TW412514B - Halogenophenoxyfatty acid derivatives - Google Patents

Halogenophenoxyfatty acid derivatives Download PDF

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TW412514B
TW412514B TW084105451A TW84105451A TW412514B TW 412514 B TW412514 B TW 412514B TW 084105451 A TW084105451 A TW 084105451A TW 84105451 A TW84105451 A TW 84105451A TW 412514 B TW412514 B TW 412514B
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Hiroshi Hamaguchi
Tomokazu Hino
Kenji Tsubata
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Nihon Nohyaku Co Ltd
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    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
    • C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
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    • C07D295/185—Radicals derived from carboxylic acids from aliphatic carboxylic acids
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    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B39/00—Halogenation
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
    • C07C235/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C235/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C235/18—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated having at least one of the singly-bound oxygen atoms further bound to a carbon atom of a six-membered aromatic ring, e.g. phenoxyacetamides
    • C07C235/20—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated having at least one of the singly-bound oxygen atoms further bound to a carbon atom of a six-membered aromatic ring, e.g. phenoxyacetamides having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
    • C07C235/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C235/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C235/18—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated having at least one of the singly-bound oxygen atoms further bound to a carbon atom of a six-membered aromatic ring, e.g. phenoxyacetamides
    • C07C235/24—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated having at least one of the singly-bound oxygen atoms further bound to a carbon atom of a six-membered aromatic ring, e.g. phenoxyacetamides having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/16—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound oxygen atoms bound to the same carbon atom of an acyclic carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/58—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the carbon skeleton
    • C07C255/60—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the carbon skeleton at least one of the singly-bound nitrogen atoms being acylated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C327/00—Thiocarboxylic acids
    • C07C327/38—Amides of thiocarboxylic acids
    • C07C327/40—Amides of thiocarboxylic acids having carbon atoms of thiocarboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/363—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/307—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms

Description

4m!4 Λ 6 Rf> 五、發明説明（2 ) 193939、62-223U0及待開平 3-99033,及待公平 3-22377 之製法裂造。 担疸些裂法可能産生有毒載奥率類副産物。且在曰本 待開昭62-223140須用過氣化氫，在日本待公平3-22377 須用含Η鹺.日本特開平3-99033須用水及二相糸，又 須氰化剤。 且由單鹵苯氣脂肪酸衍生物之鹵化來製造鹵苯氧脂肪 酸衍生物時，用豳化剤及》媒，如碘及鐵〔J.O.C., 426 Π 9 4 7 )]。但此製法有所用《媒之後處理問題。 本發明者們致力於研究開發不用觭媒而以高産率製造 鹵苯氣脂肪酸衍生物之新潁製法，終於完成本發明。 由本發明製法製造之鹵苯氣脂肪酸衍生物可當作Η藥 ，農藥及化學品之中間體，有些為未見諸文獻之如下式 (I ’）之新穎化合物：
R2_ ------- -------------------] I -------71------- (請先閲讀评面之注意事項再堉寫本頁) 經濟邪中央標準局8工消费合作钍印5¥ 〔式中R’為氰基或-C0N(R3')RV (式中及R4'可相同 或相異，各為氳，低烷基.苯基，苯基而有1〜5個可相 同或相異取代基選自齒紫，硝基，氰基，低烷·基，低豳 烷基.低烷氣基，低豳烷氣基，低烷碕基及低豳烷硫基 本紙張又度適用中國因茱抒準（CNS)甲4峴格（210 X 2M ) 82,1. 20,000 ® :郜中夹揉準局R工消费合作钍印si 412514 A6 __B6_ 五、發明說明（1 ) 本發明為有關如下式（I )豳苯氣脂肪酸衍生物之製法
