Translation by 6079_Smith_W_II
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...I've been having a bit of trouble with this one -- the scan quality of the document is not very good in either of the versions I have, there are some complicated (to me) run-on sentences, whine whine excuses etc etc... mainly the problem is I still suck at Japanese.
Here's the meat of the patent, the experimental part...
Patent: JP63203632 (1988-08-23)
Inventors: TSUJII YASUHIRO; UENISHI HISAYOSHI, KIMURA TOKIYA
Applicant: ISHIHARA SANGYO KAISHA LTD
Application: JP19870035316 (1987-02-18)
IPC: C 07 B 45/06; C 07 D 213/70
(Skipping summary description, theory stuff for now ...)
Example of Execution 1
181.5g 2-chloro-3-trifluoromethylpyridine and 114g thiourea were dissolved in 91g acetic acid, and reacted at 90°C for 1 hour. After the end of this reaction, and after the reaction mixture cooled, 600ml of 20% sodium hydroxide solution was thrown in; next the aqueous layer was washed with methylene chloride and afterwards the pH of the solution was adjusted to 6-7 with hydrochloric acid; the formed crystals were separated, washed, and dried, to obtain 166g 2-mercapto-3-triflouromethylpyridine (yield 92.7%). Furthermore, in this reaction process bad odors were not generated.
Comparison example
A reaction was performed in a similar manner to Example of Execution 1 above with the exeptions that the 91g of acetic acid was replaced with 1L of ethanol, the reaction temperature was 80 instead of 90°C, and the reaction time was 26 hours instead of 1 hour. 98.9g of the target compound was obtained (yield 55%) upon completion of this halide compound and thiourea reaction. Also, in this reaction process a bad odor was generated.
Examples of Execution 2-15
These were performed in the manner of Example of Execution 1, with the raw materials used shown in the following Table 1-1, and the reaction conditions shown in Table 1-2; results are shown in Table 1-2.
Ex. No. |
Raw materials |
||||
Halide substance |
Specific Carboxylic Acid |
thiourea |
|||
Type |
Quantity |
Type |
Quantity(g) |
||
2 |
2-chloro-5-trifluoromethylpyridine | 200 g |
acetic acid |
100 g |
167 g |
3 |
2-chloro-3-trifluoromethylpyridine | 363 g |
50% aqueous acetic acid |
360 g |
228 g |
4 |
2-fluoro-3-trifluoromethylpyridine | 16.5 g |
acetic acid |
16 g |
15.2 g |
5 |
2-bromo-3-methylpyridine | 17.2 g |
acetic acid |
8 g |
15.2 g |
6 |
2-chloro-5-hydroxycarbonylpyridine | 10 g |
acetic acid |
10 g |
7.8 g |
7 |
2-chloro-5-aminocarbonylpyridine | 5.0 g |
acetic acid |
10 g |
4.9 g |
8 |
2-chloro-5-cyanopyridine | 4.0 g |
acetic acid |
4 g |
4.4 g |
9 |
2-chloro-5-nitropyridine | 10.0 g |
acetic acid |
5 g |
9.6 g |
10 |
2,3,5-trichloropyridine | 36.5 g |
acetic acid |
18 g |
22.8 g |
11 |
2-bromopyridine | 10.0 g |
acetic acid |
5 g |
9.6 g |
12 |
5-bromo-2-chloropyridine | 10.0 g |
acetic acid |
10 g |
7.7 g |
13 |
5-bromo-3-methylene thiazole | 3.0 g |
acetic acid |
10 g |
2.6 g |
14 |
benzylbromide | 4.5 g |
acetic acid |
5 g |
4.4 g |
15 |
2-bromothiazole | 6.0 g |
acetic acid |
6 g |
5.6 g |
| Ex. No. |
Reaction Condition of Alkaline Substance |
Goal Substance |
||||
Temp |
Time |
Alkali Type |
Alkali Quantity |
Species |
Yield |
|
2 |
70-80°C |
1.3 h |
NaOH |
174g |
2-mercapto-5-trifluoromethylpyridine | 88.3% |
3 |
95-100°C |
1 h |
NaOH |
310g |
2-mercapto-3-trifluoromethylpyridine | 94.3% |
4 |
110°C |
6 h |
NaOH |
14g |
2-mercapto-3-trifluoromethylpyridine | 59% |
5 |
95°C |
1 h |
NaOH |
15g |
2-mercapto-3-methylpyridine | 53.6% |
6 |
95°C |
1 h |
NaOH |
20g |
2-mercapto-5-hydroxycarbonylpyridine | 83.3% |
7 |
95°C |
0.3 h |
NaOH |
10g |
2-mercapto-5-aminocarbonylpyridine | 91.6% |
8 |
85°C |
2 h |
NaOH |
5g |
2-mercapto-5-cyanopyridine | 94.1% |
9 |
90°C |
0.5 h |
NaOH |
10g |
2-mercapto-5-nitropyridine | 90% |
10 |
100°C |
2 h |
NaOH |
30g |
2-mercapto-3,5-dichloropyridine | 73.3% |
11 |
70°C |
2 h |
NaOH |
9.5g |
2-mercapto-pyridine | 95% |
12 |
80°C |
0.3 h |
NaOH |
8g |
5-bromo-2-mercaptopyridine | 98% |
13 |
75°C |
2 h |
NaOH |
8g |
3-methyl-5-mercaptoisothiazole | 96% |
14 |
80°C |
1 h |
NaOH |
3g |
benzylthio alcohol | 92% |
15 |
80°C |
0.5 h |
NaOH |
7g |
2-mercaptothiazole | 95% |
Similarly with the exception of the halide substance, from for example 2-bromopyrazine, 3-bromopyridazine, 4-bromo-1-methylimidazole, 2-bromo oxazole, 5-bromo-4-nitro-isoxazole, 5-bromo-1-methyl-4-nitropyrazole, 3-bromo-1,2,4-triazole, and 2-bromotriazine, used in the reaction of Examples of Execution 1-15 above, 2-mercaptopyrazine, 3-mercaptopyridazine, 4-mercapto-1-methyl-imidazole, 2-mercapto oxazole, 5-mercapto-4-nitroisoxazole, 5-mercapto-1-methyl-4-nitropyrazole, 3-mercapto-1,2,4-triazole, and 2-mercaptotriazine would be obtained.
{Invention conclusion....)