- Preparation method of 1-cyano-2-propenyl acetate
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The invention relates to a preparation method of 1-cyano-2-allyl acetate. The method comprises the following steps: (1) reacting hydrocyanic acid with acrolein in the presence of a first catalyst to obtain a reaction solution containing acrolein cyanohydrin; and (2) reacting the obtained reaction solution containing acrolein cyanohydrin with an esterifying agent in the presence of a second catalyst to obtain a reaction solution containing 1-cyano-2-propenyl acetate. The first catalyst and the second catalyst are the same or different and are respectively and independently N,N-dimethylaminopyridine carboxylate. According to the preparation method provided by the invention, the efficient catalyst N,N-dimethylaminopyridine carboxylate is used as a catalyst shared by two steps of reactions, and the two steps of main reactions can be efficiently catalyzed, so that the two steps of main reactions can be carried out according to an approximate stoichiometric ratio; the yield of the product 1-cyano-2-propenyl acetate can reach 99% or above, and the purity can reach 99.5% or above; and the investment is saved, and the product competitiveness is improved.
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Paragraph 0094-0102; 0108-0116; 0122-0130; 0136-0144; 0150
(2020/07/21)
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- Method for preparing acrolein cyanohydrins
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The present invention relates to an improved method for preparing acrolein cyanohydrins from hydrocyanic acid and the corresponding acroleins. The method is characterized in that the acrolein cyanohydrins obtained have a very low hydrocyanic acid content or are free of hydrocyanic acid and are therefore particularly well suited as intermediates for the synthesis of glufosinates.
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Paragraph 0079
(2018/11/21)
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- Preparation method of 2-hydroxyl-3-butene-1-amine
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The invention discloses a preparation method of 2-hydroxyl-3-butene-1-amine. The preparation method comprises the following specific steps: (1) taking acrolein as a start raw material to react with trimethylsilyl cyanide at room temperature in the presence of lithium perchlorate trihydrate to obtain 2-hydroxyl-3-butene-1-nitrile; (2) with diethyl ether or tetrahydrofuran as a solvent, reducing the 2-hydroxyl-3-butene-1-nitrile with lithium aluminum hydride to obtain a crude product of 2-hydroxyl-3-butene-1-amine; (3) making the crude product of 2-hydroxyl-3-butene-1-amine react with hydrochloric acid to obtain 2-hydroxyl-3-butene-1-amine hydrochloride; and (4) making the 2-hydroxyl-3-butene-1-amine hydrochloride react with alkali to finally obtain the 2-hydroxyl-3-butene-1-amine. According to the method disclosed by the invention, without a trimethylsilyl protection group removal process, the operation of reduced pressure distillation is avoided, the reaction path is shortened, and the operation is simple.
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Paragraph 0046; 0047; 0048; 0063; 0064; 0065
(2016/11/09)
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- PROCESS FOR PREPARING PHOSPHORUS-CONTAINING CYANOHYDRINS
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The present invention relates primarily to a process for preparing certain phosphorus-containing cyanohydrins of the formula (I), and also to certain phosphorus-containing cyanohydrins per se and to their use for the preparation of glufosinate and/or glufosinate salts. The present invention further relates to certain mixtures particularly suitable for preparing the phosphorus-containing cyanohydrins of the formula (I).
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Paragraph 0084
(2017/02/24)
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- A single-step, mild, neutral, catalyst-free method for cyanohydrin synthesis
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A wide variety of carbonyl compounds can be transformed to their corresponding cyanohydrins in a single step using a dimethyl sulfoxide (DMSO)-water system in excellent yields (75-94%). The major advantages of this system are that the reaction conditions are mild and neutral; the reaction proceeds without catalyst and gives the corresponding cyanohydrins in short time (15-120 min).
- Degani, Mariam S.,Kakwani, Manoj D.,Palsule Desai, Nutan H.,Bairwa, Ranjeet
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experimental part
p. 461 - 465
(2012/06/15)
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- Rhenium-catalyzed 1,3-isomerization of allylic alcohols: Scope and chirality transfer
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(Chemical Equation Presented) The scope of the triphenylsilyl perrhennate (O3ReOSiPh3, 1) catalyzed 1,3-isomerization of allylic alcohols has been thoroughly explored. It was found to be effective for a wide variety of secondary and tertiary allylic alcohol substrates bearing aryl, alkyl, and cyano substituents. Two general reaction types were found which gave high levels of product selectivity: those driven by formation of an extended conjugated system and those driven by selective silylation of a particular isomer. The efficiency of chirality transfer with various substrates was investigated, and conditions were found in which secondary and tertiary allylic alcohols could be formed with high levels of enantioselectivity. Consideration of selectivity trends with respect to the nature of the substituents around the allylic system revealed that this is a reliable and predictable method for allylic alcohol synthesis.
- Morrill, Christie,Beutner, Gregory L.,Grubbs, Robert H.
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p. 7813 - 7825
(2007/10/03)
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- Naturally occurring cyanohydrins, analogues and derivatives as potential insecticides
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Several naturally occurring cyanohydrins were tested for fumigation toxicity to two insect species, the house fly (Musca domestica L) and the lesser grain borer (Rhyzopertha dominica (F)). Synthetic analogues of these compounds were tested as well. Most of the cyanohydrins tested were more toxic as fumigants to M domestica and R dominica than chloropicrin; some compounds were nearly as toxic as dichlorvos. Naturally occurring cyanohydrins were among the most toxic tested. (C) 2000 Society of Chemical Industry.
- Peterson, Chris J.,Tsao, Rong,Coats, Joel R.
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p. 615 - 617
(2007/10/03)
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- Insecticidal activity of cyanohydrin and monoterpenoid compounds
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The insecticidal activities of several cyanohydrins, cyanohydrin esters and monoterpenoid esters (including three monoterpenoid esters of a cyanohydrin) were evaluated. Topical toxicity to Musca domestica L. adults was examined, and testing of many compounds at 100 μg/fly resulted in 100% mortality. Topical LD50 values of four compounds for M. domestica were calculated. Testing of many of the reported compounds to brine shrimp (Artemia franciscana Kellog) resulted in 100% mortality at 10 ppm, and two compounds caused 100% mortality at 1 ppm. Aquatic LC50 for values were calculated for five compunds for larvae of the yellow fever mosquito (Aedes aegypti (L.)). Monoterpenoid esters were among the most toxic compounds tested in topical and aquatic bioassays.
- Peterson, Chris J.,Tsao, Rong,Eggler, Aimee L.,Coats, Joel R.
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p. 648 - 654
(2007/10/03)
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- Indium trifluoride - A Lewis acid catalyst for the addition of TMSCN to aldehydes in water
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Indium trifluoride promoted chemoselective additions of TMSCN to various aldehydes in water gave the respective cyanohydrins in good yields.
- Loh, Teck-Peng,Xu, Kai-Chen,Ho, Diana Sook-Chiang,Sim, Keng-Yeow
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p. 369 - 370
(2007/10/03)
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- An improved synthesis of the antithyroid factor DL-goitrin
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DL-1-Amino-3-buten-2-ol H2C=CH-CH(OH)-CH2NH2 has been synthesized in a satisfactory overall yield by reduction of the protected cyanohydrin H2C=CH-CH(OR)-CN with aluminum hydride, followed by removal of the protecting group with aqueous hydrochloric acid and treatment with potassium hydroxide.The amino alcohol is a key intermediate in a synthesis of the antithyroid goitrin reported previously.
- Brandsma, L.,Bos, K. D.,Keegstra, M. A.,Verkruijsse, H. D.
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p. 132 - 133
(2007/10/02)
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- Three-Carbon Annelations. Regiocontrolled Reactivity of Trimethylsilyl- and Ethoxyethyl-Protected Cyanohydrins. Versatile Homoenolate and Acyl Anion Equivalents
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The trimethylsilyl- (2) and ethoxyethyl- (4) protected cyanohydrins of α,β-unsaturated aldehydes are utilized as three-carbon annelation reagents.Metalated reagent 2 displays exclusive α reactivity with aldehydes and ketones at -78 deg C.Metalated reagent 4 displays exclusive α reactivity at -78 deg C and exclusive γ reactivity at 0 deg C.Reagent 4 thus allows for complete regiocontrol in its addition to aldehydes and ketones which permits selective addition of either a homoenolate or an acyl anion equivalent.Metalation of the α product 11 at -78 deg C with subsequent warming to 0 deg C produces exclusively the γ product, confirming the reversible nature of the addition to the carbonyl.The derived α '-trimethylsiloxy enones 17 (R3=Me3Si), α '-hydroxy enones 17 (R3=H), α '-acetoxyenones 17 (R3=Ac), and γ-lactones 10 are useful cyclopentenone precursors.Treatment of 17 with p-TsOH in toluene at reflux produces cyclopentenones.The reaction proceeds via the postulated intermediacy of a pentadienyl cation 15 which undergoes in situ electrocyclic ring closure.
- Jacobson, Richard M.,Lahm, George P.,Clader, John W.
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p. 395 - 405
(2007/10/02)
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