CN1241570A - New process for preparation of organosilanes functionalised in the 3-position - Google Patents
New process for preparation of organosilanes functionalised in the 3-position Download PDFInfo
- Publication number
- CN1241570A CN1241570A CN 99108032 CN99108032A CN1241570A CN 1241570 A CN1241570 A CN 1241570A CN 99108032 CN99108032 CN 99108032 CN 99108032 A CN99108032 A CN 99108032A CN 1241570 A CN1241570 A CN 1241570A
- Authority
- CN
- China
- Prior art keywords
- sulfide
- sulfur
- reaction
- allyl
- thiophene
- 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.)
- Pending
Links
Abstract
The invention concerns a process for the preparation of organosilanes functionalized in the 3-position, by the reaction of suitable allyl compounds with hydrogen silanes, using platinum catalysts having one or more sulfur-containing ligands.
Description
The invention provides a process for preparing organosilanes functionalized in the 3-position from hydrosilanes and allyl compounds in the presence of platinum catalysis.
It is known that hydrosilanes can be reacted, for example, with allyl chloride in the presence of homogeneous or heterogeneous platinum catalysts to give 3-chloropropylsilane. This reaction is generally referred to as a hydrosilylation reaction (e.g., see equation I).
When soluble platinum compounds are used, e.g. the simplest H2PtCl6·6H2With O AS catalyst, this reaction is known AS a homogeneous hydrosilylation reaction (cf. DE-OS 2851456, CS-PS 176910, U.S. Pat. No. 3, 4292433, U.S. Pat. No. 3, 4292434, DE-AS 1187240, DE-PS 1165028); heterogeneous hydrosilylation reactions employ elemental platinum or platinum compounds on a carrier (cf. U.S. Pat. No. 4, 2637738, DE-PS 2012229, DE-PS 2815316).
For example, in the reaction of allyl chloride with hydrosilane to form 3-chloropropylsilane, it is known that some of the allyl chloride used reacts with hydrosilane to form propene in a side reaction, while the hydrosilane is converted to the corresponding chlorosilane (see, e.g., equation II)
Thus, for example, in the reaction of allyl chloride with trichlorosilane, 25 to 30 mol% of the allyl chloride is converted into propene by side reactions, with the formation of an equivalent amount of silicon tetrachloride. The selectivity of the reaction, measured as the molar ratio of chloropropylsilane to silicon tetrachloride formed in the crude product, is typically between 2.33: 1 (70% yield based on allyl chloride) and 3: 1 (75% yield).
It is known that the production of propylene can be suppressed by employing a special reaction method in a pressurized vessel. However, this method leads to a further quantitative reaction of the propene formed as a side reaction with the hydrosilane used to form propylsilane. Even in the conventional reaction using atmospheric pressure, propylene produced by the side reaction undergoes further side reaction with hydrosilane to produce the corresponding propylsilane (see, DE 3404703C) (e.g., see equation III).
Thus, for example, in the plant, when carrying out heterogeneous platinum-catalyzed reactions of allyl chloride and trichlorosilane in a column charged with platinum carbon, up to 230kg of propyltrichlorosilane are obtained per 1000kg of 3-chloropropyltrichlorosilane produced, based on the amount of trichlorosilane converted into the desired product, which means that an additional 28% of trichlorosilane is required (cf. DE 4119994A 1).
In addition to the need to add additional hydrosilane, these processes have the problem of complicated separation of the undesirable propylsilanes, which are otherwise of little use and which have to be disposed of by expensive methods.
This problem is improved by the method of claim 1.
In this aspect, a process is provided for preparing a 3-position functionalized propyl silane as follows: reacting at a temperature of between 0 ℃ and 200 ℃ and at a pressure of between 800mbar and 6bar, using a platinum catalyst comprising one or more sulfur-containing ligands under conditions such that the allyl compound represented by formula I is reacted
H2C＝CH-CH2X (I) wherein X may be Cl, Br, I, F, CN, SCN, SH, SR, OH, NRR1And OR, R and R1Independently of one another are C1-C6Alkyl or C3-C7An aryl group, a heteroaryl group,
to a silane represented by formula II:
R2R3R4SiH (II) wherein R2、R3、R4Each independently of the others is hydrogen, halogen, C1-C6Alkyl radical, C1-C6Haloalkyl, C3-C6Allyl radical, C1-C4Alkoxy, phenyl, aryl or aralkyl.
