CN101796013B - 环己烯衍生物及其作为增香剂的用途 - Google Patents
环己烯衍生物及其作为增香剂的用途 Download PDFInfo
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- CN101796013B CN101796013B CN200880102957XA CN200880102957A CN101796013B CN 101796013 B CN101796013 B CN 101796013B CN 200880102957X A CN200880102957X A CN 200880102957XA CN 200880102957 A CN200880102957 A CN 200880102957A CN 101796013 B CN101796013 B CN 101796013B
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- hydrogen
- thiazolinyl
- methyl
- hexamethylene
- alkyl
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/75—Reactions with formaldehyde
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- A—HUMAN NECESSITIES
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- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
- A23L27/20—Synthetic spices, flavouring agents or condiments
- A23L27/202—Aliphatic compounds
- A23L27/2024—Aliphatic compounds having oxygen as the only hetero atom
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
- A23L27/20—Synthetic spices, flavouring agents or condiments
- A23L27/202—Aliphatic compounds
- A23L27/2024—Aliphatic compounds having oxygen as the only hetero atom
- A23L27/2026—Hydroxy compounds
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
- A23L27/20—Synthetic spices, flavouring agents or condiments
- A23L27/202—Aliphatic compounds
- A23L27/2024—Aliphatic compounds having oxygen as the only hetero atom
- A23L27/2028—Carboxy compounds
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
- A23L27/20—Synthetic spices, flavouring agents or condiments
- A23L27/203—Alicyclic compounds
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
- A23L27/20—Synthetic spices, flavouring agents or condiments
- A23L27/205—Heterocyclic compounds
- A23L27/2052—Heterocyclic compounds having oxygen or sulfur as the only hetero atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/32—Oximes
- C07C251/34—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
- C07C251/44—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atom of at least one of the oxyimino groups being part of a ring other than a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C33/05—Alcohols containing rings other than six-membered aromatic rings
- C07C33/14—Alcohols containing rings other than six-membered aromatic rings containing six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
- C07C403/02—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains containing only carbon and hydrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
- C07C45/292—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups with chromium derivatives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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Abstract
本发明涉及一种制备甲酰基环己烯衍生物的方法,所述甲酰基环己烯衍生物适合原样地用作增香剂或者作为制备其他增香剂的中间体。尤其地,本发明涉及在1,3-丁二烯存在下,使用甲醛进行α,β-不饱和醛的多米诺-亚甲基化-狄尔斯-阿尔德反应。
Description
本发明涉及制备甲酰基环己烯衍生物的新方法,所述甲酰基环己烯衍生物适合本身用作增香剂(odorant)或者作为制备其他增香剂的中间体。尤其地,本发明涉及在1,3-丁二烯类存在下,使用甲醛进行α,β-不饱和醛的多米诺-亚甲基化-狄尔斯-阿尔德反应。
长久以来就已知甲醛能够将α,β-不饱和醛亚甲基化为下式的二烯
但是,这些二烯不稳定且迅速发生二聚。例如,R.Pummerer等人(Liebigs Ann.1953,583,161)描述了甲酰基丁二烯的二聚。类似地,Daiichi Seiyaku Co.在JP Kokoku 50-16791中描述了甲酰基丁二烯与不同的贫电子亲二烯体的反应。由于二烯的不稳定性,至今仍只能小心地制备甲酰基环己烯衍生物。例如,F.Brion(Angew.Chem.1981,93,900)描述了借助羰基铁配合物的弗里德尔-克拉夫茨反应,以及随后与环戊丁二烯进行反应来制备2-乙酰基丁-1,3-二烯。
令人惊讶地,发明人现在发现使用甲醛时α,β-不饱和醛就地进行亚甲基化反应,并且所得的甲酰基丁二烯与1,3-丁二烯进行有机-催化的狄尔斯-阿尔德反应,即发现了基于一锅合成的方法,在该方法中甲酰基丁二烯的二聚得到抑制。
因此,本发明的一个方面涉及一种方法,所述方法包括使式B的甲酰基丁二烯
其中
R1为氢、甲基或乙基;
R2为氢、C1-C6烷基(例如,乙基、异丙基)或C2-C6烯基(例如,1-丁-1-烯基);
R3为氢、甲基或乙基;或者
R1和R3或者R2和R3与其相连的碳原子一起形成5-或6-元碳环(例如,环戊烯基、环己烯基);
与式C的二烯反应
其中
R4、R5、R6、R7、R8和R9独立地选自氢、C1-C6烷基(例如,甲基、异丙基、叔丁基、戊基)或C2-C6烯基(例如,2-甲基-戊-2-烯-5-基、2-甲基-丙-2-烯-3-基、2-甲基-戊-2-烯-5-基);或者
R4+R9一起为选自-(CH2)n-、-C(=C(CH3)2)-和-C(=C(CH2CH3)2)-的二价残基,其中n为1或2;
得到式(Ia)和/或(Ib)的化合物
其特征在于在亚甲基化催化剂和福尔马林存在下,由式A的α,β-不饱和醛就地制备式B的甲酰基丁二烯
取决于所用的式C的二烯的特定性质,可以制备式(Ia)或(Ib)的化合物或其混合物。例如,以其中R4+R9一起形成二价残基(即,环状二烯)的式C的化合物为原料,可以选择性地制备式(Ib)的化合物。另一方面,以富电子二烯,例如二甲基-丁二烯为原料可以选择性地制备式(Ia)的化合物,而如果使用贫电子二烯,例如丁二烯、异戊二烯或月桂烯则可以制备式(Ia)和(Ib)的化合物的混合物,如下述方案1所示出的。在后一种情况下,基于式(Ia)和(Ib)的化合物的混合物的总量计,化合物(Ib)在混合物中的含量可以在5%-40%重量内变化。
方案1:
亚甲基化催化剂是所属领域公知的。例如,按照例如Anniina 等人在Journal of Organic Chemistry,71卷,2538-2541 页中的描述,可以使用仲胺和羧酸的混合物。还可以使用氨基酸,例如脯氨酸或其衍生物。基于α,β-不饱和醛(A)计,催化剂的用量可以为约1mol%至约100mol%,优选约5mol%至约50mol%,例如20mol%。
除了亚甲基化催化剂之外,任选地还可以加入助催化剂,例如三苯基膦或其他叔膦或其混合物,其可能有助于提高反应选择性和缩短反应时间。
优选地,所述新方法在约0℃至约120℃,例如约20℃至约80℃下进行约2至60小时。但是,与无助催化剂的方法的反应温度相比加入助催化剂可以使工作温度降低。
有时在实际操作中还可以加入额外的溶剂,例如甲苯、DMSO、DMF或其他有机溶剂。例如,如果将1,3-丁二烯用作二烯(C),则加入额外的溶剂可以使反应过程中可能会升高的压力反而降低。但是,从生态学角度讲,优选的是以水作为溶剂的方法。
本发明的反应方法可以在反应烧瓶或高压釜中进行。
采用所属领域熟练技术人员已知的方式,例如简单地通过分离有机相,之后再蒸馏,或者通过用有机溶剂,例如MTBE(甲基叔丁基醚)、甲苯或乙酸乙酯萃取反应混合物可以纯化式(Ia)和(Ib)的化合物。剩余的水相在甲醛富集之后可以重新用在进一步的反应中。可选地,式(Ia)和(Ib)的化合物可以采用色谱,例如在硅胶上进行分离。
式(Ia)和(Ib)的化合物可以用作调料或香料,或者可以通过下述方式将其用作制备进一步的调料和香料醇及其衍生物的中间体:在还原剂,例如LiAlH4或格氏试剂存在下还原式(Ia)和(Ib)的醛,得到其中R11为氢的式(IIa)和(IIb)的化合物,任选地之后在羧酸卤化物和碱存在下按照所属领域已知的条件进行酯化反应,得到进一步的式(IIa)和(IIb)的化合物
其中
R1-R9与式(Ia)和(Ib)中给出的含义相同;
R10为氢、直链或支链C1-C5烷基(例如,甲基、乙基、异丙基)或直链或支链C2-C5烯基(例如,丙-2-烯-3-基、丙-1-烯-3-基);和
R11为氢或COR12,其中R12为氢或直链或支链C1-C3烷基(例如,乙基、异丙基)。
在氧化剂,例如PCC(氯代铬酸吡啶鎓盐)存在下,对其中R11=氢的式(IIa)和(IIb)的化合物进行氧化得到式(IIIa)和(IIIb)的调料和香料化合物
其中
R1-R9与上述含义相同;
R10为直链或支链C1-C5烷基(例如,甲基、乙基、异丙基)或直链或支链C2-C5烯基(例如,丙-2-烯-3-基、丙-1-烯-3-基)。
