CA2019071A1 - Process for the preparation of aromatic sulfonyl chlorides - Google Patents
Process for the preparation of aromatic sulfonyl chloridesInfo
- Publication number
- CA2019071A1 CA2019071A1 CA002019071A CA2019071A CA2019071A1 CA 2019071 A1 CA2019071 A1 CA 2019071A1 CA 002019071 A CA002019071 A CA 002019071A CA 2019071 A CA2019071 A CA 2019071A CA 2019071 A1 CA2019071 A1 CA 2019071A1
- Authority
- CA
- Canada
- Prior art keywords
- acid
- chloride
- mol
- sulfamic acid
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- -1 aromatic sulfonyl chlorides Chemical class 0.000 title claims description 8
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 40
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims abstract description 33
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims abstract description 32
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 125000003118 aryl group Chemical group 0.000 claims abstract description 8
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 6
- 239000000460 chlorine Substances 0.000 claims abstract description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 5
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 5
- 239000011737 fluorine Substances 0.000 claims abstract description 5
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 4
- 125000001072 heteroaryl group Chemical group 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000000203 mixture Substances 0.000 claims description 19
- 239000011541 reaction mixture Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical class ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 230000000875 corresponding effect Effects 0.000 description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 239000005457 ice water Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- FZERHIULMFGESH-UHFFFAOYSA-N N-phenylacetamide Chemical compound CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 4
- 238000006277 sulfonation reaction Methods 0.000 description 4
- SEWNAJIUKSTYOP-UHFFFAOYSA-N 4-chloro-3-nitrobenzenesulfonyl chloride Chemical compound [O-][N+](=O)C1=CC(S(Cl)(=O)=O)=CC=C1Cl SEWNAJIUKSTYOP-UHFFFAOYSA-N 0.000 description 3
- ZLYBFBAHAQEEQQ-UHFFFAOYSA-N 4-chlorobenzenesulfonyl chloride Chemical compound ClC1=CC=C(S(Cl)(=O)=O)C=C1 ZLYBFBAHAQEEQQ-UHFFFAOYSA-N 0.000 description 3
- 101150034459 Parpbp gene Proteins 0.000 description 3
- 150000003457 sulfones Chemical class 0.000 description 3
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 2
- ASSKVPFEZFQQNQ-UHFFFAOYSA-N 2-benzoxazolinone Chemical compound C1=CC=C2OC(O)=NC2=C1 ASSKVPFEZFQQNQ-UHFFFAOYSA-N 0.000 description 2
- PLAZTCDQAHEYBI-UHFFFAOYSA-N 2-nitrotoluene Chemical compound CC1=CC=CC=C1[N+]([O-])=O PLAZTCDQAHEYBI-UHFFFAOYSA-N 0.000 description 2
- LMRKXSDOAFUINK-UHFFFAOYSA-N 3-chlorosulfonylbenzoic acid Chemical compound OC(=O)C1=CC=CC(S(Cl)(=O)=O)=C1 LMRKXSDOAFUINK-UHFFFAOYSA-N 0.000 description 2
- MWWNNNAOGWPTQY-UHFFFAOYSA-N 3-nitrobenzenesulfonyl chloride Chemical compound [O-][N+](=O)C1=CC=CC(S(Cl)(=O)=O)=C1 MWWNNNAOGWPTQY-UHFFFAOYSA-N 0.000 description 2
- GRDXCFKBQWDAJH-UHFFFAOYSA-N 4-acetamidobenzenesulfonyl chloride Chemical compound CC(=O)NC1=CC=C(S(Cl)(=O)=O)C=C1 GRDXCFKBQWDAJH-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229960001413 acetanilide Drugs 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- BCXWMIMRDMIJGL-UHFFFAOYSA-N naphthalene-1,5-disulfonyl chloride Chemical compound C1=CC=C2C(S(=O)(=O)Cl)=CC=CC2=C1S(Cl)(=O)=O BCXWMIMRDMIJGL-UHFFFAOYSA-N 0.000 description 2
- OGNVQLDIPUXYDH-ZPKKHLQPSA-N (2R,3R,4S)-3-(2-methylpropanoylamino)-4-(4-phenyltriazol-1-yl)-2-[(1R,2R)-1,2,3-trihydroxypropyl]-3,4-dihydro-2H-pyran-6-carboxylic acid Chemical compound CC(C)C(=O)N[C@H]1[C@H]([C@H](O)[C@H](O)CO)OC(C(O)=O)=C[C@@H]1N1N=NC(C=2C=CC=CC=2)=C1 OGNVQLDIPUXYDH-ZPKKHLQPSA-N 0.000 description 1
- JLWMMYZWEHHTFF-UHFFFAOYSA-N 2-[6-(3-carbamimidoylphenoxy)-4-[di(propan-2-yl)amino]-3,5-difluoropyridin-2-yl]oxy-5-(2-methylpropylcarbamoyl)benzoic acid Chemical compound OC(=O)C1=CC(C(=O)NCC(C)C)=CC=C1OC1=NC(OC=2C=C(C=CC=2)C(N)=N)=C(F)C(N(C(C)C)C(C)C)=C1F JLWMMYZWEHHTFF-UHFFFAOYSA-N 0.000 description 1
- OQFYBGANSUNUAO-UHFFFAOYSA-N 4-methyl-3-nitrobenzenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1[N+]([O-])=O OQFYBGANSUNUAO-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 1
- PFZNPQMOQYARRF-UHFFFAOYSA-N O=C1C=CC2=NC(S(=O)(=O)Cl)OC2=C1 Chemical compound O=C1C=CC2=NC(S(=O)(=O)Cl)OC2=C1 PFZNPQMOQYARRF-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- ATADHKWKHYVBTJ-UHFFFAOYSA-N hydron;4-[1-hydroxy-2-(methylamino)ethyl]benzene-1,2-diol;chloride Chemical compound Cl.CNCC(O)C1=CC=C(O)C(O)=C1 ATADHKWKHYVBTJ-UHFFFAOYSA-N 0.000 description 1
- DASJFYAPNPUBGG-UHFFFAOYSA-N naphthalene-1-sulfonyl chloride Chemical class C1=CC=C2C(S(=O)(=O)Cl)=CC=CC2=C1 DASJFYAPNPUBGG-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 150000003510 tertiary aliphatic amines Chemical class 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
- C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
- C07D263/58—Benzoxazoles; Hydrogenated benzoxazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
- C07C303/08—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with halogenosulfonic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/22—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof from sulfonic acids, by reactions not involving the formation of sulfo or halosulfonyl groups; from sulfonic halides by reactions not involving the formation of halosulfonyl groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Abstract of the disclosure Process for the preparation of aromatic sulfonyl chlorides A process for the preparation of aromatic sulfonyl chlorides of the formula I
