borneol
{{Short description|Chemical compound}}
{{chembox
| Watchedfields = changed
| verifiedrevid = 458641115
| Name = Borneol
| ImageFileL1 = Borneol.svg
| ImageSizeL1 = 140px
| ImageFileR1 = (-)-Borneol.svg
| ImageSizeR1 = 140px
| ImageFileL2 = (+)-borneol-based-on-xtal-3D-bs-17.png
| ImageNameL2 = (+)-Borneol
| ImageSizeL2 = 140px
| ImageFileR2 = (−)-borneol-based-on-xtal-3D-bs-17.png
| ImageNameR2 = (-)-Borneol
| ImageSizeR2 = 140px
| ImageCaption = (+)-Borneol (left images) and (-)-borneol (right)
| IUPACName = rel-(1R,2S,4R)-1,7,7-Trimethylbicyclo[2.2.1]heptan-2-ol
| OtherNames = 1,7,7-Trimethylbicyclo[2.2.1]heptan-2-endo-ol
endo-2-Bornanol, Borneo camphor
| SystematicName =
| Section1 = {{Chembox Identifiers
| IUPHAR_ligand = 6413
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
| ChemSpiderID = 5026296
| ChEMBL_Ref = {{ebicite|correct|EBI}}
| ChEMBL = 486208
| PubChem = 6552009
| 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
| StdInChI_Ref = {{stdinchicite|correct|chemspider}}
| StdInChI = 1S/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
| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}
| StdInChIKey = DTGKSKDOIYIVQL-WEDXCCLWSA-N
| CASNo = 507-70-0
| CASNo_Ref = {{cascite|correct|CAS}}
| CASNo_Comment = (+/-)
| KEGG_Ref = {{keggcite|correct|kegg}}
| KEGG = C01411
| UNII_Ref = {{fdacite|correct|FDA}}
| UNII = M89NIB437X
| ChEBI_Ref = {{ebicite|correct|EBI}}
| ChEBI = 15393
| EC_number = 207-352-6
| UNNumber = 1312
| SMILES = O[C@H]1C[C@H]2CC[C@]1(C)C2(C)C
}}
| Section2 = {{Chembox Properties
| C=10 | H=18 | O=1
| Appearance = colorless to white lumps
| Odor = pungent, camphor-like
| Density = 1.011 g/cm3 (20 °C){{RubberBible86th|page=3.56}}
| MeltingPtC = 208
| BoilingPtC = 213
| Solubility = slightly soluble (D-form)
| SolubleOther = soluble in chloroform, ethanol, acetone, ether, benzene, toluene, decalin, tetralin
| MagSus = {{val|-1.26|e=-4|u=cm3/mol}} }}
| Section3 = {{Chembox Hazards
| GHSPictograms = {{GHS02}}
| GHSSignalWord = Warning
| HPhrases = {{H-phrases|228}}
| PPhrases = {{P-phrases|210|240|241|280|370+378}}
| NFPA-H = 2 | NFPA-F = 2 | NFPA-R = 0
| FlashPtC = 65
| ExternalSDS = [https://fscimage.fishersci.com/msds/33824.htm External MSDS]
}}
| Section4 =
| Section5 =
| Section6 =
| Section8 = {{Chembox Related
| OtherCompounds = Bornane (hydrocarbon)
}}
}}
Borneol is a bicyclic organic compound and a terpene derivative. The hydroxyl group in this compound is placed in an endo position. The exo diastereomer is called isoborneol. Being chiral, borneol exists as enantiomers, both of which are found in nature: d-borneol (also written (+)-borneol) and l-borneol (or (−)-borneol).
Reactions
Occurrence
The compound was named in 1842 by the French chemist Charles Frédéric Gerhardt.{{cite journal|first=C. |last=Gerhardt |date=1842 |title=Sur la transformation de l'essence de valériane en camphre de Bornéo et en camphre des laurinées |trans-title=On the transformation of the essence of valerian into Borneo camphor and into laurel camphor |journal=Comptes rendus |volume=14 |page=832–835}}
[http://gallica.bnf.fr/ark:/12148/bpt6k2973d/f838.item.r=.zoom From p. 834]: "Je donne, par cette raison, à l'hydrogène carboné de l'essence de valériane, le nom de bornéène, et, au camphre lui-même, celui de bornéol." (I give, for this reason [namely, that the compound that Gerhardt had obtained from valerian oil was identical to that obtained by Pelouze from camphor from Borneo], to the hydrocarbon from valerian essence, the name bornéène, and, to camphor itself, that of borneol.) Borneol can be found in several species of Heterotheca,{{cite journal|last1=Lincoln |first1=D. E. |first2=B. M. |last2=Lawrence |date=1984 |title=The volatile constituents of camphorweed, Heterotheca subaxillaris |journal=Phytochemistry |volume=23 |issue=4 |page=933–934}} Artemisia, Rosmarinus officinalis (rosemary){{cite journal |pmid=24584866|year=2013 |last1=Begum |first1=A. |last2=Sandhya |first2=S. |last3=Shaffath Ali |first3=S. |last4=Vinod |first4=K. R. |last5=Reddy |first5=S. |last6=Banji |first6=D. |title=An in-depth review on the medicinal flora Rosmarinus officinalis (Lamiaceae) |journal=Acta Scientiarum Polonorum: Technologia Alimentaria |volume=12 |issue=1 |pages=61–73 }} Dipterocarpaceae, Blumea balsamifera and Kaempferia galanga.{{cite journal | last1 = Wong | first1 = K. C. | last2 = Ong | first2 = K. S. | last3 = Lim | first3 = C. L. | title = Composition of the essential oil of rhizomes of Kaempferia galanga L. | journal = Flavour and Fragrance Journal | year = 2006 | volume = 7 | issue = 5 | pages = 263–266 | doi = 10.1002/ffj.2730070506 }}
It is one of the chemical compounds found in castoreum. This compound is gathered from the beaver's plant food.The Beaver: Its Life and Impact. Dietland Muller-Schwarze, 2003, page 43 ([https://books.google.com/books?id=HZ5WjXB5Pr8C&pg=PA43 book at google books])
=Synthesis=
Borneol can be synthesized by reduction of camphor by the Meerwein–Ponndorf–Verley reduction (a reversible process). Industrially, a racemic mixture of camphor is used, leading to a racemic mixture of borneol and isoborneol. The chirality can be controlled by changing the chirality of camphor: (+)-camphor gives (−)-isoborneol and (+)-borneol.{{cite journal |last1=Yang |first1=Ming-Yeh |last2=Khine |first2=Aye Aye |last3=Liu |first3=Jen-Wei |last4=Cheng |first4=Hui-Chen |last5=Hu |first5=Anren |last6=Chen |first6=Hao-Ping |last7=Shih |first7=Tzenge-Lien |title=Resolution of isoborneol and its isomers by GC/MS to identify "synthetic" and "semi-synthetic" borneol products |journal=Chirality |date=November 2018 |volume=30 |issue=11 |pages=1233–1239 |doi=10.1002/chir.23017|pmid=30222211 }}
Reduction of camphor with sodium borohydride (fast and irreversible) gives instead the diastereomer isoborneol.
=Natural sources=
Industrially, natural (+)-borneol is produced from Cinnamomum burmanni (one specific chemotype){{cite journal |last1=Li |first1=Fangping |last2=Huang |first2=Shilin |last3=Mei |first3=Yu |last4=Wu |first4=Bingqi |last5=Hou |first5=Zhuangwei |last6=Zhan |first6=Penglin |last7=Hou |first7=Zhihao |last8=Huang |first8=Wenjie |last9=Zhao |first9=Junliang |last10=Wang |first10=Jihua |title=Genome assembly provided new insights into the Cinnamomum burmannii evolution and D-borneol biosynthesis differences between chemotypes |journal=Industrial Crops and Products |date=October 2022 |volume=186 |pages=115181 |doi=10.1016/j.indcrop.2022.115181}} and Cinnamomum camphora.{{cite journal |last1=Xingxing |first1=Liu |last2=Xi |first2=Zhang |last3=Xiali |first3=Guo |last4=Shangji |first4=Gong |last5=Xiangmei |first5=Jiang |last6=Yuxin |first6=Fu |last7=Liping |first7=Luo |title=Multivariate Analyses of Volatile Chemical Composition in Leaves of Different Cinnamomum camphora Chemotypes |journal=Chinese Bulletin of Botany |date=2014 |volume=49 |issue=2 |pages=161 |doi=10.3724/SP.J.1259.2014.00161}}{{cite book |title=中国药典第一部 |trans-title=Pharmacopoeia of the People's Republic of China, Volume 1|edition=2020}} [https://db.ouryao.com/yd2020/view.php?id=f69de75262 右旋 (+)] {{webarchive|url=https://web.archive.org/web/20250125204121/https://db.ouryao.com/yd2020/view.php?id=f69de75262}} [https://db.ouryao.com/yd2020/view.php?id=f93d89bae0 左旋 (-)] {{webarchive|url=https://web.archive.org/web/20250125203813/https://db.ouryao.com/yd2020/view.php?id=f93d89bae0}} [https://db.ouryao.com/yd2020/view.php?id=fa0dd3c944 合成 (racemic synthetic)] {{webarchive|url=https://web.archive.org/web/20250125203837/https://db.ouryao.com/yd2020/view.php?id=fa0dd3c944}}
Natural (-)-borneol occurs in Blumea balsamifera.
=Biosynthesis=
Borneol is synthesized using DMAPP as the starting material. DMAPP is then converted to GPP, which is acted upon by a bornyl diphosphate synthase to yield a bornyl diphosphate. A phosphatase then removes the phosphate groups, yielding borneol.{{cite journal |last1=Ma |first1=Rui |last2=Su |first2=Ping |last3=Ma |first3=Qing |last4=Guo |first4=Juan |last5=Chen |first5=Suiqing |last6=Jin |first6=Baolong |last7=Zhang |first7=Haiyan |last8=Tang |first8=Jinfu |last9=Zhou |first9=Tao |last10=Xiao |first10=Chenghong |last11=Cui |first11=Guanghong |last12=Huang |first12=Luqi |title=Identification of (−)-bornyl diphosphate synthase from Blumea balsamifera and its application for (−)-borneol biosynthesis in Saccharomyces cerevisiae |journal=Synthetic and Systems Biotechnology |date=March 2022 |volume=7 |issue=1 |pages=490–497 |doi=10.1016/j.synbio.2021.12.004 |pmid=34977393 |pmc=8671873}}
The chirality of borneol in a plant depends on the preferred chirality of the bornyl diphosphate synthase. Synthases for either chirality have been sequenced.{{cite journal |last1=Yang |first1=Zerui |last2=An |first2=Wenli |last3=Liu |first3=Shanshan |last4=Huang |first4=Yuying |last5=Xie |first5=Chunzhu |last6=Huang |first6=Song |last7=Zheng |first7=Xiasheng |title=Mining of candidate genes involved in the biosynthesis of dextrorotatory borneol in Cinnamomum burmannii by transcriptomic analysis on three chemotypes |journal=PeerJ |date=10 June 2020 |volume=8 |pages=e9311 |doi=10.7717/peerj.9311 |doi-access=free |pmid=32566406 |pmc=7293187}}
A downstream product is camphor of either chirality, a reaction catalyzed by (+)-borneol dehydrogenase or (−)-borneol dehydrogenase.
Uses
Whereas d-borneol was the enantiomer that used to be the most readily available commercially, the more commercially available enantiomer now is l-borneol, which also occurs in nature.
(+)-Borneol from Dipterocarpus spp. is used in traditional Chinese medicine. An early description is found in the Bencao Gangmu.
Borneol is a component of many essential oils[http://www.ars-grin.gov/cgi-bin/duke/highchem.pl?chem=borneol&allchems=x Plants containing borneol] {{webarchive|url=https://web.archive.org/web/20150923174038/http://www.ars-grin.gov/cgi-bin/duke/highchem.pl?chem=borneol&allchems=x |date=2015-09-23 }} (Dr. Duke's Phytochemical and Ethnobotanical Databases)] and it is a natural insect repellent.{{cite web|url=http://sun.ars-grin.gov:8080/npgspub/xsql/duke/chemdisp.xsql?chemical=BORNEOL |title=Chemical Information |publisher=sun.ars-grin.gov |access-date=2008-03-02 |url-status=dead |archive-url=https://web.archive.org/web/20041107161247/http://sun.ars-grin.gov:8080/npgspub/xsql/duke/chemdisp.xsql?chemical=BORNEOL |archive-date=2004-11-07 }} It also generates a TRPM8-mediated cooling sensation similar to menthol.{{cite journal |last1=Chen |first1=GL |last2=Lei |first2=M |last3=Zhou |first3=LP |last4=Zeng |first4=B |last5=Zou |first5=F |title=Borneol Is a TRPM8 Agonist that Increases Ocular Surface Wetness |journal=PLOS One |date=2016 |volume=11 |issue=7 |pages=e0158868 |doi=10.1371/journal.pone.0158868 |pmid=27448228|pmc=4957794 |bibcode=2016PLoSO..1158868C |doi-access=free }}
Laevo-borneol is used in perfumery. It has a balsamic odour type with pine, woody and camphoraceous facets.
Dextro-borneol (dexborneol) is used in edaravone/dexborneol, a drug approved in China for stroke.{{cite journal |last1=Xu |first1=Jie |last2=Wang |first2=Anxin |last3=Meng |first3=Xia |last4=Yalkun |first4=Gulbahram |last5=Xu |first5=Anding |last6=Gao |first6=Zhiqiang |last7=Chen |first7=Huisheng |last8=Ji |first8=Yong |last9=Xu |first9=Jun |last10=Geng |first10=Deqin |last11=Zhu |first11=Runxiu |last12=Liu |first12=Bo |last13=Dong |first13=Aiqin |last14=Mu |first14=Hua |last15=Lu |first15=Zhihong |last16=Li |first16=Shuya |last17=Zheng |first17=Huaguang |last18=Chen |first18=Xia |last19=Wang |first19=Yilong |last20=Zhao |first20=Xingquan |last21=Wang |first21=Yongjun |last22=Wang |first22=Yongjun |last23=Xu |first23=Anding |last24=Zhao |first24=Xingquan |last25=Chen |first25=Xia |last26=Wang |first26=Yongjun |last27=Meng |first27=Xia |last28=Wang |first28=Yilong |last29=Xu |first29=Jie |last30=Wang |first30=Anxin |last31=Zheng |first31=Huaguang |last32=Gao |first32=Zhiqiang |last33=Duan |first33=Lei |last34=Zhang |first34=Jinghua |last35=Li |first35=Shuya |last36=Lou |first36=Donghua |last37=Gao |first37=Zhiqiang |last38=Chen |first38=Huisheng |last39=Ji |first39=Yong |last40=Xu |first40=Jun |last41=Geng |first41=Deqin |last42=Zhu |first42=Runxiu |last43=Liu |first43=Bo |last44=Dong |first44=Aiqin |last45=Liang |first45=Qingcheng |last46=Yang |first46=Hong |last47=Guo |first47=Cunju |last48=Li |first48=Xin |last49=He |first49=Mingli |last50=Tian |first50=Xiangyang |last51=Cui |first51=Yong |last52=Zhou |first52=Junshan |last53=Wang |first53=Ning |last54=Wang |first54=Lei |last55=Zhang |first55=Xinjiang |last56=Gao |first56=Xiaoping |last57=Lu |first57=Liping |last58=Li |first58=Tong |last59=Cheng |first59=Yan |last60=Liu |first60=Kaixiang |last61=Xi |first61=Xiaokun |last62=Wang |first62=Baojun |last63=Sun |first63=Lin |last64=Zhao |first64=Shigang |last65=Chu |first65=Xiaofan |last66=Lian |first66=Yajun |last67=Yan |first67=Fuling |last68=Wang |first68=Xiaoshan |last69=Wang |first69=Dong |last70=Shao |first70=Bei |last71=Jiao |first71=Jinsong |last72=Wu |first72=Heng |last73=Li |first73=Guanglai |last74=Guo |first74=Libin |last75=Wang |first75=Yongjun |last76=Pan |first76=Suyue |last77=Xu |first77=Anding |last78=Li |first78=Heng |last79=Zhuang |first79=Jianhua |last80=Li |first80=Xin |last81=Wu |first81=Jun |last82=Wang |first82=Anxin |last83=Lou |first83=Donghua |last84=Zuo |first84=Yingting |last85=Zhang |first85=Yijun |last86=Zhang |first86=Xiaoli |last87=Feng |first87=Xiaofei |last88=Meng |first88=Xia |last89=Wang |first89=David |last90=Dong |first90=Kehui |last91=Liu |first91=Yanfang |last92=Li |first92=Hao |last93=Chen |first93=Dawei |last94=Lv |first94=Qiushi |title=Edaravone Dexborneol Versus Edaravone Alone for the Treatment of Acute Ischemic Stroke: A Phase III, Randomized, Double-Blind, Comparative Trial |journal=Stroke |date=March 2021 |volume=52 |issue=3 |pages=772–780 |doi=10.1161/STROKEAHA.120.031197|pmid=33588596 }}
Toxicology
Borneol may cause eye, skin, and respiratory irritation; it is harmful if swallowed.[https://fscimage.fishersci.com/msds/33824.htm Material Safety Data Sheet]. Fisher Scientific. Acute exposure may cause headache, nausea, vomiting, dizziness, lightheadedness, and syncope. Exposure to higher levels or over a longer period of time may cause restlessness, difficulty concentrating, irritability, and seizures.[https://nj.gov/health/eoh/rtkweb/documents/fs/0242.pdf HAZARDOUS SUBSTANCE FACT SHEET] (PDF)
= Skin irritation =
Borneol has been shown to have little to no irritation effect when applied to the human skin at doses used in fine fragrance formulation.{{Cite journal|last1=Bhatia|first1=S.P.|last2=Letizia|first2=C.S.|last3=Api|first3=A.M.|date=November 2008|title=Fragrance material review on borneol|url=https://linkinghub.elsevier.com/retrieve/pii/S0278691508003219|journal=Food and Chemical Toxicology|language=en|volume=46|issue=11|pages=S77–S80|doi=10.1016/j.fct.2008.06.031|pmid=18640181|url-access=subscription}} Skin exposure can lead to sensitization and a future allergic reaction even to small quantities.
Derivatives
The bornyl group is a univalent radical C10H17 derived from borneol by removal of hydroxyl and is also known as 2-bornyl.{{cite web|url=https://www.merriam-webster.com/dictionary/bornyl|title=Definition of BORNYL|website=www.merriam-webster.com}} Isobornyl is the univalent radical C10H17 that is derived from isoborneol.{{cite web|url=https://www.merriam-webster.com/dictionary/isobornyl|title=Definition of ISOBORNYL|website=www.merriam-webster.com}} The structural isomer fenchol is also a widely used compound derived from certain essential oils.
Bornyl acetate is the acetate ester of borneol.
Notes and references
{{Reflist|2}}
External links
- [http://webbook.nist.gov/cgi/cbook.cgi?ID=507-70-0&Units=SI&Mask=100 NIST datasheet including full spectroscopic data]
- [http://www.itmonline.org/arts/borneol.htm Borneol in Chinese medicine]
{{GABAAR PAMs}}