A new reducing agent for nitrostyrenes: bakers yeast! -Labrat

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Author  Topic:   A new reducing agent for nitrostyrenes: bakers yeast! 
Labrat
Member   posted 09-28-98 09:21 AM          
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For all those people who can't find sodium borohydride, this is for you. First check out the following articles:
JCS Perk. Trans. 1: 501 ('98)
Aus. J. Chem. 49: 1257 ('96)
JOC 54: 1802 ('89)
Heterocycles 37: 553 ('94)

In these articles, bakers yeast is used to reduce b-nitrostyrenes to b-nitrophenethanes. These latter compounds can easily be reduced to the amines in at least 90% yield by a simple aluminum amalgam reduction. So this is an alternative 2-step nitrostyrene reduction, using easy-to-get chemicals!

The reaction conditions to get the best yields are as follows:

1 mmol nitrostyrene substrate
11 g yeast
0.8 ml water per g yeast (8.8 ml)
50 ml light petroleum

A representative procedure from JCS Perk. Trans. 1: 501 ('98):
"0.3 g nitrostyrene (2 mmol), 22.13 g bakers yeast, 17.7 ml water and 200 ml light petroleum were stirred at room temp for 24 h. The solvent was removed by filtration and the yeast washed with 3x50 ml CH2Cl2. The filtrates were combined and evaporated in vacuo to give a residue of 2-nitro-1-phenylethane (0.216 g, 72% yield)."

This reaction is simplicity itself, doesn't use hard-to-get chemicals and can be scaled up to bathtub size. The yield is pretty much the same as when using NaBH4 as reducing agent, 65-75%. Isn't this great?! Lr/

quirks
Member   posted 09-28-98 09:33 AM          
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What's light petroleum?
 
Piglet
Member   posted 09-28-98 10:08 AM          
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LR: Fucking hell man! Are you on strong stimulants? The number of ideas/posts you have made recently is crazy.
Will this work with nitropropenes? This is an excellent post. Funny and serious all at once. Sweeet.

Best wishes,
Piglet 

Labrat
Member   posted 09-28-98 04:51 PM          
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quirks: light petroleum is petroleum ether.
Pig: strong stimulants? Well, I think it's more due to the great ganja we have here lately!

This nice little procedure does indeed work on nitropropenes too. When nitrostyrene was substituted for nitropropene with the same reaction conditions, a 66% yield of 2-nitrophenyl-1-propene was obtained. Lengthening the reaction time could very well give better yields.

Great you like the post. Lr/

Rhenium
Member   posted 09-28-98 07:48 PM          
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Labrat,
You continue to do the Hive proud. This is a funny but great post. If I was to tell my freak friends that I used baker's yeast to reduce my nitro-styrene's, even they would look at me funny. Pity the molar ratios are so hugely different, (0.3g:22g) but that's not a real problem, yeast can be bought by the bag. What the hell is the mechanism I wonder, I going to go get those referencs today!
Yeast? Hmmmmm... I wonder if you could use Vegemite instead?

Take care,

Rhenium

Labrat
Member   posted 09-29-98 09:41 AM          
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Thanks! I admit, using bakers yeast as a reducing agent is very freakish, but I can't help picturing somebody performing this reaction in the jaccuzy (?)! And it's a nice alternative for NaBH4 too!
BTW, what is Vegemite? A brand of bakers yeast I presume. Lr/

Snidely Whiplash
Member   posted 09-29-98 12:20 PM          
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"He just smiled and gave me a Vegemite sandwich"
- "Down Under" by Men At Work, circa ~1982

labgrrrl
Member   posted 09-29-98 08:27 PM          
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Vegemite is a yeast "spread" that you put on bread, toast, etc...it's kinda freaky stuff and not unlike Marmite. And, no you couldn't use it as a substitute for bakers yeast 
I was exposed to such delights as a little grrrl...

-labgrrrl

Rhenium
Member   posted 09-30-98 08:01 AM          
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I was just kidding about the Vegemite, but I did get those papers, very interesting...
Ah, the ingenuity of chemistst (real or clandestine) never ceases to amaze me.
Labgrrl, where were you when you were exposed to the deights of Vegemite? I'm still in Vegemite Land myself...
"The worlds richest source of Vitamin B!"
Take care,

Rhenium

Labrat
Member   posted 09-30-98 09:43 AM          
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Shit, I think I know what you mean with Vegemite. I don't know anymore what it's called around here. I do remember the intense gory salty taste and the fact that it looks like road tar. And yes, it contains vitamines B (but so do vitamin pills).
But no more questions on the bakers yeast reduction? Great, that means I've explained it clear and simple the first time. Lr/

Piglet
Member   posted 10-12-98 09:27 AM          
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US Patent 4,106,986 describes epoxide formation from alkenes.
 
Labrat
Member   posted 10-13-98 09:28 AM          
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"The production of epoxide from .alpha.-olefin or .alpha.,.omega.-diene using an epoxide producing microorganism that belongs to Nocardia genus...".
In this method a bacteria of the Nocardia genus is used. I've no idea where to find a batch of these microorganisms. You know where Piglet? Lr/

Piglet
Member   posted 10-13-98 10:05 AM          
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I hunted on the net. Apparently they are EVERYWHERE in the enviroment. Getting a PURE source, I'm not sure. Anyone?
 
Labrat
Member   posted 10-15-98 10:23 AM          
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Maybe a biologist could tell us how to select the proper bacteria genus with the right medium. But I'm no biologist, so I still ain't got a clue. Lr/
 
NectarBoy
unregistered   posted 10-26-98 05:43 PM           
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You would need to find a source,get a sample and grow it in plates of nutrient agar,then you would have to distinguish between the organisim you want and the other ones you dont want.Well,Ill read more on it an get back to all you cats
 
gyrogearloose
Member   posted 11-09-98 05:57 AM          
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I looked in my trusty Merck index and found this is an old method, not new, the yeast is there under yeast, but it really does work...
I think everyone should buy a copy and read before posting here, I felt more confident after. It has so much info.
For instance all the talk of peonut oil and cotton seed oil, both are listed as solvents for aids in pharm. work. Given this I didcided to try to distill with the aid of peanut oil and then cotton seed oil, dude, My best yeild ever for mdp2p after the formic crap.
 
Bozakium
Member   posted 11-10-98 09:27 PM          
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Will other yeasts work? Could nitrostryenes be reduced, not in vacuo but in vaguo if one's wife had a yeast infection?
 
Labrat
Member   posted 11-12-98 10:07 AM          
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First recovering that yeast from the yeast infected place with your tongue! Then give it a try, who knows, it might work!
 
dpHarma
Member   posted 11-15-98 02:01 AM          
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gyro
please post some details of the use of peanut oil after performic!
Thanks

dpHarma

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[PolytheneSam]

This looks interesting.

[foxy2]

So try it and report back


Do Your Part To Win The War

[LaBTop]

Where is this bright young fellow nowadays?
LR/, PM me! You can use PGP, my key is in my profile. LT/

WISDOMwillWIN

[otto]

hello,

otto was looking for some bakers yeast. dry yeast as in literature is put together with an emulsifier (lecithin or something) before one can buy it. this could cause a problem. fresh yeast from bakery contains too much water according to the recipies. an investigation on 0.5 g of TMP2NP is underway.

otto

[otto]

after 24 hours there is still nitropropene present as was proved by TLC. 80 g of fresh (equals ~ 22 g of dry) yeast was put togehter with 0.5 g TMP2NP in 250 ml of hexane in a 500 ml RBF.

remarks:
magnetical stirring is impossible, mixture was shaken from t2t. TMP2NP is hardly soluble in hexane. a little warming helps.

continuing...

[dmt_elvis]

I suggested all kinds of microbes that had the metabolic abolity to do all kinds of things in this area, years ago.
Got flamed by Hive idiots for my trouble.

http://members.tripod.com/Chemo_Gnostic/yeast.htm

[FlamingMaggot]

It's not our fault that your an antisocial troglodyte. You made it so easy for us to behave badly.  

Ladies and Gentleman, I axe you: Would you trust this knucklehead with anything but the removal of your garbage from the curb?



I did'nt think so...................

Btw, I noticed how you removed the, er, "bedpan" experience from your resume........... That wuz a smart career move.

[dmt_elvis]

as usual, pointless trolling from an ignorant fool with no facts and nothing important to say at all.
go find a jigsaw puzzle or something.

