JPH0788337B2 - Process for producing 5-amino-2,4,6-triiodoisophthalic acid - Google Patents
Process for producing 5-amino-2,4,6-triiodoisophthalic acidInfo
- Publication number
- JPH0788337B2 JPH0788337B2 JP62204226A JP20422687A JPH0788337B2 JP H0788337 B2 JPH0788337 B2 JP H0788337B2 JP 62204226 A JP62204226 A JP 62204226A JP 20422687 A JP20422687 A JP 20422687A JP H0788337 B2 JPH0788337 B2 JP H0788337B2
- Authority
- JP
- Japan
- Prior art keywords
- aipa
- acid
- filtrate
- amino
- hydrochloric acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- JEZJSNULLBSYHV-UHFFFAOYSA-N 5-amino-2,4,6-triiodobenzene-1,3-dicarboxylic acid Chemical compound NC1=C(I)C(C(O)=O)=C(I)C(C(O)=O)=C1I JEZJSNULLBSYHV-UHFFFAOYSA-N 0.000 title claims description 4
- 238000000034 method Methods 0.000 title description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 28
- 239000000706 filtrate Substances 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 12
- QZRGKCOWNLSUDK-UHFFFAOYSA-N Iodochlorine Chemical compound ICl QZRGKCOWNLSUDK-UHFFFAOYSA-N 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 6
- 239000003456 ion exchange resin Substances 0.000 claims description 5
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 5
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000007810 chemical reaction solvent Substances 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- KBZFDRWPMZESDI-UHFFFAOYSA-N 5-aminobenzene-1,3-dicarboxylic acid Chemical compound NC1=CC(C(O)=O)=CC(C(O)=O)=C1 KBZFDRWPMZESDI-UHFFFAOYSA-N 0.000 claims description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims 1
- 229910052740 iodine Inorganic materials 0.000 claims 1
- 239000011630 iodine Substances 0.000 claims 1
- 101100264174 Mus musculus Xiap gene Proteins 0.000 description 25
- 239000007788 liquid Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000002699 waste material Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- GVZPOILYKLKCDM-UHFFFAOYSA-N 5-amino-2-iodobenzene-1,3-dicarboxylic acid Chemical compound NC1=CC(C(O)=O)=C(I)C(C(O)=O)=C1 GVZPOILYKLKCDM-UHFFFAOYSA-N 0.000 description 4
- LKFJKQGJIDFBBA-UHFFFAOYSA-N 5-amino-4,6-diiodobenzene-1,3-dicarboxylic acid Chemical compound IC1=C(C(=C(C=C1C(=O)O)C(=O)O)I)N LKFJKQGJIDFBBA-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000002872 contrast media Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 238000001990 intravenous administration Methods 0.000 description 1
- 238000006192 iodination reaction Methods 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、５−アミノ−2,4,6−トリヨードイソフタル
酸（以下、AIPAと略する。）の製造方法に関するもので
ある。TECHNICAL FIELD The present invention relates to a method for producing 5-amino-2,4,6-triiodoisophthalic acid (hereinafter abbreviated as AIPA).
本発明により得られるAIPAは、静脈内毒性が極めて低
い、レントゲン造影剤の中間体として有用である。The AIPA obtained by the present invention is useful as an intermediate for an X-ray contrast agent, which has extremely low intravenous toxicity.
５−アミノイソフタル酸（以下、AiPAと略する。）を一
塩化沃素でトリヨード化し、AIPAを合成する一般的な製
法は英国特許第785,670号に示されている。A general method for synthesizing AIPA by triiodizing 5-aminoisophthalic acid (hereinafter abbreviated as AiPA) with iodine monochloride is shown in British Patent No. 785,670.
従来の技術では、反応終了時、３〜10重量％程度の塩酸
やAIPA及び中間体等を含む結晶分離後の濾液の処理が難
しく、煩雑で大掛かりな処理工程を必要とした。In the conventional technique, it is difficult to treat the filtrate after the crystal separation containing hydrochloric acid, AIPA and intermediates in an amount of about 3 to 10% by weight at the end of the reaction, and a complicated and large-scale treatment process is required.
本発明者らは、前述の問題点を解決するため鋭意検討し
た結果、活性炭またはイオン交換樹脂で処理した濾液を
濃縮し、余剰の水と塩酸とを留去した濃縮液を、繰り返
しAIPA製造に用いることで原料原単位を向上させ、かつ
簡単に廃液処理ができることを見出し、本発明を完成さ
せるに至った。As a result of intensive studies to solve the above-mentioned problems, the present inventors concentrated the filtrate treated with activated carbon or an ion exchange resin, and concentrated the solution obtained by distilling off excess water and hydrochloric acid, for repeated AIPA production. The inventors have found that the use of the raw material can improve the basic unit of raw material and can easily perform waste liquid treatment, and have completed the present invention.
すなわち、本発明は、AiPAを一塩化沃素を用いてトリヨ
ード化し、AIPAを製造する方法において、 製品結晶を分離して得た濾液を活性炭またはイオン交
換樹脂で処理する工程、 濾液を濃縮し、該濾液中における塩酸濃度を19〜23重
量％の範囲とする工程、 とを有し、上記、の工程後に得られる濾液を、一塩
化沃素の溶解用及び／又は反応溶媒とし、繰り返しAIPA
の製造に用いることを特徴とするAIPAの製造方法であ
る。That is, the present invention is a method of triiodizing AiPA with iodine monochloride to produce AIPA, a step of treating a filtrate obtained by separating product crystals with activated carbon or an ion exchange resin, concentrating the filtrate, A step of adjusting the concentration of hydrochloric acid in the filtrate in the range of 19 to 23% by weight, and the filtrate obtained after the above step is used as a solvent for dissolving iodine monochloride and / or a reaction solvent, and repeatedly
A method for producing AIPA, which is characterized in that it is used for the production of.
以下、本発明を詳説する。Hereinafter, the present invention will be described in detail.
本発明は、AIPAを製造して得られた結晶分離後の濾液
を、活性炭等で処理することにより脱色精製し、これを
濃縮して余分な水及び塩酸を留去し、AIPAやその他の未
反応物を含んだ約20重量％の塩酸水溶液として、これを
一塩化沃素溶解用または反応溶媒用として再度AIPA製造
に利用することで原料原単位を向上させ、かつ廃液処理
が容易にできる、AIPAの製造方法である。In the present invention, the crystal-separated filtrate obtained by producing AIPA is subjected to decolorization purification by treating with activated carbon or the like, and this is concentrated to remove excess water and hydrochloric acid, thereby removing AIPA and other An aqueous solution of hydrochloric acid containing about 20% by weight containing the reactants can be used again for AIPA production to dissolve iodine monochloride or as a reaction solvent, thereby improving the raw material consumption rate and facilitating waste liquid treatment. Is a manufacturing method.
濾液中に含まれる成分は、主にAIPA、塩酸（一塩化沃素
溶解用塩酸と副生塩酸）、水、未反応物として一塩化沃
素（過剰仕込み残分）、５−アミノモノヨードイソフタ
ル酸、５−アミノジヨードイソフタル酸及び微量の不明
成分である。The components contained in the filtrate are mainly AIPA, hydrochloric acid (hydrochloric acid for dissolving iodine monochloride and by-product hydrochloric acid), water, iodine monochloride as unreacted matter (residual excess charging residue), 5-aminomonoiodoisophthalic acid, 5-Aminodiiodoisophthalic acid and trace amounts of unknown ingredients.
濾液を活性炭処理すると脱色されるが、同時に濾液中に
溶存する生成物が一部活性炭に吸着される。生成物と
は、AIPA、５−アミノジヨードイソフタル酸、５−アミ
ノモノヨードイソフタル酸、不明成分で、この逆の順に
活性炭に吸着され易くなる。When the filtrate is treated with activated carbon, it is decolorized, but at the same time, some of the products dissolved in the filtrate are adsorbed on the activated carbon. The products are AIPA, 5-aminodiiodoisophthalic acid, 5-aminomonoiodoisophthalic acid, and unknown components, which are easily adsorbed by activated carbon in the reverse order.
すなわち、不明成分が優先的に活性炭に吸着される。し
たがって、濃縮液中の不明成分は、活性炭処理すること
により除去され、濃縮液中にはリサイクル可能な成分の
み残存し、再利用を何度でも可能にすることができる。That is, the unknown component is preferentially adsorbed on the activated carbon. Therefore, the unknown component in the concentrated liquid is removed by the treatment with activated carbon, and only the recyclable component remains in the concentrated liquid, so that it can be reused many times.
活性炭処理は、濃縮前又は濃縮後のどちらで行っても良
く、この両方で行えば更に効果的である。The activated carbon treatment may be carried out either before or after concentration, and it is more effective if carried out both of them.
活性炭の代わりにイオン交換樹脂に用いても良い。イオ
ン交換樹脂では、特にカチオン系交換樹脂が効果的であ
る。You may use it for an ion exchange resin instead of activated carbon. Of the ion exchange resins, cation exchange resins are particularly effective.
濾液中の塩酸濃度は通常３〜10重量％で、これを濃縮す
ることで20重量％前後の塩酸水溶液が得られる。これに
はAIPAの他に５−アミノジヨードイソフタル酸、５−ア
ミノモノヨードイソフタル酸が存在する。この内、反応
中間体である５−アミノモノヨードイソフタル酸と５−
アミノジヨードイソフタル酸は反応系に戻されることで
AIPAに転化するし、またAIPAはこれ以上の沃素化反応を
受けないため、反応終了後に回収される。したがって、
本方法は全く無駄のない製造方法であるといえる。The hydrochloric acid concentration in the filtrate is usually 3 to 10% by weight, and by concentrating this, an aqueous hydrochloric acid solution of about 20% by weight can be obtained. In addition to AIPA, there are 5-aminodiiodoisophthalic acid and 5-aminomonoiodoisophthalic acid. Among these, 5-aminomonoiodoisophthalic acid and 5-
Aminodiiodoisophthalic acid is returned to the reaction system
It is converted to AIPA, and since AIPA does not undergo further iodination reaction, it is recovered after the reaction is completed. Therefore,
It can be said that this method is a manufacturing method with no waste.
濃縮条件に大きな制約はないが、常圧下で行っても、減
圧下で行っても19〜23重量％の塩酸溶液を得ることは容
易である。There are no major restrictions on the concentration conditions, but it is easy to obtain a hydrochloric acid solution of 19 to 23 wt% under normal pressure or under reduced pressure.
反応系外へ出される廃液としては、濃縮時の留出分であ
る１〜５重量％程度の希塩酸水溶液のみで、これを廃液
として処理することは、極めて容易である。The waste liquid discharged to the outside of the reaction system is only a dilute hydrochloric acid aqueous solution of about 1 to 5% by weight which is a distillate at the time of concentration, and it is extremely easy to treat this as a waste liquid.
濃縮液の利用方法は、一塩化沃素の溶解用でも、反応溶
媒用でも何方でも良い。The concentrated solution may be used either for dissolving iodine monochloride or for a reaction solvent.
以下、実施例により本発明をさらに具体的に説明する。 Hereinafter, the present invention will be described in more detail with reference to Examples.
分析には、液体クトマトグラフィーを用い、不明成分の
定量は、内部標準法でAIPAの係数を用いAIPA換算として
比較データにした。For analysis, liquid chromatography was used, and for the quantification of unknown components, the coefficient of AIPA was used by the internal standard method and the comparison data was converted to AIPA.
収率は次のように求めた。The yield was determined as follows.
収率＝（B/A）×100 〔％〕 Ｂ＝（乾燥結晶重量） Ａ＝（AIPA理論生成量） AIPA理論生成量はAiPA仕込量をベースに算出した。Yield = (B / A) × 100 [%] B = (dry crystal weight) A = (AIPA theoretical production amount) The AIPA theoretical production amount was calculated based on the charged amount of AiPA.
実施例１ 撹拌機付反応器に、水約650mlとAiPA0.2モルを仕込み、
撹拌しながら90℃まで昇温した。次に、予め、0.84モル
の塩酸を水に溶解して6Nとした塩酸水溶液に一塩化沃素
0.63モルを溶解した液を、上記の液に約１時間かけて滴
下した。その後、約５時間熟成し室温まで冷却後、結晶
を濾別し、水でリンスした。結晶は、減圧下、80℃で２
時間乾燥した。このとき得られた濾液約850gを活性炭50
mlを用いた活性炭塔に約１時間かけて通液し、その後50
mlの水を活性炭塔に通し洗った。この洗浄液と濾液を混
ぜた。Example 1 A reactor equipped with a stirrer was charged with about 650 ml of water and 0.2 mol of AiPA,
The temperature was raised to 90 ° C with stirring. Next, in advance, 0.84 mol of hydrochloric acid was dissolved in water to make 6N and added to a hydrochloric acid aqueous solution, and then iodine monochloride was added.
A solution in which 0.63 mol was dissolved was added dropwise to the above solution over about 1 hour. Then, after aging for about 5 hours and cooling to room temperature, the crystals were separated by filtration and rinsed with water. The crystals are 2 at 80 ° C under reduced pressure.
Dried for hours. About 850 g of the filtrate obtained at this time was added to activated carbon 50
Pass the solution through the activated carbon tower using 1 ml for about 1 hour, then 50
ml water was washed through the activated carbon tower. The washing liquid and the filtrate were mixed.
次に、この濾液を100〜110℃で常圧濃縮し、余剰分の水
と塩酸とを留去し、19.5重量％の塩酸の濃縮液170gを得
た。Next, this filtrate was concentrated under normal pressure at 100 to 110 ° C., and excess water and hydrochloric acid were distilled off to obtain 170 g of a 19.5 wt% concentrated hydrochloric acid concentrate.
この濃縮液に一塩化沃素0.63モルを溶解し、他は全て前
述の反応条件と同じ操作でAIPAを合成した。この一連の
操作を５回繰り返して、表１の結果を得た。0.63 mol of iodine monochloride was dissolved in this concentrated solution, and AIPA was synthesized under the same conditions as the above reaction conditions except for the above. This series of operations was repeated 5 times, and the results shown in Table 1 were obtained.
〔発明の効果〕 本発明の方法によれば、原料原単位の向上と共に廃液処
理工程を全く必要としないか、又は極めて簡略化した廃
液処理操作でAIPAを製造することができる。 [Effects of the Invention] According to the method of the present invention, AIPA can be produced by improving the raw material unit and not requiring a waste liquid treatment step at all, or by an extremely simplified waste liquid treatment operation.
Claims (1)
いてトリヨード化し、５−アミノ−2,4,6−トリヨード
イソフタル酸を製造する方法において、 製品結晶を分離して得た濾液を活性炭またはイオン交
換樹脂で処理する工程、 濾液を濃縮し、該濾液中における塩酸濃度を19〜23重
量％の範囲とする工程、 とを有し、上記、の工程後に得られる濾液を、一塩
化沃素の溶解用及び／又は反応溶媒として、繰り返し５
−アミノ−2,4,6−トリヨードイソフタル酸の製造に用
いることを特徴とする５−アミノ−2,4,6−トリヨード
イソフタル酸の製造方法。1. A method for producing 5-amino-2,4,6-triiodoisophthalic acid by triiodizing 5-aminoisophthalic acid with iodine monochloride, and separating the filtrate obtained by separating product crystals. A step of treating with an activated carbon or an ion exchange resin, a step of concentrating the filtrate so that the concentration of hydrochloric acid in the filtrate is in the range of 19 to 23% by weight, and the filtrate obtained after the step of Repeat 5 times to dissolve iodine and / or as a reaction solvent
A method for producing 5-amino-2,4,6-triiodoisophthalic acid, which is used for the production of -amino-2,4,6-triiodoisophthalic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62204226A JPH0788337B2 (en) | 1987-08-19 | 1987-08-19 | Process for producing 5-amino-2,4,6-triiodoisophthalic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62204226A JPH0788337B2 (en) | 1987-08-19 | 1987-08-19 | Process for producing 5-amino-2,4,6-triiodoisophthalic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6447746A JPS6447746A (en) | 1989-02-22 |
| JPH0788337B2 true JPH0788337B2 (en) | 1995-09-27 |
Family
ID=16486928
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62204226A Expired - Fee Related JPH0788337B2 (en) | 1987-08-19 | 1987-08-19 | Process for producing 5-amino-2,4,6-triiodoisophthalic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0788337B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2841914B2 (en) * | 1991-03-30 | 1998-12-24 | 株式会社島津製作所 | Biochemical automatic analyzer |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB785670A (en) | 1955-03-21 | 1957-10-30 | Schering Corp | Improvements in or relating to chemical compounds for use as x-ray diagnostic agentsand to processes for their preparation |
-
1987
- 1987-08-19 JP JP62204226A patent/JPH0788337B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB785670A (en) | 1955-03-21 | 1957-10-30 | Schering Corp | Improvements in or relating to chemical compounds for use as x-ray diagnostic agentsand to processes for their preparation |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6447746A (en) | 1989-02-22 |
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| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |