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A Theoretical Study of Reaction of Nitrile Oxides with Ammonia "C

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A Theoretical Study of Reaction of Nitrile Oxides with Ammonia /, ,1111, j j~~I'hM _Hfl<jliid;,~;1 ilidU, I 'II ~I",I 11,111 ,I""II, '"" nlll;1 lii'l II I ~ Indian Journal of Chemistry Vol. 26A, November 1987, pp. 906-913 A Theoretical Study of Reaction of Nitrile Oxides with Ammonia KRISHAN K SHARMN & ANIL K AGGARWAL Department of Chemistry, Zakir Husain College, University of Delhi, Ajmeri Gate, Delhi 110006 Received 3 February 1987; revised 10 March 1987; accepted 16 Apri/1987 The potential energy hypersurface for the reaction of nitrile oxides, RCNO (R=H, fulminic acid; and R=CH3, acetonitrile oxide) with NH3 as a nucleophile to give oximes RNHzC = NOH has been studied by the MNDO method. The calculations have been performed with complete geometry optimisation using Davidon-Fletcher• Powell method. The bond distance C3 - Nz (denoted by R), between the carbon of nitrile oxide and nitrogen of ammonia, has been employed as the reaction coordinate. The energy along the reaction coordinate is minimised at each point by varying all the parameters (bond lengths, bond angles and the twist angles). The reaction is predict• ed to be exothermic and proceeds in two steps. The first step is the formation of zwitterionic structure as interme• diate via a transition state at R = 1.88 A. This step is the rate-determining step and requires the calculated activa• tion energy of 28.86 kcal mol- I in the case of fulminic acid and 33.10 kcal mol- I for acetonitrile oxide. The sec• ond step which involves transfer of a proton occurs very fast and requires a passage over a further barrier with an activation energy of only 1.96 and 2.17 local mol-t respectively for fulminic acid and acetonitrile oxide. This then leads to the formation of the product amidoxime of Z-configuration, as has been observed experimentally. Recently, we have reported MNDO study on the In the present work, we have carried out a the• reaction of methanol with nitrile oxide (RCNO)l. oretical study of the reactions of ammonia with The reaction involving nitrogen nucleophiles e.g. fulminic acid (HCNO; 1, R = H) and acetonitrile NH3, RNHz, RzNH etc. and nitrile oxides also oxide (CH3CNO; 1, R=CH3) using both as sub• leads to open chain oximes as the products z -7. strates. These reaction systems have been chosen The reaction of RCNO with the nucleophiles ex• as a model to make a comparative study. We were clusively occurs by an attack at carbonz,8. How• particularly interested in the stereochemistry of ever, these reactions also appear to be stereospe• the reaction and in the characteristics of the cific in nature in that only one of the two possible transition state, since the transition state geometry oxime isomers (Z or E) is invariably formed. is not observable experimentally; these can only Nitrile oxide (RCNO) (1), a typical 1,3-dipole, be checked theoretically. reacts with primary and secondary amines stere• ospecificallyz to give only the Z-amidoximes (4 Method of Calculations and5) in which the nucleophile and the - OH The calculations were carried out by the groups are in cis position. With primary amines MNDO method of Dewar and Thiel9• The meth• and ammoniaz the Z-isomer (2) is also thermody• od of Davidon-Fletcher-PowelllO was employed namically favoured but the subsequent isomerisa• for the optimisation of molecular geometries using tion to the more stable E-isomer (3) occurs with MNDO program 11. The transition states were the more bulky secondary amines. found by the usual reaction coordinate method 12, and were confirmed by checking one negative ei• 13. 3 genvalue in the diagonalised Hessian matrix R The second transition state (1'2) was located by (l) "c R transferring the proton from the nucleophile to / -N _ "-... /OH RzN \ /C=N ( the terminal oxygen of substrates at a point when the charge-transfer, from the nucleophile to the OH R~ El substrate, was maximum. The bond distance R, Rz=Mtz or (CHzI41RzNH (Z) C-N R"C ••••N (l) - / 4 NH C3 N2 (denoted by R) was taken as the reaction RNH "- OH RNHz RCNO1 ---! ~HzN / "'-OH coordinate. The heats of formation of the super• 2 molecule (RCNO + NH3) were plotted against the 4 !PhNHIII distance R. In accordance with the predictions of R R Rothman and Lohrl4, the maximum on such a (II 'C-N •• "-...C=N /OH reaction surface is the transition state provided Ph NIII/ - \.OH PhN' (E) the reaction path is continuous. All the results re• 5 ported in this paper were derived without involv- 906 '1'- 'I" jfl!ll" SHARMA & AGGARWAL: THEORETICAL STUDY OF REACTION OF NITRILE OXIDES WITH AMMONIA -6 +6 -6 H- C== N H-C==:N=-=O ,·055 1·160 1·04! ,.,6> ,,,, 0[1'0631 (1-I54J b[I'027J [1-168] (1-199] 'H·0·244 'N = 0·262 reN N R~1 'C ••-0,116 '0" -0,320 hJ3 r~o R,' ..•05 'H,"0'076 , =0'094 H H H N 9 , H ,2 10H~~ : -0.228 \ 1·3/5 4 =-0,226 I I r , ..•'r' Y,f~N , •• 0'f8~ C N N HT007 ", = '1<d.,,l_ - ,,' " ,~ H H "'H H C / \ 'H=0"98 , 'H=O:;;;--N\'N" 0'398 '0'-0'231 H 0- H Rt :H,CH;,i H3H7,HIO jH =H.,HII 4H =0·/97 Fig. 2 - Geometric parameters varied along the reaction path• Fig. 1 - Structures of fulminic acid and the formamidoxime: way. [bond lengths in (A) and the net charges in (e-) on the atoms are calculated using MNDO method]. 'Costain C C, I chern Phys, 29 (1958) 864; bsee ref. 16. For detailed structure of charge on the atoms of reactants and the product the formamidoxime see Fig. 4a. are summarised in Fig. 1. The calculated carbon• nitrogen bond length of fulminic acid (1.169 A.) approaches that of hydrogen cyanide (1.160 A.) ing configurational interaction (CI), since the indicating a partial triple bond character of C - N number of pairs of electrons is conserved in the bond. Also, the N - 0 bond has a partial double course of reaction and consequently correlation bond character as the N - 0 bond length is closer energy will be small. to N = 0 bond then to N - ° bond. The charge All the calculations were performed on VAX distribution shows that the charges are delocalised 11/750 computer. over three atoms (C, Nand 0) of the fulminic ac• id. The overall calculated structure of fulminic ac• Results and Discussion idstructuresis an intermediateH-C==N-O b~tweenand H-C=N=O.the lWo+resonatingThis (A) Geometry of reactants and products preponderance is responsible for the high dipole The optimised geometries of fulminic acid and moment of 3.51D calculated in contrast to 3.15D acetonitrile oxide have already been described 1• observed experimentallyl6. The proposed struc• The geometry for ammonia has been taken from ture is thus consistent with the experimental the work of Dewar and Thieps. For the amidox• onel7. imes, the present results agree quite well with In particular, it should be noted that the carbon those of X-ray refined structure proposed by of fulminic acid bears a net negative charge. This Hall? is inconsistent with the carbon atom being the The corresponding heats of formation of centre of attack by ammonia. Therefore, during HCNO, CH)CNO, NH), HNHzC = NOH and approach of the nucleophile NH), the electronic H)CNHzC =NOH are 50.79, 34.93, - 6.3, reorganisation should occur so as to generate an - 8.24 and -16.59 kcal mol-l respectively. The electrophilic carbon centre to facilitate the nucle• products formamidoxime and acetamidoxime are ophilic attack by NH). This is then followed by thus 52.71 and 45.22 kcal mol-l respectively the transformation of C ==N bond into C = N, the more stable than the reactants formation of a lone pair on nitrogen and finally (RCNO + NH) : R =H, CH)). The present calcul• migration of proton from nitrogen to oxygen. ations show that the Z-isomer of amidoxime is the most stable, as was also observed experimentally (C) Reaction of ReNO with NH) by Dignam et aF The stability depends on the The reaction pathway for the addition of am• equilibrium between the repulsive interactions of monia to nitrile oxides has been calculated as a adjacent hydrogens and hydrogen-oxygen or hy• function of the following parameters as defined in drogen-nitrogen attractions. Fig. 2: a, LC)NzH; (3, LN4C)NZ; y, LOSN4C); f.l, L RlC)N4; e, L HNzC); L H'NzH bond angles; (B) Description of structures NZH!, N4C3, OsN4, RlC", HNz and H'Nz bond The structural characteristics and the net' lengths; H05 distance; and H'NzHH] twist angle. 907 I /, •11, I.JHI H ",i J,,!,i I",,,, • "'Ill ". ,JJ I~"IN, ~ 11j.,; i I I,j, I 'i !J . 'I r r 1.1691.1701.2581.2621.3421.2441.2451.3581.3521.3651.2521.3711.2681.3601.3621.3631.3311.3401.3501.3541.2281.1801.2151.3662.8451.2503.6951.3563.3062.9732.9642.9433.7391.3691.2631.3823.1203.5603.1703.1582.9722.680139.42.5822.640140.7146.53.1512.6912.587122.92.6482.5853.1302.6741.022123.3123.5136.21.478123.10.958116.8]60.4]49.8120.5123.2138.5138.01.0282.545122.52.663].085123.41.0852.6691.307123.6123.91.4872.5702.564140.9139.02.7601.0842.622a1.086II1.1891.4861.0251.083122.0125.3122.2122.6121.31.3061.048].007145.4139.91.443138.8137.5124.0rl'O1.0681.069137.0120.9122.4122.7139.71.020124.72.728125.0123.7122.11.026124.2120.7125.1123.01.471131.7135.1121.21.4851.194137.71.0781.024e167.0180.0142.9121.61.4931.089128.3115.9127.4125.5109.2]80.01.0541.067118.51.4651.4691.1931.0811.192121.7123.8].0201.190121.51.1881.4881.0131.0631.468119.3127.2121.8121.91.481114.4119.21.0151.0]51.1861.19"1121.01.0071.016114.5115.7118.8118.6114.11.0]6120.61.191121.4131.516111.3114.0129.0129.5119.1118.91.101129.3119.8rRC131.7130.4]36.8130.1]20.4120.5120.4122.9121.3122.3122.2128.7121.5120.0128.9120.7120.1121.7127.3134.61.321121.01.31562.6567.7163.3749.8461.7349.6860.8062.8061.5949.6949.7349.9173.3361.4161.4661.6861.7261.7161.5851.8551.0273.3571.5973.2973.3459.8952.59 -16.59-8.2444.4928.63 INDIAN180.0 J.
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