Nitrosation
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Nitrosation
Nitrosation is a process of converting organic compounds into nitroso derivatives, i.e. compounds containing the R-NO functionality. ''C''-Nitroso compounds ''C''-Nitroso compounds, such as nitrosobenzene, are typically prepared by oxidation of hydroxylamines: :RNHOH + → RNO + H2O ''S''-Nitroso compounds ''S''-Nitroso compounds ( ''S''-nitrosothiols) are typically prepared by condensation of a thiol and nitrous acid: :RSH + HONO → RSNO + H2O ''O''-Nitroso compounds ''O''-Nitroso compounds are similar to ''S''-nitroso compounds, but are less reactive because the oxygen atom is less nucleophilic than the sulfur atom. The formation of an alkyl nitrite from an alcohol and nitrous acid is a common example: :ROH + HONO → RONO + H2O ''N''-Nitrosamines ''N''-Nitrosamines, including the carcinogenic variety, arise from the reaction of nitrite sources with amino compounds, which can happen during the curing of meat. Typically this reaction proceeds via the attack of the nitroso ...
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Nitroso
In organic chemistry, nitroso refers to a functional group in which the nitric oxide () group is attached to an organic moiety. As such, various nitroso groups can be categorized as ''C''-nitroso compounds (e.g., nitrosoalkanes; ), ''S''-nitroso compounds ( nitrosothiols; ), ''N''-nitroso compounds (e.g., nitrosamines, ), and ''O''-nitroso compounds ( alkyl nitrites; ). Synthesis Nitroso compounds can be prepared by the reduction of nitro compounds or by the oxidation of hydroxylamines. Ortho-nitrosophenols may be produced by the Baudisch reaction. In the Fischer–Hepp rearrangement aromatic 4-nitrosoanilines are prepared from the corresponding nitrosamines. Properties Nitrosoarenes typically participate in a monomer–dimer equilibrium. The dimers, which are often pale yellow, are often favored in the solid state, whereas the deep-green monomers are favored in dilute solution or at higher temperatures. They exist as ''cis'' and ''trans'' isomers. Due to the stability o ...
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Nitroso
In organic chemistry, nitroso refers to a functional group in which the nitric oxide () group is attached to an organic moiety. As such, various nitroso groups can be categorized as ''C''-nitroso compounds (e.g., nitrosoalkanes; ), ''S''-nitroso compounds ( nitrosothiols; ), ''N''-nitroso compounds (e.g., nitrosamines, ), and ''O''-nitroso compounds ( alkyl nitrites; ). Synthesis Nitroso compounds can be prepared by the reduction of nitro compounds or by the oxidation of hydroxylamines. Ortho-nitrosophenols may be produced by the Baudisch reaction. In the Fischer–Hepp rearrangement aromatic 4-nitrosoanilines are prepared from the corresponding nitrosamines. Properties Nitrosoarenes typically participate in a monomer–dimer equilibrium. The dimers, which are often pale yellow, are often favored in the solid state, whereas the deep-green monomers are favored in dilute solution or at higher temperatures. They exist as ''cis'' and ''trans'' isomers. Due to the stability o ...
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Nitrosonium
The nitrosonium ion is , in which the nitrogen atom is bonded to an oxygen atom with a bond order of 3, and the overall diatomic species bears a positive charge. It can be viewed as nitric oxide with one electron removed. This ion is usually obtained as the following salts: , (nitrosylsulfuric acid, more descriptively written ) and . The and salts are slightly soluble in acetonitrile . NOBF4 can be purified by sublimation at 200–250 °C and . is isoelectronic with CO, and . It arises via protonation of nitrous acid: :HONO + H+ NO+ + H2O Chemical properties Hydrolysis reacts readily with water to form nitrous acid: : For this reason, nitrosonium compounds must be protected from water or even moist air. With base, the reaction generates nitrite: : As a diazotizing agent reacts with aryl amines, , to give diazonium salts, . The resulting diazonium group is easily displaced (unlike the amino group) by a variety of nucleophiles. As an oxidizing agent , e.g. as ...
