CN117940541A - 环丙烷化香料化合物 - Google Patents
环丙烷化香料化合物 Download PDFInfo
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- CN117940541A CN117940541A CN202180102107.5A CN202180102107A CN117940541A CN 117940541 A CN117940541 A CN 117940541A CN 202180102107 A CN202180102107 A CN 202180102107A CN 117940541 A CN117940541 A CN 117940541A
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- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B9/00—Essential oils; Perfumes
- C11B9/0026—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring
- C11B9/003—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring the ring containing less than six carbon atoms
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B9/00—Essential oils; Perfumes
- C11B9/0003—Compounds of unspecified constitution defined by the chemical reaction for their preparation
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B9/00—Essential oils; Perfumes
- C11B9/0026—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring
- C11B9/0034—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring the ring containing six carbon atoms
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B9/00—Essential oils; Perfumes
- C11B9/0042—Essential oils; Perfumes compounds containing condensed hydrocarbon rings
- C11B9/0046—Essential oils; Perfumes compounds containing condensed hydrocarbon rings containing only two condensed rings
- C11B9/0049—Essential oils; Perfumes compounds containing condensed hydrocarbon rings containing only two condensed rings the condensed rings sharing two common C atoms
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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- Organic Chemistry (AREA)
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- Fats And Perfumes (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及某些环丙烷化化合物作为香料的用途。特别地，所述化合物提供果香和/或花香嗅觉基调。此外，本发明提供包含环丙烷化化合物的香料组合物和芳香产品以及生产芳香产品的方法。本发明还涉及生产环丙烷化化合物的方法，并且提供多种新型环丙烷化化合物。
Description
技术领域
本发明涉及某些环丙烷化化合物作为香料的用途。特别地，所述化合物提供果香和/或花香嗅觉基调。此外，本发明提供包含环丙烷化化合物的香料组合物和芳香产品以及生产芳香产品的方法。本发明还涉及生产环丙烷化化合物的方法，并且提供多种新型环丙烷化化合物。
背景技术
尽管有大量可用的香料物质，但在香水和香料行业中对新型化合物和化合物的组合物的需求仍存在。为了满足客户的需求，必须定期开发新的香料特征和复杂的嗅觉印象。因此，行业一直在寻找新的化合物，其显示特殊感官特性并可用作新型香水和香料的成分要素。
环丙烷环是在几种香料化合物中发现的基序，并且文献中描述了获得环丙烷化香料化合物的方法(EP1262474A1，化学与生物多样性(Chemistry&Biodiversity)，第11卷(2014)，1734-1751)。烯烃的环丙烷化通常提供有趣的新嗅觉特性，并会增加所产生的香料分子的稳定性。此外，香料可以通过环丙烷化而增强。因此，人们一直在努力发现新的环丙烷化化合物，并评估其在香料行业的潜力。特别希望在环丙烷化化合物中引入更多变化。
Ebner和Carreira(化学综述(Chemical Reviews),2017,117,11651-11679)以及Wu等人(有机和生物分子化学(Organic and Biomolecular Chemistry),2018,16,7315-7329)总结了环丙烷化的一般策略。Panne等人在有机快报((Organic Letter s),2008,10(14),2987-2989)中描述了铑催化的重氮酯介导的环丙烷化。然而，这种反应尚未应用于更大和复杂的分子，而该等分子可能会提供有趣的新香料。
发明内容
本发明的目的是提供具有新的有趣嗅觉特性的环丙烷化化合物。这些化合物应提供有吸引力且稳定的香料。
此外，本发明的目的是提供一种方法，该方法允许获得多种取代的环丙烷化化合物，从而提供新的有趣的香料。
通过使用式(I)化合物或者两种或更多种式(I)化合物的混合物作为香料来实现上述目的
其中R1＝COOX，X＝甲基、乙基或叔丁基，或
R1＝CH2OH，
R2＝H或甲基，以及
R3至R6的定义如以下化合物(1)至(34)中所示，
其中所述化合物选自以下化合物：
在本发明的上下文中，发现化合物(1)至(34)提供有吸引力和独特的嗅觉特性，因此化合物作为香料有用。
由于以下事实，难以找出实现本发明的合适的物质：
嗅觉感知的机制还不够清楚；
特定嗅觉感知与相关联的香料物质的化学结构之间的关联性还没有得到充分的研究；
通常即使是已知香料物质的结构设置的微小变化也会导致感官特性的重大变化，并且影响人体组织的耐受性。
根据上述用途的一个优选实施方式，式(I)化合物或者两种或更多种式(I)化合物的混合物是对映纯的、外消旋的或非对映异构体的混合物。
已经发现化合物(1)至(34)特别提供果香和花香嗅觉基调。在上述用途的一个优选实施方式中，式(I)化合物或者两种或更多种式(I)化合物的混合物具有果香和/或花香。
表1提供化合物(1)至(34)的嗅觉特性的概述，这些特性是通过对经过培训的香料专家小组的评估而确定的。
表1：化合物(1)至(34)的嗅觉特性
在上述用途的一个优选实施方式中，化合物(1)提供一种或多种选自由果香、花香、菠萝味、酯香和黄油味组成的组的嗅觉基调，和/或化合物(2)提供一种或多种选自由果香、热带香、树莓味、苹果味和花香组成的组的嗅觉基调，和/或化合物(3)提供一种或多种选自由葡萄柚味、菠萝味、大黄味和自然气味组成的组的嗅觉基调，和/或化合物(4)提供一种或多种选自由果香和大黄味组成的组的嗅觉基调，和/或化合物(5)提供一种或多种选自由果香、草绿香和熟大黄味组成的组的嗅觉基调，和/或化合物(6)提供泥土香嗅觉基调，和/或化合物(7)提供一种或多种选自由果香、草绿香和杏味组成的组的嗅觉基调，和/或化合物(8)提供一种或多种选自由果香、草莓味和菠萝味组成的组的嗅觉基调，和/或化合物(9)提供一种或多种选自由醋栗味、果香、香蕉味和黄油味组成的组的嗅觉基调，和/或化合物(10)提供一种或多种选自由草绿香、果香、香蕉味和奇异果味组成的组的嗅觉基调，和/或化合物(11)提供一种或多种选自由醋栗味、果香、香蕉味和“凉糖味”(即糖果味、甜味、清新味)组成的组的嗅觉基调，和/或化合物(12)提供一种或多种选自由果香、花香、草绿香和韭菜味组成的组的嗅觉基调，和/或化合物(13)提供一种或多种选自由果香、韭菜味和“凉糖味”(即糖果味、甜味、清新味)组成的组的嗅觉基调，和/或化合物(14)提供一种或多种选自由果香、韭菜味和“凉糖味”(即糖果味、甜味、清新味)组成的组的嗅觉基调，和/或化合物(15)提供甜瓜味嗅觉基调，和/或化合物(16)提供草绿香嗅觉基调，和/或化合物(17)提供一种或多种选自由果香、清新味、花香和紫檀味组成的组的嗅觉基调，和/或化合物(18)提供果香嗅觉基调，和/或化合物(19)提供一种或多种选自由大黄味和自然气味组成的组的嗅觉基调，和/或化合物(20)提供一种或多种选自由大黄味和自然气味组成的组的嗅觉基调，和/或化合物(21)提供果香嗅觉基调，和/或化合物(22)提供一种或多种选自由果香和黄油味组成的组的嗅觉基调，和/或化合物(23)提供清新味嗅觉基调，和/或化合物(24)提供一种或多种选自由清新味和果香组成的组的嗅觉基调，和/或化合物(25)提供果香嗅觉基调，和/或化合物(26)提供果香嗅觉基调，和/或化合物(27)提供清新味嗅觉基调，和/或化合物(28)提供果香嗅觉基调，和/或化合物(29)提供一种或多种选自由自然气味、园艺草本植物香和芳香组成的组的嗅觉基调，和/或化合物(30)提供果香嗅觉基调，和/或化合物(31)提供一种或多种选自由果香和菠萝味组成的组的嗅觉基调，和/或化合物(32)提供一种或多种选自由奶油味、木香和果香组成的组的嗅觉基调，和/或化合物(33)提供一种或多种选自由果香和菠萝味组成的组的嗅觉基调，和/或化合物(34)提供一种或多种选自由梨味和果香组成的组的嗅觉基调。
本发明还涉及一种香料组合物，其包含一种如上定义的式(I)化合物或者两种或更多种如上定义的式(I)化合物的混合物。
如上定义的式(I)的化合物可以与其他香料物质一起使用。这种香料组合物可以以通常的方式制备，例如通过简单地混合或均化各成分。这些其他香料物质可以是任何其他香料物质。可在本发明的范围内有利地与如上定义的式(I)化合物组合的香料的示例可以在例如S.Arctander，香水和香精材料(Perfume and Flavor Materials)，第I卷和第II卷，Montclair，N.J.1969，Eigenverlag、或K.Bauer等人，常见香料香精材料(CommonFragrance and Flavors Materials)，第4版，Wiley VCH，W einheim 2001中找到。
根据本发明的香料组合物可吸附到载体上，这既确保香料物质在产品中的精细分布又确保在应用过程中的受控释放。这种载体可以是诸如轻质硫酸盐、硅胶、沸石、石膏、粘土、粘土颗粒、加气混凝土等多孔无机材料、或诸如木材、纤维素基材料、糖、糊精(如麦芽糊精)的有机材料、或诸如PVC、聚乙酸乙烯酯或聚氨酯的塑料。根据本发明的组合物和载体可以表示根据本发明的芳香产品(如下文所述)。
根据本发明的香料组合物或产品也可以以微胶囊形式、喷雾干燥形式、包合物形式或挤出产品形式存在，并且在香料组合物的情况下可以以上述形式添加到待芳香化的产品中(如本文下文所述)。
如果适用，考虑到更具针对性的香味释放，可通过使用合适的材料，优选使用诸如聚乙烯醇的蜡状塑料进行所谓“涂层”，进一步优化这种改性组合物或产品的性能。所得产物就是根据本发明的产品。
例如，微胶囊化可通过使用例如聚氨酯类物质或软明胶的胶囊材料的所谓的凝聚过程实现。喷雾干燥产品优选通过喷雾干燥含有香料组合物的乳液或分散体来生产，其中改性淀粉、蛋白质、糊精和植物胶可用作载体。包合物可例如通过将香料组合物的分散体和环糊精或尿素衍生物掺入合适的溶剂中，例如水中进行制备。挤出产品可例如通过将香料组合物与合适的蜡状物质融合，并通过挤出，然后进行固化来获得，如果适用，固化在例如异丙醇的合适的溶剂中进行。
此外，本发明还涉及包含一种如上定义的式(I)化合物或者两种或更多种如上定义的式(I)化合物的混合物或者一种如上定义的香料组合物的(芳香)产品。
在一个优选的实施方式中，该产品选自由洗涤剂和清洁剂、卫生或护理产品组成的组，该产品优选属于在身体和头发护理、化妆品和家用领域。
根据一个优选的实施方式，产品选自由香水提取物、浓香水(eau de parfums)、淡香精(eau de toilettes)、须后水、古龙水、须前产品、古龙水喷雾、芳香湿巾、酸性、碱性和中性清洁剂、纺织品清新剂、熨烫助剂、液体洗衣皂、洗衣皂粉、洗衣预处理剂、织物柔软剂、清洁皂、清洁片、消毒剂、表面消毒剂、空气改良剂、气雾剂喷雾、蜡和抛光剂、身体护理产品、护手霜和乳液、护足霜和乳液、脱毛霜和乳液、须后霜和乳液、美黑霜和乳液、护发产品、除臭剂和止汗剂、装饰性化妆品产品、蜡烛、灯油、香棒、杀虫剂、驱虫剂和发泡剂(blowingagent)组成的组。
在上述实施方式中任一个描述的(芳香)产品的优选实施方式中，相对于产品的总重量，如上定义的式(I)化合物或者两种或更多种如上定义的式(I)化合物的混合物的重量为0.01wt.-％至10wt.-％，优选为0.01wt.-％至7wt.-％。
该量表示感官有效量，其中式(I)化合物或者两种或更多种式(I)化合物的混合物能够提供令人愉快的感官效果，并且产品被认为具有期望的香味。
在一个实施方式中，上述(芳香)产品包含一种或多种添加剂、赋形剂和/或活性物质。
添加剂、赋形剂和/或活性物质优选不是香料物质，并且优选选自由：保存剂(preservative)，优选为US2006/0089413中提及的保存剂；研磨剂；抗痘剂和皮脂减少剂，优选为WO 2008/046791中提及的抗痘剂和皮脂减少剂；抗老化剂，优选为WO 2005/123101中提及的抗老化剂；、抗菌剂；消脂剂；去屑剂，优选为WO 2008/046795中提及的去屑剂；抗炎剂；刺激预防剂；抗刺激物(抗炎剂、刺激抑制剂和刺激预防剂)，优选为WO 2007/042472和US2006/0089413中提及的抗刺激物；抗微生物剂，优选为WO 2005/123101中提及的抗微生物剂；抗氧化剂，优选为WO 2005/123101中提及的那些抗氧化剂；收敛剂；防腐剂(antiseptic agent)；抗静电剂；粘合剂；缓冲剂；载体材料，优选为WO 2005/123101中提及的载体材料；螯合剂，优选为WO 2005/123101中提及的螯合剂；细胞刺激剂；洁净剂；护理剂；脱毛剂；表面活性剂；除臭剂和止汗剂(优选为WO 2005/123101中提及的除臭剂和止汗剂；增塑剂；乳化剂，优选为WO 2005/123101中提及的乳化剂；酶；精油，优选为US2008/0070825中提及的精油；驱虫剂，优选为WO 2005/123101中提及的驱虫剂；纤维；成膜剂；(此外)固定剂；泡沫剂(foaming agent)；泡沫稳定剂；用于防止发泡的物质；泡沫促进剂；杀真菌剂；胶凝剂和凝胶形成剂，优选为WO 2005/123101中提及的胶凝剂和凝胶形成剂；头发护理产品；头发变形剂；直发剂；水分调节剂(滋润剂和/或润湿剂和/或保湿剂)，优选为WO2005/123 101中提及的水分调节剂；渗透剂，优选为WO 2005/123101中提及的渗透剂；相容性溶质，优选为WO 01/76572和WO 02/15686中提及的相容性溶质；漂白剂；增强剂；去污剂；光学增亮剂；浸渍剂；驱污剂；减摩剂；润滑剂；滋润霜；软膏；遮光剂；塑化剂；覆盖剂；抛光剂；增亮剂；聚合物，优选为WO 2008/046676中提及的聚合物；粉末剂；蛋白质和蛋白质水解物，优选为WO 2005/123101和WO 2008/046676中提及的蛋白质和蛋白质水解物；加脂剂(refattening agent)；研磨剂；皮肤舒缓剂；皮肤洁净剂；皮肤护理剂；皮肤修复剂，优选为含有胆固醇和/或脂肪酸和/或神经酰胺和/或假神经酰胺的皮肤修复剂，因此优选为WO2006/053912中提及的皮肤修复剂；皮肤增白剂，优选为WO 2007/110415中提及的皮肤增白剂；护肤剂；柔肤剂；皮肤清凉剂，优选WO 2005/123101中提及的皮肤清凉剂；皮肤增温剂，优选为WO 2005/123101中提及的皮肤增温剂；稳定剂；紫外线吸收剂和紫外线过滤剂，优选为WO 2005/123101中提及的紫外线吸收剂和紫外线过滤剂；亚苄基β-二羰基化合物，优选为WO 2005/107692中提及的亚苄基β-二羰基化合物；α-苯甲酰基肉桂酸腈，优选为WO2006/015954中提及的α-苯甲酰基肉桂酸腈；芳香烃受体(AhR)拮抗剂，优选为WO 2007/128723和WO 2007/060256中提及的芳香烃受体拮抗剂；洗涤剂；织物柔软剂；悬浮剂；皮肤美黑剂，优选为WO 2006/045760中提及的皮肤美黑剂、增稠剂；维生素，优选为WO 2005/123101中提及的维生素；脂肪油；蜡和脂肪，优选为WO 2005/123101中提及的蜡和脂肪；磷脂，优选为WO 2005/123101中提及的磷脂；脂肪酸(饱和脂肪酸、单不饱和或多不饱和脂肪酸、α-羟基酸、多羟基脂肪酸)，优选为WO 2005/123101中提及的脂肪酸；染料和颜色保护剂以及颜料，优选为WO 2005/123101提及的染料和颜色保护剂以及颜料；抗腐蚀剂；醇类和多元醇，优选为WO 2005/123101中提及的醇类和多元醇；表面活性剂，优选为WO 2005/123101中提及的表面活性剂；动物提取物；酵母提取物；藻类或微藻的提取物；电解质；液化剂；有机溶剂，优选为WO 2005/123101中提及的有机溶剂；毛发生长调节剂(毛发生长促进剂或毛发生长抑制剂)，优选为EP 2168570和EP 2193785中提及的毛发生长调节剂；或硅酮和硅酮衍生物，优选为WO 2008/046676中提及的硅酮和硅酮衍生物组成的组，优选选自由保存剂、无机盐、螯合剂、表面活性剂、皮肤和/或毛发护理剂、酶、乳化剂、脂肪、脂肪油、蜡、脂肪醇、硅酮、硅酮衍生物和水组成的组。
