CN1334031A - α－酮烯胺衍生物作为配料的应用 - Google Patents

α－酮烯胺衍生物作为配料的应用 Download PDF

Info

Publication number
CN1334031A
CN1334031A CN01124817A CN01124817A CN1334031A CN 1334031 A CN1334031 A CN 1334031A CN 01124817 A CN01124817 A CN 01124817A CN 01124817 A CN01124817 A CN 01124817A CN 1334031 A CN1334031 A CN 1334031A
Authority
CN
China
Prior art keywords
methyl
pyrrolidinyl
application
mpc
ketone
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN01124817A
Other languages
English (en)
Inventor
T·霍夫曼
H·奥蒂格
O·弗兰克
T·索多
C·塞伊
F·罗伯特
I·布兰克
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Societe des Produits Nestle SA
Nestle SA
Original Assignee
Societe des Produits Nestle SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Societe des Produits Nestle SA filed Critical Societe des Produits Nestle SA
Publication of CN1334031A publication Critical patent/CN1334031A/zh
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C11B9/0069—Heterocyclic compounds
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
    • A23G3/00—Sweetmeats; Confectionery; Marzipan; Coated or filled products
    • A23G3/34—Sweetmeats, confectionery or marzipan; Processes for the preparation thereof
    • A23G3/346—Finished or semi-finished products in the form of powders, paste or liquids
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
    • A23G3/00—Sweetmeats; Confectionery; Marzipan; Coated or filled products
    • A23G3/34—Sweetmeats, confectionery or marzipan; Processes for the preparation thereof
    • A23G3/36—Sweetmeats, confectionery or marzipan; Processes for the preparation thereof characterised by the composition containing organic or inorganic compounds
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
    • A23G3/00—Sweetmeats; Confectionery; Marzipan; Coated or filled products
    • A23G3/34—Sweetmeats, confectionery or marzipan; Processes for the preparation thereof
    • A23G3/50—Sweetmeats, confectionery or marzipan; Processes for the preparation thereof characterised by shape, structure or physical form, e.g. products with supported structure
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
    • A23G9/00—Frozen sweets, e.g. ice confectionery, ice-cream; Mixtures therefor
    • A23G9/32—Frozen sweets, e.g. ice confectionery, ice-cream; Mixtures therefor characterised by the composition containing organic or inorganic compounds
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
    • A23G9/00—Frozen sweets, e.g. ice confectionery, ice-cream; Mixtures therefor
    • A23G9/44—Frozen sweets, e.g. ice confectionery, ice-cream; Mixtures therefor characterised by shape, structure or physical form
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
    • A23G9/00—Frozen sweets, e.g. ice confectionery, ice-cream; Mixtures therefor
    • A23G9/52—Liquid products; Solid products in the form of powders, flakes or granules for making liquid products ; Finished or semi-finished solid products, frozen granules
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K20/00—Accessory food factors for animal feeding-stuffs
    • A23K20/10—Organic substances
    • A23K20/116—Heterocyclic compounds
    • A23K20/132—Heterocyclic compounds containing only one nitrogen as hetero atom
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K50/00—Feeding-stuffs specially adapted for particular animals
    • A23K50/40—Feeding-stuffs specially adapted for particular animals for carnivorous animals, e.g. cats or dogs
    • 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
    • A23L2/00—Non-alcoholic beverages; Dry compositions or concentrates therefor; Their preparation
    • A23L2/52—Adding ingredients
    • A23L2/56—Flavouring or bittering agents
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/41—Amines
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4906—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
    • A61K8/4913—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having five membered rings, e.g. pyrrolidone carboxylic acid
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4906—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
    • A61K8/4926—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having six membered rings
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
    • C07C225/20—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to carbon atoms of rings other than six-membered aromatic rings of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/10—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms
    • C07D295/112—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms with the ring nitrogen atoms and the doubly bound oxygen or sulfur atoms separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings
    • C07D295/116—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms with the ring nitrogen atoms and the doubly bound oxygen or sulfur atoms separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings with the doubly bound oxygen or sulfur atoms directly attached to a carbocyclic ring
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
    • A23G2200/00—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF containing organic compounds, e.g. synthetic flavouring agents
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
    • A23G2220/00—Products with special structure
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/20—Chemical, physico-chemical or functional or structural properties of the composition as a whole
    • A61K2800/24—Thermal properties
    • A61K2800/244—Endothermic; Cooling; Cooling sensation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Food Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Veterinary Medicine (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Animal Behavior & Ethology (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Zoology (AREA)
  • Inorganic Chemistry (AREA)
  • Animal Husbandry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Wood Science & Technology (AREA)
  • Dermatology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Nutrition Science (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Fats And Perfumes (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • General Preparation And Processing Of Foods (AREA)
  • Seasonings (AREA)
  • Cosmetics (AREA)
  • Hydrogenated Pyridines (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Furan Compounds (AREA)
  • Feed For Specific Animals (AREA)
  • Fodder In General (AREA)
  • Confectionery (AREA)
  • Non-Alcoholic Beverages (AREA)
  • Detergent Compositions (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Pyrrole Compounds (AREA)

