Unsaturated Aliphatic Alcohols Research Articles

Multicatalytic Approach to One-Pot Stereoselective Synthesis of Secondary Benzylic Alcohols.

One-pot procedures bear the potential to rapidly build up molecular complexity without isolation and purification of consecutive intermediates. Here, we report multicatalytic protocols that convert alkenes, unsaturated aliphatic alcohols, and aryl boronic acids into secondary benzylic alcohols with high stereoselectivities (typically >95:5 er) under sequential catalysis that integrates alkene cross-metathesis, isomerization, and nucleophilic addition. Prochiral allylic alcohols can be converted to any stereoisomer of the product with high stereoselectivity (>98:2 er, >20:1 dr).

Scientific Opinion on Flavouring Group Evaluation 5, Revision 3 (FGE.05Rev3): Branched‐ and straight‐chain unsaturated aldehydes, dienals, unsaturated and saturated carboxylic acids and related esters with saturated and unsaturated aliphatic alcohols and a phenylacetic acid related ester from chemical groups 1, 2, 3, 5 and 15

The EFSA Panel on Food Additives and Flavourings (FAF) was requested to evaluate 54 flavouring substances attributed to the Flavouring Group Evaluation 05 (FGE.05), using the Procedure as referred to in the Commission Regulation (EC) No 1565/2000. This Revision 3 includes 17 additional substances which have been cleared with respect to genotoxicity in FGE.200Rev1 ([FL‐no: 02.192, 02.231, 05.072, 05.144, 05.184, 05.189, 05.190, 05.191, 05.195, 09.247, 09.400, 09.866, 09.948]) and in FGE.203Rev2 ([FL‐no: 05.081, 05.186, 05.194, 05.196]). The substances were evaluated through a stepwise approach that integrates information on the structure–activity relationships, intake from current uses, toxicological threshold of concern (TTC), and available data on metabolism and toxicity. The Panel concluded that none of the 54 substances gives rise to safety concern at their levels of dietary intake, estimated on the basis of the ‘Maximised Survey‐derived Daily Intake’ (MSDI) approach. Besides the safety assessment of the flavouring substances, the specifications for the materials of commerce have also been considered and found adequate, except for 10 substances ([FL‐no: 08.072, 08.083, 08.101, 08.119, 08.120, 09.181, 09.329, 09.335, 09.379 and 09.637]) for which quantitative figures on the composition of stereoisomeric mixtures are missing and for [FL‐no: 09.578] complete specifications should be provided. Normal and maximum use levels were not available for [FL‐no: 08.072, 08.083, 08.101, 08.119, 08.120, 09.287, 09.326 and 09.578]. Except for flavouring substances [FL‐no: 05.072, 05.081, 05.186, 05.194, 05.196, 09.934 and 09.942], more reliable intake data should be requested for all the 46 flavouring substances, for which use levels were submitted, as their modified Theoretical Added Maximum Daily Intake (mTAMDI) exposure estimates are above the threshold of concern for structural classes I and II. This would include more reliable intake data and then, if required, additional toxicological data.

Unveiling the mechanisms and secrets of chemoselectivities in Au(i)-catalyzed diazo-based couplings with aryl unsaturated aliphatic alcohols

The mechanisms and origins of the unsaturated-aliphatic-alcohols-modulated chemoselectivity of Au-catalyzed carbene transfers from diazo compounds are disclosed by DFT studies.

Testing of the composition of e-cigarette liquids - Manufacturer-declared vs. true contents in a selected series of products

Electronic cigarettes are currently in common use. However, in Poland there is no specific legislation governing the sale of these products. At the same time, no information has been made public about the hazards e-cigarettes pose to the users and bystanders - passive smokers. The aim of the study was to determine the qualitative composition of the analyzed liquid, which is an essential element of regulating the distribution of such cigarettes. Under this study the method for determining the composition of e-cigarette liquids was developed. This method employs gas chromatography with mass spectrometry (GC-MS). Levels of nicotine and flavoring components were determined in 50 e-liquid samples. The results were compared with the information provided by the manufacturer on the packaging. The applied method of qualitative determination helped to identify the main ingredients, such as nicotine and propylene glycol (PG). Propylene glycol was found to be present in all liquids, because it was used as the solvent for nicotine and flavors. There was a good agreement between the declared and the determined content of nicotine in the analyzed samples. The agreement was considerably poorer for the remaining e-liquid ingredients, mainly flavors. There was no agreement between the flavor substances specified by the manufacturer and aroma identified in the e-cigarette liquid, which may pose a risk to users of e-cigarettes, particularly those susceptible to allergies. Several unsaturated aliphatic alcohols and aldehydes found to be present in the liquids, unstable at elevated temperatures, may be more harmful to the smoker than the original compounds. Therefore, it is essential to implement in Poland the legal provisions regarding e-cigarettes. Med Pr 2016;67(2):239-253.

