CN105153034A - Method of synthesizing cation bleaching activating agent - Google Patents
Method of synthesizing cation bleaching activating agent Download PDFInfo
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- CN105153034A CN105153034A CN201510559138.XA CN201510559138A CN105153034A CN 105153034 A CN105153034 A CN 105153034A CN 201510559138 A CN201510559138 A CN 201510559138A CN 105153034 A CN105153034 A CN 105153034A
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- triethylamine
- benzoic acid
- acid chlorides
- lactan
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D227/00—Heterocyclic compounds containing rings having one nitrogen atom as the only ring hetero atom, according to more than one of groups C07D203/00 - C07D225/00
- C07D227/02—Heterocyclic compounds containing rings having one nitrogen atom as the only ring hetero atom, according to more than one of groups C07D203/00 - C07D225/00 with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D227/06—Heterocyclic compounds containing rings having one nitrogen atom as the only ring hetero atom, according to more than one of groups C07D203/00 - C07D225/00 with only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D227/08—Oxygen atoms
- C07D227/087—One doubly-bound oxygen atom in position 2, e.g. lactams
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
- C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D207/24—Oxygen or sulfur atoms
- C07D207/26—2-Pyrrolidones
- C07D207/263—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms
- C07D207/27—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms with substituted hydrocarbon radicals directly attached to the ring nitrogen atom
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/68—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
- C07D211/72—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D211/74—Oxygen atoms
- C07D211/76—Oxygen atoms attached in position 2 or 6
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D223/00—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
- C07D223/02—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings
- C07D223/06—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D223/08—Oxygen atoms
- C07D223/10—Oxygen atoms attached in position 2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D225/00—Heterocyclic compounds containing rings of more than seven members having one nitrogen atom as the only ring hetero atom
- C07D225/02—Heterocyclic compounds containing rings of more than seven members having one nitrogen atom as the only ring hetero atom not condensed with other rings
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Abstract
The invention discloses a method of synthesizing a cation bleaching activating agent and belongs to the technical field of fine chemical engineering. The method disclosed by the invention comprises the following steps: dissolving 4-chloromethyl benzoyl chloride and caprolactam into a solvent; adding an acid binding agent into a caprolactam solution to be dissolved; gradually dropping a 4-chloromethyl benzoyl chloride solution into a caprolactam-acid binding agent solution to be mixed by stirring; finally, adding tertiary amine to react and drying the solvent by spinning after the reaction is finished; washing an obtained solid to obtain a target product. According to the method disclosed by the invention, a synthesis process of the cation bleaching activating agent is greatly simplified; conditions needed for synthesizing the cation bleaching activating agent are reduced; meanwhile, the higher yield is guaranteed and the method is applicable to industrial popularization.
Description
Technical field
The present invention relates to a kind of method of synthesizing cationic bleach-activating agent, belong to technical field of fine.
Background technology
Hydrogen peroxide is green because of it, and pollution-free is a kind of SYNTHETIC OPTICAL WHITNER of industrial widespread use.Low-temperature activated bleaching is emerging a kind of bleaching method in the last few years, and the more traditional hydrogen peroxide bleaching of this bleaching method has obvious advantage.In low-temperature activated bleaching system, the environment of hydrogen peroxide is weakly acidic pH (traditional bleaching method, pH11-12, add sodium hydroxide or sodium carbonate), normal temperature (rinsing) or moderate temperature (traditional bleaching method, nearly 100 DEG C), decrease the consumption of energy, alleviate the burden of plant effluent process; In addition, the damage treating drift matrix (as: cotton fabric) is decreased.
