TW314515B - - Google Patents
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- TW314515B TW314515B TW083107263A TW83107263A TW314515B TW 314515 B TW314515 B TW 314515B TW 083107263 A TW083107263 A TW 083107263A TW 83107263 A TW83107263 A TW 83107263A TW 314515 B TW314515 B TW 314515B
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- triazole
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
- C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles 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
- C07D249/12—Oxygen or sulfur atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
- C07C211/45—Monoamines
- C07C211/46—Aniline
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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
五、發明説明（ Α7 Β7 本發明係有關一種改良製造做為除草劑之中間體極為 有效的碕化合物之方法。 在日本特開平1-121279號公報、特開平2-1481號公報 公報 、特開平2-233665號>或特開平3-279368號公報中記載使 用各種三唑化合物做為除草劑之有效成份，係使用一般 式（® )所示之硫化合物做為此等之中間體， R.5. Description of the invention (Α7 Β7 The present invention relates to a method for improving the production of extremely potent compounds as intermediates for herbicides. In Japanese Patent Laid-Open No. 1-121279, Japanese Patent Laid-Open No. 2-1481, Japanese Patent Laid-Open No. No. 2-233665 > or Japanese Patent Laid-Open No. 3-279368 describes the use of various triazole compounds as active ingredients of herbicides, and uses sulfur compounds represented by the general formula (®) as intermediates for these, R .
N-NH-Λ； Ν (III) --------V —裝-- (請先閲诔背面之注意事項再填寫本頁) 經濟部中央揉準局貝工消费合作社印製 (其中，R 1 、R 2及R 3係表 烷基、低級烷氧基或三氟甲 因此，該硫化合物之製法 物及三唑化合物反應的方法 ，其產率低，工業生產性不 確的記載有關例如反應溫度 劑之方法與產率的關係，尤 的物之硫化合物的方法不充 所Μ，本發明人等確知此 有利地製造一般式（H )所示 本發明人等首先檢討反應 測驗重氮化合物與三唑化合 Kcal/nlo(係為極大之值 度愈低（較佳者為10DM下， 示氫原子、鹵素原 基；X係表示陰離 雖記載或揭示有關 ，惟藉由此等所記 足。在此等之文獻 及產率的關係，混 其Μ工業規横來製 分0 等公知的方法在工 之硫化合物。 溫度與產率的關係 物之反應熱结果為 故確認在本反應中 更佳者為5DM下 子、低级 子殘基）< 重氮化合 載的方法 中沒有明 有反應試 造做為目 業上無法 ,且實際 60〜70 ,反應溫 ),其產 訂 線 -3 - 本紙張尺度適用中國國家橾準（CNS ) A4規格（210X297公釐） 4515 A7 B7 五、發明説明（> ) 率愈高；而且重氮化合物及三唑化合物之混入時間（或 滴入時間）愈短者，其產率愈高。 另外，K工業規模製造目的物之硫化合物時，由於需 要長時間除熱，不易在短時間内低溫下予Μ反應。 典型例係有藉由將冷媒加入套管内Κ保持低溫的容器 内加入下述一般式（I )所示之三唑化合物溶液，N-NH-Λ; Ν (III) -------- V — installed-(Please read the precautions on the back before filling out this page) Printed by Beigong Consumer Cooperative of the Ministry of Economic Affairs Among them, R 1, R 2 and R 3 are epialkyl groups, lower alkoxy groups or trifluoromethyl. Therefore, the method for preparing the sulfur compound and the method for reacting the triazole compound have low yields, and the industrial productivity is not accurate The relationship between, for example, the method of the reaction temperature agent and the yield is described, and the method of the sulfur compound is not sufficient. The inventors have confirmed that this advantageously produces the general formula (H). The inventors first reviewed the reaction Test the combination of diazo compound and triazole Kcal / nlo (the maximum value is the lower the value (preferably 10DM, showing hydrogen atom, halogen original group; X series means that although it is recorded or revealed, but by These are enough. In the literature and the relationship between the yields, the sulfur compounds are processed by the well-known methods such as 0 according to the M industrial regulations. The result of the reaction heat of temperature and yield is the reason Confirm that the better in this reaction is the 5DM sub- and lower sub-residues) < There is no reaction trial manufacturing in the law as the industry is impossible, and the actual temperature is 60 ~ 70, the reaction temperature), its production line-3-this paper scale is applicable to the Chinese National Standard (CNS) A4 specifications (210X297 mm) 4515 A7 B7 V. Description of the invention (>) The higher the rate; and the shorter the mixing time (or dropping time) of the diazo compound and the triazole compound, the higher the yield. In addition, the K industrial scale manufacturing object For sulfur compounds, it takes a long time to remove heat, so it is not easy to react with M at a low temperature in a short period of time. A typical example is to add a refrigerant to a container that keeps the temperature low by adding the following general formula (I) Of triazole compound solution,
