Author Topic: Acetic Anhydride by a strange route  (Read 1014 times)

Hector2000

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Re: Acetic Anhydride by a strange route
« Reply #40 on: September 28, 2012, 07:30:42 AM »
I made Ac2O many times by below reactions:

AcCl + AcONa = Ac2O + NaCl

and:
Pyrolysis of Silver Acetate

and:
from sodium acetate, using S2Cl2 and S2Br2
http://www.erowid.org/archive/rhodium/chemistry/anhydrides.html

from
Ethylidene diacetate

US1720184 best and easier way for make Ethylidene diacetate
US1578454 best and easier way for make Ac2O from Ethylidene diacetate

For testing Ac2O: just add one drop of it in water and watch it.it should fall down and reach at bottom of beaker and make very small oxygen balloon on it head.(i hope you understand what i mean)also it has very pungent odor(like garlic odor for me!)

Balkan Bonehead

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Re: Acetic Anhydride by a strange route
« Reply #41 on: October 01, 2012, 04:38:27 AM »
For testing Ac2O: just add one drop of it in water and watch it.it should fall down and reach at bottom of beaker and make very small oxygen balloon on it head.(i hope you understand what i mean)

Do you mean a "bubble"?

Hector2000

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Re: Acetic Anhydride by a strange route
« Reply #42 on: October 03, 2012, 06:21:29 AM »
yup

lugh

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Re: Acetic Anhydride by a strange route
« Reply #43 on: January 06, 2013, 03:57:59 PM »
The attached patent, US 752947 titled "Process of Making Organic Acid Compounds" describes means of producing acetic anhydride and chloride by dry distillation using salts of chlorosulfonic acid  8)
Chemistry is our Covalent Bond

fishinabottle

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Re: Acetic Anhydride by a strange route
« Reply #44 on: January 07, 2013, 06:55:03 AM »
The easiest way for a hobby chemist to make acetic anhydride is probably by pyrolysis of acetone producing ketene:

https://the-collective.ws/forum/index.php?topic=11618.0;all

http://www.sciencemadness.org/talk/viewthread.php?tid=8148&page=8#pid99225

http://www.sciencemadness.org/talk/viewthread.php?tid=571#pid4991

Organikum states a copper tube works fine  8)

Coppertubes work 50cm length to 3mm diameter, last 8cm reaction temperarure something 650°C. Massive copperblock for temperature control as it gets exothermic...

But lugh, the paper you later provided, the one from the german manufacturer of ketene lamps for laboratories, with stainless steel heating elements as used in water-cookers was the best IMHO, by far the best. You still can find it?

Otherwise ferric sulfate dry destillation for SO3 and this into GAA to make the AA is not more complicated, much cheaper and much less dangerous then phosgene. Join the next local pottery course, make some retorts to use for this, and get to know all these lonely and bored housewives!  ;)

/ORG

Balkan Bonehead

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Re: Acetic Anhydride by a strange route
« Reply #45 on: January 08, 2013, 12:01:28 AM »
Quote
Otherwise ferric sulfate dry destillation for SO3 and this into GAA to make the AA is not more complicated, much cheaper and much less dangerous then phosgene. Join the next local pottery course, make some retorts to use for this, and get to know all these lonely and bored housewives!

Has that method been demonstrated to work?

fishinabottle

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Re: Acetic Anhydride by a strange route
« Reply #46 on: January 29, 2013, 12:58:01 AM »
Quote
Otherwise ferric sulfate dry destillation for SO3 and this into GAA to make the AA is not more complicated, much cheaper and much less dangerous then phosgene. Join the next local pottery course, make some retorts to use for this, and get to know all these lonely and bored housewives!

Has that method been demonstrated to work?
Yes. Joining pottery courses and similar (Yoga for example) is a proven well working method for picking up women.  ;D

/ORG

phaseolus

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Re: Acetic Anhydride by a strange route
« Reply #47 on: February 05, 2013, 01:23:23 AM »
The easiest way for a hobby chemist to make acetic anhydride is probably by pyrolysis of acetone producing ketene:

If you value your life, you would avoid building your own ketene generator. If you're a chemical engineer or know one, you could probably pull off building a safe one. Alternatively I heard you can buy ketene generators (sometimes they're called ketene lamps). (Even then, bees have said the most they got out of their setups was 100 mL per day of continuous operation.) Sure, you can use contain and ventilate the apparatus, but where are you going to release the fumes? Outside? Ketene is as toxic as HCN. It's more responsible to just fucking steal AA than do this.

AA can be made starting with sodium ethoxide (from NaOH and anhydrous EtOH (dehydration of aqueous ethanol (190 proof vodka or cheaper less pure "denatured alcohol") with anhydrous CaO)) and disulfur dichloride (from gaseous chlorine (from hypochlorite salts and hydrochloric acid; or from electrolysis of sodium chloride solution) and elemental sulfur).

Edit: I didn't remember correctly. It's not sodium ethoxide but sodium acetate. None of those reagents (NaOAc, S, Cl2) are particularly hard to get, and according to the procedure on Rhodium's old site, it's high yielding.
« Last Edit: February 05, 2013, 11:07:16 PM by phaseolus »

lugh

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Re: Acetic Anhydride by a strange route
« Reply #48 on: February 05, 2013, 02:56:08 AM »
Quote
If you value your life, you would avoid building your own ketene generator. If you're a chemical engineer or know one, you could probably pull off building a safe one.