Abstract

本发明涉及下列通式化合物:(见化学式A)单独或联合在食品、化妆品、药物和香料组合物中作为配料的应用。其中R1为N－吡咯烷基,R2为甲基,X为亚乙基,Y为氧基。

Description

α-酮烯胺衍生物作为配料的应用
本发明涉及α-酮烯胺衍生物作为配料的应用。
为了获知在热处理谷类产品期间挥发性物质的形成，近二十年来对L-脯氨酸同还原单糖的Maillard反应进行了广泛深入的研究(Tressl等.，农业食品化学杂志(J.Agric.Food Chem.)，1985a，33，919-923；Tressl等.，农业食品化学杂志(J.Agric.Food Chem.)，1985b，33，924-928；Tressl等.，农业食品化学杂志(J.Agric.Food Chem.)，1985c，33，1132-1137；Helak等.，农业食品化学杂志(J.Agric.Food Chem.)，1989a，37，400-404；Helak等.，农业食品化学杂志(J.Agric.Food Chem.)，1989b，37，405-410；Huyghues-Despoints等农业食品化学杂志(J.Agric.Food Chem.)，1994，42，2519-2524)。
通过应用GC/嗅觉测量技术例如Charm分析(Roberts，D.D.，Acree，T.InThermally Generated Flavors；Parliment T.H.，Morello M.J.，McGomn R，Eds，；ACS，华盛顿DC，1994，71-79)或芳香提取稀释分析(AEDA)(Hofmann，T.，Schieberle，P.J.农业食品化学杂志(J.Agric.Food Chem.)，1998，46，2721-2726)，在由L-脯氨酸和还原糖组成的Maillard反应系统的溶剂提取物中，这些气味活性化合物能够被成功地检测出来。在这些检测出的挥发性物质中，爆米花型味道化合物2-乙酰基-1-吡咯啉和2-乙酰基四氢吡啶被鉴定为热处理葡萄糖/脯氨酸混合物中所有气味物质中的主要成分(Hofman和Schieberle，农业食品化学杂志(J.Agric.FoodChem.)，1998，46，2270-2277)。尽管经AEDA显示：在这些烤煮处理期间形成的挥发性反应产品的主要部分没有气味活性，但不能排除：一些这样的无气味化合物可能会在舌上引起某种味道刺激例如苦感、刺鼻感(heating)或清凉感。
因此，对于还原性糖的这样反应产品的感官刺激已经有人描述。
从由烤煮葡萄糖/脯氨酸混合物得到的HPLC部分中，通过应用最近开发的味道稀释分析技术(Hofman，T.农业食品化学杂志(J.Agric.Food Chem.)，1999，47，4763-4768)，检测出两个化合物，其在舌上显示强烈的清凉感。当己糖降解产品2-羟基-3-甲基-2-环戊烯-1-酮在L-脯氨酸存在下起反应时，发现这些化合物被高浓度地形成。经柱层析分离后，得到的这两个化合物均为淡黄色油状物质，纯度高于99％。GC/MS和1D-以及2D-NMR色谱明确鉴定这两个清凉味化合物为5-甲基2-(1-吡咯烷基)-2-环戊烯-1-酮(5-MPC)和3-甲基-2-(吡咯烷酮)-2-环戊烯-1-酮(3-MPC)。
Figure A0112481700051
虽然Tressl等人(1985c)和Huyghes-Dispointes等人(1994)已经报道了这些化合物，但他们并没有报道这些化合物接触舌时能够产生清凉感。
除3-MPC和5-MPC外，我们在葡萄糖脯氨酸混合物中还鉴定了另一种具有清凉味的化合物：2，5-二甲基-4-(1-吡咯烷基)-3-(2H)-呋喃酮(DMPF)。
Figure A0112481700052
通过加热2-羟基-3-甲基-2-环戊烯-1-酮和乙酸吡咯啉的乙醇溶液，或者通过在脯氨酸存在下干燥加热2-羟基3-甲基-2-环戊烯-1-酮能够容易得到3-MPC和5-MPC。类似地，通过在乙酸吡咯啉的乙醇溶液中或在脯氨酸存在以及干燥加热条件下，4-羟基-2，5-二甲基3(2H)-呋喃酮起反应得到DMPF。
日本专利7242661记载了DMPF作为调味剂化合物能够使小麦面粉食品具有味道。该专利记载：只需加热条件下，这些食品产生味道。因此，该专利把DMPF作为味道物质前体。英国专利1096427记载了某些环戊酮作为有趣的香料类化合物。其还要求保护某些α-酮烯胺，但其仅仅提出将这些化合物作为合成其它化合物的中间体。
本发明目的是提供一类化合物，当将其在食品或其它组合物中用作配料、更特别地用作清凉剂时，所述化合物具有良好的特性。同显示强薄荷类味道的薄荷醇相比，这些化合物不具有味道或具有弱的味道，因此它们不改变食品或其它组合物的香味。
本发明目的是应用下列通式化合物：将所述化合物单独应用或联合应用，作为食品、化妆品、药物或香料组合物中的配料，其中：
R1选自：
    -N-吡咯烷基
    -N-吡啶基
    -N-(氨基-二乙基)
    -N-(2-羧基-吡咯烷基)
    -N-(2-甲氧基羰基-吡咯烷基)
R2选自：
    -H
    -甲基
X选自：
    -亚甲基
    -亚乙基
    -1-亚丙基
    -氧基
Y选自：
    -亚甲基
    -亚乙基
    -1-亚丙基
    -氧基
    -乙烷-1，2-二基
    -乙烯-1，2-二基
    -丙烷-1，2-二基
    -乙烷-1-氧-1-基。
在本申请中，“单独”指仅仅应用通式(A)化合物。但根据本发明，还可能把若干通式(A)化合物用于同一组合物中。
在本发明通式化合物第一个优选的实施方案中，R1为N-吡咯烷基，R2为氢，X为亚甲基，Y为亚乙基(5-MPC)。在本发明通式化合物另一个优选的实施方案中，R1为N-吡咯烷基，R2为甲基，X为氧基，Y为亚甲基(MPF)。在本发明通式化合物第三个优选的实施方案中，R1为N-吡咯烷基，R2为甲基，X为亚甲基，Y为氧基(4-甲基3-(1-吡咯烷基)-2(5H)-呋喃酮，2(5H)MPF)。在本发明通式化合物第四个优选的实施方案中，R1为N-吡咯烷基，R2为甲基，X为亚乙基，Y为氧基(4，5-二甲基-3-(1-吡咯烷基)-2(5H)-呋喃酮，2(5H)DMPF)。
对于食品组合物，其可以选自巧克力、冰淇淋、饮料、糖甜食和宠物食品。
对于化妆品组合物，其选自所有局部用的化妆品组合物。
对于香料组合物，其选自醇基质或水基组合物。
通式(A)化合物单独应用或联合应用的用量为整个组合物的0.01-3000mg/kg。已经如上所述，把上述通式(A)化合物加入到组合物中，这些化合物能够是所述组合物产生清凉效果。
                合成通式(A)清凉物质的一般步骤
在等摩尔量(例如400mmol)氨基化合物(例如吡咯烷)和乙酸存在下，把环烯醇酮化合物(例如100mmol)的乙醇溶液加热回流数小时(例如1-5小时)。冷却至室温后，真空除去溶剂，把残余物溶解于水中。用氢氧化钠溶液(例如30％水溶液)加入至pH10。然后用有机溶剂(如乙醚)提取该溶液，合并有机层，用碳酸钠水溶液(例如200mL；0.5mol/L)洗涤，硫酸钠干燥，真空除去溶剂。还可以用氧化铝柱色谱(碱性，活性III-IV，Merck，Darmstadt，德国)对目标化合物进行进一步纯化。进行柱色谱时可以应用不同比例的各种有机溶剂例如己烷(如200ml)、己烷/乙醚(例如7∶3，400ml)、己烷/乙醚(如3∶7，400ml)和乙醚(如400ml)。可以从乙醚获得的组份中真空除去溶剂得到目标化合物。按照该一般步骤可以合成表1中化合物。表1.合成的清凉味化合物
烯醇酮 胺 目标化合物
2-羟基-3-甲基-2-环戊烯-1-酮 吡咯烷 3-甲基-2-(1-吡咯烷)-2-环戊烯-1-酮(3-MPC)5-甲基-2-(1-吡咯烷)-2-环戊烯-1-酮(5-MPC)
2-羟基3-甲基-2-环戊烯-1-酮 哌啶 3-甲基-2-(1-哌啶)-2-环戊烯-1-酮(3-MPipC)5-甲基-2-(1-哌啶)-2-环戊烯-1-酮(5-MPipC)
2-羟基3-甲基-2-环戊烯-1-酮 二乙胺 3-甲基-2-二乙胺基-2-环戊烯-1-酮(3-MDeaC)5-甲基-2-二乙胺基-2-环戊烯-1-酮(5-MDeaC)
2-羟基3-甲基-2-环戊烯-1-酮 L-脯氨酸 3-甲基-2-(2-羧基-1-吡咯烷基)-2-环戊烯-1-酮(3-MProC)
 2-羟基-3-甲基-2-环戊烯-1-酮 L-脯氨酸甲酯 5-甲基-2-(2-甲氧基羰基-1-吡咯烷基)-2-环戊烯-1-酮(5-MMeProC)
 2-羟基-3-乙基-2-环戊烯-1-酮 吡咯烷 5-乙基-2-(1-吡咯烷基)-2-环戊烯-1-酮(5-EPC)
2-羟基-3，5-二甲基-2-环戊烯-1-酮 吡咯烷 3，5-二甲基-2-(1-吡咯烷基)-2-环戊烯-1-酮(3，5-DMPC)
2-羟基-3，4-二甲基-2-环戊烯-1-酮 吡咯烷 3，4-二甲基2-(1-吡咯烷基)-2-环戊烯-1-酮(3，4-DMPC)4，5-二甲基2-(1-吡咯烷基)-2-环戊烯-1-酮(4，5-DMPC)
2-羟基-3-甲基-2-环戊烯-1-酮 吡咯烷 3-甲基-2-(1-吡咯烷基)-2-环己烯-1-酮(3-MPCH)6-甲基-2-(1-吡咯烷基)-2-环己烯-1-酮(6-MPCH)
2，5-二甲基-4-羟基-3(2H)-呋喃酮 吡咯烷 2，5-二甲基-4-(1-吡咯烷基)-3(2H)-呋喃酮(DMPF)
4-羟基-5-甲基-3(2H)-呋喃酮 吡咯烷 5-甲基-4-(1-吡咯烷基)-3(2H)-呋喃酮(MPF)
3-羟基-4，5-二甲基-2(5H)-呋喃酮 吡咯烷 4，5-二甲基-3-(1-吡咯烷酮基)-2(5H)-呋喃酮(2(5H)-DMPF)
3-羟基-4-甲基2(5H)-呋喃酮 吡咯烷 4-甲基3-(1-吡咯烷酮)-2(5H)-呋喃酮(2(5H)-MPF)
