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The 35th Chinese Chemistry Olympiad (Final) Exam Questions November 27, 2021 Wuhan

The 35th Chinese Chemistry Olympiad (Final) Exam Questions

(November 27, 2021 8:30-11:30)

Problem 1 (14 points) A typical procedure for extracting selenium from anode slime from electrolytically refined copper is:

Combustion in the air (reaction 1), and then immersed in water for filtration; after the filtrate is neutralized with dilute sulfuric acid, filtered to obtain a selenite solution. Pass SO2 into the solution ,

Elemental Se precipitates (Reaction 2).

1-1 Take Ag2Se and Cu2Se in anode slime as examples, write the chemical reaction equation in Reaction 1.

1-1 Ag2Se + Na2CO3 + O2 ÿ 2 Ag + Na2SeO3 + CO2

Cu2Se + Na2CO3 + 2O2 ÿ 2 CuO + Na2SeO3 + CO2

1-2 Write the chemical reaction equation in Reaction 2.

1-2 H2SeO3 + 2 SO2 + H2O ÿ Se + 2H2SO4

1-3 double beta decay is a rare decay mode of atomic nucleus, which can be approximated as two consecutive beta decays. First successful observation of double beta decay
82 82
The nucleus of the image is 34Se, write the reaction equation for the double beta decay of 34Se.

1-3 Se ÿ Kr + 2 eÿÿ

1-4 GaCl3 and SeCl4 can react at room temperature to generate ionic compound R. However, equimolar amounts of SeO2, SeCl4 and

GaCl3 was reacted at 50 °C to obtain equimolar number of colorless crystals P and liquid substances Q. Single crystal X-ray diffraction tests showed that colorless crystals

In P , the Ga center has a tetrahedral coordination geometry, and the Se coordination geometry is a triangular pyramid. The molecular geometry of Q is a triangular pyramid. exist

In an inert atmosphere at 800 °C, P thermally decomposes, and the mass percentage of the remaining residue is about 11%.

1-4-1 Write the chemical formula that can indicate the structural characteristics of R, and write the chemical formula of P and Q respectively.

1-4-1 R: [SeCl3][ GaCl4]

P: GaSeCl5O

Q: SeOCl2

1-4-2 According to the relevant properties of Se, Ga chlorides and oxides, deduce the thermal decomposition products of P, and write the chemical reaction equation.

1-4-2

calculation: Since the Se:Cl ratio in GaSeCl5O is 1:5, there must be both SeCl4 and GaCl3 in the product.

Since Ga:O in GaSeCl5O is 1:1, there must be both SeO2 and Ga2O3 in the product.

Therefore, the decomposition products can only be SeCl4, GaCl3, SeO2 and Ga2O3

SeCl4, GaCl3 and SeO2 are gases at high temperature, so the final remaining solid can only be Ga2O3 100%
2×69.72+3×16.00
mGa2O3% = × = 10.96%, which is close to the experimental data, so it can be considered that
5×(69.72+78.96+5×35.45+16.00)
1 mol Ga2O3 is obtained by decomposing 5 mol GaSeCl5O .

equation:

5 GaSeCl5O ÿ 4 SeCl4ÿ + 3GaCl3ÿ + SeO2ÿ + Ga2O3

Question 2 (16 points ) In 1894, Shober and Spanutius reported that NaCP was obtained by reacting NaPH2 with CO, but there was no strong evidence.
according to. Until 2011, Grützmacher et al. repeated the experiment: NaPH2 and CO under the conditions of 1.10 × 107 Pa, 353 K, with ethylenedicarbonate

Glycol dimethyl ether (dme) was used as the solvent, and the compound X crystal containing solvent molecules and OCPÿ as the bridge ligand was obtained by the reaction , and it was confirmed that NaPH2 and

The reaction of CO yields not NaCP, but NaOCP. The structure of X contains a [Na2O2] four-membered ring, and each Na+ is six-coordinated.

2-1 Write down the chemical reaction equation of NaPH2 prepared by passing PH3 gas through the liquid ammonia solution of metallic sodium at ÿ35 °C, and NaPH2 and NaPH2 in the question.

Chemical equation for CO reaction.

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The 35th Chinese Chemistry Olympiad (Final) Exam Questions November 27, 2021 Wuhan

2-1 NaNH2 + PH3 ÿ NaPH2 + NH3

NaPH2 + CO ÿ NaOCP + H2

2-2 Draw the simplified structure of compound X (solvent molecules are represented by dme).

2-2
P

(dme)2Na Na(dme)2
O

2-3 In 2011, Cummins et al. reported that under normal temperature and pressure, using ether as solvent, through Na[{B(C6F5)3}PNb (N[Np]Ar)3] (Ar =
3,5-Me2-C6H3 , Np = neopentyl) with equimolar CO2 to prepare NaOCP synthesis method. Write the chemistry of the preparation
reaction equation.

2-3 Na[{B(C6F5)3}PNb(N[Np]Ar)3] + CO2 ÿ {B(C6F5)3}ONb(N[Np]Ar)3 + NaOCP

When 2-4 Li(dme)2OCP reacts with SO2 , OCPÿ will polymerize to form [P4C4O4] 2ÿ, which contains two five-membered rings and contains PÿP
bond, 31P NMR shows that the P atom has two chemical environments, draw the simplified structure of [P4C4O4] 2ÿ.

2
O O

P
2-4
P P
P

O O

=
2-5 NaOCP reacts with (ipc)2BCl ( ipc ) to obtain compound Y with the molecular formula B3C3P3O3(ipc)6 . Uncle Y

Under the action of butanol, it is transformed into compound Z, which has a triple axis of rotation, and its 31P NMR test shows that all P atoms have the same chemical environment.

Draw the simplified structures of Y and Z.

2-5
OB(ipc)2

Y: P P

(ipc)2BO P OB(ipc)2

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The 35th Chinese Chemistry Olympiad (Final) Exam Questions November 27, 2021 Wuhan

OH

Z: P P

HO P OH

2-6 studies found that the coordination of OCPÿ with the transition metal center would lead to the breaking of the carbon-phosphorus bond, resulting in the formation of CO molecules. When the metal center has a surplus of electrons

When , the generated CO will coordinate with the metal center; and when the metal center lacks electrons, the CO will leave the reaction system.

=
2-6-1 [W(ODipp)4] ( ODipp ) with NaOCP in the presence of ethylene glycol dimethyl ether (dme) and 12-crown-4

O
reaction to obtain product Q. Write the oxidation number of W in [W(ODipp)4], write the geometric configuration of [W(ODipp)4], and draw the ligand in product Q
The structural formula of the anion.

Oxidation number for 2-6-1 W: +4 (

Geometry of [W(ODipp)4]: Planar Square

P
DippO ODipp
The structural formula of the complex anion in Q:
W
DippO ODipp

= N N
2-6-2 [IrCl(PDIMe)] ( PDIMe ) reacted with NaOCP at low temperature, and the carbon-phosphorus bond was also broken, resulting in
N

To the bimetallic biphosphorus compound R. Write the valence electron configuration of Ir in [IrCl(PDIMe)], the molecular formula of R (abbreviation for ligand) and the ligand of Ir

digits.

2-6-2 Ir's valence electron configuration: 5d8 R

's molecular formula: Ir2P2(CO)2(PDIMe)2

Coordination number: five coordination.

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The 35th Chinese Chemistry Olympiad (Final) questions and answers November 27, 2021 Wuhan

Question 3 ( 9 points ) Single-atom site catalysts have high catalytic activity, which is one of the important directions of the current basic research on catalysis. Taking the

addition reaction of acetylene and hydrogen chloride as an example, the traditional carbon-supported Au(III)Cl3 catalyst is prone to reductive deactivation during the

reaction. In contrast, the Au single-atom site catalysts based on C, N two-dimensional materials (Fig. 3-1) can maintain high activity for a long time during the catalytic process.

Figure 3-1

3-1 Draw a proper unit cell of the two-dimensional material, and indicate the number of C and N atoms it contains, respectively.

3-1

6 Cs, 8 Ns

3-2 In addition to the structure shown in Figure 3-1, the two-dimensional material also has an isomer, and its proper unit cell area is 4/9 of the proper unit cell area of

the structure shown in Figure 3-1. Draw A proper unit cell of this isomer.

3-2

3-3 studies show that after single doping, Au is mainly located in the carbon atomic defect sites as shown in Figure 3-2, and coordinates with the surrounding three

nitrogen atoms to form Au-N3 sites. In addition to the aforementioned doping, single-doped Au may also exist in other defect sites of C and N atoms. How many

more of these defect sites are there (just write the number, ignoring lattice distortion caused by doping)?

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The 35th Chinese Chemistry Olympiad (Final) questions and answers November 27, 2021 Wuhan

Figure 3-2

3-3

4 types

The spacing of atoms in the 3-4 reaction sites has an important effect on the catalytic reaction. In this reaction, HCl binds to the Au-N3 site and is

activated, and then undergoes an addition reaction with acetylene to obtain vinyl chloride. The distance between the H atom and the Cl atom in the

activated HCl structure is an important parameter. Structural simulation (Fig. 3-3) shows that the bond lengths of Au-N(1), Au-N(2), and Au-N(3) are 203

pm, 206 pm, and 200 pm, respectively, and the bond lengths of Au-Cl bonds are 233 pm, N(1)-H bond length 102 pm, Cl-Au-N(1), Cl-Au-N(2), Cl-Au-N(3)

bond angles are 100°, 170 °, 100°, Au-N(1)-H bond angle 90°, Cl-Au-N(1)-H dihedral angle 0°, calculate the distance between H and Cl.

