The following organic structures are provided, with some hydrogen atoms labeled.

<MultiModal>![The figure shows 4 compounds, which are 1: [H:b][C@@H]1C2=CC=CC=C1C=CC=C2[H:a]; 2: [H:c]C1=C(Br)/C=C\C#C/C=C\C#C\C=C/1; 3: [H:d]C1=C/C=C/C=C\C=C\C=C\C=C/C=C/C=C/C=C/1; 4: [H:e]C1=CC=CC2C1C=CC=C2, where [H:a-e] are the five hydrogen atoms whose 1H NMR chemical shifts are to be sorted](/media/uploads/99641398-6130-4469-a050-16d593aadba7.png)</MultiModal>

Please compare the chemical shifts ($\mathrm{ppm}$) of these hydrogen atoms in the nuclear magnetic resonance hydrogen spectrum and sort them in descending order of their relative values a~e.
现有以下有机物结构，其中标出了一些氢原子。

<MultiModal>![图中有4个化合物，分别为1: `[H:b][C@@H]1C2=CC=CC=C1C=CC=C2[H:a]`；2: `[H:c]C1=C(Br)/C=C\C#C/C=C\C#C\C=C/1`；3: `[H:d]C1=C/C=C/C=C\C=C\C=C\C=C/C=C/C=C/C=C/1`; 4: `[H:e]C1=CC=CC2C1C=CC=C2`，其中[H:a-e]分别为待排序氢谱化学位移的五个氢原子](/media/uploads/99641398-6130-4469-a050-16d593aadba7.png)</MultiModal>

请比较这些氢原子的在核磁共振氢谱中的化学位移 ($\mathrm{ppm}$) ，按其相对值由大到小进行排序 a~e。
All other options are incorrect
c > a > b > e > d
c > e > a > b > d
c > a > e > b > d
a > c > e > b > d
a > e > c > b > d
e > c > a > b > d
c > a > b > d > e
c > e > b > a > d
b > c > a > e > d
e > a > c > b > d
c > b > a > e > d
a > c > b > e > d
b > a > c > e > d
e > c > b > d > a
其他选项均不正确
c > a > b > e > d
c > e > a > b > d
c > a > e > b > d
a > c > e > b > d
a > e > c > b > d
e > c > a > b > d
c > a > b > d > e
c > e > b > a > d
b > c > a > e > d
e > a > c > b > d
c > b > a > e > d
a > c > b > e > d
b > a > c > e > d
e > c > b > d > a
The compounds in the figure given in the question all have conjugated systems, so the chemical shifts of hydrogen in them are mainly affected by aromaticity.

<Checkpoint>[The chemical shifts of hydrogen are mainly affected by aromaticity](1)</Checkpoint>

For compound 1, this is a special bridged ring system with a conjugated system. The double bond conjugated system has $10\pi$ electrons and is aromatic. Due to the effect of the aromatic ring current, the hydrogen `[H:b]` on the bridgehead carbon is in the shielded region, and the chemical shift shifts to a higher field, generally less than $0$. It is less affected by the shielding effect and is around $0\sim -1\mathrm{~ppm}$; while `[H:a]` is in the deshielded region, and the chemical shift shifts to a lower field, generally around $7\sim 8\mathrm{~ppm}$.

<Checkpoint>[`[H:b]` is in the shielded region of the aromatic ring, and the chemical shift is $0\sim -1\mathrm{~ppm}$](1)</Checkpoint>

<Checkpoint>[`[H:a]` is in the deshielded region of the aromatic ring, and the chemical shift is about $7\sim 8\mathrm{~ppm}$](1)</Checkpoint>

For compound 2, it is a ring system composed of carbon-carbon double and triple bonds. Due to the steric configuration limitations of the double and triple bonds, there must be coplanar $\pi$ bonds. For this $\pi$ bond, it is an antiaromatic system of $12\pi$, so `[H:c]` inside the ring is in the deshielded region of the antiaromatic ring, and the deshielding effect of the antiaromatic ring is stronger. Therefore, the chemical shift of `[H:c]` is greater than $10\mathrm{~ppm}$.

