氯化N—[3—长链烷氧（双）乙烯氧—2—羟]丙基—N,N,N—三甲基铵的合成及性 …

以溴代烷和乙二醇或一缩二乙二醇为原料合成长链烷基（双）氧乙烯醇（收率为７５％）,然后在相转移催化条件下和环氧氢丙烷反应得到长链烷基（双）氧乙烯缩水甘油醚（收率为９０％）,后者和三甲胺盐酸盐反应得到氯化Ｎ－「３－长链烷氧（双）乙烯氧－２－羟」丙基－Ｎ,Ｎ,Ｎ－三甲基铵（收率为９１％）,其结构通过红外光谱、核磁共振氢谱和元素分析结果得以证实,测定了产物的γｃｍ及ｃｍｃ。     

溴化N-[3-长链烷氧(双)乙烯氧-2-羟]丙基-N,N,N-三甲基铵的合成及表面活性

以脂肪醇和乙二醇或一缩二乙二醇为原料合成长链烷基（双）氧乙烯醇，收率为７５％。然后在相转移催化条件下和环氧氯丙烷反应得到长链烷基（双）氧乙烯缩水甘油醚，收率为９０％。后者和三甲胺氢溴酸盐反应得到溴化Ｎ ［３ 长链烷氧（双）乙烯氧 ２ 羟］丙基 Ｎ，Ｎ，Ｎ 三甲基铵，收率为９１％。其结构通过红外光谱、核磁共振氢谱和元素分析结果得以证实，测定了其基本的表面活性，产品的表面张力为３７７～４４６ｍＮ／ｍ，临界胶束浓度（ＣＭＣ）为２５７×１０－３～４６×１０－５ｍｏｌ／Ｌ。     

溴化N—[3—长链烷氧（双）乙烯氧—2—羟]丙基—N,N,N—三甲基铵的合成及表？…

以脂肪醇和乙二醇或一缩二乙二醇为原料合成长链烷基（双）氧乙烯醇,收率为７５％。后在相转移催化条件下和环氧氯丙烷反应得到长链烷基氧乙烯缩水甘油醚,收率为９０％。     

氯化N-(3-长链烷氧-2-羟)丙基-N,N,N-三甲基铵的合成及性质

脂肪醇和环氧氯丙烷在相转移条件下反应得到长链烷基缩水甘油醚（收率97％），以此为原料和三甲胺盐酸盐反应得到氯化N－（3-长链烷氧-2-羟）丙基-N，N，N-三甲基铵（收率96％）．其结构通过红外光谱、核磁共振氢谱及元素分析结果得以证实。本文还测定了所合成产品的表面张力和临界胶束浓度．     

新型季铵盐阳离子表面活性剂的合成及结构表征

以聚氧乙烯脂肪醇和环氧氯丙烷在相转移催化条件下反应,高收率得到聚氧乙烯脂肪醇缩水甘油醚,以此为原料和三甲胺盐酸盐反应定量得到Ｎ－［３－单（双）氧乙烯长链烷氧－２－羟］丙基－Ｎ,Ｎ,Ｎ－三甲基氯化铵,通过元素分析,红外光谱和核磁共振氢谱对其结构进行了鉴定。     

溴化N—（3—长链烷氧—2—羟）丙基—N,N,N—三甲基铵的合成及性质

脂肪醇和环氧氯丙烷在相转移条件下反应得到长链烷基缩水甘油醚，以此为原料和三甲胺氢溴酸盐反应得到溴化Ｎ－（３－长链烷氧－２－羟）丙基－Ｎ，Ｎ，Ｎ－三甲基铵。其结构通过红外光谱，核磁共振氢谱及元素分析结果得以证实。本文还测定所合成产品的表面张力和临界胶束浓度等。     

氟化N-（3-长链烷氧-2-羟）丙基-N，N，N-三烷基铵的合成及性质

脂肪醇和环氧氯丙烷在相转移催化条件下反应得到长链烷基缩水甘油醚，以此为原料和三甲(乙)胺氢氟酸盐反应得到氟化N-(3-长链烷氧-2-羟)丙基-N，N，N-三甲(乙)基铵，其结构通过红外光谱、核磁共振氢谱及元素分析结果得以证实。还测定了所合成产品的表面张力和临界胶束浓度。     

N,N′-双(2,2,6,6-四甲基-4-哌啶基)己二胺的合成

本文采用两步法由三丙酮氨与己二胺合成了光稳定剂９４４ 中间体, Ｎ, Ｎ′双（２,２,６,６四甲基４哌啶基）己二胺。对其中的关键步骤,加成脱水生成席夫碱中间体的反应进行了研究,对此反应的影响因素,包括温度,催化剂与摩尔比等进行了优化。如以骨架镍为催化剂,在优化的条件下光稳定剂９４４ 中间体的收率可达７６％ 以上。     

