Steven B. Hawthorne, David J. Miller, Ted R. Aulich, and S yl vi a A. Farnum Ul i vers i ty of North Dakota Energy Research Center Box 8213, Uni vers i ty S tati on &and Forks, North Dakota 58202 ABSTRACT A general method has been developed f or the preparati on of deuterated aromatic compounds that are useful f o r coal reacti on studi os and as i nternal standards f or GC/MS anal ysi s. The method requi res l i t t l e s peci al i zed equipment or synthesis expertise. A reacti on mi xture contai ni ng DC l , D2n, and chromium i s used t o exchange deuterium f or aromatic hydrogens at temperatures of ?Ono t o 300OC. A s i ngl e set of reacti on condi ti ons can he used t o prepare a wide range of deuterated aromatics with nearl y complete exchange of aromatic hydrogen f or deuterium and l i t t l e or no chemical degradation of the reactant. When a 2D:l molar r ati o of deuterium t o aromatic hydrogen was used the i s otopi c puri ty of most species tested i ncl udi ng phenanthrene ( i s otopi c pur i ty of 94%), pyrene ( 95%) , phenol (96%), dibenzofuran (96%), carbazol e (94x1, and di benzothiophene (939;), approached the H/D exchange equi 1 i brium of 95% i n two to f i f teen hours. The method al s o works wel l with complex mi xtures as demonstrated by the deuterati on o f aromatics i n a coal - deri ved anthracene o i l . INTRODUCTION The use of deuterated aromatic organi c compounds as i nternal standards f o r the eval uati on of sample preparati on procedures and f o r the anal ysi s o f complex samples usi ng gas chromatography coupled wi th mass spectrometry (GC/MS) can greatl y increase the accuracy of anal yti cal res ul ts whi l e of ten reducing the t i me requi red f or the anal ysi s. Deuterated compounds and mi xtures are al so useful f or studying the f ate of organic compounds i n complex systems such as coal conversion reacti ons. Unfortunatel y, the widespread use of deuterated compounds i s l i mi ted by thei r hi gh cost and the l ack of avai l abi l i ty o f many compound classes. The purpose of t h i s paper i s to descri be a general method f or the synthesis of deuterated species that i s appl i cabl e t o several classes o f aromatic compounds, requi res minimal ti me and synthesi s experti se, yi el ds a chemically and i s otopi cal l y pure product, uses simple and i nexpensi ve equipment and reagents, and can he used with canplex mixtures. Thi s method al so yi el ds products wi th mul ti pl e deuteri um which i s desi rabl e t o avoid the overl ap i n the mass spectra that occurs from 13C i sotope peaks and (M-H)' i ons when unlabeled and mnodeuteri o- l abel ed compounds occur i n the same sample (1). The synthesis i s s i mi l ar t o the method of Werstiuk and Kadai (2-6) f o r the H/D exchange of aromatic protons wi th D,o/DCl except that chromium i s added t o increase the r ate of H/ D exchange. The a bi l i t y of t h i s method t o provide chemically and i sotopi cal l y pure perdeuterated products was eval uated 471 f o r several aromatic hydrocarhons and 0-, S-, and N-containing aromatics. The method was al so used t o produce perdeuterated deri vati ves of the components of a coal-derived anthracene oi l . EXPE RIME MAL A l l reacti ons were performed i n 10 m 0.d. (8 mm i.d.) x approximately 8 cm long pyrex gl ass tubes. One end of the tube was sealed wi th a flame hefore adding the reagents. The reacti on mi xture was then frozen i n l i qui d ni trogen, the tube was evacuated usi ng a small l aboratory vacuum pump, and the tuhe was sealed wi th a flame. This procedure f i l l e d approximately one-half of the tube volume wi th reagents. The sealed tubes were then placed i nto a 1.3 cm 0.d. x 15 cm stai nl ess s teel pipe. Before capping the pi pe wi th "Swagelok" f i tti ngs , approximately 2 mL o f water was added so that the pressure i ns i de and outsi de of the glass reacti on tube would be approximately equal duri ng heating. As