2.1.1 Microwave Irradiation

Microwave irradiation has emerged as a powerful technique for promoting chemical reactions.
微波辐射已成为促进化学反应的一种强效技术。
Microwaves are electromagnetic radiation ranging from 0.3 to 300 GHz, absorbed by materials that exhibit dipolar polarization or ionic conduction.
微波是一种频率范围在 0.3 至 300 GHz 的电磁辐射，可被具有偶极极化或离子传导特性的材料吸收。
The impact of microwave irradiation on chemical reactions arises from a combination of thermal and non-thermal effects.
微波辐射对化学反应的影响源于热效应与非热效应的共同作用。
The former effects primarily stem from dipolar and interfacial polarization, although conduction losses can also become significant at elevated temperatures.
前者的影响主要源于偶极极化和界面极化，尽管在高温下传导损耗也可能变得显著。
When a molecule is exposed to microwaves, it rotates to align with the applied field, resulting in continuous attempts to realign with changing fields, leading to energy absorption.
当分子暴露在微波中时，它会旋转以与施加的电场对齐，从而不断尝试与变化的电场重新对齐，导致能量吸收。
The latter effects may primarily arise from an increased probability of molecular collisions, a reduction in activation energy, and the occurrence of localized hot spots.
后者的效应可能主要源于分子碰撞概率的增加、活化能的降低以及局部热点现象的出现。
Microwaves improve synthetic processes by accelerating reaction rates, thereby reducing reaction times.
微波通过加速反应速率改善合成过程，从而缩短反应时间。
Additionally, they enable working with reduced quantities of solvent or even in solvent-free conditions.
此外，它们还能在减少溶剂用量甚至无溶剂条件下进行反应。
Furthermore, microwaves can enhance the selectivity of a synthetic process by favoring desired reactions over potential collateral processes.^{39, 40} This approach is by far the most represented green synthetic method in literature for the synthesis of phthalocyanines.
此外，微波能通过促进目标反应而非潜在的副反应，从而提高合成过程的选择性。 ^{39, 40} 迄今为止，这种方法在文献中报道的酞菁合成绿色方法中占据主导地位。
Microwave-assisted synthesis has successfully provided macrocycles functionalized with halides,^41-44 terminal alkynes,⁴⁵ crown ethers,⁴⁶ substituted phenoxy^47-49 and 1-naphthyloxy⁵⁰ groups, tetraaza,⁵¹ tetraoxamonoaza,⁵² tetrathiacyclohexadecane,⁵³ dithiadiazadioxa,⁵⁴ diazadithio⁵⁵ and tetrathiadiaza rings,^{56, 57} thiazoles,⁵⁸ functionalized triazoles,^59-62 phenylthioethanol,⁶³ monoterpenes like (1R)-(−) myrtenol and (1R,2S,5R)-(−)-menthol,⁶⁴ benzenesulfonamide,⁶⁵ pyridine⁶⁶ and azo compounds.⁶⁷ Microwaves have been also employed to synthesize silicon⁶⁸ lanthanide(III),⁶⁹ lead,^{49, 70} and platinum⁷¹ derivatives, and phthalocyanine-based polymers.^72-74 Kantar et al.
微波辅助合成已成功制备出多种功能化大环化合物，包括卤化物 ^41-44 、末端炔烃 ⁴⁵ 、冠醚 ⁴⁶ 、取代苯氧基 ^47-49 与 1-萘氧基 ⁵⁰ 基团、四氮杂 ⁵¹ 、四氧单氮杂 ⁵² 、四硫杂环十六烷 ⁵³ 、二硫二氮二氧杂 ⁵⁴ 、二氮二硫 ⁵⁵ 及四硫二氮杂环 ^{56, 57} 、噻唑 ⁵⁸ 、功能化三唑 ^59-62 、苯硫基乙醇 ⁶³ 、单萜类如(1R)-(−)桃金娘烯醇与(1R,2S,5R)-(−)-薄荷醇 ⁶⁴ 、苯磺酰胺 ⁶⁵ 、吡啶 ⁶⁶ 以及偶氮化合物 ⁶⁷ 。该技术还应用于合成硅 ⁶⁸ 、镧系(III) ⁶⁹ 、铅 ^{49, 70} 、铂 ⁷¹ 等金属衍生物及酞菁基聚合物 ^72-74 。Kantar 等研究者
used the microwave-assisted approach for the tetramerization of phthalonitriles bearing different substituents at positions 4- and 5-.
采用微波辅助法对 4 位和 5 位带有不同取代基的邻苯二甲腈进行四聚反应。
They successfully synthesized tetra- and octa-substituted metal-free, zinc, and copper phthalocyanines and compared the alternative procedure with the standard solution-based method.⁷⁵ By exploiting the different reactivity of the two chlorine atoms of 4,5 dichlorophthalonitrile when one of them is subjected to nucleophilic aromatic substitution (S_NAr), they synthesized two asymmetric precursors: 4-chloro-5-(3,5-dimethoxyphenoxy)phthalonitrile and 4-octanethio-5-(3,5-dimethoxyphenoxy)phthalonitrile.
他们成功合成了四取代和八取代的无金属酞菁、锌酞菁及铜酞菁，并将该替代方案与标准溶液法进行了对比。通过利用 4,5-二氯邻苯二甲腈中两个氯原子在亲核芳香取代反应（S_NAr）中的差异性反应活性，研究者制备出两种不对称前驱体：4-氯-5-(3,5-二甲氧基苯氧基)邻苯二甲腈和 4-辛硫基-5-(3,5-二甲氧基苯氧基)邻苯二甲腈。
Subsequently, these precursors reacted in DBU or DMAE for 8 minutes at a power of 350 W using microwave irradiation to provide MW1 and MW2 derivatives.
随后，这些前体在 DBU 或 DMAE 中通过 350 瓦功率的微波辐射反应 8 分钟，得到 MW1 和 MW2 衍生物。
In all cases investigated, the yields were at least 75 %, surpassing those of the corresponding standard procedures conducted for comparison.
在所有研究案例中，产率均不低于 75%，优于用于对比的相应标准流程所得结果。
DMAE was chosen as the reaction solvent for the synthesis of the polyfluorinated zinc phthalocyanine MW3,⁴⁴ which was subsequently grafted onto a suitably functionalized silica.
选择 DMAE 作为反应溶剂用于合成多氟化锌酞菁 MW3，随后将其接枝到适当功能化的二氧化硅上。
The resulting inorganic–organic hybrid material was used as a catalyst for the solvent-free synthesis of biologically important 1,5-benzodiazepines, and proved to be recoverable and reutilized.
所得无机-有机杂化材料被用作无溶剂合成具有重要生物活性的 1,5-苯并二氮杂䓬类化合物的催化剂，并证实其具备可回收再利用特性。
The use of the MW3-based catalyst in solvent-free reaction conditions at room temperature, led to an improvement in conversions with respect to control experiments.
在室温无溶剂反应条件下使用 MW3 基催化剂，相较于对照实验提高了转化率。
The environmentally friendly synthesis of its precursor adds significant value, further advancing the target application towards greater sustainability.
其前体的环保合成工艺显著提升了价值，进一步推动目标应用向更高可持续性发展。

