The liquid phase Beckmann rearrangement of cyclohexanone oxime (CHO) using fuming sulfuric acid as a catalyst is a traditional method for preparing ε-caprolactam (CPL). This process has drawbacks, such as environment...The liquid phase Beckmann rearrangement of cyclohexanone oxime (CHO) using fuming sulfuric acid as a catalyst is a traditional method for preparing ε-caprolactam (CPL). This process has drawbacks, such as environmental pollution, corrosion of equipment, and low added value of by-product ammonium sulfate. This article designed and prepared a green silica gel-supported trifluoromethanesulfonic acid catalyst for the liquid-phase Beckmann rearrangement of CHO to prepare (CPL). The influencing factors of catalyst preparation and the optimal reaction conditions for Beckmann rearrangement were investigated. It was found that the optimal conditions for catalyst preparation were as follows: raw material silica gel:trifluoromethanesulfonic acid = 1:0.2 (mass ratio), room temperature, stirring time of 2.5 hours, and solvent of acetonitrile, silica gel mesh size is 100 - 200. The optimal reaction conditions for Beckmann rearrangement are CHO: catalyst = 1:2 (mass ratio), temperature of 130˚C, solvent of benzonitrile, volume of 30 mL/g CHO, and reaction time of 4 hours. Under the above conditions, the conversion of CHO is 90%, and the selectivity of CPL is 90%.展开更多
Beckmann rearrangement mechanism of cyclohexanone oxime, based on the characteristic of self-catalyzed reaction and polymorphism was proposed. According to the suggested mechanism, the basic approach was the rearrange...Beckmann rearrangement mechanism of cyclohexanone oxime, based on the characteristic of self-catalyzed reaction and polymorphism was proposed. According to the suggested mechanism, the basic approach was the rearrangement of OXH+ while the SO3 acts as dehydrating agent and OXSO3 can turn to CPLSO3 ultimately. Considering self-catalyzed reaction between OXSO3 and CPLH+, kinetic model for Beckmann rearrangement was established. Corresponding parameters were estimated by using float genetic algorithm （GA） and simulation results agree well with the experimental data below -19.3℃. Industrial equipment was simulated and analyzed. Effects of key process parameters such as molar ratio of sulfuric acid to oxime and circulation ratio on the residual oxime are also discussed. The results show that the caprolactam exists as CPLH+ finally in oleum and the minimum molecular ratio of sulfuric acid to oxime can be 0.5 theoretically.展开更多
Under mild conditions, conversion of a variety of ketoximes and aldoximes to their corresponding amides and nitriles proceeded in the presence of PEG-SO3H with high yields.
Six Brnsted acidic ionic liquids（ILs） 1a―1f were synthesized and used as the dual solvent-catalyst systems for Beckmann rearrangement reactions. Among ILs 1a―1f, IL 1a exhibited the highest catalytic activity and ...Six Brnsted acidic ionic liquids（ILs） 1a―1f were synthesized and used as the dual solvent-catalyst systems for Beckmann rearrangement reactions. Among ILs 1a―1f, IL 1a exhibited the highest catalytic activity and successfully catalyzed the Beckmann rearrangement of ketoximes, and the corresponding amides were obtained in good to excellent yields（74%―92%）. In addition, IL 1a could be recovered easily and reused at least three times without any loss of catalytic activity.展开更多
Deoxo 6 deoxy 6,9 epoxy 9,9 a didehydro 9 a aza 9 a homoerythromycin A (1), 9 deoxo 11 deoxy 9,11 epoxy 9,9 a didehydro 9 a aza 9 a homoerythromycin A (2) and 9 a aza 9 a ...Deoxo 6 deoxy 6,9 epoxy 9,9 a didehydro 9 a aza 9 a homoerythromycin A (1), 9 deoxo 11 deoxy 9,11 epoxy 9,9 a didehydro 9 a aza 9 a homoerythromycin A (2) and 9 a aza 9 a homoerythromycin cyclic lactam (3) were synthesized by the Beckmann rearrangement of erythromycin A 9 (E) oxime (4). The structures of compounds (1), (2) and (3) have been identified by their spectral data. The reaction mechanism was also discussed. The yield of the Beckmann rearrangement of compounds (4) was better than that reported in literatures.展开更多
