Sciencemadness Discussion Board

Acid Chlorides

Swinfi2 - 20-2-2018 at 18:04

(Excuse me if my searching was bad but I didn't find anything on the topic)

Has anyone found the need for acid chlorides? Specifically a way to make them avoiding "schedule 3 chemical weapons" as my best idea so far is:

red P and chlorine -> PCl3
PCl3 + organic acid -> acid chloride

Purely a thought experiment at this stage, PCl3 is way above my safety/equipment capacity right now so equilibriums will have to do, but still they might be useful if there is a safer (or of less questionable legality) method out there?

Magpie - 20-2-2018 at 18:39

RCOOH + SOCl2 → RCOCl + SO2 + HCl

SOCl2, thionyl chloride, can be made at home, with much labor. See my "preparation of thionyl chloride," this forum. But SOCl2 is a "3B chemical weapons" precursor. But, then again, so is PCl3. http://www.australiagroup.net/en/precursors.html

I don't think there is a cheap and easy way to make acid chlorides if that is what you are asking. If it was many here would be doing same. It is easier to make phosphorus.

[Edited on 21-2-2018 by Magpie]

JJay - 20-2-2018 at 19:49

There is a way that has not received much attention in the scientific literature that involves mixing the carboxylic acid with acetonitrile under anhydrous conditions and gassing it with hydrogen chloride. Chem Player tried it and says it works for acetic acid. There's a thread on it around here somewhere....

Chemi Pharma - 20-2-2018 at 22:09

The video Chem Player did about making acetyl chloride from acetonitrile, acetic acid and gaseous HCl can be find here:

https://www.youtube.com/watch?v=ExDI9KUW-9Q

But this synthesis suffers from low yields, as you can see in the video.

Exist a better way to make acid chlorides with satisfactory yield, without the use of dangerous POCl3, PCl3, PCl5 or thionyl choride, using OTC Cyanuric chloride, carboxilic acid in acetone and TEA (triethylamine) with stirring at room temperature, like said in the paper attached:

Attachment: Acetyl chloride and Benzoyl chloride from Cyanuric Chloride & Carboxylic Acids.pdf (86kB)
This file has been downloaded 771 times

Magpie - 21-2-2018 at 06:04

Quote: Originally posted by Chemi Pharma  

... using OTC Cyanuric chloride, carboxilic acid in acetone...


Where do you find cyanuric chloride OTC?

woelen - 21-2-2018 at 07:10

Many people make the mistake of thinking that cyanuric chloride is the same as trichloroisocyanurate (TCCA). They are not the same. Cyanuric chloride is C3N3Cl3, while TCCA is C3N3Cl3O3. The latter is available OTC as swimming pool chlorinator. Their molecular structures are somewhat similar, both contain an alternating N-C ring with 6 atoms, adding to the confusion.

TCCA reacts slowly with water to form HOCl and cyanuric acid. Cyanuric chloride reacts with water to form cyanuric acid and hydrochloric acid.

TCCA is strongly oxidizing and certainly will not be useful for replacing hydroxyl groups with chlorine atoms in organic compounds, such as alcohols and carboxylic acids. With many organic compounds, TCCA will react very violently and strongly exothermically. Be careful when mixing that with organics!

Chemi Pharma - 21-2-2018 at 07:18

Quote: Originally posted by Magpie  
Quote: Originally posted by Chemi Pharma  

... using OTC Cyanuric chloride, carboxilic acid in acetone...


Where do you find cyanuric chloride OTC?


Sorry if it's not OTC where you live @magpie. I really don't know about it's situation world wide, but here in latin america you can find it at every chemical vendor relatively cheap. For example, I bought mine (1 kg) paying U$120,00 at a local vendor. No hard to get at all, at least here.

Cyanuric chloride it's a very useful and versatile reagent. The researchers are discovering more and more uses for it at organic chemistry nowadays. I have many papers about what you can do with it. Worth it a try to buy and do some experimentation.

Chemi Pharma - 21-2-2018 at 07:25

Quote: Originally posted by woelen  
Many people make the mistake of thinking that cyanuric chloride is the same as trichloroisocyanurate (TCCA). They are not the same. Cyanuric chloride is C3N3Cl3, while TCCA is C3N3Cl3O3. The latter is available OTC as swimming pool chlorinator. Their molecular structures are somewhat similar, both contain an alternating N-C ring with 6 atoms, adding to the confusion.

TCCA reacts slowly with water to form HOCl and cyanuric acid. Cyanuric chloride reacts with water to form cyanuric acid and hydrochloric acid.

TCCA is strongly oxidizing and certainly will not be useful for replacing hydroxyl groups with chlorine atoms in organic compounds, such as alcohols and carboxylic acids. With many organic compounds, TCCA will react very violently and strongly exothermically. Be careful when mixing that with organics!


@Woelen is right. Many people make a mistake thinking TCCA is the same of Cianuric Chloride. TCCA is a oxidanting agent and cyanuric chloride is a chlorinating agent, though TCCA can act sometimes as a chlorinating agent too.

Cyanuric chloride is the trimmer of cianogen chloride (CNCl) and a very useful and versatile reagent in organic chemistry.

Thinking better, @magpie is right. It's not so OTC than TCCA at all.

byko3y - 21-2-2018 at 07:50

Cyanuric chloride is not even close to OTC and can be obtained only from specialized chemical distributors or some secondary market (later is risky due to usually short shelf life).

Swinfi2 - 21-2-2018 at 08:28

I've just found this (http://www.sciencemadness.org/talk/viewthread.php?tid=27073) about cyanuric bromide, seems like a "safer" alternative as RT gases are avoided but it doesn't look the easiest to make. Looks like acyl halides are a ways off for me at least.

clearly_not_atara - 21-2-2018 at 08:52

The acetonitrile method deserves further consideration. A paper I dug up earlier shows that acetonitrile dimerizes in the presence of HCl to form 1-(1-chlorovinyl)-1-aza-2-aminopropene, which appears (structurally) to be a more active chlorinating agent than acetonitrile. This means that two equivalents of MeCN react with one equivalent of carboxylic acid, which explains to some extent the low yields.

Anyway HCl gassing is much safer than any other method, including the bromine bomb I posted about years ago.

EDIT: Original post, and picture:

https://www.sciencemadness.org/whisper/viewthread.php?tid=9&...

[Edited on 21-2-2018 by clearly_not_atara]

Mothman - 21-2-2018 at 11:40

Could one potentially reduce the TCCA using carbon powder or would that wind up releasing a ton of dangerous crap like cyanogen chloride and phosgene?

Chemi Pharma - 21-2-2018 at 12:54

Quote: Originally posted by Swinfi2  
I've just found this (http://www.sciencemadness.org/talk/viewthread.php?tid=27073) about cyanuric bromide, seems like a "safer" alternative as RT gases are avoided but it doesn't look the easiest to make. Looks like acyl halides are a ways off for me at least.


I found that Liebig have synthesized and discovered cyanuric chloride in 1827, by passing chlorine into a flask with dry potassium thiocyanate, what seems not too difficult. However, I found nowhere on the NET this synthesis in details. If anybody here could get it and post here, it will be much appreciated.

The industrial way to make it reacting Chlorine with HCN is far from what can be made by an amateur chemist without risk of death.

Melgar - 21-2-2018 at 13:06

Benzotrichloride seems easier to make than a lot of your suggestions, however you'd need about twice as much chlorine gas as you'd need to make phosphorus trichloride.

Phosphorus halides are the easiest way to go. Bromides and chlorides are close enough in reactivity that they're essentially interchangeable. And phosphorus isn't actually illegal to own as long as your plans for it don't include making methamphetamine.

clearly_not_atara - 21-2-2018 at 13:11

On the subject of benzotrichloride, benzoyl chlorides can be formed by chlorination of benzaldehydes. A chlorination of m-chlorobenzaldehyde is given in Organic Syntheses as part of the leadup to mCPBA. These are a little easier to handle than benzotrichloride.
Quote: Originally posted by Mothman  
Could one potentially reduce the TCCA using carbon powder or would that wind up releasing a ton of dangerous crap like cyanogen chloride and phosgene?
No; it will decompose, perhaps violently. The problem with any reduction is that in TCCA, Cl is bonded to N (a weak, thus dangerous, bond) whereas in TCT, Cl is bonded to C. Reduction cannot rearrange this bond, certainly not in a crude dry-distillation setup.

[Edited on 21-2-2018 by clearly_not_atara]

AvBaeyer - 21-2-2018 at 19:28

Acid chlorides can be prepared using TCCA and triphenylphosphine. There are several publications that deal with this some of which I have attached. Triphenylphosphine is readily available from internet sources and is not controlled or watched.

I have made some acid chlorides using these reagents and they work well. The draw backs are that the reactions can get out of control (typical of TCCA) and of course a lot of relatively useless triphenylphosphine oxide is produced.

Another very mild and convenient way to activate acids for amide and ester formation and other useful chemistry is with carbonyldiimidazole. This reagent is also easily available and though somewhat pricey is really a great one to use. If anyone is interested I can provide some references.

I hope these help.

AvB

Attachment: SynComm1999_29_1415 TCCA-TPP.pdf (172kB)
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Attachment: TetLet2005_46_5945 TCCA-TPP.pdf (105kB)
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Attachment: Aldehydes to Acid Chlorides w TCCA FR2633616A1.pdf (199kB)
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Melgar - 21-2-2018 at 19:51

Oh, if benzotrichloride is too annoying for you to work with, it can actually tun benzoic acid into benzoyl chloride, forming benzoyl chloride itself. Benzoyl chloride is good for making low-boiling point acyl chlorides, and apparently less frustrating to work with.

Chemi Pharma - 21-2-2018 at 21:48

Thanks @AVBayer for the papers. Very instructive. I had only a paper dealing with alcohols alkylations with the mix TCCA/Triphenylphosphine in acetonitrile, atached below.

I didn't know the couple TCCA/triphenylphosphine can acts the same way cyanuric chloride alone in acylation or amidation of carboxilic acids, making nitriles from amides and to make vinyl chlorides from 1,3 diketones.

Glad to know about this other OTC route.

Attachment: Alcohols to Alkyl Chlorides with TCCA and Triphenylphosphine.doc (45kB)
This file has been downloaded 537 times


Boffis - 21-2-2018 at 23:35

Thanks guys for these papers, some very interesting and useful chemistry.

FireLion3 - 22-2-2018 at 15:10

Quote: Originally posted by Chemi Pharma  

Sorry if it's not OTC where you live @magpie. I really don't know about it's situation world wide, but here in latin america you can find it at every chemical vendor relatively cheap. For example, I bought mine (1 kg) paying U$120,00 at a local vendor. No hard to get at all, at least here.


I think there is slight confusion about the term OTC. In the US, Cyanuric Chloride is readily available at many chemical vendors and online chemical stores, but such stores are not what people think of when they say OTC. I think when most people say OTC, they mean readily available at big box stores that most people can drive to in a few minutes of their house and grab off the shelf, rather than specialized chemical companies.

woelen - 22-2-2018 at 15:31

My idea of OTC vs. not OTC at all:

- TCCA can be purchased at many gardening stores, swimming pool stores and also several hardware stores. No questions asked, just pick a bottle from the shelve, pay and drive away.
- Chlorocyanuric acid can be purchased where I live, but only from a few online chemical suppliers, catering to private individuals and only after filling in a declaration of use form with corresponding ID.


Chemi Pharma - 22-2-2018 at 20:01

Quote: Originally posted by woelen  
My idea of OTC vs. not OTC at all:

- TCCA can be purchased at many gardening stores, swimming pool stores and also several hardware stores. No questions asked, just pick a bottle from the shelve, pay and drive away.
- Chlorocyanuric acid can be purchased where I live, but only from a few online chemical suppliers, catering to private individuals and only after filling in a declaration of use form with corresponding ID.



umh, now I understand the cause of the misunderstood. In my concept, I've thought OTC is the reagent you can find and purchase even at a chemical supplier, internet sites like alibaba, ebay, Mercado Livre (here at Brazil), flagrancy stores, or any kind of stores, buying the good as a private individual, withouth filling any paper, no control by authorities and sent to you by mail post or got personally at a store, and NOT OTC is those reagents hard to find at even chemical vendors, sold only to companies, that have some kind of restriction to buy, or even watched by the authorities, that is, those reagents you need someone in the middle to get if for you, paying much more than the real price.

I believe my concept was wrong until now, reading what you've posted guys. I apologize and tell you that I will not use the term OTC here in the forum anymore, to don't cause more confusions. I will only use the terms "easy or hard to find or purchase" and "watched or not watched".





[Edited on 23-2-2018 by Chemi Pharma]

clearly_not_atara - 22-2-2018 at 22:15

Triphenylphosphine is also not OTC, as far as I'm aware. It's not interesting to the fuzz, though.

Chemi Pharma - 22-2-2018 at 22:50

Quote: Originally posted by clearly_not_atara  
Triphenylphosphine is also not OTC, as far as I'm aware. It's not interesting to the fuzz, though.


May be, but as TCCA, is easier to purchase than POCl3, PCl3, PCl5 or SOCl2, cited here like an easy option to acylate carboxilic acids, which does not correspond to the truth.

If I have a good synthesis, with high yielding, using easy to purchase chemicals, like cyanuric chloride or TCCA/Triphenilphosphine couple, why do I need to use these hard to get an watched chemicals? All of them are chemical weapons precursors. Even try to make them in a home lab is a pain in the ass. Dealing with chlorine, phosphorous and SO3 is not for beginners.




[Edited on 23-2-2018 by Chemi Pharma]

FireLion3 - 25-2-2018 at 13:41

Quote: Originally posted by Chemi Pharma  

umh, now I understand the cause of the misunderstood. In my concept, I've thought OTC is the reagent you can find and purchase even at a chemical supplier, internet sites like alibaba, ebay, Mercado Livre (here at Brazil), flagrancy stores, or any kind of stores, buying the good as a private individual, withouth filling any paper, no control by authorities and sent to you by mail post or got personally at a store, and NOT OTC is those reagents hard to find at even chemical vendors, sold only to companies, that have some kind of restriction to buy, or even watched by the authorities, that is, those reagents you need someone in the middle to get if for you, paying much more than the real price.

I believe my concept was wrong until now, reading what you've posted guys. I apologize and tell you that I will not use the term OTC here in the forum anymore, to don't cause more confusions. I will only use the terms "easy or hard to find or purchase" and "watched or not watched".


There's no need to apologize; it was a harmless confusion. Usually if a chemical is only available at chemical suppliers, people will just say that it is "Commercially Available", meaning not (usually) requiring any special licensing and permits and so on. If something isn't commercially available, then that usually means it is very rare, hard to find, or must be special orders on a custom-synthesis basis.


You said you were in Latin America? Are the regulations strict there? In the US there's not that many chemicals that require filling out a bunch of paperwork to get, unless someone is trying to purchase known precursor chemicals, or purchasing ridiculous quantities of watched chemicals. For the most part the US chemical market is pretty open. At least in my opinion. I know other countries out there are far more regulated, especially in Europe.


Chemi Pharma - 25-2-2018 at 14:47

Quote: Originally posted by FireLion3  
You said you were in Latin America? Are the regulations strict there? In the US there's not that many chemicals that require filling out a bunch of paperwork to get, unless someone is trying to purchase known precursor chemicals, or purchasing ridiculous quantities of watched chemicals. For the most part the US chemical market is pretty open. At least in my opinion. I know other countries out there are far more regulated, especially in Europe.


Here in Brazil we have three kind of regulations: The first one is dicted by Army Forces and control the chemical weapons precursors. Private persons can by only 02 kgs at maximum, filling papers and attaching their documents, explaining why they have a legitimate use to that chemical.

The second one is dicted by Federal Police Department (our FBI) and control the maximum quantities of chemicals that are common employed as precursors of narcotics manufactory. Private persons can purchase monthly a few quantities without a special licence required.

The third one is dicted by the public health autorities (here called ANVISA), and restrict the commerce and manufacturing of legal psichoative chemical compounds. License is always required. The bureau also maintain a monthly list containing the banned drugs, alkaloids and narcotics for criminal law enforcement use.

The most of chemical reagents is free to purchase without restrictions and you can do that easily at chemical supliers or even on the NET. I know that many other countries like Australia get almost anything under strict control. southern Asia too. East european countries as far as I know have the most liberal rules worldwide.

May be would be interesting to create a thread about the chemical restrictions existing nowadays in every country, just for fun.:)




[Edited on 25-2-2018 by Chemi Pharma]

DrDevice - 30-6-2020 at 22:33

ChemiPharm wrote (a long time ago now)
Quote:

I found that Liebig have synthesized and discovered cyanuric chloride in 1827, by passing chlorine into a flask with dry potassium thiocyanate, what seems not too difficult. However, I found nowhere on the NET this synthesis in details. If anybody here could get it and post here, it will be much appreciated.

The industrial way to make it reacting Chlorine with HCN is far from what can be made by an amateur chemist without risk of death.


I think I have tracked down the original article. I don't speak German, and haven't Google translated yet, but there is a mention of "Schwefelcyankaliums" which translates to "sulfur cyanide potassium".


Attachment: liebig1829.pdf (1.2MB)
This file has been downloaded 377 times

woelen - 30-6-2020 at 22:53

Schwefelcyankalium stands for potassium sulfocyanide. In modern nomenclature this is potassium thiocyanate, KSCN.

DrDevice - 6-7-2020 at 06:44

I've had a go at translating the first few paragraphs. Had to tweak the OCR results a few times, and I hope the German speakers forgive for not keeping the umlauts.

Quote:

Schwefelcyankalium und Chlor.

Schmilzt man trocknes Schwefelcyankalium in einem Strom von trocknem Chlorgas, so blaht sich dieses SaIz heftig auf, wird gelb
und undurchsichtig, seine Flussigkeit verliert sich immer mehr, nach Maafgabe als dic Zersetzung vorwarts schreitet, bis dafs es zuletzt fest wird; es destillirt wie bei den vorhergehenden Zersetzungen Chlorschwefel und Chlorcyan uber; allein in einem gewissen Zeitpunkte erhebt sich ein dicker rother Dampf, der sich an dem oberen Theil des Gefafses in Gestalt einer rothen, an manchen Stellen gelbrothen Masse anlegt.

Sie lafst sich in Gestalt von Blattchen, die keine Spur von Krystallisation zeigen, von dem Gefafse ablosen, und besitzt einen starken Geruch nach Chlorcyan, der sich aber beiin Erhitzen an der Luft verliert. Sie ist im Wasser unaufloslich und wird von Sauren, aufser Salpetersaure, nicht zersetzt; in Vitriolol lost sie sich auf, wird aber beim Verdunnen wieder abgeschieden. Die verschieden gefarbten Stellen scheinen darauf hinzudeuten, dafs diese Substanz zwei verschiedene feste Verbindungen enthalt; dies bestatigt auch ihr Verhalten zum Aetzkali.

Uebergeifst man namlich diese Substanz feingepulvert mit Aetzkali, so farbt sie sich dunkelroth, und das Kali lost nichts oder nur wenig davon auf; giefst man die alkalische Flussigkeit ab, und spult den Ruckstand mit etwas Weingeist ab, so lost er sich alsdann beim Uebergiefsen mit reinem Wasser zum Theil auf, wahrend ein anderer Theil, ohne Zweifel eine hohere Schwefelungsstufe, in Gestalt von gelben Flocken zuruckbleibt.


This translates to:

Potassium thiocyante and chlorine.

If you melt dry potassium thiocyanate in a stream of dry chlorine gas, this salt inflates violently and turns yellow
and opaque, its fluidity loses itself more and more, according to the measure as the decomposition proceeds until it finally becomes solid; chlorine sulfur and cyanogen chloride distill over, as in the previous decompositions; only at a certain point in time does a thick red vapor rise, which forms a red, yellow-red mass in some places on the upper part of the vessel.

It can be in the form of leaves, which none show traces of crystallization, detach from the vessels and has a strong smell of cyanogen chloride, which is lost in the air when heated. It is insoluble in the water and is acidic, as well as Nitric acid, not decomposed; it dissolves in Vitriolol, but is deposited again when thinning. The different colored areas seem to indicate that this substance is two different solid connections contains; this also confirms their attitude towards Aetzkali.

This substance is finely powdered with aetzkali, it turns dark red, and the potash dissolves none or little of it; you pour off the alkaline liquid and rewind the a little spirit, then it partially dissolves when pouring over with pure water, while a other part, no doubt a higher level of sulfurization, remains in the form of yellow flakes.
___________


Following this is a series of description of characterisation experiments. A little later in the document though we get to:

Quote:

Der gelbe Korper lafst sich ebenfalls und viel sicherer und vortheilhafter darstellen, wenn man Chlorgas durch eine concentrirte Auflosung von Schwefelcyankalium leitet.
Sogleich, wenn die ersten Blasen Chlorgas in diese Auflosung treten, bildet sich ein gelber Niederschlag, der bestandig zunimmt; dies geschieht aber nur dann, wenn das Schwefelcyankalium- kein kohlensaures Kali enthalt, welches nach der gewohnlichen Methode, wenn man Weingeist zur Scheidung beider anwendet, Ieicht geschicht. Man verfahrt deshalb bei der Darstellung des Schwefelcyankaliums besser, wenn man, nach dem das Eisencyankalium mit Schwefel zusammengeschmolzen und im Wasser wieder aufgelost ist, das Eisenoxydul zum Theil mit kohlensaurem Kali, und nachber vollstandig mit Schwefelammonium fallt, die Flussigkeit abdampft und bis zur vollstandigen Zersetzung des Schwefelcyanammoniums schmilzt;


Der gelbe Niederschlag backt bei dem Trocknen stark zusammen, er fuhlt sich weich an und farbt sehr stark ab, er halt das Wasser beim Trocknen aufserst hartnackig zuruck. Sein Verhalten stimmt so genau mit dem der beschriebenen Schwefelcyanverbindungen uberein,
dafs man beide schon darnach fur identisch zu halten geneigt ist.


This translates as:

The yellow body can also be displayed much more safely and favorably if you pass through chlorine gas conducts a concentrated solution of potassium thiocyanate.
Immediately when the first bubbles of chlorine gas enter this solution, a yellow precipitate forms steadily increases; however, this only happens if the potassium thiocyanate - contains no potassium carbonate, which according to the usual method, if one uses wine spirit to separate the two, is easy to tell. It is therefore better to proceed with the representation of the cyanide of sulfur if one follows the cyanide of iron with Sulfur melted together and in the water again the iron oxide is partly dissolved with carbon dioxide Potash, and afterwards completely covered with sulfur ammonium, the liquid evaporates and melts until the sulfur cyanammonium has completely decomposed

The yellow precipitate bakes on drying strong together, it feels soft and colors a lot strong, it keeps the water dry when drying stubbornly back. Its behavior agrees so exactly that of the sulfur cyanide compounds described, that both are inclined to be considered identical afterwards.

So there is some archaic (?) technical German in there that Google struggles with, and some funky English in the translation, but you get the gist.

When you read things like "the smell of cyanogen chloride" you get a bit worried that the first procedure might be hazardous to one's health (more so than usual...)

Passing the chlorine into a saturate potassium thiocyanate solution seems to do something however. Cyanuric chloride though reacts with water - maybe not quickly and it can be filtered and dried?

Brave souls who regularly use chlorine might want to give this a go??

Mush - 1-10-2020 at 16:48

Reaction of Carboxylic Acids with Sulfur Monochloride Using Iodine as Catalyst
Yoshiyuki TAKADA, Toshio MATSUDA, Hotuma OKASAKA

1969 Volume 72 Issue 11 Pages 2502-2503
https://doi.org/10.1246/nikkashi1898.72.11_2502

Attachment: 1969 Volume 72 Issue 11 Pages 2502-2503.pdf (540kB)
This file has been downloaded 329 times

3) V. Auger, A. Behal, Bull. soc. chim., [ 3 ] 2. 44 (1889). -> 144

Originally posted at the hive
" OTC acetyl chloride"
https://the-hive.archive.erowid.org/forum/showflat/Cat-/Numb...

SCl2 and SOCl3 are generated in situ:

S + Cl2 -> SCl2
CH3-COOH + SCl2 + Cl2 -> CH3-COCl + SOCl3 + HCl
CH3-COOH + SOCl3 -> CH3-COCl + SO2 + HCl

V.Auger, A.Behal, Bl. (3) 2, 145 (1889)

Bl =Bull. soc. chim or Bull.

and Houben-Weyl VIII, p.475

Full title:
No 98. — Sur une nouvelle méthode de préparation du chlorure
d'acétyle et de l'acide monochloracetique; par V. AUGER et
A. BÉHAL

V.Auger, A.Behal, Bl. (3) 2, 144 (1889)_144.jpeg - 342kB V.Auger, A.Behal, Bl. (3) 2, 144 (1889)_145.jpeg - 347kB


Machine traslation of part 1. acetyl chloride:

"1. Acetyl chloride. - Sulfur tetrachloride SCI "reacts
on acetic acid according to the equation:
SCl4+ 2CH3COOH = SO2 + 2HCl + 2CH3COCl.
Here is how we operate:
We put in a balloon 1 molecule of sulfur or protochloride
of sulfur, and 2 molecules of crystallizable acetic acid. We do
pass a stream of chlorine through the mixture while cooling the
balloon in a mixture of ice and salt. When chlorine is not
more absorbed, the flask is allowed to return slowly to room temperature, then it is distilled with a very good condenser and
collects the product in a balloon surrounded by ice.
Torrents of hydrochloric acid and sulphurous acid are given off, which always entail a notable quantity of chloride
acid. The liquid which distils before 60 ° is rectified, then it is freed from the sulphurous product which it contains, by stirring it with mercury, or better still, with copper powder. It then passes pure to distillation.
The yield thus obtained has always been quite low: 500 gr.
of chloride per 600 grams of acid; but it is to think that
by the use of more vigorous refrigeration, such as
coils surrounded by ice, we would increase the efficiency
in notable proportions."

Cou - 1-10-2020 at 20:22

Using TCCA and triphenylphosphine requires column chromatography to purify the products, gross.

Oxalyl chloride is the only reagent I can get for conversion of carboxylic acids to acid chlorides. Unfortunately it's very expensive.

karlos³ - 1-10-2020 at 20:29

You should still get it, who knows how long you will be able to access that?
When I got that stuff the first time for myself, I had to drive through the half country(luckily its tiny compared to america) to pick it up because shipping by mail wasn't legally allowed.
I still did it, because it is just so valuable.
It is also one of the least nastiest and cleanest reagents for acid chlorination, unlike thionyl chloride which I think is worse(although I could get that shipped by mail), so I can only recommed to buy it.

Yes its not cheap, but ask yourself, is it worth it?
I mean, I don't know about what a price you are talking but I'm sure it will still be worth to get such an useful reagent.

draculic acid69 - 8-10-2020 at 08:52

Quote: Originally posted by Magpie  
RCOOH + SOCl2 → RCOCl + SO2 + HCl

SOCl2, thionyl chloride, can be made at home, with much labor. See my "preparation of thionyl chloride," this forum. But SOCl2 is a "3B chemical weapons" precursor. But, then again, so is PCl3. http://www.australiagroup.net/en/precursors.html

I don't think there is a cheap and easy way to make acid chlorides if that is what you are asking. If it was many here would be doing same. It is easier to make phosphorus.

[Edited on 21-2-2018 by Magpie]


In the AA sticky there's info on using sicl4 +GAA---> AA
This is easier to make than socl2+legal+ not sure to buy

draculic acid69 - 8-10-2020 at 08:59

Quote: Originally posted by Mush  
Reaction of Carboxylic Acids with Sulfur Monochloride Using Iodine as Catalyst
Yoshiyuki TAKADA, Toshio MATSUDA, Hotuma OKASAKA

1969 Volume 72 Issue 11 Pages 2502-2503
https://doi.org/10.1246/nikkashi1898.72.11_2502



3) V. Auger, A. Behal, Bull. soc. chim., [ 3 ] 2. 44 (1889). -> 144

Originally posted at the hive
" OTC acetyl chloride"
https://the-hive.archive.erowid.org/forum/showflat/Cat-/Numb...

SCl2 and SOCl3 are generated in situ:

S + Cl2 -> SCl2
CH3-COOH + SCl2 + Cl2 -> CH3-COCl + SOCl3 + HCl
CH3-COOH + SOCl3 -> CH3-COCl + SO2 + HCl

V.Auger, A.Behal, Bl. (3) 2, 145 (1889)

Bl =Bull. soc. chim or Bull.

and Houben-Weyl VIII, p.475

Full title:
No 98. — Sur une nouvelle méthode de préparation du chlorure
d'acétyle et de l'acide monochloracetique; par V. AUGER et
A. BÉHAL




Machine traslation of part 1. acetyl chloride:

"1. Acetyl chloride. - Sulfur tetrachloride SCI "reacts
on acetic acid according to the equation:
SCl4+ 2CH3COOH = SO2 + 2HCl + 2CH3COCl.
Here is how we operate:
We put in a balloon 1 molecule of sulfur or protochloride
of sulfur, and 2 molecules of crystallizable acetic acid. We do
pass a stream of chlorine through the mixture while cooling the
balloon in a mixture of ice and salt. When chlorine is not
more absorbed, the flask is allowed to return slowly to room temperature, then it is distilled with a very good condenser and
collects the product in a balloon surrounded by ice.
Torrents of hydrochloric acid and sulphurous acid are given off, which always entail a notable quantity of chloride
acid. The liquid which distils before 60 ° is rectified, then it is freed from the sulphurous product which it contains, by stirring it with mercury, or better still, with copper powder. It then passes pure to distillation.
The yield thus obtained has always been quite low: 500 gr.
of chloride per 600 grams of acid; but it is to think that
by the use of more vigorous refrigeration, such as
coils surrounded by ice, we would increase the efficiency
in notable proportions."




I always wondered why ppl weren't trying to use sulphur in situ like with red P.
If it works that's the way for sure.will it also work for benzoic and propionic acid?

Mush - 8-10-2020 at 09:19

Quote: Originally posted by draculic acid69  
Quote: Originally posted by Mush  





I always wondered why ppl weren't trying to use sulphur in situ like with red P.
If it works that's the way for sure.will it also work for benzoic and propionic acid?


RESEARCHES ON HYDANTOINS. SYNTHESIS OF THE
SOPORIFIC, 4,4-PHENYLETHYL-HYDANTOIN(NIRVANOL)
BY WILLIAM T. READ 1922

Preparation of Propionyl Chloride, CsH5COC1.-Propionyl chloride
was prepared not only by the usual methods with phosphorus trichloride
or phosphorus pentachloride, but also by the chlorination of propionic.
acid in the cold with sulfur monochloride present.
To 540 g. of propionic acid 245 g. of sulfur monochloride was added and chlorine was passed through the mixture while it was stirred for 15 hours. The chlorination proved to be incomplete at this point, since 150 g. of unchanged propionic acid was recovered. There was also considerable sulfur monochloride, which was removed from
the propionyl chloride by treatment with hydrogen sulfide. The propionyl chloride obtained amounted to 250 g. This product functioned as satisfactorily in the subsequent preparation of phenylethyl ketone as that prepared by the phosphorus halide methods.28*.

Preparation of aliphatic acid chlorides
US1805162A

A mixture of 120 grams glacial acetic
acid, 100 grams S2Cl2 and 2 grams iron
filings was cooled to —19° C, and 9 oz.
chlorine passed in. keeping the temperature
below -4° C. The reaction mixture was
allowed to stand at 0° C. for 10 hours, and
then fractionally distilled. Yield 150
grams acetyl chloride amounting to 95.5
per cent, of theory.

Similarly, i may prepare the acid chlo-
rides of propionic, butyric, valeric and
homologous aliphatic acids, as well is of
their substitution products, such as the halo-
gen substituted derivatives thereof.

[Edited on 8-10-2020 by Mush]

Pumukli - 9-10-2020 at 10:00

In theory the reaction should work with benzoic acid too. I think that solubility issues would arise though...

The issue with HCl gas could be prevented if one could use the alkali-salt of the acids. Unfortunately the same solubility problems are obvious in this case as well.

garphield - 9-10-2020 at 20:13

isn't there a thread on here somewhere where someone converted sodium acetate to acetyl chloride using sulfur chlorides? probably won't work with everything but sulfur and chlorine are very easy to get and sulfur chlorides can be generated from molten sulfur and chlorine gas very easily, especially compared to thionyl chloride or phosphourus halides.

clearly_not_atara - 10-10-2020 at 08:09

I wonder if you could oxidise sulfur with KICl4? It's a lot easier to deal with than liquid bromine. Particularly so if KICl4 will dissolve in GAA.

4 KICl4 + 3 S + 6 AcOH >> 6 AcCl + 3 SO2 + 6 HCl + 2 I2 + 4 KCl
or if I2 will be reduced
KICl4 + S + 2 AcOH >> 2 AcCl + SO2 + 2 HCl + KI



[Edited on 10-10-2020 by clearly_not_atara]

draculic acid69 - 19-10-2020 at 04:38

Quote: Originally posted by draculic acid69  
Quote: Originally posted by Magpie  
RCOOH + SOCl2 → RCOCl + SO2 + HCl

SOCl2, thionyl chloride, can be made at home, with much labor. See my "preparation of thionyl chloride," this forum. But SOCl2 is a "3B chemical weapons" precursor. But, then again, so is PCl3. http://www.australiagroup.net/en/precursors.html

I don't think there is a cheap and easy way to make acid chlorides if that is what you are asking. If it was many here would be doing same. It is easier to make phosphorus.

[Edited on 21-2-2018 by Magpie]


In the AA sticky there's info on using sicl4 +GAA---> AA
This is easier to make than socl2+legal+ not sure to buy


That should be not sus to buy.damm spellcheck.

draculic acid69 - 19-10-2020 at 04:52

Quote: Originally posted by Chemi Pharma  
Quote: Originally posted by FireLion3  
You said you were in Latin America? Are the regulations strict there? In the US there's not that many chemicals that require filling out a bunch of paperwork to get, unless someone is trying to purchase known precursor chemicals, or purchasing ridiculous quantities of watched chemicals. For the most part the US chemical market is pretty open. At least in my opinion. I know other countries out there are far more regulated, especially in Europe.


Here in Brazil we have three kind of regulations: The first one is dicted by Army Forces and control the chemical weapons precursors. Private persons can by only 02 kgs at maximum, filling papers and attaching their documents, explaining why they have a legitimate use to that chemical.

The second one is dicted by Federal Police Department (our FBI) and control the maximum quantities of chemicals that are common employed as precursors of narcotics manufactory. Private persons can purchase monthly a few quantities without a special licence required.

The third one is dicted by the public health autorities (here called ANVISA), and restrict the commerce and manufacturing of legal psichoative chemical compounds. License is always required. The bureau also maintain a monthly list containing the banned drugs, alkaloids and narcotics for criminal law enforcement use.

The most of chemical reagents is free to purchase without restrictions and you can do that easily at chemical supliers or even on the NET. I know that many other countries like Australia get almost anything under strict control. southern Asia too. East european countries as far as I know have the most liberal rules worldwide.

May be would be interesting to create a thread about the chemical restrictions existing nowadays in every country, just for fun.:)




[Edited on 25-2-2018 by Chemi Pharma]


I seen acetyl chloride pop up on a list of chems available to average Joe
otc from a well known Chem supply here in oz. I thought it was on the
No-go list like acetic anhydride but there it was at a greatly increased price
of course.$700 a litre.

clearly_not_atara - 19-10-2020 at 06:31

Quote:
In the AA sticky there's info on using sicl4 +GAA---> AA
This is easier to make than socl2+legal+ not sure to buy

SCl4 is stable only below -30 C. It is produced by adding liquid chlorine to sulfur with strong cooling. Arguably this is easier than SOCl2 via oleum etc but it is very equipment-intensive in that it requries condensing Cl2 and working with it.

