Vitus_Verdegast (Hive Bee)
04-27-03 22:46
No 429807
      fractional destillation of parsley seed oil     

Some time ago, mr. Poelzig, an acquaintance of mine, ordered 500 ml of Parsley seed oil. The parsley, Petroselinum crispum, was the Indian variety. The certificate of analysis didn't mention its constituents, only the physical parameters. So mr. Poelzig decided to distill 250 ml of this oil using fractional vacuum destillation. He uses a fridge pump, which boils safrole at 110C.

fraction 1: 78-100C, about 25 ml, strong terpene odour, reminds one of pine oil.

fraction 2: 108-115C, 140 ml, mild terpene like odour

fraction 3: 115-120C, 50 ml, strong harsh odour

fraction 4: +120C, 25 ml, undistilled, viscious syrupy oil with harsh odour when warm (assumed to be apiole).

Will distill 4th fraction when 14" apparatus and conical flasks arrive.

I can't seem to find any detailed info on the main constituents of Indian Parsley seed oil. Next to phenylpropanoids there should be mainly pinene and phellandrene in it. These are assumed to be the ingredients of fraction 1, but I cannot figure out what the chief constituent (fraction 2) could be.

http://www.ealasaid.com/fan/lorrelibrary/b-wing/bc/intro.wav
 
 
 
 
    GC_MS
(Hive Addict)
04-28-03 00:17
No 429826
      Possibly interesting
(Rated as: excellent)
    

Might be helpful:

G Mammola, V Paolini, L Balbiano. Azione dell'acetato mercurico sull'apiolo ed isoapiolo. Gazetta chimica italiana 36 (1906) 286-291.

Apiole is the principal constituent of the essential oil derived from the seeds of the plant species apium petroselinum. Its constitution is known particularly thanks to the research of Ciamician and Silber 1. They demonstrated that apiole is a pentasubstituted benzene. Because of the work for H Toms 2 we are also sure about the position of the 5 substituents, as is shown in the following scheme: [...] V Gerichten 3 described the isomere, videlicet isoapiole, at the end of 1876. Its difference from apiole is to be searched for in the C3H5 side chain, which is allylic for apiole and propenylic for isoapiole.[...]

1. Gazz chim It 21, p 164
2. Ber Deutsch chem Ges 36, p 1714
3. Ber Deutsch chem Ges 9, p 1477.

E v Gerichten. Ueber das Terpen des Petersilienoels. Ber Deutsch chem Ges 9 (1876) 258-260.

This terpene has been first described and analyzed by Huebschmann 1. [...] The parsley oil which had been used by Huebschmann, is reported to boil only at 210C [note: might be 310 as well; unclearly printed, but I guess it should be 210C]. The temperature then suddenly increased "to a point, at which the residue solidified".[...]

E v Gerichten. Ueber das Apiol. Ber Deutsch chem Ges. 9 (1876) 1477-1479.

The Berichte articles can be referred to at the Gallica website (http://gallica.bnf.fr - periodicals section). I hope the Italian translation is more or less OK... My Italian is rather rusty tongue. The German articles are not easily translated, at least not by me. Of course, I understand what is written, but I find it hard to translate it into proper English. They deal with the constitution of parsley seed oil, especially a main fraction, called the "terpene fraction". They also investigate the presence of apiole. If you can't understand the text but are really interested in it, I hope there is someone else with better translation skills frown.
I have some Berichte articles concerning the constitution of parsley (seed) oil. I hope I can find them in my mess and I'll give you a call wink. I'll have a look at Guenther's tomorrow as well.

The faster you run, the quicker you die.
 
 
 
 
    lugh
(Moderator)
04-28-03 02:25
No 429843
      Apiole Data
(Rated as: excellent)
    

