CN115181081A - 一种β-苯基-γ-丁内酯的合成方法 - Google Patents
一种β-苯基-γ-丁内酯的合成方法 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/32—Oxygen atoms
- C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
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- C07F15/06—Cobalt compounds
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- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
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Abstract
本发明涉及一种β‑苯基‑γ‑丁内酯的合成方法。其特征是采用一种离子化的金属钴配合物为手性催化剂，催化H2O2氧化3‑苯基环丁酮，不仅以较高的收率和对映选择性获得了产物β‑苯基‑γ‑丁内酯，而且实现了催化剂的分离回收和循环使用。解决了不对称Baeyer‑Villiger氧化反应中高的对映选择性与催化剂的循环使用两者不能兼得的问题。
Description
技术领域
本发明涉及一种β-苯基-γ-丁内酯的合成方法，具体地说是一种采用离子化钴配合物催化过氧化氢氧化3-苯基环丁酮得到β-苯基-γ-丁内酯的方法。属于新型催化剂的制备与应用领域。
背景技术
γ-丁内酯是制备许多药物、农用化学品、调料和香料的重要中间体。β-取代的-γ-丁内酯具有手性，在β-位有一个手性中心，其具有两种立体异构体结构。而常规的合成方法通常反应不具备立体(对映)选择性，产物中两种异构体等量存在。而使其中一种对映异构体过量的反应，即β-取代的-γ-丁内酯的不对称合成，在药物合成中具有重要的意义。
在开链酮或环酮分子中插入氧生成相应的酯或内酯的反应称为Baeyer-Villiger氧化反应。近年来，利用不对称Baeyer-Villiger氧化反应，将无手性的环酮经过手性催化剂的不对称性诱导作用，经一步催化氧化反应制备出所需要的手性内酯的研究取得了显著的成就。该反应效率高，环酮底物通常廉价易得，反应历程可控性强，因而以其为合成手性内酯的途径具有很大的潜力。
有机过氧酸作为传统的Baeyer-Villiger氧化反应的氧化剂，具有显著的缺点，如原子利用率低、副产物废酸较多且难处理等。而以H2O2作为Baeyer- Villiger反应中的氧化剂，逐渐突显其优势，如双氧水价格低廉、反应条件温和、副产物为水等，契合绿色化学发展的标准。另一方面，目前用于不对称Baeyer- Villiger氧化反应的手性催化剂，一般为金属配合物催化剂，而此类催化剂多为油溶性催化剂，在后处理过程中，通常与产物分离困难，不易再回收利用。当以H2O2为氧化剂(用H2O2水溶液)时，通常还需要伴随着表面活性剂的使用，同样存在后续分离困难的问题。因此，如何设计合成高效绿色、可回收的手性催化剂，开发一种环境友好的高效制备手性内酯的新方法，是极具挑战性的问题。
发明内容
本发明开发了一种环境友好的高效制备手性内酯的新方法。本发明采用一种离子化的金属钴配合物为手性催化剂，催化H2O2氧化3-苯基环丁酮，不仅以较高的收率和对映选择性获得了产物β-苯基-γ-丁内酯，而且实现了催化剂的分离回收和循环使用。由于以H2O2为氧化剂时，Baeyer-Villiger氧化反应一般在有机/水两相(因使用H2O2水溶液)中进行，本发明将催化剂设计成由阴阳离子组成的新一类离子型金属配合物催化剂，该新型催化剂具有相转移催化的能力，通过调控其亲水/疏水性能，使反应适合在有机/水两相界面上进行，从而显著加快Baeyer-Villiger氧化反应的速率，而无需再额外加入表面活性剂；另外，反应结束后，可实现有机相(产物相)与水相(催化剂相)的自动分离以及催化剂的回收重复使用。另一方面，该离子化的金属钴配合物结构中引入了手性配体，赋予了其催化剂手性特征，利用手性催化剂的不对称性诱导作用，使反应具有较好的对映选择性。