in which R1, R2 and R3 are identical or different and are hydrogen, fluorine, chlorine, bromine or iodine atoms, alkyl(C1-C4), acetamido, nitro or carboxyl groups, or R1 and R2 together form an aromatic or heteroaromatic ring having 5 or 6 ring members, which can be substituted by fluorine, chlorine, bromine or iodine atoms, alkyl(C1-C4), acetamido, nitro or carboxyl groups, by reaction of aromatic compounds of the formula II
in which R1, R2 and R3 are identical or different and are hydrogen, fluorine, chlorine, bromine or iodine atoms, alkyl(C1-C4), acetamido, nitro or carboxyl groups, or R1 and R2 together form an aromatic or heteroaromatic ring having 5 or 6 ring members, which can be substituted by fluorine, chlorine, bromine or iodine atoms, alkyl(C1-C4), acetamido, nitro or carboxyl groups, by reaction of aromatic compounds of the formula II
Description
2 [3 ~
HOECHST AKTIENGESEL~SCHAFT HOE 89/F 187 Dr. M~/rh Description Process for ~he preparation of aromati~ ~ulfon~l chlorides The invention relates to the preparation of aromatic sulfonyl chlorides in a manner known per se by reaction of aromatic compounds with excess chlorosulfonic acid or with chlorosulfonic acid or oleum and thionyl chloride, the reaction being carried out in ~he pres nce of sul famic acid as a catalyst.
It is known that ~he sulfonation and sulfochlorination of aromatic compounds can be umpro~ed by adding so-called sulfone inhibitors to suppress the sulfone formation observed as a secondary reaction [Ullmann's Encyclopedia of Industrial Chemistry, 5th ed., vol. A.3, p. 513].
Examples of such sulfone inhibitors which may be men-tioned are ammonium sulfate, sodi~ carbonate or potas-5ium carbonate [DE 3,501,754], and sodium chloride or ammonium chloride [DE 3,306,597]. A large num~er of other sulfonating agents are mentioned in EP 0,001,275.
It is known from Helv. ChLmica Acta 42, 1653 (1959) that dialkylformamides act as satalysts in th~ preparation of naphthalenesulfonyl chlorides ~rom the corresponding sulfonic acids.
Reference is made in DE 2,g38,744 to ths toxicological problems in the use of dLmethylformami~e in particular, and substitutes, such as, for example, pyridine/ substi-tuted pyridines, tertiary aliphatic amines and quaterna~y ammonium s lts, preferably tertiary amines, are proposed.
The compounds proposed as catalysts or auxiliarie~ for the sulfonation or sulfochlorination of aromatic com-pounds are not satisfactory for industrial use, in particular for reasons of occupational hygiene , and thus 2 ~
capable of Lmprovement .
It has now been found tha~ sulfamic acid is a novel, advantageous auxiliary for the sulfochlorination of aromatic compounds to give the coxresponding arylsulfonyl chlorides.
The invention thus relates to an Lmproved process, with respect to attainable yields and quality, for the prepar-ation of aromatic sulfonyl chlorides of the general formula I
S02Cl in which Rl, R2 and R3 are identical or different and are hydrogen, fluoxine, chlorine, bxom.ine or iodine atoms, alkyl(Cl-C~), acetamido, nitro or carboxyl groups, or Rl and R2 together form an aromatic or heteroaromatic ring having 5 or 6 ring members, which can be substituted by fluorine, chlorine, bromine or iodine atoms, alkyl(Cl-C4), acetamido, nitro or carboxyl groups~ by reaction of aromatic compounds of the general formula II
R1 ~ R3 (II~
R~
in which Rl, R~ and ~3 have the abovementioned meanings, in a manner kno~n per se with chlorosulfo~ic acid in excess or with chlorosulfonic acid or oleum and thionyl chloride, which comprises reacting in the presence of sulfamic acid as a catalyst.
~ J~
The sulfamic acld employed according to the i~vention as a catalytically active auxiliary cannot be classified in any of the known compound classes of auxiliaries or catalysts for the sulfochlorination of aromatic compounds.
The aromatic sulfonyl chlorideæ are prepared rom the aroma~ic compounds by methods known per se, for example by reac~ion of the aromatic compounds of the abovemen-tioned general formula I~ with excess chlorosulfonic acid [cf. WinnacXer-Ruchler, Chemische Technologie ~Chemical Technology), volume 6, 4~h edition~ page 181, Carl-Hauser Verlag ~unich vienna] or chlorosulfonic acid (or oleum) and thionyl chloride [DE 3,302,647].
In this connection, a procedure is expediently used in which the su:Lfamic acid i8 partially or completely added to the chlorosulfonic acid and, in the case of only partial addition at the beginning of the reaction, further sulfamic acid is metere~ in during the reaction However, it is also possible to convert the aromatic startin~ compound into the aromatic sulfonic acid first using chlorosulfonic acid or oleum~ to add the sulfamic acid to the raaction mixture produced in this ca~e and then to react further to give the arylsulfonyl chloride with thionyl chloride.
The sulfamic acid is expediently added in an amount of abou~ 0.1 to about 20 ~ by weight, preferably about 0.5 to about 5 % by weight, relative to ~he aromatic compound of said general formula (II), to the chlorosulfonic acid, whirh is used in excess ~when working without thionyl chloride)~ or after completion of the sulfonation in the firs~ step and before addition of the thionyl chloride in the second step. Addition of sulfamic acid in larger amounts is admittedly possible, but possesses no advantages.
2 ~
~ 4 --As far as the temperatures are concerned, thos~ in the known ~ulfochlorination of aromatic compounds with an excess of chlorosulfonic acid, i.e. temperatures of about -10C to about 150C, preferably of about 20C to abollt 120C~ or those in the known sulfonation of aromatic compounds with chlorosulfonic acid or oleum in the first step, i.e. temperatures of about -10C to about 150DC, preferably of abou~ 20-C to about 130C, and those in the subsequent known sulfochlorination with thionyl chloride in the second s~ep, i.e. temperatures of about 30C to about 150C, preferably about 50C to about 130C, can be used.
