Diisopropyl aniline

A simple acid-catalyzed condensation in methanol such as for 2,6-diisopropyl-aniline yielded no product. Another difference in behavior between this diimine and the one based upon 2,6-diisopropylaniline is observed in the reaction with (COD)PdCl2 or (COD)PdMeCl 2,3-bis(2,6-dibromo-4-methylphenyl)imine butane is inert toward these palladium catalyst precursors, whereas the alkyl-substituted... 

Fig. 3.4 Steric extension of 2,6-dibromo- (left), 2,6-diisopropyl-aniline (right) and overlay, front and side views.

Palladium catalysts with diimine ligands based on 2,6-diisopropyl aniline polymerize ethene to a rubbery, highly branched polyethene with low glass transition temperatures [12 a]. The interest in these materials results from their possible appheation as a rubber modifier in engineering plastics [3j,k]. However, the activity of the palladium catalysts is not satisfactory for technical use in a world scale plant We intended to improve the activity by increasing the Lewis acidity of the metal center by using relatively electron-deficient bromo phenyl diimine hgands. 

Ausnahmen sind die Synthesen des 4-Diisopropylamino-2,3-dimethyl-1 -phenyl-5-py-razolon aus Aceton und 4-Amino-2,3-dimethyl-l-phenyl-5-pyrazolon14 und die von N,N-Dialkyl-anilinen durch reduktive Aminierung von Alkanonen in Form ihrer Acetale mit Anilinen13 (vgl. S. 452). So erhalt man z.B. N,N-Diisopropyl-anilin aus 2,2-Dimethoxy-propan und Anilin iiber Palladium/Kohle (5%) (120 bar/50°) zu 56% d.Th. Mit zunehmender Kettenlange der Acetale sind die Reaktionsbedingungen auf 135-155° und 100 bar zu steigern15. 

Chlorocarbonyl isocyanate 135 has been employed to obtain a chlorocarbonyl urea 137 from 2,6-diisopropyl aniline 136 [91]. 

Diethyl aniline, 54 Diethylcarbaniazine citrate, 54 Diethyl carbamyl chloride, 54 Diethyl chlorophosphate, 54 Diethylene triamine, 54 Diethyl ether, 54 Di(2-ethylhexyl) phthalate, 54 Diethyl ketone, 54 Diethyl-p-phenylenediamine, 54 Diethyl phthalate, 54 Diethylstilbestrol, 55 Diethyl sulfate, 55 Diethyl zinc, 55 Difluoromethane chloride, 55 Digitoxin, 55 Diglycidyl ether, 55 Digoxin, 55 Diisobutyl ketone, 55 Diisopropylamine, 55 Diisopropyl ether, 55 DIKAMIN , 2,4-D, 55 DIKONIRT , 2,4-D, 55 Dimefox, 55 Dimethoate, 55 3,3 -Dimethoxybenzidine, 55 n,n-Dimethylacetamide, 56 Dimethylamine, 56 4-Dimethylaminoazobenzene, 56 Dimethylaminoethanol, 56 n,n-Dimethyl aniline, 56 7,12-Dimethylbenz[a]anthracene, 56 3,3 -Dimethylbenzidine, 56... 

A mixture of 65 parts 1 -[4,4-di-(4-fluoro-phenvl)butyl] -piperazine, 4.33 parts N-(2-chloro-acetyl)-2,6-dimethyl-aniline, 3.2 parts sodium carbonate, a few crystals of potassium iodide in 200 parts 4-methyl-2-pentanone is stirred and refluxed for 70 hours. After cooling there are added 70 parts water. The organic layer is separated, dried over potassium carbonate, filtered and evaporated. The oily residue is dissolved in 80 parts diisopropyl-ether and the solution is filtered hot. After cooling the filtrate at 0°C, the formed solid is filtered off and recystallized from 80 parts ether, yielding 1-[4,4-di-(4-fluoro-phenyl)butyl] -4-[(2,6-dimethyl-anilino-carbonvl)-mathyl] -piperazine MP 159°Cto 161°C. 

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. 

Die Aminolyse von Diisopropyl-(3-methyl-2-butcnyl)-phosphat mit sekundaren Aminen (z.B. N-Methyl-anilin) in Dirnethylformamid in Gegenwart von Diethylether-Trifluorbo-... 

Di-isopropyl 4 bromo aniline diafenthiuron Diisopropyl phosphorochloroido thioate see DIPCT Diketal sorbose dikegulac-sodium... 

The product from Step 1 (3.2mmol) was dissolved in 50ml CH2CI2 and treated with 1,T-carbonyldiimidazole (3.6 mmol) and aniline (4.4 mmol), stirred 18 hours, concentrated, and purified by chromatography on silica gel using diisopropyl ether/diethyl ether. Thereafter, the product was dissolved in 10 ml hot propan-2-ol and the solution acidified with ethereal HCl. The material crystallized upon trituration with ether and 0.897 g product isolated as dihydrochloride quarter hydrate, mp = 250-255 °C (dec.). Elemental analysis data supplied. 

Aniline (44 pL, 0.48mmol) was added at rt to a stirred soln of V)V -bis(tert-butoxycarbonyl)-6-nitro-l//-benzotriazole-l-carboximidamide (163 mg, 0.4 mmol) in dry CH2CI2 (2mL) at rt. After 2h, the mixture was diluted with diisopropyl ether (12 mL) and washed with 0.25 M aq KHSO4 (3mL), H2O (2x2mL), and brine (1 mL). The organic phase was dried (Na2S04), filtered, and concentrated. The crude product was purifi by flash chromatography (18 g silica gel, hexane/tert-butyl methylether 4 1) yield 134 mg (100%) mp 131-133 C lit.P 132-134 °C. 

Bromination. Active arenes such as phenols, aryl ethers, and anilines are brominated by ZrBr4 in the presence of diisopropyl azodicarboxylate in CH2CI2. A free para position is the preferred site for bromination. 

In plasma AES techniques several types of organic liquids can be aspirated directly into the plasma source. Suitable dilutants are hexanol, diisobutyl ketone, diisopropyl ketone, acetic acid, 2-butoxyethanol, diethyl sulfoxide, carbon tetrachloride, xylene, nitrobenzene, aniline, pyridine, benzyl alcohol, and tributyl phosphate. 

Electron-rich and ortho-substituted aryl chlorides were converted to the respective anilines in excellent yields within 1 h on a 1 mmol scale, emphasizing the exceptional activation in combination with the electron-rich phosphine. Another class of strong a-donors are N-heterocychc carbenes. Their Pd(0) complexes can undergo facile oxidative addition of aryl halides. Nolan et al. [44] used the SIPr ligand (SIPr = (l,3-bis(2,6-diisopropyl)phenyl-4,5-dihydroimidazol-2-ylidene), 19) for the Pd-catalyzed arylation of stericaUy encumbered anilines with stericaUy demanding aryl chlorides at room temperature (Scheme 13.66). 

In the same year, Shaughness/s group [24] reported a trineopentylphosphane (TNpP) (Figure 2.3) that, in combination with palladium (Pd2(dba)3 or Pd(OAc)2 at 1-2 mol%), affords a very effective catalyst for the coupling of stericaUy demanding aryl chlorides and bromides with sterically hindered anilines. Excellent yields have been obtained even with 2,6-diisopropyl substituents. It is believed that the conformational flexibility of the TNpP ligand (noncyclic) plays a key role to allow the catalyst to couple with the hindered substrates. 

N03Si2Ci5H29, Aniline, N-(trihydroxysilyl)-N-(trimethylsilyl)-2,6-diisopropyl-, 33 231 NS4ReC8H2o, Rhenale(l-), tetrathioper-, tetra-ethylammonium, 33 107 N2BrgMo3S7Ci6H4o, Molybdate(2-), heptasulli-dohexabromotri-, bis(tetiaethylammo-nium), 33 166... 

Se2eP4Rb4U4, Uranium, bis(selenido)tetrakis(di-selenido)-tetrakis(tetraselenophosphate)-tetra-, tetrarubidium, 33 128 S1N42C15H32, Aniline, N-(triaminosilyl)-N-(tri-methylsilyl)-2,6-diisopropyl-, 33 232 Si2N2SCi2H36, Sulfide, bis[bis(trimethylsilyl)-amino]-, 33 197... 

Benzyl alcohol at 155.4°C Tetrahydrofuran, acetone-carbon disulfide mixtures, methyl ethyl ketone Toluene, xylene, methylene chloride, ethylene chloride, perchloroethylene-acetone mixtures, 1,2-dichlorobenzene, tetrahydrofurfuryl alcohol, dioxane, acetone-oarbon disulfide mixtures, cyclopentanone, diisopropyl ketone, mesityl oxide, isophorone, dimethyl-formamide, nitrobenzene, hexamethyl-phosphoramide, tricresyl phosphate Aliphatic and aromatic hydrocarbons, vinyl chloride monomer, alcohols, glycols, aniline, acetone, carboxylic acids, acetic anhydride, esters, nitroparaffins, carbon disulfide, nonoxidizing mineral acids, concentrated alkalies... 

Some typical NMR spectra of ethylene propylene copolymers are shown in Figures 6.9 and 6.10. The technique has been used in various structural studies on copolymers. Thus Hashidzume and co-workers [61], in an investigation of the spontaneous copolymerisation of 2,6-diisopropyl-N-methylene aniline with phthalic anhydride or with itaconic anhydride, showed that in the case of polymerisation of 2,6-diisopropyl-N-methylene aniline and phthalic anhydride, the copolymer was formed by a coupling reaction of a zwitterion one to one adduct. Also in the case of copolymerisation of 2,6-diisopropyl-N-methylene aniline and itaconic anhydride, the copolymer is formed by the addition polymerisation through the C=C bond in the itaconic anhydride moiety. 

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