Bleach-activating agent plays vital effect in low-temperature activated bleaching system, it can react with hydrogen peroxide in aqueous as organic peroxy acid precursor, generates the peroxy acid more active than hydrogen peroxide, at lower temperatures, effectively can remove foreign pigment.Conventional bleach-activating agent is nonanoyloxybenzene sulfonate (NOBS), tetraacetyl ethylene diamine (TAED), N-4 (triethyl ammonium methylene benzoyl group) lactan (TBLC).Easily there is side reaction because of it when pH lower (close to neutral) in NOBS and TAED, water-soluble lower reason, application is very restricted respectively.TBLC the best use of pH is 7.2, have excellent water-soluble, there is no both shortcomings, and with quaternary ammonium salt cationic group in its structure, make it can have certain avidity by electronegative material surface of effects on surface in aqueous, and then better carry out bleaching process.The major cause of current restricted T BLC heavy industrialization application is that synthesis step is loaded down with trivial details, expensive.There is the research of Many researchers to TBLC to bias toward the change of its structure to obtain different application characteristics at present more, or study relative bleaching process system, such as: the number changing carbon in TBLC leavings group lactam nucleus, its stability to hydrolysis is improved; Change the structure of TBLC quaternary ammonium salt cationic group, synthesis has different structure or has the activator of dication structure, probes into its application performance; Research N-4 (triethyl ammonium methylene benzoyl group) lactan (TBCC)/H
2o
2/ NaHCO
3bleach system, finds its same H of bleaching effect at 60 DEG C
2o
2/ NaHCO
3the bleaching effect of bleach system at 90 DEG C is close, and can be good at the water absorbability changing cotton fabric.At present, seldom have investigator to probe into the synthesis step how simplifying TBLC cationoid bleach-activating agent, reducing its cost, to make it apply more extensive.
Prior art is when synthesizing cationic bleach-activating agent TBLC, and often could obtain final product through too much bathing reaction, synthesis technique is very complicated, and synthesis condition is harsh.The present invention is by single bath process synthesizing cationic bleach-activating agent, significantly simplify the synthesis technique of cationic bleach activators TBLC, reduce condition needed for synthesizing cationic bleach-activating agent, ensure that higher productive rate simultaneously, and effectively reduce the production cost of this product.For TBCC, the productive rate of single bath process of the present invention can bring up to 96% by 58% of conventional two-step, production cost but can be reduced to 544.20 yuan by 1066.01 of conventional two-step yuan, this has benefited from productive rate on the one hand and must improve, on the other hand because the temperature reducing reaction has saved energy consumption, the solution of simultaneous reactions also becomes one from two kinds and has saved cost.
Summary of the invention
Simplify the too complicated problem of TBLC cationoid bleach-activating agent building-up process for solving, the invention provides a kind of method of synthesizing cationic bleach-activating agent, step is easy.
Described method comprises the steps:
(1) utilize solvent to dissolve 4-chloromethyl benzoic acid chlorides and lactan respectively, ethylamine is in lactan solution repeatedly, obtains 4-chloromethyl benzoic acid chlorides solution and lactan-triethylamine solution;
(2) under nitrogen protection the 4-chloromethyl benzoic acid chlorides dropwise of step (1) gained is joined in lactan-triethylamine solution, temperature of reaction is 20-50 DEG C, is uniformly mixed rear acquisition lactan-triethylamine-4-chloromethyl benzoic acid chlorides solution;
(3) triethylamine hydrochloride filtering generation is crossed;
(4) tertiary amine is joined return stirring process in the solution of step (3) products therefrom, obtain reaction soln;
(5) evaporate to dryness step (4) gained reaction soln, obtains target product after washing gained solid.
The structure of described target product is such as formula shown in (I):
In formula, n is 1,2,3,4,5,6 or 7; Alkyl R
1, R
2, R
3carbon atom number be arbitrary number in 1-16.
In one embodiment of the invention, alkyl R
1, R
2, R
3carbon atom number be 1,2,4,6,8,10,12,14 or 16, the hydrophile-lipophile balance value of the cationic bleach-activating agent of adjustable.
In one embodiment of the invention, described method is according to every mol4-chloromethyl benzoic acid chlorides, adds 1 ~ 4mol triethylamine, 0.2 ~ 5mol lactan, 0.2 ~ 5mol tertiary amine.
In one embodiment of the invention, described lactan can be butyrolactam, Valerolactim, hexanolactam, oenantholactam, spicy inner formyl amine, the ninth of the ten Heavenly Stems lactan and caprinolactam;
In one embodiment of the invention, described tertiary amine can be triethylamine, dimethyl amine, dimethyl propylamine, dimethyl butylamine, dimethylamylamine, dimethylhexylamine, dimethyl heptyl amice, dimethyl octylame, dimethyl nonyl amine, dimethyldodecyl amide, dimethyl cetylamine, diethyl propylamine, diethyl butylamine, diethyl amylamine, diethylhexylamine, diethyl heptyl amice, diethyl octylame, diethyl nonyl amine, diethyl decyl amine etc.
In one embodiment of the invention, the mol ratio (2 ~ 1) of the middle triethylamine of described step (1), 4-chloromethyl benzoic acid chlorides, lactan: 1:1:1.
In one embodiment of the invention, the solvent of described step (1) is any one or the multiple mixing in toluene, tetrahydrofuran (THF), ethyl acetate, acetonitrile or acetone.
In one embodiment of the invention, the time that described step (2) is uniformly mixed under nitrogen protection is 2-10h, preferred 3h.
In one embodiment of the invention, the time of return stirring described in described step (4) is 3-8h, preferred 4h.
In one embodiment of the invention, tertiary amine in described step (4): the mol ratio of 4-chloromethyl benzoic acid chlorides is 1:1.
In one embodiment of the invention, described step (5) washing solvent for use is acetone;
In one embodiment of the invention, described method concrete steps are as follows:
(1) take acetonitrile as solvent, be 4-chloromethyl benzoic acid chlorides according to mol ratio: the ratio of lactan=1:1.1 dissolves 4-chloromethyl benzoic acid chlorides and lactan respectively, again triethylamine is dissolved in lactan solution, obtains 4-chloromethyl benzoic acid chlorides solution and lactan-triethylamine solution; Wherein according to mol ratio triethylamine: 4-chloromethyl benzoic acid chlorides=2 ~ 1:1 adds triethylamine;
(2) join in lactan-triethylamine solution by the 4-chloromethyl benzoic acid chlorides dropwise of step (1) gained, in 20-50 DEG C, stirred under nitrogen atmosphere mixing 3h, obtains lactan-triethylamine-4-chloromethyl benzoic acid chlorides solution;
(3) triethylamine hydrochloride filtering generation is crossed;
(4) be tertiary amine in molar ratio again: tertiary amine is joined return stirring process 4h in the solution of step (3) gained by the ratio of 4-chloromethyl benzoic acid chlorides=1:1, obtains reaction soln;
(5) evaporate to dryness step (4) gained reaction soln, obtains object product after utilizing washing with acetone gained solid.
Described method, for the preparation of cationic bleach activators, preferably prepares TBLC cationoid bleach-activating agent.
Beneficial effect of the present invention:
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described, but the present invention is not by the restriction of embodiment.
Following examples material therefor, reagent, instruments and methods, without specified otherwise, be this area conventional material, reagent, instruments and methods, all obtain by commercial channel.
Embodiment 1
Triethylamine 0.04mol is added after being dissolved in by butyrolactam 0.02mol in 20ml acetone.4-chloromethyl benzoic acid chlorides 0.02mol is dissolved in 20ml acetone, dropwise adds in butyrolactam-triethylamine solution, stirring at normal temperature 2h under nitrogen protection by 4-chloromethyl benzoic acid chlorides simultaneously.Cross afterwards and filter triethylamine hydrochloride, in filtrate, add triethylamine 2.02g, return stirring 3h.
Evaporate to dryness filtrate.Add 20ml acetone in gained solid, heated and stirred, filter and obtain white solid.Weigh after drying, productive rate is 85% (productive rate=actual yield/theoretical maximum production) as calculated.MS-ESI(m/z):[M]
+calculatedforC
18H
27N
2O
2 +303.2,found:303.4.
Embodiment 2
Valerolactim 0.02mol is dissolved in 20ml acetone, adds triethylamine 0.04mol.4-chloromethyl benzoic acid chlorides 0.02mol is dissolved in 20ml acetone, dropwise adds in Valerolactim-triethylamine solution, stirring at normal temperature 3h under nitrogen protection by 4-chloromethyl benzoic acid chlorides simultaneously.Cross afterwards and filter triethylamine hydrochloride, in filtrate, add triethylamine 0.02mol, return stirring 4h.
