< MOHAMMED V. UNIVERSI a | FACULTY OF MEDICAL SCIENCES MODULE: Chemistry-Biochemistry MODULE ELEMENT: Organic Chemistry for Medicine CHAPTER 2: Alkenes, Alkynes & other functional groups SEMESTER: ONE Course N°: 1 Date of sessions: 09-16 Nov 2023 Prof./Dr. Hicham Benyoucef Dr. Hassan Noukrati> Double Bond 1 1 hy | ee s “oe ‘three orbitals are hybridized hybrid orbitals = H H \ c=C i \ (ethylene) ngun BRL es «saa ¥ a, S escsmerLL ce enna | > Alkene Nomenclature ig the “ane” ending of the corresponding The systematic (IUPAC) name of an alkene is obtained by replat alkane with “ene.” » ao OC HjC=CH, — CHsCH systematic name: ethene propene ‘cyclopentene _eyclohoxene commen name: ethylene propylene 1. Number the longest continuous chain containing the functional group in the direction that gives the functional group suffix the lowest possible number. aoa hd da 12 a4 86 CHyCHCH=CH, © CHyCH=CHCH, —— CHyCH=CHCH,CHCH, ‘butene 2-butene 2-hexene ‘the longest continuous chain has elght carbons but the longest continuous chain containing ‘the functional group has sx carbons, so the parent name of the compound is hexene CHC HaCHaCHaCCH.CHCH 1CHy 2-propylt-hexene> Alkene Nomenclature Ee a 2. The name of a substituent is cited before the name of the longest continuous chain containing the functional group, together with a number to designate the carbon to which the substituent is attached. The chain is still numbered in the direction that gives the functional group suffix the lowest possible number. 3. The substituents are cited in alphabetical order. (The prefixes di, tri, sec, and tert are ignored in alphabetizing, but iso, neo, and cyclo are not ignored.) 4, If the same number for the alkene functional group suffix is obtained in both directions, the correct name is the name that contains the lowest substituent number. Brcl 2.6-dimethyt3-octene CH,CH,CH,C—CHCH,CHCH, CHyCHCH—CCHLCH, 1 CHy CH Br CH 2,5-dimethyl-toctene 2-bromo-4-methyl3-hexene not S-bromo:3-methyl-3-hexene not A.7-dimathyl-4octone because 2<3 because 2 <4LL LAL LL ae a a a ee een | 11) SEES > Alkene Nomenclature 5, In cyclic alkenes, a number is not needed to CHCH Nts a) denote the position of the functional group, orn Ck cr CH ‘CHsCHy because the ring is always numbered so that WH the double bond is between carbons 1and 2, —_|a-ethyleyclopentene _4,5-dimethyleyclohexeno _4-othyl-3-methylcyclohexene =Trerus2 +3 VY In cyclohexenes, the double bond is en between C-1 and C-2. i , ¥ You move around the ring in the direction i ae 5 that puts the lowest substituent number into the name, not in the direction that Uésichlorocydohexene _Sethy/-t-methyleylohexene gives the lowest sum of the substituent 23edichloroeydohevene _Aethyl2-methylelohexene numbers. because 1<2 ‘because 112> Alkene Nomenclature iT m Br i CH,CHCH,CH=CCHCHCHs 1o6 dy nc, wr Hs 2:romo-4-ethy-7-maty-ct 6. If both directions lead to the same number for the alkene functional group suffix and the same low number(s) for one or more of the substituents, then those substituents are ignored and the direction is chosen that gives the lowest number to one of the remaining substituents. ‘-bromo-2 Alkene structure ‘an bond ae Y It is important to remember that the m bond < represents the cloud of electrons that is above and He, below the plane defined by the two sp? carbons and 2 the four atoms bonded to them. ae ssa we > CisTrans Isomerism ¥ Rotation about the carbon-carbon double bond would break the ™ bond. ‘ra eomer V The isomer with the hydrogens on the 7 same side of the double bond is called the HC Hs HC, cis isomer, and the isomer with the Nomel al hydrogens on opposite sides of the double ae we YcH bond is called the trans isomer. | as2-butene trons2-butene> The E,Z System of Nomenclature is and trans isomers are not possible for these compounds because ‘two substituents on an sp? carbon are the same pis / Ho ‘Which Isomer Is cls and whichis trans? v If there are 4 different substituents on the two Vinylic carbons, the ,Z system of nomenclature was devised for these kinds of situations, Rule 1. The relative priorities of the two groups