ether

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(ē'thər) pronunciation
n.
  1. Any of a class of organic compounds in which two hydrocarbon groups are linked by an oxygen atom.
  2. A volatile, highly flammable liquid, C2H5OC2H5, derived from the distillation of ethyl alcohol with sulfuric acid and used as a reagent and solvent. It was formerly used as an anesthetic. Also called diethyl ether, ethyl ether.
  3. The regions of space beyond the earth's atmosphere; the heavens.
  4. The element believed in ancient and medieval civilizations to fill all space above the sphere of the moon and to compose the stars and planets.
  5. Physics. An all-pervading, infinitely elastic, massless medium formerly postulated as the medium of propagation of electromagnetic waves.

[Middle English, upper air, from Latin aethēr, from Greek aithēr.]

etheric e·ther'ic (ĭ-thĕr'ĭk, ĭ-thîr'-) adj.


Any of a class of organic compounds whose molecular structure has an oxygen atom interposed between two carbon atoms that are part of hydrocarbon molecules. Ethers have the general chemical formula ROR, in which R and R represent the hydrocarbons. They resemble alcohols but generally are less dense, less soluble in water, more volatile, and more inert. They are used in chemical processing, for extraction and separation of chemicals, and as solvents. Some are used as insecticides and soil fumigants. They are also used in medicine and pharmacology. Codeine is the methyl ether of morphine. The term ether often refers to ethyl ether (C2H5OC2H5), best known as an anesthetic but also used as a solvent, an extractant, and a reaction medium.

For more information on ether, visit Britannica.com.

(1) An invisible medium through which all light, heat and electromagnetic waves propagate. Pronounced "ee-ther" with the "th" as in the word "thought," ether was postulated from the 1600s to the 1800s. The word inspired the name Ethernet.

(2) A group of chemical compounds, the most popular of which is the colorless and transparent diethyl ether, used as a solvent and anesthetic. Diethyl ether was synthesized in the 1500s and named "ether" in the 1700s.

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In 1881 Albert A. Michelson and Edward Morley tried to measure the absolute velocity of Earth with respect to the rest of the universe. The result of their measurement showed that Earth is at rest in space, but no one believed that that could be true. The idea of a motionless Earth had been given up 300 years earlier. Something had to be wrong with the experiment.

The problem at first glance seemed to be with light. Ever since Thomas Young had demonstrated in 1803 that light produces interference patterns, it was assumed that light must be waves, a view previously held by Christiaan Huygens and others. All those who espoused the wave theory--the alternative theory was that light consisted of particles--assumed that light must be waves in something. When Augustin-Jean Fresnel began to work on the wave theory of light, he named the something ether, after Aristotle's fifth element. Fresnel was able to show that light waves are more like water waves (but in three dimensions instead of just up and down) than they are like sound waves (which are back and forth instead of up and down).

Michelson had taken a suggestion of James Clerk Maxwell, made in 1875, to develop a sensitive measuring tool based on the interference patterns of waves of light. The Michelson-Morley experiment was designed to use the interferometer, Michelson's new tool, to measure how Earth moves through the ether, which was assumed to be stationary. Michelson and Morley measured the speed of light in two perpendicular directions. The speed was found to be the same, implying that Earth stands still.

Others had different explanations. Both George Francis Fitzgerald and Hendrik Antoon Lorentz suggested that the problem could be resolved by assuming that objects contract when they move. By assigning the correct value to the contraction, the speed of light could be made to appear the same in two different directions, since the apparatus used to measure it would contract in the direction in which Earth is moving.

In 1905 Albert Einstein resolved the issue in a different way. Einstein perceived that the same physical laws must be true in all frames of reference in steady motion with respect to each other. But this requirement also means that light must have the same speed no matter how a body is moving. There can be no fixed frame of reference against which Earth moves, so Michelson and Morley got the correct result. In addition, the Fitzgerald-Lorentz contraction is a real effect, explained by Einstein's theory. Furthermore, in a separate paper, Einstein showed that light behaves like a particle as well as like a wave. Although this wave-particle duality remains difficult to picture, it has become quite clear since 1905 that light has both wave and particle properties. A particle does not require a medium the way that a wave does.

Does the ether exist? Einstein's theory of special relativity suggests that the question is irrelevant. Certainly no one thinks today that a solid medium pervades space. On the other hand, it is widely believed that there is no real vacuum. Arno Penzias and Robert Wilson detected in 1964 the cosmic background radiation, a leftover of the big bang. This radiation is pervasive and basically the same in all directions. It is possible to measure Earth's movement against this background radiation. As it turns out, Earth moves.

