Search

The n-propyl and i-propyl radicals were generated in the gas phase via pyrolysis of n-butyl nitrite [CH3(CH2)3ONO] and i-butyl nitrite [(CH3)2CHCH2ONO], respectively. Nascent radicals were promptly solvated by a beam of He nanodroplets, and the infrared spectra of the radicals were recorded in the CH stretching region. Several previously unreported bands are observed between 2800 and 3150 cm-1. The CH stretching modes observed above 3000 cm-1 are in excellent agreement with CCSD(T) anharmonic frequencies computed using second-order vibrational perturbation theory. However, between 2800 and 3000 cm-1, the spectra of n- and i-propyl radicals become congested and difficult to assign due to the presence of multiple anharmonic resonance polyads. To model the spectrally congested region, Fermi and Darling-Dennison resonances are treated explicitly using "dressed" Hamiltonians and CCSD(T) quartic force fields in the normal mode representation, and the agreement with experiment is less than satisfactory. Computations employing local mode effective Hamiltonians reveal the origin of the spectral congestion to be strong coupling between the high frequency CH stretching modes and the lower frequency CHn bending/scissoring motions. The most significant coupling is between stretches and bends localized on the same CH2/CH3 group. Spectral simulations using the local mode approach are in excellent agreement with experiment. [ABSTRACT FROM AUTHOR]

A radical nitrohalogenation/cyclization of various enynes with tert -butyl nitrite has been developed that conveniently introduces useful nitro and halo groups into organic compounds. Some control experiments were performed to elucidate the mechanism. Further functional transformations proceeded well in this reaction system. [ABSTRACT FROM AUTHOR]

We report on the photodissociation dynamics study of n-butyl nitrite and isoamyl nitrite by means of time-resolved Fourier transform infrared (TR-FTIR) emission spectroscopy. The obtained TR-FTIR emission spectra of the nascent NO fragments produced in the 355 nm laser photolysis of the two alkyl nitrite species showed an almost identical rotational temperature and vibrational distributions of NO. In addition, a close resemblance between the two species was also found in the measured temporal profiles of the IR emission of NO and the recorded UV absorption spectra. The experimental results are consistent with our ab initio calculations using the time-dependent density functional theory at the B3LYP/6-311G(d,p) level, which indicate that the substitution of one of the two γ-H atoms in n-C4H9ONO with a methyl group to form (CH3)2C3H5ONO has only a minor effect on the photodissociation dynamics of the two molecules. [ABSTRACT FROM AUTHOR]

An approach has been developed for the copper-catalyzed acetylation of phenols and anilines with potassium thioacetate as an acetylating reagent. Although only electron-rich phenols and anilines are compatible with this protocol, the reaction can provide moderate to high yields under mild conditions. Compared with other acetylating reagents, the current reagent has certain advantages, such as its low cost, easy availability, stability, insensitivity to water or air, and ease of storage. [ABSTRACT FROM AUTHOR]

Aromatic diazonium salts are valuable building blocks for organic synthesis; however, in most cases, they are unstable, unsafe, poorly soluble, and/or expensive. In this paper, we have shown that a variety of stable and safe arenediazonium triflates ArN2+ TfO– can be obtained easily and in high yields by diazotization of anilines with tert‐butyl nitrite in the presence of trifluoromethanesulfonic acid. Arenediazonium triflates are relatively shelf‐stable in the dry state. They dissolve well in water, as well as polar and even nonpolar organic solvents. Less than 800 J/g of energy is released during the thermal decomposition of these salts, which indicates their explosion safety. Arenediazonium triflates have a high reactivity in the known reactions of diazonium chemistry, and undergo an unusual metal‐free chlorodediazonization reaction with chloroform and CCl4. A variety of stable, safe, and soluble arenediazonium triflates ArN2+ TfO– were obtained easily by diazotization of anilines with tert‐butyl nitrite in the presence of triflic acid. They are highly reactive, forming aromatic iodides, azides, and boronic acids, and also undergo an unusual metal‐free chloro‐dediazonization with chloroform and CCl4. [ABSTRACT FROM AUTHOR]

