NITRO COMPOUNDS AND SULPHONIC ACIDS

DETERMINATION OF THE STRUCTURE OF AROMATIC COMPOUNDS. NITRO COMPOUNDS AND SULPHONIC ACIDS... 

Nitro, amino and sulphonic acid derivatives of alizarin are also dyes of various colors and are known as alizarin orange, alizarin maroon, alizarin red, etc. Also there is present in the madder root another dye compound known as puipurin which is 1-2-4-tri-hydroxy anthraqui-none. Isomeric tri-hydroxy anthraquinones are dyes also but it is interesting that in all of these poly-hydroxy anthraquinones which are dyes two of the hydroxyls are always in the 1-2 positions. 

Constitution.—The composition of naphthalene is represented by the formula CioHg. What is its constitution In the first place it is a hydrocarbon similar in its chemical properties to benzene and not to methane. It readily forms nitro and sulphonic acid derivatives and its hydroxyl derivatives are analogom to phenols, not to alcohols. It also yields hydrogen and halogen addition products like benzene. The true constitution of the compound has been established by reactions both of decomposition and of synthesis. 

The introduction of nitro- and sulphonic acid groups has been achieved also in excellent yields by rpio-substitution of 2a, while rpio-acylation gave the tetraacetyl derivative in only 42% yield . Calixarenes consisting of hydroquinone units have been exhaustively perbrominated to yield compounds 47 with two bromine atoms per phenolic unit. ... 

The substances formed in this way belong to important classes of compounds which will be discussed later. The nitro and sulphonic acid derivatives of the paraffins are usually made by other reactions. 

Thiophene possesses the characteristics of aromatic compounds it is converted into nitro compounds by nitric acid, into halogen derivatives by bromine and chlorine, into sulphonic acids by... 

Many substances which behave as acids in hydroxylic solvents exhibit basic properties in sulphuric acid. Thus most carboxylic acids are strong bases, forming the ion RCOOHJ, though reaction is incomplete for strong acids such as di- and tri-chloroacetic acids, which are thus weak bases in this solvent. Nitro-compounds, sulphones, and sulphonic acids also behave as weak bases, and it is in fact difficult to find substances which are soluble in sulphuric acid without detectable ionization. Since cryoscopic measurements lead only to the total number of solute particles, it is not possible to obtain quantitative measurements of base strength over a wide range, especially since there are complications caused by the self-dissociation of the solvent, and interionic effects, though small, must be taken into account. 

C. A typical aromatic amine. Best prepared by the prolonged action of concentrated ammonia solution at a high temperature upon anthraquinone-l-sulphonic acid in the presence of BaClj and by reduction of the corresponding nitro compound or by amination of the chloroanthraquinone. 

Anthraquinone can be brominated, chlorinated directly to the tetrachloro (I, 4, 5, 8-) stage, nitrated easily in the 1-position, but gives the 1,5-and 1,8-dinitro-derivalives on prolonged nitration the nitro groups in these compounds are easily displaced by neutral solutions of alkali sulphites yielding the corresponding sulphonic acids. Sulphonation with 20-30 % oleum gives the 2- 2,6- and 2,7-derivatives in the presence of Hg the 1- 1,5- and 1,8- derivatives are formed. 

Dilute sodium hydroxide solution. Carboxylic acids (RCOOH), sulphonic acids (RSO3H), phenols (ArOH), thiophenols (ArSH), mer-captans (RSH), imides (RCONHCOR), aryl sulphonamides (AxSOjNHj), arylsulphonyl derivatives of primary amines (AxSOjNHR), oximes (RCH=NOH), primary and secondary nitro compounds (RCH=NOOH and RjC=NOOH-oci forms), and some enols (e.g., of 1 3-diketones... 

The imides, primaiy and secondary nitro compounds, oximes and sulphon amides of Solubility Group III are weakly acidic nitrogen compounds they cannot be titrated satisfactorily with a standard alkaU nor do they exhibit the reactions characteristic of phenols. The neutral nitrogen compounds of Solubility Group VII include tertiary nitro compounds amides (simple and substituted) derivatives of aldehydes and ketones (hydrazones, semlcarb-azones, ete.) nitriles nitroso, azo, hydrazo and other Intermediate reduction products of aromatic nitro compounds. All the above nitrogen compounds, and also the sulphonamides of Solubility Group VII, respond, with few exceptions, to the same classification reactions (reduction and hydrolysis) and hence will be considered together. 

Sulphuric acid at 93% was added to p-nitrotoluene. The temperature reached 160°C due to a failure of the thermal control system. The sulphonic acid formed decomposed violently at this temperature. The post-accident investigation showed that the decomposition started between 160 and 190 C. In fourteen minutes the temperature rose to 190-224°C and in one minute and thirty seconds to 224-270°C. A large volume of gas was then released during the eruption. The phenomena caused by the decomposition of nitrated derivatives in the presence of sulphuric acid will be addressed several times. What these incidents have in common is the formation of large carbonised volumes. This phenomenon is common with sulphonic acids. The nitro group role is to destabilise intermediate compounds and final compounds and to generate... 

Anthraquinone-1-sulphonic acid is the traditional precursor of 1-aminoanthraquinone (6.8), the most important anthraquinone intermediate. Since it is expensive to eliminate mercury(II) ions from waste water, an alternative route via 1-nitroanthraquinone has been investigated. Nitration of anthraquinone gives, as well as the desired 1-nitro derivative, significant amounts of the 2-isomer together with 1,5- and 1,8-dinitroanthraquinones. Nevertheless, chemists at Sumitomo in Japan have optimised the nitration procedure with respect to both yield and purity of the 1-nitro compound. In particular, nitration is stopped when 80% of the anthraquinone has been substituted [5]. Nitration of anthraquinone derivatives is also of some significance. 

Salts have been prepared with optically active camphor sulphonic acids. These also are yellow crystalline bodies, but no resolution of the base has been effected. d-Camphoric acid, d-tartaric acid, and d-nitro-camphor compounds were also prepared, and again no resolution was effected. Hence it is concluded that the hydroxo- and nitroso-groups are probably in the 1-, 0-, or trans-position. 

Picric acid, the 2 4 6-trinitro derivative of phenol, cannot be prepared in good yield by the action of nitric acid upon phenol since much of the latter is destroyed by oxidation and resinous products are also formed. It is more convenient to heat the phenol with concentrated sulphuric acid whereby a mixture of o- and p-phenolsulphonic acids is obtained upon treatment of the mixture with concentrated nitric acid, nitration occurs at the two positions meta to the —SOsH group in each compound, and finally, since sulphonation is reversible, the acid groups are replaced by a third nitro group yielding picric acid in both cases ... 

The lower members of the homologous series of 1. Alcohols 2. Aldehydes 3. Ketones 4. Acids 5. Esters 6. Phenols 7. Anhydrides 8. Amines 9. Nitriles 10. Polyhydroxy phenols 1. Polybasic acids and hydro-oxy acids. 2. Glycols, poly-hydric alcohols, polyhydroxy aldehydes and ketones (sugars) 3. Some amides, ammo acids, di-and polyamino compounds, amino alcohols 4. Sulphonic acids 5. Sulphinic acids 6. Salts 1. Acids 2. Phenols 3. Imides 4. Some primary and secondary nitro compounds oximes 5. Mercaptans and thiophenols 6. Sulphonic acids, sulphinic acids, sulphuric acids, and sul-phonamides 7. Some diketones and (3-keto esters 1. Primary amines 2. Secondary aliphatic and aryl-alkyl amines 3. Aliphatic and some aryl-alkyl tertiary amines 4. Hydrazines 1. Unsaturated hydrocarbons 2. Some poly-alkylated aromatic hydrocarbons 3. Alcohols 4. Aldehydes 5. Ketones 6. Esters 7. Anhydrides 8. Ethers and acetals 9. Lactones 10. Acyl halides 1. Saturated aliphatic hydrocarbons Cyclic paraffin hydrocarbons 3. Aromatic hydrocarbons 4. Halogen derivatives of 1, 2 and 3 5. Diaryl ethers 1. Nitro compounds (tertiary) 2. Amides and derivatives of aldehydes and ketones 3. Nitriles 4. Negatively substituted amines 5. Nitroso, azo, hy-drazo, and other intermediate reduction products of nitro com-pounds 6. Sulphones, sul-phonamides of secondary amines, sulphides, sulphates and other Sulphur compounds... 

Polyhydroxy- phenols. amino acids, di- and polyamino compounds, amino alcohols. Sulphonic acids. Sulphinic acids. Salts. sulphinic acids, aminosulphonic acids and sulphonamides. Some diketones and /3-keto esters. Ethers and acetals. Lactones. Acyl halides. Diaryl ethers. intermediate reduction products of nitro compounds. Sulphones, sulphonamides of secondary amines, sulphides, sulphates and other sulphur compounds. 

Besides these direct methods of introducing nitro groups, several indirect methods are known that consist in the introduction of a group which can readily be substituted by a nitro group. In one of these which is widely used in the nitration of phenols, a compound is sulphonated and subsequently, by reaction with nitric acid, the sulpho group is replaced by the nitro group. 

As this scheme indicates, phenolsulphonic acid is first nitrated to 2-nitro-4-sul-phonic and 4-nitro-2-sulphonic acids. The former yields 2,4-dinitrophenol and 2,6-dinitro-4-sulphonic acid, and the latter 2,4-dinitro-6-sulphonic acid. All these dinitro compounds are finally converted into picric acid. 

Not Acids.—When, therefore, this hydroxyl is removed by the reaction of nitration the residue contains no remaining acid hydroxyl and the compound can not be acid. Nitro benzene and the other nitro compounds of this series are unlike the sulphonic acids then in that they are neutral compounds. 

Not Esters, Non-hydrolyzable.—The nitro compounds resemble the sulphonic acids, however, in that they are non-hydrolyzable, and, therefore, are not esters. In them the benzene ring is linked directly to the nitrogen as in the sulphonic acids the ring is linked directly to the sulphur. 

---