Selenium oxy chloride-pyridine or bipyridine complexes

1. BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to novel organic selenium compounds having antineoplastic activities.
2. Description of the Prior Art
It has already been reported that a certain type of selenium compounds have an antineoplastic or anticarcinogenic activity (see, for example Japanese Patent Kokai (Laid-Open) Nos. 20271/84 and EP-95663A).
However, no selenium compound has yet been found which is practically usable as an antineoplastic or anticancer agent.
SUMMARY OF THE INVENTION
The present invention relates to the novel selenium compounds represented by the general formula (I):
Se(O).sub.a (R).sub.b (X).sub.c (A).sub.n (Y).sub.m (I)
(wherein R, X, A and Y represent respectively the groups specified below, a represents a number of 0 or 1, b represents a number of 0, 1 or 2, and (1) when a is 0 and b is also 0, c is 4, n is 1 or 2, and m is 0, (2) when a is 1 and b is 0, c is 2, n is 1 or 2, and m is 0 or 1, and (3) when b is 1 or 2, c, n and m are all 0;
(i) When b is 2, R represents (1) a C.sub.4-10 alkoxy group substituted with a halogen atom, (2) a lower alkoxy group substituted with a halogen atom and a phenyl group, or (3) a cycloalkyloxy group substituted with a halogen atom, and (ii) when b is 1, R represents a group represented by the formula: ##STR4## (wherein R.sub.0 represents a C.sub.2-6 alkyl group); X represents a halogen atom;
A represents caffeine, theophylline, N-benzyltheophylline, N-benzyltheobromine, 2,2'-biquinoline, 1,6-naphthylidine, 1,10-phenanthroline or a compound represented by the formula: ##STR5## (wherein R.sub.1 and R.sub.2 may be the same or different and represent respectively a hydrogen atom, a hydroxyl group, a lower alkyl group, a halogen atom, a phenyl group, a cyano group, a lower alkoxycarbonyl group, a phenoxycarbonyl group, an amino group (to which a lower alkyl group, lower alkylaminocarbonyl group, lower halogenoalkylaminocarbonyl group or lower alkoxycarbonyl group may be bonded), a benzoyl group, a lower alkoxy group, a carbamyl group, or a allyloxycarbonyl group; R.sub.3 represents a C.sub.1-10 alkyl group or a benzyl group; R.sub.4 and R.sub.5 represent independently a hydrogen atom, a halogen atom or an alkyl group, or R.sub.4 and R.sub.5 may represent ##STR6## in combination; R.sub.6 represents a lower alkoxy group, a phenyl group or a phenoxy group; R.sub.7 represents a hydrogen atom, a lower alkyl group or a group represented by the formula: ##STR7## (wherein R.sub.9 represents an amino group or a lower alkoxy group); R.sub.10 represents a hydrogen atom or a nitro group; and one of B and D represents nitrogen and the other represents ##STR8## Y represents H.sub.2 O or an alcohol represented by the formula: R.sub.8 -OH (wherein R.sub.8 represents a benzyl or alkyl group which may be substituted with a lower alkoxyl group);
wherein when X is chlorine atom and m is 0, R.sub.1 and R.sub.10 represent an atom or a group other than hydrogen atom).
DETAILED DESCRIPTION OF THE INVENTION
In the above-shown general formula (I), the halogen atom can be fluorine, chlorine, bromine or iodine, but chlorine, bromine and fluorine are preferred. The lower alkyl group can be, for instance, a C.sub.1-5 alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, t-butyl, pentyl and the like. As the alkyl group, C.sub.1-10 alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, t-butyl, pentyl, hexyl, octyl and decyl can be mentioned. The lower alkoxy group can be selected from C.sub.1-5 alkoxy groups including methoxy, ethoxy, propoxy, isopropoxy and butoxy. The lower alkylamino group can be, for instance, a C.sub.1-4 mono- or dialkylamino group. The cycloalkyloxy group can be selected from the C.sub.4-8 cycloalkyloxy groups. The lower alkoxy in the lower alkoxycarbonyl group may be a C.sub.1-5 lower alkoxy. The halogen in the lower halogenoalkylaminocarbonyl and lower halogenoalkyl groups can be fluorine, bromine, chlorine or iodine. The lower alkyl can be a C.sub.1-5 lower alkyl.
In the compounds represented by the general formula (I), in case a is 1, b is 1 or 2, and c, m and n are 0, that is, in the case of SeO(R) .sub.1 or 2, the C.sub.4-10 alkoxyl group substituted with a halogen atom can be, for instance, 2-chlorobutoxy, 2-bromobutoxy, 2-chloropentyloxy, 2-bromopentyloxy, 2-chlorohexyloxy, 2-bromohexyloxy, 2-chloroheptyloxy, 2-bromoheptyloxy, 2-chlorooctyloxy, 2-bromooctyloxy, 2-chlorononanyloxy, 2-bromononanyloxy, 2-chlorodecanyloxy, 2-bromodecanyloxy, 2-chloro-1-methylethoxy, 2-chloro-1-methylpropoxy, 2-chloro-2-methylpropoxy, 2-chloro-1,1-dimethylpropoxy, 2-chloro-1,2-dimethylpropoxy, 2-chloro-1,1,2-trimethylpropoxy, 2-chloro-1-methylbutoxy, 2-chloro-2-methylbutoxy, 2-chloro-3-methylbutoxy, 2-chloro-1,1-dimethylbutoxy, 2-chloro-1,2-dimethylbutoxy, 2-chloro-1,2,3-trimethylbutoxy, 2-chloro-1,1,2,3-tetramethylbutoxy, 2-chloro-1,1,2,3,3-pentamethylbutoxy, 2-bromo-1-butylbutoxy and the like.
The lower alkoxy group substituted with a halogen atom and a phenyl group can be, for instance a C.sub.2-4 alkoxy group such as 2-chloro-1-phenylethoxy, 2-chloro-2-phenylethoxy, 2-chloro-1-phenylpropoxy, 2-chloro-2-phenylpropoxy, 2-chloro-3-phenylpropoxy, and 2-bromo-2-phenylbutoxy.
Examples of the cycloalkyloxy groups substituted with a halogen atom are the C.sub.4-8 cycloalkyloxy groups such as 2-chlorocyclobutyloxy, 2-chlorocyclopentyloxy, 2-chlorocyclohexyloxy, 2-chlorocyclooctyloxy, and 3-chloronorbonyl-2-iloxy. The C.sub.2-6 alkyl groups represented by R.sub.0 include ethyl, propyl, isopropyl, butyl, sec-butyl, t-butyl, pentyl and the like.
In the compounds represented by the general formula (I), in case b is 0, that is, in the case of the formula Se(O).sub.a (X).sub.2 or 4 (A).sub.m (Y).sub.n, the compounds represented by the formula ##STR9## include pyridine, picoline, lutidine, ethylpyridine, isopropylpyridine, t-butylpyridine, phenylpyridine, fluoropyridine, chloropyridine, bromopyridine, dichloropyridine, cyanopyridine, ethyl picolinate, methyl nicotinate, ethyl nicotinate, methyl isonicotinate, ethyl isonicotinate, phenyl isonicotinate 4-benzoylpyridine, 4-aminopyridine, 4-dimethylaminopyridine, 2-N-methylaminopyridine, methyl 3-pyridiylcarboxamate, 2-hydroxypyridine, 4-hydroxypyridine, 4-methoxypyridine, allyl isonicotinate, N-methyl-N'-(3-pyridyl)-urea, N-(2-chloro)ethyl-N'-(3-pyridyl)urea, and 6-aminonicotinamide.
Examples of the compounds represented by the ##STR10## include N-methylimidazole, N-ethylimidazole, N-hexylimidazole, N-decylimidazole, N-benzylimidazole, 1,2-dimethylimidazole, 1-methyl-5-bromoimidazole, N-methylbenzimidazole, N-benzylbenzimidazole, 1-benzylpyrazole, and the like.
Examples of the compounds of the formula ##STR11## are triphenylphosphine oxide, triphenyl phosphate, trimethyl phosphate, triethyl phosphate and the like.
Examples of the compounds of the formula ##STR12## are isoquinoline, 1-hydroxyisoquinoline, 5-hydroxyisoquinoline, 5-nitroquinoline, 6-nitroquinoline, 8-nitroquinoline, 5-nitroisoquinoline and the like.
Examples of the compounds of the formula ##STR13## are 2,2'-dipyridyl, 2,2'-bi-methylisonicotinate, 2,2'-bi-ethylisonicotinate, 2,2'-bi-4-picoline and the like. Examples of the alcohols represented by Y are methyl alcohol, ethyl alcohol, propyl alcohol, octyl alcohol, benzyl alcohol, and anise alcohol.
As for the combinations of A and n, in case A is a 2,2'-dipyridyl derivative, 2,2'-biquinoline or 1,10-phenanthroline, n is 1, and in other cases, n is 1 or 2.
Typical examples of the compounds according to this invention are listed in Table 1 below.
