CN1052676A - The directly method and the application thereof of synthetic organo-tin compound - Google Patents

The directly method and the application thereof of synthetic organo-tin compound Download PDF

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Publication number
CN1052676A
CN1052676A CN 90110146 CN90110146A CN1052676A CN 1052676 A CN1052676 A CN 1052676A CN 90110146 CN90110146 CN 90110146 CN 90110146 A CN90110146 A CN 90110146A CN 1052676 A CN1052676 A CN 1052676A
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Prior art keywords
tin
chloride
alkyl
amine
reaction
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CN 90110146
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罗莫尔多·马尔库滋
茂里滋奥·本德历
米歇尔·罗森索
阿尔伯特·W·普尔佐
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Baerlocher GmbH
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Baerlocher GmbH
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Abstract

The present invention relates to that a kind of to react direct synthesis type by metallic tin and alkyl chloride be R nS nC 14-nThe method of organo-tin compound, n=1-4 in the formula; The R representative has the straight or branched or the aliphatic alkyl of 4-18 carbon atom;
The method is characterized in that, be reflected under the ammonium chloride existence shown in amine shown in the general formula (A) and/or the formula (B) and carry out.
(A)R′ aN[(CH 2CH 2O) mCH 2CH 2OR 2] 3-α
(B)R′bN[(CH 2CH 2O) mCH 2CH 2OR 2] 4-bCl。