1,2-双(3-甲氧羰基-2-硫脲基)苯的催化合成

研究了１１种催化剂对１，２ 双（３ 甲氧羰基 ２ 硫脲基）苯的合成性能的影响，筛选得出催化剂（对氨基二甲苯胺∶Ｎ，Ｎ 二甲基苯胺∶Ｎ，Ｎ 二甲基十八胺＝１∶６∶３，质量比），在所给定的反应条件下（催化剂用量为反应物总质量的２％，时间６０ｍｉｎ，温度２５～３５℃），可使产物收率（相对邻苯二胺）达８８％以上，纯度达９８％以上。     

一种多功能表面活性剂的合成

以长链烷基替代EDTA分子中的一个乙酸基，使其改性为既具表面活性又有络合金属离子能力的多功能表面活性剂。合成分两步，先以乙二胺、溴代烷为原料，合成了中间体N－长链烷基乙二胺(R-en)，然后R－en和氯乙酸反应生成了N－长链烷基乙二胺三乙酸钠盐（RNa3edta)。用正交实验法探讨了R－en的合成条件为：n(乙二胺）：n（溴代烷）＝（2.5-3.0)：1．0，反应温度为60℃，反应时间为8－10h，其收率均达98％。终产品合成条件为n(R-en):n（氯乙酸）＝1．05：2，反应时间为10h，反应温度为80℃，收率达86％。并通过红外光谱、核磁共振氢谱对终产品结构进行了初步确认。     

Long chain fatty alcohols in normal and neoplastic tissues

Small quantities of long chain fatty alcohols (esterified or free or both) were found in four normal tissues (about 0.01% of total neutral lipids) and three neoplasms (about 0.3% of total neutral lipids). The major chain lengths (16∶0, 18∶0 and 18∶1) of the fatty alcohols in both normal and neoplastic cells qualitatively resemble the O-alkyl chain lengths of glyceryl ethers. Our data showing that long chain fatty alcohols occur in vivo support the biological significance of the metabolic pathway that uses fatty alcohols as a substrate for the alkyl chain in glyceryl ether biosynthesis.     

Fatty alcohols

“Fatty” or higher alcohols are mostly C₁₁ to C₂₀ monohydric compounds. In probably no other homologous aliphatic series is the current balance between natural and synthetic products so vividly evident. Natural sources, such as plant or animal esters (waxes), can be made to yield straight chain (normal) alcohols with a terminal (primary) hydroxyl, along with varying degrees of unsaturation. In the past, socalled fatty alcohols were prepared commercially by three general processes from fatty acids or methyl esters, occasionally triglycerides. Fatty acids add hydrogen in the carboxyl group to form fatty alcohols when treated with hydrogen under high pressure and suitable metal catalysts. By a similar reaction, fatty alcohols are prepared by the hydrogenation of glycerides or methyl esters. Fatty alcohols are also prepared by the sodium reduction of esters of fatty acids in a lower molecular weight alcohol. The sodium reduction method was ordinarily too expensive; it was displaced early by the other methods; finally most unsaturated alcohols made by this route were largely replaced. Methyl ester reduction continues to provide perhaps 20% of the saturated fatty alcohols, and selective hydrogenation with the use of special catalysts such as copper or cadmium oxides was developed for the production of oleyl alcohol. Synthetic or petroleum technology for long chain alcohols include the Ziegler process, useful for straight chain, even-numbered saturated products. A second is the carbonylation and reduction of olefins affording medium or highly branched chain alcohols. Paraffin oxidation affords mixed primary alcohols. Fatty alcohols undergo the usual reactions of alcohols. They may be reacted with ethylene oxide to yield a series of polymeric polyoxyethylene alcohols or with acetylene under pressure to yield vinyl ethers or with vinyl acetate to give vinyl ethers.     

Synthesis and characterization of surfactants <Emphasis Type="Italic">via</Emphasis> epoxidation of tall oil fatty acid

The synthesis and characterization of novel surfactants derived from tall oil fatty acid methyl esters are presented. The tall oil fatty acid methyl esters, which mainly contain methyl oleate, were converted to 9,10-epoxy derivatives and further transformed to the 9 (or 10) polyethylene glycol (PEG) ethers. Compounds with three different monomethylated PEG chain lengths with molecular weights of 350, 550, and 750, corresponding roughly to 7, 11, and 16 ethylene oxide units, were prepared. Surfactants were formed at an 89% overall yield from tall oil fatty acid. Cloud points were 46, 63, and 84°C, respectively, and surface tensions at the CMC (2.0, 1.0, and 0.4 mM, respectively) varied from 33 to 38 mN/m. Equilibrium surface tension and reflectometry measurements were made and results were similar to those of conventional long alkyl chain PEG surfactants. Results of the tensiometry and reflectometry measurements showed that the surfactants aligned better at the air-water interface than conventional surfactants. The adsorption properties for the three surfactants were similar to those of polyoxyethylene glycol alkyl ethers.     

