Antoncho (Official Hive Translator)
09-03-01 09:14
No 209756
      Possible improvements of vanillin demethylation.  Bookmark   

SWIM is recently broke so having nothing to do in the lab for the absence of essential chem's, he constantly annoys Antoncho w/crazy ideas, however sometimes making him curious.

This one is derived from the startinout's excellent research on eugenol demethylation. A topic so exciting for us, the sassafras-deprived. So far, from all of the routes tried only one was successful, the one w/pyridineHCl in microwave.

Now SWIM's primarily interested in demethylating vanillin since it was his impression that eugenol is very hard to deal with. Basically, there currently are two proc's at the Hive for this: 1st by Rhodium requires pyridine, AlCl3 & DCM; the 2nd by Startinout/Psychokitty - pyridine hydrochloride. Pyridine evrywherefrown

So the question Antoncho wants to ask the maitres is: from the chemical mechanics' point of view is triethylamine or triethylamine*HCl a conceivable alternative? From what Antoncho knows they're both strong bases and very often are employed in the same rxns. Pyridine HCl's mp is 145 and bp - 242 C, and triethylamine HCl only melts at 260 C - that should make a serious difference...

Also, is it proper to assume that by heating 1 mol NH4Cl w/3 mols CH3CHO at highest possible temp and for long enough time one will get triethylamine? - that assumption comes from Rhodium's Methylamine FAQ.

And one more note concerning the 1st route startinout researched, AlI3 in benzene/PTC. Someone named Assholium, in one of his Russian post, once said about this rxn smth like this: " can bee done, but the real problem w/these rxns is that the end product is extremely sensitive to the traces of Lewis acid catalyst, and if not washed from it very thoroughly, invariably turns to crap overnight" Having carefully read through startinout's posts i noticed that it was never done, and the whole picture falls in w/Assholium's hypothesis pretty well.

A curious note about using hydroquinone as a polymerization inhibitor is also found down the thread in the HI route by scooby_doo.

Anyone can develop these ideas somehow?

(Chief Bee)
09-03-01 11:12
No 209768
      Re: Possible improvements of vanillin demethylation.  Bookmark   

Triethylamine is a viable alternative. In the original article using Pyridine/AlCl3 they also tried an equimolar amount of triethylamine instead, and got about 25% lower yield, but it worked.

I don't think triethylamine can be made from acetaldehyde in the same manner as trimethylamine can be made from formaldehyde, as that reaction is a very special case. It can however be made by alkylating ammonia with an ethyl halide, and then distilling the triethylamine from the mixture of primary, secondary and tertiary amines produced.
(Hive Addict)
09-03-01 11:19
No 209770
      Re: Possible improvements of vanillin demethylation.  Bookmark   

Now SWIM's primarily interested in demethylating vanillin since it was his impression that eugenol is very hard to deal with.

You are suggesting that your impression is that the demethylated eugenol is less stable than the demethylated vanillin? Is this correct?

(Hive Addict)
09-03-01 22:00
No 209888
      Re: Possible improvements of vanillin demethylation.
(Rated as: excellent)

I have a reference on demethylation of a methylated olivetol derivative to olivetol using 45% HBr and acetic acid under reflux. 70-99% yeilds

j. Am. Chem. Soc.
1987, 109, 3098

And a similar compound was demethylated using an excess MeMgI.
Although yeilds in this case were poor.

j. am. chem. soc.
1948, 70, 4127

Do Your Part To Win The War
(Official Hive Translator)
09-03-01 22:29
No 209897
      Re: Possible improvements of vanillin demethylation.  Bookmark   

Hmmm.... Haloalkanes and ammonia, you say? Interesting...

Say, to make the proc. a little simpler, why not use isopropyl chloride - while being easily made and cheap, it has a charming advantage of being a liquid at room temp(bp 37 C). Whadd'yathink,  is triisopropylamine better/worse/same compared to pyridine and triethylamine? Is it too hindered, maybee?

As a side note, let me mention that, if proper proportions are used , the only byproduct of iPrCl's rxn w/NH4Cl will bee a PTC - which, BTW, can't bee had from dryer sheets (just what IS a dryer sheet?) where SWIM lives.

I couldn't find iPr3N's bp , but by extrapolation from the analogues it should bee ~120 C.

Here's another loose end to explore...

Foxy, this HBr thing surely looks interesting! Can you by any chance het this ref.? Can anyone?

Terbium: yes. At least such was startinout's opinion.

(Chief Bee)
09-04-01 02:44
No 209947
      Re: Possible improvements of vanillin demethylation.  Bookmark   

Triisopropylamine is a little bit too sterically hindered to be readily formed from isopropyl halides and ammonia, the most common crowded base I think is Hünigs base (Diisopropylethylamine, used from time to time in Tihkal).
(Official Hive Translator)
09-04-01 07:11
No 210013
      Re: Possible improvements of vanillin demethylation.  Bookmark   

Here's another route (US 5,728,888):

Preparation of 2,2',4,4'-tetrahydroxybenzophenone

440 g (3.30 mol) of AlCl.sub.3 were stirred into 120 g (1.64 mol) of dimethylformamide in such a way that the temperature remained below C. After cooling to C., 60.5 g (0.20 mol) of 2,2',4,4'-tetramethoxybenzophenone were introduced into the mixture, which was easily stirrable. The mixture was stirred at about C. for 4.5 hours and then added to 1.8 l of water to which 3 g of active carbon had been added. The hydrolyzate was filtered at about C., and then 65 g of concentrated hydrochloric acid were added to the filtrate. The precipitate was filtered off with suction at C., washed with water and dried at C. under reduced pressure.

Yield: 45.5 g

Melting point: C.

Purity (HPLC): 99.2%.

Example 4

Preparation of 2,2',4,4'-tetrahydroxybenzophenone in the presence of urea

54.8 g of 2,2'-dihydroxy-4,4'-dimethoxybenzophenone (0.20 mol) were reacted with 400 g of AlCl.sub.3 (3.0 mol) and 120 g (2.0 mol) of urea as in Example 3, and the product was worked up as described.

Yield: 40.3 g

They say when a large excess of AlCl3 is used the yields are esp-lly goodfrown

Hey, BTW, AlCl3 is soluble in CHCl3. So i guess it can bee made by chlorination of Al powder in it. Does anybee know if it's soluble in DCM or CCl4?

(Distinctive Doe)
04-03-02 12:50
No 291910
(Rated as: excellent)

Method for dealkylation of alkyl-aryl ethers
Patent US4695659
A method is disclosed for the dealkylation of alkylaryl ethers by reaction with aluminum triodide under reflux. The reaction is carried out in the presence of a catalytic amount of a quaternary ammonium iodide in a substantially non-aqueous organic solvent. The reaction product is then hydrolyzed with water. The quaternary ammonium iodide can be of the formula R4N+I-, wherein R is alkyl, and the solvent is preferably benzene or cyclohexane.  (In their claims they say that toluene or xylene also work, but give no examples/yeilds.)

Aluminium powder (2.5 g, 93 mmol) and iodine (19.0 g, 150 mmol) were mixed in 130 ml benzene (or cyclohexane) and were refluxed until the red colour of iodine disappeared (about 1.5 hours). The mixture was cooled. A solution of anisol (phenyl-methyl ether, 5.4 g, 50 mmol) and n-Bu4 N+ I- (tetra-n-butyl ammoniumiodide, 0.05 g, 0.14 mmol) dissolved in 25 ml benzene (cyclohexane) was added dropwise. The mixture was heated and was refluxed for 20 min, then cooled and hydrolysed with 150 ml water. The organic phase was separated and the water phase was extracted with 2.times.25 ml diethyl ether. The organic phases were collected and were extracted with 30 ml 2 molar NaOH. The water phase was separated, acidified with concentrated HCl and was extracted with 3.times.25 ml diethyl ether. The organic phases were dried (Na2 SO4) and were evaporated to give pure crystalline phenol. Yield=99%. M.p. 41 DEG-42 DEG C.

