維基百科

冰片

化合物

冰片（分子式：C10H18O），又名片腦、桔片、龍腦香、梅花冰片、羯布羅香、梅花腦、冰片腦、梅冰、龍腦、瑞腦、腦子、天然冰片、老梅片、梅片、莰醇等，是由2個異戊二烯結構單元組成的環狀化合物，屬於單萜衍生物[1]。根據旋光性分為左旋龍腦（(-)-龍腦）和右旋龍腦（(+)-龍腦）[2]。右旋龍腦主要來源於龍腦樟和陰香樹[3]，而左旋龍腦主要來源於菊科植物[4]。《中國藥典》中右旋者來自樟枝葉，左旋者來自艾納香。[5]

冰片
冰片
IUPAC名
endo-1,7,7-Trimethyl- bicyclo[2.2.1]heptan-2-ol
識別
CAS號 507-70-0  checkY
464-43-7（(+)）  checkY
464-45-9（(-)）  checkY
PubChem 6552009
ChemSpider 5026296
SMILES
 
  • CC1(C2(C)C)C(O)CC2CC1
InChI
 
  • 1/C10H18O/c1-9(2)7-4-5-10(9,3)8(11)6-7/h7-8,11H,4-6H2,1-3H3/t7-,8+,10+/m1/s1
InChIKey DTGKSKDOIYIVQL-WEDXCCLWBQ
ChEBI 15393
KEGG C01411
IUPHAR配體 6413
性質
化學式 C10H18O
密度 1.011 g/cm3 @ 20oC
熔點 208°C
沸點 易升華
危險性
歐盟危險性符號
有害有害 Xn
易燃易燃 F
警示術語 R：R33-R36/37/38
安全術語 S：S26-S37
MSDS 英文MSDS
若非註明，所有數據均出自標準狀態（25 ℃，100 kPa）下。

合成

生物合成

冰片的合成前體由細胞質中的甲羥戊酸途徑和質體中的4-磷酸-2-甲基赤蘚糖途徑產生的異戊烯基焦磷酸和二甲基烯丙基焦磷酸合成[6]。在香葉基焦磷酸合酶的催化作用下，這些合成物縮合生成香葉基焦磷酸[7]，隨後在二磷酸龍腦合酶的作用下環化成二磷酸龍腦，最終在鹼性磷酸酶的作用下脫去磷酸基團生成龍腦[2]。

冰片的手性具體取決於二磷酸龍腦合酶偏好的手性。目前已知一個二磷酸左旋龍腦合成酶的序列和多個二磷酸右旋龍腦合成酶的序列。[8]

此外，龍腦在龍腦脫氫酶的催化作用下被氧化成樟腦[9]。

人工合成

冰片極易被氧化成酮而生成樟腦，人工合成方法是通過Meerwein–Ponndorf–Verley還原反應將樟腦還原成冰片。中國所謂「合成冰片」是以消旋樟腦為起點，得到的冰片和異冰片的消旋混合物，實際操作中還可能有未反應的樟腦雜質[5]。「半合成冰片」則是以單獨一個手性的樟腦開始：(+)-樟腦還原可得(+)-冰片和(-)-異冰片[10]。

加入硼氫化鈉可以加快反應速率，使反應成為不可逆反應，但是產物也由於動力學控制變成異冰片。

 
樟腦被還原成異冰片

利用

冰片被認為具有抗菌、保護心腦血管、鎮痛消炎、防止血栓、促進藥物透過血腦屏障等多種作用[11]。常應用於臨床治療，作為止痛劑、鎮痛劑和麻醉劑[12]。

中國有依達拉奉/右莰醇複方藥，其中右莰醇就是右旋冰片。有注射液、舌下含片版本，批准用來改善急性缺血性腦卒中後遺症，號稱比單獨依達拉奉更有效。[13][14]

毒性

冰片具有劑量毒性，大量使用會引起毒性反應。[15]

參考資料

  1. ^ Wang, Hong; Ma, Dongming; Yang, Jinfen; Deng, Ke; Li, Meng; Ji, Xiaoyu; Zhong, Liting; Zhao, Haiying. An Integrative Volatile Terpenoid Profiling and Transcriptomics Analysis for Gene Mining and Functional Characterization of AvBPPS and AvPS Involved in the Monoterpenoid Biosynthesis in Amomum villosum. Frontiers in Plant Science. 2018-06-20, 9. doi:10.3389/fpls.2018.00846. 
  2. ^ 2.0 2.1 Chen, Changjie; Miao, Yuhuan; Luo, Dandan; Wang, Zixin; Guo, Lujuan; Zhao, Tingting; Liu, Dahui. Cloning and Functional Verification of the Borneol Dehydrogenase Encoding Gene AArBDH1 in Artemisia argyi. Chinese Bulletin of Botany. 2023-07-01, 58 (4): 560. doi:10.11983/CBB22123. 
  3. ^ Xingxing, Liu; Xi, Zhang; Xiali, Guo; Shangji, Gong; Xiangmei, Jiang; Yuxin, Fu; Liping, Luo. Multivariate Analyses of Volatile Chemical Composition in Leaves of Different Cinnamomum camphora Chemotypes. Chinese Bulletin of Botany. 2014, 49 (2): 161. doi:10.3724/SP.J.1259.2014.00161. 
  4. ^ Ho, Tsung-Jung; Hung, Chien-Che; Shih, Tzenge-Lien; Yiin, Lih-Ming; Chen, Hao-Ping. Investigation of borneols sold in Taiwan by chiral gas chromatography. Journal of Food and Drug Analysis. 2018-01, 26 (1): 348–352. doi:10.1016/j.jfda.2016.10.012. 
  5. ^ 5.0 5.1 中国药典第一部 2020.  右旋 左旋 合成
  6. ^ 徐應文; 呂季娟; 吳衛; 鄭有良. 植物单萜合酶研究进展. 生態學報. 2009, 29 (6): 3188–3197 [2024-03-10]. ISSN 1000-0933. CNKI STXB200906052. （原始內容存檔於2024-03-10）. 
  7. ^ 趙圓圓; 孫葉雯; 鄭詩敏; 李萌; 馬東明; 楊錦芬. 阳春砂龙脑基二磷酸合酶关键氨基酸位点筛选及突变体的构建. 中草藥. 2022, 53 (2): 529–537 [2024-03-10]. doi:10.7501/j.issn.0253-2670.2022.02.023. CNKI ZCYO202202022. （原始內容存檔於2024-03-10）. 
  8. ^ Ma, Rui; Su, Ping; Ma, Qing; Guo, Juan; Chen, Suiqing; Jin, Baolong; Zhang, Haiyan; Tang, Jinfu; Zhou, Tao; Xiao, Chenghong; Cui, Guanghong; Huang, Luqi. Identification of (-)-bornyl diphosphate synthase from Blumea balsamifera and its application for (-)-borneol biosynthesis in Saccharomyces cerevisiae. Synthetic and Systems Biotechnology. 2022-03, 7 (1): 490–497. PMC 8671873  . PMID 34977393. doi:10.1016/j.synbio.2021.12.004. 
  9. ^ Hurd, Matthew C.; Kwon, Moonhyuk; Ro, Dae-Kyun. Functional identification of a Lippia dulcis bornyl diphosphate synthase that contains a duplicated, inhibitory arginine-rich motif. Biochemical and Biophysical Research Communications. 2017-08, 490 (3): 963–968. doi:10.1016/j.bbrc.2017.06.147. 
  10. ^ Yang, Ming‐Yeh; Khine, Aye Aye; Liu, Jen‐Wei; Cheng, Hui‐Chen; Hu, Anren; Chen, Hao‐Ping; Shih, Tzenge‐Lien. Resolution of isoborneol and its isomers by GC/MS to identify “synthetic” and “semi‐synthetic” borneol products. Chirality. November 2018, 30 (11): 1233–1239. doi:10.1002/chir.23017. 
  11. ^ Ma, Rui; Su, Ping; Guo, Juan; Jin, Baolong; Ma, Qing; Zhang, Haiyan; Chen, Lingli; Mao, Liuying; Tian, Mei; Lai, Changjiangsheng; Tang, Jinfu; Cui, Guanghong; Huang, Luqi. Bornyl Diphosphate Synthase From Cinnamomum burmanni and Its Application for (+)-Borneol Biosynthesis in Yeast. Frontiers in Bioengineering and Biotechnology. 2021-02-11, 9. doi:10.3389/fbioe.2021.631863. 
  12. ^ Khine, Aye Aye; Lu, Pei-Chieh; Ko, Tzu-Ping; Huang, Kai-Fa; Chen, Hao-Ping. Cloning, expression, identification and characterization of borneol dehydrogenase isozymes in Pseudomonas sp. TCU-HL1. Protein Expression and Purification. 2020-11, 175: 105715. doi:10.1016/j.pep.2020.105715. 
  13. ^ 先聲藥業. 先必新 依达拉奉右莰醇舌下片说明书 (PDF). 
  14. ^ Xu, Jie; Wang, Anxin; Meng, Xia; Yalkun, Gulbahram; Xu, Anding; Gao, Zhiqiang; Chen, Huisheng; Ji, Yong; Xu, Jun; Geng, Deqin; Zhu, Runxiu; Liu, Bo; Dong, Aiqin; Mu, Hua; Lu, Zhihong; Li, Shuya; Zheng, Huaguang; Chen, Xia; Wang, Yilong; Zhao, Xingquan; Wang, Yongjun; Wang, Yongjun; Xu, Anding; Zhao, Xingquan; Chen, Xia; Wang, Yongjun; Meng, Xia; Wang, Yilong; Xu, Jie; Wang, Anxin; Zheng, Huaguang; Gao, Zhiqiang; Duan, Lei; Zhang, Jinghua; Li, Shuya; Lou, Donghua; Gao, Zhiqiang; Chen, Huisheng; Ji, Yong; Xu, Jun; Geng, Deqin; Zhu, Runxiu; Liu, Bo; Dong, Aiqin; Liang, Qingcheng; Yang, Hong; Guo, Cunju; Li, Xin; He, Mingli; Tian, Xiangyang; Cui, Yong; Zhou, Junshan; Wang, Ning; Wang, Lei; Zhang, Xinjiang; Gao, Xiaoping; Lu, Liping; Li, Tong; Cheng, Yan; Liu, Kaixiang; Xi, Xiaokun; Wang, Baojun; Sun, Lin; Zhao, Shigang; Chu, Xiaofan; Lian, Yajun; Yan, Fuling; Wang, Xiaoshan; Wang, Dong; Shao, Bei; Jiao, Jinsong; Wu, Heng; Li, Guanglai; Guo, Libin; Wang, Yongjun; Pan, Suyue; Xu, Anding; Li, Heng; Zhuang, Jianhua; Li, Xin; Wu, Jun; Wang, Anxin; Lou, Donghua; Zuo, Yingting; Zhang, Yijun; Zhang, Xiaoli; Feng, Xiaofei; Meng, Xia; Wang, David; Dong, Kehui; Liu, Yanfang; Li, Hao; Chen, Dawei; Lv, Qiushi. Edaravone Dexborneol Versus Edaravone Alone for the Treatment of Acute Ischemic Stroke: A Phase III, Randomized, Double-Blind, Comparative Trial. Stroke. March 2021, 52 (3): 772–780. PMID 33588596. doi:10.1161/STROKEAHA.120.031197. 
  15. ^ Material Safety Data Sheet, Fisher Scientific. [2022-10-01]. （原始內容存檔於2022-10-04）. 

外部連結

取自「https://zh.wikipedia.org/w/index.php?title=冰片&oldid=85427700」