[otto]

so ,after 5 days with occasional shaking (other data see above post), the nitrpropene still hadnt disappeared (TLC). the hexane layer was decanted and yeast was washed twice with hexane. the combined layers gave upon evaporation an orange - yellow oil. no cristals!

it seems that one must use instant yeast and stirring is a limiting factor. i have no further oppotunities to verify what did happen. it appers though that a conversion did take place.

otto

[sunlight]

What you are looking for is probably a yellow oil !!!

[blue]

You sure, sunlight? The reason I ask is during some dreams  reducing 2,4,5 TMP2NP w/ NaBH4 we judged the rxn complete when all yellow color had disappeared from rxn. Although when solvent was stripped it was closer to skin color. Not yellow.

Otto is that the 2,4,5 or the 3,4,5 TMP2NP?

[otto]

hello blue,

it's the 2,4,5 - isomer.

otto

[blue]

yummy, we had the best dreams reducing the nitro group using MeOH w/ 10%H2O at ambient temp. Using large XS of Al added in portions. Happy cooking.

I have the refs that dream was based on if you are interested, they are spartan though.

[sunlight]

May be the pure product is white, but a bit of coulour doesn't mean it is not enough pure. 2,5 DMN ethane is pale yellow, but a yellow-brown product is reduced to the amine perfectly.

[magic]

the reduction of alphamethylnitrostryenes rather than nitrostyrenes with bakers yeast is also enantioselective I dont know what the ee is without looking it up. But is a possible route to optically active amphets

[Stonium]

Where is this bright young fellow nowadays?

Uhm well, I'm not exactly sure about that but I think I know how to contact him via email. Heh..my very first Hive honey he was.    

The proverbial proprietor provides practical proverbs.

[foxy2]

Mechanism of the yeast mediated reduction of nitrostyrenes in light petroleum.    
McAnda, Anita F.; Roberts, Kade D.; Smallridge, Andrew J.; Ten, Abilio; Trewhella, Maurie A. 
Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry  (1998), (3), 501-504. 

Abstract
The yeast-mediated redn. of a range of a- and b-D-substituted nitrostyrenes was conducted in light petroleum contg. a small amt. of H2O or D2O.  NMR anal. of the products from these reactions allowed the detn. of the mechanism of this redn.  Initially, a reversible non-stereoselective protonation occurs at the b-center, followed by stereoselective addn. of hydride at the a-position.


Experimental Yeast reactions

Reduction of (E)-2-nitro-1-phenylethene 6.
(E)-2-Nitro-1-phenylethene 6 (0.3 g, 2.0 mmol), yeast (22.13 g, 11 g/mmol of 6), H2O (17.7 ml) (0.8 ml per g of yeast) and light petroleum (200 ml) were stirred at room temperature for 24 h. The solvent was removed by filtration and the yeast was washed with dichloromethane (3 × 50 ml). The filtrates were combined and evaporated in vacuo to give a residue which was bulb-to-bulb distilled to give 2-nitro-1-phenylethane 4 (0.216 g, 72%), bp 150 8C/0.5 mmHg;

Reduction of (E)-2-nitro-1-phenyl[1-2 H]ethene 1.
(E)-2-Nitro-1-phenyl[1-2 H]ethene 1 (0.3 g, 2.0 mmol) was stirred with yeast (21.98 g, 11 g/mmol of 1), H2O (17.5 ml) and light petroleum (150 ml) for 24 h to give 2-nitro-1-phenyl[1-2 H]ethane 2 (0.198g, 65%) bp 150 8C/0.5 mmHg;

Reduction of (E)-2-nitro-1-phenyl[2-2 H]ethene 3.
(E)-2-Nitro-1-phenyl[2-2 H]ethene 3 (0.4 g, 2.7 mmol) was stirred with yeast (29.3 g, 11 g/mmol of 3), H2 O (23.4 ml) and light petroleum (200 ml) for 24 h to give a mixture of 2-nitro-1-phenylethane and 2-nitro-1-phenyl[2-2 H]ethane 5 (0.176 g), bp 150 8C/0.5 mmHg;

Reduction of (E)-2-nitro-1-phenyl[1-2 H]prop-1-ene 7.
(E)-2-Nitro-1-phenyl[1-2 H]prop-1-ene 7 (0.3 g, 1.2 mmol) was stirred with yeast (20.10 g, 11 g/mmol of 7), H2 O (16.1 ml) and light petroleum (200 ml) for 24 h, to give 2-nitro-1-phenyl[1-2 H]propane 8 as a mixture of diastereomers (0.198 g, 66%), bp 150 8C/0.5 mmHg; 

Reduction of (E)-2-nitro-1-phenylprop-1-ene 10.
(E)-2-Nitro-1-phenylprop-1-ene 10 (0.3 g, 1.8 mmol) was stirred with yeast(12.8 g, 7 g/mmol of 10), D2O (10.2 ml) and light petroleum (150 ml) for 24 h to give a mixture of starting material and reduced products (0.201 g, 67%) bp 150 8C/0.5 mmHg;

Those who give up essential liberties for temporary safety deserve neither liberty nor safety

[foxy2]

Asymmetric reduction of nitroalkenes with baker's yeast.
Kawai, Y.; Inaba, Y.; Tokitoh, N.   
Tetrahedron: Asymmetry  (2001),  12(2),  309-318.
Abstract
Various a,b-disubstituted and trisubstituted nitroalkenes, e.g., R1R2C:CR3NO2 (R1 = H, Ph, R2 = Ph, H, 2-MeC6H4, CHMe2, etc., R3 = Me, Et), were chemoselectively reduced with baker's yeast to the corresponding nitroalkanes.  Stereoselectivities of the redn. of a,b-disubstituted nitroalkenes were modest to low, and e.e.s up to 52% were obtained.  Trisubstituted nitroalkenes could be reduced to the corresponding nitroalkanes with excellent enantioselectivities, moderate diastereoselectivities and in good yield.  The crystal structure and abs. configuration of an amine hydrochloride derived from a nonracemic nitroalkane product was detd. by x-ray anal.

General procedure for the reduction of a,b-disubstituted nitroalkenes by baker's yeast
Nitroalkene (2.5 mmol) dissolved in ethanol (5.0 mL) was added to a stirred suspension of dry baker's yeast (25 g) in water (150 mL) at 35°C. The reaction was followed by gas chromatography. When the substrate was consumed completely or after 24 h, the reaction was worked up as follows. Acetone (150 mL) was added to the reaction mixture and the mixture was filtered through hyflo super-cel®. The residue was washed three times with acetone and the washing solution was combined with the filtrate. The mixture was evaporated under reduced pressure to 100 mL and the organic materials were extracted with diethyl ether. The ether solution was dried over anhydrous magnesium sulfate. Evaporation of the solvent gave a crude product, which was purified by column chromatography on silica gel with hexane/ethyl acetate (20/1). The yields and the enantiomeric excesses are summarized in Table 2. The spectral data are shown below.


Table 2. Baker’s yeast reduction of disubstituted nitroolefins 1a–t
------------------------------------------------------------
Reaction time (h), Yield (%), %E.e.
------------------------------------------------------------
1-Phenyl-2-nitropropane 2a
2, 81, 12

1-(2'-Chlorophenyl)-2-nitropropane 2c
1.5, 52, 4

1-(3'-Chlorophenyl)-2-nitropropane 2d
3, 47, 2

1-(4'-Chlorophenyl)-2-nitropropane 2e
3, 51, 7

1-(2'-Methylphenyl)-2-nitropropane 2f
5, 65, 3

1-(3'-Methylphenyl)-2-nitropropane 2g
3, 61, 2

1-(4'-Methylphenyl)-2-nitropropane 2h
7, 58, 0

1-(2'-Methoxyphenyl)-2-nitropropane 2i
5, 72, 3

1-(3'-Methoxyphenyl)-2-nitropropane 2j
3, 68, 9

1-(4'-Methoxyphenyl)-2-nitropropane 2k
5, 66, 45

Those who give up essential liberties for temporary safety deserve neither liberty nor safety

[foxy2]

The yeast-mediated reduction of nitrostyrenes in organic solvent systems.  
Bak, Radoslaw R.; McAnda, Anita F.; Smallridge, Andrew J.; Trewhella, Maurie A.
Australian Journal of Chemistry  (1996),  49(11), 1257-1260.

Abstract
A range of nitrostyrenes were reduced with dried bakers' yeast in an org. solvent system.  The redn. proceeded smoothly to give the corresponding nitroalkanes in good yield and with higher efficiency than the corresponding aq. reaction system.  No evidence for redn. of the nitro group was obsd.  In the case of b-Me nitrostyrenes, racemic mixts. were formed, which is not due to racemization of the product. 
Those who give up essential liberties for temporary safety deserve neither liberty nor safety