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WO1996035659A1 - Amination de composes aromatiques electrophiles par substitution nucleophile vicariante - Google Patents

Amination de composes aromatiques electrophiles par substitution nucleophile vicariante Download PDF

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Publication number
WO1996035659A1
WO1996035659A1 PCT/US1996/006663 US9606663W WO9635659A1 WO 1996035659 A1 WO1996035659 A1 WO 1996035659A1 US 9606663 W US9606663 W US 9606663W WO 9635659 A1 WO9635659 A1 WO 9635659A1
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Prior art keywords
potassium
sodium
group
butoxide
trinitrobenzene
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PCT/US1996/006663
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English (en)
Inventor
Alexander R. Mitchell
Phillip F. Pagoria
Robert D. Schmidt
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University of California Berkeley
University of California San Diego UCSD
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University of California Berkeley
University of California San Diego UCSD
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Priority claimed from US08/440,024 external-priority patent/US5633406A/en
Priority claimed from US08/440,017 external-priority patent/US5569783A/en
Application filed by University of California Berkeley, University of California San Diego UCSD filed Critical University of California Berkeley
Priority to EP96916451A priority Critical patent/EP0835237A1/fr
Priority to JP8534272A priority patent/JPH11511740A/ja
Publication of WO1996035659A1 publication Critical patent/WO1996035659A1/fr
Priority to US08/967,914 priority patent/US6069277A/en
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/02—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of hydrogen atoms by amino groups

