CN100431699C - Activated carbon carried cuprous iodide catalyst, and its preparing method and use - Google Patents
Activated carbon carried cuprous iodide catalyst, and its preparing method and use Download PDFInfo
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- CN100431699C CN100431699C CNB2006100843991A CN200610084399A CN100431699C CN 100431699 C CN100431699 C CN 100431699C CN B2006100843991 A CNB2006100843991 A CN B2006100843991A CN 200610084399 A CN200610084399 A CN 200610084399A CN 100431699 C CN100431699 C CN 100431699C
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- cuprous iodide
- activated carbon
- catalyst
- active carbon
- carbon carried
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910021595 Copper(I) iodide Inorganic materials 0.000 title claims abstract description 44
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 title claims abstract description 44
- 239000003054 catalyst Substances 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims abstract description 5
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims abstract description 5
- 235000019345 sodium thiosulphate Nutrition 0.000 claims abstract description 5
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000011630 iodine Substances 0.000 claims abstract 2
- 229910052740 iodine Inorganic materials 0.000 claims abstract 2
- -1 alkylthio group aromatic compound Chemical class 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 10
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 8
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 235000010265 sodium sulphite Nutrition 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910001868 water Inorganic materials 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims 1
- 238000009388 chemical precipitation Methods 0.000 claims 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 abstract description 4
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 abstract 3
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 abstract 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 abstract 1
- 238000005804 alkylation reaction Methods 0.000 abstract 1
- 238000007598 dipping method Methods 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 239000005864 Sulphur Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 238000006053 organic reaction Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- VLXBWPOEOIIREY-UHFFFAOYSA-N dimethyl diselenide Natural products C[Se][Se]C VLXBWPOEOIIREY-UHFFFAOYSA-N 0.000 description 4
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 3
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 description 3
- 206010070834 Sensitisation Diseases 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000007809 chemical reaction catalyst Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 238000007336 electrophilic substitution reaction Methods 0.000 description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 230000008313 sensitization Effects 0.000 description 3
- 235000010269 sulphur dioxide Nutrition 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- GVPWHKZIJBODOX-UHFFFAOYSA-N dibenzyl disulfide Chemical compound C=1C=CC=CC=1CSSCC1=CC=CC=C1 GVPWHKZIJBODOX-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- LXUNZSDDXMPKLP-UHFFFAOYSA-N 2-Methylbenzenethiol Chemical compound CC1=CC=CC=C1S LXUNZSDDXMPKLP-UHFFFAOYSA-N 0.000 description 1
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- SOOARYARZPXNAL-UHFFFAOYSA-N methyl-thiophenol Natural products CSC1=CC=CC=C1O SOOARYARZPXNAL-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- HNKJADCVZUBCPG-UHFFFAOYSA-N thioanisole Chemical compound CSC1=CC=CC=C1 HNKJADCVZUBCPG-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
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- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The active carbon loaded cuprous iodide provided in this invention can be used as the catalyst of sulfur-alkylation reaction between dialkyldithio and aromatic compound, which is processed by dipping active carbon in ethanol/hydrosolvent of bluestone and iodine or bluestone and potassium iodide then to be recovered by formaldehyde, SO, H2SO3 or sodium hyposulfite.
Description
Technical field
The present invention belongs to the chemical reaction catalyst field.Be particularly related to and be used for dialkyl group two sulphur and aromatic compound reaction, the activated carbon carried cuprous iodide catalyst of preparation alkylthio group aromatic compound.
