CA2032363A1 - Sulfonated propylphenylphosphines, their preparation and use - Google Patents
Sulfonated propylphenylphosphines, their preparation and useInfo
- Publication number
- CA2032363A1 CA2032363A1 CA002032363A CA2032363A CA2032363A1 CA 2032363 A1 CA2032363 A1 CA 2032363A1 CA 002032363 A CA002032363 A CA 002032363A CA 2032363 A CA2032363 A CA 2032363A CA 2032363 A1 CA2032363 A1 CA 2032363A1
- Authority
- CA
- Canada
- Prior art keywords
- phenyl
- phosphine
- propyl
- sulfophenyl
- sulfonated
- 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
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- VGARCGGLEUCMSB-UHFFFAOYSA-N phenyl(propyl)phosphane Chemical class CCCPC1=CC=CC=C1 VGARCGGLEUCMSB-UHFFFAOYSA-N 0.000 title claims description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 11
- PZLBEUXAGBOBFG-UHFFFAOYSA-N 3-[propyl-(3-sulfophenyl)phosphanyl]benzenesulfonic acid Chemical compound C=1C=CC(S(O)(=O)=O)=CC=1P(CCC)C1=CC=CC(S(O)(=O)=O)=C1 PZLBEUXAGBOBFG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910006069 SO3H Inorganic materials 0.000 claims abstract description 6
- KNDUEWOARHQCDZ-UHFFFAOYSA-N 3-[phenyl(propyl)phosphanyl]benzenesulfonic acid Chemical compound C=1C=CC(S(O)(=O)=O)=CC=1P(CCC)C1=CC=CC=C1 KNDUEWOARHQCDZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- OWEVHIIWEQCWPS-UHFFFAOYSA-N 3-[phenyl(propyl)phosphoryl]benzenesulfonic acid Chemical class C=1C=CC(S(O)(=O)=O)=CC=1P(=O)(CCC)C1=CC=CC=C1 OWEVHIIWEQCWPS-UHFFFAOYSA-N 0.000 claims abstract description 3
- ZOEPQGNETYAXRO-UHFFFAOYSA-N 3-[propyl-(3-sulfophenyl)phosphoryl]benzenesulfonic acid Chemical compound C=1C=CC(S(O)(=O)=O)=CC=1P(=O)(CCC)C1=CC=CC(S(O)(=O)=O)=C1 ZOEPQGNETYAXRO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000011734 sodium Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- 238000006277 sulfonation reaction Methods 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 229910052936 alkali metal sulfate Inorganic materials 0.000 claims description 5
- AAXGWYDSLJUQLN-UHFFFAOYSA-N diphenyl(propyl)phosphane Chemical compound C=1C=CC=CC=1P(CCC)C1=CC=CC=C1 AAXGWYDSLJUQLN-UHFFFAOYSA-N 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 3
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 3
- 238000005227 gel permeation chromatography Methods 0.000 claims description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims description 3
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims description 2
- TZXWVGLSVDJPOQ-UHFFFAOYSA-N disulfophosphanylbenzene Chemical compound OS(=O)(=O)P(S(O)(=O)=O)C1=CC=CC=C1 TZXWVGLSVDJPOQ-UHFFFAOYSA-N 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 1
- 238000005342 ion exchange Methods 0.000 claims 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000000047 product Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- ZBMZOFSLQIPSPW-UHFFFAOYSA-N 3-bis(3-sulfophenyl)phosphanylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC(P(C=2C=C(C=CC=2)S(O)(=O)=O)C=2C=C(C=CC=2)S(O)(=O)=O)=C1 ZBMZOFSLQIPSPW-UHFFFAOYSA-N 0.000 description 2
- 238000004679 31P NMR spectroscopy Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical class PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229940032330 sulfuric acid Drugs 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 description 1
- ITPOKAFWZBFZCV-UHFFFAOYSA-N 3-diphenylphosphanylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 ITPOKAFWZBFZCV-UHFFFAOYSA-N 0.000 description 1
- 229920002307 Dextran Polymers 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920005654 Sephadex Polymers 0.000 description 1
- 239000012507 Sephadex™ Substances 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- -1 lithium aluminum hydride Chemical compound 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical class CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5022—Aromatic phosphines (P-C aromatic linkage)
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
- C07F9/5325—Aromatic phosphine oxides or thioxides (P-C aromatic linkage)
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Catalysts (AREA)
Abstract
Frankfurt, 22.12.1989 PAT/rcht-sei Hoe89/Y018 Hoechst Aktiengesellschaft, Frankfurt am Main 80 Abstract of the disclosure:
The invention relates to the chemical compounds n-propyl-(phenyl)(m-sulfophenyl)phosphine, (n-C3H7)(C6H5)-(C6H4m-SO3H)P, n-propyldi(m-sulfophenyl)phosphine, (n-C3H7)(C6H4-m-SO3H)2P the sodium salts of n-propyl-(phenyl)(m-sulfophenyl)phosphine, (n-C3H7)(C6H5)-(C6H4-m-SO3Na)P,and of n-propyldi(m-sulfophenyl)phosphine, (n-C3H7)(C6H4-m-SO3Na)2P, and the sodium salts of n-propyl-(phenyl)(m-sulfophenyl)phosphine oxide, (n-C3H7)(C6H5)-(C8H4-m-SO3Na)PO and of n-propyldi(m-sulfophenyl)phosphine oxide, (n-C3H7)(C6H4-m-SO3-Na)2PO, a process for their preparation and their use.