Guenther's states that the preferred method for the isolation of apiole from parsley seed oil is by cooling the oil to a low temperature, and recrystallizing from alcohol and petroleum ether smile Apiole can be characterized by the preparation of the tribromide by reacting with excess bromine in carbon disulfide, mp 80-80.5 C, apiole's density is 1.176, melting point of 28 C, 179 C at 34 mm Hg and 292 C at STP smile Boiling of alcoholic apiole with KOH creates isoapiole, mp 55 C-56 C, oxidation of apiole with ethyl nitrite yields apiolaldehyde, mp 102 C, a qualitative color test is to add 5 drops of a 2.5% solution of phosphomolybdic acid in dilute alcohol to 1 ml of alcoholic apiole, add .5 ml of concentrated sulfuric acid and shake, a deep blue green color changing to orange red on heating indicates apiole smile References
Ber 21 913, 1621, 2514 (1888); 22 2481 (1889); 23 862, 2283 (1890); 36 1714 ((1903); 42 1506 (1909); 50 1335 (1917)
JCS 1602, 1606, 1607 (1938)
Atti Accad Lincei (5) 18 I 375 (1909)
Gazz Chim Ital 58 380 (1928)
Bull Sci Pharm 40 344 (1933)
Bull Soc Chim Biol 17 671 (1935)
J Russ Phys Chem Soc 62 77 (1930)
Ann Med Legale Criminol Police Sci 15 59 (1935)
Die Aetherischen Oele, Vol I, 619
Also, these might bee helpful to read:
Post 62944 (Antibody2: "Distillation of Parsley oil", Chemistry Discourse)
Post 89528 (beagle boy: "Parsley oil questions.", Chemicals & Equipment)
Post 163178 (Labrat: "Purification of Essential oils", Chemicals & Equipment)
Post 198423 (Rhodium: "Re: Freezing points: Apiole?", Chemistry Discourse)
Post 322503 (hypo: "bps and mps of various propenyl and allylbenzenes", Methods Discourse)

laugh

Chemistry is our Covalent Bond
 
 
 
 
    hypo
(Hive Addict)
04-28-03 09:55
No 429937
      interesting...     

a friend of a friend of a friend of a friend's parsley seed oil
contained about 50% clear, low boiling, terpene smelling oil.
and about 50% higher boiling stinking oil (plus some dark coloured residue).

the higher boiling oil gave after (very slow) fractional distillation
about 80-90% myristicin (identified by isomerisation) and some higher
boiling viscous stuff, which didn't crystallise in freezer. (and neither
did it after isomerisation!)

distilling twice is probably a good idea!
 
 
 
 
    GC_MS
(Hive Addict)
04-28-03 11:39
No 429945
      thanks     

Guenther's states that the preferred method for the isolation of apiole from parsley seed oil is by cooling the oil to a low temperature, and recrystallizing from alcohol and petroleum ether

Thanks for saving me the trouble to look for Guenther. Now, are you possibly interested in searching for my "hidden" Berichte articles as well? smile

hypo: according to what I have read in the literature, there is an awful lot of variation in the propenylbenzene content of parsley (seed) oil. I think it won't hurt to ask the supplier for a small sample, and if they see you are serious about doing business with them, they usually don't hesitate in sending samples. I even have a whole collection of "useless" samples just to perfume my lab cool.

The faster you run, the quicker you die.
 
 
 
 
    Antibody2
(Hive Addict)
04-29-03 21:31
No 430253
      unfortunately the distillation to which lugh...     

unfortunately the distillation to which lugh had provided a link resulted in no useable fractions. on a more positive note the next litre of parsley seed oil distilled resulted in a 150ml myristicin and a 250ml apiole fraction precedded by a 500ml terpine fraction. these fractions were identified by bp and  confirmed by  pseudonitration of the propenylbenzenes and bioassay of the amine derivatives.

attempts at freeze purification resulted in only partial crystalizations of both original allylbenzenes and thier corresponding propenylbenzenes.
 
 
 
 
    Vitus_Verdegast
(Hive Bee)
05-01-03 23:15
No 430679
      freezing highest boiling fraction     

The undistilled fraction was chilled in a freezer for 3 days, and half of it solidified into a red mass.

The highest boiling fraction of dill oil (analysis shows 15% dillapiole) did not solidify, only became more viscious.

http://www.ealasaid.com/fan/lorrelibrary/b-wing/bc/intro.wav
 
 
 
 
    hypo
(Hive Addict)
05-02-03 09:26
No 430759
      ab2!     

can you confirm the low yield (10%) in the Al/Hg of
MMDP2Poxime (wow - cool acronym)? i don't understand
why this gives lower yield than for example DMMDP2Poxime.
are you sure that the ketone / oxime was pure?

gracias!
 
