Search This Blog

Wednesday, June 28, 2023

North magnetic pole

From Wikipedia, the free encyclopedia
https://en.wikipedia.org/wiki/North_magnetic_pole
 
Location of the north magnetic pole and the north geomagnetic pole in 2017. The magnetic-north of the earth as a magnet is actually on the southern hemisphere: The north side of magnets are by definition attracted to the geographic north, and opposite poles attract.

The north magnetic pole, also known as the magnetic north pole, is a point on the surface of Earth's Northern Hemisphere at which the planet's magnetic field points vertically downward (in other words, if a magnetic compass needle is allowed to rotate in three dimensions, it will point straight down). There is only one location where this occurs, near (but distinct from) the geographic north pole. The geomagnetic north pole is the northern antipodal pole of an ideal dipole model of the Earth's magnetic field, which is the most closely fitting model of Earth's actual magnetic field.

The north magnetic pole moves over time according to magnetic changes and flux lobe elongation in the Earth's outer core. In 2001, it was determined by the Geological Survey of Canada to lie west of Ellesmere Island in northern Canada at 81°18′N 110°48′W. It was situated at 83°06′N 117°48′W in 2005. In 2009, while still situated within the Canadian Arctic at 84°54′N 131°00′W, it was moving toward Russia at between 55 and 60 km (34 and 37 mi) per year. In 2013, the distance between the north magnetic pole and the geographic north pole was approximately 800 kilometres (500 mi). As of 2021, the pole is projected to have moved beyond the Canadian Arctic to 86.400°N 156.786°E.

Its southern hemisphere counterpart is the south magnetic pole. Since Earth's magnetic field is not exactly symmetric, the north and south magnetic poles are not antipodal, meaning that a straight line drawn from one to the other does not pass through the geometric center of Earth.

Earth's north and south magnetic poles are also known as magnetic dip poles, with reference to the vertical "dip" of the magnetic field lines at those points.

Recent locations of Earth's magnetic (dip) poles, IGRF-13 estimate
Year 1990 (definitive) 2000 (definitive) 2010 (definitive) 2020
North magnetic pole 78.095°N 103.689°W 80.972°N 109.640°W 85.020°N 132.834°W 86.494°N 162.867°E
South magnetic pole 64.910°S 138.902°E 64.661°S 138.303°E 64.432°S 137.325°E 64.081°S 135.866°E

Polarity

All magnets have two poles, where the lines of magnetic flux enter and emerge. By analogy with Earth's magnetic field, these are called the magnet's "north" and "south" poles. The north-seeking pole of a magnet was defined to have the north designation, according to their use in early compasses. Because opposite poles attract, this means that as a physical magnet, the magnetic north pole of the earth is actually on the southern hemisphere.

The direction of magnetic field lines is defined such that the lines emerge from the magnet's north pole and enter into the magnet's south pole.

History

Part of the carta marina of 1539 by Olaus Magnus, depicting the location of magnetic north vaguely conceived as "Insula Magnetū[m]" (Latin for "Island of Magnets"), off modern-day Murmansk. The man holding the rune staffs is the Norse hero Starkad ("Starcaterus").

Early European navigators, cartographers and scientists believed that compass needles were attracted to a hypothetical "magnetic island" somewhere in the far north (see Rupes Nigra), or to Polaris, the pole star. The idea that Earth itself acts as essentially a giant magnet was first proposed in 1600, by the English physician and natural philosopher William Gilbert. He was also the first to define the north magnetic pole as the point where Earth's magnetic field points vertically downwards. This is the current definition, though it would be a few hundred years before the nature of Earth's magnetic field was understood with modern accuracy and precision.

Expeditions and measurements

First observations

The first group to reach the north magnetic pole was led by James Clark Ross, who found it at Cape Adelaide on the Boothia Peninsula on June 1, 1831, while serving on the second arctic expedition of his uncle, Sir John Ross. Roald Amundsen found the north magnetic pole in a slightly different location in 1903. The third observation was by Canadian government scientists Paul Serson and Jack Clark, of the Dominion Astrophysical Observatory, who found the pole at Allen Lake on Prince of Wales Island in 1947.