Definitions

  • the present invention concerns the mono- and or poly-amination of electrophilic aromatic compounds.
  • the present invention concerns the discovery and use of quaternary hydrazinium salts, e.g., 1,1,1-trisubstituted hydrazinium salts, for vicarious nucleophilic substitution (VNS) of hydrogen, which provide new and improved syntheses of mono and/or poly amino-aromatic compounds, such as l,3-diamino-2,4,6- trinitrobenzene (DATB) and l,3,5-triamino-2,4,6-trinitrobenzene (TATB).
  • VNS vicarious nucleophilic substitution
  • the present invention also concerns the use of 4-amino-l,2,4-triazole, as well as hydroxylamine and its O-alkyl derivatives, to provide new and improved syntheses of aromatic amine compounds, such as DATB and TATB, by VNS reactions.
  • TBN 1,3,5- trinitrobenzene
  • TNT 2,4,6-trinitrotoluene
  • TAA l-amino-2,4,6-trinitrobenzene
  • DATB l,3-diamino-2,4,6-trinitrobenzene
  • TATB l,3,5-triamino-2,4,6- trinitrobenzene
  • DATB and TATB are highly desirable, insensitive explosives that are used primarily in specialty applications. Part of the reason that they are used in special as opposed to general explosive applications is high cost. They are too expensive to use in ordinary applications when other less expensive explosives can be used.
  • TATB is expensive is that it is usually prepared from 1,3,5-trichlorobenzene which is expensive and is not generally available from domestic suppliers.
  • the ammonium chloride byproduct (NH 4 C1) is difficult to remove completely and may cause compatibility problems in certain types of ordnance (e.g., U.S. Patent 4,032,377).
  • Additional art of interest includes, for example:
  • TNT pentanitroaniline
  • TATB triaminotrinitrobenzene
  • German patent, Ger. Offen DE 3,612,2378 teaches the use of TATB to prepare components of lyotropic liquid-crystal phases for use in display devices.
  • TATB is also valuable in non-explosive applications.
  • K. Praefake and B. Kohne, Ger. Offen. DE 3.612.238 disclose the use of TATB to prepare hexaaminobenzene derivatives which are used as components of lyotropic liquid-crystal phases, which can be used in display devices. Additional art of interest includes, for example:
  • the present invention concerns the monoamination or polyamination of electrophilic aromatic compounds.
  • the reagents used are 1,1,1- trialkylhydrazinium salts (e.g., halides) or 4-amino-l,2,4-triazole, hydroxylamine or O- alkylhydroxylamine, wherein alkyl is selected from groups having 1 to 10 carbon atoms.
  • the present invention relates to a process to produce one or more monoamino, diamino or polyamino aromatic compounds, which process comprises: (a) reacting at ambient pressure and a temperature of between about 0 and
  • Q 1 , Q 2 , Q 3 , X 1 , Y 1 , and Z 1 are each independently selected from the group consisting of -H, -NO 2 , -CH 3 , -COOH, -OCH 3 , and -NH 2 , with the proviso that at least 1 of Q 1 , Q 2 , Q 3 , X 1 , Y 1 , and Z 1 is hydrogen, with (i) an effective amount of quaternary hydrazinium salts, such as 1,1,1,- trialkylhydrazinium salt wherein alkyl is selected from methyl, ethyl, propyl, butyl or benzyl and the anion is selected from chloride, bromide, iodide, fluoride, sulfate, hydroxide, mesylate, triflate, or tetrafluoroborate, or
  • the hydroxylamine and O-alkylhydroxylamine are used with the proviso that only diamino- or polyamino- aromatic compounds are produced.
  • the present invention also relates to a process to produce l,3-diamino-2,4,6- trinitrobenzene (DATB), l,3,5-triamino-2,4,6-trinitrobenzene (TATB) or 3,5-diamino- 2,4,6-trinitrotoluene (DATNT) by:
  • X, Y, and Z are each independently selected from the group consisting of -H, -CH 3 , and -NH 2 , with the proviso that at least 1 of X, Y, and Z are hydrogen; with an amount effective to produce DATB, TATB, or DATNT of 1,1,1 -trialkyl hydrazinium salt wherein alkyl is selected from methyl, ethyl, propyl, butyl, or benzyl, and the anion of the salt is selected from chloride, bromide, iodide, fluoride, sulfate, hydroxide, mesylate, triflate, tetrafluoroborate and the like; in the presence of a strong base selected from sodium butoxide, potassium butoxide, potassium propoxide, sodium propoxide, sodium ethoxide, potassium ethoxide, sodium methoxide, potassium methoxide, and combinations thereof; in a solvent selected from the group consisting of
  • X, Y and Z are each independently selected from -H, -CH 3 , or NH 2 .
  • the present invention concerns a process to produce 1,3- diamino-2,4,6-trinitrobenzene (DATB) or l,3,5-triamino-2,4,6-trinitrobenzene (TATB):