The invention relates to the chemical compounds n-propyl-(phenyl)(m-sulfophenyl)phosphine, (n-C3H7)(C6H5)-(C6H4m-SO3H)P, n-propyldi(m-sulfophenyl)phosphine, (n-C3H7)(C6H4-m-SO3H)2P the sodium salts of n-propyl-(phenyl)(m-sulfophenyl)phosphine, (n-C3H7)(C6H5)-(C6H4-m-SO3Na)P,and of n-propyldi(m-sulfophenyl)phosphine, (n-C3H7)(C6H4-m-SO3Na)2P, and the sodium salts of n-propyl-(phenyl)(m-sulfophenyl)phosphine oxide, (n-C3H7)(C6H5)-(C8H4-m-SO3Na)PO and of n-propyldi(m-sulfophenyl)phosphine oxide, (n-C3H7)(C6H4-m-SO3-Na)2PO, a process for their preparation and their use.
Description
2~2~3 Sulfonated propylphenylphosphines, their preparation and use The invention relates to novel sulfonated propylphenyl-phosphines, the preparation of these compounds and their use as a constituent of catalyst systems.
The preparation of sulfonated phenylphosphines is known.
The sodium salt of m-sulfophenyldiphenylphosphine is thus obtained by reacting triphenylphosphine with oleum, heating the reaction mixture on a water bath, diluting the reaction product with water and neutralizing the mixture with sodium hydroxide. The desired compound then crystallizes out of the mixture ~J. Chem. Soc. 1958, page 281/282).
The sodium salts of di~m-sulfophenyl)phenylphosphine and tri(m-sulfophenyl)phosphine are also obtained by sLmilar processes. The starting substance in both cases is again triphenylphosphine, which is reacted with oleum at temperatures between 18 and 40C over a period of 15 to ; 20 63 hours. The reaction product is likewise diluted with water and neutralized with sodium hydroxide, and it should be ensured that temperatures b010w 20C are maintained in the mixture during the addition of the sodium hydroxide (German Patent 2,627,354).
Treatment of the sodium salts with a cation exchanger resin gives the free acids, which can be reacted with various bases to give other salts. The barium and the tetraethylammonium salt of tri(m-sulfophenyl)phosphine, for example, can be prepared by this route (German Patent 2,627,354).
Sulfonated arylphosphines are employed, inter alia, as components of catalyst systems~ Org nic phosphines which also additionally contain alkyl radicals bonded directly to phosphorus, as well aq sulfonated phenyl radicals, have not been described to date.
2~3~
The invention relates to representatives o~ this novel class of substance, namely the compounds n-propyl(phenyl)-(m-sulfophenyl)phosphinel (n~C~H7)(C6H5)(C6H4-m-SO~H)P, n-propyldi(m-sulfophenyl)phosphine~ (n-C3H7)(C6H4-m-SO3H)2P, the sodium salts o~ n-propyl(phenyl)(m-sulfophenyl)-phosphine, (n-C3H7)(C6H5)(C6H4-m-SO3Na)P and of n-propyl-di(m-sulfophenyl)phosphine, (n-C3H~)(C6H4-m-SO3Na)2P, and the sodium salts of n-propyl(phenyl)(m-sulfophenyl)-phosphine oxide, (n-C3H7)(C6H~)C6H4-m-SO3Na)PO and of n-propyldi(m-sulfophenyl)phosphine oxide, (n-C3H7~(C6H4-m-SO3-Na)2PO-The invention further~[lore relates to a process for the preparation of the novel compounds. It comprises sulfonating propyldiphenylphosphine with oleum at tem-peratures below 10C, hydrolyzing the sulfonation pro-duct, neutralizing the hydrolyzed product with an alkali metal carbonate or alkali metal hydroxide, separating off the alkali metal sulfate, concentrating the aqueous solution, extracting the sulfonated propylphenylphos-phines from the dry residue, separating the mono- and disulfonated product by gel chromatography and if approp-riate converting the salts of the mono- and disulfo-phenylphosphine into the free sulfonic acids by ic n exchange or into the corresponding phosphine oxides by oxidation.
