Author Topic: An easy OTC 2,5-diMeO-phenylmercaptan  (Read 3118 times)

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Sulfuryl Chloride
« Reply #20 on: May 20, 2002, 03:11:00 PM »
I'll add to what Osmium said.
Looks like the cooling of the catalytic chamber is essential.

Damn this really sounds easy!

Catalytic preparation of sulfuryl chloride.
Tarle, M.; et al.   
Bull. Mukden Arsenal  No. 8  9 pp.  (Language unknown)
CAN 29:43098    AN 1935:43098   
The prepn. of SO2Cl2 from SO2 and Cl2 in the presence of active C as catalyst was studied with the purpose of ascertaining the possibility of industrializing the process.  With 10 g. Kahlbaum active C as catalyst, 150 g. SO2O2 was obtained in 1.5 hrs. at -10°; at 0°, the yield drops to 60 g. and at +20°, practically to zero.  The catalytic activity of the active C gradually decreases after prolonged use (10-12 hrs. or more) because of poisoning by certain by-products (HCl, H2SO4).  The catalytic power of various kinds of active C increases with its activity. 

The industrial use of chlorine by way of sulfuryl chloride.
Tantzov, N. V.   
J. Chem. Ind. (Moscow)  (1933),   (No. 1),  36-40. 
CAN 27:39469    AN 1933:39469
SO2Cl2 results quantitatively from a 1:1 mixt. of SO2 and Cl2 when charcoal is used as a catalyst.  Dense charcoal is preferable to porous varieties.  SO2 and Cl2 react directly with boiling H2O giving pure, nearly anhyd. HCl and H2SO4 without the use of a catalyst.  Large amts. of air and volatile As compds. have no effect on the reaction. 

Sulfuryl chloride.    
Kroner, Gerhard.  (I. G. Farbenind. A.-G.).    (1930),

Patent DE522884

  In German 
SO2Cl2 is prepd. from Cl and SO2 by the catalytic action of active C prepd. by the decompn. of carboniferous material by the aid of other catalyzers at temps. below 400°.  An example is given.

A laboratory process for the preparation of sulfuryl chloride.
Meyer, Julius.   
Z. angew. Chem.  (1931),  44  41-2. language unknown
Danneel's process, C. A. 21, 1235, for the combination of Cl2, and SO2 with activated C is simplified.  A ball condenser with 6 balls loosely packed with glass wool and granular C was used as the catalyst chamber.  To prevent initial gas loss the charge of the top ball was moistened with 1 cc. of liquid sulfuryl chloride.  The gases enter the reaction chamber through a H2SO4 wash bottle which serves also as a flow indicator. 150 g. of SO2Cl2 may be prepd. per hr. at a gas flow of 3-4 bubbles per sec.  Quant. combination ol the gases is obtained at temps. up to 20°.  The raw product is very pure and requires only 1 fractionation.  In contrast to the Danneel process, the advantages of the method lie in the simplified app., the use of a small quantity of activated C, and the lack of a need for low temp. 

Sulfuryl chloride.    
McKee, Ralph H.; Salls, Carroll M.    (1930),    
Cl gas and SO2 are passed into a body of sulfuryl chloride contg. a minor proportion of a catalyst such as an acid-treated active C in suspension.

Laboratory apparatus for the preparation of sulfuryl chloride.    
Danneel, H.    Z. angew. Chem.  (1926),  39  1553-4.  Journal  language unknown.   CAN 21:10237    AN 1927:10237   
Sulfuryl chloride is prepd. by passing equiv.  Proportions of Cl and SO2 through activated C in a 500-cc. tube provided with an overflow.  Rubber connections may be used.  As the reaction is strongly exothermic, it is necessary to cool in an ice-salt mixt.  A 100% yield may be obtained and a kg. prepd. in an hr.

The preparation of sulfuryl chloride.    
Durrans, T. H.   
J. Soc. Chem. Ind.  (1926),  45  347-50T. 
cf. C. A. 13, 1587.  Exptl. results indicate that only substances possessing residual affinity in some form are capable of catalyzing the reaction SO2 + Cl2 ® SO2Cl2, and that this function is exerted by forming simultaneously with both Cl2 and SO2 loose compds., which then proceed to interact to form SO2Cl2 and to regenerate the free catalyst.  As the reaction is bimol. the greatest velocity is attained when the concns. of the 2 loose compds. are equal; an excess of one of the gases tends progressively to sat. the catalyst at the expense of the other gas, thus inhibiting the final reaction by disturbing the equimol. ratio.  The following compds. were found to be good catalysts: EtOAc, Me2CHCO2Et, AcCH2CO2Et, PhCH2CO2Et, BzOEt, PhCH:CHCO2Et, CH2(CO2Et)2, iso-AmO2CH, iso-AmOAc, iso-AmONO2, PhCH2OAc, PhCH2OBz, PhCH2CN, PhOAc, CH(OAc)(CH2OAc)2, CH2(OH)CHClCH2Cl, Ph3PO4, (o-MeC6H4)3PO4, Et2O, (PhCh2)2O, p-MeC6H4OMe, BzH, Ac2CH2, (CH2)5:CO, AcPh, AmCH(OMe)2, eucalyptol, Me isoeugenol, anisaidehyde, a-pinene and limonene; the following catalysts were of more moderate activity: MeCH(OEt)2, iso-BuCl, Ph2CO, Me2CO, C6H6N and carvone;  the following were inactive or nearly so: BzOMe, iso-AmOBz, ClCH2CO2Me, Cl3CCO2Bu, Me2SO4, CH(OH)(CH2OH)2, BzOH, C2H7CO2H, ClCH2CO2H, Cl2CCO2H, PhCH:CHCO2H, o HOC6H4CO2H, PhCH2CO2H, C5H12, PhH, PhMe, PhNO2, BzCl, AcCl, CHCl3, CCl4, and oleic acid. 

DAMN If these guys did it with cork stoppers then anyone can do it!!

Preparation of sulfuryl chloride.
Bert, Leonce.   
Bull. soc. chim.  (1922),  31  1264-70.
For the prepn. of large amts. of SO2Cl2 the method of Ruff (Ber. 34, 3509 (1901)) is most practicable but it contains two sources of difficulty.  Cork stoppers, even protected by Na2SiO3, are soon disintegrated by hot vapors of SO3HCl and SO2Cl2 and the interior tube of a glass reflux is frequently fractured and entrance of water into the boiling SO3HCl causes violent and dangerous explosions.  These difficulties were overcome by covering the stoppers with several layers of asbestos paper cemented with Na2SiO3 (Vorlaender and Schilling, Ann. 310, 372(1900)) and by using for the inner tube of the reflux an iron tube of 1 m. interior diam., 1 m. length and 2 mm. wall-thickness, carefully scoured throughout the interior and so much of the exterior as projects into the flask.  The iron is attacked but little and salts of Fe have practically no influence on the reaction.  With a shorter tube the SO2Cl2 contains considerable SO3HCl and mercurous salt.  A condenser jacket 70 cm. long is placed as close as possible to the upper end of the iron tube.  The flask, of vol. 250 cc. for each 300 g. of SO3HCl heated, is fixed in an inclined position.  The condenser for SO2Cl2 is set vertically and connected to the top of the iron tube by a glass tube of 8 mm. exterior diam., as short as possible, by means of asbestos thread impregnated with Na2SiO3 at the iron and a Vorlaender stopper at the condenser.  Provided a rapid current of cold water was maintained in this condenser, various types proved equally efficient and cooling the receiver by ice was unnecessary.  After the entire app. has been carefully dried, the reflux jacket is filled with cold water and the tap closed; the SO3HCl is brought to rapid boiling and as soon as vapor of SO2O2 begins to appear in the second condenser, a very small stream of water is admitted to the first so as to maintain a temp. of 70-95°.  Use of 1% of HgSO4 instead of 0.66% Hg gave yields 4% greater; 56% in 2 hrs.; 80% in 6 hrs.  For greatest efficiency and economy, after heating 1 hr.
substitute a fresh flask of SO3HCl; let the first cool; HgSO4 seps. almost completely and is filtered off by glass wool and used again; recover SO3HCl by distn. and use the residual acid to generate HCl.  After rectification by a 60-cm.  Vigreux column the yield is 1500 g. of pure SO2Cl2 for each l200 g. of SO3HCl.  For prepn. of SO3HCl use com. oleum of 70% SO3, not over 1100 g. in a 1-1. flask, and displace air by HCl throughout the train before admitting the oleum.  Connect to the flask a 50-cm. condenser, glass or iron interior tube, by a glass tube of at least 8 mm. diam., bevelled at both ends and having a lateral opening near the bevel in the flask.  Satn. with HCl is evidenced by exit of this gas at the end of the train.  Then replace the inlet tube for HCl by a tube carrying a thermometer and distil.  An ordinary cork stopper easily endures distn. of 1 kg. of SO3HCl and the product is colorless.  Two kg. can be prepd. in 8 hrs. with a single app. 