Acetynyl-substituted zinc phthalocyanines have been synthesized by Koyun et al.
Koyun 等人成功合成了乙炔基取代的锌酞菁化合物。
in a similar way.⁴⁵ By irradiating the precursors in n-pentanol at 360 W, yields up to 86 % for MW4 and 81 % for MW5 were obtained.
以类似方式。 ⁴⁵ 通过在正戊醇中以 360 瓦功率辐照前驱体，MW4 的产率可达 86%，MW5 的产率达 81%。
The MW-based approach outperformed the conventional one (79 % and 74 % yields for MW4 and MW5 respectively) and reduced the reaction time from 6 hours to 15 minutes.
微波法优于传统方法（MW4 和 MW5 的产率分别为 79%和 74%），并将反应时间从 6 小时缩短至 15 分钟。
Remarkably, the synthetic approach was efficient in providing the target products without needing to protect the terminal acetynyl functional group.
值得注意的是，该合成方法无需保护末端乙炔基官能团即可高效获得目标产物。
Chiral monoterpene derivatives (MW6 and MW7) have been recently synthesized by Gonzalez et al.⁶⁴ yielded the desired phthalocyanines with comparable yields to the conventional procedure.
手性单萜衍生物（MW6 和 MW7）最近由 Gonzalez 等人合成， ⁶⁴ 以与传统方法相当的产率获得了目标酞菁化合物。
The copper derivatives exhibited slightly higher yields than the zinc derivatives.
铜衍生物的产率略高于锌衍生物。
Notably, a significant reduction in reaction time from seven hours to one hour was observed.
值得注意的是，反应时间从七小时显著缩短至一小时。
Taking advantage of the local generation of large amounts of energy, microwaves can be exploited to obtain products that would not be synthesized using conventional methods.
利用局部产生的大量能量，微波可被用于获取那些通过传统方法无法合成的产物。
Makhseed et al.
succeeded in obtaining hexadeca(2,6-dimethylphenoxy)phthalocyanines⁷⁶ (MW8) in a 9 % yield by reacting 3,4,5,6-tetrakis(2,6-dimethylphenoxy)phthalonitrile in the presence of hydroquinone in hexanol at 350 W for 10 minutes.
通过将 3,4,5,6-四(2,6-二甲基苯氧基)邻苯二甲腈与氢醌在己醇中于 350 瓦功率下反应 10 分钟，成功以 9%的收率制得十六(2,6-二甲基苯氧基)酞菁 ⁷⁶ （MW8）。
Microwaves irradiation mitigated the decrease in reactivity of the cyano groups due to the steric hinderance and electron-donating nature of the bulky 2,6-dimethylphenoxy substituents.
微波辐射减轻了氰基反应活性的下降，这是由于体积庞大的 2,6-二甲基苯氧基取代基的空间位阻和给电子性质所致。
The related metallated derivatives were obtained in 18 %–24 % yields by adding the desired salt to the mixture.
通过向混合物中添加所需盐类，相关金属化衍生物的产率为 18%至 24%。
On the contrary, attempts using the lithium pentoxide/pentanol system to obtain the free-base or metal ion-template reactions in hexanol led to inseparable mixtures of byproducts with an overall very low yield.
相反，尝试使用五氧化二锂/戊醇体系在己醇中进行游离碱或金属离子模板反应时，生成了难以分离的副产物混合物，且总产率极低。
Several solvent-free procedures have also been reported.
此外，也有报道称存在若干无溶剂合成方法。
Sharma et al.  Sharma 等人
straightforwardly synthesized 2,9,16,23-tetrachlorophthalocyanines MW9 starting from the cheap sodium 2-carboxy-4-chlorobenzoate and a suitable anhydrous metal salt (CoCl₂, CuCl₂, NiCl₂, ZnCl₂) in presence of urea as the source of nitrogen.⁴² The reported yields are generally high (75–92 %).
以廉价的 2-羧基-4-氯苯甲酸钠和适宜的无水金属盐（CoCl ₂ 、CuCl ₂ 、NiCl ₂ 、ZnCl ₂ ）为原料，在尿素作为氮源的条件下，直接合成了 2,9,16,23-四氯酞菁 MW9。 ⁴² 文献报道的产率普遍较高（75-92%）。
The absence of a proper solvent enhanced the interaction between microwaves and reactants and drove the chemical reaction toward completion.
缺乏适当溶剂增强了微波与反应物之间的相互作用，促使化学反应趋于完全。
Moiseeva et al.
succeeded in synthesizing 1.9 grams of 2(3),9(10),16(17),23(24)-tetraiodophthalocyanine MW10 in a single batch by irradiating a mixture of 4-iodophthalonitrile and Zn(quinoline)₂Cl₂ salt in a microwave reactor at 150 W for 7 minutes.⁴³ The authors achieved a high 83 % yield at analytical grade (≥98 %) purity.
通过微波反应器在 150 瓦功率下辐照 4-碘代邻苯二甲腈与 Zn(喹啉) ₂ Cl ₂ 盐混合物 7 分钟，成功单批次合成了 1.9 克 2(3),9(10),16(17),23(24)-四碘代酞菁 MW10。作者实现了分析纯级(≥98%)纯度下 83%的高产率。
This result is promising as this molecule is a versatile intermediate, whose iodide atoms can be widely substituted by exploiting the rich palladium-catalyzed chemistry to provide functionalized derivatives with high complexity.
这一结果颇具前景，因为该分子是一种多功能中间体，其碘原子可通过丰富的钯催化化学反应被广泛取代，从而制备出具有高度复杂性的功能化衍生物。
Furthermore, it is interesting to report here the synthesis of the MW11 cobalt derivative starting from 1,2,4-benzene tricarboxylic anhydride, urea, cobalt chloride and (NH₄)₂MoO₄, carried out on a total of approximately 100 grams of reagents.
此外，值得在此报告的是以 1,2,4-苯三甲酸酐、尿素、氯化钴和钼酸铵为原料，通过总计约 100 克反应物合成 MW11 钴衍生物的实验过程。
The authors report a very high yield, equal to 90 %, validating the use of microwaves even on large quantities, although still on a laboratory scale.⁷⁷ Solventless microwave-assisted syntheses have been reported also for unsubstituted Cu(II), Mn(II), Al(III), Co(II) and Zn(II) Pcs,⁷⁸ and for nitro- and poli chlorinated-derivatives.^{79, 80} Lead phthalocyanine and lead 2(3),9(10),16(17),23(24)tetra-nitrophthalocyanine were obtained in 90–92 % yields by reacting phthalonitriles and lead oxide in a domestic microwave oven for 13–15 minutes with a range of power irradiation.⁷⁰ The method was applied to batches of reagents up to approximately six grams. Comparison reactions carried out in molten phthalonitrile at 140–180 °C for 1–4 hours consistently resulted in lower overall yields.
作者报道了高达 90%的产率，验证了微波技术即使在大规模（尽管仍属实验室规模）应用中的有效性。 ⁷⁷ 无溶剂微波辅助合成法同样适用于未取代的铜(II)、锰(II)、铝(III)、钴(II)和锌(II)酞菁化合物 ⁷⁸ ，以及硝基与多氯代衍生物。 ^{79, 80} 通过在家用微波炉中以不同功率辐照 13-15 分钟，使邻苯二甲腈与氧化铅反应，可获得酞菁铅和 2(3),9(10),16(17),23(24)-四硝基酞菁铅，产率达 90-92%。 ⁷⁰ 该方法适用于单批约六克试剂的反应。对比实验显示，在 140-180°C 熔融邻苯二甲腈中反应 1-4 小时，总体产率始终较低。
On the contrary, more complex lead derivatives (MW12, MW13) synthesized in pentanol using DBU as base provided lower yields, ranging between 19 and 46 %.⁴⁹ Although a direct comparison of such different synthetic procedures is inappropriate, it is possible that the absence of solvent may be particularly advantageous for the synthesis of this family of metallophthalocyanines.
相反，在戊醇中使用 DBU 作为碱合成的更复杂铅衍生物（MW12、MW13）产率较低，介于 19%至 46%之间。虽然直接比较这些不同的合成方法并不合适，但无溶剂条件可能特别有利于这类金属酞菁化合物的合成。
Alternatively, pentanol may not be the most suitable choice as a reaction medium in this particular case.
或者，戊醇可能并非此特定情况下最适宜的反应介质选择。
The chemical structures of the phthalocyanines discussed in this paragraph are gathered in Figure 2.
本段讨论的酞菁类化合物的化学结构汇总于图 2 中。

2.1.2 UV Irradiation

Photochemical substrate activation with UV irradiation frequently occurs without the need for additional reagents, leading to reduced formation of byproducts.
紫外光照射下的光化学底物活化通常无需额外试剂即可发生，从而减少副产物的生成。
This feature makes photochemical reactions particularly attracting within the framework of green chemistry.
这一特性使得光化学反应在绿色化学框架下显得尤为引人注目。
Moreover, certain reactions can be carried out using visible light or sunlight as a renewable energy source, further enhancing their environmental appeal.
此外，某些反应可以利用可见光或阳光作为可再生能源进行，从而进一步提升其环保吸引力。
The study of UV light to assist the synthesis of phthalocyanines dates to 1976, when Tomoda et al.
利用紫外光辅助合成酞菁的研究可追溯至 1976 年，当时 Tomoda 等人。
observed that room light could positively affect the formation of phthalocyanines, and that UV irradiation could promote it even at room temperature.⁸¹ Kharisov et al.^{31, 82} then studied the effect of solvent on the synthesis of metal-free phthalocyanine (PcH₂) in the temperature range 0–60 °C choosing different linear, branched, and cyclic alcohols, as well as in ethylene glycol and dimethylaminoethanol (DMAE) as reaction media.
研究发现，室内光线能促进酞菁化合物的形成，而紫外线照射甚至在室温条件下也能加速这一过程。 ⁸¹ 随后 Kharisov 等人 ^{31, 82} 以不同直链、支链和环状醇类，以及乙二醇和二甲基氨基乙醇（DMAE）作为反应介质，在 0-60℃温度范围内研究了溶剂对无金属酞菁（PcH ₂ ）合成的影响。
Under the best experimental conditions, using the Ethanol/CH₃ONa and Methanol/CH₃ONa systems could produce quantitative yields in the 30–60 °C temperature range.
在最佳实验条件下，使用乙醇/CH ₃ ONa 和甲醇/CH ₃ ONa 体系可在 30-60℃温度范围内实现定量产率。
The rationalization of this evidence involves the formation of free RO^⋅ radicals upon irradiation with UV light, which increases the effectiveness of nucleophilic attacks on the cyano group of phthalonitrile.
这一现象的解释涉及紫外线照射下形成游离 RO 自由基的过程，该过程增强了亲核试剂对邻苯二甲腈氰基的攻击效率。

Experimental evidence suggests that the presence of more than one hydroxy group in solvents, such as in ethylene glycol and glycerol, can enhance yields and enable reaction temperatures to be lowered, even to near-zero degrees.
实验证据表明，在溶剂中存在多个羟基（如乙二醇和甘油中）可提高产率，并能使反应温度降低，甚至接近零度。
However, it is important to note that the authors report difficulties in precisely calculating these effects due to the high viscosity of these solvents, that made the isolation of the product from the reaction mixture challenging.
然而，需要指出的是，作者报告称由于这些溶剂的高粘度，精确计算这些效应存在困难，这使得从反应混合物中分离产物具有挑战性。
Therefore, while this evidence is promising, it should be considered probable rather than fully verified.
因此，尽管这一证据前景看好，但仍应视为可能而非完全确证。
In 2010, Youssef reported the UV-assisted synthesis of metal-free 2,3,9,10,16,17,23,24-octamethoxyphthalocyanine (UV1, Figure 3) in DMAE, as a precursor for more complex alkynyl substituted derivatives.⁶⁰ The yield obtained was 60 % starting from 3.5 g of phthalonitrile, a quantity still on a lab-scale, but significant in phthalocyanine synthesis, often carried out in quantities much lower than one gram.
2010 年，Youssef 报道了在 DMAE 溶剂中通过紫外辅助合成无金属 2,3,9,10,16,17,23,24-八甲氧基酞菁（UV1，图 3）的方法，该产物可作为合成更复杂炔基取代衍生物的前驱体。 ⁶⁰ 实验以 3.5 克邻苯二甲腈为起始原料，获得了 60%的收率——虽然仍属实验室规模，但在通常以低于 1 克量级进行的酞菁合成中，这一产量已颇具意义。
Instead, any attempt to synthesize the corresponding metallophthalocyanines in the same reaction conditions failed.
然而，在相同反应条件下尝试合成相应金属酞菁的所有努力均告失败。
Saito et al.
reported the first direct synthesis of Cu and Zn phthalocyanines in nanosized micelles irradiated with UV light.⁸³ The size of the micelles, that was found to be averagely 24.7 nm, allowed to control the morphology of target products, obtaining CuPc in α-form.
报道了首例在紫外光照射下纳米胶束中直接合成铜和锌酞菁的方法。研究发现平均尺寸为 24.7 纳米的胶束可调控目标产物的形貌，最终获得α晶型的铜酞菁。
The order in which the reagents are added was found to be crucial for the success of the reaction: adding CuCl₂ before the surfactants resulted in large aggregates caused by the formation of complexes between Cu²⁺ and isoindoline intermediates outside the micelles.
研究发现，试剂的添加顺序对反应成功至关重要：若在表面活性剂之前加入 CuCl ₂ ，会因 Cu ²⁺ 与胶束外异吲哚啉中间体形成复合物而导致大量聚集体的产生。
This approach was subsequently applied to the synthesis of unsubstituted crystalline naphthalocyanines and tetrapyridoporphyradine, thus demonstrating its potential versatility.⁸⁴
该方法随后被应用于未取代结晶萘酞菁和四吡啶并卟啉的合成，从而展示了其潜在的多功能性。 ⁸⁴

