Page 239 - 《精细化工》2023年第4期

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