US 2002O161255A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2002/0161255A1 Ishii et al. (43) Pub. Date: Oct. 31, 2002

(54) PROCESS FOR PREPARING ORGANIC (52) U.S. Cl...... 558/40; 562/95 SULFURACDS OR SALTS THEREOF (76) Inventors: Yasutaka Ishii, Takatsuki-shi (JP); Tatsuya Nakano, Hyogo (JP) (57) ABSTRACT Correspondence Address: BRCH STEWART KOLASCH & BRCH A process for producing organic Sulfur acid or a Salt thereof PO BOX 747 of the present invention allows an organic Substrate to react FALLS CHURCH, VA 22040-0747 (US) with a Sulfur oxide in the presence of a metallic compound catalyst and in the absence of N-hydroxy and N-oxo cyclic (21) Appl. No.: 09/959,648 imide compounds and thereby yields a corresponding organic Sulfur acid or a Salt thereof. Such organic Substrates (22) PCT Filed: Feb. 27, 2001 include, for example, (a) homocyclic or heterocyclic com pounds having a methylene group, (b) compounds having a (86) PCT No.: PCT/JP01/01462 methine carbon atom, (c) compounds having a methyl group (30) Foreign Application Priority Data or methylene group at the adjacent position to an unsaturated bond, (d) non-aromatic heterocyclic compounds having a Mar. 2, 2000 (JP)...... O58055/2000 carbon-hydrogen bond at the adjacent position to a hetero atom, and (e) straight-chain alkanes. The Sulfur oxide Publication Classification includes, for example, Sulfur dioxide. This production pro ceSS can efficiently produce an organic Sulfur acid or a Salt (51) Int. Cl." ...... C07C 35/02; CO7C 33/04 thereof under mild conditions. US 2002/0161255 A1 Oct. 31, 2002

PROCESS FOR PREPARING ORGANIC SULFUR aromatic heterocyclic compounds each having a carbon ACDS OR SALTS THEREOF hydrogen bond at the adjacent position to a hetero atom, and (e) straight-chain alkanes. TECHNICAL FIELD 0008. The term “N-hydroxy and N-oxo cyclic imide 0001. The present invention relates to a process for compounds’ Specifically means compounds represented by producing organic Sulfur acids or Salts thereof which are following Formula (1): useful, for example, as materials for pharmaceuticals, agro chemicals and dyes or as detergents. (1) BACKGROUND ART --R C 0002) A variety of processes are known for producing f \,... organic Sulfur acids or Salts thereof. For example, Such NX processes for producing a Sulfonic acid include a process of * / oxidizing a thiol or disulfide with an oxidizing agent, a --R2 process of allowing an aromatic hydrocarbon to react with O anhydrous SO-pyridine or chlorosulfuric acid by the use of a Friedel-Crafts reaction, and a process of Synthetically obtaining a Sulfonic acid by Subjecting an unsaturated com 0009 wherein R and Rare the same or different and are pound to free-radical addition. These processes, however, each a hydrogen atom, a halogen atom, an alkyl group, an require extreme reaction conditions or inevitably produce aryl group, a cycloalkyl group, a hydroxyl group, an alkoxy large amounts of by-products. Separately, few processes for group, a carboxyl group, an alkoxycarbonyl group or an acyl directly and efficiently Sulfonating non-aromatic hydrocar group, where R' and R may be combined to form a double bons have been known. bond or an aromatic or non-aromatic ring, X is an oxygen 0003. The Chemical Society of Japan, Spring Conference atom or a hydroxyl group, where one or two of N-Substituted Proceedings (1999) reports on a sulfonation reaction of a cyclic imido group indicated in the formula (1) may be hydrocarbon with Sulfur dioxide and oxygen by catalysis of further bonded to the aforementioned R, R or to the double N-hydroxyphthalimide. This process can yield a correspond bond or aromatic or non-aromatic ring formed together by ing Sulfonic acid from a hydrocarbon Such as adamantane R and R°. through one step. However, demands have been made on a proceSS for further efficiently producing Sulfonic acids and BEST MODE FOR CARRYING OUT THE other organic Sulfur acids or Salts thereof at a lower cost. INVENTION 0010 Organic Substrate DISCLOSURE OF INVENTION 0011. The Substrates for use in the invention are not 0004. Accordingly, an object of the present invention is to Specifically limited and include a wide variety of Saturated provide a proceSS for efficiently producing an organic Sulfur or unsaturated compounds. Such compounds include, but are acid or a Salt thereof under mild conditions. not limited to, hydrocarbons (aliphatic hydrocarbons, alicy 0005 Another object of the present invention is to pro clic hydrocarbons and aromatic hydrocarbons), heterocyclic vide a proceSS for directly and efficiently producing a compounds, alcohols, ethers, esters, ketones and aldehydes. corresponding Sulfur acid or a Salt thereof from a non Each of these Substrates can be used alone or in combina aromatic hydrocarbon. tion. 0006 After intensive investigations to achieve the above 0012 Preferred substrates include, but are not limited to, objects, the present inventors have found that, by using a (a) homocyclic or heterocyclic compounds each having a metallic compound as a catalyst, a corresponding organic methylene group, (b) compounds each having a methine sulfur acid or a salt thereof can efficiently be obtained from carbon atom, (c) compounds each having a methyl group or an organic Substrate and a Sulfur oxide even in the absence a methylene group at the adjacent position to an unsaturated of N-hydroxy and N-oxo cyclic imide compounds. The bond, (d) non-aromatic heterocyclic compounds each having present invention has been accomplished based on these a carbon-hydrogen bond at the adjacent position to a hetero findings. atom, and (e) Straight-chain alkanes. In these compounds, a Sulfur acid group Such as a Sulfonic acid group or Sulfinic 0007 Specifically, the present invention provides a pro acid group is introduced into the methylene group, methine ceSS for producing an organic Sulfur acid or a Salt thereof. carbon atom, methyl group or methylene group, carbon atom The proceSS includes the Step of allowing an organic Sub at the adjacent position to the hetero atom, and carbon atom Strate to react with a Sulfur oxide in the presence of a constituting the Straight-chain alkane, respectively. metallic compound catalyst and in the absence of N-hydroxy and N-oxo cyclic imide compounds to thereby yield a 0013) Of the compounds (a), homocyclic compounds (a1) corresponding organic Sulfur acid or a Salt thereof. The having a methylene group include, but are not limited to, Sulfur oxide includes, for example, Sulfur dioxide. Such cycloalkanes (e.g., cyclopropane, cyclobutane, cyclopen organic Substrates include, for example, (a) homocyclic or tane, cyclohexane, methylcyclohexane, 1,2-diethylcyclo heterocyclic compounds each having a methylene group, (b) hexane, isopropylcyclohexane, cycloheptane, cyclooctane, compounds each having a methine carbon atom, (c) com methylcyclooctane, cyclononane, cyclodecane, cyclodode pounds each having a methyl group or methylene group at cane, cyclotridecane, cyclotetradecane, cyclopentadecane, the adjacent position to an unsaturated bond, (d) non cyclohexadecane, cyclooctadecane, cyclononadecane, and US 2002/0161255 A1 Oct. 31, 2002 other Ca-Cao cycloalkanes), cycloalkenes (e.g., cyclopro ing to a junction position when two rings commonly possess pene, cyclobutene, cyclopentene, cyclohexene, 1-methyl-1- two atoms), and a Sulfur acid group is introduced into the cyclohexene, cycloheptene, cyclooctene, cyclononene, methine carbon atom. cyclodecene, cyclododecene, and other C-C cycloalk 0018 The non-aromatic cyclic compounds (b3) each enes), cycloalkadienes (e.g., cyclopentadiene, cyclohexadi having a hydrocarbon group bonded to its ring include, for ene, cycloheptadiene, cyclooctadiene, cyclodecadiene, example, 1-methylcyclopentane, 1-methylcyclohexane, cyclododecadiene, and other Cs-Co cycloalkadienes), limonene, menthene, menthol, carvomenthone, menthone, cycloalkatrienes, cycloalkatetraenes, and condensed polycy and other alicyclic hydrocarbons each having from about 3 clic aromatic hydrocarbons each having a 5-to 8-membered to about 15 members and having a hydrocarbon group (e.g., non-aromatic ring condensed there with. an alkyl group) each having from about 1 to about 20 (preferably from about 1 to about 10) carbon atoms and 0014) Of the compounds (a), heterocyclic compounds being bonded to its ring, and derivatives of these com (a2) each having a methylene group include, for example, 5 pounds. In these compounds (b3), a Sulfur acid group is or 6-membered cyclic compounds having a hetero atom introduced into a methine carbon atom at the bonding site Selected from nitrogen, oxygen and Sulfur atoms, or con between the constitutive ring and the hydrocarbon group. densed heterocyclic compounds having an aromatic ring and 0019. The compounds (c) each having a methyl group or a 5- or 6-membered ring having a hetero atom condensed to a methylene group at the adjacent position to an unsaturated the aromatic ring. Examples of Such heterocyclic com bond include (c1) organic compounds each having a methyl pounds (a2) are dihydrofuran, tetrahydrofuran, pyran, dihy group or a methylene group at the adjacent position to a dropyran, tetrahydropyran, piperidine, piperazine, pyrroli non-aromatic carbon-carbon double bond and/or triple bond, dine and Xanthene. In the compounds (a), a Sulfur acid group (c2) compounds each having a methyl group or a methylene is introduced into the methylene group constituting a non group at the adjacent position to an aromatic ring, and (c3) aromatic ring. compounds each having a methyl group or a methylene 0.015 The compounds (b) each having a methine carbon group at the adjacent position to a carbonyl group. atom (a methylidyne group) include, for example, (b1) chain 0020. The compounds (c1) include, but are not limited to, hydrocarbons each having a tertiary carbon atom, (b2) unsaturated chain hydrocarbons each having from about 3 to bridged cyclic compounds and (b3) non-aromatic cyclic about 12 carbon atoms, Such as propylene, 1-butene, compounds each having a hydrocarbon group bonded to its 2-butene, butadiene, 1-pentene, 2-pentene, isoprene, 1-hex ring. ene, 2-hexene, 1,5-hexadiene, 2,3-dimethyl-2-butene, 0016. The chain hydrocarbons (b1) each having a tertiary 3-hexene, 1-heptene, 2-heptene, 1,6-heptadiene, 1-octene, carbon atom include, but are not limited to, isobutane, 2-octene, 3-octene, 1,7-Octadiene, 2,6-Octadiene, 2-methyl isopentane, isohexane, 3-methylpentane, 2,3-dimethylbu 2-butene, 1-nonene, 2-nonene, decene, decadiene, dodecene, tane, 2-methylhexane, 3-methylhexane, 2,3-dimethylpen dodecadiene, dodecatriene, undecene, undecadiene and tane, 2,4-dimethylpentane, 2,3,4-trimethylpentane, 3-ethyl undecatriene. In these compounds (c1), a Sulfur acid group pentane, 2,3-dimethylhexane, 2,4-dimethylhexane, 3,4- is introduced into, for example, a carbon atom at an allylic dimethylhexane, 2,5-dimethylhexane, 2-propylhexane, position. 