A visible-light photocatalytic aerobic oxidation of benzylic C(sp³)–H bonds proceeded in the presence of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, tert-butyl nitrite, and acetic acid. Advantages of this aerobic oxidation method include its relatively mild conditions, the use of visible-light irradiation instead of conventional thermal methods, the use of a low catalyst loading, and the ability to oxidize a range of alkylarenes, including xanthenes, thioxanthenes, and 9,10-dihydroacridines, to the corresponding ketones in excellent yields. [ABSTRACT FROM AUTHOR]

TBN-initiated cascade multifunctionalization of inert C–H and C–N bonds in N-arylazacycles has been realized under transition-metal free conditions, in which the synthetically useful oxime, N–NO and aldehyde functional groups were constructed in only one synthetic step. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • No use of any catalyst. • No external oxidant and additive. • Reaction in aqueous media. • Gram-scale synthesis. Abstract A convenient and precise nitration and oximation of alkenes with tert -butyl nitrite has been reported, yielding α-nitro ketoximes in satisfactory yields with broad substrate generality and excellent stereoselectivity under mild conditions. Experiments indicate that tert -butyl nitrite serves as both NO and NO 2 sources and water plays a key role in this difunctionalization reaction. [ABSTRACT FROM AUTHOR]

Abstract: tert‐Butyl nitrite (TBN) reacts differently with various internal alkenes leading to interesting and useful products. Synthesis of 1,2,5‐oxadiazole‐N‐oxides (furoxans) has been achieved from internal alkenes using tert‐butyl nitrite (TBN), quinoline and K2S2O8. Under an identical reaction condition α,β‐unsaturated carboxylic acids and cyclic and acyclic internal alkenes both afforded nitroalkenes as the sole product via decarboxylative and direct nitration path respectively. [ABSTRACT FROM AUTHOR]

Herein we report a method for PdII‐catalyzed purine‐directed ortho nitration of 6‐arylpurines via C(sp2)–H activation by using tBuONO/O2 as nitration agent. This procedure is highly efficient and produces a range of 6‐(2‐nitroaryl)‐purine derivatives with good chemoselectivity and functional‐group tolerance. The utility of the method is further illustrated in the synthesis of antibacterial agent. [ABSTRACT FROM AUTHOR]

A simple and highly efficient protocol for the AcOH-catalyzed three-component reaction among nitroalkenes, difluoroethylamine and tert -butyl nitrite through cascade aza-Michael addition/ N -nitrosation has been developed. A range of CF 2 HCH 2 -containing N -nitrosoamines were obtained in good to excellent yields. This approach features easily available cheap materials, without using additional organic solvents, simple operation under room temperature, gram scalable preparation and functionally diverse products. [ABSTRACT FROM AUTHOR]

Abstract: Regioselective C‐7 nitration of 8‐aminoquinoline amide has been achieved using tert‐butyl nitrite under metal‐free conditions at ambient temperature. The protocol is applicable to various aryl, heteroaryl as well as aliphatic carboxamides, and exhibits high functional group compatibility. The present method provides selective mononitrated quinoline derivatives. Experimental results suggest that the reaction likely proceeds through a radical pathway. [ABSTRACT FROM AUTHOR]

tert-Butyl nitrite (TBN) is an important metal-free reagent that is widely applied in various organic transformations. Besides its traditional applications in nitrosation and diazotization, its ability to activate molecular oxygen to enable the initiation of radical reactions, including nitration, oximation, oxidation, and so on, has attracted extensively attention in the past decade. This review highlights recent advances in this field to promote further exploration of this versatile compound. 1 Introduction 2 Reactions Involving TBN 2.1 Nitrosation 2.2 Oximation 2.3 Diazotization 2.4 Nitration 2.5 Oxidation 2.6 Other Reactions 3 Conclusion and Perspective [ABSTRACT FROM AUTHOR]

A mild and eco-friendly protocol for the synthesis of 1,2,3-benzotriazine-4-(3H)-ones is described using saccharin as a cheap and efficient catalyst and tert-butyl nitrite as a diazotization reagent for the first time. The current method has advantages such as cost effectiveness, energy efficiency, and simple experimental procedure, good yield of the desired product, and metal-free and environmentally benign conditions. [ABSTRACT FROM AUTHOR]

