Methane imines

The vapor-phase pyrolysis of 4-hydroxy-1,2,3-triazole and its iV-methyl derivative affords methan-imine and its A-methyl analog. Analysis of the reaction path by the MNDO method shows the presence of two stable or metastable isomers, (liif)-4-hydroxy-l,2,3-triazole and its ketone protomer <89NJC551>. 4-Diazo-1,2,3-triazoles (122) thermolyze or photolyze in benzene to 4//-l,2,3-tri-azolylidenes (123) which convert benzene to 4-phenyl-1,2,3-triazoles and/or isomerize to a-diazo-nitriles (124). Intermediates (124) react with benzene via a carbene to give addition, ring expansion or substitution products (Scheme 17) <82TL5115>. The similar thermolysis of diazotriazoles in substituted benzene gives complex mixtures in which all of the components are sometimes impossible to isolate and identify <90AHC(48)65>. 

Selective transformations Selective styrene ring opening [103] One-pot domino process for regioselective synthesis of a-carbonyl furans [104] Tandem process for synthesis of quinoxalines [105] Atmospheric oxidation of toluene [106] Cyclohexane oxidation [107] Synthesis of imines from alcohols [108] Synthesis of 2-aminodiphenylamine [109] 9H-Fluorene oxidation [110] Dehydrogenation of ethane in the presence of C02 [111] Decomposition of methane [112] Carbon monoxide oxidation [113]... 

Armesto, Horspool and coworkers have extensively studied the related rearrangement of /hy-LinsaUiraled imine derivatives, the so-called aza-di-7r-methane rearrangement37. A particularly interesting example is seen by the rearrangement of 75 to 76 (Scheme 19). Adduct 76 furnished chrysanthemic acid following a simple series of steps. It has been... 

Various substituted /J,y-unsaturated imines (equation 77) did undergo aza-di- r-methane... 

As mentioned above, iridium complexes are also active in the formation of amines via the hydrosilylation/protodesUylation of imines. In the presence of 2 equiv. of HSiEts, the cationic complex [lr bis(pyrazol-l-yl)methane (CO)2][BPh4] (C4) catalyzes the reduction of various imines, including N-alkyl and N-aryl imines and both aldimines and ketimmes. Excellent conversions directly to the amine products were achieved rapidly at room temperature in a methanol solution (Scheme 14.7) [53]. 

The aza-di-TT-methane (ADPM) rearrangement of aza-1,4-dienes via radical-cat-ions suggests the possibility that other radical-ion intermediates (e.g., radical-anions) could also be responsible for this rearrangement reaction. In order to test this proposal, the azadiene 101 was irradiated for 20 min in acetonitrile using A,iV-dimethylaniline (DMA) as an electron-donor sensitizer. The reaction leads to formation of the cyclopropylimine 102. Separation of product mixture by column chromatography on silica gel affords the aldehyde 34 (21%) resulting from hydrolysis of the imine 102, (Scheme 18) [70]. 

Reaction of bis(iodozincio)methane (3) with /9-acylcrotonate also afforded cyclopropane derivative (equation 44). As shown in equation 45, the cyclopropane ring in this product opens and reacts with an imine to give /9-aminoalkanol derivatives diastereoselectively71. 

Tt-methane rearrangement,601 generally occurs only from the triplet state), to 3,y-unsaturated imines,602 and to triple-bond systems.603... 

Di-t-butvl ketone imine (5.64 g) in dry light petroleum under dry nitrogen was treated with ethereal methyllithium (1.00 mol. eq). When methane evolution had ceased, dry carbon disulfide (3.2 ml) was added and the mixture stirred for 3h. The solvent was removed under reduced pressure at room temperature and the solid brown residue heated at 80-100°C under vacuum, and practically pure thione was distilled into a solid C02-acctonc trap (100%). The residue is yellow when the distillation is complete. Redistillation afforded the pure, deep-violet, thioketone, b.p. 61°C/14 torr. 