Figure 3-3

3-4

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The 35th Chinese Chemistry Olympiad (Final) questions and answers November 27, 2021 Wuhan

ÿ
ÿ (pm)
= 275pm

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Question 4 (7 points ) The discovery of green fluorescent protein won the 2008 Nobel Prize in Chemistry. The chromophore of green fluorescent protein is formed by three

steps of intramolecular condensation, dehydration and oxidative dehydrogenation of threonine, tyrosine and glycine. The chromophore structures of tyrosine, histidine and

the final product of the reaction are shown in Figure 4-1:

4-1 In order to adjust the absorption spectrum of fluorescent protein, its amino acid sequence can be improved. An improved method is to mutate tyrosine to histidine, which

blue-shifts the absorption peak. Draw the corresponding simplified structure of the chromophore (stereoconfiguration is not required).

4-1, (1 point)

4-2 Another way of improvement is to introduce a new tyrosine whose side chain residue is just above the original tyrosine, the structure is shown in Figure 4-2. The

absorption peak of the chromophore is red-shifted compared with the green fluorescent protein, and the reason is briefly described.

4-2, (1 point) ÿ-ÿ

stacking causes a larger electron delocalization range, a smaller energy level gap, and a red shift of the absorption peak

4-3 A red fluorescent protein whose chromophore biliverdin is produced by the oxidation of heme, while releasing ferrous ions. The reaction process is shown in Figure 4-3.

The main reasons for the departure of ferrous ions are given. 4-3, (1 point) The lone pair of electrons on the nitrogen of the oxidized amide group forms a conjugated system

with the carbonyl group, which reduces the coordination ability to ferrous ions

4-4 Green fluorescent protein has a total charge of ÿ7.88 at pH = 7.40. All amino acid species with charged side chain residues in its amino acid sequence and their side

chain pKa are shown in Figure 4-4 (negligible for water). the effect of ionization, and the effect of peptide formation on the pKa of the side chain). It is known that the number

of lysines in the amino acid sequence of green fluorescent protein is 20, the number of aspartic acid is 18, the number of glutamic acid is 16, the number of arginine (nR) is

less than 10, and the number of histidine is less than 10. (nH) is greater than 5, and the sum of the number of histidine (nH) and cysteine (nC) is 12. Calculate nR, nH and

nC values.
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4-4, a total of 4 points for this sub-question

First, the number of charges for each amino acid can be calculated at pH = 7.40 (the effect of water ionization can be ignored, and the formation of more

[Base]
peptide effect on side chain pKa), given by pH p lg ÿ Ka
ÿ
(or partition function), the number of charges can be obtained

[Acid]
1 1
n(+) ÿ

pH p
(number of positive charges for H, R, K) or n(
ÿÿ
) Kÿ
(Number of negative charges for D, E, C).
ÿ ÿK
1 10 a 1 10 ÿ p pH
a

The calculation shows that under the premise of retaining two significant digits after the decimal point, arginine (R), lysine (K), aspartic acid (D) and

Glutamate (E) is +1.00, +1.00, ÿ1.00, ÿ1.00, so their numbers will not change the decimal point of the total charge
The last two. Therefore, the number of histidines and cysteines determines the total charge to two decimal places.

The calculation shows that the average number of charges per histidine is +0.042, the average number of charges per cysteine is ÿ0.15, and the total number is

Each possible combination of conditions of 12 yields two decimal places (the total charge is negative, the number of histidines

more than 5) as follows:

Two decimal places for histidine cysteine

11 0.69 1

10 2 0.88

9 3 0.07

8 4 0.26

7 5 0.46

6 6 0.65

Since the total number of charges is ÿ7.88, it can be seen that histidine nH and cysteine nC are 10 and 2, respectively.

According to the value of histidine nH and cysteine nC, and the number of lysine is 20, the number of aspartic acid is 18, the number of glutamine

The number of acids is 16, and the calculation of the total number of charges:

(20 + nR – 18 ÿ 16) + (0.042 ÿ 10 ÿ 0.15 ÿ 2) = ÿ7.88

get nR = 6

Appendix Section:

Amino acid charge number calculation process and retention of significant figures:

1
Positively charged amino acid pH p ÿ Ka 10pHÿpK a 1ÿ10 ÿpHKp a
pH p
ÿ ÿK
1 10 a

Histidine (+) 1.36 twenty three twenty four 0.042

Arginine (+) ÿ4.70 Lysine (+) ÿ3.27 0.000020 1.000020 0.999980(1.00)

0.00054 1.00054 0.99946(1.00)

Kÿ Kÿ
1
negatively charged amino acid p pH
a
Kÿ 10p pH a 1 10 ÿ p pHa Kÿ
1 10 ÿ p pH
a

Aspartic acid (ÿ) ÿ3.69 Glutamate (ÿ) 0.00020 1.00020 0.99980(1.00)

ÿ2.89 Cysteine (ÿ) 0.74 0.0013 1.0013 0.9987(1.00)

5.5 6.5 0.15
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Question 5 (6 points ) Molecular machine refers to a series of molecules that use artificially synthesized molecules to simulate the operation and function of

natural biological macromolecular machines or macroscopic machines. He was awarded the 2016 Nobel Prize in Chemistry for his superb design ideas and

rich imagination. Recently, scientists reported a molecular machine that mimics the working principle of a "pump", which can thread the rod-shaped molecule

DB into the ring of the ring-shaped molecule CBPQT through a series of chemical processes. Figure 5-1 shows the simplified structures of CBPQT and DB and

the names of the segments contained in DB.

5-1 indicates the number of charges (indicate positive and negative) on DB and CBPQT

molecules. 5-1 This sub-question has a total of 1 point DB with +3 charge CBPQT with +4

charge

5-2 Under normal conditions, DB cannot penetrate into the ring of CBPQT. After CBPQT is reduced by 2 electrons to form a free radical, it can be penetrated

by the left end of DB and combined with fragment V after reduction by 1 electron. Explain the reason and draw the most stable structural formula of the

reduction product of CBPQT after accepting 2 electrons, and indicate the position of the charge and free radical. 5-2 This sub-question has a total of 2 points

because both CBPQT and V are positively charged, and electrostatic repulsion makes their combination unstable, and the free radical formed after reduction

is attractive to the free radical pairing

5-3 Re-oxidize both CBPQT and fragment V in the above structure, CPBQT will further cross fragment IPP, and be pushed to the area between fragment T and

fragment S like a "pump", and will not fall off, forming Figure 5 -2 product. Indicate the role played by the isopropyl group on fragment IPP.
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5-3 The steric hindrance effect of a

total of 1 isopropyl group in this sub-question prevents CBPQT already between fragment T and fragment S from slipping back to fragment V.

Through a set of "reduction-oxidation" processes, the 5-4 molecular pump promotes the occurrence of chemical reactions in which the standard Gibbs free energy

becomes much greater than 0, and plays a role in "doing work" for chemical reactions. The standard Gibbs free energy of the reaction for the penetration of the entire

DB into the CBPQT ring becomes 59 kJ molÿ1. The reaction process is represented as follows:

The first step of the CBPQT + DB ÿ CBPQT-DB

reaction uses Zn as a reducing agent (standard electrode potential of ÿ0.76 V) to reduce CBPQT and DB to

[CBPQT-DB]3ÿ. In the second step of the reaction, MB+ was used as the oxidant (standard electrode potential was 1.22 V), and [CBPQT-DB]3ÿ was oxidized to

CBPQT-DB, and MB+ was converted to MB. The standard electrode potentials of DB/DBÿ and CBPQT/CBPQT2ÿ are ÿ0.32 V and ÿ0.26 V, respectively, and the

theoretical working efficiency ÿ of the molecular pump is calculated. 5-4 This sub-question has a total of 2 points The reaction equation of the whole process is as

follows: 1.5Zn + 3MB+ + CBPQT + DB ÿ 1.5Zn2+ + 3MB + CBPQT-DB The total "work" energy of the two redox reactions is: G nFE 3 96485 ( 1.22 ( 0.76)) = ÿ573 (kJ

molÿ1 )

ÿ ÿ ÿ oÿ ÿ ÿ ÿ ÿÿ

rm

So the working efficiency of the pump is ÿ = 59/573 = 10%

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The 35th Chinese Chemistry Olympiad (Final) Exam Questions November 27, 2021 Wuhan

Question 6 (16 points) Isotope Effects

Isotopic substitution, such as the substitution of D ( 2H) for H ( 1H), may cause changes in equilibrium constants and reaction rates, which are called thermodynamic isotopes

effects and kinetic isotope effects.

6-1 Kinetic isotope effect can be used to study the reaction mechanism. The kinetics of the bromination of phenylisopropyl ketone were studied, data at 298 K

ÿ ÿ ÿ ÿ
As shown in the table below, let its rate equation be rk [KH] [H] [Br]
ÿ

apparent 2 , indicate the fractional number of each reactant and calculate the apparent rate constant.