 
 
 
    Antibody2
(Hive Addict)
05-04-03 22:03
No 431357
      hypo - it was the sickest looking oxime i ever     

hypo - it was the sickest looking oxime i ever triied to reduce. something happened in the oximation ( i've noticed it happens with other MeO-substituted ketones for reason i've yet to fanthom) all of a sudden the oximation rxn starts to turn red!! akk so instead of trying to crystalize i just crashed it out with water to stop whatever was happening. i had no properties for this oxime, and all attempts at crystalizzation failed, and i didn't know for sure it wasn't supposed to be an oil either, so this oil was what was reduced. It probably wasn't pure.

When forming the oxime from the parsley apiole ketone (2,5-MeO 3,4-MDphenylacetone) it also started to discolour at the 1.5 hour mark, but i was able to induce this oxime to crystalize with refrigeration. The lower than average yeild (50%) from this oxime,  i attribute to some cyclization of the 2 MeO group. Similar but worse problems were encoutered reducing the oxime from dillapiole ketone (2,3-MeO 4,5-MDphenylacetone)which in the end required anhydrous conditions, THF or dry EtOH.

If i were to try it again, i would keep a closer eye on the oximation to kill the reaction at the first sign of side reactions, and try using dry solvents for the Al/Hg redxn.
DMMDA is an entirely worthwhile pusuit IMHO smile. good luck
 
 
 
 
    Chromic
(Synaptic Self-Mutilator)
12-13-03 08:50
No 476577
      Ketoxime oils     

AB2, I just wanted to confirm your experience in general. I wanted to add that when reducing ketoxime oils a la AB2 (10 eq AcOH, 10 eq Al, 1 eq ketone), that, with mdp2p ketoxime, yields have been about 30% when it's been an oil, and around 80% when it's been a solid.

No idea what was happening in your particular case, but if it was an oil it was undoubtably impure and that explains the low yield. My suggestion would be to make sure the ketone is as close to pure as possible otherwise you will form an off-colored solid (at best) or more likely an off-colored ketoxime oil (reds and browns are common). (btw, also make sure to refrigerate at least 24 hours before you say it's not going to crystallize)
 
 
 
 
    Antibody2
(LinguisticBee)
12-16-03 03:02
No 477108
      it sat in the freezer for weeks :-( sigh.     

it sat in the freezer for weeksfrown sigh. But this thread reminds me just how divine DMMDA is. Too bad buying parsly oil is such an expensive crap shoot. Maybe get another litre for my B-Day

We are all just witnesses.
 
 
 
 
    Saddam_Hussein
(Stranger)
12-22-03 18:27
No 478468
      Oil of parsley
(Rated as: excellent)
    

Allow me to give you some information which can save you some frustration in the future when purchasing oil of parsley.

You have to keep in mind that parsley has three chemotypes: fruits in which the predominant constituents of the fruit oil is myristicin, apiole, or more rarely allyltetramethoxybenzene. As a rule of the thumb, oils rich in myristicin (70-90%) only contain traces of apiole and/or allyltetramethoxybenzene; oils predominantly consisting of apiole (70-90%) usually have traces of the allyltetramethoxybenzene but always seem to contain myristicin (5-15%) - important for your fractional distillation; oils rich in allyltetramethoxybenzene (ca 55%) usually have smaller fractions of both myristicin and apiole (5-20%). This, however, is for the seeds. It can happen that your parsley seed oil doesn't contain apiole, myristicin or allyltetramethoxybenzene at all! To avoid this frustrating situation, you should (a) always ask for a analysis certificate (especially since oil of parsley isn't the cheapest around) and (b) ask for a sample to check the quality.
How check the quality? TLC is the easiest and most OTC method. Back in the days, I had some nice labs to do this for me, but ... *siiigh* frown. Anyway, this is a method I have always used and has served me well:

solvent system: toluene-ethyl acetate (97:3)
detection: vanillin-sulfuric acid reagent

Vanillin-sulfuric acid reagent:
solution I: 5% EtOH sulfuric acid
solution II: 1% EtOH vanillin
The plate is sprayed vigorously with 10 mL solution I, followed immediately by 5-10 mL solution II. After hetating at 110C for 5-10 min under observation, the plate is evaluated in vis.

