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.     

Radical chlorinations of triglycerides

Several triglycerides were synthesized with an iodoaroyl group. Intramolecular radical chain transfer chlorinations were conducted that resulted in the associated pair of fatty acids of the triglyceride becoming chlorinated. The distribution of monochlorinated species was similar to that obtained by direct radical chlorination of the relevant fatty acid methyl esters. Functionalization was, as expected, away from the carboxylate group but gave no indication that either alignment of chains or the constraints of an intramolecular process could limit the manifold of products of the reaction. To gauge the effect on halogenation of a structure, bearing more than one electron-withdrawing group, methyl oleate was converted to thebis trifluoroacetate of methyl 9,10-dihydroxystearate. No products of chlorination on carbons 2–8 were observed.     

以生物甘油为原料制备环氧氯丙烷的研究

以生物甘油为原料,经氯化反应和环化反应制备了环氧氯丙烷。首先以生物甘油为原料、以氯化氢气体为氯化剂、以己二酸为催化剂,采用无水Na2SO4除水4次,制得二氯丙醇（DCP）,氯化收率达90.09%;再以二氯丙醇和氢氧化钠反应制得环氧氯丙烷,通过单因素实验,得到环化反应的最佳工艺条件为：反应时间30min、氢氧化钠与二氯丙醇摩尔比1.15∶1、反应温度95℃,在此条件下的环化收率为88.2%。     

固相法合成涂料用高氯含量氯化聚乙烯

研究了固相合成高氯含量氯化聚乙烯过程中氯取代基，氯化温度、引发方式等对氯化速度的影响，及ＨＣＰＥ的降解。结果表明，大分子链上的氯取代代基对分子链进一步氯化起阻碍作用；氯化前期使用较高的温度或引发剂将使后面的氯化速度减慢；增大前期引发剂用量时，将会再次降低后期的氯化速度；通过机械剪切作用可使具有较高相对分子质量的ＨＣＰＥ大幅度降解。     

5－氯水杨酸的合成研究

比较了氯气直接氯代法和次氯酸叔丁酯法合成５ 氯水杨酸的合成条件和产物的纯度。认为直接氯代法生成物杂质较多而不易分离，但生产成本较低；而次氯酸叔丁酯法的产物所含杂质较少，但叔丁醇及溶剂易挥发，回收率低，生产成本较高     

5－氯水杨酸的合成研究

比较了氯气直接氯代法和次氯酸叔丁酯法合成５氯水杨酸的合成条件和产物的纯度。认为直接氯代法生成物杂质较多而不易分离，但生产成本较低；而次氯酸叔丁酯法的产物所含杂质较少，但叔丁醇及溶剂易挥发，回收率低，生产成本较高     

Synthesis and Characterization of 9(10)-Bromo-9-octadecenoic Acids

9(10)-Bromo-cis-9-octadecenoic acid, m. p. 36.7° C, was prepared by dehydrobromination of threo-9,10-dibromo-stearic acid with bases and by polar addition of hydrogen bromide to stearolic acid. The trans isomer, m. p. 6°–8° C, was obtained from the corresponding erythro-dibromide. Both compounds were characterized by IR and NMR spectroscopies and a reaction scheme for their formation by dehydrobromination is suggested.     

三氯蔗糖-6-乙酯的制备及结构表征

以蔗糖为原料,原乙酸三乙酯为酯化剂,经C-6乙酰化,生成蔗糖-6-乙酯,再用氯化亚砜和DMF制备的Vilsmeier试剂与蔗糖-6-乙酯进行氯化反应,得到三氯蔗糖-6-乙酯.考察了反应物的投料比对酯化反应的影响;反应温度、反应物的投料比和反应时间等因素对氯化反应的影响.结果表明:最佳反应条件为酯化反应温度为0℃,反应时...     