a safety measure, the s tai nl es s steel pi pe was placed i ns i de a containment vessel made from a one-inch diameter thi ck- wal l ed i r on pi pe wi th threaded end caps. A small hol e was dr i l l e d through one of the end caps t o avoid a pressure increase i n the containment vessel. The enti re apparatus was then heated t o 200-30O"C f or an appropri ate time peri od i n the oven of a gas chromatograph. Caution: Since chl ori de i on degrades the strength of s tai nl es s steel, the s tai nl es s steel pi pe shoul d be replaced i f a glass tube breaks duri ng the reacti on. The deuterati on reagent consi sted o f 4% DC1 (by wt. ) i n D?O (both > 99% i s otopi cal l y pure) wi th 10 mg/mL chromium metal. Since the di s s ol uti on of the chromium metal evolves hydrogen gas, the addi ti on of chromium was performed i n a venti l ated hood. Af ter the chromium had di ssol ved (approximately one hour), the reagent mi xture was purged br i e f l y wi th helium t o removed di ssol ved hydrogen. The reagent could then be stored i ndef i ni tel y i n a desi ccator. Unless otherwise noted, the deuterati on of the i ndi vi dual pure compounds was performed usi ng a weighed amount of approximately 100 mg of tes t species and an appropri ate volume of deuterati on reagent t o gi ve a 2O:l mol ar r ati o of reagent deuterium to exchangeable protons. Each of the pure compounds was reacted at 300C f o r 2 h r and/or 15 hr. If s i gni f i cant chemical degradation occurred a t thi s temperature, an addi ti onal synthesi s was performed a t 200C f or 2 hr. The deuterati on of the anthracene o i l was performed usi ng 50 mg of sample wi th 1.0 mL of deuterati on reagent. GC/MS anal ysi s of the deuterated products was performed wi th a Hewlett- Packard model 59858 usi ng a 30 m x 0.32 mm i.d. (l um f i l m thi ckness) DB-5 fused s i l i c a capi l l ar y column ( J & W S ci enti f i c, Rancho Cordova, C.A.). A l l analyses were performed i n the el ectron impact mode wi th 70 eV i oni zi ng voltage. I s otopi c pur i ty of the products was cal cul ated from the resul tant spectra. Gas chromatography wi th flame i oni zati on detecti on (FID) was Performed on a Hewlett-Packard model 5890 GC wi th the same type o f chromatographic column as used f or GC/MS. Chemical pur i ty of the s tar ti ng materi al s and the products was deteni ned hy GC/FID anal ysi s using gr avi mtr i cal l y prepared sol uti ons of standard and product species. Proton NMR analyses of the deuterated oroducts were oerf oned on a Varian model XL- 200. tetramethyl si l ane. The deuterated products' were di ssol ved i n CD2C12 contai ni ng 0.25% 4 7 2 Since most of the tes t compounds (except the N-containing bases) were not sol ubl e i n the reagent, quanti tati ve recovery of the products was eas i l y attai ned by pi petti ng of f the l i qui d products or by removing the reagent from the s ol i d products wi th a Pasteur pi pette. The s ol i d products were washed wi th water and dri ed t o remove the resi dual reagent. The N-containing aromatic bases ( ani l i ne and qui nol i ne) were removed from the reagent by making the reacti on mi xture basi c wi th 2N NaOH and extracti ng wi th methylene chl ori de. Since the purpose of t hi s synthesi s method was t o provide l abel ed Products wi th deuterium s ubs ti tuti on i n chemically stabl e posi ti ons, the hydroxyl deuterium on the two phenols, and the two amine deuteri um on ani l i ne were exchanged for protons from H20 before being analyzed f or thei r i s otopi c puri ty. RESULTS AND DISCUSSION The success of H/D exchange usi ng the DC1/D20/chromium reagent i n synthesi zi ng perdeuterated aromatic canpounds fromseveral canpound classes i s shown i n Table I . Mass spectra of several representati ve compounds before and af ter deuterati on are shown i n F i gure 1. H/D exchanges wi th ethyl henzene, phenanthrene, pyrene, perylene, biphenyl, phenol, dibenzofuran, ani