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US2825745A - Oxidation of organic sulfides - Google Patents

Oxidation of organic sulfides Download PDF

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Publication number
US2825745A
US2825745A US574073A US57407356A US2825745A US 2825745 A US2825745 A US 2825745A US 574073 A US574073 A US 574073A US 57407356 A US57407356 A US 57407356A US 2825745 A US2825745 A US 2825745A
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sulfide
air
oxidation
reaction
sulfides
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US574073A
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Smedslund Tor Halfdan
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Stepan Co
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Stepan Chemical Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D339/00—Heterocyclic compounds containing rings having two sulfur atoms as the only ring hetero atoms
    • C07D339/08—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides

Definitions

  • This invention relates toa method for the'manufacture of sulfoxide, and more particularly, to an improved process for the manufacture of low molecular weight sulfoxides from the Corresponding sulfides.
  • United Statesletters Patent No. 2,581,050 relates to the vapor phase oxidation of dimethyl sulfide to dimethyl sulfoxide using an oxygen-containing gas which also includes a small amount of an oxygen-transmitting nitrogen oxide (such as N02), using reaction temperatures sufficient to maintain the dimethyl sulfide in the vapor phase.
  • an oxygen-containing gas which also includes a small amount of an oxygen-transmitting nitrogen oxide (such as N02)
  • United States Letters Patent No. 2,702,824 relates to the liquid phase oxidation of low molecular dialkyl sulfides to the corresponding sulfoxides by bubbling a gaseousmixture through the liquid dialkyl sulfide at a reduced temperature to maintain the dialkyl sulfide in the liquid phase.
  • the gaseous mixture bubbled through the liquid dialkyl sulfide comprises an oxygen-containing gas and a small amount of an oxygen-transmitting nitrogen oxide;
  • the instant invention consists in a process for the manufacture of a low molecular weight sulfoxidefrom thecorresponding sulfide by oxidation thereof, which comprises drying atmospheric air to reduce the relative atent C 2. humidity thereof by at least one-half and then contacting the dried air with the sulfide in the presence of an amount of oxygen transmitting. nitrogen oxide at least suflicient to catalyze the oxidation.
  • S isa nuclear atom.
  • Such compounds include 5 to 6' membered'rings having 1. to 2 nuclear S atoms and the remainder C atoms, in saturated or unsaturated rings, with l to, 2. substituents on the C atoms, preferably C C.,.alkyl substituent-s'.
  • Typical types of compounds are based on the thiophene and tetramethylene sulfide nuclei:
  • each is H or a C -C alkyl group but not more than 2 X s arealkyl" groups and the remainder are Hs.
  • Examples include tetramethylene sulfide, l-methyl tetramethylene sulfide, Z-methyl tetramethylene sulfide, 1,3-dimethy1' tetramethylene sulfide, etc. up to l-butyl tetramethylene sulfide.
  • Another heterocyclic compound is based on a 6 membered ring nucleusr wherein Y' may, be S or CX and: the, Xs have the, meaning hereinbefore given.
  • Examples. include pentamethylene sulfide, l-methyl pentamethylene sulfide, 2- methyl pentamethylene sulfide, 3-methyl pentamethylene sulfide, 1,2-dimethyl pentamet-hylene, sulfide, etc. up to the butyl pentamethylene sulfides; and dithiane. (i. e. diethylene disulfide), l-methyl dithiane, etc. up to the butyl dithianes.
  • Members of these groups whichare nor.- mally solids can be dissolved in, for example, dimethyl sulfoxide to provide a liquid composition of the sulfide that is oxidized in the'process of the invention.
  • the organic sulfide may be oxidizedv in either the liquid or the vapor phase, but in the case of the higher boilingsulfides it is ordinarily preferable to employ liquid phase oxidation at lower temperatures rather than athigher temperatures required to volatilize-the sulfide.
  • sulfides boiling at temperatures above about C. should be oxidized in the liquid phase rather than the vapor phase; and sulfides which are solids at temperatures above about 75 C.
  • the. aforementioned temperature of 75 C. should be about 40 (3., since this is a preferred maximum temperature for carrying out the instant oxidizing reaction.
  • the minimum temperature is, of course, around 10 C, or the minimum temperature at which Patented, Mar. 4, 1-958 appreciable oxidation talces 'place.
  • the preferred reac- V tion temperature range is about 2540'C.
  • drying agent such as calcium oxide
  • the humidity in the air may, of course, be reduced by passingthe air throughlany sort of drier or dehumidifier.
  • a preferred process .involves passing the atmospheric air over' calcium oxide, which efiectsa reduction in the moisture content to a relative humidityof approximately 1% at 100 F. (which is the moisture content ofapproximately 0.0005 pound per pound of 'bone dry air).
  • the dehumidification of air is relatively easy and economic '4 reaction. This causes difiiculties in control of the re action.
  • the constant consumption of. the I catalyst requires the use of greater amounts of the nitrogen oxide than would ordinarily be required; Also, the acids formed must subsequently be neutralized in the sulfoxide product.
  • V V As a demonstration of the instant invention, dimethyl? sulfide is evaporated at'a rate of 0.7 gram per minute i nto an air current of 680 milliliters per minutecontaining nitrogen dioxide introduced into the air current at-a rate of 45 milliliters per minute. 7 The resulting gaseous mixture is passed into the first of a series of four reaction. chambers, each consisting of a glass tube 4.2 centimeters in diameter and 100 centimeters in length. The reaction starts immediately,-the temperature of the reaction ture reaches about 55 C.1in the first reaction tube", about 45 C. in the second tube, abut 36 C; in the third tube and about C.'in the last tube. The crude'product.”
  • ture can be carn'edont to advantage prior to reaction.
  • Such gases include NO, N0 N 0 N 0 etc., but the predominating catalytic func- 1 tion is generally thought of on the basis of N0 as indicated in the following equations representing the reaction which is believed to take place:
  • air employed is first passed through a tube containing 200 grams of-calciumoxide so as to reduce the relative humidity of the air to about 5% at 30 C.; but the dimethyl sulfide employed contained about'0.4% water. After purification (wherein the dimethyl sulfide was'removed by heating the product to 150 C., the methane sulfonic acid was neutralized by adding slaked lime, and ii the dimethyl sulfoxide was distille in vacuum) the yield of pure dimethyl sulfoxide was 91% of the theoretical 7 yield.
  • a process for the manufacture of a di-lower alkyl sulfoxide from the corresponding sulfide by oxidation thereof which comprises contacting the sulfide in substantially anhydrous form with an oxidizing atmosphere containing air and an amount of oxygen transmitting nitrogen oxide at least sufiicient to catalyze the oxidation, the improvement which comprises contacting the sulfide with air having a moisture content below 0.002 pound per 6 pound of air.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Catalysts (AREA)

Description

United States OXIDATION OF GRGANIC SULFEDES 2 Claims. (Cl. 260-607) This invention relates toa method for the'manufacture of sulfoxide, and more particularly, to an improved process for the manufacture of low molecular weight sulfoxides from the Corresponding sulfides.
United Statesletters Patent No. 2,581,050 relates to the vapor phase oxidation of dimethyl sulfide to dimethyl sulfoxide using an oxygen-containing gas which also includes a small amount of an oxygen-transmitting nitrogen oxide (such as N02), using reaction temperatures sufficient to maintain the dimethyl sulfide in the vapor phase.
United States Letters Patent No. 2,702,824 relates to the liquid phase oxidation of low molecular dialkyl sulfides to the corresponding sulfoxides by bubbling a gaseousmixture through the liquid dialkyl sulfide at a reduced temperature to maintain the dialkyl sulfide in the liquid phase. The gaseous mixture bubbled through the liquid dialkyl sulfide comprises an oxygen-containing gas and a small amount of an oxygen-transmitting nitrogen oxide;
In eachof the foregoing operations, air is preferred as the oxygen-containing gas for obvious economic reasons; In carrying out these operations using air, however, prior to the instant invention it was found that the operating conditions were difficult to control and the yields obtained left something to be desired. The instant invention is based in part on the discovery that the use of pre-dried atmospheric air in the foregoing operations results in a distinct improvement in the, yields andta distinct improvement in the control of the operating conditions. Compared to the quantities of other ingredients used the amount of moisture in atmospheric air is extremely small. Nevertheless, it hasbeen found that this moisture in the air apparently has a very dis: tinct. harmful effect upon the reaction, and the instant invention contemplates the removal thereof from the air before carrying out the reaction. The instant invention. also contemplates the use of substantially anhydrous sulfides in thereaction mixture, since it. has also been, discoveredthat the relatively small amount of moisture ordinarily present in the sulfides has a definitely harmful. effect uponthe reaction.
It is, therefore, an important object of the instant invention to provide an improved method for oxidizing low molecular weight sulfides, to the corresponding sulfoxides.
It is a further object of the instant invention to provide an improved method for the manufacture of low molecular weight sulfoxides from the corresponding sulfides by an oxidation process which is made industrially superior by removal of moisture from the reactants prior to carrying out the oxidation reaction.
Other and further objects, features and advantages of the present invention will become apparent to those skilled in the art from the following detailed disclosure thereof.
The instant invention consists in a process for the manufacture of a low molecular weight sulfoxidefrom thecorresponding sulfide by oxidation thereof, which comprises drying atmospheric air to reduce the relative atent C 2. humidity thereof by at least one-half and then contacting the dried air with the sulfide in the presence of an amount of oxygen transmitting. nitrogen oxide at least suflicient to catalyze the oxidation.
The sulfides which may be used in the practice of the.
instant invention include the low molecular weight dialkyl sulfides having the following formula:
S isa nuclear atom. Such compounds include 5 to 6' membered'rings having 1. to 2 nuclear S atoms and the remainder C atoms, in saturated or unsaturated rings, with l to, 2. substituents on the C atoms, preferably C C.,.alkyl substituent-s'. Typical types of compounds are based on the thiophene and tetramethylene sulfide nuclei:
wherein each is H or a C -C alkyl group but not more than 2 X s arealkyl" groups and the remainder are Hs. Examples include tetramethylene sulfide, l-methyl tetramethylene sulfide, Z-methyl tetramethylene sulfide, 1,3-dimethy1' tetramethylene sulfide, etc. up to l-butyl tetramethylene sulfide.
Another heterocyclic compound is based on a 6 membered ring nucleusr wherein Y' may, be S or CX and: the, Xs have the, meaning hereinbefore given. Examples. include pentamethylene sulfide, l-methyl pentamethylene sulfide, 2- methyl pentamethylene sulfide, 3-methyl pentamethylene sulfide, 1,2-dimethyl pentamet-hylene, sulfide, etc. up to the butyl pentamethylene sulfides; and dithiane. (i. e. diethylene disulfide), l-methyl dithiane, etc. up to the butyl dithianes. Members of these groups whichare nor.- mally solids can be dissolved in, for example, dimethyl sulfoxide to provide a liquid composition of the sulfide that is oxidized in the'process of the invention.