A city which fell to the lot of the tribe of Judah (Josh 15:20, 42) when the land of Canaan was divided by Joshua among the Children of Israel (Josh 14:1); however it is also mentioned as being in the domain of Simeon (Josh 19:7). It has been suggested that these are two different cities but many scholars disagree. It was in the eastern lowlands of Judah but its present location is unknown.

Concordance
Josh 15:42; 19:7


in chemistry
in physics and astronomy

ether, any of a number of organic compounds whose molecules contain two hydrocarbon groups joined by single bonds to an oxygen atom. The most common of these compounds is ethyl ether, CH3CH2OCH2CH3, often called simply ether, a colorless, volatile liquid with a distinctive odor; its IUPAC name is ethoxyethane. Ethyl ether boils at 34.5°C and is extremely flammable. It is insoluble in water but mixes with many organic solvents and is widely used as a solvent itself, e.g., for fats and oils. Its most familiar historical application is as an anesthetic. An ether such as ethyl ether in which both hydrocarbon groups are identical is said to be a simple, or symmetrical, ether. An ether in which the two groups differ (e.g., methyl ethyl ether, CH3OCH2CH3) is said to be a mixed, or unsymmetrical, ether. Ethers are often prepared commercially by heating an alcohol with sulfuric acid; the reaction is one of dehydration. In the laboratory ethers are often prepared by reaction of an alkyl halide with a sodium alkoxide (a method called the Williamson synthesis). Ethers are usually chemically unreactive but can be cleaved (broken apart) at high temperatures by concentrated hydrogen halides; initially an alkyl halide and an alcohol are formed. Epoxides are a special class of cyclic ethers.

ether or aether, in physics and astronomy, a hypothetical medium for transmitting light and heat (radiation), filling all unoccupied space; it is also called luminiferous ether. In Newtonian physics all waves are propagated through a medium, e.g., water waves through water, sound waves through air. When James Clerk Maxwell developed his electromagnetic theory of light, Newtonian physicists postulated ether as the medium that transmitted electromagnetic waves. Ether was held to be invisible, without odor, and of such a nature that it did not interfere with the motions of bodies through space. The concept was intended to connect the Newtonian mechanistic wave theory with Maxwell's field theory. However, all attempts to demonstrate its existence, most notably the Michelson-Morley experiment of 1887, produced negative results and stimulated a vigorous debate among physicists that was not ended until the special theory of relativity, proposed by Albert Einstein in 1905, became accepted. The theory of relativity eliminated the need for a light-transmitting medium, so that today the term ether is used only in a historical context.


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pronunciation

IN BRIEF: n. - A colorless volatile highly inflammable liquid formerly used as an inhalation anesthetic; A medium that was once supposed to fill all space and to support the propagation of electromagnetic waves.

Tutor's tip: The doctor told her patient she could have "either" (one of two) no anesthetic or "ether" (a chemical) .

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As a compound class, ethers are fairly variable in flavor type. Diphenyl is a rosy character, beta naphthyl ethyl ether is sweet, aromatic, and grapey. Tetrahydropyrans are six-membered oxygen-containing heterocyclic rings. Dioxanes are six-membered heterocycles with two oxygens para to each other. Structures like pyrazines are their nitrogen-containing counterpart. Oenanthic ether is not really an ether but is a complex mixture of esters and other trace compounds.

  1. any anhydride, of general formula R1 — O — R2, formed between two (identical or nonidentical) organic hydroxy compounds.
  2. the common name for diethyl ether (or ethyl ether or ethoxyethane), C2H5 — O — C2H5.

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1. diethyl ether: a colorless, transparent, very volatile, highly inflammable liquid with a characteristic odor; given by inhalation to produce general anesthesia.
2. any organic compound containing an oxygen atom bonded to two carbon atoms.

  • spiritus e. nit. — used as a stimulant for depressed animals, both as an inhalant and in oral drenches.
  • vinyl e. — a clear colorless liquid used as an inhalation anesthetic.
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  See crossword solutions for the clue Ether.
The general structure of an ether

Ethers (play /ˈθər/) are a class of organic compounds that contain an ether group — an oxygen atom connected to two alkyl or aryl groups — of general formula R–O–R'.[1] A typical example is the solvent and anesthetic diethyl ether, commonly referred to simply as "ether" (CH3-CH2-O-CH2-CH3). Ethers are common in organic chemistry and pervasive in biochemistry, as they are common linkages in carbohydrates and lignin.

