3333-52-6

Usage

Uses

Used in Vinyl Foam Production:
TETRAMETHYLSUCCINONITRILE is used as a blowing agent for vinyl foam production. It helps to create lightweight and flexible foam materials with improved insulation properties.
Used in Pharmaceutical Industry:
TETRAMETHYLSUCCINONITRILE is used in the preparation of 4,5-Dihydro-1,2,3-triazole derivatives, which act as Farnesyltransferase inhibitors. These inhibitors have potential applications in the treatment of various diseases, including cancer and neurodegenerative disorders.
Used in Organic Synthesis:
TETRAMETHYLSUCCINONITRILE can be used as a reactant to synthesize various organic compounds, such as 3,4-Dihydro-3H-pyrrol-2-imines by reacting with aryl lithium species in the presence of TMSCl. This reaction allows for the formation of new chemical entities with potential applications in various fields.
Used in the Synthesis of Metal-Free Fused Tetraazachlorins:
TETRAMETHYLSUCCINONITRILE can also be used in the synthesis of phenyl substituted metal-free fused tetraazachlorins by condensation reaction with substituted phthalonitrile derivatives in the presence of InCl3. These compounds have potential applications in the development of new materials with unique properties.

Synthesis Reference(s)

Journal of the American Chemical Society, 87, p. 4403, 1965 DOI: 10.1021/ja00947a046

Air & Water Reactions

Insoluble in water.

Reactivity Profile

Nitriles, such as TETRAMETHYLSUCCINONITRILE, may polymerize in the presence of metals and some metal compounds. They are incompatible with acids; mixing nitriles with strong oxidizing acids can lead to extremely violent reactions. Nitriles are generally incompatible with other oxidizing agents such as peroxides and epoxides. The combination of bases and nitriles can produce hydrogen cyanide. Nitriles are hydrolyzed in both aqueous acid and base to give carboxylic acids (or salts of carboxylic acids). These reactions generate heat. Peroxides convert nitriles to amides. Nitriles can react vigorously with reducing agents. Acetonitrile and propionitrile are soluble in water, but nitriles higher than propionitrile have low aqueous solubility. They are also insoluble in aqueous acids. TETRAMETHYLSUCCINONITRILE can react violently with (LiAlH4 + H2O).

Hazard

Toxic by inhalation and skin contact. Headache, nausea, and central nervous system convulsions.

Fire Hazard

Flash point data are not available for TETRAMETHYLSUCCINONITRILE, but TETRAMETHYLSUCCINONITRILE is probably combustible.

Safety Profile

Poison by ingestion, intraperitoneal, and intravenous routes. An experimental teratogen. A human skin irritant and allergen. In the preparation of sponge rubber, an azo compound is used that decomposes to form tetramethylsuccinonitrile or TMSN. Rats exposed to a concentration of 90 ppm exhbit their first convulsion after 1.5-2 hours or less. Rats exposed to concentration of 5.5 pprn exhbited their first convulsions in 27-31 hours and were dead in 31-46 hours. Absorbed by skin. The fatal dose in humans is thought to be about 25 mg/kg of body weight. TSN is slowly detoxified by the body. This nitrile is different from other nitriles in that duosulfate is a poor antidote for intoxication. When heated to decomposition it emits toxic fumes of CNand NOx. See also NITRILES and CYANIDE.

Upstream product

• 78-67-1 2,2'-azobis(isobutyronitrile) 
• 100-53-8 phenylmethanethiol 
• 108-88-3 toluene 
• 3001-66-9 octane-2-thiol 
• 111-88-6 Octanethiol 
• 1950-78-3 p-toluenesulfonyl iodide 
• 6244-77-5 4-nitro-N-phenylthiobenzamide 
• 24850-33-7 allyltributylstanane 
• 762-73-2 trimethyl(allyl)stannane 
• 41658-69-9 2-bromo-2-methyl-propionitrile 
• 2417-90-5 bromopropionitrile 
• 34241-39-9 azobisisobutyronitrile 
• 53313-86-3 Bis-(isobutyronitril-2-azo-3'-isovaleroyl)-peroxid 
• 19334-98-6 thiobenz-p-dimethylaminoanilide 

Downstream Products

• 35046-68-5 tetramethylsuccinic anhydride 
• 630-51-3 tetramethyl succinic acid 
• 78-82-0 Isobutyronitrile 
• 13930-88-6 vanadyl phthalocyanine 
• 574-93-6 29H,31H-Phthalocyanine 

Relevant academic research and scientific papers

Reductive Termination of Cyanoisopropyl Radicals by Copper(I) Complexes and Proton Donors: Organometallic Intermediates or Coupled Proton-Electron Transfer?

