Heterocyclic compounds and their production

Disclosed is a novel heterocyclic compound selected from the group consisting of the compounds [IV] to [VII], [IX] and [X]. The heterocyclic compound is useful for reactive materials in chemical industry. A process for producing the heterocyclic compound is also disclosed.

FIELD OF THE INVENTION 
The present invention relates to novel heterocyclic compounds and their 
production. 
BACKGROUND OF THE INVENTION 
Compounds containing an isocyanate group have widely been used in the field 
of polymer chemistry because of their excellent reactivities. 
Particularly, compounds containing both a polymeric carbon-carbon 
unsaturated group and an isocyanate group in the same molecule can be used 
for a wide variety of industrial fields because each functional group 
respectively contributes to various reactions in different reaction 
mechanism. By paying attention to such an usefulness, the present 
inventors have already provided an acylisocyanate compound represented by 
the formula: 
##STR1## 
[wherein R is a lower alkyl group] (U.S. Pat. No. 4,925,982). 
The above acylisocyanate compound [I] is generally liquid which is stable 
at a normal temperature and is easily handled. Further, it contains a 
polymeric carbon-carbon unsaturated group and an isocyanate group in a 
molecule and a carbonyl group is also present between both functional 
groups while adjoining them and, therefore, activity of the carbon-carbon 
unsaturated group as well as that of the isocyanate group are enhanced. 
Thus, it is in such a state that various addition reactions can be 
conducted. Namely, various reactions (e.g. radical polymerization, anion 
polymerization, dimerization, trimerization, polarity addition, active 
hydrogen addition, etc.) based on the part A (conjugated double bond) and 
part B (acylisocyanate group) of the following formula: 
##STR2## 
[wherein R is as defined above] can be conducted by the acylisocyanate 
compound [I]. 
Accordingly, it is expected that the acylisocyanate compound [I] is widely 
used in chemical industry as reactive materials. 
For example, the present inventors have already disclosed that a compound 
represented by the formula: 
##STR3## 
[wherein each R is the same or different and is as defined above] 
(Japanese Patent Kokai No. 60-231644 corresponding to U.S. Pat. No. 
4,935,413) and a compound represented by the formula: 
##STR4## 
[wherein R is as defined above, and Z is an organic group containing a 
tertiary amino group] (Japanese Patent Kokai No. 61-17554 corresponding 
U.S. Pat. No. 4,935,413) are useful in the fields of coatings, plastics 
and the like. 
Under these circumstances, the present inventors have found that the diene 
structure part B (acylisocyanate group) containing a hetero atom in the 
acylisocyanate compound (I) makes a cyclic addition reaction with a 
suitable dienophile to form a novel heterocyclic compound, and the above 
heterocyclic compound can further make a cyclic addition reaction with the 
suitable dienophile to form an additional novel heterocyclic compound, and 
the present invention has been completed. 
OBJECTS OF THE INVENTION 
The main object of the present invention is to provide novel heterocyclic 
compounds useful for reactive materials in chemical industry. 
This object as well as other objects and advantages of the present 
invention will become apparent to those skilled in the art from the 
following description. 
SUMMARY OF THE INVENTION 
According to the present invention, there is provided the heterocyclic 
compounds [IV] to [VII], [IX] and [X] represented by the following 
formulas: 
##STR5## 
[wherein R is as defined above; R.sup.1 is an alkyl, aryl, aralkyl, 
alkenyl or alkynyl group; each R.sup.2 is the same or different and 
respectively indicates --H, --R.sup.1, --OR.sup.1, --CONR.sub.2.sup.1, 
--CONHR.sup.1, --CHO, --COR.sup.1, --CO.sub.2 R.sup.1, --NO.sub.2 or 
halogen atom, or R.sup.1 and R.sup.2 may bond together with or without O 
or N atom to form a cyclic group; 
X is 
##STR6## 
--O--, --S--, or 
##STR7## 
two substituents --R.sup.1 on N atom is the same or different when X is 
##STR8## 
and they may bond together with or without O or N atom to form a cyclic 
group; and the above substituents R.sup.1 and R.sup.2 may be substituted], 
##STR9## 
[wherein R, R.sup.1 R.sup.2 and X are as defined above], 
##STR10## 
[wherein R, R.sup.1, R.sup.2 and X are as defined above], 
##STR11## 
[wherein R and R.sup.2 are as defined above], 
##STR12## 
[wherein --A'--B'-- is a reactive residue of A'=B' as defined below, and 
R, R.sup.1, R.sup.2 and X are as defined above], and 
##STR13## 
[wherein --A'--B'-- is a reactive residue of A'=B' as defined below, and 
R, R.sup.1, R.sup.2 and X are as defined above]. 
