JPH0321018B2 - - Google Patents
Info
- Publication number
- JPH0321018B2 JPH0321018B2 JP57163137A JP16313782A JPH0321018B2 JP H0321018 B2 JPH0321018 B2 JP H0321018B2 JP 57163137 A JP57163137 A JP 57163137A JP 16313782 A JP16313782 A JP 16313782A JP H0321018 B2 JPH0321018 B2 JP H0321018B2
- Authority
- JP
- Japan
- Prior art keywords
- integer
- formula
- group
- alkyl group
- general formula
- 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
Links
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 11
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 10
- 239000011737 fluorine Substances 0.000 claims description 10
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 230000001180 sulfating effect Effects 0.000 claims description 8
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 150000001449 anionic compounds Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 150000002891 organic anions Chemical group 0.000 claims description 3
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 9
- 239000002280 amphoteric surfactant Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000000921 elemental analysis Methods 0.000 description 6
- 238000005187 foaming Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 239000013076 target substance Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000013535 sea water Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- -1 hydroxyethyl group Chemical group 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 125000005459 perfluorocyclohexyl group Chemical group 0.000 description 1
- 125000000587 piperidin-1-yl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は一般式
〔但し式中のRf，Ｚ，R1，Ｙ，R2，R3および
Q1については後述する〕にて表わされる如き、
分子内にフツ素化脂肪族基Rfとサルフアトベタ
イン基
The present invention is based on the general formula [However, R f , Z, R 1 , Y, R 2 , R 3 and
Q 1 will be explained later],
Fluorinated aliphatic group R f and sulfatobetaine group in the molecule
【式】を
含有することにより特徴づけられる新規な含フツ
素サルフアトベタインおよびその製造法に関す
る。
両性界面活性剤は、イオン性を異にした他種の
界面活性剤との相溶性にすぐれていることから、
汎用性のある界面活性剤として近年注目を集めて
いる。
含フツ素脂肪族基として例えばパーフロロアル
キル基を含有した両性界面活性剤においても、そ
の水溶液の表面張力低下能、起泡性などの界面活
性特性において炭化水素アルキル基を含有した両
性界面活性剤よりも優れていることが知られるよ
うになり、高価格という経済的デメリツトを克服
して種々の用途への応用がはかられつつある。
公知の含フツ素両性界面活性剤は分子内にメチ
ル基、エチル基あるいはヒドロキシエチル基など
により四級化された窒素原子を含むベタイン型と
して分類されうるものである。
これら公知のベタイン型両性界面活性剤は等電
点付近のPHにおいて、界面活性特性、即ち表面張
力低下能、起泡性、水への溶解性、耐硬水性など
の諸性質に関して、十分な性能を発揮し得ないも
のであつた。
本発明者は前記の観点から鋭意研究を行つた結
果、一般式〔〕で示されるサルフアトベタイン
型両性界面活性剤が種々の界面活性特性におい
て、例えば表面張力低下能、起泡性、耐硬水性あ
るいは溶解性などの諸性質において公知のベタイ
ン型両性界面活性化合物よりも予想を越えて優れ
ていることを発見し、本発明を完成するに至つた
ものである。
即ち、本発明は前記の一般式〔〕
で表わされる含フツ素サルフアトベタイン及びそ
の製造法を提供するものである。
一般式〔〕におけるRfは炭素数３〜18好ま
しくは４〜12の飽和、不飽和のフツ素化脂肪族基
を含む基であり、その様なもののうち好ましいも
のの例として、炭素数３〜18のパーフロロアルキ
ル基もしくはパーフロロアルケニル基であり直鎖
状、分岐状、環状（例えばパーフロロシクロヘキ
シルのような基）またはそれらを組合わせたもの
のいずれでもよいが、好ましくは直鎖状のもので
ある。更に主鎖中に酸素原子の介入したもの、例
えば
（CF3）2CFOCF2CF2−などでもよい。
