Application of hexachloroxylene as novel acylating chlorination reagent and efficient preparation of acyl chloride
By using hexachloroxylene to react with carboxylic acids to generate acyl chlorides, the environmental and cost issues of traditional acyl chloride reagents are solved, realizing a highly efficient and low-cost acyl chloride process suitable for the preparation of various industrial acyl chloride products.
Patent Information
- Application Number
- CN202410713743.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-06-03
- Publication Date
- 2025-12-09
AI Technical Summary
Existing acyl chlorination processes present environmental challenges, including the emission of harmful waste gases. Furthermore, traditional acyl chlorination reagents, such as trichlorotoluene, are costly and inefficient, making it difficult to achieve efficient and low-cost green preparation.
Hexachloroxylene is used as a novel acyl chloride reagent to react with carboxylic acids to produce benzoyl chloride and acyl chloride. By controlling reaction conditions such as temperature, pressure, solvent and additives, efficient separation and purification can be achieved.
The separation of acyl chloride products generated by the reaction of hexachloroxylene with carboxylic acids is simple, low-cost, and highly efficient, significantly improving the environmental friendliness and economy of the acyl chloride process.
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Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the field of new functional materials and fine chemicals, and particularly relates to hexachlorodimethylbenzene C6H4(CCl3)2 as a new acyl chloride reagent to realize efficient and low-cost green preparation of a series of carboxylic acid chlorides. BACKGROUND
[0002] Acyl chloride is an important class of functional chemical materials or organic synthesis intermediates, and has extremely wide application in the manufacture of fine chemicals, medicines, pesticides and the like. Traditionally, acyl chloride is prepared from corresponding carboxylic acid and so-called acyl chloride reagent, commonly used for example, thionyl chloride, phosphorus trichloride, phosphorus pentachloride, (solid) phosgene, oxalyl chloride and the like. The participation of these raw materials usually inevitably produces long-term environmental management problems, including but not limited to emission of harmful three wastes such as sulfur dioxide, (sub)phosphoric acid, carbon monoxide, which is a dangerous or high-emission process strictly controlled by national laws and regulations, and a new process and technology of new type green and efficient and lower cost is urgently needed in the industry.
[0003]
[0004] Another acyl chloride reagent known from the literature is trichloromethylbenzene, which is known to those skilled in the art, which reacts with carboxylic acid to form the corresponding carboxylic acid chloride and benzoyl chloride, and industrialization cases are particularly, for example, trichloromethylbenzene and benzoic acid react to form benzoyl chloride. This process only produces hydrogen chloride dry gas as a byproduct, and the hydrogen chloride dry gas can be easily absorbed by water to form hydrochloric acid solution (used as a byproduct or sold externally), or directly oxidized to generate chlorine to realize the recycling of chlorine, which is a new technology worthy of promotion.
[0005] It needs to be particularly emphasized that dichlorohexamethylbenzene, i.e. para-, meta-, or ortho-substituted hexachlorodimethylbenzene, has few disclosures in the literature and industrial applications. This is worth thinking and attention, since hexachlorodimethylbenzene is derived from petrochemical refining abundant dimethylbenzene aromatic hydrocarbon resources and chlor-alkali chemical resources, which is low in cost and large in scale, and its rationalization and environmentally friendly utilization has extremely important practical significance.
[0006] The current literature is limited to preparing p-terephthaloyl chloride or m-terephthaloyl chloride, i.e. limited to condensation reaction of p-terephthaloyl chloride or m-terephthaloyl chloride with corresponding carboxylic acid of specific molecular skeleton, specifically, p-hexachlorodimethylbenzene and p-terephthalic acid (PTA) are reacted to prepare p-terephthaloyl chloride, or m-hexachlorodimethylbenzene and m-terephthalic acid are reacted to prepare m-terephthaloyl chloride.
[0007] This is not surprising, and the conventional wisdom is that hexachlorodimethylbenzene and trichloromethylbenzene are similar, and the former is recognized by inert thinking as only a special structural derivative of the latter.
[0008] The present application surprisingly found that, because the applicant first broke through the non-illumination liquid flow automated large-scale production of hexachlorodimethyl benzene manufacturing technology, carried out detailed and in-depth research, through practice found, out of the professional practitioners of the technology, unexpectedly, hexachlorodimethyl benzene is essentially a more active than trichlorobenzene, lower cost, more efficient process of new acyl chloride raw materials; that is, it is not a special case of trichlorobenzene, more importantly, it is a more broad-spectrum acyl chloride reagent raw material than trichlorobenzene.
[0009] On the one hand, the unexpectedness of the present application is derived from the fact that the technical personnel in the field have long failed to recognize that the mass ratio of the core functional group density, i.e. the trichloromethyl unit in the unit structure, in the trichlorobenzene structure is 1.5 (i.e. trichloromethyl / benzene ring); in contrast, the mass ratio in the hexachlorodimethyl benzene structure is as high as 3.1, i.e. the latter is more than double the former.
[0010] Higher trichloromethyl active group density means lower use cost. This effect is further amplified in practice, i.e. since hexachlorodimethyl benzene carries two active trichloromethyl functional groups, while trichlorobenzene has only one trichloromethyl functional group, therefore their molar ratio with the corresponding carboxylic acid, the former is 1 / 2, the latter is only 1 / 1, the quantity relationship is doubled, the cost is essentially halved, thus further strengthening the cost reduction and efficiency improvement benefits in terms of product output equivalent and volume. That is, compared with the trichlorobenzene system, hexachlorodimethyl benzene can convert carboxylic acid to its acyl chloride with higher efficiency and lower cost.
[0011] On the other hand, the unexpectedness of the present application also comes from the fact that the technical personnel in the field have not realized that due to the strong electron-withdrawing effect of trichloromethyl, hexachlorodimethyl benzene is a significantly electron-deficient electrophile than trichlorobenzene, and thus it is easier to react with carboxylic acid to obtain higher product yield with faster speed and efficiency.
[0012] Meanwhile, further, the benzene diacyl chloride generated by hexachlorodimethyl benzene, especially terephthaloyl chloride, is solid at room temperature, which is significantly different from the liquid state of benzoyl chloride, so the product separation in the following reaction formula (I) becomes exceptionally easy due to the difference in the state of the two acyl chlorides.
[0013] The essence of the present application is to creatively replace trichlorobenzene with hexachlorodimethyl benzene in its cross-condensation reaction with different carboxylic acids of different mother nucleus structures to produce a series of industrially very important acyl chloride chemicals with lower cost and higher efficiency. Unexpectedly, although trichlorobenzene is generally recognized as the cheapest and most readily available acyl chloride reagent, the cost and efficiency benefits obtained by using the hexachlorodimethyl benzene system in the present application show a significant advantage over using the corresponding trichlorobenzene system.
[0014] The present application aims to explicitly establish hexachlorodimethylbenzene as a new generation of environmentally friendly acyl chloride reagent with broader spectrum and lower cost than trichloromethylbenzene for the first time in the industry. Its popularization and use will inevitably promote the manufacturing level of acyl chloride industry to a new height. SUMMARY
[0015] The present application has now found that hexachlorodimethylbenzene of structural formula A and carboxylic acid B (or its anhydride) react under the conditions of reaction formula (I) to co-produce benzene diacyl chloride of structural formula C and acyl chloride D. Both can be conveniently separated and purified by distillation, rectification, or crystallization, etc.
[0016]
[0017] wherein R is a branched or straight chain aliphatic hydrocarbon group containing 1-24 carbon atoms (designated as C 1 -C 24 ) containing 0-6 non-consecutive oxygen atoms, nitrogen atoms, sulfur atoms, fluorine atoms, chlorine atoms, silicon atoms, carbonyl groups, hydroxyl groups, amine groups, carboxyl groups, double bonds, triple bonds, or siloxyl substituents; or R is a C 4 -C 24 aromatic or heteroaromatic ring substituent, the (hetero)aryl group containing 0-4 C 1 -C 24 alkyl groups, OC 1 -C 24 alkoxy groups, SC 1 -C 24 alkylthio groups, NHC 1 -C 24 alkylamine groups, N(C 1 -C 24 )2alkylamine groups, or halogen substituents.
[0018] The conditions are at least one of a solvent, a temperature, a pressure (or vacuum), and an additive.
[0019] The additive is a catalyst, or an accelerator. Preferably, the additive is a metal chloride or oxide; more preferably the additive is ferric chloride, iron oxide.
[0020] Preferably, the amount of the additive used is 0.001-1000% of the reaction raw materials based on the equivalent of raw materials A or B; preferably 0.01-100%, more preferably 0.1-50%, further more preferably 0.1-30%.
[0021] The temperature is -25-450 degrees Celsius, preferably -20-300 degrees Celsius; more preferably -20-250 degrees Celsius.
[0022] The pressure refers to the reaction system is carried out under pressure or a certain vacuum degree, the pressure of the reaction process is 0.001-200 atm, preferably 0.01-100 atm, more preferably 0.1-10 atm.
[0023] The solvent is selected from at least one of substituted or unsubstituted aromatic hydrocarbons containing 1-24 carbons, straight-chain or branched aliphatic hydrocarbons, (sub) sulfones, amides, ethers, alcohols, esters, ketones, nitriles, carboxylic acids, water, amines, carbonates, ionic liquids, and supercritical carbon dioxide; or the liquid or molten substrate (including mixtures thereof) itself simultaneously serves as the solvent medium.
[0024] The use of solvent is preferred but not necessary, under certain conditions, it is preferred not to use solvent, i.e. using the solvate of the reaction raw material, the melt, or the reaction raw material is directly mixed and then carried out under heating, grinding, or gas phase conditions; and the way of using supercritical carbon dioxide as the reaction medium. The advantage of using supercritical carbon dioxide as the reaction medium is green and environmentally friendly, and conducive to the occurrence of the reaction and the separation of the product, such advantages are well known to those skilled in the art.
[0025] In some cases, it is preferred to use the anhydride form of carboxylic acid B, because the action of the anhydride and the raw material A does not release hydrochloric acid dry gas while producing acyl chloride products, and the environmental friendliness of the process is more favorable.
[0026] One limitation is that carboxylic acid B does not contain several special structures, i.e. structures with the same molecular skeleton (double-substituted benzene ring) as raw material A, including: terephthalic acid, isophthalic acid, or phthalic acid; that is, acyl chloride D does not contain terephthaloyl chloride, isophthaloyl chloride, or phthaloyl chloride.
[0027] Preferably, the exemplary but non-limiting structures of carboxylic acid B (or its anhydride) include the following compounds:
[0028]
[0029] Preferably, one way of carrying out the reaction of general formula (I) is (IA), i.e. reacting p-hexachlorodimethylbenzene and benzoic acid to co-produce terephthaloyl chloride and benzoyl chloride. Terephthaloyl chloride is a raw material for the manufacture of para-aramid, and benzoyl chloride is the most widely used acyl chloride product in industry.
[0030]
[0031] Preferably, one way of carrying out the reaction of general formula (I) is (IB), i.e. reacting m-hexachlorodimethylbenzene and benzoic acid to co-produce isophthaloyl chloride and benzoyl chloride. Isophthaloyl chloride is a key raw material for the production of meta-aramid.
[0032]
[0033] Preferably, one embodiment of the reaction of general formula (I) is (IC), i.e. the reaction of p-hexachlorobenzene and mesitric acid to co-produce terephthaloyl chloride and 2,4,6-trimethylbenzoyl chloride. 2,4,6-Trimethylbenzoyl chloride is a key raw material for the production of so-called phosphine oxide type photoinitiators, such as the photoinitiators of commercial designation TPO, TPO-L, and 819.
[0034]
[0035] Preferably, one embodiment of the reaction of general formula (I) is (ID), i.e. the reaction of p-hexachlorobenzene and cyclohexanecarboxylic acid to co-produce terephthaloyl chloride and cyclohexanoyl chloride. Cyclohexanoyl chloride is a key raw material for the manufacture of photoinitiator 184:
[0036]
[0037] Preferably, one embodiment of the reaction of general formula (I) is (IE), i.e. the reaction of p-hexachlorobenzene and isobutyl acid to co-produce terephthaloyl chloride and isobutyryl chloride. Isobutyryl chloride is a key raw material for the manufacture of photoinitiator 1173:
[0038]
[0039] Preferably, one embodiment of the reaction of general formula (I) is (IF), i.e. the reaction of p-hexachlorobenzene and oxalic acid to co-produce terephthaloyl chloride and oxalyl chloride:
[0040]
[0041] Preferably, one embodiment of the reaction of general formula (I) is (IG), i.e. the reaction of p-hexachlorobenzene and succinic acid to co-produce terephthaloyl chloride and succinyl chloride:
[0042]
[0043] Preferably, one embodiment of the reaction of general formula (I) is (IH), i.e. the reaction of p-hexachlorobenzene and adipic acid to co-produce terephthaloyl chloride and adipoyl chloride:
[0044]
[0045] Preferably, one embodiment of the reaction of general formula (I) is (II), i.e. the reaction of p-hexachlorobenzene and acetic acid (anhydride) to co-produce terephthaloyl chloride and acetyl chloride. The use of acetic anhydride is preferred to avoid the release of dry hydrogen chloride gas.
[0046] Acetyl chloride is a versatile and commodity acylating agent.
[0047]
[0048] Preferably, one of the implementations of the reaction of general formula (I) is (IO), that is, p-hexachlorodimethylbenzene and pivalic acid are reacted to coproduce terephthaloyl chloride and pivaloyl chloride:
[0049]
[0050] Preferably, one of the implementations of the reaction of general formula (I) is (IP), that is, p-hexachlorodimethylbenzene and pyromellitic acid (anhydride) are reacted to coproduce terephthaloyl chloride and pyromellitic acid chloride. When pyromellitic anhydride is used, water can be introduced into the reaction system to open it in situ to form pyromellitic acid, which then continues to participate in the acyl chloride reaction; or, preferably, pyromellitic anhydride is directly reacted, which has the advantage of not releasing hydrogen chloride acid gas.
[0051]
[0052] Preferably, one of the implementations of the reaction of general formula (I) is (IQ), that is, p-hexachlorodimethylbenzene and furandicarboxylic acid are reacted to coproduce terephthaloyl chloride and furandicarboxylic acid chloride. Furandicarboxylic acid chloride is a new raw material for preparing furan-based aramid or furan-based biodegradable materials.
[0053]
[0054] Preferably, one of the implementations of the reaction of general formula (I) is (IR), that is, p-hexachlorodimethylbenzene and phthalic anhydride are reacted to coproduce terephthaloyl chloride and phthaloyl chloride.
[0055]
[0056] In the examples, we will further illustrate.
DETAILED DESCRIPTION
[0057] The gist of the present application will be further illustrated below with specific examples:
[0058] Examples:
[0059]
[0060] A 500ml round bottom flask was charged with 210g of p-hexachlorodimethylbenzene, 164g of benzoic acid powder and 1.2g of ferric chloride, and equipped with a reflux condenser and a calcium chloride drying tube. The reaction mixture was heated at 110°C and sampled for GC analysis after in situ esterification with methanol. After 1.5 hours, the reaction was stopped and the distillation apparatus was installed. The product was distilled under reduced pressure at room temperature to give 183.5g of benzoic acid chloride (97.1% yield). The product was further distilled under reduced pressure at 100-105°C to give 49.5g of terephthaloyl chloride (99.8% purity), at 105-110°C to give 40.1g of terephthaloyl chloride (99.9% purity), and at 110-130°C to give 41.9g of terephthaloyl chloride (99.6% purity). The total yield was 128.2g of product (96.3% yield).
[0061] The reaction conditions were kept the same except that 210g of p-hexachlorodimethylbenzene was replaced by 262.4g of trichlorotoluene. The reaction was stopped after 6 hours and the product was distilled to give 347.6g of benzoic acid chloride (92.1% yield).