.
The propyldiphenylphosphine required for the preparation of the novel compounds is obtained from diphenylphosphine and propyl bromide in the presence of a suitable base, for example gOH (cf. Tsvetkov et al., Synthesis 1986, page 198 et seq.). Diphenylphosphine is accessible from chlorodiphenylphosphine by reaction with lithium aluminum hydride at 0C and subsequent hydrolytic working up (Ruchen et al., Chem. Ber. 91, 2871 (1958)~.
To introduce the sulfonic acid groups into the phenyl radicals, the alkyldiarylphosphine is treated with excess sulfur trioxide in the form of oleum as the sulfonating ~23~
agent. It has proved appropriate to employ oleum which contains 10 to 65 and in particular 20 to 30~ by weight of ~free~ sulfur trioxide. The sulfonating agent is to be used in excess, relative to the phenyl radicals. 1 to 200, preferably 3 to 30, mol o~ S03 are advantageously employed per mol of phenyl radical. In practice, the oleum is initially introduced and the phosphine is added in portions, in order to ensure a constant SO3 excess.
The sulfonation is carried out at low temperatures, i.e.
at temperatures <15C, preferably at 0 to 8C. It has proved appropriate to cool the reactor well and to introduce the phosphine slowly and in small portions into the oleum, so that the heat of reaction can be removed without effort. This means that the sulfonation does not proceed in an uncontrolled manner, but in each case only one -SO3H group enters into one or into both phenyl radicals, and in paxticular mainly in the meta-position.
After addition of all the phosphinet the after-reaction can be carried out at room temperature and essentially without external cooling. However, it is advantageous to stir the reaction mixture so that any heat of reaction possibly still arising can be uniformly distribut~d and removed without delay. Longer reaction times are neces-sary, corresponding to the low temperature. In general, the reaction has ended after 20 to 100 hours, usually after 40 to 60 hours, in the temperature ranges mentioned.
After the sulfonation~ the reaction solution is diluted (hydrolyz~d) with ice-water. During this process step it should ~e ensured that a temperature of about 30C is not exceeded, and it i advantageous to maintain temperatures in the range from 0 to 10C. The dilute solution, essen-tially containing the sulfonation product and sulfuric - acid, is then neutralized. Sui~able alkaline reagen~s are the alkali metal hydroxides and the alkali metal carbon-ates, and it is advantageous to employ sodium hydroxide.
To avoid a further increase in the volume of the reaction ~3~3 mixture and to achieve a substantial deposition of the alkali metal sulfate which forms, the neutralizing agent is used as a highly concentrated solution or in undis-solved solid form, for example caustic soda flakes or granules.
Most of the alkali metal sulfate is removed from the solution by cooling, on the basis of it~ lower solubility at low temperatures. The suitable temperatures depend on the concentration of the sulfate in the solution and its solubility as a function of the temperature. The most favorable conditions are therefore to be determined rom case ~o case by experiments. The sulfate can be removed in one or more stages, and it has proved advantageous to carry out the crystallization in two stages.
After khe deposition of the alkali metal sulfate, the solution i concentrated to dryness, preferably in the vacuum of an oil pump. The sulfonated propylphenylphos-phines are extracted from the crystal magma. Suitable extraction agents are mixture of lower alcohols, such as methanol, ethanol and propanol, with water. A mixture of 7 parts by volume of methanol and 5 parts by volume of water, for example, has proved to be a suitable extxac-tion agent. The extraction is carried out by conventional processes in one or more stages, preferably two to our - 25 stages. The extracts are combined and concentrated to dryness. The residue essentially consists of the mono-sulfonated compound (n-C3H7)P(C6H5~(C6H4-m-S03Na) and the disulfonated compound (n-C3H7)P(C6H4-m-S03Na~2 The mixture of sulfonat~d alkylarylphosphines is separa-ted by gel chromatoyraphy, a process which is described in German Patent Application P 3,822,036.9. Modified organic polymers are employed as stationary solid phases, and dextran~ crosslinked with epichlorohydrin (commerci-ally available under the name Sephadex) and oligoethylene glycol/glycidyl dLmethacrylate/pentaerythritol dimetha-crylake copclymer~ (commercially availablè under the name ~32~
Fractogel) have proved to be particularly appropriate.
