CN104447338B - A kind of D-is to the tartaric synthetic method of methyldiphenyl formyl - Google Patents
A kind of D-is to the tartaric synthetic method of methyldiphenyl formyl Download PDFInfo
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- CN104447338B CN104447338B CN201410836906.7A CN201410836906A CN104447338B CN 104447338 B CN104447338 B CN 104447338B CN 201410836906 A CN201410836906 A CN 201410836906A CN 104447338 B CN104447338 B CN 104447338B
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- methyldiphenyl formyl
- tartaric
- toluene
- methyldiphenyl
- tartrate
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- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 title claims abstract description 39
- 238000010189 synthetic method Methods 0.000 title claims abstract description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 81
- YQCGEGQXFHSZHK-UHFFFAOYSA-N 4-formyloxy-2,3-dihydroxy-4-oxobutanoic acid Chemical compound OC(=O)C(O)C(O)C(=O)OC=O YQCGEGQXFHSZHK-UHFFFAOYSA-N 0.000 claims abstract description 24
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- GPZXFICWCMCQPF-UHFFFAOYSA-N 2-methylbenzoyl chloride Chemical compound CC1=CC=CC=C1C(Cl)=O GPZXFICWCMCQPF-UHFFFAOYSA-N 0.000 claims abstract description 11
- FEWJPZIEWOKRBE-LWMBPPNESA-L D-tartrate(2-) Chemical compound [O-]C(=O)[C@@H](O)[C@H](O)C([O-])=O FEWJPZIEWOKRBE-LWMBPPNESA-L 0.000 claims abstract description 11
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 11
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 21
- 239000002994 raw material Substances 0.000 abstract description 10
- 238000011084 recovery Methods 0.000 abstract description 10
- 239000002904 solvent Substances 0.000 abstract description 7
- 238000000926 separation method Methods 0.000 abstract description 4
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000007664 blowing Methods 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-LWMBPPNESA-N levotartaric acid Chemical compound OC(=O)[C@@H](O)[C@H](O)C(O)=O FEWJPZIEWOKRBE-LWMBPPNESA-N 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A kind of D-is to the tartaric synthetic method of methyldiphenyl formyl, with D-tartrate, to methyl benzoyl chloride for raw material, copper sulfate is catalyzer, take toluene as solvent, the obtained D-of reaction is to methyldiphenyl formyl winestone acid anhydrides, to add etc. water gaging and toluene be hydrolyzed D-to methyldiphenyl formyl tartrate, wherein solvent toluene, all can reuse with water in hydrolysing step and toluene.Method technique of the present invention is simple, safety is easy to operate, and process recovery ratio reaches more than 95%, and meanwhile, raw materials cost is lower, and part material is recyclable, and finished product product purity is higher, has excellent chiral separation performance.
Description
Technical field
The present invention relates to a kind of chemical synthesis process technical field of chiral selectors, a kind of D-is to the tartaric synthetic method of methyldiphenyl formyl specifically.
Background technology
D-is a kind of white crystalline powder to methyldiphenyl formyl tartrate, easily absorbs water in atmosphere, dissolves in the organic solvent such as ethanol and methyl alcohol.Be widely used in chiral separation aminated compounds.And because it is cheap, stable in properties, and be easy to recycle and there is good industrial application value.Its molecular formula is as follows:
The defect of common synthetic method is: 1. raw material has strong and stimulating, severe corrosive, severe toxicity, not easy to operate.2. raw material availability is low, can not recycle, and production is polluted larger.3. process recovery ratio is low, and about 35%, product purity is lower, and production cost is higher.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of D-to the tartaric synthetic method of methyldiphenyl formyl, the method technique is simple, safety is easy to operate, process recovery ratio reaches more than 95%, simultaneously, raw materials cost is lower, and part material is recyclable, finished product product purity is higher, has excellent chiral separation performance.
D-to the tartaric general synthetic method of methyldiphenyl formyl is: first with D-tartrate (CAS:147-71-7), to methyl benzoyl chloride (CAS:874-60-2) and sulfur oxychloride (CAS:7719-09-7) for raw material, take toluene as solvent, the obtained D-of reaction to methyldiphenyl formyl winestone acid anhydrides, then by D-to methyldiphenyl formyl winestone acid anhydrides add water through be hydrolyzed D-to methyldiphenyl formyl tartrate.Reaction mechanism is as follows:
This method process recovery ratio about 35%.