Abstract: A tert‐butyl nitrite mediated methyl‐sulfoxidation of tetrazole‐amines in neat DMSO or methyl‐sulfinyl derivatives is revealed for the first time. The reaction exhibits good group tolerance, as well as highly selectivity to sulfinyl substitutions. This new protocol provides an expeditious and operationally simple procedure for C−S(O) bond construction. Preliminary bioactivity evaluation on selected products shows promising antifungal activities. [ABSTRACT FROM AUTHOR]

A simple and efficient method for the dimerization of primary thioamides into 1,2,4-thiadiazoles using tert -butyl nitrite is described. The optimized condition was also found to be suitable for the dimerization of benzoselenoamides into 1,2,4-selenadiazoles. All the reactions proceed smoothly at room temperature and gave the desired products in excellent yields in a short span of time. [ABSTRACT FROM AUTHOR]

A metal-free synthesis of isatins was achieved through the oxidative reactions of oxindoles with molecular oxygen in the presence of tert-butyl nitrite as an additive. This strategy provides a convenient and simple synthetic route to the construction of C=O bonds without the need for any catalyst or base. The attractive features of this reaction include its convenient procedure and mild reaction conditions. [ABSTRACT FROM AUTHOR]

The miscibility behavior of N-butylpyridinium nitrate/N-octylpyridinium blends with different compositions was studied using the inverse gas chromatography (IGC) technique. Twenty-one solvents, including alkanes, cycloalkane, aromatic hydrocarbons, alcohols, ethyl ether, acetone, and esters, with different chemical properties were studied to evaluate the interaction between N-alkylpyridinium nitrates and solvents. The interaction parameters of different ionic liquids [ILs] have been calculated. Results were consistent with the activity coefficients at infinite dilution and weight fraction activity coefficient. In addition, the miscibility term ΔH1S was significantly different in each obtained IL blend. The solubility parameters of N-butylpyridinium nitrate/N-octylpyridinium blends were derived using the calculation δ12/(RT) – χ12∞/V1 versus δ1 of probes. The altered values of the solubility parameters were consistent with those of the studied ILs based on the methylimidazolium cation. [ABSTRACT FROM AUTHOR]

A radical-radical cross-coupling reaction of phenols with tert-butyl nitrite has been developed with the use of water as an additive. This method allows the construction of C-N bonds under an air atmosphere at room temperature, providing the ortho-nitrated phenol derivative in moderate to good yields. [ABSTRACT FROM AUTHOR]

Photocatalytic aerobic benzylic C(sp3)−H oxygenations of aromatic hydrocarbons and C3-substituted indoles were studied by employing a co-catalytic system of 3DDQ* (DDQ=2,3-dichloro-5,6-dicyano-1,4-benzoquinone) and tert-butyl nitrite. The superior efficiency of these reaction conditions was demonstrated by comparison with the analogous thermal protocol, and a range of substrates could be oxidized catalytically and selectively in good yields. [ABSTRACT FROM AUTHOR]

A facile and efficient annulation of 2-aminobenzamides and tert -butyl nitrite was developed, affording 1,2,3-benzotriazine-4-(3 H )-ones in good yields under mild conditions. Notably, the reaction was carried out in the absence of strong acid and tert -butyl nitrite was employed as the nitrogen source. [ABSTRACT FROM AUTHOR]

The abuse of alkyl nitrites is common among adolescents and young adults worldwide. However, the information regarding the effects of alkyl nitrites on the central nervous system and the associated psychological abuse potential is scarce. The abuse potential of 3 representative alkyl nitrites – isobutyl nitrite, isoamyl nitrite, and butyl nitrite – was evaluated in mice using conditioned place preference tests with an unbiased method. The dopamine levels released by synaptosomes extracted from the striatal region were measured using high performance liquid chromatography. Mice treated with the test substances (50 mg/kg, i.p.) exhibited a significantly increased drug-paired place preference. Moreover, greater levels of dopamine were released by striatal region synaptosomes in response to isobutyl nitrite treatment in mice. Thus, our findings suggest that alkyl nitrites could lead to psychological dependence and dopaminergic effects. Furthermore, these results provide scientific evidence to support the regulation of alkyl nitrites as psychoactive substances in the future. [ABSTRACT FROM AUTHOR]

