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Chemistry and Technology of Explosives

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This book serves as a comprehensive resource on the chemistry and technology of explosives, addressing both theoretical and practical aspects crucial for understanding the field. The content spans chemical, physical, and physico-chemical properties, as well as manufacturing processes, presented in a detailed and accessible format. This fourth edition expands upon previous versions, ensuring it meets the current needs of researchers and practitioners.

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“HAPTER V. GENERAL INFORMATION ON NITRO COMPOUNDS
“HAPTER V. GENERAL INFORMATION ON NITRO COMPOUNDS
CHAPTER XII. NITRO DERIVATIVES OF HALOGENOBENZENES
CHAPTER XII. NITRO DERIVATIVES OF HALOGENOBENZENES
CHAPTER XV. OTHER NITRO DERIVATIVES OF PHENOLS
CHAPTER XV. OTHER NITRO DERIVATIVES OF PHENOLS
CHAPTER XX. NITRONITROSO AND NITROSO COMPOUNDS
CHAPTER XX. NITRONITROSO AND NITROSO COMPOUNDS
facts also confirm the existence of addition compounds of nitric acid and water. Thus the refractive index shows, according to Veley and Manley [12], a linear relation over the range from 78 to 91% concentration. At 91% a sharp inflection occurs, and above 98.5% the slope of the curve is reversed. The electrical conduc- tivity also shows anomalies over this concentration range, passing through a min- imum.
facts also confirm the existence of addition compounds of nitric acid and water. Thus the refractive index shows, according to Veley and Manley [12], a linear relation over the range from 78 to 91% concentration. At 91% a sharp inflection occurs, and above 98.5% the slope of the curve is reversed. The electrical conduc- tivity also shows anomalies over this concentration range, passing through a min- imum.
Fic. 7. Ultra-violet absorption spectra of solutions of N,O; in anhy- drous nitric acid. (R. N. Jones, Thorn, Lyne and E. G. Taylor [58)]).
Fic. 7. Ultra-violet absorption spectra of solutions of N,O; in anhy- drous nitric acid. (R. N. Jones, Thorn, Lyne and E. G. Taylor [58)]).
THE RAMAN LINES OF NITRIC ACID AT DIFFERENT CONCENTRATIONS various concentrations, while the line 1400 cm’ has not been observed. Further investigations of Chédin [60a-62] and of Susz, Briner and Favarger [63] have shown that a solution of nitric anhydride (NOs) in nitric acid produces both 1050 and 1400 cm’! lines. From this the assumption has been advanced that the two lines indicate the presence of N.O; in mixtures of nitric and sulphuric acids. Thus it seemed that Sapozhnikov’s theory (p, 10) had been confirmed. However. further investigations have shown that this interpretation of the results is not quite right. For Chédin stated that solutions of N,O; in carbon tetrachloride, chloroform, nitromethane and phosphorus oxychloride produced the 707, 860, 1033, 1240 and 1335 cm’ lines (in addition to the solvent line), while there were
THE RAMAN LINES OF NITRIC ACID AT DIFFERENT CONCENTRATIONS various concentrations, while the line 1400 cm’ has not been observed. Further investigations of Chédin [60a-62] and of Susz, Briner and Favarger [63] have shown that a solution of nitric anhydride (NOs) in nitric acid produces both 1050 and 1400 cm’! lines. From this the assumption has been advanced that the two lines indicate the presence of N.O; in mixtures of nitric and sulphuric acids. Thus it seemed that Sapozhnikov’s theory (p, 10) had been confirmed. However. further investigations have shown that this interpretation of the results is not quite right. For Chédin stated that solutions of N,O; in carbon tetrachloride, chloroform, nitromethane and phosphorus oxychloride produced the 707, 860, 1033, 1240 and 1335 cm’ lines (in addition to the solvent line), while there were
The triangular diagram of Sapozhnikov was modified by Vandoni, on the basis of his own experimental data, to the diagram of HNO; activities (Fig. 13). Thus instead of isobars of HNO; vapour pressures he constructed curves of equal activities. The advantage of such a diagram is, among other things, that unlike vapour pressure, activity is independent of temperature.
The triangular diagram of Sapozhnikov was modified by Vandoni, on the basis of his own experimental data, to the diagram of HNO; activities (Fig. 13). Thus instead of isobars of HNO; vapour pressures he constructed curves of equal activities. The advantage of such a diagram is, among other things, that unlike vapour pressure, activity is independent of temperature.
Fic. 14. Viscosity of solutions HNO3-H,SO,-H,O. Change in viscosity with increase of HNO; content at various temperatures (Swinarski and Piotrowski [52]).
Fic. 14. Viscosity of solutions HNO3-H,SO,-H,O. Change in viscosity with increase of HNO; content at various temperatures (Swinarski and Piotrowski [52]).
Lauer and Oda [20] assumed the existence of nitracidium sulphate (according to Hantzsch) and suggested that the mechanism of nitration with a nitrating mixture is as follows:
Lauer and Oda [20] assumed the existence of nitracidium sulphate (according to Hantzsch) and suggested that the mechanism of nitration with a nitrating mixture is as follows:
- —_ SS = — the addition mechanism. Studies of the nitration of terpenes are of interest too, as they provide evidence for the possibility of attaching a HNO; molecule to the double bond. Konovalov [24] obtained nitro derivatives from menthene, camphene, pinene and bornylen¢ on acting with nitric acid. Bouveault [25] was able to prepare an addition produc of camphene and HNO3. He obtained an oily product with a structure that could 10t be well defined. The reaction of addition of nitric acid to the double bond wa: studied in detail by Sucharda [26]. He found that on acting on pinene with nitric acid containing 33% of KNO; instead of with pure nitric acid, or by introducing nitric acid vapours diluted with dry air, nitric acid esters were obtained in ove 10% yield. When reduced with zinc dust in the presence of ammonia, the esters were converted to the corresponding alcohols. aig ates
- —_ SS = — the addition mechanism. Studies of the nitration of terpenes are of interest too, as they provide evidence for the possibility of attaching a HNO; molecule to the double bond. Konovalov [24] obtained nitro derivatives from menthene, camphene, pinene and bornylen¢ on acting with nitric acid. Bouveault [25] was able to prepare an addition produc of camphene and HNO3. He obtained an oily product with a structure that could 10t be well defined. The reaction of addition of nitric acid to the double bond wa: studied in detail by Sucharda [26]. He found that on acting on pinene with nitric acid containing 33% of KNO; instead of with pure nitric acid, or by introducing nitric acid vapours diluted with dry air, nitric acid esters were obtained in ove 10% yield. When reduced with zinc dust in the presence of ammonia, the esters were converted to the corresponding alcohols. aig ates
From bornylene they obtained isoborneol (V) and epiborneol (VI) nitrates:
From bornylene they obtained isoborneol (V) and epiborneol (VI) nitrates:
tensive investigations are those by Holleman [49-55], who in the period 1895-1924 carried out numerous experiments and systematized the data obtained. Holleman [55] gives the following data on the composition of the nitration products obtained in the nitration of different monosubstituted benzene deriva- tives with mixtures of nitric and sulphuric acids (Table 2). As appears from the data shown below, the substituent already present affects the orientation of the group which is being introduced. It is evident that nitration can be influenced by the steric factor. For exampl: tert.-butylbenzene is mainly nitrated in para (72.7%) and to a much lesser extent in ortho (15.8%) positions (H. C. Brown and Nelson [88]).
tensive investigations are those by Holleman [49-55], who in the period 1895-1924 carried out numerous experiments and systematized the data obtained. Holleman [55] gives the following data on the composition of the nitration products obtained in the nitration of different monosubstituted benzene deriva- tives with mixtures of nitric and sulphuric acids (Table 2). As appears from the data shown below, the substituent already present affects the orientation of the group which is being introduced. It is evident that nitration can be influenced by the steric factor. For exampl: tert.-butylbenzene is mainly nitrated in para (72.7%) and to a much lesser extent in ortho (15.8%) positions (H. C. Brown and Nelson [88]).
From these data Wibaut calculated the ratio of the substitution rate influenced by the CH, and Cl groups to be:
From these data Wibaut calculated the ratio of the substitution rate influenced by the CH, and Cl groups to be:
Vorozhtsov [21] referred to the nitration of m- nitroacetanilide (XIV) as a1 example of inconsistency between the results obtained and predicted, viz.:
Vorozhtsov [21] referred to the nitration of m- nitroacetanilide (XIV) as a1 example of inconsistency between the results obtained and predicted, viz.:
NITRATION OF 2,5-DICHLORONITROBENZENE
NITRATION OF 2,5-DICHLORONITROBENZENE
RELATIVE REACTIVITY TOWARDS NITRATION Among other researches, those carried out by Ingold and his co-workers [74,75. are of considerable importance. They have determined the relative reactivities o! the various ortho, meta and para positions in several substituted benzenes by competitive nitration. Relative rates of nitration were determined in experiments in which benzene and a substituted benzene derivative were nitrated together, ar insufficient quantity of nitric acid being used. The relative quantities of the products: CsH;NO, and X.C;H,.NO, gave the relative rates of nitration of benzene and of CsH;.X. When these results were combined with the relative quantities of o-, m- and p- isomers formed, it was possible to arrive at figures representing the re- lative reactivity of each of the possible substitution positions (Table 9). The results show that the methyl group is a typical ortho-para directing group. Pc cd es eee ees ge oe TY Pb gee Be, Ms pe es Whee Bed cp eee |OCU TTTES
RELATIVE REACTIVITY TOWARDS NITRATION Among other researches, those carried out by Ingold and his co-workers [74,75. are of considerable importance. They have determined the relative reactivities o! the various ortho, meta and para positions in several substituted benzenes by competitive nitration. Relative rates of nitration were determined in experiments in which benzene and a substituted benzene derivative were nitrated together, ar insufficient quantity of nitric acid being used. The relative quantities of the products: CsH;NO, and X.C;H,.NO, gave the relative rates of nitration of benzene and of CsH;.X. When these results were combined with the relative quantities of o-, m- and p- isomers formed, it was possible to arrive at figures representing the re- lative reactivity of each of the possible substitution positions (Table 9). The results show that the methyl group is a typical ortho-para directing group. Pc cd es eee ees ge oe TY Pb gee Be, Ms pe es Whee Bed cp eee |OCU TTTES
It should be borne in mind that since the advent of chromatography, it is now possible to separate and identify the constituents of complex mixtures which formerly presented some difficulty. It therefore seems desirable that some of the existing data on the composition of nitration products, particularly those obtained in earlier studies should be re-examined using up to date techniques. Finally attention must be drawn to the fact that the orienting effect of the nitro group in nucleophile and radical reactions usually differs from that in electrophilic reactions, and instead of meta orientation, ortho or para orientation takes place. The corresponding observations are referred to in chapters dealing with nucleophile and radical substitutions of nitro compounds (pp. 204, 207 and 212 respectively). A monographic description of aromatic nitration and modern approach to substitution rules was recently given by de la Mare and Ridd [78a].
It should be borne in mind that since the advent of chromatography, it is now possible to separate and identify the constituents of complex mixtures which formerly presented some difficulty. It therefore seems desirable that some of the existing data on the composition of nitration products, particularly those obtained in earlier studies should be re-examined using up to date techniques. Finally attention must be drawn to the fact that the orienting effect of the nitro group in nucleophile and radical reactions usually differs from that in electrophilic reactions, and instead of meta orientation, ortho or para orientation takes place. The corresponding observations are referred to in chapters dealing with nucleophile and radical substitutions of nitro compounds (pp. 204, 207 and 212 respectively). A monographic description of aromatic nitration and modern approach to substitution rules was recently given by de la Mare and Ridd [78a].
Another scheme of Titov [32,39] suggests that the mechanism of oxidation operates through the formation of an aryl nitrate, which is the result of attaching NO," through the oxygen atom: nitrating toluene. Since the phenolic group thus introduced then promotes the introduction of the nitro groups, the number of the latter may be relatively large. Thus, in the nitration of naphthalene to nitronaphthalene, 0.5-3.5% of 2,4-dinitro- a—naphthol is formed (Fierz-David and Sponagel [80]). Titov [39] found dinitro- phenol and picric acid in the products resulting from the nitration of benzene, trinitro-m-cresol in the products of the nitration of toluene and trinitro-m-chloro- phenol in the products of nitrating chlorobenzene. Titov believes that phenols are formed from hydrocarbons under the influence
Another scheme of Titov [32,39] suggests that the mechanism of oxidation operates through the formation of an aryl nitrate, which is the result of attaching NO," through the oxygen atom: nitrating toluene. Since the phenolic group thus introduced then promotes the introduction of the nitro groups, the number of the latter may be relatively large. Thus, in the nitration of naphthalene to nitronaphthalene, 0.5-3.5% of 2,4-dinitro- a—naphthol is formed (Fierz-David and Sponagel [80]). Titov [39] found dinitro- phenol and picric acid in the products resulting from the nitration of benzene, trinitro-m-cresol in the products of the nitration of toluene and trinitro-m-chloro- phenol in the products of nitrating chlorobenzene. Titov believes that phenols are formed from hydrocarbons under the influence
Nametkin presents the nitration mechanism as follows:
Nametkin presents the nitration mechanism as follows:
res aia The introduction of the 5-nitro group can easily be explained by nitrosation of 8-hydroxyquinoline in position 5 and subsequent oxidation of the nitroso com- yound. No similar explanation can be given with regard to the mechanism of the ntroduction of the second nitro group, in position 7, as no nitrosation of nitro- Hhenols is known and the formation of “8-hydroxy-5-nitro-7-nitrosoquinoline” loes not seem to be possible. The formation of “5,7-dimtroso-8-hydroxyquinoline” 4S an intermediate is also improbable because no instance of the introduction o: wo nitroso groups into a monophenol is known. Thus nitration most likely pro- -edes through the formation of the 5-nitroso derivative only. It has also been found that 5-nitro-8-hydroxyquinoline can be nitrated with 1% nitric acid to yield 5,7-dinitro-8-hydroxyquinoline. This excludes nitrosation
res aia The introduction of the 5-nitro group can easily be explained by nitrosation of 8-hydroxyquinoline in position 5 and subsequent oxidation of the nitroso com- yound. No similar explanation can be given with regard to the mechanism of the ntroduction of the second nitro group, in position 7, as no nitrosation of nitro- Hhenols is known and the formation of “8-hydroxy-5-nitro-7-nitrosoquinoline” loes not seem to be possible. The formation of “5,7-dimtroso-8-hydroxyquinoline” 4S an intermediate is also improbable because no instance of the introduction o: wo nitroso groups into a monophenol is known. Thus nitration most likely pro- -edes through the formation of the 5-nitroso derivative only. It has also been found that 5-nitro-8-hydroxyquinoline can be nitrated with 1% nitric acid to yield 5,7-dinitro-8-hydroxyquinoline. This excludes nitrosation
COMPOSITION OF THE PRODUCTS OF THE BUTANE NITRATION AT VARIOUS TEMPERATURES This is seen clearly in Table 10, which shows the results of nitration of butane at various temperatures.
COMPOSITION OF THE PRODUCTS OF THE BUTANE NITRATION AT VARIOUS TEMPERATURES This is seen clearly in Table 10, which shows the results of nitration of butane at various temperatures.
NITRATION OF n-DODECANE
NITRATION OF n-DODECANE
RELATION BETWEEN THE CHAIN LENGTH OF PARAFFIN HYDROCARBONX AND THE YIELD OF NITRATION PRODUCT
RELATION BETWEEN THE CHAIN LENGTH OF PARAFFIN HYDROCARBONX AND THE YIELD OF NITRATION PRODUCT
RESULTS OF NITRATION OF 1000 ml OF TOLUENE WITH NITROGEN DIOXIDE AT DIFFERENT TEMPERATURES
RESULTS OF NITRATION OF 1000 ml OF TOLUENE WITH NITROGEN DIOXIDE AT DIFFERENT TEMPERATURES
On the other hand Ingold and co-workers [144,155a] have proved that the yresence of nitrous acid in the nitrating acid decreases the rate of nitration of romatic compounds in general with the exception of phenols. The same holds rue for phenyl ethers (e.g. anisole) which are more difficult to nitrate with higher oncentrations of nitric acid in acetic acid (e.g. 8N) in the presence of nitrous cid, whereas with a less concentrated nitric acid (e.g. 5N), nitrous acid accele- ates the reaction.
On the other hand Ingold and co-workers [144,155a] have proved that the yresence of nitrous acid in the nitrating acid decreases the rate of nitration of romatic compounds in general with the exception of phenols. The same holds rue for phenyl ethers (e.g. anisole) which are more difficult to nitrate with higher oncentrations of nitric acid in acetic acid (e.g. 8N) in the presence of nitrous cid, whereas with a less concentrated nitric acid (e.g. 5N), nitrous acid accele- ates the reaction.
Nitrous esters can react with alkyl peroxides to yield alkyl nitrates [163,221] (see also Vol. ID).
Nitrous esters can react with alkyl peroxides to yield alkyl nitrates [163,221] (see also Vol. ID).
Okon and Hermanowicz [181c] have found that the nitrate I can serve as a nitrat- ing agent.
Okon and Hermanowicz [181c] have found that the nitrate I can serve as a nitrat- ing agent.
HEAT OF DILUTION OF NITRATING ACID
HEAT OF DILUTION OF NITRATING ACID
Fic. 19. Heat evolved on mixing nitric acid with sulphuric acid in relation to the water content A in these acids. Quantity of heat Q =A B (Gelfman [5]). be carried out at higher temperatures without any risk of exceeding the safety limit and due to the higher temperature, nitration can proceed more rapidly. Gelfman [5] has revised the generally accepted data for calculation of the heat generated during mixing the acids and during their dilution with water [16]. He found the absolute value of the heat generated in the reaction between sulphuric and nitric acids to be lower in the presence of water than when the acids are in an an- hydrous state. He also found it decreased on diluting the acids with water. This relationship presented graphically is close to a linear one (Fig. 19). On the diagram
Fic. 19. Heat evolved on mixing nitric acid with sulphuric acid in relation to the water content A in these acids. Quantity of heat Q =A B (Gelfman [5]). be carried out at higher temperatures without any risk of exceeding the safety limit and due to the higher temperature, nitration can proceed more rapidly. Gelfman [5] has revised the generally accepted data for calculation of the heat generated during mixing the acids and during their dilution with water [16]. He found the absolute value of the heat generated in the reaction between sulphuric and nitric acids to be lower in the presence of water than when the acids are in an an- hydrous state. He also found it decreased on diluting the acids with water. This relationship presented graphically is close to a linear one (Fig. 19). On the diagram
Fic. 21. Enthalpy of nitric acid, sulphuric acid, and water mixtures (McKinley and Brown [6]).
Fic. 21. Enthalpy of nitric acid, sulphuric acid, and water mixtures (McKinley and Brown [6]).
Fic. 22. Specific heat of nitric acid, sulphuric acid, and water mixtures (McKinley and Brown [6]). at a temperature of 32°C. The total acid content in the mixture is 50%, and the HNO; content
Fic. 22. Specific heat of nitric acid, sulphuric acid, and water mixtures (McKinley and Brown [6]). at a temperature of 32°C. The total acid content in the mixture is 50%, and the HNO; content
3830-1840.5 = 1989.5 kcal or 19.9 kcal/kg Fro. 23. Heats of dilution of nitric acid, sulphuric acid, and their mixtures (Rhodes and Nelson [4]).
3830-1840.5 = 1989.5 kcal or 19.9 kcal/kg Fro. 23. Heats of dilution of nitric acid, sulphuric acid, and their mixtures (Rhodes and Nelson [4]).
Thus, for the 100 kg mixture the enthalpies of the components at 24°C are:
Thus, for the 100 kg mixture the enthalpies of the components at 24°C are:
Fic. 24. Diagram of a plant for mixing acids. The operation of mixing is carried out in iron vessels equipped with cooling ackets and stirrer.
Fic. 24. Diagram of a plant for mixing acids. The operation of mixing is carried out in iron vessels equipped with cooling ackets and stirrer.
Fic. 26. Solubility of m- dinitrobenzene in sulphuric acid (Groggins et al. [1]).
Fic. 26. Solubility of m- dinitrobenzene in sulphuric acid (Groggins et al. [1]).
Fic. 28. Rate of nitration of benzene to dinitrobenzene as a function of the molar concentration of sulphuric acid. (Various curves correspond to various molar concentrations of H,SO,, when [HNO;] = 1.) (Hetherington and Masson [9]). Fic. 28. Rate of nitration of benzene to dinitrobenzene as a function of the molar
Fic. 28. Rate of nitration of benzene to dinitrobenzene as a function of the molar concentration of sulphuric acid. (Various curves correspond to various molar concentrations of H,SO,, when [HNO;] = 1.) (Hetherington and Masson [9]). Fic. 28. Rate of nitration of benzene to dinitrobenzene as a function of the molar
Fic. 29. Diagram of the construction of nitrator. nitrators for continuous nitration are as a rule smaller for a given output. More dangerous reactions are also carried out in nitrators of smaller size. Cast iron was the material most often used for the construction of nitrators, and forged sheet iron less so. Now stainless sheet steel is generally used. Stainless steel sheet must be welded by modern methods (under a hydrogen atmosphere), since otherwise the seam would be a site relatively easily corroded. Formerly before reliable methods of welding had been developed, metal sheets were riveted to fabri-
Fic. 29. Diagram of the construction of nitrator. nitrators for continuous nitration are as a rule smaller for a given output. More dangerous reactions are also carried out in nitrators of smaller size. Cast iron was the material most often used for the construction of nitrators, and forged sheet iron less so. Now stainless sheet steel is generally used. Stainless steel sheet must be welded by modern methods (under a hydrogen atmosphere), since otherwise the seam would be a site relatively easily corroded. Formerly before reliable methods of welding had been developed, metal sheets were riveted to fabri-
Fic. 31. Diagram of a nitrator with two external chambers. Another type of simple stirrer is one with a set of blades or bars mounted verti- cally on a vertical axis. A more complex form of this type of stirrer consists of two
Fic. 31. Diagram of a nitrator with two external chambers. Another type of simple stirrer is one with a set of blades or bars mounted verti- cally on a vertical axis. A more complex form of this type of stirrer consists of two
Fic. 30. Diagram of a nitrator with a spiral screw stirrer.
Fic. 30. Diagram of a nitrator with a spiral screw stirrer.
Fic. 32. Diagram of a nitrator with a propeller stirrer.
Fic. 32. Diagram of a nitrator with a propeller stirrer.
Fic. 34. Flow diagram, nitration, the discharge of the nitrator through tha. hattram: 7 | witreatacssc O . canneetarce 2 . AKACcHReL ane acid layer is transferred to a special tank while that of the product goes to another tank (for example direct for washing if it is an end product, or to another nitrator if it is to be nitrated further). To make practicable the transport of the two layers to different locations the discharge pipe should be equipped with a sight glass, through which the partition boundary of the phases can be seen. An advantage of discharge by means of compressed air is that the whole plant can be located in a low building. If the nitrator is emptied through an outlet in its base a high building is necessary. This is of particular importance when under-
Fic. 34. Flow diagram, nitration, the discharge of the nitrator through tha. hattram: 7 | witreatacssc O . canneetarce 2 . AKACcHReL ane acid layer is transferred to a special tank while that of the product goes to another tank (for example direct for washing if it is an end product, or to another nitrator if it is to be nitrated further). To make practicable the transport of the two layers to different locations the discharge pipe should be equipped with a sight glass, through which the partition boundary of the phases can be seen. An advantage of discharge by means of compressed air is that the whole plant can be located in a low building. If the nitrator is emptied through an outlet in its base a high building is necessary. This is of particular importance when under-
Fic. 35. Flow diagram, nitration discharge of the nitrator by means of the compressed air: 1 - nitrator; 2 - separator; 3 - pressure-egg. high temperature and cannot be kept molten it is necessary to create the necessary conditions to ensure the formation of a fine-crystalline or granular product. It is only then that bottom discharge will be feasible. The nitrator contents are then transported immediately to a centrifuge, or in the case of explosives sensitive to impact (sensitivity of the order of that of tetryl or higher), the solid product is filtered off under reduced pressure. Cg) ay a: , Ce a ey a a , , a 7. ey a.
Fic. 35. Flow diagram, nitration discharge of the nitrator by means of the compressed air: 1 - nitrator; 2 - separator; 3 - pressure-egg. high temperature and cannot be kept molten it is necessary to create the necessary conditions to ensure the formation of a fine-crystalline or granular product. It is only then that bottom discharge will be feasible. The nitrator contents are then transported immediately to a centrifuge, or in the case of explosives sensitive to impact (sensitivity of the order of that of tetryl or higher), the solid product is filtered off under reduced pressure. Cg) ay a: , Ce a ey a a , , a 7. ey a.
ULTRA-VIOLET ABSORPTION SPECTRA OF POLYNITRO COMPOUNDS
ULTRA-VIOLET ABSORPTION SPECTRA OF POLYNITRO COMPOUNDS
Fic. 40. Absorption spectra of nitroparaffins (1), and nitrodiols and _aliphitic aminonitro compounds (II) (T. Urbanski [ll]). Consequently the absorption curves of compounds I and II do not contain maxima but only shoulders (Fig. 40). They are shifted towards longer wavelength (bathochromic effect) as compared with the original nitroparaftlns.
Fic. 40. Absorption spectra of nitroparaffins (1), and nitrodiols and _aliphitic aminonitro compounds (II) (T. Urbanski [ll]). Consequently the absorption curves of compounds I and II do not contain maxima but only shoulders (Fig. 40). They are shifted towards longer wavelength (bathochromic effect) as compared with the original nitroparaftlns.
ABSORPTION SPECTRA OF NITROBENZENE Brand and his co-workers [17] carried out extensive studies on the absorption spectra of aromatic compounds in sulphuric acid solutions, i.e. in a strongly proto- nizing solvent. They found that under the influence of the sulphuric acid the maximum of the nitro group shifted. These shifts were most pronounced in the case of mononitro compounds, and the least in the case of trinitro compounds. They were smaller when sulphuric acid was used as a solvent, and larger when oleum was used. The absorption curves for 2,4-dinitrotoluene are shown in Fig.
ABSORPTION SPECTRA OF NITROBENZENE Brand and his co-workers [17] carried out extensive studies on the absorption spectra of aromatic compounds in sulphuric acid solutions, i.e. in a strongly proto- nizing solvent. They found that under the influence of the sulphuric acid the maximum of the nitro group shifted. These shifts were most pronounced in the case of mononitro compounds, and the least in the case of trinitro compounds. They were smaller when sulphuric acid was used as a solvent, and larger when oleum was used. The absorption curves for 2,4-dinitrotoluene are shown in Fig.
and Herrocks [43]. The last group of investigators determined the structure by means of two-dimensional series and projections onto the principal planes. Be- cause of limited accuracy attainable with the technique all that time the pattern obtained was not clear enough. The molecule was not planar, the benzene ring was distorted, and the N-O, bonds differed in length. It was only when Llewel- lyn’s investigations [44] were published in 1947, in which a complete three-dimensional Fourier synthesis was applied, that a definite pattern was obtained as shown in
and Herrocks [43]. The last group of investigators determined the structure by means of two-dimensional series and projections onto the principal planes. Be- cause of limited accuracy attainable with the technique all that time the pattern obtained was not clear enough. The molecule was not planar, the benzene ring was distorted, and the N-O, bonds differed in length. It was only when Llewel- lyn’s investigations [44] were published in 1947, in which a complete three-dimensional Fourier synthesis was applied, that a definite pattern was obtained as shown in
first to carry out this research were Hertel [41], Bannerjee [42] and James, King
first to carry out this research were Hertel [41], Bannerjee [42] and James, King
Fic. 46. Bond distances and angles of m- dinitrobenzene (Archer [45]). Structures of the simplest compounds containing the nitro group, such as for example, NO,, N,O,, HNO, and NO,", have already been discussed. The N-O distances for nitromethane are 1.21 A and the bond angle 127° (Brockway, Beach and Pauling [46] and Rogowski [47]).
Fic. 46. Bond distances and angles of m- dinitrobenzene (Archer [45]). Structures of the simplest compounds containing the nitro group, such as for example, NO,, N,O,, HNO, and NO,", have already been discussed. The N-O distances for nitromethane are 1.21 A and the bond angle 127° (Brockway, Beach and Pauling [46] and Rogowski [47]).
Nitrolic acids, when reacted with sodium or potassium hydroxide, produce a reddish-brown colour. The reaction is used for the detection of primary nitroparaffins. Secondary. nitroparaffins form pseudonitroles with nitric acid tee eermernite,
Nitrolic acids, when reacted with sodium or potassium hydroxide, produce a reddish-brown colour. The reaction is used for the detection of primary nitroparaffins. Secondary. nitroparaffins form pseudonitroles with nitric acid tee eermernite,
A halogen atom in the ortho or para position to the nitro group can readily undergo nucleophilic displacement. The higher the polarization ability of a halo- gen, the more readily it enters into substitution reactions. Therefore the common rule that the atoms of the lighter halogens are more reactive is not followed here. For example, the reaction of halogeno-2,4-dinitrobenzene with N-alkylaniline in nitrobenzene solution runs with the greatest rapidity in the case of bromine, and with the lowest in the case of fluorine, i.e. the reactivity varies according to the order: Br>CI>F:
A halogen atom in the ortho or para position to the nitro group can readily undergo nucleophilic displacement. The higher the polarization ability of a halo- gen, the more readily it enters into substitution reactions. Therefore the common rule that the atoms of the lighter halogens are more reactive is not followed here. For example, the reaction of halogeno-2,4-dinitrobenzene with N-alkylaniline in nitrobenzene solution runs with the greatest rapidity in the case of bromine, and with the lowest in the case of fluorine, i.e. the reactivity varies according to the order: Br>CI>F:
This reaction does not occur with nitrobenzene.
This reaction does not occur with nitrobenzene.
Aromatic hydroxylation is known to take place in animal and human organism ind therefore it is of great importance to know the metabolism of various aro matic compounds including drugs (D. Robinson, J. N. Smith, R.T. William '47]). The presence of the nitro group in a molecule, resulting in its activatior nay sometimes lead to a rather unusual course of reaction. The Richter [48] re ction might be taken as an example, in which m- bromobenzoic acid may be obtaine yy reacting potassium cyanide with p- nitrobromobenzene. Likewise, when reac ng potassium cyanide with m- nitrobromobenzene, a mixture of o- and p- bromc yenzoic acids are formed. Accordins to Bunnett and his co-workers [49.50.50al the reaction is of th
Aromatic hydroxylation is known to take place in animal and human organism ind therefore it is of great importance to know the metabolism of various aro matic compounds including drugs (D. Robinson, J. N. Smith, R.T. William '47]). The presence of the nitro group in a molecule, resulting in its activatior nay sometimes lead to a rather unusual course of reaction. The Richter [48] re ction might be taken as an example, in which m- bromobenzoic acid may be obtaine yy reacting potassium cyanide with p- nitrobromobenzene. Likewise, when reac ng potassium cyanide with m- nitrobromobenzene, a mixture of o- and p- bromc yenzoic acids are formed. Accordins to Bunnett and his co-workers [49.50.50al the reaction is of th
Holleck and Perret [51] gave the following diagrammatic presentation of nucleo- philic addition of the OH or CN ion to sym- trinitrobenzene in alkaline medium (X=OH or CN):
Holleck and Perret [51] gave the following diagrammatic presentation of nucleo- philic addition of the OH or CN ion to sym- trinitrobenzene in alkaline medium (X=OH or CN):
Here the ammo group enters the ortho or para position in relation to the itro groups.
Here the ammo group enters the ortho or para position in relation to the itro groups.
ABSORPTION SPECTRA OF COLOURED COMPOUNDS PRODUCED BY THE JANOVSKY REACTION
ABSORPTION SPECTRA OF COLOURED COMPOUNDS PRODUCED BY THE JANOVSKY REACTION
Gitis believes that compounds of the V type are the main products of the Janovsky reaction. The formula V is not in agreement with the views expressed by various autho: on the structure of the coloured products obtained by adding substances containin an active methylene group to higher nitrated aromatic compounds, starting frot m- dinitrobenzene. A number of papers have been published on the subject. They ori ginated from the Jaffe-Folin [63,64] reaction for quantitative calorimetric determ nation of creatinine. The reaction consists in the development of a red colot when solutions containing creatinine are treated with aqueous picric acid and few drops of alkali at room temperature. Many (but not all) compounds wit active CH, group are capable of giving this reaction. Several red compounds have been isolated from the red solution obtaine ny + — . ae The nature of the Janovsky’s colour reaction is not sufficiently understood Reitzenstein and Stamm [55] were the first to try to establish the structure of the compounds formed. They were able to isolate from an acetone solution a browr product (IV), resulting from the reaction of 1,2,4-chlorodinitrobenzene with th enolic form of acetone:
Gitis believes that compounds of the V type are the main products of the Janovsky reaction. The formula V is not in agreement with the views expressed by various autho: on the structure of the coloured products obtained by adding substances containin an active methylene group to higher nitrated aromatic compounds, starting frot m- dinitrobenzene. A number of papers have been published on the subject. They ori ginated from the Jaffe-Folin [63,64] reaction for quantitative calorimetric determ nation of creatinine. The reaction consists in the development of a red colot when solutions containing creatinine are treated with aqueous picric acid and few drops of alkali at room temperature. Many (but not all) compounds wit active CH, group are capable of giving this reaction. Several red compounds have been isolated from the red solution obtaine ny + — . ae The nature of the Janovsky’s colour reaction is not sufficiently understood Reitzenstein and Stamm [55] were the first to try to establish the structure of the compounds formed. They were able to isolate from an acetone solution a browr product (IV), resulting from the reaction of 1,2,4-chlorodinitrobenzene with th enolic form of acetone:
The mobile electron is most likely that associated with the free valency on the N atom.
The mobile electron is most likely that associated with the free valency on the N atom.
INHIBITION CONSTANTS IN THE POLYMERIZATION OF VINYL ACETATE AT 45°C = dallateaiaaeal Recently Inamoto and Simamura [74] investigated the interaction of I-cyano- 1-methylethyl radicals and various nitro compounds (nitrobenzene, m- dinitroben- zene, nitromethane, tetranitromethane) and Bevington and Ghanem [84] have studied the effects of picric acid and m- dinitrobenzene on the sensitized radical polymeri- zation of styrene. Picric acid proved to be a rather inefficient inhibitor. m- di- nitrobenzene was found to be a polymerization retardant. By using C-labelled specimens of the nitro compounds the authors determined the amounts of nitro sompounds incorporated in the polymer. The average number of retardant mole- cules per polymer molecule was found to be 0.5-0.7. On the basis of these experiments and of those of Inamoto and Sinamura, Bevington and Ghanem suggest the interaction of polymer radical with m- dinitro-
INHIBITION CONSTANTS IN THE POLYMERIZATION OF VINYL ACETATE AT 45°C = dallateaiaaeal Recently Inamoto and Simamura [74] investigated the interaction of I-cyano- 1-methylethyl radicals and various nitro compounds (nitrobenzene, m- dinitroben- zene, nitromethane, tetranitromethane) and Bevington and Ghanem [84] have studied the effects of picric acid and m- dinitrobenzene on the sensitized radical polymeri- zation of styrene. Picric acid proved to be a rather inefficient inhibitor. m- di- nitrobenzene was found to be a polymerization retardant. By using C-labelled specimens of the nitro compounds the authors determined the amounts of nitro sompounds incorporated in the polymer. The average number of retardant mole- cules per polymer molecule was found to be 0.5-0.7. On the basis of these experiments and of those of Inamoto and Sinamura, Bevington and Ghanem suggest the interaction of polymer radical with m- dinitro-
TABLE 28
TABLE 28
SOLUBILITY OF NITROBENZENE IN AQUEOUS SOLUTIONS OF NaHCO, The thermochemical properties of nitrobenzene are given on pp. 259-262 CHEMICAL PROPERTIES In aqueous solutions of NaHCO;, nitrobenzene dissolves with greater diffi- culty than in water. The values for 43°C are given below (Table 31):
SOLUBILITY OF NITROBENZENE IN AQUEOUS SOLUTIONS OF NaHCO, The thermochemical properties of nitrobenzene are given on pp. 259-262 CHEMICAL PROPERTIES In aqueous solutions of NaHCO;, nitrobenzene dissolves with greater diffi- culty than in water. The values for 43°C are given below (Table 31):
SOLUBILITY OF DINITROBENZENES SOLUBILITY OF m- DINITROBENZENE (%) IN SULPHURIC ACID OF VARIOUS CONCENTRATIONS
SOLUBILITY OF DINITROBENZENES SOLUBILITY OF m- DINITROBENZENE (%) IN SULPHURIC ACID OF VARIOUS CONCENTRATIONS
EUTECTICS WITH m- DINITROBENZENE
EUTECTICS WITH m- DINITROBENZENE
m- Dinitrobenzene does not undergo this reaction. This property was utilize in the past for separating m- dinitrobenzene from its isomers. Crude dinitrobenzen was shaken up with a 0.5-1.0% NaOH solution at about 80°C and the o- an p- isomers were partly extracted as corresponding nitrophenates. However, thi method was not very efficient as the purified dinitrobenzene had a low melting poir (80°C). It has now been replaced by sodium sulphite method.
m- Dinitrobenzene does not undergo this reaction. This property was utilize in the past for separating m- dinitrobenzene from its isomers. Crude dinitrobenzen was shaken up with a 0.5-1.0% NaOH solution at about 80°C and the o- an p- isomers were partly extracted as corresponding nitrophenates. However, thi method was not very efficient as the purified dinitrobenzene had a low melting poir (80°C). It has now been replaced by sodium sulphite method.
Ortho- and p- dinitrobenzene react with sodium sulphite toform the corre- spending nitrosulphonic acids: According to Golosenko (after Orlova [3]), m- dinitrobenzene reacts with sodium sulphite at 70°C according to the scheme:
Ortho- and p- dinitrobenzene react with sodium sulphite toform the corre- spending nitrosulphonic acids: According to Golosenko (after Orlova [3]), m- dinitrobenzene reacts with sodium sulphite at 70°C according to the scheme:
ADDITION PRODUCTS OF DINITROBENZENE ISOMERS
ADDITION PRODUCTS OF DINITROBENZENE ISOMERS
STATISTICS OF CASES OF POISONING CAUSED BY DINITROBENZENE
STATISTICS OF CASES OF POISONING CAUSED BY DINITROBENZENE
RESULTS OF THE NITRATION OF NITROBENZENE UNDER VARIOUS CONDITIONS (WYLER) TABLE 39
RESULTS OF THE NITRATION OF NITROBENZENE UNDER VARIOUS CONDITIONS (WYLER) TABLE 39
RESULTS OF THE NITRATION OF NITROBENZENE TO DINITROBENZENE UNDER TABLE 38
RESULTS OF THE NITRATION OF NITROBENZENE TO DINITROBENZENE UNDER TABLE 38
Their melting points are: 122°C, 62°C and 127.5°C respectively. ae Vt See Se a eee Se Se eS Re ee eee eee Purification. 4500 kg of molten dinitrobenzene (i.e. one charge of the ni- rator) are run into a washing tank (C). The tank of 12 m capacity must be made yf stainless steel, lined with tiles, and fitted with a lead coated lid and a lead oated stirrer. 3000 1. water at ca. 80°C are run into it over the dinitrobenzene, with onstant stirring. The whole is allowed to cool until granulation begins at ca. 70°C, he exact temperature depending on the stirrer and on the quality of the dinitro- enzene. Immediately granulation begins, 650 kg of sodium sulphite are introduced t a rate of 100 kg per 15 min. The temperature rises to 78°C and stirring must ye continued for another 3 hr. , i, ee, a a, ee i a ss Cw a a a ee eS oe ee, ee 7 | en, a ee ee, ee |
Their melting points are: 122°C, 62°C and 127.5°C respectively. ae Vt See Se a eee Se Se eS Re ee eee eee Purification. 4500 kg of molten dinitrobenzene (i.e. one charge of the ni- rator) are run into a washing tank (C). The tank of 12 m capacity must be made yf stainless steel, lined with tiles, and fitted with a lead coated lid and a lead oated stirrer. 3000 1. water at ca. 80°C are run into it over the dinitrobenzene, with onstant stirring. The whole is allowed to cool until granulation begins at ca. 70°C, he exact temperature depending on the stirrer and on the quality of the dinitro- enzene. Immediately granulation begins, 650 kg of sodium sulphite are introduced t a rate of 100 kg per 15 min. The temperature rises to 78°C and stirring must ye continued for another 3 hr. , i, ee, a a, ee i a ss Cw a a a ee eS oe ee, ee 7 | en, a ee ee, ee |
The problem was finally solved by Meisenheimer [40] in 1902, who found that by the addition of CH;OK to trinitrobenzene an anisole derivative was formed:
The problem was finally solved by Meisenheimer [40] in 1902, who found that by the addition of CH;OK to trinitrobenzene an anisole derivative was formed:
Similar compounds, for the most part coloured, are formed with aromatic artlines as well as with some phenols and aromatic alcohols. density
Similar compounds, for the most part coloured, are formed with aromatic artlines as well as with some phenols and aromatic alcohols. density
Preparation from m- xylene. Giua [15] suggested sym-trinitrobenzene might be prepared by the nitration of m- xylene to the trinitro derivative, followed by oxidation and decarboxylation:
Preparation from m- xylene. Giua [15] suggested sym-trinitrobenzene might be prepared by the nitration of m- xylene to the trinitro derivative, followed by oxidation and decarboxylation:
EATS OF COMBUSTION AND HEATS OF FORMATION OF BENZENE NITRO DERIVATIVES ACCORDING
EATS OF COMBUSTION AND HEATS OF FORMATION OF BENZENE NITRO DERIVATIVES ACCORDING
HEATS OF NITRATION OF BENZENE AND ITS NITRO DERIVATIVES
HEATS OF NITRATION OF BENZENE AND ITS NITRO DERIVATIVES
Fic. 54. Change of yield of MNT with the ratio acid/toluene (Orlova [2a]). Fic. 53. Influence of the rate of stirring on the rate of nitration of toluene (Or- en i Sy
Fic. 54. Change of yield of MNT with the ratio acid/toluene (Orlova [2a]). Fic. 53. Influence of the rate of stirring on the rate of nitration of toluene (Or- en i Sy
Fic. 52. Nitration of toluene with HNO3-H,SO,-H,O mixture, at temperature, of di- and trinitration 65° and 80°C respectively. Area between I and II - dinitration, to the right of II - trinitration (Gorst [2]). The distribution coefficient of HNO; between the toluene and acid layers is 0.066 at 5°C and the concentration of sulphuric acid 70% H,SO3. At lower acid concentrations it is practically zero. This means that on heterogeneous nitration nitric acid passes into the organic layer only in small quantities. Therefore there is practically no nitration in this layer.
Fic. 52. Nitration of toluene with HNO3-H,SO,-H,O mixture, at temperature, of di- and trinitration 65° and 80°C respectively. Area between I and II - dinitration, to the right of II - trinitration (Gorst [2]). The distribution coefficient of HNO; between the toluene and acid layers is 0.066 at 5°C and the concentration of sulphuric acid 70% H,SO3. At lower acid concentrations it is practically zero. This means that on heterogeneous nitration nitric acid passes into the organic layer only in small quantities. Therefore there is practically no nitration in this layer.
Fic. 55. change of the rate of nitration of toluene with temperature (Orlova [2a]). activity) on the rate of nitration of toluene:
Fic. 55. change of the rate of nitration of toluene with temperature (Orlova [2a]). activity) on the rate of nitration of toluene:
SOLUBILITY OF TECHNICAL MNT (MIXTURE OF ISOMERS) IN SULPHURIC ACID (GORST [2]) THERMOCHEMICAL PROPERTIES Garner and Abernethy [3] give the following thermochemical data for the isomers of mononitrotoluene :
SOLUBILITY OF TECHNICAL MNT (MIXTURE OF ISOMERS) IN SULPHURIC ACID (GORST [2]) THERMOCHEMICAL PROPERTIES Garner and Abernethy [3] give the following thermochemical data for the isomers of mononitrotoluene :
HEATS OF COMBUSTION AND HEATS OFFORMATION OF MONONITROTOLUENE ISOMERS From these data Gamer and Abemethy have calculated the heats of nitration of toluene (Fig. 50 p. 261):
HEATS OF COMBUSTION AND HEATS OFFORMATION OF MONONITROTOLUENE ISOMERS From these data Gamer and Abemethy have calculated the heats of nitration of toluene (Fig. 50 p. 261):
increase of the factor ®. Figure 57 gives the proportion of m- nitrotoluene when acids with 10% HNO; and various concentrations of H,SO, were used at 55°C for a period of 100 min. The factor varied from 46% to 82.7%.
increase of the factor ®. Figure 57 gives the proportion of m- nitrotoluene when acids with 10% HNO; and various concentrations of H,SO, were used at 55°C for a period of 100 min. The factor varied from 46% to 82.7%.
SPECIFICATION FOR P-NITROTOLUENE (AFTER U.S.S.R. DATA, GorstT [2])
SPECIFICATION FOR P-NITROTOLUENE (AFTER U.S.S.R. DATA, GorstT [2])
SPECIFICATION FOR O- NITROTOLUENE (AFTER U.S.S.R. DATA, GORST [2])
SPECIFICATION FOR O- NITROTOLUENE (AFTER U.S.S.R. DATA, GORST [2])
The fairly pure p- isomer may be isolated from a mixture of nitrotoluenes bj freezing and repeated crystallization.
The fairly pure p- isomer may be isolated from a mixture of nitrotoluenes bj freezing and repeated crystallization.
SOLUBILITY OF TECHNICAL DNT IN SULPHURIC ACID
SOLUBILITY OF TECHNICAL DNT IN SULPHURIC ACID
HEATS OF COMBUSTION AND HEATS OF FORMATION OF THE DINITROTOLUENE ISOMERS
HEATS OF COMBUSTION AND HEATS OF FORMATION OF THE DINITROTOLUENE ISOMERS
Under the influence of alkalis it forms a stilbene derivative, especially easily in the presence of oxidizing agents (air oxygen, NaOCl): The ease of these reactions can be explained in terms of the hyperconjugation of toluene accentuated by the influence of the nitro groups.
Under the influence of alkalis it forms a stilbene derivative, especially easily in the presence of oxidizing agents (air oxygen, NaOCl): The ease of these reactions can be explained in terms of the hyperconjugation of toluene accentuated by the influence of the nitro groups.
Fic. 59. Influence of temperature on the yield of DNT. Nitration of o- and p- nitroto- luenes in nitrating mixtures with various concentrations of sulphuric acid (Kobe. Skier and Prindle (({32]).
Fic. 59. Influence of temperature on the yield of DNT. Nitration of o- and p- nitroto- luenes in nitrating mixtures with various concentrations of sulphuric acid (Kobe. Skier and Prindle (({32]).
Fic. 60. Influence of the concentration of sulphuric acid on the yield of DNT. Nitration of o- and p- nitrotoluenes (Kobe, Skinner and Prindle ([{32]).
Fic. 60. Influence of the concentration of sulphuric acid on the yield of DNT. Nitration of o- and p- nitrotoluenes (Kobe, Skinner and Prindle ([{32]).
IG 64. Temperature change during the nitration of p- nitrotoluene (BIOS 1144)
IG 64. Temperature change during the nitration of p- nitrotoluene (BIOS 1144)
3,6 (or 2,5-)-Dinitrotoluene was obtained by Page and Heasman [33] by the oxidation of 5-nitro-o-toluidine with Caro’s acid. All other isomers are prepared by nitration of m- nitrotoluene, followed by fractional crystallization of the product.
3,6 (or 2,5-)-Dinitrotoluene was obtained by Page and Heasman [33] by the oxidation of 5-nitro-o-toluidine with Caro’s acid. All other isomers are prepared by nitration of m- nitrotoluene, followed by fractional crystallization of the product.
SOLUBILITY OF a— TRINITROTOLUENE IN SULPHURIC ACID (IN %)
SOLUBILITY OF a— TRINITROTOLUENE IN SULPHURIC ACID (IN %)
SOLUBILITY OF Q— TRINITROTOLUENE IN ACID MIXTURES
SOLUBILITY OF Q— TRINITROTOLUENE IN ACID MIXTURES
SOLUBILITY OF a— TRINITROTOLUENE IN NITRIC ACID (ACCORDING TO ORLOVA [2a}) TABLE 64
SOLUBILITY OF a— TRINITROTOLUENE IN NITRIC ACID (ACCORDING TO ORLOVA [2a}) TABLE 64
SOLUBILITY OF a—- TRINITROTOLUENE (g/100 g SOLVENT)
SOLUBILITY OF a—- TRINITROTOLUENE (g/100 g SOLVENT)
Giua and Reggiani [87] reacted sodium alcoholate with trinitrotoluene in acetone solution and obtained several addition products, containing various proportions of alcoholate (1-3 molecules of C,H;ONa for 1 molecule of trinitrotoluene). By treating the products with an inorganic acid, they obtained yellow, amorphous compounds, which they regarded as mixture of several substances, which were dibenzyl! delivatives. e.g.:
Giua and Reggiani [87] reacted sodium alcoholate with trinitrotoluene in acetone solution and obtained several addition products, containing various proportions of alcoholate (1-3 molecules of C,H;ONa for 1 molecule of trinitrotoluene). By treating the products with an inorganic acid, they obtained yellow, amorphous compounds, which they regarded as mixture of several substances, which were dibenzyl! delivatives. e.g.:
Stefanovich [88], on the basis of Meisenheimer’s formulae, ascribes the formulae VII and VIII to the addition products of &—trinitrotoluene with two or three mole- cules of potassium alcoholate respectively.
Stefanovich [88], on the basis of Meisenheimer’s formulae, ascribes the formulae VII and VIII to the addition products of &—trinitrotoluene with two or three mole- cules of potassium alcoholate respectively.
The authors isolated the intermediate product XI but the products XII and XIII are hypothetical.
The authors isolated the intermediate product XI but the products XII and XIII are hypothetical.
Trinitrotoluene reacts in a similar way with benzaldehyde in an alkaline medium to form a stilbene derivative:
Trinitrotoluene reacts in a similar way with benzaldehyde in an alkaline medium to form a stilbene derivative:
[he reaction is strongly exothermic. For example, a mixture of trinitrotoluene and yenzaldehyde, in the absence of a solvent, reacts when a few drops of piperidine we added. The reaction is so violent that the mixture may ignite. The methyl group wf trinitrotoluene reacts with other aldehydes in a similar way. For this reason rinitrotoluene should be protected against the action of aldehydes, especially in kaline media. Aldehydes may be formed under the influence of acids on wood. dence, wooden vats which were formerly used for washing TNT are hardly used. ees
[he reaction is strongly exothermic. For example, a mixture of trinitrotoluene and yenzaldehyde, in the absence of a solvent, reacts when a few drops of piperidine we added. The reaction is so violent that the mixture may ignite. The methyl group wf trinitrotoluene reacts with other aldehydes in a similar way. For this reason rinitrotoluene should be protected against the action of aldehydes, especially in kaline media. Aldehydes may be formed under the influence of acids on wood. dence, wooden vats which were formerly used for washing TNT are hardly used. ees
The methyl group is readily oxidizable, giving rise to trinitrobenzoic acid which, because of the accumulation of nitro groups, is unstable and in turn loses its CO, to form trinitrobenzene:
The methyl group is readily oxidizable, giving rise to trinitrobenzoic acid which, because of the accumulation of nitro groups, is unstable and in turn loses its CO, to form trinitrobenzene:
centration of sulphuric acid from 100 to 92% may be explained by the fact that the concentration of HSO, ions increases considerably, whereas the concentration of NO," ion decreases only slightly. Decreasing the concentration of sulphuric acid below 92% H,SO, causes the NO,” concentration to fall more rapidly than the HSO, concentration increases, thus decreasing the reaction rate. To check their theory, Bennett and his co-workers added KHSO, to the nitrating tion of dinitrotoluene to trinitrotoluene. Orlova [110a] repeated the experiments of Bennett et al., studying the kinetic of nitration of dinitrotoluene in nitrating mixtures rich in nitric acid that dissolve dinitrotoluene, i.e. in homogeneous conditions. For 0.7 mole of dinitrotoluene 3.8 mole of HNO; in 12 mole of H,SO, were used. The concentration of sulphuric acid was changed from 87 to 100% H,SO,. The temperature was 90°C. Contrary to the results of Bennett, Orlova did not find any maximum of the rate of nitra tion (Fig. 66) which she attributes to the homogeneity of the reaction medium.
centration of sulphuric acid from 100 to 92% may be explained by the fact that the concentration of HSO, ions increases considerably, whereas the concentration of NO," ion decreases only slightly. Decreasing the concentration of sulphuric acid below 92% H,SO, causes the NO,” concentration to fall more rapidly than the HSO, concentration increases, thus decreasing the reaction rate. To check their theory, Bennett and his co-workers added KHSO, to the nitrating tion of dinitrotoluene to trinitrotoluene. Orlova [110a] repeated the experiments of Bennett et al., studying the kinetic of nitration of dinitrotoluene in nitrating mixtures rich in nitric acid that dissolve dinitrotoluene, i.e. in homogeneous conditions. For 0.7 mole of dinitrotoluene 3.8 mole of HNO; in 12 mole of H,SO, were used. The concentration of sulphuric acid was changed from 87 to 100% H,SO,. The temperature was 90°C. Contrary to the results of Bennett, Orlova did not find any maximum of the rate of nitra tion (Fig. 66) which she attributes to the homogeneity of the reaction medium.
treated with 90% sulphuric acid at different temperatures is given in Table 71 and Fig. 69. Figure 70 shows the influence of the concentration of sulphuric acid at 90°C.
treated with 90% sulphuric acid at different temperatures is given in Table 71 and Fig. 69. Figure 70 shows the influence of the concentration of sulphuric acid at 90°C.
Figure 72 shows the influence of trinitrotoluene on the rate of nitration of linitrotoluene in heterogeneous systems at 90°C. It is interesting to note that the iddition of 66-70% of trinitrotoluene to dinitrotoluene more than halves the ‘ate of the nitration, Further increase in the content of trinitrotoluene promotes litration of dinitrotoluene. When the content of trinitro compound reaches 91% he yield of trinitration is almost the same as that of the pure dinitrotoluene. On the basis of her own experiments and those reported in the literature Orlova [2a] came to the conclusion that the mechanism of nitration of toluene to TNT n heterogeneous conditions can be depicted in the following terms. Nitration of toluene to mononitrotoluene and of the latter to dinitrotoluene ELD OF TRINITROTOLUENE WHEN MIXTURES OF DINITROTOLUENE
Figure 72 shows the influence of trinitrotoluene on the rate of nitration of linitrotoluene in heterogeneous systems at 90°C. It is interesting to note that the iddition of 66-70% of trinitrotoluene to dinitrotoluene more than halves the ‘ate of the nitration, Further increase in the content of trinitrotoluene promotes litration of dinitrotoluene. When the content of trinitro compound reaches 91% he yield of trinitration is almost the same as that of the pure dinitrotoluene. On the basis of her own experiments and those reported in the literature Orlova [2a] came to the conclusion that the mechanism of nitration of toluene to TNT n heterogeneous conditions can be depicted in the following terms. Nitration of toluene to mononitrotoluene and of the latter to dinitrotoluene ELD OF TRINITROTOLUENE WHEN MIXTURES OF DINITROTOLUENE
EFFECT OF TEMPERATURE ON THE SENSITIVENESS OF TNT TO IMPACT
EFFECT OF TEMPERATURE ON THE SENSITIVENESS OF TNT TO IMPACT
The sensitiveness of TNT at 90°C is of the order of that of picric acid at room temperature. ee eee In any case the handling of liquid TNT requires more safety measures than solid TNT, though the fact that detonation in molten TNT proceeds only with great diffi- culty reduces the danger. TNT becomes more sensitive when such solid substan- ces as for example ammonium nitrate, are added to it (Vol. IV). Addition of sulphur also increases the sensitiveness to impact (T. Urbanski and Pillich [93]).
The sensitiveness of TNT at 90°C is of the order of that of picric acid at room temperature. ee eee In any case the handling of liquid TNT requires more safety measures than solid TNT, though the fact that detonation in molten TNT proceeds only with great diffi- culty reduces the danger. TNT becomes more sensitive when such solid substan- ces as for example ammonium nitrate, are added to it (Vol. IV). Addition of sulphur also increases the sensitiveness to impact (T. Urbanski and Pillich [93]).
Fic. 74. Sensitiveness Of TNT to impact at various temperatures (T. Urbanski and Sikorska [114]).
Fic. 74. Sensitiveness Of TNT to impact at various temperatures (T. Urbanski and Sikorska [114]).
RATE OF DETONATION OF TNT (m/sec)
RATE OF DETONATION OF TNT (m/sec)
The azoxy compound is presumably formed during the oxidation of product II. In addition, oxidation products and oxidation-reduction products are formed:
The azoxy compound is presumably formed during the oxidation of product II. In addition, oxidation products and oxidation-reduction products are formed:
HEATS OF NITRATION OF DINITRO- TO TRINITRO-TOLUENE
HEATS OF NITRATION OF DINITRO- TO TRINITRO-TOLUENE
COLOUR REACTIONS OF THE UNSYMMETRICAL ISOMERS OF TRINITROTOLUNE WITH SODIUM HYDROXIDE
COLOUR REACTIONS OF THE UNSYMMETRICAL ISOMERS OF TRINITROTOLUNE WITH SODIUM HYDROXIDE
Reactions with ammonia or with amines lead to the formation of dinitrotoluidine or its N-substituted derivatives:
Reactions with ammonia or with amines lead to the formation of dinitrotoluidine or its N-substituted derivatives:
The reaction was first mentioned by Laubenheimer [143] when examining chloro-3,4-dinitrobenzene. However for a long time no notice was taken of the possibility of putting it into practice. It was only during World War I that the method was introduced in the U.S.A., and this happened quite accidentally. In the search for methods of removing unsymmetrical isomers from crude TNT, the reduction of trinitrotoluenes was studied. It was hoped that the nitro group in the meta position, being chemically more active, would be more easily reduced, and that the reduction product would be relatively soluble in water. Sodium polysulphide was used for the reduction. However, it was found that the product of the reaction was strongly contaminated with sulphur formed at the reaction. Among other re- ducing agents used, sodium sulphite was shown to be a very efficient one in remov- ing unsymmetrical isomers, its action consisting, however, not in the reduction of the nitro group, but its replacement by a sulpho group. As Muraour [103] found, the reaction of sodium sulphite was not confined to a HE. LT a OE | ns. ge el 2 ee ryu?e. *¢&,—hl, Qe e eee es pecan BE Je
The reaction was first mentioned by Laubenheimer [143] when examining chloro-3,4-dinitrobenzene. However for a long time no notice was taken of the possibility of putting it into practice. It was only during World War I that the method was introduced in the U.S.A., and this happened quite accidentally. In the search for methods of removing unsymmetrical isomers from crude TNT, the reduction of trinitrotoluenes was studied. It was hoped that the nitro group in the meta position, being chemically more active, would be more easily reduced, and that the reduction product would be relatively soluble in water. Sodium polysulphide was used for the reduction. However, it was found that the product of the reaction was strongly contaminated with sulphur formed at the reaction. Among other re- ducing agents used, sodium sulphite was shown to be a very efficient one in remov- ing unsymmetrical isomers, its action consisting, however, not in the reduction of the nitro group, but its replacement by a sulpho group. As Muraour [103] found, the reaction of sodium sulphite was not confined to a HE. LT a OE | ns. ge el 2 ee ryu?e. *¢&,—hl, Qe e eee es pecan BE Je
permanent and transient solubility of a-trinitrotoluene in solutions of sodium sul- phite of different concentrations. The trend of the curves is similar to that found earlier by Barbiére [145].
permanent and transient solubility of a-trinitrotoluene in solutions of sodium sul- phite of different concentrations. The trend of the curves is similar to that found earlier by Barbiére [145].
OTHER BY-PRODUCTS IN THE NITRATION OF TOLUENE
OTHER BY-PRODUCTS IN THE NITRATION OF TOLUENE
is maintained by introducing live steam. 4000 kg of molten TNT (the amount obtained from 4 nitrators) are run into the tank and stirred for half an hour. Then the stirrer is stopped and water decanted off. This operation is repeated 3-4 times, then the molten TNT is drained off at the bottom of the tank into pans (2 m x 0.6 x x 0.12 m), six of which are placed on top of each other on carts (Fig. 79). The construction of these pans is such as to allow TNT to flow down to the lowest pan after the upper ones have been filled. The TNT solidifies slowly in the and forming large crystals, separated from lower melting impurities, which accu- mulate in the lowest pan in the form of oil. This product is a grade II TNT (‘liquic INT’) used for the manufacture of mining explosives. The main product is re- moved from the pans, crushed with wooden hammers, and ground finally in a cylin- drical mill. During the grinding TNT is sprayed with water to prevent it from emitting dust. The ground TNT is ready for further purification.
is maintained by introducing live steam. 4000 kg of molten TNT (the amount obtained from 4 nitrators) are run into the tank and stirred for half an hour. Then the stirrer is stopped and water decanted off. This operation is repeated 3-4 times, then the molten TNT is drained off at the bottom of the tank into pans (2 m x 0.6 x x 0.12 m), six of which are placed on top of each other on carts (Fig. 79). The construction of these pans is such as to allow TNT to flow down to the lowest pan after the upper ones have been filled. The TNT solidifies slowly in the and forming large crystals, separated from lower melting impurities, which accu- mulate in the lowest pan in the form of oil. This product is a grade II TNT (‘liquic INT’) used for the manufacture of mining explosives. The main product is re- moved from the pans, crushed with wooden hammers, and ground finally in a cylin- drical mill. During the grinding TNT is sprayed with water to prevent it from emitting dust. The ground TNT is ready for further purification.
Fro. 80. Diagram of the lay-out of manufacture of TNT with detoluation [6].
Fro. 80. Diagram of the lay-out of manufacture of TNT with detoluation [6].
FIG. 81. Flow sheet of the old method of manufacture of TNT in U.S.S.R. (Gorst ([7]).
FIG. 81. Flow sheet of the old method of manufacture of TNT in U.S.S.R. (Gorst ([7]).
Mononitration of toluene. The nitrator is filled with toluene and nitration acid is added (Table 82). Dinitration. The nitrator is filled with MNT and nitrating mixture is added MONONITRATION OF TOLUENE
Mononitration of toluene. The nitrator is filled with toluene and nitration acid is added (Table 82). Dinitration. The nitrator is filled with MNT and nitrating mixture is added MONONITRATION OF TOLUENE
QUANTITY OF ACIDS USED FOR 1000 KG OF CRUDE TNT
QUANTITY OF ACIDS USED FOR 1000 KG OF CRUDE TNT
In this plant each of the nitrators is connected with a separator, into which the liquid from the nitrator overflows and where the nitro compound is separated from the acid. The upper, nitro compound layer then flows to the next nitrator, containing a more concentrated acid, while the lower acid layer passes through a siphon to another nitrator, where less vigorous nitration takes place. Both liquid phases-that of the acid and that of the material being nitrated-flow in counter- current to each other. Figure 85 represents a schematic diagram of a unit for contin- uous nitration (after MacNab [18]).
In this plant each of the nitrators is connected with a separator, into which the liquid from the nitrator overflows and where the nitro compound is separated from the acid. The upper, nitro compound layer then flows to the next nitrator, containing a more concentrated acid, while the lower acid layer passes through a siphon to another nitrator, where less vigorous nitration takes place. Both liquid phases-that of the acid and that of the material being nitrated-flow in counter- current to each other. Figure 85 represents a schematic diagram of a unit for contin- uous nitration (after MacNab [18]).
Fic. 86. Diagram of the German continuous nitration of toluene to TNT (CIOS XXIV 4). are arranged in a cascade so as to enable the liquid to flow down from higher vessels to lower ones. In this way the nitration mixture can be transferred from the nitra- tor to the separator, where the nitro compound rises to the surface and flows off through a drain between the separator to the next nitrator. The waste acid flows down from the bottom of the separators to storage tanks. The nitrators are 1.5 m high and 1 m in diameter. The separators are 0.75 m high and 1.5 m in diameter. Both are fabricated from cast iron. Recently F. Meissner, Wannschaff and Othmer [20] have published some data
Fic. 86. Diagram of the German continuous nitration of toluene to TNT (CIOS XXIV 4). are arranged in a cascade so as to enable the liquid to flow down from higher vessels to lower ones. In this way the nitration mixture can be transferred from the nitra- tor to the separator, where the nitro compound rises to the surface and flows off through a drain between the separator to the next nitrator. The waste acid flows down from the bottom of the separators to storage tanks. The nitrators are 1.5 m high and 1 m in diameter. The separators are 0.75 m high and 1.5 m in diameter. Both are fabricated from cast iron. Recently F. Meissner, Wannschaff and Othmer [20] have published some data
Fic. 92. Continuous crystallization of TNT (Bofors-Norell method [26]).
Fic. 92. Continuous crystallization of TNT (Bofors-Norell method [26]).
temperature below its melting point. water. For this purpose the installation described on p. 364 may be used, in which a stream of molten TNT ejected under pressure impinges on two streams of cold water at their point of contact (Fig. 84). Grains of TNT together with water fall into a tank, and are conveyed to a centrifuge or to a vacuum filter. To remove water the product is dried in a tunnel or tray drier at 50-60°C, i.e. at a temperature below its melting point. The plant for continuous washing (Fig. 96) consists of a rectangular trough, 8 m long, 1.4 m wide and 1.3 m high. The trough is made of cast iron sections screwed
temperature below its melting point. water. For this purpose the installation described on p. 364 may be used, in which a stream of molten TNT ejected under pressure impinges on two streams of cold water at their point of contact (Fig. 84). Grains of TNT together with water fall into a tank, and are conveyed to a centrifuge or to a vacuum filter. To remove water the product is dried in a tunnel or tray drier at 50-60°C, i.e. at a temperature below its melting point. The plant for continuous washing (Fig. 96) consists of a rectangular trough, 8 m long, 1.4 m wide and 1.3 m high. The trough is made of cast iron sections screwed
It can be seen from the diagram that the molten TNT to be washed flows in counter-current against a stream of hot water. In the mixers, emulsification of the TNT in water takes place. The emulsion then passes through an overflow at the top or at the bottom of the mixer (depending on the direction given by the stirrer) to the separator, where the TNT collects at the bottom and flows to the adjacent mixer by an outlet near the bottom. Water rises to the top of the separator and passes in counter-current through an overflow to another mixer. By direct steam heating a temperature 80-100°C is maintained in the trough. The cover of the latter is provided with vent ducts for escaping vapours. For 1000 kg of TNT about 2500 1. of water is used. The output amounts to 1.5 tanec anf TNIT nar hair A ftar waching thea aridity af TNT falle tn 0) 1.NIG% anf WGN.
It can be seen from the diagram that the molten TNT to be washed flows in counter-current against a stream of hot water. In the mixers, emulsification of the TNT in water takes place. The emulsion then passes through an overflow at the top or at the bottom of the mixer (depending on the direction given by the stirrer) to the separator, where the TNT collects at the bottom and flows to the adjacent mixer by an outlet near the bottom. Water rises to the top of the separator and passes in counter-current through an overflow to another mixer. By direct steam heating a temperature 80-100°C is maintained in the trough. The cover of the latter is provided with vent ducts for escaping vapours. For 1000 kg of TNT about 2500 1. of water is used. The output amounts to 1.5 tanec anf TNIT nar hair A ftar waching thea aridity af TNT falle tn 0) 1.NIG% anf WGN.
Fic. 97. Sulphitation of TNT (British method [6]).
Fic. 97. Sulphitation of TNT (British method [6]).
Fic. 100. Lay-out of a plant for continuous TNT manufacture according to Meissner [20].
Fic. 100. Lay-out of a plant for continuous TNT manufacture according to Meissner [20].
Fic. 101 Lay-out of a Bofors plant for continuous TNT manufacture [17]. (Dimensions in meters).
Fic. 101 Lay-out of a Bofors plant for continuous TNT manufacture [17]. (Dimensions in meters).
British Technical Records [6] mentioned another approach to the problem of utili- zation of sulphitation liquors. According to these data, attempts were made in Great Britain during World War I to make use of the reactivity of the sulpho group in the ortho or para position to the nitro ones. By acting with methylamine, N-methyl- dinitrotoluidine (I and II) was obtained, which, when further nitrated, yielded “methyltetryl”. All the methods mentioned proved uneconomical.
British Technical Records [6] mentioned another approach to the problem of utili- zation of sulphitation liquors. According to these data, attempts were made in Great Britain during World War I to make use of the reactivity of the sulpho group in the ortho or para position to the nitro ones. By acting with methylamine, N-methyl- dinitrotoluidine (I and II) was obtained, which, when further nitrated, yielded “methyltetryl”. All the methods mentioned proved uneconomical.
mixtures. This can be seen in the diagram (Fig. 102) illustrating the nitration of DNX to TNX. The quantity of N,O3 evolved during the reaction was taken as a criterion of the intensity of the oxidation reactions.
mixtures. This can be seen in the diagram (Fig. 102) illustrating the nitration of DNX to TNX. The quantity of N,O3 evolved during the reaction was taken as a criterion of the intensity of the oxidation reactions.
All three isomers can be obtained by nitrating m-xylene using a nitrating mixture of the composition:
All three isomers can be obtained by nitrating m-xylene using a nitrating mixture of the composition:
EUTECTICS WITH 2,4,6- TRINITRO-m-XYLENE
EUTECTICS WITH 2,4,6- TRINITRO-m-XYLENE
The reaction proceeds much more slowly than with the unsymmetrical trinitro derivatives of toluene.
The reaction proceeds much more slowly than with the unsymmetrical trinitro derivatives of toluene.
Later these observations were confirmed by Marqueyrol and Loriette [9]. From 100 parts of o- xylene, 130-135 parts of trinitro derivatives are obtained. To separate the isomers use is made of their different solubility in 75% ulphuric acid. The mixture of isomers is dissolved in the acid at 120-130°C, and hen cooled; only the 3,4,5-isomer crystallizes then. The 3,4,6-isomer left in the acid an be precipitated from the solution by adding water. The 3,4,5-isomer can be yurified by crystallization from 75% sulphuric acid, the 3,4,6-isomer by rystallization from alcohol. Both isomers react with sodium sulphite to form the corresponding sulpho ee eae
Later these observations were confirmed by Marqueyrol and Loriette [9]. From 100 parts of o- xylene, 130-135 parts of trinitro derivatives are obtained. To separate the isomers use is made of their different solubility in 75% ulphuric acid. The mixture of isomers is dissolved in the acid at 120-130°C, and hen cooled; only the 3,4,5-isomer crystallizes then. The 3,4,6-isomer left in the acid an be precipitated from the solution by adding water. The 3,4,5-isomer can be yurified by crystallization from 75% sulphuric acid, the 3,4,6-isomer by rystallization from alcohol. Both isomers react with sodium sulphite to form the corresponding sulpho ee eae
Only one trinitro-p-xylene exists, viz. 2,3,5- or 3,5,6-trinitro-p-xylene :
Only one trinitro-p-xylene exists, viz. 2,3,5- or 3,5,6-trinitro-p-xylene :
BOILING POINTS OF ISOMERIC XYLENE
BOILING POINTS OF ISOMERIC XYLENE
COMPARISON OF NITRATION CONDITIONS FOR TOLUENE AND XYLENE (PASCAL [20]) Mononitration of xylene (I. G. Leverkasen method). To the nitrator containing 1400 1. of spent acid from the previous nitration, 50 1. of xylene are added (thus the 230-300 parts of a nitrating mixture of the following composition are applied:
COMPARISON OF NITRATION CONDITIONS FOR TOLUENE AND XYLENE (PASCAL [20]) Mononitration of xylene (I. G. Leverkasen method). To the nitrator containing 1400 1. of spent acid from the previous nitration, 50 1. of xylene are added (thus the 230-300 parts of a nitrating mixture of the following composition are applied:
Dinitromesitylene can be obtained by dissolving mesitylene in fuming nitric acid, followed by the addition of water which causes dinitromesitylene to precip- itate. For the preparation of trinitromesitylene by the Blanksma [7] method, mesitylene is dissolved in sulphuric acid (partial sulphonation taking place), and the solution is added to nitric acid (sp. gr. 1.52). Trinitromesitylene then precipi- tates, as white crystals, dissolved by organic solvents only with difficulty. Kholevo [26a] nitrated mesitylene with the nitrating mixture (27% HNO3, 69% H,SOu, 4% H,O) to yield trinitromesitylene. The explosive power of trinitromesitylene is rather low - of the order of DNT.
Dinitromesitylene can be obtained by dissolving mesitylene in fuming nitric acid, followed by the addition of water which causes dinitromesitylene to precip- itate. For the preparation of trinitromesitylene by the Blanksma [7] method, mesitylene is dissolved in sulphuric acid (partial sulphonation taking place), and the solution is added to nitric acid (sp. gr. 1.52). Trinitromesitylene then precipi- tates, as white crystals, dissolved by organic solvents only with difficulty. Kholevo [26a] nitrated mesitylene with the nitrating mixture (27% HNO3, 69% H,SOu, 4% H,O) to yield trinitromesitylene. The explosive power of trinitromesitylene is rather low - of the order of DNT.
Bonecki and T. Urbanski [45] prepared the same substance, also from 2,4,6-tri- nitrotoluene, but in a different way: The next steps were analogous to those mentioned earlier. High purity trinitrostyrene was formed with m. p. 140°C.
Bonecki and T. Urbanski [45] prepared the same substance, also from 2,4,6-tri- nitrotoluene, but in a different way: The next steps were analogous to those mentioned earlier. High purity trinitrostyrene was formed with m. p. 140°C.
SOLUBILITY OF DINITRONAPHTHALENES
SOLUBILITY OF DINITRONAPHTHALENES
It was known for long time that the 1,5- and 1,8-dinitronaphthalenes react under the action of concentrated sulphuric acid to yield naphthazarine - a valuable compound for dyeing [30]. The mechanism of the formation of this compound (based on experiments of Dimroth and Ruck [18a]) probably consists in the trans- formation of the nitro compounds to quinone-oximes and the reduction of one of the nitro groups by hydroxylamine split off the oxime:
It was known for long time that the 1,5- and 1,8-dinitronaphthalenes react under the action of concentrated sulphuric acid to yield naphthazarine - a valuable compound for dyeing [30]. The mechanism of the formation of this compound (based on experiments of Dimroth and Ruck [18a]) probably consists in the trans- formation of the nitro compounds to quinone-oximes and the reduction of one of the nitro groups by hydroxylamine split off the oxime:
They are very fine crystalline, light brownish-grey products, sparingly soluble in organic solvents.
They are very fine crystalline, light brownish-grey products, sparingly soluble in organic solvents.
HEATS OF COMBUSTION AND FORMATION OF NITRONAPHTHALENES Hence, the heats of nitration are: TABLE 97
HEATS OF COMBUSTION AND FORMATION OF NITRONAPHTHALENES Hence, the heats of nitration are: TABLE 97
THERMOCHEMICAL PROPERTIES OF NITRONAPHTHALENES Due to difficulties in preparation, tetranitronaphthalenes are not applied as explosives.
THERMOCHEMICAL PROPERTIES OF NITRONAPHTHALENES Due to difficulties in preparation, tetranitronaphthalenes are not applied as explosives.
Fic. 108. Diagram of a nitrator for the nitration of naphthalene (Pascal [20a]). The mixture is prepared from 600 kg of the spent acid from the dinitronaph- thalene manufacture and 550 kg of the spent acid from mononitration, which has been re-used for washing dinitronaphthalene. In consequence the spent acid contains some of the HNO; adsorbed by dinitronaphthalene. The composition and the quantity of the mixture should be so calculated as to contain 128 kg of HNO3, required for complete nitration of 300 kg of naphthalene.
Fic. 108. Diagram of a nitrator for the nitration of naphthalene (Pascal [20a]). The mixture is prepared from 600 kg of the spent acid from the dinitronaph- thalene manufacture and 550 kg of the spent acid from mononitration, which has been re-used for washing dinitronaphthalene. In consequence the spent acid contains some of the HNO; adsorbed by dinitronaphthalene. The composition and the quantity of the mixture should be so calculated as to contain 128 kg of HNO3, required for complete nitration of 300 kg of naphthalene.
The naphthalene to be nitrated (300 kg) is added to the nitrating mixture during aperiod of 3 hr. Meanwhile the temperature has risen spontaneously up to 50°C. When all the naphthalene has been added, the nitrator contents are heated to 55°C. After the completion of the nitration process, the mixture in the nitrator is allowec to remain at rest to separate into two layers. Then the lower, acid layer is drawn off into a lead lined tank (I) (Fig. log), 1.5 m high and 1.25 m in diameter. Molten
The naphthalene to be nitrated (300 kg) is added to the nitrating mixture during aperiod of 3 hr. Meanwhile the temperature has risen spontaneously up to 50°C. When all the naphthalene has been added, the nitrator contents are heated to 55°C. After the completion of the nitration process, the mixture in the nitrator is allowec to remain at rest to separate into two layers. Then the lower, acid layer is drawn off into a lead lined tank (I) (Fig. log), 1.5 m high and 1.25 m in diameter. Molten
NITRATION OF NITRONAPHTHALENE TO TRINITRONAPHTHALENE French method [31a]
NITRATION OF NITRONAPHTHALENE TO TRINITRONAPHTHALENE French method [31a]
MATERIAL CONSUMPTION FOR 1000 kg OF DINITRONAPHTHALENE TABLE 99
MATERIAL CONSUMPTION FOR 1000 kg OF DINITRONAPHTHALENE TABLE 99
Among the six chlorodinitrobenzenes known, the 1,2,4- and 1,2,6-isomers at he most important as they are the principal products of the nitration of chlorc yenzene. 1-Chloro-2,4-dinitrobenzene results from the nitration of o- and p- chlor¢ 1itrobenzenes and 1-chloro-2,6-dinitrobenzene from the o- isomer. Apart frot hese, the 1,3,4-isomer, which forms in the nitration of m- chloronitrobenzen s of some importance.
Among the six chlorodinitrobenzenes known, the 1,2,4- and 1,2,6-isomers at he most important as they are the principal products of the nitration of chlorc yenzene. 1-Chloro-2,4-dinitrobenzene results from the nitration of o- and p- chlor¢ 1itrobenzenes and 1-chloro-2,6-dinitrobenzene from the o- isomer. Apart frot hese, the 1,3,4-isomer, which forms in the nitration of m- chloronitrobenzen s of some importance.
SOLUBILITY OF 1-CHLORO-2,4-DINITROBENZENE
SOLUBILITY OF 1-CHLORO-2,4-DINITROBENZENE
When reacted with mercaptans or thiophenols of the general formula RSH yields thioethers (Bielig and Reidies [23]):
When reacted with mercaptans or thiophenols of the general formula RSH yields thioethers (Bielig and Reidies [23]):
Stage II - gradual conversion of the product II into methyl picrate:
Stage II - gradual conversion of the product II into methyl picrate:
D,) Action of CH;O- at very low concentration on residual picryl chloride.
D,) Action of CH;O- at very low concentration on residual picryl chloride.
The 2,6-isomer is the principal product of nitration of p- dichlorobenzene, the 2,3-isomer being formed in a smaller quantity, and the 2,5-isomer to a still smaller extent.
The 2,6-isomer is the principal product of nitration of p- dichlorobenzene, the 2,3-isomer being formed in a smaller quantity, and the 2,5-isomer to a still smaller extent.
The reactivity of the nitro groups in 1,4-dichloro-2,3-dinitrobenzene and 1,4- lichloro-2,5-dinitrobenzene is exceptionally high, exceeding that of the chlorine tom.
The reactivity of the nitro groups in 1,4-dichloro-2,3-dinitrobenzene and 1,4- lichloro-2,5-dinitrobenzene is exceptionally high, exceeding that of the chlorine tom.
The most important nitro derivatives of fluorobenzene are:
The most important nitro derivatives of fluorobenzene are:
Of these only the 2,4-isomer is used in explosive compositions or as a starting material for the preparation of picric acid by one of the methods described later. The 2,6-isomer on nitration also gives picric acid but it is not used for this purpose on a commercial scale. Both these isomers may be obtained by the nitration of phenol with nitric acid. All the other isomers are prepared by indirect methods. Laurent [8] was the first to obtain dinitrophenol by nitrating phenol. Investi- gations that followed revealed that Laurent’s dinitrophenol was not a chemical individual, but a mixture of the 2,4- and 2,6-isomers. Kiirner [17] obtained pure 2,4-dinitrophenol by the nitration of p- nitrophenol and Armstrong [18] prepared 2,6-dinitrophenol along with some 2,4-isomer, starting from o- nitrophenol. Clemm [19] determined the constitution of 2,4-dinitrophenol, which was later confirmed by Salkowski [20]. Finally Hiibner and W. Schneider [21] defined the conditions under which the
Of these only the 2,4-isomer is used in explosive compositions or as a starting material for the preparation of picric acid by one of the methods described later. The 2,6-isomer on nitration also gives picric acid but it is not used for this purpose on a commercial scale. Both these isomers may be obtained by the nitration of phenol with nitric acid. All the other isomers are prepared by indirect methods. Laurent [8] was the first to obtain dinitrophenol by nitrating phenol. Investi- gations that followed revealed that Laurent’s dinitrophenol was not a chemical individual, but a mixture of the 2,4- and 2,6-isomers. Kiirner [17] obtained pure 2,4-dinitrophenol by the nitration of p- nitrophenol and Armstrong [18] prepared 2,6-dinitrophenol along with some 2,4-isomer, starting from o- nitrophenol. Clemm [19] determined the constitution of 2,4-dinitrophenol, which was later confirmed by Salkowski [20]. Finally Hiibner and W. Schneider [21] defined the conditions under which the
CHARACTERISTICS OF 2,4-DINITROPHENATES
CHARACTERISTICS OF 2,4-DINITROPHENATES
Hydrolysis of chloronitro compounds. The chlorine atom in chlorobenzene
Hydrolysis of chloronitro compounds. The chlorine atom in chlorobenzene
rom the resulting dinitrophenate, dinitrophenol is obtained by acidificatiot
rom the resulting dinitrophenate, dinitrophenol is obtained by acidificatiot
SOLUBILITY OF PICRIC ACID IN WATER The solubility of picric acid in sulphuric acid varies with the concentration of the latter. It is highest for concentrated acid and lowest in 18-20% acid. This can be seen from Table 110 [41b].
SOLUBILITY OF PICRIC ACID IN WATER The solubility of picric acid in sulphuric acid varies with the concentration of the latter. It is highest for concentrated acid and lowest in 18-20% acid. This can be seen from Table 110 [41b].
SOLUBILITY OF PICRIC ACID IN H,SO,
SOLUBILITY OF PICRIC ACID IN H,SO,
SOLUBILITY OF PICRIC ACID IN AQUEOUS SOLUTIONS OF ORGANIC SOLVENTS
SOLUBILITY OF PICRIC ACID IN AQUEOUS SOLUTIONS OF ORGANIC SOLVENTS
SOLUBILITY OF PICRIC ACID IN NITRIC ACID (DRUCKER [42]) In organic solvents picric acid dissolves more readily than in water as Table 112 shows.
SOLUBILITY OF PICRIC ACID IN NITRIC ACID (DRUCKER [42]) In organic solvents picric acid dissolves more readily than in water as Table 112 shows.
SOLUBILITY OF PICRIC ACID IN ORGANIC SOLVENTS The solubility of picric acid in aqueous solutions of methyl-, ethyl-, isopropyl- and n-propyl alcohols, as well as of acetone has also been determined (Duff and Bills [43]), Table 113.
SOLUBILITY OF PICRIC ACID IN ORGANIC SOLVENTS The solubility of picric acid in aqueous solutions of methyl-, ethyl-, isopropyl- and n-propyl alcohols, as well as of acetone has also been determined (Duff and Bills [43]), Table 113.
PARTITION COEFFICIENTS OF PICRIC ACID BETWEEN TWO LIQUID PHASES
PARTITION COEFFICIENTS OF PICRIC ACID BETWEEN TWO LIQUID PHASES
RATE OF DETONATION OF PICRIC ACID (m/sec)
RATE OF DETONATION OF PICRIC ACID (m/sec)
According to Ishiwara [71], after a 30 min action a 0.04% aqueous solution o: picric acid exhibits bactericidal activity against typhoid bacteria, staphylococci, streptococci and gonococci.
According to Ishiwara [71], after a 30 min action a 0.04% aqueous solution o: picric acid exhibits bactericidal activity against typhoid bacteria, staphylococci, streptococci and gonococci.
SULPHONATION OF PHENOL UNDER VARIOUS CONDITIONS
SULPHONATION OF PHENOL UNDER VARIOUS CONDITIONS
in the widest part, 1.35 m in height). The lids of the jars are equipped with two wide entry holes, 15 cm in diameter (Fig. 113), one for feeding the nitrator with acid anc sodium nitrate, the other for connecting the nitrator with the ventilating system. In addition to this, three smaller holes in the lid serve for introducing sulphophenol. inserting a compressed air line that reached down to the bottom of the jar and for inserting a thermometer. Naturally, various modifications of the nitrator con- struction are possible. These jar-nitrators have the disadvantage of not being equippec with heating or cooling devices: the heat is supplied by the reaction itself and the required temperature is maintained by adjusting the flow of the reactants. To this 180 kg of warm 50-70°C sulphophenol (corresponding to 30 kg of phenol) is gradually added. At the same time compressed air is passed through the nitrator ‘oO mix the reactants well. The rate of addition of sulphophenol should be so adjusted as to prevent the temperature from rising too rapidly at the beginning of the reac- ‘ion. Hence the sulphophenol should be added carefully at first, although its flow must be rapid enough to attain a temperature of 100°C, at which the main portion of the product nitrates. If the process is operated properly, 95-100°C is attained within 20 min from the beginning of the process (initial temperature 25-30°C).
in the widest part, 1.35 m in height). The lids of the jars are equipped with two wide entry holes, 15 cm in diameter (Fig. 113), one for feeding the nitrator with acid anc sodium nitrate, the other for connecting the nitrator with the ventilating system. In addition to this, three smaller holes in the lid serve for introducing sulphophenol. inserting a compressed air line that reached down to the bottom of the jar and for inserting a thermometer. Naturally, various modifications of the nitrator con- struction are possible. These jar-nitrators have the disadvantage of not being equippec with heating or cooling devices: the heat is supplied by the reaction itself and the required temperature is maintained by adjusting the flow of the reactants. To this 180 kg of warm 50-70°C sulphophenol (corresponding to 30 kg of phenol) is gradually added. At the same time compressed air is passed through the nitrator ‘oO mix the reactants well. The rate of addition of sulphophenol should be so adjusted as to prevent the temperature from rising too rapidly at the beginning of the reac- ‘ion. Hence the sulphophenol should be added carefully at first, although its flow must be rapid enough to attain a temperature of 100°C, at which the main portion of the product nitrates. If the process is operated properly, 95-100°C is attained within 20 min from the beginning of the process (initial temperature 25-30°C).
content being brought to 5-7%. The contents of 4-5 nitrators (200-300 kg of picric acid) are transferred by means of wooden ladles to a wooden washing vat (Fig. 114), where picric acid is washed several (mostly five) times with 150-200 1. portions of water. For 100 kg of picric acid 400 1. of water is used. The product is tested for purity by determining the SO,’* ions in a solution of the picric acid in distilled water. After washing, picric acid is separated from water in a centrifuge usually made of copper, the water content being brought to 5-7%. Washings are collected in special wooden tanks for settling. The spent acid is also added to the washings so as to bring the H,SO, content to 10-30% as in such an “acid water” the solubility of picric acid is at its lowest. The water is decant- ed from time to time and disposed off into the river, after being neutralized, while the settled picric acid is collected from the bottom of the tank. The recovered nicric acid nenally contains laroe quantities of mineral matter
content being brought to 5-7%. The contents of 4-5 nitrators (200-300 kg of picric acid) are transferred by means of wooden ladles to a wooden washing vat (Fig. 114), where picric acid is washed several (mostly five) times with 150-200 1. portions of water. For 100 kg of picric acid 400 1. of water is used. The product is tested for purity by determining the SO,’* ions in a solution of the picric acid in distilled water. After washing, picric acid is separated from water in a centrifuge usually made of copper, the water content being brought to 5-7%. Washings are collected in special wooden tanks for settling. The spent acid is also added to the washings so as to bring the H,SO, content to 10-30% as in such an “acid water” the solubility of picric acid is at its lowest. The water is decant- ed from time to time and disposed off into the river, after being neutralized, while the settled picric acid is collected from the bottom of the tank. The recovered nicric acid nenally contains laroe quantities of mineral matter
Fic. 116. Flow sheet of the nitration of sulphophenol to picric acid (Pascal [2]).
Fic. 116. Flow sheet of the nitration of sulphophenol to picric acid (Pascal [2]).
Fic. 117. General view of nitrators for the production of picric acid [8].
Fic. 117. General view of nitrators for the production of picric acid [8].
FIG. 120. Flow sheet of the nitration of phenol with concentrated nitrating mixture (Lebedev [5]).
FIG. 120. Flow sheet of the nitration of phenol with concentrated nitrating mixture (Lebedev [5]).
c. 123. Flow sheet of the production of picric acid from chlorobenzene (Lebedev [5]).
c. 123. Flow sheet of the production of picric acid from chlorobenzene (Lebedev [5]).
The evidence for the existence of “isopicric acid” is not convincing.
The evidence for the existence of “isopicric acid” is not convincing.
* Nitrocellulose ignites from 1 swing, gunpowder from 8 wings.
* Nitrocellulose ignites from 1 swing, gunpowder from 8 wings.
DENSITY OF AMMONIUM PICRATE FORMS
DENSITY OF AMMONIUM PICRATE FORMS
Tetranitrophenol forms by the action of 50% nitric acid followed by a 63% acid on diquinoyltrioxime at a temperature lower than the room temperature. By neutralizing the solution a sparingly soluble potassium salt is precipitated, which in turn may be converted by double decomposition into a still less soluble barium salt. From the latter, by the action of a calculated quantity of sulphuric acid, free tetranitrophenol may be obtained. from diquinoyltrioxime. The latter can exist in two isomeric forms, (Ia) and (Ib), which may be prepared by reacting hydroxylamine with dinitrosoresorcinol:
Tetranitrophenol forms by the action of 50% nitric acid followed by a 63% acid on diquinoyltrioxime at a temperature lower than the room temperature. By neutralizing the solution a sparingly soluble potassium salt is precipitated, which in turn may be converted by double decomposition into a still less soluble barium salt. From the latter, by the action of a calculated quantity of sulphuric acid, free tetranitrophenol may be obtained. from diquinoyltrioxime. The latter can exist in two isomeric forms, (Ia) and (Ib), which may be prepared by reacting hydroxylamine with dinitrosoresorcinol:
NITRO DERIVATIVES OF POLYHYDRIC PHENOLS
NITRO DERIVATIVES OF POLYHYDRIC PHENOLS
In practice the first process is applied, as it gives a higher yield of the product. The nitrosation is effected in a well known way. A weak (2.75%) aqueous solu tion of one mole of resorcinol is acidified with 2 moles of sulphuric acid. The solu tion is cooled down to -2°C and a 10% aqueous solution of 2 moles of NaNO is added, dropwise. Crystalline yellowish 2,4-dinitrosoresorcinol is precipitates in theoretical yield. The precipitate is washed and separated in a centrifuge or or a vacuum filter prior to oxidation. From dinitrosoresorcinol the divalent lead sal of dinitrosoresorcinol may be prepared, having initiating properties.
In practice the first process is applied, as it gives a higher yield of the product. The nitrosation is effected in a well known way. A weak (2.75%) aqueous solu tion of one mole of resorcinol is acidified with 2 moles of sulphuric acid. The solu tion is cooled down to -2°C and a 10% aqueous solution of 2 moles of NaNO is added, dropwise. Crystalline yellowish 2,4-dinitrosoresorcinol is precipitates in theoretical yield. The precipitate is washed and separated in a centrifuge or or a vacuum filter prior to oxidation. From dinitrosoresorcinol the divalent lead sal of dinitrosoresorcinol may be prepared, having initiating properties.
Hemmelmayer [28] presented the nitration of resorcylic acid and its subsequent lecarboxylation by the following reactions :
Hemmelmayer [28] presented the nitration of resorcylic acid and its subsequent lecarboxylation by the following reactions :
Sulphonation yields only three compounds: I, II, and III The sulphonic acids I and II can be obtained by sulphonation of resorcinol with sulphuric acid or oleum at temperatures which are not higher than 100°C (Mertz and Zetter [32]). The trisulphonic acid can only be prepared by the action of oleum at 200°C. According to Aubertein and Emeury [29], resorcinol can be sulphonated to the compound II by the action of a tenfold quantity (by weight) of sulphuric acid of concentration 92-97.5% H,SO, or oleum (105% H,SO,) at 50°C. However, a small proportion (1%) of resorcinol remains unchanged and is subjected to oxi- dation during the subsequent nitration. It is responsible for foaming during the nitration. According to the above authors, prolonged sulphonation or application of more concentrated oleum does not prevent the presence of unsulphonated resor- cinol.
Sulphonation yields only three compounds: I, II, and III The sulphonic acids I and II can be obtained by sulphonation of resorcinol with sulphuric acid or oleum at temperatures which are not higher than 100°C (Mertz and Zetter [32]). The trisulphonic acid can only be prepared by the action of oleum at 200°C. According to Aubertein and Emeury [29], resorcinol can be sulphonated to the compound II by the action of a tenfold quantity (by weight) of sulphuric acid of concentration 92-97.5% H,SO, or oleum (105% H,SO,) at 50°C. However, a small proportion (1%) of resorcinol remains unchanged and is subjected to oxi- dation during the subsequent nitration. It is responsible for foaming during the nitration. According to the above authors, prolonged sulphonation or application of more concentrated oleum does not prevent the presence of unsulphonated resor- cinol.
3,5-Dinitropyrocatechol (m. p. 164°C) was prepared by Nietzki and Moll [38] by nitrating pyrocatechol diacetate with cold cont. nitric acid, followed by hydrolysis of ester groups with sulphuric acid.
3,5-Dinitropyrocatechol (m. p. 164°C) was prepared by Nietzki and Moll [38] by nitrating pyrocatechol diacetate with cold cont. nitric acid, followed by hydrolysis of ester groups with sulphuric acid.
When boiled with ethyl alcohol trinitroanisole is converted to trinitrophenetole: It is, therefore, necessary to use methyl alcohol as the solvent for the recrystallization of trinitroanisole.
When boiled with ethyl alcohol trinitroanisole is converted to trinitrophenetole: It is, therefore, necessary to use methyl alcohol as the solvent for the recrystallization of trinitroanisole.
A mixture of the tetranitroanisole isomers may be obtained (according to Claes- sen [7]) by the nitration of m- nitroanisole. The compounds are not stable since their nitro groups in the meta position are readily hydrolysed or substituted (van Duin and van Lennep [8]). Their sensitiveness to impact is similar to that of TNT. The expansion they give in a lead block is about 135% of that given by TNT.
A mixture of the tetranitroanisole isomers may be obtained (according to Claes- sen [7]) by the nitration of m- nitroanisole. The compounds are not stable since their nitro groups in the meta position are readily hydrolysed or substituted (van Duin and van Lennep [8]). Their sensitiveness to impact is similar to that of TNT. The expansion they give in a lead block is about 135% of that given by TNT.
PENTANITRODIPHENYL ETHER
PENTANITRODIPHENYL ETHER
Neither substance is a strong enough explosive to make their rather expensive production economical.
Neither substance is a strong enough explosive to make their rather expensive production economical.
The authors state that the substance is less sensitive and more powerful than yicric acid.
The authors state that the substance is less sensitive and more powerful than yicric acid.
(G. M. Robinson and R. Robinson [13], Gosh [14], Heertjes, Dahmen and Wierda [ 11).
(G. M. Robinson and R. Robinson [13], Gosh [14], Heertjes, Dahmen and Wierda [ 11).
2,2’ ,4,4’,6,6’-Hexanitrodiphenyl sulphone (m. p. 307°C, decomposition) for yellowish crystals difficult to dissolve in most organic solvents. In 1912 Sprengstoff A. G. Carbonit [17] was granted a patent for a meth of preparation of this explosive, consisting in reacting hexanitrodiphenyl sulph with nitric acid. Since picryl chloride, as the starting material for picryl sulphi was rather expensive, another method of preparation of hexanitrodiphenyl sulpho via tetranitrodiphenyl sulphide, was also used. The latter was obtained by treat: shlorodinitrobenzene with sodium thiosulphate. Then it was nitrated and oxidiz SImuItaneously with nitric acid to hexanitrodinhenv|] sulnhone:
2,2’ ,4,4’,6,6’-Hexanitrodiphenyl sulphone (m. p. 307°C, decomposition) for yellowish crystals difficult to dissolve in most organic solvents. In 1912 Sprengstoff A. G. Carbonit [17] was granted a patent for a meth of preparation of this explosive, consisting in reacting hexanitrodiphenyl sulph with nitric acid. Since picryl chloride, as the starting material for picryl sulphi was rather expensive, another method of preparation of hexanitrodiphenyl sulpho via tetranitrodiphenyl sulphide, was also used. The latter was obtained by treat: shlorodinitrobenzene with sodium thiosulphate. Then it was nitrated and oxidiz SImuItaneously with nitric acid to hexanitrodinhenv|] sulnhone:
Although, according to Fliirscheim, tetranitroaniline has sufficient thermal stability, even a product of the highest purity does not give a satisfactory heat test. According to Ingraham [19b], tetranitroaniline has shown evidence of decom- position by the heat test at 65.5°C when only a small amount of moisture was pie- sent. The main product of decompositions was II. Prolonged heating at 75°C results in loss of a nitro group. At 120°C decomposition takes place which proceeds in a way similar to that of tetryl. The initiation temperature is 231-233°C. The specific gravity of the product is 1.867 [19]. With regard to explosive power and sensitiveness to impact tetranitroaniline 1 a ee ae 2 A @ <a cee rs r 1
Although, according to Fliirscheim, tetranitroaniline has sufficient thermal stability, even a product of the highest purity does not give a satisfactory heat test. According to Ingraham [19b], tetranitroaniline has shown evidence of decom- position by the heat test at 65.5°C when only a small amount of moisture was pie- sent. The main product of decompositions was II. Prolonged heating at 75°C results in loss of a nitro group. At 120°C decomposition takes place which proceeds in a way similar to that of tetryl. The initiation temperature is 231-233°C. The specific gravity of the product is 1.867 [19]. With regard to explosive power and sensitiveness to impact tetranitroaniline 1 a ee ae 2 A @ <a cee rs r 1
2,2’ ,4,4’,6,6’-Hexanitrodiphenylamine (m. p. 243-245°C) was first mentioned in the chemical literature in 1876 and as long ago as 1891 Haussermann [21] drew attention to its explosive properties. The product is known under the names of Dipicrylamine, Hexyl, Heksyl, Hexamite, Hexamin, etc. The annlicatian af heyy] ac an exynlacive anec hack ac far ace 1011 Tt wae widely
2,2’ ,4,4’,6,6’-Hexanitrodiphenylamine (m. p. 243-245°C) was first mentioned in the chemical literature in 1876 and as long ago as 1891 Haussermann [21] drew attention to its explosive properties. The product is known under the names of Dipicrylamine, Hexyl, Heksyl, Hexamite, Hexamin, etc. The annlicatian af heyy] ac an exynlacive anec hack ac far ace 1011 Tt wae widely
Densities obtainable under various pressures are :
Densities obtainable under various pressures are :
In addition to the 1,3,6,8-isomer a product, named by Ciamician and Silbe the Y— isomer, has been obtained, which, according to recent investigations, he proved to be the 1,2,6,8-isomer (II). From the reaction product pure compoun I may be isolated by extraction with toluene, followed by crystallization from acet acid. The pure product I may also be obtained by treating the crude product wit sodium sulphite. According to Murphy, Schwartz, Picard and Kaufman [34], tt melting point of the product may be raised in this way from 278° to 296°C ; the cost of a 10% loss of yield. The same authors found that during the nitratic process the 1,2,6,8-isomer (ID) is formed along with the principal product. Thi isomer may be obtained in a larger quantity if carbzole is subjected to sulphons tion with oleum prior to nitration. The constitution of tetranitrocarhazole (1) was determined by Borsche an
In addition to the 1,3,6,8-isomer a product, named by Ciamician and Silbe the Y— isomer, has been obtained, which, according to recent investigations, he proved to be the 1,2,6,8-isomer (II). From the reaction product pure compoun I may be isolated by extraction with toluene, followed by crystallization from acet acid. The pure product I may also be obtained by treating the crude product wit sodium sulphite. According to Murphy, Schwartz, Picard and Kaufman [34], tt melting point of the product may be raised in this way from 278° to 296°C ; the cost of a 10% loss of yield. The same authors found that during the nitratic process the 1,2,6,8-isomer (ID) is formed along with the principal product. Thi isomer may be obtained in a larger quantity if carbzole is subjected to sulphons tion with oleum prior to nitration. The constitution of tetranitrocarhazole (1) was determined by Borsche an
In a method applied at Hochst, 1896 kg of 96% sulphuric acid are charged in he sulphonator, followed by 950 kg of commercial grade carbazole (88-9 yurity). The whole is stirred at room temperature for 50 min. Then the temperatu s raised to 95°C and stirring is continued until a sample taken from the sulphonat issolves completely in water. At this stage of the process disulphonic acid is forme ‘hen the sulphonator contents are cooled to 70°C and the remainder of the sulphur cid, i.e. 1561 kg (the total quantity being 3430 kg) is added. Further sulphonati akes place, resulting in the formation of 1,3,6-trisulphonic acid. It has been proved that carrying out the reaction in two stages, as describ: ibove, makes the sulphonation process proceed more quietly and prevents t
In a method applied at Hochst, 1896 kg of 96% sulphuric acid are charged in he sulphonator, followed by 950 kg of commercial grade carbazole (88-9 yurity). The whole is stirred at room temperature for 50 min. Then the temperatu s raised to 95°C and stirring is continued until a sample taken from the sulphonat issolves completely in water. At this stage of the process disulphonic acid is forme ‘hen the sulphonator contents are cooled to 70°C and the remainder of the sulphur cid, i.e. 1561 kg (the total quantity being 3430 kg) is added. Further sulphonati akes place, resulting in the formation of 1,3,6-trisulphonic acid. It has been proved that carrying out the reaction in two stages, as describ: ibove, makes the sulphonation process proceed more quietly and prevents t
The use of hexanitro-oxanilide (m. p. 295-300°C) as an explosive material was suggested by the Societe Anonyme d’Explosifs [39].
The use of hexanitro-oxanilide (m. p. 295-300°C) as an explosive material was suggested by the Societe Anonyme d’Explosifs [39].
All the compounds are formed in the nitration of azobenzene (Werner and Stiasny Tay
All the compounds are formed in the nitration of azobenzene (Werner and Stiasny Tay
Salts of nitromethane are extremely sensitive to flame and bum readily. They are also sensitive to friction, impact and electric discharge. Mercuric salt can be transformed into mercuric fulminate (Vol. IID.
Salts of nitromethane are extremely sensitive to flame and bum readily. They are also sensitive to friction, impact and electric discharge. Mercuric salt can be transformed into mercuric fulminate (Vol. IID.
Tetranitromethane like polynitro-aromatic hydrocarbons is able to form additior compounds (p. 222, Fig. 47). Nevertheless, the existence of an addition compound of tetranitromethane with benzene has not been proved by thermal analysis, when this was carried out recently by T. Urbanski, Piskorz, Centner and Maciejewski 59]. They also examined a number of other systems by means of thermal analysis. [he compositions of various eutectics determined by the above authors are shown in Table 127.
Tetranitromethane like polynitro-aromatic hydrocarbons is able to form additior compounds (p. 222, Fig. 47). Nevertheless, the existence of an addition compound of tetranitromethane with benzene has not been proved by thermal analysis, when this was carried out recently by T. Urbanski, Piskorz, Centner and Maciejewski 59]. They also examined a number of other systems by means of thermal analysis. [he compositions of various eutectics determined by the above authors are shown in Table 127.
TABLE 128 The explosive properties of nitrobenzene-tetranitromethane solutions were examined in detail by Roth [62] who measured rates of detonation power (on a 10.5 by 7 mm crusher gauge), and sensitiveness to impact, using nitroglycerine and TNT as standards (Table 129). Lead block expansions are not included here as they were not determined by standard methods.
TABLE 128 The explosive properties of nitrobenzene-tetranitromethane solutions were examined in detail by Roth [62] who measured rates of detonation power (on a 10.5 by 7 mm crusher gauge), and sensitiveness to impact, using nitroglycerine and TNT as standards (Table 129). Lead block expansions are not included here as they were not determined by standard methods.
TABLE 130 + For the initiation a No. 8 detonator and 10 g of TNT were applied.
TABLE 130 + For the initiation a No. 8 detonator and 10 g of TNT were applied.

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