Vanillin to 3,4-Dihydroxybenzaldehyde
AlI3/ether molar ratio-4.8
ether/R4NI molar ratio-360

Isovanillin to 3,4-Dihydroxybenzaldehyde
AlI3/ether molar ratio-4.5
ether/R4NI molar ratio-120

Interesting Selective Demethylation
2,4,5-trimethoxybenzaldehyde to 4,5-Dimethoxysalicylaldehyde
(4 different)
AlI3/ether molar ratio-1.5, 3.3, 5.5, 10
ether/R4NI molar ratio-100, 100, 100, 50
Time (hours)          -14,  1.5, 1.5, 10
Yeild(%)              -88,  90,  91,  85

Those who give up essential liberties for temporary safety deserve neither liberty nor safety
(Distinctive Doe)
04-13-02 22:54
No 296703
      Interesting ether cleavage article
(Rated as: excellent)

This has a very mild method for cleaving di phenolic ethers(end of article) and a prep for 2,4,6-(MeO)3C6H2Br.

An unusual cleavage of diaryl ethers.   
Mayer, Walter; Fikentscher, Rolf; Schmidt, Johannes; Schmidt, Otto Th.   
Chem. Ber. (1960), 93 2761-76.   
CAN 55:27689   AN 1961:27689
Dehydrodigallic acid (I) and valoneaic acid dilactone were cleaved non-hydrolytically by alkali on the diphenyl ether bridge.  This cleavage of diphenyl ethers was apparently dependent on the presence of 3 vicinal, free OH groups on one of the 2 phenyl radicals.  The cleavage was an intramol. disproportionation and its mechanism regarded as a bor vinylogous b-elimination.  2,3-HO(MeO)C6H3CO2H (II) (3.5 g.) in 60 cc. Et2O treated with CH2N2-Et2O and refrigerated 2 hrs. yielded 3.4 g. Me ester (III) of II, m. 67° (2:1 MeOH-H2O) (all are cor.).  III (3.4 g.) dissolved with 1.31 g. MeOK in abs. MeOH and evapd., a 3.7-g. portion of the residue in 60 cc. abs. MeOH stirred 20 hrs. at 65° with 7 g. [Ph2I]Br, concd., and worked up with H2O and Et2O yielded 1.8 g. 3,2-MeO(PhO)C6H3CO2Me (IV), rodlets, m. 114-16° (3:2 MeOH-H2O).  IV (1.5 g.) in 20 cc. C6H6 treated with stirring with 2 g. AlBr3 in 8 cc. C6H6, refluxed 4 hrs., and treated dropwise with cooling with 25 cc. 2N HCl, and the product isolated with Et2O gave 0.46 g. 3-OH analog (V) of IV, prisms, m. 74-6° (3:1 (MeOH-H2O).  V (0.23 g.) and 30 cc. 2N NaOH refluxed 6 hrs. under a stream of H, cooled, and acidified with 2N HCl gave 0.17 g. 3,2-HO(PhO)C6H3CO2H, m. 154° (cyclohexane).  3,4-(MeO)2C6H3Br (30 g.), 26 g. PhOK, and 4 g. Cu bronze heated slowly to 170-80°, kept 2 hrs. at this temp., cooled, and decompd. with dil. aq. KOH, and the product isolated with Et2O yielded 15.5 g. 3,4-(MeO)2C6H3OPh (VI), leaflets, m. 47° (petr. ether).  VI (10 g.) in 50 cc. C6H6 refluxed 5 hrs. with 25 g. AlBr3 in 100 cc. C6H6 yielded 7.6 g. 3,4-(HO)2C6H3OPh, prisms, m. 104-6°, green with FeCl3 in MeOH. 3,4,5,2-(MeO)3(PhO)C6HCO2Me (9.5 g.) in 100 cc. C6H6 refluxed 4-5 hrs. with 25 g. AlBr3 in C6H6 and poured into 100 cc. concd. HCl and 200 g. ice gave 3,4,5,2-(HO)3(PhO)C6HCO2Me.H2O (VII.H2O), rodlets, m. 92-6° (H2O), which dried at 65°/1 mm. over P2O5 yielded 5.6 g. VII, m. 128-9°, deep blue with FeCl3.