TABLE 1-1______________________________________SeO(R).sub.1 or 2CompoundNo. Symbol______________________________________3-1 SOC1P Di-(2-chloro-1-methylpropyl)- selenite3-2 SOC2P Di-(2-chloro-2-methylpropyl)- selenite3-3 SOCB Di-(2-chlorobutyl)selenite3-4 SOCO Di-(2-chlorooctyl)selenite3-5 SOPE Di-(2-chlorophenetyl)selenite3-6 SOCH Di-(2-chlorcyclohexyl)selenite3-7 SOCN Di-(3-chloronorbonyl-2-il)selenite3-8 SOEEC 1,2-butanediolselenite3-9 SOEPC 2,2-diethyl-1,3-propanediolselenite______________________________________
TABLE 1-2______________________________________SeO(X).sub.2 (A).sub.m (Y).sub.nCom-poundNo. Symbol______________________________________1-1 SBPy Selenium oxybromide-pyridine (1:2) complex1-2 SC2Pc Selenium oxychloride-2-picoline (1:2) complex3-3 SC3Pc Selenium olxychloride-3-picoline (1:3) complex1-4 SC4Pc Selenium oxychloride-4-picoline (1:2) complex1-5 SC35Lt Selenium oxychloride-3,5-lutidine (1:2) complex1-6 SC4Et Selenium oxychloride-4-ethylpyridine (1:2) complex1-7 SC4Ip Selenium oxychloride-4-isopropyl- pyridine (1:2) complex1-8 SC4Bt Selenium oxychloride-4-t-butyl- pyridine (1:2) complex1-9 SC2Ph Selenium oxychloride-2-phenylpyridine (1:2) complex1-10 SC3Ph Selenium oxychloride-3-phenylpyridine (1:2) complex1-11 SC4Ph Selenium oxychloride-4-phenylpyridine (1:2) complex1-12 SC3Fl Selenium oxychloride-3-fluoropyridine (1:2) complex1-13 SC3Cl Selenium oxychloride-3-chloropyridine (1:2) complex1-14 SC3Br Selenium oxychloride-3-bromopyridine (1:2) complex1-15 SC35DC Selenium oxychloride-3,5-dichlor- pyridine (1:2) complex1-16 SC3Cy Selenium oxychloride-3-cyanopyridine (1:2) complex1-17 SC4Cy Selenium oxychloride-4-cyanopyridine (1:2) complex1-18 SCPE Selenium oxychloride-ethyl picolinate (1:2) complex1-19 SCNM Selenium oxychloride-methyl nicotinate (1:2) complex1-20 SCNE Selenium oxychloride-ethyl nicotinate (1:2) complex1-21 SCIE Selenium oxychloride-etyyl isonicotinate (1:2) complex1-22 SCMIm Selenium oxychloride-N--methyl- imidazole (1:2) complex1-23 SCEIm Selenium oxychloride-N--ethyl- imidazole (1:2) complex1-24 SCHIm Selenium oxychloride-N--hexyl- imidazole (1:2) complex1-25 SCTIm Selenium oxychloride-N--decylimidazole (1:2) complex1-26 SCBIm Selenium oxychloride-N--benzyl- imidazole (1:2) complex1-27 SCDIm Selenium oxychloride-1,2-dimethyl- imidazole (1:2) complex1-28 SCRIm Selenium oxychloride-1-methyl-5-bromo- imidazole (1:2) complex1-29 SCMBi Selenium oxychloride-N--methyl- benzimidazole (1:2) complex1-30 SCBBi Selenium oxychloride-N--benzyl- benzimidazole (1:2) complex1-31 SCCf Selenium oxychloride-caffein (1:2) complex1-32 SBCf Selenium oxybromide-caffein (1:2) complex1-33 SCBTf Selenium oxychloride-N--benzyl- theophylline (1:2) complex1-34 SCBTb Selenium oxychloride-N--benzyl- theobromine (1:2) complex1-35 SCBPr Selenium oxychloride-1-benzyl- pyrazole (1:2) complex1-36 SCPP Selenium oxycloride-triphenyl- phosphine oxide (1:2) complex1-37 SCPOP Selenium oxychloride-triphenyl phosphate (1:2) complex1-38 SCMOP Selenium oxychloride-trimethyl phosphate (1:2) complex1-39 SCEOP Selenium oxychloride-triethyl phos- phate (1:2) complex1-40 SClMBi Selenium oxychloride-N-methylbenz- imidazole (1:1) complex1-41 SCDp Selenium oxychloride-2,2'-dipyridyl (1:1) complex1-42 SBDp Selenium oxybromide-2,2'-dipyridyl (1:1) complex1-43 SCBPc Selenium oxychloride-2,2'-bi-4- pyrroline (1:1) complex1-44 SCBQn Selenium oxychloride-2,2'-biquinoline (1:1) complex1-45 SCPn Selenium oxychloride-1,10- phenanthroline (1:1) complex1-46 SCPy(M) Selenium oxychloride-pyridine (1:2) complex mono methyl alcoholate1-47 SCPy(E) Selenium oxychloride-pyridine (1:2) complex mono ethyl alcoholate1-48 SCPy(A) Selenium oxychloride-pyridine (1:2) complex mono anise alcoholate1-49 SCPy(O) Selenium oxychloride-pyridine (1:2) complex mono octyl alcoholate1-50 SCPy(B) Selenium oxychloride-pyridine (1:2) complex mono benzyl alcoholate1-51 SCIM Selenium oxychloride-methyl iso- nicotinate (1:2) complex1-52 SCIP Selenium olxychloride-phenyl isonicotinate (1:2) complex3-10 SC4Bz Selenium oxychloride-4-benzyl- pyridine (1:2) complex3-11 SC4Ap.aq Selenium oxychloride-4-aminopyridine (1:2) complex mono hydrate3-12 SC4MAp Selenium oxychloride-4-dimethylamino- pyridine (1:2) complex3-13 SC2Hy Selenium oxychloride-2-hydroxypyridine (1:2) complex3-14 SC4Hy.aq Selenium oxychloride-4-hydroxypyridine (1:2) complex mono hydrate3-15 SC4Mo Selenium oxychloride-4-methoxy- pyridine (1:2) complex3-18 SCIA Selenium oxychloride-allyl iso- nicotinate (1:2) complex3-19 SC16Np Selenium oxychloride-1,6-naphthylidine (1:2) complex3-20 SC5NQ Selenium oxychloride-5-nitroquinoline (1:2) complex3-21 SC6NQ Selenium oxychloride-6-nitroquinoline (1:2) complex3-22 SC8NQ Selenium oxychloride-8-nitroquinoline (1:2) complex3-23 SC5NI Selenium oxychloride-5-nitroiso- quinoline (1:2) complex3-24 SCTf Selenium oxycloride-theophylline (1:2) complex3-25 SCBIM Selenium oxychloride-2,2'-bi-methyl- isonicotinate) (1:1) complex3-26 SCBIE Selenium oxychloride-2,2'-(ethyliso- nicotinate) (1:1) complex3-28 SC2Ap.aq Selenium oxychloride-2-aminopyridine (1:2) complex mono hydrate3-29 SC25AAm Selenium oxychloride-6-amino- nicotinamide (1:2) complex3-30 SC25HN Selenium oxychloride-2-hydroxy-5- nitropyridine (1:2) complex3-31 SC4HQ Selenium oxychloride-4-hydroxy- quinoline (1:2) complex3-32 SC8HQ Selenium oxychloride-8-hydroxy- quinoline (1:2) complex3-33 SC4BI Selenium oxychloride-4-bromoiso- quinoline (1:2) complex4-1 SC3CUa.aq Selenium oxychloride-3-(2-chloro- ethylaminocarbonylamino)pyridine (1:2) complex mono hydrate4-2 SC2MAp.aq Selenium oxychloride-2-(N--methylamino)- pyridine (1:2) complex mono hydrate______________________________________
TABLE 1-3______________________________________SeX.sub.4 (A).sub.mCompoundNo. Symbol______________________________________2-1 B4SPy Tetrabromoselenium-pyridine (1:2) complex2-2 C4S3Pc Tetrachloroselenium-3-picoline (1:2) complex2-3 C4S35Lt Teltrachloroselenium-3,5-lutidine (1:2) complex2-4 C4S3Ph Tetrachloroselenium-3-phenylpyridine (1:2) complex2-5 C4S4Ph Tetrachloroselenium-4-phenylpyridine (1:2) complex2-6 C4S3Fl Tetrachloroselenium-3-fluoropyridine (1:2) complex2-7 C4S3Cy Tetrachloroselenium-3-cyanopyridine (1:2) complex2-8 C4S4Cy Tetrachloroselenium-4-cyanopyridine (1:2) complex2-9 C4SNM Tetrachloroselenium-methyl nicotinate (1:2) complex2-10 C4SIq Tetrachloroselenium-isoquinoline (1:2) complex2-11 C4SMI Tetrachloroselenium-N--methylimidazole (1:2) complex2-12 C4SCf Tetrachloroselenium-caffein (1:2) complex2-13 C4SDp Tetrachloroselenium-2,2'-dipyridinyl (1:2) complex2-14 B4SDp Tetrabromoselenium-2,2'-dipyridyl (1:2) complex______________________________________
Among these compounds, the preferred ones are, for instance, 1-7, 1-10, 1-17, 1-28, 1-30, 1-41, 1-44, 1-46, 1-47, 2-1, 2-4, 2-5, 2-6, 2-7, 2-9, 3-2, 3-6, 3-9, 3-14, 3-18, 3-21, and 3-23. Most preferred are 1-41, and 3-14.
The compounds of this invention represented by the general formula (I) can be obtained from the following reaction: ##STR14## [wherein X represents a halogen atom; a is a number of 0 or 1, and when a is 0, c' is 4 and d is 0, and when a is 1, c' is 2 and d is 0 or 1; F represents A (where A is as defined above), a straight-chain 1,2-epoxyalkane, a lower 1,2-epoxyalkane substituted with a lower alkyl or phenyl group, an epoxycycloalkane, or a compound represented by the formula: ##STR15## (wherein R.sub.0 is as defined above)].
