CN1125217A - Method for preparation of phenyl-pyruvic acid by dioxonation of benzyl halide - Google Patents
Method for preparation of phenyl-pyruvic acid by dioxonation of benzyl halide Download PDFInfo
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- CN1125217A CN1125217A CN 94119286 CN94119286A CN1125217A CN 1125217 A CN1125217 A CN 1125217A CN 94119286 CN94119286 CN 94119286 CN 94119286 A CN94119286 A CN 94119286A CN 1125217 A CN1125217 A CN 1125217A
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- China
- Prior art keywords
- catalyzer
- phenyl
- pyruvic acid
- dioxonation
- cobalt
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The prepn. method of phenyl-pyruvic acid by using dicarbonylation reaction of benzyl halide under the catalytic action of metal complex uses heteronuclear iron-cobalt cluster catalyst R4N]+FeCo3(CO)12]- etc. to make reaction for 6-10 h. at 40-70 deg.C under the condition of a certain carbon oxide pressure of 2-6 MPa. Its solvent is dioxane. Said invention has the advantages of simple preparation process and high yield. Its yield can be up to 80-90%.
Description
The present invention relates to the method for cobalt metal bunch catalytic halogenation benzyl dioxonation prepared in reaction phenyl-pyruvic acid, it comprises following several steps: pressurization dioxonation reaction under the effect of iron cobalt cluster catalyst, product through separate, acidifying, extraction, concentrate white crystals.
The synthetic method of known phenyl-pyruvic acid, severe reaction conditions not only, and need just can finish through polystep reaction with the initiator of special construction, difficulty is more.
In OE2600541 first with PhCH
2Cl in ethanol with the carbon monoxide effect, with Co
2(CO)
8For catalyzer reacts through dioxonation, obtain 71% phenyl-pyruvic acid, 29% toluylic acid, this method yield height, easy and simple to handle, product separates easily.
The objective of the invention is to select for use new type of metal heteronuclear cobalt bunch complex compound as catalyzer, overcome original Co
2(CO)
8Be catalyzer shortcoming in the prior art, thereby a kind of technology advantages of simple, feasible preparation method are provided.
Method of the present invention has been selected for use in air ratio cobalt octacarbonyl stable catalyst, obtains phenyl-pyruvic acid with the step and the starting material that may lack, and helps industrial production.
Phenyl-pyruvic acid is the intermediate of fine chemistry industry, is synthetic α-amino acid whose important intermediate, also is the important metabolic product of animals and plants and the raw material of artificial sweetener, in productions such as medical biochemistry and agricultural chemicals purposes is comparatively widely arranged.
Purpose of the present invention can reach by following measure:
It is catalyzer that the present invention selects heteronuclear cobalt bunch complex compound for use, with dioxane (C
2H
4)
2O
2Be solvent, under the effect of alkaline medium calcium hydroxide, in having the autoclave of stirring with reaction of carbon monoxide, pressure 1.0-6.0MPa, temperature is controlled at 25-70 ℃, and reacting liquid pH value is 7.1-13.5, be preferably 8-13 reactions 6-10 hours, finish afterreaction liquid and filter solid water and ether repetitive scrubbing, the solid hcl acidifying after the washing, terminal point pH is controlled between 1-3, and use extracted with diethyl ether, evaporation drying to get the crude benzol pyruvic acid, recrystallization gets white crystal.The concentration range 10-15% of the used HCl of acidifying.Mother liquor is used hcl acidifying equally, and endpoint pH is controlled at more than 3, extracted with diethyl ether, evaporation, the dry crude benzol acetate that gets.
Method of the present invention prepares the phenyl-pyruvic acid yield 28.9-95%, and purity can reach more than 97%, 155-156.5 ℃ of fusing points.
Advantage of the present invention is as follows:
1, the employed industrial chemicals of whole process of preparation is cheap and easy to get, and production technique is fairly simple, and easy to operate production phase is short.
2, selected catalyzer is comparatively stable in air.
3, feed gas containing carbon monoxide can use the industrial tail gas that is rich in CO.
The present invention below will be further described.
Example 1 is got 1.0g benzyl trimethyl quaternary ammonium salt ten dicarbapentaborane three ferro-cobalt duster compound [C
6H
5CH
2(CH
3)
3N]
+[FeCo
3(CO)
10]
-: 100ml dioxan (C
2H
4)
2O
27.7g (0.061mol) Benzyl Chloride; 9.26g (0.125mol) calcium hydroxide; 38ml water adds the high pressure that has induction stirring simultaneously. in the still, carbon monoxide with 2.0MPa washes three times, pour carbon monoxide again, 65 ℃ of temperature, the 3MPa reaction, under agitation condition, kept 8 hours, replenish carbon monoxide and keep weighing apparatus level pressure power, till carbon monoxide no longer absorbs, after reaction finishes, autoclave is chilled to normal temperature, takes out mixture and filters, solid water and ether washing three times, solid after the washing is dissolved in the hydrochloric acid, the solution extracted with diethyl ether concentrates and removes ether, gets phenyl-pyruvic acid 9.5g yield 95% after the drying.