2.1.3 Ultrasounds

For over 80 years, sonochemistry, or ultrasound-driven chemical reactions, has captivated researchers as a powerful tool.
八十余年来，声化学（即超声波驱动的化学反应）作为一种强大工具始终令研究者着迷。
The effectiveness of ultrasound stems from cavitation, where bubbles form, expand, and violently collapse within a liquid.
超声波的有效性源于空化作用，即液体中气泡形成、膨胀并剧烈破裂的过程。
These collapsing bubbles generate intense, localized bursts of high pressure (up to 1,000 bar) and temperatures up to 5,000 K, initiating high-energy radical reactions.
这些坍塌的气泡会产生强烈的局部高压（高达 1000 巴）和高温（高达 5000K），从而引发高能自由基反应。
However, sonochemistry is more than just brute force; it also facilitates micro-mixing, ensuring thorough interaction between reaction components, and enhances mass transport, allowing materials to move more freely within the system.
然而，声化学不仅仅是蛮力作用；它还能促进微观混合，确保反应组分间的充分接触，并增强传质效率，使物质在体系中更自由地移动。
Additionally, it can reduce particle size, resulting in a larger surface area and faster reaction rates.
此外，它还能减小颗粒尺寸，从而增大表面积并加快反应速率。
Studies have shown that sonochemistry can significantly enhance reaction efficiency by accelerating rates, increasing yields, and influencing product selectivity in specific cases.
研究表明，声化学能通过加速反应速率、提高产率并在特定情况下影响产物选择性，从而显著提升反应效率。
This influence may even lead to the discovery of entirely new reaction pathways.
这种影响甚至可能促成全新反应路径的发现。
Several ultrasounds-assisted organic reactions have been reported, such as the synthesis of esters,⁸⁵ hydrolysis of nitriles,⁸⁶ nucleophilic aromatic substitutions⁶⁴ and preparation of metal-organic frameworks (MOFs).^{87, 88} The literature concerning this approach for the synthesis of phthalocyanines is scarce and notably dated.
已有数例超声辅助有机反应的报道，例如酯类合成、腈类水解、亲核芳香取代反应以及金属-有机框架材料（MOFs）的制备。而关于该方法应用于酞菁类化合物合成的文献则十分稀少，且明显陈旧。
There is evidence of ultrasound-assisted synthesis of PcH₂ at low temperature (0–40 °C) using zeolites of the clinoptilolite type as solid support.^{89, 90} Ultrasound accelerates the reaction by 2–3 times compared to control experiments conducted without it.
有证据表明，在低温（0-40°C）条件下，以斜发沸石型分子筛作为固体载体，通过超声辅助可合成 PcH ₂ 。 ^{89, 90} 与未使用超声的对照实验相比，超声使反应速度加快 2-3 倍。
The authors hypothesize that this acceleration is attributable to the improved generation of radical species and the continuous exposure of new active catalytic surfaces of the zeolites themselves.
作者推测这种加速效应源于自由基物种生成效率的提高以及沸石自身新活性催化表面的持续暴露。
Differences in reaction yields observed depending on the zeolite used were attributed to calcite impurities present in the composition of one of them, which are inert with respect to the phthalonitrile cyclization reaction.
观察到的反应产率差异归因于其中一种沸石成分中存在的方解石杂质，这些杂质对邻苯二甲腈环化反应呈惰性。
As a side note, ultrasonic treatments were reported to obtain lithium phthalocyanine nanotubes from micrometer-sized particles in water.⁹¹ Combinations of high frequency ultrasound and a surfactant like sodium dodecyl sulfate (SDS) reduced their size to diameters of tens of nanometers.
值得一提的是，有研究报道通过超声波处理可在水中将微米级颗粒转化为锂酞菁纳米管。 ⁹¹ 高频超声波与十二烷基硫酸钠（SDS）等表面活性剂的联合使用，可将其直径缩小至数十纳米。
Lastly, ultrasounds have found application in processes aimed at destroying the phthalocyanine aromatic ring in decolorization processes of industrial waste.^{92, 93}
最后，超声波技术已应用于工业废水脱色过程中破坏酞菁芳香环的工艺。

2.2.1 Benign Solvents

Zanotti et al.¹⁰⁰ tested anisole, glycerol, and their mixtures as solvents for the ring formation of unsubstituted and tetra-tert-butyl substituted cobalt, copper, and zinc phthalocyanines.
Zanotti 等人测试了苯甲醚、甘油及其混合物作为溶剂，用于未取代和四叔丁基取代的钴、铜、锌酞菁的环形成反应。
Anisole was chosen because of its low toxicity and biodegradability,^{96, 101} and because it can be obtained by renewable feedstocks like lignin and guaiacol.^102-104 Glycerol is a low-impact solvent that is already utilized in organic synthesis,¹⁰⁵ is available on a large scale from the vegetable oil industry and can solubilize both inorganic salts and a large variety of organic species.^{106, 107} (Figure 4).
选择苯甲醚是因为其低毒性和可生物降解性， ^{96, 101} 并且它可以从木质素和愈创木酚等可再生原料中获得。 ^102-104 甘油是一种低影响溶剂，已用于有机合成， ¹⁰⁵ 可从植物油工业大规模获取，并能溶解无机盐和多种有机物质。 ^{106, 107} （图 4）。
The formation of phthalocyanines in the various solvents and mixtures was found to be dependent on the nature of the templating metal.
研究发现，酞菁在不同溶剂及其混合物中的形成取决于模板金属的性质。

The trend Cu(II)>Co(II)>Zn(II) is in agreement with the greater templating power of copper compared to the other two ions Conversely, zinc was found to be the least reactive metal, due to its 3d¹⁰ shell.
铜(II)的活性趋势高于钴(II)和锌(II)，这与铜离子比其他两种离子具有更强的模板效应相符。相反，由于锌的 3d ¹⁰ 电子层结构，其反应活性最低。
Some exceptions were rationalized by analyzing the reaction environment and the interactions of the solvent with the reacting species.
通过分析反应环境及溶剂与反应物间的相互作用，这些例外情况得到了合理解释。
For example, the synthesis of CuPc in anisole using DMAE as the base had the lowest yield among all, probably because of the polar aprotic nature of the solvent that may have favored competitive copper-catalyzed reactions rather than templating the tetramerization of phthalonitrile.
例如，在苯甲醚中使用 DMAE 作为碱基合成 CuPc 的产率最低，这可能是由于溶剂的极性非质子特性更有利于铜催化竞争反应，而非促进邻苯二甲腈的四聚化模板效应。
Instead, the formation of CuPc in the same solvent when using potassium hydroxide as the base provided a yield as high as 76 %.
然而，当使用氢氧化钾作为碱基时，在相同溶剂中形成的铜酞菁产率高达 76%。
It is possible that the greater nucleophilicity of KOH compared to DBU in a relatively non-polar environment allowed an effective attack on the cyano groups of phthalonitrile, aided by the extreme coordinating capacity of copper, promoting the Pc ring formation among other processes.
在相对非极性的环境中，KOH 相比 DBU 具有更强的亲核性，加之铜极强的配位能力，可能使其能有效进攻邻苯二甲腈的氰基，从而促进酞菁环的形成及其他反应过程。
KOH has generally provided much lower yields for the other metal ions because of a side-reaction involving the hydration of nitrile groups in polar environments and subsequent formation of phthalimides.
对于其他金属离子，KOH 通常产率较低，这是由于在极性环境中发生了腈基水合的副反应，并随后生成了邻苯二甲酰亚胺。
Copper has been the best performing ion also in the synthesis of tetra-tert-butylphthalocyanines, yielding the desired product in all the screened conditions although in smaller amounts than the standard protocols.
在四叔丁基酞菁的合成中，铜离子同样表现出最佳性能，在所有筛选条件下都能获得目标产物，尽管产量低于标准方案。
This evidence highlights how the choice of an alternative reaction environment can depend on parameters such as the nature of one or more reagents, in a manner that is not always easily predictable.
这一证据凸显出替代反应环境的选择可能取决于一种或多种试剂的性质等参数，而这种关联性往往难以轻易预测。
Consequently, it can be challenging to develop a general procedure with a broad spectrum of applicability.
因此，要开发出一种具有广泛适用性的通用方法可能颇具挑战性。
As a follow up of this work, Podapangi, Mancini et al.³⁴ investigated a propane-1,2-diol/anisole mixture with DBU as the base for the synthesis of the same derivatives, obtaining yields close to those of standard conditions at least for the copper and zinc tetra-tert-butylphthalocyanines.
作为这项工作的后续研究，Podapangi、Mancini 等人 ³⁴ 采用丙烷-1,2-二醇/苯甲醚混合溶剂体系，以 DBU 作为碱基合成了相同衍生物，至少对于四叔丁基铜酞菁和四叔丁基锌酞菁而言，其产率接近标准条件下的水平。
In the literature, propane-1,2-diol has been utilized as a solvent or co-solvent in reactions involving ionic liquids.¹⁰⁸ An intriguing extension of this study, aimed at broadening the range of alternative reaction media, could involve solvents like polyethylene glycols (PEGs), which have already demonstrated success in the synthesis of organic materials with high added value.^{109, 110}
文献中，1,2-丙二醇已被用作离子液体反应中的溶剂或共溶剂。 ¹⁰⁸ 本研究的一个有趣延伸方向是探索聚乙二醇（PEGs）等替代反应介质，这类溶剂在高附加值有机材料合成中已展现出显著成效，这将有助于拓宽绿色反应介质的选择范围。 ^{109, 110}