The synthesis of sulfuryl chloride in the presence of organic compounds.  
Cusmano, G.    Florence,   
Gazz. chim. ital.  (1920),  50(II),  70-80.
It has long been known that HCO2H, AcOH, C2H4 and camphor favor the reaction SO2 + Cl2 ® SO2Cl2, which without them proceeds slowly in sunlight.  The C2H4 is chlorinated during the reaction and when this is complete SO2Cl2 ceases to be formed.  HCO2H and AcOH are also altered in the reaction but without definite relation to the production of SO2Cl2.  Camphor is not changed in the reaction.  In previous work C. (C. A. 13, 1587) found that other compds. have the same effect.  In extending this investigation C. has tested some other compds. and first detd. the influence of the CO group of camphor.  Thus dihydrocamphorone, cyclohexanone, tetrahydrocarvone, menthone and fenchone were tested; all of them behave like camphor.  When their halogen derivs. are used they lose this property.  Of the terpenic ketones, carvone, pulegone, and carvotanacetone were tested and found to favor the synthesis of SO2Cl2.  These compds. contain both an unsatd. linking and a CO group.  C.'s expts. have convinced him that of these the CO group is more active than the ethylene double bond.  AcMe does not promote the reaction, probably because it is so rapidly chlorinated.  This chlorination is so much diminished at -60° that AcMe now promotes the reaction.  MeCOEt behaves similarly while Me nonyl ketone is catalytically active even at -10°.  AcPh catalyzes the reaction at -10° but is chlorinated.  BzPh and fluorenone catalyze the reaction without being chlorinated but lose the power to do so if previously brominated or nitrated.  The monocarbonyl ketones accordingly have the property in general of increasing the velocity of combination of Cl with SO2 and lose this property when halogens, NO2 or SO3H groups are introduced at any distance from the CO (as tested with a-, b- and g-monobromocamphor).  The presence of CO2H does not interfere.  The influence of the chain bound to the CO does not appear to be great.  The 1st interpretation of the reaction offered and tested is that these compds. act through the basic property of their oxygen, i.
e., by the formation of unstable oxonium salts with the Cl or SO2 or both, and these salts are not formed when a negative atom or group is introduced, because this basicity is neutralized.  In order to test this hypothesis various other compds. were tested.  Cineo'e, which favors the reaction, undergoes chlorination as the Et ester, which had to be used at -45-50° in order to give good results.  Since the formation of oxonium derivs. is characteristic of O compds. aldehydes, acids and esters were tried.  Alcs. were excluded because of their ease of chlorination.  EtCHO gave good results at -50°.  BzH and piperonylic aldehyde even at -10° did not catalyze the reaction well.  Meta- and paraldehyde gave fair results at -10°.  AcOH and BzOH promote the reaction at -10° slowly.  BzOH is not chlorinated and is therefore the best.  AcOEt and BzOEt act, but must be protected from the Cl by working at -50°.  Of other compds. containing two O functions used, ketocineole and camphorcarboxylic acid promote the synthesis, while camphorquinone, buccocamphor, benzo- and thymoquinone are inert at -10°.  In the a,a-diketones the one CO acts as a negative group toward the other and if one is converted into an oxime the compd. becomes catalytically active; isonitrosocamphor acts like camphor.  With the quinones the inactivity is probably due to the formation of relatively stable addition products with Cl or SO2.  The inactivity of dibenzalacetone and similar compds. may be explained analogously.  The results are summarized in a large table.  The compds. were used in equimol. amts., treated with excess of SO2, reduced to a detd. temp. and treated for the same period of time at the same rate with SO2 and Cl2 dried with H2SO4.  The SO2 was expelled and the SO2Cl2 removed and detd. by distn., after which the residue was examd.  In only a few cases was the compd. used for catalysis recovered unchanged.  In most cases it was chlorinated.  Blank expts. showed whether this was due to the Cl or SO2Cl2 either during the synthesis or distn.
 C. thinks that a transitory compd. is formed of the oxonium type, but that not all compds. capable of giving these derivs. necessarily favor the reaction but only those that are formed and decompd. with a certain velocity.  The ketones and esters seem to have the required properties in the right degree.  The expts. are being continued. 

Investigation of the catalytic activity of charcoal in the synthesis of sulfuryl chloride.    
Soloniewicz, Rajmund.    Politech.,  Lodz,  Pol.   
Zeszyty Nauk. Politech. Lodz., Chem.  (1961),  10  85-9.  CAN 60:49341    AN 1964:49341
Charcoal "Carbopol extra" (made in Zaklady Elektrod Weglowych, Raciborz) was used as a catalyst in the synthesis of SO2Cl2 from SO2 and Cl2.  With this catalyst (dried at 200-250°) conversion of SO2 + Cl2 mixts. (in a molar ratio 1:1) can be up to 85.5%.  The activity of the catalyst does not change over 40 hrs. of operation.  Adsorption of H2O on charcoal surface causes poisoning of the catalyst. 

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