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核磁常见溶剂峰

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NMRChemicalShiftsofCommon

LaboratorySolventsasTraceImpurities

HugoE.Gottlieb,*VadimKotlyar,and

AbrahamNudelman*

DepartmentofChemistry,Bar-IlanUniversity,Ramat-Gan52900,Israel

ReceivedJune27,1997

InthecourseoftheroutineuseofNMRasanaidfor

organicchemistry,aday-to-dayproblemistheidentifica-

tionofsignalsderivingfromcommoncontaminants

(water,solvents,stabilizers,oils)inless-than-analyti-

cally-puresamples.Thisdatamaybeavailableinthe

literature,butthetimeinvolvedinsearchingforitmay

beconsiderable.Anotherissueistheconcentration

dependenceofchemicalshifts(especially1H);results

obtainedtwoorthreedecadesagousuallyrefertomuch

moreconcentratedsamples,andrunatlowermagnetic

fields,thantoday’spractice.

Wethereforedecidedtocollect1Hand13Cchemical

shiftsofwhatare,inourexperience,themostpopular

“extrapeaks”inavarietyofcommonlyusedNMR

solvents,inthehopethatthiswillbeofassistanceto

thepracticingchemist.

ExperimentalSection

NMRspectraweretakeninaBrukerDPX-300instrument

(300.1and75.5MHzfor1Hand13C,respectively).Unless

otherwiseindicated,allwererunatroomtemperature(24(1

°C).Fortheexperimentsinthelastsectionofthispaper,probe

temperaturesweremeasuredwithacalibratedEurotherm840/T

digitalthermometer,connectedtoathermocouplewhichwas

introducedintoanNMRtubefilledwithmineraloiltoap-

proximatelythesamelevelasatypicalsample.Ateach

temperature,theD2Osampleswerelefttoequilibrateforatleast

10minbeforethedatawerecollected.

Inordertoavoidhavingtoobtainhundredsofspectra,we

preparedsevenstocksolutionscontainingapproximatelyequal

amountsofseveralofourentries,choseninsuchawayasto

preventintermolecularinteractionsandpossibleambiguitiesin

assignment.Solution1:acetone,tert-butylmethylether,di-

methylformamide,ethanol,toluene.Solution2:benzene,di-

methylsulfoxide,ethylacetate,methanol.Solution3:acetic

acid,chloroform,diethylether,2-propanol,tetrahydrofuran.

Solution4:acetonitrile,dichloromethane,dioxane,n-hexane,

HMPA.Solution5:1,2-dichloroethane,ethylmethylketone,

n-pentane,pyridine.Solution6:tert-butylalcohol,BHT,cyclo-

hexane,1,2-dimethoxyethane,nitromethane,siliconegrease,

triethylamine.Solution7:diglyme,dimethylacetamide,ethyl-

eneglycol,“grease”(engineoil).ForD2O.Solution1:acetone,

tert-butylmethylether,dimethylformamide,ethanol,2-propanol.

Solution2:dimethylsulfoxide,ethylacetate,ethyleneglycol,

methanol.Solution3:acetonitrile,diglyme,dioxane,HMPA,

pyridine.Solution4:1,2-dimethoxyethane,dimethylacetamide,

ethylmethylketone,triethylamine.Solution5:aceticacid,tert-

butylalcohol,diethylether,tetrahydrofuran.InD2Oand

CD3ODnitromethanewasrunseparately,astheprotons

exchangedwithdeuteriuminpresenceoftriethylamine.

Results

ProtonSpectra(Table1).Asampleof0.6mLofthe

solvent,containing1µLofTMS,1wasfirstrunonits

own.Fromthisspectrumwedeterminedthechemical

shiftsofthesolventresidualpeak2andthewaterpeak.

Itshouldbenotedthatthelatterisquitetemperature-dependent(videinfra).Also,anypotentialhydrogen-

bondacceptorwilltendtoshiftthewatersignaldown-

field;thisisparticularlytruefornonpolarsolvents.In

contrast,ine.g.DMSOthewaterisalreadystrongly

hydrogen-bondedtothesolvent,andsoluteshaveonlya

negligibleeffectonitschemicalshift.Thisisalsotrue

forD2O;thechemicalshiftoftheresidualHDOisvery

temperature-dependent(videinfra)but,maybecounter-

intuitively,remarkablysolute(andpH)independent.

Wethenadded3µLofoneofourstocksolutionsto

theNMRtube.Thechemicalshiftswerereadandare

presentedinTable1.Exceptwhereindicated,the

couplingconstants,andthereforethepeakshapes,are

essentiallysolvent-independentandarepresentedonly

once.

ForD2Oasasolvent,theacceptedreferencepeak(δ

)0)isthemethylsignalofthesodiumsaltof3-(trimeth-

ylsilyl)propanesulfonicacid;onecrystalofthiswasadded

toeachNMRtube.Thismaterialhasseveraldisadvan-

tages,however:itisnotvolatile,soitcannotbereadily

eliminatedifthesamplehastoberecovered.Inaddition,

unlessonepurchasesitintherelativelyexpensive

deuteratedform,itaddsthreemoresignalstothe

spectrum(methylenes1,2,and3appearat2.91,1.76,

and0.63ppm,respectively).Wesuggestthatthere-

sidualHDOpeakbeusedasasecondaryreference;we

findthatiftheeffectsoftemperaturearetakeninto

account(videinfra),thisisveryreproducible.ForD2O,

weusedadifferentsetofstocksolutions,sincemanyof

thelesspolarsubstratesarenotsignificantlywater-

soluble(seeTable1).Wealsoransodiumacetateand

sodiumformate(chemicalshifts:1.90and8.44ppm,

respectively).

CarbonSpectra(Table2).Toeachtube,50µLof

thestocksolutionand3µLofTMS1wereadded.The

solventchemicalshifts3wereobtainedfromthespectra

containingthesolutes,andtherangesofchemicalshifts

(1)ForrecommendationsonthepublicationofNMRdata,see:IUPACCommissiononMolecularStructureandSpectroscopy.PureAppl.Chem.1972,29,627;1976,45,

217.(2)I.e.,thesignaloftheprotonfortheisotopomerwithonelessdeuteriumthantheperdeuteratedmaterial,e.g.,CHCl3inCDCl3orC6D5HinC6D6.ExceptforCHCl3,thesplittingduetoJHDistypicallyobserved(toagoodapproximation,itis1/6.5ofthevalueofthecorrespondingJHH).ForCHD2groups(deuteratedacetone,DMSO,acetonitrile),thissignalisa1:2:3:2:1quintetwithasplittingofca.2Hz.(3)Incontrasttowhatwassaidinnote2,inthe13Cspectrathesolventsignalisduetotheperdeuteratedisotopomer,andtheone-bondcouplingstodeuteriumarealwaysobservable(ca.20-30

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完整word版,NMR常见溶剂峰和水峰

完整word版,NMR常见溶剂峰和水峰

溶剂 1H化学位移δ（精细多重峰数） JHD/Hz 13C化学位移δ（精细多重峰数） JCD/Hz

NMR溶剂中残余H2O或HOD的质子化学移 相对密度（20℃） 熔点/℃ 沸点/℃

丙酮—d6 2.05(5) 2.2 206.68(13)

29.92(7) 0.9

19.4 2.8 0.87 -94 57

氯仿-d 7.27(1) 77.23(3) 32.0 1.5

1.50 -64 62

重水 4.80(DSS)

4.81(TSP) 4.8 1.11 3.8 101.4

N，N-二甲基甲酰胺-d7 8.03(1)

2.92(5)

2.75(5

1.9

1.9 163.15(3)

34.89(7)

29.76(7 29.4

21.0

21.1 3.5 1.04 -61 153

二甲基亚砜-d6 2.50(5) 1.9 39.51(7) 21.0 3.3 1.18 18 189

甲醇-d4 4.87(1)

3.31(5)

1.7 49.15(7) 21.4 4.9 0.89 -98 65

注：JHD为溶剂本身的其他1H对与之相对应的1H之间的耦合常数，JCD为溶剂本身1H对13C的耦合常数，H2O和交换了D的HOD上的1H产生的即水峰的化学位移

氯仿：小、中小、中等极性

DMSO：芳香系统（日光下自然显色、紫外荧光）。对于酚羟基能够出峰。芳香化合物还是芳香甙，都为首选。

吡啶：极性大的，特别是皂甙

对低、中极性的样品，最常采用氘代氯仿作溶剂，因其价格远低于其它氘代试剂。极性大的化合物可采用氘代丙酮、重水等。

针对一些特殊的样品，可采用相应的氘代试剂：如氘代苯（用于芳香化合物、芳香高聚物） 、氘代二甲基亚砜（用于某些在一般溶剂中难溶的物质） 、氘代吡啶（用于难溶的酸性或芳香化合物）等。

NMR常见溶剂峰和水峰

NMR常见溶剂峰和水峰

.

,.. 溶剂 1H化学位移δ（精细多重峰数） JHD/Hz 13C化学位移δ（精细多重峰数） JCD/Hz

NMR溶剂中残余H2O或HOD的质子化学移 相对密度（20℃） 熔点/℃ 沸点/℃

丙酮—d6 2.05(5) 2.2 206.68(13)

29.92(7) 0.9

19.4 2.8 0.87 -94 57

氯仿-d 7.27(1) 77.23(3) 32.0 1.5

1.50 -64 62

重水 4.80(DSS)

4.81(TSP) 4.8 1.11 3.8 101.4

N，N-二甲基甲酰胺-d7 8.03(1)

2.92(5)

2.75(5

1.9

1.9 163.15(3)

34.89(7)

29.76(7 29.4

21.0

21.1 3.5 1.04 -61 153

二甲基亚砜-d6 2.50(5) 1.9 39.51(7) 21.0 3.3 1.18 18 189

甲醇-d4 4.87(1)

3.31(5)

1.7 49.15(7) 21.4 4.9 0.89 -98 65

注：JHD为溶剂本身的其他1H对与之相对应的1H之间的耦合常数，JCD为溶剂本身1H对13C的耦合常数，H2O和交换了D的HOD上的1H产生的即水峰的化学位移

氯仿：小、中小、中等极性

DMSO：芳香系统（日光下自然显色、紫外荧光）。对于酚羟基能够出峰。芳香化合物还是芳香甙，都为首选。

吡啶：极性大的，特别是皂甙

对低、中极性的样品，最常采用氘代氯仿作溶剂，因其价格远低于其它氘代试剂。极性大的化合物可采用氘代丙酮、重水等。

针对一些特殊的样品，可采用相应的氘代试剂：如氘代苯（用于芳香化合物、芳香高聚物） 、氘代二甲基亚砜（用于某些在一般溶剂中难溶的物质） 、氘代吡啶（用于难溶的酸性或芳香化合物）等。

核磁溶剂峰和杂质峰

核磁溶剂峰和杂质峰

核磁溶剂峰和杂质峰

常⽤氘代溶剂和杂质峰在1H-NMR谱中的化学位移如下表所⽰（单位：ppm）

溶剂—CDCl3(CD3)2CO(CD3)2SO C6D6CD3CN CD3OH D2O

溶剂峰—7.26 2.05 2.497.16 1.94 3.31 4.80⽔峰— 1.56 2.84 3.330.40 2.13 4.87—

⼄酸— 2.10 1.96 1.91 1.55 1.96 1.99 2.08丙酮— 2.17 2.09 2.09 1.55 2.08 2.15 2.22⼄腈— 2.10 2.05 2.07 1.55 1.96 2.03 2.06苯—7.367.367.377.157.377.33—

叔丁醇CH3 1.28 1.18 1.11 1.05 1.16 1.40 1.24 OH—— 4.19 1.55 2.18——⼄醇CH3(t) 1.25 1.12 1.060.96 1.12 1.19 1.17CH2(q) 3.72 3.57 3.44 3.34 3.54 3.60 3.65

OH(s) 1.32 3.39 3.63— 2.47——⼄酸⼄酯CH3CO 2.05 1.97 1.99 1.65 1.97 2.01 2.07 OCH2(q) 4.12 4.05 4.03 3.89 4.06 4.094.14

CH3(t) 1.26 1.20 1.170.92 1.20 1.24 1.24⼄⼆醇— 3.76 3.28 3.34 3.41 3.51 3.59 3.65正⼰烷CH3(t)0.880.880.860.890.890.90—CH2(m) 1.26 1.28 1.25 1.24 1.28 1.29—甲醇CH3 3.49 3.31 3.16 3.07 3.28 3.34 3.34 OH 1.09 3.12 4.01 2.16——正戊烷CH3(t)0.880.880.860.870.890.90—CH2(m) 1.27 1.27 1.27 1.23 1.29 1.29—异丙醇CH3(d) 1.22 1.10 1.040.95 1.09 1.50 1.17CH 4.04 3.90 3.78 3.67 3.87 3.92 4.02四氢呋喃CH2 1.85 1.79 1.76 1.40 1.80 1.87 1.88 CH2O 3.76 3.63 3.60 3.57 3.64 3.713.74甲苯CH3 2.36 2.32 2.30 2.11 2.33 2.32—CH(o/p)7.177.207.187.027.307.16—

核磁溶剂峰

核磁溶剂峰

/OrganometallicsrXXXXAmericanChemicalSocietyOrganometallicsXXXX,XXX,000–000ADOI:10.1021/om100106e

NMRChemicalShiftsofTraceImpurities:CommonLaboratorySolvents,Organics,andGasesinDeuteratedSolventsRelevanttotheOrganometallicChemistGregoryR.Fulmer,*,†ler,‡NathanielH.Sherden,‡HugoE.Gottlieb,§AbrahamNudelman,§BrianM.Stoltz,‡JohnE.Bercaw,‡andKarenI.Goldberg††DepartmentofChemistry,UniversityofWashington,Box351700,Seattle,Washington98195-1700,‡ArnoldandMabelBeckmanLaboratoriesofChemicalSynthesisandCaltechCenterforCatalysisandChemicalSynthesis,DivisionofChemistryandChemicalEngineering,CaliforniaInstituteofTechnology,Pasadena,California91125,and§DepartmentofChemistry,BarIlanUniversity,RamatGan52900,IsraelReceivedFebruary11,2010Tablesof1Hand13CNMRchemicalshiftshavebeencompiledforcommonorganiccompoundsoftenusedasreagentsorfoundasproductsorcontaminantsindeuteratedorganicsolvents.BuildingupontheworkofGottlieb,Kotlyar,andNudelmanintheJournalofOrganicChemistry,signalsforcommonimpuritiesarenowreportedinadditionalNMRsolvents(tetrahydrofuran-d8,toluene-d8,dichloromethane-d2,chlorobenzene-d5,and2,2,2-trifluoroethanol-d3)whicharefrequentlyusedinorganometalliclaboratories.Chemicalshiftsforotherorganicswhichareoftenusedasreagentsorinternalstandardsorarefoundasproductsinorganometallicchemistryarealsoreportedforallthelistedsolvents.