CN100376316C - Gemini surface active agent - Google Patents

Gemini surface active agent Download PDF

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CN100376316C
CN100376316C CNB2005101105868A CN200510110586A CN100376316C CN 100376316 C CN100376316 C CN 100376316C CN B2005101105868 A CNB2005101105868 A CN B2005101105868A CN 200510110586 A CN200510110586 A CN 200510110586A CN 100376316 C CN100376316 C CN 100376316C
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reaction
surfactant
surface active
active agent
nmr
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CN1966137A (en
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蔡良珍
刘洪来
孙永峰
周敏
陶晓春
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East China University of Science and Technology
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Abstract

The invention relates to a cationic Gemini surface active agent with pyridinyl, wherein said agent is the compound as right formula, while R is alkyl group of H or C1-C20, A is F, Cl, Br, I or IO3. The inventive surface active agent can be used in washing, disinfection, etc.

Description

A kind of Gemini surfactant
Technical field
The present invention relates to a kind of Gemini surfactant, specifically, relate to a kind of cationic Gemini surfactants that contains pyridine radicals.
Background technology
Gemini (twin) surfactant is that its structural representation formula as the formula (1) by hydrophilic a kind of surfactant that basic (or close relative's head base) adopts chamical binding to be connected together by spacer group (spacer group) of the surfactant monomer of two structures identical (or close).By formula (1) as can be known, the tight contact between Gemini surfactant activity composition, and do not destroy the hydrophilic feature of its base, thus make this class surfactant present high surface-active.
Figure C20051011058600031
The long carbochain of long carbochain ion head base spacer group ion head base
(1)
The Gemini surfactant has the surface-active more much higher than conventional surfactants, and has following characteristic:
1. easilier be adsorbed on the gas/liquid surface, thereby more effectively reduce the surface tension of water.2. easier gathering generates micelle.3. has very low Kraff point.4. as composite,, will produce bigger cooperative effect for reducing aqueous solution surface tension with conventional surfactants (especially non-ionic surface active agent).5. has good calcium soap dispersive property.6. are good wetting agents in a lot of occasions.
1971, people such as Bunton have synthesized gang's cationic Gemini surfactants first, measure their critical micelle concentration (cmc), and used it for the dynamics research of organic reaction, from then on opened the prelude of this type of surfactant system research work.Because Gemini has distinctive molecular structure and multiple specific character, in recent years. countries in the world are surging unusually to its research interest, become the research focus of international colloid science, association area and commercial Application just gradually.
Summary of the invention
The object of the invention is, a kind of cationic Gemini surfactants that contains pyridine radicals that can play a role in fields such as cleaning, sterilization and phase transfer catalysis (PTC)s is provided.
The said compound of cationic Gemini surfactants that contains pyridine radicals of the present invention for having structure shown in the formula (2)
Figure C20051011058600041
R is H or C in the formula (2) 1～C 20Alkyl, A is F, Cl, Br, I or IO 3A preferred version of the present invention is that R is C 10～C 20Chain-like alkyl: another preferred version is that A is Cl, Br, I or IO 3, best A is Br or Cl.
The method for preparing the said Gemini surfactant of the present invention is:
(1) be initiation material with the 4-picoline, get part object [compound (6)] through alkylation, amination, amidatioon connection and salt-forming reaction successively, its synthetic route is as follows:
Figure C20051011058600042
Wherein: in alkylated reaction, used alkylating reagent is R 1X (R 1Be C 2～C 20Alkyl, X=Cl, Br or I); Used alkali is lithium diisopropylamine (LDA), BuLi, NaH or NaNH 2The mol ratio of 4-picoline and alkali is 1: 1～4; Solvent for use is benzene, toluene, n-hexane, cyclohexane, benzinum, oxolane or carbon tetrachloride; The alkylated reaction temperature is-10 ℃～50 ℃, and the reaction time is 1～10 hour;
In ammoxidation, 4-substituent pyridine [compound (3)] and Sodamide (NaNH 2) mol ratio be 1: 1～6; The used solvent of ammoxidation is by 1～3 methyl substituted benzene, N, accelerine or N, and the N-diethylaniline, reaction temperature is 100 ℃～180 ℃, the reaction time is 2～10 hours;
In amidation process, the mol ratio of amidation reagent and compound (4) is 1: 2～2.4, and used amidation reagent is oxalyl chloride or diethy-aceto oxalate; Used solvent is C 1～C 6Monohydric alcohol, an ethyoxyl ethylene glycol, benzene, toluene or pyridine; Reaction temperature is 50 ℃～180 ℃, and the reaction time is 10～60 hours;
In salt-forming reaction, compound (5) is 1: 2～10 with the mol ratio of acid, and used acid is HF, HCl, HBr, HI or HIO 3Used solvent is that water, ethanol are or/and ether; Reaction temperature is 0 ℃～40 ℃, and the reaction time is 0.5～5 hour.
Or (2) be initiation material with 2-aminopyridine or 4-methyl-2 aminopyridine, gets another part object through amidatioon connection and salt-forming reaction, and its synthetic route is as follows:
Figure C20051011058600051
The condition of wherein said amination, amidatioon and salt-forming reaction is with identical described in the preamble (1).
The said Gemini surfactant of the present invention can be used for fields such as cleaning, sterilization and phase transfer catalysis (PTC).
The specific embodiment
The invention will be further described for following illustrative example, and its purpose only is better to understand content of the present invention.Therefore the cited case does not limit protection scope of the present invention:
Embodiment 1
The preparation of compound (a) [R=H, A=Br]
A. amidation process
Restrain in (0.01mol) 2-aminopyridine 0.94, add the 20ml pyridine and stir, make it molten entirely, add 0.73 gram (0.005mol) oxalyl chloride, stop after 20 hours in reaction under 40 ℃.Be cooled to room temperature, removal of solvent under reduced pressure, residue benzene recrystallization purifying gets product 1.81 grams, is white solid, yield 75%.m.p.＝163℃-164℃。
1H?NMR(CDCl 3，Me 4Si)：δ7.15(2H，dd，J＝4.9，7.4Hz)，7.79(2H，m)，8.28(2H，d，J＝8.3Hz)，8.40(2H，m，)，9.83(2H，s)。
MS(70eV)m/z(％)：242(M +，0.83)，121(64)，94(95).78(100)。
B. salt-forming reaction
2.42 gram (0.01mol) N, N '-two-2-pyridine radicals oxamides adds in the alcohol solution of 50ml, adds 4.05 gram 40%HBr (0.02mol) again, stirred 2 hours under the room temperature, remove solvent under reduced pressure, add ether and cooling then, this HBr salt crystallization is separated out, meter 2.71g, productive rate 67%.Product is recrystallized in acetone-ether or alcohol-ether solution and obtains purifying.
1H?NMR(DMSO-d 6，Me 4Si)：7.35(2H，t，J＝6.1Hz)，8.04(2H，t，J＝7.3Hz)，8.09(2H，d，J＝8.1Hz)8.47(2H，d，J＝4.4Hz)，10.93(2H，s)。
Embodiment 2
Compound (b) [R=CH 3, A=Br] preparation
A. amidation process
Except that the 2-aminopyridine that replaces with 4-methyl-2 aminopyridine among the embodiment 1, other condition is all with embodiment 1, and product is a white solid, yield 84%.m.p.＝221.5℃-223℃。
1H?NMR(CDCl 3，Me 4Si)：δ2.43(6H，s)，6.98(2H，d，J＝4.8Hz)，8.11(2H，s)，8.24(2H，d，J＝5Hz)，9.74(2H，s)。
MS(70eV)m/z(％)：270(M +，3)，135(100)，108(82)，92(41)。HRMS (EI) calculated value (calcd for) C 14H 14N 4O 2270.1117, experiment value (found) 270.1122, Δ=1.9ppm.IR (KBr compressing tablet): 3190,3070,1680,1610,1560,1500,1450.
B. salt-forming reaction
Method is with example 1, and product is a white solid, yield 82%.M.p.=176 ℃ (decomposition).
1H?NMR(DMSO-d 6，Me 4Si)：δ2.46(6H，s)，7.31(2H，d，J＝5Hz)，7.94(2H，s)，8.38(2H，d，J＝5Hz)，11.2(2H，s)。
Embodiment 3
Compound (c) [R=(CH 2) 12CH 3, A=Cl] preparation
A. alkylated reaction
Add 0.72g NaH (0.03mol), 1.86g (0.02mol) 4-picoline and 10ml oxolane in reaction bulb, the control temperature is 30 ℃, and stirs, and behind the question response liquid homogeneous, adds 4.98g (0.02mol) 1-bromo-dodecane.After 6 hours, reaction finishes, and adds 5ml EtOH, adds 16ml H again 2O destroys unreacted NaH, and the mixed liquor extracted with diethyl ether merges organic facies, uses anhydrous K 2CO 3Drying is filtered, and ether is removed in decompression.Crude product carries out column chromatography with 230-400 order silica gel, and eluent is an ethyl acetate: the mixed solution of benzinum=1: 9, obtain 4.21 gram products, and be weak yellow liquid, yield: 83%.
1H?NMR(CDCl 3，Me 4Si)：δ0.88(3H，t，J＝6.9Hz)，1.26-1.31(20H，m)，1.62(2H，m)，2.59(2H，t，J＝7.8Hz)，7.10(2H，d，J＝5.3Hz)，8.49(2H，s)。
B. aminating reaction
2.61 gram 4-tridecyl pyridine (0.01mol) and 0.39 gram NaNH 2(0.02mol) be dissolved in the 20ml mesitylene, stir and be warming up to 140 ℃, reacted 8 hours.Reaction drops to room temperature after finishing, and the cold-trap decompression removes and desolvates, and adds the 10ml frozen water, and the mixed liquor extracted with diethyl ether merges organic facies, uses anhydrous K 2CO 3Drying is filtered, and ether is removed in decompression.Crude product carries out column chromatography with 230-400 order silica gel, and eluent is an acetone: the mixed solution of benzinum=1: 1, obtain 2.20 gram products, and be white solid, yield: 80%.m.p.＝74.6-75.4℃。
1H?NMR(CDCl 3，Me 4Si)：δ0.88(3H，t，J＝6.9Hz)，1.26-1.30(20H，m)，1.56(2H，m)，2.48(2H，t，J＝7.7Hz)，4.46(2H，s)，6.34(1H，s)，6.50(1H，dd，J＝1.2，5.3Hz)7.93(1H，d，J＝5.3Hz)。
MS(70eV)m/z(％)：276(M +，25)，121(68)，108(100)。
HRMS (EI) calcd for (calculated value) C 18H 32N 2276.2565, found (experiment value) 276.2550.
IR (KBr compressing tablet): 3420,3300,1650,1610,1550,1490.
C. amidation process
Restrain in (0.01mol) 4-tridecyl-2-aminopyridines 2.76, add the 20ml pyridine and stir, make it molten entirely, add 0.73 gram (0.005mol) oxalyl chloride, stop after 20 hours in reaction under 40 ℃.Be cooled to room temperature, removal of solvent under reduced pressure, residue gets product 1.94 grams with acetone/benzinum=eluant, eluent was crossed post in 1: 9, is white solid, yield 64%.Product is crystallization purifying in ethyl acetate.m.p.＝102℃-103℃。
1H?NMR(CDCl 3，Me 4Si)：δ0.88(6H，t，J＝6.9Hz)，1.26-1.34(40H，m)，1.68(4H，m)，2.72(4H，s)，7.09(2H，s)，8.23(2H，s)，8.33(2H，s)，10.6(2H，s)。
MS(70eV)m/z(％)：606(M +，0.87)303(100)，276(23)。
HRMS (EI) calculated value (calcd for) C 38H 62N 4O 2606.4873, experiment value (found) 606.4875.
IR (KBr compressing tablet): 3450,3170,1690,1610,1560,1500,1460.
D. salt-forming reaction
6.06 gram (0.01mol) N, N '-two-2-(4-tridecyl) pyridine radicals oxamides, add in the ethanol-water solution of 50ml, add 2.03 gram 36%HCl (0.02mol) again, stirred 2 hours under the room temperature, remove solvent under reduced pressure, add ether and cooling then, this HCl salt crystallization is separated out, meter 6.30g, productive rate 100%.Product is recrystallized in acetone-ether or alcohol-ether solution and obtains purifying.
1H?NMR(CDCl 3，Me 4Si)：δ0.88(6H，t，J＝6.6Hz)，1.26-1.35(40H，m)，1.72(4H，s)，2.86(4H，s)，7.36(2H，s)，8.23(2H，s)，8.83(2H，s)，12.92(2H，s)。
Embodiment 4
Compound (d) [R=(CH 2) 16CH 3, A=Cl] preparation
A. alkylated reaction
The 1-bromo-dodecane in using 1-bromine hexadecane alternate embodiment 3, other condition is white cured shape solid under the product room temperature all with embodiment 3, yield: 71%.m.p.＝30.3℃-31.0℃
1H?NMR(CDCl 3，Me 4Si)：δ0.88(3H，t，J＝6.9Hz)，1.25-1.31(28H，m)，1.61(2H，m)，2.59(2H，t，J＝7.8Hz)，7.10(2H，d，J＝5.1Hz)，8.49(2H，s)。
B. aminating reaction
Method is with example 3, and product is a white solid, yield: 76%.m.p.＝82.4-83.5℃。
1H?NMR(CDCl 3，Me 4Si)：δ0.88(3H，m)，1.25-1.30(28H，m)，1.58(2H，m)，2.48(2H，t，J＝7.7Hz)，4.47(2H，s)，6.34(1H，s)，6.50(1H，dd，J＝1.2，5.3Hz)7.93(1H，d，J＝5.3Hz)。
MS(70eV)m/z(％)：332(M +，51)，121(100)，108(91)。
HRMS (EI) calculated value (calcd for) C 22H 40N 2332.3191, experiment value (found) 332.3179.
IR (KBr compressing tablet): 3420,3300,1650,1610,1540,1490.
C. amidation process
Method is with example 3, and product is a white solid, yield 41%.m.p.＝102.5℃-103.5℃。
1H?NMR(CDCl 3，Me 4Si)：δ0.88(6H，t，J＝7Hz)，1.26-1.33(56H，m)，1.67(4H，m)，2.69(4H，t，J＝7.6Hz)，7.03(2H，d，J＝4.3Hz)，8.21(2H，s)，8.24(2H，d，J＝5.2Hz)，10.2(2H，s)。
MS(70eV)m/z(％)：718(M +，0.58)，359(100)，332(20)。
HRMS (EI) calculated value (calcd for) C 46H 78N 4O 2718.6125, experiment value (found) 718.6132.
IR (KBr compressing tablet): 3450,3330,1690,1610,1560,1500,1470.
D. salt-forming reaction
Method is with example 3, and product is a white solid, yield 91%.
1H?NMR(CDCl 3，Me 4Si)：δ0.88(6H，t，J＝6.9Hz)，1.26-1.38(56H，m)，1.72(4H，m)，2.85(4H，t，J＝7.6Hz)，7.35(2H，d，J＝4.9Hz)，8.19(2H，d，J＝5.1Hz)，8.83(2H，s)，12.96(2H，s)。

Claims (8)

1. Gemini surfactant, its compound for having structure shown in the formula (2)
R is H or C in the formula (2) 1～C 20Alkyl, A is F, Cl, Br, I or IO 3
2. surfactant as claimed in claim 1 is characterized in that, wherein R is C 10～C 20Chain-like alkyl.
3. surfactant as claimed in claim 1 is characterized in that, wherein A is Cl, Br, I or IO 3
4. surfactant as claimed in claim 3 is characterized in that, wherein A is Br or Cl.
5. as the described surfactant of claim l, it is characterized in that wherein R is H, A is Br.
6. surfactant as claimed in claim 1 is characterized in that, wherein R is CH 3, A is Br.
7. surfactant as claimed in claim 1 is characterized in that, wherein R is (CH 2) 12CH 3, A is Cl.
8. surfactant as claimed in claim 1 is characterized in that, wherein R is (CH 2) 16CH 3, A is Cl.
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CN102746396A (en) * 2011-12-07 2012-10-24 扬州大学 Method for extracting and transferring bovine serum albumin by preparing Cm-s-Cm type surfactant into reverse micelle
CN102718854A (en) * 2012-07-02 2012-10-10 扬州大学 Method for extracting and transferring haemocyanin under neutral and alkaline conditions
CN104496893B (en) * 2014-12-29 2017-06-16 华东理工大学 Preservative Gemini Geminis quaternary ammonium salt and preservative
CN110523539A (en) * 2019-08-14 2019-12-03 江西理工大学 A kind of application method of novel surfactant on inverse floatation of bauxite

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997046513A1 (en) * 1996-06-05 1997-12-11 Henkel Kommanditgesellschaft Auf Aktien Gemini surfactants, process for their preparation, and their use for preparing surfactants
US6797687B2 (en) * 2001-08-07 2004-09-28 Cognis Deutschland Gmbh & Co. Kg Gemini surfactant compositions
CN1557535A (en) * 2004-01-13 2004-12-29 ����ʦ����ѧ Gemini quaternary surfactant containing pyridine rings and preparing method thereof
CN1593150A (en) * 2004-07-16 2005-03-16 哈尔滨工业大学 Bi-dodecyl double quaternary ammonium salt iodine attached bactericide

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997046513A1 (en) * 1996-06-05 1997-12-11 Henkel Kommanditgesellschaft Auf Aktien Gemini surfactants, process for their preparation, and their use for preparing surfactants
US6797687B2 (en) * 2001-08-07 2004-09-28 Cognis Deutschland Gmbh & Co. Kg Gemini surfactant compositions
CN1557535A (en) * 2004-01-13 2004-12-29 ����ʦ����ѧ Gemini quaternary surfactant containing pyridine rings and preparing method thereof
CN1593150A (en) * 2004-07-16 2005-03-16 哈尔滨工业大学 Bi-dodecyl double quaternary ammonium salt iodine attached bactericide

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