In order to solve the technical problem that the present invention proposes, the technical scheme that the present invention proposes especially is: a kind of D-is to the tartaric synthetic method of methyldiphenyl formyl, and synthesis step is:
(1) 1 part of D-tartrate, is got by weight and appropriate organic solvent puts into reactor, under agitation, in reactor, add 0.1-0.001 part catalyzer, afterwards, in reactor, add 1 ~ 3 part to methyl benzoyl chloride with the drop rate of 1-10mL/min, after dropwising, continue reaction 6h, then, the mixture be obtained by reacting is turned to be incorporated in whizzer and carries out centrifugation, obtain solid D-to methyldiphenyl formyl winestone acid anhydrides, for subsequent use;
Described catalyzer is copper sulfate or ferrous sulfate;
(2), the D-that step (1) is obtained is put into reactor to methyldiphenyl formyl winestone acid anhydrides, and toluene and the water of weight such as to add wherein, reflux 4-6h under 100 DEG C of conditions, afterwards, be cooled to normal temperature, the mixture obtained is transferred in whizzer and carries out centrifugation, obtain solid D-to methyldiphenyl formyl tartrate.
In step (1) and step (2), the rotating speed of centrifugation is 100-1000r/min.
Organic solvent in described step (1) is toluene.
In described step (1), the add-on of toluene and the tartaric ratio of D-are 1L/0.75kg.
Rate of temperature fall in described step (2) is 5-10 DEG C/min.
Stirring velocity in described step (1) is 500-3000r/min.
Beneficial effect compared with the method that the above method of the present invention and employing sulfur oxychloride are raw material is:
1, this synthesis D-is simple to the tartaric method technique of methyldiphenyl formyl, and manipulation is convenient, and mild condition, avoids the application of toxic substance sulfur oxychloride, improves the safe operability of technique; As the copper sulfate of catalyzer or adding of ferrous sulfate, substantially reduce the reaction times of technique, improve product yield and the quality product of technique; Meanwhile, low raw-material cost used, the recycling capable of circulation such as the solvent used in process, reduces production cost, decreases environmental pollution, be conducive to scale operation.
2, the D-of the method synthesis reaches more than 99% to methyldiphenyl formyl tartrate final product quality purity, and technique product yield reaches more than 95%, has excellent chiral separation performance.
Accompanying drawing explanation
Fig. 1 is that the obtained D-of embodiment 1 is to the tartaric XRD figure of methyldiphenyl formyl;
Fig. 2 is that the obtained D-of embodiment 2 is to the tartaric XRD figure of methyldiphenyl formyl;
Fig. 3 is that the obtained D-of embodiment 3 is to the tartaric XRD figure of methyldiphenyl formyl;
Fig. 4 is that the obtained D-of embodiment 4 is to the tartaric XRD figure of methyldiphenyl formyl;
Fig. 5 is that the obtained D-of embodiment 5 is to the tartaric XRD figure of methyldiphenyl formyl.
Embodiment
Be below specific embodiments of the invention, following embodiment is convenient to understand the present invention better, but does not limit the present invention.
A kind of D-is to the tartaric synthetic method of methyldiphenyl formyl, with D-tartrate (CAS:147-71-7), to methyl benzoyl chloride (CAS:874-60-2) for raw material, copper sulfate (CAS:7758-99-8) is catalyzer, take toluene as solvent, the obtained D-of reaction is to methyldiphenyl formyl winestone acid anhydrides, to add etc. water gaging and toluene be hydrolyzed D-to methyldiphenyl formyl tartrate, wherein solvent toluene, all can reuse with water in hydrolysing step and toluene.
Advantage: 1. various cheaper starting materials is easy to get, safety is easy to operate.
2. good product quality, content >=99%, total recovery >=95%.
Its concrete technical process is:
With D-tartrate in raw material suction reactor, and a certain amount of solvent toluene is added in reactor, open and stir, copper sulfate is dropped into from dog-house, start to drip methyl benzoyl chloride, after dropwising, continue reaction 6 hours, be discharged to whizzer, D-is obtained to methyldiphenyl formyl winestone acid anhydrides and mother liquor (can be recycled) through rejection filter, D-is dropped in reactor to methyldiphenyl formyl winestone acid anhydrides, add and the water of its equivalent and toluene, be heated to backflow, within about 5 hours, complete, be discharged to whizzer, D-is obtained to methyldiphenyl formyl tartrate and mother liquor (can be recycled) through rejection filter.
D-obtained by this technique to the tartaric detection method of methyldiphenyl formyl is: obtained D-is loaded enlightening horse c18(2 to methyldiphenyl formyl tartrate) pillar, with methyl alcohol and ammonium acetate for moving phase, 254 wavelength, flow velocity 1.0,20ul quantitative loop sample introduction.
