Amines sulfation reactions

In the first case (22), almost stoichiometric amounts of sulfuric acid or chlorosulfonic acid are used. The amine sulfate or the amine chlorosulfate is, first, formed and heated to about 180 or 130°C, respectively, to rearrange the salt. The introduction of the sulfonic acid group occurs only in the ortho position, and an almost quantitative amount of l-aminoanthraquinone-2-sulfonic acid is obtained. On the other hand, the use of oleum (23) requires a large excess of SO to complete the reaction, and inevitably produces over-sulfonated compound such as l-amino-anthraquinone-2,4-disulfonic acid. Addition of sodium sulfate reduces the byproduct to a certain extent. Improved processes have been proposed to make the isolation of the intermediate (19) uimecessary (24,25). 

Lithiation of dibenzofuran with butyllithium and mercuration both occur at the 4-position. Thallation occurs at the 2-position, however (57IZV1391). The mercury and thallium derivatives serve as a source of the iodo compounds by reaction with iodine. Bromodibenzofurans undergo bromine/lithium exchange with butyllithium and the derived lithio compounds may be converted into phenols by reaction with molecular oxygen in the presence of a Grignard reagent, into amines by reaction with O-methylhydroxylamine, into sulfinic acids by reaction with sulfur dioxide, into carboxylic acids by reaction with carbon dioxide and into methyl derivatives by reaction with methyl sulfate (Scheme 100). This last reaction... 

Catalytic cyclodehydrogenation of 5-amino-2-ethylthiophenol affords 6-aminobenzo[6]thiophene.239,241 6-Acetamido-2,3-di-bromo-,77 6-acetamido-2-bromo-3-methyl-,102 6-acetamido-3-bromo-2-methyl-,102 and 6-acetamido-3-bromobenzo[f>]thiophene107 may be obtained from the corresponding 6-acetyl compound by means of the Schmidt reaction. In some cases the 6-acetamido compound is accompanied by a smaller amount of the amine sulfate.102,107 6-Aminobenzo[6]thiophene may be converted into 6-chloro- or 6-cyanobenzo[6]thiophene by means of the Sandmeyer reaction.241... 

A solution of 20 g. (0.165 mole) of m-xylidine in 200 g. of concentrated sulfuric acid is cooled to 5°, and 16.5 g. of concentrated nitric acid is added slowly with stirring. During this operation and for an additional 30-minute stirring period, the temperature of the reaction mixture is held below 15°. Pouring the mixture on crushed ice precipitates the amine sulfate, which is separated by filtration. The solid is treated with 10% aqueous sodium carbonate solution, and the resulting free amine is recrystallized from a 50% aqueous ethanol solution. The yield of 2,4-dimethyl-5-nitroaniline is 23 g. (84%), and the product melts at 123-124°. 

N-Methyl-N-methoxycarbamoyl chloride made by phos-genation of methoxy methyl amine hydrochloride is a very useful intermediate for the synthesis of N-methoxy ureas herbicides. However, we found the method to be unsatisfactory for the production on a large scale, because of rather low yields and also of technical difficulties. To overcome these problems, we developed a new procedure based on the reaction of phosgene with methoxy methyl amine sulfate as depicted in scheme 124. Sulfuric acid formed is easily removed by decantation (Ref. 177). 

Figure 13.IS. Major sulfation reactions involving primary and secondary alcohols, phenols, hydroxy-lamines and hydroxylamides, and amines.

The oxime is obtained by the action of hydroxylamine hydrogen sulfate on cydododecanone. This operation takes place in a solvent that is immisdble with water or with concentrated sulfuric add, which are used in the next step. The most widely used solvent is isopropylcydohexane (or hydrocumene) which dissolves the oxime at the reaction temperature of 100 G Conversion is practically quantitative. It takes place in a series of reactors equipped with effective agitators, into which aqueous solutions of hydroxyl-amine sulfate are introduced, together with ammonia to keep the pH about 7. The effluent is cooled aad settled. The aqueous layer containing ammonium Sulfate is removed. The organic phase is washed with concentrated sulfuric add. The oxime sulfate solution... 

By contrast, the —OSO3H groups of aminoalkyl hydrogen sulfates can readily be replaced by reaction with ammonia or amines. The reaction of ethanolamine with aminoethyl hydrogen sulfate thus yields hydroxy-cthyl-ethylenediamine. 