The compounds represented by the formula (II) include selenium oxyhalides such as selenium oxychloride, selenium oxybromide, etc., and their 1,4-dioxane complexes, and selenium tetrahalides such as tetrachloroselenium, tetrabromoselenium, etc. (The process for producing selenium oxyhalides dioxane (1:1) complex is described in the following literature; Yarovenko et al., Zh. Obshch. Khim. Vol. 31, P40006, 1961.)
The compounds represented by A in the formula F are such as mentioned before. The straight-chain 1,2-epoxyalkane can be a C.sub.4-10 1,2-epoxyalkane such as 1,2-epoxybutane, 1,2-epoxypentane, 1,2-epoxyhexane, 1,2-epoxyheptane, 1,2-epoxyoctane, 1,2-epoxynonane, and 1,2-epoxydecane.
Examples of the lower 1,2-epoxyalkanes substituted with a lower alkyl group are C.sub.2-4 alkanes substituted with a lower alkyl group, such as 1,2-epoxypropane, 1-methyl-1,2-epoxypropane, 1,1-dimethyl-1,2-epoxypropane, 1,2-dimethyl-1,2-epoxypropane, 1,1,2-trimethyl-1,2-epoxypropane, 1-methyl-1,2-epoxybutane, 2-methyl-1,2-epoxybutane, 3-methyl-1,2-epoxybutane, 1,1-dimethyl-1,2-epoxybutane, 1,2-dimethyl-1,2-epoxybutane, 1,2,3-trimethyl-1,2-epoxybutane 1,1,2,3-tetramethyl-1,2-epoxybutane, 1,1,2,3,3-pentamethyl-1,2-epoxybutane, and 1-butyl-1,2-epoxybutane.
Examples of the lower 1,2-epoxyalkanes substituted with a phenyl group are C.sub.2-4 1,2-epoxyalkanes such as 1-phenyl-1,2-epoxyethane, 2-phenyl-1,2-epoxyethane, 1-phenyl-1,2-epoxypropane, 2-phenyl-1,2-epoxypropane, 3-phenyl-1,2-epoxypropane, and 2-phenyl-1,2-epoxybutane.
Examples of the epoxycycloalkane are C.sub.4-8 1,2-epoxycycloalkanes such as 1,2-epoxycyclobutane, 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, 1,2-epoxycycloctane, and 2,3-epoxynorbornane.
Examples of the compounds represented by the formula: ##STR16## are 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, and 1,2-octanediol.
Examples of the compounds represented by the formula: ##STR17## are 2,2-diethyl-1,3-propanediol, 2,2-propyl-1,3-propanediol, 2,2-diisopropyl-1,3-propanediol, 2,2-dibutyl-1,3-propanediol, and 2,2-dipentyl-1,3-propanediol.
For preparing the compounds of this invention, a compound represented by the formula (II) and a compound represented by the formula F are reacted, and if necessary, this reaction product is further reacted with water or an alcohol.
More specifically, the compounds of this invention represented by the general formula (I) can be obtained by reacting a compound represented by the formula (II) and a compound represented by the formula F in a solvent having a boiling point of 150.degree. C. or below, preferably 110.degree. C. or below, such as dioxane, hexane, chloroform, ether, methylene chloride, tetrahydrofuran and the like, at a temperature of preferably 0.degree. to 100.degree. C., more preferably 10.degree. to 40.degree. C., for a period of 30 minutes to 5 days, more preferably one hour to 3 days.
In this reaction, if a hydrous solvent is used, there is obtained a compound of the formula (I) where m is 1 and Y is H.sub.2 O, and if anhydrous alcohol-containing solvent is used, there is obtained a compound of the formula (I) where Y is an alcohol. In case an anhydrous non-alcoholic solvent is used, there is obtained a compound of the formula (I) where m is 0.
Further, the compounds of the formula (I) where a is 1, b is 1 or 2, and c, m and n are 0, namely, the compounds of the formula SeO(R).sub.1 or 2 can be obtained in the following way.
(1) b=2:
A selenium oxyhalide-1,4-dioxane (1:1) complex or a selenium oxyhalide is reacted with a 1,2-epoxyalkane or 1,2-epoxycycloalkane which may be substituted with an alkyl or phenyl group, which corresponds to R in the above-shown formula, in an anhydrous solvent, and then the solvent is removed. As the solvent, those mentioned before can be used. The reaction is carried out at a temperature in the range of -20.degree. to 150.degree. C., preferably 0.degree. to 100.degree. C., more preferably 10.degree. to 40.degree. C., for a period of 30 minutes to 24 hours, preferably 1 to 8 hours.
The amount of the 1,2-epoxyalkane or 1,2-epoxycycloalkane which may be substituted with an alkyl or phenyl group, which corresponds to R in the above-shown formula, should be exactly twice the amount of the starting material selenium oxyhalide-1,4-dioxane (1:1) complex or selenium oxyhalide.
(2) b=1.
A selencium oxyhalide or a selenium oxyhalide-1,4-dioxane (1:1) complex is reacted with a diol corresponding to R in the above formula in an anhydrous solvent. If this reaction is conducted in the presence of a metal salt of an organic carboxylic acid, preferably an aliphatic carboxylic acid or oxycarboxylic acid, for example, a sodium, potassium or silver salt of oxalic acid, citric acid, acetic acid, propionic acid or the like, the reaction proceeds smoothly. After the reaction ended, the solvent is removed after filtering out the precipitated metal salt in case a metal salt of an organic carboxylic acid was used.
The solvent used in this reaction may be those mentioned before. The reaction temperature is -20.degree. to 150.degree. C., preferably 0.degree. to 100.degree. C., more preferably 10.degree. to 40.degree. C. The reaction time is 0.5 to 5 days, preferably 1 to 3 days.
As for the amount of the organic carboxylic acid and the diol used in the reaction, the former is preferably used in an amount approximately twice the amount of the starting selenium compound and the latter in an amount approximately equal to the amount of the selenium compound.
The compounds of the formula (I) where b and m are 0, that is, the compounds represented by the formula: Se(O).sub.a (X).sub.2 or 4 (A).sub.1 or 2 can be obtained in the following way.
A selenium tetrahalide, a selenium oxyhalide or a selenium olxyhalide-1,4-dioxane (1:1) complex is reacted with a compound represented by A in the formula (I) in an anhydrous solvent, and then the solvent is removed.
The solvent used in this reaction may be those mentioned before. The reaction temperature is in the range of -20.degree. to 150.degree. C., preferably 0.degree. to 100.degree. C., more preferably 10.degree. to 35.degree. C., and the reaction time is 30 minutes to 24 hours, preferably 1 to 8 hours.
The amount of A added is 1 to 10 times, preferably 2 to 3 times the amount of the starting selenium compound in case of obtaining the compounds of the formula (I) where n=2, and 0.5 to 5 times, preferably 1 to 2 times the amount of said selenium compound is case of obtaining the compounds of the formula (I) wherein n=1.
The compounds of the formula (I) where a is 1, b is 0, c is 2 and m is 1, that is, the compounds represented by the formula: SeOX.sub.2 (A).sub.1 or 2 Y can be obtained by using a hydrous solvent or an anhydrous alcohol-containing solvent in the above-described reaction.
(1) The compounds of the above-shown formula where Y is H.sub.2 O can be obtained by conducting the above-said reaction (for obtaining the compounds with m=0) by using a hydrous solvent with a water content of preferably 0.05 to 15%, more preferably 0.5 to 10%, or a hydrous alcohol solvent such as hydrous methanol with a water content of 0.5 to 10%, preferably 1 to 5%. In this case, the amount of the hydrous alcohol used, though variable depending on the water content, may be about 1 to 20% based on the solvent used for the reaction.
(2) The compounds of the above-shown formula where Y is an alcohol can be obtained by following said reaction process where m is 0 but by using an anhydrous solvent prepared by mixing an alcohol represented by Y and the above-said solvent.
The compounds of the above-shown formula where Y is H.sub.2 O or an alcohol can be also obtained by reacting the compound of m=0 with water or an anhydrous alcohol. That is, water or an alcohol of the formula Y is added to the reaction solution used for synthesizing the compound of m=0, or the isolated compound of m=0 of the formula (I) is dissolved in water or an alcohol of the formula Y, or in a solvent containing water or an alcohol, preferably at 10.degree. to 40.degree. C. and allowed to stand as it is for 10 minutes to 2 hours, and then the solvent is removed. The amount of water or alcohol is not subject to any limitation as far as it is not less than one time the amount of the compound of m=0 of the formula (I), and its ratio can be selected merely according to the technical matter in carrying out the reaction.
Through the reactions described above, the objective compounds can be obtained as an oily product, amorphous powder, grease-like oily substance or crystal, and their structures were confirmed by IR and NMR analyses.
The determined property values of the typical examples of the compounds according to this invention are shown in Table 2.
