JPH0252219B2 - - Google Patents
Info
- Publication number
- JPH0252219B2 JPH0252219B2 JP60184338A JP18433885A JPH0252219B2 JP H0252219 B2 JPH0252219 B2 JP H0252219B2 JP 60184338 A JP60184338 A JP 60184338A JP 18433885 A JP18433885 A JP 18433885A JP H0252219 B2 JPH0252219 B2 JP H0252219B2
- Authority
- JP
- Japan
- Prior art keywords
- titrant
- mol
- sulfur dioxide
- heterocyclic compound
- compound
- 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 - Lifetime
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- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 44
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 20
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000005605 benzo group Chemical group 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 34
- 238000004448 titration Methods 0.000 description 18
- 239000003153 chemical reaction reagent Substances 0.000 description 14
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 12
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 10
- 229910052740 iodine Inorganic materials 0.000 description 10
- 239000011630 iodine Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- VWSLLSXLURJCDF-UHFFFAOYSA-N 2-methyl-4,5-dihydro-1h-imidazole Chemical compound CC1=NCCN1 VWSLLSXLURJCDF-UHFFFAOYSA-N 0.000 description 2
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 2
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 2
- QMHIMXFNBOYPND-UHFFFAOYSA-N 4-methylthiazole Chemical compound CC1=CSC=N1 QMHIMXFNBOYPND-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- FYADHXFMURLYQI-UHFFFAOYSA-N 1,2,4-triazine Chemical compound C1=CN=NC=N1 FYADHXFMURLYQI-UHFFFAOYSA-N 0.000 description 1
- AGMJWUBJIPQHBM-UHFFFAOYSA-N 1,2,4-trimethylimidazole Chemical compound CC1=CN(C)C(C)=N1 AGMJWUBJIPQHBM-UHFFFAOYSA-N 0.000 description 1
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 1
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 1
- RAIPHJJURHTUIC-UHFFFAOYSA-N 1,3-thiazol-2-amine Chemical compound NC1=NC=CS1 RAIPHJJURHTUIC-UHFFFAOYSA-N 0.000 description 1
- MCMFEZDRQOJKMN-UHFFFAOYSA-N 1-butylimidazole Chemical compound CCCCN1C=CN=C1 MCMFEZDRQOJKMN-UHFFFAOYSA-N 0.000 description 1
- IWDFHWZHHOSSGR-UHFFFAOYSA-N 1-ethylimidazole Chemical compound CCN1C=CN=C1 IWDFHWZHHOSSGR-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- SEULWJSKCVACTH-UHFFFAOYSA-N 1-phenylimidazole Chemical compound C1=NC=CN1C1=CC=CC=C1 SEULWJSKCVACTH-UHFFFAOYSA-N 0.000 description 1
- IYVYLVCVXXCYRI-UHFFFAOYSA-N 1-propylimidazole Chemical compound CCCN1C=CN=C1 IYVYLVCVXXCYRI-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- CGZDWVZMOMDGBN-UHFFFAOYSA-N 2-Ethylthiazole Chemical compound CCC1=NC=CS1 CGZDWVZMOMDGBN-UHFFFAOYSA-N 0.000 description 1
- -1 2-bropylimidazole Chemical compound 0.000 description 1
- SLLDUURXGMDOCY-UHFFFAOYSA-N 2-butyl-1h-imidazole Chemical compound CCCCC1=NC=CN1 SLLDUURXGMDOCY-UHFFFAOYSA-N 0.000 description 1
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 description 1
- VZWOXDYRBDIHMA-UHFFFAOYSA-N 2-methyl-1,3-thiazole Chemical compound CC1=NC=CS1 VZWOXDYRBDIHMA-UHFFFAOYSA-N 0.000 description 1
