JPH0231713B2 - 44HIDOROKISHII55HAROGENOO66ARUKIRUPIRIMIJINNOHAROGENKASUISOSANENNOSEIHO - Google Patents
44HIDOROKISHII55HAROGENOO66ARUKIRUPIRIMIJINNOHAROGENKASUISOSANENNOSEIHOInfo
- Publication number
- JPH0231713B2 JPH0231713B2 JP10375482A JP10375482A JPH0231713B2 JP H0231713 B2 JPH0231713 B2 JP H0231713B2 JP 10375482 A JP10375482 A JP 10375482A JP 10375482 A JP10375482 A JP 10375482A JP H0231713 B2 JPH0231713 B2 JP H0231713B2
- Authority
- JP
- Japan
- Prior art keywords
- hydroxy
- alkylpyrimidine
- reaction
- halogeno
- methylpyrimidine
- 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.)
- Expired - Lifetime
Links
- 150000003839 salts Chemical class 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 6
- -1 aminopyrimidine compounds Chemical class 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- LHRIUKSRPHFASO-UHFFFAOYSA-N 6-methyl-1h-pyrimidin-4-one Chemical compound CC1=CC(=O)N=CN1 LHRIUKSRPHFASO-UHFFFAOYSA-N 0.000 description 4
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical class Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- JRNVZBWKYDBUCA-UHFFFAOYSA-N N-chlorosuccinimide Chemical compound ClN1C(=O)CCC1=O JRNVZBWKYDBUCA-UHFFFAOYSA-N 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003230 pyrimidines Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- VCPXZIUQCXEVCU-UHFFFAOYSA-N 4-ethylpyrimidine Chemical compound CCC1=CC=NC=N1 VCPXZIUQCXEVCU-UHFFFAOYSA-N 0.000 description 1
- YIDUVRHFPFLCLN-UHFFFAOYSA-N 5-chloro-6-methyl-1h-pyrimidin-4-one Chemical compound CC=1NC=NC(=O)C=1Cl YIDUVRHFPFLCLN-UHFFFAOYSA-N 0.000 description 1
- BPNCSGUMGMVACS-UHFFFAOYSA-N 5-ethyl-1h-pyrimidin-6-one Chemical compound CCC1=CN=CNC1=O BPNCSGUMGMVACS-UHFFFAOYSA-N 0.000 description 1
- MQYCUOZXEJXUNU-UHFFFAOYSA-N 6-butyl-1h-pyrimidin-4-one Chemical compound CCCCC1=CC(=O)N=CN1 MQYCUOZXEJXUNU-UHFFFAOYSA-N 0.000 description 1
- QQFOXWFPCYCCJS-UHFFFAOYSA-N 6-propyl-1h-pyrimidin-4-one Chemical compound CCCC1=CC(=O)N=CN1 QQFOXWFPCYCCJS-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical class F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 230000000895 acaricidal effect Effects 0.000 description 1
- 239000000642 acaricide Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- FDRYQDWXFZBBAD-UHFFFAOYSA-N hydron;6-methyl-1h-pyrimidin-2-one;chloride Chemical compound Cl.CC1=CC=NC(=O)N1 FDRYQDWXFZBBAD-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Description
【発明の詳細な説明】
本発明は、４−ヒドロキシ−５−ハロゲノ−６
−アルキルピリミジンのハロゲン化水素酸塩の新
規製法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention provides 4-hydroxy-5-halogeno-6
- This invention relates to a new method for producing a hydrohalide salt of an alkylpyrimidine.
４−ヒドロキシ−５−ハロゲノ−６−アルキル
ピリミジンは、例えば殺虫剤あるいは殺ダニ剤な
どの農薬として有用なアミノピリミジン系化合物
の合成中間体である。例えば、前記ピリミジン類
をオキシ塩化リンと反応させ、４位のヒドロキシ
基をクロル化した後、次いでアミノ化することに
よつて、アミノピリミジン系化合物を得ることが
できる。なお、前記オキシ塩化リンとの反応にお
いて、ピリミジン類が遊離の形態の場合は、その
反応が極めて激しい状態で進行し、反応操作のコ
ントロールが難しく、副生物が多量生成するが、
一方ピリミジン類が例えばハロゲン化水素酸塩の
如き塩の形態である場合には、反応が温和な状態
でスムースに進行し、目的物の収率、選択率も高
くなる。 4-Hydroxy-5-halogeno-6-alkylpyrimidine is a synthetic intermediate for aminopyrimidine compounds useful as agricultural chemicals such as insecticides and acaricides. For example, an aminopyrimidine compound can be obtained by reacting the pyrimidine with phosphorus oxychloride, chlorinating the 4-position hydroxy group, and then aminating it. In addition, in the reaction with phosphorus oxychloride, if the pyrimidine is in a free form, the reaction proceeds in an extremely violent state, making it difficult to control the reaction operation and producing a large amount of by-products.
