a-Hydrogen exch ange during the elimination from 2-phenylethyldimethylsulphonium bromide with on- in d euterium oxide
h as been found to b e a lmost complete under certain r eactio n conditions. The product, trimethylamine, from the a n a logo u s reaction
of 2-phenylethyltrimethylammonium iodide with eith er ethoxide
ion in ethanol-0-d or with OD- in d~u terium oxide was found
to contain no d etectabl e amount of deuterium above natural
abundance

D . Pavlović

D. Stefanović

I. Murati

L. Klasinc

S. Asperger

English

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CCA-347 CR 0 AT IC A CHEMIC A ACT A 36 (1964) 209 541.124:546.11.02 Original Scientific Paper a-Hydrogen Exchange in the Reaction of 2-Phenylethyldimethyl-sulphonium Ion with Base in Aqueous Solution and of 2-Phenyl-ethyltrimethylammonium Ion with Base in Aqueous and Alcoholic Solution* S. Asperger, D. Pavlovic, L. Klasinc, D. Stefanovic, and I. Murati D epartment of Physical Chemistry, Institute »Ruder Bo!ikovic«, Zagreb, and Department of Inorganic and Physical Chemistry, Faculty of Pharmacy and Biochemistry, University of Zagreb, Zagreb , Croatia, Yugoslavia Received November 26, 1964 a-Hydrogen exch ange during the elimination from 2-phenyl-ethyldimethylsulphonium bromide with on- in deuterium oxide h as been found to be almost complete under certain r eaction con-ditions. The product, trimethylamine, from the analogous reaction of 2-phenylethyltrimethylammonium iodide with either ethoxide ion in ethanol-0-d or with OD- in d~uterium oxide was found to contain no detectable amount of deuterium above natural abundance. A ma ss..,spectrometric method for the determination of small amounts of deuterium is described. Doedng and Hoffmann1 measured the deuteroxtde--cataly.sed hydrogen exchange of methyl »onium« salts and found that trimethylsulphonium iodide and tetramethy1phosphonium iodide exchange hydrogen very rapidly while tetramethylammonium iodide exchanges hydrnigen very slowly. This was explained in terms of d-orbital resonance which lowers the energy of the transition state from the phosphonium and sulphonium ions. It was previously observed2·3 that 1,l-d1deutero-2-phenylethyldimethyl-sulphonium bromide with aqueous base exchanges deuterium during eli-mination. This excharnge has now been thoroughly r eexamined and it was found that under certain conditions it is almost quantitative. The a-hydrogen exchange in the reaction of 2-phenylethyltrimethyl-ammonium iodide with ethoxide ion in ethanol-0-d and with deuteroxide in deuterium oxide solution was also examined; n '.) excha:nge could be observed. This exchange was ,studied by mass-spectrometric determination of ratio of masses 60/ 59 in the trimethylamine collected from the elimination reaction. Any increase of deuterium above natural abundance would increase the ratio 60/ 59 arnd indicate that a-hydrogen exchange had occurred during elimi-nation. Mass 60 results from the carbon-13, nitrogen-15 and deuterium content. Thus, only 1 per cent of deuterium in trimethylamine above natural * Reported a t the International Symposium on Organic Reaction Mechanism, Cork, Ireland, July 20-25, 1964. 210 S. ASPERGER E1' AL. abundance would increase mass 60 approximately from 3.7 to 4.7 per cent of mass 59. Since one tenth of this increase could have been determined the analyses were appreciably more accurate than the deuterium analyses by the usually employed »falJi.ng drop method« which has an error of about 1 per cenit1•4 • RESULTS 1. a-Hydrogen Exchange in the Reaction of 2-Phenylethyldimethylsulphonium Bromide with Hydroxide Ion in Aqueous Solution In the first series of experiments the reaction of 0.1 M 2-phenylethyl-dimethylsulphoniUIID bromide with 0.2 M on- in deuterium oxide at 58.9° was carried to 300/o completion. The rate constant amounts to 1.14 X 10-4 sec.-1 mole-1 1 at that temperature5• The unreacted sulphonium salt was then re-covered and reduced with lithium aluminium hydride6• A liquid reaction product was obtained. The dominant component was methyl-2-phenylethyl surphide. The highest mass in the mass-spectrum was 157 corresponding to Cr;H5CH2CD 2SCD3 • When the elimination was carried out in aqueous solution with hydroxide ion under the same conditions as in deuterated media, the product ·Of reduction of the unreacted sulphonium salt with lithium alu-minium hydride had the highest mass 152 oorrespoinding to C"H 5CH.,CH2SCH". Mass-spectra showed that the extent of a-hydrogen exchange in the sulphonium salt was aipproxi:mately 990/o. The initial sulphonium salt also gave upon lithium aluminium hydride reduction a liquid product with the highest mass 152. The reduction of 2-phenylethyldimethylsulphonium ion to the methyl--2-phenylethyl su1phide has not been previously reported. The composition of the liquid reduction product-mixture is being investigated. When 2--phenylethyldi!methylsulphonium bromide was dissolved in deute-rium oxide and left under the reaction conditions uf the elimination without added base for a time corresponding to 300/o completion of the reaction, the product of the reduction with lithium aluminium hydride of the regenerated sulphonium salt had the highest mass 152, showing that no exchange occurs without base. Ln foe second series of experiments the reaction of 0.1 M 2-phenyl-ethyldimethylsulphonium bromide with 0.2 Mon- m deuterium oxide was carried out to completion at 97°C. The reaction time was approximately 150 min.5 Dimethyl sulphide was expelled from the reaction solution and col-lected in a liquid air trap. After purification the mass-spectra were recorded. The ma~n and the h ighest mass was 68 correspond-mg to S(CD3}z. Masses 68, 67, 66, 65, 64, 63, and 62 were measured and the relative magnitudes determined as 721, 94, 212, 20, 7, 4, and 19. From these data it was calculated that dimethy.l sulphide contained approximately 880/o of deutedum. In the first series of experiments the exchange was much h1gher (990/o) ·because in the recovered sulphonium salt an accumulation of deuterium took place. Iin the third series of eX'periments the reaction of 0.1 M 2-:t>henylethyl-dimethylsu1phcmi:um bromide and 0.2 Mon- in deuterium oxide was carried out at 710 to completion. The rate constant5 at 70.70° amounts to 4.32 X 10-4 sec.-1 mole-1 1. Styrene was collected in the liquid air trap. Dimethyl sulphide was removed in v.acuo and styrene distilled under reduced pressure. The a - HYDROGEN EXCHANGE 211 highest mass found in the mass-spectrum -of styrene was 106, corresponding to C6H 5CH = CD 2 • Ln uindeuterated aqueous media, blanks showed that the highest mass was 104. 2. a-Hydrogen Exchange in the Reaction of 2-Phenylethyltrimethylammonium Iodide with Base I!n the fir.st series of experiments the reaction of 0.1 M 2-;phenylethyl-trimethylammcmium iodide and 0.2 Mon- iin d euterium oxide was carried out to completion !'.nd trimethylamine collected in a liquid air trap and pu.rified. Mass-spectra of trimethylamine showed that the ratio of masses 60/ 59 remained practically equal to the ratio of the same masses iin trimethylamine collected from the reaction in aqueous undeuterated media. In the second series of experiments the reaction of 0.04 M 2-phenyl-ethyltrimethylammonium iodide and 0.14 M ethoxide ion in ethanol-0-d at 45° was carried out to completion. The .rate constant at 40.00 amoun:ed to 5.2 X 10-4 sec.-1 mole-1 1. The reach-on time for 99°/o completion of the reaction was calculated for 40.0°. The ratio of masses 60/59 in the collected tr~methylamirne was compared with the same ratio in trimethylamine collected from the reaction in undeuterated media under the same conditions. All ratios obtahied iin both series of ex;periments were also compared with that of commercial trimethylamine. A slight decrease -of the ratio of masses 60/ 59 was observed in the trimethylamine from ethanol-0-d solution. It was probably caused by impurities in ethainol-0-d. The results are given in 'Dable I. TABLE I Mass 60/59 Ratio in Trimethylamine D etermined by Mass-spectrometry A. From the reaction of 0.1 M PhCH2CH2N(CHs)3I at 970 with: 0.2 M OH- in H20 0.2 M on- in D20 B. From the reaction of 0.04 M PhCH2CH2N(CH3)sI at 450 with: 0.14 M Eto- in EtOH 0.14 M Eto- in EtOD commercial N(CHa)s theoretical ratio a Average of: 3.73 and 3.81 b Average of: 3.59 and 3.58 c Average of: 3.77, 3.71, 3.80 and 3.67 Masses 60/59 X100 3.73 3.76 3.77a 3.59b 3.73C 3.78 It can be concluded that no a -hydrogen exchange occurs in the reaction of the ammoniUJm salt. DISCUSSION Doering and Hoffmann1 foUIIld a small deuterium exchange of 1.130/o in 0.3 M tetramethylammonium iodide with 0.3 M deuteroxide in deuterium oxide solution after 358 hours at 100°. We cou1d not found a measurable exchange in trimethylamine collected during elimination from the 2-phenyl-ethyltrimethylammonium salt. It is very lilkely that the exchange of .the a-methylene-groups of the ammonium salt during elimination is also 212 S. ASPERGER ET AL. negligiible since the phenyl group should not have an important influence on the acidity of these hydrogens. The total reaction time of the elimination in aqueous solution at 97° was approximately 60 hours and in alcoholic solution at 45° approximately 14 hours. These conditions were mi1der than those of Doering and Hoffmann. Analogous mass-spectrometric measurements make possible the study of ,8-hydrogen exchange in the »Onium« salts dL~ring elimination. EXPERIMENTAL Materials 2-Phenylethyldimethylsulphonium Bromide The preparation was described earlier;;. Anal. C10H1sBrS (247.21) calc'd: Br. 32.330/o found: Br. 32.560/o 2-Phenylethyltrimethylammonium Iodide A batch previously prepared and analysed was used7. Ethanol-0-d The procedure of Salas and Wilson was applieds. The deuterated alcohol contained about 30/o of deuterium oxide which was not removed. Regeneration of the Unreacted 2-Phenyl.ethyldirnethylsulphonium Sali To the reaction solution solid silver nitrate was added which removed the base and also precipitated bromide ions. The precipitate was filtered off and styrene extracted with ether. Deuterium oxide was evaporated in vacuo and the sulphonium salt dried in a vacuum desicator. Reduction of 2-Phenylethyldimethylsulphonium Bromide 2-Phenylethyldimethylsulphonium bromide was reduced with two molar excess of lithium aluminium hydride in refluxing ether during 3 hours. The procedure of Amundsen and NelsonG was further applied. Ether was removed in vacuo and the remaining liquid distilled under reduced pressure. The product, predomi-nantly methyl-2-phenylethyl sulphide, was then introduced into the mass-spectro-meter. Collection and Purification of Dimethyl Sulphide Samples To the reaction vessel immersed in a water-bath held at 970 a condeser was attached to hold back most of the water vapour. Nitrogen, purified by passage through Ascarite and sulphuric acid, was bubbled through the reaction solution to expel the dimethyl sulphide which was collected in a liquid air trap. Purifi-cation of dimethyl sulphide samples was carried out as previously describeds. Collection and Purification of Trimethylamine Samples Trimethylamine was expelled from the reaction vessel in the same way as dimethyl sulphide. When the elimination from the 2-phenylethyltrimethylammo-nium iodide was carried out in alcoholic media trimethylamine expelled with nitrogen contained appreciable quantity of ethanol. A washing bottle with concen-trated sodium hydroxide kept at 700 held back ethanol. Trimethylamine freed from alcohol was then trapped in liquid air trap. It was further purified in a vacuum line analogously to dimethyl sulphide5, except that calcium oxide was used for drying (instead of phosphorous J?entoxide used for drying of dimethyl sulphide). Mass-spectrometry A Niers's type mass-spectrometer with a resolution of 1 :350 was used9. a - HYDROGEN EXCHANGE 213 REFERENCES 1. W. von E. Doering and A. K. Hoffmann, J. Am. Chem. Soc. 77 (1955) 521. 2. S. Asper g er, N. I 1 a k ova c, and D. Pav 1 o vi c, J. Am. Chem. Soc. 83 (1961) 5032. 3. S. Asper g er, N. I 1 a k ova c, and D. Pav 1 o vi c, Croat. Chem. Acta 34 (1962) 7. 4. A. S. Ke st o n, D. Ritt en b erg, and R. S ch o en he i mer, J. Biol. Chem. 122 (1937) 227. 5. W. H. Saunders, Jr. and S. Asper g er, J. Am. Chem. Soc. 79 (1957) 1612. 6. L. H. Am u n d s en and L. S. Ne 1 son, J. Am. Chem. Soc. 73 (1951) 242. 7. S. Asper g er, L. K 1 as inc, and D. Pav 1 o vi c, Croat. Chem. Acta 36 (1964) 161. 8. E. de Sa 1 as and C. L. W i 1 son, J. Chem. Soc. 1938, 319. 9. For the characteristics of the instrument see: Furman and V rs ca j, Re-ports J. Stefan Inst., Ljubljana, Yugoslavia, 4 (1957) 109. IZVOD Izmjena a-vodika u reakciji 2-feniletildimetilsulfonijeva iona s bazom u vodenoj otopini i 2-feniletiltrimetilamonijeva iona s bazom u vodenoj i alkoholnoj otopini s. Asperger, D. Paviovic, L. Klasinc, D. Stefanovic , I. Murati Nadeno je da je izmjena a-vodika u reakciji eliminacije 2-feniletildimetilsulfo-nijeva bromida sa OD- u teskoj vodi pod odredenim uvjetima gotovo potpuna. Ta.koder je ustanovljeno da u analognoj reakciji 2-feniletiltrimetilamonijevog jodida sa etoksi ionom u etanolu-0-d, odnosno sa OD- u teskoj vodi, reakcioni pro-dukt trimetilamin, ne saddi deuterija iznad prirodnoga sadrfaja, sto znaci da u reakciji amonijeve soli ne dolazi do izmjene a-vodika. Opisana je takoder metoda spektrografije mase za odredivanje malih koli-cina deuterija. INSTITUT »RUDER BOSKOVIC« I ZA VOD ZA ANORGANSKU I FIZIKALNU KEMIJU FARMACEUTSKO-BIOKEMI.TSKI FAKULTET ZAGREB Primljeno ~6. studenoga 1964. 

a-Hydrogen Exchange in the Re action of 2-Phenylethyldimethylsulphonium
Ion with Base in Aqueous Solution and of 2-Phenylethyltrimethylammoni
um Ion with Base in Aqueous and Alcoholic Solution

a-Hydrogen Exchange in the Re action of 2-Phenylethyldimethylsulphonium Ion with Base in Aqueous Solution and of 2-Phenylethyltrimethylammoni um Ion with Base in Aqueous and Alcoholic Solution

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