TETRAAZAANNULENE COBALT COMPLEX COMPOUNDS AND METHOD FOR PREPARATION THEREOF

Abstract: A tetraazaannulene cobalt complex compound having the general formula (I): wherein R₁, R₂ and R₃ each independently is a hydrogen atom, a C₁₋₈ alkoxy group or a C₁₋₈ alkyl group but in case of one of R₁, R₂ and R₃ being a hydrogen atom the other two groups are not hydrogen atoms at the same time, and when R₁ is a methyl group R₂ and R₃ are not hydrogen atoms at the same time.

Description: TETRAAZAANNULENE COBALT COMPLEX COMPOUNDS AND METHOD FOR PREPARATION THEREOF This invention relates to a tetraazaannulene cobalt complex compound (hereinafter referred to Co-TAA) useful as an oxygen reduction catalyst and a method for the preparation of the Co-TAA. Various kinds of oxygen reduction catalysts have been known. Especially, platinum has been well known as an oxygen reduction catalyst because of the superior catalytic properties. However, it is difficult to practically employ platininum as a catalyst in a fuel battery because platinum is expensive and a rare metal. Therefore, the development of new catalysts having a low oxygen reduction voltage and a high catalytic activity have been desired and made. However, catalysts which can take the place of platinum have not been found. The Co-TAA having the formula (VII); EMI1.1 is reported as an oxygen reduction catalyst having a high activity in F. Beck et al, Z. Naturforsch. 28a, 1009-1021(1973), and DE-OS 20 46 354. However, the catalyst life of the Co-TAA of the formula (VII) is short and, in addition, the catalyst activity is not satisfactory. Further, the Co-TAA having the formula (VIII);, EMI2.1 is reported in Y. Nishida et al, Bulletin of the Chemical Society of Japan, Vol. 50(9), 2485-2486 (1977). There is no description relating to the oxygen reduction catalyst properties of the Co-TAA of the formula (VIII) in the report. The inventors of this invention have produced the Co-TAA of the formula (VIII) to measure the catalytic properties, and found that the catalyst activity is insufficient though the catalyst life is long. A method for the preparation of the Co-TAA is described in Y. Nishida et al, Journal of Coordination Chemistry, Vol. 9, 161-166 (1979). This method, however, has the defect that the reaction procedures and the aftertreatments are difficult due to the use of sulfur and acetyl hydroperoxide in the production of the starting material, that is, dithiolium hydrogensulfate. Further, this method has such defects that the-yields of the tetraazaannulene and the Co-TAA are low, that the purity of the Co-TAA is also low and that the purification of the Co-TAA is difficult. An object of this invention is to provide a novel Co-TAA. Another object of this invention is to provide a novel method for preparing the Co-TAA including conventional Co-TAA, and a tetraazaannulene derivative which is an intermediate of the Co-TAA. Accordingly, this invention provides a novel Co-TAA having the general formula (I); EMI3.1 wherein R1, R2 and R3 each independently is a hydrogen atom, a C 1 - B alkoxy group or a C1¯ 8 alkyl group but in case of one of R1, R2 and R3 being a hydrogen atom the other two groups are not hydrogen atoms at the same time, and when R1 is a methyl group R2 and R3 are not hydrogen atoms at the same time. Suitable examples of Co-TAA of this invention of the formula (I) include; (1) R1 is a C1-8 alkoxy group, (2) R1 and R2 each independently is a Cl-s alkoxy group, (3) Ri and R2 each independently is a Cl-s alkoxy group and R3 is a hydrogen atom, (4) each of R1, R2 and R3 independently is a C1-8 alkoxy group, (5) R1 is a Ci-a alkoxy group and R2 and R3 are the same and C1-8 alkoxy groups, (6) R1 is a C1-8 alkoxy group and R2 and R3 are both hydrogen atoms, (7) R1 is a C1-8 alkoxy group and R2 and R3 each independently is a C1-8 alkyl group, (8) R1 is a C1-8 alkoxy group and R2 and R3 are the same and C1-8 alkyl groups, (9) R1 is a C1¯8 alkyl group, (10) R1 is a C1-8 alkyl group and R2 and R3 each independently is a C1-8 alkoxy group, (11) R1 is a C1-8 alkyl group and R2 and R3 are the same and C1-8 alkoxy groups, (12) each of R1, R2 and R3 independently is a C1-8 alkyl group, (13) R1 is a C1-8 alkyl group and R2 and R3 are the same and Cl-B alkyl groups, (14) R1 is a C2-8 alkyl group and R2 and R3 are both hydrogen atoms, (15) R1 is a hydrogen atom, (16) R1 is a hydrogen atom and R2 is a C1-8 alkoxy group, (17) R1 is a hydrogen atom and R2 and R3 each independently is a Ci-a alkoxy group, (18) R1 is a hydrogen atom and R2 and R3 are the same and C1-8 alkoxy groups, (19) R1 and R3 are both hydrogen atoms and R2 is a Ci-a alkoxy group, (20) R1 is a hydrogen atom and R2 is a Cl-s alkyl group, (21) R1 is a hydrogen atom and R2 and Ra each independently is a C1-8 alkyl group, (22) R1 is a hydrogen atom and R2 and R3 are the same and Cl-a alkyl groups, and (23) R1 and R3 are both hydrogen atoms and R2 is a C1-8 alkyl group. Preferred R1, R2 and Ra include a hydrogen atom, a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an iso-butoxy group, a npentyloxy group, a n-hexyloxy group, an-heptyloxy group, a n- octyloxy group, a methyl group, an ethyl group, a n-propyl group, an iso-propyl group, a n-butyl group, an iso-butyl group, a n-pentyl group, a n-hexyl group, a n-heptyl group and a n-octyl group. Preferred Co-TAA of this invention is the compound of the formula (I) where one or two of R1, R2 and R3 are methoxy groups1 for example, one or two of R1, R2 and R3'are methoxy groups and the other group or groups are hydrogen atoms, R1 is a methoxy group and R2 and R3 are the same and C4-8 alkoxy groups, R1 is a methoxy group and R2 and R3 are the same and C1-4 alkyl groups, R1 is a C48 alkoxy group and R2 and R3 are both methoxy groups; R1 is a C1-4 alkyl group and R2 and R3 are both methoxy groups, and all of R1, R2 and R3 are methoxy groups; the compound of the formula (I) where one or two of R1, R2 and Rg are methyl groups and the other group or groups are Ci- 4 alkyl groups or C4-8 alkoxy groups, for example, R1 is a methyl group and R2 and R3 are the same and C1-4 alkyl groups or C4-8 alkoxy group, and R2 and R3 are both methyl groups and R1 is a C1-4 alkyl group or a C48 alkoxy group; the compound of the formula (I) where R1, R2 and R3 are all methyl groups; the compound of the formula (I) where R1 and R2 are the same and C4-8 alkoxy groups and R3 is a hydrogen atom; the compound of the formula (I) where R1 is a C1-4 alkoxy group and R2 and R3 are the same and Ci-4 alkyl groups; or the compound of the formula (I) where R1, R2 and R1 are all n-butoxy groups. More specifically, preferred examples of the Co-TAA having a higher catalyst activity and a longer catalyst life include EMI7.1 EMI8.1 EMI9.1 Preferred examples of the Co-TAA having higher catalyst activity of this invention include EMI9.2 EMI10.1 The Co-TAA including the novel Co-TAA of this invention, which can be represented by the general formula (11); EMI11.1 wherein R4 is a hydrogen atom, a C1-8 alkoxy group, a C1-8 alkyl group, a halogen atom, a nitro group, a cyano group, a C1-8 acyloxy group, a hydroxyl group, a carboxyl group, a C1-8 alkoxycarbonyl group, a carbamoyl group, a N,N-di C1-6 alkylamino group, a C1-8 acylamino group, a C1-8 alkoxy carbonyl C13 alkyl group, a N,N-di C1-6 alkyl amino C1-3 alkyl group, or an amino group; ; n is integer of 1 to 5; and Rs and Ra each independently is a hydrogen atom, a C1-8 alkoxy group, a C18 9 alkyl group, a halogen atom, a nitro group, a cyano group, a C1-8 acyloxyl group, a hydroxyl group, a carboxyl group, a Cl-B alkoxycarbonyl group, a carbamoyl group, a N,N-di C1-6 alkylamino group, a C1-8 alkoxycarbonyl C1-3 alkyl group, or a C1-6 6 acylamino group; can be obtained by the following five methods. Method 1 EMI12.1 Method 2 EMI12.2 Method 3 EMI13.1 Method 4 EMI13.2 Method 5 EMI14.1 In the above described formulae (III), (IV), (V) and (VI), R4, R5, R6 and n are the same as defined in the formula (II); R7 is a C18 alkyl group; and R8 and R9 each independently is a C1-6 alkyl group. According to Method 1, the Co-TAA of the formula (II) can be obtained by react'ing a ss-alkoxy-a-arylacrolein of the general formula (III) with an o-phenylenediamine derivative of the general formula (IV) to prepare a tetraazaannulene derivative of the formula (V) , and then reacting the tetraazaannulene derivative (V) with a cobalt compound.: The reaction (A) between the ss-alkoxy-a-arylacrolein (III) and the o-phenylenediamine derivative (IV) can be carried out at 500C - 2500C either in the absence of a solvent or in the presence of a solvent. Preferably, the reaction (A) is carried out in the presence of a solvent at around the boiling point of the solvent employed. Preferably n in the formula (III) of the ss-alkoxy- a-arylacroleins which can be employed in the reaction (A) is one. Preferred R4 in the formula (III) of the ss-alkoxy- a-arylacroleins which can be employed in the reaction (A) is in the para position. Exemplary ss-alkoxy-a-arylacroleins (III) which can be employed in the reaction (A) include ss-ethoxy-&alpha;-phenyl- acrolein, ss-ethoxy-&alpha;-(p-nitrophenyl)acrolein, ss-ethoxy-&alpha;-(p- methoxyphenyl)acrolein, B-ethoxy-a-(p-tolyl)acrolein, S-ethoxy- &alpha;-[p-(n-butyl)phenyl]acrolein, ss-ethoxy-&alpha;-(p-cyanophenyl)- acrolein, 6-ethoxy-a-(p-chlorophenyl)acrolein, ss-ethoxy-a-(p- bromophenyl)acrolein, ss-ethoxy-&alpha;-[p-(ethoxycarbonyl)phenyl]- Acrolein, ss-ethoxy-&alpha;-(p-carboxyphenyl)acrolein, ss-ethoxy-&alpha; ;- (p-carbamoylphenyl)acrolein, B-ethoxy-a-(p-hydroxyphenyl)- acrolein, ss-ethoxy-&alpha;-[p-(N,N-dimethylaminomethyl)phenyl]- acrolein, ss-ethoxy-a-[p-(N,N-dimethylamino)phenyl]acrolein, ss-ethoxy-&alpha;-[p-(ethoxycarbonylmethyl)phenyl]acrolein and the similar acroleins as described above, whose position of the acroleins is a methoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, a n-pentyloxy group, a hexyloxy group or a cyclohexyloxy group. Preferred R4 in the formula (III) of the ss-alkoxy- a-arylacroleins which can be employed in the reaction (A) is a hydrogen atom, a methoxy group, a methyl group, a halogen atom, a nitro group, a cyano group or a carboxyl group. Accordingly, preferred e-alkoxy-a-arylacroleins (III) include B-ethoxy-a-phenylacrolein, 8-ethoxy-a-(p-nitrophenyl)acrolein, ss-ethoxy-&alpha;-(p-methoxyphenyl)acrolein, ss-ethoxy-&alpha;-(p-tolyl)- acrolein, ssethoxy-&alpha;-(p-cyanophenyl)acrolein, ss-ethoxy-&alpha;-(p- chlorophenyl) acrolein, ss-ethoxy-c-(p-bromophenyl)acrolein and ss-ethoxy-&alpha;-(p-carboxyphenyl)acrolein. Th a-alkoxy-a-arylacroleins of the general formula (III) can be obtained by hydrolyzing the ss-N,N-dialkylamino- a-arylacrolein of the general formula (VI) and reacting the compound obtained with a C1¯6 alkyl nalide. The methods for pre paring the ss-alkoxy-a-arylacroleins (III) are easier than those for preparing dithiolium hydrogen sulfate which is the starting material of known methods. Therefore, there is a good possibility that the method of this invention will be able to provide various kinds of the Co-TAA. Exemplary o-phenylenediamine derivatives (IV) which can be employed in the reaction (A) include o-phenylenediamine, 4-(CI- alkoxy)-o-penylenediamines, 4-(CI- @ alkyl)-o-phenylene- diamines, 4, 5-di C1-8 alkyl-o-phenylenediamine, 4,5-dichloro-ophenylenediamine, 4-nitro-o-phenylenediamine, 4-chloro-ophenylenediamine, 4-carbamoyl-o-phenylenediamine, 4-carboxyo-penylenediamine, 4-cyano-o-phenylenediamine, 4-dimethylamino-o-phenylenediamine, 4,5-di C1 - a alkoxy-o-phenylenediamine, 4-ethoxycarbonylmethyl-o-phenylenediamine, 4-carboxy-5methyl-o-phenylenediamine and 4-ethoxycarbonyl-o-phenylenediamine. Preferred R5 and Ra in the o-phenylenediamine derivatives (IV) which can be employed in the reaction (A) include a hydrogen atom, a methoxy group, a methyl group, a halogen atom, a nitro group and a carboxyl group. Accordingly, preferred o-phenylenediamine derivatives (IV) include o-phenylenediamine, 4-methyl-o-phenylenediamine, 4-chloro-ophenylenediamine, 4,5-dimethyl-o-phenylenediamine, 4,5dichloro-o-phenylenediamine, 4-nitro-o-phenylenediamine, 4-methoxy-o-phenylenediamine and 4-carboxy-5-methyl-o phenylenediamine. The solvents which can be employed in the reaction (A) include alcohols, phenols, cyclic ethers and non-proton polar organic solvents such as N ,N-dimethylformamide, dimethyl sul foxide, hexamethylphosphorictriamide and N-methylpyrrolidone. The reaction (A) can be preferably carried out in the presence of the non-proton (aprotic) polar organic solvent at around the boiling point of the solvent employed because the desired compounds of the formula (V) can be obtained as pure crystals in a higher yield when the reaction solution is cooled. The reaction (B) between the tetraazaannulene derivative of the formula (V) as obtained in the reaction (A) and a cobalt compound can be carried out in the presence of a solvent at 500C - 2500C. Preferably, the reaction (B) is carried out at around the boiling point of the solvent