LSD25
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Hunsdiecker-Borodin-etc. Reaction
I was told it might be an idea to put the information I have on this article in a new topic - so I have done so. This would appear to be a very useful
reaction for home chemists, particularly if it turns out that more OTC reagents could be used.
http://www.organic-chemistry.org/namedreactions/hunsdiecker-...
That said, I have no experience with this reaction so I invite comment from those that do.
Bazin, et al, 'Original 1pot MW-Promoted Hunsdiecker-Suzuki Strategy...' (2007) 48 Tet Let 4347:http://tinyurl.com/4cjyj9
| Quote: | | Abstract—An original strategy combining a Hunsdiecker-type bromodecarboxylation and a Suzuki cross-coupling reaction starting from various cinnamic
acids has been developed in one-pot and under microwave heating to give trans-1,2-diarylethenes in few minutes. |
Bernini, et al, 'Obtaining 4-VP by decarboxylation of Natural 4-OHCinnamic Acids under MW Irradiation' (2007) 63 Tet 9663: http://tinyurl.com/4l6hlr
| Quote: | | Abstract—4-Vinylphenols, useful compounds for industrial applications, were obtained by decarboxylation of 4-hydroxycinnamic acids under microwave
irradiation in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as base and basic aluminum oxide as solid support. The reactions were fast
(15–30 min). The selective extraction of the final products with ethyl acetate avoids chromatographic purifications. The conversions are
quantitative and the yields are satisfactory. Only the unstable 4-vinylcatechol was obtained in moderate yield. This procedure was successfully
extended to a natural sample of ferulic acid extracted from wheat bran to get the corresponding 4-vinylguaiacol, a FEMA GRAS (Flavor and Extract
Manufacturer’s Association; General Regarded as Safe) approved flavoring agent. |
Koo, Kim & Lee, 'Bromodecarbonylation & Bromodecarboxylation of Electron Rich Benzaldehydes...' (2002) 32(15) Synth Comm's 2275: http://tinyurl.com/3oj26a
| Quote: | Benzaldehydes and benzoic acids bearing ortho- and para- electron donating substituents having unshared electron-pair have undergone
bromodecarbonylation or bromodecarboxylation on treatment with sodium bromide in the presence of Oxone in aqueous methanol.
Key Words: Bromodercarbonylation; Bromodecarboxylation; Oxone; Sodium bromide; Electron-rich benzaldehydes; Benzoic acids |
Kuang, et al, 'Convenient & Stereoselective Synthesis of (z)-1-Br-1-Alkenes by MW-Induced Reaction' (2001) 42 Tet Let 3893: http://tinyurl.com/47r73g
| Quote: | Abstract—(Z)-1-Bromo-1-alkenes were stereoselectively prepared in high yields in a short reaction time (0.2–1.0 min) by
microwave irradiation of the corresponding 2,3-dibromoalkanoic acids in DMF in the presence of triethylamine. |
Kuang, et al, 'Stereoselective Synthesis of (E)-ß-arylvinyl bromides by MW induced Rxn...' (2005) 61 Tet 637: http://tinyurl.com/3w6oxv
| Quote: | Abstract—(E)-b-Arylvinyl bromides were stereoselectively prepared in high yields by microwave irradiation of the corresponding anti-3-
aryl-2,3-dibromopropanoic acids in AcOH in the presence of AgOAc for 0.5–3.0 min. |
Naskar & Roy, 'Cat Hunsdiecker Rxn & 1-Pot Cat H-Heck Strategy...' (2000) 56 Tet 1369: http://tinyurl.com/5xmmb4
| Quote: | Abstract—The reaction of a,b-unsaturated aromatic (or heteroaromatic) carboxylic acids with N-halosuccinimides (1 equiv.) and catalytic
tetrabutylammonium trifluoroacetate (0.2 equiv.) in dichloroethane results in facile halodecarboxylation affording the corresponding (E)-halides in
good to excellent yields. A similar reaction, but with 2 equiv. of N-halosuccinimides in acetonitrile-water (1:1 v/v) results in the exclusive
formation of the corresponding a-(dihalomethyl)benzenemethanols. Furthermore, a one-pot strategy has been developed combining catalytic Hunsdiecker
reaction (using tetrabutylammonium trifluoroacetate in dichloroethane) and Heck coupling (using palladium
acetate/triethylamine/triphenylantimony/dichloroethane) for the synthesis of 5-aryl-2,4-pentadienoic acids, esters and amides
in moderate to good yields. The natural product piperine and pipergualamine has been synthesized via the above route. Mechanistic and theoretical
studies (via AM1 calculations) provide a useful insight into the mechanism of the present halodecarboxylation reaction, suggesting an ionic pathway
involving the attack of the halogenium ion across the carbon–carbon double bond, triggering the elimination
of carbon dioxide. |
Naskar, et al, 'Is Metal Necessary in the Hunsdiecker-Borodin Reaction...' (1998) 39 Tet Let 699: http://tinyurl.com/46nogn
| Quote: | | ABSTRACT: The tetrabutylammonium trifluoroacetate (TBATFA) catalyzed conversion of a, 3-unsaturated carboxyiic acids to the corresponding halides with
N-halosuccinimides in dichloroethane is reported as the first example of a rnetal-froe catalytic version of the title reaction. The methodology was
further employed for a facile synthesis ofpiperine. |
Ramgopal, et al, 'Metal Nitrate driven Nitro Hunsdiecker Rxn with a,b-unsat Carbox Acids under Solvent-free Conditions' (2007) 48 Tet Let 4043: http://tinyurl.com/4qb4d6 (This one looks dodgy - Indians, nitrates... that combination makes me nervous)
| Quote: | Abstract—Hunsdiecker reactions with a,b-unsaturated carboxylic acids were conducted under solvent-free conditions in the presence of a few drops of
HNO3 together with a variety of metal nitrates [Mg(NO3)2, Sr(NO3)2], Al(NO3)3, Ca(NO3)2, Ni(NO3)2, Cd(NO3)2, Zn(NO3)2, Hg(NO3)2, AgNO3, ZrO(NO3)2,
UO2(NO3)2, Th(NO3)2] or ammonium nitrate. a,b-Unsaturated aromatic carboxylic acids underwent nitro decarboxylation to afford b-nitro styrenes in
moderate to good yields, while a,b-unsaturated aliphatic carboxylic acids underwent decarboxylation to yield the corresponding nitro derivatives.
(Like I said, seems too good to be true) |
Sinha, et al, '1-Pot 2-Step Synth of 4-Vinylphenols from 4-Hydroxy-sub-Benzaldehydes under MW ...' (2007) 63 Tet 960: http://tinyurl.com/3v8nvw
| Quote: | Abstract—The classical Knoevenagel–Doebner reaction is reinvestigated wherein the direct synthesis of substituted 4-vinylphenols instead of the
expected 4-hydroxycinnamic acids is described. The condensation reaction is performed on 4-hydroxy substituted benzaldehydes and malonic acid with a
mixture of acetic acid–piperidine as condensing agent under focused microwave irradiation. The occurrence of simultaneous
condensation–double decarboxylation without the use of any decarboxylating agent is a new finding, the reaction being facilitated solely by the
hydroxy substituent and microwave irradiation effect. |
THE DECARBOXYLATION OF AMINO ACIDS, PROTEINS, AND PEPTIDES BY N-BROMOSUCCINIMIDE : http://tinyurl.com/3fq3zv
| Quote: | | In the present paper, we describe a decarboxylation method, based upon work by Barakat et al. (3-6), which lends itself to the determination of amino
acids and offers considerable promise in the determination of end group carboxyls in peptides and proteins. The decarboxylating agent is
N-bromosuccinimide. This compound has had extensive use as a reagent for the bromination of unsaturated compounds and, with suitable catalysts, for
other compounds as well (7). These bromination reactions are carried out in organic solvents, usually carbon tetrachloride. Aside from the observation
that N-bromosuccinimide is hydrolyzed to hypobromous acid and succinimide in the presence of water, no serious investigation of the properties of
N-bromosuccinimide in an aqueous medium had been undertaken until the work of Barakat. He observed that certain a-substituted carboxylic acids were
decarboxylated with a concomitant evolution of bromine when allowed to react with an aqueous N-bromosuccinimide solution. Among the various
a-substituted carboxylic acids which were susceptible to this reagent was alanine. It is pertinent to note that the reaction went to completion at
room temperature. |
You & Lee, 'Halodecarboxylation of a,b-Unsaturated Carboxylic Acids...' (2001) 1 Synlett 105: http://tinyurl.com/45poeo
| Quote: | Abstract: Reaction of a,b-unsaturated carboxylic acid bearing aryl and styrenyl group at b-carbon with Oxone® and sodium halide in aqueous
acetonitrile afforded the corresponding haloalkenes.
