CN102093291A - Preparation method of N-[4-(triethyl aminomethyl) benzoyl] caprolactam bromide - Google Patents
Preparation method of N-[4-(triethyl aminomethyl) benzoyl] caprolactam bromide Download PDFInfo
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Abstract
The invention discloses a synthesis method of N-[4-(triethyl aminomethyl) benzoyl]caprolactam bromide. The method comprises the following four steps: chloridizing methylbenzoic acid and then carrying out reaction on chloridized methylbenzoic acid and caprolactam; and carrying out benzyl position-halogenation reaction and triethylamine salifying reaction so as to obtain the white solid N-[4-(triethyl aminomethyl) benzoyl] caprolactam bromide finally. The synthesis method is simple in synthesis process and convenient for operation; the N-[4-(triethyl aminomethyl) benzoyl]caprolactam bromide prepared by the synthesis method has the advantages of wide raw material source, cheap price, low production cost cleanliness and no pollution and is environment-friendly; and yield of the product is high, and the yield of the final product is 55-65%.
Description
Technical field
The present invention relates to a kind of N-[4-(triethyl aminomethyl) benzoyl] preparation method of hexanolactam bromide, belong to the field of chemical synthesis, this material is a cold bleaching washing activator, is a kind of important fine chemicals.
Background technology
N-[4-(triethyl aminomethyl) benzoyl] the halid application of hexanolactam is very extensive, can be used as the activator of cold bleaching washing.The technological innovation of dyeing has promoted the development research to this activator.Oxygen floats activator, and to carry out textile bleaching be a significant innovation to traditional hydrogen peroxide bleaching, can reduce heat and float temperature or shorten banking up the time that cold rolling heap scourings and bleaching. and improve the quality of products.The oxygen of developing and developing both at home and abroad floats activator for this reason TAED, NBOS, TBCC, TBCB and THCTS.
TAED is a tetraacetyl ethylene diamine, has the cold bleaching effect, has promoted the application of the cryogenic oxygen bleaching process of textiles, and under cold condition, whiteness has reduced fiber degree of injury at high temperature apparently higher than independent use hydrogen peroxide.But 60-70 ℃ of its bleaching optimum temps is still higher.
NOBS is called as s-generation bleach-activating agent. belong to lower efficient cryogenic type activator 20th century the mid-80 of oxygen release activation energy to the initial stage nineties. and external numerous chemical companies that enjoy high reputation, as: Proctor﹠amp; Gamble (P﹠amp; G), companies such as Shell, Dupone, Uniliver, Kao, Lion have delivered a large amount of patents with regard to the synthetic of NOBS with prescription.Crossing peroxide two n-nonanoic acids that generate the peroxide n-nonanoic acid under the oxygen anion effect and do not have oxidation capacity.40-50 ℃ can discharge nonyl peroxy acid negatively charged ion, little to fibre-tendering because temperature is low, but NOBS concentration in bleaching liquor is too high, unfavorable to bleaching.
After TAED and NOBS. developed the activator kind of cationic quaternary ammonium salt superoxide again.U.S. north california textile college of university and Turkey Istanbul university are studied the synthetic and application of cationic activation agent; in N-acyl caprolactam class; two of Application and Development kinds are: N-[4-(triethyl aminomethyl) benzoyl] hexanolactam halogenide and 6-[N; N, N-trimethylammonium ammonia methylene] the hexanolactam tosic acid.These two kinds of activators are active high, and bleaching temperature is low, have been subjected to paying close attention to widely.
N-[4-(triethyl aminomethyl) benzoyl wherein] shown in the halid structural formula of hexanolactam:
Wherein X represent halogen atom (Cl, Br);
Present N-[4-(triethyl aminomethyl) benzoyl] the halid synthetic method price of hexanolactam is higher, and therefore develop cost preparation method low, simple to operate and have great importance.
Present N-[4-(triethyl aminomethyl) benzoyl] the halid synthetic method of hexanolactam, mainly by the control of external chemical company, domesticly do not see manufacturing enterprise.External Baillity GM.The procter﹠amp; The patent US 5686015 of gamble company; reported N-[4-(triethyl aminomethyl) benzoyl in the text] hexanolactam is halid synthetic; by to chloromethyl benzoic acid chlorides respectively with diethylamine and hexanolactam dehydrochlorination, and then obtain quaternary ammonium salt with chlorine (bromine) ethane reaction.Chloromethyl benzoic acid chlorides is cost an arm and a leg, and is gas under the halogen ethane normal temperature and pressure, complicated operation, and processing unit requires high, has the hydrogenchloride toxic gas to produce in the process.
