TW426671B - Process for the preparation of [(5,6-dicarboxy-3-pyridyl)methyl] ammonium halides - Google Patents

Process for the preparation of [(5,6-dicarboxy-3-pyridyl)methyl] ammonium halides Download PDF

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TW426671B
TW426671B TW086107147A TW86107147A TW426671B TW 426671 B TW426671 B TW 426671B TW 086107147 A TW086107147 A TW 086107147A TW 86107147 A TW86107147 A TW 86107147A TW 426671 B TW426671 B TW 426671B
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Wen-Xue Wu
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American Cyanamid Co
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    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/18—Halogen atoms or nitro radicals
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    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/20—Oxygen atoms
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    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond

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  • Organic Chemistry (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pyridine Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

經濟部中央標準局員工消費合作社印策 42667 1 A7 B7 _____ 五、發明説明（’） 發明背景 [(5,6-二羧基-3-吡啶基）甲基]銨南化物係用作製備除 草5 -(烷氧甲基）-2 - ( 2 ·咪唑啉-2 -基）菸酸，酯及鹽之中間 物。將5 -甲基-2,3-吡啶二羧酸衍生物轉化成[(5,6-二羧 基-3-吡啶基）甲基]銨鹵化物之方法係敘述於美國專利第 5,3 7 8，8 4 3號中。雖然此專利之方法係有用，但更進一步 地研究以發現製備[(5,6-二羧基-3-吡啶基）甲基]銨鹵化 物之新方法。 因此，本發明之目的係提供製備[(5,6-二羧基-3-吡啶 基）甲基]敍ί化物之有用及有效之方法。 發明概要 本發明係提供製備具有構造式I之[(5，6-二羧基-3-吡啶 基）甲基]接卣化物之有用且有效之方法 f z χ·
Ϊ I 入 c〇2h (I) 其中 R，Ri及R2各分別爲C!-C4烷基，且當合在一起時，尺及 R丨可形成視情況以Ο，S或NRs插入之5_或6-元環； R_3爲Ci_C4坑基： X爲 Cl，Br 或I ; Z爲氫或由素，且 _____ -4- 本紙張尺度適用中國國家標準ί CNS ) A4規格（210X297公釐） ----Γ-----〉裝------、ΐτ------^ / 、 (請先鬩讀背面之注意事項再填寫本頁) A2667 1 . Α7 Β7 五、發明説明（2 ) Z|爲氫，鹵素，氰基或硝基， 此製程包括在水性鹼類之存在下，以過氧化氫使具有構造 式II之經取代（3 -哇啉基甲基）銨由化物氧化
