Amy Stanley

CHEM 278
Section 02
Reactions to Form Derivatives of Cyclohexanol
Results:
Mass of starting Mass of Mass of Boiling
material receiver receiver flask point
(cyclohexanol) flask + product
Product 1 12.0 g (12.47 mL) 56.858 g 62.738 g 83 °C
Table 1. Product 1 data

Mass of round Mass of round bottom

bottom flask flask + product 2
Product 2 121.625 g 124.417 g
Table 2. Product 2 data

Product 1: 1H NMR  (CDCl3) 7.2759 (s, 1H, CHCl3), 5.6869 (s, 2H, CH), 2.0153 –
1.9987 (m, 4H, CH2), 1.6434 – 1.6184 (m, 4H, CH2); 13C NMR  (CDCl3) 127.2205
(CH=CH), 77.2552 (CH2), 77.0012 (CH2), 76.4771 (CH2), 25.1303 (CH2), 22.6100
(CH2); IR (Film) 3021.65 (=CH stretching), 2924.09 (CH2 stretching), 2858.54 (CH2
stretching), 1651.96 (C=C stretching), 718.09 (RCH=CHR cis).
Product 2: 1H NMR  (CDCl3) 1.9468 – 1.9068 (m, 2H, CH), 1.6812 – 1.6275 (m, 4H,
CH2), 1.3258 – 1.2748 (m, 4H, CH2), 1.2029 – 1.1501 (m, 4H, CH2); 13C NMR  (CDCl3)
67.6573 (CCl2), 26.0571 (CH), 20.4281 (CH2), 19.0944 (CH2); IR (Film) 2939.68 (CH2
stretching), 2858.60 (CH2 stretching), 793.92 (C-Cl stretching), 752.38 (C-Cl stretching),
719.01 (C-Cl stretching), 648.20 (C-Cl stretching).
Interpretation of data and conclusion: First, it’s important to note which layer was taken in
each part of the lab. For product 1, it was the top layer because it did not dissolve in water and
the bottom layer did. This means that the top layer is the organic layer and the bottom layer is the
aqueous layer. For product 2, a drop of water was added to the separatory funnel, and it went
right through the top layer and dissolved into the second layer. This means that the top layer is
organic, and the bottom layer is the aqueous layer. So, in both cases the top layer, the organic
layer, was taken and used for the experiment because they contained the organic products [3].
The percent yield for each product can be calculated by the product divided by the starting
amount and multiplied by one hundred. It’s important to remember to subtract the mass of the
flask from the mass of the flask + product to just get the amount of product. So, for product 1 the
percent yield is ((62.738 – 56.858)/12) x 100 = 49% yield (table 1). The low percent yield could
be because the product is highly volatile and could have been lost [1]. For product 2, the starting
amount was product 1, which would be the mass of the receiver flask + product minus the
receiver flask, 62.738 – 56.858 = 5.88 g (table 1). So, the percent yield for product two is
((124.417-121.625)/5.88) x 100 = 47.5% yield (table 2). This percent yield could be low because
some of the product was poured out with the aqueous solution in the separatory funnel.
To determine the two products its important to look at the all the reagents being added. For
product one there is an alcohol going in, the cyclohexanol, and a strong acid, phosphoric acid.
 Amy Stanley
CHEM 278
Section 02
This will lead to the dehydration of the alcohol to form an alkene. The reaction is shown here
(figure 1):

Figure 1 Dehydration of cyclohexanol

As shown above, the resulting product is cyclohexene. This would match with the proton NMR
in that there are three hydrogen environments, two of them having four hydrogens and the other
having two hydrogens. The number of neighboring hydrogens also matches up with hydrogen
environment. This also matches that carbon NMR showing that there are sp2 and sp3 hybridized
carbons. Lastly, the IR spectra shows carbon-carbon double bond stretching, CH2 stretching, and
CH stretching that all matches up with cyclohexene. It can also be confirmed by the boiling
point, which is listed as 83° C on PubChem, just like in table 1 [2].
As for product 2, chloroform and sodium hydroxide are added to the cyclohexene. This will
result in an alpha elimination reaction, resulting in a cyclopropane ring where the double bond
was. The reaction proceeds by the strong base, in this case sodium hydroxide, attacking the
chloroform to form a carbene (figure 2).

Figure 2 Carbene formation [3]

Once a carbene is formed it is inserted into the double bond to form a cyclopropane ring (figure
3). The reaction uses tetrabutylammonium bromide as a phase transfer catalyst, which means it is
soluble in both the organic and the aqueous phase, so it carries the anions from the organic phase
to the aqueous phase [4]. This helps speed up the reaction.

Figure 3 Formation of product 2

 Amy Stanley
CHEM 278
Section 02
This reaction will result in the formation of 7,7-dichlorobicyclo[4.1.0]heptane. The IR spectra
confirms that this is the correct compound since it shows CH2 stretching and C-Cl stretching.
The proton NMR also shows the different hydrogen environments. The carbon NMR shows that
the carbon close to the chlorine, then the carbons in the cyclohexane ring.
References:
[1] Cooley, J. H., & Williams, R. V. (2020). Organic Chemistry Laboratory I (Online ed.).

[2] Cyclohexene. (n.d.). Retrieved November 9, 2020, from

https://pubchem.ncbi.nlm.nih.gov/compound/cyclohexene

[3] Libretexts. (2020, August 11). 8.10: Addition of Carbenes to Alkenes - Cyclopropane
Synthesis. Retrieved November 9, 2020, from
https://chem.libretexts.org/Bookshelves/Organic_Chemistry/Map:_Organic_Chemistry_(McMur
ry)/08:_Alkenes-_Reactions_and_Synthesis/8.10:_Addition_of_Carbenes_to_Alkenes_-
_Cyclopropane_Synthesis

[3] Organic Chemistry (Director). (2020, October 29). Lab 9 Cyclohexanol [Video file].
Retrieved from https://www.youtube.com/watch?v=cJrxF9_ALEI&feature=youtu.be

[4] Phase Transfer Catalysts. (n.d.). Retrieved November 09, 2020, from
https://www.tcichemicals.com/BE/en/c/12692