CN1807389A - Stannous benzoate synthesis method - Google Patents
Stannous benzoate synthesis method Download PDFInfo
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- CN1807389A CN1807389A CN 200610049287 CN200610049287A CN1807389A CN 1807389 A CN1807389 A CN 1807389A CN 200610049287 CN200610049287 CN 200610049287 CN 200610049287 A CN200610049287 A CN 200610049287A CN 1807389 A CN1807389 A CN 1807389A
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- benzoic acid
- benzoate
- solution
- stannous
- acid stannous
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Abstract
The invention provides a new synthesis method for stannous benzoate, which comprises: (1) adding benzoic acid into water, heating to 50~70Deg; stirring while dripping strong base solution to generate benzoate; (2) dripping stannite solution into former solution or water with dissolved benzoate for reaction to obtain the deposition; (3) filtering and drying to obtain the final product. This invention is practical and has high product purity.
Description
Technical field
The present invention relates to a kind of synthetic method of organometallic compound, relate in particular to a kind of benzoic acid stannous novel synthesis.
Background technology
The benzoic acid stannous method of early stage preparation is to react in water with tin protochloride and phenylformic acid to obtain the muddy mixture, use very difficult separation of solid mixture that this method prepares benzoic acid stannous gained, can't be applied to produce [J.D.Donaldson and A.Jelen, J.Chem.Soc. (A), 1986, (6): 1448].
The someone used inferior tin of synthesizing methyl cyclopentadiene or the inferior tin intermediate of methoxyl group and phenylformic acid instead and exchanged preparation [Paul F.R.Ewings and Philip G.Harrison, J.Chem.Soc.1976, (16): 1717] in benzene again afterwards.But this method is at first wanted intermediates such as inferior tin of synthesizing methyl cyclopentadiene or the inferior tin of methoxyl group, secondly, this reaction is main to prepare benzoic acid stannous through displacement in the higher organic solvent of cost, preparation process is many, the working method complexity, benzoic acid stannous cost by this method preparation is very high, only is adapted at coming usefulness as a spot of benzoic acid stannous research of preparation in the laboratory, can't carry out large-scale industrial production.
Summary of the invention
The present invention is directed to prior art and when preparation is benzoic acid stannous, form the muddy mixture, can't be applied to produce and adopt complicated technical process and the more expensive reaction solvent of price to cause the shortcoming that to carry out large-scale industrial production, a kind of benzoic acid stannous novel synthesis is provided.Novel synthesis technological process involved in the present invention is simple, production cost is lower, without organic solvent, can be applicable to large-scale industrial production.
Above-mentioned purpose of the present invention solves by the following technical programs: a kind of benzoic acid stannous novel synthesis is characterized in that being made up of following steps:
(1) benzoate is synthetic: phenylformic acid is added in the entry, be heated to 50～70 ℃, under agitation drip strong base solution and make phenylformic acid generate benzoate and soluble in water, keeping the pH value of solution is 8～11, the time that drips is 30～60 minutes, obtains benzoate solution after the reaction;
(2) benzoic acid stannous sedimentary synthetic: in above-mentioned benzoate solution or directly use the aqueous solution that drips tin salt in the benzoate dissolved aqueous solution, be full of nitrogen or other rare gas element, react under the condition that temperature is 50～70 ℃, wherein the time of Di Jiaing is 30～60 minutes, reacts to obtain benzoic acid stannous throw out after 10～30 minutes;
(3) filtration, drying: above-mentioned reacted solution is filtered, and drying obtains benzoic acid stannous.
Phenylformic acid itself is water insoluble, need in strong alkali solution, generate ionic stronger benzoate, drip the aqueous solution of tin salt then in benzoate solution, the time of dropping is 30～60 minutes, drips the benzoic acid stannous caking that too fast meeting makes generation; The mistake that drips influences reaction efficiency slowly; Secondly, because that tin salt is exposed in the air is very easily oxidized, so reaction process of the present invention is carried out in the environment of nitrogen or rare gas element.The mol ratio of the consumption of phenylformic acid or benzoate and tin salt is 2: 1 in the present invention.