ÿ1
No. Buffer pH [KH]0 (mol Lÿ1 ) [Br2]0 (mol Lÿ1 ) Initial rate r0 (mol Lÿ1 h )

1 2.70 1.00ÿ10ÿ3 1.00ÿ10ÿ3 2.3ÿ10ÿ4

2 2.70 2.00ÿ10ÿ3 1.00ÿ10ÿ3 4.6ÿ10ÿ4

3 3.70 1.00ÿ10ÿ2 1.00ÿ10ÿ2 2.3ÿ10ÿ4

4 3.70 1.00ÿ10ÿ2 2.00ÿ10ÿ2 2.3ÿ10ÿ4

As shown in Figure 6-1, KH represents phenyl isopropyl ketone molecule, and KD represents its deuterium substituted molecule.

Figure 6-1

6-1

Knowing from (3) (4) that the number of Br2 grades is 0 Combined with (1) and (2), the number of grades of KH is 1.

ÿ
From (1) (3), it is known that the hydrogen ion classification number is 1 which is rk
0 [H] [KH]
ÿ

apparent 0 0

4 1 1
2.3 ÿ10 mol Lh k mol L 1.001 ÿ10 mol
10 2.70 ÿ L
3 1
ÿ ÿ ÿ ÿ ÿ ÿ ÿ

Take the first set of data as an example

ÿ ÿ
apparent

4
2.3 10 ÿ
ÿ

2 1 1
k
ÿ ÿ

ÿ ÿÿ
Solutions have to
1.2 10 (L mol h )
apparent
10ÿ

2.70
ÿ 1.00 10
ÿ
ÿ

The bromination of 6-2 -phenylisopropyl ketone is an acid-catalyzed reaction. The possible mechanisms are generally considered to be:

ÿ k1 ÿ
KH H ÿ HK-H K
k ÿ

1 eq

HK-H ÿ
ÿÿÿ
k2
Enol(Enol ) ÿH
ÿ

Enol Br 2
k3 ÿ
K-Br H Br ÿ ÿÿÿ ÿÿ
ÿ

Using the steady-state approximation, a reasonable approximation is made to derive the rate equation for the total reaction. Point out the rate-controlling step for this reaction and explain why.

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The 35th Chinese Chemistry Olympiad (Final) Exam Questions November 27, 2021 Wuhan

6-2 Make steady-state approximation for HK+, we have

ÿ
d [HK-H] ÿ ÿ ÿ
ÿÿ
k
0 [KH][H] k
[HK-H] [HK-H]
1
ÿ

1
ÿ

k 2
dt

ÿ
k [KH][H]
1
ÿ

[HK-H] ÿ

kk ÿ ÿ

1 2

If the second step is a quick control step, then

kk [KH][H] ÿ

ÿÿ
rk
2 [HK-H]
2
ÿ ÿ 12

rtotal _
kk ÿ ÿ

1 2

a. The rate equation obtained by the assumption is the same as the experimental rate equation; if the third step is a rate control step, [Br2] will appear in the rate equation,

The number of levels is not 0. b. Due to the fast diffusion rate of hydrogen ions in the solution, the proton transfer step is a fast reaction; the second step is single-molecule bond breaking

reaction, the activation energy is generally larger, so it is reasonable for the second step to be a rate-controlled step;

6-3 Keep the concentration of the reactants and the pH value of the buffer solution unchanged, and the bromination reaction rate of phenylisopropyl ketone at 308 K is doubled compared with that at 298 K.

ÿ KH H
Estimate the activation energy for the rate-controlling step of this reaction. Known reaction
ÿ
HK-H ÿ
ÿH = 30 kJÿmolÿ1.

6-3

6-3

k (308K) E 1 1 ÿ
a , apparent ÿ
by the Arrhenius equation Apparent ln k ÿÿ
ÿ
ÿ
ÿ
ln 2
Apparent
(298K) R ÿ 308K 298K ÿÿ

E ÿ
52.9 kJ mol-1
,
aAppearance _

kk1 2 kk1 2
From the x-2 results, the apparent rate constant of the total packet reaction k ÿ ÿÿ k 2eq
K
apparent
kkk1 ÿ
ÿ

2 ÿ

E ÿ ÿ ÿ ÿ ÿ EEEEH
ÿ a, apparent
2 1 ÿ

1 2

EEH ÿ

a,
ÿ ÿ ÿ 52.9 30 23 (kJ mol )
apparent
ÿÿ
-1
a,2

kk1 2 kk1 2
From the x-2 results, the apparent rate constant of the total packet reaction k ÿ ÿ ÿ
k 2eq
K
apparent
kkk1 ÿ
ÿ