The examples and comparison examples below are used to illustrate the process according to the invention without limiting it thereto.
~xample 1 (4-Chlorobe~zenesulfonyl chloride) 112.6 g (1.0 mol) of chlorobenzene are added dropwise at 70C over a period of 1 hour to 122 g (1.05 mol) of chlorosulfonic acid and l g of sulfamic acid. The mixture is then stirred at this temperatur~a for 15 minutes.
180 g (1.5 mol) of thionyl chloride are then added dropwise at 70C over a period of 2 hours and the mixture is stirred until evolution of gas has ended. The exce~s thionyl chloride is distilled off and the residue is slowly added to ice water. The precipi~ated 4-chloro-benzenesulfonyl chloride is filtered off with suction and washed with ice water. 202.3 g of moist 4-chloro-benzenesulfonyl chloride having a water content of 4 %
are obtained. This corresponds to 194.2 ~ of 4-chlorv-benzenesulfonyl chloride (92 ~ of theory~, calculated asdry material, ha~ing a purity of 95 %.
2 ~ 7 :~
s E~a~ple 2 (4-Chlorobenze~esulionyl chloride) 112.6 g (1.0 mol) of chlorobenzene are added dropwise at 70C over a period of 1 hour to 122 g (1.05 mol) of chlorosulfonic acid. The mixture is then stirred at this temperatur0 for 15 minutes. 1 g of sulfamic acid is then added and 180 g (1.5 mol) of thionyl chloride are added dropwise at 70C in the course of 2 hours. Working up is carried out as described in ~xample 1. 228.3 g of moist 4-chlorobenz~nesulfonyl chloride having a water content of 12 % are obtained. This corresponds to 200.9 ~ of 4-chlorobenzenesulfonyl chloride (94.9 % of theory), calculated as dry material~ having a purity of 95 %.
~ample 3 (4-Chlorobenzenesulonyl ~hloride);
Compari~on example without use of ~lfamic acid 122 g (1.05 mol) of chlorosulfonic acid, 112.6 g (1.0 mol) of chlorobenzene and 180 g (l.S mol) of thionyl chloride are reacted as described in Example 1, but without addition of sulfamic acid.
172.8 g of moist 4-chlorobenzenesu]Lfonyl chloride having a water content of 7.1 ~ are obtained. Thi6 corresponds to 160.5 g o~ 4-chloroben~ene~ulfonyl chloride (76 % of theory) having a purity of 94 ~.
~ample~ 4 to 11 1 mol oi an aromatic compound from Table 1 below i~ added dropwise at 70C to 1 mol of chloro~ulfonic acid. ~he mixture is then stirred for lS minutesO 1 g of sulfamic acid is then added first, as indicated in Table 1, after which 2 mol of thionyl chloride are added dropwi~2 and finally the mixture is stirred until the evolution of gas haæ ended. For working up, the mixture is distilled.
The reaction without addition of sulfamic acid is also carried out for comparison.
- 6 ~ 2 ~ rJ :`~
Table 1 . Aroma~ic Cata- b.p~ ~ield Purity ~o. ~ompound lyæt (% of ~GC s~rfa~e th~ory) area ~) . - _ __ _ 4 benzene with 142~C/40 torr 88.9 98.3 benzene with- 142C/40 ~orr 78.6 98.3 out 6 fluoro- with 124C/ 8 torr 84.8 97.0 benzene 7 fluoro~ with- 124C/ 8 torr 76.0 96.9 benzene out 8 toluene with 110C/ 2 torr 89.9 76 p-24 o-9 toluene with- 110C/ 2 torr 80.3 76 p-out 24 o-cumene with 136C/ 2 torr 85.8 96.7 11 cumene with- 136C/ 2 torr 67.5 94.0 out 20 E::~ample 12 (2-Nitrotoluene-4-~ulfo~nyl chloride) 137.1 g (1.0 mol) of o-nitrotoluene are added dropwise to 535.9 g (4.6 mol) of chlorosulfonic acid and 2 ~ of sulfamic acid uch that the temperature does not exceed 40C. The mixture is then stirred at 40C for 1 hour and slowly heated to 105C. It is then stirred at 105C for 6 hours, cooled and added dropwise to ice water at 0 to 5C. The precipitated crystal~ are filt~red of~ with suction and washed with ice water. 286.1 g of 2-nitrotol-uene-4-sulfonyl chloride (water content 10.8 %), cor-responding to 210.6 g ~89 ~ of theory), having a melting point of 40C are obtained.
~ample 13 (2-Nitrotol~ene-4-~ulfo~yl chloride) - C~pari~on E~ample -535.9 g ~4.6 mol) of chlorosul~onic acid are reacted with 2 ~ 7 ~
137.1 g (1.0 mol) of o-nitrotoluene analogously to ~xample 12, but without 6ulfamic acid. Yield 700.7 g (water content 6.3 %~, corresponding to 188.1 g (80 % of theory).
S ~ample 14 (4-~cetamidobenzenesulfonyl chloride~
135.2 g (1.0 mol) of acetanilide are added in portions ~o 349.5 g (3.0 mol) of chlorosulfonic acid and 2 g of sulfamic acid such that the temperature remains at 40C.
The mixture is then heated to 60C and stirred a this tempera~ure for 60 minute~, then 142.8 g (1.2 mol~ of thionyl chloride are added dropwise over the cour~e of 2 hours and the mixture is stirred until evolution of gas has ended. For working up, the mixture is dripped into ice water, and the precipitated crystals are filtered off with suction and washed with water. 334.9 g of 4-acet-amidobenzenesulfonyl chloride (water content: 41.7 %;
chloride content: 58.1 %), corresponding to 230.2 g ~98.5 %) calculated as dry material, having a melting point of 139C are obtained.
