You are watching: N-cinnamylidene-m-nitroaniline
To synthesize N-cinnamyl-m-nitroaniline (2° amine) by forming the imine indigenous the condensation between cinnamaldehyde and 3-nitroaniline (1° amine), followed by selective reductive amination with sodium boronhydride (NaBH4).
Since cinnamaldehyde and 3-nitroaniline reacts in the mole proportion of 1:1, therefore, 3-nitroaniline is the limiting reagent.
The an initial part the this experiment to be to synthesize the intermediary imine A, N-cinnamylidene-m-nitroaniline. A magnetic stirring bar was placed inside the round bottomed flask come ensure constant and homogenous mixing of both reactants.
Excess cinnamaldehye was added carefully into the ring bottomed flask containing 3-nitroaniline in a drop-wise manner. Warmth was only applied after all the cinnamaldehyde had actually been added, together heating the solution prior to addition may reason the 3-nitroaniline to decompose explosively, producing toxic NO2 gas<1>. The heat used was likewise controlled together excess heating might lead to 1,4 conjugate addition instead of the desired 1,2 direct addition.
Formation of intermediate A, N-cinnamylidene-m-nitroaniline
The lone pair top top N atom act together a nucleophile to strike the electrophilic C of the carbonyl. After ~ a collection of protonations, the water leaves producing the imine intermediate.
Upon collecting 22cm3 of distillate, the mixture to be cooled and the staying residue was liquified in 25cm3 of 95% ethanol before 0.7838g the NaBH4 liquified in 25cm3 that 95% ethanol was included in a drop-wise manner.
Formation of link B, N-cinnamyl-m-nitroaniline
After the mixture to be refluxed because that 15 minutes, one orange-red equipment was obtained. NaBH4, gift a mild reducing agent, walk not mitigate the alkene or nitrobenzene yet reduce the iminium group, developing N-cinnamyl-m-nitroaniline, one orange-red compound. The enhancement of 50cm3 the water come the cooled refluxed mixture ‘destroyed’ the NaBH4 and‘quenched’ the reduction. The mixture was cooled in an ice water bathtub for more crystal growth and also the crude product was obtained via vacuum filtration.
Ethanol was used as the solvent, rather of water. This is due to the fact that it is only weakly protic. Also, together an organic solvent, it deserve to dissolve the essential reactants and also products.
Hydrolysis the cinnamaldehyde
Water is created from the condensation in between 3-nitroaniline and trans-cinnamaldehyde. It might react v the reagent, trans-cinnamaldehyde to kind an unwanted diol and lower the as whole yield.
1,4 conjugate addition to cinnamaldehyde
When the mixture is heated for as well long during the condensation the 3-nitroaniline and also cinnamaldehyde, 1,4 conjugate addition may take place instead that the preferred 1,2 direct addition. This produces the thermodynamic product rather of the kinetic product.
NaBH4 is a base the is perceptible to water. If water is present, BH4- will certainly deprotonate the to type hydrogen gas and borohydride. The BH3 formed can more react with the hydroxide ion. Thus, NaBH4 is ‘destroyed’.
Side reaction of sodium borohydride and also remaining cinnamaldehyde
Since 3-nitroaniline is the limiting reagent, NaBH4 will reduce the remaining cinnamaldehyde to 1o alcohol. This to reduce the lot of NaBH4 because that reducing imine A.
The big amount of rudely product (7.188g) obtained indicates the existence of next products and also impurities.
The pure N-cinnamyl-m-nitroaniline is then obtained via recrystallisation. Throughout crystallization, the crude product was liquified in adequate 95% ethanol come ensure that no N-cinnamyl-m-nitroaniline is lost which may influence the yield, and also the mixture to be heated mildly. A few drops of warm ethanol was added to ensure that all the rudely product to be dissolved and also to dispel the cloudiness. Then, the heater was revolve off and the systems was allowed to cool come room temperature.
The saturated equipment was allowed to cool slowly with minimum disturbance to administer sufficient time for the newly dissolved crystals come assemble right into their optimal decision pattern. Quick cooling reasons the solid come precipitate out quickly and trap the impurities within the crystals. Hence, the equipment was cooled at room temperature before further cooling in an ice cream bath. The lower temperature that the ice bath will reason the more N-cinnamyl-m-nitroaniline to crystallize hence increasing the yield.
It was noticed that, upon reaching the temperature that 78.0° C, boiling suggest of ethanol, the temperature remained continuous and distillate to be generated. Thus, it have the right to be concluded that the ethanol offered as solvent to be distilled out.
Imines space unstable and are conveniently hydrolysed to earlier to your amine and also carbonyl form. Hence, in stimulate to drive the reaction to the ideal (synthesize an ext imine), over there is a must remove the water produced. Hence, azeotropic distillation, a procedure in i beg your pardon a fluid mixture is separated into pure contents with the assist of secondary substance or solvent, is brought out.<2> In this case, the solvent is ethanol.
In the mixture, both water and ethanol to be present. Return the boiling point of water is 100° C, ethanol and also water form a minimum-boiling azeotrope (78.0° C) <3>, hence water generated throughout condensation is continuously gotten rid of by distilling ethanol-water azeotrope during the course of reaction. <4>
The contents in the 22 cm3 distillate are ethanol and water. Water boils in ~ 100 ºC and also ethanol boils at 78.0 ºC. Thus the mixture will certainly boil in ~ 78.2 ºC providing a compostion around 95.5% by massive of ethanol and also 4.5% by fixed of water as this is the azeotropic ratio.<2> The ethanol has actually a higher composition because the boiling allude of ethanol (78.0° C), is closer to the 78.2 ºC, wherein the vapour and also liquid compositions becomes identical.
One of the assumptions is that the composition of ethanol-water is the very same as that of the distillate. Another assumption is that the temperature is assumed to be continuous at the vapour-liquid interface and vapour totally free stream room at the bubble suggest and dew suggest respectively. The mass and heat transfer procedures in the azeotropic distillation are assumed to it is in vapour-phase controlled and also the interaction in between diffusion fluxes (water and also ethanol) is negligibly small.
The speculative yield tabulated was just 57.7%. There room several determinants that deadline to together a yield.
Firstly, the manufacturing for imine A is in a dynamic equilibrium. The is not feasible for every the reaction to kind the imine product. Thus, percentage yield of 100% cannot be achieved.
Other than the equilibration, side reactions may an outcome in either the shed of reactants or the lost of the NaBH4 reduce agent. Native the system of side reactions, highlighted in web page 3. Reactions (i), (ii) and (iv), ‘destroyed’ the cinnamaldehyde reactant because that the exactly condensation v 3-nitroaniline. Hence, v a reduced amount the cinnamaldehyde, according to the Le Chatelier’s Principle, the position of equilibrium the the reaction would transition left, leading to a lower yield in the imine product, which later then influence the yield because that N-cinnamyl-m-nitroaniline.
Reaction (iii) highlights the truth that the reduce agent, NaBH4 may additionally be lost as result of reaction v the water presence in the air. However, the is highly unlikely that such side reaction had actually occurred, together no effervescence that hydrogen gas was observed. In addition, NaBH4 was added in excess, thus, the minute lot loss due to exposure to moisture is minimum. However, a far-ranging amount of NaBH4 could be lost when it react v the staying cinnamaldehyde, as highlighted in reaction (iv). Thus, this side reaction could contribute to the lower yield that N-cinnamyl-m-nitroaniline.
As the ready of the amine and also the purification the the N-cinnamyl-m-nitroaniline involved many measures of transferring, the tiny amounts that reagents shed in every step added up to a significant amount eventually. Thus, incomplete transport of all the assets resulted in the lose of some N-cinnamyl-m-nitroaniline.
Lastly, part N-cinnamyl-m-nitroaniline might be lost as result of incomplete recrystallization. The low yield may additionally be attributed to too lot ethanol added to dissolve the solid. When excess solvent was used, less solute will certainly crystallize out, together the saturation is lowered.
In order to determine the purity the the N-cinnamyl-m-nitroaniline synthesized, melting allude measurement to be conducted.Pure crystalline compounds possess characteristic melting points, thus any kind of deviations in the experimental melting points indigenous the theoretical melting point range would suggest the presence of impurities as impurities have tendency to depress and also broaden the melting range. Existence of impurities affects the melting allude of the compound due to colligative properties.
The theoretical melting point selection of N-cinnamyl-m-nitroaniline is 106.0°C – 107.0°C. <6>The experimental melting point selection of N-cinnamyl-m-nitroaniline is 105.0°C – 105.3°C
The experimental melting point range lies slightly out of the theoretical melt point range as the experiment was not carried under conventional conditions.
See more: Which Of The Following Is The Most Cited Source Of New Business Ideas?
Also, there are some experimental errors during the measure of the melt point. Once determining the melting variety of the crystals, there was challenge in observing once the an initial crystals melts as the particles room small. To get rid of this, recurring readings need to be required to narrow down the melting range and obtain an ext accurate readings. Furthermore, the packing of crystals might not be tight enough, enabling air sachets to influence the conduction that heat in between the molecules, hence melting point may vary. Dust particles from the bordering may likewise inevitably floor in the mixtures to reduced the purity the the crystals as soon as they are lugged to check for your melting points.
The intermediary imine A is N-Cinnamylidene-m-nitroaniline, while link B is N-cinnamyl-m-nitroaniline. Mass and percentage productivity of N-cinnamyl-m-nitroaniline derived is 2.9343g and 57.7% respectively. That experimentally determined melting-point variety is 105.0 °C – 105.3 °C.
<1> 3-nitroanilinehttp://www.analytyka.com.mx/english/MSDS/N/N0038.htm<2> Azeotropic Distillationhttp://www.answers.com/topic/azeotropic-distillation#ixzz1Y1tthHq3<3> Oxford University. (2003, September 8). Safety data because that Ethanol/water Azeotrope. Retrieved august 28, 2011, indigenous Oxford MSDS: http:// msds.chem.ox.ac.uk/azeotropes/Ethanol-water_azeotrope.html<5> optimistic deviations native Raoult’s Lawhttp://www.chemguide.co.uk/physical/phaseeqia/nonideal.html <4> <6> john C. Gilbert, Stephen F. Martin, speculative Organic Chemistry: A Miniscale and Microscale Approach, Thomson Brooks/Cole, fifth ed, United claims (2010) pp572-575
Q1 is reply under the section, Discussion, Azeotropic distillation. Q2 is likewise answered under the exact same section. Q3 is reply under the section, Discussion, Mechanism