2 ÿ

k (308K) K eq
k2 (308K) (308K) k2 (308K) K eq (308K)
apparent
ÿ ÿ ÿ
ÿ
2
kapparent
(298 K) k 2 (298K) K
(298K) (298K) k2 K (298K)
eq eq

eq (308K) ÿH 1 30000 1 ( 1 1
Kln _ ÿ
)
ÿ
ÿ ÿ
ÿ
) 0.393
K eq (298K)
R ( 298K 308K 8.314 298 308

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The 35th Chinese Chemistry Olympiad (Final) Exam Questions November 27, 2021 Wuhan

K eq (308K) 0.3931
k (308 K)
ÿe ÿ
1.48 so there are 2 ÿ
1.35
K eq (298K) k (298K)
2

k (308 K) E 1 1 ÿ
a ,2 ÿ
by the Arrhenius equation 2 ln ÿÿ
ÿ
ÿ

k 2 (298K) R ÿ 308K 298K ÿÿ

k2 (308K) ÿ 1 1 ÿ 1
ER 23 kJ mol
ÿ

a,2
ÿÿ
ln ÿ
ÿ
ÿ

k 2 (298K) 308K
ÿ 298K ÿÿ

6-4 takes the kinetic isotope effect of the CH bond dissociation reaction as an example, and the description is as follows. The bond stretching vibration can be approximated by a simple harmonic vibration.

1 ÿ
ÿ is the force constant (the force constant of CH and ÿ
vibration frequency
ÿ
CD ÿ , in the formula
2ÿ ÿ

mm
Wait), ÿ is the equivalent quality, taking CH as an ÿexample . ÿ . Molecules in vibrational basis
mm ÿ
C H

1
The energy in the state is called the zero-point energy E0, E 0hv ÿ , where h is Planck's constant.
2
As shown in Figure 6-2, the zero-point energies of CD and CH reactants are different, but due to the transition state

The force constant of the stretching vibration is very small, and the difference between the zero-point energies of the CD and CH transition states can usually be

To ignore, therefore, the activation energy of CD bond dissociation is greater than that of CH bond dissociation. Approximate recognition

If the Arrhenius exponents of the two reactions are equal, then the change in the reaction rate constant Figure 6-2

can be calculated quantitatively. Calculate the rate of the rate-controlling step of the bromination reaction of KH and KD at 298K

rate constant ratio. It is known that ÿC-H = 2950 cmÿ1, and the relative atomic masses of H and D are 1.007 and 2.000, respectively.

6-4 Consider the kinetic isotope effect,

ÿ
1.007 12.01

ÿ CH 1.007 12.01
12.01
ÿ 2.000 ÿ

1
ÿ ÿ
ÿ ÿ
2950 ÿ ÿ
CD CH 2172 (cm )
ÿ
ÿ CD
ÿ
2.000 12.01

ÿ1 ÿ
hcN (ÿ
ÿ

ÿ )
k ÿE ÿ2 A CH CD ÿ

CD ÿÿ 0
exp( ) exp
ÿ ÿÿ ÿ

k RT ÿ RT
CH ÿÿ
ÿÿÿ

34 10
6.626 10 ÿ
ÿ

ÿ
ÿ 2.998ÿ 10 6.022
ÿ ÿ ÿ
twenty three

10 (2950 2172) ÿÿ
ÿ

ÿ
ÿ
exp ÿ
ÿ
ÿ
0.153
ÿ
2 8.314
ÿÿ 298

k
or CH
ÿ
6.54
kCD

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The 35th Chinese Chemistry Olympiad (Final) Exam Questions November 27, 2021 Wuhan

6-5 Under alkaline conditions, the reaction mechanism of KH chlorination will change, and the apparent rate equation of the total reaction is:

r k[Cl ][OH
ÿ

2 ][KH] ÿ . Try to draw up the reaction mechanism of KH chlorination reaction.

ÿ k1 ÿ

6-5 KH OH ÿ KH O2
kÿ 1
ÿ2

k ÿ

K Clÿÿÿ ÿ2 KCl Cl ÿ

The second step is the speed control step. According to the equilibrium approximation, the total package reaction rate equation can be obtained as

rk K[Cl
2 ][OH
ÿ

2 ][KH] ÿ
consistent with the experimental equation

The effect of 6-6 deuteration on the equilibrium constant of chemical reactions can also be discussed from the zero-point energy. Acetic acid is known to ionize at 298K

ÿ
HOAc HO ÿ 2
OAc HOÿ pKa =3 4.74, and the vibrational wave numbers of the OH bond in H3O+ and HOAc are 3000 cmÿ1 and 2800 , respectively

cm ÿ1. Determine how the ionization reaction pKa of DOAc in D2O changes compared to the pKa of HOAc ionization reaction in H2O and explain why (no

required to calculate the pKa value).

