、發明説明（i 本發明係有關製備通式10-(2_羥基烷基）肟之方法 R2〆 C== N 0-— CH-2. Description of the invention (i. The invention relates to a method for preparing an oxime of the general formula 10- (2-hydroxyalkyl) R2〆 C == N 0-— CH-
CH3 I • CH — OH (I) 經濟部中央橾隼局員工消費合作社印裂 此處Rl與R2各爲具有1到10個碳原子之烷基，抑或與攜有 其兩者之碳原子一起鍵結成爲5_或7_員之環烷基。 0 - ( 2 -羥烷基）肟作爲供作物保護劑用之中間體具有非常 I重要性（參見例如，早期之德國申請案DE-A44i5 887)。 利用經基胺之0·烷化作用製備j類型化合物中，多少總會 生成I之異構化合物，其係于鄰近肟氧位置之C原子上攜 CH3基團。 „ 先前所述環氧乙烷氫化作用致形成一級醇或二級與一級醇 的混合物（參見例如US 4,〇64，;i86&H〇uben_Weyl，Meth〇den der Organischen Chemie]：有機化學之方法]，Ge〇rg ThiemeVedag，Stuttgart，Vol. 6/3,第 4 版，1965, 442_446頁）。 本發明目的爲提供對〇-(2_羥基烷基）肟1而言達成具較高 區域選擇性及大體上無副產物形成之方法。 吾等頃發現，該目的可經由包含使用催化性氯化通式 〇-(2,3·環㈣基）Μ製備式㈣介祕祕）狀方法而 達成。 C — Ν —— 0- (請先閱讀背面之注意事項再填寫本頁) 訂 線' R2- 0 ’CH2— CH· CH, (II) 下文中，H〇uben-Weyl文獻，考資料係：H〇uben Wey卜 Methoden der Organischen Chemie(有機化學之方法），第4版 ，Thieme Verlag，Stuttgart。 於可根據本發明方法製備之化合物，較佳者爲其"丨 -4- 本紙張尺度適用中國國家標準（CNS ) A4規格（2I0X297公釐CH3 I • CH — OH (I) Printed by the Consumer Cooperative of the Central Government Bureau of the Ministry of Economic Affairs. Here R1 and R2 are each an alkyl group with 1 to 10 carbon atoms, or they are bonded together with a carbon atom carrying both of them. Form a 5- or 7-membered cycloalkyl. 0- (2-hydroxyalkyl) oxime is of great importance as an intermediate for crop protection agents (see, for example, the earlier German application DE-A44i5 887). In the preparation of type j compounds by the 0 · alkylation of alkylamines, the isomers of I will always be formed to some extent, which carry the CH3 group on the C atom adjacent to the oxime oxygen position. „The hydrogenation of ethylene oxide previously described results in the formation of a primary alcohol or a mixture of secondary and primary alcohols (see, for example, US 4, 〇64, i86 & Houben_Weyl, Methoden der Organischen Chemie): methods of organic chemistry ], Georg ThiemeVedag, Stuttgart, Vol. 6/3, 4th edition, 1965, pages 442-446). The object of the present invention is to provide a higher regional selection for 0- (2-hydroxyalkyl) oxime 1. And substantially no by-product formation methods. We have found that this purpose can be achieved by a method comprising the use of a catalytic chlorinated general formula 0- (2,3. Achieved. C — Ν —— 0- (Please read the notes on the back before filling in this page) Order line 'R2- 0' CH2— CH · CH, (II) In the following, Houben-Weyl literature, test data Department: Houben Wey, Methoden der Organischen Chemie (Method of Organic Chemistry), 4th edition, Thieme Verlag, Stuttgart. For compounds that can be prepared according to the method of the present invention, the preferred one is " 丨 -4- this paper Standards apply to Chinese National Standard (CNS) A4 specifications (2I0X297 mm
經濟部中央標準局員工消費合作社印製 與R2個爲Ονον燒基，而特別係Ci_C3·燒基，抑或與攜有其兩 者之反原子齊形成環戊基或環己基環。尤佳爲Rl與R2個 爲甲基或乙基，特別是兩者均爲甲基。 0-(2,3-環氧烷基）肟！！爲一般已知者，或可藉已知方法 獲得，特別爲利用於偶極非質子性溶劑中使用游離肟行對應 之表鹵代醇之驗催化反應（參見例如Zh. 〇rg. Khim. 5(1969)， 1353 頁至 1355 頁）。 ’ 對氨化作用而言適當之催化劑如例如H〇uben_Weyl， Volume 4/lc中所述乃爲此目的之一般習用的催化劑。 較佳I氳化作用催化劑爲含根據週期表11^八(：分類8到 肤金屬者，較佳爲元素鈷，铑及釕〜族者，特別是元素鉑及鎳 ’而尤其爲免。 孩等催化劑可如此使用，或較佳爲撑載於撑體上。慣用撑 體物質，像是梦;5 '氧化銘、二氧化钦、#酸鹽及滞石，特 別是活性炭，爲合適者。 對經撑載催化劑製備而言，可額外使用粘合劑或成型助劑 。孩催化劑可以小片狀，擠出物，錠劑或球形式使用。 通常每莫耳待氫化化合物Π使用〇 .丨至丨重量％的催化劑， 此疋量數據與不含撑體物質之催化劑的有效質量有關。 氫化作用可連續或較佳以批次方式進行。 液相之批次方法中，氫化作用可在溶劑存在下進行。適當 落劑爲譬如醜及醇以及其混合物之極性溶劑。較佳落劑爲具 有多達6個碳原子的醚或醇類_如丨，2_二甲氧基乙烷、乙 醇、正-丙醇、異丙醇及正_ 丁醇。 壓力可在大範圍中作選擇，由！巴延伸至4〇〇巴，但反應 較佳于範圍係1至1 0 〇巴，特別是丨〇至7 〇巴，尤佳是3 〇至 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公瘦 (請先閱讀背面之注意事項再填寫本頁) 訂 線- 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（3 ) 5 0巴下進行。 氫化作用期間之溫度較佳爲〇到10(rc，特別是1〇到5(rc 而尤其是2 5到3 0 °C。 反應產物I利用本身屬已知之方法分離，較佳爲利用蒸餾 作用，化合物I之產率一般爲7〇到90 %，選擇率通常則超過 9 8%。 根據本發明方法所得〇_(2_羥基烷基）肟1適合作爲除草劑 之前驅體，特別是環己晞酮型式者（參見例如DE-A 44 15 887)。 實例 2-丙酮〇-(2-羥基丙基)肪之製備 〜 · 用4克麵/碳（1〇重量％把）處理13〇克（〇 94莫耳）2_丙酮〇_ (2-環氧丙基）肟（參見 EP-A 23 560; Zh. Org. Khim. 5(1969)， 1353頁至1355頁）及600毫升乙醇，並于25。匚及50巴氫壓下氫化 該混合物。1 7小時後反應完全。過濾掉催化劑。然後移除 溶劑並通過長爲50公分而直徑爲5公分的填充管柱蒸餾殘餘 物。該管柱係填充有直徑爲3毫米的線網環狀物（溶點：74°C /20毫巴）。 2 -丙酮〇 - ( 2 -羥基丙基）肟之產率爲8 4 %，純度爲9 9.8 % 。本情況中無2 -丙酮0-(2 -羥基-1-曱基-乙基）肪異構物形 成。 本纸張尺度適用中國國家標準（CNS ) A4规格（210X 297公瘦） (請先聞讀背面之注意事項再填寫本頁)Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs and R2 are Ονον fired bases, and especially Ci_C3 · fired bases, or they form a cyclopentyl or cyclohexyl ring together with their counteratoms. It is particularly preferred that R1 and R2 are methyl or ethyl, and especially both are methyl. 0- (2,3-epoxyalkyl) oxime! !! Khim. 5 is generally known, or can be obtained by known methods, in particular, by using a free oxime in a dipolar aprotic solvent to test the corresponding epihalohydrin (see, for example, Zh. 〇rg. Khim. 5 (1969), pages 1353 to 1355). A catalyst suitable for the amination is described in, for example, Houben_Weyl, Volume 4 / lc, and is a catalyst conventionally used for this purpose. The preferred catalysts for tritiation are those containing metals to skin metals according to the Periodic Table 11 ^ 8 (: Classification 8), preferably the elements cobalt, rhodium and ruthenium ~, especially the elements platinum and nickel. Such catalysts can be used as such, or they are preferably supported on a support. Conventional support materials, such as dreams; 5'-oxide, dioxin, acid salt and stagnation, especially activated carbon, are suitable. For the preparation of supported catalysts, additional binders or molding aids can be used. The catalysts can be used in the form of tablets, extrudates, pastilles, or balls. Usually used per mole of compound to be hydrogenated. To 丨 wt% of the catalyst, this amount of data is related to the effective mass of the catalyst without supporting substances. Hydrogenation can be performed continuously or preferably in a batch manner. In the liquid phase batch method, the hydrogenation can be performed in a solvent It is carried out in the presence of a suitable solvent, such as polar solvents such as ugly alcohol and mixtures thereof. Preferred solvents are ethers or alcohols having up to 6 carbon atoms. , N-propanol, isopropanol and n-butanol. Choose from a wide range, extending from! Bar to 400bar, but the reaction is better than the range of 1 to 100bar, especially 丨 0 to 70bar, especially preferably 30 to this paper size. China National Standard (CNS) A4 specification (210X297 male thin (please read the precautions on the back before filling out this page) Threading-Printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (3) 5 0 bar The temperature during the hydrogenation is preferably 0 to 10 (rc, especially 10 to 5 (rc and especially 25 to 30 ° C). The reaction product I is separated by a method known per se, preferably By distillation, the yield of compound I is generally 70 to 90%, and the selectivity is usually more than 98%. The 0- (2-hydroxyalkyl) oxime 1 obtained according to the method of the present invention is suitable as a precursor of a herbicide. Especially cyclohexanone type (see, for example, DE-A 44 15 887). Example 2-Preparation of acetone 0- (2-hydroxypropyl) fat ~ · 4 g of noodles / carbon (10% by weight) Treatment of 130 grams (〇94 mol) of 2-acetone and 0- (2-epoxypropyl) oxime (see EP-A 23 560; Zh. Org. Khim. 5 (1969) (Pages 1353 to 1355) and 600 ml of ethanol, and the mixture was hydrogenated at 25 ° C. and 50 bar hydrogen pressure. The reaction was complete after 17 hours. The catalyst was filtered off. The solvent was then removed and the diameter was 50 cm. 5 cm packed column distillation residue. This column is filled with a wire mesh ring with a diameter of 3 mm (melting point: 74 ° C / 20 mbar). 2-Acetone 0- (2-Hydroxypropyl The yield of oxime was 84% and the purity was 99.8%. In this case, no 2-acetone 0- (2-hydroxy-1-fluorenyl-ethyl) fatty isomer was formed. This paper size applies to China National Standard (CNS) A4 (210X 297 male thin) (Please read the precautions on the back before filling this page)