Summary of the invention
The object of the invention is in order to solve above-mentioned N-[4-(triethyl aminomethyl) benzoyl] expensive raw material price among the hexanolactam bromide preparation method; complicated operation; processing unit requires high; building-up process problems such as toxic gas discharging are arranged and provide that a kind of raw materials cost is lower, building-up process is simple, easy and simple to handle, no toxic gas discharging etc., and high N-[4-(triethyl aminomethyl) benzoyl of final yield] preparation method of hexanolactam bromide.
Technical scheme of the present invention
A kind of N-[4-of the present invention (triethyl aminomethyl) benzoyl] synthetic method of hexanolactam bromide, with the p-methylbenzoic acid is raw material, after chlorination, react with hexanolactam, at process benzyl position halo, last and triethylamine salify is final product N-[4-(triethyl aminomethyl) benzoyl] the hexanolactam bromide, specifically comprise 4 steps, the reaction formula synoptic diagram of its building-up process is as shown in Figure 1: promptly the chlorination reaction of p-methylbenzoic acid generates that (wherein p-methylbenzoic acid is a raw material to methyl benzoyl chloride, sulfur oxychloride is a chlorination reagent, and chloroform is a solvent); Methyl benzoyl chloride and hexanolactam reaction are generated methyl benzoyl hexanolactam (be raw material to methyl benzoyl chloride and hexanolactam wherein, triethylamine provides alkaline environment); It (is raw material to the methyl benzoyl hexanolactam wherein that methyl benzoyl hexanolactam benzyl position bromo-reaction is generated the brooethyl benzoyl caprolactam; the NBS(N-bromo-succinimide) is brominated reagent; the AIBN(Diisopropyl azodicarboxylate) or the BPO(benzoyl peroxide) as initiator, CCl
4Be solvent); At last brooethyl benzoyl caprolactam and triethylamine salt-forming reaction are finally generated N-[4-(triethyl aminomethyl) benzoyl] hexanolactam bromide (to brooethyl benzoyl group hexanolactam and triethylamine is raw material, and acetone is solvent).
A kind of N-[4-(triethyl aminomethyl) benzoyl] synthetic method of hexanolactam bromide, comprise following concrete steps:
(1), the chlorination of p-methylbenzoic acid generates methyl benzoyl chloride
Add the chloroformic solution of p-methylbenzoic acid in there-necked flask, the back adds sulfur oxychloride, and oil bath is warming up to reflux state under the mechanical stirring condition, reaction 2～4h, and removal of solvent under reduced pressure and remaining sulfur oxychloride get little yellow liquid to methyl benzoyl chloride;
P-methylbenzoic acid is a p-methylbenzoic acid with the molecular volume ratio of chloroform in the chloroformic solution of wherein said p-methylbenzoic acid: chloroform concentration is preferably 1mol:0.6L and calculates;
The amount of the sulfur oxychloride that adds is the amount of sulfur oxychloride by its mol ratio with p-methylbenzoic acid: the amount of p-methylbenzoic acid is 1.2～1.6:1 calculating;
(2), methyl benzoyl chloride and hexanolactam reaction are generated the methyl benzoyl hexanolactam
In there-necked flask, add hexanolactam, trichloromethane and triethylamine stirring and dissolving, get solution A, at ambient temperature, with step (1) gained methyl benzoyl chloride is dissolved in the chloroform, must be to the methyl benzoyl chloride chloroformic solution, after it slowly is added drop-wise in the above-mentioned gained solution A again, dripping the process control drop rate is 0.1ml/s, be warming up to reflux state after dropwising, reaction 2h, removal of solvent under reduced pressure gets little yellow solid, behind the less water thorough washing, with acetone or recrystallizing methanol, get white solid again to the methyl benzoyl hexanolactam;
Described in the embodiment of the invention in the chloroformic solution of methyl benzoyl chloride to the volume ratio of methyl benzoyl chloride and chloroform by to methyl benzoyl chloride: chloroform is preferably 3:10 and calculates;
