Page 239 - 《精细化工》2023年第4期
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す 4 ᱌                 䧌⦉㏏喑ぶ: CuI ϸᄩ Reformatsky ࣺᏁ倅᩵व᜽ ȕ-㓌ധ䚜ㆨࡃव➖                         g925g


            OCH 2 ), 2.91~2.66 (m, 2H, CH 2 ), 2.24 (s, 3H, Ar-CH 3 ),   त 1Ƞ2喎ȡߍڒ CuCl喑ࡃव➖ 1 ϔ⢴ᰶγᒵ๔᣽倅喑
            1.71~1.69 (m, 2H, COHCH 3 ), 1.04 (t, J = 7.2 Hz, 3H,   䓫ݝ 47%喍Ꮌत 3喎ȡाࣺᏁҀ㈨͚⌨ߍ 1.0 mmol
                                         13
            CH 3 ), 0.69 (t, J = 7.4 Hz, 3H)ȡ CNMR (101 MHz,   NaI喑ҬĔb ̻ NaI ࣾ⩌࢑࣌ၽϑᢏ⩌᜽࣌᫆Ĕa喑
            CDCl 3 ),  į: 173.06 (O==C), 142.23 (Ar-C), 136.19
            (Ar-C), 128.79 (Ar-C), 125.07 (Ar-C), 75.15 (COH),   ں̻ēa ࣺᏁ喑ࡃव➖ 1 ϔ⢴෋ߍݝ 69%喍Ꮌत 4喎ȡ
            60.67 (CH 2 O), 44.94  (CH 2 CO), 35.96  (COHCH 3 ),   ᒀិĔb ᢏͧ≨ᕔᰡ倅⮱ 2-ⷅΆ䚥Ά䚜喍Ĕa喎ᬣ喑
            20.99 (Ar-CH 3 ), 14.00 (CH 3 ), 7.85  (CH 3 )ȡESI-MS,   ࡃव➖ 1 ϔ⢴Όᰶᬻ᭫෋ߍ喍Ꮌत 5喎ȡБϧ๴ᕗ⮱
                        +
            m/Z喟[M+H] ⤳䃧թ 237.14喠჋≸թ 237.12ȡ                   ᭜喑ाࣺᏁҀ㈨͚ߍڒ 0.2 mmol CF 3 CO 2 H ᬣ喑ࡃव
                 3-㓌ധ-2,2-ι⅌-3-㠜ധ̮䚥Ά䚜喍32喎喟ᬍ㞟⇦                  ➖ 1 ϔ⢴᭫㦄෋ߍݝ 82%喍Ꮌत 6喎ȡ䔆᭜⩞λౕࣺ
                                          1
            ⟣➖  [32] 喑200.1 mg喑ϔ⢴ 82%ȡ HNMR (400 MHz,          Ꮑड़ߕݺ喑CF 3 CO 2 H 㘪⏣㼐יࡃݯ䨹ㆶ㶕䲏⮱⅔ࡃ
            CDCl 3 ), į: 7.52 (d, J = 7.3 Hz, 2H, Ar-H), 7.39~7.29   ➖喑䊤ݝ≨ࡃ䨹ㆶ⮱҉⩕喑㔹᪴⡛[23]䰭㺮ౕࣺᏁ
            (m, 3H, Ar-H), 4.15 (q, J = 7.2 Hz, 2H, OCH 2), 3.20 (s,   ݺ⩕䚥≄䨹ㆶ喑̻᪴⡛Ⱕ℁キࡃγ᧺҉ₒ俑ȡ䔈̭
            1H, OH), 1.75 (br, 3H, COHCH 3 ), 1.11 (t, J = 7.2 Hz,   ₒ㔰ᄌγχ䨉⯽ᄦࡃव➖ 1 ϔ⢴⮱ᒞ৺喍Ꮌत 7Ƞ8喎喑
                       13
            3H, CH 3 )ȡ CNMR (101 MHz, CDCl 3 ),  į: 163.87
            (O==C), 163.55 (Ar-C), 139.58 (Ar-C), 128.23 (Ar-C),   䮼Ɑχ䨉⯽͚࢑࣌ၽࡷᒱ෋ߍ喑χ䨉⯽⮱יࡃ᩵᳉
            126.03 (Ar-C), 117.43 (Ar-C), 112.24 (Ar-C), 75.91   ᰡສ喑ᒀВ CuI ͧϸᄩᬣ喑ࡃव➖ 1 ϔ⢴ᰭ倅喑䓫
            (CF 2 O), 75.67 (CF 2 O), 62.95 (COH), 23.35       ݝ 89%喍Ꮌत 8喎ȡ
                                                     +
            (COHCH 3 ), 13.63 (CH 3 )ȡESI-MS, m/Z喟[M+H] ⤳䃧         В 1.0 mmol  ēa হ 1.5 mmol  Ĕa ͧ࣌᫆Ƞ
            թ 245.10喠჋≸թ 245.11ȡ                               0.2 mmol  CuIȠ3.0 mmol 䨹ㆶͧיࡃݯȠ0.2 mmol
                                                               CF 3 CO 2 H ͧ⌨ߍݯ喑ౕ⏣ݯ 2 mLȠბ⍖̸䔈㵹ࣺᏁ喑
            2   㐀᳉̻䃕䃧
                                                               㔰ᄌγ⏣ݯᄦࡃव➖ 1 ϔ⢴⮱ᒞ৺喑㐀᳉݄λ㶕 2ȡ

