CN103529032A - Detection method for measuring content of N-methylmorpholine - Google Patents

Detection method for measuring content of N-methylmorpholine Download PDF

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Publication number
CN103529032A
CN103529032A CN201210233209.3A CN201210233209A CN103529032A CN 103529032 A CN103529032 A CN 103529032A CN 201210233209 A CN201210233209 A CN 201210233209A CN 103529032 A CN103529032 A CN 103529032A
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Prior art keywords
titration
methylmorpholine
content
perchloric acid
conical flask
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Inventor
梁光义
安巧
曹佩雪
潘卫东
刘昌孝
黄正明
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Guizhou Bailing Group Pharmaceutical Co ltd
Tianjin Institute of Pharmaceutical Research Co Ltd
CHINA 302 MILITARY HOSPITAL OF PLA
Key Laboratory of Natural Product Chemistry of Guizhou Academy of Sciences
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Guizhou Bailing Group Pharmaceutical Co ltd
Tianjin Institute of Pharmaceutical Research Co Ltd
CHINA 302 MILITARY HOSPITAL OF PLA
Key Laboratory of Natural Product Chemistry of Guizhou Academy of Sciences
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Priority to CN201210233209.3A priority Critical patent/CN103529032A/en
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Abstract

The invention provides a detection method for measuring the content of N-methylmorpholine. The detection method comprises the following steps of quantitatively dissolving the N-methylmorpholine by taking acetic anhydride as a solvent, performing titration by perchloric acid titration liquid by taking crystal violet as an indicating agent, and measuring the content of the N-methylmorpholine by an indicating agent titration method. The method has the advantages of small using amount of samples, simplicity in operation, good repetitiveness and the like.

Description

A kind of detection method of measuring N-methylmorpholine content
Technical field
The present invention relates to a kind of detection method of measuring N-methylmorpholine content.
Background technology
N-methylmorpholine is a kind of important organic chemical industry's reagent, in order to control better the quality of N-methylmorpholine, applicant has carried out a large amount of research to the content assaying method of N-methylmorpholine in reagent, and a kind of detection method of measuring N-methylmorpholine content by non-aqueous titration is provided.
The relevant information of N-methylmorpholine described in the present invention is:
Chinese: N-methylmorpholine
Chinese another name: 4-methyl morpholine; N-methylmorpholine; 4-methylmorpholine; 4-methyl morpholine; Isosorbide-5-Nitrae-oxaza heptane; Methyl morpholine.
English name: N-methylmorpholine, is called for short: NMM.
Molecular formula: C5H11NO
Relative molecular mass: 101.15.
Summary of the invention
Technical matters to be solved by this invention is: a kind of detection method of measuring N-methylmorpholine content is provided; Described detection method is quick, accurate, highly sensitive, reproducible.
The detection method of mensuration N-methylmorpholine content of the present invention is such:
Measure a detection method for N-methylmorpholine content, adopt indicator titration method, step is as follows: take N-methylmorpholine sample, put in conical flask, add aceticanhydride and dissolve, add crystal violet indicator solution, to conical flask, dropwise drip perchloric acid titration liquid, limit edged jolting conical flask, observes the variation of color in conical flask, and the color in conical flask becomes green, and colour-fast in 30 seconds, arrive titration end-point, write down now registration, and the result of titration is proofreaied and correct with blank test.
Specifically, the detection method of described mensuration N-methylmorpholine content is: adopt indicator titration method, step is as follows: take N-methylmorpholine sample 0.2g, put in conical flask, adding aceticanhydride 20-50mL dissolves, adding crystal violet indicator solution 1-5 drips, control buret and dropwise drip to conical flask the perchloric acid titration liquid that concentration is 0.01-0.15mol/L, limit edged jolting conical flask, observe the variation of color in conical flask, color in conical flask becomes green, and colour-fast in 30 seconds, arrive titration end-point, write down now registration, and the result of titration is proofreaied and correct with blank test.
The content of N-methylmorpholine is calculated as follows:
Wherein: V samplefor titration Potassium Hydrogen Phthalate, consume the volume number (ml) of perchloric acid liquid to terminal time; V emptythe perchloric acid volume number (ml) consuming to terminal time for titration blank; C is the concentration (mol/L) of perchloric acid titration liquid; W is the Potassium Hydrogen Phthalate amount (mg) taking.
The detection method of aforesaid mensuration N-methylmorpholine content, the addition of described aceticanhydride is 30mL.
The detection method of aforesaid mensuration N-methylmorpholine content, the addition of described crystal violet indicator solution is 2.
The detection method of aforesaid mensuration N-methylmorpholine content, the concentration of described perchloric acid titration liquid is 0.1 mol/L.
The detection method of aforesaid mensuration N-methylmorpholine content, described in while taking N-methylmorpholine sample, should be accurate to 0.0001g
The detection method of aforesaid mensuration N-methylmorpholine content, the hop point of titration end-point color during with potentiometric titration is as the criterion.
The present invention is the chemical constitution in view of N-methylmorpholine itself, contains amido structure in its molecule, can react with perchloric acid, can be used for surveying its content.Reaction principle is:
Detection method of the present invention is the preferred plan obtaining through a large amount of shaker tests, and following experimental study is preferred process of the present invention:
experimental example 1.
One, the selection of solvent
Titration curve when investigating respectively mixed solution with glacial acetic acid, glacial acetic acid and aceticanhydride different proportion, aceticanhydride etc. and making solvent, result shows that, while making solvent with aceticanhydride, the scope of titration is large compared with other solvents, therefore selects aceticanhydride to make solvent, sees accompanying drawing 1.Wherein: 1. glacial acetic acid; 2. glacial acetic acid: aceticanhydride (25:5); 3. glacial acetic acid: aceticanhydride (20:10); 4. glacial acetic acid: aceticanhydride (15:15); 5. aceticanhydride.
Two, titration end-point determines
Take N-methylmorpholine sample 0.2g(and be accurate to 0.0001g), add 30ml aceticanhydride it is dissolved, add 2 of crystal violet indicator solutions, according to potentiometric titration, with 0.1mol/L perchloric acid titration liquid, carry out titration, use current potential directing terminal, when result shows terminal, solution is aobvious green.Draw titration curve and titration curve first order derivative figure, in Table 1, accompanying drawing 2 and accompanying drawing 3.