The add-on of hexanolactam, trichloromethane and triethylamine is by hexanolactam: trichloromethane: triethylamine is 1mol:0.4L:1mol;
(3), methyl benzoyl hexanolactam benzyl position halogenating reaction is generated the brooethyl benzoyl caprolactam
In there-necked flask, add step (2) gained to the methyl benzoyl hexanolactam, the NBS(N-bromo-succinimide), the AIBN(Diisopropyl azodicarboxylate) or the BPO(benzoyl peroxide), add tetracol phenixin under stirring and make solvent, be warming up to reflux state, reaction 4～5h;
Remove and desolvate,, use the acetone or alcohol recrystallization again, get white solid the brooethyl benzoyl caprolactam with an amount of water thorough washing;
Wherein to methyl benzoyl hexanolactam, NBS, BPO(AIBN) and the proportioning of tetracol phenixin promptly to methyl benzoyl hexanolactam, NBS, BPO(AIBN) and tetracol phenixin 1mol:1mol:0.08mol:1.6L
(4), brooethyl benzoyl caprolactam and triethylamine salt-forming reaction are generated N-[4-(triethyl aminomethyl) benzoyl] the hexanolactam bromide
In there-necked flask, add step (3) gained to the brooethyl benzoyl caprolactam, triethylamine mix to stir down and adds acetone again, is warming up to reflux state, reaction 2h;
Remove and desolvate, use the dehydrated alcohol recrystallization, final white solid N-[4-(triethyl aminomethyl) benzoyl that gets] the hexanolactam bromide;
Wherein the proportioning of brooethyl benzoyl caprolactam, triethylamine and acetone is pressed the brooethyl benzoyl caprolactam: triethylamine: acetone (acetonitrile) is 1mol:1～3mol:1.60L.
Beneficial effect of the present invention
The present invention has adopted tolyl acid, lactan and triethylamine as raw material; synthetic N-[4-of the present invention (triethyl aminomethyl) benzoyl] raw material sources that adopted of the halid synthetic method of hexanolactam are wide; therefore low price has the low characteristics of production cost.
Because building-up process of the present invention is popular response, it is simple to have building-up process, characteristics easy and simple to handle.
The material that does not have during the present invention is synthetic to poison produces, the process cleanliness without any pollution, and reaction process is environmentally friendly.
In addition, N-[4-of the present invention (triethyl aminomethyl) benzoyl group] preparation method of hexanolactam bromide, the total recovery of the finished product of the present invention is 55～65%, therefore synthetic total recovery is higher.
Embodiment
Below by embodiment the present invention is further set forth, but do not limit the present invention.
Used raw material, the reagent of the present invention is commercially available AR, CP level.
Gained intermediate product of the present invention and final product adopt nucleus magnetic resonance to detect.
The calculation formula of the intermediate product of gained of the present invention and the productive rate of final product and yield is as follows:
To the productive rate of methyl benzoyl hexanolactam with respect to p-methylbenzoic acid:
P-methylbenzoic acid in the following formula, to the methyl benzoyl hexanolactam, the methylbenzene acyl caprolactam is meant its quality respectively;
To the brooethyl benzoyl caprolactam with respect to productive rate to the methyl benzoyl hexanolactam:
In the following formula to the methyl benzoyl hexanolactam, to the brooethyl benzoyl caprolactam, the brooethyl benzoyl caprolactam is meant its quality respectively;
N-[4-(triethyl aminomethyl) benzoyl] the hexanolactam bromide is with respect to the productive rate to the brooethyl benzoyl caprolactam:
In the following formula to the brooethyl benzoyl caprolactam, (N-[4-(triethylamine methyl) benzoyl group] the hexanolactam bromide, the brooethyl benzoyl caprolactam is meant its quality respectively;
N-[4-(triethyl aminomethyl) benzoyl] total recovery=W of hexanolactam bromide
1* W
2* W
3
Embodiment 1