Embodiment 1:
A kind of D-is to the tartaric synthetic method of methyldiphenyl formyl, and it comprises the steps:
Get D-tartrate 150g, toluene 200ml is placed in 1000ml there-necked flask, under stirring, add 1.5g copper sulfate, start to drip methyl benzoyl chloride 330g, within 3 hours, drip off, continue reaction 6 hours, be discharged to whizzer, rejection filter obtains D-to methyldiphenyl formyl winestone acid anhydrides 495.4g, by it input 2000ml there-necked flask, add water each 495.4g with toluene, is warming up to backflow, keeps 5 hours, be cooled to normal temperature blowing, rejection filter obtains D-to methyldiphenyl formyl tartrate 374.4g.
The D-obtained by the present embodiment carries out TEM test to methyldiphenyl formyl tartrate, and as shown in Figure 1, as seen from the figure, finished product D-is 99.61% to methyldiphenyl formyl tartrate purity content to test structure, total recovery 96.6%.
Peak, peak name retention time peak height peak area content
13.4971594.68712165.8050.1808
25.077283.5123246.9530.0483
316.77343.552263.2000.0039
418.205336.6099885.0380.1469
520.810102906.2506701954.00099.6059
649.25837.127280.2480.0042
753.89532.034224.9960.0033
854.71234.168257.9030.0038
959.83832.386192.7980.0029
Embodiment 2:
A kind of D-is to the tartaric synthetic method of methyldiphenyl formyl, and it comprises the steps:
In 10L there-necked flask, drop into D-tartrate 1.5kg, toluene 2L, under stirring, add 20g copper sulfate, start to drip methyl benzoyl chloride 3.5kg, within 3 hours, drip off, continue reaction 6 hours, be discharged to whizzer, rejection filter obtains D-to methyldiphenyl formyl winestone acid anhydrides 4.88kg, by it input 20L there-necked flask, add water each 4.88kg with toluene, is warming up to backflow, keeps 5 hours, be cooled to normal temperature blowing, rejection filter obtains D-to methyldiphenyl formyl tartrate 3.71kg.
The D-obtained by the present embodiment carries out TEM test to methyldiphenyl formyl tartrate, and as shown in Figure 2, as seen from the figure, finished product D-is 99.76% to methyldiphenyl formyl tartrate purity content to test structure, total recovery 95.9%.
Peak, peak name retention time peak height peak area content
13.4984862.37240533.6720.1214
24.09592.816777.7000.0023
35.070431.0154684.4500.0140
46.41283.041899.0500.0027
56.880196.7222425.4000.0073
67.52725.541148.9070.0004
77.92229.305204.4000.0006
89.755682.00012441.5510.0373
910.55528.232234.4150.0007
1012.23574.4871348.0610.0040
1114.95341.885638.7500.0019
1215.51534.461228.7500.0007
1316.43221.021177.5000.0005
1418.538278028.56333312572.00099.7603
1526.315254.07813142.2520.0394
1627.32327.781146.5750.0004
1727.95731.362357.3250.0011
1828.77245.4491270.7490.0038
1930.46744.150396.9340.0012
Embodiment 3:
A kind of D-is to the tartaric synthetic method of methyldiphenyl formyl, and it comprises the steps:
In 50L reactor, drop into D-tartrate 7.5kg, toluene 10L, under stirring, add 120g copper sulfate, start to drip methyl benzoyl chloride 18kg, within 4 hours, drip off, continue reaction 6 hours, be discharged to whizzer, rejection filter obtains D-to methyldiphenyl formyl winestone acid anhydrides 24.9kg, by it input 100L reactor, add water each 24.9kg with toluene, is warming up to backflow, keeps 5 hours, be cooled to normal temperature blowing, rejection filter obtains D-to methyldiphenyl formyl tartrate 18.5kg.
The D-obtained by the present embodiment carries out TEM test to methyldiphenyl formyl tartrate, and as shown in Figure 3, as seen from the figure, finished product D-is 99.34% to methyldiphenyl formyl tartrate purity content to test structure, total recovery 95.2%.
Peak, peak name retention time peak height peak area content
12.808176.340794.0000.0411
24.163275.4882521.3000.1307
34.638284.8671917.2500.0994
46.242800.51010835.2000.1615
58.958229.2732655.3500.0376
620.212194.0645270.8010.0732
724.678224.2877677.9910.0979
826.50335478.9301897602.50099.3419
929.31021.598323.4000.0168
Embodiment 4:
A kind of D-is to the tartaric synthetic method of methyldiphenyl formyl, and it comprises the steps:
In 500L reactor, drop into D-tartrate 75kg, toluene 100L, under stirring, add 1kg copper sulfate, start to drip methyl benzoyl chloride 200kg, within 5 hours, drip off, continue reaction 6 hours, be discharged to whizzer, rejection filter obtains D-to methyldiphenyl formyl winestone acid anhydrides 257.5kg, by it input 1000L reactor, add water each 257.5kg with toluene, is warming up to backflow, keeps 5 hours, be cooled to normal temperature blowing, rejection filter obtains D-to methyldiphenyl formyl tartrate 185.9kg.
