IUPAC Nomenclature Notes (Page-by-Page)
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- Topic: How to Name Alkanes, Alkyl Halides, and Alcohols using the IUPAC System.
- IUPAC system: one of the most commonly used nomenclature systems today.
- Fundamental principle: Each different compound shall have a unique name.
- Emphasis: IUPAC system provides a universal, unambiguous naming method for organic compounds.
Key terms:
- IUPAC = International Union of Pure and Applied Chemistry.
- Nomenclature = system for naming chemical compounds.
Significance:
- Enables precise communication in science and commerce across languages and regions.
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- While IUPAC names are standard, common (trivial) names are still widely used by chemists and in commerce.
- Learning common names for frequently used chemicals can be important for practical understanding and communication.
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- Alkanes: general formula CnH{2n+2}.
- Example: hexane with formula C6H{14}.
- Cycloalkanes: general formula CnH{2n}.
- Example: cyclohexane with formula C6H{12}.
- Distinguishing feature: Alkanes are open-chain; cycloalkanes contain rings.
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- The common alkane name ending: -ane.
- The names of most alkanes derive from Greek/Latin roots:
- 1 → meth- (methyl), 2 → eth- (ethyl), 3 → prop- (propyl), 4 → but- (butyl), 5 → pent- (pentyl).
- This page emphasizes the root system used for straight-chain alkanes.
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- Provides a quick reference of simple alkanes and their structures in the unbranched series:
- Methane: ext{CH}_4
- Ethane: ext{CH}3 ext{CH}3
- Propane: ext{CH}3 ext{CH}2 ext{CH}_3
- Butane: ext{CH}3 ext{CH}2 ext{CH}2 ext{CH}3
- Pentane: ext{CH}3( ext{CH}2)3 ext{CH}3
- Hexane: ext{CH}3( ext{CH}2)4 ext{CH}3
- Heptane: ext{CH}3( ext{CH}2)5 ext{CH}3
- Octane: ext{CH}3( ext{CH}2)6 ext{CH}3
- Nonane: ext{CH}3( ext{CH}2)7 ext{CH}3
- Decane: ext{CH}3( ext{CH}2)8 ext{CH}3
- Note: The slide also lists cycloalkanes like cyclohexane with formula C6H{12} as part of the broader alkane family.
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- 3A. How to Name Unbranched Alkyl Groups.
- Alkyl group defined as the removal of one hydrogen atom from an alkane.
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- Alkyl group (continued):
- Methane yields methyl group (Me).
- Ethane yields ethyl group (Et).
- Propane yields propyl group (Pr).
- Diagrammatic note: removing a terminal hydrogen from the corresponding alkane yields the alkyl group.
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- 3B. How to Name Branched-Chain Alkanes – Rule 1:
- Use the longest continuous carbon chain as the parent name.
- Example sketches show branches such as 3-methylheptane and 2-ethylhexane.
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- Rule (Cont’d):
- After selecting the longest chain, apply Rule 2 to designate the location of the substituent(s).
- The rule set also emphasizes choosing the lowest possible locants for substituents.
- Examples illustrate how numbering is chosen to minimize substituent positions.
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- Rule 4 (in the course of rules for substituents):
- For two or more substituents, use the lowest possible individual numbers for the parent chain.
- Substituents should be listed in alphabetical order.
- In alphabetizing, disregard multiplying prefixes like di-, tri-, etc.
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- Example illustrations of naming with multiple substituents, showing how to assign numbers and order:
- Example name like (6-Ethyl-2-methyloctane) is given.
- The “NOT” figures indicate numbers that would be incorrect under the rules.
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- Rule 5: When two substituents appear on the same carbon, use that number twice (e.g., 4-ethyl-4-methyloctane).
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- Rule 6: For identical substituents, use prefixes di-, tri-, tetra-, etc. (e.g., 2,4-dimethylhexane).