Project Polaris

At the start of the Cold War, the United States Department of War recognized a need for a comprehensive survey of the North American Arctic and asked the United States Army to undertake the task. An assignment was made in 1946 for the Army Air Forces' recently formed Strategic Air Command to explore the entire Arctic Ocean area. The exploration was conducted by the 46th (later re-designated the 72nd) Photo Reconnaissance Squadron and reported on as a classified Top Secret mission named Project Nanook. This project in turn was divided into many separate, but identically classified, projects, one of which was Project Polaris, which was a radar, photographic (trimetrogon, or three-angle, cameras) and visual study of the entire Canadian Archipelago. A Canadian officer observer was assigned to accompany each flight.

Frank O. Klein, the director of the project, noticed that the fluxgate compass did not behave as erratically as expected—it oscillated no more than 1 to 2 degrees over much of the region—and began to study northern terrestrial magnetism. With the cooperation of many of his squadron teammates in obtaining many hundreds of statistical readings, startling results were revealed: The center of the north magnetic dip pole was on Prince of Wales Island some 400 km (250 mi) NNW of the positions determined by Amundsen and Ross, and the dip pole was not a point but occupied an elliptical region with foci about 400 km (250 mi) apart on Boothia Peninsula and Bathurst Island. Klein called the two foci local poles, for their importance to navigation in emergencies when using a "homing" procedure. About three months after Klein's findings were officially reported, a Canadian ground expedition was sent into the Archipelago to locate the position of the magnetic pole. R. Glenn Madill, Chief of Terrestrial Magnetism, Department of Mines and Resources, Canada, wrote to Lt. Klein on 21 July 1948:

… we agree on one point and that is the presence of what we can call the main magnetic pole on northwestern Prince of Wales Island. I have accepted as a purely preliminary value the position latitude 73°N and longitude 100°W. Your value of 73°15'N and 99°45’W is in excellent agreement, and I suggest that you use your value by all means.

— R. Glenn Madill

(The positions were less than 30 km (20 mi) apart.)

Modern (post-1996)

The movement of Earth's north magnetic pole across the Canadian Arctic in recent centuries, continuing in recent years across the Arctic Ocean towards Siberia
 
Speed of the north magnetic pole drift according to the IGRF-12 model

The Canadian government has made several measurements since, which show that the north magnetic pole is moving continually northwestward. In 2001, an expedition located the pole at 81°18′N 110°48′W.

In 2007, the latest survey found the pole at 83°57′00″N 120°43′12″W. During the 20th century it moved 1,100 km (680 mi), and since 1970 its rate of motion has accelerated from 9 to 52 km (5.6 to 32.3 mi) per year (2001–2007 average; see also polar drift). Members of the 2007 expedition to locate the magnetic north pole wrote that such expeditions have become logistically difficult, as the pole moves farther away from inhabited locations. They expect that in the future, the magnetic pole position will be obtained from satellite data instead of ground surveys.

This general movement is in addition to a daily or diurnal variation in which the north magnetic pole describes a rough ellipse, with a maximum deviation of 80 km (50 mi) from its mean position. This effect is due to disturbances of the geomagnetic field by charged particles from the Sun.

As of early 2019, the magnetic north pole is moving from Canada towards Siberia at a rate of approximately 55 km (34 mi) per year.

Exploration

The first team of novices to reach the magnetic north pole did so in 1996, led by David Hempleman-Adams. It included the first British woman Sue Stockdale and first Swedish woman to reach the Pole. The team also successfully tracked the location of the Magnetic North Pole on behalf of the University of Ottawa, and certified its location by magnetometer and theodolite at 78°35′42″N 104°11′54″W.

The Polar Race was a biannual competition that ran from 2003 until 2011. It took place between the community of Resolute, on the shores of Resolute Bay, Nunavut, in northern Canada and the 1996 location of the north magnetic pole at 78°35′42″N 104°11′54″W, also in northern Canada.