On the other hand, when the pyrimidine is in the form of a salt such as a hydrohalide, the reaction proceeds mildly and smoothly, and the yield and selectivity of the target product are high.
従来、４−ヒドロキシ−５−ハロゲノ−６−ア
ルキルピリミジンの製法として、Tetrahedron22
(8)2401〜2412（1961）には、クロロホルム溶媒中、
４−ヒドロキシ−６−アルキルピリミジンにＮ−
ハロゲノコハク酸イミドを作用させる方法につき
提案がなされている。しかしこの方法では、目的
物のピリミジン類は使用された溶媒に溶けやすい
遊離の形態で得られるため、目的物と副生物およ
び未反応原料との分離にはん雑な操作を必要とす
る。また、目的物が塩の形態で得られないため、
前記の如くオキシ塩化リンとの反応においても、
不都合をきたす。さらに該方法は、使用されるＮ
−ハロゲノコハク酸イミドは極めて高価で、しか
も入手しにくい物質である、など工業的に多くの
問題点を有している。 Conventionally, as a method for producing 4-hydroxy-5-halogeno-6-alkylpyrimidine, Tetrahedron 22
(8) 2401-2412 (1961), in chloroform solvent,
N- to 4-hydroxy-6-alkylpyrimidine
Proposals have been made regarding methods for causing halogenosuccinimides to act. However, in this method, the target pyrimidine is obtained in a free form that is easily soluble in the solvent used, and therefore, complicated operations are required to separate the target product from by-products and unreacted raw materials. In addition, since the target product cannot be obtained in the form of a salt,
As mentioned above, in the reaction with phosphorus oxychloride,
cause inconvenience. Furthermore, the method includes the use of N
- Halogenosuccinimide has many problems industrially, such as being extremely expensive and difficult to obtain.
またJ.A.C.S.、70 1753〜1756（1948）には、
ピリミジン類を直接ハロゲン化し、５−ハロゲノ
ピリミジン類を製造する方法につき提案されてい
る。 Also in JACS, 70 1753-1756 (1948),
A method for producing 5-halogenopyrimidines by directly halogenating pyrimidines has been proposed.
この方法では、塩化鉄が触媒として使用されて
いるが、目的物はやはり遊離の形態で得られてお
りしかもその収率も約20％程度と極めて低いもの
である。なお該方法では、本発明の如きピリミジ
ン類については、対象とされていない。 In this method, iron chloride is used as a catalyst, but the target product is still obtained in a free form, and the yield is extremely low at about 20%. Note that this method does not target pyrimidines such as those of the present invention.
本発明者らは、前記農薬の合成中間体として有
用な、４−ヒドロキシ−５−ハロゲノ−６−アル
キルピリミジンを、工業的有利にしかも前記理由
から塩の形態で製造できる方法を開発することを
目的とし、鋭意研究を行つた。その結果、４−ヒ
ドロキシ−６−アルキルピリミジンを、意外にも
前記塩化鉄を触媒として用いることなく、ハロゲ
ンと直接接触させれば、極めて高収率、高選択率
で４−ヒドロキシ−５−ハロゲノ−６−アルキル
ピリミジンをその使用に供したハロゲンに対応す
るハロゲン化水素酸塩の形態で製造できることを
見い出し、本発明を完成するに到つた。 The present inventors aimed to develop a method for producing 4-hydroxy-5-halogeno-6-alkylpyrimidine, which is useful as a synthetic intermediate for the above-mentioned agricultural chemicals, in the form of a salt, which is industrially advantageous and for the above-mentioned reasons. With this goal in mind, we conducted extensive research. As a result, surprisingly, when 4-hydroxy-6-alkylpyrimidine was brought into direct contact with halogen without using the aforementioned iron chloride as a catalyst, 4-hydroxy-5-halogen was produced in extremely high yield and high selectivity. It has been discovered that -6-alkylpyrimidine can be produced in the form of a hydrohalide salt corresponding to the halogen used, and the present invention has been completed.
すなわち本発明は、溶媒中で、４−ヒドロキシ
−６−アルキルピリミジンとハロゲンとを反応さ
せることによる、４−ヒドロキシ−５−ハロゲノ
−６−アルキルピリミジンのハロゲン化水素酸塩
の製法に関するものである。 That is, the present invention relates to a method for producing a hydrohalide salt of 4-hydroxy-5-halogeno-6-alkylpyrimidine by reacting 4-hydroxy-6-alkylpyrimidine with a halogen in a solvent. .
本発明における反応は、次式に従つて進行す
る。 The reaction in the present invention proceeds according to the following formula.
（ただし式中Ｒはアルキル基を示し、Ｘはハロゲ
ン原子を示す。）
本発明における出発原料である４−ヒドロキシ
−６−アルキルピリミジンとしては、４−ヒドロ
キシ−６−メチルピリミジン、４−ヒドロキシ−
６−エチルピリミジン、４−ヒドロキシ−６−プ
ロピルピリミジン、４−ヒドロキシ−６−ブチル
ピリミジン、４−ヒドロキシ−６−ペンチルピリ
ミジンなど、６位に低級アルキル基の置換した４
−ヒドロキシ−ピリミジン類を挙げることができ
る。 (However, in the formula, R represents an alkyl group, and X represents a halogen atom.) Examples of 4-hydroxy-6-alkylpyrimidine, which is a starting material in the present invention, include 4-hydroxy-6-methylpyrimidine, 4-hydroxy-
4 with a lower alkyl group substituted at the 6-position, such as 6-ethylpyrimidine, 4-hydroxy-6-propylpyrimidine, 4-hydroxy-6-butylpyrimidine, and 4-hydroxy-6-pentylpyrimidine.
-Hydroxy-pyrimidines may be mentioned.
本発明では、まずこれらの４−ヒドロキシ−６
−アルキルピリミジンを溶媒に溶解させる。使用
に供される溶媒としては、出発原料を良く溶かす
ものであればいずれも有用である。かかる溶媒と
しては、例えば酢酸、プロピオン酸などの脂肪
酸、クロロフオルム、四塩化炭素などのハロゲン
化炭化水素を挙げることができるが、これらの中
でも反応速度、生成物の純度などの観点から酢酸
が特に有用である。これらの溶媒は、目的生成物
である４−ヒドロキシ−５−ハロゲノ−６−アル
キルピリミジンのハロゲン化水素酸塩をほとんど
溶かさないため、反応終了後、過などの簡単な
操作で該目的生成物を単離取得することができ
る。なおこれら溶媒の使用量には、特別の規定を
設ける必要はないが、通常出発原料である４−ヒ
ドロキシ−６−アルキルピリミジン１重量部に対
し、１〜20重量部、好ましくは４〜10重量部用い
られる。 In the present invention, first, these 4-hydroxy-6
- Dissolving the alkylpyrimidine in a solvent. Any solvent is useful as long as it dissolves the starting material well. Examples of such solvents include fatty acids such as acetic acid and propionic acid, and halogenated hydrocarbons such as chloroform and carbon tetrachloride. Among these, acetic acid is particularly useful from the viewpoint of reaction rate, product purity, etc. It is. These solvents hardly dissolve the desired product, the hydrohalide salt of 4-hydroxy-5-halogeno-6-alkylpyrimidine, so after the reaction is complete, the desired product can be removed by simple operations such as filtration. It can be isolated and obtained. There is no need to set any special regulations on the amount of these solvents used, but it is usually 1 to 20 parts by weight, preferably 4 to 10 parts by weight, per 1 part by weight of 4-hydroxy-6-alkylpyrimidine, which is the starting material. part is used.
次いで、ハロゲンを導入し反応を行う。ハロゲ
ンは、塩素、フツ素の場合はガス状で導入され、
また臭素、ヨウ素の場合は液状で系内に導入され
るのが好ましい。またハロゲンは、出発原料の４
−ヒドロキシ−６−アルキルピリミジン１モルに
対し、1.0〜５モル、好ましくは１〜２モル用い
られる。 Next, halogen is introduced and a reaction is carried out. Halogens are introduced in gaseous form in the case of chlorine and fluorine,
In the case of bromine and iodine, it is preferable to introduce them into the system in liquid form. In addition, halogen is the starting material 4
The amount used is 1.0 to 5 mol, preferably 1 to 2 mol, per 1 mol of -hydroxy-6-alkylpyrimidine.
