JPS5948449A - Straight-chain fluorine-containing anionic compound and its preparation - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is characterized by having a boria 0-roalkyl group as an essential group, and a urea bond, a thiourea bond, or a carbonamide group in the molecule.

The present invention relates to a novel linear intercalated fluorine anionic surfactant having excellent surfactant properties and a method for producing the same.

Up to now, anionic fluorine-containing surfactants containing a carbonamide group have been disclosed in U.S. Patent No. 411,602 and Japanese Patent Application Laid-open No. 84524/1983, but in such cases, the carbonamide group is , is a connecting group for introducing a nonionic hydrophilic group, and is a linear fluorine-containing anionized @JJl represented by the general formula CD of mJ in the present invention.
Of course, in that respect, it is clearly conventional, including Notsuba aniono world 101 activities (・F i'jllv, 11, foaming (/15.1 (・
L stability, humidity, j cases, etc., fI! + surface activity P! times<
'i+/+- is 14j, so foam fire extinguishing? 1
11.1 [((foam stabilizer,?! heart 1-IA'l, j(%
J, i41qll1, etc. However, the conventional fluorine-containing anion surface activity 1']
, the agent is insolubilized in hard water or in a water bath tIV, exhibits sufficient surface activity i'lEZ +/i, and q:11. Due to its small size, its usage conditions are limited.

The present invention is based on these fi'! / Fu Karaei Pai+If'
As a result of performing y'+:, a linear intercalated fluorine anion compound represented by the general formula [l] containing any one of a urea bond, a thiourea bond, and a carbonyl amide group in the molecule is 111 Hard water containing a large amount of inorganic salts, such as water, and soluble in water with a wide range of
The present inventors have discovered that the present invention has excellent surfactant properties, and has completed the present invention. In addition, in hard water and wide p
Amphoteric surfactants have attracted attention as they form stable aqueous solutions over the H range, but the pka values of the urea bond, thiourea bond, and carbonamide group are -2.
-1, and the compounds represented by the general formula [] of the present invention are clearly distinguished from such amphoteric surfactants in that they have no particular basicity.

That is, the novel compound of the present invention is a linear intercalated fluorine anion compound represented by the general formula [1].

In the general formula [1], Rf is a polyfluoroalkyl group, a polyfluoroalkenyl group, a polyfluorocyclohexyl group, a polyfluorocyclohexylalkyl group, a polyfluorocyclohexylalkenyl group having 1 to 20 carbon atoms, preferably 4 to 15 carbon atoms. Examples of preferable groups include per70roalkyl group or perfluoro IJ group.
It is an alkenyl group, and may be linear, branched, ring υ (for example, a group such as a cyclo-gycyl group), or a combination thereof, but a linear one is preferable.

Furthermore, those with oxygen atoms intervening in the main chain, such as (CF,
), CFOCF2CF2-, etc. may be used.

2 is a divalent linking group, preferably -Z, -N-1 [However, Z is a divalent linking group, -5O7-1-CO-1
So CH, CHt snow SO, -1+C
-oo(:0-5-Ctl, CHClr, -1-CE(
, C, H, -1 item -(0CH2CH27)-, or -CH2CH2S
C112CI2 CO-', R1 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, (-C11 or soCJT2CTT20→, Ifield (Ijl-11)
is 1-4! is the number of At, d is the rudder O of 1 to 20, the island is water; (is diatomic or an argyl group having 1 to 6 carbon atoms); It is an oxygen atom or a sulfur atom ((BL, when a is 00, it is limited to Y-yama dissolution atoms).

6 Norisa. ) or -CH2Cl CH2-, but is OH or +-(-lit% ClI2+CHt% (provided that S and V are integers from 0 to 6).

A is Ia, tyt/JJt child group-C--cooe,
-SO2'', -osop, or 0P(OH)Oe.

M is a hydrogen atom or an organic or inorganic cation;
■, [N(H)z(R”)m) (where RJ is an alkyl group or hydroxyethyl group having 1 to 4 carbon atoms, l and m are integers from 0 to 4, and l0m=4 is a maximum of 7 ) is preferred.

The basic structure of the linear sandwiched fluorinated anionic surfactant according to the present invention is that a polyfluoroalkyl group, a group containing any one of a urea bond, a thiourea bond, and a carbonamide group, and an anionic It is characterized in that three of the groups are connected in a linear chain, and it goes without saying that the present invention is not limited to the above-mentioned connecting groups among the many divalent connecting groups. be.

As the straight button-shaped fluorine-containing anionic compound of the present invention, the following '9
A specific example is a n-gimono.

(S’) (S) CH.

(S) 111( C1l, CH, OHCH2Cl, OH 0 (S) II, II CeF1sSO2NC)]2CHCH2N CN
CH2SO3Nal CH2CH20CH2CH,CH3 (S) (S) (S) 1 C7Fl s CON CHt CHCH2N CN
CII2 S Os Na1 CII, CH, OHCH, CH, OH (S) (S) ? 1°C)■.

(S) (S) (S) (S) (S) 1 U mountain OH0 1 H 0 C, F, 6-CF=CH-CH, -NCClI2 CH
2COOLi(S) (S) (8) (S) (S) C8F+ y Cl12 cH2S 02 N f C
JTt *; N CN ClT2C00I(Il,
HH (3) 1 The linear fluorine-containing anionic compound according to the present invention can be produced by various synthesis methods, and the main production methods include the following methods.

