Sulfur diimide

Sulfur diimides are chemical compounds of the formula S(NR)2. The parent member, S(NH)2, is of only theoretical interest. Other derivatives where R is an organic group are stable and useful reagents.

Structure of S(NBu-t)2.

Organic derivatives

A particularly stable derivative is di-t-butylsulfurdiimide.[1] A yellow oil, it is prepared by reaction of tert-butylamine with sulfur dichloride to give the intermediate "S(N-t-Bu)", which decomposes at 60 °C to give the diimide. Other routes to sulfur diimides involve treatment of sulfur tetrafluoride with amines. A third route involves transimidation of disulfonylsulfodiimide:

S(NSO2Ph)2 + 2 RNH2 → S(NR)2 + 2 PhSO2NH2

N,N-Bis(methoxycarbonyl)sulfur diimide (MeO2C-N=S=N-CO2Me) is obtained from methylcarbamate.[2]

Structure, bonding, reactions

These compounds are related to SO2. They have planar SN2C2 cores, although both syn and anti isomers are observed.

Sulfur diimides are electrophilic. They undergo Diels-Alder reaction with dienes.[1] Organolithium compounds add to give the corresponding anions:

R'Li + S(NR)2 → R'S(NR)(NRLi)

The triimido analogues of sulfite can be generated by treating the sulfur diimides with amide:[3]

4 LiNHBu-t + 2 S(NBu-t)2 → 2 Li2S(NBu-t)3 + 2 t-BuNH2
gollark: We are not a COUNTRY.
gollark: For users who are citizens of the European Union, we will now be requesting permission before initiating organ harvesting. This software uses an army of frogs that throw cookies in the general direction of your computer. By using it, you agree that these frogs may throw cookies.
gollark: We may use your data for various purposes, such as: responding appropriately to user input/commands providing and managing mandatory software updates communication with users, where necessary - for example to provide notifications about upcoming events and product announcements [LEVEL 5 CLEARANCE REQUIRED] anything PotatOS Things are programmed to do entertainment and/or random messing around helping to deliver, create, develop, improve, design, operate, manage, produce, modernize, complicate, nationalize, placate, evolve, alter, amend, change, obliterate, or worsen our products and services anything whatsoever
gollark: We wish to remind all users that regardless of recent rumors, potatOS is not responsible for and not associated with SCP-3125. SCP-3125 must not be interacted with. “██████ Siri” (PS#ABB85797) must not be interacted with.
gollark: THE SOFTWARE IS PROVIDED “AS IS”, WITHOUT WARRANTY OF ANY KIND, EXPRESS OR IMPLIED, INCLUDING BUT NOT LIMITED TO THE WARRANTIES OF MERCHANTABILITY, FITNESS FOR A PARTICULAR PURPOSE AND NONINFRINGEMENT. IN NO EVENT SHALL THE AUTHORS OR COPYRIGHT HOLDERS BE LIABLE FOR ANY CLAIM, DAMAGES OR OTHER LIABILITY, WHETHER IN AN ACTION OF CONTRACT, TORT OR OTHERWISE, ARISING FROM, OUT OF OR IN CONNECTION WITH THE SOFTWARE OR THE USE OR OTHER DEALINGS IN THE SOFTWARE.

References
  1. Kresze, G.; Wucherpfennig, W., "Organic synthesis with imides of sulfur dioxide", Angew. Chem. Int. Ed. Engl. 1967, volume 6, 149-167. doi:10.1002/anie.196701491
  2. Kresze, Günter; Braxmeier, Hans; Münsterer, Heribert (1987). "Allylcarbamates by the Aza-Ene Reaction: Methyl N-(2-Methyl-2-Butenyl)Carbamate". Organic Syntheses. 65: 159. doi:10.15227/orgsyn.065.0159.
  3. Fleischer, R.; Stalke, D., "A new route to sulfur polyimido anions S(NR)nm-: reactivity and coordination behavior", Coord. Chem. Rev. 1998, 176, 431-450. doi:10.1016/S0010-8545(98)00130-1
This article is issued from Wikipedia. The text is licensed under Creative Commons - Attribution - Sharealike. Additional terms may apply for the media files.