在a)溶于醇溶剂,例如甲醇中的羟胺、b)甲醇或乙醇或者c)二醇,例如乙二醇或丙二醇存在下,对式(Ia)、(Ib)、(IIIa)和(IIIb)的化合物的羰基进行转化,得到本文下面描述的式(IVa)和(IVb)的进一步的调料和香料化合物。羰基的转化在所属领域熟练技术人员已知的条 件下进行。
采用上述方法可以制备适宜用作调料和/或香料的已知的和新的化合物。例如,可以以生态有利的方式制备紫苏醛(4-(丙-1-烯-2-基)环己-1-烯甲醛)和紫苏醇(1-(4-(丙-1-烯-2-基)环己-1-烯基)乙醇),即使用水作为溶剂采用有机催化方法。另一个例子是4-乙酰氧基薄荷-1,8-二烯,P.Schreier等人在Deutsche Lebensmittel-Rundschau 1984,80,335中已经鉴定了该化合物,其是芒果果肉的酶法液化物中的一种挥发性成分。但是,除了新发现的化合物具有挥发性这一事实之外,其中没有给出其它性质。Raharivelomanana等人(Journal of NaturalProducts,Vol.56(2),1993,272-274)在Neocallitropsis pancheri的树精油中首次发现了没药烯醇(Bisabolenol)((4-(6-甲基庚-1,5-二烯-2-基)环己-1-烯基)甲醇)和没药烯醛(bisabolenal)(4-(6-甲基庚-1,5-二烯-2-基)环己-1-烯甲醛)。但是,文献中没有指出所述化合物适合作为调料或香料成分。从现有技术中只能得知倍半萜烯醇具有抗茵性质,并因此可以用于例如制备干燥的除臭剂(WO2005/087181)。
尽管一些化合物已知可用作调料或香料,但是现有技术中指出大部分化合物不具有器官感觉性质,因此其构成了本发明的进一步的方面。
因此,在进一步的实施方案中,本发明涉及式(IVa)的化合物用作调料或香料的用途
其中
R1为氢、甲基或乙基;
R2为氢、C1-C6烷基(例如,乙基、异丙基)或C2-C6烯基(例如,1- 丁-1-烯基);
R3为氢或甲基;或者
R1和R3或R2和R3与其所连接的碳原子一起形成5-或6-元碳环(例如,环戊烯基或环己烯基);
R4、R5、R6、R7、R8和R9独立地选自氢、直链或支链C1-C6烷基(例如,甲基、异丙基、叔丁基、戊基)或直链或支链C2-C6烯基(例如,2-甲基-戊-2-烯-5-基、2-甲基-丙-2-烯-3-基);
R10为氢、C1-C5烷基(例如,甲基、异丙基、戊基)或C2-C5烯基(例如,丙-1-烯-3-基、丙-2-烯-3-基、2-甲基-丙-1-烯-3-基);和
R为氢,R′选自羟基或-OCOR13,其中R13为氢或C1-C3烷基(例如,乙基、异丙基),
R和R′选自甲氧基和乙氧基,或者
R和R′与其所连接的碳原子一起形成二氧戊环、二氧己环、羰基或C=N-OH;
条件是排除4-乙酰氧基薄荷-1,8-二烯和其中R1、R4-R6、R8和R9为氢,R7为甲基且R+R′与其所连接的碳原子一起形成羰基或者R为氢且R′为羟基的式(IVa)的化合物。
非限制性的例子为其中R4、R5、R6、R7、R8和R9中的至少两个不为氢的那些式(IVa)的化合物,例如其中R4和R7为甲基且R5、R6、R8和R9为氢的式(IVa)的化合物。
进一步的非限制性例子为其中R4、R5、R6、R7、R8和R9中的两个为甲基,优选R4和R7为甲基,且R1为氢或甲基的那些式(IVa)的化合物。
进一步的非限制性例子为其中R1为氢,R2为C1-C6烷基(例如,乙基、异丙基)或C2-C6烯基(例如,1-丁-1-烯基),优选甲基,且R3为氢或甲基的那些式(IVa)的化合物。
式(IVa)的化合物具有花香、果香的气味香型。
在特殊的实施方案中,式(IVa)的化合物可以选自
2,4-二甲基-1-乙烯基环己-3-烯甲醛,
(2,4-二甲基-1-乙烯基环己-3-烯基)甲醇,
(2,4-二甲基-1-乙烯基环己-3-烯基)乙醇,
1-(2,4-二甲基-1-乙烯基环己-3-烯基)乙酮,
(2,4-二甲基-1-乙烯基环己-3-烯基)甲基乙酸酯,
(2,4-二甲基-1-乙烯基环己-3-烯基)丁-3-烯-1-醇,
(2,4-二甲基-1-乙烯基环己-3-烯基)丁-3-烯-1-酮,
2,4-二甲基-1-(丙-1-烯-2-基)环己-3-烯甲醛,
1-(2,4-二甲基-1-(丙-1-烯-2-基)环己-3-烯基)乙醇,
1-(2,4-二甲基-1-(丙-1-烯-2-基)环己-3-烯基)乙基乙酸酯,
1-(2,4-二甲基-1-(丙-1-烯-2-基)环己-3-烯基)-2-甲基丙-1-醇,
1-(2,4-二甲基-1-(丙-1-烯-2-基)环己-3-烯基)-2-甲基丙-1-酮,
1-(2,4-二甲基-1-(丙-1-烯-2-基)环己-3-烯基)乙酮,
1-(2,4-二甲基-1-(丙-1-烯-2-基)环己-3-烯基)丁-3-烯-1-醇,
1-(2,4-二甲基-1-(丙-1-烯-2-基)环己-3-烯基)丁-3-烯-1-酮,
1-(2,4-二甲基-1-(丙-1-烯-2-基)环己-3-烯基)丁-2-烯-1-酮,
1-(丁-1,3-二烯基)-2,4-二甲基环己-3-烯甲醛,
3,4-二甲基-1-乙烯基环己-3-烯甲醛,
2-甲基-1-(2-甲基丙-1-烯基)环己-3-烯甲醛,
2,4-二甲基-1-(2-甲基丙-1-烯基)环己-3-烯甲醛,
1-(2,4-二甲基-1-(2-甲基丙-1-烯基)环己-3-烯基)乙醇,
1-环戊烯基-2,4-二甲基(dimentyl)环己-3-烯甲醛,
4,5-二甲基-2-(2-甲基丙-1-烯基)-1-乙烯基环己-3-烯甲醛,
2-甲基-4-(4-甲基戊-3-烯基)-1-乙烯基环己-3-烯甲醛,
3-甲基-1-乙烯基-环己-3-烯-甲醛,
4-甲基-1-乙烯基-环己-3-烯甲醛肟,
3-甲基-1-乙烯基-环己-3-烯-甲醛肟,
1-(丙-1-烯-2-基)环己-3-烯甲醛,
1-(丁-1-烯基)-2,4-二甲基环己-3-烯甲醛,
4-甲基-1-(丙-1-烯-2-基)环己-3-烯甲醛,
3-甲基-1-(丙-1-烯-2-基)环己-3-烯甲醛,和
1-乙烯基环己-3-烯甲醛,或其混合物。
在进一步的方面中,本发明涉及式(IVb)的化合物作为调料或香料的用途
其中
R1为氢、甲基或乙基;
R2为氢、C1-C6烷基(例如,乙基、异丙基)或C2-C6烯基(例如,1-丁-1-烯基);
R3为氢或甲基;或者
R1和R3或者R2和R3与其所连接的碳原子一起形成5-或6-元碳环(例如,环戊基);
R4、R5和R6为氢;
R7和R8独立地为氢、C1-C6烷基(例如,甲基、叔丁基、戊基)或C2-C6烯基(例如,2-甲基-戊-2-烯-5-基);
R9为氢、甲基或乙基;或者
R4+R9一起为选自-(CH2)n-、-C(=C(CH3)2)-和-C(=C(CH2CH3)2)-的二价残基,其中n为1或2;
R10为氢、C1-C5烷基(例如,甲基、乙基、异丙基、戊基)或C2-C5烯基(例如,丙-1-烯-3-基、丙-2-烯-3-基、2-甲基-丙-1-烯-3-基);和
R为氢且R′选自羟基或-OCOR13,其中R13为氢或C1-C3烷基(例如,乙基、异丙基),
R和R′选自甲氧基和乙氧基,或者
R和R′与其所连接的碳原子一起形成二氧戊环、二氧己环、羰基 或C=N-OH;
条件是排除其中R1-R6、R8和R9为氢且R7为甲基的式(IVb)的化合物。
非限制性例子为其中R3、R4、R5和R9为氢且R和R′与其所连接的碳原子一起形成羰基或R为氢且R′为羟基的那些式(IVb)的化合物。
进一步的非限制性的例子为其中R3和R5为氢,R6和R7独立地选自氢和甲基且R4+R9一起为选自-(CH2)n-、-C(=C(CH3)2)-的二价残基的那些式(IVb)的化合物,其中n为1或2。
进一步的非限制性例子为其中R10为氢或甲基且R和R′与其所连接的碳原子一起形成羰基或C=N-OH的那些式(IVb)的化合物。
进一步的非限制性例子为其中R10和R独立地选自氢或甲基且R′为羟基的那些式(IVb)的化合物。
式(IVb)的化合物具有青香的气味香型。
在特殊的实施方案中,式(IVb)的化合物可以选自
4-乙烯基环己-1-烯甲醛,
(4-乙烯基环己-1-烯基)甲醇,
1-(4-乙烯基环己-1-烯基)乙醇,
2-甲基-4-乙烯基环己-1-烯甲醛,
(2-甲基-4-乙烯基环己-1-烯基)甲醇,
3a,4,7,7a-四氢-1H-茚-6-甲醛,
3a,4,7,7a-四氢-1H-茚-6-甲醛肟,
(3a,4,7,7a-四氢-1H-茚-6-基)甲醇,
1-(3a,4,7,7a-四氢-1H-茚-6-基)乙酮,
5-甲基-3a,4,7,7a-四氢-1H-茚-6-甲醛,
(5-甲基-3a,4,7,7a-四氢-1H-茚-6-基)甲醇,
1-(亚丙-2-基)-3a,4,7,7a-四氢-1H-茚-6-甲醛,
2-甲基-3a,4,7,7a-四氢-1H-茚-6-甲醛,
3-甲基-3a,4,7,7a-四氢-1H-茚-6-甲醛,
4-乙基-3a,4,7,7a-四氢-1H-茚-6-甲醛,
1,4,4a,7,8,8a-六氢化萘-2-甲醛,和
4-(6-甲基庚-1,5-二烯-2-基)环己-1-烯甲醛,或其混合物。
尽管一些落入通式(IVa)或(IVb)之中的化合物已经在现有技术中被公开,但是大部分化合物并未被公开,因此其是新的。例如,F.Brion等人(Angew.Chem,1981,93,900)描述了1-(3a,4,7,7a-四氢-1H-茚-6-基)乙酮,即其中R1-R8和R10为氢,R和R′与其所连接的碳原子一起形成羰基且R4+R9一起为亚甲基的式(IVb)的化合物的制备。但是,现有技术并未提及任何器官感觉性质。
因此,本发明的另一个方面提供式(IVa)的化合物
其中
R1为氢、甲基或乙基;
R2为氢、C1-C6烷基(例如,乙基、异丙基)或C2-C6烯基(例如,1-丁-1-烯基);
R3为氢或甲基;或者
R1和R3或R2和R3与其所连接的碳原子一起形成5-或6-元碳环(例如,环戊烯基或环己烯基);
R4、R5、R6、R7、R8和R9独立地选自氢、直链或支链C1-C6烷基(例如,甲基、异丙基、叔丁基、戊基)或直链或支链C2-C6烯基(例如,2-甲基-戊-2-烯-5-基、2-甲基-丙-2-烯-3-基);
R10为氢、C1-C5烷基(例如,甲基、异丙基、戊基)或C2-C5烯基(例如,丙-1-烯-3-基、丙-2-烯-3-基、2-甲基-丙-1-烯-3-基);和
R为氢且R′选自羟基或-OCOR13,其中R13为氢或C1-C3烷基(例如,乙基、异丙基),
R和R′选自甲氧基和乙氧基,或者
R和R′与其所连接的碳原子一起形成二氧戊环、二氧己环、羰基或C=N-OH;
条件是排除4-乙酰氧基薄荷-1,8-二烯和其中R1、R4-R6、R8和R9为氢,R7为甲基且R+R′与其所连接的碳原子一起形成羰基或者R为氢且R′为羟基的式(IVa)的化合物。
本发明进一步的方面涉及式(IVb)的化合物
其中
R1为氢、甲基或乙基;
R2为氢、C1-C6烷基(例如,乙基、异丙基)或C2-C6烯基(例如,1-丁-1-烯基);
R3为氢或甲基;或者
R1和R3或R2和R3与其所连接的碳原子一起形成5-或6-元碳环(例如,环戊基);
R4、R5和R6为氢;
R7和R8独立地为氢、C1-C6烷基(例如,甲基、叔丁基、戊基)或C2-C6烯基(例如,2-甲基-戊-2-烯-5-基);
R9为氢、甲基或乙基;或者
R4+R9一起为选自-(CH2)n-、-C(=C(CH3)2)-和-C(=C(CH2CH3)2)-的二价残基,其中n为1或2;
R10为氢、C1-C5烷基(例如,甲基、乙基、异丙基、戊基)或C2-C5烯基(例如,丙-1-烯-3-基、丙-2-烯-3-基、2-甲基-丙-1-烯-3-基);和
R为氢且R′选自羟基或-OCOR13,其中R13为氢或C1-C3烷基(例如, 乙基、异丙基),
R和R′选自甲氧基和乙氧基,或者
R和R′与其所连接的碳原子一起形成二氧戊环、二氧己环、羰基或C=N-OH;
条件是排除1-(3a,4,7,7a-四氢-1H-茚-6-基)乙酮、其中R1-R6、R8和R9为氢且R7为甲基或2-甲基-戊-2-烯-5-基的式(IVb)的化合物。
除非另外指明,否则针对式(Ia)-(IVa)和(Ib)-(IVb)的化合物所用的“烷基”和“烯基”指直链或支链烷基和烯基。