Preferred embodiments will be described in detail in the dependent claims. X is preferably halogen, particularly preferably chlorine.
The method can be carried out under the conditions of normal pressure, pressurization and partial vacuum. Preferably, the operating pressure is between 800mbar and 6 bar. Pressures of 800mbar to 2bar are particularly suitable.
The process of the invention is generally carried out by reacting the allyl compound with a slight excess of hydrosilane at a temperature between 0 ℃ and 200 ℃ in a suitable vessel until all the allyl chloride has reacted to completion.
Silanes useful as starting materials in the present invention include those represented by structural formula II
R2R3R4SiH (II) wherein R2、R3、R4Each independently is hydrogenHalogen, C1-C6Alkyl radical, C1-C6Alkoxy radical, C1-C6Haloalkyl, C3-C6Allyl, phenyl, aryl or aralkyl.
The silanes used in the reaction according to the invention are preferably trichlorosilane or mixed-substituted silanes, such as methyl, ethyl, propylhydrogendichlorosilane or dimethylhydrochlorosilane.
The platinum catalyst employed may be in any oxidation state. In principle, the catalyst can be prepared beforehand and then added to the reaction mixture, or can be formed only in the actual reaction mixture (in situ formation). The catalytic reaction can be homogeneous or heterogeneous, i.e.the platinum compounds used can also be attached to a support (cf. U.S. Pat. No. 4, 2637738, DE-PS 2012229, DE-PS 2815316). The catalyst may be used in stoichiometric or catalytic amounts, for example in amounts of from 0.1 to 10000ppm, preferably from 10 to 500ppm, based on the allyl compound employed. The preparation of platinum compounds is outlinedin the Gmelins handbook of inorganic chemistry (Gmelins Handbuch der Anorganischen Chemie), 8 th edition, volume 68, part D ("komplexverbindundingen [ des Platins]mit neutralen Liginden").
To have the effect according to the invention, the catalyst must have a sulfur-containing ligand. Wherein the sulfur-containing ligand is sufficient to constitute a simple donor/acceptor interaction between the core platinum. The sulfur-containing ligand may be monodentate or polydentate and may be a thioether, sulfoxide, sulfane, polysulfane or thiol, or in general a monosulfide, wherein the sulfur has an oxidation state of-2. These compounds are known to the person skilled in the art from the literature (Houben-Weyl, volume E11, G Thieme Verlag, Stuttgart 1985, in particular pages 158, 669, 129, 147, 32). The sulfur-containing compounds may be used alone or in combination. The process of the present invention comprises a sulfur-containing compound represented by the following structural type:
R5SR6、R7S(O)R8、R9SzR10、R9SzR10Sy-R11wherein R is5、R6、R7、R8、R9、R10、R11Can be any organic group or H, and z and y are integers from 2 to 6 respectively. Examples of sulfur-containing ligands which can be used are: sulfanes, such as methylethyl sulfide, ethylphenyl sulfide, allylphenyl sulfide, benzyl-2, 2, 2-trifluoroethyl sulfide, bis (2-mercaptoethyl) sulfide, bis (trimethylsilylmethyl) sulfide, 2-chloroethylmethyl sulfide, 2-chloroethylphenyl sulfide, 2-chloro-3, 4-dimethyl-5-phenyl-1, 3, 2-oxazaphosphorine-2-sulfide, chlorodimethyl sulfide, chloromethylphenyl sulfide, diethyl sulfide, diallyl sulfide, dibenzyl sulfide, thioethers, thio,Dibutyl