Ether

From Wikipedia, the free encyclopedia Jump to: navigation, search This article is about a general class of organic compounds. For other uses, see Aether.

The general structure of an ether Ethers ( /ir/) are a class of organic compounds that contain an ether group an oxygen atom connected to two alkyl or aryl groups of general formula ROR'.[1] A typical example is the solvent and anesthetic diethyl ether, commonly referred to simply as "ether" (CH3-CH2-OCH2-CH3). Ethers are common in organic chemistry and pervasive in biochemistry, as they are common linkages in carbohydrates and lignin.

Contents
[hide]

1 Structure and bonding 2 Nomenclature o 2.1 Polyethers o 2.2 Related compounds 3 Physical properties 4 Reactions o 4.1 Ether cleavage o 4.2 Peroxide formation o 4.3 Lewis bases o 4.4 Alpha-halogenation 5 Synthesis o 5.1 Dehydration of alcohols o 5.2 Williamson ether synthesis o 5.3 Ullmann condensation o 5.4 Electrophilic addition of alcohols to alkenes o 5.5 Preparation of epoxides 6 Important ethers 7 References 8 External links

[edit] 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

[edit] 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 (-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.

[edit] Polyethers
Polyethers are compounds with more than one ether group. The crown ethers are examples of low-molecular weight 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 Name of the polymers with low to polymers with high medium molar mass molar mass Polyoxymethylene Paraformaldehyde (POM) or polyacetal or polyformaldehyde Polyethylene oxide Polyethylene glycol (PEO) or (PEG) polyoxyethylene (POE) Polypropylene oxide Polypropylene glycol (PPO) ou (PPG) polyoxypropylene) (POP) Polytetramethylene glycol (PTMG) or Polytetrahydrofuran Polytetramethylene (PTHF) ether glycol (PTMEG) Aromatic polyethers

Preparation

Repeating unit

Examples of trade names Delrin from DuPont Carbowax from Dow

Step-growth polymerisation of -CH2Oformaldehyde Ring-opening polymerization of -CH2CH2Oethylene oxide Anionic ringopening -CH2CH(CH3)Opolymerization of propylene oxide

Terathane Acid-catalyzed from Invista ring-opening and polymerization of CH2CH2CH2CH2OPolyTHF tetrahydrofuran from BASF

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).

[edit] Related compounds

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

[edit] 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 CO 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 m.p. b.p. Solubility in 1 liter of Ether Structure (C) (C) H2 O Dimethyl ether CH3-O-CH3 -138.5 -23.0 70 g CH3CH2-ODiethyl ether -116.3 34.4 69 g CH2CH3 Tetrahydrofuran O(CH2)4 -108.4 66.0 Miscible Dioxane O(C2H4)2O 11.8 101.3 Miscible

Dipole moment (D) 1,30 1.14 1.74 0.45

[edit] 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]

[edit] 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.

[edit] 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.

[edit] 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.

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

[edit] Synthesis
Ethers can be prepared in the laboratory in several different ways.

[edit] 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.

[edit] 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

[edit] 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.

[edit] 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.

[edit] Preparation of epoxides

Main article: epoxide 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.

[edit] Important ethers

Ethylene oxide

The smallest cyclic ether. An aerosol spray propellant. A potential renewable alternative fuel for diesel engines with a cetane rating as high as 56-57. A common low boiling solvent (b.p. 34.6 C), and an early anaesthetic. Used as starting fluid for diesel engines. A high boiling solvent (b.p. 85 C): A cyclic ether and high boiling solvent (b.p. 101.1 C).

Dimethyl ether

Diethyl ether Dimethoxyethane (DME) Dioxane

Tetrahydrofuran (THF)

A cyclic ether, one of the most polar simple ethers that is used as a solvent.

Anisole (methoxybenzene)

An aryl ether and a major constituent of the essential oil of anise seed.

Crown ethers

Cyclic polyethers that are used as phase transfer catalysts.

Polyethylene glycol A linear polyether, e.g. used in cosmetics and (PEG) pharmaceuticals.

[edit]

Eter
Dari Wikipedia bahasa Indonesia, ensiklopedia bebas Belum Diperiksa Langsung ke: navigasi, cari Artikel ini berisi tentang sebuah golongan utama dari senyawa organik. Untuk senyawa yang lebih spesifik, lihat dietil eter. Untuk teknologi jaringan komputer, lihat ethernet.

Struktur umum dari eter Eter adalah suatu senyawa organik yang mengandung gugus ROR', dengan R dapat berupa alkil maupun aril.[1] Contoh senyawa eter yang paling umum adalah pelarut dan anestetik dietil eter (etoksietana, CH3-CH2-O-CH2-CH3). Eter sangat umum ditemukan dalam kimia organik dan biokimia, karena gugus ini merupakan gugus penghubung pada senyawa karbohidrat dan lignin.