5-甲基-2-(1-吡咯烷基)-2-环戊烯-1-酮(5-MPC)和3-甲基-2-(1-吡咯烷基)-2-环戊烯-1-酮(3-MPC)的合成
1、从2-羟基3-甲基-2-环戊烯-1-酮(甲基环戊烯醇酮)和乙酸吡咯啉的乙醇液制备。把甲基环戊烯醇酮(100mmol)、吡咯烷(400mmol)和乙酸(400mmol)的乙醇(600ml)溶液回流2小时。冷至室温，真空除去溶剂，把残余物溶解于水(300mL)，用氢氧化钠溶液(30％水溶液)调节pH至10。用乙醚(5×150ml)提取该溶液，合并有机层，用碳酸钠水溶液洗涤(200mL，0.5mol/L)，硫酸钠干燥，真空除去溶剂。把残余油状物溶解于戊烷/乙醚(6/4，v/v，10mL)，然后将其施加于装有氧化铝(碱性，活性III-IV，Merck，Darmastadt，德国)的戊烷浆液的柱(30×500mm)上。进行层析时应用戊烷(300mL，A部分)、戊烷/乙醚(9/1，v/v；300mL；B部分)、戊烷/乙醚(8/2，v/v；300mL；C部分)、戊烷/乙醚(7/3，v/v，300mL，D部分)、戊烷/乙醚(6/4，v/v；300mL；E部分)，然后应用戊烷/乙醚(5/5，v/v；300mL，F部分)。收集含有5-MPC(1.65g，10％产率)的B部分和含有3-MPC(1.32g，8％产率)的D部分，真空除去溶剂，得到淡黄色油状的目标化合物。
Figure A0112481700091
3-甲基2-(1-吡咯烷基)-2-环戊烯-1-酮(3-MPC)和5-甲基-2-(1-吡咯烷基)-2-环戊烯-1-酮(5-MPC)的合成制备2、从2-羟基-3-甲基2-环戊烯-1-酮(甲基环戊烯醇酮)和脯氨酸在氧化铝上干燥加热制备。把甲基环戊烯醇酮(100mmol)和脯氨酸(100mmol)的混合物同氧化铝(20g，碱性，活性III-IV)磨碎，然后在180℃下干燥加热10分钟。将混合物悬浮于水(100mL)，过滤，用氢氧化钠溶液调节至pH10(30％水溶液)，然后用乙醚提取。按照上面用于(甲基环戊烯醇酮)/乙酸吡咯啉混合物详细描述的方法处理该反应混合物。得到淡黄色油状的目标化合物5-MPC(120mg)和3-MPC(33mg)。光谱数据：3-MPC：MS(EI)：165(100；[M]+)，164(47)，137(34)，136(38)，122(53)，109(136)，108(43)，94(27)，81(26)，67(21)，41(27)。1H NMR(360MHz；CDCl3，COSY，TOCSY)：δ1.77-1.81(m，2×2H，CH2)，2.13(s，3H，CH3)，2.34-2.35(m，2H，CH2)，2.39-2.41(m，2H，CH2)，3.40-3.44(m，2×2H，CH2).13C NMR(360MHz；CDCl3；DEPT，HMQC，HMBC)：δ17.8[CH3]，24.9[2×CH2]，30.0[CH2]，34.1[CH2]，49.5[2×CH2]，143.7[C]，145.9[C]，205.9[CO].5-MPC：MS(EI)：165(100；[M]+)，164(32)，150(26)，137(22)，136(37)，122(87)，108(34)，95(34)，94(31)，70(21)，67(24)，54(24)，41(25).1H NMR(360MHz；CDCl3，COSY，TOCSY)：δ1.16-1.18(d，3H，J＝7.5Hz，CH3)，1.82-1.88(m，2×2H，CH2)，2.06-2.11(dd，J＝17.7，2.2Hz，1H，CHaH)，2.35-2.43(m，1H，J＝7.5，2.2；CH)，2.71-2.78(dd，J＝17.7，3.1Hz，1H，CHHb)，3.22-3.33(m，2×2H，CH2)，5.82-5.83(t，J＝3.1Hz，1H，CH).13C NMR(360MHz；CDCl3；DEPT，HMQC，HMBC)：δ16.5[CH3]，24.8[2×CH2]，32.6[CH2]，40.2[CH]，48.1[2×CH2]，123.6[CH]，146.7[C]，207.4[CO].5-甲基-4-(1-吡咯烷酮)-3(2H)-呋喃酮(MPF)的合成1、从木糖和吡咯烷制备。把木糖(0.1mol)和吡咯烷(0.1mol)的甲醇(90ml)溶液回流3小时，然后加入乙酸(0.1mol)，再持续加热2小时。冷却后，真空除去溶剂，将残余物溶解于水(100ml)，用乙酸乙酯提取(100ml，5次)，合并有机层，用0.1M氢氧化钠水溶液(3×50ml)提取，干燥有机相(硫酸钠)，应用在正己烷中平衡的氧化铝(碱性，活性III-IV；Merck，Darstadt，德国)柱进行层析。进行层析时所用的洗脱剂为：己烷(200ml)、己烷/乙醚7∶3(400mL)、3∶7(400ml)和乙醚(400ml)。把由乙醚洗脱得到的部分真空除去溶剂，得到纯度高于99％的无色油状目标化合物MPF(0.9mmol；0.9％)。2、从4-羟基-5-甲基2H-呋喃-3-酮和吡咯烷酮制备。把4-羟基-5-甲基-2H-呋喃-3-酮(10mmol)和吡咯烷酮(20mmol)和乙酸(20mmol)的甲醇(50ml)混合物回流3小时。冷却后，真空除去溶剂，把残余物溶解于水(100ml)，用乙酸乙酯提取(100ml×5次)，合并有机层，用0.1M氢氧化钠水溶液(3×50ml)提取，干燥有机相(硫酸钠)，如上详述进行柱层析分离。得到纯度高于99％的无色油状目标化合物MPF(0.5mmol；5％产率)。MPF的光谱数据：GC/MS(EI)：42(100)，167(95)，54(93)，96(76)，124(74)1H NMR(360MHz；CDCl3，COSY，TOCSY)：1.82(m，2×2H，CH2)，2.23(s，3H，CH3)，3.11(m，2×2H，CH2)，4.38(s，2H，CH2)13C-NMR(360MHz ；CDCl3)：14.2(CH3)，24.7(2×CH2)，50.6(2×CH2)，72.9(CH2)，126.3(C)，183.0(C)，198.9(CO)4，5-二甲基-3-(1-吡咯烷酮)-2(5H)-呋喃酮[2(5H)DMPF]的合成
从3-羟基-4，5-二甲基-2(5H)-呋喃酮和乙酸吡咯啉的乙醇溶液制备。把3-羟基-4，5-二甲基2(5H)-呋喃酮(10mmol)、乙酸(10mmol)和吡咯烷(10mmol)的乙醇(50mL)溶液回流3小时。冷却至室温，真空除去溶剂，把残余物溶解于水(25ml)。用乙醚提取(5×10ml)该溶液，合并有机层，用硫酸钠干燥，然后真空除去溶剂。把残余油溶解于戊烷/乙醚(4/1，v/v；5mL)，然后施加于装有氧化铝(碱性，活性III-IV、Merck，Darmstadt，德国)戊烷浆液的柱(30×500mm)上。进行层析时，洗脱剂为戊烷(300mL，A部分)、戊烷/乙醚(9/1，v/v；400mL；B部分)、戊烷/乙醚(80/20，v/v；400mL；C部分)、戊烷/乙醚(70/30，v/v，400mL，D部分)、戊烷/乙醚(60/40，v/v；400mL；E部分)。收集含有2(5H)-DMPF的(0.64g，36％产率)的E部分，真空除去溶剂，得到无色油状的目标化合物。2(5H)-DMPF的光谱数据；MS(EI)：181(82；[M]+)，166(76)，138(28)，136(49)，122(100)，110(74)，108(93)，94(37)，82(36)，68(26)，55(43)，54(26)，53(24)，43(31)，41(44).1H NMR(360MHz；CDCl3，COSY，TOCSY)：δ1.35-1.36(d，3H，J＝6.6Hz，CH3)，1.79-1.86(m，2×2H，CH2)，2.03(s，3H，CH3)，3.47-3.57(m，2×2H，CH2)，4.66-4.72(q，1H，J＝6.6Hz，CH).13C NMR(360MHz；CDCl3； DEPT，HMQC，HMBC)：δ11.8[CH3]，19.2[CH3]，24.9[2×CH2]，49.3[2×CH2]，78.0[CH]，128.7[C]，130.5[C]，170.4[CO].4-甲基-3-(1-吡咯烷)-2(5H)-呋喃酮[2(5H)-MPF]的合成从4-甲基-二氢-呋喃-2，3-二酮和乙酸吡咯啉的乙醇溶液制备。把4-甲基-二氢-呋喃2，3-二酮(100mmol，按照Fleck等.，Helv.Chim.Acta 1950，33，130所述方法制备)和乙酸(100mmol)和吡咯烷(100mmol)的乙醇(225mL)溶液回流2.5小时。冷却至室温，真空除去溶剂，把残余物溶解于水(200mL)。用乙醚(5×100ml)提取该溶液，合并有机层，用硫酸钠干燥，真空除去溶剂。把残余油溶解于戊烷/乙醚(3/2，v/v；10ml)，然后将其施加于装有氧化铝(碱性，活性III-IV，Merck，Darmstadt，德国)的戊烷浆状液的柱(30×500mm)上。进行层析所用洗脱剂为戊烷(300mL，A部分)、戊烷/乙醚(9/1，v/v；400mL；B部分)、戊烷/乙醚(80/20，v/v；400mL；C部分)、戊烷/乙醚(70/30，v/v，400mL，D部分)、戊烷/乙醚(60/40，v/v；400mL；E部分)、戊烷/乙醚(50/50，v/v；400mL，F部分)。收集含有2(5H)-MPF(2.25g，14％产率)的F部分，真空除去溶剂，得到淡黄色油状的目标化合物。2(5H)-MPF的光谱学数据：MS(EI)：167(94；[M]+)，166(63)，139(58)，138(45)，122(93)，120(43)，111(54)，110(46)，108(32)，95(26)，94(100)，82(25)，81(24)，80(23)，68(67)，67(21)，55(36)，54(27)，53(23)，41(58).1H NMR(360MHz；CDCl3，COSY，TOCSY)：δ1.80-1.86(m，2×2H，CH2)，2.09(s，3H，CH3)，3.49-3.54(m，2×2H，CH2)，4.53(s，2H，CH2).13C NMR(360MHz；CDCl3； DEPT，HMQC，HMBC)：δ12.4[CH3]，25.1[2×CH2]，49.5[2×CH2]，71.7[CH2]，124.3[C]，130.7[C]，171.6[CO].感觉分析
