CN101343287A - Synthesis of sicycle-ring hexyl di-thiophosphinic acid - Google Patents
Synthesis of sicycle-ring hexyl di-thiophosphinic acid Download PDFInfo
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- CN101343287A CN101343287A CNA2008101192130A CN200810119213A CN101343287A CN 101343287 A CN101343287 A CN 101343287A CN A2008101192130 A CNA2008101192130 A CN A2008101192130A CN 200810119213 A CN200810119213 A CN 200810119213A CN 101343287 A CN101343287 A CN 101343287A
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- diethyl ether
- bromocyclohexane
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Abstract
The invention discloses a synthetic method of dicyclohexyl dithiophosphinate. The method comprises: taking bromo cyclohexane as a raw material which is firstly reacted with a magnesium rod for obtaining a Grignard reagent, forming a linked phosphorus intermediate through the reaction between the acquired Grignard reagent and phosphorus thiochloride, obtaining a crude product of dicyclohexyl dithiophosphinate through steps of sulfurization and acidification, then gaining a pure product of dicyclohexyl dithiophosphinate through amine salt formation, recrystallization and acidification. Compared with the current methods, the method of the invention has the advantages of easy obtaining of materials, less synthesis steps, simple process, high yield and low toxicity.
Description
Technical field
The invention belongs to the synthetic method of compound in the organic chemistry, relate in particular to the synthetic method of sicycle-ring hexyl di-thiophosphinic acid.
Background technology
The dithiophosphinic acids compounds is a class flotation agent of broad research in the metallurgical industry, and the structure of its some type as Cynaex301, has good complex coordination and separating power to the group of the lanthanides actinium series.The synthetic method of dialkyl dithio phospho acid has multiple, passes through the phenyl ring of phenyl ring or replacement at AlCl as the structure that aromatic base replaces more
3Catalysis down and P
2S
5Reaction makes; The synthetic method of the compound that the one-level alkyl replaces is many, can begin to obtain intermediate secondary phosphine from different reaction raw materials, this intermediate makes dithiophosphinic acids or salt through over cure, also can obtain salt through joining the reaction of phosphorus intermediate and sulphur and sodium sulphite, salt provides dithiophosphinic acids through acidifying; The synthetic main sulfuration by the secondary phosphine of secondary alkyl and cyclohexyl dithiophosphinic acids realizes.But volatility, the pungency of secondary phosphine are more intense, thereby toxicity is bigger.
Summary of the invention
The object of the present invention is to provide the synthetic method of sicycle-ring hexyl di-thiophosphinic acid, compare with existing method, the inventive method raw material is easy to get, yield height, toxicity are little.
The present invention is to be raw material with the phosphorus thiochloride, and the Yu Geshi reagent react obtains sicycle-ring hexyl di-thiophosphinic acid through steps such as sulfuration, acidifying, purifications.Its reaction formula is as follows:
Realize that technical scheme of the present invention is as follows:
The synthetic method of sicycle-ring hexyl di-thiophosphinic acid of the present invention comprises the preparation of Grignard reagent, the preparation of connection phosphorus intermediate, and the synthetic and purifying of sicycle-ring hexyl di-thiophosphinic acid, concrete steps are as follows:
(1) preparation of Grignard reagent: be that 1: 1～2 ratio is put into magnesium rod and anhydrous diethyl ether according to weightmeasurement ratio in the there-necked flask of the reflux condensing tube that sealed stirrer, constant pressure funnel and band drying tube are housed, add 3～5 iodine grains again; In constant pressure funnel be 1: 2～2.5 mixed bromocyclohexane and anhydrous diethyl ether according to volume ratio, add bromocyclohexane and magnesium mol ratio be 1: 1～1.1; Bromocyclohexane diethyl ether solution in the constant pressure funnel is dropped in the there-necked flask, leave standstill initiation reaction; Drip remaining bromocyclohexane diethyl ether solution then while stirring, rate of addition is as the criterion to keep the reaction mixture gentle reflux; After the bromocyclohexane diethyl ether solution dropwised, the reacting by heating mixed solution kept refluxing and disappears until magnesium rod, and ice bath cooling then obtains the grey clarified liq, is Grignard reagent;
(2) preparation of connection phosphorus intermediate: with ice-water bath step (1) gained Grignard reagent being cooled to below 10 ℃, is that 1: 0.25 ratio drips SPCl with constant pressure funnel in Grignard reagent according to mol ratio then