The methods where chlorine gas is introduced to a suspension of S in GAA do not make SCl4, but they do effectively transfer four electrons from one sulfur atom to four chlorine atoms. I imagine they also have the potential to produce significant amounts of chloroacetic acid and its chloride.

draculic acid69 - 20-10-2020 at 02:59

Quote: Originally posted by clearly_not_atara  
Quote:
In the AA sticky there's info on using sicl4 +GAA---> AA
This is easier to make than socl2+legal+ not sure to buy

SCl4 is stable only below -30 C. It is produced by adding liquid chlorine to sulfur with strong cooling. Arguably this is easier than SOCl2 via oleum etc but it is very equipment-intensive in that it requries condensing Cl2 and working with it.

The methods where chlorine gas is introduced to a suspension of S in GAA do not make SCl4, but they do effectively transfer four electrons from one sulfur atom to four chlorine atoms. I imagine they also have the potential to produce significant amounts of chloroacetic acid and its chloride.


I know I should be using capital letters and being more accurate for this exact reason:
It's silicon tetrachloride I wrote as sicl4 in the above paragraph.scl4 is close. sicl4 is not sus to buy.
It's seems the easiest way to acid chlorides in my opinion without using hard to obtain,
rare,smelly,toxic or restricted chems.It could also be made in an amatuer setting.sulfur chlorides "can" also be made in amatuer settings but if U live with or near other ppl or U care at all about the habitability of the structure U r using for chemistry U probably shouldn't make sulfur chlorides in an amatuer setting.
[Edited on 20-10-2020 by draculic acid69]

[Edited on 20-10-2020 by draculic acid69]

draculic acid69 - 20-10-2020 at 03:44

Anyway for theoretical interest in trying to make acid chlorides with out to much toxic smelly middle stages above it says one molecule of sulfur to two molecules of gaa,
Now how much sulfur is this in grams as sulfur like phosphorus which is P4 or bromine which is usually br2 sulfur is usually represented as S8 or something so how many grams sulfur would one use for this? I'm a bit confused when it comes to this.
Is it 32grams or 8times this?

njl - 20-10-2020 at 05:11

That's a really interesting question that I'd also like to have answered. That said, as long as the different allotropes of sulfur react in the same way in this situation, it shouldn't matter. Don't worry about how many sulfur atoms are in a molecule, as long as you are using the molar mass of a single sulfur atom your math will work out.

clearly_not_atara - 20-10-2020 at 05:59

It's wrong when it says one molecule of sulfur, basically. It should say one mole of sulfur atoms. You need to reduce one mole of chlorine to eliminate one mole of water; formally:

Cl2 + H2O + 2 e- >> 2 HCl + O(2-)

Each sulfur atom provides four electrons:

S + 2 O(2-) >> SO2 + 4 e-

Neither reaction is actually possible without the other but they do happen in tandem. Naturally you get one mole of anhydride for consuming one mole of water.

So you get two moles of Ac2O per gram-atom of S alternatively 16 moles Ac2O for one mole S8.

draculic acid69 - 20-10-2020 at 06:17

So how many grams of yellow garden product does one put in the flask with the 120 grams of acetic acid?

Also clearly not atara I was referring to the above synth of the acid chlorides where sulfur is used in place of phosphorus not the synth of the anhydrides.it seems that the rxn of sulfur halides with the sodium salts of carboxylic acids goes all the way to anhydride but with just the free acid it only makes the acid chloride.no sodium to absorb the halide no anhydride.

njl - 20-10-2020 at 06:26

Most garden sulfur is grossly impure as far as I know, including metal impurities that could interfere with your reaction. I don't know of many good ways to purify sulfur other than recrystallization from hot toluene which is a pain in the ass due to low solubility. That doesn't mean it isn't worth a try, but just something to keep in mind.

draculic acid69 - 20-10-2020 at 17:06

Let's just say that is irrelevant.can anyone clearly state how many grams of sulfur powder go in the flask?

clearly_not_atara - 20-10-2020 at 19:35

One mole of Ac2O or one mole of AcCl makes no difference; you just add or subtract HCl (easy).

But really you want an excess of AcOH. Otherwise your reaction mixture will probably boil away! AcCl has a low boiling point and the rxn between S and Cl2 is quite exothermic. What I can tell you is that 16 grams of sulfur will produce, theoretically, about 78.5 grams of acetyl chloride from 60 grams of acetic acid and should probably be used with oh I don't know 120 grams of AcOH might be safe, just keep an eye on the temperature ^,~

mr_bovinejony - 30-10-2020 at 16:01

I've been thinking about this one lately and after seeing chem players video could anhydrous oxalic acid be substituted for gaa? I'm not sure of the solubility of oxalic acid in acetonitrile but surely there must be a solvent that can dissolve the acid and be miscible with acetonitrile

clearly_not_atara - 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.

mr_bovinejony - 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!

mr_bovinejony - 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?

clearly_not_atara - 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.

karlos³ - 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.

mr_bovinejony - 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

njl - 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.

clearly_not_atara - 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

mr_bovinejony - 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

mr_bovinejony - 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

Mateo_swe - 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 527 times


mr_bovinejony - 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

Mush - 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 246 times

Attachment: DE151864C.pdf (190kB)
This file has been downloaded 233 times


[Edited on 13-3-2021 by Mush]