Daftar isi
[sembunyikan]

1 Struktur dan ikatan o 1.1 Struktur Serupa 2 Sifat-sifat fisika 3 Reaksi o 3.1 Pembelahan eter o 3.2 Pembentukan peroksida o 3.3 Sebagai basa Lewis 4 Sintesis o 4.1 Dehidrasi alkohol o 4.2 Sintesis eter Williamson o 4.3 Kondensasi Ullmann o 4.4 Adisi elektrofilik alkohol ke alkena o 4.5 Pembuatan epoksida 5 Beberapa eter penting 6 Referensi

[sunting] Struktur dan ikatan

Eter memiliki ikatan C-O-C yang bersudut ikat sekitar 110 dan jarak C-O sekitar 140 pm. Sawar rotasi ikatan C-O sangatlah rendah. Menurut teori ikatan valensi, hibridisasi oksigen pada senyawa eter adalah sp3. Oksigen lebih elektronegatif daripada karbon, sehingga hidrogen yang berada pada posisi alfa relatif terhadap eter bersifat lebih asam daripada hidrogen senyawa hidrokarbon. Walau demikian, hidrogen ini kurang asam dibandingkan dengan alfa hidrogen keton.

[sunting] Struktur Serupa

Eter tidak boleh disamakan dengan gugus-gugus sejenis berikut yang mempunyai stuktur serupa - R-O-R.

Senyawa aromatik seperti furan di mana oksigen adalah sebahagian daripada sistem aromatik. Senyawa dengan atom-atom karbon yang bersebelahan dengan oksigen terikat dengan oksigen, nitrogen, atau sulfur: o Ester R-C(=O)-O-R o Asetal R-CH(-O-R)-O-R o Aminal R-CH(-NH-R)-O-R o Anhidrida R-C(=O)-O-C(=O)-R

[sunting] Sifat-sifat fisika

Molekul-molekul eter tidak dapat berikatan hidrogen dengan sesamanya, sehingga mengakibatkan senyawa eter memiliki titik didih yang relatif rendah dibandingkan dengan alkohol. Eter bersifat sedikit polar karena sudut ikat C-O-C eter adalah 110 derajat, sehingga dipol C-O tidak dapat meniadakan satu sama lainnya. Eter lebih polar daripada alkena, namun tidak sepolar alkohol, ester, ataupun amida. walau demikian, keberadaan dua pasangan elektron menyendiri pada atom oksigen eter, memungkinkan eter berikatan hidrogen dengan molekul air.Eter dapat dipisahkan secara sempurna melalui destilasi. Eter siklik seperti tetrahidrofuran dan 1,4-dioksana sangat larut dalam air karena atom oksigennya lebih terpapar ikatan hidrogen dibandingkan dengan eter-eter alifatik lainnya. Beberapa alkil eter Titik lebur Titidk didih Kelarutan dalam 1 L Momen (C) (C) H2 O dipol (D) -138,5 -23,0 70 g 1,30 -116,3 -108,4 34,4 66,0 69 g Larut pada semua perbandingan 1,14 1,74

Eter Dimetil eter Dietil eter

Struktur CH3-O-CH3 CH3CH2-OCH2CH3

Tetrahidrofuran O(CH2)4

Dioksana

O(C2H4)2O

11,8

101,3

Larut pada semua perbandingan

0,45

[sunting] Reaksi
Eter secara umumnya memiliki reaktivitas kimia yang rendah, walaupun ia lebih reaktif daripada alkana. Beberapa contoh reaksi penting eter adalah sebagai berikut.[2]

[sunting] Pembelahan eter

Walaupun eter tahan terhadap hidrolisis, ia dapat dibelah oleh asam-asam mineral seperi asam bromat dan asam iodat. Asam klorida hanya membelah eter dengan sangat lambat. Metil eter umumnya akan menghasilkan metil halida: ROCH3 + HBr CH3Br + ROH Reaksi ini berjalan via zat antara onium, yaitu [RO(H)CH3]+Br-. Beberapa jenis eter dapat terbelah dengan cepat menggunakan boron tribomida (dalam beberapa kasus aluminium klorida juga dapat digunakan) dan menghasilkan alkil bromida.[3] Berganting pada substituennya, beberapa eter dapat dibelah menggunakan berbagai jenis reagen seperti basa kuat.

[sunting] Pembentukan peroksida

Eter primer dan sekunder dengan gugus CH di sebelah oksigen eter, dapat membentuk peroksida, misalnya dietil eter peroksida. Reaksi ini memerlukan oksigen (ataupun udaara), dan dipercepat oleh cahaya, katalis logam, dan aldehida. Peroksida yang dihasilkan dapat meledak. Oleh karena ini, diisopropil eter dan tetrahidrofuran jarang digunakan sebagai pelarut.

