3274-12-2

Basic information

• Product Name: 4-METHYL-4-TRICHLOROMETHYL-2,5-CYCLOHEXADIEN-1-ONE)
• Synonyms: 4-METHYL-4-TRICHLOROMETHYL-2,5-CYCLOHEXADIEN-1-ONE);4-Methyl-4-(trichloromethyl)-2,5-cyclohexadiene-1-one;4-Trichloromethyl-4-methyl-2,5-cyclohexadien-1-one;4-Methyl-4-(trichloroMeth yl)-2,5-cyclohexadienone;4-Methyl-4-(trichloroMethyl)cyclohexa-2,5-dien-1-one;2,5-Cyclohexadien-1-one,4-Methyl-4-(trichloroMethyl)-;NSC 407523;4-Methyl-4-(trichloromethyl)cyclohexa-2,5-dienone
• CAS NO: 3274-12-2
• Molecular Formula: C₈H₇Cl₃O
• Molecular Weight: 225.499580
• Mol File: 3274-12-2.mol
• Article Data: 4

Chemical Properties

• Melting Point: 103-104℃ (ligroine )
• Boiling Point: 289 °C at 760 mmHg
• Flash Point: 120.6 °C
• Appearance: /
• Density: 1.419 g/cm³
• Vapor Pressure: 0.00226mmHg at 25°C
• Refractive Index: 1.548
• Storage Temp.: 2-8°C
• CAS DataBase Reference: 4-METHYL-4-TRICHLOROMETHYL-2,5-CYCLOHEXADIEN-1-ONE)(CAS DataBase Reference)
• NIST Chemistry Reference: 4-METHYL-4-TRICHLOROMETHYL-2,5-CYCLOHEXADIEN-1-ONE)(3274-12-2)
• EPA Substance Registry System: 4-METHYL-4-TRICHLOROMETHYL-2,5-CYCLOHEXADIEN-1-ONE)(3274-12-2)

Safety Data

• Hazardous Substances Data: 3274-12-2(Hazardous Substances Data)

Usage

General Description

4-Methyl-4-trichloromethyl-2,5-cyclohexadien-1-one is a synthetic chemical compound with the molecular formula C8H7Cl3O. It is a highly reactive and volatile compound known for its strong odor and potential use as a pesticide and antimicrobial agent. 4-METHYL-4-TRICHLOROMETHYL-2,5-CYCLOHEXADIEN-1-ONE) is classified as a trichloromethyl ketone, and its chemical structure includes a cyclohexadienone ring with a methyl group and three chlorine atoms attached. It is important to handle this chemical with caution, as it is known to be toxic and may pose health risks if not used properly.

InChI:InChI=1/C8H7Cl3O/c1-7(8(9,10)11)4-2-6(12)3-5-7/h2-5H,1H3

Synthetic route

tetrachloromethane (56-23-5) + p-cresol (106-44-5) → 4-methyl-4-(trichloromethyl)cyclohexa-2,5-dien-1-one (3274-12-2)

Conditions	Yield
With aluminum (III) chloride In 1,2-dichloro-ethane at 5 - 38℃; for 2h; Solvent; Temperature;	34%
With aluminium trichloride In carbon disulfide at 45℃; for 2h;	30%
With aluminium trichloride at 100℃;

tetrachloromethane (56-23-5) + p-cresol (106-44-5) → 4-methyl-4-(trichloromethyl)cyclohexa-2,5-dien-1-one (3274-12-2) + 4-chloro-5-methyl-2,4,6-cycloheptatrien-1-one (95258-01-8)

Conditions	Yield
With aluminium trichloride Heating;	A 12% B 0.007 g

tetrachloromethane (56-23-5) + aluminium trichloride (7446-70-0) + p-cresol (106-44-5) → 4-methyl-4-(trichloromethyl)cyclohexa-2,5-dien-1-one (3274-12-2)

