Author Topic: OTC way to amphs, F.C w/ Al?  (Read 7730 times)

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lugh

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Nef's Article
« Reply #40 on: August 01, 2004, 04:32:00 AM »
The article by Nef Ann 335 247-333 (1904):



8)


moo

  • Guest
Monochloroacetone ketal
« Reply #41 on: October 11, 2004, 04:34:00 AM »
Here is an article where the chlorination of ketones in alcohols is studied, a method used in a patent posted earlier in this thread. They say:


Addition of HCl or HClO4 at the start of chlorination in methanol, or brief irradiation with a sunlamp, shortened the induction period at the beginning of the reaction but had no effect on the final product distribution. [...] The Chlorination of acetone in ethylene glycol gives the cyclic ketal of chloroacetone as the only product. Even with excess chlorine no dichloro products are observed. The chloro ketal separates from the ethylene glycol solution and does not react further.




Chlorination of aliphatic ketones in methanol.
Gallucci, R. R.; Going, R.
Journal of Organic Chemistry, 46(12), 2532-8 (1981). CAN 95:6437  ISSN 0022-3263
 
Abstract
The chlorination of aliph. ketones in MeOH showed that the product distributions in MeOH differ substantially from those obtained by chlorination in CCl4.  The reaction in MeOH favors addn. of chlorine to the least substituted carbon a to the carbonyl group.  The effect is esp. pronounced if an a carbon bearing two substituents is present.  The distribution of products is detd. by the relative stability of the enol ethers formed from the ketone under the reaction conditions.  Under the reaction conditions, free radical chlorination is unimportant.






Organikum

  • Guest
Monochloroacetone with TCCA
« Reply #42 on: October 11, 2004, 02:27:00 PM »
Keywords: Chlorination of ketones, TCCA, chloroacetone, chlorocyclohexanone

By the method described in the

Patent FR2633614

. On page six is a comprehensive table for all not speaking french btw.

Ratios & conditions:
4,3 mol acetone (0,5 reactand/3,8 solvent)
0,167 mol TCCA
300 ppm H2SO4
0°C temp.
100% yield on TCCA
(at 42°C reaction temperature yield is only 33%!)

To the cooled acetone in a icebath is added the H2SO4. Then the TCCA is added in small chunks one by one, the reaction takes place when cyanuric acid precipitates. Dont confuse this with TCCA dissolving in the acetone. The reaction temperature should not exceed 4°C.


The reaction was tried and works. 300ppm H2SO4 is hard to determine, 5ml H2SO 94% with 400ml acetone straight from the box were used. A tiny drop of HCl ensures that the reaction kicks in. Adding too much TCCA without getting the reaction started will cause a runwaway and the mixture containing chloroacetone will drop from the ceiling, whats NOT very funny. No HCl is evolved.
Neutralize with a mild base like sodium (bi)carbonate or chalk and separate by washing with water, salting out with CaCl2 and/or distillation. The workup is actually the most complicated part, therefor....

...information on azeotropes of monochloroacetone is needed urgently.
In special azeotropes formed with:
- water
- acetone
- benzene
- chlorinated hydrocarbons: chloroform/DCM.

An azeotrope of monochloroacetone with preferable benzene, so exist, would make the workup and further proceeding easy and tearfree.


Any help here is highly appreciated.

regards
ORG


java

  • Guest
Ref: Info on Azeotropes
« Reply #43 on: October 11, 2004, 09:06:00 PM »
You might try looking in Lang's Text which I posted in chemistry forum, however I looked and didn't find your compound, but found this databank.........java

http://eweb.chemeng.ed.ac.uk/chem_eng/azeotrope_bank.html




lugh

  • Guest
Purification of Chloroacetone
« Reply #44 on: October 12, 2004, 02:25:00 AM »
As far as the questions you posed, chloroacetone forms an azeotrope with toluene, which boils at 109.2° C, containing 28.5% chloroacetone: isobutyl alcohol, boiling at 105.8° C containing 36% chloroacetone; ethyl n-butyrate, boiling at 117.2° C containing 53% chloroacetone and isobutyl acetate, boiling at 116.7° C containing 30% chloroacetone; further information as to other azeotropes of chloroacetone can be found in:

Lecat, Ann Soc Sci Bruxelles 4 21-7 (1927); Cent II, 226, (1927)

Drying of chloroacetone can be accomplished using CaSO4; for more details see:

Patent DE584776

 ;)


psychokitty

  • Guest
What about IPA?
« Reply #45 on: October 12, 2004, 04:16:00 AM »
If IPA (isopropylalcohol) forms an azeotrope with chloroacetone, using it would be ideal.  IPA is one of the only solvents that reacts rapidly and completely with TCICA, and it's use could prevent an excess of TCICA from being present in excess at the end of the chloroacetone synthesis.