A highly practical metal-free catalytic system has been developed for aerobic oxidation of alcohols to corresponding ketones and aldehydes using catalytic amount of N -hydroxyphthalimide (NHPI) and tert -butyl nitrite (TBN) with molecular oxygen serving as the terminal oxidant. A variety of aliphatic, aromatic, allylic, and heterocyclic alcohols were smoothly converted to desired products with moderate to excellent yields. Moreover, a possible radical mechanism was proposed. [ABSTRACT FROM AUTHOR]

A highly efficient method for direct nitration-oximization of styrene derivatives using tert-butyl nitrite ( t-BuONO) in DMSO was developed. The present method offers a convenient and practical approach for the synthesis of α-nitrooximes in moderate to high yields. The salient features entail mild reaction conditions, metal-free reagent, environmentally benign solvent and simple experimental procedure. [ABSTRACT FROM AUTHOR]

The development of new CH functionalization protocols based on inexpensive cobalt catalysts is currently attracting significant interest. Functionalized 8-aminoquinoline compounds are high-potential building blocks in organic chemistry and pharmaceutical compounds and new facile routes for their preparation would be highly valuable. Recently, copper has been applied as catalyst for the functionalization of 8-aminoquinoline compounds and found to operate through a single electron transfer (SET) mechanism, although requiring elevated reaction temperatures. Herein, we described the first example of a cobalt-catalyzed remote CH functionalization of 8-aminoquinoline compounds operating through a SET mechanism, exemplified using a practical and mild nitration protocol. The reaction uses inexpensive cobalt nitrate hexahydrate [Co(NO3)2⋅6 H2O] as catalyst and tert-butyl nitrite (TBN) as nitro source. This methodology offers the basis for the facile preparation of many new functionalized 8-aminoquinoline derivatives. [ABSTRACT FROM AUTHOR]

The enthalpy and activation energy of reactions involving attack by MeO and MeO on CH groups of 2-butyl nitrite and 2-nitrosobutane have been calculated by quantum chemical methods. The abstraction of a hydrogen atom is accompanied, in the former case, by concerted N-O bond breaking and, in the latter case, by concerted C-N bond breaking, resulting in NO• formation. On the basis of the results obtained, an algorithm has been developed within the intersecting parabolas model for calculating the enthalpies, activation energies, and rate constants of these types of reactions involving alkyl, alkoxyl, aminyl, peroxyl, phenoxyl, thiyl, and hydroxyl radicals. [ABSTRACT FROM AUTHOR]

A simple and effective approach for highly selective preparation of nitrocyclohexane from cyclohexane using tert-butyl nitrite as a nitrating agent under atmospheric pressure has been successfully developed in this work. The results indicate that the N-hydroxyphthalimide catalyst gave the best results with 27.3 % of cyclohexane conversion and 88.0 % of selectivity to nitrocyclohexane under optimal reaction conditions. The present reaction provides a novel strategy for the synthesis of nitroalkanes from the nitration of low-carbon alkanes because of the mild reaction condition, simple experimental procedure and high selectivity towards the desired product. This method may be very significant to establish such a synthesis method for aliphatic nitro-compounds from the low-carbon alkanes in organic fields. [ABSTRACT FROM AUTHOR]

Alkyne C=C bond breaking, outside of alkyne metathesis, remains an underdeveloped area in reaction discovery. Recently, nitrogenation has been reported to allow nitrile formation from alkynes. A new protocol for the metal-free C=C bond cleavage of terminal alkynes to produce nitriles is reported. This method provides an opportunity to synthesize a vast range of nitriles containing aryl, heteroaryl, and natural product derivatives (38 examples). In addition, the potential of tBuONO to act as a powerful nitrogenating agent for terminal aryl alkynes is demonstrated. [ABSTRACT FROM AUTHOR]

