4422-95-1

Usage

Uses

Used in Specialty Organic Synthesis:
1,3,5-Benzenetricarboxylic acid chloride is used as a key intermediate in the synthesis of chiral azoaromatic dendrimeric systems. It is also used to study the structure of activated composite membranes containing organophosphorus extractants as carriers, which are important in the separation and purification of various chemical species.
Used in Self-Assembling Systems:
1,3,5-Benzenetricarboxylic acid chloride serves as the starting material for two tritopic amides derived from 3and 4-methylaminopyridine. These amides can self-assemble into nanoballs upon treatment with palladium(II) nitrate in DMSO, which is a promising approach for the development of new materials with unique properties and potential applications in various fields.

InChI:InChI=1/3C9H6O6.3ClH/c3*10-7(11)4-1-5(8(12)13)3-6(2-4)9(14)15;;;/h3*1-3H,(H,10,11)(H,12,13)(H,14,15);3*1H/p-3

Synthetic route

benzene-1,3,5-tricarboxylic acid (554-95-0) → 1,3,5-benzene tris(carbonyl chloride) (4422-95-1)

Conditions	Yield
With thionyl chloride In N,N-dimethyl-formamide for 8h; Heating;	100%
With thionyl chloride In N,N-dimethyl-formamide for 3h; Heating;	100%
With thionyl chloride; N,N-dimethyl-formamide for 3h; Heating / reflux;	100%

thionyl chloride (7719-09-7) + benzene-1,3,5-tricarboxylic acid (554-95-0) → 1,3,5-benzene tris(carbonyl chloride) (4422-95-1)

Conditions	Yield
In N,N-dimethyl-formamide for 8h; Reflux;	96%

1,3,5-tris(trichloromethyl)benzene (729-80-6) → 1,3,5-benzene tris(carbonyl chloride) (4422-95-1)

Conditions	Yield
With water; iron(III) chloride at 140℃;
With iron(III) chloride; benzene-1,3,5-tricarboxylic acid In melt at 100 - 110℃;

1,3,5-benzene tris(carbonyl chloride) (4422-95-1) + aniline (62-53-3) → N,N'N"-Trisphenyl-1,3,5-benzenetricarbonamide (71764-61-9)

Conditions	Yield
With pyridine In dichloromethane at 20℃; for 1h;	100%
Stage #1: 1,3,5-benzene tris(carbonyl chloride); aniline In pyridine; dichloromethane at 0℃; for 1h; Stage #2: In pyridine; dichloromethane at 0 - 20℃; for 4h;	90%
In 5,5-dimethyl-1,3-cyclohexadiene at 30℃; for 0.583333h; Sonication;	83%

1,3,5-benzene tris(carbonyl chloride) (4422-95-1) + Propargylamine (2450-71-7) → N1,N3,N5-tri-propargylbenzenetricarboxamide (902136-65-6)

Conditions	Yield
With N-ethyl-N,N-diisopropylamine In dichloromethane at 20℃; for 24h; Inert atmosphere;	100%
With dmap; triethylamine In dichloromethane at 0 - 20℃; for 3.25h;	73%
With triethylamine In dichloromethane at 0℃; for 3h;	44%

[4-(Diazo(phenyl)methyl)phenyl]methanol (1008513-62-9) + 1,3,5-benzene tris(carbonyl chloride) (4422-95-1) → C51H36N6O6 (1242462-30-1)

Conditions	Yield
With dmap; triethylamine In dichloromethane at 0 - 20℃;	100%

1,3,5-benzene tris(carbonyl chloride) (4422-95-1) + 8-(2-aminoethyleneaminocarbonyl)-octyl 4-O-(2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-β-D-galactopyranosyl)-2,3,6-tri-O-acetyl-β-D-galactopyranoside → C120H177N9O57

Conditions	Yield
With triethylamine In dichloromethane at 20℃; for 0.166667h; Acylation;	99%

1,3,5-benzene tris(carbonyl chloride) (4422-95-1) + tert-butyl 3-[(2-tert-butoxycarbonyl-ethyl)-(3-hydroxy-propyl)-amino]-propionate (644968-23-0) → benzene-1,3,5-tricarboxylic acid tris-{3-[bis-(2-tert-butoxycarbonyl-ethyl)-amino]-propyl} ester