式(IVa)和(IVb)的化合物可以单独使用,或与基质材料结合使用。如本文中所用的,“基质材料”包括所有已知的增香剂分子,其选自目前能够获得的大范围的天然和合成分子,例如精油和提取物、醇类、醛类和酮类、醚类和缩醛类、酯类和内酯类、大环化合物类和杂环化合物类、和/或与一种或多种通常与香料组合物中的增香剂结合使用的成分或赋形剂,例如载体物质,以及其它常用于本领域的助剂,例如溶剂,如一缩二丙二醇、十四烷酸异丙酯和柠檬酸三乙酯相混合。
如本文中所用的,“香料组合物”意指包含至少一种选自式(IVa)和(IVb)的化合物的化合物和基质材料的任何组合物,所述基质材料例如为通常与增香剂结合使用的稀释剂,如一缩二丙二醇(DPG)、十四烷酸异丙酯(IMP)、柠檬酸三乙酯(REC)、邻苯二甲酸二乙酯(DEP)和醇(例如,乙醇)。
下列清单包括已知的增香剂分子的实例,其可以与本发明的化合物结合:
-精油和提取物,例如橡苔净油、罗勒油、热带果油如香柠檬油和橘子油、乳香树净油(mastic absolute)、香桃木油、玫瑰草油、广藿香油、橙叶油、苦艾油、熏衣草油、玫瑰油、茉莉油、依兰-依兰油和檀香油;
-醇类,例如顺式-3-己烯醇、肉桂醇、香茅醇、 丁子香酚、法呢醇、香叶醇、薄荷醇、橙花醇、玫瑰醇、Super MuguetTM、里哪醇、苯乙醇、 萜品醇和 (1-(2,2,6-三甲 基环己基)己-3-醇)。
-醛类和酮类,例如柠檬醛、羟基香茅醛、 甲基壬基乙醛、茴香醛、烯丙基紫罗兰酮、马鞭草烯酮、诺卡酮、香叶基丙酮、α-戊基肉桂醛、GeorgywoodTM、羟基香茅醛、Iso E (甲基紫罗兰酮)、 麦芽酚、甲基柏木酮和香草醛。
-酯类和内酯类,例如乙酸苄酯、乙酸柏木酯、γ-癸内酯、 γ-十一烷酸内酯、乙酸岩兰草酯、丙酸肉桂酯、乙酸香茅基酯、乙酸癸酯、二甲基苄基甲基酯、乙酰乙酸乙酯、顺式-3-己烯基异丁酸酯、乙酸里哪醇酯和乙酸香叶醇酯。
-大环化合物类,例如黄葵内酯、十三烷二酸亚乙基酯或
-杂环化合物类,例如异丁基喹啉。
式(IVa)和(IVb)的化合物或其混合物可以用在宽范围的香料应用中,例如用在精细和功能香料的任何领域中,如香水、家用产品、洗衣产品、身体护理产品和化妆品。取决于特定应用以及其他增香剂成分的性质和质量,所述化合物可以以宽范围变化的用量使用。其比例通常为用品的0.0001-2wt%。在一个实施方案中,本发明的化合物可以以0.0001-0.005wt%的量用在纤维软化剂中。在另一个实施方案中,所述化合物可以以0.01-3wt%,更优选0.5-2wt%的量用在醇溶液中。然而,这些值仅仅是以实例的形式给出,因为有经验的香料商还可以通过较低或较高浓度(例如最多为香料组合物的约50wt%)获得效果或者可以得到新的香调(accord)。
使式(IVa)和(IVb)的化合物或其混合物或香料组合物与消费品基质直接混合就可以将所述化合物用在消费品基质中,或者可以在之前的步骤中用捕集物质对其进行捕集,所述捕集物质例如为聚合物、胶囊、微胶囊和纳米胶囊、脂质体、膜形成物、吸收剂,例如碳或沸石、 环状低聚糖及其混合物,或者其可以化学键合在基质上,键合后的物质在经历诸如光、酶等的外部刺激时易于释放香料分子,随后释放物再与用品混合。
因此,本发明还提供制备香料用品的方法,所述方法使用常规技术和方法将式(IVa)和/或式(IVb)的化合物直接混入消费品基质中,或者混合包含式(IVa)的化合物和/或式(IVb)的化合物或其前体的香料组合物,随后可以再将其混入到消费品基质中,从而将所述化合物作为香料成分结合进来。
通过加入嗅觉可接受的量的式(IVa)和/或式(IVb)的化合物,消费品基质的气味特征将会得到改善、增强或改变。
尤其地,“前体”指式(IVa)或(IVb)的化合物与包含至少一个选自伯胺、仲胺、巯基(硫醇基)、羟基和羧基官能团的化合物之间的反应产物,其中式(IVa)和(IVb)的化合物各自的至少一个碳原子与所述包含至少一个官能团的化合物的至少一个杂原子(N、S和O)之间形成共价键。
在进一步的方面中,本发明提供通过下述方式改善、增强和改变消费品基质的方法,向消费品基质中加入嗅觉可接受的量的、选自式(IVa)和(IVb)的化合物的化合物或其混合物。
本发明还提供香料用品,所述香料用品包含:
a)作为增香剂的选自式(IVa)和(IVb)的化合物的化合物及其混合物;和
b)消费品基质。
如本文中所用的,“消费品基质”意指用作消费品以实现特定功能,例如清洁、软化和护理等功能的组合物。这种产品的例子包括精细香料,例如香水和化妆水;织物护理品、家用产品和个人护理产品,例如洗衣护理用洗涤剂、漂洗调理剂、个人清洗组合物、洗碗机用洗涤剂、表面清洁剂;洗衣产品,例如软化剂、漂白剂、洗涤剂;身体护理产品,例如洗发香波、洗浴胶;空气护理产品和化妆品,例如除臭剂、雪花膏。该列产品只是用于说明,不应将其视为以任何方式进 行限制。
现在参考下列非限制性实施例对本发明作进一步地描述。这些实施例仅仅是为了说明目的,应该理解所属领域熟练技术人员能够进行改变和变型。
实施例1:2,4-二甲基-1-乙烯基环己-3-烯甲醛
向巴豆醛(165.2g,2.36mol)、2-甲基-戊-1,3-二烯(361.6g,4.41mol)和福尔马林(37%在水中(200g,2.46mol)中加入吡咯烷(16.0g,0.22mol)和丙酸(17.0g,0.23mol)的混合物。将所述混合物放入高压釜中并加热至60-100℃保持8h。将反应混合物冷却至室温、用饱和NaHCO3稀释并用MTBE(200ml)萃取3次。用盐水(200ml)洗涤合并的有机层、干燥(MgSO4)并真空蒸发。剩余物经蒸馏纯化,得到2,4-二甲基-1-乙烯基环己-3-烯甲醛(产率50%)。沸点:50-53℃/0.15毫巴。
气味描述:青香、清鲜香气、樟脑香。
1H-NMR(300MHz,CDCl3):9.52(s,1H,CHO),5.79(dd,J=10.9,17.7Hz,1H,CH=CH2),5.36(bs,1H,3-H),5.30(d,J=10.9Hz,1H,CH=CHcHt),5.11(d,J=17.7Hz,1H,CH=CHcHt),2.49(bs,1H,2-H),2.01-1.90(m,2H),1.74-1.59(m,2H),1.66(bs,3H,4-CH3),1.02(d,J=7.1Hz,3H,2-CH3)ppm。13C-NMR(75MHz,CDCl3):202.9(d,CHO),138.4(d,CH=CH2),134.0(s,C-4),124.7(d,C-3),177.6(t,CH=CH2),54.2(s,C-1),34.8(d,C-2),27.1(t,C-5),24.9(t,C-6),23.3(q,4-CH3),17.1(q,2-CH3)ppm。GC/MS(EI),内型-异构体(主要的):164(M+,11),149(10),135(22),107(51),93(38),82(100),67(86),55(24),41(26)。IR(纯的,v/cm-1):2965s,2933s,2729w,1722s,1631w,1451m,921m。
实施例2:(2,4-二甲基-1-乙烯基环己-3-烯基)甲醇
5℃下向LiAlH4(0.114g,30mmol)的乙醚(20ml)悬浮液中加入2,4-二甲基-1-乙烯基环己-3-烯甲醛(56mmol)的乙醚(10ml)溶液。室温下搅拌混合物1h。小心地滴加0.1ml水、0.1ml 16%的NaOH 水溶液和0.3ml水。搅拌混合物2h,之后过滤并真空浓缩。剩余物经色谱纯化,得到(2,4-二甲基-1-乙烯基环己-3-烯基)甲醇(产率76%)。
气味描述:花香、类似鸢尾属的香味(iris-like)、木香。
1H-NMR(300MHz,CDCl3):5.75(dd,J=10.9,17.7Hz,1H,CH=CH2),5.23(bs,1H,3-H),5.19(d,J=10.9Hz,1H,CH=CHcHt),5.13(d,J=17.7Hz,1H,CH=CHcHt),3.50(d,J=10.9Hz,1H,CHaHbO),3.42(d,J=10.9Hz,1H,CHaHbO),2.21(b s,1H,2-H),2.02-1.86(m,3H),1.74-1.55(m,1H),1.62(s,3H),1.42-1.32(m,1H),0.91(d,J=7.2Hz,3H,2-CH3)ppm。GC/MS(EI):166(M+,2),148(11),135(28),120(11),107(27),91(27),82(100),67(59),55(14),41(15)。
实施例3:(2,4-二甲基-1-乙烯基环己-3-烯基)乙醇
10℃下向甲基溴化镁溶液(40mmol,1M,在THF中)中滴加2,4-二甲基-1-乙烯基环己-3-烯甲醛(34mmol)溶液。室温下搅拌混合物1h,之后将其冷却至5℃。滴加NH4Cl饱和水溶液,用MTBE(3×50ml)萃取混合物。用水和盐水洗涤合并的有机相、干燥(MgSO4)并真空浓缩。剩余物经色谱纯化,得到(2,4-二甲基-1-乙烯基环己-3-烯基)乙醇(产率53%)。
气味描述:樟脑香、木香。
2个异构体的比例为1∶1。1H-NMR(300MHz,CDCl3):5.66,5.61(2dd,J=17.7,10.9Hz,1H),5.37-5.35(m,1H),5.22,5.20(2d,J=10.9Hz,1H),5.10,5.09(2d,J=17.7Hz,1H),3.66,3.54(2dq,J=6.8,6.8Hz,1H),2.46-1.6(m,4H),1.57(s,3H),1.53-1.17(m,2H),1.12,1.07,1.01,0.90(4d,J=6.8Hz)ppm。GC/MS(EI):180(M+,2),162(18),147(15),136(40),121(70),107(100),93(61),82(72),67(43),55(22),41(20)。
实施例4:1-(2,4-二甲基-1-乙烯基环己-3-烯基)乙酮
室温下向(2,4-二甲基-1-乙烯基环己-3-烯基)乙醇(20mmol)的 CH2Cl2(40ml)溶液中加入PCC(40mmol)。室温下将混合物搅拌过夜,之后用己烷稀释、经硅藻土垫过滤并真空浓缩。剩余物经色谱纯化,得到1-(2,4-二甲基-1-乙烯基环己-3-烯基)乙酮(产率83%)。
气味描述:青香、花香、木香。
主要的(内型)异构体:
1H-NMR(300MHz,CDCl3):5.74(dd,J=10.6,17.7Hz,1H,CH=CH2),5.34(bs,1H,3-H),5.29(d,J=10.6Hz,1H,CH=CHcHt),5.09(d,J=17.7Hz,1H,CH=CHcHt),2.54-2.43(m,1H,2-H),2.05(s,3H,CH3CO),1.85-1.60(m,4H),1.58(s,3H),0.81(d,J=6.8Hz,3H)ppm。GC/MS(EI):178(M+,9),163(6),145(26),135(98),120(40),107(100),93(91),82(55),67(42),55(46),43(86)。IR(纯的,v/cm-1):3082w,2963s,1708s,1633w,1451m,1355m,1217m,917m。
实施例5:(2,4-二甲基-1-乙烯基环己-3-烯基)甲基乙酸酯
向(2,4-二甲基-1-乙烯基环己-3-烯基)甲醇(3.50g,21.1mmol)、三乙胺(3.83g,38mmol)和催化量的DMAP在Et2O(30ml)中形成的溶液中加入Ac2O(3.22g,31.6mmol)。搅拌混合物5h、将其倾入水中并用Et2O萃取。用水和盐水洗涤合并的有机层、干燥并真空蒸发。剩余物经球瓶-球瓶(bulb-to-bulb)蒸馏,得到为无色油的(2,4-二甲基-1-乙烯基环己-3-烯基)甲基乙酸酯(3.81g,86%)。
气味描述:花香、茉莉香、柚香。
1H-NMR(300MHz,CDCl3):5.76(dd,J=10.9,17.7Hz,1H,CH=CH2),5.18(bs,1H,3-H),5.07(d,J=10.9Hz,1H,CH=CHcHt),5.02(d,J=17.7Hz,1H,CH=CHcHt),4.01(d,J=10.9Hz,1H,CHaHbO),3.96(d,J=10.9Hz,1H,CHaHbO),2.22(b s,1H,2-H),2.01(s,3H,CH3O2),1.91-1.79(m,2H),1.76-1.66(m,1H),1.61(s,3H),1.46-1.37(m,1H),0.88(d,J=7.5Hz,3H)ppm。GC/MS(EI):208(M+,1),166(1),148(18),133(16),120(14),107(21),91(19),82(100),67(55),55(8),43(31)。
