CN106316902A - Method for preparing dimethyl cyanodithioiminocarbonate - Google Patents
Method for preparing dimethyl cyanodithioiminocarbonate Download PDFInfo
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- CN106316902A CN106316902A CN201610701460.6A CN201610701460A CN106316902A CN 106316902 A CN106316902 A CN 106316902A CN 201610701460 A CN201610701460 A CN 201610701460A CN 106316902 A CN106316902 A CN 106316902A
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- reaction
- dimethyl
- cyanodithioiminocarbonate
- sodium
- isopropanol
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- IULFXBLVJIPESI-UHFFFAOYSA-N bis(methylsulfanyl)methylidenecyanamide Chemical compound CSC(SC)=NC#N IULFXBLVJIPESI-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 17
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 40
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 39
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000706 filtrate Substances 0.000 claims abstract description 22
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 20
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims abstract description 19
- MYFXBBAEXORJNB-UHFFFAOYSA-N calcium cyanamide Chemical compound [Ca+2].[N-]=C=[N-] MYFXBBAEXORJNB-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000007069 methylation reaction Methods 0.000 claims abstract description 18
- 238000001914 filtration Methods 0.000 claims abstract description 17
- 230000008014 freezing Effects 0.000 claims abstract description 17
- 238000007710 freezing Methods 0.000 claims abstract description 17
- 239000012065 filter cake Substances 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 4
- 239000000047 product Substances 0.000 claims description 29
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- MVXMNHYVCLMLDD-UHFFFAOYSA-N 4-methoxynaphthalene-1-carbaldehyde Chemical compound C1=CC=C2C(OC)=CC=C(C=O)C2=C1 MVXMNHYVCLMLDD-UHFFFAOYSA-N 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 14
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 12
- 159000000000 sodium salts Chemical class 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 4
- STRTXDFFNXSZQB-UHFFFAOYSA-N calcium;cyanamide Chemical compound [Ca+2].NC#N STRTXDFFNXSZQB-UHFFFAOYSA-N 0.000 claims description 3
- 230000001186 cumulative effect Effects 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract 4
- 229910052708 sodium Inorganic materials 0.000 abstract 4
- 239000011734 sodium Substances 0.000 abstract 4
- 238000005406 washing Methods 0.000 abstract 2
- 238000003889 chemical engineering Methods 0.000 abstract 1
- 239000012043 crude product Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000012847 fine chemical Substances 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 13
- 239000002253 acid Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 238000013019 agitation Methods 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 2
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 2
- FPFFJBYKCLCHSC-UHFFFAOYSA-N [K]C Chemical class [K]C FPFFJBYKCLCHSC-UHFFFAOYSA-N 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- KEDVUOWPLAHMLZ-UHFFFAOYSA-N 1-cyano-3-[2-[(5-methyl-1h-imidazol-4-yl)methylsulfanyl]ethyl]-2-prop-2-ynylguanidine Chemical compound CC=1NC=NC=1CSCCNC(NC#N)=NCC#C KEDVUOWPLAHMLZ-UHFFFAOYSA-N 0.000 description 1
- NWYRNCMKWHKPAI-UHFFFAOYSA-N C(=O)=O.[Na] Chemical compound C(=O)=O.[Na] NWYRNCMKWHKPAI-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- CCGSUNCLSOWKJO-UHFFFAOYSA-N cimetidine Chemical compound N#CNC(=N/C)\NCCSCC1=NC=N[C]1C CCGSUNCLSOWKJO-UHFFFAOYSA-N 0.000 description 1
- 229960001380 cimetidine Drugs 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- FKTUXVQEOXYNMO-UHFFFAOYSA-N cyanocarbamodithioic acid Chemical compound SC(=S)NC#N FKTUXVQEOXYNMO-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229950007285 etintidine Drugs 0.000 description 1
- 238000006206 glycosylation reaction Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 230000001035 methylating effect Effects 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 238000007867 post-reaction treatment Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
- C07C321/02—Thiols having mercapto groups bound to acyclic carbon atoms
- C07C321/04—Thiols having mercapto groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
- C07C321/12—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to acyclic carbon atoms
