402-54-0

Usage

Uses

Used in Chemical Synthesis:
4-Nitrobenzotrifluoride is used as a chemical intermediate for the production of other chemicals. Its unique structure and reactivity make it a valuable building block in the synthesis of a wide range of compounds, including pharmaceuticals, agrochemicals, and specialty chemicals.
Used in Pharmaceutical Industry:
In the pharmaceutical industry, 4-Nitrobenzotrifluoride is used as a key intermediate in the synthesis of various drug molecules. Its presence in the molecular structure can impart specific biological activities, making it an essential component in the development of new medications.
Used in Agrochemical Industry:
4-Nitrobenzotrifluoride is also utilized in the agrochemical industry for the production of pesticides and other crop protection agents. Its incorporation into these compounds can enhance their effectiveness in controlling pests and diseases, ultimately contributing to increased crop yields and food security.
Used in Specialty Chemicals:
In the specialty chemicals sector, 4-Nitrobenzotrifluoride is employed in the development of high-performance materials with unique properties. These materials can be used in various applications, such as in the electronics, automotive, and aerospace industries, where their specific characteristics are highly valued.

Synthesis Reference(s)

Synthesis, p. 932, 1980 DOI: 10.1055/s-1980-29276Tetrahedron Letters, 32, p. 91, 1991 DOI: 10.1016/S0040-4039(00)71226-3

Air & Water Reactions

Insoluble in water.

Health Hazard

Highly toxic, may be fatal if inhaled, swallowed or absorbed through skin. Contact with molten substance may cause severe burns to skin and eyes. Avoid any skin contact. Effects of contact or inhalation may be delayed. Fire may produce irritating, corrosive and/or toxic gases. Runoff from fire control or dilution water may be corrosive and/or toxic and cause pollution.

Fire Hazard

Combustible material: may burn but does not ignite readily. Containers may explode when heated. Runoff may pollute waterways. Substance may be transported in a molten form.

InChI:InChI=1/C7H5Cl2F/c8-7(9)5-2-1-3-6(10)4-5/h1-4,7H

Upstream product

• 14505-17-0 p-nitrobenzylidyne tribromide 
• 402-14-2 2-nitro-5-(trifluoromethyl)aniline 
• 62-23-7 4-nitro-benzoic acid 
• 636-98-6 p-nitrobenzene iodide 
• 2314-97-8 iodotrifluoromethane 
• 1514-87-0 metyhyl chlorodifluoroacetate 
• 680-15-9 2,2-difluoro-2-(fluorosulfonyl)acetate 
• 371-76-6 bis(trifluoromethyl)mercury 
• 2923-18-4 sodium 2,2,2-trifluoroacetate 
• 120120-26-5 (trifluoromethyl)triethylsilane 
• 455-14-1 4-trifluoromethylphenylamine 
• 74087-85-7 3,3-dimethyldioxirane 
• 98-08-8 α,α,α-trifluorotoluene 
• 619-50-1 4-nitrobenzoic acid methyl ester 

Downstream Products

• 455-14-1 4-trifluoromethylphenylamine 
• 1030-22-4 1,2-bis(4-cyanophenyl)diazene oxide 
• 75-07-0 acetaldehyde 
• 35848-46-5 4-(α,α,α-Trifluoromethyl)nitrobenzene radical anion 
• 122947-73-3 2-Dichloromethyl-1-nitro-4-trifluoromethyl-benzene 
• 122947-74-4 2-Dibromomethyl-1-nitro-4-trifluoromethyl-benzene 
• 67-64-1 acetone 
• 89303-21-9 2-Benzenesulfonylmethyl-1-nitro-4-trifluoromethyl-benzene 
• 117508-93-7 1-(5-trifluoromethyl-2-nitrophenyl)ethyl phenyl sulphone 
• 2367-02-4 1-phenoxy-4-(trifluoromethyl)benzene 
• 402-17-5 2-nitro-5-trifluoromethylphenol 
• 102512-07-2 N-(4-(trifluoromethyl)phenyl)hydroxylamine 
• 3284-64-8 1-nitro-4-(trichloromethyl)benzene 
• 34913-29-6 4,4′-bis(trifluoromethyl)azobenzene 

Relevant academic research and scientific papers

Aromatic trifluoromethylation catalytic in copper

Cu(i)-diamine complexes were found to catalyse the trifluoromethylation of aryl iodides. In the presence of a small amount of CuX (X = Cl, Br, I) and 1,10-phenanthroline (phen), the cross-coupling reactions of iodoarenes with trifluoromethylsilanes proceeded smoothly to afford trifluoromethylated aromatics in good yields.