We have discovered that variousα-nitro ketoximes can be synthesized in good yields starting from styrenes andtert-butyl nitrite. The success of the reaction was critically dependent on the use of a mixture solvent of dimethylsulfoxide and water. The reaction can tolerate a wide variety of substituents including electron-withdrawing and electron-donating groups. [ABSTRACT FROM AUTHOR]

A new method for the nitrative spirocyclization of alkynes is described. This method involves the oxidative difunctionalization of alkynes initiated by a radical attack pathway using t-BuONO ( tert-butyl nitrite) combined with water as the nitro source and TEMPO [(2,2,6,6-tetramethyl-piperidin-1-yl)oxyl] as the initiator, and it represents a new example of oxidative alkyne difunctionalization via the formation of CN/CC bonds for the assembly of nitroalkene unit-containing spirocycles. [ABSTRACT FROM AUTHOR]

A method for the synthesis of gem-difluorinated nitroso compounds is described. The reaction involves interaction of organozinc reagents with (bromodifluoromethyl)trimethylsilane followed by nitrosation of difluorinated organozinc species with an n-butyl nitrite/chlorotrimethylsilane system. [ABSTRACT FROM AUTHOR]

An efficient method for the synthesis of quinoxaline N-oxides proceeds by the dehydrogenative N-incorporation of simple imines by C(sp2)-H and C(sp3)-H bond functionalization. The overall transformation involves the cleavage of three C-H bonds. The reaction is easily handled and proceeds under mild conditions. Simple and readily available tert-butyl nitrite (TBN) was employed as the NO source. [ABSTRACT FROM AUTHOR]

A novel iminoxyl radical-involvedmetal-free approach to vicinaloxyoximation and aminooximation of unactivated alkenes is developed.This method utilizes the dichotomous reactivity of the iminoxyl radicalto furnish a general difunctionalization on alkenes using simple tert-butyl nitrite (TBN) as the iminoxyl radical initiatoras well the carbon radical trap. By using this protocol, oxime featured4,5-dihydroisoxazoles and cyclic nitrones were facilely prepared fromβ,γ- and γ,δ-unsaturated ketoximes, respectively. [ABSTRACT FROM AUTHOR]

An efficient protocol for the Pd-catalyzed regiospecific ortho-nitration of ( E)-azoarenes has been achieved for the first time using tBuONO as a nitrating agent under atmospheric oxygen. A series of both symmetrical and unsymmetrical azoarenes were nitrated efficiently by this procedure providing excellent chemo- and regioselectivity and compatibility with a broad array of functional groups. [ABSTRACT FROM AUTHOR]

Tertiary butyl nitrite (TBN) is an acid-free and safe nitrating agent that provides preferentiallyβ-nitrostyrenes with cinnamic acids and corresponding nitro derivatives with phenols in good yields under classical conditions. However, ultrasonic and microwave-assisted reactions reduced the reaction times substantially and enhanced the yields from good to excellent. Supplemental materials are available for this article. Go to the publisher's online edition ofSynthetic Communications® to view the free supplemental file. [ABSTRACT FROM PUBLISHER]

Nitroolefins are essential elements for both synthetic chemistry and medicinal research. Despite significant improvements in nitration of olefin an efficient metal-freesynthesis remains elusive so far. Herein, we disclose a new set of reagents to access nitroolefins in a single step under metal-free conditions. A wide range of olefins with diverse functionalities has been nitrated in synthetically useful yields. This transformation is operationally simple and exhibits excellent E-selectivity. Furthermore, site selective nitration in a complex setup makes this method advantageous. [ABSTRACT FROM AUTHOR]

Abstract: A facile and efficient protocol for the oxidative deprotection of benzyl-type ethers has been developed. The reaction was performed with catalytic amounts of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and tert-butyl nitrite (TBN) under atmospheric pressure of O2. Under the optimal reaction conditions, a variety of p-methoxybenzyl (PMB), p-phenylbenzyl (PPB), and benzyl (Bn) ethers can be deprotected to their corresponding alcohols in excellent conversions and selectivities. [Copyright &y& Elsevier]