~ample 15 ~4-Acetamidobenzenesulfon~l chloride) - Co~pari~nn ~xample -135.2 g (1.0 mol) of acetanilide, 349.5 g (3.0 mol) of chlorosulfonic acid and 142.8 g (1.2 mol) of thionyl chloride are reacted analogously to Example 14, but without sulfamic acid. 358.5 g of 4-acetamidobenzene-sulfonyl chloride (wa~er content: 39.4 %, chloride content: 60.2 %), corresponding to 217 3 g ~93.0 ~ of theory), calculated as dry material, having a melting point of 139C are obtained.
E~ampl~ 16 ~3-Chlorosulfonylbenz~nic acid) 122.1 g (1.0 mol) of benzoic acid are introduced into a mixture of 349.5 g ~3.0 mol~ of chlorosulfonic acid, 20 of 96 ~ strength sulfuric acid and 1 g of sulfamic acid.
2 ~
Th~ reaction mixkure thus obtained i6 heated to 120C in the course of 3 hours and stirred until evolution of gas has ended. The mixture is then cooled to 70C and 119.0 g (1.0 mol) of ~hionyl chloride are added dropwise over the course of 2 hours. After it has been stirred at 80C for 30 minutes, the reaction mixture is added dropwise at lO~C to ice water, and the precipi~ated cry~tals are filtered off with suction and washed with ice water.
232.1 g of 3-chlorosulfonylbenzoic acid (water content:
10 %), corresponding to 208.g g ~94~7 % of theo~y), calculated as dry material, having a melting point of 129-131C are obtained.
Example 17 (3-Chlorosulfonylbe~zoic acid~
- Comparison ~sample -122.1 g (1.0 mol) of benzoic acid, 349.5 g (3.0 mol) of chlorosulonic acid, 20 g of 96 ~ stxength sulfuric acid and 119 g (1.0 mol) of thionyl chloride are reacted analogously to Ex~mple 16, but without addition of sul-famic acid. 198.3 g of 3-chlorosulfonylbenzoic acid (water content: 8.2 %), correspondi.ng to 182.0 g (82.5 of theo~y), calculated as dry material, are obtained.
E~ample 18 (6-Be~zoxazoleæ~lfonyl chloride) 135 g (l.0 mol) of benzoxazolnne are introduced into 349.5 g (3.0 mol~ of chlorosulfonic acid and 1 g of sulfamic acid in ~uch a way that the temperature does not rise above 40C. The mixture is then heated to 60C and stirred at this temperature for 1 hour. 142.8 g (1.2 mol) of thionyl chloride are then added dropwisa and the mixture is stirred until the evolution of gas iB com-plete. The reaction mixture is dripped into ice water, and the precipitated crystals are filtered off with 6uction and washed with water. 264.2 g of moist 6-benzox-azole sulfonyl chloride having a water content of 21.2 %
and a melting point of 188-190C, corresponding to a yield of 208.5 g ~89.3 ~ of theory), are obtained.
_ 9 _ E~ample 19 t6 Ben~oxa~olonesulfonyl chloride) - Comparison Exsmple -34g.5 g (3.0 mol) of chlorosulfonic acid, 13S g (1.0 mol) of benzoxazolone and 142.8 g (1.2 mol) of thionyl chlor-ide are reacted as described in Example lB, bu~ without addition of sulfamic acid.
231.7 g of 6-benzoxazolonesulfonyl chloride ha~ing a water content of 19.4 %, corresponding to a yield of 186.8 g (80.0 % of theory), are obtained.
~ample 20 (3-~itrobenzene~ulfo~yl chloride) 123.1 g (1.0 mol) of nitrobenzene are allowed to run rapidly into 582.5 g (5.0 mol) of chlorosulfonic acid and 1 g of sulfamic acid at room temperature. ~he mixture is then heated to 105C and stirred at: this temperature for 6 hoursO For working up~ the reaction mlxture is dripped into ice water. The precipitated crystals are filtered off with suction and washed with water. 194.6 g of dry 3-nitrobenzenesulfonyl chloride having a melting point of 59-61C, corresponding to a yield of 87.8 % of theory, are obtained.
l~ampl~ 21 ( 3-Nit~obenzene;ul:Eonyl chl~ride~
- Compari~ion B~ample -123.1 g (1.0 mol) of nitrobenzene and 582.5 g ~5.0 mol) of chlorosulfonic acid are reacted as d0scribed in Example 20, but without addition of sulfamic acid.
175.1 g of dry 3-nitrobenzenesulfonyl chloride, cor-responding to a yield o 79.0 ~ of theory, are obtained.
E~ampl~ 22 (2-~itrochlorobenzene-4-sulfonyl chloride) 157.6 g (1.0 mol) of 2-chloronitrobenzene are added to 699 g (6.0 mol) of chlorosulfonic acid and 2 g of sulfamic acid such that the temperature does not exceed 2~ 3l~
40C. After addition is complete, the mixture is heated ~o 100C and stirred at this temperature for 6 hours. The reaction mixture is dripped into water at 15C, and the precipitated crystal~ are filtered off with suction and washed with water. 236.~ g of 2-ni~rochlorobenzene-4-sulfonyl chloride having a water content of 1.5 ~, corresponding to 232.7 g of 2-nitrochlorobenzene-4-sulfonyl chloride (90.8 % of theory), are obtained.
~ample 23 (2-~itrochlorobenzene-4-~ulfonyl chloride) - Co~pari~on ~ample -157.6 g (1.0 mol) of 2-chloronitrobenzene and 699 g (6.0 mol) of chlorosulfonic acid are reacted as in Example 22, but without addition of sulfamic acid.
212.8 g of 2-nitrochlorobenzene-4-sulfonyl chloride having a water content of 1.2 ~, corresponding to 21n.2 g of 2-nitrochlorobenzene-4-sulfonyl chloride (82.1 % of theory), are obtained.
Example 24 (Naphthalene-1,5-di~ulfonyl chloride) 64.1 g (0.5 mol) of naphthalene ar~e introduced with ice cooling into 640.7 g (5.5 mol) of chlorosulfonic acid, to which 1 g of sulfamic acid has been added. The mixture is then stirred at room temperature for 4 hours. The reac-tion mixture is added dropwise to ice water, and the precipitated crystals are filtered ~ff with ~uction and washed with water. 172.1 g of naphthalene-1,5-disulfonyl chloride having a water content of 26.5 % and a chloride content of 71.6 %j corresponding to 123.2 g (75.7 ~), are obtained.
