[Ingeniosuccinimide]

Hello,


I have a couple of reactions in which it is required to add a very small amount (around 1,5 mL) of sulfuryl chloride and in another case thionyl chloride (both dropwise over a period of 15 minutes).

Since I have only large addition funnels, I was considering using a polymer or glass syringe with classic Luer tip needle.

Will polymer syringes and steel needles (I have only these) be corroded or react with SOCl/SOCl2? If yes, can you give me an advice about what to do and how to add these compounds?

[discodermolide]

It would be better to use glass syringes.
The steel needles will corrode.
Why not dissolve them in some inert solvent say 5-10 mL and add them. Beg borrow or steal a small addition funnel first.
Otherwise you could use teflon tubing and cannulate them into the reaction solution.

[Ingeniosuccinimide]

Thanks for the advice, we have small addition funnels (15~20 mL).

However, in my case it's really dubious if I might dissolve the chlorides in something inert, since I have a really unpleasant procedure, you might have a look if you are interested:

http://www.sciencedirect.com/science/article/pii/S0040403900842938

Maybe the teflon tubings are not too expensive. Hope these will do well.

[Babcock_Hall]

Making a sulfinyl chloride may be in my future.  Please let us know how your synthesis turned out.

[discodermolide]

Making a sulfinyl chloride may be in my future.  Please let us know how your synthesis turned out.

Babcock, I wish you good luck.

[408]

I have never used sulfuryl chloride, but have used thionyl countless times.  A plastic syringe and stainless needle will be just fine for a 15 min addition.  The plastic will swell and pushing the plunger will be more difficult but it works.  Glass syringe and stainless needle will have no issues. For a short addition like this and with so little liquid I would just do the addition by hand as it is only 0.1 mL per min.

[Babcock_Hall]

I used sulfuryl chloride many years ago.  I found that it was necessary or at least desirable to distill the commercial product to remove low-boiling impurities.

[Ingeniosuccinimide]

Babcock, I wish you good luck.

I understand your reply very well... after 6 weeks of painful work with these...

I used sulfuryl chloride many years ago.  I found that it was necessary or at least desirable to distill the commercial product to remove low-boiling impurities.

In my case it's particularly interesting since the authors of the paper I used state that the simple arylsulfinyl chlorides are not to be distilled due to danger of explosion.. 

[Babcock_Hall]

I don't know anything about the product you are making.  I was solely referring to distilling SO₂Cl₂, sulfuryl chloride.  My recollection is that I used a simple distillation, but perhaps it would have been better to distill from a small fractional set-up (it took a large volume of material before the boiling point became constant).  IIRC I worked with sulfuryl chloride in dichloromethane as the solvent, but I would need to double check this to be certain.

[opsomath]

IIRC (late to the party) I used small 10 mL and under qtys. of thionyl chloride with a plastic syringe and clean, dry stainless needle with no problem.

[Ingeniosuccinimide]

Update:

I managed somehow to produce the phenylsulfinyl chloride. The authors of the same paper state that for purpose of full characterization the product should be converted to phenyl sulfinate, folowed just by note: (ethanol\pyridine).

I suppose that reaction is somewhat analogous to standard ester formation from acyl chloride and alcohol.

Could sb explain or paste some procedure of forming ethyl esters with ethanol in pyridine? I don't have access to SciFinder, otherwise I would have checked it...

[opsomath]

You can probably get away with distilling off excess SOCl2, then in one pot adding DCM, absolute ethanol dried over sieves, and one equiv. of dry pyridine. Pyridinium chloride should ppt out. But definitely check Org Synth first.

[BobfromNC]

I will warn people that chlorosulfonic acid DOES have a bad tendency to dissolve plastic syringes, rubber parts, and much more, not the same as what you are doing now, but if you ever try to make a sulfonyl chloride with it, please be very cautious, and use glass pipettes or syringes.   An old lab mate almost hurt themselves trying to use a plastic syringe with it once.  You should wear heavier gloves (not latex exam gloves) with working with it as well.   Just a safety note based on my experience.