Anilino acetic acid

Anilino Acetic Acid, CH2(C6H6—NH)—COOH Phenyl Glycine... 

Dye-borate systems were disclosed to initiate radical polymerization [P C 08, PAC 01, KAB 98] but the sensitivity significantly increases by addition of iodonium borates to a dye-borate system [SIM 09]. This combination avoids ion exchange in systems comprising a cationic polymethine dye and an iodonium ion because both comprise the same counter ion. Ion exchange can lead to undesired events (i.e. crystallization) affecting sensitivity of the lithographic material. Further studies on dye-borate systems discuss the efficiency of electron transfer from the borate to the acceptor excited [SCH 90]. Moreover, oxidation of the (anilino)acetic acid results in fast generation of the aminyl radical and the release of CO2 as shown in equation [7.5]. 

The reaction of 2-anilino-l,4-naphthoquinone 374 with benzoylacetic acid hydrazide gives 3-hydrazino-pyrazolyl derivative 375, that is acetylated to produce 5-[[l,4-dihydro-l,4-dioxo-3-(phenylamino)-2-naphthalenyl]sulfonyl]-3-methyl-6-phenyl-5/7-pyrazolo[5,l-c][l,2,4]triazole 51. This latter derivative is also obtained in 51% yield from reaction of 374 with benzoylacetic acid hydrazide in the presence of a mixture of acetic acid-sodium acetate <2004PS(179)1907> (Scheme 39). 

The reaction is best carried out in the appropriate anhydrous aldehyde or ketone, which thus functions as reactant and solvent, or in ethanol, in the presence of an optimum of 1.5 equivalents of strong acid per equivalent of arylbiguanide (base). Acetic acid as a catalyst produces, anomalously, the "base-catalysed anilino-triazines (126, 443). The reaction time varies from one hour to two weeks. The rates diminish in the following order ... 

Indoxyls and their oxygen and sulfur analogues are prepared by the cyclization of anilino-, phenoxy-and phenylthio-acetic acids, respectively (64 — 65), with NaNH2 (for Z = NH), P205 (for Z = O) and H2S04 (for Z = S). 

Treating formaldehyde phenylhydrazone (803) with acetic acid affords 4-anilino-2-phenyl-2,3,4,5-tetrahydro-l,2,4-triazine (805). The first step in this reaction is the dimerization of (803) to give 2-(2-phenylhydrazino)acetaldehyde phenylhydrazone (804) which is cyclized by formaldehyde, probably formed by hydrolysis of (803) (73AJC1297). 

A variant on this reaction makes use of l-anilino-l-methylmercapto-2-nitroethylene as the nitro-synthon. This leads to the 2-anilino-3-nitro-quinolines 88.7S The reaction is best carried out in acetic acid. The condensed thiophene derivatives 89 have been prepared similarly. The use of anthra-... 

The total synthesis of ellipticine by Miller el al. [11] is one of the first syntheses of naturally occurring indole alkaloids using Pd(OAc), via the oxidative cyclization mechanism (Scheme 2). Exposure of 6-anilino-5,8-dimethylisoquinoline (9) to two equivalents of Pd(OAc)j in TFA/AcOH facilitated the oxidative cyclization to the desired ellipticine (10). Recently, the same indole formation strategy that uses the Pd(OAc),-mediated oxidative cyclization has been the cornerstone of several synthetic approaches directed toward ellipticine analogs. For instance, oxidative cyclization of diphenylamine 11 was carried out with Pd(OAc), in acetic acid to provide... 

This reaction was initially reported by Diels and Reese in 1934. It is the conjugate addition between hydroazobenzene and dimethyl acetylene-dicarboxylate. The resulting adduct can be transformed into three different heterocyclic compounds under various experimental conditions (i.e pyrazolones with acid, indoles upon heating in xylene, and quinolones with base ). For example, l,2-diphenyl-3-carbomethoxy-5-pyrazolone will be generated from the adduct in acetic acid (acidic condition), whereas dimethyl indole-2,3-dicarboxylate is produced in xylene (neutral condition) and 2-hydroxy-3-anilino-4-carbomethoxy-quinoline is yielded in pyridine (basic condition). The latter can be further converted into 2,3-dihydroquinoline upon decarboxylation and hydrolysis." This reaction has been extended to heat the 1 1 adduct in picoline. ... 

Deoxyalloxazines. 6-Anilino -4-hydroxy -5-p- nitrophenylazo -2- phenylpyrimidine heated 3 hrs. at 130-140° with coned. H2SO4 in glacial acetic acid 2-phenyl-2-deoxyalloxazine. Y 83%. F. e. s. F. Yoneda et al., Chem. Commun. 1971, 23. 

