Optically Active Reference Compounds for Environmental Analysis Obtained by Preparative Enantioselective Gas Chromatography.код для вставкиСкачать
COMMUNICATIONS 7.3 (m. Pli). 5.6 (s. Cp). 3.62 (m. T H F ) . 1 78 (m. T H F ) . 1.05 (br.s, rBu); 13C NMR ( 2 5 C ) : d =138.6 (d. C,,,. Ph; 'J(P-"C) = 44.3 Hz. 'J(1y5Pt-13C)= 30.2 Hz). 134.X(d.C',.,,,,,.Ph. './(P-"C) = 1 3 . 4 H 7 , 3 5 ( 1 9 ~ P t - 1 3 C =)25.5 Hz). 129.6(d. C,,,,,z. Ph. "./(P-'.'C') = 2 H L ) . 128.1 (d, C,,,,. Ph, ' J ( P - 1 3 C )=10.1 Hz), 105.1 ( 5 , Cp), 77.8 (s. CiCH,),). 6X.1 (5. T H F ) . 32.6 (s. C(CH,),). 26 (a. THF): ( - 92 C). (7 = 136.3 (d. c',!,~,,. Ph. 'J(P-"C) = 45 Hz). 133.7 (d. C 1 .3 c') = 1.3.4 H r ) . 129.1 (s. Cp0,".Ph). 127.4 (d. C,,.,,,. Ph. 'J(P-"C) = 9.4 Hz). 104 (s, Cpl. 77 5 (\. C(CH,),). 67.4 (s, T H F ) . 31.4 (7. C(C'H,),). 35.1 i s . T H F ) : " P I ' H ; NMR (CDCI,. 8 5 % H,PO,, 25 C): 6 = 42.0 (l.l("'Pt. P) = 4577 Hz): EIMS.iri :(",") =799(47)[Mi + H].535(46)[!4' - PPh,].453(100)[PtPPh3]+. Received: April 8. 1994 Revised version: June 28. 1994 [Z 6833 IE] German version: Angrir. C'hc~rir.1994, 106. 2196 [ I ] K. \rasufuku. H. XmiaLaki. Bid//. C'/ri~n1.Soi.J / m . 1972. 45. 2664.  M. C'iriano. J. .A. K. Howard. J. L. Spencer. F. G. A. Stone, H Wadepohl. J C'/JCWI SOC.I>ri/tot~7h111.s. 1979. 1749. [ 3 ] H L i n g . M. Herres. L. Zsolnai. W. Imhof, J: Or~nnonwr.C/imm. 1991.40Y. C7. 1993. 12. 5008.  H. Lang. M Herrea. L. Zsolnai. Orgrri~~~n~rrrr//ic.s [ S ] H. L'ing. L. Zsolnai. J. Orgmroniet C/wm. 1991. 406. C 5 . [h] H. L,ing. W. Imhof. C l t m Bw. 1992. 125. 1307.  S. 1. Troyanov. V. Varga, K. Mach. Or~unoti~crollic.~ 1993. 12. 2820. [XI J. R R e r e i i p x . L. R. F;ilvello. J Fornies. E. Lalinde. M. Tomis, Orh.(i~io~ii~,r(i//ii~,\ 1993, 12. 6 . [Y] J. Fornik. M. A . Comer-Saso. E. Lalinde. F. Martinez, M. T. Moreno. O ~ , ~ ~ I ~ I ~ 1992. I I I11, J 2873 ~ ~ I C ~ ~ / I ~ ~ ~ [lo] Crystal data for 3: C,,H,,O,, ,PPtTi. M , = 833.8, monoclinic. space group ('2,<.. LI = 11.674(4). h = 9.343(2). < = 36.425(7) A. = 92.23(3) . V = 7370(3) 43.Z = 8 , p ',,, = 1.50 gcm-'. ;.(MoLz)= 0.71073 A. / I = 40.8 cm-', F(OO0) = 3344. 7 = 293 K. crystal dimensions 0.13 x 0.38 x 0.63 mm. Crystallographic data here collected by Crystallytics Co. (Lincoln, Nebraska) on a Nicolet (Siemens) Autodiffractometer, 3 < 28 < 46 (01 scan); 5081 independent reflections. 2741 with F > 4u(F) were observed and used for structure refincmrnt (program system SHELXTL-PLUS I l l ] ) . Cell constants were refined from 31) reflections (including Friedel pairs) with 15 < 20 < 30 . An ;ibsorptioii correction bascd on Y scans was applied. Six standard reflections were me:isurcd every 300 retlecrions but showed no decay. The structure was ~ o l \ t . db> direct methods and refined on lFol to R = R' = 0.043 Tor 397 variuhles (weighting scheme = o'(F,) 0.0004F~2),highest shift:error 0.001. Goodnesi of f i t 1.13. All non-hydrogen atoms, except those of the solvent molecule were refined anisotropically. All hydrogen atoms were included in calculated positions and refined as riding atoms (C-H 0.96 and I ' = 0.1065 .