CN1112350C - Compound phase-transferring quaternary ammonium salt catalyst in beta-hydroxyl structure and its preparation - Google Patents

Compound phase-transferring quaternary ammonium salt catalyst in beta-hydroxyl structure and its preparation Download PDF

Info

Publication number
CN1112350C
CN1112350C CN 00109759 CN00109759A CN1112350C CN 1112350 C CN1112350 C CN 1112350C CN 00109759 CN00109759 CN 00109759 CN 00109759 A CN00109759 A CN 00109759A CN 1112350 C CN1112350 C CN 1112350C
Authority
CN
China
Prior art keywords
transfer catalyst
ammonium salt
thiophosphate
alkyl
oxy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN 00109759
Other languages
Chinese (zh)
Other versions
CN1287021A (en
Inventor
罗必奎
尹应武
任鹰
陈梓林
郑长春
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing Tsinghua Unisplendour Insight Chemical Technology LLC
Original Assignee
Beijing Tsinghua Unisplendour Insight Chemical Technology LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Beijing Tsinghua Unisplendour Insight Chemical Technology LLC filed Critical Beijing Tsinghua Unisplendour Insight Chemical Technology LLC
Priority to CN 00109759 priority Critical patent/CN1112350C/en
Publication of CN1287021A publication Critical patent/CN1287021A/en
Application granted granted Critical
Publication of CN1112350C publication Critical patent/CN1112350C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Landscapes

  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention relates to a compound phase-transferring catalyst and a preparation method thereof, and the catalyst contains quaternary ammonium salt in a beta-hydroxyl structure.