  • DATB 1,3- diamino-2,4,6-trinitrobenzene
  • TATB l,3,5-triamino-2,4,6-trinitrobenzene
  • alkyl is selected from methyl, ethyl, propyl, butyl, or benzyl and the anion of the salt is selected from chloride, bromide, iodide, fluoride, sulfate, hydroxide, mesylate, triflate, tetrafluoroborate and the like to produce compound III or compound IV; in the presence of a strong base selected from sodium butoxide, potassium butoxide, potassium propoxide, sodium propoxide, sodium ethoxide, potassium ethoxide, sodium methoxide, potassium methoxide, or combinations thereof; in a solvent selected from the group consisting of methanol, ethanol, propanol, butanol, dimethylsulfoxide, N-methylpyrrolidone, hexamethylphosphoramide, dimethylformamide, di
  • X, Y, and Z are each independently selected from the group consisting of -H, and -NH 2 , with the proviso that at least 1 of X, Y, and Z is hydrogen; with an effective amount of 1 , 1 , 1 -trialkylhydrazinium salt wherein alkyl is selected from methyl, ethyl, propyl, butyl, or benzyl, and the anion of the salt is selected from chloride, bromide iodide, fluoride, sulfate, hydroxide, mesylate, trifiate, tetrafluoroborate and the like.
  • a base selected from the group consisting of sodium butoxide, potassium butoxide, potassium propoxide, sodium propoxide, sodium ethoxide, potassium ethoxide, sodium methoxide, potassium methoxide, and mixtures thereof
  • a solvent selected from the group consisting of methanol, ethanol, propanol, butanol, dimethylsulphoxide, N-methylpyrrolidone, hexamethylphosphoramide, dimethylformamide, dimethylacetamide, and mixtures thereof;
  • DATB is produced when the 1,1,1-trialkylhydrazinium salt is present in between about 1.9 and 2.3 molar equivalents per mole of compound V.
  • starting material is selected from 1,3,5-trinitrobenzene, 2,4,6- trinitroaniline, or l,3-diamino-2,4,6-trinitrobenzene.
  • the 1 , 1 , 1 -trialkylhydrazinium salt is 1 , 1 , 1 -trimethylhydrazinium iodide.
  • the strong base is selected from sodium methoxide or potassium tert- butoxide.
  • the solvents are selected from the group consisting of methanol, ethanol, propanol, butanol, dimethylsulphoxide, N-methylpyrrolidone, hexamethylphosphoramide, dimethylformamide, dimethylacetamide and mixtures thereof, provided that when alcohols are present primarily DATB and picramide are formed.
  • TATB is produced when the 1,1,1 -trialkylhydrazinium salt is present in between about 3.9 and 5.5 molar equivalents per mole of compound V.
  • the present process includes reacting:
  • X, Y, and Z are each independently selected from the group consisting of -H, - CH 3 , and -NH 2 , with the proviso that at least 1 of X, Y, and Z is hydrogen, with an effective amount of 1 , 1 , 1 -trialkylhydrazinium salt wherein alkyl is selected from methyl, ethyl, propyl or butyl and anion is selected from chloride, bromide, iodide, fluoride, sulfate, hydroxide, mesylate, triflate, tetrafluoroborate, and the like.
  • a base selected from the group consisting of sodium butoxide, potassium butoxide, potassium propoxide, sodium propoxide, sodium ethoxide, potassium ethoxide, sodium methoxide, potassium methoxide, and mixtures thereof
  • a solvent selected from the group consisting of methanol, ethanol, propanol, butanol, dimethylsulphoxide, N-methylpyrrolidone, hexamethylphosphoramide, dimethylformamide, dimethylacetamide, and mixtures thereof; and (B) isolating the DATB, or TATB produced.
  • reaction temperature is between about 10 and 30°C.
  • present invention concerns a process to produce aminated aromatic compounds, which process comprises:
  • an electrophilic aromatic compound which is selected from benzene, naphthalene, quinoline, quinoxaline, pyridine, pyrazine, pyrimidine, pyrazole, imidazole, and the like.
  • the electrophilic aromatic compound may be substituted with one or more electron withdrawing groups, such as -SO 3 H, -NO 2 , -CN, -CF 3 , -COOR, -
  • nitrobenzenes examples include:
  • R 2 , R 3 , and R 4 are each independently selected from -H, -CH 3 , -F, -Cl, - Br, -I, -CN, -COOH, -COOR 11 where R 11 is Cl to CIO alkyl, or -OCH 3 , and R 5 - R 9 are each independently selected from -H, -CH 3 , -F, -Cl, -Br, -I, -CN, -COOH, or -OCH 3 or mixtures thereof;
  • dialkyl is selected from methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, (-CH 2 (CH 2 ) n CH 2 -), -(CH,CH 2 )O(CH 2 CH 2 )-, hexyl, dodecyl, or pyridyl, and n is 1 to 10.