TABLE 2__________________________________________________________________________Com- NMR (60 MHz)pound (Solvent A: chloroform-d.sub.1No. Appearance B: dimethyl sulfoxide-d.sub.6 ) (ppm) IR [KBr, (cm.sup.-1)]__________________________________________________________________________1-1 Yellow A.: 8.19(m, 4H), 8.76(m, 2H), 9.07 1641, 1607, 1537, powder (m, 4H) 1488, 904, 752, 6781-2 Light- A.: 2.66(s, 6H), 7.53-7.76(m, 4H) 1638, 1624, 1546 yellow 8.07-8.36(m, 2H), 8.69(br d, j=5.2Hz, 1480, 890, 764, 700, powder, 2H) 660 hygroscopic1-3 White powder, A.: 2.46(s, 6H), 7.77(dd, J=8.0, 1638, 1620, 1559 hygroscopic 5.4Hz, 2H), 8.21(brd, j=8.0Hz, 1480, 895, 792, 677 2H), 8.68 (br d, J=5.4Hz, 2H), 8.73(br s, 2H)1-4 White A.: 2.69(s, 6H), 7.96(brd, J=6.2Hz, 1645, 1613, 1512, powder, 4H), 8.83 (br d, J=6.2Hz, 4H) 1204, 895, 793, 705, hygroscopic 6601-5 White A.: 2.48(s, 12H), 8.34(br s, 2H), 8.68 2070, 1630, 1571, powder, (br s, 4H) 1275, 890, 860, 725, hygroscopic 6801-6 White A.: 1.27(d, J=7.6Hz, 6H), 2.93 (q, 1645, 1608, 1508, powder, J=7.6Hz, 4H), 7.99 (br d, J=6.4Hz, 1205, 890, 822, 774, hygroscopic 4H), 8.87(br d, J=6.4Hz, 4H) 6501-7 White A.: 1.27(d, J=7.0Hz, 12H), 3.14 (septet, 1644, 1610, 1509, powder, J=7Hz, 2H), 7.82 (br d, J=6.0Hz, 1208, 1060, 892, 820, hygroscopic 4H), 8.76(br d, J=6.0Hz, 4H) 6561-8 White A.: 1.38(s, 18H), 8.04(br d, J=6.0Hz, 1644, 1610, 1508, 931, powder, 4H), 8.84(br d, J=6.0Hz, 4H) 880, 843, 819, 656 hygroscopic1-9 Yellow A.: 7.45-7.78(m, 8H), 8.03-8.21(m, 8H), 1618, 1583, 1540, oil 8.79(ddd, J=4.8, 1.2, 1.2Hz, 2H) 1501, 1472, 1441, viscous 1393, 1278, 906, 840, 795, 757, 730, 6911-10 White A.: 7.52-8.09(m, 12H), 8.69(ddd, J=8.0 1624, 1558, 1502, powder, 2.4, 1.6Hz, 2H), 8.78 (br d, 1474, 1446, 893, 818, hygroscopic J=4.8Hz, 2H), 9.21(br s, 2H) 758, 694, 6801-11 White A.: 7.62-7.72(m, 6H), 7.94-8.17(m, 4H), 1640, 1606, 1599, powder, 8.42(br d, J=7.2Hz, 4H), 9.01 (br 1523, 1489, 1293 hygroscopic d, J= 7.2Hz, 4H) 877, 848, 837, 824, 7601-12 Yellow A.: 7.58-7.95(m, 2H), 8.12(ddd, J=8.6, 1616, 1553, 1477, oil 3.0, 1.4Hz, 2H), 8.64 (br d, 1242, 895, 839, 826, J=4.4Hz, 2H), 8.83(br s, 2H) 807, 6681-13 Light-yellow A.: 7.66(dd, J=8.4, 4.8Hz, 2H), 8.18 1625, 1532, 1460, fine crystal, (ddd, J=8.4, 2.4, 1.4Hz, 2H), 1125, 890, 800, 730, hygroscopic 8.6-8.9(m, 4H) 6651-14 Light- A.: 7.60(dd, J=8.0, 4.8Hz, 2H), 8.30 1620, 1595, 1520, yellow fine (ddd, J=8.0, 2.4, 1.4Hz, 2H), 8.74 1464, 1452, 1246, crystal (br d, J=4.8Hz, 2H), 8.92(br s, 2H) 1108, 1015, 884, 857, 790, 6641-15 White B.: 7.87(t, J=2.1Hz, 2H), 8.61(d, 1536, 1417, 1250, fine J=2.1Hz, 4H) 1121, 1108, 911, 848, crystal 821, 687, 6581-16 White A.: 7.71(ddd, J=7.9, 4.8, 0.9Hz, 2H), 2254, 1639, 1611, crystal 8.39(ddd, J=7.9, 1.9, 1.8Hz, 2H), 1558, 1465, 904, 837, 8.91(br d, J=4.8Hz, 2H), 9.07(br s, 810, 771, 730, 678, 2H) 6691-17 Light- A.: 7.95(dd, J=4.4, 1.6Hz, 4H), 8.90 2250, 2088, 2006, yellow (br d, J=4.4Hz, 4H) 1638, 1598, 1499, crystal 1338, 1303, 1235, 1006, 899, 882, 820, 6651-18 Yellow A.: 1.35(t, J=7.0Hz, 6H), 4.38(q, 1745, 1611, 1537, oil J=7.0Hz, 4H), 7.58-7.93(m, 2H), 1459, 1332, 1291, 8.03-8.14(m, 4H), 8.75(br d, 1160, 1008, 901, 861, J=4.2Hz, 2H) 750, 6751-19 White fine A.: 3.98(s, 6H), 7.89(br dd, J=8.8, 1747, 1735, 1640, crystal 4.8Hz, 2H), 8.63(ddd, J=8.0, 2.0, 1612, 1542, 1468, hygroscopic 1.8Hz, 2H), 9.03(br d, J=4.8Hz, 1457, 1438, 1300, 2H), 9.27(br s, 2H) 1135, 1112, 956, 907, 883, 832, 740, 692, 6711-20 Light- A.: 1.36(t, J=7.0Hz, 6H), 4.41(q, 1735, 1640, 1610, yellow oil J=7.0Hz, 4H), 7.85(br dd, J=8.0, 1470, 1375, 1300, 4.8Hz, 2H), 8.59(ddd, J=8.0, 2.0, 1136, 1112, 1018, 1.8Hz, 2H), 8.98(br d, J=4.8Hz, 897, 868, 832, 740, 2H), 9.21(br s, 2H) 690, 6711-21 Light- A.: 1.38(t, J=7.0Hz, 6H), 4.44(q, 1735, 1605, 1510, yellow fine J=7.0Hz, 4H), 8.22(dd, J=4.8, 1319, 1296, 1235, 874, crystal 1.6Hz, 4H), 9.05(br d, J=4.8Hz, 4H) 859, 846, 775, 6841-22 Light-yellow A.: 3.88(s, 6H), 7.59(br s, 2H), 7.65 1580, 1548, 1440, powder (br s, 2H), 8.93(br s, 2H) 1280, 1084, 890, 820, hygroscopic 750, 6551-23 White fine A.: 1.51(t, J=7.2Hz, 6H), 4.18(q, 1581, 1552, 1453, crystal, J=7.2Hz, 4H), 7.13(br s, 2H), 7.33 1298, 1094, 896, 824, hygroscopic (br s, 2H), 8.36(br s, 2H) 758, 6551-24 White B.: 0.8-1.2(m, 6H), 1.2-1.7(m, 12H), 1568, 1550, 1463, powder, 1.83(m, 4H), 4.16(t, J=7.4Hz, 4H), 1287, 1089, 890, 840, hygroscopic 7.11(br s, 2H), 7.35(br s, 2H), 8.55 760 (br s, 2H)1-25 Light-yellow B.: 0.7-1.1(m, 6H), 1.1-1.6(m, 28H), 1578, 1551, 1468, powder, 1.87(m, 4H), 4.27(t, J=7.2Hz, 4H), 1315, 1290, 1095, 890, hygroscopic 7.17(br s, 2H), 7.46(br s, 2H), 9.14 840, 805, 763 (br s, 2H)1-26 White B.: 5.50(s, 4H), 7.16(br s, 2H), 7.42(br 1577, 1548, 1460, powder, s, 12H), 9.44(br s, 2H) 1280, 1087, 890, 840, hygroscopic 825, 780, 760, 7101-27 White fine B.: 2.60(s, 6H), 3.77(s, 6H), 7.52(d, 1610, 1542, 1445, powder, J=2.0Hz, 2H), 7.61(d, J=2.0Hz, 2H) 1287, 930, 900, 755, hygroscopic 6501-28 Light-brown B.: 3.96(s, 6H), 7.65(br s, 2H), 1566, 1555, 1304, powder, 9.53(br s, 2H) 1106, 910, 825, 676 hygroscopic1-29 White B.: 4.03(s, 6H), 7.2-7.6(m, 6H), 7.7-8.0 1567, 1462, 1442, powder, (m, 2H), 9.04(br s, 2H) 1154, 1135, 891, 865, hygroscopic 850, 820, 778, 7491-30 White B.: 5.68(s, 4H), 7.37(s, 10H), 7.2-7.6 1550, 1450, 1378, 897, powder (m, 6H), 7.8-8.2(m, 2H), 9.57(br s, 845, 812, 773, 743, 2H) 717, 6971-31 White fine B.: 3.43(s, 6H), 3.65(s, 6H), 4.07(s, 1706, 1680, 1670, crystal 6H), 7.90(s, 2H) 1660, 1580, 1556, hygroscopic 1490, 1425, 980, 925, 870, 760, 7451-32 Yellow B.: 3.42(s, 6H), 3.65(s, 6H), 1705, 1680, 1670, powder 3.97(s, 6H), 7.66(s, 2H) 1660, 1576, 1554, 1488, 1440, 980, 930, 860, 759, 7451-33 Light-yellow B.: 3.42(s, 6H), 3.63(s, 6H), 1709, 1670, 1550, fine 5.61(s, 4H), 7.40(s, 10H), 1452, 1377, 1233, crystal 7.97(s, 2H) 1029, 877, 