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 PDFInfo
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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 invention relates to a composite phase transfer catalyst for catalyzing the synthesis of omethoate intermediate oxygen thiophosphate, which contains more than one cationic type, in particular quaternary ammonium salt (or tertiary amine) phase transfer catalyst, or at least one cationic type quaternary ammonium salt (or tertiary amine) phase transfer catalyst combined with the nonionic phase transfer catalyst.
Specifically, the composite phase transfer catalyst contains a cationic quaternary ammonium salt (or tertiary amine) phase transfer catalyst, and is a quaternary ammonium salt compound with the following general formula (I) and a tertiary amine compound with the general formula (II):
[R1R2R3R4N]+Cl- (I)
R1R2R3N (II)
in the formula (I)
R1Is C1～C18Alkyl or O2N--CH(OH)CH(CH2OH)，
R2、R3Is C1～C18An alkyl group, a benzyl group,
R4is benzyl, C1～C18Alkyl, -CH2COO(CH2)nCH3、-CH2CONH(CH2)nCH3、
Wherein n is an integer of 0 to 8,
x is Cl, Br, I,
with the proviso that,
when R is1Is C4～C18When it is alkyl
R2、R3Is C1～C8An alkyl group, a carboxyl group,
R4is C1～C18Alkyl, benzyl, -CH2COO(CH2)nCH3、-CH2CONH(CH2)nCH3，
Wherein n is an integer of 0 to 8,
when R is1Is O2N-Ph-CH(OH)CH(CH2OH) in the presence of a nitrogen-containing gas,
R2、R3is C1～C18Alkyl, benzylThe base group is a group of a compound,
R4is C1～C18Alkyl, benzyl, -CH2COO(CH2)nCH3、-CH2CONH(CH2)nCH3，
In the formula (II)
R1Is C1～C23The alkyl group or the benzyl group of (a),
R2、R3is C1～C18Alkyl or benzyl;
with the proviso that,
when R is1＝C1～C23When the alkyl group is used, the alkyl group,
R2、R3＝C1～C18alkyl or benzyl or H;
when R isiWhen the compound is a benzyl group, the compound is,
R2、R3＝C1～C18alkyl or benzyl or H
The composite phase transfer catalyst of the present invention contains a nonionic phase transfer catalyst such as polyols, polyethers, etc
Polyethylene glycol with the molecular weight of 400-20000,
the general formula is HO (CH)2CH2O) nH n is an integer of 10 to 460;
the general formula is RO (CH)2CH2O) condensation products of higher alcohols of nH with ethylene oxide, where R is C6～C23N is an integer of 6 to 23;
general formula is R-Ph- (CH)2CH2O) nH condensates of alkylphenols with ethylene oxide, where R is C6～C23N is an integer of 6 to 23;
the general formula is RCOO (CH)2CH2O) condensation products of fatty acids of nH with ethylene oxide, where R is C6～C23N is an integer of 6 to 23;
in sixty to eighty years, a plurality of data (including patents) report the synthesis method of omethoate at home and abroad, and the main method comprises the following steps: pre-ammonolysis, methyl isocyanate, Bunte salt and post-ammonolysis. Among them, the post-amination method reported in the east de patent DD110883 has the advantages of easily available raw materials, simple process operation conditions and convenient post-treatment, and is a currently and generally adopted omethoate production method in China. The synthetic intermediate of the omethoate is a key synthetic step influencing the total yield of the omethoate, and no report that a catalyst is used for the synthetic step of the omethoate exists at home and abroad. The patent of CN94117723.8 of the present inventor discloses that the synthesis of omethoate oxysulfate by using quaternary ammonium salts of carbon eight to dioctadecyl as phase transfer catalysts has good catalytic effect, and has the following disadvantages to be further improved.
(1) In the synthesis of omethoate, when a single cationic quaternary ammonium salt is used for phase inversion
When the catalyst is shifted, the cationic quaternary ammonium salt phase shift catalyst with small molecular weight has larger dosage,
and less catalytic activity. (2) The cationic quaternary ammonium salt phase transfer catalyst with large molecular weight has the problem of serious emulsification
Problems, resulting in a cascade during distillation and residues in the product, affecting the next stage
And (4) production.
The present inventors have made extensive studies on a cationic quaternary ammonium salt (or tertiary amine) phase transfer catalyst in combination with the practice of producing an omethoate intermediate, based on long-term studies on the phase transfer catalyst, and as a result, have found that a complex using a cationic quaternary ammonium salt (or tertiary amine) phase transfer catalyst, or a complex made of one or more cationic quaternary ammonium salt (or tertiary amine) phase transfer catalysts and a nonionic phase transfer catalyst, has unexpectedly excellent effects, and have accomplished the present invention.
One of the objectives of the present invention is to provide a composite phase transfer catalyst for synthesizing omethoate intermediate, which contains more than one cationic quaternary ammonium salt (or tertiary amine) type phase transfer catalyst, or at least one cationic quaternary ammonium salt (or tertiary amine) type phase transfer catalyst in combination with a nonionic phase transfer catalyst. The composite phase transfer catalyst of the invention can overcome the defects of the single cation type phase transfer catalyst in application, and is greatly optimized to the single cation type phase transfer catalyst in catalytic activity.
Another object of the present invention is to provide a process for preparing a quaternary ammonium salt novel compound having the general formula (I) in the composite phase transfer catalyst of the present invention.
Another object of the present invention is to provide a process for preparing the composite phase transfer catalyst of the present invention.
