Carbonylation of Amino Amides and Amines to Ureas and Formamides

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Material Information

Title:
Carbonylation of Amino Amides and Amines to Ureas and Formamides
Physical Description:
1 online resource (128 p.)
Language:
english
Creator:
Johns, Jennifer Ilene
Publisher:
University of Florida
Place of Publication:
Gainesville, Fla.
Publication Date:

Thesis/Dissertation Information

Degree:
Doctorate ( Ph.D.)
Degree Grantor:
University of Florida
Degree Disciplines:
Chemistry
Committee Chair:
MCELWEE-WHITE,LISA ANN
Committee Co-Chair:
VEIGE,ADAM S
Committee Members:
APONICK,AARON
MILLER,STEPHEN ALBERT
PERCIVAL,SUSAN S

Subjects

Subjects / Keywords:
carbonylation -- dihydrouracil -- formamide -- hydantoin
Chemistry -- Dissertations, Academic -- UF
Genre:
Chemistry thesis, Ph.D.
bibliography   ( marcgt )
theses   ( marcgt )
government publication (state, provincial, terriorial, dependent)   ( marcgt )
born-digital   ( sobekcm )
Electronic Thesis or Dissertation

Notes

Abstract:
W(CO)6-catalyzed oxidative carbonylation ofamines to ureas provides an alternative to stoichiometric reaction of amineswith phosgene or its derivatives such as 1,1-carbonyldiimidazole (CDI). Due tothe successful synthesis of a range of cyclic targets employing W(CO)6 as catalyst, CO as the carbonyl source, and I2 as oxidant, alpha- and beta-amino amides were explored as carbonylation substrates to afford hydantoins and dihydrouracils. Hydantoins were synthesized in moderate to good yields with substitution at the amide and C-5 position. Carbonylation of beta-amino amides proved to be sensitive to substitution at the beta-alkyl position, as the beta-alkyl and aryl substituted substrates resulted in acyclic urea formation, whereas a-alkyl substitution or no substitution resulted in carbonylation to the dihydrouracil.The catalytic method was also expanded to the synthesis of unsymmetrical diarylureas that were previously inaccessible from carbonylation of aniline substrates. Reaction scope was successfully extended to new classes ofbiologically active molecules with hydantoins, dihydrouracils, and diarylureas. Base-mediatedcarbonylation of amines to formamides provides a metal-free alternative synthesis which does not involve high temperatures or stoichiometric amounts of formic acid. The optimized reaction conditions for the synthesis of formamides from benzyl amines were 35 atm CO and 3 equivalents of K2CO3in methanol solvent for 7 h at room temperature. A reaction time of 24 hensured the reaction completed for less reactive substrates. Carbonylation toformamides had reasonably broad substrate scope including primary, cyclicsecondary, and substituted benzylamines. Electron rich benzylamines proved tobe the most reactive and gave the best yields
General Note:
In the series University of Florida Digital Collections.
General Note:
Includes vita.
Bibliography:
Includes bibliographical references.
Source of Description:
Description based on online resource; title from PDF title page.
Source of Description:
This bibliographic record is available under the Creative Commons CC0 public domain dedication. The University of Florida Libraries, as creator of this bibliographic record, has waived all rights to it worldwide under copyright law, including all related and neighboring rights, to the extent allowed by law.
Statement of Responsibility:
by Jennifer Ilene Johns.
Thesis:
Thesis (Ph.D.)--University of Florida, 2013.
Local:
Adviser: MCELWEE-WHITE,LISA ANN.
Local:
Co-adviser: VEIGE,ADAM S.
Electronic Access:
RESTRICTED TO UF STUDENTS, STAFF, FACULTY, AND ON-CAMPUS USE UNTIL 2015-12-31

Record Information

Source Institution:
UFRGP
Rights Management:
Applicable rights reserved.
Classification:
lcc - LD1780 2013
System ID:
UFE0046187:00001