Term
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Definition
| compound of formula R-O-R', where R and R' can be an alkyl or aryl group |
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Term
| difference between alcohols and ethers |
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Definition
in alcohols, one H is replaced by an alkyl group
in ethers, both H's are replaced by an alkyl group |
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Term
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Definition
| relatively unreactive, except for epoxides |
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Term
| bp of ethers compared to alcohols of identical molecular weights |
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Definition
| ethers tend to have boiling points about 100°C lower than those of alcohols of identical weight |
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Term
| the intermolecular forces ethers do have |
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Definition
-London forces
-dipole-dipole interactions |
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Term
| molecules ethers can H-bond with |
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Definition
| molecules that have a O-H or N-H group; these molecules can donate a H-bond to the ether and the ether can accept it |
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Term
| the ions ether tends to solvate better |
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Definition
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Term
| the ions ether tends to not solvate as well |
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Definition
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Term
| why alcohols can't be used as solvents for bases stronger than the alkoxide ion |
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Definition
| because the hydroxy group quickly protonates the base |
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Term
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Definition
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Term
| how ether interacts with Grignard reagent |
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Definition
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Definition
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Term
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Definition
large cyclic polyether that specifically solvates a certain metal cation by complexing it in the center of the ring
[image] |
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Term
| an important use of crown ethers |
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Definition
| helps polar inorganic salts dissolve in nonpolar inorganic solvents; complexes with the cation and leaves the anion bare and highly reactive |
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Term
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Definition
| contains a ring in which at least one member is something other than C |
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Term
| reagent that is often used to convert alkenes to epoxides |
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Definition
peroxybenzoic acid
[image] |
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Term
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Definition
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Definition
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Term
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Definition
4-membered cyclic ether
[image] |
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Definition
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Definition
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Definition
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Definition
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Term
| tetrahydrofuran (THF) (oxolane) |
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Definition
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Term
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Definition
| tetrahydrofuran (THF) (oxolane) |
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Term
| something THF can be used for |
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Definition
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Definition
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Term
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Definition
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Term
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Definition
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Term
| tetrahydropyran (THP) (oxane) |
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Definition
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Term
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Definition
| tetrahydropyran (THP) (oxane) |
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Term
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Definition
| 6-membered heterocyclic ethers with 2 O's in the ring |
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Term
| how IR spectroscopy can be used to determine whether or not the compound is an ether |
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Definition
| ethers and many other compounds give a C-O stretch around 1000 to 1200 cm-1 in the fingerprint region, but if a molecule containing an oxygen has no O-H or C=O group, then it's possibly an ether |
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Term
| the most common fragmentation of ethers |
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Definition
| cleavage next to one of the C atoms bonded to O |
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Term
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Definition
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Term
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Definition
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Term
| why α Cleavage is favorable for an ether |
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Definition
| because the resulting oxonium ion is resonance-stabilized |
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Term
| another common cleavage of ether |
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Definition
| loss of either of the 2 alkyl groups, yielding an oxonium ion or an alkyl cation |
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Term
| cleavage of ether by loss of alkyl group |
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Definition
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Term
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Definition
| cleavage of ether by loss of alkyl group |
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Term
| the most reliable an versatile method of ether synthesis |
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Definition
| Williamson ether synthesis |
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Term
| mechanism for Williamson ether synthesis |
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Definition
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Term
| why use of a secondary alkyl halide is less effective than primary in Williamson ether synthesis |
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Definition
| because elimination competes, often resulting in poor yields |
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Term
| alkoxymercuration-demurcuration |
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Definition
adds an -OR group on one end of the double bond; puts that -OH group in the Markovnikov position
[image] |
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Term
| the cheapest method of synthesizing symmetrical ethers |
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Definition
| bimolecular condensation of alcohols |
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Term
| bimolecular condensation of alcohols |
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Definition
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Term
| the type of alcohol that must be used in bimolecular condensation of alcohols |
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Definition
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Term
| cleavage of ethers using HBr and HI |
