Anilines isopropylation

In a similar way the use of the 2-methyl-3-isothiocyanato-4-thiocyanato-hept-3-ene (252) prepared from thiocyanogen and the oxoal-kylene phosphorane (251) yields the 2-anilino-4-propyl-5-isopropyl-thiazole (253) by condensation with aniline (Scheme 128). 

This residue is dissolved in isopropyl alcohol and 1 gram N-bis-chloroethyl-aniline is added to it. The mixture is refluxed for 3 hours. The solvent is removed at a reduced pressure, the residue is treated with 50% potassium carbonate, and extracted with ether. By treating with ethereal hydrochloric acid, 2-N -m-chlorophenylpiperazino-propyl-s-triazole-[4,3-al-pyridine-3-one hydrochloride is precipitated MP 223°C. 

Baltrop and Bunce (Ref 20) employed a variety of radiation wavelengths, nitrocompds and solvents. For wavelengths less than 2900A, aniline was the main product, while above 2900A, bimolecular species such as azobenzene predominated. Since oxygen had little effect on aniline production, expts were performed in the presence of oxygen. For nitrobenzene in isopropyl alcohol, no azoxybenzene was produced as with Hurley and Testa (See above Ref 17). They concluded that the excited state abstracts H-atoms, and suggest that the nitrobenzene triplet is in tt, ti, and that nitrosobenzene is an unobserved intermediate... 

Benzaldehyde, 4-(l,l-dimethylethyl)- [Benzaldehyde, 4-rerf-butyl-], 55, 10 Benzaldehyde, 4 (1-methylethyl- [Benzaldehyde, 4 isopropyl ], 55, 10 Benzenamine, 2-bromo- [Aniline, 2 bromo ], p-bronnnation of, 55, 23 Benzenamine, 3-bromo- [Aniline, 3-bromo-], p-bromination of, 55, 23 BENZENAMINE, 4-bromo-yV,V-dimethyl-... 

The following liquids may be used (boiling points are given in parentheses) — chlorobenzene (132-3°) bromobenzene (155°) p-cymene (176°) o-dichloro-benzene (180°) aniline (184°) methyl benzoate (200°) tetralin (207°) ethyl benzoate (212°) 1 2 4-trichlorobenzene (213°) isopropyl benzoate (218°) methyl salicylate (223°) n-propyl benzoate (231°) diethyleneglycol (244°) -butyl benzoate (250°) diphenyl (255°) diphenyl ether (259°) dimethyl phthalate (282°) diethyl phthalate (296°) diphenylamine (302°) benzophenone (305)° benzyl benzoate (316°). 

Process development of the synthesis of iodoaniline 28 began with an improved synthesis of l-(4 -aminobenzyl)-l,2,4-triazole (6) (Scheme 4.7), which was prepared in the medicinal chemistry synthesis, albeit with poor regioselectivity (Scheme 4.1). We found that this aniline intermediate 6 could be readily prepared in three steps in >90% overall yield from 4-amino-l,2,4-triazole (30) and 4-nitrobenzyl bromide (4) based on a modified literature procedure [9]. The condensation of 30 and 4 in isopropyl alcohol followed by deamination gave the nitro... 

Dimethyl and diethyl phosphorofluoridate were hydrolysed much more quickly, the order being Me>Et>Pr complete hydrolysis of the ethyl ester took about 4 hr. Small quantities of the di-isopropyl, but not the diethyl ester, could be steam-distilled. Bi-isopropyl phosphorochloridate can be readily identified by allowing it to react with aniline to give the crystalline phenylphosphoramidate ... 

Di-isopropyl phosphorofluoridate does not, like the phosphoro-chloridate, give the anilinophosphonate on treatment with aniline. 

It has not yet been determined which structure [3] or [3 ] the triazoline has. The reaction mechanism of triazoline formation proposed by P.Scheiner, suggests that the structure may be 5-isopropyl-l-phenyl-A -i,3-triazoline(structure[3]). This conclusion was also supported by the fact that 3-methy 1-2-butylidene-aniline[5] was obtained by the decomposition of the triazoline (vide infra). 

Water was used as the catalyst phase for the palladiiun complex of TPPTS and toluene or an excess of the substrate anihne served as the non-polar product phase. To determine an appropriate solvent system cloud titrations were performed at 90 °C, 60 °C, 40 °C and 25 °C. A solution of 4-chloro-nitroben-zene in aniline and water were mixed in a weight ratio of 1 1 and semi-polar solvents were added as a mediator until a homogeneous solution was formed. As the mediator the following solvents were apphed methanol, ethanol, isopropyl alcohol, n-butanol, DMF, DMSO, ethylene glycol, N-methylpyrrohdone (NMP), 1.4-dioxane and acetonitrile. The cloud titrations were repeated whereby the substrate 4-chloro-nitrobenzene was replaced with the product 4-nitrodiphenylamine. In all cases more of the semi-polar mediator is required for the product mixture at 25 °C than for the reaction mixture at 60 °C to obtain a clear solution. 

