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Imidate
Carboximidates (or more general imidates) are organic compounds, which can be thought of as esters formed between a carboximidic acid (R-C(=NR')OH) and an alcohol, with the general formula R-C(=NR')OR". They are also known as imino ethers, since they resemble imines (>C=N-) with an oxygen atom connected to the carbon atom of the C=N double bond. Synthesis Imidates may be generated by a number of synthetic routes, but are in general formed by the Pinner reaction. This proceeds via the acid catalyzed attack of nitriles by alcohols. Imidates produced in this manner are formed as their hydrochloride salts, which are sometimes referred to as Pinner salts. Carboximidates are also formed as intermediates in the Mumm rearrangement and the Overman rearrangement. Imidate/amidate anions An amidate/imidate anion is formed upon deprotonation of an amide or imidic acid. Since amides and imidic acids are tautomers, they form the same anion upon deprotonation. The two names are thus syn ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Chapman Rearrangement
Carboximidates (or more general imidates) are organic compounds, which can be thought of as esters formed between a carboximidic acid (R-C(=NR')OH) and an alcohol, with the general formula R-C(=NR')OR". They are also known as imino ethers, since they resemble imines (>C=N-) with an oxygen atom connected to the carbon atom of the C=N double bond. Synthesis Imidates may be generated by a number of synthetic routes, but are in general formed by the Pinner reaction. This proceeds via the acid catalyzed attack of nitriles by alcohols. Imidates produced in this manner are formed as their hydrochloride salts, which are sometimes referred to as Pinner salts. Carboximidates are also formed as intermediates in the Mumm rearrangement and the Overman rearrangement. Imidate/amidate anions An amidate/imidate anion is formed upon deprotonation of an amide or imidic acid. Since amides and imidic acids are tautomers, they form the same anion upon deprotonation. The two names are thus sy ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Pinner Reaction
The Pinner reaction refers to the acid catalysed reaction of a nitrile with an alcohol to form an imino ester salt (alkyl imidate salt); this is sometimes referred to as a Pinner salt. The reaction is named after Adolf Pinner, who first described it in 1877. Pinner salts are themselves reactive and undergo additional nucleophilic additions to give various useful products: * With an excess of alcohol to form an orthoester * With ammonia or an amine to form an amidine (di-nitriles may form imidines, for instance succinimidine from succinonitrile) * With water to form an ester * With hydrogen sulfide to form a thionoester Commonly the Pinner salt itself is not isolated, with the reaction being continued to give the desired functional group (orthoester etc.) in one go. It should be appreciated that the Pinner reaction refers specifically to an acid catalyzed process, but that similar results can often be achieved using base catalysis. The two approaches can be complementary, with ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Imidic Acid
In chemistry, an imidic acid is any molecule that contains the -C(=NH)-OH functional group. It is the tautomer of an amide and the isomer of an oxime. The term "imino acid" is an obsolete term for this group that should not be used in this context because it has a different molecular structure.{{GoldBookRef , file=I02959 , title=Imino acids , accessdate=2012-04-02 Imidic acids can be formed by metal-catalyzed dehydrogenation of geminal amino alcohols. For example, methanolamine, the parent compound of the amino alcohols, can be dehydrogenated to methanimidic acid, the parent compound of the imidic acids. :H2NCH2OH → HNCHOH + H2 (tautomer of formamide) Geminal amino alcohols with side chains similarly form imidic acids with the same side chains: :H2NCHROH → HNCROH + H2 Another way to form imidic acids is the reaction of carboxylic acids with azanone. For example, the reaction for carbamic acid: :H2NCOOH + HNO → H2NCNHOH + O2 (tautomer of urea) And the general reaction f ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Trichloroacetonitrile
Trichloroacetonitrile is an organic compound with the formula CCl3CN. It is a colourless liquid, although commercial samples often are brownish. It is used commercially as a precursor to the fungicide etridiazole. It is prepared by dehydration of trichloroacetamide. As a bifunctional compound, trichloroacetonitrile can react at both the trichloromethyl and the nitrile group. The electron-withdrawing effect of the trichloromethyl group activates the nitrile group for nucleophilic additions. The high reactivity makes trichloroacetonitrile a versatile reagent, but also causes its susceptibility towards hydrolysis. Synthesis The production of trichloroacetonitrile by dehydration of trichloroacetamide was first described in 1873 by L. Bisschopinck at the Katholieke Universiteit Leuven. : Trichloroacetonitrile can be obtained by chlorination of acetonitrile on a zinc, copper and alkaline earth metal halide-impregnated activated carbon catalyst at 200–400 °C with a ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Hydrolysis
Hydrolysis (; ) is any chemical reaction in which a molecule of water breaks one or more chemical bonds. The term is used broadly for substitution reaction, substitution, elimination reaction, elimination, and solvation reactions in which water is the nucleophile. Biological hydrolysis is the cleavage of biomolecules where a water molecule is consumed to effect the separation of a larger molecule into component parts. When a carbohydrate is broken into its component sugar molecules by hydrolysis (e.g., sucrose being broken down into glucose and fructose), this is recognized as saccharification. Hydrolysis reactions can be the reverse of a condensation reaction in which two molecules join into a larger one and eject a water molecule. Thus hydrolysis adds water to break down, whereas condensation builds up by removing water. Types Usually hydrolysis is a chemical process in which a molecule of water is added to a substance. Sometimes this addition causes both the substance and w ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Benzyl Alcohol