X R
(II) 其中 (請先閱讀背面之注意事項再填寫本頁) .¾. 經濟部中央標準局貝工消費合作杜印褽 R ’ Ri ’ R2 ’ X，乙及义丨均如上面式I之敘述； R4，R5，汉6及尺7各分別爲氫，幾基，肖基，〇C(〇)R8， 鹵素，NR9R10，（^-(：4 烷氧基，S03H，S02C1 或 SH，其條件爲R4，R5 ’尺6及尺7之一非爲氫或鹵素； R 8爲C 1 - C 4娱•基’ C 1 - C 4規氧基，苯基或1SIR i 5 R丨2 ; R9 ’ Rl。’ Rii及Ri2各分別爲氫，Ci-C4燒基或苯基； 其N -氧化物；及 其酸加成鹽。 發明之詳細敘述 本發明之較佳具體例中，式II代表之經取代(^〃奎，林基 甲基）銨自化物係在較好約5 0 "C至1 0 0 6C，更好約7 5 i 9 5 °C之溫度範園内，在至少約1莫耳當量，較好約4至l 〇 莫耳當量之水性鹼存在下，以至少約8莫耳當量之過氧化 氫氧化。 有利地是，經發現以本發明有用且有效之方法可依高產 -5 - 本紙張尺度適用中國國家搮牵（CNS > Α4規格（210X297公釐）
，1T 經濟部中央標牟局員工消費合作社印製 42667 1 a7 ^ A 7 B7 五、發明説明（3 ) 率及純度製得[(5,6-二羧基-3-吡啶基）甲基]銨鹵化物。 產物[(5,6 -二羧基-3-吡啶基）曱基]銨由化物亦可藉由 以無機酸酸化反應混合物分離，且以標準步驟收集所得之 式I產物。相對地，反應混合物可整合於製程中，用於製 備最終之除草劑，而不需分離式I之化合物。 對於Z，Z!，R4，R5，及R7之上述鹵素之實例爲 氟，氣，漠及蛾，且以氣較佳。 適用於本發明製程中之水性檢包含驗金屬氫氧化物，如 氫氧化鈉及氫氧化鉀，鹼土金屬氫氧化物如氫氧化鈣，鹼 金屬碳酸鹽如碳酸鈉及碳酸鉀，鹼土金屬碳酸鹽如碳酸 劈，及其混合物。較佳之水性驗包含水性氫氧化納及水性 氫氧化鉀。 有利地是，式II之經取代（3-喹啉基甲基）銨齒化物高度 溶於水性鹼中《通常，鹼濃度自約35至65重量％較佳， 且鹼濃度自約40至60%更佳。過去，某些喳啉係在濃度 達到約35重量％之水性鹼存在下，以過氧化氫氧化（見美 國專利第4,8 1 6,5 88號）。然而，利用更濃之水性鹼係需 要的，因爲其降低產生之水性廢棄物之量。本發明製程之 另一優點爲不需要其水互溶之輔溶劑，因爲經取代之（3-喳啉基甲基）銨_化物高度溶於水性鹼中。 最小需要8莫耳當量之過氧化氫，以完全氧化式π經取 代（3 -喹啉基甲基）銨鹵化物。較好使用約8至60莫耳當量 之3 0 %至5 0 %水性過氧化氫，更好約8至4 0莫耳當量之 3 0 °/◦至5 0 %之水性過氧化氫，以氧化式π之化合物。 -6- 本纸張尺度適用中國國家標準（CNS ) A4規格（2|〇χ297公釐） (請先聞讀背面之注意事項再填寫本頁) 、1T- 4 266 經濟部中央標準局貝工消費合作杜印製 A7 B7 五、發明説明（4 ) 本發明之較佳製程中， R，1^及112各分別爲匚厂匚*烷基； X爲C1或Br ; 冗及乙丨爲氫； 尺4，R5，尺6及117之至少之一爲羥基，硝基或oc(o)r8 ;且 尺8爲<^1-〇4恍基，C1-C4規*氧基或笨基。 本發明之更好製程中， R，1及112爲甲基； X爲 Br ; R5，R6，R7，ZJ5LZ]爲氫； R4爲羥基，硝基或0C(0)Rs ;且 心爲“-。烷基或Ci-C4烷氧基。 式II之經取代（3-喹啉基曱基）銨齒化物可藉由在溶劑之 存在及視情況之催化量之游離基起始劑之存在下，以_化 劑鹵化式III之經取代3 -甲基嗤》林，形成式IV之經取代之 3 -鹵甲基>»奎淋，且在溶劑之存在下使式IV之化合物與至 少約一莫耳當量之式V之胺反應製備。反應程序示於流程 圖I中。 本紙張尺度適用中國國家標準（CNS ) A4規格（2丨0X297公釐） (請先閲讀背面之注意事項再填寫本頁)
426671 A7 B7 五、發明説明（5
流程圖I
2 R
R R· (III) 鹵化 (請先閲讀背面之注意事項再填寫本頁) ¾.
Y
2 R
R. R NRR R 1 2
V (V) 經濟部中央標準局員工消費合作社印製 RI _ Z R R.