Because the present invention is ionic reaction, reaction is very fast, without any need for catalyzer, not with an organic solvent, greatly reduces production cost.
As preferably, in above-mentioned benzoic acid stannous novel synthesis, drip strong base solution in the described step (1) and guarantee that the pH value of water medium is 9～10, temperature is 55～60 ℃.
Strong base solution is one or both mixed aqueous solutions in sodium hydroxide or the potassium hydroxide in the described step (1).The benzoate that uses sodium hydroxide or potassium hydroxide to be generated in step 1 is Sodium Benzoate or potassium benzoate.
In above-mentioned benzoic acid stannous novel synthesis, the tin salt in the described step (2) is tin protochloride or stannous sulfate; Use tin protochloride and stannous sulfate mainly to be because the price of chlorion and sulfate ion is lower in the present invention, stannous ion is difficult for oxidation, thus the benzoic acid stannous yield higher (93.3～97.0%) that generates.
In above-mentioned benzoic acid stannous novel synthesis, reaction conditions is for being full of nitrogen protection in the described step (2), and temperature is 55～60 ℃.Because other rare gas element price is more expensive,, in reaction process of the present invention, mainly use nitrogen as preferably.
In above-mentioned benzoic acid stannous novel synthesis, in above-mentioned benzoate solution, drip the aqueous solution of tin salt in the described step (2), wherein the time of Di Jiaing is 40～50 minutes.
Therefore the present invention has the following advantages:
1, it is simple to adopt novel synthesis of the present invention to prepare benzoic acid stannous production technique, and production cost is low, can be used for large-scale industrial production.
2, adopt benzoic acid stannous novel synthesis of the present invention in the benzoic acid stannous process of preparation, benzoic acid stannous yield is higher, also can not lump to form the muddy mixture, and it is purer to draw product through ultimate analysis.
Embodiment
Below by specific embodiment, technical scheme of the present invention is described in further detail; But the present invention is not limited to these embodiment.
Embodiment 1
With phenylformic acid (366g, 3.0mol) and water (2000ml) add in the 5000ml there-necked flask, begin to stir and heated 15 minutes to 50 ℃, (134g, 3.35mol) the 500ml aqueous solution dropwised in 60 minutes to drip NaOH, phenylformic acid all dissolves, in solution, feed nitrogen then, remove the oxygen in the solution neutralization reaction bottle, and in being full of the environment of nitrogen, add tin protochloride (SnCl
22H
2O, 339g, 1.5mol) the 500ml aqueous solution, after dropwising in 60 minutes, 50 ℃ of reactions 30 minutes, the benzoic acid stannous particulate state that is settled, filter, the dry air product, it is benzoic acid stannous to obtain 505g, yield 505/541.4 * 100%=93.3%.The ultimate analysis value (is formed C
14H
10O
4Sn) (%) C:42.03 (46.59), H:3.23 (2.79), Sn:32.70 (32.89), 94 ~ 100 ℃ of fusing points (under air, measuring).
Embodiment 2
With phenylformic acid (366g, 3.0mol) and water (2000ml) add in the 5000ml there-necked flask, begin to stir and heated 20 minutes to 55 ℃, (187g, 3.35mol) the 500ml aqueous solution dropwised in 45 minutes to drip KOH, phenylformic acid all dissolves, in solution, feed nitrogen then, remove the oxygen in the solution neutralization reaction bottle, and in being full of the environment of argon gas, add tin protochloride (SnCl
22H
2O, 339g, 1.5mol) the 500ml aqueous solution, after dropwising in 45 minutes, 55 ℃ of reactions 20 minutes, the benzoic acid stannous particulate state that is settled, filter, the dry air product, it is benzoic acid stannous to obtain 510g, yield 510/541.4 * 100%=94.2%.The ultimate analysis value (is formed C
14H
10O
4Sn) (%) C:42.53 (46.59), H:3.20 (2.79), Sn:32.80 (32.89), 94 ~ 100 ℃ of fusing points.
