CN103274924B - Compound 1,3-dicarboxyl-2,2-bis(carbethoxy)propane and synthesis method thereof - Google Patents
Compound 1,3-dicarboxyl-2,2-bis(carbethoxy)propane and synthesis method thereof Download PDFInfo
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- CN103274924B CN103274924B CN201310198180.4A CN201310198180A CN103274924B CN 103274924 B CN103274924 B CN 103274924B CN 201310198180 A CN201310198180 A CN 201310198180A CN 103274924 B CN103274924 B CN 103274924B
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Abstract
The invention relates to a compound 1,3-dicarboxyl-2,2-bis(carbethoxy)propane the molecular formula of which is C(CH2COOH)4. A synthesis method of the compound is divided into two steps: a first step of subjecting the polyhalogenated hydrocarbon 1,3-dibromo-2,2-bis(brooethyl)propane, which takes water as a solvent, to catalyzed synthesis of 1,3-dicyanona-2,2-bis(cyanomethyl)propane under the action of a cyanation agent and by using a phase transfer catalyst and ligand-free copper; and a second step of hydrolyzing the 1,3-dicyanona-2,2-bis(cyanomethyl)propane under the action of inorganic strong acid to obtain the 1,3-dicarboxyl-2,2-bis(carbethoxy)propane. The 1,3-dicarboxyl-2,2-bis(carbethoxy)propane provided by the invention comprises four carboxyl functional groups, which can be subjected to intramolecular decarboxylation reaction in subsequent steps to further synthesize a spiral compound, and therefore, the compound can be applied to epoxy resin to reduce volume shrinkage of the epoxy resin in a curing process.
Description
Technical field
The present invention relates to a kind of new multicomponent carboxylic compound and preparation method thereof, a kind of compound 1 specifically, 3-dicarboxyl-2,2-bis-(acetoxyl) propane and synthetic method thereof.
Background technology
1, 3-dicarboxyl-2, 2-bis-(acetoxyl) propane is the important intermediate of a class, the present invention is from initial product simple and easy to get 1, 3-bis-bromo-2, 2-bis-(brooethyl) propane prepares itrile group compound, under inorganic acid, hydrolysis obtains carboxylic acid cpd, it can be used as chemical intermediate especially, in subsequent experimental, make decarboxylation in its molecule form Spirocyclic compound volution tetracarboxylic acid dianhydride (2, 4, 8, 10-tetra-carbonyl-3, 9-dioxa volution [5.5] undecane), be applied under certain condition in the curing system of epoxy resin, can effectively reduce the cure shrinkage of epoxy-resin systems.The experimental procedure that current only dihalo hydrocarbon is prepared di-carboxylic acid compound is complicated, condition harshness and reactant severe toxicity, and harm is large, and product is difficult for making.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of compound 1 for the deficiency of above-mentioned prior art existence, 3-dicarboxyl-2,2-bis-(acetoxyl) propane, in subsequent step, can there is decarboxylic reaction in molecule in its four carboxyl functional groups that contain, form Spirocyclic compound volution tetracarboxylic acid dianhydride (2,4,8,10-tetra-carbonyl-3,9-dioxa volution [5.5] undecane).
Another object of the present invention is to provide a kind of compound 1,3-dicarboxyl-2, the synthetic method of 2-bis-(acetoxyl) propane.
The present invention is that the technical scheme that the problem of the above-mentioned proposition of solution adopts is:
A kind of compound 1,3-dicarboxyl-2,2-bis-(acetoxyl) propane, its molecular formula is C (CH
2cOOH)
4, structural formula is
A kind of compound 1,3-dicarboxyl-2, the synthetic method of 2-bis-(acetoxyl) propane, is divided into two steps:
Step (1), by polyhalohydrocarbon 1,3-bis-is bromo-2, and 2-bis-(brooethyl) propane be take water as solvent, under the effect of nitrilation agent, by phase-transfer catalyst with without the copper of part, catalyzes and synthesizes 1,3-dinitrile-2,2-bis-(nitrile methyl) propane;
Step (2), 1,3-dinitrile-2,2-bis-(nitrile methyl) propane is hydrolyzed and obtains 1,3-dicarboxyl-2.2-bis-(acetoxyl) propane under inorganic acid effect.