- C07C321/14—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing dimethyl cyanodithioiminocarbonate, and belongs to the technical field of fine chemical engineering. The method comprises the following steps: firstly, performing a salt-forming reaction, namely sequentially dispersing and dissolving lime nitrogen and sodium carbonate in water, dropwise adding carbon disulfide to generate a mixed liquid of sodium cyanodithioiminocarbonate, filtering the mixed liquid of sodium cyanodithioiminocarbonate when being hot, sufficiently washing a filter cake with a proper amount of hot water, and mixing the filtrates to obtain an aqueous solution of sodium cyanodithioiminocarbonate; and then, performing a methylation reaction, namely adding acetone or isopropanol into the aqueous solution of sodium cyanodithioiminocarbonate, dropwise adding dimethyl carbonate, reacting to generate a crude product of dimethyl cyanodithioiminocarbonate, and adding acetone and isopropanol once again after the reaction is finished, freezing and crystallizing at low temperature of 20 DEG C below zero, separating out solid, filtering when the solid is still cold, washing and drying to obtain the dimethyl cyanodithioiminocarbonate. The method has the technical characteristics of low-price and easily available raw materials, no pollution and simple and convenient operation process, and is suitable for industrial production.
Description
Technical field:
The invention belongs to technical field of fine, be specifically related to the preparation method of a kind of N-cyanoimido-S, S-dimethyl-dithiocarbonate.
Background technology:
N-cyanoimido-S, S-dimethyl-dithiocarbonate is the intermediate of cimetidine, etintidine, can be widely applied to agricultural chemical insecticide and
The intermediate of antibacterial.The synthesis of N-cyanoimido-S, S-dimethyl-dithiocarbonate is the method using cyanamide to react with Carbon bisulfide all the time,
Its main technological process is: being first prepared as cyanamide base famine acid calcium salt, then carry out methylation reaction, final refining obtains finished product.
Analyzing from its historical background synthesized, the synthesis report of N-cyanoimido-S, S-dimethyl-dithiocarbonate sees the paper " The of 1967 the earliest
Chemistry of CyanodithioimidocarbonicAcid " (Journal ofOrganic Chemistry, 32 (5),
1566 1572), it is raw material that the document describes one cyanamide base dithioacid di-potassium, with acetone as solvent, divides two with iodomethane
There is the method that methylation reaction obtains product in step, its yield is up to 58%.1977, Zeitschrift F ü
RAnorganische Chemie paper " Untersuchungen uber N-Hydroxydithiocarbamidsaure
I.Darstellung und Eigenschaften von N-Hydroxydithiocarbamaten und von
Hydroxylammoniumdithiocarbama " (434 (1), 110 114) report employing cyanamide base dithioacid di-potassium it is
Raw material, the method obtaining product with iodomethane generation methylation reaction, its yield is up to 60%.
The synthetic method of cyanogen amino S,S-Dimethyl cyanoimidodithiocarbonate is described the most all sidedly: use cyanamide in patent PCT9426706
It is Material synthesis dithioacid sodium salt or waste acid potassium salt with Carbon bisulfide, then with dithioacid di-potassium or waste acid methyl monopotassium salt and halogen
Acute pyogenic infection of nails alkane or dimethyl sulfate carry out methylation reaction and obtain product, and its yield is up to 80%.The Organic of 1998
Preparation and Procedures International, " An Improved Preparation of S, S'-
Dimethyl Ncyanodi-thioimino-carbonate ", 30 (4), 473-476 reports with cyanamide and Carbon bisulfide
For Material synthesis dithioacid sodium salt or waste acid potassium salt, then carry out methylation reaction with waste acid methyl monopotassium salt with halide and obtain
Product, yield reaches more than 80%.At home, paper " synthesis in water of the S,S-Dimethyl cyanoimidodithiocarbonate " (Chinese delivered for 2006
Journal ofPharmaceuticals, 37 (5), 303-304) report and with lime nitrogen (main component is nitrolim) be
Raw material, reacts the method generating cyanogen amino famine acid disodium salt, cyanogen in the presence of a phase transfer catalyst with Carbon bisulfide, sodium carbonate
Amino famine acid disodium salt obtains thick product with dimethyl sulfate generation methylation reaction again, obtains crystal product with acetone refining, its
Yield reaches 72%.