Dissolve 0.1 g of an amine in 2 mL of water to which 8 drops of concentrated sulfuric acid have been added. Use a large test tube. Often, a considerable amount of solid forms in the reaction of an amine with sulfuric acid. This solid is likely to be the amine sulfate salt. Add about 4 mL of water to help dissolve the salt. Any remaining solid will not interfere with the results of this test. Cool the solution to 5°C or less in an ice bath. Also cool 2 mL of 10% aqueous sodium nitrite in another test tube. In a third test tube, prepare a solution of 0.1 g j8-naphthol in 2 mL of aqueous 10% sodium hydroxide, and place it in an ice bath to cool. Add the cold sodium nitrite solution, drop by drop while shaking, to the cooled solution of the amine. Look for bubbles of nitrogen gas. Be careful not to confuse the evolution of the colorless nitrogen gas with an evolution of brown nitrogen oxide gas. Substantial evolution of gas at 5°C or below indicates a primary aliphatic amine, RNH2. The formation of a yellow oil or a yellow solid usually indicates a secondary amine, RjNH. Either tertiary amines do not react, or they behave like secondary amines. 

The amines are isolated either by liberation from the crystalline amine sulfate, or by steam distillation of the alkalized water extract of the reaction mixture, or by ether extraction of the alkaline solution. In the preparation of amino acids the isolation may be effected by forming an appropriate derivative such as a picrate or phosphotungstate. ... 

Wheieas the BPO—DMA ledox system works well for curing of unsaturated polyester blends, it is not a very effective system for initiating vinyl monomer polymerizations, and therefore it generally is not used in such appHcations (34). However, combinations of amines (eg, DMA) and acyl sulfonyl peroxides (eg, ACSP) are very effective initiator systems at 0°C for high conversion suspension polymerizations of vinyl chloride (35). BPO has also been used in combination with ferrous ammonium sulfate to initiate emulsion polymerizations of vinyl monomers via a redox reaction (36). 

Ma.nufa.cture. Nickel carbonyl can be prepared by the direct combination of carbon monoxide and metallic nickel (77). The presence of sulfur, the surface area, and the surface activity of the nickel affect the formation of nickel carbonyl (78). The thermodynamics of formation and reaction are documented (79). Two commercial processes are used for large-scale production (80). An atmospheric method, whereby carbon monoxide is passed over nickel sulfide and freshly reduced nickel metal, is used in the United Kingdom to produce pure nickel carbonyl (81). The second method, used in Canada, involves high pressure CO in the formation of iron and nickel carbonyls the two are separated by distillation (81). Very high pressure CO is required for the formation of cobalt carbonyl and a method has been described where the mixed carbonyls are scmbbed with ammonia or an amine and the cobalt is extracted as the ammine carbonyl (82). A discontinued commercial process in the United States involved the reaction of carbon monoxide with nickel sulfate solution. 

Ritter Reaction (Method 4). A small but important class of amines are manufactured by the Ritter reaction. These are the amines in which the nitrogen atom is adjacent to a tertiary alkyl group. In the Ritter reaction a substituted olefin such as isobutylene reacts with hydrogen cyanide under acidic conditions (12). The resulting formamide is then hydroly2ed to the parent primary amine. Typically sulfuric acid is used in this transformation of an olefin to an amine. Stoichiometric quantities of sulfate salts are produced along with the desired amine. 

Alkali moderation of supported precious metal catalysts reduces secondary amine formation and generation of ammonia (18). Ammonia in the reaction medium inhibits Rh, but not Ru precious metal catalyst. More secondary amine results from use of more polar protic solvents, CH OH > C2H5OH > Lithium hydroxide is the most effective alkah promoter (19), reducing secondary amine formation and hydrogenolysis. The general order of catalyst procUvity toward secondary amine formation is Pt > Pd Ru > Rh (20). Rhodium s catalyst support contribution to secondary amine formation decreases ia the order carbon > alumina > barium carbonate > barium sulfate > calcium carbonate. 

Other Applications. Hydroxylamine-O-sulfonic acid [2950-43-8] h.2is many applications in the area of organic synthesis. The use of this material for organic transformations has been thoroughly reviewed (125,126). The preparation of the acid involves the reaction of hydroxjlamine [5470-11-1] with oleum in the presence of ammonium sulfate [7783-20-2] (127). The acid has found appHcation in the preparation of hydra2ines from amines, aUphatic amines from activated methylene compounds, aromatic amines from activated aromatic compounds, amides from esters, and oximes. It is also an important reagent in reductive deamination and specialty nitrile production. 