  • R is selected from H, Cl - C20 alkyl, or aryl, and anion is selected from chloride, bromide, iodide, fluoride, sulfate, hydroxide, mesylate, triflate, tetrafluoroborate, and the like.
  • a base selected from the group consisting of sodium butoxide, potassium butoxide, potassium propoxide, sodium propoxide, sodium ethoxide, potassium ethoxide, sodium methoxide, potassium methoxide, and mixtures thereof
  • a solvent selected from the group consisting of methanol, ethanol, propanol, butanol, dimethylsulphoxide, N-methylpyrrolidone, hexamethylphosphoramide, dimethylformamide, dimethylacetamide, and mixtures thereof;
  • the present invention concerns a process to produce 1,3- diamino-2,4,6-trinitrobenzene (DATB) or l,3,5-triamino-2,4,6,-trinitrobenzene (TATB) by:
  • X, Y, and Z are each independently selected from the group consisting of -H and -NH 2 , with the proviso that at least 1 of X, Y, and Z is hydrogen, with an effective amount of 4-amino-l,2,4-triazole (ATA) to produce DATB or TATB or hydroxylamine or O-alkylhydroxylamine, wherein alkyl has 1 to 10 carbon atoms, to primarily produce DATB; in the presence of a strong base selected from sodium butoxide, potassium butoxide, potassium propoxide, sodium propoxide, sodium ethoxide, potassium ethoxide, sodium methoxide, potassium methoxide, and combinations thereof; in a solvent selected from the group consisting of methanol, ethanol, propanol, butanol, dimethylsulphoxide, N-methylpyrrolidone, hexamethylphosphoramide, dimethylformamide, dimethylacetamide and mixtures thereof, provided that when alcohol
  • the present invention concerns a process to produce 1,3- diamino-2,4,6-trinitrobenzene (DATB) or l,3,5-triamino-2,4,6,-trinitrobenzene (TATB): (a) by obtaining an aromatic compound of the structure:
  • ATA hydroxylamine or O-alkylhydroxylamine
  • a strong base selected from sodium butoxide, potassium butoxide, potassium propoxide, sodium propoxide, sodium ethoxide, potassium ethoxide, sodium methoxide, potassium methoxide, and combinations thereof; in a solvent selected from the group consisting of dimethylsulphoxide, N- methylpyrrolidone, hexamethylphosphoramide, dimethylformamide, dimethylacetamide, or mixtures thereof, and isolating the product which is compound III;
  • X, Y, and Z are each independently selected from the group consisting of -H and -NH 2 , with the proviso that at least 1 of X, Y, and Z is hydrogen; with an effective amount of 4-amino-l,2,4-triazole, hydroxylamine or O- alkylhydroxylamine wherein alkyl contains 1 to 10 carbon atoms; in the presence of a base selected from the group consisting of sodium butoxide, potassium butoxide, potassium propoxide, sodium propoxide, sodium ethoxide, potassium ethoxide, sodium methoxide, potassium methoxide, and mixtures thereof; in a solvent selected from the group consisting of methanol, ethanol, propanol, butanol, dimethylsulphoxide, N-methylpyrrolidone, hexamethylphosphoramide, dimethylformamide, dimethylacetamide, and mixtures thereof, with the proviso that when alcohol is present or hydroxylamine and its
  • DATB is produced when ATA, hydroxyl amine or O- alkylhydroxylamine is present in between about 1.9 and 2.3 molar equivalents per mole of compound V.
  • structure V is selected from 1,3,5-trinitrobenzene, 2,4,6-trinitroaniline, or 1 ,3-di_-mino-2,4,6-trinitrobenzene.
  • the strong base is selected from sodium methoxide or potassium tert- butoxide.
  • the solvents are selected from methanol, ethanol, propanol, butanol, dimethylsulphoxide, N-methylpyrrolidone, hexamethylphosphoramide, dimethylformamide, dimethylacetamide and mixtures thereof, provided that when alcohols are present or hydroxylamine and its O-alkyl derivatives replace ATA, primarily DATB and picramide are formed.
  • TATB is produced when ATA is present in between about 3.9 and 5.5 molar equivalents per mole of starting compound V.
  • 4-amino-l,2,4-triazole, hydroxylamine, or O-alkylhydroxylamine are used with the proviso that diamino or polyamino aromatic compounds are produced.
  • Alkyl refers to alkyl groups, having 1 to 10 carbon atoms and includes alkylaryl groups such as benzyl or ethylenephenyl (-CH 2 CH 2 -phenyl).
  • Aromatic compound refers to any organic compound which has a conjugated ring structure and exhibits aromatic structure properties. It includes carbocyclic structures where only carbon atoms are present having substituents which include any electron withdrawing group recited herein. It includes heterocyclic aromatic compounds as defined herein.
  • ATA refers to 4-amino-l,2,4-triazole.
  • DMF dimethylformamide
  • DMAC dimethylacetamide