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Curing (food Preservation)
Curing is any of various food preservation and flavoring processes of foods such as meat, fish and vegetables, by the addition of salt, with the aim of drawing moisture out of the food by the process of osmosis. Because curing increases the solute concentration in the food and hence decreases its water potential, the food becomes inhospitable for the microbe growth that causes food spoilage. Curing can be traced back to antiquity, and was the primary method of preserving meat and fish until the late 19th century. Dehydration was the earliest form of food curing. Many curing processes also involve smoking, spicing, cooking, or the addition of combinations of sugar, nitrate, and nitrite."Historical Origins of Food Preservation."
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Oxidation
Redox (reduction–oxidation, , ) is a type of chemical reaction in which the oxidation states of substrate change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is the gain of electrons or a decrease in the oxidation state. There are two classes of redox reactions: * ''Electron-transfer'' – Only one (usually) electron flows from the reducing agent to the oxidant. This type of redox reaction is often discussed in terms of redox couples and electrode potentials. * ''Atom transfer'' – An atom transfers from one substrate to another. For example, in the rusting of iron, the oxidation state of iron atoms increases as the iron converts to an oxide, and simultaneously the oxidation state of oxygen decreases as it accepts electrons released by the iron. Although oxidation reactions are commonly associated with the formation of oxides, other chemical species can serve the same function. In hydrogenation, C=C (and other) bonds ar ...
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Hydroxylamines
Hydroxylamine is an inorganic compound with the formula . The material is a white crystalline, hygroscopic compound.Greenwood and Earnshaw. ''Chemistry of the Elements.'' 2nd Edition. Reed Educational and Professional Publishing Ltd. pp. 431–432. 1997. Hydroxylamine is almost always provided and used as an aqueous solution. It is consumed almost exclusively to produce Nylon-6. It is also an intermediate in biological nitrification. The oxidation of to hydroxylamine is a step in biological nitrification. History Hydroxylamine was first prepared as hydroxylammonium chloride in 1865 by the German chemist Wilhelm Clemens Lossen (1838-1906); he reacted tin and hydrochloric acid in the presence of ethyl nitrate. It was first prepared in pure form in 1891 by the Dutch chemist Lobry de Bruyn and by the French chemist Léon Maurice Crismer (1858-1944). The coordination complex , known as Crismer's salt, releases hydroxylamine upon heating. Production Hydroxylamine or its salts can be ...
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S-Nitrosothiol
In organic chemistry, ''S''-nitrosothiols, also known as thionitrites, are organic compounds or functional groups containing a nitroso group attached to the sulfur atom of a thiol. ''S''-Nitrosothiols have the general formula , where ''R'' denotes an organic group. Originally suggested by Ignarro to serve as intermediates in the action of organic nitrates, endogenous S-nitrosothiols were discovered by Stamler and colleagues (S-nitrosoalbumin in plasma and S-nitrosoglutathione in airway lining fluid) and shown to represent a main source of NO bioactivity ''in vivo''. More recently, S-nitrosothiols have been implicated as primary mediators of protein S-nitrosylation, the oxidative modification of cysteine thiol that provides ubiquitous regulation of protein function. S-Nitrosothiols have received much attention in biochemistry because they serve as donors of both the nitrosonium ion and of nitric oxide and thus best rationalize the chemistry of NO-based signaling in livin ...
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Condensation Reaction
In organic chemistry, a condensation reaction is a type of chemical reaction in which two molecules are combined to form a single molecule, usually with the loss of a small molecule such as water. If water is lost, the reaction is also known as a dehydration synthesis. However other molecules can also be lost, such as ammonia, ethanol, acetic acid and hydrogen sulfide. The addition of the two molecules typically proceeds in a step-wise fashion to the addition product, usually in equilibrium, and with loss of a water molecule (hence the name condensation). The reaction may otherwise involve the functional groups of the molecule, and is a versatile class of reactions that can occur in acidic or basic conditions or in the presence of a catalyst. This class of reactions is a vital part of life as it is essential to the formation of peptide bonds between amino acids and to the biosynthesis of fatty acids. Many variations of condensation reactions exist. Common examples include the ...
