Identification of nine acetylenic fatty acids, 9-hydroxystearic acid and 9,10-epoxystearic acid in the seed oil ofJodina rhombifolia hook et arn. (Santalaceae)

In addition to some usual fatty acids, the seed oil ofJodina rhombifolia (Santalaceae) contains nine acetylenic fatty acids [9-octadecynoic acid (stearolic acid) (1.1%),trans-10-heptadecen-8-ynoic acid (pyrulic acid) (20.1%), 7-hydroxy-trans-10-heptadecen-8-ynoic acid (2.3%),trans-10,16-heptadecadien-8-ynoic acid (0.7%), 7-hydroxy-trans-10,16-heptadecadien-8-ynoic acid (0.1%),trans-11-octadecen-9-ynoic acid (ximenynic acid) (20.3%), 8-hydroxy-trans-11-octadecen-9-ynoic acid (12.2%),trans-11,17-octadecadien-9-ynoic acid (1.5%), 8-hydroxy-trans-11,17-octadecadien-9-ynoic acid (1.3%), 9-hydroxystearic acid (<0.1%) and 9,10-epoxystearic acid (0.7%)]. The fatty acids have been analyzed by gas chromatography/mass spectrometry of their methyl ester and 4,4-dimethyloxazoline derivatives. The hydroxy fatty acid methyl esters have been examined also as trimethyl-silyl ethers. Furthermore, the fatty acid methyl esters (FAME) have been fractionated according to their polarity (FAME-A: nonhydroxy; FAME-B: hydroxy fatty acids) and to their degree of unsaturation (FAME-A1/A2; FAME-B1/B2) by preparative thin-layer chromatography and argentation chromatography, respectively. All of these fractions have been analyzed by ultraviolet and infrared spectroscopy, and the fractions FAME-A and FAME-B have been analyzed further by nuclear magnetic resonance (¹H,¹³C, 2D H/C, attached proton test) spectroscopy and gas chromatography/mass spectrometry. This work is dedicated to the 65th birthday of Prof. Dr. K. Pfeilsticker, Institut of Food Science, University Bonn (Germany).     

Acetylenic compounds in stored packaged carrots

Stored carrots vacuum packed in plastic shrink bags showed significant variations in the concentration of certain important secondary compounds. In the acetylene group, 18 compounds were isolated and measured. Only eight of these compounds have previously been reported as carrot constituents. The concentrations of 10 of the 18 increased with storage time, and six were present only in stored samples.     

High-performance liquid chromatography of the triacylglycerols ofVernonia galamensis andCrepis alpina seed oils

The triacylglycerols ofVernonia galamensis andCrepis alpina seed oils were characterized because these oils have high concentrations of vernolic (cis-12,13-epoxy-cis-9-octadecenoic) and crepenynic (cis-9-octadecen-12-ynoic) acids, respectively. The triacylglycerols were separated from other components of crude oils by solid-phase extraction, followed by resolution and quantitation of the individual triacylglycerols by reversed-phase high-performance liquid chromatography with an acetonitrile/methylene chloride gradient and flame-ionization detection. Isolated triacylglycerols were characterized by proton and carbon nuclear magnetic resonance and by capillary gas chromatography of their fatty acid methyl esters. The locations of the fatty acids on the glycerol moieties in the oils were obtained by lipolysis. TheVernonia galamensis oil contained 50% trivernoloyl and 21% divernoloyllinoleoyl glycerols along with 20% triacylglycerols with one vernolic and two other fatty acids. TheCrepis alpina oil contained 36% tricrepenynoyl and 33% dicrepenynoyllinoleoyl glycerols, 17% triacylglycerols with two crepenynic and one other fatty acid and 7% triacylglycerols with one crepenynic acid and two other fatty acids. Vernolic acid was found at both the 1(3)- and 2-glycerol carbons but was more abundant at the 1,(3)-position in theVernonia galamensis oil. Crepenynic acid was found at both glycerol carbon positions but was more abundant at the 2-position in theCrepis alpina oil. Visiting scientist from Technical Research Institute, Snow Brand Milk Company, Ltd., Saitana, Japan.     

Hetero-Diels–Alder reactions of hetaryl thiochalcones with acetylenic dienophiles

Hetaryl-substituted thiochalcones react with acetylenic mono- and diesters in the THF solution in the presence of LiClO₄ at 65°C to give, after 24?h, 4H-thiopyran carboxylates and dicarboxylates, respectively, in moderate to good yields. The same reactions were performed also in the THF solution without a catalyst under microwave irradiation. In that case, the reaction time was reduced to three minutes and, in most cases, an improvement in the yield of the [4+2]-cycloadduct was observed. The reactions with methyl propiolate occurred regioselectively and the 3-carboxylates were formed exclusively.     