[0062] As shown in the above comparison, p-hexachlorodimethylbenzene exhibited lower raw material consumption, higher acyl chloride reactivity, faster reaction rate, and higher product yield than trichlorotoluene.
[0063] Example:
[0064]
[0065] A 500ml round bottom flask was charged with 237g of m-hexachlorodimethylbenzene, 185.3g of benzoic acid powder and 1.3g of ferric chloride, and equipped with a reflux condenser and a calcium chloride drying tube. The reaction mixture was heated at 120°C and sampled for GC analysis after in situ esterification with methanol. After 2 hours, the reaction was stopped and the distillation apparatus was installed. The product was distilled under reduced pressure at room temperature to give 205.9g of benzoic acid chloride (96.4% yield). The product was further distilled under reduced pressure at 115-135°C to give 143.6g of isophthaloyl chloride (95.5% yield).
[0066] Example:
[0067]
[0068] A mixture of 125 g of p-hexachlorodimethylbenzene and 131.2 g of 2,4,6-trimethylbenzoic acid powder and 1.2 g of ferric chloride was mixed in a 0.5 L round bottom flask, equipped with a reflux condenser and a calcium chloride drying tube. The system was heated at 150°C. The reaction mixture was sampled and esterified in situ with methanol and then analyzed by gas chromatography (GC). After about 2 hours of reaction, the mixture was washed with petroleum ether at 0°C. The organic phase was concentrated and distilled under reduced pressure to obtain 2,4,6-trimethylbenzoyl chloride (134.3 g, 92% yield); the residual solid was p-phthaloyl chloride (77 g, 95% yield).
[0069] Example:
[0070]
[0071] A mixture of 186.8 g of p-hexachlorodimethylbenzene and 153.1 g of cyclohexanecarboxylic acid powder and 1.1 g of ferric chloride was mixed in a 0.5 L round bottom flask, equipped with a reflux condenser and a calcium chloride drying tube. The system was heated at 120°C. The reaction mixture was sampled and esterified in situ with methanol and then analyzed by gas chromatography (GC). After about 3 hours of reaction, the distillation apparatus was used, and cyclohexanoyl chloride (168.1 g, 96% yield) was distilled off first, followed by the collection of p-phthaloyl chloride fraction (115.8 g, 96% overall yield) at 110-130°C.
[0072] Example:
[0073]
[0074] A mixture of 196.8 g of p-hexachlorodimethylbenzene and 128.5 g of tert- butyl acid powder and 1.2 g of ferric chloride was mixed in a 0.5 L round bottom flask, equipped with a reflux condenser and a calcium chloride drying tube. The system was heated at 105°C. The reaction mixture was sampled and esterified in situ with methanol and then analyzed by gas chromatography (GC). After about 3 hours of reaction, the distillation apparatus was used, and tert-butyl chloride (143 g, 94% yield) was distilled off first, followed by the collection of p-phthaloyl chloride fraction (122 g, 95% overall yield) under reduced pressure.
[0075] Example:
[0076]
[0077] A mixture of 186.6 g of p-hexachlorodimethylbenzene and 88.9 g of adipic acid and 1.2 g of ferric chloride was placed in a 0.5 L round bottom flask, equipped with a reflux condenser and a drying device with anhydrous calcium chloride, and the system was heated to 110°C. After the reaction was completed, the system was cooled to 0°C and the product was treated with benzene. The benzene organic phase was concentrated to remove the solvent and then distilled under reduced pressure to obtain 99.6 g of adipoyl chloride as a yellowish liquid (91% yield). The residual solid was dried to obtain 109 g of terephthaloyl chloride (90% yield).
[0078] Example:
[0079]
[0080] A mixture of 186.6 g of p-hexachlorodimethylbenzene and 88.9 g of adipic acid and 1.2 g of ferric chloride was placed in a 0.5 L round bottom flask, equipped with a reflux condenser and a drying device with anhydrous calcium chloride, and the system was heated to 110°C. After the reaction was completed, the system was cooled to 0°C and the product was treated with benzene. The benzene organic phase was concentrated to remove the solvent and then distilled under reduced pressure to obtain 99.6 g of adipoyl chloride as a yellowish liquid (91% yield). The residual solid was dried to obtain 109 g of terephthaloyl chloride (90% yield).
