Vibrating_Lights (Hive Bee)
09-30-01 20:52
No 218791
      Idiosafrole <NaI +H2SO4>with Safrole in DMSO  Bookmark   

A Simple distillation apparatus is erected and in the recieving flask Saforle and DMSO and GAA are added.ice water is started throught thew condensor. NAI is placed in the  2 kneck distilling flask. H2SO4is driped onto the salt. the hi produced will condense in the condenser and dirp in to the recieving that is being stirred in the ice bath.  Continue to stirr in icebath for 4 hrs after the hi is done dripping. The ice is very important due to carbocation rearangement.If it is not kept cold the -1- position will be halogenated. After stiring is complete flood the rxn mixture with water, seperate product, extract the aq.layer with Dcm, combine product and extracts wash with bicarb solutions and water, strip solvent under vacume to yeild iodiosafrole which can be animated through the same prosceses as bromosafrole. NaI and H2SO4 are plenty ful and cheap the solvent is about 1$/OZ wink
 
 
 
 
    Rhodium
(Chief Bee)
09-30-01 20:58
No 218795
      Re: Idiosafrole <NaI +H2SO4>with Safrole in DMSO  Bookmark   

What is your yield of iodosafrole? How was it characterized and purified?
 
 
 
 
    Vibrating_Lights
(Hive Bee)
09-30-01 21:12
No 218799
      Re: Idiosafrole <NaI +H2SO4>with Safrole in DMSO  Bookmark   

? haven't done it yet.still just thinking about it.I think it will be beautifulif it works well. A completely otc amine synth could be coming in order. what are your thoughts.
 
 
 
 
    PEYOTE
(Hive Bee)
09-30-01 21:23
No 218802
      Re: Idiosafrole <NaI +H2SO4>with Safrole in DMSO  Bookmark   

Referring to:

the hi produced will condense in the condenser

Ehm, HI is a gas, isn't it? His boiling point is -35C. How can it condense if the water in the condenser is 'at maximum' at 1C?
 
 
 
 
    terbium
(Old P2P Cook)
09-30-01 21:44
No 218809
      Re: Idiosafrole <NaI +H2SO4>with Safrole in DMSO  Bookmark   

NAI is placed in the  2 kneck distilling flask. H2SO4is driped onto the salt. the hi produced will condense in the condenser and dirp in to the recieving that is being stirred in the ice bath.
This has already been discussed extensively over the past several months, principally considering HBr for bromosafrole but the considerations are the same or even more so for HI and iodosafrole. It has been generally agreed that your scheme won't work. If you want to know why then read the HBr/bromosafrole posts of the past several months.
 
 
 
 
    foxy2
(Distinctive Doe)
10-01-01 05:39
No 218930
      Re: Idiosafrole <NaI +H2SO4>with Safrole in DMSO  Bookmark   

Preparation of Pure Anhydrous Solutions of Hydrogen Iodide in Acetic Acid

Org. Proc. Res. Dev., 1 (1), 88-89, 1997.

Abstract:
The presence of molecular iodine in anhydrous solutions of hydrogen iodide in acetic acid gives rise to unstable impurities during the hydriodination of isolated double bonds.(diiodides) This can be overcome by using aqueous hydriodic acid, as the source of hydrogen iodide, from which the iodine has been removed by washing with a solution of an organic soluble ion exchange resin.

9- and 10-Iodostearic Acids (ISA, 2 and 3).
Into an argon-purged separation vessel fitted with a mechanical stirrer is placed hydriodic acid (2.165 L, specific gravity 1.91, 65.0% w/w). A solution of Amberlite LA-2 (0.395 kg) in toluene (5.0 L) is then added to the vessel, and the agitator is used to mix the layers for 2 min. After the layers are allowed to separate, the colourless hydriodic acid layer is run into an argon-purged holding vessel prior to returning to the separator for a single wash with a quantity of degassed toluene. For solutions heavily contaminated with molecular iodine, a second wash with the LA-2 resin solution is required.

Into an argon-purged reaction vessel is then placed acetic anhydride (6.94 L, 99.7%, 73.33 mol) which is vacuum degassed. Washed hydriodic acid (1.973 L, 19.15 mol of HI, 73.33 mol of H2O) is added to the mechanically stirred solution at such a rate that the temperature is maintained below 55 C. If the temperature is allowed to rise above this limit, there is some loss of water vapour by entrainment, and this results in incomplete hydrolysis of the acetic anhydride.

The mixture is stirred for a further 60 min after completion of the addition of the aqueous acid and is then cooled to 20 C prior to the addition of a vacuum-degassed solution of oleic acid (1.362 kg, 4.822 mol) in glacial acetic acid (2.0 L) over a period of 10 min.

After completion of the addition, the mixture is stirred for a further 16 h prior to removal of the majority of the acetic acid by vacuum codistillation with 10 volumes of toluene (50 mmHg, <50 C). The dark residue is dissolved in toluene (14.0 L) and then transferred to a separating vessel followed by washing with a 5% solution of sodium thiosulphate (2.0 L) and then deionised water. The thiosulphate wash is first back-washed with a small quantity of toluene, which is combined with the main solution of product.

The organic solution is dried over magnesium sulphate and filtered through a short bed of 100-200 mesh Florisil prior to removal of the toluene under reduced pressure, to leave the product as a colourless to very pale yellow oil (1.8728 kg, 4.564 mol, 94.6%). Yield range: 90-97%.







Publication date: 1997-03-31  
Inventor(s): YAMAGUCHI TAKAICHI; KURIHARA MEGUMI; HONDA KATSUTO; YASUHARA SHIGEO  
Applicant(s):: TORI CHEM KENKYUSHO:KK  
Requested Patent: JP9086902 

Abstract
HI gas is manufd. by reaction of aq. phosphoric acid with P2O5 and metal iodides.  Alternatively, the manuf. is carried out by mixing and heating the above raw materials.  Optionally the HI gas obtained is dehydrated and purified.  The HI gas obtained is useful as etching gas in manuf. of semiconductor devices.

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