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Thiol
In organic chemistry, a thiol (; ), or thiol derivative, is any organosulfur compound of the form , where R represents an alkyl or other organic substituent. The functional group itself is referred to as either a thiol group or a sulfhydryl group, or a sulfanyl group. Thiols are the sulfur analogue of alcohols (that is, sulfur takes the place of oxygen in the hydroxyl () group of an alcohol), and the word is a blend of "''thio-''" with "alcohol". Many thiols have strong odors resembling that of garlic or rotten eggs. Thiols are used as odorants to assist in the detection of natural gas (which in pure form is odorless), and the "smell of natural gas" is due to the smell of the thiol used as the odorant. Thiols are sometimes referred to as mercaptans () or mercapto compounds, a term introduced in 1832 by William Christopher Zeise and is derived from the Latin ('capturing mercury')''Oxford American Dictionaries'' (Mac OS X Leopard). because the thiolate group () bonds very strong ...
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Nitrous Acid
Nitrous acid (molecular formula ) is a weak and monoprotic acid known only in Solution (chemistry), solution, in the gas phase and in the form of nitrite () salts. Nitrous acid is used to make diazonium salts from amines. The resulting diazonium salts are reagents in azo coupling reactions to give azo dyes. Structure In the gas phase, the planar nitrous acid molecule can adopt both a ''syn'' and an ''anti'' form. The ''anti'' form predominates at room temperature, and infrared spectroscopy, IR measurements indicate it is Gibbs free energy, more stable by around 2.3 kJ/mol. p. 462. Image:Trans-nitrous-acid-2D-dimensions.png , Dimensions of the ''anti'' form(from the rotational spectroscopy, microwave spectrum) Image:Trans-nitrous-acid-3D-balls.png , ball-and-stick model, Model of the ''anti'' form Image:Cis-nitrous-acid-3D-balls.png , ''syn'' form Preparation Nitrous acid is usually generated by acidification of aqueous solutions of sodium nitrite with a mineral acid ...
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Nitrosobenzene
Nitrosobenzene is the organic compound with the formula C6H5NO. It is one of the prototypical organic nitroso compounds. Characteristic of its functional group, it is a dark green species that exists in equilibrium with its pale yellow dimer. Both monomer and dimer are diamagnetic. Monomer-dimer equilibrium Nitrosobenzene and other nitrosoarenes typically participate in a monomer-dimer equilibrium. The dimers are often favored in the solid state, whereas the deeply colored monomers are favored in dilute solution or at higher temperatures. The dimers can be formulated as Ar(O−)N+=N+(O−)Ar. They exist as ''cis''- and ''trans''-isomers due to the presence of the N–N double bond. The dimers are sometimes called azobenzenedioxides. The cis-trans isomerization occurs via the intermediacy of the monomer. In the case of nitrosobenzene itself, the metastable monomeric form could be prepared by sublimation onto a cold finger. The monomeric material is selectively sublimed due to ...
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Nucleophile
In chemistry, a nucleophile is a chemical species that forms bonds by donating an electron pair. All molecules and ions with a free pair of electrons or at least one pi bond can act as nucleophiles. Because nucleophiles donate electrons, they are Lewis bases. ''Nucleophilic'' describes the affinity of a nucleophile to bond with positively charged atomic nuclei. Nucleophilicity, sometimes referred to as nucleophile strength, refers to a substance's nucleophilic character and is often used to compare the affinity of atoms. Neutral nucleophilic reactions with solvents such as alcohols and water are named solvolysis. Nucleophiles may take part in nucleophilic substitution, whereby a nucleophile becomes attracted to a full or partial positive charge, and nucleophilic addition. Nucleophilicity is closely related to basicity. History The terms ''nucleophile'' and ''electrophile'' were introduced by Christopher Kelk Ingold in 1933, replacing the terms ''anionoid'' and ''cationoid' ...
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