Patented Apr. 6, 1948 2439,345 UNITED STATE S PAT ENT OFFICE 2,439,845 YOROCARBON-SUBSTITUTED THIACY - CLOPENTANE-1,1-DioxIDE Rupert C. Morris, Berkeley, Calif., assignor to Shell Development Company, San Francisco, Calif., a corporation of Delaware No Drawing. Application July 13, 1943 . . . Serial No. 494,587 - 4 Claims. (C. 260-329) 1 2 This invention relates to a novel and particu as well as the various derivatives thereof, i.e. larly useful class of compounds. More particu sulfolenes in which various radicals are substi larly, the invention pertains to a certain novel tuted for one or more of the hydrogen atoms of and useful class of substituted cyclic sulfones, the above structures. Specifically, the invention is directed to sul It is an object of the present invention to pro folanes and sulfolenes having at least one sub vide a new class of chemical compounds. A fur stituted or unsubstituted unsaturated hydrocar ther object is to provide a novel class of com bon radical attached to a nuclear carbon atom pounds possessing unexpectedly useful proper Of the Sulfolane or sulfolene ring by means of a ties. Other objects will be apparent from the single carbon-to-carbon linkage. O following description of the present invention. The term 'sulfolene,' as employed herein and Unsubstituted sulfoliane, as well as both unsub in the appended claims, refers to an unsaturated stituted sulfolenes, i. e. 2-sulfolene and 3-sul structure containing four carbon atoms, a single folene, have been known for SOme time. Also, olefin linkage between any two adjoining carbon some substituted solfolanes and Sulfolenes have atoms, and a sulfur atom in a ring, the sulfur is been previously prepared. In all of these com aton of this five-membered heterocyclic un pounds the side chain or chains attached via a Saturated ring having two oxygen atoms attached carbon-to-carbon bond to the ring consisted of thereto. This compound has also been called Saturated aliphatic Or aromatic radicals. Sub "thia cyclopentene-1,1-dioxide.” Similarly, the stituted sulfolanes and sulfolenes containing a term "sulfolane,' as employed herein and in the methylene group directly attached to a nuclear appended claims, refers to a saturated sulfolene. carbon atom by a double bond are also known. In other words, the sulfolane contains or con It has now been discovered that sulfolane and Sists of a saturated five-membered ring of four sulfolene derivatives containing a substituted or carbon atoms and a sulfur atom, which latter has unsubstituted unsaturated hydrocarbon radical two oxygen atoms attached thereto. The gen attached to the ring by a single carbon-to-car eral structural formula of the simple unsubsti bon linkage, surprisingly possess inherent prop tuted sulfolane, therefore, is: erties which render said compounds unexpectedly, and markedly superior to those of the corre-, HC--CH sponding sulfolane or sulfolene derivatives con Hit. H taining an aromatic or saturated aliphatic side S chain, or those containing a methylene group o1 So directly attached to the nucleus by a double bond, These properties could not beforeseen and are of This compound has also been termed "thiacyclo such a nature that they make the compounds of pentane - 11 - dioxide," "thiolane-1,1-dioxide,' the present invention particularly useful in 'Cyclotetramethylene sulfone' or “dihydro buta various applications. diene Sulfone.' Generically, the term 'sulfolane' Broadly, the novel compounds of the present covers not only the above compound, but also invention consist of substituted sulfolanes and the substituted derivatives of this compound. As sulfolenes containing at least one substituted stated, the double bond in the sulfolenes may be and/or unsubstituted, unsaturated hydrocarbon. between any two of the adjacent carbon atoms of radical attached to the sulfolane or sulfolene ring the ring, the generic, term "sulfolene' covering via a single carbon-to-carbon linkage. In the both the simple, unsubstituted sulfolenes, i. e., case of the sulfolane derivatives, the novel com 3-sulfolene having the structure: ponds may be represented by the following gen 5 H.HC-EuCH &H, eral structural formula: N s^ o1 No n- - and 2-sulfolene having the structure: H.