Contents

Structure and bonding

Ethers feature C-O-C linkage defined by a bond angle of about 104.5° and C-O distances of about 140 pm. The barrier to rotation about the C-O bonds is low. The bonding of oxygen in ethers, alcohols, and water is similar. In the language of valence bond theory, the hybridization at oxygen is sp3.

Oxygen is more electronegative than carbon, thus the hydrogens alpha to ethers are more acidic than in simple hydrocarbons. They are far less acidic than hydrogens alpha to carbonyl groups (such as in ketones or aldehydes), however.

Depending on the groups at R and R', ether is classified into two types:

1) Simple ethers or symmetrical ethers 2) Mixed ethers or asymmetrical ethers

Nomenclature

The names for simple ethers (i.e. those with none or few other functional groups) are a composite of the two substituents followed by "ether." Ethyl methyl ether (CH3OC2H5), diphenylether (C6H5OC6H5). IUPAC rules are often not followed for simple ethers. As for other organic compounds, very common ethers acquired names before rules for nomenclature were formalized. Diethyl ether is simply called "ether," but was once called sweet oil of vitriol. Methyl phenyl ether is anisole, because it was originally found in aniseed. The aromatic ethers include furans. Acetals (α-alkoxy ethers R-CH(-OR)-O-R) are another class of ethers with characteristic properties.

In the IUPAC nomenclature system, ethers are named using the general formula "alkoxyalkane", for example CH3-CH2-O-CH3 is methoxyethane. If the ether is part of a more complex molecule, it is described as an alkoxy substituent, so -OCH3 would be considered a "methoxy-" group. The simpler alkyl radical is written in front, so CH3-O-CH2CH3 would be given as methoxy(CH3O)ethane(CH2CH3). The nomenclature of describing the two alkyl groups and appending "ether", e.g. "ethyl methyl ether" in the example above, is a trivial usage.

Polyethers

Polyethers are compounds with more than one ether group.

The crown ethers are examples of low-molecular polyethers. Some toxins produced by dinoflagellates such as brevetoxin and ciguatoxin are in a class known as cyclic or ladder polyethers.

Polyether generally refers to polymers which contain the ether functional group in their main chain. The term glycol is reserved for low to medium range molar mass polymer when the nature of the end-group, which is usually a hydroxyl group, still matters. The term "oxide" or other terms are used for high molar mass polymer when end-groups no longer affect polymer properties.

Aliphatic polyethers

Name of the polymers with low to medium molar mass Name of the polymers with high molar mass Preparation Repeating unit Examples of trade names
Paraformaldehyde Polyoxymethylene (POM) or polyacetal or polyformaldehyde Step-growth polymerisation of formaldehyde -CH2O- Delrin from DuPont
Polyethylene glycol (PEG) Polyethylene oxide (PEO) or polyoxyethylene (POE) Ring-opening polymerization of ethylene oxide -CH2CH2O- Carbowax from Dow
Polypropylene glycol (PPG) Polypropylene oxide (PPO) ou polyoxypropylene) (POP) Anionic ring-opening polymerization of propylene oxide -CH2CH(CH3)O-
Polytetramethylene glycol (PTMG) or Polytetramethylene ether glycol (PTMEG) Polytetrahydrofuran (PTHF) Acid-catalyzed ring-opening polymerization of tetrahydrofuran -CH2CH2CH2CH2O- Terathane from Invista and PolyTHF from BASF

Aromatic polyethers

The phenyl ether polymers are a class of polyethers containing aromatic cycles in their main chain: Polyphenyl ether (PPE) and Poly(p-phenylene oxide) (PPO).

Related compounds

Many classes of compounds with C-O-C linkages are not considered ethers: Esters (R-C(=O)-O-R), hemiacetals (R-CH(-OH)-O-R), carboxylic acid anhydrides (RC(=O)-O-C(=O)R).

Physical properties

Ether molecules cannot form hydrogen bonds with each other, resulting in a relatively low boiling points compared to those of the analogous alcohols. The difference, however, in the boiling points of the ethers and their isometric alcohols becomes lower as the carbon chains become longer, as the van der Waals interactions of the extended carbon chain dominates over the presence of hydrogen bonding.