在感觉分析前，用GC/MS检测合成的味觉化合物的纯度。应用受过训练的参加者进行清凉感以及芳香阈值的确定。应用自来水作为溶剂通过三角测试确定鼻味阈值(Guth，H.；Grosch，W.J.Am.Oil Chem.Soc.1993，70，513-518)以及清凉感阈值。样品按照浓度增加的顺序提供，把三个独立测定(sessions)所评价的阈值平均。个体和独立测定之间的值相差不超过一个稀释步骤。
表2中总结了感官分析的结果。除薄荷醇外，5-MPC、2(5H)-DMPF、MPF和2(5H)-MPF具有最低的清凉阈值。气味阈浓度的比较表明：薄荷醇产生强的薄荷型芳香气味而新的清凉剂显示明显高的芳香阈值。清凉阈值和芳香阈值的比值计算明显证明：没有芳香或仅仅有弱芳香味的本发明化合物能够用作清凉剂化合物，并且不产生强气味。相反，对于薄荷醇，其气味阈值比其清凉阈值低9.5倍，这样表明其非常难以在不产生显著薄荷味的条件下产生清凉效果。这些数据还显示：通过应用新的清凉化合物，能够在消费非薄荷型食品组合物期间产生一定清凉效果，其中所述食品组合物例如甜食产品、麦芽型饮料和水果香料或棕色香料(brown flavour)。特别是2(5H)-DMPF、MPF和2(5H)-MPF，它们同薄荷醇相比具有低得多的清凉阈值/气味阈值之比，因此是非常有效的冷却物质。
表2.选择化合物的清凉和气味阈值的比较
 清凉物质  清凉阈值a  气味阈值a 气味性质 清凉/气味比值
3-MProC 490-735 - 无味 ＜＜0.01
 5-MMeproC  112-188   - 无味 ＜＜0.01
 DMPF  100-140  30-60 坚果味，烧烤味 2.7
 3-MPCH  90-150  45-75 弱薄荷味 2.0
 4.5-DMPC  68-113  136-226 弱薄荷味 0.5
 3-MPipC  60-100  80-120 弱胺味 0.8
 3，4-DMPC  51-86  26-43 橡胶味 2.0
 3，5-DMPC  33-54  16-27 橡胶味 2.0
 3-MPC  29-44  44-73 弱胺味 0.8
 6-MPCH  27-45  3.4-5.6 橡胶味 8.0
 5-EPC  27-43  13-22 弱薄荷味 2.0
 5-MPipC  16-24  12-20 弱薄荷味 2.7
 5-MDeaC  12-20  6.0-9.0 姜黄味 2.1
 5-MPC  4.5-9  2.6-5.2 弱薄荷味 1.7
 2(5H)-DMPF  2.0-4.0  32-64 弱薄荷味 0.06
 MPF  1.5-3.0   - 无味 ＜＜0.01
 2(5H)-MPF  0.02-0.06   - 无味 ＜＜0.01
 (-)薄荷醇  0.9-1.9  0.1-0.2 薄荷味 9.5
a在水中测定的阈值[mg/kg]。
在一个另外的实验中，测定了3-MPC、5-MPC、MPF、2(5H)-MPF和2(5H)-DMPF在巧克力中的清凉阈值。如表3所示，在巧克力中，2(5H)-MPF的清凉阈值最低，约0.25-0.5mg/100g，然而，5-MPC清凉阈值显示比上述阈值8倍还高。
      表3.MPF、3-MPC和5-MPC在牛奶巧克力中的清凉阈值
   清凉化合物    清凉效果[mg/100g巧克力]
   2(5H)-MPF        0.25-0.5
   MPF              0.8-1.5
   5-MPC            2.3-3.7
   2(5H)-DMPF       5.0-7.5
   3-MPC            38-63炒麦芽中5-甲基-2-(1-吡咯烷基)-2-环戊烯-1-酮(5-MPC)、3-甲基2-(1-吡咯烷基)-2-环戊烯-1-酮(3-MPC)和2，5-二甲基-4-(1-吡咯烷基)-3(2H)-呋喃酮(DMPF)的鉴定
把深色麦芽(50g，Caraffa special)在液氮中冷冻，然后将其在研钵研磨。将粉末同二氯甲烷(2×400mL)一起搅拌过夜。合并有机层，真空浓缩至50mL，然后在25℃下，高真空蒸馏分离麦芽组份中的挥发性组份。把得到的蒸馏物浓缩至约1mL，然后用柱色谱(0.9×100mm)分离，柱中装有氧化铝(碱性，活性III-IV，Merck，德国Darmstadt)，其中氧化铝先用戊烷平衡。进行色谱所用洗脱剂为戊烷(100mL，A部分)、戊烷/乙醚(9/1，v/v；100mL；B部分)、戊烷/乙醚(8/2，v/v；100mL；C部分)、戊烷/乙醚(7/3，v/v，100mL，D部分)、戊烷/乙醚(6/4，v/v；100mL；E部分)、戊烷/乙醚(4/6，v/v；100mL，F部分)、戊烷/乙醚(2/8、v/v；100mL；G部分)，然后应用乙醚(100ml，H部分)。分别收集B部分、D部分和G部分，用GC/MS分析。把其保留时间和质谱(EI、CI)同合成的参照化合物相比，B部分可以鉴定为5-MPC(101.3μg/kg)、D部分可以鉴定为3-MPC(9.4μg/kg)，G部分可以鉴定为DMPF(11.5μg/kg)。
实施例1：在矿泉水中应用5-甲基2-(1-吡咯烷基)-2-环戊烯-1-酮(5-MPC)和5-甲基-4-(1-吡咯烷基)-3(2H)-呋喃酮(MPF)
用VittelTM矿泉水分别稀释10％1-薄荷醇、5％5-MPC和10％MPF的乙醇溶液。然后品尝这些溶液，将其同纯净的VittelTM矿泉水比较。
样品                             味道
VittelTM                        中性芳香味和味道
含1-薄荷醇的VittelTM(10g/ml)    明显清凉效果，强的薄荷醇味
含5-MPC的VittelTM               明显清凉效果，弱的薄荷醇味
含MPC的VittelTM                 明显清凉效果，中性芳香味实施例2：柑橘汁中应用5-MPC和MPF
在柑橘汁中评价若干清凉物质。1-薄荷醇在20mg/L时产生强的冷却效果。其还显示强薄荷式芳香味、因此使该果汁中总味道不平衡。新的冷却化合物5-MPC，以200mg/L的浓度加入时，也显示强的清凉效果。除清凉效果外，其还显示弱薄荷醇型草芳香味，但味道没有1-薄荷醇明显。把MPF以1000mg/L加入到柑橘汁中，在口腔中产生明显的清凉效果，并且没有附加的芳香味。因此，MPF适合增加柑橘汁的清凉效果，并且不改变其芳香味道特性，这是应用1-薄荷醇所不能达到的效果。实施例3：在糖甜食中应用5-MPC和MPF
在烧杯中加入糖(100g)和水(15g)，将其置于电热板上加热。当混合物变成澄清溶液后，继续加热该糖浆直至因水分蒸发而变粘。然后分别加入5-MPC(20mg)和MPF(100mg)。把该粘性液体倾入到模中(3g/模)，使其冷却至室温。把从模中形成的糖果脱模，用于品尝。同不含清凉物质的对照品相比，分别含有5-MPC和MPF的两种糖果在口中具有明显的冷却效果。含有MPF的糖果不显示附加的味觉特点，同具有弱油腻和弱薄荷味的含5-MPC的糖果相比，其更优越些。实施例4：在冰淇淋中应用5-MPC
把全脂奶油(250g)、牛奶(250ml)和糖(100g)混合，搅拌直至糖溶解。然后把该混合物倾入到冰淇淋机器(II Gelataio Super，Sigmac Inc.，Gessate，意大利)的接受器中，搅拌下冷冻30分钟。通式，制备含有5-MPC(20mg/kg)的冰淇淋。含有5-MPC的冰淇淋显示明显长时间的冷却效果。这种冰淇淋的清凉新鲜感持续时间远远长于不加调味物质的对照品。实施例6：5-MPC、2(5H)-DMPF、2(5H)-MPF和MPF的局部测试
清凉化合物5-MPF、2(5H)-DMPF、2(5H)-MPF和MPF的阈值测量如下：把含有0.05、0.1、0.2、0.5或1.0％清凉剂的等量水溶液(0.5mL)加入到右前臂内侧、手腕和手肘之间中途表皮的圆形区域(10cm2)，然后摩擦1分钟。并列地，把等份(0.5ml)纯净自来水作为空白施加于左臂皮肤的区域。1分钟后，干燥皮肤。按照从0(无效果)到5(效果非常强)的清凉强度等级，请10个评委(男性和女性)进行评分。把两天三个不同实验所评价的值进行平均。各个值和独立实验值之间的差别不超过2分。
前臂内侧表面上5-MPC和MPF的局部测试
 浓度[％]                        冷却强度a
 2(5H)-MPF  2(5H)-DMPF  MPF  5-MPC
 0.00020  0  0  0
 0.00039  1  0  0
 0.00078  2  0  0
 0.00156  3  0  0
 0.00313  5  0  0
 0.00625  5  0  0  0
 0.0125  n.d.  1  0  0
 0.025  n.d.  3  0  0
 0.05  n.d.  5  1  0
 0.1  n.d.  5  2  0
 0.2  n.d.  5  4  1
 0.5  n.d.  5  5  3
 1.0  n.d.  5  5  5
a在自来水中测定皮肤的清凉效果，按照从0(无效果)至5(效果很强)的清凉强度等级进行局部测试评分。n.d.表示未检测出清凉效果。

