Surfactants containing ethylene oxide: Relationship of structure to biodegradability

Anionic ethoxy sulfate and nonionic ethoxylate surfactants were prepared from the following straight-chain hydrophobes: fatty or Ziegler primary alcohols, oxo alcohols derived from straight-chain olefins, secondary straight-chain alcohols and straight-chain alkylphenols. These were studied to relate biodegrability to the following elements of structure: the nature of the connecting link, its position of attachment to the hydrophobe, the chain length of the hydrophobe, and the length of the ethylene oxide chain used. Previously described methods were used to estimate both rate and completeness of degradation in river water as well as activated sludge environments. Data are presented to support the following conclusions.

1. 1)
   All surfactants derived from straight-chain primary and secondary alcohols are rapidly and completely degraded with loss of surfactant properties. The length of the ethylene oxide chain from zero up to ten units has no effect on the rate or the completeness of degradation. In such surfactants, the ethylene oxide chain is completely degraded.     
   
   

The preparation of alkyl esters from highly unsaturated triglycerides

The alcoholysis reaction has been applied to the preparation of highly unsaturated alkyl esters from menhaden oil. This reaction proceeded very rapidly, and nearly quantitative yields were obtained with virtually, no loss in double-bond structure. The formation of esters was studied, using straight- and branched-chain alcohols having 1–6 carbon atoms. The reactions were monitored by the technique of thin-layer chromatography (TLC). Maximum conversion of straight-chain esters was found to be a linear function with respect to the number of carbon atoms in the alcohol. Reaction time varied from 2 min for methanol to 60 min for n-hexanol. Branched-chain alcohols reacted more slowly than did the corresponding straight-chain compounds. This reaction was found to be applicable to laboratory and large scale preparations of highly unsaturated alkyl esters. Presented at the AOCS meeting, St. Louis, Mo., 1961.     

Studies on kinetics and preparation of C36 dimer acid esters

C₃₆ Dimer acids were esterified with various short-chain alcohols, namely 2-propanol, n-butanol, n-hexanol, n-octanol, 2-octanol and 2-ethyl-1-hexanol by using sulfuric acid as catalyst and benzene as an azeotropic solvent. Various reaction parameters were standardized. In case of isopropyl esters, acid-to-alcohol mole ratio of 1:5 and sulfuric acid concentration of 2% based on the weight of dimer acids were found to be optimum. In case of straight-chain primary alcohols, namely n-butanol, n-hexanol and n-octanol, 1:2.5 mole ratio of acid to alcohol and 1% by weight of sulfuric acid were found satisfactory. Esterification reaction rates were determined from the fall in acid value of the product. The reaction followed pseudo first order kinetics. The reaction rates increased with the increase in chainlength of straight-chain primary alcohols from n-butanol to n-octanol. The rate of reaction decreased from n-octanol to 2-ethyl-1-hexanol to 2-octanol due to the branching of the chain in 2-ethyl-1-hexanol and secondary nature of the −OH group in 2-octanol.     

Lipase-catalyzed esterification of lactic acid with straight-chain alcohols

Enzymatic synthesis of esters of lactic acid and straight-chain alcohols with different chain lengths (C₆–C₁₈) were investigated in batch reactions with hexadecanol (C₁₆) as the model alcohol. Cyclohexane was the best solvent for higher ester yields, and the best biocatalyst was the immobilized Candida antarctica lipase B (Novozym 435) as well as the textile-immobilized Candida sp. lipase. A method was established to obtain ester yields in the range of 71 to 82% for the different alcohols, and the most favorable conditions for the esterification reaction using Novozym 435 were an equimolar ratio of lactic acid to alcohol, each at a concentration of 120 mM each; a 50°C reaction temperature; 190 rpm shaking speed; and the addition of 100 mg molecular sieves (4 Å) for drying. The ester yield increased with increasing lipase load, and a yield of 79.2% could be obtained after 24 h of reaction at 20 wt% of Novozym 435. The immobilized Candida sp. lipase prepared in the laboratory also could be used to produce esters of lactic acid and straight-chain alcohols, but it had a much lower activity than Novozym 435 with a temperature optimum of 40°C.     

Solubility increase of coal by alkylation with various alcohols

A vitrinite concentrate of Taiheyio coat has been reacted with various alcohols using ZnCl₂ as a catalyst under nitrogen pressure. The reaction conditions such as the reaction time, reaction temperature, initial nitrogen pressure and the effect of other Lewis acids as catalysts have been examined using methanol. The product from the reaction with methanol at 400 °C is fully soluble in pyridine, 57% in benzene and 26% in straight-chain hexane. This result is similar to that obtained when coal is hydrogenated under 10 MPa hydrogen pressure. Higher temperature, higher initial nitrogen pressure and longer reaction times give increased solubility. ZnCl₂ and FeCl₃ are the best catalysts. Of the various alcohols, branched alcohols give better results.     

