CA1335673C - Process for producing singly or multiply substituted organyl oxysilyl-functional thioureas and said compounds - Google Patents
Process for producing singly or multiply substituted organyl oxysilyl-functional thioureas and said compoundsInfo
- Publication number
- CA1335673C CA1335673C CA000603784A CA603784A CA1335673C CA 1335673 C CA1335673 C CA 1335673C CA 000603784 A CA000603784 A CA 000603784A CA 603784 A CA603784 A CA 603784A CA 1335673 C CA1335673 C CA 1335673C
- Authority
- CA
- Canada
- Prior art keywords
- c2h5o
- thioureas
- atoms
- amine
- oxysilyl
- 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 - Fee Related
Links
- 150000003585 thioureas Chemical class 0.000 title claims abstract description 13
- 125000001190 organyl group Chemical group 0.000 title claims abstract description 6
- 238000000034 method Methods 0.000 title claims description 6
- 150000001875 compounds Chemical class 0.000 title description 10
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000012990 dithiocarbamate Substances 0.000 claims abstract description 14
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 claims abstract description 10
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 6
- -1 aminoalkyl silane Chemical compound 0.000 claims description 12
- 150000001412 amines Chemical class 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims 8
- 125000000753 cycloalkyl group Chemical group 0.000 claims 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical compound [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 150000003335 secondary amines Chemical class 0.000 abstract description 3
- ZPZDIFSPRVHGIF-UHFFFAOYSA-N 3-aminopropylsilicon Chemical compound NCCC[Si] ZPZDIFSPRVHGIF-UHFFFAOYSA-N 0.000 abstract description 2
- 150000004756 silanes Chemical class 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- 230000000875 corresponding effect Effects 0.000 description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 108020001305 NR1 subfamily Proteins 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229940086542 triethylamine Drugs 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 150000004659 dithiocarbamates Chemical class 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- RWLDCNACDPTRMY-UHFFFAOYSA-N 3-triethoxysilyl-n-(3-triethoxysilylpropyl)propan-1-amine Chemical compound CCO[Si](OCC)(OCC)CCCNCCC[Si](OCC)(OCC)OCC RWLDCNACDPTRMY-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000000370 acceptor Substances 0.000 description 2
- YNNGZCVDIREDDK-UHFFFAOYSA-N aminocarbamodithioic acid Chemical compound NNC(S)=S YNNGZCVDIREDDK-UHFFFAOYSA-N 0.000 description 2
- DCYNAHFAQKMWDW-UHFFFAOYSA-N azane;carbamodithioic acid Chemical class N.NC(S)=S DCYNAHFAQKMWDW-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 101150009274 nhr-1 gene Proteins 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 150000003961 organosilicon compounds Chemical class 0.000 description 2
- 239000003880 polar aprotic solvent Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- GWQWBFBJCRDINE-UHFFFAOYSA-M sodium;carbamodithioate Chemical compound [Na+].NC([S-])=S GWQWBFBJCRDINE-UHFFFAOYSA-M 0.000 description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KCOYHFNCTWXETP-UHFFFAOYSA-N (carbamothioylamino)thiourea Chemical compound NC(=S)NNC(N)=S KCOYHFNCTWXETP-UHFFFAOYSA-N 0.000 description 1
- 125000004066 1-hydroxyethyl group Chemical group [H]OC([H])([*])C([H])([H])[H] 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- KUBPFQNPLTWBHU-UHFFFAOYSA-N 3-silylpropyl carbamodithioate Chemical compound C(N)(SCCC[SiH3])=S KUBPFQNPLTWBHU-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- DBAOJMMXPQSAKW-UHFFFAOYSA-M sodium;n-(3-triethoxysilylpropyl)carbamodithioate Chemical compound [Na+].CCO[Si](OCC)(OCC)CCCNC([S-])=S DBAOJMMXPQSAKW-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 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
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
-
- 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
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The present invention relates to the production of N-and N'-singly or multiply substituted organyl oxysilyl-functional silanes by reacting an aminopropyl silane with carbon disulphide and by heating the nascent dithiocarbamate with a secondary or tertiary amine. The present invention also relates to N,N,N'-, N,N',N'- and N,N,N',N'-substituted thioureas that can thus be produced.
Description
~ ~ 133567 ~
The present invention relates to a process for producing N- and N'-singly or multiply substituted organyl oxysilyl-functional thioureas and to the compounds that can thus be produced.
The reaction of aminopropyl trialkoxy silanes with alkyl isothiocyanates which results in N,N'-disubstituted thioureas having the formula (Ro)3si-(cH2)3 - NH - CS - NH -R' wherein R represents ethyl and Rl represents phenyl, allyl, is known from A~ Baigozhin, Zh, Obshch, Khim. 43 (1973, 1408 (C~A~ 79:66463r).
These compounds are used for modifying silicon-containing polymers and coatings.
A symmetric N,N'-substituted compound is described by N.G. Voronkov et al. in Zh. Obshch, Khim. 54 (1984), 1098 (CoA~ 101:192031j). It is obtained by reacting aminopropyl tr;alkoxysilanes with thiourea.
((R0)3 Si - (CH2)3 - NH - CS - NH - (CH2)3 - Si (OR)3).
It is the aim of the present invention to find a novel process for producing substituted organyl oxysilyl-functional thioureas which, with the use of available starting compounds, results in the desired compounds with good yields.
Novel thioureas are a further aim of the present invention.