(1), in the there-necked flask of 100mL, add 6.8g (0.05mol) p-methylbenzoic acid, add 4.38mL (0.06mol) sulfur oxychloride under the 30mL chloroform stirring and dissolving, oil bath is warming up to reflux state under the mechanical stirring condition, the reaction 2～4h;
Removal of solvent under reduced pressure and remaining sulfur oxychloride get little yellow liquid to methyl benzoyl chloride;
(2), in there-necked flask, add 5.6g (0.05mol) hexanolactam, 20mL trichloromethane and 7.22ml(0.05mol) the triethylamine stirring and dissolving, at ambient temperature, with step (1) gained methyl benzoyl chloride is dissolved in the 20mL chloroform, slowly drip, be warming up to reflux state after dropwising, reaction 2h;
Little yellow solid of removal of solvent under reduced pressure behind the less water thorough washing, is used the acetone or alcohol recrystallization again, gets white solid to the methyl benzoyl hexanolactam; Mp:130～132 ° C is with respect to the productive rate 85% of p-methylbenzoic acid;
(3), in the there-necked flask of 250mL, add the white solid of 14.43g (0.0624mol) step (2) gained to the methyl benzoyl hexanolactam, 11.12g (0.0624mol) NBS, 1.12gAIBN stirs adding 100mL tetracol phenixin down, be warming up to reflux state, reaction 5h;
Remove and desolvate,, use the acetone or alcohol recrystallization again, get white solid the brooethyl benzoyl caprolactam with an amount of water thorough washing; Mp:120～122 ° C is 75% with respect to the productive rate to the methyl benzoyl hexanolactam;
(4), in the there-necked flask of 50mL, add 7.6g(0.0245mol) the white solid of the final gained of step (3), 11mL(0.0736mol) triethylamine stirs and adds 40mL acetone down, is warming up to reflux state, reaction 2h;
Remove and desolvate, get white solid N-[4-(triethyl aminomethyl) benzoyl with the anhydrous methanol recrystallization] the hexanolactam bromide; Mp:214～215 ° C, with respect to the productive rate 86% to the brooethyl benzoyl caprolactam, total recovery is 55%.
Embodiment 2
(1), in the there-necked flask of 100mL, add 6.8g (0.05mol) p-methylbenzoic acid, the 30mL chloroform, stirring and dissolving adds 5.12mL (0.07mol) sulfur oxychloride, oil bath is warming up to reflux state under the mechanical stirring condition, reaction 2-4h,
Removal of solvent under reduced pressure and remaining sulfur oxychloride get little yellow liquid to methyl benzoyl chloride;
(2), in the 100mL there-necked flask, add 5.6g (0.05mol) hexanolactam, 20mL trichloromethane and 7mL
The triethylamine stirring and dissolving under the ice-water bath condition, with step (1) gained methyl benzoyl chloride is dissolved in the 20ml chloroform, slowly drips, and reacts 2h after dropwising at ambient temperature;
Little yellow solid of removal of solvent under reduced pressure behind the less water thorough washing, is used acetone recrystallization again, gets white solid to the methyl benzoyl hexanolactam; The mp:130-132 of gained white solid ° C is with respect to the productive rate 70% of p-methylbenzoic acid;
(3), in the there-necked flask of 250mL, add the white solid of 5.35g (0.023mol) step (2) gained to the methyl benzoyl hexanolactam, 4.12g (0.023mol) NBS, 0.28gBPO stirs adding 40mL tetracol phenixin down, be warming up to reflux state, reaction 4～5h;
Remove and desolvate, with an amount of water thorough washing, use acetone recrystallization again, get white solid to the brooethyl benzoyl caprolactam, mp:120-122 ° of C is 87% with respect to the productive rate to the methyl benzoyl hexanolactam;
(4), in the there-necked flask of 100mL, add 7.6g(0.0245mol) the white solid of the final gained of step (3), 6.81mL(0.049mol) triethylamine stirs and adds 40mL acetone down, is warming up to reflux state, reaction 2h;
Remove and desolvate, get white solid N-[4-(triethyl aminomethyl) benzoyl with the anhydrous methanol recrystallization] the hexanolactam bromide, mp:213～215 ° C, with respect to the productive rate 88% to the brooethyl benzoyl caprolactam, total recovery is 54%.