Claims (10)

1、下列通式化合物单独或联合在食品、化妆品、药物和香料组合物中作为配料的应用，
Figure A0112481700021
其中：R1选自：
-N-吡咯烷基
-N-吡啶基
-N-(氨基-二乙基)
-N-(2-羧基-吡咯烷基)
-N-(2-甲氧基羰基-吡咯烷基)
R2选自：
-H
-甲基X选自：
-亚甲基
-亚乙基
-1-亚丙基
-氧基Y选自：
-亚甲基
-亚乙基
-1-亚丙基
-氧基
  -乙烷-1，2-二基
  -乙烯-1，2-二基
  -丙烷-1，2-二基
  -乙烷-1-氧-1-基。
2、权利要求1的应用，其中R1为N-吡咯烷基、R2为氢、X为亚甲基、Y为亚乙基。
3、权利要求1的应用，其中R1为N-吡咯烷基、R2为甲基、X为氧基和Y为亚甲基。
4、权利要求1的应用，其中R1为N-吡咯烷基、R2为甲基、X为亚甲基和Y为氧基。
5、权利要求1的应用，其中R1为N-吡咯烷基、R2为甲基、X为亚乙基、Y为氧基。
6、权利要求1—5任意一项的应用，其中食品组合物选自巧克力、冰淇淋、饮料、糖甜食和宠物食品。
7、权利要求1—5任意一项的应用，其中化妆品组合物选自所有局部用的化妆品组合物。
8、权利要求1—5任意一项的应用，其中香料组合物选自油基或水基组合物。
9、权利要求1—8任意一项的应用，其中通式(A)化合物单独或联合应用的用量为整个组合物的0.01-3000mg/kg。
10、通式(A)化合物单独或联合在产生清凉效果中的应用。
CN01124817A 2000-05-23 2001-05-23 α－酮烯胺衍生物作为配料的应用 Pending CN1334031A (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP00110886 2000-05-23
EP00110886.9 2000-05-23

