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    Working With Hazardous Chemicals: A Publication of Reliable Methods For The Preparation of Organic Compounds

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    Edgardo Ed Ramirez
    Synthesis

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    © All Rights Reserved
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    Working With Hazardous Chemicals: A Publication of Reliable Methods For The Preparation of Organic Compounds

    Uploaded by

    Edgardo Ed Ramirez
    54 views4 pages
    Synthesis

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    synthesis

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    © © All Rights Reserved

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    Synthesis

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    54 views4 pages

    Working With Hazardous Chemicals: A Publication of Reliable Methods For The Preparation of Organic Compounds

    Uploaded by

    Edgardo Ed Ramirez
    Synthesis

    Copyright:

    © All Rights Reserved
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    A Publication

    of Reliable Methods
    for the Preparation
    of Organic Compounds

    Working with Hazardous Chemicals

    The procedures in Organic Syntheses are intended for use only by persons with proper
    training in experimental organic chemistry. All hazardous materials should be handled
    using the standard procedures for work with chemicals described in references such as
    "Prudent Practices in the Laboratory" (The National Academies Press, Washington, D.C.,
    2011; the full text can be accessed free of charge at
    http://www.nap.edu/catalog.php?record_id=12654). All chemical waste should be
    disposed of in accordance with local regulations. For general guidelines for the
    management of chemical waste, see Chapter 8 of Prudent Practices.

    In some articles in Organic Syntheses, chemical-specific hazards are highlighted in red


    “Caution Notes” within a procedure. It is important to recognize that the absence of a
    caution note does not imply that no significant hazards are associated with the chemicals
    involved in that procedure. Prior to performing a reaction, a thorough risk assessment
    should be carried out that includes a review of the potential hazards associated with each
    chemical and experimental operation on the scale that is planned for the procedure.
    Guidelines for carrying out a risk assessment and for analyzing the hazards associated
    with chemicals can be found in Chapter 4 of Prudent Practices.

    The procedures described in Organic Syntheses are provided as published and are
    conducted at one's own risk. Organic Syntheses, Inc., its Editors, and its Board of
    Directors do not warrant or guarantee the safety of individuals using these procedures and
    hereby disclaim any liability for any injuries or damages claimed to have resulted from or
    related in any way to the procedures herein.

    These paragraphs were added in September 2014. The statements above do not supersede any specific
    hazard caution notes and safety instructions included in the procedure.
    DOI:10.15227/orgsyn.031.0045

    Organic Syntheses, Coll. Vol. 4, p.364 (1963); Vol. 31, p.45 (1951).

    2,6-DINITROANILINE
    [Aniline, 2,6-dinitro-]

    Submitted by Harry P. Schultz1


    Checked by Arthur C. Cope and Douglas S. Smith.

    1. Procedure
    In a 1-l. round-bottomed flask fitted with a mechanical stirrer are placed 50 ml. (55.4 g., 0.49 mole)
    of chlorobenzene (Note 1), 300 ml. of concentrated sulfuric acid (sp. gr. 1.84), and 50 ml. (92 g.) of
    fuming sulfuric acid (containing approximately 25% free sulfur trioxide). The mixture is stirred and
    heated on a steam bath for 2 hours and then cooled to room temperature. The stirrer is removed from the
    reaction flask and replaced with a thermometer. To the clear solution is added 170 g. (1.68 moles) of
    potassium nitrate in 4 portions. The temperature of the mixture during this time is held at 40–60° by
    cooling the flask and its contents in ice water. After the mixture has been swirled briefly in the reaction
    flask to dissolve most of the potassium nitrate, it is heated to 110–115° (Note 2) and held at that
    temperature for 20 hours. The hot contents of the flask are poured onto 2 kg. of cracked ice. After the
    ice has melted, the yellow precipitate is filtered with suction and pressed as dry as possible.
    Without further drying, the potassium 4-chloro-3,5-dinitrobenzenesulfonate is recrystallized from
    600 ml. of boiling water (Note 3). Insoluble material is removed by decantation and filtration of the hot
    solution. The solution is cooled to 5–10° for 12 hours, and the crystalline potassium salt is collected on
    a suction filter, pressed as dry as possible, and placed at once in a solution of 400 ml. of concentrated
    ammonium hydroxide (sp. gr. 0.90) in 400 ml. of water. The solution is boiled for 1 hour under a reflux
    condenser which has been connected to a gas absorption trap,2 and then is cooled at 5–10° for 12 hours.
    The orange, crystalline potassium 4-amino-3,5-dinitrobenzenesulfonate is filtered with suction and
    pressed as dry as possible on a 10-cm. Büchner funnel.
    The damp salt is placed in a solution of 200 ml. of concentrated sulfuric acid (sp. gr. 1.84) and 200
    ml. of water in a 1-l. round-bottomed flask, and the mixture is boiled vigorously under reflux for 6 hours
    (Note 4). The hot acid solution is poured onto 1 kg. of cracked ice, filtered on a 7.5-cm. Büchner funnel,
    slurried twice with 100-ml. portions of water, and pressed as dry as possible on the funnel. The damp,
    impure 2,6-dinitroaniline is dissolved in 500 ml. of hot 95% ethanol, and the solution is boiled under
    reflux for 10 minutes with 3 g. of Norit and 3 g. of filter aid. The hot ethanol solution is filtered through
    a heated funnel (Note 5) and cooled slowly to room temperature. Light-orange needles of 2,6-
    dinitroaniline separate and are collected on a suction filter and air-dried. The yield is 27.4–32.3 g. (30–
    36%) (Note 6), m.p. 139–140°.