Description

The directly method and the application thereof of synthetic organo-tin compound
The present invention relates to the method for the organo-tin compound shown in a kind of directly synthetic general formula (1), and the mixture of these compounds and application thereof.
N=1-4 in the formula;
The R representative has straight or branched or the cycloalphatic alkyl that 4-18 is a carbon atom.
Industrial, come to synthesize organo-tin compound usually by the following method, the organotin muriate shown in the especially above-mentioned formula (1):
-tin tetrachloride and alkylidene group reactive aluminum method;
The refined synthesis method of-Green.
Carry out directly when synthetic being set out by metallic tin by following reaction formula (2), molecular balance is on the equation left side, and if there is not suitable catalyzer, then the productive rate of required compound is not high:
There are following side reaction in alkyl tin chloride and alkyl chloride and/or metallic tin:
In addition, reactant ligand (Auto-Komproportionierungs-reaktionen) also may take place to divide automatically:
And the formation by product, especially from SnCl 2By product:
In above-mentioned synthesizing, may there be following compound in the reaction mixture:
R 14Sn, R 13SnCl, R 1SnCl 2, R 1SnCl 3And SnCl 2
In each case, all above-claimed cpds are in industrial all useful application, because they can change required final product into by known response:
When above-mentioned one or more side reactions and main reaction are reacted in the lump, or during mutual superposition, then can form the tin halides (SnCl of various content 2), the latter can reclaim or be used for the next step separately again.
The directly synthetic halid method of organotin especially uses alkyl bromide and alkyl iodide as raw material, existing narration in many patent documentations.
For example, known in 857,868 from US3, in the presence of tertiary amine and/or quaternary ammonium salt, can carry out direct building-up reactions, wherein the latter can form from tertiary amine and the alkylogen " original place " that is adopted.
Be reflected at polar solvent and/or can with the tin catalyst for reaction in carry out.Be this purpose, adopt alcohol, ester or acid amides sometimes.When direct synthesis of alkyl tin halides, to compare with alkyl iodide with corresponding alkyl bromide, alkyl chloride is relatively low to the reactive behavior of metallic tin.Alkyl carbon atoms number in the increase alkyl chloride can improve the yield of speed of reaction and required product, wherein adopts C 4-alkyl chloride (Butyryl Chloride) directly building-up reactions has been difficult to carry out.Therefore, the alkyl tin chloride can technical scale, from tin tetrachloride by preparing with trialkyl aluminium compound reaction, the refined synthesis method of Green or improved Wurtz synthesis method, but additional many expenses, method steps is long.
The objective of the invention is to use the direct method of synthetic organo-tin compound of alkyl chloride with 4 or more carbon atoms, this method is simple and yield is high.
This purpose of the present invention is finished by above-mentioned a kind of method, it is characterized in that: be reflected under the ammonium chloride existence shown in amine shown in the general formula (A) and/or the formula (B) and carry out:
A=0 in the formula, 1 or 2;
B=0,1,2 or 3;
R 1Representative has the straight or branched or the cycloalphatic alkyl of 2-24 carbon atom, aryl, alkylaryl or substituted aryl, and if a=2 or b=2 or 3, then R 1Can be identical or different;
R 2Represent H, have the straight or branched alkyl of 1-20 carbon atom, aryl, substituted aryl or alkylaryl; And
m＝1-20。
The invention particularly relates to the method for directly synthesizing organo-tin compound from alkyl chloride, because the corresponding alkyl bromide of reactivity ratio and the alkyl iodide of alkyl chloride are low, its use is more difficult, but it is the low advantage of alkyl chloride expense that raw material is arranged, do not need the work down of required usually pressure, because its low boiling point uses moieties to have the alkyl chloride that is lower than 4 carbon atoms.
Surprisingly, if utilize the present invention's reaction of the directly synthetic organo-tin compound of metallic tin and alkyl chloride in the presence of above-mentioned formula (A) amine or formula (B) ammonium chloride, to carry out then very effective.Under the situation of amine shown in the formula of the use A, but the original place forms ammonium salt.
Reaction suits under 20-200 ℃ of temperature, under 140-190 ℃, carries out in the presence of 0.1-4mol formula (A) amine and/or formula (B) ammonium chloride (every relatively mol tin) more fortunately.Reaction times is suitably 3-24 hour, is preferably 6-10 hour.And every relatively mol tin, alkyl chloride is suitably 1-6mol, is preferably 2-3mol.
Although not necessarily, there is the I of trace 2Or Br 2, especially 10 -3-0.2 better is 10 -2The I of mol 2Or Br 2(every relatively mol tin) benefits to this reaction.I 2And/or Br 2Can directly add in the reaction or dissolving and alkyl chloride add in the lump.
After reaction is finished, can reclaim amine and/or ammonium chloride in succession by known chemical process.
For reaction is carried out smoothly, the concentration of alkyl chloride can not be too high so that serve as solvent, though this point is not necessarily extremely important.Therefore, preferably under the temperature of selecting, drip alkyl chloride lentamente to keep chosen temperature.Reaction can be carried out in appropriate solvent so that reaction mixture is enough rare.
After reaction was finished, filter reaction mixture was to separate unreacted tin according to a conventional method.Then can be with reusing after washing with acetone and the drying.
Underpressure distillation filtrate is to reclaim unreacted alkyl chloride and/or possible solvent.
When using amine and/or ammonium chloride, form the dialkyl group tindichloride, the mixture of trialkyl tin chloride and tetraalkyl tin and tindichloride with the tin equimolar amount.When using amine and/or ammonium chloride greater than equimolar amount, reaction product mainly is the trialkyl tin chloride, obtains the tetraalkyl tin and the tindichloride of various content in addition.With 0.5mol, especially 0.1-0.33mol(is to every mol tin) when catalytic amount used amine and/or ammonium chloride, reaction product was nearly pure dialkyl group tin chloride and a spot of alkyl tin trichloride.