            2.1   ᲎Уよ䔶
                                                                              㶕 2   ⏣ݯ⮱よ䔶
                 仃ٵ喑В㠜⩟䛈喍ēa喎হ 2-ⷅΆ䚥Ά䚜喍Ĕa喎                                 Table 2    Screening of solvent
            ⮱ࣺᏁͧ὎ᲬࣺᏁ喑ౕბ⍖̸喑ВΆ㙵ͧ⏣ݯ喑ᄦ
            χ䨉⯽䔈㵹γよ䔶喠Ꭳ䔈̭ₒ㔰ᄌγ⏣ݯᄦࣺᏁ⮱
            ᒞ৺喑хࡃγव᜽ࣺᏁ᲎Уȡ
                 ڤҀ᲎Уͧ喟ܳݘߍڒ 1.0 mmol  ēaȠ1.5 mmol               Ꮌत           ⏣ݯ           ࣺᏁᬣ䬡/h      ϔ⢴/%
            ĔaȠ0.2 mmol χ䨉⯽喍[Cu]喎Ƞ3.0 mmol 䨹ㆶͧי                  1    Ά㙵                      24        89
                                                                 2    V(Ά㙵)ńV(Ⅱ)=1ń1          12        95
            ࡃݯ喑ౕ 2 mL Ά㙵͚ბ⍖̸ࣺᏁ 24 h喑㔰ᄌγ 2-                       3    Ⅱ                       24        54
            ࢑Ά䚥Ά䚜͚⮱࢑࣌ၽ喍X喎Ƞχ䨉⯽ᄦࡃव➖ 1 ϔ                            4    ఈ⅏ॸર喍THF喎               24        64
            ⢴⮱ᒞ৺喑㐀᳉݄λ㶕 1ȡ                                        5    Ά䛇喍Et 2O喎               24        69
                                                                 6    1,4-ι⅔ښ⣜                24        67
                                                                 7    ⩟㠜                      24        62
                           㶕 1   יࡃݯ⮱よ䔶                          8    ₐጞ☤                     24        61
                       Table 1    Screening of catalysts         9    ι⅜⩟☤喍DCM喎               24        72

                                                                   ⩞㶕 2 जⴒ喑̺ह⏣ݯᄦࡃव➖ 1 ϔ⢴⮱ᒞ৺
                                                               䒰๔ȡᰶᱧ⏣ݯ⮱ᲮᕔᄦࣺᏁ⮱ᒞ৺䒰๔喑ᰶᱧ⏣

                                                     ŗ
               Ꮌत      X     [Cu]    ⏣ݯ         ϔ⢴/%           ݯ⮱Ხᕔ๔ᄦࣺᏁᰶݖ喑ВᲮᕔ䒰๔⮱Ά㙵ͧ⏣ݯ
                1      Br    ÿ       Ά㙵           13           ࣺᏁ㣤ᓄγ䒰ສ⮱㐀᳉喍Ꮌत 1喎ȡ䔈̭ₒⵁ⾣ࣾ⣝喑
                2      I     ÿ       Ά㙵           26           ⅡᄦΆ㙵ͧ⏣ݯ⮱ēaহĔa⮱ࣺᏁ㘪䊤ݝᒵສ⮱Ӱ
                3      Br    CuCl    Ά㙵           47           䔈҉⩕   [16] 喑́㘪Ხ๔ౝۼᄾࣺᏁᬣ䬡喍Ꮌत 2喎ȡ♣
                4 Ř    Br    CuCl    Ά㙵           69
                5      I     CuCl    Ά㙵           74           㔹ࢂ㏜ВⅡͧ⏣ݯ喑ࣺᏁϔ⢴ᬻ̸᭫䭺喍Ꮌत 3喎喑
                6 ř    I     CuCl    Ά㙵           82           䔆᭜⩞࣌᫆ēa হĔa ౕⅡ͚⏣㼐Ꮣጛ᝭㜡ȡВ 2 mL
                7 ř    I    CuBr     Ά㙵           85           V(Ά㙵)ńV(Ⅱ)=1ń1 ⮱⌤व⋟ͧ⏣ݯᬣ喑ࡃव➖ 1
                8 ř    I     CuI     Ά㙵           89
                                                               ϔ⢴ᰭສ喑䓫ݝ 95%喍Ꮌत 2喎ȡౕڣЃᰶᱧ⏣ݯ͚
                 ŗܳ⻨ϔ⢴喑̸ह喠Řߍڒ 1.0 mmol NaI喠řߍڒ 0.2 mmol
            CF 3CO 2Hȡ                                         ࣺᏁΌ㘪䒰ສౝ䔈㵹喑ѳࡃव➖ 1 ϔ⢴ᬻ̸᭫䭺喍Ꮌ
                                                               त 4~9喎ȡ
                 ⩞㶕 1 जⴒ喑̺ह⮱χ䨉⯽㣤ᓄ⮱ࣺᏁ㐀᳉ጛ                            㐩̷喑䔶Ⴧ⮱ᰭхࣺᏁ᲎Уͧ喟В 0.2 mmol CuI
            ᐯ䒰๔喑⇎ᰶߍڒχ䨉⯽喑ࡃव➖ 1 ϔ⢴ᒵጛ喍Ꮌ                           ͧϸᄩȠ3.0 mmol 䨹ㆶͧיࡃݯȠ0.2 mmol CF 3 CO 2 H
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