Conditions	Yield
With dmap In toluene for 4h; Heating;	99%
Stage #1: tert-butyl 3-[(2-tert-butoxycarbonyl-ethyl)-(3-hydroxy-propyl)-amino]-propionate With dmap In toluene for 3h; Reflux; Stage #2: 1,3,5-benzene tris(carbonyl chloride) In toluene for 6h; Reflux;	60%
With dmap In toluene at 110℃; for 6h;

H2NC3H6Si(CH3)2C5H4FeC5H3[P(C6H5)2]CH(CH3)P(C6H11)2 (182227-33-4) + 1,3,5-benzene tris(carbonyl chloride) (4422-95-1) → C132H171Si3P6N3O3Fe3

Conditions	Yield
In not given slight excess of ferrocenyl diphosphine; chromy.;	99%

(C5H4Si(CH3)2(CH2)3NH2)Fe(C5H3(P(C6H5)2)(CHCH3P(C6H11)2)) + 1,3,5-benzene tris(carbonyl chloride) (4422-95-1) → ((C5H4Si(CH3)2CH2CH2CH2NHCO)Fe(C5H3(P(C6H5)2)(CHCH3P(C6H11)2)))3C6H3

Conditions	Yield
With triethylamine In not given	99%

1,3,5-benzene tris(carbonyl chloride) (4422-95-1) + 4-(salicylideneamino)benzyl alcohol → tris[4-(salicylaldimine)benzyl]benzene-1,3,5-tricarboxylate

Conditions	Yield
With triethylamine In dichloromethane at 20℃;	99%

1,3,5-benzene tris(carbonyl chloride) (4422-95-1) → benzene-1,3,5-tris(carboperoxoic) acid (63556-80-9)

Conditions	Yield
Stage #1: 1,3,5-benzene tris(carbonyl chloride) With methanesulfonic acid at 50℃; Stage #2: With dihydrogen peroxide In water at 50℃; for 0.5h;	99%

1,3,5-benzene tris(carbonyl chloride) (4422-95-1) + <3--1,3,5-triazin-2-yl>amino>-5-bromobenzoyl>-N-<<4-(1,1-dimethylethyl)phenyl>methyl>amino>phenyl>amine (147355-09-7) → N,N',N''-tris<3--1,3,5-triazin-2-yl>amino>-5-bromobenzoyl>-N-<<4-(1,1-dimethylethyl)phenyl>methyl>amino>phenyl>-1,3,5-benzenetricarboxamide (129001-73-6)

Conditions	Yield
With N-ethyl-N,N-diisopropylamine In dichloromethane for 1h; Ambient temperature;	98%

2-furoic acid hydrazide (3326-71-4) + 1,3,5-benzene tris(carbonyl chloride) (4422-95-1) → C24H18N6O9

Conditions	Yield
With potassium carbonate In tetrahydrofuran; water	98%

1,3,5-benzene tris(carbonyl chloride) (4422-95-1) + p-toluic hydrazide (3619-22-5) → C33H30N6O6

Conditions	Yield
With potassium carbonate In tetrahydrofuran; water	98%

1,3,5-benzene tris(carbonyl chloride) (4422-95-1) + N-phenyl-1,2-benzenediamine (534-85-0) → N1,N3,N5-tris(2-(phenylamino)phenyl)benzene-1,3,5-tricarboxamide (950766-71-9)

Conditions	Yield
In tetrahydrofuran at 20℃; Industrial scale;	98%
In methylpyrrolidin-2-one; 1- (NMP) at 20 - 50℃; for 2h; Heating / reflux;	70%
In 1-methyl-pyrrolidin-2-one at 20 - 50℃; for 2.5h;

1-hydroxy-3,5-bis(1-oxa-2-aza-2-[3,5-bis(6-[(S(P))-1-diphenylphosphino-2-[1R-(dicyclohexylphosphino)ethyl]-1'-ferrocenyl]-6-dimethyl-1-oxo-2-aza-6-silahexyl)phenyl])benzene*2.5H2O + 1,3,5-benzene tris(carbonyl chloride) (4422-95-1) → 12-cascade:benzene[3-1,3,5]:(5-(1-oxo-2-oxa)-1,3-phenylene):(5-(1-oxo-2-aza)-1,3-phenylene):1'-(1-dimethyl-6-oxo-5-aza-1-silahexyl)-(S(P))-1-diphenylphosphino-2-[1R-(dicyclohexylphosphino)-ethyl]ferrocene