Water or water/solvent mixtures are used as the liquid phase, "solvent" being a water-miscible organic solvent, preferably methanol and other lower alcohols.
The free acids can be prepared from the salt3 by treat-ment of the solutions of the sodium salts of the sulfonated alkylarylphosphines with a cation exchanger in the H+ form, and they can be isolated in bulk by concen-trating the aqueous solutions. Other salts of the novel sulfonated alkylarylphosphines can be prepared from the acids by reaction with hydroxides, carbonates, ammonia or amines.
The novel compounds are colorless, crystalline sub-stances. The sodium salts contain up to one molecule of water per sodium ion, depending on the degree of drying.
Complete deh~dration is possible by heating of the hydrate forms at 60 to 100C, preferably 65 to 80C, in a high vacuum for several hours (3 to 15 hours). The protection claimed therefore extends both to the hydrated and to the anhydrous compounds.
The novel compounds ha~e proved suitable as components of catalyst systems, in particular those which contain metals of group VIII ~ of the Periodic Table and wat~r-so~uble phosphines. They contribute towards increasing the thermal sta~ility of such systems.
The pr~paration of the novel compounds is described in the following e~ample.
Example Sulfonation of (n-propyl)diphenylphosphine - 30 29.1 g (128 mmol) of propyldiphenylphosphine are added dropwise to 290 ml of oleum (S03 content: 20% by weight~
in a 500 ml three-necked flask fitted with an internal thermometer and dropping funnel at 5~C under temperature 20323~3 control in the course of one hour. The mixture is cooled in an ice-bath so that the internal temperature does not exceed 8C during the phosphine addition. The reaction mixture is stirred at room temperature for two days and then poured onto 3 kg of crushed ice for hydrolysis of the excess oleum. It is then ne11tralized with 0.45 kg of sodium hydroxide in 1 1 of water and the solution is brought to a pH of about 7 by addition of sulfuric acid and stored at 6C for three days. The crystallization of sodium sulfate is then started by stirring and the salt is filtered off and washed with ice-water. The filtrate and wash water are concentrated in the vacuum of a rotary oil pump over a cold trap. The mono- and disulfonated product are separated from one another by gel chromato-lS graphy. Sodium sulfate run the fastest. This is followedby the disulfonated product, which thus forms the second zone. The monosulfonation product finally runs as the 3rd zone. Detection of the product is by W/VIS spectroscopy or by refractometry. The products are dried in the vacuum of an oil pump in a water bath (28C) for 10 hours.
a) (n-C3H7)P(C6H5)(C6H4-m-SO3Na) ~ HzO
Characterization:
31P-NMR (109.3 MHz, D2O, 5C): ~ = -15.51 (s) lH-NMR (270 MHz, D20, 28C: ~ = 0.61 ppm (br, 3H), ~ = 1.05 ppm (br, 2H) = 1.66 ppm (br, 2H), ~ = 6.g6 - 7.72 ppm (m, 9H) - abbreviation: br = broad signal form.
Elemental analysis: (Cl5H18NaO4PS; 348.32) calculated C 51.72 H 5.21 O 18.37 P 8.89 S 9.19 found C 52.96 H 5.0~ O 18.10 P 9.06 S 9.02 b) (n-C3H~)P~C~H4-m-SO3Na)2 2 H2O
Characterization:
31P-NMR (109.3 MHz, D2O, 5C): ~ = 15.05 ppm (s) 2 ~ 3 Elemental analysis: ~C15H1gNa2O8PS2; 468.99) calculated C 38.42 H 4.08 O 27.29 P 6.60 S 13.67 found C 38.30 H 4.11 O 27.91 P 6.53 S 14.20 The two propyldiarylphosphines can be oxidized quantita-tively to the corresponding phosphine oxides with excess 30% strength hydrogen peroxide in aqueous solution if the components are heated at about 80C for 5 minutes. If the pure propyldiarylphosphines are used as the starting substances (see above), further purification of the phosphine oxides (for example by gel chromatography, which is possible in principle), is no longer necessary.
