JP7402574B1 - α-Iodo-substituted carboxylic acid - Google Patents
α-Iodo-substituted carboxylic acid Download PDFInfo
- Publication number
- JP7402574B1 JP7402574B1 JP2023041284A JP2023041284A JP7402574B1 JP 7402574 B1 JP7402574 B1 JP 7402574B1 JP 2023041284 A JP2023041284 A JP 2023041284A JP 2023041284 A JP2023041284 A JP 2023041284A JP 7402574 B1 JP7402574 B1 JP 7402574B1
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- JP
- Japan
- Prior art keywords
- acid
- iodo
- group
- substituted carboxylic
- carboxylic 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.)
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- 150000001732 carboxylic acid derivatives Chemical class 0.000 title claims abstract description 50
- 239000002253 acid Substances 0.000 claims abstract description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 12
- 125000003118 aryl group Chemical group 0.000 claims abstract description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- -1 2-iodo-2-methylmalonic acid Chemical compound 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- XIWYAAPVEZZWFT-UHFFFAOYSA-N 2-iodo-2-methylpropanoic acid Chemical compound CC(C)(I)C(O)=O XIWYAAPVEZZWFT-UHFFFAOYSA-N 0.000 claims description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 7
- 230000000087 stabilizing effect Effects 0.000 claims description 5
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- ZGPRANYVOMBLFL-UHFFFAOYSA-N 2-iodo-2-phenylacetic acid Chemical compound OC(=O)C(I)C1=CC=CC=C1 ZGPRANYVOMBLFL-UHFFFAOYSA-N 0.000 claims description 2
- 238000010586 diagram Methods 0.000 abstract 1
- 239000007864 aqueous solution Chemical class 0.000 description 9
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 8
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- 230000000052 comparative effect Effects 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 7
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- 238000010494 dissociation reaction Methods 0.000 description 6
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- 238000010526 radical polymerization reaction Methods 0.000 description 6
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- 238000002835 absorbance Methods 0.000 description 2
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- 239000000178 monomer Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
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- 125000005923 1,2-dimethylpropyloxy group Chemical group 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
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- XXSPGBOGLXKMDU-UHFFFAOYSA-N 2-bromo-2-methylpropanoic acid Chemical compound CC(C)(Br)C(O)=O XXSPGBOGLXKMDU-UHFFFAOYSA-N 0.000 description 1
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- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
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- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000005920 sec-butoxy group Chemical group 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005922 tert-pentoxy group Chemical group 0.000 description 1
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical group C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 125000001113 thiadiazolyl group Chemical group 0.000 description 1
- 125000001984 thiazolidinyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/50—Use of additives, e.g. for stabilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
- C07C53/15—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen containing halogen
- C07C53/19—Acids containing three or more carbon atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
【課題】熱や光等に対する安定性に優れる、α－ヨード置換カルボン酸を提供する。
【解決手段】下記一般式（１）
（式中、Ｒ１及びＲ２はそれぞれ独立して水素原子、カルボキシル基、脂肪族基又は芳香族基を表す。）で示され、含水量が０．１～１５．０質量％の範囲、かつ酸成分含有量が０．１５～３．０質量％の範囲である、α－ヨード置換カルボン酸。
【選択図】なしThe present invention provides an α-iodo-substituted carboxylic acid that has excellent stability against heat, light, etc.
[Solution] The following general formula (1)
(wherein R 1 and R 2 each independently represent a hydrogen atom, a carboxyl group, an aliphatic group, or an aromatic group), and the water content is in the range of 0.1 to 15.0% by mass, and an α-iodo-substituted carboxylic acid having an acid component content in the range of 0.15 to 3.0% by mass.
[Selection diagram] None
Description
本発明は、α－ヨード置換カルボン酸に関する。 The present invention relates to alpha-iodo substituted carboxylic acids.
ヨウ素及びヨウ素化合物はその生理活性、抗菌性、Ｘ線吸収能等の独自の性質や、高い反応性等を活かし、殺菌剤、造影剤、色素、医薬品、農薬、電荷輸送材、酸化剤、精密重合、触媒等の種々の用途に広く用いられている（例えば非特許文献１等を参照）。 Iodine and iodine compounds take advantage of their unique properties such as physiological activity, antibacterial properties, X-ray absorption ability, and high reactivity, and are used as disinfectants, contrast agents, dyes, pharmaceuticals, agricultural chemicals, charge transport materials, oxidizing agents, precision medicines, etc. It is widely used in various applications such as polymerization and catalysts (see, for example, Non-Patent Document 1).