sulfide, dimethyl sulfide, dioctyl sulfide, diphenyl sulfide, dipropyl sulfide,2-hydroxyethyl methyl sulfide, 2-hydroxyethyl phenyl sulfide, phenyl vinyl sulfide, tetraphosphorus trisulfide, propylene sulfide, tetraethylthiuram disulfide, tetramethylthiuram disulfide, tris (methylthio) methane, bis [3- (triethoxysilyl) propyl]sulfide]A thioether; cyclic sulfanes, such as 1, 4-oxathiane, 2, 5-dihydroxy-1, 4-dithiane, 1, 3-dithiane, ethyl 1, 3-dithiane-2-carboxylate, hexamethyldisilathiane, 2-methyl-1, 3-dithiane, thianthrene, 2-trimethylsilyl-1, 3-dithiane, 1, 3, 5-trithiane, tetrahydrothiophene, trimethylene sulfide, 1, 4, 7-trithiocyclononane, 1, 4, 7-trithiocyclodecane; disulfanes and polysulfides, e.g. bis (2-nitrophenyl) disulfide, bis [3- (triethoxysilyl) propyl]Tetrakis, bis [3- (triethoxysilyl) propyl]sulfide]Disulfide, diallyl disulfide, dibenzyldisulfide, ditert-butyl disulfide, dibutyl disulfide, dimethyl disulfide, diphenyl disulfide, dipropyl disulfide; sulfoxides, such as allylphenyl sulfoxide, chloromethylphenyl sulfoxide, dibenzylsulfoxide, dimethyl sulfoxide, diphenyl sulfoxide, ethylthiomethylsulfoxide, DL-methionine sulfoxide, methylmercapto-methyl sulfoxide, methylphenylsulfoxide, R (+) -methyl-p-tolylsulfoxide, S (-) -methyl-p-tolylsulfoxide, phenylvinyl sulfoxide, 1-carbonyltetrahydrothiophene; thiophenes, e.g. thiophene, 2-acetylthiophene, 3-acetylthiophene, 2-ethylthiophene, DL-d-aminothiophene-2-acetic acid, benzothiophene, 2, 5-bis (5-tert-butylbenzo-o)Oxazol-2-yl) thiophene, 2' -bithiophene, 2-bromothiophene, 3-bromothiophene, 2-chlorothiophene, 2, 3-dibromothiophene, 3, 4-dibromothiophene, 6, 7-dihydro-4-benzo [ b]b]Thiophene, 2, 5-dimethylthiophene, 2-hydroxymethylthiophene, 2-iodothiophene, methoxythiophene, 2-methylthiophene, 3-methylthiophene-2-carbaldehyde, 5-methylthiophene-2-carboxylic acid, 2 ', 5', 2 "-tetrathiophene, thiophene-2-acetonitrile, thiophene-3-acetonitrile, thiophene-2-acetyl chloride, thiophene-2-carbaldehyde, thiophene-3-carbaldehyde,Thiophene-2-carboxylic acid, thiophene-3-carboxylic acid, thiophene-2-carboxylicacid chloride, thiophene-2-acetic acid, thiophene-3-acetic acid, thiophene-2-methyl acetate, 2-mercaptothiophene; thiazoles, e.g. thiazole, 2-acetylthiazole, 2-aminobenzothiazole, 2-amino-5-nitrothiazole, 2- (4-aminophenyl) -6-methylbenzothiazole, 2-aminothiazole, 2-amino-2-thiazoline, ethyl 2-amino-4-thiazolylacetate, 2' -azine-bis (3-ethylbenzothiazoline-6-sulfonic acid), benzothiazole, 3- (benzothiazol-2-ylthio) -1-propanesulfonic acid, 2-bromothiazole, 2-chlorobenzothiazole, 2, 3-dihydro-3, 3-dimethyl-1, 2-benzisothiazole-1, 1-dioxide, thiobenzoxazole, thioxazole, thiazyl, thia, 2, 5-dimethylbenzothiazole, 2' -dithio-bis (4-methylthiazole), 2-fluoro-3, 3-dimethyl-2, 3-dihydro-1, 2-benzisothiazole-1, 1-dioxide, 5- (2-hydroxyethyl) -4-methylthiazole, 3-hydroxy-4-methyl-2 (3H) -thiazothion, 2-mercaptobenzothiazole, 2-mercapto-2-thiazoline, 2-methylbenzothiazole, 2- (methylmercapto) -2-thiazoline, 2-methylnaphtho [1, 2-d]]Thiazole, 5-methylthiazole, 2-methyl-2-thiazoline, R- (-) -2-oxothiazolidine-4-carboxylic acid, succinylsulfathiazole, L-thiazolidine-4-carboxylic acid, 2, 4-thiazolidinedione, 1- (2-thiazolazo) -2-naphthol, 4- (2-thiazolazo) resorcinol, R (-) -2-thiothiazolidine-4-carboxylic acid, 2- (trimethylsilyl) thiazole.