In. the practice of the invention, the organic sulfide may be oxidizedv in either the liquid or the vapor phase, but in the case of the higher boilingsulfides it is ordinarily preferable to employ liquid phase oxidation at lower temperatures rather than athigher temperatures required to volatilize-the sulfide. Ingeneral, sulfides boiling at temperatures above about C. should be oxidized in the liquid phase rather than the vapor phase; and sulfides which are solids at temperatures above about 75 C. should be oxidized in the liquid phase in solution in a sulfoxide such as dimethyl sulfoxide (or anyother solvent which is not reactive with the ingredients here present, namely, the sulfide, sulfoxide, NO and N0 preferably, the. aforementioned temperature of 75 C. should be about 40 (3., since this is a preferred maximum temperature for carrying out the instant oxidizing reaction. The minimum temperature is, of course, around 10 C, or the minimum temperature at which Patented, Mar. 4, 1-958 appreciable oxidation talces 'place. The preferred reac- V tion temperature range is about 2540'C.
The sulfides used in the practice of the instant invendried air, still better results are'obtained using th'e substantially anhydrous sulfide.
same in liquid or vapor form over a suitable drying agent, such as calcium oxide.
Although air at 80 F. having 50% relative humldity contains only about 0.01 pound of water per pound of air this 'apparentlyinsignificant amount of water has been V foundito beextremel'y. harmful. In fact,it is.possible to The sulfide 'rnay beobtained in substantially anhydrous form -(i'. e., containing less than about 0.1% by weight of water) bypassing the obtain adistinctl advantage in the practice of the instant invention 'merelybyreducing the relative humidity. of the air by atleastone-half' of the initial relativehumidity. Preferably, however, this reduction in relative humidity also results in a reduction of the moisture content in the air to belowabout 0.002 pound per pound of air. Best resultsare obtained if the moisture contentis reduced to below about 0.001 pound per pound of air.
The humidity in the air may, of course, be reduced by passingthe air throughlany sort of drier or dehumidifier. A preferred process .involves passing the atmospheric air over' calcium oxide, which efiectsa reduction in the moisture content to a relative humidityof approximately 1% at 100 F. (which is the moisture content ofapproximately 0.0005 pound per pound of 'bone dry air). ,The dehumidification of air is relatively easy and economic '4 reaction. This causes difiiculties in control of the re action. In addition, the constant consumption of. the I catalyst requires the use of greater amounts of the nitrogen oxide than would ordinarily be required; Also, the acids formed must subsequently be neutralized in the sulfoxide product. It is further believed that the presence of the moisture actually interferes with the catalytic function so that lower yields of the sulfoxide are obtained. V V As a demonstration of the instant invention, dimethyl? sulfide is evaporated at'a rate of 0.7 gram per minute i nto an air current of 680 milliliters per minutecontaining nitrogen dioxide introduced into the air current at-a rate of 45 milliliters per minute. 7 The resulting gaseous mixture is passed into the first of a series of four reaction. chambers, each consisting of a glass tube 4.2 centimeters in diameter and 100 centimeters in length. The reaction starts immediately,-the temperature of the reaction ture reaches about 55 C.1in the first reaction tube", about 45 C. in the second tube, abut 36 C; in the third tube and about C.'in the last tube. The crude'product."
andfor this reason yery definite advantage from a prac- V tical point of view is obtained merely'by drying the air, while using the commercial (undried) sulfide. In the vapor phase reaction, however, the rier for the sulfide to conduct. the same into the reaction zone, and d'ehumidification of the air-sulfide vapor 'mix-.
ture can be carn'edont to advantage prior to reaction.
. The amounts and types of oxygen-transmitting nitrogen oxides used in the practice of the instant invention are described in detail in said U..S. Patents No. 2,581,050
and 2,702,824 and neednot be described with'further particularity herein." Such gases include NO, N0 N 0 N 0 etc., but the predominating catalytic func- 1 tion is generally thought of on the basis of N0 as indicated in the following equations representing the reaction which is believed to take place:
oxide grouping. It will be noted that theactual oxidation of the sulfide to the sulfoxide is believed to be causedby reaction between the sulfide. S atom and N0 but the resulting NO is instantly regenerated to NO by the.
presence of the oxygen in the air. ciated, only a small amountof the As will be appreoxygen-transmitting nitrogen oxide, such as about 10% to 15% by volume,
the oxidation of the sulfide.
Although it is not desired to limit the invention'to any particular theory,
following equation 3 2NO +H 0 HN0 +HNO Theacids'thus formed tend to condense out with the sulfoxide product and the concentration of catalyst is 4 thus constantly being varied (in fact, reduced) during the air is used as a car-1 contained traces of dimethyl sulfide and nitrogendioxide, about 2% methane sulfonic acid and small amounts (i. e. about 0.3%) of water. In this demonstration, the
air employed is first passed through a tube containing 200 grams of-calciumoxide so as to reduce the relative humidity of the air to about 5% at 30 C.; but the dimethyl sulfide employed contained about'0.4% water. After purification (wherein the dimethyl sulfide was'removed by heating the product to 150 C., the methane sulfonic acid was neutralized by adding slaked lime, and ii the dimethyl sulfoxide was distille in vacuum) the yield of pure dimethyl sulfoxide was 91% of the theoretical 7 yield. If the foregoing procedure is repeated using sub--; stantially' anhydrous dimethyl sulfide (containing .less than0.1% moisture) a yield of 94%='is obtained; but if f atmospheric air at about 60%. relative humidity -isused with the undried sulfide the yield is only about 75% (and it is now believed that the reason why ,such small amounts of water can produce such a notice 7 able efiectupon the reaction is that the water apparentlyi reacts with the N0 to form acids as indicated in the of commercial grade, the
C. and 35 C. 'in thatorder). Partial' dryingof such' atmospheric air to reduce therelative humidity by about one-half to 30% (at 30 C.)'; results in a'- distinct improvementgin the yield to about 78%,;although this is] much less than the yield obtained'by theusefofsubs'tantially dried air. 1 I I As another demonstratioma single reaction chamber comprising a glass tube 4.3 centimeters in diameter and 50 j centimeters in length is'provided with a gas inlet at the 1 bottom and a gas'distributing plate. ;A charge of 500 grams of dimethyl sulfide was placed .inwtheg chambei'f which was also filled with filling material near the bottom 1' 7 thereof to increase the reaction surface. The upper part of the reaction chamber is provided with a cooler maiutained at minus 10 C. Air containing;12l5% NO (which'is volume percent based on the'oxygen content" of i the air) is fed into the bottom of the chamber. The rate at which oxygen is thus fed into the bottom of the chain-' her is 6-10 liters per hour. 7 As the'reaction progressed the temperature. was raised up to 40-45 9 C. and as the reaction was completed the temperature dropped back to room temperature. Using undried atmospheric air having a relative humidity of about 60% at ,30" C. it was found that the yield obtained was about 80% of theoretical. Using air which has been dried to a re1ative"hu-" midityof about 1% at 30 C. (in the manner hereinbefore; described), the yield obtained is about oftheoretical, 3 If substantially anhydrous dimethyl sulfide is used instead" yield is further increasedsto about 93% of theoretical. 7 H It will be understood that modifications and variations may beeffected without departing from the spirit and, scope of the novel concepts of this invention.
I claim as my invention: 1 1; In a process for the manufacture of a di-lower alkyl' sulfoxide from the corresponding sulfide by oxidation ;v
thereof, which comprises contacting the sulfide with an oxidizing atmosphere containing air and an amount of oxygen transmitting nitrogen oxide at least sufiicient to catalyze the oxidation, the improvement which comprises contacting the sulfide with air having a moisture content below 0.002 pound per pound of air.
2. In a process for the manufacture of a di-lower alkyl sulfoxide from the corresponding sulfide by oxidation thereof, which comprises contacting the sulfide in substantially anhydrous form with an oxidizing atmosphere containing air and an amount of oxygen transmitting nitrogen oxide at least sufiicient to catalyze the oxidation, the improvement which comprises contacting the sulfide with air having a moisture content below 0.002 pound per 6 pound of air.
References Cited in the file of this patent UNITED STATES PATENTS Smedslund Jan. 1, 1952

Claims (1)

1. IN A PROCESS FOR THE MANUFACTURE OF A DI-LOWER ALKYL SULFOXIDE FROM THE CORRESPONDING SULFIDE BY OXIDATION THEREOF, WHICH COMPRISES CONTACTING THE SULFIDE WITH AN OXIDIZING ATMOSPHERE CONTAINING AIR AND AN AMOUNT OF OXYGEN TRANSMITTING NITROGEN OXIDE AT LEAST SUFFICIENT TO CATALYZE THE OXIDATION, THE IMPROVEMENT WHICH COMPRISES CONTACTING THE SULFIDE WITH AIR HAVING A MOISTURE CONTENT BELOW 0.002 POUND PER POUND OF AIR.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3179556A (en) * 1962-01-25 1965-04-20 Stauffer Chemical Co Method of controlling fungi by means of an organic disulfide

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2581050A (en) * 1944-07-18 1952-01-01 Centrallaboratorium Ab Method for the production of dimethyl sulfoxide

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2581050A (en) * 1944-07-18 1952-01-01 Centrallaboratorium Ab Method for the production of dimethyl sulfoxide

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3179556A (en) * 1962-01-25 1965-04-20 Stauffer Chemical Co Method of controlling fungi by means of an organic disulfide

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