2.2.2 Solvothermal Synthesis

Solvothermal synthesis is a method used to produce chemical compounds that involves placing a solvent containing reagents into an autoclave and subjecting it to high pressure and temperature.
溶剂热合成法是一种用于制备化合物的方法，其过程是将含有反应试剂的溶剂置于高压釜中，并施以高温高压条件。
Under these conditions, many substances dissolve more readily in the solvent compared to standard conditions.
在此条件下，相较于标准条件，许多物质更容易溶解于溶剂中。
This increased solubility enables reactions that might not occur under normal circumstances otherwise.
这种增加的溶解度使得在通常情况下可能不会发生的反应得以进行。
This approach is mostly applied to synthesize inorganic materials, while for the synthesis of phthalocyanines there have been limited successful attempts starting from several organic precursors, the first of which dates to 2008 and involves the use of harmful solvents like quinoline at temperatures >200 °C.¹¹¹ Over the past fifteen years, research efforts in solvothermal synthesis have mainly focused on identifying solvents with fewer environmental concerns.
该方法主要应用于无机材料的合成，而在酞菁类化合物的合成中，从多种有机前驱体出发的成功尝试较为有限，其中最早可追溯至 2008 年——该方案需在 200℃以上高温环境中使用喹啉等有害溶剂。 ¹¹¹ 过去十五年间，溶剂热合成领域的研究重点主要集中在寻找环境友好型溶剂。
This focus has resulted in the synthesis of phthalocyanines with diverse central metals and a restricted range of ring substituents.
这种关注导致了酞菁化合物的合成具有多样化的中心金属和有限的环取代基范围。
Notably, the products are often obtained as single crystals, rendering the solvothermal approach a valuable strategy for synthesizing highly organized materials.
值得注意的是，产物通常以单晶形式获得，这使得溶剂热法成为合成高度有序材料的一种重要策略。
These materials offer a platform for investigating fundamental and structural properties that would otherwise be inaccessible.
这些材料为研究原本无法触及的基础和结构特性提供了平台。
In 2015, Li et al.
2015 年，Li et al.
reported the synthesis of manganese phthalocyanine in ethanol at 190 °C for 3 hours.¹¹² Interestingly, both the synthesis and the purification steps do not require obnoxious solvents, since water is the only other chemical required to accomplish the task.
报道了在 190℃乙醇中反应 3 小时合成锰酞菁的方法。值得注意的是，该合成与纯化步骤均无需使用有害溶剂，仅需水作为辅助化学试剂即可完成。
The size of the crystals obtained is considerable, and in some cases exceeds 10 mm.
所得晶体尺寸相当可观，部分情况下甚至超过 10 毫米。
The resulting crystals were characterized by SEM measurements, which showed a well-defined quadrangular shape and different morphologies on the top/bottom planes.
通过扫描电子显微镜(SEM)表征显示，所得晶体呈现明确的四边形结构，且上下晶面具有不同形貌特征。
X-ray diffraction disclosed a monoclinic phase.
X 射线衍射显示为单斜晶相。
The same author successfully synthesized ZnPc and CoPc with a similar procedure, screening three different alcohols to individuate the best experimental conditions to maximize the length of the resulting crystals.¹¹³ Benzyl alcohol gave the best performances among the choices, providing ZnPc crystals up to 8 mm and CoPc up to 1 mm.
同一作者采用类似流程成功合成了锌酞菁(ZnPc)和钴酞菁(CoPc)，通过筛选三种不同醇类确定了最佳实验条件以最大化晶体生长尺寸。 ¹¹³ 在候选溶剂中，苯甲醇表现最优异，最终获得长达 8 毫米的 ZnPc 晶体和 1 毫米的 CoPc 晶体。
TEM images of ZnPc crystals obtained in different solvents provide interesting information, as their morphology significantly changes with the reaction media: benzyl alcohol gave quadrangular prisms with smooth surfaces along with some multilayer plates.
在不同溶剂中获得的酞菁锌晶体 TEM 图像提供了有趣的信息，其形貌随反应介质发生显著变化：苯甲醇溶剂中形成了表面光滑的四方棱柱体，同时伴随有多层板状结构生成。
1-pentanol provided rougher surfaces with nanosheet arrays intersecting on the exterior surface.
1-戊醇产生了更粗糙的表面，其外表面交错排列着纳米片阵列。
Ethanol-derived crystals displayed a quadrangular contour with additional secondary structures observed on their surface.
乙醇衍生的晶体呈现出四边形轮廓，其表面还观察到次级结构。
Conversely, the smoothest surface for CoPc was obtained with ethanol.
相反，使用乙醇可获得最光滑的 CoPc 表面。
This evidence suggests that the reaction media interactions with the reactants and the induced reactivity on the OH and cyano group, perhaps as well as the reaction temperature, play a crucial role in defining the morphology of the resulting products.
这一证据表明，反应介质与反应物的相互作用以及对羟基和氰基基团诱导的反应活性（可能还包括反应温度）在决定产物形貌方面起着关键作用。
The synthesis of a ZnPc hierarchical nanostructure with hollow interior space using ethylene glycol as a solvent has also been reported.¹¹⁴ More recently, the solvothermal synthesis of a metal-free Pc in non-harmful solvents was achieved.¹¹⁵ Since the reaction cannot take advantage of the templating effect of metal ions, DBU or 1,5-diazabicyclo-[4.3.0]-non-5-ene (DBN) were necessary to obtain the final product.
以乙二醇为溶剂合成具有中空内部结构的酞菁锌分级纳米结构已有报道。 ¹¹⁴ 最近，研究人员在无害溶剂中实现了无金属酞菁的溶剂热合成。 ¹¹⁵ 由于该反应无法利用金属离子的模板效应，必须使用 DBU 或 1,5-二氮杂双环[4.3.0]壬-5-烯（DBN）才能获得最终产物。
Additionally, ethanol emerged as the better solvent option.
此外，乙醇被证明是更优的溶剂选择。
The presence of a protic functional group on the solvent was found to be fundamental for the reaction to happen, attempts in pyridine, tetrahydrofuran, and acetonitrile failed in giving the phthalocyanine.
研究发现，溶剂中质子性官能团的存在是该反应发生的关键因素，在吡啶、四氢呋喃和乙腈中尝试合成酞菁均未成功。
Solvothermal synthesis has also been exploited to obtain rod-like iron phthalocyanine^{116, 117} and hierarchical tetranitrophthalocyanines with potential application in photocatalysis and for capacitive energy storage^{118, 119} The solvothermal synthesis of copper phthalocyanine nanotubes and nanostructures in ethylene glycol has been recently reported for the electrosynthesis of urea¹²⁰ and ammonia¹²¹ respectively.
溶剂热合成法也被用于制备棒状铁酞菁 ^{116, 117} 和具有光催化及电容储能应用潜力的多级结构四硝基酞菁 ^{118, 119} 。近期研究报道了在乙二醇中溶剂热合成铜酞菁纳米管及纳米结构，分别用于电合成尿素 ¹²⁰ 和氨 ¹²¹ 。