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Definition
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Term
| mechanism for cleavage of ethers using HBr and HI |
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Definition
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Term
| conditions under which ethers can react |
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Definition
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Term
| the mechanism that usually takes place in cleavage of ethers using HBr and HI |
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Definition
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Term
| iodide and bromide ions are ______ nucleophiles |
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Definition
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Term
| iodide and bormide ions are ______ bases |
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Definition
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Term
| type of alcohol where the HBr and HI won't convert it to an alkyl halide |
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Definition
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Term
| the type of substitution that occurs when a protonated alcohol reacts with bromide or iodide ion |
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Definition
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Term
| hydrohalic acids in order of their reactivity towards the cleavage of ethers |
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Definition
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Term
| why phenols do not react to produce halides |
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Definition
| because the sp2 hybridized C atom of the phenol can't do the SN2 or SN1 rxn needed to make the halide |
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Term
| mechanism of phenyl ethers reacting with HBr and HI |
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Definition
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Term
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Definition
oxidation of ethers when stored in presence of atmospheric O; this forms hydroperoxides and dialkyl peroxides
[image] |
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Term
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Definition
| ethers with a S in place of the O |
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Definition
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Definition
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Definition
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Term
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Definition
| ethers with a substituted Si atom replacing one of the alkyl groups of an ether |
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Term
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Definition
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Term
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Definition
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Term
| difference between ethers and thioethers aka sulfides |
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Definition
| thioethers can undergo oxidation and alkylation of the S atom |
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Term
| difference between silyl ethers and ethers |
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Definition
| silyl ethers are more easily formed and more easily hydrolyzed |
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Term
| important use of silyl ethers |
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Definition
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Term
| mechanism of synthesizing thioethers using Williamson ether synthesis |
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Definition
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Term
| generation of thiolate ions |
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Definition
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Term
| reactivity of sulfides vs. reactivity of ethers |
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Definition
| sulfides are much more reactive than ethers |
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Term
| oxidation of sulfide aka thioester |
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Definition
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Definition
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Definition
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Definition
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Definition
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Definition
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Definition
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Definition
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Term
| formation of a sulfonium salt |
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Definition
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Definition
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Term
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Definition
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Term
| why sulfonium salts are strong alkylating agents |
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Definition
| because sulfonium salts polarize the C atom, making it electrophilic |
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Term
| nucleophilic attack on a sulfonium salt |
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Definition
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Term
| characteristics of a good protecting group |
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Definition
-easy to add to the group it protects
-resistant to the reagents used to modify other parts of the molecule
-easy to remove to restore the original functional group |
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Term
| a type of ether that's a good protecting group |
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Definition
| silicon-based ethers (silyl ethers) |
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Term
| why the fluoride ion removes silyl ethers under gentle conditions |
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Definition
| because the Si-F bond is exceptionally strong |
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Term
| a type of silyl ether that makes a good protecting group |
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Definition
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Term
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Definition
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Term
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Definition
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Term
| synthesis of triisopropylsilyl (TIPS) |
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Definition
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Term
| triisopropyl ether (TIPS) being used as a protecting group |
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Definition
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Term
| reagent often used in synthesis of triisopropylsilyl ether (TIPS) |
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Definition
| tertiary amine, such as Et3N |
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Term
| example of triisopropyl ether being used as a protecting group |
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Definition
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Definition
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Term
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Definition
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Term
| synthesis of epoxide using epoxyacid |
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Definition
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Term
| conditions under which the epoxide opens to a glycol |
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Definition
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Term
| desirable conditions under which to make an epoxide |
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Definition
| in the absence of strong acids |
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Term
| peroxyacid that is often used in peroxyacid epoxidation |
