Skip to main content
Chemistry LibreTexts

21.13: Solutions to Additional Exercises

  • Page ID
    183148
  • General Review

    23-1

    EgDYSkLzWAot_qkGyb8dp750cGEt_uurnWlS6gmrSu5wAPQ78EJFrb3LNzxftVwXVob2qOK81qvzeCS8G7lOfS_7DpR_rjvWIV14khffM_VDZayYpX5pQFbtYSSIJy26HkeBoaBu

    When a bulky base, such as LDA, is used, it will almost always deprotonate the least hindered position. In this case, the reaction is performed under low temperatures (to prevent the thermodynamic product from forming) and we get the kinetic product. When we use a strong base that is not bulky, it will favor deprotonating the position that will provide the most stable product at equilibrium. As a result, the enolate that forms when using NaH or NaOEt is more substituted and more stable.

    23-2

    6TAiOH3bVns-u0KPoHhsJmJkbOJ2AE1Ib1m7Yoz7VXNL6UtbtVn-rmrDQnW9zY99Df0RaGBT-vz-Yod_1frKl273NuRvz-XDW-ARpQDaGRziFCpIIhoNPiQFmPDSRVDdyd1LXXDj

    23-3 When acetophenone is halogenated at the α-position, the α-carbon becomes more acidic as a result of the electron-withdrawing halogen. This makes it more likely to go through α-halogenation again, until it no longer has any α-protons. When the base performs a nucleophilic attack on the ketone, the triiodomethyl group becomes a good leaving group. The resulting products are sodium benzoate and triiodomethane.

    23-4

    Jr2mhMGEINdsGC8_y-9sRKMJhWfZgdiZGMmpfjmon05kz5WfHiWBFkHfx5WXeCEDCl8bOaNUNY7AhtuP9V_oFqM3c9zCcXtUO7qIr0s0l-07NHceFJ5WBRmePIGZUUn3sVqI5THW

    23-5

    FctSyjk9npzMxx95dPC5Qw2U40XDZkijbrVcgKssbfhzF6cHEuk2xo4SYBv1HcWuNYkAVdJv6i40RbdvmdhEY_ta9Q2arf7BY-YuutDLsn-6wKx38mqBWZPQtOdkVsiLhxj0XCEd

    23-6

    gbFshhEHC8RWYC2XtM9MvGraQWXY75Z8yQZMhexBWkydDWo52m2Fd65cyL9NapMjq20nBQWrTIQTEDIEO5kM-MCRJuz8-52_8uLE6Ar0KJIgSBXU-MF6ctpk0YKm0f8PQFPNex7Y

    23-7

    eeIzwyQZEVslGDgda9UjvgjDQOOVXNRxB0RsP3C93IhS_JQfKDkDNdHkgd1lF9DPHX2iYVQT4rWXgXE41-WnApN1rOQNmu6O1DdF35Xqr2wxVNxGaCPbKJXOaHEBqvPl0dTk-XtN

    Enols and Enolate Ions

    23-8:

    Answer: B

    CsMHfFBXLLkkoXQv1rmfAf3Hb0fNj9EC1t5QRgUHwbnBw5UDq_9YCM4vDKKGlrpzrEMuX66SNkE5XnguOKd6tmPa_Cj2s6VOPJBDY1LR6QDEO1A7b4OSoCFYAS_wTFLcLwMjEHri

    23-9:

    -jM1lt_n4YfmICwptXbRSH9z1jY2glUP_2KroiFTc6YTSw-dYoRsPihXGzX8NsV_R5N0LP0cNiDo0G6_5DdLLmwPtvWMdPHcsxoITe1y6GUtv2wlC-bLWS_a1NXrpO21bdietmkq

    23-10:

    ciWV46xGejaDl_zWBmY9sXrBBCA1tNwFN5XVzIKPX-H8pXTl545teSfsKapCbbTynP8ByETIrdqwJsamPpHtP06GwpMY9tEMso-ICpOhEqVjQBAKhJZnV7vgBthgaQrbmFh50-Hu

    Formation and Alkylation of Enamines

    23-11:

    Answer: A

    srUvVwZj01vYmDPkM1_LGEnAxknKaYy8ZpepW1owBvjvJRcXpzoEM8jHZmVd-7hknaGVH__MCUVLQ8WL6p4yru6kbGZdKII9mhlq60yRYoU0BoMxRE1ICHS8qmD_EyJgqyn70fhd

    23-12:

    kDoo6aWYpg0fgfVIdkfkPxX56PTrXYQTs0a0h0WWJMTFJLyroQYFq6-igYI4ww-rEKYnM6bR4hzDknDwkMWPCGQ3uFWnxA9b5BIlEgOzU_U3DOOmXqGfGJhocGnANP-dGPGdlRH5

    23-13:

    T0uUJvOkzMpdoFl_odTh_a-5sTyUommh3b40Nf5O8Mh3KCb4ygUpXu7Iw83ACjDxDHZOEgb94rKVRM4NJahfiHA6AXoT9Edo6Em-mk5iB27Hv12Z6N1llL3GscAHvv46ASai18TO