The present invention also provides a process for producing the hydrocyclic 
compounds [IV] to [VII], [IX] and [X].

DETAILED EXPLANATION OF THE INVENTION 
In the above formulas, R is a lower alkyl group and examples thereof 
include those having 1 to 6 carbon atoms. 
The substituent represented by R.sup.1 may be, for example, alkyl, aryl, 
aralkyl, alkenyl or alkynyl group. Examples of the alkyl group include 
those which are described as to the above substituent R, examples of the 
aryl group include phenyl group, naphthyl group, etc., examples of the 
aralkyl group include benzyl group, phenethyl group, etc., examples of the 
aryl group include allyl group, etc., and examples of the alkynyl group 
include propargyl group and the like. 
X is a substituent represented by the formula: 
##STR14## 
[wherein R.sup.1 is as defined above], --O--, --S--or 
##STR15## 
Further, when X is a group of the formula [XII], --X--R.sup.1 is 
##STR16## 
[wherein R.sup.1 is as defined above], but two substituents are the same 
or different. Further, these two substituents R.sup.1 may bond together 
with or without O or N atom to form a cyclic group. 
The above substituents R.sup.1 and R.sup.2 may be substituted with a 
suitable substituent. The suitable substituent may be, for example, 
aliphatic group, aromatic group, alicyclic group, hetero substituent and 
the like. Examples of the aliphatic group include alkyl group (e.g. 
methyl, ethyl, propyl, butyl, etc.), alkenyl group (e.g. vinyl, allyl, 
etc.), aralkyl group (e.g. benzyl, etc.), alkynyl group (e.g. ethynyl, 
propargyl, etc.) and the like. Examples of the aromatic group include aryl 
group (e.g. phenyl, naphthyl, etc.) and the like. Examples of the 
alicyclic group include cyclopropyl, cyclopentyl, cyclohexyl and the like. 
Examples of the hetero substituent include alkoxy group, halogen atom, 
acyl group, ester group, nitro group, cyano group, sulfide group, sulfone 
group, tertiary amino group, silicon and the like. 
The compounds [IV] to [VII] of the present invention can be selectively 
obtained as a mixture by reacting the compound [I] with the compound of 
the formula: 
EQU A.dbd.B [II] 
As the the compound [I], for example, there are methacryloyl isocyanate, 
acryloyl isocyanate and the like. 
As the compound [II], for example, there are vinyl ethers, enamines, vinyl 
thioethers, alkoxyalkynes, thioalkoxyalkynes, ynamines, N-substituted 
maleimides, maleic anhydride, maleic acid and esters thereof, fumaric acid 
and esters thereof, acetylenemonocarboxylic acids and esters thereof, 
acetylenedicarboxylic acids and esters thereof, phenylacetylenes, acylated 
acetylenes, (meth)acrylic acid and esters thereof, (meth)acrylonitrile, 
quinones, cyanoethylenes, isocyanates, ketenes, ketenimines, 
carbodiimides, thioketenes, sulfinylimines, ketones, isocyanides, 
carbenes, allenes, isothiocyanates, sulfines, carbon bisulfide, 
sulfondiimides, azomethine compounds, nitriles, oxiranes, nitrons, nitrile 
oxides, thiiranes and azirines, and it may be substituted or have a cyclic 
structure. 
For example, the above compound [II] may be a compound represented by the 
formula: 
##STR17## 
[wherein R, R.sup.1, R.sup.2 and X are as defined above]. 