860, 761, 750, 732, 6921-34 Light-yellow B.: 3.61(s, 6H), 4.04(s, 6H), 1708, 1687, 1668, powder 5.18(s, 4H), 7.1-7.6(m, 10H), 1555, 1438, 951, 928, 7.97(s, 2H) 892, 872, 830, 759, 743, 724, 6991-35 Light- B.: 5.57(s, 4H), 6.44(dd, J=2.3, 2.2Hz, 1501, 1456, 1440, yellow oil 2H), 7.37(s, 10H), 7.53(d, J=2.3Hz, 1419, 1102, 920, 903, 2H), 7.82(d, J=2.0Hz, 2H) 779, 7081-36 Light-yellow B.: 7.35-7.90(m, 30H) 1590, 1486, 1438, powder, 1100, 1066, 1024, 996, hygroscopic 935, 724, 717, 6851-37 White fine B.: 7.29(m, 30H) 1592, 1487, 1298, crystal 1200, 1183, 1166, hygroscopic 1013, 965, 957, 935, 770, 6901-38 Colorless B.: 3.78(d, J=11.2Hz, 18H) 1452, 1240, 1192, oil 1045, 952, 855, 750, 6951-39 Light B.: 1.35(t, J=6.7Hz, 18H), 1484, 1450, 1400, yellow oil 4.14(dq, J=7.8, 6.7Hz, 12H) 1375, 1295, 1230, 1172, 1005, 1035, 985, 830, 8051-40 Light yellow B.: 4.25(s, 3H), 7.4-7.8(m, 3H), 1618, 1601, 1565, powder, 7.8-8.1(m, 1H), 10.0(s, 1H) 1461, 1449, 1348, hygroscopic 1272, 1158, 1138, 1106, 870, 854, 758, 687, 6551-41 Light yellow A.: 7.91(ddd, J=7.2, 5.0, 1.5Hz, 2H), 1625, 1605, 1590, fine 8.44(ddd, J=8.0, 7.2, 1.7Hz, 2H), 1535, 1439, 1290, crystal, 8.75(br d, J=8.0Hz, 2H), 8.94(br 1180, 920, 890, 862, hygroscopic d, J=5.0Hz, 2H) 780, 7581-42 White A.: 7.94(ddd, J=7.3, 5.0, 1.2Hz), 8.35 1625, 1608, 1587, powder (ddd, J=7.8, 7.3, 1.6Hz, 2H), 1532, 1460, 1438, 8.66(br d, J=7.8Hz, 2H), 8.97(br d, 1181, 923, 890, 865, J=5.0Hz, 2H) 7621-43 White fine A.: 2.63(s, 6H), 7.82(br d, J=5.4Hz, 1625, 1604, 1509, crystal 2H), 8.67(br s, 2H), 8.82(d, 1435, 1296, 1222, J=5.4Hz, 2H) 1120, 858, 826, 6641-44 Yellow fine A.: 7.62-8.41(m, 8H), 8.70(d, J=8.8Hz, 1635, 1604, 1540, crystal 2H), 8.89(d, J=8.8Hz, 2H) 1511, 1385, 1218, 934, 889, 872, 830, 7441-45 White A.: 8.28(dd, J=8.0, 4.8Hz, 2H), 1620, 1598, 1548, powder 8.40(s, 2H), 9.16(dd, J=8.0, 1.6Hz, 1470, 950, 885, 876, 2H), 9.37(dd, J=4.8, 1.6Hz, 2H) 849, 716, 6961-46 Light yellow A.: 3.44(s, 3H), 8.10-8.35(m, 4H), 1640, 1610, 1537, greasy oil 8.64-8.95(m, 2H), 9.09(dd, J=6.2, 1490, 912, 864, 745, 1.2Hz, 4H) 6731-47 Light A.: 1.13(t, J=7.0Hz, 3H), 3.72(q, 1642, 1609, 1539, yellow J=7.0Hz, 2H), 8.00-8.26(m, 4H), 1490, 910, 870, 747, greasy oil 8.53-8.85(m, 2H), 8.99(dd, J=6.0, 677 1.2Hz, 4H)1-48 Brown A.: 3.76(s, 3H), 4.73(br s, 2H), 6.90 1640, 1616, 1531, greasy oil (d, J=8.6Hz, 2H), 7.31(d, J=8.6Hz, 1520, 1490, 1252, 2H), 7.96-8.21(m, 4H), 8.48-8.79 1180, 1031, 908, 850, (m, 2H), 8.96(dd, J=6.4, 1.2Hz, 820, 748, 675 4H)1-49 Light brown A.: 0.7-1.1(m, 3H), 1.1-1.7(m, 12H), 1639, 1614, 1602, greasy oil 3.79(m, 2H), 7.94-8.20(m, 4H), 1531, 1482, 1058, 8.47-8.79(m, 2H), 8.95(dd, J=6.2, 1050, 907, 748, 677 1.2Hz)1-50 Yellow A.: 4.91(br s, 2H), 7.43(m, 5H), 1640, 1615, 1606, greasy oil 8.00-8.25(m, 4H), 8.53-8.84(m, 2H), 1540, 1532, 1491, 9.03(br d, J=5.2Hz, 4H) 908, 747, 6751-51 Light A.: 3.99(s, 6H), 8.13(dd, J=4.4, 1.6Hz, 1734, 1610, 1514, yellow fine 4H), 9.03(br d, J=4.4Hz, 4H) 1430, 1299, 1121, crystal 868, 849, 830, 754, 6921-52 Light brown A.: 7.2-7.7(m, 10H), 8.21(dd, J=4.4, 1750, 1599, 1488, fine crystal 1.6Hz, 4H), 9.00(br dd, J=4.4, 1281, 1272, 1191, 1.6Hz, 4H) 914, 845, 749, 696, 6812-1 Red powder B.: 8.37(br dd, J=7.6, 6.4Hz, 4H), 1637, 1600, 1532, 8.55-8.86(m, 2H), 9.27(dd, J=6.4 1481, 1324, 1195, 1.6Hz, 4H) 1045, 902, 873, 850, 740, 6752-2 Yellow B.: 3.51(s, 6H), 7.94(br dd, J= 8.0, 1633, 1618, 1558, powder 5.6Hz, 2H), 8.44(br d, J=8.0Hz, 1475, 1390, 1268, 2H), 8.76(br d, 5.6Hz, 2H), 8.81 1185, 1121, 888, 822, (br s, 2H) 783, 6732-3 Yellow B.: 2.45(s, 12H), 8.23(br s, 2H), 1631, 1558, 1470, powder 8.60(br s, 4H) 1385, 1328, 1274, 1264, 920, 846, 817, 721, 6702-4 Yellow B.: 7.53-7.70(m, 6H), 7.82-8.03(m, 4H), 1610, 1548, 1500, powder, 8.16(m, 2H), 8.90-9.08(m, 4H), 1471, 1441, 1347, hygroscopic 9.32(d, J=1.6Hz, 2H) 1265, 1115, 918, 788, 737, 684, 6532-5 Yellow B.: 7.56-7.72(m, 6H), 7.88-8.11(m, 4H), 1636, 1593, 1486, powder 8.42(m, 4H), 8.98(m, 4H) 1290, 1212, 1066, 1007, 812, 756, 715, 6822-6 Yellow B.: 7.86(m, 2H), 8.23(m, 2H), 1550, 1477, 1280, powder, 8.69(m, 2H), 8.94(m, 2H) 1245, 1108, 917, 830, hygroscopic 801, 766, 6602-7 Yellow fine B.: 7.68(ddd, J=8.0, 5.2, 0.8Hz, 2H), 2256, 1639, 1605, crystal 8.39(ddd, J=8.0, 2.0, 1.6Hz, 2H), 1548, 1463, 1187, 8.88(dd, J=5.2, 2.0Hz, 2H), 1118, 898, 801, 777, 9.06(dd, J=1.6, 0.8Hz, 2H) 6702-8 Orange B.: 8.11(dd, J=5.3, 1.1Hz, 4H), 2250, 1642, 1608, powder, 8.98(br d, J=5.3Hz, 4H) 1507, 1362, 1250, hygroscopic 1228, 1215, 1007, 901, 8022-9 Orange B.: 3.94(s, 6H), 7.96(br dd, J=7.4, 1745, 1640, 1604, gum, 4.2Hz, 2H), 8.71(br d, J=7.4Hz, 1541, 1464, 1434, hygroscopic 2H), 9.01(br d, J=4.2Hz, 2H), 1298, 1193, 1135, 9.22(br s, 2H) 1114, 954, 859, 826, 734, 690, 6702-10 Yellow B.: 7.88-8.80(m, 12H), 9.96(br s, 2H) 1642, 1611, 1578, powder 1540, 1488, 1392, 1371, 932, 795, 759, 7362-11 Yellow B.: 3.89(br s, 6H), 7.64-7.71(m, 4H), 1585, 1554, 1438, powder, 9.14(br s, 2H) 1282, 1085, 914, 848, hygroscopic 810, 7572-12 Yellow B.: 3.21(s, 6H), 3.40(s, 6H), 1715, 1680, 1650, powder, 3.88(s, 6H), 8.03(br s, 2H) 1578, 1552, 1440, 970, hygroscopic 878, 795, 758, 743, 7252-13 Yellow B.: 7.91(ddd, J=7.2, 5.2, 1.4Hz, 2H), 1614, 1601, 1528, powder 8.42(ddd, J=7.6, 7.2, 1.6Hz, 2H), 1445, 1290, 950, 934, hygroscopic 8.74(br d, J=7.6Hz, 2H), 761 8.90(br d, J=5.2Hz, 2H)2-14 Brown B.: 7.83-8.95(m, 2H), 8.33-8.61(m, 2H), 1603, 1586, 1532, powder 8.82(br d, J=7.0Hz, 2H), 1446, 1433, 1314, 9.02(br d, J=5.0Hz, 2H) 1174, 1018, 923, 7593-1 Light B.: 1.13(d, J=6.0Hz, 6H), 1.40(d, 1387, 1264, 1108, yellow J=6.4Hz, 6H), 3.52-4.23(m, 4H) 1012, 891, 859, 782, oil 6683-2 Yellow B.: 1.49(s, 12H), 3.44(s, 4H) 1392, 1377, 1270, 1148, oil 1108, 972, 920, 869, 770, 6643-3 Yellow B.: 0.71-1.08(m, 6H), 1.2-2.0(m, 4H), 1262, 1112, 857, 685, oil 3.4-3.6(m, 4H), 3.6-4.1(m, 2H) 6643-4 