IL46304A

IL46304A - Process for preparing tricyclohexyltin derivatives

Info

Publication number: IL46304A
Application number: IL46304A
Authority: IL
Original assignee: Oxon Italia Spa
Priority date: 1973-12-28
Filing date: 1974-12-20
Publication date: 1977-11-30
Also published as: FR2256172B1; BR7410597D0; NL169184B; DE2460288C3; GB1450490A; BE823838A; ES433351A1; FR2256172A1; JPS5096544A; AU7668774A; IT1002391B; NL7416648A; DE2460288A1; DE2460288B2; NL169184C; IL46304A0; JPS5745760B2

Description

Pxocesa for preparing T Derivatives The present Invention relates to a process for the production of derivatives in particular of trloyclohexyltln ha ides Sn wherein X designates halogen or 6 3 It is known to produce trloyclohexyltln by the reactions which comprises wn techniques and It also known that by this reaction the desired product is obtained in very low yields when carried out by adding the tin tetrahalide to the Qrlgnard but still not satisfactory are achieved by reversin the order of introduction of the reactants into the reaction accordance with Italian Patent still better yield can be obtained by the same but by the reactants simultaneously the reaction vessel such manner that they react always in the ratio of 3 1 provided by the reaction accordance Italian Patent of the same even in this las the yields are not entirely satisfactory and a rather sophisticated technique has to be The reason fo the low of halide of the described reaction lies thejeasy formation of derivatives of tetrasubstltuted to a smaller extent of and This drawback is obviated by the present which relates to a process which makes possible to obtain trloyclohexyltln haiides high yields and with a degree of mole of an addition obtained by reacting one mol of tin tetrahallde with two moles of an aromatic or reacted three moles of reagent complexed in known manner an aromatic or cyclic ether and dissolved a aooordanoe with the following reactio Sn wherein X is as The reagent for reaotion may be by the known from magnesium and a cycloalkyl or chlorides or in the presenoe of an aliphatic ether such as diethyl ether or butyl or the presence Of particular complexing agents such as or the presence or not of aliphatic or aromatio The additio compound of tin tetrahalide of the formula may be selected from series of solid products which are stable in th A oertaln number these including that with ethyl have been describe by and in 335 while suc as the complexes with tetrahydrofuran and which also very bee described by Pfahler and Mattalr 3821 Al these produots are prepared by causing two equivalents of the ether seleoted among those mentioned above to drip into a solution of tin tetrahalide in an aliphatic or aromatio At the end of this a white crystalline precipitate or a complex soluble the reaotion medium is always a is the first the precipitate suspended in a suitable hydrocarbon and added in this way to the Qrignard In this reagent is added In this manner the reaction referred to hereinbefore takes the result of which is the formation of the compound of the formula with high yields and without obtaining of the nature of there are as moderate amounts of products of the nature of The absence of tetrasubstituted products which are difficult to parate from tri substituted products because they have similar cophysical assumes particular importance in this case because of the considerable simplifications deri ing therefrom in the field of industrial It is also important to point out that the best practical results are obtained when tetrahal ide insoluble in the reaction are The invention will now be further illustrated following to which no limitative character should evidently be Example 1 In a reaction vessel equipped with a a a condenser with a calcium chloride and a there are placed 400 ml of anhydrous toluene and 78 g of tin added 450 ml of a solution of 1 mole of complexed cyclohexylmagnesium chloride with mole of tetrahydrofuran in The reaction mass must be well while the time for carrying out the addition should be 10 to 120 preferably about 30 the temperature being maintained between and preferably and by suitable The addition having been the reaction mass is heated to preferably for 2 cooled to room temperature and by pouring it into a 5 solution of hydrochloric organic phase evaporated until dry under a vacuum of mm at a temperature of The resulting crystalline mass is dissolved 320 ml of tertbutyl On re lux of the a clear is Obtained after precipitates a white crystalline After filtration and 109 g of trlcyclohexyltin are The yield is about Example 2 In a reaction equipped with a a a reflux condenser with a calcium chloride and a there are placed 400 ml of anhydrous toluene and 78 g 65 ml anhydrous ethyl ether ar added dropwlse to the suitably oooled th being held betwee and A white crystalline precipitate to which are added ml of a solutio of 1 mole of cyolohexylmagnesium chloride Operating under the conditions in Example g of trioyclohexylti are this the yield reaches operation carried out as described Example with the difference that ml of a solution 1 mole of comirlexed cyolohexylmagnesium chloride with 1 mole of tetrahydrofuran in toluene are added to the tin ether 103 g of are The yield at least Example The opeatlon is carried ut in accordance with Example with the difference that solution of 1 mole of chloride in ether is to the tin 103 g of trlcyclohexyltin are is Example 5 tin tetrahallde complex Toeing prepared with isopropyl g of are The yield about Example 6 The carried ou in acco tetrahallde complex prepared in 100 g of are The yield is about Example operation The is carried out as described in the tetrahallde complex being prepared with g of are The yield is Example 8 She operation is carried out as described in Example the with tetrahallde complex being prepared 101 g of SnC are The yield is It understood that any changes the process of the present Illustrated the previous will become apparent to those skilled the art and that these fall entirely within the SCOpe the subject to the scope of the appended insufficientOCRQuality

Claims

1. . Process forj reparing tr1cyclohexylt1n hal lde, characterized in that one mole of an addition compound , obtained by reacting one mole of tin terahal ide with two moles of an aliphatic , aromatic or cyclic ether, 1s reacted with three moles of Grignard reagent complexed In known manner In an al iphatic, aromatic or cycl ic ether and dissolved 1n a hydrocarbon , In accordance with the following reaction: 3(C6Hn )Mg. R£0 + SnX4.2R£0 ^ (C6Hll )3SnX + 3M9X2 + 5R2° wherein X 1s a halogen chosen from bromine and chlorine and R20 Is an al iphatic, aromatic or cycl ic ether apt to form a stable addition compound with the tin tetrahal lde.

2. Process as claimed In claim 1 , wherein the reagents are added one to the other at 20° to 50°C , after which the reaction %'§.-:■'■ continued at a temperature between 70°C and 100°C.

3. Process as claimed in cl aim 2, wherein the first temperature?! 1s 40 - 45°C.

4. Process as claimed in any of cl aims 1 to 3 wherein the Grignard reagent (CgH^ jMgX.RgO 1s added , in the ratio of 3:1 , to a suspension or sol ution of SnX4.2R20 in an al iphatic or aromatic hydrocarbon , during a time 10 - 120 minutes.

5. Process as claimed 1n claim 4 , wherein the said hydrocarbon 1s toluene and the time is 10 - 30 minutes.

6. Process as claimed 1n any of claims 1 to 5 wherein R20 is chosen among ethyl ether, isopropyl ether , n-butyl ether, tetrahydrofuran, tetrahydropyran , dloxan and an 1 sole.

7. Process as claimed 1n claim 6, wherein RgO is an ether which forms with the tin tetrahal lde an addition compound Insol uble 1n the said hydrocarbon. 46304/2 I

8. Process as claimed in claims 1 to 7, wherein RgO 1s tetrahy droduran.

9. Process as claimed in claim 8, wherein the mass 1s heated to 70*0 to 100°C, preferably 80°C for 2 hours.

10. A process according to claim 1 for the production of tricycio hexyltin hal lde, substantially as hereinbefore described and with reference to any of the examples. ttorneys or pp cant