TW519534B - Processes for preparing pesticidal intermediates - Google Patents

Processes for preparing pesticidal intermediates Download PDF

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TW519534B
TW519534B TW088105957A TW88105957A TW519534B TW 519534 B TW519534 B TW 519534B TW 088105957 A TW088105957 A TW 088105957A TW 88105957 A TW88105957 A TW 88105957A TW 519534 B TW519534 B TW 519534B
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Jean Erick Ancel
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Rhone Poulenc Agriculture
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    • C07D213/00—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
    • C07D213/02—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
    • C07D213/89—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 with hetero atoms directly attached to the ring nitrogen atom
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    • C07D213/04—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
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    • C07D213/77—Hydrazine radicals
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
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    • C07C255/65—Carboxylic acid nitriles containing cyano groups and nitrogen atoms further bound to other hetero atoms, other than oxygen atoms of nitro or nitroso groups, bound to the same carbon skeleton with the nitrogen atoms further bound to nitrogen atoms
    • C07C255/66—Carboxylic acid nitriles containing cyano groups and nitrogen atoms further bound to other hetero atoms, other than oxygen atoms of nitro or nitroso groups, bound to the same carbon skeleton with the nitrogen atoms further bound to nitrogen atoms having cyano groups and nitrogen atoms being part of hydrazine or hydrazone groups bound to the same carbon skeleton
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    • C07D213/04—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
