Reaction of 3-methyl phenol with methyl α-eleostearate

The aromatic ring substitution reaction of 3-methyl phenol with methyl α-eleostearate under acidic conditions was carried out. The product was analyzed to find out if 3-methyl phenol was subjected to the ring substitution reaction with methyl α-eleostearate at its conjugated double bonds. Up to two molecules of 3-methyl phenol were addition-reacted with the conjugated triene of the eleostearyl group of methyl α-eleostearate. The 4-position of 3-methyl phenol was preferentially subjected to the cresol's ring substitution. When 3-methyl phenol was reacted with a relatively large amount of methyl α-eleostearate, the substitution reaction occurred at the 6- as well as 4-position of 3-methyl phenol, to yield a methyl α-eleostearate dimer having 3-methyl phenol units in its molecule. The above results were confirmed by infrared (IR), nuclear magnetic resonance (NMR), and high-speed liquid chromatographic (HLC) analyses, and the results of a previous paper connected with reaction of 3-methyl phenol were supported by the results of this paper.     

Reactions of phenols with tung oil

As regards the aromatic ring substitution reactions of various kinds of phenols with tung oil under acidic conditions, an investigation was made on the influences of the kinds and substitution positions of alkyl groups of the phenlos on the reaction. Alkyl phenols increased in reactivity in the order of ortho, meta, and para in the position of alkyl substitution. This can be attributed to the preferential para addition of tung oil to the phenol nucleus as reported in the previous paper. The larger alkyl group gave increased reactivities in the reactions of alkyl phenols with tung oil. This has something to do with compatibilities between phenols and tung oil (differences in solubility parameter between phenols and tung oil).     

桐油改性曼尼期碱固化剂的合成及性能研究

桐油的共轭双键具有极强的反应活性,易与苯酚芳环上邻或对位的活性氢发生傅氏取代反 应。余下的两个活性氢位置仍然能与胺类、醛类发生曼尼期碱的缩合反应。本文研究了桐油改性 曼尼期碱的合成反应的条件、影响因素及产品的固化性能,并指出桐油改性曼尼期减为一综合性 能优异的环氧树脂固化剂。     

桐马酸二辛一甲酯合成及增塑PVC研究

选用具有丰富不饱和共轭三键的桐油为原料,并通过酯交换、D–A反应对其改性合成了具有六元环结构的多酯类化合物3–正丁基–6–(9–癸烯酸甲酯–10基)–4–环己烯二酸二异辛酯(METATM),并对其改性聚氯乙烯(PVC)的各项性能进行了研究。结果表明,桐油具有丰富的α–桐酸,其甲酯与马来酸二异辛酯合成METATM的最佳工艺为:桐油甲酯与马来酸二异辛酯的物质的量之比为1∶1,反应温度为220℃,反应时间为5 h,转化率达97.4%;其产品闪点与加热减量均优于邻苯二甲酸二辛酯(DOP),对PVC具有较好的增塑性能,但效果不及DOP,更适合作为辅助增塑剂与DOP复配使用,可有效降低非环保增塑剂的使用量。     

Untersuchungen des Reaktionsverlaufes und der Produkte der säurekatalysierten Reaktion von Phenolen mit Holzöl, 2. Vergleichende untersuchungen an verschiedenen phenolen

In this paper the acid-catalysed reaction between phenols and tung oil is investigated for 4 different phenols (phenol, o-, m- and p-cresol). This reaction is important for the production of modified resins for electrical insulating laminates. In particular by means of ¹³C-NMR- and IR-method it is proved that phenols are C-alkylated by tung oil in the manner of a Friedel-Crafts-reaction exceptionally. The reaction positions at the phenols are determined. Further, the rates of the reaction of phenol with the eleostearic acid esters are compared for the four different phenols.     

新型含磷阻燃型桐油基聚氨酯硬泡的制备及性能表征

桐油与甘油在甲醇钠为催化剂的条件下发生醇解反应得到桐油醇解产物（GTO）,GTO经环氧化得到环氧化桐油醇解产物（EGTO）,EGTO与9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物（DOPO）发生开环反应生成新型含磷阻燃型桐油基多元醇（PTOP）。PTOP部分取代聚醚多元醇（PPG4110）与异氰酸酯及助剂反应,通过一步法制备聚氨酯硬泡（RPUF）。采用万能试验机、热导率测定仪、热重分析仪和锥形量热仪分别考察RPUF的力学性能、热稳定性和燃烧行为。结果表明：随着PTOP替代石油基多元醇的比率增大,RPUF的压缩强度、密度、热导率先增大后减小,热稳定性提高,极限氧指数（LOI）由18.1%提高至26.0%,而总放热量先减小后增大,这主要是由于PTOP结构中的DOPO基团具有阻燃作用而PTOP结构中含有的桐油基脂肪链易于燃烧且热释放量较大。以上结果表明PTOP部分取代PPG4110制备的RPUF具有良好的阻燃性能和热稳定性。     

Untersuchungen des Reaktionsverlaufes und der Produkte der säurekatalysierten Reaktion von Phenolen mit Holzöl, 1. Phenol und Holzöl

In this paper the acid-catalyzed reaction between phenol and tung oil is investigated. This reaction is important for the production of modified phenolic resins for electrical insulating laminates. Based on the characterization of reaction products by means of gas- and liquid chromatography, IR, ¹H-NMR, ¹³C-NMR spectroscopy and MS is established, that phenol is C-alkylated by tung oil in the manner of a Friedel-Crafts-reaction. Phenol reacts only with the double bonds of the eleostearic acid links of the tung oil.     

桐油改性酚醛树脂的研究

通过桐油和本酚在催化剂存在下反应，然后再在碱性催化剂存在下与甲醛反应成功地制得了一种桐油改性甲阶酚醛树脂。利用红外光谱和1H—核磁共振谱等分析技术对这类改性树脂的结构的基本性能进行了表征。用这类桐油改性酚醛树脂代替橡胶改性酚醛树脂作为基作树脂所压制的石棉基汽车刹车片，其摩擦性能显著提高并超过GBn257—86所规定的技术要求，可望用作耐高温摩阻材料。     

Conjugated hydrogenation of triglyceride oil containing conjugated acid

Conjugated hydrogenation of tung oil (fatty acid composition: elaeostearic 57.0%, linoleic 25.8%, oleic 11.2% and saturated 6.0%) has been investigated to ascertain the influence of hydrogen donors, namely primary and secondary alcohols, on rate and selectivity under different operating conditions. 2-Propanol, in general, reflects faster rate and greater degree of reduction but less selectivity towards the reduction of unsaturated acids than ethanol, when tung oil is treated at 200 C, 225 C and 250 C with 2% Ni (optimum catalyst level) and theoretical as well as 100% excess of theoretical amount of the two hydrogen donors to ensure complete hydrogenation of the oil. The rate and degree of reduction with ethanol are less influenced by its amount and amount of catalyst, but with 2-propanol these depend considerably on both the amount of hydrogen donor and amount of catalyst. During conjugated hydrogenation of tung oil, deposition of gel-like mass in minor amount occurs only at the wall of the reaction vessel. This is evidently due to polymerization of the conjugated trienoic acid. Presented at the IXth ISF Congress, Rotterdam, September 1968.     

Polymerization of tung oil by reaction of phenols with tung oil

Investigation was made on the mechanism of polymerization in reactions of tung oil and phenols in the presence of an acid catalyst. It was made by means of comparative HLC and NMR analyses of the products of tung oil self-polymerization, other varied vegetable oil-various phenol reactions, and tung oil-various-in-functionality phenol reactions under given conditions. As a result, it was confirmed that polymerization in reactions of tung oil and phenols is attributed not to tung oil self-polymerization but to di- or trialkylation, with tung oil, of phenols, which can serve as crosslinking agents of tung oil.     

4-叔戊基-2-(α-甲苄基)苯酚的合成

以对叔戊基苯酚和苯乙烯为起始原料,浓磷酸作催化剂,设计合成铷、铯萃取剂4-叔戊基-2-(α-甲苄基)苯酚。考察反应温度、反应时间、原料配比和催化剂用量为对4-叔戊基-2-(α-甲苄基)苯酚产率的影响。确定最佳反应条件为:反应温度140℃,反应时间3 h,n(苯乙烯)∶n(对叔戊基苯酚)=1.4,催化剂用量为对叔戊基苯酚质量的24.63%。此条件下,4-叔戊基-2-(α-甲苄基)苯酚产率为58.76%。     

Über die Struktur cyclisierter Fettsäureester

The Structure of Cyclised Fatty Acid Esters It is proved that the cyclic fatty acids which are obtained from tung and linseed oils by alkali-treatment contain mainly two types of products. Approximately 30% of these consist of 1,2-disubstituted cyclohexadiens, whose one double bond of the ring is in the 1-position and the other one is conjugated to the former. Approximately 60% of the mixture is comprised of ω-(2-alkyliden-cyclohexenyl)-fatty acid esters. The double bond in the ring is predominantly in the 3-position. As a result of the rearrangement of double bonds before cyclisation, R′varies from C₂ to C₁₁ and R″ from C₀ to C₉.     

