Nitration processes

Abstract

The present invention relates to improvements in processes of preparing dinitrated .[.aromatic compounds, particularly dinitrated aniline and dinitrated substituted aniline compounds, employing relatively dilute and then more concentrated nitric acid as the nitrating agent.]. .Iadd.aniline and substituted phenol compounds in a two-step process, employing, in the first or mononitration step the spent nitric acid from the second of dinitration step. .Iaddend.

I claim: 
     
       1. A continuous process of dinitrating a dinitratable substituted aniline compound which comprises continously supplying (1) an aqueous nitric acid of about 10-40% HNO 3  by weight and substantially free of sulfuric acid, (2) a substituted aniline compound and (3) a liquid, inert, water-immiscible organic solvent for said aniline compound, in a mole ratio of about 1:1 to about 1:1.3 .Iadd.of .Iaddend.HNO 3  to said aniline compound, to a reaction zone at a temperature of about 40° to about 70° C. and atmospheric pressure, thereby forming in said zone an emulsion containing a salt of said nitric acid and aniline compound, continuously conveying the overflow emulsion from said zone to a separation zone to allow continuous separation of said emulsion into an aqueous phase and an organic phase containing said salt and solvent, continuously conveying said organic phase to a second and third reaction zone and reacting said salt in the organic phase in said zones with an aqueous nitric acid of 65%-80% by weight HNO 3  and substantially free of sulfuric acid at a temperature of about 40° C. to about 70° C. at atmospheric pressure, in a mole ratio of HNO 3  to salt of about 1.9:1 to about 2.5:1, until the dinitro derivative of said aniline compound is formed and continuously removing said derivative in said organic solvent from the third reaction zone, said substituted aniline compound having the structural formula: ##STR4## wherein: R 7  is CH 3 , C 2  H 5 , C 3  H 7  --n, C 3  H 7  --i, .[.C 4  H 9  13 i.]. .Iadd.C 4  H 9  --i, .Iaddend.CF 3  or Cl;   X is CH 3 , --CH 2  --O--CH 3  or .[.--CH(CH 3 )O--CH 3  .]. .Iadd.--CH(CH 3 )--O--CH 3  .Iaddend.; and   R 5  is C 3  -C 7  secondary alkyl, or monochloralkyl C 3  -C 4 .   
     
     
       2. A process according to claim 1, wherein said aniline compound is n-sec. butyl-3, 4-xylidine, N-(1-ethylpropyl)-3, 4-xylidine or N-(1-methylbutyl)-3, 4-xylidine. 
     
     
       3. The continuous process defined in claim 1, wherein, in the step in which the said dinitro derivative is formed, a spent nitric acid is yielded in a concentration of about 10%-50% HNO 3  by weight, characterized in that the said spent acid so yielded is thereafter used in the first defined supplying step of said continuous process. 
     
     
       4. A process of dinitrating a dinitratable substituted aniline compound which comprises reacting (1) an aqueous nitric acid of about 10-40% HNO 3  by weight and substantially free of sulphuric acid with (2) a substituted aniline compound in the presence of a liquid, inert, water-immiscible organic solvent for said aniline compound, in a mole ratio of about 1:1 to about 1:1.3 of HNO 3  to said aniline compound and at a temperature of about 40° to about 70° C. and atmospheric pressure, thereby forming an emulsion containing a salt of said nitric acid and aniline compound dissolved in said solvent, separating said emulsion into an aqueous phase and an organic phase containing said salt, separating the organic phase from the aqueous phase and reacting said salt in the organic phase with an aqueous nitric acid of 65-80% by weight HNO 3  and substantially free of sulphuric acid in a mole ratio of HNO 3  to said salt of about 1.9:1 to about 2.5:1 and at a temperature of about 40°  C. to about 70° C. and at atmospheric pressures until a reactive mixture containing the dinitro derivative of said compound is formed, said substituted aniline compound having the structural formula: ##STR5## wherein: R 5  is C 3  -C 7  secondary alkyl or monochloralkyl C 3  -C 4  ; X is CH 3 , --CH 2  --O--CH 3  or --CH(CH 3 )--O--CH 3  ; and   R 7  is CH 3 , C 2  H 5 , C 3  H 7  --n, C 3  H 7  --i, C 4  H 9  --i, CF 3  or Cl.   
     
     
       5. A process according to claim 4, wherein said aniline compound is n-sec. butyl-3, 4-xylidine N-(1-ethylpropyl)-3, 4-xylidine, or N-(1-methylbutyl)-3, 4-xylidine. 
     
     
       6. The process defined in claim 4 wherein the reaction mixture containing said dinitro derivative also contains spent nitric acid in a concentration of 10%-50% HNO 3  by weight, together with the subsequent step of repeating said process utilizing the said spent nitric acid in the said first-defined reacting step. .Iadd. 
     
     
       7.  The process of dinitrating a dinitratable substituted phenol compound without use of sulfuric acid which comprises the steps of: (A) supplying the following ingredients: an aqueous nitric acid of about 10% to 50% HNO 3  by weight and substantially free of sulfuric acid; a dinitratable substituted phenol compound; and a liquid, inert, water-immiscible organic solvent for said substituted phenol compound;   (B) reacting said ingredients, thereby forming an emulsion containing a mononitrated derivative of the said compound;   (C) permitting the separation of said emulsion into an organic phase containing the mononitrated derivative of said compound, and an aqueous phase containing aqueous spent nitric acid as a waste;   (D) reacting said separated organic phase with aqueous nitric acid of 60% to 100% by weight HNO 3  and substantially free of sulfuric acid, thereby forming a second mixture;   (E) permitting the separation of said second mixture into an aqueous phase consisting of spent nitric acid of 10% to 50% by weight, and an organic phase containing the dinitrated derivative of said substituted phenol compound;   (F) removing said organic phase containing the dinitrated derivative, thus leaving the said spent nitric acid of step (E), and   (G) repeating the foregoing steps (A) to (F), inclusive, utilizing as the acid in step (A) the said spent nitric acid of step (E),   whereby the aqueous waste of step (C) is the only waste generated in the process..Iaddend. .Iadd.8. The process as defined in claim 7, wherein the said spent nitric acid of step (E) is diluted to substantially 10% concentration prior to its utilization as the acid in step (A)..Iaddend. .Iadd.9. The process of dinitrating a dinitratable aniline compound without the use of sulfuric acid, which comprises the steps of:   (A) supplying the following ingredients: an aqueous nitric acid of about 10% to 50% HNO 3  by weight and substantially free of sulfuric acid; a dinitratable aniline compound; and a liquid, inert, water-immiscible organic solvent for said aniline compound;   (B) reacting said ingredients thereby forming an emulsion containing a mononitrated derivative of the said compound;   (C) permitting the separation of said emulsion into an organic phase containing the mononitrated derivative of said compound and an aqueous phase containing aqueous spent nitric acid as a waste;   (D) reacting said separated organic phase with aqueous nitric acid of 60% to 100% by weight HNO 3  and substantially free of sulfuric acid, thereby forming a second mixture;   (E) permitting the separation of said second mixture into an aqueous phase consisting of spent nitric acid of 10% to 50% by weight, and an organic phase containing the dinitrated derivative of said aniline compound;   (F) removing said organic phase containing the dinitrated derivative, thus leaving the said spent nitric acid, and   (G) repeating the foregoing steps (A) to (F), inclusive utilizing as the acid in step (A) the said spent nitric acid of step (E),   whereby the aqueous waste of step (C) is the only waste generated in the process..Iaddend. .Iadd.10. The process as defined in claim 9, wherein the residual nitric acid of the aqueous phase of said step (C) is substantially 10% by weight nitric acid or less..Iaddend.