CA1251794A - Process for synthesis of 2-vinyl-4,6-diamino-s- triazine - Google Patents
Process for synthesis of 2-vinyl-4,6-diamino-s- triazineInfo
- Publication number
- CA1251794A CA1251794A CA000471897A CA471897A CA1251794A CA 1251794 A CA1251794 A CA 1251794A CA 000471897 A CA000471897 A CA 000471897A CA 471897 A CA471897 A CA 471897A CA 1251794 A CA1251794 A CA 1251794A
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- CA
- Canada
- Prior art keywords
- triazine
- diamino
- process according
- reduced pressure
- imidazolyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Abstract
Abstract of the Disclosure Disclosed is a process for the synthesis of 2-vinyl-4,6-diamino-S-triazine having the following structural formula:
which comprises heating an imidazolyl-S-triazine compound represented by the following general formula:
which comprises heating an imidazolyl-S-triazine compound represented by the following general formula:
Description
~L2~L7~
PROCESS FOR SYNT~IESIS OF 2-VINYL-4,6-DIAMINO-S-TR:[AZINE
Background of_the Invention (1) Field of the Invention The present invention rela-tes to a process for the synthesis of 2-vinyl-4,6-diamino-S--triazine (hereinafter referred to as "Vq"'). More particularly, the present invention provides a process for preparing VT in large quantities at low costs.
PROCESS FOR SYNT~IESIS OF 2-VINYL-4,6-DIAMINO-S-TR:[AZINE
Background of_the Invention (1) Field of the Invention The present invention rela-tes to a process for the synthesis of 2-vinyl-4,6-diamino-S--triazine (hereinafter referred to as "Vq"'). More particularly, the present invention provides a process for preparing VT in large quantities at low costs.
(2) Description of the Prior Art Vq' is a compound which is valuable as a comonomer, and it is Icnown that if a diamino-S--triazine is introduced into side chains of a polymer, the softening point and glass transition poin-t of -the polymer are greatly elevated as compared with those of the unintroduced polymer, and the specific gravity is increased and the solubili-ty is prominently changed (see, for example, Nadao and Kakurai: Collection o~ Polymer Theses, 32, 308 (1975) ancl T. Seo, K. Abe, H. ~lonma and T. Kakurai: Polym. Prepn., 20, 661 (1979)).
Several processes as described below are known for the synthesis of VT. Namely, there can be mentioned a process in which biguanide is reacted with acrylic acid chlor-ide (C. G. Overberger et al: J.A.C.S., 80, 988 (1958)), a process in which dicyandiamide is reacted with ~-dimethylaminopropionitrile (French Patent No.
1,563,255 (1967) to Hoechst AG), a process in which 1,2-di( Ll, 6-diamino-S-triazinyl-(2))-cyclobutane is heated at 320C under reduced pressure (Japanese Patent Publication No. 35068/71 to Asahi Kasei), and a process in which 2-~-methoxyethyl-4,6-diamino-S-triazine is heated a-t 350C in a nitrogen current (Suddeutsche Kalksticks-toff Werke A.G.: Offen. 2, 135, 881 (1973)).
However, -these known processes are defective in tha-t the starting materials are expensive or the reaction procedures are complicated. Accordingly, none of these known processes are suitable for industrial working.
S mary of the Invention It is therefore a primary object of the present inven-tion to provide a process for synthesizing VT in large quantities at low costs, which is suitable for industrial working.
More specifically, in accordance with the present invention, there is provided a process for the synthesis of 2-vinyl-4,6-diamino-S--triazine having the following str~lctural formula:
~NH2 N - C
// ~
CH2 = CH - C N
N = C
which comprises heating an imidazolyl-S-triazine compound represented by the following general formula:
~ N - C~
N N ~ CH2CH2 ~ C N
Rl NH2 wherein Rl stands for a hydrogen atom, a methyl group or an ethyl group, and R2 stands for a hydrogen atom or a methyl group,
Several processes as described below are known for the synthesis of VT. Namely, there can be mentioned a process in which biguanide is reacted with acrylic acid chlor-ide (C. G. Overberger et al: J.A.C.S., 80, 988 (1958)), a process in which dicyandiamide is reacted with ~-dimethylaminopropionitrile (French Patent No.