&?). A difference map following convergence showed no peaks highcr than 1 e k 3 (maximum!minimum difference density 0.76.' - 1 .I1 C A P ) . Further details of thecrystal structureinvestigation areavailable on i-equest fi-om the Director of Cambridge Crystallographic Data Centre. 12 Union Road. GB-Cambridge CB2 IEZ ( U K ) . on quoting the full journal citaI , I F Optically Active Reference Compounds for Environmental Analysis Obtained by Preparative Enantioselective Gas Chromatography** Wilfried A. Konig,* Ingo H. H a r d t , Barbel G e h r c k e , Detlev H. H o c h m u t h , Heinrich Hiihnerfuss, Bernd Pfaffenberger, and G e r h a r d R i m k u s Dedicated t o Projkssor Hansjijrg Sinn on the occasion qf'his 65th birthday The distribution and behavior of toxicologically relevant xenobiotics in the environment is of increasing scientific interest. Chirdl. biologically active compounds whose enantiomers produce fundamentally different effects and whose biologiccil degradation is, as a rule, enantioselective itre of prticular importance in this context. These properties have been observed in "cyclodiene" insecticides"' and. more recently, in chiral x 1,2,3.4,5,6-hexachlorocyclohexane (.A-HCH),[21 the enantiomers of which are selectively accumulated in living organisms. Using gas chromatography on modified cyclodextrins (CDs). we have been able to separate a number of polychlorinated hydrocarbons (PCHs) into their enantiomers: heptachlor and cis- and [runs-chlordane, which were used as insecticides for decades; their metabolites cis-heptachlor epoxide and oxychlordane;[31 the atropisomeric polychlorinated biphenyls ( P C B S ) ; ~and ~] bromocy~len[~1 (Fig. 1 ) . Other groups have also used enantiose- + A cis-chlordane van.-chlordane oxychlordane t1011. [l I ] S H C L . Y T L - P L l ' S Sofruwe Puckuge for I/W Dererniinurioi~of Crj..uu/ Strucr i i r ( ' \ . Release 4.0; Siemens Analytical X-ray Instruments. Inc.. Madison. WI. USA. 1990. (121 F. Ozawa. J. W Park, P. B. Mackenzie. P. W. Schaefer, L. M. Henling. R. H. Gruhhs. J ,4111. C'/im?. Soc 1989. /If. 1319.  M. c'. Bard. P r r ~ Irrorg. . Chi!. 1968. 9. 1.  a ) G . Erker. W. FrDmberg, R. Mynott. B. Gabor. C. Kruger. Angov. C/wrn. 1986. 98. 458. A I I ~ C'hcm. ~ . In/. M.Engl. 1986. 25. 463; b) C. Erker, W. Friimberg. R. Benn. R. Mynott. K. Angermund. C. Kruger, Orgunomrrrr//i~.~ van. - heptachlor epoxide cis-heptachlor epoxide heptachlor 1989.,Y.911. [I51 The t-eaction of 2 (0.216 g. 0.29mmol) and [Cp,Ti(C=CPh)l] (0.11 g. 0.29 iiimol) in T H F gave a mixture ofproducts. The first fraction obtained by cryst;illi;.atioii l'rom THF!hexane was a yellow solid (0.045 g). The 3 1 PNMR spectrum indicates this to be a mixture ofcomplexes. The second fraction. an orange microci-ystalline product (0.1 g, 41 'A yield) was identified by elemental analysis. inas5 spectrum. and IR and NMR spectra as the previously reported [C'p2Ti(c'~CPIi),Pt(PPh ,)I [?I. [I61 H. Lang. D. Seyferth, Z. .tviirurfor.sch. B 1990. 45. 212.  R . A . Head. / I M J I . , ~ .S y i / / i . 