Copper(I) chloride catalyzed cross-dehydrocoupling reactions between silanes and ethynyl compounds. A new method for the copolymerization of silanes and alkynes
In the presence of an amine, copper(I) chloride is an effective catalyst for the cross-dehycrocoupling of silanes with alkynes. The reactions proceed at useful rates above 100 °C, but rates drop dramatically on going from 1° to 2° to 3° organosilanes. Primary silanes, RSiH 3 (R = Ph,n-hexyl), react...
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| Veröffentlicht in: | Canadian journal of chemistry 1990-07, Vol.68 (7), p.1100-1105 |
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| container_title | Canadian journal of chemistry |
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| creator | Liu, Hua Qin Harrod, John F |
| description | In the presence of an amine, copper(I) chloride is an effective catalyst for the cross-dehycrocoupling of silanes with alkynes. The reactions proceed at useful rates above 100 °C, but rates drop dramatically on going from 1° to 2° to 3° organosilanes. Primary silanes, RSiH
3
(R = Ph,n-hexyl), react in a stepwise fashion with phenylacetylene to give the products RSiH
3−x
(CCPh)
x
(x = 1-3), each of which has been isolated and characterized. The secondary silanes RR′SiH
2
(R = R′ = Ph; R = Ph, R′ = Me; R = n-Bu, R′ = Me) also give mono- and diphenylethynyl products. The dehydrocoupling reaction has been applied to the synthesis of new polymers containing both acetylene units and silicon atoms in the backbone. 1,3-Diethynylbenzene gives polymers of relatively high molecular weight
with phenylsilane and phenylmethylsilane, but reactions of phenylmethyldiethynylsilane are too slow to give anything beyond low molecular weight oligomers. Keywords: organosilanes, alkynes, dehydrocoupling, copper(I) chloride, polymers, catalysis. |
| doi_str_mv | 10.1139/v90-170 |
| format | Article |
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3
(R = Ph,n-hexyl), react in a stepwise fashion with phenylacetylene to give the products RSiH
3−x
(CCPh)
x
(x = 1-3), each of which has been isolated and characterized. The secondary silanes RR′SiH
2
(R = R′ = Ph; R = Ph, R′ = Me; R = n-Bu, R′ = Me) also give mono- and diphenylethynyl products. The dehydrocoupling reaction has been applied to the synthesis of new polymers containing both acetylene units and silicon atoms in the backbone. 1,3-Diethynylbenzene gives polymers of relatively high molecular weight
with phenylsilane and phenylmethylsilane, but reactions of phenylmethyldiethynylsilane are too slow to give anything beyond low molecular weight oligomers. Keywords: organosilanes, alkynes, dehydrocoupling, copper(I) chloride, polymers, catalysis.</description><identifier>ISSN: 0008-4042</identifier><identifier>EISSN: 1480-3291</identifier><identifier>DOI: 10.1139/v90-170</identifier><identifier>CODEN: CJCHAG</identifier><language>eng</language><publisher>Ottawa, Canada: NRC Research Press</publisher><subject>Chemistry ; Exact sciences and technology ; Organic chemistry ; Organometalloidal and organometallic compounds ; Preparations and properties ; Si derivatives</subject><ispartof>Canadian journal of chemistry, 1990-07, Vol.68 (7), p.1100-1105</ispartof><rights>1991 INIST-CNRS</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c317t-febb3ccd907ef6e39d95262fdbc6e8983f189690b3bc88188cbd0981dbe96a943</citedby></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://cdnsciencepub.com/doi/pdf/10.1139/v90-170$$EPDF$$P50$$Gnrcresearch$$H</linktopdf><linktohtml>$$Uhttps://cdnsciencepub.com/doi/full/10.1139/v90-170$$EHTML$$P50$$Gnrcresearch$$H</linktohtml><link.rule.ids>314,780,784,2932,27924,27925,64428,65234</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=19359853$$DView record in Pascal Francis$$Hfree_for_read</backlink></links><search><creatorcontrib>Liu, Hua Qin</creatorcontrib><creatorcontrib>Harrod, John F</creatorcontrib><title>Copper(I) chloride catalyzed cross-dehydrocoupling reactions between silanes and ethynyl compounds. A new method for the copolymerization of silanes and alkynes</title><title>Canadian journal of chemistry</title><addtitle>Revue canadienne de chimie</addtitle><description>In the presence of an amine, copper(I) chloride is an effective catalyst for the cross-dehycrocoupling of silanes with alkynes. The reactions proceed at useful rates above 100 °C, but rates drop dramatically on going from 1° to 2° to 3° organosilanes. Primary silanes, RSiH
3
(R = Ph,n-hexyl), react in a stepwise fashion with phenylacetylene to give the products RSiH
3−x
(CCPh)
x
(x = 1-3), each of which has been isolated and characterized. The secondary silanes RR′SiH
2
(R = R′ = Ph; R = Ph, R′ = Me; R = n-Bu, R′ = Me) also give mono- and diphenylethynyl products. The dehydrocoupling reaction has been applied to the synthesis of new polymers containing both acetylene units and silicon atoms in the backbone. 1,3-Diethynylbenzene gives polymers of relatively high molecular weight