1,563,255 (1967) to Hoechst AG), a process in which 1,2-di( Ll, 6-diamino-S-triazinyl-(2))-cyclobutane is heated at 320C under reduced pressure (Japanese Patent Publication No. 35068/71 to Asahi Kasei), and a process in which 2-~-methoxyethyl-4,6-diamino-S-triazine is heated a-t 350C in a nitrogen current (Suddeutsche Kalksticks-toff Werke A.G.: Offen. 2, 135, 881 (1973)).
However, -these known processes are defective in tha-t the starting materials are expensive or the reaction procedures are complicated. Accordingly, none of these known processes are suitable for industrial working.
S mary of the Invention It is therefore a primary object of the present inven-tion to provide a process for synthesizing VT in large quantities at low costs, which is suitable for industrial working.
More specifically, in accordance with the present invention, there is provided a process for the synthesis of 2-vinyl-4,6-diamino-S--triazine having the following str~lctural formula:
~NH2 N - C
// ~
CH2 = CH - C N
N = C
which comprises heating an imidazolyl-S-triazine compound represented by the following general formula:
~ N - C~
N N ~ CH2CH2 ~ C N
Rl NH2 wherein Rl stands for a hydrogen atom, a methyl group or an ethyl group, and R2 stands for a hydrogen atom or a methyl group,
- 3 ~
or an isocyanuric acid-addition product -thereof under reduced pressure in the presence of a polymerization inhibitor.
Detailed Description of the Invention -The process of the present invention can be expressed by the following reaction formula:
~ 1 N - C~ 2 ~ \N ---- C/
R
under reduced ~NH2 R2 pressure //N-- C~
~ CH = CH-C N -~ N NH
heating N~l2 R
wherein Rl and R2 are as defined above, or _ 4 _ ~ 7 ~ N~--C~
N N-CH2CH2-C\ N ~ C
`~ ~ N.-_ C HN NH
Rl \NH2 C
Il under reduced N-- C R~2C C
pressure /~
_ ~, CH2=CH-C N + N NH + ¦ l heating N =-C ~ HN NH
Rl \ /
o wherein Rl and R2 are as defined above.
The starting imidazolyl-S-triazine compound used in -the process of the present invention is e.asily obtained from acrylonitrile, an imidazole compound and dicyandiamide according to the process disclosed in Japanese Patent Publication No. 36391/72.
An isocyanuric acid-addition product of the imidazoly]-S-triazine compound is easily obtained by reacting an imidazolyl-S-triazine compound with isocyanuric acid according to the process disclosed in U. S. Patent No. 4,205,156.
The yield in the reaction of forming the imidazolyl-S-triazine compound or its isocyanuric acid-addi-tion product from the imidazole compound is very good, and the operation procedures for forming VT from this starting substance are very simple and the yield is 5 ~5~75~'~
very good~ which will readily be understood from Examples given hereinafter. Accordingly, the reaction of -the present invention is very suitable for working on an industrial scale.
Embodiments of the reaction of the present invention will now be described in detail.
The starting imidazolyl-S-triazine compound is heated at a temperature of 180 to 320C under a reduced pressure of about 5 to about 20 mmHg for an appropriate time in the presence of an appropriate polymerization inhibitor in an appropriate reaction vessel in which a reduced pressure as described above can be maintained.
By -this heating, VT and the imidazole compound are sublimated to adhere to the wall of the upper portion of the reac-tion vessel. It is preferred that the wall of the upper portion of the reaction vessel be air-cooled or water-cooled.
The adhering reaction product is collected and washed with water to remove the imidazole compound, and the residue is recrystallized from water to obtain intended VT.
When the isocyanuric acid-addition adduct of the imidazolyl-S-triazi.ne compound is used, the adduct is hea-ted at 180 to 320C under a reduced pressure of about 5 to about 20 mm~lg for an appropriate time in the presence of an appropriate polymerization inhibitor in an appropriate reaction vessel in which a reduced pressure as described above can be maintained. VT and the imidazole compound are sublimated to adhere to the wall of the upper portion of the reaction vessel. It is preferred that the wall of the upper portion of the reaction vessel be air-cooled or water-cooled.