The Chemical Composition of the Essential Oils of Cirsium palustre and C. rivulare and their Antiproliferative Effect

The composition of the essential oils of Cirsium palustre and C. rivulare and their antiproliferative activity against breast adenocarcinoma cells (MCF-7 and MDA-MBA-231) were investigated. The essential oils obtained by hydro-distillation from the roots (yield 0.2 and 0.1% v/w, respectively), leaves and inflorescences (yield below 0.01%), were analyzed by gas chromatography coupled with mass spectrometry (GC-MS). The composition of the essential oils in the respective organs of each plant differed considerably. On the other hand, similarities were observed in the composition of root and leaf oils. In C. palustre and C. rivulare root oil, 50 and 39 constituents were identified, accounting for 95.3% and 92.4% of the total content. The main components were aplotaxene and its derivatives, representing 78.6% and 46.6% of the total content. In leaf oils of both species, 59 and 49 compounds, respectively, were identified, representing 67.4% and 78.3% of the total content. The major constituents were beta-damascenone (4.1% and 13.4%, respectively) and beta-ionone (6.7% and 5.3%, respectively). Short-chain saturated and unsaturated aliphatic alcohols and aldehydes constituted another important group of compounds (17.7% and 9.0%, respectively). The essential oils of the roots have moderate anti-proliferative activity, with IC50 values ranging from 110 to 140 microg/mL. These concentrations were below the level able to inhibit the proliferation of healthy cells.

Identification of volatile components in Chinese Sinkiang fermented camel milk using SAFE, SDE, and HS-SPME-GC/MS

The volatile components of Chinese Sinkiang fermented camel milk were isolated by solvent assisted flavour evaporation (SAFE), simultaneous distillation extraction (SDE, dichloromethane and diethyl ether as solvent, respectively) and headspace solid-phase microextraction (HS-SPME, CAR/PDMS, PDMS/DVB and DVB/CAR/PDMS fibre extraction, respectively) and analysed by GC/MS. A total of 133 volatile components were identified under 6 different conditions, including 30 esters, 20 acids, 18 saturated alcohols, 15 unsaturated aliphatic alcohols, 8 saturated ketones, 9 saturated aldehydes, 8 unsaturated aliphatic aldehydes, 6 furans, 5 sulphur-containing compounds, 5 ethers, 5 lactones, 3 other compounds, and 1 unsaturated aliphatic ketone. Three pretreatment methods were compared, assisted by principal component analysis (PCA). The results indicated that the volatile components obtained using different methods varied greatly both in categories and in content, and therefore, a multi-pretreatment method should be adopted together with GC/MS. A total of 71 aroma-active compounds were detected by gas chromatography-olfactometry (GC–O), among which 66 aroma-active compounds were found by SDE (60, dichloromethane as solvent; 24, diethyl ether as solvent), 26 by SAFE.

Cellulose swelling by protic solvents: which properties of the biopolymer and the solvent matter?

