107-16-4

The equilibrium constant, Kan(H2CO), for the formation of α-aminoacetonitrile from formaldehyde, ammonia and hydrogen cyanide was evaluated at 25 deg C.A first estimation of Kan(H2CO) was obtained from extrathermodynamic relationships of the type log K' vs Σ?*.The final value was then obtained from a comparison of the experimental and calculated pH dependences of α-hydroxy- and α-aminoacetonitrile concentrations.From these results, it appears that, after equilibrium, the ratio between the concentrations of the two precursors glycine and hydroxyethanoic acid, is a linear function of the concentration of free ammonia, i.e. /=21 at 25 deg C.

A chemoenzymatic process for the production of high-purity glycolic acid has been demonstrated, starting with the reaction of formaldehyde and hydrogen cyanide to produce glycolonitrile in > 99 % yield and purity. The resulting aqueous glycolonitrile was used without further purification in a subsequent biocatalytic conversion of glycolonitrile to ammonium glycolate. A high-activity biocatalyst based on an Acidovorax facilis 72W nitrilase was developed, where protein engineering and optimized protein expression in an E. coli transformant host were used to improve microbial nitrilase specific activity by 33-fold compared to the wild-type strain. A biocatalyst productivity of > 1000 g glycolic acid/g dry cell weight was achieved using a glutaraldehyde/ polyethylenimine cross-linked carrageenan-immobilized E. coli MG1655 transformant expressing the A. facilis 72W nitrilase mutant, where 3.2M ammonium glycolate was produced in consecutive batch reactions with biocatalyst recycle, or in a continuous stirred-tank reactor. Direct conversion of the unpurified ammonium glycolate product solution to high-purity aqueous glycolic acid was accomplished by fixed-bed ion exchange over a strong acid cation resin.

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Reactions of oxygen atoms and acetonitrile have been investigated in solid argon at 14-17 K.Primary photoproducts include hydroxyacetonitrile (HOCH2CN) and acetonitrile N-oxide (CH3CNO).Hydroxyacetonitrile forms hydrogen-bonded complexes with acetonitrile and acetonitrile N-oxide as the secondary products.Acetonitrile N-oxide is suggested to be formed by a simple bimolecular addition reaction of atomic oxygen with the nitrile nitrogen.The participation of O(1D) atoms is considered to increase the yield of hydroxyacetonitrile as compared to acetonitrile N-oxide via H-atom abstraction or insertion reactions.The spectral characteristics of hydroxyacetonitrile, acetonitrile N-oxide, and hydrogen-bonded hydroxyacetonitrile-acetonitrile complex isolated in argon matrices are given.

Available data on the kinetics of oxidations of amino-acids by sodium N-chloro toluene-p-sulphonamide (chloramine T) in acid and alkaline media have been critically examined.General mechanisms have been proposed for both acid and alkaline medium oxidations.The oxidation process in acid media has been shown to proceed via two paths, one involving the direct interaction of N-chlorotoluene-p-sulphonamide (RNHCl) with the neutral amino-acid in a slow step leading to the formation of the monochloroamino-acid which subsequently interacts with another molecule of RNHCl, in a fast step, to give the NN-dichloroamino-acid which in turn undergoes molecular rearrangement and elimination to yield the products, and the other involving the interaction of Cl2 or H2OCl(1+), produced from the disproportionation of RNHCl in the presence or absence of Cl(1-), with the substrate to give the products.In the alkaline medium mechanisms involving the interaction of RNHCl, HOCl, RNCl(1-), and OCl(1-) with the substrate are proposed.The mechanisms proposed and the derived rate lows are consistent with the observed kinetics.The rate constants predicted by the derived rate laws, as the concentrations of substrate and Cl(1-) ion change, are in excellent agreement with the observed rate constants thus further verifying the rate laws and hence the proposed mechanisms.

In cyanation reactions, the cyanide source is often directly added to the reaction mixture, which restricts the choice of conditions. The spatial separation of cyanide release and consumption offers higher flexibility instead. Such a setting was used for the cyanation of iminium ions with a variety of different easy-to-handle HCN sources such as hexacyanoferrate, acetonitrile or α-amino acids. The latter substrates were first converted to their corresponding nitriles through oxidative decarboxylation. While glycine directly furnishes HCN in the oxidation step, the aliphatic nitriles derived from α-substituted amino acids can be further converted into the corresponding cyanohydrins in an oxidative C-H functionalization. Mn(OAc)2 was found to catalyze the efficient release of HCN from these cyanohydrins or from acetone cyanohydrin under acidic conditions and, in combination with the two previous transformations, permits the use of protein biomass as a non-toxic source of HCN.