实施例6:(2,4-二甲基-1-乙烯基环己-3-烯基)丁-3-烯-1-醇
类似于实施例3,以2,4-二甲基-1-乙烯基环己-3-烯甲醛和烯丙基氯化镁为原料制备(2,4-二甲基-1-乙烯基环己-3-烯基)丁-3-烯-1-醇(产率78%)。
气味描述:青香、花香、木香。
2个异构体的比例为1∶1。1H-NMR(300MHz,CDCl3):6.00-5.78(m,1H),5.74-5.60(m,1H),5.74-5.60(m,1H),5.36(bs,1H),5.25-5.00(m,4H),3.47-3.38(m,1H),2.54-1.43(m,8H),1.58(s,3H),1.02,0.92(2d,J=6.8Hz,3H)ppm。GC/MS(EI):206(M+,1),188(3),165(40),147(41),136(39),121(91),107(100),93(57),82(63),67(46),55(36),42(41)。
实施例7:(2,4-二甲基-1-乙烯基环己-3-烯基)丁-3-烯-1-酮
按照实施例4中描述的一般步骤,以(2,4-二甲基-1-乙烯基环己-3-烯基)丁-3-烯-1-醇为原料制备(2,4-二甲基-1-乙烯基环己-3-烯基)丁-3-烯-1-酮(产率56%)。
气味描述:青香、花香、木香。
1H-NMR(300MHz,CDCl3):6.00-5.87(m,1H),5.76(d,J=10.9,17.7Hz,1H),5.39-5.33(m,1H),5.24(d,J=10.9Hz,1H),5.13(d,J=17.7Hz,1H),5.16-5.03(m,2H),3.32-3.31(m,2H),2.60-2.48(m,1H),1.96-1.65(m,4H),1.61(s,3H),0.83(d,J=6.8Hz,3H)ppm。GC/MS(EI):(M+,2),189(3),163(29),145(19),135(100),120(32),107(83),93(73),79(36),69(40),55(34),41(54)。IR(纯的,v/cm-1):3081m,2966s,1710s,1631m,1449m,1378w,1141m,917m。
实施例8:2,4-二甲基-1-(丙-1-烯-2-基)环己-3-烯甲醛
按照实施例1中描述的一般步骤,以2-甲基-戊-1,3-二烯和3-甲基-丁-2-烯醛(prenal)为原料制备1,2,4-二甲基-1-(丙-1-烯-2-基)环己-3-烯甲醛(产率52%;沸点62-65℃/0.15毫巴)。
气味描述:花香、木香、壤香。
1H-NMR(300MHz,CDCl3):9.40(s,1H),5.34(b s,1H),5.15(s,1H),4.89(s,1H),2.75-2.63(m,1H),2.07-1.70(m,4H),1.70(s,3H),1.60(s,3H),1.00(d,J=7.1Hz)ppm。13C-NMR(75MHz,CDCl3):202.8(d,CHO),141.8(s,CH2=CCH3),133.5(s,4-C),124.9(d,3-C),116.0(t,CH2=CCH3),57.6(s,1-C),32.0(d,2-C),27.2(t,5-C),23.2(q,4-CH3),22.8(t,6-C),20.0(CH2=CCH3),17.3(q,2-CH3)ppm。GC/MS(EI):178(M+,54),163(28),149(74),136(35),121(58),107(60),91(53),82(100),67(84),55(15),41(33)。IR(纯的,v/cm-1):2966s,2693w,1721s,1636w,1447m,1378m,900m。
实施例9:1-(2,4-二甲基-1-(丙-1-烯-2-基)环己-3-烯基)乙醇
按照实施例3中描述的一般步骤,以2,4-二甲基-1-(丙-1-烯-2-基)环己-3-烯甲醛为原料制备1-(2,4-二甲基-1-(丙-1-烯-2-基)环己-3-烯基)乙醇,产率92%。
气味描述:清鲜香气、青香、木香。
2个异构体以6∶4的比例形成的混合物。1H-NMR(300MHz,CDCl3):5.45-5.37(m,1H),5.18,5.12(2s,1H),4.84,4.77(2s,1H),3.74,3.57(2dq,J1=6.4,6.4Hz,J2=11.0,6.4Hz,1H),2.76-2.66,2.48-2.39(2m,1H),2.07-1.23(m,4H),1.84(s,3H),1.59(s,3H),1.14,1.09(2d,J=6.4Hz,3H),1.06,0.95(2s,J=6.4Hz,3H)ppm。GC/MS(EI):194(M+,1),176(10),161(15),150(31),135(100),121(45),107(98),91(47),82(32),67(27),55(16),41(29)。IR(纯的,v/cm-1):3437br,3085w,2964s,1631w,1451m,1373m,833m。
实施例10:1-(2,4-二甲基-1-(丙-1-烯-2-基)环己-3-烯基)乙基乙酸酯
类似于实施例5,以1-(2,4-二甲基-1-(丙-1-烯-2-基)环己-3-烯基)乙醇为原料制备1-(2,4二甲基-1-(丙-1-烯-2-基)环己-3-烯基)乙基乙酸酯。
气味描述:花香、辛香、丁子香酚味。
2个异构体以6∶4的比例形成的混合物。1H-NMR(300MHz,CDCl3):5.41-5.36,5.32-5.28(2m,1H),5.12,5.10(2s,1H),4.84,4.77(2s,1H),5.01,4.86(2q,J1=6.4Hz,J2=6.4Hz,1H),2.64-2.55,2.48-2.38(2m,1H),2.06,2.04(2s,3H),2.00-1.44(m,4H),1.87,1.84(2s,3H),1.59,1.58(2s,3H),1.14,1.10,0.99,0.93(4d,J=6.4Hz,6H)ppm。GC/MS(EI):236(M+,1),194(1),176(37),161(76),147(24),134(49),119(75),107(89),91(46),82(55)。IR(纯的,v/cm-1):2963s,1738s,1633m,1451m,1374m,1247s。
实施例11:1-(2,4-二甲基-1-(丙-1-烯-2-基)环己-3-烯基)-2-甲基丙-1-醇
向Mg(1.2g,50mmol)、Li(0.35g,50mmol)和2,4-二甲基-1-(丙-1-烯-2-基)环己-3-烯甲醛(8.9g,50mmol)的混合物中加入2-溴丙烷(7.5g,60mmol)。在氩气氛下搅拌混合物24h,之后将其倾注到冰冷的饱和NH4Cl溶液中。用MTBE(3×50ml)萃取混合物。用水和盐水洗涤合并的有机相、干燥(MgSO4)并真空浓缩。剩余物在Kugelrohr炉中蒸馏,得到8.0g(72%)无色的油。
气味描述:果香、青香、柚子味、强烈。
1H-NMR(300MHz,CDCl3):5.38(bs,1H),5.11,4.99(2s,1H),4.93,4.85(2s,1H),3.30-3.22(m,1H),2.74-2.65,2.58-2.50(2m,1H),2.23-2.47(m,5H),1.85,1.83(2s,3H),1.58(s,3H),1.05,1.01,0.99,0.93,0.86,0.77(6d,J=6.8Hz,9H)ppm。GC/MS(EI):222(M+,1),204(1),189(1),179(3)161(6),150(29),135(100),122(53),107(66),93(26),82(18),67(15),55(12),41(24)。IR(纯的,v/cm-1):3501br,2962s,1453m,1374m,1003m,888m。
实施例12:1-(2,4-二甲基-1-(丙-1-烯-2-基)环己-3-烯基)-2-甲基丙-1-酮
按照实施例4中描述的一般步骤,以1-(2,4-二甲基-1-(丙-1-烯 -2-基)环己-3-烯基)-2-甲基丙-1-醇为原料制备1-(2,4-二甲基-1-(丙-1-烯-2-基)环己-3-烯基)-2-甲基丙-1-酮(产率75%)。
气味描述:果香、柚子味、木香。
主要的(内型)异构体:
1H-NMR(300MHz,CDCl3):5.34-5.31(m,1H),5.15(s,1H),5.04(s,1H),2.99(sept,J=6.8Hz,1H),2.87-2.75(m,1H),1.94-1.70(m,4H),1.66(s,3H),1.57(s,3H),1.04(d,J=6.8Hz,3H),1.00(d,J=6.8Hz,3H),0.85(d,J=6.8Hz,3H)ppm。13C-NMR(75MHz,CDCl3):217.5(s),142.5(s),132.3(s),125.0(d),115.8(t),60.3(s),35.3(d),32.9(d),27.4(t),23.1(q),22.3(q),21.5(t),20.7(q),20.1(q),18.7(q)ppm。GC/MS(EI):220(M+,2),205(3),187(11),177(10),159(43),149(73),121(77),107(100),91(48),71(54),55(14),43(78)。IR(纯的,v/cm-1):2969s,1705s,1637m,1447s,1379m,896m。
实施例13:1-(2,4-二甲基-1-(丙-1-烯-2-基)环己-3-烯基)乙酮
按照实施例4中描述的一般步骤,以1-(2,4-二甲基-1-(丙-1-烯-2-基)环己-3-烯基)乙醇为原料制备1-(2,4-二甲基-1-(丙-1-烯-2-基)环己-3-烯基)乙酮(产率70%)。
气味描述:青香、果香、木香。
1H-NMR(300MHz,CDCl3):5.33-5.28(m,1H),5.10(s,1H),5.00(s,1H),2.71-2.61(m,1H),2.02(s,3H),1.91-1.62(m,4H),1.62(s,3H),1.56(s,3H),0.82(s,J=6.7Hz,3H)ppm。GC/MS(EI):192(M+,7),177(14),150(56),135(47),121(82),107(100),91(51),83(29),77(24),67(22),55(15),43(56)。IR(纯的,v/cm-1):3091w,2964s,1708s,1639m,1446s,1378m,1354m,1211m,1155m,898m。
实施例14:1-(2,4-二甲基-1-(丙-1-烯-2-基)环己-3-烯基)丁-3-烯-1-醇
类似于实施例3,以2,4-二甲基-1-(丙-1-烯-2-基)环己-3-烯甲 醛和烯丙基氯化镁为原料制备1-(2,4-二甲基-1-(丙-1-烯-2-基)环己-3-烯基)丁-3-烯-1-醇(产率91%)。
气味描述:果香、清鲜香气、木香。
4个异构体的混合物。1H-NMR(300MHz,CDCl3)6.00-5.78(m,1H),5.53-5.36(m,1H),5.17-4.71(m,4H),3.52-3.38(m,1H),2.81-1.50(m,7H),1.85,1.83(4s,3H),1.65,1.64,1.59,1.58(4s,3H),1.06,0.96,0.85,0.80(4d,J=6.8Hz,3H)ppm。GC/MS(E I):主要的异构体:220(M+,1),202(1),179(12),161(17),150(25),135(100),121(43),107(87),93(40),91(39),82(22),67(25),55(17),41(45)。IR(纯的,v/cm-1):3487br,3079m,2962s,1449m,992m,910m。
实施例15:1-(2,4-二甲基-1-(丙-1-烯-2-基)环己-3-烯基)丁-3-烯-1-酮
按照实施例4中描述的一般步骤,以2个异构体的比例为8∶2的1-(2,4-二甲基-1-(丙-1-烯-2-基)环己-3-烯基)丁-3-烯-1-醇混合物为原料制备1-(2,4-二甲基-1-(丙-1-烯-2-基)环己-3-烯基)丁-3-烯-1-酮。
气味描述:果香、胡椒味、清鲜香气、木香。
1H-NMR(300MHz,CDCl3):6.03-5.88(m,1H),5.47-5.31(m,1H),5.15-5.02(m,4H),3.24-3.15(m,2H),2.85-2.65(m,1H),2.13-1.56(m,4H),1.64(s,3H),1.59(s,3H),0.83,0.73(2d,J=6.8Hz,3H)ppm。GC/MS (EI):218(M+,5),203(5),177(26),159(17),149(77),135(36),121(82),107(100),91(42),69(38),41(52)。IR(纯的,v/cm-1):2962s,1710s,1631s,1446m,1139w,897m。
实施例16:1-(2,4-二甲基-1-(丙-1-烯-2-基)环己-3-烯基)丁-2-烯-1-酮
室温下将1-(2,4-二甲基-1-(丙-1-烯-2-基)环己-3-烯基)丁-3-烯-1-酮(2.5g,11.5mmol)和三乙胺(2g)的CH2Cl2溶液搅拌过夜。 蒸发掉溶剂和过量的三乙胺,剩余物经球瓶-球瓶蒸馏,得到为浅黄色油的标题化合物(80%)。
气味描述:辛香、黑胡椒味、大马酮味、果香。
4个异构体的混合物,主要的异构体:1H-NMR(300MHz,CDCl3):6.94(dq,J=15.5,7.1Hz,1H),6.37(d,J=15.5Hz,1H),5.31(bs,1H),5.12(s,1H),5.03(s,1H),2.68-2.55(m,1H),1.85-1.53(m,13H),0.80(d,J=7.1Hz,3H)ppm。13C-NMR(75MHz,CDCl3):201.2(s),143.0(s),141.9(d),132.6(s),127.0(d),124.6(d),115.1(t),58.2(s),32.8(d),27.3(t),23.2(q),21.1(t),19.9(q),18.2(q),18.1(q)ppm。GC/MS(EI):218(M+,5),203(8),176(24),133(57),121(59),107(72),91(37),69(100),41(49)。IR(纯的,v/cm-1):3089m,2968s,1696s,1631s,1445s,1377m,1142m,895s。
实施例17:1-(丁-1,3-二烯基)-2,4-二甲基环己-3-烯甲醛
按照实施例1中描述的一般步骤,以2-甲基-戊-1,3-二烯和山梨醛为原料制备标题化合物(产率50%)。
气味描述:果香、苹果香、温和的花香。
4个异构体的比例为9∶5∶2∶1。1H-NMR(300MHz,CDCl3):9.62,9.51,9.47,9.39(4s,1H),6.44-6.01(m,2H),5.63-5.05(m,4H),2.62-2.40(m,1H),1.95-1.60(m,7H),0.99,0.98,0.92,0.91(4d,J=7.1Hz,3H)ppm。主要的异构体:13C-NMR(75MHz,CDCl3):202.1(d),136.7(d),134.1(s),134.0(d),133.3(d),124.6(d),117.4(t),53.6(s),35.2(d),27.1(t),25.0(t),23.3(q),17.16(q)ppm。GC/MS(EI):190(M+,37).175(5),161(16),147(12),133(12),119(27),105(40),91(45),82(100),67(65),55(13),41(20)。IR(纯的,v/cm-1):2963s,2710m,1718s,1449m,1378m,1006m,907m。
实施例18:3,4-二甲基-1-乙烯基环己-3-烯甲醛
按照实施例1中描述的一般步骤,以2,3-二甲基-丁-1,3-二烯和 巴豆醛为原料制备标题化合物。
气味描述:清鲜香气、青香、萜品香、果香、樟脑香。
1H-NMR(300MHz,CDCl3):9.33(s,1H),5.67(dd,J=17.6,10.5Hz,1H),5.23(d,J=10.5Hz,1H),5.09(d,J=17.6Hz,1H),2.36-1.60(m,6H),1.66(s,3H),1.57(s,3H)ppm。13C-NMR(75MHz,CDCl3):202.1(d),138.1(d),125.7(s),122.8(s),116.7(t),52.4(s),35.8(t),28.4(t),27.6(t),19.2(q),18.8(q)ppm。GC/MS(EI):164(M+,32),149(23),135(71),121(42),107(93),91(100),79(86),67(80),55(41),41(56)。IR(纯的,v/cm-1):2920s,1729s,1441m,997w,921m。
实施例19:2-甲基-1-(2-甲基丙-1-烯基)环己-3-烯甲醛
按照实施例1中描述的一般步骤,以戊-1,3-二烯和4-甲基-戊-2-烯醛为原料制备标题化合物。
实施例20:2,4-二甲基-1-(2-甲基丙-1-烯基)环己-3-烯甲醛
按照实施例1中描述的一般步骤,以2-甲基戊-1,3-二烯和4-甲基-戊-2-烯醛为原料制备标题化合物。2个异构体的比例为9∶1。
气味描述:果香、苹果香、玫瑰花瓣香味、水香。
1H-NMR(300MHz,CDCl3):9.41(s,1H),5.28(s,1H),4.95(s,1H),2.34-2.24(m,1H),1.90-1.70(m,4H),1.71(s,3H),1.61(s,3H),1.49(s,3H),0.85(d,J=7.1Hz,3H)ppm。
13C-NMR(75MHz,CDCl3):203.3(d),137.6(s),134.6(s),124.8(d),124.1(d),52.9(s),36.9(d),27.4(t),27.1(q),23.3(q),21。9(t),18.6(q),17.3(q)ppm。GC/MS(EI):192(M+,63),177(21),163(31),135(19),121(27),107(69),95(35),82(100),67(46),55(14),41(23)。IR(纯的,v/cm-1):2912s,2712m,1721s,1449m,1378m,821w。
实施例21:1-(2,4-二甲基-1-(2-甲基丙-1-烯基)环己-3-烯基)乙醇
按照实施例3中描述的一般步骤,以2,4-二甲基-1-(2-甲基丙-1- 烯基)环己-3-烯甲醛为原料制备标题化合物。2个异构体的比例为1∶1。
气味描述:壤香、干木香、樟脑香。
1H-NMR(300MHz,CDCl3):5.33-5.20(m,1H),4.81,4.76(2bs,1H),2.80-3.70,3.61-3.52(2m,1H),2.41-2.31(m,1H),1.84,1.76,1.75,1.73,1.60,1.60(6s,9H),2.01-1.39(m,5H),1.18,1.10(2d,J=6.4Hz,3H),1.00,0.87(2d,J=7.2Hz,3H)ppm。GC/MS(EI):208(M+,5),190(4),175(5),163(61),135(20),121(42),107(100),93(52),83(34),69(30),55(23),41(22)。IR(纯的,v/cm-1):3422br,2967s,1451m,1374m,1102m。
实施例22:1-环戊烯基-2,4-二甲基(dimentyl)环己-3-烯甲醛
按照实施例1中描述的一般步骤,以2-甲基戊-1,3-二烯和2-亚环戊基-乙醛为原料制备标题化合物(20%)。2个异构体的比例为8∶2。
气味描述:铃兰味、果香
主要的异构体:1H-NMR(300MHz,CDCl3):9.40(s,1H),5.58(s,1H),5.33(s,1H),2.67(bs,1H),2.36-1.70(m,10H),1.60(s,3H),0.98(d,J=6.9Hz,3H)ppm。13C-NMR(75MHz,CDCl3):202.2(d),141.5(s),133.4(s),129.5(d),125.0(d),54.6(s),33.0(d),32.8(t),32.0(t),27.3(t),23.3(q),23.2(2t),17.3(q)ppm。GC/MS(E I):204(M+,30),189(4),175(10),147(19),133(10),119(14),105(20),91(31),82(100),67(49),55(10),41(23)。
实施例23:4,5-二甲基-2-(2-甲基丙-1-烯基)-1-乙烯基环己-3-烯甲醛
按照实施例1中描述的一般步骤,以别罗勒烯和巴豆醛为原料制备标题化合物。2个异构体的比例为85∶15。
气味描述:轻微果香、青香、微弱
主要的异构体:1H-NMR(300MHz,CDCl3):9.13(s,1H),5.70-5.59(m,1H),5.24-4.76(m,4H),3.32-3.19(m,1H), 2.12-1.15(m,4H),1.63,1.59,1.59(3s,9H),0.99(d,J=6.8Hz,3H)ppm。13C-NMR(75MHz,CDCl3):201.4(d),138.2(s),137.9(d),133.6(s),123.7(d),121.5(d),118.0(t),55.4(s),38.8(d),32.7(t),30.6(d),25.9(q),21.1(q),19.3(q),18.3(q)ppm。GC/MS(EI):218(M+,4),203(1),189(2),175(1),161(1),147(3),136(56),121(100),105(12),91(12),77(6),67(2),55(4),41(5)。IR(纯的,v/cm-1):2967s,1725s,1445m,1377m,921w。
实施例24:2-甲基-4-(4-甲基戊-3-烯基)-1-乙烯基环己-3-烯甲醛
按照实施例1中描述的一般步骤,以2-甲基-6-亚甲基壬-2,7-二烯和巴豆醛为原料制备标题化合物(产率50%)。
气味描述:铃兰味、果香。
(内型:外型-异构体的比例为8∶2)。内型-异构体:1H-NMR(300MHz,CDCl3):9.49(s,1H),5.76(dd,J=17.7,10.9Hz,1H),5.37-5.33(m,2H),5.27(d,J=10.9Hz,1H),5.08(d,J=17.7Hz,1H),2.55-2.43(m,1H),2.09-2.65(m,8H),1.67(s,3H),1.58(s,3H),1.00(d,J=7.1Hz,3H)ppm。13C-NMR(75MHz,CDCl3):203.0(d),138.3(d),137.5(s),131.4(s),124.4(d),124.0(d),117.4(t),54.3(s),37.3(t),34.7(d),26.4(t),25.7(q),25.3(t),25.0(t),17.7(q),17.2(q)ppm。GC/MS(EI):232(M+,5),217(6),203(14),189(12),171(6),150(22),135(20),119(23),107(100),91(35),79(30),69(92),55(28),41(68)。
实施例25:4-甲基-1-乙烯基-环己-3-烯甲醛、3-甲基-1-乙烯基-环己-3-烯-甲醛和紫苏醛(比例5.5∶3∶1.5)
按照实施例1中描述的一般步骤,以异戊二烯和巴豆醛为原料获得4-甲基-1-乙烯基-环己-3-烯甲醛、3-甲基-1-乙烯基-环己-3-烯甲醛和紫苏醛(比例为5.5∶3∶1.5)的混合物(产率为31%)。用色谱分离各组分(洗脱液己烷∶MTBE 50∶1-10∶1)。以此方式获得的外消旋紫苏醛的分析数据与可信试样的数据相同。
混合物的气味描述:强烈、清鲜香气、青香、果香、辛香。
4-甲基-1-乙烯基-环己-3-烯甲醛:1H-NMR(300MHz,CDCl3):9.35(s,1H),5.69(dd,J=17.7,10.7Hz,1H),5.40(bs,1H),5.26(d,J=10.7Hz,1H),5.13(d,J=17.7Hz,1H),2.44(bs,1H),2.41(bs,1H),2.10-1.64(m,5H),1.63(s,3H)ppm。13C-NMR(75MHz,CDCl3):202.0(d),138(d),134.4(s),118.0(d),116.9(t),51.4(s),29.8(t),27.3(t),26.9(t),22.0(q)ppm。GC/MS(EI):150(M+,23),135(24),121(45),107(33),93(100),79(98),67(54),55(37),39(38)。
3-甲基-1-乙烯基-环己-3-烯甲醛:1H-NMR(300MHz,CDCl3):9.36(s,1H),5.71(dd,J=10.7,17.7Hz,1H),5.37(b s,1H),5.27(d,J=10.7Hz,1H),5.12(d,J=17.7Hz,1H),2.37(b s,1H),2.33(bs,1H),2.10-1.64(m,5H),1.72(s,3H)ppm。13C-NMR(75MHz,CDCl3):201.7(d),137.9(d),131.2(s),120.9(d),116.8(t),52.2(s),34.1(t),26.7(t),23.6(q),22.2(t)ppm。GC/MS(EI):150(M+,10),135(16),121(78),107(29),93(100),79(88),67(32),55(31),39(32)。I R(纯的,v/cm-1):2917s,2854m,2707w,1726s,1632w,1439m,921m。
实施例26:4-甲基-1-乙烯基-环己-3-烯甲醛肟、3-甲基-1-乙烯基-环己-3-烯-甲醛肟(比例为6∶4)
50℃下将4-甲基-1-乙烯基-环己-3-烯甲醛和3-甲基-1-乙烯基-环己-3-烯-甲醛(6∶4,1.5g,10mmol)、羟胺盐酸盐(1.04g,15mmol)和NaHCO3(1.26g,15mmol)混合物的Et OH/水(20ml,3∶1)溶液搅拌4h。用水稀释混合物并用MTBE萃取3次。用水和盐水洗涤合并的有机层、干燥(MgSO4)并真空蒸发。经球瓶-球瓶蒸馏之后得到为无色油的4-甲基-1-乙烯基-环己-3-烯甲醛肟和3-甲基-1-乙烯基-环己-3-烯-甲醛肟(比例为6∶4,产率70%)。
混合物气味描述:花香、紫罗兰叶味、青香
1H-NMR(300MHz,CDCl3):8.43,8.35(2bs,1H),7.32(s,1H), 5.82(dd,J=17.7,10.6Hz,1H),5.38(bs,1H),5.14-5.01(m,2H),2.28-1.64(m,6H),1.70,1.65(2s,3H)ppm。GC/MS(EI):165(M+,2),148(24),131(24),120(25),105(100),91(44),79(30),68(96),53(28),39(25)。IR(纯的,(/cm-1):3315br,2927s,1635m,1439s,922s。
实施例27:1-(丙-1-烯-2-基)环己-3-烯甲醛
按照实施例1中描述的一般步骤,以1,3-丁二烯和3-甲基-丁-2-烯醛为原料制备标题化合物(产率31%)。
气味描述:清鲜香气、青香、樟脑香、类似紫苏醛的香味。
1H-NMR(300MHz,CDCl3):9.23(s,1H),5.72-5.60(m,2H),5.07(s,1H),4.91(s,1H),2.54-2.44(m,1H),2.18-2.71(m,5H),1.68(s,3H)ppm。13C-NMR(75MHz,CDCl3):201.4(d),143.0(s),126.8(d),124.4(d),114.4(t),54.4(s),29.0(t),25.5(t),22.4(t),19.5(q)ppm。GC/MS(EI):150(M+,9),135(17),121(36),107(21),93(73),79(100),67(21),55(24),41(27)。IR(纯的,(/cm-1):3028w,2923s,2698m,1725s,1668m,1634m,1440m,1377m,901m。
实施例28:1-(丁-1-烯基)-2,4-二甲基环己-3-烯甲醛
按照实施例1中描述的一般步骤,以2-甲基-戊-1,3-二烯和2-己醛为原料制备标题化合物(产率71%)。
气味描述:果香、类似苹果的香味、花香。
4个异构体的比例为5∶2∶7∶1。1H-NMR(300MHz,CDCl3):9.62,9.53,9.45,9.36(4s,1H),5.60-5.14(m,3H),2.63-2.33(m,1H),2.13-1.61(m,9H),1.01-0.90(m,6H)ppm。
13C-NMR(75MHz,CDCl3):主要的异构体:203.3(d),137.3(d),134.6(s),129.0(d),124.1(d),53.3(s),36.6(d),27.3(t),27.1(t),23.3(q),22.7(t),17.2(q),14.1(q)ppm。GC/MS(EI):192(M+,20),163(20),135(13),121(16),107(35),93(24),82(100),67(46),55(18),41(20)。IR(纯的,v/cm-1):1964s,2874m,2711w, 1721s,1451m。
实施例29:4-甲基-1-(丙-1-烯-2-基)环己-3-烯甲醛和3-甲基-1-(丙-1-烯-2-基)环己-3-烯甲醛
按照实施例1中描述的一般步骤,以异戊二烯和3-甲基-丁-2-烯醛为原料制备4-甲基-1-(丙-1-烯-2-基)环己-3-烯甲醛和3-甲基-1-(丙-1-烯-2-基)环己-3-烯甲醛的混合物(产率31%)。
气味描述:青香、果香、芒果香、大马酮味、李子味。
异构体以6∶4的比例形成的混合物。1H-NMR(300MHz,CDCl3):9.22,9.21(2s,1H),5.04-4.83(m,3H),2.51-2.33(m,2H),2.17-1.72(m,5H),1.70,1.68,1.67,1.60(4s,6H)ppm。4-甲基-1-(丙-1-烯-2-基)环己-3-烯甲醛:13C-NMR(75MHz,CDCl3):201.7(d),143.0(s),134.0(s),118.4(d),114.4(t),54.2(s),29.3(t),27.2(t),26.0(t),23.2(q),19.6(q)ppm。GC/MS(EI):164(M+,20),149(31),135(68),121(35),107(71),93(100),79(64),67(40),55(28),41(38)。3-甲基-1-(丙-1-烯-2-基)环己-3-烯甲醛:201.5(d),143.0(s),131.6(s),120.6(d),114.3(t),55.0(s),33.7(t),25.4(t),23.6(q),22.4(t),19.6(q)ppm。GC/MS(EI):164(M+,18),149(32),135(68),121(34),107(72),93(100),79(64),67(41),55(27),41(38)。IR(纯的,v/cm-1):2967m,2921s,1726s,1635m,1441m,1377m,899m。
实施例30:1-乙烯基环己-3-烯甲醛和4-乙烯基环己-1-烯甲醛
按照实施例1中描述的一般步骤,以1,3-丁二烯和巴豆醛为原料制备1-乙烯基环己-3-烯甲醛和4-乙烯基环己-1-烯甲醛的混合物(产率42%)。
混合物的气味描述:青香、果香、苹果香、甜瓜味、花香、紫罗兰味。
1-乙烯基环己-3-烯甲醛:1H-NMR(300MHz,CDCl3):9.38(s,1H),5.77-5.63(m,3H),5.29(d,J=10.6Hz,1H),5.16(d,J=17.7Hz,1H),2.53-1.67(m,6H)ppm。13C-NMR(75MHz,CDCl3):201.8 (d),137.9(d),127.1(d),123.9(d),117.0(t),51.7(s),29.4(t),26.9(t),22.0(t)ppm。GC/MS(EI):136(M+,5),118(17),107(28),91(46),79(100),67(9),53(14),39(23)。
4-乙烯基环己-1-烯甲醛:1H-NMR(300MHz,CDCl3):9.41(s,1H),6.79(b s,1H),5.81(ddd,J=17.0,10.2,6.6Hz,1H),5.04(d,J=17.0Hz,1H),4.99(d,J=10.2Hz,1H),2.55-2.05(m,5H),1.91-1.83(m,1H),1.44-1.30(m,1H)ppm。13C-NMR(75MHz,CDCl3):194.0(d),150.1(d),142.0(d),141.3(s),113.5(t),37.1(d),32.0(t),27.2(t),20.8(t)ppm。GC/MS(EI):136(M+,21),121(14),107(60),91(41),79(88),67(27),54(100),39(49)。IR(纯的,v/cm-1):2928s,1686s,1643m,1420w,1178w,916w。
实施例31:(4-乙烯基环己-1-烯基)甲醇
按照实施例2中描述的一般步骤,以4-乙烯基环己-1-烯甲醛为原料制备标题化合物(产率85%)。
气味描述:辛香、肉桂味、玫瑰味、果香、青香。
1H-NMR(300MHz,CDCl3):5.48(ddd,J=17.0,10.2,6.4Hz,1H),5.68(bs,1H),5.03(d,J=17.0Hz,1H),4.96(d,J=10.2Hz,1H),4.00(s,2H),2.27-1.81(m,6H),1.60(bs,OH),1.48-1.35(m,1H)ppm。GC/MS(EI):138(M+,9),120(26),105(58),91(64),79(100),67(33),55(57),41(35)。IR(纯的,v/cm-1):3332br,3079m,2914s,1640m,1435m,995s,912s。
实施例32:1-(4-乙烯基环己-1-烯基)乙醇
按照实施例3中描述的一般步骤,以4-乙烯基环己-1-烯甲醛味原料制备标题化合物(产率66%)。
气味描述:肉桂味、果香、苹果香、青香
2个异构体以1∶1的比例形成的混合物。1H-NMR(300MHz,CDCl3):5.92-5.80(m,1H),5.66(b s,1H),5.05-4.93(m,2H),4.24-4.12(m,1H),2.32-1.79(m,6H),1.48-1.31(m,1H),1.25(2d,J=6.5Hz,3H)ppm。GC/MS(EI):主要的异构体:152(M+,9),134(35), 119(33),105(53),91(60),79(100),67(34),55(24),43(68)。IR(纯的,v/cm-1):3369br,3080m,2973m,2925s,1436m,1071m,912m。
实施例33:2-甲基-4-乙烯基环己-1-烯甲醛
按照实施例1中描述的一般步骤,以1,3-丁二烯和3-甲基-丁-2-烯醛为原料制备标题化合物(产率12%)。
气味描述:青香、果香、肉桂味。
1H-NMR(300MHz,CDCl3):10.12(s,1H),5.79(ddd,J=17.0,10.2,6.1Hz,1H),5.06-4.95(m,2H),2.48-1.22(m,7H),2.14(s,3H)ppm。13C-NMR(75MHz,CDCl3):191.0(d),155.2(s),142.2(d),133.3(s),113.4(t),39.2(t),37.0(d),27.5(t),21.9(t),18.3(q)ppm。GC/MS(EI):150(M+,42),135(45),121(47),107(55),93(87),79(100),67(94),54(57),41(54)。IR(纯的,v/cm-1):2921s,1714s,1666s,1440m,1379m,1244m,914m。