烃类化合物炔键选择加氢Pd-Pb/CaCO3催化剂的改进

利用XRD和SEM研究了EDTA、草酸等助剂对沉淀CaCO3显微结构的影响，结果表明，CaCO₃晶型及形貌随助剂不同而变化，甚至同一助剂不同添加量亦会导致其晶相的显著差异。XRD分析表明，在草酸存在下，沉积物为单一的方解石相，该晶型的CaCO₃对Pd-Pb/CaCO₃催化剂呈现明显的模板效应。不同还原方法的尝试说明，水合肼是一种好的还原剂。TEM研究表明，在适宜条件下对催化剂老化处理，表面金属钯颗粒发生聚并，并且由此带来部分氢化选择性的较大提高。     

生成空间异构体对酮的炔化反应平衡的影响

导出了丁酮和４－甲基－２－戊酮乙炔化而生成空间异构体的化学平衡方程式．考虑到有关的炔－醇和炔二醇没有旋光性，论证了生成各空间异构体的有关反应的平衡常数的相对大小，并给以适当假定．把考虑生成空间界构体的平衡计算结果与不考虑生成空间异构体的计算结果进行了比较．前一种情况的炔二醇最大产率要比后者的高出８～１２％．     

Metal‐Tuned Acetylene Linkages in Hydrogen Substituted Graphdiyne Boosting the Electrochemical Oxygen Reduction

Different from graphene with the highly stable sp²‐hybridized carbon atoms, which shows poor controllability for constructing strong interactions between graphene and guest metal, graphdiyne has a great potential to be engineered because its high‐reactive acetylene linkages can effectively chelate metal atoms. Herein, a hydrogen‐substituted graphdiyne (HsGDY) supported metal catalyst system through in situ growth of Cu₃Pd nanoalloys on HsGDY surface is developed. Benefiting from the strong metal‐chelating ability of acetylenic linkages, Cu₃Pd nanoalloys are intimately anchored on HsGDY surface that accordingly creates a strong interaction. The optimal HsGDY‐supported Cu₃Pd catalyst (HsGDY/Cu₃Pd‐750) exhibits outstanding electrocatalytic activity for the oxygen reduction reaction (ORR) with an admirable half‐wave potential (0.870 V), an impressive kinetic current density at 0.75 V (57.7 mA cm^?2) and long‐term stability, far outperforming those of the state‐of‐the‐art Pt/C catalyst (0.859 V and 15.8 mA cm^?2). This excellent performance is further highlighted by the Zn–air battery using HsGDY/Cu₃Pd‐750 as cathode. Density function theory calculations show that such electrocatalytic performance is attributed to the strong interaction between Cu₃Pd and C?C bonds of HsGDY, which causes the asymmetric electron distribution on two carbon atoms of C?C bond and the strong charge transfer to weaken the shoulder‐to‐shoulder π conjugation, eventually facilitating the ORR process.     

顺式α-砜基烯丙醇的合成及其晶体结构

在10 mol%的CuCN催化下,1-苯基-2-对甲苯砜基乙炔与对甲基苯基溴化镁发生碳镁化反应得到α-砜基烯基格氏试剂,其进一步与苯甲醛反应得到目标产物为α-砜基烯丙醇类化合物（Z）-1,3-二苯基-3-对甲基苯基-2-对甲苯砜基烯丙醇,并将目标产物用1HNMR,13C NMR,IR,Anal.Calc.和MS进行了表征.其晶体结构由单晶X-射线衍射法测定.晶体属单斜晶系,空间群P2（1）/c,晶胞参数：a=9.853 1（8）,b=11.796 9（9）,c=21.141 2（17）;a=90°,β=95.279（2）°,γ=90°.V=2 446.9（3）3,T=293 K,Z=4,Dc=1.23 4 g/cm,μ=0.16 mm-1,λ=0.710 73,F（000）=960,结构偏离因子R=0.115 6,wR2=0.238 9,共收集到5 870个衍射点,其中3 382个独立衍射点.     

Structural investigation of polydiacetylenes: A variable temperature solid state13C CP/MAS NMR study

The spectral features in the solid state¹³C CP/MAS NMR of poly (1,1,6,6-tetraphenylhexadiyn diamine) (poly(THD)) are compared with X-ray diffraction. The NMR data suggests that acetylenic carbons are nonequivalent in the unit cell resulting in two resonances. On the other hand, a single acetylenic carbon resonance was observed for poly (1,6-di-N-carbozolyl-2,4-hexadiyne) (poly(DCH)). The orientation of side groups in the crystal structures of poly(DCH) and poly(THD) are responsible for equivalence and nonequivalence of acetylenic carbons. The structural changes due to thermochromic transitions are monitored by variable temperature solid state NMR. The solid state VT NMR data suggest that the backbone and side chain conformations of blue phase and red phases of poly(bis-n-propyl urethane of 5,7-dodecadin-1,12-diol) (poly(PUDO)) are distinctly different. For the first time, we present a solid state NMR spectrum showing the presence of both the blue and red phases of this polymer at the thermochromic transition temperature (ca. 115–125°C).     

Synthesis of heterocyclic phosphonato esters by reaction between triphenyl phosphite and acetylenic diesters in the presence of sulfur-containing heterocyclic compounds

The reaction between triphenyl phosphite and acetylenic esters in the presence of some heterocyclic compounds such as oxazolo[4,5-b]pyridine-2(3H)-thione, 2-mercaptobenzothiazole or 2-mercaptopyrimidine led to the formation of phosphonato esters in high yield.