Thermosetting polymers from cationic copolymerization of tung oil: Synthesis and characterization

The cationic copolymerization of tung oil with the divinylbenzene comonomer initiated by boron trifluoride diethyl etherate produces promising plastics. The gel times are largely dependent on the relative composition and the reaction conditions and vary from a few seconds to 1 h. Controlled reactions producing homogeneous materials can be obtained by (1) lowering the reaction temperature or (2) decreasing the initiator concentration to less than 1 wt % or (3) adding a certain amount of a less reactive oil, such as soybean oil, low saturation soybean oil (LoSatSoy), or conjugated LoSatSoy to the reaction. The resulting polymers are rigid and dark brown in color. The weight % of the starting materials converted to the crosslinked polymer is ∼85–98% as determined by Soxhlet extraction with methylene chloride. The structure of the bulk product is that of a crosslinked polymer network plasticized by a small amount of low molecular weight oil. The chemical composition of the bulk polymers varies with the original composition of the tung oil system. Dynamic mechanical analysis shows that the resulting products are typical thermosetting polymers with densely crosslinked structures. The modulus of the plastics is approximately 2.0 × 10⁹ Pa at room temperature. One broad glass transition is observed at approximately 100°C. Thermogravimetric analysis shows that the tung oil polymers are thermally stable below 200°C with a 10% weight loss in air around 430°C. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1044–1056, 2000     

A novel method for the introduction of a methyl group into the furan ring of a 2,5-disubstituted C18 furanoid fatty estervia a malonic acid function

Furan ring opening with benzohydroxamic acid of methyl 9,12-epoxy-9,11-octadecadienoate gave a mixture of positional isomers of conjugated methyl 3-phenyl-1,4,2-dioxazolyl C₁₈-enone esters 6a,6b. Michael addition of diethyl malonate anion to the conjugated enone system of 6a,6b furnished the corresponding malonyl intermediates 7a,7b, which upon removal of the dioxazole ring by hydrolysis gave methyl 10- and 11-dicarbethoxymethyl-9,12-dioxooctadecanoate 8a,8b. Cyclization of the latter gave the trisubstituted C₁₈ furanoid fatty esters 9a,9b, containing the malonate ester function at the 3-/4-position of the furan ring. Base hydrolysis of compounds 9a,9b gave the corresponding tricarboxylic acid derivatives 10a,10b, which were esterified to the trimethyl esters 11a,11b in BF₃/MeOH. When a mixture of 9a,9b was refluxed with Na₂CO₃/MeOH, hydrolysis of the malonate ester function was followed by decarboxylation to yield a-CH₂COOH substituent at the 3-/4-position of the furan ring (12a, 12b). Esterification of the latter with BF₃/MeOH gave the corresponding methyl diester derivatives 13a,13b. When a mixture of tricarboxylic acids 10a,10b was heated at 160–180°C for 6 hr, exhaustive decarboxylation of malonic acid function furnished a methyl group at the 3-/4-position of the furan nucleus. Esterification of the decarboxylated product gave a mixture of trisubstituted furanoid compounds 14a,14b (overall yield 28%). The procedure constitutes a novel method for the introduction of a methyl groupvia a malonic acid group to the 3-/4-position of the furan ring of a 2,5-disubstituted C₁₈ furanoid fatty ester.     

Preparation of pressure-sensitive adhesives from tung oil via Diels-Alder reaction

In this study, tung oil was polymerized with a dimaleimide (4,4’-methylene-bis(N-phenylmaleimide) (MPMI) and two diacrylates (poly(propylene glycol) diacrylate (PPGDA) and bisphenol A glycerolate diacrylate (BPAGDA) via Diels-Alder reaction (DA reaction) to prepare pressure-sensitive adhesives (PSAs). On the one hand, the polymer of tung oil and MPMI was readily prepared however it was too rigid to serve as a PSA. On the other hand, the polymerization of tung oil with PPGDA or BPAGDA resulted in PSAs with peel strengths ranging from 0.1 to 0.2 N cm⁻¹ and loop tacks ranging from 0.4 to 0.5 N. Nevertheless, tung oil reacted readily with acrylic acid to form adducts (TOAA) with lower content of conjugated diene groups than those of tung oil. The use of TOAAs instead of tung oil to polymerize PPGDA failed to increase the peel strength of the resulting PSAs. However, polymerizations of TOAAs with BPAGDA resulted in PSAs with much higher peel strengths and much higher loop tacks than the polymerization of tung oil with BPAGDA. In addition, the introduction of a small amount of MPMI in the polymerization of TOAA and PPGDA significantly shortened the curing time.     