1990. 2K. 134. bromocyclen a-HCH Fig. 1. Structural formulae of chiriil xenobiotics [*I Prof. Dr. W. A. Konig. Dipl.-Chem. I. H. Hardt. DiplLChem. B. Gehrcke. Dip[.-Chem. D. H. Hochmuth, Priv.-Doz. Dr. H. Huhnerfuss. DipLChem. B. Ppdffenberger lnstitut fur Organische Cheinir der Universitidt Martin-Luther-King-Platz 6, D-20146 Hamburg ( F R G ) Telefax: Int. code + (40)4123-2893 Dr. G . Rimkus Lebensmittel- und Veteriniiruntersuchungsamt des Landes Schles*ig-Holstein, D-24537 Nrumunster [**I This research was sponsored by the Deutsche Forschungsgemeinschaft, the Fonds der Chemischen Industrie. and the Bundesministerium fur Forschung und Technologie. COMMUNICATIONS lective gas chromatography in the analysis of PCHs isolated from different compartments of the environment, and, in several cases. they have shown that these compounds are metabolized enantioseIectiveIy.['l Optically active samples of these compounds have already been obtained by enantioselective dehydrochlorination, separation of the enantiomers by liquid chromatography (%-HCH['.'I). and enantioselective synthesis (heptachlor. heptachlor epoxide, cis- and trun.s-chlordane['. 91); however, enantiomerically pure (or enriched) reference substances. which can be used in gas chromatography to determine the sequence of elution of enantiomers, are not commercially available. Using preparative gas chromatography columns with modified CDs as the chiral stationary phase, we have now succeeded in separating the enantiomers of a selection of PCHs on a milligram scale and with enantiomeric excesses of between 42 and over 99% (Fig. 2, Table 1 ) .I1 21 So far, preparative separations on columns packed with CDs have only been described for the highly volatile inhalation anesthetics enflurane" 31 and i ~ o f l u r a n e , [which ' ~ ~ have separation factors x > 2 on capillary columns." In the examples reported here, the separation factors are between 1.02 (e.g.. heptachlor, trun.r-heptachlor epoxide. bromocyclen) and 1.10 (2-HCH). Al- Table 1 Isolated yield and enantiomeric excess ((w) obtained in the preparative resolution o l the enantiomers of chiral xenobiotics by gas chromatography on cyclodextrin (CD) derivatives. I n each case, the racemate (ca. 2 mg) in acetone (ca. 20 m L ) was injected at an injector temperature of 200 C ; the total weight of sample was ca. 20 mg. Conipound ( + )-Heptachlor [a] ( - )-Heptachlor ( +)-ci-Heptachlor cpoxide ( - )-cr.\-Heptachlor epoxide [a] + I-i,.anv-Hepatachlor epoxide [a] ( - )-rnriic-Heptachlor epoxide ( + )-m-Chlordane [a] ( ( - )-crc-Chlordaiie ( +)-rr.ufwChlordane [a] ( - )rron.\-Chlordaiie ( +)-Oxychlordane (-)-Oxqchlordane [a] ( + )-Bromocyclen ( - )-Bromocyclen [.I] ( + )-z-HCH [c] (-)-o-HCH [a] [ii] Yield [mgl er 2.3 13 1.4 1.1 51.2 65.2 94 6 98.8 h l .0 83.2 50.5 70.5 92.6 9X.3 50.1 3.5 2.0 2.6 1 3 1.5 1. I 2.7 3.5 1.8 1.6 8.7 7.0 CD derivative ['yo1 42.8 53.8 49.3 >99 >99 2.6-di-O-methyl-3-O-pentyl-/~-CD[I01 ?.6-di-O-methyl-3-O-pentyl-/~-CD 2.6-di-0-methyl-3-U-pentyl-~-~D [lo] 2.6-di-O-mcthyl-3-O-pentyl-;.