有機ヨウ素化合物の中でもα－ヨード置換カルボン酸は、制御ラジカル重合とも称されるリビングラジカル重合におけるラジカル発生剤や分子量制御剤、各種ファインケミカルの合成原料又は中間体等として有用である。しかし、α－ヨード置換カルボン酸は、熱や光に晒されたり、酸化還元条件下で分解されやすく、その安定性（長期保存性）には改善の余地があった。
本発明の目的は、熱や光等に対し安定化され、分解が抑制されるα－ヨード置換カルボン酸を提供することにある。
本発明者らは、鋭意研究を重ねた結果、水分及び酸成分を特定範囲でα－ヨード置換カルボン酸に含有させることで前記課題を解決できることを見出し、本発明を完成した。
Among organic iodine compounds, α-iodo-substituted carboxylic acids are useful as radical generators and molecular weight control agents in living radical polymerization, also called controlled radical polymerization, and as raw materials or intermediates for the synthesis of various fine chemicals. However, α-iodo-substituted carboxylic acids are easily decomposed when exposed to heat or light or under redox conditions, and there is room for improvement in their stability (long-term storage).
An object of the present invention is to provide an α-iodo-substituted carboxylic acid that is stabilized against heat, light, etc. and whose decomposition is suppressed.
As a result of extensive research, the present inventors have discovered that the above-mentioned problems can be solved by incorporating moisture and acid components within a specific range into an α-iodo-substituted carboxylic acid, and have completed the present invention.
本発明は、下記の態様を有する。
［１］ 下記一般式（１）
で示され、含水量が０．１～１５．０質量％の範囲、かつ酸成分含有量が０．１５～３．０質量％の範囲である、α－ヨード置換カルボン酸。
［２］ 前記酸成分の酸解離定数(ｐＫａ）が、２．８以下である、前記［１］に記載のα－ヨード置換カルボン酸。
［３］ 前記酸成分が、無機酸である、前記［１］又は［２］に記載のα－ヨード置換カルボン酸。
［４］ 下記一般式（１）
[1] General formula (1) below
An α-iodo-substituted carboxylic acid having a water content in the range of 0.1 to 15.0% by mass and an acid component content in the range of 0.15 to 3.0% by mass.
[2] The α-iodo-substituted carboxylic acid according to [1] above, wherein the acid component has an acid dissociation constant (pKa) of 2.8 or less.
[3] The α-iodo-substituted carboxylic acid according to [1] or [2] above, wherein the acid component is an inorganic acid.
[4] General formula (1) below
本発明によれば、熱や光等に対し安定化され、分解が抑制されるα－ヨード置換カルボン酸を提供できる。 According to the present invention, it is possible to provide an α-iodo-substituted carboxylic acid that is stabilized against heat, light, etc. and whose decomposition is suppressed.
本発明は、下記一般式（１）
本発明のα－ヨード置換カルボン酸は、熱や光等に対する安定性に優れており、分解が抑制され、また、長期に亘る保存後も着色が抑制される。
このような効果が発現する詳細な理由は不明であるが、α－ヨード置換カルボン酸におけるカルボキシル基の水存在下における解離平衡が、酸成分が特定量の範囲で存在することにより、水素イオンが解離しない側に傾くため、α－ヨード置換カルボン酸としての安定性が高まり、ヨウ素の遊離等の分解が抑制されると推定される。
The present invention is based on the following general formula (1)
The α-iodo-substituted carboxylic acid of the present invention has excellent stability against heat and light, suppresses decomposition, and suppresses discoloration even after long-term storage.
Although the detailed reason for such an effect is unknown, the dissociation equilibrium of the carboxyl group in the α-iodo-substituted carboxylic acid in the presence of water is such that the presence of the acid component within a certain range causes hydrogen ions to be released. It is presumed that because it leans toward the non-dissociating side, its stability as an α-iodo-substituted carboxylic acid increases, and decomposition such as liberation of iodine is suppressed.
一般式（１）において、Ｒ１及びＲ２がそれぞれ独立して表す脂肪族基としては、直鎖又は分岐状の脂肪族炭化水素基、脂環式炭化水素基が挙げられる。
直鎖又は分岐状の脂肪族炭化水素基の炭素数は１～１２が好ましく、例えばメチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ｎ－ヘキシル基、ｎ－オクチル基、２－エチルヘキシル基、デシル基、ドデシル基等が挙げられる。
脂環式炭化水素基の炭素数は３～１２が好ましく、例えばシクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロオクチル基、ビシクロヘキシル基等が挙げられる。
中でも、脂肪族基として、炭素数は１～１２の直鎖又は分岐状の脂肪族炭化水素基が好ましく、メチル基、エチル基、プロピル基、ブチル基がより好ましい。
In general formula (1), examples of the aliphatic groups each independently represented by R 1 and R 2 include a linear or branched aliphatic hydrocarbon group and an alicyclic hydrocarbon group.
The straight chain or branched aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert -butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, decyl group, dodecyl group, etc.
The alicyclic hydrocarbon group preferably has 3 to 12 carbon atoms, and includes, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, and a bicyclohexyl group.
Among these, the aliphatic group is preferably a linear or branched aliphatic hydrocarbon group having 1 to 12 carbon atoms, and more preferably a methyl group, ethyl group, propyl group, or butyl group.
一般式（１）において、Ｒ１及びＲ２がそれぞれ独立して表す芳香族基としては、芳香族炭化水素基、芳香族複素環基が挙げられる。
芳香族炭化水素基の炭素数は６～２０が好ましく、例えばフェニル基、ナフチル基、ビフェニル基、アントラセニル基、フェナントレニル基、アズレニル基、ターフェニル基等が挙げられる。
芳香族複素環基の炭素数は６～２０が好ましく、例えばフリル基、チエニル基、ピロリル基、ピラゾリル基、ピリジル基、イミダゾリル基、イソキサゾリル基、チアゾリル基、チアジアゾリル基、ベンゾフラニル基、インドリル基、ベンゾチアゾリル基、カルバゾリル基等が挙げられる。
In general formula (1), the aromatic groups each independently represented by R 1 and R 2 include an aromatic hydrocarbon group and an aromatic heterocyclic group.
The aromatic hydrocarbon group preferably has 6 to 20 carbon atoms, and includes, for example, phenyl, naphthyl, biphenyl, anthracenyl, phenanthrenyl, azulenyl, and terphenyl.
The aromatic heterocyclic group preferably has 6 to 20 carbon atoms, such as furyl group, thienyl group, pyrrolyl group, pyrazolyl group, pyridyl group, imidazolyl group, isoxazolyl group, thiazolyl group, thiadiazolyl group, benzofuranyl group, indolyl group, benzothiazolyl group. group, carbazolyl group, etc.
上述した脂肪族基又は芳香族基は、置換基を有していてもよい。かかる置換基としては、水酸基、シアノ基、カルボキシル基、ニトロ基；フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子；メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロへキシル基等のアルキル基；メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、イソプロポキシ基、イソブトキシ基、ｔｅｒｔ－ブトキシ基、ｓｅｃ－ブトキシ基、イソペンチルオキシ基、ネオペンチルオキシ基、ｔｅｒｔ－ペンチルオキシ基、１，２－ジメチルプロポキシ基等のアルコキシル基等が挙げられる。 The aliphatic group or aromatic group mentioned above may have a substituent. Such substituents include hydroxyl group, cyano group, carboxyl group, nitro group; halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group. Alkyl groups such as isobutyl group, sec-butyl group, tert-butyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group; methoxy group, ethoxy group, propoxy group, butoxy group, isopropoxy group, Examples include alkoxyl groups such as isobutoxy group, tert-butoxy group, sec-butoxy group, isopentyloxy group, neopentyloxy group, tert-pentyloxy group, and 1,2-dimethylpropoxy group.
また、一般式（１）において、Ｒ１及びＲ２が互いに結合して環構造を形成していてもよい。かかる環構造としては、例えばシクロペンタン環、シクロヘキサン環、テトラヒドロフラン環、ジオキサン環、ピロリジン環、ピペリジン環、オキサゾリジン環、ピペラジン環、モルホリン環、チアゾリジン環、テトラヒドロチオフェン環、ピロール環、トリアゾール環、ピペラジノン環等が挙げられる。 Furthermore, in the general formula (1), R 1 and R 2 may be bonded to each other to form a ring structure. Examples of such ring structures include a cyclopentane ring, a cyclohexane ring, a tetrahydrofuran ring, a dioxane ring, a pyrrolidine ring, a piperidine ring, an oxazolidine ring, a piperazine ring, a morpholine ring, a thiazolidine ring, a tetrahydrothiophene ring, a pyrrole ring, a triazole ring, and a piperazinone ring. etc.
一般式（１）で示されるα－ヨード置換カルボン酸の具体例としては、２－ヨード酢酸、２－ヨードプロピオン酸、２－ヨード－２－メチルプロピオン酸、２－ヨードペンタン酸、２－ヨード－２－フェニル酢酸、２－ヨードマロン酸、２－ヨード－２－メチルマロン酸、２，５－ジヨードアジピン酸、２，５－ジヨード－２，５－ジメチルアジピン酸、２－ヨードアセト酢酸、２－ヨード－２－メチルアセト酢酸等が挙げられる。
中でも、本発明の安定化の効果がより奏される観点から、α－ヨード置換カルボン酸として２－ヨード－２－メチルプロピオン酸、２－ヨード－２－フェニル酢酸、２－ヨード－２－メチルマロン酸、２－ヨード－２－メチルアセト酢酸が好ましい。
Specific examples of the α-iodo-substituted carboxylic acid represented by general formula (1) include 2-iodoacetic acid, 2-iodopropionic acid, 2-iodo-2-methylpropionic acid, 2-iodopentanoic acid, and 2-iodopropionic acid. -2-phenylacetic acid, 2-iodomalonic acid, 2-iodo-2-methylmalonic acid, 2,5-diiodoadipic acid, 2,5-diiodo-2,5-dimethyladipic acid, 2-iodoacetoacetic acid, 2 -iodo-2-methylacetoacetic acid and the like.
Among them, 2-iodo-2-methylpropionic acid, 2-iodo-2-phenylacetic acid, 2-iodo-2-methyl Malonic acid and 2-iodo-2-methylacetoacetic acid are preferred.
α－ヨード置換カルボン酸に、水と共に含有させる酸成分は、α－ヨード置換カルボン酸以外の酸であり、有機酸でも無機酸でもよく、ブレンステッド酸でもルイス酸でもよい。本発明において、酸成分としてルイス酸を用いる場合は、水と共存させることで無機酸を発生し、かかる無機酸が本発明の安定化作用を奏する場合もある。例えば塩化アルミニウムを使用する場合は、水が共存すると塩化水素を発生し、塩酸と同様の作用を奏する。 The acid component contained in the α-iodo-substituted carboxylic acid together with water is an acid other than the α-iodo-substituted carboxylic acid, and may be an organic acid or an inorganic acid, and may be a Brønsted acid or a Lewis acid. In the present invention, when a Lewis acid is used as an acid component, an inorganic acid is generated by coexistence with water, and such an inorganic acid may exhibit the stabilizing effect of the present invention. For example, when aluminum chloride is used, it generates hydrogen chloride when water coexists, and has the same effect as hydrochloric acid.
酸成分としては、本発明において、α－ヨード置換カルボン酸の熱や光等に対する安定性をより高められる観点から、酸解離定数（ｐＫａ）が２．８以下である酸が好ましい。酸解離定数（ｐＫａ）の下限に厳密な意味での制限はないが、取扱い性等の観点から－９以上であることが好ましい。なお、酸解離定数（ｐＫａ）は、化学便覧 基礎編 改訂６版（令和３年１月２０日発行）に示される、２５℃での値である。また、酸成分が２価又はそれ以上の価数の酸である場合には、本明細書におけるｐＫａは、ｐＫａ１（第１解離段）の値を意味する。
好適な酸成分としては、例えば臭化水素酸、塩酸、硫酸、リン酸、トリフルオロ酢酸、トリクロロ酢酸、シュウ酸等が挙げられる。
中でも、安価で工業的に入手容易である観点、酸成分の含有量の制御が容易であり、本発明の効果を奏しやすい観点から、無機酸がより好ましく、硫酸（－３．２９）又は塩酸（－５．９）がさらに好ましい。ここで、括弧内の数値は各々の酸のｐＫａ値を示す。
In the present invention, the acid component is preferably an acid having an acid dissociation constant (pKa) of 2.8 or less, from the viewpoint of further increasing the stability of the α-iodo-substituted carboxylic acid against heat, light, etc. Although there is no strict limit to the lower limit of the acid dissociation constant (pKa), it is preferably −9 or more from the viewpoint of ease of handling. Note that the acid dissociation constant (pKa) is the value at 25°C shown in the Chemical Handbook, Basic Edition, Revised 6th Edition (published on January 20, 2021). Furthermore, when the acid component is a divalent or higher valence acid, pKa in this specification means the value of pKa 1 (first dissociation stage).
Suitable acid components include, for example, hydrobromic acid, hydrochloric acid, sulfuric acid, phosphoric acid, trifluoroacetic acid, trichloroacetic acid, oxalic acid, and the like.
Among these, inorganic acids are more preferable from the viewpoint of being inexpensive and easily available industrially, the content of the acid component is easy to control, and the effects of the present invention are easily achieved, and sulfuric acid (-3.29) or hydrochloric acid are preferred. (-5.9) is more preferable. Here, the numbers in parentheses indicate the pKa value of each acid.
本発明において、α－ヨード置換カルボン酸が含有する酸成分の含有量は、０．１５質量％以上であり、０．２質量％以上であるのが好ましく、０．３質量％以上がより好ましい。酸成分の含有量は３．０質量％以下であり、２．０質量％以下であるのが好ましく、１．０質量％以下がより好ましい。 In the present invention, the content of the acid component contained in the α-iodo-substituted carboxylic acid is 0.15% by mass or more, preferably 0.2% by mass or more, and more preferably 0.3% by mass or more. . The content of the acid component is 3.0% by mass or less, preferably 2.0% by mass or less, and more preferably 1.0% by mass or less.
また、本発明におけるα－ヨード置換カルボン酸の含水量は、０．１質量％以上であり、０．５質量％以上であるのが好ましく、１．０質量％以上がより好ましい。含水量は１５．０質量％以下であり、１０．０質量％以下が好ましく、５．０質量％以下がより好ましい。
本発明においては、α－ヨード置換カルボン酸の含水量が０．１～５．０質量％の範囲であり、かつ酸成分の含有量が０．１５～１．０質量％の範囲であるのが、熱や光等に対する安定性をより高められ、分解を抑制でき、長期に亘る保存後も着色が抑制される観点から好ましい。
本発明のα－ヨード置換カルボン酸は、換言すれば、α－ヨード置換カルボン酸と、水及び酸成分とをそれぞれ特定量含有する組成物であるとも言える。すなわち、本発明では、α－ヨード置換カルボン酸が、酸成分の含有量及び含水量が共に上記した範囲であることで、熱や光等に対する安定性に優れており、分解が抑制され、また長期に亘る保存後も着色が抑制される。
Further, the water content of the α-iodo-substituted carboxylic acid in the present invention is 0.1% by mass or more, preferably 0.5% by mass or more, and more preferably 1.0% by mass or more. The water content is 15.0% by mass or less, preferably 10.0% by mass or less, and more preferably 5.0% by mass or less.
In the present invention, the water content of the α-iodo-substituted carboxylic acid is in the range of 0.1 to 5.0% by mass, and the content of the acid component is in the range of 0.15 to 1.0% by mass. However, it is preferable from the viewpoint that stability against heat, light, etc. can be further improved, decomposition can be suppressed, and coloring can be suppressed even after long-term storage.
In other words, the α-iodo-substituted carboxylic acid of the present invention can be said to be a composition containing the α-iodo-substituted carboxylic acid and specific amounts of water and acid components, respectively. That is, in the present invention, the α-iodo-substituted carboxylic acid has an acid component content and a water content both within the above-mentioned ranges, so that it has excellent stability against heat, light, etc., decomposition is suppressed, and Coloration is suppressed even after long-term storage.
α－ヨード置換カルボン酸は、例えば国際公開２０１８／１８０５４７号に記載される方法等で製造できる。得られたα－ヨード置換カルボン酸に、上述した所定量の範囲で水及び酸成分を添加して、本発明のα－ヨード置換カルボン酸を得る。
ここで、水及び酸成分は得られたα－ヨード置換カルボン酸に直接添加してもよく、酸成分を水に溶解させた水溶液として、公知の方法で得たα－ヨード置換カルボン酸に接触させることもできる。操作性の観点からは、酸成分を水に溶解させた水溶液として、公知の方法で得たα－ヨード置換カルボン酸に接触させることが好ましい。
酸成分を水に溶解させた水溶液を接触させる際の接触時間に特に制限はないが、操作性や生産性の観点から、通常、１分～２４時間の範囲であるのが好ましい。また、接触温度は、発熱等を抑制する観点から、通常、０℃～４０℃以下の範囲が好ましく、０℃～２０℃以下の範囲がより好ましい。
The α-iodo-substituted carboxylic acid can be produced, for example, by the method described in International Publication No. 2018/180547. The α-iodo-substituted carboxylic acid of the present invention is obtained by adding water and an acid component in the above-mentioned predetermined amounts to the obtained α-iodo-substituted carboxylic acid.
Here, water and the acid component may be added directly to the obtained α-iodo-substituted carboxylic acid, or an aqueous solution in which the acid component is dissolved in water is contacted with the α-iodo-substituted carboxylic acid obtained by a known method. You can also do it. From the viewpoint of operability, it is preferable to contact an α-iodo-substituted carboxylic acid obtained by a known method as an aqueous solution in which the acid component is dissolved in water.
There is no particular restriction on the contact time when an aqueous solution of an acid component dissolved in water is brought into contact, but from the viewpoint of operability and productivity, it is usually preferably in the range of 1 minute to 24 hours. Further, from the viewpoint of suppressing heat generation, the contact temperature is usually preferably in the range of 0°C to 40°C, more preferably 0°C to 20°C.
酸成分を水に溶解させた水溶液との接触後、濾過、遠心分離等の通常の分離操作により、本発明のα－ヨード置換カルボン酸を得る。
本発明のα－ヨード置換カルボン酸を得るに際しての含水量及び酸成分含有量の制御は、例えば、接触時に用いる水及び酸成分の量の調整により、好適には酸成分を水に溶解させた水溶液において酸成分の濃度を調整することにより、行うことができる。また、水及び酸成分を接触させた後の分離時に、本発明で規定する範囲内に水及び酸成分が残留する程度に、分離操作を行ってもよい。さらには、水が過剰に残留する状態となるように分離操作を行い、次いで減圧下に水を留去して、本発明で規定する範囲内に含水量を調節してもよい。
After contact with an aqueous solution in which an acid component is dissolved in water, the α-iodo-substituted carboxylic acid of the present invention is obtained by conventional separation operations such as filtration and centrifugation.
When obtaining the α-iodo-substituted carboxylic acid of the present invention, the water content and acid component content can be controlled, for example, by adjusting the amounts of water and acid component used during contact, preferably by dissolving the acid component in water. This can be done by adjusting the concentration of the acid component in the aqueous solution. Moreover, at the time of separation after bringing water and acid components into contact, the separation operation may be performed to such an extent that water and acid components remain within the range defined by the present invention. Furthermore, the water content may be adjusted within the range specified by the present invention by performing a separation operation so that an excessive amount of water remains, and then distilling off the water under reduced pressure.