Example 25 ~aphthalene-l,S di~ulfonyl chloride) - Compari~on ~xa~ple -64.1 g (0.5 mol~ of naphthalene and 640.7 g (5.5 mol) of chlorosulfonic acid are reacted as in Example 26, but without addition of sulfamic acid. 139.4 g of 2 ~ 7 ~l naphthalene-1,5 disulfonyl chloride having a water content of 25.8 % and a chloride conten of 72.5 %, corresponding to 101.1 g ~62.2 %), are obtained.
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HOECHST AKTIENGESEL~SCHAFT HOE 89/F 187 Dr. M~/rh Description Process for ~he preparation of aromati~ ~ulfon~l chlorides The invention relates to the preparation of aromatic sulfonyl chlorides in a manner known per se by reaction of aromatic compounds with excess chlorosulfonic acid or with chlorosulfonic acid or oleum and thionyl chloride, the reaction being carried out in ~he pres nce of sul famic acid as a catalyst.
It is known that ~he sulfonation and sulfochlorination of aromatic compounds can be umpro~ed by adding so-called sulfone inhibitors to suppress the sulfone formation observed as a secondary reaction [Ullmann's Encyclopedia of Industrial Chemistry, 5th ed., vol. A.3, p. 513].
Examples of such sulfone inhibitors which may be men-tioned are ammonium sulfate, sodi~ carbonate or potas-5ium carbonate [DE 3,501,754], and sodium chloride or ammonium chloride [DE 3,306,597]. A large num~er of other sulfonating agents are mentioned in EP 0,001,275.
It is known from Helv. ChLmica Acta 42, 1653 (1959) that dialkylformamides act as satalysts in th~ preparation of naphthalenesulfonyl chlorides ~rom the corresponding sulfonic acids.
Reference is made in DE 2,g38,744 to ths toxicological problems in the use of dLmethylformami~e in particular, and substitutes, such as, for example, pyridine/ substi-tuted pyridines, tertiary aliphatic amines and quaterna~y ammonium s lts, preferably tertiary amines, are proposed.
The compounds proposed as catalysts or auxiliarie~ for the sulfonation or sulfochlorination of aromatic com-pounds are not satisfactory for industrial use, in particular for reasons of occupational hygiene , and thus 2 ~
capable of Lmprovement .
It has now been found tha~ sulfamic acid is a novel, advantageous auxiliary for the sulfochlorination of aromatic compounds to give the coxresponding arylsulfonyl chlorides.
The invention thus relates to an Lmproved process, with respect to attainable yields and quality, for the prepar-ation of aromatic sulfonyl chlorides of the general formula I
S02Cl in which Rl, R2 and R3 are identical or different and are hydrogen, fluoxine, chlorine, bxom.ine or iodine atoms, alkyl(Cl-C~), acetamido, nitro or carboxyl groups, or Rl and R2 together form an aromatic or heteroaromatic ring having 5 or 6 ring members, which can be substituted by fluorine, chlorine, bromine or iodine atoms, alkyl(Cl-C4), acetamido, nitro or carboxyl groups~ by reaction of aromatic compounds of the general formula II
R1 ~ R3 (II~
R~
in which Rl, R~ and ~3 have the abovementioned meanings, in a manner kno~n per se with chlorosulfo~ic acid in excess or with chlorosulfonic acid or oleum and thionyl chloride, which comprises reacting in the presence of sulfamic acid as a catalyst.
~ J~
The sulfamic acld employed according to the i~vention as a catalytically active auxiliary cannot be classified in any of the known compound classes of auxiliaries or catalysts for the sulfochlorination of aromatic compounds.
The aromatic sulfonyl chlorideæ are prepared rom the aroma~ic compounds by methods known per se, for example by reac~ion of the aromatic compounds of the abovemen-tioned general formula I~ with excess chlorosulfonic acid [cf. WinnacXer-Ruchler, Chemische Technologie ~Chemical Technology), volume 6, 4~h edition~ page 181, Carl-Hauser Verlag ~unich vienna] or chlorosulfonic acid (or oleum) and thionyl chloride [DE 3,302,647].
In this connection, a procedure is expediently used in which the su:Lfamic acid i8 partially or completely added to the chlorosulfonic acid and, in the case of only partial addition at the beginning of the reaction, further sulfamic acid is metere~ in during the reaction However, it is also possible to convert the aromatic startin~ compound into the aromatic sulfonic acid first using chlorosulfonic acid or oleum~ to add the sulfamic acid to the raaction mixture produced in this ca~e and then to react further to give the arylsulfonyl chloride with thionyl chloride.
The sulfamic acid is expediently added in an amount of abou~ 0.1 to about 20 ~ by weight, preferably about 0.5 to about 5 % by weight, relative to ~he aromatic compound of said general formula (II), to the chlorosulfonic acid, whirh is used in excess ~when working without thionyl chloride)~ or after completion of the sulfonation in the firs~ step and before addition of the thionyl chloride in the second step. Addition of sulfamic acid in larger amounts is admittedly possible, but possesses no advantages.
2 ~
~ 4 --As far as the temperatures are concerned, thos~ in the known ~ulfochlorination of aromatic compounds with an excess of chlorosulfonic acid, i.e. temperatures of about -10C to about 150C, preferably of about 20C to abollt 120C~ or those in the known sulfonation of aromatic compounds with chlorosulfonic acid or oleum in the first step, i.e. temperatures of about -10C to about 150DC, preferably of abou~ 20-C to about 130C, and those in the subsequent known sulfochlorination with thionyl chloride in the second s~ep, i.e. temperatures of about 30C to about 150C, preferably about 50C to about 130C, can be used.
The examples and comparison examples below are used to illustrate the process according to the invention without limiting it thereto.
~xample 1 (4-Chlorobe~zenesulfonyl chloride) 112.6 g (1.0 mol) of chlorobenzene are added dropwise at 70C over a period of 1 hour to 122 g (1.05 mol) of chlorosulfonic acid and l g of sulfamic acid. The mixture is then stirred at this temperatur~a for 15 minutes.
180 g (1.5 mol) of thionyl chloride are then added dropwise at 70C over a period of 2 hours and the mixture is stirred until evolution of gas has ended. The exce~s thionyl chloride is distilled off and the residue is slowly added to ice water. The precipi~ated 4-chloro-benzenesulfonyl chloride is filtered off with suction and washed with ice water. 202.3 g of moist 4-chloro-benzenesulfonyl chloride having a water content of 4 %
are obtained. This corresponds to 194.2 ~ of 4-chlorv-benzenesulfonyl chloride (92 ~ of theory~, calculated asdry material, ha~ing a purity of 95 %.
