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ENT OFFICE 2,439,845 YOROCARBON-SUBSTITUTED THIACY - CLOPENTANE-1,1-Dioxide Rupert C

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ENT OFFICE 2,439,845 YOROCARBON-SUBSTITUTED THIACY - CLOPENTANE-1,1-Dioxide Rupert C 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: HH.-E. 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.
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