Technical background
Many alkylthio group aromatic hydrocarbons (for example thioanisole, to methylthiophenol, 2,4-diaminourea-3,5-diformazan sulfenyl toluene, 2,6-diaminourea-3,5-diformazan sulfenyl toluene etc.) be important meticulous synthetic intermediate raw material, be widely used in the synthetic of agricultural chemicals and rubber and plastic auxiliary agent.The electrophilic substitution reaction of dialkyl group two sulphur and aromatic hydrocarbons is one of important method of preparation alkylthio group aromatic hydrocarbons, dialkyl group two sulphur wherein mainly comprise DMDS, diethyl two sulphur, benzyl disulfide, dicyclohexyl two sulphur etc., aromatic hydrocarbons mainly comprises the aromatic compound by the electron donating group activation, for example phenol, aniline, 2,4-diaminotoluene, 2,6-diaminotoluene, 2,4 (2,6)-toluenediamine mixture, to methylaniline etc.The of paramount importance Lewis of being acid is absolutely necessary as above-mentioned catalyst for reaction, and Lewis acid catalyst commonly used has cuprous iodide, zinc chloride, alchlor etc., and the catalytic effect of cuprous iodide is best.U.S. Pat 4594453, US5015770, US5210304, US5302755 etc. have reported DMDS and 2,4 (2,6)-reaction of toluenediamine mixture, preparation 2,4-diaminourea-3,5-diformazan sulfenyl toluene and 2,6-diaminourea-3, the method of 5-diformazan sulfenyl toluene mixture, the catalyst of use all is a cuprous iodide.
Commercially available cuprous iodide product is generally 20 purpose bulky grain powders, because cuprous iodide bulky grain powder proportion is bigger, so being used in the electrophilic substitution reaction of dialkyl group two sulphur and aromatic hydrocarbons prepares in the process of alkylthio group aromatic compound, it is serious to occur the sedimentation of cuprous iodide bulky grain powder in the reaction system, catalysis efficiency is low, causes the problems such as consumption increase of cuprous iodide catalyst.In order to reduce the consumption of cuprous iodide catalyst, improve its catalysis efficiency, industry generally is that adopting the pulverizing of 20 order bulky grain powder cuprous iodides is the method for 200～400 order fine powders.But cuprous iodide catalyst is a kind of photaesthesia compound, and it is more serious that loss is decomposed in the sensitization of fine powder cuprous iodide in pulverizing and catalytic applications two processes.The price of cuprous iodide is again than higher, so cuprous iodide is shared 2 as the loss height of catalyst, and 4-diaminourea-3,5-diformazan sulfenyl toluene and 2,6-diaminourea-3, the production cost ratio height of 5-diformazan sulfenyl toluene mixture.
Summary of the invention
Activated carbon carried cuprous iodide catalyst provided by the invention, purpose are to reduce the density contrast between catalyst and the organic reaction system, improve the decentralization of cuprous iodide in the organic reaction system, improve its catalysis efficiency; Utilize the black protection cuprous iodide of active carbon, avoid the sensitization of cuprous iodide in use and storage process to decompose loss, to reduce the production cost of alkylthio group aromatic compound.
The preparation method of activated carbon carried cuprous iodide catalyst provided by the invention is that active carbon is immersed in the water of copper sulphate and KI, is made by the reduction of reducing agents such as formaldehyde, sulfur dioxide, sodium sulfite or sodium thiosulfate.Perhaps active carbon is immersed in the ethanol water mixed solvent of copper sulphate and iodine, is made by the reduction of reducing agents such as formaldehyde, sulfur dioxide, sodium sulfite or sodium thiosulfate.
The described active carbon of the preparation method of activated carbon carried cuprous iodide catalyst provided by the invention can be spherical, column, round barrel shape, amorphous granular shape, also can be pulverous.In order to improve the decentralization of cuprous iodide on activated carbon surface or in the cavity, active carbon is immersed in the aqueous solution of copper sulphate and KI or active carbon is immersed in the ethanol water mixed solvent of copper sulphate and iodine, should heat earlier and boil 1～4 hour, and then adding reducing agent formaldehyde, sulfur dioxide, sodium sulfite or sodium thiosulfate etc., the cuprous iodide of Sheng Chenging just can be uniformly dispersed in active carbon like this.
