Nucleophiles hydrazine

The kinetics of the aminolysis reactions of the a-effect nucleophiles hydrazine and hydroxyiamine with Y-phenyl X-benzoates (8) have been reported." The results demonstrated that the magnitude of the a-effect decreases with increasing electron-withdrawing ability of the acyl substituents. The authors propose that hydrazine stabilizes the transition state (9) by intramolecular H-bonding. ... 

The distracting paraphernalia that surrounds compound I may be considerably simplified by realizing that on one hand, the phthalimido and lactone rings disappear in the process, probably under the attack of the strongly nucleophilic hydrazine. This is suggested by the presence of hydroxymethylene and acylhydrazide groupings in II. 

The enolate ion, 3-61, will pick up a proton from solvent, and the hydrazinium ion will lose a proton to a base, such as a molecule of hydrazine. The distance between the groups in the molecule makes intramolecular transfer of a proton quite unlikely. The nucleophilic hydrazine group in the neutral intermediate, 3-62, can react intramolecularly with the electrophilic carbon of the carbonyl group. 

The partial inhibition of the hydrolysis observed at pH < 4, and the negative salt effect, may be attributed to a specific cation-anion interaction. The proposed mechanism receives further support from the observed effects on the hydrolysis rates of increased viscosity of the medium and of added inorganic nucleophiles. Hydrazine or alkylhydrazines cleave and recyclize 1,3,4-thiadiazolium salts (114) to 1,2- or l,4-dihydro-l,2,4,5-tetrazines (115) in high yield. The action of arylhydrazine results in the alternative recyclization of the probable intermediate ArNHN=CR2NR N=CR SH, to 4-amino-1,2,4-triazolium salts (116). 5-Amino-2-imino-3-phenacyl-l,3,4-thiadiazolines (117) isomerize in boiling ethanol to 5-amino-3-mercapto-l-phenacyl-l,2,4-triazoles (118). This example... 

The phthaloyl (Phth) derivatives of amines, formed from amines and N-ethoxy-carbonylphthalimide (G.H.L. Nefkens, 1960), are acid-resistant imides, which can be easily deblocked by nucleophilic reagents, most conveniently by hydrazine. 

Nucleophilic addition of 2-aminothiazole to the double bond of di-maleic acid hydrazine has been reported (206). No spectroscopic proof, however, is given to establish the proposed structure (60) for the resulting product (Scheme 41). 

The principal reactions of this class of compounds are summarized in Scheme 172. In most of these reactions the reactive nucleophilic center is the terminal NHj group, although the other exocyclic nitrogen may also be involved, as shown by acetylation, which yields 284 and 285. However, the structure of compound 281 is not the one proposed in a recent report (1582) that attributes the attack to the other exocyclic nitrogen. The formation of osazones (287) from sugars, 2-hydrazinothiazoles, and hydrazine has been reported (525, 531). 

Hydrazine cleaves amide bonds to form acylhydrazides according to the general mechanism of nucleophilic acyl substitution discussed in Chapter 20... 

The ionic hydrazides are extremely sensitive and explode on contact with ak or upon heating. The alkaline-earth hydrazides, which have the general formula M(N2H2), appear to be less sensitive (15). Hydrazides such as aluminum hydrazide [25546-96-7] Al(N2H2)3, have also been made (16). The hydrazide anion is more nucleophilic than hydrazine and undergoes reactions not possible using hydrazine itself (17). Thus, styrene in ethyl ether solution at 0°C is... 

Hydrazine as Nucleophile. Reaction of hydrazine and carbon dioxide or carbon disulfide gives, respectively, hydrazinecarboxyhc acid [471-31-8], NH2NHCOOH, and hydrazinecarbodithioic acid [471-32-9], NH2NHCSSH, in the form of the hydrazinium salts. These compounds are useful starting materials for further synthesis. For example, if carbon disulfide reacts with hydrazine in basic medium with an alkyl haUde, an alkyl dithiocarbazate ester is obtained in a one-step reaction ... 

Aluminum chloride [7446-70-0] is a useful catalyst in the reaction of aromatic amines with ethyleneknine (76). SoHd catalysts promote the reaction of ethyleneknine with ammonia in the gas phase to give ethylenediamine (77). Not only ammonia and amines, but also hydrazine [302-01-2] (78), hydrazoic acid [7782-79-8] (79—82), alkyl azidoformates (83), and acid amides, eg, sulfonamides (84) or 2,4-dioxopyrimidines (85), have been used as ring-opening reagents for ethyleneknine with nitrogen being the nucleophilic center (1). The 2-oxopiperazine skeleton has been synthesized from a-amino acid esters and ethyleneknine (86—89). 

The most useful syntheses of pyridazines and their alkyl and other derivatives begins with the reaction between maleic anhydride and hydrazine to give maleic hydrazide. This is further transformed into 3,6-dichloropyridazine which is amenable to nucleophilic substitution of one or both halogen atoms alternatively, the halogen(s) can be replaced by hydrogen as shown in Scheme 110. In this manner a great number of pyridazine derivatives are prepared. 

Nucleophilic substitution of the chlorine atom in 2-chloropyrazine and 2-chloroquinoxa-lines has been effected with a variety of nucleophiles, including ammonia and amines, oxygen nucleophiles such as alkoxides, sodium azide, hydrazine, sulfur containing nucleophiles, cyanide, etc., and reactions of this type are typical of the group (see Chapter 2.02). 

Reactive halogens in various series have been removed by catalytic hydrogenation with either platinum or palladium catalysts, and other nucleophiles which have been used in chloride displacements include hydroxide ion, alkoxides, hydrosulflde, hydrazine and toluene-p-sulfonylhydrazine, and trimethyl phosphite. 

In forcing conditions with excess of reagents the 5,8-bis derivative was obtained in the above cases, with hydrazine and with sulfur nucleophiles. Other authors have also observed selective reactions in the pyrido[2,3-[Pg.242]

Many other examples are known of non-selective reactions of halo groups in pyridopyridazines with amines, alkoxides, sulfur nucleophiles such as hydrosulfide and thiolate ions, or thiourea, hydrazine(s), cyanide ion and dimethyl sulfoxide, or on catalytic reduction. 

Thione or alkylthio groups have also been involved in nucleophilic substitutions with hydrazine, or amines, and by desulfurization using Raney nickel or aluminum amalgam. 

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