Light B.: 0.87(br t, J=5.0Hz, 6H), 1467, 1382, 1268, yellow 1.3(br s, 20H), 3.45-3.78(m, 4H), 1110, 1088, 1059, 920, oil 3.8-4.2(m, 2H) 856, 6663-5 Yellow B.: 3.98(d, J=6.6Hz, 4H), 5.13(t, 1498, 1457, 1067, oil, viscous J=6.6Hz, 2H), 7.46(m, 10H) 1030, 973, 937, 914, 847, 760, 722, 695, 660 (oil film)3-6 Light yellow B.: 1.2-2.3(m, 16H), 3.4-4.5(m, 4H) 1453, 1130, 1080, oil, viscous 1012, 961, 925, 900, 869, 848, 736, 660 (oil film)3-7 Yellow oil, B.: 0.89-2.16(m, 16H), 3.7-4.3(m, 4H) 1352, 1149, 1078, viscous 1013, 998, 917, 902, 856, 692, 6583-8 Colorless A.: 1.06(br t, J=3.3Hz, 3H), 1465, 1385, 1354, oil 1.5-2.1(m, 2H), 3.8-5.1(m, 3H) 1334, 1223, 1108, 1081, 1059, 1030, 1012, 984, 931, 848, 775, 715, 664, (oil film)3-9 Light yellow A.: 0.91(t, J=7.6Hz, 6H), 1.82(J=7.6Hz, 1465, 1387, 1063, 993, oil, viscous 4H), 3.61(br d, J=12.0Hz, 2H), 936, 922, 900 4.77(br d, J=12.0Hz, 2H)3-10 Light yellow B.: 7.4-8.1(m, 10H), 8.05(dd, J=4.4, 1678, 1601, 1330, powder 1.8Hz, 4H), 9.04(dd, J=4.4, 1316, 1285, 948, 932, 1.6Hz, 4H) 842, 786, 742, 720, 6933-11 White B.: 6.96(br d, J=7.3Hz, 4H), 1660, 1600, 1535, powder, 8.18(br d, J=7.3Hz, 4H), 1197, 996, 850, 806 hygroscopic 8.36(br s, 2H), 9.58(br, s, 4H)3-12 White B.: 3.22(s, 12H), 7.02(m, 4H), 1652, 1565, 1217, 999, powder 8.26(m, 4H) 944, 913, 899, 882, 853, 8073-13 Light yellow B.: 6.52-6.82(m, 4H), 7.65-7.96(m, 4H), 1640, 1543, 1372, powder, 13.66(s, 2H) 1338, 1165, 1101, 994, hygroscopic 860, 820, 772, 7253-14 White fine B.: 7.32(m, 4H), 8.52(m, 4H), 1647, 1614, 1535, crystal 11.3-12.8(br s, 4H) 1517, 1390, 1378, 1327, 1225, 1196, 850, 8163-15 White fine B.: 4.13(s, 6H), 7.61(m, 4H), 1640, 1602, 1532, crystal 8.83(m, 4H) 1515, 1325, 1307, 1198, 1013, 993, 8303-18 Yellowish B.: 4.81-4.93(m, 4H), 5.19-5.59(m, 4H), 1738, 1645, 1608, brown oil, 5.79-6.41(m, 2H), 8.10(dd, J=4.8, 1323, 1285, 1237, greasy 1.4Hz, 4H), 8.95(br d, J=4.8Hz, 4H) 1133, 939, 845, 756, 6833-19 Light brown B.: 8.10(dd, J=9.0, 4.6Hz, 2H), 8.52(d, 1658, 1610, 1556, powder J=6.2Hz, 2H), 9.08(d, J=6.2Hz, 2H), 1496, 1444, 1331, 9.10(dd, J=9.0, 1.6Hz, 2H), 9.56(dd, 1292, 1277, 839, 819 J=4.6, 1.6Hz, 2H), 10.11(s, 2H)3-20 Yellow B.: 7.87(dd, J=8.6, 4.2Hz, 2H), 8.02(dd, 1639, 1614, 1598, fine crystal J=8.8, 7.8Hz, 2H), 8.47(br d, 1535, 1371, 1346, J=7.8Hz, 2H), 8.50(br d, J=8.8Hz, 1305, 1238, 1221 2H), 8.93(br d, J=8.6Hz, 2H), 1199, 1148, 1000, 9.14(dd, J=4.2, 1.6Hz, 2H) 878, 858, 805, 729, 687, 6623-21 Light B.: 7.85(dd, J=8.4, 4.4Hz, 2H), 8.28 1647, 1608, 1557, yellow (d, J=9.2Hz, 2H), 8.55(dd, J=9.2, 1540, 1486, 1386, powder 2.4Hz, 2H), 8.89(br d, J=8.4Hz, 1357, 1305, 1128, 907, 2H), 9.13-9.28(m, 4H) 901, 858, 809, 766, 6593-22 Orange B.: 7.72-7.98(m, 4H), 8.33-8.47(m, 4H), 1641, 1598, 1535, powder 8.69(dd, J=8.2, 1.8Hz, 2H), 9.15 1352, 1277, 1268, (dd, J=4.2, 1.8Hz, 2H) 1190, 877, 842, 832, 788, 7593-23 Light B.: 8.04(dd, J=8.0, 7.6Hz, 2H), 8.56 1657, 1621, 1582, yellow (br d, J=6.4Hz, 2H), 8.71-8.90(m, 1532, 1487, 1341, powder 6H), 9.81(br s, 2H) 1267, 880, 859, 817, 793, 6683-24 White B.: 3.40(s, 6H), 3.62(s, 6H), 5.4-5.7 1725, 1674, 1570, powder (br s, 2H), 8.43(s, 2H) 1446, 1195, 982, 7413-25 Yellow A.: 4.10(s, 6H), 8.36(dd, J=5.2, 1.6Hz, 1739, 1440, 1363, gum 2H), 9.17(br s, 2H), 9.20(br d, 1300, 1267, 1250, J=5.2Hz, 2H) 1129, 962, 758, 721, 6953-26 Yellow A.: 1.51(t, J=7.2Hz, 6H), 4.58(d, 1735, 1377, 1368, gum J=7.2Hz, 4H), 8.29(dd, J=5.2, 1293, 1259, 1141, 1.6Hz, 2H), 9.19(br s, 2H), 1112, 1021, 759, 689 9.29(br d, J=5.2Hz, 2H)3-28 Yellow oil, B.: 3.34(br s, 2H), 6.95-7.37(m, 4H), 1662, 1620, 1548, viscous 8.01-8.31(m, 4H), 8.5(br s, 4H) 1478, 1380, 1326, 1241, 1166, 995, 881, 763 (oil film)3-29 White fine B.: 7.08(d, J=9Hz, 2H), 7.61(br s, 2H), 1700-1652, 1631, 1597, crystal 8.22(br s, 2H), 8.31(dd, J=9 and 1554, 1485, 1426, 2Hz, 2H), 8.54(d, J=2Hz, 2H), 1400, 1356, 1255, 8.6(br, 4H), 1164, 1143, 1053, 857, [FT-NMR (400MHz)] 834, 771, 7393-30 White B.: 6.48(d, J=10.2Hz, 2H), 8.20(dd, 1675, 1600, 1639, needle J=10.2, 3.2Hz, 2H), 8.48(br s, 1571, 1510, 1434, crystal 2H), 8.72(d, J=3.2Hz, 2H) 1351, 1254, 1123, 917, 888, 835, 759, 716, (nujol)3-31 White fine B.: 7.25(d, J=7Hz, 2H), 7.76(dd, J=8 and 1646, 1620, 1591, crystal 7Hz, 2H), 8.03(dd, J=8 and 7Hz, 1500, 1412, 1350, 2H), 8.13(d, J=8Hz, 2H), 8.32(d, 1306, 876, 829, 781, J=8Hz, 2H), 8.80(d, J=7Hz, 2H), 759 [FT-NMR (400MHz)]3-32 Yellow B.: 7.59(d, J=5Hz, 2H), 7.76-7.79(m, 4H), 1632, 1600, 1558, powder 8.05(dd, J=8 and 5Hz, 2H), 9.11 1420, 1395, 1302, (d, J= 5Hz, 2H), 9.12(d, J=8Hz, 2H), 1098, 911, 887, 835, 12.15(br s, 2H), 820, 797 [FT-NMR (400MHz)]3-33 White B.: 8.00(dd, J=8 and 7Hz, 2H), 8.20(dd, 1635, 1610, 1578, fine J=8 and 7Hz, 2H), 8.24(d, J=8Hz, 1544, 1492, 1381, crystal 2H), 8.47(d, J=8Hz, 2H), 8.97(s, 2H), 1364, 1262, 1239, 9.72(s, 2H), 1208, 897 [FT-NMR (400MHz)]4-1 White B.: 3.3-3.9(m, 8H), 7.17(m, 2H), 7.90 3342, 1707, 1562, crystal (dd, J=8.8, 5.6Hz, 2H), 8.37(ddd, 1544, 1527, 1452, J=8.8, 2.5, 1.4Hz, 2H), 8.48 1355, 1233, 878, 807, (bd d, J=5.6Hz, 2H), 9.08(br d, 761, 727, 676 J=2.5Hz, 2H), 10.47(br s, 2H), 10.7-11.5(br, 2H)4-2 White B.: 3.01(s, 6H), 6.81(br t, J=6.5Hz, 2H), 1675, 1626, 1578, crystal 7.08(br d, J=8.2Hz, 2H), 7.70-7.97 1493, 1456, 1405, hygroscopic (m, 4H), 8.5-10.0(br, 4H) 1382, 1284, 1236, 1164, 1071, 860, 764, 685__________________________________________________________________________
The compounds of this invention are expected to serve as an antineoplastic agent as described below. Various known methods can be used for the preparation of medicaments with these compounds and their administration. As the way of administration, injection, peroral administration, rectal application, etc., are possible. As for the form of medicaments, they may take the form of injection, powder, granules, tablet, suppository, etc.
