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blogfast25
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Oxidation of leaf alcohol?
I’m pretty desperate for OTC feedstocks of C5/C6/C7 (preferably linear) materials, anything from 1-ols, 1-halos, 1-aldehydes, 1-carboxylic acids and
even 2-ketones. Searching I came across a fairly OTC substance commonly called ‘leaf alcohol’, IUPAC: cis-3-hexen-1-ol.
Could this be easily oxidised to the corresponding carboxylic acid using K2Cr2O7/acid (maybe in acetone, and/or using another oxidising agent) without
affecting the double bond, to cis-3-hexenoic acid (CAS 1775-43-5)?
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ItalianChemist
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KMnO4 is stronger than dichromate! I suggest you to use KMnO4 if yo want carboxylic acid and heating until the red color becomes brown.
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DJF90
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@ItalianChemist: Two things suggest you have no idea what you're talking about - the first is that permanganate is likely to have a greater propensity
to "tickle" that alkene; the second is that the colour change you give is incorrect (permanganate is purple, not red. The colour arises from a LMCT
band).
@Blogfast: There are oxidisers that will successfully effect the desired transformation. I'd suggest looking at the literature, something is bound to
have been mentioned.
[Edited on 18-5-2011 by DJF90]
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Magpie
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Perhaps nitric acid would work. It worked for me making malonic acid. Also my procedure for same in Prepublication lists a reference IIRC.
Where is leaf alcohol OTC? What's its OTC use?
The single most important condition for a successful synthesis is good mixing - Nicodem
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Neil
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There is a patent for using gold catalysts Oxidative dehydrogenation of alcohols to aldehydes and ketones.
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The WiZard is In
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Quote: Originally posted by Magpie  | Perhaps nitric acid would work. It worked for me making malonic acid. Also my procedure for same in Prepublication lists a reference IIRC.
Where is leaf alcohol OTC? What's its OTC use? |
Perfume perhaps. The Chemical Week Buyers Guide only
lists one supplier in la US of A.
Google it.
Getting my monies worth out of The Merck Index 14th ed.
It came w/ a CD allowing for online access good for one year,
I have just opened it.
Trivia - What were the first editions of now what is called The
Merck Index labeled?
Monograph Number: 0004700
Title: 3-Hexen-1-ol
CAS Registry Number: 544-12-7
Additional Names: Leaf alcohol
Trademarks: Blätteralkohol
Molecular Formula: C6H12O
Molecular Weight: 100.16
Percent Composition: C 71.95%, H 12.08%, O 15.97%
Line Formula: CH3CH2CH=CHCH2CH2OH
Literature References: Occurs in leaves of odoriferous plants (including shrubs and trees). Isoln from Japanese oil of peppermint: Walbaum J.
Prakt. Chem. [2] 96, 245 (1917); Walbaum, Rosenthal, Ber. Schimmel 1929 Jubiläums-Ausg., p 205; from raspberry juice: Bohnsack, Ber. 75, 72 (1942).
The natural product has the cis configuration: Crombie, Harper, J. Chem. Soc. 1950, 873; Harper, Smith, ibid. 1955, 1512.
Properties: Liquid. Strong odor resembling that of isoamyl alc, approaching the odor of green leaves when highly dil. d1522 0.846. bp 156-157°;
bp9 55-56°. nD20 1.4389.
Boiling point: bp 156-157°; bp9 55-56°
Index of refraction: nD20 1.4389
Density: d1522 0.846
[Edited on 19-5-2011 by The WiZard is In]
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The WiZard is In
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Having a moment to kill....
This from Ullmann's 5th. A11:148
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Neil
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You can purchase it from number of suppliers in the flavor/scent/perfume supplies industry. Bloody expensive by my standards...
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blogfast25
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| Quote: Originally posted by Magpie | Perhaps nitric acid would work. It worked for me making malonic acid. Also my procedure for same in Prepublication lists a reference IIRC.
Where is leaf alcohol OTC? What's its OTC use? |
It’s mainly sold as ‘leaf acetate’, the acetic acid ester of said alcohol. It’s basically a flagrance thingy, derived from a menthol plant. An
Indian company offers it at reasonable prices although shipping is something else.
Nitric may be the way to go. I remember your exploits with making malonic acid and the runaway you got!  I’d probably have to experiment with some alcohol like n-butanol or amyl alcohol to get the conditions more or less
right: oxidation reactions of primary alcohols to acids are seriously exothermic.
KMnO4 would almost certainly crack the double bond.
K2Cr2O7 isn’t suitable for allylic alcohols but a cis-3-alkene may survive if the oxidation of the hydroxyl group is carried out in mild
conditions…
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blogfast25
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| Quote: Originally posted by Neil | | You can purchase it from number of suppliers in the flavor/scent/perfume supplies industry. Bloody expensive by my standards...
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I’ve found that all these C5/C6/C7s (or slightly higher) or precursors to them are all quite expensive.
Days ago I extracted about 40 ml of pelargonic acid (nonanoic acid) from Bayer weed killer: a 3 % solution of some pelargonate soap in water at £6/L!
Food ‘supplement’ stores stock caprylic acid (octanoic acid) tablets: assuming complete recovery of the acid is possible the price of the product
thus obtained is roughly £10 for about 50 g.
And interesting stuff like tetrahydro myrcenol (a branched 2-octanol) no one wants to sell to me 
[Edited on 19-5-2011 by blogfast25]
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Magpie
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| Quote: Originally posted by blogfast25 |
Nitric may be the way to go. I remember your exploits with making malonic acid and the runaway you got! I’d probably have to experiment with some alcohol like n-butanol or amyl alcohol to get the conditions more or less
right: oxidation reactions of primary alcohols to acids are seriously exothermic.
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Yes, by all means experiment with small quantities. As I remember the secret to taming these reactions of nitric acid/alcohol is to bring one
reactant up to temperature, say 60-80C, then add the other reactant dropwise. This keeps the reaction under good control.
I did such a reaction yesterday, adding B2O3 slowly to hot methanol to make methyl borate. I think that scale of the reaction is important here also.
The smaller the scale the easier it is to control due to the inverse relationship of the ratio of surface area to volume.
================================
That's an interesting citation form the Merck Index, Wizard. I wonder if it would be worthwhile to extract it from Mulberry leaves with say, ethyl
alcohol, using a soxhlet extractor. I used to have a mulberry tree but cut it down -- it was making a real mess, and was in a bad spot.
[Edited on 19-5-2011 by Magpie]
The single most important condition for a successful synthesis is good mixing - Nicodem
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unionised
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Would C8 help
http://resources.metapress.com/pdf-preview.axd?code=b5284m82...
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The WiZard is In
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| Quote: Originally posted by Magpie |
That's an interesting citation form the Merck Index, Wizard. I wonder if it would be worthwhile to extract it from Mulberry leaves with say, ethyl
alcohol, using a soxhlet extractor. I used to have a mulberry tree but cut it down -- it was making a real mess, and was in a bad spot.
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The apparently do it in India, the Devil is in the details! Extracting
natural products is a mess ... unless you have a really specific
solvent. A check of Google.com/books or Google can't hurt.
Byda did you ever eat mulberry fruits? I have seen people on
the street on NYC eat them ... so I tired. They rank right up there
with — cactus pairs - cassava - bread fruit - plantains for having
little/no taste neat. Creative cooking can work wonders.
I remember a salad bar on President Street in Brooklyn they had
the best cassava and plantain it has been luck to eat. Another
take-away on Manhattan's Thomas Street on Wednesday had
tripe that I never missed.
Reminds me of a cooking joke.
How do you cook kidneys?
You cook the piss out of them.
(Most soak them overnight, except veal kidneys
which can be cooked straight out of the frig.)
[Edited on 19-5-2011 by The WiZard is In]
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The WiZard is In
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| Quote: Originally posted by Magpie |
That's an interesting citation form the Merck Index, Wizard. I wonder if it would be worthwhile to extract it from Mulberry leaves with say, ethyl
alcohol, using a soxhlet extractor. I used to have a mulberry tree but cut it down -- it was making a real mess, and was in a bad spot.
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NB — It's WiZard.
http://tinyurl.com/3lnyx7f
If'n its in the oil - expressing the oil could a good start
to limiting extraneous products.
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Magpie
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| Quote: Originally posted by The WiZard is In |
Byda did you ever eat mulberry fruits? I have seen people on
the street on NYC eat them ... so I tired. They rank right up there
with — cactus pairs - cassava - bread fruit - plantains for having
little/no taste neat. Creative cooking can work wonders.
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I 'm sure I tried them - but as you say I don't remember any food value. The birds ate them, however.
I've also eaten elderberries. Not much food value there either but much better than mulberries.
The single most important condition for a successful synthesis is good mixing - Nicodem
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unionised
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I strongly suspect that steam distilling the oil would work a whole lot better and I also suspect that the yield (based on weight of leaves) will be
less than 1%.
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blogfast25
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Yes, it would and 2-octanol would be a valued prize! But that procedure, simple as it might be on semi-industrial scale, would require serious
adaptations for my use. But it could be worth trying even for lower yields. Thanks!
Wizzard:
I cook lambs kidneys w/o soaking all the time. Added to beef stews it gives that 'je ne sais pas quoi' difference...
[Edited on 19-5-2011 by blogfast25]
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Magpie
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Would 2-ethyl hexan-1-ol be of any interest? I obtained this as a by-product while making phthalic acid from vinyl glove plasticizer.
If so, see: http://www.sciencemadness.org/talk/viewthread.php?tid=6573&a...
The single most important condition for a successful synthesis is good mixing - Nicodem
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blogfast25
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Yes, it would. I'll be scrutinising that thread tomorrow. Thanks!
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The WiZard is In
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| Quote: Originally posted by Magpie |
================================
That's an interesting citation form the Merck Index, Wizard. I wonder if it would be worthwhile to extract it from Mulberry leaves with say, ethyl
alcohol, using a soxhlet extractor. I used to have a mulberry tree but cut it down -- it was making a real mess, and was in a bad spot.
|
Shoxlet? Here is just what you need.
http://www.wilmad-labglass.com/group/1081
The LG-6911-104 one.
Leaf - Leaf alcohol content —
http://tinyurl.com/3rk3r8e
Granted Content and extractable ....!
By da this dobe the problem w/ natural products.
From one of my favorite (albeit expensive) books.
JW Purseglove & et al
Spices
Longman 1981
2 Volumes
   
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blogfast25
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Interesting extraction from something very OTC. And the obtained phthalic acid is good too.
How about the following mods? Extract DOP from gloves (or other pPVC product) with alcohol. Evaporate alcohol (or most of it anyway), leaving behind
the reasonably pure plasticizer. Saponify more or less stoiciometrically with NaOH or KOH, using only little water. The alcohol should be floating on
top, decant off.
Treat phthalic acid soap with stoichiometric amount of HCl to recover phthalic acid. Recrystallise for work up.
Magpie, any particular reason for the choice of IPA? From what I read DOP is supposed to be soluble in most lower alcohols.
[Edited on 20-5-2011 by blogfast25]
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Magpie
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| Quote: Originally posted by blogfast25 |
Magpie, any particular reason for the choice of IPA? From what I read DOP is supposed to be soluble in most lower alcohols.
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IIRC other forum members were using IPA, and it is readily and cheaply available in 99% concentration at my local drugstore (pharmacy).
The single most important condition for a successful synthesis is good mixing - Nicodem
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Paddywhacker
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Here is that book mentioned by Wizz.
Attachment: Common Fragrance & Flavor Materials - 4th edition - Baur, Garbe & Surburg - 2001.pdf (1.7MB)
This file has been downloaded 8021 times
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blogfast25
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Thanks Paddywhacker, it’s been saved.
As a much cheaper source of OTC DOP, I’d suggest waste electrical wire covers and (most) waste garden hose. Probably lower DOP content than vinyl
domestic gloves but totally FOC!
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The WiZard is In
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Natural green top notes
How 'bout — Bottom notes?!
THE SPERM TREES OF LOS ANGELES: THE SEARCH CONTINUES
Dear Cecil [Adams]:
I am writing in regard to the identity of the "semen tree" discussed recently in your
column. May I suggest that what the writer was talking about was the female ginkgo
tree? In the fall it drops many small apricot-colored fruits. When the fruit ripens, it
smells more like vomit than semen. Orientals (I lived in Japan for ten years)
consider the nut within this fruit (the ginkgo nut) to be a delicacy. In the early
morning old people put Baggies over their hands, push the smelly fruit away from
the nut, drop the nuts into a bag, and take them home. They are washed and dried
(during which they lose their smell), cracked open, and the nut meat boiled or
baked. Ginkgo nuts are great, but the fruit is still disgusting. --Elyse A., Evanston,
Illinois
[They smell like well worn gym socks to me. /djh/]
Dear Elyse:
Considering I ran the original letter as an example of a question so stupid that nobody
could possibly be interested in it, the sperm trees of LA have generated an extraordinary
response. In addition to vomit, I have heard about trees that smell like, um, fecal matter.
Another tree supposedly smells like a certain well-known female orifice. A recent
graduate of Vassar College in lovely Poughkeepsie, New York, reports that while on
campus she, too, noticed certain trees that smell like vomit. However, another former
Vassar inmate--believe me, I check this stuff out--says the indicated trees are definitely
not ginkgoes. Knowing the party-hearty predilections of college women these days, I'm
not sure the smell is entirely botanical in origin. Similarly, Cecil's longtime buddy and
spiritual adviser Uncle Pat suggests that the smell of the LA tree may be the result of the
city's notorious deve community having its way with the local plant life. I have taken this
under advisement. Gratz Beehler of Washington, D.C.--a fine fellow despite his dubious
moniker--says there is a tall (50-60 feet) and spindly (six to ten inches in diameter) plant
in Florida known as the "punk tree," which has "very spikelike flowers" (hence the name,
presumably). It blooms in March and October, smells "like rotten stuff" (if not
necessarily semenlike), and is known to grow in LA. Gratz promises to try to rustle up a
sample so we can get a positive ID. Meanwhile, I am still waiting patiently for somebody
to send me a specimen of sperm-tree foliage. C'mon, kids--there's a Nobel Prize in this
somewhere.
MORE OPINIONS
Dear Cecil:
Regarding the "sperm trees" of Los Angeles, I've checked with several people, and
they all agree. California privet (sorry, I don't know the scientific name) is your
culprit. I've seen it in hedge and tree form. I've seen its hairy flowers bloom in
spring and fall; however, it only smells for a few weeks in the spring. That's when
swarm of bees are attracted to it. --C.H., Glendale, California
Dear Cecil:
. . . carob trees. Said trees abound, for example, in the Los Feliz area north of
Franklin near Edgemont. The trees smell like sperm, or Clorox on some days, and
have nothing to do with appearing or acting like sperm. --Frank W., Thousand
Oaks, California
Dear Cecil:
. . . the carob tree. These trees emit this odor only in the fall when they show a
hairlike pollen-tipped fuzz growing from the bark near the tips of narrow branches.
--Tom K., Los Angeles
Dear Cecil:
. . . the carob tree. We had a small one growing in our schoolyard in Arizona. One of
the reasons it may be hard to identify is that it does not always smell. It seems to
have a cycle, but not a yearly one. --M.N., Long Beach, California
Cecil replies:
The mail at this point is running about 2-to-1 carob tree, so I guess we'll declare it the
winner. Unfortunately, the one sample of sperm tree blossom we received had been
dumped into an ordinary envelope (rather than, say, a baggie), giving it time to dry out
and disintegrate before we could get it to an expert for analysis. Let's use our heads out
there, gang.
LATE NEWS ON THE SPERM TREES OF LOS ANGELES (01-Nov-1996)
Longtime readers will recall the heated debate in this space some years ago over the
identity of a tree, originally spotted in Los Angeles, that at certain times of the year
smelled like, uh, sperm. (To be precise, like semen. But you know what we mean.)
It wasn't our idea to get into this repulsive topic. It did, however, capture the imagination
of the Teeming Millions. Not that the Teeming Millions were much help getting to the
bottom of it. Despite repeated pleas, no one ever sent us an identifiable sample, and we
never settled the matter.
The controversy flared anew on our America Online message board last summer. But this
time our call for samples got results. In fact, we got two samples--one from Robert
Williams, the other from Brian Maffitt.
Just one little problem. They weren't the same tree. What's more, neither of them was one
of the trees suggested in our previous go-round on this subject.
I quote from a letter from the experts at the plant clinic at the Morton Arboretum near
Chicago, to whom I sent the above-mentioned samples.
The two specimens you sent us arrived in, well, somewhat poor shape.
[Hey, so I delayed a little sending them out. I'm a busy guy.]
Although you mentioned semen as the putative odor given off by the trees,
and one of the specimens had degraded to what looked like a baggie full of
the bodily fluid, we found the odor much more offensive than an innocent
penis could possibly produce.
However, one brave soul examined the samples long enough to determine
their identity.
The Williams sample is a chestnut (Castanea sp.), known to produce
flowers with an offensive odor (offensive to humans but revered by
pollinating insects). It is likely a Chinese chestnut or hybrid chestnut since
our American chestnut was pretty much wiped out by a fungal disease
introduced to the U.S. around 1906, and there are very few American
chestnuts that reach flowering age.
The Maffitt sample is undoubtedly a tree of heaven (Ailanthus altissima),
although, in honesty, we lacked the courage to pull a leaf out of the
'semen-filled' bag. Tree of heaven is said to stink to high heaven as its
flowers produce a decidedly disagreeable stench.
Interestingly, it is the male flowers that produce the stench, while the
female flowers are aroma-free (there are separate male and female trees
for this species). So perhaps the connection your reader made with male-
produced semen is not too far off.
Very good, except that previously the consensus was that the sperm tree was the carob
tree, with one radical holding out for the California privet. Now we've got three or four
possible sperm trees out there.
So there you have it. The truth ain't pretty. But I feel you need to know.
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