The phosphine oxides are characterized in a simple manner by 31P-N~ spectroscopy in D2O solution at 21C and a measurement frequency of 109.3 MHz:
(n-c3H7)(c6Hs)(c6H4-m-so3Na)p=o = 41.58 ppm (singlet) (n-C3H7)(c6H4-m-so3Na)2p=o = 41.08 ppm (singlet) These are colorless substances which are stable in air and heat-stable to far above 100C.
The preparation of sulfonated phenylphosphines is known.
The sodium salt of m-sulfophenyldiphenylphosphine is thus obtained by reacting triphenylphosphine with oleum, heating the reaction mixture on a water bath, diluting the reaction product with water and neutralizing the mixture with sodium hydroxide. The desired compound then crystallizes out of the mixture ~J. Chem. Soc. 1958, page 281/282).
The sodium salts of di~m-sulfophenyl)phenylphosphine and tri(m-sulfophenyl)phosphine are also obtained by sLmilar processes. The starting substance in both cases is again triphenylphosphine, which is reacted with oleum at temperatures between 18 and 40C over a period of 15 to ; 20 63 hours. The reaction product is likewise diluted with water and neutralized with sodium hydroxide, and it should be ensured that temperatures b010w 20C are maintained in the mixture during the addition of the sodium hydroxide (German Patent 2,627,354).
Treatment of the sodium salts with a cation exchanger resin gives the free acids, which can be reacted with various bases to give other salts. The barium and the tetraethylammonium salt of tri(m-sulfophenyl)phosphine, for example, can be prepared by this route (German Patent 2,627,354).
Sulfonated arylphosphines are employed, inter alia, as components of catalyst systems~ Org nic phosphines which also additionally contain alkyl radicals bonded directly to phosphorus, as well aq sulfonated phenyl radicals, have not been described to date.
2~3~
The invention relates to representatives o~ this novel class of substance, namely the compounds n-propyl(phenyl)-(m-sulfophenyl)phosphinel (n~C~H7)(C6H5)(C6H4-m-SO~H)P, n-propyldi(m-sulfophenyl)phosphine~ (n-C3H7)(C6H4-m-SO3H)2P, the sodium salts o~ n-propyl(phenyl)(m-sulfophenyl)-phosphine, (n-C3H7)(C6H5)(C6H4-m-SO3Na)P and of n-propyl-di(m-sulfophenyl)phosphine, (n-C3H~)(C6H4-m-SO3Na)2P, and the sodium salts of n-propyl(phenyl)(m-sulfophenyl)-phosphine oxide, (n-C3H7)(C6H~)C6H4-m-SO3Na)PO and of n-propyldi(m-sulfophenyl)phosphine oxide, (n-C3H7~(C6H4-m-SO3-Na)2PO-The invention further~[lore relates to a process for the preparation of the novel compounds. It comprises sulfonating propyldiphenylphosphine with oleum at tem-peratures below 10C, hydrolyzing the sulfonation pro-duct, neutralizing the hydrolyzed product with an alkali metal carbonate or alkali metal hydroxide, separating off the alkali metal sulfate, concentrating the aqueous solution, extracting the sulfonated propylphenylphos-phines from the dry residue, separating the mono- and disulfonated product by gel chromatography and if approp-riate converting the salts of the mono- and disulfo-phenylphosphine into the free sulfonic acids by ic n exchange or into the corresponding phosphine oxides by oxidation.
.
The propyldiphenylphosphine required for the preparation of the novel compounds is obtained from diphenylphosphine and propyl bromide in the presence of a suitable base, for example gOH (cf. Tsvetkov et al., Synthesis 1986, page 198 et seq.). Diphenylphosphine is accessible from chlorodiphenylphosphine by reaction with lithium aluminum hydride at 0C and subsequent hydrolytic working up (Ruchen et al., Chem. Ber. 91, 2871 (1958)~.
To introduce the sulfonic acid groups into the phenyl radicals, the alkyldiarylphosphine is treated with excess sulfur trioxide in the form of oleum as the sulfonating ~23~
agent. It has proved appropriate to employ oleum which contains 10 to 65 and in particular 20 to 30~ by weight of ~free~ sulfur trioxide. The sulfonating agent is to be used in excess, relative to the phenyl radicals. 1 to 200, preferably 3 to 30, mol o~ S03 are advantageously employed per mol of phenyl radical. In practice, the oleum is initially introduced and the phosphine is added in portions, in order to ensure a constant SO3 excess.