Description

The quaternary ammonium salt complex phase transfer catalyst and the preparation thereof of beta-hydroxy structure
It contains the cationic of more than one to the present invention relates to be used for Catalytic Oxygen Rogor intermediate oxy-thiophosphate synthetic composite phase transfer catalyst, especially quaternary ammonium salt (or tertiary amine) phase-transfer catalyst, or contain at least a cationic quaternary ammonium salt (or tertiary amine) phase-transfer catalyst with the combination of non-ionic type phase-transfer catalyst.
Specifically, composite phase transfer catalyst of the present invention contains cationic quaternary ammonium salt (or tertiary amine) phase-transfer catalyst, is the quarternary ammonium salt compound with following general formula (I), the tertiary amine compound of general formula (II):
[R 1R 2R 3R 4N] +Cl - (I)
R 1R 2R 3N (II)
In the formula (I)
R 1Be C 1～C 18Alkyl or O 2N--CH (OH) CH (CH 2OH),
R 2, R 3Be C 1～C 18Alkyl, benzyl,
R 4Be benzyl, C 1～C 18Alkyl ,-CH 2COO (CH 2) nCH 3,-CH 2CONH (CH 2) nCH 3,
Wherein n is 0～8 integer,
X is Cl, Br, I,
Its condition is,
Work as R 1Be C 4～C 18During alkyl
R 2, R 3Be C 1～C 8Alkyl,
R 4Be C 1～C 18Alkyl, benzyl ,-CH 2COO (CH 2) nCH 3,-CH 2CONH (CH 2) nCH 3,
Wherein n is 0～8 integer,
Work as R 1Be O 2N-Ph-CH (OH) CH (CH 2OH) time,
R 2, R 3Be C 1～C 18Alkyl, benzyl,
R 4Be C 1～C 18Alkyl, benzyl ,-CH 2COO (CH 2) nCH 3,-CH 2CONH (CH 2) nCH 3,
In the formula (II)
R 1Be C 1～C 23Alkyl or benzyl,
R 2, R 3Be C 1～C 18Alkyl or benzyl;
Its condition is,
Work as R 1=C 1～C 23During alkyl,
R 2, R 3=C 1～C 18Alkyl or benzyl or H;
Work as R iDuring=benzyl,
R 2, R 3=C 1～C 18Alkyl or benzyl or H
The non-ionic type phase-transfer catalyst that composite phase transfer catalyst of the present invention contains for example is, polyalcohols, polyether compound, as
Molecular weight is 400～20000 polyoxyethylene glycol,
General formula is HO (CH 2CH 2O) nH n is 10～460 integer;
General formula is RO (CH 2CH 2O) condenses of the higher alcohols of nH and oxyethane, wherein R is C 6～C 23Alkyl, n is 6～23 integer;
Logical is R-Ph-(CH 2CH 2O) condenses of the alkylphenol of nH and oxyethane, wherein R is C 6～C 23Alkyl, n is 6～23 integer;
General formula is RCOO (CH 2CH 2O) condenses of the lipid acid of nH and oxyethane wherein is that R is C 6～C 23Alkyl, n is 6～23 integer;
60～the eighties once had many data to report (comprising patent) synthetic method of omethoate both at home and abroad, and its main method has: preceding amine-decomposing method, methyl isocyanate method, Bunte salt method, rear amine-decomposing.Wherein, the rear amine-decomposing of reporting among the Deutsches Wirtschafts Patent DD110883 has raw material and is easy to get, and process conditions is simple, and the advantage of convenient post-treatment is the at present domestic omethoate production method that generally adopts.Wherein the synthetic intermediate oxy-thiophosphate of omethoate is the key synthesis step that influences the omethoate total recovery, and the report that uses catalyzer to be used for the oxy-thiophosphate synthesis step is not all arranged both at home and abroad.The present inventor makes the synthetic omethoate oxy-thiophosphate of phase-transfer catalyst catalysis in the patent disclosure of CN94117723.8 with the quaternary ammonium salt of carbon eight to 28, has good catalytic effect, just also exists following shortcoming to require further improvement.
(1) in omethoate oxy-thiophosphate synthetic, when using single cationic quaternary ammonium salt face to change
During shifting catalyst, the cationic quaternary ammonium salt phase shifting catalyst that molecular weight is little, large usage quantity,
And catalytic activity is less.(2) there be serious the asking of emulsification again in the cationic quaternary ammonium salt phase transfer catalyst that molecular weight is big
Topic, thereby waterfall material when causing distilling, and in product, have residually, influence next workshop section
Produce.
The present inventor is for overcoming defective of the prior art, on the basis of being engaged in phase-transfer catalyst research for a long time, in conjunction with the practice that omethoate intermediate oxy-thiophosphate is produced cationic quaternary ammonium salt (or tertiary amine) phase-transfer catalyst has been done detailed research, found that the mixture that adopts cation quaternary ammonium salt (or tertiary amine) phase-transfer catalyst, perhaps, the mixture that one or more cation quaternary ammonium salt (or tertiary amine) phase-transfer catalyst and non-ionic type phase-transfer catalyst are made, beat all excellent effect is arranged, so finished the present invention.
One of purpose of the present invention provides and is used for omethoate intermediate oxy-thiophosphate synthetic composite phase transfer catalyst, it contains more than one cationic quaternary ammonium salt (or tertiary amine) class phase-transfer catalysts, or contains at least a cationic quaternary ammonium salt (or tertiary amine) the class phase-transfer catalyst that makes up with the non-ionic type phase-transfer catalyst.Composite phase transfer catalyst of the present invention can overcome the deficiency of single cationic phase-transfer catalyst on using, and optimizes greatly again in single cationic phase-transfer catalyst on catalytic activity.
Another object of the present invention provides the preparation method of the quaternary ammonium salt new compound with general formula (I) in the composite phase transfer catalyst of the present invention.
Another object of the present invention provides the preparation method of composite phase transfer catalyst of the present invention.
In petrochemical complex, agricultural chemicals, medicine and fine chemistry industry were produced, a lot of reaction systems were liquid～liquid nonhomogeneous system, solid-liquid nonhomogeneous system, are difficult to thorough mixing between material and the material.For example, omethoate intermediate oxy-thiophosphate is exactly a liquid～liquid nonhomogeneous system, and in order to allow it fully react, one to remove the technological reaction temperature too high, and the reaction times is long, thereby causes by product to increase, and influences the content and the yield of oxy-thiophosphate.We are being engaged on the research basis of phase-transfer catalyst for a long time, be used for the practice of the omethoate intermediate oxy-thiophosphate production of big industry at cationic phase-transfer catalyst, we are existing to make mixture with one or more cation quaternary ammonium salt (or tertiary amine) phase-transfer catalyst and the phase-transfer catalyst of non-ionic type, to reducing the temperature of omethoate intermediate oxy-thiophosphate, shorten the reaction times, reduce the generation of impurity, improve the content and the yield of omethoate intermediate oxy-thiophosphate, have better catalytic performance.This mainly is different in the partition ratio of water and organic phase because of the different phase-transfer catalyst of molecular structure, the partition ratio of some phase-transfer catalyst in water is big, and the phase-transfer catalyst that has partition ratio in organic phase is big, and it is favourable to adjust suitable branch pairing reaction.The phase shifting catalyst of used non-ionic type is a class polyalcohols, polyether compound among the present invention, owing to have the oxygen of unpaired electron on the chain, can improve hydrophilic, the lipophilicity of ionic phase-transfer catalyst, change the partition ratio of ionic phase-transfer catalyst in water and oil phase, thereby speed of response is accelerated; In addition, the oxygen on polyalcohols, the polyether compound chain has complexing action to the positive ion of reactant, and the negative ion number of reaction system is increased relatively, thus the reduction of the activation energy that helps reacting, and speed of response is accelerated; Moreover the adding of composite catalyst has reduced the interfacial tension of water and organic phase, makes two alternate contacts more abundant, and speed of response is accelerated greatly.From structure, quaternary ammonium salt positive charge ortho position has the compound of polar group that promoting catalysis is arranged, and speed of response is accelerated.
