A polymer-bound 1,3-diketone: A highly efficient scavenger for hydrazines, and primary amines

Synlett

Volumn , Issue 7, 2003, Pages 983-986

  Schön, Uwe ^b   Messinger, Josef ^b   Merayo, Nuria ^a   Juszkiewicz, Grzegorz ^b   Kirschning, Andreas ^a  

^a LEIBNIZ UNIVERSITY HANNOVER   (Germany)

^b Solvay Pharmaceuticals GmbH   (Germany)

Author keywords

Amines; Combinatorial chemistry; Hydrazines; Polymer supported reagent; Scavenger resin

Indexed keywords

1,3 DIKETONE; AMINE; ENAMINE; HYDRAZINE DERIVATIVE; KETONE DERIVATIVE; PYRAZOLE DERIVATIVE; RESIN; SCAVENGER; UNCLASSIFIED DRUG;

ALKYLATION; ARTICLE; CHEMICAL BINDING; CHEMICAL PROCEDURES; PURIFICATION; REDUCTION;

EID: 0037562429     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-2003-39295     Document Type: Article

References (24)

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19. 5. The dried resin (ca. 2.2 g) was suspended in dry dichloromethane (30 mL) and sodium iodide (8.24 g, 55 mmol) was added. Gentle stirring was continued under nitrogen and trimethylchlorosilane (6.98 mL, 55 mmol) and acetylacetone (1.65 mL, 16 mmol) were added separately during 6 h via a syringe pump. The mixture was gently stirred overnight at r.t. and then treated with water (50 mL). After 10 min the resin was filtered and successively washed with methanol, water, methanol, acetone, dichloromethane, methanol, and dried in high vacuum. It has to be pointed out that after thorough optimization we had to notice the need for excessive washing of the resin before use, because it tends to bind impurities including iodine. Resin 3 can be stored at 4 °C and stays active for months. The commercial Merrifield resin 5 as well as 1,3-diketone resin 3 were analyzed by combustion analysis. Found for 5: C 77.63, H 6.37, C1 15.69 (equals about 4.42 mmol/g loading); found for 3: C 79.55, H 7. 17, Cl 0.47 (equals about 3.37 mmol/g loading).
20. 2 at room temperature within eight hours.
21. Typical scavenger procedure with 1: To a solution of ethylcarbazate (16 mg, 0.165 mmol) in dichloromethane (1 mL) was added benzaldehyde resin 1 (150 mg, 3.0 mmol aldehyde/g) and stirred at r.t. until all hydrazine has reacted. The procedure was monitored with TLC or GC. After 72 h the suspension was filtered, the resin was washed with dichloromethane (3 x 2 mL), and the combined filtrates were evaporated in high vacuum. No residue remained in the flask. Typical scavenger procedure with 3: To a solution of ethylcarbazate (17 mg, 0.165 mmol) in dichloromethane (1 mL) was added 2,4-pentandione resin 3 (100 mg, 3.3 mmol diketone/g) and stirred at r.t. until all hydrazine has reacted. The procedure was monitored with TLC or GC. After 3 h the suspension was filtered, the resin was washed with dichloromethane (3 x 2 mL), and the combined filtrates were evaporated under high vacuum. No residue was found in the flask.
22. Commonly, hydrazines were completely scavenged within the given time. Occasionally, we observed a residue after filtration and evaporation of the solvent which originated from resin impurities.
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24. Kirschning, A.; Monenschein, H.; Wittenberg, R. Chem.-Eur. J. 2000, 6, 4445.