Abstract: The oxidation of primary and secondary benzylic alcohols was achieved by using tert-butyl nitrite (t-BuONO) as a stoichiometric oxidant. Various substrates were effectively converted into the corresponding ketones or aldehydes in good to excellent yields. The reaction presumably proceeded by a nitrosyl exchange and a subsequent thermal decomposition of benzylic nitrites. This process would realize an oxidation of alcohols with oxygen in theory by combining with a reproduction of alkyl nitrites from NO and alcohols under an O2 atmosphere. In addition, almost pure oxidized products were readily obtained by simple evaporation of the reaction mixtures since t-BuONO produced only volatile side products. [Copyright &y& Elsevier]

The article outlines a process for the synthesis of 4-Chloro-1H-indazole, which is described as being a more efficient and economic procedure than those previously used. The utilization of the commercially available 3- chloro-2-methylaniline as a starting material is outlined, as well as the acetylation of its NH2 group which produces N-acetyl-3-chloro-2-methylaniline. Money saving aspects of this procedure are highlighted, including the usage of tert-Butyl nitrite instead of iso-amyl nitrite, and the used of NaOH instead of LiOH.

Tert-butyl nitrite easily releasing alkoxyl radical and NO in combination with compressed CO2under metal free condition was applied to efficiently and selectively initiate aerobic cleavage of benzylic CC bonds. Notably, compressed CO2in this study not only provides a safe reaction environment but also tunes the selectivity. [ABSTRACT FROM AUTHOR]

Structure-H hydrate has been highlighted due to its higher gas storage capacity and favorable thermal stability. Here, we introduce a new structure-H hydrate former, tert-butyl nitrite, and identify it through spectroscopic analysis. The hydrate structure and guest distribution were examined by using powder X-ray diffraction, Raman spectroscopy, and solid-state high-power decoupling 13C NMR spectroscopy. The phase equilibria (Lw+ H + Lg+ V) of tert-butyl nitrite + CH4hydrate were measured at pressures from (3 to 4.5) MPa and at temperatures from (277 to 282) K. We also investigated the kinetic behavior of this new high-polarity hydrate former. [ABSTRACT FROM AUTHOR]

Abstract: The detailed theoretical investigation on the dissociation of n-butyl nitrite leading to OH has been performed using the G3B3 method in both the S 0 and T 1 states. The calculations reveal that there exist three main dissociative mechanisms, which are α-H, β-H and δ-H transfer mechanisms, respectively. Additionally, some complexes have been located in the potential energy surfaces. Moreover, we also reexamine the optimized geometries of the conformers of n-butyl nitrite. Compared with the computational results by McLaughlin et al. [Spectrochim. Acta, Part A 67 (2007) 178], some new conformers are optimized in the present work. [Copyright &y& Elsevier]

The purpose of this study was to examine the prevalence, patterns, and predictors of nitrite inhalant use in antisocial adolescents. Face-to-face interviews were conducted with 723 Missouri youth (Mage = 15.5, SD = 1.2) in residential care for antisocial behavior. The lifetime prevalence of nitrite inhalant use was 1.7% (1.3% for boys; 4.3% for girls, p = .06), a figure somewhat higher than comparable estimates from the MTF and NSDUH national surveys. Most lifetime users reported nitrite use in the prior year (92%) and experienced intoxication (83%) during periods of nitrite inhalation. Nitrite users had significantly higher scores on measures of somatization, obsessive-compulsive traits, interpersonal sensitivity, impulsivity, fearlessness, suicidality, and polydrug use and were significantly more likely to have suffered a serious head injury and to be White than their non-nitrite-using counterparts. Nitrite users also reported significantly higher levels of current psychiatric distress related to periods of faintness or dizziness, hot or cold spells, difficulty making decisions, and their "mind going blank" than did non-nitrite users. Antisocial adolescent nitrite users are at substantially elevated risk for serious functional impairments given their high rates of lifetime head injury, comparatively more varied and intensive levels of involvement with psychoactive drugs, and symptom reports suggestive of psychiatric and cognitive dysfunction. [ABSTRACT FROM AUTHOR]