(II) (其中Μ係表示鹼金屬或驗土金臑） 然後將下述一般式（I)所示之重氮錨鹽化合物溶液滴入 三唑溶液中R, Ra(II) (where M represents alkali metal or earth test gold) then drop the solution of diazo anchor salt compound represented by the following general formula (I) into the triazole solution R, Ra
N +三 NX (I) 經濟部中央橾準局肩工消费合作社印装 (其中，Ri 、R2及R3係表示氫原子、鹵素原子、低级 烷基、低鈒烷氧基或三氟甲基；X係表示陰離子殘基）。 在該習知的方法中，需要一段不可預測的長時間以滴入 反應試劑，而導致工業上製造低產率的目的產物。 本發明之目的係提供Μ工業規模、高產率、且於工業 上有利的製造目的物之硫化合物的方法。 本發明係提供一種硫化合物之製法，其係在使一般式 (I )所示之重氮化合物及一般式（Π)所示之三唑化合物 ---------------ΐτ----->0(請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐）N + Tri NX (I) Printed by the Central Business Bureau of the Ministry of Economic Affairs of the Consumer Cooperative (where Ri, R2 and R3 represent hydrogen atoms, halogen atoms, lower alkyl groups, lower alkyloxy groups or trifluoromethyl groups; X represents an anion residue). In this conventional method, an unpredictable long time is required to drip the reaction reagent, resulting in industrial production of the target product with low yield. The object of the present invention is to provide a method for producing a sulfur compound of interest on an industrial scale, high yield, and industrially advantageous. The present invention provides a method for preparing a sulfur compound, which uses a diazo compound represented by general formula (I) and a triazole compound represented by general formula (Π) ------------- --lsτ ----- > 0 (Please read the precautions on the back before filling in this page) This paper size is applicable to China National Standard (CNS) Α4 specification (210X297mm)
AA
經濟部中央揉準局wc工消費合作杜印装 係度 。 上使，} 法溫 圖 造制法(I 方的明 製強方式 良液說 地現的般 改應 的 利發度 一 其反器 有i溫或 3,制容 上Η液丨。 物 结 I ”控應 業以應{熱 以以反器 ΗΗ反式應 Η器 a 0 Hu整般反 流" 2換器反 有調一去 ¾2¾1ΛΜ^除 U熱交 DR 研Ρ器上地 S部熱之 人以換人效 I外部物器深2.1交滴有 (I於 外合泵換三D熱内可 式環有化環交再ITf部間且 }般循置器氮循熱經)^外時 ， 彡一液明設慝重制部管等II於短物 {得應說為反含強外套人(I環在合 明製反單係；明式循量^ 説，使簡1; : : ; i發般液儘之 W應制式圖12345本一應可示 發反強圖 述反係所 而且，例如亦可以考慮在減壓條件下迴流反應溶劑， 藉由彼之蒸發潛熱予Μ除去反應熱，惟該反應由於會生 生與一般式（I)所示之重氮化合物相對莫耳的氮氣，故 真空糸之排氣量極大，此法係為不適。 此外，本發明人等發現本發明之方法中，藉由間斷式 滴入上述一般式（I )或一般式（I)任一種的反應試劑以 達到除去反應熱的效果，此係具有提高產率效果的作用。 換言之，本發明人等經過再三研究工業上製造上述一 般式（I)所示之硫化合物方法之有利條件，结果發現若 是上述一般式（I )或一般式（Π )所示化合物之實質滴人 時間為短時間時，即使開始滴入至滴完為止之時間為長 時間，其降低產率的情形極小；而且發現藉由間斷地滴 入上述一般式（I )或一般式（H )所示之任一種的反應試 劑，可以顯著地提高產率。 因此，本發明之最佳實施形態，係組合強制循環於外 部熱交換器之方法，及間斷地滴入上述一般式（I)或一 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） ----------^------1T------ά. (請先閲讀背面之注意事項再填寫本頁)The Ministry of Economic Affairs Central Bureau of Accreditation WC Industrial and Consumer Cooperation Du Printing System. The use of the method, the method of making the temperature and temperature map (I's method of making the liquid better in the way of making a strong solution, and the normal level of resilience is that it has a temperature of 3 or 3, and the volume is made up of liquid 丨. I ”Control the application industry to respond to {the heat to the reactor ΗΗ reverse-type reactor a 0 Hu general reverse flow " 2 converter anti-adjustment go to ¾2¾1ΛΜ ^ except U thermal cross DR researcher device on the ground S The hot person has the effect of changing the I. The external object has a depth of 2.1. Outside, 彡 一 液 clearly set up the remanufacturing department tube and so on II in the short thing {should be said to be anti-contained strong coat person (I ring in the Heming system anti-single system; the Ming Dynasty ^ said, make Jane 1; ::; I should be able to show the exhaustive W diagram in Figure 12345. It should be able to show a strong representation of the reaction system. For example, it can also be considered to reflux the reaction solvent under reduced pressure, by its latent heat of evaporation to Μ The heat of reaction is removed, but the reaction will generate nitrogen gas that is relatively molar to the diazo compound shown in the general formula (I), so the exhaust volume of the vacuum pad is extremely large, and this method is not suitable. In addition, the inventors found that The method of the invention In which, by intermittently dropping the reaction reagent of the above general formula (I) or any of the general formula (I) to achieve the effect of removing the reaction heat, this has the effect of improving the yield. In other words, the inventors have passed Re-examination of the industrial conditions for manufacturing the sulfur compound represented by the general formula (I) above, and found that if the actual drop time of the compound represented by the above general formula (I) or the