  • DATB l,3-diamino-2,4,6-trinitrobenzene
  • DMSO dimethylsulphoxide
  • Heterocyclic aromatic compound refers to any organic compound which as a conjugated ring structure, has at least one heteroatom in the ring, e.g., N, O, S, etc. and exhibits aromatic structure properties. Nitrogen containing rings are preferred.
  • HMPA refers to hexamethylphosphoramide.
  • NB refers to nitrobenzene.
  • NMP refers to N-methypyrrolidone.
  • NT refers to nitrotoluene.
  • Picramide or “TNA” refers to l-amino-2,4,6-trinitrobenzene.
  • Salt refers to the anions described herein. Halide is preferred.
  • TATB refers to l,3,5-triamino-2,4,6-trinitrobenzene.
  • TAHI refers to trialkylhydrazium iodide.
  • TMHI refers to triamethylhydrazinium iodide.
  • TMA refers to l-amino-2,4,6-trinitrobenzene.
  • TNB 1,3,5-trinitrobenzene
  • TNT 2,4,6-trinitrotoluene
  • DATNT 3,5-diamino-2,4,6-trinitrontoluene
  • the present invention includes the preparation of monoamino-, diamino-, or polyamino- aromatic compounds, e.g., DATB, TATB, and DATNT.
  • DATB monoamino-, diamino-, or polyamino- aromatic compounds
  • TATB is also useful in the preparation of liquid crystals.
  • an electrophilic aromatic compound e.g., a mononitrated, dinitrated or trinitrated aromatic compound or heterocyclic compound
  • a solvent at between about 0 and 50°C and ambient pressure for between about 0.1 and 24 hr, preferably between about 1 and 5 hr.
  • the temperature is between about 10 and 30°C, and more preferably about ambient temperature (i.e. 20°C).
  • the electrophilic aromatic compound is reacted with 1,1,1 -trialkylhydrazinium salt to provide amino-substituted aromatic compounds by VNS.
  • the reaction conditions for the VNS of specific aromatic substrates are described herein below for DATB and/or TATB. Examples include the conversion of 3-substituted nitrobenzenes to the corresponding nitroanilines, and conversion of trinitroarenes to the corresponding polyaminotrinitroarenes.
  • the extent of the amination of carbocyclic aromatic compounds or heterocyclic aromatic compounds using the 1,1,1 -trialkylhydrazinium salt is normally controlled by one of skill in the art by judicious choice of temperature, time, solvents, strong base and amount of 1,1,1 -trialkylhydrazinium salt.
  • Alcohol solvents usually limit the reaction to production of nitroar ⁇ matic compounds, such as DATB and picramide, because alcohols appear to slow or stop complete amination.
  • the amount of reagent is also important to produce DATB, i.e. between about 1.9 and 2.3 molar equivalents per mole of structure V, preferably about 2.1 eq.
  • solvents which are preferred include aliphatic alcohols having 1-6 carbon atoms (all isomers), cycloalkyl alcohols having 1-6 carbon atoms and the like.
  • Useful dipolar aprotic solvents include, dimethylsulphoxide, N- methylpyrrolidone, hexamethylphosphoramide, dimethylformamide, diethylformamide, dimethylacetamide and the like.
  • the solvent may also include diluents (benzene, chloroform) as needed to optimize conditions and product yields. Mixtures of solvents are also claimed.
  • strong bases are usually the alkali metal salts of alcohols.
  • Alcohols having 1-15 carbon atoms are preferred, more preferred are alcohols having 1-10 carbon atoms, and most preferably are alcohols having 1-6 carbon atoms.
  • Especially preferred alcohols include methanol, ethanol, propanol, (n- or iso-) and butanol (n-, iso-, sec-, or tert-).
  • the VNS reaction is applied to substituted aromatics bearing at least one electron- withdrawing group, e.g., a nitro-group.
  • the aromatics include heterocycles such as substituted and unsubstituted pyridine, pyrimidine, pyrazine, quinoline, quinoxaline, imidazole, triazole and pyrazole.
  • the spent polymeric VNS reagent is then regenerated by reaction with chloramine.
  • the starting material e.g. trinitrated benzene structure is contacted with strong base in the presence of one or more solvents at between about 0 and 50°C and ambient pressure for between about 0.1 and 24 hr, preferably between about 1 and 12 hr, more preferably between about 1 and 5 hr.
  • the temperature is between about 10 and 30°C, and more preferably about ambient temperature (i.e. about 20°C).
  • the trinitrated aromatic compound is reacted with ATA.
  • the extent of the amination using 4-amino-l,2,4-triazole is normally controlled by one of skill in the art by judicious choice of temperature, time, solvents, strong base and amount of ATA.