Conditions	Yield
With 4-pyrrolidin-1-ylpyridine In dichloromethane react. ferrocene, 4-(pyrrolidino)pyridine, and benzene-1,3,5-tricarboxylic acid trichloride in CH2Cl2, 2 h at room temp.; flash chromy. on silica (hexane-EtOAc + 1 % NEt3); elem. anal.;	98%

C37H52N4OS6 + 1,3,5-benzene tris(carbonyl chloride) (4422-95-1) → C120H156N12O6S18

Conditions	Yield
With triethylamine In dichloromethane at 0 - 20℃; Inert atmosphere;	98%

1,3,5-benzene tris(carbonyl chloride) (4422-95-1) + 2,2-dimethoxyethylamine (22483-09-6) → 1,3,5-tris(2,2-dimethoxyethylaminocarbonyl)benzene

Conditions	Yield
With N-ethyl-N,N-diisopropylamine In chloroform at 20℃; for 24h;	98%
With N-ethyl-N,N-diisopropylamine In chloroform at -15 - 20℃; for 24h;	98%

fluorobenzene (462-06-6) + 1,3,5-benzene tris(carbonyl chloride) (4422-95-1) → [3,5-bis(4-fluorobenzoyl)phenyl](4-fluorophenyl)methanone (267668-44-0)

Conditions	Yield
Stage #1: fluorobenzene; 1,3,5-benzene tris(carbonyl chloride) With aluminum (III) chloride at 20℃; for 12h; Friedel-Crafts Alkylation; Stage #2: at 90℃; for 2h;	98%
With aluminum (III) chloride at 20 - 90℃;	98%
With aluminum (III) chloride at 85 - 97℃; for 2h;	92.7%

1,3,5-benzene tris(carbonyl chloride) (4422-95-1) + 4-hydroxy-benzaldehyde (123-08-0) → C30H18O9

Conditions	Yield
With triethylamine In tetrahydrofuran at 10 - 20℃; for 2h;	98%

2-thienylhydrazide (2361-27-5) + 1,3,5-benzene tris(carbonyl chloride) (4422-95-1) → C24H18N6O6S3

Conditions	Yield
With potassium carbonate In tetrahydrofuran; water	97%

4-aminopyridine (504-24-5) + 1,3,5-benzene tris(carbonyl chloride) (4422-95-1) → N1,N3,N5-tris(pyridin-4-yl)benzene-1,3,5-tricarboxamide (725274-03-3)

Conditions	Yield
In N,N-dimethyl-formamide at 20℃;	97%
In N,N-dimethyl-formamide at 20℃;	97%
In N,N-dimethyl-formamide at 20℃; for 12h;	96%

1-(3-(chloromethyl)phenyl)-2-hydroxy-2-methylpropan-1-one (1308332-52-6) + 1,3,5-benzene tris(carbonyl chloride) (4422-95-1) → C42H42O12 (1399234-66-2)

Conditions	Yield
With dmap; triethylamine In dichloromethane at 0℃; for 2h; Inert atmosphere;	97%
With dmap; triethylamine In dichloromethane at 0 - 20℃; for 2h; Inert atmosphere;	97%

1,3,5-benzene tris(carbonyl chloride) (4422-95-1) + methyl (L)-leucinate hydrochloride (7517-19-3) → C30H45N3O9 (905751-50-0)

Conditions	Yield
With triethylamine In dichloromethane at 20℃; for 18h;	97%

1,3,5-benzene tris(carbonyl chloride) (4422-95-1) + N-acetyl-N-(8-amino-3,6-dioxaoctyl)-O-benzylhydroxylamine (126385-15-7) → N,N',N''-tris<8-acetyl(benzyloxy)amino-3,6-dioxaoctyl>benzene-1,3,5-tricarboxamide (126385-21-5)

Conditions	Yield
With triethylamine In dichloromethane 0 deg C, 1 h, Rt, 2 h;	96%

1,3,5-benzene tris(carbonyl chloride) (4422-95-1) + benzylamine (100-46-9) → N1,N3,N5- tribenzylbenzene-1,3,5-tricarboxamide (86375-10-2)