employed. Exemplary cobalt compounds which can be employed in the reaction (B) include cobalt salts of organic acids such as cobalt (II) carbonate, cobalt (II) acetate, cobalt (II) lactate, cobalt (II) oxalate, cobalt (tri) citrate, cobalt (II) tartarate and cobalt (II) gluconate; cobalt salts of inorganic acids such as cobalt (II) chloride, cobalt (II) bromide and cobalt (II) iodide; and cobalt complex salts such as cobalt (II) acetylacetonate. The solvents which can be employed in the reaction (B) include alcohols, phenols, cyclic ethers and non-proton polar organic solvents such as N,N-dimethylformamide, dimethyl sulfoxide, hexamethylphosphorictriamide and N-methylpyrrolidone. The reaction (B) can be preferably carried out in the presence of the non-proton polar organic solvent at around the boiling point of the solvent employed because the products of the formula (II) can be obtained in the pure form in a higher yield. According to Method 2, the Co-TAA of the formula (II) can be obtained by reacting a ss-alkoxy-a-arylacrolein of the general formula (III) with an o-phenylenediamine derivative of the general formula (IV) in the presence of a cobalt compound. The reaction (C) among the -alkoxy-a-arylacrolein (III), the o-phenylenediamine derivative (IV) and the cobalt compound can be carried out at 500C - 2500C either in the absence of a solvent or in the presence of a solvent. Preferably, the reaction (C) is carried out in the presence of a solvent at around the boiling point of the solvent employed. The mol ratio of the B-alkoxy-a-arylacrolein (III): the o-phenylenediamine derivative (IV): the cobalt compound which can be employed in the reaction (C) is 2:2:1. Preferred n in the ss-alkoxy-a-arylacroleins of the formula (III) which can be employed in the reaction (C) is one. Preferred R4 in the 8-alkoxy-a-arylacroleins of the formula (III) which can be employed in the reaction (C) is in the para position. Exemplary ss-alkoxy-a-arylacroleins (III) which can be employed in the reaction (C) include the same acroleins as those employed in the reaction (A) of Method 1. Preferred R4 in the ss-alkoxy-a-arylacroleins of the formula (III) which can be employed in the reaction (C) includes a hydrogen atom, a methoxy group, a methyl group, a halogen atom, a nitro group and a cyano group. Accordingly, preferred ss-alkoxy-a-arylacroleins (III) which can be employed in the reaction (C) include ss-ethoxy-a-phenylacrolein, ss- ethoxy-a-(p-nitrophenyl)acrolein, ss-ethoxy-a-(p-methoxy- phenyl)acrolein, ss-ethoxy-&alpha;-(p-tolyl)acrolein, ss-ethoxy-&alpha;- (p-cyanophenyl)acrolein, ss-ethoxy-&alpha;-(p-chlorophenyl)acrolein and ss-ethoxy-&alpha;-(p-bromophenyl)acrolein. Exemplary o-phenylenediamine derivatives (IV) which can be employed in the reaction (C) include the same o phenylenediamines as those employed in the reaction (A) of Method 1. Preferred R5 and R8 in the o-phenylenediamine derivative (TV) which can be employed in the reaction (C) include a hydrogen atom, a methoxy group, a methyl group and a halogen atom. Accordingly, preferred o-phenylenediamine derivatives (IV) include o-phenylenediamine, 4-methyl-ophenylenediamine, 4-chloro-o-phenylenediamine, 4,5-dimethylo-phenylenediamine, 4,5-dichloro-o-phenylenediamine and 4methoxy-o-phenylenediamine. Exemplary cobalt compounds and the solvents which can be employed in the reaction (C) include the same as those employed in the reaction (B) of Method 1. The reaction (C) can be preferably carried out in the presence of the non-proton polar organic solvent at around the boiling point of the solvent employed because the products of the formula (II) can be obtained in the pure form in a higher yield. Further, the yield of the products obtained in Method 2 is higher than that of Method 1. According to Method 3, the Co-TAA of the formula (11) can be obtained by reacting a B-N,N-dialkylamino-a-arylacroiein of the general formula (VI) with an o-phenylenediamine derivative of the general formula (IV) to prepare a tetraazaannulene derivative of the formula (V), and reacting the tetraazaannulene derivative with a cobalt compound. The reaction (D) between the B-N,N-dialkylamino-a- arylacrolein (VI) and the o-phenylenediamine derivative (IV) can be carried out at 500C - 2500C either in the absence of or in the presence of a solvent. Preferably, the reaction (D) is carried out in the presence of a solvent at around the boiling point of the solvent employed. Preferred n in the B-N,N-dialkylamino-a-arylacrolein of the formula (VI) which can be employed in the reaction (D) is one. Preferred R4 in the B-N,N-dialkylamino-a-arylacrolein of the formula (VI) which can be employed in the reaction (D) is in the para position. Exemplary B-N,N-dialkylamino-a-arylacroleins (VI) which can be employed in the reaction (D) include ss-dimethyl- amino-&alpha;-phenylacrolein, ss-dimethylamino-&alpha;-[p-(C1-8 alkoxy)phenyl]acroleins, ss-dimethylamino-&alpha;[p-(C1-8 alkyl)phenyl]acroleins, ss-dimethylamino-&alpha;-(p-nitrophenyl)acrolein, ss dimethylamino-a [p-(dimethylamino)phenyl]acrolein, ss-dimethyl- amino-&alpha;-(p-cyanophenyl)acrolein, ss-dimethylamino-&alpha;-(p-chloro- phenyl)acrolein, ss-dimethylamino-&alpha;-[p-(ethoxycarbonylmethyl)- phenyl]acrolein, ss-dimethylamino-&alpha;-(p-carboxyphenyl)acrolein, ss-dimethylamino-&alpha; ;-(p-carbamoylphenyl)acrolein, ss-dimethylamino &alpha;-(p-hydroxyphenyl)acrolein, ss-dimethylamino-&alpha;-[p-(ethoxy- carbonyl)phenyl]acrolein and the similar acroleins as described abDve,where in position of the acroleins is a diethylamino group, a dipropylamino group, a dibutylamino group, a (Nmethyl,N-ethyl) amino group or a (N-methyl,N-butyl) amino group. Preferred R4 in the ss-N,N-dialkylamino-&alpha;-arylacroleins (VI) which can be employed in the reaction (D) is a hydrogen atom, a Cl-a alkoxy group, a C18 alkyl group, a nitro group or an ethoxycarbonyl group. Preferred R8 and R9 in the ss-N,N-dialkylamino-&alpha;- arylacroleins (VI2 which can be employed in the reaction (D) include a methyl group, an ethyl group, a n-propyl group and a n-butyl group. The ss-N,N-dialkylamino-&alpha;-arylacroleins of the general formula (VI) can be produced by referring to the methods de scribed in Z. Arnold, Collection of Czechoslov. Chem. Commun. Vol. 26, 3051(1961). Exemplary o-phenylenediamine derivatives (IV) which can be employed in the reaction (D) include the same-o-phenylene- diamines as those employed in the reaction (A) of Method 1. Preferred R5 and R6 in the o-phenylenediamine derivatives (IV) which can be employed in the reaction (D) include a hydrogen atom, a C1-8 alkoxy group, a halogen atom and a C1a B alkyl group. The solvents which can be employed in the reaction, (D) include the same solvents as those employed in the reaction (A) of Method 1. The reaction (D) can be preferably carried out in the presence of the non-proton polar organic solvent at around the boiling point of the solvent employed because the compounds of the formula (V) can be obtained in the pure form in a higher yield. The reaction (E) between the tetraazaannulene derivative of the formula (V) as obtained in the reaction (D) and a cobalt compound can be carried out in the presence of a solvent at 500C - 2500C. Preferably, the reaction (E) is carried out at around the boiling point of the solvent employed. The cobalt compounds and the solvents which can be employed in the reaction (E) include the same as those employed in the reaction (B) of Method 1. The reaction (E) can be preferably carried out in the presence of the non-proton polar organic solvent at around the boiling point of the solvent employed because the products of the formula (II) can be obtained in the pure form in a higher yield. According to Method 4, the Co-TAA of the formula (II) can be obtained by reacting a B-N,N-dialkylamino-a-arylacrolein of the general formula (VI) with an o-phenylenediamine derivative of the formula (IV) in the presence of a cobalt compound. The reaction (F) among the ss-N,N-dialkylamino-a- arylacrolein (VI), the o-phenylenediamine derivative (IV) and the cobalt compound can be carried out at 500C - 2500C either in the absence of or in the presence of a solvent. Preferably, the reaction (F) is carried out in the presence of a solvent at around the boiling point of the solvent employed. The mol ratio of the B ss-N,N-dialkylamino-a-aryl- acrolein (VI): the o-phenylenediamine derivative (IV): the cobalt compound which can be employed in the reaction (F) is 2:2:1. Preferred n in the S-N,N-dialkylamino-a-arylacroleins (VI) which can be employed in the reaction (F) is one. Preferred R4 in the B-N,N-dialkylamino-a-arylacroleins (VI) which can be employed in the reaction (F) is in the para position. Exemplary B-N,N-dialkylamino-a-arylacroleins (VI) which can be employed in the reaction (F) include the same acroleins as those employed in the reaction (D) of Method 3. Preferred R4 in the ss-N,N-dialkylamino-&alpha;-arylacroleins of the formula (VI) which can be employed in the reaction (F) is a hydrogen atom, a C18 alkoxy group, a C1-8 alkyl group, a halogen atom, a nitro group, a cyano group or an ethoxyQ carbonyl group. Preferred R8 and Rs in the B-N,N-dialkylamino-a- arylacroleins (VI) which can be employed in the reaction' (F) include a methyl group, an ethyl group, a n-propyl group and a n-butyl group. Exemplary o-phenylenediamine derivative (IV) which can be employed in the reaction (F) include the same o-phenylenediamines as those employed in the reaction (D) of Method 3. Preferred R5 and R8 in the o-phenylenediamine derivatives (TV) which can be employed in the reaction (F) include a hydrogen atom, a C18 alkoxy group, a C18 alkyl group and a halogen atom. Exemplary cobalt compounds and the solvents which can be employed in the reaction (F) include the same as those employed in the reaction (E) of Method 3. The reaction (F) can be preferably carried out in the presence of the non-proton polar organic solvent at around the boiling point of the solvent employed because the products of the formula (II) can be obtained in the pure form in a higher yield. Further, the yield of the products obtained in Method 4 is higher than that of Method 3. The novel compound (I) of this invention can be prepared by reacting the ss-C1-8 alkoxy-a-(p-hydroxyphenyl) acrolein with an o-phenylenediamine derivative (IV) where Rs and Ra each independently is a hydrogen atom, a C1-8 alkoxy group or a C18 alkyl group in the presence of a cobalt com pound, and reacting the compound obtained with a C28 , alkyl halide. (Method 5) The reaction (G) between the ss-C1-8 alkoxy a-(p-hydroxyphenyl)acrolein, the o-phenylenediamine derivative (IV) and the cobalt compound can be carried out under the same reaction conditions as those of the reaction (F). The reaction between the compound as obtained in the reaction (G) and the C2-8 alkyl halide can be carried out in the presence of a solvent for the compound at 250C -1000C. In each of Method 1 - 5, the products are confirmed as the Co-TAA of the formula (I) or the formula (II), or the tetraazaannulene derivatives of the formula (V) by the value of physical properties such as elementary analysis, Mass spectra and visible spectra of the products obtained. The Co-TAA of the formulae (I) and (II) are useful as an oxygen reduction catalyst and the tetraazaannulene derivatives of the formula (V) are useful as the intermediate of the Co-TAA. The following examples illustrate the present invention in more detail, but they are given for illustrative purposes only and are not to be construed as limiting the invention. Example 1 EMI27.1 In 20 ml of N,N-dimethylformamide were dissolved 5 millimol (540 mg) of o-phenylenediamine and 2.5 millimol (623 mg) of cobalt (II) acetate tetrahydrate, and the solution was heated at 1200C for 30 minutes. The solution was added with 5 millimol (1025 mg) of B-dimethylamino-a- (p-methoxyphenyl)- acrolein and refluxed under heating for 3 hours. The reaction solution was cooled, filtered, washed with methanol and dried to give dark purple crystals in a yield of 60.0%. The crystals have the following physical values. Mass Spectrum: Calcd.: 557.5 Found : 557 Elementary Analysis: Calcd.: C:H:N = 68.94:4.70:10.05 Found : C:H:N = 68.83:4.76:10.25 Visible Spectrum (nm) [in DMF]: 380(s) , 397, 429(s) and 522 * : (s) means a shoulder of a peak. Example 2 EMI28.1 In 10 ml of N,N-dimethylformamide were dissolved 2.5 millimol (270 mg) of o-phenylenediamine and 1.25 millimol (312 mg) of cobalt (II) acetate tetrahydrate, and the solution was heated at 1200C for 30 minutes. Then, the solution was added with 2.5 millimol (612.5 mg) of B-dimethylamino-a-(p- n-butoxyphenyl)acrolein and refluxed under heating for 3 hours. The reaction solution was cooled, filtered, washed with methanol and dried to give dark purple crystals in a yield of 45.4t. The crystals have the following physical values. Mass Spectrum: Calcd.: 641.7 Found : 641 Elementary Analysis: Calcd.: C:H:N = 71.13:5.97:8.73 Found : C:H:N = 70.95:6.01:8.77 Visible Spectrum (nm) [in DMF]: 380(s)*, 397, 429(s) and 522 * : (s) means a shoulder of a peak. Example 3 EMI29.1 In 10 ml of N,N-dimethylformamide were dissolved 2.5 millimol (420 mg) of 4,5-dimethoxy-o-phenylenediamine, 1.25 millimol (312 mg) of cobalt (II) acetate tetrahydrate and 2.5 millimol (513 mg) of B-dimethylamino-a-(p-methoxy- phenyl)acrolein, and the solution was refluxed under heating in an argon gas atmosphere for 5 hours. The reaction solution was cooled, filtered, washed with methanol and dried to give dark purple crystals in a yield of 17.0%. The crystals have the following physical values. Mass Spectrum: Calcd.: 667.6 Found : 667 Elementary Analysis: Calcd.: C:H:N = 63.81:5.06:8.27 Found : C:E:N = 63.77:4.88:8.40 Visible Spectrum (nm) [in DMF: 384, 395(s) , 430, 457 and 525 * : (s) means a shoulder of a peak. Example 4 Step 1 EMI30.1 In 20 ml of N,N-dimethylformamide were dissolved 5 millimol (690 mg) of 4-methoxy-o-phenylenediamine and 2.5 millimol (625 mg) of cobalt (II) acetate tetrahydrate, and the solution was heated at 1200C for 30 minutes. Then, the solution was added with 5 millimol (955 mg) of B-dimethylamino-a (p-hydroxyphenyl)acrolein, and refluxed underheat1ng in an argon gas atmosphere for 5 hours. The reaction solution was cooled and added with methanol to precipitated crystals. The crystals were separated by filtration, washed with methanol and dried. The yield was 7.5%. Step 2 EMI31.1 In 10 ml of N,N-dimethylformamide was dissolved the crystals obtained in Step 1. To the solution obtained were added 6 times amount of propyl iodide based on the millimol of the crystals and 6 times amount of potassium carbonate based on the millimol of the crystals. Then, the mixture was stirred at 250C for 12 hours. To the reaction mixture was added excess of water to precipitated crystals. The crystals were obtained by filtration, washed with methanol and dried to give dark purple crystals in a yield of 50%. The crystals have the following physical values. Mass Spectrum: Calcd.: 673.7 Found : 673 Elementary Analysis: Calcd.: C:H:N = 67.75:5.69:8.32 Found : C:H:N = 68.01:5.55:8.25 Visible Spectrum (nm) [in DMFj: 399, 420(s), 443(s), 388(s) and 520 * : (s) means a shoulder of a peak. EMI32.1 In 10 ml of N,N-dimethylformamide were dissolved 2.5 millimol (473 mg) of ss-dimethylamino-&alpha;-(p-methylphenyl)- acrolein, 1.25 millimol (312 mg) of cobalt (II) acetate tetrahydrate and 2.5 millimol (340 mg) of 4,5-dimethyl-o-phenylene diamine, and the solution was refluxed under heating for 5 hours. The reaction solution was cooled, filtered, washed with methanol and dried to give brown crystals in a yield of 68.8%. The crystals have the following physical values. Mass Spectrum: Calcd.: 581.6 Found : 581 Elementary Analysis: Calcd.: C:H:N = 74.34:5.89:9.63 Found : C:H:N = 74.43:5.87:9.61 Visible Spectrum (nm) [in DMF]: 384, 398, 423, 440(s) and 524 * : (s) means a shoulder of a peak. Examples 6 # 209 Co-TAA of this invention was prepared by the methods as shown in Table 1. The results are also shown in Table 1. EMI34.1 Table <SEP> 1-1 <tb> # <SEP> # <SEP> Example <SEP> No. <SEP> # <tb> Example <SEP> of <SEP> Reaction <SEP> Yield <SEP> Crystal <tb> No. <SEP> R1 <SEP> R2 <SEP> R3 <SEP> Conditions <SEP> (%) <SEP> Color <SEP> R1 <SEP> R2 <SEP> R3 <tb> 6 <SEP> -OC2H5 <SEP> -H <SEP> -H <SEP> 2 <SEP> 43.6 <SEP> Dark <SEP> -OC2H5 <SEP> -H <SEP> -H <tb> Purple <tb> 7 <SEP> -OCH2CH2CH3 <SEP> -H <SEP> -H <SEP> 2 <SEP> 42.2 <SEP> -ditto- <SEP> -OCH2CH2CH3 <SEP> -H <SEP> -H <tb> 8 <SEP> -H <SEP> -OCH3 <SEP> -H <SEP> 1 <SEP> 8.9 <SEP> -ditto- <SEP> -H <SEP> -OCH3 <SEP> -H <tb> 9 <SEP> -H <SEP> -OC2H5 <SEP> -H <SEP> 3 <SEP> 7.7 <SEP> -ditto- <SEP> -H <SEP> -OC2H5 <SEP> -H <tb> 10 <SEP> -OCH(CH3)2 <SEP> -H <SEP> -H <SEP> 2 <SEP> 40.7 <SEP> -ditto- <SEP> -OCH(CH3)2 <SEP> -H <SEP> -H <tb> CH3 <SEP> CH3 <tb> 11 <SEP> -OCHCH2CH3 <SEP> -H <SEP> -H <SEP> 2 <SEP> 44.1 <SEP> -ditto- <SEP> -OCHCH2CH3 <SEP> -H <SEP> -H <tb> 12 <SEP> -OCH2CH(CH3)2 <SEP> -H <SEP> -H <SEP> 2 <SEP> 46.3 <SEP> -ditto- <SEP> -OCH2CH(CH3)2 <SEP> -H <SEP> -H <tb> 13 <SEP> -H <SEP> -OCH3 <SEP> -OCH3 <SEP> 3 <SEP> 0.52 <SEP> Reddish <SEP> -H <SEP> -OCH3 <SEP> -OCH3 <tb> Purple <tb> Table 1-1 (-continued) Elementary Analysis Mass Spectrum C:H:N (%) Example Visible Spectrum [DMF] No. Calcd. Found Formula Calcd. Found (nm) *1) 6 585.6 585 C34H30N4O2.Co 69.74:5.16:9.57 69.61:5.22:9.56 380(s), 397, 429(s) 522 7 613.6 613 C36H34N4O2.Co 70.47:5.59:9.13 69.99:5.65:8.98 380(s), 397, 429(s), 522 8 557.5 557 C32H26N4O2.Co 68.94:4.70:10.05 69.04:4.70:10.01 388, 419, 438, 522 9 585.6 585 C34H30N4O2.Co 69.74:5.16:9.57 69.66:5.23:9.47 388, 419, 438, 522 10 613.6 613 C36H34N4O2.Co 70.47:5.59:9.13 70.58:5.63:9.01 380(s), 397, 429(s), 522 11 641.7 641 C38H38N4O2.Co 71.13:5.97:8.73 71.02:5.88:8.65 380(s), 397, 429(s), 522 12 641.7 641 C38H38N4O2.Co 71.13:5.97:8.73 71.21:6.05:8.59 380(s), 397, 429(s), 522 13 617.6 617 C34H30N4O4.Co 66.12:4.90:9.07 65.97:5.02: :9.01 382, 426, 453, -520#2) EMI36.1 Table <SEP> 1-2 <tb> # <tb> # <SEP> # <SEP> Example <tb> No. <SEP> of <tb> Reaction <tb> Example <SEP> Condi- <SEP> Yield <SEP> Crystal <SEP> # <tb> No. <SEP> R1 <SEP> R2 <SEP> R3 <SEP> tions <SEP> (%) <SEP> Color <SEP> R1 <SEP> R2 <SEP> R3 <tb> 14 <SEP> -H <SEP> -OCH2CH2CH3 <SEP> -H <SEP> 3 <SEP> 6.2 <SEP> Dark <SEP> -H <SEP> -OCH2CH2CH3 <SEP> -H <tb> Purple <tb> 15 <SEP> -H <SEP> -OCH2(CH2)2CH3 <SEP> -H <SEP> 3 <SEP> 9.8 <SEP> -ditto- <SEP> -H <SEP> -OCH2(CH2)2CH3 <SEP> -H <tb> 16 <SEP> -H <SEP> -OC2H5 <SEP> -OC2H5 <SEP> 3 <SEP> 0.95 <SEP> Reddish <SEP> -H <SEP> -OC2H5 <SEP> -OC2H5 <tb> Purple <tb> 17 <SEP> -H <SEP> -OCH2CH2CH3 <SEP> -OCH2CH2CH3 <SEP> 3 <SEP> 1.4 <SEP> -ditto- <SEP> -H <SEP> -OCH2CH2CH3 <SEP> -OCH2CH2CH3 <tb> 18 <SEP> -H <SEP> -OCH2(CH2)2CH3 <SEP> -OCH2(CH2)2CH3 <SEP> 3 <SEP> 1.0 <SEP> Dark <SEP> -H <SEP> -OCH2(CH2)2CH3 <SEP> -OCH2(CH2)2CH3 <tb> Purple <tb> 19 <SEP> -OCH3 <SEP> -OCH3 <SEP> -H <SEP> 1 <SEP> 15.0 <SEP> Reddish <SEP> -OCH3 <SEP> -OCH3 <SEP> -H <tb> Purple <tb> 20 <SEP> -OCH3 <SEP> -OC2H5 <SEP> -H <SEP> 3 <SEP> 13.2 <SEP> -ditto- <SEP> -OCH3 <SEP> -OC2H5 <SEP> -H <tb> 21 <SEP> -OCH3 <SEP> -OCH2CH2CH3 <SEP> -H <SEP> 3 <SEP> 12.6 <SEP> -ditto- <SEP> -OCH3 <SEP> -OCH2CH2CH3 <SEP> -H <tb> Table 1-2 (-continued) Elementary Analysis Mass Spectrum C:H:N (%) Example Visible Spectrum [DMF] No. Calcd. Found Formula Calcd. Found (nm) 14 613.6 613 C36H34N4O2.Co 70.47:5.57:9.13 70.56:5.70:9.10 388 419, 438, 522 15 641.7 641 C38H38N4O2.Co 71.13:5.97:8.73 71.11:6.04:8.82 388, 419, 437, 522 16 673.7 673 C38H38N4O4.Co 67.75:5.69:8.32 67.97:5.52:8.30 382, 427, 454, -520 17 729.7 729 C42H46N4O4.Co 69.12:6.35:7.68 69.28:6.40:7.52 383, 429, 454, -520 18 785.9 785 C46H54N4O4.Co 70.30:6.93:7.13 70.51:7.02:7.00 383, 428, 454, -520 19 617.6 617 C34H30N4O4.Co 66.12:4.90:9.07 66.22:4.79:9.13 388(s), 399, 420(s), 444(s), 522 20 645.6 645 C36H34N4O4.Co 66.78:5.31:8.68 67.07:5.41:8.62 388(s), 399, 420(s), 444(s), 522 21 673.7 673 C38H38N4O4.Co 67.75:5.67:8.32 68.01:5.55:8.43 388(s), 399, 420(s), 443(s), 522 EMI38.1 Table <SEP> 1-3 <tb> # <SEP> # <SEP> # <tb> Example <SEP> No. <tb> Example <SEP> of <SEP> Reaction <SEP> Yield <SEP> Crystal <tb> No. <SEP> R1 <SEP> R2 <SEP> R3 <SEP> Conditions <SEP> (%) <SEP> Color <SEP> R1 <SEP> R2 <SEP> R3 <tb> 22 <SEP> -OCH3 <SEP> -OCH(CH3)2 <SEP> -H <SEP> 3 <SEP> 11.5 <SEP> Reddish <SEP> -OCH3 <SEP> -OCH(CH3)2 <SEP> -H <tb> Purple <tb> 23 <SEP> -OCH3 <SEP> -OCH2(CH2)2CH3 <SEP> -H <SEP> 3 <SEP> 18.8 <SEP> -ditto- <SEP> -OCH3 <SEP> -OCH2(CH2)2CH3 <SEP> -H <tb> 24 <SEP> -OCH3 <SEP> -OCHCH2CH3 <SEP> -H <SEP> 3 <SEP> 15.3 <SEP> -ditto- <SEP> -OCH3 <SEP> -OCHCH2CH3 <SEP> -H <tb> CH3 <SEP> CH3 <tb> 25 <SEP> -OCH3 <SEP> -OCH2CH(CH3)2 <SEP> -H <SEP> 3 <SEP> 17.7 <SEP> -ditto- <SEP> -OCH3 <SEP> -OCH2CH(CH3)2 <SEP> -H <tb> 26 <SEP> -OCH3 <SEP> -OC(CH3)3 <SEP> -H <SEP> 3 <SEP> 10.6 <SEP> -ditto- <SEP> -OCH3 <SEP> -OC(CH3)3 <SEP> -H <tb> 27 <SEP> -OCH3 <SEP> -OC2H5 <SEP> -OC2H5 <SEP> 3 <SEP> 3.0 <SEP> Dark <SEP> -OCH3 <SEP> -OC2H5 <SEP> -OC2H5 <tb> Purple <tb> 28 <SEP> -OCH3 <SEP> -OCH2CH2CH3 <SEP> -OCH2CH2CH3 <SEP> 3 <SEP> 14.4 <SEP> -ditto- <SEP> -OCH3 <SEP> -OCH2CH2CH3 <SEP> -OCH2CH2CH3 <tb> 29 <SEP> -OCH3 <SEP> -OCH(CH3)2 <SEP> -OCH(CH3)2 <SEP> 3 <SEP> 9.6 <SEP> -ditto- <SEP> -OCH3 <SEP> -OCH(CH3)2 <SEP> -OCH(CH3)2 <tb> Table 1-3 (-continued) Elementary Analysis Mass Spectrum C:H:N (%) Example Visible Spectrum [DMF] No. Calcd. Found Formula Calcd. Found (nm) 22 673.7 673 C38H38N4O4.Co 67.75:5.67:8.32 68.01:5.55:8.43 388(s), 399, 420(s), 443(s), 521 23 701.7 701 C40H42N4O4.Co 68.47:6.03:7.98 68.34:5.97:7.87 388(s), 399, 420(s), 443(s), 521 24 701.7 701 C40H42N4O4.Co 68.47:6.03:7.98 68.62:5.95:7.90 388(s), 399, 420(s), 443(s), 521 25 701.7 701 C40H42N4O4.Co 68.47:6.03:7.98 68.58:5.93:8.10 388(s), 399, 420(s), 443(s), 521 26 701.7 701 C40H42N4O4.Co 68.47:6.03:7.98 68.35:6.11:8.03 388(s), 399, 420(s), 443(s), 521 27 733.7 733 C40H42N4O6.Co 65.48:5.77:7.64 65.59:5.65:7.70 384, 395(s), 430, 457, -525 28 789.8 789 C44H50N4O6.Co 66.91:6.38:7.09 66.83:6.36:7.12 384, 395(s), 430, 457, -524 29 789.8 789 C44H50N4O6.Co 66.91:6.38:7.09 67.12:6.35:6.87 384, 395(s), 430, 457, -524 EMI40.1 Table <SEP> 1-4 <tb> # <tb> # <SEP> # <SEP> Example <tb> No. <SEP> of <tb> Reaction <tb> Example <SEP> Condi- <SEP> Yield <SEP> Crystal <SEP> # <tb> No. <SEP> R1 <SEP> R2 <SEP> R3 <SEP> tions <SEP> (%) <SEP> Color <SEP> R1 <SEP> R2 <SEP> R3 <tb> 30 <SEP> -OCH3 <SEP> -OCH2(CH2)2CH3 <SEP> -OCH2(CH2)2CH3 <SEP> 3 <SEP> 7.5 <SEP> Dark <SEP> -OCH3 <SEP> -OCH2(CH2)2CH3 <SEP> -OCH2(CH2)2CH3 <tb> Brown <tb> CH3 <SEP> CH3 <tb> 31 <SEP> -OCH3 <SEP> -OCHCH2CH3 <SEP> -OCHCH2CH3 <SEP> 3 <SEP> 6.3 <SEP> -ditto- <SEP> -OCH3 <SEP> -OCHCH2CH3 <SEP> -OCHCH2CH3 <tb> CH3 <SEP> CH3 <tb> 32 <SEP> -OCH3 <SEP> -OCH2CH(CH3)2 <SEP> -OCH2CH(CH3)2 <SEP> 3 <SEP> 7.9 <SEP> -ditto- <SEP> -OCH3 <SEP> -OCH2CH(CH3)2 <SEP> -OCH2CH(CH3)2 <tb> 33 <SEP> -OC2H5 <SEP> -OCH3 <SEP> -H <SEP> 3 <SEP> 6.6 <SEP> Reddish <SEP> -OC2H5 <SEP> -OCH3 <SEP> -H <tb> Purple <tb> 34 <SEP> -OC2H5 <SEP> -OC2H5 <SEP> -H <SEP> 3 <SEP> 14.2 <SEP> -ditto <SEP> -OC2H5 <SEP> -OC2H5 <SEP> -H <tb> 35 <SEP> -OC2H5 <SEP> -OCH2CH2CH3 <SEP> -H <SEP> 3 <SEP> 5.9 <SEP> -ditto- <SEP> -OC2H5 <SEP> -OCH2CH2CH3 <SEP> -H <tb> 36 <SEP> -OC2H5 <SEP> -OCH(CH3)2 <SEP> -H <SEP> 3 <SEP> 4.8 <SEP> -ditto- <SEP> -OC2H5 <SEP> -OCH(CH3)2 <SEP> -H <tb> 37 <SEP> -OC2H5 <SEP> -OCH2(CH2)2CH3 <SEP> -H <SEP> 3 <SEP> 7.3 <SEP> Dark <SEP> -OC2H5 <SEP> -OCH2(CH2)2CH3 <SEP> -H <tb> Purple <tb> Table 1-4 (-continued) Elementary Analysis Mass Spectrum C:H:N (%) Example Visible Spectrum [DMF] No. Calcd. Found Formula Calcd. Found (nm) 30 845.9 845 C48H58N4O6.Co 68.16:6.91:6.62 68.06:7.11:6.69 384, 395(s), 429, 458, -525 31 845.9 845 C48H58N4O6.Co 68.16:6.91:6.62 68.11:6.82:6.79 384, 395(s), 430, 457, -525 32 845.9 845 C48H58N4O6.Co 68.16:6.91:6.62 68.07:6.98:6.83 384, 395(s), 430, 458, -525 33 645.6 645 C36H34N4O4.Co 66.98:5.31:8.68 66.90:5.41:8.61 388(s), 399, 420(s), 444(s), 523 34 673.7 673 C38H38N4O4.Co 67.75:5.69:8.32 67.51:5.67:8.19 388(s), 399, 420(s), 443(s), 522 35 701.7 701 C40H42N4O4.Co 68.47:6.03:7.78 68.33:6.21:8.08 388(s), 399, 420(s), 443(s), 522 36 701.7 701 C40H42N4O4.Co 68.47:6.03:7.78 68.63:5.92:7.84 388(s), 399, 420(s), 443(s), 522 37 729.8 729 C42H46N4O4.Co 69.12:6.35:7.68 69.30:6.48:7.57 388(s), 399, 420(s), 443(s), 522 EMI42.1 Table <SEP> 1-5 <tb> # <SEP> # <tb> # <SEP> Example <tb> No. <SEP> of <tb> # <SEP> # <SEP> # <SEP> Reaction <tb> Example <SEP> Condi- <SEP> Yield <SEP> Crystal <SEP> # <tb> No. <SEP> R1 <SEP> R2 <SEP> R3 <SEP> tions <SEP> (%) <SEP> Color <SEP> R1 <SEP> R2 <SEP> R3 <tb> 38 <SEP> -OC2H5 <SEP> -OCH3 <SEP> -OCH3 <SEP> 3 <SEP> 15.2 <SEP> Dark <SEP> -OC2H5 <SEP> -OCH3 <SEP> -OCH3 <tb> Purple <tb> 39 <SEP> -OC2H5 <SEP> -OC2H5 <SEP> -OC2H5 <SEP> 3 <SEP> 10.5 <SEP> -ditto- <SEP> -OC2H5 <SEP> -OC2H5 <SEP> -OC2H5 <tb> 40 <SEP> -OC2H5 <SEP> -OCH2CH2CH3 <SEP> -OCH2CH2CH3 <SEP> 3 <SEP> 7.5 <SEP> Dark <SEP> -OC2H5 <SEP> -OCH2CH2CH3 <SEP> -OCH2CH2CH3 <tb> Brown <tb> 41 <SEP> -OC2H5 <SEP> -OCH2(CH2)2CH3 <SEP> -OCH2(CH2)2CH3 <SEP> 3 <SEP> 4.8 <SEP> -ditto- <SEP> -OC2H5 <SEP> -OCH2(CH2)2CH3 <SEP> -OCH2(CH2)2CH3 <tb> 42 <SEP> -OCH2CH2CH3 <SEP> -OC2H5 <SEP> -H <SEP> 3 <SEP> 5.2 <SEP> Reddish <SEP> -OCH2CH2CH3 <SEP> -OC2H5 <SEP> -H <tb> Purple <tb> 43 <SEP> -OCH2CH2CH3 <SEP> -OCH2CH2CH3 <SEP> -H <SEP> 3 <SEP> 16.8 <SEP> -ditto- <SEP> -OCH2CH2CH3 <SEP> -OCH2CH2CH3 <SEP> -H <tb> 44 <SEP> -OCH2CH2CH3 <SEP> -OCH2(CH2)2CH3 <SEP> -H <SEP> 3 <SEP> 6.5 <SEP> Dark <SEP> -OCH2CH2CH3 <SEP> -OCH2(CH2)2CH3 <SEP> -H <tb> Purple <tb> 45 <SEP> -OCH2CH2CH3 <SEP> -OCH3 <SEP> -OCH3 <SEP> 3 <SEP> 9.8 <SEP> -ditto- <SEP> -OCH2CH2CH3 <SEP> -OCH3 <SEP> -OCH3 <tb> Table 1-5 (-continued) Elementary Analysis Mass Spectrum C:H:N (%) Example Visible Spectrum [DMF] No. Calcd. Found Formula Calcd. Found (nm) 38 705.7 705 C38H38N4O6.Co 64.68:5.43:7.94 64.61:5.53:7.86 384, 395(s), 430, 457, -525 39 761.8 761 C42H46N4O6.Co 66.22:6.09:7.35 66.19:6.20:7.44 384, 395(s), 431, 456, -525 40 817.9 817 C46H54N4O6.Co 67.55:6.66:6.85 67.63:6.85:6.91 384, 