Activated carbon carried cuprous iodide provided by the invention has following advantage as dialkyl group two sulphur with the electrophilic substitution reaction catalyst of aromatic hydrocarbons: the relative organic reaction system density of activated carbon carried cuprous iodide catalyst difference reduces, activated carbon carried cuprous iodide catalyst is equal dispersed high the organic reaction system, and the catalytic active center that the activated carbon carried cuprous iodide catalytic activity of equal weight is compared cuprous iodide catalyst is many; Utilize the black of active carbon can effectively protect cuprous iodide to avoid the sensitization decomposition; improve the efficient that recycles of activated carbon carried cuprous iodide catalyst; reduce the consumption of catalyst in the production of alkylthio group aromatic compound: the isolated by filtration of activated carbon carried cuprous iodide catalyst and organic reaction objects system and organic reaction product system is convenient, has simplified activated carbon carried cuprous iodide catalyst and has told process.
Following examples further specify activated carbon carried cuprous iodide catalyst provided by the invention, preparation method and application.
Embodiment 1
Activated carbon carried cuprous iodide catalyst and preparation method
In the reaction flask that agitator, reflux condenser, dropping funel are housed, add 200 milliliters of 0.21 mole of cupric sulfate pentahydrates, 0.2 mole of KI, 200 grams, 60 order active carbons, deionized water, stir down, being warming up to boiling and keeping 2 hours.Be cooled to room temperature, stir the saturated aqueous solution that splashes into 0.22 mole of sodium sulfite, react after 1 hour, collect filter cake, filter cake spends deionised water earlier 3～5 times, back absolute ethanol washing 3～5 times, the drying of finding time can make activated carbon carried cuprous iodide catalyst.
Embodiment 2
Activated carbon carried cuprous iodide catalyst and preparation method
In the reaction flask that agitator, reflux condenser, dropping funel are housed, add 0.21 mole of cupric sulfate pentahydrate, 0.2 mole of smart iodine, 200 grams, 60 order active carbons, 100 milliliters of ethanol, 100 milliliters of deionized waters, stir down evenly, be warming up to boiling 2 hours.Be cooled to room temperature, stirring splashes into 37% formalin 20 grams, reacts after 1 hour, collects filter cake, and filter cake spends deionised water earlier 3～5 times, back absolute ethanol washing 3～5 times, and the drying of finding time can make activated carbon carried cuprous iodide catalyst.
Embodiment 3
The application of activated carbon carried cuprous iodide catalyst
In the reaction flask that agitator, reflux condenser, dropping funel are housed, add just distilled 2,4-diaminotoluene and 2,6-diaminotoluene mixture (80: 20) 100 grams and embodiment 1 prepared activated carbon carried cuprous iodide catalyst 30 restrain.N
2Protection is stirred and is warming up to 130～135 ℃ down, splashes into DMDS 160 grams in 3 hours, drips off DMDS and continues to keep 130～135 ℃ of reactions 2 hours.Be cooled near 50 ℃, vacuum filtration, filtrate vacuum distillation can tell 2,4-diaminourea-3,5-diformazan sulfenyl toluene and 2,6-diaminourea-3,5-diformazan sulfenyl toluene mixture 231 grams, productive rate 94.4%.Filter cake recycles and can reach more than 8 times, still keeps high yield.
Claims (4)
1. the activated carbon carried cuprous iodide catalyst application process in preparation alkylthio group aromatic compound, the cuprous iodide that it is characterized in that chemical precipitation is deposited on the active carbon and is applied to dialkyl group disulfide and aromatic compound prepared in reaction alkylthio group aromatic compound as catalyst, and the content of cuprous iodide is 5%.
2. according to the described method of claim 1, it is characterized in that described activated carbon carried cuprous iodide catalyst is to be immersed in the aqueous solution of copper sulphate and KI or active carbon is immersed in the mixed solution of the ethanol of copper sulphate and iodine and water by active carbon, by the reducing agent reduction and make.
3. according to the described method of claim 2, it is characterized in that described reducing agent is selected from a kind of in formaldehyde, sulfur dioxide, sodium sulfite or the sodium thiosulfate.
