Oximes iodide

SYNS 2-FORMYL-l-METHYLPYRIDINIUM IODIDE OXIME 2-FORMYL-N-METHYLPYRIDINIUM OXIME IODIDE 2-HYDROXYIMINOMETHYL-l-METHYLPYRIDINIUM IODIDE l-METHYL-2-ALDOXIMINOPYRIDINTUM IODIDE l-METHYL-2-HYDROXYIMINOMETHYLPYRIDINIUM IODIDE N-METHYLPYRIDINE-2-ALDOXIME IODIDE N-METHYLPYRIDINIUM-2-ALDOXIME IODIDE NSC-7760 PAM (CZECH) 2-PAM IODIDE PRALIDOX-... 

The reaction of 3,5-diphenyl-2-isoxazoline with lithium diisopropylamide produced with 2 equivalents of base a chalcone oxime, while in the presence of 1 equivalent and an alkyl iodide, ring alkylation occurred at the 4-position of the nucleus (Scheme 48) (80LA80, 78TL3129). 

The present procedure was developed from those of Wallach and Freylon, based upon the general method discovered by Leuckart. a-Phenylethylamine also can be prepared satisfactorily by the reduction of acetophenone oxime with sodium and absolute alcohol or sodium amalgam, but the reagents are more expensive and the processes less convenient. The amine has been obtained by reducing acetophenone oxime electro-lytically, by reducing acetophenone phenylhydrazone with sodium amalgam and acetic acid, from a-phenylethyl bromide and hexamethylenetetramine, and by the action of methyl-magnesium iodide upon hydrobenzamide, as well as by other methods of no preparative value. 

Cotarnine with methyl iodide furnishes cotarnine hydriodide and cotarnine methine methiodide, CiiHu04NMe3l (IX), which is decomposed by alkalis into trimethylamine and cotarnone (X), CuHioO, rhombic plates, m.p. 78°. The latter yields an oxime, m.p. 130-2°, and is oxidised by potassium permanganate to a mixture of cotarnic acid (VI) and cotamlactone, CuHjqOj (XI), brilliant leaflets, m.p. 154°, which is convertible into the corresponding acid, cotarnonelactone acid, leaflets, m.p. 90-100° dec.). The lactone on further oxjdiltion yields cotarnic aeid. ... 

Oxime 26 was prepared from 5,ll-dihydro-dibenzo[a,d]cyclohepten-10-one. The Hoch-Campbell reaction of 26 with 3-dimethylaminopropylmagnesium bromide produced aziridine 27 in 46% yield after acidic workup. Extension of the Hoch-Campbell reaction to steroids has also been reported. Thus, treatment of 3(3-hydroxy-5-pregnen-20-one oxime (28) with methylmagnesium iodide furnished a mixture of diastereomers, 20ot/20P,21-imino-20-methyl-5-pregnen-3P-ol (29) in a 50% combined yield and a 3 1 ratio. On the other hand, homo-adamantan-4-one oxime (30) was transformed to homo-adamantano[4,5-b]-2 -ethylaziridine (31) in 76% yield upon the action of... 

The radical alkylation of ketones is achieved by their conversion into the desired N-silyloxy enamines 81 (Scheme 13). The reaction of 81 with diethyl bromomalonate in the presence of EtsB (0.5 equiv) in benzene was performed in open air and stirred at room temperature for 3h. With nitro compounds it is achieved by their conversion into the desired ]V-bis(silyloxy)enamines (82) (Scheme 13). When the reaction is carried out with 82 and alkyl iodides with an electron-withdrawing substituent at the a-position, using V-70 as radical initiator (2,2 -azobis(4-methoxy-2,4-dimethylvaleronitrile)), it underwent a clean radical alkylation reaction to yield an oxime ether. Successful radical alkylation of... 

O-Acylated or mesylated oximes such as the ethyl carbonate of acetophenone-oxime 1772 react with TIS 17, with Beckmann rearrangement to the imidoyl iodide 1773, which adds phenylmagnesium bromide in situ to give 61% of the sec-... 