反応は、余り高温で行うと目的物が塩の形態で
取得しにくくなるため、通常常温〜100℃、好適
には40〜70℃の温度で行われる。また反応時間
は、0.5〜２時間程度で十分である。 If the reaction is carried out at too high a temperature, it becomes difficult to obtain the target product in the form of a salt, so it is usually carried out at a temperature of room temperature to 100°C, preferably 40 to 70°C. Further, a reaction time of about 0.5 to 2 hours is sufficient.
反応終了後、例えば過などの簡単な操作によ
り、目的生成物、すなわち４−ヒドロキシ−５−
ハロゲノ−６−アルキルピリミジンのハロゲン化
水素酸塩を取得することができる。その具体例と
しては、４−ヒドロキシ−５−ハロゲノ−６−メ
チルピリミジン、４−ヒドロキシ−５−ハロゲノ
−６−エチルピリミジン、４−ヒドロキシ−５−
ハロゲノ−６−プロピルピリミジン、４−ヒドロ
キシ−５−ハロゲノ−６−ブチルピリミジン、４
−ヒドロキシ−５−ハロゲノ−６−ペンチルピリ
ミジンなどの塩酸塩、臭化水素酸塩、フツ化水素
酸塩およびヨウ化水素酸塩を挙げることができ
る。 After the reaction is completed, the desired product, i.e. 4-hydroxy-5-
Hydrohalide salts of halogeno-6-alkylpyrimidines can be obtained. Specific examples include 4-hydroxy-5-halogeno-6-methylpyrimidine, 4-hydroxy-5-halogeno-6-ethylpyrimidine, and 4-hydroxy-5-ethylpyrimidine.
Halogeno-6-propylpyrimidine, 4-hydroxy-5-halogeno-6-butylpyrimidine, 4
Mention may be made of hydrochlorides, hydrobromides, hydrofluorides and hydroiodides such as -hydroxy-5-halogeno-6-pentylpyrimidine.
なお反応液から目的生成物を単離、取得した残
液は、若干の未反応原料および目的生成物を含ん
でいるが、該液はそのまま循環使用することもで
きる。 Note that the residual liquid obtained by isolating and obtaining the target product from the reaction liquid contains some unreacted raw materials and the target product, but the liquid can also be recycled and used as is.
この様に本発明は、従来公知の方法と比較し高
収率、高選択率で目的生成物を得ることができ、
しかも目的物はハロゲン化水素酸塩の形態で得ら
れるため、その単離が極めて容易であり、さらに
前記オキシ塩化リンとの反応に供した場合、極め
て好都合である、など工業的に多くの利点を有し
ている。 As described above, the present invention can obtain the desired product in higher yield and higher selectivity than conventionally known methods.
Moreover, since the target product is obtained in the form of a hydrohalide salt, it is extremely easy to isolate, and furthermore, it has many industrial advantages, such as being extremely convenient when subjected to the reaction with the phosphorus oxychloride. have.
次に、本発明の実施例および比較例を挙げる。 Next, examples of the present invention and comparative examples will be given.
実施例 １
酢酸140mlに、４−ヒドロキシ−６−メチルピ
リミジン22ｇ（0.2モル）を溶解させ、撹拌下に
1.5倍モル量（21.3ｇ）の塩素ガスを系内の温度
が60℃以上にならないようにゆつくりと吹き込ん
だ。次いで、40℃で１時間撹拌を行つた後、反応
液を冷却し析出した結晶を取した。集物を、
少量の冷酢酸で洗浄後、乾燥し、融点194〜197℃
（分解）を有する無色粉状晶の５−クロロ−４−
ヒドロキシ−６−メチルピリミジン塩酸塩31.2ｇ
（収率；86％）を得た。そのC5H5N2ClO・HClと
しての元素分析値は、次の通りであつた。Example 1 22 g (0.2 mol) of 4-hydroxy-6-methylpyrimidine was dissolved in 140 ml of acetic acid, and the mixture was stirred.
Chlorine gas of 1.5 times the molar amount (21.3 g) was slowly blown into the system so that the temperature within the system did not rise above 60°C. Next, after stirring at 40°C for 1 hour, the reaction solution was cooled and the precipitated crystals were collected. collection,
After washing with a small amount of cold acetic acid, drying, melting point 194-197℃
5-chloro-4- of colorless powder crystals with (decomposition)
Hydroxy-6-methylpyrimidine hydrochloride 31.2g
(yield: 86%). Its elemental analysis value as C 5 H 5 N 2 ClO.HCl was as follows.
Ｃ(%) Ｈ(%) Ｎ(%)
計算値 33.17 3.34 15.47
実測値 33.42 3.59 15.80
実施例 ２
酢酸70mlに、４−ヒドロキシ−６−メチルピリ
ミジン11ｇ（0.1モル）を溶解させ、撹拌下に
19.2ｇ（0.12モル）の臭素を系内の温度が50℃以
上にならないようにゆつくり滴下した。次いで40
〜50℃で１時間撹拌を行つた後、反応液を冷却し
析出した結晶を取した。集物を、少量の酢酸
で洗浄後、乾燥し、融点214〜217℃（分解）を有
する淡黄色粉状晶の５−ブロモ−４−ヒドロキシ
−６−メチルピリミジン臭化水素酸塩21.9ｇ（収
率；81％）を得た。そのC5H5N2BrO・HBrとし
ての元素分析値は、次の通りであつた。 C (%) H (%) N (%) Calculated value 33.17 3.34 15.47 Actual value 33.42 3.59 15.80 Example 2 11 g (0.1 mol) of 4-hydroxy-6-methylpyrimidine was dissolved in 70 ml of acetic acid, and the mixture was stirred.
19.2 g (0.12 mol) of bromine was slowly added dropwise so that the temperature in the system did not rise above 50°C. then 40
After stirring at ~50°C for 1 hour, the reaction solution was cooled and the precipitated crystals were collected. The collected material was washed with a small amount of acetic acid and dried to obtain 21.9 g of 5-bromo-4-hydroxy-6-methylpyrimidine hydrobromide (5-bromo-4-hydroxy-6-methylpyrimidine hydrobromide) as pale yellow powder crystals having a melting point of 214-217°C (decomposition). Yield: 81%) was obtained. The elemental analysis value as C 5 H 5 N 2 BrO.HBr was as follows.
Ｃ(%) Ｈ(%) Ｎ(%)
計算値 22.25 2.24 10.38
実測値 22.27 2.26 10.50
比較例
４−ヒドロキシ−６−メチルピリミジン11ｇ
（0.1モル）とＮ−クロルコハク酸イミド13.3ｇ
（0.1モル）をクロロフオルム200ml中に加え、３
時間加熱還流した後、減圧下クロロフオルムを留
去した。得られた結晶に酢酸エチル300mlを加え
加熱撹拌した後、不溶分を取した。次いで集
物をエタノールより再結晶し、融点194〜196℃を
有する無色板状晶の５−クロロ−４−ヒドロキシ
−６−メチルピリミジン6.8ｇ（収率；47％）を
得た。 C(%) H(%) N(%) Calculated value 22.25 2.24 10.38 Actual value 22.27 2.26 10.50 Comparative example 4-hydroxy-6-methylpyrimidine 11g
(0.1 mol) and N-chlorosuccinimide 13.3 g
(0.1 mol) into 200 ml of chloroform,
After heating under reflux for an hour, chloroform was distilled off under reduced pressure. After adding 300 ml of ethyl acetate to the obtained crystals and stirring with heating, insoluble matter was removed. The collected product was then recrystallized from ethanol to obtain 6.8 g (yield: 47%) of colorless plate-like 5-chloro-4-hydroxy-6-methylpyrimidine having a melting point of 194-196°C.
Claims (1)
リミジンとハロゲンとを反応させることを特徴と
する、４−ヒドロキシ−５−ハロゲノ−６−アル
キルピリミジンのハロゲン化水素酸塩の製法。1. A method for producing a hydrohalide salt of 4-hydroxy-5-halogeno-6-alkylpyrimidine, which comprises reacting 4-hydroxy-6-alkylpyrimidine with a halogen in a solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10375482A JPH0231713B2 (en) | 1982-06-18 | 1982-06-18 | 44HIDOROKISHII55HAROGENOO66ARUKIRUPIRIMIJINNOHAROGENKASUISOSANENNOSEIHO |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10375482A JPH0231713B2 (en) | 1982-06-18 | 1982-06-18 | 44HIDOROKISHII55HAROGENOO66ARUKIRUPIRIMIJINNOHAROGENKASUISOSANENNOSEIHO |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58222070A JPS58222070A (en) | 1983-12-23 |
| JPH0231713B2 true JPH0231713B2 (en) | 1990-07-16 |
Family
ID=14362336
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10375482A Expired - Lifetime JPH0231713B2 (en) | 1982-06-18 | 1982-06-18 | 44HIDOROKISHII55HAROGENOO66ARUKIRUPIRIMIJINNOHAROGENKASUISOSANENNOSEIHO |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0231713B2 (en) |
-
1982
- 1982-06-18 JP JP10375482A patent/JPH0231713B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58222070A (en) | 1983-12-23 |
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