The addition of platinum over the B2O3/TiO2-ZrO2 remarkably enhanced its catalytic stability in the vapor phase Beckmann rearrangement of cyclohexanone oxime under the carder gas of H2. The content of coke deposited ...The addition of platinum over the B2O3/TiO2-ZrO2 remarkably enhanced its catalytic stability in the vapor phase Beckmann rearrangement of cyclohexanone oxime under the carder gas of H2. The content of coke deposited on catalyst surface was decreased from 1.92% over the B2O3/TiO2-ZrO2 to 1.14% over the platinum promoted B2O3/TiO2-ZrO2 after reaction of six hours. This result indicates that the platinum added on the B2O3/TiO2-ZrO2 catalyst plays an important role in reducing the coke formation on the catalyst surface.展开更多
Silica sulfuric acid in which sulfuric acid is immobilized on the surface of silica gel via covalent bond has been proved to be green catalyst for liquid-phase Beckmann rearrangement of oximes in dried dioxane at room...Silica sulfuric acid in which sulfuric acid is immobilized on the surface of silica gel via covalent bond has been proved to be green catalyst for liquid-phase Beckmann rearrangement of oximes in dried dioxane at room temperature. Excellent conversion and selectivity were acquired in the Beckmann rearrangement of cyclohexanone oxime. The catalyst system was recycled and reused.展开更多
Beckmann rearrangements of oximes to lactams often require harsh conditions and/or the use of large amounts of acid catalyst. To reduce the amount of Bronsted acid required, and to avoid the formation of a large amoun...Beckmann rearrangements of oximes to lactams often require harsh conditions and/or the use of large amounts of acid catalyst. To reduce the amount of Bronsted acid required, and to avoid the formation of a large amount of undesirable byproducts under mild reaction conditions, a low environmental load process was developed. Beckmann rearrangements of cyclohexanone oxime and cyclooctanone oxime were achieved using a combination of a Bronsted acid and cobalt tetra-fluoroborate hexahydrate. Various Bronsted acid catalysts (10 - 20 mol%) were used to obtain the corresponding lactams in high yields at 80℃.展开更多
A production technique with the high yield and environmentally friendly process need be developed forε-Caprolactam(CPL)in the chemical industry.This technology is highly desired to design and synthesize high--perform...A production technique with the high yield and environmentally friendly process need be developed forε-Caprolactam(CPL)in the chemical industry.This technology is highly desired to design and synthesize high--performance catalysts for liquid phase Beckmann rearrangement of cyclohexanone oxime(CHO)to CPL.In this work,3-methyl-1-(propyl-4-sulfonyl)imidazolium methanesulfonate([PHSO_(3)MIM][MSA])with highly efficient and excellent yield is synthesized successfully.When the optimum molar ratio of ZnCl_(2)over[PHSO_(3)MIM][MSA]was 0.02,it exhibits the high selectivity(94%)of CPL at 90℃for 1 h.Interestingly,Fourier-transform infrared(FT-IR)investigations show that the functional Br∅nsted-Lewis acidic types of ionic liquids(ILs)are formed by the uniformly distributed ZnCl_(2)and[PHSO_(3)MIM][MSA].In addition,the hydrogen bond(H-bond)is formed between CHO and ILs.After ten reaction cycles,no significant structure changes are observed in the recovered[PHSO_(3)MIM][MSA]-ZnCl_(2).The solubilities of ILs are predicted by using COSMO-RS model,the results show that[PHSO_(3)MIM][MSA]is a promising candidate for the liquid phase Beckmann rearrangement of CHO into CPL.Finally,a theoretical model of the H-bond interactions between ILs and CHO is further confirmed to support the advance of reaction mechanism.A feasible way is provided for the CPL production technique in the liquid phase Beckmann rearrangement reaction.展开更多
Developing efficient and stable zeolites for vapor-phase Beckmann rearrangement of cyclohexanone oxime is still a great challenge to realizeε-caprolactam(CPL)green production.In this work,the hierarchical porous sili...Developing efficient and stable zeolites for vapor-phase Beckmann rearrangement of cyclohexanone oxime is still a great challenge to realizeε-caprolactam(CPL)green production.In this work,the hierarchical porous silicalite-1 zeolites with multiple hollow structure(S-1-M)are explored by in-situ desilication−recrystallization post-treatment of spongy highway-like zeolites(S-1-S),which are synthesized through silanization synthesis of conventional bulky silicalite-1(S-1).Compared to S-1,S-1-M achieves superior catalytic performance,with improving the CPL selectivity from 85.7%to 94.1%and prolonging the catalyst lifetime from 74 to 126 h at a weight hourly space velocity(WHSV)of 6 h^(−1).Comprehensive physiochemical studies demonstrate that the highly dispersed intracrystalline cavities within S-1-M endow greater mass diffusion and better quasi acidity inducing by the enhanced H-bonds among abundant H-bonded silanols,which is cooperatively responsible for its superior catalytic performance.展开更多