The oxidative decarboxylation of amino acids to nitriles was achieved in aqueous solution by in situ halide oxidation using catalytic amounts of tungstate exchanged on a [Ni,Al] layered double hydroxide (LDH), NH4Br, and H2O2 as the terminal oxidant. Both halide oxidation and oxidative decarboxylation were facilitated by proximity effects between the reactants and the LDH catalyst. A wide range of amino acids was converted with high yields, often > 90%. The nitrile selectivity was excellent, and the system is compatible with amide, alcohol, and in particular carboxylic acid, amine, and guanidine functional groups after appropriate neutralization. This heterogeneous catalytic system was applied successfully to convert a pro-tein-rich byproduct from the starch industry into useful biobased N-containing chemicals.

Diethyl bromomalonate and bromoacetonitrile, respectively, react with trimethylammonium acetic acid betaine in ethanol to give diethyl tartronate and glycolic acid nitrile, respectively.By analogy, ethyl α-chloroacetonate and ethyl bromopyruvate yield the respective hydroxy derivatives which were identified by their osazones 2 and 3.Under the same experimental conditions, mesoxalic acid and its dimethyl ester, respectively, are formed from dibromo malonic acid and its dimethyl ester and were characterized by their known hydrazones 8 and 9. - Keywords: Trimethylammonium acetic acid betaine; Diethyl tartronate; 1-Carbethoxy-2-methyl-(2,4-dinitrophenyl) osazone; 1-Carbetoxy-(2,4-dinitrophenyl) osazone; Glycolic acid nitrile.

Provided herein are compounds, compositions and methods for inhibition of herpesviruses. In some cases, the subject compounds inhibit a herpesvirus in a cell. Also provided are compounds, compositions and methods for treating a herpesvirus in an individual. In some cases, the methods include administering to an individual a therapeutically effective amount of a subject compound to treat the individual for the herpesvirus. In certain embodiments, the compounds disclosed herein are cytomegalovirus (CMV) inhibitors. In certain embodiments, the compounds disclosed herein are human cytomegalovirus (CMV) inhibitors.

The invention discloses a process for synthesizing ethylenediamine-N-N'-disodium oxalic acid, and belongs to the field of technologies for synthesizing chemical compounds. The process includes carrying out reaction on glycolonitrile aqueous solution and ethylenediamine to obtain an intermediate ethylenediamine-N-N'-diacetonitrile; carrying out alkaline hydrolysis on the intermediate and dehydrating and drying the intermediate to obtain the ethylenediamine-N-N'-disodium oxalic acid. The intermediate and liquid caustic soda are mixed with each other to obtain mixtures when alkaline hydrolysis is carried out on the intermediate, the mixtures are heated until the temperature of the mixtures reaches 60-65 DEG C at first, then heat is preserved for 2-2.5 h, the mixtures are further heated until the temperature of the mixtures reaches 110-115 DEG C, and reflex heat preservation is carried out for 2-2.5 h to obtain alkaline hydrolysis liquid. The process has the advantages that the process is environmentally friendly, ammonia gas which is a byproduct can be absorbed by water to obtain ammonia water, and accordingly generation of waste gas, wastewater and industrial residues can be prevented; the alkaline hydrolysis temperatures are controlled, accordingly, generation of impurities such as disodium ethylenediamine nitrilotriacetic acid, ethylenediamine-sodium acetate and ethylenediamine tetraacetic acid disodium salt can be effectively controlled, and the ethylenediamine-N-N'-disodium oxalic acid which is a product is high in purity.

The invention relates to a preparation method of 2-hydroxy acid ester and belongs to the technical field of organic synthesis. According to the preparation method of 2-hydroxy acid ester, 2-hydroxy alkyl cyanogens is taken as a raw material to be added to a reaction solution formed by hydrogen chloride, alcohol and water, and after reaction, 2-hydroxy acid ester is obtained. According to the preparation method of 2-hydroxy acid ester, use of a large amount of nonpolar solvent is not needed, and a target product can be obtained by a one-pot method, thus lowering production cost, improving production efficiency and the purify of the target product, and having energy-saving and environment-friendly effects.

