El_Zorro (Hive Bee)
07-05-02 20:05
No 329088
      Poosible new source for syringaldehyde?  Bookmark   

Well, I've been looking for backdoor routes to syringaldehyde or 3,4,5 methoxybenzaldehyde.  So I searched in chemfinder for the substructure of a benzene ring, with oxygens at the 3,4,5 positions, and a terminal ethene at the 2 position.(Does that make sense?)  I was looking for a compound that could have its double bond cleaved to the aldehyde by the CuO procedure.  Well, I didn't find too many hopefuls, but I did find this. 

Syringin, a.k.a lilacin, a.k.a. cinnamic alcohol. 

I don't know if it is watched or not, so somebody'll have to check that out.  But it is a component of the bark of the lilac tree.  I know that lilac trees are prized for their wonderful fragrance, but I don't know if syringin is responsible for it.  I couldn't find any essential oil of lilac, or of lilac bark, but someone might want to look.  The only real info I could find on syringin was that it could be extracted from the bark as a crystalline compound.


Edit:  Well, I looked on chemexper.com, and their syringin listing was a compound just like chemfinder's syringin, but had som kind of cycohexane ether with some hydroxy's attached to what would be the 4-position methoxy group.

Chemexper.com didn't even have chemfinder's syringin structure listed.

Which is correct?
07-05-02 23:54
No 329144
      Re: Well, I looked on chemexper.  Bookmark   

Well, I looked on chemexper.com, and their syringin listing was a compound just like chemfinder's syringin, but had som kind of cycohexane ether with some hydroxy's attached to what would be the 4-position methoxy group

It's a sugar compound. If you can break the ether bond, you'll end up with sugar and 4-hydroxy-3,5-dimethoxy cinnamic alcohol.

-[ A Friend With W33D Is A Friend Indeed ]-
(Old P2P Cook)
07-06-02 05:04
No 329213
      Essential oil.  Bookmark   

Post 276557 (terbium: "Re: Mescaline synthesis questions", Newbee Forum)
(Hive Bee)
07-06-02 20:06
No 329363
      Re: It's a sugar compound.  Bookmark   

It's a sugar compound. If you can break the ether bond, you'll end up with sugar and 4-hydroxy-3,5-dimethoxy cinnamic alcohol.

Yeah, that's what I thought, so it wouldn't really be that much trouble to get from the chemexper structure to the chemfinder structure, but I just want to know which one is the correct structure for the compound found in lilac bark.

Do not go gentle into that good night.  Rage, Rage, against the dying of the light.  --Dylan Thomas
(Official Hive Translator)
07-09-02 18:39
No 330440
      Here's a ref for you, if you're interested:  Bookmark   

.....syringaldehyde was 1st isolated in 1888 by Korner [Gazz. Chim. Ital. 18, 210 (1888)] by the decomposition with the aid of sulfuric acid of the emulsion of glucosyringaldehyde which in turn was prepared by cautious oxidation of syringin with dilute chromic acid.

It's from Patent US2516412

(Hive Bee)
07-09-02 20:49
No 330467
      So it is the compound listed on chemexper.com?  Bookmark   

So it is the compound listed on chemexper.com?  So I guess this mean SWIM could extract lilac bark, run the CuO procedure on the resulting extract, and then do a sulfuric acid hydrolisis on that, and distill out the Syringaldehyde?

Do not go gentle into that good night.  Rage, Rage, against the dying of the light.  --Dylan Thomas
(Hive Bee)
07-11-02 05:17
No 331127
      syringaldehyde  Bookmark   

i've read about eucalyptus as a source. swim'd love to fit that in as a little experiment seeing how the shit grows like weeds around swims parts. i have found plenty of fragrance oils of lilic which are basically synthetics used to emulate the natural plant odor. hmmm. i wonder what the chemical constituents of the fragrance are. posible something useful. i'll visit the local hippie shop and ask about lilac essential oils.

My brain should be a Schedule 1 organ.
(Hive Bee)
07-11-02 18:45
No 331306
      Yeah, I read that too, the guys just dumped some ...  Bookmark   

Yeah, I read that too, the guys just dumped some eucalyptus sawdust in a reactor and ran an oxidation on it, and got varying yeilds of syringaldehyde and vanillin.  The bad thing is I think they had to run a chromotography column on the product to separate the two.  Too much work for a fatass like me.tongue

I also saw some lilac fragrance oils, but no essential oils.  I hope the guy workin' at the local aromatherepy shop is good at chemistry!

Do not go gentle into that good night.  Rage, Rage, against the dying of the light.  --Dylan Thomas
(Hive Addict)
03-24-03 19:21
No 420865
      US Patent 2516412 (Syringaldehyde from pyrogallol)
(Rated as: excellent)

US Patent 2516412

Method of Synthesizing Syringaldehyde

The synthesis of syringaldehyde in good yield and on a large scale from 1,3-dimethoxy-2-hydroxybenzene, obtained from distillate of beechwood tar or is obtained from the controlled methylation of pyrogallol.  (The following reactions begin with pyrogallol.)

Example 1:

Preparation of 1,2-dimethoxy-2-hydroxybenzene

From: Krauss and Crede, J. Am. Chem. Soc. 39, 1433 (1917)

A flask containing 126 parts of pyrogallol is connected to a reflux condensor.  Methyl bromide is passed into the flask by a glass tube ending in a capillary and passing through the condensor to near the bottom of the flask until the air is displaced.  A solution of sodium methylate (prepared by dissolving 57.5 parts of sodium in 640 parts of absolute methanol) is run into the flask together with a continuous stream of methyl bromide.  The flask in heated  on the water bath and the current of methyl bromide continued until the reaction is nearly neutral.  The gas is rapidly absorbed and sodium bromide appears.  The 1,3-dimethoxy-2-hydroxybenzene is isolated as follows:  Water is added until the sodium bromide dissolves.  The methanol is evaporated and the residue is steam distilled.  Any 1,2,3-trimethoxybenzene present passes over in the steam.  The residue is acidified and extracted with ether.  The ether is removed and the residue is fractionated under reduced pressure. The pure 1,3-dimethoxy-2-hydroxybenzene is obtained as white crystals that had; MP: 55-56*C

Example 2:


A mixture of 154 parts of 1,3-dimethoxy-2-hydroxybenzene, 133 parts of allyl bromide and 180 parts of anhydrous potassium carbonate in 400 parts dry acetone was heated to boiling under reflux with occasional shaking for eight hours.  The solvent was removed by distillation, the residue was diluted with water and extracted with ether.  The ether was washed with dilute sodium hydroxide solution, the with water, dried with calcium chloride and distilled under reduced pressure on a steam bath to remove the ether and excess allyl bromide. The residual liquid was distilled under high vacuum and was obtained as an almost colorless oil  that had; BP: 102*C/2mmHg, 130*C/9mmHg, nD22 = 1.5300.  The yield of 2-allyloxy-1,3-dimethoxybenzene was 184 parts (95%)

Example 3:


2-allyoxy-1,3-dimethoxybenzene (104 parts) was boiled under relflux  at 75mmHg for 1 hour and was then distilled under high vacuum.  3,5-dimethoxy-4-hydroxyallylbenzene distilled as a colorless oil that had; BP: 123-125*C/2mmHg, nD21 = 1.5478. The  yield was 147 parts (90%)

Example 4:


A mixture of 100 parts of 3,5-dimethoxy-4-hydroxyallylbenzene, 50 parts of potassium hydroxide and 200 parts of water was placed in a flask connected to a distillation assembly and heated to boiling.  The clear solution soon became thick with a precipitate.  When the temperature reached 100*C, it had set to almost solid.  At this point 450 parts of aniline were added and the mixture distilled again.  After about 100 parts of distillate were collected, the solution became thick with precipitate.  This precipitate disappeared when the last bit of water was removed and the temperature began to rise.  About 150 parts of distillate had been collected at this point.  The distillation was continued until approximately 100 parts of aniline were collected and the temperature of boiling was 178-180*C. The hot mixture was allowed to cool and a mixture of aniline and the potassium salt of 3,5-dimethoxy-4-hydroxypropenylbenzene solidified.

Example 5:


The solid mass from Example 4 was dissolved in water and extracted with ether.  The alkaline aqueous layer was acidified with dilute hydrochloric acid.  The oil which separated was extracted with ether and the ether solution was washed with dilute hydrochloric acid, then with water, then dried. The ether was removed, the the residue was distilled to give 93 parts of 3,5-dimethoxy-4-hydroxypropenylbenzene that had; BP: 107-108*C/0.05mmHg as a colorless oil, nD27 = 1.5741. 

Example 6:

Syringaldehyde from alkali metal salt of 3,5-dimethoxy-4-hydroxypropenylbenzene

The solidified mixture of the potassium salt of 3,5-dimethoxy-4-hydroxypropenylbenzene and aniline obtained when hot (178-180*C) mixture of Example 4 was cooled was covered with 300 parts of nitrobenzene and 100 parts of 1:1 sodium hydroxide solution.  The resulting mixture was heated to 100-105*C with stirring for two hours, allowed to cool and diluted with water.  The solution was extracted with ether and the aqueous layer was acidified. The acid mixture was extracted with ether and the ether extracted with a 21% sodium bisulfite solution.  The bisulfite solution was acidified with sulfuric acid and aspirated to remove the dissolved sulfur dioxide.  Crystalline syringaldehyde separated and was filtered and washed with water.  Ether extraction of the filtrate and washings yielded more syringaldehyde.  The total yield of crude syringaldehyde that had; MP: 109-110*C was 78 parts (84%).  Recrystallization from ligroin raised the MP to 110-111*C.

Example 7:

Syringaldehyde from the isolated intermediate

195 parts  3,5-dimethoxy-4-hydroxypropenylbenzene are added to a cupric oxide mixture freshly prepared. (prepared from 1000 parts hydrated copper sulfate, 600 parts sodium hydroxide and 3000 parts water) The mix is refluxed for 8 hours.  The separated red cuprous oxide is filtered and washed with water.  The alkaline filtrate and washings are acidified and extracted with ether. Bisulfite purification of the ether extract should give 165 parts (90%) of syringaldehyde

Notes: The cuprous oxidation may also utilize Fehlingís or Benedictís solutions with same results.

Example 4 and 6 may be combined to one step by allowing the temperature in Example 4 to fall to the temperature in Example 6 and continuing by adding the necessary reagents. 

Example 2 may utilize with equal results in an organic solvent which is alkaline such as pyridine, dimethylaniline, aniline, etc.

You're Welcome Rhodium
(Hive Addict)
07-21-03 22:57
No 448880
      patent RU2119427  Bookmark   

Patent Number: RU2119427 
Publication date: 1998-09-27 
Requested Patent:  RU2119427 
Application Number: RU19970101245 19970124 
Priority Number(s): RU19970101245 19970124 
IPC Classification: B27K5/00; C07C59/185; C07C51/00; C07C47/56; C07C47/575; C07C47/58 
EC Classification:  

FIELD: fine organic synthesis, more specifically, technology of production of vanilla, syringaldehyde and levulinic acid from wood used in pharmaceutical, confectionery and perfume industries and in polymer technology. SUBSTANCE: products are produced by catalytic oxidation of small-leaved wood (aspen, birch, poplar) with oxygen in alkali medium with subsequent acid hydrolysis of cellulose residue. The method is distinguished by use of wood of small-leaved species (aspen, birch, poplar) and processing of solid residue of oxidation process into levulinic acid by acid hydrolysis. EFFECT: four-fold increase of assortment and yield of products; reduced consumption of alkali by two times on the basis of produced aldehydes.
Am i reading this right?  Vanilla and syringaldehyde can be made from birch and poplar??? Seeing as those are more readily available than eucalypt sawdust and nitrobenzene. But haven't seen the whole patent anybody here able to translate that?

Data supplied from the esp@cenet database - l2

Yes, That pic really is me!
07-21-03 23:26
No 448888
      RU2119427  Bookmark   

Why don't you post the link? Patent RU2119427
(Chief Bee)
07-21-03 23:52
No 448894
      Halfapint's legacy: Syringaldehyde from cardboard  Bookmark   

Am i reading this right?  Vanilla and syringaldehyde can be made from birch and poplar???

You can even make syringaldehyde from cardboard (and apparently in higher yield than from eucalyptus), read up on the research by the late halfapint:

Post 190600 (halfapint: "Lignin Syringaldehyde Again", Novel Discourse)
Post 214730 (halfapint: "The Hibbert Ketones of Lignin", Novel Discourse)
07-22-03 11:08
No 449033
      bleach + sawdust??  Bookmark   

what would happen if you bleached sawdust?? syringaldehyde??
When swim tried, the jar of sawdust got hot, and the reacted bleach solution took on a very different feel, and went cloudy, maybe he then should have tried an extraction with sodium bisulfite.