2.2.3 Ionic Liquids

Ionic liquids have gained momentum as appealing reaction media for organic synthesis because of their low vapor pressure, high thermal stability, high ionic conductivity, and ease of recovery.
离子液体因其低蒸气压、高热稳定性、高离子导电性和易于回收等特点，已成为有机合成中极具吸引力的反应介质。
Due to their ionic nature, ionic liquids are particularly advantageous for reactions involving charged reactive species.
由于其离子特性，离子液体特别适用于涉及带电活性物种的反应。
Their high chemical stability and low volatility guarantee that emissions from ionic liquids pose minimal environmental concerns.
它们的高化学稳定性和低挥发性确保了离子液体的排放对环境的影响微乎其微。
However, this same characteristic renders them persistent substances in natural environments, thus potentially leading to pollution.
然而，这一特性也使得它们在自然环境中成为持久性物质，从而可能造成污染。
The debate regarding the classification of ionic liquids as sustainable reaction media persists in the literature.
关于离子液体是否应归类为可持续反应介质的争论在文献中持续存在。
We include them in this review because, based on our analysis of the articles, they have demonstrated recyclability for a certain number of cycles under the specified conditions and are typically used in modest quantities on a lab-scale.
我们将这些方法纳入本综述，因为根据对文献的分析，它们已在特定条件下展现出一定次数的可循环使用性，且通常在实验室规模中以适量使用。
Their use in the formation of the phthalocyanine ring can be advantageous, as ionic liquids can generally enhance the reactivity of nucleophiles, thereby reducing the yield of side products formed.^{122, 123} In addition to their use as reaction media, ionic liquids have been employed in the removal of the central metal of the macrocycle.¹²⁴ Some ionic liquids successfully used in the synthesis of phthalocyanines are shown in Figure 5. In 2005, Lo et al.
它们在酞菁环形成过程中的应用具有优势，因为离子液体通常能增强亲核试剂的反应活性，从而减少副产物的生成。 ^{122, 123} 除了作为反应介质外，离子液体还被用于脱除大环化合物的中心金属。 ¹²⁴ 图 5 展示了部分成功应用于酞菁合成的离子液体。2005 年，Lo 等人
explored the potential of tetrabutylammonium bromide (TBAB) as a solvent for obtaining alkylthio, alkoxy, and phenoxy-substituted phthalonitriles by S_NAr and for subsequent cyclization to obtain the corresponding phthalocyanines (IL1-IL6).¹²⁵ It is interesting to note that the S_NAr step did not require the presence of a base, as is normally necessary in this type of reaction, probably because the ionic nature of the solvent increases the nucleophilicity of the thiol and alcohol groups.
探讨了四丁基溴化铵（TBAB）作为溶剂在通过 S _N Ar 反应获取烷硫基、烷氧基和苯氧基取代邻苯二甲腈，以及后续环化反应合成相应酞菁（IL1-IL6）中的应用潜力。 ¹²⁵ 值得注意的是，该 S _N Ar 反应步骤无需像此类反应通常所需的那样添加碱，这可能是由于溶剂的离子特性增强了硫醇和醇基团的亲核性。
The phthalocyanines were then synthesized in the same ionic liquid using varying amounts of DBU, in yields comparable to reactions carried out with conventional procedures.
随后在相同离子液体中，使用不同量的 DBU 合成了酞菁化合物，其产率与传统合成方法相当。
As a collateral reaction, the authors report the formation of significant amounts of metal-free tetrakis(alkylthio) phthalocyanines when four equivalents of thiols were used in the nucleophilic aromatic substitution of 4-nitrophthalonitrile.
作为副反应，作者报告称，在 4-硝基邻苯二甲腈的亲核芳香取代反应中使用四当量硫醇时，会生成大量无金属四(烷硫基)酞菁化合物。

It would have been interesting to investigate this occurrence further, as the possibility of pushing this side reaction would have led to the final product reducing both reaction time and required chemicals.
若能进一步探究这一现象将颇具意义，因为推动该副反应的可能性有望缩短反应时间并减少所需化学品，从而获得最终产物。
TBAB has been employed also in the synthesis of unsubstituted, chlorinated and nitro phthalocyanines bearing several metal ions.¹²⁶ Phthalonitriles, phthalimides and phthalic anhydrides have been used as reactants, in the classic reaction system involving urea and ammonium heptamolybdate.
TBAB 还被用于合成带有多种金属离子的未取代、氯化和硝基酞菁化合物。在包含尿素和七钼酸铵的传统反应体系中，邻苯二甲腈、邻苯二甲酰亚胺和邻苯二甲酸酐被用作反应物。
Overall, the reactions were found to proceed at least an order of magnitude faster than their standard counterparts.
总体而言，这些反应的进行速度至少比标准反应快一个数量级。
Tests have indicated a general tendency for phthalonitriles to necessitate shorter reaction times and achieve higher yields than other precursors.
测试表明，与其他前体相比，邻苯二甲腈通常需要更短的反应时间并能获得更高的产率。
Furthermore, phthalonitriles required lower amounts of urea, aligning with the reduced need for a nitrogen source compared to phthalimides and phthalic anhydrides.
此外，与邻苯二甲酰亚胺和邻苯二甲酸酐相比，邻苯二甲腈所需的尿素量更少，这符合对氮源需求的降低。
The ionic liquid was found to be recyclable up to 4 times, although with a progressive decrease in yield from 95 % to 70 %.
研究发现该离子液体可循环使用多达 4 次，但产率会从 95%逐步下降至 70%。
Nickel phthalocyanine has been synthesized in 1-butyl-3-methylimidazolium tetrafluoroborate giving a high yield of one-dimensional structures without using a template or stabilizing agent.¹²⁷ This occurrence was rationalized with the unique π-π stacking of the imidazole ring that induces a specific directed growth of the phthalocyanine product.
在 1-丁基-3-甲基咪唑四氟硼酸盐中成功合成了镍酞菁，无需使用模板或稳定剂即可获得高产率的一维结构。这一现象可归因于咪唑环独特的π-π堆积作用，它能诱导酞菁产物发生特定的定向生长。
1,1,3,3-Tetramethylguanidinium trifluoroacetate (TMGT) and TBAB have been investigated as ionic liquid and as phase transfer reagent, respectively, for the synthesis of PcH₂.¹⁰⁸ These studies were conducted under both conventional heating conditions or microwave irradiation using hexamethyldisylylazane, sodium sulfide or urea as co-reactants.
1,1,3,3-四甲基胍三氟乙酸盐（TMGT）和四丁基溴化铵（TBAB）分别作为离子液体和相转移试剂被研究用于酞菁（PcH）的合成。这些研究在常规加热条件或微波辐射下进行，使用六甲基二硅氮烷、硫化钠或尿素作为共反应物。
In all the examined cases, microwaves promoted the efficient formation of target product in 3–5 minutes depending on the reaction system, with high yields (up to 80 %) comparable to those of conventional heating.
在所有研究案例中，微波均能在 3-5 分钟内高效促成目标产物的形成（具体时长取决于反应体系），且产率高达 80%，与传统加热方式相当。
All in all, the best performances were obtained with TMGT regardless of the experimental procedure.
总体而言，无论采用何种实验方案，TMGT 均展现出最佳性能。
The authors rationalize this evidence with the formation of 1,1,3,3-tetramethylguanidine (TMG) and trifluoroacetic acid (TFA) due to thermal dissociation of TMGT.
作者们通过 1,1,3,3-四甲基胍（TMG）和三氟乙酸（TFA）的形成解释了这一现象，认为这是 TMGT 热解离的结果。
The nucleophilicity of the nitrogen atom of TMG is strong enough to react with one cyano group, assisted by its activation with a strong protic acid such as TFA or the conjugated acid of TMG itself, and initiate the tetramerization of phthalonitrile.
TMG 中氮原子的亲核性足够强，在强质子酸（如 TFA 或 TMG 自身共轭酸）的活化辅助下，可与一个氰基发生反应，从而引发邻苯二甲腈的四聚反应。
Chauchan et al.  Chauchan 等
investigated the effect of ionic liquid composition on the synthesis of phthalocyanines IL1, IL7, IL8, and IL9.¹²⁸ A selection of functional ammonium-, pyridinium- and imidazolium ILs in the presence of DBU were examined, resulting in a pyridinium>imidazolium>ammonium general reactivity scale.
研究了离子液体组成对酞菁 IL1、IL7、IL8 和 IL9 合成的影响。 ¹²⁸ 在 DBU 存在下考察了一系列功能性铵盐、吡啶鎓盐和咪唑鎓盐离子液体，得出反应活性总体规律为：吡啶鎓盐>咪唑鎓盐>铵盐。
Pyridinium-based materials degraded quickly due to the presence of the organic base.
由于有机碱的存在，吡啶鎓基材料会快速降解。
The imidazolium-IL effectiveness was explained with the deprotonation of the ring with generation of a negatively charged nucleophilic ion reacting with CN groups of phthalonitrile.
咪唑鎓离子液体的有效性可通过环状结构的去质子化作用来解释，该过程会生成带负电的亲核离子，进而与邻苯二甲腈的氰基发生反应。
All in all, hydroxylated ionic liquids gave the best result due to the formation of alkoxy anions, that similarly attack cyano groups.
总体而言，羟基化离子液体因能形成同样可攻击氰基的烷氧基阴离子而展现出最佳反应效果。
A dependance on the nature of the ionic liquid anion was also reported.
研究还指出，这种依赖性受离子液体阴离子性质的影响。
Once that N-(2-hydroxyethyl)-N,N-dimethylbutan-1-aminium bromide ([bhyeda][Br]) was identified as the best-performing reaction medium, it was used to synthesize methyl-, methoxy-, alkoxy- and nitro-substituted phthalocyanines with several metal ions.
在确定 N-(2-羟乙基)-N,N-二甲基丁-1-溴化铵([bhyeda][Br])为最佳反应介质后，研究人员利用该介质合成了带有甲基、甲氧基、烷氧基和硝基取代基的多种金属酞菁化合物。
Target products were synthesized in generally high yields, up to 74 %.
目标产物的合成收率普遍较高，最高可达 74%。
The structures of the phthalocyanines discussed in this paragraph are illustrated in Figure 6.
本段讨论的酞菁结构如图 6 所示。

