US3067225A - Process of preparing tetraaryl tin - Google Patents
Process of preparing tetraaryl tin Download PDFInfo
- Publication number
- US3067225A US3067225A US708748A US70874858A US3067225A US 3067225 A US3067225 A US 3067225A US 708748 A US708748 A US 708748A US 70874858 A US70874858 A US 70874858A US 3067225 A US3067225 A US 3067225A
- Authority
- US
- United States
- Prior art keywords
- tin
- aryl
- tetraaryl
- alkali metal
- grams
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims description 19
- 238000000034 method Methods 0.000 title claims description 14
- 229910052783 alkali metal Inorganic materials 0.000 claims description 13
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 12
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 12
- 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 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical class [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- -1 diaryl-tin halide Chemical class 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- CRHIAMBJMSSNNM-UHFFFAOYSA-N tetraphenylstannane Chemical compound C1=CC=CC=C1[Sn](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 CRHIAMBJMSSNNM-UHFFFAOYSA-N 0.000 description 3
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical compound CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000007323 disproportionation reaction Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- KSMWLICLECSXMI-UHFFFAOYSA-N sodium;benzene Chemical compound [Na+].C1=CC=[C-]C=C1 KSMWLICLECSXMI-UHFFFAOYSA-N 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- ZBTMRBYMKUEVEU-UHFFFAOYSA-N 1-bromo-4-methylbenzene Chemical compound CC1=CC=C(Br)C=C1 ZBTMRBYMKUEVEU-UHFFFAOYSA-N 0.000 description 1
- PLOSSHSFATUNTF-UHFFFAOYSA-N [K]C1=CC=CC=C1 Chemical compound [K]C1=CC=CC=C1 PLOSSHSFATUNTF-UHFFFAOYSA-N 0.000 description 1
- MKZIXXFZWGUNJM-UHFFFAOYSA-L bis(4-methylphenyl)tin(2+);dichloride Chemical compound C1=CC(C)=CC=C1[Sn](Cl)(Cl)C1=CC=C(C)C=C1 MKZIXXFZWGUNJM-UHFFFAOYSA-L 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/22—Tin compounds
- C07F7/2208—Compounds having tin linked only to carbon, hydrogen and/or halogen
Definitions
- the present invention relates to a process leading to much more favorable yields of 85-90% of the theoretical yield calculated upon the tin tetrahalide used.
- the process is based on the surprising observation that an aryl-tin halide, particularly diaryl-tin halide, but also triaryl-tin monohalide or monoaryl-tin trihalide, reacts in a more favorable manner with aryl alkali metal than tin tetrahalide.
- a part of the tin tetraaryl compound, the desired end product disproportionates with tin tetrahalide to give an aryl-tin halide (cf. Kocheshkov, Ber.
- the first reaction phase viz. the disproportionation of the tetraaryl tin
- the second phase viz. the reaction of the aryl-tin halide with aryl alkali metal to yield the tin tetraaryl compound, takes place at temperatures between 20 C. and +80 C., preferably between +4 C. and +5 C. In this case it is advisable to apply the aryl alkali metal in an excess of -25%.
- alkali metal aryl compounds may be used aryllithium and aryl-potassium.
- Example 1 1st phase: 1280 grams of tetraphenyl tin are slowly heated with 782 grams of tin tetrachloride to 220-230 C. and maintained for 2 hours at this temperature. After cooling, the reaction product is dissolved in 1200 cc. of benzene;
- Example 2 instead of the phenyl sodium used in Example 1, there may also be used phenyl potassium that is obtained by reaction of 1820 grams of chlorobenzene with potassium.
- Example 1 The method of working and the starting materials used a are the same as indicated in Example 1.
- Example 3 967 grams of tetra-para-tolyl-tin are reacted within 3 hours at 240 C. with 532 grams of tin tetrachloride to mainly di-para-tolyl-tin-dichloride and the reaction product is dissolved in 800 cc. of benzene. To this solution is slowly added, while stirring and permanently cooling to +5 C., a suspension of para-tolyl-sodium obtained from 460 grams of sodium, 1365 grams of para-chlorotoluene or 1845 grams of para-bromotoluene and 1800 cc. of benzene. After a reaction period of about 3 hours the reaction mixture is refluxed for about 30 minutes. The tetra-para-tolyl-tin thus obtained is worked up as described in Example 1. There are obtained 1750 grams of tetra-para-tolyl-tin melting at 235-236 C.