2-methylheptane, 4-methylheptane, 2-ethylheptane, 3-ethyl 0021. The compounds (c2) include, but are not limited to, heptane, 2,6-dimethylheptane, 2-methyloctane, 3-methyloc aromatic hydrocarbons each having an alkyl group (e.g., tane, 2,7-dimethyloctane, 2-methylnonane, and other ali toluene, Xylene, mesitylene, durene, ethylbenzene, propyl phatic hydrocarbons each having from about 4 to about 20 benzene, cumene, methylethylbenzene, methylnaphthalene, (preferably from about 4 to about 10) carbon atoms. In the dimethylnaphthalene, methylanthracene, dimethylan compounds (b1), a Sulfur acid radical is introduced into the thracene, trimethylanthracene, dibenzyl, diphenylmethane tertiary carbon atom. and triphenylethane); and heterocyclic compounds each having an alkyl group e.g., methylfuran, methylchroman, 0017. The bridged cyclic compounds (b2) include, but methylpyridine (picoline), dimethylpyridine (lutidine), tri are not limited to, decalin, bicyclo2.2.0 hexane, bicyclo methylpyridine (collidine), ethylpyridine, methylguinoline, 2.2.2]octane, bicyclo3.2.1]octane, bicyclo4.3.2unde methylindole, indan, indene, tetralin and fluorene. In these cane, thujone, carane, pinane, pinene, bornane, bornylene, compounds (c2), a Sulfur acid group is introduced into a norbornane, norbornene, camphor, camphoric acid, cam phene, tricyclene, tricyclo[4.3.1.1°undecane, tricyclo So-called benzylic position. 5.2.1.0 decane, exotricyclo[5.2.1.0° decane, endotricy 0022. The compounds (c3) include, for example, alde cloS.2.1.0°-decane, endotricyclo5.2.2.0°undecane, hydes, ketones, carboxylic acids and derivatives thereof. adamantane, 1-adamantanol, 1-chloroadamantane, 1-methy Such aldehydes include, but are not limited to, aliphatic ladamantane, 1,3-dimethyladamantane, 1-methoxyadaman aldehydes (e.g., acetaldehyde, propionaldehyde, butyralde tane, 1-carboxyadamantane, 1-methoxycarbonyladaman hyde, isobutyraldehyde, pentyl aldehyde, hexyl aldehyde, tane, 1-nitroadamantane, 2-adamantanone, tetracyclo heptyl aldehyde, octyl aldehyde, nonyl aldehyde, decyl 4.4.0.1° 17'dodecane, perhydroanthracene, aldehyde, and other C-C alkyl monoaldehydes, malonal perhydroacenaphthene, perhydrophenanthrene, perhydro dehyde, Succinaldehyde, adipaldehyde, Sebacaldehyde, and phenalene, perhydroindene, quinuclidine, and other bicyclic, other aliphatic polyaldehydes), alicyclic aldehydes (e.g., tricyclic or tetracyclic bridged hydrocarbons or bridged formylcyclohexane and cycloneral), and heterocyclic alde heterocyclic compounds and derivatives of these com hydes. pounds. These bridged cyclic compounds (b2) each have a 0023 The ketones include, but are not limited to, ali methine carbon atom at a bridgehead position (correspond phatic ketones (e.g., acetone, methyl ethyl ketone, methyl US 2002/0161255 A1 Oct. 31, 2002 isopropyl ketone, methyl isobutyl ketone, methyl t-butyl yield a corresponding Sulfonic acid in a high yield. The ketone, 2-pentanone, 3-pentanone, 2-hexanone, 3-hexanone, oxygen may be either pure oxygen or oxygen diluted with an 2-heptanone, 3-heptanone, 4-heptanone, 2-octanone, 3-oc inert gas Such as carbon dioxide, nitrogen, helium or argon tanone, 4-octanone, 2-nonanone and 2-decanone), cyclic gas. The oxygen Source can also be air. AS Sulfur trioxide, ketones (e.g., cyclopentanone, cyclohexanone, methylcyclo fuming Sulfuric acid containing Sulfur trioxide can be hexanone, dimethylcyclohexanone, cycloheptanone, iso employed. phorone, cyclooctanone, cyclononanone, cyclodecanone, cyclohexadione, cyclooctadione, and other non-aromatic 0030 The amount of the sulfur oxide can be selected cyclic mono- or poly-ketones, and C-tetralone, B-tetralone, according to the amount of Sulfur acid groups (e.g., Sulfonic indanone, and other cyclic ketones each having an aromatic acid groups or Sulfinic acid groups) introduced into the ring), bridged cyclic ketones (e.g., adamantanone, methy organic Substrate, and is, for example, from about 1 to about ladamantanone and dimethyladamantanone), aromatic 50 moles, and preferably from about 1.5 to about 30 moles ketones (e.g., acetophenone and propiophenone) and hetero relative to 1 mole of the Substrate. The reaction can be cyclic ketones (e.g., inden-1-one, and fluoren-9-one) The performed in an atmosphere of the Sulfur oxide in large carboxylic acids and derivatives thereof include, for excess. When the Sulfur oxide such as sulfur dioxide (SO) example, aliphatic dicarboxylic acids and derivatives thereof is used in combination with oxygen, the molar ratio of the (e.g., malonic acid and its esters, Succinic acid and its esters, Sulfur oxide to oxygen is Such that the former/the latter is glutaric acid and its esters). In the compounds (c3), a Sulfur from about 1/99 to about 99/1, and preferably from about acid group is introduced into, for example, a So-called active 10/90 to about 90/10, and more preferably from about 20/80 methylene group or methyl group. to about 80/20. 0024. In the non-aromatic heterocyclic compounds (d) 0031 Catalyst each having a carbon-hydrogen bond at the adjacent position 0032. According to the process of the present invention, to a hetero atom, non-aromatic heterocyclic rings include, a metallic compound is used as a catalyst. Each of Such but are not limited to, 3- to 20-membered (preferably 5- to metallic compounds can be used alone or in combination. 12-membered, and more preferably 5- or 6-membered) 0033 Metallic elements for constituting the metallic heterocyclic rings each having at least one hetero atom compounds are not specifically limited and can be any of Selected from nitrogen, oxygen and Sulfur atoms. To each of metallic elements of the Groups 1 to 15 of the Periodic Table the heterocyclic rings, one or more benzene rings, cyclo of Elements. The term “metallic element” as used herein hexane rings, pyridine rings or other aromatic or non also includes boron, B. Examples of the metallic elements aromatic rings may be condensed. Examples of the hetero include, of the Periodic Table of Elements, Group 1 elements cyclic rings include dihydrofuran, tetrahydrofuran, pyran, (e.g., Li, Na and K), Group 2 elements (e.g., Mg, Ca,Sr and dihydropyran, tetrahydropyran, pyrrolidine, piperidine, pip Ba), Groups 3 elements (e.g., Sc, lanthanoid elements and erazine, morpholine, indoline, chroman and isochroman. actinoid elements), Group 4 elements (e.g., Ti, Zr and Hf), 0025 The straight-chain alkanes (e) include, but are not Group 5 elements (e.g., V), Group 6 elements (e.g., Cr, Mo limited to, methane, ethane, propane, butane, pentane, heX and W), Group 7 elements (e.g., Mn), Group 8 elements ane, heptane, octane, nonane, decane, dodecane, tetrade (e.g., Fe and Ru), Group 9 elements (e.g., Co and Rh), Group cane, hexadecane, and other Straight-chain alkanes each 10 elements (e.g., Ni, Pd and Pt), Group 11 elements (e.g., having from about 1 to about 30 carbon atoms, and prefer Cu), Group 12 elements (e.g., Zn), Groups 13 elements (e.g., ably from about 1 to about 20 carbon atoms. B, Al and In), Group 14 elements (e.g., Sn and Pb) and Group 15 elements (e.g., Sb and Bi). Preferred metallic 0026. These substrates may have an appropriate func elements include transition metal elements (elements of tional group Substituted thereto. Such functional groups Groups 3 to 12 of the Periodic Table of Elements). Among include, for example, halogen atoms, alkyl groups, alkenyl them, elements of the Groups 5 to 11 of the Periodic Table groups, alkynyl groups, cycloalkyl groups, aryl groups, of Elements are more preferred, of which Vanadium and aralkyl groups, acyl groups, hydroxyl group, alkoxy groups, other Group 5 elements are typically preferred. The Valences acyloxy groups, mercapto group, carboxyl group, alkoxy of the metallic elements are not specifically limited and may carbonyl groups, amino group, N-Substituted amino groups, be about 1 to 6, and are from about 3 to about 5 in many carbamoyl group, N-Substituted carbamoyl groups, nitro group, cyano group, Sulfonyl group, Sulfinyl group, phos CSCS. phino group, heterocyclic groups and OXO group. 0034. The metallic compounds include, but are not lim ited to, elementary Substances, hydroxides, oxides (includ 0027 Sulfur Oxide and Oxygen ing complex oxides), halides (fluorides, chlorides, bromides 0028. The Sulfur oxides can be shown by the formula: and iodides), Salts of oxoacids (e.g., nitrates, Sulfates, phos SO, wherein X is an integer of 1 or 2; and y is an integer of phates, borates, and carbonates), oxoacids, isopolyacids, 1 to 7. In the compounds of the formula, y is usually an heteropolyacids, and other inorganic compounds of the aforementioned metallic elements, Salts of organic acids integer of 1 to 4 when X is 1, and y is generally 3 or 7 when (e.g., Salts of acetic acid, propionic acid, hydrocyanic acid, X is 2. naphthenic acid and Stearic acid), complexes, and other 0029 Such sulfur oxides include, but are not limited to, organic compounds of the metallic elements. Ligands for SO, S.O., SO, SO, SO, and SO. Each of these sulfur constituting the complexes include OH (hydroxo), alkoxy oxides can be used alone or in combination. A preferred (e.g., methoxy, ethoxy, propoxy, and butoxy), acyl (e.g., sulfur oxide includes Sulfur dioxide (SO). The sulfur oxide acetyl and propionyl), alkoxycarbonyl (e.g., methoxycarbo can be used in combination with oxygen. For example, the nyl and ethoxycarbonyl), acetylacetonato, cyclopentadienyl combination use of Sulfur dioxide (SO) with oxygen can group, halogen atoms (e.g., chlorine and bromine), CO, CN, US 2002/0161255 A1 Oct. 31, 2002