2 ~ 7 :~
s E~a~ple 2 (4-Chlorobenze~esulionyl chloride) 112.6 g (1.0 mol) of chlorobenzene are added dropwise at 70C over a period of 1 hour to 122 g (1.05 mol) of chlorosulfonic acid. The mixture is then stirred at this temperatur0 for 15 minutes. 1 g of sulfamic acid is then added and 180 g (1.5 mol) of thionyl chloride are added dropwise at 70C in the course of 2 hours. Working up is carried out as described in ~xample 1. 228.3 g of moist 4-chlorobenz~nesulfonyl chloride having a water content of 12 % are obtained. This corresponds to 200.9 ~ of 4-chlorobenzenesulfonyl chloride (94.9 % of theory), calculated as dry material~ having a purity of 95 %.
~ample 3 (4-Chlorobenzenesulonyl ~hloride);
Compari~on example without use of ~lfamic acid 122 g (1.05 mol) of chlorosulfonic acid, 112.6 g (1.0 mol) of chlorobenzene and 180 g (l.S mol) of thionyl chloride are reacted as described in Example 1, but without addition of sulfamic acid.
172.8 g of moist 4-chlorobenzenesu]Lfonyl chloride having a water content of 7.1 ~ are obtained. Thi6 corresponds to 160.5 g o~ 4-chloroben~ene~ulfonyl chloride (76 % of theory) having a purity of 94 ~.
~ample~ 4 to 11 1 mol oi an aromatic compound from Table 1 below i~ added dropwise at 70C to 1 mol of chloro~ulfonic acid. ~he mixture is then stirred for lS minutesO 1 g of sulfamic acid is then added first, as indicated in Table 1, after which 2 mol of thionyl chloride are added dropwi~2 and finally the mixture is stirred until the evolution of gas haæ ended. For working up, the mixture is distilled.
The reaction without addition of sulfamic acid is also carried out for comparison.
- 6 ~ 2 ~ rJ :`~
Table 1 . Aroma~ic Cata- b.p~ ~ield Purity ~o. ~ompound lyæt (% of ~GC s~rfa~e th~ory) area ~) . - _ __ _ 4 benzene with 142~C/40 torr 88.9 98.3 benzene with- 142C/40 ~orr 78.6 98.3 out 6 fluoro- with 124C/ 8 torr 84.8 97.0 benzene 7 fluoro~ with- 124C/ 8 torr 76.0 96.9 benzene out 8 toluene with 110C/ 2 torr 89.9 76 p-24 o-9 toluene with- 110C/ 2 torr 80.3 76 p-out 24 o-cumene with 136C/ 2 torr 85.8 96.7 11 cumene with- 136C/ 2 torr 67.5 94.0 out 20 E::~ample 12 (2-Nitrotoluene-4-~ulfo~nyl chloride) 137.1 g (1.0 mol) of o-nitrotoluene are added dropwise to 535.9 g (4.6 mol) of chlorosulfonic acid and 2 ~ of sulfamic acid uch that the temperature does not exceed 40C. The mixture is then stirred at 40C for 1 hour and slowly heated to 105C. It is then stirred at 105C for 6 hours, cooled and added dropwise to ice water at 0 to 5C. The precipitated crystal~ are filt~red of~ with suction and washed with ice water. 286.1 g of 2-nitrotol-uene-4-sulfonyl chloride (water content 10.8 %), cor-responding to 210.6 g ~89 ~ of theory), having a melting point of 40C are obtained.
~ample 13 (2-Nitrotol~ene-4-~ulfo~yl chloride) - C~pari~on E~ample -535.9 g ~4.6 mol) of chlorosul~onic acid are reacted with 2 ~ 7 ~
137.1 g (1.0 mol) of o-nitrotoluene analogously to ~xample 12, but without 6ulfamic acid. Yield 700.7 g (water content 6.3 %~, corresponding to 188.1 g (80 % of theory).
S ~ample 14 (4-~cetamidobenzenesulfonyl chloride~
135.2 g (1.0 mol) of acetanilide are added in portions ~o 349.5 g (3.0 mol) of chlorosulfonic acid and 2 g of sulfamic acid such that the temperature remains at 40C.
The mixture is then heated to 60C and stirred a this tempera~ure for 60 minute~, then 142.8 g (1.2 mol~ of thionyl chloride are added dropwise over the cour~e of 2 hours and the mixture is stirred until evolution of gas has ended. For working up, the mixture is dripped into ice water, and the precipitated crystals are filtered off with suction and washed with water. 334.9 g of 4-acet-amidobenzenesulfonyl chloride (water content: 41.7 %;
chloride content: 58.1 %), corresponding to 230.2 g ~98.5 %) calculated as dry material, having a melting point of 139C are obtained.
~ample 15 ~4-Acetamidobenzenesulfon~l chloride) - Co~pari~nn ~xample -135.2 g (1.0 mol) of acetanilide, 349.5 g (3.0 mol) of chlorosulfonic acid and 142.8 g (1.2 mol) of thionyl chloride are reacted analogously to Example 14, but without sulfamic acid. 358.5 g of 4-acetamidobenzene-sulfonyl chloride (wa~er content: 39.4 %, chloride content: 60.2 %), corresponding to 217 3 g ~93.0 ~ of theory), calculated as dry material, having a melting point of 139C are obtained.
E~ampl~ 16 ~3-Chlorosulfonylbenz~nic acid) 122.1 g (1.0 mol) of benzoic acid are introduced into a mixture of 349.5 g ~3.0 mol~ of chlorosulfonic acid, 20 of 96 ~ strength sulfuric acid and 1 g of sulfamic acid.
2 ~
Th~ reaction mixkure thus obtained i6 heated to 120C in the course of 3 hours and stirred until evolution of gas has ended. The mixture is then cooled to 70C and 119.0 g (1.0 mol) of ~hionyl chloride are added dropwise over the course of 2 hours. After it has been stirred at 80C for 30 minutes, the reaction mixture is added dropwise at lO~C to ice water, and the precipi~ated cry~tals are filtered off with suction and washed with ice water.