Evaporate to dryness filtrate.Add 20ml acetone in gained solid, heated and stirred, filter and obtain white solid.Weigh after drying, calculating productive rate is 91%.MS-ESI(m/z):[M]
+calculatedforC
19H
29N
2O
2 +317.2,found:317.1。
Embodiment 3
Hexanolactam 0.1mol is dissolved in 20ml acetone, adds triethylamine 0.08mol.4-chloromethyl benzoic acid chlorides 0.02mol is dissolved in 20ml acetone, dropwise adds in hexanolactam-triethylamine solution, stirring at normal temperature 10h under nitrogen protection by 4-chloromethyl benzoic acid chlorides simultaneously.Cross afterwards and filter triethylamine hydrochloride, in filtrate, add triethylamine 0.1mol, return stirring 8h.
Evaporate to dryness filtrate.Add 20ml acetone in gained solid, heated and stirred, filter and obtain white solid.Weigh after drying, productive rate is 83%.MS-ESI(m/z):[M]
+calculatedforC
20H
31N
2O
2 +331.2,found:331.2。
Embodiment 4
Hexanolactam 0.02mol is dissolved in 20ml acetone, adds triethylamine 4.04g.4-chloromethyl benzoic acid chlorides 0.02mol is dissolved in 20ml acetone, dropwise adds in hexanolactam-triethylamine solution, stirring at normal temperature 2h under nitrogen protection by 4-chloromethyl benzoic acid chlorides simultaneously.Cross afterwards and filter triethylamine hydrochloride, in filtrate, add triethylamine 0.02mol, return stirring 5h.
Evaporate to dryness filtrate.Add 20ml acetone in gained solid, heated and stirred, filter and obtain white solid.Weigh after drying, productive rate is 87%.
Embodiment 5
Oenantholactam 0.02mol is dissolved in 20ml acetone, adds triethylamine 0.04mol.4-chloromethyl benzoic acid chlorides 0.02mol is dissolved in 20ml acetone, dropwise adds in oenantholactam-triethylamine solution, stirring at normal temperature 4h under nitrogen protection by 4-chloromethyl benzoic acid chlorides simultaneously.Cross afterwards and filter triethylamine hydrochloride, in filtrate, add triethylamine 0.02mol, return stirring 4h.
Evaporate to dryness filtrate.Add 20ml acetone in gained solid, heated and stirred, filter and obtain white solid.Weigh after drying, productive rate is 93%.MS-ESI(m/z):[M]
+calculatedforC
21H
33N
2O
2 +345.2,found:345.3。
Embodiment 6
Spicy inner formyl amine 0.02mol is dissolved in 20ml acetone, adds triethylamine 0.04mol.4-chloromethyl benzoic acid chlorides 0.02mol is dissolved in 20ml acetone, dropwise adds in spicy inner formyl amine-triethylamine solution, stirring at normal temperature 5h under nitrogen protection by 4-chloromethyl benzoic acid chlorides simultaneously.Cross afterwards and filter triethylamine hydrochloride, in filtrate, add triethylamine 0.03mol, return stirring 4h.
Evaporate to dryness filtrate.Add 20ml acetone in gained solid, heated and stirred, filter and obtain white solid.Weigh after drying,
Productive rate is 89%.MS-ESI(m/z):[M]
+calculatedforC
22H
35N
2O
2 +359.3,found:359.2。
Embodiment 7
Lactan 0.02mol in the ninth of the ten Heavenly Stems is dissolved in 20ml acetone, adds triethylamine 0.02mol.4-chloromethyl benzoic acid chlorides 0.02mol is dissolved in 20ml acetone, dropwise adds in lactan-triethylamine solution in the ninth of the ten Heavenly Stems, stirring at normal temperature 3h under nitrogen protection by 4-chloromethyl benzoic acid chlorides simultaneously.Cross afterwards and filter triethylamine hydrochloride, in filtrate, add triethylamine (2.02g, 0.02mol), return stirring 4h.
Evaporate to dryness filtrate.Add 20ml acetone in gained solid, heated and stirred, filter and obtain white solid.Weigh after drying, productive rate is 85%.MS-ESI(m/z):[M]
+calculatedforC
23H
37N
2O
2 +373.3,found:373.2。
Embodiment 8
Caprinolactam 0.02mol is dissolved in 20ml acetone, adds triethylamine 0.02mol.4-chloromethyl benzoic acid chlorides 0.1mol is dissolved in 20ml acetone, dropwise adds in caprinolactam-triethylamine solution, stirring at normal temperature 10h under nitrogen protection by 4-chloromethyl benzoic acid chlorides simultaneously.Cross afterwards and filter triethylamine hydrochloride, in filtrate, add triethylamine 0.02mol, return stirring 8h.