Publications (1)

Publication Number Publication Date
CN1334031A true CN1334031A (zh) 2002-02-06

Family

ID=8168804

Family Applications (1)

Application Number Title Priority Date Filing Date
CN01124817A Pending CN1334031A (zh) 2000-05-23 2001-05-23 α－酮烯胺衍生物作为配料的应用

Country Status (13)

Country Link
US (1) US6592884B2 (zh)
JP (1) JP2002084990A (zh)
CN (1) CN1334031A (zh)
AT (1) ATE380474T1 (zh)
AU (1) AU781119B2 (zh)
BR (1) BR0102083A (zh)
CA (1) CA2348301A1 (zh)
DE (1) DE60131804D1 (zh)
HU (1) HUP0102160A3 (zh)
NZ (1) NZ511903A (zh)
PL (1) PL347668A1 (zh)
SG (1) SG108255A1 (zh)
ZA (1) ZA200104188B (zh)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102203073A (zh) * 2009-02-02 2011-09-28 波兰纽克大学有机化学学院 烯氨羰基化合物及其用途
CN103783658A (zh) * 2014-01-21 2014-05-14 杨成云 一种电子烟液香料的制备方法
CN110981862A (zh) * 2019-12-11 2020-04-10 中国烟草总公司郑州烟草研究院 一种化合物及其合成方法、应用、烟草制品
CN111004224A (zh) * 2019-12-11 2020-04-14 中国烟草总公司郑州烟草研究院 一种环甲位烯胺酮类化合物及其合成方法、应用、烟草制品