[sunting] Sebagai basa Lewis

Eter dapat berperan sebagai basa Lewis maupun basa Bronsted. Asam kuat dapat memprotonasi oksigen, menghasilkan "ion onium". Contohnya, dietil eter dapat membentuk kompleks dengan boron trifluorida, yaitu dietil eterat (BF3.OEt2). Eter juga berkooridasi dengan Mg(II) dalam reagen Grignard. Polieter (misalnya eter mahkoya) dapat mengikat logam dengan sangat kuat.

[sunting] Sintesis
Eter dapat disintesis melalui beberapa cara:

[sunting] Dehidrasi alkohol

Dehidrasi senyawa alkohol dapat menghasilkan eter:

2 R-OH R-O-R + H2O Reaksi ini memerlukan temperatur yang tinggi (sekitar 125 C). Reaksi ini dikatalisis oleh asam, biasanya asam sulfat. Metode ini efektif untukn menghasilkan eter simetris, namun tidak dapat digunakan untuk menghasilkan eter tak simetris. Dietil eter dihasilkan dari etanol menggunakan metode ini. Eter siklik dapat pula dihasilkan menggunakan metode ini.

[sunting] Sintesis eter Williamson

Eter dapat pula dibuat melalui substitusi nukleofilik alkil halida oleh alkoksida R-ONa + R'-X R-O-R' + NaX Reaksi ini dinamakan sintesis eter Williamson. Reaksi ini melibatkan penggunaan alkohol dengan basa kuat, menghasilkan alkoksida, yang diikuti oleh adisi pada senyawa alifatik terkait yang memiliki gugus lepas (R-X). Gugus lepas tersebut dapat berupa iodida, bromida, maupun sulfonat. Metode ini biasanya tidak bekerja dengan baik dengan aril halida (misalnya bromobenzena). Reaksi ini menghasilkan rendemen reaksi yang tinggi untuk halida primer. Halida sekunder dan tersier sangat rawan menjalani reaksi eliminasi E2 seketika berpaparan dengan anion alkoksida yang sangat basa. Dalam reaksi lainnya yang terkait, alkil halida menjalani substitusi nukleofilik oleh fenoksida. RX tidak dapat digunakan untuk bereaksi dengan alkohol. Namun, fenol dapat digunakan untuk menggantikan alkohol. Oleh karena fenol bersifat asam, ia dapat bereaksi dengan basa kuat seperti natrium hidroksida, membentuk ion fenoksida. Ion fenoksida ini kemudian mensubstitusi gugus -X pada alkil halida, menghasilkan eter dengan gugus aril yang melekat padanya melalui mekanisme reaksi SN2. C6H5OH + OH- C6H5-O- + H2O C6H5-O- + R-X C6H5OR

[sunting] Kondensasi Ullmann

Kondensasi Ullmann mirip dengan metode Williamson, kecuali substratnya adalah aril halida. Reaksi ini umumnya memerlukan katalis, misalnya tembaga.

[sunting] Adisi elektrofilik alkohol ke alkena

Alkohol dapat melakukan reaksi adisi dengan alkena yang diaktivasi secara elektrofilik. R2C=CR2 + R-OH R2CH-C(-O-R)-R2 Katalis asam diperlukan agar reaksi ini dapat berjalan. Biasanya merkuri trifluoroasetat (Hg(OCOCF3)2) digunakan sebagai katalis.

[sunting] Pembuatan epoksida

Artikel utama untuk bagian ini adalah: epoksida Epoksida biasanya dibuat melalui oksidasi alkena. Eposida yang paling penting dalam industri adalah etilena oksida, yang dihasilkan melalui oksidasi etilena dengan oksigen. Epoksida lainnya dapat dihasilkan melalui dua cara:

Melalui oksidasi alkena dengan peroksiasam seperti Asam meta-kloroperoksibenzoat (mCPBA). Melalui substitusi nukleofilik intramolekuler halohidrin.

[sunting] Beberapa eter penting

Etilena oksida Eter siklik yang paling sederhana. Merupakan propelan pada aerosol. Merupakan bahan bakar alternatif yang potensial untuk mesin diesel karena mempunyai bilangan cetan sebesar 5657. Merupakan pelarut umum pada suhu rendah (b.p. 34.6 C), dan dulunya merupakan zat anestetik. Digunakan sebagai cairan starter kontak pada mesin diesel. Pelarut pada suhu tinggi (b.p. 85 C): Merupakan eter siklik dan pelarut pada suhu tinggi (b.p. 101.1 C).

Dimetil eter

Dietil eter Dimetoksimetana (DME) Dioksana

Tetrahidrofuran (THF)

Eter siklik, salah satu eter yang bersifat paling polar yang digunakan sebagai pelarut.

Anisol (metoksibenzena)

Merupakan eter aril dan komponen utama minyak esensial pada biji adas manis.

Eter mahkota

Polieter siklik yang digunakan sebagai katalis transfer fase.

Polietilen glikol (PEG)

Merupakan polieter linear, digunakan pada kosmetik dan farmasi.

[sunting]