In the production of petrochemical industry, pesticides, medicines and fine chemical industry, many reaction systems are liquid-liquid heterogeneous systems and solid-liquid heterogeneous systems, and materials are difficult to be fully mixed. For example, the omethoate intermediate, the oxysulfate, is a liquid-liquid heterogeneous system, and in order to allow the reaction to be fully performed, the reaction temperature of the one-pass process is too high, and the reaction time is too long, so that the number of by-products is increased, and the content and the yield of the oxysulfate are influenced. On the basis of long-term research on a phase transfer catalyst, in the practice that the cationic phase transfer catalyst is used for producing the omethoate intermediate product of the industry, one or more than one cationic quaternary ammonium salt (or tertiary amine) phase transfer catalyst and a nonionic phase transfer catalyst are prepared into a compound, so that the catalyst has better catalytic performance for reducing the temperature of the omethoate intermediate product, shortening the reaction time, reducing the generation of impurities and improving the content and yield of the omethoate intermediate product of the oxygen thiophosphate. The main reason is that the distribution ratio of the phase transfer catalysts with different molecular structures in the water phase is different from that of the organic phase, some phase transfer catalysts have larger distribution ratio in water, and some phase transfer catalysts have larger distribution ratio in the organic phase, so that the reaction is facilitated by adjusting the proper distribution. The nonionic phase shift catalyst used in the invention is a polyol or polyether compound, and because the chain has oxygen with unpaired electrons, the hydrophilicity and lipophilicity of the ionic phase transfer catalyst can be improved, and the distribution ratio of the ionic phase transfer catalyst in a water phase and an oil phase is changed, so that the reaction speed is accelerated; in addition, oxygen on the polyol and polyether compound chains has a complexing effect on positive ions of reactants, so that the number of negative ions in a reaction system is relatively increased, the reduction of the activation energy of the reaction is facilitated, and the reaction speed is accelerated; moreover, the addition of the composite catalyst reduces the interfacial tension between the water phase and the organic phase, so that the two phases are more fully contacted, and the reaction speed is greatly accelerated. From the structure, the compound of quaternary ammonium salt with the positive charge ortho-position polar group has the catalytic effect and also accelerates the reaction speed.
The composite phase transfer catalyst contains more than one cationic quaternary ammonium salt (or tertiary amine) phase transfer catalyst or more than one cationic quaternary ammonium salt (or tertiary amine) phase transfer menstruating agent combined with a nonionic phase transfer agent.
Specifically, the cationic quaternary ammonium salt (or tertiary amine) phase transfer catalyst contained in the composite phase transfer catalyst of the invention is a quaternary ammonium salt compound with the following general formula (I) and a tertiary amine compound with the general formula (II):
[R1R2R3R4N]+Cl- (I)
R1R2R3N (II)
in the formula (I)
R1Is C1～C18Alkyl or O2N-Ph-CH(OH)CH(CH2OH)，
R2、R3Is C1～C18Alkyl, benzyl and H, and the alkyl is a substituent,
R4is benzyl, C1～C18Alkyl, -CH2COO(CH2)nCH3、-CH2CONH(CH2)nCH3，
Wherein n is an integer of 0 to 8,
x is Cl, Br, I. With the proviso that,
when R is1Is C4～C18When the alkyl group is used, the alkyl group,
R2、R3is C1～C8An alkyl group, a benzyl group,
R4is C1～C18Alkyl, -CH2COO(CH2)nCH3、-CH2CONH(CH2)nCH3，
Wherein n is an integer of 0 to 8,
when R is1Is O2N-Ph-CH(OH)CH(CH2OH) in the presence of a nitrogen-containing gas,
R2、R3is C1～C18Alkyl, benzyl and H, and the alkyl is a substituent,
R4is C1～C18Alkyl, benzyl, -CH2COO(CH2)nCH3、-CH2CONH(CH2)nCH3，
Wherein n is an integer of 0 to 8.
In the composite phase transfer catalyst of the present invention, the cationic quaternary ammonium salt catalyst preferably comprises:
a: a quaternary ammonium salt compound having the general formula (I) defined below,
in the formula R1＝C4～C18An alkyl group, a carboxyl group,
Ri、R3＝C1～C8the alkyl group of (a) is,
R4is benzyl, C1～C8The alkyl group of (a) is,
x ═ Cl, Br, I; or,
b: a quaternary ammonium salt compound having the general formula (I) defined below,
in the formula R1＝C4～C18An alkyl group, a carboxyl group,
R2、R3＝C1～C8the alkyl group of (a) is,
R4＝-CH2COO(CH2)nCH3(n is an integer of 0 to 8),
x ═ Cl, Br, I; or,
c: a quaternary ammonium salt compound having the general formula (I) defined below,
in the formula R1＝C4～C18An alkyl group, a carboxyl group,
R2、R3＝C1～C8the alkyl group of (a) is,
R4＝-CH2CONH(CH2)nCH3(n is an integer of 0 to 8),
x ═ Cl, Br, I; or:
d: a quaternary ammonium salt compound having the general formula (I) defined below,
in the formula: r1＝O2N-Ph-CH(OH)CH(CH2OH)，
R2、R3、R4＝C1～C18The alkyl group or the benzyl group of (a),
x ═ Cl, Br, I; or:
e: a quaternary ammonium salt compound having the general formula (I) defined below,
in the formula: r1＝O2N-Ph-CH(OH)CH(CH2OH)，
R2、R3＝C1～C18The alkyl group or the H group of (a),
R4＝-CH2COO(CH2)nCH3(n is an integer of 0 to 8),
x ═ Cl, Br, I; or:
f: a quaternary ammonium salt compound having the general formula (I) defined below,
in the formula: r1＝O2N-Ph-CH(OH)CH(CH2OH)，
R2、R3＝C1～C18The alkyl group or the H group of (a),
R4＝-CH2CONH(CH2)nCH3(n is an integer of 0 to 8),
x ═ Cl, Br, I; in the formula (II)
R1Is C1～C23The alkyl group or the benzyl group of (a),
R2、R3is C1～C18Alkyl or benzyl of (a);
with the proviso that,
when R is1Is C1～C23In the case of the alkyl group of (a),
R2、R3is C1～C18Alkyl or benzyl or H;
when R is1When the compound is a benzyl group, the compound is,
R2、R3＝C1～C18alkyl or benzyl or H.
