Pyridine, 2-imino

Reaction of 2-aminothiazole with -phenethylchloride in anhydrous pyridine is reported to yield 76% 2-(/3-phenethylamino)thia2ole (43), the remaining 24% could be 2-imino-30-phenethylamino)-4-thiazoline (44) (Scheme 32) (188). 

The high reactivity of the exocyclic 4-NH- group is again illustrated by the reaction of 2-imino-3-phenyl-4-amino-5-(ethoxycarbonyl)-4-thiazoline with EtOjCCH SCN, which yields 134 (296), and by the intramolecular preparation of the dihydrothiazolo[4,5-h]pyridine derivative 136 (297) (Scheme 89). 

Iminoselenazolidin-4-one is benzoylated on the imino" nitrogen with benzoyl chloride in pyridine solution (77),... 

The electronic environment of an a-substituent on pyridine (319) approaches that of a substituent on the corresponding imino compound (320) and is intermediate between those of substituents on benzene and substituents attached to carbonyl groups (321, 322) (cf. discussion in Chapter 2.02). Substituents attached to certain positions in azole rings show similar properties to those of a- and y-substituents on pyridine. However, the azoles also possess one heteroatom which behaves as an electron source and which tends to oppose the effect of other heteroatom(s). 

Pyridinium ylide, 1-ethoxycarbonylimino-photolysis, 2, 313 Pyridinium ylide, N-imino-photolysis, 2, 314 synthesis, 2, 185 Pyridinium ylides, 2, 336 photolysis, 2, 313-314 Pyridin-2-one, 3-acetyl-synthesis... 

The fact that the equilibrium for aminopyridine 1-oxides is displaced further in favor of the amino form than is the equilibrium for aminopyridines is in accord with the mesomerism of these compounds. The stabilization of the amino forms (e.g., 241) by structures of type 240 is more effective than the corresponding stabilization in the pyridine series since the negative charge is associated with the oxygen atom. The stabilization of the imino form (e.g., 242) by structures of type 243 is less than in the pyridine series because of the adverse inductive effect of the oxygen atom. ... 

It is evident that in this ring transformation the C-3-C-4 bond in the pyridine ring has undergone fission. This bond breaking very probable occurs in the covalent o-adduct at C-4. After ring opening the imino-acetylene derivative is formed it is in equilibrium with the iminoketenimine, in which cyclization easily occurs (Scheme 45). 

Demethylation of trequinsin (3) with a 65 35 mixture of AcOH and 48% HBr at 115 °C for 3 h gave mainly 10-hydroxyl derivatives 148 (R = r = H), which was accompanied by traces of its 9-hydroxyl and 9,10-dihydroxy derivatives. In boiling 48% HBr for 2 h its 9,10-dihydroxy derivative formed in 63% yield (98IJC(B)1). 9-Methoxy group of 3 and that of its 2-[(2,6-dimethyl-4-carboxyphenyl)imino] derivative 178 (R = COOH) was selectively demethylated by the treatment with 60% NaOH and EtSH in HMPA. Treatment of 3 with pyridine HCl in boiling pyridine for 20 min afforded its 9,10-dihydroxy-3-desmethyl derivative in 65% yield. 4 -Hydroxymethyl... 

Malonsaurc-dinitrile und deren Monosubstitutions-Produkte werden zu 3-Imino-pro-pansaure-nitrilen reduziert, die sich zu3-Amino-acrylnitrilen isomerisieren. So erhalt man z.B. aus Malonsaure-dinitril selbst 40% d.Th. cis- und trans-3-Amino-acrylnitril neben 7% d. Th. 2-Amino-3-cyan-pyridin (bei langer Reaktionsdauer und Lithiumalanat-Ober-schuG auch 2% d.Th. 3-Cyan-pyridin) ... 

Bis(imino)pyridine iron complex 5 as a highly efficient catalyst for a hydrogenation reaction was synthesized by Chirik and coworkers in 2004 [27]. Complex 5 looks like a Fe(0) complex, but detailed investigations into the electronic structure of 5 by metrical data, Mossbauer parameters, infrared and NMR spectroscopy, and DFT calculations established the Fe(ll) complex described as 5 in Fig. 2 to be the higher populated species [28]. 