By the especially suitable midbody product of the organo-tin compound of the inventive method preparation as preparation thermo-stabilizer such as tin alkyl sulfhydryl compound (for preparation polyvinyl chloride resin).
Following examples are in order to explanation the present invention.
The transformation efficiency of used metallic tin represents that with % wherein all tin compound kinds (wherein tin does not exist with metallic forms, for example exists with the tindichloride form sometimes) all are useful products in reaction product.
Reaction product is analyzed by tlc.
Embodiment 1
At room temperature, with glass putty (36g, 0.3mol) with octyl group chlorine (14.9g, 0.1mmol) and I 2(0.4g, 1.57 * 10mol) are suspended in the amine (C of average composition in the lump 13H 27N[(CH 2CH 2O) 1,3CH 2CH 2OH] 2(120.3g, 0.3mol) in.
Stir down reaction mixture is heated to 170-175 ℃, under this temperature, last 6 hours and add octyl group chlorine again that (120.1g 0.81mol), in whole reinforced process, keeps described temperature.After all octyl group chlorine added, reaction was under agitation proceeded 3 hours in 170-175 ℃.
Temperature is cooled to 80-90 ℃ then, leaches unreacted tin, and use washing with acetone, drying is also weighed.The transformation efficiency of tin is 84%.
Learn that through the tlc analysis main component in the product is R 3SnCl and R 2SnCl 2(wherein first composition is main amount), the RSnCl of trace in addition 3And R 4Sn.
Embodiment 2
With glass putty (60g, 0.5mol) with octyl group chlorine (14.9g, 0.1mol) and I 2(0.635g, 2.5 * 10 -3Mol) be suspended in the amine (C of average composition in the lump 13H 27N[(CH 2CH 2O) 1,3CH 2CH 2OH] 2(40.1g; 0.1mol) in.Reaction mixture is heated to 175 ℃, under this temperature, under agitation last 6 hours and add again octyl group chlorine (148.5g, 1.0mol).
After adding material, reaction is under agitation proceeded 3 hours in 175 ℃.Be cooled to 80-90 ℃ then, leach unreacted tin, use washing with acetone, drying is also weighed.
The transformation efficiency of tin is 65%.
Learn that through the TLC analysis product is mainly by R 2SnCl 2And RSnCl 3Form, first kind of composition is main amount.Also there is a certain amount of R 3SnCl also detects the R of trace 4Sn.
Embodiment 3
With glass putty (36g, 0.3mol) with octyl group chlorine (178.2g, 1.2mol) and I 2(0.76g, 3 * 10 -3Mol) be suspended in the lump trans-(3, the 6-dioxaheptyl) amine (194g, 0.6mol) in, and 175 ℃ of following stirring reactions 12 hours.
When reaction finishes, temperature is cooled to 80-90 ℃, leaches unreacted tin, washing, dry and weigh.
The transformation efficiency of tin is 78%.The TLC spectrum analysis shows that product is mainly by R 3SnCl and R 2SnCl forms, and wherein first kind of composition is a large amount of.
Embodiment 4
With glass putty (36g, 0.3mol) with octyl group chlorine (14.9g, 0.1mol) and I 2(0.76g, 3 * 10 -3Mol) be suspended in the lump diethyl ethoxy ethanol amine (96.75g, 0.4mol) in.
Under agitation reaction mixture is heated to 170-175 ℃, under this temperature, last 4 hours and add in addition octyl group chlorine (74.2g, 0.5mol).After adding material, react on 175 ℃ of stirring reactions 4 hours.
After being cooled to 80-90 ℃, leach unreacted tin, washing, drying is also weighed.The transformation efficiency of tin is 66.6%.
The TLC analysis revealed, product is by R 3SnCl, R 4Sn and R 2SnCl 2Form, first kind of composition is main amount.
Embodiment 5
(24g is 0.2mol) with octyl group chlorine (118.8g, 0.8mol) I with glass putty 2(0.51g, 2 * 10 -3Mol) be suspended in the amine C of average composition in the lump 18H 37N[(CH 2CH 2O) 3,5CH 2CH 2OH] 2(66.3g, 0.1mol) in.
Reaction mixture was under agitation kept 12 hours in 160 ℃.After the cooling, leach unreacted tin, washing, dry and weigh.
The transformation efficiency of tin is 81.8%, and product is mainly by R 3SnCl and R 2SnCl 2Form.
Embodiment 6
With glass putty (36g, 0.3mol) and I 2(0.76g, 3 * 10 -3Mol) be suspended in the amine C of average composition in the lump 13H 27N[(CH 2CH 2O) 1,3CH 2CH 2OH] 2(83.3g, 0.9mol) in, by one be inserted in the reaction subsurface probe (83.3g 0.9mol) is added drop-wise in the reaction mixture that is heated to 170-175 ℃, and keeps temperature of reaction with Butyryl Chloride.
Then, reaction mixture is in 80 ℃ of filtrations.Leach unreacted tin, washing, drying are also weighed.
The transformation efficiency of used tin is 76.4%.
Product is mainly by R 3SnCl forms.
Embodiment 7
With glass putty (36g, 0.3mol) and I 2(0.76g, 3 * 10 -3Mol) be suspended in the lump in the diethyl ethoxy ethanol amine.Press embodiment 6 described same procedure, last 7.5 hours, under agitation drip Butyryl Chloride (83.3g, 0.9mol).Add material postcooling reaction mixture, leach unreacted tin, washing, drying are also weighed.
The transformation efficiency of used tin is 64.5%.
Product is mainly by R 3SnCl and R 4Sn and R 2SnCl 2Form.
Embodiment 8
With glass putty (60g, 0.5mol) be suspended in fusion ammonium salt diethyl-two-(ethoxy ethanol) ammonium chloride (71.5g, 0.25mol) in.Stir down and be heated to 180 ℃, last 5 hours dropping octyl group chlorine (185.5g, 1.25mol).
After adding whole octyl group chlorine, reaction under agitation continues to stir 7 hours in 180-185 ℃.
Then, be cooled to 80-90 ℃, leach unreacted tin, and washing, dry and weigh.
The transformation efficiency of used tin is 86.5%.
Product is mainly by R 3SnCl and R 2SnCl 2Form, first kind of composition is slightly many.
Embodiment 9
With formula is (C 4H 9) 2N(CH 2CH 2OCH 2CH 2OCH 2CH 2Amine OH) (28.8g, 0.11mol) and I 2(0.63g, 2.5 * 10 -3Mol) be heated to 130 ℃ in the lump.
Under this temperature, (40g 0.34mol) suspends wherein, and (143.4g 0.7mol), and is heated to 180-190 ℃ with temperature to last 7.5 hours and be added dropwise to lauryl chloride with glass putty.
Reaction is proceeded 2.5 hours.
After being cooled to 80-90 ℃, leach unreacted tin, washing, drying are also weighed.The transformation efficiency of used tin is 90%.Product is mainly by R 2SnCl 2Form, a spot of R is arranged 3SnCl.

Claims (8)

1, the method for directly synthesizing the organo-tin compound shown in the following formula by metallic tin and alkyl chloride reaction:
The R representative has the straight or branched or the cycloalphatic alkyl of 4-18 carbon atom,
The method is characterized in that reaction is to carry out in the presence of the ammonium chloride shown in amine shown in the general formula (A) and/or the formula (B):
A=0 in the formula, 1 or 2;
B=0,1,2 or 3;
R 1Representative has the straight or branched or the cycloalphatic alkyl of 2-24 carbon atom, aryl, and alkaryl or substituted phenyl, and if a=2, or b=2 or 3, then R ' group can be identical or different;
R 2Represent H, have the straight or branched alkyl of 1-20 carbon atom, aryl, substituted aryl or alkylaryl; And
m=1-20。
2, the method for claim 1 is characterized in that R 2It is straight or branched alkyl with 1-4 carbon atom.
3, claim 1 or 2 method is characterized in that m=1-10, especially 1-3.
4, at least one described method among the claim 1-3 is characterized in that, as alkyl chloride, can adopt Butyryl Chloride, octyl group chlorine or lauryl chloride.
5, at least one described method among the claim 1-4 is characterized in that for every mole of tin, the used amine and/or the ratio of ammonium chloride are the 0.1-0.33 mole.
6, at least one described method among the claim 1-4 is characterized in that, with respect to tin, adopts the amine and/or the ammonium chloride of equimolar amount.
7, at least one described method among the claim 1-4 is characterized in that, with respect to tin, adopts amine and/or ammonium chloride greater than equimolar amount.
8, according to the application in the thermo-stabilizer of preparation polyvinyl chloride of the organo-tin compound of the described method of claim 1-7 preparation as intermediate product.
CN 90110146 1989-12-18 1990-12-18 The directly method and the application thereof of synthetic organo-tin compound Pending CN1052676A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 90110146 CN1052676A (en) 1989-12-18 1990-12-18 The directly method and the application thereof of synthetic organo-tin compound

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP89123402.3 1989-12-18
CN 90110146 CN1052676A (en) 1989-12-18 1990-12-18 The directly method and the application thereof of synthetic organo-tin compound

Publications (1)

Publication Number Publication Date
CN1052676A true CN1052676A (en) 1991-07-03

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