carbamic acid-(2-vinylmercapto-ethyl ester) | 114983-42-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: carbamic acid-(2-vinylmercapto-ethyl ester)
• 英文别名: Carbamidsaeure-(2-vinylmercapto-aethylester)；1-Carbamoyloxy-2-vinylmercapto-aethan；2-Ethenylsulfanylethyl carbamate
• CAS: 114983-42-5
• 化学式: C₅H₉NO₂S
• mdl: MFCD19209110
• 分子量: 147.198
• InChiKey: BIFPZKWFWLTBAN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  9
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  77.6
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  1-乙烯基硫基乙醇 、 尿素 在 potassium cyanate 作用下， 生成 carbamic acid-(2-vinylmercapto-ethyl ester)
  参考文献：
  名称：

  Unsaturated carbamato ethers and thioethers, polymers thereof, and methods of making them

  摘要：

  碳酸酯醚和硫醚的化学式为<;FORM:0840891/IV(a)/1>;（其中Y为氧或硫；A为环己亚烷，提供至少2个C原子的链，相邻的O和Y原子之间，或者链被一个或多个O原子中断，使得在-YAO-中，每两个相邻的杂原子之间被一个C2-C4烷基链分隔，其中至少有两个C原子在杂原子之间延伸；R和R1要么共同代表一个四元、五元或3-氧代五元亚甲基基团，要么分别代表单独的基团，其中R为氢、苯基或C1-C6烷基，R1为氢、环己基、苯基、氯苯基、萘基、苄基、油酸烯基或C1-C22烷基），以及这些化合物的N-甲氧基和N-(C1-C4烷氧基)甲基衍生物，其中R和R1中的一个或两个为氢时，用作合成树脂或纤维素或纤维素衍生物的增塑剂或改性剂，或用于聚合或共聚。纤维素材料，如棉、纸或人造丝织物，可以与单体发生反应，并通过引入能与其他不饱和化合物（如苯乙烯、丙烯酸酯、丙烯酰胺和丙烯腈）发生反应的基团进行改性。羰酸酯醚与丙烯腈的共聚物可用于生产丝和薄膜，例如通过在二甲基甲酰胺中溶解后挤出，或通过浇铸和加热固化。棉织物可以浸渍在2-(乙烯硫)基-N-甲醛基碳酸酯溶液中，干燥并经热固化，形成一种可与二硫化碳反应以形成黄药醋酸盐的反应性材料，适合在氢氧化钠溶液中溶解后挤出以形成丝丝。2-乙烯氧基乙基-N,N-二甲基碳酸酯在石油醚中悬浮，加热并加入偶氮二异丁基氰，形成一种聚合物，可用作纤维素醋酸盐或丁酸盐的增塑剂。碳酸酯醚可用于改性脲、三嗪和硫脲-甲醛树脂，这些树脂可用于成型、铸造或涂层。单体可以在BF3、SO2或其他阳离子或酸性催化剂存在下聚合，或者如果它们首先转化为亚砜或砜，那么可以使用碱性催化剂，如氢化钠。也可以使用偶氮催化剂，聚合可以在中性或微碱性条件下在块状、溶液、乳液或悬浮体系中进行。用于共聚的催化剂包括有机过氧化物和过硫酸盐。可以与碳酸酯醚共聚的指定化合物包括丙烯酸、醇的酯与丙烯酸的饱和和不饱和醇的酯、乙烯酯、乙烯醚、乙烯氧基丙氧乙醇、丙烯腈、丙烯酰胺、乙烯卤代物、氯氟乙烯、乙酰基丁二烯、乙烯二丙烯酸酯和双(乙烯氧基乙基)脲。碳酸酯醚的同聚物，其中化学式中的R和R1都是氢，是水溶性的，而单体的同聚物，其中R和R1中只有一个或两个不是氢，是水不溶的，但可溶于有机溶剂。这些溶液或乳液可用于对纺织品（如棉、人造丝、尼龙和羊毛）进行浆料、涂层或浸渍，或用于涂覆纸张、木材、皮革或金属。这些聚合物可在施加到基材后通过加热或其他方法进行固化。

  公开号：

  US02806838A1

文献信息

• Unsaturated carbamato ethers and thioethers, polymers thereof, and methods of making them
  申请人：ROHM &

  公开号：US02806838A1

  公开（公告）日：1957-09-17

  Carbamato-ethers and -thioethers of the formula <;FORM:0840891/IV(a)/1>; (where Y is oxygen or sulphur; A is cyclohexylene, a C2-C10 alkylene group providing a chain of at least 2 C atoms between adjacent O and Y atoms, or an alkylene group the chain of which is interrupted by one or more O atoms such that in -YAO- every two adjacent hetero atoms are separated by a C2-C4 alkylene group, of which at least two C atoms extend in a chain between the hetero atoms; R and R1 either collectively represent a single tetra-, penta- or 3-oxapenta-methylene group, or individually represent separate groups, R being hydrogen, phenyl, or C1-C6 alkyl, and R1 being hydrogen, cyclohexyl, phenyl, chlorophenyl, naphthyl, benzyl, oleyl, or C1-C22 alkyl) and the N-methylol and N-(C1-C4 alkoxy) methyl derivatives of those compounds where one or both of R and R1 are hydrogen, are employed as plasticizers or modifiers of synthetic resins or cellulose or cellulose derivatives, or are subjected to polymerization or copolymerization. Cellulosic materials such as cotton, paper, or rayon fabrics may be reacted with the monomers and modified by the introduction of groups which are capable of reacting with other unsaturated compounds such as styrene, acrylates, acrylamides, and acrylonitrile. Copolymers of the carbamatoethers with acrylonitrile may be used for the production of filaments and films, e.g. by extrusion of a solution in dimethyl formamide, or by casting and curing by heat. A cotton fabric may be impregnated with a solution of 2-(vinylthio) ethyl N-methylol carbamate, dried and heatcured to form a reactive material which may be reacted with carbon bisulphide to form a xanthate suitable for extrusion to form filaments after solution in caustic soda. A suspension of 2 - vinyloxyethyl - N,N - dimethylcarbamate in petroleum ether is heated in presence of azo-di-isobutyronitrile to form a polymer which may be used as a plasticizer for cellulose acetate or butyrate. The carbamatoethers may be used for modifying urea-, triazine-, and thiourea-formaldehyde resins which may be used for moulding, casting, or coating. The monomers may be polymerized in the presence of BF3, SO2 or other cationic or acidic catalyst, or if they are first converted to sulphoxides or sulphones there may be used a basic catalyst such as sodamide. Azo catalysts may be used and polymerization may take place in bulk, solution, emulsion, or suspension under neutral or slightly alkaline conditions. Catalysts employed for co-polymerization include organic peroxides, and persulphates. Specified compounds which may be copolymerized with the carbamato-ethers include methacrylic acid, esters of saturated and unsaturated alcohols with methacrylic acid, vinyl esters, vinyl ethers, vinyloxypropoxyethanol, methacrylamide, vinyl halides, chloro-fluoro ethylene, acetoxy butadiene, ethylene diacrylate, and bis (vinoxyethyl) urea. Hompolymers from carbamato ethers, in which both R and R1 of the formula are hydrogen, are water-soluble, and those from monomers, in which only one or neither of R and R1 is hydrogen, are water-insoluble but are soluble in organic solvents. The solutions or emulsions may be used for sizing, coating, or impregnating textiles, e.g. cotton, rayon, nylon and wool, or for coating paper, wood, leather, or metals. The polymers may be treated with formaldehyde before or after application to a substratum to provide groups which may be condensed on heating. Examples describe the preparation of copolymers of methyl methacrylate with 2-(vinylthio) ethyl-N-tthyl carbamate and the modification of these by the admixture of N.N1-bis-methoxymethyl ethyleneurea so as to obtain products which on heating become resistant to organic solvents. The polymerization of vinyl-thiopentyl N - p - chlorophenylcarbamate by heating a solution thereof in presence of dimethyl azo - di - isobutyrate is described. The polymer so obtained is used for plasticizing polyvinyl chloride resins.ALSO:The invention comprises compounds of the general formula <;FORM:0840891/IV(b)/1>; where Y is oxygen or sulphur, A is cyclohexylene, a C2-C10 alkylene group which provides a chain of at least 2 carbon atoms between adjacent O and Y atoms, or an alkylene group the chain of which is interrupted by one or more oxygen atoms and which is such that, in the group -YAO- every two adjacent hetero atoms are separated by a C2-C4 alkylene group of which at least two carbon atoms extend in a chain between them. R and R1 are either collectively a tetramethylene, pentamethylene, or 3 oxapentamethylene group, or separate groups, in which case R is hydrogen, phenyl or C1-C6 alkyl, and R1 is hydrogen, cyclohexyl, phenyl, chlorophenyl, naphthyl, benzyl, a C1-C22 alkyl group or an oleyl group, or R2OCH2, where R2 is hydrogen or C1-C4 alkyl. Compounds of the general formula <;FORM:0840891/IV(b)/2>; are used as a starting material together with