- Examples show how to place multiple identical substituents on the parent chain with correct numbering.
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- Rule 7: When two chains have equal length, prefer the chain with more substituents as the parent.
- Example: a tricyclic scenario showing 2,3,5-trimethyl-4-propylheptane as a preferred name over a chain with fewer substituents.
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- Rule 8: When branching starts at equal distances from either end of the longest chain, choose the name that gives the lower number at the first point of difference.
- Demonstrated with a comparison of two naming options.
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- Example 1 (Find the longest chain as parent): shows a structure with several possible parent chains; choose the longest chain as the parent.
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- Example 1 (Cont’d): two methyl substituents (dimethyl) on the chosen chain; use the lowest possible numbering for the substituents.
- Finalization leads to a name such as dimethylheptane with the correct numbering.
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- Example 1 (Cont’d): complete name for the given structure is (3,4-Dimethylheptane).
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- Example 2 introduction (longer chain): appears to set up a second naming example with different substituents.
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- Example 2 (Cont’d): process begins with determining whether a longer chain exists or if a different parent should be chosen; starting with a 6-carbon chain in the first impression.
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- Example 2 (Cont’d): evaluation leads to an 8- or 9-carbon chain; the correct parent is Nonane (a 9-carbon chain) in the illustrated solution.
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- Example 2 (Cont’d): use the lowest numbering for substituents: numbers shown from 1 to 9 vs. a reversed set, choosing the set that yields the lowest set of locants.
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- Substituents in Example 2: 3,7-dimethyl and 4-ethyl.
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- Substituents arranged in alphabetical order, disregarding di- in dimethyl (i.e., Ethyl comes before dimethyl).
- Complete name given: (4-Ethyl-3,7-dimethylnonane).
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- 3C. How to Name Branched Alkyl Groups:
- For alkanes with more than two carbon atoms, more than one derived alkyl group is possible.
- Examples: Propyl, Isopropyl (or 1-methylethyl).
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- Four-carbon groups: tert-butyl (or 1,1-dimethylethyl); sec-butyl (1-methylpropyl); Butyl family includes isobutyl.
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- A neopentyl group is referenced (2,2-dimethylpropyl).
- Neopentyl is also part of the branched-alkyl naming discussion.
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- Example 1 (unspecified molecular structure in this page): indicates there is an illustrative example for naming.
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- Example 1 (Cont’d) parts (a), (b), (c), (d) show different possible parent chain lengths (6-, 7-, 8-, 9-carbon chains) to determine the longest chain as parent.
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- Example 1 (Cont’d): shows final selection of the longest chain and numbering for substituents to minimize locants.
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- Example 1 (Cont’d): final substitution numbering (e.g., 4,5 or 5,6) is chosen based on the lowest locants; two alternative drawings show equivalent options, with one preferred by locant rules.
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- Example 1 (Cont’d): substituents identified as isopropyl and tert-butyl; the final name is 4-tert-Butyl-2-methyl-1-heptene.
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- Example 1 (Cont’d): substitutes arranged alphabetically (tert-Butyl before isopropyl when applying the “ignore di- for alphabetization” rule).
- Final complete name: 5-tert-Butyl-4-isopropylnonane is shown earlier; note that the exact drawing in this page leads to 5-tert-Butyl-4-isopropylnonane in one part and 4-tert-Butyl-2-methyl-1-heptene in another depending on the chosen parent chain and presence of a double bond.
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- Example 2 introduction (unlabeled structure): introduces a second example to apply the rules.
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- Example 2 (Cont’d): determine the longest-chain parent; ends with 8-, 9-, or 10-carbon chain suggestions; toward choosing Decane as parent in the given example.
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- Example 2 (Cont’d): two alternative depictions of the same naming problem; focuses on obtaining the correct substituent locants.
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- Example 2 (Cont’d): final substitution numbering and substituents listed; shows the logic for choosing the lowest set of locants when multiple options exist.