    Alpha Halogenation of Ketones

    23-14:

    yAghY2Z4bo4QaSWIPR9q3yyBWgh8IDt1Lukj3fpXofirGIra-2zIsOGa91aBJefifg5wBSJL_qeuivz-c1oCsJqUoqbUG3t8OC51txu0p0XuUjjUv2_7MmpmoVtDR8McfQUEzikx

    23-15:

    K4SEsgGOgg8J-eBKvGFm1aOxPoQiAomi9v7qhrpbr2qVuwvkM8eQE6qZH46z2mKD3-D25YPzS5pt656j4GAYLGf_T4bKbxy-azvd9uTISpg1VjsHCZWzmsY_GfwpfC2F4Si4n0C0

    23-16:

    NknZa1m82EPQHn2HywS4tMoNHaaBXtrCb3yyWTfCm62GY5QYNbEJUtI3nJ81tmbyU8S6-57o3Qetgt6vPyV71EXtfEyDpEYKS-Hmrm5pn3dl38V2uHmZpFhji_LzKo5UIc5ItITU

    Alpha Bromination of Acids: The HVZ Reaction

    23-17:

    xX0p0wdVaIJ8rCqLeh09B-sIW7QrYAuG7HfnMvUfh4gfhdxArUlrXpETqDYTORo1ZuciCym3LQyUfYvhtRmqJr6PxPvnkgEt-opeGFZKMTTK1T2wbI-OQSTCX78DDuA3XuljUbYL

    23-18:

    Answer: B

    23-19:

    4GuqT-GRgRp0GbesW0JZCvCvl2uDlpynrOuA9tlbHmm4pgOhEN1Em9PeIkGW-2LwmQvwcNw2ja9i3SbcBefSv7k9t5Cuus9_2iCGp1goTaZk_JtbWy8wGn4ETyigapiYBW5ZoxxJ

    The Aldol Condensation of Ketones and Aldehydes

    23-20:

    PVPxTCSgNkg6uY7nHxXGiig7JMIGYyf1MwDS4e74EG6kq9Kua9PrmKg5DPEVEbBh4BMKKB-7l7FHFgstnwCMMfEgMPTnpVCDsKWqWpyZoiDBzMe0gTfPXzlsiArPrVF6J886rvQT

    23-21:

    a0imclXi84wu5xc-Ii4Y1WYqI583dHjuYc1lTQN-dhouJkoGEjjlWvABQJEG5f4d_35_3Y0XbziWZEMVSmSZVcW-2nm25AvYGkz38M4uV0Mnj1vAtZZiUFmsuS2IoYiKBialG2dC

    23-22:

    baLA5IT4Vaf-_HvHbld0WAqOkXdxWnQO3dnvXMAKyT3TPJtl3I43UE84_v2OYcDjXTiyr_21ER-hXle3U4Oht8lqaXNwjDzTybk-l3dbavBQHMRbD5rALbp11uI8XkH9Dj7Heh4R

    Dehydration of Aldol Products

    23-23:

    Answer: B

    23-24:

    wagmPKEIfRRn8zjtgTvZ9HbFfF5lXAOoODi5NL1B9iNaVCwVqN4Y5DxbjG_YjiXqI7e1n3IE0r5-KoxUr_-ykLjlzaHwymDK_el1VyZpsWKD7z1B2ca7xP4nrqVIhUBSH5vTlh55

    23-25:

    7mwjL0BZ-18l7-py5WGJ8uBeAACvJQAgfA7dqB5jgMT7FrE8RDDSTzx32PimUpWMvkftxj_YMs23QYR9ANb-JXKRFQbgydARjVfSkGMzWS-2XG1R7nbOp-b__5a1iLPpLl-S5ur1

    Crossed Aldol Condensations

    23-26:

    b4j8FR2rkxI4HFkaWjWVoQBP36q5uFvavODAyf0QJEKZJVhaIakjZ41SAdxaKnRU2J7HcNOuLoAtf5pmoYczJ41fj3cmSZciWOqhpMagQ6CW5oEzSusaZfLgZ392XRDiJysYyNDh

    23-27:

    PzhCbvekWgM4DxgnNzqmZGsNSQa3V6NLloScwcFXPEgoQC8zJPRHzRwx4bK4EBG_AvEuTOXKlb7jfatGeqOVSjNNl8Py4tlKTq82PzZWkBQPI3IUSHIwwcWw4S9UnZz0q5sn_bFs

    23-28:

    uSmVW7LN6H4NxttnO06oBNRx-qiPZJcj2mseE08BFp3z8ZNMQ5BIm3oj0jUyLh-fekkL1nfmcAGLPZEpGfBjeLgdAc0BRXJHp1OtLaVUQfxU1DBC8VgXyfnCtjEP2z4AsX0ni8n3

    Aldol Cyclizations

    23-29:

    l0owsARe-WpxiPONgbYjWCXGnW1gHwD_cKObCCplBdHFVYm0Ib7kSow48vkqoRIku8cwk1Fwt4e77CnWOSftDfOij75weZ_E69L2BNu6WLxuAemRZjaur8cPXEANaGOHwf6KXqfx

