CN101519371B - Preparation method of cartap hydrochloride intermediate, i.e., 2-N, N-dimethyl-1, 3-dithio-cyano propane - Google Patents
Preparation method of cartap hydrochloride intermediate, i.e., 2-N, N-dimethyl-1, 3-dithio-cyano propane Download PDFInfo
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- CN101519371B CN101519371B CN200810062030XA CN200810062030A CN101519371B CN 101519371 B CN101519371 B CN 101519371B CN 200810062030X A CN200810062030X A CN 200810062030XA CN 200810062030 A CN200810062030 A CN 200810062030A CN 101519371 B CN101519371 B CN 101519371B
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000001294 propane Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- MSHXTAQSSIEBQS-UHFFFAOYSA-N s-[3-carbamoylsulfanyl-2-(dimethylamino)propyl] carbamothioate;hydron;chloride Chemical compound [Cl-].NC(=O)SCC([NH+](C)C)CSC(N)=O MSHXTAQSSIEBQS-UHFFFAOYSA-N 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 239000002904 solvent Substances 0.000 claims abstract description 27
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 11
- IRUJZVNXZWPBMU-UHFFFAOYSA-N cartap Chemical compound NC(=O)SCC(N(C)C)CSC(N)=O IRUJZVNXZWPBMU-UHFFFAOYSA-N 0.000 claims description 34
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical group CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- MYKZLATVIJZNTH-UHFFFAOYSA-N azane;cyano thiocyanate Chemical compound N.N#CSC#N MYKZLATVIJZNTH-UHFFFAOYSA-N 0.000 claims description 3
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 claims description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 abstract description 57
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 abstract description 49
- 238000000926 separation method Methods 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 238000001914 filtration Methods 0.000 description 10
- 238000006460 hydrolysis reaction Methods 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- 238000009413 insulation Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000007710 freezing Methods 0.000 description 6
- 230000008014 freezing Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 4
- 230000008030 elimination Effects 0.000 description 4
- 238000003379 elimination reaction Methods 0.000 description 4
- 229910017053 inorganic salt Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- -1 carbamoylthio Chemical class 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- QHTQREMOGMZHJV-UHFFFAOYSA-N Thiobencarb Chemical compound CCN(CC)C(=O)SCC1=CC=C(Cl)C=C1 QHTQREMOGMZHJV-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000026030 halogenation Effects 0.000 description 2
- 238000005658 halogenation reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000003444 phase transfer catalyst Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 231100000004 severe toxicity Toxicity 0.000 description 2
- 238000006365 thiocyanation reaction Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229940022663 acetate Drugs 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Abstract
The invention relates to a preparation method for cartap hydrochloride intermediate, i.e., 2-N, N-dimethyl-1, 3-dithio-cyano propane, which takes 1-N, N-dimethyl-2, 3- propylamine dihalide, thiocyanate as the raw material, obtains the mixture of 2-N, N-dimethyl-1, 3-dithio-cyano propane and 3-N, N-dimethyl-1, 2-dithio-cyano propane by reaction with the existence of a solvent, and obtains 2-N, N-dimethyl-1, 3-dithio-cyano propane with high content by separation; simultaneously, 3-N, N-dimethyl-1, 2-dithio-cyano propane isomer participates the reaction circularly, thus having high yield, good product quality, small amount of three wastes, and better industrial application prospect.
Description
Technical field
The present invention relates to a kind of cartap midbody 2-N, N-dimethyl--1, the preparation method of 3-dithiocyano propane.
Technical background
2-N; N-dimethyl--1,3-dithiocyano propane (abbreviation thiocyanide) are the necessary midbodys of preparation sterilant cartap, US3332943, denomination of invention " carbamoylthio derivatives "; Relate to the method for preparing cartap by cartap midbody thiocyanide; And relate to positive structure body of midbody thiocyanide and isomer, and corresponding positive structure body of cartap and the cartap isomer of obtaining after the hydrolysis, structural formula is following:
Formula A:2-N, N-dimethyl--1,3-dithiocyano propane (the positive structure body of thiocyanide); Formula B: the positive structure body of cartap
Formula C:3-N, N-dimethyl--1,2-dithiocyano propane (thiocyanide isomer)
Formula D: cartap isomer
It almost all is positive structure body that the former medicine of the required cartap of existing market demand requires, and because of the disosultap of low levels has more isomer, it is lower to obtain thiocyanide content through cyanogenation, does not generally adopt.For obtaining high-load cartap, be through of the sodium cyanide reaction of high-load benthiocarb at present with severe toxicity, prepare cartap midbody thiocyanide earlier; The thiocyanide content that obtains like this is higher, almost all is positive structure body, obtains high-load cartap through hydrolysis then; Resulting cartap almost all is positive structure body; Useless cartap isomer impurities content is less, and higher advantage is arranged on the quality product, and reaction formula is following:
But in preparation during thiocyanide, separating with hypertoxic sodium cyanide reaction solution, in the washing operation, not only having poor working environment, poison dangerous greatly, and produce a large amount of cyanide wastewater, processing cost is high.CN1060913C, denomination of invention " preparation method of cartap "; Disclose a kind of by improving one's methods for the feedstock production cartap such as benthiocarb, sodium cyanide, methyl alcohol, hydrogen chloride gas; Though in operation, improvement has been arranged, but has not avoided using the sodium cyanide raw material of severe toxicity.CN1830957A, denomination of invention " 2-N, N-dimethyl--1,3-two sulfhedryl propane new preparation processes " disclose a kind of with 1-N; N-dimethyl--2,3-dichloro-propyl-amine hydrochloride (abbreviation muriate) is a raw material, is neutralized into free alkali with alkali earlier; Add aromatic solvent according to a certain ratio, the proportioning of muriate and aromatic hydrocarbons is 1: 500-1000 (mol: L), drip the Sodium Thiocyanate 99 alcoholic solution for preparing; Reaction obtains 2-N, N-dimethyl--1,3-dithiocyano propane.Patent does not disclose the content of positive structure body of midbody thiocyanide and isomer; Low about 50%～60% through experiment showed, according to the positive structure body burden of patent CN1830957A gained midbody thiocyanide, gained cartap content is lower behind hydrolysis reaction; Contain more cartap isomer impurities; The positive structure body of cartap yield is lower, and gained cartap effective constituent is lower like this, does not have industrial applications to be worth.Adopt non-cyaniding route to synthesize thiocyanide; The more thiocyanide isomer of inevitable generation; Though can through change reaction conditions as: reduce measures such as temperature of reaction, improve the positive structure body burden of thiocyanide, the yield of thiocyanide can be lower; And the content of thiocyanide do not reach the requirement of doing high-load cartap yet, and product does not just have the industriallization meaning like this.In order to overcome above shortcoming, the present invention provides the preparation method of the thiocyanide of a kind of high-content, high yield, and quantity of three wastes is few, and process implementing is convenient, has the industrial applications prospect, and the gained thiocyanide obtains the cartap of the high yield of high-content through hydrolysis.
Summary of the invention
Purpose of design: avoid the weak point in the background technology, design a kind of cartap midbody 2-N of the thiocyanide of a kind of high-content, high yield, N-dimethyl--1, the preparation method of 3-dithiocyano propane.
Plan: in order to realize above-mentioned purpose of design.The present invention is with 1-N, N-dimethyl--2, and 3-dihalo propylamine is a raw material, structural formula is following:
Wherein X is halogen (Cl; Br I) reacts the mixture (formula two) of the thiocyanide that obtains containing positive structure, isomery, according to conditions such as different solvents, reaction times in the presence of solvent with thiocyanate-; The positive structure body burden of thiocyanide is generally 40～80%, and structural formula is following:
The thiocyanide mixture obtains the positive structure body of high-content thiocyanide through separation; The thiocyanide isomer of separating simultaneously returns next reaction system, and recycled is under processing condition of the present invention; Find that positive structure body of thiocyanide and isomer reach a running balance; The positive structure body of thiocyanide total recovery increases substantially like this, has also solved simultaneously the low levels thiocyanide and has got into next step hydrolysis reaction, converts the cartap isomer to and reduces yield; Reduce the shortcoming of quality product, have very high industriallization application prospect.
The raw materials used 1-N of the present invention, N-dimethyl--2,3-dihalo propylamine normally obtains aminate by propenyl chloride and n n dimetylaniline reaction; Through the acidifying salify, halogenation obtains corresponding 1-N again, N-dimethyl--2,3-dihalo propylamine hydrogen salt; Halogenation can be chlorination, bromination or iodate, is preferably chlorination, and the gained hydrochloride is neutralized into 1-N with alkali; N-dimethyl--2, the 3-dichloro-propyl-amine, directly or be used for the thiocyanation reaction after the layering.
The raw materials used thiocyanate-of the present invention, available Sodium Thiocyanate 99, Rhocya, ammonium thiocyanide etc. preferably use Sodium Thiocyanate 99.Thiocyanate-and 1-N, N-dimethyl--2, the consumption proportion of 3-dihalo propylamine are 2～3: 1 (mol ratio), and consumption is many to be improved not quite reaction yield, and optimum ratio is 2.0～2.5: 1 (mol ratio).
Described reaction solvent in the scope of the invention, available alcohols, as: methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, sec-butyl alcohol etc.; The benzene class, as: benzene, toluene, ethylbenzene, YLENE, chlorobenzene etc.; The ester class, as: ETHYLE ACETATE, propyl acetate, butylacetate etc.; Ketone, as: acetone, butanone, pentanone etc.; Ethers: propyl ether, isopropyl ether, butyl ether etc.; Nitrile, as: acetonitrile, butyronitrile etc.; Halogenated hydrocarbon, as: ethylene dichloride, trichloromethane, tetracol phenixin etc.; The aprotic polar solvent class, as: N, DMSO 99.8MIN., THF, N-Methyl pyrrolidone etc.Solvent load is 1-N, N-dimethyl--2, and 1～10 times (weight) of 3-dihalo propylamine raw material, solvent is many with causing unnecessary loss, preferably uses 2～6 times (weight); Described separate sulfur prussiate carries out in solvent in the scope of the invention, is to utilize the thiocyanide isomer; Cooling back preferential crystallization is separated out in solvent, thereby separates the thiocyanide isomer earlier, and cover capable of circulation is used for reaction next time; The solvent filtrating that obtains after the separation is the positive structure body of high-load thiocyanide; According to different solvents, can from solvent, separate the positive structure body of thiocyanide and obtain the positive structure body of high-load thiocyanide product through freezing and crystallizing, the precipitation or add methods such as elutriation goes out of reducing pressure; Also can in solvent, directly be used for next step hydrolysis reaction.Described separation solvent in the scope of the invention can be with a kind of solvent with reaction solvent, also homogeneous solvent not; Solvent load is 1-N, N-dimethyl--2,1～10 times (weight) of 3-dihalo propylamine raw material; Solvent is many preferably to use 2～6 times (weight) with causing unnecessary loss, and the reaction back is steamed earlier and removed reaction solvent; Obtain the positive isomer mixture of thiocyanide, add another kind of solvent again and carry out Crystallization Separation, for simplifying the operation; The present invention reaction with separates solvent and preferably uses with a kind of solvent, alcohols, benzene class, ketones solvent especially are suitable as and react and separate solvent; The said temperature of reaction of the scope of the invention is carried out under 45～85 ℃, carries out under preferred 60～75 ℃; Reaction times is generally 2～10 hours (in 2～10 hours scopes value and comprise end value) arbitrarily; Reaction times is too short; Yield can reduce, and the reaction times is long, can produce some side reactions; Yield is corresponding can be reduced, preferred 3～6 hours (in 3～6 hours scopes value and comprise end value) arbitrarily.
Described preparation method in the scope of the invention, reaction system can allow the existence of water, helps the dissolving of thiocyanate-, can shorten the reaction times, but the water yield can influence reaction yield and product separating effect more for a long time; Reaction system can allow the existence of phase-transfer catalyst simultaneously, and the existence of phase-transfer catalyst can be shortened the reaction times.
The present invention compares with background technology, and the one, the positive structure body burden of gained thiocyanide >=98% has positive structure body yield height, and gained cartap product content >=98% has the industrial applications prospect after the hydrolysis; The 2nd, quantity of three wastes is few, and process implementing is convenient, has the industrial applications prospect, and the gained thiocyanide obtains the cartap of the high yield of high-content through hydrolysis.
Embodiment
Embodiment 1: drop into the 400g propyl carbinol in the reaction flask, Sodium Thiocyanate 99 115g, 110g content are 95% 1-N, N-dimethyl--2,3-dichloro-propyl-amine; Heat up 45～85 ℃ (in 45～85 ℃ of scopes value and comprise end value) arbitrarily, insulation reaction 5 hours, thiocyanide just, isomer proportion: positive structure body 51%; Isomer 48% filters the sodium-chlor inorganic salt that elimination generates, and crystallization is separated out in the filtrating cooling; Filtration obtains thiocyanide isomer solid crystal (positive structure body 5%, isomer 94%), the 57g that gives money as a gift, filtrating freezing and crystallizing; Filtration obtains the positive structure body of thiocyanide (positive structure body 97%, isomer 2%), the 54g that gives money as a gift, the positive structure body of thiocyanide yield 39%.