A higher degree of the pressure reduction is preferred, but about 5 mmHg is sufficient. The reaction time is within one hour.
The adhering reaction product is washed with water to remove the imidazole compound and isocyanuric acid.
The residue is recrystallized from wa-ter to obtain in-tended VT.
As typical examples of the polymerization inhibitor to be used in the present invention, there can be mentioned sodium sulfide, potassium sulfide, hydroquinone, copper sulfa-te and ~-naphthylamine. Among these cornpounds, sodium sulfide gives a highest polymerization-inhibiting effect.
In carrying out the process of the present invention, a powdery or granular hea-t-conducting medium may be present in -the reaction system so as to increase the heat conductivity in the reaction sys-tem. As typical ins-tances of the powdery or granular heat-conducting medium to bc used in -the presen-t invention, there can bc mentioned quartz sand, sea sand, river sand, glass powder, silica powder, alumina powder, iron powder, copper powder, brass powder, bronze powder, aluminum powder and zinc powder. I-t is preferred that the size of the powdery or granular hea-t-conducting medium be in the range of 32 to 7 mesh according -to -the Tyler standard. It also is preferred that the powdery or granular heat-conducting medium be mixed with the starting substance so that the amount of the medium is larger than the amount of the starting substance based on the weight, and the reaction be then carried Otlt.
3 The properties of VT are now described.
Melting Point:
239 to 241C
Solubility Characteristics:
_ 7 _ ~ ~7~L~
Soluble in hot water and difficultly soluble in hot methanol, hot ethanol and hot acetone.
Basicity:
Substantially neutral.
Polymerizabili-ty:
A po]ymer insoluble in hot water is obained when VT
is dissolved in ho-t water and azobisisobutyronitrile is added to the solution.
TLC (alumina, silica and EtOH):
Rf = 0.0 KBr 3340, 3170, 1680 (fourth absorption), 1655 (second absorption), 1550 (first absorption), 1460 (fifth absorpi-ton), 1425 (third absorption), 1370, 1265, 1130, 985, 960, 835 (sixth absorption) NMR (d6-DMSO),~ :
6.76 (multiplet, LIH), 6.35-6.45 (triplet, 2H), 5.59-5.72 (quadruplet, lH) Elementclry Analysis Values:
C = 4ll.28%, H = 5.07%, N = 50.52%
The present invention will now be described in detail with reference -to the following Examples that by no means limi-t the scope of the invention.
Example 1 In 7 m~ of wa-ter were dissolved 20.5 g (0.1 mole) of a crystal of 2-(~ -imidazolyl-1')-ethyl-l1,6-diamino-S-triazine and 2.2 g (O. oo8 mole) of Na2S-9H20, and the aqueous solution was sufficiently mixed and dried and solidified under reduced pressure to obtain a starting material. This operation was performed so that the polymerization inhibitor was uniformly stuck to the crys-tal of -the imidazolyl-S-triazine compound.
7~
The so-obtained starting material and 25 g of quartz sand (havlng a size of 16 Tyler mesh) were charged in a Claisen flask having a side arm and an inner capacity of about 100 m~, and the bottom portion of the flask was wrapped with a hood on an electric hea-ter and heating was carried out under a reduced pressure of 3 mmHg. Thus, the iner tempeature of the flask was maintaiend at 250C for 0.5 hour. After natural cooling, the sublimation product adhering to the inner wall of the upper portion and side arm of the flask was cQllected, and 36 m~ of water was added to the collected sublimation product and the mixture was stirred at room temperature for a while. The insoluble substance (crude VT) was recovered by filtration and recrystallized from 100 mm of water to obtain 8.5 g (the yield being 62%) of intended VT characterized by a melting point of 239 to 24].C and a TLC value (silica and EtOH, coloration wi-th I2) of Rf = 0.00 to 0.01. The filtrate was distilled under reduced pressure to ~.9 g of imidazole (the recovery ratio was 72%).