SuIfona.tlon, Sulfonation is a common reaction with dialkyl sulfates, either by slow decomposition on heating with the release of SO or by attack at the sulfur end of the O—S bond (63). Reaction products are usually the dimethyl ether, methanol, sulfonic acid, and methyl sulfonates, corresponding to both routes. Reactive aromatics are commonly those with higher reactivity to electrophilic substitution at temperatures > 100° C. Tn phenylamine, diphenylmethylamine, anisole, and diphenyl ether exhibit ring sulfonation at 150—160°C, 140°C, 155—160°C, and 180—190°C, respectively, but diphenyl ketone and benzyl methyl ether do not react up to 190°C. Diphenyl amine methylates and then sulfonates. Catalysis of sulfonation of anthraquinone by dimethyl sulfate occurs with thaHium(III) oxide or mercury(II) oxide at 170°C. Alkyl interchange also gives sulfation. 

OC-Hydroxycarboxylic Acid Complexes. Water-soluble titanium lactate complexes can be prepared by reactions of an aqueous solution of a titanium salt, such as TiCl, titanyl sulfate, or titanyl nitrate, with calcium, strontium, or barium lactate. The insoluble metal sulfate is filtered off and the filtrate neutralized using an alkaline metal hydroxide or carbonate, ammonium hydroxide, amine, or alkanolamine (78,79). Similar solutions of titanium lactate, malate, tartrate, and citrate can be produced by hydrolyzation of titanium salts, such as TiCl, in strongly (>pH 10) alkaline water isolation of the... 

Sulfation. Sulfated castor oil, also known as turkey-red oil, represents one of the earliest chemical derivatives of castor oil. The traditional method of preparing turkey-red oil is to add concentrated sulfuric acid at a controlled rate to castor oil over a period of several hours with constant cooling and agitation of the reaction mass to maintain a temperature of 25—30°C. After acid addition is complete, the reaction mass is washed then neutralized using an alkaU solution or an amine. 

The properties of 1,1-dichloroethane are Hsted ia Table 1. 1,1-Dichloroethane decomposes at 356—453°C by a homogeneous first-order dehydrochlofination, giving vinyl chloride and hydrogen chloride (1,2). Dehydrochlofination can also occur on activated alumina (3,4), magnesium sulfate, or potassium carbonate (5). Dehydrochlofination ia the presence of anhydrous aluminum chloride (6) proceeds readily. The 48-h accelerated oxidation test with 1,1-dichloroethane at reflux temperatures gives a 0.025% yield of hydrogen chloride as compared to 0.4% HCl for trichloroethylene and 0.6% HCl for tetrachloroethylene. Reaction with an amine gives low yields of chloride ion and the dimer 2,3-dichlorobutane, CH CHCICHCICH. 2-Methyl-l,3-dioxaindan [14046-39-0] can be prepared by a reaction of catechol [120-80-9] with 1,1-dichloroethane (7). 

Bake sulfonation is an important variant of the normal sulfonation procedure. The reaction is restricted to aromatic amines, the sulfate salts of which ate prepared and heated (dry) at a temperature of approximately 200°C in vacuo. The sulfonic acid group migrates to the ortho or para positions of the amine to give a mixture of orthanilic acid [88-21-1] and sulfanilic acid [121 -57-3] respectively. This tendency is also apparent in polynuclear systems so that 1-naphthylamine gives 1-naphthy1amine-4-su1fonic acid. 

Ethylamines. Mono-, di-, and triethylamines, produced by catalytic reaction of ethanol with ammonia (330), are a significant outlet for ethanol. The vapor-phase continuous process takes place at 1.38 MPa (13.6 atm) and 150—220°C over a nickel catalyst supported on alumina, siUca, or sihca—alumina. In this reductive amination under a hydrogen atmosphere, the ratio of the mono-, di-, and triethylamine product can be controlled by recycling the unwanted products. Other catalysts used include phosphoric acid and derivatives, copper and iron chlorides, sulfates, and oxides in the presence of acids or alkaline salts (331). Piperidine can be ethylated with ethanol in the presence of Raney nickel catalyst at 200°C and 10.3 MPa (102 atm), to give W-ethylpiperidine [766-09-6] (332). 

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