Press such scheme, the mol ratio of described aqueous solvent and copper catalyst is 5:1～7:1.
Press such scheme, described nitrilation agent is anhydrous K
4fe (CN)
6.
Press such scheme, described nitrilation agent anhydrous K
4fe (CN)
6with polyhalohydrocarbon 1,3-bis-is bromo-2, and the mol ratio of 2-bis-(brooethyl) propane is 3:2～5:4.
Press such scheme, described phase-transfer catalyst is Tetrabutyl amonium bromide (TBAB), without the copper catalyst of part, is Cu (OAc)
2.
Press such scheme, described phase-transfer catalyst TBAB and polyhalohydrocarbon 1,3-bis-is bromo-2, and the mol ratio of 2-bis-(brooethyl) propane is 1:1～1:1.5, without the copper catalyst Cu (OAc) of part
2account for phase-transfer catalyst total mass 8%～10%.
Press such scheme, 160 ℃～200 ℃ of described step (1) temperature of reaction, reaction times 50～80min.
Press such scheme, described hydrolysis reaction step is passed through under inorganic acid exists, and 1,3-dinitrile-2,2-bis-(nitrile methyl) propane reacts with water, the consumption of described hydrolysis reaction water and 1,3-dinitrile-2, the mol ratio of 2-bis-(nitrile methyl) propane is 1:1.5～1:2.0.
Press such scheme, described inorganic acid is 98% vitriol oil, the vitriol oil and 1,3-dinitrile-2, and the mol ratio of 2-bis-(nitrile methyl) propane is 1:1～1.5:1.
A kind of compound 1,3-dicarboxyl-2, the synthetic method of 2-bis-(acetoxyl) propane, concrete steps are as follows:
(1) according to mol ratio, be 3:2～5:4, prepare nitrilation agent anhydrous K
4fe (CN)
6bromo-2 with 1,3-bis-, 2-bis-(brooethyl) propane is standby; Bromo-2 according to transfer catalyst TBAB and 1,3-bis-, the mol ratio of 2-bis-(brooethyl) propane is that 1:1～1:1.5 prepares TBAB; Copper catalyst Cu (OAc) without part
2account for phase-transfer catalyst total mass 8%～10%; According to the mol ratio of the amount of aqueous solvent and copper catalyst, be that 5:1～7:1 water intaking is standby.
By Cu (OAc)
2catalyzer is stirred to homogeneous phase in joining in aqueous solvent, then adds anhydrous K
4[Fe (CN)
6], TBAB and 1,3-bis-is bromo-2,2-bis-(brooethyl) propane, by after container sealing in 160 ℃～200 ℃ reacting by heating 50min～80min, after reaction finishes, make system naturally cool to room temperature, use extracted with diethyl ether product three times, with Rotary Evaporators, revolve steaming ether, GC detects analysis, and make product 1, and 3-dinitrile-2,2-bis-(nitrile methyl) propane is by chromatographic column purifying;
(2), under nitrogen atmosphere, in room temperature to being equipped with in the reactor of agitator, add 2/3 (total amount of required water and 1,3-dinitrile-2, the mol ratio of 2-bis-(nitrile methyl) propane is 1:1.5～1:2.0) of required water cumulative volume, topple over subsequently 98%H
2sO
4, sulfuric acid and 1, 3-dinitrile-2, 2-bis-(nitrile methyl) propane mol ratio 1:1～1.5:1, , make temperature of reaction system be increased to 120 ℃, then in 1h, introduce above-mentioned steps prepared 1, 3-dinitrile-2, 2-bis-(nitrile methyl) propane, temperature of reaction system is controlled at 120 ℃, at this temperature, be incubated after 20～40min subsequently, in 10min, add 1/3 of required water cumulative volume remainder, and temperature is elevated to 130 ℃ of maintenance 6h, after finishing, reaction stops stirring, reaction medium layering, make it to naturally cool to 90 ℃, upper strata and lower layer of water are separated, obtain 1, 3-dicarboxyl-2.2-bis-(acetoxyl) propane.