2.2.4 Deep Eutectic Solvents

Deep eutectic solvents (DESs) have garnered widespread attention as efficient and innovative media in the past decade.
过去十年间，低共熔溶剂（DESs）作为一种高效创新的介质获得了广泛关注。
The environmentally friendly nature of deep eutectic solvents (DESs) stems from several key properties, including low vapor pressure, non-flammability, recyclability, biodegradability, and non-toxicity.
低共熔溶剂（DESs）的环保特性源于其多项关键性质，包括低蒸气压、不易燃性、可回收性、可生物降解性以及无毒特性。
DESs typically consist of two components: a hydrogen bond donor (HBD) and a hydrogen bond acceptor (HBA) the nature of which influences their physical properties.
DESs 通常由两种组分组成：氢键供体（HBD）和氢键受体（HBA），其性质会影响它们的物理特性。
By mixing the HBA and HBD components (quaternary ammonium salt or metal salt and species like alcohols, amides, amines, acids, urea, sugars, carboxylic acids, and glycerol, among others, respectively) in a specific molar ratio, a homogeneous solvent is commonly formed with a melting point lower than that of its pure constituents.¹²⁹ DESs share similar features with ionic liquids but offer considerable advantages, including being derived from biodegradable and non-toxic starting materials, having a cheaper production process, lower cost of raw materials, and importantly, being obtainable from renewable feedstocks and rapidly degradable in the environment.¹³⁰ Nowadays, DESs have been applied in fields such as inorganic¹³¹ and organic synthesis^131-133 and biocatalysis.¹³⁴ To the best of our knowledge, only a few papers discuss the synthesis of phthalocyanines in DESs.
将氢键受体（HBA）与氢键供体（HBD）组分（分别为季铵盐/金属盐和醇类、酰胺类、胺类、酸类、尿素、糖类、羧酸及甘油等物质）按特定摩尔比混合时，通常会形成熔点低于纯组分的均相溶剂。 ¹²⁹ 低共熔溶剂（DESs）与离子液体特性相似，但具有显著优势：其原料可生物降解且无毒、生产工艺更经济、原料成本更低，更重要的是可从可再生原料获取并在环境中快速降解。 ¹³⁰ 目前 DESs 已应用于无机 ¹³¹ 与有机合成 ^131-133 及生物催化 ¹³⁴ 等领域。据我们所知，仅有少数文献探讨了酞菁类化合物在 DESs 中的合成。
Shaabani et al.¹³⁵ report the use of several deep eutectic systems based on choline chloride (ChCl) and several hydrogen donors.
Shaabani 等人 ¹³⁵ 报道了基于氯化胆碱（ChCl）与多种氢供体的几种低共熔体系的应用。
After optimizing the system and identifying urea as the best choice, ChCl-urea mixtures in a 2 : 1 molar ratio were used for the synthesis of a wide range of unsubstituted and tetra-nitro-substituted metallophthalocyanines with variable yields in times between 10 and 60 minutes.
在优化系统并确定尿素为最佳选择后，采用摩尔比为 2:1 的氯化胆碱-尿素混合物合成了多种未取代及四硝基取代的金属酞菁化合物，反应时间介于 10 至 60 分钟之间，产率各异。
In particular, the synthesis of copper phthalocyanine at 120 °C with a yield of 83 % in just 15 minutes deserves attention, as the result obtained is comparable to those deriving for example from microwave syntheses.
特别是铜酞菁在 120°C 下仅需 15 分钟即可获得 83%收率的合成方法值得关注，其效果可与微波合成等工艺相媲美。
The shorter reaction times, if compared with other procedures in solvents, makes this approach quite interesting and deserving more investigations, especially to evaluate the tolerance of the solvent system to the functional groups possibly present on the starting phthalonitrile and the possibility of recycling it to reuse it several times.
与其他溶剂工艺相比，更短的反应时间使该方法颇具研究价值，值得进一步探索，特别是评估该溶剂体系对起始邻苯二甲腈中可能存在的官能团的耐受性，以及回收溶剂实现多次循环利用的可能性。
In 2020 CuPc was synthesized using the same DES.¹³⁶ The highest yield was 90 % and was obtained with 1 : 3–1 : 4 mixtures of choline chloride and urea.
2020 年，研究人员采用相同的低共熔溶剂（DES）合成了铜酞菁（CuPc）。当氯化胆碱与尿素以 1:3 至 1:4 的比例混合时，可获得最高 90%的产率。
The authors prove recyclability of the reaction medium up to five times before observing degradation of the components.
作者证实该反应介质可循环使用五次后才会出现组分降解。

2.2.5 Solid-State Synthesis

Solid state syntheses take the minimization of the quantities of solvent used to extreme consequences, avoiding its use altogether or reducing it by orders of magnitude compared to conventional procedures.
固态合成法将溶剂用量的最小化推向极致，与传统工艺相比完全避免使用溶剂或将其用量减少数个数量级。
Energy input can be provided by heating or mechanochemistry, thus employing mechanical forces to enable chemical reactivity.
能量输入可通过加热或机械化学方式提供，即利用机械力实现化学反应活性。
When heating, reaction temperatures equal to or higher than the melting temperature of one or more reagents are frequently chosen, to increase contact between them and improve yields.
加热时，常选择等于或高于一种或多种试剂熔点的反应温度，以增加它们之间的接触并提高产率。
We point out that, for simplicity, we will refer to this specific type of procedure as “solid state” even though it technically occurs in a liquid phase due to the reaction conditions.
需要说明的是，为简化表述，我们将这类特定操作流程统称为"固态"反应，尽管在反应条件下该过程实际发生于液相中。
The main drawback of syntheses in molten mixtures is the high temperatures required, often equal to or higher than those of corresponding solution-based methods.
熔融混合物合成的主要缺点在于所需温度较高，通常等于或高于相应溶液法的反应温度。
Additionally, the thermal energy involved, combined with the high concentration of reagents and reaction intermediates, can promote degradation processes or the formation of by-products, potentially catalyzed or influenced by impurities such as oxygen or humidity if the reaction setup is not meticulously controlled.
此外，所涉及的热能，加上高浓度的试剂和反应中间体，可能促进降解过程或副产物的形成，如果反应装置未得到精细控制，这些过程还可能受到氧气或湿度等杂质的催化或影响。
Nonetheless, we believe it is worthwhile to describe some methodologies where temperatures are kept within 150–170 °C, such as those reported for solvents like glycerol and anisole in this review.
尽管如此，我们认为仍有必要介绍一些将温度控制在 150-170°C 范围内的合成方法，例如本综述中提及的以甘油和苯甲醚为溶剂的案例。
Molten urea is typically employed both as a solvent and a source of nitrogen when phthalic precursors are used,¹³⁷ though there are also reports of its use with phthalonitriles.¹³⁸ In 2013, Lokesh et al.
当使用邻苯二甲酸前体时，熔融尿素通常既作为溶剂又作为氮源， ¹³⁷ 不过也有报道称其可与邻苯二甲腈配合使用。 ¹³⁸ 2013 年，Lokesh 等人
reported on the synthesis of functionalized palladium phthalocyanines, achieving some derivatives by simply mixing phthalonitriles with a desired salt and heating to 140–160 °C.¹³⁹ While the yields are promising, the authors suggest possible contaminations by impurities, likely due to the formation of phthalocyanine oligomers as suggested by evidence in the Q-band absorption region of the UV-Vis spectra and small discrepancies between theoretical and experimental elemental analysis values.
报道了功能化钯酞菁的合成方法，通过简单混合邻苯二甲腈与目标盐并在 140–160°C 加热即可获得部分衍生物。尽管产率表现良好，但作者指出可能存在杂质污染，这可能是由于酞菁低聚物的形成所致——紫外-可见光谱 Q 吸收带的证据及元素分析理论值与实验值的微小差异均支持这一推断。
Reducing the environmental impact of synthesizing palladium derivatives is a pertinent topic, given their potential catalytic activity in palladium-mediated C−C couplings.
鉴于钯衍生物在钯介导的碳-碳偶联反应中潜在的催化活性，降低其合成过程对环境的影响已成为一个重要议题。
This has recently been demonstrated to be feasible for Sonogashira coupling of triple bonds with aryl halides at room temperature without the need for phosphine ligands.¹⁴⁰ Remaining within the topic of catalysis and transitioning to the equally broad and relevant subject of producing biofuels and carbon-based chemicals through CO₂ reduction, we highlight the solventless synthesis of tetra-nitro cobalt phthalocyanine in molten urea starting from 4-nitrophthalonitrile, cobalt chloride hexahydrate, and a catalytic amount of ammonium heptamolybdate tetrahydrate ((NH₄)₆Mo₇O₂₄ ⋅ 4H₂O), reported in 2019 by Wu et al.¹¹ This compound, obtained in a 44 % yield, serves as a direct precursor to tetra-amino cobalt phthalocyanine, which is among the first transition-metal-based molecular electrocatalysts capable of performing the six-electron reduction of CO₂ to methanol with an appreciable activity and selectivity when immobilized on carbon nanotubes.
最近研究表明，在室温下无需膦配体即可实现三键与芳基卤化物的 Sonogashira 偶联反应。 ¹⁴⁰ 围绕催化主题，我们转向同样广泛且相关的领域——通过 CO ₂ 还原制备生物燃料及碳基化学品。值得关注的是 Wu 等人于 2019 年报道的无溶剂合成法：以 4-硝基邻苯二甲腈、六水合氯化钴及催化量四水合七钼酸铵((NH ₄ ) ₆ Mo ₇ O ₂₄ ·4H ₂ O)为原料，在熔融尿素中合成四硝基钴酞菁。 ¹¹ 该化合物以 44%收率获得，可作为四氨基钴酞菁的直接前体。后者作为首批过渡金属分子电催化剂，当固定在碳纳米管上时，能以显著活性和选择性实现 CO ₂ 六电子还原制甲醇。
In 2022, Langterreiter et al.
2022 年，Langterreiter 等人
investigated the solid-state synthesis of tetra-tert-butylphthalocyanines.¹⁴¹ They developed a synthetic procedure based on a combination of mechanochemical liquid-assisted grinding and aging at a certain temperature, optimizing it by systematically varying a series of variables.
研究了四叔丁基酞菁的固态合成方法。他们开发了一种基于机械化学液体辅助研磨与特定温度下老化相结合的合成工艺，并通过系统改变一系列变量对其进行了优化。
In particular, the use or not of the ball mill as the initial step, the quantity of DMAE and DBU and the temperature and aging time were systematically varied obtaining conversions of up to 99 %.
特别是通过系统调整是否使用球磨作为初始步骤、DMAE 和 DBU 的用量以及温度和老化时间，转化率最高可达 99%。
The procedure was then successfully applied to a series of metal ions to verify their tolerability.
随后，该方法被成功应用于一系列金属离子以验证其耐受性。
Regarding scalability, the reaction was tested up to 2 grams of reagent without substantial changes in conversion, a remarkable result in the context of the synthesis of phthalocyanines on a laboratory scale.
关于可放大性，该反应在试剂用量高达 2 克时仍能保持转化率基本不变，这一结果在实验室规模酞菁合成领域堪称卓越。
Mechanochemical synthesis is so far generally underexplored in the literature regarding phthalocyanines.
目前关于酞菁类化合物的机械化学合成在文献中研究相对不足。
Recently, Fan et al.
最近，Fan 等
reported the synthesis of a series of phthalocyanine polymeric materials with hierarchical porosity by exploiting a mechanochemical approach (Figure 7).¹⁴² The possibility of working with reagents that are poorly soluble and have a high melting temperature by exploiting the mechanical energy of the ball mill allows for easy access to classes of materials that would otherwise be difficult to obtain.
报道了通过机械化学方法合成一系列具有分级孔隙结构的酞菁聚合物材料（图 7）。 ¹⁴² 利用球磨机的机械能处理难溶且高熔点的试剂，使得这类通常难以获得的材料能够被轻松制备。