Benzyl alcohol is an aromatic alcohol with the formula C6H5CH2OH. The benzyl group is often abbreviated "Bn" (not to be confused with "Bz" which is used for benzoyl), thus benzyl alcohol is denoted as BnOH. Benzyl alcohol is a colorless liquid with a mild pleasant aromatic odor. It is a useful solvent due to its polarity, low toxicity, and low vapor pressure. Benzyl alcohol has moderate solubility in water (4 g/100 mL) and is miscible in alcohols and diethyl ether. The anion produced by deprotonation of the alcohol group is known as benzylate or benzyloxide. Natural occurrences Benzyl alcohol is produced naturally by many plants and is commonly found in fruits and teas. It is also found in a variety of essential oils including jasmine, hyacinth and ylang-ylang. It is also found in castoreum from the castor sacs of beavers. Benzyl esters also occur naturally. Preparation Benzyl alcohol is produced industrially from toluene via benzyl chloride, which is hydrolyzed ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Protecting Group
A protecting group or protective group is introduced into a molecule by chemical modification of a functional group to obtain chemoselectivity in a subsequent chemical reaction. It plays an important role in multistep organic synthesis. In many preparations of delicate organic compounds, some specific parts of their molecules cannot survive the required reagents or chemical environments. Then, these parts, or groups, must be protected. For example, lithium aluminium hydride is a highly reactive but useful reagent capable of reducing esters to alcohols. It will always react with carbonyl groups, and this cannot be discouraged by any means. When a reduction of an ester is required in the presence of a carbonyl, the attack of the hydride on the carbonyl has to be prevented. For example, the carbonyl is converted into an acetal, which does not react with hydrides. The acetal is then called a protecting group for the carbonyl. After the step involving the hydride is complete, the acet ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Benzyl 2,2,2-trichloroacetimidate
In organic chemistry, benzyl is the substituent or molecular fragment possessing the structure . Benzyl features a benzene ring () attached to a methylene group () group. Nomenclature In IUPAC nomenclature, the prefix benzyl refers to a substituent, for example benzyl chloride or benzyl benzoate. Benzyl is not to be confused with phenyl with the formula . The term benzylic is used to describe the position of the first carbon bonded to a benzene or other aromatic ring. For example, is referred to as a "benzylic" carbocation. The benzyl free radical has the formula . The benzyl cation or phenylcarbenium ion is the carbocation with formula ; the benzyl anion or phenylmethanide ion is the carbanion with the formula . None of these species can be formed in significant amounts in the solution phase under normal conditions, but they are useful referents for discussion of reaction mechanisms and may exist as reactive intermediates. Abbreviations The abbreviation "Bn" denotes ben ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Newman–Kwart Rearrangement
The Newman–Kwart rearrangement is a type of rearrangement reaction in which the aryl group of an ''O''-aryl thiocarbamate, ArOC(=S)NMe2, migrates from the oxygen atom to the sulfur atom, forming an ''S''-aryl thiocarbamate, ArSC(=O)NMe2. The reaction is named after its discoverers, Melvin Spencer Newman and Harold Kwart. The reaction is a manifestation of the double bond rule. : Mechanism The Newman–Kwart rearrangement is intramolecular; it proceeds ''via'' a four-membered cyclic transition state. : Use for preparation of thiophenols The Newman–Kwart rearrangement is an important prelude to the synthesis of thiophenols. A phenol (1) is deprotonated with a base followed by treatment with a thiocarbamoyl chloride (2) to form an ''O''-aryl thiocarbamate (3). Heating 3 to around 250 °C causes it undergo Newman–Kwart rearrangement to an ''S''-aryl thiocarbamate (4). Alkaline hydrolysis or similar cleavage yields a thiophenol (5). : See also * Smiles rearrangement * Cha ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Arthur William Chapman
Arthur is a common male given name of Brythonic origin. Its popularity derives from it being the name of the legendary hero King Arthur. The etymology is disputed. It may derive from the Celtic ''Artos'' meaning “Bear”. Another theory, more widely believed, is that the name is derived from the Roman clan '' Artorius'' who lived in Roman Britain for centuries. A common spelling variant used in many Slavic, Romance, and Germanic languages is Artur. In Spanish and Italian it is Arturo. Etymology The earliest datable attestation of the name Arthur is in the early 9th century Welsh-Latin text ''Historia Brittonum'', where it refers to a circa 5th to 6th-century Briton general who fought against the invading Saxons, and who later gave rise to the famous King Arthur of medieval legend and literature. A possible earlier mention of the same man is to be found in the epic Welsh poem ''Y Gododdin'' by Aneirin, which some scholars assign to the late 6th century, though this is still a ma ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Organic Reactions
Organic reactions are chemical reactions involving organic compounds. The basic organic chemistry reaction types are addition reactions, elimination reactions, substitution reactions, pericyclic reactions, rearrangement reactions, photochemical reactions and redox reactions. In organic synthesis, organic reactions are used in the construction of new organic molecules. The production of many man-made chemicals such as drugs, plastics, food additives, fabrics depend on organic reactions. The oldest organic reactions are combustion of organic fuels and saponification of fats to make soap. Modern organic chemistry starts with the Wöhler synthesis in 1828. In the history of the Nobel Prize in Chemistry awards have been given for the invention of specific organic reactions such as the Grignard reaction in 1912, the Diels-Alder reaction in 1950, the Wittig reaction in 1979 and olefin metathesis in 2005. Classifications Organic chemistry has a strong tradition of naming a specific reac ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