From above-mentioned pertinent literature report it can be seen that (1) cyanogen amino famine hydrochlorate synthesis in general be use cyanamide,
Carbon bisulfide and inorganic base react prepared, used inorganic base in organic solvent and are generally sodium hydroxide or potassium hydroxide, and
And product yield is relatively low；(2) methylation reaction uses alkyl halide or dimethyl sulfate, and post-reaction treatment is cumbersome, behaviour
Making technique loaded down with trivial details, and the toxicity of dimethyl sulfate is relatively big, relatively big to harm, the by-product of simultaneous reactions has dirt to environment
Dye, it is difficult to meet the demand that industrialization cleaning produces.
Summary of the invention:
The present invention is in order to overcome the technical problem of existing N-cyanoimido-S, S-dimethyl-dithiocarbonate synthesis technique, it is provided that a kind of more environmentally friendly and
The preparation method of the N-cyanoimido-S, S-dimethyl-dithiocarbonate of high yield.The preparation side of a kind of N-cyanoimido-S, S-dimethyl-dithiocarbonate provided by the present invention
Method specifically comprises the following steps that
(1) salt-forming reaction: by lime nitrogen and sodium carbonate successively dispersing and dissolving in water, and drip Carbon bisulfide, dropping speed
Degree is 5～6mL/min, after dropping, continues reaction 4h～6h, generate cyanamide base dithioacid sodium salt at a temperature of 40 DEG C～45 DEG C
Mixed liquor；By the mixed liquor filtered while hot of described cyanamide base dithioacid sodium salt, filter cake fully washs with appropriate hot water, merging filtrate
The aqueous solution obtaining cyanamide base dithioacid sodium salt treats that next step reacts.
(2) methylation reaction: acetone or isopropanol are added the water-soluble of the described cyanamide base dithioacid sodium salt that step (1) obtains
In liquid, and dripping dimethyl carbonate, rate of addition is 1mL/min, and temperature 20 DEG C～40 DEG C, response time 3h～5h carries out first
Glycosylation reaction generates the thick product of N-cyanoimido-S, S-dimethyl-dithiocarbonate, and reaction adds acetone or isopropanol, again at-20 DEG C of low temperature after terminating
Lower freezing and crystallizing, takes advantage of cold filtration after solid separates out, and uses suitable quantity of water washed product, dried prepared cyanogen amino dithioacid diformazan
Ester, the filtrate after product filters can continue to place freezing and crystallizing under-20 DEG C of low temperature, still has portioned product to separate out；Described lime nitrogen
Be mainly composed of nitrolim, wherein nitrogen content 19wt%, the content of equivalent calcium cyanamide is 56wt%, described cyanamide
The mol ratio of calcium, Carbon bisulfide, sodium carbonate and dimethyl carbonate is 1:(1～1.5): 1:(1.5～3)；Third added for the first time
The volume of ketone or isopropanol is (0.5～1) with the volume ratio of step (1) described water: 1, acetone required in reaction or isopropyl
The cumulative volume of alcohol is (1～2) with the volume ratio of step (1) described water: 1.
Salt-forming reaction and the chemical equation of methylation reaction in the inventive method are as follows:
VWater∶V(isopropanol or acetone)=1: (1～2).