l i ne, carbazole, and dibenzothiophene a l l approached equi l i bri um with the deuterium pool (assumed t o be 95% i s otopi c pur i ty based on the 20:l molar r ati o o f D/H) i n ei ther two or 15 hours wi th no s i gni f i cant chemical degradation. The i s otopi c puri ty of those species that attai n exchange equi l i bri um (95% i s otopi c puri ty) can be improved, i f desired, hy i ncreasi ng the r ati o of reagent D t o exchangeable H or by performing mul ti pl e exchange reacti ons. Qui nol i ne al so showed no chemical degradation, but was onl y 73% i s otopi cal l y pure af ter 15 hours. However, such products can s t i l l be useful f or i sotope di l uti on analysis. F or example, the mass spectra of 73% i s otopi cal l y pure qui nol i ne- d7 has a base peak o f 134 compared t o 129 f or undeuterated qui nol i ne and, si nce no detectabl e overl ap i n t he i r mass spectra occurs i n the molecular i on region, the 73% i s otopi cal l y pure product i s s t i l l useful as an i nternal standard (F i gure 1). Longer reacti on times and/or hi gher reagent 0 t o reactant H rati os coul d be used t o increase the i s otopi c puri ty. Only three species, 2,4-dimethylphenol, ani sol e, and 2-methylthiophene, showed enough degradation that the synthesis a t 300C was judged to be unsuitable. Mi l der condi ti ons of 200C f o r 2 hr. were used f or each of these species i n an attempt t o reduce degradation. Both 2,4-dimethylphenol and 2- methylthiophene were reasonably stabl e under these condi ti ons and yi el ded products wi th i s otopi c pur i ti es of 89% and 85%, respecti vel y (Table I ). The methyl hydrogens of 2-methylthiophene exchanged readi l y and were i ncl uded i n the cal cul ati on of i s otopi c puri ty. Anisole continued t o be converted t o phenol even at these mi l der condi ti ons wi th onl y 43% o f the ori gi nal ani sol e remaining af ter the reaction. Under these condi ti ons, onl y three pos i ti ons on ani sol e underwent s i gni f i cant H/D exchange. These posi ti ons were shown by 200 MHz proton NMR t o be the ortho- and para- posi ti ons, as would be expected si nce the methoxy group acti vates those posi ti ons f or el ectrophi l i c substi tuti on. The same res ul t i s obtai ned when phenol undergoes the synthesis a t 20DY f o r 2 hr. These res ul ts i ndi cate that thi s method may be useful t o produce aromatic compounds l abel ed at s peci f i c (ortho-, para- vs. meta-) posi ti ons by caref ul sel ecti on of the reacti on temperature. 473 The use of t h i s synthesi s t o produce perdeuterated deri vati ves i n complex mixtures was demonstrated wi th a coal deri ved anthracene o i l contai ni ng predominantly aromatic hydrocarbons. F i gure 2 shows the res ul ts obtained when the anthracene o i l underwent H/D exchange f o r 2 hours a t 300C. N3 detectabl e chemical degradation of the sample occurred as determined by a canparison of the GC/ F I D chromatograms of the o i l before and af ter the synthesis. The molecular i on regi ons of the mass spectra ohtained before and af ter the synthesis are shown f or several representati ve species (F i gure 2). The i sotopi c puri ti es were naphthalene (97%), dihenzofuran (98%), dihenzothiophene (99%), phenanthrene (96%), and pyrene (97%). Aromatic compounds having al i phati c protons al s o showed nearl y quanti tati ve exchange of aromatic protons f or deuterium, and some exchange of the al i phati c protons. For example, the base peak f or 2-methylnaphthalene-d7 ( i f onl y aromatic protons exchanged f o r D) would be a t m/z 149. The i ntense peaks a t m/z 151 and 152 show that some al i phati c protons al so exchanged (F i gure 2). The res ul ts of the perdeuterati on studi es of pure compounds (Table I ) and the anthracene o i l demonstrate that the method presented here i s useful f or synthesi zi ng perdeuterated aromatic compounds from several compound classes as wel l as i n complex mixtures. A l l of the species that have been tested yi el d products wi th both hi gh i s otopi c pur i ty and (except f or ani sol e) hi gh chemical puri ty. The cost of the reagent i s low ( l es s than 20 dol l ars f o r thi s enti re study) and the synthesi s i s simple t o perform. CREDIT The authors would l i ke t o thank the U.S. Department o f Energy for parti al support of thi s work under contract number DE-FG22-86PC90911. REFERENCES 1. Blom, K.; Schuhardt, J . ; Munson, B. Anal. Chem. 1985, 57, 1986-1988. 