Evaporate to dryness filtrate.Add 20ml acetone in gained solid, heated and stirred, filter and obtain white solid.Weigh after drying, obtaining productive rate is 81%.MS-ESI(m/z):[M]
+calculatedforC
24H
39N
2O
2 +387.3,found:387.1。
Embodiment 9
Butyrolactam 0.02mol is dissolved in 20ml acetone, adds triethylamine 0.02mol.4-chloromethyl benzoic acid chlorides 0.02mol is dissolved in 20ml acetone, dropwise adds in butyrolactam solution, stirring at normal temperature 3h under nitrogen protection by 4-chloromethyl benzoic acid chlorides simultaneously.Cross afterwards and filter triethylamine hydrochloride, in filtrate, add dimethyl amine 0.02mol, return stirring 4h.
Evaporate to dryness filtrate.Add 20ml acetone in gained solid, heated and stirred, filter and obtain white solid.Weigh after drying, productive rate is 91%.MS-ESI(m/z):[M]
+calculatedforC
16H
23N
2O
2 +275.2,found:275.1。
Embodiment 10
Hexanolactam 0.02mol is dissolved in 20ml acetonitrile, adds triethylamine 0.02mol.4-chloromethyl benzoic acid chlorides 0.02mol is dissolved in 20ml acetonitrile, dropwise adds in lactan solution, stirring at normal temperature 3h under nitrogen protection by 4-chloromethyl benzoic acid chlorides simultaneously.Cross afterwards and filter triethylamine hydrochloride, in filtrate, add dimethyl amine 0.02mol, return stirring 4h.
Evaporate to dryness filtrate.Add 20ml acetone in gained solid, heated and stirred, filter and obtain white solid.Weigh after drying, productive rate is 87%.Nucleus magnetic resonance and and mass spectrometric measurement data as follows:
1HNMR(400MHz,CDCl
3):δ7.74(d,J＝8.1Hz,2H),7.52(d,J＝8.1Hz,2H),5.08(s,2H),3.96(s,2H),3.62(q,J＝7.2Hz,2H),3.18(s,6H),2.66(d,J＝6.4Hz,2H),1.82(s,6H),1.39(t,J＝7.2Hz,3H)；
13CNMR(100MHz,CDCl
3):δ177.6,172.8,138.5,133.0,130.2,127.7,65.9,59.2,48.8,44.8,38.6,29.2,28.9,23.5,8.4；MS-ESI(m/z):[M]
+calculatedforC
18H
27N
2O
2 +303.2,found:303.1。
Embodiment 11
Hexanolactam 0.02mol is dissolved in 20ml toluene, adds triethylamine 0.02mol.4-chloromethyl benzoic acid chlorides 0.02mol is dissolved in 20ml toluene, dropwise adds in lactan solution, stirring at normal temperature 3h under nitrogen protection by 4-chloromethyl benzoic acid chlorides simultaneously.Cross afterwards and filter triethylamine hydrochloride, in filtrate, add dimethyl butylamine 0.03mol, return stirring 4h.
Evaporate to dryness filtrate.Add 20ml acetone in gained solid, heated and stirred, filter and obtain white solid.Weigh after drying, productive rate is 85%.Nucleus magnetic resonance and and mass spectrometric measurement data as follows:
1HNMR(400MHz,CDCl3)δ7.72(d,J＝8.1Hz,2H),7.52(d,J＝8.1Hz,2H),5.07(s,2H),3.96(s,2H),3.54–3.38(m,2H),3.21(s,6H),2.66(d,J＝6.3Hz,2H),1.82(s,6H),1.75(s,2H),1.36(dd,J＝14.8,7.4Hz,2H),0.94(t,J＝7.3Hz,3H).
13CNMR(100MHz,CDCl
3)δ177.8,173.0,138.7,133.2,130.3,127.9,66.6,63.5,49.6,45.0,38.7,29.4,29.0,24.5,23.6,19.6,13.7.HRMS-ESI:calculatedfor[M]
+(C
20H
31N
2O
2):m/z331.2386found:331.0853。
Embodiment 12
Hexanolactam 0.02mol is dissolved in 20ml acetonitrile, adds triethylamine 0.02mol.4-chloromethyl benzoic acid chlorides 0.02mol, is dissolved in 20ml acetonitrile, dropwise adds in lactan solution, stirring at normal temperature 3h under nitrogen protection by 4-chloromethyl benzoic acid chlorides simultaneously.Cross afterwards and filter triethylamine hydrochloride, in filtrate, add dimethylhexylamine 0.03mol, return stirring 4h.
Evaporate to dryness filtrate.Add 20ml acetone in gained solid, heated and stirred, filter and obtain white solid.Weigh after drying, productive rate is 89%.Nucleus magnetic resonance and and mass spectrometric measurement data as follows:
1HNMR(400MHz,CDCl
3)δ7.73(d,J＝8.1Hz,2H),7.52(d,J＝8.1Hz,2H),5.12(s,2H),3.95(s,2H),3.5–3.33(m,2H),3.23(s,6H),2.66(d,J＝6.4Hz,2H),1.82(s,6H),1.75(s,2H),1.27(d,J＝10.0Hz,6H),0.84(t,J＝6.8Hz,3H).
13CNMR(100MHz,CDCl
3)δ177.7,172.9,138.9,133.2,130.2,127.9,66.5,63.8,49.6,45.0,38.8,31.3,29.4,29.1,25.9,23.7,22.8,22.3,13.9.HRMS-ESI:calculatedfor[M]
+(C
22H
35N
2O
2):m/z359.2699found:359.1041。
Embodiment 13
Hexanolactam 0.02mol is dissolved in 20ml tetrahydrofuran (THF), adds triethylamine 0.02mol.4-chloromethyl benzoic acid chlorides 0.02mol is dissolved in 20ml tetrahydrofuran (THF), dropwise adds in lactan solution, stirring at normal temperature 2h under nitrogen protection by 4-chloromethyl benzoic acid chlorides simultaneously.Cross afterwards and filter triethylamine hydrochloride, add dimethyl amino dodecane 0.03mol in filtrate, return stirring 3h.
Evaporate to dryness filtrate.Add 20ml acetone in gained solid, heated and stirred, filter and obtain white solid.Weigh after drying, productive rate is 83%.Nucleus magnetic resonance and and mass spectrometric measurement data as follows:
1HNMR(400MHz,CDCl
3)δ7.72(d,J＝8.1Hz,2H),7.52(d,J＝8.1Hz,2H),5.13(s,2H),3.95(s,2H),3.54–3.36(m,2H),3.23(s,6H),2.66(d,J＝6.2Hz,2H),1.82(s,6H),1.74(s,2H),1.40–1.09(m,18H),0.84(t,J＝6.8Hz,3H).
13CNMR(100MHz,CDCl
3)δ177.7,173.0,138.9,133.2,130.3,128.0,66.6,63.8,49.6,45.0,38.8,31.8,29.5,29.4,29.2,29.2,29.1,26.3,23.7,22.9,22.6,14.1.HRMS-ESI:calculatedfor[M]
+(C
28H
47N
2O
2):m/z443.3638found:443.1593。
Embodiment 14
Hexanolactam 0.02mol is dissolved in 20ml acetonitrile, adds triethylamine 0.02mol.4-chloromethyl benzoic acid chlorides 0.02mol is dissolved in 20ml acetonitrile, dropwise adds in lactan solution, stirring at normal temperature 3h under nitrogen protection by 4-chloromethyl benzoic acid chlorides simultaneously.Cross afterwards and filter ammonium chloride, add dimethyl cetylamine 0.03mol in filtrate, return stirring 4h.
Evaporate to dryness filtrate.Add 20ml acetone in gained solid, heated and stirred, filter and obtain white solid.Weigh after drying, productive rate is 89%.Nucleus magnetic resonance and and mass spectrometric measurement data as follows:
1HNMR(400MHz,CDCl
3)δ7.73(d,J＝8.1Hz,2H),7.52(d,J＝8.0Hz,2H),5.12(s,2H),3.96(s,2H),3.54–3.35(m,2H),3.23(s,6H),2.66(d,J＝6.0Hz,2H),1.82(s,6H),1.74(s,2H),1.23(s,26H),0.85(t,J＝6.7Hz,3H).