The present invention relates to a process for producing N- and N'-singly or multiply substituted organyl oxysilyl-functional thioureas, which is characterized in that a) an amino-alkyl silane having the general formula (I) (CH3)b (RO)3-b Sli-(CHX)a - NHR1, wherein b represents 0, 1 or 2, preferably 0, R represents all~yl containing 1 to 6 C atoms, preferably methyl or ethyl, cylcoalkyl contAin;ng 5 to 7 C atoms, aryl, preferably phenyl, X represents hydrogen when a = 1, 3, 4, 5 or 6, preferably a =3, or X represents -CH2 ~ -CH2-, when a _ 1, Rl represents hydrogen, -(CH2)3 - Si(R)3-b (CH3)b, is reacted in an organic solvent with carbon disulphide in the presence of a tertiary amine (A) or alkali alcoholate (MOR), b) that the dithiocarbamate thus formed which has the general formula (II) (CF3)b (RO)3-b Si - (CHX)a - NRl - CS - S AH~/ M~
is isolated and mixed with at least the e~uimolar amount of an amine having the general formula (III) wherein R2 represents hydrogen, R2, R3 are identical or different from each other and represent alkyl cont~;n;ng 1 to 8 C atoms, alkenyl containing 2 to 8 C atoms and aryl particularly phenyl, naphthyl, aralkyl, particularly benzyl, phenethyl, or 1~3S673 - ( CH2) 3 - 1; (OR) 3-b ( C H 3 ) b that this mixture is heated until the reaction is completed and the resulting product having the general formula (III) (CH3)b (R0) S; - tCHX) - NR1 _ CS - NRZR3 3-b a is subsequently isolated by means of conventional methods.
Compounds wherein -(CHX)a~ represents -(CH2)3- are pre-ferred.
The desired compounds are produced from aminoalkylsilanes, C2 and primary or secondary amines according to the fol-lowing basic pattern via the dithiocarbamate intermediate stages that are capable of being isolated:
(~0)3S;-(CHX)a ~ NHR1 + CS2 + A (A: tertiary amlne) (1) (MOR: alkali alcoholate) (R0)3Si-(CHX)a - NR1 - CS - S~AH~/M~
z 3 "dithiocarbamate"
The present invention relates to a process for producing N- and N'-singly or multiply substituted organyl oxysilyl-functional thioureas and to the compounds that can thus be produced.
The reaction of aminopropyl trialkoxy silanes with alkyl isothiocyanates which results in N,N'-disubstituted thioureas having the formula (Ro)3si-(cH2)3 - NH - CS - NH -R' wherein R represents ethyl and Rl represents phenyl, allyl, is known from A~ Baigozhin, Zh, Obshch, Khim. 43 (1973, 1408 (C~A~ 79:66463r).
These compounds are used for modifying silicon-containing polymers and coatings.
A symmetric N,N'-substituted compound is described by N.G. Voronkov et al. in Zh. Obshch, Khim. 54 (1984), 1098 (CoA~ 101:192031j). It is obtained by reacting aminopropyl tr;alkoxysilanes with thiourea.
((R0)3 Si - (CH2)3 - NH - CS - NH - (CH2)3 - Si (OR)3).
It is the aim of the present invention to find a novel process for producing substituted organyl oxysilyl-functional thioureas which, with the use of available starting compounds, results in the desired compounds with good yields.
Novel thioureas are a further aim of the present invention.
The present invention relates to a process for producing N- and N'-singly or multiply substituted organyl oxysilyl-functional thioureas, which is characterized in that a) an amino-alkyl silane having the general formula (I) (CH3)b (RO)3-b Sli-(CHX)a - NHR1, wherein b represents 0, 1 or 2, preferably 0, R represents all~yl containing 1 to 6 C atoms, preferably methyl or ethyl, cylcoalkyl contAin;ng 5 to 7 C atoms, aryl, preferably phenyl, X represents hydrogen when a = 1, 3, 4, 5 or 6, preferably a =3, or X represents -CH2 ~ -CH2-, when a _ 1, Rl represents hydrogen, -(CH2)3 - Si(R)3-b (CH3)b, is reacted in an organic solvent with carbon disulphide in the presence of a tertiary amine (A) or alkali alcoholate (MOR), b) that the dithiocarbamate thus formed which has the general formula (II) (CF3)b (RO)3-b Si - (CHX)a - NRl - CS - S AH~/ M~
is isolated and mixed with at least the e~uimolar amount of an amine having the general formula (III) wherein R2 represents hydrogen, R2, R3 are identical or different from each other and represent alkyl cont~;n;ng 1 to 8 C atoms, alkenyl containing 2 to 8 C atoms and aryl particularly phenyl, naphthyl, aralkyl, particularly benzyl, phenethyl, or 1~3S673 - ( CH2) 3 - 1; (OR) 3-b ( C H 3 ) b that this mixture is heated until the reaction is completed and the resulting product having the general formula (III) (CH3)b (R0) S; - tCHX) - NR1 _ CS - NRZR3 3-b a is subsequently isolated by means of conventional methods.
Compounds wherein -(CHX)a~ represents -(CH2)3- are pre-ferred.
The desired compounds are produced from aminoalkylsilanes, C2 and primary or secondary amines according to the fol-lowing basic pattern via the dithiocarbamate intermediate stages that are capable of being isolated:
(~0)3S;-(CHX)a ~ NHR1 + CS2 + A (A: tertiary amlne) (1) (MOR: alkali alcoholate) (R0)3Si-(CHX)a - NR1 - CS - S~AH~/M~
z 3 "dithiocarbamate"
(2) ~ HNR R
- H2S / Ml~S
(RO)3S;- (CHX)a - NR1 _ CS - NR R
The reaction according to equation (1) is preferably carried out in a non-polar aprotic solvent when tertiary amines '~''5' B are used as proton~ acceptors. In that case particularly suit-.
`~ 1 33s6 73 able solvents are (halogenated) hydrocarbons or (cyclic) ethers such as n-pentane or tetrahydrofuran or their mixtures.
B When using alkali alcoholate as proton~ acceptor, then I polar aprotic solvents, as for example, dimethyl formamide, and even specific polar protic solvents, as for example, alcohols, are suitable. In the latter case it is particularly advantageous to produce the alkali alcoholate directly by reacting alkali metal, particularly sodium or potassium, with an alcohol, partic-ularly methanol or ethanol, by means of conventional methods andto use this reaction solution directly for the reaction to the dithiocarbamate.
It is an important prerequisite for the suitability as solvent that it must dissolve the aminosilane on the one hand and that on the other the dithiocarbamate should be precipitated as quantitatively as possible since otherwise it would be inert.
The reactants aminopropyl silane, carbon disulphide and tertiary amine or alkali alcoholate are applied in a molar ratio of approximately 1:1:1 without excluding, for example, a variation of up to 10% from the stoichiometrically required amounts. Cor-responding molar ratios also apply to the reactants dithiocarba-mate and amine according to equation (2).
Amines, wherein R2 and/or R3 represent (CIH3)b -(CH2)3-s; (OR)3 b were known according to DE-OS 31 20 214 and J.L. Speier at al., J. Org. Chem. 36 (1971), 3120 ff. Triethyl amine or pyridine are preferably applied as amines.
The reaction according to e~uation (1) is preferably carried out at temperatures below the boiling point of carbon 1335~73 disulphide, particularly at temperatures of 0 to 46C. The organosilicon compound is added with advantage to the carbon disulphide, which, under certain conditions, ls present in a sto-ichiometric excess. The precipitated "dithiocarbamate" is fil-tered off and freed from the solvent residues under vacuum.
Dithiocarbamates like those obtained by means of the reaction according to equation (1) are known in several instances from the literature. However, according to the prior art they 0 are reacted with acrylonitrile (DE-OS 20 00 224) or converted by hydrolysis into a polysiloxane compound (U.S. Patent 2,938,046).
According to the present invention the "dithiocarba-mates", obtained as bright yellow crystal powder, are converted into thioureas. According to reaction step (2) primary or sec-onardy amines, preferably in equimolar amounts, are heated with the organosilicon compounds, usually without the addition of sol-vents, to temperatures of 80 to 140C while stirring.
In a favourable embodiment with the use of an ammonium dithiocarbamate the nascent hydrogen sulphide and the separating tertiary amine are drawn off under vacuum. The thioureas thus obtained in high yields require no further purification.
However, no hydrogen sulphide is formed when using alkali dithiocarbamates but the corresponding alkali hydrogen sulphide is formed. It is separated from the desired product by precipitating with a suitable solvent, for example, acetone.
The present invention also relates to N,N,N'- or N,N'N'- and N,N,N',N'-substituted thioureas having the general fo~mula (III) (I 3 b ~ 1 `' (R0)3 b s; - (CHX)a - NR1 _ Cs - NR2R3 , -wherein a, b, X, R, Rl and R3 have the above defined meaning with the proviso that Rl and R2 or R3 are not H.
These compounds are used with advantage in halogen ruhber mixtures because of their vulcanization-accelerating ef*ect.
Examples of Production:
1. 3-trialkoxysilyl-propyl dithiocarbamates (Examples 1-4):
Example 1: triethyl ammonium (3-trimethoxy-silyl-propyl)dithiocarbamate.
(CH30)3Si-(CH2)3-NH-CS-S~ HN(C2H5)ffl,1:
789 g of 3-aminopropyl trimethoxysilane (4.4 moles) and 465.5 g of triethyl amine (4.6 moles, excess) are put into 1200 ml of THT at room temperature and mixed dropwise with 351.5 g of carbon disulphide (4.6 moles, excess) within six hours while cooling with ice. The precipitated bright yellow deposit is filtered off and freed from the solvent in vacuo.
1337 g of a yellow powder are obtained corresponding to 85.2%
of the theoretical yield.
C13H32N2o3S2Si (356,624):
C(%) H(%) N(%) S(%) computed: 43.78 9.04 7.86 17.98 obtained: 43.3 9.3 7.7 18.5 Example 2: triethyl ammonium (3-triethoxysilyl-propyl) dithiourea (C2H5o)3si-(cH2)3-NH-cs- ~ HN(C2Hs)3~ ,2:
, 1335~ 3 637.6 g of triethyl amine (6.3 moles,^ excess) and 502.3 g of carbon disulphide (6.6 moles, excess) are put into 1.5 litres of THF and mixed with 1328.3 g of 3-aminopropyl tri-ethoxysilane (6 moles) within 4 hours while cooling with ice.
Towards the end of the silane addition the desired silyl-propyl dithiocarbamate precipitates.
In order to complete the precipitation, 1.5 litres of petroleum other are added, followed by filtering. On removing the volatile components 2131.4 g of a yellow powder are obtained corresponding to 89.1% of the theoretical yield.
Example 3: sodium (3-triethoxysilyl-propyl)dithiocarbamate (C2H5 j3s;-(cl~2)3-NH-cs-s Na ~ 3 221.4 g of 3-aminopropyl triethoxysilane (1 mole) and 83O7 g of carbon disulphide (1.1 moles, excess) are simultane-ously added dropwise at room temperature within one hour to a sodium methylate solution obtained by feeding 23 g of sodium mole) into 500 ml of ethanol. The temperature of the reaction solution increases to 45C of its own accord. The product solu-tion thus obtained is freed from the ethanol on a rotation eva-porator so that 312.7 g of a yellow solid matter are obtained corresponding to 97.9% of the theoretical yield. The signal positions observed for the trimethylene group in the lH-NMR
spectrum correspond to those for the ammonium dithiocarbamate produced according to Example 2 so that the identity of the sodium-analogous compound is assured.
Example 4: sodium (bis(3-triethoxysilyl-propyl))dithiocarbamate ~ 133S67~
((C2H5O)3si-(cH2)3)2 N-CS-S~ Na~,4:
A mixture of 212.9 g of bis(3-triethoxysilyl-propyl) (0 5 mole), 41.9 g of carbon disulphide (0.55 mole, excess) and 150 ml of ethanol are added dropwise at room temperature wit;hin one hour to a sodium methylate solution obtained by feeding 11.5 g of sodium (0.5 mole) into 250 ml of ethanol.
The temperature of the reaction mixture is maintained at approximately 30C with the aid of a water bath. Upon removing the solvent in vacuo 261 g of a highly viscous yellow liquid are obtained corresponding to a yield of 99.7 of the theoretical yield.
Cl9H42o6NNas2si2 (523,836):
C(%) H(%) N(%) S(%) computed: 43.57 8.08 2.67 12.24 obtained: 43.4 8.3 2.4 12.5 II N-(3-trialkoxysilyl-propyl)-N'-alkyl thioureas General rules for the productions:
Equimolar amounts of the ammonium dithiocarbamates 1, 2 and of a primary amine (in the case of amines having boiling points lower than 100C an excess of amine can be applied) are mixed in a flask having a bridge-shaped still head arc and gradually heated while stirring. Starting at a bottom temperature of 80C triethyl amine begins to distill over. A
-- ~}
~ ^ 1335673 generation of H2S is observed at the same time. At a bottom temperature of 80C distillate is no longer obtained.
Finally a water jet vacuum is applied for the removal of the volatile components. In fact the crude products thus obt:ained usually have a yellowish or orange coloration but are elementary-analytically and lH-NMR- spectro-scopically pure so that further purification can be dispensed with.
(Examples 5 to 7) General rule for the production:
Equimolar amounts of the ammonium dithiocarbamates 1, 2 and of a secondary amine are mixed in a flask provided with bridge-shaped stillhead and are heated to approximately 120C
as described under II and processed.
Example 5: N-(3-triethoxysilyl-propyl)-N'-N~-dibutyl thiourea (c2H5o)3si-(cH2)3-NH-cs-N(c4Hs)2~ 5:
Production from 199.3 g of 2 (0.5 mole) and 64.4 g of di-n-butyl amine (0.5 mole). Yield: 190.7 g corresponding to 97.1% of the theoretical yield, dark yellow viscous liquid.
~ ^ ` 1335~73 ClgH40N2o3SSi (392,679):
C(%) H(%) N(%) S(%) computed: 55.06 10.27 7.13 8.16 ob~ained: 55.0 10.3 7.8 8.2 Example 6: N-(3-triethoxysilyl-propyl)-N'-N'-diallyl thiourea (C2HsO)3Si-CH2-CH2-CH2-NH-CS-N(CH2-CH=CH2)2, 6:
Production from 199.3 g of 2 (0.5 mole) and 48.6 g of diallyl amine (0.5 mole). Yield: 170.9 g corresponding to 94.8% of the theoretical yield; orange-coloured liquid.
C16H32N2o3SSi (360,593):
C(%) H(%) N(%) S(%) computed: 53.30 8.95 7.77 8.89 obtained: 52.6 8.5 8.1 8.8 The lH-NMR spectrum of 11 is shown in Figure 2.
Example 7: N-(triethoxysilyl-propyl)-N'-N'-bis-(3-triethoxy-silyl-propyl)thiourea (c2H5o)3si-(cH2)3-NH-cs-N((cH2)3si(oc2H5)3)2~7 .,. :~.
r .:
~ - 1335673 Production from 99.7 g of 2 (0.25 mole) and 106.4 g of bis(3-triethoxysilyl-propyl)amine (0.25 mole). Yield: 169.7 g corresponding to 98.5% of the theoretical yield, yellowish brown liquid.
C2~H64N2O9ssi3 (689,147) C(%) H(%) N(%) S(%) computed: 48.80 9.36 4.07 4.65 obtained: 48.5 10.1 4.6 4.3 IV N,N-bis(3-trialkoxysilyl-propyl)-N'-N'-dialkyl thioureas (Examples 8 and 9):
Example 8: N-N-bis(3-triethoxysilyl-propyl)-N'-N'-dibutyl thiourea ((C2H50)3si-(cH2)3)2 N-CS-N(C4Hg)2, 8:
A mixture of 87.0 g of the sodium dithiocarbamate 4 (0.17 mole) and 64.6 g of di-n-butyl amine (0.5 mole, excess) are heated for 4 hours to 160C while stirring until the backflow of the amine applied starts. Excess amine is subsequently distilled off and the highly viscous residue is mixed with 300 ml of acetone. Upon filtering off the precipitated deposit (8.9 g corresponding to 95.6%
of the theoretical amount) and removal of the . ~
133S67~
solvent in vacuum 11.7 g of a highly viscous yellowish-brown liq-uid are obtained (corresponding to 92.5% of the theoretical yield).
