The Vespiary

The Hive => Methods Discourse => Topic started by: El_Zorro on June 25, 2003, 10:17:00 PM

Title: does trioxane sub for paraform in every case?
Post by: El_Zorro on June 25, 2003, 10:17:00 PM
I've looked through TFSE, and everyone seems to agree that trioxane can be used in place of paraformaldehyde in the NH4Cl+Paraformaldehyde synth for methylamine. I also saw a ref where it was used for chloromethylations.  My question is, does anyone have any actual, real-life success stories using trioxane in either the methylamine synth or a chloromethylation?

Title: Trioxane as (para)formaldehyde substitute
Post by: Rhodium on June 26, 2003, 03:23:00 AM
Trioxane (1,3,5-Trioxymethylene: (https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000442513-file_lct2.gif)) seems to be a perfectly good (para)formaldehyde substitute, among other things as a source od the methylene unit (-CH2-) in chloromethylation of aromatics.

See the following articles for details:

Kinetic Equation for the Chloromethylation of Benzene with Trioxane and Hydrogen Chloride Using Zinc Chloride as a Catalyst

Ind. Eng. Chem. hod. Res. Dev. 21, 87-93 (1982) (https://www.thevespiary.org/rhodium/Rhodium/pdf/chloromethylation.benzene-trioxane-zncl2-hcl.pdf)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/chloromethylation.benzene-trioxane-zncl2-hcl.pdf)

Chloromethylation of Benzene and Alkylbenzenes with Bis(chloromethyl) Ether, 1,4-Bis(chloromethoxy)butane, 1-Chloro-4-chloromethoxybutane, and Formaldehyde Derivatives

J. Org. Chem., Vol. 41, No. 9, pp. 1627-1631 (1976) (https://www.thevespiary.org/rhodium/Rhodium/pdf/chloromethylation.methylene-synthon-comparison.pdf)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/chloromethylation.methylene-synthon-comparison.pdf)

Trioxane as a Source of Formaldehyde

Ind. Eng. Chem. 39(8), 974-977 (1947) (https://www.thevespiary.org/rhodium/Rhodium/pdf/trioxane-formaldehyde.pdf)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/trioxane-formaldehyde.pdf)
Title: Re: Chloromethylation of Benzene and ...
Post by: El_Zorro on June 26, 2003, 04:05:00 PM

Chloromethylation of Benzene and Alkylbenzenes with Bis(chloromethyl) Ether, 1,4-Bis(chloromethoxy)butane, 1-Chloro-4-chloromethoxybutane, and Formaldehyde Derivatives




So am I correct in thinking that all they did in this ref was do a normal chloromethylation, but use GAA as the solvent, trioxane as the formaldehyde source, and SnCl4 as the acid catalyst, and then just bubble in HCl as usual?

I like this little idea, considering that trioxane can be had in the form of fuel tablets for about $15US for 3.5kg.