Ｚは２価の連結基で−SO2−、−CO−、
The present invention relates to a novel fluorine-containing sulfatobetaine characterized by containing the formula: and a method for producing the same. Amphoteric surfactants have excellent compatibility with other types of surfactants with different ionic properties, so
It has recently attracted attention as a versatile surfactant. Among amphoteric surfactants containing perfluoroalkyl groups as fluorine-containing aliphatic groups, for example, amphoteric surfactants containing hydrocarbon alkyl groups are considered effective in terms of surface active properties such as the ability to lower the surface tension of aqueous solutions and foaming properties. It has become known that these materials are superior to other materials, and efforts are being made to overcome the economic disadvantage of high price and apply them to a variety of uses. Known fluorine-containing amphoteric surfactants can be classified as betaine type surfactants containing a nitrogen atom quaternized by a methyl group, ethyl group, hydroxyethyl group, etc. in the molecule. These known betaine-type amphoteric surfactants have sufficient performance in terms of surfactant properties, i.e. surface tension lowering ability, foaming properties, solubility in water, hard water resistance, etc., at a pH near the isoelectric point. It was something that I could not demonstrate. As a result of intensive research from the above-mentioned viewpoint, the present inventors found that the sulfatobetaine type amphoteric surfactant represented by the general formula The inventors discovered that the present invention is superior to known betaine-type amphoteric surfactant compounds in various properties such as stability and solubility beyond expectations, leading to the completion of the present invention. That is, the present invention relates to the general formula [] The present invention provides a fluorine-containing sulfatobetaine represented by: and a method for producing the same. R f in the general formula [] is a group containing a saturated or unsaturated fluorinated aliphatic group having 3 to 18 carbon atoms, preferably 4 to 12 carbon atoms. 18 perfluoroalkyl group or perfluoroalkenyl group, which may be linear, branched, cyclic (for example, a group such as perfluorocyclohexyl), or a combination thereof, but preferably linear. It is. Furthermore, the main chain may contain an oxygen atom, such as (CF 3 ) 2 CFOCF 2 CF 2 -. Z is a divalent linking group -SO 2 -, -CO-,
【式】【formula】
【式】−（CH2）aSO2−、又は
−（CH2）aCO−（但しａは１〜10の整数を表わす）
であり、好ましくは−SO2−、−CO−、
[Formula] -(CH 2 ) a SO 2 -, or -(CH 2 ) a CO- (where a represents an integer from 1 to 10)
and preferably -SO2- , -CO-,
【式】
−（CH2）aSO2−である。
R1は水素原子、炭素数１〜12、好ましくは１
〜６のアルキル基、−（CH2）bOR3、又は−
（CH2CH2O）dR3（但しｂは１〜10の整数、ｄは１
〜20の整数、R3は低級アルキル基もしくはアル
コキシ基好ましくは炭素数１〜３のアルキル基も
しくはアルコキシ基を表わす）である。
Ｙは−（CH2）e−、−（CH2）−pＯ−（CH2）−2O−
−（
CH2）−q、又は−（CE2）gＯ（CH2）h−（但しｅは２
〜12の整数、ｐ，ｑは２あるいは３、ｇ，ｈは１
〜６の整数を表わす）である。
R2，R3は同一でも相異つていてもよく、炭素
数１〜18好ましくは１〜６のアルキル基、アルケ
ニル基であり、炭素数１〜18のヒドロキシ置換ア
ルキル基もしくは芳香族基置換アルキル基あるい
はこれらのアルキル基の炭素数が好ましくは１〜
６であり、−（CH2CH2O）iＨ（但しｉは２〜20の整
数を表わす）又はR2とR3が互に連結して隣接す
る窒素原子と共に環を形成するもので、例えばモ
ルホリノ基、ピペリジノ基などでもよい。
Q1は−（CH2）j−、[Formula] −(CH 2 ) a SO 2 −. R 1 is a hydrogen atom, having 1 to 12 carbon atoms, preferably 1
-6 alkyl group, -( CH2 ) bOR3 , or -
(CH 2 CH 2 O) d R 3 (b is an integer from 1 to 10, d is 1
an integer of ~20, R3 represents a lower alkyl group or an alkoxy group, preferably an alkyl group or an alkoxy group having 1 to 3 carbon atoms. Y is -( CH2 ) e- , -( CH2 ) -pO- ( CH2 ) -2O-
−(
CH 2 ) − q or −(CE 2 ) g O(CH 2 ) h − (where e is 2
An integer of ~12, p, q are 2 or 3, g, h are 1
to 6). R 2 and R 3 may be the same or different, and are an alkyl group or alkenyl group having 1 to 18 carbon atoms, preferably 1 to 6 carbon atoms, and are hydroxy-substituted alkyl groups or aromatic group-substituted groups having 1 to 18 carbon atoms. The number of carbon atoms in the alkyl group or these alkyl groups is preferably 1 to
6, -(CH 2 CH 2 O) i H (where i represents an integer from 2 to 20) or R 2 and R 3 are connected to each other to form a ring with the adjacent nitrogen atom, For example, it may be a morpholino group or a piperidino group. Q 1 is −(CH 2 ) j −,
【式】又は−
（CH2CH2O）k−CH2CH2−
（但しｊは２〜12の整数、ｋは１〜50好ましく
は１〜20の整数を表わす。）である。
本発明の含フツ素サルフアトベタインは種々の
合成法により製造され得るが、本発明では
一般式〔〕
〔Rf，Ｚ，Ｙ，R1，R2，R3，Q1は前記と同意
義である。Ｘ
は無機又は有機のアニオンであ
る。〕
あるいは一般式〔〕
〔Rf，Ｚ，Ｙ，R1，R2，R3，Q1は前記と同意
義である。〕
で表わされる化合物をサルフエート化剤例えばク
ロルスルホン酸、濃硫酸、発煙硫酸、三酸化イオ
ウ等の等モル以上を用いたことを特徴とする２種
の製造法が提供される。
例えば次のごとき反応例などによつて合成され
得る。
ここでＸ
は無機又は有機のアニオンであり例
えばOH
、Cl
、Br
、Ｉ
、ClO4
、1/2
SO4 2
、CH3SO4
、NO3
、CH3COO
および
リン酸基等が挙げられる。
本発明の製造法においては反応をアセトニトリ
ル、ジオキサン、テトラヒドロフラン、クロロホ
ルムなどの不活性溶媒中で実施することができ
る。又、反応促進剤を用いても良く例えばピリジ
ン、トリエチルアミン、トリブチルアミン、トリ
プロピルアミン、Ｎ−メチルピロリジン等の有機
第三級アミンの共存下に、あるいはこれらアミン
を溶媒として反応を行い高収率で目的の含フツ素
サルフアトベタインを得ることができる。
反応温度は−20゜〜150℃、好ましくは0゜〜100
℃であり反応時間は通常５〜20時間程度が適当で
ある。
かかる方法によれば目的化合物の収率を70％以
上に高めることができ、前述の条件を選ぶことに
よりほぼ100％にすることも可能である。
本発明において、サルフエート化剤としては一
般式〔〕あるいは〔〕の末端ヒドロキシ基を
−OSO3
に置き換え得るものであれば、特に限
定されることなく種々例示可能である。好適なサ
ルフエート化剤としてはクロルスルホン酸、濃硫
酸、発煙硫酸、三酸化イオウなどがあげられる。
サルフエート化剤は通常一般式〔〕又は〔〕
の化合物に対し等モルが用いられるが、R2が例
えば−CH2CH2OH基である場合には２倍モル以
上使用することにより分子中にサルフエート基を
２個導入することもできる。このような化合物に
は例えば[Formula] or - (CH 2 CH 2 O) k -CH 2 CH 2 - (where j is an integer of 2 to 12, and k is an integer of 1 to 50, preferably 1 to 20). The fluorine-containing sulfatobetaine of the present invention can be produced by various synthetic methods, but in the present invention, the general formula [] [R f , Z, Y, R 1 , R 2 , R 3 , and Q 1 have the same meanings as above. X is an inorganic or organic anion. ] Or general formula [] [R f , Z, Y, R 1 , R 2 , R 3 , and Q 1 have the same meanings as above. ] Two types of production methods are provided which are characterized in that the compound represented by the following formula is used in an equimolar or more amount of a sulfating agent such as chlorosulfonic acid, concentrated sulfuric acid, fuming sulfuric acid, sulfur trioxide, or the like. For example, it can be synthesized by the following reaction example. Here, X is an inorganic or organic anion, such as OH, Cl, Br, I, ClO4 , 1/2
Examples include SO 4 2 , CH 3 SO 4 , NO 3 , CH 3 COO and phosphoric acid groups. In the production method of the present invention, the reaction can be carried out in an inert solvent such as acetonitrile, dioxane, tetrahydrofuran, or chloroform. Further, a reaction accelerator may be used, for example, the reaction may be carried out in the presence of an organic tertiary amine such as pyridine, triethylamine, tributylamine, tripropylamine, N-methylpyrrolidine, etc., or by using these amines as a solvent to achieve a high yield. The desired fluorine-containing sulfatobetaine can be obtained. The reaction temperature is -20° to 150°C, preferably 0° to 100°C.
℃, and the reaction time is usually about 5 to 20 hours. According to this method, the yield of the target compound can be increased to 70% or more, and by selecting the above-mentioned conditions, it is possible to increase the yield to almost 100%. In the present invention, the sulfating agent is not particularly limited and can be exemplified in various ways as long as it can replace the terminal hydroxyl group of the general formula [] or [] with -OSO3 . Suitable sulfating agents include chlorosulfonic acid, concentrated sulfuric acid, fuming sulfuric acid, sulfur trioxide, and the like.
The sulfating agent usually has the general formula [] or []
An equimolar amount is used for the compound, but if R 2 is, for example, a -CH 2 CH 2 OH group, two sulfate groups can be introduced into the molecule by using twice the mole or more. Such compounds include e.g.
【式】（但しQ1′は
同一か又は異つたQ1を表わす）で表わされる優
れた界面活性効果を有し、両性界面活性剤として
有用であることがすでに本発明者により見出され
ている。
本発明でクロルスルホン酸、濃硫酸、発煙硫
酸、三酸化イオウの如きサルフエート化剤により
得られる一般式The present inventor has already discovered that it has an excellent surfactant effect represented by the formula: (where Q 1 ′ represents the same or different Q 1 ) and is useful as an amphoteric surfactant. There is. The general formula obtained in the present invention by using sulfating agents such as chlorosulfonic acid, concentrated sulfuric acid, fuming sulfuric acid, and sulfur trioxide
冷却用コンデンサーおよび撹拌器を備えた１
の４つ口丸底フラスコに
66.5ｇとアセトニトリル400ｇを採取し、充分に
撹拌して加熱溶解した。クロルスルホン酸14ｇを
30℃で強力に撹拌しながら発熱に注意しつつゆつ
くりと滴下した。滴下後さらに40℃で４時間撹拌
し反応を完結させた。続いて28％NaOCH3メタ
ノール溶液を46.2ｇ加えて中和した後、アセトニ
トリルおよびメタノールを減圧下で留去した。
黄褐色固体残渣を50℃で減圧乾燥し、エタノー
ルから再結晶して精製し、目的物質
が60ｇ得られた。
元素分析
1 with cooling condenser and stirrer
into a four-necked round-bottomed flask. 66.5 g and 400 g of acetonitrile were collected, thoroughly stirred, and heated to dissolve. 14g of chlorsulfonic acid
The mixture was slowly added dropwise at 30°C while stirring vigorously while being careful not to generate heat. After the dropwise addition, the mixture was further stirred at 40°C for 4 hours to complete the reaction. Subsequently, 46.2 g of 28% NaOCH 3 methanol solution was added to neutralize the mixture, and then acetonitrile and methanol were distilled off under reduced pressure. The yellowish brown solid residue was dried under reduced pressure at 50°C, purified by recrystallization from ethanol, and the target substance was purified. 60g of was obtained. elemental analysis
実施例１と同様の反応器に
56.5ｇピリジン400ｇを仕込み、30℃でクロルス
ルホン酸14ｇを発熱に注意しつつゆつくりと滴下
し、５時間反応せしめた。反応終了後28％
NaOCH3メタノール溶液46.2ｇを加え充分に撹拌
して中和した後、ピリジンおよびメタノールを減
圧下で留去した。褐色固体残渣をエタノールから
再結晶させたところ、目的物質
が51.3ｇ得られた。
元素分析
In the same reactor as in Example 1 56.5 g of 400 g of pyridine was charged, and 14 g of chlorosulfonic acid was slowly added dropwise at 30° C. while being careful not to generate heat, and the mixture was allowed to react for 5 hours. 28% after reaction completion
After adding 46.2 g of NaOCH 3 methanol solution and thoroughly stirring to neutralize, pyridine and methanol were distilled off under reduced pressure. When the brown solid residue was recrystallized from ethanol, the target substance was obtained. 51.3g of was obtained. elemental analysis
実施例１と同様の反応器に
62.8ｇピリジン300ｇを仕込み、70℃に加熱して
溶解した。滴下ロートを用いて濃硫酸10ｇを発熱
に注意しながらゆつくりと滴下70℃で７時間反応
せしめた。室温に冷却し、析出物をロ過して取出
し、エタノールから再結晶させたところ目的物質
が50.5ｇ得られた。
元素分析
In the same reactor as in Example 1 62.8g of pyridine (300g) was charged and heated to 70°C to dissolve it. Using a dropping funnel, 10 g of concentrated sulfuric acid was slowly added dropwise while being careful not to generate heat, and the mixture was allowed to react at 70°C for 7 hours. After cooling to room temperature, the precipitate was filtered out and recrystallized from ethanol, resulting in the desired substance. 50.5g of was obtained. elemental analysis
【表】
IRおよびNMRスペクトルは実施例１のものと完
全に一致した。
〔実施例 ４〜10〕
を第１表の出発物質に変更させると共にその記載
された量用いた以外は、実施例１と同様の操作を
行ない、第１表の生成物質を各欄に記載した量だ
け得た。
その得られた生成物質を元素分析、IR，NMR
にて分析した結果を第１表に併せて示し、記載し
たが、これにより目的物質の得られたことを確認
した。[Table] The IR and NMR spectra were completely consistent with those of Example 1. [Examples 4 to 10] The same procedure as in Example 1 was carried out, except that the starting materials in Table 1 were used and the amounts listed were used, and the products listed in Table 1 were obtained in the amounts listed in each column. Elemental analysis, IR, NMR of the resulting product
The results of the analysis were also shown and described in Table 1, and it was confirmed that the target substance was obtained.
【表】【table】
【表】【table】
【表】【table】
冷却用コンデンサーおよび撹拌器を備えた１
の４つ口丸底フラスコに、
186.9ｇとピリジン400ｇを仕込み、30℃でクロル
スルホン酸12ｇを発熱に注意しつつゆつくりと滴
下し、５時間反応せしめた。反応終了後28％
NaOCH3メタノール溶液46.2ｇを加え充分に撹拌
して中和した後、ピリジンおよびメタノールを減
圧下で留去した。褐色粘稠残渣を熱エタノールか
ら再沈殿させたところ、目的物質
96ｇが得られた。
元素分析
1 with cooling condenser and stirrer
In a four neck round bottom flask, 186.9 g of pyridine and 400 g of pyridine were charged, and 12 g of chlorosulfonic acid was slowly added dropwise at 30° C. while being careful not to generate heat, and the mixture was allowed to react for 5 hours. 28% after reaction completion
After adding 46.2 g of NaOCH 3 methanol solution and thoroughly stirring to neutralize, pyridine and methanol were distilled off under reduced pressure. When the brown viscous residue was reprecipitated from hot ethanol, the target substance was found. 96g was obtained. elemental analysis
冷却用コンデンサーおよび撹拌器を備えた１
の４つ口丸底フラスコに、
69.7ｇピリジン400ｇを仕込み、30℃でクロルス
ルホン酸14ｇを発熱に注意しつつゆつくりと滴下
し、５時間反応せしめた。反応終了後28％
NaOCH3メタノール溶液46.2ｇを加え充分に撹拌
して中和した後、ピリジンおよびメタノールを減
圧下で留去した。褐色固体残渣をエタノールから
再結晶させたところ、目的物質
55.3ｇが得られた。
元素分析
1 with cooling condenser and stirrer
In a four neck round bottom flask, 69.7 g of 400 g of pyridine was charged, and 14 g of chlorosulfonic acid was slowly added dropwise at 30° C. while being careful not to generate heat, and the mixture was allowed to react for 5 hours. 28% after reaction completion
After adding 46.2 g of NaOCH 3 methanol solution and thoroughly stirring to neutralize, pyridine and methanol were distilled off under reduced pressure. When the brown solid residue was recrystallized from ethanol, the target substance was obtained. 55.3g was obtained. elemental analysis
実施例１〜12にて合成された本発明化合物の界
面活性特性値（水溶液の表面張力および起泡性）
を第２表にまとめて示す。
尚、表面張力はウイルヘルミー法で25℃にて測
定し、起泡性はロス−マイルス法で25℃にて泡立
て直後および５分経過後の泡高を測定した。
但し、溶媒としてはそれぞれ蒸留水および合成
海水を使用し、合成海水の組成は
NaCl 2.50％
MgCl2・6H2O 1.10％
Na2SO4 0.40％
CaCl2・2H2O 0.16％
で、残りは蒸留水である。
Surface active property values of the compounds of the present invention synthesized in Examples 1 to 12 (surface tension and foaming properties of aqueous solutions)
are summarized in Table 2. The surface tension was measured at 25°C by the Wilhelmy method, and the foaming property was measured by the Ross-Miles method at 25°C, by measuring the foam height immediately after foaming and after 5 minutes. However, distilled water and synthetic seawater were used as solvents, and the composition of synthetic seawater was NaCl 2.50% MgCl 2 6H 2 O 1.10% Na 2 SO 4 0.40% CaCl 2 2H 2 O 0.16%, and the rest was distilled water. It's water.
【表】【table】
【表】【table】
【表】
但し、表中、上段は蒸留水溶液、下段
は合成海水溶液を表わす、濃度はいず
れも0.1重量％である。
又、実施例３は実施例１と同一物質なので省略
した。[Table] However, in the table, the upper row represents the distilled aqueous solution, and the lower row represents the synthetic seawater solution, and the concentration is 0.1% by weight in both cases.
Moreover, since Example 3 is the same material as Example 1, it is omitted.
Claims (1)
不飽和 のフツ素化脂肪族基、Ｚは−SO2−、−CO−、 【式】 【式】−（CH2）a SO2−、又は−（CH2）aCO−（但しａは１〜10の
整 数を表わす）を表わし、R1は水素原子、炭素数
１〜12 のアルキル基、−（CH2）bOR3、又は−
（CH2CH2O）d R3（但しｂは１〜10の整数、ｄは１〜20の整数、 R3は低級アルキル基もしくはアルコキシ基を表
わす） を表わし、Ｙは−（CH2）e−、−（CH2）p−Ｏ− （CH2）2−Ｏ−（CH2）ｑ−、又は−（CH2）ｇ−
Ｏ−（CH2）h−（但しｅは２〜12の整数、ｐ，ｑは
２あ るいは３、ｇ，ｈは２〜６の整数を表わす） R2，R3は炭素数１〜18のアルキル基、アルケニ
ル 基、ヒドロキシ置換アルキル基、もしくは芳香族
基置換 アルキル基、−（CH2CH2O）iＨ（但しｉは２〜20の 整数を表わす。）又はR2とR3が互に連結して隣接
する 窒素原子と共にQ1は−（CH2）j−、
【式】 又は−（CH2CH2O）k−CH2CH2−、 （但し、ｊは２〜12の整数、ｋは１〜50の整数を
表〕 わす）を表わす。 にて表わされる含フツ素サルフアトベタイン。 ２ Rfがパーフロロアルキル基又はパーフロロ
アルケニル基である特許請求の範囲第１項記載の
含フツ素サルフアトベタイン。 ３ 一般式〔〕 〔但し式中Rfは３〜18の飽和もしくは不飽和
のフツ素化脂肪族基を表わし、Ｚは−SO2−、−
CO−、 【式】 【式】−（CH2）a SO2−、−（CH2）aCO−（但しａは１〜10の整数 を表わす）を表わし、R1は水素原子、炭素数１
〜12 のアルキル基、−（CH2）bOR3、又は−
（CH2CH2O）d R3（但しｂは１〜10の整数、ｄは１〜20の整数、 R3は低級アルキル基又はアルコキシ基を表わす）
を表 わし、Ｙは−（CH2）e−、−（CH2）−pＯ−（CH2）−2
O −（CH2）−q又は−（CE2）g−Ｏ−（CH2）h− （但し、ｅは２〜12の整数、ｐ，ｑは２あるいは
３、 ｇ，ｈは２〜６の整数を表わす）R2，R3は炭素
数 １〜18のアルキル基、アルケニル基、ヒドロキシ
置 換アルキル基、もしくは芳香族置換アルキル基、 −（CH2CH2O）iＨ（但しｉは２〜20の整数を表わ す）、又はR2とR3が互に連結して隣接する窒素原
子 と共に環を形成するもの、 Q1は−（CH2）j−、又は−（CH2CH2O）k−CH2 CH2−（但し、ｊは２〜12の整数、ｋは１〜50の 整数を表わす）Ｘ は無機又は有機のアニオン〕 で表わされる化合物にサルフエート化剤を作用さ
せ必要に応じ中和して一般式〔〕 〔但し式中Rf，Ｚ，R1，Ｙ，R2，R3およびQ1
は前記に同じ〕 にて表わされる化合物を生成せしめることを特徴
とする含フツ素サルフアトベタインの製造法。 ４ サルフエート化剤としてクロルスルホン酸、
濃硫酸、発煙硫酸又は三酸化イオウを使用する特
許請求の範囲第３項記載の製造法。 ５ 一般式〔〕 〔但し式中Rf，Ｚ，Ｙ，R2，R3およびQ1は前
記に同じ〕 で表わされる化合物にサルフエート化剤を作用さ
せ 一般式〔〕 〔但しRf，Ｚ，Ｙ，R2，R3，およびQ1は前記
に同じ〕 にて表わされる化合物を生成せしめることを特徴
とする含フツ素サルフアトベタインの製造法。 ６ サルフエート化剤としてクロルスルホン酸、
濃硫酸、発煙硫酸又は三酸化イオウを使用する特
許請求の範囲第６項記載の製造法。[Claims] 1. General formula [] [However, in the formula, R f is a saturated or unsaturated fluorinated aliphatic group having 3 to 18 carbon atoms, Z is -SO 2 -, -CO-, [Formula] [Formula] -(CH 2 ) a SO 2 -, or -(CH 2 ) a CO- (where a represents an integer of 1 to 10), R 1 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, -(CH 2 ) b OR 3 , Or-
(CH 2 CH 2 O) d R 3 (where b is an integer of 1 to 10, d is an integer of 1 to 20, R 3 represents a lower alkyl group or an alkoxy group), and Y is -(CH 2 ) e −, −(CH 2 ) p −O− (CH 2 ) 2 −O−(CH 2 )q−, or −(CH 2 )g−
O-(CH 2 ) h - (where e is an integer of 2 to 12, p and q are 2 or 3, g and h are integers of 2 to 6) R 2 and R 3 are carbon atoms of 1 to 18 an alkyl group, an alkenyl group, a hydroxy-substituted alkyl group, an aromatic group-substituted alkyl group, -(CH 2 CH 2 O) i H (where i represents an integer from 2 to 20), or R 2 and R 3 are mutually Q 1 together with the adjacent nitrogen atom connected to −(CH 2 ) j −,
[Formula] or −(CH 2 CH 2 O) k −CH 2 CH 2 −, (where j is an integer from 2 to 12 and k is an integer from 1 to 50). Fluorine-containing sulfatobetaine represented by 2. The fluorine-containing sulfatobetaine according to claim 1, wherein R f is a perfluoroalkyl group or a perfluoroalkenyl group. 3 General formula [] [However, in the formula, R f represents a 3 to 18 saturated or unsaturated fluorinated aliphatic group, and Z is -SO 2 -, -
CO-, [Formula] [Formula] -(CH 2 ) a SO 2 -, -(CH 2 ) a CO- (where a represents an integer from 1 to 10), R 1 is a hydrogen atom, and the number of carbon atoms is 1
~12 alkyl groups, -( CH2 ) bOR3 , or -
(CH 2 CH 2 O) d R 3 (where b is an integer of 1 to 10, d is an integer of 1 to 20, R 3 represents a lower alkyl group or an alkoxy group)
, and Y is -( CH2 ) e- , -( CH2 ) -pO- ( CH2 ) -2
O - (CH 2 ) - q or - (CE 2 ) g - O - (CH 2 ) h - (where e is an integer of 2 to 12, p and q are 2 or 3, g and h are 2 to 6 ( represents an integer of ~20), or R 2 and R 3 are linked together to form a ring with adjacent nitrogen atoms, Q 1 is -(CH 2 ) j -, or -(CH 2 CH 2 O ) k -CH 2 CH 2 - (where j is an integer of 2 to 12, k is an integer of 1 to 50) X is an inorganic or organic anion] Neutralize according to the general formula [] [However, in the formula R f , Z, R 1 , Y, R 2 , R 3 and Q 1
is the same as above] A method for producing fluorine-containing sulfatobetaine, characterized by producing a compound represented by the following. 4 Chlorsulfonic acid as a sulfating agent,
The manufacturing method according to claim 3, which uses concentrated sulfuric acid, fuming sulfuric acid, or sulfur trioxide. 5 General formula [] [However, in the formula, R f , Z, Y, R 2 , R 3 and Q 1 are the same as above] A sulfating agent is applied to the compound represented by the general formula [] [However, R f , Z, Y, R 2 , R 3 , and Q 1 are the same as above] A method for producing fluorine-containing sulfatobetaine, which is characterized by producing a compound represented by the following. 6 Chlorosulfonic acid as a sulfating agent,
The manufacturing method according to claim 6, which uses concentrated sulfuric acid, fuming sulfuric acid, or sulfur trioxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57163137A JPS5953448A (en) | 1982-09-21 | 1982-09-21 | Fluorine-containing sulfato betaine and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57163137A JPS5953448A (en) | 1982-09-21 | 1982-09-21 | Fluorine-containing sulfato betaine and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5953448A JPS5953448A (en) | 1984-03-28 |
| JPH0321018B2 true JPH0321018B2 (en) | 1991-03-20 |
Family
ID=15767901
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57163137A Granted JPS5953448A (en) | 1982-09-21 | 1982-09-21 | Fluorine-containing sulfato betaine and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5953448A (en) |
-
1982
- 1982-09-21 JP JP57163137A patent/JPS5953448A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5953448A (en) | 1984-03-28 |
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