Ethers are slightly polar. The C-O-C bond angle in the functional group is about 110°, and the C-O dipoles do not cancel out. Ethers are more polar than alkenes but not as polar as alcohols, esters, or amides of comparable structure. However, the presence of two lone pairs of electrons on the oxygen atoms makes hydrogen bonding with water molecules possible.

Cyclic ethers such as tetrahydrofuran and 1,4-dioxane are miscible in water because of the more exposed oxygen atom for hydrogen bonding as compared to aliphatic ethers.

Selected data about some alkyl ethers
Ether Structure m.p. (°C) b.p. (°C) Solubility in 1 liter of H2O Dipole moment (D)
Dimethyl ether CH3-O-CH3 -138.5 -23.0 70 g 1,30
Diethyl ether CH3CH2-O-CH2CH3 -116.3 34.4 69 g 1.14
Tetrahydrofuran O(CH2)4 -108.4 66.0 Miscible 1.74
Dioxane O(C2H4)2O 11.8 101.3 Miscible 0.45

 

Reactions

Structure of the polymeric diethyl ether peroxide

Ethers in general are of low chemical reactivity, but they are more reactive than alkanes (epoxides, ketals, and acetals are unrepresentative classes of ethers and are discussed in separate articles). Important reactions are listed below.[2]

Ether cleavage

Although ethers resist hydrolysis, they are cleaved by mineral acids such as hydrobromic acid and hydroiodic acid. Hydrogen chloride cleaves ethers only slowly. Methyl ethers typically afford methyl halides:

ROCH3 + HBr → CH3Br + ROH

These reactions proceed via onium intermediates, i.e. [RO(H)CH3]+Br-.

Some ethers rapidly cleave with boron tribromide (even aluminium chloride is used in some cases) to give the alkyl bromide.[3] Depending on the substituents, some ethers can be cleaved with a variety of reagents, e.g. strong base.

Peroxide formation

When stored in the presence of air or oxygen, ethers tend to form explosive peroxides, such as diethyl ether peroxide. The reaction is accelerated by light, metal catalysts, and aldehydes. In addition to avoiding storage conditions likely to form peroxides, it is recommended, when an ether is used as a solvent, not to distill it to dryness, as any peroxides that may have formed, being less volatile than the original ether, will become concentrated in the last few drops of liquid.

Lewis bases

Ethers serve as Lewis bases and Bronsted bases. Strong acids protonate the oxygen to give "onium ions." For instance, diethyl ether forms a complex with boron trifluoride, i.e. diethyl etherate (BF3.OEt2). Ethers also coordinate to Mg(II) center in Grignard reagents. Polyethers, including many antibiotics, cryptands, and crown ethers, bind alkali metal cations strongly.

Alpha-halogenation

This reactivity is akin to the tendency of ethers with alpha hydrogen atoms to form peroxides. Chlorine gives alpha-chloroethers.

Synthesis

Ethers can be prepared in the laboratory in several different ways.

Dehydration of alcohols

The Dehydration of alcohols affords ethers:

2 R-OH → R-O-R + H2O at high temperature

This direct reaction requires elevated temperatures (about 125 °C). The reaction is catalyzed by acids, usually sulfuric acid. The method is effective for generating symmetrical ethers, but not unsymmetrical ethers. Diethyl ether is produced from ethanol by this method. Cyclic ethers are readily generated by this approach. Such reactions must compete with dehydration of the alcohol:

R-CH2-CH2(OH) → R-CH=CH2 + H2O

The dehydration route often requires conditions incompatible with delicate molecules. Several milder methods exist to produce ethers.

Williamson ether synthesis

Nucleophilic displacement of alkyl halides by alkoxides

R-ONa + R'-X → R-O-R' + NaX

This reaction is called the Williamson ether synthesis. It involves treatment of a parent alcohol with a strong base to form the alkoxide, followed by addition of an appropriate aliphatic compound bearing a suitable leaving group (R-X). Suitable leaving groups (X) include iodide, bromide, or sulfonates. This method usually does not work well for aryl halides (e.g. bromobenzene (see Ullmann condensation below). Likewise, this method only gives the best yields for primary halides. Secondary and tertiary halides are prone to undergo E2 elimination on exposure to the basic alkoxide anion used in the reaction due to steric hindrance from the large alkyl groups.

In a related reaction, alkyl halides undergo nucleophilic displacement by phenoxides. The R-X cannot be used to react with the alcohol. However, phenols can be used to replace the alcohol, while maintaining the alkyl halide. Since phenols are acidic, they readily react with a strong base like sodium hydroxide to form phenoxide ions. The phenoxide ion will then substitute the -X group in the alkyl halide, forming an ether with an aryl group attached to it in a reaction with an SN2 mechanism.