Table 1 potentiometric titration result
Consume perchloric acid liquid long-pending (ml) Voltage (mV) dV(ml) dE(mV) dE/dV(mV/ml)
0.000 101 ? ? ?
0.250 126 0.250 25 100
1.000 168 0.750 42 56
1.500 187 0.500 19 38
2.000 201 0.500 14 28
2.500 213 0.500 12 24
3.000 222 0.500 9 18
3.500 231 0.500 9 18
4.000 239 0.500 8 16
4.500 247 0.500 8 16
5.000 253 0.500 6 12
5.500 259 0.500 6 12
6.000 265 0.500 6 12
6.500 270 0.500 5 10
7.000 275 0.500 5 10
7.525 279 0.525 4 8
8.000 283 0.475 4 8
8.500 287 0.500 4 8
9.000 291 0.500 4 8
9.500 296 0.500 5 10
10.000 300 0.500 4 8
10.500 303 0.500 3 6
11.000 307 0.500 4 8
11.500 311 0.500 4 8
12.000 315 0.500 4 8
12.500 319 0.500 4 8
13.000 323 0.500 4 8
13.500 327 0.500 4 8
14.000 332 0.500 5 10
14.500 336 0.500 4 8
15.000 341 0.500 5 10
15.500 345 0.500 4 8
16.000 350 0.500 5 10
16.500 356 0.500 6 12
17.000 363 0.500 7 14
17.100 364 0.100 1 10
17.200 365 0.100 1 10
17.300 367 0.100 2 20
17.400 368 0.100 1 10
17.500 370 0.100 2 20
17.600 372 0.100 2 20
17.700 373 0.100 1 10
17.800 376 0.100 3 30
17.900 378 0.100 2 20
18.000 380 0.100 2 20
18.100 382 0.100 2 20
18.200 385 0.100 3 30
18.300 387 0.100 2 20
18.400 390 0.100 3 30
18.500 393 0.100 3 30
18.600 397 0.100 4 40
18.700 402 0.100 5 50
18.800 406 0.100 4 40
18.900 413 0.100 7 70
19.000 421 0.100 8 80
19.050 428 0.050 7 140
19.100 435 0.050 7 140
19.150 440 0.050 5 100
19.200 461 0.050 21 420
19.250 501 0.050 40 800
19.275 551 0.025 50 2000
19.300 667 0.025 116 4640
19.313 682 0.012 15 1200
19.325 696 0.012 14 1120
19.338 704 0.013 8 640
19.350 711 0.012 7 560
19.363 715 0.012 4 320
19.375 720 0.012 5 400
19.388 724 0.012 4 320
19.400 727 0.013 3 240
19.450 738 0.150 71 473
19.500 744 0.050 6 120
19.550 751 0.050 7 140
19.600 755 0.050 4 80
19.650 761 0.050 6 120
19.700 764 0.050 3 60
19.800 770 0.100 6 60
19.900 774 0.100 4 40
20.000 777 0.100 3 30
Three, the preparation of 0.1mol/L perchloric acid titration liquid: get anhydrous glacial acetic acid and (calculate by water cut, every 1g water adds aceticanhydride 5.22ml) 750ml, add perchloric acid (70%~72%) 8.5ml, shake up, at room temperature slowly drip aceticanhydride 24ml, limit edged shakes, and after adding, jolting is even again, lets cool, add anhydrous glacial acetic acid and make in right amount 1000ml, shake up, place 24 hours, standby.
Four, the demarcation of perchloric acid titration liquid: be taken at 105 ℃ of about 0.16g of benchmark Potassium Hydrogen Phthalate that are dried to constant weight, accurately weighed, adding anhydrous glacial acetic acid 20ml makes to dissolve, add 1 of crystal violet indicator solution (5g/L), with this liquid, be slowly titrated to blueness, and the result of titration is proofreaied and correct with blank test.The perchloric acid titration liquid (0.1mol/L) of every 1ml is equivalent to the Potassium Hydrogen Phthalate of 20.42mg.According to the amount of taking of the consumption of this liquid and Potassium Hydrogen Phthalate, calculate the concentration of this liquid, obtain.
Figure 433812DEST_PATH_IMAGE001
Wherein: V samplefor titration Potassium Hydrogen Phthalate, consume the volume number (ml) of perchloric acid liquid to terminal time; V emptythe perchloric acid volume number (ml) consuming to terminal time for titration blank; C is the concentration (mol/L) of perchloric acid titration liquid; W is the Potassium Hydrogen Phthalate amount (mg) taking.
Because the expansion coefficient of glacial acetic acid is larger, so if when titration sample and the temperature difference while demarcating perchloric acid titration liquid surpass 10 ℃, re-start demarcation, if while not surpassing 10 ℃, reply temperature causes that the change of volume proofreaies and correct.
Five, sample replica test
Take N-methylmorpholine sample (lot number 090420) 0.2g(and be accurate to 0.0001g), adding aceticanhydride 30mL dissolves, add 2 of crystal violet indicator solutions, with perchloric acid titration liquid (0.1 mol/L), be titrated to solution aobvious green, and the result of titration is proofreaied and correct with blank test.With 6 parts, this law replicate determination sample, the results are shown in Table 2.
Table 2 sample replica test result
Six, reference substance replica test
Take N-methylmorpholine reference substance 0.2g(and be accurate to 0.0001g), add aceticanhydride 30mL and dissolve, add 2 of crystal violet indicator solutions, with perchloric acid titration liquid (0.1 mol/L), be titrated to solution aobvious green, and the result of titration is proofreaied and correct with blank test.With 6 parts, this law replicate determination sample, the results are shown in Table 3.
Table 3 reference substance replica test result
Seven, sample size is measured
Take respectively N-methylmorpholine sample 0.2g(and be accurate to 0.0001g), add aceticanhydride 30mL and dissolve, add 2 of crystal violet indicator solutions, with perchloric acid titration liquid (0.1 mol/L), be titrated to solution aobvious green, and the result of titration is proofreaied and correct with blank test.3 parts of every batch sample replicate determinations, the results are shown in Table 4.
Table 4 sample size measurement result