-CD 2.6-di-0-methyl-3-0-pentyl-l(-CD 2,6-di-O-meth~.l-3-O-pentyl-P-CD ?.h-diO-metliyl-3-O-pentyI-/~-CD 2.6-di-O-methyl-3-0-pentyl-/l-CD 2.6-di-0-methyl-3-O-pentyl-/l-CD 2.6-di-0-methyI-3-0-pentyl-/l-CD 6-0-tex-2.3-dimethyl-/~-CD[b] [I I] h-O-tex-2.3-dimethyl-~~-CD [b] h-O-tex-2,3-dimethyl-/~-CD[b] 6-0-tex-2,3-dimethyl-/I-CD [b] 7,6-di-O-methyl-3-O-pentyl-;~-CD 1.6-di-O-methyl-3-O-pentyl-;.-CD Enantiomer eluted first. [h] t e = ~ dimethylthexylsilql. [c] [r];" = 127.6 ( c = 2. acctone) though the quantity of sample injected in each individual run ranged from 2 to 7 mg, satisfactory to very high enantiomeric purity (with yields of 20-90% for each enantiomer) was obtained by fractionation. In each case, the enantiomers were characterized by measurement of optical rotation; the order of elution of the enantiomers can thus be determined for any CD derivative." 1' The toxic compounds mentioned above are ubiquitous and are highly persistent contaminants in the environment; they are accumulated in the adipose tissue of higher organisms. Sea gull eggs. liver of roe deer and hare, and different seal organs were examined; the ratio of enantiomers for the metabolites cis-heptachlor epoxide and oxychlordane deviated significantly from 1.O in all cases (Table 2). It is not only noticeable that the selectivity of metabolism differs greatly from one organism to the next, but also that the (+)-enantiomers are enriched in sea gull eggs and Table 2. Enmtiomer ratio ( + II-_ determined bq gas chromatography) of ci.\-heptachlor epoxidc and oxychlordane in various samples ot' sea gull eggs. harc liver. roe-deer liver (from Schlesnig-Holstein). and adipose tissue from seals (from Iceland) 86.1 0 ' 9 ee Sample A L i 0 20 40 tlmin I 60 0 20 40 tlmin 60 Fig. 2. Determination <if the eniintionieric purity of heptachlor (left) by enantiosclective gas chromatography on a "fused silica" capillary column (25 m ) containing heplnkis(2.h-di-O-~iefhyl-3-~-pentyl)-~-cyclodextrin 111 polyailoxane OV 1701 (20"/0) at 130 C and of ci\-heptachlor epoxide (right) on a "fused qilica" capillary column (25 m) containing heptakis(2.6-di-O-inethyl-3-O-pentyl)-~-cyclodextrin in polysiloxane OV 1701 (20%) at 160 C; injector temperature 200 C. detector temperature 250 C . carrier gas. hydrogen. Sea gull egg. 1 Sea gull egg. 2 Sea gull egg. 3 Sea gull egg, 4 Sca gull egg. 5 Hare liver. 1 Hare liver. 2 H x c livei-. 3 Hare I i v x . 4 Hare live[-. 5 Roe-deer liver. I Roe-deer liver. 2 Roe-deer liver. 3 Roc-deer liver, 4 Roe-deer liver, 5 Scat. 1 ('idipose tissue) Seal. 2 (adipose tissue) Seal. 1 (liver) Seal, 2 (liver) Seal. I (brain) Seal. 2 (brain) < is-Heptachlor epoxide 2.7 1.6 3.3 Osychlordane 2.3 2.1 1.8 15 1.5 1.1 1 5 1 .0 3.7 1.3 2.6 3.2 1 1.3 1 .5 7 6 7 9 0.14 0 18 0.06 0.05 0.11 9 12 14 17 12 0.66 0.54 0.57 0.45 0.57 0.48 COMMUNICATIONS in the liver of roe deer and hare, whereas the (-)-enantiomers predominate in the adipose tissue of seals. Bromocyclen, which is used in Europe to counter parasitic infestations of pets and has been found in fresh water fish, in some cases, in