C6H5OH + OH- → C6H5-O- + H2O
C6H5-O- + R-X → C6H5OR

Ullmann condensation

The Ullmann condensation is similar to the Williamson method except that the substrate is an aryl halide. Such reactions generally require a catalyst, such as copper.

Electrophilic addition of alcohols to alkenes

Alcohols add to electrophilically activated alkenes.

R2C=CR2 + R-OH → R2CH-C(-O-R)-R2

Acid catalysis is required for this reaction. Often, mercury trifluoroacetate (Hg(OCOCF3)2) is used as a catalyst for the reaction, geneating an ether with Markovnikov regiochemistry. Using similar reactions, tetrahydropyranyl ethers are used as protective groups for alcohols.

Preparation of epoxides

Epoxides are typically prepared by oxidation of alkenes. The most important epoxide in terms of industrial scale is ethylene oxide, which is produced by oxidation of ethylene with oxygen. Other epoxides are produced by one of two routes:

  • By the oxidation of alkenes with a peroxyacid such as m-CPBA.
  • By the base intramolecular nucleophilic substitution of a halohydrin.

Important ethers

Chemical structure of ethylene oxide Ethylene oxide The smallest cyclic ether.
Chemical structure of dimethyl ether Dimethyl ether An aerosol spray propellant. A potential renewable alternative fuel for diesel engines with a cetane rating as high as 56-57.
Chemical structure of diethyl ether Diethyl ether A common low boiling solvent (b.p. 34.6 °C), and an early anaesthetic. Used as starting fluid for diesel engines.
Chemical structure of dimethoxyethane Dimethoxyethane (DME) A high boiling solvent (b.p. 85 °C):
Chemical structure of dioxane Dioxane A cyclic ether and high boiling solvent (b.p. 101.1 °C).
Chemical structure of THF Tetrahydrofuran (THF) A cyclic ether, one of the most polar simple ethers that is used as a solvent.
Chemical structure of anisole Anisole (methoxybenzene) An aryl ether and a major constituent of the essential oil of anise seed.
Chemical structure of 18-crown-6 Crown ethers Cyclic polyethers that are used as phase transfer catalysts.
Chemical structure of polyethylene glycol Polyethylene glycol (PEG) A linear polyether, e.g. used in cosmetics and pharmaceuticals.

References

  1. ^ Nic, M.; Jirat, J.; Kosata, B., eds. (2006–). "ethers". IUPAC Compendium of Chemical Terminology (Online ed.). doi:10.1351/goldbook.E02221. ISBN 0-9678550-9-8. http://goldbook.iupac.org/E02221.html. 
  2. ^ Wilhelm Heitmann, Günther Strehlke, Dieter Mayer "Ethers, Aliphatic" in Ullmann's Encyclopedia of Industrial Chemistry" Wiley-VCH, Weinheim, 2002. doi:10.1002/14356007.a10_023
  3. ^ J. F. W. McOmie and D. E. West (1973), "3,3'-Dihydroxylbiphenyl", Org. Synth., http://www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?prep=CV5P0412 ; Coll. Vol. 5: 412 

External links


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Dansk (Danish)
n. - æter

Nederlands (Dutch)
ether, opperste hemelsfeer, stof dat opperste hemelsfeer vult (filosofie)

Français (French)
n. - (Chim, Phys) éther, les éthers, les espaces célestes (littér)

Deutsch (German)
n. - Äther

Ελληνική (Greek)
n. - (χημ.) αιθήρ. αιθέρας

Italiano (Italian)
etere

Português (Portuguese)
n. - éter (m) (Quím.)

Русский (Russian)
эфир, небесное пространство

Español (Spanish)
n. - éter

Svenska (Swedish)
n. - eter

中文(简体)(Chinese (Simplified))
乙醚, 以太, 醚, 太空, 苍穹

中文(繁體)(Chinese (Traditional))
n. - 乙醚, 以太, 醚, 太空, 蒼穹

한국어 (Korean)
n. - 하늘, 빛, 열, 전자기의 복사 현상의 가상적 매체

日本語 (Japanese)
n. - エーテル, 天空上層の空間, ラジオ

العربيه (Arabic)
‏(الاسم) السماء, الأثير‏

עברית (Hebrew)
n. - ‮אתר, סם הרדמה‬


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