Figure 581077DEST_PATH_IMAGE005
Eight, middle precision test
Take N-methylmorpholine sample (lot number: 090420) 0.2g(is accurate to 0.0001g), adding aceticanhydride 30mL dissolves, add 2 of crystal violet indicator solutions, with perchloric acid titration liquid (0.1 mol/L), be titrated to solution aobvious green, and the result of titration is proofreaied and correct with blank test.The results are shown in Table 5.
Precision test result in the middle of table 5
Beneficial effect of the present invention is: the present invention be take aceticanhydride as solvent, quantitatively dissolve N-methylmorpholine, take crystal violet as indicator, with perchloric acid titration liquid, carry out titration, adopt indicator titration method to measure the content of N-methylmorpholine, the results show, described detection method is quick, accurate, highly sensitive, reproducible, can effectively control the quality of N-methylmorpholine, and the method amount of samples is little, simple to operate.Reached goal of the invention.
accompanying drawing explanation:
Fig. 1 is the titration curve figure that solvent is selected; Wherein: 1. glacial acetic acid; 2. glacial acetic acid: aceticanhydride (25:5); 3. glacial acetic acid: aceticanhydride (20:10); 4. glacial acetic acid: aceticanhydride (15:15); 5. aceticanhydride;
Fig. 2 is potentiometric titration curve figure;
Fig. 3 is a differential curve figure of potentiometric titration curve.
Embodiment
Embodiment 1.
The detection method of described mensuration N-methylmorpholine content is: adopt indicator titration method, step is as follows: take N-methylmorpholine sample 0.2g(and be accurate to 0.0001g), put in conical flask, adding aceticanhydride 30mL dissolves, add 2 of crystal violet indicator solutions, control buret and dropwise drip to conical flask the perchloric acid titration liquid that concentration is 0.1mol/L, limit edged jolting conical flask, observe the variation of color in conical flask, color in conical flask becomes green, and colour-fast in 30 seconds, arrive titration end-point, the hop point of titration end-point color during with potentiometric titration is as the criterion, write down now registration, and the result of titration is proofreaied and correct with blank test, the content of N-methylmorpholine is calculated as follows:
Figure 608256DEST_PATH_IMAGE001
Wherein: V samplefor titration Potassium Hydrogen Phthalate, consume the volume number (ml) of perchloric acid liquid to terminal time; V emptythe perchloric acid volume number (ml) consuming to terminal time for titration blank; C is the concentration (mol/L) of perchloric acid titration liquid; W is the Potassium Hydrogen Phthalate amount (mg) taking.
Embodiment 2.
The detection method of described mensuration N-methylmorpholine content is: adopt indicator titration method, step is as follows: take N-methylmorpholine sample 0.2g(and be accurate to 0.0001g), put in conical flask, adding aceticanhydride 50mL dissolves, add 5 of crystal violet indicator solutions, control buret and dropwise drip to conical flask the perchloric acid titration liquid that concentration is 0.15mol/L, limit edged jolting conical flask, observe the variation of color in conical flask, color in conical flask becomes green, and colour-fast in 30 seconds, arrive titration end-point, the hop point of titration end-point color during with potentiometric titration is as the criterion, write down now registration, and the result of titration is proofreaied and correct with blank test, the content of N-methylmorpholine is calculated as follows:
Figure 807156DEST_PATH_IMAGE001
Wherein: V samplefor titration Potassium Hydrogen Phthalate, consume the volume number (ml) of perchloric acid liquid to terminal time; V emptythe perchloric acid volume number (ml) consuming to terminal time for titration blank; C is the concentration (mol/L) of perchloric acid titration liquid; W is the Potassium Hydrogen Phthalate amount (mg) taking.
Embodiment 3.
The detection method of described mensuration N-methylmorpholine content is: adopt indicator titration method, step is as follows: take N-methylmorpholine sample 0.2g(and be accurate to 0.0001g), put in conical flask, adding aceticanhydride 20mL dissolves, add 1 of crystal violet indicator solution, control buret and dropwise drip to conical flask the perchloric acid titration liquid that concentration is 0.01mol/L, limit edged jolting conical flask, observe the variation of color in conical flask, color in conical flask becomes green, and colour-fast in 30 seconds, arrive titration end-point, the hop point of titration end-point color during with potentiometric titration is as the criterion, write down now registration, and the result of titration is proofreaied and correct with blank test, the content of N-methylmorpholine is calculated as follows:
Figure 413718DEST_PATH_IMAGE001
Wherein: V samplefor titration Potassium Hydrogen Phthalate, consume the volume number (ml) of perchloric acid liquid to terminal time; V emptythe perchloric acid volume number (ml) consuming to terminal time for titration blank; C is the concentration (mol/L) of perchloric acid titration liquid; W is the Potassium Hydrogen Phthalate amount (mg) taking.