R. R- (II) 本紙張又度適用中國國家橾準（CNS ) A4規格（210 X 297公釐） 4266 7 1 第861〇7〗47號專鈿申請案 中文説明書修正頁(87年9月） 五、發明説明（6 ) 本發明亦提供製備具下式之除草5-(烷氧甲基）_2_(2、味 峻p林-2-基）於酸，g旨及遵化合物之方法 z
(VI) 其中 Z及Ζ ί係如上面定義； A爲0或S ; Κ·Ι2 爲 C1-C4 坡基’ 視情沉以1至3個(：i - C 4烷基或鹵素原子取代之苯基，
Rl3爲Ci-C4燒基；
Rl4爲C1-C4燒基，C3-C6壤境基’或尺13及Rl4當與其連 接之原子合在一起時，係代表視情況以甲基取代之 C 3 - C 6環坡基及 R 1 5爲氫，二低級烷基亞胺基， 經濟部中央標準局員工消費合作社印製 ---------K — f請先閱磺背面之注意事喟再填寫本耳) 視情況以下列基之一取代之C[-Ci2拔i基：匸[-〇3坡1氧 基’鹵素，經基’ 環規基，字氧基’勿基’笨 基，齒苯基，低級烷苯基，低級烷氧苯基，硝基苯 基，羧基，低級烷氧羰基，氰基或三低級烷基胺； 視情況以下列基之一取代之C 3 - C ! 2烯基：C i · C 3烷氧 基，苯基，鹵素，或低級烷氧羰基，或具有二個 -9- 本紙張尺度適用中囷國家標準（CNS ) Μ規格（210XM7公f ) 426671 經濟部中央標準局貝工消費合作社印製 Α7 Β7 五、發明説明（7 ) C1-C3'坑氧基或二個鹵素基； 视情況以一個或二個C i - C 3烷基取代之C 3 - C 6環烷基； 或較好選自包含鹼金屬，鹼土金屬，錳，銅，鐵，鋅， 钴，鉛，銀，鎳，銨及有機銨之陽離子。 當RisKRm代表不同之取代物時，其光學上之異構物； 此製程包括： (a)以上面定義之製程製備式I之化合物
(I) 其中Z ’ Z!，R，Ri，尺2及)（係如上面定義；及 (b)將式I之該化合物轉化成式VI之化合物。 上面所用有關於烷基及烷氧基之“低級，，一詞意指含1至 6個，較好1至4個碳原子之烷基或烷氧基。 式I之化合物轉化成式VI之化合物可依各種方法進行。 其一可遵循已知同於將一羧酸衍生物轉化成另一個之結 合反應進行。 用於製造咪唑啉酮除草劑之方法係説明於CRC Press， Boca Raton, Florida 於 1991 年出版，由 D.L. Shaner 及S · L · 0 ’ C ο η η o r编輯之“咪峻琳酮除草劑” 一書中，尤 其是參考第二章，標題爲《咪唑啉酮除草劑之合成”，第 8 -1 4頁，及其中所列之參考。下列專利文獻參考例亦説 _ -10- 本紙張尺度適用中國國家樣準（CNS > Α4規格（210x297公釐） ^m» - —i— ^^^1 In - n^i I In In ^^^1 FJ^i f (請先閱讀背面之注意事項再填寫本頁) 2 66 7 Α7 Β7 五、發明説明（8 ) 明可用於轉化羧酸衍生物成爲咪唑啉酮最終產物之方法。 美國專利第 5,378,843 ; 5，371,229 ; 5，520,694 ; 5,1 1 0,93 0 ； 5,1 22,608 ； 5,206,3 6 8 ： 4,925,944 ； 4,921,961 ; 4,959,476 ; 5，103,009 ; 4,816,588 ; 4,757,146 ; 4,798,619 ； 4,766,218 ； 5,001,254 ； 5.021.078 ； 4,723,011 ； 4,709,036 ； 4,658,030 ； 4.608.079 ； 4,719,303 ； 4,562,257 ； 4,5 1 8,780 ； 4,4474,962 ； 4,623,726 ； 4,750,978 ； 4,638,068 ； 4,439,607 ； 4,459,408 ： 4,459,409 ; 4,460,776 ； 4，125,727及4,758,667及歐洲專利申請案第[?-八-0· 041，623 ; ΕΡ-Α-0·331，899 及 ΕΡ-Α-0·3 8 8,6 1 9 號。 爲了有助於進一步了解本發明，下列實例主要係用於更 詳細之説明.本發明應不受實例之限制，本發明之全部範 園係如申請專利範圍中所定義。 實例1 製備Κ5,6-二藉基-3-吡啶基）甲基1三甲某肱诡π# .ΤΪ 訂 / (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印袋 -11 - 本紙張尺度適用中國國家標準（CNS > A4规格（210X297公釐） 4 266 7 1 A7 B7 五、發明説明（9
2 、 I 1 N
Br_ (CH3) 3N+ch2
。丫 A ο η2〇2/η2〇
NaOH/H2〇
V
I