Reaction process of the present invention is as follows:
Of the present invention 1,3-dicarboxyl-2.2-bis-(acetoxyl) propane can be used for synthetic 2,4,8,10-, tetra-carbonyl-3,9-dioxa volution [5.5] undecane, concrete steps are as follows: by 1,3-dicarboxyl-2, under the condition that 2-bis-(acetoxyl) propane exists at inertia dewatering agent, be heated to boiling point, carry out azeotropic dehydration, while no longer including droplet generation in water trap, show to dewater completely, obtain 2,4,8,10-, tetra-carbonyl-3,9-dioxa volution [5.5] undecane; Described inertia dewatering agent is dimethylbenzene.
Above-mentioned synthetic 2,4,8,10-tetra-carbonyl-3, the undecanoic reaction formula of 9-dioxa volution [5.5] is as follows:
Compared with prior art, the invention has the advantages that:
First, 1,3-dicarboxyl-2,2-bis-(acetoxyl) propane is the important intermediate of a class, in subsequent step, can there is decarboxylic reaction in molecule in its four carboxyl functional groups that contain, and then synthesizing spiro shape compound, be applied in epoxy resin, can effectively reduce the volumetric shrinkage of epoxy resin in solidification process.
The second, the present invention is polyhalohydrocarbon 1, and 3-bis-is bromo-2, and 2-bis-(brooethyl) propane is take water as solvent, with nontoxic and cheap K
4[Fe (CN)
6] be nitrilation agent, by TBAB, be phase-transfer catalyst and without the Cu (OAc) of part
2for catalyst synthetic 1,3-dinitrile-2,2-bis-(nitrile methyl) propane, then by 1,3-dinitrile-2,2-bis-(nitrile methyl) propane is hydrolyzed and obtains 1,3-dicarboxyl-2.2-bis-(acetoxyl) propane under inorganic acid effect, and this method is simple and easy to do, nontoxic inexpensive, reaction conditions is gentle, and products collection efficiency high purity is large, can obtain than the longer polycarboxylic acid of raw material hydro carbons carbochain.
Accompanying drawing explanation
Fig. 1 is 1,3-dicarboxyl-2,2-bis-(acetoxyl) propane molecular structure.
Fig. 2 is 1,3-dicarboxyl-2,2-bis-(acetoxyl) propane preparation were established figure.
Fig. 3 is 1,3-dicarboxyl-2, the infrared spectrogram of 2-bis-(acetoxyl) propane.
Embodiment
In order to understand better the present invention, below in conjunction with example, further illustrate content of the present invention, but the present invention is not only confined to the following examples.
Anhydrous K of the present invention
4fe (CN)
6through following method, obtain, by K
4fe (CN)
63H
2the O particle that is ground into powder in mortar, is laid on watch-glass, and watch-glass is placed in vacuum drying oven, and 75 ℃ dry.Certainly, the anhydrous K that other techniques obtain
4fe (CN)
6also be applicable to the present invention.
Embodiment 1
(1) a kind of 1,3-dinitrile-2, the synthetic method of 2-bis-(nitrile methyl) propane, step is as follows:
According to mol ratio, be 3:2, prepare nitrilation agent anhydrous K
4fe (CN)
6bromo-2 with 1,3-bis-, 2-bis-(brooethyl) propane is standby; Bromo-2 according to transfer catalyst TBAB and 1,3-bis-, the mol ratio of 2-bis-(brooethyl) propane is that 1:1 prepares TBAB; Copper catalyst Cu (OAc) without part
2account for phase-transfer catalyst total mass 10%, according to the mol ratio of the amount of aqueous solvent and copper catalyst, be that 5:1 water intaking is standby;
By Cu (OAc)
2catalyzer joins in aqueous solvent, is stirred to homogeneous phase, then adds anhydrous K
4[Fe (CN)
6], TBAB and 1,3-bis-is bromo-2,2-bis-(brooethyl) propane, by after container sealing in 180 ℃ of reacting by heating 50min, after reaction finishes, make system naturally cool to room temperature, use extracted with diethyl ether product three times, with Rotary Evaporators, revolve steaming ether, GC detects analysis, and make product 1, and 3-dinitrile-2,2-bis-(nitrile methyl) propane is by chromatographic column purifying;
Reaction formula:
(2) a kind of 1, the preparation process of 3-dicarboxyl-2.2-bis-(acetoxyl) propane is as follows:
Under nitrogen atmosphere, in room temperature to being equipped with in the reactor of agitator, add 2/3 (total amount of required water and 1,3-dinitrile-2, the mol ratio of 2-bis-(nitrile methyl) propane is 1:1.5) of required water cumulative volume, topple over subsequently 98%H
2sO
4, sulfuric acid and 1, 3-dinitrile-2, 2-bis-(nitrile methyl) propane mol ratio 1:1, , make temperature of reaction system be increased to 120 ℃, then in 1h, introduce above-mentioned steps prepared 1, 3-dinitrile-2, 2-bis-(nitrile methyl) propane, temperature of reaction system is controlled at 120 ℃, at this temperature, be incubated after 20min subsequently, in 10min, add 1/3 of required water cumulative volume remainder, and temperature is elevated to 130 ℃ of maintenance 6h, after finishing, reaction stops stirring, reaction medium layering, make it to naturally cool to 90 ℃, upper strata and lower layer of water are separated, obtain 1, 3-dicarboxyl-2.2-bis-(acetoxyl) propane.Through distillation, extraction, recrystallization, obtaining productive rate is 91%, and the infrared figure of product is shown in Fig. 3.Reaction formula is as follows:
Infared spectrum is analyzed as follows, and known product is really 1,3-dicarboxyl-2,2-bis-(acetoxyl) propane.
Embodiment 2
(1) a kind of 1,3-dinitrile-2, the synthetic method of 2-bis-(nitrile methyl) propane, step is as follows:
According to mol ratio, be 4:3, prepare nitrilation agent anhydrous K
4fe (CN)
6bromo-2 with 1,3-bis-, 2-bis-(brooethyl) propane is standby; Bromo-2 according to transfer catalyst TBAB and 1,3-bis-, the mol ratio of 2-bis-(brooethyl) propane is that 1:1.5 prepares TBAB; Copper catalyst Cu (OAc) without part
2account for phase-transfer catalyst total mass 9%, according to the mol ratio of the amount of aqueous solvent and copper catalyst, be that 7:1 water intaking is standby;
By Cu (OAc)
2catalyzer joins in aqueous solvent, is stirred to homogeneous phase, then adds anhydrous K
4[Fe (CN)
6], TBAB and 1,3-bis-is bromo-2,2-bis-(brooethyl) propane, by after container sealing in 200 ℃ of reacting by heating 75min, after reaction finishes, make system naturally cool to room temperature, use extracted with diethyl ether product three times, with Rotary Evaporators, revolve steaming ether, GC detects analysis, and make product 1, and 3-dinitrile-2,2-bis-(nitrile methyl) propane is by chromatographic column purifying;
(2) a kind of 1, the preparation process of 3-dicarboxyl-2.2-bis-(acetoxyl) propane is as follows:
Under nitrogen atmosphere, in room temperature to being equipped with in the reactor of agitator, add 2/3 (total amount of required water and 1,3-dinitrile-2, the mol ratio of 2-bis-(nitrile methyl) propane is 1:2.0) of required water cumulative volume, topple over subsequently 98%H
2sO
4, sulfuric acid and 1, 3-dinitrile-2, 2-bis-(nitrile methyl) propane mol ratio 1.5:1, , make temperature of reaction system be increased to 120 ℃, then in 1h, introduce above-mentioned steps prepared 1, 3-dinitrile-2, 2-bis-(nitrile methyl) propane, temperature of reaction system is controlled at 120 ℃, at this temperature, be incubated after 40min subsequently, in 10min, add 1/3 of required water cumulative volume remainder, and temperature is elevated to 130 ℃ of maintenance 6h, after finishing, reaction stops stirring, reaction medium layering, make it to naturally cool to 90 ℃, upper strata and lower layer of water are separated, obtain 1, 3-dicarboxyl-2.2-bis-(acetoxyl) propane.Through distillation, extraction, recrystallization, obtaining products collection efficiency is 92.5%.