Embodiment 3
(1), in the there-necked flask of 100mL, add 6.8g (0.05mol) p-methylbenzoic acid, the dissolving of 30mL chloroform is stirred and is added 5.84mL (0.08mol) sulfur oxychloride down, oil bath is warming up to reflux state under the mechanical stirring condition, reaction 2～4h;
Removal of solvent under reduced pressure and remaining sulfur oxychloride get little yellow liquid to methyl benzoyl chloride;
(2), in there-necked flask, add 5.6g (0.05mol) hexanolactam, 20mL trichloromethane and 7mL triethylamine stirring and dissolving, at ambient temperature, with step (1) gained methyl benzoyl chloride is dissolved in the 20mL chloroform, slowly drip, be warming up to reflux state after dropwising, reaction 2h;
Little yellow solid of removal of solvent under reduced pressure behind the less water thorough washing, is used the acetone or alcohol recrystallization again, gets white solid to the methyl benzoyl hexanolactam; Mp:130～132 ° C is with respect to the productive rate 87% of p-methylbenzoic acid;
(3), in the there-necked flask of 250mL, add the white solid of 5.5g (0.023mol) step (2) gained, 4.12g (0.023mol) NBS, 0.28gBPO stirs and adds the 40mL acetonitrile down, is warming up to reflux state, reaction 4～5h;
Remove and desolvate, refrigeration is filtered, and with an amount of water thorough washing, uses acetone recrystallization again, gets white solid to the brooethyl benzoyl caprolactam, and mp:120～122 ° C is 86% with respect to the productive rate to the methyl benzoyl hexanolactam;
(4), in the there-necked flask of 100mL, add 7.7g(0.0245mol) white of the final gained of step (3)
Solid, 3.4mL(0.024mol) triethylamine stirs adding 40mL acetonitrile down, is warming up to backflow
State, reaction 2h;
Remove and desolvate, get white solid N-[4-(triethyl aminomethyl) benzoyl with the anhydrous methanol recrystallization] the hexanolactam bromide, mp:214～215 ° C, with respect to the productive rate 84% to the brooethyl benzoyl caprolactam, total recovery is 63%.
Above said content only is the basic explanation of the present invention under conceiving, and according to technical scheme of the present invention institute
Any equivalent transformation of doing all should belong to protection scope of the present invention.
Claims (6)
1. a N-[4-(triethyl aminomethyl) benzoyl] synthetic method of hexanolactam bromide; it is characterized in that with the p-methylbenzoic acid being raw material; after chlorination, react with hexanolactam; at process benzyl position halo, last and triethylamine salify is final product N-[4-(triethyl aminomethyl) benzoyl] the hexanolactam bromide.
2. a kind of N-[4-as claimed in claim 1 (triethyl aminomethyl) benzoyl] synthetic method of hexanolactam bromide, it is characterized in that its concrete synthesis step is as follows:
(1), the chlorination of p-methylbenzoic acid generates methyl benzoyl chloride
Add the chloroformic solution of p-methylbenzoic acid in there-necked flask, the back adds sulfur oxychloride, and oil bath is warming up to reflux state under the mechanical stirring condition, reaction 2～4h, and removal of solvent under reduced pressure and remaining sulfur oxychloride get little yellow liquid to methyl benzoyl chloride;
The amount of the sulfur oxychloride that adds is the amount of sulfur oxychloride by the mol ratio of itself and p-methylbenzoic acid: the amount of p-methylbenzoic acid is 1.2
～1.6:1 calculate;
(2), methyl benzoyl chloride and hexanolactam reaction are generated the methyl benzoyl hexanolactam
In there-necked flask, add hexanolactam, trichloromethane and triethylamine stirring and dissolving, get solution A, at ambient temperature, with step (1) gained methyl benzoyl chloride is dissolved in the chloroform, must be to behind the methyl benzoyl chloride chloroformic solution, it slowly is added drop-wise in the above-mentioned gained solution A again, dripping the process control drop rate is 0.1ml/s, be warming up to reflux state after dropwising, reaction 2h, removal of solvent under reduced pressure gets little yellow solid, behind the less water thorough washing, with acetone or recrystallizing methanol, get white solid again to the methyl benzoyl hexanolactam;