4-methyl-4-(trichloromethyl)cyclohexa-2,5-dien-1-one (3274-12-2) → 4-methyl-4-trichloromethyl-2,5-cyclohexadien-1-one oxime (81294-21-5)

Conditions	Yield
With hydroxylamine hydrochloride In pyridine; ethanol at 85℃; for 5h;	94%
With ethanol; hydroxylamine hydrochloride; water Behandeln mit Natronlauge;

4-methyl-4-(trichloromethyl)cyclohexa-2,5-dien-1-one (3274-12-2) + 4-methoxy-aniline (104-94-9) → N-(4-methylphenyl)-4-methoxyaniline (39253-43-5) + (4-Methoxy-phenyl)-(4-methyl-4-trichloromethyl-cyclohexa-2,5-dienylidene)-amine (129332-85-0)

Conditions	Yield
With toluene-4-sulfonic acid In toluene Heating; 24-28 h;	A 4% B 87%

4-methyl-4-(trichloromethyl)cyclohexa-2,5-dien-1-one (3274-12-2) + aniline (62-53-3) → 4-methyldiphenylamine (620-84-8) + 1-Phenylimino-4-methyl-4-trichloromethyl-2,5-cyclohexadiene (51590-71-7)

Conditions	Yield
With toluene-4-sulfonic acid In toluene Heating; 24-28 h;	A 12% B 86%
With toluene-4-sulfonic acid In toluene Heating; 24-28 h, other activating reagent; other arylamines;	A 12% B 84%

bis(ethylene)rhodium(I) chloride dimer + 4-methyl-4-(trichloromethyl)cyclohexa-2,5-dien-1-one (3274-12-2) → (C8H7Cl3O)2Rh2Cl2 (186820-98-4)

Conditions	Yield
In dichloromethane stirring (3 h, 20°C); evapn., washing (Et2O), drying (vac.); elem. anal.;	80%

4-methyl-4-(trichloromethyl)cyclohexa-2,5-dien-1-one (3274-12-2) + p-aminoiodobenzene (540-37-4) → (4-Iodo-phenyl)-(4-methyl-4-trichloromethyl-cyclohexa-2,5-dienylidene)-amine (129332-88-3)

Conditions	Yield
With toluene-4-sulfonic acid In toluene Heating; 24-28 h;	78%

4-methyl-4-(trichloromethyl)cyclohexa-2,5-dien-1-one (3274-12-2) + cyclopenta-1,3-diene (542-92-7) → 1-cyclopentadienylidene-4-methyl-4-trichloromethylcyclohexa-2,5-diene (185307-47-5)

Conditions	Yield
With pyrrolidine In methanol at 20℃; for 1.5h; Condensation;	78%

4-methyl-4-(trichloromethyl)cyclohexa-2,5-dien-1-one (3274-12-2) + cyclopropylmagnesium bromide (23719-80-4) → C11H13Cl3O

Conditions	Yield
Grignard Reaction;	75%

4-methyl-4-(trichloromethyl)cyclohexa-2,5-dien-1-one (3274-12-2) → 4-chloro-5-methyl-2,4,6-cycloheptatrien-1-one (95258-01-8)

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0) In benzene at 20℃; for 24h;	65%

4-methyl-4-(trichloromethyl)cyclohexa-2,5-dien-1-one (3274-12-2) + 1,1-bis-(4-aminophenyl)cyclohexane (3282-99-3) → 1-<4-<1-(4'-p-Toluidinophenyl)cyclohexyl>imino>-4-methyl-4-trichloromethyl-2,5-cyclohexadiene (131822-52-1) + C34H32Cl6N2 (129332-89-4)

Conditions	Yield
With toluene-4-sulfonic acid In toluene Heating; 24-28 h;	A 12% B 60%

4-methyl-4-(trichloromethyl)cyclohexa-2,5-dien-1-one (3274-12-2) + 2-Hydroxy-4-methylanilin (2835-98-5) → 5-methyl-2-(p-tolylamino)phenol + 5-methyl-2-(4-methyl-4-trichloromethylcyclohexa-2,5-dienylideneamino)phenol

Conditions	Yield
With sodium sulfate In toluene for 2.5h; Heating;	A 0.9% B 34.8%

tetrachloromethane (56-23-5) + 4-methyl-4-(trichloromethyl)cyclohexa-2,5-dien-1-one (3274-12-2) → 2-Chloro-4,5-dimethyl-4-trichloromethyl-2,5-cyclohexadiene-1-one (128729-12-4)

Conditions	Yield
With aluminium trichloride at 60 - 65℃; for 2h;	30%

4-methyl-4-(trichloromethyl)cyclohexa-2,5-dien-1-one (3274-12-2) → 3,3-dichloro-3a,4'-dimethyl-4'-trichloromethyl-2,3,3a,6,7,8-hexahydrospiro(benzofuran-2,1'-cyclohexa-2',5'-dien)-6-one

Conditions	Yield
With n-butyllithium In tetrahydrofuran; hexane at -60 - 0℃;	24%

4-methyl-4-(trichloromethyl)cyclohexa-2,5-dien-1-one (3274-12-2) + dimedone (126-81-8) → 4,4-dimethyl-1-(4-trichloromethyl-4-methylcyclohexa-2,5-dienylidene)cyclohexane-2,6-dione (117780-33-3)

Conditions	Yield
With piperidine In ethanol for 24h; Heating;	7%

carbon disulfide (75-15-0) + 4-methyl-4-(trichloromethyl)cyclohexa-2,5-dien-1-one (3274-12-2) → 2,3,5,6-tetrachloro-4-methyl-4-trichloromethyl-cyclohexanone (861316-50-9)

Conditions	Yield
beim Chlorieren im Sonnenlicht;

methyl magnesium iodide (917-64-6) + 4-methyl-4-(trichloromethyl)cyclohexa-2,5-dien-1-one (3274-12-2) → 1,4-dimethyl-4-trichloromethyl-2,5-cyclohexadien-1-ol (343855-23-2)

4-methyl-4-(trichloromethyl)cyclohexa-2,5-dien-1-one (3274-12-2) + 4-nitrophenylhydrazine hydrochloride (636-99-7) → 4-methyl-4-trichloromethyl-cyclohexa-2,5-dienone-(4-nitro-phenylhydrazone)

Conditions	Yield
With ethanol

4-methyl-4-(trichloromethyl)cyclohexa-2,5-dien-1-one (3274-12-2) + lithium acetylide (70277-75-7) → 1-ethynyl-4-methyl-4-trichloromethyl-cyclohexa-2,5-dienol (102541-41-3)

4-methyl-4-(trichloromethyl)cyclohexa-2,5-dien-1-one (3274-12-2) + ethoxyethynylmagnesium bromide (36678-63-4) → 3,3,3-trichloro-2-p-tolyl-propionic acid ethyl ester (7498-59-1)

Conditions	Yield
With benzene Behandeln des Reaktionsprodukts in Aether mit wss. H2SO4;

4-methyl-4-(trichloromethyl)cyclohexa-2,5-dien-1-one (3274-12-2) + phenylmagnesium bromide → 4-methyl-1-phenyl-4-trichloromethyl-cyclohexa-2,5-dienol (100717-00-8)

4-methyl-4-(trichloromethyl)cyclohexa-2,5-dien-1-one (3274-12-2) → 4-chloro-2-methylbenzoic acid (7499-07-2)

Conditions	Yield
With PPA
With phosphorus pentachloride Destillieren im Vakuum und Verseifen des Destillats mit Natronlauge;

4-methyl-4-(trichloromethyl)cyclohexa-2,5-dien-1-one (3274-12-2) → 4-methyl-4-trichloromethyl-cyclohexa-2,5-dienol (13630-61-0)

Conditions	Yield
With aluminum isopropoxide; isopropyl alcohol at 120℃;
With sodium tetrahydroborate

4-methyl-4-(trichloromethyl)cyclohexa-2,5-dien-1-one (3274-12-2) → 2-chloro-4-methyl-4-trichloromethyl-cyclohexa-2,5-dienone (129399-22-0)

Conditions	Yield
With tetrachloromethane; iodine; chlorine Kochen des Reaktionsprodukts mit Kaliumacetat und Eisessig;
With iodine; chlorine Irradiation;

4-methyl-4-(trichloromethyl)cyclohexa-2,5-dien-1-one (3274-12-2) → 2,6-dibromo-4-methyl-4-trichloromethyl-cyclohexa-2,5-dienone (91019-94-2)

Conditions	Yield
With bromine Irradiation.mit Sonnenlicht;
With bromine; iodine

4-methyl-4-(trichloromethyl)cyclohexa-2,5-dien-1-one (3274-12-2) → 2,3,5,6-tetrachloro-4-methyl-4-trichloromethyl-cyclohexanone (861316-50-9)

Conditions	Yield
With carbon disulfide beim Chlorieren;

4-methyl-4-(trichloromethyl)cyclohexa-2,5-dien-1-one (3274-12-2) + ethyl bromoacetate (105-36-2) → (4-methyl-4-trichloromethyl-cyclohexa-2,5-dienyliden)-acetic acid ethyl ester (104850-09-1)

Conditions	Yield
With toluene; zinc; benzene Behandeln des Reaktionsprodukts mit Ameisensaeure;

4-methyl-4-(trichloromethyl)cyclohexa-2,5-dien-1-one (3274-12-2) + ethyl bromoacetate (105-36-2) → (1-hydroxy-4-methyl-4-trichloromethyl-cyclohexa-2,5-dienyl)-acetic acid ethyl ester (100389-43-3)

Conditions	Yield
With zinc; benzene

methanol (67-56-1) + 4-methyl-4-(trichloromethyl)cyclohexa-2,5-dien-1-one (3274-12-2) → trans-5-Methoxy-4-<1.1-dichlor-propenyl-(2)>-cyclopenten-(2)-on (20060-24-6)

Conditions	Yield
at 0℃; for 1h; Product distribution; Irradiation; temperature dependence investigation;
With calcium carbonate Irradiation;

4-methyl-4-(trichloromethyl)cyclohexa-2,5-dien-1-one (3274-12-2) → 4-Methyl-4-trichlormethylcyclohex-2-en-1-on (31236-72-3)

Conditions	Yield
With Wilkinson's catalyst; hydrogen

Upstream product

• 56-23-5 tetrachloromethane 
• 106-44-5 p-cresol 
• 7446-70-0 aluminium trichloride 

Downstream Products

• 861316-50-9 2,3,5,6-tetrachloro-4-methyl-4-trichloromethyl-cyclohexanone 
• 31236-72-3 4-Methyl-4-trichlormethylcyclohex-2-en-1-on 
• 13630-15-4 1-Chlor-3-methyl-4-trichlormethyl-benzol 
• 30858-08-3 4-methyl-4-trichloromethyl-cyclohexanone 
• 13630-14-3 1-Methyl-1-trichlormethyl-4,4-dichlor-cyclohexadien-(2,5) 
• 128729-12-4 2-Chloro-4,5-dimethyl-4-trichloromethyl-2,5-cyclohexadiene-1-one 
• 106-44-5 p-cresol 
• 131822-51-0 N,N'-Bis-(4-methyl-4-trichloromethyl-cyclohexa-2,5-dienylidene)-benzene-1,4-diamine 
• 129332-87-2 (4-Methyl-4-trichloromethyl-cyclohexa-2,5-dienylidene)-(4-phenoxy-phenyl)-amine 
• 4413-31-4 Methylchlor 
• 19671-08-0 2-<2,4-Dichlor-phenyl>-2-<4-methyl-phenyl>-1,1,1-trichlor-aethan 
• 6956-79-2 2,6-dichloro-4-methyl-4-trichloromethyl-cyclohexa-2,5-dienone 
• 39594-84-8 4-methylphenyl chlorothioformate 
• 2976-38-7 p-tolyltrichloromethylsulfide 