The nonionic phase transfer catalyst in the composite phase transfer catalyst of the invention is preferably a polyol or polyether compound, such as:
polyethylene glycol with the molecular weight of 600-20000,
the general formula is HO (CH)2CH2O) nHn is an integer of 10 to 460;
the general formula is RO (CH)2CH2Condensation products of O) nH higher alcohols with ethylene oxide
Wherein R is C6～C23The alkyl group n is an integer of 6 to 23;
the general formula is R-Ph-O (CH)2CH2O) condensates of an alkyl phenol of nH with ethylene oxide,
wherein R is C6～C23The alkyl group n is an integer of 6 to 23;
the general formula is RCOO (CH)2CH2Condensation products of O) nH fatty acids with ethylene oxide
Wherein R is C6～C23The alkyl group n is an integer of 6 to 23;
the quaternary ammonium salt (or tertiary amine) type compound in the composite phase transfer catalyst of the present invention may be commercially available, or prepared by a conventional method known in the art, or prepared according to the method of the examples below. Polyols and polyethers are commercially available.
For example, the quaternary ammonium salt may be: [ (CH)3CH2)4N]+Br-、[(CH3CH2CH2CH2)4N]+Br-Trimethylbenzyl chloride ingot, trimethylbenzylBenzalkonium bromide, triethylbenzylammonium chloride, triethylbenzylammonium bromide, tributylbenzylammonium bromide, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, octadecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, dodecyltrimethylammonium bromide, tetraoctylammonium bromide, trioctylbenzylammonium chloride, trioctylmethylammonium iodide, tert-octylmethylammonium bromide, tert-octyltrimethylammonium bromide, tert-,
[O2N-Ph-CH(OH)CH(CH2OH)(CH2Ph)3N]+Cl-、
[O2N-Ph-CH(OH)CH(CH2CH3)N]+I-、
[O2N-Ph-CH(OH)CH(CH2OH)(CH2Ph)2(CH2COOCH3)N]+Cl-、
[O2N-Ph-CH(OH)CH(CH2OH)(CH2Ph)2(CH2CONHCH3)+Cl-、
[CH3(CH2)13N(CH3)2CH2CONHCH3]+Cl-、
[CH3(CH2)13N(CH3)2CH2Ph]+Br-、
[CH3(CH2)13N(CH3)2CH2COOCH3]+Cl-、
[CH3(CH2)15N(CH3)2CH2Ph]+Br-、
[CH3(CH2)13N(CH3)2(CH2Ph)]+Cl-、
[CH3(CH2)11N(CH3)2CH2Ph]+Br-、
[CH3(CH2)15N(CH3)2CH2CONHCH3]+Cl-、
[CH3(CH2)17N(CH3)2CH2Ph]+Br-、
[CH3(CH2)15N(CH3)2CH2COOCH3]+Cl-、
[CH3(CH2)17N(CH3CH3)2CH2Ph]+Br-、
[CH3(CH2)15N(CH3)2(CH2Ph)]+Cl-、
[CH3(CH2)15N(CH2CH3)2CH2Ph]+Br-、
[CH3(CH2)17N(CH3)2CH2CONHCH3]+Cl-、
[CH3(CH2)15N(CH2CH3)2CH2Ph]+Br-、
[CH3(CH2)17N(CH3)2CH2COOCH3]+Cl-、
[CH3(CH2)11N(CH2CH3)2CH2Ph]+Br-、
[CH3(CH2)17N(CH3)2(CH2Ph)]+Cl-、
[CH3(CH2)17N(CH2CH3)2CH2Ph]+Cl-、
[CH3(CH2)11N(CH3)2CH2CONHCH3]+Cl-、
[CH3(CH2)15N(CH2CH3)2CH2Ph]+Cl-、
[CH3(CH2)11N(CH3)2CH2COOCH3]+Cl-、
[CH3(CH2)15N(CH2CH3)2CH2Ph]+Cl-、
[CH3(CH2)11N(CH3)2(CH2Ph)]+Cl-、
[CH3(CH2)11N(CH2CH3)2CH2Ph]+Cl-、
[O2N-Ph-CH(OH)CH(CH2OH)(CH2Ph)2(CH2COOCH2CH3)N]+Cl-、
[O2N-Ph-CH(OH)CH(CH2OH)(CH2Ph)2N(CH2CONHCH2CH3)]+Cl-、
[CH3(CH2)13N(CH3)2CH2CONHCH2CH3]+Cl-、
[CH3(CH2)13N(CH2CH3)2CH2Ph]+Br-、
[CH3(CH2)13N(CH3)2CH2COOCH2CH3]+Cl-、
[CH3(CH2)15N(CH2CH3)2(CH2Ph)]+Br-、
[CH3(CH2)13N(CH2CH3)2CH2 Ph]+Cl-、
[CH3(CH2)11N(CH2 CH3)2CH2Ph]+Br-、
[CH3(CH2)15N(CH3)2CH2CONHCH2CH3]+Cl-、
[CH3(CH2)17N(CH2CH3)2CH2Ph]+Br-、
[CH3(CH2)15N(CH3)2CH2COOCH2CH3]+Cl-、
[CH3(CH2)17N(CH2CH2CH3)2CH2Ph]+Br-、
[CH3(CH2)15N(CH2CH3)2(CH2Ph)]+Cl-、
[CH3(CH2)15N(CH2CH2CH3)2CH2Ph]+Br-、
[CH3(CH2)17N(CH3)2CH2CONHCH2CH3]+Cl-、
[CH3(CH2)13N(CH2CH2CH3)2CH2Ph]+Br-、
[CH3(CH2)17N(CH3)2CH2COOCH2CH3]+Cl-、
[CH3(CH2)11N(CH2CH2CH3)2CH2Ph]+Cl-、
[CH3(CH2)17N(CH2CH3)2(CH2Ph)]+Cl-、
[CH3(CH2)17N(CH2CH2CH3)2CH2Ph]+Cl-、
[CH3(CH2)11N(CH3)2CH2CONHCH2CH3]+Cl-、
[CH3(CH2)15N(CH2CH2CH3)2CH2Ph]+Cl-、
[CH3(CH2)11N(CH3)2CH2COOCH2CH3]+Cl-、
[CH3(CH2)13N(CH2CH2CH3)2CH2Ph]+Cl-、
[CH3(CH2)11N(CH2CH3)2(CH2Ph)]+Cl-、
[CH3(CH2)11N(CH2CH2CH3)2CH2Ph]+Cl-And so on.