Methylmercapto-4,5-trimethylene-l,2-dithiolium iodide warmed gently with aniline and methanol until a clear soln. results, then neutralized with glacial acetic acid methyl 2-anilino-l-cyclopentenedithiocarboxylate. Y 64%. F. e., also with other nucleophilic agents, s. R. Mayer and H. Hartmann, B. 97, 1886 (1964). 

Similar to the nucleobase-calixarene cmijugates described above, Shi et al. designed a caUx[4]arene derivative with a uracil moiety at the upper rim by coupling uracil acetic acid directly to a mono-anilino caUx[4]arene. The obtained It—A isotherms again indicate the formation of supramolecular complexes at the air-water interface, that rely on the base pairing between uracil and adenine moieties. Furthermore ESl-MS experiments showed that the uracil calixarene conjugate is able to recognize adenine and adenosine from other nucleotides and bases [36],... 

Benzaldehyde and a little acetic acid added to an ethanolic soln. of 3-(o-amino-anilino)-5,5-dimethyl-2-cyclohexen-l-one, and allowed to stand 1 hr. at room temp. 3,3-dimethyl-2,3,4,5,10,ll-hexahydro-ll-phenyl-lH-dibenzo[b,e][l,4]di-azepin-l-one. Y 94.3%. F. e, s. S. Miyano and N. Abe, Chem. Pharm. Bull. 20, 1588 (1972). 

Embelin heated 3 hrs. at 100° with aniline in glacial acetic acid 5-anilino-2-hydroxy-3-undecyl-l,4-benzoquinone. Y 98%. F. e. s. B. S. Joshi and V.N.Kamat, Indian J. Chem. 13, 795 (1975). 

Benzo-l,4-thiazines and Related Compounds.— The chemical behaviour of the Vilsmeier product (111), derived from l,4-benzothiazin-3(4H)-one, has been the subject of detailed studies. Hydrolysis under different conditions affords the acid (112), the aldehyde (114), or the chloro-aldehyde (113), depending on the method of hydrolysis. Treatment of the perchlorate of (111) with DMSO leads to the displacement of the chlorine atom to give the dimethylsulphoxonium derivative (115), while reaction with pyridine proceeds with selective attack at the aminomethylene function, yielding the pyridinium salt (116). This latter reacts readily with aniline in acetic acid medium to give, along with 2-formyl-3-anilino-l,4-benzothiazine (117), the anilinomethylene derivative (120), whose formation probably involves an intramolecular rearrangement of the intermediate pyridinium salt (118), as depicted. 

Another category Ic indole synthesis involves cyclization of a-anilino aldehydes or ketones under the influence of protonic or Lewis acids. This corresponds to retro.synthetic path d in Scheme 4.1. Considerable work on such reactions was done in the early 1960s by Julia and co-workers. The most successful examples involved alkylation of anilines with y-haloacetoacetic esters or amides. For example, heating IV-substituted anilines with ethyl 4-bromoacetoacetate followed by cyclization w ith ZnClj gave indole-3-acetate esterfi]. Additional examples are given in Table 4.3. 

Preparation of 2 -Anilino-6 - [N- (3-bromopropyl) -N-ethylaminoJ-3 -methylfluoran (89). To a mixture of 2 -anilino-6 -[/V-ethyl-Af-( 3-methoxy-propyl)amino]-3 -methylfluoran (0.1 mol) and 48% hydrobromic acid (150 ml) was added dropwise concentrated sulfuric acid (20 ml) with vigorous stirring. Then, the resulting mixture was stirred at 110-115 °C for 1 h, poured into ice water (1000ml), and made alkaline by aqueous sodium hydroxide. The pale violet precipitate was filtered off, and recrystallized from ethyl acetate-isopropanol to give 2 -anilino-6 -[/V-(3-bromopropyl)-,V-ethylamino]-3 -methylfluoran in 96% yield, mp 160-162 °C. 

Amino-5-methylamino-l,2,4-thiadiazole similarly gives a 3-toluene-p-sulfonamido111,122 (237) and a monobenzamido derivative (for structure, see ref. 122) an excess of the appropriate reagent yields non-acidic di- and tri-substitution products, the latter probably of structure 239. With acetic anhydride, however, acylation terminates with the formation of the 3-monoacyl derivative.111,122 Similar observations areon record concerning 3-amino-5-anilino-1,2,4-thiadiazole86 the only anomalous observation is the ability of this compound to form di- and tri-acetyl derivatives.58... 

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