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41.
42.
All four possible enantiomers of the 3-hydroperoxy-4-penten-1-ols 2a, b and their corresponding 4-pentene-1,3-diols 4a,b have been prepared for the first time in high enantiomeric purity (up to 98% ee) and in preparative amounts according to two distinct ways: First the photooxygenation of the racemic homoallylic alcohols 1 gave the racemic hydroperoxy alcohols 2, which have subsequently been kinetically resolved by horseradish peroxidase (HRP); alternatively, first the lipase-catalyzed resolution afforded the optically active homoallylic alcohols 1 and subsequent photooxygenation led to the enantiomerically enriched hydroperoxy alcohols 2. 相似文献
43.
Summary A new simplified version of a closed on-column injector is introduced. Because of its design isobaric injection conditions do not have to be followed and a wide range of injection temperatures above the boiling point of the sample solvent can be chosen for on-column injections in capillary gas chromatography. Also, when following certain basic injection rules, injections of large sample volumes (20 l or more) give accurate and reproducible results without further problems.Presented at the 17th International Symposium on Chromatography, September 25–30, 1988, Vienna, Austria. 相似文献
44.
This paper presents a method for programming the flow rate of liquids inside open microfluidic networks (MFNs). A MFN comprises a number of independent flow paths, each of which starts with an open filling port, has a sealed microchannel in which assays can be performed, and an open capillary pump (CP). The MFN is placed over Peltier elements and its flow paths initially fill owing to capillary forces when liquids are added to the filling ports. A cooling Peltier element underneath the filling ports dynamically prevents evaporation in all filling ports using the ambient temperature and relative humidity as inputs. Another Peltier element underneath the CPs heats the pumps thereby inducing evaporation in the CPs and setting the flow rate in the microchannels. This method achieves flow rates in the microchannels ranging from approximately 1.2 nL s(-1) to approximately 30 pL s(-1), and is able to keep 90% of a 0.6 microL solution placed in an open filling port for 60 min. This simple and efficient method should be applicable to numerous assays or chemical reactions that require small and precise flow of liquids and reagents inside microfluidics. 相似文献
45.
Anil Kumar PG Pregosin PS Schmid TM Consiglio G 《Magnetic resonance in chemistry : MRC》2004,42(9):795-800
Three new salts of Rh(I), [Rh(1,5-COD)(Biphemp)]X, Biphemp = (6,6'-dimethylbiphenyl-2,2'-diyl)bis(diphenylphosphine), X = BF4-, 2a, PF6-, 2b, and CF3SO3-, 2c, were prepared and studied using PGSE diffusion, 1H-19F HOESY and inverse 103Rh (amongst other) NMR methods. Although the immediate coordination sphere of the cation does not sense the change in the anion, the PGSE diffusion and 1H-19F HOESY data suggest that, in addition to some ion pairing, each of the anions in 2 demonstrates selectivity in its approach towards the cation. 相似文献
46.
Summary The purpose of this study is to find out whether the previously applied procedures for determining hot water soluble boron trace contents in soils using dianthrimide or azomethin-H can be substituted by ICP-AES. Research was made into chemical and spectral interferences which can arise in all three methods. The 249.678 nm boron emission line is not affected by the sample matrix indicated. The boron content from more than 60 extracts was determined using the three methods mentioned and the results were compared by means of regression calculations. It was found that ICP-AES and the dianthrimide procedure do not differ significantly, whereas the azomethin-H technique leads to somewhat higher values. The accuracy of the results achieved by means of ICP-AES was confirmed by a collaborative study. In order to determine the concentration of boron in soils in the range of 0–2 mg/kg the ICP-AES can be applied following the hot water extraction without further pretreatment of samples. This method is superior in particular when additional elements are to be considered in the soil. 相似文献
47.
Armbruster P Agarwal YK Brüchle W Brügger M Dufour JP Gaggeler H Hessberger FP Hofmann S Lemmertz P Münzenberg G Poppensieker K Reisdorf W Schadel M Schmidt K Schneider JH Schneider WF Sümmerer K Vermeulen D Wirth aG Ghiorso A Gregorich KE Lee D Leino M Moody KJ Seaborg GT Welch RB Wilmarth P Yashita S Frink C Greulich N Herrmann G Hickmann U Hildebrand N Kratz JV Trautman N Fowler MM Hoffman DC Daniels WR von Gunten HR Dornhöfer H 《Physical review letters》1985,54(5):406-409
48.
The acid catalysed dienone-phenol rearrangement of methyl substituted o-propargyl-cyclohexadienones (scheme 3) was investigated. The rearrangements were carried out in acetic anhydride containing about 10/00 sulfuric acid. Under these conditions acetoxy benzenium ions are formed as intermediates. These then undergo charge-controlled [3s, 4s]- and [1s, 2s]-sigmatropic rearrangements. Thus, the [3s, 4s]-process leads to the formation of the corresponding allenyl-phenol acetates ( 19 , 21 , 23 , 25 , 28 , 30 ) whereas the [1s, 2s]-process yields propargyl-phenol acetates ( 20 , 22 , 24 , 26 , 29 ), respectively (cf. scheme 4). 相似文献
49.
When dissolved in trifluoroacetic or fluorosulfonic acid, 6-methylene-tricyclo[3.2.1.02,7]oct-3-ene-8-one derivatives of type 2 (;scheme 1); give polymethyltropylium salts in moderate to good yields by CO-extrusion. These tropylium salts can be isolated pure as hexachloroplatinates. Thus the tricyclic compound 6 gives 1,2,4-trimethyltropylium trifluoroacetate 19 in trifluoroacetic acid (;scheme 3);. This salt in CDCl3 is in equilibrium with its covalent cycloheptatriene (;tropilidene); form 20 , the ratio of the two forms being 1.5–2.1/1. The tropylium salt 19 is reduced by lithium aluminium hydride to a mixture of 1,2,4-trimethylcycloheptatrienes, isomeric with respect to the double bonds, which on hydride abstraction with trityl-tetrafluoroborate gives again the 1,2,4-trimethyltropylium salt 19 (;scheme 3);. From the trimethyl-substituted tricyclic compounds 7 and 8 , in trifluoroacetic acid, are obtained respectively the 1,2,4,6- and 1,2,3,4-tetramethyltropylium ions (; 22 and 24 ); (;schemes 4 and 5);. In this way the 1,2,3,5,6-pentamethyl-tropylium ion (; 26 ); was obtained from 9 (;scheme 6);. With the higher substituted tropylium trifluoroacetates in CDCl3 the equilibrium tropylium trifluoroacetate ? trifluoroacetoxycycloheptatrienes lies well to the left. The hexamethylated tricyclic compound 10 gives a small quantity of heptamethyltropylium trifluoroacetate (; 27 ); and as the main product the C(;3);-protonated species 28 (;scheme 7);, which when treated with aqueous sodium hydrogencarbonate yielded unchanged educt 10 . - The heptamethyltropylium ion (; 27 ); was, apart from polymeric species, the only product from the treatment of starting material 10 with fluorosulfonic acid (;50%);; its salts have as yet not been isolated in their pure form, however. The mechanism for the rearrangement of the tricyclic compounds of type 2 into tropylium salts is presented for compound 6 in scheme 8: The first step is the protonation at C(;9);. Ring opening of the cyclopropane of the tertiary carbenium ion 29 gives the allylic ion 30 , which then yields the aromatic tropylium salt 19 by carbon monoxide extrusion in a linear cheletropic reaction. The smooth conversion with strong acids of the easily accessible tricyclic compounds of type 2 to the corresponding polymethylated tropylium salts, presents a new and useful method for the synthesis of the latter compounds. 相似文献
50.