The Beckmann rearrangement has been predominantly studied for the synthesis of amide and lactam.By strategically using the in situ generated Appel’s salt or Mitsunobu’s zwitterionic adduct as the de-hydrating agent,...The Beckmann rearrangement has been predominantly studied for the synthesis of amide and lactam.By strategically using the in situ generated Appel’s salt or Mitsunobu’s zwitterionic adduct as the de-hydrating agent,a series of Beckmann rearrangement and following cascade reactions have been devel-oped herein.The protocol allows the conversion of various ketoximes into amide,thioamide,tetrazole and imide products in modular procedures.The generality and tolerance of functionalities of this method have been demonstrated.展开更多
Four different ZSM 5 zeolites are tested for the gas phase Beckmann rearrangement of cyclohexanone oxime (CHO) into lactam. B ZSM 5 derived titanosilicalite (Ti ZSM 5) exhibits catalytic performances comparabl...Four different ZSM 5 zeolites are tested for the gas phase Beckmann rearrangement of cyclohexanone oxime (CHO) into lactam. B ZSM 5 derived titanosilicalite (Ti ZSM 5) exhibits catalytic performances comparable to hydrothermally synthesized titanosilicalite (TS 1), much better than B ZSM 5 and Al ZSM 5. The effect of reaction conditions (solvent, feed space velocity, and water) on the catalytic performance of Ti ZSM 5 is studied. It is found that a quantitative relationship exists among the feed space velocity, the reaction time, and the CHO constant conversion. Ethanol or methanol as solvent shows higher activity, lactam selectivity, and stability than benzene and n hexanol. The addition of water to the rearrangement with a maximum amount of 1.0 mole per mole CHO results in the increase of CHO conversion while no meaningful changes in lactam selectivity and stability are observed.展开更多
Silicalite-1 was hydrothermally synthesized in the presence of different concentrations of Na+using tetrapropylammonium hydroxide(TPAOH)as a template.The synthesis was followed by a base treatment.The silicalite-1samp...Silicalite-1 was hydrothermally synthesized in the presence of different concentrations of Na+using tetrapropylammonium hydroxide(TPAOH)as a template.The synthesis was followed by a base treatment.The silicalite-1samples were characterized using X-ray diffrac-tion,scanning electron microscopy,N2 adsorption,X-ray photoelectron spectroscopy,Fourier transform infrared spectroscopy and NH3 temperature-programmed deso-rption.The samples were used as catalysts for the vapor phase Beckmann rearrangement of cyclohexanone oxime.During the synthesis,the sodium ions were incorporated onto the silicalite-1 crystals,but were then removed by the base treatment.All the catalysts exhibited nearly complete conversion of cyclohexanone oxime toε-caprolactam with selectivities grater than 95%.Addition of less than 2.5 mol-%Na^(+)(relative to TPAOH)did not influence the catalytic properties.However,for Na+concentrations≥5 mol-%,the particle sizes of silicalite-1 increased and the catalytic activities decreased,which can be attributed to carbon deposition.The results in this work are of great importance for the polymer industry.展开更多
A facile and efficient approach to the synthesis of secondary thioamides from ketoximes via Beckmann rearrangement has been established, using phosphorus pentasulfide as a dehydrating and thiating agent. It is also ef...A facile and efficient approach to the synthesis of secondary thioamides from ketoximes via Beckmann rearrangement has been established, using phosphorus pentasulfide as a dehydrating and thiating agent. It is also efficient for the preparation of primary thiobenzamide from benzaldoxime. This approach features simple-operation, easy-control and good to excellent yields.展开更多
An efficient Beckrnann rearrangement of ketoximes was developed using carbon tetrabromide/triphenylphos- phine as an organocatalyst without addition of any acids or metals. The reaction showed good functional group to...An efficient Beckrnann rearrangement of ketoximes was developed using carbon tetrabromide/triphenylphos- phine as an organocatalyst without addition of any acids or metals. The reaction showed good functional group tol- erance and gave various amides in moderate to good yields.展开更多
