Post by Anders Hoveland on Feb 1, 2011 11:54:57 GMT -8
I found a mention to 1,2-diazetidine-1,2-di-N-oxides, which seems potentially interesting. Oxidizing polynitrogenous rings can actually increase stability of the molecule. I would be very interested in 1,3-diazo bridge substituted cyclobutane cages, if they exist. (with a formula C4H6N2).
The name for the cage would be 2,3-diazobicyclo[2.1,1]hexane.
The structure of bicyclo[2.1,1]hexane can be seen here:
elchem.kaist.ac.kr/jhkwak/OkanaganPdb97/nomenclature/pdb/al0059.gif
(the two carbon atoms connected to 3 other carbons are in the 1- and 4- positions.
The 2- and 3- positions are in the ethylene (--CH2CH2--) group which bridges the 1- and 4- positions.
The 5- and 6- positions are in the methylene bridges (--CH2--))
The molecule could best be described by plain text as:
.....CH2CH2
...../......l
HC-CH2-CH
...l......./
.....CH2
"A novel and efficient method for the synthesis of 1,2-diazetidines"
Wei Miaoa, Weiliang Xua, Zhiliu Zhanga, Rujian Ma, Shu-Hui Chena, Ge Li
Summary : A novel and efficient method has been developed for the preparation of racemic or optically pure 1,2-diazetidine from 1-(1-hydroxy-propan-2-yl)hydrazine-1,2-dicarboxylate under very mild conditions with excellent yield.
Basically, HOCH2CH(R)--N(CO2H)--NH(CO2H) either undergoes a Mitsunobu reaction, or reacts with methanesulfonyl chloride CH3SO2Cl. I think the later option is very similar to the Mitsunobu reaction, because
I found an image for EtOCONHN(SO2CH3)CO2Et (there are not any N--O bonds in the structure),
which can be seen here: journals.iucr.org/e/issues/2007/04/00/hg2206/hg2206contents.gif
Then the intermediate is reacted with a base.
Apparently this reaction produces the diazetidine derivitive (R)C2H3N2(CO2H) in 85-96% yield.
This article: www.ncbi.nlm.nih.gov/pubmed/8103389 suggests that 1,2-diazetidine-1,2-di-N-oxides exist, although I am not sure how stable they are. This has an oxygen atom on each nitrogen atom.
One would therfore wonder whether 1-hydroxy-2-hydrazino-cyclobutane could similarly undergo a Mitsunobu reaction to form 2,3-diazobicyclo[2.1,1]hexane. (with a diazo bridge connected to the 1- and 3- positions of the cyclobutane ring, forming a caged molecule.
Alternatively, starting with 1,3-diamino cyclobutane...
upload.wikimedia.org/wikipedia/commons/c/cf/SulfonamideSynthesisfromSO2.png
www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?prep=cv6p0078
The name for the cage would be 2,3-diazobicyclo[2.1,1]hexane.
The structure of bicyclo[2.1,1]hexane can be seen here:
elchem.kaist.ac.kr/jhkwak/OkanaganPdb97/nomenclature/pdb/al0059.gif
(the two carbon atoms connected to 3 other carbons are in the 1- and 4- positions.
The 2- and 3- positions are in the ethylene (--CH2CH2--) group which bridges the 1- and 4- positions.
The 5- and 6- positions are in the methylene bridges (--CH2--))
The molecule could best be described by plain text as:
.....CH2CH2
...../......l
HC-CH2-CH
...l......./
.....CH2
"A novel and efficient method for the synthesis of 1,2-diazetidines"
Wei Miaoa, Weiliang Xua, Zhiliu Zhanga, Rujian Ma, Shu-Hui Chena, Ge Li
Summary : A novel and efficient method has been developed for the preparation of racemic or optically pure 1,2-diazetidine from 1-(1-hydroxy-propan-2-yl)hydrazine-1,2-dicarboxylate under very mild conditions with excellent yield.
Basically, HOCH2CH(R)--N(CO2H)--NH(CO2H) either undergoes a Mitsunobu reaction, or reacts with methanesulfonyl chloride CH3SO2Cl. I think the later option is very similar to the Mitsunobu reaction, because
I found an image for EtOCONHN(SO2CH3)CO2Et (there are not any N--O bonds in the structure),
which can be seen here: journals.iucr.org/e/issues/2007/04/00/hg2206/hg2206contents.gif
Then the intermediate is reacted with a base.
Apparently this reaction produces the diazetidine derivitive (R)C2H3N2(CO2H) in 85-96% yield.
This article: www.ncbi.nlm.nih.gov/pubmed/8103389 suggests that 1,2-diazetidine-1,2-di-N-oxides exist, although I am not sure how stable they are. This has an oxygen atom on each nitrogen atom.
One would therfore wonder whether 1-hydroxy-2-hydrazino-cyclobutane could similarly undergo a Mitsunobu reaction to form 2,3-diazobicyclo[2.1,1]hexane. (with a diazo bridge connected to the 1- and 3- positions of the cyclobutane ring, forming a caged molecule.
Alternatively, starting with 1,3-diamino cyclobutane...
upload.wikimedia.org/wikipedia/commons/c/cf/SulfonamideSynthesisfromSO2.png
www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?prep=cv6p0078