1,1-Dichloro-2,2,2-trihaloethyl Isocyanates and N-(1-Chloro-2,2,2-trihaloethylidene)urethanes in the Synthesis of 4-Trihalomethyl-2H-1,3-benzoxazin-2-ones

4-Trihalomethyl-2H-1,3-benzoxazin-2-ones have been synthesized by the reaction of 1,1-dichloro-2,2,2-trihaloethyl isocyanates or N-(1-chloro-2,2,2-trihaloethylidene)urethanes with 3-dialkylamino(alkoxy)phenols. The character of the products from the addition of nucleophiles has been shown to depend on the nature of the nucleophile and the trihalomethyl group.     

Confirmation of the E and Z attribution to the isomers of 3-ethylidene-1-azabicyco-[2,2,2]octane by CMR spectroscopy

CMR spectra of the following bicyclo[2,2,2]octane compounds were measured: 1-azabicyclo[2,2,2]octan-3-one ( 3 ), 2-azabicyclo[2,2,2]octan-3-one ( 5 ), bicyclo[2,2,2]octaone ( 4 ), 3-ethyl-1-azabicyclo[2,2,2]oct-2-ene ( 6 ) and of the Z and E isomers of 3-ethylidene-1-azabicyclo-[2,2,2]octane ( 1 and 2 ). The attribution of the signals and confirmation of the Z and E configuration of isomers ( 1 ) and ( 2 ) is described.     

Synthesis and Properties of N-(2,2,2-Trichloroethyl)-2-thiophenesulfonamides

Chlorination of 2-thiophenesulfonamide gave unstable N,N-dichloro-2-thiophenesulfonamide which was brought into reactions with 1,2-polyhaloethenes. The condensation of 2-thiophenesulfonamide with trichloroacetaldehyde afforded N-(2,2,2-trichloro-1-hydroxyethyl)-2-thiophenesulfonamide which reacted with benzene, toluene, 2-chlorothiophene, and phenol to form the corresponding N-(1-aryl-2,2,2-trichloroethyl)-2-thiophenesulfonamides. Under more severe conditions, the latter were converted into 1,1-diaryl-2,2,2-trichloroethanes. The reaction of N-(2,2,2-trichloro-1-hydroxyethyl)-2-thiophenesulfonamide with substituted arenes, including phenol, was regioselective: only the corresponding para-substituted products were obtained. Hydrolysis of N-[2,2,2-trichloro-1-(4-tolyl)ethyl]-2-thiophenesulfonamide yielded N-(2-thienylsulfonyl)-2-(4-tolyl)glycine.     

Selective nitrogen protection of hydroxyalkylbenzimidazoles using 2,2,2-trichloroethylchloroformate

A method for selective N-protection of hydroxyalkylbenzimidazoles using 2,2,2-trichloroethylchloroformate (Troc-Cl) applicable to various alkyl chain lengths has been developed. In the specific case of 5-(1-[2,2,2-trichloroethyl formyl]-benzimidazol-2-yl)-propan-1-ol, migration of Troc from the benzimidazole to the primary alcohol occurs in the presence of triethylamine, allowing the choice of selective N-Troc or O-Troc protection.     

An asymmetric synthesis of both enantiomers of 2,2,2-trifluoro-1-furan-2-yl-ethylamine and 3,3,3-trifluoroalanine from 2,2,2-trifluoro-1-furan-2-yl-ethanone

The selective conversion of 2,2,2-trifluoro-1-furan-2-yl-ethanone into (E)- and (Z)-oximes and oxime ethers and subsequent oxazaborolidine-catalyzed enantioselective reduction using different amino alcohols furnished both enantiomers of the important chiral building block 2,2,2-trifluoro-1-furan-2-yl-ethylamine with e.e. of up to 88%. Oxidation of the furan ring afforded both enantiomers of 3,3,3-trifluoroalanine in 91–93% yields.     