、CO_H 過氧化氫溶液（20克，3 0 wt/wt%，12當量）於85。至 90°C下，於15分鐘内加於[(8-乙醯氧基）-3_喳啉基）甲基】 二甲基按溴化物（5.0克’ 14.7毫莫耳）及氫氧化納溶液 (9,45克，50 wt/wt%，8當量）之攪拌溶液中。所得反應 混合物在85。至90°C下攪拌90分鐘，在85。(：下以額外之 過氧化氫溶液（26克，30 wt/wt%，15.6當量）處理3〇分 鐘’且在8 5。至9 0 C下揽拌一小時。最終反應混合物之 L C分析顯示目標產物係依8 0 %產率製成。 實例2-4 使用基本上與實例1中所述相同之步驟，但使用各種的 [(8-取代-3-喹啉基）甲基]三甲基銨溴化物，[(5,6•二幾 基-3-吡啶基）甲基]三甲基銨溴化物係依表I中所示之產率 製成。 -12 本纸張尺度適用中國國家標隼（CNS ) A4規格（2丨0X297公釐） -^^1- n^i nt nt m n I 、一-SJ - (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局貝工消費合作社印製 4 266 7 1 > A7 B7 五、發明説明（10) p ocpp
〇H W4 MI)
Br>{CH,)„3+CH_ s / 9.8 50 wtAvt% zaoH锊淬 /ivy}. 32 58 38 30 wt/wt%11202犄淬 經濟部中央標準局員工消f合作社印製 2 ·58 1.75 1,83 s 86 聆85。阼900 (I)
Br (CH:-N α^^Γ^8κ 洳 I 濟齑【(5,6-卜^髁-3-矣^^)-«^】^^-3^淞^今# (請先閱讀背面之注意事項再填寫本頁) >裝· 訂 -13- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 3
4266 7 1 > A7 B7 五、發明説明（Μ) 實例5 製備8 -乙醯氧基-3-甲基喳啉
〇 HCl + NaOH + {CH C) 〇 3 广 (
含8-羥基-3-曱基喳啉（2〇〇克，ίο〗毫莫耳）之氫氣化 物鹽及氫氧化鈉（102克，2.55莫耳）混合物之水（1〇〇〇毫 升）在0。至10。〇下以乙酸酐（208克，2.04莫耳）處理1小 時’且在至溫下揽摔〗小時。添加額外部份之乙酸肝（5〇 克’ 0 · 4 9莫耳）’且揽拌所得之混合物1小時，以標準之 碳酸氫鈉溶液（1 0 0毫升）處理，且過濾得到固體。固體以 水洗澈，於眞空烘箱6 0T下乾燥，且於乙酸乙酯/庚烷溶 液中再結晶’得到白色針狀之目標產物（1 6 8 . 5克，8 2 % 產率）。 -14- 本紙張尺度適用中國國家標準（CNS ) A4規格（2fOX297公釐） 訂------〆 、'-(請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印裝 經濟部中央標準局員工消費合作社印製 A7 B7 _ 五、發明説明（12) 實例6 锶借8 -苯醢氧基-3 -甲基崦啉 0
含8 -羥基-3-甲基喳啉之氫氣化物鹽（1〇克，0.051莫耳） 及三乙胺（15_5克’ 0_15莫耳）混合物之二氣甲烷（100毫 升）在0。至10°C下以苯醯氣化物（ΐ〇·8克，0.077莫耳）處 理1小時，在室溫下攪拌三小時，且以水稀釋。相經分 離’且以水洗滌有機相，在無水硫酸鎂上乾燥，且在眞空 中濃縮得到固體。因體自庚烷/甲苯溶液中再結晶，得到 淡黃結晶之目標產物（8 . 8克，6 5 %產率）。 -15- 本紙乐尺度適用中國國家榡牟（CNS ) Α4規格（210Χ297公釐） 丨L---：--------雀------訂------^ (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 4 2 66 7 1 " A7 B7 五、發明説明（13 ) 實例7 製備丨（8 -乙硫氧基林基）甲基1三曱基敍·溴化物
〇 1} γΛ N~Br
Si Ο 2) N(CH3)3 ψ
含8 -乙醯氧基_3_甲基喹啉（168.5克，0.84莫耳），Ν-溴琥珀醯亞胺（1 77.9克，1 ·〇〇莫耳）及2,2、偶氮雙異丁 腈（6.7克，0.04莫耳）之氣苯（1.675毫升）溶液充以氮 氣，在氮氣，8 0。至9 (TC下加熱2小時，冷卻至室溫且過 濾。含過濾物混合物之丙酮（700毫升）在0。至5°C下以三 -16- 本紙張尺度適用中國國家標準（CNS ) A4規格< 2】OX297公釐） 策------訂------洋 (請先閲讀背面之注項再填寫本頁) 426671 A7 B7 五 、發明説明（14 ) 乙胺（"75.4克，1.28莫耳）處理，在5〇至1〇。匸下攪拌3〇分 鐘，在室溫下攪拌1小時，且過濾得到固體。固體以水洗 條，且在眞空烘箱中60。(：下乾燥，得到白色固體之目擦 產物（1 8 0克，6 3 %總體產率）。 使用基本上相同之步驟，但使用各種的8_取代-3-甲基 喳啉，得到下列之化合物。
Br'iCH) N
