- A new synthesis of alkyl nitrites: The reaction of alkyl alcohols with nitric oxide in organic solvents
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In a nonaqueous solvent, alkyl nitrites can be easily achieved through the reaction of alkyl alcohols and gaseous NO. In the presence of air, the nitric oxide can in fact be oxidized to nitrous anhydride, which acts as a nitrosating agent. A quantitative
- Grossi, Loris,Strazzari, Samantha
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- Synthetic method of alpha-cyanobenzoxime sodium
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The invention relates to a synthesis method of alpha-cyanobenzoxime sodium, which comprises the following two steps: step 1, reacting an alcohol (alcohol: sodium nitrite: acid = 1: 1-3.5: 1-5) solution and a sodium nitrite (alcohol: sodium nitrite: acid =
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Paragraph 0024
(2021/01/29)
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- Direct cyclohexanone oxime synthesis: Via oxidation-oximization of cyclohexane with ammonium acetate
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An unexpected cascade reaction for oxidation-oximization of cyclohexane with ammonium acetate was developed for the first time to access cyclohexanone oxime with 50.7% selectivity (13.6% conversion). Tetrahedral Ti sites in Ni-containing hollow titanium silicalite can serve as bifunctional catalytic centers in the reaction. This methodology not only provides a direct approach to prepare cyclohexanone oxime, but also simplifies process chemistry. Various available nitrogen sources, such as ammonium salt and even ammonia can be used as starting materials.
- Peng, Ling,Liu, Chan,Li, Na,Zhong, Wenzhou,Mao, Liqiu,Kirk, Steven Robert,Yin, Dulin
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supporting information
p. 1436 - 1439
(2020/02/11)
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- Method and device for continuously preparing alkyl nitrite through channelization
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The invention discloses a method and device for continuously preparing alkyl nitrite through channelization. The method comprises the following steps: storing alkyl alcohol and concentrated HCl aqueous solution in a first container and storing sodium nitrite aqueous solution in a second container; continuously conveying the solution in the first container and the second container into a static mixer for mixing by a first metering pump and a second metering pump respectively, enabling mixed solution to continuously enter a tubular reactor for reaction at the temperature of -20 DEG C-5 DEG C for1-250s, enabling feed liquid after reaction to enter a liquid separation tank and performing aftertreatment on the feed liquid in the liquid separation tank, so as to obtain alkyl nitrite. The preparation method disclosed by the invention has the advantages of being good in process safety and easy in control of reaction conditions, achieving continuous production, being high in product yield andachieving large-scale production only through less investment in the industry.
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Paragraph 0035-0038
(2019/07/04)
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- Novel and highly selective conversion of alcohols and thiols to alkyl nitrites with triphenylphosphine/2,3-dichloro-5,6-dicyanobenzoquinone/Bu 4NNO2 system
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Alkyl nitrites were prepared in good to excellent yields by treatment of alcohols and thiols with triphenylphosphine/2,3-dichloro-5,6- dicyanobenzoquinone/Bu4NNO2 in acetonitrile. This method is highly selective for the conversion of primary alcohols to alkyl nitrites in the presence of secondary and tertiary alcohols and thiols.
- Akhlaghinia, Batool,Pourali, Ali Reza
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p. 1747 - 1749
(2007/10/03)
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- LIF Spectra of Cyclohexoxy Radical and Direct Kinetic Studies of Its Reaction with O2
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The laser-induced fluorescence (LIF) excitation spectrum of cyclohexoxy radical has been measured for the first time. The dominant vibrational progression is consistent with computations, at CIS/6-31+G(d), of the C-O stretch frequency of the axial conformer of cyclohexoxy radical. LIF intensity was used as a probe in direct kinetic studies of the reaction of cyclohexoxy radicals with O2. The Arrhenius expression obtained was k O2 = (5.8 ± 2.3) × 10-12 exp[(-14.3 ± 0.8) kJ/mol/RT] cm-3 molecule-1 s-1 (225-302 K), independent of pressure in the range 50-125 Torr. The room temperature rate constant for this reaction is a factor of 2 higher than the commonly recommended value, but the observed activation energy is 9 times larger than the recommended value of 1.6 kJ/mol. Combining our results with the ratio of rate constants, kO2/kscission, measured in chamber experiments, we obtained an Arrhenius expression for kscission, the rate constant for β C-C scission of cyclohexoxy radical. However, the resulting Arrhenius preexponential factor of 4.5 × 1015 s -1 is unreasonably high compared with the value of ~2 × 1013 s-1 obtained in our RRKM/Master Equation calculations as well as in calculations and experiments reported for other alkoxy radicals. The apparent discrepancy is resolved by examining the uncertainties in the values of kscission and the limited temperature range spanned by the relative rate experiments. A part of the discrepancy might also be explained by the observation that the O2 rate constant measured here is only for a single conformer of cyclohexoxy radical, whereas the relative rate experiments represent some averaging over both conformers.
- Zhang, Lei,Kitney, Katherine A.,Ferenac, Melissa A.,Deng, Wei,Dibble, Theodore S.
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p. 447 - 454
(2007/10/03)
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- Preparation of alkyl nitrates, nitrites, and thiocyanates from alcohols utilizing trichloroisocyanuric acid with triphenylphosphine
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Alcohols in acetonitrile are converted into alkyl nitrates, nitrites, or thiocyanates by the action of triphenylphosphine and trichloroisocyanuric acid along with silver nitrate, silver nitrite, or sodium thiocyanate, respectively.
- Hiegel, Gene A.,Nguyen, Jeremiah,Zhou, Yan
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p. 2507 - 2511
(2007/10/03)
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- Cyclodextrin catalysis in the basic hydrolysis of alkyl nitrites
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The influence of β-cyclodextrin (β-CD) on the hydrolysis reaction of a variety of structural types of alkyl nitrites (RONO) is studied in acid and in basic aqueous solutions.Acid-catalysed hydrolysis of alkyl nitrites is inhibited by the presence of β-cyclodextrin.The results are accounted for by assuming the formation of host-guest complexes between β-cyclodextrin and alkyl nitrite, which are unreactive or much less reactive than the uncomplexed RONO.We propose that the result is a concenquence of the orientation of alkyl nitrite in the cavity of CD.The degree of inhibition increases with the greater inclusion of the alkyl nitrite in the CD cavity.The kinetic data are quantitatively analyzed to afford the stability constants of the host-guest complexes.On the contrary, the presence of β-cyclodextrin strongly increases the rate of hydrolysis of alkyl nitrites in a basic medium, that is at a pH value higher than the pKa of β-cyclodextrin.This feature suggests the formation of a reactive complex between the alkyl nitrite and β-cyclodextrin, whose ionized CD hydroxy group promotes a nucleophilic attack in the rate-limiting step.This behaviour is consistent with a higher reactivity towards alkyl nitrites of an ionized CD hydroxy groups as compared with the OH-; the contrary occurs in the case of esters, whose cleavage by cyclodextrin in basic aqueous media has been studied extensively over the last several years.
- Iglesias, Emilia,Fernandez, Aurora
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p. 1691 - 1700
(2007/10/03)
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- Oxidative Cleavage of Ethers by Metallic Nitrates Supported on Silica Gel
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Metallic nitrates supported on silica gel efficiently cleave and oxidize ethers to the corresponding aldehydes or ketones under mild conditions.Silica gel is essential for the efficient oxidation, and Cu(NO3)2 and Zn(NO3)2 are suitable for practical use.Overoxidation of the product aldehydes is not observed.In some cases alkyl nitrites are isolated in addition to the carbonyl compounds, and the decomposition of alkyl nitrites to the corresponding carbonyl compounds is promoted by the presence of metallic nitrates supported on silica gel.Mechanistic study suggests nitrogen dioxide is an active species.
- Nishiguchi, Takeshi,Bougauchi, Masahiro
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p. 5606 - 5609
(2007/10/02)
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- Convenient Oxidative Cleavage of Ethers by Metallic Nitrates Supported on Silica Gel
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Several metallic nitrates supported on silica gel efficiently cleaved and oxidized primary and secondary ethers to the corresponding aldehydes and ketones.Especially, Cu(NO3)2 and Zn(NO3)2 are suitable for practical use.Silica gel was essential for the efficient oxidation.Overoxidation of the formed aldehydes to carboxylic acids was not observed.This ether oxidation seems to be useful for organic synthesis because of easy experimental operations, high yields of products, and mild reaction conditions.Some mechanistic studies suggest that the key step of the process involves the formation of radical species.
- Nishiguchi, Takeshi,Bougauchi, Masahiro
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p. 3001 - 3002
(2007/10/02)
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- CLAY-SUPPORTED REAGENTS; III THE INTERMEDIACY OF NITROUS ESTERS IN THE OXYDATION OF ALCOHOLS BY CLAY-SUPPORTED FERRIC NITRATE.
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Stereospecific intermediate nitrite formation occurs in the title reaction.
- Cornelis, Andre,Herze, Pierre-Yves,Laszlo, Pierre
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p. 5035 - 5038
(2007/10/02)
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