depend on the atomic numbers of the atoms that are bonded directly to the sp? carbon. V The greater the atomic number, the higher is the priority. CH; CHsCHy \. Sa ‘ wou if low priority mc’ priority low prioiy high priority rionty P rovity the Z omer]> The E,Z System of Nomenclature Gs cicth HCH ve ye of ‘oes cic, HOH the Z isomer: the Fisomer Rule 2. If the two substituents bonded to an sp? carbon start with the same atom (there is a tie), you must move outward from the point of attachment and consider the atomic numbers of the atoms that are attached to the “tied” atoms. Rule 3. If an atom is doubly bonded to another atom, the - priority system treats it as if it were singly bonded to two of those atoms. ¥ If an atom is triply bonded to another atom, the priority system treats it as if it were singly bonded to three of those atoms. [the Zisomer the Eisomer ‘CHCHy V IUPAC prefers the £ and Z designations because they can be used for all alkene isomers.> The Structure of Alkynes 180° bend fomedby Y Atriple bond is composed of a o bond and two n Peseta bonds. ~, ye V In the structure of ethyne each carbon is sp te n-chchn hybridized, so each has two sp orbitals and two p «@ bond formed by| orbitals, te a Y One sp orbital overlaps the s orbital of a hydrogen ¥ the other sp orbital overlaps with an sp orbital of the other carbon. Y Because the sp orbitals are oriented as far from each other as possible to minimize electron repulsion, ethyne is a linear molecule with bond angles of 180°. zLATTA eee | || | SEE, > Nomenclature Y Alkynes are hydrocarbons that contain a carbon-carbon triple bond. ¥ The systematic name of an alkyne is obtained by replacing the “ane” ending of the alkane name with “yn ¥ Analogous to the way compounds with other functional groups are named, the longest continuous chain containing the carbon-carbon triple bond is numbered in the direction that gives the alkyne functional group suffix as low a number as possible. ¥ Ifthe triple bond is at the end of the chain, the alkyne is classified as a terminal alkyne. Y Alkynes with triple bonds located elsewhere along the chain are called internal alkynes. 43 2 12 34s HC=cH — CH,CH,C=CH CH,C=CCH,CH, systematic: _ethyne 1-butyne 2-pentyne 4-methyl-2-hexyne ‘Common: acetylene ethylacetylene ethylmethylacetylene —_sec-butylmethyF- a terminal alkyne ‘an Internal alkyne acetylene 1 Br gt CH.CHCH CinCHC=CCH;CH:Br 3-bromo-2-chloro-4-octyne 4-bromo-5-methyl-3-hexyne not 6-bromo-7-chloro-4-octyne not 6-bromo-2-methyL3-hexyne a) Beat ae Pease> Commercial Use of Ethyne Y Most of the ethyne produced commercially is used as a starting material for polymers that we encounter daily, such as vinyl flooring, plastic piping, Teflon, and acrylics. Y Polymers are large molecules that are made by linking together many small molecules “monomers”. ¥ poly(vinyl chloride), known as PVC, is the soft elastic vinyl commonly used both as a substitute for leather and in the manufacture of such things as garbage bags and shower curtains. ¥ Poly(acrylonitrile) looks like wool when it is made into fibers. It is marketed under the trade names Orlon® (DuPont), Creslan® (Sterling Fibers), and Acrilan® (Monsanto). ny lorie HC=CH + He! — H,c=cxcr —Polmmentzaton , Tt a polytvny| chloride) Pvc oe HO=CH + HCN —> H,C—CHCN Semester ‘CH;—CH- — nl, as Orion sho ae> Examples YA few drugs contain alkyne functional groups, ° ou U cH. HF YaC=CH *—NH(CH3)CHs i Pars ocHec etka’ crlcy,cecn Nomen’ sinova i suit ENCE vast! HN’ co parsalmide pargyine ‘mestranol an analgesic an anthypertensive 4 component in oral contraceptives V The triple-bond-containing propargyl group is used in common nomenclature. ¥ {tis analogous to the double-bond-containing allyl group HC=CCH;— ——-H,C=CHCH,— propargyl group allyl group HC=SCCH2Br H,C—CHCH,OH propargyl bromide allyl aleohol[chapter 2. Orner FUNCHO SEOUL Sc st > Epoxides V Ethers in which the oxygen atom is incorporated into a three-membered ring are called epoxides or oxiranes. The common name of an epoxide uses the common name of the alkene, followed by “oxide,” assuming that the oxygen atom is where the rt bond of an alkene would be. The simplest epoxide is ethylene oxide. 