实施例34:(2-甲基-4-乙烯基环己-1-烯基)甲醇
按照实施例2中描述的一般步骤,以2-甲基-4-乙烯基环己-1-烯甲醛为原料制备标题化合物(产率92%)。
气味描述:金属味、花香、玫瑰味。
1H-NMR(300MHz,CDCl3):5.82(ddd,J=17.0,10.2,6.4Hz,1H),5.01(d,J=17.0Hz,1H),4.95(d,J=10.2Hz,1H),4.16(d,J=10.9Hz,1H),4.07(d,J=10.9Hz,1H),2.26-1.92(m,7H),1.71(s,3H)ppm。GC/MS(EI):152(M+,7),134(43),119(77),93(100),91(98),79(94),69(43),55(36),41(54)。IR(纯的,v/cm-1):3349br,3079w,2920s,1640w,1436s,995s,910m。
实施例35:3a,4,7,7a-四氢-1H-茚-6-甲醛
按照实施例1中描述的一般步骤,以环戊二烯和巴豆醛为原料制备标题化合物(产率40%;沸点:65-70℃/0.54毫巴)。
气味描述:青香、甜瓜味、黄瓜味、苹果香、海洋味、花香。
1H-NMR(300MHz,CDCl3):9.40(s,1H),6.93(dd,J=4.9,4.9 Hz,1H),5.65-5.53(m,2H),2.99-2.91(m,1H),2.58-2.35(m,4H),2.23-2.13(m,1H),2.05-1.91(m,2H)ppm。13C-NMR(75MHz,CDCl3):192.7(d),152.4(d),142.7(s),134.9(d),130.4(d),43.0(d),39.8(t),34.6(d),29.3(t),24.3(t)ppm。GC/MS(EI):148(M+,26),133(6),120(10),105(6),91(18),77(13),66(100),55(6),39(12)。IR(纯的,v/cm-1):3050m,2924s,2717m,1678s,1171m。
实施例36:3a,4,7,7a-四氢-1H-茚-6-甲醛肟
类似于实施例26,以3a,4,7,7a-四氢-1H-茚-6-甲醛为原料制备标题化合物,产率为65%。
气味描述:辛香、花香、微弱。
1H-NMR(300MHz,CDCl3):8.85(br,OH),7.74(s,1H),6.16(dd,J=5.1,5.1Hz,1H),5.69-5.66(m,1H),5.59-5.56(m,1H),2.90(bs,1H),2.57-2.35(m,4H),2.15-1.96(m,3H)ppm。13C-NMR(75MHz,CDCl3):152.5(d),136.3(s),135.2(d),134.2(s),130.2(d),42.8(d),39.8(d),34.7(t),28.5(t),26.6(t)ppm。GC/MS(EI):163(M+,17),146(18),129(6),115(7),91(9),77(9),66(100),39(8)。I R(纯的,v/cm-1):3302br,3047m,2924s,1631m,1446m,1311w,953s。
实施例37:(3a,4,7,7a-四氢-1H-茚-6-基)甲醇
按照实施例2中描述的一般步骤,以3a,4,7,7a-四氢-1H-茚-6-甲醛为原料制备标题化合物(产率53%)。
气味描述:黄瓜味、青香、壬二烯醇味。
1H-NMR(300MHz,CDCl3):5.78-5.73(m,1H),5.65-5.53(m,2H),3.97(s,2H),2.88-2.78(m,1H),2.56-1.79(m,8H)ppm。GC/MS(EI):150(M+,1),132(30),117(25),104(4),91(16),79(14),66(100),55(5),39(9)。
实施例38:1-(3a,4,7,7a-四氢-1H-茚-6-基)乙酮
按照实施例4中描述的一般步骤,以1-(3a,4,7,7a-四氢-1H-茚 -6-基)乙醇为原料制备标题化合物(产率30%)。
气味描述:青香、果香、花香、甜瓜味。
1H-NMR(300MHz,CDCl3):7.05(dd,J=5.3,5.3Hz,1H),5.67-5.63(m,1H),5.56-5.51(m,1H),2.97-2.88(m,1H),2.70-2.34(m,4H),2.28(s,3H),2.11-1.92(m,3H)ppm。GC/MS(EI):162(M+,27),147(6),119(26),97(20),91(18),77(9),66(100),53(8),43(40)。
实施例39:5-甲基-3a,4,7,7a-四氢-1H-茚-6-甲醛
按照实施例1中描述的一般步骤,以环戊二烯和3-甲基-丁-2-烯醛为原料制备标题化合物(产率35%;沸点90℃/0.41毫巴)。
气味描述:青香、果香、甜瓜味。
1H-NMR(300MHz,CDCl3):10.04(s,1H),5.61-5.58(m,1H),5.46-5.43(m,1H),3.04-2.94(m,1H),2.59-2.46(m,2H),2.40-2.28(m,2H),2.16(s,3H),2.13-2.00(m,2H),1.93-1.81(m,1H)ppm。13C-NMR(75MHz,CDCl3):188.8(d),159.7(s),135.0(s),133.3(d),130.9(d),44.1(d),40.0(t),37.7(t),34.4(d),25.6(t),18.8(q)ppm。GC/MS(EI):162(M+,46),147(22),131(10),115(6),105(9),91(20),77(14),66(100),51(6),39(12)。I R(纯的,v/cm-1):3048m,2925s,2848s,1665s,1632m,1434m,1377m。
实施例40:(5-甲基-3a,4,7,7a-四氢-1H-茚-6-基)甲醇
按照实施例2中描述的一般步骤,以5-甲基-3a,4,7,7a-四氢-1H-茚-6-甲醛为原料制备标题化合物(产率98%)。
气味描述:辛香、风信子味、果香、苹果香、青香。
1H-NMR(300MHz,CDCl3):5.67-5.63(m,1H),5.53-5.47(m,1H),5.17-4.08(m,2H),2.96-2.85(m,1H),2.61-2.44(m,2H),2.27-2.15(m,2H),2.04-1.82(m,4H),1.75(s,3H)ppm。GC/MS(EI):164(M+,1),146(69),131(87),117(19),105(30),91(40),79(33),66(100),53(7),41(13)。IR(纯的,v/cm-1):3327br,3047m, 2925s,1668w,1444m,996s。
实施例41:rac-1-(亚丙-2-基)-3a,4,7,7a-四氢-1H-茚-6-甲醛
按照实施例1中描述的一般步骤,以6,6-二甲基富烯和巴豆醛为原料制备标题化合物(产率42%)。
气味描述:果香、青香、木香。
1H-NMR(300MHz,CDCl3):9.44(s,1H,CHO),6.95(ddd,J=5.9,4.5,1.5Hz,1H,5-H),6.34(dd,J=5.7,2.3Hz,1H,2-H),5.70(bd,J=5.7Hz,1H,3-H),3.24-3.17(m,1H,3a-H),2.92(ddd,J=7.5,7.5,7.5Hz,1H,7a-H),2.72-2.62(m,2H,4-Ha,7-Ha),2.27-2.17(dddd,J=16.6,6.1,4.5,1.5Hz,1H,4-Hb),1.91(dd,J=15.5Hz,8.3Hz,1H,7-Hb),1.79(s,3H,(CH3)a),1.74(s,H,CH3)b)ppm。13C-NMR(75MHz,CDCl3):192.1(d,CHO),151.8(d,C-5),143.7(s,C-6),142.9(s,C-1),136.7(d,C-3),131.4(d,C-2),122.6(s,C(CH3)2),43.4(d,C-3a),39.4(d,C-7a),29.3(t,C-4),23.8(t,C-7),21.1(q,(CH3)a),21.0(q,(CH3)b)ppm。GC/MS(EI):188(M+,30),173(4),159(2),145(5),128(6),115(7),106(100),91(40),77(7),65(6),53(4),39(5)。IR(纯的,v/cm-1):2910s,2716m,1681s,1443m,1374m。
实施例42:2-甲基-3a,4,7,7a-四氢-1H-茚-6-甲醛和3-甲基-3a,4,7,7a-四氢-1H-茚-6-甲醛(混合物的比例为2∶1)
按照实施例1中描述的一般步骤,以甲基环戊二烯和巴豆醛为原料制备2-甲基-3a,4,7,7a-四氢-1H-茚-6-甲醛和3-甲基-3a,4,7,7a-四氢-1H-茚-6-甲醛(产率35%)。
气味描述:青香、清鲜香气、辛香、果香、枯茗味、茴香味。
1H-NMR(300MHz,CDCl3):9.45,9.44(2s,1H),6.99-6.96(m,1H),5.28-5.27,5.18-5.17(2m,1H),2.98-2.93,2.74-2.68(2m,1H),2.59-2.39(m,4H),2.24-2.16(m,1H),2.07-2.02(m,1H),1.94-1.85(m,1H),1.69,1.67(2s,3H)ppm。GC/MS(EI):主要的异构体:162(M+,21),147(5),134(6),115(5),105(5),91(13), 80(100),65(6),53(7),39(10)。IR(纯的,v/cm-1):3037m,2917s,2842m,1679s,1442m,1377m,1176m,831m。
实施例43:4-乙基-3a,4,7,7a-四氢-1H-茚-6-甲醛
按照实施例1中描述的一般步骤,以环戊二烯和2-己醛为原料制备标题化合物(产率42%)。
气味描述:青香、果香、微弱。
1H-NMR(300MHz,CDCl3):9.42,9.40(2s,1H),6.84-6.83,6.74-6.72(2m,1H),5.74-5.53(m,2H),3.26-3.13(m,1H),2.87-2.75(m,1H),2.66-1.46(m,7H),1.06,1.02(2t,J=7.5Hz,3H)ppm。主要的异构体:13C-NMR(75MHz,CDCl3)192.7(d),157.3(d),142.4(s),132.5(d),130.3(d),49.1(d),41.2(d),41.0(t),34.4(d),25.1(t),24.9(t),12.44(q)ppm。GC/MS(EI):176(M+,28),147(23),117(13),105(8),91(21),77(14),66(100),41(10)。较少的异构体:13C-NMR(75MHz,CDCl3):192.7(d),156.3(d),142.5(s),133.9(d),130.2(d),49.4(d),41.9(d),39.4(t),35.5(d),27.1(t),24.7(t),11.63(q)ppm。IR(纯的,v/cm-1):3054m,2961s,2929s,1683s,1447m。
实施例44:1,4,4a,7,8,8a-六氢化萘-2-甲醛
按照实施例1中描述的一般步骤,以环己二烯和巴豆醛为原料制备标题化合物(产率19%)。
气味描述:花香、青香、辛香、木香。
1H-NMR(300MHz,CDCl3):9.39(s,1H),6.70(s,1H),5.59(s,2H),2.60-2.49(m,1H),2.39-1.98(m,7H),1.54(d,J=12.8Hz,1H),1.51(d,J=12.8Hz,1H)ppm。13C-NMR(75MHz,CDCl3):194.4(d),149.1(d),140.1(s),131.0(d),127.1(d),32.1(d),31.5(t),29.5(d),25.0(t),24.6(t),24.1(t)ppm。GC/MS(EI):162(M+,53),147(9),133(16),139(15),115(6),105(12),91(39),80(100),65(9),53(9),39(13)。I R(纯的,v/cm-1):3018m,2923s,2719w,1684s,1647m,1455m,1175m。