Families Citing this family (91)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20010018579A1 (en) 1998-12-18 2001-08-30 Walter Klemp Disposable absorbent garment having stretchable side waist regions
AU2002361809A1 (en) * 2001-12-19 2003-07-09 Vector Tobacco Inc. Method and compositions for imparting cooling effect to tobacco products
US20050137166A1 (en) * 2003-12-19 2005-06-23 Alcon, Inc. Use of cooling agents to relieve mild ocular irritation and enhance comfort
US20050153014A1 (en) * 2004-01-09 2005-07-14 Farnham William F. Creamy alcoholic beverages and methods for making same
US20060029628A1 (en) * 2004-04-23 2006-02-09 Joerg Kleinwaechter Use of a volatile cooling sensate on fibrous tissues to provide a sensation of rhinological decongestion
US8343534B2 (en) * 2004-04-23 2013-01-01 The Procter & Gamble Company Tissue including a volatile rhinological composition
US20070148284A1 (en) 2004-08-25 2007-06-28 Cadbury Adams Usa Llc. Liquid-filled chewing gum
AU2005323206C1 (en) 2005-01-04 2010-01-07 Teikoku Pharma Usa, Inc. Cooling topical patch preparation
EP1940377A4 (en) 2005-10-24 2010-12-08 Teikoku Pharma Usa Inc TOPICAL AEROSPECTIVE COMPOSITIONS OF N, 2,3-TRIMETHYL-2-ISOPROPYLBUTAMIDE AND METHOD OF USE THEREOF
US7432413B2 (en) 2005-12-16 2008-10-07 The Procter And Gamble Company Disposable absorbent article having side panels with structurally, functionally and visually different regions
US8057450B2 (en) 2006-03-31 2011-11-15 The Procter & Gamble Company Absorbent article with sensation member
US8491558B2 (en) 2006-03-31 2013-07-23 The Procter & Gamble Company Absorbent article with impregnated sensation material for toilet training
US8664467B2 (en) 2006-03-31 2014-03-04 The Procter & Gamble Company Absorbent articles with feedback signal upon urination
CN102871802B (zh) 2006-12-04 2016-06-01 宝洁公司 包括图形的吸收制品
CN100551908C (zh) * 2007-07-20 2009-10-21 云南瑞升烟草技术（集团）有限公司 α-酮基烯胺衍生物凉味剂(5-MPC)的合成方法及其应用
CN101883499A (zh) * 2007-11-29 2010-11-10 吉百利亚当斯美国有限责任公司 具有活性物的多区咀嚼型胶基糖
CA2717044C (en) 2008-02-27 2013-08-27 Cadbury Adams Usa Llc Multi-region confectionery
EP2484220A1 (en) 2008-05-02 2012-08-08 Kraft Foods Global Brands LLC Sugar free mannitol confectionery and methods of making same
CN102438463A (zh) 2009-01-22 2012-05-02 卡夫食品环球品牌有限责任公司 糖食加工
US8632342B2 (en) * 2009-05-28 2014-01-21 Nike, Inc. Training system for an article of footwear
EP2459152A2 (en) 2009-07-30 2012-06-06 The Procter & Gamble Company Oral care article
EP3689150A1 (en) 2009-10-08 2020-08-05 Intercontinental Great Brands LLC Co-extruded layered candy and gum apparatus and methods
EP2316279B1 (en) 2009-10-30 2013-10-09 Intercontinental Great Brands LLC Sugar free confectionery; methods of making same; and use in preparing multilayered confectionery.
WO2011084760A2 (en) 2009-12-21 2011-07-14 Kraft Foods Global Brands Llc Particulate coating compositions, coated confectionery, and methods of making the same
WO2011163152A1 (en) 2010-06-25 2011-12-29 Kraft Foods Global Brands Llc Enhanced release of lipophilic ingredients from chewing gum with hydrocolloids
US20120014883A1 (en) 2010-07-19 2012-01-19 Douglas Craig Scott Compositions Comprising Derivatives Of Essential Oil Compounds And Use In Personal Care Products
MX349338B (es) 2010-10-01 2017-07-21 The Procter & Gamble Company * Composiciones para el cuidado bucal con sabor mejorado.
ES2673730T3 (es) 2010-10-01 2018-06-25 The Procter & Gamble Company Composiciones para el cuidado bucal con dulzor mejorado
WO2012112515A1 (en) 2011-02-14 2012-08-23 Kraft Foods Global Brands Llc Confectionary with multiple flavors and textures
US20140295024A1 (en) 2011-02-23 2014-10-02 Intercontinental Great Brands Llc Flavor pre-blends for chewing gum, methods of making flavor pre-blends and chewing gum compositions thereof
PL2683251T3 (pl) 2011-03-11 2021-12-13 Intercontinental Great Brands Llc Sposób wytwarzania wielowarstwowych wyrobów cukierniczych
CN108925737A (zh) 2011-07-21 2018-12-04 洲际大品牌有限责任公司 用于形成和冷却咀嚼型胶基糖的系统和方法
US20130042482A1 (en) 2011-08-16 2013-02-21 Valerie Jean Bradford Skin Engaging Member Comprising An Anti-Irritation Agent
WO2013033090A1 (en) 2011-09-01 2013-03-07 The Procter & Gamble Company Oral care compositions with improved rheology
WO2013170433A1 (en) 2012-05-15 2013-11-21 The Procter & Gamble Company Absorbent article having characteristic waist end
US20130315843A1 (en) 2012-05-25 2013-11-28 The Procter & Gamble Company Composition for reduction of trpa1 and trpv1 sensations
PL2861083T3 (pl) 2012-06-19 2019-04-30 Intercontinental Great Brands Llc Pakowana luzem, niepowlekana guma do żucia
US20150201644A1 (en) 2012-08-22 2015-07-23 Intercontinental Great Brands Llc Chewing gum compositions and methods of making thereof
AU2013323689B2 (en) 2012-09-28 2016-09-22 The Gillette Company Llc A skin engaging shaving aid member comprising at least one thermally resilient sensate
RU2664731C2 (ru) 2012-09-28 2018-08-22 Дзе Жиллетт Компани Контактирующий с кожей элемент, содержащий по меньшей мере одно термоустойчивое вещество, оказывающее сенсорное воздействие
WO2014128566A2 (en) 2013-02-21 2014-08-28 Mondelez International Chewing gum and methods of making thereof field
US10278408B2 (en) 2013-03-29 2019-05-07 Intercontinental Great Brands Llc Transparent and transluscent liquid filled candy; process of making thereof; sugar-free liquid edible composition; and use thereof
CN105283082A (zh) 2013-05-31 2016-01-27 洲际大品牌有限责任公司 具有硬质无定形内含物的咀嚼型胶基糖及其制备方法
WO2015051056A1 (en) 2013-10-02 2015-04-09 Intercontinental Great Brands Llc Particulate coated chewing gum and confectionery; and methods of making the same
US9884130B2 (en) 2013-11-13 2018-02-06 The Procter & Gamble Company Compositions for delivery of oral comfort sensations
MX2016011170A (es) 2014-02-27 2016-12-16 Procter & Gamble Composiciones para el cuidado bucal con una percepcion reducida de sabor amargo.
ES2953728T3 (es) 2014-02-28 2023-11-15 Intercontinental Great Brands Llc Método para recubrir núcleos comestibles y el uso de un método para limitar la adherencia de los núcleos comestibles a la pared interior del tambor
US10334867B2 (en) 2014-03-03 2019-07-02 Intercontinental Great Brands Llc Method for manufacturing a comestible
US20150273711A1 (en) 2014-03-26 2015-10-01 The Gillette Company Razor Comprising A Molded Shaving Aid Composition Comprising A Thermally Resilient Sensate
US20150272847A1 (en) 2014-03-26 2015-10-01 The Gillette Company Skin Engaging Shaving Aid Comprising A Thermally Resilient Sensate And A TRPA1 Receptor Inhibitor
BR112016024691A2 (pt) 2014-04-23 2017-08-15 Procter & Gamble ciclo-hexanocarboxamida com propriedades de resfriamento
MX2016014941A (es) 2014-05-15 2017-04-11 Intercontinental Great Brands Llc Goma de mascar multitexturada y metodos para su fabricacion.
AU2015301965B2 (en) 2014-08-15 2018-10-04 The Procter & Gamble Company Oral care compositions and regimens
CA2956964C (en) 2014-08-15 2019-07-16 The Procter & Gamble Company Oral care compositions with an enhanced sensory experience
EP3180092A1 (en) 2014-08-15 2017-06-21 The Procter and Gamble Company Dentifrice with incremental chemistries
SG11201703353RA (en) 2014-11-26 2017-06-29 Gillette Co Llc A skin engaging member comprising ethylene vinyl acetate
US9951295B2 (en) 2015-02-19 2018-04-24 The Procter & Gamble Company Compositions for deposition on biological surfaces
BR112017021315A2 (pt) 2015-04-09 2018-06-26 Procter & Gamble redução da aversão ao sabor de cpc através da redução da ativação de cpc dos receptores de trpa1, receptores de tprv1, ou ambos
AU2016342264A1 (en) 2015-10-22 2018-04-05 The Procter & Gamble Company Synthesis of cyclohexane carboxamide derivatives useful as sensates in consumer products
CA3000021C (en) 2015-10-22 2020-10-13 The Procter & Gamble Company Method of separating stereoisomers using supercritical fluid chromatography
BR112018012071A2 (pt) 2015-12-18 2018-11-27 Procter & Gamble síntese de derivados de éster de ciclo-hexano úteis como elementos sensoriais nos produtos destinados ao consumidor
BR112018069979A2 (pt) 2016-04-01 2019-02-05 Procter & Gamble composições para tratamento bucal contendo nitrato de potássio e peróxido
WO2017173197A1 (en) 2016-04-01 2017-10-05 The Procter & Gamble Company Oral care compositions containing a gel network phase and potassium nitrate
CA3018555A1 (en) 2016-04-01 2017-10-05 The Procter & Gamble Company Oral care compositions containing a gel network phase
CA3018559A1 (en) 2016-04-01 2017-10-05 The Procter & Gamble Company Oral care compositions with an effective flavor display
CA3018598A1 (en) 2016-04-01 2017-10-05 The Procter & Gamble Company Oral care compositions containing gel networks and potassium nitrate
US20170334082A1 (en) 2016-05-18 2017-11-23 The Gillette Company Llc Skin Engaging Member Comprising Ethylene Vinyl Acetate
US11198972B2 (en) 2016-10-25 2021-12-14 The Procter & Gamble Company Fibrous structures
CA3037098C (en) 2016-10-25 2023-01-17 The Procter & Gamble Company Differential pillow height fibrous structures
EP3535028A1 (en) 2016-11-03 2019-09-11 The Gillette Company LLC Skin engaging member comprising ethylene vinyl acetate
US10898425B2 (en) 2016-11-17 2021-01-26 The Gillette Company Llc Skin engaging member comprising ethylene vinyl acetate and a fragrance
ES2968660T3 (es) 2017-02-06 2024-05-13 Intercontinental Great Brands Llc Producto de confitería con textura doble; y métodos para elaborar el mismo
ES2969320T3 (es) 2017-06-05 2024-05-17 Perfetti Van Melle Benelux B V Composiciones de goma de mascar y métodos para su fabricación
DK3668326T3 (da) 2017-08-18 2024-01-08 Perfetti Van Melle Benelux B V Tyggegummisammensætninger og fremgangsmåder til fremstilling deraf
WO2019078185A1 (ja) 2017-10-16 2019-04-25 高砂香料工業株式会社 ２，２，６－トリメチルシクロヘキサンカルボン酸誘導体を含有する冷感剤組成物
DE102017127776A1 (de) * 2017-11-24 2019-05-29 Henkel Ag & Co. Kgaa Hydrolyselabile Heterocyclen von Riechstoffketonen oder -aldehyden
CN112867400A (zh) 2018-10-26 2021-05-28 洲际大品牌有限责任公司 中心填充的糖食产品、带包衣的产品以及制备方法
WO2020248229A1 (en) 2019-06-14 2020-12-17 The Procter & Gamble Company Leave-on oral care compositions
WO2020248239A1 (en) 2019-06-14 2020-12-17 The Procter & Gamble Company Leave-on oral care compositions
WO2020248232A1 (en) 2019-06-14 2020-12-17 The Procter & Gamble Company Leave-on oral care compositions
AU2020327947B2 (en) 2019-08-14 2023-11-23 Intercontinental Great Brands Llc Confectionery chip product; and methods of making the same
WO2021168696A1 (en) 2020-02-26 2021-09-02 The Procter & Gamble Company Oral care compositions for gum health
WO2021168684A1 (en) 2020-02-26 2021-09-02 The Procter & Gamble Company Oral care compositions for gum health
CA3190969A1 (en) 2020-09-28 2022-03-31 The Procter & Gamble Company Oral care composition comprising hops and flavor
WO2022072605A1 (en) 2020-09-30 2022-04-07 Lubrizol Advanced Materials, Inc. Oral care compositions with improved stability
CN116322343A (zh) 2020-10-09 2023-06-23 洲际大品牌有限责任公司 未包裹的硬糖果产品、异麦芽酮糖醇糖食、其制备方法和用途
WO2022241412A1 (en) 2021-05-11 2022-11-17 The Procter & Gamble Company Oral care compositions comprising block copolymer
WO2023023886A1 (en) 2021-08-23 2023-03-02 The Procter & Gamble Company Oral care compositions for gum health
CA3229223A1 (en) 2021-08-23 2023-03-02 The Procter & Gamble Company Oral care compositions for gum health
WO2023191852A1 (en) 2022-03-28 2023-10-05 Lubrizol Advanced Materials, Inc. Stable dentifrice compositions with high sodium bicarbonate loading
WO2023248187A1 (en) 2022-06-24 2023-12-28 Nicoventures Trading Limited Oral composition comprising a receptor modulator