本发明β-苯基-γ-丁内酯的合成方法，包括如下步骤：
将一定摩尔比的3-苯基环丁酮和离子化钴配合物、一定量的内标物联苯、以及一定量的去离子水，加入到配有回流冷凝管及温度计的三口烧瓶中，开启磁力搅拌，搅拌5min后，缓慢滴加一定量的H2O2水溶液(30wt％)，在一定温度下反应一定时间。反应结束后，用乙酸乙酯萃取产物，合并有机相，经无水硫酸镁干燥后旋蒸浓缩，最后利用气相色谱定量分析反应中3-苯基环丁酮的转化率、产物β-苯基-γ-丁内酯的产率和对映选择性；水相经旋蒸和真空干燥后重新获得催化剂，可进行循环利用。
本发明方法所述的催化剂用量占原料摩尔量的5～10％，3-苯基环丁酮和氧化剂H2O2的摩尔比为1:4～1:10，反应温度为10～40℃，反应时间为4～8h。
反应式如下：
催化剂的结构式如下：
其中R为C4～C12的直链烷基。
本发明的有益效果体现在：
提供了一种具有相转移催化性能、并可有效与产物分离的手性催化剂，用于催化H2O2氧化3-苯基环丁酮，不仅以较高的收率和对映选择性获得了产物β- 苯基-γ-丁内酯，而且有效的实现了催化剂的分离回收和循环使用，解决了不对称Baeyer-Villiger氧化反应中高的对映选择性与催化剂的循环使用两者不能兼得的问题。
具体实施方法
下列实施例用来进一步说明本发明，但不因此而限制本发明。
实施例1：催化剂的制备
(a)氯甲基化产物2的制备
在100mL三口烧瓶中依次加2.54g5-硝基水杨醛1、1.00g多聚甲醛、 0.20g氯化锌、以及10mL浓盐酸，充分搅拌混合。将混合物在HCl气氛中于 40℃下连续搅拌反应24h。用无水乙醚萃取3次，去离子水洗涤乙醚层3次，干燥后旋蒸除乙醚，即得氯甲基化产物2。
(b)离子液体3的制备
在100mL三口烧瓶中依次加入2.15g氯甲基化产物2、1.37gN-正丁基咪唑、以及25mL无水乙腈，混合溶液在60℃冷凝回流反应24h。旋转蒸发除溶剂，产物用乙醚洗涤，真空干燥后得离子液体产物3。
(c)离子型配体4的制备
在100mL三口烧瓶中依次加入1.22g离子液体3、10mL无水乙醇、以及0.25g1,2-环己二胺，混合液在60℃冷凝回流下搅拌反应15h。旋转蒸发除溶剂，随后用乙醚洗涤，真空干燥即可获得离子型配体4。
(d)离子化配合物5的制备
在100mL三口烧瓶中依次加入1.38g离子型配体4、10mL无水乙醇、以及0.498g四水合醋酸钴Co(OAc)2·4H2O，混合溶液在60℃冷凝回流反应24h，抽滤收集滤液。旋转蒸发滤液，对产物用乙酸乙酯-乙醚1:1混合溶液洗涤。真空干燥后即得离子化钴配合物5(R为正丁基)，即为目标催化剂。
催化剂的制备流程如下：
实施例2：
在配有球形冷凝管及温度计的25mL三口烧瓶中，先后加入0.0438g(0.3 mmol)3-苯基环丁酮、0.03mmol催化剂(R为正丁基)、一定量内标物联苯、以及1mL去离子水，待反应液搅拌5min催化剂充分溶解后，滴加2.7mmol 的30wt％H2O2溶液，在15℃下恒温水浴连续搅拌反应8h。反应结束后，用乙酸乙酯萃取产物2次，合并有机相，经无水硫酸镁干燥后旋蒸浓缩，最后利用气相色谱进行定量分析，得到3-苯基环丁酮的转化率为98％，产物β-苯基-γ-丁内酯的收率为75％，内酯的对映选择性为63％。
实施例3：
在配有球形冷凝管及温度计的25mL三口烧瓶中，先后加入0.0438g(0.3 mmol)3-苯基环丁酮、0.03mmol催化剂(R为正丁基)、一定量内标物联苯、以及1mL去离子水，待反应液搅拌5min催化剂充分溶解后，滴加2.7mmol 的30wt％H2O2溶液，在15℃下恒温水浴连续搅拌反应6h。反应结束后，用乙酸乙酯萃取产物2次，合并有机相，经无水硫酸镁干燥后旋蒸浓缩，最后利用气相色谱进行定量分析，得到3-苯基环丁酮的转化率为97％，产物β-苯基-γ-丁内酯的收率为74％，内酯的对映选择性为65％。
实施例4：
在配有球形冷凝管及温度计的25mL三口烧瓶中，先后加入0.0438g(0.3 mmol)3-苯基环丁酮、0.03mmol催化剂(R为正丁基)、一定量内标物联苯、以及1mL去离子水，待反应液搅拌5min催化剂充分溶解后，滴加3.0mmol 的30wt％H2O2溶液，在15℃下恒温水浴连续搅拌反应8h。反应结束后，用乙酸乙酯萃取产物2次，合并有机相，经无水硫酸镁干燥后旋蒸浓缩，最后利用气相色谱进行定量分析，得到3-苯基环丁酮的转化率为98％，产物β-苯基-γ-丁内酯的收率为72％，内酯的对映选择性为61％。