[0081] Example:
[0082]
[0083] A mixture of 186.6 g of p-hexachlorodimethylbenzene and 88.9 g of adipic acid and 1.2 g of ferric chloride was placed in a 0.5 L round bottom flask, equipped with a reflux condenser and a drying device with anhydrous calcium chloride, and the system was heated to 110°C. After the reaction was completed, the system was cooled to 0°C and the product was treated with benzene. The benzene organic phase was concentrated to remove the solvent and then distilled under reduced pressure to obtain 99.6 g of adipoyl chloride as a yellowish liquid (91% yield). The residual solid was dried to obtain 109 g of terephthaloyl chloride (90% yield).
[0084] Example:
[0085]
[0086] A mixture of 186.6 g of p-hexachlorodimethylbenzene and 88.9 g of adipic acid and 1.2 g of ferric chloride was placed in a 0.5 L round bottom flask, equipped with a reflux condenser and a drying device with anhydrous calcium chloride, and the system was heated to 110°C. After the reaction was completed, the system was cooled to 0°C and the product was treated with benzene. The benzene organic phase was concentrated to remove the solvent and then distilled under reduced pressure to obtain 99.6 g of adipoyl chloride as a yellowish liquid (91% yield). The residual solid was dried to obtain 109 g of terephthaloyl chloride (90% yield).
[0087] Example:
[0088]
[0089] A mixture of 122.8 g of p-hexachlorodimethylbenzene and 116 g of phthalic anhydride powder and 1.1 g of ferric chloride was prepared in a 0.5 L round bottom flask, equipped with a reflux condenser and a drying device with anhydrous calcium chloride, and the system was heated to 160°C. After about 3 hours of reaction, the mixture was cooled to 0°C, extracted three times with benzene, and the organic phase was combined and distilled to obtain 136.8 g of phthaloyl chloride with a yield of 86%. The residue of the extraction was 75 g of terephthaloyl chloride with a yield of 94%.
[0090] It is important to emphasize that the examples described above are merely illustrative and not limiting, and that any modification or variation of the reaction conditions or parameters, which a person skilled in the art could normally adopt, would not depart from the scope of the present application, the scope of protection of which should be determined by the relevant claims.
Claims
1. A novel process for manufacturing a series of acyl chlorides based on hexachloroxylene (C6H4(CCl3)2) as a broad-spectrum acyl chloride reagent. As shown in reaction formula (I), hexachloroxylene (Structural Formula A) and carboxylic acid B (or its anhydride) react under the following reaction conditions to co-produce benzoic acid chloride (Structural Formula C) and acyl chloride D: Where R represents carbon atoms (labeled C) ranging from 1 to 24. 1 -C 24 A branched or straight-chain aliphatic hydrocarbon group containing 0-6 discontinuous oxygen, nitrogen, sulfur, fluorine, chlorine, silicon, carbonyl, hydroxyl, amino, carboxyl, double, triple, or siloxy substituents; or R is C 4 -C 24 Aromatic or heteroaryl substituents, wherein the (hetero)aryl group contains 0-4 carbon atoms 1 -C 24 Alkyl, OC 1 -C 24 Alkoxy, SC 1 -C 24 Alkylthio, NHC 1 -C 24 Alkylamine group, N(C) 1 -C 24 )2 alkylamine group, or halogen substituent. The conditions are at least one of the following: solvent, temperature, pressure (or vacuum), and additive. The additive is a catalyst or promoter of the reaction.
2. According to claim (1), preferably, the additive is a metal chloride or oxide; more preferably, the additive is ferric chloride or iron oxide; preferably, the amount of the additive used is 0.001-1000% of the reactant, based on the equivalent of raw material A or B; preferably 0.01-100%, more preferably 0.1-50%, and even more preferably 0.1-30%.