The said composite phase transfer catalyst of the present invention contains more than one cationic quaternary ammonium salt (or tertiary amine) phase-transfer catalyst, and cation quaternary ammonium salt (or tertiary amine) phase transition of more than one of inclusive NAND ionic phase transition agent combination is urged through agent.
Specifically, cationic quaternary ammonium salt (or tertiary amine) phase-transfer catalyst that composite phase transfer catalyst of the present invention contains is the quaternary ammonium compound with following general formula (I), the tertiary amine compounds of general formula (II):
[R 1R 2R 3R 4N] +Cl - (I)
R 1R 2R 3N (II)
In the formula (I)
R 1Be C 1～C 18Alkyl or O 2N-Ph-CH (OH) CH (CH 2OH),
R 2, R 3Be C 1～C 18Alkyl, benzyl, H,
R 4Be benzyl, C 1～C 18Alkyl ,-CH 2COO (CH 2) nCH 3,-CH 2CONH (CH 2) nCH 3,
Wherein n is 0～8 integer,
X is Cl, Br, I.Its condition is,
Work as R 1Be C 4～C 18During alkyl,
R 2, R 3Be C 1～C 8Alkyl, benzyl,
R 4Be C 1～C 18Alkyl ,-CH 2COO (CH 2) nCH 3,-CH 2CONH (CH 2) nCH 3,
Wherein n is 0～8 integer,
Work as R 1Be O 2N-Ph-CH (OH) CH (CH 2OH) time,
R 2, R 3Be C 1～C 18Alkyl, benzyl, H,
R 4Be C 1～C 18Alkyl, benzyl ,-CH 2COO (CH 2) nCH 3,-CH 2CONH (CH 2) nCH 3,
Wherein n is 0～8 integer.
Cationic quaternary ammonium salt catalyst in the composite phase transfer catalyst of the present invention, the preferred employing:
A: have quarternary ammonium salt compound as the general formula (I) of giving a definition,
R in the formula 1=C 4～C 18Alkyl,
R i, R 3=C 1～C 8Alkyl,
R 4=benzyl, C 1～C 8Alkyl,
X=Cl, Br, I; Perhaps,
B: have quarternary ammonium salt compound as the general formula (I) of giving a definition,
R in the formula 1=C 4～C 18Alkyl,
R 2, R 3=C 1～C 8Alkyl,
R 4=-CH 2COO (CH 2) nCH 3(n is 0～8 integer),
X=Cl, Br, I; Perhaps,
C: have quarternary ammonium salt compound as the general formula (I) of giving a definition,
R in the formula 1=C 4～C 18Alkyl,
R 2, R 3=C 1～C 8Alkyl,
R 4=-CH 2CONH (CH 2) nCH 3(n is 0～8 integer),
X=Cl, Br, I; Perhaps:
D: have quarternary ammonium salt compound as the general formula (I) of giving a definition,
In the formula: R 1=O 2N-Ph-CH (OH) CH (CH 2OH),
R 2, R 3, R 4=C 1～C 18Alkyl or benzyl,
X=Cl, Br, I; Perhaps:
E: have quarternary ammonium salt compound as the general formula (I) of giving a definition,
In the formula: R 1=O 2N-Ph-CH (OH) CH (CH 2OH),
R 2, R 3=C 1～C 18Alkyl or H,
R 4=-CH 2COO (CH 2) nCH 3(n is 0～8 integer),
X=Cl, Br, I; Perhaps:
F: have quarternary ammonium salt compound as the general formula (I) of giving a definition,
In the formula: R 1=O 2N-Ph-CH (OH) CH (CH 2OH),
R 2, R 3=C 1～C 18Alkyl or H,
R 4=-CH 2CONH (CH 2) nCH 3(n is 0～8 integer),
X=Cl, Br, I; In the formula (II)
R 1Be C 1～C 23Alkyl or benzyl,
R 2, R 3Be C 1～C 18Alkyl or benzyl;
Its condition is,
Work as R 1Be C 1～C 23Alkyl the time,
R 2, R 3Be C 1～C 18Alkyl or benzyl or H;
Work as R 1During=benzyl,
R 2, R 3=C 1～C 18Alkyl or benzyl or H.
Nonionic facies pattern phase-transfer catalyst in the composite phase transfer catalyst of the present invention is a class polyalcohols, polyether compound preferably, as:
Molecular weight is 600～20000 polyoxyethylene glycol,
General formula is HO (CH 2CH 2O) nHn is 10～460 integer;
General formula is RO (CH 2CH 2O) condenses of the higher alcohols of nH and oxyethane
Wherein R is C 6～C 23Alkyl n be 6～23 integer;
General formula is R-Ph-O (CH 2CH 2O) condenses of the alkylphenol of nH and oxyethane,
Wherein R is C 6～C 23Alkyl n be 6～23 integer;
General formula is RCOO (CH 2CH 2O) condenses of the lipid acid of nH and oxyethane
Wherein R is C 6～C 23Alkyl n be 6～23 integer;
Quaternary ammonium salt in the composite phase transfer catalyst of the present invention (or tertiary amine) compounds can be buied from the market, or by conventional method known in the art preparation, or according to the method preparation of hereinafter embodiment.Polyalcohols, polyether compound can be buied from the market.
For example, quaternary ammonium salt can be: [(CH 3CH 2) 4N] +Br -, [(CH 3CH 2CH 2CH 2) 4N] +Br -Trimethyl benzyl chlorination ingot, tri-methyl benzyl ammonium bromide, triethyl benzyl ammonia chloride, triethyl benzyl brometo de amonio, tributyl benzyl brometo de amonio, tributyl benzyl brometo de amonio, palmityl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, Dodecyl trimethyl ammonium chloride, cetyl trimethylammonium bromide, the octadecyl trimethylammonium bromide, Tetradecyl Trimethyl Ammonium Bromide, Trimethyllaurylammonium bromide, four octyl group brometo de amonios, the trioctylphosphine benzyl ammonium chloride, trioctylphosphine methyl ammonium iodide;
[O 2N-Ph-CH(OH)CH(CH 2OH)(CH 2Ph) 3N] +Cl -、
[O 2N-Ph-CH(OH)CH(CH 2CH 3)N] +I -、
[O 2N-Ph-CH(OH)CH(CH 2OH)(CH 2Ph) 2(CH 2COOCH 3)N] +Cl -、
[O 2N-Ph-CH(OH)CH(CH 2OH)(CH 2Ph) 2(CH 2CONHCH 3) +Cl -、
[CH 3(CH 2) 13N(CH 3) 2CH 2CONHCH 3] +Cl -、
[CH 3(CH 2) 13N(CH 3) 2CH 2Ph] +Br -、
[CH 3(CH 2) 13N(CH 3) 2CH 2COOCH 3] +Cl -、
[CH 3(CH 2) 15N(CH 3) 2CH 2Ph] +Br -、
[CH 3(CH 2) 13N(CH 3) 2(CH 2Ph)] +Cl -、
[CH 3(CH 2) 11N(CH 3) 2CH 2Ph] +Br -、
[CH 3(CH 2) 15N(CH 3) 2CH 2CONHCH 3] +Cl -、
[CH 3(CH 2) 17N(CH 3) 2CH 2Ph] +Br -、
[CH 3(CH 2) 15N(CH 3) 2CH 2COOCH 3] +Cl -、
[CH 3(CH 2) 17N(CH 3CH 3) 2CH 2Ph] +Br -、
[CH 3(CH 2) 15N(CH 3) 2(CH 2Ph)] +Cl -、
[CH 3(CH 2) 15N(CH 2CH 3) 2CH 2Ph] +Br -、
[CH 3(CH 2) 17N(CH 3) 2CH 2CONHCH 3] +Cl -、
[CH 3(CH 2) 15N(CH 2CH 3) 2CH 2Ph] +Br -、
[CH 3(CH 2) 17N(CH 3) 2CH 2COOCH 3] +Cl -、
[CH 3(CH 2) 11N(CH 2CH 3) 2CH 2Ph] +Br -、
[CH 3(CH 2) 17N(CH 3) 2(CH 2Ph)] +Cl -、
[CH 3(CH 2) 17N(CH 2CH 3) 2CH 2Ph] +Cl -、
[CH 3(CH 2) 11N(CH 3) 2CH 2CONHCH 3] +Cl -、
[CH 3(CH 2) 15N(CH 2CH 3) 2CH 2Ph] +Cl -、
[CH 3(CH 2) 11N(CH 3) 2CH 2COOCH 3] +Cl -、
[CH 3(CH 2) 15N(CH 2CH 3) 2CH 2Ph] +Cl -、
[CH 3(CH 2) 11N(CH 3) 2(CH 2Ph)] +Cl -、
[CH 3(CH 2) 11N(CH 2CH 3) 2CH 2Ph] +Cl -、
[O 2N-Ph-CH(OH)CH(CH 2OH)(CH 2Ph) 2(CH 2COOCH 2CH 3)N] +Cl -、
[O 2N-Ph-CH(OH)CH(CH 2OH)(CH 2Ph) 2N(CH 2CONHCH 2CH 3)] +Cl -、
[CH 3(CH 2) 13N(CH 3) 2CH 2CONHCH 2CH 3] +Cl -、
[CH 3(CH 2) 13N(CH 2CH 3) 2CH 2Ph] +Br -、
[CH 3(CH 2) 13N(CH 3) 2CH 2COOCH 2CH 3] +Cl -、
[CH 3(CH 2) 15N(CH 2CH 3) 2(CH 2Ph)] +Br -、
[CH 3(CH 2) 13N(CH 2CH 3) 2CH 2?Ph] +Cl -、
[CH 3(CH 2) 11N(CH 2?CH 3) 2CH 2Ph] +Br -、
[CH 3(CH 2) 15N(CH 3) 2CH 2CONHCH 2CH 3] +Cl -、
[CH 3(CH 2) 17N(CH 2CH 3) 2CH 2Ph] +Br -、
[CH 3(CH 2) 15N(CH 3) 2CH 2COOCH 2CH 3] +Cl -、
[CH 3(CH 2) 17N(CH 2CH 2CH 3) 2CH 2Ph] +Br -、
[CH 3(CH 2) 15N(CH 2CH 3) 2(CH 2Ph)] +Cl -、
[CH 3(CH 2) 15N(CH 2CH 2CH 3) 2CH 2Ph] +Br -、
[CH 3(CH 2) 17N(CH 3) 2CH 2CONHCH 2CH 3] +Cl -、
[CH 3(CH 2) 13N(CH 2CH 2CH 3) 2CH 2Ph] +Br -、
[CH 3(CH 2) 17N(CH 3) 2CH 2COOCH 2CH 3] +Cl -、
[CH 3(CH 2) 11N(CH 2CH 2CH 3) 2CH 2Ph] +Cl -、
[CH 3(CH 2) 17N(CH 2CH 3) 2(CH 2Ph)] +Cl -、
[CH 3(CH 2) 17N(CH 2CH 2CH 3) 2CH 2Ph] +Cl -、
[CH 3(CH 2) 11N(CH 3) 2CH 2CONHCH 2CH 3] +Cl -、
[CH 3(CH 2) 15N(CH 2CH 2CH 3) 2CH 2Ph] +Cl -、
[CH 3(CH 2) 11N(CH 3) 2CH 2COOCH 2CH 3] +Cl -、
[CH 3(CH 2) 13N(CH 2CH 2CH 3) 2CH 2Ph] +Cl -、
[CH 3(CH 2) 11N(CH 2CH 3) 2(CH 2Ph)] +Cl -、