Reaction with Propargyl Halides. The indium-mediated coupling of propargyl bromide with a variety of imines and imine oxides afforded homo-propargylamine derivatives in aqueous media under mild conditions.78 Propargylation of glyoxylic oxime ether in the presence of a catalytic amount of palladium(O) complex and indium(I) iodide in aqueous media was also studied (Eq.11.47).79... 

Clerici and Porta reported that phenyl, acetyl and methyl radicals add to the Ca atom of the iminium ion, PhN+Me=CHMe, formed in situ by the titanium-catalyzed condensation of /V-methylanilinc with acetaldehyde to give PhNMeCHMePh, PhNMeCHMeAc, and PhNMeCHMe2 in 80% overall yield.83 Recently, Miyabe and co-workers studied the addition of various alkyl radicals to imine derivatives. Alkyl radicals generated from alkyl iodide and triethylborane were added to imine derivatives such as oxime ethers, hydrazones, and nitrones in an aqueous medium.84 The reaction also proceeds on solid support.85 A-sulfonylimines are also effective under such reaction conditions.86 Indium is also effective as the mediator (Eq. 11.49).87 A tandem radical addition-cyclization reaction of oxime ether and hydrazone was also developed (Eq. 11.50).88 Li and co-workers reported the synthesis of a-amino acid derivatives and amines via the addition of simple alkyl halides to imines and enamides mediated by zinc in water (Eq. 11.51).89 The zinc-mediated radical reaction of the hydrazone bearing a chiral camphorsultam provided the corresponding alkylated products with good diastereoselectivities that can be converted into enantiomerically pure a-amino acids (Eq. 11.52).90... 

Domino radical transformations on solid support can also be used, as shown by Naito and coworkers [18]. Thus, immobilized oxime ether 10-55 (Wang resin) afforded the tetrahydrofuranones 10-57 after removal of the resin, when it was exposed to BEt3 in the presence of different alkyl iodides 10-56 (Scheme 10.14). 

A similarly high performance has been reported for oxime-derived (125) and benzylsulfide-derived (126) palladacycles.438 These precatalysts are effective in the cross-coupling of arylboronic acids,438,439 organotin compounds,440 and terminal acetylenes441 with aryl iodides and bromides, and of activated aryl chlorides. SC-palladacycles can effect the Suzuki-Miyaura reaction even at room temperature. 

This protocol could be extended to a range of different ,/i-unsaturated carbonyl compounds and either activated or deactivated aryl iodides [22], An application of related Heck chemistry to the synthesis of methylated resveratrol (3,4, 5-trihydroxy-( )-stilbene) is shown in Scheme 6.4 [23]. The phytoalexin resveratrol exhibits a variety of interesting biological and therapeutic properties, among them activity against several human cancer cell lines. Botella and Najera have shown that the trimethyl ether of resveratrol (Scheme 6.4) can be rapidly prepared by microwave-assisted Heck reaction of the appropriate aryl iodide and styrene derivatives, using the same oxime-derived palladacycle as indicated in Scheme 6.3. 

Electrophilic substitution of the ring hydrogen atom in 1,3,4-oxadiazoles is uncommon. In contrast, several reactions of electrophiles with C-linked substituents of 1,3,4-oxadiazole have been reported. 2,5-Diaryl-l,3,4-oxadiazoles are bromi-nated and nitrated on aryl substituents. Oxidation of 2,5-ditolyl-l,3,4-oxadiazole afforded the corresponding dialdehydes or dicarboxylic acids. 2-Methyl-5-phenyl-l,3,4-oxadiazole treated with butyllithium and then with isoamyl nitrite yielded the oxime of 5-phenyl-l,3,4-oxadiazol-2-carbaldehyde. 2-Chloromethyl-5-phenyl-l,3,4-oxadiazole under the action of sulfur and methyl iodide followed by amines affords the respective thioamides. 2-Chloromethyl-5-methyl-l,3,4-oxadia-zole and triethyl phosphite gave a product, which underwent a Wittig reation with aromatic aldehydes to form alkenes. Alkyl l,3,4-oxadiazole-2-carboxylates undergo typical reactions with ammonia, amines, and hydrazines to afford amides or hydrazides. It has been shown that 5-amino-l,3,4-oxadiazole-2-carboxylic acids and their esters decarboxylate. 