A facile synthesis for cyanochlorin related to chlorophyll from a formyl-substituted chlorin, by the oxidation of methyl （pyro）pheophorbide-a, was accomplished. These readily available chlorin aldehydes were assembl...A facile synthesis for cyanochlorin related to chlorophyll from a formyl-substituted chlorin, by the oxidation of methyl （pyro）pheophorbide-a, was accomplished. These readily available chlorin aldehydes were assembled together with hydroxylamine hydrochloride in a tandem process to produce the corresponding chlorin nitriles in moderate to good yields. The formation of chlorin nitrile was discussed and a possible mechanism for the corresponding cyanation reaction was tentatively proposed.展开更多
文摘The liquid phase Beckmann rearrangement of cyclohexanone oxime (CHO) using fuming sulfuric acid as a catalyst is a traditional method for preparing ε-caprolactam (CPL). This process has drawbacks, such as environmental pollution, corrosion of equipment, and low added value of by-product ammonium sulfate. This article designed and prepared a green silica gel-supported trifluoromethanesulfonic acid catalyst for the liquid-phase Beckmann rearrangement of CHO to prepare (CPL). The influencing factors of catalyst preparation and the optimal reaction conditions for Beckmann rearrangement were investigated. It was found that the optimal conditions for catalyst preparation were as follows: raw material silica gel:trifluoromethanesulfonic acid = 1:0.2 (mass ratio), room temperature, stirring time of 2.5 hours, and solvent of acetonitrile, silica gel mesh size is 100 - 200. The optimal reaction conditions for Beckmann rearrangement are CHO: catalyst = 1:2 (mass ratio), temperature of 130˚C, solvent of benzonitrile, volume of 30 mL/g CHO, and reaction time of 4 hours. Under the above conditions, the conversion of CHO is 90%, and the selectivity of CPL is 90%.
基金Project(20233040) supported by the National Natural Science Foundation of China and SI NOPEC
文摘Beckmann rearrangement mechanism of cyclohexanone oxime, based on the characteristic of self-catalyzed reaction and polymorphism was proposed. According to the suggested mechanism, the basic approach was the rearrangement of OXH+ while the SO3 acts as dehydrating agent and OXSO3 can turn to CPLSO3 ultimately. Considering self-catalyzed reaction between OXSO3 and CPLH+, kinetic model for Beckmann rearrangement was established. Corresponding parameters were estimated by using float genetic algorithm （GA） and simulation results agree well with the experimental data below -19.3℃. Industrial equipment was simulated and analyzed. Effects of key process parameters such as molar ratio of sulfuric acid to oxime and circulation ratio on the residual oxime are also discussed. The results show that the caprolactam exists as CPLH+ finally in oleum and the minimum molecular ratio of sulfuric acid to oxime can be 0.5 theoretically.
基金support from the Natural Science Foundation of Gansu Province(No.3ZS061-A25-019)the Scientific Research fund of Gansu Provincial Education Department(No.0601-25)
文摘Under mild conditions, conversion of a variety of ketoximes and aldoximes to their corresponding amides and nitriles proceeded in the presence of PEG-SO3H with high yields.
基金Supported by the National Natural Science Foundation of China(Nos.20771030,20671025)
文摘Six Brnsted acidic ionic liquids（ILs） 1a―1f were synthesized and used as the dual solvent-catalyst systems for Beckmann rearrangement reactions. Among ILs 1a―1f, IL 1a exhibited the highest catalytic activity and successfully catalyzed the Beckmann rearrangement of ketoximes, and the corresponding amides were obtained in good to excellent yields（74%―92%）. In addition, IL 1a could be recovered easily and reused at least three times without any loss of catalytic activity.
文摘Deoxo 6 deoxy 6,9 epoxy 9,9 a didehydro 9 a aza 9 a homoerythromycin A (1), 9 deoxo 11 deoxy 9,11 epoxy 9,9 a didehydro 9 a aza 9 a homoerythromycin A (2) and 9 a aza 9 a homoerythromycin cyclic lactam (3) were synthesized by the Beckmann rearrangement of erythromycin A 9 (E) oxime (4). The structures of compounds (1), (2) and (3) have been identified by their spectral data. The reaction mechanism was also discussed. The yield of the Beckmann rearrangement of compounds (4) was better than that reported in literatures.
