The synthesis of 3 chloro 2 nitrotoluene using 2,6 dichloroaniline as starting material by diazotization, substitution, condensation, decarboxylic reaction was studied and the best conditions of the synthetic proc...The synthesis of 3 chloro 2 nitrotoluene using 2,6 dichloroaniline as starting material by diazotization, substitution, condensation, decarboxylic reaction was studied and the best conditions of the synthetic procedures were confirmed. Dichloronitrobenzene was obtained in 78.9% yield based on 2,6 dichloroaniline. The reaction of 2,6 dichloronitrobenzene and methyl cyanoacetate with potassium carbonate catalyst in N,N dimethyl formamide gave methyl 2 cyano 2 (3′ chloro 2′ nitrophenyl) acetate in 80.2% yield. The third procedure product 3 chloro 2 nitrophenylacetic acid was obtained by hydrolysis in 82.6% yield. Decarboxylation reaction of 3 chloro 2 nitrophenylacetic acid produced 3 chloro 2 nitrotoluene in 72.9% yield.The structure of products was identified by IR and NMR.展开更多
Little is known about the toxic activity of the atrazine (a herbicide, commonly used in agricultural production) on the thyroid gland. In this study the compound was administered orally in female albino rats at sublet...Little is known about the toxic activity of the atrazine (a herbicide, commonly used in agricultural production) on the thyroid gland. In this study the compound was administered orally in female albino rats at sublethal exposure equivalent to 0.2 LD50 doses for 6 and 12 days. At termination of dosing the anesthetized animals were killed and blood was drawn for the determination of serum triiodothyronine (T3) and thyroxin (T4). A dose-dependent decrease of serum T3 concentration was observed in all the groups (control: 0.57 nmol·L-1; 6 days: 0.35 nmol·L-1; 12 days: 0.21 nmol·L-1). The thyroid gland was examined light-microscopically. Bouin's solution-fixed thyroids were embedded in paraffin and sections cut at 6 μm, stained separately with toluidine blue according to Slinchenko's method. Histologically in experimental groups epithelium featured small cuboidal cells and occasional structures of the follicles confluence within epitheliomers. A dose-dependent changes of the following parameters were observed: (a) increasing of number of follicle-building thyroid cells; (b) increasing of follicular volume, (c) decreasing of nucleus volume. Investigation of the whole population of thyroid mast cells disclosed no change in degranulation intensity. By contrast, degranulation intensity was decreased in perifollicular mast cells from groups treated with atrazine in dose-dependent manner.There are no changes observed in degranulation of stromal mast cells. These results suggesting that differences in response to the atrazine might account for an aspect of the functional heterogeneity within the rat thyroid mast cell population.展开更多
Chloro ethane dimethyl sulfoxide,C_2H_5Cl·DMSO(ECI·DMSO)was prepared by interaction of acrylic acid with conc.Hydrochloric acid in dimethyl sulfoxide(DMSO)and subsequent decarboxylation with H_2O_2 solution....Chloro ethane dimethyl sulfoxide,C_2H_5Cl·DMSO(ECI·DMSO)was prepared by interaction of acrylic acid with conc.Hydrochloric acid in dimethyl sulfoxide(DMSO)and subsequent decarboxylation with H_2O_2 solution.The formation of the compound was confirmed by spectral and analytical methods;the molecular weight was determined by cryoscopic method.The solubility of poly(vinyl alcohol)(PVA)in different solvents or mixed solvents at 40℃,50℃and 60℃temperature in the presence of 0.01% of EC1·-DMSO was determined.It tu...展开更多
The reaction of cis- 2- chloro- 4- phenyl- 5, 5- dimethyl- 1, 3. 2-dioxaghosghor inan-2- thione (Ⅰ) with methoxide or phenoxide at room temperatute takes place with retent ion of configuration. while refluxing cis- ...The reaction of cis- 2- chloro- 4- phenyl- 5, 5- dimethyl- 1, 3. 2-dioxaghosghor inan-2- thione (Ⅰ) with methoxide or phenoxide at room temperatute takes place with retent ion of configuration. while refluxing cis- (1) and methoxide in methanol, gartial isomerization of cis-thioghosphate (2) to its trans isomer occursand an acyclic intermediate (3) is found to be involved in this grocess展开更多
The total synthesis of the labeled componed from immediacetic acid through esterifying, reducing with LiAID: as a labeling agent, chlerinating and phosphory, lating reactions was first, reported in this paper.
