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    7 views4 pages

    NMR Chem Shifts

    Uploaded by

    Dr. P. Ramu Sridhar

    Copyright:

    © All Rights Reserved
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    7512 J. Org. Chom. 1997, 62, 7512-7515 NMR Chemical Shifts of Common Laboratory Solvents as Trace Impurities Hugo E, Gottieb,* Vadun Kodyar, and Abraham Nadelman* Department of Chesnistry. Barllan University. "Rarsat-Gar 82900, Israel Reecived June 27, 1907 In the course of the routine use of NMR as an aid for organic chemistry, a day-to-day problem is the identifica- tion of signals deriving frem commen contaminants (ater, solvents, stabilizers, olls) in Tess-than-analyt cally-pure sampies. This data may be available in the literature, but the time Involved in searching for it may he considerable. Another issue is the concentration dependence of chemical shifts (especially 'H); results obtained two or three decades ago usually refer to much ‘more concentrated samples, and run at lower magnetic flelds, than today's practice. We’ therefore decided to collect 'H and 8C chemical shifs of what are, in our experience, the most popular “extra peaks” in a variety of commonly used NMR solvents, in the hope that this will be of assistance to the practicing chemist. Experimental Section NMR spectra were taken in a Bruker DPX-200 instrume (900.1 and 755 Nila for !Hf and 19C, respectively). Unless ‘therwise indicated, all were run at reom temperature (24 41 °C), Fortheexpermentsm the ast econ ois paper, probe temperatures were measured with a allbrated Eurathersi 8AN/L digital thermemstor. connected to 2 thermocouple which was introduced Into an NMR tube Billed with mineral al to ap proxmaiely tie same level as a typical sample. At eae femperature the D;0 samples were left co equilibrate fr atleast IM'min before the data were collected. In ardor to avoid having to ebtain hundreds of spectra, om prepared seven stuck solutions containing approximately equal mounts of several af Our entries, chesen im such @ Way 3& (> prevent intermolerular interactions and possible ambiguities in Essignmet. ‘Solution I" acetone, fr-buty! methyl ether. A tethylfermersice, ethandl, toluene. Selution 2: benzene, d meth sulfodde, ethyl acetate, methanol, Soludon 3: acetic seid, chiorofoem, dietiyl ether. Zpropanol, tetrahydrofuran Solution 4 acetonitrile, dichloromettane, diaxane, rhexane HMPA" Solan 5: 1,é-dichlorocthane, ethyl methyl Ketone, inpentane pyridine. Solution terebuty! sleobol, BET, eyde hexane, I 2dmethoxyertane, aitrametiane, sihcone grease, ‘wiethslemine, Solution 7- digyme, cimethylacstaraide.ethy! tne glycol, "greace” engine el. For Dz0. Solution I: acetone, texebutyl medhyledher dimethyllonrmmnile,ethandl, 2- propanol Solution 2: dimethyl sulfoade, ethyl acetate, ethiviene gical, methanol. Solution 3 acstonitcle, diglyme, dioxane, HMPA pyridine. Selution 4. 1,2cimethonyethane, dimethycetamide, yl tell ketone, wiedhylarine. Scutign 5 acct acd ere Duty alcohol, clechyl ether, cotraiydroturan. In D0 and CD;OD nitromethane was run separately, as the protons ‘exchanged with deuterium in presene» of tlechylamine. Results Proton Spectra (Table 1), Asample of 0.6 mL of the solvent, containing 1 yl, of TMS," was first run on its ‘own. From this spectrum we determined the chemical shifis of the solvent residual peak? and the water peak. It should be noted that the latter is quite temperature (I) For reconmendatons on the publeation NMR data, soe PAC Comsmlasion na Molecule Suvurtre and Spsewesingy. Pure Appl Chern 1812 29.620, 1976.4 217 1100 chericl ain reo sro 1. Chemical shift af FIDO asa fanesion ol dependent (vide ina). Also, any potential hydrogen: bond acceptor will tend to shift the water signal down- fiold; this is particularly true for nonpolar solveres.. In contrast, in eg. DMSO the water is already strongly hydrogen-bonded to the solvent, and solutes have only a negligible effect on its chemical shit, This is also true for D.O; the chemical shift of the residual HDO is very ‘temperature-dependent (vide infra) but, maybe counter- intuitively, remarkably