The invention relates to a preparation and pre-use treatment method for glycolonitrile with cyanide-containing tail gas as the raw material. According to the method, the cyanide-containing tail gas is introduced into multiple stages of reaction stills containing formaldehyde and a catalyst to be directly subjected to an addition reaction, and a glycolonitrile product with a certain concentration is obtained; after material transferring, the glycolonitrile product is stored under the effect of a stabilizer for use, and before use, the pH is regulated with base or weak base till the glycolonitrile product is neutral. The catalyst is one of basic compounds including Na2SO3, Na2CO3, NaHCO3 and NaOH, the mass concentration of formaldehyde is 35%-37%, the mol ratio of formaldehyde to the catalyst is 1:(0.001-0.05), and the reaction temperature is 5-20 DEG C. According to the method, HCN in industrial waste gas of a steroid drug is chemically absorbed through formaldehyde, the catalyst and the stabilizer, glycolonitrile is generated through the reaction and serves as a raw material for biological preparation of glycollic acid, and therefore the cyanide-containing tail gas is fully absorbed and utilized and prevented from being directly exhausted to the atmosphere and polluting the environment.

PROBLEM TO BE SOLVED: efficiently in a relatively mild conditions aminonitrile compd. and to provide a manufacturing method. SOLUTION: vanadium, phosphorus, and silicon-containing aluminum oxide in the presence of a catalyst, ammonia and methanol and oxygen containing gas phase catalytic reaction cyamic obtd. reaction gas, contained in the reaction gas and including cyamic cyamic compound having a double bond in the molecule and and by the reaction of a nitrile compound. Selected drawing: no (by machine translation)

Disclosed is a process for producing a cyanohydrin, the process comprising reacting a carbonyl compound with hydrocyanic acid in a buffer solution with a pH less than 7 to obtain the cyanohydrin.

Bromide-assisted electrochemical decarboxylation efficiently produces valuable nitriles in high yields from a wide range of naturally occurring amino acids in a single step. Bromide salts are used as both redox mediators and supporting electrolytes in a simple one-compartment setup. As demonstrated for lysine, the selectivity of the decarboxylation can be tuned towards nitriles, amines or amides. An electrochemical system is developed that allows the selective decarboxylation of a wide range of amino acids. Valuable nitriles are obtained in high yields in a single step by using bromide salts as both redox mediators and supporting electrolytes. The product selectivity of lysine can be tuned towards nitriles, amines, or amides.

A process for preparing EDDN and/or EDMN by conversion of FA, HCN and EDA, the reaction being effected in the presence of water, and, after the conversion, water being depleted from the reaction mixture in a distillation column, which comprises performing the distillation in the presence of an organic solvent which has a boiling point between water and EDDN and/or EDMN at the distillation pressure existing in the column or which forms a low-boiling azeotrope with water.

A process for reacting formaldehyde cyanohydrin (FACH) with ethylenediamine (EDA) in a reactor with limited backmixing at a temperature in the range from 20 to 120° C., wherein the residence time in the reactor is 300 seconds or less.

In one aspect, the invention relates to substituted lH-benzo[d][l,2,3]triazol-l-ol analgoues, derivatives thereof, and related compound; synthetic methods for making the compounds; pharmaceutical compositions comprising the compounds; and methods of treating disorders, e.g. various tumors and cancers, associated with β-catenin/Tcf protein- protein interaction dysfunction using the compounds and compositions. This abstract is intended as a scanning tool for purposes of searching in the particular art and is not intended to be limiting of the present invention.

1-Methylhydantion is a compound, which was isolated from Oviductus Ranae for the first time. In our study, we found that it showed good antitussive and anti-inflammatory activity. It is also the first report which illustrates the antitussive activity of hydantion derivative. A series of hydantion derivatives were synthesized and evaluated for their anti-inflammatory and antitussive activity in vivo. The pharmacological tests showed that compounds 7a, 7c and 7d have good anti-inflammatory and antitussive activity compared to Ibuprofen and codeine. Compound 7a in particular showed two-fold stronger anti-inflammatory activity than Ibuprofen.

A process for preparation of the compound (I) and salts thereof is provided. The process comprises reacting an alkali cyanide and paraformaldehyde to form a slurry of glycolonitrile followed by neutralizing, mixing the neutralized slurry containing glycolonitrile with an alkali ethoxide and an cyanoacetate to obtain the alkali salt of compound (I), and neutralizing the alkali salt of compound (I) to obtain the compound (I), wherein R represents a straight or branched chain alkyl having C1-C18 carbon atoms.

The invention relates to a process for preparing tetraethylenepentamine (TEPA) by hydrogenation of diethylenetriaminediacetonitrile (DETDN) over a catalyst. If appropriate, DETDN can also be present as a constituent of an amino nitrile mixture which additionally comprises diethylenetriaminemonoacetonitrile (DETMN).

The invention relates to a process for preparing triethylenetetramine (TETA), which comprises hydrogenating ethylenediaminediacetonitrile (EDDN) in the presence of a catalyst and a solvent.

The invention relates to a process for preparing an ethylene amine mixture, which comprises hydrogenating an amino nitrile mixture comprising at least two α-amino nitriles in an amount of at least 5% by weight in each case in the presence of a catalyst and, if appropriate, a solvent.

The invention relates to a process for preparing triethylenetetramine (TETA), which, comprises the following steps: a) reaction of ethylenediamine (EDA) with formaldehyde and hydrocyanic acid (HCN) in a molar ratio of EDA to formaldehyde to HCN of from 1:1.5:1.5 to 1:2:2 to give ethylenediaminediacetonitrile (EDDN),b) hydrogenation of the EDDN obtained in step a) in the presence of a catalyst and a solvent.

The preparation of protected 1-aminocyclopropanecarboxylic acid was performed from readily available and inexpensive starting materials, using titanium-catalyzed cyclopropanation as the key step. As an extension of this methodology, a diastereoselective synthesis of the cis-2-vinyl-substituted analogue is presented. Georg Thieme Verlag Stuttgart.

Disclosed is a method for producing glycolic acid which has a simple production process and purification process while consuming less energy. This method comprises a first step wherein glycolonitrile is obtained from formaldehyde and prussic acid, and a second step wherein glycolic acid is directly obtained by hydrolyzing the glycolonitrile or glycolic acid is obtained via a glycolate. In this method, the yield of glycolic acid, activity of glycolic acid production, and accumulated concentration of glycolic acid are improved by continuously performing the first step and the second step as a single step, or storing the glycolonitrile obtained in the first step at a pH of 4 or less and performing the hydrolysis in the second step at a pH of 5-9, and whereby the purity and quality of the thus-obtained glycolic acid are improved.

The invention relates to compounds having an anti-parasitic, in particular antimalarial activity, characterized in that they correspond to general formula (I) Applications in particular as compounds with anti-parasitic activity.

A substantially solid composition, the composition having therein a compound with the structure of Formula (I) wherein A, R1, R2, R3, Y and Z are as defined in the disclosure.

The second-order rate constants k2 (M-1 s-1) for the alkaline hydrolysis of substituted alkyl benzoates, C6H5CO(O)R (R = CH3, CH2Cl, CH2CN, CH2C≡CH, CH2C6H5, CH2CH2Cl, CH2CH2OCH3), were measured in aqueous 2.25 M n-Bu4NBr and in 80% (v/v) DMSO solution at several temperatures. The log k values were analyzed using the equation log k = log k0 + ρσ + δEsB. The EsB scale has been proposed for the steric effect of alkyl substituents in the alkyl part of esters: EsB = (log kR - log kCH(3))H+, where k is the rate constant for the acidic hydrolysis of substituted alkyl benzoates or acetates in water. As polar substituent parameters, both Taft σ* and σI constants were used. The dual parameter treatments of the log k values with σ and EsB constants gave excellent correlations (R = 0.997). For 2.25 M n-Bu4NBr, 80% (v/v) DMSO and pure water at 25 °C, calculated susceptibilities to the inductive effect of alkyl substituents ρ* were found to be 2.07, 2.21 and 1.64, respectively. The corresponding ρI values were 4.64, 4.94 and 3.64. The dependence of ρI on solvent and temperature in the alkaline hydrolysis of substituted alkyl benzoates was similar to that observed earlier for meta- and para-substituents in the alkaline hydrolysis of substituted phenyl benzoates and tosylates. The substituent dependence of the activation energy, E, was found to be completely caused by the polar effect. Susceptibility to steric effect in the alkaline hydrolysis of alkyl benzoates (δ ≈ 1) appeared to be independent of the solvent and temperature. Copyright

Kinetics of oxidative decarhoxylation of amino acids by chloramine-T in the presence of chloride have been studied in aqueous perchloric acid over a wide range. The rate-[H+] plots show nearly bell-shaped profiles in the presence of added chloride. The rate-dependence in [CAT] changes from second order to first order as [H+] and [Cl-] are varied. The reactions generally show fractional order kinetics in [AA] and inverse dependence in [H+] except in the acid range 0.05-0.20 mol dm-3. Mechanisms consistent with the observed results are discussed. The rate-limiting steps have been identified and constants of these steps calculated. Activation parameters corresponding to these steps have also been computed. Validity of Taft equation has been tested. The study establishes the significant role of chloride in chloramine-T oxidations in acid medium. The chloride effect is more pronounced at high acid concentrations.

Nitric oxide synthase (NOS) catalyzes the conversion of L-arginine to L- citrulline and nitric oxide. N5-(1-iminoethyl)-L-ornithine (L-NIO, 5) is a natural product known to inactivate NOS, but the mechanism of inactivation is unknown. Upon incubation of iNOS with L-NIO a type I binding difference spectrum is observed, indicating that binding at the substrate binding site occurs. L-NIO is shown to be a time-dependent, concentration-dependent, and NADPH-dependent irreversible inhibitor of iNOS with K(I) and k(inact) values of 13.7 ± 1.6 μM and 0.073 ± 0.003 min-1, respectively. During inactivation the heme chromophore is partially lost (Figure 1); HPLC shows that the loss corresponds to about 50% of the heine. Inclusion of catalase during incubation does not prevent heine loss. N5-(1-Imino-2-[14C]ethyl)- L-ornithine (11) inactivates iNOS, but upon dialysis or gel filtration, no radioactivity remains bound to the protein or to a cofactor. The only radioactive product detected after enzyme inactivation is N(ω)-hydroxy-L- NIO (12); no C(ω)-hydroxy-L-NIO (13) or N(δ)-acetyl-L-ornithine (14) is observed (Figure 2). The amount of 12 produced during the inactivation process is 7.7 ± 0.2 equiv per inactivation event. Incubations of 12 with iNOS show time-, concentration-, and NADPH-dependent inactivation that is not reversible upon dilution into the assay solution. Incubations that include an excess of L-arginine or with substitution of NADP+ for NADPH result in no significant loss of enzyme activity. The K(I) and k(inact) values for 12 are 830 ± 160 μM and 0.0073 ± 0.0007 min-1, respectively. The magnitude of these kinetic constants (compared with those of 5) suggest that 12 is not an intermediate of L-NIO inactivation of iNOS. Compound 12 also is a substrate for iNOS, exhibiting saturation kinetics with K(m) and k(cat) values of 800 ± 85 μM and 2.22 min-1, respectively; the product is shown to be N(δ)- acetyl-L-ornithine (14) (Figure 3). The k(cat) and k(inact) values for 12 can be compared directly to give a partition ratio (k(cat)/k(inact)) for inactivation of 304; i.e., there are 304 turnovers to give NO per inactivation event. This high partition ratio further supports the notion that 12 is not involved in L-NIO inactivation of iNOS. C(ω)-Hydroxy-L-NIO (13) is not an inactivator of iNOS. These results suggest that L-NIO inactivation occurs after an oxidation step (NADPH is required for inactivation) but prior to a hydroxylation step (12 and 13 are not involved). Inactivation of iNOS by N5-(1-imino-2-[2H3]-ethyl)-L-ornithine (15) exhibits 3 kinetic isotope effect (H)k(inact)/(D)k(inact) of 1.35 ± 0.08 and on (H)(k(inact)/k(I)/(D)-(k(inact)/K(I) of 1.51 ± 0.3, suggesting that the methyl C-H bond is cleaved in a partially rate-determining step prior to hydroxylation, and that leads to inactivation. A new NADPH-dependent 400 nm peak in the HPLC of L-NIO-inactivated iNOS is produced (Figure 4). LC- electrospray mass spectrometry (Figure 5) demonstrates the m/z of the new metabolite to be 583, which is shown to correspond to biliverdin (23) (Figures 6 and 7). Two possible mechanisms for the formation of biliverdin during inactivation are proposed (Schemes 10 and 11). When 14 is incubated with iNOS, time-, concentration-, and NADPH-dependent loss of enzyme activity is observed (K(I) and k(inact) values are 490 mM and 0.24 min-1, respectively); iNOS inactivation by 14 can be prevented by inclusion of L- arginine, but not D-arginine, in the inactivation mixtures, suggesting that the inactivator acts at the arginine binding site. However, 14 is not produced from L-NIO (Figure 2) and, therefore, is not involved in L-NIO inactivation.

The D-manno-configured N-anisylated β-lactam 40, the β-lactam carboxylic acids 4 and 43, and the corresponding phosphonic-acid isosters 49 and 50 have been synthesized from D-glucose in 8-10 steps, respectively. None of these compounds exhibited a significant inhibitory activity in vitro against the sialidases of Vibrio cholerae, Salmonella typhimurium, Influenza A (N9), and Influenza B virus. Cycloaddition of the in situ generated imines derived from the D-erythroses 6, 16, and 17 with the ketene from mesyloxyacetyl chloride (20) gave the 2-mesyloxy-D-hexono-1,3-lactams 25, 27a/b, 28a/b/c, and 29 in 23, 69, 57, and 90% yield, respectively (Scheme 3). Transformation of 27a/b and 29 (> 85%) to the corresponding azides, followed by oxidative N-deprotection, gave 30a/b (45%) and 34 (80%). Subsequent alkylation of the ring N-atom in 31a with benzyl bromoacetate and dibenzyl (triflyloxymethyl)phosphonate 46 gave the carboxylate 41 (77%) and the phosphonate 47 (55%; Schemes 4 and 5). Hydrogenolysis of 41 gave the β- lactam amino acid 43, besides its hydrolysis product 44. Reductive N- acylation of the azido group in 41 (93%), followed by hydrogenolytic debenzylation, yielded the 2-trifluoroacetamido N-(carboxymethyl)-β-lactam 4 (56%). Similarly, 47 gave the 2-trifluoroacetamide 48 (89%), and hence, the 2-amino-N-(phosphonoylmethyl)-β-lactams 49 (40%) and 50, resulting from deacylation of 49 (14%). Aminolysis and carbamoylation of the protected β- lactams 31a and 35 led to the 2,3-diamino-2,3-dideoxy-D-mannonamides 51 and 53, respectively (Scheme 6).

The invention relates to novel bis-benzimidazole compounds which have the ability to bind to the minor groove of DNA and to alkylate DNA, to methods of preparing the compounds, and the use of the compounds in the treatement of neoplastic disease.

Oxiranecarbonitrile in basic aqueous solution at room temperature reacts regioselectively with inorganic phosphate to give the cyanohydrin of 2-oxoethyl phosphate ('glycolaldehyde phosphate'), a source of (the hydrate of) the free aldehyde, preferably in the presence of formaldehyde.In aqueous phosphate solution buffered to nearly neutral pH, oxiranecarbonitrile produces the phosphodiester of glycolaldehyde as its bis-cyanohydrin in good yield.In contrast to mono- and dialkylation, trialkylation of phosphate with oxiranecarbonitrile is difficult, and the triester derivative is highly sensitive to hydrolysis.Glycolaldehyde phosphate per se is of prebiotic interest, since it had been shown to aldomerize in basic aqueous solution regioselectively to rac-hexose 2,4,6-triphosphates and- in the presence of formaldehyde - mainly to rac-pentose 2,4-diphosphates with, under appropriate conditions, rac-ribose 2,4-diphosphate as the major reaction product.However, the question as to whether oxiranecarbonitrile itself has the potential of having been a prebiological natural constituent remains unanswered.Backbone structures of hexopyranosyl-oligonucleotides with phosphodiester linkages specifically between the positions 6'->4',6'->2', or 4'->2' of the sugar residues can formally be derived via the (hypothetical) aldomerization pathway, a combinatorial intermolecular aldomerization of glycolaldehyde phosphate and bis(glycolaldehyde)phosphodiester in a 1:1 ratio.The constitutional relationships revealed by this synthetic analysis has played a decisive role as a selection criterion in the pursuit of our experimental studies toward a chemical etiology of the natural nucleic acids' structure.The Discussion in this paper delineates how the analysis contributed to the conception of the structure of p-RNA.The English Footnotes to Schemes 1-11 provi de an extension of this summary.

Pharmaceutically useful nitrogen containing cyclic oxime and amine substituted compounds of the following general Formulas I, II and III are disclosed: STR1 Specifically the compounds are azabicyclo [2. 2.1] omimes, azabicyclo [2.2.2] oximes, azabicyclo [2.2.1] amines, azabicyclo [2.2.2] amines, azabicyclo [3.2.1] oximes and amine containing heterocyclic oximes wherein the heterocyclic ring contains from 4 to 5 [3 to 7] carbon atoms.

Kinetics of oxidation of several α-amino acids (AA) by dichloramine-B have been studied in aqueous acetic acid in presence of perchloric acid.The rates of oxidations shown two ranges in with zero and inverse fractional order in +>.The reactions generally show second order kinetics in in both the acid ranges and fractional order in , although the magnitudes of the fractional orders are different.Oxidations of some amino acids have also been investigated in the presence of sodium acetate.Under these conditions the rates are independent of .The results indicate the participation of acetate ions in the reaction in addition to the secondary salt effect.Increase in acetic acid composition of the solvent decreases the rates of oxidations.Two-pathway mechanisms consistent with observed results have been considered.The coefficients of the rate-limiting steps at different temperatures and the corresponding activation parameters are also computed.

The effects of borate buffers on the pseudo first-order rate constants for the hydration of hydroxyacetonitrile (1) have been examined on the pH range 8.6-10.3 at 80 deg C.Kinetic results are compatible with a reaction of the neutral cyanohydrin with borate anion or any other kinetically equivalent mechanism.Cyanohydrin structural effects are consistent with a pathway involving the pre-equilibrium formation of a borate-substrate adduct, followed by a rate-determining intramolecular nucleophilic attack on the nitrile group.Phenylboronate ion has also been shown to act as an efficient catalyst, but it was not possible to detect any influence due to disubstituted borate ions.Thus, it is suggested that a trigonal borate anion actually acts as a nucleophile.

In a novel approach starting from O-trimethylsilyl protected or unprotected cyanohydrins and oxalyl chloride or bromide, a series of unknown 6-substituted 3,5-dihalo-2H-1,4-oxazin-2-ones were prepared.The method was shown to be efficient for various types of cyanohydrins; however cyclization was not obtained with cyanohydrins containing bulky substituents, electron-rich aryl or heteroaryl groups.A mechanism is proposed.

The kinetics of oxidation of amino acids by bromamine-T (BAT) have been investigated both in the presence and absence of formaldehyde in perchloric acid medium.The reaction is first order in , zero order in both and and fractional order in in the presence of formaldehyde, and first order each in , and and inverse first order in in the absence of formaldehyde.Addition of p-toluenesulphonamide or variation in ionic strength of the medium does not have any significant effect on the rate, but the decrease in dielecrtic constant of the reaction medium decreases the rate.Activation parameters have been computed from the Arrhenius plots and mechanisms in conformity with the observed kinetics have been suggested and related rate laws deduced.The oxidation process in the presence of formaldehyde proceeds via two pathways.

Kinetics of oxidation of glycine, serine, alanine and leucine by bromamine-T (BAT) have been studied in sulphuric acid (0.05 to 0.15 mol dm-3) at 35 deg C.The reaction shows a first order dependence each in 0, 0 and inverse first order in .Added sulphate ions increase the rate while bisulphate ions retard the reaction.The rate of oxidation increases in the order: leucine > alanine > serine > glycine.The mechanism assumes the interaction of zwitterion of substrate with monobromamine-T in the rate-limiting step.

The kinetics of oxidation of amino acids in aqueous medium were reinvestigated.The rate of oxidation follows second order with respect to chloramine-T (CAT) and an inverse dependence on (RNH2).At constant the rate of the reaction can be represented as (in the absence of chloride ion) .A linear relationship exists between pK1 and the rate constants.This shows the electrophilic attack of the oxidant at the carboxylato group of the amino acid.The effect of chloride ion on kobsd is catalytic.The mechanisms of the reactions are discussed in terms of the kinetic results.

Novel phenoxyphenoxyalkyl-, phenoxyphenylthioalkyl- or phenoxyphenylsulfonylalkyl-substituted phosphinates and phosphonates, related compounds, synthesis thereof, intermediates therefor, and the use of said novel compounds for the control of weeds.

Novel phenoxyphenoxyalkyl-, phenoxyphenylthioalkyl- or phenoxyphenylsulfonylalkyl-substituted phosphinates and phosphonates, related compounds, synthesis thereof, intermediates therefor, and the use of said novel compounds for the control of weeds.