As the compound [III], for example, there are 
1-pyrrolidino-1-phenylenamine, ethyl vinyl ether, methyl vinyl ether, 
butyl vinyl ether, isobutyl vinyl ether, 2-chloromethyl vinyl ether, 
4-vinylanisole, ketene acetal, phenylvinylz sulfide, 2-vinyl thioethyl 
acetate, 1-piperidino isobutene, 1-dimethylamino-2-nitroethylene, 
3-aminocrotonate, 1-acetyl-2-methylaminopropane, 
1-acetyl-2-anilinopropene, ethyl-.beta.-dimethylaminocronate, 
2-morpholino-2-butene, 2-morpholino-2-pentene, 
1,2-dimethoxycarbonyl-1-aziridinoethylene, 
ethyl-.beta.-dimethylaminoacrylate, 
4-(N,N-diethylamino)-4-phenyl-3-butenenitrile, N,N-dimethylvinyl amine, 
N-methyl-N-propenyl aniline, 1-chloro-N,N-dimethylpropenylaniline and the 
like. 
Further, the compound [III] may be those in which R.sup.1 and R.sup.2 as 
well as the other substituent (e.g. the other R.sup.2, etc.) bond together 
with O, N or S atom to form a cyclic group. For example, the compound 
[III] may be a compound represented by the formula: 
##STR18## 
[wherein --(CH.sub.2).sub.n -- is a methylene chain in which O, N or S 
atom may be present in a chain, which may have a substituent or have a 
fused ring structure; n is an integer of 2 to 20; and R and X are as 
defined above]. 
In the above compound [XIII], a cyclic methylene chain may have a 
substituent, or fused with the other ring. As the above substituent, for 
example, there are alkyl group (e.g. methyl ethyl, etc.), aryl group (e.g. 
phenyl group, etc.) and the like. Further, as the other ring, for example, 
there are aromatic ring (e.g. benzene ring, etc.). Examples of the above 
compound [XIII] include 5,6-dihydro-4-methoxy-2H-pyran, 
morpholinocyclohexane, pyrrolidinoindene, morpholinocyclopentene, 
morpholinodihydrothiophene, 1-methyl-2-phenyl-1-azacycloheptane, 
N-methyl-2-phenylpyrroline, N-methyl-2-butylpyrroline, 
N-methyl-2-ethylpyrroline, N-methyl-2-[6'-methoxynaphthyl-(2')]pyridine, 
pyrrolidinocyclohexene, pyrrolidinocyclopentene, pyrrolidinocycloheptane, 
pyrrolidinocyclooctene, pyrrolidino2-methylcycloheptene, 
pyrrolidinocyclooctene, pyrrolidino2-methylcyclohexene, 
pyrrolidino2-phenylcyclohexene, pyrrolidinocyclononene and the like. 
In the case of the above reaction, if necessary, a catalyst may be added. 
Further, the above reaction may be conducted in the absence or presence of 
an inert solvent. As the inert solvent, for example, there are aliphatic 
hydrocarbons (e.g. pentane, hexane, etc.), aromatic hydrocarbons (e.g. 
benzene, toluene, xylene, etc.), alicyclic hydrocarbons (e.g. cyclohexane, 
cyclopentane, etc.), halogenated hydrocarbons (e.g. chloroform, 
dichloromethane, dichlorobenzene, bromobenzene, etc.), ketones (e.g. 
acetone, methyl ethyl ketone (MEK), cyclohexane, etc.), esters (e.g. ethyl 
acetate, butyl acetate, etc.), ethers (e.g. diethyl ether, dioxane, 
diisopropyl ether, anisole, diphenyl ether, etc.), nitriles (e.g. 
acetonitrile, benzonitrile, etc.), amides (e.g. dimethylformamide, 
N-methylpyrrolidone, etc.), nitrobenzene, dimethylsulfoxide and the like. 
The reaction composition may be essentially based on a stoichiometric 
ratio, for example, the reaction is conducted using 1 to 30 molar 
equivalent of the compound [II]. The reaction is normally conducted by 
mixing with stirring at -20.degree. to 200.degree. C. Thereafter, if 
necessary, the solvent is distilled off and filtered, and then a normal 
refining operation (e.g. recrystallization, column chromatography, etc.) 
is conducted to obtain novel compounds [IV] to [VII] of the present 
invention. 
Among them, the compounds [IV] and [V] have the diene part (CH.sub.2 
.dbd.C--C.dbd.N) in a molecule and, therefore, they further react with a 
compound represented by the formula: 
EQU A'.dbd.B' [VIII] 
to produce an additional novel heterocyclic compound [IX] or [X]. 
As the above compound [VIII], for example, there are N-substituted 
maleimides, maleic anhydride, maleic acid and esters thereof, fumaric acid 
and esters thereof, acetylenemonocarboxylic acid and esters thereof, 
acetylenedicarboxylic acid and esters thereof, phenylacetylenes, acylated 
acetylenes, (meth)acrylic acid and esters thereof, (meth)acrylonitrile, 
quinones, cyanoethylenes and the like. 