another suitable compound, depending upon the nature of R and R1. When both R and R1 are hydrogen, preferably equal quantities of urea and the compound of formula II are mixed and heated between 100 DEG C. and 160 DEG C., preferably in the presence of a basic catalyst, e.g. sodium, potassium or lithium carbonates or cyanates or zinc oxide, and in the presence of vacuum or an inert gas e.g. nitrogen to assist the removal of ammonia. It is preferable to use anhydrous reaction conditions, and the product may be recovered by distillation or recrystallization from e.g. water or ethyl acetate. For compounds where R is hydrogen and R1 is one of the other groups defined above, an organic isocyanate of general formula R1NCO is reacted with the compound of formula II in equimolar amounts generally in the presence of e.g. benzene, ether or carbon tetrachloride preferably with a small amount of basic catalyst e.g. triethylamine benzyl dimethylamine, sodium and potassium methoxides, at a temperature 20-100 DEG C. for 4-16 hours. In the case where R1 is CH2OR2 an alkoxymethyl isocyanate of general formula R2OCH2NCO is used under similar conditions, or formaldehyde with or without a C1-C4 alkanol is reacted with a compound of general formula I where at least one of R and R1 are hydrogen. When neither R nor R1 are hydrogen but are radicals as defined above the required compounds are obtained by reacting a carbamyl chloride of formula RR1NC11Cl with the compound of formula II in the presence of a tertiary amine e.g. triethylamine, pyridine, benzyl dimethylamine, or sodium or potassium hydroxides or carbonates. An organic solvent e.g. acetonitrile, ether, benzene or carbon tetrachloride, or water may be present. The reaction is carried out at 0-100 DEG C. for 2-12 hours. Many examples are given.ALSO:Carbamato-ethers and thioethers containing a vinyl group (see Group IV(b)), their N-methylol and N-(C1-C4 alkoxy) methyl derivatives, and their polymerization or co-polymerization products are used for treating textile materials so as to produce such effects as crease-resistance, shrink-resistance and stiffening, improving handle and modifying water absorption. Specified compounds with which the ethers or thio ethers, may be co-polymerized include methacrylic acid, esters of saturated and unsaturated alcohols with methacrylic acid, vinyl esters, vinyl ethers, vinyloxypropoxyethanol, acrylonitrile, acrylamide, vinylhalides, chlorofluoroethylene, acetoxybutadiene, ethylene, styrene, ethylene diacrylate and bis(vinoxyethyl) urea. Specified textile materials are cotton, wool, nylon and viscose rayon. Homopolymers of the ethers may be used as dye strippers to remove substantive dyes from dyed fabrics. In Examples (18) a cotton fabric is treated with 2-(vinylthio) ethyl N-methylol carbamate to give a water-repellent fabric when dried and cured and reacted with such compounds as acrylonitrile, and a rubbery fabric when reacted with butyl methacrylate; (32) wool is treated with the copolymer of butyl acrylate and 2(vinylthio) ethyl-N-ethylcarbamate to produce a shrink-resistant fabric.ALSO:Carbamato-ethers and thio ethers containing a vinyl group (see Group IV (b)), their N-methylol and N-(C1-C4 alkoxy) methyl derivatives, and their polymers, copolymers and condensation products are used for coating surfaces such as wood, glass, masonry, brick, cement, plaster and metal. The monomers and polymers may be used as anti-oxidants in lubricating oils and in drying-oil paints. The monomers and their methylol compounds may be incorporated in aminoplast resins such as urea-, melamine-, and thiourea-formaldehyde resins and these may be used as coating or adhesive resins for wood or glass e.g. in the production of plywood and safety glass. Homopolymers and copolymers may be applied to substrata from solutions or emulsions to provide protective coatings. After application the coatings may be cured by heating or other means. In examples: (1) vinylthioethyl carbamate is converted with aqueous formaldehyde into a methylol derivative and applied by brushing or dipping to cellulose, nylon, wood, glass, or other substratum, and the coating is dried and heated; the treated article may then be firmly bonded to polyester-vinyl type resin coatings applied thereon in the form of solutions and then dried and cured; (4) 2-(vinylthio ethyl N-ethylcarbamate is added to the extent of 0.25-2.0% to a drying-oil paint as an anti-oxidant and anti-skinning agent; (7) a copolymer of methyl methacrylate and 2-(vinylthio) ethyl N-ethylcarbamate is mixed with N.N1-bis-methoxymethyl ethylene urea and a catalyst, the solution is formed into film-coatings on glass and metal plates, and the coatings are cured by heating; (9) vinyl-thiopentyl N-p-chlorophenyl-carbamate is incorporated to the extent of 0.25-1.0% as an antioxidant in a cutting oil; (15) a mixed vinylthioethyl N-tert. alkyl carbamate in which the alkyl groups have an average of 13 carbon