Versatile 2-amino-4-substituted-1,3-thiazoles: synthesis and reactions

Syntheses and reactions of 2-amino-4-substituted-1,3-thiazoles are reviewed in a formal way. The title compounds are most easily accessible by various approaches, and even waste-free solid-state procedures have been developed. The substitution in 4-position has synthetic reasons and therefore most interest accumulates around these derivatives of 2-aminothiazole. The high reactivity of both the amino group and the positions 3 and 5 of the 1,3-thiazole ring are used for numerous syntheses in a comprehensive way. The reactions are subdivided in groups that cover reactions at the amino substituent without touching the thiazole ring, reactions which involve both nitrogens in the formal amidine system to give thiazolo-pyrimidinones and -imidazoles as well as more involved polycondensed N,S-heterocycles with multiple possibilities for substituents, and substitution reactions at the 5-position of the thiazole ring. Most of the imaginable reaction types have been successfully applied and used, as many of the synthesized compounds exhibit interesting biological activity in various fields.     

嘧螨酯的合成技术与防治效果

以氰胺和异丙醇制备异丙氧基脒甲烷磺酸盐,再与三氟乙酰乙酸乙酯反应制得2-异丙氧基-4-羟基-6-三氟甲基嘧啶,最后与(E)-2-[2-(氯甲基)苯基]-3-甲氧基丙烯酸甲酯反应合成目标嘧螨酯,通过试验考察了物料配比、反应时间、反应温度、催化剂用量等因素对反应的影响,确定了合成中较佳的试验条件:第一步反应时间12h,摩尔比为n1(三氟乙酰乙酸乙酯):n2(异丙氧基脒甲烷磺酸盐)=1.086:1,PH值为9.2时;第二步反应时间为5h,反应温度为80oC,以K2CO3作缚酸剂,DMF作溶剂,催化剂用量为2.4%。在此条件下,反应的总收率可达43%以上,原药纯度达到97.9%,且催化剂重复使用6次仍然保持较高活性。其结构经核磁、红外验证。生物活性测定结果表明该化合物具有良好的杀螨活性。     

7-氨基-3-(1-吡啶甲基)头孢烯酸氯化物的合成

7-氨基-3-(1-吡啶甲基)头孢烯酸(7-APCA)氯化物是合成头孢他啶的重要中间体.以GCLE为原料经过3步反应,首先GCLE和NaI反应制备碘化物,进一步和吡啶反应得到3位取代产物,然后经过脱除7位和4位的保护基得到7-APCA的卤化物,总收率为77%,各化合物均通过1H-NMR确证结构.     

Studies in the expression of oil from tung fruit

Summary 1. Tests indicated that best results in yield of crude and filtered oil by an expression procedure are obtained with a tung meal containing 4.2% moisture and 20% shell. 2. The drying of tung meal using an initial air temperature of 320° F. appeared to adversely affect the yield of filtered oil from the expeller process. 3. A filtration test was developed for determining the amount of foots in a crude tung oil. 4. It was found difficult to obtain efficient oil expression from tung meals containing filter cake; in one test with this material the resulting press cake was high in oil content, while in another test the crude tung oil contained about twice as much foots material as was present in crude tung oil from tung meal containing no filter cake. 5. The expression of tung oil from a tung meal consisting of ground old tung kernels and tung shell was found difficult if not impossible. This difficulty appeared to be due, at least partly, to the fact that the meal from old kernels will not plasticize when subjected to heat and pressure. When these kernels were mixed with new kernels no difficulty was experienced in expressing the tung oil from the meal. 6. Tests indicated that hulling the moist tung fruit in the grove does not interfere with the expression of the oil if the moist dehulled tung fruits are properly dried before pressing. 7. A process was developed for producing a clear tung oil by treating the crude oil with a chemical agent to precipitate certain non-oil constituents in the crude tung oil followed by either pressure filtration or centrifugation. 8. When tung oil filter cake was mixed with an equal amount of tung press cake, over 98 percent of the oil could be solvent-extracted by petroleum solvents. Presented at the American Oil Chemists’ Society meeting, New Orleans, La., May 10–12, 1944. Some of the material was presented at the American Tung Oil Association meeting. Pensacola, Fla., April 28–29, 1944, and published in the proceedings. Agricultural Chemical Research Division Contribution No. 145.     

高强度多胶粉云母带粘合剂的研制

在苯甲酸铅的作用下,将自制的改性剂引入环氧－双马来酰亚胺－ＴＯＡ体系中,获得了综合性能良好的高强度多胶粉云母带用粘合剂Ｉａ。该粘合剂不仅具有长的室温贮存期（大于四个月）,而且其固化体系在维持优良的介电性能的同时,胶条的室温冲击强度为１３．６ｋＪ／ｍ~２,１５５℃的静态弯曲强度为１３．０ＭＰａ;用玻璃布增强的云母板材,室温冲击强度为８１．５ｋＪ／ｍ~２,室温或１５５℃的静态弯曲强度为２８３．４ＭＰａ或１２９．ＩＭＰａ。此外,在温度低于 ２００℃时,固化物的动态力学模量均大于 １００ＭＰａ。