The add-on of hexanolactam, trichloromethane and triethylamine is by hexanolactam: trichloromethane: triethylamine is 1mol:0.8L:0.14L;
(3), methyl benzoyl hexanolactam benzyl position halogenating reaction is generated the brooethyl benzoyl caprolactam
In there-necked flask, add step (2) gained to the methyl benzoyl hexanolactam, the NBS(N-bromo-succinimide), the BPO(benzoyl peroxide), add tetracol phenixin under stirring and make solvent, be warming up to reflux state, reaction 4～5h, remove and desolvate, with an amount of water thorough washing, use the acetone or alcohol recrystallization again, get white solid to the brooethyl benzoyl caprolactam;
Wherein to the proportioning of methyl benzoyl hexanolactam, NBS, BPO and tetracol phenixin promptly to methyl benzoyl hexanolactam, NBS, BPO and tetracol phenixin 1mol:1mol:0.08mol:1.6L
(4), brooethyl benzoyl caprolactam and triethylamine salt-forming reaction are generated N-[4-(triethyl aminomethyl) benzoyl] the hexanolactam bromide
In there-necked flask, add step (3) gained to the brooethyl benzoyl caprolactam, triethylamine, mix to stir and add acetone down again, be warming up to reflux state, reaction 2h, remove and desolvate, use the dehydrated alcohol recrystallization, final white solid N-[4-(triethyl aminomethyl) benzoyl that gets] the hexanolactam bromide;
Wherein the proportioning of brooethyl benzoyl caprolactam, triethylamine and acetone is pressed the brooethyl benzoyl caprolactam: triethylamine: acetone is 1mol:3mol:1.60L.
3. a kind of N-[4-as claimed in claim 2 (triethyl aminomethyl) benzoyl] synthetic method of hexanolactam bromide, it is characterized in that BPO AIBN(Diisopropyl azodicarboxylate in its synthesis step (3)) alternative.
4. a kind of N-[4-as claimed in claim 2 (triethyl aminomethyl) benzoyl] synthetic method of hexanolactam bromide, it is characterized in that acetone substitutes with acetonitrile in its synthesis step (4).
5. as claim 2,3 or 4 arbitrary described a kind of N-[4-(triethyl aminomethyl) benzoyls] synthetic method of hexanolactam bromide, it is characterized in that the molecular volume ratio of p-methylbenzoic acid and chloroform is a p-methylbenzoic acid in the chloroformic solution of the p-methylbenzoic acid described in its synthesis step (1): chloroform concentration 1mol:0.6L calculates.
6. as the arbitrary described a kind of N-[4-of claim 5 (triethyl aminomethyl) benzoyl] synthetic method of hexanolactam bromide, it is characterized in that described in its synthesis step (1) in the chloroformic solution of methyl benzoyl chloride to the volume ratio of methyl benzoyl chloride and chloroform by to methyl benzoyl chloride: chloroform is that 3:10 calculates.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105330531A (en) * | 2015-12-14 | 2016-02-17 | 山东凯盛新材料有限公司 | Continuous production process of p-Methyl benzoyl chloride |
| CN105330532A (en) * | 2015-12-14 | 2016-02-17 | 山东凯盛新材料有限公司 | Preparation method of p-Methyl benzoyl chloride |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1124037A (en) * | 1993-05-20 | 1996-06-05 | 普罗格特-甘布尔公司 | Bleaching compositions comprising N-acyl caprolactam activators |
| CN1151158A (en) * | 1994-04-21 | 1997-06-04 | 普罗格特-甘布尔公司 | Cationic bleach activators |
| US5686015A (en) * | 1994-08-31 | 1997-11-11 | The Procter & Gamble Company | Quaternary substituted bleach activators |
-
2010
- 2010-12-10 CN CN201010581964A patent/CN102093291B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1124037A (en) * | 1993-05-20 | 1996-06-05 | 普罗格特-甘布尔公司 | Bleaching compositions comprising N-acyl caprolactam activators |
| CN1151158A (en) * | 1994-04-21 | 1997-06-04 | 普罗格特-甘布尔公司 | Cationic bleach activators |
| US5686015A (en) * | 1994-08-31 | 1997-11-11 | The Procter & Gamble Company | Quaternary substituted bleach activators |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105330531A (en) * | 2015-12-14 | 2016-02-17 | 山东凯盛新材料有限公司 | Continuous production process of p-Methyl benzoyl chloride |
| CN105330532A (en) * | 2015-12-14 | 2016-02-17 | 山东凯盛新材料有限公司 | Preparation method of p-Methyl benzoyl chloride |
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