Chloro 2 diethylaminoethyl 3(2H) pyridazinone was synthesized by the reaction of 6 chloro 3(2H) pyridazinone and 2 diethylamionethyl chloride reaction in methylbenzene. Then the structure was characterized by...Chloro 2 diethylaminoethyl 3(2H) pyridazinone was synthesized by the reaction of 6 chloro 3(2H) pyridazinone and 2 diethylamionethyl chloride reaction in methylbenzene. Then the structure was characterized by means of 1H NMR, IR, UV. By the method of ab initio HF and density functional theory (DFT) B3LYP, the geometric structures of the reagent intermediate, the product and its isomer were optimized and their total energies were calculated. The properties for the frontier molecular orbitals and the rules for energy distribution were analyzed systematically. It was shown that the energy of the nitrogen alkyl compound is lower than that of the oxy alkyl compound and the former is stable than the latter . This result is in accordance with the fact that 6 chloro 2 diethylaminoethyl 3(2H) pyridazinone is synthesized by the reaction of \{6 chloride \}2 diethylaminoethyl 3(2H) pyridazinone and 2 diethylaminoethyl chloride.展开更多
A series of new complexes, CpTiCl[S2P(OR)2]2 (where R) Et, n-Pr, i-Pr, Bui, Ph) and CpTiCl [S2POGO]2 (where G) –CH2CMe2CH2-, -CMe2CMe2-) have been prepared by the drop wise addition of the appropriate O, O’-dialkyl ...A series of new complexes, CpTiCl[S2P(OR)2]2 (where R) Et, n-Pr, i-Pr, Bui, Ph) and CpTiCl [S2POGO]2 (where G) –CH2CMe2CH2-, -CMe2CMe2-) have been prepared by the drop wise addition of the appropriate O, O’-dialkyl or -alkylene dithiophosphoric acid to cyclopentadienyl titanium trichloride in 1:2 molar ratio and refluxed in benzene solution. The new compounds were characterized by molecular weight measurements elemental analyses and spectroscopic studies (1H, 13C, and 31P NMR, and in-frared). We suggest a distorted tetrahedron structure of these new complexes and the dithioligand behaves as bidentate ligand.展开更多
4-Amino-3-mercapto-6-methyl-l,2,4-triazin-5（4H）-one 1 converted to 4-amino-6-methy-3-（methylthio）-1,2,4-triazin-5（4H）-one by methylation with methyl iodide.Controlled hydrazination of the resulting compound affo...4-Amino-3-mercapto-6-methyl-l,2,4-triazin-5（4H）-one 1 converted to 4-amino-6-methy-3-（methylthio）-1,2,4-triazin-5（4H）-one by methylation with methyl iodide.Controlled hydrazination of the resulting compound afforded 4-amino-3-hydrazinyl-6- methyl-l,2,4-triazin-5（4H）-one 2 as a building block,to the synthesis of some novel derivatives of[1,2,4]triazino- [4,3,b][1,2,4,5]tetrazepine 3-6,by the reaction with 3-chloropentane-2,4-dione,chloro acetonitrile,1,3-dichloroacetone,and methyl bromoacetate.This general synthetic procedure can be extended to the preparation of wide variety of tetrazepines using 1,2- bielectrophiles derivatives.展开更多
Synthesis of a new high sensitive water soluble chromogenic reagent mes o tetra (2 chloro 4 sulfophenyl)prophyrin and the conditions for the reaction of this reagent with cadmiun(Ⅱ) were studied. The apparent...Synthesis of a new high sensitive water soluble chromogenic reagent mes o tetra (2 chloro 4 sulfophenyl)prophyrin and the conditions for the reaction of this reagent with cadmiun(Ⅱ) were studied. The apparent molar absorption coefficient at 434 nm is 5.20×10 5 L·mol -1 ·cm -1 . The method has been applied to the determination of 5.0×10 -9 (content by weight) Cadmium(Ⅱ) in honey.展开更多
For water to become suitable for human consumption in most water treatment plants this occurs by making use of the chlorination process where the organic matter is destroyed by the action of chlorine. Chlorine is a di...For water to become suitable for human consumption in most water treatment plants this occurs by making use of the chlorination process where the organic matter is destroyed by the action of chlorine. Chlorine is a disinfectant that at low concentrations meets requirements such as not being toxic to humans and inactivating microorganisms. The reaction of chlorine with organic compounds results in chlorination byproducts, many potentially harmful to human health, such as trihalomethanes, haloacetic acids, among others. The present work aimed to collect and analyze samples of treated water from reservoirs from public schools in the city of Maringá, Brazil. Analyses of haloacetic