with phenylsilane and phenylmethylsilane, but reactions of phenylmethyldiethynylsilane are too slow to give anything beyond low molecular weight oligomers. Keywords: organosilanes, alkynes, dehydrocoupling, copper(I) chloride, polymers, catalysis.</description><subject>Chemistry</subject><subject>Exact sciences and technology</subject><subject>Organic chemistry</subject><subject>Organometalloidal and organometallic compounds</subject><subject>Preparations and properties</subject><subject>Si derivatives</subject><issn>0008-4042</issn><issn>1480-3291</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>1990</creationdate><recordtype>article</recordtype><recordid>eNp9kE1LAzEQhoMoWKv4F3LxE7Ymm-02OZbiR6HgRc9LNpm4q2myJFvL9tf4U91aQTzoaWaYh2eYF6FTSkaUMnHzLkhCJ2QPDWjGScJSQffRgBDCk4xk6SE6ivG1HyckHQ_Qx8w3DYTL-RVWlfWh1oCVbKXtNqCxCj7GREPV6eCVXzW2di84gFRt7V3EJbRrAIdjbaWDiKXTGNqqc53Fyi8bv3I6jvAUO1jjZb_xGhsfcFv1V3zjbbeEUG_k1oa9-eWR9q3r-2N0YKSNcPJdh-j57vZp9pAsHu_ns-kiUYxO2sRAWTKltCATMDkwocU4zVOjS5UDF5wZykUuSMlKxTnlXJWaCE51CSKXImNDdLHzfv0cwBRNqJcydAUlxTbYog-26IPtybMd2ciopDVBOlXHH1ywseBj1nPXO84FFSCCDKr6R3r-N_wNFY027BNFVpiH</recordid><startdate>19900701</startdate><enddate>19900701</enddate><creator>Liu, Hua Qin</creator><creator>Harrod, John F</creator><general>NRC Research Press</general><general>National Research Council of Canada</general><scope>IQODW</scope><scope>AAYXX</scope><scope>CITATION</scope></search><sort><creationdate>19900701</creationdate><title>Copper(I) chloride catalyzed cross-dehydrocoupling reactions between silanes and ethynyl compounds. A new method for the copolymerization of silanes and alkynes</title><author>Liu, Hua Qin ; Harrod, John F</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c317t-febb3ccd907ef6e39d95262fdbc6e8983f189690b3bc88188cbd0981dbe96a943</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>1990</creationdate><topic>Chemistry</topic><topic>Exact sciences and technology</topic><topic>Organic chemistry</topic><topic>Organometalloidal and organometallic compounds</topic><topic>Preparations and properties</topic><topic>Si derivatives</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Liu, Hua Qin</creatorcontrib><creatorcontrib>Harrod, John F</creatorcontrib><collection>Pascal-Francis</collection><collection>CrossRef</collection><jtitle>Canadian journal of chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Liu, Hua Qin</au><au>Harrod, John F</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Copper(I) chloride catalyzed cross-dehydrocoupling reactions between silanes and ethynyl compounds. A new method for the copolymerization of silanes and alkynes</atitle><jtitle>Canadian journal of chemistry</jtitle><addtitle>Revue canadienne de chimie</addtitle><date>1990-07-01</date><risdate>1990</risdate><volume>68</volume><issue>7</issue><spage>1100</spage><epage>1105</epage><pages>1100-1105</pages><issn>0008-4042</issn><eissn>1480-3291</eissn><coden>CJCHAG</coden><abstract>In the presence of an amine, copper(I) chloride is an effective catalyst for the cross-dehycrocoupling of silanes with alkynes. The reactions proceed at useful rates above 100 °C, but rates drop dramatically on going from 1° to 2° to 3° organosilanes. Primary silanes, RSiH
3
(R = Ph,n-hexyl), react in a stepwise fashion with phenylacetylene to give the products RSiH
3−x
(CCPh)
x
(x = 1-3), each of which has been isolated and characterized. The secondary silanes RR′SiH
2
(R = R′ = Ph; R = Ph, R′ = Me; R = n-Bu, R′ = Me) also give mono- and diphenylethynyl products. The dehydrocoupling reaction has been applied to the synthesis of new polymers containing both acetylene units and silicon atoms in the backbone. 1,3-Diethynylbenzene gives polymers of relatively high molecular weight
with phenylsilane and phenylmethylsilane, but reactions of phenylmethyldiethynylsilane are too slow to give anything beyond low molecular weight oligomers. Keywords: organosilanes, alkynes, dehydrocoupling, copper(I) chloride, polymers, catalysis.</abstract><cop>Ottawa, Canada</cop><pub>NRC Research Press</pub><doi>10.1139/v90-170</doi><tpages>6</tpages></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 0008-4042 |
| ispartof | Canadian journal of chemistry, 1990-07, Vol.68 (7), p.1100-1105 |
| issn | 0008-4042 1480-3291 |
| language | eng |
| recordid | cdi_crossref_primary_10_1139_v90_170 |
| source | NRC Research Press; EZB-FREE-00999 freely available EZB journals; Free Full-Text Journals in Chemistry |
| subjects | Chemistry Exact sciences and technology Organic chemistry Organometalloidal and organometallic compounds Preparations and properties Si derivatives |
| title | Copper(I) chloride catalyzed cross-dehydrocoupling reactions between silanes and ethynyl compounds. A new method for the copolymerization of silanes and alkynes |
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