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Definition
| meta-chloroperoxybenzoic acid (mCPBA) |
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Term
| meta-chlorperoxybenzoic acid (mCPBA) |
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Definition
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Term
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Definition
| meta-chlorperoxybenzoic acid (mCPBA) |
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Term
| mechanism for epoxide synthesis using peroxyacid |
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Definition
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Term
| magnesium monoperoxyphthalate (MMPP) |
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Definition
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Term
| synthesis of an epoxide using MMPP |
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Definition
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Term
| mechanism for base-promoted cyclization of halohydrins |
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Definition
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Term
| mechanism for forming a chlorohydrin |
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Definition
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Term
| mechanism for displacing a chlorohydrin to form an epoxide |
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Definition
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Term
| base that is often used in converting halohydrins into cyclic ethers (5, 6, 7, and occasionally 4-membered rings) |
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Definition
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Definition
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Term
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Definition
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Term
| mechanism for converting chlorohydrin into cyclic ether using 2,6-lutidine |
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Definition
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Term
| base-promoted cyclization of halohydrins |
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Definition
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Term
| what epoxides do in acidic conditions |
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Definition
| they open to form glycols |
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Term
| mechanism of acid-catalyzed opening of epoxides in water |
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Definition
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Term
| direct hydroxylation of alkenes |
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Definition
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Term
| what acid-catalyzed opening of an epoxide in alcohol produces |
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Definition
| an alkoxy alcohol with anti stereochemistry, because the alcohol becomes an alkoxide ion |
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Term
| mechanism for acid-catalyzed opening of epoxides in alcohol |
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Definition
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Term
| opening epoxides using hydrohalic acids |
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Definition
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Term
| why most ethers do not undergo nucleophilic substitution |
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Definition
| because alkoxide ion is a poor leaving group |
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Term
| base-catalyzed opening of epoxides |
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Definition
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Term
| rxn coordinate diagram comparing epoxides to acyclic ethers |
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Definition
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Term
| mechanism for base-catalyzed opening of epoxides |
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Definition
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Term
| what base-catalyzed opening of epoxides produces |
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Definition
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Term
| a type of amine that can open an epoxide |
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Definition
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Term
| mechanism for opening epoxide using aqueous ammonia (NH3) |
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Definition
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Term
| ethanolamine further reacting with epoxides |
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Definition
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Term
| opening of epoxide under acid-catalyzed conditions |
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Definition
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Term
| opening of epoxide under base-catalyzed conditions |
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Definition
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Term
| mechanism for base-catalyzed opening of an epoxide |
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Definition
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Term
| mechanism for acid-catalyzed opening of an epoxide |
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Definition
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Term
| the carbon that gets attacked in acid-catalyzed opening of epoxides |
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Definition
| the more substituted one, since it has more + charge |
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Term
| the carbon that gets attacked in base-catalyzed opening of epoxides |
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Definition
| the less substituted one, since it's less hindered |
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Term
| comparison of acid-catalyzed and base-catalyzed opening of epoxide |
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Definition
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Term
| opening of epoxide with Grignard or organolithium reagent |
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Definition
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Term
| mechanism for opening of epoxide with Grignard reagent |
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Definition
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Term
| which type of reagent is more selective? Grignard or organolithium? |
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Definition
| organolithium reagents are more selective (Grignards can attack more substituted C's) |
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Term
| how epoxy resins form good quality glues as they harden |
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Definition
by polymerizing with each other
[image]
[image]
[image] |
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Term
| how cross-links are formed between chains of epoxy polymers in glue |
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Definition
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Term
| Acid-catalyzed epoxide opening in water |
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Definition
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Term
| Acid-catalyzed epoxide opening in alcohol |
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Definition
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Term
| using hydrohalic acids to open epoxides |
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Definition
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Term
| base-catalyzed epoxide opening with alkoxodes or hydrides |
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Definition
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Term
| base-catalyzed epoxide opening with organometallics |
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Definition
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Term
| the reagent that must be used to remove the silyl ether (R-O-SiR3) group |
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Definition
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