Particularly preferred sulfur-containing ligands are diethyl sulfide, dimethyl sulfoxide, tetrahydrothiophene, benzothiazole, thiophene, dibenzyl sulfide, 1, 3-dithiane, tris (methylthio) methane, dimethyl sulfide, dibenzyl sulfide, diallyl sulfide.
The term "alkyl" refers to both "straight-chain" and "branched" alkyl groups. The term "straight chain alkyl" refers to groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl. The term "branched alkyl" refers to a group such as isopropyl or tert-butyl. The term "halogen" refers to fluorine, chlorine, bromine or iodine. The term "alkoxy" refers to a group such as methoxy, ethoxy, propoxy, butoxy, isopropoxy, isobutoxy, or pentoxy.
In the context of the present invention, "aryl" means substituted by C1-C6Alkyl radical, C1-C6Alkoxy, halogen or heteroatoms such as N, O, phenolic groups, P-or S-substituted phenyl groups, biphenyl groups or other benzene-like compounds. For "aralkyl" is N, O, phenol, P or S substituted. "aralkyl" means an "aryl" group as defined above through C1-C6Alkyl chains bound to silicon atoms, in which the alkyl groups may be substituted by C1-C4Alkyl or halogen substitution. If "aryl" contains heteroatoms such as O or S, C1-C6The alkyl chain may be attached to the silicon atom through the heteroatom.
When a substituent such as C is selected1-C4When alkoxy, the subscript numbers refer to the total carbon atoms of the group.
The following examples 1 to 4 describe the process of the invention. Examples 5 to 7 are comparative examples.
The selectivity given here is the molar ratio of the target product 3-chloropropyltrichlorosilane (Cl-PTS) to silicon tetrachloride. The selectivity achieved by the examples of the invention and the yield of 3-chloropropyltrichlorosilane indicate that the novel process is superior to conventional processes (see comparative examples 5 to 7). Examples
Example 1
100g (472mmol) of 3-chloropropyltrichlorosilane, 76.6g (1mol) of allyl chloride and 142.3g (1.05mol) of trichlorosilane are mixed together in a 500ml three-necked flask equipped with a mushroom-shaped heater, a magnetic stirrer, an internal thermometer and a reflux condenser which is cooled vigorously to-30 ℃. 37.0mg (0.10mmol) of DMSO (C) are then added2H4)PtCl2(V.Y.Kukushkin et al, inorg. chim Acta 185(1991), 143) and the mixture is heated to boiling. The internal temperature rises during the reaction as a result of the conversion of the low-boiling components into the higher-boiling components. The reaction was terminated when the boiling remained highly stable for a considerable time. The reaction mixture was then cooled and the resulting product mixture was analyzed by gas chromatography. When removed as a solventAfter 3-chloropropyltrichlorosilane (g), the product was found to have the following composition:
2.12 wt% Trichlorosilane (TCS)
0.04 wt% allyl chloride (ACl)
16.72 wt% Silicon Tetrachloride (STC)
2.73 wt% Propyltrichlorosilane (PTS)
78.38 wt% 3-chloropropyltrichlorosilane (Cl-PTS)
Thus, the selectivity of the reaction was 3.76: 1 based on the amount of starting material, corresponding to a yield of 79.0% based on allyl chloride of 3-chloropropyltrichlorosilane.
