Chlorinated alcohols: I. Preparation from chlorinated acids

Rhenium, ruthenium and rhodium oxides, hydrogenolysis catalysts for stearic acid at 150 C, were tried for the conversion of 9,10-dichloro-stearic acid to the dichloro alcohol but only ReO₃ was effective in some degree (yield 14%). Dehydrochlorination or hydrogenolysis at the carbon-chlorine bond was the principal reaction. Reductions with diborane or with lithium aluminum hydride, however, were found to be excellent methods for preparing 9,10-dichloro-stearyl alcohol.     

Extraction of anions by a liquid cation-exchanger

The distribution ratio has been measured for the extraction of tracer quantities of a number of metals from aqueous solutions of HX or LiX (X = Cl, Br) by the liquid cation-exchangers 0·1 M dinonyl naphthalene sulphonic acid and 0·1 M lithium dinonyl naphthalene sulphonate in n-heptane. In several cases at high halide concentrations the partition behaviour shows marked deviation from that to be expected from the cation exchange process. The effect arises in instances where the metal is very strongly taken up by anion exchangers and anomalous extraction is always greater from lithium halide solution than from the corresponding aqueous halogen hydracid.

The dinonyl naphthalene sulphonates occur in the organic layers in micellar form and the composition of such aggregates containing invaded supporting electrolyte and water has been ascertained.

Spectrophotometric and stoichiometric measurements on lithium dinonyl naphthalene sulphonate in n-heptane extracts of macro-quantities of metals M(III) or M(II) from concentrated lithium halide solutions have demonstrated the presence of anionic metal halide complexes in organic phases. Slope-analysis of partition data obtained with the metals present at trace concentration gives results in agreement with these conclusions, and the anomalous extraction behaviour can be formulated as involving equivalent exchange of a complex metal-halide anion with invaded halide associated with micelles in the organic medium.     

Products from the reaction of fatty acids with ketones and their characteristic properties as cutting fluids additives

Hydroxy acids were synthesized in good yields from ketones and fatty acids by the use of lithium naphthalene in the presence of diethylamine. For example, from cyclohexanone and undecylenic acid (I), 2-(1-hydroxy-1-cyclohexyl)-10-undecenoic acid (III) was obtained in 92% yield. Hydroxy acids were treated withp-toluenesulphonic acid to give corresponding unsaturated fatty acids. From the reaction of (III), 2-(1-cyclohexenyl)-10-undecenoic acid (IV), a 3,4-unsaturated acid was obtained (yield 59%). Corrosion and lubricity tests for these products as water-based cutting fluid additives were carried out. We have found that triethanolamine salts of 2-cyclohexenyl and 2-hydroxycyclohexyl fatty acids showed effective rust-inhibiting and antiwear properties for water-based cutting fluids.     

The Direct Synthesis of β-hydroxy-acids by Lithium Naphthalene and Acetic Acid

Lithium naphthalene reacts with acetic acid to give α-anion of lithium acetate. The reaction of this anion with various ketones gives the corresponding β-hydroxy-acids in good yield.     

磺酸萘在超临界水中氧化降解路径的研究

采用GC-MS对1-氨基-2-羟基-4-磺酸萘有机污染物在超临界水中氧化降解的产物进行了分析和鉴别,通过对中间产物的鉴别和结合相关研究提出了其在超临界水中氧化降解的路径。1-氨基-2-羟基-4-磺酸萘氧化降解的路径可用纵横交叉模式描述,即纵向的氧化开环降解反应和横向的耦合反应,该污染物及其带芳环中间产物进一步氧化都经过苯酚,并由其继续开环氧化降解。     

Reactions of fatty materials with oxygen. XV. Formation of 9,10-dihydroxystearic acid and cleavage products in the oxidation of oleic acid and methyl oleate in acetic acid

Summary The autoxidation of oleic acid and methyl oleate in acetic acid solution at 25–30°, 65°, and 115–120° with a cobalt salt as catalyst has been studied. Samples were withdrawn at intervals and the oxidation products were analyzed and then separated into high-melting 9,10-dihydroxystearic acid, cleavage products, unoxidized and hydroxy materials, and polymers. The best yields of desired oxidation products were obtained at 65°. Yields of pure 9,10-dihydroxystearic acid, m.p. ≧128°, were 12–17% and cleavage products 64–68%, thus accounting for about 80% of the starting material. At 25–30° and 115–120°, yields of the above-mentioned products were low. A mechanism is proposed which accounts for the formation oftrans-9,10-epoxystearic acid from both oleic and elaidic acid autoxidized in the absence of solvent, and the consequent isolation of high-melting 9,10-dihydroxystearic acid when acetic acid is the solvent. Paper XIV is reference 10. Presented at the Fall Meeting of the American Oil Chemists’ Society, Chicago, Ill., Nov. 2–4, 1953. One of the laboratories of the Bureau of Agricultural and Industrial Chemistry, Agricultural Research Service, U. S. Department of Agriculture.     

Chlorinated alcohols: IV. The chlorination of oleic acid

Chlorination of oleic acid gave mainly 9,10-dichlorosteraic acid but other products were also formed. By-products included the dimer, 9(10)-(9,10-dichlorostearolyoxy)-10(9)-chlorostearic acid, and the related trimer, formed independent of temperature in the range examined (−20 to +29 C). Higher solvent-oleic acid ratios decreased the amounts of dimer and trimer; chlorination in the presence of hydrogen chloride did not. The equivalent weight of 9,10-dichlorostearic acid was found to increase markedly upon treatment with chlorine and light, but in the dark the acid was apparently unchanged. These effects were independent of temperature. E. Utilis. Res. Dev., ARS, USDA, Philadelphia, Pa.     

Derivatives of long chain fatty acids as lubricant components

Soaps ofcis-9,10-epiminostearic acid have been synthesized and tested as components of lubricating greases. The lithium, sodium and potassium soaps were obtained by the reaction ofβ-iodocarbamates with the proper alkali metal hydroxides in the ring closure step of the iodine isocyanate (INCO) procedure for the synthesis of internal aziridines. The soaps of other metals, namely barium, lead, aluminum and indium, were prepared from the alkali metal epiminostearates by metathetical reactions. As a result of this method of preparation, the aluminum and the indium soaps were isolated as the dicarboxylates rather than as the tricarboxylates. For the purpose of comparison a sample of lithium 9,10-epiminostearate was also prepared from theβ-chlorocarbamate obtained by the addition of dichlorourethane (DCU) to methyl oleate. Since DCU addition is nonstereospecific, the soap obtained in this preparation was a mixture ofcis- andtrans-aziridines. Evaluation of the metal soaps as grease thickeners was made. The lithium derivative showed considerable promise as thickener having additional desirable properties. Presented at the AOCS-ISF World Congress, Chicago, September 1970. E. Market. Nutr. Res. Div. ARS, USDA.     

新型蓝光材料ADN衍生物的合成及表征

采用还原（6-叔丁基）萘基锂与取代蒽醌的加成物制成了3种有机电致蓝光材料——9,10-二（6-叔丁基）萘-2-甲基蒽（MDTBADN）,9,10-二（6-叔丁基）萘-2-乙基蒽（EDTBADN）和9,10-二（6-叔丁基）萘-2-叔丁基蒽（TTBADN）。并对其结构进行了^1HNMR、^13CNMR和MS表征。MDTBADN,EDTBADN及TTBADN的光制发光（PL）波长分别为448,443,442nm;UV分别为（235．0,263．0nm）,（234．0,263．5nm）,（234．5,263．5nm）;其玻璃化温度分别为131,179,130．88℃。实验结果表明,这3种化合物是一类新型的ADN系列蓝光材料,具有较好的应用前景。     

Photodegradation of some Oxygenated Polycyclic Aromatic Hydrocarbons

In order to obtain information about the degradability of oxygenated polycyclic aromatic hydrocarbons (oxy-PAHs) in environment, photodegradation in acetonitrile solution was studied on 9,10-phenanthrenequinone, 9-phenanthrenecarbaldehyde (phenanthrene-9-carboxaldehyde) and 1,8-naphthalenedicarboxylic anhydride (1,8-naphthalic anhydride), which are formed by fuel combustion or by photoirradiation of PAHs. A solution of the substrate was irradiated under atmospheric conditions using a xenon lamp. Photodegradation rates and information about products were obtained using HPLC with fluorescence and photodiode array detectors and GC/MS.