在另一个方面，本发明涉及一种生产优选为如上述实施方式中任一个所述的产品的芳香产品的方法，所述方法包括以下步骤：
(i)提供一种如上定义的式(I)化合物或者两种或更多种如上定义的式(I)化合物的混合物或者一种如上定义的香料组合物，
(ii)提供芳香产品的其他组分，以及
(iii)使步骤(ii)中提供的芳香产品的其他组分与感官有效量的一种如上定义的式(I)化合物或者两种或更多种如上定义的式(I)化合物的混合物或者一种如上定义的香料组合物接触。
“感官有效量”是指产生感官效果的化合物或化合物的混合物的总量。感官效果可以是赋予、增强和/或改变某些嗅觉基调和/或掩盖和/或减少不愉快基调。因此，感官有效量是，与不包含化合物或化合物的混合物的产品相比，用户可在产品中感知到化合物或化合物的混合物的感官效果的量。关于产品的上文中已给出提供这种效果的合适用量。
最后，本发明还涉及一种生产如上定义的式(I)化合物的方法，所述方法包括以下步骤：
(i)在铑配合物的存在下，使式(II)的重氮化合物与式(III)的烯烃反应，
其中R1＝COOX，X＝甲基、乙基或叔丁基，且
R2＝H或甲基
其中R3至R6按照如上定义的所得化合物(1)至(15)、(17)至(31)和(33)至(34)中所示被定义，或其中R3至R6按照如所得化合物(35)和(36)中所示被定义
以形成选自由化合物(1)至(15)、(17)至(31)和(33)至(36)组成的组的化合物，以及
在步骤(i)中形成化合物(35)或(36)的情况下，包括另一步骤(ii)还原化合物(35)或(36)以形成如上定义的化合物(16)或化合物(32)。
令人惊讶地，发现上述反应可成功地用于生产复杂的香料化合物，特别是本文定义的香料化合物。由于反应为催化反应，因此可方便地在室温下进行，并且不需要加热。此外，令人惊讶地，这些反应可应用于具有复杂立体化学性质和不同取代基的各种化合物，因此显著拓宽了可获得的环丙烷化香料化合物的范围。
在生产上述式(I)化合物的方法的一个优选实施方式中，铑配合物是具有羧酸配体的铑(II)配合物，特别是四(三苯基乙酸)二铑(II)。
本领域技术人员已知许多合适的具有羧酸配体的铑(I I)配合物。特别地，四(三苯基乙酸)二铑(II)提供了良好的结果，但具有羧酸配体的其他铑(II)配合物也起作用。
有利的是，如上文提及，反应可在约室温下进行，而不需要任何加热步骤。在一个优选实施方式中，步骤(i)中的反应在10℃至30℃、优选为15℃至25℃的温度下进行。
用于步骤(i)中进行的反应的合适溶剂是二氯甲烷。用于反应的其他溶剂可以是：氯化和非氯化烷烃类，例如己烷；环烷烃类，例如环己烷；和芳香族溶剂，例如甲苯。
在生产上述式(I)化合物的方法的另一优选实施方式中，通过蒸馏对反应产物进行纯化。
通过蒸馏如上定义的式(I)化合物以使其从反应混合物中纯化，可获得良好的产率和高纯度，这不一定可通过其他方法实现。
在生产上述式(I)化合物的方法的另一优选实施方式中，还原步骤(ii)通过使化合物(35)或(36)与LiAlH4、AlH3或Li(Et)3BH反应来进行。
最后，本发明还提供具有令人愉快香味的新型环丙烷化化合物。如上定义的化合物(3)、(4)、(7)、(15)、(16)、(17)、(19)、(20)、(21)、(23)、(24)、(25)、(26)、(27)、(28)、(29)、(30)、(32)、(33)和(34)未在现有技术中公开。
因此，本发明还涉及一种化合物或者两种或更多种化合物的混合物，化合物选自由化合物(3)、化合物(4)、化合物(7)、化合物(15)、化合物(16)、化合物(17)、化合物(19)、化合物(20)、化合物(21)、化合物(23)、化合物(24)、化合物(25)、化合物(26)、化合物(27)、化合物(28)、化合物(29)、化合物(30)、化合物(32)、化合物(33)和化合物(34)组成的组。
本发明的特征进一步通过以下实施例来说明。
具体实施方式
分析仪器和材料
核磁共振波谱法(NMR)
在室温下，通过布鲁克(BRUKER)Avance 400(400MHz)记录所有NMR光谱。在所有测量中使用从EURISOTOP获得的氘代氯仿作为溶剂。显示相对于残留氯仿峰的化学位移δ(1H：7.26ppm，13C：77.2ppm)。以下缩写用于描述质子分裂模式：d＝双重峰，t＝三重峰，q＝四重峰，m＝多重峰，td＝三重峰的双峰，br＝宽峰等，并且相应的耦合常数以赫兹(Hz)为单位给出。用二维相关光谱(COSY)、异核单量子相干(HSQ C)和异核多键相关(HMBC)对新化合物的信号进行归属。
薄层色谱法(TLC)
所有反应均通过薄层色谱法(TLC)使用涂覆有二氧化硅的铝板(默克(MERCK),硅胶60,F254)进行监测。在每种情况下均使用Seebach溶液作为TLC染色剂。
气相色谱-质谱法(GC-MS)
气相色谱-质谱法(GC-MS)测量在安捷伦科技(Agilent Technologies)6890N型气相色谱仪(电子轰击电离)上进行，该仪器配备有安捷伦19091S-433柱(5％的甲基苯基硅氧烷，30m，0.25μm)和带涡轮泵的5975B VL MSD检测器。氦气用作载气。通过对来自粗产物光谱的相应信号进行积分来确定非对映异构体比例(d.r.)
红外光谱法(IR)
利用衰减全反射(ATR)技术在布鲁克(BRUKER)Alpha ATR上记录红外光谱。吸收带的位置以波数表示，并根据吸收强度用以下缩写进行分类：vs(非常强，0-9％)、s(强，10-39％)、m(中等，40-69％)、w(弱，70-89％)、vw(非常弱，90-100％)。
质谱法
在配备有HESI II探针的赛默飞(Thermo Fisher)Q-Exactive(轨道阱(orbitrap))质谱仪上记录电喷雾电离(ESI)实验，以记录高分辨率。通过分子峰[M]+、质子化分子峰[M+H]+、和特征碎片离子峰来解释光谱。信号以质荷比(m/z)给出。在高分辨率测量的情况下，最大容许误差为±5ppm。
溶剂和化学品
除非另有说明，否则未进一步纯化而使用市售溶剂和化学品(购自Fisher、CarlRoth、abcr、Alfa Aesar、TCI、Sigma Aldrich、VWR Chemicals、Fluka、Bernd Kra ft)。为了空气和水分的敏感反应，通过Mbraun制溶剂纯化系统获得无水溶剂，并在氩气的惰性气氛下通过分子筛将该无水溶剂储存在舒伦克瓶中。未进一步纯化而使用从Symrise AG获得的用于环丙烷化反应的离析物。
操作方法
使用由水/冰(0℃)或氯化钠/冰(-21℃)组成的冷浴来冷却反应混合物。通过T LC和GC-MS监测反应。通过柱色谱法对粗化合物进行纯化。使用石英砂(经过烘烤和用盐酸的洗涤)和二氧化硅(默克，硅胶60，0.040x0.063mm，260-400目，美国材料试验协会(ASTM)标准)。对溶剂进行体积测量。所有玻璃器皿在使用前都进行烘干。使用不锈钢套管向一次性塑料注射器中添加液体。用Sage Instruments的341B型注射泵和Landgraf Laborsysteme的LA100型注射泵缓慢添加液体。使用旋转蒸发器在40℃的减压下蒸发溶剂。
实施例1：四(三苯基乙酸)二铑(II)(Rh2(TPA)4)的合成
和饱和NaCl水溶液(50mL)洗涤。将有机层分离并用Na2SO4干燥。在减压下蒸发溶剂得到深绿色固体形式的粗产物，将该粗产物溶解在二氯甲烷(5mL)中并通过柱色谱法(DCM/EtOAc,3:1)纯化。在80℃下真空干燥8小时后获得深绿色固体状的标题化合物(382mg,282μmol,83％)。发现它与一当量的乙酸乙酯配位，乙酸乙酯可通过进一步加热去除。
Rf＝0.98(DCM/EtOAc,3:1)。
1H NMR(400MHz,CDCl3,ppm)δ＝7.00(t,J＝7.3Hz,12H,HAr),6.79(t,J＝7.7Hz,24H,HAr),6.55(d,J＝7.9Hz,24H,HAr)。
分析数据与文献[1]中报道的数据相匹配。
实施例2：重氮化合物的合成
合成重氮酯的一般程序
通过对Searle[2]描述的方法进行轻微修改来制备重氮酯。在配备有氩气入口、温度计和滴液漏斗的三颈烧瓶中将相应的氨基酸酯盐酸盐(79.6mmol，1当量)溶于水(25mL)和二氯甲烷(60mL)中。烧瓶充满氩气并冷却至-5℃。在搅拌下逐滴加入冰冷的亚硝酸钠(95.6mmol，1.2当量)的水(25mL)溶液，同时将温度保持在-5℃。添加完成后，将温度降至-9℃，并以温度不超过0℃的速率添加硫酸(5％水溶液，9.5m L)。由于不再释放热量，反应在15分钟内终止。
将有机层分离并加入到冷的NaHCO3(5％水溶液，100mL)中。用二氯甲烷(10mL)萃取水层。剧烈摇晃合并的有机层和NaHCO3溶液，直到没有痕量酸残留。分离黄色有机层，并用Na2SO4干燥。在减压下除去溶剂以获得标题化合物，该标题化合物不用进一步纯化即可使用。必须小心蒸发溶剂，因为重氮酯在加热下可能引起爆炸。
2-重氮丙酸叔丁酯
6g，8.71mmol，87％)。
Rf＝0.34(正戊烷/Et2O，30:1)。
1H NMR(400MHz,CDCl3,ppm)δ＝1.68(s,3H,CH3),1.47(s,9H,C(CH3)3)。
2-重氮乙酸甲酯
ol,55％)。
Rf＝0.35(正戊烷/Et2O，30:1)。
1H NMR(400MHz,CDCl3,ppm)δ＝4.74(s,1H,CHN2),3.75(s,3H,CH3)。
实施例3：环丙烷化化合物的合成
烯烃的环丙烷化的一般程序
在舒伦克瓶中，在20℃下将相应的烯烃(1当量)和Rh2(TPA)4(1mol％)溶解于二氯甲烷(0.2M)中。以1mL/h的速率向该溶液中添加重氮酯的二氯甲烷(0.4M)溶液。添加后，将溶液搅拌过夜。真空去除溶剂，残留物通过柱色谱法纯化，得到环丙基化合物。
2-环己基环丙烷-1-羧酸乙酯(化合物(1))
甲烷(22.7mL)溶液为起始材料制备。粗产物通过柱色谱法(正戊烷/Et2O，30:1)纯化，得到无色油状物形式的标题化合物(335mg,1.71mmol,75％)。
d.r.＝1:1.2
Rf＝0.43、0.47(正戊烷/Et2O,30:1)。
GC-MS(5％甲基苯基硅氧烷,30m,0.25μm,He)：tR1＝9.104分钟(45％,[M]+196.1),tR2＝9.376分钟(55％,[M]+196.1)。
1H NMR(400MHz,CDCl3,ppm)δ＝4.12–3.98(m,2H,C6-H2),1.77–1.50(m,5H,5×CHCy),1.31(dt,J＝8.5,4.4Hz,1H,C4-H),1.19(dt,J＝7.1,3.6Hz,3H,C7-H3),1.16–0.92(m,7H,5×CHCy,C2-H,C3-H),0.69–0.54(m,2H,C1-H,C3-H)。
13C NMR(101MHz,CDCl3,ppm)δ＝174.86(C5),173.37(C5),60.39(C6),60.33(C6),41.77(C1),32.79,32.58(2xCH2Cy),29.47(C2),26.52,26.26,26.08,(3x CH2Cy)19.10(C4),14.41(C7),14.31(C3)。
IR(ATR,cm-1)2922(s),2850(m),1806(vw),1800(vw),1793(vw),1724(vs),1656(w),1618(w),1601(w),1591(w),1571(w),1562(w),1557(w),1541(w),1514(w),1477(w),1448(s),1407(m),1373(m),1358(w),1349(w),1330(m),1300(w),1279(w),1264(m),1237(w),1201(m),1174(vs),1159(vs),1115(m),1096(m),1084(m),1037(s),996(m),977(w),941(m),892(w),853(m),830(m),795(w),788(w),747(w),714(w),694(w),681(w),645(w),622(w),609(w),599(w),579(w),567(w),554(w),537(w),514(w),492(w),482(w),477(w),458(w),443(w),435(w),428(w),421(w),411(w),407(w),391(w),381(w)。
HRMS(ESI+,[M+H]+,C12H21O2 +)计算值：197.1537；求得值：197.1534。
分析数据与文献[3]中报道的数据相匹配。
1-甲基二环[3.1.0]己烷-6-羧酸乙酯(化合物(2))
溶液为起始材料制备。粗产物通过柱色谱法(正戊烷/Et2O，30:1)纯化，得到无色油状物形式的标题化合物(145mg,859μmol,71％)。
d.r.＝1:1.1
Rf＝0.43、0.48(正戊烷/Et2O,30:1)。
GC-MS(5％甲基苯基硅氧烷,30m,0.25μm,He)：tR1＝7.2分钟(48％,[M]+168.1),tR2＝7.49分钟(52％,[M]+168.1)。
1H NMR(400MHz,CDCl3,ppm)δ＝4.10–3.99(m,2H,C9-CH2),1.98–1.47(m,6H,3×CH2Cp),1.42(d,J＝3.5Hz,1H,C7-CH),1.26(s,3H,C6-CH3),1.22–1.20(m,1H,C1-CH),1.18(dd,J＝7.2,2.1Hz,3H,C10-CH3)。
13C NMR(101MHz,CDCl3,ppm)δ＝173.07(C8),171.84(C8),60.23(C9),60.17(C9),42.47,41.49,41.01,36.32,36.22,35.58,35.23,33.87,33.65,33.12,32.52,32.07,30.65,30.43,29.20,28.05(CCpr),27.81,26.64,26.12(CCpr),24.50,23.97,22.76,22.71,21.02,20.58,19.58,18.90,16.72,15.09(C6),14.54,14.46,14.42,14.25(CCpr)。
IR(ATR,cm-1)2864(w),1721(vs),1655(w),1601(vw),1584(vw),1554(vw),1543(vw),1446(m),1415(m),1383(w),1367(m),1344(m),1313(w),1302(w),1272(m),1261(w),1222(s),1205(m),1174(vs),1163(vs),1149(vs),1092(vs),1051(s),1038(vs),1009(m),963(m),921(w),902(w),890(w),854(m),815(w),766(w),734(w),721(w),669(w),649(w),623(w),609(w),595(w),585(w),574(w),552(w),520(w),511(w),490(w),472(w),458(w),445(w),436(w),429(w),418(w),404(w),395(w),385(w),380(w)。
HRMS(ESI+,[M+H]+,C10H17O2 +)计算值：169.1223；求得值：169.1218。
2-甲基-3-戊基环丙烷-1-羧酸乙酯(化合物(18))
0当量)的二氯甲烷(17.8mL)溶液为起始材料制备。粗产物通过柱色谱法(正戊烷/Et2O，30:1)纯化，得到无色油状物形式的标题化合物(292mg,1.47mmol,83％)。
d.r.＝1:1.9
Rf＝0.34(正戊烷/Et2O，30:1)。
GC-MS(5％甲基苯基硅氧烷,30m,0.25μm,He)：tR1＝8.390分钟(39％,[M]+198.1),tR2＝8.529分钟(61％,[M]+198.1)。
1H NMR(400MHz,CDCl3,ppm)δ＝4.18–4.04(m,2H,C10-CH2),1.47–0.92(m,17H,包括0.88(m,1H,HCpr),0.91–0.82(m,3H,C1-CH3)。
13C NMR(101MHz,CDCl3,ppm)δ＝173.10,173.02(C9),60.18(C10),34.27,33.23,31.65,31.15,29.41,29.11,28.80(CCpr),26.81,26.51,25.84,23.83,22.78(CCpr),22.75,22.48,22.33,18.13,14.54,14.52,14.18(CCpr),12.20。
IR(ATR,cm-1)2956(w),2924(m),2871(w),2856(w),1723(vs),1656(w),1649(vw),1639(vw),1629(vw),1619(vw),1612(vw),1605(vw),1596(vw),1585(vw),1578(vw),1571(vw),1561(vw),1547(vw),1534(vw),1527(vw),1523(vw),1507(vw),1458(m),1445(m),1373(m),1349(m),1317(w),1302(w),1265(w),1235(w),1174(vs),1163(vs),1126(m),1112(m),1096(s),1071(m),1044(s),990(w),948(w),897(w),880(w),856(m),839(w),819(w),807(w),789(w),766(w),745(w),724(w),684(w),664(w),647(w),637(w),626(w),613(w),606(w),596(w),586(w),575(w),567(w),558(w),537(w),521(w),499(w),486(w),473(w),466(w),453(w),445(w),432(w),424(w),416(w),408(w),399(w),391(w)。
HRMS(ESI+,[M+H]+,C12H23O2 +)计算值：199.1693；求得值：199.1690。
分析数据与文献[4]中报道的数据相匹配。
2-(3,5-二甲基己-4-烯-1-基)环丙烷-1-羧酸乙酯(化合物(3))
7mmol,3.0当量)的二氯甲烷(8.7mL)溶液为起始材料制备。粗产物通过柱色谱法(正戊烷/Et2O，30:1)纯化，得到无色油状物形式的标题化合物(214mg,953μmol,82％)。
d.r.＝1:1.3
Rf＝0.45、0.55(正戊烷/Et2O 30:1)。
GC-MS(5％甲基苯基硅氧烷,30m,0.25μm,He)：tR1＝9.673分钟(44％,[M]+224.1),tR2＝9.829分钟(56％,[M]+224.1)。
1H NMR(400MHz,CDCl3,ppm)δ＝4.89–4.81(m,1H,C4-H),4.16–4.04(m,2H,C13-CH2),2.36–2.25(m,1H,C6-H),1.66(s,3H,C1-CH3),1.58(s,3H,C2-CH3),1.55–1.35(m,2H,C8-CH2),1.34–1.29(m,1H,HCpr),1.28–1.26(m,2H,C7-CH2),1.26–1.22(m,3H,C14-CH3),1.21–1.16(m,1H,HCpr),1.01–0.92(m,1H,HCpr),0.90–0.87(m,3H,C5-CH3),0.71–0.61(m,1H,HCpr)。
13C NMR(101MHz,CDCl3,ppm)δ＝173.19(C12),173.13(C12),131.52(C4),131.45(C4),60.41(C13),60.33(C13),37.85,37.23,32.41,32.29(C6),32.25(C6),31.13(CCpr),29.21(CCpr),27.82,25.92,25.25,25.17,23.20,22.77,22.20,22.13,21.45,21.30,20.59,20.40(CCpr),20.30(CCpr),19.58,18.43,18.07,15.74(CCpr),15.62(CCpr),14.52,14.43,14.26,13.49,13.43。
IR(ATR,cm-1)2917(w),2867(w),1725(vs),1656(vw),1649(vw),1630(vw),1623(vw),1611(vw),1605(vw),1591(vw),1584(vw),1572(vw),1561(vw),1543(vw),1534(vw),1523(vw),1509(vw),1448(m),1405(m),1378(m),1354(w),1332(w),1300(w),1265(w),1225(w),1162(vs),1096(m),1082(m),1068(m),1045(m),984(m),969(w),938(w),857(m),830(m),775(w),758(w),728(w),679(w),669(w),646(w),639(w),632(w),623(w),609(w),596(w),581(w),569(w),555(w),545(w),533(w),514(w),501(w),484(w),476(w),453(w),439(w),426(w),418(w),412(w),402(w),395(w),380(w)。
HRMS(ESI+,[M+H]+,C14H25O2 +)计算值：225.1849；求得值：225.1845。
2-(6-甲基庚-5-烯-2-基)环丙烷-1-羧酸乙酯(化合物(4))
制备。粗产物通过柱色谱法(正戊烷/Et2O，30:1)纯化，得到无色油状物形式的标题化合物(76mg,339μmol,31％)。
d.r.＝1:1.2:2.4:3.7:3.6
Rf＝0.4、0.53、0.66(正戊烷/Et2O 30:1)。
GC-MS(5％甲基苯基硅氧烷,30m,0.25μm,He)：tR1＝8.981分钟(8.1％,M+-CH3209.2),tR2＝9.106分钟(9.5％,M+-CH3209.2),tR3＝9.617分钟(20.3％,M+224.2),tR4＝9.798分钟(31.8％,M+224.2),tR5＝9.944分钟(30.2％,M+224.2)。
1H NMR(400MHz,CDCl3,ppm)δ＝5.15–4.85(m,1H,C4-CH),4.20–4.02(m,2H,C13-CH2),2.15–1.87(m,2H,C5-CH2),1.71–0.65(m,19H)。
13C NMR(101MHz,CDCl3,ppm)δ＝174.88,174.67,173.34,173.18(C12),144.61,131.53,131.29,124.99,124.94,124.73(C4),112.89,112.74(C3),60.42(C13),60.36,60.24,60.18,59.75,41.69,37.79,37.73,37.65,37.18,37.04,36.94,36.88,36.81,36.58,36.46,34.13,33.81,33.29,33.18,33.12,31.51,30.96,29.79,29.63,29.31,29.24,28.76,26.56,25.90,25.83(C5),25.79(C1/C2),25.68,25.49,21.34,21.22,21.13,21.06,20.52,20.41,20.26,20.12,19.75,19.63,19.57,19.42,19.18,18.98,17.77(C1/C2),17.69,15.57,14.63,14.53,14.48,14.41,13.99,13.81,12.48。
IR(ATR,cm-1)2925(w),2917(w),2871(w),1724(vs),1448(m),1405(w),1377(m),1346(w),1300(w),1265(w),1237(w),1163(vs),1113(m),1095(m),1079(m),1038(m),983(w),925(w),858(m),830(m),795(w),785(w),745(w),728(w),681(w),664(w),636(w),626(w),609(w),599(w),591(w),572(w),561(w),552(w),543(w),524(w),507(w),500(w),490(w),482(w),475(w),448(w),429(w),411(w),402(w),397(w),385(w),378(w)。
HRMS(ESI+,[M+H]+,C14H25O2 +)计算值：225.1849；求得值：225.1846。
2-(6-甲基庚-1,5-二烯-2-基)环丙烷-1-羧酸乙酯(化合物(5))
材料制备。粗产物通过柱色谱法(正戊烷/Et2O，30:1)纯化，得到无色油状物形式的标题化合物(128mg,575μmol,53％)。
d.r.＝1.5:1:3.2
Rf＝0.33、0.4、0.5(正戊烷/Et2O,30:1)。
GC-MS(5％甲基苯基硅氧烷,30m,0.25μm,He)：tR1＝9.588分钟(26.2％,[M]+222.1),9.820分钟(17.4％,[M]+222.1),10.080分钟(56.3％,[M]+222.1)。
1H NMR(400MHz,CDCl3,ppm)δ＝5.86–5.61(m,1H,C4-CH),5.21–4.91(m,2H,C8-CH2),4.18–4.03(m,2H,C13-CH2),2.32–1.91(m,4H,C5-CH2,C6-CH2),1.87–0.79(m,13H)。
13C NMR(101MHz,CDCl3,ppm)δ＝173.97,172.04,171.45(C12),147.59,143.60(C3),141.85(C4),136.81,131.79,131.64,124.22,124.18,124.01,123.93(C7),115.56,113.08,112.60,108.79,60.69,60.64,60.52,60.40(C13),37.29,37.19,35.96,32.85,32.71,29.90,28.66,27.49,27.19,26.69,26.62,26.46,25.95,25.82,25.46,21.62,20.70,20.46,20.35,17.84,17.80,17.72,14.91,14.52,14.47,14.42,10.97。
IR(ATR,cm-1)2968(w),2925(w),2874(w),2859(w),1724(vs),1638(w),1595(vw),1445(m),1400(m),1380(m),1354(w),1336(w),1320(w),1265(w),1242(w),1162(vs),1096(m),1062(m),1040(m),990(m),897(m),857(m),843(m),834(m),799(w),783(w),758(w),742(w),717(w),694(w),677(w),666(w),653(w),645(w),637(w),630(w),623(w),616(w),581(w),568(w),552(w),545(w),538(w),523(w),507(w),484(w),476(w),453(w),443(w),432(w),424(w),414(w),404(w),391(w),384(w)。
HRMS(ESI+,[M+H]+,C14H23O2 +)计算值：223.1693；求得值：223.1689。
1,1a,1b,2,5,5a,6,6a-八氢-2,5-桥亚甲基环丙烷[α]茚-1-羧酸乙酯(化合物(6))
纯化，得到无色油状物形式的标题化合物(87mg,400μmol,35％)。化合物需要进一步纯化或分离异构体。
d.r.＝1:1.5:1.6:3.6
Rf＝0.16、0.3、0.34、0.5(正戊烷/Et2O,30:1)。
GC-MS(5％甲基苯基硅氧烷,30m,0.25μm,He)：tR1＝10.787分钟(13％,[M]+218.1),tR2＝11.070分钟(19.4％,[M]+218.1),tR3＝11.149分钟(21.2％,[M]+218.1),tR4＝11.287分钟(46.4％,[M]+218.1)。
1H NMR(400MHz,CDCl3,ppm)δ＝6.15(ddd,J＝22.1,5.7,2.8Hz,1H CH＝CH),5.78–5.63(m,1H,CH＝CH),4.15–4.02(m,2H,C13-CH2),2.93–2.89(m,1H),2.88–2.83(m,1H),2.81–2.70(m,1H,C5-CH2),2.68(dd,J＝8.2,4.0Hz,1H,C5-CH2),2.45–2.40(m,1H),1.75–1.69(m,1H),1.61–1.57(m,1H),1.50–1.45(m,1H),1.44–1.28(m,2H),1.27–1.20(m,3H),1.04(t,J＝3.1Hz,1H)。
13C NMR(101MHz,CDCl3,ppm)δ＝174.50(C12),173.76(C12),138.82(C2/C3),138.36(C2/C3),136.02(C2/C3),135.64(C2/C3),135.27(C2/C3),134.57(C2/C3),134.53(C2/C3),60.60(C13),60.22(C13),60.13(C13),59.73,56.38,55.88,55.54,54.80,54.52,52.91,51.96,51.90,49.88,49.52,48.88,47.25,47.04,46.84,46.53,45.53,45.47,45.36,45.27,43.23,42.83,39.52,38.34,38.26,34.53,33.21,32.98,32.27,32.06,31.55,31.48,31.36,30.42,30.17,29.70,27.97,27.12,24.89,24.00,23.64,23.52,21.10,20.08,19.41,16.10,15.57,14.41,14.31,14.08。
IR(ATR,cm-1)2932(w),2904(w),2867(w),1720(vs),1655(w),1649(w),1616(w),1572(w),1561(w),1551(w),1543(w),1534(w),1523(w),1509(w),1477(w),1451(w),1408(s),1385(m),1367(w),1347(w),1317(m),1286(s),1266(s),1237(m),1210(w),1160(vs),1095(m),1051(s),1031(m),1011(s),992(m),970(m),952(w),931(w),919(w),907(w),904(w),892(w),870(m),841(s),802(w),788(m),738(s),730(s),714(s),693(m),677(w),666(w),629(w),611(w),599(w),589(w),579(w),571(w),560(w),550(w),527(w),518(w),487(w),469(w),455(w),438(w),425(w),416(w),408(w),398(w),381(w)。
HRMS(ESI+,[M+H]+,C14H19O2 +)计算值：219.1380；求得值：219.1379。
2-(2-乙氧基-2-氧代乙基)二环[3.1.0]己烷-6-羧酸乙酯(化合物(15))
6mL)溶液为起始材料制备。粗产物通过柱色谱法(正戊烷/Et2O，30:1)纯化，得到绿色油状物形式的标题化合物(34mg,143μmol,30％)。化合物需要进一步纯化。
d.r.＝1:4.3:2.7
Rf＝0.19、0.21(正戊烷/Et2O 10:1)。
GC-MS(5％甲基苯基硅氧烷,30m,0.25μm,He)：tR1＝10.863分钟(12.5％,[M]+240.1),tR2＝10,962分钟(53.7％,[M]+240.1),tR3＝11.176分钟(33.7％,[M]+240.1)。
1H NMR(400MHz,CDCl3,ppm)δ＝4.17–4.05(m,4H,C2-CH2,C13-CH2),2.70–2.17(m,3H,C4-CH2,C5-CH),2.04–1.34(m,7H,C6-CH2,C7-CH2,C8-CH,C9-CH,C10-CH),1.29–1.22(m,6H,C1-CH3,C13-CH3)。
13C NMR(101MHz,CDCl3,ppm)δ＝173.88,173.74,172.93(C3),172.79,172.61,171.41(C11),165.39,129.93,61.37,60.51(C12),60.43(C2),41.06,39.63,38.11,36.88,36.78,35.68,32.99,32.40,29.91,29.60,28.87,28.59,27.92,27.33,26.69,26.25,25.92,25.21,24.39,24.25,23.84,22.96,22.27,19.12,14.39,14.31,14.15。
IR(ATR,cm-1)2955(w),2939(w),2908(w),2871(w),1721(vs),1649(w),1596(vw),1561(vw),1551(vw),1541(vw),1537(vw),1507(vw),1465(w),1446(w),1414(m),1388(w),1371(m),1332(w),1298(m),1258(vs),1163(vs),1150(vs),1113(s),1095(s),1031(vs),946(w),918(w),867(w),841(m),806(w),744(w),722(m),681(w),670(w),656(w),630(w),609(w),585(w),547(w),535(w),521(w),509(w),496(w),484(w),472(w),462(w),456(w),445(w),433(w),426(w),414(w),397(w),380(w)。
HRMS(ESI+,[M+Na]+,C13H20O4Na)计算值：263.1259；求得值：263.1250。
2-(2-乙酰氧基-6-甲基庚-5-烯-2-基)环丙烷-1-羧酸乙酯(化合物(25))
10:1)纯化，得到绿色油状物形式的标题化合物(81mg,287μmol,37％)。化合物需要进一步纯化。
Rf＝0.44、0.54(正戊烷/Et2O 10:1)。
GC-MS(5％甲基苯基硅氧烷,30m,0.25μm,He)：tR1＝10.885分钟([M]+282.1)。
1H NMR(400MHz,CDCl3,ppm)δ＝5.11–4.96(m,1H,C4-CH),4.10–3.96(m,2H,C15-CH2),2.09-0.84(m,24H,包括2.06–1.94(m,2H,C5-CH2),1.62–1.44(m,6H,C1/C2-CH3),1.22–1.16(m,3H,C16-CH3))。
13C NMR(101MHz,CDCl3,ppm)δ＝174.23,174.14,172.95(C14),171.89,171.85,171.62,170.03,169.87(C9),142.06,141.89,141.76,132.02,131.90,131.83,124.05,123.91,123.82,113.39,113.32,113.24(C4),83.21,83.00,82.94,82.80,81.99,81.57,81.49,60.71(C15),60.26(C15),59.82,40.10,39.68,39.64,38.92,38.85,33.73,33.32,33.05,30.50,30.39,30.12,29.83,29.22,28.63,25.80,25.52,23.96,23.75,23.70,23.32,23.14,22.96,22.86,22.70,22.65,22.36,22.30,22.23,22.08,21.96,21.22,21.02,19.84,18.77,17.78,17.67,17.62,17.37,16.63,14.51,14.40,14.37,14.24,12.18,10.97,10.50(CCpr)。
IR(ATR,cm-1)2931(w),2873(w),1725(vs),1646(w),1596(w),1571(w),1561(w),1544(w),1536(w),1523(w),1507(w),1453(m),1449(m),1407(w),1367(s),1343(w),1324(m),1300(w),1241(vs),1176(vs),1111(s),1089(s),1020(s),943(m),929(m),891(w),858(m),837(m),798(w),773(w),748(w),720(w),700(w),694(w),666(w),656(w),649(w),609(m),567(w),555(w),544(w),537(w),527(w),518(w),513(w),482(w),452(w),438(w),422(w),411(w),388(w),378(w)。
HRMS(ESI+,[M+Na]+,C16H26O4Na)计算值：305.1729；求得值：305.1721。
2-(6-乙酰氧基-6-甲基庚烷-2-基)环丙烷-1-羧酸乙酯(化合物(23))
/Et2O，10:1)纯化，得到淡黄色油状物形式的标题化合物(163mg,573μmol,76％)。化合物需要进一步纯化，并且在GC-MS测量条件下不稳定。
d.r.＝2.1:8:1
Rf＝0.3、0.36(正戊烷/Et2O,10:1)。
GC-MS(5％甲基苯基硅氧烷,30m,0.25μm,He)：tR1＝9.751分钟(18.6％,[M]+181.1),tR2＝9.986分钟(72.4％,[M]+181.1),tR3＝10.061分钟(9％,[M]+＝181.1)。
1H NMR(400MHz,CDCl3,ppm)δ＝4.17–4.06(m,2H,C15-CH2),1.95(s,3H,C1-CH 3),1.72–1.32(m,12H,C3-CH3,C5-CH3,C6-CH2,C7-CH2,C10-CH,HCpr),1.27–1.22(m,4H,HCpr,C16-CH3),1.17–0.63(m,7H,C8-CH2,C9-CH3,2×HCpr)。
13C NMR(101MHz,CDCl3,ppm)δ＝174.83,174.61,173.40,173.34,170.64,170.59,82.56,82.51,61.38,60.45,60.39(C15),41.19,41.01,37.86,37.76,37.39,37.19,37.14,31.53,31.04,29.82,29.68,29.37,29.31,26.21,26.16,26.10,22.61(C1),22.47,21.62,21.55,21.39,21.32,20.42,20.36,20.30,19.66,19.55,19.19,19.00,17.72,15.58,14.49,14.41,14.24,14.19,14.15,13.88,13.78,12.50。
IR(ATR,cm-1)2955(w),2935(w),2907(w),2871(w),2850(vw),1723(vs),1602(w),1575(w),1558(w),1545(w),1513(w),1459(w),1446(w),1405(w),1367(s),1258(vs),1203(s),1173(vs),1160(vs),1115(m),1095(m),1082(m),1037(s),1018(s),982(m),943(m),928(m),858(m),832(m),775(w),764(w),745(w),728(w),700(w),683(w),673(w),666(w),659(w),652(w),642(w),633(w),611(w),569(w),552(w),537(w),530(w),516(w),504(w),484(w),467(w),432(w),419(w),411(w),399(w),382(w),377(w)。
HRMS(ESI+,[M+Na]+,C16H28O4Na)计算值：307.1885；求得值：307.1878。
2-(3-乙酰氧基-3,5-二甲基己-4-烯-1-基)环丙烷-1-羧酸乙酯(化合物(21))
O，10:1)纯化，得到淡黄色油状物形式的标题化合物(118mg,420μmol,48％)。化合物需要进一步纯化。
d.r.＝1:1.3:2.5
Rf＝0.34、0.42(正戊烷/Et2O,10:1)。
GC-MS(5％甲基苯基硅氧烷,30m,0.25μm,He)：tR1＝9.959分钟(20.9％,[M-C2H4O2]+222.2),tR2＝10.064分钟(27.9％,[M-C2H4O2]+222.2),tR3＝10.146分钟(51.2％,[M-C2H4O2]+222.2)。
1H NMR(400MHz,CDCl3,ppm)δ＝4.20–4.09(m,2H,C15-CH2),1.39–1.34(m,1H,HCpr),1.32–1.25(m,3H,C16-CH3),0.76–0.68(m,1H,HCpr)。
13C NMR(101MHz,CDCl3,ppm)δ＝173.19,145.68,142.39,142.28,137.34,136.97,128.24,127.43,127.28,126.06,125.94,125.81,125.70,124.50,114.07,113.93,113.51,112.99,112.87,77.48,77.16,76.84,60.46,60.41(C15),40.86,40.31,37.75,37.35,32.69,32.19,32.11,31.75,31.00,27.07,26.84,26.76,26.10,25.84,25.72,24.25,23.94,23.90,23.84,22.74,22.67,22.01,21.78,21.65,21.57,20.36,20.31,19.99,19.71,19.65,18.44,18.33,17.97,17.92,17.26,15.57(CCpr),15.23,14.52,14.42,13.52,13.48,13.36。
IR(ATR,cm-1)2932(w),2873(w),1721(vs),1618(w),1543(vw),1533(vw),1524(vw),1517(vw),1506(vw),1446(m),1407(m),1378(s),1357(m),1332(w),1300(w),1266(m),1173(vs),1164(vs),1094(s),1079(s),1041(s),994(s),908(m),890(m),858(m),830(s),730(w),680(w),671(w),663(w),636(w),626(w),603(m),582(m),555(m),547(m),535(m),521(m),506(m),482(m),466(m),453(m),446(m),439(m),426(m),416(m),411(m),399(m),392(m),382(m)。
2-(环己-3-烯-1-基)环丙烷-1-羧酸乙酯(化合物(8))
的二氯甲烷(6.9mL)溶液为起始材料制备。粗产物通过柱色谱法(正戊烷/Et2O，30:1)纯化，得到无色油状物形式的标题化合物(124mg,637μmol,46％)。
d.r.＝1:1.5
Rf＝0.46、0.55(正戊烷/Et2O,30:1)。
GC-MS(5％甲基苯基硅氧烷,30m,0.25μm,He)：tR1＝9.340分钟(40％,[M]+194.1),tR2＝9.628分钟(60％,[M]+194.1)。
1H NMR(400MHz,CDCl3,ppm)δ＝5.68–5.58(m,1H,CH＝CH),5.01–4.85(m,1H,CH＝CH),4.18–4.05(m,2H,C11-CH2),2.22–1.70(m,4H,C1-CH2,C4-CH2),1.63–0.72(m,10H,C5-CH2,C6-CH,C7-CH,C8-CH,C9-CH2,C12-CH3)。
13C NMR(101MHz,CDCl3,ppm)δ＝174.73,174.69,173.28,173.23(C10),144.93,144.25,143.61,143.41,127.16,127.08(C2),126.36,126.17,126.12,112.91,112.67,112.40(C3),60.46,60.40,60.00(C11),38.17,37.88,37.75,37.71,36.17,35.61,31.90,31.85,31.68,31.28,31.08,29.53,28.88,28.79,28.63,28.58,28.40,28.22,28.16,28.09,28.00,27.56,26.97,26.30,26.06,25.91,25.35,25.07,24.96,24.81,24.48,23.32,22.87,22.80,22.52,22.42,21.24,21.16,19.49,19.22,19.07,18.17,18.07,17.10,16.57,15.60,14.56,14.52,14.46,14.41,14.21,12.70,12.58。
IR(ATR,cm-1)2979(w),2924(w),2874(w),2856(w),2839(vw),1721(vs),1639(w),1476(w),1446(w),1411(w),1378(w),1373(w),1354(w),1339(w),1327(w),1309(w),1265(w),1249(w),1221(w),1171(vs),1164(vs),1095(m),1041(m),993(m),949(w),911(m),861(m),839(w),800(w),790(w),756(w),722(m),711(w),683(w),653(s),601(w),591(w),578(w),568(w),562(w),543(w),537(w),527(w),511(w),497(w),472(w),459(w),446(w),435(w),425(w),419(w),411(w),397(w),382(w)。
HRMS(ESI+,[M+H]+,C12H19O2 +)计算值：195.1380；求得值：195.1378。
二环[4.1.0]庚烷-7-羧酸乙酯(化合物(9))
溶液为起始材料制备。粗产物通过柱色谱法(正戊烷/Et2O，30:1)纯化，得到无色油状物形式的标题化合物(162mg,1.14mmol,62％)。
d.r.＝1:1.5
Rf＝0.34、0.57(正戊烷/Et2O,30:1)。
GC-MS(5％甲基苯基硅氧烷,30m,0.25μm,He)：tR1＝8.178分钟(40％,[M]+168.1),tR2＝8.418分钟(60％,[M]+168.1)。
1H NMR(400MHz,CDCl3,ppm)δ＝4.16–4.04(m,2H,C9-CH2),1.94–1.79(m,2H,C1-CH,C6-CH),1.74–1.63(m,2H,2×CH Cy),1.60–1.50(m,2H,2×CHCy),1.37(t,J＝4.3Hz,1H,C7-CH),1.33-1.10(m,7H,包括1.25(t,J＝7.2Hz,3H),6×CHCy)。
13C NMR(101MHz,CDCl3,ppm)δ＝175.05,172.12(C8),62.42,61.46,60.32(C9),59.92,26.41,25.83,22.87(C6),22.27,22.21,21.36,21.09,18.69(C1),16.47(C7),14.55,14.45(C10),14.24。
IR(ATR,cm-1)2929(m),2857(w),1720(vs),1647(w),1618(w),1578(vw),1571(vw),1553(vw),1545(vw),1462(w),1446(m),1425(m),1390(w),1377(w),1367(m),1347(w),1303(vs),1262(m),1210(w),1184(vs),1166(vs),1150(vs),1116(m),1095(s),1047(s),1020(m),982(m),956(m),945(m),867(w),853(w),836(m),820(w),812(w),793(w),779(s),730(w),703(m),670(w),653(w),632(w),611(w),601(w),588(w),571(w),555(w),541(w),521(w),499(w),490(w),469(w),450(w),438(w),424(w),411(w),378(m)。
HRMS(ESI+,[M+H]+,C10H17O2 +)计算值：169.1223；求得值：169.1220。
分析数据与文献[5]中报道的数据相匹配。
3-甲基二环[4.1.0]庚烷-7-羧酸乙酯(化合物(10))
(10.9mL)溶液为起始材料制备。粗产物通过柱色谱法(正戊烷/Et2O，30:1)纯化，得到无色油状物形式的标题化合物(261mg,1.43mmol,92％)。
d.r.＝1:2.3(30.1:69.9)
Rf＝0.39、0.64(正戊烷/Et2O,30:1)。
GC-MS(5％甲基苯基硅氧烷,30m,0.25μm,He)：tR1＝8.528分钟(30.1％,[M]+182.1),tR2＝8.831分钟(69.9％,[M]+182.1)。
1H NMR(400MHz,CDCl3,ppm)δ＝4.16–4.03(m,2H,C10-CH2),2.14–0.76(m,16H包括1.24,t,J＝7.0Hz,3H,C11-CH3)。
13C NMR(101MHz,CDCl3,ppm)δ＝174.98,172.11(C9),62.41,61.45,60.32(C10),59.91,32.21,31.55,30.63,29.46,28.88,28.81,28.59,28.18,26.95,26.60,26.36,26.29,25.93,23.99,23.31,22.94,22.68,22.57,22.51,22.47,22.38,22.27,22.13,21.97,21.27,19.94,18.44,18.29,16.95,15.59,14.55,14.45,14.24,14.20。
IR(ATR,cm-1)2951(w),2924(w),2868(w),2854(w),1721(vs),1647(vw),1458(m),1445(m),1428(m),1367(w),1343(w),1330(w),1312(s),1296(m),1261(m),1230(w),1211(w),1171(vs),1150(vs),1095(m),1048(s),1006(m),992(m),977(m),955(w),918(w),907(w),897(w),888(w),861(w),826(w),806(m),799(m),772(w),731(w),707(m),666(w),654(w),623(w),609(w),594(w),584(w),572(w),552(w),544(w),526(w),518(w),503(w),490(w),472(w),449(w),438(w),424(w),411(w),404(w),391(w),375(w)。
HRMS(ESI+,[M+H]+,C11H19O2 +)计算值：183.1380；求得值：183.1377。
2-(环己基甲基)环丙烷-1-羧酸乙酯(化合物(30))
的二氯甲烷(7.6mL)溶液为起始材料制备。粗产物通过柱色谱法(正戊烷/Et2O，30:1)纯化，得到无色油状物形式的标题化合物(209mg,992μmol,82％)。
d.r.＝1:3.2
Rf＝0.4、0.49(正戊烷/Et2O,30:1)。
GC-MS(5％甲基苯基硅氧烷,30m,0.25μm,He)：tR1＝9.907分钟(24％,[M]+211.2),tR2＝9.961分钟(76％,[M]+211.2)。
1H NMR(400MHz,CDCl3,ppm)δ＝4.15–4.07(m,2H,C7-CH2),1.65–1.59(m,2H,C2-CH2),1.44–0.88(m,17H,包括1.31(dt,J＝8.4,4.4Hz,1H,C4-CH),1.28–1.22(m,3H,C8-CH3),1.03–0.94(m,1H,C1-CH),2×HCpr,5×HCy),0.65(ddd,J＝8.2,6.4,4.0Hz,1H,HCpr)。
13C NMR(101MHz,CDCl3,ppm)δ＝174.80,173.27(C6),60.40,60.31(C7),41.11,38.44,38.18,34.55,33.42,33.34,33.25,26.76,26.71,26.55,26.52,26.44,21.12,20.56,20.14,18.40,15.87(CCpr),14.52,14.44,13.53。
IR(ATR,cm-1)2980(w),2921(s),2850(m),1724(vs),1656(w),1649(w),1598(w),1578(vw),1561(vw),1541(w),1536(w),1528(vw),1516(vw),1509(vw),1448(s),1407(m),1380(m),1370(m),1341(w),1322(w),1307(w),1264(m),1203(m),1163(vs),1113(m),1095(m),1081(m),1062(m),1037(s),990(m),963(w),948(m),914(w),891(w),875(m),860(m),844(m),829(m),806(w),765(w),737(w),694(w),679(w),669(w),643(w),635(w),619(w),609(w),598(w),585(w),564(w),552(w),545(w),537(w),521(w),511(w),493(w),473(w),462(w),446(w),441(w),418(w),409(w),404(w),394(w),388(w),384(w)。
HRMS(ESI+,[M+H]+,C13H23O2 +)计算值：211.1693；求得值：211.1689。
2-(环戊基甲基)环丙烷-1-羧酸乙酯(化合物(34))
二氯甲烷(8.5mL)溶液为起始材料制备。粗产物通过柱色谱法(正戊烷/Et2O，30:1)纯化，得到无色油状物形式的标题化合物(218mg,1.11mmol,82％)。
d.r.＝1:1.5
Rf＝0.34、0.43(正戊烷/Et2O,30:1)。
GC-MS(5％甲基苯基硅氧烷,30m,0.25μm,He)：tR1＝9.242分钟(40％,[M]+197.2),tR2＝9.320分钟(60％,[M]+197.2)。
1H NMR(400MHz,CDCl3,ppm)δ＝4.11(qd,J＝7.1,5.5Hz,2H,C7-CH2),1.90-0.88(m,17H,包括1.36–1.31(m,1H,HCpr),1.24(td,J＝7.2,2.3Hz,3H,C8-CH3),1.16–1.04(m,1H,HCpr),C1-CH,4×CH2Cp),0.72–0.63(m,1H,HCpr)。
13C NMR(101MHz,CDCl3,ppm)δ＝174.76,173.27(C6),60.39,60.31(C7),40.71,40.44,39.70,39.40(C8),32.98,32.73,32.67(CCpr),32.61(CCpr),32.55,31.57,25.19,25.14,22.47,21.38,20.45(CCpr),18.38,15.71(CCpr),14.50,14.42,13.49。
IR(ATR,cm-1)2948(m),2908(w),2867(w),1724(vs),1656(vw),1618(vw),1448(w),1405(m),1380(m),1370(w),1354(w),1340(w),1315(w),1303(w),1264(w),1160(vs),1115(m),1095(m),1081(m),1038(m),993(w),963(w),926(w),875(w),858(m),829(m),812(w),806(w),796(w),737(w),670(w),643(w),630(w),619(w),598(w),581(w),568(w),561(w),550(w),538(w),527(w),514(w),503(w),484(w),479(w),459(w),445(w),426(w),414(w),404(w),392(w),378(w)。
HRMS(ESI+,[M+H]+,C12H21O2 +)计算值：197.1536；求得值：197.1534
2-甲基-3-((2,2,3-三甲基环戊基)甲基)环丙烷-1-羧酸乙酯(化合物35))
(6.8mL)溶液为起始材料制备。粗产物通过柱色谱法(正戊烷/Et2O，30:1)纯化，得到无色油状物形式的标题化合物(172mg,0.68mmol,76％)。
d.r.＝1:2.3
Rf＝0.49、0.54(正戊烷/Et2O,30:1)。
GC-MS(5％甲基苯基硅氧烷,30m,0.25μm,He)：tR1＝10.905分钟(70％,[M]+252.2),tR2＝11.035分钟(30％,[M]+252.2)。
1H NMR(400MHz,CDCl3,ppm)δ＝4.10(q,J＝7.1,2H),1.95-0.71(m,26H,包括1.25(t,J＝7.1Hz,3H,C16-CH3),0.89–0.72(m,9H,C4-CH3,C6-CH3,C7-CH3)。
13C NMR(101MHz,CDCl3,ppm)δ＝174.86(C14),60.33(C16),51.23,51.10,45.25,45.15,42.56,42.38,30.30,30.19,28.36,28.29,28.21,27.83,27.50,25.73,22.67,21.48,14.56,14.48,14.37,14.05,12.61,12.00。
2-甲基-3-((2,2,3-三甲基环戊-3-烯-1-基)甲基)环丙烷-1-羧酸乙酯(化合物(36))
溶液为起始材料制备。粗产物通过柱色谱法(正戊烷/Et2O，30:1)纯化，得到无色油状物形式的标题化合物(151mg,0.60mmol,66％)。
d.r.＝1:5.5:1.1:18.3:12.5
Rf＝0.48、0.53、0.61(正戊烷/Et2O,30:1)。
GC-MS(5％甲基苯基硅氧烷,30m,0.25μm,He)：tR1＝10.460分钟(2.6％,[M-CH3]+235.2),tR2＝10.565分钟(14.4％,[M-CH3]+235.2),tR3＝10.669分钟(2.9％,[M-CH3]+235.2),tR4＝10.792分钟(47.6％,[M]+250.1),tR5＝10.910分钟(32.5％,[M]+250.1)。
1H NMR(400MHz,CDCl3,ppm)δ＝5.46–5.26(m,1H,C2-CH),4.17–4.03(m,2H,C15-CH2),2.41-0.69(m,23H,包括1.58(s,3H,C4-CH3),1.28-1.22(m,3H,C16-CH3)。
13C NMR(101MHz,CDCl3,ppm)δ＝174.82,174.78,173.29,172.42,172.35,172.13(C14),149.09,148.97,148.80,148.68(C2/C3),130.97,130.11,129.89(C2/C3),124.16,123.91,121.98,121.85,121.73,60.41,60.35,60.19,59.78(C15),51.03,50.77,50.67,50.61,47.07,46.96,46.80,45.19,44.96,44.64,43.49,43.08,42.60,39.87,35.71,35.67,35.64,35.26,33.91,32.34,31.75,31.59,31.28,28.24,27.94,27.79,27.65,27.55,27.30,27.01,26.77,26.68,25.89,25.84,25.81,25.76,24.52,24.27,23.06,22.57,22.22,21.99,21.95,21.42,21.34,21.28,20.91,20.45,20.21,20.08,19.75,19.63,19.39,19.22,18.71,18.01,14.55,14.49,14.46,14.37,14.26,12.92,12.75,12.57,11.97,9.83,7.84,7.36。
IR(ATR,cm-1)2955(m),2931(m),2867(w),1723(vs),1655(w),1639(w),1630(w),1619(w),1602(w),1579(w),1571(w),1561(w),1544(w),1534(w),1524(w),1509(w),1460(m),1443(m),1417(w),1402(w),1381(m),1363(m),1319(m),1299(w),1282(w),1261(w),1235(w),1220(m),1173(vs),1153(vs),1118(m),1095(s),1075(m),1044(s),1013(m),986(w),963(m),919(w),891(w),860(w),849(w),826(w),798(m),776(w),713(m),701(w),654(w),637(w),620(w),613(w),598(w),582(w),538(w),517(w),507(w),500(w),487(w),473(w),465(w),448(w),432(w),398(w),380(w)cm–1。
HRMS(ESI+,[M+H]+,C16H27O2 +)计算值：251.2006,求得值：251.2001
2-环己基环丙烷-1-羧酸甲酯(化合物(12))
2mL)溶液为起始材料制备。粗产物通过柱色谱法(正戊烷/Et2O，30:1)纯化，得到无色油状物形式的标题化合物(204mg,1.12mmol,82％)。
d.r.＝1:1.1
Rf＝0.31、0.43(正戊烷/Et2O,30:1)。
GC-MS(5％甲基苯基硅氧烷,30m,0.25μm,He)：tR1＝8.528分钟(47％,[M]+182.1),tR2＝8.840分钟(53％,[M]+182.1)。
1H NMR(400MHz,CDCl3,ppm)δ＝3.65(s,3H,C6-CH3),1.81–1.54(m,5H,5×CHCy),1.41–1.33(m,1H,C3-CH),1.26–0.99(m,7H,5×CHCy,C1-CH,CHCpr),0.99–0.91(m,1H,CHCpr),0.75–0.62(m,2H,CHCpr)。
13C NMR(101MHz,CDCl3,ppm)δ＝175.27(C5),173.87(C5),51.71(C6),51.65(C6),37.39,35.88,33.41,33.34,33.24,32.75,32.57,29.57(CCpr),28.82,26.57,26.50,26.23,26.18,26.08,18.86(CCpr),17.78(CCpr),15.40(CCpr),14.39(CCpr)。
IR(ATR,cm-1)2922(s),2850(m),1727(vs),1657(w),1599(w),1578(w),1571(w),1550(w),1527(w),1510(w),1446(s),1436(s),1401(w),1381(m),1367(m),1336(m),1322(w),1299(w),1278(m),1265(m),1238(w),1193(vs),1160(vs),1118(m),1099(m),1082(m),1077(m),1043(m),1031(m),992(m),933(m),909(w),887(s),873(m),843(m),824(m),782(w),773(w),747(w),711(w),684(w),666(w),637(w),630(w),622(w),603(w),592(w),586(w),568(w),554(w),535(w),516(w),507(w),492(w),482(w),470(w),455(w),442(w),426(w),415(w),399(w),390(w),375(w)。
HRMS(ESI+,[M+H]+,C11H19O2 +)计算值：183.1380；求得值：183.1377。
1-甲基二环[3.1.0]己烷-6-羧酸甲酯(化合物(11))
为起始材料制备。粗产物通过柱色谱法(正戊烷/Et2O，30:1)纯化，得到无色油状物形式的标题化合物(182.2mg,1.182mmol,97％)。
d.r.＝1:1.2
Rf＝0.31、0.40(正戊烷/Et2O,30:1)。
GC-MS(5％甲基苯基硅氧烷,30m,0.25μm,He)：tR1＝6.514分钟(45％,[M]+154.1),tR2＝6.806分钟(55％,[M]+154.1)。
1H NMR(400MHz,CDCl3,ppm)δ＝3.64(s,3H,C9-CH3),2.01–1.52(m,6H,3×HCp),1.50(d,J＝3.5Hz,1H,C7-CH),1.45–1.25(m,4H,C6-CH3,C1-CH)。
13C NMR(101MHz,CDCl3,ppm)δ＝173.49,172.28(C8),51.54,51.43,50.92(C9),35.54,35.33,33.86(CCp),33.38,33.06,32.53,32.27,30.29,28.03,26.61,25.92(CCpr),24.50,22.68,20.99,15.10(CCpr)。
IR(ATR,cm-1)2929(m),2856(w),1723(vs),1655(w),1649(w),1619(w),1579(w),1560(w),1554(w),1543(vw),1534(vw),1527(vw),1509(vw),1438(vs),1378(w),1349(w),1306(vs),1283(w),1265(m),1193(vs),1183(s),1166(vs),1152(vs),1081(m),1048(m),1018(m),960(s),950(m),916(m),866(w),851(w),839(w),815(w),793(w),779(s),715(m),704(m),654(w),633(w),592(w),577(w),568(w),547(w),534(w),518(w),504(w),489(w),460(w),432(w),415(w),407(w),399(w),378(w)。
HRMS(ESI+,[M+H]+,C9H15O2 +)计算值：155.1067；求得值：155.1063。
2-(3,5-二甲基己-4-烯-1-基)环丙烷-1-羧酸甲酯(化合物(19))
产物通过柱色谱法(正戊烷/Et2O，30:1)纯化，得到无色油状物形式的标题化合物(142mg,675μmol,62％)。
d.r.＝1:1.2
Rf＝0.45、0.55(正戊烷/Et2O,30:1)。
GC-MS(5％甲基苯基硅氧烷,30m,0.25μm,He)：tR1＝9.103分钟(47％,[M]+210.2),tR2＝9.254分钟(53％,[M]+210.2)。
1H NMR(400MHz,CDCl3,ppm)δ＝4.91–4.79(m,1H,C4-CH),3.66(s,3H,C13-CH3),2.38–2.23(m,1H,C6-CH),1.66(s,3H.C1-CH3),1.58(s,3H,C2-CH3),1.47–0.92(m,7H,C7-CH2,C8-CH2,3×HCpr),0.90–0.86(m,3H,C5-CH3),0.71–0.64(m,1H,HCpr)。
13C NMR(101MHz,CDCl3,ppm)δ＝173.65,173.58(C12),131.51,131.45(C3),131.24,131.21(C4),130.23,130.02,129.97,51.71,51.59(C13),37.79,37.40,37.22,32.44(C6),32.35,32.26,32.22,31.13,25.90,25.18,25.15(C2),23.33,22.26,22.20,21.43,21.26,20.17,20.08,18.20,18.16,18.05(C1),15.81,15.69(CCpr),13.67,13.59(C5)。
IR(ATR,cm-1)2952(w),2919(w),2866(w),2854(w),1730(vs),1677(w),1656(vw),1649(vw),1629(vw),1619(vw),1528(vw),1516(vw),1509(vw),1436(s),1401(w),1378(m),1353(w),1334(w),1317(w),1302(w),1268(w),1194(vs),1166(vs),1132(m),1084(m),1069(w),1045(m),977(w),967(w),946(w),918(w),898(w),866(w),843(m),823(m),776(w),758(w),728(w),683(w),666(w),626(w),615(w),602(w),591(w),581(w),571(w),557(w),547(w),540(w),530(w),514(w),497(w),483(w),475(w),465(w),455(w),448(w),433(w),419(w),411(w),398(w),385(w)。
HRMS(ESI+,[M+H]+,C13H23O2 +)计算值：211.1693；求得值：211.1689。
2-(6-甲基庚-5-烯-2-基)环丙烷-1-羧酸甲酯(化合物(20))
起始材料制备。粗产物通过柱色谱法(正戊烷/Et2O，30:1)纯化，得到无色油状物形式的标题化合物(67mg,319μmol,29％)。
Rf＝0.36、0.49(正戊烷/Et2O,30:1)。
GC-MS(5％甲基苯基硅氧烷,30m,0.25μm,He)：tR1＝9.637分钟([M]+210.1)。
1H NMR(400MHz,CDCl3,ppm)δ＝5.13–4.88(m,1H,C4-CH),3.70–3.61(m,3H,C13-CH3),2.14–1.88(m,2H,C5-CH2),1.67(s,3H,C1/C2-CH3),1.58(s,3H,C1/C2-CH3),1.51–0.66(m,10H,C6-CH2,C8-CH,C7-CH3,4×HCpr)。
13C NMR(101MHz,CDCl3,ppm)δ＝175.31,175.11(C12),173.86,124.98,124.94,124.70(CH＝C),112.92,112.78,112.56(CH＝C),51.76,51.70,51.66,51.48,51.11(C13),42.07,37.81,37.72,37.62,37.16,37.03,36.97,36.90,36.77,36.56,36.44,34.24,34.05,32.97,32.90,31.55,30.92,29.93,29.80,29.32,29.28,28.54,26.27,26.23,25.90(C1/C2),25.85(C5),25.82,25.67,25.42,21.32,21.10,20.53,20.38,20.28,20.18,20.04,19.64,19.39,19.00,18.78,17.79,17.75,17.70,17.51(C1/C2),15.69,14.37,14.11,13.99,12.60。
IR(ATR,cm-1)2918(w),2871(w),2856(w),1728(vs),1639(w),1612(vw),1602(vw),1589(vw),1578(vw),1571(vw),1561(vw),1544(vw),1527(vw),1510(vw),1436(s),1398(w),1377(m),1354(m),1268(w),1193(s),1167(vs),1115(m),1095(m),1082(m),1045(w),1030(w),993(w),912(m),880(w),840(m),824(m),782(w),748(w),741(w),727(w),705(w),683(w),664(w),632(w),620(w),603(w),589(w),578(w),568(w),562(w),557(w),547(w),538(w),521(w),516(w),503(w),487(w),465(w),445(w),433(w),426(w),419(w),404(w),382(w)。
HRMS(ESI+,[M+H]+,C13H23O2 +)计算值：211.1693；求得值：211.1691。
2-(6-甲基庚-1,5-二烯-2-基)环丙烷-1-羧酸甲酯(化合物(29))
粗产物通过柱色谱法(正戊烷/Et2O，30:1)纯化，得到无色油状物形式的标题化合物(97mg,466μmol,42％)。
d.r.＝1:1:1.8
Rf＝0.3、0.39、0.49(正戊烷/Et2O,30:1)。
GC-MS(5％甲基苯基硅氧烷,30m,0.25μm,He)：tR1＝9.352分钟(26.6％,[M]+208.1),tR2＝9.577分钟(25.6％,[M]+208.1),tR3＝9.853分钟(47.8％,[M]+208.1)。
1H NMR(400MHz,CDCl3,ppm)δ＝5.83–5.63(m,1H,C4-CH),5.20–4.85(m,2H,C8-CH2),3.70–3.59(m,3H,C13-CH3),2.34–1.82(m,4H,C5-CH2,C6-CH2),1.79–0.79(m,10H,C1-CH3,C2-CH3,4×HCpr)。
13C NMR(101MHz,CDCl3,ppm)δ＝174.40,172.48,172.00,171.88(C12),147.46,143.54,141.67(C4),138.83,136.74(C4),132.06,132.02,131.81,131.66,124.14,123.94,123.89,120.94,120.68,116.26,115.62,113.40,113.21,112.70,108.89,51.91,51.85,51.74,51.64,51.60,51.49(C13),37.23,37.14,35.94,35.58,35.23,33.85,32.91,32.80,31.38,31.09,31.04,30.99,30.95,29.91,28.88,28.44,28.26,28.16,27.90,27.48,27.29,27.21,27.17,27.04,26.67,26.43,26.16,25.90,25.81,25.45,23.62,23.58,23.53,21.99,21.83,21.38,21.05,20.99,20.52,20.49,19.68,17.82,17.78,17.70,14.91,11.08。
IR(ATR,cm-1)2924(w),2856(w),1728(vs),1639(w),1594(w),1578(w),1571(w),1560(w),1543(w),1534(w),1527(w),1523(w),1509(w),1499(w),1490(w),1436(s),1383(m),1341(w),1323(w),1269(w),1242(w),1193(s),1166(vs),1101(m),1061(w),1050(w),990(w),898(m),868(m),836(m),790(w),758(w),747(w),739(w),700(w),681(w),673(w),656(w),652(w),633(w),620(w),602(w),588(w),569(w),545(w),527(w),513(w),494(w),480(w),463(w),452(w),438(w),415(w),402(w),392(w),375(w)。
HRMS(ESI+,[M+H]+,C13H21O2 +)计算值：209.1536；求得值：209.1534。
1,1a,1b,2,5,5a,6,6a-八氢-2,5-桥亚甲基环戊烷[α]茚-1-羧酸甲酯(化合物(26))
30:1)纯化，得到无色油状物形式的标题化合物(81mg,397μmol,35％)。化合物需要进一步纯化。
d.r.＝1.2:1.6:1:1.4
Rf＝0.15、0.31、0.34、0.51(正戊烷/Et2O,30:1)。
GC-MS(5％甲基苯基硅氧烷,30m,0.25μm,He)：tR1＝10.271分钟(23.3％,[M]+204.1),tR2＝10.583分钟(30.8％,[M]+204.1),tR3＝10.698分钟(18.9％,[M]+204.1),tR4＝10.831分钟(27.0％,[M]+204.1)。
1H NMR(400MHz,CDCl3,ppm)δ＝6.20–6.09(m,1H,CH＝CH),5.74–5.51(m,1H,CH＝CH),3.72–3.57(m,3H,C13-CH3),2.88–2.83(m,1H),2.79(dt,J＝8.4,4.1Hz,1H),2.76–2.71(m,1H),2.67(ddd,J＝7.9,4.1,2.9Hz,1H),2.46–2.39(m,1H),2.37–2.30(m,1H),1.76–1.69(m,1H),1.50–1.43(m,2H,C8-CH2),1.33–1.27(m,1H)。
13C NMR(101MHz,CDCl3,ppm)δ＝175.04(C12),174.31(C12),174.00(C12),172.78(C12),138.94,138.41,136.17,135.83,135.75,135.38(CH＝CH),134.71,134.67(CH＝CH),132.91(CH＝CH),130.29(CH＝CH),56.59,56.03,55.68,54.64,53.03,52.08,52.03,51.66,51.58(C13),,51.48(C13),,51.19(C13),50.04,49.98,49.65,49.02,47.38,47.17,46.98,46.66,45.64,45.47,45.40,42.95,39.65,38.37,34.81,34.67,33.44,33.22,32.55,31.61,31.49,31.46,30.89,30.68,30.29,29.95,29.90,29.15,28.10,27.06,25.06,24.17,23.54,23.46,21.28,15.56。
IR(ATR,cm-1)3030(vw),2951(m),2866(w),2184(vw),2179(vw),2128(vw),2116(vw),2105(vw),2091(vw),2081(vw),2068(vw),2058(vw),2053(vw),2047(vw),2027(vw),2019(vw),1999(vw),1985(vw),1977(vw),1949(vw),1942(vw),1932(vw),1919(vw),1912(vw),1904(vw),1891(vw),1881(vw),1873(vw),1857(vw),1850(vw),1843(vw),1826(vw),1817(vw),1807(vw),1781(vw),1773(vw),1724(vs),1664(w),1655(w),1615(w),1572(w),1560(w),1547(w),1536(w),1528(w),1520(w),1509(w),1436(vs),1400(s),1347(w),1320(m),1302(m),1288(s),1268(s),1238(m),1191(vs),1163(vs),1147(vs),1089(m),1054(m),1030(m),1011(m),996(m),962(m),948(m),929(w),911(m),887(m),850(s),833(m),822(w),813(w),792(m),768(w),756(w),730(s),714(s),693(m),677(w),664(w),623(w),618(w),603(w),594(w),572(w),564(w),550(w),526(w),511(w),489(w),467(w),446(w),429(w),412(w),405(w),398(w),385(w)。
HRMS(ESI+,[M+Na]+,C13H16O2Na)计算值：227.1048；求得值：227.1042
2-(2-乙氧基-2-氧代乙基)二环[3.1.0]己烷-6-羧酸甲酯(化合物(24))
液为起始材料制备。粗产物通过柱色谱法(正戊烷/Et2O，10:1)纯化，得到无色油状物形式的标题化合物(81mg,397μmol,35％)。化合物需要进一步纯化。
d.r.＝1:3.6:3.3
Rf＝0.24、0.31(正戊烷/Et2O,10:1)。
GC-MS(5％甲基苯基硅氧烷,30m,0.25μm,He)：tR1＝10.423分钟(12.6％,[M]+226.1),tR2＝10.542分钟(45.4％,[M]+226.1),tR3＝10.763分钟(42.0％,[M]+226.1)。
1H NMR(400MHz,CDCl3,ppm)δ＝4.12(qdd,J＝7.2,3.5,1.2Hz,2H,C2-CH2),3.68–3.60(m,3H,C12-CH3),2.77–2.16(m,3H,C4-CH2,C5-CH),2.08–1.31(m,7H,3×HCpr,2×CH2Cp),1.24(tdd,J＝7.2,3.3,1.9Hz,3H,C1-CH3)。
13C NMR(101MHz,CDCl3,ppm)δ＝174.29,174.16,173.67(C11),172.94,172.88,172.77,172.58,171.89(C3),60.52,60.44,60.26(C2),54.09,52.45,52.34,51.78,51.71(C12),41.04,39.59,38.06,37.55,36.85,36.74,35.68,34.25,33.06(CCpr),32.51,29.99,29.78,29.09,28.64,28.14,27.99,27.31,26.64,26.21,25.93,25.20,24.60,24.25,23.72,22.71,22.46,22.07,18.91,14.38,14.34,14.18(C1)。
IR(ATR,cm-1)2952(w),2871(vw),1724(vs),1655(w),1629(w),1560(vw),1553(vw),1528(vw),1438(s),1407(m),1373(m),1339(w),1299(m),1258(s),1167(vs),1147(vs),1095(m),1069(m),1030(s),972(w),962(w),935(w),888(w),846(m),822(w),807(w),788(w),762(w),724(w),687(w),677(w),656(w),633(w),592(w),584(w),558(w),548(w),526(w),511(w),504(w),470(w),463(w),449(w),429(w),421(w),411(w),397(w),380(w)。
HRMS(ESI+,[M+Na]+,C12H18O2Na)计算值：249.1103；求得值：249.1094。
2-(2-乙酰氧基-6-甲基庚-5-烯-2-基)环丙烷-1-羧酸甲酯(化合物(27))
到黄色油状物形式的标题化合物(81mg,287μmol,37％)。化合物需要进一步纯化，并且在GC-MS测量条件下不稳定。
Rf＝0.27、0.35(正戊烷/Et2O,10:1)。
GC-MS(5％甲基苯基硅氧烷,30m,0.25μm,He)：tR1＝9.493分钟([M-C2H4O2]+208.1)。
1H NMR(400MHz,CDCl3,ppm)δ＝5.12–4.96(m,1H,C4-CH),3.80–3.52(m,3H,C15-CH3),2.10-0.73(m,16H,包括1.90–1.83(m,2H,C5-CH2)。
13C NMR(101MHz,CDCl3,ppm)δ＝174.66,174.57,173.36,172.26,172.09,170.27,170.12,170.00,169.89,169.84,169.50(C9),161.74,142.02,141.89,141.74,139.75,132.04,131.93,131.85,130.47,124.01,123.86,123.77(C4),113.39,113.31,113.25,83.12,82.96,81.84,81.56,81.41,66.23,53.41,53.32,52.62,52.24,52.05,51.97,51.89,51.50,51.14(C15),40.17,39.65,39.52,39.00,38.77,33.83,33.59,32.82,30.61,30.41,30.04,29.81,29.17,28.39,27.85,25.79,25.68,24.01,23.78,23.69,23.35,23.29,22.94,22.83,22.63,22.45,22.35,22.28,22.21,22.04,21.90,21.17,21.04,19.58,18.49,17.73,17.68,17.63,17.57,17.22,16.41,14.22,14.18,12.21,11.05,10.59,9.26。
IR(ATR,cm-1)2931(w),2918(w),2871(w),2861(w),2111
(w),1728(vs),1649(w),1567(w),1526(w),1507(w),1438(s),1401(w),1367(s),1329(m),1241(vs),1215(vs),1194(vs),1171(vs),1113(s),1086(s),1047(m),1018(s),936(m),921(m),891(m),850(m),837(m),793(m),769(m),744(m),727(w),705(w),686(w),670(w),609(m),569(w),554(w),545(w),535(w),517(w),489(w),480(w),462(w),449(w),439(w),422(w),402(w),392(w),385(w),377。
HRMS(ESI+,[M+Na]+,C15H24O2Na)计算值：291.1572；求得值：291.1565。
2-(6-乙酰氧基-6-甲基庚烷-2-基)环丙烷-1-羧酸甲酯(化合物(28))
得到黄色油状物形式的标题化合物(123mg,455μmol,60％)。化合物需要进一步纯化，并且在GC-MS测量条件下不稳定。
Rf＝0.23、0.29、0.35(正戊烷/Et2O,10:1)。
GC-MS(5％甲基苯基硅氧烷,30m,0.25μm,He)：tR1＝9.236分钟(主峰,[M-C2H4O2]+210.1)。
1H NMR(400MHz,CDCl3,ppm)δ＝3.69–3.63(m,3H,C14-CH3),1.95(s,3H,C1-CH 3),1.74–1.31(m,12H,C3-CH3,C5-CH3,C6-CH2,C7-CH2,C9-CH,HCpr),1.29–1.21(m,1H,HCpr),1.18–0.65(m,7H,C8-CH2,C10-CH3,2xHCpr)。
13C NMR(101MHz,CDCl3,ppm)δ＝175.25,175.03,173.84,170.64,170.27,169.50,133.54,130.47,127.87,82.54,82.47,66.24,53.40,53.32,52.62,52.44,52.33,52.24,51.76,51.71,51.63(C14),41.17,41.12,40.99,37.84,37.73,37.35,37.20,37.16,37.11,31.54,31.02,29.93,29.82,29.36,26.16,26.12,22.59,22.56,22.46(C1),21.60,21.52,21.36,21.27,20.41,20.35,20.12,19.65,19.49,19.01,18.77,17.46,15.67,14.17,13.96,13.93,12.54。
IR(ATR,cm-1)2952(w),2871(w),2850(w),1725(vs),1598(w),1571(w),1531(w),1521(w),1517(w),1507(w),1436(m),1400(w),1366(s),1305(w),1258(vs),1196(vs),1167(vs),1084(m),1044(m),1017(s),984(w),942(m),918(m),881(w),866(w),843(w),824(m),781(w),764(w),745(w),728(w),701(w),686(w),662(w),640(w),628(w),611(m),584(w),558(w),535(w),528(w),517(w),509(w),493(w),480(w),467(w),455(w),449(w),441(w),429(w),425(w),418(w),402(w),394(w),378(w)。
HRMS(ESI+,[M+Na]+,C15H26O2Na)计算值：293.1729；求得值：293.1719。
2-(环己-3-烯-1-基)环丙烷-1-羧酸甲酯(化合物(22))
(8.7mL)溶液为起始材料制备。粗产物通过柱色谱法(正戊烷/Et2O，30:1)纯化，得到无色油状物形式的标题化合物(115mg,640μmol,46％)。
d.r.＝1:1.2
Rf＝0.41、0.50(正戊烷/Et2O,30:1)。
GC-MS(5％甲基苯基硅氧烷,30m,0.25μm,He)：tR1＝9.096分钟(45％,[M]+180.1),tR2＝9.448分钟(55％,[M]+180.1)。
1H NMR(400MHz,CDCl3,ppm)δ＝5.70–5.57(m,1H,CH＝CH),5.00–4.83(m,1H,CH＝CH),3.68–3.61(m,3H,C11-CH3),2.19–1.76(m,4H,C2/C5-CH2),1.72–0.71(m,7H,C6-CH2,C1-CH,C7-CHCpr,C8-CHCpr,C9-CH2Cpr)。
13C NMR(101MHz,CDCl3,ppm)δ＝175.19,175.14,175.10,173.77,173.73,172.49,172.38(C10),144.88,144.19,143.54,143.34,127.14,127.07(CH＝CH),126.29,126.11,112.93,112.69,112.44,112.41(CH＝CH),51.76,51.73,51.67,51.28(C11),38.17,37.83,37.74,37.71,36.10,35.55,31.83,31.63,31.24,31.06,29.50,28.79,28.72,28.67,28.36,28.18,28.15,28.09,28.05,27.60,26.92,26.10,26.01,25.71,25.27,25.04,25.01,24.94,24.78,24.45,23.41,22.90,22.84,22.49,22.36,22.26,21.35,21.27,19.43,18.99,18.83,18.06,17.89,17.79,17.35,16.78,15.80,14.50,14.29,14.19,12.91,12.72。
IR(ATR,cm-1)3002(vw),2970(vw),2948(w),2921(w),2853(w),2840(w),1725(vs),1650(w),1639(w),1612(w),1585(w),1578(w),1571(w),1561(w),1553(w),1544(w),1534(w),1523(w),1517(w),1509(w),1499(w),1490(w),1436(s),1404(w),1381(m),1368(w),1332(w),1312(m),1296(w),1286(w),1268(m),1249(w),1221(w),1191(vs),1167(vs),1081(m),1043(m),1024(w),993(m),960(m),942(w),909(s),888(m),874(w),866(w),851(w),824(m),803(m),789(w),778(w),756(w),739(w),721(m),684(w),653(s),615(w),591(w),578(w),562(w),545(w),540(w),528(w),514(w),500(w),490(w),479(w),470(w),458(w),446(w),436(w),428(w),411(w),394(w),378(w)。
HRMS(ESI+,[M+H]+,C11H17O2 +)计算值：181.1223；求得值：181.1220
二环[4.1.0]庚烷-7-羧酸甲酯(化合物(14))
起始材料制备。粗产物通过柱色谱法(正戊烷/Et2O，30:1)纯化，得到无色油状物形式的标题化合物(241mg,1.57mmol,86％)。
d.r.＝1:1.9
Rf＝0.34、0.59(正戊烷/Et2O,30:1)。
GC-MS(5％甲基苯基硅氧烷,30m,0.25μm,He)：tR1＝7.578分钟(34％,[M]+154.1),tR2＝7.842分钟(66％,[M]+154.1)。
1H NMR(400MHz,CDCl3,ppm)δ＝3.65(s,3H,C9-CH3),1.95–1.80(m,2H,CH2Cy),1.74–1.61(m,3H,CH2Cy,C1/C6-CH),1.58(ddt,J＝4.1,3.0,1.6Hz,1H,C1/C6-CH),1.38(t,J＝4.3Hz,1H,C7-CH),1.33–1.10(m,4H,2×CH2Cy)。
13C NMR(101MHz,CDCl3,ppm)δ＝175.45,172.54(C8),51.61,51.22(C9),25.63,22.84(CCpr),22.38,22.06(CCpr),21.32,21.05,18.66,16.69(CCpr)。
IR(ATR,cm-1)2929(m),2856(w),1723(vs),1655(w),1649(w),1630(vw),1619(vw),1612(vw),1579(vw),1561(vw),1553(vw),1544(vw),1534(vw),1528(vw),1523(vw),1509(vw),1438(vs),1422(w),1378(w),1350(w),1306(vs),1283(w),1265(m),1193(vs),1183(s),1166(vs),1152(vs),1081(m),1048(m),1018(m),960(s),950(m),916(m),866(w),851(w),839(w),815(w),793(w),779(s),715(m),703(m),660(w),652(w),632(w),609(w),599(w),589(w),574(w),564(w),555(w),547(w),528(w),510(w),494(w),489(w),482(w),475(w),460(w),433(w),419(w),411(w),404(w),390(w)。
HRMS(ESI+,[M+H]+,C9H15O2 +)计算值：155.1067；求得值：155.1064。
3-甲基二环[4.1.0]庚烷-7-羧酸甲酯(化合物(13))
(9.8mL)溶液为起始材料制备。粗产物通过柱色谱法(正戊烷/Et2O，30:1)纯化，得到无色油状物形式的标题化合物(151mg,898μmol,58％)。
d.r.＝1.4:1
Rf＝0.49、0.69(正戊烷/Et2O,30:1)。
GC-MS(5％甲基苯基硅氧烷,30m,0.25μm,He)：tR1＝7.970分钟(59％,[M]+168.1),tR2＝8.309分钟(41％,[M]+168.1)。
1H NMR(400MHz,CDCl3,ppm)δ＝3.66–3.61(m,3H,C10-CH3),2.14–0.87(m,10H,C8-CH,C7-CH,3×CH2Cy,C3-CH,C1-CH),0.86–0.77(m,3H,C4-CH3)。
13C NMR(101MHz,CDCl3,ppm)δ＝175.39(C9),51.62(C10),51.22,32.19,31.52,30.59,29.40,28.86,28.82,28.56,28.12,26.93,26.54,26.26,26.17,25.74,24.10,23.29,23.05,22.93,22.70,22.44,22.36,22.26,22.12(C4),22.08,21.39,19.88,18.72,18.27,17.23,17.18,15.80。
IR(ATR,cm-1)2949(w),2922(m),2867(w),2853(w),1724(vs),1655(w),1649(w),1639(w),1630(w),1619(w),1611(w),1587(vw),1578(vw),1571(vw),1561(vw),1544(vw),1534(vw),1528(vw),1517(vw),1509(vw),1499(vw),1490(vw),1438(vs),1377(w),1346(w),1330(w),1313(s),1296(m),1286(m),1264(m),1231(w),1191(vs),1169(vs),1153(vs),1089(w),1054(m),987(w),963(m),922(m),899(w),891(w),863(w),840(w),827(w),802(m),772(w),748(w),707(m),654(w),626(w),611(w),603(w),599(w),589(w),578(w),565(w),551(w),540(w),531(w),526(w),520(w),503(w),496(w),463(w),450(w),436(w),421(w),416(w),404(w),382(w)。
HRMS(ESI+,[M+H]+,C10H17O2 +)计算值：169.1223；求得值：169.1221。
2-(环己基甲基)环丙烷-1-羧酸甲酯(化合物(31))
烷(7.5mL)溶液为起始材料制备。粗产物通过柱色谱法(正戊烷/Et2O，30:1)纯化，得到无色油状物形式的标题化合物(186mg,949μmol,79％)。
d.r.＝1:2.3
Rf＝0.39、0.49(正戊烷/Et2O,30:1)。
GC-MS(5％甲基苯基硅氧烷,30m,0.25μm,He)：tR1＝9.455分钟(30.4％,[M]+197.1),tR2＝9.543分钟(69.6％,[M]+197.1)。
1H NMR(400MHz,CDCl3,ppm)δ＝3.66(s,3H,C7-CH3),1.78–0.80(m,16H,包括1.66–1.61(m,2H,C2-CH2),1.36–1.29(m,1H,C4-CH),1.17–1.10(m,2H,2×HCpr),C1-CH,5×CH2Cy),0.67(ddd,J＝8.1,6.4,4.0Hz,1H,HCpr)。
13C NMR(101MHz,CDCl3,ppm)δ＝175.24,173.76(C6),51.75,51.62(C7),41.12,38.43,38.16,34.53,33.42,33.34,33.26,29.73,26.74,26.69,26.54,26.51,26.43,21.23,20.35,20.23(CCpr),18.19,15.95(CCpr),13.70。
IR(ATR,cm-1)2850(m),1728(vs),1691(w),1664(w),1656(w),1642(w),1630(w),1619(w),1596(w),1578(w),1571(vw),1560(w),1543(w),1534(w),1527(w),1509(w),1499(vw),1446(s),1436(s),1401(w),1383(m),1356(w),1349(w),1323(w),1309(w),1268(m),1193(vs),1167(vs),1082(m),1045(m),1033(w),970(w),958(w),928(w),890(m),875(m),866(m),841(m),822(m),809(w),786(w),775(w),765(w),737(w),707(w),683(w),666(w),633(w),620(w),611(w),596(w),588(w),581(w),565(w),551(w),537(w),516(w),499(w),486(w),473(w),452(w),435(w),422(w),415(w),399(w),381(w)。
HRMS(ESI+,[M+H]+,C12H21O2 +)计算值：197.1536；求得值：197.1533。
2-(环戊基甲基)环丙烷-1-羧酸甲酯(化合物(33))
(8.5mL)溶液为起始材料制备。粗产物通过柱色谱法(正戊烷/Et2O，30:1)纯化，得到无色油状物形式的标题化合物(198mg,1.09mmol,80％)。
d.r.＝1:3.5
Rf＝0.37、0.49(正戊烷/Et2O,30:1)。
GC-MS(5％甲基苯基硅氧烷,30m,0.25μm,He)：tR1＝8.834分钟(22.2％,[M]+182.1),tR2＝9.015(77.8％,[M]+182.1)。
1H NMR(400MHz,CDCl3,ppm)δ＝3.66(s,3H,C7-CH3),1.90–0.88(m,14H,4×CH2Cp,3×HCpr,C1-CH,C2-CH2),0.72–0.66(m,1H,HCpr)。
13C NMR(101MHz,CDCl3,ppm)δ＝175.22,173.76(C6),51.74,51.63(C7),40.72,40.43,39.40,32.96,32.74,32.69,32.59,32.57,25.28,25.19,25.13,22.61,21.49,20.24,18.16,15.80(CCpr),13.67。
IR(ATR,cm-1)2948(m),2910(w),2866(w),1728(vs),1691(w),1656(w),1649(w),1639(w),1629(w),1619(w),1611(vw),1604(vw),1596(vw),1587(vw),1579(vw),1571(vw),1560(vw),1543(w),1534(w),1528(w),1517(vw),1509(vw),1436(s),1401(w),1381(m),1360(w),1344(m),1316(w),1268(m),1242(w),1193(vs),1163(vs),1096(m),1082(m),1044(m),970(w),939(w),914(m),882(w),864(m),846(w),823(m),775(w),737(w),683(w),666(w),629(w),612(w),606(w),582(w),568(w),561(w),550(w),533(w),526(w),507(w),482(w),472(w),458(w),448(w),436(w),416(w),409(w),401(w),391(w),381(w)。
HRMS(ESI+,[M+H]+,C11H19O2 +)计算值：183.1380；求得值：183.1378。
(2-甲基-3-((2,2,3-三甲基环戊基)甲基)环丙基)甲醇(化合物(16))
-羧酸乙酯(150mg,594μmol,1.0当量)在无水Et2O(5mL)中的溶液缓慢添加到回流的LiAlH4(30.0mg,790μmol,1.3当量)在无水Et2O(10mL)中的悬浮液中。将混合物加热回流1小时。反应完成后(TLC对照)，将反应混合物在冰浴中冷却，并小心地交替地缓慢加入乙酸乙酯(50mL)和水(50ml)。分离有机层，并用乙酸乙酯(3×25mL)萃取水层。将合并的有机层用水(2×25mL)洗涤。用硫酸钠干燥有机层，真空蒸发溶剂。将所得油状物通过柱色谱法(环己烷/EtOAc，4:1)纯化，得到淡黄色油状物形式的标题化合物(71.8mg,341μmol,57％)。
d.r.＝3.5:6.5:1:2.3
Rf＝0.45(环己烷/EtOAc,4:1)。
GC-MS(5％甲基苯基硅氧烷,30m,0.25μm,He)：tR1＝10.117分钟(26.2％,[M-CH3]+195.1),tR2＝10.240分钟(49.0％,[M-CH3]+195.1),tR3＝10.544分钟(7.5％,[M-CH3]+195.1),tR4＝10.588分钟(17.3％,[M-CH3]+195.1)。
1H NMR(400MHz,CDCl3,ppm)δ＝3.78–3.37(m,2H,C14-CH2),1.96–0.39(m,23H)。
(2-甲基-3-((2,2,3-三甲基环戊-3-烯-1-基)甲基)环丙基)甲醇(化合物32))。
1.2当量)在无水Et2O(10mL)中的悬浮液中。将混合物加热回流1小时。反应完成后(TLC对照)，将反应混合物在冰浴中冷却，并小心地交替地缓慢加入乙酸乙酯(50mL)和水(50ml)。分离有机层，并用乙酸乙酯(3×25mL)萃取水层。将合并的有机层用水(2×25mL)洗涤。用硫酸钠干燥有机层，真空蒸发溶剂。将所得油状物通过柱色谱法(环己烷/EtOAc，4:1)纯化，得到淡黄色油状物形式的标题化合物(75.8mg,364μmol,87％)。
d.r.＝1:1:1.1:2.8:3.8
Rf＝0.48(环己烷/EtOAc,4:1)。
GC-MS(5％甲基苯基硅氧烷,30m,0.25μm,He)：tR1＝10.166分钟(10.3％,[M]+208.1),tR2＝10.273分钟(10.4％,[M]+208.1),tR3＝10.318分钟(11.0％,[M]+208.1),tR4＝10.408分钟(28.5％,[M-CH3]+193.2),tR5＝10.596分钟(39.8％,[M-CH3]+193.2)。
1H NMR(400MHz,CDCl3,ppm)δ＝5.46–5.27(m,1H,C2-CH),3.99–3.57(m,2H,C14-CH2),2.45–0.42(m,21H,包括1.60(s,3H,C4-CH3)。
13C NMR(101MHz,CDCl3,ppm)δ＝148.91,148.85(C2/C3),130.29,125.19,123.95,123.87,121.98,121.93,121.88,67.53,67.49,63.78,60.72,59.87,59.67,51.48,51.15,51.08,50.99,48.24,46.98,46.91,46.82,45.18,43.05,35.84,35.73,34.27,33.96,32.53,31.61,29.84,29.08,29.01,28.72,28.12,27.58,27.46,27.41,26.00,25.95,25.89,25.86,25.00,24.12,23.15,23.03,22.48,22.17,22.11,21.12,20.71,20.46,20.23,20.08,20.01,19.82,19.68,19.63,18.33,17.75,16.17,14.99,14.20,13.13,12.97,12.93,12.76,12.62,12.05,11.16,8.26,7.60。
IR(ATR,cm-1)3384(w),3354(w),3336(w),3327(w),3315(w),3306(w),3292(w),3259(w),3224(w),3203(w),2995(w),2952(s),2925(vs),2864(s),2775(w),1874(w),1851(w),1832(w),1824(w),1819(w),1806(w),1800(w),1793(w),1782(w),1773(w),1762(w),1752(w),1737(w),1720(w),1708(w),1701(w),1686(w),1676(w),1670(w),1655(w),1649(w),1638(w),1629(w),1618(w),1609(w),1598(w),1578(w),1571(w),1561(w),1544(w),1534(w),1523(w),1509(w),1459(s),1443(s),1402(m),1383(s),1360(s),1324(m),1299(m),1283(m),1251(m),1220(m),1214(m),1179(w),1143(m),1113(m),1088(m),1079(m),1068(m),1011(vs),966(s),918(m),882(m),861(m),834(m),798(vs),754(s),703(s),657(s),628(s),608(s),584(s),550(s),527(s),518(m),506(m),500(m),476(m),469(m),462(m),449(m),425(m),418(m),408(m),399(m),388(m),380(m)。
HRMS(ESI+,[M+H2O]+,C14H23 +)计算值：191.1794；求得值：191.1792
参考文献
[1]C.G.Espino和J.Du Bois,德国应用化学国际版(Angew.Chem.Int.Ed)，第40卷，第3期，第598-600页，2001年
[2]N.E.Searle，有机合成汇编(Org.Syn.Coll.)，第4卷，第424页，1963年
[3]M.A.Shaw,R.A.Croft,W.G.Whittingham和J.F.Bower，美国化学会志(J.Am.Chem.Soc.)，第137卷，第25期，第8054-8057页，2015年
[4]A.G.M.Barrett,D.C.Braddock,I.Lenoir和H.Tone，有机化学杂志(J.Org.Chem.)，第66卷，第24期，第8260-8263页，2001年
[5]K.Keigo,K.Toshihiro和M.Noritaka，化学快报(Chem.Lett.)，第39卷，第702-703页，2010年
Claims (15)
1.一种式(I)化合物或者两种或更多种式(I)化合物的混合物作为香料的用途
其中R1＝COOX，X＝甲基、乙基或叔丁基，或
R1＝CH2OH，
R2＝H或甲基，以及
R3至R6的定义如以下化合物(1)至(34)中所示，
其中所述化合物选自由以下化合物组成的组：
化合物(1)
化合物(4)
化合物(5)
化合物(6)
化合物(7)
化合物(8)
化合物(9)
化合物(10)
化合物(11)
化合物(12)
化合物(13)
化合物(14)
化合物(15)
化合物(16)
化合物(17)
化合物(18)
化合物(19)
化合物(20)
化合物(21)
化合物(22)
化合物(23)
化合物(24)
化合物(25)
化合物(26)
化合物(27)
化合物(28)
化合物(29)
化合物(30)
化合物(31)
化合物(32)
化合物(33)，和
化合物(34)。
2.根据权利要求1所述的用途，其中所述式(I)化合物或者两种或更多种式(I)化合物的混合物是对映纯的、外消旋的或非对映异构体的混合物。
3.根据权利要求1或2所述的用途，其中所述式(I)化合物或者两种或更多种式(I)化合物的混合物具有果香和/或花香。
4.根据权利要求1至3中任一项所述的用途，其中所述化合物(1)提供一种或多种选自由果香、花香、菠萝味、酯香和黄油味组成的组的嗅觉基调，和/或所述化合物(2)提供一种或多种选自由果香、热带香、树莓味、苹果味和花香组成的组的嗅觉基调，和/或所述化合物(3)提供一种或多种选自由葡萄柚味、菠萝味、大黄味和自然气味组成的组的嗅觉基调，和/或所述化合物(4)提供一种或多种选自由果香和大黄味组成的组的嗅觉基调，和/或所述化合物(5)提供一种或多种选自由果香、草绿香和熟大黄味组成的组的嗅觉基调，和/或所述化合物(6)提供泥土香嗅觉基调，和/或所述化合物(7)提供一种或多种选自由果香、草绿香和杏味组成的组的嗅觉基调，和/或所述化合物(8)提供一种或多种选自由果香、草莓味和菠萝味组成的组的嗅觉基调，和/或所述化合物(9)提供一种或多种选自由醋栗味、果香、香蕉味和黄油味组成的组的嗅觉基调，和/或所述化合物(10)提供一种或多种选自由草绿香、果香、香蕉味和奇异果味组成的组的嗅觉基调，和/或所述化合物(11)提供一种或多种选自由醋栗味、果香、香蕉味和“凉糖味”(即糖果味、甜味、清新味)组成的组的嗅觉基调，和/或所述化合物(12)提供一种或多种选自由果香、花香、草绿香和韭菜味组成的组的嗅觉基调，和/或所述化合物(13)提供一种或多种选自由果香、韭菜味和“凉糖味”(即糖果味、甜味、清新味)组成的组的嗅觉基调，和/或所述化合物(14)提供一种或多种选自由果香、韭菜味和“凉糖味”(即糖果味、甜味、清新味)组成的组的嗅觉基调，和/或所述化合物(15)提供甜瓜味嗅觉基调，和/或所述化合物(16)提供草绿香嗅觉基调，和/或所述化合物(17)提供一种或多种选自由果香、清新味、花香和紫檀味组成的组的嗅觉基调，和/或所述化合物(18)提供果香嗅觉基调，和/或所述化合物(19)提供一种或多种选自由大黄味和自然气味组成的组的嗅觉基调，和/或所述化合物(20)提供一种或多种选自由大黄味和自然气味组成的组的嗅觉基调，和/或所述化合物(21)提供果香嗅觉基调，和/或所述化合物(22)提供一种或多种选自由果香和黄油味组成的组的嗅觉基调，和/或所述化合物(23)提供清新味嗅觉基调，和/或所述化合物(24)提供一种或多种选自由清新味和果香组成的组的嗅觉基调，和/或所述化合物(25)提供果香嗅觉基调，和/或所述化合物(26)提供果香嗅觉基调，和/或所述化合物(27)提供清新味嗅觉基调，和/或所述化合物(28)提供果香嗅觉基调，和/或所述化合物(29)提供一种或多种选自由自然气味、园艺草本植物香和芳香组成的组的嗅觉基调，和/或所述化合物(30)提供果香嗅觉基调，和/或所述化合物(31)提供一种或多种选自由果香和菠萝味组成的组的嗅觉基调，和/或所述化合物(32)提供一种或多种选自由奶油味、木香和果香组成的组的嗅觉基调，和/或所述化合物(33)提供一种或多种选自由果香和菠萝味组成的组的嗅觉基调，和/或所述化合物(34)提供一种或多种选自由梨味和果香组成的组的嗅觉基调。
5.一种香料组合物，其包含一种权利要求1所定义的式(I)化合物或者两种或更多种权利要求1所定义的式(I)化合物的混合物。
6.一种芳香产品，其包含一种权利要求1所定义的式(I)化合物或者两种或更多种权利要求1所定义的式(I)化合物的混合物或者一种权利要求5所定义的香料组合物。
7.根据权利要求6所述的芳香产品，其中所述产品选自由香水提取物、浓香水、淡香精、须后水、古龙水、须前产品、古龙水喷雾、芳香湿巾、酸性、碱性和中性清洁剂、纺织品清新剂、熨烫助剂、液体洗衣皂、洗衣皂粉、洗衣预处理剂、织物柔软剂、清洁皂、清洁片、消毒剂、表面消毒剂、空气改良剂、气雾剂喷雾、蜡和抛光剂、身体护理产品、护手霜和乳液、护足霜和乳液、脱毛霜和乳液、须后霜和乳液、美黑霜和乳液、护发产品、除臭剂和止汗剂、装饰性化妆品产品、蜡烛、灯油、香棒、杀虫剂、驱虫剂和发泡剂组成的组。
8.根据权利要求6或7所述的芳香产品，其中相对于所述产品的总重量，所述权利要求1所定义的式(I)化合物或者两种或更多种权利要求1所定义的式(I)化合物的混合物的重量为0.01wt.-％至10wt.-％，优选为0.01wt.-％至7wt.-％。
9.一种生产芳香产品的方法，所述方法包括以下步骤：
(i)提供一种权利要求1所定义的式(I)化合物或者两种或更多种权利要求1所定义的式(I)化合物的混合物或者一种权利要求5所定义的香料组合物，
(ii)提供所述芳香产品的其他组分，以及
(iii)使步骤(ii)中提供的所述芳香产品的其他组分与感官有效量的一种权利要求1所定义的式(I)化合物或者两种或更多种权利要求1所定义的式(I)化合物的混合物或者一种权利要求5所定义的香料组合物接触。
10.一种生产权利要求1所定义的式(I)化合物的方法，所述方法包括以下步骤：
(i)在铑配合物的存在下，使式(II)的重氮化合物与式(III)的烯烃反应，
其中R1＝COOX，X＝甲基、乙基或叔丁基，且
R2＝H或甲基
其中R3至R6按照权利要求1所定义的所得化合物(1)至(15)、(17)至(31)和(33)至(34)中所示被定义，或其中R3至R6按照如所得化合物(35)和(36)中所示被定义
化合物(35)，
化合物(36)
以形成选自由化合物(1)至(15)、(17)至(31)和(33)至(36)组成的组的化合物，以及
在步骤(i)中形成化合物(35)或(36)的情况下，包括另一步骤(ii)还原化合物(35)或(36)以形成权利要求1所定义的化合物(16)或化合物(32)。
11.根据权利要求10所述的方法，其中所述铑配合物是具有羧酸配体的铑(II)配合物。
12.根据权利要求10或11所述的方法，其中所述步骤(i)中的反应在10℃至30℃、优选为15℃至25℃的温度下进行。
13.根据权利要求10至12中任一项所述的方法，其中所述反应产物通过蒸馏被纯化。
14.根据权利要求10至13中任一项所述的方法，其中所述还原步骤(ii)通过使所述化合物(35)或(36)与LiAlH4、AlH3或Li(Et)3BH反应来进行。
15.一种化合物或化合物的混合物，所述化合物选自由化合物(3)、化合物(4)、化合物(7)、化合物(15)、化合物(16)、化合物(17)、化合物(19)、化合物(20)、化合物(21)、化合物(23)、化合物(24)、化合物(25)、化合物(26)、化合物(27)、化合物(28)、化合物(29)、化合物(30)、化合物(32)、化合物(33)和化合物(34)组成的组。
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| US3059020A (en) * | 1960-09-30 | 1962-10-16 | Smith Kline French Lab | Substituted cyclopropylamines and cyclopropylcarbamates |
| FR2491461B1 (fr) * | 1980-10-03 | 1985-08-23 | Roussel Uclaf | Nouveaux derives de l'acide cyclopropane carboxylique, leur procede de preparation et leur application a la preparation de compositions parfumantes |
| FR2494265A1 (fr) * | 1980-11-18 | 1982-05-21 | Roussel Uclaf | Nouveaux derives de l'acide cyclopropane carboxylique, leur procede de preparation et leur application a la preparation de compositions parfumantes |
| FR2496652A1 (fr) * | 1980-12-23 | 1982-06-25 | Roussel Uclaf | Nouveaux derives de l'acide cyclopropane carboxylique substitues en 3 par une chaine vinylique, leur procede de preparation et leur utilisation comme agents parfumants |
| FR2499071A1 (fr) * | 1981-02-05 | 1982-08-06 | Roussel Uclaf | Nouveaux derives de l'acide cyclopropane carboxylique substitue en 3 par une chaine vinylique, leur procede de preparation et leur application comme agents parfumants |
| DE50104611D1 (de) | 2000-04-12 | 2004-12-30 | Bitop Ag | Verwendung von kompatiblen soluten als substanzen mit radikalfangenden eigenschaften |
| SE0002960D0 (sv) | 2000-08-21 | 2000-08-21 | Eurotube Ab | Engångs-smådjursfälla |
| EP1262474A1 (en) | 2001-06-01 | 2002-12-04 | Givaudan SA | Cycloalkanecarboxylic acid derivatives as fragrants with musk characteristics |
| DE10254872A1 (de) | 2002-11-25 | 2004-06-03 | Symrise Gmbh & Co. Kg | Anthranilsäureamide und deren Derivate als kosmetische und pharmazeutische Wirkstoffe |
| DE102004029239A1 (de) | 2004-05-03 | 2005-12-01 | Symrise Gmbh & Co. Kg | Benyliden-β-dicarbonylverbindungen als neue UV-Absorber |
| US9987217B2 (en) | 2004-06-18 | 2018-06-05 | Symrise Ag | Blackberry extract |
| DE102004038485A1 (de) | 2004-08-07 | 2006-02-23 | Symrise Gmbh & Co. Kg | alpha-Benzoyl-zimtsäurenitrile als neue UV-Absorber |
| WO2006045760A1 (en) | 2004-10-25 | 2006-05-04 | Symrise Gmbh & Co. Kg | Use of glycosylated flavanones for the browning of skin or hair |
| ATE425732T1 (de) | 2004-11-22 | 2009-04-15 | Symrise Gmbh & Co Kg | Formulierungen mit ceramiden und/oder pseudoceramiden und (alpha-)bisabolol zur behandlung von hautschaden |
| EP1937366B1 (en) | 2005-10-14 | 2011-12-14 | Symrise AG | Synergistic mixtures of bisabolol and ginger extract |
| DE102005056890A1 (de) | 2005-11-28 | 2007-05-31 | Institut für Umweltmedizinische Forschung gGmbH | Kosmetisches Verfahren zur Beeinflussung der Melaninbildung in der Haut |
| WO2007110415A2 (en) | 2006-03-27 | 2007-10-04 | Symrise Gmbh & Co. Kg | Use of diacetyl trimers and cosmetic or therapeutic formulations containing these compounds |
| JP5474533B2 (ja) | 2006-05-03 | 2014-04-16 | シムライズ アーゲー | Ａｈ受容体アンタゴニスト |
| DE102006043587A1 (de) | 2006-09-16 | 2008-03-27 | Symrise Gmbh & Co. Kg | 2-Methyl-2-alkenyl-substituierte 1,3-Dioxane als Riechstoffe |
| EP1915982A1 (de) | 2006-10-20 | 2008-04-30 | Symrise GmbH & Co. KG | Verwendung von 1,2-Decandiol zur Sebumreduktion bzw. zur Unterstützung des Eindringens von Wirkstoffen in Hautbereiche, sowie kosmetische und/oder dermatologische Zubereitungen umfassend 1,2-Decandiol |
| DE102006050398A1 (de) | 2006-10-20 | 2008-04-24 | Henkel Kgaa | Kosmetisches Mittel enthaltend Purin und/oder Purinderivat und Taurin |
| EP1923041A1 (de) | 2006-10-20 | 2008-05-21 | Symrise GmbH & Co. KG | Verwendung von C10-C14-Alkandiolen zur Herstellung eines Mittels zur Prophylaxe und/oder Behandlung von Malassezia-induzierter Schuppenbildung, sowie Zubereitungen enthaltend C10-C14-Alkandiole |
| EP2168570B1 (en) | 2008-09-30 | 2013-12-25 | Symrise AG | Extracts of isochrysis sp. |
| EP3348255B1 (en) | 2008-12-05 | 2021-11-10 | Symrise AG | Extracts of tetraselmis sp. for cosmetic and therapeutic purposes |
| WO2015163023A1 (ja) * | 2014-04-21 | 2015-10-29 | 高砂香料工業株式会社 | 新規化合物及び該化合物を含有する香料組成物 |
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