Page 235 - 《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➖ g921g

[6]
Reformatsky ࣺᏁ⩞ SERGIUS λ 1887 Ꭱ仃⁎ 䱿ᇈ⊤∸ࡃጒᰶ䭽ڙथȡ჋侹⩕Ⅱ౴ͧࣨ⻨ၽⅡȡ
្䖀喑ౕ䛾ᆋ䨹ႅ̸ౕ喑Į-࢑А䚥䚜̻䛈ᝃ䚛ࣺᏁ Bruker Avance 400 MHz ᵥⷮڞᡜ∏䅞З喑ᓤప
⩌᜽ ȕ-㓌ധ䚥䚜喑ȕ-㓌ധ䚥䚜䔈̭ₒ㙞Ⅱᓄݝ Į,ȕ- Bruker ڙथ喠Agilent 6210 䉕䅞З喑㒻ప Agilent ڙथȡ
̺亞হ㓔䚥䚜喑᭜̭ㆨ䛺㺮⮱Ჱᐧ CÿC 䩛⮱ࣺᏁ 1.2 ࡃव➖⮱ݣิ
͸̭ [7-8] ȡ䓾ᎡᲒ喑̺ह䛾ᆋ喍䨹ㆶ [9-10] Ƞᰶᱧ䨹 [11-12] Ƞ В 3-㓌ധ-3-㠜ധ͆䚥Ά䚜喍1喎⮱व᜽ͧҸȡ
Mg [13-15] ȠMn [16] ȠIn [17] ȠSm [18] ぶ喎Ӱ䔈⮱ Reformatsky ౕ 10 mL Schlenk ノ͚喑ܳݘߍڒ㠜⩟䛈 106.1 mg
ࣺᏁःᓄγᲮ๔ࣾᆂȡѳ̷䔝ࣺᏁႅౕ᧺҉ฺᱯȠ 喍1.0 mmol喎Ƞ2-ⷅΆ䚥Ά䚜 177.5 ȝL喍1.5 mmol喎Ƞ
ࣺᏁᬣ䬡䪬喑ϔ⢴ѻぶ̺䋠ȡ఍ₑ喑ᐭࣾᰡキࢂȠ CuI 38.0 mg喍0.2 mmol喎Ƞ䨹ㆶ 192.0 mg喍3.0 mmol喎
᏶ФȠ倅᩵⮱ Reformatsky ࣺᏁ㜠ڠ䛺㺮ȡ ͧיࡃݯ喑̶⅌Ά䚥喍CF 3 CO 2 H喎15.0 ȝL喍0.2 mmol喎
䮼ⱭϧЙᄦ⣜ධ䛺㺮ᕔ⮱䃑䃳喑㐬㞟ࡃ႓䊷Გ ͧ⌨ߍݯ喑2 mL V(Ά㙵)ńV(Ⅱ)=1ń1 ⮱⌤व⋟ͧ
䊷ऄݝϧЙ⮱ڠ∕ [19] ȡэ㐌⮱ Reformatsky ࣺᏁ䰭㺮Ҭ ⏣ݯ喑ბ⍖̸ࣺᏁ喑Ҭ⩕㪱ᅯ㞟䅞∂喍TLC喎䌌䍗
⩕๔䛼ᰶᱧ⏣ݯ [20] 喑ຯ฼㞠㤺ぶ [16] ᐭࣾγ ̭ ⻺ ࣺᏁ䔈⼸喑ᆂᐭݯͧ V(Ά䚥Ά䚜)ńV(ⴠ⇦䛇)=1ń
Reformatsky יࡃҀ㈨喑჋⣝γⷅАΆ䚥Ά䚜̻䛈䚛⮱ 50 ⮱⌤व⋟ȡࣺᏁ㐀᲌ऻ喑ߍڒࣨ⻨ၽⅡ喍5 mL喎
Reformatsky ࣺᏁ喑䄒Ҁ㈨ВΆ㙵ࣺͧᏁ⏣ݯ喑̺こव ⌙▚ࣺᏁ喑ںߍڒ亞হ NH 4 Cl ⏣⋟͚হ喑♣ऻᄳࣺ
㐬㞟ࡃ႓⮱⤳ᔢȡ఍ₑ喑ⵁ⾣ⅡⰥ Reformatsky ࣺ Ꮑ⌤व➖⩕Ά䚥Ά䚜喍30 mL喎ܳ 3 ⁎㤰ः喑वᎣᰶ
Ꮑڤᰶ࡮ܳ䛺㺮⮱⤳䃧ᘼͶহ⣝჋ᘼͶȡⰛݺ喑ጟ ᱧᅯ喑⩕ᬍⅡ⶘䚥䩮᎟✒喑᫸᎟ᰶᱧ⏣ݯᓄݝ㇄ϔ
