Kinetics and Mechanism of the Pyridinolysis of Dimethyl Isothiocyanophosphate in Acetonitrile

Adhikary, Keshab Kumar,Lee, Hai-Whang Korean Chemical Society 2012 Bulletin of the Korean Chemical Society Vol.33 No.7

The kinetics and mechanism of the pyridinolysis ($XC_5H_4N$) of dimethyl isothiocyanophosphate are investigated in acetonitrile at $55.0^{\circ}C$. The Hammett and Br$\ddot{o}$nsted plots for substituent X variations in the nucleophiles exhibit two discrete slopes with a break region between X = 3-Ac and 4-Ac. These are interpreted to indicate a mechanistic change at the break region from a concerted to a stepwise mechanism with a rate-limiting expulsion of the isothiocyanate leaving group from the intermediate. The relatively large ${\beta}x$ values imply much greater fraction of frontside nucleophilic attack TSf than that of backside attack TSb. The steric effects of the two ligands play an important role to determine the pyridinolysis rates of isothiocyanophosphates.

Significant Substituent Effects on Pyridinolysis of Aryl Ethyl Chlorophosphates in Acetonitrile

Adhikary, Keshab Kumar,Lee, Hai Whang Korean Chemical Society 2014 Bulletin of the Korean Chemical Society Vol.35 No.5

The substituent effects on the pyridinolysis (XC5H4N) of Y-aryl ethyl chlorophosphates are investigated in acetonitrile at $35.0^{\circ}C$. The two strong ${\pi}$-acceptor substituents, X = 4-Ac and 4-CN in the X-pyridines, exhibit large positive deviations from the Hammett plots but little positive deviations from the Br$\ddot{o}$nsted plots. The substituent Y effects on the rates are really significant and the Hammett plots for substituent Y variations in the substrates invariably change from biphasic concave downwards via isokinetic at X = H to biphasic concave upwards with a break point at Y = 3-Me as the pyridine becomes less basic. These are interpreted to indicate a mechanistic change at the break point from a stepwise mechanism with a rate-limiting bond formation (${\rho}_{XY}$ = -6.26) for Y = (4-MeO, 4-Me, 3-Me) to with a rate-limiting leaving group expulsion from the intermediate (${\rho}_{XY}$ = +5.47) for Y = (4-Me, H, 3-MeO). The exceptionally large magnitudes of ${\rho}_{XY}$ values imply frontside nucleophilic attack transition state.

Kinetics and Mechanism of the Pyridinolysis of Diethyl Isothiocyanophosphate in Acetonitrile

Adhikary, Keshab Kumar,Lee, Hai-Whang Korean Chemical Society 2012 Bulletin of the Korean Chemical Society Vol.33 No.3

The kinetics and mechanism of the pyridinolysis ($XC_5H_4N$) of diethyl isothiocyanophosphate are investigated in acetonitrile at $55.0^{\circ}C$. The Hammett and Bronsted plots for substituent X variations in the nucleophiles exhibit the two discrete slopes with a break region between X = 3-Ac and 4-Ac. These are interpreted to indicate a mechanistic change at the break region from a concerted to a stepwise mechanism with rate-limiting expulsion of the isothiocyanate leaving group from a trigonal bipyramidal pentacoordinated intermediate. The relatively large ${\beta}_x$ values with more basic and less basic pyridines imply much greater fraction of frontside nucleophilic attack TSf than that of backside attack TSb.

One-Pot Conversion of Carbohydrates into Pyrrole-2-carbaldehydes as Sustainable Platform Chemicals

Adhikary, Nirmal Das,Kwon, Sunjeong,Chung, Wook-Jin,Koo, Sangho American Chemical Society 2015 Journal of organic chemistry Vol.80 No.15

<P>A practical conversion method of carbohydrates into <I>N</I>-substituted 5-(hydroxymethyl)pyrrole-2-carbaldehydes (pyrralines) was developed by the reaction with primary amines and oxalic acid in DMSO at 90 °C. Further cyclization of the highly functionalized pyrralines afforded the pyrrole-fused poly-heterocyclic compounds as potential intermediates for drugs, food flavors, and functional materials. The mild Maillard variant of carbohydrates and amino esters in heated DMSO with oxalic acid expeditiously produced the pyrrole-2-carbaldehyde skeleton, which can be concisely transformed into the pyrrole alkaloid natural products, 2-benzyl- and 2-methylpyrrolo[1,4]oxazin-3-ones <B>8</B> and <B>9</B>, lobechine <B>10</B>, and (−)-hanishin <B>11</B> in 23–32% overall yields from each carbohydrate.</P><P><B>Graphic Abstract</B> <IMG SRC='http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/joceah/2015/joceah.2015.80.issue-15/acs.joc.5b01349/production/images/medium/jo-2015-01349v_0011.gif'></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/jo5b01349'>ACS Electronic Supporting Info</A></P>