Examples 2 to 4
Various other homogeneous catalysts were employed under conditions similar to those described in example 1. The results are given in the table below
| Catalyst and process for preparing same Dosage of | Product composition (wt%) | Selectively (in allyl Calculated yield of chlorine base) | |
| Practice of Example 2 | 44.0mg(0.10mmol) THT2PtCl2 (THT ═ tetrahydrothiophene, E. Cox et al, J. Chem.Soc.A(1934)， 182) | TCS： 0.04 ACl： 0.13 STC： 17.80 PTS： 1.50 Cl-PTS： 80.36 | 3.62∶1(78.4％) |
| Practice of Example 3 | 42.0mg(0.10mmol) DMSO2PtCl2 (dimethylsulfoxide, j.h. Pierce et al, Inorg. Chem.11(1972)， 1280) | TCS： 1.03 ACI： 0.02 STC： 18.23 PTS： 2.13 Cl-PTS： 77.36 | 3.40∶1(77.3％) |
| Practice of Example 4 | 45.0mg(0.10mmol) (Et2S)2PtCl2 (e.g. cox et al, J. Chem.Soc.A(1934)， 182) | TCS： 1.03 ACl： 0.02 STC： 18.46 PTS： 2.09 Cl-PTS： 78.37 | 3.40∶1(77.3％) |
Examples 5 to 7 (comparative example)
Various other homogeneous catalysts were employed under conditions similar to those described in example 1. The results are shown in the following table.
| Catalyst and process for preparing same Dosage of | Product composition (wt%) | Optionally (with allyl groups Yield calculated for chlorine) | |
| Example 5 | H2PtCl6·6H2O (CPA)， 41mg | TCS： 0.15 ACl： 1.67 STC： 21.71 PTS： 3.54 Cl-PTS： 72.88 | 2.69∶1(72.9％) |
| Example 6 | (Ph3P)2PtCl2 (P.J.Stang et al, J. Organomet.Chem. 388(1990)，215) | TCS： 1.78 ACl： —— STC： 22.77 PTS： 2.14 Cl-PTS： 73.78 | 2.60∶1(72.2％) |
| Example 7 | CPA (0.1M propanol solution) Liquid), 0.2ml + dppe (0.1M benzene solution), 0.1ml | TCS： 1.19 ACl： —— STC： 20.12 PTS： 1.45 Cl-PTS： 77.06 | 3.07∶1(75.4％) |
Claims (9)
1. a process for preparing 3-functionalized organosilanes, in which an allyl compound of the formula I is reacted at a temperature of between 0 ℃ and 200 ℃ and a pressure of between 800mbar and 6bar, using a platinum catalyst containing one or more sulfur-containing ligands under the conditions mentioned above
H2C＝CH-CH2X (I) wherein X ═ Cl, Br, I, F, CN, SCN, SH, SR, OH, NRR1And OR, R and R1Independently of one another are C1-C6Alkyl or C3-C7An aryl group, a heteroaryl group,
to a silane represented by formula II:
R2R3R4SiH (II) wherein R2、R3、R4Each independently of the others is hydrogen, halogen, C1-C6Alkyl radical, C1-C6Haloalkyl, C3-C6Allyl radical, C1-C4Alkoxy, phenyl, aryl or aralkyl.
2. The method of claim 1, wherein X ═ F, Cl, Br, or I.
3. The method of claim 1 or 2, wherein X ═ Cl.
4. The method as claimed in any of the preceding claims, characterized in that trichlorosilane, methylhydrodichlorosilane, ethylhydrogendichlorosilane, propylhydrogendichlorosilane or dimethylhydrochlorosilane is used as silane of the general formula II.
5. A process according to any preceding claim, wherein the sulphur-containing ligand is monodentate or polydentate and is a thioether, sulfoxide, sulfane, polysulfane or thiol.
6. The process of claim 5, wherein diethyl sulfide, dimethyl sulfoxide, tetrahydrothiophene, benzothiazole, thiophene, dibenzyl sulfide, 1, 3-dithiane, tris (methylthio) methane, dimethyl sulfide, dibenzyl sulfide, diallyl sulfide or mixtures thereof are used as sulfur-containing ligands.
7. The process according to any of the preceding claims, wherein the catalyst is present in a concentration of 0.1 to 10000ppm, preferably 10 to 500ppm, based on the allyl compound employed.
8. The process according to any of the preceding claims, wherein the reaction is carried out at a pressure of 800mbar to 2 bar.