This method is commonly applied to screen the components of essential oils via TLC. Apiole (Rf 0.75) and myristicin (Rf 0.8) are coloured brown-violet. Allyltetramethoxybenzene gives weaker coloured bands.

Ref: H Wagner. Plant Drug Analysis, p 82.

Additional note: the chemotypes are region INdependant! Parsley seed oil from Hungary can be rich in myristicin, apiole or allyltetramethoxybenzene, just as seed oil from France, Pakistan or Australia. Trusting on the region of origin is impossible.

President of the Iraqi Chemical Weapons of Mass Destruction Development Society
 
 
 
 
    Rhodium
(Chief Bee)
06-09-04 18:01
No 512415
      trans-4-Methoxy-2,3-methylenedioxycinnamaldehyde
(Rated as: good read)
    

trans-4-Methoxy-2,3-methylenedioxycinnamaldehyde:A new aromatic aldehyde from Apium petroselinum seeds
N K Anand, (Miss) S Bhanumati & S R Gupta, Indian Journal of Chemistry Vol. 29B, 187 (1990)

Summary
trans-4-Methoxy-2,3-methylenedioxycinnamaldehyde has been isolated from Apium petroselinum seeds besides isoimperatorin, umbelliferone and 4-hydroxycinnamic acid.

In a broad programme in our laboratory on the chemical constituents of Apium petroselinum1-8, we report herein the isolation and characterization of a new natural product, trans-4-methoxy-2,3-methylenedioxycinnamaldehyde. In addition 5-O-prenylpsoralin, umbelliferone and 4-hydroxycinnamic acid were also isolated. The structure of the new aldehyde was finally settled by its oxidation9 with neutral KMnO4 in the cold acetone to 4-methoxy-2,3-methylenedioxybenzaldehyde10, mp 78-79C.

Experimental

Isolation of compounds
The petrol defatted seeds (5 kg) of A. petroselinum were thoroughly extracted with benzene. The benzene extract was concentrated and the residue subjected to column chromatography over silica gel. Successive elution with petrol-benzene (1:1), petrol-benzene (1:3), benzene and benzene-ethyl acetate (19:1) gave trans-4-methoxymethylenedioxycinnamaldehyde, isoimperatorin, umbelliferone and 4-hydroxycinnamic acid respectively as identified from their spectral data and by comparison with authentic samples.

Identification of the new aldehyde
It was obtained as yellowish brown needles (25 mg), mp 138-139C; Rf 0.56 (acetone-benzene; 1:24). It gave a positive 2,4-DNP test and also a positive sulphuric acid-gallic acid test.

Permanganate oxidation of the new aldehyde
A solution of the aldehyde (5 mg) in dry acetone (1 ml) was treated with neutral KMnO4 (50 mg) in dry acetone (15 ml). The reaction mixture was left at room temperature for 24 hr, manganese dioxide was filtered off and the solvent removed. The residue was dissolved in ether and washed carefully with 20% aq. NaHCO3. The ether solution on standing gave crystals of 4-methoxy-2,3-methylenedioxybenzaldehyde (2 mg), mp and mixed mp 78-79C.


References

[1] Garg SK, Gupta S R & Sharma N D, Phytochemistry, 17 (1978)2135.
[2] Garg S K, Gupta S R & Sharma N D, Phytochemistry, 18 (1979) 352.
[3] Garg S K, Gupta S R & Sharma N D, Phytochemistry, 18 (1979)1580.
[4] Garg S K, Gupta S R & Sharma N D, Phytochemistry, 18 (1979)1764.
[5] Garg S K, Gupta S R & Sharma N D, Planta Medica, 38 (1980)186.
[6] Garg S K, Gupta S R & Sharma N D, Planta medica, 38 (1980)363.
[7] Garg S K, Gupta S R & Sharma N D, Planta Medica, 43 (1981)806.
[8] Anand N K, Sharma N D & Gupta S R, Nat. Acad. Sci. Lett, 4, 249 (1981)
[9] Mohandas J, Slaytor M & Wastson T R, Aust J Chem, 22, 1803 (1969) Post 247833 (Rhodium: "Carpacin isolation & Physical Data", Chemistry Discourse)
[10] Campbell K N, Hopper P F & Campbell B K, J. Org. Chem. 16, 1736 (1951) (../rhodium/pdf /methylenedioxymethoxybenzaldehydes.pdf)

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