For example, the compound [VIII] may be a compound represented by the 
formula: 
##STR19## 
[wherein each R.sup.3 is the same or different and respectively indicates 
--R.sup.2 --CO.sub.2 H or --CN, or 
##STR20## 
C.dbd.C.dbd.O, C.dbd.N--R.sup.2 or C.dbd.O, or 
##STR21## 
is C.dbd.C, and R.sup.3 may bond together with or without O or N atom to 
form a cyclic group; and R.sup.2 is as defined above]. The above 
substituent R.sup.3 is the same or different. Examples of the substituent 
represented by R.sup.3 include --R.sup.2, --CO.sub.2 H, --CN and the like 
Further, the substituent represented by R.sup.3 may be those in which the 
same R.sup.3 or two substituents R.sup.3 on the adjacent carbon atom bond 
together to form a functional group, for example, those in which 
##STR22## 
(methylene group), C.dbd...dbd.O (ketene group), C.dbd.N--R.sup.2 (imino 
group) or C.dbd.O (carbonyl group), or 
##STR23## 
is C.dbd.C. 
Further, the substituent R.sup.3 and the other substituent R.sup.3 may bond 
together with or without O or N atom to form a cyclic group. For example, 
the cyclic group is formally represented by bonding each radical group 
--R., which is formed by abstracting hydrogen radical from each atom on 
each R.sup.3 to be bonded, together with or without O atom or N atom. 
Examples of the cyclic group include acid anhydride group (--COOCO--) of a 
structure wherein radical --COO. formed by abstracting radical H. from 
--CO.sub.2 H group is bonded with radical --CO. formed by abstracting 
radical H. from --CHO; N-substituted imide group (--CONR.sup.1 CO--) of a 
structure wherein --CONR.sup.1. is bonded with the above radical --CO.; 
unsaturated dicarbonyl group [--COC(R.sup.2).dbd.C(R.sup.2)CO--] of a 
structure wherein --CO(R.sup.2).dbd.C(R.sup.2). formed by abstracting 
radical H. from --COC(R.sup.2).dbd.C(R.sup.2)H is bonded with the above 
radical --CO. and the like. 
As the compound [XI], for example, there are maleic anhydride, N-methyl 
maleimide, N-phenyl maleimide, dimethyl fumarate, dimethyl maleate, 
dimethyl acetylenedicarboxylate, methyl propionate, methyl ethyl ketone, 
phenyl benzoyl acetylene ethyl-2-phenyl propionate, phenyl acetylene, 
allene, quinone, benzoquinone, tetracyanoethylene, tetracyanoquinone, 
diphenyl ketene and the like. 
In the above reaction, Lewis acid may be used as a catalyst. Examples of 
the Lewis acid include zinc chloride, tin chloride, aluminum chloride, 
BF.sub.3. (C.sub.2 H.sub.5).sub.2 O and the like. Further, the reaction 
may be conducted in the above inert solvent. The rection composition may 
be based on a stoichiometric ratio. For example, the reaction is conducted 
using 1 to 30 molar equivalent of the compound [VIII] based on the 
compound [IV] or IV]. The reaction is normally conducted by mixing with 
stirring at -20.degree. to 200.degree. C. Thereafter, if necessary, the 
solvent is distilled off and filtered, and then a normal refining 
operation (e.g. recrystallization, column chromatography, etc.) is 
conducted to obtain novel copounds [IX] to [X] of the present invention. 
In particular, when the compound [XI] is used as the compound [VIII], novel 
compounds represented by the following formulas: 
##STR24## 
[wherein R, R.sup.1, R.sup.2, R.sup.3 and X are as defined above], and 
##STR25## 
[wherein R, R.sup.1, R.sup.2, R.sup.3 and X are as defined above] are 
obtained. 
In the present invention, according to a novel method for employing whole 
conjugated system of an acylisocyanate group in the isocyanate compound 
[I], novel compounds [IV] to [VII] could be obtained and, further, the 
compounds [IX] to [V] (particularly, the compounds [IX'] to [X']) could be 
obtained. The heterocyclic compounds [IV] and [V] have conjugated double 
bond structures, as shown in the following formula: 
##STR26## 
The above conjugated double bond structure has polymerization reactivity 
and, therefore, the heterocyclic compounds [IV] and [V] can be used for 
the production of a homopolymer or copolymer. For example, the compound is 
used for the modification of a synthetic fiber, synthetic resin, natural 
high polymer and the like after subjecting it to a graft polymerization. 
Further, the compound is used for the production of a varnish, coating, 
adhesive, plastic, elastomer and the like after polymerizing it as it is 
or polymerizing it with the other comohomer. 
Further, the above conjugated double bond structure makes a cyclic addition 
reaction with various dienofiles to provide various heterocyclic compounds 
represented by novel compounds [IX'] to [X'] of the present invention. In 
these heterocyclic compounds, various functional groups can be introduced 
by varying dienophile, and various bioactivities may be expected from 
their molecular structures. Therefore, they become significant 
intermediates for synthetic raw materials in the fields of fine chemicals 
(e.g. medicines, pesticides, etc.). 
As described above, novel heterocyclic compounds [IV] to [VII], [IX] and 
[X] have a wide variety of applications for industrial raw materials. 
Further, these heterocyclic compounds can be easily conducted with simple 
operation. 
Further, the acylisocyanate compound [I] as a raw substance can be produced 
by reacting .alpha.-alkyl acrylamide with oxalyl halide. The reaction is 
normally conducted at a temperature of 0.degree. to 100.degree. C. under 
the presence of an inert solvent such as halgenated hydrocarbon. Further, 
in order to avoid an unnecessary polymerization of a terminal double bond, 
a polymerization inhibitor may be added to the reaction system. Examples 
of the polymerization inhibitor include hydroquinone, p-methoxyphenol, 
2,6-di-t-butyl-4-methylphenol, 4-t-butyl catechol, bis-dihydroxybenzyl 
benzene, 2,2'-methylene-bis(6-t-butyl-3-methylphenol), 
4,4'-butylidene-bis(6-t-butyl-3-methylphenol), 
4,4'-thio-bis(6-t-butyl-3-methylphenol), p-nitrosophenol, diisopropyl 
xanthogensulfide, N-nitrosophenylhydroxyamine ammonium salt, 
1,1-diphenyl-2-picrylhydrazyl, 1,3,5-triphenylfeldazyl, 
2,6-di-t-butyl-.alpha.-(3,5-di-t-butyl-4-oxo-2,5-cyclohexadiene-1-ylidene) 
-p-trioxy, 2,2,6,6,-tetramethyl-4-piperidone-1-oxyl, dithiobenzoyl sulfide, 
p,p'-ditolyl trisulfide, p,p'-ditolyl tetrasulfide, dibenzyl tetrasulfide, 
tetraethylthiuram sulfide and the like. 
The following Examples further illustrate the present invention in detail 
but are not to be construed to limit the scope thereof. 
EXAMPLES 1 TO 7 
Preparation of Heterocyclic Compound [IV] 
According to a composition shown in Table 1, methacryloyl isocyanate [I] 
was reacted with each compound [III'] under the reaction conditions shown 
in Table 1. After the reaction was completed, the deposited crystal was 
filtered off to obtain each heterocyclic compound [IV]. Yield and various 
physical properties of each heterocyclic compound [IV] are shown in Table 
2. 
TABLE 1 
__________________________________________________________________________ 
##STR27## 
##STR28## 
##STR29## 
[I] mg (mmol) 
R.sup.1 X 
R.sup.2 
R.sup.2 ' 
mg (mmol) 
Solvent 
Temperature 
Time 
__________________________________________________________________________ 
Ex. 1 
280 (2.5) 
##STR30## 
Ph H 530 (3.1) 
-- Room Temp. 
5 minutes 
Ex. 2 
500 (4.5) 850 (4.9) 
##STR31## 
Room Temp. 
3 hours 
Ex. 3 
1780 (16) 
##STR32## 
Ph H 3020 (16) 
CH.sub.3 CN 
Room Temp. 