On 25 July 2007, the Top Gear: Polar Special was broadcast on BBC Two in the United Kingdom, in which Jeremy Clarkson, James May, and their support and camera team claimed to be the first people in history to reach the 1996 location of the north magnetic pole in northern Canada by car. Note that they did not reach the actual north magnetic pole, which at the time (2007) had moved several hundred kilometers further north from the 1996 position.

Magnetic north and magnetic declination

Magnetic declination from true north in 2000.

Historically, the magnetic compass was an important tool for navigation. While it has been widely replaced by Global Positioning Systems, many airplanes and ships still carry them, as do casual boaters and hikers.

The direction in which a compass needle points is known as magnetic north. In general, this is not exactly the direction of the north magnetic pole (or of any other consistent location). Instead, the compass aligns itself to the local geomagnetic field, which varies in a complex manner over Earth's surface, as well as over time. The local angular difference between magnetic north and true north is called the magnetic declination. Most map coordinate systems are based on true north, and magnetic declination is often shown on map legends so that the direction of true north can be determined from north as indicated by a compass.

In North America the line of zero declination (the agonic line) runs from the north magnetic pole down through Lake Superior and southward into the Gulf of Mexico (see figure). Along this line, true north is the same as magnetic north. West of the agonic line a compass will give a reading that is east of true north and by convention the magnetic declination is positive. Conversely, east of the agonic line a compass will point west of true north and the declination is negative.

North geomagnetic pole

As a first-order approximation, Earth's magnetic field can be modeled as a simple dipole (like a bar magnet), tilted about 10° with respect to Earth's rotation axis (which defines the geographic north and geographic south poles) and centered at Earth's center. The north and south geomagnetic poles are the antipodal points where the axis of this theoretical dipole intersects Earth's surface. If Earth's magnetic field were a perfect dipole then the field lines would be vertical at the geomagnetic poles, and they would coincide with the magnetic poles. However, the approximation is imperfect, and so the magnetic and geomagnetic poles lie some distance apart.

Like the north magnetic pole, the north geomagnetic pole attracts the north pole of a bar magnet and so is in a physical sense actually a magnetic south pole. It is the center of the region of the magnetosphere in which the Aurora Borealis can be seen. As of 2015 it was located at approximately 80°22′12″N 72°37′12″W, over Ellesmere Island, Canada but it is now drifting away from North America and toward Siberia.

Geomagnetic reversal

Over the life of Earth, the orientation of Earth's magnetic field has reversed many times, with magnetic north becoming magnetic south and vice versa – an event known as a geomagnetic reversal. Evidence of geomagnetic reversals can be seen at mid-ocean ridges where tectonic plates move apart and the seabed is filled in with magma. As the magma seeps out of the mantle, cools, and solidifies into igneous rock, it is imprinted with a record of the direction of the magnetic field at the time that the magma cooled.

Ester

From Wikipedia, the free encyclopedia
An ester of carboxylic acid. R stands for any group (organic or inorganic, typically hydrogen or organyl) and R′ stands for organyl group.

In chemistry, an ester is a compound derived from an acid (organic or inorganic) in which the hydrogen atom (H) of at least one acidic hydroxyl group (−OH) of that acid is replaced by an organyl group (−R). Analogues derived from oxygen replaced by other chalcogens belong to the ester category as well. According to some authors, organyl derivatives of acidic hydrogen of other acids are esters as well (e.g. amides), but not according to the IUPAC.

Glycerides are fatty acid esters of glycerol; they are important in biology, being one of the main classes of lipids and comprising the bulk of animal fats and vegetable oils. Lactones are cyclic carboxylic esters; naturally occurring lactones are mainly 5- and 6-membered ring lactones. Lactones contribute to the aroma of fruits, butter, cheese, vegetables like celery and other foods.

Esters can be formed from oxoacids (e.g. esters of acetic acid, carbonic acid, sulfuric acid, phosphoric acid, nitric acid, xanthic acid), but also from acids that do not contain oxygen (e.g. esters of thiocyanic acid and trithiocarbonic acid). An example of an ester formation is the substitution reaction between a carboxylic acid (R−C(=O)−OH) and an alcohol (R'−OH), forming an ester (R−C(=O)−O−R'), where R stands for any group (organic or inorganic, typically hydrogen or organyl) and R′ stands for organyl group.

Organyl esters of carboxylic acids typically have a pleasant smell; those of low molecular weight are commonly used as fragrances and are found in essential oils and pheromones. They perform as high-grade solvents for a broad array of plastics, plasticizers, resins, and lacquers, and are one of the largest classes of synthetic lubricants on the commercial market. Polyesters are important plastics, with monomers linked by ester moieties. Esters of phosphoric acid form the backbone of DNA molecules. Esters of nitric acid, such as nitroglycerin, are known for their explosive properties.

There are compounds in which an acidic hydrogen of acids mentioned in this article are not replaced by an organyl, but by some other group. According to some authors, those compounds are esters as well (e.g. according to them, trimethylstannyl acetate (or trimethyltin acetate) CH3COOSn(CH3)3 is a trimethylstannyl ester of acetic acid, and dibutyltin dilaurate (CH3(CH2)10COO)2Sn((CH2)3CH3)2 is a dibutylstannylene ester of lauric acid).

Nomenclature

Etymology

The word ester was coined in 1848 by a German chemist Leopold Gmelin, probably as a contraction of the German EssigÀther, "acetic ether".

IUPAC nomenclature

The names of esters that are formed from an alcohol and an acid, are derived from the parent alcohol and the parent acid, where the latter may be organic or inorganic. Esters derived from the simplest carboxylic acids are commonly named according to the more traditional, so-called "trivial names" e.g. as formate, acetate, propionate, and butyrate, as opposed to the IUPAC nomenclature methanoate, ethanoate, propanoate, and butanoate. Esters derived from more complex carboxylic acids are, on the other hand, more frequently named using the systematic IUPAC name, based on the name for the acid followed by the suffix -oate. For example, the ester hexyl octanoate, also known under the trivial name hexyl caprylate, has the formula CH3(CH2)6CO2(CH2)5CH3.

Butyl acetate, an ester derived from butanol (right side of the picture, blue) and acetic acid (left side of the picture, orange). The acidic hydrogen atom from acetic acid is replaced by a butyl group.

The chemical formulas of organic esters formed from carboxylic acids and alcohols usually take the form RCO2R' or RCOOR', where R and R' are the organyl parts of the carboxylic acid and the alcohol, respectively, and R can be a hydrogen in the case of esters of formic acid. For example, butyl acetate (systematically butyl ethanoate), derived from butanol and acetic acid (systematically ethanoic acid) would be written CH3CO2(CH2)3CH3. Alternative presentations are common including BuOAc and CH3COO(CH2)3CH3.

Cyclic esters are called lactones, regardless of whether they are derived from an organic or inorganic acid. One example of an organic lactone is γ-valerolactone.

Orthoesters

An uncommon class of esters are the orthoesters. One of them are the esters of orthocarboxylic acids. Those esters have the formula RC(OR′)3, where R stands for any group (organic or inorganic) and R′ stands for organyl group. For example, triethyl orthoformate (HC(OCH2CH3)3) is derived, in terms of its name (but not its synthesis) from esterification of orthoformic acid (HC(OH)3) with ethanol.

Esters of inorganic acids

A phosphoric acid ester, where R stands for an organyl group.

Esters can also be derived from inorganic acids.

Inorganic acids that exist as tautomers form two or more kinds of esters.

Some inorganic acids that are unstable or elusive form stable esters.

In principle, all metal and metalloid alkoxides, of which many hundreds are known, could be classified as esters of the hypothetical acids, e.g. aluminium triethoxide (Al(OCH2CH3)3) could be classified as an ester of aluminic acid which is aluminium hydroxide, tetraethyl orthosilicate (Si(OCH2CH3)4) could be classified as an ester of orthosilicic acid, and titanium ethoxide (Ti(OCH2CH3)4) could be classified as an ester of orthotitanic acid.