  • the amount of ATA reagent is also important to produce DATB, i.e. between about 1.9 and 2.3 molar equivalents per mole of structure V, preferably about 2.1 eq.
  • Hydroxylamine and its O-alkyl derivatives are also used to replace a stoichiometrically equivalent amount of ATA, and these reagents produce primarily DATB.
  • the starting material an electrophic aromatic compound, such as a trinitrated benzene structure
  • an electrophic aromatic compound such as a trinitrated benzene structure
  • the temperature is between about 10 and 30°C, and more preferably about ambient temperature (i.e. about 20°C).
  • the electrophilic aromatic compound is reacted with ATA.
  • ATA 4-amino-l,2,4-triazole
  • ATA 4-amino-l,2,4-triazole
  • the extent of the amination using 1 -amino- 1,2,4-triazole is normally controlled by judicious choice of temperature, time, solvents, strong base and amount of ATA.
  • the amount of ATA reagent is also important to produce DATB, i.e. between about 1.9 and 2.3 molar equivalents per mole of structure V, preferably about 2.1 eq.
  • Aromatic structures produced by the present invention include, but are not limited to:
  • R 43 is an electron withdrawing group, and at least one on R 41 to R 43 is an amino group; and for the five-membered heterocyclic rings containing one, two, or three nitrogens, at least one of R 51 to R 54 is an electron withdrawing group, and at lest one of R 51 to R 54 is an amino group, for indole at lest one of R 61 to R 65 is an electron withdrawing group, and at least one of R 61 to R 65 is an amino group; for fused pyridine have two six-membered rings, at least one of R 71 to R 76 is an electron withdrawing group, and at least one of R" to R 76 is an amino group; wherein R 80 is alkyl having 1 to 6 carbon atoms; wherein the electron withdrawing group is selected from -CN, -NO 2 , -COR, - CO 2 R hinder -CONR 2 , -SO 2 R, -SO 3 H, -CF 3 , -F, -Cl, -Br,
  • substituents may be selected from either electron-withdrawing or electron- donating substituents and may be selected from but not restricted to the following:
  • the number of amino groups which may be added to the ring may equal the number of electron withdrawing groups.
  • solvents which are preferred include dipolar aprotic solvents including, but not limited to, dimethylsulphoxide N-methylpyrrolidone, hexamethylphosphoramide, dimethylformamide, diethylformamide, dimethylacetamide and the like.
  • the solvent may also include diluents (benzene, chloroform) as needed to optimize conditions and product yields. Mixtures of solvents are also included.
  • General Picramide is obtained from commercial sources or prepared according to EN.
  • 1,3,5-Trinitrobenzene is obtained from commercial sources or prepared according to Organic Synthesis.
  • 2,4,6-Trinitrotoluene is obtained from commercial sources or is prepared according to any literature source.
  • DMSO is dried and stored over 4A molecular sieves.
  • ATA 4-Amino-l,2,4-triazole
  • the reactions were performed in TEFLON® capped reaction vessels or reaction vessels equipped with drying tubes containing anhydrous calcium sulfate to protect VNS reactions from atmospheric moisture.
  • Example 2(b) Similarly, Example 2(a) is repeated except that 1,1,1 -trimethylhydrazinium iodide is replaced by a stoichiometrically equivalent amount of 1,1,1-triethylhydrazinium chloride, and a similar amount of DATB is produced.
  • Example 2(a) when Example 2(a) is repeated except that DMSO is replaced by a volumetrically equivalent amount of methanol, ethanol n-propanol, iso-propanol or normal butanol, and the base is sodium methoxide, sodium ethoxide, sodium n-propoxide, sodium isopropoxide, or potassium tert-butoxide, a mixture of picramide and DATB is produced.
  • the DATB is purified by crystallization from DMF or DMSO.
  • Example 3 (b) Similarly, Example 3 (a) is repeated except that 1,1,1 -trimethylhydrazinium iodide is replaced by a stoichiometrically equivalent amount of 1,1,1-triethylhydrazinium chloride, and a similar amount of TATB is produced.
  • Example 4(a) is repeated except that 1,1,1 -trimethylhydrazinium iodide is replaced by a stoichiometrically equivalent amount of 1 , 1 , 1 -triethylhydrazinium chloride, and a similar amount of DATB is produced.
  • Example 4(a) when Example 4(a) is repeated except that DMSO is replaced by a volumetrically equivalent amount of DMF or DMAC and sodium methoxide is replaced by a stoichiometrically equivalent amount of sodium ethoxide, sodium n- propoxide, sodium isopropoxide, or sodium tert-butoxide respectively, a mixture of picramide and DATB is produced.