The sulfonation is carried out at low temperatures, i.e.
at temperatures <15C, preferably at 0 to 8C. It has proved appropriate to cool the reactor well and to introduce the phosphine slowly and in small portions into the oleum, so that the heat of reaction can be removed without effort. This means that the sulfonation does not proceed in an uncontrolled manner, but in each case only one -SO3H group enters into one or into both phenyl radicals, and in paxticular mainly in the meta-position.
After addition of all the phosphinet the after-reaction can be carried out at room temperature and essentially without external cooling. However, it is advantageous to stir the reaction mixture so that any heat of reaction possibly still arising can be uniformly distribut~d and removed without delay. Longer reaction times are neces-sary, corresponding to the low temperature. In general, the reaction has ended after 20 to 100 hours, usually after 40 to 60 hours, in the temperature ranges mentioned.
After the sulfonation~ the reaction solution is diluted (hydrolyz~d) with ice-water. During this process step it should ~e ensured that a temperature of about 30C is not exceeded, and it i advantageous to maintain temperatures in the range from 0 to 10C. The dilute solution, essen-tially containing the sulfonation product and sulfuric - acid, is then neutralized. Sui~able alkaline reagen~s are the alkali metal hydroxides and the alkali metal carbon-ates, and it is advantageous to employ sodium hydroxide.
To avoid a further increase in the volume of the reaction ~3~3 mixture and to achieve a substantial deposition of the alkali metal sulfate which forms, the neutralizing agent is used as a highly concentrated solution or in undis-solved solid form, for example caustic soda flakes or granules.
Most of the alkali metal sulfate is removed from the solution by cooling, on the basis of it~ lower solubility at low temperatures. The suitable temperatures depend on the concentration of the sulfate in the solution and its solubility as a function of the temperature. The most favorable conditions are therefore to be determined rom case ~o case by experiments. The sulfate can be removed in one or more stages, and it has proved advantageous to carry out the crystallization in two stages.
After khe deposition of the alkali metal sulfate, the solution i concentrated to dryness, preferably in the vacuum of an oil pump. The sulfonated propylphenylphos-phines are extracted from the crystal magma. Suitable extraction agents are mixture of lower alcohols, such as methanol, ethanol and propanol, with water. A mixture of 7 parts by volume of methanol and 5 parts by volume of water, for example, has proved to be a suitable extxac-tion agent. The extraction is carried out by conventional processes in one or more stages, preferably two to our - 25 stages. The extracts are combined and concentrated to dryness. The residue essentially consists of the mono-sulfonated compound (n-C3H7)P(C6H5~(C6H4-m-S03Na) and the disulfonated compound (n-C3H7)P(C6H4-m-S03Na~2 The mixture of sulfonat~d alkylarylphosphines is separa-ted by gel chromatoyraphy, a process which is described in German Patent Application P 3,822,036.9. Modified organic polymers are employed as stationary solid phases, and dextran~ crosslinked with epichlorohydrin (commerci-ally available under the name Sephadex) and oligoethylene glycol/glycidyl dLmethacrylate/pentaerythritol dimetha-crylake copclymer~ (commercially availablè under the name ~32~
Fractogel) have proved to be particularly appropriate.
Water or water/solvent mixtures are used as the liquid phase, "solvent" being a water-miscible organic solvent, preferably methanol and other lower alcohols.
The free acids can be prepared from the salt3 by treat-ment of the solutions of the sodium salts of the sulfonated alkylarylphosphines with a cation exchanger in the H+ form, and they can be isolated in bulk by concen-trating the aqueous solutions. Other salts of the novel sulfonated alkylarylphosphines can be prepared from the acids by reaction with hydroxides, carbonates, ammonia or amines.
The novel compounds are colorless, crystalline sub-stances. The sodium salts contain up to one molecule of water per sodium ion, depending on the degree of drying.
Complete deh~dration is possible by heating of the hydrate forms at 60 to 100C, preferably 65 to 80C, in a high vacuum for several hours (3 to 15 hours). The protection claimed therefore extends both to the hydrated and to the anhydrous compounds.
The novel compounds ha~e proved suitable as components of catalyst systems, in particular those which contain metals of group VIII ~ of the Periodic Table and wat~r-so~uble phosphines. They contribute towards increasing the thermal sta~ility of such systems.
The pr~paration of the novel compounds is described in the following e~ample.
Example Sulfonation of (n-propyl)diphenylphosphine - 30 29.1 g (128 mmol) of propyldiphenylphosphine are added dropwise to 290 ml of oleum (S03 content: 20% by weight~
in a 500 ml three-necked flask fitted with an internal thermometer and dropping funnel at 5~C under temperature 20323~3 control in the course of one hour. The mixture is cooled in an ice-bath so that the internal temperature does not exceed 8C during the phosphine addition. The reaction mixture is stirred at room temperature for two days and then poured onto 3 kg of crushed ice for hydrolysis of the excess oleum. It is then ne11tralized with 0.45 kg of sodium hydroxide in 1 1 of water and the solution is brought to a pH of about 7 by addition of sulfuric acid and stored at 6C for three days. The crystallization of sodium sulfate is then started by stirring and the salt is filtered off and washed with ice-water. The filtrate and wash water are concentrated in the vacuum of a rotary oil pump over a cold trap. The mono- and disulfonated product are separated from one another by gel chromato-lS graphy. Sodium sulfate run the fastest. This is followedby the disulfonated product, which thus forms the second zone. The monosulfonation product finally runs as the 3rd zone. Detection of the product is by W/VIS spectroscopy or by refractometry. The products are dried in the vacuum of an oil pump in a water bath (28C) for 10 hours.
a) (n-C3H7)P(C6H5)(C6H4-m-SO3Na) ~ HzO
Characterization:
31P-NMR (109.3 MHz, D2O, 5C): ~ = -15.51 (s) lH-NMR (270 MHz, D20, 28C: ~ = 0.61 ppm (br, 3H), ~ = 1.05 ppm (br, 2H) = 1.66 ppm (br, 2H), ~ = 6.g6 - 7.72 ppm (m, 9H) - abbreviation: br = broad signal form.
Elemental analysis: (Cl5H18NaO4PS; 348.32) calculated C 51.72 H 5.21 O 18.37 P 8.89 S 9.19 found C 52.96 H 5.0~ O 18.10 P 9.06 S 9.02 b) (n-C3H~)P~C~H4-m-SO3Na)2 2 H2O
Characterization:
31P-NMR (109.3 MHz, D2O, 5C): ~ = 15.05 ppm (s) 2 ~ 3 Elemental analysis: ~C15H1gNa2O8PS2; 468.99) calculated C 38.42 H 4.08 O 27.29 P 6.60 S 13.67 found C 38.30 H 4.11 O 27.91 P 6.53 S 14.20 The two propyldiarylphosphines can be oxidized quantita-tively to the corresponding phosphine oxides with excess 30% strength hydrogen peroxide in aqueous solution if the components are heated at about 80C for 5 minutes. If the pure propyldiarylphosphines are used as the starting substances (see above), further purification of the phosphine oxides (for example by gel chromatography, which is possible in principle), is no longer necessary.
The phosphine oxides are characterized in a simple manner by 31P-N~ spectroscopy in D2O solution at 21C and a measurement frequency of 109.3 MHz:
(n-c3H7)(c6Hs)(c6H4-m-so3Na)p=o = 41.58 ppm (singlet) (n-C3H7)(c6H4-m-so3Na)2p=o = 41.08 ppm (singlet) These are colorless substances which are stable in air and heat-stable to far above 100C.
Claims (9)
1. The chemical compounds n-propyl(phenyl)(m-sulfo-phenyl)phosphine, (n-C3H7)(C6H5)(C6H4-m-SO3H)P, n-propyl di(m-sulfophenyl)phosphine, (n-C3H7)(C6H4-m-SO3H)2P, the sodium salts of n-propyl(phenyl)(m-sulfophenyl)phosphine, (n-C3H7)(C6H5)(C6H4-m-SO3Na)P and of n-propyldi(m-sulfo-phenyl)phosphine, (n-C3H7)(C6H4-m-SO3Na)2P, the sodium salts of n-propyl(phenyl)(m-sulfophenyl)phosphine oxide, (n-C3H7)(C6H5)(C6H4-m-SO3Na)PO and of n-propyldi(m-sulfo-phenyl)phosphine oxide, (n-C3H7)(C8H4-m-SO3-Na)2PO-
2. A process for the preparation of a compound as claimed in claim 1, which comprises sulfonating propyl-diphenylphosphine with oleum at temperatures below 10°C, hydrolyzing the sulfonated product, neutralizing the hydrolyzed product with an alkali metal carbonate or alkali metal hydroxide, separating off the alkali metal sulfate, concentrating the aqueous solution, extracting the sulfonated propylphenylphosphine from the dry resi-due, separating the mono- and disulfonated product by gel chromatography and if appropriate converting the salt of the mono- and/or disulfophenylphosphine into the free sulfonic acid by ion exchange or into the corresponding phosphine oxide by oxidation.