6-6

pKa reduction

noted K=k+/k

kÿ ÿ E0 hcN (ÿ ,HOAc
AOH
ÿ

ÿ OD, DOAc ÿ ) ÿ
For forward and reverse reactions: ,DOAc ÿ
exp( exp
ÿ ÿ ÿÿ )
ÿ

k ÿ ,HOAc RT 2 RT
ÿ ÿ

k ÿ
+ ÿE0 hcN A (ÿ +
ÿ

ÿ
+ ÿ)
,DO
3 OH,HO 3 OD, DO
3
ÿÿ
exp( ÿ ÿ ÿÿ )
exp ÿ

k +
RT 2 RT
ÿ
ÿ
ÿ

,HO
3 ÿÿ

o
K DOAc/DO 2 ÿ k ÿ
ÿ
,DOAc ÿ ÿ ÿ ÿ ÿ
k ÿ

,DO
+ ÿ
N Ahc ÿ
3
ÿ
ÿ ÿ
exp ÿ ÿ ÿ OH, HO3 ÿ
ÿ OD, DO3 ÿ
)( ÿ OH,HOAc ÿ OD, DOAc ÿ
ÿ ÿÿ ÿ

o ÿ ÿ ÿ)
K HOAc/HO 2
ÿÿ
k ÿ ,HOAc k ÿ

,HO
+ ÿÿ2
RT (ÿ ÿ
ÿ
3 ÿÿÿ

Because OH in H3O + has a larger vibrational wavenumber than OH in HOAc, the wavenumber after deuteration becomes smaller by the same multiple, then after deuterium

(ÿ OH, HO
ÿ
3
ÿ

ÿ OD, DO
3
ÿ
)(
ÿÿ

ÿ OH,HOAc ÿ

ÿ OD, DOAc )
is a positive value.

o
again K
p(DOAc) lg( Kÿÿ ) , so the pKa decreases
a DOAc/DO 2

Page 6 of 8
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The 35th Chinese Chemistry Olympiad (Final) Exam Questions November 27, 2021 Wuhan

The 35th Chinese Chemistry Olympiad (Final) Exam Questions (November

27, 2021 8:30-11:30)

Question 7 (10 points ) Acidity and polarity of organic compounds

7-1 Acid-base theory is of great significance to the development of organic chemistry.

The acidity of 7-1-1 benzoic acid derivatives is closely related to the nature of its substituents. As shown below, the pKa value of compound B is significantly smaller than the other three compounds. A

reasonable explanation is given for this result.

The acidity of 7-1-2 dicarboxylic acid is closely related to the distance between two carboxyl groups. For example, the pKa1 of oxalic acid is smaller than that of malonic acid, and the pKa1 of phthalic acid is

smaller than that of isophthalic acid . A reasonable explanation is given for this result.

The pKa of 7-1-3 2,6-dimethyl-4-nitrophenol is smaller than that of 3,5-dimethyl-4-nitrophenol , which gives a reasonable explanation for this result.

7-1 Answer:

7-1-1 Due to the intramolecular hydrogen bonding of the ortho-phenolic hydroxyl group to the carboxylate anion, the anion is stabilized.

7-1-2 weakened with the extension of the carbon chain due to the electron-withdrawing induction effect of the carboxyl group.

In 7-1-3 , the substitution of the 3- and 5 -position methyl groups reduces the coplanarity of the nitro group with the benzene ring, which leads to the weakening of the delocalized dispersion ability of the negative charge of the phenolic oxygen,

thereby reducing its acidity and increasing its pKa .

7-2 In 2015, a British research team first synthesized all-cis 1,2,3,4,5,6-hexafluorocyclohexane (1). This is the most polar nonionic organic compound known to date. The synthetic route of 1 is shown in the

figure below: using myo-inositol (2) as the starting material, the intermediate 3 is synthesized through 6-step transformation, and then undergoes a 6-step reaction with deoxyfluorination and nucleophilic

fluorination as the key steps. Preparation 1. (Hint: DeoxoFluor is a commonly used deoxyfluorination reagent that converts hydroxyl to fluorine and generates SOF2. Et3N•3HF is a commonly used nucleophilic

fluorination reagent)
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The 35th Chinese Chemistry Olympiad (Final) Exam Questions November 27, 2021 Wuhan

7-2-1 How many stereoisomers are there in 1,2,3,4,5,6-hexafluorocyclohexane (just the number)? Draw the simplified structural formula for one of the enantiomers.

7-2-2 draws the simplified structure of compound 4 .

7-2-3 detection showed that the 19F NMR spectrum of compound 1 only had two signals of –212.8 ppm and –217.3 ppm. Draw the stable conformation of 1 and explain why it has large polarity.

7-2-4 briefly describes the main reason for the low yield of the last step reaction ( synthesis of 1 from 8 ).

7-2 Answers:

7-2-1 9 stereoisomers; 2 enantiomeric structures.

