JPH10298156A - Production of substituted halomethylphenylcarbamic acid esters - Google Patents
Production of substituted halomethylphenylcarbamic acid estersInfo
- Publication number
- JPH10298156A JPH10298156A JP9125056A JP12505697A JPH10298156A JP H10298156 A JPH10298156 A JP H10298156A JP 9125056 A JP9125056 A JP 9125056A JP 12505697 A JP12505697 A JP 12505697A JP H10298156 A JPH10298156 A JP H10298156A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- substituted
- compound
- formula
- halomethylphenylcarbamic
- 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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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は農薬分野の新規殺虫
剤として有用な３−（３−ピリジルメチルアミノ）−
３，４−ジヒドロ−２（１Ｈ）−キナゾリノン誘導体を
製造するための中間体化合物である置換ハロメチルフェ
ニルカルバミド酸エステル類の製造方法に関するもので
ある。The present invention relates to 3- (3-pyridylmethylamino)-useful as a novel insecticide in the field of agrochemicals.
The present invention relates to a method for producing a substituted halomethylphenylcarbamic acid ester which is an intermediate compound for producing a 3,4-dihydro-2 (1H) -quinazolinone derivative.
【０００２】[0002]
【従来の技術】特開平８−３２５２３９号公報には、本
発明で製造される一般式（Ｉ）で表される３−（３−ピ
リジルメチルアミノ）−３，４−ジヒドロ−２（１Ｈ）
−キナゾリノン誘導体、該化合物が殺虫剤として有用で
あること及びその製造方法が記載されている。Collect.
Czech. Chem. Commn. (Vol.55), 752(1990) にイソシア
ン酸 ２−メチルフェニルをハロゲン化し、次いで低級
アルコールと反応させる方法が記載されている。2. Description of the Related Art JP-A-8-325239 discloses 3- (3-pyridylmethylamino) -3,4-dihydro-2 (1H) represented by the general formula (I) produced by the present invention.
-Quinazolinone derivatives, their usefulness as insecticides and their preparation are described. Collect.
Czech. Chem. Commn. (Vol. 55), 752 (1990) describes a method in which 2-methylphenyl isocyanate is halogenated and then reacted with a lower alcohol.
【化３】 又、特開昭６３−１４６８８１号公報には、置換２−ア
ミノベンジルアルコール類をカーバメート化後、ハロゲ
ン化する反応が記載されている。Embedded image JP-A-63-146881 describes a reaction in which substituted 2-aminobenzyl alcohols are carbamated and then halogenated.
【化４】 Embedded image
【０００３】[0003]
【発明が解決しようとする課題】上記文献記載の方法で
は、原料化合物であるイソシアン酸エステル類及び置換
２−アミノベンジルアルコール類が高価であり、取扱面
で困難な原料化合物であり、工業的には不利であるの
で、経済性及び実用性の面から新たな製造方法が望まれ
ている。According to the methods described in the above-mentioned documents, the raw material compounds, isocyanate esters and substituted 2-aminobenzyl alcohols, are expensive, are difficult to handle, and are industrially difficult. Is disadvantageous, and a new manufacturing method is desired from the viewpoint of economy and practicality.
【０００４】[0004]
【課題を解決するための手段】本発明者らは置換ハロメ
チルフェニルカルバミド酸エステル類の新規な製造方法
を開発すべく、鋭意研究を重ねた結果、本発明を見い出
したものである。本発明の製造方法を、例えば図式的に
示すと以下のとおり示すことができる。Means for Solving the Problems The present inventors have conducted intensive studies in order to develop a novel method for producing substituted halomethylphenylcarbamic acid esters, and have found the present invention. The production method of the present invention can be schematically shown as follows, for example.
