Pomzazed
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Camphor: Any interesting experiment?
Beside of sulfonating it to camphorsulfonic acid (and use it as organic acid), or oxidize it to its several ring-opened camphor acids. Any interesting
or spectacular reaction to mess with camphor?
I just recieve a free 3kg of this, standing in my room.
Don't stare at me making fumes... I'm just experimenting with some gas...
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UnintentionalChaos
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I don't know about single, simple experiments, but if you have optically pure material, it opens the way to several chiral products.
For example, a Baeyer-Villager oxidation will insert an O into the ring between the ketone and the quaternary carbon. Opening this with base will give
you a pair of stereocenters; a tertiary alcohol and a carboxylic acid chain.
From here, you could do a few things
-Directly epoxidize it. The carboxylic acid wagging about may be enough to force the epoxidation mostly to the opposite side. I'm not so sure on this.
-Do a bromo/iodolactonization. The bromine will add solely to the opposite face of the molecule, though where the carboxylic acid attacks the
bromonium ion is uncertain, as the electronically favored site is sterically hindered. In either case, lactone cleavage with KOH or similar will
simultaneously ring close the epoxide, which will be on the same face of the molecule as the acid group.
Nucleophilic ring-opening of the epoxide prepared by the first method (if it works) under basic conditions must then insert the new group on the same
face as the carboxylic acid. You will also have inverted the stereochemistry of the tertiary alcohol.
If you ring open the second epoxide, the nucleophile will add to the opposite side as the carboxylic acid group and you will have regenerated your
tertiary alcohol. Maybe you could use the anion of diethyl malonate and then decarboxylate the product.
I'm not really going anywhere with this, just thinking out loud. It would be an interesting lesson in chiral pool synthesis and ring-based
stereocontrol.
Department of Redundancy Department - Now with paperwork!
'In organic synthesis, we call decomposition products "crap", however this is not a IUPAC approved nomenclature.' -Nicodem
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argyrium
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Take roughly equal sized (volume) pieces of camphor and p-dichlorobenzene and place one on top of the other. Observe what happens.
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S.C. Wack
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Rast
Sulfuryl chloride. See Biltz & Biltz.
Rast method for determination of molecular weight, i.e.
http://www.jbc.org/content/75/1/289
And the attached article among others.
Attachment: jacs_65_2023_1943.pdf (291kB)
This file has been downloaded 845 times
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Arrhenius
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You could make Oppolzer's camphor-derived sultam. I would call that synthesis a pain in the ass, haha, but it's good stuff. On a side note, try
drawing a mechanism for the sulfonation of camphor to CSA 
http://www.sigmaaldrich.com/catalog/ProductDetail.do?lang=en...
In my opinion, this is the best chiral auxiliary - along with pseudoephedrine.
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Pomzazed
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Aw, wouldn't camphorsultam require reductive amination, sulfonation, and condensation in some order?
But chiral auxilaries don't have much use to me anyway at home lab. I do not have chiral detector. At most what can be done is to construct a
polarized sodium D-line, but that's it.
As camphor is quite a compact structure of carbons, any more experiment worth trying?
| Quote: | | try drawing a mechanism for the sulfonation of camphor to CSA |
does this involve a nonclassical carbocation formation?
Don't stare at me making fumes... I'm just experimenting with some gas...
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Nicodem
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Personally, I very much like the idea of deriving heterocycles from chiral terpenes. Camphor is just perfect for nice products of this type. Camphor condensed pyrazines can be prepared relatively easily even in an amateur setting using cheap reagents. All the intermediates are solids
and thus no chromatography is needed. You can then do some coordination compounds with metals. The alpha-nitrosated or the alpha-oxo intermediate can
both be used to prepare camphor condensed imidazoles (DOI:10.1016/j.tetasy.2008.10.026 and DOI: 10.1021/cg701085c).
Camphor can also be chlorinated or brominated on the alpha keto position. The products are again solids and could be potentially used for the
synthesis of a variety of heterocycles (for example, if successful, the condensation with thiourea would give you a chiral aminothiazole not yet
described in the literature). You can try the chlorination by using trichloroisocyanuric acid in acetic acid as solvent and a few mol% of H2SO4 as
catalyst (test on small scale!). This should be much simpler than using Cl2 and the precipitation of cyanuric acid gives a rough indication of the
reaction progress (in case you can't do TLC monitoring). After purification and recrystalization you check if you got the right product by melting
point determination. The chlorocamphor can then be used as a starting material for several experiments in organic and heterocycles synthesis.