Step‐growth polymerization of 5‐[(9,10‐dihydro‐9,10‐ethanoanthracene‐11,12‐dicarboximido)‐3‐methylbutanoyl‐amino]isophthalic acid with aromatic diols

cis‐9,10‐dihydro‐9,10‐ethanoanthracene‐11,12‐dicarboxylic acid anhydride ( 1 ) was converted to imide acid ( 2 ) by reaction with S‐valine. Compound 2 was converted to the acid chloride ( 3 ) by reaction with thionyl chloride and then treated with 5‐aminoisophthalic acid in dry N,N‐dimethylacetamide to obtain 5‐[(9,10‐dihydro‐9,10‐ethanoanthracene‐11,12‐dicarboximido)‐3‐methylbutanoylamino]isophthalic acid ( 4 ). Direct step‐growth polymerization of this novel chiral diacid monomer 4 with a series of different diols in a system of tosyl chloride, pyridine, and N,N‐dimethylformamide was carried out. The optically active polyesters (PEs) were obtained with good yield and moderate inherent viscosity ranging from 0.23 to 0.48 dL/g. The resulting polymers were characterized with FTIR, ¹H‐NMR, and elemental analysis techniques. The prepared PEs showed good thermal stability up to 320°C as measured by thermogravimetric analysis. Specific rotation experiments demonstrated the induction of optical activity due to successful insertion of S‐valine in the structure of pendant groups. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and properties of 1,5- and 1,8-dichloro-substituted poly(9,10-dihydroanthracene-9,10-diylidene)s

Two new dichloro-substituted poly(9,10-dihydroanthracene-9,10-diylidene)s were prepared by self-condensation of 1,5-dichloroanthrone and 1,8-dichloroanthrone. The bromination and thermal and semiconductive properties were investigated.     

2-氨基-6-溴吡啶的合成研究

2-氨基-6-溴吡啶及其衍生物是重要的药物中间体,以2-氨基-6-甲基吡啶为原料,经重氮化、溴代、氧化、氯化、氨解、霍夫曼降解合成2-氨基-6-溴吡啶。重点考察了氯化、氨解及霍夫曼降解反应条件对收率的影响,总收率34.6%,产品结构经红外、核磁得到确认。     

6-(1-溴乙基)-4-氯-5-氟嘧啶的合成工艺研究

以5-氟尿嘧啶为起始原料,经三氯氧磷氯化,溴化乙基镁格氏反应乙基化,经水解、还原、氯化,再经N-溴代琥珀酰亚胺溴化制得目标产物6-(1-溴乙基)-4-氯-5-氟嘧啶。总收率为51.6%。     

Synthesis of phenyl substituted C18 furanoid fatty esters

Methyl 9,12-epoxy-10-phenyl-9,11-octadecadienoate was prepared by acid catalyzed cyclization of methyl 9,12-dioxo-10-phenyloctadecanoate, which was derived from the oxidation of methyl 9-hydroxy-12-oxo-10-phenyloctadecanoate. The latter was exclusively obtained from methylcis-9,10-epoxy-12-oxooctadecanoate with phenyllithium in the presence of copper (I) bromide. A mixture of positional isomers, methyl 9,12-epoxy-10(11)-phenyl-9,11-octadecadienoates, was also prepared by another route. The spectroscopic properties of the various intermediates and products were studied. The positional isomers of the phenyl substituted furanoid fatty esters were characterized by¹³C nuclear magnetic resonance spectrometry.     

On the synthesis of LaCl3 catalysts for oxidative chlorination of methane

LaCl₃ is an active and selective catalyst for oxidative chlorination of methane to methyl chloride, generated in situ by chlorination from LaOCl. The latter is prepared by precipitation of La(OH)₂Cl and subsequent calcination. The synthesis route was modified by using different bases in order to synthesize high surface area LaOCl catalyst precursors. Ammonium hydroxide and the organic bases tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide are used as precipitating agents. The marked increase of the specific surface area by using organic bases indicates also that they may act as templating agents. After chlorination the specific surface areas of pure LaOCl samples decrease drastically, lanthanum carbonate, however, acts as structural promoter stabilizing the specific surface area during chlorination.     

High-performance composites from polyimide matrix resins that utilize a cross linking reaction of biphenylene end-caps with acetylene units in the main chain

Graphite-reinforced composites were prepared with oligomeric polyimides having biphenylene end-caps and acetylene linkages in the polymer chain. The oligomers were crosslinked by the reaction of the biphenylenes with the diphenyl acetylenes to form 9,10-diphenylphenanthrene units. The resulting composites had good mechanical properties. Thermal oxidative aging studies show that the unidirectional graphite fiber composites maintained good mechanical properties up to 1200 h at 316°C.     

3，5-二氯苯甲酰氯的制备

以邻氨基苯甲酸为原料通过氯代、重氮化、酰氯化制备出了3，5-二氯苯甲酰氯，总收率达到了86％。     

醚桥联二聚体合成的关键中间产物-9，10-脱水青蒿素

以二氢青蒿素为反应原料在制备不对称醚桥联二聚体时得到了关键的中间产物9,10-脱水青蒿素。9,10-脱水青蒿素保留了母体化合物青蒿素中的过氧基团并且含有一个C=C双键,其抗疟活性与蒿乙醚的抗疟活性相似。9,10-脱水青蒿素在合成蒿醚类衍生物时,是关键的中间产物。培养9,10-脱水青蒿素的单晶,通过X射线表征其结构。运用Puckering分析方法对9,10-脱水青蒿素结构中环的构象进行了半定量描述。其中几个六元环分别呈现椅式、扭船式、信封式构象。     

Selective Chlorination of Side-chains in Friedel-Crafts Polymers

Aralkyl polymers with ethyl side-chains were prepared by Friedel-Crafts reactions. Ethylbenzene and bis(p-chloromethyl)benzene (BCMB) were reacted together in the presence of stannic chloride to produce polymers of various molecular weights. A study was then carried out of the chlorination of these polymers, using (a) molecular chlorine, (b) molecular chlorine with a peroxide catalyst and phosphorus pentachloride, (c) sulphuryl chloride. The objective was to determine the best conditions for chlorination to occur selectively at the α-carbon atom of the ethyl group, with minimal chlorination at either the β-position or the main-chain methylene groups. Analysis of ¹H nuclear magnetic resonance spectra of the chlorinated polymers suggests that in most cases chlorination occurs extensively both in the side-chain and in the main-chain methylene groups. Conditions were found, however, which favour chlorination at the α-position. The greatest selectivity was achieved when molecular chlorine, a peroxide catalyst and phosphorus pentachloride were used in benzene solvent.     

MEK wiping prior to chlorination to improve the adhesion of vulcanized SBR rubber containing paraffin wax

In this study, it was shown that the degree of effectiveness produced by halogenation with trichloroisocyanuric acid (TCI) was influenced by previous methyl ethyl ketone (MEK) wiping of a synthetic vulcanized styrene-butadiene rubber (R2) surface. The MEK wiping of the R2 rubber surface prior to chlorination with TCI removed the paraffin wax layer from the surface, which favoured the chlorination and oxidation reactions of the rubber. Chlorination with TCI decreased the contact angle values (increased the wettability) mainly due to the creation of C–Cl and C=O moieties, as well as roughness. The amount of these chemical moieties increased when the MEK wiping was applied prior to chlorination, so higher degrees of chlorination and oxidation were obtained on the R2 rubber surface. T-peel strength values increased more markedly if the MEK wiping was carried out before chlorination with TCI, in agreement with the higher degree of modifications produced in the R2 rubber surface. In fact, a cohesive failure in the R2 rubber was obtained in the adhesive joint produced with MEK wiped + TCI chlorinated R2 rubber.     

Synthetic detergents from animal fats. IV. Sodium 9,10-dichlorooctadecyl sulfates

Summary Sodium 9,10-dichlorooctadecyl sulfates were prepared by the addition of chlorine to oleyl and to elaidyl alcohols, and sulfation of the dichlorooctadecanols with chlorosulfonic acid. The sodium 9,10-dichlorooctadecyl sulfates are readily soluble in water at 25°C and resemble sodium oleyl sulfate in detergent and surface-active properties. Tallow alcohols can be chlorinated by the addition of chlorine and sulfated with one of the usual sulfating agents to produce an adequately soluble detergent and surface-active agent. I, II, and III in this series are references (5), (4), and (7), respectively. Presented at the meeting of the American Oil Chemists' Society in Minneapolis, October 1954. A laboratory of the Eastern Utilization Research Branch, Agricultural Research Service, U. S. Department of Agriculture.