文摘The addition of platinum over the B2O3/TiO2-ZrO2 remarkably enhanced its catalytic stability in the vapor phase Beckmann rearrangement of cyclohexanone oxime under the carder gas of H2. The content of coke deposited on catalyst surface was decreased from 1.92% over the B2O3/TiO2-ZrO2 to 1.14% over the platinum promoted B2O3/TiO2-ZrO2 after reaction of six hours. This result indicates that the platinum added on the B2O3/TiO2-ZrO2 catalyst plays an important role in reducing the coke formation on the catalyst surface.
文摘Silica sulfuric acid in which sulfuric acid is immobilized on the surface of silica gel via covalent bond has been proved to be green catalyst for liquid-phase Beckmann rearrangement of oximes in dried dioxane at room temperature. Excellent conversion and selectivity were acquired in the Beckmann rearrangement of cyclohexanone oxime. The catalyst system was recycled and reused.
文摘Beckmann rearrangements of oximes to lactams often require harsh conditions and/or the use of large amounts of acid catalyst. To reduce the amount of Bronsted acid required, and to avoid the formation of a large amount of undesirable byproducts under mild reaction conditions, a low environmental load process was developed. Beckmann rearrangements of cyclohexanone oxime and cyclooctanone oxime were achieved using a combination of a Bronsted acid and cobalt tetra-fluoroborate hexahydrate. Various Bronsted acid catalysts (10 - 20 mol%) were used to obtain the corresponding lactams in high yields at 80℃.
基金financial support from the National Natural Science Foundation of China(grant numbers 21776300,21890763 and 22078355)Science and Technology Department of Qinghai Province(grant number 2022-GX-152)
文摘A production technique with the high yield and environmentally friendly process need be developed forε-Caprolactam(CPL)in the chemical industry.This technology is highly desired to design and synthesize high--performance catalysts for liquid phase Beckmann rearrangement of cyclohexanone oxime(CHO)to CPL.In this work,3-methyl-1-(propyl-4-sulfonyl)imidazolium methanesulfonate([PHSO_(3)MIM][MSA])with highly efficient and excellent yield is synthesized successfully.When the optimum molar ratio of ZnCl_(2)over[PHSO_(3)MIM][MSA]was 0.02,it exhibits the high selectivity(94%)of CPL at 90℃for 1 h.Interestingly,Fourier-transform infrared(FT-IR)investigations show that the functional Br∅nsted-Lewis acidic types of ionic liquids(ILs)are formed by the uniformly distributed ZnCl_(2)and[PHSO_(3)MIM][MSA].In addition,the hydrogen bond(H-bond)is formed between CHO and ILs.After ten reaction cycles,no significant structure changes are observed in the recovered[PHSO_(3)MIM][MSA]-ZnCl_(2).The solubilities of ILs are predicted by using COSMO-RS model,the results show that[PHSO_(3)MIM][MSA]is a promising candidate for the liquid phase Beckmann rearrangement of CHO into CPL.Finally,a theoretical model of the H-bond interactions between ILs and CHO is further confirmed to support the advance of reaction mechanism.A feasible way is provided for the CPL production technique in the liquid phase Beckmann rearrangement reaction.
基金the National Key Basic Research Development Plan“973”Project(No.2006CB202508)the National Key R&D Program of China(No.2021YFA1502600)+2 种基金State Key Laboratory of Catalytic Materials and Reaction Engineering(RIPP,SINOPEC)(No.33600000-20-ZC0607-0024)the SINOPEC Project(Nos.411058 and 413025)the National Natural Science Foundation(Nos.21808244,22178347,and 22072182).
文摘Developing efficient and stable zeolites for vapor-phase Beckmann rearrangement of cyclohexanone oxime is still a great challenge to realizeε-caprolactam(CPL)green production.In this work,the hierarchical porous silicalite-1 zeolites with multiple hollow structure(S-1-M)are explored by in-situ desilication−recrystallization post-treatment of spongy highway-like zeolites(S-1-S),which are synthesized through silanization synthesis of conventional bulky silicalite-1(S-1).Compared to S-1,S-1-M achieves superior catalytic performance,with improving the CPL selectivity from 85.7%to 94.1%and prolonging the catalyst lifetime from 74 to 126 h at a weight hourly space velocity(WHSV)of 6 h^(−1).Comprehensive physiochemical studies demonstrate that the highly dispersed intracrystalline cavities within S-1-M endow greater mass diffusion and better quasi acidity inducing by the enhanced H-bonds among abundant H-bonded silanols,which is cooperatively responsible for its superior catalytic performance.
基金supported by National Key Research and Development Project (No. 2021YFC2100100)National Natural Science Foundation of China (No. 21901123)+1 种基金Natural Science Foundation of Jiangsu Province (No. BK20190694)Jiangsu Specially Appointed Professor Plan
文摘The Beckmann rearrangement has been predominantly studied for the synthesis of amide and lactam.By strategically using the in situ generated Appel’s salt or Mitsunobu’s zwitterionic adduct as the de-hydrating agent,a series of Beckmann rearrangement and following cascade reactions have been devel-oped herein.The protocol allows the conversion of various ketoximes into amide,thioamide,tetrazole and imide products in modular procedures.The generality and tolerance of functionalities of this method have been demonstrated.
基金the Foundations for Basic Research ofTsinghua U niversity and of China Petrochem icalCompany
文摘Four different ZSM 5 zeolites are tested for the gas phase Beckmann rearrangement of cyclohexanone oxime (CHO) into lactam. B ZSM 5 derived titanosilicalite (Ti ZSM 5) exhibits catalytic performances comparable to hydrothermally synthesized titanosilicalite (TS 1), much better than B ZSM 5 and Al ZSM 5. The effect of reaction conditions (solvent, feed space velocity, and water) on the catalytic performance of Ti ZSM 5 is studied. It is found that a quantitative relationship exists among the feed space velocity, the reaction time, and the CHO constant conversion. Ethanol or methanol as solvent shows higher activity, lactam selectivity, and stability than benzene and n hexanol. The addition of water to the rearrangement with a maximum amount of 1.0 mole per mole CHO results in the increase of CHO conversion while no meaningful changes in lactam selectivity and stability are observed.
文摘Silicalite-1 was hydrothermally synthesized in the presence of different concentrations of Na+using tetrapropylammonium hydroxide(TPAOH)as a template.The synthesis was followed by a base treatment.The silicalite-1samples were characterized using X-ray diffrac-tion,scanning electron microscopy,N2 adsorption,X-ray photoelectron spectroscopy,Fourier transform infrared spectroscopy and NH3 temperature-programmed deso-rption.The samples were used as catalysts for the vapor phase Beckmann rearrangement of cyclohexanone oxime.During the synthesis,the sodium ions were incorporated onto the silicalite-1 crystals,but were then removed by the base treatment.All the catalysts exhibited nearly complete conversion of cyclohexanone oxime toε-caprolactam with selectivities grater than 95%.Addition of less than 2.5 mol-%Na^(+)(relative to TPAOH)did not influence the catalytic properties.However,for Na+concentrations≥5 mol-%,the particle sizes of silicalite-1 increased and the catalytic activities decreased,which can be attributed to carbon deposition.The results in this work are of great importance for the polymer industry.
文摘A facile and efficient approach to the synthesis of secondary thioamides from ketoximes via Beckmann rearrangement has been established, using phosphorus pentasulfide as a dehydrating and thiating agent. It is also efficient for the preparation of primary thiobenzamide from benzaldoxime. This approach features simple-operation, easy-control and good to excellent yields.
文摘An efficient Beckrnann rearrangement of ketoximes was developed using carbon tetrabromide/triphenylphos- phine as an organocatalyst without addition of any acids or metals. The reaction showed good functional group tol- erance and gave various amides in moderate to good yields.
基金supported by research grants from the National Natural Science Foundation of China (No. 21272048)Natural Science Foundation of Shandong Province (No. ZR2015BQ012)the Scientific Research Foundation for the Returned Overseas Chinese Scholars, State Education Ministry (to J. Li)
文摘A facile synthesis for cyanochlorin related to chlorophyll from a formyl-substituted chlorin, by the oxidation of methyl （pyro）pheophorbide-a, was accomplished. These readily available chlorin aldehydes were assembled together with hydroxylamine hydrochloride in a tandem process to produce the corresponding chlorin nitriles in moderate to good yields. The formation of chlorin nitrile was discussed and a possible mechanism for the corresponding cyanation reaction was tentatively proposed.