Further investigations revealed that this hydrogenation is accelerated in pentane solution. These results are shown in brackets in Table 3 [31]. Under optimized reaction conditions high catalyst TOF up to 5,300 were achieved when 10 was used. In the absence of both hydrogen and nitrogen, 10 was converted into the q -arene complexes such as the bis(imino)pyridine iron q -phenyl complex, 10-Phenyl, and the corresponding q -2,6-diisopropylphenyl complex, 10-Aryl, in the 85 15 ratio in... 

Scheme 7 Intramolecular arene coordination in bis(imino)pyridine iron complex 10...

Bis(imino)pyridine iron complex 5 acts as a catalyst not only for hydrogenation (see 2.1) but also for hydrosilylation of multiple bonds [27]. The results are summarized in Table 10. The reaction rate for hydrosilylations is slower than that for the corresponding hydrogenation however, the trend of reaction rates is similar in each reaction. In case of tra s-2-hexene, the terminal addition product hexyl (phenyl)silane was obtained predominantly. This result clearly shows that an isomerization reaction takes place and the subsequent hydrosilylation reaction dehvers the corresponding product. Reaction of 1-hexene with H2SiPh2 also produced the hydrosilylated product in this system (eq. 1 in Scheme 18). However, the reaction rate for H2SiPh2 was slower than that for H3SiPh. In addition, reaction of diphenylacetylene as an atkyne with phenylsilane afforded the monoaddition product due to steric repulsion (eq. 2 in Scheme 18). 

The comparison of a bis(imino)pyridine iron complex and a pyridine bis (oxazoline) iron complex in hydrosilylation reactions is shown in Scheme 24 [73]. Both iron complexes showed efficient activity at 23°C and low to modest enantioselectivites. However, the steric hindered acetophenone derivatives such as 2, 4, 6 -trimethylacetophenone and 4 -ferf-butyl-2, 6 -dimethylacetophenone reacted sluggishly. The yields and enantioselectivities increased slightly when a combination of iron catalyst and B(CeF5)3 as an additive was used. 

Scheme 24 The comparison of a bis(imino)pyridine iron complex and a pyridine bis(oxazoline) iron complex for hydrosilylation of ketones...

In 2009, Chirik reported a hydrogen-mediated reductive enyne cyclization catalyzed by the bis(imino)pyridine iron complex 5 (Scheme 37) [119]. In the... 

As an alternative method for the C-C bond formation, oligomerization and polymerization reactions of olefins catalyzed by a bis(imino)pyridine iron complex are also well known (Scheme 40) [121-124]. 

A head-to-head dimerization of a-olefin catalyzed by a bis(imino)pyridine iron complex has been reported by Small and Marcucci [126]. This reaction delivers linear internal olefins (up to 80% linearity) from a-oleftns. The linearity of products, however, depends on the catalyst structure and the reaction conditions. 

Fink and Babik reported that propylene polymerization was achieved by a bis (imino)pyridine iron complex with Ph3C[B(C6p5)]4] and ttialkylaluminium as additives [127]. Both 3-methyl-"butyl and "butyl endgroups were observed by NMR spectrum when ttiisobutylaluminium as an activator was used, whereas the only "propyl endgroup was formed in case of triethylaluminium activation. In addition, this polymerization proceeds two times faster with than without a hydrogen atmosphere, but the value decreases and the M IM value rises up. 

Acidic treatment of prechilenine (139) (Section III,C) afforded the imino keto acid 377 via the imminium salt 140 (Scheme 68). Neutralization and work-up furnished the known y-lactol 371 in 90% overall yield from 139 (96, 181). Kondo et al. (183) obtained 139 from the epidioxide 122 by treatment with pyridine hydrochloride in pyridine along with 377 and norhydrastine. The acid 377 was converted to the known imino ester 373 through N,0-dimethylation. 

Pyridine derivatives with additional donor functions and sterically demanding substituents have been used with the intention of producing complexes of Cd (and of other metals) with low coordination number one of these ligands is the tridentate, planar-bonding 2,6-bis[(2,6-dimethyl-phenylimino)methyl] pyridine (pydim a Schiff base derived from 2,6-pyridine dialdehyde), which with Cd(BF4)2 and thiocyanate gives a dinuclear complex [(pydim)Cd(/x-NCS-S,N)]2(BF4)2 with N-dominated coordination sphere.191 As centrosymmetric Plijc, Z= 2), the complex has an antiparallel /x-1,3 NCS double bridge with Cd—N and Cd—S bonds (224.6 pm and 255.5 pm, respectively) the Cd—N(py) bond is clearly shorter than the Cd—N(imino) bonds (225.6 pm and 245.0 pm,... 

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