Hydrolysis isothiocyanates

Azoles containing a free NH group react comparatively readily with acyl halides. N-Acyl-pyrazoles, -imidazoles, etc. can be prepared by reaction sequences of either type (66) -> (67) or type (70)->(71) or (72). Such reactions have been carried out with benzoyl halides, sulfonyl halides, isocyanates, isothiocyanates and chloroformates. Reactions occur under Schotten-Baumann conditions or in inert solvents. When two isomeric products could result, only the thermodynamically stable one is usually obtained because the acylation reactions are reversible and the products interconvert readily. Thus benzotriazole forms 1-acyl derivatives (99) which preserve the Kekule resonance of the benzene ring and are therefore more stable than the isomeric 2-acyl derivatives. Acylation of pyrazoles also usually gives the more stable isomer as the sole product (66AHCi6)347). The imidazole-catalyzed hydrolysis of esters can be classified as an electrophilic attack on the multiply bonded imidazole nitrogen. 

Several related derivatives have also been utilized in this type of synthesis. Imino-chloromethanesulfenyl chlorides (184), prepared by the controlled addition of chlorine to isothiocyanates, react with amidines (161) to give 1,2,4-thiadiazolines (185) (71T4117). Chlorocarbonylsulfenyl chloride (186), prepared by the hydrolysis of trichloromethanesulfenyl chloride with sulfuric acid, reacted with ureas, thioureas and guanidines to give 1,2,4-thiadiazolidine derivatives (187) <70AG(E)54, 73CB3391). 

A major advance was devised by Pehr Edrnan (University of Lund, Sweden) that has become the standard method for N-terminal residue analysis. The Edman degradation is based on the chemistry shown in Figure 27.12. A peptide reacts with phenyl isothiocyanate to give a phenylthiocarbamoyl (PTC) derivative, as shown in the first step. This PTC derivative is then treated with an acid in an anhydrous medium (Edrnan used nitrornethane saturated with hydrogen chloride) to cleave the amide bond between the N-terminal anino acid and the remainder of the peptide. No other peptide bonds are cleaved in this step as amide bond hydrolysis requires water. When the PTC derivative is treated with acid in an anhydrous medium, the sulfur atom of the C=S unit acts as... 

The thiono derivatives of tetrahydro-1,3-oxazine became a subject matter of some interest since Kjaer and Jensen discovered that products of enzymatic hydrolysis of Malcolma maritima contain 6-methyl- and 6,6-dimethyl-2-thionotetrahydro-l,3-oxazine (26). The authors proved the identity of these compounds with the products of cyclization of 3-hydroxypropyl-isothiocyanate in an alkaline medium. 

If the acid hydrolysis of 1,3-oxazine derivatives is followed by acting with phenyl-isothiocyanate, thiourea derivatives can be formed. ... 

Allyl isothiocyanate, CHj CH. CH N C S, also known as artificial mustard oil, is the principal constituent of natural oil of mustard. This body results from the hydrolysis of the glucoside sinigrin under the influence of the ferment myrosin, according to the equation—... 

Propose two structures for a tripeptide that gives Leu.. Ala, and Phe on hydrolysis but does not react with phenyl isothiocyanate. 

In a 5-I. round-bottomed flask, equipped with a reflux condenser connected to a gas trap (Note 1), are placed 2 1. (12.r moles) of 20 per cent hydrochloric acid and 500 g. (5.05 moles) of allyl isothiocyanate (Note 2). The mixture is refluxed over a free flame until the upper layer of allyl isothiocyanate has completely disappeared, about fifteen hours being required for the hydrolysis. When the reaction is complete, the solution is -poured into a 3-I. beaker and concentrated on the steam bath until crystals begin to form in the hot solution. This occurs when the volume is approximately 400 cc. (Note 3). 

Allylamine has been prepared from allyl isothiocyanate by hydrolysis with dilute sulfuric 1 or hydrochloric2 acid. 

Related to this process is the hydrolysis of isocyanates or isothiocyanates" where addition of water to the carbon-nitrogen double bond would give an N-substituted carbamic acid (3). Such compounds are unstable and break down to carbon dioxide (or COS in the case of isothiocyanates) and the amine ... 

NASTRUZZI C, CORTESI R, ESPOSITO E, MENEGATTI E, LEONI O, lORI R and PALMIERI S (2000) In vitro antiproliferative activity of isothiocyanates and nitriles generated hy myrosinase-mediated hydrolysis of glucosinolates from seeds of cruciferous vegetables , JAgric Food Chem, 48 3572-5. 

Albin, D. M., Wubben, J. E., and Gabert, V. M., Effect of hydrolysis time on the determination of amino acids in samples of soybean products with ion-exchange chromatography or precolumn derivatization with phenyl isothiocyanate,. Agr. Food Chem., 48, 1684, 2000. 

TRITC is relatively insoluble in water, but it can be dissolved in DMF or DMSO as a concentrated stock solution prior to its addition to an aqueous reaction mixture. The isothiocyanate group is reasonably stable in aqueous solution for short periods, but will degrade by hydrolysis. TRITC also is more stable to photobleaching than FITC (Section 1, this chapter), and its absorption and emission spectra are less sensitive to environmental conditions, such as plT. It is best, however, to use only fresh reagent for modification purposes. Storage should be done under desiccated conditions, protected from light, and at -20°C. 

Some cyclic thioacetals have an A-SE2 hydrolysis mechanism,206 as do some 2-aryl-2-methyl-l,3-dithianes, except for the 4-NO2 derivative, which looks more A2-like.207 In 10 vol% dioxane/aqueous HC104 mixtures, reactive 2-aryl-2-phenyl-l,3-dithianes are believed to have an A-SE2 hydrolysis mechanism, whereas the least reactive ones have an A2 mechanism.130 Isothiocyanates are believed to hydrolyze by a mechanism that involves simultaneous proton transfer to nitrogen and attack of water at carbon in a cyclic transition... 

Figure 13.1 Degradation of glucosinolates. Hydrolysis is catalyzed by myrosinases and gives rise to different degradation products dependent on the structure of the glucosinolate side chain and the hydrolysis conditions. (I) isothiocyanates, the major product at pH >7 (II) nitriles, the major product at pH <4 (ID) thiocyanates, produced from 2-propenyl-, benzyl-, and 4-methylthiobutylglucosinolates (IV) oxazolidine-2-thiones, produced from glucosinolates with P-hydroxylated side chains, (V) epithionitriles, produced in the presence of epithiospecifier proteins.

Amino-2-deoxy aldoses. The behaviour of O-unprotected sugars is exemplified in D-gluco series after basic hydrolysis of the starting 2-benzamidoglycoside followed by buffering the medium with carbon dioxide and treatment with thiophosgene, an intermediate isothiocyanate was obtained.320 However, NMR revealed a temperature-dependent equilibrium of this isothiocyanate with a trans-fused OZT (Scheme 5). 

Both sulfonyl chloride and isothiocyanate will hydrolyze in aqueous conditions therefore, the solutions should be made freshly for each labeling reaction. Absolute ethanol or dimethyl formamide (best grade available, stored in the presence of molecular sieve to remove water) should be used to dissolve the reagent. The hydrolysis reaction is more pronounced in dilute protein solution and can be minimized by using a more concentrated protein solution. Caution DMSO should not be used with sulfonyl chlorides, because it reacts with them. 

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