A completely similar reaction occurs when Ru2(CO)6(R-Pyca R R2 ) (R-Pyca R R2 = 6-R NC5H3-2-C(R2) = NR with R = alkyl or aryl Rl = H, Me and R2 = H, Me) is reacted with excess pyridinimine.164 The facile reaction leads to the formation of Ru2(CO)5(APM) (APM — bis(/i-t-butylamino)(2-pyridyl)methane-N) (ref. 162, footnote). (The crystal structure of this compound shows two C—C-coupled pyridin-2-imines which bridge a non-bonding Ru2 metal pair. The... 

These compounds, according to the US NavOrdLab Memorandum 10068, 3/24/1949, are characterized by low mp, good heat stability and moderate sensitivity Aliphatic Amines and Imines, Nitrated Derivatives. A number of these compds are of interest in the field of explosives and are discussed under the individual compds, such as amino methane, aminoethane, amino-guanidine, etc... 

Treatment of amino acid 156, imine and 2-chloro-l-methylpyridinium iodide (Mukaiyama s reagent) in the presence of triethylamine in refluxing dichloro-methane afforded spiro-(3-lactams 157,158. These were obtained as a 1.8 1 mixture of diastereoisomers and separated by column chromatography. The reaction of 159 and imine under the usual experimental conditions resulted in the formation of a single diastereoisomer 160. The absolute (3 S, 4 S, 7 -configuration was assigned on the basis of mechanistic considerations and XH NMR spectra. The presence of the stereocenter affords complete diastereoselectivity (only trans diastereoisomers 157, 158) and enantioselectivity (160). 

Rink resin derived imines have been reported to give cycloaddition reactions with acetyl chlorides (or equivalent) using triethylamine as the base and dichloro-methane as the solvent at temperature ranging from 0°C to room temperature [70], The resin-bound p-lactam could be cleaved by using 50% trifluoroacetic acid (TFA) in dichloromethane, to afford the /V-unsubstituted p-lactam. 

Bis(phosphoranimine) ligands, chromium complexes, 5, 359 Bis(pinacolato)diboranes activated alkene additions, 10, 731—732 for alkyl group functionalization, 10, 110 alkyne additions, 10, 728 allene additions, 10, 730 carbenoid additions, 10, 733 diazoalkane additions, 10, 733 imine additions, 10, 733 methylenecyclopropane additions, 10, 733 Bisporphyrins, in organometallic synthesis, 1, 71 Bis(pyrazol-l-yl)borane acetyl complexes, with iron, 6, 88 Bis(pyrazolyl)borates, in platinum(II) complexes, 8, 503 Bispyrazolyl-methane rhodium complex, preparation, 7, 185 Bis(pyrazolyl)methanes, in platinum(II) complexes, 8, 503 Bis(3-pyrazolyl)nickel complexes, preparation, 8, 80-81 Bis(2-pyridyl)amines... 

Such an example has been demonstrated by Johnson and Sames, who chose a platinum-mediated dehydrogenation as a key step in the synthesis of the antimitotic rhazinilam 33 (Scheme 6) [20], The key intermediate 27 was converted into the imine 28, which was allowed to react with Me Pt(//-SMe2)]2 to afford the platinum complex 29. Subsequent treatment with triflic acid resulted in elimination of methane and furnished the cationic complex 30. Upon thermolysis in trifluoroethanol, the complex lost a second methane molecule, which resulted in the activation of the ethyl group. A subsequent /1-hydride elimination gave the hydrido-Pt(n) complex 31. Treatment with aqueous KCN followed by hydrox-ylamine removed the platinum and yielded the liberated amine 32. Johnson and Sames added a homologization and a macrolactamization and completed the total synthesis of rhazinilam (33) by removal of the carboxyl group. 

J. -A.F., and Perez-Ossorio, R. (1986) The synthesis and photochemical reactivity of p/y-unsaturated imines. An azadi-Jt-methane rearrangement of 1-azapenta-... 

The diruthenium complex having Ru-H-Si interactions Ru(CO)2SiTol2H) 2(ju-dppm)(p-q2 q2-H2SiTol2), where dppm is bis(diphenylphosphine)methane and Tol isp-tolyl, has been recently reported to be very effective in the hydrosilylation of various ketones (Eq. 95) and imines (Eq. 96) with dihydrosilanes [150]. 

Setzt man jedoch Aldehyd-imine ein, erhalt man in guten Ausbeuten Amino-phenyl-methan- bzw. 1-Amino-alkanphosphonsauren17 ... 

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