Embodiment 3
With phenylformic acid (366g, 3.0mol) and water (2000ml) add in the 5000ml there-necked flask, begin to stir and heated 24 minutes to 60 ℃, (134g, 3.35mol) the 600ml aqueous solution dropwised in 40 minutes to drip NaOH, phenylformic acid all dissolves, in solution, feed nitrogen then, remove the oxygen in the solution neutralization reaction bottle, and in being full of the environment of nitrogen, add tin protochloride (SnCl
22H
2O, 339g, 1.5mol) the 500ml aqueous solution, after dropwising in 40 minutes, 60 ℃ of reactions 20 minutes, the benzoic acid stannous particulate state that is settled, filter, the dry air product, it is benzoic acid stannous to obtain 520g, yield 520/541.4 * 100%=96.0%.The ultimate analysis value (is formed C
14H
10O
4Sn) (%) C:42.73 (46.59), H:3.17 (2.79), Sn:32.85 (32.89), 94 ~ 100 ℃ of fusing points.
Embodiment 4
With phenylformic acid (366g, 3.0mol) and water (2000ml) add in the 5000ml there-necked flask, stir and heated 30 minutes to 70 ℃, (134g, 3.35mol) the 500ml aqueous solution dropwised in 30 minutes to drip NaOH, phenylformic acid all dissolves, in solution, feed nitrogen then, remove the oxygen in the solution neutralization reaction bottle, and in being full of the environment of nitrogen, add tin protochloride (SnCl
22H
2O, 339g, 1.5mol) the 500ml aqueous solution, after dropwising in 30 minutes, 70 ℃ of reactions 10 minutes, the benzoic acid stannous particulate state that is settled, filter, the dry air product, it is benzoic acid stannous to obtain 525g, yield 525/541.4 * 100%=97.0%.The ultimate analysis value (is formed C
14H
10O
4Sn) (%) C:43.54 (46.59), H:3.04 (2.79), Sn:32.85 (32.89), 94 ~ 100 ℃ of fusing points.
Embodiment 5
With phenylformic acid (366g, 3.0mol) and water (2000ml) add in the 5000ml there-necked flask, begin to stir and heated 24 minutes to 60 ℃, (134g, 3.35mol) the 500ml aqueous solution dropwised in 40 minutes to drip NaOH, phenylformic acid all dissolves, in solution, feed nitrogen then, remove the oxygen in the solution neutralization reaction bottle, and in being full of the environment of nitrogen, add stannous sulfate (SnSO
4, 322g, 1.5mol) the 500ml aqueous solution, after dropwising in 40 minutes, 60 ℃ of reactions 20 minutes, the benzoic acid stannous particulate state that is settled, filter, the dry air product, it is benzoic acid stannous to obtain 525g, yield 524/541.4 * 100%=96.8%.The ultimate analysis value (is formed C
14H
10O
4Sn) (%) C:42.94 (46.59), H:3.08 (2.79), Sn:32.68 (32.89), 94 ~ 100 ℃ of fusing points.
Embodiment 6
With Sodium Benzoate (432g, 3.0mol) and water (3000ml) add in the 5000ml there-necked flask, begin to stir and heated 30 minutes to 60 ℃, Sodium Benzoate all dissolves, in solution, feed nitrogen then, remove the oxygen in the solution neutralization reaction bottle, and in being full of the environment of nitrogen, add tin protochloride (SnCl
22H
2O, 339g, 1.5mol) the 500ml aqueous solution, after dropwising in 40 minutes, 60 ℃ of reactions 20 minutes, the benzoic acid stannous particulate state that is settled, filter, the dry air product, it is benzoic acid stannous to obtain 524g, yield 522/541.4 * 100%=96.4%.The ultimate analysis value (is formed C
14H
10O
4Sn) (%) C:42.86 (46.59), H:3.14 (2.79), Sn:32.82 (32.89), 94 ~ 100 ℃ of fusing points.