Structure and bonding

Esters derived from carboxylic acids and alcohols contain a carbonyl group C=O, which is a divalent group at C atom, which gives rise to 120° C–C–O and O–C–O angles. Unlike amides, carboxylic acid esters are structurally flexible functional groups because rotation about the C–O–C bonds has a low barrier. Their flexibility and low polarity is manifested in their physical properties; they tend to be less rigid (lower melting point) and more volatile (lower boiling point) than the corresponding amides. The pKa of the alpha-hydrogens on esters is around 25.

Many carboxylic acid esters have the potential for conformational isomerism, but they tend to adopt an S-cis (or Z) conformation rather than the S-trans (or E) alternative, due to a combination of hyperconjugation and dipole minimization effects. The preference for the Z conformation is influenced by the nature of the substituents and solvent, if present. Lactones with small rings are restricted to the s-trans (i.e. E) conformation due to their cyclic structure.

Ester conformers.png
Metrical details for methyl benzoate, distances in picometers.

Physical properties and characterization

Esters derived from carboxylic acids and alcohols are more polar than ethers but less polar than alcohols. They participate in hydrogen bonds as hydrogen-bond acceptors, but cannot act as hydrogen-bond donors, unlike their parent alcohols. This ability to participate in hydrogen bonding confers some water-solubility. Because of their lack of hydrogen-bond-donating ability, esters do not self-associate. Consequently, esters are more volatile than carboxylic acids of similar molecular weight.

Characterization and analysis

Esters are generally identified by gas chromatography, taking advantage of their volatility. IR spectra for esters feature an intense sharp band in the range 1730–1750 cm−1 assigned to ÎœC=O. This peak changes depending on the functional groups attached to the carbonyl. For example, a benzene ring or double bond in conjugation with the carbonyl will bring the wavenumber down about 30 cm−1.

Applications and occurrence

Esters are widespread in nature and are widely used in industry. In nature, fats are, in general, triesters derived from glycerol and fatty acids. Esters are responsible for the aroma of many fruits, including apples, durians, pears, bananas, pineapples, and strawberries. Several billion kilograms of polyesters are produced industrially annually, important products being polyethylene terephthalate, acrylate esters, and cellulose acetate.

Representative triglyceride found in a linseed oil, a triester (triglyceride) derived of linoleic acid (bottom right), alpha-linolenic acid (left), and oleic acid (top right).

Preparation

Esterification is the general name for a chemical reaction in which two reactants (typically an alcohol and an acid) form an ester as the reaction product. Esters are common in organic chemistry and biological materials, and often have a pleasant characteristic, fruity odor. This leads to their extensive use in the fragrance and flavor industry. Ester bonds are also found in many polymers.

Esterification of carboxylic acids with alcohols

The classic synthesis is the Fischer esterification, which involves treating a carboxylic acid with an alcohol in the presence of a dehydrating agent:

RCO2H + R'OH ⇌ RCO2R' + H2O

The equilibrium constant for such reactions is about 5 for typical esters, e.g., ethyl acetate. The reaction is slow in the absence of a catalyst. Sulfuric acid is a typical catalyst for this reaction. Many other acids are also used such as polymeric sulfonic acids. Since esterification is highly reversible, the yield of the ester can be improved using Le Chatelier's principle:

  • Using the alcohol in large excess (i.e., as a solvent).
  • Using a dehydrating agent: sulfuric acid not only catalyzes the reaction but sequesters water (a reaction product). Other drying agents such as molecular sieves are also effective.
  • Removal of water by physical means such as distillation as a low-boiling azeotropes with toluene, in conjunction with a Dean-Stark apparatus.

Reagents are known that drive the dehydration of mixtures of alcohols and carboxylic acids. One example is the Steglich esterification, which is a method of forming esters under mild conditions. The method is popular in peptide synthesis, where the substrates are sensitive to harsh conditions like high heat. DCC (dicyclohexylcarbodiimide) is used to activate the carboxylic acid to further reaction. 4-Dimethylaminopyridine (DMAP) is used as an acyl-transfer catalyst.