…there is a human touch of the cultist “believer” in every theorist that he must struggle against as being
unworthy of the scientist. Some of the greatest men of science have publicly repudiated a theory which earlier they hotly defended. In this lies their
scientific temper, not in the scientific defense of the theory. - Weston La Barre (Ghost Dance, 1972)
Read the The ScienceMadness Guidelines!
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Sandmeyer
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An obvious OTC reaction that comes to mind and giving a fairly complex product is Fischer indole synthesis using phenylhydrazine (OTC). However the
carbonyl of camphor is very hindered so I doubt the reaction will work well. You can also obtain carvacrol if you treat camphor with iodine (OTC) at
elevated temperature. EDIT: You can do a ring-expansion to lactone by baeyer villiger oxidation - peracetic acid from acetic acid (OTC) and H2O2
(OTC), also Beckmann rearrangement... If you are interested in these reactions I could check the literature but it has to be after weekend...
[Edited on 16-4-2010 by Sandmeyer]
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Paddywhacker
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Camphor smells nice, and you could explore that avenue, looking for interesting smells.
My idea for you is to try aldol condensations. Camphor has an -CH2-CO- although, as pointed out by Sandmeyer, it is somewhat hindered. Would
condensations with formaldehyde, acetaldehyde, acetone or benzaldehyde yield anything nicely smelly. I'd sure like to hear of your trials.
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Arrhenius
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Yes, I believe it does involve a non-classical carbocation (see Winstein, Cram et al). May not be the most exciting product, but it's a very useful
dry organic acid (TsOH is a monohydrate) and the mechanism is neat. 
You could probably sell a chiral sultam on ebay for a nice price Legal
chemistry for profit.
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The WiZard is In
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Quote: Originally posted by Pomzazed  | Beside of sulfonating it to camphorsulfonic acid (and use it as organic acid), or oxidize it to its several ring-opened camphor acids. Any interesting
or spectacular reaction to mess with camphor?
I just recieve a free 3kg of this, standing in my room. |
Mix with cellulose nitrate and make exploding billiard balls.
Extracted from :--
Journal of the Society of Chemical Industry.
No. 5, Vol,. XXXIII. MARCH 16, 1914.
New York Section.
Meeting held at Rumford Hall, New York, on Friday, January 23rd, 1914.
Mr.. C. W. THOMPSON IN THE CHAIR.
PRESENTATION OF THE PERKIN MEDAL TO Mr. JOHN WESLEY HYATT.
At this meeting of the Now York Section of the Society of Chemical Industry, it is our
pleasant duty to award the Perkin medal to the person selected as most worthy
for valuable work done in applied chemistry………
What is the mental faculty which has made the recipients of the Perkin medal
what they are ? In what respect do these men differ from their fellow chemists, so
as to render them especially successful in the application of chemistry to the arts
........ in the case of Hyatt, who saw in the drop of dried collodion the possibility of
producing a plastic mass, which was finally obtained in celluloid.
Mr. JOHN WESLEY HYATT acknowledged the receipt of the medal in the
following words :—
From my earliest experiments in nitrocellulose, incited by accidentally finding a
dried bit of collodion the size and thickness of my thumb nail, and by my very
earnest efforts to find a substitute for ivory billiard balls……
Other seriously objectionable features became apparent. In order to secure
strength and beauty only colouring pigments were added, and in the least
quantity ; consequently a lighted cigar applied would at once result in a serious
flame, and occasionally the violent contact of the balls would produce a mild
explosion like a percussion guncap. We had a letter from a billiard saloon
proprietor in Colorado, mentioning this fact and saving he did not care so much
about it, but that instantly every man'n the room pulled a gun…..
