Synthesis and evaluation of some new oxazolones and imidazolones as antioxidant additives for Egyptian lubricating oils

Oxazolone derivative 2 was utilized as a key intermediate for synthesis of some new oxazolone and imidazolone derivatives. Reaction of oxazolone derivative 2 with diamines under different conditions afforded the corresponding imidazolone derivatives 3-8, respectively. Moreover, oxazolone 2 reacted with some heterocyclic amines in glacial acetic acid giving the corresponding imidazolone derivatives 9-14, respectively. Cyclocondensation of thiosemicarbazide with compound 2 in dry pyridine afforded compound 15. Addition of secondary amines to olefin double bond of compound 2 gave the corresponding addition products 16-19, respectively. Michael addition of compound 2 with some active methylene compounds afforded oxazolone derivatives 20-23, respectively. These prepared products were evaluated as antioxidant and corrosion inhibitors for gasoline lubricating oil and compounds 6a-c, 10 and 15 exhibited the highest antioxidant and anticorrosive activities. The effect of concentration of additives was studied to recommend the optimum concentration to be used. The results showed, for additive 15, 0.1 g for 1 L oil was the more effective concentration. Measurements for thermal analysis and of surface tension of oil after oxidation were also carried out.     

The Evaluation of Some Heterocycles as Antioxidant Additives for Lubricating Oils

Abstract

2-Phenyl-4-thienylidene-2-oxazolin-5-one I was prepared and reacted with 2-aminothiazole, p-aminophenol, and p-aminoacetophenone in the presence of acetic acid containing catalytic amounts of freshly fused sodium acetate to give the corresponding imidazolone derivatives II, III, and IV, respectively. A Claisen reaction of IV with ethylacetate gave the corresponding imidazolone V, which on reaction with phenylhydrazine in ethanol afforded the corresponding pyrazolinoimidazolone VI. On the other hand, I reacted with o- and p-phenylenediamines in ethanol and yielded the corresponding o- and p-aminophenylcarboxamide of α-phenyl carboxamido-β-thiophenoacrylic acids VII and VIII, respectively. The prepared products were evaluated as antioxidant additives for Egyptian lube oils. Some of these products showed good results.     

相转移剂对光催化TiO2氧化苯并噻吩的影响

 采用光催化TiO₂氧化脱硫技术，以十二烷基苯磺酸钠、十六烷基三甲基溴化铵和聚乙二醇-400为相转移催化剂，冰乙酸为溶剂，对含苯并噻吩的油品进行光催化氧化脱硫反应，考察了光催化反应时间、相转移剂和TiO₂用量及冰乙酸/油品体积比对油品脱硫率的影响。结果表明，3类相转移剂的加入，都能显著提高油品的光催化TiO₂氧化脱硫率；在冰乙酸/油品体积比为1、TiO₂用量1%和光催化反应时间为3h的条件下，最大脱硫率达50%以上，此时，相转移剂ABS的用量最少（0.25%），明显低于CTAB（0.50%）和PEG-400（1.1%）的用量；光催化反应时间越长，脱硫率越高。     

直馏柴油应用离子液体一锅法脱硫研究

以实验室合成的Zn[C₆H₁₁NO]₃Cl₂、N-甲基咪唑溴化物、Zn[CO(NH₃)₂]₃Cl₂、1-丁基-3-甲基咪唑四氟硼酸盐和磷酸酯类离子液体作为脱硫萃取剂,H₂O₂-冰醋酸体系作为氧化剂,采用"一锅法"对直馏柴油进行脱硫,考察了离子液体种类和用量、H₂O₂和冰醋酸用量、反应时间及氧化温度对脱硫率的影响。结果表明,磷酸酯类离子液体对直馏柴油的脱硫效果相对较好,在离子液体体积分数为20%、H₂O₂体积分数为8%、冰醋酸体积分数为4%、20 min、80℃条件下,柴油中硫质量分数由1425 μg/g降至676 μg/g,脱硫率达到52.6%;且回收的离子液体使用5次,其脱硫效率仍达到40%以上。     

Ion-pairing RP-HPLC method for determining tetrazene in water and soil

Abstract

Ion-pairing reversed phase-high performance liquid chromatography methods were developed to determine tetrazene in water and soil. Determinations were achieved using an LC-18 column, a mobile phase of 2/3 v/v methanol-water containing 0.01 M 1-decane-sulfonic acid sodium salt, and a UV detector set at 280 nm. The pH of the mobile phase was adjusted to 3 with glacial acetic acid, which was optimal for separation of tetrazene from potential interferences by other explosives. The retention time for tetrazene was 2.8 minutes.