  碳酸酯醚和硫醚的化学式为<;FORM:0840891/IV(a)/1>;（其中Y为氧或硫；A为环己亚烷，提供至少2个C原子的链，相邻的O和Y原子之间，或者链被一个或多个O原子中断，使得在-YAO-中，每两个相邻的杂原子之间被一个C2-C4烷基链分隔，其中至少有两个C原子在杂原子之间延伸；R和R1要么共同代表一个四元、五元或3-氧代五元亚甲基基团，要么分别代表单独的基团，其中R为氢、苯基或C1-C6烷基，R1为氢、环己基、苯基、氯苯基、萘基、苄基、油酸烯基或C1-C22烷基），以及这些化合物的N-甲氧基和N-(C1-C4烷氧基)甲基衍生物，其中R和R1中的一个或两个为氢时，用作合成树脂或纤维素或纤维素衍生物的增塑剂或改性剂，或用于聚合或共聚。纤维素材料，如棉、纸或人造丝织物，可以与单体发生反应，并通过引入能与其他不饱和化合物（如苯乙烯、丙烯酸酯、丙烯酰胺和丙烯腈）发生反应的基团进行改性。羰酸酯醚与丙烯腈的共聚物可用于生产丝和薄膜，例如通过在二甲基甲酰胺中溶解后挤出，或通过浇铸和加热固化。棉织物可以浸渍在2-(乙烯硫)基-N-甲醛基碳酸酯溶液中，干燥并经热固化，形成一种可与二硫化碳反应以形成黄药醋酸盐的反应性材料，适合在氢氧化钠溶液中溶解后挤出以形成丝丝。2-乙烯氧基乙基-N,N-二甲基碳酸酯在石油醚中悬浮，加热并加入偶氮二异丁基氰，形成一种聚合物，可用作纤维素醋酸盐或丁酸盐的增塑剂。碳酸酯醚可用于改性脲、三嗪和硫脲-甲醛树脂，这些树脂可用于成型、铸造或涂层。单体可以在BF3、SO2或其他阳离子或酸性催化剂存在下聚合，或者如果它们首先转化为亚砜或砜，那么可以使用碱性催化剂，如氢化钠。也可以使用偶氮催化剂，聚合可以在中性或微碱性条件下在块状、溶液、乳液或悬浮体系中进行。用于共聚的催化剂包括有机过氧化物和过硫酸盐。可以与碳酸酯醚共聚的指定化合物包括丙烯酸、醇的酯与丙烯酸的饱和和不饱和醇的酯、乙烯酯、乙烯醚、乙烯氧基丙氧乙醇、丙烯腈、丙烯酰胺、乙烯卤代物、氯氟乙烯、乙酰基丁二烯、乙烯二丙烯酸酯和双(乙烯氧基乙基)脲。碳酸酯醚的同聚物，其中化学式中的R和R1都是氢，是水溶性的，而单体的同聚物，其中R和R1中只有一个或两个不是氢，是水不溶的，但可溶于有机溶剂。这些溶液或乳液可用于对纺织品（如棉、人造丝、尼龙和羊毛）进行浆料、涂层或浸渍，或用于涂覆纸张、木材、皮革或金属。这些聚合物可在施加到基材后通过加热或其他方法进行固化。