115年 - [無官方正解]115 國立中山大學_碩士班考試入學招生考試試題_化學系：有機化學及無機化學#138420

1. Which of the following methods is NOT suitable for the synthesis of Compound X?
(A) 3-methylbut-1-yne
(B) 3-methylbutan-2-ol +
(C) methyl 2-methylpropanoate
(D) acetonitrile
(E) acetyl chloride 

2. How many peaks do you expect to see in the 1H NMR of Compound X (assuming the peaks do not overlap with each other)?
(A) 2
(B) 3
(C) 4
(D) 5
(E) 6

3. Which of the following would be suitable reagents in Step 1?
(A) i) KMnO₄, ii) isopropanol, concentrated HCl
(B) i) NaBH₄, ii) CH₃COCl
(C) isopropanol, NaH
(D) m-chloroperbenzoic acid
(E) isopropanol, HCl

4. Which of the following would be the correct ¹H NMR of Compound Y?
(A)
(B)
(C)
(D)
(E) None of the above is correct

5. What is the most likely structure of product Z?
(A) 
(B)
(C)
(D)
(E)

6. Which of the following descriptions about the TLC analysis of Compound G and H is incorrect?

(A) If "TLC 1" is a normal phase silica TLC plate, Compound H is more polar than Compound G.
(B) If Compound G and H are analyzed again with a reverse phase silica TLC plate in EtOAc:n-hexane (3:2) then "TLC 2" could be the result.
(C) "TLC 2" could be the result of running a normal phase silica TLC plate with EtOAc:n-hexane (2:3).
(D) The Rf values of both compounds would change if the TLC is run with different ratios of EtOAc and n-hexane.
(E) All of the above are incorrect

7. The highest occupied molecular orbital (HOMO) of 1,3,5-hexatriene is:
(A)
(B)
(C)
(D)
(E)

8. What would be the major product of the following reaction?

(A) 
(B)
(C)
(D)
(E)

9. The reaction in question 8 is classified as a ...
(A) [3,3] sigmatropic rearrangement
(B) [6π] electrocyclization
(C) [4+2] cycloaddition
(D) [2+2] cycloaddition
(E) [3+3] cycloaddition

10. What would be the major product of the following reaction?
(A)
(B)
(C)
(D)
(E)

11. Which of the following is/are nonaromatic?

(A) 1 and 2
(B) 3 and 5
(C) 3
(D) 4
(E) 4 and 5

12. What is the complete systematic IUPAC name for Compound J?
(A) (1S,4R)-1-hydroxy-4-isopropylcyclopent-2-ene
(B) (1R,4S)-1-hydroxy-4-isopropylcyclopent-2-ene
(C) (1S,4R)-4-isopropylcyclopent-2-en-1-ol
(D) (1R,4R)-4-isopropylcyclopent-2-en-1-ol
(E) (1S,4R)-1-isopropylcyclopent-2-en-4-ol

13. What is the most likely structure of Compound K?
(A) structure A with HO group
(B) structure B with OH group
(C) structure C with OH groups
(D) ketone structure D
(E) ketone structure E

14. How would you use the following sets of reagents to synthesize Compound M from benzene (providing that ortho and para products can be separated)?
1) NaOMe, MeOH, heat 2) HNO₃, H₂SO₄ 3) Cl₂, FeCl₃ 4) NaNO₂, HCl
(A) 3 then 1 then 2
(B) 2 then 3 then 1
(C) 3 then 2 then 1
(D) 4 then 3 then 1
(E) 3 then 4 then 1

15. What is the most likely structure of Compound N?
(A)
(B)
(C)
(D)
(E)

16. 18 electrons can generally be the most stable configuration for most organometallic compounds due to:
(A) electrons filling in antibonding orbitals in the molecular orbitals
(B) no electron filling in antibonding orbitals in the molecular orbitals
(C) electrons filling in non-bonding orbitals in the molecular orbitals
(D) no electrons filling in non-bonding orbitals in the molecular orbitals
(E) None of the above

17. What is the point group of a water molecule?
(A) C_2v
(B) C₂
(C) C_3v
(D) σ_d
(E) None of the above

18. X-rays have a shorter wavelength than visible light?
(A) True
(B) NOT True
(C) No such thing called X-ray
(D) No such thing called visible light
(E) None of the above

19. In a two-dimensional crystal lattice, which one of the following indices corresponds to the smallest density of lattice points?
(A) (10)
(B) (13)
(C) (21)
(D) (11)
(E) (41)

20. AgCl has a higher solubility than AgI, can be most likely explained by:
(A) dipole interaction
(B) redox chemistry
(C) Hard and Soft Acids and Bases
(D) corrosion chemistry
(E) None of the above