Conditions	Yield
In toluene	96%
With triethylamine In chloroform at 20℃; for 0.0222222h; Flow reactor;	90%

1,3,5-benzene tris(carbonyl chloride) (4422-95-1) + histamine (51-45-6) → N,N',N''-tris(2-(1H-imidazole-5-yl)ethyl)benzene-1,3,5-tricarboxamide

Conditions	Yield
With triethylamine In chloroform a) RT, 20 h, b) reflux, 2 h;	96%

(1R,2S)-2-Amino-1,2-diphenylethanol (23190-16-1) + 1,3,5-benzene tris(carbonyl chloride) (4422-95-1) → 1,3,5-{[(1S,2R)-PhCH(OH)CH(Ph)]NHC(O)}3C6H3

Conditions	Yield
With triethylamine In dichloromethane for 4h; Heating;	96%
With triethylamine In dichloromethane Heating;

(S)-valinol (2026-48-4) + 1,3,5-benzene tris(carbonyl chloride) (4422-95-1) → N,N',N''-tris[(1S)-1-hydroxymethyl-2-methylpropyl]-1,3,5-benzenetricarboxamide

Conditions	Yield
With triethylamine In dichloromethane at 0 - 20℃; Inert atmosphere;	96%
With triethylamine In dichloromethane Heating;
With triethylamine In dichloromethane at 20℃; for 4 - 6h;
With triethylamine In dichloromethane at 0 - 20℃; Inert atmosphere;

1,3,5-benzene tris(carbonyl chloride) (4422-95-1) + 4-amino-phenol (123-30-8) → 1,3,5-tris((4'-hydroxyphenyl)carbamoyl)benzene (1216665-32-5)

Conditions	Yield
With methyloxirane In N,N-dimethyl acetamide at 0 - 20℃; for 6.5h; Inert atmosphere;	96%

C17H35NO2S*C7H8O3S + 1,3,5-benzene tris(carbonyl chloride) (4422-95-1) → tri-N-[(D)-(3-thio-butyl)dodecyloxycarbonymethyl]benzene-1,3,5-tricarboxamide

Conditions	Yield
With triethylamine In dichloromethane at 0 - 20℃; for 36 - 42h; Inert atmosphere; Schlenk technique;	96%

Upstream product

• 554-95-0 benzene-1,3,5-tricarboxylic acid 
• 7719-09-7 thionyl chloride 
• 729-80-6 1,3,5-tris(trichloromethyl)benzene 

Downstream Products

• 118927-16-5 1,3,5-tris(3,5-dimethylpyrazolyl-1-carbonyl)benzene 
• 111798-88-0 benzene-1,3,5-tricarboxylic acid tris-(2-nitro-anilide) 
• 76098-43-6 Benzene-1,3,5-tricarboxylic acid tris-[1-chloro-1-pyrrolidin-1-yl-meth-(Z)-ylideneamide] 
• 98603-10-2 benzene-1,3,5-tris(10-oxoundecyl)tricarboxylate 
• 79087-33-5 N,N',N''-trimethylbenzene-1,3,5-tricarboxamide 
• 91452-12-9 tris(3-chloro-1-propyl)benzene-13,5-tricarboxylate 
• 161579-53-9 C₆₀H₆₆N₆O₁₈ 
• 171253-95-5 1,3,5-tris<<γ-(3-benzyloxy-2-methyl-4-pyridinon-1-yl)propyl>carbamido>benzene 

Relevant academic research and scientific papers

Synthesis and geometric structure of N, N, N'-tris(Benzoyl)trimesinic acid dihydrazide

N, N, N'-Tris(benzoyl) trimesinic acid dihydrazide was synthesized from benzoyl hydrazine and trischloride and the structures of N,N,N'- tris(benzoyl) trimesinic acid dihydrazide had been characterized by Fourier transform infrared spectroscopy, 1H nuclear magnetic resonance techniques. The reaction condition was investigated by orthogonal experiment and the optimized reaction condition by orthogonal experiment is molar ratio of benzoyl hydrazine: trischloride 5:1, reaction time 4 h, reaction temperature 70°C, the yield is 65.7 %. SEM showed the particles of N,N,N'-tris(benzoyl)trimesinic acid dihydrazide were not completely regular and the average size of the particles was 3-4 μm. At the same time, the optimized geometric structure of N,N,N'-tris(benzoyl)trimesinic acid dihydrazide was carried out by theoretical calculations using the semiempirical method PM3.