- WYKHSBAVLOPISI-UHFFFAOYSA-N 2-phenyl-1,3-thiazole Chemical compound C1=CSC(C=2C=CC=CC=2)=N1 WYKHSBAVLOPISI-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- BKCCAYLNRIRKDJ-UHFFFAOYSA-N 2-phenyl-4,5-dihydro-1h-imidazole Chemical compound N1CCN=C1C1=CC=CC=C1 BKCCAYLNRIRKDJ-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- CGOVTZGCKPMLMN-UHFFFAOYSA-N 4-ethyl-1,3-thiazole Chemical compound CCC1=CSC=N1 CGOVTZGCKPMLMN-UHFFFAOYSA-N 0.000 description 1
- VJXRKZJMGVSXPX-UHFFFAOYSA-N 4-ethylpyridine Chemical compound CCC1=CC=NC=C1 VJXRKZJMGVSXPX-UHFFFAOYSA-N 0.000 description 1
- KXCQDIWJQBSUJF-UHFFFAOYSA-N 4-phenyl-1,3-thiazole Chemical compound S1C=NC(C=2C=CC=CC=2)=C1 KXCQDIWJQBSUJF-UHFFFAOYSA-N 0.000 description 1
- YOTBOYFKPMRBAG-UHFFFAOYSA-N 5-butyl-1h-imidazole Chemical compound CCCCC1=CNC=N1 YOTBOYFKPMRBAG-UHFFFAOYSA-N 0.000 description 1
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- XMBWDFGMSWQBCA-AKLPVKDBSA-N iodane Chemical compound [130IH] XMBWDFGMSWQBCA-AKLPVKDBSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229960004011 methenamine Drugs 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000001420 substituted heterocyclic compounds Chemical class 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/16—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using titration
- G01N31/168—Determining water content by using Karl Fischer reagent
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Molecular Biology (AREA)
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Description
【発明の詳細な説明】
本発明は、複素環式化合物、二酸化硫黄及びヨ
ウ素を含有する滴定剤に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a titrant containing a heterocyclic compound, sulfur dioxide and iodine.
周知のごとく、液体及び固体の含水量を滴定法
で定量することはカール−フイツシヤーにより開
発された。この方法は次式
2H2O＋SO2＋I2H2SO4＋2HI
に従う水の存在下でのヨウ素による二酸化硫黄の
酸化に基づいている。通常この反応は無水メタノ
ール中で行われる。この試薬（KF試薬）はピリ
ジン790ｇ、液体亜硫酸192ｇ及びヨウ素254ｇの
無水メタノール５より成る溶液から成る
Angew.Chem.48巻（1935）、394頁を参照〕。この
溶液は貯蔵上安定でないので、実際には一般に二
成分の試薬が使用され、その一方はメタノールに
二酸化硫黄及びピリジンを溶解した溶液から成
り、他方はメタノールにヨウ素を溶解し溶液から
成る。 As is well known, the titrimetric determination of the water content of liquids and solids was developed by Karl-Fischer. The method is based on the oxidation of sulfur dioxide with iodine in the presence of water according to the following formula: 2H 2 O + SO 2 +I 2 H 2 SO 4 +2HI. This reaction is usually carried out in anhydrous methanol. This reagent (KF reagent) consists of a solution of 790 g of pyridine, 192 g of liquid sulfite and 254 g of iodine in anhydrous methanol 5.
See Angew. Chem. vol. 48 (1935), p. 394]. Since this solution is not storage stable, in practice two-component reagents are generally used, one consisting of a solution of sulfur dioxide and pyridine in methanol and the other consisting of a solution of iodine in methanol.
又、既に知られているように、ピリジンの代り
に他の窒素含有化合物例えばキノリン、アニリ
ン、ジメチルアニリン、トリ−ｎ−ブチルアミン
及びトリエタノールアミンも使用されたが、満足
な結果はもたらされなかつたJ.Amer.Chem.
Soc.1939、2407頁参照］。ピリジンの代りに使用
することがもくろまれた他の化合物はエタノール
アミン及びヘキサメチレン−テトラミンなるアミ
ンである；しかしこれらのアミンは、安定な滴定
点を示さないか又はめんどうな沈殿を起こすとい
う欠点をもつと言われている〔Analytic.
