Aminomethylenation

Ethoxymethylene- and aminomethylene-amino intermediates are also of use for preparation of 4-ones and 4-imines, e.g. (121) — (122) — (123) from o-aminopyridine esters (78KGS1671) and nitriles (e.g. 75JCS(P1)2182>. 

Similar intermediates including o-ethoxycarbonyl-, o-cyano- and o-dimethyl-aminomethylene-piperidones or their imines have been used to give partially reduced analogues, e.g. (244), in the [2,3-. 

Hydroxymethylene-isoxazolin-5-ones undergo reaction with SOCI2 to form 4-chloromethylenes, with alcohols they form ethers (62HC(17)1, p. 7) and with amines aminomethylenes are obtained (Scheme 58) (73T4291, 60ZOB600). 

The hydrogenation of fV-substituted isoxazolin-5-one ethyl esters produced amino-methylenemalonates (74G715), while hydrogenation of 4-benzoyl-3-phenylisoxazolin-5-one generated an a-aminomethylene-/3-keto acid (Scheme 64). 

Methylisoxazole (297 R = Me) and its homologs can be synthesized by reaction of hydroxylamine hydrochloride with 1-alkyl-3-dimethylamino-2-propen-l-one (296) (54IZV47), the anilino derivatives of acetoacetaldehyde (47G556), 3-dimethyl-aminomethylene-l-propyne (equation 7) (69ZOR1179) and the /3-ketoaldehyde (293) (66JOC3193). 

Barbituric acid — see also Pyrimidine-2,4,6-trione, perhydro-acidic pK, 3, 60 bromination, 3, 70 fluorination, 3, 70 structure, 3, 68 tautomerism, 2, 27 in thermography, 1, 392 Barbituric acid, iV-alkyl-chlorination, 3, 70 Barbituric acid, 5-aminomethylene-synthesis, 3, 524 Barbituric acid, 5-arylidene-pyridopyrimidines from, 3, 227 Barbituric acid, 1,3-dicyclohexyl-synthesis, 3, 113 Barbituric acid, 2-thio-sensitizing dye... 

Despite the fact that the two main components of UF-resins are urea and formaldehyde, a broad variety of possible reactions and structures in the resins can be obtained. At the molecular level, the basic characteristics of UF-resins can be explained as follows (1) high reactivity (2) water solubility and dispersibility, which renders the resins ideal for use in the woodworking industry and (3) the reversibility of the aminomethylene link, which also explains the low resistance of the UF-resins against the influence of water and moisture, especially at higher temperatures. This is also one of the reasons for the subsequent formaldehyde emission. 

Table 4.17. Azacrowns containing the benzene-1,3-bis(aminomethylene) subunit...

The application of this addition to aminomethylene ketones provides a convenient synthesis of monoamides of pimelic acid (508). It should be noted that the corresponding oxidation of hydroxy methylene cyclohexanone leads to ring contraction and formation of cyclopentanoic acid. 

When the enamine is in conjugation with a carbonyl function, as in a-aminomethylene aldehydes (528,529), ketones (530), or esters (531), a Michael addition is found in vinylogous analogy to the reactions of amides. An application to syntheses in the vitamin A series employed a vinyl lithium compound (532). 

At low temperature a 1 1 adduct of thioacetic acid and an enamine could be prepared (709). The previously described reaction of aminomethylene ketones with hydrogen peroxide was extended to bisaminomethylene compounds. However, acylated cyclohexenamines led to cyclopentane-carboxamides (770), Trichloromethyl adducts of enamines and the rearranged amine derivatives were described in a further study (777). 

Phenylmercury derivatives of 3-aminomethylene-l-methyloxindols have also been investigated (79KGS65). For studies of the effect of substituents on the electronic structure of silver and potassium salts of 3-(aryl)imi-nooxindole see 76MI2. The keto-enol and imino-enamine tautomerism of compounds of type 127 (with 128 and 129) has been investigated (85KGS921). 

Whereas vicinal hydroxy, mercapto, and hydroselenoaldimines of azoles strongly prefer the aminomethylene tautomeric form (Section II,E,2), their metal chelates 380 are characterized by.pronounced equalization of bond lengths within the chelate ring, which makes their structures similar to those expected for the aldimine tautomeric type. 

Aminomethylene-5-thio(oxo, seleno)pyrazole (in Russian), Thesis Cand. Chem. Sci. Diss., Rostov State University, Ros-tovon-Don, 1989. 

Shaw concluded that hydrogenation of 3-alkyl-4-aminomethylene isoxazol-5-ones (184) in the presence of palladium catalyst resulted in the saturation of either the endocyclic double carbon-nitrogen bond or the exocyclic double C—C bond with the retention of the heterocyclic nitrogen-oxygen bond. Recent data reported by Kochetkov et al. on the properties, and in particular on hydrogenation, of isoxazolid-5-ones - indicate, however, that Shaw had probably ob-... 

R = H, R =Br, R" =Et) was prepared by cyclization of aroylacetate 314 (R = H, R =Br, r2 = H, X = F) (OOMIPIO). 9,10-Difluoro-3(5)-methyl-7-oxo-7//-pyrido[l,2,3- /e]-l,4-benzoxazine-6-carboxylic acid and its racemic form were prepared in the reaction of ethyl 2-(2,3,4,5-tetrafluorobenzoyl)-2-ethoxymethyleneacetate and (R)- or (i ,5)-2-aminopropanol and subsequent hydrolysis of the ring closed tricyclic esters (98MI45). Cyclization of ethyl 2-(2,3-difluoro-5-iodobenzoyl)-2-[A-(2-hydroxyethyl)aminomethylene]acetate 315 in the presence of K2CO3 in DMF at 95 °C for 3.5 h yielded 9-iodo-7-oxo-2,3-dihydro-7//-pyrido[l,2,3- /e]-l,4-benzoxazine-6-carboxylate (01MIP2). 

Scheme 21 Formation of 5-(aminomethylene)cyclopentenones 101 and 2-(r-aminoalkenyl)-cyclopentenones 102 by formal [2+2+1] cycloadditions. Conditions A THF, 50-55 °C. B THF/ MeCN (9/1), 65 °C [82,83]. For further details see Table 4...

Oxo-3,4-dihydro-2-quinoxalinecarboxamide (23) gave 3-chloro-A -(dimethyl-aminomethylene)-2-quinoxalinecarboxamide (24) (POCI3, Me2NCHO, 20°C 70°C, 8h 65%)7 ... 

The protecting reaction of the enamino pyrrolidinone with t-butoxycarbonyl anhydride was carried out by mixing 4-(N-/-butoxycarbonyl)-4-aminomethylene-pyirolidin-3-one (Boc-AMP) with 1.2 molar equivalents of t-butoxycarbonyl anhydride (/-BoczO) to make l-(N-f-butoxycarbonyl)-4-(N-t-butoxycarbonyl)-ammomethylene-pyrrolidin-3-one (B0C2-AMP). Several types of reactors, including batch reactors, a continuous stirred tank reactor (CSTR),... 

Oxo-3,4-dihydro-2-quinoxalinecarboxamide (117) gave 3-chloro-/V-dimethyl aminomethylene-2-quinoxalinecarboxamide (118) (POCl3, Me2NCHO, 0°C > 70°C, 8 h 65%).748... 

Scale inhibitors may also be used in acidizing. These include alcohol ethoxysulfonic acids (152). Scale inhibitors are also used in water and enhanced oil recovery injection wells and include low molecular weight poly(vinylsulfonate), poly(methylmethacrylate-co-ethylenediamine) (153), bis(phosphonomethylene)aminomethylene carboxylic acid, and poly(acrylic acid-co-3-acrylamido-3-methylbu-tanoic acid). Ethylenediaminetetraacetic acid and similar complex-ing agents have been used to remove scale from formation surfaces near wellbores. 

In analoger Weise bildet der in der Primarreaktion von s-Triazin mit Benzoylessigester gebildete Aminomethylen-benzoylessigester (Lie) iiber LVIII und LIX das 4-Phenyl-5-carbathoxypyrimidin (LX). 

The use or safe disposal of the iron residues from zinc production (see Figure 7) presents a major technical problem.204 The use of chelating aminomethylene phosphonic acid extractants such as (28) and (29) to recover iron from these residues has been proposed.205 These give much higher FenI/Znn selectivity than D2EHPA but are more difficult to strip. A reductive-stripping process is proposed.187,205... 

Primary amino methylene substituents were introduced by a sequence of cya-nodehalogenation and subsequent reduction of the resulting nitrile with borane dimethyl sulfide. To incorporate tertiary aminomethylene substituents into the 2-pyri-done framework, a microwave-assisted Mannich reaction using preformed iminium salts proved to be effective. 

Coronaridine subtype alkaloids are widely spread in Tabernaemontana. The iboga skeleton is particularly susceptible to oxidation at aminomethylenes C-3 and C-5 and at benzylic C-6. Very often, the fundamental compounds are accompanied by the oxidation products at these positions. 

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