Relevant articles and documents

A 4-methyl-4-trichloromethyl -2,5-cyclohexadiene-1-one preparation method (by machine translation)

The invention discloses a method for preparing 4-methyl-4-trichloromethyl-2, 5-cyclohexadiene-1-ketone. The method comprises the following steps that p-cresol and carbon tetrachloride serve as a raw material, aluminum chloride serves as a catalyst, and hydrochloric ether serves as a solvent to have a reaction at the temperature of 33 DEG C to 45 DEG C; water is added into mixed liquor prepared in the S1 to carry out quenching reaction, and the quenching reaction time ranges from 15 min to 45 min; liquor separating is carried out, the liquor separating temperature ranges from 5 DEG C to 20 DEG C, the solvent is removed, and residue is obtained; alcoholic solutions and activated carbon are added into the obtained residue and stirred, the temperature ranges from 50 DEG C to 78 DEG C, the stirring time ranges from 0.5h to 1h, heat filtering is carried out, cooling is carried out until a solid body is not separated out, filtering and drying are carried out, and the 4-methyl-4-trichloromethyl-2, 5-cyclohexadiene-1-ketone is obtained. The preparation method is safe in technological operation, a purification technology is simple, the production period is short, industrialization production is facilitated, raw material cost is low, and the yield is stable.

Crystal Structure and Nuclear Quadrupole Resonance. The Bond Length C-Cl and 35Cl NQR

The intramolecular distances dC-Cl for chlorine bound to sp2 carbon and to sp3 carbon, respectively, and the 35Cl NQR frequencies assigned to the corresponding Cl atoms correlate quite well according to the theory: ν(35Cl) ca. (dC-Cl)-3.The relation is ν(35Cl) = (4 +/- 6) MHz + (166 +/- 31)*1E6*(dC-Cl)-3* MHz*pm3 for 2-C>-Cl and ν(35Cl) = (21 +/- 5) MHz + (101 +/- 25) *1E6 * (dC-Cl)-3 *MHz * pm3 for 3-C>-Cl.The crystal structures and chemical bonds of (1) (4-methyl-4-trichloromethyl-2,5-cyclohexadiene-1-one), (2) (2-chloro-4,5-dimethyl-4-trichloromethyl-2,5-cyclohexadiene-1-one), (3) (4,5-dichloro-1- phenyl-pyridazine-6-one), and (4) ( 2,2,4,5-tetrachloro-cyclopentene-1,3-dione) were studied by single crystal X-ray diffraction and 35Cl nuclear quadrupole resonance (NQR). (1) crystallizes with the space group D152h-Pbca, Z = 8.The lattice constants are a= 1206.0(3) pm, b= 1341.3(3) pm, and c = 1178.8(3) pm. (2) crystallizes monoclinic, space group C52h-P21/c, Z = 4, a = 696.3(3) pm, b = 1404.0(5) pm, c = 1151.4(5) pm, and β = 100.23(1) deg. (3) crystallizes in the orthorhombic space group D42-P212121 , Z = 4, a = 4303(1) pm, b = 586.8(2) pm, and c = 390.5(1) pm. (4) crystallizes cubic, space group T4h-Fd3, with 48 molecules in the unit cell, a = 2181.5(5) pm.The 35Cl NQR spectra were observed for the two 2,5-cyclohexadiene-1-ones, (1) and (2) in the temperature range 77 less equal T/K less melting point.For (3), the 35Cl NQR spectra was determined at T = 77 K and T = 295 K.No phase transition has been found for the three compounds in the temperature range in which the 35Cl NQR spectroscopy was performed.