〔式中R為《基，-CON(R3)R4 (式中R3及R4可相同 或相異，各為氳，低烷基，苯基，苯基而有1〜5個可相 同或相異取代基選自鹵素，硝基，氡基，低烷基，低豳 烷基，低烷氣基，低鹵烷氣基，低烷硫基及低鹵烷硫基 ，苄基或苄基而有1〜5傾可相同或相異取代基選自低烷 基，低豳烷基，低烷氧基，低鹵烷氣基，低烷硫基及低 鹵烷硫基，R3及R4可共為伸烷基）或-COARs (式中 Rs為氫，低烷基，苯基，苯基而有1〜5傾可相同或相 異取代基選自鹵素，硝基，«基，低烷基，低鹵烷基， 低烷氧基，低鹵烷氣基，低烷硫基及低鹵烷硫基，苄基 或苄鸯而有1〜5館可相同或相異取代基選自低烷基，低 齒烷基，低烷氣基，低鹵烷氣基，低烷硫基及低鹵烷硫 基，A為氣或硫），R1及R2可相同或相異，各為氫或 低烷基，X為鹵素或低烷基，Y為鹵素]. 及有關由該製法所得之豳苯氣脂肪酸之部分。 在本文中低烷基等中低乃指Ci - 6。 一般，鹵苯氣脂肪酸衍生物乃由單苯酚經齒化而得 之二鹵苯酚來製造。該二鹵苯酚乃依日本待開昭60- -3- 本紙張尺度迺用中aa家樣，（CN’S) 1* <规格（210 X 297公* > 82.1. 20,000 ---------------------------装------ir------象 <請先閲讀背面之注*事項再項W本頁)_ Μ _I_ __Β6_ 五 '發明説明（7 ) 此為已知化合物，熔點及rtMR與文獻（CA 124017«)—致D 産率83 . 0% 例2 2, 4 -二氮苯《乙匿胺（化合物10)之製造
將1.86克（0.01莫耳）4 -氛苯氣乙g胺在50X：加熱溶 在11 m 1乙酸.而在同溫以1 2 . 3a 1 /分之速度通人氣氣5 0 分。 反應终了後，加3nl 10Χ硫代硫酸納水而減壓蒸除溶 劑.加2 0 b 1 1 0 %硪酸氫鈉水，而以乙酸乙酯（3 0 m 1 X 2 ) 萃取。 將有機層以無水硫酸鈉乾燥而滅壓濃縮成結晶後，以 正己烷洗淨，得2.02克所求2, 4 -二氛苯氣乙醛胺。 産率92 . 0% 此為己知化合物，熔點及HMR與文獻（J0C第428頁，1947)者一致。 例3 2, 4 -二氮苯氧乙酸（化合物17)之製造 ----------------,--------裝------.玎----——線 (請先《ίί背面之注意寧項再填寫本頁} 烴濟部中央標準局8工消t合作社印¾
1 . 8 7克（0 . 0 1其耳）4 -氱苯《乙酸投入1 0 m丨二甲基甲 -9 - 本紙张尺Λ通州中《國家樣苹（CNS)甲4现格（210 X 297 ) 82.1. ΙΌ 000 4m!4 Λ 6 Rf> 五、發明説明（2 ) 193939、62-223U0及待開平 3-99033,及待公平 3-22377 之製法裂造。 担疸些裂法可能産生有毒載奥率類副産物。且在曰本 待開昭62-223140須用過氣化氫，在日本待公平3-22377 須用含Η鹺.日本特開平3-99033須用水及二相糸，又 須氰化剤。 且由單鹵苯氣脂肪酸衍生物之鹵化來製造鹵苯氧脂肪 酸衍生物時，用豳化剤及》媒，如碘及鐵〔J.O.C., 426 Π 9 4 7 )]。但此製法有所用《媒之後處理問題。 本發明者們致力於研究開發不用觭媒而以高産率製造 鹵苯氣脂肪酸衍生物之新潁製法，終於完成本發明。 由本發明製法製造之鹵苯氣脂肪酸衍生物可當作Η藥 ，農藥及化學品之中間體，有些為未見諸文獻之如下式 (I ’）之新穎化合物：
R2_ ------- -------------------] I -------71------- (請先閲讀评面之注意事項再堉寫本頁) 經濟邪中央標準局8工消费合作钍印5¥ 〔式中R’為氰基或-C0N(R3')RV (式中及R4'可相同 或相異，各為氳，低烷基.苯基，苯基而有1〜5個可相 同或相異取代基選自齒紫，硝基，氰基，低烷·基，低豳 烷基.低烷氣基，低豳烷氣基，低烷碕基及低豳烷硫基 本紙張又度適用中國因茱抒準（CNS)甲4峴格（210 X 2M ) 82,1. 20,000 Α6 Β6 五、發明説明（8 ) 醯胺，而在50C«拌下以12.3n丨/分之速度通入氰氣45 分。 反應終了後，加10%硫代硫酸納水.滅®蒸除溶劑。 於殘渣加2〇ml 10%碩酸氳納水，而以乙酸乙酯（30ml X 2)萃取。 有機層以無水硫酸鈉乾燥而減壓港縮成結晶後，以正 己烷洗淨.得2.07克所求2, 4 -二氣苯氣乙酸。 産率93 . 6% 此為己知化合物，熔點及NMR與文獄（J0C第428頁， 1 947)者一致。 表3乃示仿例1〜3製造之鹵苯氧脂肪酸衍生物（I)之 範例。 因表3之化合物為己知，故以文獻之熔點，NMR及IR 鑑定。 例4 2-氣-4-氟苯氣乙胺（化合物1之製造）
F 普 o-ch2cnh; C1； C1