- a method of raising the yield of tetraaryl tin to at least 80%, calculated upon the tin tetrachloride used which comprises combining in a first step at a temperature between 200 and 230 C. tin tetrachloride and tetraaryl tin to form an aryl-tin chloride, and reacting in a second step the aryltin chloride so obtained with aryl alkali metal at a temperature between +4 and +5 C. to form tetraaryl tin, said aryl being a member selected from the group consisting of phenyl and tolyl, and said alkali metal being a member selected from the group consisting of sodium, potassium and lithium.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
United States Patent 3,067,225 PROCESS OF PREPARING TETRAARYL TIN Eugen Reindl and Klaus Boidol, Burgkirchen an der All,
Germany, assignors to Farbwerke Hoechst Aktiengeselischaft vormals Meister Lucius & Briining, Frankfurt am Main, Germany, a company of Germany No Drawing. Filed Jan. 14, 1958, Ser. No. 708,748
Claims priority, application Germany Jan. 18, 1957 3 Claims. (Cl. 260-4293) it is known to prepare tin tetraaryl compounds by reaction of tin tetrahalide with sodiumaryl or with chlorobenzene and metallic sodium. A part of the tin tetrahalide is reduced to the stanno stage or to metallic tin. For this reason, the yields mentioned in the literature scarcely exceed 65% of the theoretical yield calculated upon the tin tetrachloride used.
The present invention relates to a process leading to much more favorable yields of 85-90% of the theoretical yield calculated upon the tin tetrahalide used. The process is based on the surprising observation that an aryl-tin halide, particularly diaryl-tin halide, but also triaryl-tin monohalide or monoaryl-tin trihalide, reacts in a more favorable manner with aryl alkali metal than tin tetrahalide. According to the invention, a part of the tin tetraaryl compound, the desired end product, disproportionates with tin tetrahalide to give an aryl-tin halide (cf. Kocheshkov, Ber. 62, 996 and 67, 1348) and this disproportionation product is then reacted with aryl alkali metal to form the tin tetraaryl compound. In the case of the diaryl-tin dihalide the process operates according to the following reaction scheme R Sn+SnX4+2R SnX ZRQSII (R=aryl, X=halogen, Y: alkali metal) As regards the stoichiometry, this process corresponds completely to the hitherto known and used reaction but with the decisive difference that the new two-phase reaction avoids the disturbing reductions and, therefore, gives much higher yields. A certain portion of tetraaryl tin that depends on the amount of the starting material continuously circulates in the process, unchanged in its quantity.
The first reaction phase, viz. the disproportionation of the tetraaryl tin, is carried out at temperatures above 200 C., advantageously between 220 and 230 C. The second phase, viz. the reaction of the aryl-tin halide with aryl alkali metal to yield the tin tetraaryl compound, takes place at temperatures between 20 C. and +80 C., preferably between +4 C. and +5 C. In this case it is advisable to apply the aryl alkali metal in an excess of -25%.
As alkali metal aryl compounds may be used aryllithium and aryl-potassium.
The following examples serve to illustrate the invention but they are not intended to limit it thereto:
Example 1 1st phase: 1280 grams of tetraphenyl tin are slowly heated with 782 grams of tin tetrachloride to 220-230 C. and maintained for 2 hours at this temperature. After cooling, the reaction product is dissolved in 1200 cc. of benzene;
2nd phase: Phenyl sodium obtained from 690 grams of metallic sodium and 1820 grams of chlorobenzene is suspended in 2500 cc. of benzene and the solution obtained under (1) is added dropwise while stirring at 5-6 C. within about 2 hours. After the exothermic reaction has subsided, the reaction mixture is heated to 3,067,225 Patented Dec. 4, 1962 'ice about C., refluxed for 30 minutes and, after cooling, freed from sodium chloride by washing with water and then extracted by means of toluene. Tetraphenyl tin crystallizes from the toluene upon concentration. It is obtained in the form of white to weakly yellow needles melting from 223-224" C. The yield amounts to 2413 grams of pure tetraphenyl tin corresponding to 88.4% of the theoretical yield and calculated upon the tin tetrachloride used.
