Process for making 5-introbarbituric acid and salts thereof

• US 5,428,165 A
• Filed: 01/10/1994
• Issued: 06/27/1995
• Est. Priority Date: 01/06/1994
• Status: Expired due to Fees

• Current Assignee: Alliant Techsystems Incorporated (Northrop Grumman Corporation)
• Original Assignee: Thiokol Corporation (Howmet Aerospace, Inc.)
• Inventors: Wardle, Robert W.
• Primary Examiner(s): TSANG, CECILIA J
• Application Number:
  US08/179,737
• Time in Patent Office: 533 Days
• Field of Search: 544/301
• US Class Current: 544/301
• CPC Class Codes: C07D 239/62 Barbituric acids

Abstract

A process for preparing salts of 5-nitrobarbituric acid involves allowing an in situ generated a compound represented by formula (I): ##STR1## wherein R₁ and R₂ are the same or different and are, H, C₁ to C₈ alkyl or substituted C₁ to C₈ alkyl, aryl or substituted aryl, to condense with urea to obtain a condensation product; and neutralizing the condensation product with at least one organic base and another cation source (MX) at a pH≧7 and recovering the thus formed salt of 5-nitrobarbituric acid.

Claims

1. A process for preparing salts of 5-nitrobarbituric acid comprising allowing an in situ generated diethyl nitro malonate to condense with urea to obtain 5-nitrobarbituric acid and neutralizing said acid with a nitrogen containing organic base, ammonium, hydrazinium, alkali metal salts, alkaline earth metal salts, salts of transition metals, or mixtures thereof, and recovering the thus formed salt of 5-nitrobarbituric acid without distillation or isolation of intermediate products during the preparation of the 5-nitrobarbituric acid salts.

2. A process according to claim 1, wherein said organic base comprises a cation selected from the group consisting of guanidinium, aminoguanidinium, diaminoguanidinium, triaminoguanidinium, biguanidinium, aminotriazolium, guanizinium, aminotetrazolium, and hydrazino tetrazolium.

3. A process according to claim 1, wherein the nitrated diethyl malonate is obtained by nitrating diethyl malonate with a nitrating reagent.

4. A process according to claim 3, wherein said nitrating reagent is selected from the group consisting of nitric acid, nitric acid and acetic anhydride, and a mixture of acetic acid and acetic anhydride with ammonium nitrate or at least one metal nitrate.

5. A process according to claim 4, wherein said nitrating reagent is acetic acid or acetic anhydride and a metal nitrate selected from the group consisting of Mn(NO3)₂, Cu(NO₃)₂, NANO₃, Ca(NO₃)2, Mg(NO₃)₂, and Sr(NO₃)₂.

6. A process according to claim 1, wherein the nitrated diethyl malonate is generated in situ by allowing at least one haloacetic acid to react with a cyanide anion source to obtain cyanoacetic acid, and allowing the cyanoacetic acid to react with ethanol in the presence of a nitrating reagent.

7. A process according to claim 6, wherein said haloacetic acid is bromoacetic acid, chloroacetic acid, or a mixture thereof.

8. A process according to claim 6, wherein said cyanide anion source is selected from the group consisting of alkali metal cyanides and alkaline earth metal cyanides.

9. A process according to claim 8, wherein said cyanide anion source is selected from the group consisting of sodium cyanide, potassium cyanide and cupric cyanide.

10. A process according to claim 6, wherein the reaction of cyanoacetic acid with ethanol is conducted at a pH≦

about 2.

11. A process according to claim 6, wherein said nitrating reagent is selected from the group consisting of nitric acid, nitric acid and acetic anhydride, and a mixture of acetic acid and acetic anhydride with ammonium nitrate or at least one metal nitrate.

12. A process according to claim 6, wherein said nitrating reagent is a mixture of acetic acid and acetic anhydride and at least one metal nitrate selected from the group consisting of Mn(NO3)₂, Cu(NO₃)₂, NANO₃, Ca(NO₃)₂, Mg(NO₃)₂, and Sr(NO₃)₂.

13. A process for preparing salts of 5-nitrobarbituric acid comprising allowing an in situ generated a compound represented by formula (I):

##STR5## wherein R_l and R₂ are the same or different and are, H, C₁ to C₈ alkyl or substituted C₁ to C₈ alkyl, aryl or substituted aryl, to condense with urea to obtain a condensation product; and

neutralizing the condensation product with at least one member selected from the group consisting of an organic base and another cation source (MX), and recovering the thus formed salt of 5-nitrobarbituric acid without distillation or isolation of intermediate products during the preparation of the 5-nitrobarbituric acid salts.

14. A process for preparing a salt of 5-nitrobarbituric acid comprising adding a dehydrating reagent to nitromalonic acid and urea, and neutralizing the reaction product thereof to obtain a salt of 5-nitrobarbituric acid without distillation or isolation of intermediate products during the preparation of the 5-nitrobarbituric acid salts.

15. A process according to claim 14, wherein said dehydrating reagent is an organic anhydride.

16. A process according to claim 15, wherein said dehydrating reagent is selected from the group consisting of acetic anhydride, propionic anhydride, butyric anhydride, and benzoic anhydride.

17. A process according to claim 14, wherein said neutralization is carried out with a reagent having a cation selected from the group consisting of ammonium and hydrazinium, guanidinium, aminoguanidinium, diaminoguanidinium, triaminoguanidinium, biguanidinium, aminotriazolium, guanizinium, aminotetrazolium, and hydrazino tetrazolium.

18. A process for preparing 5-nitrobarbituric acid comprising generating in situ diethyl nitromalonate and condensing the diethyl nitromalonate with urea and recovering the thus formed 5-nitrobarbituric acid.