For example, tertiary amines are compounds corresponding to the above quaternary ammonium salt phase transfer catalysts.
For example, the polyols, polyethers may be: polyethylene glycol 600, polyethylene glycol 800, polyethylene glycol 20000, polyethylene glycol 2000, polyethylene glycol 1000, emulsifier TX-8, emulsifier TX-9, emulsifier TX-10, emulsifier TX-12, emulsifier TX-15, emulsifier OP-7, emulsifier OP-9, emulsifier OP-10, emulsifier OP-15, emulsifier SE, lactalbumin A, penetrant JFC, detergent JU and the like.
The preparation method of the composite phase transfer catalyst comprises the following steps:
according to the first method, a cationic quaternary ammonium salt (or tertiary amine) phase transfer catalyst and a nonionic phase transfer catalyst are added into water at the temperature of 20-60 ℃ according to the proportion, and are stirred and dissolved into a homogeneous phase, wherein the concentration of the homogeneous phase can be selected within the range of 20-85%.
And secondly, adding the cationic quaternary ammonium salt (or tertiary amine) phase transfer catalyst and the nonionic phase transfer catalyst into the reaction kettle at the temperature of 60-80 ℃ according to the proportion, and stirring to dissolve a homogeneous phase to obtain the product. For example, the following catalysts are shown: main composition of serial number catalyst 1 [ PhCH2N(CH2CH3)3]+Cl-、
[O2N-Ph-CH(OH)CH(CH2OH)N(Ph CH2)3N]+Cl-、
[CH3(CH2)15N(CH3)3]+Cl-Polyethylene glycol 200002 [ PhCH ]2N(CH2CH3)3]+Br-、
[O2N-Ph-CH(OH)CH(CH2OH)N(PhCH2)2(CH2COOCH3)]+Cl-、
[CH3(CH2)15(CH3)2N(CH2Ph]+Cl-Polyethylene glycol 20003 [ PhCH2N(CH2)3CH3)3]+Cl-、
[O2N-Ph-CH(OH)CH(CH2OH)(PhCH2)2N(CH2COOCH3)]+Cl-、
[CH3(CH2)13(CH3)2NCH2Ph]+Cl-And a penetrant JFC. 4 [ PhCH2N(CH2)3CH)3]+Br-、
[O2N-Ph-CH(OH)CH(CH2OH)N(PhCH2)2(CH3)]+I-、
[CH3(CH2)13(CH3)2N(CH2COOCH3)]+Cl-Polyethylene glycol 6005 [ (CH)3CH2CH2CH2)4N]+Br-、
[O2N-Ph-CH(OH)CH(CH2OH)N(PhCH2)2(CH3)]+I-、
[CH3(CH2)13(CH3)2N(CH2CONHCH3)]+Cl-And an emulsifier TX-15. 6 [ PhCH2N(CH2)7CH3)3]+Cl-、
[O2N-Ph-CH(OH)CH(CH2OH)N(Ph CH2)3N]+Cl-、
[CH3(CH2)13(CH3)2NCH2Ph]+Cl-Detergent JU7 [ PhCH ]2(CH3)2(CH2)13CH3]+Cl-、
[O2N-Ph-CH(OH)CH(CH2OH)(PhCH2)3N]+Cl-、
[CH3(CH2)15(CH3)3]+Cl-And an emulsifier SE. 8 [ (PhCH)2)(CH3CH2)2N(CH2)17CH3]+Cl-Polyethylene glycol 400,
[(CH3CH2CH2CH2)4N]+Cl-、[(CH3CH2)3NCH2COOCH3]+Cl-、9 [(CH3CH2CH2CH2)3N(CH2COOCH3)]+Cl-Emulsifier TX-7
[PhCH2N(CH2CH3)]+Cl-、
[O2N-Ph-CH(OH)CH(CH2OH)N(PhCH2)3]+Cl-、10 [O2N-Ph-CH(OH)CH(CH2OH)N(PhCH2)2(CH3)]+I-、
[PhCH2N(CH3)2(CH2CONHCH2CH3)]+Cl-、
[(CH3CH2)4N]+Cl-And an emulsifier SE. 11 PhCH2N(CH3)2、(CH3CH2CH2CH2)3N、
(CH3CH2)3N, polyethylene glycol 2000
The weight combination ratio of the cationic quaternary ammonium salt (or tertiary amine) phase transfer catalyst and the nonionic phase transfer catalyst in the composite catalyst can be
1.0: 0.05-10, the best combination ratio is 1.0: 0.05-1.0;
the proportion of the cationic quaternary ammonium salt (or tertiary amine) in the composite catalyst of the invention has no special requirements, and the proportion of the cationic quaternary ammonium salt (or tertiary amine) and the selection of which cationic quaternary ammonium salt (or tertiary amine) can be selected and completed by general experiments by those skilled in the art.
The amount of the composite transfer catalyst of the present invention is determined according to the reaction type, and is generally 1 to 10% by weight of the reaction reference.
When the composite phase transfer catalyst is used for synthesizing the oxyphosphorous ester, the production time of the oxyphosphorous ester can be shortened by one third, the temperature is reduced by 5 ℃, and the yield is improved by 10-18%;
the following examples will further illustrate the invention and are not intended to limit the invention in any way.
Examples
[O2N-Ph-CH(OH)CH(CH2OH)N(CH2Ph)3]+Cl-Preparation of
Firstly, 0.1mol of O is added into a reaction bottle2N-Ph-CH(OH)CH(CH2OH)NH280ml of n-butyl alcohol, 0.2mol of benzyl chloride and 0.2mol of sodium bicarbonate are fully and uniformly stirred, slowly heated, reacted for 5 hours at the temperature of 100 ℃, decompressed, removed of n-butyl alcohol, washed by 100ml of water to remove inorganic salt, filtered and dried to obtain white solid.
Adding 0.1mol of the obtained white solid into a reaction bottle, adding 0.1mol of benzyl chloride and 100ml of n-butanol, slowly heating, reacting at 100 ℃ for 5 hours, evaporating the n-butanol under reduced pressure, adding a proper amount of ethyl acetate, and recrystallizing to obtain white crystals (namely the prepared ammonium salt).
Example 2
[O2N-Ph-CH(OH)CH(CH2OH)(CH2Ph)2NCH3]+I-Preparation of
0.1mol of the white solid obtained in the first step of example 1 was taken and charged into a reaction flask, 0.1mol of methyl iodide and 100ml of methanol were added and reacted at 70 ℃ for 5 hours, the methanol was distilled off, and an appropriate amount of ethyl acetate was added and recrystallized to obtain white crystals (i.e., the prepared ammonium salt).
Example 3[ O ]2N-Ph-CH(OH)CH(CH2OH)(CH2Ph)2NCH2COOCH3]+Cl-Preparation of
Firstly, 0.1mol of O is added into a reaction bottle2N-Ph-CH(OH)CH(CH2OH)NH280ml of n-butyl alcohol, 0.2mol of benzyl chloride and 0.2mol of sodium bicarbonate are fully and uniformly stirred, slowly heated, reacted for 5 hours at the temperature of 100 ℃, decompressed, removed of n-butyl alcohol, washed by 100ml of water to remove inorganic salt, filtered and dried to obtain white solid.
Adding 0.1mol of the obtained white solid into a reaction bottle, adding 0.1mol of methyl chloroacetate and 100ml of methanol, slowly heating, reacting at 70 ℃ for 3 hours, evaporating the methanol under reduced pressure, adding a proper amount of ethyl acetate, and recrystallizing to obtain a white crystal (namely the prepared ammonium salt).
Example 4
[O2N-Ph-CH(OH)CH(CH2OH)(CH2Ph)2NCH2CONHCH3]+Cl-Preparation of
0.1mol of the white crystal obtained in example 2 was taken and added to a reaction flask, and 0.1mol of monomethylamine and 50ml of methanol were added to react at 0 ℃ for 1 hour, and the methanol was distilled off to obtain a pale yellow solid (i.e., the prepared ammonium salt).
Example 5
[CH3(CH2)17N(CH3)2CH2Ph]+Preparation of Br
0.1mol of CH is added into a reaction bottle3(CH2)13N(CH3)280ml of methanol and 0.1mol of methyl chloroacetate are fully and uniformly stirred, slowly heated, reacted for 3 hours at 70 ℃, decompressed and evaporated to remove the methanol, recrystallized by ethyl acetate, filtered by suction and dried to obtain a white solid (namely the prepared ammonium salt).
Example 6
[CH3(CH2)13N(CH3)2CH2CONHCH3]+Cl-Preparation of
0.1mol of the white crystal obtained in example 4 was taken and added into a reaction flask, 0.1mol of monomethylamine and 50ml of methanol were added and reacted at 0 ℃ for 1 hour, and the methanol was distilled off to obtain a pale yellow viscous substance (i.e., the prepared ammonium salt).
Example 7
[CH3(CH2)13N(CH3)2CH2Ph]+Cl-Preparation of
0.1mol of CH is added into a reaction bottle3(CH2)13N(CH3)280ml of methanol and 0.1mol of benzyl chloride are fully and uniformly stirred, slowly heated, reacted for 3 hours at 100 ℃, decompressed and evaporated to remove butanol, recrystallized by ethyl acetate, filtered by suction and dried to obtain white solid (namely the prepared ammonium salt).
Examples 1 to 7 above are typical methods for preparing six types of quaternary ammonium salts, and other quaternary ammonium salts required by the present invention were also prepared by these types of methods. For example,
[CH3(CH2)13N(CH3)2CH2Ph]+Br-、
[CH3(CH2)13N(CH3)2CH2COOCH3]+Cl-、
[CH3(CH2)15N(CH3)2CH2Ph]+Br-、
[CH3(CH2)13N(CH3)2(CH2Ph)]+Cl-、
[CH3(CH2)11N(CH3)2CH2Ph]+Br-、
[CH3(CH2)15N(CH3)2CH2CONHCH3]+Cl-、
[CH3(CH2)17N(CH3)2CH2Ph]+Br-、
[CH3(CH2)15N(CH3)2CH2COOCH3]+Cl-、
[CH3(CH2)17N(CH2CH3)2CH2Ph]+Br-、
[CH3(CH2)15N(CH3)2(CH2Ph)]+Cl-、
[CH3(CH2)15N(CH2CH3)2CH2Ph]+Br-、
[CH3(CH2)17N(CH3)2CH2CONHCH3]+Cl-、
[CH3(CH2)13N(CH2CH3)2CH2Ph]+Br-、
[CH3(CH2)17N(CH3)2CH2COOCH3]+Cl-、
[CH3(CH2)11N(CH2CH3)2CH2Ph]+Br-、
[CH3(CH2)17N(CH3)2(CH2Ph)]+Cl-、
[CH3(CH2)17N(CH2CH3)2CH2Ph]+Cl-、
[CH3(CH2)11N(CH3)2CH2CONHCH3]+Cl-、
[CH3(CH2)15N(CH2CH3)2CH2Ph]+Cl-、
[CH3(CH2)11N(CH3)2CH2COOCH3]+Cl-、
[CH3(CH2)13N(CH2CH3)2CH2Ph]+Cl-、
[CH3(CH2)11N(CH3)2(CH2Ph)]+Cl-、
[CH3(CH2)11N(CH2CH3)2CH2Ph]+Cl-、
[O2N-Ph-CH(OH)CH(CH2OH)(CH2Ph)2(CH2COOCH3)N]+Cl-、
[O2N-Ph-CH(OH)CH(CH2OH)(CH2Ph)2N(CH2 CONHCH2CH3)N]+Cl-、
[CH3(CH2)13N(CH3)2CH2CONHCH2CH3]+Cl-、
[CH3(CH2)13N(CH2CH3)2CH2Ph]+Br-、
[CH3(CH2)13N(CH3)2CH2COOCH2CH3]+Cl-、
[CH3(CH2)15N(CH2CH3)2CH2Ph]+Br-、
[CH3(CH2)13N(CH2CH3)2(CH2Ph)]+Cl-、
[CH3(CH2)11N(CH2CH3)2CH2Ph]+Br-、
[CH3(CH2)15N(CH3)2CH2CONHCH2CH3]+Cl-、
[CH3(CH2)17N(CH2CH3)2CH2Ph]+Br-、
[CH3(CH2)15N(CH3)2CH2COOCH2CH3]+Cl-、
[CH3(CH2)17N(CH2CH2CH3)2CH2Ph]+Br-、
[CH3(CH2)15N(CH2CH3)2(CH2Ph)]+Cl-、
[CH3(CH2)15N(CH2CH2CH3)2CH2Ph]+Br-、
[CH3(CH2)17N(CH3)2CH2CONHCH2CH3]+Cl-、
[CH3(CH2)13N(CH2CH2CH3)2CH2Ph]+Br-、
[CH3(CH2)17N(CH3)2CH2COOCH2CH3]+Cl-、
[CH3(CH2)11N(CH2CH2CH3)2CH2Ph]+Br-、
[CH3(CH2)17N(CH2CH3)2(CH2Ph)]+Cl-、
[CH3(CH2)17N(CH2CH2CH3)2CH2Ph]+Cl-、
[CH3(CH2)11N(CH3)2CH2CONHCH2CH3]+Cl-、
[CH3(CH2)15N(CH2CH2CH3)2CH2Ph]+Cl-、
[CH3(CH2)11N(CH3)2CH2COOCH2CH3]+Cl-、
[CH3(CH2)13N(CH2CH2CH3)2CH2Ph]+Cl-、
[CH3(CH2)11N(CH2CH3)2(CH2Ph)]+Cl-、
[CH3(CH2)11N(CH2CH2CH3)2CH2Ph]+Cl-、
and so on.
Example 8
Preparation of composite phase transfer catalyst I
Triethylbenzylammonium chloride 20g, [ O ]2N-Ph-CH(OH)CH(CH2OH)N(CH2Ph)3]+Cl50g, 10g of trimethyl hexadecyl ammonium chloride, 50g of polyethylene glycol (20000) and 100g of water. Slowly raising the temperature to 80 ℃ under stirring, stirring for 3 hours at constant temperature, cooling and discharging to obtain the composite phase transfer catalyst I.
Example 9
Preparation of composite phase transfer catalyst II
Ethylbenzylammonium bromide 20g [ O ]2N-Ph-CH(OH)CH(CH2OH)(CH2Ph)2N(CH2COOCH3)]+50g of Clc, 10g of dimethyl hexadecyl benzyl ammonium chloride, 100g of polyethylene glycol (2000) and 100g of water. Slowly raising the temperature to 80 ℃ under stirring, stirring for 3 hours at constant temperature, cooling and discharging to obtain the composite phase transfer catalyst II.
Example 10
Preparation of composite phase transfer catalyst III
Tributylbenzyl ammonium chloride 20, [ O ]2N-Ph-CH(OH)CH(CH2OH)N(CH2CONHCH3]+Cl-50g of dimethyl tetradecyl benzyl ammonium chloride, 10g of penetrating agent JFC200g and 100g of water. Slowly raising the temperature to 80 ℃ under stirring, stirring for 3 hours at constant temperature, cooling and discharging to obtain the composite phase transfer catalyst III.
Example 11
Preparation of composite phase transfer catalyst IV
Trioctylbenzyl ammonium bromide 20g, [ O ]2N-Ph-CH(OH)CH(CH2OH)N(CH2Ph)2(CH3)]+I-50g、[CH3(CH2)13N(CH3)2CH2COOCH3]+Cl-10g, 300g of polyethylene glycol (600) and 100g of water. Slowly raising the temperature to 80 ℃ under stirring, stirring for 3 hours at constant temperature, cooling and discharging to obtain the composite phase transfer catalyst IV.
Example 12
Preparation of composite phase transfer catalyst V
[O2N-Ph-CH(OH)CH(CH2OH)N(CH2Ph)2(CH3)]+Cl- 50g、[CH3(CH2)13N(CH3)2CH2CONHCH3]+Cl-10g of emulsifier TX-15300 g and 100g of water. Slowly raising the temperature to 80 ℃ under stirring, stirring for 3 hours at constant temperature, cooling and discharging to obtain the composite phase transfer catalyst V.
Example 13
Preparation of composite phase transfer catalyst VI
Trioctylbenzylammonium chloride, [ O ]2N-Ph-CH(OH)CH(CH2OH)N(CH2Ph)3]+Cl-50g、[CH3(CH2)13N(CH3)2(CH2Ph)]+Cl-10g of detergent JU300g and 100g of water. Slowly raising the temperature to 80 ℃ under stirring, stirring for 3 hours at constant temperature, cooling and discharging to obtain the composite phase transfer catalyst VI.
Example 14
Preparation of composite phase transfer catalyst VII
10g, [ O ] of trimethylhexadecylammonium chloride2N-Ph-CH(OH)CH(CH2OH)N(CH2Ph)3]+Cl-50g、[CH3(CH2)13N(CH3)2(CH2Ph)]+Cl-10g of emulsifier SE 300g and 100g of water. Slowly raising the temperature to 80 ℃ under stirring, stirring for 3 hours at constant temperature, cooling and discharging to obtain the composite phase transfer catalyst VII.