B4 OC (O) c6h5 OC(0)OCH3 NO, (请先閲讀背而之注意事項存填寫本夷〕 1ί 鯉濟部中央標率局員工消費合作社印聚 -17 本紙張尺度適用中國國家標準（CMS > A4規格（210X 297公釐） 五、發明説明（ 15 A7 B7
0 Δ ch3〇h
V
經濟部中央標準局員工消費合作社印製 含[(8 -乙醯氧基_3_喹啉基）甲基]三曱基銨溴化物（5〇 克’ 14.7毫莫耳）之甲醇溶液回流135小時，且在眞空中 濃縮’得到殘留物。殘留物在6 〇 .c之眞空烘箱中乾燥， 得到灰色固體之目標產物（4 4克，1〇〇%產率）β -18- 本紙張尺度適用中國國家標準（CNS ) Α4規格（別乂加公董 IL--------f------訂------一 (請先閲讀背面之注意事項再填窝本頁)

Claims (1)

  1. 4 266 第86107147號專利申請案 A8 B8 中文申請專利範圍再修正本（89年ug88 六、申讀 r—-——w—焚範, 衣 修正.卬，丨vO 褚充 件丨1 n a 1. 一種製備具有構造式丨之[(5，石:顯吡啶基）甲基] 鍵鹵化物之方法 X' I 2 R-. I I CO-Η
    Ν CO Κ 其中 CD R ’ {^及!^各分別4Cl-C4烷基，且當合在一起時，R 及R丨可形成視情況以Ο，S或NR3插入之5 -或6 -元 環； R3為Ci-C4坑基； X 為 C 1 ’ B r 或 I ; Z為氫或鹵素，且 Z 1為氩，鹵素，氰基或硝基， 此製程包括在1至10莫耳當量之水性鹼類之存在下，於 50艽至loot之溫度下，以8至60莫耳當量之過氧化氫 使具有構造式II之經取代（3-喳啉基甲基）銨齒化物氧化
    本紙張尺度適用中國國家梯準（CNS ) A4規格（2丨0X297公釐） --------茉------^----- } (請先W讀背面之注意事項再填寫本頁) 經濟部中央橾準局貝工消費合作社印製 4 2 6 6 7 1 A8 B8 C8 ______D8 六、申請專利範圍 R，Ri ’ R2，X，Z及乙丨均如上面式I之敘述； R4為氩’羥基，硝基或oc(o)r8 ; R5，R6及R7各分別為氫： Rs為Ci-Cijfe基，Ci-Cijife乳基或私基| 其N-氧化物；及 其酸加成鹽。 2·根據申請專利範圍第1項之方法，其中 R，1^及112分別為Ci-C4烷基； X為C1或Br ;及 Z及Z 1為氫。 3. 根據申請專利範圍第2項之方法，其中 R，^^及尺】為甲基； X 為 Br ; R5，R6 ’ R7，ZKZ,為氫； R4為氫基，硝基或0C(0)R8 :且 Rg為(31-〇4境>基，或C|，C4捷机基。 4. 根據申請專利範圍第1項之方法’其中水性鹼係以4至 10莫耳當量之量存在。_ - 5·根據申請專利範圍第1項之方法，其中水性鹼為水性氫 氧化納或水性氫氧化钾。 6. 根據申請專利範圍第8項之方法’其中溫度為7 5 °C至 9 5°C。 τ 7. —種製備具式VI之除草咪唑啉酮化合物之方法， 本紙張尺度適用中國國家標準（CNS> A4規格（210X297公釐） (請先聞讀背面之注$項再填寫本頁) ，1T 經濟部中央標準局身工消費合作社印製 426671 AS BS C8 ---—_______Dg 六、申請專利範圍 •2
    其中 Z&Zl係如申請專利範圍第1項之定義；. A為〇或S ; RuSCi-Cq院基， 視情況以I至3個(^-(：4烷基或鹵素原子取代之苯基’ Ri^Ci-CVJ^ 基； 烷基’ c3-c6環烷基，或r13及r14當與其 連接之原子合在一起時，係代表視情況以甲基取代 之匸3-(：6環烷基及 R15為氫，二低級烷基亞胺基， 視情況以下列基之一取代之C i _ C丨2烷基：C , - C 3烷氧 基’鹵素’羥基，C3-C6環烷基，苄氧基，芴基， 苯基，函苯基，低級埤苯基，低級烷氧苯基，-硝基 苯基，羧基，低級烷氧羰基，氰基或三低級烷基 胺； 視情況以下列基之一取代之c3-c 12烯基：c,-c3烷氧 基，苯基，由素，或級烷氧羰基，或具有二個 (^-(:3烷氧基或二個鹵素基； 視情況以一個或二個Ct-C3烷基取代之(：3-(：6環烷基；或 -3- 本纸張尺度適用中國國家標準（CNS) A4規格（2丨以297公藿) " (請先聞讀背面之注項再填寫本頁)
    426671, A8 B8 C8 D8
    經濟部中央標準局員工消背合作社印«. 4 κ、申請專利範圍 陽離子；且當 R I 3及R Ν代表不同之取代物時，其光學異構物， 此製程包括： (a)以申請專利範圍第1項所申請之方法製備式I之化合物 COjH C〇sK (I) 其中Z，Zi，R，Ri，RAX係如申請專利範圍第1項 中之定義；及 (b)將式I之該化合物轉化成式VI之化合物。 本紙張尺度適用中國圉家揉率（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁}