xample 2 In 7 m~ of water were dissolved 21.9 g (0.1 mole) of a crystal of 2~ (2'-methylimidazolyl-1'))-ethyl-Ll,6-diamino-S-triazirle and 2.2 g (O. oo8 mole) of Na2S-9H20, and the aqueous solution was sufficiently mixed,and dried and solidified under reduced pressure to obtain a starting material. This operation was performed so that -the polymerization inhibitor was uniformly stuck to the crystal of the imidazolyl-S-triazine compound., The 3 starting material was charged in a Claisen flask having a side arm and an inner capacity of about 100 m~ and the bottom portion of the flask was wrapped with a hood on an electric hea-ter. Heating was carried out under a ~5$~
reduced pressure of 5 mmHg and the inner temperature of the flask was maintained at 240C for 1 hour. After natural cooling, the sublimation produc-t adhering to the inner wall of the upper portion and side arm of the flask was collected, and 35 m~ of water was added to the collec-ted sublimation produc-t and the mixture was stirred at room temeprature for a while. The insoluble subs-tance (crude VT) was collected by filtration and was recrystallized from 110 m~ of water to obtain 11 g (the yield being 80~o) of intended VT characterized by a melting point of 239 to 241C and a TLC value (silica and EtOH, coloration with I2) of Rf = 0.00 to 0.01. The fil-trate was distilled under reduced pressure to recover 5 . 8 g of 2-methylimidazole having a mel-ting point of 115 -to 118C (-the recovery ratio was 71%).
Example 3 In '7 mR of water were dissolved 2LI.7 g (0.1 mole) of a crystal of 2~ (2'-ethyl-l~'(5')-methylimidazolyl-l'))-ethyl-L~,6-diamillo-S-triazirle and l~. 8 g (0. 02 mole) 20 of Na2S-9~l20, and -the aqueous solution was sufficiently mixed, and dried and solidified under reduced pressure to obtain a starting ma-terial. The starting ma-terial was charged in a Claisen flask having a side arm and an inner capacity of abou-t 100 m~. The bottom portion of 25 the flask was wrapped with a hood on an electric heater and heating was carried out under a reduced pressure of 5 mmHg to maintain the inner temperature of the flask at 300C for 1 hour. After natural cooling, the distillation product adhering to the upper portion and 3 side arm of the flask was collected and washed with 35 m~
of methanol at room temperature, and the insoluble substance (crude VT) was recovcered by filtration in an amount of 9.6 g (0.07 mole) (the yield being 70%). The melting point of the recovered insoluble substance was 235 to 240C. The insoluble substance was recrystallized from wa-ter to obtain 8.9 g (0.065 mole) (the yield being 65%) of purified intended VT
5 characterized by a melting point of 239 to 241C and a TLC value (silica and ~tOH, coloration with I2) of Rf -0.00 to 0.01. The filtrate was distilled under reduced pressure to recover 9.35 g of 2-methyl-4(5)-methylimidazole (o.o85 mole, the yield being 85 %).
Example 4 In 12 m~ of water were dissolved 34.8 g (0.1 mole) of a crystal of 2-(~-(2'-methylirnidazolyl-1'))-ethyl-
or an isocyanuric acid-addition product -thereof under reduced pressure in the presence of a polymerization inhibitor.
Detailed Description of the Invention -The process of the present invention can be expressed by the following reaction formula:
~ 1 N - C~ 2 ~ \N ---- C/
R
under reduced ~NH2 R2 pressure //N-- C~
~ CH = CH-C N -~ N NH
heating N~l2 R
wherein Rl and R2 are as defined above, or _ 4 _ ~ 7 ~ N~--C~
N N-CH2CH2-C\ N ~ C
`~ ~ N.-_ C HN NH
Rl \NH2 C
Il under reduced N-- C R~2C C
pressure /~
_ ~, CH2=CH-C N + N NH + ¦ l heating N =-C ~ HN NH
Rl \ /
o wherein Rl and R2 are as defined above.
The starting imidazolyl-S-triazine compound used in -the process of the present invention is e.asily obtained from acrylonitrile, an imidazole compound and dicyandiamide according to the process disclosed in Japanese Patent Publication No. 36391/72.