2 LN (XN H,C=CH, H,C—CH, H,C=CHCH, —-H,C—CHCH, ethylene ethylene oxide propylene propylene oxide There are two systematic ways to name epoxides. Y Method 1: calls the three membered oxygen-containing ring “oxirane,” with oxygen occupying the 1-position of the ring. Thus, 2-ethyloxirane has an ethyl substituent at the 2-position of the oxirane ring. Y Method 2: an epoxide can be named as an alkane, with an “epoxy” prefix that identifies the carbons to which the oxygen is attached. A a fs H,C—CHCH.CH, cu,ch—cHcH, Hc 2ethyloxirane 2,34limethyloxirane CH; seepoxybutane 2:3epoxybutane 2.2-dimethyloxirane 1.2-2poxy-2-methyipropane> Thiols Y Thiols are sulfur analogs of alcohols. ¥ Thiols used to be called mercaptans because they form strong complexes with heavy metal cations such as mercury and arsenic (they capture mercury). 2CH;CH,SH + Hg —> CH,CH,S—Hg—SCH,CH,; + 2H™ athlol mercuric lon ¥ Thiols are named by adding the suffix “thiol” to the name of the parent hydrocarbon. Y If there is a second functional group in the molecule, the SH group can be indicated by its substituent name, “mercapto’. Y Like other substituent names, it is cited before the name of the parent hydrocarbon. CH; I CH,CH;SH —— CH;CH,CH,SH CH,CHCH,CH,SH HSCH,CH,OH ethanethiol ‘-propanethiol_--3-methyl-1-butanethiol___—_-2-mercaptoethanolEL a as > Carbonyl groups ¥ Carbonyl compounds can be divided into two classes > (Class | & Class Il), ° 9 Y Class | carbonyl compounds are those in which the acyl a aw ss group is attached to an atom or a group that can be @ replaced by another group. ¥ Carboxylic acids, acyl halides, acid anhydrides, esters, and amides belong to this class. All of these compounds contain a group or that can be replaced by a ° 9 nucleophile. i t & j Ro a lan ¥ Acyl halides, acid anhydrides, esters, and amides are all aon a x oa called carboxylic acid derivatives because they differ a Sse from a carboxylic acid only in the nature of the group — that has replaced the OH group of the carboxylic acid. a carbonyl group acyl groups [compounds with groups that can be replaced by a nucleophile [compounds with aroups that cen be replaced by a nucleophile i i i 3 i t b é. é é eS e RN v RSS RNR ancy corde ancy bromide amides x haldesTA eee | | SBE > Carbonyl groups ¥ Class Il carbonyl compounds are those in which the acyl not be rep [eo group is attached to a group that cannot be readily cannot betreeiaced bys 10 il Il replaced by another group. ¥ Aldehydes and ketones belong to this class. t. V The -H and alkyl groups of aldehydes and ketones cannot ROH ROR be replaced by a nucleophile. an aldehyde aketone 4 Carboxylic Acids ¥ In systematic nomenclature, a carboxylic aci is named by replacing the terminal “e” of the alkane name with “oie acid’. a q i i An, oN AN . non cus Son cacy ~on —ciycH.cHy ~on ‘ystematicname: methanol acd ethinok add) propanol ald tana acid “emmonname: "“fomiesdd” — “aatiescd ‘propionate gnc add a i i i é pentanole acd hhexanole aed propenoicacld _benzenecarboxyite acd Valeri adi ‘aprotc acid acrylic add ‘benzoic ald us> Carbonyl groups Carboxylic Acids =copH com carbon! aroup are reaver ‘Sov taba fe oe bu, ‘rans metiyeycdopetanecrbon Se Y The functional group of a carboxylic acid is called a carboxyl group. ¥ Carboxylic acids in which a carboxyl group is attached to a ring are named by adding “carboxylic acid” to the name of the cyclic compound. codohanecabarie 24 + Acyl Halides Y Acyl halides are compounds that have a halogen atom in place of the OH group of a carboxylic acid. The most common acyl halides are acyl chlorides and acyl bromides. ¥ Acyl halides are named by using the acid name and replacing “ic acid” with “yl chloride” (or “yl bromide”). Y For acids ending with “carboxylic acid”, the “carboxylic acid” is replaced with “carbonyl chloride” (or “bromide"). ° I ° x. I cH, ‘ oo Lae “ ana cncuducn ar systematicname: ethanoyl chloride 3:methyipentanoy brome cylopentanecarbonyt ommonname “aceyconde, ——methynalent bromide chloride> Carbonyl groups * Acid Anhydrides 9 ¥ Loss of water from two molecules of a carboxylic acid t 3 I g results in an acid anhydride. “Anhydride” means Re NOH HO“ NR RN O NR “without water.” ‘an acid anhydride Y If the two carboxylic acid molecules forming the acid anhydride are the same, the anhydride is a symmetrical anhydride. If the two carboxylic acid molecules are different, the anhydride is a mixed anhydride. ‘symmetrical anhydrides are named by using the acid name and replacing “acid” with “anhydride.” Mixed anhydrides are named by stating the names of both acids in alphabetical order, followed by “anhydride.” i 2 i 2 Cc, SSN nN, AN cHy ~o~ ~cH, cHy “07 ~H systematic name: ethanole anhydride ethanolc methanolc anhydride ‘common name: acetic anhydride ‘acetic formic anhydride asymmetrical anhydride a mixed anhydride> Carbonyl groups — Esters [geen ones] ¥ An ester is a compound that has an OR’ group in place of the OH group of a carboxylic acid. R™ oR’ | ¥ Innaming an ester, the name of the group (R’) attached to the carboxyl oxygen is [Eieatomea stated first, followed by the name of the acid, with “ic acid” replaced by “ate” - =o. 9 9 6 7 q wf AN, An, Fcc eA cH SOCH:CH, —CHSCHY OC cHCHCH,~ OCH; Cy OCH:CH, sytematename: ehylathaneate phenyl propsneate methyl 3bromobutaoate ethyl ydohexanecaboxlte riemmanrame; “ebylacate, phenyl propionate V Salts of carboxylic acids are named in the same way. The cation is named first, followed by the name of the acid, again with “ic acid” replaced by “ate”. F , i i H7 SO" Nat cHy Yo kt POON NAME soctu formate potassium acetate Sodium benzoate meocneprers; ten unctouat sours > Carbonyl groups Esters Y Cyclic esters are called lactones. Y_Insystematic nomenclature, they are named as “2-oxacycloalkanones’. Y Their common names are derived from the common name of the carboxylic acid, which designates the length of the carbon chain, and a Greek letter to indicate the carbon to which the carboxyl oxygen is attached. ¥_ 4-membered ring lactones are B-lactones (the carboxyl oxygen is on the B-carbon) ¥ 5-membered ring lactones are y-lactones ¥_6-membered ring lactones are 6-lactones ° 9 9 9 Lo 0 D if aA ¥ ° CHs CH,CH, 2oxacyclopentanone 2-oxacyclohexanone 3-methyl2-oxacyclohexanone _3-ethyl-2-oxacyclopentanone ‘y-butyrolactone —_-valerolactone ‘S-caprolactone ‘y-caprolactoneEA oe > Carbonyl groups Amides ¥ Anamide has an NH,, NHR, or NR, group in place of the OH group of a carboxylic acid. ¥ Amides are named by using the acid name, replacing “oic acid” or “ic acid” with “amide” Y For acids ending with “carboxylic acid,” “ylic acid” is replaced with “amide” 2 2 & ©. cu Nt, cice.cH.cus* ~NH; systemetlcname: ethanamide _&clorobutanamide “common name: acetamide ‘ehorobutyamide Y Ifa substituent is bonded to the nitrogen, the name of the substituent is stated first (if there is more than ‘one substituent bonded to the nitrogen, they are stated alphabetically), followed by the name of the amide. ¥ The name of each substituent is preceded by a capital N to indicate that the substituent is bonded to a nitrogen. z i i i As, aN, oN, a, Suc, thy. motiypentanamide ——_nytethytbutanamideiL LT LLL LL ae eS | || REE > Carbonyl groups “ Amides Y Cyclic amides are called lactams. ¥ Their nomenclature is similar to that of lactones. ¥ They are named as “2-azacycloalkanones” in systematic nomenclature (“aza” is used to designate the nitrogen atom). Y In their common names, the length of the carbon chain is indicated by the common name of the carboxylic acid, and a Greek letter indicates the carbon to which the nitrogen is attached. ° o a7 NH wt a 6 ol NH Zazacyclohexanone 2-azacyclopentanone —2-azacyclobutanone S-valerolactam ‘y-butyrolactam B-proplolactamY Nitriles are compounds that contain C=N a functional group. ¥ Nitriles are considered carboxylic acid derivatives because, like all Class | carbonyl compounds, they react with water to form carboxylic acids. v In systematic nomenclature, ni Y Notice that the triple bonded carbon of the nitrile group is counted the longest continuous chain. Y In common nomenclature, nitriles are named by replacing “ic acid” of the carboxylic acid name