2. Werstiuk, N.H.; Kadai, T. Can. J . Chem. 1973, 51, 1485-1486. 3. Werstiuk, N.H.; Kadai, T. Can. J. Chem. 1974, 52, 2169-2171. 4. Werstiuk, N.H.; Yadai, T. I n "Proceedings of the F i r s t I nternati onal Conference on S tabl e I sotopes i n Chemistry, Bi ol ogy, and Medicine"; Kl ei n, P.Y.; Peterson, S.V.; Eds; 1973, NT I S CONF-730525, pp. 13-19. 5. 6. Werstiuk, N.H.; Timmins, G. Can. J . Chem. 1981, 59, 3218-3219. Werstiuk, N.H.; Timmins, G. Can. J . Chem. 1981, 51, 1485-1486. 474 Table I Synthesis of Perdeuterated Aromatic Compounds ethyl benzene phenanthrene biphenyl pyrene peryl ene phenol 2,4-dimethyl phenol ani sole dibenzofuran ani l i ne qui no1 i ne car b azo 1 e E-methyl t hi ophene dibenzothi ophene na - 5 10 10 10 12 6 4 5 8 7 7 8 6b 8 I s otopi c P uri ty (%) 2 hr 15 hr 2 hrs 3o0c 3n0c mn0c --- 50 97 94 94 84 96 - 95 - 95 94 96 100' 89 - - 97c 52 96 95 96 29 73 93 94 - - 85b 95 93 Chemical P uri ty (%) 2 hr 15 hr 2 h r 3nnoc 3on0c 2nnoc inn ino ion inn - - - ion 95 - 100 - 100 88 39 100 99 100 <5d 493 i n0 100 7 J d ion i on 94 89 99 99 e e 89 aThe number of exchangeable protons, n, i s used f or cal cul ati ng the quanti ty of reagent requi red t o gi ve a D/H r a t i o o f 21131 i n the reacti on mi x t ur e. b A l l s i x of the protons on 2-methylthiophene exchanged readi l y so n=6 was used t o determine the quanti ty of deuterati on reagent and f or the cal cul ati on o f i sotopi c puri ty. CI sotopi c puri ty was based on 3 rather than 5 H/D exchanges (see text). dThe degradation product was phenol. eNo 2-methylthiophene or i denti f i abl e degradation product was recovered. 475 Bef or e Deuterati on After Deuterati on 202 d,. -pyrene pyrene 40 20 20 106 :j, , , , 1 ~ , , , , , . , ;, , 11.. , 0 0 . . . . : :I. . . . :. . 40 80 80 100 120 140 I60 180 200 220 10 60 80 100 120 140 160 80 ZOO 220 20 40 60 80 100 120 1 . 0 i i 40 I I II 2 12 192 I 100 (64 I d,-dibenzothiophene C - 100 dibenzothiophene - . ; ii .,,,,, I.T., ;,, , , , , ,I,.< ; ; I , , , , ! , E ~ , ~ ~ , , , , ,,, ~ , , 1,. 152 18 160 a 2o 0 40 60 80 100 120 140 160 I60 200 40 60 80 100 120 140 160 180 200 1 : : 1 , d , , q; ; ; ,L , ,121 , , , . . , 6 1 , ~, , d,-quinoline ,dly- , ,;I , 1,. , , , , 80 10 20 0 20 102 40 60 80 100 120 140 160 180 40 60 80 100 I20 140 160 160 i.1 , , carbazole : ,, , , , , , , , , ,!, , , , j , 1 ; j i d. -carbazole 20 8. 138 145 10 0 40 60 80 100 120 140 160 I80 40 60 80 100 120 140 I60 180 ml z ml z Fi g u r e 1: El ec t r o n i mpact mass s pec t r a o f r e r es en t at i v e PAH and 0-, S-, and N- c o n t ai n i n g ar omat i c s b ef o r e ( Pe f t s i d e of f i g u r e ) and a f t e r ( r i g h t s i d e) d eu t er at i o n f o r 15 hour s a t 300OC. I s o t o p i c and chemi cal p u r i t i e s ar e gi ven i n Tab l e I . 476 ! ! 0 , , I m 120 140 C 0 136 .- * c : a 0 n i , , ,,I,, , T 120 140 140 160 150 160 180 I I-L 1 0 2 0 0 170 190 J L 200 2 2 0 .I 200 220 / L I r 5 10 15 2 0 Retenti on Time (mi d Fi g u r e 2: A compar i son of t h e mass s p ec t r al mol ec ul ar i o n r egi ons of r ep r es en t at i v e s pec i es b ef o r e ( upper s p ec t r a) and a f t e r ( l o wer s p ec t r a) d eu t er at i o n o f a c o al - d er i v ed ant hr acene oi l . Reac t i on c o n d i t i o n s , i s o t o p i c p u r i t i e s , and gas chr omat ogr aphi c c o n d i t i o n s a r e g i v en i n t h e t e x t . 477