Almost thirteen years ago very clever member built a keten lamp and posted how he did it on the Hive:

      hypo
      (Hive Bee)
      02-22-02 08:03
      No 271991
           first encouraging ketenelamp experiment 

      1m of standard restistance wire (the expensive one for $2/roll) was coiled using a glassrod and attached to 2 pieces of thick copper wire. the copper wires were put through a rubber stopper and attached to a 220V variac. the rubber stopper was placed in the central neck of a 2-neck adapter which was placed on a RB with some acetone in it. on the other neck of the
      2-neck adapter were placed 2 condensers in series, the upper one being cooled with water. the top of the upper condenser was attached to a pipette in order to bubble the formed gasses through water. the flask was heated until the acetone was refluxing from the upper condenser. the aparatus was left in this state for 5 min, then current was turned on. when the resistance wire started glowing red, gas was produced. the amount of gas produced was easily controlled by the amount of current. after about 5 min a strange smell was noticeable and the experimentor experienced a cough reflex. the experiment was stopped at this moment.

      what do we learn from this?
      - it's time to stop wasting Br2, S, PCl3 and other valuable chemicals.
      - no need for special nichrome wire. standard resistance wire will do.
      - no need for special apparatus ala vogel.
      - heat seems not to be a big problem. the rubber stopper showed no signs of burning.
      - the rate of ketene production is easily controllable
      - ventillation seems to be a problem. either the apparatus had a leak or ketene is not as reactive as SO2.

      this seems too easy to be true... 


He lived through that and subsequent experiments with the lamp to continue to frustrate many other members as the Couch Terrorist 8)
« Last Edit: February 05, 2013, 03:36:03 AM by lugh »
Chemistry is our Covalent Bond

fishinabottle

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Re: Acetic Anhydride by a strange route
« Reply #49 on: February 05, 2013, 09:17:13 AM »
The easiest way for a hobby chemist to make acetic anhydride is probably by pyrolysis of acetone producing ketene:

If you value your life, you would avoid building your own ketene generator. If you're a chemical engineer or know one, you could probably pull off building a safe one. Alternatively I heard you can buy ketene generators (sometimes they're called ketene lamps). (Even then, bees have said the most they got out of their setups was 100 mL per day of continuous operation.) Sure, you can use contain and ventilate the apparatus, but where are you going to release the fumes? Outside? Ketene is as toxic as HCN. It's more responsible to just fucking steal AA than do this.

AA can be made starting with sodium ethoxide (from NaOH and anhydrous EtOH (dehydration of aqueous ethanol (190 proof vodka or cheaper less pure "denatured alcohol") with anhydrous CaO)) and disulfur dichloride (from gaseous chlorine (from hypochlorite salts and hydrochloric acid; or from electrolysis of sodium chloride solution) and elemental sulfur).

Do you generally tend to hysteria or are you somehow traumatized with ketene?

A little aspirator vacuum solves all problems of leaks and excess keten is washed down the drain for good. It dissolves reasonable enough in water to pose no problem in such a setup.
Albeit leaks should be no problem if you have just a little experience and some overpressure in the system is good for yields and furthers the reaction of keten with GAA which is astonishing slow as is the reaction of acetic anhydride with water btw. too. Excess keten is burnt off, at the end of the line comes a flameback arrestor and then a open flame and thats that. It will always burn for the methane but why not.

There have been many different incarnations of devices one can call "ketene lamp" and most worked  some even good. The last stage of evolution used a SS heating element from a water heater or like this (courtesy lugh for providing the article and information) what eliminated the main problem of sooth formation almost completely (what was the main issue with the copper tubes).

The task is technically not trivial but nowadays with PID controllers costing 10 bucks and SSRs up to nothing, it is far easier then it was 8 or 10 years ago.
With the opportunity to present planned construction and to get quality feedback here or even elsewhere - SCM if you want to avoid the druggie thing a bit - its also pretty safe if one has a rest of reason left in ones brain.
Risky are other things, like crossing the main street on rush hour. Thats risky.
(For you have much more control on such a project then on mad drivers, yes?)

It is just that people nowadays are even less willing to invest real time and real money into something like this for they expect the manna to fall from heaven if they bark at the moon long enough.
And that why not so much informtion is thrown out onto the slightest question, because thats got annoying and boring and endless frustrating.

For me at least.

I though still enjoy the practice of installations which make a certain kind of people hysteric. Not because of this but because I love this technical tinkering....


phaseolus

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Re: Acetic Anhydride by a strange route
« Reply #50 on: February 05, 2013, 11:28:50 PM »
fishinabottle, I have never made ketene, although I seriously considered it at one point. What made me change my mind was just how lethal the shit is. See hxxp://www.cdc.gov/niosh/npg/npgd0367.html (yes folks, it's written by the government, get over it). The "Immediately Dangerous to Life or Health" level is 5 ppm. Compare that to hydrogen cyanide: hxxp://www.cdc.gov/niosh/npg/npgd0333.html, which is 50 ppm. The level is defined as "an atmosphere that poses an immediate threat to life, would cause irreversible adverse health effects." Ketene as well as acetone are extremely flammable.

There is a better way to AA that's just as OTC as acetone. I know guys who have had success with it.
« Last Edit: February 11, 2013, 01:54:23 AM by phaseolus »

4studiesonly

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Re: Acetic Anhydride by a strange route
« Reply #51 on: February 06, 2013, 08:48:11 AM »
There is a better way to AA that's just as OTC as acetone. I know guys who have had success with it.

In a claim like that, if you say ´A´ you have to.....
So lets hear it, if people here indeed will find it the better way....
I have my hopes up
Bis zum bitteren ende

phaseolus

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Re: Acetic Anhydride by a strange route
« Reply #52 on: February 07, 2013, 12:24:58 AM »
In a claim like that, if you say ´A´ you have to.....
So lets hear it, if people here indeed will find it the better way....
I have my hopes up

The method is nothing new. It's the same method I referred to earlier. It uses an acetate salt and in situ disulfur dichloride from sulfur and gaseous chlorine.