【化５】 （式中、Ｒは(C1-C10)アルキル基を示し、Ｒ1 は同一又
は異なっても良く、水素原子、ハロゲン原子、(C1-C5)
アルコキシ基又は(C1-C5) アルコキシカルボニル基から
選択される１〜４個の置換基を示し、Ｘはハロゲン原子
を示す。） 一般式(II)で表される化合物を触媒及び不活性溶媒の存
在下にハロゲン化することにより一般式(I) で表される
置換ハロメチルフェニルカルバミド酸エステル類を製造
することができる。Embedded image (Wherein, R represents a (C 1 -C 10 ) alkyl group, and R 1 may be the same or different and include a hydrogen atom, a halogen atom, (C 1 -C 5 )
It represents 1 to 4 substituents selected from an alkoxy group and a (C 1 -C 5 ) alkoxycarbonyl group, and X represents a halogen atom. The substituted halomethylphenylcarbamic acid esters represented by the general formula (I) can be produced by halogenating the compound represented by the general formula (II) in the presence of a catalyst and an inert solvent.
【０００５】本反応で使用する不活性溶媒としては、本
反応の進行を著しく阻害しないものであれば良く、例え
ばジクロロメタン、クロロホルム、四塩化炭素、エチレ
ンジクロリド等のハロゲン化炭化水素類、ベンゼン、モ
ノクロロベンゼン、モノフルオロベンゼン等の芳香族炭
化水素類、酢酸等の脂肪族カルボン酸類を例示すること
ができ、これらの不活性溶媒は単独で、又は２種以上混
合して使用することができる。ハロゲン化剤としては、
例えば塩素、臭素、Ｎ−ハロスクシンイミド、スルフリ
ルクロリド、次亜ハロゲン酸ｔ−ブチル、トリクロロメ
タンスルホン酸ハロゲニド、ジブロモメルドラム酸等の
ハロゲン化剤を使用することができ、ハロゲン化剤の使
用量は一般式(II)で表される化合物に対して等モル量使
用すれば良いが、若干の過剰量使用するのが好ましい。The inert solvent used in the present reaction may be any solvent which does not significantly inhibit the progress of the present reaction. Examples of the inert solvent include halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride and ethylene dichloride, benzene and monochloride. Examples thereof include aromatic hydrocarbons such as chlorobenzene and monofluorobenzene, and aliphatic carboxylic acids such as acetic acid. These inert solvents can be used alone or in combination of two or more. As the halogenating agent,
For example, a halogenating agent such as chlorine, bromine, N-halosuccinimide, sulfuryl chloride, t-butyl hypohalite, halogenide trichloromethanesulfonate, dibromomerdrum acid, etc. can be used. It may be used in an equimolar amount with respect to the compound represented by the general formula (II), but it is preferable to use a slight excess.
【０００６】触媒としてはベンゾイルパーオキサイド
（ＢＰＯ）等の過酸化物、アゾビスイソブチロニトリル
（ＡＩＢＮ）等のアゾビス系化合物の他に、光照射下で
行うことも可能である。触媒の使用量は基質に対して
０．１〜２０重量％、好ましくは０．１〜５重量％の範
囲で使用すれば良い。反応温度は０℃〜１３０℃の範囲
から適宜選択して行えば良く、好ましくは６０℃〜９０
℃の範囲である。反応時間は反応規模、反応温度等によ
り一定しないが、数分〜４８時間の範囲で行えば良い。
反応終了後、目的物を含む反応系から常法により単離
し、必要に応じて精製することもできる。As a catalyst, in addition to peroxides such as benzoyl peroxide (BPO) and azobis compounds such as azobisisobutyronitrile (AIBN), it is also possible to carry out the reaction under light irradiation. The catalyst may be used in an amount of 0.1 to 20% by weight, preferably 0.1 to 5% by weight, based on the substrate. The reaction temperature may be appropriately selected from the range of 0 ° C to 130 ° C, and is preferably 60 ° C to 90 ° C.
It is in the range of ° C. The reaction time is not constant depending on the reaction scale, the reaction temperature and the like, but may be in the range of several minutes to 48 hours.
After completion of the reaction, it can be isolated from the reaction system containing the target substance by a conventional method, and can be purified if necessary.
【０００７】[0007]
【発明の実施の形態】以下に本発明の代表的な実施例を
例示するが、本発明はこれらに限定されるものではな
い。 実施例１．メチル ２−クロロメチルフェニルカーバメ
ートの製造DESCRIPTION OF THE PREFERRED EMBODIMENTS Representative examples of the present invention will be described below, but the present invention is not limited thereto. Embodiment 1 FIG. Production of methyl 2-chloromethylphenylcarbamate
【化６】 １−１ １６．５ｇのメチル ２−メチルフェニルカーバメート
と０．８２ｇのＡＩＢＮを２００ｍｌのモノクロロベン
ゼンに溶解し、８０℃で１６．２ｇのスルフリルクロリ
ドを約４５分間で滴下し、滴下後３０分攪拌下に反応を
行った。反応終了後、反応液を室温まで冷却し、チオ硫
酸ナトリウム水溶液、炭酸水素ナトリウム水溶液及び飽
和食塩水で洗浄し硫酸マグネシウムで乾燥後、有機層を
濃縮することにより白色結晶として目的物１９．３ｇを
得た。この白色結晶はガスクロマトグラフ分析でメチル
２−クロロメチルフェニルカーバメートが８３％の収
率で生成したことを示していた。 物性：ｍ．ｐ．１０９−１１０℃ Ｈ−ＮＭＲ（ＣＤＣｌ3 、δ値(ppm) ） 3.8(3H,s), 4.6(2H,s), 6.8-7.5(4H,m), 7.8-8.0(1H,
m).Embedded image 1-1 16.5 g of methyl 2-methylphenylcarbamate and 0.82 g of AIBN are dissolved in 200 ml of monochlorobenzene, and 16.2 g of sulfuryl chloride is added dropwise at 80 ° C. in about 45 minutes, and stirred for 30 minutes after the addition. The reaction was performed below. After completion of the reaction, the reaction solution was cooled to room temperature, washed with an aqueous solution of sodium thiosulfate, an aqueous solution of sodium hydrogen carbonate and saturated saline, dried over magnesium sulfate, and concentrated to obtain 19.3 g of the desired product as white crystals. Obtained. The white crystals showed by gas chromatography analysis that methyl 2-chloromethylphenylcarbamate was formed in a yield of 83%. Physical properties: m. p. 109-110 ° C H-NMR (CDCl 3 , δ value (ppm)) 3.8 (3H, s), 4.6 (2H, s), 6.8-7.5 (4H, m), 7.8-8.0 (1H,
m).
【０００８】１−２ １６．５ｇのメチル ２−メチルフェニルカーバメート
と０．８２ｇのＡＩＢＮを２００ｍｌのモノフルオロベ
ンゼンに溶解し、８０℃で９．２３ｇの塩素を約４５分
間で導入し、導入後１５分攪拌下に反応を行った。反応
終了後、反応液を室温まで冷却し、チオ硫酸ナトリウム
水溶液、炭酸水素ナトリウム水溶液及び飽和食塩水で洗
浄し硫酸マグネシウムで乾燥後、有機層を濃縮すること
により白色結晶として目的物１９．３ｇを得た。得られ
た白色結晶のガスクロマトグラフ分析の結果メチル ２
−クロロメチルフェニルカーバメートが８３％の収率で
生成したことを示していた。 １−３ 実施例１−２で使用したＡＩＢＮをＢＰＯ（１ｇ）にか
えて同様の反応を行い、白色結晶として目的物１９．０
ｇを得た。この白色結晶のガスクロマトグラフ分析はメ
チル ２−クロロメチルフェニルカーバメートが７８％
の収率で生成したことを示していた。1-2 16.5 g of methyl 2-methylphenylcarbamate and 0.82 g of AIBN are dissolved in 200 ml of monofluorobenzene, and 9.23 g of chlorine are introduced at 80 ° C. for about 45 minutes. The reaction was carried out under stirring for 15 minutes. After completion of the reaction, the reaction solution was cooled to room temperature, washed with an aqueous solution of sodium thiosulfate, an aqueous solution of sodium hydrogen carbonate and saturated saline, dried over magnesium sulfate, and concentrated to obtain 19.3 g of the desired product as white crystals. Obtained. As a result of gas chromatography analysis of the obtained white crystal, methyl 2 was obtained.
-Chloromethyl phenyl carbamate had been formed in a yield of 83%. 1-3 The same reaction was carried out by replacing AIBN used in Example 1-2 with BPO (1 g), and the target compound was obtained as white crystals, 19.0.
g was obtained. Gas chromatographic analysis of the white crystals showed 78% methyl 2-chloromethylphenylcarbamate.
It was shown to be produced in a yield of
【０００９】１−４1-4
【表１】 [Table 1]
【００１０】実施例２．メチル ２−ブロモメチル−３
−フルオロフェニルカーバメートの製造Embodiment 2 FIG. Methyl 2-bromomethyl-3
-Production of fluorophenyl carbamate
【化７】 ３．６６ｇのメチル ３−フルオロ−２−メチルフェニ
ルカーバメート、０．１６ｇのＡＩＢＮ及び３．５６ｇ
のＮ−ブロモスクシンイミドを４０ｍｌの四塩化炭素に
加えて４時間加熱還流下に反応を行った。反応終了後、
反応液を室温まで冷却し、塩を濾過して除去し、有機層
を濃縮することにより白色結晶として目的物を４．９ｇ
得た。この白色結晶のガスクロマトグラフ分析はメチル
２−ブロモメチル−３−フルオロフェニルカーバメー
トが９３％の収率で生成したことを示していた。 Ｈ−ＮＭＲ（ＣＤＣｌ3 、δ値(ppm) ） 3.8(3H,s), 4.55(2H,s), 6.8-7.9(2H,m), 7.25-7.35(1
H,m), 7.68(1H,d).Embedded image 3.66 g of methyl 3-fluoro-2-methylphenylcarbamate, 0.16 g of AIBN and 3.56 g
Of N-bromosuccinimide was added to 40 ml of carbon tetrachloride, and the mixture was reacted under heating and refluxing for 4 hours. After the reaction,
The reaction solution was cooled to room temperature, salts were removed by filtration, and the organic layer was concentrated to give 4.9 g of the desired product as white crystals.
Obtained. Gas chromatographic analysis of the white crystals indicated that methyl 2-bromomethyl-3-fluorophenylcarbamate was formed in 93% yield. H-NMR (CDCl 3 , δ value (ppm)) 3.8 (3H, s), 4.55 (2H, s), 6.8-7.9 (2H, m), 7.25-7.35 (1
H, m), 7.68 (1H, d).
【００１１】実施例３．メチル ２−ブロモメチルフェ
ニルカーバメートの製造Embodiment 3 FIG. Production of methyl 2-bromomethylphenylcarbamate
【化８】 ３−１ １ｇのメチル ２−メチルフェニルカーバメートを１５
ｍｌのモノフルオロベンゼンに溶解し、８０℃で外部か
ら１００Ｗタングステンランプを照射した。該反応液に
０．６３ｇの臭素を９０分かけて加え、その後３０分間
反応を行った。反応終了後、実施例１と同様にすること
により白色結晶として１．３ｇの目的物を得た。この白
色結晶のガスクロマトグラフ分析はメチル ２−ブロモ
メチルフェニルカーバメートが８４％の収率で生成した
ことを示していた。 Ｈ−ＮＭＲ（ＣＤＣｌ3 、δ値(ppm) ） 3.8(3H,s), 4.5(2H,s), 6.8(1H,brs), 7.0-7.4(3H,m),
7.8-7.9(1H,d). ３−２ 実施例３−１で使用した光触媒をＡＩＢＮ（Ｏ．０５
ｇ）にかえて同様の反応を行い、白色結晶として目的物
を１．３ｇ得た。この白色結晶のガスクロマトグラフ分
析はメチル ２−ブロモメチルフェニルカーバメートが
８０％の収率で生成したことを示していた。Embedded image 3-1 1 g of methyl 2-methylphenylcarbamate was added to 15
The mixture was dissolved in ml of monofluorobenzene and irradiated with a 100 W tungsten lamp from outside at 80 ° C. 0.63 g of bromine was added to the reaction solution over 90 minutes, and the reaction was performed for 30 minutes. After completion of the reaction, 1.3 g of the target product was obtained as white crystals by the same procedure as in Example 1. Gas chromatographic analysis of the white crystals indicated that methyl 2-bromomethylphenylcarbamate was formed in 84% yield. H-NMR (CDCl 3 , δ value (ppm)) 3.8 (3H, s), 4.5 (2H, s), 6.8 (1H, brs), 7.0-7.4 (3H, m),
7.8-7.9 (1H, d). 3-2 The photocatalyst used in Example 3-1 was AIBN (0.05).
The same reaction was carried out in place of g) to obtain 1.3 g of the desired product as white crystals. Gas chromatographic analysis of the white crystals indicated that methyl 2-bromomethylphenylcarbamate was formed in 80% yield.
─────────────────────────────────────────────────────
────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成１０年４月２２日[Submission date] April 22, 1998
【手続補正１】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００２[Correction target item name] 0002
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【０００２】[0002]
【従来の技術】特開平８−３２５２３９号公報には、本
発明で製造される一般式（Ｉ）で表される置換ハロメチ
ルフェニルカルバミド酸エステル類を中間化合物とする
３−（３−ピリジルメチルアミノ）−３，４−ジヒドロ
−２（１Ｈ）−キナゾリノン誘導体、該化合物が殺虫剤
として有用であること及びその製造方法が記載されてい
る。Ｃｏｌｌｅｃｔ．Ｃｚｅｃｈ．Ｃｈｅｍ．Ｃｏｍｍ
ｎ．（Ｖｏｌ．５５），７５２（１９９０）にイソシア
ン酸 ２−メチルフェニルをハロゲン化し、次いで低級
アルコールと反応させる方法が記載されている。2. Description of the Related Art Japanese Unexamined Patent Publication (Kokai) No. 8-325239 discloses a substituted halomethyl compound represented by the general formula (I) produced by the present invention.
A 3- (3-pyridylmethylamino) -3,4-dihydro-2 (1H) -quinazolinone derivative using a ruphenylcarbamic acid ester as an intermediate compound, that the compound is useful as an insecticide, and a method for producing the same. Have been described. Collect. Czech. Chem. Comm
n. (Vol. 55), 752 (1990) describes a method in which 2-methylphenyl isocyanate is halogenated and then reacted with a lower alcohol.
【化３】 又、特開昭６３−１４６８８１号公報には、置換２−ア
ミノベンジルアルコール類をカーバメート化後、ハロゲ
ン化する反応が記載されている。Embedded image JP-A-63-146881 describes a reaction in which substituted 2-aminobenzyl alcohols are carbamated and then halogenated.
【化４】 Embedded image
【手続補正２】[Procedure amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００５[Correction target item name] 0005
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【０００５】本反応で使用する不活性溶媒としては、本
反応の進行を著しく阻害しないものであれば良く、例え
ばジクロロメタン、クロロホルム、四塩化炭素、エチレ
ンジクロリド等のハロゲン化炭化水素類、ベンゼン、モ
ノクロロベンゼン、モノフルオロベンゼン等の芳香族炭
化水素類、酢酸等の脂肪族カルボン酸類を例示すること
ができ、これらの不活性溶媒は単独で、又は２種以上混
合して使用することができる。ハロゲン化剤としては、
例えば塩素、臭素、Ｎ−ハロスクシイミド、スルフリル
クロリド、次亜ハロゲン酸ｔ−ブチル、トリクロロメタ
ンスルホン酸ハロゲニド、ジブロモメルドラム酸等のハ
ロゲン化剤を使用することができ、ハロゲン化剤の使用
量は一般式（ＩＩ）で表される化合物に対して等モル量
使用すれば良いが、若干の過剰量使用するのが好まし
い。The inert solvent used in the present reaction may be any solvent which does not significantly inhibit the progress of the present reaction. Examples of the inert solvent include halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride and ethylene dichloride, benzene and monochloride. Examples thereof include aromatic hydrocarbons such as chlorobenzene and monofluorobenzene, and aliphatic carboxylic acids such as acetic acid. These inert solvents can be used alone or in combination of two or more. As the halogenating agent,
For example, halogenating agents such as chlorine, bromine, N-halosuccinimide , sulfuryl chloride, t-butyl hypohalite, halogenide trichloromethanesulfonate, and dibromomerdrum acid can be used. The compound may be used in an equimolar amount to the compound represented by the formula (II), but it is preferable to use a slight excess amount.
Claims (1)
は異なっても良く、水素原子、ハロゲン原子、(C1-C5)
アルコキシ基又は(C1-C5) アルコキシカルボニル基から
選択される１〜４個の置換基を示す。）で表される化合
物を触媒及びハロゲン化剤の存在下にハロゲン化するこ
とを特徴とする一般式(I) 【化２】 （式中、Ｒ及びＲ1 は前記に同じくし、Ｘはハロゲン原
子を示す。）で表される置換ハロメチルフェニルカルバ
ミド酸エステル類の製造方法。1. A compound of the general formula (II) (Wherein, R represents a (C 1 -C 10 ) alkyl group, and R 1 may be the same or different and include a hydrogen atom, a halogen atom, (C 1 -C 5 )
And 1 to 4 substituents selected from an alkoxy group and a (C 1 -C 5 ) alkoxycarbonyl group. Wherein the compound of formula (I) is halogenated in the presence of a catalyst and a halogenating agent. (Wherein, R and R 1 are as defined above, and X represents a halogen atom.) A method for producing a substituted halomethylphenylcarbamic acid ester represented by the formula:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9125056A JPH10298156A (en) | 1997-04-28 | 1997-04-28 | Production of substituted halomethylphenylcarbamic acid esters |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9125056A JPH10298156A (en) | 1997-04-28 | 1997-04-28 | Production of substituted halomethylphenylcarbamic acid esters |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10298156A true JPH10298156A (en) | 1998-11-10 |
Family
ID=14900736
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9125056A Pending JPH10298156A (en) | 1997-04-28 | 1997-04-28 | Production of substituted halomethylphenylcarbamic acid esters |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10298156A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005123695A1 (en) * | 2004-06-22 | 2005-12-29 | Nihon Nohyaku Co., Ltd. | Process for producing iminoquinazolinone derivative |
| JP2015532262A (en) * | 2012-09-28 | 2015-11-09 | 武田薬品工業株式会社 | Method for producing thienopyrimidine derivative |
| CN110698416A (en) * | 2019-12-16 | 2020-01-17 | 湖南速博生物技术有限公司 | Preparation method of pyridine quinazoline intermediate |
-
1997
- 1997-04-28 JP JP9125056A patent/JPH10298156A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005123695A1 (en) * | 2004-06-22 | 2005-12-29 | Nihon Nohyaku Co., Ltd. | Process for producing iminoquinazolinone derivative |
| JP2015532262A (en) * | 2012-09-28 | 2015-11-09 | 武田薬品工業株式会社 | Method for producing thienopyrimidine derivative |
| US9758528B2 (en) | 2012-09-28 | 2017-09-12 | Takeda Pharmaceutical Company Limited | Production method of thienopyrimidine derivative |
| US10150778B2 (en) | 2012-09-28 | 2018-12-11 | Takeda Pharmaceutical Company Limited | Production method of thienopyrimidine derivative |
| US10464945B2 (en) | 2012-09-28 | 2019-11-05 | Takeda Pharmaceutical Company Limited | Crystalline forms of thienopyrimidine derivative |
| US10544160B2 (en) | 2012-09-28 | 2020-01-28 | Takeda Pharmaceutical Company Limited | Production method of thienopyrimidine derivative |
| US11053257B2 (en) | 2012-09-28 | 2021-07-06 | Takeda Pharmaceutical Company Limited | Production method of thienopyrimidine derivative |
| US11731983B2 (en) | 2012-09-28 | 2023-08-22 | Takeda Pharmaceutical Company Limited | Production method of thienopyrimidine derivative |
| US11795178B2 (en) | 2012-09-28 | 2023-10-24 | Takeda Pharmaceutical Company Limited | Compositions of thienopyrimidine derivatives |
| CN110698416A (en) * | 2019-12-16 | 2020-01-17 | 湖南速博生物技术有限公司 | Preparation method of pyridine quinazoline intermediate |
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