is selected from the group of saturated, unsaturated or halogen substituted linear, cyclic or branch-chained hydrocarbons and R2is a linear, cyclic or branch-chained alkyl or aminoalkyl group ranging from two to 200 carbon atoms, preferably two to 50 carbons, more preferably 6 to 36 carbons, even 6 to 24 carbons, said urethane compound being substantially free from terminal hydroxyl groups.
- -
-
-
- Monohydric alcohol derived urethanes and their use in cosmetic formulations
-
The present invention relates to a dimeric urethane compounds derived from monohydric alcohols, generally fatty alcohols, and a diisocyanate according to the following reaction scheme: wherein R1 is selected from the group of saturated, unsaturated or halogen substituted linear, cyclic or branch-chained hydrocarbons and R2 is a linear, cyclic or branch-chained alkyl or aminoalkyl group ranging from two to 200 carbon atoms, preferably two to 50 carbons, more preferably 6 to 36 carbons, even 6 to 24 carbons, said urethane compound being substantially free from terminal hydroxyl groups.
- -
-
-
- Synthesis of α,ω-dicarboxylic acid dimethyl esters from cycloalkanones
-
Reaction of cycloalkanones with [hydroxy(2,4-dinitrobenzenesulfonyloxy)iodo]benzene and subsequent treatment of α-[(2,4-dinitrobenzene)sulfonyl]oxy cycloalkanone intermediates with Oxone and PTSA in MeOH-H2O (6:1, v/v) solution provided dicarboxylic acid dimethyl esters in high yields.
- Lee, Jong Chan,Ku, Chang Hoe
-
p. 1679 - 1680
(2007/10/03)
-
- Monohydric alcohol derived urethanes and their use in cosmetic formulations
-
The present invention relates to a dimeric urethane compounds derived from monohydric alcohols, generally fatty alcohols, and a diisocyanate according to the following reaction scheme: STR1 wherein R1 is selected from the group of saturated or halogen substituted linear, cyclic or branch-chained hydrocarbons and R2 is a linear, cyclic or branch-chained alkyl or aminoalkyl group ranging from two to 200 carbon atoms, preferably two to 50 carbons, more preferably 6 to 36 carbons, said urethane compound being substantially free from terminal hydroxyl groups.
- -
-
-
- Esterification in dry media using ferric perchlorate adsorbed on silica gel
-
Adsorption of Fe(ClO4)3(H2O)6 onto chromatographic grade silica gel in the presence of alcohol ( to be used for esterification ) produces a supported reagent, Fe(ClO4)3(ROH)6/SiO2. This reagent, has been found effective for the rapid and high yield of esters, on grinding in the presence of carboxylic acids using pestle and mortar in the solid state.
- Parmar, Anupama,Kaur, Jatinder,Goyal, Rita,Kumar, Baldev,Kumar, Harish
-
p. 2821 - 2826
(2007/10/03)
-
- α-nitrocycloalkanones as a source of α,ω,-dicarboxylic acid dimethyl esters
-
α,ω-Dicarboxylic acid dimethyl esters arc easily obtained by ring cleavage of α-nitrocycloalkanones. Thus, reaction of the latter compounds with three equivalents of potassium persulfate, in methanol and in presence of sulfuric acid at 80 °C, provides α,ω-dicarboxylic acid dimethyl esters in high yields. Long-chain, and alkylated α,ω-dicarboxylic acid dimethyl esters can be also efficiently obtained.
- Ballini, Roberto,Bosica, Giovanna
-
p. 16131 - 16138
(2007/10/03)
-
- Process for the preparation of bis(amidocarboxylic acids)
-
A process is reported for the preparation of bis(amidocarboxylic acid) involving reacting an ester with an aminocarboxylate compound, the latter being formed from lactams or aminocarboxylic acids and salts thereof. The ester and aminocarboxylate compound are present in a weight ratio of about 1:1 to about 1:4, and reaction is conducted in a mono- or polyhydric alcohol solvent.
- -
-
-
- Lip treatment composition
-
A lip-treatment composition for topical application to the lips comprising a base comprising oil, water and a structurant, and at least one active component active with regard to the lips, gums, teeth, throat, or oral mucosa.
- -
-
-
- Cosmetic composition
-
A composition suitable for topical application to mammalian skin or hair for inducing, maintaining or increasing hair growth comprises: (i) a first chemical inhibitor chosen from proteoglycanase inhibitors, glycosaminoglycanase inhibitors, glycosaminoglycan chain cellular uptake inhibitors or mixtures thereof; and (ii) a cosmetically acceptable vehicle for the chemical inhibitor; provided that when the first chemical inhibitor is a weak inhibitor, such that a 1 mM aqueous solution of the inhibitor reduces proteoglycanase activity, glycosaminoglycanase activity or cellular uptake of glycosaminoglycan chains, by from 5 to 50%, in accordance with at least one of the assay tests as herein described, then there is also present in the composition a second chemical inhibitor and/or an activity enhancer. When minoxidil is the sole chemical inhibitor, then the activity enhancer is a penetration enhancer chosen from a limited number of materials, including certain esters and cationic polymers. The total amount of chemical inhibitor present in the composition is sufficient to increase hair growth in the rat, when said composition is applied topically thereto, by at least 10% more than that obtainable using a control composition from which the said inhibitors have been omitted.
- -
-
-