Reactions of 1-aryl-2,2,2-trifluoroethanone oximes with tetrasulfur tetranitride: Novel synthesis of 5-aryl-5-trifluoromethyl-4H-1,3,2,4,6-dithiatriazines and 1-aryl-2,2,2-trifluoro-ethanonylidenaminosulfenamides

The reactions of 1-aryl-2,2,2-trifluoroethanone oximes with tetrasulfur tetranitride (S₄N₄) in toluene at reflux gave 5-aryl-5-trifluoromethyl-4H-1,3,2,4,6-dithiatriazines 2 , 1-aryl-2,2,2-trifluoroethanonyliden-aminosulfenamides 3 and sulfur in 0–37%, 7–53%, and 2–41% yields, respectively. Treatment of 2 with tributyltin hydride in the presence of azobisisobutyronitrile in benzene at 80° afforded 3 in excellent yields.     

N-(2,2,2-Trichloroethylidene)- and N-(1-Hydroxy-2,2,2-trichloroethyl)amides in C-Amidoalkylation Reaction of Functionally-substituted Aromatic Compounds

A reaction with phenol and pyrocatechol of N-(2,2,2-trichloroethylidene)arenesulfonyl-, ethoxycarbonylamides and 1-hydroxy-substituted N-(2,2,2-trichloroethyl)amides of arenesulfonic, carbamic, and acetic acids in the presence of oleum or in sulfuric acid provided the corresponding (1-amido-2,2,2-trichloroethyl)-substituted phenols. N-(2,2,2-Trichloroethylidene)-4-chlorobenzenesulfonamide reacted with salicylamide in the presence of oleum to afford 3-aminocarbonyl-4-[2,2,2-trichloro-1-(4-chlorobenzenesulfonamido)ethyl]benzene whereas the 1-hydroxy-2,2,2-trichloroethylamides of the acetic, carbamic, and arenesulfonic acids did not enter into such reactions.     

Alkylation of Phenols with N-(2,2,2-Trichloroethylidene)- and N-(2,2,2-Trichloroethyl)arenesulfonamides

N-(2,2,2-Trichloroethylidene)- and N-(2,2,2-trichloroethyl)arenesulfonamides react with phenol, 2-chlorophenol, and 2-methylphenol in the presence of oleum or sulfuric acid to give the corresponding 4-(2,2,2-trichloro-1-arylsulfonylaminoethyl)phenols in good yields.     

Formation of Fluoroderivatives of 1,2,3,4-Tetrahydro-1,3-diazafluorene from 2-Dialkylamino- 3-(1-imino-2,2,2-trifluoroethyl)hexafluoroindenes

2-Dimethylamino-3-(1-imino-2,2,2-trifluoroethyl)hexafluoroindene in the presence of DMSO or NEt₃ undergoes isomerization into 1-methyl-4-trifluoromethyl-5,6,7,8,9,9-hexafluoro-1,2,3,4-tetrahydro-1,3-diazafluorene, and from 1-(1-amino-2,2,2-trifluoroethylidene)octafluoroindane by the treatment with water solution of NHEt₂ 2-methyl-4-trifluoromethyl-1-ethyl-5,6,7,8,9,9-hexafluoro-1,2,3,4-tetrahydro-1,3-diazafluorene was obtained.     

Chlorinations of derivatives of 2,2,2-trichlorobenzo-1,3,2-dioxaphospholes

By ³¹P, ¹³C, ¹³C-{¹H}, and ¹H NMR spectroscopy the chlorination of 4-and 5-methyl-2,2,2-trichlorobenzo-1,3,2-dioxaphosphols was shown to provide in quantitative yield 4-methyl-2,2,2,5-tetrachloroand 6-methyl-2,2,2,5-tetrachlorobenzo-1,3,2-dioxaphosphols. Their hydrolysis led to the formation of difficultly available 4-methyl-5-chloro-and 3-methyl-4-chloro-1,2-dihydroxybenzenes. The structure of the latter compound was established by XRD analysis. The 5-methyl-2-chlorobenzo-1,3,2-dioxaphosphol treated with excess chlorine was converted in succession into 5-methyl-2,3,4,5,6,6-hexachlorocyclohex-1-en-3-yl dichlorophosphate and 5-methyl-1,2,4,4,5,6-hexachlorocyclohex-1-en-3-yl dichlorophosphate. The hydrolysis resulted in 5-methyl-2,3,4,5,6,6-hexachlorocyclohex-2-en-1-yl dihydrophosphate. The configuration of three chiral carbon atoms in the latter was established by XRD study. In the course of the chlorination the aromaticity of the ortho-phenylene fragment was distorted and 3,3-sigmatropic shift of the dichlorophosphoryl group occurred. The reaction with chlorine of 5-tert-butyl-2,2,2-trichlorobenzo-1,3,2-dioxaphosphol and 2,2,2-trichloro-benzo-1,3,2-dioxaphosphol was not selective: The reaction product obtained in excess chlorine transformed on hydrolysis into tetrachloropyrocatechol. Its solvates with water and dioxane were studies by XRD analysis.     

1-Aryl-1-chloro-2,2,2-trifluoroethylisocyanates—convenient reagents for synthesis of 2-aryl-2-trifluoromethyl-2,3-dihydro-4H-benzo[e][1,3]oxazin-4-ones

1-Aryl-1-chloro-2,2,2-trifluoroethylisocyanates react with 3-alkoxyphenols to form N-(1-aryl-2,2,2-trifluoroethylidene)-O-(3-alkoxyphenyl)urethanes, which undergo intramolecular thermal cyclization into derivatives of 2-aryl-2-trifluoromethyl-2,3-dihydro-4H-benzo[e][1,3]oxazin-4-ones.     

Synthesis and Crystal Structure of [K（2,2,2-crypt）]2HP11

[K（2,2,2-crypt]2HP11 has been prepared from the reaction of K3P11 with the mixed ethylenediamine/2,2,2-crypt solution. The crystal structure was determined by singlecrystal X-ray diffraction. The crystal is of tdgonal system, space group P^-3c1 with a = 12.068（2）, b = 12.068（2）, c = 22.319（6）A, V = 2815.0（10）A^3, Dc = 1.384 g/cm^3, C36h73K2N4O12P11, Mr = 1172.85, F（000） = 1232,μ = 0.536 mm^-1, Z= 2, R = 0.0678 and wR = 0.2211 for 1763 observed reflections （I 〉 2σ（I））. In this compound, the P11 cluster has ideal 32-D3 symmetry, and the three-fold axis, corresponds to the crystallographic c axis. The （HP11）^2- anions are stable due to the completely sequestered alkali metal cations through only ion-ion interactions.     

Synthesis and properties of esters and amido esters of 1-(2-thienyl)-2,2,2-trichloroethylphosphorous acid

Conclusions The esterification of amido- and ester-amidophosphites with 1-(2-thienyl)-2,2,2-trichloroethanol gave the l-(2-thienyl)-2,2,2-trichloroethyl dialkyl- and 1-(2-thienyl)-2,2,2-trichloroethyl alkylamidophosphites, which easily add sulfur or are oxidized to the corresponding thiophosphates and phosphates.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 182–187, January, 1981.     

Sodium dithionite initiated reactions of 1-bromo-1-chloro-2,2,2-trifluoroethane with enol ethers of cyclic ketones

Sodium dithionite initiated reactions of 1-bromo-1-chloro-2,2,2-trifluoroethane (1) with methyl and trimethylsilyl ethers of cyclopentanone and cyclohexanone enols (2a-d) in a MeCN/H₂O system were investigated. 2-(2,2,2-Trifluoroethylidene)cyclopentanone (4a) and 2-(2,2,2-trifluoroethylidene)-cyclohexanone (4b), respectively, were obtained as the main products and isolated in reasonable yields. The reaction with a 1:1 mixture of 5- and 3-methyl substituted 1-methoxycyclohexenes, 2e and 2f, revealed strong influence of steric hindrance on the reaction rate; a mixture of 2-(2,2,2-trifluoroethylidene)-5-methylcyclohexanone (6) and 2-(2,2,2-trifluoroethylidene)-3-methylcyclohexanone (7) in a 9:1 ratio was formed. Ketones 4a and 4b were reduced to the corresponding alcohols 8 and 9 and the reaction of 4b with hydrazine gave an indazole derivative 10.     