3, and keep the reaction mixture temperature at 0～10 ℃; Drip SPCl
3After finishing, remove ice-water bath, at room temperature the stirring reaction mixed solution is 18～26 hours; Reaction mixture slowly is poured in 8～12% sulphuric acid solns that contain ice cube while stirring then; Use extracted with diethyl ether again 2～3 times, merge ether phase, concentrated, dry, obtain colourless oil liquid, the gained colourless oil liquid is (C
6H
11)
4P
2S
2
(3) sicycle-ring hexyl di-thiophosphinic acid is synthetic: the ratio that according to mol ratio is 1: 1: 1 is to sealed stirrer, reflux condensing tube, constant pressure funnel being housed and colourless oil liquid, the Na that adds step (2) gained in the there-necked flask of nitrogen protection being arranged
2S9H
2O and S powder, and according to Na
2S9H
2Weightmeasurement ratio is 1: 8～10 ratio adding 1 between the O, the 4-dioxane, and heating makes reaction mixture refluxed 18～24h then; The filtered while hot reaction solution obtains yellow solution; Steaming desolventizes, and obtains the reddish-brown solid; Being that 1: 15～20 ratio is dissolved in the reddish-brown solid in the deionized water according to weightmeasurement ratio, dividing the layer that deoils, is colourless with 30～60 ℃ of petroleum ether to petroleum ether layer, in the aqueous solution, add 2mol/L hydrochloric acid, separate out white precipitate, filter, obtain faint yellow solid; The faint yellow solid of gained is a dicyclohexyl dithiophosphlic acid crude product;
(4) purifying of sicycle-ring hexyl di-thiophosphinic acid: be that 1: 5～12 ratio is dissolved in step (3) gained faint yellow solid in the hexanaphthene according to weightmeasurement ratio, feed ammonia, generate white precipitate, filter, get faint yellow solid, (1/50, mixed solvent recrystallization v/v) gets white crystal through dehydrated alcohol/benzene; Be that 1: 8～12 ratio is dissolved in white crystal in the distilled water according to weightmeasurement ratio then, and be that 1: 5～6 ratio adds 2M HCl according to weightmeasurement ratio between white crystal and the HCI, mix, use extracted with diethyl ether again 2～3 times, merging, concentrated, dry, obtain pulverous white crystal, be sicycle-ring hexyl di-thiophosphinic acid.
Magnesium rod described in the above-mentioned synthetic method step (1) and the weightmeasurement ratio between the anhydrous diethyl ether are 1: 2.
Volume ratio in the bromocyclohexane diethyl ether solution described in the above-mentioned synthetic method step (1) between bromocyclohexane and the anhydrous diethyl ether is 1: 2.
Faint yellow solid described in the above-mentioned synthetic method step (4) and the weightmeasurement ratio between the hexanaphthene are 1: 5～10.
Dehydrated alcohol described in the above-mentioned synthetic method step (4) and the volume ratio between the benzene are 1: 50.
Advantages such as advantage of the present invention: it is cheap and easy to get that the inventive method has raw material, and yield height, toxicity are less relatively.Gained sicycle-ring hexyl di-thiophosphinic acid of the present invention can be used for metal flotation and high activity liquid waste aftertreatment.
Embodiment
The present invention is described in detail with embodiment below, but embodiment does not produce any restriction to the present invention.
The preparation of embodiment 1 sicycle-ring hexyl di-thiophosphinic acid
Carry out according to following steps:
(1) preparation of Grignard reagent: in the 500ml there-necked flask of the reflux condensing tube that sealed stirrer and band drying tube are housed, put into magnesium rod 12.2 (0.5mol) g, anhydrous diethyl ether 20ml and 3 iodine mix bromocyclohexane 61ml (0.5mol) and anhydrous diethyl ether 130ml in constant pressure funnel; Drip 20ml bromocyclohexane diethyl ether solution earlier, leave standstill initiation reaction; Start then to stir and also dropwise add remaining bromocyclohexane diethyl ether solution, maintenance reaction mixture gentle reflux; Dropwise the post-heating reaction mixture and make it to reflux, disappear substantially until magnesium rod, ice bath cooling then obtains the grey clarified liq, is Grignard reagent.
(2) preparation of connection phosphorus intermediate: with ice-water bath step (1) gained Grignard reagent is cooled to 5 ℃, drips 13ml SPCl with constant pressure funnel
3(0.125mol), keep the reaction mixture temperature to be lower than 10 ℃; After dropwising, remove ice-water bath, stirring at room 24 hours; While stirring mixed solution slowly is poured into then in 10% sulphuric acid soln that contains ice cube, standing demix is used extracted with diethyl ether lower floor water three times, merges all ether phases, concentrated, dry, obtains the 22.7g colourless oil liquid.