A linear model with zero intercept was found to adequately describe the calibration data for concentration ranges of 6.1 to 122 μg/L for water samples and 0.204 to 40.8 μg/g for soil samples. Method accuracy was 100% for most water samples and varied from 68–88% for soil samples. Reporting limits of 3.04 μg/L and 1.10 μg/g were estimated for water and soil, respectively.

Water samples are analyzed directly without pretreatment or preconcentration. Soils are extracted on a platform, orbital shaker with 55/45 v/v methanol-water containing 0.01 M 1-decane-sulfonic acid sodium salt.

Tetrazene was found to be unstable in an aqueous medium at room temperature. Concentrations decreased by 96–100% over 24 hours. The rate of degradation was reduced significantly when solutions were maintained near 0°C.     

3-N-丙酰基-2-芳基-5-(3-碘苯基)-1,3,4-(口恶)唑啉类化合物的合成及表征

以3-碘苯甲酸为原料,在浓硫酸作用下与乙醇反应制得3-碘苯甲酸乙酯(1),再以无水乙醇为溶剂,在105℃化合物1与80％的水合肼反应8 h,制得3-碘苯甲酰肼(2)。在无水乙醇中,在90～95℃化合物2分别与4-甲基苯甲醛、2-氯苯甲醛、4-氯苯甲醛、4-羟基苯甲醛、2,4-二氯苯甲醛、4-甲氧基苯甲醛、3-硝基苯甲醛、4-硝基苯甲醛和4-二甲氨基苯甲醛反应得到相应的酰腙[3(a～i)]。最后化合物3(a～i)分别与丙酸酐脱水环化成了3-N-丙酰基-2-芳基-5-(3-碘苯基)-1,3,4-(口恶)唑啉类化合物[4(a～i)],收率分别为86．2％,70．5％, 80．1％,68．2％,62．4％,75．2％,73．2％,70．5％和63．2％。并通过元素分析,IR,1H NMR和MS对化合物4(a～i)的结构进行了表征。     

硬脂酸二乙醇胺酯型柔软剂的合成

合成了低成本的硬脂酸二乙醇胺酯型柔软剂。通过研究尿素和硬脂酸的量、二乙醇胺与尿素的反应条件以及甲酸和乙酸成盐对产品性能的影响 ,获得了较佳配方和工艺 ,即通入氮气 ,以亚磷酸为催化剂 ,二乙醇胺 /尿素 (摩尔比 ) =1∶1,在 15 0℃反应 3～ 4h ,然后升温到 170℃反应 3h ,稍冷加入硬脂酸 (与二乙醇胺摩尔比为 1.8∶1)于 180℃反应 4h ,冷却到 90℃加入甲酸 (与二乙醇胺摩尔比为 1∶1) ,升温到 12 0℃反应 1h ,冷却得产品。性能测试结果表明 ,它是热水开料的弱阳离子表面活性剂 ,泛黄低、w =10 %的水剂度稠度高、柔软效果好     

由α-庚烯合成γ-壬内酯的研究

用α-庚烯、醋酐作原料,以醋酸锰作氧化剂,在冰醋酸溶剂中一步合成γ-壬内酯。氧化剂的制造是将二价无水醋酸锰溶于冰醋酸中,用高锰酸钾将其氧化成三价醋酸锰。     

Isophthalic dimethyloxaziridine as a potential bonding agent for Rocket Solid Propellants

Abstract

The synthesis, reactions and crystal structure of Isophthalic dimethyl oxaziridine are presented here. The synthesis was carried out utilising hydroxylamine-O-sulfonic acid to produce oxaziridine unsubsituted on the nitrogen, which was reacted in situ with isophthaloyl dichloride to give the corresponding Isophthatic dimethyl oxaziridine. It is an analogue of Isophthalic 2-methyl aziridine, a product which has been used as a bonding agent for Composite Solid Propellant. The oxaziridine was tested in oxidative reactions of sulfides to sulfoxides, styrene oxide, cyclohexene to cyclohexene oxide, and 1-(2-cyclohexenyl)-2-propanone to [1-(2-cyclohexenyl)-2-propanone] oxide.     

Oxidative-extractive desulfurization of liquid fuel using stannous chloride-acetic acid mixture as catalyst

Present study reports catalytic oxidative-extractive desulfurization (COEDS) of model oil (dibenzothiophene (DBT) dissolved in iso-octane) using an acid mixture (composed of Lewis acid and organic acid (glacial acetic acid)) as catalyst and inorganic oxysalt, potassium dichromate, as oxidant. A series of acid mixtures were prepared by mixing different amount of Lewis acids (SnCl₂, CaCl₂ or CuCl₂) in specific amount of acetic acid and tested for the removal of sulfur from model oil. SnCl₂, which performed best as a Lewis acid, was used in further studies. Effect of Lewis acid to sulfur (molar) ratio was studied in the range of 1–5. Effects of other parameters i.e. oxidant to sulfur (O/S) molar ratio, temperature and time on desulfurization efficiency were also investigated. Fourier transform infrared (FTIR) spectroscopy of SnCl₂-CH₃COOH mixture, model oil (before COEDS), raffinate and extract layers was carried out to understand the removal mechanism. Apparent activation energy for COEDS process with SnCl₂-CH₃COOH system was calculated as 11.65 kJ/mol. At the optimized conditions of oxidant to sulfur molar ratio (O/S = 2:1) and Lewis acid to sulfur molar ratio (SnCl₂/S = 5:1), maximum 61.3% sulfur removal was observed from model oil containing 1000 ppm of sulfur at 308 K.     

N-denitration of octahydro-1, 3, 5, 7-tetranitro-1, 3, 5, 7-tetrazocine (HMX) by hydrazine catalyzed by palladium

Abstract

In palladium-catalyzed reactions between HMX (1) and hydrazine, the nitramine was denitrated. The ultimate products depended on particular reaction conditions. The initial intermediate in the presence of excess hydrazine in organic solvents or water is the reactive species formaldazine (4). Under oxidizing conditions with catalyst, this reacts further to form 4-amino-4H-1, 2, 4-triazole (5) as a final product. In neat hydrazine as solvent, hexamethylenetetramine (2) and reactive intermediates such as 1, 2, 4-triazolidine (6) are formed in situ following N-denitration.     

乙酰苯胺的合成

以苯胺、乙酸酐、乙酸为原料合成乙酰苯胺,考察了乙酸酐用量、乙酸用量、反应时间对乙酰苯胺收率的影响。确定了最佳工艺条件:n(苯胺):n(乙酸):n(乙酸酐)=1:2.0:0.2,反应时间为4.5 h。此条件下,乙酰苯胺收率达98.2％～98.4％,纯度达99.58％～99.82％。     

PW_(12)/SiO_2催化合成乙酸苄酯

采用苯甲醇和冰乙酸为原料,以PW_(12)/SiO_2为催化剂合成了乙酸苄酯,并通过红外光谱、XRD等对其结构进行了表征。最佳合成的工艺条件为:n(苯甲醇):n(冰乙酸)=1:2.5,回流温度,反应时间2 h,w(催化剂)=3.08%,w(甲苯)=15%。在此条件下,酯化率可达90%以上。     

高通量MOR型分子筛膜的制备及在乙酸酯化反应中的应用

采用含氟体系制备了高性能MOR型分子筛膜。采用XRD和SEM表征了MOR型分子筛膜及其参与8次酯化反应后膜层的微观结构。将高通量MOR型分子筛膜用于Zr(SO₄)₂/H-β催化的乙酸与乙醇酯化反应,基于2级动力学假设建立了膜反应器中进行的酯化反应动力学模型,考察了醇/酸摩尔比、催化剂用量和反应温度,以及MOR型分子筛膜的重复使用对乙酸转化率的影响。结果表明,含氟体系与无氟体系相比,所制备的MOR型分子筛膜的渗透通量可提高1.4倍。动力学模型模拟结果与实验数据吻合良好。MOR型分子筛膜反应器打破了乙酸酯化反应的化学平衡,由于生成的水可通过膜分离移出反应体系,反应12 h后乙酸几乎完全转化,同时分子筛膜重复使用8次对乙酸转化率无明显影响。     

H_3PW_(12)O_(40)催化合成三乙酸甘油酯及产物精制

对H3PW12 O4 0 ·xH2 O(PW12 )和PW12 /C催化乙酸和甘油酯化合成三乙酸甘油酯进行了研究。考察了催化剂用量、甘油 /乙酸 (摩尔比 )、反应温度、反应时间等因素对反应结果的影响。固载型杂多酸催化剂重复使用 9次 ,活性没有明显下降。粗产物可用活性炭脱色。较适宜的酯化反应条件是 :甘油 /乙酸 (摩尔比 ) 1∶4.0 ,催化剂 /甘油 (质量比 ) 2 .5 %,醋酐 /甘油 (质量比 ) 2 0 %,总反应时间 4～ 5h ,反应温度 <12 5℃ ,甘油酯化率大于 98%,纯度大于 99%。     

MECHANISTIC CONSIDERATIONS CONCERNING THE STABILITY TOWARDS DIOXYGEN OF EVOLUTIVE FUELS.

Abstract

The interaction of phenalenonc and 2-methylindole in presence of stoechiomctric amounts of paratoluenesulfonic acid in methanol under argon, yields twelve compounds which have been spectroscopically characterised. Seven compounds or sets of compounds could be scpareted by flash chromatography. Phenalene 4. and phenalanone 8 result from a disproportionalion reaction of a key intermediate 18. 2-Methylindolylphenalene 5 and bis(2-methyl)indolylphenalene 6 and 7 exist under the form of a complex mixture of lauiomers. 2-Methylindolylphenalanones 9 and 10. 2-methylindolylphenalenones 11. 12. 1 3. and bis(2-methylindolyl)phenalenones 14 and 15. could also be isolated from the reaction mixture. In presence of air and light compounds 5, 6, and 7. oxidize into 11, 12, 13, 14, and 15 via the corresponding phenalenyl radical. The mechanism of formation and interconversion of these products is discussed and experimentally supported. The peculiar reactivity of the phenalenic derivatives is analysed and it is suggested that such structures are present in asphaltenes. An hypothesis about their genesis is proposed.     

Preparation of 1-substituted-3,3-dinitroazetidines

Abstract

DNAZ (3,3-dinitroazetidine), 1, readily undergoes nucleophilic addition reactions with electron deficient haloaromatics, cyanogen bromide, S-methyl-N-nitroisothiourea and dichloroglyoxime to afford novel, energetic 1-substituted-3,3-dinitroazetidines. N-Nitrosation of DNAZ readily occurs, and Mannich condensations of DNAZ with poly-nitroalcohols are also described. The synthesis and properties of the energetic materials derived from these reactions will be discussed.     

负载型磷化镍催化剂上乙酸加氢制乙醇反应宏观动力学

通过等体积浸渍和N2流中热处理过程制备了Ni2P/SiO2催化剂,采用固定床反应装置进行乙酸加氢反应,取得不同条件下的乙酸转化率、乙醇等产物产率实验结果,进行了乙酸加氢制乙醇反应动力学研究。在确定乙酸加氢反应流体为气体、分析反应气体变化的基础上,经过推导,确定了乙酸转化及乙醇等产物生成动力学模型方程。利用反应实验数据,确定了各反应的速率常数和表观活化能。统计检验结果显示,乙酸加氢和乙醇生成反应动力学模型均具有较高的模拟计算精度。模型预测分析结果表明,随着反应温度升高、反应压力提高、质量空速减小、氢/酸摩尔比减小,乙酸转化率和乙醇产率均持续增大,在反应温度375℃、反应压力25 MPa、质量空速10 h-1、氢/酸摩尔比10的反应条件下,乙酸转化率和乙醇产率分别达到9992%和9479%。     

以己二腈为溶剂制备六苯基取代联苯双酚

以己二腈为溶剂 ,以 2 ,3 ,6-三苯基苯酚为原料经氧化偶合反应合成了 2 ,2′ ,3 ,3′ ,6,6′ -六苯基 -4 ,4′ -联苯双酚。考察了反应温度和溶剂对反应的影响。筛选了初产物的还原方法。经TLC、HPLC、1 H -NMR、ESR和IR及聚合的方法表征了产物的结构。结果表明用价廉易得的己二腈作为反应溶剂是可行的 ,初产物可用Zn粉、SnCl2 、乙酸还原     

Potentiometric method of determination of base numbers of nitrogen-containing additives

Summary For the determination of base numbers of succinimide additives, a method has been proposed, consisting of a potentiometric titration in nonaqueous medium. The recommended solvent is a mixture of chloroform and glacial acetic acid in 1/1 ratio, and the titrant is a 0.1 N solution of perchloric acid in glacial acetic acid.The results of base number determinations on succinimide additives by the proposed method are higher than those obtained by GOST 11362-65; the results by the proposed method are in essential agreement with the theoretical values.Translated from Khimiya i Tekhnologiya Topliv i Masel, No. 5, pp. 55–56, May, 1973.