CN101891606B - New method for synthesizing rhodium caprylate (II) - Google Patents
New method for synthesizing rhodium caprylate (II) Download PDFInfo
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- CN101891606B CN101891606B CN 201010239635 CN201010239635A CN101891606B CN 101891606 B CN101891606 B CN 101891606B CN 201010239635 CN201010239635 CN 201010239635 CN 201010239635 A CN201010239635 A CN 201010239635A CN 101891606 B CN101891606 B CN 101891606B
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Abstract
The invention discloses a new method for synthesizing rhodium caprylate (II), which is characterized by comprising the following steps: dissolving a certain amount of rhodium chloride in water; adding 120 to 300 theoretical percent of octylic acid into the water, and adjusting the pH valve of the obtained solution to between 4.5 and 6.5 by using alkali; heating the solution to the temperature of between 90 DEG C and 100 DEG C, reacting for 3 to 5 hours, and filtering the solution when the solution is hot; and fully washing by using water, and drying to obtain a green rhodium caprylate (II) product. The method for synthesizing the rhodium caprylate (II) has the advantages of high reaction speed, high yield (over 95 percent), high product purity (over 99 percent), small environmental pollution, and suitability for industrial production.
Description
Technical field
The present invention relates to the synthetic method of a kind of rhodium homogeneous catalyst-sad rhodium (II), belong to chemical field.
Background technology
Sad rhodium (II) is widely used in basic chemical industry and field of medicine and chemical technology because cyclopropanization reaction and hydrogenation of olefins formylation reaction are had significant catalytic activity, is an important rhodium homogeneous catalyst.Sad rhodium (II) be the earliest 1986 by Giround-Godguin, the people such as A.M. report.Yet they only mention and adopt the ligand exchange method to synthesize, concrete synthetic method does not have play-by-play, and its characterizing method also only limits to ultimate analysis (Giround-Godguin AM, Marchon JC, Daniel G, AntoineS, Discotic Mesophases of Dirhodlum Tetracarboxylates, J Phys Chem, 1986,90,5502-5503).Chisholm subsequently, M.H. employing acetic acid rhodium (II) and the sad ligand exchange reaction that carries out synthesize sad rhodium (II) method to have waited people's play-by-play, but its reaction process is long, yield is low, is not suitable for industrial production (Chisholm MH, Christou G, Folting K, Huffman JC, JamesCA, Samuels JA, Wesemann JL, and.Woodruff WH, Solution Studies ofRu
2(O
2CR)
4 N+Complexes (n=0,1; O
2CR=Octanoate, Crotonate, Dimethylacrylate, Benzoate, p-Toluate) and Solid-State Structures ofRu
2(O
2C-p-tolyl)
4(THF)
2, [Ru
2(O
2C-p-tolyl)
4(THF)
2]
+[BF4]
-, andRu
2(O
2C-p-tolyl)
4(CH
3CN)
2: Investigations of the Axiai Ligation of the Ru
2Core, Inorg.Chem.1996,35,3643-3658).The people such as Qin Yongnian adopt apparatus,Soxhlet's that acetic acid rhodium (II) and sad reaction yield are brought up to more than 98% on the basis of ligand exchange method, but calculate from the raw material Trichlororhodium, total recovery only about 70%, and equally also there are the shortcomings such as reactions steps is many, long reaction time, complicated operation in its reaction.In addition; the ligand exchange method all relates to the separation problem of a sad and sad rhodium (II); because the solubleness of sad rhodium (II) in sad is very large; simultaneously sad boiling point very high (237 ℃); therefore its separation is very difficult; usually all need to use the toxic reagents such as toluene, chlorobenzene, be unfavorable for environment protection.
Summary of the invention
The novel method that the purpose of this invention is to provide a kind of synthetic sad rhodium (II), the method are take rhodium mineral compound Trichlororhodium commonly used as starting raw material, direct and sad reaction in the aqueous solution, and a step obtains sad rhodium (II) product.This reactions steps is few, and productive rate is high, and the product purity that obtains is high; Because the employed solvent of synthetic method of the present invention is water, therefore can overcome the environmental issue in synthetic sad rhodium (II) process of ligand exchange method simultaneously.
Synthetic method of the present invention is with Trichlororhodium and sad being dissolved in the aqueous solution, regulates certain pH value with alkali, and reacting by heating is after for some time, and filtration, washing, drying obtain sad rhodium (II) product.
The preferred used alkali of the present invention is the oxyhydroxide of basic metal or alkaline-earth metal.
The preferred used pH value of the present invention is 4.5～6.5.
Preferred preparation method of the present invention may further comprise the steps:
Trichlororhodium is water-soluble, add the sad of theoretical amount 120%～300%, the pH value of regulator solution is 4.5～6.5, be heated to 90～100 ℃, reacted 3～5 hours, then filtered while hot, after water fully washed, drying obtained green sad rhodium (II) product.
The characteristics of sad rhodium of the present invention (II) synthetic method be adopt simple inorganic rhodium compound Trichlororhodium with sad in the aqueous solution single step reaction obtain sad rhodium (II) product, this speed of response is fast, productive rate height (＞95%); Product purity high (＞99%); Environmental pollution is little, is fit to industrialization production requirements.
Embodiment
Taking by weighing 5.30 gram (22.5mmol) three water Trichlororhodiums is dissolved in the 100mL water, it is sad under agitation to add 9.5mL, is heated to boiling, and the NaOH solution with 10% is regulated pH value to 5, back flow reaction 4 hours, temperature of reaction is 95 ℃, obtains green product, filtered while hot, be neutral with hot wash to washing lotion, 80 ℃ of vacuum-dryings got 7.55 gram sad rhodiums (II) in 2 hours, productive rate 96.5%, and adopting the HPLC purity assay is 98.7%.
Feature structure parameter:＜1〉ultimate analysis: measured value C 49.3%, H 7.8%, Rh 26.3% and theoretical value C 49.4%, H 7.8%, and Rh 26.5% is consistent.<2>MS-FAB
+m/z：727([M-Octanoate+glycerin]
+，100％)，778(M
+，45％)，871([M+glycerin+1]
+，55％)。<3>IR(cm
-1，KBr)2954，2922，2851(m，v
C-H)，1567(s，v
asC＝0)，1433，1412(s，v
sC＝0)。<4>
1H-NMR(CDCl
3+CD
3OD，ppm)：0.80(t，12H，4CH
3)，1.05-1.22(m，32H，16CH
2(4-7))，1.38(m，8H，4CH
2(3))，2.08(t，8H，4CH
2(2)).<5>
13C-NMR(CDCl
3+CD
3OD，ppm)：13.89(CH
3)，22.47，25.73，28.75，28.82，31.58，37.06(CH
2)，193.56(COO)。These parameters meet the chemical structure of the compound of inventing.
Claims (1)
1. the method for a synthetic sad rhodium (II) is characterized in that preparation process may further comprise the steps:
Taking by weighing 5.30 grams, three water Trichlororhodiums is dissolved in the 100mL water, it is sad under agitation to add 9.5mL, be heated to boiling, the NaOH solution with 10% is regulated pH value to 5, back flow reaction 4 hours, temperature of reaction is 95 ℃, obtain green product, filtered while hot is neutral with hot wash to washing lotion, 80 ℃ of vacuum-dryings got 7.55 gram sad rhodiums (II), productive rate 96.5% in 2 hours.
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| CN 201010239635 CN101891606B (en) | 2010-07-29 | 2010-07-29 | New method for synthesizing rhodium caprylate (II) |
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| CN101891606A CN101891606A (en) | 2010-11-24 |
| CN101891606B true CN101891606B (en) | 2013-03-13 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102180783B (en) * | 2011-02-25 | 2013-06-12 | 昆明贵金属研究所 | Method for selectively separating rhodium (II) acetate from rhodium (II) acetate recrystallization waste liquor |
| CN102786406A (en) * | 2012-08-08 | 2012-11-21 | 陕西瑞科新材料股份有限公司 | Preparation method of rhodium caprylate |
| CN105669429B (en) * | 2016-03-10 | 2018-08-10 | 昆明理工大学 | A kind of preparation method of rhodium caprylate |
| CN106831399B (en) * | 2017-01-23 | 2020-05-05 | 杭州凯大催化金属材料股份有限公司 | Synthetic method of 2-ethylhexanoic acid rhodium (II) |
| CN109111357A (en) * | 2018-09-03 | 2019-01-01 | 贵研铂业股份有限公司 | It is a kind of can volume production rhodium caprylate dimer synthetic method |
| CN111718253B (en) * | 2020-06-24 | 2022-12-13 | 上海沃凯生物技术有限公司 | Preparation method of rhodium caprylate dimer |
| CN112961189A (en) * | 2021-02-09 | 2021-06-15 | 上海沃凯生物技术有限公司 | Synthetic method of rhodium (II) carboxylate dimer |
| CN114573443A (en) * | 2022-03-17 | 2022-06-03 | 金川集团股份有限公司 | Low-chlorine preparation method of rhodium caprylate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101353301A (en) * | 2008-09-19 | 2009-01-28 | 浙江省冶金研究院有限公司 | Synthetic process of rhodium caprylate dimer |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101353301A (en) * | 2008-09-19 | 2009-01-28 | 浙江省冶金研究院有限公司 | Synthetic process of rhodium caprylate dimer |
Non-Patent Citations (6)
| Title |
|---|
| "Discotic mesophases of dirhodium tetracarboxylates";Anne-Marie Giroud-Godquin et al.;《Journal of Physical Chemistry》;19861231;第90卷;第5502-5503页 * |
| "Homoleptic dirhodium tetraoctanoate and its pyridine adduct:synthesis and crystal structures ";Qing-Song Ye et al.;《Transition Metal Chemistry》;20100521;第35卷;第585-590页 * |
| "TETRAKIS(ACETAT0)DIRHODIUM (II) AND SIMILAR CARBOXYLATO COMPOUNDS";G.A.REMPEL et al.;《Inorganic Syntheses》;19721231;第13卷;第90-91页 * |
| Anne-Marie Giroud-Godquin et al.."Discotic mesophases of dirhodium tetracarboxylates".《Journal of Physical Chemistry》.1986,第90卷第5502-5503页. |
| G.A.REMPEL et al.."TETRAKIS(ACETAT0)DIRHODIUM (II) AND SIMILAR CARBOXYLATO COMPOUNDS".《Inorganic Syntheses》.1972,第13卷第90-91页. |
| Qing-Song Ye et al.."Homoleptic dirhodium tetraoctanoate and its pyridine adduct:synthesis and crystal structures ".《Transition Metal Chemistry》.2010,第35卷第585-590页. |
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| CN101891606A (en) | 2010-11-24 |
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Application publication date: 20101124 Assignee: Your research resources (Yimen) Co. Ltd. Assignor: Guiyan Platinum Industry Co., Ltd. Contract record no.: 2013530000030 Denomination of invention: New method for synthesizing rhodium caprylate (II) Granted publication date: 20130313 License type: Exclusive License Record date: 20130419 |
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Effective date of registration: 20160321 Address after: 650106 No. 988, science and technology road, Kunming hi tech Development Zone, Yunnan Patentee after: R & D testing technology (Yunnan) Co., Ltd. Address before: 650106, 988 hi tech Development Zone, Yunnan, Kunming (Limited by Share Ltd) Patentee before: Guiyan Platinum Industry Co., Ltd. |