surprisingly high concentrations of > 1 mg kg- I , is also metabolized enantioselectively."] The ratio of enantiomers (peak area ratio of (+)-enantiomer/( -)-enantiomer) lies between I .25 and 1.06. The toxicological implications of these findings are not yet clear; however. the results show that the enzymatic degradation of the xenobiotics dicussed here is possible for at least one enantiomer. Degradation of both enantiomers may also be occurring at different rates. Enantioselective gas chromatography has not only proven to be a sensitive and selective analytical method for distinguishing between enzymatic and non-enzymatic degradation of chiral toxic compounds, but can also be used for the virtually complete preparative-scale resolution of enantiomers with low separation factors. The Versatility of the Azido Ligand: Linkage of Ni" Centers to Form a Chain with One End-toEnd and Three End-On Bridges in Alternation** Joan Ribas," Montserrat M o n f o r t , Barindra Kumar Ghosh, and Xavier S o l a n s In recent years several groups have investigated the correlation between magnetic and structural properties of p-azidonickel(r1) complexes.[', We are now working systematically in this fieIdl3-'] and have prepared two types of systems whose structures depend on the amino ligand employed (Scheme 1 ) . ferromagnetic coupling antiferromagnetic coupling N N MdN ReceiLjed: April 2. 1994 [26X191E] German version: Aiigcw. Cheiii. 1994. 106, 21 75 "I 'N' N / "N\ M M \NNN/ N [I] A. Miyuziki. T. Hotta. S. Marumo, M. Sakai. J. .4gric. F O I JC'hoii. ~ 1978. 26. 975 977: A . Miyamki. M. Sakai, S. Marumo. ihid. 1979.27, 1403-1405: i M . 1980. 28. 1310- 1311.  R. Kallenborn. H. Huhnerfuss, W. A. Konig. A i i g w . C'/i[mi. 1991. 103. 328329: .Aiigm. Ciiciii. / i i / . Ed. Eiigi. 1991. 30, 320-321; H. Huhnerfuss. J. Faller. R K;illenborn. W. A. Konig. P. Ludwig, B. Phffenberger. M. Oehme, G. Rimkii\. Ciirrulirv 1993. 5, 393-399.  W. A K6nig. D. Icheln. T. Runge, B. Pfaffenherger. P. Ludwig. H . Huhnerfuss. J H i g h R r , C'hroiiiarogr. 1991. 14. 530-536. 141 W. A KOnig, B. Gehrcke. T. Runge. C. Wolf. .I High Rm. Ciiroiiiorogr. 1993, 16. 376 378.  B. Plhffenbrreer. H. Huhnerfuss. B. Gehrcke. I . H. Hardt. W. A. Kijnig. G. Riinkui. ('/iciiio\phrre. in press.  H.-R. Bmcr. M. D. Muller. h i d C'1wiii. 1992, 64. 3168 -3175; H.-R. Buser. M .D Mullei-. C. Rappr h l ' i l ' l J i i . Sci. E3ch~io/. 1992. 26. 1533-1540; H:R. Busel. M D. Muller. ihid. 1993. 27. 1211 -1220; M. D. Muller. M. Schlabach. M. Oehnie. ihirl. 1992. 26. 566. S. Mossner. T. R . Spraker. P. R. Becker, K. Ballschmiter. ~ ' l i i l c r i i o . \ p / i o . c1992. 24. 1171 1180; R. Kallenhorn, M. Oehme. W Vertcr, H . Parlar. hid. 1994. 28. 89-98, 171 S. .I. C't-istol. J Aiu. C h o i i . .Yo<.1949. 71. 1894. [XI K . Mollcr. ( ' Bretzke. H . Hiihnerfiiss, R . Kallenhorn. J N.Kinkel. 1. Kopf. G . Rimku\. . - l i i , y m . Climir. 1994. UM.91 1-912: Aiigru. C/wnr.h i t . Ed. Eiigl. 1994. 33. X 8 1 8x4. [Y] H. Klmnsycr. W Thieinann. C/ieiiro.s/~/ierE1986. 15. 