Embodiment 2: drop into the 400g propyl carbinol in the reaction flask, and embodiment 1 gained isomer 57g, Sodium Thiocyanate 99 58g, 55g content are 95% 1-N; N-dimethyl--2, the 3-dichloro-propyl-amine, 45～85 ℃ (in 45～85 ℃ of scopes value and comprise end value) arbitrarily heat up; Insulation reaction 5 hours, thiocyanide just, isomer proportion, positive structure body 51%; Isomer 47% filters the sodium-chlor inorganic salt that elimination generates, and crystallization is separated out in the filtrating cooling; Filtration obtains thiocyanide isomer solid crystal (positive structure body 6%, isomer 93%), the 58g that gives money as a gift, filtrating freezing and crystallizing; Filtration obtains the positive structure body of thiocyanide (positive structure body 98%, isomer 1%), the 53g that gives money as a gift, the positive structure body of thiocyanide yield 77%.
Embodiment 3: drop into 500g acetone in the reaction flask, and embodiment 2 gained isomer 58g, Sodium Thiocyanate 99 58g, 55g content are 95% 1-N; N-dimethyl--2, the 3-dichloro-propyl-amine, 45～70 ℃ (in 45～70 ℃ of scopes value and comprise end value) arbitrarily heat up; Insulation reaction 5 hours, thiocyanide just, isomer proportion, positive structure body 50%; Isomer 48% filters the sodium-chlor inorganic salt that elimination generates, and crystallization is separated out in the filtrating cooling; Filtration obtains thiocyanide isomer solid crystal (positive structure body 5%, isomer 94%), the 58g that gives money as a gift, filtrating freezing and crystallizing; Filtration obtains the positive structure body of thiocyanide (positive structure body 98%, isomer 1%), the 52g that gives money as a gift, the positive structure body of thiocyanide yield 76%.
Embodiment 4: drop into 500g toluene, water 100ml, four butyl bromation amine 4g, embodiment 3 gained isomer 58g in the reaction flask; Ammonium thiocyanide 55g, 80g content are 95% 1-N, N-dimethyl--2, and 3-dibromo propylamine, 45～85 ℃ (in 45～85 ℃ of scopes value and comprise end value) arbitrarily heat up; Insulation reaction 6 hours, thiocyanide just, isomer proportion, positive structure body 52%; Isomer 47%, branch vibration layer while hot, crystallization is separated out in the solvent layer cooling; Filtration obtains thiocyanide isomer solid crystal (positive structure body 5%, isomer 94%), the 58g that gives money as a gift, filtrating freezing and crystallizing; Filtration obtains the positive structure body of thiocyanide (positive structure body 98%, isomer 1%), the 52g that gives money as a gift, the positive structure body of thiocyanide yield 75%.
Embodiment 5: drop into toluene mother liquor, water layer, the thiocyanide isomer that embodiment 4 obtains in the reaction flask, drop into Sodium Thiocyanate 99 58g, 55g content again and be 95% 1-N, N-dimethyl--2; The 3-dichloro-propyl-amine, heat up 45～85 ℃ (in 45～85 ℃ of scopes value and comprise end value) arbitrarily, insulation reaction 6 hours; Filtered while hot elimination inorganic salt, the solvent layer branch vibration layer, crystallization is separated out in the solvent layer cooling; Filtration obtains thiocyanide isomer solid crystal (positive structure body 5%, isomer 94%), the 57g that gives money as a gift, filtrating freezing and crystallizing; Filtration obtains the positive structure body of thiocyanide (positive structure body 98%, isomer 1%), the 54g that gives money as a gift, the positive structure body of thiocyanide yield 78%.
Embodiment 6: drop into methyl alcohol 200g in the reaction flask, the positive structure body of embodiment 2 gained thiocyanides 50g feeds the exsiccant hydrogen chloride gas at 10～15 ℃, to all dissolvings; Stop logical hydrogen chloride gas, be warming up to 20～25 ℃ of insulations 3 hours, lower the temperature about 10 ℃; Filter, the small amount of methanol washing gets white cartap solid crystal (positive structure body 98.4%, isomer 0.1%); Oven dry 64g, 179～181 ℃ of fusing points, yield 94%.
Comparative example 1: drop into 400g ethanol in the reaction flask, Sodium Thiocyanate 99 116g, 110g content are 95% 1-N, N-dimethyl--2; The 3-dichloro-propyl-amine heats up 65～75 ℃ insulation reaction 6 hours; After filtrate decompression steams solvent; Add elutriation and go out, filter and obtain thiocyanation materialization thing (positive structure body 50%, isomer 48%), oven dry 106g.