C27H60N206SSi2 (597,022):
C(%) H(%) N(%) S(%~
computed: 54.32 10.13 4.69 5.37 obtained: 53.4 lo.o 4.1 4.9 10~ Example ~ : tetra-(3-triethoxysilyl-propyl)thiourea ttC H5)3S;-tCH2)3)2 N-CS N ttcH2 3 2 5 3 2 A mixture of 87.0 g of the sodium dithiocarbamate 4 (0.17 mole) and 85.1 g of bis(3-triethoxysilyl-propyl)amine ~0.2 mole, excess) are heated for 6 hours to 140C while stirring.
Excess amine is subsequently distilled off in high vacuum. The highly viscous residue is then mixed with 450 ml of acetone.
Upon filtering off the precipitate (9.1 g corresponding to 97.8%
of the theoretical amount) and removal of the solvent 136.9 g of a honey-like viscous red-brown li~uid are obta~ne~ (corresponding to 92.3% of the expected amount).
C37H84N2Ol2ssi4 (893,489):
C~%) H(%) Nt%) S(%) computed: 49.74 9.48 3.14 3.59 obtained: 48.9 9.9 2.9 3.1
- H2S / Ml~S
(RO)3S;- (CHX)a - NR1 _ CS - NR R
The reaction according to equation (1) is preferably carried out in a non-polar aprotic solvent when tertiary amines '~''5' B are used as proton~ acceptors. In that case particularly suit-.
`~ 1 33s6 73 able solvents are (halogenated) hydrocarbons or (cyclic) ethers such as n-pentane or tetrahydrofuran or their mixtures.
B When using alkali alcoholate as proton~ acceptor, then I polar aprotic solvents, as for example, dimethyl formamide, and even specific polar protic solvents, as for example, alcohols, are suitable. In the latter case it is particularly advantageous to produce the alkali alcoholate directly by reacting alkali metal, particularly sodium or potassium, with an alcohol, partic-ularly methanol or ethanol, by means of conventional methods andto use this reaction solution directly for the reaction to the dithiocarbamate.
It is an important prerequisite for the suitability as solvent that it must dissolve the aminosilane on the one hand and that on the other the dithiocarbamate should be precipitated as quantitatively as possible since otherwise it would be inert.
The reactants aminopropyl silane, carbon disulphide and tertiary amine or alkali alcoholate are applied in a molar ratio of approximately 1:1:1 without excluding, for example, a variation of up to 10% from the stoichiometrically required amounts. Cor-responding molar ratios also apply to the reactants dithiocarba-mate and amine according to equation (2).
Amines, wherein R2 and/or R3 represent (CIH3)b -(CH2)3-s; (OR)3 b were known according to DE-OS 31 20 214 and J.L. Speier at al., J. Org. Chem. 36 (1971), 3120 ff. Triethyl amine or pyridine are preferably applied as amines.
The reaction according to e~uation (1) is preferably carried out at temperatures below the boiling point of carbon 1335~73 disulphide, particularly at temperatures of 0 to 46C. The organosilicon compound is added with advantage to the carbon disulphide, which, under certain conditions, ls present in a sto-ichiometric excess. The precipitated "dithiocarbamate" is fil-tered off and freed from the solvent residues under vacuum.
Dithiocarbamates like those obtained by means of the reaction according to equation (1) are known in several instances from the literature. However, according to the prior art they 0 are reacted with acrylonitrile (DE-OS 20 00 224) or converted by hydrolysis into a polysiloxane compound (U.S. Patent 2,938,046).
According to the present invention the "dithiocarba-mates", obtained as bright yellow crystal powder, are converted into thioureas. According to reaction step (2) primary or sec-onardy amines, preferably in equimolar amounts, are heated with the organosilicon compounds, usually without the addition of sol-vents, to temperatures of 80 to 140C while stirring.
In a favourable embodiment with the use of an ammonium dithiocarbamate the nascent hydrogen sulphide and the separating tertiary amine are drawn off under vacuum. The thioureas thus obtained in high yields require no further purification.
However, no hydrogen sulphide is formed when using alkali dithiocarbamates but the corresponding alkali hydrogen sulphide is formed. It is separated from the desired product by precipitating with a suitable solvent, for example, acetone.
The present invention also relates to N,N,N'- or N,N'N'- and N,N,N',N'-substituted thioureas having the general fo~mula (III) (I 3 b ~ 1 `' (R0)3 b s; - (CHX)a - NR1 _ Cs - NR2R3 , -wherein a, b, X, R, Rl and R3 have the above defined meaning with the proviso that Rl and R2 or R3 are not H.
These compounds are used with advantage in halogen ruhber mixtures because of their vulcanization-accelerating ef*ect.
Examples of Production:
1. 3-trialkoxysilyl-propyl dithiocarbamates (Examples 1-4):
Example 1: triethyl ammonium (3-trimethoxy-silyl-propyl)dithiocarbamate.
(CH30)3Si-(CH2)3-NH-CS-S~ HN(C2H5)ffl,1:
789 g of 3-aminopropyl trimethoxysilane (4.4 moles) and 465.5 g of triethyl amine (4.6 moles, excess) are put into 1200 ml of THT at room temperature and mixed dropwise with 351.5 g of carbon disulphide (4.6 moles, excess) within six hours while cooling with ice. The precipitated bright yellow deposit is filtered off and freed from the solvent in vacuo.
1337 g of a yellow powder are obtained corresponding to 85.2%
of the theoretical yield.
C13H32N2o3S2Si (356,624):
C(%) H(%) N(%) S(%) computed: 43.78 9.04 7.86 17.98 obtained: 43.3 9.3 7.7 18.5 Example 2: triethyl ammonium (3-triethoxysilyl-propyl) dithiourea (C2H5o)3si-(cH2)3-NH-cs- ~ HN(C2Hs)3~ ,2:
, 1335~ 3 637.6 g of triethyl amine (6.3 moles,^ excess) and 502.3 g of carbon disulphide (6.6 moles, excess) are put into 1.5 litres of THF and mixed with 1328.3 g of 3-aminopropyl tri-ethoxysilane (6 moles) within 4 hours while cooling with ice.
Towards the end of the silane addition the desired silyl-propyl dithiocarbamate precipitates.
In order to complete the precipitation, 1.5 litres of petroleum other are added, followed by filtering. On removing the volatile components 2131.4 g of a yellow powder are obtained corresponding to 89.1% of the theoretical yield.
Example 3: sodium (3-triethoxysilyl-propyl)dithiocarbamate (C2H5 j3s;-(cl~2)3-NH-cs-s Na ~ 3 221.4 g of 3-aminopropyl triethoxysilane (1 mole) and 83O7 g of carbon disulphide (1.1 moles, excess) are simultane-ously added dropwise at room temperature within one hour to a sodium methylate solution obtained by feeding 23 g of sodium mole) into 500 ml of ethanol. The temperature of the reaction solution increases to 45C of its own accord. The product solu-tion thus obtained is freed from the ethanol on a rotation eva-porator so that 312.7 g of a yellow solid matter are obtained corresponding to 97.9% of the theoretical yield. The signal positions observed for the trimethylene group in the lH-NMR
spectrum correspond to those for the ammonium dithiocarbamate produced according to Example 2 so that the identity of the sodium-analogous compound is assured.
Example 4: sodium (bis(3-triethoxysilyl-propyl))dithiocarbamate ~ 133S67~
((C2H5O)3si-(cH2)3)2 N-CS-S~ Na~,4:
A mixture of 212.9 g of bis(3-triethoxysilyl-propyl) (0 5 mole), 41.9 g of carbon disulphide (0.55 mole, excess) and 150 ml of ethanol are added dropwise at room temperature wit;hin one hour to a sodium methylate solution obtained by feeding 11.5 g of sodium (0.5 mole) into 250 ml of ethanol.
The temperature of the reaction mixture is maintained at approximately 30C with the aid of a water bath. Upon removing the solvent in vacuo 261 g of a highly viscous yellow liquid are obtained corresponding to a yield of 99.7 of the theoretical yield.
Cl9H42o6NNas2si2 (523,836):
C(%) H(%) N(%) S(%) computed: 43.57 8.08 2.67 12.24 obtained: 43.4 8.3 2.4 12.5 II N-(3-trialkoxysilyl-propyl)-N'-alkyl thioureas General rules for the productions:
Equimolar amounts of the ammonium dithiocarbamates 1, 2 and of a primary amine (in the case of amines having boiling points lower than 100C an excess of amine can be applied) are mixed in a flask having a bridge-shaped still head arc and gradually heated while stirring. Starting at a bottom temperature of 80C triethyl amine begins to distill over. A
-- ~}
~ ^ 1335673 generation of H2S is observed at the same time. At a bottom temperature of 80C distillate is no longer obtained.
Finally a water jet vacuum is applied for the removal of the volatile components. In fact the crude products thus obt:ained usually have a yellowish or orange coloration but are elementary-analytically and lH-NMR- spectro-scopically pure so that further purification can be dispensed with.
(Examples 5 to 7) General rule for the production:
Equimolar amounts of the ammonium dithiocarbamates 1, 2 and of a secondary amine are mixed in a flask provided with bridge-shaped stillhead and are heated to approximately 120C
as described under II and processed.
Example 5: N-(3-triethoxysilyl-propyl)-N'-N~-dibutyl thiourea (c2H5o)3si-(cH2)3-NH-cs-N(c4Hs)2~ 5:
Production from 199.3 g of 2 (0.5 mole) and 64.4 g of di-n-butyl amine (0.5 mole). Yield: 190.7 g corresponding to 97.1% of the theoretical yield, dark yellow viscous liquid.
~ ^ ` 1335~73 ClgH40N2o3SSi (392,679):
C(%) H(%) N(%) S(%) computed: 55.06 10.27 7.13 8.16 ob~ained: 55.0 10.3 7.8 8.2 Example 6: N-(3-triethoxysilyl-propyl)-N'-N'-diallyl thiourea (C2HsO)3Si-CH2-CH2-CH2-NH-CS-N(CH2-CH=CH2)2, 6:
Production from 199.3 g of 2 (0.5 mole) and 48.6 g of diallyl amine (0.5 mole). Yield: 170.9 g corresponding to 94.8% of the theoretical yield; orange-coloured liquid.
C16H32N2o3SSi (360,593):
C(%) H(%) N(%) S(%) computed: 53.30 8.95 7.77 8.89 obtained: 52.6 8.5 8.1 8.8 The lH-NMR spectrum of 11 is shown in Figure 2.
Example 7: N-(triethoxysilyl-propyl)-N'-N'-bis-(3-triethoxy-silyl-propyl)thiourea (c2H5o)3si-(cH2)3-NH-cs-N((cH2)3si(oc2H5)3)2~7 .,. :~.
r .:
~ - 1335673 Production from 99.7 g of 2 (0.25 mole) and 106.4 g of bis(3-triethoxysilyl-propyl)amine (0.25 mole). Yield: 169.7 g corresponding to 98.5% of the theoretical yield, yellowish brown liquid.
