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 210°C [note: might be 310° as well; unclearly printed, but I guess it should be 210°C]. 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 (http://gallica.bnf.fr)
- periodicals section). I hope the Italian translation is more or less OK... My Italian is rather rusty :P . 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 :( .
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 ;) . I'll have a look at Guenther's tomorrow as well.
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 :) 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 :) 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 :) 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 (missing)
(Antibody2: "Distillation of Parsley oil", Chemistry Discourse)
Post 89528 (missing)
(beagle boy: "Parsley oil questions.", Chemicals & Equipment)
Post 163178 (missing)
(Labrat: "Purification of Essential oils", Chemicals & Equipment)
Post 198423 (missing)
(Rhodium: "Re: Freezing points: Apiole?", Chemistry Discourse)
Post 322503 (https://www.thevespiary.org/talk/index.php?topic=8874.msg32250300#msg32250300)
(hypo: "bps and mps of various propenyl and allylbenzenes", Methods Discourse)
;D
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 78-79°C.
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 138-139°C; 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 78-79°C.
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 (missing)
(Rhodium: "Carpacin isolation & Physical Data", Chemistry Discourse)
[10] Campbell K N, Hopper P F & Campbell B K, J. Org. Chem. 16, 1736 (1951) (https://www.thevespiary.org/rhodium/Rhodium/pdf/methylenedioxymethoxybenzaldehydes.pdf)
(https://www.thevespiary.org/rhodium/Rhodium/pdf/methylenedioxymethoxybenzaldehydes.pdf)