CN101528272A - 恶臭冲消组合物 - Google Patents
恶臭冲消组合物 Download PDFInfo
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- CN101528272A CN101528272A CNA2007800397283A CN200780039728A CN101528272A CN 101528272 A CN101528272 A CN 101528272A CN A2007800397283 A CNA2007800397283 A CN A2007800397283A CN 200780039728 A CN200780039728 A CN 200780039728A CN 101528272 A CN101528272 A CN 101528272A
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- chemical compound
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- ethyl
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- 239000000203 mixture Substances 0.000 title claims abstract description 68
- 150000001875 compounds Chemical class 0.000 claims abstract description 94
- -1 methoxyl group Chemical group 0.000 claims description 21
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 21
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 16
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 15
- 229920002554 vinyl polymer Polymers 0.000 claims description 9
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Natural products OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- GLZPCOQZEFWAFX-UHFFFAOYSA-N KU0063794 Natural products CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 claims description 7
- 239000005792 Geraniol Substances 0.000 claims description 6
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 claims description 6
- NGHOLYJTSCBCGC-UHFFFAOYSA-N cis-cinnamic acid benzyl ester Natural products C=1C=CC=CC=1C=CC(=O)OCC1=CC=CC=C1 NGHOLYJTSCBCGC-UHFFFAOYSA-N 0.000 claims description 6
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 6
- 239000001530 fumaric acid Substances 0.000 claims description 6
- 229940113087 geraniol Drugs 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- NGHOLYJTSCBCGC-VAWYXSNFSA-N benzyl cinnamate Chemical compound C=1C=CC=CC=1/C=C/C(=O)OCC1=CC=CC=C1 NGHOLYJTSCBCGC-VAWYXSNFSA-N 0.000 claims description 4
- 239000002537 cosmetic Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 229940114081 cinnamate Drugs 0.000 claims description 2
- UPQZOUHVTJNGFK-UHFFFAOYSA-N diethyl 2-methylpropanedioate Chemical compound CCOC(=O)C(C)C(=O)OCC UPQZOUHVTJNGFK-UHFFFAOYSA-N 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- NBFNGRDFKUJVIN-VAWYXSNFSA-N phenyl (e)-3-phenylprop-2-enoate Chemical compound C=1C=CC=CC=1/C=C/C(=O)OC1=CC=CC=C1 NBFNGRDFKUJVIN-VAWYXSNFSA-N 0.000 claims description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 claims 1
- 239000000047 product Substances 0.000 description 25
- YYPNJNDODFVZLE-UHFFFAOYSA-N 3-methylbut-2-enoic acid Chemical compound CC(C)=CC(O)=O YYPNJNDODFVZLE-UHFFFAOYSA-N 0.000 description 15
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 15
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical class CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 13
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- 239000007788 liquid Substances 0.000 description 11
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- QPBVYDIIQIYFQO-UHFFFAOYSA-N 3,7-dimethyloct-6-enyl prop-2-enoate Chemical compound CC(C)=CCCC(C)CCOC(=O)C=C QPBVYDIIQIYFQO-UHFFFAOYSA-N 0.000 description 8
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- 208000035985 Body Odor Diseases 0.000 description 6
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- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
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- 235000002639 sodium chloride Nutrition 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
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- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 3
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- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 240000004784 Cymbopogon citratus Species 0.000 description 2
- 235000017897 Cymbopogon citratus Nutrition 0.000 description 2
- 241000628997 Flos Species 0.000 description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 230000001166 anti-perspirative effect Effects 0.000 description 2
- 239000003213 antiperspirant Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000004494 ethyl ester group Chemical group 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- OSWPMRLSEDHDFF-UHFFFAOYSA-N methyl salicylate Chemical compound COC(=O)C1=CC=CC=C1O OSWPMRLSEDHDFF-UHFFFAOYSA-N 0.000 description 2
- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical compound COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- LEHBURLTIWGHEM-UHFFFAOYSA-N pyridinium chlorochromate Chemical compound [O-][Cr](Cl)(=O)=O.C1=CC=[NH+]C=C1 LEHBURLTIWGHEM-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- CMXPERZAMAQXSF-UHFFFAOYSA-M sodium;1,4-bis(2-ethylhexoxy)-1,4-dioxobutane-2-sulfonate;1,8-dihydroxyanthracene-9,10-dione Chemical compound [Na+].O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=CC=C2O.CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC CMXPERZAMAQXSF-UHFFFAOYSA-M 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- MGSRCZKZVOBKFT-UHFFFAOYSA-N thymol Chemical compound CC(C)C1=CC=C(C)C=C1O MGSRCZKZVOBKFT-UHFFFAOYSA-N 0.000 description 2
- RUVINXPYWBROJD-ONEGZZNKSA-N trans-anethole Chemical compound COC1=CC=C(\C=C\C)C=C1 RUVINXPYWBROJD-ONEGZZNKSA-N 0.000 description 2
- FQTLCLSUCSAZDY-UHFFFAOYSA-N (+) E(S) nerolidol Natural products CC(C)=CCCC(C)=CCCC(C)(O)C=C FQTLCLSUCSAZDY-UHFFFAOYSA-N 0.000 description 1
- NOOLISFMXDJSKH-UTLUCORTSA-N (+)-Neomenthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@@H]1O NOOLISFMXDJSKH-UTLUCORTSA-N 0.000 description 1
- CRDAMVZIKSXKFV-FBXUGWQNSA-N (2-cis,6-cis)-farnesol Chemical compound CC(C)=CCC\C(C)=C/CC\C(C)=C/CO CRDAMVZIKSXKFV-FBXUGWQNSA-N 0.000 description 1
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- 239000004405 propyl p-hydroxybenzoate Substances 0.000 description 1
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- QELSKZZBTMNZEB-UHFFFAOYSA-N propylparaben Chemical compound CCCOC(=O)C1=CC=C(O)C=C1 QELSKZZBTMNZEB-UHFFFAOYSA-N 0.000 description 1
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- 239000011746 zinc citrate Substances 0.000 description 1
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- 229940068475 zinc citrate Drugs 0.000 description 1
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Abstract
一种恶臭冲消组合物,包括至少一种式(A)的化合物和至少一种式(B)的化合物其中n、X、Y和R1-R4如说明书所定义。
Description
本发明涉及恶臭冲消组合物。更特别地,本发明涉及含有两种不同类羧酸酯的特定香料组合物。
恶臭是在空气中和在许多基质如织物、硬质表面、皮肤和头发上碰到的难闻的气味。恶臭起源于个人或者环境。例如汗、尿、和粪便的恶臭起源于个人,而厨房、汽油、烹饪、烟草烟尘等恶臭起源于环境。尽管个人的恶臭容易沉积在织物、头发和皮肤上,但环境的恶臭也具有沉淀在这些基质上的倾向。个人和环境恶臭的结合构成了复合的恶臭,其包括许多油溶性、水溶性以及固体组分,这些组分易挥发并且因此容易被人察觉。
已使用了几种方法冲消恶臭。这些方法包括通过用令人愉悦的较浓烈的气味叠加在恶臭上的屏蔽法,通过阻断恶臭嗅神经受体的交叉-适应法,通过与引起拉乌尔定律负向偏差的成分混合从而抑制恶臭的方法,通过化学反应消除恶臭的方法,通过多孔或笼状结构体吸收恶臭的方法,和通过诸如抗菌剂和酶抑制剂之类的路线避免恶臭形成的方法。尽管所有这些方法或多或少地有效,但目前仍需要更加有效的产品,该产品可以使得在最终产品中使用较低浓度的活性化合物。
现在发现将如例如WO02/051788和US4,305,930中描述的已知种类的恶臭冲消剂分子与所选种类的羧酸酯结合,产生非常有效的恶臭冲消剂组合物。令人吃惊地,如下在此描述的,两类分子的特定结合使冲消性能产生预想不到的协同增加。
因此,本发明一方面涉及一种组合物,包括
a)至少一种式(A)的化合物
其中
R1是直链或支化C1-C12烷基,例如乙基和己基,直链或支化C3-C12烯基,例如香茅基,C6-C11芳基,例如苯基,C7-C12芳烷基,例如苄基,或被至少一个O或N原子取代的C7-C12芳烷基;
R2是直链或支化C1-C10烷基,例如甲基、乙基和异丙基,C6-C10芳基,例如苯基,C7-C10烷氧基芳基,例如4-甲氧基苯基,C4-C10烷氧基羰基,例如己氧基羰基;
R4是氢或甲基;并且
R2和R4相对于酯基是E或Z构型;
和
b)至少一种式(B)的化合物
其中
n是0或1;
X选自二价残基-C(CH3)2-和-C(O)-;
Y选自二价残基-O-、-CH(CH3)-和-CH2-;
R3选自C1-C3烷基如甲基或乙基、C2-C3烯基如乙烯基、C3-C5环烷基如环丙基或环丁基、C1-C3烷氧基如甲氧基或乙氧基、和NR’R”,其中R’和R”相互独立地为氢、甲基或乙基;和
C-1与C-2、和C-1与C-6之间的键是单键;或C-1与C-2、和C-1与C-6之间的键中的一个与虚线一起表示双键。
在一个优选实施方式中,式(A)的化合物可以选自甲基巴豆酸香茅酯(=3-甲基丁-2-烯酸3,7-二甲基辛-6-烯基酯)、巴豆酸香叶酯、富马酸二己酯、肉桂酸苄基酯、肉桂酸苯基酯和2-乙基-己基-对甲氧基-肉桂酸酯(=辛基甲氧基肉桂酸酯)。
式(B)的化合物可以选自表1和表2中所列的化合物。
表1:式(B)的化合物,其中n是0。
化合物 | X= | R3= | C-1和C-2 | C-1和C-6 |
A | -C(CH3)2- | 甲基 | SB | SB |
B | -C(O)- | 甲基 | SB | SB |
C | -C(O)- | -O-C2H5 | SB | SB |
D | -C(CH3)2- | -O-C2H5 | SB | SB |
E | -C(CH3)2- | 乙基 | SB | SB |
SB=单键
表2:式(B)的化合物,其中n是1。
化合物 | X= | Y= | R3= | C-1和C-2 | C-1和C-6 |
1 | -C(CH3)2- | -O- | 乙基 | SB | SB |
2 | -C(O)- | -O- | 乙基 | SB | SB |
3 | -C(CH3)2- | -O- | 乙基 | DB | SB |
4 | -C(CH3)2- | -O- | 环丙基 | SB | SB |
5 | -C(O)- | -O- | 环丙基 | SB | SB |
6 | -C(CH3)2- | -O- | 环丙基 | DB | SB |
7 | -C(CH3)2- | -O- | 乙烯基 | SB | SB |
8 | -C(O)- | -O- | 乙烯基 | SB | SB |
9 | -C(CH3)2- | -O- | 乙烯基 | DB | SB |
10 | -C(CH3)2- | -CH2- | 甲基 | SB | SB |
11 | -C(O)- | -CH2- | 甲基 | SB | SB |
12 | -C(O)- | -CH2- | 甲氧基 | SB | SB |
13 | -C(O)- | -CH(CH3)- | 甲基 | SB | SB |
14 | -C(O)- | -CH(CH3)- | 甲氧基 | SB | SB |
15 | -C(O)- | -CH(CH3)- | -N(CH3)2 | SB | SB |
16 | -C(O)- | -CH2- | 乙氧基 | SB | SB |
SB=单键;DB=双键
如上文所描述的组合物优选包括式(A)化合物和式(B)化合物的混合物,二者的比例为约1∶99-约99∶1,优选90∶10-50∶50,例如80∶20(A∶B)。
本发明的组合物可以进一步包括其他恶臭冲消剂如恶臭中和剂和恶臭吸收剂。“恶臭中和剂”是指与恶臭化合物如特定胺、硫醇和短链脂族酸反应的材料或其混合物。它们可以优选选自醛如烷基醛、苯甲醛和香草醛;和环烷基叔醇如4-环己基-4-甲基-2-戊酮。“恶臭吸收剂”是指能够吸收恶臭的任何大表面积的材料。例如,这类恶臭吸收剂包括分子筛如沸石、二氧化硅、硅铝酸盐、环糊精、活性炭、粘土、干燥的柑橘渣、樱桃核提取物、玉米穗轴及其混合物。
本发明的组合物可以进一步包括延迟由细菌分解引起的恶臭增长率的成分,例如抗菌剂和酶抑制剂。例如,这类抗菌剂和酶抑制剂包括金属盐如柠檬酸锌、氧化锌、除虫菊酮锌、和octopirox;有机酸如山梨酸、苯甲酸及其盐;对羟基苯甲酸酯如对羟基苯酸甲酯、对羟基苯甲酸丙酯、对羟基苯甲酸丁酯、对羟基苯甲酸乙酯、对羟基苯甲酸异丙酯、对羟基苯甲酸异丁酯、对羟基苯甲酸苄酯及其盐;醇如苯甲醇、苯乙醇;硼酸;2,4,4’-三氯-2-羟基-二苯醚(TriclosanTM);酚类化合物如苯酚、2-甲基苯酚、4-乙基苯酚;精油如迷迭香、百里香、熏衣草、丁子香酚、天竺葵、茶树、丁香、柠檬草、薄荷油或它们的活性组分如茴香脑、麝香草酚、桉树脑、双三醇、薄荷醇、柠檬油精、水杨酸甲酯、水杨酸、萜品醇、橙花叔醇、香叶醇及其混合物。
任选地,如上定义的组合物,即包括至少一种式(A)化合物和至少一种式(B)化合物的组合物可以与已知的增香剂分子结合使用。例如,这类分子描述于“Perfume and Flavor Materials of Natural Origin”,S.Arctander,Ed.,Elizabeth,N.J.,1960;“Perfume and FlavorChemicals”,S.Arctander,Ed.,Vol.I & II,Allured PublishingCorporation,Carol Stream,USA,1994中。优选通常称为除臭剂香料组分的增香剂,如例如在US 4,663,068中公开的,在此将其引入作为参考。
也可以以本领域公认的量向本发明的组合物中添加助剂成分如溶剂、染料和抗氧剂。
用于本发明的溶剂可以是极性的,如乙醇、异丙醇、二甘醇单乙醚、一缩二丙二醇、邻苯二甲酸二乙酯、柠檬酸三乙酯和三甘醇,或非极性的,如豆蔻酸异丙酯和异链烷烃。可以将极性和非极性溶剂混合。可以选择极性和非极性溶剂的比例,从而提供适宜的应用性能和式(A)和式(B)化合物的释放速率,如上文所描述。
可以将本发明的组合物添加到多种消费产品中,如有香味或无香味的家用产品、个人护理产品和化妆品。
可以包括根据本发明组合物的家用产品包括织物洗涤粉和洗涤液、去垢剂、表面清洁剂(包括硬表面清洁剂)、空气清新剂、软化剂、漂白剂、织物清新剂和室内喷雾、消毒产品、洗净剂和猫砂。所列的家用产品是以说明的方式给出,不应将其视为以任何方式进行限制。
可以包括根据本发明组合物的个人护理产品和化妆品包括洗液,例如须后洗液、香波、调节剂、定型喷雾剂、摩丝、凝胶体、头发擦洗剂、发胶、发蜡、泡浴和淋浴凝胶、浴盐、卫生产品、除臭剂、止汗剂、雪花膏、脱毛剂、爽身粉和月经用品。所列的个人护理产品是以说明的方式给出,不应将其视为以任何方式进行限制。
典型地,基于该产品,产品包括约0.0001重量%-约20重量%,优选约0.001重量%-约10重量%的如上文所定义的至少一种式(A)化合物和至少一种式(B)化合物。有效量取决于混合物所混入的产品的类型。例如,如果用于织物清新剂中,它可以1重量%左右添加到香料组合物中,然后将香料组合物以0.1重量%左右添加到该产品中,即该织物清新剂包括约0.001重量%的如上文所描述的组合物。或者,在液电(liquid electrical)空气清新剂组合物中,基于空气清新剂组合物,其可以20重量%左右添加。
因此,本发明另一方面涉及一种消费产品,该消费产品包括有效恶臭冲消数量的包括至少一种式(A)化合物和至少一种式(B)化合物的组合物。
本发明另一方面在于从空气或从表面除去恶臭的方法,包括向那里施用有效量的包括如上文所描述的至少一种式(A)化合物和至少一种式(B)化合物的组合物。
本发明另一方面涉及增强消费产品的恶臭减少性能的方法,该消费产品如家用产品、个人护理产品和化妆品,包括向该产品混入如上文所描述的至少一种式(A)化合物和至少一种式(B)化合物。
尽管有些属于式(B)定义的化合物称作香料,但有些从未描述于文献中。
因此,本发明另一方面涉及一种式(B’)的化合物
其中
C-1与C-2、和C-1与C-6之间的键是单键;或C-1与C-2、和C-1与C-6之间的键中的一个与虚线一起表示双键;和
I)n是1;
X选自二价残基-C(CH3)2-和-C(O)-;
Y选自二价残基-CH(CH3)-和-CH2-;和
R3选自CH3、OCH3、OC2H5和N(CH3)2;
II)n是0;
X是-C(CH3)2-;
R3选自C1-C3烷基如甲基或乙基、C2-C3烯基如乙烯基、C3-C5环烷基如环丙基或环丁基、C1-C3烷氧基如甲氧基或乙氧基、或NR’R”,其中R’和R”相互独立地为氢、甲基或乙基;或
III)n是0;
X是-C(O)-;和
R3选自C2-C3烷基如甲基或异丙基、C2-C3烯基如乙烯基、C3-C5环烷基如环丙基或环丁基、甲氧基、和NR’R”,其中R’和R”相互独立地为氢、甲基或乙基;条件是不包括1-(3,3-二甲基环己基)乙基甲基丙二酸酯。
式(B’)的化合物包括至少一个手性中心,因而它们可以作为对映异构体和非对映异构体混合物而存在,或者它们可以拆分为对映异构和非对映异构纯形式。然而,拆分立体异构体增加了制备和纯化这些化合物的复杂性,因此仅仅出于经济原因,优选使用作为其立体异构体的混合物形式的式(B’)的化合物。然而,如果希望制备纯立体异构体,则可以根据本领域中已知的方法来实现。因此本发明另一方面涉及以其异构体任何一种形式和其混合物形式的式(B’)化合物。
在本领域技术人员已知的条件下,可以如方案1所示经由cyclademol(1-(3,3-二甲基环己基)乙醇)或其不饱和类似物(I)和适当的酸/酰氯(II)的酯化作用,或者如方案2所示从cyclademol/不饱和类似物(I)和适当的取代琥珀酸酐(III)制备其中X是-C(O)-的式(B’)化合物。
方案1:
方案2:
可以如方案3所示从cyclademol/不饱和类似物(I)和巴豆酸甲酯(IV其中R3=烷氧基)或异亚丙基酮(IV其中R3=烷基、烯基、环烷基(cycloylkyl))开始经由1,4-加成来制备其中X是-C(CH3)2-的式(B’)化合物。
方案3:
也可以根据如方案4所示的通用步骤制备式(B’)化合物,其中C-1与C-2、和C-1与C-6之间的键是单键并且Y是-CH(CH3)-或-CH2-。
方案4:
在方案1-4中,X、Y、n和R3具有如上面式(B)所指明的含义。在方案1-3中所表示的反应是常规反应,其特定条件详细描述于实施例中。
现在将参考以下非限制性实施例对本发明作进一步描述。这些实施例仅仅用于说明,并且应当理解本领域技术人员可以对其作出改变和改进。
在本申请中,术语“%”或“百分比”将是指重量%,除非上下文中明显指明不是。
实施例1:测定恶臭的减少潜能(potential)
在1升玻璃顶空(headspace)收集(collection)广口瓶内部放入25ml塞好的玻璃容器,该玻璃容器中含有0.5g如表3所示的试验化合物/化合物的混合物。将作为典型的恶臭的10μl己胺注入顶空广口瓶中。使其在25℃下经过15分钟达到平衡。通过TenaxTM顶空捕集器以1毫升/分钟抽取顶空1分钟。移除捕集器并分析,从而测定恶臭的起始浓度。从容器上移除玻璃塞并使试验组分与恶臭在25℃下接触60分钟。通过TenaxTM顶空捕集器以1毫升/分钟抽取顶空1分钟,从而测定恶臭的剩余量。使Tenax捕集器加热解吸到Agilent 6890GC/MS中,从而分析己胺的量。结果为下面表3所示。
表3:己胺的减少百分比
化合物/化合物混合物 | 己胺的减少% | |
1. | 甲基巴豆酸香茅酯 | 53.6 |
2. | 50%化合物450%甲基巴豆酸香茅酯 | 61.8 |
3. | 肉桂酸苄基酯 | 23.5 |
4. | 50%化合物450%肉桂酸苄基酯 | 61.4 |
5. | 辛基甲基肉桂酸酯 | 54.1 |
6. | 50%化合物450%辛基甲基肉桂酸酯 | 66.7 |
7. | 巴豆酸香叶酯 | 64.7 |
8. | 50%化合物450%巴豆酸香叶酯 | 78.4 |
9. | 富马酸二己酯 | 68.7 |
10. | 50%化合物450%富马酸二己酯 | 79.3 |
从以上结果可以看出,将化合物4即环丙烷甲酸2-[1-(3,3-二甲基环己基)乙氧基]-2-甲基丙基酯与类别A化合物结合使用显著增加了类别A化合物的有效性。
实施例2:测定不同化合物的恶臭减少潜能
遵循与实施例1中描述相同的方法,将根据式(B)的化合物与等量的甲基巴豆酸香茅酯混合。相对于作为典型恶臭的10μl己胺,测试0.5g得到的混合物。结果如以下表4所示。
表4:己胺的减少百分比
化合物/化合物混合物 | 己胺的减少% | |
1. | 甲基巴豆酸香茅酯 | 61.3 |
2. | 50%化合物1050%甲基巴豆酸香茅酯 | 72.4 |
3. | 50%化合物150%甲基巴豆酸香茅酯 | 64.4 |
4. | 50%化合物C50%甲基巴豆酸香茅酯 | 82.5 |
5. | 50%化合物750%甲基巴豆酸香茅酯 | 72.1 |
6. | 50%化合物450%甲基巴豆酸香茅酯 | 74.7 |
从以上结果可以看出,将式(B)化合物与类别A化合物即甲基巴豆酸香茅酯结合使用,显著增加了这种已知恶臭冲消剂分子的有效性。
实施例3:测定与已知恶臭冲消剂分子混合的化合物的恶臭减少
潜能
遵循与实施例1中描述相同的方法,将5-(1-(3,3-二甲基-环己基)乙氧基)-5-甲基己-2-酮(化合物10)与等量的式(A)化合物混合。相对于作为典型恶臭的10μl己胺,测试0.5g得到的混合物。结果如以下表5所示。
表5:己胺的减少百分比
化合物/化合物混合物 | 己胺的减少% | |
1. | 巴豆酸香叶酯 | 71.0 |
2. | 50%化合物1050%巴豆酸香叶酯 | 80.6 |
3. | 富马酸二己酯 | 78.1 |
4. | 50%化合物1050%富马酸二己酯 | 87.4 |
5. | 肉桂酸苄基酯 | 62.1 |
6. | 50%化合物1050%肉桂酸苄基酯 | 71.5 |
7. | 辛基甲基肉桂酸酯 | 58.7 |
8. | 50%化合物1050%辛基甲基肉桂酸酯 | 74.8 |
实施例4:测定不同混合物的恶臭减少潜能
以表6中所给出的比例制备每种式(A)化合物和式(B)化合物的试验混合物(10%乙醇溶液)。将0.5g 1%的合成狐臭剂的乙醇溶液放到棉垫上。将0.4g试验混合物的乙醇溶液分别放到各个狐臭剂处理的棉垫上。作为对照,对一个垫不进行处理。使各垫干燥15分钟。使试验棉垫随机化,使用5人专家组来测定恶臭的强度。要求每位小组成员使用Labeled Magnitude Scale(LMS)检查代表狐臭味强度的盒子(BarryG.Green,Pamela Dalton,Beverly Cowart,Greg Shaffer,KrystynaRankin和Jennifer Higgins)。Evaluating the Labeled MagnitudeScale for Measuring Sensations of Taste and Smell.Chemical Senses.第21卷,第323-334页,1996)。
恶臭的减少%计算:
减少%=(平均LMS对照物-平均LMS试验物)/平均LMS对照物
表6:狐臭味的减少百分比
%狐臭味减少 | |
20%化合物480%巴豆酸香叶酯 | 71.0 |
30%化合物470%巴豆酸香叶酯 | 71.3 |
100%甲基巴豆酸香茅酯 | 51.0 |
80%化合物1020%甲基巴豆酸香茅酯 | 71.3 |
50%化合物1050%甲基巴豆酸香茅酯 | 67.4 |
20%化合物1080%甲基巴豆酸香茅酯 | 58.2 |
实施例5:
使用实施例4中描述的感官测试比较Givaudan香料组合物(组合物A)和香料组合物(组合物B)的MOC效力,所述Givaudan香料组合物(组合物A)含有以20%溶解的一缩二丙二醇,所述香料组合物(组合物B)是采用10%的化合物4和巴豆酸香叶酯的混合物(1∶9)代替其中10%的一缩二丙二醇。结果为下面表7所示。
表7:狐臭味的减少
组合物A | 组合物B | |
恶臭减少% | 75.7 | 80.2 |
实施例6:5-[1’-(3”,3”-二甲基环己基)乙氧基]-5-甲基己-2-酮
将氯铬酸吡啶(15.6g,72.4mmol)一下掷到强力搅拌的(16.0g)的CH2Cl2(200mL)淤浆中。在20分钟内,添加可根据WO2002 096852获得的2-[1’-(3”,3”-二甲基环己基)乙氧基]-2-甲基丙-1-醇(15.0g,65.7mmol)的CH2Cl2(200mL)溶液中,在硅胶垫上过滤之前,在室温下将得到的反应混合物整夜搅拌,并使用CH2Cl2(2×100mL))洗涤滤饼。将洗液和滤液混合,并将溶剂在旋转蒸发器中减压除去。通过快速色谱(硅胶;戊烷/Et2O,19∶1;Rf=0.63)纯化得到的残留物,从而提供2-[1’-(3”,3”-二甲基环己基)乙氧基]-2-甲基丙醛(10.0g,67%),其为无色有臭味的液体。
在N2氛围下,将2-(二乙氧基磷酰基)乙酸乙酯(8.92g,39.8mmol)的DME(10mL)溶液在室温下逐滴添加到搅拌的95%NaH(1.00g,39.4mmol)的DME(40mL)悬浮液中,接着升温至45℃。在30分钟内逐滴加2-[1’-(3”,3”-二甲基环己基)乙氧基]-2-甲基丙醛(9.00g,39.8mmol)的DME(20mL)溶液之前,将反应混合物加热回流15分钟。在进一步整夜回流后,使反应混合物冷却到室温,并将其倾倒到冰(400g)上。在通过添加AcOH(2mL,34.9mmol)酸化之后,使用Et2O(3×400mL)萃取产品。将混合的乙醚萃取物用水(400mL)和盐水(200mL)洗涤,干燥(Na2SO4),并在旋转蒸发器中减压浓缩。通过快速色谱(硅胶;戊烷/Et2O,19∶1;Rf=0.41)纯化得到的残留物(11.5g),从而得到4-[1’-(3”,3”-二甲基环己基)乙氧基]-4-甲基戊-2-烯酸乙酯(10.9g,92%),其为无色液体。
将由此制备的4-[1’-(3”,3”-二甲基环己基)乙氧基]-4-甲基戊-2-烯酸乙酯(8.50g,28.7mmol)吸收在EtOH/水(1∶1,150mL)中,并在搅拌条件下添加NaOH颗粒(5.74g,143.6mmol)后,将得到的反应混合物整夜回流。然后将EtOH在旋转蒸发器中减压除去,并用水(500mL)稀释得到的残留物和用Et2O(2×500mL)洗涤。将洗液丢弃,用浓缩的H3PO4水溶液酸化水层,然后使用Et2O(3×500mL)萃取。将混合的有机萃取液干燥(Na2SO4)并在旋转蒸发器中减压蒸干,从而提供4-[1’-(3”,3”-二甲基环己基)-5-[1’-(3”,3”-二甲基环己基)乙氧基]-5-甲基己-3-烯-2-酮(600mg,2.25mmol)乙氧基]-4-甲基戊-2-烯酸(7.54g,98%)。
在0℃下在N2气氛下,将MeLi在Et2O的溶液(1.6M,14.0mL,22.4mL)逐滴添加到搅拌的4-[1’-(3”,3”-二甲基环己基)乙氧基]-4-甲基戊-2-烯酸(2.40g,8.94mmol)的Et2O(45mL)溶液中。在添加完后,移除冷水浴,并将反应混合物在搅拌下加热回流2小时。然后GC对照物指明转化完成,并因此移除热源和再次用冷水浴替换。在0℃下通过添加HCl水溶液(5N,20mL)将反应混合物淬火,然后用水(100ml)稀释。使用Et2O(2×300mL)萃取产品,并在旋转蒸发器中减压除去溶剂之前,将混合的乙醚萃取物用水(200mL)和盐水(100mL)洗涤。通过快速色谱(硅胶;戊烷/Et2O,19∶1;Rf=0.25)纯化得到的残留物(2.25g),从而提供5-[1’-(3”,3”二甲基环己基)乙氧基]-5-甲基己-3-烯-2-酮(1.25g,53%),其为无色有臭味的液体。
将5-[1’-(3”,3”-二甲基环己基)乙氧基]-5-甲基己-3-烯-2酮(600mg,2.25mmol)和10%Pd/C(100mg,0.09mmol)的EtOAC(10mL)悬浮液排空两次,并使用N2吹扫。使用H2进行两轮的吹扫和排空之后,在H2的正压力下将反应混合物在室温下整夜搅拌。在用GC检测到转化完成后,在垫上通过真空过滤除去催化剂之前,将反应烧瓶排空并使用N2吹扫。使用EtOAC(2×25mL)洗涤滤饼,并将洗液与滤液混合并在旋转蒸发器中减压浓缩。通过泡对泡(bulb-to-bulb)蒸馏纯化得到的残留物(570mg),从而在85-100℃/0.05mbar下提供标题的化合物(480mg,84%),其为无色有臭味的液体。
IR(ATR):v=1718(s,vC=O),1364/1383(s,δCH3),1072(s,vsC-O-C),1155/1135(m,vasC-O-C),1461(m,δC-H)cm-1。1H NMR(CDCl3):δ=0.70-0.85(m,1H,2”-Hb),0.86/0.87/0.89/0.90(4s,6H,3”-Me2),1.01/1.02(2d,J=6.5Hz,3H,2’H3),1.10/1.13(2s,6H,5-Me2),1.32-1.67(m,8H,1”-H,2”-Ha,4”-H2-6”-H2),1.72(t,J=7.0Hz,2H,4-H2),2.16(s,3H,1-H3),2.53(t,J=7.0Hz,2H,3-H2),3.32/3.33(2quint,J=6.5Hz,1H,1’-H).13C NMR(CDCl3):δ=19.2/19.4(2q,C-2’),22.2/22.3(2t,C-5”),24.5/24.6(2q,3”-Meax),25.6/25.7/26.1/26.2(4q,5-Me2),27.9/29.2(2t,C-6”),29.8/29.9(2q,C-1),30.5/30.6(2s,C-3”),33.5/33.6(2q,3”-Meeq),36.0/36.1(2t,C-4),38.6/38.7(2t,C-4”),39.2/39.3(2t,C-3),40.2/40.3(2d,C-1”),41.3/42.2(2t,C-2”),70.8/70.9(2d,C-1’),73.7/73.8(2s,C-5),209.2/209.3(2s,C-2).MS(70eV):m/z(%)=157(2)[C10H21O+],139(5)[C10H21O+-H2O],123(8)[C9H15 +],113(100)[C7H13O+],97(24)[C10H21O+-H2O-C3H6],69(38)[C5H9 +],55(28)[C4H7 +],43(87)[C3H5 +]。
气味描述:具有果香的麝香-玫瑰味型,梨型细微差别并且使人想起一些乙酸香叶酯。
Claims (13)
1.组合物,包括
a.至少一种式(A)的化合物
其中
R1是直链或支化C1-C12烷基、直链或支化C3-C12烯基、C6-C11芳基、C7-C12芳烷基、或被至少一个O或N原子取代的C7-C12芳烷基;
R2是直链或支化C1-C10烷基、C6-C10芳基、C7-C10烷氧基芳基、C4-C10烷氧基羰基;
R4是氢或甲基;并且
R2和R4相对于酯基是E或Z构型;
和
b.至少一种式(B)的化合物
其中
n是0或1;
X选自二价残基-C(CH3)2-和-C(O)-;
Y选自二价残基-O-、-CH(CH3)-和-CH2-;
R3选自C1-C3烷基、C2-C3烯基、C3-C5环烷基、C1-C3烷氧基、和NR’R”,其中R’和R”相互独立地为氢、甲基或乙基;和
C-1与C-2、和C-1与C-6之间的键是单键;或C-1与C-2、和C-1与C-6之间的键中的一个与虚线一起表示双键。
2.根据权利要求1的组合物,其中式(A)的化合物选自3-甲基丁-2-烯酸3,7-二甲基辛-6-烯基酯、巴豆酸香叶酯、富马酸二己酯、肉桂酸苄基酯、肉桂酸苯基酯和2-乙基-己基-对甲氧基-肉桂酸酯。
3.根据权利要求1或2的组合物,其中式(B)的化合物选自以下化合物,其中n是0,C-1与C-2、和C-1与C-6之间的键是单键,并且
X=-C(CH3)2-和R3=甲基;或
X=-C(O)-和R3=甲基;或
X=-C(O)-和R3=-O-C2H5;或
X=-C(CH3)2-和R3=-O-C2H5;或
X=-C(CH3)2-和R3=乙基。
4.根据权利要求1或2的组合物,其中式(B)的化合物选自以下化合物,其中n是1,C-1与C-2、和C-1与C-6之间的键是单键,并且
X=-C(CH3)2-,Y=-O-和R3=乙基;或
X=-C(O)-,Y=-O-和R3=乙基;或
X=-C(CH3)2-,Y=-O-和R3=环丙基;或
X=-C(O)-,Y=-O-和R3=环丙基;或
X=-C(CH3)2-,Y=-O-和R3=乙烯基;或
X=-C(O)-,Y=-O-和R3=乙烯基;或
X=-C(CH3)2-,Y=-CH2-和R3=甲基;或
X=-C(O)-,Y=-CH2-和R3=甲基;或
X=-C(O)-,Y=-CH2-和R3=甲氧基;或
X=-C(O)-,Y=-CH(CH3)-和R3=甲基;或
X=-C(O)-,Y=-CH(CH3)-和R3=甲氧基;或
X=-C(O)-,Y=-CH(CH3)-和R3=-N(CH3)2;或
X=-C(O)-,Y=-CH2-和R3=乙氧基。
5.根据权利要求1或2的组合物,其中式(B)的化合物选自以下化合物,其中n是1,C-1与C-6之间的键是单键,C-1与C-2之间的键和虚线一起是双键,X是-C(CH3)2-,Y是-O-和R3是乙基、乙烯基或环丙基。
6.根据上述权利要求任一项的组合物,另外包括至少一种增香剂。
7.消费产品,包括有效量的如权利要求1-6中任一项所定义的组合物。
8.根据权利要求7的消费产品,其中该消费产品选自家用产品、个人护理产品和化妆品。
9.从空气或从表面除去恶臭的方法,包括向那里施加有效量的如权利要求1-6任一项中所定义的组合物。
10.增强消费产品的恶臭减少性能的方法,包括向该产品中混入如权利要求1中所定义的至少一种式(A)的化合物和至少一种式(B)的化合物。
11.式(B’)的化合物
其中
C-1与C-2、和C-1与C-6之间的键是单键;或C-1与C-2、和C-1与C-6之间的键中的一个与虚线一起表示双键;和
I)n是1;
X选自二价残基-C(CH3)2-和-C(O)-;
Y选自二价残基-CH(CH3)-和-CH2-;和
R3选自CH3、OCH3、OC2H5和N(CH3)2;
II)n是0;
X是-C(CH3)2-;
R3选自C1-C3烷基、C2-C3烯基、C3-C5环烷基、C1-C3烷氧基、和NR’R”,其中R’和R”相互独立地为氢、甲基或乙基;或
III)n是0;
X是-C(O)-;和
R3选自C2-C3烷基、C2-C3烯基、C3-C5环烷基、甲氧基、和NR’R”,其中R’和R”相互独立地为氢、甲基或乙基;条件是不包括1-(3,3-二甲基环己基)乙基甲基丙二酸酯。
12.根据权利要求11的化合物,其中式(B’)的化合物选自以下化合物,其中n是0,C-1与C-2、和C-1与C-6之间的键是单键,并且
X=-C(CH3)2-和R3=甲基;或
X=-C(CH3)2-和R3=-O-C2H5;或
X=-C(CH3)2-和R3=乙基。
13.根据权利要求11的化合物,其中式(B’)的化合物选自以下化合物,其中n是1,C-1与C-2、和C-1与C-6之间的键是单键,并且
X=-C(CH3)2-,Y=-CH2-和R3=甲基;或
X=-C(O)-,Y=-CH2-和R3=甲基;或
X=-C(O)-,Y=-CH2-和R3=甲氧基;或
X=-C(O)-,Y=-CH(CH3)-和R3=甲基;或
X=-C(O)-,Y=-CH(CH3)-和R3=甲氧基;或
X=-C(O)-,Y=-CH(CH3)-和R3=-N(CH3)2;或
X=-C(O)-,Y=-CH2-和R3=乙氧基。
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EP (1) | EP2079487A1 (zh) |
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CN102379918A (zh) * | 2011-10-26 | 2012-03-21 | 延安常泰药业有限责任公司 | 地椒挥发油在制备治疗腋臭药物中的应用 |
CN102872467A (zh) * | 2012-10-12 | 2013-01-16 | 苏州谷力生物科技有限公司 | 一种除臭剂 |
CN110755284A (zh) * | 2019-11-08 | 2020-02-07 | 奥伦国际有限公司 | 除臭留香的组合物 |
CN111333509A (zh) * | 2020-04-14 | 2020-06-26 | 东莞波顿香料有限公司 | 苹果风味化合物及其制备方法和食品添加剂 |
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US3493650A (en) * | 1966-05-13 | 1970-02-03 | Universal Oil Prod Co | Perfume and deodorizing with citronellyl senecioate |
US5559271A (en) * | 1995-07-26 | 1996-09-24 | Phillips Petroleum Company | Organic polysulfide compositions having reduced odor |
ATE231834T1 (de) * | 1998-09-09 | 2003-02-15 | Firmenich & Cie | Ester mit moschusgeruch und ihre anwendung in der parfümerie |
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EP1262474A1 (en) * | 2001-06-01 | 2002-12-04 | Givaudan SA | Cycloalkanecarboxylic acid derivatives as fragrants with musk characteristics |
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GB0227807D0 (en) * | 2002-11-29 | 2003-01-08 | Givaudan Sa | Improvements in or relating ot organic compounds |
ES2265618T3 (es) * | 2003-03-19 | 2007-02-16 | Firmenich Sa | Compuestos odorantes. |
-
2007
- 2007-10-22 MX MX2009004132A patent/MX2009004132A/es not_active Application Discontinuation
- 2007-10-22 EP EP07816205A patent/EP2079487A1/en not_active Withdrawn
- 2007-10-22 CN CNA2007800397283A patent/CN101528272A/zh active Pending
- 2007-10-22 WO PCT/CH2007/000522 patent/WO2008049257A1/en active Application Filing
- 2007-10-22 US US12/444,752 patent/US20100034766A1/en not_active Abandoned
- 2007-10-22 JP JP2009533635A patent/JP2010507414A/ja active Pending
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Cited By (6)
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CN102872467A (zh) * | 2012-10-12 | 2013-01-16 | 苏州谷力生物科技有限公司 | 一种除臭剂 |
CN110755284A (zh) * | 2019-11-08 | 2020-02-07 | 奥伦国际有限公司 | 除臭留香的组合物 |
CN111333509A (zh) * | 2020-04-14 | 2020-06-26 | 东莞波顿香料有限公司 | 苹果风味化合物及其制备方法和食品添加剂 |
CN111333509B (zh) * | 2020-04-14 | 2022-06-10 | 东莞波顿香料有限公司 | 苹果风味化合物及其制备方法和食品添加剂 |
CN112089636A (zh) * | 2020-10-16 | 2020-12-18 | 广州博氏化妆品有限公司 | 除臭组合物及其制备方法和应用 |
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