    2. Notes
    1. The best grade of Eastman Kodak Company chlorobenzene was used.
    2. Since the reaction is moderately exothermic during the first 4 hours, the temperature of the reaction
    mixture must be controlled carefully. A gas trap2 may be used to absorb the small amount of nitrogen
    dioxide evolved, or the reaction may be carried out in a hood. Excessive fuming is avoided if the
    temperature is kept in the range 110–115°.
    3. If the potassium 4-chloro-3,5-dinitrobenzenesulfonate is not recrystallized before ammonolysis very
    impure 2,6-dinitroaniline is obtained.
    4. The condenser should be cleared occasionally with a small glass rod to remove the 2,6-dinitroaniline
    that may collect there.
    5. The funnel must be heated to avoid crystallization during filtration.
    6. The solubility of pure 2,6-dinitroaniline in 95% ethanol at room temperature is about 0.4 g. per 100
    ml.

    3. Discussion
    2,6-Dinitroaniline has been prepared by the ammonolysis of 2,6-dinitroanisole,3 2,6-
    dinitroiodobenzene,4 2,6-dinitrophenyl 4-nitrobenzyl ether,5 and 2,6-dinitrochlorobenzene;6 by the
    rearrangement of o-nitrophenylnitramine;7 and by the desulfonation of potassium 4-amino-3,5-
    dinitrobenzenesulfonate.8,9,10 The method described above is based on the procedures of Ullmann8 and
    Welsh.9
    This preparation is referenced from:

    z Org. Syn. Coll. Vol. 4, 160

    References and Notes

    1. University of Miami, Coral Gables, Florida.


    2. Org. Syntheses Coll. Vol. 2, 4 (1943).
    3. Salkowski, Ann., 174, 273 (1874).
    4. Koerner, Gazz. chim. ital., 4, 324 (1874).
    5. Kumpf, Ann., 224, 118 (1884).
    6. Borsche and Rantscheff, Ann., 379, 162 (1911).
    7. Hoff, Ann., 311, 108 (1900).
    8. Ullmann, Engi, et al., Ann., 366, 102 (1909).
    9. Welsh, J. Am. Chem. Soc., 63, 3276 (1941).
    10. Fisher and Joullie, J. Org. Chem., 23, 1944 (1958).

    Appendix
    Chemical Abstracts Nomenclature (Collective Index Number);
    (Registry Number)

    ethanol (64-17-5)

    sulfuric acid (7664-93-9)

    sulfur trioxide (7446-11-9)

    Norit (7782-42-5)

    chlorobenzene (108-90-7)

    nitrogen dioxide (10102-44-0)

    ammonium hydroxide (1336-21-6)

    potassium (7440-09-7)

    potassium nitrate (7757-79-1)

    2,6-dinitrochlorobenzene (606-21-3)

    2,6-Dinitroaniline,
    Aniline, 2,6-dinitro- (606-22-4)

    potassium 4-chloro-3,5-dinitrobenzenesulfonate

    potassium 4-amino-3,5-dinitrobenzenesulfonate

    2,6-dinitroanisole

    2,6-dinitroiodobenzene

    2,6-dinitrophenyl 4-nitrobenzyl ether

    o-nitrophenylnitramine

    Copyright © 1921-2005, Organic Syntheses, Inc. All Rights Reserved

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