general formula (Π) is a short time, even The time from the start of dripping to the end of dripping is a long time, and it is extremely rare to reduce the yield; and it was found that by intermittently dropping any of the reaction reagents shown in the above general formula (I) or general formula (H), The productivity can be significantly improved. Therefore, the best embodiment of the present invention combines the method of forced circulation in an external heat exchanger, and intermittently drops the above general formula (I) or a paper standard to apply the Chinese national standard ( CNS) Α4 specification (210Χ297mm) ---------- ^ ------ 1T ------ ά. (Please read the notes on the back before filling this page)
A7 B7 五、發明説明（4 ) 般式（I)所示之任一種的反應試劑之方法，亦即併用的 方法。此時，更可併用在反應器内設置通過有冷媒的線 圈，且使冷媒通過反應器内部之套管的辅助除熱方法。 下述中，更為詳细地說明本發明。 本發明所使用的一般式（I )所示之重氮銳鹽化合物， 係藉由使下述一般式（IV ) R | R 1 ^-NH: (IV) R3 (其中，Rl 、R2及R3係表不氬原子、齒素原子、低级 烷基、低級烷氧基、或三氟甲基） 所示之苯胺衍生物，使用鹽酸、硫酸等無機酸及亞硝酸 納予Μ偶氮化之習知方法而製得。 而且，上述一般式（I)所示之苯胺衍生物，具體而言 例如苯胺、2-氯苯胺、3-氯苯胺、4-氯苯胺、2-氯ΜΕ 氟甲基 苯胺、 2-三 氟甲基 苯胺、 3-三 氟甲基 苯胺、 4-三氟甲基笨胺、2-甲基苯胺、3-甲基苯胺、4-甲基苯胺 、4-乙基苯胺、2-甲氧基苯胺、3-甲氧基苯胺、4-甲氧 基笨胺、3,5-二氯苯胺、2, 4-二氟苯胺、3,5-二甲基笨 胺、2,4-二甲基苯胺、2,6-三甲基苯胺、2 -甲基-6-乙 基苯胺、2 -甲氧基-5-三氟甲基苯胺、3 -甲氧基-5-三氟 甲基苯胺、2,4,6-三甲氧基笨胺、2,4,5-三甲基苯胺、 2,4,5-三甲基-6-甲氧基苯胺等。 本紙張尺度適用中國國家標準（CNS ) Λ4规格（210X297公釐） I v —裝 訂 '—線 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央揉準局貝工消费合作社印製 Β7 五、發明説明（r ) 所，，所此可N,及 法 Μ 物I)。 亦、 物 方。 中生(I行需喃 合 的鹼 物。衍式進所呋 化 液入。 合等胺般 Μ 其氫 唑 溶滴驗 化鎂苯一予視四 三 鹽中及 唑、之與應，、 之。錨液物 三鈣示 g 反類烷 示法氮合合 之、所 g 中醇茂 所方重混化 示鉀IV)幽情等5«Π)種人之ηφ 所、 <氮溶醇、。(1[各滴物三 I)鈉式重性乙烷劑式述中合入 (I為般其惰、噁溶般下液化滴 式係一使在酵二他一用溶唑注 般靨使且，甲4-其與使鹽三併 一 金係 ，鹽用 1’ 之液慮鹼與中 之土 ，化之使、等溶考之液液 用鹼法氮物係腈胺氮可物溶溶 使或方偶合體乙釀重係合鹽鹽 所屬的中化氣、乙述，化錨錨 明金明酸氮性 _ 基上法唑氮氮 發鹼發機疊惰丙甲合方三重重 本的本無之，用二組之在在在 示 在示時併Ν-鹼 abc (請先閲讀背面之注意Ϋ項再填寫本頁) 經濟部中央揉準局貝工消費合作杜印裝 d在三唑化合物之溶液中併注滴入重氮鏘鹽溶液與鹼。 此時，各反應試劑之反應莫耳比.對一般式（E)所示 之三唑化合物的鹽類而言，一般式（I)所示之重氮化合 物為0.9〜1.5莫耳比，較佳者為1.0〜1.3莫耳比。 而且，反應所需之鹼量，對上述疊氱化合物而言，為 1.0〜3.5萁耳比，較佳者為2.2〜2.6莫耳比。 反應溫度為-20¾〜20t：,較佳者為-1〇·〇〜10C ;反 應時間通常為5〜60分鐘，較佳者為10〜30分鐘。 反應係在全部滴入的同時结束，惟滴入終了後，予以 携拌數分鐘〜數小時完结。A7 B7 5. Description of the invention (4) The method of any one of the reaction reagents shown in the general formula (I), that is, the method used in combination. In this case, it is also possible to use an auxiliary heat removal method in which a coil passing through a refrigerant is provided in the reactor and the refrigerant is passed through a sleeve inside the reactor. In the following, the present invention will be described in more detail. The diazonium salt compound represented by the general formula (I) used in the present invention is obtained by using the following general formula (IV) R | R 1 ^ -NH: (IV) R3 (wherein R1, R2 and R3 It does not represent the aniline derivatives represented by argon atom, halogen atom, lower alkyl group, lower alkoxy group, or trifluoromethyl group. The use of inorganic acids such as hydrochloric acid and sulfuric acid and nitrite to prepare nitrozobenzenes Know the method and made. Furthermore, the aniline derivatives represented by the above general formula (I), specifically, for example, aniline, 2-chloroaniline, 3-chloroaniline, 4-chloroaniline, 2-chloroMEF fluoromethylaniline, 2-trifluoromethyl Aniline, 3-trifluoromethylaniline, 4-trifluoromethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-ethylaniline, 2-methoxyaniline , 3-methoxyaniline, 4-methoxybenzylamine, 3,5-dichloroaniline, 2,4-difluoroaniline, 3,5-dimethylbenzylamine, 2,4-dimethylaniline , 2,6-trimethylaniline, 2-methyl-6-ethylaniline, 2-methoxy-5-trifluoromethylaniline, 3-methoxy-5-trifluoromethylaniline, 2 , 4,6-trimethoxybenzylamine, 2,4,5-trimethylaniline, 2,4,5-trimethyl-6-methoxyaniline, etc. This paper scale is applicable to the Chinese National Standard (CNS) Λ4 specification (210X297mm) I v —binding ”—line (please read the precautions on the back before filling in this page) Printed by the Ministry of Economic Affairs Central Bureau of Customs Beigong Consumer Cooperatives Β7 Fifth, the description of the invention (r), so it can be N, and method I). Also, the object. Mesozoic (line I needs to be alkalinated. The formula is added into the furfuration solution. It is combined with other amines such as its azole solution. The magnesium benzene is tested in the four or three salts and the azole is corresponding to it. The anchor liquid tricalcium shows the anti-alkane method, the nitrogen is combined, the g in the alcohol is remixed and the potassium is shown. IV) Youqing, etc. 5 «Π) The ηφ of the human species, < nitrogen soluble alcohol ,. (1 [each drop three I] sodium type heavy ethane agent is incorporated in the formula In addition, A4-It is combined with the salt and the gold series, the salt is considered to be alkaline and the middle soil with a 1 'solution, and the liquid solution is made to be soluble in the alkali method. Make or square coupling body B brewing heavy system with the combination of salt and salt belongs to the chemical gas, ethium, chemical anchoring mingling acid nitrous acid _ based on the fazole nitrogen nitrogen generator base lazy propane trimethine triple heavy If there is no such thing, use the two groups at the time of the display and display the N-base abc (please read the note Ϋ on the back side and then fill in this page). The solution of the azole compound is added dropwise into the solution of diazonium salt and alkali. At this time, the reaction molar ratio of each reaction reagent. For the salts of triazole compounds shown in the general formula (E), the general formula ( I) The diazo compound shown is 0.9 to 1.5 mol ratio, preferably 1.0 to 1.3 mol ratio. Furthermore, the amount of alkali required for the reaction is 1.0 to 3.5 moles for the above-mentioned stacked tritium compound Better than 2.2 ~ 2.6 molar ratio. The reaction temperature is -20¾ ~ 20t :, preferably -1〇 · 〇 ~ 10C; the reaction time is usually 5 ~ 60 minutes, preferably 10 ~ 30 minutes. The reaction system is in all The dripping is completed at the same time, but after the dripping is completed, it is carried and mixed for a few minutes to several hours.
本發明特徵之強制使反應液循環於外部熱交換器予W -7- 本紙張尺度適用中國國家揉準（CNS ) A4規格（210X297公釐） 經濟部中央揉準局只工消费合作社印製 A7 B7 五、發明説明（、） 調整反應液的溫度之方法，具體而言可藉由例如下述之 方法予Μ進行。 藉由圖面說明熱交換器之一例。圖1係為反應器内連 接外部熱交換器時之槪念圖；圖1中1係表示反應器， 2係表加入重氮化合物之反應器，3係表示為強制循 環所設的泵，4係表示外部熱交換器，5係表示套管。 在反應器1設置外部熱交換器（如層板式熱交換器4 ) ，且Μ泵3予以強制循環。此外，此時反應器1内使冷 卻鹽水等送至套管5予Μ調整溫度。 本發明之具體操作，例如先將一般式（I)所示之三唑 化合物之鹼鹽的甲醇溶液加入反應器1内，再自反應器 1強制取出該反應器，且經由熱交換器4再強制循環至 反應器1 。 然後，另外藉由將在反應器2中所製得的一般式（I) 所示之重氮化合物之溶液滴入反應器1 ，開始本發明之 反應。而且，此時藉由反應熱提昇反應溫度時，必須使 滴入速度減慢等。此外，可在反應器1内設置通過冷媒 的線圈等，且調整溫度做為此時之輔肋方法。 本發明人等發現若上述一般式（I )或一般式（Π )之化 合物的實質滴入時間為短時間時，即使開始滴入至滴完 的時間為長時間，其產率的降低情形很小；因此，在本 發明中藉由間斷地滴入上逑一般式（I )或一般式（I)之 化合物的任一種反應試劑，可得更佳的结果。該間斷地 滴入方法，具體而言可藉由如下述之方法予以進行。 -8- 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） --------V, —裝------訂-----.‘線 (請先Μ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 314515 A7 B7 五、發明説明（7 ) 如上所述，藉由將一般式（I)所示之重氮化合物之溶 液滴入，開始本發明之反應，藉此時之反應熱所提昇的 反應溫度，需在所定的溫度範圍内間斷地予Μ滴入，且 調整其滴入時間。該間斷滴入於第1次滴入終了後，藉 由外部熱交換器及套管等外部冷卻使反應液的溫度再達 到所定溫度，再進行第2次滴入。 如此保持所定的反應溫度，反覆地間斷滴人，完成反 應。間斷滴入的次數，因反應的規模，調整溫度的程度 而不同，沒有特別的限制，惟一般為3〜10次，尤Κ5〜 7次有利於實腌。 如上所述，藉由併用強制使反應液循環於外部熱交換 器以調反應液之溫度的方法Μ及上述間斷滴入的方法， 實質上更可縮短滴入時間及開始滴入至滴完的時間，係 為本發明之較佳實腌形態。 藉由本發明可以工業規模有效地工業上製造做為目的 之硫化物的產率佳。 而且，本發明之方法特別藉由併用上述之間斷滴入方 法，亦即倂用在反應器的外部設置熱交換器，Μ泵等強 制循環的方法Κ及間斷滴入的方法，可得更佳的结果。 於下述中，藉由實施例更具體的說明本發明之方法， 惟本發明不受此等之實施例所限制。 實施例1 在300 S·不銹鋼製反應鍋內加人20.4kg甲醇、8.66kg 3 -痴基-1H-1,2, 4 -三唑，然後在一邊攪拌、一逷冷卻旳 -9- 本紙張尺度適用中國國家揉準（CNS ) Α4規格（210X297公釐） --------"—裝------訂------ ά. (請先閲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杜印製 A7 B7 五、發明説明（f ) 情形下慢慢地加入13.25kg、95S；苛性鉀。苛性鉀完全加 入後，使-12^0鹽水通過設置在外部循環系之長度為80» 的板式熱交換器及300Α反應鍋之套管，Κ泵使其循環， 直至内液冷卻至-5t：為止。另外，在200JI玻璃管製反 應媧中加人82kg甲酵、11.65kg2,4,6-三甲基苯胺、18.75 kg、35%鹽酸，在冷卻為0〜5D下滴人14.6kg、40.7¾硝 酸納溶液，Μ形成重氮鹽。 Μ定量泉，將所形成的重氮鹽Κ 20分鐘Κ上的時間滴 入3-蹄基-1Η-1, 2,4-三唑之鉀鹽溶液中。反應溫度自〇υ 上升至9·Ό。使反應液加熱以餾去甲酵，且加入150Α水 後，Μ35ΪΚ鹽酸中和至pH為7。過滤、水洗、乾燥所析出 的结晶而得13.9kg目的物之硫化物。 產率：74S；(M3-蓣基-1H-1,2,4-三唑為基準） 純度：883!(LC面積百分率之值） 實施例2 在300 JL 不銹鏑製反應鍋内加入20.4kg甲醇、8.66kg 3-S[基-1H-1,2,4 -三唑，且在一邊授拌、一邊冷卻旳情 形下慢慢地加入13.25kg、955；苛性鉀。苛性鉀完全加人 後，使- lOt鹽水通過設置在外部循環系之長度為80m的 板式熱交換器及3001L反應鍋之套管，Μ泵使其循環直 至內液冷卻至-3¾為止。另外，在200 jl玻璃管製反應 鍋中加入98kg甲酵、14kg2, 4,6-三甲基苯胺、22.55kg 、35%鹽酸，在冷卻為0〜5C下滴入17.5kg、40.7¾硝酸 納溶液，Μ形成重氮鹽。 -10- 本紙張Α度適用中國國家標準（CNS ) Α4规格（210X297公釐） --------- —裝------訂-----~ I線 (請先閲讀背面之注意事項再填寫本頁) oonr ifci ,,,.The feature of the present invention is to force the reaction liquid to circulate in the external heat exchanger to W -7- The paper size is applicable to the Chinese National Standardization (CNS) A4 specification (210X297 mm). The A7 is printed by the Ministry of Economic Affairs, Central Bureau of Standardization, and only the Consumer Cooperative. B7 V. Description of the Invention (,) The method of adjusting the temperature of the reaction liquid can be specifically carried out by, for example, the following method. An example of the heat exchanger will be described with reference to the drawings. Figure 1 is a schematic diagram of the reactor when an external heat exchanger is connected; in Figure 1, 1 represents the reactor, 2 represents the reactor with diazo compounds added, 3 represents the pump for forced circulation, 4 The series represents the external heat exchanger, and the 5 series represents the bushing. An external heat exchanger (such as a layered plate heat exchanger 4) is provided in the reactor 1, and the M pump 3 is forced to circulate. In addition, at this time, in the reactor 1, cooled brine or the like is sent to the casing 5 to adjust the temperature. For the specific operation of the present invention, for example, a methanol solution of a basic salt of a triazole compound represented by general formula (I) is first added to the reactor 1, and then the reactor is forcibly taken out from the reactor 1, and then passed through the heat exchanger 4. Forced circulation to reactor 1. Then, by additionally dropping the solution of the diazo compound represented by the general formula (I) prepared in the reactor 2 into the reactor 1, the reaction of the present invention is started. Furthermore, when the reaction temperature is raised by the heat of reaction at this time, the dripping rate must be slowed down. In addition, a coil or the like passing through a refrigerant may be provided in the reactor 1, and the temperature may be adjusted as a supplementary rib method at this time. The present inventors have found that if the actual dropping time of the compound of the general formula (I) or the general formula (Π) is a short time, even if the time from the start of the dropping to the end of the dropping is a long time, the decrease in the yield is very serious Therefore, in the present invention, by intermittently dropping any reaction reagent of the compound of the general formula (I) or the general formula (I), better results can be obtained. This intermittent dropping method can be carried out specifically by the following method. -8- This paper scale is applicable to China National Standard (CNS) Α4 specification (210X297mm) -------- V, —installed ------ order -----. 'Line (please first Μ Read the precautions on the back and fill in this page) 314515 A7 B7 printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (7) As mentioned above, by combining the diazo compounds represented by the general formula (I) When the solution is dropped, the reaction of the present invention is started, and the reaction temperature increased by the reaction heat at this time needs to be intermittently dropped into M within a predetermined temperature range, and the dropping time is adjusted. After the intermittent drip is completed, the first drip is completed, and the temperature of the reaction liquid reaches the predetermined temperature again by external cooling such as an external heat exchanger and a sleeve, and then the second drip is added. In this way, the predetermined reaction temperature is maintained, and people are dropped repeatedly to complete the reaction. The number of intermittent drops is different depending on the scale of the reaction and the degree of temperature adjustment. There are no special restrictions, but it is generally 3 to 10 times, especially 5 to 7 times. As described above, by using the method M of forcibly circulating the reaction liquid in an external heat exchanger to adjust the temperature of the reaction liquid and the above-mentioned intermittent dripping method, the dripping time can be substantially shortened and the dripping can be started until the dripping is completed. Time is the preferred actual pickling form of the present invention. The present invention can efficiently produce industrially produced sulfides with good yield on an industrial scale. In addition, the method of the present invention can be better achieved by using the above-mentioned intermittent drip method, that is, the method of providing a heat exchanger outside the reactor, a forced circulation method such as an M pump, and the intermittent drip method. the result of. In the following, the method of the present invention is described more specifically by examples, but the present invention is not limited by these examples. Example 1 In a 300 S · stainless steel reaction pot, 20.4 kg of methanol and 8.66 kg of 3-kiloyl-1H-1,2,4-triazole were added, and then stirred while cooling to cool-9-this paper The standard is applicable to China National Standard (CNS) Α4 specification (210X297mm) -------- " —installation ------ order ------ ά. (Please read the notes on the back first Please fill in this page again) A7 B7 of the Beigong Consumer Cooperation of the Central Bureau of Economic Affairs of the Ministry of Economic Affairs. Fifth, the description of the invention (f) In the case of slowly adding 13.25kg, 95S; caustic potash. After the caustic potash is completely added, the -12 ^ 0 brine is passed through the plate heat exchanger with a length of 80 »set in the external circulation system and the casing of the 300Α reaction pot, and the K pump circulates it until the internal liquid is cooled to -5t: until. In addition, add 82kg formazan, 11.65kg 2,4,6-trimethylaniline, 18.75kg, 35% hydrochloric acid to 200JI glass control reaction wa, and drop 14.6kg, 40.7¾ nitric acid under cooling to 0 ~ 5D In the sodium solution, M forms a diazonium salt. In the quantitative spring, the formed diazonium salt K was dropped into the potassium salt solution of 3-hootyl-1H-1, 2,4-triazole for 20 minutes. The reaction temperature rose from 0υ to 9 · Ό. The reaction solution was heated to distill off the formazan, and after adding 150A water, the M35ΪHCl hydrochloric acid was neutralized to pH 7. The precipitated crystals were filtered, washed with water, and dried to obtain 13.9 kg of the target sulfide. Yield: 74S; (M3-hexyl-1H-1,2,4-triazole as a reference) Purity: 883! (Value of LC area percentage) Example 2 Add 20.4 to a 300 JL stainless dysprosium reaction pot kg methanol, 8.66kg 3-S [yl-1H-1,2,4-triazole, and slowly add 13.25kg, 955; caustic potassium while mixing and cooling. After the caustic potash is completely added, make -10t brine pass through the 80m long plate heat exchanger and the 3001L reactor pot casing set in the external circulation system, and the M pump circulates it until the internal liquid cools to -3¾. In addition, add 98kg formazan, 14kg2, 4,6-trimethylaniline, 22.55kg, 35% hydrochloric acid to a 200 jl glass controlled reaction pot, and drop 17.5kg, 40.7¾ sodium nitrate under cooling at 0 ~ 5C In solution, M forms a diazonium salt. -10-This paper is suitable for China National Standard (CNS) Α4 specification (210X297mm) --------- —installed ------ ordered ----- ~ I line (please first Read the notes on the back and fill in this page) oonr ifci ,,,.
Ilf- A7 年月日Ilf- A7
經濟部中央橾準局負工消費合作杜印製 五、發明説明（5 ) 以定最泵，將所形成的重氮鹽，分成4次滴人反應鍋 之三唑中。每次滴入所需時間如下所示： 第1次 -2分鐘 第2次 -3分鐘 第3次 -4分鐘 第4次 -5分鐘 全部滴入時間共為14分鐘。第1次滴入後溫度上升至7Ό ，惟30分鐘後溫度為-3Ό時，再滴人第2次。如此滴完4 次從第1次滴入起至最後一次滴完共130分。加熱餾去甲 醇後，以水稀釋，以35%鹽酸中和至pH為7。仿黄施例1 過濾、水洗及乾燥所析出的結晶而得1 4 . 3 k g硫化物。 產率：7 8 iK ( Μ 3 -痂基-1 Η - 1 , 2 , 4 -三唑為基準） 純度：88JULC面積百分率之值） 比較例1 在300 1不銹鋼製反應鍋内加人20.4kg甲醇、8.66kg 3-琉基-1H-1,2,4-三唑，在一邊授拌、一邊冷卻旳情形 下慢慢地加入13.25kg、95¾苛性鉀。加人完畢後使-12Ό 鹽水300A反應鍋之套管，且冷卻至- 5C。另外，在200JI 玻璃管製反應鍋中加入82kg甲醇、11.65kg2,4,6 -三甲基 苯胺、18.75kg、35¾鹽酸，在冷卻為0〜5¾下滴人14.6kg 、40.7¾硝酸納而得重氮錨鹽。 在上述及三唑反應媧内溫保持在0〜10 =下，滴入所 得的重氮錨鹽，自開始滴入至終了需2小時。使反應液 加熱Μ餾去甲醇，且加入150JI水後，以35%鹽酸中和至 -1 1 - 本紙張尺度適用中國國家揉準（CNS > Α4说格（210X297公釐） 裝 訂 (請先閲讀背面之注意事項再填寫本頁) A7 314515 B7 五、發明説明（、。） pH為7 。過濾、水洗、乾燥所析出之结晶而得7.7kg目 的物之硫化物。 產率：41HM3-疏基-1H-1,2,4-三唑為基準） 純度：76%(LC面積百分率之值） 實施例3 在300又不銹鋼製反應鍋內加入20.4kg甲酵、8.66kg 3-薙基-1H-1,2,4-三唑，在一邊攪拌、一邊冷卻旳情形 下慢慢地加入13.25kg、95S；苛性鉀。加入完畢後，使 -12¾¾水通過300JI反應鍋之套管，使溫度冷卻至-5Ό 為止。另外，在200A玻璃製反應鍋内加入82kg甲醇、 1 1 . 6 5 k g 2 , 4 , 6 -三甲基苯胺、1 8 . 7 5 k g、3 5 鹽酸，且在 冷卻為0〜5C下滴入14.6kg、40. 7¾硝酸納溶液而得重 氮銪鹽。 K定最泵，使該重氮_鹽溶液分6次滴人上述之三唑 反應鍋中。每次滴入所需時間如下所示： 第1次 -1 . 5分鐘 第2次 -2分鐘 第3次 -2 . 5分鐘 第4次 -3分鐘 第5次 -4分鐘 第6次 -5分鐘 全部滴入時間共為18分鐘。第1次滴入後，溫度上升至 60,惟30分鐘後溫度為-20時滴入第2次的部份。如 此滴完6次。第1次滴入時間開始至第6次滴完的時間 -12-Printed and printed by the Ministry of Economic Affairs, Central Bureau of Preservation and Duty. 5. Description of the invention (5) To determine the maximum pump, the formed diazonium salt is divided into three triazoles in a reaction pot. The time required for each drop is as follows: 1st time-2 minutes 2nd time-3 minutes 3rd time-4 minutes 4th time-5 minutes The total drip time is 14 minutes. After the first drop, the temperature rose to 7Ό, but when the temperature was -3Ό after 30 minutes, the second drop was made. After 4 drops in this way, there are 130 points from the first drop to the last drop. After the methanol was distilled off by heating, it was diluted with water and neutralized to pH 7 with 35% hydrochloric acid. Imitation yellow Example 1 The precipitated crystals were filtered, washed with water and dried to obtain 14.3 k g of sulfide. Yield: 7 8 iK (Μ 3 -scabyl-1 Η -1,2,4-triazole as a reference) Purity: 88JULC area percentage value) Comparative Example 1 Add 20.4kg to 300 1 stainless steel reaction pot Methanol, 8.66kg 3-luryl-1H-1,2,4-triazole, slowly add 13.25kg, 95¾ caustic potassium while mixing and cooling. After the addition is completed, the casing of the -12Ό brine 300A reactor is cooled to -5C. In addition, add 82kg methanol, 11.65kg 2,4,6-trimethylaniline, 18.75kg, 35¾ hydrochloric acid to the 200JI glass control reaction pot, and then drop 14.6kg, 40.7¾ sodium nitrate under cooling to 0 ~ 5¾. Diazo anchor salt. After the above and the internal temperature of the triazole reaction wa were kept at 0 ~ 10 =, the resulting diazo anchor salt was added dropwise, and it took 2 hours from the start of the drop to the end. The reaction solution was heated to distill off methanol, and after adding 150JI water, it was neutralized with 35% hydrochloric acid to -1 1-This paper size is suitable for China National Standard (CNS > Α4 said grid (210X297mm) binding (please first Read the precautions on the back and fill out this page) A7 314515 B7 V. Description of the invention (,.) The pH is 7. The crystallization of the precipitated crystals by filtration, water washing, and drying yields 7.7 kg of the target sulfide. Yield: 41HM3- Base-1H-1,2,4-triazole as a reference) Purity: 76% (value of LC area percentage) Example 3 Add 20.4kg of formazan and 8.66kg of 3-octyl in a 300 stainless steel reactor 1H-1,2,4-triazole, slowly add 13.25kg, 95S; caustic potash while stirring and cooling. After the addition is complete, allow -12¾¾ water to pass through the 300JI reactor pot sleeve and allow the temperature to cool to -5Ό. In addition, in a 200A glass reaction pot, add 82kg of methanol, 11.65 kg of 2, 4, 6-trimethylaniline, 18.75 kg, and 35 hydrochloric acid, and drop at a cooling of 0 ~ 5C Into 14.6kg, 40. 7¾ sodium nitrate solution to get diazonium europium salt. K set the pump to make the diazonium salt solution drop into the triazole reaction kettle 6 times. The time required for each drop is as follows: 1st time-1. 5 minutes 2nd time-2 minutes 3rd time-2. 5 minutes 4th time-3 minutes 5th time-4 minutes 6th time-5 The total dropping time in minutes is 18 minutes. After the first drip, the temperature rose to 60, but after 30 minutes, the temperature was -20 and the second part was dripped. 6 drops are done. Time from the start of the first drip to the end of the sixth drip -12-
In· n^i ^^^1 In HI ^ In In 1^1 ^^^1--eJIn— am nn HI I (請先閲讀背面之注意事項再填寫本頁) 經濟部中央揉準局貝工消费合作社印製 本紙張尺度適用中國國家標準（CNS > A4規格（210X297公釐） 經濟部中央標準局貝工消費合作社印製 A7 B7 五、發明説明（*·) 為210分鐘。使反應液加熱Μ餾去甲酵，且加入150A 水後，M 35¾鹽酸中和至pH為7 。過漶、水洗、乾燥所 析出的结晶而得14.3 目的之硫化物。 產率：72S；(M3-铳基-1H-1,2,4-三唑為基準） 純度：8 7 % ( L C面積百分率之值） 實施例4 在300 i 不銹網製反應鍋内加人20.4kg甲醇、8.66kg 3 -铳基-1H-1,2,4 -三唑，且在一邊攪拌、一逢冷卻旳情 形下慢慢地加人13.25kg、95S；苛性鉀。苛性鉀滴人完畢 後，使- ίου鹽水通過設置於外部循環糸之板式熱交換 器及3001反應鍋之套管，Μ泵使其循環，直至内液冷 卻至-3υ為止。另外，在200Λ玻璃管製反應鍋中加入 98kg甲醇、14kg2, 4,6-三甲基苯胺、22.5 5 kg、35%鹽酸 ，且在冷卻為0〜5P下滴入17.5kg、40.7¾硝酸納而得 重氮錨鹽。 Μ定量泵使該重氮鐵鹽溶液分為5次滴入上述之三唑 反應鍋中。每次滴入所需時間如下所示： 第 1 次 -2 分鐘 第 2 次 ~ 2 · 5分鐘 第 3 次 -3 分 鐘 第 4 次 -4 分 鐘 第 5 次 -5 分 鐘 全部滴入時間共為16.5分鐘。第1次滴入後，溫度上升 至7·Ό,惟30分鐘後溫度為-3C時，再滴入第2次的部 本紙張尺度適用中國國家揉準（CNS ) A4规格（210X297公釐） --------- —裝------訂------線 (請先閲讀背面之注意Ϋ項再填寫本頁) 314515 A7 A7 B7 五、發明説明（p) 份。如此滴入5次份。第1次滴入開始至第5次滴完的時 間為155分鐘。與實施例1相同餾去甲醇，且Μ水稀釋 ,Μ35%鹽酸中和至pH為7 。過濾、水洗、乾燥所析出 的结晶而得1 4 . 3 k g硫化物。 產率：78%(W3 -薙基-1H-1,2,4 -三唑為基準） 純度：89MLC面積百分率之值） (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局貝工消费合作社印装 -14- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）In · n ^ i ^^^ 1 In HI ^ In In 1 ^ 1 ^^^ 1--eJIn— am nn HI I (please read the notes on the back before filling this page) The paper printed by the consumer cooperative applies the Chinese national standard (CNS> A4 specification (210X297 mm). The A7 B7 is printed by the Beigong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. 5. The description of the invention (* ·) is 210 minutes. After heating to distill off the enzyme and adding 150A of water, M 35¾ hydrochloric acid was neutralized to pH 7. The precipitated crystals were washed, dried and dried to obtain the sulfide of the purpose of 14.3. Yield: 72S; (M3- 铳Based on -1H-1,2,4-triazole) Purity: 87% (value of LC area percentage) Example 4 Add 20.4kg methanol and 8.66kg 3 in a 300i stainless steel reaction pot铳 基 -1H-1,2,4-triazole, and slowly add 13.25kg, 95S; caustic potassium while stirring and cooling once in a while. After the dripping of caustic potassium is completed, let-ίου brine pass It is installed in the plate heat exchanger of the external circulation tank and the casing of the 3001 reaction pot, and the M pump circulates it until the internal liquid cools to -3. In addition, in the 200Λ glass tube 98kg methanol, 14kg 2,4,6-trimethylaniline, 22.5 5 kg, 35% hydrochloric acid were added to the reaction pot, and 17.5kg, 40.7¾ sodium nitrate was added dropwise under cooling to 0 ~ 5P to obtain diazo anchor salt. Μ quantitative pump makes the diazonium iron salt solution drop into the above triazole reaction pot 5 times. The time required for each drop is as follows: 1st-2 minutes 2nd ~ 2 · 5 minutes 3 times-3 minutes 4 times-4 minutes 5 times-5 minutes The total infusion time is 16.5 minutes. After the first infusion, the temperature rises to 7 · Ό, but after 30 minutes when the temperature is -3C, The standard of the second part of the paper to be dripped in is applicable to the Chinese National Standardization (CNS) A4 specification (210X297 mm) --------- —installed ------ ordered ------ Line (please read the note Ϋ on the back before filling in this page) 314515 A7 A7 B7 5. Description of the invention (p) copies. 5 drops are added in this way. The time from the start of the first drop to the end of the fifth drop is 155 minutes. Methanol was distilled off in the same manner as in Example 1, and M water was diluted, and M35% hydrochloric acid was neutralized to pH 7. The precipitated crystals were filtered, washed with water, and dried to obtain 14.3 kg of sulfide. Yield: 78 % (W3-薙 基 -1H- 1,2,4 -Triazole as the standard) Purity: 89MLC area percentage value (Please read the notes on the back before filling this page) Printed by the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs-14- This paper size is applicable China National Standard (CNS) A4 specification (210X297mm)
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21908693A JP3501477B2 (en) | 1993-08-10 | 1993-08-10 | Method for producing sulfide compound |
| JP5219085A JPH0753531A (en) | 1993-08-10 | 1993-08-10 | Production of sulfide compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| TW314515B true TW314515B (en) | 1997-09-01 |
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ID=26522909
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
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| TW083107263A TW314515B (en) | 1993-08-10 | 1994-08-09 |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR100290617B1 (en) |
| CN (1) | CN1058711C (en) |
| TW (1) | TW314515B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1092605C (en) * | 1998-05-14 | 2002-10-16 | 中国科学技术大学 | Radiation synthetic preparing method for nanometer metal sulfide |
| CN102775360B (en) * | 2012-03-06 | 2015-05-06 | 南开大学 | Triazole ring-containing asymmetric disulfide ether compounds, synthesis method and usage thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8429307D0 (en) * | 1984-11-20 | 1984-12-27 | Shell Int Research | Heterocyclic herbicides |
| EP0332133B1 (en) * | 1988-03-07 | 1994-08-24 | Chugai Seiyaku Kabushiki Kaisha | Novel triazole compounds, process for producing the same, and herbicidal compositions containing the same |
-
1994
- 1994-08-09 TW TW083107263A patent/TW314515B/zh active
- 1994-08-09 KR KR1019940019892A patent/KR100290617B1/en not_active IP Right Cessation
- 1994-08-10 CN CN94109027A patent/CN1058711C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1058711C (en) | 2000-11-22 |
| KR100290617B1 (en) | 2001-11-26 |
| CN1101643A (en) | 1995-04-19 |
| KR950005814A (en) | 1995-03-20 |
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