That is, the first manufacturing method is based on the general formula (IT) [wherein "
, zs Ql , R, Y, "s Qy has the same meaning as above, and X is a chlorine atom, a bromine atom, or an iodine atom."], an alkali metal sulfite salt, for example, a sulfite This is a production method that involves reacting with potassium, sodium sulfite, etc.

The second manufacturing method is based on the general formula [III]Rf-Z-Ql
-N-C(-NqQ3-CH=CH2(JJD(l) [In the formula, Rf, Z, Ql, R, Y, a are the same as above 1~, and Q3 is cHt'q (However, j is 1
~10! l number. ). ] The fluorine-containing compound represented by
This is a production method in which 'tta is reacted with potassium dihydrogen.

In the first and second production methods, the reaction solvent includes methanol, ethanol, inglobil alcohol, methyl cellosolve, ethyl cellosolve, butyl cellosolve,
A mixed system of water and an organic solvent that is 0T soluble in water, such as butyl cardol, dimethyl sulfoxide, dimethyl formamide, acetonitrile, etc., is suitable. Suitable reaction temperature and reaction time are 0 to 150°C and 6 to 25 hours. If necessary, the product can be recrystallized and purified.

Furthermore, the compound of general formula [11] and the compound of general formula (Ill) necessary for production are preferably those of general formula [V
[lζ nt -Z-Q, -NH[V] [Wherein, Rf, Z, Q+, and R have the same meanings as above.

] The fluorine-containing amine represented by the general formula Y=C=N-Q2-X [V
r:]]x-C-Q, -XC■]1 Y=C=N-Q, -CH=CH, Cv+u) or X-CQs CH" CH2CIX:]1 [In the formula, Ql, X, Y, Q has the same meaning as above, and X may be the same or different.] can be synthesized in good yield by reacting the compound represented by the following in the presence of a base catalyst.

In the case of the reaction between the fluorine-containing amine of the general formula [■] and the compound of the general formula [■1] or [■], for example, an aprotic amine such as tetrahydrofuran or benzene may be used.
1 medium, preferably at a temperature of 0 to 60°C! Range 1-5
[Time] You just have to worship.

Furthermore, the fluorine-containing amine of general formula [V] and the general formula 1! l
] or [1'X), pyridine,
Usually -8
It is preferable to stir at a temperature of 6 to 50° C. for 1 to 20 hours.

Furthermore, as a sixth manufacturing method, the previous RI2 general "formula [■
This is a Mζ1≠ production method in which a fluorine-containing amine represented by the following formula is reacted with an anhydrous succinic plate in the presence of a basic catalyst such as pyridine or in the presence of a frl-free medium.

In this method, the reaction temperature is suitably 0 to 120°C and the reaction time is suitably 1 to 20 hours.

The fourth method is to hydrolyze a compound represented by the general formula [ID, where Rf% Z, Q+, R, 7%'', Q2 has the same meaning as above]. This is a production method in which a fluorine-containing compound represented by the formula is synthesized, and then this is reacted with equimolar or more of a sulfating agent such as chlorosulfonic acid, concentrated 111-diacid, fuming acid, or S03.

In this production method, the reaction can be carried out in an inert solvent such as -acetonitrile, dioxane, tetrahydrofuran, or chloroform. Furthermore, when the reaction is carried out in the presence of amines such as pyridine, triethylamine, and tributylamine, or by using these amines as a bath medium, the desired product can be obtained in high yield. The reaction temperature is -20~15
The temperature is 0°C, preferably 0 to 100°C, and the reaction time is usually 5 to 20 hours.

The following Table 1 shows the foaming properties and surface tensions of the main direct Kt, i-type fluorinated cumulative anionic compounds according to the present invention.
It is a collection of gender.

As shown in Table 2 below, the linear fluorine-containing anionic compound according to the present invention is completely soluble in distilled water even under a strongly acidic pH of 3, and can be dissolved in any of the acidic, neutral, and alkaline pH ranges. However, it is excellent in that it does not reduce its surface active properties. The stability of the compound of the present invention against pH changes provides a surfactant that is extremely useful in practice.
220 21+S 2089
210 220 214 20111
215 219 2L5 205 Prison
The foam height was measured immediately after the completion of dropping by the Ross-Mi Ies method.

Furthermore, as shown in Table 6, 4 (the compound of the invention is -,
Unlike known anion activators, calcium ion activators
Is it good for stability in Japan? 1, Table-3 A > [1[]1. 'IB
>500 []E
>50 [10! >50
00 J >5000 L,, >50tlOM
4500 modified Ifardt method.

In this way, the compound j developed by the present invention has excellent foaming properties and surface tension lowering ability not only in pure water but also in seawater, and has a property of hard water.
Due to its excellent stability against pH changes, it can be suitably used in foam fire extinguishers, water film-forming fire extinguishers, foaming agents, cleaning agents, wetting agents, penetrating agents, etc. It is also suitable for applications such as emulsifiers, leveling agents, paint additives, rust preventive agents, antifouling agents, oil repellents, plastic additives, antistatic agents, mold release agents, anti-mist agents, antibacterial agents, etc.

Next, synthesis examples of the compounds of the present invention will be shown to further specifically illustrate the present invention.