Example 2 Instead of the phenyl sodium used in Example 1, there may also be used phenyl potassium that is obtained by reaction of 1820 grams of chlorobenzene with potassium.
The method of working and the starting materials used a are the same as indicated in Example 1.
The yield amounts to 89.5% calculated upon tin tetrachloride.
Example 3 967 grams of tetra-para-tolyl-tin are reacted within 3 hours at 240 C. with 532 grams of tin tetrachloride to mainly di-para-tolyl-tin-dichloride and the reaction product is dissolved in 800 cc. of benzene. To this solution is slowly added, while stirring and permanently cooling to +5 C., a suspension of para-tolyl-sodium obtained from 460 grams of sodium, 1365 grams of para-chlorotoluene or 1845 grams of para-bromotoluene and 1800 cc. of benzene. After a reaction period of about 3 hours the reaction mixture is refluxed for about 30 minutes. The tetra-para-tolyl-tin thus obtained is worked up as described in Example 1. There are obtained 1750 grams of tetra-para-tolyl-tin melting at 235-236 C.
The yield amounts to calculated upon tin tetrachloride. Obviously many modifications and variations of the present invention are possible in the light of the above teachings. It is, therefore, to be understood that within the scope of the appended claims the invention may be practiced otherwise than as specifically described.
We claim:
1. In the process of manufacturing tetraaryl tin from tin tetrachloride and aryl alkali metal, a method of raising the yield of tetraaryl tin to at least 80%, calculated upon the tin tetrachloride used, which comprises combining in a first step at a temperature between 200 and 230 C. tin tetrachloride and tetraaryl tin to form an aryl-tin chloride, and reacting in a second step the aryltin chloride so obtained with aryl alkali metal at a temperature between +4 and +5 C. to form tetraaryl tin, said aryl being a member selected from the group consisting of phenyl and tolyl, and said alkali metal being a member selected from the group consisting of sodium, potassium and lithium.
2. A process according to claim 1 wherein the steps are carried out in a medium of inert solvent.
3. A process as claimed in claim 1 wherein the aryl alkali metal is applied in an excess of 20 to 25% calculated' on the stoichiometric amount required for the reaction with aryl-tin chloride formed in the first step.
References Cited in the file of this patent UNITED STATES PATENTS 2,431,038 Harris Nov. 18, 1947 2,570,686 Johnson et a1 Oct. 9, 1951 2,599,557 Johnson et al June 10, 1952 OTHER REFERENCES Austin: J.A.C.S. 54, 3726-3729 (1932).
Kozeschkow: Chem. Berichte, 66, pages 1661-4665 (1933).
Coates: Organo-Metallic Compounds, New York, John Wiley & Sons, Inc., 1956, page relied on.
Claims (1)
1. IN THE PROCESS OF MANUFACTURING TETRAARYL TIN FROM TIN TETRACHLORIDE AND ARYL ALKALI METAL, A METHOD OF RAISING THE YEILD OF TETRAARYL TIN TO AT LEAST 80%, CALCULATED UPON THE TIN TETRACHLORIDE USED, WHICH COMPRISES COMBINING IN A FIRST STEP AT A TEMPERATURE BETWEEN 200 AND 230*C. TIN TETRACHLORIDE AND TETRAARYL TIN TO FORM AN ARYL-TIN CHLORIDE, AND REACTING IN A SECOND STEP THE ARYLTIN CHLORIDE SO OBTAINED WITH ARYL ALKALI METAL AT A TEMPERATURE BETWEEN +4 AND +5*C. TO FORM TETRAAYL TIN, SAID ARYL BEING A MEMBER SELECTED FROM THE GROUP CONSISTING OF PHENYL AND TOLYL, AND SAID ALKALI METAL BEING A MEMBER SELECTED FROM THE GROUP CONSISTING OF SODIUM, POTASSIUM AND LITHIUM.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF22163A DE1027669B (en) | 1957-01-18 | 1957-01-18 | Process for the production of tetraaryl tin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3067225A true US3067225A (en) | 1962-12-04 |
Family
ID=7090342
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US708748A Expired - Lifetime US3067225A (en) | 1957-01-18 | 1958-01-14 | Process of preparing tetraaryl tin |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US3067225A (en) |
| BE (1) | BE564074A (en) |