3. The process as claimed in claim 2, wherein oleum which contains 10 to 65, in particular 20 to 30% by weight of free sulfur trioxide is employed for the sulfonation.
4. The process as claimed in claim 2 or 3, wherein 1 to 200, preferably 3 to 30 mol of sulfur trioxide are employed per mol of phenyl radical.
5. The process as claimed in one or more of claims 2 to 4, wherein the sulfonation is carried out at temper-atures below 15°C, preferably 0 to 8°C.
6. The process as claimed in one or more of claims 2 to 5, wherein the hydrolysis of the sulfonation product is carried out at temperatures up to approximately 30°C, preferably in the range from 0 to 10°C.
7. The process as claimed in one or more of claims 2 to 6, wherein the extraction of the sulfonated propylphenylphosphines is carried out with a mixture of lower alcohols and water.
8. The process as claimed in claim 7, wherein a mixture of 7 parts by volume of methanol and 5 parts by volume of water is employed as the extraction agent.
9. The use of a compound as claimed in claim 1 as a component of a catalyst system.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3942791.9 | 1989-12-23 | ||
| DE3942791A DE3942791A1 (en) | 1989-12-23 | 1989-12-23 | SULPHONATED PROPYLPHENYL PHOSPHANS, THEIR PREPARATION AND USE |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2032363A1 true CA2032363A1 (en) | 1991-06-24 |
Family
ID=6396319
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002032363A Abandoned CA2032363A1 (en) | 1989-12-23 | 1990-12-14 | Sulfonated propylphenylphosphines, their preparation and use |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0435073A1 (en) |
| JP (1) | JPH04298243A (en) |
| KR (1) | KR910011875A (en) |
| AU (1) | AU629720B2 (en) |
| BR (1) | BR9006440A (en) |
| CA (1) | CA2032363A1 (en) |
| DE (1) | DE3942791A1 (en) |
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|---|---|---|---|---|
| DE4435189A1 (en) * | 1994-09-30 | 1996-04-04 | Hoechst Ag | New sulfonated phosphines, processes for their preparation and their use as a component of catalyst systems |
| FR2773368B1 (en) * | 1998-01-06 | 2001-03-02 | Sarl Soc Rhodanienne De Transa | PROCESS FOR THE PREPARATION OF SULFONYLARYLPHOSPHINE AND METALLOID DERIVATIVES AND SULFONYLARYLPHOSPHINE AND METALLOID DERIVATIVES |
| DE10339292A1 (en) * | 2003-08-27 | 2005-04-07 | Audi Ag | Device for oscillation dampening on chain drives esp. for motor vehicles has at least one wo-part chain of hub and rim, engaging via projections and apertures and with damper oil between transmission surfaces |
| CA2622112C (en) * | 2005-09-15 | 2013-12-10 | Dow Global Technologies Inc. | Process for the monosulfonation of aromatic phosphines, and zwitterionic product derived therefrom |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2549840B1 (en) * | 1983-07-28 | 1986-03-21 | Rhone Poulenc Sante | NOVEL SULPHONE CHIRAL PHOSPHINES, THEIR PREPARATION AND THEIR USE IN ASYMMETRIC CATALYSIS |
-
1989
- 1989-12-23 DE DE3942791A patent/DE3942791A1/en not_active Withdrawn
-
1990
- 1990-12-12 EP EP90123913A patent/EP0435073A1/en not_active Withdrawn
- 1990-12-14 KR KR1019900020648A patent/KR910011875A/en not_active Application Discontinuation
- 1990-12-14 CA CA002032363A patent/CA2032363A1/en not_active Abandoned
- 1990-12-17 JP JP2402862A patent/JPH04298243A/en active Pending
- 1990-12-18 BR BR909006440A patent/BR9006440A/en not_active Application Discontinuation
- 1990-12-21 AU AU68371/90A patent/AU629720B2/en not_active Ceased
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| Publication number | Publication date |
|---|---|
| JPH04298243A (en) | 1992-10-22 |
| EP0435073A1 (en) | 1991-07-03 |
| KR910011875A (en) | 1991-08-07 |
| AU629720B2 (en) | 1992-10-08 |
| DE3942791A1 (en) | 1991-06-27 |
| AU6837190A (en) | 1991-06-27 |
| BR9006440A (en) | 1991-10-01 |
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