The D-obtained by the present embodiment carries out TEM test to methyldiphenyl formyl tartrate, and as shown in Figure 4, as seen from the figure, finished product D-is 99.76% to methyldiphenyl formyl tartrate purity content to test structure, total recovery 96.1%.
Peak, peak name retention time peak height peak area content
13.4934940.27240663.5740.1313
24.078118.1381043.2500.0034
35.062573.3286348.7000.0205
46.42276.1171119.8000.0036
56.87052.705878.1500.0028
68.68268.7861561.9000.0050
79.788634.28912471.4000.0403
811.88549.299457.4000.0015
912.17323.000157.6000.0005
1012.40320.421189.1500.0006
1113.17567.884810.1330.0026
1218.763265818.31330900420.00099.7596
1325.50020.21881.4500.0003
1425.75855.162789.3870.0025
1526.372188.8807882.1380.0254
Embodiment 5:
A kind of D-is to the tartaric synthetic method of methyldiphenyl formyl, and it comprises the steps:
In 3000L reactor, drop into D-tartrate 450kg, toluene 600L, under stirring, add 5kg copper sulfate, start to drip methyl benzoyl chloride 1000kg, within 6 hours, drip off, continue reaction 6 hours, be discharged to whizzer, rejection filter obtains D-to methyldiphenyl formyl winestone acid anhydrides 1281.4kg, by it input 5000L reactor, add water each 1281.4kg with toluene, is warming up to backflow, keeps 5 hours, be cooled to normal temperature blowing, rejection filter obtains D-to methyldiphenyl formyl tartrate 1121.2kg.
The D-obtained by the present embodiment carries out TEM test to methyldiphenyl formyl tartrate, and as shown in Figure 5, as seen from the figure, finished product D-is 99.50% to methyldiphenyl formyl tartrate purity content to test structure, total recovery 96.3%.
Peak, peak name retention time peak height peak area content
12.307378.4712011.0020.0089
22.537915.4635183.2660.0228
32.665146.870937.9000.0041
42.938121.305658.8950.0029
53.46825383.475276037.7810.2161
64.2721621.92313959.9500.0615
75.497934.6529782.7500.0431
811.062305.8125432.6000.0239
920.2923364.16094370.8050.0157
1023.290248060.12522132184.00099.5010
1132.3171586.50689152.0000.0927
1238.6081216.06369732.6020.0072。
Claims (4)
1. D-is to the tartaric synthetic method of methyldiphenyl formyl, it is characterized in that, synthesis step is:
(1) 1 part of D-tartrate, is got by weight and q. s. toluene puts into reactor, the add-on of toluene and the tartaric ratio of D-are 1L/0.75kg, under agitation, 0.1-0.001 part catalyzer is added in reactor, afterwards, in reactor, 1 ~ 3 part is added to methyl benzoyl chloride with the drop rate of 1-10mL/min, after dropwising, continue reaction 6h, then, the mixture be obtained by reacting is turned to be incorporated in whizzer and carries out centrifugation, obtain solid D-to methyldiphenyl formyl winestone acid anhydrides, for subsequent use;
Described catalyzer is copper sulfate or ferrous sulfate;
(2), the D-that step (1) is obtained is put into reactor to methyldiphenyl formyl winestone acid anhydrides, and toluene and the water of weight such as to add wherein, reflux 4-6h under 100 DEG C of conditions, afterwards, be cooled to normal temperature, the mixture obtained is transferred in whizzer and carries out centrifugation, obtain solid D-to methyldiphenyl formyl tartrate.
2. a kind of D-according to claim 1 is to the tartaric synthetic method of methyldiphenyl formyl, it is characterized in that: in step (1) and step (2), the rotating speed of centrifugation is 100-1000r/min.
3. a kind of D-according to claim 1 is to the tartaric synthetic method of methyldiphenyl formyl, it is characterized in that: the rate of temperature fall in described step (2) is 5-10 DEG C/min.
4. a kind of D-according to claim 1 is to the tartaric synthetic method of methyldiphenyl formyl, it is characterized in that: the stirring velocity in described step (1) is 500-3000r/min.
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| Title |
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| 左或右旋二对甲苯甲酰酒石酸合成工艺的改进;曾善麟;《化学试剂》;20021231;第24卷(第5期);309、311 * |
| 拆分剂(+)-2, 3-二对甲苯甲酰氧丁二酸的合成;贺蕴普 等;《化学试剂》;19991231;第21卷(第2期);106-107 * |
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