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Title: Photochemical dimerization of organic compounds

Abstract

At least one of selectivity and reaction rate of photosensitized vapor phase dimerizations, including dehydrodimerizations, hydrodimerizations and cross-dimerizations of saturated and unsaturated organic compounds is improved by conducting the dimerization in the presence of hydrogen or nitrous oxide.

Inventors:
 [1];  [2];  [3];  [4]
  1. (Bethany, CT)
  2. (Princeton, NJ)
  3. (New Haven, CT)
  4. (Branford, CT)
Publication Date:
Research Org.:
Yale University
OSTI Identifier:
868239
Patent Number(s):
US 5104503
Assignee:
Yale University (New Haven, CT) CHO
DOE Contract Number:
FG02-84ER13297
Resource Type:
Patent
Country of Publication:
United States
Language:
English
Subject:
photochemical; dimerization; organic; compounds; selectivity; reaction; rate; photosensitized; vapor; phase; dimerizations; including; dehydrodimerizations; hydrodimerizations; cross-dimerizations; saturated; unsaturated; improved; conducting; presence; hydrogen; nitrous; oxide; photochemical dimerization; reaction rate; organic compound; organic compounds; vapor phase; nitrous oxide; unsaturated organic; /204/

Citation Formats

Crabtree, Robert H., Brown, Stephen H., Muedas, Cesar A., and Ferguson, Richard R. Photochemical dimerization of organic compounds. United States: N. p., 1992. Web.
Crabtree, Robert H., Brown, Stephen H., Muedas, Cesar A., & Ferguson, Richard R. Photochemical dimerization of organic compounds. United States.
Crabtree, Robert H., Brown, Stephen H., Muedas, Cesar A., and Ferguson, Richard R. Wed . "Photochemical dimerization of organic compounds". United States. doi:. https://www.osti.gov/servlets/purl/868239.
@article{osti_868239,
title = {Photochemical dimerization of organic compounds},
author = {Crabtree, Robert H. and Brown, Stephen H. and Muedas, Cesar A. and Ferguson, Richard R.},
abstractNote = {At least one of selectivity and reaction rate of photosensitized vapor phase dimerizations, including dehydrodimerizations, hydrodimerizations and cross-dimerizations of saturated and unsaturated organic compounds is improved by conducting the dimerization in the presence of hydrogen or nitrous oxide.},
doi = {},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Wed Jan 01 00:00:00 EST 1992},
month = {Wed Jan 01 00:00:00 EST 1992}
}

Patent:

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  • This patent describes improvement in a Group IIb photosensitized vapor phase dimerization of an organic compound in which a gaseous mixture of a Group IIB metal and the organic compound is irradiated in a reaction zone with a photosensitizing amount of radiant energy. The improvement comprises: a continuous stream of the gaseous mixture is passed as a vapor phase in a single pass through the reaction zone at a temperature at which the thus-produced dimer condenses immediately upon the formation thereof; the starting gaseous mixture comprises hydrogen and two ethylenically unsaturated compounds selected from the group consisting of alkenes ofmore » at least six carbon atoms, unsaturated nitriles, unsaturated epoxides, unsaturated silanes, unsaturated amines, unsaturated phosphines, and fluorinated alkenes; the gaseous mixture comprises nitrous oxide and the organic compound is a saturated compound with C-H bond strengths greater than 100 kcal/mol or a mixture of the saturated compound and an alkene; or the starting gaseous comprises an activating amount of hydrogen and the dimerization is a dehydrodimerization or cross-dimerization of a saturated hydrocarbon.« less
  • The space-time yield and/or the selectivity of the photochemical dimerization of alkanes, ethers, primary alcohols and tertiary silanes with Hg and U.V. light is enhanced by refluxing the substrate in the irradiated reaction zone at a temperature at which the dimer product condenses and remains condensed promptly upon its formation. Cross-dimerization of the alkanes, ethers and silanes with primary alcohols is disclosed, as is the functionalization to aldehydes of the alkanes with carbon monoxide.
  • The space-time yield and/or the selectivity of the photochemical dimerization of alkanes, ethers, primary and secondary alcohols, phosphine oxides and primary, secondary and tertiary silanes with Hg and U.V. light is enhanced by refluxing the substrate in the irradiated reaction zone at a temperature at which the dimer product condenses and remains condensed promptly upon its formation. Cross-dimerization of the alkanes, ethers and silanes with primary alcohols is disclosed, as is the functionalization to aldehydes of the alkanes with carbon monoxide.
  • The space-time yield and/or the selectivity of the photochemical dimerization of alkanes, ethers, primary alcohols and tertiary silanes with Hg and U.V. light is enhanced by refluxing the substrate in the irradiated reaction zone at a temperature at which the dimer product condenses and remains condensed promptly upon its formation. Cross-dimerization of the alkanes, ethers and silanes with primary alcohols is disclosed, as is the functionalization to aldehydes of the alkanes with carbon monoxide.
  • The space-time yield and/or the selectivity of the photochemical dimerization of alkanes, ethers, primary and secondary alcohols, phosphine oxides and primary, secondary and tertiary silanes with Hg and U.V. light is enhanced by refluxing the substrate in the irradiated reaction zone at a temperature at which the dimer product condenses and remains condensed promptly upon its formation. Cross-dimerization of the alkanes, ethers and silanes with primary alcohols is disclosed, as is the functionalization to aldehydes of the alkanes with carbon monoxide.