[CH 3(CH 2) 11N (CH 2CH 2CH 3) 2CH 2Ph] +Cl -, or the like.
For example, tertiary amines is the pairing compound of above-mentioned quaternary ammonium salt phase transfer catalyst.
For example, polyalcohols, polyether compound can be: Polyethylene Glycol-600, polyoxyethylene glycol 800, Macrogol 2000 0, Macrogol 2000, cetomacrogol 1000, emulsifying agent TX-8, emulsifying agent TX-9, emulsifying agent TX-10, emulsifying agent TX-12, emulsifying agent TX-15, polyoxyethylene nonylphenol ether-7, polyoxyethylene nonylphenol ether-9, emulsifier op-10, polyoxyethylene nonylphenol ether-15, emulsifying agent SE, milky white clever A, penetrating agent JFC, detergent JU or the like.
The present invention's composite phase transfer catalyst, its preparation method is as follows:
Method one with cationic quaternary ammonium salt (or tertiary amine) phase-transfer catalyst and non-ionic type phase-transfer catalyst, according to described ratio, adds in the entry under 20～60 ℃, and stirring and dissolving becomes homogeneous phase, and its concentration can be selected in 20～85% scopes.
Method two, with cationic quaternary ammonium salt (or tertiary amine) phase-transfer catalyst and non-ionic type phase-transfer catalyst, according to described ratio, in 60～80 ℃ of following adding reactors, the stirring and dissolving homogeneous phase promptly gets product of the present invention.For example, the catalyzer shown in following: the main constituent 1 [PhCH of sequence number catalyzer 2N (CH 2CH 3) 3] +Cl -,
[O 2N-Ph-CH(OH)CH(CH 2OH)N(Ph?CH 2) 3N] +Cl -、
[CH 3(CH 2) 15N (CH 3) 3] +Cl -, Macrogol 2000 02 [PhCH 2N (CH 2CH 3) 3] +Br -,
[O 2N-Ph-CH(OH)CH(CH 2OH)N(PhCH 2) 2(CH 2COOCH 3)] +Cl -、
[CH 3(CH 2) 15(CH 3) 2N (CH 2Ph] +Cl -, Macrogol 2000 3 [PhCH 2N (CH 2) 3CH 3) 3] +Cl -,
[O 2N-Ph-CH(OH)CH(CH 2OH)(PhCH 2) 2N(CH 2COOCH 3)] +Cl -、
[CH 3(CH 2) 13(CH 3) 2NCH 2Ph] +Cl -, penetrating agent JFC.4 [PhCH 2N(CH 2) 3CH) 3] +Br -、
[O 2N-Ph-CH(OH)CH(CH 2OH)N(PhCH 2) 2(CH 3)] +I -、
[CH 3(CH 2) 13(CH 3) 2N (CH 2COOCH 3)] +Cl -, Polyethylene Glycol-600 5 [(CH 3CH 2CH 2CH 2) 4N] +Br -,
[O 2N-Ph-CH(OH)CH(CH 2OH)N(PhCH 2) 2(CH 3)] +I -、
[CH 3(CH 2) 13(CH 3) 2N (CH 2CONHCH 3)] +Cl -, emulsifying agent TX-15.6 [PhCH 2N(CH 2) 7CH 3) 3] +Cl -、
[O 2N-Ph-CH(OH)CH(CH 2OH)N(Ph?CH 2) 3N] +Cl -、
[CH 3(CH 2) 13(CH 3) 2NCH 2Ph] +Cl -, detergent JU7 [PhCH 2(CH 3) 2(CH 2) 13CH 3] +Cl -,
[O 2N-Ph-CH(OH)CH(CH 2OH)(PhCH 2) 3N] +Cl -、
[CH 3(CH 2) 15(CH 3) 3] +Cl -, emulsifying agent SE.8 [(PhCH 2) (CH 3CH 2) 2N (CH 2) 17CH 3] +Cl -, poly(oxyethylene glycol) 400,
[(CH 3CH 2CH 2CH 2) 4N] +Cl -, [(CH 3CH 2) 3NCH 2COOCH 3] +Cl -, 9 [(CH 3CH 2CH 2CH 2) 3N (CH 2COOCH 3)] +Cl -, emulsifying agent TX-7
[PhCH 2N(CH 2CH 3)] +Cl -、
[O 2N-Ph-CH(OH)CH(CH 2OH)N(PhCH 2) 3] +Cl -、10 [O 2N-Ph-CH(OH)CH(CH 2OH)N(PhCH 2) 2(CH 3)] +I -、
[PhCH 2N(CH 3) 2(CH 2CONHCH 2CH 3)] +Cl -、
[(CH 3CH 2) 4N] +Cl -, emulsifying agent SE.11 PhCH 2N(CH 3) 2、(CH 3CH 2CH 2CH 2) 3N、
(CH 3CH 2) 3N, Macrogol 2000
The weight combinations ratio of the cation quaternary ammonium salt in the composite catalyst of the present invention (or tertiary amine) phase-transfer catalyst and non-ionic type phase-transfer catalyst can for
1.0: 0.05～10, the best of breed ratio is 1.0: 0.05～1.0;
Proportioning between the cation quaternary ammonium salt in the composite catalyst of the present invention (or tertiary amine) does not have particular requirement, ratio between the cation quaternary ammonium salt (or tertiary amine), and to select which kind of cation quaternary ammonium salt (or tertiary amine) be those skilled in the art just can select and finish by general experiment.
It is fixed that the add-on of the present invention's composite transferring catalyzer is come according to reaction type, is generally 1～10% of reaction standard substance weight.
The present invention's composite phase transfer catalyst is used for oxy-thiophosphate when synthetic, can make the production time of omethoate oxy-thiophosphate shorten 1/3rd, and temperature reduces by 5 ℃, and yield improves 10～18%;
Following embodiment will explain the present invention further, and not limit the present invention in any way.
Embodiment
[O 2N-Ph-CH (OH) CH (CH 2OH) N (CH 2Ph) 3] +Cl -Preparation
The O that in reaction flask, adds 0.1mol earlier 2N-Ph-CH (OH) CH (CH 2OH) NH 2, the 80ml propyl carbinol, 0.2mol benzyl chlorine, the 0.2mol sodium bicarbonate stirs, the slow intensification, 100 ℃ of reactions 5 hours, the decompression still removed propyl carbinol, removed inorganic salt with the 100ml washing, and suction filtration, drying get the white solid thing.
Get the above-mentioned white solid thing 0.1mol that makes and add in the reaction flask, add 0.1mol benzyl chlorine again, the 100ml propyl carbinol, slowly heat up, at 100 ℃ of reactions 5 hours, pressure reducing and steaming propyl carbinol, add an amount of re-crystallizing in ethyl acetate, get white crystal (being prepared ammonium salt).
Embodiment 2
[O 2N-Ph-CH (OH) CH (CH 2OH) (CH 2Ph) 2NCH 3] +I -Preparation
Get the white solid thing 0.1mol that embodiment 1 the first step makes and add in the reaction flask, add the 0.1mol methyl iodide again, 100ml methyl alcohol 70 ℃ of reactions 5 hours, boils off methyl alcohol, adds an amount of re-crystallizing in ethyl acetate, white crystal (being prepared ammonium salt).
Embodiment 3[O 2N-Ph-CH (OH) CH (CH 2OH) (CH 2Ph) 2NCH 2COOCH 3] +Cl -Preparation
The O that in reaction flask, adds 0.1mol earlier 2N-Ph-CH (OH) CH (CH 2OH) NH 2, the 80ml propyl carbinol, 0.2mol benzyl chlorine, the 0.2mol sodium bicarbonate stirs, the slow intensification, 100 ℃ of reactions 5 hours, the decompression still removed propyl carbinol, removed inorganic salt with the 100ml washing, and suction filtration, drying get the white solid thing.
Get the above-mentioned white solid thing 0.1mol that makes and add in the reaction flask, add the 0.1mol methyl chloroacetate again, 100ml methyl alcohol, slowly heat up, at 70 ℃ of reactions 3 hours, pressure reducing and steaming methyl alcohol, add an amount of re-crystallizing in ethyl acetate, get white crystal (being prepared ammonium salt).
Embodiment 4
[O 2N-Ph-CH (OH) CH (CH 2OH) (CH 2Ph) 2NCH 2CONHCH 3] +Cl -Preparation
Get the white crystal thing 0.1mol that embodiment 2 makes and add in the reaction flask, add the 0.1mol Monomethylamine again, 50ml methyl alcohol 0 ℃ of reaction 1 hour, boils off methyl alcohol, faint yellow solid thing (being prepared ammonium salt).
Embodiment 5
[CH 3(CH 2) 17N (CH 3) 2CH 2Ph] +The preparation of Br
The CH that in reaction flask, adds 0.1mol earlier 3(CH 2) 13N (CH 3) 2, 80ml methyl alcohol, the 0.1mol methyl chloroacetate stirs, and slowly heats up, and 70 ℃ of reactions 3 hours, pressure reducing and steaming methyl alcohol was used re-crystallizing in ethyl acetate, suction filtration, drying gets white solid thing (being prepared ammonium salt).
Embodiment 6
[CH 3(CH 2) 13N (CH 3) 2CH 2CONHCH 3] +Cl -Preparation
Get the white crystal thing 0.1mol that embodiment 4 makes and add in the reaction flask, add the 0.1mol Monomethylamine again, 50ml methyl alcohol 0 ℃ of reaction 1 hour, boils off methyl alcohol, faint yellow thick thing (being prepared ammonium salt).
Embodiment 7
[CH 3(CH 2) 13N (CH 3) 2CH 2Ph] +Cl -Preparation
The CH that in reaction flask, adds 0.1mol earlier 3(CH 2) 13N (CH 3) 2, 80ml methyl alcohol, the 0.1mol Benzyl Chloride stirs, and slowly heats up, and 100 ℃ of reactions 3 hours, the pressure reducing and steaming butanols was used re-crystallizing in ethyl acetate, suction filtration, drying gets white solid thing (being prepared ammonium salt).
