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Author: Subject: Acid Chlorides
clearly_not_atara
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[*] posted on 30-10-2020 at 16:14


The best anyone can do with that is "maybe" since we don't have a very good idea of how (or when) the acetonitrile reaction even works. It could all decompose or it could go through a bis-imidoanhydride intermediate and give some oxalyl chloride.

But at a glance I would guess oxalic acid is decently soluble in acetonitrile, which makes it easier to try.




[Edited on 04-20-1969 by clearly_not_atara]
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mr_bovinejony
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[*] posted on 30-10-2020 at 16:22


That's what I was thinking too, at least with the information I found about the dihydrate form and its polarity. I guess i have a new project to work on!
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mr_bovinejony
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[*] posted on 15-11-2020 at 16:45


Has anyone tried to use n chloro saccharin with oxalic acid? In this paper here
https://jpharmsci.org/article/S0022-3549(15)37404-9/pdf
It is mentioned that because the pka of saccharin is lower than that of other acids used for chlorination, it is a stronger chlorinator. If the pka of cyanuric acid is 6.88 and it is known to work for making acyl halides via cyanuric chloride, would it make sense for chloro saccharin to work as well when saccharin has a pka of of 1.31?
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clearly_not_atara
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[*] posted on 15-11-2020 at 19:12


You're confusing electrophilic chlorination with nucleophilic chlorination. C3N3Cl3 transfers Cl-. ClN(SO2)COPh transfers Cl+. The two are not interchangeable.



[Edited on 04-20-1969 by clearly_not_atara]
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karlosĀ³
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[*] posted on 15-11-2020 at 19:26


That won't work as much as you can't halogenate acids with any of the other N-haloimides.
They are a source of monoatomic radical halogen ion, and that does not result in haloacids.

Cyanuric chloride is entirely different to TCCA if you drew that connection, the former is like an acid chloride of cyanuric acid, but the latter is like the N-haloimide of cyanuric acid.
You see, TCCA is more like NBS and, and cyanuric chloride, which is a special case anyway.
Look at tautomerism of isocyanuric and cyanuric acid, the latter is the trialcohol, and in cyanur chloride those three alcohols are chlorinated, and in isocyanuric acid of course the nitrogen groups.
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mr_bovinejony
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[*] posted on 15-11-2020 at 21:51


https://onlinelibrary.wiley.com/doi/10.1002/9780470771273.ch...

Check this out. I'm not sure where to find an alpha chloro ether, but this paper has some interesting pathways
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njl
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[*] posted on 16-11-2020 at 06:23


Alpha chloro ethers are byproducts of some reactions, chloromethyl-methyl ether being a notable one. They aren't particularly good for you. Cool paper though, some of the other routes are interesting.
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clearly_not_atara
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[*] posted on 16-11-2020 at 07:40


The best way I know to make alpha-halo ethers is to use the reaction of acetals with ZnCl2 and acetyl chloride :D



[Edited on 04-20-1969 by clearly_not_atara]
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mr_bovinejony
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[*] posted on 16-11-2020 at 08:25


Ah for fucks sake! Well we at least know acetyl chloride is doable thanks to chemplayer. I'm going to be trying his method using oxalic acid in 3 days and if that doesn't work I'll try this way
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mr_bovinejony
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[*] posted on 2-12-2020 at 10:13


For the synthesis of acid chlorides from cyanuric chloride, are acetone and triethylamine absolutely necessary? I think separating of the compounds from acetone would be difficult, and although triethylamine is easy to get and cheap, amines are stinky and I dont enjoy using them much
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Mateo_swe
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[*] posted on 2-12-2020 at 12:23


That paper you linked is very nice.
It takes up many different ways of preparation.
I include it for those who cant access it.


Attachment: Preparation of acyl halides.pdf (2.2MB)
This file has been downloaded 185 times

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mr_bovinejony
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[*] posted on 22-12-2020 at 09:18


Cyanuric chloride is kinda shitty to work with. I've had two volcanoes so far but I think the third time is the charm.

45 g of cyanuric chloride
20 g propionic acid
100 mls dmf
50 mls dcm

The cyanuric chloride is dissolved into the dmf with small portions and about 2 minutes in between each portion. This is very important unless you want a neat volcano and chlorine tears. At the end of the additions, not all had dissolved into the dmf but strong stirring was used and the acid added in dcm. No reaction was observed. This will be stirred for 4 hours and worked up with a water wash and solvent evap.

This half assed write up is more of a warning for people working with cyanuirc chloride. Take great care with it, within my first 30 minutes of it being unpacked 70 grams and 200 mls of dmf had gone up in the volcano
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[*] posted on 13-3-2021 at 12:28


The preparation of organic compounds
Barnett, E. de Barry , 1912, p73

SULPHURYL CHLORIDE (SO2Cl2 ). Sulfuryl chloride
is but little used in the laboratory, but is employed to
a large extent technically for preparing acid chlorides
from the corresponding salts
3 (cf. p. 60). The
calcium salts give the best results. The reaction
takes place at the ordinary temperature, but very
intimate mixing is required.

CHLORSULPHONIC ACID (SO 2 OHC1). Chlorsulphonic
acid, obtained by passing dry hydrochloric acid gas
into oleum, is chiefly used for preparing the chlorides
of sulphonic acids directly from the aromatic hydro-
carbons. A large excess of the acid is used and
rise in temperature prevented. The yields are
excellent. 4

1, M. 22, III.
2, B. 37, 1453.
3, D.R.P. 151,864, 63,593.
4, D.R.P. 98,030 ; B. 12, 1848 ; 42, 1802, 2057.

DE63593C "poor yields are obtained"
"The process is not technically feasible"

Present DE151864C claims technically sufficient acetyl chloride
from raw, wood acetic acid lime (gray lime, calcium acetate) can be produced. Barium acetate also can be used. Disadvantage of this process is that grinding of the reaction mass is necessary in ball mill.

Attachment: DE63593C.pdf (81kB)
This file has been downloaded 68 times

Attachment: DE151864C.pdf (190kB)
This file has been downloaded 62 times


[Edited on 13-3-2021 by Mush]
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