232.1 g of 3-chlorosulfonylbenzoic acid (water content:
10 %), corresponding to 208.g g ~94~7 % of theo~y), calculated as dry material, having a melting point of 129-131C are obtained.
Example 17 (3-Chlorosulfonylbe~zoic acid~
- Comparison ~sample -122.1 g (1.0 mol) of benzoic acid, 349.5 g (3.0 mol) of chlorosulonic acid, 20 g of 96 ~ stxength sulfuric acid and 119 g (1.0 mol) of thionyl chloride are reacted analogously to Ex~mple 16, but without addition of sul-famic acid. 198.3 g of 3-chlorosulfonylbenzoic acid (water content: 8.2 %), correspondi.ng to 182.0 g (82.5 of theo~y), calculated as dry material, are obtained.
E~ample 18 (6-Be~zoxazoleæ~lfonyl chloride) 135 g (l.0 mol) of benzoxazolnne are introduced into 349.5 g (3.0 mol~ of chlorosulfonic acid and 1 g of sulfamic acid in ~uch a way that the temperature does not rise above 40C. The mixture is then heated to 60C and stirred at this temperature for 1 hour. 142.8 g (1.2 mol) of thionyl chloride are then added dropwisa and the mixture is stirred until the evolution of gas iB com-plete. The reaction mixture is dripped into ice water, and the precipitated crystals are filtered off with 6uction and washed with water. 264.2 g of moist 6-benzox-azole sulfonyl chloride having a water content of 21.2 %
and a melting point of 188-190C, corresponding to a yield of 208.5 g ~89.3 ~ of theory), are obtained.
_ 9 _ E~ample 19 t6 Ben~oxa~olonesulfonyl chloride) - Comparison Exsmple -34g.5 g (3.0 mol) of chlorosulfonic acid, 13S g (1.0 mol) of benzoxazolone and 142.8 g (1.2 mol) of thionyl chlor-ide are reacted as described in Example lB, bu~ without addition of sulfamic acid.
231.7 g of 6-benzoxazolonesulfonyl chloride ha~ing a water content of 19.4 %, corresponding to a yield of 186.8 g (80.0 % of theory), are obtained.
~ample 20 (3-~itrobenzene~ulfo~yl chloride) 123.1 g (1.0 mol) of nitrobenzene are allowed to run rapidly into 582.5 g (5.0 mol) of chlorosulfonic acid and 1 g of sulfamic acid at room temperature. ~he mixture is then heated to 105C and stirred at: this temperature for 6 hoursO For working up~ the reaction mlxture is dripped into ice water. The precipitated crystals are filtered off with suction and washed with water. 194.6 g of dry 3-nitrobenzenesulfonyl chloride having a melting point of 59-61C, corresponding to a yield of 87.8 % of theory, are obtained.
l~ampl~ 21 ( 3-Nit~obenzene;ul:Eonyl chl~ride~
- Compari~ion B~ample -123.1 g (1.0 mol) of nitrobenzene and 582.5 g ~5.0 mol) of chlorosulfonic acid are reacted as d0scribed in Example 20, but without addition of sulfamic acid.
175.1 g of dry 3-nitrobenzenesulfonyl chloride, cor-responding to a yield o 79.0 ~ of theory, are obtained.
E~ampl~ 22 (2-~itrochlorobenzene-4-sulfonyl chloride) 157.6 g (1.0 mol) of 2-chloronitrobenzene are added to 699 g (6.0 mol) of chlorosulfonic acid and 2 g of sulfamic acid such that the temperature does not exceed 2~ 3l~
40C. After addition is complete, the mixture is heated ~o 100C and stirred at this temperature for 6 hours. The reaction mixture is dripped into water at 15C, and the precipitated crystal~ are filtered off with suction and washed with water. 236.~ g of 2-ni~rochlorobenzene-4-sulfonyl chloride having a water content of 1.5 ~, corresponding to 232.7 g of 2-nitrochlorobenzene-4-sulfonyl chloride (90.8 % of theory), are obtained.
~ample 23 (2-~itrochlorobenzene-4-~ulfonyl chloride) - Co~pari~on ~ample -157.6 g (1.0 mol) of 2-chloronitrobenzene and 699 g (6.0 mol) of chlorosulfonic acid are reacted as in Example 22, but without addition of sulfamic acid.
212.8 g of 2-nitrochlorobenzene-4-sulfonyl chloride having a water content of 1.2 ~, corresponding to 21n.2 g of 2-nitrochlorobenzene-4-sulfonyl chloride (82.1 % of theory), are obtained.
Example 24 (Naphthalene-1,5-di~ulfonyl chloride) 64.1 g (0.5 mol) of naphthalene ar~e introduced with ice cooling into 640.7 g (5.5 mol) of chlorosulfonic acid, to which 1 g of sulfamic acid has been added. The mixture is then stirred at room temperature for 4 hours. The reac-tion mixture is added dropwise to ice water, and the precipitated crystals are filtered ~ff with ~uction and washed with water. 172.1 g of naphthalene-1,5-disulfonyl chloride having a water content of 26.5 % and a chloride content of 71.6 %j corresponding to 123.2 g (75.7 ~), are obtained.
Example 25 ~aphthalene-l,S di~ulfonyl chloride) - Compari~on ~xa~ple -64.1 g (0.5 mol~ of naphthalene and 640.7 g (5.5 mol) of chlorosulfonic acid are reacted as in Example 26, but without addition of sulfamic acid. 139.4 g of 2 ~ 7 ~l naphthalene-1,5 disulfonyl chloride having a water content of 25.8 % and a chloride conten of 72.5 %, corresponding to 101.1 g ~62.2 %), are obtained.
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.
Claims (7)
1 A process for the preparation of aromatic sul-fonyl chlorides of the formula I
(I) in which R1, R2 and R3 are identical or different and are hydrogen, fluorine, chlorine, bromine or iodine atoms, alkyl(C1-C4), acetamido, nitro or carboxyl groups, or R1 and R2 together form an aromatic or heteroaromatic ring having 5 or 6 ring members, which can be substituted by fluorine, chlorine, bromine or iodine atoms, alkyl(C1-C4), acetamido, nitro or carboxyl groups, by reaction of aromatic compounds of the formula II
(II) in which R1, R2 and R3 have the abovementioned meanings, with chlorosulfonic acid in excess or with chlorosulfonic acid or oleum and thionyl chloride, which comprises reacting in the presence of sulfamic acid as a catalyst.
(I) in which R1, R2 and R3 are identical or different and are hydrogen, fluorine, chlorine, bromine or iodine atoms, alkyl(C1-C4), acetamido, nitro or carboxyl groups, or R1 and R2 together form an aromatic or heteroaromatic ring having 5 or 6 ring members, which can be substituted by fluorine, chlorine, bromine or iodine atoms, alkyl(C1-C4), acetamido, nitro or carboxyl groups, by reaction of aromatic compounds of the formula II
(II) in which R1, R2 and R3 have the abovementioned meanings, with chlorosulfonic acid in excess or with chlorosulfonic acid or oleum and thionyl chloride, which comprises reacting in the presence of sulfamic acid as a catalyst.
2. The process as claimed in claim 1, which com-prises reacting in the presence of about 0.1 to about 20 % by weight of sulfamic acid, relative to the aromatic compound of said formula II.
3. The process as claimed in at least one of claims 1 and 2, which comprises reacting in the presence of about 0.5 to about 5 % by weight of sulfamic acid, relative to the aromatic compound of said formula II.
4. The process as claimed in at least one of claims 1 to 3, which process is carried out at normal or elevated pressure.
5. The process as claimed in at least one of claims 1 to 4, wherein the sulfamic acid is completely added to the chlorosulfonic acid at the start of the reaction.
6. The process as claimed in at least one of claims 1 to 4, wherein the sulfamic acid is only partial-ly added to the chlorosulfonic acid at the start of the reaction and further sulfamic acid is metered in during the course of the reaction.
7. The process as claimed in at least one of claims 1 to 4, wherein, when using chlorosulfonic acid or oleum as the sulfonating agent, the sulfamic acid is added to the reaction mixture obtained after reaction of the aromatic compound of said formula II with said sulfonating agent and the mixture is then reacted with thionyl chloride to give arylsulfonyl chloride.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3919840.5 | 1989-06-17 | ||
| DE3919840A DE3919840A1 (en) | 1989-06-17 | 1989-06-17 | METHOD FOR PRODUCING AROMATIC SULPHONIC ACID CHLORIDES |
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| Publication Number | Publication Date |
|---|---|
| CA2019071A1 true CA2019071A1 (en) | 1990-12-17 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002019071A Abandoned CA2019071A1 (en) | 1989-06-17 | 1990-06-15 | Process for the preparation of aromatic sulfonyl chlorides |
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|---|---|
| EP (1) | EP0403947B1 (en) |
| JP (1) | JP2839653B2 (en) |
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| DE4006666A1 (en) * | 1990-03-03 | 1991-09-05 | Hoechst Ag | METHOD FOR PRODUCING 3-NITROBENZENE SULPHONIC ACID CHLORIDE |
| US5325893A (en) * | 1991-10-04 | 1994-07-05 | Tokushu Paper Mfg. Co., Ltd. | Air duct and paper therefor |
| DE59301858D1 (en) * | 1992-08-07 | 1996-04-18 | Hoechst Ag | Process for the preparation of 3-sulfobenzoic acid and its alkali salts |
| DE19645217A1 (en) * | 1996-11-02 | 1998-05-07 | Mst Automotive Gmbh | Airbag module for motor vehicle steering wheels |
| DE19747625A1 (en) * | 1997-10-29 | 1999-05-06 | Bayer Ag | Process for the preparation of 3,5-dimethylisoxazole-4-sulfochloride |
| RU2177941C1 (en) * | 2000-10-13 | 2002-01-10 | Институт органической химии им. Н.Д. Зелинского РАН | Method of synthesis of 4-(adamantyl-1)-benzenesulfochloride |
| BR0208796A (en) | 2001-04-09 | 2004-03-09 | Tibotec Pharm Ltd | Broad-spectrum 2- (substituted amino) -benzoxazole sulfonamide hiv protease inhibitors |
| JP2007170739A (en) * | 2005-12-21 | 2007-07-05 | Kumagai Gumi Co Ltd | Duct parts |
| CN103483230B (en) * | 2013-09-09 | 2015-07-08 | 南通柏盛化工有限公司 | The preparation method of p-aminobenzenesulfonamide |
| CN116589384A (en) * | 2023-04-19 | 2023-08-15 | 贵州微化科技有限公司 | A kind of method utilizing microchannel reactor to synthesize 3-nitro-4-methylbenzenesulfonyl chloride |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2743540C2 (en) * | 1977-09-28 | 1987-04-09 | Bayer Ag, 5090 Leverkusen | Process for the preparation of sulfonic acid chlorides |
| JPS6055061B2 (en) * | 1981-08-31 | 1985-12-03 | 三井東圧化学株式会社 | Method for producing 4-chlorobenzenesulfonyl chloride |
| DE3302647A1 (en) * | 1983-01-27 | 1984-08-02 | Hoechst Ag, 6230 Frankfurt | METHOD FOR PRODUCING 4-CHLORPHENYLSULFONYL COMPOUNDS |
| DE3501754A1 (en) * | 1985-01-21 | 1986-07-24 | Sandoz-Patent-GmbH, 7850 Lörrach | Sulphonation of ortho-nitrochlorobenzene, para-nitrochlorobenzene and ortho-nitrotoluene |
-
1989
- 1989-06-17 DE DE3919840A patent/DE3919840A1/en not_active Withdrawn
-
1990
- 1990-06-13 DE DE59006480T patent/DE59006480D1/en not_active Expired - Fee Related
- 1990-06-13 EP EP90111175A patent/EP0403947B1/en not_active Expired - Lifetime
- 1990-06-15 JP JP2155545A patent/JP2839653B2/en not_active Expired - Lifetime
- 1990-06-15 CA CA002019071A patent/CA2019071A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| JP2839653B2 (en) | 1998-12-16 |
| DE3919840A1 (en) | 1991-01-17 |
| EP0403947A3 (en) | 1991-02-27 |
| DE59006480D1 (en) | 1994-08-25 |
| EP0403947B1 (en) | 1994-07-20 |
| JPH0331251A (en) | 1991-02-12 |
| EP0403947A2 (en) | 1990-12-27 |
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