An isocyanuric acid-addition product of the imidazoly]-S-triazine compound is easily obtained by reacting an imidazolyl-S-triazine compound with isocyanuric acid according to the process disclosed in U. S. Patent No. 4,205,156.
The yield in the reaction of forming the imidazolyl-S-triazine compound or its isocyanuric acid-addi-tion product from the imidazole compound is very good, and the operation procedures for forming VT from this starting substance are very simple and the yield is 5 ~5~75~'~
very good~ which will readily be understood from Examples given hereinafter. Accordingly, the reaction of -the present invention is very suitable for working on an industrial scale.
Embodiments of the reaction of the present invention will now be described in detail.
The starting imidazolyl-S-triazine compound is heated at a temperature of 180 to 320C under a reduced pressure of about 5 to about 20 mmHg for an appropriate time in the presence of an appropriate polymerization inhibitor in an appropriate reaction vessel in which a reduced pressure as described above can be maintained.
By -this heating, VT and the imidazole compound are sublimated to adhere to the wall of the upper portion of the reac-tion vessel. It is preferred that the wall of the upper portion of the reaction vessel be air-cooled or water-cooled.
The adhering reaction product is collected and washed with water to remove the imidazole compound, and the residue is recrystallized from water to obtain intended VT.
When the isocyanuric acid-addition adduct of the imidazolyl-S-triazi.ne compound is used, the adduct is hea-ted at 180 to 320C under a reduced pressure of about 5 to about 20 mm~lg for an appropriate time in the presence of an appropriate polymerization inhibitor in an appropriate reaction vessel in which a reduced pressure as described above can be maintained. VT and the imidazole compound are sublimated to adhere to the wall of the upper portion of the reaction vessel. It is preferred that the wall of the upper portion of the reaction vessel be air-cooled or water-cooled.
A higher degree of the pressure reduction is preferred, but about 5 mmHg is sufficient. The reaction time is within one hour.
The adhering reaction product is washed with water to remove the imidazole compound and isocyanuric acid.
The residue is recrystallized from wa-ter to obtain in-tended VT.
As typical examples of the polymerization inhibitor to be used in the present invention, there can be mentioned sodium sulfide, potassium sulfide, hydroquinone, copper sulfa-te and ~-naphthylamine. Among these cornpounds, sodium sulfide gives a highest polymerization-inhibiting effect.
In carrying out the process of the present invention, a powdery or granular hea-t-conducting medium may be present in -the reaction system so as to increase the heat conductivity in the reaction sys-tem. As typical ins-tances of the powdery or granular heat-conducting medium to bc used in -the presen-t invention, there can bc mentioned quartz sand, sea sand, river sand, glass powder, silica powder, alumina powder, iron powder, copper powder, brass powder, bronze powder, aluminum powder and zinc powder. I-t is preferred that the size of the powdery or granular hea-t-conducting medium be in the range of 32 to 7 mesh according -to -the Tyler standard. It also is preferred that the powdery or granular heat-conducting medium be mixed with the starting substance so that the amount of the medium is larger than the amount of the starting substance based on the weight, and the reaction be then carried Otlt.
3 The properties of VT are now described.
Melting Point:
239 to 241C
Solubility Characteristics:
_ 7 _ ~ ~7~L~
Soluble in hot water and difficultly soluble in hot methanol, hot ethanol and hot acetone.
Basicity:
Substantially neutral.
Polymerizabili-ty:
A po]ymer insoluble in hot water is obained when VT
is dissolved in ho-t water and azobisisobutyronitrile is added to the solution.
TLC (alumina, silica and EtOH):
Rf = 0.0 KBr 3340, 3170, 1680 (fourth absorption), 1655 (second absorption), 1550 (first absorption), 1460 (fifth absorpi-ton), 1425 (third absorption), 1370, 1265, 1130, 985, 960, 835 (sixth absorption) NMR (d6-DMSO),~ :
6.76 (multiplet, LIH), 6.35-6.45 (triplet, 2H), 5.59-5.72 (quadruplet, lH) Elementclry Analysis Values:
C = 4ll.28%, H = 5.07%, N = 50.52%
The present invention will now be described in detail with reference -to the following Examples that by no means limi-t the scope of the invention.
Example 1 In 7 m~ of wa-ter were dissolved 20.5 g (0.1 mole) of a crystal of 2-(~ -imidazolyl-1')-ethyl-l1,6-diamino-S-triazine and 2.2 g (O. oo8 mole) of Na2S-9H20, and the aqueous solution was sufficiently mixed and dried and solidified under reduced pressure to obtain a starting material. This operation was performed so that the polymerization inhibitor was uniformly stuck to the crys-tal of -the imidazolyl-S-triazine compound.
7~
The so-obtained starting material and 25 g of quartz sand (havlng a size of 16 Tyler mesh) were charged in a Claisen flask having a side arm and an inner capacity of about 100 m~, and the bottom portion of the flask was wrapped with a hood on an electric hea-ter and heating was carried out under a reduced pressure of 3 mmHg. Thus, the iner tempeature of the flask was maintaiend at 250C for 0.5 hour. After natural cooling, the sublimation product adhering to the inner wall of the upper portion and side arm of the flask was cQllected, and 36 m~ of water was added to the collected sublimation product and the mixture was stirred at room temperature for a while. The insoluble substance (crude VT) was recovered by filtration and recrystallized from 100 mm of water to obtain 8.5 g (the yield being 62%) of intended VT characterized by a melting point of 239 to 24].C and a TLC value (silica and EtOH, coloration wi-th I2) of Rf = 0.00 to 0.01. The filtrate was distilled under reduced pressure to ~.9 g of imidazole (the recovery ratio was 72%).
xample 2 In 7 m~ of water were dissolved 21.9 g (0.1 mole) of a crystal of 2~ (2'-methylimidazolyl-1'))-ethyl-Ll,6-diamino-S-triazirle and 2.2 g (O. oo8 mole) of Na2S-9H20, and the aqueous solution was sufficiently mixed,and dried and solidified under reduced pressure to obtain a starting material. This operation was performed so that -the polymerization inhibitor was uniformly stuck to the crystal of the imidazolyl-S-triazine compound., The 3 starting material was charged in a Claisen flask having a side arm and an inner capacity of about 100 m~ and the bottom portion of the flask was wrapped with a hood on an electric hea-ter. Heating was carried out under a ~5$~
reduced pressure of 5 mmHg and the inner temperature of the flask was maintained at 240C for 1 hour. After natural cooling, the sublimation produc-t adhering to the inner wall of the upper portion and side arm of the flask was collected, and 35 m~ of water was added to the collec-ted sublimation produc-t and the mixture was stirred at room temeprature for a while. The insoluble subs-tance (crude VT) was collected by filtration and was recrystallized from 110 m~ of water to obtain 11 g (the yield being 80~o) of intended VT characterized by a melting point of 239 to 241C and a TLC value (silica and EtOH, coloration with I2) of Rf = 0.00 to 0.01. The fil-trate was distilled under reduced pressure to recover 5 . 8 g of 2-methylimidazole having a mel-ting point of 115 -to 118C (-the recovery ratio was 71%).
Example 3 In '7 mR of water were dissolved 2LI.7 g (0.1 mole) of a crystal of 2~ (2'-ethyl-l~'(5')-methylimidazolyl-l'))-ethyl-L~,6-diamillo-S-triazirle and l~. 8 g (0. 02 mole) 20 of Na2S-9~l20, and -the aqueous solution was sufficiently mixed, and dried and solidified under reduced pressure to obtain a starting ma-terial. The starting ma-terial was charged in a Claisen flask having a side arm and an inner capacity of abou-t 100 m~. The bottom portion of 25 the flask was wrapped with a hood on an electric heater and heating was carried out under a reduced pressure of 5 mmHg to maintain the inner temperature of the flask at 300C for 1 hour. After natural cooling, the distillation product adhering to the upper portion and 3 side arm of the flask was collected and washed with 35 m~
of methanol at room temperature, and the insoluble substance (crude VT) was recovcered by filtration in an amount of 9.6 g (0.07 mole) (the yield being 70%). The melting point of the recovered insoluble substance was 235 to 240C. The insoluble substance was recrystallized from wa-ter to obtain 8.9 g (0.065 mole) (the yield being 65%) of purified intended VT
5 characterized by a melting point of 239 to 241C and a TLC value (silica and ~tOH, coloration with I2) of Rf -0.00 to 0.01. The filtrate was distilled under reduced pressure to recover 9.35 g of 2-methyl-4(5)-methylimidazole (o.o85 mole, the yield being 85 %).