13CNMR(100MHz,CDCl
3)δ177.7,173.00,138.9,133.2,130.3,128.0,66.7,63.7,59.8,49.6,38.8,31.9,29.7,29.6,29.6,29.6,29.5,29.4,29.3,29.3,29.1,27.4,26.3,23.7,22.9,22.7,14.1.HRMS-ESI:calculatedfor[M]
+(C
32H
55N
2O
2):m/z499.4264found:499.1897.
Although the present invention with preferred embodiment openly as above; but it is also not used to limit the present invention, any person skilled in the art, without departing from the spirit and scope of the present invention; all can do various changes and modification, what therefore protection scope of the present invention should define with claims is as the criterion.
Claims (10)
1. a method for synthesizing cationic bleach-activating agent, is characterized in that, described method comprises the steps:
1) utilize solvent to dissolve 4-chloromethyl benzoic acid chlorides and lactan respectively, ethylamine is in lactan solution repeatedly, obtains 4-chloromethyl benzoic acid chlorides solution and lactan-triethylamine solution;
2) under nitrogen protection by step 1) the 4-chloromethyl benzoic acid chlorides dropwise of gained joins in lactan-triethylamine solution, and temperature of reaction is 20-50 DEG C, is uniformly mixed rear acquisition lactan-triethylamine-4-chloromethyl benzoic acid chlorides solution;
3) triethylamine hydrochloride filtering generation is crossed;
4) tertiary amine is joined step 3) return stirring process in the solution of products therefrom, obtain reaction soln;
5) evaporate to dryness step 4) gained reaction soln, obtain target product after washing gained solid.
2. method according to claim 1, it is characterized in that, described method is according to every mol4-chloromethyl benzoic acid chlorides, adds 1 ~ 4mol triethylamine, 0.2 ~ 5mol lactan, 0.2 ~ 5mol tertiary amine.
3. method according to claim 1, it is characterized in that, the structure of described target product is such as formula shown in (I):
In formula, n is 1,2,3,4,5,6 or 7; Alkyl R
1, R
2, R
3carbon atom number be arbitrary number in 1-16.
4. method according to claim 3, is characterized in that, described alkyl R
1, R
2, R
3carbonatoms be 1,2,4,6,8,10,12,14 or 16.
5. method according to claim 1, is characterized in that, step 2) described in time of being uniformly mixed be 2-10h.
6. method according to claim 1, is characterized in that, step 4) time of described return stirring is 3-8h.
7. method according to claim 1, it is characterized in that, described triethylamine, 4-chloromethyl benzoic acid chlorides, lactan, tertiary amine add according to mol ratio (2 ~ 1): 1:1:1.
8. method according to claim 1, is characterized in that, step 1) described solvent is any one or the two or more mixing in toluene, tetrahydrofuran (THF), ethyl acetate, acetonitrile or acetone.
9. method according to claim 3, it is characterized in that, concrete steps are as follows:
1) take acetonitrile as solvent, be 4-chloromethyl benzoic acid chlorides according to mol ratio: the ratio of lactan=1:1.1 dissolves 4-chloromethyl benzoic acid chlorides and lactan respectively, again triethylamine is dissolved in lactan solution, obtains 4-chloromethyl benzoic acid chlorides solution and lactan-triethylamine solution; According to mol ratio triethylamine: 4-chloromethyl benzoic acid chlorides=2 ~ 1:1 adds triethylamine;
2) by step 1) the 4-chloromethyl benzoic acid chlorides dropwise of gained joins in lactan-triethylamine solution, and in 20-50 DEG C, stirred under nitrogen atmosphere mixing 3h, obtains lactan-triethylamine-4-chloromethyl benzoic acid chlorides solution;
3) triethylamine hydrochloride filtering generation is crossed;
4) more in molar ratio for tertiary amine: tertiary amine is joined step 3 by the ratio of 4-chloromethyl benzoic acid chlorides=1:1) return stirring process 4h in the solution of gained, obtain reaction soln;
5) evaporate to dryness step 4) gained reaction soln, obtain object product after utilizing washing with acetone gained solid.
10. the cationic bleach activators that described in claim 1-9, arbitrary described method obtains.
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Application publication date: 20151216 |