 VII (2 g.) in Et2O treated dropwise with CH2N2Et2O, refrigerated 2 hrs., concd., and chromatographed on Al2O3 and then on silicone-impregnated cellulose powder yielded 0.180 g. 3,5,4,2-(HO)2(MeO)(PhO)C6HCO2Me (VIII), m. 117° (H2O).  VIII (0.107 g.) and 30 cc. 2N NaOH refluxed 6 hrs. under a stream of H, acidified, and extd. 24 hrs. with Et2O, and the ext. worked up gave 3,5,4,2(HO)2(MeO)(PhO)C6HCO2H (IX), prisms, m. 155-7° (H2O).  The Rf values (given) in 10:2:4 BuOH-AcOH-2H2O and in 2% aq. AcOH, and the color (given) with diazotized sulfanilic acid were detd. for the following compds.: VIII, 0.90, 0.74, orange; IX, 0.86, 0.74, orange-yellow; 3,5,4(HO)2(MeO)C6H2CO2H, 0.76, 0.60, red-brown.  3,4,5,2-(MeO)3(PhO)C6HCO2H (7 g.) in 100 cc. C6H6 refluxed 4 hrs. with stirring with 25 g. AlBr3 in 100 cc. C6H6, cooled, treated dropwise with 10 cc. H2O and 4 cc. concd. HCl, and filtered, the residue dissolved in 250 cc. H2O and extd. continuously with Et2O, and the ext. worked up gave 4.25 g. 3,4,5,2(HO)3(PhO)C6HCO2H (X), prisms, m. 172-95° (decompn.), deep blue with FeCl3.  X (2.85 g.) in 50 cc. Me2NH heated 1 hr. at 190-200° in a stream of H, cooled, treated with 500 cc. 2N H2SO4, and extd. 12 hrs. with Et2O gave 2.0 g. 2,3,4-(HO)3C6H2OPh (XI), yellowish prisms, m. 125-7° (H2O), which with CH2N2 gave 2,3,4-(MeO)3C6H2OPh, leaflets, m. 56-8°.  Syringic acid Me ester (4.3 g.) and an equiv. amt. 4N KOMe evapd., the residue in MeOH treated with 7.2 g. [Ph2I]Br, refluxed 20 hrs. with stirring, concd., dild. with H2O, and extd. with Et2O, and the residue from the ext. refluxed 4 hrs. with 4N NaOH and acidified gave 2 g. 4,2,6-HO2C(MeO)2C6H2OPh (XII), rodlets, m. 207-9° (H2O).  XII (1.3 g.) in 80 cc. C6H6 treated in the usual manner with 5 g. AlBr3 gave 0.7 g. 4,2,6-HO2C(HO)2C6H2OPh, m. 196-8°, orange-red with diazotized sulfanilic acid.  3,4,5-(MeO)3C6H2I (8 g.), an equiv. amt. PhOK, and 2 g. Cu bronze heated slowly to 150-60°, kept 2 hrs. at 150-60 and 2 hrs. at 180-90° and cooled yielded 1.9 g.
3,4,5(MeO)3C6H2OPh (XIII), prisms, m. 84-6°.  XIII (2.6 g.) in 65 cc. C6H6 cleaved with 9 g. AlBr3 yielded 1.2 g. 3,4,5(HO)3C6H2OPh, leaflets, m. 135-7° (C6H6), gray-blue with FeCl3.  1,3,5-C6H3(OMe)3 (10 g.) in 120 cc. CHCl8 (8, thats what is says, but I assume its chloroform) treated dropwise with stirring with 3 cc. Br gave 10 g. 2,4,6-(MeO)3C6H2Br (XIV), m. 97-9° (1:1 EtOH-H2O).  XIV (8 g.) and 4.4 g. PhOK heated with 2 g. Cu bronze 2 hrs. at 150-70°, 2 hrs. at 180-90°, and 2 hrs. at 200-10°, and worked up in the usual manner gave 0.6 g. 2,4,6-(MeO)3C6H2OPh (XV), m. 94-5° (aq. MeOH).  XV (2.4 g.), 20 cc. AcOH, 10 cc. Ac2O, and 25 cc. 57% HI refluxed 3 hrs. in the presence of a small amt. of red P, cooled, and dild. with 40 cc. H2O, and the product isolated with Et2O, sublimed at 150-70°, and recrystd. from C6H6 yielded 1.13 g. 2,4,6-(HO)3C6H2OPh, rodlets, m. 175-7°, red-brown with diazotized sulfanilic acid. 1,2,3-C6H3(OH)3 (XVI) (5 g.), 12 g. Na2SO3, and 1.6 g. NaOH in 100 cc. H2O treated 5-6 hrs. with a stream of air, acidified with 6N HCl, extd. 48 hrs. with Et2O, treated with Ba(OAc)2, filtered, passed through Amberlite IR-120, treated with C, and evapd., and the residue dried 48 hrs. at 70°/0.2 mm. over P2O5 yielded 4 g. 4(5)-SO3H deriv. (XVII) of XVI, m. 158-60° (decompn. from 115°), Rf 0.86 (10% aq. AcOH), blue with FeCl3, and ruby-red with aq. KCN.  XVII and 4N HCl heated 3 hrs. at 140° gave a resin and XVI, Rf 0.71 (10% AcOH).  XVII (1 g.) with CH2N2-Et2O kept 2 hrs. in the refrigerator yielded 1 g. tetra-Me ester (XVIII) of XVII, prisms, m. 123-4° (MeOH).  X (1.1-1.4 g.) added under H to 50 cc. 2N KOH, heated 6 hrs. at 100° under a stream of H, and acidified with 2N HCl gave 31% PhOH; 24-hr. heating gave 49.5% PhOH.  X and 2% aq. Na2CO3 heated 6 hrs. at 100° gave 62% PhOH, 49% 3,4,5-(HO)3C6H2CO2H (XIX), and 22% unchanged X; 24-hr. heating yielded 77% PhOH and 47% XIX.  X and NaOAc-AcOH buffer of pH 5.7 heated 6 hrs. at 100° resulted in the decarboxylation of X to XI; after 12 hrs., small amts. (5%) of PhOH and XIX were formed.
 X (1.7 g.) in NaOAc-AcOH buffer heated 72 hrs. yielded in addn. to PhOH, XIX, and XI 0.022 g. unidentified solid which sublimed from 265° with darkening, but without melting.  The Rf values were detd. for the following compds. in 2% AcOH and in 10:2:4 BuOH-AcOH-H2O: XIX, 0.40, 0.63; X, 0.65, 0.82.  XI and 2% aq. Na2CO3 heated 6 hrs. at 100° gave 8.2% PhOH; XIII gave similarly 14% PhOH.  XIII and 2N NaOH heated 6 and 20 hrs. at 100° gave 20% PhOH in both cases.  I and 3.8% aq. Na2CO3 refluxed 4 hrs. gave 0.59 g. XIX; the mother liquor methylated with CH2N2 and sapond. with alkali gave 0.015 g. (MeO)3C6H2CO2H and 0.070 g. 1,2,3-C6H3(OMe)3.  I (1.48 g.), 1.2 g. Na2CO3, and 2.0 g. Na2SO3 in 60 cc. H2O refluxed 4 hrs. under a stream of H, treated with 10 cc. 6N HCl, and extd. continuously with Et2O, and the ext. evapd. gave 0.69 g. XIX[/b]; the aq. phase treated with BaCl2, filtered, passed through Amberlite IR-120, and evapd. gave 0.4 g. XVII.  X (0.080 g.), 0.6 g. Na2CO3, 1 g. Na2SO3, and 30 cc. H2O refluxed 6 hrs. gave XIX, m. 236-7°, and XVIII.

Those who give up essential liberties for temporary safety deserve neither liberty nor safety
(Hive Bee)
04-14-02 15:22
No 296929
      FeCl3?  Bookmark   

what's up with all the FeCl3? is that some form of analytical technique to test for the presence of HO groups?

(Stoni's sexual toy)
04-15-02 01:23
No 297135
      For phenolic OH groups, yes.  Bookmark   

For phenolic OH groups, yes.

I'm not fat just horizontally disproportionate.
05-19-02 14:34
No 310938
      What's wrong with pyridine?  Bookmark   

What's wrong with pyridine for the demethylation of eugenol?

OK - I already know - it stinks. But for those of you who think they might be having trouble getting hold of it how about niacin as a precursor-precursor?

Niacin (nicotinamide) is pyridine with a carboxylic acid. It ought to be easy to get rid of that carboxylic acid to leave pyridine.

Niacin is available everywhere in pills or capsules (with hardly any filler) or in the pure form.
05-19-02 20:02
No 311096
      So are there any synths out there for.....  Bookmark   

So has there been any success in synthing pyridine from niacin?  I've heard of a few proposals using copper II hydroxide.

Resistance to government is so valuable on certain occasions that I wish it to be always kept alive.
05-22-02 11:30
No 312535
      I know it`s possible.  Bookmark   

It`s possible to decarboxylate niacin, just requires harsh conditions.
Picoline is another carboxylic acid of pyridine it decarboxylates more easily because the carboxyl group is closer to the nitrogen atom.
If you study Decarboxylation mechanisms, I think it`s because
the aza-nitrogen has electron withdrawling properties with respect to the carbon that the carboxyl group is bound to.
Maybe tautomerism would explain it.
Look at that thread entitled "pyridine"
In the general discourse.
SWIM is curios to know if that aluminum trihalide demethylation of eugenol would work on codiene.
The boron tribromide demethylation goes by the same mechanism as the alumium demethylation.
They are both group 3A elements.
Boron and aluminum that is.
Would somebody know about these things?
It seems it would go, or is this trihalide too strong of a
Lewis acid, which would Wreak havok on that phenanthrene skeleton?

(Chief Bee)
05-22-02 13:02
No 312563
      > SWIM is curios to know if that aluminum ...  Bookmark   

> SWIM is curios to know if that aluminum trihalide
> demethylation of eugenol would work on codiene.

I think the codeine is a too delicate molecule for that, and you will probably end up with a lot of apomorphine. Use any of the other codeine demethylation methods that can be found on my page.
05-22-02 17:26
No 312705
      I beleive you are right,,,  Bookmark   

However, since the mechanism of apomorphine formation starts by protic attack at C-14, then a chain reaction ensues which transfers thru the C-7,8 double bond SWIM believes this can be circumvented by reducing the 7,8 double bond.
This explains why there are processes for demethylating oxycodone using hydrobromic acids.
The yields are low (35%) but it works.
On there was a discussion called "hypothetical hydromorphone failure"
Where a guy catalytically rearranges codiene with Pd black in HCl, then goes on to demethylate it with hydroiodic acid.
At first he fucked it up, but on the second try he got 15%
Yeilds, and if you look closely at how he did it he was sloppy.
Because he refluxed it too long (1 hour), and in most journals they specify 15 minutes at 135 degress centigrate, add the dihydro (phenanthrene) whatever, when the acid (48% HBr) reflux is underway and not before, etc.
So it the personal conviction of SWIM that codeine can conveniently be converted to hydrocodone, then hydromorphone, using very accessible chems, an opiate for the masses type mission.
The link for that thread is:

I think there is another possible side reaction in this case
(H-X) demethylation, that could screw things up.
That is, H-X cleavage of the oxygen bridge on the phenanthrene skeleton to the catechol.
Rice,K.C., J.MED.Chem., (1977),20,164
For details.
He also rambles on in that thread that he tries to demethylate hydrocodone with pyridine.HCl and got a discouraging 5-7 %, so that`s a no go.
If you were to use any method to prepare hydrococdone that gives anything less than quantitative yields from codiene SWIM would recommend that you seperate unreacted codiene from the hydrocodone by forming bitatrate salts of the two.
codiene bitartrate is water insoluble, hydrocodone bitartrate is water soluble, hence seperation.
If you overshoot the tartaric acid in this titration you`ll get tartrate salts which are both soluble, hence no seperation.
Failure to do so in this case will result in you blowing chunks for some time.
(Gee blowing chunks was never this fun !)

Regarding pyridine via decarboxylation of aryl type acids
See: "copper quinoline decarboxylation of aromatic acids"
Nilsson M., Acta. Chem. Scand. 1966, 20, 423-426

Any more info on this would be welcome.
Spisshak Out!
05-22-02 18:01
No 312729
      whoops!  Bookmark   

Got the tough shit response when I tried that link, hope this fixes things.

05-24-02 15:57
No 313762
      Since triethylamine can be used on vanillin?  Bookmark   

Could triethylamine hydrochloride be used to demethylate codiene, albeit in lower yeilds than with pyridine.
Also why hydrochloride why not hydrobromide or hydroiodide,
These Ions have lower enthalapy of dissociation than hydrochloride Ion which makes me think that the demethylation would proceed at a lower temperature.

No sources! /Rhodium

(Chief Bee)
05-24-02 21:07
No 313880
      Yes  Bookmark   

Could triethylamine hydrochloride be used to demethylate codiene

Yes, that is probably possible.
05-25-02 09:50
No 314055
      Thanks!  Bookmark   

Appreciate the help, I`ll take heed, just rying to bee helpful.
05-25-02 10:02
No 314057
      OTC prep of triethylamine  Bookmark   

get Diethyl toulamide from your friendly wakyworld.
Hydrolize with aq KOH, extract diethylamine with toulene, then work up (distill)
React absolute ethanol with Red P and iodine to get ethyl iodide, distill.
React ethyl iodide with diethylamine from your insect repellant.
(Chief Bee)
05-25-02 11:40
No 314075
      tetraethylammonium iodide  Bookmark   

I wouldn't reccommend that method - you will overalkylate to tetraethylammonium iodide. Better react diethylamine with acetaldehyde and reduce the imine with Al/Hg.
05-25-02 16:27
No 314184
      Condensation products?  Bookmark   

Say you condensed acetylaldehyde on diethylamine, would the product be the enamine?
Are enamines more stable than shiff`s (imine) bases?
(Chief Bee)
05-25-02 19:34
No 314263
      enamine stability  Bookmark   

Yes, the product would be an enamine. Cyclic five- and six-membered enamines (such as those derived from morpholine, piperidine and pyrrolidine) are more stable than usual, but the one from diethylamine should behave like an ordinary imine.
05-25-02 21:14
No 314299
      Al/Hg workup (removing mercury salts)  Bookmark   

In most typical Al/Hg reductions saline washes are employed to remove any  residual mercury salts from the organic phase.
I believe that salt water increases miscibility of mercury salts (in water) via Ion pairing.
If one were to use mercuric iodide I have heard that it is more soluble in aqueous solutions of sodium iodide.
And sparingly, if soluble at all in just plain water.
Could Sodium Chloride be useful to increase miscibility of mercuric iodide?
As opposed to sodium iodide?
This is Important because small details like this being overlooked could lead to Mercury contamination (YUK!).
Would anyone know of this particular case?
Also would mercuric complexes of amines be too strong to be
seperated by these means (washing with salt solutions)?