<Checkpoint>[`[H:c]` is in the deshielded region of the antiaromatic ring, and the chemical shift of `[H:c]` is greater than $10\mathrm{~ppm}$](1)</Checkpoint>

For compound 3, this is a typical aromatic 18-annulene structure, in which `[H:d]` inside the ring is subject to the strong shielding effect of the aromatic ring current, and the chemical shift moves to a higher field. Its value is less than the chemical shift of `[H:b]`, approximately around $-3\mathrm{~ppm}$.

<Checkpoint>[`[H:d]` is subject to the strong shielding effect of the aromatic ring current, the chemical shift is less than `[H:b]`, around $-3\mathrm{~ppm}$](1)</Checkpoint>

For compound 4, it is 9,10-dihydronaphthalene, which has two conjugated diene systems and is not aromatic. The chemical shift of `[H:e]` is the shift of hydrogen on the carbon of the conjugated diene, approximately $5.5\sim 6.5\mathrm{~ppm}$.

<Checkpoint>[Since there is no aromaticity, the chemical shift of `[H:e]` is about $5.5\sim 6.5\mathrm{~ppm}$](1)</Checkpoint>

Finally, the relative values of the chemical shifts are sorted from largest to smallest as c > a > e > b > d.

<Checkpoint>[The relative values of the chemical shifts are sorted from largest to smallest as c > a > e > b > d](1)</Checkpoint>

Select option D.
题目所给图的化合物均具有共轭体系，因此其中氢的化学位移主要受芳香性的影响。 

<Checkpoint>[氢的化学位移主要受芳香性的影响](1)</Checkpoint>

对于化合物 1 而言，这是一个特殊的桥环体系的共轭系统，双键共轭体系中有 $10\pi$ 电子，具有芳香性，由于芳香环电流的影响，桥头碳上的氢 `[H:b]` 在屏蔽区，化学位移向高场偏移，一般而言小于 $0$，其受屏蔽效应影响较小，在 $0\sim -1\mathrm{~ppm}$ 附近；而 `[H:a]` 在去屏蔽区，化学位移向低场偏移，一般而言在 $7\sim 8\mathrm{~ppm}$ 左右。

<Checkpoint>[`[H:b]` 在芳环的屏蔽区，化学位移为 $0\sim -1\mathrm{~ppm}$](1)</Checkpoint>

<Checkpoint>[`[H:a]` 在芳环的去屏蔽区，化学位移约为 $7\sim 8\mathrm{~ppm}$](1)</Checkpoint>

对于化合物 2 而言，是由碳碳双键和三键构成的环系，由于双键、三键的立体构型限制，一定存在共平面的 $\pi$ 键，而对于这个 $\pi$ 键而言，为 $12\pi$ 的反芳香性体系，因此，在环内部的 `[H:c]` 处于反芳香环的去屏蔽区，且反芳香环的去屏蔽效应更强，因此 `[H:c]` 的化学位移大于 $10\mathrm{~ppm}$。

<Checkpoint>[`[H:c]` 处于反芳香环的去屏蔽区，`[H:c]` 的化学位移大于 $10\mathrm{~ppm}$](1)</Checkpoint>

对于化合物 3 而言，这是一个典型的芳香性 18-轮烯的结构，其环内部的 `[H:d]` 受到强的芳香环电流的屏蔽效应，化学位移向高场移动，其值小于 `[H:b]` 的化学位移，大约为 $-3\mathrm{~ppm}$ 附近。

<Checkpoint>[`[H:d]` 受到强的芳香环电流的屏蔽效应，化学位移小于 `[H:b]`，在 $-3\mathrm{~ppm}$ 附近](1)</Checkpoint>

对于化合物 4 而言，其为 9,10-二氢化萘，有两个共轭二烯体系，无芳香性，`[H:e]` 化学位移为共轭二烯烃碳上的氢的位移，大约为 $5.5\sim 6.5\mathrm{~ppm}$。

<Checkpoint>[由于没有芳香性，`[H:e]` 化学位移约为 $5.5\sim 6.5\mathrm{~ppm}$](1)</Checkpoint>

最终，得到化学位移相对值由大到小进行排序为 c > a > e > b > d。

<Checkpoint>[化学位移相对值由大到小进行排序为 c > a > e > b > d](1)</Checkpoint>

选择选项 D。