The question posed in the title has been addressed by studying the swelling of celluloses at 20 °C by twenty protic solvents, including water; linear- and branched-chain aliphatic alcohols; unsaturated aliphatic alcohols, and alkoxyalcohols. The biopolymers investigated included microcrystalline cellulose, MC, native and never-dried mercerized cotton cellulose, cotton and M-cotton, and native and never-dried mercerized eucalyptus cellulose, eucalyptus and M-eucalyptus, respectively. In most cases, better correlations with the physico-chemical properties of the solvents were obtained when the swelling was expressed as number of moles of solvent/anhydroglucose unit, nSw, rather than as % increase in sample weight. The descriptors employed in these correlations included, where available, Hildebrand’s solubility parameters, Gutmann’s acceptor and donor numbers, solvent molar volume, VS, as well as solvatochromic parameters. The latter, employed for the first time for correlating the swelling of biopolymers, included empirical solvent polarity, ET(30), solvent “acidity”, αS, “basicity”, βS, and dipolarity/polarizability, π S * , respectively. Small regression coefficients and large sums of the squares of the residues were obtained when values of nSw were correlated with two solvent parameters. Much better correlations were obtained with three solvent parameters. The most statistically significant descriptor in the correlation equation depends on the cellulose, being π S * for MC, cotton, and eucalyptus, and VS for M-cotton and M-eucalyptus. The best correlations were obtained with the same set of four parameters for all celluloses, namely, solvent pKa (or αS) βS, π S * , and VS, respectively. These results indicate that the supra-molecular structure of the biopolymer, in particular the average sizes of crystallites and micro-pores, and the presence of its chains in parallel (cellulose I) or anti-parallel (cellulose II) arrangements control its swelling. At least for the present biopolymer/solvent systems, use of solvatochromic parameters is a superior alternative to Hildebrand’s solubility parameters and/or Gutmann’s acceptor and donor numbers. The relevance of these results to the accessibility of the hydroxyl groups of cellulose, hence to its reactivity, is briefly discussed.

Electrophysiological and behavioural responses of Melolontha melolontha to saturated and unsaturated aliphatic alcohols

AbstractMale Melolontha cockchafers are known to use green leaf volatiles induced by female feeding on host plants for their mate location. Earlier studies of the response of the European cockchafer, Melolontha melolontha L. (Coleoptera: Scarabaeidae), to different green leaf aldehydes, alcohols, and acetates revealed that only green leaf alcohols were attractive to males in the field. Females were not attracted at all by these volatiles. Here, we present a study that aimed to elucidate the structure–activity relationships of aliphatic alcohols. Both behavioural and physiological responses were studied in male and female M. melolontha by field tests and electroantennography. The compounds tested were saturated aliphatic alcohols with chain lengths between five and eight carbon atoms. Furthermore, the cockchafer's response to six‐carbon alcohols with (E)‐2‐, (E)‐3‐, (Z)‐2‐, (Z)‐3‐, and (Z)‐4‐configurated double bonds was tested. All compounds elicited dose‐dependent responses on the antennae of both sexes. In general, males showed a stronger normalized EAG response to the stimuli than females. However, only the naturally occurring six‐carbon alcohols, i.e., 1‐hexanol (E)‐2‐, (Z)‐3, and (E)‐3‐hexen‐1‐ol were attractive to M. melolontha males in the field. Females were not attracted to any of the tested compounds, confirming previous results on the olfactory orientation of Melolontha cockchafers.

Long chain n-alkyl diols, hydroxy ketones and sterols in a marine eustigmatophyte, Nannochloropsis gaditana, and in Brachionus plicatilis feeding on the algae

Base-hydrolyzed sterols and long-chain alcohols of a marine eustigmatophyte, Nannochloropsis gaditana have been studied. Sterol composition of N. gaditana is similar to that of other member of this genus, with predominance of cholest-5-en-3β-ol and 24-ethylcholest-5-en-3β-ol. The C29:2 and C30:1 unsaturated aliphatic alcohols were predominant. Saturated and monounsaturated C28 to C36n-alkyl diols occurred as a mixture of positional isomers with ω16 predominating among the C28 alkyl diols, ω18 among C30, C32, C34 and C36 alkyl diols and ω17 for the odd chain alkyl diols. C28–C32 hydroxy ketones were identified for the first time in a marine organism, with a distribution parallelling the alkyl diol mixtures and suggesting a biosynthetic relation between both alcohol classes. N. gaditana was fed to Brachionus plicatilis and the distribution of alkyl diol positional isomers remained the same in the algae and the rotifer fecal pellets. However, digestion resulted in an increase in C30 diols relative to C32 diols and in an enrichment of unsaturated long-chain alcohols relative to alkyl diols.

The identification of odorous metabolites produced from algal monocultures

Four algal species commonly found in the River Seine were cultured for a comprehensive investigation of their odorous metabolites. Closed loop stripping analysis (CLSA), open stripping analysis (OSA) and steam distillation extraction (SDE) were used to extract and concentrate a wide range of metabolites. The odour causing compounds were identified by a combination of chemical (gas chromatography-mass spectrometry (GC-MS)) and sensory (sensory-gas chromatography (sensory-GC), flavour profile analysis (FPA)) analyses. The compounds found responsible for unpleasant odours were alkenes, saturated and unsaturated aliphatic alcohols, aldehydes, ketones, sulphides and pyrazines. Some of the odorous compounds responsible for septic and muddy/musty odours may have been of bacterial or fungal origin as the cultures were non-axenic. Sensory-GC was found to be a valuable tool in identifying compounds of very low odour thresholds, which were present at or below the detection limits of the GC-MS.

The identification of odorous metabolites produced from algal monocultures

Four algal species commonly found in the River Seine were cultured for a comprehensive investigation of their odorous metabolites. Closed loop stripping analysis (CLSA), open stripping analysis (OSA) and steam distillation extraction (SDE) were used to extract and concentrate a wide range of metabolites. The odour causing compounds were identified by a combination of chemical (gas chromatography-mass spectrometry (GC-MS)) and sensory (sensory-gas chromatography (sensory-GC), flavour profile analysis (FPA)) analyses. The compounds found responsible for unpleasant odours were alkenes, saturated and unsaturated aliphatic alcohols, aldehydes, ketones, sulphides and pyrazines. Some of the odorous compounds responsible for septic and muddy/musty odours may have been of bacterial or fungal origin as the cultures were non-axenic. Sensory-GC was found to be a valuable tool in identifying compounds of very low odour thresholds, which were present at or below the detection limits of the GC-MS.

Rate constants for the gas‐phase reactions of Ozone with unsaturated Aliphatic Alcohols

AbstractThe gas‐phase reaction of ozone with unsaturated alcohols in air has been investigated at atmospheric pressure and ambient temperature (288–291 K). Cyclohexane was added to scavenge the hydroxyl radical which forms as a product of the ozone–unsaturated alcohol reaction. The reaction rate constants, in units of 10−18 cm3 molecule−1 s−1, are 16.2 ± 0.7 for (±) 3‐buten‐2‐ol, 17.9 ± 1.8 for 1‐penten‐3‐ol, 10.0 ± 0.3 for 2‐methyl‐3‐buten‐2‐ol, 169 ± 25 for cis‐2 penten‐1‐ol, and 251 ± 41 for 2‐buten‐1‐ol (mixture of isomers). Substituent effects on reactivity are discussed. The reactivity of unsaturated alcohols towards ozone is similar to that of their alkene structural homologues. Implications of these results with respect to the atmospheric persistence of unsaturated alcohols are briefly discussed. © 1994 John Wiley & Sons, Inc.

Volatile Odorous Excretion Products of Algae and Their Occurrence in the Natural Aquatic Environment

Members of many algal groups (Chrysophyceae, Cryptophyceae, Dinophyceae, Chlorophyceae and Bacillariophyceae) have been reported to impart characteristic odours to water when blooms of these organisms occur. The volatile compounds isolated from algal cultures under controlled laboratory conditions and from surface waters during algal bloom periods are listed. The substances identified as responsible for odour problems are alkenes, saturated and unsaturated aliphatic alcohols, aldehydes, ketones, esters, thioesters and sulfides. Experimental conditions and criteria enabling one to distinguish between algal excretion products and contaminants, or pollution products are put forward.

ChemInform Abstract: THE FORMATION OF ETHERS FROM UNSATURATED ALIPHATIC ALCOHOLS IN THE PRESENCE OF BORON TRIFLUORIDE ETHERATE

AbstractDie Etherbildung der Alkohole (I), (IV), (V) und (X) in Gegenwart von katalytischen Mengen BF3‐etherat wird untersucht.

The Formation of Ethers from Unsaturated Aliphatic Alcohols in the Presence of Boron Trifluoride Etherate

Abstract Unsaturated acyclic alcohols of carbon numbers four and five reacted with boron trifluoride etherate to give eight ethers. Of these ethers, novel acyclic di- and tri-ethers were found in the reaction products of 2-methyl-2-propen-1-ol. Boron trifluoride etherate catalyzes double-bond migration, allylic rearrangement, intermolecular dehydration, and Markownikov addition reactions in unsaturated aliphatic alcohols.

Reactions of hydroxyl radicals with unsaturated aliphatic alcohols in aqueous solution. Spectroscopic and electron spin resonance radiolysis study

Reactions of hydroxyl radicals with unsaturated aliphatic alcohols in aqueous solution. Spectroscopic and electron spin resonance radiolysis study