Claims (7)

1. a detection method of measuring N-methylmorpholine content, is characterized in that: adopt indicator titration method, step is as follows: take N-methylmorpholine sample, put in conical flask, add aceticanhydride and dissolve, add crystal violet indicator solution, to conical flask, dropwise drip perchloric acid titration liquid, limit edged jolting conical flask, observes the variation of color in conical flask, and the color in conical flask becomes green, and colour-fast in 30 seconds, arrive titration end-point, write down now registration, and the result of titration is tested to correction by blank; Then be calculated as follows the content of N-methylmorpholine content:
Figure 2012102332093100001DEST_PATH_IMAGE001
Wherein: V samplethe volume that consumes perchloric acid liquid to terminal time for titration Potassium Hydrogen Phthalate is counted ml; V emptythe perchloric acid volume consuming to terminal time for titration blank is counted ml; C is the concentration mol/L of perchloric acid titration liquid; W is the Potassium Hydrogen Phthalate amount mg taking.
2. measure as claimed in claim 1 the detection method of N-methylmorpholine content, it is characterized in that: adopt indicator titration method, step is as follows: take N-methylmorpholine sample 0.2g, put in conical flask, adding aceticanhydride 20-50mL dissolves, adding crystal violet indicator solution 1-5 drips, control buret and dropwise drip to conical flask the perchloric acid titration liquid that concentration is 0.01-0.15mol/L, limit edged jolting conical flask, observe the variation of color in conical flask, color in conical flask becomes green, and colour-fast in 30 seconds, arrive titration end-point, write down now registration, and the result of titration is proofreaied and correct with blank test, then be calculated as follows the content of N-methylmorpholine content:
Figure 197970DEST_PATH_IMAGE001
Wherein: V samplethe volume that consumes perchloric acid liquid to terminal time for titration Potassium Hydrogen Phthalate is counted ml; V emptythe perchloric acid volume consuming to terminal time for titration blank is counted ml; C is the concentration mol/L of perchloric acid titration liquid; W is the Potassium Hydrogen Phthalate amount mg taking.
3. measure as claimed in claim 2 the detection method of N-methylmorpholine content, it is characterized in that: the addition of described aceticanhydride is 30mL.
4. measure as claimed in claim 2 the detection method of N-methylmorpholine content, it is characterized in that: the addition of described crystal violet indicator solution is 2.
5. measure as claimed in claim 2 the detection method of N-methylmorpholine content, it is characterized in that: the concentration of described perchloric acid titration liquid is 0.1 mol/L.
6. measure as claimed in claim 1 or 2 the detection method of N-methylmorpholine content, it is characterized in that: described in while taking N-methylmorpholine sample, should be accurate to 0.0001g.
7. measure as claimed in claim 1 or 2 the detection method of N-methylmorpholine content, it is characterized in that: the hop point of titration end-point color during with potentiometric titration is as the criterion.
CN201210233209.3A 2012-07-06 2012-07-06 Detection method for measuring content of N-methylmorpholine Pending CN103529032A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114152605A (en) * 2021-11-23 2022-03-08 镇江威特药业有限责任公司 Method for detecting content of amino acid in feed

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JAMES E. RUCH ET AL: "Determination of SmaH Amounts of Tertiary Amines in the Presence of Primary and Secondary Amines", 《ANALYTICAL CHEMISTRY》 *
杨速兵等: "非水滴定法测定叔胺和季胺盐含量", 《广东化工》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114152605A (en) * 2021-11-23 2022-03-08 镇江威特药业有限责任公司 Method for detecting content of amino acid in feed

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