    4266 7 1 第861〇7〗47號專鈿申請案 中文説明書修正頁(87年9月） 五、發明説明（6 ) 本發明亦提供製備具下式之除草5-(烷氧甲基）_2_(2、味 峻p林-2-基）於酸，g旨及遵化合物之方法 z
    (VI) 其中 Z及Ζ ί係如上面定義； A爲0或S ; Κ·Ι2 爲 C1-C4 坡基’ 視情沉以1至3個(：i - C 4烷基或鹵素原子取代之苯基， Rl3爲Ci-C4燒基； Rl4爲C1-C4燒基，C3-C6壤境基’或尺13及Rl4當與其連 接之原子合在一起時，係代表視情況以甲基取代之 C 3 - C 6環坡基及 R 1 5爲氫，二低級烷基亞胺基， 經濟部中央標準局員工消費合作社印製 ---------K — f請先閱磺背面之注意事喟再填寫本耳) 視情況以下列基之一取代之C[-Ci2拔i基：匸[-〇3坡1氧 基’鹵素，經基’ 環規基，字氧基’勿基’笨 基，齒苯基，低級烷苯基，低級烷氧苯基，硝基苯 基，羧基，低級烷氧羰基，氰基或三低級烷基胺； 視情況以下列基之一取代之C 3 - C ! 2烯基：C i · C 3烷氧 基，苯基，鹵素，或低級烷氧羰基，或具有二個 -9- 本紙張尺度適用中囷國家標準（CNS ) Μ規格（210XM7公f ) 4 266 第86107147號專利申請案 A8 B8 中文申請專利範圍再修正本（89年ug88 六、申讀 r—-——w—焚範, 衣 修正.卬，丨vO 褚充 件丨1 n a 1. 一種製備具有構造式丨之[(5，石:顯吡啶基）甲基] 鍵鹵化物之方法 X' I 2 R-. I I CO-Η
    Ν CO Κ 其中 CD R ’ {^及!^各分別4Cl-C4烷基，且當合在一起時，R 及R丨可形成視情況以Ο，S或NR3插入之5 -或6 -元 環； R3為Ci-C4坑基； X 為 C 1 ’ B r 或 I ; Z為氫或鹵素，且 Z 1為氩，鹵素，氰基或硝基， 此製程包括在1至10莫耳當量之水性鹼類之存在下，於 50艽至loot之溫度下，以8至60莫耳當量之過氧化氫 使具有構造式II之經取代（3-喳啉基甲基）銨齒化物氧化
    本紙張尺度適用中國國家梯準（CNS ) A4規格（2丨0X297公釐） --------茉------^----- } (請先W讀背面之注意事項再填寫本頁)
TW086107147A 1996-06-10 1997-05-27 Process for the preparation of [(5,6-dicarboxy-3-pyridyl)methyl] ammonium halides TW426671B (en)

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US6190332B1 (en) 1998-02-19 2001-02-20 Percusurge, Inc. Core wire with shapeable tip
US6355016B1 (en) 1997-03-06 2002-03-12 Medtronic Percusurge, Inc. Catheter core wire

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GB331899A (en) * 1929-03-08 1930-07-08 Heinrich Schluepmann Improvements in two-stroke cycle internal combustion engines
GB388619A (en) * 1932-05-26 1933-03-02 Sunsaloon Bodies Ltd Improvements in beading and cover strips particularly for use on vehicles
US4723011A (en) * 1985-10-28 1988-02-02 American Cyanamid Company Preparation of substituted and disubstituted-pyridine-2,3-dicarboxylate esters
US4816588A (en) * 1986-09-12 1989-03-28 American Cyanamid Company Method for the preparation of pyridine-2,3-dicarboxylic acids
DE3771153D1 (de) * 1986-09-12 1991-08-08 American Cyanamid Co Verfahren zur herstellung von pyridin-2,3-dicarboxylsaeuren.
IL89142A (en) * 1988-03-10 1993-04-04 American Cyanamid Co Method for the sequential oxidation of substituted 8-hydroxyquinolines to produce substituted pyridine-2,3- dicarboxylic acids
US5369022A (en) * 1988-12-30 1994-11-29 American Cyanamid Company Method to improve the protection of crops from herbicidal injury
EP0388619B1 (en) * 1989-03-22 1994-08-10 American Cyanamid Company Method for the sequential oxidation of substituted quinolines to produce substituted-pyridine-2,3-dicarboxylic acids
US5288866A (en) * 1991-12-20 1994-02-22 American Cyanamid Company 5,6-disubstituted-3-pyridylmethyl ammonium halide compounds useful for the preparation of 5- (substituted methyl)-2,3-pyridinedicarboxylic acids
DE69409776T2 (de) * 1993-12-28 1998-09-24 American Cyanamid Co Verfahren zur Herstellung Pyridin-2,3-dicarboxylicsäure
US5633380A (en) * 1995-06-05 1997-05-27 American Cyanamid Company Substituted quinoline herbicide intermediates and process
US5625068A (en) * 1995-06-05 1997-04-29 American Cyanamid Company Substituted quinoline herbicide intermediates and process

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ES2174185T3 (es) 2002-11-01
YU24197A (sh) 2000-12-28
AU2475897A (en) 1997-12-18
JPH1059941A (ja) 1998-03-03
EP0812828B1 (en) 2002-03-13
ATE214370T1 (de) 2002-03-15
ZA975075B (en) 1998-12-09
TR199700476A2 (xx) 1997-12-21
AU709900B2 (en) 1999-09-09
CZ288272B6 (en) 2001-05-16
CA2207379A1 (en) 1997-12-10
KR980002026A (ko) 1998-03-30
SG50845A1 (en) 1998-07-20
CO5040015A1 (es) 2001-05-29
AR007523A1 (es) 1999-11-10
DK0812828T3 (da) 2002-07-01
US6002012A (en) 1999-12-14
NZ314904A (en) 1998-06-26
DE69710948T2 (de) 2002-07-04
DE69710948D1 (de) 2002-04-18
HU218875B (hu) 2000-12-28
SK73897A3 (en) 1998-02-04
CZ170697A3 (en) 1997-12-17
PT812828E (pt) 2002-09-30
HU9701022D0 (en) 1997-08-28
RU2142943C1 (ru) 1999-12-20
CN1172802A (zh) 1998-02-11
IL121032A (en) 2001-01-28
HUP9701022A1 (hu) 1998-04-28
EP0812828A1 (en) 1997-12-17
PL320464A1 (en) 1997-12-22
CN1100758C (zh) 2003-02-05
BR9703506A (pt) 1998-10-06
IN183352B (zh) 1999-11-27
IL121032A0 (en) 1997-11-20
MX9704259A (es) 1998-07-31

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