Comparative example 2: drop into methyl alcohol 400g in the reaction flask, comparative example 1 gained thiocyanide 100g feeds the exsiccant hydrogen chloride gas at 10～15 ℃; To all dissolving is transparent, stop logical hydrogen chloride gas, be warming up to 20～25 ℃; Be incubated 3 hours, lower the temperature about 10 ℃, filter; The small amount of methanol washing gets white cartap solid crystal, oven dry 72g (positive structure body 73%, isomer 26%).
What need understand is: though the foregoing description is to the present invention's detailed explanation of contrasting; But these explanations, just to simple declaration of the present invention, rather than limitation of the present invention; Any innovation and creation that do not exceed in the connotation of the present invention all fall into protection scope of the present invention.
Claims (5)
1. cartap midbody 2-N, N-dimethyl--1, the preparation method of 3-dithiocyano propane, it is by 1-N; N-dimethyl--2,3-dihalo propylamine, thiocyanate-are raw material, prepared in reaction is separating obtained in the presence of solvent, it is characterized in that: isomer products 3-N; N-dimethyl--1,2-dithiocyano propane cycles are participated in reaction, 1-N wherein, N-dimethyl--2; 3-dihalo propylamine raw material is selected from 1-N, N-dimethyl--2,3-dichloro-propyl-amine or 1-N, N-dimethyl--2; 3-dibromo propylamine or 1-N, N-dimethyl--2,3-diiodo-propylamine; Thiocyanate-is selected from Sodium Thiocyanate 99 or Rhocya or ammonium thiocyanide.
2. cartap midbody 2-N according to claim 1, N-dimethyl--1, the preparation method of 3-dithiocyano propane is characterized in that: used 1-N, N-dimethyl--2,3-dihalo propylamine raw material is 1-N, N-dimethyl--2,3-dichloro-propyl-amine.
3. cartap midbody 2-N according to claim 1, N-dimethyl--1, the preparation method of 3-dithiocyano propane is characterized in that: used thiocyanate-is a Sodium Thiocyanate 99.
4. cartap midbody 2-N according to claim 1, N-dimethyl--1, the preparation method of 3-dithiocyano propane is characterized in that: solvent is butanols, acetone or toluene.
5. cartap midbody 2-N according to claim 1, N-dimethyl--1, the preparation method of 3-dithiocyano propane is characterized in that: temperature of reaction is: 45～85 ℃, the reaction times is: 2～10 hours.
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| CN104774167A (en) * | 2014-11-27 | 2015-07-15 | 湖南昊华化工有限责任公司 | Cartap intermediate 1, 3-thiocyanide normal compound preparation method |
| CN106748937B (en) * | 2017-01-10 | 2018-06-19 | 仪征市海帆化工有限公司 | The synthetic method of cartap |
| CN106905209B (en) * | 2017-01-21 | 2018-10-30 | 宁波科诺华化工有限公司 | A kind of synthesis technology of cartap intermediate |
| CN106905210B (en) * | 2017-01-21 | 2018-10-30 | 宁波科诺华化工有限公司 | A kind of preparation method of cartap intermediate |
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| GB1264207A (en) * | 1968-04-04 | 1972-02-16 | ||
| CN1263089A (en) * | 1998-09-18 | 2000-08-16 | 武田药品工业株式会社 | Preparation of thiol-carbamate and sulfocyanic ester compound |
| CN1830957A (en) * | 2005-03-09 | 2006-09-13 | 梁建忠 | Novel process for preparing 2-N,-N-dimethyl-1, 3-thiocyanato propane |
| CN101103725A (en) * | 2007-07-23 | 2008-01-16 | 江苏天容集团股份有限公司 | Cartap environment-friendly type preparing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1264207A (en) * | 1968-04-04 | 1972-02-16 | ||
| CN1263089A (en) * | 1998-09-18 | 2000-08-16 | 武田药品工业株式会社 | Preparation of thiol-carbamate and sulfocyanic ester compound |
| CN1830957A (en) * | 2005-03-09 | 2006-09-13 | 梁建忠 | Novel process for preparing 2-N,-N-dimethyl-1, 3-thiocyanato propane |
| CN101103725A (en) * | 2007-07-23 | 2008-01-16 | 江苏天容集团股份有限公司 | Cartap environment-friendly type preparing method |
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