7-2-2 4 Structure
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The 35th Chinese Chemistry Olympiad (Final) Exam Questions November 27, 2021 Wuhan

7-2-3 Compound 1 has the classic chair conformation of cyclohexane; the side where fluorine is located is negatively charged, and the side where hydrogen is located is positively charged, with positive and negative charges

The center separation is obvious. Therefore, it has a large dipole moment.

8-2-4 Reason for the low yield: The nucleophile F ÿ approaches the molecule from the side where the 5 Fs are dense to participate in the reaction. The extremely electronegative F is densely located on the same side of the substrate, and the F ÿ

produce strong dipole repulsion.

Question 8 (11 points ) New organic reagents, new reactions and synthetic applications

8-1 Diazomethane (CH2N2) can be widely used in organic synthesis as methylation reagent, carbene precursor, nucleophile and dipole. Due to the high toxicity and safety (boiling point –23 ºC,

flammable and explosive) of CH2N2 , scientists have developed its alternative reagent: trimethylsilyldiazomethane (Me3SiCHN2, boiling point 96 ºC).

8-1-1 Draw two stable resonance equations of Me3SiCHN2.

H H
N N N N
8-1-1
Me3Si Me3Si

8-1-2 Me3SiCHN2 is often used as a one-carbon synthesis unit in the carbonization reaction. Write the structural formula of the following reaction product, and write the reaction mechanism expressed

by the structural formula (hint: Sc(OTf)3 is a Lewis acid, and the trimethylsilyl group can undergo [1,3]-ÿ migration).

O
Me
Ph
product: ;

mechanism:
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The 35th Chinese Chemistry Olympiad (Final) Exam Questions November 27, 2021 Wuhan

H [Sc]
O [Sc] N N N2
O O
Me O
Sc(OTf)3 Me3Si Me
Me Me SiMe3 SiMe3
Ph Ph
Ph Ph 1,2-migration

SiMe3
O O
Me H3O Me
Ph Ph

8-1-3 utilized a dipolar cycloaddition reaction involving Me3SiCHN2 in the total synthesis of the natural product amathaspiramide A. Draw the simplified structures of compounds C,

D, and F in the total synthetic route shown below (disregarding the stereochemistry of the products).

8-1-3
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The 35th Chinese Chemistry Olympiad (Final) Exam Questions November 27, 2021 Wuhan

The 8-2 olefin metathesis reaction (olefin exchange reaction) can synthesize new olefins from two olefins, revolutionizing the design logic of molecular synthesis. In recent years,

Chemists also developed the metathesis of alkenes and ketones. According to the transformation mode of the olefin metathesis reaction, the main product G of the following reaction is inferred, and the transformation is given.

Simplified structures of two key intermediates in the chemistry process.

8-2

G
mechanism:
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The 35th Chinese Chemistry Olympiad (Final) Exam Questions November 27, 2021 Wuhan

F3B F3B BF3

O O
O O
BF3 •OEt2 TM

Question 9 (11 points ) Application of organic chemistry in drug synthesis

Remdesivir is a new type of nucleotide antiviral drug developed by Gilead. In November 2021, the antiviral drug molnupiravir developed by Merck was launched in the UK. The antiviral mechanisms of both

Remdesivir and molnupiravir inhibit viral replication by blocking the synthesis of RNA polymerase (RdRp).

Recently, Chinese scientists have made important improvements to the synthetic route of remdesivir: by developing a chiral imidazole organic small molecule catalyst,

It solves the problem of efficient construction of the phosphorus chiral center of remdesivir. Some of the synthetic routes are as follows:

9-1 indicates the absolute configuration of carbon (C1) and phosphorus at position 1 in the molecular structure of remdesivir.

9-2 Draw the structural formula of the first step reaction intermediate 4 (without separation and purification, directly used in the next step reaction) and raw material 5 , and explain the function of the first step reaction. 9-3

Compound 6 synthesized by this route is a mixture of a pair of C1 epimers (ÿ:ÿ = 3:1), but compound 7 is a single configuration product. Draw the simplified structure of 7 and explain the transformation of 6 to the single

configuration 7 using reaction intermediates .

9-4 Molnupiravir exists in two tautomers that mimic cytidine C and uridine U, respectively, resulting in increased mutation rates during viral RNA replication. Write down another tautomer of molnupiravir, determine the main

base pairing modes that these two tautomers are involved in, and draw its schematic diagram.
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The 35th Chinese Chemistry Olympiad (Final) Exam Questions November 27, 2021 Wuhan

Answer:

9-1

The role of the first step in 9-2 is to protect the amine group.

9-3
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The 35th Chinese Chemistry Olympiad (Final) Exam Questions November 27, 2021 Wuhan

10-4