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P H E N Y L - 2 - N I T RO P R O P E N E
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P H E N Y L - 2 - N I T R O P R O P E N E ( M E T H Y L A M I N E C A T A L Y SI S )
Writ ten by GC_MS
Ph e ny l- 2 - N it ropr ope ne la Ba r ium : 1 m ol benzaldehyde, 1.2 m ol nit roet hane and 15 m L diluted aqueous
m et hylam ine in 150 m L alcohol. St irred and slight ly heat ed for ca 4 hours. The react ion m ixt ure is brought ov er into
a beaker and cooled in the fridge ( 4 C) . I f precipit at ion doesn't com m ence at t his point, wat er is poured in and t he
m ixt ure put back in t he fridge. The P2NP oil layer will slowly ( or som et im es quickly) st art form ing a cryst alline layer.
I f it doesn't , scrat ching t he wall wit h e.g. a glass rod will help. I f ev en t his won't help, it m eans you probably fucked
som ething up. The yields I have had using t his "adapt at ion": 81% ( i- PrOH) , 79% ( i- PrOH) , 75% ( Et OH) and 71%
( Et OH) ( yields calculat ed aft er crystallizing once; I store m y cryst als in t he freezer and also recryst allize t hem prior
to use) .

P H E N Y L - 2 - N I T R O P R O P E N E ( C Y C L O H E X Y L A M I N E C A T A L Y SI S )
Writ ten by Dream er
To 55 g ( 0.5m ol) Benzaldehy de in a 500m L Flask were
added 40 g ( 0.5m ol) Nit roet hane and 10m L
Cyclohexylam ine. All was refluxed for 6h on a wat er
bat h. The result were 2 layers. One orange layer at
the bot t om wit h phenyl- 2- nit ropropene and a clear
lay er at the top with cyclohexylam ine and m aybe a
lit t le bit ( ~ 1m L) of H2 O. 50m L of H 2 O were added and
then sucked off wit h a pipet t e unt il t he phenyl- 2nitropropene cryst allized ( it cryst allized when it cam e in contact wit h air in presence of 15m L H2 O) . I added 200m L
95% denat urat ed et hanol t o the orange cryst als. The color of t he now needle- lik e cryst als changed from orange to
whit e- y ellow. The cryst als were filt ered. Yield 65 g, 78% of theory.

P H E N Y L - 2 - N I T R O P R O P E N E ( N - B U T Y L A M I N E C A T A L Y SI S )
Writ ten by Zorohustra
CH E M I C A L S

80 m L Toluene ( ACS)

40 m L Benzaldehyde ( ~ 99% )

30 m L Nit roet hane ( > 99% )

10 m L n- Buty lam ine ( p.a.)