395(s), 430, 458, -524 41 874.0 873 C50H62N4O6.Co 68.71:7.15:6.41 68.55:7.08:6.32 384, 395(s), 429, 458, -525 42 701.7 701 C40H42N4O4.Co 68.47:6.03:7.98 68.53:6.00:7.91 388(s), 399, 420(s), 433(s), 522 43 729.8 729 C42H46N4O4.Co 69.12:6.35:7.68 69.06:6.20:7.70 388(s), 399, 420(s), 442(s), 521 44 757.8 757 C44H50N4O4.Co 69.74:6.65:7.39 69.87:6.54:7.45 388(s), 399, 420(s), 442(s), 521 45 733.7 733 C40H42N4O6.Co 65.48:5.77:7.64 65.32:5.91:7.60 384, 395(s), 430, 457, -525 EMI44.1 Table <SEP> 1-6 <tb> # <tb> # <SEP> # <SEP> Example <tb> No. <SEP> of <tb> Reaction <tb> Example <SEP> Condi- <SEP> Yield <SEP> Crystal <SEP> # <tb> No. <SEP> R1 <SEP> R2 <SEP> R3 <SEP> tions <SEP> (%) <SEP> Color <SEP> R1 <SEP> R2 <SEP> R3 <tb> 46 <SEP> -OCH2CH2CH3 <SEP> -OC2H5 <SEP> -OC2H5 <SEP> 3 <SEP> 2.3 <SEP> Dark <SEP> -OCH2CH2CH3 <SEP> -OC2H5 <SEP> -OC2H5 <tb> Purple <tb> 47 <SEP> -OCH2CH2CH3 <SEP> -OCH2CH2CH3 <SEP> -OCH2CH2CH3 <SEP> 3 <SEP> 8.1 <SEP> Dark <SEP> -OCH2CH2CH3 <SEP> -OCH2CH2CH3 <SEP> -OCH2CH2CH3 <tb> Brown <tb> 48 <SEP> -OCH2CH2CH3 <SEP> -OCH2(CH2)2CH3 <SEP> -OCH2(CH2)2CH3 <SEP> 3 <SEP> 3.2 <SEP> -ditto- <SEP> -OCH2CH2CH3 <SEP> -OCH2(CH2)2CH3 <SEP> -OCH2(CH2)2CH3 <tb> 49 <SEP> -OCH(CH3)2 <SEP> -OCH3 <SEP> -H <SEP> 3 <SEP> 7.8 <SEP> Reddish <SEP> -OCH(CH3)2 <SEP> -OCH3 <SEP> -H <tb> Purple <tb> 50 <SEP> -OCH(CH3)2 <SEP> -OCH(CH3)2 <SEP> -H <SEP> 3 <SEP> 6.2 <SEP> -ditto- <SEP> -OCH(CH3)2 <SEP> -OCH(CH3)2 <SEP> -H <tb> 51 <SEP> -OCH(CH3)2 <SEP> -OCH3 <SEP> -OCH3 <SEP> 3 <SEP> 8.7 <SEP> Dark <SEP> -OCH(CH3)2 <SEP> -OCH3 <SEP> -OCH3 <tb> Purple <tb> 52 <SEP> -OCH2(CH2)2CH3 <SEP> -OCH3 <SEP> -H <SEP> 3 <SEP> 47.0 <SEP> Reddish <SEP> -OCH2(CH2)2CH3 <SEP> -OCH3 <SEP> -H <tb> Purple <tb> 53 <SEP> -OCH2(CH2)2CH3 <SEP> -OC2H5 <SEP> -H <SEP> 3 <SEP> 10.1 <SEP> Dark <SEP> -OCH2(CH2)2CH3 <SEP> -OC2H5 <SEP> -H <tb> Brown <tb> Table 1-6 (-continued) Elementary Analysis Mass Spectrum C:H:N (%) Example Visible Spectrum [DMF] No. Calcd. Found Formula Calcd. Found (nm) 46 789.8 789 C44H50N4O6.Co 66.91:6.38:7.09 67.09:6.20:7.13 384, 395(s), 431, 456, -526 47 845.7 845 C48H58N4O6.Co 68.16:6.91:6.62 67.97:7.01:6.77 384, 396(s), 431, 458, -524 48 902.1 901 C52H66N4O6.Co 69.24:7.37:6.21 69.11:7.53:6.15 384, 396(s), 429, 459, -525 49 673.7 673 C38H38N4O4.Co 67.75:5.67:8.32 67.88:5.55:8.40 388(s), 399, 420(s), 443(s), 522 50 729.8 729 C42H46N4O4.Co 69.12:6.35:7.68 68.98:6.39:7.75 388(s), 399, 420(s), 443(s), 521 51 733.7 733 C40H42N4O6.Co 65.48:5.77:7.64 65.61:5.67:7.55 384, 395(s), 430, 457, -524 52 701.7 701 C40H42N4O4.Co 68.47:6.03:7.98 68.58:6.15:7.83 388(s), 399, 420(s), 442(s), 521 53 729.8 729 C42H46N4O4.Co 69.12:6.35:7.68 69.31:6.38:7.78 388(s), 399, 420(s), 442(s), 521 EMI46.1 Table <SEP> 1-7 <tb> # <tb> # <SEP> # <SEP> Example <tb> No. <SEP> of <tb> Reaction <tb> Example <SEP> Condi- <SEP> Yield <SEP> Crystal <SEP> # <tb> No. <SEP> R1 <SEP> R2 <SEP> R3 <SEP> tions <SEP> (%) <SEP> Color <SEP> R1 <SEP> R2 <SEP> R3 <tb> 54 <SEP> -OCH2(CH2)2CH3 <SEP> -OCH2CH2CH3 <SEP> -H <SEP> 3 <SEP> 11.0 <SEP> Dark <SEP> -OCH2(CH2)2CH3 <SEP> -OCH2CH2CH3 <SEP> -H <tb> Brown <tb> 55 <SEP> -OCH2(CH2)2CH3 <SEP> -OCH2(CH2)2CH3 <SEP> -H <SEP> 3 <SEP> 13.3 <SEP> -ditto- <SEP> -OCH2(CH2)2CH3 <SEP> -OCH2(CH2)2CH3 <SEP> -H <tb> 56 <SEP> -OCH2(CH2)2CH3 <SEP> -OCH3 <SEP> -OCH3 <SEP> 3 <SEP> 5.3 <SEP> -ditto- <SEP> -OCH2(CH2)2CH3 <SEP> -OCH3 <SEP> -OCH3 <tb> 57 <SEP> -OCH2(CH2)2CH3 <SEP> -OC2H5 <SEP> -OC2H5 <SEP> 3 <SEP> 1.9 <SEP> -ditto- <SEP> -OCH2(CH2)2CH3 <SEP> -OC2H5 <SEP> -OC2H5 <tb> 58 <SEP> -OCH2(CH2)2CH3 <SEP> -OCH2CH2CH3 <SEP> -OCH2CH2CH3 <SEP> 3 <SEP> 4.7 <SEP> -ditto- <SEP> -OCH2(CH2)2CH3 <SEP> -OCH2CH2CH3 <SEP> -OCH2CH2CH3 <tb> 59 <SEP> -OCH2(CH2)2CH3 <SEP> -OCH2(CH2)2CH3 <SEP> -OCH2(CH2)2CH3 <SEP> 3 <SEP> 6.9 <SEP> -ditto- <SEP> -OCH2(CH2)2CH3 <SEP> -OCH2(CH2)2CH3 <SEP> -OCH2(CH2)2CH3 <tb> CH3 <SEP> CH3 <tb> 60 <SEP> -OCHCH2CH3 <SEP> -OCH3 <SEP> -H <SEP> 3 <SEP> 37.8 <SEP> Reddish <SEP> -OCHCH2CH3 <SEP> -OCH3 <SEP> -H <tb> Purple <tb> CH3 <SEP> CH3 <SEP> CH3 <SEP> CH3 <tb> 61 <SEP> -OCHCH2CH3 <SEP> -OCHCH2CH3 <SEP> -H <SEP> 3 <SEP> 8.1 <SEP> Dark <SEP> -OCHCH2CH3 <SEP> -OCHCH2CH3 <SEP> -H <tb> Purple <tb> Table 1-7 (-continued) Elementary Analysis Mass Spectrum C:H:N (%) Example Visible Spectrum [DMF] No. Calcd. Found Formula Calcd. Found (nm) 54 757.8 757 C44H50N4O4.Co 69.74:6.65:7.39 69.97:6.60:7.33 388(s), 399, 420(s), 442(s), 521 55 785.9 785 C46H34N4O4.Co 70.30:6.93:7.13 70.20:6.76:7.33 388(s), 399, 420(s), 442(s), 521 56 761.8 761 C42H46N4O6.Co 66.22:6.09:7.35 66.19:6.01:7.55 383, 394(s), 430, 457, -525 57 817.9 817 C46H54N4O6.Co 67.55:6.66:6.85 67.85:6.55:6.73 384, 395(s), 930, 457, -525 58 874.0 873 C50H62N4O6.Co 68.71:7.15:6.41 68.82:7.01:6.33 384, 396(s), 431, 458, -523 59 930.1 929 C54H70N4O6.Co 69.73:7.59:6.02 69.78:7.53:6.21 385, 396(s), 429, 459, -524 60 701.7 701 C40H42N4O4.Co 68.47:6.03:7.98 68.29:6.15:8.06 388(s), 399, 420(s), 444(s), 522 61 785.9 785 C46H54N4O4.Co 70.30:6.93:7.13 70.48:7.05:6.95 388(s), 399, 420(s), 443(s), 522 EMI48.1 Table <SEP> 1-8 <tb> # <tb> # <SEP> # <SEP> Example <tb> No. <SEP> of <tb> Reaction <tb> Example <SEP> Condi- <SEP> Yield <SEP> Crystal <SEP> # <tb> No. <SEP> R1 <SEP> R2 <SEP> R3 <SEP> tions <SEP> (%) <SEP> Color <SEP> R1 <SEP> R2 <SEP> R3 <tb> CH3 <SEP> CH3 <tb> 62 <SEP> -OCHCH2CH3 <SEP> -OCH3 <SEP> -OCH3 <SEP> 3 <SEP> 7.2 <SEP> Dark <SEP> Brown <SEP> -OCHCH2CH3 <SEP> -OCH3 <SEP> -OCH3 <tb> 63 <SEP> -OCH2CH(CH3)2 <SEP> -OCH3 <SEP> -H <SEP> 3 <SEP> 42.7 <SEP> Reddish <SEP> Purple <SEP> -OCH2CH(CH3)2 <SEP> -OCH3 <SEP> -H <tb> 64 <SEP> -OCH2CH(CH3)2 <SEP> -OCH2CH(CH3)2 <SEP> -H <SEP> 3 <SEP> 12.4 <SEP> Dark <SEP> Purple <SEP> -OCH2CH(CH3)2 <SEP> -OCH2CH(CH3)2 <SEP> -H <tb> 65 <SEP> -OCH2CH(CH3)2 <SEP> -OCH3 <SEP> -OCH3 <SEP> 3 <SEP> 10.3 <SEP> Dark <SEP> Brown <SEP> -OCH2CH(CH3)2 <SEP> -OCH3 <SEP> -OCH3 <tb> 66 <SEP> -OC(CH3)3 <SEP> -H <SEP> -H <SEP> 2 <SEP> 33.2 <SEP> Dark <SEP> Pueple <SEP> -OC(CH3)3 <SEP> -H <SEP> -H <tb> 67 <SEP> -OC(CH3)3 <SEP> -OCH3 <SEP> -H <SEP> 3 <SEP> 27.3 <SEP> -ditto- <SEP> -OC(CH3)3 <SEP> -OCH3 <SEP> -H <tb> 68 <SEP> -OC(CH3)3 <SEP> -OCH3 <SEP> -OCH3 <SEP> 3 <SEP> 5.9 <SEP> Dark <SEP> Brown <SEP> -OC(CH3)3 <SEP> -OCH3 <SEP> -OCH3 <tb> 69 <SEP> -OCH2(CH2)3CH3 <SEP> -H <SEP> -H <SEP> 3 <SEP> 46.2 <SEP> Dark <SEP> Purple <SEP> -OCH2(CH2)3CH3 <SEP> -H <SEP> -H <tb> Table 1-8 (-continued) Elementary Analysis Mass Spectrum C:H:N (%) Example Visible Spectrum [DMF] No. Calcd. Found Formula Calcd. Found (nm) 62 761.8 761 C42H46N4O6.Co 66.22:6.09:7.35 66.34:5.98:7.29 384, 395(s), 430, 457, -525 63 701.7 701 C40H42N4O4.Co 68.47:6.03:7.98 68.33:6.05:8.12 388(s), 399, 420(s), 443(s), 522 64 785.9 785 C46H54N4O4.Co 70.30:6.93:7.13 70.25:7.07:7.01 388(s), 399, 420(s), 443(s), 522 65 761.8 761 C42H46N4O6.Co 66.22:6.09:7.35 66.18:6.04:7.44 384, 395(s), 430, 457, -525 66 641.7 641 C38H38N4O2.Co 71.13:5.97:8.73 70.95:6.11:8.67 380(s), 397, 429(s), 522 67 701.7 701 C40H42N4O4.Co 68.47:6.03:7.98 68.63:5.97:8.06 388(s), 399, 420(s), 443(s), 522 68 761.8 761 C42H46N4O6.Co 66.22:6.09:7.35 66.34:5.96:7.43 384, 395(s), 430, 457, -524 69 669.7 669 C40H42N4O2.Co 71.74:6.32:8.37 71.83:6.30:8.34 380(s), 397, 429(s), 522 EMI50.1 Table <SEP> 1-9 <tb> # <tb> # <SEP> # <SEP> Example <tb> No. <SEP> of <tb> Reaction <tb> Example <SEP> Condi- <SEP> Yield <SEP> Crystal <SEP> # <tb> No. <SEP> R1 <SEP> R2 <SEP> R3 <SEP> tions <SEP> (%) <SEP> Color <SEP> R1 <SEP> R2 <SEP> R3 <tb> 70 <SEP> -OCH2(CH2)6CH3 <SEP> -H <SEP> -H <SEP> 3 <SEP> 38.9 <SEP> Dark <SEP> -OCH2(CH2)6CH3 <SEP> -H <SEP> -H <tb> Purple <tb> 71 <SEP> -H <SEP> -OCH2(CH2)3CH3 <SEP> -H <SEP> 3 <SEP> 10.3 <SEP> -ditto- <SEP> -H <SEP> -OCH2(CH2)3CH3 <SEP> -H <tb> 72 <SEP> -H <SEP> -OCH2(CH2)6CH3 <SEP> -H <SEP> 3 <SEP> 6.5 <SEP> -ditto- <SEP> -H <SEP> -OCH2(CH2)6CH3 <SEP> -H <tb> 73 <SEP> -OCH2(CH2)3CH3 <SEP> -OCH3 <SEP> -H <SEP> 3 <SEP> 28.1 <SEP> Brown <SEP> -OCH2(CH2)3CH3 <SEP> -OCH3 <SEP> -H <tb> 74 <SEP> -OCH2(CH2)6CH3 <SEP> -OCH3 <SEP> -H <SEP> 3 <SEP> 23.6 <SEP> Dark <SEP> -OCH2(CH2)6CH3 <SEP> -OCH3 <SEP> -H <tb> Brown <tb> 75 <SEP> -OCH3 <SEP> -OCH2(CH2)3CH3 <SEP> -H <SEP> 3 <SEP> 31.8 <SEP> Reddish <SEP> -OCH3 <SEP> -OCH2(CH2)3CH3 <SEP> -H <tb> Brown <tb> 76 <SEP> -OCH3 <SEP> -OCH2(CH2)6CH3 <SEP> -H <SEP> 3 <SEP> 25.5 <SEP> Brown <SEP> -OCH3 <SEP> -OCH2(CH2)6CH3 <SEP> -H <tb> 77 <SEP> -OCH2(CH2)3CH3 <SEP> -OCH(CH3)2 <SEP> -H <SEP> 3 <SEP> 13.7 <SEP> Dark <SEP> -OCH2(CH2)3CH3 <SEP> -OCH(CH3)2 <SEP> -H <tb> Brown <tb> Table 1-9 (-continued) Elementary Analysis Mass Spectrum C:H:N (%) Example Visible Spectrum [DMF] No. Calcd. Found Formula Calcd. Found (nm) 70 753.9 753 C46H54N4O2.Co 73.29:7.22:7.43 73.36:7.19:7.37 380(s), 397, 429(s), 522 71 669.7 669 C40H42N4O2.Co 71.74:6.32:8.37 71.85:6.29:8.31 388, 419, 437, 522 72 753.9 753 C46H54N4O2.Co 73.29:7.22:7.43 73.35:7.16:7.45 389, 419, 437, 521 73 729.8 729 C42H46N4O4.Co 69.12:6.35:7.68 69.05:6.32:7.71 399, 420(s), 442(s), 388(s), 522 74 813.9 813 C48H58N4O4.Co 70.83:7.18:6.88 70.77:7.23:6.90 399, 420(s), 442(s), 388(s), 521 75 729.8 729 C42H46N4O4.Co 69.12:6.35:7.68 69.21:6.40:7.58 388(s), 399, 420(s), 442(s), 523 76 813.9 813 C48H58N4O4.Co 70.83:7.18:6.88 70.76:7.23:6.92 388(s), 399, 420(s), 441(s), 522 77 785.9 785 C46H54N4O4.Co 70.30:6.93:7.13 70.41:6.85:7.09 399, 420(s), 443(s), 388(s), 522 EMI52.1 Table <SEP> 1-10 <tb> # <tb> # <SEP> # <SEP> Example <tb> No. <SEP> of <tb> Reaction <tb> Example <SEP> Condi- <SEP> Yield <SEP> Crystal <SEP> # <tb> No. <SEP> R1 <SEP> R2 <SEP> R3 <SEP> tions <SEP> (%) <SEP> Color <SEP> R1 <SEP> R2 <SEP> R3 <tb> 78 <SEP> -OCH2(CH2)6CH3 <SEP> -OCH(CH3)2 <SEP> -H <SEP> 3 <SEP> 11.0 <SEP> Dark <SEP> -OCH2(CH2)6CH3 <SEP> -OCH(CH3)2 <SEP> -H <tb> Brown <tb> 79 <SEP> -OCH(CH3)2 <SEP> -OCH2(CH2)3CH3 <SEP> -H <SEP> 3 <SEP> 18.9 <SEP> -ditto- <SEP> -OCH(CH3)2 <SEP> -OCH2(CH2)3CH3 <SEP> -H <tb> 80 <SEP> -OCH(CH3)2 <SEP> -OCH2(CH2)6CH3 <SEP> -H <SEP> 3 <SEP> 15.3 <SEP> -ditto- <SEP> -OCH(CH3)2 <SEP> -OCH2(CH2)6CH3 <SEP> -H <tb> CH3 <SEP> CH3 <tb> 81 <SEP> -OCHCH2CH3 <SEP> -OCH2(CH2)3CH3 <SEP> -H <SEP> 3 <SEP> 21.2 <SEP> -ditto- <SEP> -OCHCH2CH3 <SEP> -OCH2(CH2)3CH3 <SEP> -H <tb> CH3 <SEP> CH3 <tb> 82 <SEP> -OCHCH2CH3 <SEP> -OCH2(CH2)6CH3 <SEP> -H <SEP> 3 <SEP> 12.3 <SEP> -ditto- <SEP> -OCHCH2CH3 <SEP> -OCH2(CH2)6CH3 <SEP> -H <tb> CH3 <SEP> CH3 <tb> 83 <SEP> -OCH2(CH2)3CH3 <SEP> -OCHCH2CH3 <SEP> -H <SEP> 3 <SEP> 14.3 <SEP> -ditto- <SEP> -OCH2(CH2)3CH3 <SEP> -OCHCH2CH3 <SEP> -H <tb> CH3 <SEP> CH3 <tb> 84 <SEP> -OCH2(CH2)6CH3 <SEP> -OCHCH2CH3 <SEP> -H <SEP> 3 <SEP> 10.6 <SEP> -ditto- <SEP> -OCH2(CH2)6CH3 <SEP> -OCHCH2CH3 <SEP> -H <tb> 85 <SEP> -OCH2CH(CH3)2 <SEP> -OCH2(CH2)3CH3 <SEP> -H <SEP> 3 <SEP> 18.7 <SEP> -ditto- <SEP> -OCH2CH(CH3)2 <SEP> -OCH2(CH2)3CH3 <SEP> -H <tb> Table 1-10 (-continued) Elementary Analysis Mass Spectrum C:H:N (%) Example Visible Spectrum [DMF] No. Calcd. Found Formula Calcd. Found (nm) 78 870.1 869 C52H66N4O4.Co 71.79:7.65:6.44 71.87:7.59:6.51 399, 420(s), 443(s), 388(s), 522 79 785.9 785 C46H54N4O4.Co 70.30:6.93:7.13 70.42:6.85:7.08 388(s), 399, 420(s), 442(s), 522 80 870.1 869 C52H66N4O4.Co 71.79:7.65:6.44 71.92:7.58:6.41 388(s), 399, 420(s), 442(s), 522 81 813.9 813 C48H58N4O4.Co 70.83:7.18:6.88 70.92:7.07:6.93 388(s), 399, 420(s), 442(s), 522 82 898.1 897 C54H70N4O4.Co 72.22:7.86:6.24 72.18:7.99:6.17 388(s), 399, 420(s), 442(s), 522 83 813.9 813 C48H58N4O4.Co 70.83:7.18:6.88 70.94:7.09:6.93 388(s), 399, 420(s), 442(s), 521 84 898.1 897 C54H70N4O4.Co 72.22:7.86:6.24 72.33:7.78:6.12 388(s), 399, 420(s), 442(s), 522 85 813.9 813 C48H58N4O4.Co 70.83:7.18:6.88 70.95:7.06:6.93 388(s), 399, 420(s), 442(s), 522 EMI54.1 Table <SEP> 1-11 <tb> # <tb> # <SEP> # <SEP> Example <tb> No. <SEP> of <tb> Reaction <tb> Example <SEP> Condi- <SEP> Yield <SEP> Crystal <SEP> # <tb> No. <SEP> R1 <SEP> R2 <SEP> R3 <SEP> tions <SEP> (%) <SEP> Color <SEP> R1 <SEP> R2 <SEP> R3 <tb> 86 <SEP> -OCH2CH(CH3)2 <SEP> -OCH2(CH2)6CH3 <SEP> -H <SEP> 3 <SEP> 14.5 <SEP> Dark <SEP> -OCH2CH(CH3)2 <SEP> -OCH2(CH2)6CH3 <SEP> -H <tb> Brown <tb> 87 <SEP> -OCH2(CH2)3CH3 <SEP> -OCH2CH(CH3)2 <SEP> -H <SEP> 3 <SEP> 19.6 <SEP> -ditto- <SEP> -OCH2(CH2)3CH3 <SEP> -OCH2CH(CH3)2 <SEP> -H <tb> 88 <SEP> -OCH2(CH2)6CH3 <SEP> -OCH2CH(CH3)2 <SEP> -H <SEP> 3 <SEP> 12.8 <SEP> -ditto- <SEP> -OCH2(CH2)6CH3 <SEP> -OCH2CH(CH3)2 <SEP> -H <tb> 89 <SEP> -OC(CH3)3 <SEP> -OCH2(CH2)3CH3 <SEP> -H <SEP> 3 <SEP> 19.3 <SEP> -ditto- <SEP> -OC(CH3)3 <SEP> -OCH2(CH2)3CH3 <SEP> -H <tb> 90 <SEP> -OC(CH3)3 <SEP> -OCH2(CH2)6CH3 <SEP> -H <SEP> 3 <SEP> 15.5 <SEP> -ditto- <SEP> -OC(CH3)3 <SEP> -OCH2(CH2)6CH3 <SEP> -H <tb> 91 <SEP> -OCH2(CH2)3CH3 <SEP> -OC(CH3)3 <SEP> -H <SEP> 3 <SEP> 18.2 <SEP> -ditto- <SEP> -OCH2(CH2)3CH3 <SEP> -OC(CH3)3 <SEP> -H <tb> 92 <SEP> -OCH2(CH2)6CH3 <SEP> -OC(CH3)3 <SEP> -H <SEP> 3 <SEP> 11.1 <SEP> -ditto- <SEP> -OCH2(CH2)6CH3 <SEP> -OC(CH3)3 <SEP> -H <tb> 93 <SEP> -OCH2(CH2)3CH3 <SEP> -OCH2(CH2)3CH3 <SEP> -H <SEP> 3 <SEP> 14.7 <SEP> -ditto- <SEP> -OCH2(CH2)3CH3 <SEP> -OCH2(CH2)3CH3 <SEP> -H <tb> Table 1-11 (-continued) Elementary Analysis Mass Spectrum C:H:N (%) Example Visible Spectrum [DMF] No. Calcd. Found Formula Calcd. Found (nm) 86 898.1 