acids (HAA5: monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, bromoacetic acid and dibromoacetic acid), natural organic compounds and free residual chlorine were performed (the latter analysis, in loco). The water collection points were chosen in order to maximize the concentration of haloacetic acids that characterize network distant points from treatment station and also samples near the water treatment plant. With the results, the formation of haloacetic acids between the entrance water of the school and the water of the reservoir of the collection points were compared, where higher values were obtained in the reservoirs. Furthermore, the haloacetic acid levels of water supplied to the population close to the treatment station and distant points of the treatment station were compared, resulting in larger values at the distant points. The value of 0.170 mg/L in haloacetic acid (the maximum value allowed by the legislation is 0.080 mg/L) was obtained at a point distant in the network from the treatment plant. The Consolidation Ordinance n.5/2017, current legislation for treated water in Brazil, was used in relation to the maximum allowable values for free residual chlorine and haloacetic acids.展开更多
PdCl 2 (CH 3) 3CC 6H 4SC 4H 9- S 2, C 28 H 44 Cl 2S 2Pd, M r =622.0756, triclinic, space group P1, a=10.403(2), b=12.346(2), c=13.475(2) , α=89 11(1)°, β=75.44(1)°, γ=69.52(...PdCl 2 (CH 3) 3CC 6H 4SC 4H 9- S 2, C 28 H 44 Cl 2S 2Pd, M r =622.0756, triclinic, space group P1, a=10.403(2), b=12.346(2), c=13.475(2) , α=89 11(1)°, β=75.44(1)°, γ=69.52(1)°, V=1564.2(5) 3, Z=2, D c =1.32 g/cm 3, Mo Kα radiation, μ =9.00 cm -1 , F(000)=647.95, R =0.0316 for 4561 observed reflections with I≥3σ(I) . Pd(Ⅱ) is coordinated by two chloride atoms and two sulfur atoms of organic ligands, forming a rhombic quadrilateral plane with Pd-S of 2.325(1) and Pd-Cl of 2.295(1) .展开更多
Poly(3-hydroxyalkanoates) (PHAs) are a promising class of biodegradable polymers,exhibiting properties comparable to traditional petroleum-based counterparts.Nonetheless,the widespread commercialization of PHAs is hin...Poly(3-hydroxyalkanoates) (PHAs) are a promising class of biodegradable polymers,exhibiting properties comparable to traditional petroleum-based counterparts.Nonetheless,the widespread commercialization of PHAs is hindered by the absence of an efficient and economically viable catalytic system,impeding their competitiveness against non-biodegradable polymers.In an effort to address this challenge,we present a study on a newly developed chloro-bridged dimeric salphen zirconium cobaltate complex for the direct synthesis of PHAs via carbonylative polymerization of epoxides.The catalytic system demonstrates favorable activity under mild reaction conditions,enabling complete monomer conversion and an impressive 92% selectivity towards PHA formation.Through meticulous control experiments and mechanistic studies,we have gained crucial insights into the polymerization process.Remarkably,our findings challenge the prevailing notion of sequential ring-opening polymerization of in-situ generated β-lactones as the primary pathway.Instead,we demonstrate that the polymerization predominantly proceeds through direct co-polymerization of epoxide and carbon monoxide,unveiling a unique and efficient mechanism for PHA synthesis.展开更多
Most of the organolanthanides are prepared by using their chlorides as starting materials. It is easy to obtain the trichlorides of lanthanides. Cerium tetrachloride has not been prepared owing to its thermal instabil...Most of the organolanthanides are prepared by using their chlorides as starting materials. It is easy to obtain the trichlorides of lanthanides. Cerium tetrachloride has not been prepared owing to its thermal instability. Some of the chloro-complexes of cerium(Ⅳ) with a variety of cations and a few of its complexes with neutral donor ligands have been isolated.展开更多
The circulating cooling water consumes about 80% industrial water in the world. In order to save water resources, using microbiocide in recirculating cooling water system is one of the important technique. One of the ...The circulating cooling water consumes about 80% industrial water in the world. In order to save water resources, using microbiocide in recirculating cooling water system is one of the important technique. One of the authors observed the bactericidal activities of p-chloro-β-dimethyl-aminopropiophenone during screening biocides. The test of water flooding showed that p-chloro-β-dimethyl-aminopropiophenone exhibited展开更多
Six sterically hindered chloro meso-tetra-ortho-alkylphenylporphinato irons (T(o-R)PPFe(III)Cl, R = Me, Et, n-Pr, i-Pr, n-Bu, t-Bu) were synthesized and used to catalyze the monooxygenation of cyclohexane with PhIO. B...Six sterically hindered chloro meso-tetra-ortho-alkylphenylporphinato irons (T(o-R)PPFe(III)Cl, R = Me, Et, n-Pr, i-Pr, n-Bu, t-Bu) were synthesized and used to catalyze the monooxygenation of cyclohexane with PhIO. Both the yields of cyclohexanol and the relative rates of monooxygenation of cyclohexane catalyzed by T(o-R) PPFe(IIl)Cl were higher than those of TPPFe(III)Cl respectively. The order of the yields(%) of cyclohexanol and the rate of cyclohexanol formation in the monooxygenation of cyclohexane catalyzed by T(o-R)PPFe(III)Cl for the different substituents are: i-Pr(58) > Et(57) > n-Pr(52) > Me(51) > n-Bu(48) > t-Bu(46) > H(35) and i-Pr > Et > t-Bu > n-PT greater than or equal to Me greater than or equal to n-Bu greater than or equal to H respectively. The special steric effect on the catalytic character of these different alkyl substituents in T(o-R)PPFe(III)Cl is proposed on the basis of the results.展开更多
文摘The synthesis of 3 chloro 2 nitrotoluene using 2,6 dichloroaniline as starting material by diazotization, substitution, condensation, decarboxylic reaction was studied and the best conditions of the synthetic procedures were confirmed. Dichloronitrobenzene was obtained in 78.9% yield based on 2,6 dichloroaniline. The reaction of 2,6 dichloronitrobenzene and methyl cyanoacetate with potassium carbonate catalyst in N,N dimethyl formamide gave methyl 2 cyano 2 (3′ chloro 2′ nitrophenyl) acetate in 80.2% yield. The third procedure product 3 chloro 2 nitrophenylacetic acid was obtained by hydrolysis in 82.6% yield. Decarboxylation reaction of 3 chloro 2 nitrophenylacetic acid produced 3 chloro 2 nitrotoluene in 72.9% yield.The structure of products was identified by IR and NMR.
文摘Little is known about the toxic activity of the atrazine (a herbicide, commonly used in agricultural production) on the thyroid gland. In this study the compound was administered orally in female albino rats at sublethal exposure equivalent to 0.2 LD50 doses for 6 and 12 days. At termination of dosing the anesthetized animals were killed and blood was drawn for the determination of serum triiodothyronine (T3) and thyroxin (T4). A dose-dependent decrease of serum T3 concentration was observed in all the groups (control: 0.57 nmol·L-1; 6 days: 0.35 nmol·L-1; 12 days: 0.21 nmol·L-1). The thyroid gland was examined light-microscopically. Bouin's solution-fixed thyroids were embedded in paraffin and sections cut at 6 μm, stained separately with toluidine blue according to Slinchenko's method. Histologically in experimental groups epithelium featured small cuboidal cells and occasional structures of the follicles confluence within epitheliomers. A dose-dependent changes of the following parameters were observed: (a) increasing of number of follicle-building thyroid cells; (b) increasing of follicular volume, (c) decreasing of nucleus volume. Investigation of the whole population of thyroid mast cells disclosed no change in degranulation intensity. By contrast, degranulation intensity was decreased in perifollicular mast cells from groups treated with atrazine in dose-dependent manner.There are no changes observed in degranulation of stromal mast cells. These results suggesting that differences in response to the atrazine might account for an aspect of the functional heterogeneity within the rat thyroid mast cell population.
文摘Chloro ethane dimethyl sulfoxide,C_2H_5Cl·DMSO(ECI·DMSO)was prepared by interaction of acrylic acid with conc.Hydrochloric acid in dimethyl sulfoxide(DMSO)and subsequent decarboxylation with H_2O_2 solution.The formation of the compound was confirmed by spectral and analytical methods;the molecular weight was determined by cryoscopic method.The solubility of poly(vinyl alcohol)(PVA)in different solvents or mixed solvents at 40℃,50℃and 60℃temperature in the presence of 0.01% of EC1·-DMSO was determined.It tu...