The present invention has a techniques below feature:
1, dimethyl carbonate is as methylating reagent, low toxicity, environmental protection.
2, reacted aqueous sodium carbonate can reduce cost with recycled.
3, after the aqueous solution of cyanamide base dithioacid sodium salt and dimethyl carbonate generation methylation reaction, on low temperature (-20 DEG C of left sides
Right) under freezing and crystallizing overnight, i.e. have a large amount of light yellow needles to separate out, wash after filtration, dry, i.e. can get highly purified
Cyanogen amino S,S-Dimethyl cyanoimidodithiocarbonate, productivity is up to 80～86%, and purity is up to 99.5%.
It is 4, mother liquid obtained containing water, sodium carbonate, acetone or isopropanol with a small amount of cyanogen amino S,S-Dimethyl cyanoimidodithiocarbonate in preparation process,
The acetone distilled out or isopropanol can recycle, do not distill out aqueous sodium carbonate can be with recycled.
5, raw material of the present invention is cheap and easy to get, pollution-free, and operating procedure is easy, can be used for industrialized production.
Detailed description of the invention:
Embodiment 1: the content of lime nitrogen is 19%, equivalent containing calcium cyanamide 56%.Feed molar proportioning, calcium cyanamide:
Carbon bisulfide: sodium carbonate: dimethyl carbonate=1:1:1:1.5.Preparation process is as follows:
(1) salt-forming reaction:
140mL is added in the 250mL three neck round bottom flask being furnished with water-bath, mechanical agitation, thermometer, constant pressure funnel
Water, is slowly added to 36.05g (252.00mmol) lime nitrogen, uniform stirring, and adds 26.71g (252.00mmol) sodium carbonate,
Then 18.69g (252.00mmol) Carbon bisulfide (rate of addition is 5～6mL/min) it is slowly added dropwise.After dropping, 40
DEG C～45 DEG C at a temperature of continue reaction 4h.Reacting complete, filter, filter cake 40mL hot water fully washs, and merging filtrate treats next
Step reaction.
(2) methylation reaction:
With the above-mentioned filtrate of 100mL isopropanol and mixed liquor is transferred in the reaction bulb of 500mL, protects at nitrogen
Under, at a temperature of 0 DEG C, it is slowly added dropwise 34.05g (378.00mmol) dimethyl carbonate (rate of addition is 6～8mL/min), drips
After adding, at a temperature of 20 DEG C, continue reaction 2h.After reaction terminates, 160mL isopropanol is added in reaction mixture, low
Under temperature (about-20 DEG C) freezing, have crystal to separate out after about 4h, take advantage of cold sucking filtration, dry to obtain 27.96g light yellow cyanamide base dithioacid two
Methyl ester product, purity 99.5%, yield 76%.
Continue to place under low temperature (about-20 DEG C) by the filtrate after sucking filtration freezing, have crystal to separate out after about 6h, take advantage of cold taking out
Filter, be dried to obtain 1.47g light yellow N-cyanoimido-S, S-dimethyl-dithiocarbonate product, purity 98.9%, yield 4%.Total recovery 80%.
Embodiment 2: the content of lime nitrogen is 19%, equivalent containing calcium cyanamide 56%.Feed molar proportioning, calcium cyanamide:
Carbon bisulfide: sodium carbonate: dimethyl carbonate=1:1.2:1:1.5.Preparation process is as follows:
(1) salt-forming reaction:
140mL is added in the 250mL three neck round bottom flask being furnished with water-bath, mechanical agitation, thermometer, constant pressure funnel
Water, is slowly added to 36.05g (252.00mmol) lime nitrogen, uniform stirring, and adds 26.71g (252.00mmol) sodium carbonate,
Then 22.43g (302.40mmol) Carbon bisulfide (rate of addition is 5～6mL/min) it is slowly added dropwise.After dropping, 40
DEG C～45 DEG C at a temperature of continue reaction 4h.Reacting complete, filter, filter cake 40mL hot water fully washs, and merging filtrate treats next
Step reaction.
(2) methylation reaction:
Dilute above-mentioned filtrate with 100mL acetone and mixed liquor is transferred in the reaction bulb of 500mL, under nitrogen protection,
At a temperature of 2 DEG C, it is slowly added dropwise 34.05g (378.00mmol) dimethyl carbonate (rate of addition is 6～8mL/min), drips
Bi Hou, continues reaction 2h at a temperature of 20 DEG C.After reaction terminates, 150mL acetone is added in reaction mixture, at low temperature (-20
About DEG C) under freezing, have crystal to separate out after about 5h, take advantage of cold sucking filtration, be dried, obtain 26.49g light yellow N-cyanoimido-S, S-dimethyl-dithiocarbonate product
Product, purity 99.5%, yield 72%.
Continue to place under low temperature (about-20 DEG C) by the filtrate after sucking filtration freezing, have crystal to separate out after about 6h, take advantage of cold taking out
Filter, be dried to obtain 3.31g light yellow N-cyanoimido-S, S-dimethyl-dithiocarbonate product, purity 98.8%, yield 9%.Total recovery 81%.
Embodiment 3: the content of lime nitrogen is 19%, equivalent containing calcium cyanamide 56%.Feed molar proportioning, calcium cyanamide:
Carbon bisulfide: sodium carbonate: dimethyl carbonate=1:1.2:1:2.Preparation process is as follows:
(1) salt-forming reaction:
140mL is put in the 250mL three neck round bottom flask being furnished with water-bath, mechanical agitation, thermometer, constant pressure funnel
Water, is slowly added to 36.05g (252.00mmol) lime nitrogen, uniform stirring, and adds 26.71g (252.00mmol) Carbon Dioxide
Sodium, is then slowly added dropwise 22.43g (302.40mmol) Carbon bisulfide (rate of addition is 1mL/min), after dropping, 40
DEG C～45 DEG C at a temperature of continue reaction 5h.Reacting complete, filter, filter cake 40mL hot water fully washs, and merging filtrate treats next
Step reaction.
(2) methylation reaction:
With the above-mentioned filtrate of 110mL isopropanol and mixed liquor is transferred in the reaction bulb of 500mL, protects at nitrogen
Under, at a temperature of 5 DEG C, it is slowly added dropwise 45.40g (504.00mmol) dimethyl carbonate (rate of addition is 5～6mL/min), dropping
After, at a temperature of 20 DEG C, continue reaction 3h.After reaction terminates, 160mL isopropanol is added in reaction mixture, at low temperature
Under (about-20 DEG C), freezing, has crystal to separate out after about 4h, takes advantage of cold sucking filtration, is dried, obtains 28.70g light yellow cyanamide base dithioacid diformazan
Ester product, purity 99.6%, yield 78%.
Continue to place under low temperature (about-20 DEG C) by the filtrate after sucking filtration freezing, have crystal to separate out after about 6h, take advantage of cold taking out
Filter, be dried to obtain 2.58g light yellow N-cyanoimido-S, S-dimethyl-dithiocarbonate product, purity 98.8%, yield 7%.Total recovery 85%.
Embodiment 4: the content of lime nitrogen is 19%, equivalent containing calcium cyanamide 56%.Feed molar proportioning, calcium cyanamide:
Carbon bisulfide: sodium carbonate: dimethyl carbonate=1:1.5:1:1.5.Preparation process is as follows:
(1) salt-forming reaction:
140mL is added in the 250mL three neck round bottom flask being furnished with water-bath, mechanical agitation, thermometer, constant pressure funnel
Water, is slowly added to 36.05g (252.00mmol) lime nitrogen, uniform stirring, and adds 26.71g (252.00mmol) sodium carbonate,
Then 28.03g (378.00mmol) Carbon bisulfide (rate of addition is 5～6mL/min) it is slowly added dropwise, after dropping, 40
DEG C～45 DEG C at a temperature of continue reaction 4h.Reacting complete, filter, filter cake 40mL hot water fully washs, and merging filtrate treats next
Step reaction.