本発明のα－ヨード置換カルボン酸は、各種ファインケミカルの合成原料又は中間体として有用である。また、本発明のα－ヨード置換カルボン酸は、例えばリビングラジカル重合におけるラジカル発生剤や分子量制御剤として有用である。
ここで、リビングラジカル重合では、アゾイソブチロニトリル等のアゾ化合物；過酸化水素、過硫酸カリウム、過硫酸アンモニウム等の無機過酸化物；過酸化ベンゾイル、ジｔ－ブチルパーオキシド、クメンヒドロパーオキシド等の有機過酸化物；レドックス系触媒；等のラジカル重合開始剤と、本発明のα－ヨード置換カルボン酸を併用することができる。
また、ラジカル重合可能なモノマーとしては、例えば（メタ）アクリル酸、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ブチル、（メタ）アクリル酸ヒドロキシエチル、（メタ）アクリル酸アミド、（メタ）アクリロニトリル等の、（メタ）アクリル酸若しくはその塩、エステル、アミド又はニトリル等の（メタ）アクリル酸誘導体；スチレン、α－メチルスチレン、ｏ－メチルスチレン、ｐ－メチルスチレン、ヒドロキシスチレン、ジクロロスチレン等の、スチレン又はスチレン誘導体；エチレン、プロプレン、ブテン、イソブテン、ヘキセン、オクテン、デセン、ドデセン、ピネン、リモネン、インデン等のオレフィン；ブタジエン、イソプレン、シクロペンタジエン、ビシクロペンタジエン、エチリデンノルボルネン等のジエン；酢酸ビニル、ピバリン酸ビニル等のビニルエステル；ブチルビニルエーテル等のビニルエーテル；等が挙げられる。
本発明のα－ヨード置換カルボン酸は、上述したモノマーのリビングラジカル重合において、ラジカル発生剤や分子量制御剤として有効に適用できる。
The α-iodo-substituted carboxylic acid of the present invention is useful as a raw material or intermediate for the synthesis of various fine chemicals. Further, the α-iodo-substituted carboxylic acid of the present invention is useful, for example, as a radical generator or molecular weight control agent in living radical polymerization.
Here, in living radical polymerization, azo compounds such as azoisobutyronitrile; inorganic peroxides such as hydrogen peroxide, potassium persulfate, ammonium persulfate; benzoyl peroxide, di-t-butyl peroxide, cumene hydroperoxide; The α-iodo-substituted carboxylic acid of the present invention can be used in combination with a radical polymerization initiator such as an organic peroxide such as a redox catalyst;
Examples of monomers that can be radically polymerized include (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hydroxyethyl (meth)acrylate, and (meth)acrylate. (meth)acrylic acid or its salts, esters, amides, or (meth)acrylic acid derivatives such as nitrile, such as acid amide, (meth)acrylonitrile; styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, Styrene or styrene derivatives such as hydroxystyrene and dichlorostyrene; Olefins such as ethylene, proprene, butene, isobutene, hexene, octene, decene, dodecene, pinene, limonene, and indene; butadiene, isoprene, cyclopentadiene, bicyclopentadiene, ethylidenenorbornene dienes such as; vinyl esters such as vinyl acetate and vinyl pivalate; vinyl ethers such as butyl vinyl ether; and the like.
The α-iodo-substituted carboxylic acid of the present invention can be effectively applied as a radical generator or molecular weight control agent in the above-mentioned living radical polymerization of monomers.
本発明はまた、前述した一般式（１）で示されるα－ヨード置換カルボン酸に、水を０．１～１５．０質量％の範囲、かつ酸成分を０．１５～３．０質量％の範囲で含有させる、α－ヨード置換カルボン酸の安定化方法である。
例えば国際公開２０１８／１８０５４７号に記載される方法等で得たα－ヨード置換カルボン酸に、水及び酸成分を上記範囲で含有させることで、α－ヨード置換カルボン酸の熱や光等に対する安定性が改善され、分解が抑制され、長期に亘る保存後も着色が抑制される。
α－ヨード置換カルボン酸、酸成分の詳細や、水及び酸成分を上記範囲で含有させる手段の詳細は、上述した通りである。
The present invention also provides the α-iodo-substituted carboxylic acid represented by the general formula (1) above, water in a range of 0.1 to 15.0% by mass, and acid component in a range of 0.15 to 3.0% by mass. This is a method for stabilizing α-iodo-substituted carboxylic acid by containing it within the range of .
For example, by incorporating water and acid components in the above range into α-iodo-substituted carboxylic acid obtained by the method described in International Publication No. 2018/180547, etc., the α-iodo-substituted carboxylic acid can be stabilized against heat, light, etc. properties are improved, decomposition is suppressed, and coloration is suppressed even after long-term storage.
The details of the α-iodo-substituted carboxylic acid and the acid component, and the means for containing water and the acid component in the above ranges are as described above.
以下、実施例により本発明を具体的に説明する。ただし、本発明は下記の実施例に限定されない。各評価における分析は以下のようにして行った。
〔純度〕
各実施例及び比較例で得た試料をジクロロメタンに溶解させ、ガスクロマトグラフィー分析によるクロマトグラムのピーク面積値より算出した。測定条件は以下のとおりである。
機器：島津製作所社製「ＧＣ－２０１０」
カラム：ＨＰ－ＵＬＴＲＡ１（Ａｇｉｌｅｎｔ社製、２５ｍ×０．３２ｍｍＩ．Ｄ．）
キャリアガス：ヘリウム
温度：５０℃で３分保持→３０℃／分で昇温→２５０℃で保持
検出器：水素炎イオン化検出器（ＦＩＤ）
Hereinafter, the present invention will be specifically explained with reference to Examples. However, the present invention is not limited to the following examples. Analysis for each evaluation was performed as follows.
〔purity〕
The samples obtained in each Example and Comparative Example were dissolved in dichloromethane, and the values were calculated from the peak area values of the chromatograms analyzed by gas chromatography. The measurement conditions are as follows.
Equipment: “GC-2010” manufactured by Shimadzu Corporation
Column: HP-ULTRA1 (manufactured by Agilent, 25m x 0.32mm I.D.)
Carrier gas: Helium Temperature: Hold at 50°C for 3 minutes → Increase temperature at 30°C/min → Hold at 250°C Detector: Flame ionization detector (FID)
〔遊離ヨウ素量〕
各実施例及び比較例で得た試料２ｇと、１，２－ジクロロエタン（ＤＣＥ）１８ｇとをそれぞれ精秤して混合し、試料を完全に溶解させて溶液を調製した。この溶液の吸光度（４９８ｎｍ、７００ｎｍ）を吸光光度計（日本分光社製「Ｖ－７３０ｉＲＭ」）で測定し、ヨウ素濃度を変化させたＤＣＥ溶液を用いて別途予め作成した吸光度検量線より、試料中の遊離ヨウ素濃度（ｐｐｍ）を求めた。
[Free iodine amount]
2 g of the sample obtained in each Example and Comparative Example and 18 g of 1,2-dichloroethane (DCE) were each accurately weighed and mixed to completely dissolve the sample to prepare a solution. The absorbance (498nm, 700nm) of this solution was measured using an absorption photometer (JASCO Corporation "V-730iRM"), and the absorbance calibration curve prepared separately using DCE solutions with varying iodine concentrations was used to determine the amount of light in the sample. The free iodine concentration (ppm) was determined.
＜製造例１：２－ヨード－２－メチルプロピオン酸の製造＞
２－ブロモ－２－メチルプロピオン酸１０．０質量部をアセトン１６０質量部に溶解させ、この溶液にヨウ化ナトリウム４４．９質量部を加えて、５５℃で１８時間撹拌した。反応混合物からアセトンを減圧下で留去し、残留物にジクロロメタン及び水を加えて分液した。
得られた有機層を飽和食塩水で洗浄して硫酸ナトリウムで乾燥後、濃縮して、２－ヨード－２－メチルプロピオン酸１０．１質量部を結晶として得た。
<Production Example 1: Production of 2-iodo-2-methylpropionic acid>
10.0 parts by mass of 2-bromo-2-methylpropionic acid was dissolved in 160 parts by mass of acetone, 44.9 parts by mass of sodium iodide was added to this solution, and the mixture was stirred at 55° C. for 18 hours. Acetone was distilled off from the reaction mixture under reduced pressure, and dichloromethane and water were added to the residue to separate the layers.
The obtained organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated to obtain 10.1 parts by mass of 2-iodo-2-methylpropionic acid as crystals.
［実施例１］
製造例１の方法で得た２－ヨード－２－メチルプロピオン酸１００質量部に、硫酸水溶液（濃度１７．４質量％）１００質量部を加え、５℃で３０分間撹拌した。その後、遠心効果３９０Ｇで１０分、遠心分離することにより、含水量４．２３質量％、酸成分含有量（硫酸含有量）０．２１質量％である２－ヨード－２－メチルプロピオン酸を得た。
ここで、含水量は、得られた２－ヨード－２－メチルプロピオン酸を所定量秤量して五酸化二リンを乾燥剤とするデシケーター中に配置して恒量とし、乾燥前後の質量減量分より算出した。また、酸成分の含有量は、上記で算出された含水量に基づいて算出した。
[Example 1]
To 100 parts by mass of 2-iodo-2-methylpropionic acid obtained by the method of Production Example 1, 100 parts by mass of an aqueous sulfuric acid solution (concentration 17.4% by mass) was added, and the mixture was stirred at 5° C. for 30 minutes. Thereafter, 2-iodo-2-methylpropionic acid having a water content of 4.23% by mass and an acid component content (sulfuric acid content) of 0.21% by mass was obtained by centrifugation for 10 minutes at a centrifugal effect of 390G. Ta.
Here, the water content is determined by weighing a predetermined amount of the obtained 2-iodo-2-methylpropionic acid and placing it in a desiccator using diphosphorus pentoxide as a desiccant to maintain a constant weight. Calculated. Moreover, the content of the acid component was calculated based on the water content calculated above.
［実施例２～３］
実施例１において、硫酸水溶液に代えて塩酸又はシュウ酸水溶液を用いた以外は、実施例１と同様の操作を行い、表１に示す含水量及び酸成分含有量である２－ヨード－２－メチルプロピオン酸を得た。
［比較例１］
実施例１において、硫酸水溶液に代えて純水を用いた以外は、実施例１と同様の操作を行い、表１に示す含水量である２－ヨード－２－メチルプロピオン酸を得た。
[Example 2-3]
In Example 1, the same operation as in Example 1 was performed except that hydrochloric acid or oxalic acid aqueous solution was used in place of the sulfuric acid aqueous solution, and 2-iodo-2- with the water content and acid component content shown in Table 1 was prepared. Methylpropionic acid was obtained.
[Comparative example 1]
In Example 1, the same operation as in Example 1 was performed except that pure water was used instead of the sulfuric acid aqueous solution, and 2-iodo-2-methylpropionic acid having the water content shown in Table 1 was obtained.
＜評価例１＞
実施例１～３、及び比較例１で得た２－ヨード－２－メチルプロピオン酸を、アルゴン雰囲気下で容量６ｍｌのサンプル瓶に入れて蓋をした後、４０℃の恒温槽中で静置し、静置直後（０日）、４日後、１０日後の純度を測定し、安定性を評価した。
結果を表１に示す。本発明の規定を満足するα－ヨード置換カルボン酸は、熱に対する安定性に優れる。一方、酸成分を含有せず含水量のみが本発明で規定する範囲である場合は、純度が経時的に低下し、熱に対する安定性を維持できないことがわかる。
<Evaluation example 1>
The 2-iodo-2-methylpropionic acid obtained in Examples 1 to 3 and Comparative Example 1 was placed in a 6 ml sample bottle under an argon atmosphere, capped, and left to stand in a constant temperature bath at 40°C. Then, the purity was measured immediately after standing (0 days), 4 days later, and 10 days later, and the stability was evaluated.
The results are shown in Table 1. An α-iodo-substituted carboxylic acid that satisfies the requirements of the present invention has excellent stability against heat. On the other hand, when the acid component is not contained and only the water content is within the range specified by the present invention, the purity decreases over time and it is found that the stability against heat cannot be maintained.
［実施例４～６、比較例２］
実施例１において、硫酸濃度を変化させた水溶液を用いた以外は、実施例１と同様の操作を行い、表２に示す含水量及び酸成分含有量である２－ヨード－２－メチルプロピオン酸を得た。
＜評価例２＞
実施例４～６、及び比較例２で得た２－ヨード－２－メチルプロピオン酸を、アルゴン雰囲気下で容量６ｍｌのサンプル瓶に入れて蓋をした後、４０℃の恒温槽中で静置し、静置直後（０日）、６日後及び２０日後の純度及び遊離ヨウ素量の経時変化を追跡して、安定性を評価した。
結果を表２に示す。本発明の規定を満足するα－ヨード置換カルボン酸は、熱に対する安定性に優れ、着色も抑制される。一方、比較例２より、酸成分である硫酸の含有量が本発明で規定する範囲を下回ると、遊離ヨウ素の発生が増大し、着色の要因となる。
[Examples 4 to 6, Comparative Example 2]
In Example 1, the same operation as in Example 1 was performed except that aqueous solutions with varying sulfuric acid concentrations were used, and 2-iodo-2-methylpropionic acid having the water content and acid component content shown in Table 2 was prepared. I got it.
<Evaluation example 2>
The 2-iodo-2-methylpropionic acid obtained in Examples 4 to 6 and Comparative Example 2 was placed in a 6 ml sample bottle under an argon atmosphere, covered, and left to stand in a constant temperature bath at 40°C. The stability was evaluated by tracking changes over time in purity and amount of free iodine immediately after standing (0 days), 6 days later, and 20 days later.
The results are shown in Table 2. An α-iodo-substituted carboxylic acid that satisfies the requirements of the present invention has excellent thermal stability and is suppressed from coloring. On the other hand, from Comparative Example 2, when the content of sulfuric acid, which is an acid component, is below the range specified by the present invention, the generation of free iodine increases, which becomes a cause of coloration.
本発明のα－ヨード置換カルボン酸は安定性に優れ、例えばリビングラジカル重合におけるラジカル発生剤や分子量制御剤、各種ファインケミカル製造における原料又は中間体等に有効に使用できる。
The α-iodo-substituted carboxylic acid of the present invention has excellent stability and can be effectively used, for example, as a radical generator or molecular weight control agent in living radical polymerization, or as a raw material or intermediate in the production of various fine chemicals.
Claims (3)
で示されるα－ヨード置換カルボン酸、水及び酸成分を含有するα－ヨード置換カルボン酸含有組成物であって、
前記酸成分は、塩酸、硫酸、シュウ酸から選択される少なくとも１種であり、
前記組成物は、含水量が０．１～１５．０質量％の範囲、かつ酸成分含有量が０．１５～３．０質量％の範囲である、α－ヨード置換カルボン酸含有組成物。 General formula (1) below
An α-iodo-substituted carboxylic acid-containing composition containing an α-iodo-substituted carboxylic acid represented by, water and an acid component ,
The acid component is at least one selected from hydrochloric acid, sulfuric acid, and oxalic acid,
The composition is an α-iodo-substituted carboxylic acid- containing composition having a water content in the range of 0.1 to 15.0% by mass and an acid component content in the range of 0.15 to 3.0% by mass.
前記酸成分は、塩酸、硫酸、シュウ酸から選択される少なくとも１種であるα－ヨード置換カルボン酸の安定化方法。 General formula (1) below
A method for stabilizing an α-iodo-substituted carboxylic acid, wherein the acid component is at least one selected from hydrochloric acid, sulfuric acid, and oxalic acid .
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