897 C54H70N4O4.Co 72.22:7.86:6.24 72.34:7.91:6.11 388(s), 399, 420(s), 441(s), 522 87 813.9 813 C48H58N4O4.Co 70.83:7.18:6.88 70.72:7.23:6.94 388(s), 399, 420(s), 441(s), 521 88 898.1 897 C54H70N4O4.Co 72.22:7.86:6.24 72.30:7.79:6.18 388(s), 399, 420(s), 442(s), 522 89 813.9 813 C48H58N4O4.Co 70.83:7.18:6.88 70.95:7.07:6.93 389(s), 399, 421(s), 443(s), 523 90 898.1 897 C54H70N4O4.Co 72.22:7.86:6.24 72.10:7.93:6.29 388(s), 399, 420(s), 442(s), 522 91 813.9 813 C48H58N4O4.Co 70.83:7.18:6.88 70.91:7.11:6.82 388(s), 399, 420(s), 443(s), 522 92 898.1 897 C54H70N4O4.Co 72.22:7.86:6.24 72.32:7.77:6.21 388(s), 399, 420(s), 442(s), 521 93 842.0 841 C50H62N4O4.Co 71.32:7.42:6.65 71.44:7.36:6.58 388(s), 399, 420(s), 442(s), 522 EMI56.1 Table <SEP> 1-12 <tb> R1 <SEP> R1 <tb> # <SEP> # <tb> R1 <tb> R2 <SEP> NH2 <SEP> Example <tb> # <SEP> No. <SEP> of <tb> R3 <SEP> NH2 <SEP> Reaction <tb> Example <SEP> Condi- <SEP> Yield <SEP> Crystel <tb> No. <SEP> R1 <SEP> R2 <SEP> R3 <SEP> tions <SEP> (%) <SEP> Color <SEP> R1 <SEP> R2 <SEP> R3 <tb> 94 <SEP> -OCH2(CH2)4CH3 <SEP> -OCH2(CH2)4CH3 <SEP> -H <SEP> 3 <SEP> 9.3 <SEP> Dark <SEP> -OCH2(CH2)4CH3 <SEP> -OCH2(CH2)4CH3 <SEP> -H <tb> Brown <tb> 95 <SEP> -OCH2(CH2)3CH3 <SEP> -OCH2(CH2)5CH3 <SEP> -H <SEP> 3 <SEP> 7.6 <SEP> -ditto- <SEP> -OCH2(CH2)5CH3 <SEP> -OCH2(CH2)5CH3 <SEP> -H <tb> 96 <SEP> -OCH2(CH2)6CH3 <SEP> -OCH2(CH2)6CH3 <SEP> -H <SEP> 3 <SEP> 6.3 <SEP> -ditto- <SEP> -OCH2(CH2)6CH3 <SEP> -OCH2(CH2)6CH3 <SEP> -H <tb> 97 <SEP> -OCH2(CH2)3CH3 <SEP> -OCH3 <SEP> -OCH3 <SEP> 3 <SEP> 11.6 <SEP> -ditto- <SEP> -OCH2(CH2)3CH3 <SEP> -OCH3 <SEP> -OCH3 <tb> 98 <SEP> -OCH2(CH2)4CH3 <SEP> -OCH3 <SEP> -OCH3 <SEP> 3 <SEP> 8.7 <SEP> -ditto- <SEP> -OCH2(CH2)4CH3 <SEP> -OCH3 <SEP> -OCH3 <tb> 99 <SEP> -OCH2(CH2)5CH3 <SEP> -OCH3 <SEP> -OCH3 <SEP> 3 <SEP> 7.9 <SEP> -ditto- <SEP> -OCH2(CH2)5CH3 <SEP> -OCH3 <SEP> -OCH3 <tb> 100 <SEP> -OCH2(CH2)6CH3 <SEP> -OCH3 <SEP> -OCH3 <SEP> 3 <SEP> 15.7 <SEP> -ditto- <SEP> -OCH2(CH2)6CH3 <SEP> -OCH3 <SEP> -OCH3 <tb> 101 <SEP> -OCH3 <SEP> -OCH2(CH2)3CH3 <SEP> -OCH2(CH2)3CH3 <SEP> 3 <SEP> 19.2 <SEP> -ditto- <SEP> -OCH3 <SEP> -OCH2(CH2)3CH3 <SEP> -OCH2(CH2)3CH3 <tb> Table 1-12 (-continued) Elementary Analysis Mass Spectrum C:H:N (%) Example Visible Spectrum [DMF] No. Calcd. Found Formula Calcd. Found (nm) 94 898.1 897 C54H70N4O4.Co 72.22:7.86:6.24 72.29:7.78:6.19 388(s), 399, 420(s), 442(s), 521 95 954.2 953 C58H78N4O4.Co 73.01:8.24:5.87 73.14:8.15:5.78 388(s), 399, 420(s), 441(s), 521 96 1010.3 1009 C62H86N4O4.Co 73.71:8.58:5.55 73.65:8.63:5.48 388(s), 399, 420(s), 441(s), 522 97 789.8 789 C44H50N4O6.Co 66.91:6.38:7.09 67.04:6.31:7.03 383, 395(s), 430, 457, 525 98 817.9 817 C46H54N4O6.Co 67.55:6.66:6.85 67.54:6.58:6.92 383, 394(s), 430, 457, 525 99 845.9 845 C48H58N4O6.Co 68.15:6.91:6.62 68.32:6.82:6.57 383, 395(s), 429, 457, 526 100 874.0 873 C50H62N4O6.Co 68.71:7.15:6.41 68.63:7.17:6.50 383, 395(s), 429, 457, 526 101 902.1 901 C52H66N4O6.Co 69.24:7.38:6.21 69.40:7.36:6.18 384, 396(s), 429, 457, 525 EMI58.1 Table <SEP> 1-13 <tb> # <tb> # <SEP> # <SEP> Example <tb> # <SEP> No. <SEP> of <tb> Reaction <tb> Example <SEP> Condi- <SEP> Yield <SEP> Crystal <tb> No. <SEP> R1 <SEP> R2 <SEP> R3 <SEP> tions <SEP> (%) <SEP> Color <SEP> R1 <SEP> R2 <SEP> R3 <tb> 102 <SEP> -OCH3 <SEP> -OCH2(CH2)4CH3 <SEP> -OCH2(CH2)4CH3 <SEP> 3 <SEP> 16.3 <SEP> Dark <SEP> -OCH3 <SEP> -OCH2(CH2)4CH3 <SEP> -OCH2(CH2)4CH3 <tb> Brown <tb> 103 <SEP> -OCH3 <SEP> -OCH2(CH2)5CH3 <SEP> -OCH2(CH2)5CH3 <SEP> 3 <SEP> 13.3 <SEP> -ditto- <SEP> -OCH3 <SEP> -OCH2(CH2)5CH3 <SEP> -OCH2(CH2)5CH3 <tb> 104 <SEP> -OCH3 <SEP> -OCH2(CH2)6CH3 <SEP> -OCH2(CH2)6CH3 <SEP> 3 <SEP> 7.5 <SEP> -ditto- <SEP> -OCH3 <SEP> -OCH2(CH2)6CH3 <SEP> -OCH2(CH2)6CH3 <tb> 105 <SEP> -OCH(CH3)2 <SEP> -OCH2(CH2)3CH3 <SEP> -OCH2(CH2)3CH3 <SEP> 3 <SEP> 12.6 <SEP> -ditto- <SEP> -OCH(CH3)2 <SEP> -OCH2(CH2)3CH3 <SEP> -OCH2(CH2)3CH3 <tb> 106 <SEP> -OCH(CH3)2 <SEP> -OCH2(CH2)6CH3 <SEP> -OCH2(CH2)6CH3 <SEP> 3 <SEP> 8.7 <SEP> -ditto- <SEP> -OCH(CH3)2 <SEP> -OCH2(CH2)6CH3 <SEP> -OCH2(CH2)6CH3 <tb> 107 <SEP> -OCH2(CH2)3CH3 <SEP> -OCH(CH3)2 <SEP> -OCH(CH3)2 <SEP> 3 <SEP> 10.8 <SEP> -ditto- <SEP> -OCH2(CH2)3CH3 <SEP> -OCH(CH3)2 <SEP> -OCH(CH3)2 <tb> 108 <SEP> -OCH2(CH2)6CH3 <SEP> -OCH(CH3)2 <SEP> -OCH(CH3)2 <SEP> 3 <SEP> 7.1 <SEP> -ditto- <SEP> -OCH2(CH2)6CH3 <SEP> -OCH(CH3)2 <SEP> -OCH(CH3)2 <tb> CH3 <SEP> CH3 <tb> 109 <SEP> -OCHCH2CH3 <SEP> -OCH2(CH2)3CH3 <SEP> -OCH2(CH2)2CH3 <SEP> 3 <SEP> 10.8 <SEP> -ditto- <SEP> -OCHCH2CH3 <SEP> -OCH2(CH2)3CH3 <SEP> -OCH2(CH2)3CH3 <tb> Table 1-13 (-continued) Elementary Analysis Mass Spectrum C:H:N (%) Example Visible Spectrum [DMF] No. Calcd. Found Formula Calcd. Found (nm) 102 958.2 957 C56H74N4O6.Co 70.20:7.78:5.85 70.08:7.84:5.92 383, 396(s), 430, 457, 525 103 1014.3 1013 C60H82N4O6.Co 71.05:8.15:5.52 71.21:8.08:5.44 384, 395(s), 429, 458, 525 104 1070.4 1069 C64H90N4O6.Co 71.82:8.48:5.23 71.88:8.55:5.12 384, 396(s), 429, 459, 525 105 958.2 957 C56H74N4O6.Co 70.20:7.78:5.85 70.19:7.67:5.95 383, 396(s), 428, 457, 524 106 1126.5 1125 C68H98N4O6.Co 72.50:8.77:4.97 72.43:8.68:5.13 385, 396(s), 429, 459, 525 107 902.1 901 C52H66N4O6.Co 69.24:7.38:6.21 69.33:7.51:6.08 384, 396(s), 430, 458, 525 108 986.2 985 C58H78N4O6.Co 70.64:7.97:5.68 70.75:8.12:5.56 384, 396(s), 430, 457, 525 109 986.2 985 C58H78N4O6.Co 70.64:7.97:5.68 70.73:8.03:5.72 384, 396(s), 430, 458, 525 EMI60.1 Table <SEP> 1-14 <tb> # <tb> # <SEP> # <SEP> Example <tb> No. <SEP> of <tb> Reaction <tb> Example <SEP> Condi- <SEP> Yield <SEP> Crystal <tb> No. <SEP> R1 <SEP> R2 <SEP> R3 <SEP> tions <SEP> (%) <SEP> Color <SEP> R1 <SEP> R2 <SEP> R3 <tb> CH3 <SEP> CH3 <tb> 110 <SEP> -OCHCH2CH3 <SEP> -OCH2(CH2)6CH3 <SEP> -OCH2(CH2)6CH3 <SEP> 3 <SEP> 9.4 <SEP> Dark <SEP> -OCHCH2CH3 <SEP> -OCH2(CH2)6CH3 <SEP> -OCH2(CH2)6CH3 <tb> CH3 <SEP> Brown <tb> CH3 <tb> 111 <SEP> -OCH2(CH2)3CH3 <SEP> -OCHCH2CH3 <SEP> -OCHCH2CH3 <SEP> 3 <SEP> 4.7 <SEP> -ditto- <SEP> -OCH2(CH2)3CH3 <SEP> -OCHCH2CH3 <SEP> -OCHCH2CH3 <tb> CH3 <SEP> CH3 <tb> CH3 <SEP> CH3 <tb> 112 <SEP> -OCH2(CH2)6CH3 <SEP> -OCHCH2CH3 <SEP> -OCHCH2CH3 <SEP> 3 <SEP> 3.2 <SEP> -ditto- <SEP> -OCH2(CH2)6CH3 <SEP> -OCHCH2CH3 <SEP> -OCHCH2CH3 <tb> CH3 <SEP> CH3 <tb> 113 <SEP> -OCH2CH(CH3)2 <SEP> -OCH2(CH2)3CH3 <SEP> -OCH2(CH2)3CH3 <SEP> 3 <SEP> 13.9 <SEP> -ditto- <SEP> -OCH2CH(CH3)2 <SEP> -OCH2(CH2)3CH3 <SEP> -OCH2(CH2)3CH3 <tb> 114 <SEP> -OCH2CH(CH3)2 <SEP> -OCH2(CH2)6CH3 <SEP> -OCH2(CH2)6CH3 <SEP> 3 <SEP> 10.1 <SEP> -ditto- <SEP> -OCH2CH(CH3)2 <SEP> -OCH2(CH2)6CH3 <SEP> -OCH2(CH2)6CH3 <tb> 115 <SEP> -OCH2(CH2)3CH3 <SEP> -OCH2CH(CH3)2 <SEP> -OCH2CH(CH3)2 <SEP> 3 <SEP> 5.6 <SEP> -ditto- <SEP> -OCH2(CH2)3CH3 <SEP> -OCH2CH(CH3)2 <SEP> -OCH2CH(CH3)2 <tb> 116 <SEP> -OCH2(CH2)3CH3 <SEP> -OCH2CH(CH3)2 <SEP> -OCH2CH(CH3)2 <SEP> 3 <SEP> 4.4 <SEP> -ditto- <SEP> -OCH2(CH2)6CH3 <SEP> -OCH2(CH(CH3)2 <SEP> -OCH2CH(CH3)2 <tb> 117 <SEP> -OC(CH3)3 <SEP> -OCH2(CH2)3CH3 <SEP> -OCH2(CH2)3CH3 <SEP> 3 <SEP> 12.4 <SEP> -ditto- <SEP> -OC(CH3)3 <SEP> -OCH2(CH2)3CH3 <SEP> -OCH2(CH2)3CH3 <tb> Table 1-14 (-continued) Elementary Analysis Mass Spectrum C:H:N (%) Example Visible Spectrum [DMF] No. Calcd. Found Formula Calcd. Found (nm) 110 1154.5 1153 C70H102N4O6.Co 72.82:8.91:4.85 72.78:9.11:4.72 384, 396(s), 429, 459, 525 111 958.2 957 C56H74N4O6.Co 70.20:7.78:5.85 70.12:7.93:5.77 385, 395(s), 429, 458, 525 112 1042.3 1041 C62H86N4O6.Co 71.44:8.32:5.38 71.40:8.43:5.32 385, 396(s), 429, 459, 525 113 986.2 985 C58H78N4O6.Co 70.64:7.97:5.68 70.59:7.82:5.73 384, 396(s), 429, 459, 525 114 1154.5 1153 C70H102N4O6.Co 72.82:8.91:4.85 72.76:9.03:4.82 384, 395(s), 429, 458, 525 115 958.2 957 C56H74N4O6.Co 70.20:7.78:5.85 70.25:7.82:5.74 385, 396(s), 429, 459, 525 116 1042.3 1041 C62H86N4O6.Co 71.44:8.32:5.38 71.32:8.36:5.43 384, 395(s), 429, 458, 525 117 986.2 985 C58H78N4O6.Co 70.64:7.97:5.68 70.70:7.86:5.72 383, 396(s), 428, 457, 524 EMI62.1 Table <SEP> 1-15 <tb> # <tb> # <SEP> # <SEP> Example <tb> No. <SEP> of <tb> Reaction <tb> Example <SEP> Condi- <SEP> Yield <SEP> Crystal <tb> No. <SEP> R1 <SEP> R2 <SEP> R3 <SEP> tions <SEP> (%) <SEP> Color <SEP> R1 <SEP> R2 <SEP> R3 <tb> 118 <SEP> -OC(CH3)3 <SEP> -OCH2(CH2)6CH3 <SEP> -OCH2(CH2)6CH3 <SEP> 3 <SEP> 10.6 <SEP> Dark <SEP> -OC(CH3)3 <SEP> -OCH2(CH2)6CH3 <SEP> -OCH2(CH2)6CH3 <tb> Brown <tb> 119 <SEP> -OCH2(CH2)3CH3 <SEP> -OC(CH3)3 <SEP> -OC(CH3)3 <SEP> 3 <SEP> 3.3 <SEP> -ditto- <SEP> -OCH2(CH2)3CH3 <SEP> -OC(CH3)3 <SEP> -OC(CH3)3 <tb> 120 <SEP> -OCH2(CH2)6CH3 <SEP> -OC(CH3)3 <SEP> -OC(CH3)3 <SEP> 3 <SEP> 2.1 <SEP> -ditto- <SEP> -OCH2(CH2)6CH3 <SEP> -OC(CH3)3 <SEP> -OC(CH3)3 <tb> 121 <SEP> -OCH2(CH2)3CH3 <SEP> -OCH2(CH2)3CH3 <SEP> -OCH2(CH2)3CH3 <SEP> 3 <SEP> 9.8 <SEP> -ditto- <SEP> -OCH2(CH2)3CH3 <SEP> -OCH2(CH2)3CH3 <SEP> -OCH2(CH2)3CH3 <tb> 122 <SEP> -OCH2(CH2)4CH3 <SEP> -OCH2(CH2)4CH3 <SEP> -OCH2(CH2)4CH3 <SEP> 3 <SEP> 8.6 <SEP> -ditto- <SEP> -OCH2(CH2)4CH3 <SEP> -OCH2(CH2)4CH3 <SEP> -OCH2(CH2)4CH3 <tb> 123 <SEP> -OCH2(CH2)5CH3 <SEP> -OCH2(CH2)5CH3 <SEP> -OCH2(CH2)5CH3 <SEP> 3 <SEP> 4.7 <SEP> -ditto- <SEP> -OCH2(CH2)5CH3 <SEP> -OCH2(CH2)5CH3 <SEP> -OCH2(CH2)5CH3 <tb> 124 <SEP> -OCH2(CH2)6CH3 <SEP> -OCH2(CH2)6CH3 <SEP> -OCH2(CH2)6CH3 <SEP> 3 <SEP> 5.2 <SEP> -ditto- <SEP> -OCH2(CH2)6CH3 <SEP> -OCH2(CH2)6CH3 <SEP> -OCH2(CH2)6CH3 <tb> 125 <SEP> -H <SEP> -CH3 <SEP> -CH3 <SEP> 3 <SEP> 55.0 <SEP> Reddish <SEP> -H <SEP> -CH3 <SEP> -CH3 <tb> Brown <tb> Table 1-15 (-continued) Elementary Analysis Mass Spectrum C:H:N: (%) Example Visible Spectrum [DMF] No. Calcd. Found Formula Calcd. Found (nm) 118 1154.5 1153 C70H102N4O6.Co 72.82:8.91:4.85 72.87:8.98:4.72 384, 396(s), 429, 459, 525 119 958.2 957 C56H74N4O6.Co 70.20:7.78:5.85 70.17:7.74:5.81 384, 395(s), 430, 457, 525 120 1042.3 1041 C62H86N4O6.Co 71.44:8.32:5.38 71.62:8.25:5.33 383, 394(s), 430, 457, 525 121 1014.3 1013 C60H82N4O6.Co 71.05:8.15:5.52 70.97:8.22:5.57 384, 397(s), 429, 459, 525 122 1098.4 1097 C66H94N4O6.Co 72.17:8.63:5.10 72.32:8.55:5.02 384, 396(s), 430, 458, 524 123 1182.6 1181 C72H106N4O6.Co 73.13:9.04:4.74 73.22:8.97:4.70 385, 396(s), 429, 459, 525 124 1266.8 1265 C78H118N4O6.Co 73.96:9.39:4.42 74.11:9.27:4.46 385, 396(s), 429, 459, 525 125 553.6 553 C94H30N4.Co 73.77:5.46:10.12 73.91:5.39:10.07 388, 419, 436(s), 524 EMI64.1 Table <SEP> 1-16 <tb> # <tb> # <SEP> # <SEP> Example <tb> No. <SEP> of <tb> Reaction <tb> Example <SEP> Condi- <SEP> Yield <SEP> Crystal <tb> No. <SEP> R1 <SEP> R2 <SEP> R3 <SEP> tions <SEP> (%) <SEP> Color <SEP> R1 <SEP> R2 <SEP> R3 <tb> 126 <SEP> -OCH3 <SEP> -CH3 <SEP> -CH3 <SEP> 3 <SEP> 37.3 <SEP> Reddish <SEP> -OCH3 <SEP> -CH3 <SEP> -CH3 <tb> Brown <tb> 127 <SEP> -OC2H5 <SEP> -CH3 <SEP> -CH3 <SEP> 3 <SEP> 35.7 <SEP> -ditto- <SEP> -OC2H5 <SEP> -CH3 <SEP> -CH3 <tb> 128 <SEP> -OCH2CH2CH3 <SEP> -CH3 <SEP> -CH3 <SEP> 3 <SEP> 32.2 <SEP> -ditto- <SEP> -OCH2CH2CH3 <SEP> -CH3 <SEP> -CH3 <tb> 129 <SEP> -OCH(CH3)2 <SEP> -CH3 <SEP> -CH3 <SEP> 3 <SEP> 29.3 <SEP> -ditto- <SEP> -OCH(CH3)2 <SEP> -CH3 <SEP> -CH3 <tb> 130 <SEP> -OCH2(CH2)2CH3 <SEP> -CH3 <SEP> -CH3 <SEP> 3 <SEP> 40.5 <SEP> -ditto- <SEP> -OCH2(CH2)2CH3 <SEP> -CH3 <SEP> -CH3 <tb> CH3 <SEP> CH3 <tb> 131 <SEP> -OCHCH2CH3 <SEP> -CH3 <SEP> -CH3 <SEP> 3 <SEP> 33.6 <SEP> -ditto- <SEP> -OCHCH2CH3 <SEP> -CH3 <SEP> -CH3 <tb> 132 <SEP> -OCH2CH(CH3)2 <SEP> -CH3 <SEP> -CH3 <SEP> 3 <SEP> 31.6 <SEP> -ditto- <SEP> -OCH2CH(CH9)2 <SEP> -CH3 <SEP> -CH3 <tb> 133 <SEP> -OC(CH3)2 <SEP> -CH3 <SEP> -CH3 <SEP> 3 <SEP> 27.7 <SEP> -ditto- <SEP> -OC(CH3)3 <SEP> -CH3 <SEP> -CH3 <tb> Table 1-16 (-continued) Elementary Analysis Mass Spectrum C:H:N: (%) Example Visible Spectrum [DMF] No. Calcd. Found Formula Calcd. Found (nm) 126 613.6 613 C36H34N4O2.Co 70.47:5.59:9.13 70.52:5.53:9.06 386(s), 400, 423(s), 442(s), 527 127 641.7 641 C38H38N4O2.Co 71.13:5.97:8.93 71.06:6.12:8.87 386(s), 400, 421(s), 442(s), 527 128 669.7 669 C40H42N4O2.Co 71.74:6.32:8.37 71.69:6.25:8.52 386(s), 400, 423(s), 442(s), 527 129 669.7 669 C40H42N4O2.Co 71.74:6.32:8.37 71.67:6.24:8.55 385(s), 400, 423(s), 442(s), 527 130 697.8 697 C42H46N4O2.Co 72.29:6.64:8.03 72.13:6.72:8.15 384(s), 400, 422(s), 443(s), 526 131 697.8 697 C42H46N4O2.Co 72.29:6.64:8.03 72.41:6.47:8.10 384(s), 400, 422(s), 443(s), 526 132 697.8 697 C42H46N4O2.Co 72.29:6.64:8.03 72.36:6.74:7.88 385(s), 400, 422(s), 442(s), 526 133 697.8 697 C42H46N4O2.Co 72.29:6.64:8.03 72.44:6.52:7.97 386(s), 400, 423(s), 442(s), 527 EMI66.1 Table <SEP> 1-17 <tb> # <tb> # <SEP> # <SEP> Example <tb> No. <SEP> of <tb> Reaction <tb> Example <SEP> Condi- <SEP> Yield <SEP> Crystal <tb> No. <SEP> R1 <SEP> R2 <SEP> R3 <SEP> tions <SEP> (%) <SEP> Color <SEP> R1 <SEP> R2 <SEP> R3 <tb> 134 <SEP> -OCH2(CH2)3CH3 <SEP> -CH3 <SEP> -CH3 <SEP> 3 <SEP> 38.5 <SEP> Brown <SEP> -OCH2(CH2)3CH3 <SEP> -CH3 <SEP> -CH3 <tb> 135 <SEP> -OCH2(CH2)4CH3 <SEP> -CH3 <SEP> -CH3 <SEP> 3 <SEP> 35.4 <SEP> -ditto- <SEP> -OCH2(CH2)4CH3 <SEP> -CH3 <SEP> -CH3 <tb> 136 <SEP> -OCH2(CH2)5CH3 <SEP> -CH3 <SEP> -CH3 <SEP> 3 <SEP> 31.7 <SEP> -ditto- <SEP> -OCH2(CH2)5CH3 <SEP> -CH3 <SEP> -CH3 <tb> 137 <SEP> -OCH2(CH2)6CH3 <SEP> -CH3 <SEP> -CH3 <SEP> 3 <SEP> 28.1 <SEP> -ditto- <SEP> -OCH2(CH2)6CH3 <SEP> -CH3 <SEP> -CH3 <tb> 138 <SEP> -OCH3 <SEP> -C2H5 <SEP> -C2H5 <SEP> 3 <SEP> 39.9 <SEP> Reddish <SEP> -OCH3 <SEP> -C2H5 <SEP> -C2H5 <tb> Brown <tb> 139 <SEP> -OCH3 <SEP> -CH2CH2CH3 <SEP> -CH2CH2CH3 <SEP> 3 <SEP> 17.6 <SEP> -ditto- <SEP> -OCH3 <SEP> -CH2CH2CH3 <SEP> -CH2CH2CH3 <tb> 140 <SEP> -OCH3 <SEP> -CH2(CH2)2CH3 <SEP> -CH2(CH2)2CH3 <SEP> 3 <SEP> 30.1 <SEP> Brown <SEP> -OCH3 <SEP> -CH2(CH2)2CH3 <SEP> -CH2(CH2)2CH3 <tb> 141 <SEP> -OCH3 <SEP> -CH2(CH2)3CH3 <SEP> -CH2(CH2)3CH3 <SEP> 3 <SEP> 26.3 <SEP> -ditto- <SEP> -OCH3 <SEP> -CH2(CH2)3CH3 <SEP> -CH2(CH2)3CH3 <tb> Table 1-17 (-continued) Elementary Analysis Mass Spectrum C:H:N (%) Example Visible Spectrum [DMF] No. Calcd. Found Formula Calcd. Found (nm) 134 725.8 725 C44H50N4O2.Co 72.81:6.94:7.72 72.72:7.13:7.64 384(s), 400, 422(s), 443(s), 526 135 753.9 753 C46H54N4O2.Co 73.29:7.22:7.43 73.22:7.13:7.59 384(s), 400, 423(s), 442(s), 525 136 782.0 781 C48H58N4O2.Co 73.73:7.48:7.17 73.88:7.38:7.13 384(s), 400, 423(s), 443(s), 525 137 810.0 809 C50H62N4O2.Co 74.14:7.72:6.92 74.08:7.86:6.85 384(s), 400, 423(s), 443(s), 525 138 669.7 669 C40H42N4O2.Co 71.74:6.32:8.37 71.70:6.19:8.55 386(s), 400, 423(s), 442(s), 527 139 725.8 725 C44H50N4O2.Co 72.81:6.94:7.72 72.91:6.89:7.67 385(s), 400, 423(s), 442(s), 527 140 782.0 781 C48H58N4O2.Co 73.73:7.48:7.17 73.66:7.59:7.12 386(s), 400, 422(s), 442(s), 526 141 838.1 837 C52H66N4O2.Co 74.53:7.94:6.69 74.47:7.86:6.83 386(s), 400, 423(s), 442(s), 526 EMI68.1 Table <SEP> 1-18 <tb> # <tb> # <SEP> # <SEP> Example <tb> No. <SEP> of <tb> Reaction <tb> Example <SEP> Condi- <SEP> Yield <SEP> Crystal <tb> No. <SEP> R1 <SEP> R2 <SEP> R3 <SEP> tions <SEP> (%) <SEP> Color <SEP> R1 <SEP> R2 <SEP> R3 <tb> 142 <SEP> -OCH3 <SEP> -CH2(CH2)4CH3 <SEP> -CH2(CH2)4CH3 <SEP> 3 <SEP> 23.7 <SEP> Brown <SEP> -OCH3 <SEP> -CH2(CH2)4CH3 <SEP> -CH2(CH2)4CH3 <tb> 143 <SEP> -OCH3 <SEP> -CH2(CH2)5CH3 <SEP> -CH2(CH2)5CH3 <SEP> 3 <SEP> 18.8 <SEP> Dark <SEP> -OCH3 <SEP> -CH2(CH2)5CH3 <SEP> -CH2(CH2)5CH3 <tb> Brown <tb> 144 <SEP> -OCH3 <SEP> -CH2(CH2)6CH3 <SEP> -CH2(CH2)6CH3 <SEP> 3 <SEP> 15.6 <SEP> -ditto- <SEP> -OCH3 <SEP> -CH2(CH2)6CH3 <SEP> -CH2(CH2)6CH3 <tb> 145 <SEP> -OC2H5 <SEP> -C2H5 <SEP> -C2H5 <SEP> 3 <SEP> 30.0 <SEP> Brown <SEP> -OC2H5 <SEP> -C2H5 <SEP> -C2H5 <tb> 146 <SEP> -OCH2CH2CH3 <SEP> -CH2CH2CH3 <SEP> -CH2CH2CH3 <SEP> 3 <SEP> 17.9 <SEP> -ditto- <SEP> -OCH2CH2CH3 <SEP> -CH2CH2CH3 <SEP> -CH2CH2CH3 <tb> 147 <SEP> -OCH2(CH2)2CH3 <SEP> -CH2(CH2)2CH3 <SEP> -CH2(CH2)2CH3 <SEP> 3 <SEP> 24.9 <SEP> Dark <SEP> -OCH2(CH2)2CH3 <SEP> -OCH2(CH2)2CH3 <SEP> -OCH2(CH2)2CH3 <tb> Brown <tb> 148 <SEP> -OCH2(CH2)3CH3 <SEP> -CH2(CH2)3CH3 <SEP> -CH2(CH2)3CH3 <SEP> 3 <SEP> 23.1 <SEP> -ditto- <SEP> -OCH2(CH2)3CH3 <SEP> -CH2(CH2)3CH3 <SEP> -CH2(CH2)3CH3 <tb> 149 <SEP> -OCH2(CH2)4CH3 <SEP> -OCH2(CH2)4CH3 <SEP> -CH2(CH2)4CH3 <SEP> 3 <SEP> 18.4 <SEP> -ditto- <SEP> -OCH2(CH2)4CH3 <SEP> -CH(CH2)4CH3 <SEP> -CH2(CH2)4CH3 <tb> Table 1-18 (-continued) Elementary Analysis Mass Spectrum C:H:N (%) Example Visible Spectrum [DMF] No. Calcd. Found Formula Calcd. Found (nm) 142 894.2 893 C56H74N4O2.Co 75.22:8.34:6.27 75.09:8.42:6.35 385(s), 400, 422(s), 442(s), 525 143 950.3 949 C60H82N4O2.Co 75.84:8.70:5.90 75.99:8.62:5.78 384(s), 400, 422(s), 442(s), 526 144 1006.4 1005 C64H90N4O2.Co 76.38:9.01:5.57 76.51:8.87:5.60 384(s), 400, 422(s), 442(s), 526 145 697.8 697 C42H46N4O2.Co 72.29:6.64:8.03 72.36:6.72:7.87 386(s), 400, 421(s), 443(s), 527 146 782.0 781 C48H56N4O2.Co 73.73:7.48:7.17 73.92:7.37:7.10 385(s), 400, 422(s), 443(s), 526 147 860.1 859 C54H64N4O2.Co 75.41:7.50:6.51 75.38:7.46:6.49 385(s), 400, 422(s), 442(s), 526 148 950.3 949 C60H82N4O2.Co 75.84:8.70:5.90 75.77:8.87:5.79 385(s), 400, 423(s), 443(s), 526 149 1034.4 1033 C66H94N4O2.Co 76.63:9.16:5.42 76.81:9.07:5.35 384(s), 400, 422(s), 442(s), 525 EMI70.1 Table <SEP> 1-19 <tb> # <tb> # <SEP> # <SEP> Example <tb> No. <SEP> of <tb> Reaction <tb> Example <SEP> Condi- <SEP> Yield <SEP> Crystal <tb> No. <SEP> R1 <SEP> R2 <SEP> R3 <SEP> tions <SEP> (%) <SEP> Color <SEP> R1 <SEP> R2 <SEP> R3 <tb> 150 <SEP> -OCH2(CH2)5CH3 <SEP> -CH2(CH2)5CH3 <SEP> -CH2(CH2)5CH3 <SEP> 3 <SEP> 19.5 <SEP> Dark <SEP> -OCH2(CH2)5CH3 <SEP> -CH2(CH2)5CH3 <SEP> -CH2(CH2)5CH3 <tb> Brown <tb> 151 <SEP> -OCH2(CH2)6CH3 <SEP> -CH2(CH2)6CH3 <SEP> -CH2(CH2)6CH3 <SEP> 3 <SEP> 11.8 <SEP> -ditto- <SEP> -OCH2(CH2)6CH3 <SEP> -CH2(CH2)6CH3 <SEP> -CH2(CH2)6CH3 <tb> 152 <SEP> -H <SEP> -CH3 <SEP> -H <SEP> 3 <SEP> 27.2 <SEP> Reddish <SEP> -H <SEP> -H <SEP> -CH3 <tb> Brown <tb> 153 <SEP> -CH3 <SEP> -OCH3 <SEP> -OCH3 <SEP> 3 <SEP> 23.7 <SEP> Dark <SEP> -CH3 <SEP> -OCH3 <SEP> -OCH3 <tb> Brown <tb> 154 <SEP> -C2H3 <SEP> -OCH3 <SEP> -OCH3 <SEP> 3 <SEP> 25.8 <SEP> -ditto- <SEP> -C2H5 <SEP> -OCH3 <SEP> -OCH3 <tb> 155 <SEP> -CH2CH2CH3 <SEP> -OCH3 <SEP> -OCH3 <SEP> 3 <SEP> 20.6 <SEP> -ditto- <SEP> -CH2CH2CH3 <SEP> -OCH3 <SEP> -OCH3 <tb> 156 <SEP> -CH(CH3)2 <SEP> -OCH3 <SEP> -OCH3 <SEP> 3 <SEP> 17.5 <SEP> -ditto- <SEP> -CH(CH3)2 <SEP> -OCH3 <SEP> -OCH3 <tb> 157 <SEP> -CH2(CH2)2CH3 <SEP> -OCH3 <SEP> -OCH3 <SEP> 3 <SEP> 22.7 <SEP> -ditto- <SEP> -CH2(CH2)2CH3 <SEP> -OCH3 <SEP> -OCH3 <tb> Table 1-19 (-continued) Elementary Analysis Mass Spectrum C:H:N (%) Example Visible Spectrum [DMF] No. Calcd. Found Formula Calcd. Found (nm) 150 1118.6 1117 C72H106N4O2.Co 77.31:9.55:5.01 77.45:9.61:4.84 384(s), 400, 423(s), 443(s), 526 151 1202.8 1201 C78H118N4O2.Co 77.89:9.89:4.66 77.81:10.02:4.59 384(s), 400, 422(s), 443(s), 526 152 525.5 525 C32H26N4.Co 73.14:4.99:10.66 73.28:4.95:10.58 379(s), 389, 418, 430(s), 522 153 645.6 645 C36H34N4O4.Co 66.97:5.31:8.68 67.07:5.27:8.63 383, 428, 454, 527 154 673.7 673 C38H38N4O4.Co 67.75:5.69:8.32 67.68:5.82:8.19 383, 428, 454, 527 155 701.7 701 C40H42N4O4.Co 68.46:6.03:7.98 68.41:5.98:8.13 383, 429, 456, 528 156 701.7 701 C40H42N4O4.Co 68.46:6.03:7.98 68.33:6.10:8.04 383, 429, 455, 527 157 729.8 729 C42H46N4O4.Co 69.12:6.35:7.68 69.18:6.19:7.73 384, 428, 454, 526 EMI72.1 Table <SEP> 1-20 <tb> # <tb> # <SEP> # <SEP> Example <tb> No. <SEP> of <tb> Reaction <tb> Example <SEP> Condi- <SEP> Yield <SEP> Crystal <tb> No. <SEP> R1 <SEP> R2 <SEP> R3 <SEP> tions <SEP> (%) <SEP> Color <SEP> R1 <SEP> R2 <SEP> R3 <tb> CH3 <SEP> CH3 <tb> 158 <SEP> -CHCH2CH3 <SEP> -OCH3 <SEP> -OCH3 <SEP> 3 <SEP> 17.6 <SEP> Dark <SEP> -CHCH2CH3 <SEP> -OCH3 <SEP> -OCH3 <tb> Brown <tb> 159 <SEP> -CH2CH(CH3)2 <SEP> -OCH3 <SEP> -OCH3 <SEP> 3 <SEP> 11.1 <SEP> -ditto- <SEP> -CH2CH(CH3)2 <SEP> -OCH3 <SEP> -OCH3 <tb> 160 <SEP> -C(CH3)3 <SEP> -OCH3 <SEP> -OCH3 <SEP> 3 <SEP> 8.9 <SEP> -ditto- <SEP> -C(CH3)3 <SEP> -OCH3 <SEP> -OCH3 <tb> 161 <SEP> -CH2(CH2)3CH3 <SEP> -OCH3 <SEP> -OCH3 <SEP> 3 <SEP> 19.3 <SEP> -ditto- <SEP> -CH2(CH2)3CH3 <SEP> -OCH3 <SEP> -OCH3 <tb> 162 <SEP> -CH2(CH2)4CH3 <SEP> -OCH3 <SEP> -OCH3 <SEP> 3 <SEP> 16.5 <SEP> -ditto- <SEP> -CH2(CH2)4CH3 <SEP> -OCH3 <SEP> -OCH3 <tb> 163 <SEP> -CH2(CH2)5CH3 <SEP> -OCH3 <SEP> -OCH3 <SEP> 3 <SEP> 14.9 <SEP> -ditto- <SEP> -CH2(CH2)5CH3 <SEP> -OCH3 <SEP> -OCH3 <tb> 164 <SEP> -CH2(CH2)6CH3 <SEP> -OCH3 <SEP> -OCH3 <SEP> 3 <SEP> 13.0 <SEP> -ditto- <SEP> -CH2(CH2)6CH3 <SEP> -OCH3 <SEP> -OCH3 <tb> 165 <SEP> -CH3 <SEP> -OC2H5 <SEP> -OC2H5 <SEP> 3 <SEP> 24.2 <SEP> -ditto- <SEP> -CH3 <SEP> -OC2H5 <SEP> -OC2H5 <tb> Table 1-20 (-continued) Elementary Analysis Mass Spectrum C:H:N (%) Example Visible Spectrum [DMF] No. Calcd. Found Formula Calcd. Found (nm) 158 729.8 729 C42H46N4O4.Co 69.12:6.35:7.68 69.20:6.41:7.56 383, 428, 455, 527 159 729.8 729 C42H46N4O4.Co 69.12:6.35:7.68 69.28:6.28:7.59 383, 428, 455, 527 160 729.8 729 C42H46N4O4.Co 69.12:6.35:7.68 69.05:6.52:7.60 383, 429, 454, 527 161 757.8 757 C44H50N4O4.Co 69.74:6.65:7.39 69.67:6.62:7.53 383, 429, 456, 527 162 785.9 785 C46H54N4O4.Co 70.30:6.93:7.13 70.17:7.02:7.18 383, 428, 454, 526 163 813.9 813 C48H58N4O4.Co 70.83:7.18:6.88 70.92:7.03:6.93 383, 428, 454, 526 164 842.0 841 C50H62N4O4.Co 71.32:7.42:6.65 71.39:7.53:6.47 383, 428, 455, 527 165 701.7 701 C40H42N4O4.Co 68.46:6.03:7.98 68.51:6.05:8.01 383, 428, 454, 527 EMI74.1 Table <SEP> 1-21 <tb> # <tb> # <SEP> # <SEP> Example <tb> No. <SEP> of <tb> Reaction <tb> Example <SEP> Condi- <SEP> Yield <SEP> Crystal <tb> No. <SEP> R1 <SEP> R2 <SEP> R3 <SEP> tions <SEP> (%) <SEP> Color <SEP> R1 <SEP> R2 <SEP> R3 <tb> 166 <SEP> -CH3 <SEP> -OCH2CH2CH3 <SEP> -OCH2CH2CH3 <SEP> 3 <SEP> 17.5 <SEP> Dark <SEP> -CH3 <SEP> -OCH2CH2CH3 <SEP> -OCH2CH2CH3 <tb> Brown <tb> 167 <SEP> -CH3 <SEP> -OCH(CH3)2 <SEP> -OCH(CH3)2 <SEP> 3 <SEP> 14.4 <SEP> -ditto- <SEP> -CH3 <SEP> -OCH(CH3)2 <SEP> -OCH(CH3)2 <tb> 168 <SEP> -CH3 <SEP> -OCH2(CH2)2CH3 <SEP> -OCH2(CH2)2CH3 <SEP> 3 <SEP> 20.8 <SEP> -ditto- <SEP> -CH3 <SEP> -OCH2(CH2)2CH3 <SEP> -OCH2(CH2)2CH3 <tb> CH3 <SEP> CH3 <tb> 169 <SEP> -CH3 <SEP> -OCHCH2CH3 <SEP> -OCHCH2CH3 <SEP> 3 <SEP> 15.3 <SEP> -ditto- <SEP> -CH3 <SEP> -OCHCH2CH3 <SEP> -OCHCH2CH3 <tb> CH3 <SEP> CH3 <tb> 170 <SEP> -CH3 <SEP> -OCH2CH(CH3)2 <SEP> -OCH2CH(CH3)2 <SEP> 3 <SEP> 16.7 <SEP> -ditto- <SEP> -CH3 <SEP> -OCH2CH(CH3)2 <SEP> -OCH2CH(CH3)2 <tb> 171 <SEP> -CH3 <SEP> -OC(CH3)3 <SEP> -OC(CH3)3 <SEP> 3 <SEP> 12.3 <SEP> -ditto- <SEP> -CH3 <SEP> -OC(CH3)3 <SEP> -OC(CH3)3 <tb> 172 <SEP> -CH3 <SEP> -OCH2(CH2)3CH3 <SEP> -OCH2(CH2)3CH3 <SEP> 3 <SEP> 19.6 <SEP> -ditto- <SEP> -CH3 <SEP> -OCH2(CH2)3CH3 <SEP> -OCH2(CH2)3CH3 <tb> 173 <SEP> -CH3 <SEP> -OCH2(CH2)4CH3 <SEP> -OCH2(CH2)4CH3 <SEP> 3 <SEP> 17.8 <SEP> -ditto- <SEP> -CH3 <SEP> -OCH2(CH2)4CH3 <SEP> -OCH2(CH2)4CH3 <tb> Table 1-21 (-continued) Elementary Analysis Mass Spectrum C:H:N (%) Example Visible Spectrum [DMF] No. Calcd. Found Formula Calcd. Found (nm) 166 757.8 757 C44H50N4O4.Co 69.74:6.65:7.39 69.70:6.74:7.33 384, 428, 456 528 167 757.8 757 C44H50N4O4.Co 69.74:6.65:7.39 69.58:6.72:7.30 384, 428, 456, 528 168 813.9 813 C48H58N4O4.Co 70.83:7.18:6.88 70.68:7.23:6.94 383, 429, 455, 527 169 813.9 813 C48H58N4O4.Co 70.83:7.18:6.88 70.78:7.13:6.82 384, 429, 456, 528 170 813.9 813 C48H58N4O4.Co 70.83:7.18:6.88 70.91:7.15:6.80 384, 428, 456, 527 171 813.9 813 C48H58N4O4.Co 70.83:7.18:6.88 70.95:7.07:6.92 383, 428, 455, 527 172 870.1 869 C52H66N4O4.Co 71.79:7.65:6.44 71.85:7.72:6.29 384, 429, 455, 526 173 926.2 925 C56H74N4O4.Co 72.62:8.05:6.05 72.84:7.98:5.97 383, 428, 455, 527 EMI76.1 Table <SEP> 1-22 <tb> # <tb> # <SEP> # <SEP> Example <tb> No. <SEP> of <tb> Reaction <tb> Example <SEP> Condi- <SEP> Yield <SEP> Crystal <tb> No. <SEP> R1 <SEP> R2 <SEP> R3 <SEP> tions <SEP> (%) <SEP> Color <SEP> R1 <SEP> R2 <SEP> R3 <tb> 174 <SEP> -CH3 <SEP> -OCH2(CH2)5CH3 <SEP> -OCH2(CH2)5CH3 <SEP> 3 <SEP> 16.0 <SEP> Dark <SEP> -CH3 <SEP> -OCH2(CH2)5CH3 <SEP> -OCH2(CH2)5CH3 <tb> Brown <tb> 175 <SEP> -CH3 <SEP> -OCH2(CH2)6CH3 <SEP> -OCH2(CH2)6CH3 <SEP> 3 <SEP> 13.1 <SEP> -ditto- <SEP> -CH3 <SEP> -OCH2(CH2)6CH3 <SEP> -OCH2(CH2)6CH3 <tb> 176 <SEP> -C2H5 <SEP> -OC2H5 <SEP> -OC2H5 <SEP> 3 <SEP> 24.6 <SEP> -ditto- <SEP> -C2H5 <SEP> -OC2H5 <SEP> -OC2H5 <tb> 177 <SEP> -CH2CH2CH3 <SEP> -OCH2CH2CH3 <SEP> -OCH2CH2CH3 <SEP> 3 <SEP> 21.7 <SEP> -ditto- <SEP> -CH2CH2CH3 <SEP> -OCH2CH2CH3 <SEP> -OCH2CH2CH3 <tb> 178 <SEP> -CH2(CH2)CH3 <SEP> -OCH2(CH2)2CH3 <SEP> -OCH2(CH2)2CH3 <SEP> 3 <SEP> 18.7 <SEP> -ditto- <SEP> -CH2(CH2)2CH3 <SEP> -OCH2(CH2)2CH3 <SEP> -OCH2(CH2)2CH3 <tb> #179 <SEP> -CH2(CH2)3CH3 <SEP> -OCH2(CH2)3CH3 <SEP> -OCH2(CH2)3CH3 <SEP> 3 <SEP> 16.2 <SEP> -ditto- <SEP> -CH2(CH2)3CH3 <SEP> -OCH2(CH2)3CH3 <SEP> -OCH2(CH2)3CH3 <tb> #180 <SEP> -CH2(CH2)4CH3 <SEP> -OCH2(CH2)4CH3 <SEP> -OCH2(CH2)4CH3 <SEP> 3 <SEP> 16.6 <SEP> -ditto- <SEP> -CH2(CH2)4CH3 <SEP> -OCH2(CH2)4CH3 <SEP> -OCH2(CH2)4CH3 <tb> #181 <SEP> -CH2(CH2)5CH3 <SEP> -OCH2(CH2)5CH3 <SEP> -OCH2(CH2)5CH3 <SEP> 3 <SEP> 15.5 <SEP> -ditto- <SEP> -CH2(CH2)5CH3 <SEP> -OCH2(CH2)5CH3 <SEP> -OCH2(CH2)5CH3 <tb> Table 1-22 (-continued) Elementary Analysis Mass Spectrum C:H:N (%) Example Visible Spectrum [DMF] No. Calcd. Found Formula Calcd. Found (nm) 174 982.3 981 C60H82N4O4.Co 73.37:8.41:5.70 73.23:8.60:5.61 383, 428, 455, 527 175 1038.4 1037 C64H90N4O4.Co 74.03:8.74:5.40 73.98:8.67:5.57 383, 428, 455, 527 176 729.8 729 C42H46N4O4.Co 69.12:6.35:7.68 68.97:6.42:7.74 384, 428, 454, 526 177 813.9 813 C48H58N4O4.Co 70.83:7.18:6.88 70.91:7.24:6.73 384, 428, 454, 527 178 898.1 897 C54H70N4O4.Co 72.22:7.86:6.24 72.37:7.78:6.17 383, 429, 455, 527 179 982.3 981 C60H82N4O4.Co 73.37:8.41:5.70 73.28:8.57:5.62 383, 428, 454, 526 180 1066.4 1065 C66H94N4O4.Co 74.33:8.88:5.25 74.28:8.79:5.44 383, 428, 454, 526 181 1150.6 1149 C72H106N4O4.Co 75.16:9.29:4.87 75.03:9.36:4.92 383, 427, 454, 526 EMI78.1 Table <SEP> 1-23 <tb> # <tb> # <SEP> # <SEP> Example <tb> No. <SEP> of <tb> Reaction <tb> Example <SEP> Condi- <SEP> Yield <SEP> Crystal <tb> No. <SEP> R1 <SEP> R2 <SEP> R3 <SEP> tions <SEP> (%) <SEP> Color <SEP> R1 <SEP> R2 <SEP> R3 <tb> 182 <SEP> -CH2(CH2)6CH3 <SEP> -OCH2(CH2)6CH3 <SEP> -OCH2(CH2)6CH3 <SEP> 3 <SEP> 11.7 <SEP> Dark <SEP> -CH2(CH2)6CH3 <SEP> -OCH2(CH2)6CH3 <SEP> -OCH2(CH2)6CH3 <tb> Brown <tb> 183 <SEP> -C2H5 <SEP> -H <SEP> -H <SEP> 3 <SEP> 48.3 <SEP> -ditto- <SEP> -C2H5 <SEP> -H <SEP> -H <tb> 184 <SEP> -CH2(CH2)6CH3 <SEP> -H <SEP> -H <SEP> 3 <SEP> 37.3 <SEP> Black <SEP> -CH2(CH2)6CH3 <SEP> -H <SEP> -H <tb> 185 <SEP> -C2H5 <SEP> -CH3 <SEP> -CH3 <SEP> 5 <SEP> 65.3 <SEP> Brown <SEP> -C2H5 <SEP> -CH3 <SEP> -CH3 <tb> 186 <SEP> -CH2CH2CH3 <SEP> -CH3 <SEP> -CH3 <SEP> 5 <SEP> 59.2 <SEP> -ditto- <SEP> -CH2CH2CH3 <SEP> -CH3 <SEP> -CH3 <tb> 187 <SEP> -CH(CH3)2 <SEP> -CH3 <SEP> -CH3 <SEP> 5 <SEP> 43.2 <SEP> -ditto- <SEP> -CH(CH3)2 <SEP> -CH3 <SEP> -CH3 <tb> 188 <SEP> -CH2(CH2)2CH3 <SEP> -CH3 <SEP> -CH3 <SEP> 5 <SEP> 54.4 <SEP> -ditto- <SEP> -CH2(CH2)2CH3 <SEP> -CH3 <SEP> -CH3 <tb> CH3 <SEP> CH3 <tb> 189 <SEP> -CHCH2CH3 <SEP> -CH3 <SEP> -CH3 <SEP> 5 <SEP> 37.0 <SEP> -ditto- <SEP> -CHCH2CH3 <SEP> -CH3 <SEP> -CH3 <tb> Table 1-23 (-continued) Elementary Analysis Mass Spectrum C:H:N (%) Example Visible Spectrum [DMF] No. Calcd. Found Formula Calcd. Found (nm) 182 1234.8 1233 C78H118N4O4.Co 75.87:9.63:4.54 75.94:9.51:4.60 383, 428, 455, 526 183 553.6 553 C34H30N4.Co 73.76:5.46:10.12 73.81:5.53:9.98 380(s), 393, 428(s), 522 184 722.0 721 C46H54N4.Co 76.53:7.54:7.76 76.50:7.49:7.72 380(s), 393, 428(s), 522 185 609.7 609 C38H38N4.Co 74.86:6.28:9.19 74.81:6.33:9.21 384, 398, 422, 439(s), 525 186 637.7 637 C40H42N4.Co 75.34:6.64:8.79 75.36:6.64:8.75 385, 398, 422, 438(s), 525 187 637.7 637 C40H42N4.Co 75.34:6.64:8.79 75.40:6.61:8.82 384, 397, 421, 438(s), 525 188 665.8 665 C42H46N4.Co 75.77:6.96:8.42 75.69:6.99:8.43 385, 397, 421, 438(s), 524 189 665.8 665 C42H46N4.Co 75.77:6.96:8.42 75.78:6.92:8.43 385, 397, 421, 438(s), 525 EMI80.1 Table <SEP> 1-24 <tb> # <tb> # <SEP> # <SEP> Example <tb> No. <SEP> of <tb> Reaction <tb> Example <SEP> Condi- <SEP> Yield <SEP> Crystal <tb> No. <SEP> R1 <SEP> R2 <SEP> R3 <SEP> tions <SEP> (%) <SEP> Color <SEP> R1 <SEP> R2 <SEP> R3 <tb> 190 <SEP> -CH2CH(CH3)2 <SEP> -CH3 <SEP> -CH3 <SEP> 5 <SEP> 40.3 <SEP> Brown <SEP> -CH2CH(CH3)2 <SEP> -CH3 <SEP> -CH3 <tb> 191 <SEP> -C(CH3)3 <SEP> -CH3 <SEP> -CH3 <SEP> 5 <SEP> 28.7 <SEP> -ditto- <SEP> -C(CH3)3 <SEP> -CH3 <SEP> -CH3 <tb> 192 <SEP> -CH2(CH2)3CH3 <SEP> -CH3 <SEP> -CH3 <SEP> 5 <SEP> 51.2 <SEP> -ditto- <SEP> -CH2(CH2)3CH3 <SEP> -CH3 <SEP> -CH3 <tb> 193 <SEP> -CH2(CH2)4CH3 <SEP> -CH3 <SEP> -CH3 <SEP> 5 <SEP> 48.7 <SEP> -ditto- <SEP> -CH2(CH2)4CH3 <SEP> -CH3 <SEP> -CH3 <tb> 194 <SEP> -CH2(CH2)5CH3 <SEP> -CH3 <SEP> -CH3 <SEP> 5 <SEP> 36.5 <SEP> -ditto- <SEP> -CH2(CH2)5CH3 <SEP> -CH3 <SEP> -CH3 <tb> 195 <SEP> -CH2(CH2)6CH3 <SEP> -CH3 <SEP> -CH3 <SEP> 5 <SEP> 21.9 <SEP> -ditto- <SEP> -CH2(CH2)6CH3 <SEP> -CH3 <SEP> -CH3 <tb> 196 <SEP> -CH3 <SEP> -C2H5 <SEP> -C2H5 <SEP> 5 <SEP> 63.5 <SEP> -ditto- <SEP> -CH3 <SEP> -C2H5 <SEP> -C2H5 <tb> 197 <SEP> -CH3 <SEP> -CH2CH2CH3 <SEP> -CH2CH2CH3 <SEP> 5 <SEP> 52.4 <SEP> -ditto- <SEP> -CH3 <SEP> -CH2CH2CH3 <SEP> -CH2CH2CH3 <tb> Table 1-24 (-continued) Elementary Analysis Mass Spectrum C:H:N (%) Example Visible Spectrum [DMF] No. Calcd. Found Formula Calcd. Found (nm) 190 665.8 665 C42H46N4.Co 75.77:6.96:8.42 75.82:6.91:8.41 385, 397, 421, 438(s), 525 191 665.8 665 C42H46N4.Co 75.77:6.96:8.42 75.83:6.93:8.45 384, 398, 422, 439(s), 525 192 693.8 693 C44H50N4.Co 76.17:7.26:8.08 76.24:7.19:8.10 385, 397, 421, 438(s), 525 193 721.9 721 C46H54N4.Co 76.54:7.54:7.76 76.48:7.57:7.81 385, 397, 421, 438(s), 525 194 750.0 749 C48H58N4.Co 76.88:7.80:7.47 76.94:7.72:7.48 385, 397, 421, 438(s), 525 195 778.0 777 C50H62N4.Co 77.19:8.03:7.20 77.27:7.93:7.26 386, 397, 421, 438(s), 525 196 637.7 637 C40H42N4.Co 75.34:6.64:8.79 75.41:6.58:8.83 384, 398, 422, 439(s), 524 197 693.8 693 C44H50N4.Co 76.17:7.26:8.08 76.07:7.33:8.14 385, 398, 422, 439(s), 525 EMI82.1 Table <SEP> 1-25 <tb> # <tb> # <SEP> # <SEP> Example <tb> No. <SEP> of <tb> Reaction <tb> Example <SEP> Condi- <SEP> Yield <SEP> Crystal <tb> No. <SEP> R1 <SEP> R2 <SEP> R3 <SEP> tions <SEP> (%) <SEP> Color <SEP> R1 <SEP> R2 <SEP> R3 <tb> 198 <SEP> -CH3 <SEP> -CH2(CH2)2CH3 <SEP> -CH2(CH2)2CH3 <SEP> 5 <SEP> 47.3 <SEP> Brown <SEP> -CH3 <SEP> -CH2(CH2)2CH3 <SEP> -CH2(CH2)2CH3 <tb> 199 <SEP> -CH3 <SEP> -CH2(CH2)3CH3 <SEP> -CH2(CH2)3CH3 <SEP> 5 <SEP> 39.2 <SEP> -ditto- <SEP> -CH3 <SEP> -CH2(CH2)3CH3 <SEP> -CH2(CH2)3CH3 <tb> 200 <SEP> -CH3 <SEP> -CH2(CH2)4CH3 <SEP> -CH2(CH2)4CH3 <SEP> 5 <SEP> 28.9 <SEP> -ditto- <SEP> -CH3 <SEP> -CH2(CH2)4CH3 <SEP> -CH2(CH2)4CH3 <tb> 201 <SEP> -CH3 <SEP> -CH2(CH2)5CH3 <SEP> -CH2(CH2)5CH3 <SEP> 5 <SEP> 19.8 <SEP> -ditto- <SEP> -CH3 <SEP> -CH2(CH2)5CH3 <SEP> -CH2(CH2)5CH3 <tb> 202 <SEP> -CH3 <SEP> -CH2(CH2)6CH3 <SEP> -CH2(CH2)6CH3 <SEP> 5 <SEP> 18.2 <SEP> -ditto- <SEP> -CH3 <SEP> -CH2(CH2)6CH3 <SEP> -CH2(CH2)6CH3 <tb> 203 <SEP> -C2H5 <SEP> -C2H5 <SEP> -C2H5 <SEP> 5 <SEP> 60.2 <SEP> -ditto- <SEP> -C2H5 <SEP> -C2H5 <SEP> -C2H5 <tb> 204 <SEP> -CH2CH2CH3 <SEP> -CH2CH2CH3 <SEP> -CH2CH2CH3 <SEP> 5 <SEP> 55.6 <SEP> -ditto- <SEP> -CH2CH2CH3 <SEP> -CH2CH2CH3 <SEP> -CH2CH2CH3 <tb> #205 <SEP> -CH2(CH2)2CH3 <SEP> -CH2(CH2)2CH3 <SEP> -CH2(CH2)2CH3 <SEP> 5 <SEP> 43.3 <SEP> -ditto- <SEP> -CH2(CH2)2CH3 <SEP> -CH2(CH2)2CH3 <SEP> -CH2(CH2)2CH3 <tb> Table 1-25 (-continued) Elementary Analysis Mass Spectrum C:H:N (%) Example Visible Spectrum [DMF] No. Calcd. Found Formula Calcd. Found (nm) 198 750.0 749 C48H58N4.Co 76.88:7.80:7.47 76.92:7.71:7.50 384, 397, 422, 439(s), 525 199 806.1 805 C52H66N4.Co 77.48:8.25:6.95 77.39:8.15:7.04 385, 398, 421, 439(s), 524 200 862.2 861 C56H74N4.Co 78.01:8.65:6.50 77.93:8.63:6.58 385, 398, 421, 439(s), 525 201 918.3 917 C60H82N4.Co 78.48:9.00:6.10 78.60:8.92:6.05 385, 397, 421, 439(s), 525 202 974.4 973 C64H90N4.Co 78.89:9.31:5.75 78.93:9.30:5.72 386, 397, 421, 439(s), 525 203 665.8 665 C42H46N4.Co 75.77:6.96:8.42 75.85:6.92:8.38 385, 397, 421, 438(s), 524 204 750.0 749 C48H58N4.Co 76.88:7.80:7.47 76.95:7.74:7.44 385, 397, 421, 438(s), 525 205 834.1 833 C54H70N4.Co 77.76:8.46:6.72 77.64:8.53:6.80 385, 397, 421, 439(s), 525 EMI84.1 Table <SEP> 1-26 <tb> # <tb> # <SEP> # <SEP> Example <tb> No. <SEP> of <tb> Reaction <tb> Example <SEP> Condi- <SEP> Yield <SEP> Crystal <tb> No. <SEP> R1 <SEP> R2 <SEP> R3 <SEP> tions <SEP> (%) <SEP> Color <SEP> R1 <SEP> R2 <SEP> R3 <tb> #206 <SEP> -CH2(CH2)3CH3 <SEP> -CH2(CH2)3CH3 <SEP> -CH2(CH2)3CH3 <SEP> 5 <SEP> 38.0 <SEP> Brown <SEP> -CH2(CH2)3CH3 <SEP> -CH2(CH2)3CH3 <SEP> -CH2(CH2)3CH3 <tb> #207 <SEP> -CH2(CH2)4CH3 <SEP> -CH2(CH2)4CH3 <SEP> -CH2(CH2)4CH3 <SEP> 5 <SEP> 26.8 <SEP> -ditto- <SEP> -CH2(CH2)4CH3 <SEP> -CH2(CH2)4CH3 <SEP> -CH2(CH2)4CH3 <tb> #208 <SEP> -CH2(CH2)5CH3 <SEP> -CH2(CH2)5CH3 <SEP> -CH2(CH2)5CH3 <SEP> 5 <SEP> 13.2 <SEP> -ditto- <SEP> -CH2(CH2)5CH3 <SEP> -CH2(CH2)5CH3 <SEP> -CH2(CH2)5CH3 <tb> #209 <SEP> -CH2(CH2)6CH3 <SEP> -CH2(CH2)6CH3 <SEP> -CH2(CH2)6CH3 <SEP> 5 <SEP> 11.3 <SEP> -ditto- <SEP> -CH2(CH2)6CH3 <SEP> -CH2(CH2)6CH3 <SEP> -CH2(CH2)6CH3 <tb> Table 1-26(-continued) Elementary Analysis Mass Spectrum C:H:N (%) Example Visible Spectrum [DMF] No. Calcd. Found Formula Calcd. Found (nm) 206 918.3 917 C60H82N4.Co 78.48:9.00:6.10 78.53:8.94:6.07 385, 397, 421, 439(s), 525 207 1002.4 1001 C66H94N4.Co 79.08:9.45:5.59 79.03:9.51:5.57 385, 397, 421, 439(s), 525 208 1086.6 1085 C72H106N4.Co 79.59:9.83:5.16 79.66:9.80:5.11 385, 397, 421, 439(s), 525 209 1170.8 1169 C78H118N4.Co 80.02:10.16:4.79 79.96:10.20:4.83 386, 397, 421, 438(s), 525 # 1) : (s) means a shoulder of a peak. # 2) : - means a center wave length of a plateau peak. Example 210 The oxygen reduction catalyst activities of Co TAA as obtained in Examples 1, 3, 8, 19, 93, 96, 126, 140, f 154, 168, 188 and 198 were measured. The measurement was carried out in accordance with the cyclic voltammetry metbod by using a potentiostat. In 1 Q of chloroform or 1 Q of N,N-dimethylformamide was dissolved 800 mg of Co-TAA,and into the solution was dipped a Glassy Carbon trade name; product of Tokai Denkyoku Seizo K.K.) whose surface was mirror-plane finished for 30 minutes. The Glassy Carbon was taken out from the solution and left to stand to dryness. The treated glassy carbon was employed as a cathode electrode. A platinum coil was employed as an anode electrode and a calomel electrode was employed as a reference electrode. The electrolyte solution was IN sulfuric acid and the measurement temperature was 250C. The measurement was carried out by introducing a high-purity oxygen gas into the electrolytic solution and recording the electric current generated by varying the voltage from +800 mV to -600 mV at a velocity of 25 mV/sec. The catalyst activity was evaluated by the generated electric current value at +375 mV. The measurement was repeated 10 times and the catalyst life was evaluated by the tenth measurement result, that is, the tenth catalyst activity. 5The measurement results are shown in Table 2. Table 2 Catalyst obtained in Catalyst Activity Catalyst Life Example No. (pA/cm2) ( A/cmê) t 1 125 125 3 165 165 8 138 138 19 167 167 93 158 158 96 157 157 126 145 145 140 152 152 154 150 149 168 144 144 188 144 144 198 147 147 Comparative Example The catalyst activity and the catalyst life of Co-TAA having the formula (VII) were measured by the same methods as those of this invention. The Co-TAA has a catalyst activity of 145 pA/cm2 and a catalyst life of 30 A/cmê. Example 211 EMI88.1 In 25 ml of N,N-dimethylformamide were dissolved 0.02 mol of a 6-ethoxy-a-arylacrolein and 0 02 mol of an ophenylenediamine derivative as set forth in Table 3. The solution was refluxed under heating for 5 hours The reaction solution was cooled to 259C to give a compound. The compound obtained was separated by filtration, washed with methanol and dried. The yield is shown in Table 3. All the compounds were confirmed as tetraazaannulene derivatives. Table 3 EMI89.1 Experiment Yield No. R4 R5 R6 (%) 1 H- H- H- @ 34 2 O2N- H- H- 26 3 CH3O- H- H- 27 4 CH3- H- H- 31 5 NC- H- H- 30 6 HOOC- H- H- 30 7 C- H- H- 27 8 Br- H- H- 28 9 H- CH3- H- 18 10 H- CH3- CH3- 29 11 H- C- H- 16 12 H- C- C@- 33 13 H- CH3O- H- 3 14 H- COOH- CHa- 3 15 H- O2N- H- 5 Step 2 EMI90.1 In 10 ml of N,N-dimethylformamide were dissolved 5 millimol of each of the tetraazaannulene derivatives obtained in Step I and 5 millimol of cobalt (II) acetate tetrahydrate, and the solution was refluxed under heating for 5 hours. The reaction solution was cooled to 250C to give a compound. The compound was filtered, washed with methanol and dried. All the compounds were obtained at a yield of 90- 958, and identified as Co-TAA having the formula (III) by elementary analysis, the mass spectra and visible spectra thereof. Example 212 EMI90.2 In 25 ml of N,N-dimethylformamide were dissolved 0.02 mol of a B-alkoxy-a-phenylacrolein as set forth in Table 4 and 2.16 g (0.02 mol) of o-phenylenediamine, and the solution was refluxed under heating for 5 hours. The reaction solution was cooled to 250C to give a compound. The compound obtained was separated by filtration, washed with methanol and dried. The yield is shown in Table 4. All the compounds were confirmed as the tetraazaannulene derivative. Table 4 EMI92.1 <tb> <SEP> Q <SEP> 4 <SEP> X <SEP> t <tb> <SEP> 0 <SEP> 0 <tb> Experiment <SEP> R7 <SEP> Yield <SEP> [in <SEP> DMF] <tb> <SEP> No. <SEP> R7 <SEP> (%) <SEP> (no) <tb> <SEP> 1 <SEP> CH3- <SEP> 33 <SEP> 390, <SEP> 427, <SEP> 446 <tb> <SEP> 2 <SEP> CH3CH2- <SEP> 34 <SEP> 390, <SEP> 427, <SEP> 446 <tb> <SEP> 3 <SEP> CH3CH2CH2- <SEP> 32 <SEP> 390, <SEP> 427, <SEP> 446 <tb> <SEP> 4 <SEP> CH3(CH2)3- <SEP> 33 <SEP> 390, <SEP> 427, <SEP> 446 <tb> <SEP> 5 <SEP> CH3(CH2)5- <SEP> 34 <SEP> 390, <SEP> 427, <SEP> 446 <tb> <SEP> 6 <SEP> CH2-CH2 <SEP> 30 <SEP> 390, <SEP> 427, <SEP> 446 <tb> <SEP> C2 <SEP> FH <tb> <SEP> - <SEP> CH2-CH2 <tb> <SEP> 7 <SEP> CH3NCH <SEP> 32 <SEP> 390, <SEP> 427, <SEP> 446 <tb> <SEP> CH3 <tb> EMI92.2 EMI92.3 In 20 ml of N,N-dimethylformamide were dissolved 5 millimol of an o-phenylenediamine derivative as set forth in Table 5 and 623 mg (2.5millimol) of cobalt (II) acetate tetrahydrate, and the solution was heated at 1200C. The solution was added with 5 millimol of a ss-ethoxy-&alpha;-arylaerolein as set forth in Table 5 and refluxed under heating for 5 hours. /The reaction solution was cooled, filtered, washed with methanol and dried to give a compound at a yield as shown in Table 5. All the compounds were confirmed as Co-TAA. Table 5 EMI93.1 EMI93.2 Experiment C2H5O O R6 NH2 Yield No. R4 R6 Ra (%) 1 H- H- H- 52 2 02N- H- H- 38 3 CHlO- H- H- 37 4 CH3- H- H- 37 5 NC- H- H- 40 6 H- CH3- H- 31 7 H- CH3- CE3- 35 8 H- C2- H- 22 9 H- C- C- 40 10 H- CH3O- H- 8 11 CH3O- C- H- 47 12 O2N- CH3- H- 36 13 CH3- CE3- CH3- 66 Example 214 The same procedures as described in Experiment No. 1 of Example 213 were repeated except that a ss-ethoxy-a- arylacrolein as set forth in Table 6 was employed instead of the ss-ethoxy-&alpha;-phenylacrolein. All the compounds obtained were confirmed as Co-TAA. The yield of Co-TAA is shown in Table 6. Table 6 EMI94.1 Experimental Yield No. R4 Position of Rk (%) 1 CH3- ortho 31 2 CH30- ortho 25 3 CH3- meta 43 4 CH3O meta 37 5 5 C- ortho 28 6 C- meta 34 Example 215 EMI95.1 In 20 ml of N,N-dimethylformamide were dissolved 5 millimol (540 mg) of o-phenylenediamine and 2.5 millimol (623 mg) of cobalt (II) acetate tetrahydrate, and the solution was heated to 1200C. Then, the solution was added with 5 millimol of a B-alkoxy-a-phenylacrolein as set forth in Table 7, and refluxed under heating for 5 hours. The reaction solution was cooled, filtered, washed with methanol and dried to give a compound at a yield as shown in Table 7. All the compounds were confirmed as Co-TAA. Table 7 EMI96.1 <tb> <SEP> Visible <SEP> Spectrum <tb> <SEP> O <SEP> o <tb> Experiment <SEP> R¯ <SEP> Yield <SEP> [in <SEP> DMF] <tb> <SEP> No. <SEP> R7 <SEP> (%) <SEP> (nm) <tb> <SEP> I <SEP> CH3- <SEP> 52 <SEP> 377(s), <SEP> 388, <SEP> 425(s), <tb> <SEP> 522 <tb> <SEP> 2 <SEP> CH3CH2- <SEP> 54 <SEP> 377(s), <SEP> 388, <SEP> 425(s), <tb> <SEP> 522 <tb> <SEP> 3 <SEP> CE3CH2CH2- <SEP> 50 <SEP> 377(s), <SEP> 388, <SEP> 425(s), <tb> <SEP> 522 <tb> <SEP> 4 <SEP> CH3(CH2)3- <SEP> 51 <SEP> 377(s), <SEP> 388, <SEP> 425(s), <tb> <SEP> 522 <tb> <SEP> 5 <SEP> CH3(CH2)5- <SEP> 50 <SEP> 377(s), <SEP> 388, <SEP> 425(s), <tb> <SEP> 522 <tb> <SEP> ,-CH2-CH2 <tb> <SEP> CH2 <SEP> ,,,,,CH- <SEP> 49 <SEP> 377(s), <SEP> 388, <SEP> 425(s), <tb> <SEP> CHZ-CH2 <SEP> 522 <tb> <SEP> 7 <SEP> CH3-cE <SEP> 53 <SEP> 377(s), <SEP> 388, <SEP> 425(s), <tb> <SEP> CH3' <SEP> 522 <tb> # : (s) means a shoulder of a peak EMI97.1 In 30 ml of N,N-dimethylformamide were dissolved 0.02 mol of a ss-dimethylamino-a-arylacrolein and 0.02 mol of an o-phenylenediamine derivative as set forth in Table 8, and the solution was refluxed under heating for 5 hours. The reaction solution was cooled to 250C to separate a compound. The compound obtained was separated by filtration, washed with methanol and dried under reduced pressure. The yield is shown in Table 8. All the compounds were confirmed as tetraazaannulene derivatives. Table 8 EMI98.1 EMI98.2 EMI98.3 Experiment <SEP> ------ <SEP> Yield <tb> <SEP> No. <SEP> R4 <SEP> Rs <SEP> Ra <SEP> (%) <tb> <SEP> 1 <SEP> H- <SEP> H- <SEP> H- <SEP> 54 <tb> <SEP> 2 <SEP> O2N- <SEP> H- <SEP> H- <SEP> 39 <tb> <SEP> 3 <SEP> CH3O- <SEP> H- <SEP> H- <SEP> 39 <tb> <SEP> 4 <SEP> CH3- <SEP> H- <SEP> H- <SEP> 49 <tb> <SEP> 5 <SEP> H- <SEP> CH3- <SEP> H- <SEP> 25 <tb> <SEP> 6 <SEP> H- <SEP> CH3- <SEP> CH3- <SEP> 52 <tb> <SEP> 7 <SEP> H- <SEP> CH3O- <SEP> H- <SEP> 5 <tb> <SEP> t <SEP> CH3- <SEP> CH3O- <SEP> H- <SEP> 4 <tb> <SEP> 9 <SEP> CH3- <SEP> CH30- <SEP> CH2O- <SEP> - <SEP> 7 <tb> <SEP> 10 <SEP> O2N- <SEP> CH3 <SEP> - <SEP> CK3- <SEP> 59 <tb> <SEP> 11 <SEP> CH3O- <SEP> CH30- <SEP> H- <SEP> 8 <tb> <SEP> 12 <SEP> C2H5OC- <SEP> CH3O- <SEP> H- <SEP> 6 <tb> <SEP> 0 <tb> <SEP> 13 <SEP> CH3O- <SEP> CH3O- <SEP> CH2O- <SEP> 10 <tb> Step 2 EMI99.1 In 10 ml of N,N-dimethylformamide were dissolved 5-1 millimol of each of the tetraazaannulene derivatives obtained and 5 ml of cobalt (II) acetate tetrahydrate, and the solution was refluxed under heating for 5 hours. The reaction solution was cooled to 250C to give a compound. The compound obtained was separated by filtration, washed with methanol and dried. All the compounds were obtained at a yield of 90-95%, and confirmed as Co-TAA. Example 217 EMI99.2 In 30 ml of N,N-dimethylformamide were dissolved 0.02 mol of a S-dialkylamino-a-phenylacrolein as set forth in Table 9 and 2.16 g (0.02 mol) of o-phenylenediamine, and the solution was refluxed under heating for 5 hours.reaction solution was cooled to 250C to give a compound The compound obtained was separated by filtration, washed with methanol and dried under reduced pressure. The yield is shown in Table 9. All the compounds were confirmed as the tetraazaannulene derivative. Table 9 EMI100.1 <tb> <SEP> X+H <tb> <SEP> /N\O <SEP> Visible <SEP> Spectrum <tb> Experiment <SEP> Ra <SEP> Rg <SEP> Yield <SEP> [in <SEP> D1F3 <tb> <SEP> No. <SEP> Ra <SEP> Rs <SEP> (%) <SEP> ) <SEP> (nm) <tb> <SEP> 1 <SEP> CH3- <SEP> CH3- <SEP> 54 <SEP> 390, <SEP> 427, <SEP> 446 <tb> <SEP> 2 <SEP> CH3CH2- <SEP> CH3CH2- <SEP> 51 <SEP> 390, <SEP> 427, <SEP> 446 <tb> <SEP> 3 <SEP> CH3- <SEP> CH3CH2- <SEP> 53 <SEP> 390, <SEP> 427, <SEP> 446 <tb> <SEP> 4 <SEP> CH3- <SEP> CH3(CH2)3- <SEP> 50 <SEP> 390, <SEP> 427, <SEP> 446 <tb> <SEP> 5 <SEP> CH3(CH2)3- <SEP> CH3(CH2)3- <SEP> 52 <SEP> 390, <SEP> 427, <SEP> 446 <tb> In N,N-dimethylformamide were dissolved the tetraazaannulene obtained and the equimolar amount of cobalt (II) acetate tetrahydrate, and the solution was refluxed under heating for 5 hours. The reaction solution was cooled to 250C to give a compound. The compound obtained was separated by filtration, washed with methanol and dried. All the compounds were obtained in a yield of 90-95%, and confirmed as Co-TAA. Example 218 EMI101.1 In 20 ml of N,N-dimethylformamide were dissolved 5 millimol of an o-phenylenediamine derivative as set forth in Table 10 and 623 mg (2.5 millimol) of cobalt (II) acetate tetrahydrate, and the solution was heated at 1200C for 30 minutes. The solution was added with 5 millimol of a B- dimethylamino-a-arylacrolein as set forth in Table 10, and refluxed under heating for 5 hours. The reaction solution was cooled, filtered, washed with methanol and dried to give a compound. The yield is shown in Table 10. All the compounds were confirmed as Co-TAA. Table 10 EMI102.1 EMI102.2 EMI102.3 <tb> Experiment <SEP> ------ <SEP> Yield <tb> <SEP> No. <SEP> ¯ <SEP> R4 <SEP> Rs <SEP> R6 <SEP> (%) <tb> <SEP> 1 <SEP> CH3- <SEP> H- <SEP> H- <SEP> 58 <tb> <SEP> 2 <SEP> O2N- <SEP> H- <SEP> H- <SEP> 63 <tb> <SEP> 3 <SEP> CH3O- <SEP> H- <SEP> H- <SEP> 60 <tb> <SEP> 4 <SEP> C±- <SEP> H- <SEP> H- <SEP> 67 <tb> <SEP> 5 <SEP> H- <SEP> CH3- <SEP> H- <SEP> 45 <tb> <SEP> 6 <SEP> H- <SEP> CH3- <SEP> CH3- <SEP> 72 <tb> <SEP> 7 <SEP> H- <SEP> .C- <SEP> C- <SEP> 54 <tb> <SEP> 8 <SEP> CH3- <SEP> CH30- <SEP> H- <SEP> 9 <tb> <SEP> 9 <SEP> CH3- <SEP> CHsO- <SEP> CH3O- <SEP> 14 <tb> <SEP> 10 <SEP> NC- <SEP> C±- <SEP> C- <SEP> 67 <tb> <SEP> 11 <SEP> C2HsOC- <SEP> CH30- <SEP> H- <SEP> 10 <tb> <SEP> II <tb> <SEP> 0 <tb> <SEP> 12 <SEP> 02N- <SEP> Cr"3- <SEP> CH3- <SEP> 73 <tb> <SEP> 13 <SEP> CH3O- <SEP> CR30- <SEP> H- <SEP> 15 <tb> <SEP> 14 <SEP> CR30- <SEP> CH3O- <SEP> CH3O- <SEP> 17 <tb> Example 219 EMI103.1 In 20 ml of N,N-dimethylformamide were dissolved 5 millimol (540 mg) of o-phenylenediamine and 2.5 millimol (623 mg) of cobalt (II) acetate tetrahydrate, and the solution was heated at 1200C for 30 minutes. The solution was added with 5 millimol of a B-dialkylamino-a-phenylacrolein as set forth in Table 11, and refluxed under heating for 3 hours. The reaction solution was cooled, filtered, washed with methanol and dried to give a compound at a yield as shown in Table 11. All the compound obtained were confirmed as Co-TAA. Table 11 EMI104.1 <SEP> 0 <SEP> -H <tb> <SEP> \ <SEP> Visible <SEP> Spectrum <tb> Experimental <SEP> Re <SEP> R9 <SEP> Yield <SEP> in <SEP> DMF1 <tb> <SEP> No. <SEP> Ra <SEP> Rg <SEP> - <SEP> (%) <SEP> (nm) <SEP> ,, <tb> <SEP> 1 <SEP> CH3- <SEP> CE3- <SEP> 72 <tb> <SEP> 425(s), <SEP> 52'2 <tb> <SEP> 2 <SEP> CH3CH2- <SEP> CH3CH2- <SEP> 63 <SEP> 377(s), <SEP> 388 <tb> <SEP> 425(s), <SEP> 522 <tb> <SEP> 3 <SEP> CH3- <SEP> CH3CH2- <SEP> 68 <SEP> 377(s), <SEP> 388 <tb> <SEP> 425(s), <SEP> 522 <tb> <SEP> 4 <SEP> CH3- <SEP> CH3(CH2)3- <SEP> 64 <SEP> 377(s), <SEP> 388 <tb> <SEP> 425(s), <SEP> 522 <tb> <SEP> 5 <SEP> CH3(CH2)3- <SEP> CH3(CH2)3- <SEP> 65 <SEP> 377(sir <SEP> 388 <tb> <SEP> 425(s), <SEP> 522 <tb> * : (s) means a shoulder of a peak Example 220 EMI104.2 In 25 ml of N,N-dimethylformamide were dissolved 0.02 mol of a ss-ethoxy-&alpha;-arylacrolein and 0.02 mol of an ophenylenediamine derivative as set forth in Table 12, and the solution was refluxed under heating for 5 hours.- The' reaction solution was cooled to 250C to give a compound. The compound obtained was separated by filtration, washed with methanol and dried. The yield is shown in Table 12.' All the compounds were confirmed as tetraazaannulene derivatives. Table 12 EMI105.1 Experiment Position Yield No. R4 of R4 R5 Ra (%) 1 CH2- ortho H- H- - 13 2 CH3- meta H- H- 18 3 CH3O- ortho H- H- 15 4 CHaO- meta H- H- 17 5 C- ortho H- H- 14 6 C2- meta H- H- 19 7 O2N- ortho H- X- 17 8 02N- meta H- H- 21 9 CH3O- ortho C- C- 16 10 CH3O- meta C- C- 20 Example 221 EMI106.1 In 25 ml of N ,N-dimethylformamide were dissolved 0.02 mol of a 6-dimethylamino-a-arylacrolein and 0.02 mol of an o-phenylenediamine derivative as set forth in Table 13, and the solution was refluxed under heating for 5 hours. The reaction solution was cooled to 250C to give a compound. The compound obtained was separated by filtration, washed with methanol and dried. The yield is shown in Table 13. All the compounds were confirmed as tetraazaannulele derivatives. Table 13 EMI107.1 Experiment Position Yield No. R4 of R4 R5 R6 (%) 1 CH3- ortho H- H- 15 2 CH3- meta H- H- 22 3 CH3O- ortho H- H- 20 4 CH3O- meta H- H- 23 5 C#- ortho H- H- 21 6 C#- meta H- H- 25 7 02N- ortho H- H- 24 8 O2N- meta H- H- 27 9 CH3O- ortho C#- C#- 23 10 CH3O- meta C#- C#- 28

Claims: WHAT IS CLAIMED IS: 1. A tetraazaannulene cobalt complex compound having the general formula (I); EMI108.1 wherein R1, R2 and R3 each independently is a hydrogen atom, a C1-8 alkoxy group or a Ci-a alkyl group but in case one of R1, R2 and R3 being a hydrogen atom the other two groups are not hydrogen atoms at the same time, and when R1 is a methyl group R2 and R3 are not hydrogen atoms at the same time. 2. A method for preparing a tetraazaannulene cobalt complex compound having the general formula (II); EMI108.2 wherein R4 is a hydrogen atom, a C1-8 alkoxy group, a C1-8 alkyl group, a halogen atom, a nitro group, a cyano group, a C1-8 acyloxyl group, a hydroxyl group, a, carboxyl group, a C1-8 alkoxycarbonyl group, a carbamoyl group, a N,N-di Ci-a alkylamino group, a C-a acylamino group, an amino group, a C1-a alkoxycarbonyl C1-8 @ alkyl group or a N,N-di Ci-a alkylamino C1-8 alkyl group; n is integer of 1 to 5; and R5 and R6 each independently is a hydrogen atom, a C1-8 alkoxy group, a C1-8 alkyl group, a halogen atom, a nitro group, a cyano group, a C1-8 acyloxyl group, a hydroxyl group, a carboxyl group, a C1-8 alkoxycarbonyl group, a carbamoyl group, a N,N-di C1-6 alkylamino group, a Ci-a acylamino group, or a Cl-a alkoxycarbonyl C1-8 alkyl group; which comprises reacting a S-alkoxy-a-arylacrolein of the general formula (III); EMI109.1 wherein R4 and n are the same as defined in the formula (II); and R7 is a C16 alkyl group; with an o-phenylenediamine derivative of the general formula (IV); EMI110.1 wherein Rs and R6 are the same as defined in the formula (II); to prepare a tetraazaannulene derivative of the formula (V); EMI110.2 wherein R4, Rs, R6 and n are the same as defined in.the formula (II); and reacting the tetraazaannulene derivative of the formula (V) with a cobalt compound. 3 . The method of Claim 2, wherein the reaction between the ss-alkoxy-&alpha;-arylacrolein of the general formula (III) and the o-phenylenediamine derivative of the general formula (IV) and/or the reaction between tetraazaannullne derivative of the formula (V) and the cobalt compound are carried out at 50 - 250 C. 4. A method for preparing a tetraazaannulene cobalt complex compound having the general formula (II) which com-' prises reacting a B-alkoxy-a-arylacrolein of the general formula (III) and an o-phenylenediamine derivative of the general formula (IV) in the presence of a cobalt compound.' 5. The method of Claim 4', wherein the reaction is carried out at 50 - 250 C. 6 A method for preparing a tetraazaannulene cobalt complex compound having the general formula (II) which comprises reacting a H-dialkylamino-a-arylacrolein of the general formula (VI); EMI111.1 wherein R4 and n are the same as defined in the formula (II); and Ra and Rs each independently is a C1- 6 alkyl group; with an o-phenylenediamine derivative of the general formula (IV) to prepare a tetraazaannulene derivative of the formula (V), and reacting the tetraazaannulene derivative with a cobalt compound. 7 . The method of Claim 6, wherein the reaction between the B-dialkylamino-a-arylacrolein of the general formula (VI) and the o-phenylenediamine derivative of the general formula (IV) and/or the reaction between the tetraazaannulene deriva tive of the formula (V) and the cobalt compound are carried out at 50 - 250 OC. 8. A method for preparing a tetraazaannulene cobalt complex compound having the general formula (II) which comprises reacting a S-aialkylamino-a-arylacrolein of the general formula (VI) with an o-phenylenediamine derivative of the general formula (IV) in the presence of a cobalt compound. 9. A method for preparing a tetraazaannulene derivative of the formula (V) which comprises reacting a ss-alkoxy-&alpha;- arylacrolein of the general formula (III) with an o-phenylene diaminederivative of the general formula (IV). 101 A method for preparing a tetraazaannulene derivative of the formula (V) which comprises reacting a 6-dialkylamino- a-aryl'acrolein of the general formula (VI) with an o-phenylene gamine derivative of the general formula (IV). 11. The method of any of the claims 8, 9 and 10, wherein the reaction is carried out at 50 - 250 OC.

Inventors: AKASHI, KAGEYASU ASAHIKASEI-NISHI-APARTMENT, SUGA, NOBUHIKO
Applicants: ASAHI KASEI KOGYO KABUSHIKI KAISHA
Application year: 1982
Main classification: C07D257
IPC codes: C07D257