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- Example 2 (Cont’d): substituents identified as sec-butyl and neopentyl; which has precedence affects the final naming.
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- Example 2 (Cont’d): due to precedence of sec-butyl over neopentyl, the complete name is 10,8,6,4,2-5 ext{-sec-Butyl-6-neopentyldecane} (illustrative ordering shown; the key is sec-butyl takes precedence and locants are chosen accordingly).
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- 3D. How to Classify Hydrogen Atoms:
- 1° (primary) hydrogens, 2° (secondary) hydrogens, 3° (tertiary) hydrogens.
- Illustrates how different hydrogen environments are categorized on hydrocarbon frameworks.
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- 3E. How to Name Alkyl Halides:
- Halogens are treated as substituents (prefix position), not as the main functional group.
- Halogen names: F → fluoro, Br → bromo, Cl → chloro, I → iodo.
- Naming follows rules similar to alkyl substituents.
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- 3E. Examples:
- 1,2-Bromo-1-chlorobutane (structure illustrated).
- 1,4-Dichloro-3-methylhexane (structure illustrated).
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- 3F. How to Name Alcohols:
- IUPAC substitutive nomenclature can include up to four features: locants, prefixes, parent, suffix.
- Example: 4-Methyl-1-hexanol (or 4-Methylpentan-1-ol).
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- Rules for naming alcohols:
- Select the longest continuous carbon chain to which the hydroxyl (OH) is directly attached.
- Change the name of the corresponding alkane by dropping the final -e and adding the suffix -ol.
- Number the chain to give the carbon bearing the OH the lowest possible number; use this number as the locant for the OH.
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- Examples:
- 2-Propanol (isopropyl alcohol).
- 4-Methyl-1-pentanol (or 4-Methylpentan-1-ol) – note that 2-Methyl-5-pentanol is NOT used here.
- 1,2,3-Butanetriol (glycerol) with correct numbering for three OH groups.
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- Example 4 introduction (structure shown): demonstrates naming with multiple OH groups and substituents.
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- Example 4 (Cont’d): identify the longest chain that contains the OH group; if the chain containing OH is not the longest, select the longest that contains OH for naming.
- Example shows Heptane as parent with OH substituent at position 7 to illustrate the rule.
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- Example 4 (Cont’d): assign the lowest possible locant to the carbon bearing OH; display: OH at position 1 or 2 as appropriate to minimize the locant.
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- Example 4 (Cont’d): final name for the example given as 2-Heptanol or other variant depending on chosen chain; illustrates prioritization of OH-bearing chain.
- Substituents considered and named accordingly locally.
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- 4. How to Name Cycloalkanes – 4A. Monocyclic Cycloalkanes:
- For cycloalkanes with a single ring, attach the prefix cyclo- to the name of the ring (e.g., cyclopropane, cyclopentane).
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- Substituted cycloalkanes: examples include isopropylcyclopropane, methylcyclobutane, tert-Butylcyclopentane.
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- Example 1 for monocyclic systems:
- 1-Ethyl-3-methylcyclopentane
- 1-Ethyl-4-methylcyclopentane
- 3-Ethyl-1-methylcyclopentane (not 3-Ethyl-1-methyl- cyclopentane in a misordered form)
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- Example 2 for monocyclic systems:
- 4-Bromo-2-ethyl-1-methylcyclohexane
- 1-Bromo-3-ethyl-4-methylcyclohexane
- Note on lowest substituent numbers: 1,2,4 is preferred over 1,3,4 when applicable.
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- Example 3 for monocyclic systems:
- 4-Ethyl-3-methylcyclohexene
- 1-Ethyl-2-methylcyclohexan-4-ol (and related notations) – OH is present on cyclohexane ring/C=C contexts.
- The guiding principle remains that the carbon bearing OH (if present) should have the lowest possible number when the ring contains an OH group.
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- Cycloalkylalkanes: naming when a single ring is attached to a longer chain:
- Example: 1-Cyclobutylpentane.