Embodiment 7
With potassium benzoate (480g, 3.0mol) and water (3000ml) add in the 5000ml there-necked flask, begin to stir and heated 30 minutes to 60 ℃, potassium benzoate all dissolves, in solution, feed nitrogen then, remove the oxygen in the solution neutralization reaction bottle, and in being full of the environment of nitrogen, add tin protochloride (SnCl
22H
2O, 339g, 1.5mol) the 500ml aqueous solution, after dropwising in 40 minutes, 60 ℃ of reactions 20 minutes, the benzoic acid stannous particulate state that is settled, filter, the dry air product, it is benzoic acid stannous to obtain 518g, yield 518/541.4 * 100%=95.7%.The ultimate analysis value (is formed C
14H
10O
4Sn) (%) C:43.04 (46.59), H:3.16 (2.79), Sn:32.90 (32.89), 94 ~ 100 ℃ of fusing points.
Specific embodiment described in the present invention only is that the present invention's spirit is illustrated.The technician of the technical field of the invention can make various modifications or replenishes or adopt similar mode to substitute described specific embodiment, but can't depart from spirit of the present invention or surmount the defined scope of appended claims.
Although the present invention has been made detailed explanation and has quoted some specific exampless as proof, to those skilled in the art, only otherwise leave that the spirit and scope of the present invention can be done various variations or correction is obvious.
Claims (7)
1, a kind of benzoic acid stannous novel synthesis is characterized in that being made up of following steps:
(1) benzoate is synthetic: phenylformic acid is added in the entry, be heated to 50～70 ℃, under agitation drip strong base solution and make phenylformic acid generate benzoate and soluble in water, keeping the pH value of solution is 8～11, the time that drips is 30～60 minutes, obtains benzoate solution after the reaction;
(2) benzoic acid stannous sedimentary synthetic: in above-mentioned benzoate solution or directly use the aqueous solution that drips tin salt in the benzoate dissolved aqueous solution, be full of nitrogen or other rare gas element, react under the condition that temperature is 50～70 ℃, wherein the time of Di Jiaing is 30～60 minutes, reacts to obtain benzoic acid stannous throw out after 10～30 minutes;
(3) filtration, drying: above-mentioned reacted solution is filtered, and drying obtains benzoic acid stannous.
2, benzoic acid stannous novel synthesis according to claim 1 is characterized in that, drips strong base solution in the described step (1) and guarantees that the pH value of water medium is 9～10, and temperature is 55～60 ℃.
3, benzoic acid stannous novel synthesis according to claim 1 is characterized in that, strong base solution is one or both mixed aqueous solutions in sodium hydroxide or the potassium hydroxide in the described step (1).
4, benzoic acid stannous novel synthesis according to claim 3 is characterized in that, the benzoate that is generated in the described step (1) is Sodium Benzoate or potassium benzoate.
5, benzoic acid stannous novel synthesis according to claim 1 is characterized in that, the tin salt in the described step (2) is tin protochloride or stannous sulfate.
6, benzoic acid stannous novel synthesis according to claim 1 and 2 is characterized in that, reaction conditions is for being full of nitrogen protection in the described step (2), and temperature is 55～60 ℃.
7, benzoic acid stannous novel synthesis according to claim 1 and 2 is characterized in that, drips the aqueous solution of tin salt in the described step (2) in above-mentioned benzoate solution, and wherein the time of Di Jiaing is 40～50 minutes.
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| CN100526282C CN100526282C (en) | 2009-08-12 |
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| CA2461798C (en) * | 2003-03-31 | 2012-04-24 | Nof Corporation | Low melting point tin salt of carboxylic acid and method for producing the same |
| CN1657520A (en) * | 2004-12-08 | 2005-08-24 | 云南锡业集团有限责任公司研究设计院 | Process for preparing methyl stannous sulfonate using tin powder |
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