-Ozzie Sabina
The above summaries of aromas are generally along the correct lines, but
seriously oversimplified. Bananas involve a bunch (couldn't resist) of
acetates in the butyl and amyl range. Octyl acetate isn't very orange-y by
itself, and isn't one of the top considerations in duplicating orange. And
ethyl butyrate figures in just about every fruit. But having grumped that
much, consider ethyl heptanoate, which is pretty pineapple-like (I don't
think heptanoates are found in fruit). Or consider the propyl acetates,
which (to me) smell like they should be some kind of fruit, but aren't (we're
talking moderate levels here, not saturated air). A lot of people
experience methyl anthranilate as grape, and methyl N-methylanthranilate as
mandarin orange. Are those simple enough? And the ethyl ester of
methylphenylglycidic acid is moderately strawberry-like (various 5-carbon
carboxylic acids enhance that illusion wonderfully).
I'm barely even a trainee at this stuff. It's pretty remarkable how close you
can get to decent aromas with maybe 4 components. It's even more remarkable,
though, what's needed to go from there to something that is really
convincing. Hardly any commercial flavor would have fewer than 15 components;
many have 30 or more.
Another ester: ethyl cinnamate for your pineapple (not everyone smells it this
way).
Steve s...@chinet.chi.il.us
It's important to realize that the taste and fragrance associated
with fruits are not the result of any single ester, but are usually the
result of a combination of *many* esters, in addition to alcohols, ethers,
aldehyes, ketones, terpenes (especially), etc.
>For example, butyl acetate
>is the odor of bananas, octyl acetate is oranges, and ethyl butyrate is
>pineapples. Out of curiosity, what other fruit odors are from which simple
>esters?
Offhand, here are a few esters and some of the fruits in which
they are found. Bear in mind that in both natural and synthetically
created flavors and fragrances, these esters are *always* found in
combination with themselves and other substances. A complete list
is virtually endless!
allyl caproate pineapple
amyl acetate apple, banana
amyl butyrate apricot, pear, pineapple
amyl caproate apple, pineapple
amyl valerate apple
benzyl acetate pear, strawberry
bornyl acetate pine tree flavor :-)
iso-butyl acetate cherry, raspberry, strawberry
ethyl acetate peach, pineapple, raspberry
ethyl butyrate banana, pineapple, strawberry
ethyl caproate strawberry
ethyl cinnamate cinnamon
ethyl formate lemon, strawberry
ethyl heptoate grape, pineapple
ethyl isovalerate apple
ethyl heptanoate apricot, cherry, grape, raspberry
ethyl lactate grape
ethyl pelargonate grape
geranyl acetate geranium
geranyl butyrate cherry
geranyl valerate apple
linalyl acetate lavender, sage
linalyl butyrate peach
linalyl formate apple, peach
menthyl acetate peppermint
methyl benzyl acetate cherry
methyl cinnamate strawberry
methyl phenyl acetate honey
methyl salicylate root beer, wintergreen
methyl anthranilate grape, jasmine
nonyl caprylate orange
octyl butyrate parsnip
terpenyl butyrate cherry
>Do any esters have pleasant (to most people) fruity odors yet
>don't correspond to any known fruits?
The reason such esters may seem fruity yet not correspond to any
known fruit is that such esters do not appear *alone* in nature. Offhand,
the best example I can think of is methyl acetate, which (to me, at least)
appears "fruity", but yet corresponds to no one particular fruit odor.
Larry Lippman @ Recognition Research Corp. "Have you hugged your cat today?"
VOICE: 716/688-1231 {boulder, rutgers, watmath}!ub!kitty!larry
FAX: 716/741-9635 [note: ub=acsu.buffalo.edu] uunet!/ \aerion!larry
(1) Although these esters occur in fruits, are they toxic and if so what
do they do to you in sufficient doses ?
(2) How hard are they to synthesize if, like me, you do not know your
gluteus maximum from your olekranon ?
(3) How hard is it to extract them from a piece of fruit, given the same
limitations on competence as in (2), and what yields can one expect ?
(4) Since I am always on the lookout for interesting crystals, what kinds
crystals do they form, how large can they be grown by someone with
the competence described in (2), and where would one look up their
principle dielectric constants (I am assuming they are biaxial) ?
(5) Do all crystals from substances like these tend to sublime ? Naively
I would expect that since I would guess that goes with having a strong
smell. If so, how long does it take for the crystal to disappear in a
hood ?
(6) I tend to think of fruit juices as sticky ? Are the crystals sticky ?
Someday when I have an education, I will ask better questions. Right now,
this is the best I can do.
Allan Adler
gh...@ms.uky.edu
He said that you can't get a really good strawberry flavor/odor unless
you use about 50 components, but most commercial strawberry flavorings
use about 5. This explains a lot about strawberry milkshakes.
He also literally turned a lot of heads on the NY subways by coming home
reeking of grapes in the middle of winter.
You must bear in mind that my list was but a small fraction of esters
which have been identified in fruits.
>(1) Although these esters occur in fruits, are they toxic and if so what
> do they do to you in sufficient doses ?
Many esters have toxic effects resulting from exposure to significant
concentrations; however, in comparison to many other organic compounds,
esters are rather benign.
A good example is amyl acetate, the mixed isomers of which are
commonly called "banana oil". Amyl acetate smells decidedly like bananas,
and in *very* dilute concentration tastes like bananas. Pure amyl acetate
is a not only a rather good solvent, but is highly flammable. If you
tasted *pure* amyl acetate, I can assure you that you would not taste
anything else for quite some hours, although the experience would probably
result in no permanent injury. Breathing significant concentrations of
amyl acetate can result in headache, nausea, irritation to mucous membranes,
and possibly unconsciousness. Amyl acetate in high concentrations has a
narcotic effect.
Comparatively few esters used in fragrances and flavoring are
suspected carcinogens. However, any such carcinogenicity no doubt results
from prolonged exposure to significant concentrations. Since many esters
are used as industrial solvents, such exposure can occur. As an example,
offhand, I believe that ethyl formate is a suspected carcinogen. Chronic
exposure to ethyl acetate from use as an industrial solvent can result in
secondary anemia, fatty degeneration of the liver, leucocytosis, etc., but
I do not believe it is a suspected carcinogen, per se. Nevertheless, ethyl
acetate in minute quantities is used in the formulation of flavorings and
fragrances.
>(2) How hard are they to synthesize if, like me, you do not know your
> gluteus maximum from your olekranon ?
Esters are comparatively easy to synthesize when such synthesis
is performed in a laboratory environment with suitable apparatus and
suitable analytical instrumentation to evaluate the product and efforts
at purification. Proper synthesis also requires "finesse", which is solely
the product of experience in a laboratory.
I suspect your real question is: can esters be synthesized in
a home laboratory environment? The simple answer is probably "yes"
if one has previous organic synthesis experience and some kind of
suitable glassware. If one is attempting such a synthesis for the
first time on their own at home, then anything is possible - ranging
from success to utter disaster.
>(3) How hard is it to extract them from a piece of fruit, given the same
> limitations on competence as in (2), and what yields can one expect ?
This is really the same answer as in the previous question, but
I suspect that extraction and separation is probably easier for certain
esters than synthesis.
If you are going to try something at home, I would first recommend
an effort at extraction. You can probably build a simple filter press
using an inexpensive hydraulic auto jack with a metal frame and a simple
housing for the filter pads. It is neither difficult nor particularly
expensive to acquire the apparatus necessary for fractional distillation.
The challenge, however, is to scrounge apparatus necessary for analysis
of the products; after all, what is the point of synthesizing or extracting
esters if you cannot be certain of their identification? Such analytical
apparatus is not inexpensive, even in the used equipment marketplace. If
I had to recommend one single piece of analytical apparatus that could be
the most useful for the analysis and identification of esters - and yet
still be affordable and maintainable, it would be an Abbe refractometer.
While an IR spectrophotometer would be nice, there are generally
only two types of IR spec's to be found as used apparatus: (1) functional
and (2) inexpensive. Unfortunately, there is little hope of finding a used
IR spec that is *both* functional and inexpensive. :-) Inexpensive used
IR specs often have defective detectors and/or deteriorated salt optics,
the cost to repair being prohibitive for either condition.
>(4) Since I am always on the lookout for interesting crystals, what kinds
> crystals do they form, how large can they be grown by someone with
> the competence described in (2), and where would one look up their
> principle dielectric constants (I am assuming they are biaxial) ?
Most of the esters used in flavorings and fragrances are liquids,
so you won't find much in the way of crystals. Those esters which are
solids tend to have low melting points. An example is benzyl cinnamate,
which has a melting point of less than 40 deg C.
>(5) Do all crystals from substances like these tend to sublime ? Naively
> I would expect that since I would guess that goes with having a strong
> smell. If so, how long does it take for the crystal to disappear in a
> hood ?
In the case of the above example of benzyl cinnamate, the crystals
clearly fuse and melt, and I would not consider this as "sublimation". The
same characteristic is true of cinnamyl cinnamate, methyl anthranilate and
methyl cinnamate. Some of these melting points are around 30 deg C.
>(6) I tend to think of fruit juices as sticky ? Are the crystals sticky ?
I would not consider the comparatively few solid esters as
"sticky". Don't forget that the presence of sugars no doubt accounts
for any "stickiness" in evaporating fruit juices!
>Someday when I have an education, I will ask better questions. Right now,
>this is the best I can do.
You do allright. You seem to sincerely want to learn about
chemistry - more so than anyone I have yet encountered on the Net.
From what I have seen in my travels, development of formulations
for synthetic flavorings and fragrances is more "art" than "science".!
>He said that you can't get a really good strawberry flavor/odor unless
>you use about 50 components, but most commercial strawberry flavorings
>use about 5. This explains a lot about strawberry milkshakes.
A good cherry is supposed to be even tougher to formulate. Here
is an example of a *minimum* synthetic cherry flavoring:
ethyl methyl p-tolyl glycidate 16.0 %
iso-amyl acetate 12.0 %
iso-butyl acetate 12.0 %
p-methyl benzyl acetate 11.0 %
benzaldehyde 8.0 %
vanillin 7.0 %
benzyl alkcohol 5.5 %
piperonal 5.0 %
ethyl caprate 4.0 %
cinnamic aldehyde dimethyl acetal 3.0 %
p-tolyl aldehyde 3.0 %
cinnamyl anthranilate 3.0 %
ethyl caproate 2.0 %
geranyl butyrate 2.0 %
terpenyl butyrate 0.5 %
Sorta makes you wonder why someone decided to add the 0.5 %
terpenyl butyrate, don't it? :-)
>He also literally turned a lot of heads on the NY subways by coming home
>reeking of grapes in the middle of winter.
I have in the past accidentally spilled on myself concentrated
fragrances used in soaps and cosmetics; regardless of how much I scrubbed
and showered, it still required days for the odor to go away.
I've got a couple more questions:
Where would I look for references on the composition of flavors or essences?
The Merck manual has a tantalizing glimpse of this fascinating subject, but
it only mentions flavorings in passing. Is there a Journal of Savory Smells,
Archives of Abstracts of Essences, or equivalent?
Does anyone know what the heck the extremely volatile odor/flavor components
of coriander leaves are? Not the seeds, which have a different flavor.
I'd settle for a reliable extraction procedure so I could extract 10Kg of
cilantro in late summer when it's available, strong, and cheap....
thanks,
geoff steckel (gw...@wjh12.harvard.EDU)
(...!husc6!wjh12!omnivore!gws)
Disclaimer: I am not affiliated with Sun Microsystems, despite the From: line.
This posting is entirely the author's responsibility.
For contemporary textbooks you might consider: "Source Book of
Flavors", "Flavor Chemistry and Technology", "Common Flavor and Fragrance
Materials", etc. There are also various older textbooks which contain a
wealth of information.
For periodicals you might consider: "Perfumer & Flavorist", "Flavour
& Fragrance Journal", "Flavouring Ingredients Processing & Packaging", etc.
In addition, various manufacturers of flavors and fragrances, such
as Norda, publish application literature giving details about composition
of flavors and fragrances.
>Does anyone know what the heck the extremely volatile odor/flavor components
>of coriander leaves are? Not the seeds, which have a different flavor.
Coriander contains d-linalool (3,7-dimethyl-1,6-octadien-3-ol)
and d-pinene. These constituents are found in coriander *fruit*; I cannot
speak with certainty about the seeds. Linalool is also found in oranges,
cinnamon, sassafras and other plants. Pinene is also the major constituent
of turpentine (blech!).
>I'd settle for a reliable extraction procedure so I could extract 10Kg of
>cilantro in late summer when it's available, strong, and cheap....
I would guess that steam distillation of coriander fruit is used
to obtain coriander oil. You could probably use a filter press, which
would be easier to construct, although it would not be as efficient as
direct steam distillation. The oil resulting from filter pressing could
then be refined with conventional fractional distillation.
-Mike
:)
-Oz
IUPAC is a great idea - if we could suddenly wake up one morning
and magically find that all present and past chemical literature has been
translated to IUPAC nomenclature, in addition to having our collective
chemical education so translated.
IUPAC is only very slowly being adopted by chemical industry and
commerce in the U.S. I would gladly attempt to learn and utilize more
IUPAC if only the people I deal with knew what I would be referring to!
>[Don't you think that the IUPAC was introduced to make life less miserable!]
There are times when I have my doubts. :-)
Okay, here's your "translation". I will not stake my life upon
the correctness of all translations, especially the cycloalkyls.
|>allyl caproate 2-propen-1-yl hexanoate
|>amyl acetate pentyl ethanoate
|>amyl butyrate pentyl butanoate
|>amyl caproate pentyl hexanoate
|>amyl valerate pentyl pentanoate
|>benzyl acetate benzyl ethanoate
|>bornyl acetate 1,7,7-trimethylbicyclo[2.2.1]heptan-2-ol ethanoate
|>iso-butyl acetate 2-methylpropyl ethanoate
|>ethyl acetate ethyl ethanoate
|>ethyl butyrate ethyl butanoate
|>ethyl caproate ethyl hexanoate
|>ethyl cinnamate ethyl 3-phenyl-2-propenoate
|>ethyl formate ethyl methanoate
|>ethyl isovalerate ethyl 3-methylbutanoate
|>ethyl heptanoate ethyl heptanoate [How 'bout dat! :-) ]
|>ethyl lactate ethyl 2-hydroxypropanoate
|>ethyl pelargonate ethyl nonanoate
|>geranyl acetate 3,7-dimethyl-2,6-octadien-3-yl ethanoate
|>geranyl butyrate 3,7-dimethyl-2,6-octadien-3-yl butanoate
|>geranyl valerate 3,7-dimethyl-2,6-octadien-3-yl pentanoate
|>linalyl acetate 3,7-dimethyl-1,6-octadien-3-yl ethanoate
|>linalyl butyrate 3,7-dimethyl-1,6-octadien-3-yl butanoate
|>linalyl formate 3,7-dimethyl-1,6-octadien-3-yl methanoate
|>menthyl acetate 5-methyl-2-(1-methylethyl)cyclohexanol ethanoate
|>methyl benzyl acetate methylbenzene ethanoate
|>methyl cinnamate methyl 3-phenyl-2-propenoate
|>methyl phenyl acetate methylphenyl ethanoate
|>methyl salicylate methyl 2-hydroxybenzoate
|>methyl anthranilate methyl 2-aminobenzoate
|>nonyl caprylate nonyl octanoate
|>octyl butyrate octyl butanoate
|>terpenyl butyrate 1,7,7-trimethylbicyclo[2.2.1]hept-2-yl ethanoate
After doing the above list, I now have a headache. I know there
are some white pills that I should take for it, but I can't recall their
IUPAC name... :-)
Thank you very much indeed for providing me the complete list of the translation[shown incompletely above]
The U.S was one of the last countries to adopt the SI/Metric system and it will perhaps be one of the last ones to adopt the IUPAC system. Why is america
so resistant to reformative change. It's not as hard as it seems. Or is it?
Anyway, I'll try out some of these esters some day!
That's interesting! I always knew about the terpene alcohol,
coriandrol (d-linalool or 3,7-dimethyl-1,6-octadien-3-ol) as being the
primary constituent of coriander oil. The linalools (d, l, and dl) have
rather pronounced odors and flavors.
I checked a few references, and they all agree on the above. They
add that the terpene, d-pinene (2,6,6-trimethylbicyclo[3.1.1.]hept-2-ene)
is also present in coriander. d-pinene also has a rather pronounced odor.
Could there possibly be a straight chain aldehyde (7-dodecenal)
present in coriander in enough quantitity to override the effects of
d-linalool and d-pinene?
>Other flavors with similar impact compounds are parsley, orange and
>violet leaf.
I certainly agree with the violet leaf, since such is the odor I
perceive from d-linalool.
>From the fact that these are VERY different from each other,
>it's safe to conclude that details of composition (ratios of high-impact
>compounds, presence of different low-impact compounds) are important in
>these high-aldehyde flavors.
They certainly are different!
I wonder if the explanation for the straight chain aldehydes
is that they are in the coriander leaf, as opposed to the coriander
fruit - with the latter being the source of coriander oil?
FOR YOU HISTORY BUFFS..
"Methode de Nomenclature Chimique", Guyton de Morveau, Lavoisier,
Berthollet, and Fourcroy, 1787.
1889... International Commission on the Reform of Chemical
Nomenclature
... many more attempts ...1947 Organic Commission of IUPAC
1949 Nomenclature of Organic Compounds (IUPAC)
AND NOW FOR THE TRADITIONALISTS...
"... natural products are usually designated by short nonsystematic
names. Rules for assigning such names are far from comprehensive...
...
Whenever practicable, a natural product should be designated by the
systematic name..." Nomenclature of Organic Compounds, Advances in
Chemistry Series #126, ACS 1974.
___________________________________________________________
|Mike Whitbeck | whit...@unssun.unr.edu |
|Desert Research Inst. | whit...@wheeler.wrc.unr.edu |
|POB 60220 | whit...@sanjuan.UUCP |
Was? Past tense? Aside from some random lip service, I havn't
noticed that we've done anything of the sort. I still buy meat by the
pound, gasoline by the gallon, and measure how fast I'm going in miles per
hour. And while the rest of the world is stripped down to shorts and a
T-shirt when it's 30 degrees outside, I'm still wearing my winter coat.
> Why is america so resistant to reformative change.
Ah, that's the problem with those damn fer'ners. They think just
because they outnumber us 20 to 1, we should do things their way! :-) I
remember a funny conversation I had with our building's operations guy a few
years back when we were laying ethernet. He was born and raised in Italy,
but has been here long enough to get used to our funny way of measuring
things. I was explaining to him that I was putting in 150 meters of cable
to reach from here to there and he was insisting that I was way off in my
calculations of how much wire I'd need. It took a few iterations for him to
realize that he had gotten so used to Americans using feet that he hadn't
even noticed I said meters!
--
Roy Smith, Public Health Research Institute
455 First Avenue, New York, NY 10016
r...@alanine.phri.nyu.edu -OR- {att,cmcl2,rutgers,hombre}!phri!roy
"Arcane? Did you say arcane? It wouldn't be Unix if it wasn't arcane!"
Yes, the US still does live in medieval times, if this is the measure - and so
does much of the rest of the world. Take a look at any of the major
international organic chemistry journals (JACS, Tetrahedron, Angewandte
Chemie, JCS, Helvetica Chimica Acta, etc.) and see how much trivial
nomenclature is still in wide use. Do the preps say to use ethyl acetate
or ethyl ethanoate? Are natural products still named things like
srilankenyne (a naturally occurring purple alkyne extracted from sea slugs
off the coast of Sri Lanka), or are the jaw-breaking IUPAC equivalents
used instead?
There is a place for IUPAC nomenclature, but there is also a place for
trivial nomenclature. Personally, I think the best place to use IUPAC
names is in literature and computer searches, but not in day-to-day lab
work...
Bob Murphy
bob...@autodesk.com
I always thought the stuff tasted like turpentine when I
happened to bite into a high-potency chunk of it!
--
Mike Van Pelt I would like to electrocute everyone who uses the
Headland Technology word 'fair' in connection with income tax policies.
(was: Video Seven) -- William F. Buckley
...ames!vsi1!v7fs1!mvp
According to Fowler's Modern English Usage, both "meter" and "metre" are
correct spellings for the measurement unit, with the latter being preferred in
Commonwealth countries. Interestingly, the "meter" spelling is older,
"metre" having been adopted from French at a relatively late date.
(Fowler doesn't say exactly when.) The confusion between the older and newer
forms are readily apparent when you ask a Canadian, Brit or Australian to spell
out km: you're roughly equally likely to get "kilometre" as "kilometer"
(both being correct, especially when you consider the recessive accent
in this word).
Marc R. Roussel
mrou...@alchemy.chem.utoronto.ca
>In article <96...@castle.ed.ac.uk> Julian Bradfield <j...@lfcs.ed.ac.uk> writes:
>>In <1991Apr16....@phri.nyu.edu> r...@phri.nyu.edu (Roy Smith) writes:
>>>even noticed I said meters!
>>And even when you do use them, you get them wrong!
> According to Fowler's Modern English Usage, both "meter" and "metre" are
>correct spellings for the measurement unit, with the latter being preferred in
>Commonwealth countries. Interestingly, the "meter" spelling is older,
>"metre" having been adopted from French at a relatively late date.
I suppose it depends on whether you think you're using SI units or
not. If you are, then the name of the unit is determined by the CGPM,
and is "metre". If you think you're using a French revolutionary unit
of length, then "meter" is one spelling.