Dynamic analysis of water storage tank with rigid block at bottom

Adhikary, Ranjan,Mandal, Kalyan Kumar Techno-Press 2018 Ocean systems engineering Vol.8 No.1

The present paper deals with the finite element analysis of water tanks with rigid baffle. Fluid is discretized by two dimensional eight-node isoparametric elements and the governing equation is simulated by pressure based formulation to reduce the degrees of freedom in the domain. Both free vibration and force vibration analysis are carried out for different sizes and positions of block at tank bottom. The fundamental frequency depends on block height and it reduces with the increase of block height. The variation of hydrodynamic pressure on tank walls not only depends of the exciting frequency but also on the size and position of rigid block at tank bottom. The hydrodynamic pressure has higher value when the exciting frequency is equal and lower than the fundamental frequency of the water in the tank. Similarly, the hydrodynamic pressure increases with the increase of width of the block for all exciting frequencies when the block is at the centre of tank. The left and right walls of tank have experienced different hydrodynamic pressure when the block is placed at off-centre. However, the increase in hydrodynamic pressure on nearest tank wall becomes insignificant after a certain value of the distance between the wall and the rigid block.

Pyridinolysis of O,O-Diphenyl S-Phenyl Phosphorothiolates in Acetonitrile

Adhikary, Keshab Kumar,Lumbiny, Bilkis Jahan,Kim, Chan-Kyung,Lee, Hai Whang Korean Chemical Society 2008 Bulletin of the Korean Chemical Society Vol.29 No.4

The reactions of O,O-diphenyl Z-S-phenyl phosphorothiolates with X-pyridines have been studied kinetically in acetonitrile at $35.0{^{\circ}C}$. The Hammett plots for substituent (Z) variations in the leaving group (log $k_2$ vs. $\sigma$ Z) are biphasic concave downwards with breaks at Z = H. The large magnitudes of ${\rho}X(\rho_{nuc})$, ${\beta}X(\rho_{nuc})$, and the cross-interaction constant, $\rho$XZ, suggest frontside nucleophilic attack toward the leaving group. The sign reversal of $\rho$Z from positive in $\sigma$ Z $\leq$ 0 to negative in $\sigma$ Z $\geq$ 0 is interpreted as the change in mechanism from concerted to stepwise with rate-limiting expulsion of the leaving group. The anomalous negative sign of $\rho$ Z for leaving groups with electron-withdrawing substituents is interpreted as the intramolecular ligand exchange process of the leaving group from the equatorial position in the intermediate to the apical position in the TS.

Kinetics and Mechanism of the Pyridinolysis of Aryl Ethyl Chlorothiophosphates in Acetonitrile

Adhikary, Keshab Kumar,Lee, Hai-Whang Korean Chemical Society 2011 Bulletin of the Korean Chemical Society Vol.32 No.11

The nucleophilic substitution reactions of Y-aryl ethyl chlorothiophosphates with X-pyridines are studied kinetically in acetonitrile at $55.0^{\circ}C$. The Hammett and Bronsted plots for substituent X variations in the nucleophiles exhibit biphasic concave upwards with a break point at X = 3-Me. The substituents of X = 4-CN and 4-Ac show great positive deviations from both the Hammett and Bronsted plots. The Hammett plots for substituent Y variations in the substrates exhibit biphasic concave upwards with a minimum point at Y = H. The obtained values of the cross-interaction constants (${\rho}_{XY}$) are all in spite of the biphasic free energy correlations for both substituent X and Y variations, since the ${\rho}_X$values with both the strongly and weakly basic pyridines are almost constant. A stepwise mechanism with a rate-limiting leaving group departure from the intermediate is proposed where the distance between X and Y does not vary from the intermediate to the second transition state. A frontside attack is proposed with the strongly basic pyridines based on the considerably great magnitudes of ${\rho}_X$ and ${\beta}_X$ values and a backside attack is proposed with the weakly basic pyridines based on the relatively small magnitudes of ${\rho}_X$ and ${\beta}_X$. The positive deviations of the two strong ${\pi}$-acceptor parasubstituents, X = 4-Ac and 4-CN, from both the Hammett and Bronsted plots are rationalized by the great extents of bond formation and breaking.

Kinetics and Mechanism of the Benzylaminolysis of O,O-Diethyl S-Aryl Phosphorothioates in Dimethyl Sulfoxide

Adhikary, Keshab Kumar,Lee, Hai-Whang Korean Chemical Society 2011 Bulletin of the Korean Chemical Society Vol.32 No.10

The reactions of O,O-diethyl Z-S-aryl phosphorothioates with X-benzylamines are kinetically investigated in dimethyl sulfoxide at $85.0^{\circ}C$. The Hammett (log $k_2$ vs ${\sigma}x$) and Br$\ddot{o}$nsted [log $k_2$ vs $pK_a$(X)] plots are biphasic concave downwards for substituent X variations in the nucleophiles with a break point at X = H. The signs of the cross-interaction constants (${\rho}xz$) are positive for both the strongly and weakly basic nucleophiles. Considerably great magnitude of ${\rho}xz$ (= 6.56) value is observed with the weakly basic nucleophiles, while ${\rho}xz$ = 0.91 with the strongly basic nucleophiles. Proposed reaction mechanism is a stepwise process with a rate-limiting leaving group expulsion from the intermediate involving a backside nucleophilic attack with the strongly basic nucleophiles and a frontside attack with the weakly basic nucleophiles. The kinetic results are compared with those of the benzylaminolysis of O,O-diphenyl Z-S-aryl phosphorothioates.

Kinetics and Mechanism of the Pyridinolysis of Aryl Phenyl Isothiocyanophosphate in Acetonitrile

Adhikary, Keshab Kumar,Lee, Hai-Whang,Lee, Ik-Choon Korean Chemical Society 2003 Bulletin of the Korean Chemical Society Vol.24 No.8

The kinetics and mechanism of the pyridinolysis $(XC_5H_4N)$ of Y-aryl phenyl isothiocyanophosphates (1;$(YC_6H_4O)\;(C_6H_5O)$P(=O)NCS) are investigated in acetonitrile at 55.0 ℃. The Hammett plots for substituent (Y) variations in the substrate (log k₂ vs σY) exhibit a convex upward biphasic type with breaks at Y = H. For electron-donating Y groups the Hammett coefficients, ρY, are positive and cross-interaction constant ρXY is negative, while those for electron-withdrawing Y groups ρY values are negative with a positive ρXY. These results are interpreted to indicate mechanistic change at the breakpoint (σY = 0) from a concerted to a stepwise mechanism with rate-limiting expulsion of the $^-NCS$ group from a trigonal bipyramidal pentacoordinated (TBP-5C) intermediate. Biphasic plots of log k₂ vs σX or $pK_a$(X) with steeper slopes for the more basic nucleophiles are obtained suggesting an equatorial nucleophilic attack in contrast to an apical attack for the less basic nucleophiles with smaller magnitude of ρX or βx.

Transition State Variation in the Anilinolysis of O-Aryl Phenyl Phosphonochloridothioates in Acetonitrile

Adhikary, Keshab Kumar,Lumbiny, Bilkis Jahan,Dey, Shuchismita,Lee, Hai-Whang Korean Chemical Society 2011 Bulletin of the Korean Chemical Society Vol.32 No.8

The nucleophilic substitution reactions of Y-O-aryl phenyl phosphonochloridothioates with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are kinetically investigated in acetonitrile at $55.0^{\circ}C$. The deuterium kinetic isotope effects (DKIEs) invariably increase from an extremely large secondary inverse ($k_H/k_D$ = 0.439; min) to a primary normal ($k_H/k_D$ = 1.34; max) as both substituents of nucleophile (X) and substrate (Y) change from electron-donating to electron-withdrawing. These results are opposite to the DKIEs on Y-O-aryl methyl phosphonochloridothioates, and can be rationalized by the gradual transition state (TS) variation from backside to frontside attack. The trigonal bipyramidal pentacoordinate TS is proposed for a backside attack, while the hydrogen-bonded, four-center-type TS is proposed for a frontside attack. The negative values of the cross-interaction constants (${\rho}_{XY(H)}$ = -0.38 for $XC_6H_4NH_2$ and ${\rho}_{XY(D)}$ = -0.29 for $XC_6H_4ND_2$) indicate that the reactions proceed by a concerted $S_N2$ mechanism.