Example 1 4 dry silica gel tubes and 4i1'P vessels! ifi got 3
L] N-(3-methylaminopropyl) perfluorohexyl sulfonamide 31 (0,064 mol) and fully dehydrated tetrahydrofuran 170 me were weighed into a 17 ug six-necked round bottom flask under an indoor atmosphere, Stir at room temperature fa8'? did. β-chloroethyl isocyaner)
7.1,! 11 (0,067 mol)) was heated vigorously at room temperature.
After stirring, it was added dropwise from step 1. After the addition was complete, it was filtered at room temperature for 4 hours, and tetrahydrofuran was distilled off under reduced pressure.
2g was obtained.

Elemental analysis CHN F Phase separation 1 direct (%) 27.2 2.6
7,2 42.9H1″ calculationjii (%)
27.1 2.6 7.3 43.0
IR spectrum 1570m'(-3O2NriI'ag) 164
5cm (7N-CO-NH-) NMR spectrum (
cD3cocD3 bath medium, TMS standard) 1.82ppm (
N-(3-[3-(β-chloroethyl )-1-methylureido]glopyr) bar 70 hexylsulfonamide 10.10.0174 mol),
Ethanol 70p, water 50g, sodium sulfite 6.6
g (0,026 mol) was weighed out and stirred at 90°C for 4 hours.

Ethanol and water were distilled off under reduced pressure, and the solid residue was purified by ladle crystallization from methanol. The decomposition temperature was -186°C.

Elemental analysis CHN F Analysis value (%) 24.5 2.2 6.4
38.7 Tears initial value (%) 24.3 2.5
6,5 38.4IR spectrum 121 Dcra-' (SO3Na νas)1
370cnL' (-8O2N/I/FIS)\1640cm (/N co Nfl, )NM
R spectrum (D20 solvent, to DSS group A) 1.83p
pm (m, 2H), 2.95 ppm (s, 3J (
) 5.2 (II-3,75ppm (m, 8) 1) Example 2 ■ (1) ”sF+tSO2NCHtCHtCH2NC
Synthesis of NCHzCH2C1 HHif 35.6 g (0,064
mol) and fully dehydrated tetrahydrofuran i7omg
was weighed out under a nitrogen atmosphere, and stirred and dissolved at room temperature. 20 ml of a tetrahydrone bath solution in which 7.1 g (0,067 mol) of β-chloroethyl isocyaner was dissolved was added dropwise at room temperature with strong stirring. After completion of the dropwise addition, the mixture was stirred at room temperature for 6 hours, and tetrahydrofuran was distilled off under reduced pressure to obtain a pale yellow oily substance 41. +g was obtained.

Elemental analysis I It spectrum 1370Cvt-'(-8o2N' νa8)
\ 1645CTL (,N-Co -Nu-)N ki R
Spectrum (CD, COCD, bath medium, TMS standard J1
-82 ppm (m, 2H), 3.25-3.75 rlPm (m, 8H) (Ill
CsF+7SO2NCH2CH2CH2NCNCH2
Synthesis of CHzSO3Na II HH Cooling condenser and stirrer (iii) 21J
Add N-(ro-[3-
<β-chloroethyl)ureido]solopyl)perfluorooctyl sulfomide 11.5. V (0,0174
mol), 7°J of ethanol, 50 g of water, and 3.3 g (1,026 mol) of sodium chloride 11 were taken and stirred at 90°C for 5 hours. Ethanol and water were distilled off under reduced pressure, and the residue was purified by recrystallization from methanol. The decomposition temperature was 178°C. Elemental analysis CHN F analysis value (%) 24.5 2.0 6.2
47.1 Calculated value (%) 24.7 1.
9 6.2 47.4IR spectrum 1195cIrL' (-8O, Na νas
)1370c1rL-' (-8OzN,, ν
as) NMR spectrum (D20 solvent, DSS standard) 1
．． 87ppm (m, 2H), 5.15-3.65ppm
(m, 8H) Example 3 N-(2-hydroxyethyl) was added to a 3 oomg third round bottom flask equipped with a dry silica gel tube and a J-shaft stirrer.
-N-(2-Hydroxyl 6-amif 1 mouth pill ``'' hexyl sulfonamide 33.!/(D, t)
64 mol) Tetrahydrofuran 170 mol
m1 was weighed out under an atmosphere of ';4i:+:I77, and at Muroran] YL stirring h! N = I did. 2Qme of a tetrahydrofuran solution containing 12.1,9 (0,067 mol) of r-bromoprobyl isothiocyaner was stirred at room temperature for 19 hours and added dropwise. After completion of dropping, 311 at room temperature;
, stirred for a while, and distilled off tetrahydrofuran under reduced pressure'1-
By doing so, 44.7 g of 4'i dry colored oil was obtained.

Elemental analysis value (%) 26.1 2.7 6.1
55. ') Calculated value (%) 25.9 2
．． 7 6.0 35.5 IR spectrum 137 om-' (-8o, Nri νas)) NMR spectrum (CD3CoCD3 solvent, TMS standard) 1.76 ppm (m, 2H), 2.2 D PI) m
(t, 2H) 5.15-3. S5TII)m(m,
10H), 4.00ppm (m, 1kl) 3 of 2DOmA with cooling condenser and stirrer
In a round-bottomed round-bottomed flask, add N-(2-hydroquineyl)-N-(2-hydroxy[3-(γ-bromopropinoone thioureido] globil) burn j70hexylsulfonamide 12.1.?( 0,0174 mo/l-)
, -hytanol 70μ, water 50g, sodium sulfite 3
．． 1 (0,026 mol) was taken in tF and stirred at 90°C for 5 hours. Ethanol and water were distilled off under reduced pressure, and the solid residue was purified from methanol.