实施例5：
在配有球形冷凝管及温度计的25mL三口烧瓶中，先后加入0.0438g(0.3 mmol)3-苯基环丁酮、0.024mmol催化剂(R为正丁基)、一定量内标物联苯、以及1mL去离子水，待反应液搅拌5min催化剂充分溶解后，滴加2.7mmol 的30wt％H2O2溶液，在15℃下恒温水浴连续搅拌反应8h。反应结束后，用乙酸乙酯萃取产物2次，合并有机相，经无水硫酸镁干燥后旋蒸浓缩，最后利用气相色谱进行定量分析，得到3-苯基环丁酮的转化率为95％，产物β-苯基-γ-丁内酯的收率为70％，内酯的对映选择性为57％。
实施例6：
在配有球形冷凝管及温度计的25mL三口烧瓶中，先后加入0.0438g(0.3 mmol)3-苯基环丁酮、0.03mmol催化剂(R为正丁基)、一定量内标物联苯、以及1mL去离子水，待反应液搅拌5min催化剂充分溶解后，滴加2.7mmol 的30wt％H2O2溶液，在25℃下恒温水浴连续搅拌反应8h。反应结束后，用乙酸乙酯萃取产物2次，合并有机相，经无水硫酸镁干燥后旋蒸浓缩，最后利用气相色谱进行定量分析，得到3-苯基环丁酮的转化率为97％，产物β-苯基-γ-丁内酯的收率为74％，内酯的对映选择性为61％。
实施例7
在配有球形冷凝管及温度计的25mL三口烧瓶中，先后加入0.0438g(0.3 mmol)3-苯基环丁酮、0.03mmol催化剂(R为正辛基)、一定量内标物联苯、以及1mL去离子水，待反应液搅拌5min催化剂充分溶解后，滴加2.7mmol 的30wt％H2O2溶液，在25℃下恒温水浴连续搅拌反应8h。反应结束后，用乙酸乙酯萃取产物2次，合并有机相，经无水硫酸镁干燥后旋蒸浓缩，最后利用气相色谱进行定量分析，得到3-苯基环丁酮的转化率为94％，产物β-苯基-γ-丁内酯的收率为72％，内酯的对映选择性为58％。
实施例8-10：
实验条件与反应步骤同实施例1，反应结束后，水相经旋蒸和真空干燥后重新获得催化剂，将重新获得的催化剂按实施例1的实验条件与反应步骤进行 3次重复实验。催化剂在循环使用3次后，3-苯基环丁酮的转化率为94％，产物β-苯基-γ-丁内酯的收率为70％，内酯的对映选择性为62％。
对比例1：
在实施例1的催化剂合成中，将起始原料5-硝基水杨醛1直接与第三步中的1,2-环己二胺反应，生成配体，再和醋酸钴反应，生成未离子化的双(5-硝基)水杨基-1,2-环己二胺-钴配合物。将实施例2中的催化剂换成未离子化的钴配合物，其它条件同实施例2。3-苯基环丁酮的转化率为43％，产物β-苯基-γ- 丁内酯的收率为32％，内酯的对映选择性为40％。
对比例2：
在实施例1的催化剂合成中，将起始原料5-硝基水杨醛1换成5-叔丁基水杨醛，其它条件和步骤同实施例1。将最终合成的催化剂取代实施例2中的催化剂，其它条件同实施例2。3-苯基环丁酮的转化率为87％，产物β-苯基-γ-丁内酯的收率为56％，内酯的对映选择性为45％。
对比例3：
在实施例1的催化剂合成中，将第四步中的醋酸钴换成同摩尔量的醋酸锰，其它条件和步骤同实施例1。将最终合成的锰配合物催化剂取代实施例2中的钴配合物催化剂，其它条件同实施例2。3-苯基环丁酮的转化率为82％，产物β- 苯基-γ-丁内酯的收率为51％，内酯的对映选择性为52％。
Claims (4)
1.一种离子化钴配合物催化3-苯基环丁酮氧化合成β-苯基-γ-丁内酯的方法，其特征在于，以3-苯基环丁酮为原料，30wt％H2O2水溶液为氧化剂，离子化的钴配合物为催化剂，在一定温度下反应一定时间，所述的催化剂的结构式如下：
其中R为C4～C12的直链烷基。
2.如权利要求1所述的方法，其特征在于，催化剂的合成路线如下：
3.如权利要求1所述的方法，其特征在于，催化剂的用量为3-苯基环丁酮用量的5～10mol％，3-苯基环丁酮和氧化剂H2O2的摩尔比为1:4～1:10，反应温度为10～40℃，反应时间为4～8h。
4.如权利要求1所述的方法，其特征在于，反应结束后，用乙酸乙酯萃取产物，下层水相中的催化剂经脱水后可循环再利用。
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