实施例45:4-(6-甲基庚-1,5-二烯-2-基)环己-1-烯甲醛
按照实施例1中描述的一般步骤,以月桂烯和巴豆醛为原料制备标题化合物(产率10%)。
气味描述:青香、果香、油脂味。
分析数据依据Raharivelomanana等人,Journal of NaturalProducts,Vol.56(2),1993,272-274中的参考数据。
实施例46:香料组合物
香料组合物具有水果、苹果和辛香特征
Agrumex(2-叔丁基环己基乙酸酯) 300
1-乙烯基环己-3-烯甲醛 13
4-乙烯基环己-1-烯甲醛 7
Belambre(1,7,7-三甲基-2′-(1-甲基乙基)螺[双环[2.2.1]
庚烷-2,4′-[1,3]二氧己环])50%,在IPM中 10
烯丙基环己基丙酸酯 15
乙基香草醛 1
纯Fraise(乙基甲基苯基缩水甘油酸酯) 3
Galaxolide(1,3,4,6,7,8-六氢-4,6,6,7,8,8-六甲基
环戊烯并[g]-2-苯并吡喃)66%,在DEP中 200
Galbanone 10(1-(5,5-二甲基环己-1-烯基)戊-4-烯-1-酮) 50
Jasmacyclene(3a,4,5,6,7,7a-六氢-4,7-亚甲基-1H-
茚-6-醇乙酸酯) 50
纯Peche(5-庚基二氢呋喃-2(3H)-酮) 50
邻苯二甲酸二乙酯 50
Pomarose(5,6,7-三甲基辛-2,5-二烯-4-酮) 1
Hercolyn DW(二氢枞酸甲酯) 250
1000
在香料中,1-乙烯基环己-3-烯甲醛和4-乙烯基环己-1-烯甲醛赋予天然清鲜果香,具有上乘的头香(sparkling top note)。
Claims (14)
2.根据权利要求1的方法,所述方法包括随后对式(Ia)的化合物进行还原,得到式(IIa)的化合物
其中
R1为氢、甲基或乙基;
R2为氢、C1-C6烷基或C2-C6烯基;
R3为氢、甲基或乙基;或者
R1和R3或R2和R3与其所连接的碳原子一起形成5-或6-元碳环;
R4、R5、R6、R7、R8和R9独立地选自氢、C1-C6烷基或C2-C6烯基;或者
R4+R9一起为选自-(CH2)n-、-C(=C(CH3)2)-和-C(=C(CH2CH3)2)-的二价残基,其中n为1或2;
R10为氢、直链或支链C1-C5烷基或直链或支链C2-C5烯基;和
R11为氢。
3.根据权利要求2的方法,所述方法包括随后在羧酸卤化物和碱存在下对式(IIa)的化合物进行酯化,得到其中R11为COR12、R12为氢或直链或支链C1-C3烷基的式(IIa)的化合物。
5.根据权利要求1或4的方法,所述方法包括随后在下述物质存在下对选自式(Ia)和(IIIa)的化合物的羰基进行转化
a)羟胺;
b)甲醇或乙醇;或者
c)二醇;
得到式(IVa)的化合物
其中
R1为氢、甲基或乙基;
R2为氢、C1-C6烷基或C2-C6烯基;
R3为氢、甲基或乙基;或者
R1和R3或R2和R3与其所连接的碳原子一起形成5-或6-元碳环;
R4、R5、R6、R7、R8和R9独立地选自氢、C1-C6烷基或C2-C6烯基;或者
R4+R9一起为选自-(CH2)n-、-C(=C(CH3)2)-和-C(=C(CH2CH3)2)-的二价残基,其中n为1或2;和
R10为氢、直链或支链C1-C5烷基或直链或支链C2-C5烯基;
R为氢且R′选自羟基或-OCOR13,其中R13为氢或C1-C3烷基;
R和R′选自甲氧基和乙氧基;或者
R和R′与其所连接的碳原子一起形成二氧戊环、羰基、二氧己环或C=N-OH。
7.根据权利要求6的方法,所述方法包括随后在羧酸卤化物和碱存在下对其中R11为氢的式(IIb)的化合物进行酯化,得到其中R11为COR12、R12为氢或直链或支链C1-C3烷基的式(IIb)的化合物。
9.根据权利要求1或8的方法,所述方法包括随后在下述物质存在下,对选自式(Ib)和(IIIb)的化合物的羰基进行转化,
a)羟胺;
b)甲醇或乙醇;或者
c)二醇;
得到式(IVb)的化合物
其中
R1为氢、甲基或乙基;
R2为氢、C1-C6烷基或C2-C6烯基;
R3为氢、甲基或乙基;或者
R1和R3或R2和R3与其所连接的碳原子一起形成5-或6-元碳环;
R4、R5、R6、R7、R8和R9独立地选自氢、C1-C6烷基或C2-C6烯基;或者
R4+R9一起为选自-(CH2)n-、-C(=C(CH3)2)-和-C(=C(CH2CH3)2)-的二价残基,其中n为1或2;和
R10为氢、直链或支链C1-C5烷基或直链或支链C2-C5烯基;
R为氢且R′选自羟基或-OCOR13,其中R13为氢或C1-C3烷基;
R和R′选自甲氧基和乙氧基;或者
R和R′与其所连接的碳原子一起形成二氧戊环、羰基、二氧己环或C=N-OH。
10.式(IVa)的化合物
其中
R1为氢、甲基或乙基;
R2为氢、C1-C6烷基或C2-C6烯基;
R3为氢、甲基或乙基;或者
R1和R3或R2和R3与其所连接的碳原子一起形成5-和6-元碳环;
R4、R5、R6、R7、R8和R9独立地选自氢、C1-C6烷基或C2-C6烯基;或者
R4+R9一起为选自-(CH2)n-、-C(=C(CH3)2)-和-C(=C(CH2CH3)2)-的二价残基,其中n为1或2;和
R10为氢、直链或支链C1-C5烷基或直链或支链C2-C5烯基;
R为氢且R′选自羟基或-OCOR13,其中R13为氢或C1-C3烷基;
R和R′选自甲氧基和乙氧基;或者
R和R′与其所连接的碳原子一起形成二氧戊环、二氧己环、羰基或C=N-OH;
条件是排除4-乙酰氧基薄荷-1,8-二烯和其中R1、R4-R6、R8和R9为氢,R7为甲基且R+R′与其所连接的碳原子一起形成羰基或者R为氢且R′为羟基的式(IVa)的化合物。
11.根据权利要求10的式(IVa)的化合物,所述化合物选自
2,4-二甲基-1-乙烯基环己-3-烯甲醛,
(2,4-二甲基-1-乙烯基环己-3-烯基)甲醇,
(2,4-二甲基-1-乙烯基环己-3-烯基)乙醇,
1-(2,4-二甲基-1-乙烯基环己-3-烯基)乙酮,
(2,4-二甲基-1-乙烯基环己-3-烯基)甲基乙酸酯,
(2,4-二甲基-1-乙烯基环己-3-烯基)丁-3-烯-1-醇,
(2,4-二甲基-1-乙烯基环己-3-烯基)丁-3-烯-1-酮,
2,4-二甲基-1-(丙-1-烯-2-基)环己-3-烯甲醛,
1-(2,4-二甲基-1-(丙-1-烯-2-基)环己-3-烯基)乙醇,
1-(2,4-二甲基-1-(丙-1-烯-2-基)环己-3-烯基)乙基乙酸酯,
1-(2,4-二甲基-1-(丙-1-烯-2-基)环己-3-烯基)-2-甲基丙-1-醇,
1-(2,4-二甲基-1-(丙-1-烯-2-基)环己-3-烯基)-2-甲基丙-1-酮,
1-(2,4-二甲基-1-(丙-1-烯-2-基)环己-3-烯基)乙酮,
1-(2,4-二甲基-1-(丙-1-烯-2-基)环己-3-烯基)丁-3-烯-1-醇,
1-(2,4-二甲基-1-(丙-1-烯-2-基)环己-3-烯基)丁-3-烯-1-酮,
1-(2,4-二甲基-1-(丙-1-烯-2-基)环己-3-烯基)丁-2-烯-1-酮,
1-(丁-1,3-二烯基)-2,4-二甲基环己-3-烯甲醛,
3,4-二甲基-1-乙烯基环己-3-烯甲醛,
2-甲基-1-(2-甲基丙-1-烯基)环己-3-烯甲醛,
2,4-二甲基-1-(2-甲基丙-1-烯基)环己-3-烯甲醛,
1-(2,4-二甲基-1-(2-甲基丙-1-烯基)环己-3-烯基)乙醇,
1-环戊烯基-2,4-二甲基环己-3-烯甲醛,
4,5-二甲基-2-(2-甲基丙-1-烯基)-1-乙烯基环己-3-烯甲醛,
2-甲基-4-(4-甲基戊-3-烯基)-1-乙烯基环己-3-烯甲醛,
3-甲基-1-乙烯基-环己-3-烯-甲醛,
4-甲基-1-乙烯基-环己-3-烯甲醛肟,
3-甲基-1-乙烯基-环己-3-烯-甲醛肟,
1-(丙-1-烯-2-基)环己-3-烯甲醛,
1-(丁-1-烯基)-2,4-二甲基环己-3-烯甲醛,
4-甲基-1-(丙-1-烯-2-基)环己-3-烯甲醛,
3-甲基-1-(丙-1-烯-2-基)环己-3-烯甲醛,和
1-乙烯基环己-3-烯甲醛。
12.式(IVa)的化合物作为调料或香料的用途
其中
R1为氢、甲基或乙基;
R2为氢、C1-C6烷基或C2-C6烯基;
R3为氢、甲基或乙基;或者
R1和R3或R2和R3与其所连接的碳原子一起形成5-或6-元碳环;
R4、R5、R6、R7、R8和R9独立地选自氢、C1-C6烷基或C2-C6烯基;或者
R4+R9一起为选自-(CH2)n-、-C(=C(CH3)2)-和-C(=C(CH2CH3)2)-的二价残基,其中n为1或2;和
R10为氢、直链或支链C1-C5烷基或直链或支链C2-C5烯基;
R为氢且R′选自羟基或-OCOR13,其中R13为氢或C1-C3烷基;
R和R′选自甲氧基和乙氧基;或者
R和R′与其所连接的碳原子一起形成二氧戊环、羰基、二氧己环或C=N-OH;
条件是排除4-乙酰氧基薄荷-1,8-二烯和其中R1、R4-R6、R8和R9为氢、R7为甲基且R+R′与其所连接的碳原子一起形成羰基或者R为氢且R′为羟基的式(IVa)的化合物。
13.通过向消费品基质中加入权利要求12中定义的式(IVa)的化合物或其混合物而改善、增强或改变消费品基质的方法。
14.香料用品,所述香料用品包含:
a)作为增香剂的选自权利要求12中定义的式(I Va)的化合物的化合物及其混合物;和
b)消费品基质。
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DE102011005947A1 (de) * | 2011-03-23 | 2012-09-27 | Henkel Ag & Co. Kgaa | Diels-Alder-Addukte als thermisch spaltbare Riechstoffvorläufer |
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AR099860A1 (es) * | 2014-03-26 | 2016-08-24 | Procter & Gamble | Sistemas de perfume |
CN104433927B (zh) * | 2014-10-23 | 2017-11-10 | 广东比伦生活用纸有限公司 | 一种手帕纸的加香工艺及制得的香味手帕纸 |
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CN109651149B (zh) * | 2017-10-11 | 2021-06-01 | 中国科学院大连化学物理研究所 | 一种制备1,2-环己烷二甲酸酯或邻苯二甲酸酯的方法 |
CN111495289B (zh) * | 2020-04-27 | 2021-01-12 | 肇庆市高要华新香料有限公司 | 一种气液两相连续反应装置及山梨醛的制备方法 |
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US8304380B2 (en) | 2012-11-06 |
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US20100204084A1 (en) | 2010-08-12 |
US20130035278A1 (en) | 2013-02-07 |
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GB0715496D0 (en) | 2007-09-19 |
EP3112338A2 (en) | 2017-01-04 |
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