Star-Shaped Conjugated Molecules with Oxa- or Thiadiazole Bithiophene Side Arms

Star-shaped conjugated molecules, consisting of a benzene central unit symmetrically trisubstituted with either oxa- or thiadiazole bithiophene groups, were synthesized as promising molecules and building blocks for application in (opto)electronics and electrochromic devices. Their optical (Eg(opt)) as well as electrochemical (Eg(electro)) band gaps depended on the type of the side arm and the number of solubilizing alkyl substituents. Oxadiazole derivatives showed Eg(opt) slightly below 3 eV and by 0.2 eV larger than those determined for thiadiazole-based compounds. The presence of alkyl substituents in the arms additionally lowered the band gap. The obtained compounds were efficient electroluminophores in guest/host-type light-emitting diodes. They also showed a strong tendency to self-organize in monolayers deposited on graphite, as evidenced by scanning tunneling microscopy. The structural studies by X-ray scattering revealed the formation of supramolecular columnar stacks in which the molecules were organized. Differences in macroscopic alignment in the specimen indicated variations in the self-assembly mechanism between the molecules. The compounds as trifunctional monomers were electrochemically polymerized to yield the corresponding polymer network. As shown by UV/Vis-NIR spectroelectrochemical studies, these networks exhibited reversible electrochromic behavior both in the oxidation and in the reduction modes.

Uncommon hexagonal microtubule based gel from a simple trimesic amide

A small molecule of N,N′,N″-tris(3-methylpyridyl)-trimesic amide was assembled into a novel hexagonal microtube through intermolecular hydrogen bonds, and simultaneously formed a gel system in H2O-THF mixed solvent. Tuning gelator concentration or the preparation method can effectively control the size of the hexagonal tubes. The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2008.

Cobalt Metallogel Interface for Selectively Sensing l -Tryptophan among Essential Amino Acids

The development of metallogels widens the span of sensing activity as it opens new opportunities to develop chemosensors through metal-ligand interactions. Herein, a new nitrile-substituted 1,3,5-tricarboxamide-based gelator G4 has been fabricated and shows aggregate-induced enhanced emission (AIEE) after gelation in the presence of water. A dimethylformamide (DMF) solution of the gelator shows rapid crystallization, but addition of water to a DMF solution of gelator G4 leads to gelation at room temperature. In addition, gelator G4 was used for the formation of metallogels, and among them, the cobalt metallogel has been found to be effective for sensing l-tryptophan in the gel state through the quenching of AIEE. Interestingly, the gel is also effective in sensing bovine serum albumin protein at the nanomolar level, which contains an l-tryptophan residue. The limit of detection of Co(II)G4 for selective sensing of tryptophan has been found to be 2.4 × 10-8 M. To the best of our knowledge, there have been no reports to date of a metallogel being utilized to discriminate and selectively sense an amino acid and a protein. The gelation properties of the organic gelator molecule and metallogels have been explored through various spectroscopic tools and physicochemical experiments.

Tuning of Bistability, Thermal Stability of the Metastable States, and Application Prospects in the C3-Symmetric Designs of Multiple Azo(hetero)arenes Systems

Light-responsive molecular systems with multiple photoswitches in C3-symmetric designs have enormous application potential. The design part of such molecular systems is critical due to its influence in several properties associated with the photoswitches. In order to tune, and in the evaluation of the design–property relationship, we synthesized 18 tripodal systems with variations in the core, linkers, connectivity, and azo(hetero)arene photoswitches. Through extensive spectroscopic and computational studies, we envisaged the factors controlling near-quantitative photoisomerization in both the directions (bistability) and the thermal stability of the metastable states. Furthermore, we also evaluated the impact of designs in obtaining reversible photo-responsive sol-gel phase transitions, solvatochromism, photo- and thermochromism.

Br?nsted acid-catalyzed chlorination of aromatic carboxylic acids

The chlorination of aromatic carboxylic acids with SOCl2 has been effectively performed by reacting with a Br?nsted acid as the catalyst. Based on this discovery, an efficient catalytic method that is cheaper than traditional catalytic methods was developed. 20 substrates were chlorinated offering excellent yields in a short reaction time. And the SOCl2/Br?nsted acid system has been used in a larger scale preparative reaction. A dual activation mechanism was proposed to prove the irreplaceable system of SOCl2/Br?nsted acid.

Instant Photochromism Caused by Radical Formation in Photocatalytic Decarboxylation of Dihydrothiazole Derivative?

A pair of new enantiomeric compounds, (R)/(S)-1,3,5-benzene-triyl-2,2',2”-tris(4,5-dihydrothiazole-4-carboxylic acid) (H3LRRR and H3LSSS) are synthesized in one step synthetic route with high yield. Instant photochromism has been investigated to elaborate the photocatalytic decarboxylation of the dihydrothiazole derivative by electron paramagnetic resonance spectroscopy (EPR), photoluminescence (PL), FT-IR, high resolution mass spectra, X-ray photoelectron spectroscopy and UV-Vis spectroscopic techniques. The results indicate that the photochromic transformation is originated from the formation of the radical during the photocatalytic decarboxylation of the 4,5-dihydrothiazole-4-carboxylic acid units.

Citrate plasticizer

The invention discloses a citrate plasticizer and a preparation method thereof, and the preparation method of citrate comprises the following steps: firstly, citric acid and alcohol react to prepare citric acid triester, and then dianhydride acylation is carried out to prepare carboxyl-containing citric acid triester. After chlorination, the carboxyl-containing citric acid triester and the tris(2-ethoxyl) isocyanurate are subjected to esterification reaction to prepare triester citrate containing the isocyanurate. According to the present invention, the preparation method has characteristics of simple operation, wide raw material source and mild reaction condition, and meets the industrial production, the prepared triester citrate containing isocyanurate has a good plasticizing effect and excellent thermal stability, low-temperature flexibility, solvent extraction resistance, migration resistance and flame retardance, and can be widely applied to plastic rubber plasticizers.

C3 The symmetry contains a chiral ligand H3L of an amide bond. Preparation method and application

The invention discloses C. 3 Chiral ligand H with symmetric amide bond3 L Relates to the technical field of material chemistry and chiral chemistry. The invention further provides the chiral ligand H. 3 L Preparation method and application thereof. The present invention has the advantage that the chiral ligand H of the present invention is a chiral ligand. 3 The L has a higher C. 3 The symmetric and flexible amide group enables coordination of the lanthanide metal ions with high coordination number and high oxygen affinity to be assembled into a novel structure-structure lanthanide metal chiral porous coordination cage. Moreover, the abundant chiral amide groups and amino acid residues on the ligand framework can be directly introduced into the synthesized lanthanide metal chiral porous coordination cage, thereby being beneficial to generating multiple chiral recognition sites and unique chiral microenvironments which mimic the biological enzyme binding pocket and further realize the purpose of high enantioselectivity separation of a series of chiral small molecule compounds.

Homochiral Dodecanuclear Lanthanide "cage in Cage" for Enantioselective Separation

It is extremely difficult to anticipate the structure and the stereochemistry of a complex, particularly when the ligand is flexible and the metal node adopts diverse coordination numbers. When trivalent lanthanides (LnIII) and enantiopure amino acid ligands are utilized as building blocks, self-assembly sometimes yields rare chiral polynuclear structures. In this study, an enantiopure carboxyl-functionalized amino acid-based ligand with C3 symmetry reacts with lanthanum cations to give a homochiral porous coordination cage, (Δ/λ)12-PCC-57. The dodecanuclear lanthanide cage has an unprecedented octahedral "cage-in-cage"framework. During the self-assembly, the chirality is transferred from the enantiopure ligand and fixed by the binuclear lanthanide cluster to give 12 metal centers that have either Δor λ homochiral stereochemistry. The cage exhibits excellent enantioselective separation of racemic alcohols, 2,3-dihydroquinazolinones, and multiple commercially available drugs. This finding exhibits a rare example of a multinuclear lanthanide complex with a dual-walled topology and homochirality. The highly ordered self-assembly and self-sorting of flexible amino acids and lanthanides shed light on the chiral transformation between different complicated artificial systems that mimic natural enzymes.