The foregoing description 1～embodiment 7 is typical preparation methods of six class quaternary ammonium salts, has also prepared other quaternary ammonium salt required for the present invention with these a few class preparation methods.For example,
[CH 3(CH 2) 13N(CH 3) 2CH 2Ph] +Br -、
[CH 3(CH 2) 13N(CH 3) 2CH 2COOCH 3] +Cl -、
[CH 3(CH 2) 15N(CH 3) 2CH 2Ph] +Br -、
[CH 3(CH 2) 13N(CH 3) 2(CH 2Ph)] +Cl -、
[CH 3(CH 2) 11N(CH 3) 2CH 2Ph] +Br -、
[CH 3(CH 2) 15N(CH 3) 2CH 2CONHCH 3] +Cl -、
[CH 3(CH 2) 17N(CH 3) 2CH 2Ph] +Br -、
[CH 3(CH 2) 15N(CH 3) 2CH 2COOCH 3] +Cl -、
[CH 3(CH 2) 17N(CH 2CH 3) 2CH 2Ph] +Br -、
[CH 3(CH 2) 15N(CH 3) 2(CH 2Ph)] +Cl -、
[CH 3(CH 2) 15N(CH 2CH 3) 2CH 2Ph] +Br -、
[CH 3(CH 2) 17N(CH 3) 2CH 2CONHCH 3] +Cl -、
[CH 3(CH 2) 13N(CH 2CH 3) 2CH 2Ph] +Br -、
[CH 3(CH 2) 17N(CH 3) 2CH 2COOCH 3] +Cl -、
[CH 3(CH 2) 11N(CH 2CH 3) 2CH 2Ph] +Br -、
[CH 3(CH 2) 17N(CH 3) 2(CH 2Ph)] +Cl -、
[CH 3(CH 2) 17N(CH 2CH 3) 2CH 2Ph] +Cl -、
[CH 3(CH 2) 11N(CH 3) 2CH 2CONHCH 3] +Cl -、
[CH 3(CH 2) 15N(CH 2CH 3) 2CH 2Ph] +Cl -、
[CH 3(CH 2) 11N(CH 3) 2CH 2COOCH 3] +Cl -、
[CH 3(CH 2) 13N(CH 2CH 3) 2CH 2Ph] +Cl -、
[CH 3(CH 2) 11N(CH 3) 2(CH 2Ph)] +Cl -、
[CH 3(CH 2) 11N(CH 2CH 3) 2CH 2Ph] +Cl -、
[O 2N-Ph-CH(OH)CH(CH 2OH)(CH 2Ph) 2(CH 2COOCH 3)N] +Cl -、
[O 2N-Ph-CH(OH)CH(CH 2OH)(CH 2Ph) 2N(CH 2?CONHCH 2CH 3)N] +Cl -、
[CH 3(CH 2) 13N(CH 3) 2CH 2CONHCH 2CH 3] +Cl -、
[CH 3(CH 2) 13N(CH 2CH 3) 2CH 2Ph] +Br -、
[CH 3(CH 2) 13N(CH 3) 2CH 2COOCH 2CH 3] +Cl -、
[CH 3(CH 2) 15N(CH 2CH 3) 2CH 2Ph] +Br -、
[CH 3(CH 2) 13N(CH 2CH 3) 2(CH 2Ph)] +Cl -、
[CH 3(CH 2) 11N(CH 2CH 3) 2CH 2Ph] +Br -、
[CH 3(CH 2) 15N(CH 3) 2CH 2CONHCH 2CH 3] +Cl -、
[CH 3(CH 2) 17N(CH 2CH 3) 2CH 2Ph] +Br -、
[CH 3(CH 2) 15N(CH 3) 2CH 2COOCH 2CH 3] +Cl -、
[CH 3(CH 2) 17N(CH 2CH 2CH 3) 2CH 2Ph] +Br -、
[CH 3(CH 2) 15N(CH 2CH 3) 2(CH 2Ph)] +Cl -、
[CH 3(CH 2) 15N(CH 2CH 2CH 3) 2CH 2Ph] +Br -、
[CH 3(CH 2) 17N(CH 3) 2CH 2CONHCH 2CH 3] +Cl -、
[CH 3(CH 2) 13N(CH 2CH 2CH 3) 2CH 2Ph] +Br -、
[CH 3(CH 2) 17N(CH 3) 2CH 2COOCH 2CH 3] +Cl -、
[CH 3(CH 2) 11N(CH 2CH 2CH 3) 2CH 2Ph] +Br -、
[CH 3(CH 2) 17N(CH 2CH 3) 2(CH 2Ph)] +Cl -、
[CH 3(CH 2) 17N(CH 2CH 2CH 3) 2CH 2Ph] +Cl -、
[CH 3(CH 2) 11N(CH 3) 2CH 2CONHCH 2CH 3] +Cl -、
[CH 3(CH 2) 15N(CH 2CH 2CH 3) 2CH 2Ph] +Cl -、
[CH 3(CH 2) 11N(CH 3) 2CH 2COOCH 2CH 3] +Cl -、
[CH 3(CH 2) 13N(CH 2CH 2CH 3) 2CH 2Ph] +Cl -、
[CH 3(CH 2) 11N(CH 2CH 3) 2(CH 2Ph)] +Cl -、
[CH 3(CH 2) 11N(CH 2CH 2CH 3) 2CH 2Ph] +Cl -、
Or the like.
Embodiment 8
The preparation of composite phase transfer catalyst I
Triethyl benzyl ammonia chloride 20g, [O 2N-Ph-CH (OH) CH (CH 2OH) N (CH 2Ph) 3] +Cl50g, trimethylammonium cetyl chloride ammonium 10g, polyoxyethylene glycol (20000) 50g, water 100g.Stir down and slowly be warming up to 80 ℃, constant temperature stirred 3 hours, and cooling discharging promptly gets composite phase transfer catalyst I.
Embodiment 9
The preparation of composite phase transfer catalyst II
Ethylbenzyl brometo de amonio 20g[O 2N-Ph-CH (OH) CH (CH 2OH) (CH 2Ph) 2N (CH 2COOCH 3)] +Clc 50g, dimethyl hexadecyl benzyl ammonium chloride 10g, polyoxyethylene glycol (2000) 100g, water 100g.Stir down and slowly be warming up to 80 ℃, constant temperature stirred 3 hours, and cooling discharging promptly gets composite phase transfer catalyst II.
Embodiment 10
The preparation of composite phase transfer catalyst III
Tributyl benzyl ammonium chloride 20, [O 2N-Ph-CH (OH) CH (CH 2OH) N (CH 2CONHCH 3] +Cl -, 50g, dimethyl tetradecyl benzyl ammonium chloride 10g, penetrating agent JFC 200g, water 100g.Stir down and slowly be warming up to 80 ℃, constant temperature stirred 3 hours, and cooling discharging promptly gets composite phase transfer catalyst III.
Embodiment 11
The preparation of composite phase transfer catalyst IV
Trioctylphosphine benzyl brometo de amonio 20g, [O 2N-Ph-CH (OH) CH (CH 2OH) N (CH 2Ph) 2(CH 3)] +I -50g, [CH 3(CH 2) 13N (CH 3) 2CH 2COOCH 3] +Cl -, 10g, polyoxyethylene glycol (600) 300g, water 100g.Stir down and slowly be warming up to 80 ℃, constant temperature stirred 3 hours, and cooling discharging promptly gets composite phase transfer catalyst IV.
Embodiment 12
The preparation of composite phase transfer catalyst V
[O 2N-Ph-CH (OH) CH (CH 2OH) N (CH 2Ph) 2(CH 3)] +Cl -50g, [CH 3(CH 2) 13N (CH 3) 2CH 2CONHCH 3] +Cl -10g, emulsifying agent TX-15 300g, water 100g.Stir down and slowly be warming up to 80 ℃, constant temperature stirred 3 hours, and cooling discharging promptly gets composite phase transfer catalyst V.
Embodiment 13
The preparation of composite phase transfer catalyst VI
The trioctylphosphine benzyl ammonium chloride, [O 2N-Ph-CH (OH) CH (CH 2OH) N (CH 2Ph) 3] +Cl -50g, [CH 3(CH 2) 13N (CH 3) 2(CH 2Ph)] +Cl -10g, detergent JU300g, water 100g.Stir down and slowly be warming up to 80 ℃, constant temperature stirred 3 hours, and cooling discharging promptly gets composite phase transfer catalyst VI.
Embodiment 14
The preparation of composite phase transfer catalyst VII
Trimethylammonium cetyl chloride ammonium 10g, [O 2N-Ph-CH (OH) CH (CH 2OH) N (CH 2Ph) 3] +Cl -50g, [CH 3(CH 2) 13N (CH 3) 2(CH 2Ph)] +Cl -10g, emulsifying agent SE 300g, water 100g.Stir down and slowly be warming up to 80 ℃, constant temperature stirred 3 hours, and cooling discharging promptly gets composite phase transfer catalyst VII.
The foregoing description 8-embodiment 14 is typical synthetic methods of the present invention's composite catalyst, utilizes aforesaid quaternary ammonium salt can synthesize different complex phase transfer catalysts with non-ionic compound with these methods.
Industry comparative examples 15
Synthesizing of omethoate intermediate oxy-thiophosphate
With the omethoate ammonium phosphate sulfate salt brine solution of 1300Kg 43.52%, drop in the reactor, add mineral acid and transfer pH value to equal 7.5, drop into the 1600Kg methyl chloroacetate again, heat up, under agitation, 58～62 ℃ of controlled temperature reacted discharging 120 minutes, left standstill 30 minutes, layering is carried out underpressure distillation with thick oxy-thiophosphate, and smart oxy-thiophosphate must be measured and be 601.3Kg, gas-chromatography content is 81.15%, and yield is 64.08%.
Industrial implementation example 15
Synthesizing of composite phase transfer catalyst I Catalytic Oxygen Rogor intermediate oxy-thiophosphate
With the omethoate ammonium phosphate sulfate salt brine solution of 1300Kg 41.77%, drop in the reactor, add mineral acid and transfer pH value to equal 7.5, drop into the 1600Kg methyl chloroacetate again, add the present invention's complex phase transfer catalyst I 10.5Kg, heat up, under agitation, 55～58 ℃ of controlled temperature reacted 80 minutes, layering was left standstill in discharging 30 minutes, thick oxy-thiophosphate is carried out underpressure distillation, smart oxy-thiophosphate must be measured and be that 702Kg, gas-chromatography content are 82.05%, and yield is 78.82%.
Embodiment 16
Synthesizing of complex phase transfer catalyst Catalytic Oxygen Rogor intermediate oxy-thiophosphate
The omethoate ammonium phosphate sulfate salt brine solution of 120g 45.12% drops in the reaction flask, adds mineral acid and transfers pH value to equal 7.5, drop into the 150g methyl chloroacetate again, add the present invention's complex phase transfer catalyst II 1.0g, heat up, under agitation, 55～58 ℃ of controlled temperature reacted 80 minutes, layering was left standstill in discharging 30 minutes, thick oxy-thiophosphate is carried out underpressure distillation, smart oxy-thiophosphate must be measured and be that 68.3g, gas-chromatography content are 86.82%, and yield is 81.63%.
Comparative examples 16
Synthesizing of omethoate intermediate oxy-thiophosphate