(2) methylation reaction:
With the above-mentioned filtrate of 120mL isopropanol and mixed liquor is transferred in the reaction bulb of 500mL, protects at nitrogen
Under, at a temperature of 5 DEG C, it is slowly added dropwise 34.05g (378.00mmol) dimethyl carbonate (rate of addition is 6～8mL/min), dropping
After, at a temperature of 20 DEG C, continue reaction 2h.After reaction terminates, 140mL isopropanol is added in reaction mixture, at low temperature
Under (about-20 DEG C), freezing, has crystal to separate out after about 5h, takes advantage of cold sucking filtration, is dried, obtains 27.59g light yellow cyanamide base dithioacid diformazan
Ester product needle-like product, purity 99.5%, yield 75%.
Continue to place under low temperature (about-20 DEG C) by the filtrate after sucking filtration freezing, have crystal to separate out after about 6h, take advantage of cold taking out
Filter, be dried to obtain 2.58g light yellow N-cyanoimido-S, S-dimethyl-dithiocarbonate product, purity 98.8%, yield 7%.Total recovery 82%.
Embodiment 5: the content of lime nitrogen is 19%, equivalent containing calcium cyanamide 56%.Feed molar proportioning, calcium cyanamide:
Carbon bisulfide: sodium carbonate: dimethyl carbonate=1:1.2:1:2.Preparation process is as follows:
(1) salt-forming reaction:
140mL is added in the 250mL three neck round bottom flask being furnished with water-bath, mechanical agitation, thermometer, constant pressure funnel
Water, is slowly added to 36.05g (252.00mmol) lime nitrogen, uniform stirring, and adds 26.71g (252.00mmol) sodium carbonate,
Then 22.43g (302.40mmol) Carbon bisulfide (rate of addition is 5～6mL/min) it is slowly added dropwise, after dropping, 40
DEG C～45 DEG C at a temperature of continue reaction 5h.Reacting complete, filter, filter cake 40mL hot water fully washs, and merging filtrate treats next
Step reaction.
(2) methylation reaction:
Dilute above-mentioned filtrate with 100mL acetone and mixed liquor is transferred in the reaction bulb of 500mL, under nitrogen protection,
At a temperature of 5 DEG C, it is slowly added dropwise 45.40g (504.00mmol) dimethyl carbonate (rate of addition is 6～8mL/min), drips
Bi Hou, continues reaction 2h at a temperature of 20 DEG C.After reaction terminates, 160mL acetone is added in reaction mixture, at low temperature (-20
About DEG C) under freezing, have crystal to separate out after about 5h, take advantage of cold sucking filtration, be dried and to obtain 28.70g light yellow N-cyanoimido-S, S-dimethyl-dithiocarbonate product
Product, purity 99.6%, yield 78%.
Continue to place under low temperature (about-20 DEG C) by the filtrate after sucking filtration freezing, have crystal to separate out after about 8h, take advantage of cold taking out
Filter, be dried to obtain 2.94g light yellow N-cyanoimido-S, S-dimethyl-dithiocarbonate product, purity 98.9%, yield 8%.Total recovery 86%.
Embodiment 6:
The content of lime nitrogen is 19%, equivalent containing calcium cyanamide 56%.Feed molar proportioning, calcium cyanamide: Carbon bisulfide:
Sodium carbonate: dimethyl carbonate=1:1.5:1:3.Preparation process is as follows:
(1) salt-forming reaction:
140mL is put in the 250mL three neck round bottom flask being furnished with water-bath, mechanical agitation, thermometer, constant pressure funnel
Water, is slowly added to 36.05g (252.00mmol) lime nitrogen, uniform stirring, and adds 26.71g (252.00mmol) sodium carbonate,
Then 28.03g (378.00mmol) Carbon bisulfide (rate of addition is 5～6mL/min) it is slowly added dropwise, after dropping, 40
DEG C～45 DEG C at a temperature of continue reaction 4h.Reacting complete, filter, filter cake 40mL hot water fully washs, and merging filtrate treats next
Step reaction.
(2) methylation reaction:
With the above-mentioned filtrate of 140mL isopropanol and mixed liquor is transferred in the reaction bulb of 500mL, protects at nitrogen
Under, at a temperature of 4 DEG C, it is slowly added dropwise 68.10g (756.00mmol) dimethyl carbonate (rate of addition is 6～8mL/min), dropping
After, at a temperature of 20 DEG C, continue reaction 2h.After reaction terminates, 140mL isopropanol is added in reaction mixture, at low temperature
Freezing under (about-20 DEG C), about 4h has crystal to separate out, and takes advantage of cold sucking filtration, is dried, obtains the light yellow N-cyanoimido-S, S-dimethyl-dithiocarbonate of 27.59g
Product, purity 99.5%, yield 75%.
Continue to place under low temperature (about-20 DEG C) by the filtrate after sucking filtration freezing, have crystal to separate out after about 6h, take advantage of cold taking out
Filter, be dried to obtain 1.84g light yellow N-cyanoimido-S, S-dimethyl-dithiocarbonate product, purity 98.9%, yield 5%.Total recovery 80%.
Should be noted that above content, only in order to technical scheme to be described, is not limitation of the present invention,
In the range of present inventive concept, the interpolation that carried out, convert, replacement etc. belongs to protection scope of the present invention.
Claims (1)
1. the preparation method of a N-cyanoimido-S, S-dimethyl-dithiocarbonate, it is characterised in that the method specifically comprises the following steps that
(1) salt-forming reaction: by lime nitrogen and sodium carbonate successively dispersing and dissolving in water, and dripping Carbon bisulfide, rate of addition is 5
～6mL/min, after dropping, at a temperature of 40 DEG C～45 DEG C, continue reaction 4h～6h, generate the mixed of cyanamide base dithioacid sodium salt
Close liquid；By the mixed liquor filtered while hot of described cyanamide base dithioacid sodium salt, filter cake fully washs with appropriate hot water, and merging filtrate obtains
The aqueous solution of cyanamide base dithioacid sodium salt treats that next step reacts；
(2) methylation reaction: acetone or isopropanol are added the aqueous solution of the described cyanamide base dithioacid sodium salt that step (1) obtains
In, and dripping dimethyl carbonate, rate of addition is 1mL/min, and temperature 20 DEG C～40 DEG C, response time 3h～5h carries out methyl
Changing reaction and generate the thick product of N-cyanoimido-S, S-dimethyl-dithiocarbonate, reaction adds acetone or isopropanol, under-20 DEG C of low temperature after terminating again
Freezing and crystallizing, takes advantage of cold filtration after solid separates out, and uses suitable quantity of water washed product, dried prepared described cyanogen amino dithioacid diformazan
Ester；Described lime nitrogen be mainly composed of nitrolim, wherein nitrogen content 19wt%, the content of equivalent calcium cyanamide is
56wt%, the mol ratio of described calcium cyanamide, Carbon bisulfide, sodium carbonate and dimethyl carbonate is 1:(1～1.5): 1:(1.5～
3)；The acetone added for the first time or the volume of isopropanol are (0.5～1) with the volume ratio of step (1) described water: 1, institute in reaction
The acetone needed or the cumulative volume of isopropanol are (1～2) with the volume ratio of step (1) described water: 1.
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| CN112979555A (en) * | 2021-02-24 | 2021-06-18 | 盐城凯利药业有限公司 | Process for synthesizing cimetidine |
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