    • C07D213/24—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 substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/26—Radicals substituted by halogen atoms or nitro radicals
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—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
    • C07D213/02—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
    • C07D213/04—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
    • C07D213/24—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 substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
    • C07D213/30—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—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
    • C07D213/02—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
    • C07D213/04—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
    • C07D213/24—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 substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
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    • C07D213/34—Sulfur atoms to which a second hetero atom is attached
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—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
    • C07D213/02—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
    • C07D213/04—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
    • 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
    • C07D213/61—Halogen atoms or nitro radicals

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Description

519534 五、發明說明（1) --- 本發明係關於用於製備殺蟲劑之中間體（特是2 —(芳美餅 基）破站膳化合物及3_(方基亞餅基）玻轴膳化合物）之新顆 製法。 歐洲專利公告案第0 2 9 5 1 1 7及0 2 3 4 1 1 9號描述了具殺蟲劑 活性之苯基吡唑之製法以及用於合成該化合物之5 -胺基 一 1-芳基-3-氰基吡唑之製法。、 該等化合物之許多製法谗已知。本發明係尋求提出製備 该等殺蟲劑及用於製作該等殺蟲劑之中間體之改善或是更 經濟之製法。 德國專利公告案第3 6 1 2 9 4 0號揭示了如下式可以用來作_ 為製備具有殺草劑或是殺蟲劑性質化合物之中間體之5 _胺 基〜1〜芳基吡唑衍生物之製法：
人〆N —八γ"
At 於其中Ar代表經取代之苯基或是吡啶基，經由將芳基肼 翼酸鹽與下式之甲醯乙腈鈉鹽反應：
NaOCH=CH-CN 而得如下式之亞肼化合物：
Ar-NH-N-CH-CH2-CN
519534