Engineering yeast alcohol dehydrogenase. Replacing Trp54 by Leu broadens substrate specificity

Analysis of a crystal structure of alcohol dehydrogenase (Adh)from horse liver suggests that Trp54 in the homologous yeastalcohol dehydrogenase prevents the yeast enzyme from efficientlycatalysing the oxidation of long-chain primary alcohols withbranching at the 4 position (e.g. 4-methyl-1-pentanol, cinnamylalcohol). This residue has been altered to Leu by site-directedmutagenesis. The alteration yields an enzyme that serves asan effective catalyst for both longer straight-chain primaryalcohols and branched chain alcohols.     

The acid-catalyzed addition of alkoxyl groups to the olefinic double bonds of soybean oil

The acid-catalyzed reaction of soybean oil with the homologous series of straight-chain alcohols: methyl, ethyl, n-propyl, n-butyl and n-hexyl in a pressurized system yielded completely transesterified products and 18-31% substituted alkyl ethers. Mass spectrometry of the hydrogenated methyl ester derivatives showed that the addition reaction occurred at one of three double bonds of the unsaturated fatty acids. The reaction with three secondary alcohols yielded only 0.1-2.5% substituted alkyl ethers. Presented at the AOCS Meeting in Phoenix, AZ, in May 1988. Deceased.     

Novel Synthesis Method of Alumina Having a Large Pore-Volume

The reaction of alumina isopropoxide (AIP) in straight-chain primary alcohols at high temperatures yields the alkyl derivatives of boehmite. Crystallinity of the alkyl derivatives of boehmite can be controlled by the feed ratio of AIP/alcohol. The alumina samples derived from the products having poor crystallinity had large pore-volumes (1.16–3.24 cm³/g).     

Long-chain unsaturated alcohols from jojoba oil by sodium reduction

Summary Jojoba oil is a liquid wax composed essentially of C₂₀ and C₂₂ straight-chain monoethylenic acids and alcohols in the form of esters. Sodium reduction of the wax fatty esters in jojoba oil yielded quantitatively a mixture of unsaturated, long-chain alcohols from the acid moiety of the jojoba oil. Yields of about 91% were obtained in the laboratory-scale experiments and 82 to 86 for the pilot-plant experiments. Analytical data, including detailed infrared spectra information, are given for the resulting product alcohols. Presented at the fall meeting, American Oil Chemists' Society, Cincinnati, O., September 29-October 2, 1957. One of the laboratories of the Southern Utilization Research and Development Division, Agricultural Research Service, U. S. Department of Agriculture.     

Development of a correlation between the non-polar solubility parameter,refractive index and molecular structure. II. Aliphatic ethers and alcohols

A relationship between the non-polar solubility parameter (λ) for polar aliphatic solvents and their refractive index has been developed. The use of structural group increments for branched isomers avoids the ambiguous choice between similarity in structure, reduced temperature and molal volume for the polar compound and its hydrocarbon homomorph. For straight-chain compounds, where a direct comparison with λ as calculated from a homomorph correlation function is possible, the mean discrepancy in λ is 0.07% for ethers and 0.14% for alcohols at 25°C.     

Attraction of moth species of Tortricidae,Gelechiidae, Geometridae,Drepanidae, Pyralidae,and Gracillariidae families to field traps baited with conjugated dienes

Field surveys of a series of conjugated diunsaturated straight-chain primary alcohols, acetates, and aldehydes (dienes), including the 3,5-dode-cadienyl, 8,10-dodecadienyl, 3,5-tetradecadienyl, 8,10-tetradecadienyl, 9,11-tetradecadienyl, and 10,12-tetradecadienyl primary alcohols, acetates, and most aldehydes, and the related monounsaturated straight-chain primary alcohols, acetates, and aldehydes (monoenes), including the 3-dodecadienyl alcohol and acetates, attracted the following species from the title families. Diene attractants have been demonstrated for at least onePhyllonorycter sp.,Chionodes lugubrella (Fabr.),Leptostales ferruminaria (Zell.),Drepana bilineata (Pack.),Pyrausta fodinalis (Led.),Notocelia purpurissatana Heinr.,Phaneta alterana Heinr. Monoene attractants were demonstrated forHedya separatana (Kft.),Cydia fletcherana (Kft.),Barbara mappana Free.,Ancylis burgessiana (Zell.),Ancylis nubeculana Clem.,Evippe prunifoliella Cham.,Phlyctaenia coronata tertialis (Gn.), aChionodes sp., a Gelechiidae sp., and an unidentifiedPhyllonorycter sp. Replicated field experiments showed attraction-inhibition relationships for most species. Electroantennagram data are presented forLeptostales ferruminaria andDrepana bilineata.     