with “nitrile” They can also be named as alkyl cyanides—stating the name of the alkyl group that is attached to the C=N group. "” to the parent alkane name. the number of carbons in imEA a > Carbonyl groups + Aldehydes ¥ The systematic name of an aldehyd hydrocarbon with “al” Y a one-carbon aldehyde is methanal ¥ atwo-carbon aldehyde is ethanal Y The position of the carbonyl carbon does not have to be designated, because itis always at the end of the parent hydrocarbon and therefore always has the 1-position. obtained by replacing the terminal “e” from the name of the parent Y For the common name of an aldehyde the “aldehyde” is substituted for “ic acid” (or “oic acid”). Y The carbonyl carbon is not designated; the carbon adjacent to the carbonyl carbon is the alpha-carbon. ie } aot & Hq” “MH [ cH,CH~ cauericey CH,CHCHy systematcname: _methanal ethanal L. 4 du, cSmmon name: formaldehyde acetaldehyde 3-chlorobutanal 3:mothylbutanat 2-bromopropanal ctnlorabutyraldel jaleraldehyde a-bromoproplonaldehyde immense HattaEe eee) Class Sutfiy Name Carboxylic acid -oic acid Ester -oate Amide -amide Nitrile -nitrile Aldehyde Aldehyde Ketone Alcohol ‘Amine Alkene Allkyne Alkane Ether Alkyl halide Prefix Name Carboxy Alkoxycarbony! Amido cyano ‘0x0 (0) Formyl (~CH=0) ‘0x0 =0) Hydroxy Amino Alkeny! Alkynyl Alkyl Alkoxy HaloCAL LL ee ee || > Carbonyl groups Aldehydes ‘a carbonyl group has a higher nomenclature priority than an alcohol or an amine group. all carbonyl compounds do not have the same priority. If a compound has two functional groups, the one with the lower priority is indicated by its prefix. The prefix of an aldehyde oxygen that is part of the parent hydrocarbon is “oxo” The prefix of a one-carbon aldehyde group that is not part of the parent hydrocarbon is “formyl” + KSA K i cascricns oi i | oe Ha cxcaducnycns 3-hydroxybutanal methyl 5-oxopentanoate ethyl 4-formylhexanoate ¥ If the compound has both an alkene and an aldehyde functional group, the alkene is cited first, with the “e” ending omitted to avoid two successive vowels CH;CH=CHCHS 3-pentenal> Carbonyl groups “ Ketones Y The systematic name of a ketone is obtained by removing the “e” from the name of the parent hydrocarbon and adding “one”. Y The chain is numbered in the dire n that gives the carbonyl carbon the smaller number. V Frequently, derived names are used for ketones—the substituents attached to the carbonyl group are cited in alphabetical order, followed by “ketone”. 1 ae CHY CH, —CHCHY) ~CH,CH;CH) —- CHyCHCH,CH:CHY CH systematicname: propanone 3-hexanone 6-methyl-2-heptanone common name: acetone derived name: dimethyl ketone ethyl propyl ketone Isohexyl methyl ketoneCEE > Carbonyl groups “> Ketones ¥ Inthe case of cyclic ketones, a number is not necessary because the carbonyl carbon is assumed to be at the 1-position. g & cH, onaer. A 8 cu Scug Sc crycr—crcny ory systematicname: cyclohexanone butanedione —_—2,4-pentanedione: ‘.hoxen-2-0ne common name: ‘acotylacetone, ¥ Ifthe ketone has a second functional group of higher naming priority, the ketone oxygen is indicated by the prefix “oxo” © 6 yh °° or 1" 5 Acca, | systomatlename: Goxopentanal methyl 3anobutancate—Y2-oxopeny)- i ‘yclohexanoneLA ee | | > Other heterocycles V Asaturated cyclic amine—a cyclic amine without any double bonds—can be named as a cycloalkane, using the prefix “aza” to denote the nitrogen atom Y There are, however, other acceptable names and commonly used . ¥ Notice that heterocyclic rings are numbered so that the heteroatom has the lowest po: le number. CH, C - OS CL .) K NH ny NCH, | 3 LJ H H CH;CH; scgrapam azacyoptane >methyarscripartane 2etiyeencchecae | ayaa V Heterocycles with oxygen and sulfur heteroatoms are named similarly. The prefix for oxygen is “oxa” and that for sulfur is “thia” 0, 3; mi és LA Z\ | 0 oxacyclopropane thiacyclopropane oxacyclobutane oxacyclopentane oxirane ‘thilrane ‘oxetane ethylene oxide tetrahydrofuran WWMM]. OT; itl FACULTY OF MEDICAL SCIENCES Tutorials Office: B60 (Emines 1st Floor) Time: on request Date of session: 09-16 Nov 2023 Prof./Dr. Hicham Benyoucef Dr. Hassan Noukrati