Preparation and properties of double- or triple- chain surfactants with two sulfonate groups derived fromN- Acyldiethanolamines

Bis(sulfonate) types of amphipathic compounds with three long- chain alkyl groups were prepared by the reaction ofN- (long- chain acyl)diethanolamine diglycidyl ethers with long- chain fatty alcohols, followed by the reaction with propanesultone. The diglycidyl ethers were easily obtained from the correspondingN- acyldiethanolamines and epichlorohydrin in the presence of a phasetransfer catalyst. The same types of compounds with two longchain alkyl groups were also prepared from Nacetyldiethanolamine according to similar procedures. All these new double- or triple- chain surfactants were soluble in water and showed much better micelle forming and ability to lower surface tension than general types of single- chain surfactants with one sulfonate group. The critical micelle concentration (CMC) and γ_CMC values of the triple- chain compounds were still much smaller than those of the corresponding double- chain compounds with two common alkyl groups. The efficiency of adsorption at the water/air interface (pC₂₀) of these surfactants was very high. Their foaming properties, wetting ability toward a felt chip, and lime- soap dispersing ability were measured. To whom correspondence should be addressed at Department of Applied Chemistry, Faculty of Engineering, Osaka University, Yamadaoka 2-1, Suita, Osaka 565, Japan.     

Glyceryl ethers in insects: Biosynthesis of ethanolamine phosphoglycerides containing alkyl and alk-1-enyl glyceryl ether linkages

When¹⁴C-labeled acetate, fatty acids or fatty alcohols were injected into or fed to the tobacco budworm, acyl, alkyl and alk-1-enyl moieties of the phospholipids incorporated radioactivity. Fatty acids were the principal precursor in acyl bond formation and fatty alcohols in the synthesis of alkyl and alk-1-enyl glyceryl ethers. Detailed analysis of the etherlinked phosphoglycerides revealed that most of the radioactivity was in the ethanolamine phosphoglycerides, and very little¹⁴C was found in the choline phosphoglycerides. In experiments of a short duration, the alkyl glyceryl ethers incorporated more radioactivity than the alk-1-enyl glyceryl ethers. The reverse was found with long term experiments, when the alk-1-enyl ethers had higher radioactivity. In addition to demonstrating the synthesis of ether-linked ethanolamine phosphoglycerides, the data suggested that fatty alcohols and acids were interconverted by insects and that the alk-1-enyl ethers were derived from the alkyl ethers. Presented at the AOCS Meeting, Houston, May 1971. The following abbreviations and terminology will be used: PE, PC, PI and PS for the generic terms ethanolamine, choline, inositol and serine phosphoglycerides, respectfully. Alkyl glyceryl ether for 1-alkyl-2-acyl-sn-glycerol-3-phosphoryl-, and alk-1-enyl glyceryl ether for 1-alk-1′-enyl-2-acyl-sn-glycerol-3-phosphoryl-(commonly called plasmalogen). These are adapted from the tentative rules published inJ. Lipid Res. 8:522–528 (1967).     

Enol esters XVI: Enol ethers in synthesis

The synthesis of isopropenyl octadecyl ether is reported. This compound is a useful reagent for the synthesis of wax esters by reaction with long chain fatty acids, and of symmetrical or unsymmetrical ethers via reaction with long chain alcohols. The long chain alkyl isopropenyl ether is more sensitive to hydrolysis than the corresponding enol ester and forms successively the ketal 2,2-dioctadecyloxypropane, and octadecanol and acetone. Glycerol reacts with propyne yielding glycerol acetonide, glycerol acetonide isopropenyl ether and diglycerol bisacetonide. New crystalline derivatives of diglycerol are described, useful for the characterization of that substance. E. Market. Nutr. Res. Div., ARS, USDA.     

Glyceryl ether,wax ester and triglyceride composition of the mouse preputial gland

Major lipid classes of the preputial gland of the mouse have been identified as wax ester, neutral plasmalogen, glyceryl ether diester and triglyceride. The chain lengths and degree of unsaturation in the aliphatic moieties of the alk-1-enyl and alkyl glyceryl ethers are similar to those of the fatty alcohols of the wax ester fraction. This lends support to the theory that long chain fatty alcohols can be direct precursors of the aliphatic chains of glyceryl ethers. The striking qualitative, as well as quantitative, similarities between the alkyl and alk-1-enyl moieties of the glyceryl ethers in the neutral lipid fraction suggest that they share a common pathway of biosynthesis or are interconvertible. Neutral plasmalogens and glyceryl ether diesters contain significant amounts of odd-numbered and branched fatty acids, unlike the fatty acids of the triglycerides; therefore, the biosynthesis of neutral plasmalogens and glyceryl ether diesters may not be related to the biosynthesis of triglycerides. Presented at the AOCS Meeting, Chicago, October, 1967. Taken from a dissertation submitted to Tulane University in partial fulfillment of the requirement for the degree of Doctor of Philosophy by Gail Sansone.