20 hours 
Ex. 4 
640 (5.8) 1100 (5.8) 
CH.sub.3 CN 
reacted at room temp. 
for 2 hours, followed 
by refluxing for 4 hours 
Ex. 5 
2550 (23) 
H.sub.5 C.sub.2 O 
H H 2160 (30) 
CH.sub.3 CN 
reacted at room temp. 
for 8 hours, followed 
by refluxing for 7 hours 
Ex. 6 
2550 (23) 
H.sub.3 CO 
H.sub.3 C 
H 2880 (40) 
CH.sub.3 CN 
reacted at room temp. 
for 48 hours, followed by 
at 50 to 60.degree. C. for 9 
hours 
Ex. 7 
2550 (23) 1656 (23) 
CH.sub.3 CN 
reacted at room temp. 
for 5 hours, followed by 
at 50 to 55.degree. C. for 10 
hours 
with providing ultrasonic 
vibration 
__________________________________________________________________________ 
TABLE 2 
__________________________________________________________________________ 
##STR33## 
Melting MS (Mass spectrum) 
Yield point 
IR .sup.1 H-NMR 
m/z (Relative 
(%) R.sup.1 X 
R.sup.2 
R.sup.2 ' 
(.degree.C.) 
(KBr, cm.sup.-1) 
(CDCl.sub.3, .delta.) 
intensity, 
__________________________________________________________________________ 
%) 
Ex. 1 Ex. 2 
34 55 
##STR34## 
Ph H 178 .intg. 180 
-- -- -- 
Ex. 3 Ex. 4 
53 46 
##STR35## 
Ph H 144 --intg. 147 
-- -- 
Ex. 5 
24 H.sub.5 C.sub.2 O 
H H 71 3280 (OH), 
1.38(3H, t, J=7Hz), 
183 (M, 19), 
.intg. 
1710 (CN), 
2.00(3H, d, J=2Hz), 
72 (19), 
72.5 1620 (CC) 
4.00(2H, q, J=7Hz), 
71 (base peak) 
5.57(1H, q, J=2Hz), 
6.00(1H, S), 6.32(1H, 
d, J=12Hz), 9.65(1H, 
br.s) 
Ex. 6 
35 H.sub.3 CO 
H.sub.3 C 
H 110 3240 (OH) 
2.00(3H, d, J=2Hz), 
183 (M, 20) 
Ex. 7 
33 .intg. 
1630 (CN) 
2.37(3H, S), 3.77 
99 (100) 
113 (3H, S), 5.55(1H, q, 
J=2Hz), 5.88(1H, S), 
6.55(1H, S), 8.63 
(1H, br.s) 
__________________________________________________________________________ 
EXAMPLE 8 
Production of Heterocyclic Compound [IX'] 
2-Isopropenyl-4-hydroxy-6-morpholino-6-phenyloxazine (0.88 g, 2.9 mmole), 
N-methylmaleimide (0.6 g, 5.4 mmol) and zinc chloride (41 mg) were added 
to xylene (10 ml) and the mixture was heated at reflux for 6 hours. After 
cooling in air, xylene was distilled off under reduced pressure and the 
residue was subjected to silica gel chromatography to obtain an adduct as 
a crystal having a melting point of 241.degree. to 243.degree. C. Various 
physical properties of the resulting adduct are as follows. 
IR (KBr); 1770, 1700 (C.dbd.O) cm.sup.-1 
.sup.1 H-NMR (CDCl.sub.3); .delta.=2.24-2.52 (4H, m, N(CH.sub.2).sub.2), 
2.60-3.12 (5H, m, CH.sub.2 .times.2, CH), 2.90 (3H, s, CH.sub.3), 3.07 
(3H, s, N-CH.sub.3), 3.28-3.64 (5H, m, O(CH.sub.2).sub.2, CH), 6.88-7.44 
(5H, m, Ar-H) 
Mass spectrum m/z (relative intensity, %) 411 (M.sup.+, 45), 300 (M.sup.+ 
-N-methylmaleimide, 19), 299 (base peak) 
Elemental analysis (%), 
Calcd. for C.sub.22 H.sub.25 N.sub.3 O.sub.5 : C, 64.24; H, 6.08; N, 10.22 
Found: C, 64.43; H, 6.15; N, 10.14 
##STR36## 
EXAMPLES 9 TO 14 
Production of Heterocyclic Compounds [VII and [VII] 
According to a composition shown in Table 3, methacryloyl isocyanate [I] 
was reacted with each compound [XIII] under the reaction conditions shown 
in Table 3. After the reaction was completed, the deposited crystal was 
filtered off to obtain heterocyclic compounds [VI] and [VII]. Various 
physical properties of each heterocyclic compound [VI] obtained in 
Examples 10 and 11 are shown below. 
Heterocyclic compound [VI] of the Example 10: 
IR (KBr); 3270, 3160 (NH), 1750, 1690 cm.sup.-1 (C.dbd.O) 
.sup.1 H-NMR (CDCl.sub.3); .delta.=0.84-2.56 (14H, m, CH.sub.2), 1.20 (3H, 
s, CH.sub.3), 2.60-3.00 (4H, m, N(CH.sub.2).sub.2), 8.40 (1H, brs, NH) 
Mass spectrum m/z (relative intensity, %) 285 (M.sup.+, 68), 194 (100) 
Heterocyclic compound [VI] of Example 11: 
IR (KBr); 3222, 3106 (NH), 1734, 1709 cm.sup.-1 (C.dbd.O) 
.sup.1 H-NMR (CDCl.sub.3); .delta.=0.83-2.83 (12H, m, 5,6,7,8-H, 
N(CH.sub.2).sub.2), 1.25 (3H, s, CH.sub.3), 2.00 (2H, s, 4-H), 3.17-4.00 
(4H, m, O(CH.sub.2).sub.2), 8.18 (1H, brs, NH) 
Mass spectrum m/z (relative intensity, %) 278 (M.sup.+, 86), 193 (100) 
TABLE 3 
__________________________________________________________________________ 
##STR37## 
Example 
9 10 11 12 13 14 
__________________________________________________________________________ 
Methacryloyl isocyanate[I] 
1110 1110 1110 1110 
1110 1110 
mg (mmol) (10) (10) (10) (10) (10) (10) 
Compound [VIII] 
(CH.sub.2 ) .sub.n 
(CH.sub.2 ) .sub.3 
(CH.sub.2 ) .sub.4 
(CH.sub.2 ) .sub.4 
(CH.sub.2 ) .sub.5 
##STR38## 
R.sup.1 X 
##STR39## 
##STR40## 
##STR41## 
##STR42## 
##STR43## 
mg (mmol) 
1530 (10) 
1510 (10) 
1670 (10) 
1670 (10) 
1810 (10) 
1850 (10) 
Reaction 
Solvent 
CH.sub.3 CN 
CH.sub.3 CN/C.sub.6 H.sub.6 
CH.sub.3 CN 
m-xylene 
CH.sub.3 CN 
CH.sub.3 CN 
conditions 
Room temp. 
12 18 12 3 1 1 
(hour) 
Reflux 20 2 20 7 20 20 
(hour) 
Product 
Yield (%) 
5 -- 15 -- 11 2 
[VII] (CH.sub.2 ) .sub.n 
(CH.sub.2 ) .sub.3 
(CH.sub.2 ) .sub.4 
(CH.sub.2 ) .sub.4 
(CH.sub.2 ) .sub.5 
##STR44## 
Melting 
188.about.190 
-- 163.about.164 
140.about.143 
192.about.195 
point (.degree.C.) 
Product 
Yield (%) 
-- 5 24 24 -- -- 
[VI] (CH.sub.2 ) .sub.n 
(CH.sub.2 ) .sub.3 
(CH.sub.2 ) .sub.4 
(CH.sub.2 ) .sub.4 
(CH.sub.2 ) .sub.5 
##STR45## 
XR.sup.1 
##STR46## 
##STR47## 
##STR48## 
##STR49## 
##STR50## 
Melting 
-- 227.about.228 
205.about.207 
-- -- 
point (.degree.C.) 
__________________________________________________________________________ 
EXAMPLE 15 
Methacryloyl isocyanate (1.11 g, 10 mmol) and 1-morpholino-1-phenylpropene 
(2.03 g, 10 mmol) were stirred in acetonitrile at room temperature for 12 
hours, followed by stirring under heating at reflux for 20 hours. The 
reaction mixture was subjected to a column chromatography to obtain a 
heterocyclic compound (7.8%). 
##STR51## 
Melting point: 168.degree.-170.degree. C. 
IR (KBr, cm.sup.-1); 3188, 1707 
.sup.1 H-NMR (CDCl.sub.3, .delta.); 1.32 (3H, d), 1.66 (3H, s), 1.86 (1H, 
dd), 2.40(1H, dd), 2.80 (1H, ddd), 7.20-8.00 (5H, m), 8.66 (1H, bs)