solute (and pH) independent. We then added 3 pl, of one of our stock solutions to the NMR tube. ‘The chemical shifts were read and are presented in Table 1. Except where indicated, the «coupling constants, and therefore the peak shapes, are essentially solvent independent and are presented only For D:0 as a solvent, the accepted reference peak (8 = 0) the metiyl signal ofthe sodium sat of 3-(trimeth- ylsily)propanesuifonicacic one erystal ofthis was added teach NMR tube. This material has several disedvan- tages, however: itis nct volatile, so i¢ cannot be readily climinated ifthe sample has tobe recovered. In addition, unless one purchases it in the relatively expensive deuterated form, it adds three more signals to the spectrum (metlylenes 1, 2, and 3 appear at 2.81, 1.76, and 0163 pom. respectively). We suggest that the re- sidual HDO peaik be used as a secondary reference: We find that if the effects of temperature are taken into ‘account (vide infra), this is very reproducible. For D:O, We used a different set of stock solutions, since many of the less polar substrates are not significantly water- soluble (See Table 1). We also ran sodium acetate and sodium formate (chemical shifts: 190 and 8.44 ppm, respectively). Carbon Spectra (Table 2). To each tube. 50 yl. of the stock solution and 3 al. of TMS! were added. The solvent chemical shifts’ were obtained from the spectra ‘containing the solutes, and the ranges of chemical shifts Shee deuterium than the peraectirated materi CHCIy im CDC ot SSSR erate cera etary USGS eee mone Te niew ara e ‘Siegel Bee cats aa ever gal na 2 gine wt png oe. 2 ac own we 2 “Ca Sharma ar emer See $0022.2263(97)01176.6 CCC: $14,00 © 1007 American Chemical Secioy Netes J. Org. Chem, Vol. 62, No 21, 1997 1818 ‘Table 1. NMR Data proton mak CDC (CDs:CO_(CDISO__GiDe CDN CD,GD__—D.O ‘Solvent residual pale 776 2.0% 250716194 aa a7 10 . 15e 2k ame (M213, ae cece acid che 5 zi 1.80 rot 155196 og 208 fcczone CH 5 2 109 209133208 zus ae meecentrse on 5 20 205 zor 155196 20s 205 benzene cH . Tae 76 Ti 731 7 ‘erebuty aleabol cH, 5 128 Las Ml 13116 a0 12 on 5 41900 15s terebutyl methyl ether CCH 5 Lis Las ior 114 nas OCH 5 3a 3a sol 3s sa sz He Ae : Bor 596 05897 id on . 501 4m a0 Ach os zat aaa 2m 2a 2ar AIC) s 143 La 13 139 140 berm cH 5 726 Bue bis 758 790 eyeonexsne cH 5 148183 Tao 1a tas 12-diehervethane cH. . a7 aT 290 38) ae dichloromernare cn 5 San 53 a BAL 549 iediylether cH re rel ano sur cH G7 348 Sa 3a 342 349 358 aigiyme cH Es Bes 356 345 353 iB B6r cH m gsr X07 Sa 445 35k 36 oct : a0 48 sil 320 238237 Lzamettoxyethare CH: s 3400 88 3uz 3z8 335337 cH 5 3556 33343 352 300 icnetylacetamide == CHC s 208187 10 207 208 NCH 5 302 400 257 a3) Son NCH : 20283 2.05 292 200 amecnytormamite CH 5 Boz 80 703 Tor tee cH 5 2960 eet 238 299 Sut cH 5 288 28 186 2B 28 mech ubloice cH : 26 252 1s 26s 271 ‘loxane cH i an 450 335 e827 fanaa, cn e1, as Lae 086 lie Ltr cs arm 3m sar 34 3605.65 oH Sa a9 byl avetate caco | t 205187 165 2) 27 CHOH, a7 412 405 20 foo uk ccs = NT 1280 os ia 12 cttylmetyiketene = HCD S zu 207 138 zie 219 CHC aT HG 2a re 250 lB Cac oT 1080.86, ass, Tol 125 ethylene pleat cH . a7 UR aa 50368 grease’ cH, a rT ou oe cH: es 125129 1.30 129 hexane cus t Oss 088 om a8 90 cH m 125 La 12 124 129 MAS cH aos 265 750 vs 20 2a 2a. seshano! cH # a4 a aie 407 au Rat on Sop 3g 41 sitcomsthane CH s 433s 4a 294 a 4a pentane cH LT O88 08 035 087 090 cH = rua i 123 128 2.propanal cH, as 12110 rot 05 aso 47 ar s.0 401390 37% eT am de pyridine Caz) m Be B88 aos Bat ase Cag m 7 135 1B 66 1a 45 CH = res 776 7 6 o8 yas Tar siticame grease! cn : oor oa 020 ow lecanydroturan cH a 1859 176140 187188 Gio = 37 38a so Sar sn a4 toluene i 5 235232 i 2 2m Cle Tit imma Tig To ne CH) ta i281 716 tetechyizmine au, ty 10) ae. 093086 105 cH qT 25324 BB 240 258 + In these solvents the mcermlecUlar ate of exchange ts slow coought that a peak due to HDO is usually also observed app 2.1 and 30 ppm ia acetone and DSO, respectively. Ta the former soWvent, it often seen as a 111 erplet, with “Jap SDipDimerhyl-tertbatylphendl.

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