-E.H ba, YY a N 55 wherein at least one of the R radicals attached O O to the nuclear carbon atoms is an unsubstituted 2,439,845 3 or substituted, unsaturated hydrocarbon radi tached to the ring, each by means of a single cal attached to the nuclear carbon atom via a carbon-to-carbon linkage. This group may be single carbon-to-carbon linkage, and wherein exemplified by 2,5-divinyl-3-sulfolene which has the other R. radicals are the same or different the following structural formula: substituents comprising the hydrogen atom, a halogen atom, a hydroxyl radical and/or an or CEs-C ganic radical, preferably a hydrocarbon radical, C=C H-bit &H-CH=c such as an alkyl, alkenyl, cyclo-alkyl, cyclo a's2 n alkenyl, aryl, aralkyl or alkaryl group. O O Similarly, in the case of the novel sulfolene O The unsaturated, unsubstituted or substituted derivatives, the general structural formula is sub radicals attached to the sulfolane or sulfolene stantially the same as that presented above, with ring include: the unsaturated hydrocarbon the exception that the sulfolene ring contains at radicals having a single bond for attachment to least one double bond between two adjacent the ring, e. g. vinyl, allyl, propenyl, crotyl, methyl carbon atoms of the ring structure, For instance, s vinyl carbinyl, buttenyl, pentenyl, hexenyl, meth with a double bond in the beta- or 3-position, allyl, isocrotyl, cyclopentenyl, cyclohexenyl, iso the novel sub-class of compounds of the present pentenyl, octenyl, nonenyl, oleyl, cinnamyl and invention is represented by the following general phenyl vinyl carbinyl radicals, as well as the un structural formula: saturated radicals of the type of R-C-C-R CH=CH-CH=CH-CH R R N / C-C-C-C-CE R^ C Yr ch, o? So ch,--CH-CH-CH-i-CH-CHCE bH, wherein at least one of the R radicals is an un CI-CII substituted or substituted, unsaturated hydro / carbon radical attached to a nuclear carbon atom cy CH-CH by a single carbon-to-carbon linkage, while the 30 C=CH remaining R radicals are the same or different substituents of the character described above with the halo-substituted derivatives of the above and reference to the corresponding novel sub-class other similar unsaturated hydrocarbon radicals, of substituted Sulfolane derivatives. such as 2-chlor-allyl, 3-chlor-allyl, 2-brom-allyl, A preferred sub-group of novel compounds 35 2-bromcrotyl, 2-chlor-crotyl, and the like; the comprises the Sulfolanes and sulfolenes in which oxygenated derivatives of the above class of un a single unsubstituted or substituted, unsaturated saturated hydrocarbon radicals, i. e. their alde hydrocarbon radical is attached via a single hydes, alcohols, glycols, ethers, esters, ketones, carbon-to-carbon linkage to the ring at the 2- or and similar Oxygenated derivatives, all of which 3-position, the remaining free bonds of the 40 derivatives have a single bond for the attachment nuclear carbon atoms being taken up by hydro of the radical to the sulfolane or sulfolene ring gen atoms, halogen atoms, hydroxyl radicals via a Carbon-to-carbon connection, the following and/or saturated aliphatic radicals. being examples of such radicals: The numbering system of the sulfolane (thiol 45 -CH=CH-CHOF ane) or sulfolene ring is indicated below: -CBs C-CB-CEI C-C bH ( , -CH=(-CHoH Ys’ 50 bH, This is in accordance with the accepted system -CH-g-CHOH of numbering as exemplified by the compounds of this type of ring structure given on page 44 bu, of Patterson and Capell, The Ring Index, Rein ---CH-C=CH-CHO hold Publishing Corp., New York, 1940; Am. -C=C-CB-COH Chem. Soc. Monograph No. 84. The system may exemplified by the compound having the struc &H re: -C-C-COH C-C-C-C-CB bHon. ba, le, -C-O-CeC Ys -CH=CH-0-CH=CH, of2 SaSo -CH=CH-O-CH-CH which is named 3-allyl sulfolane, and the com -C-O-CH-CH=CH pound C-O-CH-CH=CH CassCB -bH ch–ch-be bH, &H-0-CH-CH=CH, N/ -C-C-O-C-C-CH 1 SaSo O which is called 2-vinyl-3-sulfolene. Another sub group of novel compounds comprises the sulfol anes and Sulfolenes having two or more of the aforementioned unsaturated substituents at 2,439,845 5 6 beta-(2-A-sulfolenyl) divinyl ether, 2-(2-hy -CHCH-O-C-Cis droxyallyl). A -sulfolene, 2-(4-hydroxy-2- butenyl) - A -sulfolene, beta - (3-A- sulfolenyl) O - acrolein, alphae (4-vinyl-2-sulfolanyl) acetalde hyde, vinyl 3-sulfolanyl ketone, isopropenyl -ch-0--0-chi-ch=ch, 3-sulfolanyl ketone, allyl 2,4-dimethyl-3-A-sul -CH=CH-CHO folenyl ketone, allyl beta-(3-sulfolanyl)-ethyl -CH-CH=CH-CHO amine, diallyl beta-(3-sulfolanyl)-ethyl amine, -CH=CH-CH-CHO N-beta-(3-sulfolanyl)-ethyl acrylamide, N-allyl O 3-sulfolanylcarboxamide, N,N-diallyl 3-sulfol -CH-CH=C-CHO anyl-carboxanide, 3-allyl-4-sulfolany p-toluene &n, sulfonate, and the like. w The novel compounds of the present invention may be produced in a number of various ways 5 depending in part on the specific starting mate and the like, and their homologues and analogues; rial or materials employed and/or on the desired unsaturated organic compounds containing a novel Compound sought to be formed. For, in sulfur atom (such as the unsaturated thio-ether stance, a 3-sulfolene derivative containing one radicals) and/or a nitrogen atom or atoms, e. g. or more unsaturated acyclic hydrocarbon side radicals or groups of the type of 20 chains may be prepared by reacting a suitable poly-olefinic hydrocarbon containing at least --CH=CH-S-CE: three olefinic linkages, at least two of which are -CH=CH-s-CH-CH. in conjugated position, with sulfur dioxide under Conditions favoring an addition reaction. The -C-C-NE following is a specific example of the application --CH=CH-NH-CH of this procedure to the production of 2-vinyl-3- and the like, and their homologues and analogues; sulfolene. Substantially peroxide-free hexatri as well as combinations thereof, e. g. unsaturated ene (i. e. a hydrocarbon having the general struc amide or sulfonate radicals. In all of these cases, tural formula CH2=CH-CH=CH-CH=CH) is the unsaturated organic radical is attached dil 30 mixed with liquid sulfur dioxide, which is prefer rectly to a carbon atom of the sulfone ring via a ably employed in an amount which is at least single carbon-to-carbon linkage. As mentioned stoichiometrically sufficient to react, mol per above, the novel class of sulfolanes and Sulfolenes mol, with said hexatriene. These reactants are contains at least one such unsaturated organic. then heated to an elevated temperature which is radical, the remaining free bonds of the carbons 35 however below that at which the cyclic mono of the sulfolane or sulfolene ring being satisfied sulfones thus formed will decompose. Gener with the same or different atoms or groups, such ally, this reaction temperature is in the neigh as hydrogen atoms, halogen atoms, hydroxyl borhood of about 100° C. However, somewhat radicals, or organic radicals, which are prefer higher temperatures may also be used as long as ably hydrocarbon radicals, and especially satu 40 they are below the aforementioned decomposi rated acyclic radicals. tion temperature. The reaction is conducted for Excluded from the scope of the invention are a period of time sufficient to effect the desired those compounds wherein the Substituent or sub degree of interaction between the sulfur dioxide stituents attached to the sulfone ring contain no and the poly-olefin, this residence time depend other carbon-to-carbon double bonds except ing on the specific poly-olefin treated, the em those of an aryl, e. g. a phenyl, group. This is ployed mol ratio of sulfur dioxide to the poly because a phenyl group is not considered by those olefin, the operating pressure, and other operat skilled in the art to be an unsaturated radical. ing conditions. Thus, the above hexatriene reacts Thus, a phenyl group does not possess the neces readily with sulfur dioxide when the reaction is sary unsaturation within the meaning of the term 50 effected at the above-mentioned temperature "unsaturated' as used herein, and it is the pres and at a pressure which maintains the reactants ence of the unsaturated group or groups (which in the liquid state, or at least maintains a liquid are in the side chain proper, and not between the phase in the reaction zone (e.g. a pressure of be ring and said chain) which gives the compounds tween about 100 lbs, per sq. in. and about 500 lbs. of the invention their characteristic Superior 55 per sq. in.), particularly when the sulfur dioxide properties as compared to the corresponding or is employed in an amount which is greatly in ex similar substituted sulfolanes or substituted sul Cess of that necessary to combine with the hexa folenes devoid of such unsaturation. It will be triene. On the other hand, acyclic poly-olefins understood, however, that the compounds which containing a tertiary unsaturated carbon atom. possess unsaturated groups in addition to the 60 which carbon atom is one of the two to which the aryl group are not to be construed as excluded sulfur dioxide adds to form the cyclic unsaturated from the scope of the invention, reference being sulfone, require a comparatively considerably made for instance to compounds such as 3-cin longer residence time to attain the same degree namyl sulfoliane, 2(2-phenylallyl) sulfolane, and of conversion. As stated, under the optimum the like. 65 conditions of operation mentioned above (i. e. As examples of particular new compounds in a reaction temperature of about 100° C., a super cluded within the scope of the present invention atmospheric pressure sufficient to maintain the are: 2- vinyl-2-sulfolene, 2- vinyl-3-sulfolene, reactants in the liquid state, and the use of for 2-vinyl sulfolane, 3-vinyl sulfolane, 3-allylsulfol example about 4 mols of liquid sulfur dioxide per ane, 2-(2-chlorallyl)-2-sulfolene, 2,4-divinyl-3- 70 mol of the hexatriene), a substantially quantita sulfolene, 3-methallylsulfolane, 3-vinyl-4-chlor tive conversion to 2-vinyl-3-sulfolene will be at 3-sulfolene, 2-(2-bromallyl) sulfolane, 2-allyl-3- tained by effecting the above reaction between hydroxy sulfolane, 2-(2-hydroxyaly) sulfolane, hexatriene and sulfur dioxide for a period of only 2-cyclopentenyl sulfolane, 2-cyclopentenyl-3- a few minutes, e.g. a residence time of less than sulfolene, allyl ether of 3-methylol sulfolane, one hour, the reaction product containing only 2,439,845 7 8 minor amounts, if any, of by-products of the type Similarly, 2,3-dimethyl-2-bromo-sulfolane may of hydrocarbon polymers and/or poly-sulfones. be reacted with crotylmagnesium bromide to pro The corresponding 2-vinyl-sulfolane may be duce 2,3-dimethyl-2-crotyl-sulfolane. . prepared, for example, by subjecting 2-vinyl-3- The products of the present invention are of sulfolene to the action of hydrogen at substan value in a large variety of industries and as tially atmospheric pressures and temperatures, intermediates in various chemical syntheses. For and in the presence of a suitable hydrogenation instance, at least some of these Compounds are ... catalyst, e. g. pyrophoric nickel metal catalyst, highly useful as plasticizers and tackifiers in nat platinum, or the like, to form 2-ethyl-sulfolane, ural and synthetic compositions, while some of this latter being then catalytically dehydrogen O the same and other compounds of the novel class ated to produce the desired 2-vinyl-sulfolane. are of value in the resin and lacquer industry Care should be taken to conduct the last-men as solvents and plasticizers for the manufacture tioned dehydrogenation reaction under such con of dopes, fabric coatings, sprays and moulding ditions and for such a period of time that dehy compositions. Other uses are as insecticides, an drogenation occurs only in the side-chain (and 15 tioxidants, pourpoint depressants, extracting even this only to the desired degree) and that agents, ingredients in cosmetics, as base mate there is no or substantially no dehydrogenation rials and fixing agents in the preparation of per of the sulfolane ring proper. fumes, as softening agents for the leather indus Another method of producing sulfolanes con try, and as selective solvents in extractive dis ... taining an unsaturated hydrocarbon radical at 20 tillation processes. tached to the ring via a single carbon-to-carbon I claim as my invention: linkage comprises a reaction between a poly-ole 1. 2-Vinyl-sulfoliane having the general struc finic ester, e. g. a poly-olefinic acetate, and Sul tural formula, fur dioxide to form the corresponding substituted sulfolene, this latter being then hydrogenated CH-CH and the reaction product thus produced being 25 then treated, e. g. by heating to a suitable tem chi-ch-r S B. perature to split of acetic acid. For instance, 2 Sa hexadiene acetate may be reacted with sulfur O O dioxide under the above-Outlined conditions 30 2. A hydrocarbon-substituted thiacyclopen which favor the formation of the following sub tane-1,1-dioxide containing as the sole substitu stituted sulfolene derivative: ent an alkenyl radical attached to a nuclear car CaC bon atom of the thiacyclopentane-1,1-dioxide bH, &H-CH-OH,-o-c-CH, ring via a single carbon-to-carbon linkage. N/ 3. A hydrocarbon-substituted thiacyclopen a'a O tane-1,1-dioxide containing as the sole substitu o1 nO ent an alkenyl radical of not more than four This compound may then be subjected to hydro carbon atoms attached directly to a nuclear car genation, for example, by reacting it with hydro bon atom of the thiacyclopentane-1,1-dioxidering gen under substantially atmospheric pressure and 40 via a single carbon-to-carbon linkage. in the presence of a hydrogenation catalyst, such 4. A hydrocarbon-substituted thiacyclopen as pyrophoric nickel, to saturate the double bond tane-1,1-dioxide having an unsubstituted unsat in the sulfone ring. When this saturated con urated hydrocarbon radical, which radical is di pound is then heated, for instance to a temper rectly attached to a nuclear carbon atom of the ature of from about 200° C. to about 500 C, 45 thiacyclopentane-1,1-dioxide ring via a single acetic acid is split off, thus producing 2-vinyl carbon-to-carbon linkage, said unsaturated hy sulfolane, drocarbon radical containing at least one unsatu Still another method of producing the novel rated linkage between two carbon atoms of all compounds of this invention includes the step of phatic character. interacting a sulfolane or sulfolene derivative 50 RUPERT C. MORRIS. having an active substituent, e. g. a halogen atom, directly attached to a ring carbon atom, with a REFERENCEs CITED Grignard reagent which contains an unsaturated The following references are of record in the hydrocarbon, e. g. alkenyl, radical. For exam file of this patent: ple, 2,4-dimethyl-3-chloro-A*-sulfolene may be 55 Backer, Recueil Des Travaux Chimiques Des formreacted 2,4-dimethyl-3-methallyl-A*-sulfolene. with methallylmagnesium chloride to Pays-Bas, vol. 58 (1939), pages 778-784.