9,10-Phenanthrenequinone rapidly degraded by irradiation of light and yielded diphenic acid, diphenic acid anhydride, phthalic acid anhydride and some unknown compounds. Diphenic acid was a main product and it was produced at maximum upon 5-hour irradiation when degradation rate approached 100%. This reaction seems not to obey first-order equation. 9-Phenanthrenecarbaldehyde degraded slower than 9,10-phenanthrenequinone and yielded a polar unknown compound as a main product. While 1,8-naphthalenedicarboxylic anhydride showed quite stable character under irradiation of light.     

5,12-(二苯乙炔基)丁省的合成及其化学发光

由邻苯二甲酸酐与萘作用生成2-α-萘羰基苯甲酸,产率63%。2-α-萘羰基苯甲酸在无水A lC l3、NaC l催化下脱水重排,得到5,12-丁省醌,产率68%。5,12-丁省醌与苯乙炔基锂在二氧六环,DMF中反应4 h,水解后的混合物不经分离直接与氯化亚锡的盐酸溶液避光反应10 h,一步法合成目标物,收率53%。     

Structural and Optical Properties of New Naphthalene and Perylene Imide Imidazoles

ABSTRACT

New unsymmetrically substituted naphthalene and perylene imide imidazoles, N-(2-ethylhexyl)-naphthalene-3,4-(4,5-dicyano-1,2-benzimidazole)-9,10-dicarboxyimide and N-(1-heptyloctyl)-perilene-3,4-(4,5-dicyano-1,2-benzimid-azole)-9,10-dicarboxyimide, were synthesized via condensation reactions of diaminophthalonitrile and aromatic monoimide monoanhydride derivatives. Their structural analyses have been conducted by using general spectroscopic methods including FT-IR, ¹H- and ¹³C-NMR, mass and elemental analysis. The molecular structure of naphthalene derivative was also determined by single crystal x-ray diffraction. Electronic absorption and emission properties were investigated on comparison. For studied compounds, both DFT and TDDFT calculations were carried out with the 6-311G(d,p) basis set, taking into account solvation effects by means of polarizable continuum model as implemented in the Gaussian 09 package.     

Tomato CYP74C3 is a multifunctional enzyme not only synthesizing allene oxide but also catalyzing its hydrolysis and cyclization

The mechanism of the recombinant tomato allene oxide synthase (LeAOS3, CYP74C3) was studied. Incubations of linoleic acid (9S)-hydroperoxide with dilute suspensions of LeAOS3 (10-20 s, 0 degrees C) yield mostly the expected allene oxide (12Z)-9,10-epoxy-10,12-octadecadienoic acid (9,10-EOD), which was detected as its methanol-trapping product. In contrast, the relative yield of 9,10-EOD progressively decreased when the incubations were performed with fourfold, tenfold, or 80-fold larger amounts of LeAOS3, while alpha-ketol and the cyclopentenone rac-cis-10-oxo-11-phytoenoic acid (10-oxo-PEA) became the predominant products. Both the alpha-ketol and 10-oxo-PEA were also produced when LeAOS3 was exposed to preformed 9,10-EOD, which was generated by maize allene oxide synthase (CYP74A). LeAOS3 also converted linoleic acid (13S)-hydroperoxide into the corresponding allene oxide, but with about tenfold lower yield of cyclopentenone. The results indicate that in contrast to the ordinary allene oxide synthases (CYP74A subfamily), LeAOS3 (CYP74C subfamily) is a multifunctional enzyme, catalyzing not only the synthesis, but also the hydrolysis and cyclization of allene oxide.     