Cyanoisopropyl radicals, generated thermally by the decomposition of azobis(isobutyronitrile) (AIBN), participate in reductive radical termination (RRT) under the combined effect of copper(I) complexes and proton donors (water, methanol, triethylammonium salts) in acetonitrile or benzene. The investigated copper complexes were formed in situ from [CuI(MeCN)4]+BF4- in CD3CN or CuIBr in C6D6 using tris[2-(dimethylamino)ethyl]amine (Me6TREN), tris(2-pyridylmethyl)amine (TPMA), and 2,2′-bipyridine (BIPY) ligands. Upon keeping all other conditions constants, the impact of RRT is much greater for the Me6TREN and TPMA systems than for the BIPY system. RRT scales with the proton donor acidity (Et3NH+ a‰? H2O > CH3OH), it is reduced by deuteration (H2O > D2O and CH3OH > CD3OD), and it is more efficient in C6D6 than in CD3CN. The collective evidence gathered in this study excludes the intervention of an outer-sphere proton-coupled electron transfer (OS-PCET), while an inner-sphere PCET (IS-PCET) cannot be excluded for coordinating proton donors (water and methanol). On the other hand, the strong impact of RRT for the noncoordinating Et3NH+ in CD3CN results from the formation of an intermediate CuI-radical adduct, suggested by DFT calculations to involve binding via the N atom to yield keteniminato [L/Cu-N=C=CMe2]+ derivatives with only partial spin delocalization onto the Cu atom.

Practical protocols for organotellurium-mediated living radical polymerization by in situ generated initiators from AIBN and ditellurides

A new initiating system for TERP was developed using shelf stable diazo compounds and ditellurides. The obtained polymer possesses an organotellanyl end group, which would be useful for polymer-end manipulations and for block copolymer synthesis.

Solvent and external pressure effects on the ratio of the cyanoisopropyl radical recombination and disproportionation rates

A GC-MS analysis of the azobisisobutyronitrile thermal decomposition products of in solutions at 80 C showed that the ratio of recombination and disproportionation rates of the cyanoisopropyl radical does not depend on the medium viscosity, but increases when the internal pressure of the solvent increases according to the log(k dispr/k rec) = -1.25 + 0.096 P int 0.5 law. This means that the activation volume corresponding to recombination is larger than that corresponding to disproportionation. It follows from the relationship log(k dispr/k rec) = (ΔV rec ≠ - Δv dispr ≠)ΔP/RT that, for the decomposition of the substrate in benzene under a pressure of 0.5-4.0 kbar, the difference between the activation volumes is ΔV rec ≠ - ΔV dispr ≠ = 8 cm3/mol.

Synthesis of difluoromethylselenoesters from aldehydes: Via a radical process

Difluoromethylselenoester compounds, another important kind of organoselenium compounds, are reported herein for the first time. They can be efficiently synthesized from aldehydes and BnSeCF2H. The synthetic method features mild reaction conditions, broad substrate scope, good tolerance of functional groups, and importantly, no metal is involved in the reaction.

The Effect of Viscosity on the Diffusion and Termination Reaction of Organic Radical Pairs

The effect of viscosity on the diffusion efficiency (Fdif) of an organic radical pair in a solvent cage and the termination mechanism, that is, the selectivity of disproportionation (Disp) and combination (Comb) of the geminated caged radical pair and the diffused radicals encountered, were investigated quantitatively by following the photolysis of dimethyl 2,2′-azobis(2-methylpropionate) (V-601) in the absence and presence of PhSD. Fdif and Disp/Comb selectivity outside the cage [Disp(dif)/Comb(dif)] are highly sensitive to the viscosity. In contrast, the Disp/Comb selectivity inside the cage [Disp(cage)/Comb(cage)] is rather insensitive. The difference in viscosity dependence between Disp(cage)/Comb(cage) and Disp(dif)/Comb(dif) is explained by the spin state of the radical pair inside and outside the cage and the spin state dependent configurational changes of the radical pair upon their collision. Given that the configurational change of the radicals associates the displacement and reorganization of solvents around the radicals, the termination outside the cage, which requires larger change than that inside the cage, is highly viscosity dependent. Furthermore, while the bulk viscosity of each solvent shows good correlation with Fdif and Disp/Comb selectivity, microviscosity is the better parameter predicting Fdif and Disp(dif)/Comb(dif) selectivity regardless of the solvents.

