Purification technique for the removal of ruthenium from olefin metathesis reaction products

Tetrahedron Letters

Volumn 40, Issue 22, 1999, Pages 4137-4140

  Maynard, Heather D ^a   Grubbs, Robert H ^a  

^a California Institute of Technology   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE; CROWN ETHER; PHOSPHINE DERIVATIVE; RUTHENIUM; RUTHENIUM COMPLEX;

AQUEOUS SOLUTION; ARTICLE; CATALYST; DECOMPOSITION; DISTILLATION; ISOLATION PROCEDURE; POLYMERIZATION; PURIFICATION;

EID: 0033612175     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(99)00726-1     Document Type: Article

References (22)

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3. (b) Schwab, P.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1996, 118, 100-110.
4. For recent reviews of olefin metathesis see: (a) Schuster, M.; Blechert, S. Angew. Chem., Int. Ed. Engl. 1997, 36, 2036-3056. (b) Grubbs, R. H.; Chang, S. Tetrahedron 1998, 54, 4413-4450. (c) Ivin, K. J. J. Mol. Cat. A-Chem. 1998, 133, 1-16.
5. For recent reviews of olefin metathesis see: (a) Schuster, M.; Blechert, S. Angew. Chem., Int. Ed. Engl. 1997, 36, 2036-3056. (b) Grubbs, R. H.; Chang, S. Tetrahedron 1998, 54, 4413-4450. (c) Ivin, K. J. J. Mol. Cat. A-Chem. 1998, 133, 1-16.
6. For recent reviews of olefin metathesis see: (a) Schuster, M.; Blechert, S. Angew. Chem., Int. Ed. Engl. 1997, 36, 2036-3056. (b) Grubbs, R. H.; Chang, S. Tetrahedron 1998, 54, 4413-4450. (c) Ivin, K. J. J. Mol. Cat. A-Chem. 1998, 133, 1-16.
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16. Typical RCM procedure was followed. For example of RCM reaction procedures, see: Kirkland, T.A.; Grubbs, R. H. J. Org. Chem. 1997, 62, 7310-7318.
17. A typical purification procedure is as follows: 3,3-Diethylester-pentene (100 mg, 0.472 mmol) in methylene chloride (0.5 mL) was added to a solution of 2 (293 mg, 2.36 mmol) and triethylamine (657 μg, 4.72 mmol) in methylene chloride (1.5 mL) and stirred for 10 minutes. Water (∼2 mL) was added and the biphasic solution vigorously stirred for 15 mintues. The aqueous layer was separated and the methylene chloride removed in vacuo to isolate the product as a yellow oil.
18. 4]Cl. See reference 4.
19. Samples of approximately 5 mg were precisely weighed on a microbalance, digested overnight with concentrated nitric acid, and diluted to 1% nitric acid. The samples were each measured 10 times and the intensities were obtained for ruthenium isotopes 99, 101, and 102. The intensity of pure 1% nitric acid was subtracted from the sample intensities to give the net intensities. To determine the actual concentration of ruthenium in the samples, the net intensities were compared to that of ruthenium standards. The standards were obtained by diluting a ruthenium standard of 980 μg/mL Ru in 5 wt.% HCl (obtained from Aldrich) with 1% nitric acid to get 2.04, 1.49, 0.98, 0.47, 0.1, 0.05, and 0.01 μg/mL Ru standards where each sample contained less than 0.01 wt.% HCl. The numbers given indicate the average amount of ruthenium obtained for the three isotopes measured.
20. Shido, T.; Okazaki, T.; Ichikawa, M. J. Catal. 1995, 157, 436-449.
21. Marsella, M. J.; Maynard, H. D.; Grubbs, R. H. Angew. Chem., Int. Ed. Engl. 1997, 36, 1101-1103.
22. Vinyl ethers react irreversibly with 1 to form a species inert to metathesis.