The decomposition temperature was 167°C. Elemental analysis CHN F calculated value (%) 25.0. 2.6 5,83
4.4IIζ Spectrum 121 C3,5t-' (SO3Na νas)
1370cm-' (-8OzN,,, νas)
NMR spectrum (D20 bath medium, DSS standard) 1.81
ppm (m, 2H), 2.20 ppm (t,
2H), 3.05-3.65ppm (m, 10H),
4, I Qppm (m, IH) Example 4 CyF+! Co H+ CHt9 C¥J, CH2
(Synthesis of Jlz S Os Na Into a 300 ml Mitsuhimaru/jE flask equipped with a dry silica gel tube and a stirrer, 32.7 g (0,064 mol) and 170 ml of sufficiently dehydrated tetrahydrofuran were weighed out under a nitrogen atmosphere and dissolved with stirring at room temperature.Tetrahydrofuran solution in which β-Rya loethyl incyanar) 7.1, F (0,067 mol) was dissolved. 2Qml was added dropwise at room temperature with strong stirring.
By stirring with W and distilling off tetrahydrofuran under reduced pressure, a pale yellow mail-like substance 39. D, 9! It was.

Elemental analysis Cit N l' Analysis value (%) 33.6 2.2 664
6.7 1 shift (%) 33.4 2.
1 6,9 46.6 IR spectrum 1646 crn-' (-CON-) 1■ NMR spectrum (CDs COCDs bath medium, TMS group J9 1.55 ppm (m, 8H), 3.20-3.7
5 ppm (m, FH()) N-(6-45-(β-chloroethyl)ureido]hexyl) into a 70-neck round bottom flask equipped with a cooling condenser and a stirrer. Butylcarbo77mide 10.6.!l/(0,0174 mo#),
Weigh out 70 g of ethanol, 40 g of water, 1'fl'&3,3.ji' (0,026 mol) of sodium,
Stirred at 0°C for 6 hours. Ethanol and water were distilled off under reduced pressure, and the solid residue was purified by recrystallization from methanol. Minute M
The temperature was 185°C.

Elemental analysis value (%) 29.8 2.7 <S
, 3 41.4 IR spectrum 1210 m-' (-8O3Na νas) 163
5 cm-' (-N-Co-N-)Hkl 1655 cm-' (C0N-) I NMR spectrum (D20 bath medium'', DSS crystal standard) 1.
58 ppm (m, 8 Jl), 3.10-3.75 p
pm (m, (3II) Example 5 Dry silica gel tube and stirrer (300
In the 6th round bottom flask of t17i, add 10. V(
0.rJ 22 mol) and optically dehydrated tetrahydrofuran 17[]+uJ were weighed out under a nitrogen atmosphere and dissolved with stirring at room temperature. 1.9 g of 1-p[copenyl isocyanate (
0,023 mol) tetrahydrofuran liquid 2
0 mg was added dropwise to the solution at room temperature with stirring. After finishing washing, the mixture was directly pounded at room temperature for 3 hours, and detrahydrofuran was removed from W4 under reduced pressure to obtain 11.6 g of a pale yellow paste.

Elemental analysis value (%) 2B, 8 2.4 7.9
45.3 Total January shifts (%) 2B, 9
2.6 7.8 45.8IR spectrum 1370cm'(-8OtN< J/a8)
15ro0cTrL' (-N-Co -N-)
H 1845CnL-' (terminal vinyl group) NMR spectrum (CDsCOCDs solvent, TMS standard) 1.81
ppm (m, 2H), 3.26 ppm (m,
4H) 5.82ppm (d, 2)t), 5.00ppm
N-(3-
[3-(1-propenyl)ureido]globil)perfluorohexylsulfonamide 1(115+(0,018
5 mol), 80 g of ethanol, 50 g of water, 1 [fCi
Wrinkle water sodium 2.9 &([1,(] 28 mol)
was weighed out and stirred at 90°C for 1 m hour.Ethanol and water were distilled off under reduced pressure, and the residue was purified by crystallization from methanol.11 The decomposition temperature was 182°C.

Elemental analysis value (%) 28.6 -2.8 7,5
45.7il calculated value (%) 28.9 2.
8 7.8 45.8IR spectrum 1210cm-' (-8O3Na νa3)1
570cm-' (-8o2N\νas)1540
The absorption of the terminal vinyl group of cra-' (-N-CO-N -) Hll 1845C1n' disappeared.

NMR spectrum (D20 solvent, DSS standard) 1.80
ppm (m, 2H), 1.9/lpm (m, 21()
, 3.20-365 ppm (m, 8H) Example 6 N-(3-methylaminopropyl) 4
[1,8,V (0,064 mol) and light power jl-2
110 rnl of watered futrahydrofuran was stirred at 4" IJl (L, pear 4゛1A) under a nitrogen atmosphere. Allyl isothiocyaner) 6.6jl (0, [] 6
7 mol)/aM'+ in tetrahydrofuran bath H2O
ml was added dropwise to 41 L at room temperature while stirring vigorously. 4.
After completing the first step, stir in chamber Y8fr for 1 minute and add tetrahydrofuran to °d.! /, By removing with In'F, yellow pasty I snout 47. Obtained Og.

Elemental analysis Analysis I direct(゛n) ro9.4'l)
,9 5.6 4ro5IR spectrum 1670cm' (-so, N< νas)N M
R spectrum (CDs COCDs m medium, TMS standard) 1.80 ppm (m, 211), 2.92
ppm (s, 3H), 3.19ppm (m, 4H
), 3.77 ppm (d, 2H) 5.10 ppm (
m, 211), 5.80 ppm (m, 1H
) 7.00-7.55T) pm (m, l) 6 round 7jt of 200 lbs equipped with cooling condenser and stirrer
In a flask, add N-(3-[1-methyl-6-(1-propenyl)thioureido]propyl Jp-Valle fluorononenyloxybenzene 13.6
g (0, [) 185 mol), ethanol 80〃, water 40
y1 Sodium bisulfite 2.9. ! / (0,028
Take 1 mole).

The mixture was stirred at 90° C. for 1 hour. Ethanol and water were removed under reduced pressure, and the solid residue was purified by recrystallization from methanol.

The minute 1'+'l degree was 174°C.

Elemental analysis analysis IIα (%) 34.5 2.5 4
．． 9 3B, 8nth? 41 shift (ln) 34
．． 2 2.5 5.0 38.4I
R spectrum 121 Dr:m' (SO3Na νaS)
1570cm'(5O2N<νas) 1845m
1 loss or disappearance of the terminal vinyl group of '.

NMR spectrum (D20, medium, I) SS] (quasi)
1.791') Pm (m, 2) 1), 1.83 ppm
(m, 2 If) 2.97 ppm (s + 31
1), 3.29ppm (m, 611) 3.6Qppm
(t, 2J() Example 7 0 N-(3-methylaminopropyl)
Perfluorohexylsulfonamide 479 (0.10 mol), fully dehydrated tetrahydrofuran 200 ml,
Then, 10,110.10 mol of triethylamine) was weighed out under a crab atmosphere, and 60 ml of a tetrahydrofuran solution in which 12.7 p (0.10 mol) of 2-chloropropionic acid chloride had been dissolved was added dropwise at 0° C. with strong stirring. . After the addition was completed, the mixture was stirred at room temperature for 3 hours, and the triethylamine salt 8 salt was separated. By distilling off tetrahydrofuran, 566 g of a yellow transparent oil was obtained.

Gen et al.: Da analysis analysis value (%) 27.8 2.4 5,1
44.1r R spectrum, Tor NMR spectrum (CD, COCD, foil wire, TMS
Standard) 1.79 ppm (m, 2H), 2.88 ppm
m (t, 211), 3.10 ppm (s, 31
1)1,! 1.15-3.90 ppm (m, 6ki)
Cooling condenser and stirrer (Iiii)
In the third round bottom flask of mtV, add N-[N-methyl-N
-(2-chloroethylcarbonyl-5-aminopropyl)-(-fluorohexylsulfonamide 9.79 (
0.1]174 mol), ethanol 70g, water 50.9
, 3.3 g (0,026 mol) of sodium sulfite was weighed out and stirred at 90° C. for 6 hours at 4”jt.

Ethanol and water were distilled off under reduced pressure, and solid 'Alfi was recrystallized from methanol to produce fd. Decomposition temperature is 278℃
Met.

Elemental analysis value (%) 24.9 2,! + 4
．． 4 39.2 IR spectrum 1210CIrL-' (-8o, Na νas)
1ro70crn-' (-3o, N, νaa
) 1640 cm (, N11i) NMR spectrum (D, O bath medium, DSS group I) 1.80 ppm (m, 2H), 3.10 pp+n (s
, 3H), 3.15-3.65Ppm (m, 611
), 3.79 ppm (t , 2H) Example 8 3[JOm/6] equipped with dry silica gel tube and R batter
In a 9 μt mouth flask, 60 g (0.10 mol) of N-methyl-N-(2-hydroxy-3-methylaminopropyl) perfluorooctyl sulfonamide, 1 oomt of thoroughly dehydrated tetrahydrofuran, and triethylamine in, i g (0.10 mol)! :4 elemental atmosphere 1
Remove 1 ml of zeolite under 7f4 atmosphere and add 14 ml of chlorobutyric acid chloride.
．． 0. 30 ml of a tetrahydrofuran solution in which li' (0.10 mol) was dissolved was added dropwise at 0° C. while stirring vigorously. After completion of the dropwise addition, the mixture was stirred at room temperature for 3 hours, and triethylamine hydrochloride was separated. By distilling off the tetrahydrofuran, a yellow transparent oil 63.0.9 was obtained.

Elemental analysis value (%) 29.3 2.2 6,9
45.8 calculation 1ff (%) 29.1
2.2 4. [l 46. [+IR spectrum 1370crrL-' (-8OzNs νas
)1640儂-1('>Nhi) NMR spec]ru(CD, Co CD, medium, TMS
Standard) 1.73 ppm (m, 2H), 2.20 ppm
(t, 211) 3.10 ppm (s, 3H
), 5.15 ppm (s, 3H) 315~! 1.
<501111) m (m, 6H), 4.09 ppm
(m, IH) 200 mg of 6 with cooling condenser and stirrer
In a round bottom flask, add 12.2 g (0,0174 mol) of N-methyl-N-[2-hydroxy-N-methyl-N-(3-chloropropylcarbonyl)=3-aminopropylcoperfluorooctylsulfonamide. , ethanol 7
0 g, water 30 g, and sodium arousite 3.1 (0026 mol) were weighed out and stirred at 90° C. for 6 hours. Ethanol and water were distilled off under reduced pressure, and the solid residue was recrystallized from methanol to prepare M[l. The decomposition temperature was 274°C.