Embodiment 3
(1) a kind of 1,3-dinitrile-2, the synthetic method of 2-bis-(nitrile methyl) propane, step is as follows:
According to mol ratio, be 5:4, prepare nitrilation agent anhydrous K
4fe (CN)
6bromo-2 with 1,3-bis-, 2-bis-(brooethyl) propane is standby; Bromo-2 according to transfer catalyst TBAB and 1,3-bis-, the mol ratio of 2-bis-(brooethyl) propane is that 1:1.2 prepares TBAB; Copper catalyst Cu (OAc) without part
2account for phase-transfer catalyst total mass 8%, according to the mol ratio of the amount of aqueous solvent and copper catalyst, be that 6:1 water intaking is standby;
By Cu (OAc)
2catalyzer joins in aqueous solvent, is stirred to homogeneous phase, then adds anhydrous K
4[Fe (CN)
6], TBAB and 1,3-bis-is bromo-2,2-bis-(brooethyl) propane, by after container sealing in 160 ℃ of reacting by heating 80min, after reaction finishes, make system naturally cool to room temperature, use extracted with diethyl ether product three times, with Rotary Evaporators, revolve steaming ether, GC detects analysis, and make product 1, and 3-dinitrile-2,2-bis-(nitrile methyl) propane is by chromatographic column purifying;
(2) a kind of 1, the preparation process of 3-dicarboxyl-2.2-bis-(acetoxyl) propane is as follows:
Under nitrogen atmosphere, in room temperature to being equipped with in the reactor of agitator, add 2/3 (total amount of required water and 1,3-dinitrile-2, the mol ratio of 2-bis-(nitrile methyl) propane is 1:1.7) of required water cumulative volume, topple over subsequently 98%H
2sO
4, sulfuric acid and 1, 3-dinitrile-2, 2-bis-(nitrile methyl) propane mol ratio 1.3:1, , make temperature of reaction system be increased to 120 ℃, then in 1h, introduce above-mentioned steps prepared 1, 3-dinitrile-2, 2-bis-(nitrile methyl) propane, temperature of reaction system is controlled at 120 ℃, at this temperature, be incubated after 30min subsequently, in 10min, add 1/3 of required water cumulative volume remainder, and temperature is elevated to 130 ℃ of maintenance 6h, after finishing, reaction stops stirring, reaction medium layering, make it to naturally cool to 90 ℃, upper strata and lower layer of water are separated, obtain 1, 3-dicarboxyl-2.2-bis-(acetoxyl) propane.Through distillation, extraction, recrystallization, obtaining products collection efficiency is 91.6%.
Application examples:
1,3-dicarboxyl-2.2-bis-(acetoxyl) propane is for the synthesis of 2,4,8,10-, tetra-carbonyl-3,9-dioxa volution [5.5] undecane, and concrete steps are as follows:
By 1,3-dicarboxyl-2, under the condition that 2-bis-(acetoxyl) propane exists at inertia dewatering agent dimethylbenzene, are heated to boiling point, carry out azeotropic dehydration, while no longer including droplet generation in water trap, show to dewater completely, obtain 2,4,8,10-, tetra-carbonyl-3,9-dioxa volution [5.5] undecane.
This New-type spiro compound-volution tetracarboxylic acid dianhydride (2,4,8,10-tetra-carbonyl-3,9-dioxa volution [5.5] undecane) be a kind of novel swelling and curing agent for epoxy-resin systems, be mainly used in poured with epoxy resin and fibre reinforced composites field thereof, in order to reduce epoxy resin and matrix material thereof the volumetric shrinkage in solidification process, the system volumetric shrinkage of this technology is reduced to 0～0.5%.
Application method is as follows: count by weight 100 parts of E51 epoxy resin; 33 parts of volution tetracarboxylic acid dianhydrides, mix, pour into a mould, arrange bubble, are heated to 150 ℃ of curing 4h; 170 ℃ of after fixing 2h; 190 ℃ of after fixing 2h; 210 ℃ of after fixing 2h, the volume change of employing dilatometer tracking measurement reaction system, measures the volumetric shrinkage of epoxy resin in solidification process lower than 0.5%.
Claims (8)
1. a compound 1,3-dicarboxyl-2, the synthetic method of 2-bis-(acetoxyl) propane, is characterized in that it is divided into two steps:
Step (1), by polyhalohydrocarbon 1,3-bis-is bromo-2, and 2-bis-(brooethyl) propane be take water as solvent, under the effect of nitrilation agent, by phase-transfer catalyst with without the copper catalyst of part, catalyzes and synthesizes 1,3-dinitrile-2,2-bis-(nitrile methyl) propane;
Step (2), 1,3-dinitrile-2,2-bis-(nitrile methyl) propane is hydrolyzed and obtains 1,3-dicarboxyl-2.2-bis-(acetoxyl) propane under inorganic acid effect;
Wherein, described nitrilation agent is anhydrous K
4fe (CN)
6, described phase-transfer catalyst is Tetrabutyl amonium bromide, without the copper catalyst of part, is Cu (OAc)
2, described inorganic acid is 98% vitriol oil.
2. a kind of compound 1 according to claim 1,3-dicarboxyl-2, the synthetic method of 2-bis-(acetoxyl) propane, is characterized in that the amount of described aqueous solvent and the mol ratio of copper catalyst are 5:1～7:1.
3. a kind of compound 1 according to claim 1,3-dicarboxyl-2, the synthetic method of 2-bis-(acetoxyl) propane, is characterized in that described nitrilation agent is anhydrous K
4fe (CN)
6, described anhydrous K
4fe (CN)
6with polyhalohydrocarbon 1,3-bis-is bromo-2, and the mol ratio of 2-bis-(brooethyl) propane is 3:2～5:4.
4. a kind of compound 1 according to claim 1,3-dicarboxyl-2, the synthetic method of 2-bis-(acetoxyl) propane, it is characterized in that described phase-transfer catalyst Tetrabutyl amonium bromide and polyhalohydrocarbon 1,3-bis-bromo-2, the mol ratio of 2-bis-(brooethyl) propane is 1:1～1:1.5, without the copper catalyst Cu (OAc) of part
2account for 8%～10% of phase-transfer catalyst total mass.
5. a kind of compound 1 according to claim 1,3-dicarboxyl-2, the synthetic method of 2-bis-(acetoxyl) propane, is characterized in that 160 ℃～200 ℃ of described step (1) temperature of reaction, reaction times 50～80min.
6. a kind of compound 1 according to claim 1,3-dicarboxyl-2, the synthetic method of 2-bis-(acetoxyl) propane, it is characterized in that described hydrolysis reaction step is by under existing at inorganic acid, 1,3-dinitrile-2,2-bis-(nitrile methyl) propane reacts with water, the consumption of described hydrolysis reaction water and 1,3-dinitrile-2, the mol ratio of 2-bis-(nitrile methyl) propane is 1:1.5～1:2.0.
7. a kind of compound 1 according to claim 1,3-dicarboxyl-2, the synthetic method of 2-bis-(acetoxyl) propane, is characterized in that the described vitriol oil and 1,3-dinitrile-2, the mol ratio of 2-bis-(nitrile methyl) propane is 1:1～1.5:1.
8. a kind of compound 1 according to claim 1,3-dicarboxyl-2, the synthetic method of 2-bis-(acetoxyl) propane, is characterized in that concrete steps are as follows:
(1) according to mol ratio, be 3:2～5:4, prepare nitrilation agent anhydrous K
4fe (CN)
6bromo-2 with 1,3-bis-, 2-bis-(brooethyl) propane is standby; Bromo-2 according to transfer catalyst Tetrabutyl amonium bromide and 1,3-bis-, the mol ratio of 2-bis-(brooethyl) propane is that 1:1～1:1.5 prepares Tetrabutyl amonium bromide; Copper catalyst Cu (OAc) without part
2account for 8%～10% of phase-transfer catalyst total mass; According to the mol ratio of the amount of aqueous solvent and copper catalyst, be that 5:1～7:1 water intaking is standby;
By Cu (OAc)
2catalyzer joins in aqueous solvent, is stirred to homogeneous phase, then adds anhydrous K
4[Fe (CN)
6], Tetrabutyl amonium bromide and 1,3-bis-is bromo-2,2-bis-(brooethyl) propane, by after container sealing in 160 ℃～200 ℃ reacting by heating 50min～80min, after reaction finishes, make system naturally cool to room temperature, use extracted with diethyl ether product three times, with Rotary Evaporators, revolve steaming ether, GC detects analysis, and make product 1, and 3-dinitrile-2,2-bis-(nitrile methyl) propane is by chromatographic column purifying;
(2) under nitrogen atmosphere, in room temperature to being equipped with in the reactor of agitator, add 2/3 of required water inventory volume, the total amount of required water and 1,3-dinitrile-2, the mol ratio of 2-bis-(nitrile methyl) propane is 1:1.5～1:2.0, topple over subsequently 98%H
2sO
4, sulfuric acid and 1, 3-dinitrile-2, 2-bis-(nitrile methyl) propane mol ratio 1:1～1.5:1, make temperature of reaction system be increased to 120 ℃, then in 1h, introduce above-mentioned steps prepared 1, 3-dinitrile-2, 2-bis-(nitrile methyl) propane, temperature of reaction system is controlled at 120 ℃, at this temperature, keep after 20～40min subsequently, in 10min, add 1/3 of required water cumulative volume remainder, and temperature is elevated to 130 ℃ of maintenance 6h, after finishing, reaction stops stirring, reaction medium layering, make it to naturally cool to 90 ℃, upper strata and lower layer of water are separated, obtain 1, 3-dicarboxyl-2.2-bis-(acetoxyl) propane.
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| US3767598A (en) * | 1971-09-23 | 1973-10-23 | Milchem Inc | Detergent builder |
| CN101641318A (en) * | 2006-11-24 | 2010-02-03 | 罗地亚运作公司 | Method for converting nitrile compounds into corresponding carboxylic acids and esters |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3767598A (en) * | 1971-09-23 | 1973-10-23 | Milchem Inc | Detergent builder |
| CN101641318A (en) * | 2006-11-24 | 2010-02-03 | 罗地亚运作公司 | Method for converting nitrile compounds into corresponding carboxylic acids and esters |
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| Title |
|---|
| Crystal structure and properties of the carboxylic acid derivatives of Schizonpeta mulifida (L.) Briq.;Liu, Ju-Tao,et al;《Chinese Journal of Chemistry》;2008;第26卷(第6期);1129-1132 * |
| Liu, Ju-Tao,et al.Crystal structure and properties of the carboxylic acid derivatives of Schizonpeta mulifida (L.) Briq..《Chinese Journal of Chemistry》.2008,第26卷(第6期),1129-1132. |
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