The above examples 8 to 14 are typical synthesis methods of the composite catalyst of the present invention, and different composite phase transfer catalysts can be synthesized by using the above quaternary ammonium salt and nonionic compound.
Industrial control example 15
Synthesis of omethoate intermediate oxygen thiophosphate
1300Kg of 43.52% aqueous solution of ammonium salt of omethoate sulfur and phosphorus is put into a reaction kettle, mineral acid is added to adjust the pH value to be 7.5, 1600Kg of methyl chloroacetate is put into the reaction kettle, the temperature is raised, the temperature is controlled to be 58-62 ℃ under stirring, the reaction lasts 120 minutes, the discharging is carried out, the standing is carried out for 30 minutes, the layering is carried out, the crude sulfur and phosphorus oxide ester is subjected to reduced pressure distillation, the yield of the refined sulfur and phosphorus oxide ester is 601.3Kg, the content of a gas chromatography is 81.15%, and the yield is 64.08%.
Industrial example 15
Synthesis of omethoate intermediate oxygen sulfur phosphorus ester by composite phase transfer catalyst I catalysis
1300Kg of 41.77% aqueous solution of ammonium omethoate, which is put into a reaction kettle, is added with mineral acid to adjust the pH value to be 7.5, and then 1600Kg of methyl chloroacetate is added with 10.5Kg of the composite phase transfer catalyst I of the invention, the temperature is raised, the temperature is controlled to be 55-58 ℃ under stirring, the reaction is carried out for 80 minutes, the discharging is carried out, the standing is carried out for 30 minutes, the layering is carried out, the crude oxygen sulfur phosphate is subjected to reduced pressure distillation, the yield of the refined oxygen sulfur phosphate is 702Kg, the content of the gas chromatography is 82.05%, and the yield is 78.82%.
Example 16
Synthesis of omethoate intermediate oxygen sulfur phosphorus ester catalyzed by composite phase transfer catalyst
120g of 45.12 percent aqueous solution of ammonium omethoate, putting the aqueous solution into a reaction bottle, adding mineral acid to adjust the pH value to be 7.5, then adding 150g of methyl chloroacetate, adding 1.0g of the composite phase transfer catalyst II, heating, stirring, controlling the temperature to be 55-58 ℃, reacting for 80 minutes, discharging, standing for 30 minutes, layering, carrying out reduced pressure distillation on crude sulfur oxychloride, wherein the yield of refined sulfur oxychloride is 68.3g, the content of gas chromatography is 86.82 percent, and the yield is 81.63 percent.
Comparative example 16
Synthesis of omethoate intermediate oxygen thiophosphate
Putting 120g of 44.09% aqueous solution of omethoate ammonium sulfate into a reaction bottle, adding mineral acid to adjust the pH value to be 7.5, then adding 150g of methyl chloroacetate, heating, stirring, controlling the temperature to be 58-62 ℃, reacting for 120 minutes, discharging, standing for 30 minutes, layering, and carrying out reduced pressure distillation on crude oxygen thiophosphate, wherein the yield of the refined oxygen thiophosphate is 56.8g, the content of a gas chromatography is 79.0%, and the yield is 63.01%.
Example 17
Compositions respectively added with composite phase transfer catalyst for catalyzing synthesis of omethoate intermediate oxygen thiophosphate
Putting 120g of 44.04% aqueous solution of ammonium omethoate, adding mineral acid to adjust the pH value to 7.5, putting 150g of methyl chloroacetate, and adding the cationic quaternary ammonium salt phase transfer catalysts (0.2 g of triethylbenzylammonium chloride, 0.1g of dimethylhexadecylbenzylammonium chloride and [ O ] to form the composite phase transfer catalyst of the invention2N-Ph-CH(OH)CH(CH2OH)(CH2Ph)2NCH3]+I-0.2g of non-ionic phase transfer catalyst (polyethylene glycol 20000)0.5g, heating, stirring, controlling the temperature to 55-58 ℃, reacting for 80 minutes, discharging, standing for 30 minutes, layering, carrying out reduced pressure distillation on crude thiophosphate, and obtaining refined thiophosphate with the yield of 65.6g, the content of gas chromatography of 87.01% and the yield of 80.49%.
Example 18
Synthesis of omethoate intermediate oxygen sulfur phosphorus ester by composite phase transfer catalyst III catalysis
Putting 120g of 46.02% aqueous solution of ammonium omethoate, adding mineral acid to adjust the pH value to be 7.5, then adding 150g of methyl chloroacetate, adding 1.0g of the composite phase transfer catalyst III, heating, stirring, controlling the temperature to be 55-58 ℃, reacting for 80 minutes, discharging, standing for 30 minutes, layering, carrying out reduced pressure distillation on crude oxygen thiophosphate, and obtaining 71.4g of refined oxygen thiophosphate, wherein the content of a gas chromatography is 84.92%, and the yield is 81.84%.
Example 19
Synthesis of omethoate intermediate oxygen sulfur phosphorus ester by composite phase transfer catalyst IV catalysis
Putting 120g of 45.5% aqueous solution of ammonium omethoate, adding mineral acid to adjust the pH value to be 7.5, then putting 150g of methyl chloroacetate, adding 1.0g of the composite phase transfer catalyst IV of the invention, heating, controlling the temperature to be 55-58 ℃ under stirring, reacting for 80 minutes, discharging, standing for 30 minutes, layering, carrying out reduced pressure distillation on crude sulfur oxychloride, and obtaining 68.0g of refined sulfur oxychloride with the gas chromatography content of 88.23%, wherein the yield is 81.9%.