With the omethoate ammonium phosphate sulfate salt brine solution of 120g 44.09%, drop in the reaction flask, add mineral acid and transfer pH value to equal 7.5, drop into the 150g methyl chloroacetate again, heat up, under agitation, 58～62 ℃ of controlled temperature reacted discharging 120 minutes, left standstill 30 minutes, layering is carried out underpressure distillation with thick oxy-thiophosphate, and smart oxy-thiophosphate must be measured and be 56.8g, gas-chromatography content is 79.0%, and yield is 63.01%.
Embodiment 17
Constituent Catalytic Oxygen Rogor intermediate oxy-thiophosphate synthetic that adds composite phase transfer catalyst respectively
Omethoate ammonium phosphate sulfate salt brine solution with 120g 44.04%, drop in the reaction flask, adding mineral acid transfers pH value to equal 7.5, drop into the 150g methyl chloroacetate again, add cationic quaternary ammonium salt phase transfer catalyst (triethyl benzyl ammonia chloride 0.2g, dimethyl hexadecyl benzyl ammonium chloride the 0.1g, [O of the complex phase transfer catalyst that constitutes the present invention respectively 2N-Ph-CH (OH) CH (CH 2OH) (CH 2Ph) 2NCH 3] +I -0.2g non-ionic type phase-transfer catalyst (Macrogol 2000 0) 0.5g heats up, under agitation, 55～58 ℃ of controlled temperature reacted discharging 80 minutes, left standstill 30 minutes, layering is carried out underpressure distillation with thick oxy-thiophosphate, and smart oxy-thiophosphate must be measured and be 65.6g, gas-chromatography content is 87.01%, and yield is 80.49%.
Embodiment 18
Synthesizing of composite phase transfer catalyst III Catalytic Oxygen Rogor intermediate oxy-thiophosphate
With the omethoate ammonium phosphate sulfate salt brine solution of 120g 46.02%, drop in the reaction flask, add mineral acid and transfer pH value to equal 7.5, drop into the 150g methyl chloroacetate again, add the present invention's complex phase transfer catalyst III 1.0g, heat up, under agitation, 55～58 ℃ of controlled temperature reacted 80 minutes, layering was left standstill in discharging 30 minutes, thick oxy-thiophosphate is carried out underpressure distillation, smart oxy-thiophosphate must be measured 71.4g, and gas-chromatography content 84.92%, yield are 81.84%.
Embodiment 19
Synthesizing of composite phase transfer catalyst IV Catalytic Oxygen Rogor intermediate oxy-thiophosphate
With the omethoate ammonium phosphate sulfate salt brine solution of 120g 45.5%, drop in the reaction flask, add mineral acid and transfer pH value to equal 7.5, drop into the 150g methyl chloroacetate again, add the present invention's complex phase transfer catalyst IV 1.0g, heat up, under agitation, 55～58 ℃ of controlled temperature reacted 80 minutes, layering was left standstill in discharging 30 minutes, thick oxy-thiophosphate is carried out underpressure distillation, smart oxy-thiophosphate must be measured 68.0g, and gas-chromatography content 88.23%, yield are 81.9%.
Embodiment 20
Synthesizing of composite phase transfer catalyst V Catalytic Oxygen Rogor intermediate oxy-thiophosphate
With the omethoate ammonium phosphate sulfate salt brine solution of 120g 47.1%, drop in the reaction flask, add mineral acid and transfer pH value to equal 7.5, drop into the 150g methyl chloroacetate again, add the present invention's complex phase transfer catalyst V1.0g, heat up, under agitation, 55～58 ℃ of controlled temperature reacted 80 minutes, layering was left standstill in discharging 30 minutes, thick oxy-thiophosphate is carried out underpressure distillation, smart oxy-thiophosphate must be measured 71.8g, and gas-chromatography content 86.5%, yield are 81.9%.
Embodiment 21
Synthesizing of composite phase transfer catalyst VI Catalytic Oxygen Rogor intermediate oxy-thiophosphate
With the omethoate ammonium phosphate sulfate salt brine solution of 120g 46.5%, drop in the reaction flask, add mineral acid and transfer pH value to equal 7.5, drop into the 150g methyl chloroacetate again, add the present invention's complex phase transfer catalyst VI 1.0g, heat up, under agitation, 55～58 ℃ of controlled temperature reacted 80 minutes, layering was left standstill in discharging 30 minutes, thick oxy-thiophosphate is carried out underpressure distillation, smart oxy-thiophosphate must be measured 71.6g, and gas-chromatography content 85.8%, yield are 82.05%.
Embodiment 22
Synthesizing of composite phase transfer catalyst VII Catalytic Oxygen Rogor intermediate oxy-thiophosphate
With the omethoate ammonium phosphate sulfate salt brine solution of 120g 44.02%, drop in the reaction flask, add mineral acid and transfer pH value to equal 7.5, drop into the 150g methyl chloroacetate again, add the present invention's complex phase transfer catalyst VII 1.0g, heat up, under agitation, 55～58 ℃ of controlled temperature reacted 80 minutes, layering was left standstill in discharging 30 minutes, thick oxy-thiophosphate is carried out underpressure distillation, smart oxy-thiophosphate must be measured 66.8g, and gas-chromatography content 85.75%, yield are 80.83%.
Embodiment 23
Synthesizing of single quaternary ammonium salt Catalytic Oxygen Rogor intermediate oxy-thiophosphate
With the omethoate ammonium phosphate sulfate salt brine solution of 120g 44.09%, drop in the reaction flask, add the mineral acid adjust pH and equal 7.5, drop into the 150g methyl chloroacetate again, add trimethyl benzyl ammonia chloride 1.0g, heat up, under agitation, 55～58 ℃ of controlled temperature reacted 80 minutes, layering was left standstill in discharging 30 minutes, thick oxy-thiophosphate is carried out underpressure distillation, smart oxy-thiophosphate must be measured 60.89g, and gas-chromatography content 82.3%, yield are 70.38%.
Embodiment 24
Synthesizing of compound quaternary ammonium salt Catalytic Oxygen Rogor intermediate oxy-thiophosphate
With the omethoate ammonium phosphate sulfate salt brine solution of 120g 43.96%, drop in the reaction flask, add mineral acid and transfer pH value to equal 7.5, drop into the 150g methyl chloroacetate again, [O 2N-Ph-CH (OH) CH 2(CH 2OH) (CH 2Ph) 2NCH 3] +I -, trimethyl benzyl ammonia chloride 1.0g heats up, under agitation, and 55～58 ℃ of controlled temperature, reacted 80 minutes, layering was left standstill in discharging 30 minutes, thick oxy-thiophosphate is carried out underpressure distillation, and smart oxy-thiophosphate must be measured 63.4g, and gas-chromatography content 84.10%, yield are 75.10%.
Embodiment 25
Synthesizing of compound tertiary amine consisting of phase-transferring agent Catalytic Oxygen Rogor intermediate oxy-thiophosphate
Omethoate ammonium phosphate sulfate salt brine solution with 120g 43.96%, drop in the reaction flask, adding mineral acid transfers pH value to equal 7.5, drop into the 150g methyl chloroacetate again, the equal proportion mixture 2.0g that adds Diethyl Aniline, triethylamine, Tributylamine, Macrogol 2000, heat up, under agitation, 55～58 ℃ of controlled temperature, reacted 80 minutes, layering was left standstill in discharging 30 minutes, thick oxy-thiophosphate is carried out underpressure distillation, smart oxy-thiophosphate must be measured 62.5g, and gas-chromatography content 84.90%, yield are 74.74%.
From above-mentioned enforcement as seen, big industrial production omethoate intermediate oxygen sulphur phosphorus adds the present invention's phase-transfer catalyst, can make the oxy-thiophosphate yield improve about 15%, in little experiment, add the present invention's phase-transfer catalyst, can make the oxy-thiophosphate yield improve 10～18%.
No matter be big industrial production or little experiment,, all can make the reaction times shorten 1/3rd in case add the present invention's phase-transfer catalyst.