In preparation of medicaments, various types of carriers and adjuvants ordinarily used in pharmaceutical preparations, such as stabilizer, aseptic, anodyne, emulsifier, etc., may be used as occasion demands so long as they give no adverse effect to the selenium compound used as base material.
The content of the selenium compound in a piece of medicament may vary over a wide range according to the form of the medicament and other factors, but usually the selenium compound is contained in a ratio of 0.01 to 100%, preferably 0.1 to 70% (by weight), the rest of the medicament comprising the carrier and other adjuvants.
The recommended dosage per day of the compounds of this invention, as determined from the basic potency experiments, is 0.01 to 10 mg/kg, preferably 0.1 to 2 mg/kg in the case of peroal administration, 0.01 to 5 mg/kg, preferably 0.1 to 1 mg/kg in the case of injection, and 0.01 to 10 mg/kg, preferably 0.1 to 2 mg/kg in the case of suppository.
The antineoplastic and antimutagenic activities of the compounds of this invention, as determined experimentally, are shown below.
Test Example 1
Antineoplastic activity against Enrlich carcinoma
Testing method:
Approximately 10.sup.6 cells/0.2 ml of Enrlich carcinoma were inoculated into the abdominal cavity of each of the 5-week-old ICR mice (male) used for the test, and the test compounds were administered intraperitoneally to the mice of the treated group once a day for a period of 7 days, starting from the day after said inoculation. The mice of the control group was administered with a saline solution in the same way. Observation of the animals of both groups was continued for 60 days after the administration, and the life prolongation rate (T/C%, T/C.times.100) was determined from the average duration (days) of life of the mice of the treated group (T) and that of the mice of the control group (C). Also, the 50% lethal dose (LD.sub.50) was determined from the number of the mice in the treated group which died due to the toxicity of the compound administered.
The results are shown in Table 3.
TABLE 3______________________________________ LD.sub.50Compound Life prolongation rate (T/C %) (mg/kg/No. 2.0* 4.0* 8.0* 16.0* day .times. 7)______________________________________1-1 165 173 181 130 Note 1) 8-161-2 176 169 194 75 8-161-3 200 222 180 83 8-161-4 208 232 168 108 8-161-5 207 174 249 59 (Note 1) 8-161-6 173 209 244 103 (Note 1) 8-161-7 175 222 256 201 (Note 1) 8-161-8 183 220 171 157 (Note 1) 8-161-9 171 204 229 228 >161-10 251 192 203 199 >161-11 166 180 230 221 >161-12 194 219 201 140 (Note 2) 8-161-13 142 172 158 84 (Note 1) 8-161-14 163 179 202 147 (Note 1) 8-161-15 154 174 191 162 (Note 1) 8-161-22 214 208 233 118 (Note 3) 8-161-23 219 181 203 226 (Note 2) 8-161-24 168 185 199 181 >161-25 163 141 179 149 >161-26 119 227 153 106 (Note 1) 8-161-27 168 234 224 88 (Note 3) 8-161-28 138 217 215 264 (Note 1) >161-29 147 205 164 106 (Note 1) 8-161-30 258 220 219 198 >161-31 192 182 281 189 >161-32 168 176 208 195 >161-33 138 213 214 205 >161-34 122 159 187 190 >161-35 135 195 225 149 8-161-36 155 186 225 197 >161-37 106 123 214 127 >161-38 181 180 160 126 (Note 1) 8-161-39 191 227 240 135 161-40 214 230 243 123 (Note 2) 8-161-41 230 237 312 60 8-161-42 163 176 206 151 (Note 4) 8-161-43 247 220 238 52 (Note 3) 8-161-44 183 268 253 123 (Note 1) 8-161-45 184 170 203 84 (Note 1) 8-161-46 229 248 188 59 (Note 3) 8-161-47 238 241 241 24 (Note 3) 8-161-17 208 212 339 166 (Note 1) 8-162-1 185 171 222 146 >162-2 142** 199** 193** 95** 8-162-4 152** 227** 235** 173** >162-5 142** 214** 247** 159** >162-6 138** 163** 233** 97** 162-7 201** 243** 214** 67** 8-162-8 199** 187** 191** 138** 8-162-9 214 221 224 151 >162-10 169 215 175 175 >162-11 112 132 186 218 >162-12 122 123 140 187 >162-13 152 180 185 97 (Note 5) >162-14 158 127 187 165 >16 LD.sub.50Compound Life prolongation rate (T/C %) (mg/kg/No. 1.0* 2.0* 4.0* 8.0* 16.0* day .times. 7)______________________________________3-1 -- 177 179 193 90 8-163-2 -- 178 232 207 63 (Note 2) 8-163-3 172 205 230 212 -- >83-4 -- 156 208 180 53 (Note 1) 8-163-5 -- 154 194 223 167 (Note 5) >163-6 -- 210 216 253 95 (Note 3) 8-163-7 -- 143 148 201 119 (Note 1) 8-163-8 208 250 194 212 -- >83-9 -- 152 204 223 194 >163-10 -- 192 238 229 109 8-163-11 -- 160 252 279 240 >163-12 -- 169 183 232 190 >163-13 -- 138 160 171 165 >163-14 -- 130 170 243 242 >163-15 -- 111 153 192 214 >16______________________________________ *Dose (mg/kg/day), **Solvent used: DMSO (Note 1) Administered for 4 days. (Note 2) Administered for 2 days. (Note 3) Administered for 3 days. (Note 4) Administered for 5 days. (Note 5) Administered for 6 days.
Test Example 2
Antimutagenic activity
Testing method:
The antimutagenic activity was examined according to the Ames method by using Salmonella typhimurium TA-98 as test bacterium and Benzo(.alpha.)pyrene (B(.alpha.)P) as (TA-98) mutagen.
To a solution of 5 .mu.g of B(.alpha.)P and a proper amount of a compound of this invention in 0.1 ml of DMSO were added 0.5 ml of S-9 mix and 0.1 ml of a TA-98 suspension, and the mixture was subjected to preincubation at 37.degree. C. for 20 minutes.
This preincubated mixture was further added with 2 ml of soft agar, and after sufficient mixing, the mixture was uniformly spread on a gluclose minimum agar medium plate and incubated at 37.degree. C. for 48 hours. Thereafter, the number of the colonies produced by reverse mutation was counted.
The number of the colonies existing in the medium containing neither B(.alpha.)P nor the compound of this invention was given as background.
The antimutagenic activity was determined as a mutation inhibition rate from the following formula: ##EQU1##
The results are shown in Table 4.
TABLE 4__________________________________________________________________________Inhibitory activity of the compound of thisinvention against mutagenic action of benzpyreneCom- Back- Amount of compound used (.mu.g/plate)pound ground 0 0.5 1 5 10 50 100 500__________________________________________________________________________1-41 Number of 33 298 238 234 209 149 119 96 16 colonies (Inhibition -- (0) (22.6) (24.2) (33.6) (56.2) (67.5) (76.2) (100) rate)__________________________________________________________________________
The compounds of this invention have a high antineoplastic activity against the malignant tumors such as ascitic cancer, liver cancer, etc. They also have an antimutagenic activity, and their effective use as an antineoplastic agent is expected.
The preparation process of the compounds of this invention will be described concretely below by showing the examples thereof.

EXAMPLE 1-1
Synthesis of Compound No. 1-22
386 mg (1.52 mmol) of a selenium oxychloride-1,4-dioxane complex was weighted and dissolved in 4 ml of anhydrous methylene chloride. To this solution was added dropwise at room temperature 4.2 ml of a solution prepared by diluting 250 mg (3.04 mmol) of N-methylimidazole with anhydrous methylene chloride. The resulting pale-yellow solution was allowed to stand for about 30 minutes and then concentrated and evaporated to dryness under reduced pressure to obtain 503 mg of yellow fine crystals (yield: 100.0%).
Compound No.s 1-2 to 1-31, 1-33 to 1-39, 1-51 and 1-52 were synthesized in the same way as described above by using the corresponding compounds in place of N-methylimidazole.
Also, compound Nos. 1-1 and 1-32 were synthesized by using a selenium oxybromide-1,4-dioxane (1:1) complex in place of the selenium oxychloride-1,4-dioxane (1:1) complex and by reacting it with the corresponding compounds.
The properties of these compounds are shown in Table 2.
EXAMPLE 1-2
Synthesize of compound No. 1-41
419 mg (1.65 mmol) of a selenium oxychloride-1,4-dioxane (1:1) complex was dissolved in 2 ml of anhydrous methylene chloride. To this solution, 2 ml of an anhydrous methylene chloride solution of 258 mg (1.65 mmol) of 2,2'-dipyridyl was added dropwise gradually under shaking at room temperature. After the dropwise addition, the mixture was left standing for one hour. Thereafter, the supernatant was removed, leaving the produced fine crystal powder. The reside was washed with a small quantity of anhydrous methylene chloride and then dried in vacuo to obtain 508 mg of slightly yellowish white fine crystal powder (yield: 95.6%).
Compound Nos. 1-40 and 1-43 to 1-45 were synthesized in the similar way by using the corresponding compounds in place of 2,2'-dipyridyl.
Compound No. 1-42 was synthesized by using a selenium oxybromide-dioxane (1:1) complex as starting material and reacting it with 2,2'-dipyridyl.
The properties of these compounds are shown in Table 2.
EXAMPLE 1-3
Synthesis of compound No. 1-47
310 mg (1.22 mmol) of selenium oxychloride-1,4-dioxane (1:1) complex was dissolved in 3 ml of anhydrous methylene chloride, and to this solution was added dropwise a 1.6 ml of anhydrous methylene chloride solution of 193 mg (2.44 mmol) of anhydrous pyridine under shaking at room temperature. 15 minutes thereafter, a 1 ml of anhydrous methylene chloride solution of 118 mg (2.56 mmol) of anhydrous ethyl alcohol was further added dropwise thereto under shaking. After the dropwise addition ended, the mixture was left standing for 30 minutes and then the solvent was removed gradually under reduced pressure to obtain 453 mg of white wet powder (yield: 100.3%).
Compound Nos. 1-46 and 1-48 to 1-50 were synthesized by the same reaction procedure as above but using the corresponding alcohols in place of ethanol.
The properties of these compounds are shown in Table 2.
EXAMPLE 2-1
Synthesis of compound No. 2-13 (C4SDp)
250 mg (1.23 mmol) of tetrachloroselenium was weighed and dissolved in 10 ml of anhydrous tetrahydrofuran. To the resulting light-yellow solution was added dropwise 3.8 ml of an anhydrous tetrahydrofuran solution of 177 mg (1.13 mmol) of 2,2'-dipyridyl under ice-water cooling. Thereafter, the mixture was left standing under ice-water cooling for one hour. After the end of the reaction, the supernatant was removed, leaving the produced yellow crystal powder. The residue was washed with a small quantity of anhydrous tetrahydrofuran and then dried in vacuo to obtain 380 mg of yellow fine crystal powder (yield: 89.1%).
EXAMPLE 2-2
Synthesis of compound No. 2-5 (C4S4Ph)
255 mg (1.16 mmol) of tetrachloroselenium was weighed and dissolved in 4 ml of anhydrous tetrahydrofuran to form a light-yellow solution. To this solution was added dropwise 4.6 ml of an anhydrous tetrahydrofuran solution of 358 mg (2.31 mmol) of 4-phenylpyridine at room temperature. Thereafter, the mixture was allowed to stand at room temperature for 2 hour. After the end of the reaction, the reaction mixture was concentrated and evaporated to dryness under reduced pressure to obtain 615 mg of yellow fine crystal powder (yield: 100.2%).
Compound Nos. 2-1 to 2-12 were synthesized by the similar reaction procedure as above.
EXAMPLE 2-3
Synthesis of compound No. 2-14 (B4SDp)
448 mg (1.12 mmol) of tetrabromoselenium was weighed and dissolved in 10 ml of anhydrous diethyl ether. To this solution was added dropwise 5 ml of an anhydrous diethyl ether solution of 175 mg (1.12 mmol) of 2,2'-dipyridyl at room temperature. Thereafter, the mixture was allowed to stand at room temperature for 2 hours. After the end of the reaction, the supernatant was removed, leaving the produced light-brown powder. The latter was washed with a small quantity of anhydrous diethyl ether and then dried in vacuo to obtain 574 mg of light-brown powder (yield: 92.1%).
EXAMPLE 3-1
Synthesis of compound No. 3-6 (SOCH)
370 mg (1.457 mmol) of selenium oxychloride-1,4-dioxane (1:1) complex was dissolved in 11 ml of anhydrous methylene chloride, and to this solution was slowly added dropwise a 3 ml of anhydrous methylene chloride solution of 286 mg (2.91 mmol) of cyclohexene oxide under shaking at room temperature. 3 hours thereafter, the mixed solution was concentrated under reduced pressure and then the solvent was removed completely to obtain 513 mg of a slightly yellowish viscous oil of bis-(2-chlorocyclohexyl)selenite (SOCH) (yield: 97.2%).
In the same way, compound Nos. 3-1 to 3-7 were synthesized by using the corresponding oxides shown below.
______________________________________ Obtained compoundOxide No.______________________________________2,3-epoxybutane 3-12-methyl-1,2-epoxypropane 3-21,2-epoxybutane 3-31,2-epoxyoctane 3-4Styrene oxide 3-52,3-epoxynorbornane 3-7______________________________________
EXAMPLE 3-2
Synthesis of compound No. 3-8 (SOEEC)
3.33 g (0.0131 mmol) of selenium oxychloride-1,4-dioxane (1:1) complex was dissolved in 33 ml of anhydrous 1,4-dioxane, and to this solution was added 2.83 g (0.0288 mol) of anhydrous potassium acetate, followed by stirring at room temperature. 24 hours later, 1.125 g (0.0125 mol) of 1,2-butanediol was added and the mixture was further stirred for 2 days. Thereafter, the mixed solution was subjected to suction filtration and the byproduced potassium chloride was removed. The solution portion was concentrated and then distilled under reduced pressure to obtain 1.657 g of 1,2-butanediolselenite (SOEEC) as a colorless oil having a boiling point of 110.5.degree.-112.0.degree. C. (6 mmHg) (yield: 72.5%).
EXAMPLE 3-3
Synthesis of compound No. 3-9 (SOEPC)
828 mg (4.99 mmol) of selenium oxychloride was dissolved in 25 ml of anhydrous diethyl ether, and to this solution was added 1,078 mg (10.98 mmol) of anhydrous potassium acetate and stirred at room temperature. 20 hours, later, 660 mg (4.99 mmol) of 2,2-diethyl-1,3-propanediol was added and the mixture was further stirred for 24 hours. Thereafter, the mixture was subjected to suction filtration and the byproduced potassium chloride was removed. The resulting transparent solution was concentrated under reduced pressure and then the solvent was removed perfectly to obtain 1,019 mg of 2,2-diethyl-1,3-propanediol as a slightly yellowish viscous oil (yield: 90.7%).
EXAMPLE 3-4
Synthesis of compound No. 3-14 (SC4Hy.aq)
1.6 ml of methanol containing 1.5-2% of water and 16 ml of methylene chloride were added to 306 mg (3.22 mmol) of 4-hydroxypyridine and the latter was dissolved. To this solution was added dropwise a 4 ml anhydrous methylene chloride solution of 409 mg (1.61 mmol) of selenium oxychloride-1,4-dioxane complex under shaking over a period of 6 minutes. 2 Hours thereafter, the resulting transparent solution was concentrated under reduced pressure to obtain 633 mg of white fine crystals (yield: 107.8%). This product was washed several times with a small quantity of anhydrous methylene chloride and dried in vacuo to obtain 428 mg of a selenium oxychloride-4-hydroxypyridine (1:2) complex mono hydrate as white fine crystals (yield: 72.9%).
Compound Nos. 3-11, 3-28, 4-1 and 4-2 were synthesized in the same way as described above by using the following compounds of A in the formula (I) in place of 4-hydroxypyridine.
______________________________________ ObtainedStarting compound compound(A in the formula (I)) No.______________________________________4-aminopyridine 3-112-aminopyridine 3-28N--(2-chloroethyl)-N'-- 4-1(3-pyridyl)urea2-(N--methylamino)pyridine 4-2______________________________________
EXAMPLE 3-5
Synthesis of compound No. 3-23 (SC5NI)
396 mg (1.56 mmol) of selenium oxychloride-1,4-dioxane complex was dissolved in 4 ml of anhydrous methylene chloride. To this solution was added dropwise at room temperature 5 ml of an anhydrous methylene chloride solution containing 544 mg (3.12 mmol) of 5-nitroisoquinoline. The resulting light-yellow solution was left standing as it was for about 60 minutes and then concentrated and evaporated to dryness under reduced pressure to obtain 809 mg of yellow fine crystals (yield: 100.6%).
Compound No.s 3-10, 3-12, 3-13, 3-15, 3-18 to 3-22, 3-24 to 3-26, and 3-29 to 3-33 were synthesized by conducting the same operations as described above but by using the following compounds of A in the formula (I) in place of 5-nitroisoquinoline.
______________________________________ ObtainedStarting compound compound(A in the formula (I)) No.______________________________________4-benzoylpyridine 3-104-dimethylaminopyridine 3-122-hydroxypyridine 3-134-methoxypyridine 3-15allyl isonicotinate 3-181,6-naphthylidine 3-195-nitroquinoline 3-206-nitroquinoline 3-218-nitroquinoline 3-22Theophylline 3-242,2'-bi-(methyl isonicotinate) 3-252,2'-bi(ethyl isonicotinate) 3-266-aminonicotinamide 3-292-hydroxy-5-nitropyridine 3-204-hydroxyquinoline 3-318-hydroxyquinoline 3-324-bromoisoquinoline 3-33______________________________________

Number	Date	Country
60-254694	Nov 1985	JPX
61-107589	May 1986	JPX
61-110697	May 1986	JPX

Number	Date	Country
0095663	Dec 1983	EPX
0182317	May 1986	EPX
59-20274	Feb 1984	JPX

Selenium oxy chloride-pyridine or bipyridine complexes

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