Chlorinated alcohols: II. The chlorination of oleyl alcohol

Chlorination of oleyl alcohol gives mainly 9,10-dichlorostearyl alcohol but a variety of other products are also formed. By-products include 9(10)-(9,10-dichlorostearoxy)-10(9)-chlorostearyl alcohol (14%) and 9,10-dichlorostearyl 9,10-dichlorostearate (3–4%) in addition to three or four less clearly defined products (12%). One group of products is apparently derived from participation of the hydroxyl group in the chlorine addition step while the other products formed by the reaction of the hydroxyl group with chlorine or chlorine and hydrogen chloride.     

Alkylation of naphthalene with n-butene catalyzed by liquid coordination complexes and its lubricating properties

With the development of coal chemical industry, large amounts of naphthalene and n-butene are produced, and converting them into high value-added products through alkylation has gained particular importance and interest. In this work, liquid coordination complexes (LCCs) were used as acid catalysts for the first time in the naphthalene alkylation reaction under mild conditions to obtain multi-butylnaphthalenes with high yield. Various reaction conditions were thoroughly investigated. The LCC consisting of urea and AlCl₃ showed excellent catalytic performance under optimal reaction conditions, giving 100% conversion of naphthalene and 99.66% selectivity towards multi-butylnaphthalenes. Combining the catalyst properties and catalytic results, a plausible reaction mechanism was proposed. The lubricating properties of the synthesized products were investigated for their potential application as lubricating base oils. The synthesized multi-butylnaphthalenes showed comparable physicochemical properties and tribological performances as the commercial cycloalkyl base oil.     

Dimerisation of isoprene

Isoprene was dimerised by lithium naphthalene to linear isoprene dimer, a mixture of 2,6-dimethyl-2,6-octadiene and 2,7-dimethyl-2,6-octadiene, in 80% yield.     

氨基磺酸系高性能减水剂的研究和生产应用

介绍了氨基磺酸系高性能减水剂的合成方法及生产应用。对反应温度、投料顺序和速度、溶液的酸碱度等条件进行控制,并以工业产品进行水泥净浆流动度与其经时变化的实验,以及与萘系高效减水剂复配实验。结果表明：氨基磺酸系高性能减水剂除具有很高的分散性（减水率高达30％）,还具有良好的保塑性能;和萘系高效减水剂复配效果好,能够解决其泌水的问题。     

Electrocarboxylation of 2-methylhalogen-9,10-anthraquinones

Herein we propose a new synthetic route for the production of 9,10-anthraquinone-2-ethanoic acid (AQEA) by electrocarboxylation of 9,10-anthraquinone-2-bromo-methyl (BrMAQ) or 9,10-anthraquinone-2-chloro-methyl (ClMAQ). Electrocarboxylation of anthraquinones appears as an alternative for synthesizing their respective carboxylic acids. Electrosyntheses were carried out using N,N-dimethylformamide (DMF) as solvent, NaClO₄ as electrolyte and metallic magnesium as sacrificial anode. One of electrolysis products was AQEA, which was isolated, purified and then analysed by IR, RMN and high performance liquid chromatography (HPLC). Electrocarboxylation selectivity to AQEA ranged on average from 32 to 40% using ClMAQ and BrMAQ, respectively.     

负离子双锂引发剂体系的研究 Ⅰ.从萘锂-锂粉可逆平衡体系合成双锂短链引发剂及其机理的探讨

探讨了四氢呋喃存在下，在苯中合成萘锂－锂粉复合引发剂的原因和机理，认为苯的共轭π键对金属锂的高度分散和高活性起很大作用。利用量子化学计算讨论和分析了丁二烯负离子自由基的结构及偶合方式。借助气相色谱－质谱联用法分析了丁二烯二聚体的结构，从而为偶合机理提供了可靠的证据。