9. Use of a platinum catalyst with a sulfur-containing ligand in an addition reaction according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99108032 CN1241570A (en) | 1998-06-10 | 1999-06-10 | New process for preparation of organosilanes functionalised in the 3-position |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19825793.7 | 1998-06-10 | ||
| CN 99108032 CN1241570A (en) | 1998-06-10 | 1999-06-10 | New process for preparation of organosilanes functionalised in the 3-position |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1241570A true CN1241570A (en) | 2000-01-19 |
Family
ID=5273087
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 99108032 Pending CN1241570A (en) | 1998-06-10 | 1999-06-10 | New process for preparation of organosilanes functionalised in the 3-position |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1241570A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100352090C (en) * | 2002-11-26 | 2007-11-28 | 德·诺拉电极股份公司 | Metal alloy for electrochemical oxidation reactions and method of production thereof |
| CN108467486A (en) * | 2017-12-30 | 2018-08-31 | 深圳市安品有机硅材料有限公司 | Sulfur poisoning-resistant platinum catalyst and preparation method thereof |
-
1999
- 1999-06-10 CN CN 99108032 patent/CN1241570A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100352090C (en) * | 2002-11-26 | 2007-11-28 | 德·诺拉电极股份公司 | Metal alloy for electrochemical oxidation reactions and method of production thereof |
| CN108467486A (en) * | 2017-12-30 | 2018-08-31 | 深圳市安品有机硅材料有限公司 | Sulfur poisoning-resistant platinum catalyst and preparation method thereof |
| CN108467486B (en) * | 2017-12-30 | 2021-01-26 | 深圳市安品有机硅材料有限公司 | Sulfur poisoning resistant platinum catalyst and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6191297B1 (en) | Process for the preparation of organosilanes functionalized in the 3-position | |
| Steudel | The Chemistry of Organic Polysulfanes R− S n− R (n> 2) | |
| KR100374897B1 (en) | Manufacturing Method of Silane Polysulfide | |
| CS212279B2 (en) | Method of making the organo-silicious compounds containing the sulphur | |
| KR20050071668A (en) | Process for manufacture of blocked mercaptosilane coupling agents | |
| JP4268039B2 (en) | Method for producing sulfur-containing organosilicon compound using buffer phase transfer catalyst method | |
| RU2008137650A (en) | FREE CURRENT FILLER COMPOSITION BASED ON FUNCTIONALIZED ORGANOSILANE | |
| KR20030005047A (en) | Siloxane oligomers, a process for their production and their use | |
| JP2006249086A (en) | Method for producing organosilane | |
| BRPI0720721B1 (en) | SILADO CYCLIC NUCLEUS POLYSULPHETS, PROCESS FOR PREPARATION AND COMPOSITION OF RUBBER UNDERSTANDING THE SAME | |
| RU2008137586A (en) | ORGANOFUNCTIONAL SILANS AND THEIR MIXTURES | |
| CA2180884A1 (en) | Process for the preparation of organosilicon disulfide compounds | |
| KR100886037B1 (en) | Process for the preparation of sulfur-containing organosilicon compounds | |
| CN1241570A (en) | New process for preparation of organosilanes functionalised in the 3-position | |
| US6294683B1 (en) | Solid/liquid phase transfer system | |
| EP1439183B1 (en) | Use of a composition comprising a salt of a mercaptosilane | |
| EP0718302A1 (en) | Process for the preparation of organosilicon disulfide compounds | |
| JP2004521945A (en) | Method for producing sulfur-containing organosilicon compound | |
| JP4638568B2 (en) | Propylsilane production method | |
| KR100776923B1 (en) | Process for the preparation of organosilylalkylpolysulfanes | |
| MXPA99005307A (en) | Process for the preparation of organosilanes functionalized in the 3-position | |
| US4649208A (en) | Process for making amino group-containing organosilicon compounds | |
| Seltzer | Reactions of organotin chlorides with the cyanodithioimidocarbonate anion | |
| EP2099809B1 (en) | Process for preparing organic silane compounds having beta-cyano ester group | |
| Degl'Innocenti et al. | Organosilanes in Sulfur Chemistry: Silicon Mediated Synthesis and Reactivity of Sulfur-Containing Molecules |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |