环十五酮

环十五酮
识别
CAS号	502-72-7
PubChem	10409
SMILES	C1CCCCCCCCCCCCCC1=O;
EC编号	207-951-2
性质
化学式	C15H28O
摩尔质量	224.38 g·mol−1
外观	无色或白色针状晶体
气味	强烈麝香
密度	0.897 g·cm−3
熔点	63—65 °C（336—338 K）
沸点	120 °C（393 K）（0.3 mmHg）
溶解性（水）	0.5989 mg/L
溶解性	与乙醇、苯混溶，可溶于丙酮
危险性
	致死量或浓度：
LD50（中位剂量）	>5000 mg·kg−1（兔子，经皮给药（英语：Transdermal））
	若非注明，所有数据均出自标准状态（25 ℃，100 kPa）下。

环十五酮是一种环酮，也是大环化合物，化学式C₁₅H₂₈O。它的结构与麝香酮相似，两者只差一个甲基。它存在于大灵猫的臭腺（英语：Scent gland）中。^[5]^[6]

制备

环十五酮最早由拉沃斯拉夫·鲁日奇卡于1926年通过加热分解十六烷二酸的钍盐合成，产率只有2%。^[7]在此之后也有用噻吩^[8]或环十二酮^[9]开始的合成方法。

性质

环十五酮是有强烈麝香的无色或白色针状晶体，难溶于水。^[1]它的晶体结构已用晶体X射线衍射表征，15个碳原子基本共面，羰基中的氧原子则位于此平面外。环十五酮呈单斜晶系，空间群P2₁/c（No. 14），晶格参数 a = 15.6634 Å、b = 5.5531 Å、c = 17.6928 Å 、β = 116.315°。^[10]

反应

环十五酮经过与乙二醇反应生成缩酮，用苯基三甲基三溴化铵溴化，经DBN 脱溴，再用酸水解，最终与甲基溴化镁在氯化亚铜存在下反应，生成麝香酮。^[11]

用处

环十五酮可用作香水的芳香味化合物和固定剂，^[12]^[13]也存在于肥皂、洗发精等个人护理产品中。^[14]全球每年都会有几十吨的环十五酮应用于此。^[12]

毒性

环十五酮造成的健康风险非常小。给大鼠口服5 g/kg的环十五酮，以及给小鼠口服10 g/kg的环十五酮都没有出现毒性。^[4]环十五酮不刺激皮肤^[4]，没有基因毒性和光毒性，在埃姆斯试验中不表现为突变原。^[12]

参考资料

^ ^1.0 ^1.1 ^1.2 ^1.3 ^1.4 Api, A.M.; Belsito, D.; Botelho, D.; Bruze, M.; Burton, G.A.; Buschmann, J.; Cancellieri, M.A.; Dagli, M.L.; Date, M.; Dekant, W.; Deodhar, C.; Fryer, A.D.; Jones, L.; Joshi, K.; Kumar, M.; Lapczynski, A.; Lavelle, M.; Lee, I.; Liebler, D.C.; Moustakas, H.; Na, M.; Penning, T.M.; Ritacco, G.; Romine, J.; Sadekar, N.; Schultz, T.W.; Selechnik, D.; Siddiqi, F.; Sipes, I.G.; Sullivan, G.; Thakkar, Y.; Tokura, Y. RIFM fragrance ingredient safety assessment, cyclopentadecanone, CAS Registry Number 502-72-7. Food and Chemical Toxicology. 2021, 156: 112474. doi:10.1016/j.fct.2021.112474.
^ ^2.0 ^2.1 来源：Sigma-Aldrich Co., product no. C111201 .
^ Lide, David R. CRC Handbook of Chemistry and Physics. CRC Press. 1995-03-09: 3-142. ISBN 978-0-8493-0595-5.
^ ^4.0 ^4.1 ^4.2 McGinty, D.; Letizia, C.s.; Api, A.M. Fragrance material review on cyclopentadecanone. Food and Chemical Toxicology. 2011, 49: S142–S148. doi:10.1016/j.fct.2011.07.041.
^ Buckingham, John. Dictionary of Natural Products, Supplement 2. London: CRC Press. 1995-12-07: 68. ISBN 978-0-412-60420-1.
^ Danute Pajaujis Anonis. Civet and civet compounds (PDF). Perfumer & flavorist. 1997 [2024-01-17]. （原始内容存档 (PDF)于2024-01-18）.
^ Sytniczuk, Adrian; Leszczyńska, Agnieszka; Kajetanowicz, Anna; Grela, Karol. Preparation of Musk‐Smelling Macrocyclic Lactones from Biomass: Looking for the Optimal Substrate Combination. ChemSusChem. 2018-09-21, 11 (18): 3157–3166. ISSN 1864-5631. doi:10.1002/cssc.201801463.
^ Taits, S. Z.; Gol'dfarb, Ya. L. A new synthesis of cyclopentadecanone (exaltone). Bulletin of the Academy of Sciences of the USSR Division of Chemical Science. 1960, 9 (9): 1574–1576. ISSN 0568-5230. doi:10.1007/BF00909832.
^ Nozaki, H.; Mori, T.; Noyori, R. A novel synthesis of cyclopentadecanone from cyclododecanone. Tetrahedron Letters. 1967, 8 (9): 779–780. doi:10.1016/S0040-4039(00)71561-9.
^ Noe, Eric A.; Pawar, Diwakar M.; Fronczek, Frank R. Cyclopentadecanone. Acta Crystallographica Section C Crystal Structure Communications. 2008-02-15, 64 (2): o67–o68. ISSN 0108-2701. doi:10.1107/S0108270107066139.
^ Mookherjee, B. D.; Patel, R. R.; Ledig, W. O. Synthesis of dl-muscone from exaltone (cyclopentadecanone). The Journal of Organic Chemistry. 1971, 36 (26): 4124–4125. ISSN 0022-3263. doi:10.1021/jo00825a024.
^ ^12.0 ^12.1 ^12.2 Api, A.M.; Belsito, D.; Botelho, D.; Bruze, M.; Burton, G.A.; Buschmann, J.; Cancellieri, M.A.; Dagli, M.L.; Date, M.; Dekant, W.; Deodhar, C.; Fryer, A.D.; Jones, L.; Joshi, K.; Kumar, M.; Lapczynski, A.; Lavelle, M.; Lee, I.; Liebler, D.C.; Moustakas, H.; Na, M.; Penning, T.M.; Ritacco, G.; Romine, J.; Sadekar, N.; Schultz, T.W.; Selechnik, D.; Siddiqi, F.; Sipes, I.G.; Sullivan, G.; Thakkar, Y.; Tokura, Y. RIFM fragrance ingredient safety assessment, cyclopentadecanone, CAS Registry Number 502-72-7. Food and Chemical Toxicology. 2021, 156: 112474. doi:10.1016/j.fct.2021.112474.
^ Eisenbrand, Gerhard; Schreier, Peter. RÖMPP Lexikon Lebensmittelchemie, 2. Auflage, 2006. Georg Thieme Verlag. 2014-05-28: 386. ISBN 978-3-13-179532-8 （德语）.
^ Nakata, Haruhiko; Hinosaka, Mari; Yanagimoto, Hayato. Macrocyclic-, polycyclic-, and nitro musks in cosmetics, household commodities and indoor dusts collected from Japan: Implications for their human exposure. Ecotoxicology and Environmental Safety. 2015, 111: 248–255. doi:10.1016/j.ecoenv.2014.09.032.

[:2-1] 1.0 ^1.1 ^1.2 ^1.3 ^1.4 Api, A.M.; Belsito, D.; Botelho, D.; Bruze, M.; Burton, G.A.; Buschmann, J.; Cancellieri, M.A.; Dagli, M.L.; Date, M.; Dekant, W.; Deodhar, C.; Fryer, A.D.; Jones, L.; Joshi, K.; Kumar, M.; Lapczynski, A.; Lavelle, M.; Lee, I.; Liebler, D.C.; Moustakas, H.; Na, M.; Penning, T.M.; Ritacco, G.; Romine, J.; Sadekar, N.; Schultz, T.W.; Selechnik, D.; Siddiqi, F.; Sipes, I.G.; Sullivan, G.; Thakkar, Y.; Tokura, Y. RIFM fragrance ingredient safety assessment, cyclopentadecanone, CAS Registry Number 502-72-7. Food and Chemical Toxicology. 2021, 156: 112474. doi:10.1016/j.fct.2021.112474.

[Sigma-2] 2.0 ^2.1 来源：Sigma-Aldrich Co., product no. C111201 .

[David_R._Lide-3] Lide, David R. CRC Handbook of Chemistry and Physics. CRC Press. 1995-03-09: 3-142. ISBN 978-0-8493-0595-5.

[:3-4] 4.0 ^4.1 ^4.2 McGinty, D.; Letizia, C.s.; Api, A.M. Fragrance material review on cyclopentadecanone. Food and Chemical Toxicology. 2011, 49: S142–S148. doi:10.1016/j.fct.2011.07.041.

[Dict-5] Buckingham, John. Dictionary of Natural Products, Supplement 2. London: CRC Press. 1995-12-07: 68. ISBN 978-0-412-60420-1.

[:1-6] Danute Pajaujis Anonis. Civet and civet compounds (PDF). Perfumer & flavorist. 1997 [2024-01-17]. （原始内容存档 (PDF)于2024-01-18）.

[7] Sytniczuk, Adrian; Leszczyńska, Agnieszka; Kajetanowicz, Anna; Grela, Karol. Preparation of Musk‐Smelling Macrocyclic Lactones from Biomass: Looking for the Optimal Substrate Combination. ChemSusChem. 2018-09-21, 11 (18): 3157–3166. ISSN 1864-5631. doi:10.1002/cssc.201801463.

[8] Taits, S. Z.; Gol'dfarb, Ya. L. A new synthesis of cyclopentadecanone (exaltone). Bulletin of the Academy of Sciences of the USSR Division of Chemical Science. 1960, 9 (9): 1574–1576. ISSN 0568-5230. doi:10.1007/BF00909832.

[9] Nozaki, H.; Mori, T.; Noyori, R. A novel synthesis of cyclopentadecanone from cyclododecanone. Tetrahedron Letters. 1967, 8 (9): 779–780. doi:10.1016/S0040-4039(00)71561-9.

[10] Noe, Eric A.; Pawar, Diwakar M.; Fronczek, Frank R. Cyclopentadecanone. Acta Crystallographica Section C Crystal Structure Communications. 2008-02-15, 64 (2): o67–o68. ISSN 0108-2701. doi:10.1107/S0108270107066139.

[11] Mookherjee, B. D.; Patel, R. R.; Ledig, W. O. Synthesis of dl-muscone from exaltone (cyclopentadecanone). The Journal of Organic Chemistry. 1971, 36 (26): 4124–4125. ISSN 0022-3263. doi:10.1021/jo00825a024.

[:0-12] 12.0 ^12.1 ^12.2 Api, A.M.; Belsito, D.; Botelho, D.; Bruze, M.; Burton, G.A.; Buschmann, J.; Cancellieri, M.A.; Dagli, M.L.; Date, M.; Dekant, W.; Deodhar, C.; Fryer, A.D.; Jones, L.; Joshi, K.; Kumar, M.; Lapczynski, A.; Lavelle, M.; Lee, I.; Liebler, D.C.; Moustakas, H.; Na, M.; Penning, T.M.; Ritacco, G.; Romine, J.; Sadekar, N.; Schultz, T.W.; Selechnik, D.; Siddiqi, F.; Sipes, I.G.; Sullivan, G.; Thakkar, Y.; Tokura, Y. RIFM fragrance ingredient safety assessment, cyclopentadecanone, CAS Registry Number 502-72-7. Food and Chemical Toxicology. 2021, 156: 112474. doi:10.1016/j.fct.2021.112474.

[Alfred_Hagen_Meyer-13] Eisenbrand, Gerhard; Schreier, Peter. RÖMPP Lexikon Lebensmittelchemie, 2. Auflage, 2006. Georg Thieme Verlag. 2014-05-28: 386. ISBN 978-3-13-179532-8 （德语）.

[14] Nakata, Haruhiko; Hinosaka, Mari; Yanagimoto, Hayato. Macrocyclic-, polycyclic-, and nitro musks in cosmetics, household commodities and indoor dusts collected from Japan: Implications for their human exposure. Ecotoxicology and Environmental Safety. 2015, 111: 248–255. doi:10.1016/j.ecoenv.2014.09.032.

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