文摘The reaction of cis- 2- chloro- 4- phenyl- 5, 5- dimethyl- 1, 3. 2-dioxaghosghor inan-2- thione (Ⅰ) with methoxide or phenoxide at room temperatute takes place with retent ion of configuration. while refluxing cis- (1) and methoxide in methanol, gartial isomerization of cis-thioghosphate (2) to its trans isomer occursand an acyclic intermediate (3) is found to be involved in this grocess
文摘The total synthesis of the labeled componed from immediacetic acid through esterifying, reducing with LiAID: as a labeling agent, chlerinating and phosphory, lating reactions was first, reported in this paper.
基金Supported by the National Natural Science Foundation of China(No. 2 0 16 2 0 0 5 ) .
文摘Chloro 2 diethylaminoethyl 3(2H) pyridazinone was synthesized by the reaction of 6 chloro 3(2H) pyridazinone and 2 diethylamionethyl chloride reaction in methylbenzene. Then the structure was characterized by means of 1H NMR, IR, UV. By the method of ab initio HF and density functional theory (DFT) B3LYP, the geometric structures of the reagent intermediate, the product and its isomer were optimized and their total energies were calculated. The properties for the frontier molecular orbitals and the rules for energy distribution were analyzed systematically. It was shown that the energy of the nitrogen alkyl compound is lower than that of the oxy alkyl compound and the former is stable than the latter . This result is in accordance with the fact that 6 chloro 2 diethylaminoethyl 3(2H) pyridazinone is synthesized by the reaction of \{6 chloride \}2 diethylaminoethyl 3(2H) pyridazinone and 2 diethylaminoethyl chloride.
文摘A series of new complexes, CpTiCl[S2P(OR)2]2 (where R) Et, n-Pr, i-Pr, Bui, Ph) and CpTiCl [S2POGO]2 (where G) –CH2CMe2CH2-, -CMe2CMe2-) have been prepared by the drop wise addition of the appropriate O, O’-dialkyl or -alkylene dithiophosphoric acid to cyclopentadienyl titanium trichloride in 1:2 molar ratio and refluxed in benzene solution. The new compounds were characterized by molecular weight measurements elemental analyses and spectroscopic studies (1H, 13C, and 31P NMR, and in-frared). We suggest a distorted tetrahedron structure of these new complexes and the dithioligand behaves as bidentate ligand.
文摘4-Amino-3-mercapto-6-methyl-l,2,4-triazin-5（4H）-one 1 converted to 4-amino-6-methy-3-（methylthio）-1,2,4-triazin-5（4H）-one by methylation with methyl iodide.Controlled hydrazination of the resulting compound afforded 4-amino-3-hydrazinyl-6- methyl-l,2,4-triazin-5（4H）-one 2 as a building block,to the synthesis of some novel derivatives of[1,2,4]triazino- [4,3,b][1,2,4,5]tetrazepine 3-6,by the reaction with 3-chloropentane-2,4-dione,chloro acetonitrile,1,3-dichloroacetone,and methyl bromoacetate.This general synthetic procedure can be extended to the preparation of wide variety of tetrazepines using 1,2- bielectrophiles derivatives.
文摘Synthesis of a new high sensitive water soluble chromogenic reagent mes o tetra (2 chloro 4 sulfophenyl)prophyrin and the conditions for the reaction of this reagent with cadmiun(Ⅱ) were studied. The apparent molar absorption coefficient at 434 nm is 5.20×10 5 L·mol -1 ·cm -1 . The method has been applied to the determination of 5.0×10 -9 (content by weight) Cadmium(Ⅱ) in honey.
基金Centro Universitario de Maringa(UNICESUMAR)for the financial and technical support
文摘For water to become suitable for human consumption in most water treatment plants this occurs by making use of the chlorination process where the organic matter is destroyed by the action of chlorine. Chlorine is a disinfectant that at low concentrations meets requirements such as not being toxic to humans and inactivating microorganisms. The reaction of chlorine with organic compounds results in chlorination byproducts, many potentially harmful to human health, such as trihalomethanes, haloacetic acids, among others. The present work aimed to collect and analyze samples of treated water from reservoirs from public schools in the city of Maringá, Brazil. Analyses of haloacetic acids (HAA5: monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, bromoacetic acid and dibromoacetic acid), natural organic compounds and free residual chlorine were performed (the latter analysis, in loco). The water collection points were chosen in order to maximize the concentration of haloacetic acids that characterize network distant points from treatment station and also samples near the water treatment plant. With the results, the formation of haloacetic acids between the entrance water of the school and the water of the reservoir of the collection points were compared, where higher values were obtained in the reservoirs. Furthermore, the haloacetic acid levels of water supplied to the population close to the treatment station and distant points of the treatment station were compared, resulting in larger values at the distant points. The value of 0.170 mg/L in haloacetic acid (the maximum value allowed by the legislation is 0.080 mg/L) was obtained at a point distant in the network from the treatment plant. The Consolidation Ordinance n.5/2017, current legislation for treated water in Brazil, was used in relation to the maximum allowable values for free residual chlorine and haloacetic acids.
文摘PdCl 2 (CH 3) 3CC 6H 4SC 4H 9- S 2, C 28 H 44 Cl 2S 2Pd, M r =622.0756, triclinic, space group P1, a=10.403(2), b=12.346(2), c=13.475(2) , α=89 11(1)°, β=75.44(1)°, γ=69.52(1)°, V=1564.2(5) 3, Z=2, D c =1.32 g/cm 3, Mo Kα radiation, μ =9.00 cm -1 , F(000)=647.95, R =0.0316 for 4561 observed reflections with I≥3σ(I) . Pd(Ⅱ) is coordinated by two chloride atoms and two sulfur atoms of organic ligands, forming a rhombic quadrilateral plane with Pd-S of 2.325(1) and Pd-Cl of 2.295(1) .
基金supported by C1 Gas Refinery Program(2018M3D3A1A01018006)Direct Air Capture and Utilization(DACU)grant(RS-2023-00259920)through the National Research Foundation of Korea funded by the Ministry of Science,ICTFuture Planning,Republic of Korea.
文摘Poly(3-hydroxyalkanoates) (PHAs) are a promising class of biodegradable polymers,exhibiting properties comparable to traditional petroleum-based counterparts.Nonetheless,the widespread commercialization of PHAs is hindered by the absence of an efficient and economically viable catalytic system,impeding their competitiveness against non-biodegradable polymers.In an effort to address this challenge,we present a study on a newly developed chloro-bridged dimeric salphen zirconium cobaltate complex for the direct synthesis of PHAs via carbonylative polymerization of epoxides.The catalytic system demonstrates favorable activity under mild reaction conditions,enabling complete monomer conversion and an impressive 92% selectivity towards PHA formation.Through meticulous control experiments and mechanistic studies,we have gained crucial insights into the polymerization process.Remarkably,our findings challenge the prevailing notion of sequential ring-opening polymerization of in-situ generated β-lactones as the primary pathway.Instead,we demonstrate that the polymerization predominantly proceeds through direct co-polymerization of epoxide and carbon monoxide,unveiling a unique and efficient mechanism for PHA synthesis.
文摘Most of the organolanthanides are prepared by using their chlorides as starting materials. It is easy to obtain the trichlorides of lanthanides. Cerium tetrachloride has not been prepared owing to its thermal instability. Some of the chloro-complexes of cerium(Ⅳ) with a variety of cations and a few of its complexes with neutral donor ligands have been isolated.
文摘The circulating cooling water consumes about 80% industrial water in the world. In order to save water resources, using microbiocide in recirculating cooling water system is one of the important technique. One of the authors observed the bactericidal activities of p-chloro-β-dimethyl-aminopropiophenone during screening biocides. The test of water flooding showed that p-chloro-β-dimethyl-aminopropiophenone exhibited
基金Project supported by the National Natural Science Foundation of China.
文摘Six sterically hindered chloro meso-tetra-ortho-alkylphenylporphinato irons (T(o-R)PPFe(III)Cl, R = Me, Et, n-Pr, i-Pr, n-Bu, t-Bu) were synthesized and used to catalyze the monooxygenation of cyclohexane with PhIO. Both the yields of cyclohexanol and the relative rates of monooxygenation of cyclohexane catalyzed by T(o-R) PPFe(IIl)Cl were higher than those of TPPFe(III)Cl respectively. The order of the yields(%) of cyclohexanol and the rate of cyclohexanol formation in the monooxygenation of cyclohexane catalyzed by T(o-R)PPFe(III)Cl for the different substituents are: i-Pr(58) > Et(57) > n-Pr(52) > Me(51) > n-Bu(48) > t-Bu(46) > H(35) and i-Pr > Et > t-Bu > n-PT greater than or equal to Me greater than or equal to n-Bu greater than or equal to H respectively. The special steric effect on the catalytic character of these different alkyl substituents in T(o-R)PPFe(III)Cl is proposed on the basis of the results.