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH464182A (de) * 1965-03-31 1968-10-31 Givaudan & Cie Sa Verfahren zur Herstellung von Cyclopentenonen
GB1514910A (en) * 1974-07-02 1978-06-21 Unilever Ltd Amadori compounds and their use to flavour foods
JPH07242661A (ja) * 1994-03-04 1995-09-19 Shiono Koryo Kk 小麦粉食品の加熱香気を有する香料化合物ならびに香料組成物

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102203073A (zh) * 2009-02-02 2011-09-28 波兰纽克大学有机化学学院 烯氨羰基化合物及其用途
CN102203073B (zh) * 2009-02-02 2014-06-25 波兰纽克大学有机化学学院 烯氨羰基化合物及其用途
CN103783658A (zh) * 2014-01-21 2014-05-14 杨成云 一种电子烟液香料的制备方法
CN110981862A (zh) * 2019-12-11 2020-04-10 中国烟草总公司郑州烟草研究院 一种化合物及其合成方法、应用、烟草制品
CN111004224A (zh) * 2019-12-11 2020-04-14 中国烟草总公司郑州烟草研究院 一种环甲位烯胺酮类化合物及其合成方法、应用、烟草制品
CN111004224B (zh) * 2019-12-11 2021-03-12 中国烟草总公司郑州烟草研究院 一种环甲位烯胺酮类化合物及其合成方法、应用、烟草制品
CN110981862B (zh) * 2019-12-11 2021-03-12 中国烟草总公司郑州烟草研究院 一种化合物及其合成方法、应用、烟草制品

Also Published As

Publication number Publication date
JP2002084990A (ja) 2002-03-26
AU781119B2 (en) 2005-05-05
US6592884B2 (en) 2003-07-15
HU0102160D0 (en) 2001-07-30
US20020022039A1 (en) 2002-02-21
ATE380474T1 (de) 2007-12-15
PL347668A1 (en) 2001-12-03
NZ511903A (en) 2002-12-20
CA2348301A1 (en) 2001-11-23
HUP0102160A2 (hu) 2002-05-29
ZA200104188B (en) 2002-11-22
AU4619401A (en) 2001-11-29
DE60131804D1 (de) 2008-01-24
HUP0102160A3 (en) 2003-09-29
BR0102083A (pt) 2002-03-19
SG108255A1 (en) 2005-01-28

Similar Documents

Publication Publication Date Title
CN1334031A (zh) α－酮烯胺衍生物作为配料的应用
JP2615345B2 (ja) 呈味改善剤及び呈味改善方法
US9642381B2 (en) Orally consumable formulations comprising certain sweet-tasting triterpenes and triterpene glycosides
EP1901618B1 (en) Hydroxyphenylalkadiones and their use for masking bitter taste and/or for intensifying sweet taste
US20060249167A1 (en) Flavor ingredients for cooling preparations
EP2334201B1 (en) Thiol-containing fragrance and flavor materials
JP2008537951A (ja) ホットフレーバーおよび皮膚感覚組成物
EP0605261B1 (en) Use of a flavone derivative as taste modifier and a method of modifying taste
JP5224234B2 (ja) 血小板凝集抑制剤
US20120165552A1 (en) 7,10,13-cyclohexadecatrien-16-olide, and flavor or fragrance composition, fragrance or cosmetic product, food product or beverage or toiletry product comprising the same
DE102009002268A1 (de) 4,4'-Dihydroxydeoxybenzoine und deren Verwendung als Geschmacksverbesserer
KR101685829B1 (ko) 항산화 활성이 증진된 겨우살이 추출 발효물의 제조방법
US3769293A (en) Oxazoline flavoring agents and flavor extenders
US20090069551A1 (en) Flavorant Compounds
EP1157617A2 (en) Use of alpha-keto enamine derivatives as ingredients
US20040052828A1 (en) Consumable product including consumable component and alpha-keto enamine derivatives
JP2008079557A (ja) （−）−４β，１０α−アロマデンドランジオールを含有する呈味改善剤
JP2987365B1 (ja) 抗酸化剤
JP4953627B2 (ja) アラキドン酸代謝抑制剤
JP2002322191A (ja) セサミノール配糖体、その製造方法及び抗酸化剤
JP2006219471A (ja) アラキドン酸代謝抑制剤
JP2009091262A (ja) カルシウム拮抗剤
JP5527736B2 (ja) 血小板凝集抑制剤
EP4212025A1 (en) Mouth-coating feel enhancer
EP1240832A2 (en) Antibacterial agent

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication