06-26-04 04:44
No 515478
Found this info on another website and thought I would run it by the bees here at the hive.
BENZAL CHLORIDE
Synonyms: benzylidene chloride; (dichloromethyl)benzene; benzyl dichloride; benzylene chloride; benzylidene dichloride; chlorobenzal; dichloro methyl-benzene; a,a-dichlorotoluene; dichlorophenylmethane
Synthesis: Place 58 mL (50 g) of toluene in a round bottom 100-mL flask. Attach a Clasien adapter to the flask. On the angled arm of the adapter, attach a condenser set up for refluxing. Since excess chlorine gas will be released from the top of the condenser, affix a one-holed stopper with a short length of glass tubing connected to a long hose, direct the hose to a well ventilated area. On the straight arm of the adapter, attach a length of glass tubing with a bubbler at the end that extends below the surface of the toluene. The top of this tube is connected to a chlorine generator.
Position the setup such that the flask is in direct sunlight, or very strong light. Sunlight is superior. Heat the toluene to boiling while a current of dry chlorine gas is bubbled in, the chlorine can be dried by passing it through two drying bottles filled with concentrated sulfuric acid. The course of the reaction is best judged by weighing the product; the reaction is complete when the toluene has increased by 40 g, the total weight being 90 g. By weighing the flask beforehand, and periodically interrupting the flow of chlorine to cool and weigh the flask, the completeness of the reaction can be determined. Without weighing, it is very difficult to gauge this reaction as the length varies greatly.
In the summer, in direct midday sunlight, the reaction is complete in a few hours. In winter, or low light, the reaction needs 12-24 hours to complete. Adding 4 g of phosphorus pentachloride to the toluene can enhance the reaction. The crude benzal chloride thus obtained can be directly used to make benzaldehyde.
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BENZALDEHYDE
Synonyms: almond artificial essential oil; artificial almond oil; artificial bitter almond oil; artificial essential oil of almond; benzenecarbonal; benzene carboxaldehyde; benzene methylal; benzoic aldehyde; benzoyl hydride; oil of bitter almond; phenylmethanal
Synthesis: To prepare benzaldehyde, start with the crude benzal chloride obtained from its synthesis. Into a round-bottomed flask with the benzal chloride, add a solution of 500 mL of water and 150 g of calcium carbonate. Set the flask up for reflux and heat for 4 hours on an oil bath. Keep the oil bath at 130 °C by checking the oil itself with a thermometer.
After refluxing, steam distill the product to obtain crude benzaldehyde oil. (The portion that did not distill over contains some benzoic acid. It can be discarded, or purified by filtering while hot through a piece of fluted filter paper, then adding concentrated hydrochloric acid to the filtrate. On cooling the benzoic acid will precipitate, it is filtered and recrystallized from hot water.) The crude benzaldehyde oil is treated with a concentrated solution of sodium bisulfite, after shaking for a long time the oil should have dissolved into solution. If any crystals happen to form during the shaking, add water until they dissolve.
After most of the oil is dissolved, filter the solution over fluted filter paper, and then treat the filtrate with sodium carbonate until it is strongly alkaline. This liquid is now steam distilled to obtain pure benzaldehyde. The product can be further purified by mixing with ether, letting the ether evaporate, and distilling (normal, not steam) the benzaldehyde.
If you have obtained benzaldehyde from other sources, it must be purified if it is anything less than ACS grade. It should be washed with sodium carbonate solution, dried, and distilled with minimum atmospheric exposure. Only the fraction collected at 178-180 °C is kept.
The info was found here:
http://www.roguesci.org/megalomania/synt
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The first write-up concerning benzyl chloride is similar to info that is already here. Post 502746 (amalgum: "Re: I recall Dwarfer mentioning using ttt as a", Stimulants) but couldn't find anything identical to the 2nd proceedure concerning BzCl to Benzaldehyde, here in the archives.
Is this 2nd piece of info accurate?
Refuse/Resist
(Wonderful Personality)
06-26-04 05:00
No 515479
Is this 2nd piece of info accurate?
NO.
(Hive Bee)
06-29-04 03:41
No 516150
try hypochorite in toluene use a water bath as if it goes over 105 C it blows. then use a sommelett dont use acetic acid as ethanol is heaps cheaper and works just well trust me I do it all the time now even tried the MnO2 this is the best way as far as I can see I can make about 100G of benzaldehyde from toluene in one day.
e3500 console login: root
bash-2.05#
(Hive Addict)
06-29-04 05:11
No 516181
Is this 2nd piece of info accurate?
