<MultiModal>![The image depicts an organic tandem reaction: CC(C)C([H])=O>O=S(Cl)(Cl)=O>[*],[*]>O=S(O)(O)=O>[B],[B}>[C],[C]>[D].](/media/uploads/673fcf7b-aaf2-4294-a513-7a1f343a9795.png)</MultiModal>

Known information about the reaction in the image:
1. **A** contains a carbonyl group.  
2. Reaction conditions for **B** to **C**: (a) $\mathrm{NaOH, 185\degree C}$; (b) $\mathrm{t-BuOK, 75\degree C}$.  
3. Reaction conditions for **C** to **D**: (c) $\mathrm{O_3, DCM, MeOH, -78\degree C}$; (d) $\mathrm{O_3, DCM, -78\degree C; then~ Me_2S}$.  
4. $\mathrm{1 ~mol}$ of **D** decomposes above $\mathrm{-40\degree C}$ to yield a single gaseous product, with a volume of approximately $\mathrm{74 ~L}$ at room temperature and atmospheric pressure, and a density of about $\mathrm{1.8 ~kg/m^3}$.  

Which of the following statements about the unknowns **A-D** is correct?
<MultiModal>![该图描述了一个有机串联反应：CC(C)C([H])=O>O=S(Cl)(Cl)=O>[*],[*]>O=S(O)(O)=O>[B],[B}>[C],[C]>[D].](/media/uploads/673fcf7b-aaf2-4294-a513-7a1f343a9795.png)</MultiModal>

关于上图的反应已知：
1. **A**具有羰基。
2. **B**到**C**可供选择的反应条件：（a) $\mathrm{NaOH, 185\degree C}$; (b) $\mathrm{t-BuOK, 75\degree C}$。
3. **C**到**D**可供选择的反应条件：(c)$\mathrm{O_3, DCM, MeOH,  -78\degree C}$; (d)$\mathrm{O_3, DCM, -78\degree C; then~ Me_2S}$。
4. $\mathrm{1 ~mol}$ **D**在$\mathrm{-40\degree C}$以上分解生成的唯一产物是一种气体，在室温大气压下体积约为$\mathrm{74 ~L}$，密度约为$\mathrm{1.8 ~kg/m^3}$。

下列关于未知物**A-D**说法正确的是：
**A** is acidic
**C** The average molecular weight of the completely hydrolyzed product does not exceed 85.
There are two chemical environments for hydrogen atoms in **D**.
To achieve a higher reaction yield for the conversion of **B** to **C**, reaction condition (a) should be selected.
In order to achieve a higher reaction yield for the generation of **D** from **C**, reaction condition (d) should be selected.
None of the above statements are correct
**A**具有酸性
**C**完全水解的产物的平均分子量不超过85。
**D**的氢原子化学环境有两种
为使得**B**生成**C**的反应产率更高，应选择反应条件(a)。
为使得**C**生成**D**的反应产率更高，应选择反应条件(d)。
以上说法均不正确
The substrate is an aldehyde. Since **A** contains a carbonyl group, the aldehyde functional group should be retained. Thionyl chloride serves as the chlorinating reagent, leading to α-halogenation of the aldehyde, and the product is CC(C)(Cl)C([H])=O. This compound lacks α-hydrogens, and the aldehyde hydrogen is difficult to dissociate, rendering it essentially non-acidic. Option A is incorrect.  

<Checkpoint>[α-Halogenation of the aldehyde occurs](1)</Checkpoint>  

<Checkpoint>[**A** is CC(C)(Cl)C([H])=O](1)</Checkpoint>  

The reaction from **A** to **B** is relatively difficult to deduce, so we start with the decomposition of **D**. Based on the fact that **D** decomposes to produce only one gas, and using the ideal gas law, the properties of the gas can be determined:  

$\mathrm{n=pV/RT=3.03 ~mol}$  

$\mathrm{M=\rho V_m=44.01}$  

This indicates that the gas is carbon dioxide, and $\mathrm{3~mol}$ is produced. Therefore, the chemical formula of **D** is inferred to be $\mathrm{C_3O_6}$, and its structure can only be O=C(OC(O1)=O)OC1=O. This structure contains no hydrogen atoms, so option C is incorrect.  

<Checkpoint>[**D** decomposes to produce only carbon dioxide, generating $\mathrm{3~mol}$](1)</Checkpoint>  

<Checkpoint>[The chemical formula of **D** is $\mathrm{C_3O_6}$, and its structure can only be O=C(OC(O1)=O)OC1=O](1)</Checkpoint>  

The conversion of **C** to **D** is clearly an ozonolysis reaction of a double bond, where the double bond cleaves to form carbonyl groups. Thus, the structure of **C** can be deduced as C/C(C)=C(O/C(O/1)=C(C)\C)/OC1=C(C)/C. Complete hydrolysis of this structure yields only CC(C(O)=O)C, with a molecular weight of 88, so option B is incorrect.  