Cross-Coupling through Ag(I)/Ag(III) Redox Manifold

In ample variety of transformations, the presence of silver as an additive or co-catalyst is believed to be innocuous for the efficiency of the operating metal catalyst. Even though Ag additives are required often as coupling partners, oxidants or halide scavengers, its role as a catalytically competent species is widely neglected in cross-coupling reactions. Most likely, this is due to the erroneously assumed incapacity of Ag to undergo 2e? redox steps. Definite proof is herein provided for the required elementary steps to accomplish the oxidative trifluoromethylation of arenes through AgI/AgIII redox catalysis (i. e. CEL coupling), namely: i) easy AgI/AgIII 2e? oxidation mediated by air; ii) bpy/phen ligation to AgIII; iii) boron-to-AgIII aryl transfer; and iv) ulterior reductive elimination of benzotrifluorides from an [aryl-AgIII-CF3] fragment. More precisely, an ultimate entry and full characterization of organosilver(III) compounds [K]+[AgIII(CF3)4]? (K-1), [(bpy)AgIII(CF3)3] (2) and [(phen)AgIII(CF3)3] (3), is described. The utility of 3 in cross-coupling has been showcased unambiguously, and a large variety of arylboron compounds was trifluoromethylated via [AgIII(aryl)(CF3)3]? intermediates. This work breaks with old stereotypes and misconceptions regarding the inability of Ag to undergo cross-coupling by itself.

Ipso Nitration of Aryl Boronic Acids Using Fuming Nitric Acid

The ipso nitration of aryl boronic acid derivatives has been developed using fuming nitric acid as the nitrating agent. This facile procedure provides efficient and chemoselective access to a variety of aromatic nitro compounds. While several activating agents and nitro sources have been reported in the literature for this synthetically useful transformation, this report demonstrates that these processes likely generate a common active reagent, anhydrous HNO3. Kinetic and mechanistic studies have revealed that the reaction order in HNO3 is >2 and indicate that the ?NO2 radical is the active species.

NOVEL METHOD FOR PRODUCING PERFLUOROALKYLATING AGENTS USING MONOHYDROPERFLUOROALKANE AS STARTING MATERIAL, AND METHOD FOR PRODUCING AROMATIC PERFLUOROALKYL COMPOUNDS USING THE SAME

To provide a simple method for producing silylated trifluoromethylcarbinol from trifluoromethane.SOLUTION: There is provided a method for producing a compound represented by the formula [1], in which the compound is obtained by reacting a monohydroperfluoroalkane, a carbonyl compound, and NaH in an organic solvent and then reacting the reaction solution with a silylating agent. [In the formula, RF is an alkyl group such as a linear chain of C1 to 2, and a perfluoroalkyl group in which all H on C is substituted with F; R1 and R2 are independently alkyl groups such as a linear chain of H or C1 to 2, or the like respectively; R1 and R2 may be integrated to form a ring; and R3, R4 and R5 are independently H or C1 to 2 linear alkyl groups, or the like respectively.]SELECTED DRAWING: None

NOVEL METHOD FOR PRODUCING PERFLUOROALKYLATING AGENTS USING MONOHYDROPERFLUOROALKANE AS STARTING MATERIAL, AND METHOD FOR PRODUCING AROMATIC PERFLUOROALKYL COMPOUND USING THE SAME

PROBLEM TO BE SOLVED: To provide a simple method for producing trifluoromethyltriol borate potassium from trifluoromethane. SOLUTION: There is provided a method for producing a compound represented by the formula [7], comprising: reacting a monohydroperfluoroalkane with a base and trialkyl borate in an organic solvent; and then reacting the reaction solution with triol. [In the formula, RF is an alkyl group such as a linear chain of C1-2, and a perfluoroalkyl group in which all H on C is substituted with F; R6 is H or a C1-2 linear alkyl group, or the like; M may be a metal or the like belonging to Group I, Group II, Group III, Group IV, Group V, Group VI, Group VII, Group VIII, Group IX, Group X, Group XI, Group XII, and Group XIII in the periodic table of elements, and they may be a single substance or a mixture of a plurality of substances and y corresponds to the oxidation number of the substance represented by M.] SELECTED DRAWING: None COPYRIGHT: (C)2021,JPOandINPIT

NOVEL METHOD FOR PRODUCING PERFLUOROALKYLATING AGENTS USING MONOHYDROPERFLUOROALKANE AS STARTING MATERIAL, AND METHOD FOR PRODUCING AROMATIC PERFLUOROALKYL COMPOUND USING THE SAME

PROBLEM TO BE SOLVED: To provide a method for producing an aromatic perfluoroalkyl compound using silylated trifluoromethyl carbinol. SOLUTION: There is provided a method for producing an aromatic perfluoroalkyl compound represented by the general formula [10], in which a compound represented by the formula [9] and a compound represented by the formula [1] are reacted in an organic solvent in the presence of a copper catalyst, a nitrogen ligand and a metal fluoride. R7-X...[9], RF-R7...[10] [In the formula, R7 is an aryl group or the like which may have a substituent; X is F, Cl, Br or I; RF is an alkyl group such as a linear chain of C1-2, and a perfluoroalkyl group in which all H on C is substituted with F; R1 and R2 are each independently H or a C1-2 linear alkyl group, or the like; R1 and R2 may be integrated to form a ring; and R3, R4 and R5 are each independently H or a C1-2 linear alkyl group, or the like.] SELECTED DRAWING: None COPYRIGHT: (C)2021,JPOandINPIT

Mechanistic Insight into Copper-Mediated Trifluoromethylation of Aryl Halides: The Role of CuI

The synthesis, characterization, and reactivity of key intermediates [Cu(CF3)(X)]-Q+ (X = CF3 or I, Q = PPh4) in copper-mediated trifluoromethylation of aryl halides were studied. Qualitative and quantitative studies showed [Cu(CF3)2]-Q+ and [Cu(CF3)(I)]-Q+ were not highly reactive. Instead, a much more reactive species, ligandless [CuCF3] or DMF-ligated species [(DMF)CuCF3], was generated in the presence of excess CuI. On the basis of these results, a general mechanistic map for CuI-promoted trifluoromethylation of aryl halides was proposed. Furthermore, on the basis of this mechanistic understanding, a HOAc-promoted protocol for trifluoromethylation of aryl halides with [Ph4P]+[Cu(CF3)2]- was developed.

Solvated Nickel Complexes as Stoichiometric and Catalytic Perfluoroalkylation Agents**

The acetonitrile-solvated [(MeCN)Ni(C2F5)3]? was prepared in order to compare and contrast its reactivity with the known [(MeCN)Ni(CF3)3]? towards organic electrophiles. Both [(MeCN)Ni(CF3)3]? and [(MeCN)Ni(C2F5)3]? successfully react with aryl iodonium and diazonium salts as well as alkynyl iodonium salts to give fluoroalkylated organic products. Electrochemical analysis of [(MeCN)NiII(C2F5)3]? suggests that, upon electro-oxidation to [(MeCN)nNiIII(C2F5)3], reductive homolysis of a perfluoroethyl radical occurs, with the concomitant formation of [(MeCN)2NiII(C2F5)2]. Catalytic C?H trifluoromethylations of electron-rich arenes were successfully achieved using either [(MeCN)Ni(CF3)3]? or the related [Ni(CF3)4]2?. Stoichiometric reactions of the solvated nickel complexes reveal that “ligandless” nickel is exceptionally capable of serving as reservoir of CF3 groups under catalytically relevant conditions.

Rational Design and Development of Low-Price, Scalable, Shelf-Stable and Broadly Applicable Electrophilic Sulfonium Ylide-Based Trifluoromethylating Reagents

The development of two highly reactive electrophilic trifluoromethylating reagents (trifluoromethyl)(4-nitrophenyl)bis(carbomethoxy)methylide (1g) and (trifluoromethyl)(3-chlorophenyl)bis(carbomethoxy)methylide (1j) through structure-activity study was described. Under mild conditions, reagent 1g reacted with β-ketoesters and silyl enol ethers to give α-trifluoromethylated-β-ketoesters or α-trifluoromethylated ketones in high yields. In addition, reagent 1g could serve as a trifluoromethyl radical for a variety of trifluoromethylative transformations under visible light irradiation, including radical trifluoromethylation of electron-rich indoles and pyrroles and sodium aryl sulfinates as well as trifluoromethylative difunctionalization with styrene derivatives. On the other hand, as a complimentary, under reductive coupling conditions, reagent 1j reacted with a variety of (hetero)aryl iodides for the formation of trifluoromethylated (hetero)arenes.

N-Nitroheterocycles: Bench-Stable Organic Reagents for Catalytic Ipso-Nitration of Aryl- And Heteroarylboronic Acids

Photocatalytic and metal-free protocols to access various aromatic and heteroaromatic nitro compounds through ipso-nitration of readily available boronic acid derivatives were developed using non-metal-based, bench-stable, and recyclable nitrating reagents. These methods are operationally simple, mild, regioselective, and possess excellent functional group compatibility, delivering desired products in up to 99% yield.