Example 4 In 12 m~ of water were dissolved 34.8 g (0.1 mole) of a crystal of 2-(~-(2'-methylirnidazolyl-1'))-ethyl-
4, 6-diamino-S--triazine/isocyanuric acid adduct and 1.2 g ( 5 mole) of Na2S-9H20, and the aqueous solution was sufficiently stirred, and dried and solidified under reduced pressure to obtain a starting ma-terial. The starting material was charged in a Claisen flask having a side arln and an inner capacity of about 100 m~, and the bottom portion of the flaslc was wrapped with a hood on an electric heater. Heating was carried ou-t under a reduced pressure of 5 mmHg and the inner tempera-ture of the flaslc was maintained at 240C for 1 hour. Af-ter natural cooling, -the sublimation product adhering to the inner wall of the upper portion and side arm of the flask was collected. Then, 50 m~ of a 0.2N NaOH aqueous solution was added -to the collected sublimation product and the mixture was heated and stirred for a while. The insolbule (crude VT) was recovered by filtration and recyrstallized from 100 mQ of water to obtain 10.4 g (the yield being 76%) of intended VT charac-terized by a melting point of` 239 to 241C and a TLC value (silica and EtOH, coloration with I2) of Rf = 0.00 to 0.01.
Example 5 In 7 m~ of water were dissolved 21.9 g (0.1 mole) of 2- (f3 - ( 2'-me-thylimidazolyl-1'))-ethyl-4,6-diamino-S-triazine and 2.2 g (o.oo8 mole) of Na2S-9H20, and the aqueous solution was sufficiently mixed, and dried and solidified under reduced pressure to form a starting material. The starting material and 25 g of alumina powder were charged in a Claisen flask having a side arm and an inner capacity of about 100 m~, and the bottom portion of the flask was wrapped with a hood on an electric heater. Heating was carried out under a reduced pressure of 5 mmHg and the inner temperature of the flasl~ was maintained at 320C for 45 minu-tes. After natural cooling, -the sublimation product adhering to the inner wall of -the upper portion and side arm of the flaslc was collected, and 50 m.~ of a 0.2N NaOH aqueous solution was added to the collected sublimation product and the mlxt~lre was heated and stirred for a while. The insoluble substance (curde VT) was recovered by filtration and recrystallized from 100 m~ of wa-ter -to obtain 10.7 g (the yield being 78 %) of intended VT
characterized by a melting point of 239 -to 241C and a TLC value (silica and EtOH, coloration wi-th I2) of Rf =
0.00 to 0.01. Incidentally, the recovery ratio of 2-methylimidazole was 82%.
Example 5 In 7 m~ of water were dissolved 21.9 g (0.1 mole) of 2- (f3 - ( 2'-me-thylimidazolyl-1'))-ethyl-4,6-diamino-S-triazine and 2.2 g (o.oo8 mole) of Na2S-9H20, and the aqueous solution was sufficiently mixed, and dried and solidified under reduced pressure to form a starting material. The starting material and 25 g of alumina powder were charged in a Claisen flask having a side arm and an inner capacity of about 100 m~, and the bottom portion of the flask was wrapped with a hood on an electric heater. Heating was carried out under a reduced pressure of 5 mmHg and the inner temperature of the flasl~ was maintained at 320C for 45 minu-tes. After natural cooling, -the sublimation product adhering to the inner wall of -the upper portion and side arm of the flaslc was collected, and 50 m.~ of a 0.2N NaOH aqueous solution was added to the collected sublimation product and the mlxt~lre was heated and stirred for a while. The insoluble substance (curde VT) was recovered by filtration and recrystallized from 100 m~ of wa-ter -to obtain 10.7 g (the yield being 78 %) of intended VT
characterized by a melting point of 239 -to 241C and a TLC value (silica and EtOH, coloration wi-th I2) of Rf =
0.00 to 0.01. Incidentally, the recovery ratio of 2-methylimidazole was 82%.