Claims (3)

1. complex phase transfer catalyst with beta-hydroxy structure, it is characterized in that: it contains the quaternary ammonium compound of following general formula
[R 1R 2R 3R 4N] +X -R in the formula 1Be O 2N-Ph-CH (OH) CH (CH 2OH),
R 2, R 3Be C 1～C 18Alkyl, benzyl,
R 1Be benzyl, C 1～C 18Alkyl ,-CH 2COO (CH 2) nCH 3,-CH 2CONH (CH 2) nCH 3Wherein n is 0～8 integer,
X is Cl, Br.
2. according to the complex phase transfer catalyst of the beta-hydroxy structure described in the claim 1, it is characterized in that:
R in formula 1Be O 2N-Ph-CH (OH) CH (CH 2OH) time,
R 2, R 3Be the alkyl of C1～C18,
R 4Be alkyl or the benzyl of C1～C18,
X is Cl, Br.
3. according to the complex phase transfer catalyst of the beta-hydroxy structure described in the claim 2, it is characterized in that:
R in formula 1Be O 2N-Ph-CH (OH) CH (CH 2OH) time,
R 2, R 3Be C 2Alkyl,
R 4Be C 12Alkyl,
X is Br.
CN 00109759 2000-07-05 2000-07-05 Compound phase-transferring quaternary ammonium salt catalyst in beta-hydroxyl structure and its preparation Expired - Fee Related CN1112350C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 00109759 CN1112350C (en) 2000-07-05 2000-07-05 Compound phase-transferring quaternary ammonium salt catalyst in beta-hydroxyl structure and its preparation