C2~H64N2O9ssi3 (689,147) C(%) H(%) N(%) S(%) computed: 48.80 9.36 4.07 4.65 obtained: 48.5 10.1 4.6 4.3 IV N,N-bis(3-trialkoxysilyl-propyl)-N'-N'-dialkyl thioureas (Examples 8 and 9):
Example 8: N-N-bis(3-triethoxysilyl-propyl)-N'-N'-dibutyl thiourea ((C2H50)3si-(cH2)3)2 N-CS-N(C4Hg)2, 8:
A mixture of 87.0 g of the sodium dithiocarbamate 4 (0.17 mole) and 64.6 g of di-n-butyl amine (0.5 mole, excess) are heated for 4 hours to 160C while stirring until the backflow of the amine applied starts. Excess amine is subsequently distilled off and the highly viscous residue is mixed with 300 ml of acetone. Upon filtering off the precipitated deposit (8.9 g corresponding to 95.6%
of the theoretical amount) and removal of the . ~
133S67~
solvent in vacuum 11.7 g of a highly viscous yellowish-brown liq-uid are obtained (corresponding to 92.5% of the theoretical yield).
C27H60N206SSi2 (597,022):
C(%) H(%) N(%) S(%~
computed: 54.32 10.13 4.69 5.37 obtained: 53.4 lo.o 4.1 4.9 10~ Example ~ : tetra-(3-triethoxysilyl-propyl)thiourea ttC H5)3S;-tCH2)3)2 N-CS N ttcH2 3 2 5 3 2 A mixture of 87.0 g of the sodium dithiocarbamate 4 (0.17 mole) and 85.1 g of bis(3-triethoxysilyl-propyl)amine ~0.2 mole, excess) are heated for 6 hours to 140C while stirring.
Excess amine is subsequently distilled off in high vacuum. The highly viscous residue is then mixed with 450 ml of acetone.
Upon filtering off the precipitate (9.1 g corresponding to 97.8%
of the theoretical amount) and removal of the solvent 136.9 g of a honey-like viscous red-brown li~uid are obta~ne~ (corresponding to 92.3% of the expected amount).
C37H84N2Ol2ssi4 (893,489):
C~%) H(%) Nt%) S(%) computed: 49.74 9.48 3.14 3.59 obtained: 48.9 9.9 2.9 3.1
Claims (12)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for producing N- and N'-substituted singly or multiply substituted organyl oxysilyl-functional thioureas, wherein a) an aminoalkyl silane having the formula I
where b is 0, 1 or 2, R is alkyl containing 1 to 6 C atoms, cycloalkyl containing 5 to 7 C atoms, aryl X is hydrogen when a=1, 3, 4, 5 or 6 or X is when a= 1 R1 is hydrogen, or is reacted in an organic solvent with carbon disulphide in the presence of a tertiary amine (A) or alkali alcoholate (MOR), b) the dithiocarbamate thus formed and having the general formula II
is isolated in and reacted with at the least the equimolar amount of an amine having the general formula where R2 is hydrogen R2, R3 identical or different from each other represent alkyl containing 1 to 8 C atoms, alkenyl containing 2 to 8 C
atoms, aralkyl, or this mixture is heated and the resulting product having the general formula is subsequently isolated.
where b is 0, 1 or 2, R is alkyl containing 1 to 6 C atoms, cycloalkyl containing 5 to 7 C atoms, aryl X is hydrogen when a=1, 3, 4, 5 or 6 or X is when a= 1 R1 is hydrogen, or is reacted in an organic solvent with carbon disulphide in the presence of a tertiary amine (A) or alkali alcoholate (MOR), b) the dithiocarbamate thus formed and having the general formula II
is isolated in and reacted with at the least the equimolar amount of an amine having the general formula where R2 is hydrogen R2, R3 identical or different from each other represent alkyl containing 1 to 8 C atoms, alkenyl containing 2 to 8 C
atoms, aralkyl, or this mixture is heated and the resulting product having the general formula is subsequently isolated.
2. A method as claimed in claim 1 wherein R2 or R3 is benzyl.
3. N,N,N'-, N,N',N'- and N,N,N',N'- substituted thioureas having the general formula (CH3)b (RO)3-b Si-(CHX)a-NR1-CS-NR2-R3 where a, b, X, R, R1, R2 and R3 have the meanings defined in claim 1 or 2, with the proviso that R1 and R2 are not H.
4. (CH3O)3Si-(CH2)3-NH-CS-S- HN(C2H5)?.
(C2H5O)3Si-(CH2)3-NH-CS-S- HN(C2H5)?.
6. (C2H5O)3Si-(CH2)3-NH-CS-S- Na+.
7. ((C2H5O)3Si-(CH2)3)2-N-CS-S- Na+.
8. (C2H5O)3Si-(CH2)3-NH-CS-N(C4H9)2.
9. (C2H5O)3Si-CH2-CH2-CH2-NH-CS-N(CH2-CH=CH2)2.
10. (C2H5O)3Si-(CH2)3-NH-CS-N((CH2)3Si(OC2H5)3)2.
11. ((C2H5O)3Si-(CH2)3)2N-CS-N(C4H9)2.