    23-30:

    hxFXrk22F2x1MoIdvFR2jmK1nvaJlhg-Nk52W7-nSxiqQTIaCn9wLOnpaK96H3jnCJTgSIKUEwuvSqK3YF1gCWWV9jNFDEDDJv_ofQ0j4BDKi4xeGyHdhoZ1TqhkBgRGYpsD11dY

    23-31:

    Several answers possible. One plausible method of synthesis:

    TckQr_On754byeQTbV7wqwf8XDSo3ehy-woYmW0Bd9IrvkdnbPcrLU03tqOErnbm68UT0vMOpGuk2zIMdWZOjwqBUPo1XoHkOdGKqh3fS7Glk46naLiDnS-b6dN9sRSNczeud3Yx

    Claisen Condensations

    23-32:

    yuF2SA4wAS-JQyuSzJnBFzT4rBb7NOm61J0IqSSWmkhFuuxkBMoH8PiskZlzq1mCYRx00q_Ex-UMLMYkqIMa69TBJbpbnsKt53qgM_vqiWnj3psQ6mz_MT1Zz0c4QHs5BeKSNwaf

    23-33:

    vUpeJpS5XG5vtceTUlulL8g936mqL-R374z3BFBr4hKRA5o3Kui4BcK8rUMlUaUZJpg5Uc1f9PDnySygFqryEwsXMgfPjd9S3UVbQoFU1t4HjGr-iXYUmri6hwgYbpx4cu8klNX6

    23-34:

    P3mLslLc5ylOAZNwvzR-FhTbtsSrtlbX6Up-IlQTTTGzeSKS2IZz0lljw-F-TmwLoICnWb3Pxs0Y5BGxRom2eZn7l_lP-i2pxnAy6zgzDvkI8SW8TZtljh6Izg70gKuvLOxMNrdz

    Syntheses Using β-Dicarbonyl Compounds

    23-35:

    Bcxl1NFNpLCKumtpsdcnO5vI3nYgzrGLeFW4FuU_fxqNt04qlAd-rH9HTwZ8HchI_QVAVu-XzHtsw21XfzFDp-49IBAnZzFV5z3L82tOBOkL32pvmRmKvOIKXwGe4_89nA601bHD

    23-36:

    Answer: B

    23-37:

    Possible route of synthesis:

    hQlZ0vy9LJrBjr2eQu9CAl7cUE3D21dX-aZgte6jpWI1NgiGfwF-jN3gm1B3ALCQWFNeT7zqZ2UJZe5Uc71tR4uD5J_S_F-kD3cWr3K_l_Js6hiGvisLwzBN6zR1WNjNvveNZPcT

    Conjugate Additions: The Michael Reaction

    23-38:

    Michael acceptors are generally α,β-unsaturated ketones; however, aldehydes or acid derivatives can also function as acceptors. Michael donors are weak bases/strong nucleophiles.

    T3O46629O0Yvlr1LR6OHRzGW7djfyrvulzod5qmn7p3U0OaT8W85ba2nR2snpbIs0k4eyQm8X5d5ehKuibLxobCoLYUy5MUn-dTlno-Qh7gtpfbi0HuNkJT4trD4Oi52Q3o-YrV1

    23-39:

    1rNZIsycHWbNlOuMxW9zKn4ykDXhoRafOjseMp9bMciCI7K3aWP1fqJJzD62A5pLe9bfmzvdD8N10PnexLTbHfxpc6BdbcrBSrpeJHsOAX5GIKJRM1Cm8MqUcl4mtrKRqmcFCyRD

    23-40

    Answer: C

    BTO2duq0PK_jbM7OzeytcoeIme8L25MGcv4BS8lJWoq13UZsjtADZbHKsY3s342v_JZhBVHcsNx8guE2zo-uLKHJh8K33EZLWD2dBwlVz4g1da83ftesowjqBnsKP02PE-jCyA7S

    The Robinson Annulation

    23-41:

    AikDGVN3NH_WX9qEvxuQ5cArT_1oa-Ws9rQQIscgZzK67MSKD73B2GXkxjSMi5KvFnDGP0A5DyJxsQFy8K-qIa7T9ufGQ-VM9--pcP09M7vcl5l_5Dvq4Aqvtxc1xD3Ty0sfNWqh

    23-42:

    ERKaXjpraHWDPuWDq6Ux0qpG--rMu2gurHCNJM5Rff6OHkR5h6JLCrp-fh0rMq9y0vbhTP8bYnKa7ErUxSASoG1Je0TOJ9tt9eLZ8aBloC7ZLyMB6L21TGsmhgNfPRIBSbBLVCpS

    23-43:

    z99bbINwNa42jcZwymfM-xz48wNC9HeYt-ZkmdpRSQJEU2P7ce7560uqnL_evsbjsN8oRqQFFGtQ9cSlpNBPm9QGPYx82fp_0k6mXzSlsGDooRsELq_6qpohoTeciCqPM8lbIIfL