3. According to claim (1), the temperature in the conditions is -25 to 450 degrees Celsius, preferably -20 to 300 degrees Celsius; more preferably -20 to 250 degrees Celsius.
4. According to claim (1), the pressure in the conditions refers to the reaction system being carried out under pressure or a certain vacuum, and the pressure of the reaction process is 0.001-200 atmospheres, preferably 0.01-100 atmospheres, and more preferably 0.1-10 atmospheres.
5. According to claim (1), the solvent in the conditions is selected from at least one of substituted or unsubstituted aromatic hydrocarbons containing 1-24 carbons, straight-chain or branched aliphatic hydrocarbons, (sulfoxide) sulfones, amides, ethers, alcohols, esters, ketones, nitriles, carboxylic acids, water, amines, carbonates, ionic liquids, and supercritical carbon dioxide; or preferably, the liquid or molten substrate (including mixtures thereof) itself also acts as a solvent medium.
6. According to claim (1), an exemplary, and not limiting, structure of carboxylic acid B (or its anhydride) is a compound that is:
7. According to claim (1), one embodiment of the reaction formula (I) is (IA), namely, the co-production of terephthaloyl chloride and benzoyl chloride by reacting p-hexachloroxylene and benzoic acid:
8. According to claim (1), one embodiment of the reaction formula (I) is (IB), namely, the co-production of isophthaloyl chloride and benzoyl chloride by reacting m-hexachloroxylene and benzoic acid:
9. According to claim (1), one embodiment of the reaction formula (I) is (IC), namely, the co-production of terephthaloyl chloride and 2,4,6-trimethylbenzoic acid by reacting p-hexachloroxylene and 2,4,6-trimethylbenzoic acid:
10. According to claim (1), one embodiment of the reaction formula (I) is (ID), namely, the co-production of terephthaloyl chloride and cyclohexyl chloride by reacting p-hexachloroxylene and cyclohexylformic acid:
11. According to claim (1), one embodiment of the reaction formula (I) is (IE), namely, the co-production of terephthaloyl chloride and isobutylyl chloride by reacting p-hexachloroxylene and isobutyl acid:
12. According to claim (1), one embodiment of the reaction formula (I) is (IF), namely, the co-production of terephthaloyl chloride and oxaloyl chloride by reacting p-hexachloroxylene and oxalic acid:
13. According to claim (1), one embodiment of the reaction formula (I) is (IG), namely, the co-production of terephthaloyl chloride and succinic acid by reacting p-hexachloroxylene and succinic acid:
14. According to claim (1), one embodiment of the general formula (I) is (IH), namely, the co-production of terephthaloyl chloride and adipic acid by reacting p-hexachloroxylene and adipic acid:
15. According to claim (1), one embodiment of the reaction formula (I) is (II), namely, the co-production of terephthaloyl chloride and acetyl chloride by reacting p-hexachloroxylene and acetic acid (anhydride):
16. According to claim (1), one embodiment of the reaction formula (I) is (IO), namely, the co-production of terephthaloyl chloride and pivaloyl chloride by reacting p-hexachloroxylene and pivaloyl acid:
17. According to claim (1), one embodiment of the reaction formula (I) is (IP), namely, the co-production of terephthaloyl chloride and pyromellitic acid (anhydride) by reacting p-hexachloroxylene and pyromellitic acid (anhydride):
18. According to claim (1), one embodiment of the reaction formula (I) is (IQ), namely, the co-production of terephthaloyl chloride and furanyl chloride by reacting p-hexachloroxylene and furanyl dicarboxylic acid:
19. According to claim (1), one embodiment of the reaction formula (I) is (IR), namely, the co-production of terephthaloyl chloride and phthalic anhydride by reacting p-hexachloroxylene and phthalic anhydride:
20. The application of p-hexachloroxylene, m-hexachloroxylene, o-hexachloroxylene, or mixtures thereof as novel acyl chloride reagents in carboxylic acid acyl chloride reactions, as substitutes for trichlorotoluene (PhCCl3), according to claims (1-19):