The phosphate method has not been synthetically useful for alkylation of anilines of low basicity such as -nitro- or p-trifluoroaniline. Only monoalkylation occurs in introducing branched-chain alkyl groups such as isopropyl. Use of this method for alkylation of aliphatic amines has not been reported. 

Note May contain acetone, aniline, 2-methylphenol, or ethyl acetate to prevent corrosion with aluminum, iron, and zinc. To prevent acid formation, stabilizers added to tetrachloroethylene may include tert-butylglycidyl ether, diallylamine, 2,3-epoxypropyl isopropyl ether, diisopropylamine, 4-methylmorpholine, diallylamine, tripropylene, cyclohexene oxide, and benzotriazole. 

Acetamido-4-amino-6-chloro-s-triazine, see Atrazine Acetanilide, see Aniline, Chlorobenzene, Vinclozolin Acetic acid, see Acenaphthene, Acetaldehyde, Acetic anhydride. Acetone, Acetonitrile, Acrolein, Acrylonitrile, Aldicarb. Amyl acetate, sec-Amyl acetate, Bis(2-ethylhexyl) phthalate. Butyl acetate, sec-Butyl acetate, ferf-Butyl acetate, 2-Chlorophenol, Diazinon. 2,4-Dimethylphenol, 2,4-Dinitrophenol, 2,4-Dinitrotoluene, 1,4-Dioxane, 1,2-Diphenylhydrazine, Esfenvalerate. Ethyl acetate, Flucvthrinate. Formic acid, sec-Hexyl acetate. Isopropyl acetate, Isoamyl acetate. Isobutyl acetate, Methanol. Methyl acetate. 2-Methvl-2-butene. Methyl ferf-butvl ether. Methyl cellosolve acetate. 2-Methvlphenol. Methomvl. 4-Nitrophenol, Pentachlorophenol, Phenol. Propyl acetate. 1,1,1-Trichloroethane, Vinyl acetate. Vinyl chloride Acetoacetic acid, see Mevinphos Acetone, see Acrolein. Acrylonitrile. Atrazine. Butane. 

Isopropyl salicylic acid, see Isofenphos p-Ketoadipic acid, see Aniline, Diethyl phthalate, Hydroquinone... 

The solvents most commonly employed are water, ethyl and methyl alcohol, ether, benzene, petroleum ether, acetone, glacial acetic acid also two or three solvents may be mixed to get the desired effect as described later. If you still cannot dissolve the compound, try some of these chloroform, carbon disulfide, carbon tetrachloride, ethyl acetate, pyridine, hydrochloric acid, sulfuric acid (acids are usually diluted first), nitrobenzene, aniline, phenol, dioxan, ethylene dichloride, di, tri, tetrachloroethylene, tetrachloroethane, dichloroethyl ether, cyclohexane, cyclohexanol, tetralin, decalin, triacetin, ethylene glycol and its esters and ethers, butyl alcohol, diacetone alcohol, ethyl lactate, isopropyl ether, etc. 

Use of a large, lipophilic nitrogenous component results in a 1idocaine like, local anesthetic type cardiac anti-arrhythmic drug, lorcainide (20). Synthesis begins with the Schiff s base (1 ) derived by reaction of p-chloro-aniline and borohydride followed by acylation with phenyl acetyl chloride produces amide 1 . Selective hydrolysis with HBr followed by alkylation with isopropyl bromide completes the synthesis of lorcainide (20). ... 

Substituted anilines behave similarly to the phenols, although relatively little data are available. A-phenyl-iV -isopropyl-p-phenylenediamine is an efficient inhibitor in the polymerization of styrene only in the presence of oxygen [Winkler and Nauman, 1988], However, the effectiveness of phenothiazine as an inhibitor in the polymerization of acrylic acid is independent of oxygen [Levy, 1985],... 

Fusion of 2-methylpyrido[2,3- [l>3]oxazin -one 555 with ammonium acetate, hydrazine hydrate, benzylamine, and aniline in the presence of anhydrous zinc chloride at 150-160 °C gave the pyrido[2,3-. Also, amination of the 2-isopropyl or isobutyl analogues of 555 (R = = H) with benzylamine in ethylene glycol... 

Bei der Reaktion von Diisopropylamin mit l-Chlor-2,4-dinitro-benzol in Benzol bei 60° entsteht das erwartete N,N-Diisopropyl-2,4-dinitro-anilin nur in sehr geringer Ausbeute als Hauptprodukt entsteht das nur eine Isopropyl-Gruppe enthaltende 2,4-Dinitro-N-iso-propyl-anilin neben einer geringeren Menge an 2,4-Dinitro-N propyl-anilin1. Ahnliche Er-gebnisse erhalt man mit dem entsprechenden Aryl-fluorid und -bromid sowie bei Durch-fiihrung der Reaktion in Methanol oder Dimethyl-sulfoxid. 

QrHH [OberschuB an Aceton] Na[BH,]/H3C - COONa 3 H20/ H3C-COOH/H20/C2H5OH N-Isopropyl-anilin 91 5... 

CsH5 H Cli, N-Isopropyl-an ilin N-Isopropyl-N-methyl-anilin 74 77 (Schmp. 89-90°) (Schmp. 43-44°) ... 

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