<Checkpoint>[The structure of **C** is C/C(C)=C(O/C(O/1)=C(C)\C)/OC1=C(C)/C](1)</Checkpoint>  

<Checkpoint>[Hydrolysis of **C** yields only CC(C(O)=O)C](1)</Checkpoint>  

The conversion of **B** to **C** occurs under strong base conditions. Based on the double-bond structure of **C**, this is likely an elimination reaction. Combining this with the structure of **A**, it can be inferred that the conversion of **A** to **B** is a trimerization reaction. Under acidic conditions, the carbonyl group is protonated and then attacked by another carbonyl molecule, leading to trimerization. Thus, **B** is CC(C)(Cl)C1OC(C(C)(Cl)C)OC(C(C)(Cl)C)O1.  

<Checkpoint>[**B** is CC(C)(Cl)C1OC(C(C)(Cl)C)OC(C(C)(Cl)C)O1](1)</Checkpoint>  

The conversion of **B** to **C** is an elimination reaction. However, under high-temperature, strongly basic conditions, hydroxide ions act as strong nucleophiles, making the six-membered ring prone to hydrolysis. Therefore, using a less nucleophilic base like potassium tert-butoxide results in higher yields, so option D is incorrect.  

<Checkpoint>[The conversion of **B** to **C** is an elimination reaction; using a less nucleophilic base like potassium tert-butoxide yields higher efficiency](1)</Checkpoint>  

The conversion of **C** to **D** involves ozonolysis of the double bond. If dimethyl sulfide is used to treat the resulting ozonide intermediate, the strong nucleophilicity of the sulfide may open the six-membered ring. Hence, reaction condition (c) is preferable, so option E is incorrect.  

<Checkpoint>[The conversion of **C** to **D** is an ozonolysis reaction; the strong nucleophilicity of the sulfide may open the six-membered ring](1)</Checkpoint>  

In conclusion, options A-E are all incorrect, and option F is correct.
底物为醛，由于**A**存在羰基，所以醛基官能团应当得以保留；硫酰氯为氯化试剂，从而应当发生醛的α-卤代，产物为CC(C)(Cl)C([H])=O。该化合物无α-氢，醛氢难以解离，基本无酸性，选项A错误。

<Checkpoint>[发生醛的α-卤代](1)</Checkpoint>

<Checkpoint>[**A**为CC(C)(Cl)C([H])=O](1)</Checkpoint>

从**A**生成**B**的反应比较难以推断，先从**D**分解的反应入手；根据**D**分解生成唯一气体，以及理想气体状态方程可知分解的气体性质：

$\mathrm{n=pV/RT=3.03 ~mol}$

$\mathrm{M=\rho V_m=44.01}$

可以判断该气体为二氧化碳，且生成了$\mathrm{3~mol}$；因此推断**D**的化学式为$\mathrm{C_3O_6}$，结构只能为O=C(OC(O1)=O)OC1=O；该结构无氢原子，选项C错误。

<Checkpoint>[**D**分解生成唯一气体为二氧化碳，且生成了$\mathrm{3~mol}$](1)</Checkpoint>

<Checkpoint>[**D**的化学式为$\mathrm{C_3O_6}$，结构只能为O=C(OC(O1)=O)OC1=O](1)</Checkpoint>

**C**生成**D**很明显为双键的臭氧化反应，双键断裂生成羰基，从而倒退**C**的结构为C/C(C)=C(O/C(O/1)=C(C)\C)/OC1=C(C)/C。该结构完全水解只生成CC(C(O)=O)C，分子量为88，选项B错误。

<Checkpoint>[**C**的结构为C/C(C)=C(O/C(O/1)=C(C)\C)/OC1=C(C)/C](1)</Checkpoint>

<Checkpoint>[**C**水解只生成CC(C(O)=O)C](1)</Checkpoint>

**B**生成**C**为强碱条件，根据**C**的双键结构很可能为消除反应；从而结合**A**的结构可以发现**A**生成**B**为三聚反应，酸性条件下羰基被质子化后被另一分子羰基进攻发生三聚，从而**B**为CC(C)(Cl)C1OC(C(C)(Cl)C)OC(C(C)(Cl)C)O1。

<Checkpoint>[**B**为CC(C)(Cl)C1OC(C(C)(Cl)C)OC(C(C)(Cl)C)O1](1)</Checkpoint>

**B**生成**C**为消除反应，但高温强碱环境下，氢氧根作为强亲核基团，六元环结构容易水解，并且高温条件下不利于多聚体生成。因此选择亲核能力差的叔丁醇钾作为碱产率更高，选项D错误。

<Checkpoint>[**B**生成**C**为消除反应，选择亲核能力差的叔丁醇钾作为碱产率更高](1)</Checkpoint>

**C**生成**D**为双键的臭氧化反应，如果利用二甲基硫醚处理生成的臭氧化物中间体，会导致还原产生的氧负离子使六元环开环分解，从而反应条件(c)更好，选项E错误。

<Checkpoint>[**C**生成**D**为双键的臭氧化反应，可能因为硫醚的强亲核性使六元环开环](1)</Checkpoint>

综上，选项A-E均错误，选项F正确。