PRO CE D U RE
The reactants and am ine cat alysts wer e dissolved in t he t oluene in a 250m L RB flask , boiling st ones were added and
a Dean- St ark set up was rigged ( 10m L trap) . The goal was to boil the solut ion quite heavily t o achieve fast dripping
from t he double surface condenser, a heating m ant le was used.
When t he solution had boiled for an hour 2.7m L wat er was in t he t rap. At six hours som et hing like 7.0m L ( 100% of
theory) had set t led in t he t rap, perhaps t his happened som e t hirty m inut es earlier, because t he chem ist t ook a short
nap. The solut ion was dum ped int o a 250m L beaker, and allowed to cool t o room tem perat ure, it was seeded with
som e pheny lnit ropropene cry st als, and slowly cooled t o around - 10 C ( freezer) . The cry st als looked really nice and
no furt her purification was needed ( Yield 35g) . The filtrat e was concent rat ed under v acuum and cooled like above.
Dirty crystals fell and t hey were recry st allized from 50m L MeOH ( Yield 6g) . The t ot al y ield from bot h crops
am ounted t o 41g ( 64% )
Hm m , hm m the chem ist t hought , perhaps Benzene will increase t he yield, it s lower boiling point would probably
decrease dest ruct ion of form ed phenylnit ropropene. Said and done, t he sam e procedure, set up and chem icals as
above was used in a second experim ent , but wit h 80m L of nice 99.9% benzene as solv ent inst ead of t he toluene.
Aft er boiling t he solut ion for 6h, 3.3m L of wat er was collect ed, aft er 14h 6.7m L, and after 19h 6.9m L was collect ed,
and t he chem ist turned t he heat ing off, t hinking: "I will never get 7.0m L due to t he higher solubilit y of wat er in
Benzene then in Toluene, I 'm j ust k illing yield now"
The solut ion was concent rat ed under vacuum , care taken never even t o sm ell any Benzene. Dum ped t he solut ion in
a 250m L beaker, it solidified com plet ely and j ust 150m L of MeOH was added. This was enough to dissolv e t he
cryst als when boiling. Yield: 42g ( 65.6% ) .
All right , t he yield is j ust above 60% with bot h Toluene and Benzene, lower tem perat ure result s in a slower react ion.
But t here are cases when n- Buty lam ine is a m uch fast er cat alyst and t he t em perat ure is even lower, such as when
using MeOH as solvent . The chem ist decided t o t ry t he reaction and setup once m ore but wit h 60m L cyclohex ane as
solvent , but aft er 20h of boiling only 4.2m L wat er had collect ed in t he t rap, and when cooling down the clear yellow
react ion m ix ture cry st als refused t o form , so t he solut ion is concent rat ed under vacuum to give cry st als, but t he
yield sucked as less t han 10g of product could be isolat ed ( < 15% yield) .

L I T E RA T U RE MET H O D S
PH EN Y L - 2 - N I T RO PRO P EN E
n- Buty lam ine Cat alysis1
One m ole of benzaldehyde, one m ole of nitroethane, 5 m L of n- but ylam ine and 100 m L of anhydrous ethanol were
refluxed for 8 hours in a 1000 m L round- bot t om ed flask. When t he cont ents were cooled and st irred a heavy ,
yellow, cryst alline m ass form ed im m ediat ely. Aft er r ecry st allization from anhydrous et hanol, t he 1- phenyl- 2nitropropene weighed 105 g ( 64% ) , m p 65 C.

PH EN Y L - 2 - N I T RO PRO P EN E
Cyclohexylam ine Cat alysis2
Nit roethane ( 1.0 m L, 13.9 m m ol) and cyclohexylam ine ( 1.3 m L) were added t o benzaldehyde ( 1.0 m L, 9.8 m m ol) in
glacial acet ic acid ( 5.3 m L) . The m ixt ure was held at 100 C for 6 h, cooled and diluted wit h wat er ( 1 m L) . The
react ion m ix ture was cooled overnight in a water bat h. The crystals form ed were filt ered and air dried. The crude
solid was recryst allised from et hanol t o giv e ( E) - 2- nit ro- 1- pheny lprop- 1- ene ( 0.99 g, 62% ) , m p 6465 C.

PH EN Y L - 2 - N I T RO PRO P EN E
Am m onium Acet at e Cat alysis3
A solut ion of benzaldehyde ( 6.4 g) and am m onium acetat e ( 1.0 g) in nit roet hane ( 20 m L) was heat ed t o reflux for 5
h. On cooling, aft er rem oval of t he solvent, t he residue was purified by colum n chrom at ography on silica gel 60 N
( neut ral; hexane- chloroform , 2: 1, v/ v) , t hen recrystallized from hexane and gave 1- phenyl- 2- nit ropropene as a light
yellow crystals weighing 6.2g ( 63% ) , m p 71- 73 C.

RE F E R E N C E S
1 . J. Org. Chem ., Vol. 15, p. 8 ( 1950)
2 . J. Chem . Soc. Perkin Trans. 1, No. 3, pp. 501- 504 ( 1998)
3 . J. Chin. Chem . Soc., Vol. 49, pp. 505- 508 ( 2002)