Steglich-1.svg

Another method for the dehydration of mixtures of alcohols and carboxylic acids is the Mitsunobu reaction:

RCO2H + R'OH + P(C6H5)3 + R2N2 → RCO2R' + OP(C6H5)3 + R2N2H2

Carboxylic acids can be esterified using diazomethane:

RCO2H + CH2N2 → RCO2CH3 + N2

Using this diazomethane, mixtures of carboxylic acids can be converted to their methyl esters in near quantitative yields, e.g., for analysis by gas chromatography. The method is useful in specialized organic synthetic operations but is considered too hazardous and expensive for large-scale applications.

Esterification of carboxylic acids with epoxides

Carboxylic acids are esterified by treatment with epoxides, giving β-hydroxyesters:

RCO2H + RCHCH2O → RCO2CH2CH(OH)R

This reaction is employed in the production of vinyl ester resin from acrylic acid.

Alcoholysis of acyl chlorides and acid anhydrides

Alcohols react with acyl chlorides and acid anhydrides to give esters:

RCOCl + R'OH → RCO2R' + HCl
(RCO)2O + R'OH → RCO2R' + RCO2H

The reactions are irreversible simplifying work-up. Since acyl chlorides and acid anhydrides also react with water, anhydrous conditions are preferred. The analogous acylations of amines to give amides are less sensitive because amines are stronger nucleophiles and react more rapidly than does water. This method is employed only for laboratory-scale procedures, as it is expensive.

Alkylation of carboxylate salts

Although rarely employed for esterifications, carboxylate salts (often generated in situ) react with electrophilic alkylating agents, such as alkyl halides, to give esters. Anion availability can inhibit this reaction, which correspondingly benefits from phase transfer catalysts or such highly polar aprotic solvents as DMF. An additional iodide salt may, via the Finkelstein reaction, catalyze the reaction of a recalcitrant alkyl halide. Alternatively, salts of a coordinating metal, such as silver, may improve the reaction rate by easing halide elimination.

Transesterification

Transesterification, which involves changing one ester into another one, is widely practiced:

RCO2R' + CH3OH → RCO2CH3 + R'OH

Like the hydrolysation, transesterification is catalysed by acids and bases. The reaction is widely used for degrading triglycerides, e.g. in the production of fatty acid esters and alcohols. Poly(ethylene terephthalate) is produced by the transesterification of dimethyl terephthalate and ethylene glycol:

(C6H4)(CO2CH3)2 + 2 C2H4(OH)21/n[(C6H4)(CO2)2(C2H4)]n + 2 CH3OH

A subset of transesterification is the alcoholysis of diketene. This reaction affords 2-ketoesters.

(CH2CO)2 + ROH → CH3C(O)CH2CO2R

Carbonylation

Alkenes undergo "hydroesterification" in the presence of metal carbonyl catalysts. Esters of propanoic acid are produced commercially by this method:

H2C=CH2 + ROH + CO → CH3CH2CO2R

A preparation of methyl propionate is one illustrative example.

H2C=CH2 + CO + CH3OH → CH3CH2CO2CH3

The carbonylation of methanol yields methyl formate, which is the main commercial source of formic acid. The reaction is catalyzed by sodium methoxide:

CH3OH + CO → HCO2CH3

Addition of carboxylic acids to alkenes and alkynes

In hydroesterification, alkenes and alkynes insert into the O−H bond of carboxylic acids. Vinyl acetate is produced industrially by the addition of acetic acid to acetylene in the presence of zinc acetate catalysts: Presently, zinc acetate is used as the catalyst:

H2C=CH2 + CH3CO2H → CH3CO2CH=CH2

Vinyl acetate can also be produced by palladium-catalyzed reaction of ethylene, acetic acid, and oxygen:

2 H2C=CH2 + 2 CH3CO2H + O2 → 2 CH3CO2CH=CH2 + 2 H2O

Silicotungstic acid is used to manufacture ethyl acetate by the alkylation of acetic acid by ethylene:

H2C=CH2 + CH3CO2H → CH3CO2CH2CH3

From aldehydes

The Tishchenko reaction involve disproportionation of an aldehyde in the presence of an anhydrous base to give an ester. Catalysts are aluminium alkoxides or sodium alkoxides. Benzaldehyde reacts with sodium benzyloxide (generated from sodium and benzyl alcohol) to generate benzyl benzoate. The method is used in the production of ethyl acetate from acetaldehyde.

Other methods

Reactions

Esters react with nucleophiles at the carbonyl carbon. The carbonyl is weakly electrophilic but is attacked by strong nucleophiles (amines, alkoxides, hydride sources, organolithium compounds, etc.). The C–H bonds adjacent to the carbonyl are weakly acidic but undergo deprotonation with strong bases. This process is the one that usually initiates condensation reactions. The carbonyl oxygen in esters is weakly basic, less so than the carbonyl oxygen in amides due to resonance donation of an electron pair from nitrogen in amides, but forms adducts.

Hydrolysis and saponification

Esterification is a reversible reaction. Esters undergo hydrolysis under acidic and basic conditions. Under acidic conditions, the reaction is the reverse reaction of the Fischer esterification. Under basic conditions, hydroxide acts as a nucleophile, while an alkoxide is the leaving group. This reaction, saponification, is the basis of soap making.

Ester saponification (basic hydrolysis)

The alkoxide group may also be displaced by stronger nucleophiles such as ammonia or primary or secondary amines to give amides: (ammonolysis reaction)

RCO2R' + NH2R″ → RCONHR″ + R'OH

This reaction is not usually reversible. Hydrazines and hydroxylamine can be used in place of amines. Esters can be converted to isocyanates through intermediate hydroxamic acids in the Lossen rearrangement.

Sources of carbon nucleophiles, e.g., Grignard reagents and organolithium compounds, add readily to the carbonyl.

Reduction

Compared to ketones and aldehydes, esters are relatively resistant to reduction. The introduction of catalytic hydrogenation in the early part of the 20th century was a breakthrough; esters of fatty acids are hydrogenated to fatty alcohols.

RCO2R' + 2 H2 → RCH2OH + R'OH

A typical catalyst is copper chromite. Prior to the development of catalytic hydrogenation, esters were reduced on a large scale using the Bouveault–Blanc reduction. This method, which is largely obsolete, uses sodium in the presence of proton sources.

Especially for fine chemical syntheses, lithium aluminium hydride is used to reduce esters to two primary alcohols. The related reagent sodium borohydride is slow in this reaction. DIBAH reduces esters to aldehydes.

Direct reduction to give the corresponding ether is difficult as the intermediate hemiacetal tends to decompose to give an alcohol and an aldehyde (which is rapidly reduced to give a second alcohol). The reaction can be achieved using triethylsilane with a variety of Lewis acids.

Claisen condensation and related reactions

As for aldehydes, the hydrogen atoms on the carbon adjacent ("α to") the carboxyl group in esters are sufficiently acidic to undergo deprotonation, which in turn leads to a variety of useful reactions. Deprotonation requires relatively strong bases, such as alkoxides. Deprotonation gives a nucleophilic enolate, which can further react, e.g., the Claisen condensation and its intramolecular equivalent, the Dieckmann condensation. This conversion is exploited in the malonic ester synthesis, wherein the diester of malonic acid reacts with an electrophile (e.g., alkyl halide), and is subsequently decarboxylated. Another variation is the Fráter–Seebach alkylation.

Other reactions

Protecting groups

As a class, esters serve as protecting groups for carboxylic acids. Protecting a carboxylic acid is useful in peptide synthesis, to prevent self-reactions of the bifunctional amino acids. Methyl and ethyl esters are commonly available for many amino acids; the t-butyl ester tends to be more expensive. However, t-butyl esters are particularly useful because, under strongly acidic conditions, the t-butyl esters undergo elimination to give the carboxylic acid and isobutylene, simplifying work-up.

Hazards

Esters react with strong oxidizing acids, which may cause a violent reaction that is sufficiently exothermic to ignite the esters and the reaction products. Heat is also generated by the interaction of esters with alkali solutions. Very flammable hydrogen gas is generated by mixing esters with alkali metals and ionic hydrides.

List of ester odorants

Many esters have distinctive fruit-like odors, and many occur naturally in the essential oils of plants. This has also led to their common use in artificial flavorings and fragrances which aim to mimic those odors.

Ester name Structure Odor or occurrence
Allyl hexanoate Prop-2-enyl hexanoate.svg pineapple
Benzyl acetate Benzyl acetate-structure.svg pear, strawberry, jasmine
Bornyl acetate Bornyl acetate.svg pine
Butyl acetate Butylacetat.svg apple, honey
Butyl butyrate Butyl butyrate2.svg pineapple
Butyl propionate Butyl propionate.png pear drops, apple
Ethyl acetate Ethyl acetate2.svg nail polish remover, model paint, model airplane glue, pears
Ethyl benzoate Ethyl benzoate.svg sweet, wintergreen, fruity, medicinal, cherry, grape
Ethyl butyrate Ethyl butyrate2.svg banana, pineapple, strawberry
Ethyl hexanoate Ethyl-hexanoate.svg pineapple, waxy-green banana
Ethyl cinnamate Ethyl-cinnamate.svg cinnamon
Ethyl formate Ethyl formate Structural Formulae.svg lemon, rum, strawberry
Ethyl heptanoate Ethyl-heptanoate.svg apricot, cherry, grape, raspberry
Ethyl isovalerate Ethyl isovalerate structure.svg apple
Ethyl lactate Ethyl lactate.svg butter, cream
Ethyl nonanoate Ethyl-nonanoate.svg grape
Ethyl pentanoate Ethyl valerate.svg apple
Geranyl acetate Geranyl-acetate.svg geranium
Geranyl butyrate Geranyl butyrate.svg cherry
Geranyl pentanoate Geranyl pentanoate.svg apple
Isobutyl acetate Isobutyl-acetate.svg cherry, raspberry, strawberry
Isobutyl formate Isobutyl formate.svg raspberry
Isoamyl acetate Isoamyl acetate.svg pear, banana (flavoring in Pear drops)
Isopropyl acetate Isopropyl acetate.svg fruity
Linalyl acetate Linalyl acetate.svg lavender, sage
Linalyl butyrate Linalyl butyrate.svg peach
Linalyl formate Linalyl formate.svg apple, peach
Methyl acetate Methyl-acetate.svg glue
Methyl anthranilate Methyl anthranilate.svg grape, jasmine
Methyl benzoate Methyl benzoate.svg fruity, ylang ylang, feijoa
Methyl butyrate (methyl butanoate) Buttersauremethylester.svg pineapple, apple, strawberry
Methyl cinnamate Methyl cinnamate.svg strawberry
Methyl formate Methyl formate.png pleasant, ethereal, rum, sweet
Methyl pentanoate (methyl valerate) Methyl pentanoate.svg flowery
Methyl phenylacetate Methyl phenylacetate.svg honey
Methyl salicylate (oil of wintergreen) Methyl salicylate.svg Modern root beer, wintergreen, Germolene and Ralgex ointments (UK)
Nonyl caprylate Nonyl caprylate.svg orange
Octyl acetate Octyl acetate.svg fruity-orange
Octyl butyrate Octyl butyrate.svg parsnip
Amyl acetate (pentyl acetate) Amyl acetate.svg apple, banana
Pentyl butyrate (amyl butyrate) Pentyl butyrate.svg apricot, pear, pineapple
Pentyl hexanoate (amyl caproate) Pentyl hexanoate.svg apple, pineapple
Pentyl pentanoate (amyl valerate) Pentyl pentanoate.svg apple
Propyl acetate Propyl acetate.svg pear
Propyl hexanoate Propyl-hexanoate.svg blackberry, pineapple, cheese, wine
Propyl isobutyrate Propyl isobutyrate.svg rum
Terpenyl butyrate Terpenyl butyrate.svg cherry

Authorship of the Bible

From Wikipedia, the free encyclopedia ...