ᰶⅡⰥ͚䛾ᆋיࡃ Reformatsky ࣺᏁ⮱Ⱕڠ្䖀喑 ➖ȡ㇄ϔ➖⩕⵲㘣ᴞᅯᲽȲV(Ά䚥Ά䚜)ńV(ⴠ⇦
ຯ Zn/Fe [21] ȠMg [15] ȠIn [17] ȠSm/BiCl 3 [22] ぶ喑ѳ䔆ψ 䛇)=1ń50 ⮱⌤व⋟ȳ㏜ࡃ喑ᓄݝ叱㞟⇦⟣➖ࡃव
1
ࣺᏁႅౕϔ⢴ᒵѻȠ䛾ᆋᬯ䉢ȠҬ⩕⃿ᕔ䒰๔⮱ ➖ 1 [26] 喑184.3 mg喑ϔ⢴ 95%ȡ HNMR (400 MHz,
BiCl 3 হ CdCl 2 喑̺こव㐬㞟ࡃ႓⮱⤳ᔢぶ̺䋠ȡ䨉 CDCl 3 ), į: 7.28~7.16 (m, 5H, Ar-H), 5.08~4.97 (m,
Ꭼ∈ႅౕλౝภহ⊤∸͚喑䉱⎽͝ჹ喑Фᵩѻ᏶́ 1H, CHOH), 4.06 (q, J = 7.2 Hz, 2H, OCH 2 ), 3.47 (s,
1H, OH), 2.70~2.53 (m, 2H, CH 2 ), 1.15 (t, J = 7.2 Hz,
ᄦ⣜ධ࢞რᄼȡጟᰶᄾ䛼ڠλ䨹יࡃহχ䨉⯽ϸᄩ 3H, CH 3 )ȡ CNMR (101 MHz, CDCl 3 ), į: 172.40
13
⮱ⅡⰥ Reformatsky ࣺᏁ⮱្䖀 [23-25] 喑ѳ䔆ψࣺᏁ (O==C), 142.68 (Ar-C), 128.54 (Ar-C), 127.78 (Ar-C),
ႅౕ̭ψ̺䋠喟㺮ٵݣิ Zn/Cu יࡃݯ [23] 喑ᄩ㜡᧺ 125.73 (Ar-C), 70.33 (COH), 60.90 (CH 2 O), 43.48
+
҉㍮⤽喠ग䔯⩕λ̭ψ➦₷Ꮒ➖喑ຯࣹ⅌㓝ധ/χ㘧 (CH 2 ), 14.16 (CH 3 )ȡESI-MS, m/Z喟[M+H] ⤳䃧թ
ࡃव➖ [24-25] ぶ喑ᄩ㜡Ꮒ➖䔯⩕㠰డ⾱ȡݺ᱌ⵁ⾣͚喑 195.11喠჋≸թ 195.10ȡ㶕ᒮ㐀᳉̻᪴⡛[26]̭㜡ȡ
ࣾ⣝ВⅡͧ⏣ݯ喑Ά㙵ͧߖ⏣ݯ喑ౕ᏶Фᭀᓄ⮱ CuI ڣ҆ࡃव➖⮱व᜽䓴⼸हࡃव➖ 1ȡ
ϸᄩ̸喑В䨹ㆶͧיࡃݯ喑㘪倅᩵יࡃ Reformatsky 3-㓌ധ-3-(3-⩟㠜ധ)͆䚥Ά䚜喍2喎喟叱㞟⇦⟣➖ [27] 喑
1
ࣺᏁ喑ࣺᏁ͚Ά㙵Ҭ⩕䛼๔๔ۼᄾ喑こव㐬㞟ࡃ႓ 189.3 mg喑ϔ⢴ 91%ȡ HNMR (400 MHz, CDCl 3 ), į:
⮱⤳ᔢȡ 7.17~6.98 (m, 4H, Ar-H), 5.03~4.96 (m, 1H, CHOH),
఍ₑ喑᱙᪴᠌ౕ CuI ϸᄩ̸喑В䨹ㆶͧיࡃݯ喑 4.08 (q, J = 7.2 Hz, 2H, OCH 2 ), 3.35 (s, 1H, OH),