Free radicals generated by zinc and alkyl iodides easily add to oxime ethers (e.g. 106, equation 75), providing good yield of corresponding hydroxylamines 107. This reaction has also been performed in solid-phase bound oxime ethers. ... 

Recent advances in radical reactions have greatly benefited from the efficiency of organotin reagents as mediators. Radical reaction of alkyl iodides with trifluoromethyl phenylsulfonyl oxime ether 69 and hexamethylditin at 300 nm in benzene afforded the corresponding trifluoromethyl oxime ethers 70 in high yields (Scheme 37) . 

Radical cyclization of oxime ethers having allylic substiffients to five-membered rings including furan and pyrrole derivatives was described in reviews A thiophenol-promoted radical cyclization of oxime ethers into tetrahydrofurans was recently described. For example, oxime derivative 36 in the presence of thiophenol and azobisisobuty-ronitrile (AIBN) afforded substimted tetrahydrofurans 37 and 38 in a ratio 1.2-3 1 (equation 17) . Radical cyclization of oxime ethers 39 to tetrahydrofurans 40 was successfully realized in the presence of alkyl iodides and EtsB in refluxing toluene (equation 18) . ... 

Acetylenic oximes undergo in a similar manner conversion to 3,5-disubstituted isoxazoles. Thus, oximes 195 in the system K2C03/Me0H at room temperature afforded isoxazoles 196 in excellent yields (equation 85). a, S-Unsaturated ketoximes 197 can be also easily transformed to the corresponding 5-arylisoxazoles 198 (yield up to 95%) by treatment with iodine and potassium iodide. The presence of isoxazoline was detected in the reaction mixture (equation 86) . a, S-Unsaturated ketoximes in the presence of palladium catalyst afforded isoxazolines . 

Lehman, R.A., and Nicholls, M.E. Antagonism of phosphollne (echothiophate) iodide by certain quaternary oximes. Proc. Soc. Exp. Biol. Med. 104 550-554, i960. 

Other salts of N-methylpyridinium-2-formyl oxime are identified by the abbreviation 2-PAH followed by the common symbols for elemental anions (such as 2-PAM I for the iodide) or the names of organic anions (such as 2-PAM tartrate). Other salts of N.N -trimethyl-ene-bis (4-formylpyridinlum oxime) are identified by appending the designation for the anion to the abbreviation TMB-4. 

In the rat, absorption of III from a single-loop intestinal preparation during 1 h was found to be only about 13% of that of 2-PAM 1.37 The rate of absorption of I was somewhat lower than that of the iodide II was absorbed at nearly the same rate as the iodide.38 Three hours after the oximes were put into intestinal loops, slightly more than one-third as much of III had been absorbed as of 2-PAM I. 

Kondrltzer et al.,130 n searching for a salt of 2-PAM that would be more soluble than 2-PAM I in water, made a number of other salts. Most of these were considerably more soluble in water than 2-PAM I. One of the most soluble was the lactate, with a solubility of 1 g/ml. Unfortunately, this salt was found to be quite unstable in aqueous solution with respect to heat. I was less soluble in water than the lactate, but more than 13 times as soluble as the iodide. Furthermore, solutions of I at a pH of 3.5-4.3 could be autoclaved at 120°C for 15 min with only a 4% loss. Solutions of this salt stored at 50-70°C for 1-3 mo contained at least 78% of the original oxime and no more than 0.1% of hydrogen cyanide. When the aged solutions were examined for lethality to experimental animals, their lethal activities were exactly those expected on the basis of their oxime concent rat ions. 

Kaiser, S.C. 1959. Metabolism of 2-formyl-l-methyl pyrldlnlum Iodide oxime (2-PAM). CWLR 2347. 

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