synthesis of quinoline from 1,1,3,3-tetramethoxypropane

8/13/2019 Synthesis of Quinoline from 1,1,3,3-Tetramethoxypropane

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Honors Cup Synthetic Proposal

Section: 270-IVGroup Members: Lynne Fiore, Chris Grondin

Title: Synthesis of Quinoline from 1,1,3,3-Tetramethoypropane

!ntro"uction: Quinoline is used mainly as an intermediate in the manufacture of other productsQuinoline is also used as a catalyst, a preser!ati!e for anatomical specimens, and a corrosioninhi"itor #dditionally it is also !alua"le the manufacture of dyes, polymers and a$riculturalchemicals and as a sol!ent for resins and terpenes It is "est %no&n to students as a theoreticalpoison catalyst that pre!ents a car"on triple "ond from "ein$ saturated "y hydro$en, causin$ thereaction to rather stop at a car"on-car"on dou"le "ond It is primarily e'tracted from coal tar,thou$h throu$h a some&hat e'pensi!e and not too relia"le process Quinoline is commonlyproduced "y or$anic chemists throu$h synthesis so as to create a readily a!aila"le source of(uinoline )he Com"es reaction, carried out here in the second and third steps, &as first

documented in the late *++0s as an efficient model for the synthesis of the molecule

#$erall syntheticreaction scheme:

O

O

O

O

O O

N

NH2

O

N

*,*,,-tetrametho'ypropane

Cl

.alondialdehyde

#niline

Quinoline

2/01

/tep *

/tep 2

/tep

-phenylimino3propanal


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Step 1

Synthetic transformation 1:

O

O

O

O

O O

*,*,,-tetrametho'ypropane

Cl

.alondialdehyde

/tep *

%perimental 1:)he transformation of malondialdehyde is performed nearly as detailed in the cited articles )hearticles did not include any particular amounts of *,*,,-tetrametho'ypropane or Cl so

amounts ha!e "een created to fit our purposes )here is also no e'plicit mention of a percentyield, "ut the reaction is e'tremely fa!ora"le, rapidly occurs, and is implied to ha!e *004 yield#ny non-reaction should "e considered ne$li$i"le )he reaction produces 1 molecules ofmethanol for e!ery molecule of malondialdehyde # procedure to separate the t&o compounds&as ne!er discussed, "ut can easily "e performed throu$h e'ploitation of differin$ "oilin$ points

*0 mL of *,*,,-tetrametho'ypropane &as placed into a "ea%er and 5 mL of 0* . hydrochloricacid added )he reaction &as allo&ed to ta%e place for 0 seconds )he resultin$ solution &asheated on a hot plate to 65 de$rees Celsius under the hood nce the solution reached thistemperature, the "yproducts of the reaction, methanol and Cl, &ill ha!e "oiled off lea!in$ puremalondialdehyde

%pecte" yiel": 1&& ' ()(*+ malon"ial"ehy"e

Safety, "isposal an" +reen issues 1 :

# la" apron, $o$$les, and $lo!es are re(uired for all sta$es of step *

#lthou$h an e'cess of malondialdehyde &as produced, &astin$ chemicals and not follo&in$en!ironmentally friendly protocol, this &as necessary in order for the reaction to "e completedon a realistically lar$e scale

*,*,,-tetrametho'ypropane is flamma"le and in case of contact &ith eyes, rinse immediately&ith plenty of &ater and see% medical ad!ice It can "e disposed of in the li(uid or$anic &aste"uc%et


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.ethanol is hi$hly flamma"le, and e'tremely to'ic upon inhalation, in$estion, or s%ina"sorption .ethanol must "e "oiled off under the hood, &ith !entilation on )his can "edisposed of in the li(uid or$anic &aste "uc%et

ydrochloric #cid is corrosi!e and flamma"le Inhalation or in$estion can cause serious inury,

and e'posure to s%in and eyes can cause se!ere dama$e )he catalytic amount of Cl used must"e "oiled off under the hood &ith !entilation on )here is no need for disposal as this "yproduct&ill "e "oiled off

.alondialdehyde is harmful "y inhalation, in$estion, and can cause eye and s%in irritation8ispose of this chemical in the li(uid or$anic &aste "uc%et

Step

Synthetic transformation :

O O

N

NH2

O

.alondialdehyde

#niline

/tep 2


%perimental :

)he procedure &as modified primarily "y su"stitutin$ aniline for p-toluidine the reactant used inthe article3, a su"stituted aniline &ith a methyl $roup para to the nitro$en attached to the "en9enerin$ )his modification &as considered minor and &as assumed to ha!e a ne$li$i"le effect onthe outcome and o!erall effecti!eness of the reaction )he second chan$e made &as to adust theratio of reactants outlined "y the article Instead of *: ** malondialdehyde : aniline mol ratio, a*:* ratio &as adopted )his &as "ecause the ournals (uantities &ere desi$ned to ensurecompletion and their e'periment &as not affected "y the presence of e'cess reactant o&e!er,since the t&o chemicals react in a *:* ratio, follo&in$ the ournals procedure &ould createe'cess aniline that mi$ht affect the follo&in$ steps of this e'periment and thus &as not follo&ed)he last modification carried out &as to decrease the amounts of the reactants, since the desiredyield of the final product &as only 05 $rams

7;02 $ malondialdehyde &ere com"ined &ith 5 mL aniline in a 25 mL round "ottomed "ea%erand heated to a li$ht "oil under reflu' for *5 hours 20 mL &ater &ere added and the mi'ture&as thorou$hly sha%en 20 mL "en9ene &as added and the or$anic layer &as separated #nother20 mL of &ater &as added or$anic layer e'tracted a$ain /olution &as dried o!er anhydrous


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sodium sulfate /olution heated to *00 if it is in$ested a physician should "e notified Itshould "e disposed of as a to'ic or$anic &aste

?en9ene is a %no&n carcino$en, so it should "e handled &ith care &hen used It should "e usedin a hood &ith $ood !entilation to minimi9e contact It is also hi$hly flamma"le and should "e

disposed of in to'ic &aste

-phenylimino3propanal should "e produced as a solid @'cess should "e disposed of in theli(uid or$anic &aste "uc%et

Step 3

Synthetic transformation 3:

N

O

N

Quinoline

2/01

/tep


%perimental 3:

)he ournal specified no particular amounts or reactants, so the procedure &as not chan$ed at allin re$ard to scale o&e!er, the ournal also offered no methods for purification of the (uinolinefrom the sulfuric acid solution it only tested for the presence of the reactant to demonstrate thatthe reaction had $one to completion3 )herefore the method for remo!in$ the sulfuric acid from(uinoline "y the addition of copper II3 o'ide from the sulfuric acid had to "e de!ised &ithoutournal support

*+557 mL sulfuric acid &as cooled in ice "ath to 5


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&as then heated to *00


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Gutterid$e, E . CAnalytical Biochemistry1(*/, 69, 5*+-526

/tep 2:o"erts, @> )urner, @ @J. Chem. Soc.1(*, 132, *+2-*+57

?radsher, C Chem. Rev.1(5*, 87, *277-*2;7

/tep :)urner, @ @ J. Chem. Soc. 1(1*, 111, *-1

Eohnson, /> .athe&s, F EJ. Am. Chem. Soc.1(66, 66, 2*0-2*5

synthesis of quinoline from 1,1,3,3-tetramethoxypropane

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