Selective synthetic routes to sterically hindered unsymmetrical diaryl ketones via arylstannanes

Bulky arylstannanes and bulky aroyl chlorides are good reaction partners for the synthesis of two-, three-, and even four-ortho-substituted benzophenones, in good to excellent isolated yields (47-91%). Three simple and direct routes, with differential advantages, are proposed: (i) a catalyst-free protocol, in o-dichlorobenzene (ODCB) at 180 °C; (ii) a room temperature protocol, using AlCl(3) (0.5 equiv), in dichloromethane (DCM); and (iii) a solvent-free, indium-promoted procedure. A radical mechanism is proposed for the indium-mediated reactions.     

Glued trees algorithm under phase damping

We study the behaviour of the glued trees algorithm described by Childs et al. in [1] under decoherence. We consider a discrete time reformulation of the continuous time quantum walk protocol and apply a phase damping channel to the coin state, investigating the effect of such a mechanism on the probability of the walker appearing on the target vertex of the graph. We pay particular attention to any potential advantage coming from the use of weak decoherence for the spreading of the walk across the glued trees graph.     

Preparation of 5-amino-7(6H)-furazano[3,4-d]pyrimidinone an analog of pterin

5-Aminofurazano[3,4-d]pyrimidines carrying a variety of substituents at position 7 suffer ring cleavage by either acid or base to give 4-guanidino-3-furazancarboxylic acid ($\text{6}$), the esters of which can be recyclised to give the pterin analog 5-amino-7(6H)-furazano[3,4-d]pyrimidinone (9). The pyrimidine ring of (9) is cleaved by hydrolysis, and the furazan ring by hydrogenolysis.     

The expected norm of random polynomials

The results of this paper concern the expected norm of random polynomials on the boundary of the unit disc (equivalently of random trigonometric polynomials on the interval ). Specifically, for a random polynomial

let

Assume the random variables , are independent and identically distributed, have mean 0, variance equal to 1 and, if 2$">, a finite moment . Then

and

as .

In particular if the polynomials in question have coefficients in the set (a much studied class of polynomials), then we can compute the expected norms of the polynomials and their derivatives

and

This complements results of Fielding in the case, Newman and Byrnes in the case, and Littlewood et al. in the case.

     

The determination of iodide in the presence of other halides by enzymatic enthalpimetry

Iodide in the range 0.7–9.2 mg can be determined rapidly in the presence of other halides by means of its peroxidase-catalysed oxidation with hydrogen peroxide; the relative standard deviations are 0.3–2%.     

The enthalpimetric determination of the michaelis constant of the α-chymotrypsin-catalysed hydrolysis of n-acetyl-l-tyrosine ethyl ester based on the integrated michaelis—menten equation

An enthalpimetric method is discussed for the determination of the Michaelis constant (K_m )for the α-chymotrypsin-catalysed hydrolysis of N-acetyl-L-tyrosine ethyl ester (ATEE). The integrated form of the Michaelis—Menten equation is used to achieve a graphical determination of K_m in a single experiment (s_r = 7.6%). The inhibitory effect of ethanol is briefly described.     

Photostimulated reactions of vinyl phosphate esters with triorganostannides. evidence for an SRN1 vinylic mechanism

Ketones are converted into vinyl diethyl phosphate esters (VinDEP), which under photostimulation reacted with sodium trimethylstannide (1) or sodium triphenylstannide (2) in liquid ammonia affording vinylstannanes via a vinylic S(RN)1 mechanism. Thus, (1-phenylvinyl)DEP (3), (3,4-dihydro-1-naphthyl)DEP (7), (3,4-dihydro-2-naphthyl)DEP (9), (E)-(1,2-diphenylvinyl)DEP (12), (E/Z)-(1-methyl-2-phenylvinyl)DEP (14) and (E)-(1-phenyl-2-methylvinyl)DEP (16) react with 1 and 2, under photostimulation, leading to the corresponding substitution products in good to excellent yields (45-89%). On the other hand, there is no reaction between (1-cyclohexenyl)DEP (5) or (1-benzylvinyl)DEP (18) with either 1 or 2, under similar conditions. These reactions appear to be strongly dependent on structural features of the vinyl phosphate since only conjugated vinyl phosphates afforded substitution products. These substitution reactions are completely regioselective and stereoconvergent. It seems to be the first example of a vinylic S(RN)1 process involving organotin anions as nucleophiles.     

Synthesis of substituted furo[3,2-e][1,2,4]triazolo[4,3-c]pyrimidines and furo[3,2-e]tetrazolo[1,5-c]pyrimidines

A series of substituted furo[3,2-e][1,2,4]triazolo[4,3-c]pyrimidines and furo[3,2-e]tetrazolo[1,5-c]pyrimidines were obtained from reactions of substituted 2-dimemylamino-4-hydrazmofuro[2,3-d]pyrimidines with orthoesters or sodium nitrite in acetic acid, respectively.