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    Delepine Amine Synthesis

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    The Delépine amine synthesis involves reacting an alkyl halide with hexamethylenetetramine to form a salt, which is then cleaved with ethanolic HCl to yield a primary amine. This reaction works well for reactive halides such as benzyl, allyl halides, and α-halo-ketones. The mechanism proceeds through an SN2 reaction between the alkyl halide and hexamethylenetetramine to form an intermediate salt, which is then hydrolyzed to form the amine product and byproducts. Delépine developed this synthesis method in the late 19th century.

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    Delepine Amine Synthesis

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    The Delépine amine synthesis involves reacting an alkyl halide with hexamethylenetetramine to form a salt, which is then cleaved with ethanolic HCl to yield a primary amine. This reaction works well for reactive halides such as benzyl, allyl halides, and α-halo-ketones. The mechanism proceeds through an SN2 reaction between the alkyl halide and hexamethylenetetramine to form an intermediate salt, which is then hydrolyzed to form the amine product and byproducts. Delépine developed this synthesis method in the late 19th century.

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    The Delépine amine synthesis involves reacting an alkyl halide with hexamethylenetetramine to form a salt, which is then cleaved with ethanolic HCl to yield a primary amine. This reaction works well for reactive halides such as benzyl, allyl halides, and α-halo-ketones. The mechanism proceeds through an SN2 reaction between the alkyl halide and hexamethylenetetramine to form an intermediate salt, which is then hydrolyzed to form the amine product and byproducts. Delépine developed this synthesis method in the late 19th century.

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    83 views2 pages

    Delepine Amine Synthesis

    Uploaded by

    p
    The Delépine amine synthesis involves reacting an alkyl halide with hexamethylenetetramine to form a salt, which is then cleaved with ethanolic HCl to yield a primary amine. This reaction works well for reactive halides such as benzyl, allyl halides, and α-halo-ketones. The mechanism proceeds through an SN2 reaction between the alkyl halide and hexamethylenetetramine to form an intermediate salt, which is then hydrolyzed to form the amine product and byproducts. Delépine developed this synthesis method in the late 19th century.

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    of 2

    187

    Delpine amine synthesis


    The reaction between alkyl halides and hexamethylenetetramine, followed by
    cleavage of the resulting salt with ethanolic HCl to yield primary amines.
    Cf. Gabriel synthesis, where the product is also amine and Sommelet reaction,
    where the product is aldehyde. The Delpine works well for active halides such as
    benzyl, allyl halides, and D-halo-ketones.

    N
    Ar

    N
    N

    N
    N

    N
    N

    HX

    Ar

    Ar

    NH3
    X

    hexamethylenetetramine

    [ArCH2-C6H12N4]+X
    = ArCH2NH2HX

    Ar

    SN2
    X

    3NH4Cl

    H
    N

    N
    N

    N
    N

    Ar
    X

    H2O:

    O
    CH2

    6CH2O

    + 6H2O

    N:

    N
    N

    3HCl

    N
    N
    N

    Ar

    N
    N

    O H
    Ar

    H
    N
    N
    N

    Ar

    Ar

    NH3
    X

    Example 14

    O
    Br

    1. (CH2)6N4, NaHCO3
    15 h, EtOH, H2O
    OH 2. HCl, EtOH, reflux, 15 h, 85%

    O
    H2N

    OH

    188

    Example 28

    Br

    hexamethylenetetramine

    Br

    CH2Cl2, refux, 5 h, then

    30 oC

    Br

    N
    +

    N4C6H12 Br

    conc. HCl, EtOH


    reflux, 1 d
    78%, 2 steps

    Br

    N
    NH2

    References
    1.

    2.
    3.
    4.
    5.
    6.

    Delpine, M. Bull. Soc. Chim. Paris 1895, 13, 355; 1897, 17, 290. Stephe Marcel
    Delpine (18711965) was born in St. Martin le Gaillard, France. He was a professor
    at the Collge de France after working for M. Bertholet at that institute. Delpines
    long and fruitful career in science encompassed organic chemistry, inorganic chemistry, and pharmacy.
    Delpine, M. Compt. Rend. Acad. Sci. 1895, 120, 501. 1897, 124, 292.
    Galat, A.; Elion, G. J. Am. Chem. Soc. 1939, 61, 3585.
    Wendler, N. L. J. Am. Chem. Soc. 1949, 71, 375.
    Quessy, S. N.; Williams, L. R.; Baddeley, V. G. J. Chem. Soc., Perkin Trans. 1 1979,
    512.
    Blazevi, N.; Kolnah, D.; Belin, B.; unji, V.; Kafje, F. Synthesis 1979, 161. (Re-

    view).
    7.
    8.

    Henry, R. A.; Hollins, R. A.; Lowe-Ma, C.; Moore, D. W.; Nissan, R. A. J. Org.
    Chem. 1990, 55, 1796.
    Charbonnire, L. J.; Weibel, N.; Ziessel, R. Synthesis 2002, 1101.

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