21. The first time you are going to operate an unfamiliar high-temperature tube furnace (or a high-pressure autoclave), what would you do?
(甲) Just follow what senior lab members told me—after doing it once, I'll know how.
(乙) Read the SOP/manual first and confirm the safety limits (temperature, heating/cooling rate, atmosphere, pressure).
(丙) Perform a dummy run (blank run) to check that the temperature control and gas flow are functioning properly.
(丁) Set all parameters to the maximum to test the limits.
(戊) Verify ventilation, exhaust/effluent handling, emergency shutoff, and required personal protective equipment (PPE) in advance
(A) 乙丙戊
(B) 丙丁
(C) 甲丁戊
(D) 乙丁
(E) 甲乙丙丁戊

22. For a low-spin d⁴ case, it is expected to show a stronger Jahn-Teller effect than that of high-spin one.
(A) True
(B) NOT True
(C) the same
(D) No such thing called Jahn-Teller effect
(E) None of the above

23. Which of the following statements is correct?
(A) The concepts of labile/inert are thermodynamic concepts
(B) In octahedral complexes, weak field ligands in the spectrochemical series increase the Δo of the complexes.
(C) A metal with six d electrons in an octahedral configuration will be diamagnetic if high-spin.
(D) In the selection rules, transition between different spin multiplicities is forbidden
(E) All of the above

24. What is the formal name for [Cu(NH₃)₄]SO₄?
(A) tetraamminecopper(II) sulfide
(B) tetraamminecopper sulfide
(C) fouramminecopper (II) sulfide
(D) tetraamminecopper(II) sulfate
(E) None of the above

25. Which of the following theory models can explain that there are two lone pairs in a water molecule?
(A) Hard and Soft Acids and Bases
(B) Lewis structure model
(C) molecular orbital
(D) Le Chatelier's principle
(E) Ligand field theory

26. In a group meeting, you are asked a question that you do not know how to answer. What would you do?
(A) Talk your way out through bad chemicals.
(B) Be silent and wait until the meeting ends
(C) Change the subject
(D) Blame the instrument
(E) Admit that you do not know, explain how you would verify it or what additional experiments you would do, and report back next time with a careful data analysis.

27. As a new graduate student, you are about to begin a research project. Which of the following practices should you follow to get started?
(甲) Search and read the literature for one time
(乙) Keep searching and reading the literature all the time
(丙) The results and theory from the literature are always correct. I should not argue with them.
(丁) Always questioning the results published in scientific papers and in the literature
(戊) Before starting any experiment, form a logical expectation (hypothesis) for the outcome.
(A) 甲丁
(B) 乙丁戊
(C) 乙丁
(D) 丙戊
(E) None of the above

28. If a reaction suddenly cannot be repeated under your operation, what is your first step?
(A) Do other reactions or experiments, so my Professor will forget to ask me about it later
(B) Report to my professor, and he/she will tell me what to do next.
(C) Make a variable checklist (e.g., temperature, concentrations, solvent, reagent purity, atmosphere, stirring, equipment, and batch-to-batch differences), and then carefully check all the variables one after one until knowing what the problem is.
(D) Increase the temperature first to see whether it improves.
(E) None of the above

29. Which of the following statements regarding zeolite materials is incorrect?
(A) mainly octahedral frameworks
(B) mainly tetrahedral frameworks
(C) doping transition metals in the framework is possible
(D) selective catalysts for industry
(E) All of the above

30. What information is not provided by XPS (X-ray Photoelectron Spectroscopy) data?
(A) oxidation states
(B) binding energy
(C) chemical environments
(D) crystallinity
(E) All of the above

1. Explain why deuterated solvents are used in the sample preparation for measuring 1H NMR? (2%)

a)

b)

c)

d)

3. Draw a reasonable mechanism for the following transformation. (3%) 

4. Provide a stepwise synthesis (give reagents) for the following transformation. (3%)
 

5. Cubic close packing (ccp) and hexagonal close packing (hcp) are two common closest-packed structures. Explain the key differences between ccp and hcp. (4%)

a) Please determine whether the unknown crystalline sample is simple cubic, face-centered cubic (fcc), or body-centered cubic (bcc). Explain your reasons.

b) Please give the possible (hkl) of x, y, and z.

c) If a very weak peak appears at 2θ=30.5° (relative intensity 1%), how would you determine whether it arises from a second/impure phase, or it still corresponds to a single phase? (10%)

7. A molecular orbital diagram of a ML6 octahedral complex with sigma-donor and pi-acceptor interaction is shown below. Please fill out all the square blank fields (i - xx) with the proper irreducible representation. (6%)
Please give your answer with the corresponding label of the empty field.
Note: sigma-donor symmetry representation: A_1g, T_lu, E_g
pi-acceptor symmetry representation: T_1g, T_2g, T_lu, T_2u
The figure credit: adapted from 5th Ed. "Inorganic Chemistry" by Gary L. Miessler