Synthesis and properties of bis(biphenyl)chromium(i) 1,4-di(2- cyanoisopropyl)-1,4-dihydrofulleride and 1-(2-cyanoisopropyl)-1,2- dihydrofullerene

Radical-ion salts bis(biphenyl)chromium(i) 1,4-di(2-cyanoisopropyl)-1,4- dihydrofulleride [(Ph2)2Cr]+?[1,4- (CMe2CN)2C60]-? and bis(biphenyl)chromium(i) 1-(2-cyanoisopropyl)-1,2-

Reversible addition-fragmentation chain transfer polymerization: End group modification for functionalized polymers and chain transfer agent recovery

A simple reaction which leads to the full removal of thiocarbonyl, the thio end group from the polymeric chains, and the recovery of the chain transfer agent was discussed. Methyl methacrylate was mixed with S- methoxycarbonylphenylmethyl dithiobenzoate (

Iodine atom transfer addition reaction of 1-iodoalkyl phosphonates to alkenes in the presence of α,α′-azoisobutyronitrile (AIBN): Mechanistic aspects

The objectives of this work were to elucidate the mechanistic pathway of the title reaction, which constitutes the first example of a radical iodine atom transfer addition reaction of non-fluorine-containing phosphonates, and to determine whether 2-iodo-2-methylpropionitrile, 8, can serve as a competing iodine donor with the starting diethyl 1-iodoalkyl phosphonates, 1a,b. The title reaction was found to proceed with AIBN as the sole radical initiator, not requiring poisonous tin reagents as co-initiators, and gave diethyl 3-iodoalkylphosphonates 3a-e (the final products of the propagation step, isolated in 59-95% yield), tetramethylsuccinodinitrile, 9, diethyl methylphosphonate, 4 and tetraethyl ethylenebisphosphonate 5 (all termination products, 0-10% yields). The radical character of this reaction was demonstrated using TEMPO as a radical trap. 8 (the intermediate of the initiation step), synthesized independently from AIBN and iodine, caused complete inhibition of the reaction when added to the reaction mixture, indicating that it does not behave as an iodine donor in the transfer stage, but rather as an inhibitor.

Regioselectivity of the photochemical addition of ammonia, phosphine, and silane to olefinic and acetylenic nitriles

An investigation of the regioselectivity and mechanisms of the photochemical addition of NH3, PH3, and SiH4 to olefinic and acetylenic nitriles is described. The photolysis of NH3 in the presence of acrylonitrile led to the α-addition product 2-aminopropanenitrile (2), propanenitrile, and 2,3-dimethylbutanedinitrile (3). When NH3 was photolyzed in the presence of substituted derivatives (crotononitrile, methacrylonitrile, or 1-cyclohexenecarbonitrile), the α-addition products were still obtained. However, under similar reaction conditions, only the β-addition products, 7 and 8, were obtained from acrylonitrile and PH3, or acrylonitrile and SiH4, respectively. On the other hand, the photolysis of 2-butynenitrile and NH3 gave the β-addition products, (Z)- and (E)-3-aminocrotononitrile (10). The photolysis of these acetylenic nitriles with PH3 or SiH4 also gave the β-adducts (12) and (13). The α-addition of NH3 proceeds by the stepwise addition of H· and ·NH2, respectively, to the α,β-unsaturated nitriles. The β-addition products are formed by a radical chain mechanism initiated by photochemically generated radicals. The radical chain pathway provides an explanation for a number of previously described photochemical additions to olefins and acetylenes. Photochemical processes similar to the addition of ammonia and phosphine to unsaturated organic compounds may have played a role in the evolution of the atmosphere of the primitive Earth, and may even be currently occurring in the atmospheres of other planets.

Reaction of Arenesulphonyl Halides with Free Radicals. Part 3.

The decomposition of azoisobutyronitrile (AIBN) and t-butyl phenylperacetate in the presence of toluene-p-sulphonyl bromide and iodide were studied; results are explained on the basis of free radical reactions.The relative reactivities of several alkane- and arene-sulphonyl chlorides towards phenyl, benzyl, and trichloromethyl radicals were measured in competition experiments.Results are rationalized on the grounds of a balance between polar effects in the initial and in the transition state.