Key words: halodecarboxylation, Hunsdiecker reaction, Oxone,
sodium halide, a,b-unsaturated aromatic carboxylic acid |
There are also two others, cited in the CHCl3-CCl4 thread, from ACS, which appear to be closely related to this. Is it possible to gain access to the
PDF's of those?
All in all, these appear to hold promise - but more information is needed - preferably using either the oxone variant or TCCA for preference.
[Edited on 7-4-2008 by LSD25]
Whhhoooppps, that sure didn't work
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not_important
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this thread
http://www.sciencemadness.org/talk/viewthread.php?tid=9855&a...
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LSD25
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I think the idea was to provide a good hit on TFSE. The links are already on this site and I was basically warned off putting any more on this where
it was being discussed (it would have dragged the thread off-topic), so I figure that is the reason why I was told to start a thread . Figured for once I might just do as I'm told
PS For the sake of clarity and full disclosure - Solo got a lot of these articles.
Whhhoooppps, that sure didn't work
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MagicJigPipe
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Thanks LSD25! I almost forgot about that site! It is an extremely excellent quick reference for reactions of all types.
"There must be no barriers to freedom of inquiry ... There is no place for dogma in science. The scientist is free, and must be free to ask any
question, to doubt any assertion, to seek for any evidence, to correct any errors. ... We know that the only way to avoid error is to detect it and
that the only way to detect it is to be free to inquire. And we know that as long as men are free to ask what they must, free to say what they think,
free to think what they will, freedom can never be lost, and science can never regress." -J. Robert Oppenheimer
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smuv
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THE DEGRADATION OF CARBOXYLIC ACID SALTS BY MEANS OF HALOGEN
Johnson, R. G.; Ingham, R. K. Chem. Rev. 1956, 56, 219
here
REACTIONS OF THE HALOGENS WITH THE SILVER SALTS OF CARBOXYLIC ACIDS
Kleinberg Chem. Rev., 40(3), 381.
here
The first is a more comprehensive review than the second; It reports the preparation of acetyl bromide from silver pyruvate.
EDIT: Ok I have tried uploading the files 4 times, they always become corrupt; the source files are good, I test them every time before and after i
put them up. The answer, I'll host 'em on my webspace for a while, someone more competent than me can upload them.
[Edited on 7-4-2008 by smuv]
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solo
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smuv....the best way to do multiple files is to zip the files and make it your attachment......solo
It's better to die on your feet, than live on your knees....Emiliano Zapata.
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JohnWW
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Smuv - the file is corrupt - "unexpected end of archive", and the PDF could not be opened or extracted.
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not_important
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There is a problem with the board software, even has its own thread, where the very end of files get stepped on. With most simple PDFs this lands
someplace that doesn't harm the file, but with ZIPs it corrupts the zip directory.
Also ZIP or RAR compression of PDFs rarely saves that much storage, given the problem with the board software it is better to leave single PDF files
as PDF format.
[Edited on 8-4-2008 by not_important]
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smuv
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I know this fact, but the pdf was too large to upload 1 shot, so I needed to split it up to stay below the max file size.
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Nicodem
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LSD25, thanks for the compilation. I only have a couple of comments for better understanding. Some of the cited papers are not about the Hunsdiecker
reaction:
- Bernini et al is a about the decarboxylation of cinnamic acids: Ar-CH=CH-COOH > Ar-CH=CH2
- Koo, Kim and Lee is about the observed ipso bromination of benzoic acids using their oxone/bromide method
- both Kuang, et al are about brominating the double bond of cinnamic acids followed by HBr&CO2 elimination (not necessarily trough their
mechanism proposal but surely not trough the Hunsdiecker reaction)
- Naskar et al does not appear to be about a Hunsdiecker reaction even though the authors claim it as such (yet their mechanism proposal effectively
rules out the occurrence of the Hunsdiecker reaction and so does the substrate specificity)
- Ramgopal et al is similar in that the authors call it a Hunsdiecker reaction already in the tittle yet the paper is about the long know
decarboxylative nitration of cinnamic acids (which is at least a century known reaction, yet nothing to do with Hunsdiecker)
- Sinha et al is at least honest in claiming no relation to Hunsdiecker while describing their method of Knoevenagel condensation with malonic acid
and decarboxylation in a one pot method
- Chappelle and Luck is about the observation that NBS oxidatively decarboxylates most amino acids without determining the mixture of products.
…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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LSD25
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Yeah, I got told that last time I believe (n_i) - but that is what comes up with the search term and also decarboxylation - it is all useful for
someone in the future I hope - just remember, I have to log in monthly to keep this info current, so if anyone downloads it and puts it somewhere
accessible that would be great.
Getting slightly off-topic, in your estimation, would the Ramgopal, et al, approach via cinnamic (or for the criminally inclined, a-methylcinnamic to
get the b-nitrostyrene you were probably interested in) be worth a shot? What about the aliphatic carboxylic acids (acetic/propionic)?
PS I think the confusion on my part grew from finding the initial reference, which I believe was the Naskar, et al, which was then linked on the
database to the others as references for the most part. This then led me to search 'decarboxylation + succinimide' and variants, which led to the
rest. I hope you note that the folder that this is contained in is merely termed 'decarboxylation' not 'Hunsdiecker Rxn' as it once was. I think
perhaps I should also modifiy the name of the thread for search engine purposes. Unfortunately I cannot do so, can you? Please?
[Edited on 9-4-2008 by LSD25]
Whhhoooppps, that sure didn't work
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Nicodem
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If you are interested in the ipso substitution of the COOH group by nitration of cinnamic acids (let's call it "decarboxylative nitration" in
general, since not all are electrophilic substitutions; some proceed as radical reactions) check these references:
Tetrahedron Letters, 47 (2006) 1885-1888.
Tetrahedron Letters, 46 (2005) 8141-8143.
Journal of the Chinese Chemical Society (Taipei, Taiwan), 52 (2005) 173-180.
Synthetic Communications 34 (2004) 3317-3324.
Tetrahedron Letters, 45 (2004) 1179-1181.
Organic Letters, 4 (2002) 3055-3058.
Canadian Journal of Chemistry, 66 (1988) 1670-1674.
PS: I think the thread title is fine as is for now. Unfortunately there are no review papers on the Hunsdiecker reaction in the literature that I’m
aware of so there is an interest in compiling the information about it. Even though up to now we actually have no paper posted about the Hunsdiecker
reaction, I’m sure that adding information on other type of reactions involving decarboxylation will not bother anybody.
…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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S.C. Wack
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US2176181
JOC 21, 1388 (1956)
JOC 26, 280 (1961)
JOC 30, 415 (1965)
JOC 44, 3405 (1979)
Attachment: 8_joc_pages.pdf (965kB)
This file has been downloaded 2283 times
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