687 -692. [lo] W. A . Khnig. B. Grhrcke. D. Icheln. P. Evers, J. Donnecke. W. Wang. J. High Ri.5 ( ' / i r ( i i i i o / i i ~ q r .1992. I S . 367-372. [l I ] W A . K6nig. B. Gchrcke. D. H. Hochmuth. C. Mlynek. H. Hopf. T c , / r u / i d v i i d . \ j i l i i t i . 1994. i. 347- 350. 1121 Steel c.oJ~i~iins (1m x 5 3 mm) packed with equal proportiona by weight of cyclodexti-in derivative and polysiloxane OV 1701 ( 2 . 5 % ) o n chromosorh CiH P (I00 120 mesh) were used at temperatures between 110 and 160 C with helium :is thc'carrier gds at a pressure ofbetween 310 and 600 kPa (corresponds to a llow, iiirr of 240 and 620 m L m t n - l . respectively): see also 1. H. Hardt. W. A. Konig. J C%ioirturog.r. ' 4 . 1994, 666. 611-615. [I31 V Scliui-ip. H . G~-osenick.B. S. Green. Angcii Chcwi 1993. / 0 5 , 1690-16Y1; Aiig(.ii. C ' / i < ~ i l ~Iiir. . Ed. Olgl. 1993. 32, 1662 1663. [I41 D. U Stacrk. A . Sliitangkoon. G . Vigh. J. Chroiilorogr. A . 1994. 663. 79-85 [I51 J. Meiii~'iild. K. Thompson, D. L. Pearson. W A. Kanig. T. Runge. W. Franckc. ,S"X~IIW1991. 251. 560 561. (161 Refercnce siiniplcs can he obtained from Dr. Ehrenstorfer GnibH. B g m S c h l o w - - S t r .ha. D-X6199 Augsburf ( F R G ) ~ end-on end- to-end Schcme I . Possible coordination modes for azido ligands. The bridging ligand with its end-to-end (EE) coordination mode affords antiferromagnetic (AF) d i n ~ c l e a r [ ~and " ~ one-dimensional (ID) s y s t e ~ n s . [ ~ End-on ~ - ~ ] (EO) coordination is observed in some d i n ~ c l e a r , [ b1 ~ +one t e t r a n u c l e a ~ - , [and ~ ~ ~several one-dimensional polymeric ferromagnetic (F) compounds.[4h1 A new unexDected two-dimensional (2D) complex (Fig. 1 ) with both EE and EO bridges has also been characterized['] and displays overall A F behavior with canting phenomenon at low temperatures. This variation in coordination modes. EE and EO. causes different magnetic couplings which appear to be general for the metal ions C U " , ~Mn",['] ~~ Mn1I1,[81 and Co11, In continuation of our in$i vestigations we considered that the 2 D system presents Fig. 1 Schematic representation of the one terminal azido ligand structurc of the 2D complex [Ni(N,)?on each Ni" atom (Fig. I ) , (dmpd)],, (dmpd = '.'-dimethylpropane-l Jdiamine). showing the differand it should thus be posent kinds of a d o coordination €0. sible to have three EO EE, and terminal [ j ] . bridges. We report here on the synthesis and characterization of [Ni(N,),(tmeda)], (tmeda = N,N,N',N'-tetramethylethylenediamine), a novel compound in which the Ni" centers are linked alternately by one EE and three EO bridges to form a chain (Fig. 2).['01 Each Ni" center completes its distorted octahedral coordination by binding to one bidentate tmeda lig- [*I [**I Prof. J. Ribas. Dr. M. Monfort, Dr. B. K . Ghosh Departament de Quimicd Inorganica. Univcrsitat de Barcelona Diagonal, 647. E-08028-Barcelona (Spain) Telefax' Int. code + (343) 411-1492 Prof X. Solans Universitat de Barcelona (Spain) This work was supported by the Spanish Direccibn General de lnvestigacion Cieniifica y Tecnica (project PBY1-0241).