12. ((C2H5O)3Si-(CH2)3)2N-CS-N((CH2)3-Si(OC2H5)3)2.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3821465A DE3821465A1 (en) | 1988-06-25 | 1988-06-25 | METHOD FOR THE PRODUCTION OF SINGLE OR MULTIPLE SUBSTITUTED ORGANYLOXYSILYL-FUNCTIONAL THIOUROSES AND THESE COMPOUNDS |
| DEP3821465.2 | 1988-06-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1335673C true CA1335673C (en) | 1995-05-23 |
Family
ID=6357229
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000603784A Expired - Fee Related CA1335673C (en) | 1988-06-25 | 1989-06-23 | Process for producing singly or multiply substituted organyl oxysilyl-functional thioureas and said compounds |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0348620B1 (en) |
| JP (1) | JP2746663B2 (en) |
| AT (1) | ATE110731T1 (en) |
| CA (1) | CA1335673C (en) |
| DE (2) | DE3821465A1 (en) |
| ES (1) | ES2059604T3 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108218910A (en) * | 2017-12-29 | 2018-06-29 | 烟台市裕盛化工有限公司 | Silane of a kind of sulfur-bearing urea structure and preparation method thereof |
| US10913805B2 (en) | 2017-07-31 | 2021-02-09 | Lg Chem, Ltd. | Modifier, method for preparing the same, and modified conjugated diene-based polymer including the same |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3925356A1 (en) * | 1989-07-31 | 1991-02-07 | Degussa | N, N'-DISUBSTITUED AND N, N, N '- / N, N', N'-TRISUBSTITUTED THIOUROSES AND METHOD FOR THE PRODUCTION THEREOF (II) |
| CA2311671A1 (en) * | 1999-08-13 | 2001-02-13 | Thierry Florent Materne | Nitrogen containing siloxy compounds |
| DE10053545A1 (en) * | 2000-10-27 | 2002-05-08 | Henkel Kgaa | Polymers with urea groups and silyl groups, their production and use |
| US7074491B2 (en) * | 2003-11-04 | 2006-07-11 | Dionex Corporation | Polar silanes for binding to substrates and use of the bound substrates |
| JP2012240922A (en) * | 2011-05-16 | 2012-12-10 | Shin-Etsu Chemical Co Ltd | Organosilicon compound and method for producing the same, compounding agent for rubber, rubber composition, and tire |
| US9731221B2 (en) | 2011-05-25 | 2017-08-15 | Cidra Corporate Services, Inc. | Apparatus having polymer surfaces having a siloxane functional group |
| ES2936663T3 (en) | 2011-05-25 | 2023-03-21 | Cidra Corporate Services Inc | Separation by flotation using spheres or bubbles containing polydimethylsiloxane |
| GB201115823D0 (en) * | 2011-09-13 | 2011-10-26 | Novel Polymer Solutions Ltd | Mineral processing |
| JP6291442B2 (en) * | 2015-03-12 | 2018-03-14 | 京セラ株式会社 | Thermistor sensor casting resin composition and thermistor sensor |
| JP7208109B2 (en) * | 2019-06-05 | 2023-01-18 | 信越化学工業株式会社 | Organosilanes, surface treatment agents, coating compositions and coated articles |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2938046A (en) * | 1956-10-11 | 1960-05-24 | Union Carbide Corp | Dithiocarbamyl-containing silicon compounds |
| US3642855A (en) * | 1969-01-03 | 1972-02-15 | Gen Electric | Silyl-containing dithiocarbamates with functional groups on sulfuralkyl ester side chain |
| US3646089A (en) * | 1969-01-31 | 1972-02-29 | Gen Electric | Process for producing organosilicon compounds with isothiocyanate substituent bonded through divalent bridge |
| US4645846A (en) * | 1985-04-12 | 1987-02-24 | Scm Corporation | Silane compositions |
| DE3706521A1 (en) * | 1987-02-28 | 1988-09-08 | Degussa | ORGANOSILANES CONTAINING BENZOYLTHIOHURINE GROUPS, METHOD FOR THE PRODUCTION THEREOF |
-
1988
- 1988-06-25 DE DE3821465A patent/DE3821465A1/en not_active Withdrawn
-
1989
- 1989-04-19 ES ES89106989T patent/ES2059604T3/en not_active Expired - Lifetime
- 1989-04-19 DE DE58908261T patent/DE58908261D1/en not_active Expired - Fee Related
- 1989-04-19 AT AT89106989T patent/ATE110731T1/en not_active IP Right Cessation
- 1989-04-19 EP EP89106989A patent/EP0348620B1/en not_active Expired - Lifetime
- 1989-06-23 CA CA000603784A patent/CA1335673C/en not_active Expired - Fee Related
- 1989-06-26 JP JP1161007A patent/JP2746663B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10913805B2 (en) | 2017-07-31 | 2021-02-09 | Lg Chem, Ltd. | Modifier, method for preparing the same, and modified conjugated diene-based polymer including the same |
| CN108218910A (en) * | 2017-12-29 | 2018-06-29 | 烟台市裕盛化工有限公司 | Silane of a kind of sulfur-bearing urea structure and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0348620A2 (en) | 1990-01-03 |
| EP0348620A3 (en) | 1990-11-07 |
| ES2059604T3 (en) | 1994-11-16 |
| DE3821465A1 (en) | 1989-12-28 |
| ATE110731T1 (en) | 1994-09-15 |
| EP0348620B1 (en) | 1994-08-31 |
| JP2746663B2 (en) | 1998-05-06 |
| JPH0245491A (en) | 1990-02-15 |
| DE58908261D1 (en) | 1994-10-06 |
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