Chem.28巻（1956）、1166頁を参照〕。これらの変
更されたKF試薬は酸化剤、還元剤及びアミンの
含水量の測定に使用された。 As is already known, other nitrogen-containing compounds have also been used in place of pyridine, such as quinoline, aniline, dimethylaniline, tri-n-butylamine and triethanolamine, but these have not given satisfactory results and J.Amer.Chem.
See Soc. 1939, p. 2407]. Other compounds contemplated for use in place of pyridine are the amines ethanolamine and hexamethylene-tetramine; however, these amines have the disadvantage of not exhibiting stable titration points or of causing troublesome precipitation. It is said to have [Analytic.
See Chem. vol. 28 (1956), p. 1166]. These modified KF reagents were used to measure the water content of oxidizing agents, reducing agents, and amines.
本発明の目的は、ピリジンの代りに事実上無毒
の複素環式化合物を含有しそして貯蔵上安定な、
少量の水を定量するのに適する試薬を提供するこ
とである。 It is an object of the present invention to contain a virtually non-toxic heterocyclic compound in place of pyridine and which is storage stable.
The object of the present invention is to provide a reagent suitable for quantifying small amounts of water.
本発明は複素環式化合物、二酸化硫黄及びヨウ
素を含有する滴定剤において、複素環式化合物
が、五員又は六員の、場合により置換されてい
る、複素環式化合物−ただし少なとも２個のヘテ
ロ原子をもち、少なくとも１個のヘテロ原子が窒
素原子である複素環式化合物−であることを特徴
とする滴定剤に関する。 The present invention provides a titrant containing a heterocyclic compound, sulfur dioxide and iodine, in which the heterocyclic compound is a five- or six-membered, optionally substituted heterocyclic compound - provided that at least two The present invention relates to a titrant characterized in that it is a heterocyclic compound having a heteroatom, at least one of which is a nitrogen atom.
滴定剤中に含まれている本発明による複素環式
化合物は、環の員数が５個又は６個でありそして
場合によつては、好ましくは炭素原子数１〜４の
１個、２個もしくは３個のアルキル基または１
個、２個もしくは３個のフエニル基または１個の
ベンゾ基で置換されている。この複素環式化合物
は少なくとも２個、殊に２個もしくは３個のヘテ
ロ原子を含み、それらの中の少なくとも１個は窒
素原子である。特に適するものは５員の、２個の
窒素原子をヘテロ原子として含む、場合により置
換されている、複素環式化合物である。複素環式
化合物の二酸化硫黄に対するモル比は一般に10：
１から0.3：１まで、殊に２：１から0.5：１まで
の範囲内である。 The heterocyclic compounds according to the invention contained in the titrants have 5 or 6 ring members and, as the case may be, preferably 1, 2 or 4 carbon atoms. 3 alkyl groups or 1
substituted with 1, 2 or 3 phenyl groups or 1 benzo group. This heterocyclic compound contains at least 2, in particular 2 or 3, heteroatoms, at least one of which is a nitrogen atom. Particularly suitable are 5-membered, optionally substituted, heterocyclic compounds containing two nitrogen atoms as heteroatoms. The molar ratio of heterocyclic compounds to sulfur dioxide is generally 10:
It is in the range from 1 to 0.3:1, in particular from 2:1 to 0.5:1.
複素環式化合物としては、イミダゾール又はイ
ミダゾール誘導体、殊に式
〔式中Ｒ、R1及びR2は、同一であるか又は相違
していて、それぞれ水素原子、低級アルキル基
（これは１個から４個までの炭素原子を含んでい
るのが好ましい）、又はフエニル基を意味する〕
で示される容易が特に適する。 As heterocyclic compounds, imidazole or imidazole derivatives, especially those of the formula [wherein R, R 1 and R 2 are the same or different, each a hydrogen atom, a lower alkyl group (which preferably contains from 1 to 4 carbon atoms), or phenyl group] is particularly suitable.
本発明で使用される複素環式化合物の例は取分
け次のものである：イミダゾール、１−メチルイ
ミダゾール、１−エチルイミダゾール、１−プロ
ピルイミダゾール、１−ブチルイミダゾール、２
−メチルイミダゾール、２−エチルイミダゾー
ル、２−ブロピルイミダゾール、２−ブチルイミ
ダゾール、４−メチルイミダゾール、４−ブチル
イミダゾール、１，２−ジメチルイミダゾール、
１，２，４−トリメチルイミダゾール、１−フエ
ニルイミダゾール、２−フエニルイミダゾール及
びベンゾイミダゾール、更にイミダゾリン、２−
メチルイミダゾリン（リシジン）、２−フエニル
イミダゾリン並びにチアゾール、２−メチルチア
ゾール、２−エチルチアゾール、４−メチルチア
ゾール、４−エチルチアゾール、２−フエニルチ
アゾール、４−フエニルチアゾール、ベンゾチア
ゾール、ピリミジン、４−メチルピリジン、４−
エチルピリジン、１，３，５−トリアジン、１，
２，４−トリアジン、モルホリン、ピペリジンお
よびピペラジン。 Examples of heterocyclic compounds used in the invention are inter alia: imidazole, 1-methylimidazole, 1-ethylimidazole, 1-propylimidazole, 1-butylimidazole, 2
-Methylimidazole, 2-ethylimidazole, 2-bropylimidazole, 2-butylimidazole, 4-methylimidazole, 4-butylimidazole, 1,2-dimethylimidazole,
1,2,4-trimethylimidazole, 1-phenylimidazole, 2-phenylimidazole and benzimidazole, as well as imidazoline, 2-
Methylimidazoline (lysidine), 2-phenylimidazoline and thiazole, 2-methylthiazole, 2-ethylthiazole, 4-methylthiazole, 4-ethylthiazole, 2-phenylthiazole, 4-phenylthiazole, benzothiazole, pyrimidine , 4-methylpyridine, 4-
Ethylpyridine, 1,3,5-triazine, 1,
2,4-triazine, morpholine, piperidine and piperazine.
本発明による滴定剤の反応成分のための溶剤と
しては、無水の低分子量のアルコール、殊にメタ
ノール又はエチレングリコールモノメチルエーテ
ルが（アミン1molに対して）2molから50molま
で、殊に5molから20molまでの量で使用される。 Suitable solvents for the reaction components of the titrants according to the invention include anhydrous low-molecular-weight alcohols, in particular methanol or ethylene glycol monomethyl ether (per mol of amine) from 2 mol to 50 mol, in particular from 5 mol to 20 mol. used in quantity.
二酸化硫黄は酸、殊にカルボン酸との混合物で
も使用することができる。その場合、二酸化硫黄
の酸に対するモル比は20：１から１：５まで、殊
に２：１から１：２までである。適当な酸は例え
ば蟻酸、シユウ酸、硫酸、ヨウ化水素酸及び特に
酢酸である。 Sulfur dioxide can also be used in mixtures with acids, especially carboxylic acids. In that case, the molar ratio of sulfur dioxide to acid is from 20:1 to 1:5, in particular from 2:1 to 1:2. Suitable acids are, for example, formic acid, oxalic acid, sulfuric acid, hydroiodic acid and especially acetic acid.
本発明による滴定剤は複素環式化合物、二酸化
硫黄及びヨウ素をアルコールに、場合により15℃
から50℃まで、殊に20℃から40℃までの温度に冷
却しながら、溶解させることにより製造する。そ
の際（それぞれ溶液１に対して）アミンの量は
0.1molから10molまで、殊に0.5molから5molま
で、二酸化硫黄の量は0.1molから10molまで、殊
に0.5molから3molまで、そしてヨウ素の量は
0.01molから3molまで、殊に0.1molから1molま
でになる。溶液は、普通の方法で空気の湿気を排
除して且つ精製された出発物質を使用して製造さ
れる。 The titrant according to the invention contains a heterocyclic compound, sulfur dioxide and iodine in an alcohol, optionally at 15°C.
to 50°C, in particular by melting with cooling to a temperature of 20°C to 40°C. In that case, the amount of amine (for each solution 1) is
The amount of sulfur dioxide is from 0.1 mol to 10 mol, especially from 0.5 mol to 3 mol, and the amount of iodine is from 0.1 mol to 10 mol, especially from 0.5 mol to 5 mol.
From 0.01 mol to 3 mol, especially from 0.1 mol to 1 mol. The solutions are prepared in the usual way, excluding atmospheric moisture and using purified starting materials.
本発明による滴定剤は、カール−フイツシヤー
法により少量の水を定量するのに非常に適する。 The titrant according to the invention is very suitable for determining small amounts of water by the Karl-Fischer method.
本発明による滴定剤を使用して固体又は液体の
含水量、例えば無機塩、有機溶剤、脂肪、油、食
料品及び製剤の含水量が測定される。 The titrants according to the invention are used to determine the water content of solids or liquids, such as inorganic salts, organic solvents, fats, oils, foodstuffs and preparations.
本発明による滴定剤は高い貯蔵安定性の点がす
ぐれている。それは二成分の試薬としても一成分
の試薬としても適する。二成分試薬の形ではその
貯蔵安定性は少なくとも２年である。一成分試薬
の形では約１年間安定である。本発明による滴定
剤の特別の長所は、該滴定剤が高い反応速度を可
能にするという事である（使用例を参照）。更に、
この滴定剤は、滴定の終点が無色からかつ色への
色の変化により視覚で十分に認められるという点
がすぐれている。この滴定剤を（ボルタメーター
で指示するか又は死点を指示する）市販の自動滴
定装置で使用すると、非常に安定な終点が得られ
るので、水分測定の高い精度が保証される。この
滴定剤は更に、クーロメーターで水分を測定する
ための電解質として適する。 The titrant according to the invention is distinguished by high storage stability. It is suitable both as a two-component reagent and as a one-component reagent. In the form of a two-component reagent, its storage stability is at least 2 years. In the form of a one-component reagent, it is stable for approximately one year. A particular advantage of the titrant according to the invention is that it allows high reaction rates (see examples of use). Furthermore,
This titrant is distinguished by the fact that the end point of the titration is well recognized visually by the change in color from colorless to colored. The use of this titrant in commercially available automatic titrators (with voltammetric or dead point indication) provides a very stable endpoint, thus ensuring a high accuracy of the moisture determination. This titrant is furthermore suitable as an electrolyte for coulometer moisture determination.
以下、例を挙げて本発明を更に詳しく説明す
る。使用例(a)，(b)及び(c)による滴定の経過は市販
の自動滴定装置により軌録される。得られた曲線
は図面に示してある。曲線Ａは使用例(a)による滴
定を示し、曲線Ｂは使用例(b)による滴定を示し、
そして曲線Ｃは使用例(c)（比較例）による滴定を
示す。 Hereinafter, the present invention will be explained in more detail by giving examples. The progress of the titrations according to usage examples (a), (b) and (c) is recorded using a commercially available automatic titrator. The resulting curves are shown in the drawings. Curve A shows the titration according to use example (a), curve B shows the titration according to use example (b),
And curve C shows the titration according to use example (c) (comparative example).
例 １
(a) 420mlのメタノールを250ｇ（2.87mol）のモ
ルホリンと混合し、この混合物中へ35ないし40
℃の温度に冷却しながら190ｇ（2.97mol）の
二酸化硫黄を導入する（溶液Ａ）。モルホリン
のSO2に対するモル比は0.97：１である。Example 1 (a) Mix 420 ml of methanol with 250 g (2.87 mol) of morpholine and add 35 to 40
190 g (2.97 mol) of sulfur dioxide are introduced while cooling to a temperature of °C (solution A). The molar ratio of morpholine to SO2 is 0.97:1.
(b) 85ｇ（0.67mol）のヨウ素を１のメタノー
ルに溶解させる（溶液Ｂ）。(b) Dissolve 85 g (0.67 mol) of iodine in 1 part of methanol (solution B).
(c) 溶液Ａ＋Ｂは二成分試薬となつている。溶液
Ａは被検液に加えられ、そして溶液Ｂで滴定が
行われる。(c) Solution A+B is a two-component reagent. Solution A is added to the test liquid and titrated with solution B.
例 ２
(a) 200ｇの２−アミノチアゾール（2mol）を
550mlのメタノールに溶解させる。次に、絶え
ず15ないし20℃の温度に冷却しながら、130ｇ
の気体の二酸化硫黄（2.03mol）を導入する
（溶液Ａ）。モル比チアゾール：SO2は0.98：１
である。Example 2 (a) 200g of 2-aminothiazole (2mol)
Dissolve in 550ml methanol. Next, while constantly cooling to a temperature of 15 to 20°C, 130 g
of gaseous sulfur dioxide (2.03 mol) is introduced (solution A). Molar ratio thiazole: SO2 is 0.98:1
It is.
(b) 85ｇ（0.67mol）のヨウ素を１のメタノー
ルに溶解させる（溶液Ｂ）。(b) Dissolve 85 g (0.67 mol) of iodine in 1 part of methanol (solution B).
(c) 溶液Ａ＋Ｂは二成分試薬となつている。溶液
Ａは被検液に加えられ、溶液Ｂは滴定に役立
つ。(c) Solution A+B is a two-component reagent. Solution A is added to the test liquid and solution B serves for the titration.
例 ３
(a) 120ｇ（1.86mol）の二酸化硫黄を先ず700ml
のメタノール中へ20℃の温度に冷却しながら導
入する。次に、撹拌及び冷却しながら、300ｇ
（3.65mol）の２−メチルイミダゾールを温度
が30℃を越えないように徐々に加える。モル比
イミダゾール：SO2は1.96：１である。Example 3 (a) 120g (1.86mol) of sulfur dioxide is first added to 700ml.
into methanol with cooling to a temperature of 20°C. Next, while stirring and cooling, add 300g
(3.65 mol) of 2-methylimidazole is gradually added so that the temperature does not exceed 30°C. The molar ratio imidazole: SO2 is 1.96:1.
(b) 溶液Ｂは例７の溶液Ｂと同一である。(b) Solution B is the same as solution B of Example 7.
例 ４
204ｇ（3mol）のイミダゾールを700ｇのエチ
レングリコールモノメチルエーテルに溶解させ
る。次に、128ｇ（2mol）の二酸化硫黄を、温度
を冷却により25ないし30℃に保ちながら導入す
る。次に、100ｇ（0.8mol）のヨウ素を加える。
このようにして得られた一成分試薬１年間使用す
ることができる。Example 4 204 g (3 mol) of imidazole are dissolved in 700 g of ethylene glycol monomethyl ether. Then 128 g (2 mol) of sulfur dioxide are introduced, keeping the temperature between 25 and 30° C. by cooling. Next, add 100g (0.8mol) of iodine.
The one-component reagent thus obtained can be used for one year.
使用例
(a) 40mgの水を含有する20mlのメタノールを、例
３で得た滴定剤で滴定する。滴定は80秒後に終
つている（図面の曲線Ａを参照）。滴定の終点
は、無色からかつ色への色の変化で示されるの
で、視覚で決定することもできる。Application example (a) 20 ml of methanol containing 40 mg of water are titrated with the titrant obtained in Example 3. The titration is finished after 80 seconds (see curve A in the figure). The end point of the titration can also be determined visually as it is indicated by a change in color from colorless to colored.
(b) 40mgの水を例４による溶液で、滴定装置によ
り滴定する。滴定は、190秒後に終つており、
40mgの水の予定値を正確に達成し、この値は更
に10分間変らず示される（図面の曲線Ｂを参
照）。(b) Titrate 40 mg of water with the solution according to Example 4 in a titrator. The titration ended after 190 seconds.
The expected value of 40 mg of water is exactly achieved and this value remains unchanged for a further 10 minutes (see curve B in the drawing).
(c) エチレングリコールモノメチルエーテル１
当りピリジン250ｇ（3.16mol）、二酸化硫黄90
ｇ（1.40mol）そしてヨウ素140ｇ（1.10mol）
を含有する既知のKF試薬を使用して試験(a)を
繰返す。滴定は、当量点で満足な色の変化を示
さないので、市販の自動滴定装置を使用するこ
とによつてだけ行うことができる。滴定時間は
545秒である（図面の曲線Ｃを参照）；終点は一
定にとどまらない。(c) Ethylene glycol monomethyl ether 1
250g (3.16mol) of pyridine, 90% of sulfur dioxide
g (1.40 mol) and iodine 140 g (1.10 mol)
Repeat test (a) using the known KF reagent containing . Titration can only be carried out by using commercially available automatic titration equipment, since it does not show a satisfactory color change at the equivalence point. The titration time is
545 seconds (see curve C in the drawing); the end point does not remain constant.
(d) メタノール１当りピリジン700ｇ
（8.85mol）、二酸化硫黄81ｇ（1.27mol）そし
てヨウ素130ｇ（1.02mol）を含有し、ピリミ
ジンのSO2に対するモル比が７：１である既知
のKF試薬を使用して試験(a)を繰返す。滴定時
間は350秒である。(d) 700g of pyridine per methanol
Repeat test (a) using the known KF reagent containing (8.85 mol), sulfur dioxide 81 g (1.27 mol) and iodine 130 g (1.02 mol), with a molar ratio of pyrimidine to SO 2 of 7:1. . Titration time is 350 seconds.
図は、自動滴定装置で記録した使用例(a)、(b)及
び(c)による滴定の経過を示す図である。
Ａ……使用例(a)による滴定の経過を示す曲線、
Ｂ……使用例(b)による滴定の経過を示す曲線、Ｃ
……使用例(c)（比較例）による滴定の経過を示す
曲線。
The figure shows the progress of titration according to usage examples (a), (b), and (c) recorded with an automatic titrator. A...Curve showing the progress of titration according to usage example (a),
B...Curve showing the progress of titration according to usage example (b), C
...Curve showing the progress of titration according to usage example (c) (comparative example).
Claims (1)
有する滴定剤において、複素環式化合物が五員又
は六員の、場合により置換されている化合物−た
だし、少なくとも２個のヘテロ原子をもち、その
少なくとも１個のヘテロ原子が窒素原子である複
素環式化合物−であることを特徴とする滴定剤。 ２ 複素環式化合物の二酸化硫黄に対するモル比
が10：１から0.3：１までの範囲内である特許請
求の範囲第１項記載の滴定剤。 ３ 複素環式化合物が、炭素原子数１〜４の１、
２又３個のアルキル基又は１、２又３個のフエニ
ル基又は１個のベンゾ基で置換されている化合物
である特許請求の範囲第１項記載の滴定剤。 ４ 複素環式化合物がヘテロ原子として２個の窒
素原子を有する化合物である特許請求の範囲第３
項記載の滴定剤。 ５ 複素環式化合物がイミダゾール又はイミダゾ
ール誘導体である特許請求の範囲第４項記載の滴
定剤。 ６ 二酸化硫黄が酸と混合状態で存在しており、
その際二酸化硫黄と酸とのモル比が20：１〜１：
５である特許請求の範囲第１項記載の滴定剤。 ７ 酸がカルボン酸である特許請求の範囲第６項
記載の滴定剤。[Scope of Claims] 1. A titrant containing a heterocyclic compound, sulfur dioxide and iodine, in which the heterocyclic compound is a five- or six-membered, optionally substituted compound - provided that at least two heterocyclic compounds A titrant characterized in that it is a heterocyclic compound having atoms, at least one of which is a nitrogen atom. 2. The titrant according to claim 1, wherein the molar ratio of heterocyclic compound to sulfur dioxide is within the range of 10:1 to 0.3:1. 3 The heterocyclic compound has 1 to 4 carbon atoms,
The titrant according to claim 1, which is a compound substituted with two or three alkyl groups, one, two or three phenyl groups, or one benzo group. 4 Claim 3 in which the heterocyclic compound is a compound having two nitrogen atoms as heteroatoms
Titrant as described in section. 5. The titrant according to claim 4, wherein the heterocyclic compound is imidazole or an imidazole derivative. 6 Sulfur dioxide is present in a mixed state with an acid,
At that time, the molar ratio of sulfur dioxide and acid is 20:1 to 1:
5. The titrant according to claim 1, which is 7. The titrant according to claim 6, wherein the acid is a carboxylic acid.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3008421A DE3008421C2 (en) | 1980-03-05 | 1980-03-05 | Titration agent and its use |
| DE3008421.0 | 1980-03-05 | ||
| DE3039511.0 | 1980-10-20 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61111463A JPS61111463A (en) | 1986-05-29 |
| JPH0252219B2 true JPH0252219B2 (en) | 1990-11-09 |
Family
ID=6096337
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2999781A Granted JPS56137250A (en) | 1980-03-05 | 1981-03-04 | Titrating agent and method of using same |
| JP60184338A Granted JPS61111463A (en) | 1980-03-05 | 1985-08-23 | Titration agent |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2999781A Granted JPS56137250A (en) | 1980-03-05 | 1981-03-04 | Titrating agent and method of using same |
Country Status (3)
| Country | Link |
|---|---|
| JP (2) | JPS56137250A (en) |
| DE (1) | DE3008421C2 (en) |
| ZA (1) | ZA811422B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3010436A1 (en) * | 1980-03-19 | 1981-09-24 | Merck Patent Gmbh, 6100 Darmstadt | PYRIDINE-FREE KARL-FISCHER REAGENT AND METHOD FOR DETERMINING WATER BY MEANS OF THIS REAGENT |
| US4720464A (en) * | 1983-12-28 | 1988-01-19 | Mitsubishi Chemical Industries, Limited | Electrolytes for Karl Fischer coulometric titration |
| DE3407014A1 (en) * | 1984-02-27 | 1985-08-29 | Merck Patent Gmbh, 6100 Darmstadt | KARL FISCHER REAGENZ AND METHOD FOR DETERMINING WATER BY MEANS OF THIS REAGENT |
| DE3904992A1 (en) * | 1989-02-18 | 1990-08-23 | Riedel De Haen Ag | REAGENT FOR COULOMETRIC WATER DETERMINATION |
| JP2563881B2 (en) * | 1993-08-31 | 1996-12-18 | 道弘 村瀬 | Decorative board having bent portion and method for manufacturing the same |
-
1980
- 1980-03-05 DE DE3008421A patent/DE3008421C2/en not_active Expired
-
1981
- 1981-03-04 ZA ZA00811422A patent/ZA811422B/en unknown
- 1981-03-04 JP JP2999781A patent/JPS56137250A/en active Granted
-
1985
- 1985-08-23 JP JP60184338A patent/JPS61111463A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| DE3008421A1 (en) | 1981-09-10 |
| ZA811422B (en) | 1982-04-28 |
| DE3008421C2 (en) | 1982-08-26 |
| JPS56137250A (en) | 1981-10-27 |
| JPS6154182B2 (en) | 1986-11-21 |
| JPS61111463A (en) | 1986-05-29 |
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