1. Pavia 31, page 277 Borneol  Iso Borneol

2. Rules of oxidation Oxidation = loss of electrons For organics
Inorganic Feo  Fe+2 + 2e-1
For organics
Oxygen always -2 charge
- O 1 electron from carbon, one elsewhere
=O 2 electrons from carbon
Hydrogen always +1 charge
Carbon gets what’s left for electrical neutrality

3. Inorganic REDOX

4. Organic REDOX criteria is oxygen content

5. Organic REDOX examples

6. More REDOX examples (a) Carbon@ -1  Carbon @ +1 = oxidized (b) Carbon@ +3  Carbon @ +1 = reduced

7. Oxidation of Methane Methane Carbon charge is -4 due to 4x H+
CO2 carbon charge is +4 due to 2x =O
Carbon OXIDIZED (lost electrons)
Oxygen reduced (gained electrons)
Water byproduct not shown

8. Cartoon Version

9. Starting Material #1 Borneol C10H18O
MP= 208oC ,
BP= 213oC
Density =1.011g/mL,
FW= g/mole
Solubility “slight” (25oc)
LD50 = 5800mg/kg (rat),
or … 406g for 154 lb person

10. Borneol
Borneol, abundant in rosemary oil, shares properties of other terpene alcohols; as skin tonic, local anesthetic, sedative, & antispasmodic.
Terpene Alcohols are valued for fragrance, gentle skin & membrane reaction plus healing properties, referred to as "Friendly Molecules".
These alcohols are among strongest antimicrobial compounds in essential oils, but lack the irritant properties of antimicrobial constituents like phenols. 
Used in Chinese medicine & insect repellents

11. Starting Material #2 “PCC” C5H5NHClCrO3
MP= 205oC ,
BP= decompose
Density =1.011g/mL,
FW = g/mole
Solubility = reacts with water

12. https://en.wikipedia.org/wiki/Pyridinium_chlorochromate
PCC is highly effective in oxidizing primary and secondary alcohols to aldehydes and ketones.
A typical PCC oxidation involves addition of the alcohol to a suspension of PCC in dichloromethane
In practice the chromium byproduct deposits as a sticky black tar, which can complicate workup.
Addition of an inert adsorbent such as crushed molecular sieves or silica gel allows the sticky byproduct to adsorb to the surface, and makes workup easier.
Disadvantages to using PCC are the tedious reaction workup and its toxicity.

13. PCC risks

14. http://www. masterorganicchemistry

15. Intermediate Material #3 Camphor C10H18O
MP= 176oC ,
BP= 209oC
Density = 0.992g/mL,
FW= g/mole
Solubility = 1.2g/L
LD50 = 1310mg/kg (mouse)
92g for 70kg person

16. Camphor uses
 Dried rosemary leaves, in the mint family, contain up to 20% camphor. It is used for its scent, as an ingredient in cooking (mainly in India), as an embalming fluid, for medicinal purposes, and religious ceremonies.
Camphor is readily absorbed through the skin, producing either a coolness or warmth sensation, and acts as slight local anesthetic and antimicrobial substance.
Camphor is an active ingredient (with menthol) in vapor-steam products, such as Vicks VapoRub. It is used as cough suppressant and decongestant.
Camphor may be administered orally in small quantities (50 mg) for minor heart symptoms and fatigue. .
Camphor was used in ancient Sumatra to treat sprains, swellings, and inflammation. Camphor is a component of paregoric, an opium/camphor tincture from the 18th century. Also in the 18th century,, camphor (dissolved in alcohol) was also successfully used to treat the  cholera epidemics in Naples.[

17. Starting Material #4 Sodium Borohydride, NaBH4
MP = 400oC
BP = 500oC
Density = 1.074g/mL
MW = g/mole
Solubility, reacts with water
LD50 = 160mg/kg (rat)
MP = 400oC
BP = 500oC
Density = 1.074g/mL
MW = g/mole
Solubility, reacts with water
LD50 = 160mg/kg (rat)
11.2g for 70kg person

18. Reduction of Camphor products will likely be a mix of isomers

19. Product Iso-Borneol C10H18O
MP= oC ,
BP= 415oC
Density = 1.01g/mL,
MW= g/mole
Solubility in water 1.19g/L
MSDS =5800mg/kg (rat)
406g for 70kg person

20. Iso-Borneol

21. TUESDAY LAB – Part A Add 1.0g PCC + 1.0g silica gel in mortar
Grind together to fine powder >3min minimum
Above powder + 10mL CH2Cl2 into 50mL flask
Add 0.360g Borneol to above mix, stir 20min
Prep vacuum filter layer of Celite + silica gel
Filter reaction mix, rinse with 2x 10mL CH2Cl2
Evaporate solvent with gentle air stream
Dispose of Cr residue as directed
Re-dissolve Camphor in 4mL CH2Cl2
Dry over NaSO4
Sublimation to recover solid Camphor

22. THURSDAY LAB – Part B Weigh dried product from Tuesday
Calculate yield
Verify camphor, test for residual Borneol using IR
Carbonyl peak replaces hydroxide
Adjust Camphor sample size to >0.10g, if needed
Add 2mL MeOH (per 0.10g Camphor)
Slowly add 0.10g NaBH4 (per 0.10g Camphor)
Boil mix on hot plate for 2 min to evaporate MeOH
When cool, add 5mL cold water
Collect solids via vacuum filter, dry product
Dissolve in 5mL CH2Cl2 , 25mL pre-weighed flask
Dry In hood, reweigh to obtain product mass
Melting point, literature value = 212oC
FTIR + NMR (save scans to desktop)

23. Borneol

24. Camphor, no O-H, but =O

25. Iso-Borneol , O-H band returns, no =O looks nearly identical to Borneol, how to differentiate?

27. 2 possibilities in reduction of camphor NMR can identify % of Borneol & Iso-Borneol by proton shift side nearest bridge is called “exo”, under the bridge is “endo”

28. NMR for Borneol Iso-Borneol yields peak at 3.6 vs. 4.0 for Borneol

29. Isomer Ratio from NMR signals example from “reduction of Camphor SP14” pdf

30. Isomer Percentage using values from prior page example
Integrated signals, same carbon number of 1H
Borneol value 4.0ppm = 2.314
Isoborneol value 3.6ppm = 9.497
Percentage of isomer is individual / total value
Borneol = / ( ) = 19.7%
Isoborneol = 9.497/( ) = 80.3%

32. To the benches !