Analysis of surfactant mixtures. I

Summary Some data on the use of 93% phosphoric acid as a reagent for recovering the hydrophobic portion of surfactants are presented, and their application to the analysis of surfactant mixtures is discussed. Aromatic sulfonates, straight-chain alkyl sulfates, fatty acid amides, and fatty acid esters decomposed to give good yields of the starting hydrophobic materials. Dioctylsulfosuccinate gave a mixture of octyl alcohols and olefins while the ethylene oxide condensates of lauryl alcohol, tridecyl alcohol, and tertiary dodecyl mercaptan gave olefins derived from the starting hydrophobic materials. Diisobutylene phenol-ethylene oxide condensate decomposed to olefins, conjugated olefins, and alcohols formed by rupture of the aromatic ring. The products are characteristic of the hydrophobic oils, and in most cases products from mixtures of surfactants can be separated by known analytical methods.Alpha-sulfo fatty acids or alkane sulfonates do not give recoverable oils by this treatment.     

邻苯二甲酸酯的合成及其性能研究

以邻苯二甲酸酐和脂肪醇为原料,硫酸氢钠为催化剂酯化合成了一系列邻苯二甲酸酯。考察了脂肪醇的链长度、类型及支链醇含量等因素对合成酯性能的影响,进而得出其结构与性能的变化规律,并为高性能油品的合成提供理论依据。结果表明,随着脂肪醇链长的增加,合成酯的粘度和粘度指数逐渐增大,倾点和闪点也呈升高趋势;碳原子数目相同的支链醇酯较直链醇酯具有更高的粘度、倾点和闪点以及更低的粘度指数;在直链醇中引入支链醇,所得合成酯的粘度增大,粘度指数减小,倾点和闪点升高;且随着支链醇含量的增加,合成酯的粘度总体呈增大趋势,粘度指数逐渐减小,倾点和闪点呈锯齿型变化。     

Volatile Components in Metatarsal Glands of Sika Deer, Cervus nippon

GC-MS analysis of the metatarsal gland secretion from a female sika deer, Cervus nippon, showed 35 major volatile compounds that included 13 straight-chain carboxylic acids, a single branched-chain carboxylic acid, 9 straight-chain aldehydes, 3 monounsaturated aldehydes, 5 long-chain alcohols, a ketone, and cholesterol. The four most abundant compounds were heptanal, nonanal, octanoic acid, and 6-methyl-2-heptanone. Many of the compounds have previously been found in cervid secretions, but the unsaturated aldehydes, (E)-2-octenal, (E)-2-nonenal, and (E)-2-decenal, have not previously been reported in the glands of any cervid. The compounds in this gland may be pheromones, since metatarsal gland odor has been implicated in chemical communication among conspecifics of other cervids.     

Unusual C<Subscript>21</Subscript> linear polyacetylenic alcohols from an Atlantic ascidian

Four novel straight-chain polyacetylenic alcohols were isolated from a marine ascidian (Phylum Chordata, subphyllum Urochordata) collected off Vigo, along the Atlantic coast of northwestern Spain. The chemical structures, which exhibit an uncommon dienyne group, were characterized by spectroscopic methods, mainly mono- and bi-dimensional NMR. This is the first finding of acetylenic lipids from an organism belonging to phylum Chordata.     

Predicting cetane numbers of n-alcohols and methyl esters from their physical properties

Cetane numbers (C#) for the homologous series of straight-chain, saturated n-alcohols, C₅−C₁₂ and C₁₄, were determined according to ASTM D 613. Measured C# ranged from 18.2–80.8 and increased linearly with carbon number (CN). Regression analyses developed equations that related various physical properties or molecular characteristics of these alcohols to calculated C#. The degree of relationship between measured and calculated C# was expressed as R². The decreasing order of the precision with which these properties correlated with C# was: boiling point (bp)>melting point (mp)>CN>heat of combustion (HG)>refractive index (n²⁰ _D)>density (d). This ranking was based upon R² (0.99–0.96) and the Average % error (2.8–7.2%). C# were also determined for straight-chain homologs of saturated methyl esters with CN of 6, 10, 12, 14, 16 and 18. C# ranged from 18.0–75.6 and increased curvilinearly with CN. Equations were also developed that related physical properties of these esters to C#. The precision with which these properties correlated with C# was: bp>viscosity (V)>heat of vaporization (HV)>HG>CN>surface tension (ST)>mp>n²⁰ _D>d. R² ranged from 0.99 for bp to 0.98 for d. Equations for the alcohols were linear or quadratic, while equations for the esters were linear, quadratic or cubic based upon statistical considerations that included a Student’s t-test. With related physical properties and these equations, accurate predictions of C# can be made for saturated n-alcohols and methyl esters.     

Propionates and Acetates of Chiral Secondary Alcohols: Novel Sex Pheromone Components Produced by a Lichen Moth Barsine expressa (Arctiidae: Lithosiinae)

Females of a lichen moth, Barsine expressa (Arctiidae, Lithosiinae), which inhabit Iriomote Island in Japan, were captured by a black-light trap, and the pheromone gland extract was analyzed by gas chromatography (GC) with an electroantennographic (EAG) detector, and by GC coupled with mass spectrometry. The females produced several EAG-active esters, and the mass spectrum of a major component indicated the mixture consists of propionates derived from C₁₇-saturated secondary alcohols, which were inseparable on the capillary GC column. In addition to these main components, the pheromone glands included two acetate derivatives of C₁₇ alcohols, and other propionates of C₁₆ and C₁₅ alcohols. The crude extract was treated with K₂CO₃, and a 1:1 mixture of C₁₇ alcohols with a C₆- or C₇-chain moiety was obtained. The two alcohols were uniformly converted into monodeuterated n-heptadecane by mesylation and succeeding LiAlD₄ reduction. This result revealed a straight-chain structure of the C₁₇ alcohols with the acyl groups located at the 7- or 8-position. Field tests on Iriomote Island showed that the synthetic esters were behaviorally active. A 1:1 mixture of racemic 7-propioxyheptadecane and 8-propioxyheptadecane, which were prepared from the secondary alcohols synthesized by a Grignard coupling reaction, attracted male moths. Furthermore, propionates of the alcohols synthesized enantioselectively by using a hydrolytic kinetic resolution with Jacobsen’s catalyst were evaluated. Only the traps baited with a mixture of the two esters with the same S-configuration significantly attracted B. expressa males. In the Tokyo area, the propionate mixture attracted a closely related species, Barsine aberrans aberrans.     

Stereocomplex formation between isotactic PMMA and syndiotactic polymers of methacrylates of straight-chain alcohols

Summary Stereocomplex formation between isotactic (iso-) poly(methyl methacrylate) (PMMA) and syndiotactic (syn-) polymers of methacrylates of straight-chain alcohols such as ethyl, propyl, butyl and allyl alcohols was found to occur in acetone to form gel. The solid complexes recovered from the gels in acetone showed endotherms in their DSC thermograms due to the melting of the complexes. The melting points of the complexes are 143.0°C, 125.4°C, 101.5°C and 141.5°C, respectively. The X-ray powder patterns of these complexes showed reflection peaks at 2=4.3–4.4° and 6.8–10.6°. The former reflections are commonly observed for all stereocomplexes including PMMA stereocomplex and should correspond to the fiber period. The degree of the latter decreased as the size of ester group increased corresponding to the increasing distances between two double-stranded helices, if we adopt the Challa's double-stranded helical model for the stereocomplex.     

Identification of straight-chain fatty acids in coal extracts and their geochemical relation with straight-chain alkanes

Mono-carboxylic, straight-chain fatty acids are present in extracts of lignite and subbituminous coal (0.4–1.0 wt%, daf basis), but not in those of a bituminous coal. They are removed with nearly equal ease by both solvent and supercritical gas (SCG) extraction. Octacosanoic acid is the major constituent, and values of the carbon preference index (even over odd) lie between 2 and 6. Solvent extraction of the coals also removes small quantities (< 0.08 wt%) of straight-chain alkanes which are closely related in composition to the straight-chain fatty acids and are probably derived from them during maturation. However, previous SCG extraction of the coals yielded much larger quantities of straight-chain alkanes (0.3–0.7 wt%). Pyrolysis experiments with a lignite fatty acid fraction and with tetracosanoic acid show that these acids largely survive SCG extraction and, therefore, are not the main source of the relatively large quantity of straight-chain alkanes in these extracts.     

Surface-active Agents in Textile Processes and their Effect on Effluents

Various types of surface-active agent and their applications in textile processing are reviewed. In choosing a product for a particular application, the user must consider many factors, such as the biodegradability of the agent and its subsequent influence on effluents, waste treatment, and water pollution. A very wide choice of branded products is currently available, but approximately 95 % of the materials are based on a limited number of organic chemicals, the most important of which are the ethylene oxide condensates of alkylphenols and straight-chain alcohols, secondary alkyl sulphates, the alkylbenzenesulphonates (both branched- and straight-chain), and the primary alcohol sulphates. The biodegradability of these materials is discussed in relation to their chemical structures. Many of the surface-active materials now in use are biologically degradable. However, many non-ionic agents are biologically hard. Considerable attention is being focused on them since, at very low concentrations, they have a synergistic effect on the foaming of surface waters when traces of anionic detergents are present. Desirably, these biologically hard materials should be replaced by materials that do not have objectionable properties with regard to water purity. When new biodegradable products are being developed full consideration should also be given to their applicational characteristics.