Dimethylaniline phosgene

Aldehydes N,N -Carbonylimidazole. Ethoxymethyleneaniline. Ethyleneimine. For-maldoxime. Imidazole. N-Methyl-N-phenylcarbamyl chloride. p-Nitro-N.N-dimethylaniline. Phosgene. Silver tosylate. Sodium ethoxide. Sodium hypophosphite. Sodium 2-nitropro-panenitronate. Trimethylamine oxide. 

Dimethylaniline is also used for the preparation of tetra-methyldiaminobenzophenone(Michler s compound), which forms the basis of many colouring matters, and is obtained by acting upon dimethylaniline with phosgene (see p. 314))... 

Treatment of 2,6-dimethylaniline (121) with phosgene and triethylamine affords the corre-S]ionding isocyanate (122). Condensation of that reactive intermediate with N-isopropylpropyl-cne-1,3-diamine leads to formation of urea 123. This product, recainam (123), acts as membrane Stabilizing agent and thus exhibits both local anesthetic and antiarrhythmic activity [30]. 

A cooled 10% solution of 1 mol of phosgene in toluene was added with stirring to a cooled solution of 1 mol of 2-methyl-2-propyl-1,3-propanediol and 2 mols of dimethylaniline also dissolved in toluene, at such a rate that the temperature of the mixture was maintained at about 25°C. The mixture was allowed to remain at this temperature for several hours, then... 

Michler s ketone is prepared industrially by the interaction of phosgene (COClg) and dimethylaniline. 

The compound is obtained from Michler ketone (128) and dimethylaniline in the presence of POCl3. Michler ketone in turn is synthesized from dimethylaniline (DMA) and phosgene with zinc chloride ... 

The formation of the acid dye bmzaurin takes place in a quite analogous manner. p-Tetramethyldiaminobenzophenone (Michler s ketone), which is prepared technically from dimethylaniline and phosgene, can, like benzaldehyde, be condensed with dimethylaniline in the presence of phosphorus oxychloride. In this case, however, it is not a methane derivative, a leuco-compound, which is obtained, but, as the equation shows, the carbinol stage is at once reached. As will soon be shown, however, this stage in acid solution is equivalent to the formation of the dye. 

Chlorination of methyl 2,3(l >4//)-quinoxalinedion-5-ylcarboxylate was efficiently achieved by reaction with phosgene in DMF at room temperature in 90% yield <1999JHC1271>. Other procedures using phosphoryl chloride alone or with phosphoms pentachloride or A, A -dimethylaniline decrease remarkably the yields of dichloroquinoxaline. 

Centr 2 was first prepd by Michler(Refs 1 2) on passing phosgene thru boiling dimethylaniline. Michler 8t Zimmermann(Refs 1 3) prepd it by heating methylphenylcarbamyl chloride with methylaniline some Zn dust. Dains et al(Refs 1 4) prepd it by heating equimolecular quantities of N-methyl-N,N -diphenylthiourea with methylphenylcarbamyl chloride at 150°. Mailhe(Refs 1 7) prepd it by passing vapor of N methyiformanilide(yel, viscous oil, bp 286°) over finely divided nickel at 380 400°... 

A solution of 32 g (0.30 mol) phosgene in 200 ml benzene is added dropwise at 30°C to a stirred solution of 53.5 g (0.32 mol) 3-o-toloxy-l,2-propanediol in 400 ml benzene. The mixture is stirred for an hour after the addition is completed, and a solution of 39 g of dimethylaniline in 100 ml benzene is then added, and stirring continued for a half-hour. Ice water (about one-third volume) is then added, and the benzene layer formed is separated and stirred with 500 mi concentrated ammonia at 5°C for six hours. The precipitated solid (weighing about 55 g) is recovered and recrystallized from water. The product thus obtained in a yield of about 53 g is 3-(o-toloxy)-2-hydroxypropyl carbamate it is a crystalline solid melting at about 93°C, and having a lower water-solubility and higher oil-solubility than 3-o-toloxy-l,2-propanediol. 

The manufacture of crystal violet (1), however, is a special case which does not involve the isolation of the intermediate Michler s ketone (Fig. 3). Thus, phosgene is treated with excess dimethylaniline in the presence of zinc chloride. Under these conditions, the highly reactive intermediate "ketone dichloride" is formed in good yield this intermediate further condenses with another mole of dimethylaniline to give the dye. 

The condensation of dimethylaniline with phosgene yields, besides the p,p product, considerable quantites of the o,o and o,p compounds. The phosgene necessary for the reaction is taken from a phosgene cylinder, 3 and a small excess of dimethylaniline is used in order to be sure that all of the hydrogen chloride formed is taken up. 

Direct introduction of the carboxyl group into an aromatic ring is accomplished with urea hydrochloride, phosgene, oxalyl chloride, or carbon dioxide. Carboxylation of benzene is effected in 15-58% yields by treating with liquid phosgene and aluminum chloride. No catalyst is required in the conversion of dimethylaniline and phosgene to p-dimethyl-aminobenzoic acid (50%). 9-Anthroic acid (67%) is prepared from anthracene by heating to 240° with oxalyl chloride and nitrobenzene. ... 

The reaction of phosgene with dimethylaniline when carried out in the presence of aluminium trichloride or zinc chloride gives Crystal Violet,... 

Like phosgene, as in the decomposition by heat or in presence of aluminium chloride thus it reacts with dimethylaniline forming Crystal Violet. ... 

Dimethylamidobenzoic chloride is produced by action of phosgene on dimethylaniline ... 

This is effected on a large scale in one operation, phosgene (COCI2) being allowed to act on dimethylaniline in presence of... 

Preparation.1 The carbonate (1) is prepared in 65-70% yield by treatment of benzoin (1.0 eq.) and phosgene (1.1 eq.) in benzene with distilled N,N-dimethylaniline at 5°. After stirring overnight at room temperature the amine hydrochloride is filtered, and the filtrate refluxed for 3 hr. to cyclize the initially formed chloroformate. 

Derivation From dimethylaniline by reaction with phosgene. 

When phosgene is combined with A ,iV-dimethyianiiine in the presence of aluminium(III) chloride, Michler s ketone, 4,4 -bis(dimethylamino)benzophenone, is produced (see Section 10.2.1.1), which undergoes further reaction with lV,N-dimethylaniline (also in the presence of aluminium(ni) chloride or POCij) to give the colouring material "crystal violet", used in the production of methyl violet indicator paper. When Michler s ketone is warmed with Ai-phenyl-1-naphthylamine in the presence of POCI3, Victoria blue (4.13) is formed, which is used as a dye for natural fibres [718a]. 

Desulfurization of petroleum feedstock (FBR), catalytic cracking (MBR or FI BR), hydrodewaxing (FBR), steam reforming of methane or naphtha (FBR), water-gas shift (CO conversion) reaction (FBR-A), ammonia synthesis (FBR-A), methanol from synthesis gas (FBR), oxidation of sulfur dioxide (FBR-A), isomerization of xylenes (FBR-A), catalytic reforming of naphtha (FBR-A), reduction of nitrobenzene to aniline (FBR), butadiene from n-butanes (FBR-A), ethylbenzene by alkylation of benzene (FBR), dehydrogenation of ethylbenzene to styrene (FBR), methyl ethyl ketone from sec-butyl alcohol (by dehydrogenation) (FBR), formaldehyde from methanol (FBR), disproportionation of toluene (FBR-A), dehydration of ethanol (FBR-A), dimethylaniline from aniline and methanol (FBR), vinyl chloride from acetone (FBR), vinyl acetate from acetylene and acetic acid (FBR), phosgene from carbon monoxide (FBR), dichloroethane by oxichlorination of ethylene (FBR), oxidation of ethylene to ethylene oxide (FBR), oxidation of benzene to maleic anhydride (FBR), oxidation of toluene to benzaldehyde (FBR), phthalic anhydride from o-xylene (FBR), furane from butadiene (FBR), acrylonitrile by ammoxidation of propylene (FI BR)... 

Compounds of this type are usually prepared from the corresponding quinoxaline-2,3-diones. A variety of chlorinating reagents have been used, including phosphoryl chloride," phosgene," thionyl chloride, and mixtures of phosphoryl chloride with N,N-dimethylaniline or N,N-diethylaniline" " or phosphorus pentachloride." The reactions are normally carried out under reflux in an open vessel for periods of about... 

Examples acetophenone from benzene and acetic anhydride (2 molecules) Michler s ketone from dimethylaniline and phosgene (3 molecules) caoutchouc from isoprene (many molecules). 

In a Friedel-Crafts type of reaction phosgene leads to carboxylic acids or their chlorides or to ketones 603 p-(dimethylamino)benzoic acid, for instance, is obtained in 50% yield from dimethylaniline and phosgene without a catalyst 604... 

More recently it has almost always been recommended to use the combination dimethylformamide-phosgene (e.g., for formylation of A, -dimethyl-aniline828) or dimethylformamide-phosphoryl chloride derivatives of 1,2-methylenedioxybenzene836 and of thiophen,837 as well as azulene838 and ferrocene,839 have been formylated in this way, some of them in excellent yield. Organic Syntheses contains directions for formylation of indole (97% yield of the 3-carbaldehyde)840 and W,W-dimethylaniline (80-84% yield of the para-aldehyde).841 The following is a further example in detail ... 

Benzanilide and phosgene have been used to introduce a benzoyl group into dimethylaniline (85% yield) 828 and other acylations can be effected analogously, as when ethyl 8-(l-azulenyl)-8-oxooctanoate is obtained in 80% yield from azulene, ethyl 7-(Ar,Ar-dimethylcarbamoyl)heptanoate, and phos-phoryl chloride.855... 

The alkylation process enters into dye manufacture in two ways, because dyes may be formed from alkylated intermediates, or in a lesser numt>er of instances, an intermediate may be subjected to alkylation as a final step. For instance, dimethylaniline is condensed with phosgene to give tetra-methyldiaminobenzophenone (Michler s ketone). From this ketone are formed many dyes, such as crystal violet and Victoria blue. On the other hand, the alkylation process may be almost the last step in the manufacture of a dye, for example, when the disazostilbene dye, paper yellow 3G, is ethylated to give crysophenine G. 

An important substitution-product of benzophenone that is used in the dye-stuff industry is the tetramethyldiamino derivative, which is called Michler s ketone. It is made by heating dimethylaniline with phosgene in an autoclave —... 

Methyl-2- -propyl-l, 3-propane diol dissolved in toluene is condensed at 0°C with phosgene in the presence of dimethylaniline gives the chloroformate diester, which when subjected to ammonolysis yields meprobamate. 

Methyl-2-propyl-l, 3-propanediol is prepared by reacting diethyl methylpropyl malonate in ether in the presence of lithium aluminium hydride and then treated with dilute sulphuric acid. This on treatment with phosgene in toluene by means of dimethylaniline yields 2-methyl-2-propyl-3 -hydroxypropyl chlorocarbonate, which on reaction with n-butylamine forms 2-methyl-2-propyl-3-hydroxypropyl butylcarbamate. The resulting product on treatment with ethyl urethane in the presence of aluminium isopropoxide in boiling xylene yields ethanol during transesterification which is removed from the reaction mixture simultaneously and tybamate is obtained. 

---