4. according to the described method of claim 2, it is characterized in that ethanol and water volume ratio are 2: 8～8: 2 in the mixed solution of described ethanol and water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100843991A CN100431699C (en) | 2006-05-23 | 2006-05-23 | Activated carbon carried cuprous iodide catalyst, and its preparing method and use |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2006100843991A CN100431699C (en) | 2006-05-23 | 2006-05-23 | Activated carbon carried cuprous iodide catalyst, and its preparing method and use |
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|---|---|
| CN1891338A CN1891338A (en) | 2007-01-10 |
| CN100431699C true CN100431699C (en) | 2008-11-12 |
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| CNB2006100843991A Expired - Fee Related CN100431699C (en) | 2006-05-23 | 2006-05-23 | Activated carbon carried cuprous iodide catalyst, and its preparing method and use |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105825990B (en) * | 2016-03-30 | 2017-11-14 | 淮北师范大学 | A kind of CuI Fe3O4The preparation method of magnetic nanocomposites |
| CN105883895A (en) * | 2016-05-25 | 2016-08-24 | 浙江汇能生物股份有限公司 | Preparation method of copper iodide |
| CN106115764B (en) * | 2016-06-23 | 2017-12-12 | 淮北师范大学 | The method that one pot of ball milling solid phase method prepares CuI nano-powders |
| CN106187823B (en) * | 2016-07-04 | 2018-06-22 | 江苏省原子医学研究所 | A kind of method for preparing meta iodobenzyl guanidine |
| CN115612857B (en) * | 2022-10-25 | 2023-10-20 | 昆明理工大学 | Method for selectively recycling gold (III) in waste circuit board leaching solution |
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|---|---|---|---|---|
| EP0132915A1 (en) * | 1983-07-20 | 1985-02-13 | Hidefumi Hirai | Method of preparing solid adsorbent for unsaturated hydrocarbon and process for separation of unsaturated hydrocarbon from gas mixture |
| US5210304A (en) * | 1991-03-11 | 1993-05-11 | Ethyl Corporation | Process for preparing hydrocarbyl aromatic amines |
| US5302755A (en) * | 1991-05-31 | 1994-04-12 | Ethyl Corporation | Method for DMTDA production |
| CN1388117A (en) * | 1998-06-18 | 2003-01-01 | 弗·哈夫曼－拉曼切有限公司 | Process for prodcing 3-aryl sulfate iso-hydroximic acid |
| US6638489B2 (en) * | 2000-09-28 | 2003-10-28 | Japan Pionics Co., Ltd. | Cleaning process and cleaning agent for harmful gas |
-
2006
- 2006-05-23 CN CNB2006100843991A patent/CN100431699C/en not_active Expired - Fee Related
Patent Citations (5)
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|---|---|---|---|---|
| EP0132915A1 (en) * | 1983-07-20 | 1985-02-13 | Hidefumi Hirai | Method of preparing solid adsorbent for unsaturated hydrocarbon and process for separation of unsaturated hydrocarbon from gas mixture |
| US5210304A (en) * | 1991-03-11 | 1993-05-11 | Ethyl Corporation | Process for preparing hydrocarbyl aromatic amines |
| US5302755A (en) * | 1991-05-31 | 1994-04-12 | Ethyl Corporation | Method for DMTDA production |
| CN1388117A (en) * | 1998-06-18 | 2003-01-01 | 弗·哈夫曼－拉曼切有限公司 | Process for prodcing 3-aryl sulfate iso-hydroximic acid |
| US6638489B2 (en) * | 2000-09-28 | 2003-10-28 | Japan Pionics Co., Ltd. | Cleaning process and cleaning agent for harmful gas |
Non-Patent Citations (2)
| Title |
|---|
| A general method for the formation of diaryl selenides usingcopper(I) catalysts. Rttan K. Gujadhur et al.Tetrahedron Letters,Vol.44 . 2003 |
| A general method for the formation of diaryl selenides usingcopper(I) catalysts. Rttan K. Gujadhur et al.Tetrahedron Letters,Vol.44 . 2003 * |
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