- When more than one ring is attached to a single chain:
- Example: 1,3-Dicyclohexylpropane.
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- 4B. Bicyclic Cycloalkanes:
- Bicycloalkanes are alkanes containing two fused or bridged rings.
- Example principle: total number of carbons determines the base name; e.g., bicycloheptane for seven carbons.
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- Bridgehead naming concept: describe relationships between bridge atoms.
- Example: Bicyclo[2.2.1]heptane (two-carbon left bridge, two-carbon right bridge, one-carbon middle bridge).
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- Other bicyclic examples:
- 7-Methylbicyclo[4.3.0]nonane
- 1-Isopropylbicyclo[2.2.2]octane
Page 59
- 5. How to Name Alkenes & Cycloalkenes:
- Rule 1: Select the longest chain that contains C=C as the parent and change the ending from -ane to -ene.
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- Rule 2: Number the chain to include both carbons of the C=C, starting from the end nearer the C=C; the position of C=C is given by the first carbon of the C=C as the prefix (the locant for the -ene suffix may precede the parent name or be placed immediately before the suffix).
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- Examples:
- 1-Butene (not 3-Butene)
- 2-Hexene (not 4-Hexene)
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- Rule 3: Indicate the locations of substituent groups by the numbers of the attached carbon atoms.
- Example: 2-Methyl-2-butene (not 3-Methyl-2-butene).
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- Rule 3 (Cont’d): more examples: 2,5-Dimethyl-2-hexene and 2,5-Dimethyl-4-hexene; ensure proper locant placement.
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- Rule 4: For cycloalkenes, number to give the C=C carbons as 1 and 2, and give substituents lower numbers at the first point of difference.
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- Example 3,5-Dimethylcyclohexene vs 4,6-Dimethylcyclohexene; shows first-difference rule in action for cycloalkenes.
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- Rule 5: Name compounds containing both a C=C and an alcohol group as alkenols (or cycloalkenols); give the alcohol-bearing carbon the lower number.
- Example: 2-Methyl-2-cyclohexen-1-ol (or 2-Methylcyclohex-2-en-1-ol).
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- Examples (Cont’d): 4-Methyl-3-penten-2-ol (or 4-Methylpent-3-en-2-ol).
- OH group positioning is prioritized in the presence of C=C.
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- Rule 6: Vinyl group and allyl group:
- Vinyl group: ethenylcyclopropane (or vinylcyclopropane).
- Allyl group: prop-2-en-1-yl.
- Example: 3-(Prop-2-en-1-yl)cyclohexan-1-ol (or 3-allylcyclohexanol).
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- Rule 7: Cis vs. Trans isomerism:
- Cis: identical or substantial groups on the same side of the C=C.
- Trans: identical or substantial groups on opposite sides of the C=C.
- Examples: cis-1,2-dichloroethene and trans-1,2-dichloroethene.
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- Visual examples illustrating cis/trans relationships (diagrammatic).
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- Example (Cont’d): complete name formation from a labeled structure including stereochemistry considerations in some drawings.
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- Example (Cont’d): final naming for a given structure with a tert-butyl substituent and other substituents on a heptene framework (illustrated as 4-tert-Butyl-2-methyl-1-heptene in the notes).
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- 6. How to Name Alkynes:
- Alkynes are named similarly to alkenes but end with -yne.
- Example: 2-Heptyne (structure shown).
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- Example (Cont’d): more complex alkynes such as 9-Bromo-7-iodo-6-isopropyl-8-methyl-3-decyne.
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- OH group priority over C≡C:
- When both OH and C≡C are present, OH takes precedence for naming order.
- Example: 3-Butyn-1-ol (with OH given the lowest possible number position in the presence of a triple bond).
- Another example: 2-Methyl-5-octyn-2-ol demonstrates the prioritization of OH over the alkyne in determining locants and substituent positions.