oxygen atom, H2O (aquo), phosphines (e.g., triphenylphos each having from about 6 to about 14 carbon atoms. Sub phine and other triarylphosphines), and other phosphorus Stituents which the hydrocarbon groups may have include, compounds, NH (ammine), NO, NO (nitro), NO (nitrato), but are not limited to, halogen atoms, OXO group, hydroxyl ethylenediamine, diethylenetriamine, pyridine, phenanthro group, Substituted oxy groups (e.g., alkoxy groups, aryloxy line, and other nitrogen-containing compounds. groups and acyloxy groups), carboxyl group, Substituted 0035. By taking cobalt compounds as example, examples oxycarbonyl groups, Substituted or unsubstituted carbamoyl of the metallic compounds include cobalt hydroxide, cobalt groups, cyano group, nitro group, Substituted or unsubsti oxide, cobalt chloride, cobalt bromide, cobalt nitrate, cobalt tuted amino groups, alkyl groups (e.g., methyl, ethyl, and Sulfate, cobalt phosphate, and other inorganic compounds, other C-C alkyl groups), cycloalkyl groups, aryl groups cobalt acetate, cobalt naphthenate, cobalt Stearate, and other (e.g., phenyl and naphthyl groups), and heterocyclic groups. Salts of organic acids, acetylacetonatocobalt and other com The preferred hydrocarbon groups include, for example, plexes, and other divalent or trivalent cobalt compounds. alkyl groups each having from about 1 to about 30 carbon Illustrative Vanadium compounds include Vanadium hydrox atoms, and aromatic hydrocarbon groups (especially, phenyl ide, Vanadium oxide, Vanadium chloride, Vanadyl chloride, or naphthyl group) each having from about 6 to about 14 Vanadium Sulfate, Vanadyl Sulfate, Sodium Vanadate, ammo carbon atoms. The aforementioned Substituted oxy groups nium phosphomolybfovanadate, and other inorganic com include, but are not limited to, alkoxy groups, aryloxy pounds; acetylacetonatovanadium e.g., V(acac), vanadyl groups and aralkyloxy groups. acetylacetonato e.g., VO(acac), vanadyl Stearate 0040 Typical examples of the organic salts include IVO(C-HCOO)), Vanadyl isopropoxide organic ammonium Salts, organic phosphonium Salts, IVO(OCH(CH))3), and other organic vanadium com organic Sulfonium Salts, and other organic onium Salts. pounds (including complexes) each having a valence of 2 to Examples of the organic ammonium Salts include tetram 5. Examples of compounds of the other metallic elements ethylammonium chloride, tetraethylammonium chloride, include compounds corresponding to the above-mentioned tetrabutylammonium chloride, tetrahexylammonium chlo cobalt or Vanadium compounds. Among them, Vanadium ride, trioctylmethylammonium chloride, triethylphenylam compounds are typically preferred as the metallic com monium chloride, tributyl(hexadecyl)ammonium chloride, pounds. di (octadecyl) dimethylammonium chloride, and other qua 0.036 The proportion of the metallic compound is, for ternary ammonium chlorides, and corresponding quaternary example, from about 0.0001 to about 0.7 mole, preferably ammonium bromides, and other quaternary ammonium Salts from about 0.001 to about 0.5 mole, and more preferably each having four hydrocarbon groups bonded to its nitrogen from about 0.0015 to about 0.1 mole relative to 1 mole of the atom; dimethylpiperidinium chloride, hexadecylpyridinium Substrate. The metallic compound is often used in a propor chloride, methylguinolinium chloride, and other cyclic qua tion of from about 0.0015 to about 0.05 mole relative to 1 ternary ammonium Salts. Examples of the organic phospho mole of the Substrate. nium Salts include tetramethylphosphonium chloride, tet rabutylphosphonium chloride, 0037 To improve the rate and/or selectivity of the reac tributyl(hexadecyl)phosphonium chloride, triethylphe tion, a promoter (co-catalyst) can be used in combination nylphosphonium chloride, and other quaternary phospho with the metallic compound, according to necessity, in the nium chlorides, and corresponding quaternary phosphonium process of the present invention. Such promoters include, bromides, and other quaternary phosphonium Salts each but are not limited to, organic Salts each comprising a having four hydrocarbon groups bonded to its phosphorus polyatomic cation or a polyatomic anion and its counterion, atom. Examples of the organic Sulfonium Salts include which polyatomic cation or anion contains a Group 15 or triethylsulfonium iodide, ethyldiphenylsulfonium iodide, Group 16 element of the Periodic Table of Elements having and other Sulfonium Salts each having three hydrocarbon at least one organic group bonded thereto. Each of these groupS bonded to its Sulfur atom. promoters can be used alone or in combination. 0041. The organic salts also include methanesulfonates, 0.038. In the organic salts, the Group 15 elements of the ethaneSulfonates, octaneSulfonates, dodecaneSulfonates, and Periodic Table of Elements include N, P, AS, Sb and Bi. The other alkyl-Sulfonates (e.g., Co-Cs alkylsulfonates); benze Group 16 elements of the Periodic Table of Elements neSulfonates, p-toluenesulfonates, naphthaleneSulfonates, include, for example, O, S, Se andTe. Preferred elements are decylbenzeneSulfonates, dodecylbenzeneSulfonates, and N, P, AS, Sb and S, of which N, P and S are typically other aryl-sulfonates which may be substituted with an alkyl preferred. group (e.g., Co-Cs) alkyl-arylsulfonates); Sulfonic acid 0039. Organic groups to be bonded to the atoms of the type ion exchange resins (ion exchangers); and phosphonic elements include, for example, hydrocarbon groups which acid type ion exchange resins (ion exchangers). may have a Substituent, and Substituted oxy groups. The hydrocarbon groups include, but are not limited to, methyl, 0042. The amount of the organic salt is, for example, ethyl, propyl, isopropyl, butyl, isobutyl, S-butyl, t-butyl, from about 0.0001 to about 0.7 mole, preferably from about pentyl, hexyl, octyl, decyl, tetradecyl, hexadecyl, octadecyl, 0.001 to about 0.5 mole, more preferably from about 0.002 allyl, and other Straight- or branched-chain aliphatic hydro to about 0.1 mole, and often from about 0.005 to about 0.05 carbon groups (alkyl groups, alkenyl groups and alkynyl mole relative to 1 mole of the Substrate. groups) each having from about 1 to about 30 carbon atoms 0043. In the process of the present invention, the pres (preferably from about 1 to about 20 carbon atoms); cyclo ence of a peroxide such as t-butyl hydroperoxide (TBHP) in pentyl, cyclohexyl, and other alicyclic hydrocarbon groups a reaction System can enhance or promote the reaction and each having from about 3 to about 8 carbon atoms, and thereby Significantly increases the yield of a target com phenyl, naphthyl, and other aromatic hydrocarbon groups pound. The amount of the peroxide is, for example, from US 2002/0161255 A1 Oct. 31, 2002

about 0.0001 to about 0.2 mole, preferably from about 0.001 dyes and as detergents, polymer materials, light-acti to about 0.1 mole, and more preferably from about 0.003 to Vatable acid generators or materials therefor. about 0.05 mole relative to 1 mole of the Substrate. INDUSTRIAL APPLICABILITY 0044) Reaction 0055. The process of the present invention can efficiently 004.5 The reaction can be performed in the presence of, produce an organic Sulfur acid or a Salt thereof by catalysis or in the absence of, a Solvent. Such Solvents include, but are of a Small amount of an easily available catalyst under mild not limited to, benzene and other aromatic hydrocarbons, conditions, without the use of the imide compounds of dichloromethane, chloroform, dichloroethane, dichloroben Formula (1) such as N-hydroxyphthalimide. Additionally, Zene, and other halogenated hydrocarbons, t-butanol, t-amyl the process can directly and efficiently yield a corresponding alcohol, and other alcohols, acetonitrile, benzonitrile, and organic Sulfur acid or a Salt thereof from a non-aromatic other nitriles, acetic acid, propionic acid, and other organic hydrocarbon. acids; formamide, acetamide, dimethylformamide (DMF), dimethylacetamide, and other amides, and mixtures of these EXAMPLES Solvents. 0056. The present invention will now be illustrated in 0046) The process of the present invention is distinguish more detail with reference to Several examples below, which able from conventional equivalents in that Sulfonation and are not intended to limit the Scope of the invention. In the other reactions can Smoothly proceed even under relatively examples, a benzylthiuronium Salt of a produced Sulfonic mild conditions. In addition, the reaction does not require acid was obtained by extracting a reaction mixture with light irradiation and can Smoothly proceed even under dark water, neutralizing the extract with an aqueous Sodium conditions. A reaction temperature can be selected within the hydroxide Solution, adjusting the resulting Solution with range from about 0° C. to about 150 C., preferably from hydrochloric acid to weak acidity, adding an exceSS of an about 10 C. to about 125 C., and more preferably from aqueous benzylisothiourea hydrochloride to the resulting about 15 C. to about 100° C. The reaction can be performed Solution, and recovering the precipitated Solid by filtration. either under atmospheric pressures or under a pressure (under a load), in any of a batch System, a semi-batch System Example 1 and a continuous System. 0057. A mixture of 2 mmol of adamantane, 0.01 mmol of 0047 The reaction can yield an organic sulfur acid such acetylacetonatovanadium IV(acac) and 10 ml of acetic as a Sulfonic acid or Sulfinic acid corresponding to the acid was stirred at 40 C. in an atmosphere of sulfur dioxide Substrate. For example, the combination use of Sulfur diox (SO) (0.5 atm=50.5 kPa) and oxygen (0.5 atm=50.5 kPa) ide and oxygen can produce Sulfonic acid in a good yield. for 2 hours. The resulting reaction mixture was analyzed by The formed organic Sulfur acid can be converted into a high performance liquid chromatography to find that 1-ada corresponding salt thereof (e.g., a thiuronium salt) according mantanesulfonic acid was produced in a yield of 47% to conventional techniques. For example, the Salt can be (selectivity: 94%) with a conversion from adamantane of obtained by reacting the organic Sulfur acid with an alkali 50%. metal hydroxide, alkali metal carbonate, alkali metal hydro Example 2 gencarbonate, alkaline earth metal hydroxide, alkaline earth metal carbonate, amine, thiourea, or isothiourea in an appro 0058. The procedure of Example 1 was repeated, except priate Solvent Such as water. that 0.01 mmol of vanadyl acetylacetonato (VO(acac). 0.048. After the completion of the reaction, reaction prod was used instead of acetylacetonatovanadium IV(acac), ucts can be easily Separated and purified in a conventional and thereby yielded 1-adamantaneSulfonic acid in a yield of manner Such as filtration, concentration, distillation, extrac 42% (selectivity: 98%) with a conversion from adamantane tion, crystallization, recrystallization, column chromatogra of 43%. phy and other Separation and purification means, or any Example 3 combination of these means. 0059. The procedure of Example 1 was repeated, except 0049 Important compounds that can be obtained by the that 0.01 mmol of vanadyl stearate VO(C.H.COO) was process of the present invention include, for example, used instead of acetylacetonatovanadium IV(acac), and thereby yielded 1-adamantanesulfonic acid in a yield of 49% 0050 1-adamantanesulfonic acid; (selectivity: 88%) with a conversion from adamantane of 0051 3,5-dimethyl-1-adamantanesulfonic acid, 56%. 0052 3-carboxy-1-adamantanesulfonic acid, Example 4 0053 3-chloro-1-adamantanesulfonic acid, 0060. The procedure of Example 1 was repeated, except 0054 4-oxo-1-adamantanesulfonic acid, and other that O.O1 mmol of vanadyl isopropoxide 1-adamantaneSulfonic acid derivatives each having a VO(OCH(CH)) was used instead of acetylacetonatova Substituent Such as methyl group, carboxyl group, nadium IV(acac), and thereby yielded 1-adamantane halogen atom or OXO group on an adamantane ring; sulfonic acid in a yield of 29% (selectivity: 78%) with a cyclohexaneSulfonic acid, cyclooctaneSulfonic acid, conversion from adamantane of 37%. and other cycloalkaneSulfonic acids, octaneSulfonic acid, 2,5-dimethylhexaneSulfonic acid, and other Example 5 alkaneSulfonic acids. These compounds are useful as 0061 The procedure of Example 1 was repeated, except raw materials for pharmaceuticals, agrochemicals and that 0.01 mmol of vanadyl chloride (VOCl) was used US 2002/0161255 A1 Oct. 31, 2002 instead of acetylacetonatovanadium IV(acac), and thereby 0073 Spectral Data of 3-Carboxy-1-adamantane yielded 1-adamantanesulfonic acid in a yield of 33% (selec sulfonic Acid tivity: 85%) with a conversion from adamantane of 39%. 0074) 'C-NMR (CDOD) 8: 1800, 58.8, 42.8, 39.6, Example 6 39.2, 38.8, 37.2, 36.2, 30.3 0075) H-NMR (CDOD) 8: 6.24 (br, -SOH), 2.15 0062) The procedure of Example 1 was repeated, except 1.60 (m, 14H) that 0.01 mmol of ammonium phosphomolybdovanadate was used instead of acetylacetonatovanadium IV(acac), 0.076 Spectral Data of Benzylthiuronium Salt (HO) of and thereby yielded 1-adamantaneSulfonic acid in a yield of 3-Carboxy-1-adamantanesulfonic Acid 15% (selectivity: 60%) with a conversion from adamantane 0077 °C-NMR (CDOD) 8: 1806,135.1, 130.1, 130.0, of 25%. 129.4, 56.9, 42.4, 39.4, 39.0, 37.1, 36.3, 36.2, 29.7 0078 H-NMR (CDOD) 8: 743-7.32 (m, 5H), 4.89 (s. Example 7 4H), 4.43 (s, 2H), 2.14-1.67 (m, 14H) 0.063 A mixture of 2 mmol of 1,3-dimethyladamantane, 0079 FT-IR (cm):3061,2819,2664, 1693, 1460, 1202, 0.01 mmol of vanadyl acetylacetonato IVO(acac) and 10 1161, 1036, 701, 625 ml of acetic acid was stirred at 40 C. in an atmosphere of sulfur dioxide (SO) (0.5 atm =50.5 kPa) and oxygen (0.5 Example 10 atm=50.5 kPa) for 5 hours. The resulting reaction mixture was analyzed by high performance liquid chromatography to 0080 A mixture of 2 mmol of 1-chloroadamantane, 0.01 find that 3,5-dimethyl-1-adamantaneSulfonic acid was pro mmol of vanadyl acetylacetonato IVO(acac) and 10 ml of duced in a yield of 50% with a conversion from 1,3- acetic acid was stirred at 40 C. in an atmosphere of Sulfur dimethyladamantane of 54%. dioxide (SO) (0.5 atm=50.5 kPa) and oxygen (0.5 atm=50.5 kPa) for 5 hours. The resulting reaction mixture was ana 0.064 Spectral Data of 3,5-Dimethyl-1-adamantane lyzed by high performance liquid chromatography to find sulfonic Acid that 3-chloro-1-adamantaneSulfonic acid was produced in a 0065 'C-NMR (CDOD) 8:59.8, 52.4,444, 44.3,372, yield of 53% with a conversion from 1-chloroadamantane of 33.1, 32.3 56%. 0.066 H-NMR (CDOD) 8: 5.59 (br, -SOH), 2.16 0081 Spectral Data of 3-Chloro-1-adamantanesulfonic 2.10 (m, 1H), 1.85-1.83 (m, 2H), 1.70-1.50 (m, 4H), 1.50 Acid 1.30 (m, 4H), 1.30-1.10 (m, 2H), 0.83 (s, 6H) 0082) 'C-NMR (CDOD) 8: 68.2, 60.0, 47.3, 36.2, 35.2, 32.9 0067 Spectral Data of Benzylthiuronium Salt of 3,5- Dimethyl-1-adamantaneSulfonic Acid 0083) H-NMR (CDOD) 8: 5.58 (br, -SOH), 2.33 1.60 (m, 14H) 0068 C-NMR (CDOD) 8: 135.9, 130.9, 130.8, 1302, 59.5, 52.4, 44.8, 44.5, 37.4, 37.0, 33.2, 31.7 0084) Spectral Data of Benzylthiuronium Salt of 3-Chloro-1-adamantanesulfonic Acid 0069 H-NMR (CDOD) 8: 743-7.32 (m, 5H), 4.85 (s, 4H), 4.43 (s, 2H), 2.15-2.12 (m, 1H), 1.85-1.84 (m, 2H), 0085 °C-NMR (CDOD) 8: 135.1, 1302,130.1, 129.5, 1.69-1.58 (m, 4H), 1.34 (s, 4H), 1.13 (m, 2H), 0.85 (m, 6H) 68.3, 59.7, 47.7, 42.6, 36.4, 36.2, 35.4, 32.7 0070 FT-IR (cm): 3323,3133,2942,2900, 1455, 1388, 0086) H-NMR (CDOD) 8: 7.40-7.34 (m, 5H), 4.85 (s, 1088, 1041, 708, 692 4H), 4.43 (s, 2H), 2.33-1.63 (m, 14H) 0087 FT-IR (cm) 3088,2910, 1666, 1495, 1334, 1174, EXAMPLE 8 1013, 714, 629 0071. The procedure of Example 7 was repeated, except Example 11 that the reaction was performed at 25 C. for 24 hours, and thereby yielded 3,5-dimethyl-1-adamantanesulfonic acid in 0088. The procedure of Example 10 was repeated, except a yield of 45% with a conversion from 1,3-dimethylada that the reaction was performed in an atmosphere of Sulfur mantane of 50%. dioxide (SO) (0.67 atm=67.7 kPa) and oxygen (0.33 atm= 33.3 kPa), and thereby yielded 3-chloro-1-adamantane Example 9 sulfonic acid in a yield of 75% with a conversion from 1-chloroadamantane of 82%. 0.072 A mixture of 2 mmol of 1-adamantanecarboxylic acid, 0.01 mmol of vanadyl acetylacetonato IVO(acac) 2 Example 12 and 10 ml of acetic acid was stirred at 40 C. in an atmosphere of Sulfur dioxide (SO) (0.5 atm=50.5 kPa) and 0089. A mixture of 2 mmol of 2-oxoadamantane, 0.01 oxygen (0.5 atm=50.5 kPa) for 5 hours. The resulting mmol of vanadyl acetylacetonato IVO(acac) and 10 ml of reaction mixture was analyzed by high performance liquid acetic acid was stirred at 40 C. in an atmosphere of Sulfur chromatography to find that 3-carboxy-1-adamantane dioxide (SO) (0.5 atm=50.5 kPa) and oxygen (0.5 atm=50.5 sulfonic acid was produced in a yield of 65% with a kPa) for 30 hours. The resulting reaction mixture was conversion from 1-adamantanecarboxylic acid of 70%. analyzed by high performance liquid chromatography to find US 2002/0161255 A1 Oct. 31, 2002

that 4-oxo-1-adamantaneSulfonic acid was produced in a Example 15 yield of 20% with a conversion from 2-oxoadamantane of 26%. 0106 The procedure of Example 14 was repeated, except that the reaction was performed for 24 hours, and thereby 0090 Spectral Data of 4-Oxo-1-adamantanesulfonic yielded cyclooctanesulfonic acid in a yield of 62% with a Acid conversion from cyclooctane of 68%. 0091 °C-NMR (CDOD) 8: 106.6, 57.6, 37.4, 34.9, 34.8, 33.3, 28.9, 28.3 Example 16 0092 'H-NMR (CDOD) 8: 6.95 (br, -SOH), 2.50 0107. A mixture of 2 mmol of 2,5-dimethylhexane, 0.01 1.40 (m, 13H) mmol of vanadyl acetylacetonato IVO(acac) and 10 ml of acetic acid was stirred at 60° C. in an atmosphere of Sulfur EXAMPLE 13 dioxide (SO) (0.5 atm=50.5 kPa) and oxygen (0.5 atm=50.5 0093. A mixture of 2 mmol of cyclohexane, 0.01 mmol of kPa) for 24 hours. The resulting reaction mixture was Vanadyl acetylacetonato VO(acac) and 10 ml of acetic analyzed by high performance liquid chromatography to find acid was stirred at 40 C. in an atmosphere of Sulfur dioxide that 2,5-dimethylhexaneSulfonic acid was produced in a (SO) (0.5 atm=50.5 kPa) and oxygen (0.5 atm=50.5 kPa) yield of 6% with a conversion from 2,5-dimethylhexane of for 24 hours. The resulting reaction mixture was analyzed by 18%. high performance liquid chromatography to find that cyclo hexanesulfonic acid was produced in a yield of 36% with a Example 17 conversion from cyclohexane of 46%. 0108. A mixture of 2 mmol of n-octane, 0.01 mmol of 0094) Spectral Data of Benzylthiuronium Salt (HO) of Vanadyl acetylacetonato IVO(acac) and 10 ml of acetic Cyclohexanesulfonic Acid acid was stirred at 60° C. in an atmosphere of sulfur dioxide 0.095 °C-NMR (CDOD) 8: 135.9, 130.9, 130.8, 1302, (SO) (0.67 atm=67.7 kPa) and oxygen (0.33 atm=33.3 kPa) 61.4, 37.0, 29.5, 27.5, 27.4 for 15 hours. The resulting reaction mixture was analyzed by high performance liquid chromatography to find that octane 0096) H-NMR (CDOD) 8: 744-7.30 (m, 5H), 4.88 (s, Sulfonic acid was produced with a conversion from n-octane 4H), 4.43 (s, 2H), 2.65-2.55 (m, 1H), 2.18-2.14 (m, 2H), of 64%. 1.84-1.14 (m, 8H) 0097 FT-IR (cm) 3087,2838, 1669, 1451, 1225, 1044, 0109) Spectral Data of Octanesulfonic Acid 698,526 0110 °C-NMR (CDOD) 8:56.6,540, 53.1, 39.3,37.3, Example 14 29.7, 18.7, 15.5, 13.9, 13.7, 13.2, 11.4, 9.1 0098. A mixture of 2 mmol of cyclooctane, 0.01 mmol of Vanadyl acetylacetonato VO(acac) and 10 ml of acetic acid was stirred at 40 C. in an atmosphere of Sulfur dioxide 1. A process for producing an organic Sulfur acid or a Salt (SO) (0.5 atm=50.5 kPa) and oxygen (0.5 atm=50.5 kPa) thereof, the proceSS comprising the Step of allowing an for 5 hours. The resulting reaction mixture was analyzed by organic Substrate to react with a Sulfur oxide in the presence high performance liquid chromatography to find that of a metallic compound catalyst and in the absence of cyclooctaneSulfonic acid was produced in a yield of 45% N-hydroxy and N-oxo cyclic imide compounds to thereby with a conversion from cyclooctane of 53%. yield a corresponding organic Sulfur acid or a Salt thereof. 0099 Spectral Data of Cyclooctanesulfonic Acid 2. The proceSS for producing an organic Sulfur acid or a Salt thereof according to claim 1, wherein Sulfur dioxide is 01.00 °C-NMR (CDOD) 8: 61.9, 28.8, 28.4, 28.3, 37.6 used as the Sulfur oxide. 01.01 H-NMR (CDOD) 8: 7.45 (br, -SOH), 3.00 3. The proceSS for producing an organic Sulfur acid or a 2.70 (m, 1H), 2.40-1.25 (m, 14H) Salt thereof according to claim 1, wherein the organic Substrate is one Selected from (a) homocyclic or heterocyclic 0102) Spectral Data of Benzylthiuronium Salt of compounds each having a methylene group; (b) compounds Cyclooctanesulfonic Acid each having a methine carbon atom; (c) compounds each 0103) 'C-NMR (CDOD) 8: 136.0, 130.9, 130.8, 1303, having a methyl group or a methylene group at the adjacent 62.0, 37.1, 30.0, 28.4, 28.3, 27.5 position to an unsaturated bond; (d) non-aromatic heterocy clic compounds each having a carbon-hydrogen bond at the 01.04] 'H-NMR (CDOD) 8: 743-7.32 (m, 5H), 4.85 (s, adjacent position to a hetero atom; and (e) Straight-chain 4H), 4.43 (s, 2H), 2.84-2.80 (m, 1H), 2.21-2.17 (m, 2H), alkanes. 1.73-1.54 (m, 12H) 01.05 FT-IR (cm): 3094,2927, 1670, 1454,1188, 1040, 761, 611