五、發明說明（2)
然後該化合物再於一種鹼存在下 於其中Ar定義如前述 環化。 然而在此最好獲得一種純的亞肼化合物以利於i後 成殺蟲劑。已知之步驟可能導致所形成之亞肼受 5 -胺基-1 -芳基吡唑污染。 & κ 本申請人很意外地發現一種新穎之亞肼化合物之製法 不會產生環化現象。然後該亞肼化合物可以提供作為—種 製造5-胺基-卜芳基吡唑之新方法，一或是在一個新穎的方 法中經由加入一種氰化物而獲得2_(芳基肼）琥珀腈衍生 物，該衍生物再進一步加工作成重要的5_胺基芳基_3一 氰基吡唑化合物’而這化合物係製備殺蟲劑時非常有"'價 之中間體。- ' 美國專利案第4, 824, 960號描述了下式可以用來作為製 備具有殺草劑或是殺蟲劑性質化合物之中間體之5 —胺臭& - 1 -芳基D比嗤衍生物之製法： N I Ar
I 經由將具有下 於其中Ar代表經取代之苯基或是吼咬基 式之方基讲·
Ar-NH-NH2 於其中Ar定義如前述，與具有下式之烯腈反應：
第6頁 519534 五、發明說明（3) NC-CH-CH, 在第一階段中，在一種稀釋劑與選擇性的一種催化劑存 在下可得下式之3-芳基肼丙腈化合物：
Ar-NH-NH-CH2-CH2-CN 於其中Ar定義如前述，接著在第二步之處理時再氧化與 環化。 然而若是希望將上述之3 -芳基肼丙腈氧化（不要環化成 5 -胺基-1 -芳基吡唑）而形成3 -芳基亞肼丙腈，然後再進一 步將該化合物加工作成製備殺蟲劑時有價值之5-胺基-1 -芳基-3 -氰基吡唑化合物，則此時必須採用一種不同的方 法。 據此本發明提出一種式（I)化合物之一種製法（A ) ··
NC
W
HOST
(I) R2. 於其中W代表氮或是-CR3 ;
519534 五、發明說明（4) 、 〜----- R1代表鹵素，鹵烷基（較佳者為三敦甲 (較佳者為三氟曱氧基），R4S(0)n_，或〜sf);，鹵烷氧基 R2代表氫或是鹵素（例如氣或是溴）； 5 R代表鹵素（例如氯或是漠）； κ代表燒基或疋鹵院基，以及 n代表0，1或是2 ;該方法包含了將式f (1 Π )之芳基肼一種酸加成鹽反應·· 化合物與式 ^ΗΝη2
(II) 於其中R5及R6各自代表烷基或是一 個碳原子之烯鏈，R1，R2及W之定義如^'表一個含有2至3 可以為順式與反式異構物之混合物:味。式（I)化合物 式存在。 疋為各別之異構物形 除非在本說明中另有說明，"烷基 佳者為1至3個）碳原子之直鏈或是 ’、q具有1至6個（較 有說明，"鹵烷基”及i烷氧基,，係鏈之烷基。除非另 佳者為1至3個）碳原子之直鏈或是有 曰具有1至6個（較 基，其中被-個或多個選自：疋氣有之产基或燒氧. 通常在式（⑴中R4R6 <系代表相或之廣广之乱原子所取代。 基或是乙基。 表相同之烷基，較佳者為甲 519534
式 ^丨/1)化合物之酸加成鹽較佳者係由諸如礦物酸之強 常該 酸（例如硫酸或是#社十碱純、a / ^ ^ ^ 4疋旱乂 4之鹽酸）所形成之酸加成趟。通 該反應 極 等鹽類係預先形成但是亦可擇性的在此時才形：一 可以在水存在下在一種極性或是非極性之溶劑内進行 性溶劑之實例包括有水；諸如甲醇及乙醇之醇類，·諸如6 腈之腈類；諸如N-甲基吡咯酮或是二甲基亞楓之亞楓。# ，性溶劑之實例包括氣化烴，較佳者為四氯化碳；及諸如 環己烧之烴。反應溫度通常係自2 Q t至1 〇 〇它，較传者自 50 °C至90 °c。通常使用等當量之式（π)及式（m)化合 物。所存在水的量可以自一種催化量至大量過量。 在式（I )，（ I I I)及接下來所描繪之結構式中，符號之权 佳值如下：一 R1代表鹵烷基（較佳者為三氟曱烷），鹵烷氧基（較偻者 為三氟曱氧基）或-SF5 ; w代表-CR3 ;其中R3代表鹵素； 一個最佳之式（I)化合物為3-(2，6 -二氯-4-三敗f基菜 基亞肼基）丙腈。 一個更佳之式（I )化合物為3-(2 -氯-4-三氟甲基苯基爻 讲基）丙膳。 式（I I)及式（I I I )化合物係一般文獻中已知。 本發明方法之特點可由下列許多優點描述。利用本發明 方法可以尋求以立即可得之起始物質以高產率獲得式（I) 之3-芳基亞肼基-丙腈。甚至進行該反應非常容易而且經 濟，以及可以直接分離該產物。甚者所獲得之式（丨）化合
O:\58\58002.PTD 第9頁 519534 五 '發明說明（6) 物實質上未發生環化反應。 根據本發明之進一步特點在於提出以方法（B )製備式（I ) 化合物，其中W，R1及R2定義如前述，該方法包括了將式 (I V)化合物與式（I I I )化合物反應： /0R7 /
NC (IV) 其中R7代表烷基（較佳者為曱基或乙基），其中R1，R2及W · 定義如前述。其反應條件與前述以式（I I)化合物與式 (II I )化合物之酸加成鹽來製備式（I )化合物之方法所用之 條件相同。 式（I V)化合物係一般文獻中已知。 根據本發明之進一步特黠在於提出以方法（C)製備式（I) 化合物，其中W，R1及R2定義如前述，該方法包括了將式 (V)化合物氧化：
第10頁 519534 五、發明說明（7) 在前述反應中用來氧化形成式（I )化合物之氧化劑包括 有諸如苯醌之醌，諸如過氧化氫之過氧化物，諸如次氯酸 納之次鹵酸鹽；或是較佳者為金屬鹽或是氧化物例如氯化 銅或是氧化汞。氧化反應通常在溶劑中進行。適用之溶劑 包括有諸如曱苯或是氯苯之芳香族鹵化或非鹵化烴，諸如 乙腈之腈，或是諸如N，N -二曱基甲醯胺之醯胺。反應溫度 一般係自約2 0 °C至約1 5 0 °C，較佳者係自約5 0 °C至約1 0 0 °C 〇 氧化物對式（V)化合物之莫耳比率一般係自0. (Η : 1至 5 : 1，較佳者係自1 : 1至3 : 1。 根據本發明之進一步特點在於提出一個式（V I )化合物之 製法（D) ··
其中R1，R2及W定義如前述；該反應在於將式（I)化合物 (其中R1，R2及W定義如前述）與一種來源之氰化氫反應。式 (VI)化合物可以R-及S-的型式或是其混合物的型式存在。 當該反應係選擇性地在一種諸如吼唆之鹼存在才進行
第11頁 519534 五、發明說明（8) 時，該氰化氫之來源可以為氰化氫氣體本身；但是最好還 是由金屬氰化物鹽類（一般係一種驗金屬氰化物，例如氰 化鈉或氰化鉀）在一種酸存在下就地產生（以避免直接使用 氰化氫）。適當之酸包括有機酸諸如脂肪族羧酸，例如乙 酸，或是鹵化脂肪族羧酸例如氯基乙酸，三氟乙酸；諸如 苯石黃酸，4 -甲基苯石黃酸或是甲基石黃酸之石黃酸；或是諸如氫 氯酸或硫酸之無機酸。 其他氰化氫之來源（亦為就地產生）係三甲基矽基氰化物 在水中，或是在諸如二氯曱烧或是四氫咲喃溶劑内之三曱 基石夕基氰化物與一種路易士酸之混合物，例如四氯化錫 · (I V )，在自2 0 °C至1 0 0 °C之溫度下產生，較佳之溫度為3 0 QC至6 0 °C。反應最好在加壓之條件下進行因為可以加速反 應。 由式（I )化合物製備式（V I )化合物可以在一種極性或是 非極性之溶劑中進行。可用之極性溶劑之實例包括有水； 諸如曱醇或是乙醇之醇；N，N-二曱基曱醯胺；N，N -二曱基 亞楓；或是諸如乙酸之烷醯酸。非極性溶劑之實例包括有 諸如己院之烴，或諸如四氫咲喃或二氧六圜之_或是諸如 二乙基醚之二烷基醚；或是諸如乙腈之腈。當使用者為在 酸存在下之金屬氰化物時，較佳之溶劑為水或是水與可與· 水掺合溶劑之混合物。可以使用等當量或是過量之來源氰 化物，通常使用量為1至4莫耳當量。反應溫度一般係自0 °C至1 0 (TC，較佳者係自2 (ΓC至5 (ΓC。 一個最佳之式（VI)化合物為2-(2，6 -二氯-4 -三氟曱基苯
第12頁 519534 五、發明說明（9) '一"—- 基讲基）號拍膳。 一個更佳之式（VI)化合物為2-(2〜氯-4—三氟甲基苯 基）琥珀腈。 根據本發明一個進一步之特點為步驟（A)至（]))可以合併 由式（I I I)化合物製備一個式（VI )化合物。 " 根據本發明一個進一步之特點為步驟（Β)至（D)可以合併 由式（I I I)化合物製備一個式（VI )化合物。 ° 根據本發明一個進一步之特點為步驟（c)與（D)可以合併 由式（V)化合物製備一個式（VI)化合物。 根據本發明個進步之特點為步驟（C)與（D )之組合可·_ 以再與另一個步驟（E)合併’該步驟包括了將一種式（丨丨j) 之芳基肼化合物（其中w ’R1及R2定義如前述）與一種式 (V I I )之丙烯腈化合物反應 nc-ch=ch2 (νΠ) 而得定義如前述之式（v)化合物。 式（V II )化合物係已知。 由本發明方法（A )或（B )或（C)所獲得之式（I )化合物可以 根據下列反應流程來製備具有殺蟲劑活性之式（V I I I ) 5-❿ 胺基-1 -芳基吡唑衍生物：
O:\58\58002.PTD 第13頁 519534
第14頁 519534 、發明說明（Η) 其中R1，R1及W定義如<、、 式（X )化合物可以雜則述。 氧化之適當氧化劑包：由將式(VI)化气曰物氣化而製得。供 氧化物，諸如次氡$諸如苯醌：-比二諸如過氧化氫之 氧化納之鹼金屬^之次齒酸鹽：在空氣存在下諸如 仏μ心备几細+ β孔化物，或是权佳者為金屬鹽或县备 五 過 氫氧化納之鹼金屬卜之次齒酸鹽’在空氣存在下諸如 化物例如氯化銅或是J化物，或是較：者為金屬鹽或是氧 Γ。適用之溶劑以化果。氧化f應，在溶劑中進 非函化烴，诸如乙腈之腈，或是諸如N，N-二甲化或 _。反應溫度-般係自⑽。C裏約150〇C，較土胺之 約。氧化劑對式(VI)的莫耳比率It 0.01:1至5:1，較佳者為自Η至3:1。 般自 式（ΧΟ化=物可以由已知之方法自式⑴化合物製 下列非限制性之實例係用來說明本發明。記 ^ 譜係以二氘曱烷作為溶劑。 Τ之賴1^先 實例1 氟曱基苯基 自2,2 —二甲氧基丙腈製備3-（2,6 -二氯-4-亞肼基）丙腈
1 ，6_二氯―3 4 5 6—三氟甲基苯基肼鹽酸鹽係將氫氯酸氣體直 2 接冒泡通入2, 6 -二氯-4-三氟甲基苯基肼在乙醚之溶液再 3 過濾鹽酸鹽而得，其產出可達完全。將四氯化碳（5瓜丨）及释 4 3, 3 -二甲氧基丙腈（141微升）依序加入前述2, 二氣—4_三 5 敦甲基苯基肼鹽酸鹽（〇·349克）在水（5毫升）之溶液内再於 6 5 C加熱1 〇小時。冷卻之混合液經萃取（二氯曱烷），萃洗 (水）’脫水（硫酸鎂）再減壓蒸餾而得該標題化合物（〇 . 3 5 8 519534
五、發明說明（13) 時之後將反應混合液加到飽和之碳酸氫鈉水溶液内，經萃 取（二氯甲烷），萃洗（水），脫水（硫酸鎂）再減壓蒸餾而^ 含有40%該欲得之標題化合物，NMR 3.1 (m，2H ) 4 5 (ra，1 Η )，5 · 8 9 (m，1 η )，6 · 9 4 (d，1 Η )，7 · 7 1 ( s 2Η)，與60%未反應起始亞肼之混合物。 ’ 實例5 自3-(2,6 -二氣-4 -三氟甲基苯基肼基）丙腈製備3_(2,6 — 二氯-4 -三氟曱基苯基亞肼基）丙腈 ’ 將氯化銅（0 · 6 7 3克，2 · 5當量）一次加入3 - ( 2，6 -二氯-4 -二氟甲基苯基肼基）丙腈（0.591克，2 mmol)在氯苯之溶液. 内’然後將μ合液在6 5 C加熱5 0分鐘。反應經評估完全後 冷卻，萃洗（水），脫水（硫酸鎂），減壓蒸餾再於矽凝膠層 析分離而得3-(2, 6 -二氯-4_三氟甲基苯基亞肼基）丙腈， NMR 3.37 (d, 2H), 7.03 (t, 1H), 7.5 (s, 2H), 7 75 (s, 1H) (35 %產率）’以及3-（2，6 -二氯-4 -三氟曱基苯基 偶氮基）丙腈，NMR 3·0 (t，2H)，4.6 (t，2H)，7.6 (s， 2H) (60% 產率）。 實例6 製備2 -（2，6 -二氯-4 -三氟曱基笨基肼基）琥珀腈 將2-（2, 6 -二氯-4 -三氟甲基苯基亞肼基）琥珀腈（0.296❸ 克，1 mmol)，氰化鈉（0.196克，4當量），水（1 mi)及乙 酸（5 m 1)依序加到一個管子内。將管子密封後在2 〇 °c反應 4 0小時。將反應混合液加到飽和之竣酸氫納水溶液内，經 萃取（二氯甲烷），萃洗（水），脫水（硫酸鎂）再減壓蒸餾而
O:\58\58002.PTD 第17頁 519534 五、發明說明（14) 付含有40%該欲得之標題化合物，NMR 31 (m，2Η)，4·5 (m，1Η)，5·89 (m，1Η)，6·94 "，1Η)，7·71 (s， 2 Η )，與6 0 %未反應起始亞肼之混合物。 多考實例 1)製備2—(2，j—二氯—4-三氟甲基苯基亞肼基）琥珀腈 將2—(2, 6—二氯一三氟甲基苯基肼基）琥珀腈（0· 3 23克） 及虱化銅（0· 175克）之混合物在氯苯中以6〇它加熱6小時。 過濾之後減壓蒸餾可得標題化合物與5—胺基-3—氰基 ^1^2, 6一二^一4—三氟甲基苯基）吡唑7: 1之混合物。在矽 凝f上進行管柱層析以二氯甲烷溶離可得該標題化合物， 所得為順式與反式異構物之混合物，NMR (反式異構物）3 6 (s，2H)，7·57 (s，2H)，8·82. (s，1H，可與 D2〇 互換）， ii)製備5 -胺基—3 -氰基—ι — (2, 6 -二氯-4- NMR(順式異構物）3·56 (s，2Η)，7·59 (s，2η)，8·υ (s，1H，可與D2〇互換）Λ ’ 曱基苯 基）吼°圭 在〇 C將氨（2 0微升之8 %氨水溶液）加到前述2 — ( 2，β —二氯 -4 -二氟曱基苯基亞肼基）琥珀腈（〇.〇77克）於乙醇（1毫升） 及水（0 · 2耄升）之混合液中。經1 〇分鐘之後，將混合物萃 取（一氯甲烧）再減壓蒸德可得5 —胺基-3 -氰基(2, β —二 氯一4_三氟甲基苯基）吡唑（0· 0 76克，產率97%)。純度98% (以h ρ 1 c分析）。
O:\58\58002.PTD 第18頁

Claims (1)

  1. 519534 案號8810 修止 m 月：> 丨曰 修正本 六、申請專利範圍 1 · 一種式（I)化合物之製備方法： NC HbT
    .N 其中W代表氮或是-CR3 ; 或匕-C4鹵烷氧基 R1代表鹵素，Ci-C〗函烧基 R2代表氫或鹵素； R3代表i素； 該方法包含 (A) 將式（I I )化合物 PR5 NC 、OR6 (II) 其中R5及R6各自代表烧基或一起代表含有2至3個碳原子 之烯鏈，與式（III)芳基肼之酸加成鹽反應：
    O:\58\58002-911021.ptc 第20頁 519534 案號88105957 Ή年'>丨日 修正
    O:\58\58002-911021.ptc 第21頁 519534 修正 案號 88105957 六、申請專利範圍 其中R1，R2及W之定義如前述。 2 .根據申請專利範圍第1項之方法，其中R1代表i素，三 氟曱基或三氟甲氧基。 3. 根據申請專利範圍第1項之方法，其中R2代表氫，氯或 溴。 4. 根據申請專利範圍第1項之方法，其中R3代表氯或溴。 5. 根據申請專利範圍第1項之方法，其中（C)中R5及R6各 自代表曱基或乙基。 6 .根據申請專利範圍第1項之方法，其中（B)中R7代表曱 基或乙基。 7.根據申請專利範圍第1項之方法，其中（A)或（B)中式 (I I I )化合物之酸加成鹽係由強酸所形成之鹽類。 8 .根據申請專利範圍第1項之方法，其中（A )或（B )中有 水存在。 9.根據申請專利範圍第1項之方法，其中（C)中氧化式 (V)化合物之氧化劑為金屬鹽或是氧化物。 1 0.根據申請專利範圍第1項之方法，其中該（C)方法係 於溶劑中進行。 1 1.根據申請專利範圍第1項之方法，其中（C)中氧化劑 對式（V)化合物之莫耳比率係自0 . 0 1 : 1至5 : 1。 1 2.根據申請專利範圍第1 1項之方法，其中該莫耳比率
    O:\58\58002-911021.ptc 第22頁 519534 修正 案號 88105957 六、申請專利範圍 係自1 : 1至3 : 1。 1 3. —種式.(V I)化合物製備方法：
    (VI) i 其中R1，R2及W係為如申請專利範圍第1項中所定義者； 該方法包含將式（I )化合物，其中R1，R2及W係為如申請專 利範圍第1項中所定義者，與氰化氫之來源反應。 1 4.根據申請專利範圍第1 3項之方法，其中該氰化氫係 由金屬氰化物在酸存在下製得。 1 5.根據申請專利範圍第1 3或1 4項之方法，其中該反應 係在加壓下進行。 1 6.根據申請專利範圍第1 3項之方法，其中該式（I )化合 物係根據申請專利範圍第1項之方法（A)製得。 1 7.根據申請專利範圍第1 3項之方法，其中該式（I)化合 物係根據申請專利範圍第1項之方法（B)製得。 1 8.根據申請專利範圍第1 3項之方法，其中該式（V I )化
    O:\58\58002-911021.ptc 第23頁 519534 修正 _案號 88105957 六、申請專利範圍 合物係經氧化並視情況與鹼反應而製成式（X )或式（XI)化 合物：
    於其中W，R1及R1係為如申請專利範圍第1項中所定義 者。 1 9.根據申請專利範圍第1項之方法，接著將（C)所得之 式（I )化合物與氰化氫之來源反應而製得式（V I )化合物， 於其中R1，R1及W係如申請專利範圍第1項中所定義者。 20.根據-申請專利範圍第1項之方法，其中（C)中該式（V) 化合物係將式（I I I )化合物，其中R1，R1及W係為如申請專 利範圍第1項中所定義者，與式（V I I )之丙烯腈反應而製 得： NC-CH=CH2 (VII)。
    O:\58\58002-911021.ptc 第24頁 1 1.根據前述申請專利範圍第1項之方法，其中（C)中R1代 519534 _案號88105957_Μ年㈧月>U 修正_ 六、申請專利範圍 表*^-C4鹵烷基或(^-(：4 i烷氧基； W代表-CR3 ;且R3代表鹵素。 2 2.根據申請專利範圍第2 1項之方法，其中R1表代表三氟 甲基或三氟甲氧基。 2 3.根據前述申請專利範圍第1項之方法，其中（C )中R1代 表三氟曱基，W代表-CR3，且R2及R3代表氯。
    O:\58\58002-911021.ptc 第25頁
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