Structure and temperature effects on the cyclization of rigid bisacetylenes

Journal of Organic Chemistry

Volumn 65, Issue 5, 2000, Pages 1588-1589

  Höger, Sigurd ^a   Bonrad, Klaus ^a   Karcher, Lars ^a   Meckenstock, Anne Désirée ^a  

^a MAX PLANCK INSTITUTE FOR POLYMER RESEARCH   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

ACETYLENE DERIVATIVE;

ARTICLE; CYCLIZATION; DIMERIZATION; OXIDATION; REACTION ANALYSIS; SYNTHESIS; TEMPERATURE DEPENDENCE;

EID: 0042795959     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo991644w     Document Type: Article

References (28)

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15. A solution of 0.2 mmol of 1 in 10 mL of dry pyridine was added to a suspension of 1.75 g of CuCl and 0.35 g of CuCb in 40 mL of pyridine in 96 h (with the help of a syringe pump). After completion of the addition, the mixture was allowed to stir for an additional 4 days and then poured into CrCU and water. The organic phase was extracted with water, 25% NHs solution (in order to remove the copper salts), water, 10% acetic acid, water, 10% NaOH solution, and brine and dried over MgSU4. After evaporation of the solvent to a small volume (about 5 mL), the coupling products were precipitated by the addition of methanol and collected by filtration to give the crude product in nearly quantitative yield. The GPC diagrams were measured in THF (flow rate 1 mL min∼:) at room temperature, using a combination of three styragel columns (porosity 103, 105, and 106 A) and an UV detector operating at A = 254 nm.
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18. +L
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24. (0 That solvent molecules can act as templates in the bxidative acetylene coupling has also been proposed: Berscheid, R.; Vögtle, F. Synthesis 1992, 58.
25. An increase of the addition time from 4 to 7 days has within the experimental error no influence on the composition of the crude product. This is in accordance with theoretical predictions, which indicate that the yield of dimer is not a very sensitive function of the rate of addition, and a remarkable increase can only be observed if the rate of addition is changed by several orders of magnitude: Fastrez, J. Tetrahedron Lett. 1987, 28, 419.
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28. +) Da. As also observed previously (ref 11), we were not able to purify the reaction products, either by column chromatography or recrystallization.