Fluorinated chromenes 1: 2,2,2-trifluoroethoxy precocene analogs and their corresponding 3,4-epoxides

Preparation of potential insect antijuvenile hormone agents 2,2-dimethyl-7-(2,2,2-trifluoroethoxy)-2H-chromene ($\text{3a}$), 6-methoxy-2,2-dimethyl-7-(2,2,2-trifluoroethoxy)-2$\text{H}$-chromene ($\text{3b}$) and 7-methoxy-2,2-dimethyl-6--(2,2,2-trifluoroethoxy)-2$\text{H}$-chromene ($\text{3c}$) and the corresponding 3,4-epoxides $\text{5a}$ and $\text{5b}$ is reported.     

Reactions of 2,2,2-trifluorodiazoethane with carbon-nitrogen and carbon-oxygen multiple bonds

2,2,2-Trifluorodiazoethane reacts with trifluoroacetonitrile in the dark at room temperature to give a 2-(2,2,2-trifluoroethyl)-4, 5-bis(trifluoromethyl)triazole, the 1,2,3-triazole structure being preferred to the 1,2,4-isomer on the basis of the ¹⁹F n.m.r. spectrum. The diazoethane reacts more slowly with trichloroacetonitrile, again forming the N-alkylated triazole even in the presence of an excess of the nitrile. No identifiable adduct resulted with acetonitrile. Hexafluoroisopropyl-ideneimine is first N-alkylated and then undergoes addition to form 1-(2,2,2-trifluoro-1-trifluoromethyl)ethyl-4,5-bis(trifluoromethyl)-?-1,2,3-triazoline, but N-methylhexafluoroisopropylideneimine failed to react. Trifluoroacetaldehyde and trichloroacetaldehyde give mixtures of the ketone (formed by insertion of the CF₃CH group into the aldehyde CH bond) and the $\text{cis}$- and $\text{trans}$-oxirans, apparently $\text{via}$ a β-hydroxydiazoalkane.     

Synthesis of substituted N-(2,4-dioxo-1,2,3,4-tetrahydroquinazolinyl)benzamides and N-(2-thiono-4-oxo-1,2,3,4-tetrahydroquinazolinyl)benzamides

Substituted N-(2,4-Dioxo-1,2,3,4-tetrahydroquinazolinyl)benzamides ( 3a-g ) and substituted N-(2-Thiono-4-oxo-1,2,3,4-tetrahydroquinazolinyl)benzamides ( 4a-g ) were synthesized in one step from the reaction of methyl anthranilate with 2-aryl-1,3,4-oxadiazolin-5-ones ( 1a-g ) and 2-aryl-1,3,4-oxadiazoline-5-thiones ( 2a-g ), respectively, in m-cresol at 150–160°. Alternative routes leading to the formation of 3a and 4a are also reported.     

DI-(2,2,2-Trichloroethyl)-Carbonate: Byproduct in Reactions with 2,2,2-Trichloroethyl Chloroformate

2,2,2-Trichloroethyl chloroformate (1) in higher boiling solvents, particularly in the presence of potassium carbonate and potassium bicarbonate, affords undesired di-(2,2,2-trichloroethyl)-carbonate (2) as a byproduct. When chemically pure chloroformate was used, addition of carbonates was found to be unnecessary in N-demethylation reactions.     

Synthesis of carbazoles via an intramolecular cyclization of 2-(6-substituted 3(Z)-hexen-1,5-diynyl)anilines and their related molecules

Various 2-(6-substituted 3(Z)-hexen-1,5-diynyl)anilines 1a-g were treated with potassium tert-butoxide or potassium 3-ethylpentanoxide in NMP at 60 degrees C for 2 h to give the corresponding 5-substituted carbazoles 2a-g in 36-65% yields together with indoles 9a-g in 21-40% yields, respectively. Exposing the trifluoroacetamide analogues 10h-k under the same reaction conditions gave the carbazoles 2b-e in 37-57% yields and indoles 9b-e in 15-27% yields. Subsequent cyclizations of acetamide analogues 10a-g gave carbazoles 2a-g in 53-86% yields.     

Synthesis and crystal structure of 5-tert-butyldimethylsilyl-2-(2,2,2-trifluoro-hydroxyiminoethyl)furan

The oximation of 5-tert-butylmethylsilyl-2-(trifluoroacetyl)furan with hydroxylamine leads to the exclusive formation of the E-isomer of 5-tert-butyldimethylsilyl-2-(2,2,2-trifluorohydroxyiminoethyl)- furan.