JPS5865256A - Compound containing polyfluoroalkyl group, its preparation and surface active agent - Google Patents

Abstract

NEW MATERIAL:The polyfluoroalkyl group-containing compound of formulaI [Rf<1> and Rf<2> are perfluoroalkyl of formula -CnF2n+1; Q<1> and Q<2> are -SO2NR<3>- (R<3> is lower alkyl) or -CONR<4>- (R<4> is lower alkyl); R<1> and R<2> are alkylene of formula -CmH2m; x, y and p are 0 or 1; n is 4-14; m is 1-3]. EXAMPLE:Bis(1H, 1H, 2H, 2H-perfluorodecyl) L-glutamate p-toluenesulfonic acid salt. USE:Precursor of surface active agent of formula II. The characteristic features of the compound of formula II are low frothing tendency and surface tension lowering activity. PROCESS:The compound of formulaIcan be prepared by reacting an alcohol of formula III (Rf is Rf<1> or Rf<2>; Q is Q<1> or Q<2>; R is R<1> or R<2>, t is x or y) with glutamic acid or aspartic acid. The compound of formulaIcan be converted easily to the surface active agent of formula II by converting the active hydrogen of the -NH2 group to the hydrophilic group Z.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides novel polyfluoroalkyl group-containing compounds,
The present invention relates to its production method and surfactant.

Conventionally, various surfactants such as anionic threads, cationic threads, and nonionic surfactants have been known, and polyfluoroalkyl groups such as perfluoroalkyl groups (hereinafter referred to as P
fluorinated field n+i having Tl' (abbreviated as A group)
? i'r ('l Wll is also known.

Fluorinated surfactants exhibit unique surfactant properties and are therefore suitable for use as evaporation inhibitors (extinguishing agents) for volatile liquids, leveling agents for photographic gelatin layers, paint additives, and other various uses. In addition, in the anionic fluorinated world, η activators are widely used as emulsifiers in the production of fluorocarbons and fats. As an amphoteric surfactant that is less sensitive to salts and is less affected by salts, it has the characteristic 'P,!?
A fluorinated hermaphrodite m+ activator has also been proposed (4).

On the other hand, a typical surfactant whose hydrophobic part is a monoargyl group forms a spherical micelle as a molecular aggregation in an aqueous solution, and the water part forms a spherical micelle as a sialyl ammonium-enriched sialkyl phosphate. It is known that a single drug forms endoplasmic reticulum (vesicles) with a bimolecular Jla 'rttt structure.
Dansicles with this structure have an internal aqueous phase, and there is a phase transition between gel phase and liquid crystal phase. Attempts have been reported to use vesicles not only as a simple site for reproducing conventional biological reactions, but also as a site for various organic reactions to control reactions.

The present inventor has proposed that PFA be added to glutamic acid or aspartic acid.
By reacting a group-containing alcohol, P is added to the molecule.
It has been found that a new compound having two FA groups can be obtained. The inventors have also found that by appropriately converting the active hydrogen of the -NH2 group of such a new compound into a hydrophilic group, a new surfactant having two PFA groups can be obtained. The surfactant dissolves in water to form a bilayer membrane packing vesicle, and this bilayer membrane is extremely stable and has a higher ability to retain hydrophilic compounds and a barrier ability against hydroxyl ions than conventional hydrocarbon-type vesicles. It has characteristics that are much more rigid than bilayer membrane vesicles.

The present invention has been completed based on the above findings, and firstly, a PFA group-containing compound (I) represented by the general formula
H's 9 Q-(Q2)y-R2-0-C-CH21 P Tl' A, lit, containing j difference α1
1 active agent (1t) is newly provided. Wow [~
In the above-mentioned set of anchors, the binding and RT are -an"2n
-1-1-fluoroalkyl group, Ql
and Q2N, -8O2NR3- or -CONH2-, R
1 and R217]', an alkylene group represented by -CrnH2m-, x, y and p are 0 or 1, Z is a hydrophilic group,
Y is a hydrogen atom or Z, n is a positive integer of 4 to 14,
The m-th positive 4y numbers 1 to 3, R3 and R4 are lower alkyl groups.

The present invention also provides a new method for producing a PFA group-containing compound (I) by reacting an alcohol with the general formula Rf-(Q)t-R-OH with glutamic acid or aspartic acid. In this case, Rf is the above-mentioned R,
f or Bi, Q is the above-mentioned Ql or Q2, t is the above-mentioned X, and R is the above-mentioned R1 or R2.

In the present invention, it is important to have two PFA groups in the molecule, which allows the surfactant (I
Various excellent characteristics as I) are exhibited. That is, the surfactant (n) dissolves in water to form a vesicle with a bilayer membrane structure, and this bilayer membrane is very stable and has a high ability to retain hydrophilic compounds in the aqueous phase within the vesicle and a vesicle with a bilayer membrane structure. It is characterized by a strong barrier ability against ions. In addition, the aqueous solution of the surfactant (1) has the characteristic that it hardly foams, and has a surface tension lowering ability of Nl? , get caught. □By mixing it with a normal fluorinated surfactant, it is possible to obtain a surfactant with low foaming properties and high surface activity.

(7) ゛1 of the present invention? The FA group-containing compound (T) can be produced by various synthetic methods, but usually has the general formula Rf as described above.
(Q) t-R-OH can be smoothly and advantageously synthesized by an esterification reaction between a fluoroalcohol and glutamic acid or aspartic acid. In such a synthesis method, the reaction is carried out using benzene, toluene, cyclohexane, -+,
It is preferable to carry out the reaction in an inert solvent such as 2-dimethoxyethane or 1,2-dichloroethane. Usually, an esterification reaction catalyst, such as sulfur 11β'', phosphoric acid +
Acids such as p-toluenesulfonic acid/III! /11
! It is preferably carried out in the presence of. The reaction temperature is 5() to 1
The temperature is preferably about 50°C, preferably about 70 to 100°C.

The amount of catalyst used is preferably about 1 to 15 moles per mole of glutamic acid or aspartic acid.

15 to 3 ml of fluoroalcohol per mole of glutamic acid or aspartic acid. , preferably a molar ratio of about 2 to 24 moles.

On the other hand, in the present invention, the agent (II) containing T''II' It can be easily synthesized by conversion. In this case, the conversion reaction is not particularly limited and a wide variety of methods can be adopted.

Of course, Y in the specific surfactant (I) may be a hydrogen atom, or Y may be any of various hydrophilic groups 2.

In the latter case, the two fins and water curtains 2 may be of the same species or of different species.

For example, the following synthesis route may be exemplified.

Specific examples of the 4111-type specific surfactant (l) of the present invention include the following.

That is, ■ ○ ■ RfCH2CH20COCHNHCOCTJ2N
(CH,), -C1RfCH2CH20CO(CH
2) 2 RfCH2CH20CO(CH2)2 (1-) ■ ■ RfCH,,CH20COCI(NHCOCH,N
(CH,)2CH2Co.

For example, The formation of such a molecular structure has been confirmed by means such as NMR spectroscopy, elemental analysis, and MR spectroscopy.

In the present invention, 1'(f is perfluoroalkylnot represented by -C11'' 2 n+1, and n is 4 to
14, (10) Preferably a positive integer from 6 to 12 is selected.

Of course, Rf may be linear or branched, and R and R may be the same or anisotropic. However, R4 may be a mixture of a plurality of different n values. Similarly, R can also be linear or sub-branched, but it is usually m-2 CH2CH2
- is exemplified as a preferred one, and R1 and R2 may be different. Note that t is O or 1, but t-0 is preferable as in the above-mentioned preferred embodiment. In the case of t-1, Q is -8o2NR3- or -CONH2, but in such a case, fluoroalcohol and R
fSo2NR1R-OH or RfC0NR4-R-OH
may be used for reaction with glutamic acid or aspartic acid.

As the hydrophilic group 2, a wide range of cationic, anionic, nonionic, and amphoteric groups such as betaine can be employed. Examples include the quaternary ammonium type as shown in (1), (2) and (2) above, the betaine type as shown in (2) above, the polyoxyethylene type as shown in (2) above, and the amine oxide (11) type as shown in (2) above.

- The specific surfactant (]l) of the present invention can be widely employed in various uses utilizing the above-mentioned properties. For example, it exhibits excellent effects as a wetting agent for photographic emulsions, a leveling agent for floor waxes, a wetting agent for paints, a dispersant for synthetic latex, and a dispersant for powdered agricultural chemicals.

Next, embodiments of the present invention will be specifically explained in terms of Tj-+, but it goes without saying that the present invention is not limited in any way by such iy1. In addition, in the following examples,
Surface tension and 71′i′! Foam 1f1. The measurement was carried out as follows. That is, surface tension d: A surfactant water bath solution diluted to a predetermined concentration is kept at 25°C and
Measured using the hanging plate method. The foaming property is also 25.
O,] at °C, using a Tll volume-related aqueous solution: Ross
&Miles' method.

Example 1 An internal volume of 500 ntl was equipped with a stirrer, a Dean-Stark 14 tl vessel, a reflux condenser, and a thermometer.

into a flask, L-glutamine 8: (12) C11', (C'F'2), 0H2CH20)I40
9 (0,086 mol), p-toluenesulfonic acid 9
P (0,047 mol) and 300 mJ of toluene were charged, and the contents were kept in a suspended state by pressing down, and the resulting water was heated under reflux for 4 hours without separating it. After the reaction, the precipitated solid was collected by cooling and recrystallized from ethanol to a melting point of 1.
35 g of white powder at 10° C. was obtained. The yield based on the raw material fluoroalcohol was 85%, and it was confirmed that the product was the L-glutamic acid bis-(IH+IH+2H+2H-berfluorodedyl) ester-p-toluenesulfonate.

(13) Example 2 Internal volume 30 equipped with stirrer, dropping funnel and thermometer
0WLl? The p-toluenesulfonate obtained in Example 1 was placed in a flask of 8,! ? , (6,6X 10-3 mol), triethylamine 1.59 (0,015 mol) and chloroform 10 (Ime) were prepared and dissolved (6,
A solution of 9×10 −3 mol) in chloroform was slowly introduced dropwise. Thereafter, a stirring reaction was carried out at Hayabusa temperature for 24 hours. After the reaction, the solvent chloroform was distilled off under reduced pressure, water was added to the residue, and insoluble matter was collected and recrystallized from methanol. White powder with a melting point of 925-94°C8. ] fj was turned down. The yield of raw material p-toluene sulfone lv is 94
%, and elemental analysis, engineering R spectrum, and NMR spectrum showed that the white powder was L-glutamic acid N [p (ω-promoptylated)-benzoylcybis-(IH2I H,2
The product was confirmed to be H,2H-berfluorodecyl) ester.

Example 3 A flask with an internal volume of 1007 πg was charged with 2.9 (1,5X 10-3 mol) of the ester obtained in Example 2 and 50 ml of tetrahydrofuran/benzene (volume ratio 1/1), and a large excess of trimethylamine gas was added. I blew it.

Thereafter, the container was tightly stoppered and reacted with stirring for 50 hours while keeping it wet. After the reaction, the precipitated white solid was collected and crystallized from ethanol/n-hexane. 1.3 g of a white powder with a melting point of 140° C. and a thermal decomposition temperature of 255° C. was obtained, so the yield was 65% based on Konbak ester. The actual elemental analysis value of the compound is C: 34.41. H: 2.79°N: 2.0
9, C39 horse, N20. The calculated value as BrF,4 is C: 34.61, )(: 2.61,
N: 2.07. From the NMR spectrum,
The compound is (15) Bromide-L-glutamic acid-N-1:p-(ω-trimethylammoniumbutyloxy)-benzoylcybis-(IH,IH,2H,2H-)-fluorodecyl) ester ( b).

Example 4 In Example 2, C1,-C(ke0(CII,,)4
C8F, 7CH2CH20COCHN was obtained with a yield of 90% based on the raw material p-)luenesulfonate by the same procedure except that ClCH2COCl was used instead of -BrO.
HCOCH,C1C8F,7C)(2CH20CO(C
A compound named H2)2 was obtained.

Example 5 A compound (16) C8F17CH2C1(20CO(CH2)2) was prepared by the same procedure as in Example 3 except that the compound obtained in Example 4 was used instead of the ester obtained in Example 2. A) was obtained.

Example 6 In place of trimethylamine in Example 5, (CH,)
The following compound was obtained except that 2NCH2CH2NHcooCH2@ was used. Next, this compound was reacted with hydrogen bromide to obtain the following compound (c).

Example 7 Internal volume 500 mA equipped with stirrer, reflux condenser with Dean-Stark separator and thermometer! in the flask of
L-aspartic acid 5.5 g (o, 041 mol), R
Imo cH2ca, oH (R imoke C,?,%12F.

(17) has a uniform CO”IQ of 43.9 (0,
083 mol), 1)-) luenesulfonic acid 9,9(0,
047 mol) and 300 tne of toluene were charged, the contents were kept in a suspended state under stirring, and the mixture was heated under reflux for 5 hours while separating the produced water. After the reaction, the precipitated solid was collected by cooling and recrystallized from ethanol to 130-135°C.
4 og of white powder with a softening point of . The yield based on the raw material fluoroalcohol was 90%, and the white powder was L-aspartic acid bis-(IH, IH).

1)- of 2H,2H-perfluoroargyl) ester
) It was confirmed that it was luensulfone Osakishio.

Example 8 Using the I)-1 toluenesulfonate obtained in Example 7 and following the same procedure as in Example 4, a compound (18) was prepared with a yield of 95% based on the raw material I)-toluenesulfonate. I got it. This compound was the same as that of Example 3).

Example 9 In a flask with an internal volume of 200 tnB, 1 p-) of the 1p-) luenesulfonate obtained in Example 7, 1 o y of water, 0.5 fI of sodium chloride and 10 ml of tetrahydrone
0 vtl was added and heated to 50°C. The reaction mixture was heated for 5 hours while vigorously stirring and blowing ethylene oxide at a rate of 10 nt/mm to obtain a compound (e).

Allopatric activator (I) of the present invention synthesized by the above means
Table (19) of an aqueous solution is a typical example. ), (c), ni), i (
? +) i17 respectively as follows (20)

Claims (1)

[Scope of Claims] 1-Carrier ゛ O Call R′f-(Ql) Alkyl group, Ql and Ql are -8
O□NR3- or -CONH2-, R1 and R2 are -C
an alkylene group represented by mH2m-, x; y and p are IO or 1, n is a positive integer of 4 to 14, m is a positive integer of 1 to 3, and R3 and R4 are lower alkyl groups). 1-containing compound. 2 General formula O (However, R8 and R41t 'n'2n-1-
1 perfluoroalkyl group Ql and Ql are -SO□NR3- or -CONH2-, R1 and R2 are alkylene groups represented by -CmH2m-, x. y and p are 0 or 1, Z is a parent, water is 10, Y is a hydrogen atom or 2, n Id: a positive integer from 4 to 14, m is 1
A polyfluoroalkyl group-containing surfactant represented by a positive integer of ˜3, where R3 and R4 are lower alkyl groups. 3 General formula Rf-(Q)t-R-OH (R in the formula
f is a perfluoroalkyl group represented by R or Ri or Cn]2 rl+1, Q is Ql or id:
Ql is a divalent group flanked by 5o2NR3- or -CONH2-, R is R1 or R2, and 10InH
2m- is a fake Alleki Lenz old, tke XX is Y
T is a number selected from 0 or 1, and n is 4 to 14
(m is a positive integer of 1 to 3, R3 and R4 are lower alkyl groups) and glutamic acid or aspartic acid are reacted to obtain the general formula %)) A method for producing a characteristic polyfluoroalkyl group-containing compound.