Example 2 by example 1 described condition and process, changes catalyzer into chlormethine nine carbonyls three cobalt ClCCo
3(CO)
9Get 1.0g under the 3.0MPa reaction pressure, react 6 hours product 8.0g yield 77.2%.
Example 3 by example 1 described condition and process, is used catalyzer (C instead
2H
5)
4N
-[FeCo
3(CO)
12] 0.5g, reaction pressure 3.0MPa in 6 hours reaction times, gets phenyl-pyruvic acid 5.5g yield 53.1%.
Example 4, by example 1 described reaction conditions and process, using catalyzer instead is (C
4H
9)
4N
+[FeCo
3(CO)
12] all the other conditions of 0.5g are identical with example 1, phenyl-pyruvic acid 5.0g yield 48.3%.
Example 5 by example 1 described condition and process, changes catalyzer into ClCo
3(CO)
9, get 1.0g under 3.0MPa, humidity is controlled at 50 ℃ of reactions 6 hours, gets phenyl-pyruvic acid 8.0g yield 77.2%.
Example 6 is got load iron cobalt cluster catalyst
With example 1 described condition and process, get phenyl-pyruvic acid 6.0g, productive rate 57.9%.
Example 7 is got 0.5g example 1 catalyst system therefor, and all the other conditions and process are with example 1.Change reaction pressure and all can obtain phenyl-pyruvic acid, experimental result shows that two carbonyl reactions increase with the increase phenyl-pyruvic acid yield of reaction pressure.Work as P
CODuring=1.0MPa, in the short reaction times, equally also can get the dioxonation product.See Table 1:NO P
CO(MPa) Time (hr) Cat (g) PPA (g) PPA (％) PA (g) PA (％)P-13-32 6.0 8 0.5 8.0 77.2 1.0 11.7P-14-33 5.0 6 0.5 5.0 48.3 2.0 23.3P-15-34 4.0 6 0.5 6.0 57.9 1.0 11.7P-17-42 3.0 6 0.5 4.2 40.5 1.4 16.3P-18-48 2.0 6 0.5 3.7 35.7 1.7 19.8P-19-413 1.0 6 0.5 3.0 28.9 3.5 40.7
Claims (8)
1, a kind of method of Benzyl Chloride dioxonation prepared in reaction phenyl-pyruvic acid comprises:
(1) use a heteronuclear bunch complex compound to make catalyzer;
(2) use a cobalt bunch complex compound to make catalyzer;
(3) use the supported metal cluster complex compound to make catalyzer;
(4) with carbon monoxide as unstripped gas;
(5) use dioxane to make solvent;
(6) low pressure is carried out the dioxonation reaction in the presence of alkaline medium.
2, the method for claim 1 is characterized in that catalyzer is benzyl trimethyl quaternary ammonium salt ten dicarbapentaborane two ferro-cobalt duster compound [C
6H
5CH
2(CH
3)
3N]
+[FeCo
3(CO)
12]
-
3, the method for claim 1 is characterized in that catalyzer is chlormethine nine carbonyls three cobalt ClCCo
3(CO)
9
4, the method for claim 1 is characterized in that catalyzer is (C
2H
5)
4B[FeCo
3(CO)
12].
5, the method for claim 1 is characterized in that catalyzer is YCCo
3(CO)
9(Y=alkyl, ester, halogen, aryl), [B
4N]
+[FeCo
3(CO)
12]
-
6, the method for claim 1 is characterized in that alkaline medium is a calcium hydroxide.
7, the method for claim 1 is characterized in that being reflected at 25-70 ℃, and 1.0-6.0MPa, pH carry out under 7.1-13.5 conditions.
8, the method for claim 1 is characterized in that reacting liquid pH value is 8-13.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94119286 CN1125217A (en) | 1994-12-23 | 1994-12-23 | Method for preparation of phenyl-pyruvic acid by dioxonation of benzyl halide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94119286 CN1125217A (en) | 1994-12-23 | 1994-12-23 | Method for preparation of phenyl-pyruvic acid by dioxonation of benzyl halide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1125217A true CN1125217A (en) | 1996-06-26 |
Family
ID=5039178
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 94119286 Pending CN1125217A (en) | 1994-12-23 | 1994-12-23 | Method for preparation of phenyl-pyruvic acid by dioxonation of benzyl halide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1125217A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1112346C (en) * | 2000-01-21 | 2003-06-25 | 华中理工大学 | Process for synthesizing phenylpyruvic acid by catalytic dioxonation |
-
1994
- 1994-12-23 CN CN 94119286 patent/CN1125217A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1112346C (en) * | 2000-01-21 | 2003-06-25 | 华中理工大学 | Process for synthesizing phenylpyruvic acid by catalytic dioxonation |
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| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |