26776-28-3

Hazards Identification

Hazards Summary:

Linear alkyl diacids cluster: Group members and supporting chemicals demonstrate eye irritation in rabbits; no evidence of skin sensitization; low oral repeated dose systemic toxicity and developmental toxicity; no adverse effects to reproductive organs in repeated-dose studies; no evidence of mutagenicity; [EPA ChAMP: Hazard Characterization] May cause irritation; [Acros Organics MSDS]

Usage

InChI:InChI=1/C9H16O4/c10-8(11)6-4-2-1-3-5-7-9(12)13/h1-7H2,(H,10,11)(H,12,13)

Upstream product

• 56-23-5 tetrachloromethane 
• 112-79-8 Elaidic acid 
• 509-14-8 tetranitromethane 
• 74244-64-7 cycloheptadec-9-en-1-one 
• 79-21-0 peracetic acid 
• 506-24-1 Stearolic acid 
• 23875-96-9 5t-[2]furyl-penta-2t,4-dienoic acid 
• 334-43-0 1-chloro-7-fluoro-heptane 
• 15719-64-9 methylammonium carbonate 
• 506-25-2 octadec-17-ene-9,11-diynoic acid 
• 593-25-9 9-undecenoic acid 
• 112-80-1 cis-Octadecenoic acid 
• 544-72-9 9-cis,11-trans,13-cis-octadecatrienoic acid 
• 506-23-0 eleostearic acid 

Downstream Products

• 83327-23-5 Azelainsaeure-ditetrahydrofurfurylester 
• 7507-11-1 azelaic acid bis-(3-tetrahydro[2]furyl-propyl ester) 
• 7702-52-5 azelaic acid bis-(1-methyl-3-tetrahydro[2]furyl-propyl ester) 
• 4471-27-6 1,4-dioxacyclotridecane-5,13-dione 
• 74783-04-3 1,4,14,17-tetraoxa-cyclohexacosane-5,13,18,26-tetraone 
• 1842-72-4 1,7-heptanedicarboxamide 
• 96310-16-6 nonanedioic acid bis-(4-isopropyl-benzyl ester) 
• 108748-30-7 nonanedioic acid mono-sec-butyl ester 
• 57983-36-5 di-2-butyl azelate 
• 25960-11-6 Azelainsaeure-dioctadecylester 
• 97361-62-1 Azelainsaeure-monoisopentylester 
• 693-46-9 1,7-Difluor-heptan 
• 129577-60-2 4-Ethoxy-benzoic acid 4-((E)-2-pyridin-4-yl-vinyl)-phenyl ester; compound with nonanedioic acid 
• 106664-96-4 bis(2,5-dioxopyrrolidin-1-yl) nonanedioate 

Relevant academic research and scientific papers

Scalable, sustainable and catalyst-free continuous flow ozonolysis of fatty acids

A simple and efficient catalyst-free protocol for continuous flow synthesis of azelaic acid is developed from the renewable feedstock oleic acid. An ozone and oxygen mixture was used as the reagent for oxidative cleavage of double bond without using any metal catalyst or terminal oxidant. The target product was scaled up to more than 100 g with 86% yield in a white powder form. Complete recycling and reuse of the solvent were established making it a green method. The approach is significantly energy efficient and also has a very small chemical footprint. The methodology has been successfully tested with four fatty acids making it a versatile platform that gives value addition from renewable resources.

FLOW CHEMISTRY SYNTHESIS OF ISOCYANATES

The disclosure provides, inter alia, safe and environmentally-friendly methods, such as flow chemistry, to synthesize isocyanates, such as methylene diphenyl diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and tetramethylxylene diisocyanate.

METHOD FOR MANUFACTURING PELARGONIC ACID AND AZELAIC ACID

The present invention relates to a method for producing pelargonic acid and azelaic acid, and more specifically, provides a method for producing pelargonic acid and azelaic acid, which comprises the following steps of: a) reacting an unsaturated carboxylic acid compound under a tungstic acid catalyst to obtain an intermediate product comprising vicinal diol; and b) reacting the intermediate product under a transition metal hydroxide catalyst to obtain the pelargonic acid and azelaic acid. The production method is capable of producing the pelargonic acid and azelaic acid in a high yield from the unsaturated carboxylic acid compound.

Oxidative carbon-carbon bond cleavage of 1,2-diols to carboxylic acids/ketones by an inorganic-ligand supported iron catalyst

The carbon-carbon bond cleavage of 1,2-diols is an important chemical transformation. Although traditional stoichiometric and catalytic oxidation methods have been widely used for this transformation, an efficient and valuable method should be further explored from the views of reusable catalysts, less waste, and convenient procedures. Herein an inorganic-ligand supported iron catalyst (NH4)3[FeMo6O18(OH)6]·7H2O was described as a heterogeneous molecular catalyst in acetic acid for this transformation in which hydrogen peroxide was used as the terminal oxidant. Under the optimized reaction conditions, carbon-carbon bond cleavage of 1,2-diols could be achieved in almost all cases and carboxylic acids or ketones could be afforded with a high conversion rate and high selectivity. Furthermore, the catalytic system was used efficiently to degrade renewable biomass oleic acid. Mechanistic insights based on the observation of the possible intermediates and control experiments are presented.

Process for preparing azelaic acid

A process for preparing azelaic acid is disclosed. In particular, the process for preparing azelaic acid is an ozone free process. The process for preparing azelaic acid comprises a step of decarboxylation of tetra-carboxylic acid in the presence of a organic sulfonic acid.

Reactive Species and Reaction Pathways for the Oxidative Cleavage of 4-Octene and Oleic Acid with H2O2over Tungsten Oxide Catalysts

Oxidative cleavage of carbon-carbon double bonds (C-C) in alkenes and fatty acids produces aldehydes and acids valued as chemical intermediates. Solid tungsten oxide catalysts are low cost, nontoxic, and selective for the oxidative cleavage of C-C bonds with hydrogen peroxide (H2O2) and are, therefore, a promising option for continuous processes. Despite the relevance of these materials, the elementary steps involved and their sensitivity to the form of W sites present on surfaces have not been described. Here, we combine in situ spectroscopy and rate measurements to identify significant steps in the reaction and the reactive species present on the catalysts and examine differences between the kinetics of this reaction on isolated W atoms grafted to alumina and on those exposed on crystalline WO3 nanoparticles. Raman spectroscopy shows that W-peroxo complexes (W-(η2-O2)) formed from H2O2 react with alkenes in a kinetically relevant step to produce epoxides, which undergo hydrolysis at protic surface sites. Subsequently, the CH3CN solvent deprotonates diols to form alpha-hydroxy ketones that react to form aldehydes and water following nucleophilic attack of H2O2. Turnover rates for oxidative cleavage, determined by in situ site titrations, on WOx-Al2O3 are 75% greater than those on WO3 at standard conditions. These differences reflect the activation enthalpies (ΔH?) for the oxidative cleavage of 4-octene that are much lower than those for the isolated WOx sites (36 ± 3 and 60 ± 6 kJ·mol-1 for WOx-Al2O3 and WO3, respectively) and correlate strongly with the difference between the enthalpies of adsorption for epoxyoctane (ΔHads,epox), which resembles the transition state for epoxidation. The WOx-Al2O3 catalysts mediate oxidative cleavage of oleic acid with H2O2 following a mechanism comparable to that for the oxidative cleavage of 4-octene. The WO3 materials, however, form only the epoxide and do not cleave the C-C bond or produce aldehydes and acids. These differences reflect the distinct site requirements for these reaction pathways and indicate that acid sites required for diol formation are strongly inhibited by oleic acids and epoxides on WO3 whereas the Al2O3 support provides sites competent for this reaction and increase the yield of the oxidative cleavage products.

Conversion of oleic acid into azelaic and pelargonic acid by a chemo-enzymatic route

A chemo-enzymatic approach for the conversion of oleic acid into azelaic and pelargonic acid is herein described. It represents a sustainable alternative to ozonolysis, currently employed at the industrial scale to perform the reaction. Azelaic acid is produced in high chemical purity in 44% isolation yield after three steps, avoiding column chromatography purifications. In the first step, the lipase-mediated generation of peroleic acid in the presence of 35% H2O2 is employed for the self-epoxidation of the unsaturated acid to the corresponding oxirane derivative. This intermediate is submitted to in situ acid-catalyzed opening, to afford 9,10-dihydroxystearic acid, which readily crystallizes from the reaction medium. The chemical oxidation of the diol derivative, using atmospheric oxygen as a stoichiometric oxidant with catalytic quantities of Fe(NO3)3·9·H2O, (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO), and NaCl, affords 9,10-dioxostearic acid which is cleaved by the action of 35% H2O2 in mild conditions, without requiring any catalyst, to give pelargonic and azelaic acid.

Synthesis of Branched Biolubricant Base Oil from Oleic Acid

The mature manufacturing of synthetic lubricants (poly-α-olefins, PAO) proceeds through oligomerization, polymerization, and hydrogenation reactions of petrochemical ethylene. In this work, we utilize the inexpensive bio-derived oleic acid as raw material to synthesize a crotch-type C45 biolubricant base oil via a full-carbon chain synthesis without carbon loss. It contains several cascade chemical processes: oxidation of oleic acid to azelaic acid (further esterification to dimethyl azelate) and nonanoic acid (both C9 chains). The latter is then selectively hydrogenated to nonanol and brominated to the bromo-Grignard reagent. In a next step, a C45 biolubricant base oil is formed by nucleophilic addition (NPA) of excessive C9 bromo-Grignard reagent with dimethyl azelate, followed by subsequent hydrodeoxygenation. The specific properties of the prepared biolubricant base oil are almost equivalent to those of the commercial lubricant PAO6 (ExxonMobil). This process provides a new promising route for the production of value-added biolubricant base oils.

Characterization of Bitter-Tasting Oxylipins in Poppy Seeds (Papaver somniferum L.)

Activity-guided fractionation of poppy seed (Papaver somniferum L.) extracts and analysis of fatty acid oxidation model experiments, followed by liquid chromatography time-of-flight mass spectrometry, tandem mass spectrometry, and one-/two-dimensional nuclear magnetic resonance experiments, revealed the chemical structures of five bitter-tasting fatty acids (1-5), three monoglycerides (6-8), six C18-lipidoxidation products (9-14), and four lipid oxidation degradation products (15 and 17-19) as well as two previously unreported monoglyceride oxidation degradation products, namely, 9-(2′,3′-dihydroxypropyloxy)-9-oxononaic acid (1-azeloyl-rac-glycerol, 16) and 1-(2′,3′-dihydroxypropyl)-8-(5″-oxo-2″,5″-dihydrofruan-2″-yl)-octonoate (1-ODFO-rac-glycerol, 20). Sensory studies exhibited low bitter taste threshold concentrations between 0.08 and 0.29 mmol/L, particularly for the higher oxidated C18-fatty acids trihydroxyoctadecenoic acid (THOE, 12), 12,13-dihydroxy-9-oxo-10-octadecenoic acid (12,13-diOH-9-oxo, 13), and 9,10-dihydroxy-13-oxo-11-octadecenoic acid (9,10-diOH-13-oxo, 14) as well as for the lipidoxidation degradation products 4-hydroxy-2-noneic acid (4-HNA, 17), 4-hydroxy-2-docecendienoic acid (HDdiA, 18), and 8-(5′-oxo-2′,5′-dihydrofuran-2′-yl)-octanoic acid (ODFO, 20).

Preparation method of biomass-based azelaic acid

The invention discloses a preparation method of biomass-based azelaic acid. The method comprises the following steps: 1) in an aqueous solution, carrying out aldol condensation reaction on 5-formyl-2-furancarboxylic acid and pyruvic acid on a base catalyst to generate a C9 condensation product; 2) carrying out hydrogenation reaction on the C9 condensation product in the presence of a hydrogenationcatalyst to generate a C9 saturated product; and 3) performing hydrogenolysis reaction on the C9 saturated product on the hydrogenolysis catalyst to generate azelaic acid. According to the invention,biomass-based platform molecules are used as reaction raw materials, water is used as a reaction solvent, a heterogeneous catalyst which is easy to recycle is adopted, the catalyst has high catalyticactivity and cycling stability, and the reaction process is green, pollution-free and environment-friendly.