What about ethylacetate?  Does it form an azeotrope with chloroacetone?  If it does, the chloroacetone synthesis could be performed in ethylacetate since TCICA is VERY soluble in it.

TCICA is not very soluble in toluene, trichloroethylene, and  xylene.  And the byproduct cyanuric acid is pretty much insoluble in everything.  Hence, the precipitation of cyanuric acid from the solvent mixture is a good indication just how far and well the reaction is proceeding.  And as for the lewis acid required to initiate the reaction, just about any lewis acid or inorganic acid will do. 

BTW, I realize that IPA and probably ethylacetate are incompatible with the Friedel-Crafts synthesis; even so, it's nice to know of different and safe ways to purify a variety of substances.

Let's see, what else? . . . Use aqueous ammonia, preferably as a 50:50 mixture with acetone, to deal with a-haloketone spills.  I heard a rumor that this works wonders . . .

psychokitty

  • Guest
Journal of Chemical Education
« Reply #46 on: October 12, 2004, 04:57:00 AM »
I know that I've read many a paper about the Friedel-Crafts alkylation and acylation reaction using aluminum metal as the catalyst in the Journal of Chemical Education.

1.     GC/MS experiments for the organic laboratory: II. Friedel-Crafts alkylation of p-xylene (MODLAB).
   Novak, Michael; Heinrich, Julie.    1993, 70, A150
    Full text
2.    A simple preparation of 1,4-di-tert-butylbenzene without AICI3: An undergraduate organic chemistry experiment.
   Castrillon, Jose.    1991, 68, 793
    Full text
3.    Friedel-Crafts alkylation products (LTE).
   Kolb, Kenneth E.; Field, Kurt W.    1991, 68, 86
    Full text
4.    Friedel Crafts acylation and alkylation with acid chlorides.
   Jarret, Ronald M.; Keil, Nora; Allen, Susan; Cannon, Lisa; Coughlan, Julie; Cusumano, Leonarda; Nolan, Brian.    1989, 66, 1056
    Full text
5.    Friedel Crafts alkylation using elemental aluminum catalyst: An undergraduate laboratory experiment.
   Meeks, B. Spencer; Lucas, Anita R.    1989, 66, 176
    Full text
6.    Alkylation of chlorobenzene: An experiment illustrating kinetic versus thermodynamic control.
   Kolb, Kenneth E.; Standard, Jean M.; Field, Kurt W.    1988, 65, 367
    Full text
7.    The synthesis of 4,4'-di-tertbutyl biphenyl: a sophomore organic chemistry experiment.
   Horne, Deane A.    1983, 60, 246
    Full text
8.    Acylation of ferrocene: Effect of temperature on reactivity as measured by reverse phase high performance liquid chromatography.
   McKone, Harold T.    1980, 57, 380
    Full text
9.    Friedel-Crafts acylation: An experiment incorporating spectroscopic structure determination.
   Schatz, Paul F.    1979, 56, 480
    Full text
10.    Acetylation of ferrocene: Monitoring a chemical reaction by high pressure liquid chromatography.
   Haworth, D. T.; Liu, T.    1976, 53, 730
    Full text
11.    The Friedel-Crafts pathway to diarylcyclopropenones. An undergraduate organic experiment.
   Agranat, Israel; Tapuhi, Yitzhak.    1976, 53, 531
    Full text
12.    Stereospecific thermal cycloadditions and catalyzed isomerizations: An organic laboratory project.
   Pasto, D. J.; Duncan, J. A.; Silversmith, E. F.    1974, 51, 277
   
13.    Acetylation of ferrocene: A chromatography experiment for elementary organic laboratory.
   Bozak, Richard E.    1966, 43, 73
   
14.    The Friedel-Crafts alkylation of benzene: A first year organic laboratory experiment.
   Dunathan, H. C.    1964, 41, 278
   
15.    Friedel-Crafts alkylation (TE).
   Marsi, Kenneth L.; Wilen, Samuel H.    1963, 40, 214
   
16.    Apparatus for the Friedel-Crafts reaction.
   Kremer, Chester B.; Wilen, Samuel H.    1961, 38, 306
   
17.    The Friedel-Crafts reaction in elementary organic laboratories.
   Wright, Oscar L.; Fuhlhage, Donald; Sheridan, Earl.    1952, 29, 620
   
18.    A new Friedel-Crafts synthesis for the beginning student.
   Hart, Harold.    1950, 27, 398
   
19.    Friedel-Crafts reactions for the elementary organic laboratory.
   Dermer, O. C.    1938, 15, 268

Organikum

  • Guest
Huh?
« Reply #47 on: October 12, 2004, 12:13:00 PM »

f IPA (isopropylalcohol) forms an azeotrope with chloroacetone, using it would be ideal.  IPA is one of the only solvents that reacts rapidly and completely with TCICA, and it's use could prevent an excess of TCICA from being present in excess at the end of the chloroacetone synthesis.


Makes no sense to me. TCCA is never left over in the syntesis of 1-chloro-2-propanone as acetone is to be used in large excess always to avoid di-chlorinated byproducts.
Usining TCCA with ethylene-glycol and acetone is for sure worth a try, dissolving TCCA in acetone (1/3mol to 1 mol), and dripping this into excess ethylene-glycol which is spiced up with HCl and some H2SO4 should work fine.
Any comments to ning´s idea to use the monochloroacetone-cyclic-ketal in a FC reaction? Sounds advantageous so possible.

1-chloro-2-propanone can be dried by using CaCl2, this is the usual way to do this. First salt water out with CaCl2, separate and dry with CaCl2 to complete dryness. The process using gypsum as described in the german patent cannot convince me, large amounts of CaSO4 are necessary and I know there will be lots of the desired compound held back in then. Distillation from the gypsum will probably cause instant polymerisation.

When distilling a postreaction mixture of acteone/chloroacetone/water the distillate comes over in three fractions at:
- 59°C will be acetone
- 78°C thats a good one isnt it?
- 99°C water
Temperatures as read from my thermometer so not absolute  ;) , just distillation without column.
The last fraction containes no chloroacetone as a quick "spill/cry" test indicates.

I may have overlooked it, but there is a azeotrope of water and 1-chloro-2-propanone yes? And has a boiliong point and composition of????
Or do I just remember something wrong here and there is an azeotrope of 1/1-dichloroacetone and water?


regards
ORG




Organikum

  • Guest
Love ya moo :)
« Reply #48 on: October 15, 2004, 12:38:00 PM »
Thats really helpful.

I found the information that chloroacetone is subject to steamdestillation, can be steamdistilled. This resembles a heterogenous azeotrope, right?

The chloro-ketal as reactand in a FC reaction will be tried and results reported, I first have to find ethylene-glycol, antifreeze is a very impure mixture formed as byproduct in PE production says the Ullmann.  :(


Captain_America

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Orgy
« Reply #49 on: October 17, 2004, 06:04:00 PM »
This is a distillation from the book The war gases, chemistry and analysis, 1939 that you might find interesting.

Keywords: Halognated ketones, chloroacetone, bromoacetone, 1-bromopropan-2-one, 1-chloropropan-2-one, chlorine, bromine, fridel-crafts, p2p









For the complete file (4,5 mb)

http://bcis.pacificu.edu/~polverone/war_gases.html



Props to polverone for hosting such great books...

Organikum

  • Guest
From "Lachrymators"
« Reply #50 on: October 17, 2004, 07:43:00 PM »
Keywords: Lachrymators, halognated ketones, chloroacetone, bromoacetone, 1-bromopropan-2-one, 1-chloropropan-2-one

Excerpt from the article:
Lachrymators, by Kirby E. Jackson and Margaret Arthur Jackson, Department of Chemistry, Vanderbilt University, Nashville, Tennessee 1934
(no further information is available to me)

The part on chloro- and bromo- acetone was extracted.




Thanks Vitus_Amerika!  ;D  The lab-preparation of chloroacetone is very helpful and was plainly overlooked by me although I have the book "War-Gases".  :-[
Uuups.


moo

  • Guest
More observations
« Reply #51 on: October 18, 2004, 11:18:00 PM »
Steam distillation is not exactly the same thing as azeotropic distillation. It doesn't matter, especially because the

Patent US2260262

already mentioned in this thread, where the ketal was simply used to separate the isomers, says:

"The corresponding halogenated ketones may then be recovered by distilling separately said cyclic ketals in the presence of acid. Relatively dilute acids, for example, mineral acids of 1% to 20% concentration, may be satisfactorily employed for this purpose. The halogenated ketone thus liberated is distilled off as a constant boiling mixture with water, from which it is recovered in a chemically pure state while the water is continuously returned to the distillation vessel, until said ketone is completely removed. A portion of the glycol, together with the acid used, generally remains in the reaction vessel, and may be utilized in a subsequent run."

This has the word "azeotrope" written all over it, so to say. I'm convinced that the azeotrope exists. The guys who compiled the azeotrope databooks missed one ref :P . I'm surprised they managed to notice the other patent! And look, the density of  chloroacetone is higher than that of water -- a Dean-Stark will do if one is to actually use this trick. :)

I had already forgot all about the mention until I decided to have a look at those patents again...