Derivatives hydrazones

Hydroxybenzaldehyde has extensive use as an intermediate in the synthesis of a variety of agricultural chemicals. Halogenation of Nhydroxybenzaldehyde, followed by conversion to the oxime, and subsequent dehydration results in the formation of 3,5-dihalo-4-hydroxybenzonitrile (2). Both the dibromo- and dhodo-compounds are commercially important contact herbicides, hromoxynil [1689-84-5] (2) where X = Br, and ioxynil [1689-83-4]( where X = I respectively (74). Several hydrazone derivatives have also been shown to be active herbicides (70). 

Some advantages of this reaction are high yield if the tosylate is in a sterically accessible position excellent isotopic purity of the product (usually higher than-95%) and perhaps most important, access to stereospecifically labeled methylene derivatives. For example, deuteride displacement of 3j -tosylates (183) yields the corresponding Sa-d derivative (185) in 96-98% isotopic purity. Application of this method to the labeled sulfonate (184), obtained. by lithium aluminum deuteride reduction of a 3-ketone precursor (see section HI-A) followed by tosylation, provides an excellent synthesis of 3,3-d2 labeled steroids (186) without isotopic scrambling at the adjacent positions. The only other method which provides products of comparable isotopic purity at this position is the reduction of the tosyl-hydrazone derivative of 3-keto steroids (section IV-B). 

The Hurd-Mori 1,2,3-thiadiazole synthesis is the reaction of thionyl chloride with the N-acylated or tosylated hydrazone derivatives 1 to provide the 1,2,3-thiadiazole 4 in one simple step. ... 

DCCI reacts with hydrazone derivatives or with the thiourea 83 to give nitrogen ylides such as 84 and hence by protonation 3-aminotriazolopyridines (88CC506, 93JCS(P1)705). A solution of iodine in pyridine reacts with propional... 

The phosgene can be replaced by methyl or ethyl chloroformate the resulting hydrazone derivatives 7 or 8 readily cyclize to benzotriazepinones (Method C). The products are often accompanied by a quinazolinone.354... 

Methyl or ethyl chloroformate (70 mmol) was added dropwise to a stirred solution of a hydrazone derivative (60 mmol) of 2-amino-5-chlorobcnzophenone in a mixture of CIICI, (200 mL) and pyridine (15 mL) at 10 C. The mixture was left overnight and treated with a further amount of the alkyl chloroformate (40 mmol) and stirred at 20 C for 2 h. If /V-aryl-substituted hydrazones were used, the mixture was refluxed for 3-6 h. The mixture was poured into ice-water and the organic layer was washed successively with H2Oand 10% aq NaH0O3, dried (MgSO ) and evaporated in vacuo to yield 7 or 8 or a mixture of the two. 

Coupling of 2-diazoimidazole 445 with meldrum s acid occurred instantaneously to give hydrazone derivative 446. Cyclization and decarboxylation could be carried out in one pot by heating in acetic acid to afford (88JOC887) imidazotriazine 447, which on further heating gave 448. Meth-ylation of 448 under basic conditions takes place exclusively on N-l and N-2. In the absence of base, a complex mixture may be obtained (Scheme 96). 

Cyclization of the hydrazone derivatives of 4-benzoyl[ 1,2,3]triazole 695 by reaction with one carbon inserting agent such as an orthoester, an aldehyde, a ketone, or a phosgene afforded triazolotriazine 696 or 697 (88JHC743). The newly created C—N bond displays particular sensitivity due to the electron-attracting effect of the triazole ring (Scheme 147). 

S)- and (+ )-(7 )-l-Amino-2-(methoxymethyl)pyrrolidine- (SAMP and RAMP)-hydrazones derived from methyl ketones and chiral hydrazines are metalated regioselectively at the methyl... 

Metalated SAMP- or RAMP-hydrazones derived from alkyl- or arylethyl ketones 3 add to arylaldehydes both diastereo- and enantioselectively. Substituted / -hydroxy ketones with relative syn configuration of the major diastereomer are obtained with de 51-80% and 70-80% ee. However, recrystallization of the aldol adducts, followed by ozonolysis, furnishes diastereo- and enantiomerically pure (lS, S )-. yn-a-mcthyl-/3-hydroxy ketones 5 in 36-51% overall yield. The absolute configuration of the aldol adducts was established by X-ray crystallographic analysis. Starting from the SAMP- or RAMP-hydrazone either enantiomer, (S,S) or (R,R), is available using this methodology16. 

Oximes, hydrazones and analogues are named directly as oxime or hydrazone derivatives etc. 

Hydrazone derivatives 214 cyclize in refluxing ethanol in the presence of a catalytic amount of triethylamine to furnish the corresponding pyridopyrazolotriazines 215 (Equation 24) <1998HAC571>. 

The number of hydrazine groups per protein molecule can be determined by reacting a small portion of the hydrazine-modified protein with p-nitrobenzaldehyde, which forms a chromogenic product upon formation of the hydrazone derivative (Figure 1.111). 

The hydrazinium nicotinate group on these reagents commonly is protected against reaction with the active ester by the addition of acetone to form the acetone hydrazone derivative. This hydrazone protective group is readily reversible at neutral or mildly acidic pH and will immediately exchange with a benzaldehyde on the corresponding chemoselective partner to form a stable hydrazone linkage. 

Pyrazolo[3,2-c]pyrido[4,3- ][l,2,4]triazine oxides704 were prepared by cyclization of the hydrazone derivatives 703 with ethanolic sodium hydroxide. Subsequent reduction of 704 gave 705 (76JPR835). Hydrazone 703 was prepared by condensation of 4-hydrazino-3-nitropyridine with 702. The mass spectral fragmentation patterns for 704 and 705 and their benzo analogues were studied (77ZC142). 

The 4-hydrazino-pyrazolo[3,4-rf]pyrimidine derivative 80 yields pyrazolo[4,3-e]-[l,2,4]triazolo[4,3-c]pyrimidinones 82 through hydrazone derivatives 81 <00JCS(P1)33>, these compounds being a new class of potential xanthine oxidase inhibitors. 

We believe that the intermediate generated by anodic oxidation of 3 is the cation 3a and not nitrilimine 3b. The generation of the cation intermediate was postulated in several papers on the anodic oxidation of hydrazone derivatives [38-41], W also believe that both heteroaromatic and Schiff bases react with the cation 3a as nucleophiles rather than dipolarophiles. The most likely mechanism of the oxidation of the hydrazone 3 in the presence of heteroaromatic and Schiff bases, which would best fit the observed electrochemical and preparative results, can be described in the form of Scheme 8. 

Amino-4,5-dihydro-5-hydroxy-l,2,4-triazine (82B) exhibits a temperature-dependent equilibrium with the open-chain hydrazide-hydrazone derivative 82A in CDCI3 solution, as shown by the H-NMR data (85LA78). 

Treatment of hydrazones derived from 1-adamantyl phenyl ketone, pivalophe-none and benzophenone with sulfur monochloride gave pentathianes 232 and hexathianes 233 along with the corresponding ketones and thioketones as the main products (1997H255 Scheme 124). 

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