Thank you Rhodium for the help.
It is much appreciated.
(Stoni's sexual toy)
05-27-02 02:13
No 314694
      > In most typical Al/Hg reductions saline ...  Bookmark   

> In most typical Al/Hg reductions saline washes are
> employed to remove any  residual mercury salts from the
> organic phase

That's one of the hard to get rid of hive myths. There won't be any Hg salts left over you can wash out. All the Hg salts will be reduced to the elemental state. And the Hg metal cannot be removed by aqueous washes. But it should all settle to the bottom and will be trapped in the Al sludge. If you are worried about Hg contamination I suggest you throw in some Al foil into your filtered post reaction solution and swirl it around for half an hour. The Al should absorb all the Hg which might still be present.

I'm not fat just horizontally disproportionate.
05-27-02 02:45
No 314699
      Iron  Bookmark   

Aluminum foil works well, but iron/steel turnings are much cheaper, and work better Post 228769 (lugh: "Re: proper waste disposal", Chemistry Discourse) smile
05-27-02 06:12
No 314749
      demethylation  Bookmark   

Demethylation of 3-methoxy-4,5-dioxyphenylethylamine by heating with conc. HCl in a closed ampoule.
K. Hahn, Ber., 71, 2141 (1938) someone can try to find that.

and i've just scanned an article about purification of nicotinic acid by sublimation and decarboxylation it to pyridine by 1,5 hours of heating it at 320°C with CaO 1:1.2 in an ampoule.
05-27-02 10:48
No 314831
      Please post it!  Bookmark   

Iv`e been itchin to know about decarboxylation of nicotinic acid please post it!
05-27-02 13:13
No 314880
      decarboxylation  Bookmark   

the authors of this article had only 6 mg of nicotinic acid they've obtained from some bacteriums and they had to purify it and decarboxylate it to obtain pyridine and prove that it was nicotinic acid. so after sublimating they put their 6 mg of acid and CaO in a ratio 1:1.2 in an ampoule, soldered it and then made a neck in the middle of it. then they bent this ampoule on it's neck about 45°. then they put the whole ampoule in a sand bath, gradually increased temp. of the bath to 320°C and maintained it for 1.5 hours. then, working with forceps they took the empty bent side of the ampoule and waited for drops to appear in it. then heating was turned off but the aumpule was standing in a bath for 30 min more. then they broke the ampoule and got 86-90% of pyridine. so they decarboxylated acid and distilled the product in one ampoule.

soon i'll post this in russian at my webpage and you will be able to see pictures.
05-27-02 14:59
No 314915
      Reference please?  Bookmark   

Can you provide the reference to this it sounds interesting.
I don`t care if it is Russian, I can have this translated..
Or the url to the webpage if that is not asking too much?
(Official Hive Translator)
05-31-02 02:53
No 316245
      The ref  Bookmark   

Can you provide the reference to this it sounds interesting.
I don`t care if it is Russian, I can have this translated..

Dear Spisshak!

Diafrag asked me to translate the reference for you to avoid any possibility of mistake. It's (i'm not quite certain myself if that's the proper namesmile) -

Applied biochemistry and microbiology, v. IX, 1, p. 138

or, as transcripted from Russian -

Prikl. Bioch. i Microbiol., <et cetera>

I am also looking forward very much to seeing that article, BTW!

Great job, Diafrag!wink


05-31-02 03:24
No 316249
      thanks antoncho !  Bookmark   

I'll stay tuned for that article.
06-01-02 13:30
No 316726
      Here you are!  Bookmark
(Hive Bee)
09-29-02 15:25
No 362076
      Pyridine Demethylation  Bookmark   

When pyridine hcl is used to demethylate aryl methyl ethers what is the pyridine degradation product? i know that the pyridine scavenges acid byproducts but how - most importantly is the hetrocycle ring destroyed? a reaction sequence-mechanism would be helpful. swim's thinking is along the lines of how easy it would be to reclaim the pyridine after successive batch runs - since obtaining pyridine otc always seems to be the bottleneck.