An expl ode to John Hyatt
Now John Hyatt's 'Wild West' billiard balls
Where the talk of the saloons and halls
When they hit the road
They were apt to explode
You can bet that they started some brawls
PEC
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Nicodem
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| Quote: Originally posted by Sandmeyer | | An obvious OTC reaction that comes to mind and giving a fairly complex product is Fischer indole synthesis using phenylhydrazine (OTC). However the
carbonyl of camphor is very hindered so I doubt the reaction will work well. |
That would be a structurally nice looking product for those terpene-heterocycle fetishists like myself. Here are the only three entries from SciFinder
and they are not particularly optimistic:
| Quote: | Indole cyclization of camphor phenylhydrazone. Isolation of interesting collateral products. Sparatore, Fabio. Univ. Genoa,
Gazzetta Chimica Italiana (1958), 88 755-68. CODEN: GCITA9 ISSN: 0016-5603. Journal language unavailable. CAN 53:122385 AN 1959:122385
CAPLUS
Abstract
To clarify the mechanism of the Fischer indole synthesis various secondary products reported in the cyclization of camphor phenylhydrazone (I)
(Kuroda, C.A. 17, 3031) were reinvestigated. I (5 g.), prepd. according to Agostinelli (C.A. 7, 1882), freshly distd. in vacuo, triturated with 15 g.
anhyd. ZnCl2, the mixt. heated 30 min. at 100 (preheated metal bath) then 4 min. at 180 (2nd preheated metal bath), the cooled mass taken up in H2O,
the aq. layer extd. with Et2O, the residual resin taken up in the Et2O ext., the filtered soln. shaken with 0.5N HCl and H2O, the aq. washings united
with the acid ext. (II), the dried Et2O ext. evapd., and the residue distd. at 0.2 mm. gave a small amt. of campholenonitrile, b0.2 100, some camphor
(sublimation on the cold wall), and a heavy dark oil, b0.2 170. The oil fractionated in C6H14 gave a cryst. product (III), m. 153-4 (C6H6), and the
C6H14 filtrate refrigerated yielded the known camphoindole, m. 92-4, giving an intense rose-purple color with Ehrlich reagent. III gave no Ehrlich
reaction and no color with FeCl3 in MeOH. III (30 mg.) heated 3 hrs. on a steam bath in 5 ml. 0.5N NaOH, the cooled soln. extd. with Et2O, the washed
and dried ext. concd., and refrigerated gave a 2nd neutral substance, m. 215-18, insol. in dil. alkali and in dil. acid, giving no color with FeCl3 in
MeOH. II made alk. with NH4OH, extd. with Et2O, the washed and dried ext. evapd., and the product distd. at 0.2 mm. gave clear yellow oily PhNH2; a
2nd fraction, b0.2 90-110, recrystd. (C6H14) gave authentic .omicron.-C6H4(NH2)2 (IV), m. 103, .lambda. 237, 265 (min.), 294 m.mu. (log .epsilon.
3.78, 2.70, 3.45)(Grammaticakis, C.A. 46, 3401g), and a 3rd fraction, b0.2 160-80, washed with Et2O and the residue sublimed at 150-60/0.2 mm. to give
a benzimidazole deriv. (V), C16H22N2, m. 208-10, .lambda. 243, 274, 280 m.mu. (log .epsilon. 3.79, 3.80, 3.86, alc.), 236, 268, 275 m.mu. (log
.epsilon. 3.64, 3.90, 3.95, N HCl), entirely superimposable on the curve of 2-methylbenzimidazole (Leandri, et al., C.A. 50, 2291i).
The possibility of the passage from camphor phenylenediamine to V was confirmed by condensation of IV with the more active pernitrosocamphor (VI).
IV (1 g.) in 2 ml. alc. heated on a steam bath with 2 g. VI to cessation of evolution of N2O, the alc. evapd. in vacuo, the residue heated 5 min. at
180-90 (metal bath), and the product distd. at 0.2 mm. gave, in addn. to campholenonitrile and unchanged IV, a heavy orange-yellow oil, b0.2 115-40,
cleaving in dil. HCl to camphor and IV, and a cryst. fraction, b0.2 150-70, which washed with Et2O and sublimed in vacuo gave authentic V.
Indolic cyclization of camphor phenylhydrazone. II. Sparatore, Fabio. Univ. Genoa, Gazzetta Chimica Italiana (1962), 92
596-605. CODEN: GCITA9 ISSN: 0016-5603. Journal language unavailable. CAN 58:66619 AN 1963:66619 CAPLUS
Abstract
cf. CA 53, 22054d. To clarify the structure of secondary products, the cyclization of camphor phenylhydrazone (I) was reinvestigated. Thus, 16 g. I
heated at 100 and mixed with anhyd. ZnCl2, the mixt. kept 30 min. at 100 and 5 min. at 180, cooled, treated with 2N HCl, extd. with Et2O, the aq.
soln. (A) stored, the org. layer dried (Na2SO4), the solvent evapd. and the residue (6.6 g.) distd. gave a first fraction, b0.2 100-50, from which, by
chromatography on Al2O3, 2.3 g. of crude campholenonitrile (C6H6 as eluent) and 0.6 g. .beta.-campholenic amide (II) (C6H6-5% EtOH as eluent) were
isolated. II m. 90-1 (C6H6-petr. ether). A second fraction (1.8 g.), b0.2 150-80, purified by chromatography on Al2O3, yielded 1 g.
camphoindole(III), m. 92 (petr. ether). The soln. A, decolorized with C and basified with NH3, was extd. with Et2O and the ext. dried (Na2SO4) and
evapd. to give 5.9 g. residue which was distd. to give PhNH2 as fore-run, then a fraction (a), b0.2 90-120 and a fraction (b), b0.2 160-85. Fraction
(a) on standing sepd. a cryst. product, m. 139-40, identified as .alpha.-(camphor)-aminocamphor (IV), .lambda. 302 m.mu. (log .epsilon. 2.30). In the
oily residue o-C6H4(NH2)2 was identified. Fraction (b) on standing sepd. the benzimidazole deriv. (V), m. 197-8 (dil. EtOH). The isolation of IV
suggested a reaction mechanism involving a break of the N-N bond of I to give free radicals which may condense in different ways to III-V.
Indolic cyclization of camphor phenylhydrazone. III. Structure of so-called camphorindole. Sparatore, Fabio; Pirisino, Gerolamo.
Univ. Sassari, Sardinia, Gazzetta Chimica Italiana (1965), 95(5), 546-55. CODEN: GCITA9 ISSN: 0016-5603. Journal written in Italian.
CAN 63:46392 AN 1965:446392 CAPLUS
Abstract
cf. CA 11404h; Kuroda, CA 17, 3031. Camphor phenylhydrazone in contact with anhyd. ZnCl2 at 180 reacts yielding the compd. C16H19N (I), which is
called camphorindole. Assumed structure of I yields a strong violet color reaction with the Ehrlich reagent. Tetrahydrocarbazole (II) having a very
similar structure does not undergo the same reaction. Also uv absorption spectra of I and II show a clear difference: therefore structure I appears
to be not suitable. The only possible exact structure for compd. I is III. A compd. which has indubitably structure III has been prepd. by
cyclization of .beta.-campholenic aldehyde phenylhydrazone. The latter was prepd. by reduction of N-methylanilide of .beta.-campholenic acid.
Complete identity of compd. prepared by this way and so-called camphorindole is a definite proof that structure III is the true structure of
camphorindole.
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But these are only attempts with the ZnCl2 catalysed Fischer indolization. Other methods might give better results, though side products derived from
the Wagner-Meerwein rearrangements seem quite unavoidable.
(Can't find the "Kuroda, C.A. 17, 3031" reference in the electronic version of Chemical abstracts.)
Edit: Found and added another CA entry.
[Edited on 18/4/2010 by Nicodem]
…there is a human touch of the cultist “believer” in every theorist that he must struggle against as being
unworthy of the scientist. Some of the greatest men of science have publicly repudiated a theory which earlier they hotly defended. In this lies their
scientific temper, not in the scientific defense of the theory. - Weston La Barre (Ghost Dance, 1972)
Read the The ScienceMadness Guidelines!
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benzylchloride1
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Terpene chemistry, one of my favorite fields. Camphorquinone which is really a diketone can be produced via a selenium dioxide oxidation of camphor,
see organic syntheses for the preparation or from camphor by producing the nitroso compound on the alpha carbon. This can then be hydrolyzed to the
diketone. See one of the older advanced organic chemistry lab manuals available in the library. Another interesting experiment would be to produce
camphor from turpentine. A really good base is needed to produce camphene from bornyl chloride produced from the addition of HCl to the double bond of
alpha pinene. Some interesting chemistry can be done with alpha pinene, taxol was synthesized via 2 routes, one starting from alpha pinene, the other
starting from camphor. I am currently working on trying to replicate at least part of the synthesis starting from alpha pinene.Camphor can also be
oxidized to camphoric acid with dilute nitric acid.
Amateur NMR spectroscopist
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peach
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I'm almost ashamed to post this, lowering the tone of the exploding balls as it does, but the principle component of brown camphor oil is
5-(2-propenyl)-1,3-benzodioxole
Discussion over 
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