  • the DATB is purified by crystallization from DMF and DMSO.
  • TNB (0.148 g, 0.693 mmol) and TMHI (1.03 g, 5.10 mmol) are dissolved in DMSO (10 ml) prior to the addition of sodium methoxide (0.600 g, 11.1 mmol).
  • DMSO 10 ml
  • the dark brown suspension is stirred for 20 hr at ambient temperature.
  • the reaction mixture is poured into cold 0.12 N aqueous HC1 (200 ml).
  • the resulting precipitate is washed with water and dried to give 0.158 g (61%) of a light brown powder having the IR spectrum of TATB.
  • Example 5 (b) Similarly, Example 5 (a) is repeated except that 1,1,1 -trimethylhydrazinium iodide is replaced by a stoichiometrically equivalent amount of 1,1,1 -triethylhydrazinium chloride, and a similar amount of TATB is produced.
  • Example 6(a) is repeated except that 1,1,1 -trimethylhydrazinium iodide is replaced by a stoichiometrically equivalent amount of 1 , 1 , 1 -triethylhydrazinium chloride, and a similar amount of nitroanilines are produced.
  • TMHI is reacted with the same 3- substituted nitrobenzene substrates used with 4-amino-l,2,4-triazole (ATA) as reported by A.R. Katritzky and K.S. Laurenzo, Journal of Organic Chemistry, vol. 51, pp. 5039-5040 (1986).
  • ATA 4-amino-l,2,4-triazole
  • the nitroaromatic substrate (1.3 mmol) and TMHI (1.4 - 1.9 mmol) are dissolved in dry DMSO (7 ml), and solid alkoxide (sodium methoxide or potassium tert-butoxide) is added with stirring. The solution immediately becomes nearly black in color. After 4-17 hr of stirring at room temperature, the reaction is quenched with 10% HC1.
  • Precipitated solids are collected by filtration and washed with cold water.
  • the filtrate is extracted with ethyl acetate and the crude products obtained upon evaporation of the solvent are subjected to chromatography on silica.
  • the identity of all products is confirmed by comparison of melting points and/or ⁇ NMR with authentic standards. The results are summarized in Table I.
  • Table I shows that TMHI is not as selective as ATA, producing in most cases multiple regioisomeric products.
  • TMHI displays a tendency to aminate in the 2-position which contrasts with exclusive 4-amination in the case of ATA.
  • the very high reactivity of TMHI is of interest and with m-dinitrobenzene diamination takes place even under stoichiometric conditions.
  • Example 8(a) is repeated except that 1,1,1 -trimethylhydrazinium iodide is replaced by a stoichiometrically equivalent amount of 1,1,1 -triethylhydrazinium chloride, and a similar amount of DATNT is produced.
  • Example 9(b) Similarly, when Example 9(a) is repeated except that methanol is replaced by a volumetrically equivalent amount of ethanol, n-propanol, iso-propanol or tert- butanol, and sodium methoxide is replaced by a stoichiometrically equivalent amount of sodium ethoxide, sodium n-propoxide, sodium isopropoxide, or sodium tert-butoxide respectively, a similar amount of DATB is produced.
  • Example 10(a) when Example 10(a) is repeated except that sodium methoxide is replaced by a stoichiometrically equivalent amount of sodium ethoxide, sodium n- propoxide, sodium isopropoxide, or potassium tert-butoxide respectively, a similar amount of DATB is produced.
  • Example 11(b) Similarly, when Example 11(a) is repeated except sodium methoxide is replaced by a stoichiometrically equivalent amount of sodium ethoxide, sodium n- propoxide, sodium isopropoxide, or potassium tert-butoxide respectively, a similar amount of DATB is produced.
  • Example 12(b) Similarly, when Example 12(a) is repeated except sodium methoxide is replaced by a stoichiometrically equivalent amount of sodium ethoxide, sodium n- propoxide, sodium isopropoxide, or potassium tert-butoxide respectively, a similar amount of TATB is produced.
  • Example 13(a) Similarly, when Example 13(a) is repeated except sodium methoxide is replaced by a stoichiometrically equivalent amount of sodium ethoxide, sodium n- propoxide, sodium isopropoxide, or potassium tert-butoxide respectively, a similar amount of TATB is produced.
  • Example 15(b) Similarly, when Example 15(a) is repeated except sodium methoxide is replaced by a stoichiometrically equivalent amount of sodium ethoxide, sodium n- propoxide, sodium isopropoxide, or potassium tert-butoxide respectively, a similar amount of DATNT is produced.
  • Example 2(a) is repeated except that the picramide is replaced by a stoicheometrically equivalent amount of mononitro or dinitropyrazole and the corresponding monoamino and diamino-nitropyrazole is produced.

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Abstract

La présente invention se rapporte à un processus d'amination de composés aromatiques électrophiles par substitution nucléophile vicariante d'hydrogène au moyen de sels d'hydrazinium quaternaire. L'invention concerne l'utilisation d'iodure de triméthylhydrazinium, et également d'hydroxylamine, d'alcoxylamines et de 4-amino-1,2,4-triazole en vue de l'obtention de structures aromatiques aminées, telles que le 1,3-diamino-2,4,6-trinitrobenzène (DATB), le 1,3,5-triamino-2,4,6-trinitrobenzène (TATB) et le 3,5-diamino-2,4,6-trinitrotoluène (DATNT). Le DATB et le TATB sont utilisés comme explosifs brisants à risques atténués. Le TATB sert également à la préparation de benzènehexamine, produit de départ servant à la synthèse de nouvelles matières (dispositifs optiques d'imagerie, cristaux liquides, composés ferromagnétiques).
PCT/US1996/006663 1995-05-12 1996-05-10 Amination de composes aromatiques electrophiles par substitution nucleophile vicariante Ceased WO1996035659A1 (fr)

Priority Applications (3)

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EP96916451A EP0835237A1 (fr) 1995-05-12 1996-05-10 Amination de composes aromatiques electrophiles par substitution nucleophile vicariante
JP8534272A JPH11511740A (ja) 1995-05-12 1996-05-10 求電子性芳香族化合物の代償性求核置換によるアミノ化
US08/967,914 US6069277A (en) 1995-05-12 1997-11-12 Amination of electrophilic aromatic compounds by vicarious nucleophilic substitution

Applications Claiming Priority (4)

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US08/440,017 1995-05-12
US08/440,024 1995-05-12
US08/440,024 US5633406A (en) 1995-05-12 1995-05-12 Vicarious nucleophilic substitution using 4-amino-1,2,4-triazole, hydroxylamine or O-alkylhydroxylamine to prepare 1,3-diamino-2,4,6-trinitrobenzene or 1,3,5-triamino-2,4,6-trinitrobenzene
US08/440,017 US5569783A (en) 1995-05-12 1995-05-12 Vicarious nucleophilic substitution to prepare 1,3-diamino-2,4,6-trinitrobenzene or 1,3,5-triamino-2,4,6-trinitrobenzene

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FR2843112B1 (fr) * 2002-07-30 2004-10-22 Clariant Procede de preparation d'amines primaires.
US8404897B2 (en) * 2009-11-03 2013-03-26 Pacific Scientific Energetic Materials Company Facile synthesis of 3-aminopicric acid

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US5466871A (en) * 1993-07-22 1995-11-14 Sumitomo Chemical Company, Limited Process for preparing nitroaniline derivatives

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US5466871A (en) * 1993-07-22 1995-11-14 Sumitomo Chemical Company, Limited Process for preparing nitroaniline derivatives

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Title
JOURNAL OF ORGANIC CHEMISTRY, 1986, Vol. 51, KATRITZKY et al., pages 5039-5040. *

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