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 00109759 CN1112350C (en) 2000-07-05 2000-07-05 Compound phase-transferring quaternary ammonium salt catalyst in beta-hydroxyl structure and its preparation

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
CN96105028A Division CN1060779C (en) 1996-05-16 1996-05-16 Compounded phase transfering catalyst used for catalyzing omethoate intermediate synthesis and its prepn.

Publications (2)

Publication Number Publication Date
CN1287021A CN1287021A (en) 2001-03-14
CN1112350C true CN1112350C (en) 2003-06-25

Family

ID=4579848

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 00109759 Expired - Fee Related CN1112350C (en) 2000-07-05 2000-07-05 Compound phase-transferring quaternary ammonium salt catalyst in beta-hydroxyl structure and its preparation

Country Status (1)

Country Link
CN (1) CN1112350C (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106916071A (en) * 2017-03-24 2017-07-04 吴琏 The synthetic method of benzalkonium chloride mixture
CN106946716B (en) * 2017-03-24 2019-03-01 广东洛斯特制药有限公司 A kind of benzalkonium chloride monomer synthesis technology
CN106946717B (en) * 2017-03-24 2019-02-19 广东洛斯特制药有限公司 Benzalkonium chloride monomer synthesis technology
CN106831446B (en) * 2017-03-24 2019-02-19 广东洛斯特制药有限公司 A kind of improved pharmaceutical grade benzalkonium chloride monomer production method
CN106916068B (en) * 2017-03-24 2019-03-01 广东洛斯特制药有限公司 A kind of simple and convenient benzalkonium chloride production method

Also Published As

Publication number Publication date
CN1287021A (en) 2001-03-14

Similar Documents

Publication Publication Date Title
CN1319860C (en) Magnesium hydroxide particles, flame retardant resin composition and formed products thereof
CN1061945C (en) Process and equipment for producing iron carbide
CN1204131C (en) Process for the preparation of alpha-methylene lactones
CN1860237A (en) Method for purifying succinic acid from fermentation broth
CN1771085A (en) Catalyst for oxidation or ammoxidation
CN1200935C (en) Method for preparing benzofuran or benzothiophene compound
CN101050157A (en) Method for preparing compound in biphenyl class
CN1009340B (en) Production method of composite oxide catalysts
CN1197765C (en) Process for producing persulfate
CN1268601C (en) Intermediates for making benzofuran or benzothiophene derivative nitrated in position 5 and uses thereof
CN1273447C (en) Process for producing diphenyl sulfone compound
CN1717385A (en) Phenolic antioxidants in crystalline form
CN1097591C (en) Process for preparing pyrimidine derivatives
CN1112350C (en) Compound phase-transferring quaternary ammonium salt catalyst in beta-hydroxyl structure and its preparation
CN1102041A (en) Novel oil and alcohol repellent fluorinated surfactants and intermediates, derivates and uses thereof
CN1100883C (en) Process for production of L-aspartic acid
CN1958632A (en) Method for synthesizing latex of heat-resistant resin in maleimide class
CN1258527C (en) Method for preparing aryl alkyl hydrogen peroxide
CN1043492A (en) 2, the selection production of 6-diethylna-phthalene
CN1060779C (en) Compounded phase transfering catalyst used for catalyzing omethoate intermediate synthesis and its prepn.
CN1160307C (en) Process for hydrogenating dinitriles in aminonitriles
CN1872887A (en) Method for synthesizing latex of heatresistant resin in maleimide class
CN1246298C (en) Process for the preparation of ketimines
CN1717269A (en) Method and device for hydrolytically obtaining a carboxylic acid and alcohol from the corresponding carboxylic ester
CN1030069C (en) Process for producing desulfurized fats and oils of fatty acid esters and process for producing alcohols by using said desulfurized fats and oils or fatty acid esters

Legal Events

Date Code Title Description
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C06 Publication
PB01 Publication
C14 Grant of patent or utility model
GR01 Patent grant
C19 Lapse of patent right due to non-payment of the annual fee
CF01 Termination of patent right due to non-payment of annual fee