| DE (1) | DE1027669B (en) |
| FR (1) | FR1197949A (en) |
| GB (1) | GB861459A (en) |
| NL (2) | NL223989A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3454610A (en) * | 1966-05-26 | 1969-07-08 | Dow Chemical Co | Synthesis of organometallic halides by redistribution |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2431038A (en) * | 1944-07-24 | 1947-11-18 | Monsanto Chemicals | Tin hydrocarbon compounds and process for making same |
| US2570686A (en) * | 1948-05-04 | 1951-10-09 | Metal & Thermit Corp | Process for making tin hydrocarbons |
| US2599557A (en) * | 1948-03-24 | 1952-06-10 | Metal & Thermit Corp | Process for making organotin halides |
-
0
- NL NL106537D patent/NL106537C/xx active
- NL NL223989D patent/NL223989A/xx unknown
- BE BE564074D patent/BE564074A/xx unknown
-
1957
- 1957-01-18 DE DEF22163A patent/DE1027669B/en active Pending
-
1958
- 1958-01-14 US US708748A patent/US3067225A/en not_active Expired - Lifetime
- 1958-01-17 GB GB1765/58A patent/GB861459A/en not_active Expired
- 1958-01-17 FR FR1197949D patent/FR1197949A/en not_active Expired
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2431038A (en) * | 1944-07-24 | 1947-11-18 | Monsanto Chemicals | Tin hydrocarbon compounds and process for making same |
| US2599557A (en) * | 1948-03-24 | 1952-06-10 | Metal & Thermit Corp | Process for making organotin halides |
| US2570686A (en) * | 1948-05-04 | 1951-10-09 | Metal & Thermit Corp | Process for making tin hydrocarbons |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3454610A (en) * | 1966-05-26 | 1969-07-08 | Dow Chemical Co | Synthesis of organometallic halides by redistribution |
Also Published As
| Publication number | Publication date |
|---|---|
| BE564074A (en) | 1900-01-01 |
| NL223989A (en) | 1900-01-01 |
| DE1027669B (en) | 1958-04-10 |
| FR1197949A (en) | 1959-12-03 |
| GB861459A (en) | 1961-02-22 |
| NL106537C (en) | 1900-01-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Bither et al. | Trialkyl-and Triaryl (iso) cyanosilanes1 | |
| US2703814A (en) | Process of preparing organic phosphorus compounds | |
| US3248411A (en) | Process for the conversion of highly alkylated tin compounds into lower alkylated tin halides | |
| US3067225A (en) | Process of preparing tetraaryl tin | |
| US2690451A (en) | Method for preparation of sulfur-containing esters of phosphoric acid | |
| US2757117A (en) | N, n', n''-hexaalkylphosphorohalogenidotriamidothioic acid esters | |
| US2964550A (en) | Organosilylalkyl derivatives of phosphorus, arsenic, antimony, and bismuth | |
| US2920094A (en) | Organosilicon compounds | |
| US3446860A (en) | Method of making phenyllithium | |
| US3053874A (en) | Process for the production of cyanoalkylfluorosilane | |
| US3082239A (en) | Thiophosphoric acid esters and process for their production | |
| US2437798A (en) | New secondary organic phosphorus halides and processes for making the same | |
| US3082256A (en) | Preparation of phosphine oxide compounds | |
| US3485863A (en) | Partial phenylation of chlorosilanes | |
| US3347890A (en) | Triorganotin carbodhmides and isoureas and the preparation thereof | |
| US3544608A (en) | Tricyclohexyltin isothiocyanate and a process for making organotin salts | |
| US2570686A (en) | Process for making tin hydrocarbons | |
| US3417116A (en) | Omega-cyano-polymethylenetin lewis acid complexes and the preparation thereof | |
| US3031509A (en) | Preparation of dialkyl phosphines | |
| US3041364A (en) | Process of preparing 4, 4'-diisocyanatodiphenyl sulfides | |
| US3432534A (en) | Method for preparing organoantimony halides | |
| US3361782A (en) | Process for the production of alkali metalorganic complex compounds of aluminum | |
| US3649701A (en) | Preparation of solutions of cyclohexyllithium | |
| US4173590A (en) | Process for making tetramethyldiphosphinomethane | |
| US2805234A (en) | Process for production of tetra-alkyl tin compound having at least 10 carbon atoms per alkyl radical |