Example 20
Synthesis of omethoate intermediate oxygen sulfur phosphorus ester by composite phase transfer catalyst V catalysis
Putting 120g of 47.1% aqueous solution of omethoate ammonium sulfate into a reaction bottle, adding mineral acid to adjust the pH value to be 7.5, then adding 150g of methyl chloroacetate, adding 1.0g of the composite phase transfer catalyst, heating, stirring, controlling the temperature to be 55-58 ℃, reacting for 80 minutes, discharging, standing for 30 minutes, layering, carrying out reduced pressure distillation on crude sulfur oxychloride, wherein the yield of refined sulfur oxychloride is 71.8g, the content of gas chromatography is 86.5%, and the yield is 81.9%.
Example 21
Synthesis of omethoate intermediate oxygen sulfur phosphorus ester by composite phase transfer catalyst VI catalysis
Putting 120g of 46.5% ammonium salt water solution of omethoate sulfur, adding mineral acid to adjust the pH value to be 7.5, then putting 150g of methyl chloroacetate, adding 1.0g of the composite phase transfer catalyst VI of the invention, heating, controlling the temperature to be 55-58 ℃ under stirring, reacting for 80 minutes, discharging, standing for 30 minutes, layering, carrying out reduced pressure distillation on crude sulfur oxychloride, wherein the yield of refined sulfur oxychloride is 71.6g, the content of gas chromatography is 85.8%, and the yield is 82.05%.
Example 22
Synthesis of omethoate intermediate oxygen sulfur phosphorus ester by composite phase transfer catalyst VII catalysis
Putting 120g of 44.02% aqueous solution of ammonium omethoate, adding mineral acid to adjust the pH value to be 7.5, then adding 150g of methyl chloroacetate, adding 1.0g of the composite phase transfer catalyst VII of the invention, heating, stirring, controlling the temperature to be 55-58 ℃, reacting for 80 minutes, discharging, standing for 30 minutes, layering, carrying out reduced pressure distillation on crude sulfur oxychloride, wherein the yield of refined sulfur oxychloride is 66.8g, the content of gas chromatography is 85.75%, and the yield is 80.83%.
Example 23
Synthesis of omethoate intermediate oxygen sulfur phosphorus ester by single quaternary ammonium salt catalysis
Putting 120g of 44.09% aqueous solution of omethoate ammonium sulfate into a reaction bottle, adding mineral acid to adjust the pH value to be 7.5, then adding 150g of methyl chloroacetate, adding 1.0g of trimethyl benzyl ammonium chloride, heating, stirring, controlling the temperature to be 55-58 ℃, reacting for 80 minutes, discharging, standing for 30 minutes, layering, carrying out reduced pressure distillation on crude oxygen thiophosphate, obtaining 60.89g of refined oxygen thiophosphate, wherein the content of a gas chromatography is 82.3%, and the yield is 70.38%.
Example 24
Synthesis of omethoate intermediate oxygen sulfur phosphorus ester by composite quaternary ammonium salt catalysis
Putting 120g of 43.96% aqueous solution of ammonium omethoate, adding mineral acid to adjust the pH value to 7.5, and putting 150g of methyl chloroacetate, [ O ]2N-Ph-CH(OH)CH2(CH2OH)(CH2Ph)2NCH3]+I-1.0g of trimethyl benzyl ammonium chloride, heating, stirring, controlling the temperature to be 55-58 ℃, reacting for 80 minutes, discharging, standing for 30 minutes, layering, carrying out reduced pressure distillation on crude oxygen sulfur phosphate, and refiningThe yield of the thiophosphate is 63.4g, the content of the thiophosphate is 84.10 percent by gas chromatography, and the yield is 75.10 percent.
Example 25
Synthesis of omethoate intermediate oxygen thiophosphate by catalysis of composite tertiary amine phase transfer agent
Putting 120g of 43.96% omethoate ammonium salt aqueous solution into a reaction bottle, adding mineral acid to adjust the pH value to be 7.5, then adding 150g of methyl chloroacetate, adding 2.0g of an equal proportion mixture of diethylaniline, triethylamine, tributylamine and polyethylene glycol 2000, heating, stirring, controlling the temperature to be 55-58 ℃, reacting for 80 minutes, discharging, standing for 30 minutes, layering, carrying out reduced pressure distillation on crude oxygen thiophosphate, and obtaining 62.5g of refined oxygen thiophosphate, wherein the content of gas chromatography is 84.90%, and the yield is 74.74%.
From the implementation, the addition of the phase transfer catalyst can improve the yield of the oxyphosphorus thiotepa by about 15 percent when the oxyphosphorus thiotepa intermediate in large-scale industrial production is added, and the yield of the oxyphosphorus thiotepa can be improved by 10 to 18 percent when the phase transfer catalyst is added in a small experiment.
The reaction time can be shortened by one third once the phase transfer catalyst of the invention is added, whether for large industrial production or small experiments.
Claims (3)
1. A composite phase transfer catalyst having a β -hydroxy structure, characterized by: it contains quaternary ammonium salt compound of the following general formula
[R1R2R3R4N]+X-In the formula R1Is O2N-Ph-CH(OH)CH(CH2OH)，
R2、R3Is C1～C18An alkyl group, a benzyl group,
R1is benzyl, C1～C18Alkyl, -CH2COO(CH2)nCH3、-CH2CONH(CH2)nCH3Wherein n is an integer of 0 to 8,
x is Cl or Br.
2. The composite phase transfer catalyst of β -hydroxy structure according to claim 1, characterized in that:
when in the formula R1Is O2N-Ph-CH(OH)CH(CH2OH) in the presence of a nitrogen-containing gas,
R2、R3is an alkyl group having 1 to 18 carbon atoms,
R4is C1-C18 alkyl or benzyl,
x is Cl or Br.
3. The composite phase transfer catalyst of β -hydroxy structure according to claim 2, characterized in that:
when in the formula R1Is O2N-Ph-CH(OH)CH(CH2OH) in the presence of a nitrogen-containing gas,
R2、R3is C2An alkyl group, a carboxyl group,
R4is C12An alkyl group, a carboxyl group,
x is Br.
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