2.69~2.54 (m, 2H, CH 2 ), 2.26 (s, 3H, Ar-CH 3 ), 1.16 (t,
יࡃ 2-ⷅΆ䚥Ά䚜̻㟠䛈/㟠䚛⮱ Reformatsky ࣺ
13
J = 7.2 Hz, 3H, CH 3 )ȡ CNMR (101 MHz喑CDCl 3 ), į:
Ꮑ喑В᱌倅᩵व᜽ 32 ͗ ȕ-㓌ധ䚜ㆨࡃव➖ 1~32喑
172.46 (O==C), 142.61 (Ar-C), 138.19 (Ar-C), 128.53
ڣࣺᏁᐼຯ̸᝭⹧ȡ (Ar-C), 128.45 (Ar-C), 126.41 (Ar-C), 122.77 (Ar-C),
70.35 (COH), 60.87 (CH 2 O), 43.46 (CH 2 ), 21.47
+
(Ar-CH 3 ), 14.17 (CH 3 )ȡESI-MS, m/Z喟[M+H] ⤳䃧
թ 209.11喠჋≸թ 209.12ȡ
3-㓌ധ-3-(4-⩟㠜ധ)͆䚥Ά䚜喍3喎喟叱㞟⇦⟣➖ [28] 喑
1
191.4 mg喑ϔ⢴ 92%ȡ HNMR (400 MHz, CDCl 3 ), į:
7.13 (d, J = 8.0 Hz, 2H, Ar-H), 7.03 (d, J = 8.0 Hz, 2H,
Ar-H), 4.97~4.85 (m, 1H, CHOH), 4.03 (q, J = 7.1 Hz,
1 ჋侹䘕ܳ
2H, OCH 2 ), 3.42 (br, 1H, OH), 2.67~2.50 (m, 2H,
CH 2 ), 2.22 (s, 3H, Ar-CH 3 ), 1.13 (t, J = 7.1 Hz, 3H,
1.1 䄂ݯ̻Зக 13
CH 3 )ȡ CNMR (101 MHz, CDCl 3 ), į: 172.35 (O==C),
̺ह㟠䛈/㟠䚛Ƞ2-ⷅΆ䚥Ά䚜Ƞ䨹ㆶȠχ䨉⯽喑 139.87 (Ar-C), 137.36 (Ar-C), 129.17 (Ar-C), 125.70
䉕䛼ܳ᪝ō98%喑䭬៶̮䄂ݯ(̷⊤)ᰶ䭽ڙथ喠Ά䚥 (Ar-C), 70.19 (COH), 60.81 (CH 2 O), 43.53 (CH 2 ),
Ά䚜Ƞⴠ⇦䛇喍PE喑60~90 Ď喎ぶ䄂ݯ喑౴ͧ AR喑 21.13 (Ar-CH 3 ), 14.16 (CH 3 )ȡESI-MS, m/Z喟[M+H] +
๖≒ጯ๔㠯ࡃ႓䄂ݯࢯ喠ᴞᅯᲽ⵲㘣喍200~300 Ⱋ喎喑 ⤳䃧թ 209.11喠჋≸թ 209.12ȡ