O-CHiCNHi ------------------------^------.玎------線 (請先閲筇背面之注意事項再塡寫本頁) 經濟部中央標準局β工消費合作社印- 將1.69克（Θ.01莫耳）4-氬苯氣乙醛胺溶在llil乙酸 中，並在50它下予以加熱，而在501下以12.3ig1/分之 速度通入氮氣50分。 完成反塍後，加3 ID 1 1 0%硫代硫酸鈉水溶液，而減壓 蒸除溶劑，加2 0 is 1 1 0 S：磺酸氫鈉水溶液，以乙酸乙酯（ 30®1X2)萃取目的産物。 將有機層以無水硫酸鈉乾燥而減壓濃縮成結晶後，以 正己烷洗淨，得1.84克所求2-氛-4-氣苯氧乙_胺。 熔點：14 8 . 3 産率9Θ . 4% -1 0 - 本紙張尺度過用中國國家半（CNS)平4峴格UlO X 297 乂坫）
82.1, ^O.OUD 412514 A6 B6
五、發明説明（3 ) ，苄基或苄基而有1〜5鍺可相同或相異取代基苗自低院 基.低鹵烷基，低烷《基，低鹵烷氣基，低烷硫基及低 鹵烷硫基，R1'及R2/可相同或相異，各為氳或低烷基， 乂’為氣，碘，溴或低烷基，¥^為鹵素，但當|{1/及1?2'為 氳，X ’為氟，Y ·為氮時，fT不為氰基〕。 本發明之豳苯氣脂肪酸衍生物可由如下製法製造 R1 R2 (II) (式中R.Ri.RS.X及Υ同前）。 所求鹵苯氣脂肪酸衍生物可將苯氣脂昉酸（I)在惰性 溶劑中以鹵化劑鹵化來遘搽製造。 用於本發明之惰性溶剤可為任何不阻礙上述反應進行 者，例如，齒化烴，如二氣甲烷，氣仿，四氣化硪及全 氛乙烷；羧酸，如甲酸，.乙酸及丙酸；芳族烴，如硝苯 ，氣苯.二氡苯及三氣苯；醋，如乙酸乙酯；腈.如乙 膪，及苄腈；醛胺，如二甲基甲薛胺及二甲基乙趦胺， 四亞甲袓，二甲确，二甲亞δΛ, 1, 3 -二甲基-2 -味唑二 瞬.及水。這些愤性溶劑可各單獨使用或併用。 至於豳化劑.可用例如氮，溴，碘，鹽酸-過《化氫 I.裝------#------線 <揞先W讀背面之注意事項再墦鸾衣頁} 經濟部t央標準局R工消費合作社印Κ 衣紙張又度遴用中理31家捸苹（CNS)甲4规格（21ϋ X 297公釐〉 82,1. 20,000 412^14 Λβ Β6 五、發明説明（4) ,iiiSft,五氯化铱.N, H -二氰脲.N -氰丁二雔亞胺 .N-溴丁二酵亞胺，次鹵酸第三丁酯.三«之聚異氰酸 及三氮甲磺趦囪。鹵化劑之fi可對每契耳苯缜脂肪酸 (I )任意選自0.1M耳〜過量其耳倍。 必要時.在本發明製法中可用有機鹺，無機鹼或有機 鹽。有機鹺之例為如三乙胺及吡啶等胺，無機飴之例為 鹾金屬或齡土金®氫《化物，如NaOH, KOH, Ca(OH)2 &Ba(0H)2 ,及齡金靥或鹸土金屬硝酸鹽，如碩酸納， 硝酸鉀及硪酸鈣，有機鹽之例為有機酸之龄金屬或齡土 金屬鹽，如乙酸鈉，乙酸鉀，乙酸鈣及苯甲酸納及乙酸 銨。其用量對每莫耳苯氣脂肪酸（E)可任意選自0.1莫 耳〜過量莫耳倍。 反應溫度可任意選自-20 C〜所用情性溶劑之沸點。 反應時間取決於反應溫度及反應規模，但可選自數分 〜4 8小時。 反應完成後，目的物之單離可甩常法，例如以溶劑萃 取，必要時精裂以柱層層析，再结晶，蒸晡等，則可産 生齒苯氣脂肪酸衍生物U )或（I ’）。 屬於新潁化合物（I')之代表例如下表1。 (請先閱讀背面之注意事項再碩鸾本頁) 娩濟·邵中央揉準局S工消費合作社印*'·"- 本紙ft又度迫和中國两家標竿（CNS>甲4现格（210 X 2D7 乂» ) 82.1. *<?0,000 五、發明説明（5 )
X
ΛΓ» B6 (!') .编 號 X1 Y' Rl* R2- R* 産率 (%} 性質 (m.p./°C) 1 F Cl H H conh2 90.4 148.3 2 F Cl H H CONHCH3 92.0 87*9-88.1 3 F Cl H H CONHC2H5 75*6 66*8—67*0 4 F Cl H H CONHC3H7-i 81·5 117.1 5 F Cl H H CON (CH3)2 74.7 79,8-81,7 Cl 6 F Cl H H CONH-^ 〇Xci 81.6 151.6-152.5 7 X Cl H H c〇tC 84.7 103.6 8 F Cl ch3 H CN 80.6 Oil 9 ch3 Cl H H CONH5 70 · 2 Oil 在表1之性質檷中「油」者化合物之ΝΜϋ數據如表2 冬紙張尺度過祀taa家標苹（CNS) f 4規格（210 X 297公货> 82J. 20,000 (請先M讀背面之注意事項再填寫本頁) -裝， -- 412514 ΛΓ> Β6 五、發明説明（6 ) 表 2 编號 1H-NHR(CDC13, ppm) 8 1.63 {3H, d), 4.97 (1H, m), 6.99 (1H, m), 7.08 (1H, (3. d), 7·17 (1H, d. d). 9 2.27 (3H, s), 4.49 (2H, s), 5.64 (1H, br)f.6.79 (1H, br), 6.80 (1H, d), 7.02 (1H, d. d), 7.20 (1H, d). 本發明以如下非限制範例説明之。 例1 2-氛-4-氩苯氧乙腈（化合物25之製造） .C1 先Μ讀背面之注Φ事項再播窝本頁)
F ch2cn
Cl2
F—( 〇 )~ 0-CH2CN 烴濟部中央標竿局8Η消費合作社印3衣 將1.51克（0.01莫耳）4-氟苯氣乙腈及0.82克（0.01 莫耳）乙酸鈉溶在7b1乙酸及3m丨水之混液，而在50¾¾ 拌下以12.3nl /分之速度通入氣氣60分。 完成反應後，加3nl 10%碕代碕酸納水，而減®蒸除 溶劑，加20nl 10¾¾酸氳鈉水.以乙酸乙酯（30alx2) 萃取，以無水硫酸鈉乾燥，減壓港縮而蒸脯，得1.54克 2-氯-4-S苯氧乙脯。 "8 本紙張又度通用中aa家標準（CNS>甲Ο見格（2〗0 X 25)7公) 82.1. 20,0ϋ0 Μ _I_ __Β6_ 五 '發明説明（7 ) 此為已知化合物，熔點及rtMR與文獻（CA 124017«)—致D 産率83 . 0% 例2 2, 4 -二氮苯《乙匿胺（化合物10)之製造
將1.86克（0.01莫耳）4 -氛苯氣乙g胺在50X：加熱溶 在11 m 1乙酸.而在同溫以1 2 . 3a 1 /分之速度通人氣氣5 0 分。 反應终了後，加3nl 10Χ硫代硫酸納水而減壓蒸除溶 劑.加2 0 b 1 1 0 %硪酸氫鈉水，而以乙酸乙酯（3 0 m 1 X 2 ) 萃取。 將有機層以無水硫酸鈉乾燥而滅壓濃縮成結晶後，以 正己烷洗淨，得2.02克所求2, 4 -二氛苯氣乙醛胺。 産率92 . 0% 此為己知化合物，熔點及HMR與文獻（J0C第428頁，1947)者一致。 例3 2, 4 -二氮苯氧乙酸（化合物17)之製造 ----------------,--------裝------.玎----——線 (請先《ίί背面之注意寧項再填寫本頁} 烴濟部中央標準局8工消t合作社印¾
1 . 8 7克（0 . 0 1其耳）4 -氱苯《乙酸投入1 0 m丨二甲基甲 -9 - 本紙张尺Λ通州中《國家樣苹（CNS)甲4现格（210 X 297 ) 82.1. ΙΌ 000 Α6 Β6 五、發明説明（8 ) 醯胺，而在50C«拌下以12.3n丨/分之速度通入氰氣45 分。 反應終了後，加10%硫代硫酸納水.滅®蒸除溶劑。 於殘渣加2〇ml 10%碩酸氳納水，而以乙酸乙酯（30ml X 2)萃取。 有機層以無水硫酸鈉乾燥而減壓港縮成結晶後，以正 己烷洗淨.得2.07克所求2, 4 -二氣苯氣乙酸。 産率93 . 6% 此為己知化合物，熔點及NMR與文獄（J0C第428頁， 1 947)者一致。 表3乃示仿例1〜3製造之鹵苯氧脂肪酸衍生物（I)之 範例。 因表3之化合物為己知，故以文獻之熔點，NMR及IR 鑑定。 例4 2-氣-4-氟苯氣乙胺（化合物1之製造）
F 普 o-ch2cnh; C1； C1
O-CHiCNHi ------------------------^------.玎------線 (請先閲筇背面之注意事項再塡寫本頁) 經濟部中央標準局β工消費合作社印- 將1.69克（Θ.01莫耳）4-氬苯氣乙醛胺溶在llil乙酸 中，並在50它下予以加熱，而在501下以12.3ig1/分之 速度通入氮氣50分。 完成反塍後，加3 ID 1 1 0%硫代硫酸鈉水溶液，而減壓 蒸除溶劑，加2 0 is 1 1 0 S：磺酸氫鈉水溶液，以乙酸乙酯（ 30®1X2)萃取目的産物。 將有機層以無水硫酸鈉乾燥而減壓濃縮成結晶後，以 正己烷洗淨，得1.84克所求2-氛-4-氣苯氧乙_胺。 熔點：14 8 . 3 産率9Θ . 4% -1 0 - 本紙張尺度過用中國國家半（CNS)平4峴格UlO X 297 乂坫）
82.1, ^O.OUD A6 B6 五、發明説明（9 )
X
堙濟部中央標準局負工消贽合作杜印製 编號 X1 y1 Rl* R2' R1 産率（％) 10 C1 Cl H H CONH2 92.0 11 C1 Cl H H CONHCH3 94*4 12 C1 Cl H H CONHC2H5 93.3 13 C1 Cl H H CONHC3H7-i 87_5 14 C1 Cl H H con(ch3)2 77.4 Cl 15 C1 Cl H H CONH — (〇yci 81*7 ϋϊ 16 C1 Cl H H /~ CON^^ 96,2 17 C1 Cl H H COOH 93.6 18 C1 Cl H H c〇〇ch3 81.5 19 C1 Cl H H C00C2H5 83,6 20 C1 Cl H H COOC3H7 -i 87.1 21 F Cl H H COOH 80,6 22 F Cl H H COOCH3 84.2 23 F Cl H H COOC2H5 76,3 24 F Cl H H COOC3H7 -i 80.9 25 F Cl H H CN 83.0 26 C1 Cl ch3 H COOH 82.0 27 C1 Cl ch3 H CONH2 88.9 28 C1 Cl ch3 H /~\ CON ) 74.5 29 C1 Cl ch3 H COOCH3 81.5 '30 F Br H H COOH 81.2 31 F Br ch3 H COOH 78.9 -11- 裝 訂 缘. 本紙张又度適用中Ββ家镖準（CNS)甲4规格（210 X 297公* ) A6 B6 五、發明説明（10)齒苯氧脂肪酸衍生物（I )為重要之中間體供製迫曰本 待開平3-163063中除草劑。最後産品典型除草劑可由如 下製法製造。
Cfi2=CHOC4Hg —η 0 II R3"〇-C-OR3" 觸媒 (揞先Mir背面之注意事項再場窝本頁)
V
R1 I O-C-R I R2 m II ο R3"-C-CH2C 'ii II ο ο
環化
OH 薛化 γ
R 1 R 1 煙濟部中央標準局負工消f合作社印"
ο I 2 cl R /Λ/
N
N— R
'OR
R /Λ/ - o R1—c·
Y
N N- -12- 本紙张尺及適用家標芊4峴格（210 X 297公货> a Η 5 R b
2 R
4 R 82·]. 20,rn)0 412814 %： A6 B6 五 '發明説明（11) (式中R, R 1 , R 2 . X及Y同前，R3"為低烷氣基，R4" 為低烷基或低鹵烷基.R5"為低烷基或低豳烷基 Hal為齒 素）0 (請先閱讀背面之注意事項再填寫夂莨) 經濟·邵中央標準局S工消費合作社印κ -13- 本紙張尺度迺用中两國家愫苹（CNS)甲Ο见格（210 X 297公a > 82Α. ^α,ουο

Claims (1)

  1. 4 1 25 412 X 8 8 8 8 ,ABCD 申請專利乾圍 第S 4 1 0 5 4 5 1號「s苯氣脂肪酸衍生物」專利菜 U7年L 与1 1曰修正$ 年月 巧申請專利範圍： 丄.一種如下式（Γ)鹵苯氧脂防酸衍生物
    工丨） R2, 〔式中R ’為氰基或-CON (R3' ) R〃（式中R3;及R4'可相 同或相異，各為氫原子，Cl - 3烷基，或具有選自 氯原子之1〜2個取代基之苯基，及R3'和ΪΤ'可共為伸 烷基），Ri為氳原子或C i - 3烷基，為氫原子， X'為氟原子或k - 6烷基，V為氣原子，但當R1'及 Rf為氳原子，X'為氟原子和Y’為氯原子時，R'不為 第基〕。 ‘ ^^^1 mi in^i —^ϋ ^^^^1 In Bn·—- fn ^ ^ *^s^. 浲 i 务 {請先閱讀背面之注意事項再填寫本頁) 經濟部中夹標车局員工消費合作社印製 本紙張尺度逋用中國國家橾準（CNS > A4規格（2丨0X297公釐） 4 1 25 412 X 8 8 8 8 ,ABCD 申請專利乾圍 第S 4 1 0 5 4 5 1號「s苯氣脂肪酸衍生物」專利菜 U7年L 与1 1曰修正$ 年月 巧申請專利範圍： 丄.一種如下式（Γ)鹵苯氧脂防酸衍生物
    工丨） R2, 〔式中R ’為氰基或-CON (R3' ) R〃（式中R3;及R4'可相 同或相異，各為氫原子，Cl - 3烷基，或具有選自 氯原子之1〜2個取代基之苯基，及R3'和ΪΤ'可共為伸 烷基），Ri為氳原子或C i - 3烷基，為氫原子， X'為氟原子或k - 6烷基，V為氣原子，但當R1'及 Rf為氳原子，X'為氟原子和Y’為氯原子時，R'不為 第基〕。 ‘ ^^^1 mi in^i —^ϋ ^^^^1 In Bn·—- fn ^ ^ *^s^. 浲 i 务 {請先閱讀背面之注意事項再填寫本頁) 經濟部中夹標车局員工消費合作社印製 本紙張尺度逋用中國國家橾準（CNS > A4規格（2丨0X297公釐）
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