NO.
would that be temperatures yeild or general procedure mate? or do you mean not practical as in there are other methods covered that are better?
FEAR MY GEAR
epistemologicide
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(Hive Bee)
06-29-04 06:02
No 516191
na tried nearly every way to aldehyde I could and found this
to work every single time with no problem.
the chloride is pritty nasty I also found that you dont have to distill the chloride just boil off excess toluene
then do the somolett. once somellet is compleate sep with
a bit of water to get rid of ethanols solvent properties
then put the aldehyde in a flask with water and steam distill
no vacume can be done with very little glass I sware it works every fucking time.
ps rhodium you can make benzene from benzoic acid and calcium oxide I did it last night.
e3500 console login: root
bash-2.05#
(Stranger)
07-06-04 09:11
No 517721
Any chance of having quantum's cipher translated into english, or am i missing something here,.?
The toluene to benzal chloride bit is fine, just his proceedure on making the crude benzal chloride into the aldehyde seems sketchy,.
If you are there quantum, please could you elaborate,.
What OTC goodies will convert Benzal chloride into benzaldehyde,.
CaO, Bi-carb,???
ambi
(Chief Bee)
07-06-04 10:18
No 517731
He is referring to the Sommelet Reaction, read more aboyt the mechanism in this thread: Post 495772 (Daphuk_up: "Sommelet vs. Delepine", Newbee Forum)
An example of that reaction being used to turn benzyl chlorides to benzaldehydes can be found in Post 276019 (psychokitty: "Re: piperonyl chloride ---> piperonal", Chemistry Discourse)
The Hive - Clandestine Chemists Without Borders
(Hive Bee)
07-13-04 05:44
No 519039
I think it goes 78g of benzyl chloride 168g of hexamine
300ml of ethanol 100ml of water boil for 2 hours the use
200ml of HCl to turn any left over amines into water soluble
salts reflux this mix for 15 min then sep with water and toulene. make sure your benzyl choride is filtered as
any left over hypo could explode.
e3500 console login: root
bash-2.05#
(Wonderful Personality)
07-13-04 07:02
No 519043
(Rated as: good read)
"Method of production of aromatic aldehydes by the Sommelet reaction"
BASF AG, Germany
Patent US4321412, in german: Patent DE2942894
The disclosed method avoids the need for alcohol and uses a molar ratio of chlorinated compound to hexamine of 1/1 to 1/1,5.
The patent describes the whole process from chlorination to the final product benzaldehyde.
Using 160gram hexamine for 120gram benzylchloride was tried and works fine. The hexamine can be added directly to the result of the chlorination if chlorine-gas is used. If hypochlorite is used this doesnt work, the reaction product has to be filtered or distilled then, whats a mess and unhealthy. If the chlorination is done with Cl2 it is advantageous to add 0,1% hexamine to the toluene at start - this suppresses ringchlorination.
Remark: Dont try the Loomis method (hypochlorite/toluene) for producing benzalchloride or even benzotrichloride! It works well for benzylchloride though.
ORG
1
(Stranger)
07-28-04 09:23
No 522189
yes, just confirming that loomins, and sommellot do indeed do what they say, Bzcl does not need to be distilled of,
Sommelot goes as documented,
A very nice reaction indeed,.
ambi
(Hive Bee)
09-16-04 11:14
No 531588
Thanks for that info Orgy, most appreciated.
I also experimented with the reaction between hexamine and benzyl chloride with good results.
Used a similar ratio of 365g distilled benzyl chloride with 450g powdered hexamine.
Added 1000ml water, and heated to 100degC for 4 hours
Then added 120ml 30-35% HCL and refluxed for 15 minutes
Then let sit for about 30 minutes and again added 100mls more HCL: so that pH acidic.
Briefly reheated to reflux and then cooled.
Extracted organic into DCM, evaporated DCM
Added lots of water to the flask, and steam distilled the resulting benzaldehyde by dsitilling the water from the flask.
Not totally sure of the yield, because i added some previously made benzaldehyde to this batch without measuring.
I suspect i got around 250g from the 365g benzyl chloride in this reaction.
The pH of the distilled water layer around 3.5 so not very acidic,
But just in case, the combined benzaldehyde was washed with sodium bicarbonate solution, and then vacuum distilled. Stored away from light in a tightly sealed bottle
Abacus