Claims (12)
1. A process for the synthesis of 2-vinyl-4,6-diamino-S-triazine having the following structural formula:
which comprises heating an imidazolyl-S-triazine compound represented by the following general formula:
wherein R1 stands for a hydrogen atom, a methyl group or an ethyl group, and R2 stands for a hdyrogen atom or a methyl group, or an isocyanuric acid-addition product thereof under reduced pressure in the presence of a polymerization inhibitor.
which comprises heating an imidazolyl-S-triazine compound represented by the following general formula:
wherein R1 stands for a hydrogen atom, a methyl group or an ethyl group, and R2 stands for a hdyrogen atom or a methyl group, or an isocyanuric acid-addition product thereof under reduced pressure in the presence of a polymerization inhibitor.
2. A process according to claim 1, wherein the imidazolyl-S-triazine compound is 2-(.beta.-imidazolyl-(1'))-ethyl-4,6-diamino-S-triazine.
3. A process according to claim 1, wherein the imidazolyl-S-triazine compound is 2-(.beta.-(2'-methylimidazolyl-1'))-ethyl-4,6-diamino-S-triazine.
4. A process according -to claim 1, wherein the imidazolyl-S-triazine compound is 2-(.beta.-(2'-ethyl-4'(5')-methylimidazolyl-1'))-ethyl-4,6-diamino-S-triazine.
5. A process according to claim 1, wherein the isocyanuric acid-addition product of the imidazolyl-S-triazine compound is an isocyanuric acid-addition product of 2-(.beta.-(2'-methylimidazolyl-1'))-ethyl-4,6-diamino-S-triazine represented by the following formula:
6. A process according to claim 1, wherein the polymerization inhibitor is sodium sulfide.
7. A process according to claim 1, wherein the heating under reduced pressure is carried out in the co-presence of a powdery or granular heat-conducting medium.
8. A process according to claim 7, wherein the heat-conducting medium is quartz sand.
9. A process according to claim 7, wherein the heat-conducting medium is alumina powder.
10. A process according to claim 1, 2 or 3, wherein the heating under reduced pressure is carried out at a temperature of 180 to 320°C at a pressure of from about 5 to about 20 mmHg in a reaction vessel, whereby the produced 2-vinyl-4,6-diamino-S-triazine sublimates and adheres to an upper portion of the vessel which is cooled by air or water.
11. A process according to claim 4, 5 or 6, wherein the heating under reduced pressure is carried out at a temperature of 180 to 320°C at a pressure of from about 5 to about 20 mmHg in a reaction vessel, whereby the produced 2-vinyl-4,6-diamino-S-triazine sublimates and adheres to an upper portion of the vessel which is cooled by air or water.
12. A process according to claim 7, 8 or 9, wherein the heating under reduced pressure is carried out at a temperature of 180 to 320°C at a pressure of from about 5 to about 20 mmHg in a reaction vessel, whereby the produced 2-vinyl-4,6-diamino-S-triazine sublimates and adheres to an upper portion of the vessel which is cooled by air or water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000471897A CA1251794A (en) | 1985-01-11 | 1985-01-11 | Process for synthesis of 2-vinyl-4,6-diamino-s- triazine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000471897A CA1251794A (en) | 1985-01-11 | 1985-01-11 | Process for synthesis of 2-vinyl-4,6-diamino-s- triazine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1251794A true CA1251794A (en) | 1989-03-28 |
Family
ID=4129555
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000471897A Expired CA1251794A (en) | 1985-01-11 | 1985-01-11 | Process for synthesis of 2-vinyl-4,6-diamino-s- triazine |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1251794A (en) |
-
1985
- 1985-01-11 CA CA000471897A patent/CA1251794A/en not_active Expired
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