(3) sicycle-ring hexyl di-thiophosphinic acid is synthetic: the 22.7 gram colourless oil liquid (C that add gained in the step (2) in the 250ml there-necked flask of sealed stirrer, reflux condensing tube, constant pressure funnel and nitrogen protection is housed
6H
11)
4P
2S
2(0.05mol) and Na
2S9H
2O (11.9g, 0.05mol) (1.6g 0.05mol), adds 1 again, 4-dioxane 200ml, reflux 24h with the sulphur powder; Then reacting liquor while hot is filtered and obtain yellow solution, steaming desolventizes, and obtains reddish-brown solid 22.3g; With this reddish-brown solid 400ml deionized water dissolving, divide the layer that deoils, be colourless with 30～60 ℃ of petroleum ether to petroleum ether layer, in the aqueous solution, add the 2mol/L hydrochloric acid of 100ml, generate white precipitate, filter, obtain faint yellow solid 20g, be the sicycle-ring hexyl di-thiophosphinic acid crude product.
(4) purifying of sicycle-ring hexyl di-thiophosphinic acid: 20g is dissolved in the 200ml hexanaphthene with step (3) gained faint yellow solid, feed ammonia, generate white precipitate, filter faint yellow solid 18.5g, (1/50, mixed solvent recrystallization v/v) gets white crystal 16g through dehydrated alcohol/benzene, be the sicycle-ring hexyl di-thiophosphinic acid ammonium, its fusing point is 178.7～179.8 ℃.
Gained white crystal 0.98g is dissolved in the 10ml distilled water, mixes with the 2M HCl of 5ml, with ether 10ml extraction 2 times, merging, concentrated, dry obtains white crystalline powder shape product 0.79g, and its fusing point is 100.7～101.8 ℃.With SPCl
3For starting raw material calculates, overall yield of reaction is 40%.The gained end product characterizes through proton nmr spectra, carbon spectrum, phosphorus spectrum, the relevant spectrum of hydrogen hydrogen, hydrocarbon relevant spectrum, high resolution flight time mass spectrum, is defined as the target product sicycle-ring hexyl di-thiophosphinic acid.Nuclear magnetic spectrum and interpretation of mass spectra data are as follows:
1H NMR (600MHz, CD
3OD) δ ppm 1.13 (q, J
4a, 3a=J
4a, 5a=13.0Hz, J
4a, 4e=12.4Hz, 2H
4a), 1.24 (q, J
3a, 3e=J
5a, 5e=12.4Hz, J
3a, 2a=J
3a, 4a=J
5a, 6a=J
5a, 4a=13.0Hz, 4H, 2H
3a, 2H
5a), 1.36 (m, 4H, 2H
2a, 2H
6a), 1.63 (d, J
4a, 4e=12.4Hz, 2H
4e), 1.76 (d, J
3a, 3e=J
5a, 5e=11.04Hz, 4H, 2H
3e, 2H
5e), 1.90 (s, 4H, 2H
2e, 2H
6e), 1.96 (m, 2H
1).
13C NMR (150MHz, CD
3OD) δ ppm 25.56,25.58,25.67,25.83,25.93 (10C), 41.49,41.80 (2C
1).
31P NMR (240MHz, CD
3OD) δ ppm 87.33.TOF HRMS EI
+Calc.For C
12H
23PS
2(M+H)
+262.0979 Found 262.0981.
Claims (5)
1, the synthetic method of sicycle-ring hexyl di-thiophosphinic acid comprises the steps:
(1) is that 1: 1～2 ratio is put into magnesium rod and anhydrous diethyl ether in the there-necked flask of the reflux condensing tube that sealed stirrer, constant pressure funnel and band drying tube are housed according to weightmeasurement ratio, adds 3～5 iodine grains again; In constant pressure funnel be 1: 2～2.5 mixed bromocyclohexane and anhydrous diethyl ether according to volume ratio, add bromocyclohexane and magnesium mol ratio be 1: 1～1.1; Bromocyclohexane diethyl ether solution in the constant pressure funnel is dropped in the there-necked flask, leave standstill initiation reaction; Drip remaining bromocyclohexane diethyl ether solution then while stirring, rate of addition is as the criterion to keep the reaction mixture gentle reflux; After the bromocyclohexane diethyl ether solution dropwised, the reacting by heating mixed solution kept refluxing and disappears until magnesium rod, and ice bath cooling then obtains the grey clarified liq, is Grignard reagent;
(2) with ice-water bath step (1) gained Grignard reagent being cooled to below 10 ℃, is that 1: 0.25 ratio drips SPCl with constant pressure funnel in Grignard reagent according to mol ratio then
3, and keep the reaction mixture temperature at 0～10 ℃; Drip SPCl
3After finishing, remove ice-water bath, at room temperature the stirring reaction mixed solution is 18～26 hours; Reaction mixture slowly is poured in 8～12% sulphuric acid solns that contain ice cube while stirring then; Use extracted with diethyl ether again 2～3 times, merge ether phase, concentrated, dry, obtain colourless oil liquid;
(3) be that 1: 1: 1 ratio is to sealed stirrer, reflux condensing tube, constant pressure funnel being housed and colourless oil liquid, the Na that adds step (2) gained in the there-necked flask of nitrogen protection being arranged according to mol ratio
2S9H
2O and S powder, and according to Na
2S9H
2Weightmeasurement ratio is 1: 8～10 ratio adding 1 between the O, the 4-dioxane, and heating makes reaction mixture refluxed 18～24h then; The filtered while hot reaction solution obtains yellow solution; Steaming desolventizes, and obtains the reddish-brown solid; Being that 1: 15～20 ratio is dissolved in the reddish-brown solid in the deionized water according to weightmeasurement ratio, dividing the layer that deoils, is colourless with 30～60 ℃ of petroleum ether to petroleum ether layer, in the aqueous solution, add 2mol/L hydrochloric acid, separate out white precipitate, filter, obtain faint yellow solid; The faint yellow solid of gained is a dicyclohexyl dithiophosphlic acid crude product;
(4) be that 1: 5～12 ratio is dissolved in step (3) gained faint yellow solid in the hexanaphthene according to weightmeasurement ratio, feed ammonia, generate white precipitate, filter, faint yellow solid, through the mixed solvent recrystallization of dehydrated alcohol/benzene, white crystal; Be that 1: 8～12 ratio is dissolved in white crystal in the distilled water according to weightmeasurement ratio then, and be that 1: 5～6 ratio adds 2M HCl according to weightmeasurement ratio between white crystal and the HCI, mix, use extracted with diethyl ether again 2～3 times, merging, concentrated, dry, obtain pulverous white crystal, be sicycle-ring hexyl di-thiophosphinic acid.
2,, it is characterized in that the weightmeasurement ratio between described magnesium rod of its step (1) and the anhydrous diethyl ether is 1: 2 according to the described synthetic method of claim 1.
3,, it is characterized in that the volume ratio between the bromocyclohexane and anhydrous diethyl ether is 1: 2 in the described bromocyclohexane diethyl ether solution of its step (1) according to the described synthetic method of claim 1.
4,, it is characterized in that the weightmeasurement ratio between described faint yellow solid of its step (4) and the hexanaphthene is 1: 5～10 according to the described synthetic method of claim 1.
5,, it is characterized in that dehydrated alcohol described in its step (4) and the volume ratio between the benzene are 1: 50 according to the arbitrary described synthetic method of claim 1 to 4.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101619074B (en) * | 2009-07-27 | 2012-07-04 | 清华大学 | Asymmetric dithiophosphinic acid synthesis method |
| CN108727633A (en) * | 2018-06-28 | 2018-11-02 | 浙江大学 | Dialkyl dithio hypophosphites, the halogen-free flame-retardant system of inorganic phosphite and nitrogenous compound collaboration and its application |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| PH31603A (en) * | 1994-03-22 | 1998-11-03 | Goro Nickels S A | Process for the extraction and separation of nickel and/or cobalt. |
| US5759512A (en) * | 1996-06-04 | 1998-06-02 | Cytec Technology Corp. | Regeneration of dithiophosphorus acid metal extractants |
-
2008
- 2008-08-29 CN CN2008101192130A patent/CN101343287B/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101619074B (en) * | 2009-07-27 | 2012-07-04 | 清华大学 | Asymmetric dithiophosphinic acid synthesis method |
| CN108727633A (en) * | 2018-06-28 | 2018-11-02 | 浙江大学 | Dialkyl dithio hypophosphites, the halogen-free flame-retardant system of inorganic phosphite and nitrogenous compound collaboration and its application |
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