Elemental analysis value (%) 26.3 2.2 6.7
41.6IR spectrum 121 Dc1rL' (-8O3Na νas
)1570cm-' (-so, N<I'a8)
1640cr/L-'(\NC-)'11 NMR spectrum (D, 0 solvent, DSS standard) 1.77
ppm (m, 2H) 1. ! 1.06 ppm (s,
5H) 6.20-3.60 ppm (m, 6H), Otsu, 80 ppm (t, 2)L), 4.0
5 ppm (m, IH) Example 9 "Room 3" equipped with dry silica gel tube and stirrer
In a round-bottomed round-bottomed flask, add N-(3-aminopropyl)p-
Perfluorononenyloxybenzene carponamide 62
4 g (o, io mol), fully dehydrated tetrahydrofuran 150 ml, so 7 triethylamine: /101
．． ! i' (0.10 mol) was taken in 4F under nitrogen atmosphere,
1-Buteno-r-acid chloride 10.49 (Q,
10 mol) (I! solution of tetrahydrofuran bath solution 30
m1 was added dropwise at 0° C. with vigorous stirring. After completion of the dropwise addition, the mixture was filtered and stirred at room temperature for a period of time to remove triethylamine hydrochloride. By distilling off tetrahydrofuran, yellow transparent oil 6809 was obtained.

Elemental analysis CHNF analysis value (%) 39.9 2.4 4,0
46.6 Calculated value (%) 39.9 2.
5 4.0 46.7IR spectrum 1370cm-' (-8o, Ngu νaa) 184
5 cm' (terminal vinyl group) NMR spectrum (CD, CoCD3 solvent, TMS standard) 1.82 ppm (m, 2H), 3.26 ppm (m
,4H)s,s2ppm(d,2H),5. OOpp
m (m, 2H) 5.80 ppm (m, IK
) Cooling condenser and stirrer (2QQ)
ffl/, N-(N-(1-
propenyl)carbonyl-6-amituprovir]p-perfluorononenyloxybenzenecarbonamide 12.
8 g < 0.0185 mol), 70 I ethanol, 4 mol water
0. S/, aqueous sodium nitrite 2.9! j(0,0
+("14!/, L, for 11 hours at 90°C. Ethanol and water were distilled off downstream to σ, and the solid residue was recrystallized from methanol to produce rt'i. Decomposition temperature The temperature was 286°C.

Elemental analysis analysis value (%) 34.6 2.0 'y, 6
40.3 Total p value (%) 34.7 2.1
3,5 40.6IR spectrum 1210va-' (-80, Na l7as
) The absorption of the terminal vinyl group at 1845 cm-' disappeared.

NMR spectrum (D20 solvent, DSS standard → 1.78
ppm (m, 2H), 1.8! +ppm (m, 2H),
3.15-5.60 ppm (m, 6i(), 3.80
ppm (t, 2H), 7, D ~ 7.6 ppm (m, 4H) Example 1
N-(N-methyl-6-amituprovir) perfluorohexyl sulfonamide 30.5' (0
, 064 mol), pyridine 70I, and 9.6 g (0,096 mol) of succinic anhydride were weighed out and stirred at room temperature for 4 hours. Pyridine was distilled off under reduced pressure, and 150 ethyl acetate (3me and 2(N)) and 150 ml of hydrochloric acid were added to the brown oil residue.
m1 was added and washed. After further washing with 100 ml of water, the ethyl acetate layer was separated from the anhydrous 1'+? , sodium 20.9 for 24 hours. The ethyl acetate layer gave a white paste 33.4.9.

Elemental analysis Asahi (%) 29.72.5 11.9
4ro6IR spectrum/1370cm' (-8O2N J/H)\164[]cx'(ゝNC-)/11 1710cm-'' (-COOH) NMR spectrum (CDs COCDah medium, T
hi S standard) 1.80ppm (m, 2H), 2.0
6 ppm (t, 211), 2.60 ppm (t, 2H
), 3.11 ppm (s, 3H), s, 25pp
m(t, 2H), 3.51 Tlpm(t, 2H
) Example 11 N-(N-methyl-ro-aminopropyl)2-perfluorooctylethanesulfonamide 59 was added to a 30ON 6 day round bottom flask equipped with a dry silica gel tube and a stirrer.
．． 8 g (0.10 mol), 133 mJ of fully dehydrated tetrahydrofuran, and 101 g of triethylamine (
0.10 mol) was weighed out under a nitrogen atmosphere, and 60 ml of a tetrahydrofuran solution in which 14.0 g (0.10 mol) of 2-chloropropionic acid chloride was dissolved was added dropwise at 0° C. with strong stirring. After completion of dropping, filter time at room temperature f+:
J: Stir and remove l-ethylamine JMf salt.

By removing tetrahydrofuran y4, 65.5 g of a yellow invention oil was obtained.

Elemental analysis fiAc'>o) 29.7 2.5
ii, [J 46.6IR spectrum 13 y []Cm, -' (-8o2N,
vas) 16401'(ゝNC-) /11 N ki R spectrum/l/ (medium to CD3COCD,
T M S group '137L ) 1.83 ppm (m
, 2f(), 2. rl 9 ppm (t, 2H)
2.25 ppm (t, 2) (), 5. ID
ppm (n, 3H) 3.15-3.45 ppm (m
, 8H) 200 with cooling condenser and stirrer
N-[N-methyl-N-
(2-chloroethylcarbonyl)-6-aminopropyl]2-perfluorooctylethanesulfonamide 12.
0. V (0,0174 mol), ethanol 70g, water 4
0,9. 5.3.9 (0,026 mol) of sodium sulfite was weighed out and stirred at 90°C for 10 hours. Ethanol and water were distilled off under reduced pressure, and the solid residue was purified by recrystallization from methanol. The decomposition temperature was 290°C.

Elemental analysis value (%) 27.2 2.6 3.5
42.4 Calculation frequency (%) 27.0
2.4 3.7 42.7IR spectrum 1210crrL-' (-8O1Na vas
) 1370m, -” (802!~T〈vas)
-1 of 1640 (NC-) /11 NMT (spectrum (D20 intoxicant, DSS standard) 1
．． 81 ppm (m, 2H), 2.05 ppm (
t, 2H) 3.10 ppm (s, 3H), 3.10
~3.55 ppm (m, 811) 3.80 ppm (t
, 2H) Example 12 In a 300 ml 6-necked round bottom flask equipped with a dry silica gel tube and a stirrer, N-(2-hydroxy-6-aminopropyl)2-perfluorooctylethanecarbonamide)'' 36.1 .F (0064 mol) and 170 ml of sufficiently dehydrated tetrahydrofuran were weighed out under a nitrogen atmosphere,
The mixture was stirred at room temperature. 20 ml of a tetrahydrofuran bath solution in which β-chloroethyl isocyanate 6,0.9 (0,067 mol) was dissolved was added dropwise at room temperature with strong stirring. After completion of M'+T-, the mixture was stirred at room temperature for 3 hours, and tetrahydrofuran was distilled off under reduced pressure to obtain a slightly yellow oily substance 42.0.9.

Elemental analysis value (%) 30.2 2.4 6.3
48.2 Calculation frequency (%) 30.5
2.5 6.3 48.3IR
Spectrum 1 to 70 crrL-' (-8o, N, νas
)1640crn' (-N-Co-N-)
II II NMR spectrum (C1) 3 Co CD, common medium, 1M
S standard) 2.09ppm (t, 2H), 2.23ppm
(m, 41()5, 10-3.60 pprn(m,
611), 3.99ppm (m, IH) 2oomt 6 with cooling condenser and stirrer
In a round bottom flask, add N-(2-hydroxy-3-[3
-(β-chloroethyl)ureido]propyl)2-perfluorooctylethanecarbonamide 11.6,! ?
(0,0174 mol), 70 g of ethanol, 50 g of water,
1lli(I(, sodium acid 3.3.!i'(0,
026 mol) was weighed out and stirred at 90°C for 5 hours. Ethanol and water were distilled off under reduced pressure, and the solid residue was purified by recrystallization from methanol. The decomposition temperature of this substance is 1
The temperature was 81°C.

Elemental analysis analysis 1 [1 (%) 27.7 2.1 5
．． 5 43.9 Calculated value (%) 27.7
2.3 5.7 45.8IR spectrum 1210m-' (-8O3Na νas )N
MR spectrum (D20ie medium, DSS standard) 2.00
ppm(t, 2)(), 2.25 ppm(t, 2
H) 6.15-3.55 ppm (m, 6H), 3.85
ppm (t, 2H), 4. OOppm (m, IH) Example 16 301Jm with dry silica gel tube and (1)
In a third round bottom flask of ε, 45.1 g (0,064 mol) of N-(1)-aminehexyl)p-perfluorononenyloxybenzenesulfonamide and 170 mg of fully dehydrated tetrahydrofuran were added under a nitrogen atmosphere. Weigh out,
In room 1sho (1), it's stirring ri'rJW L. 20 ml of a tetrahydrofuran bath containing 5.69 (0,067 l) of allyl isocyanate was added dropwise at room temperature with vigorous stirring. ? +P, after finishing under i, ζ temperature measurement 4iL for 6 hours
The mixture was stirred and tetrahydrofuran was distilled off under reduced pressure (i) to obtain a slightly yellow oily substance 50.5.9.

Elemental analysis value (%) 3B, 2 3.6 5.2
41. IIR spectrum 1570CrrL-' (5O2N,, 1eas
)1530cm-' (-N-Co-N-)H
H 1850cIrL-' (terminal vinyl group → NMR spectrum (CD3COCD3 bath medium, 7MS standard) N55p
pm (m, 8H), 3.22ppm (m, 4H) 3.8
0 ppm (d, 2H), 5.00 ppm (m,
2H) 5.50 ppm (m, IH), 7.0
9 to 7.60 ppm (m, N-(6-[3-(1-propenyl)ureide] hexyl 1■)-barfluoronoi, nyloxybensene sulfonamide 14.5&(0,0185 mol),
80g of ethanol, 301g of water. Weigh out 2.9 g (28 moles of o, o) of sodium sulfite and heat at 90'C.
The mixture was stirred at #41 for 12 hours. Ethanol and water were removed under reduced pressure, and solid IM (ti) was purified by recrystallization from methanol.

Elemental analysis analysis tweet (%n 33.9 2.9 4,7
36.6IR spectrum 1210Crn-' (5O1Na νas)
1370tyn-' (-80,N, νa8)
154 Dcnt-' (-N-Co -N -)H
The absorption of the terminal vinyl group of H1845bo-1 disappeared.

NMR spectrum (D, 0 solvent, DSS standard) 1.55
ppm (m +' 8H), 1.79ppm (m, 2H
) 5, 10-3.55 ppm (m, 6B), 6
．． 8+6 ppm (t, 2H), 7.10-7.50 ppm (m, 4H) in a 500 ml round bottom flask equipped with a cooling condenser and a stirrer.
N-(3-[:Ro-(β-ri[10ethyl)-1-methylureide]p[1 building) bar 70 mouths Gysyl sulfonamide 51 (0,087 cells), Instinct potassium Z3.
I/(013 mol, ethanol 150M and water 15
1 was weighed out, and 1) was pressed for 3 hours to remove ethanol with pressure, and the precipitated white solid 1- 1” combing/, -L11 solid f
Dry line at 50'C; +I] crystallize from ethanol/water to 4+1? '4. This item's collection f4t is 6Ig and 7゛.

mp (l: i point) = 213”C Elemental analysis analysis (1 (L 27.9 2
．． 9 7,5 44.5IIζ spectrum 1370crfL-'(5OtN<νas)1
(545C'IrL(/N 27.9 g (0.05 mol) of 1-methylureidopropyl)perfluorohexylsulfonamide and 200 g of acetonitrile were weighed out and dissolved by heating.

8.7 g (0,075 mol) of chlorosulfonic acid was added to 40
The mixture was stirred vigorously at ℃ and added dropwise from the IL. After the dropwise addition was completed, the mixture was further stirred for 5 hours. After neutralizing with an aqueous solution of 1N hydroxide, acetonitrile and water were distilled off under reduced pressure.

The yellow solid residue was purified by recrystallization from ethanol. The view of this object was 23y.

mP=56°C Elemental analysis N M R7, Vector (D20k, D S
S j (1, t"+") 1.80 ppm (m, 2H)
, 2.96 pprn(a, 3B)6゛2D~3
．． 80 ppm (m, BIT) Patent Applicant Niken Nippon Ink Kagaku Kuwa Co., Ltd. Kawamura Rikagaku Kenkyusho Death Center ■Applicant Yomura Rikagaku Kenkyusho Foundation 2-7-8-372 Kamikizaki, Urawa City

Claims (1)

[Scope of Claims] 1 A linear fluorine-containing anion compound represented by the general formula [ ] % formula % [ . 2 z is -Z, -N- [However, 2. -802-1-C
O-1R. child CH2CH, thickness so, -1(CH,CJ(,)j-C
o-1 (where l is an integer of 1 to 10), -〇beOso, - or -O-C>CO-, and R1 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and CH
, Meng OR? , or 4 CH, C horse O shakudori (however, b is an integer from 1 to 4, d is an integer from 1 to 20, and R2
is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms. )
It is. ] The compound according to claim 1. 6. General formula [■] Rf-2-Q, -N-C+N+&Q, -X [■] 1 X is a chlorine atom, a bromine atom, or an iodine atom. General formula [[']1)I Rt -Z-Q, -N-c+N→-Qt -5O1N, characterized by reacting a fluorine-containing compound represented by with 1F alkali metal sulfate.
a [I']II' [In the formula, Rf, Z, Q, , R, Y, Qt, 1 have the same meanings as above. ] A method for producing a linear fluorine-containing anionic compound. 4. General formula [■ Old H Rf-z-Q+-N-C (N+Qs-CH=C&
Reacting a fluorine-containing compound represented by [tn]+1' with nitrous acid, sodium hydrogen oxide, or sulfurous acid potassium ii! General formula [[“] Y [However, Rf, Z, Q, , +t, y, Q,
, a is the same as the above. ] A method for producing a linear fluorine-containing anionic compound represented by 5 A fluorine-containing compound represented by the general formula [1■] was used as a Zulfe-1 inhibitor, chlorosulfonic acid, ? /-'J11iC acid, fuming acid or so, general formula [ge] 1 I Rf-Z-Ql-N-C4N-)-Q20SO,M
[”) II 8 [wherein, Rfs Zs Ql s Rs Ys Qt
, " is the same H':FA as above, and M is a hydrogen atom or an organic or inorganic cation." 6 General formula [■] Rf- Z-Ql-NH(V:] R is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group. A fluorine-containing amine compound represented by Below, succinic anhydride and Ji,
Li); general formula [['''') Rt-z-Q, -N-c-cx, c*r2cooI(
[t″″]1 [In the formula, Rf, Z, Ql, R are 6+ as shown,
k] on C1. ] Double phrase S fluorine anion compound 9no) 5.'4:i, i'+method. 7. Z is -Z, -N- [However, zl is -5o2-1
-CO-1R7 4CH, cI+t%5O2-1+ CIIz CH2%
Co (world, shi, i is an integer from 1 to -10), -o Os o, -1 and shi' -〇→5co-, R1 is a hydrogen atom, alkyl with a carbon prime number of 1 to 12 base, f
CH, -'); OIζ2, or + C) I, C
) 1209I4 (However, b is an integer of 1 to 4, d is a fatty number of 1 to 200, and R7 is a hydrogen atom or a carbon number of 1
~B is the alkyl group. ). ] The method according to claim 3, 'f; 4, 5 or 6 of IUJ.