Boehme, Horst published the artcileCleavage of aminals and of α-dialkylamino ethers by simple and mixed anhydrides, Related Products of piperidines, the publication is Justus Liebigs Annalen der Chemie (1965), 78-93, database is CAplus.
Cleavage of aminals R2NCH2NR2 with (RSO2)2O, [(RO)2P(O)]2O and [(RO)2P]2O (Ia) affords an equimolar mixture of a dialkylmethyleneimmonium salt [R2N: CH2]+X– of the corresponding acid, and its amide. With mixed anhydrides, the immonium salt of a stronger acid results together with an amide of the weaker one. α-Dialkylamino ethers react in the same manner giving rise to esters instead of amides. In the case of Ia the intermediate immonium salts rearrange by Michaelis-Arbuzov rearrangement into the esters of dialkylaminomethylphosphonic acids. Acetyl nitrate cleaves aminals in a different manner giving rise to a mixture of dialkyl nitramines and acetoxymethyldialkylamines. Consistently with the above scheme, mixed anhydrides are converted with MeOH or HCl to a mixture of a free stronger acid and an ester or chloride, resp., of the weaker one. All reactions were run under N and with a strict exclusion of air moisture. Into a solution of 10.2 g. (Me2N)2CH2 (I) in Et2O was added dropwise 17.4 g. (MeSO2)2O (II) in HCONMe2 to yield 93% [Me2N:CH2]+MeSO3– (III); the mother liquor afforded MeSO2NMe2, m. 48-9° (CCl4). Analogously, 18.2 g. (C5H10N)2CH2 (IV) (C5H10N is piperidino throughout the abstract) and 17.4 g. II afforded 72% N-methylenepiperidineimmonium methanesulfonate [C5H10N:CH2]+MeSO3– (V) and MeSO2NC5H10, m. 48-9° (CCl4). An ice-cold solution of 20 g. MeSO3H in tetrahydrofuran was treated with CH2:C:O, the solvent evaporated, and the residue distilled to give MeSO2OAc (VI), b0.01 56° (air bath). Reaction of 10.2 g. I and 13.8 g. VI in Et2O gave 87% III and AcNMe2 from mother liquors. Analogously, 18.2 g. IV afforded 70% V and C5H10NAc, b12 100-1°, n20D 1.4804. To an ice-cold solution of 17.6 g. PhSO2Cl in 50 cc. dioxane was added dropwise a solution of 12.2 g. BzOH and 7.9 g. pyridine in 50 cc. dioxane. Pyridine-HCl was filtered off, the solvent evaporated, and the residue crystallized from CH2Cl2 to give 46% hygroscopic PhSO2OBz (VII), m. 74-6°. From 10.2 g. I and 25.2 g. VII in Et2O, there was obtained 92% [Me2N:CH2]+PhSO3– (VIII) and, from the mother liquors, BzNMe2, b2 100° m.p. 42°. Analogously 18.2 g. IV and 26.2 g. VII gave 77% crystalline [C5H10N:CH2]+PhSO3– (IX) and C5H10NBz. Also, 17.1 g. piperidinomethyl butyl ether (X) and 26.2 g. VII afforded 73% IX and BzOBu. A solution of 2 g. VII in MeOH was refluxed briefly and Et2O added to precipitate 65% PhSO3H, m. 51°; from the mother liquor, 60% BzOMe was obtained by distillation An ethereal solution of VII was treated with gaseous HCl to give, on chilling, 90% PhSO3H and BzCl. To an ice-cold solution of 14 g. BzCl in 50 cc. dioxane was added dropwise a solution of 14.2 g. PhSO2H and 7.9 g. pyridine in 50 cc. dioxane. After filtering off pyridine-HCl, 48% PhS(O)OBz (XI), b0.01 82°, was obtained. A reaction of 10.2 g. I and 24.6 g. XI in Et2O gave 85% [Me2N:CH2]+PhSO2– (XII) and BzNMe2. Analogously, 18.2 g. IV and 24.6 g. XI gave rise to 86% [C5H10N:CH2]+PhSO2– (XIII) and C5H10NBz. Also, 17.1 g. X and 24.6 g. XI afforded 75% XIII besides BzOBu. A solution of 2 g. XI in MeOH was heated to reflux temperature, concentrated, and distilled in vacuo to yield 45% of BzOMe and 39% PhSO2H, m. 84°. A solution of 2 g. XI in Et2O was treated with gaseous HCl, concentrated in vacuo, and distilled to yield PhSOCl, b0.01 73-5° and BzOH. Similarly, a solution of 14.2 g. PhSO2H and 7.9 g. pyridine in dioxane was added dropwise to an ice-cold solution of 17.6 g. PhSO2Cl in dioxane; the precipitated pyridine-HCl filtered off and the filtrate concentrated to give 53% PhSO2OSOPh (XIV), m. 93-5° (CH2Cl2). As above, 10.2 g. I and 28.2 g. XIV in Et2O afforded 88% VIII and PhS(O)NMe2, b2 93-5°. Analogously, 18.2 g. IV and 28.2 g. XIV gave 79% IX and PhS(O)NC5H10, m. 83° (aqueous EtOH). A reaction of 17.1 g. X with 28.2 g. XIV gave rise to 87% IX, and PhS(O)OBu, b0.01 90-5°. By refluxing a solution of 2 g. XIV in MeOH, and by subsequent precipitation with Et2O, there was obtained 52% PhSO3H, and PhS(O)OMe, b0.01 75°. On treatment with gaseous HCl, a solution of 2 g. XIV in Et2O afforded PhSO3H and PhSOCl, b0.01 73-5°. By the general procedure, 10.2 g. I and 29 g. tetraethyl pyrophosphate [(EtO)2P(O)]2O (XV) in Et2O gave 79% [Me2N:CH2]+(EtO)2P(O)O– (XVI) and, from the mother liquors, 78% (EtO)2P(O)NMe2 (XVII), b10 93°, n20D 1.4231. Analogously, 18.2 g. IV and 29 g. XV reacted to give 80% [C5H10N:CH2]+(EtO)2P(O)O– (XVIII) and 69% (EtO)2P(O)NC5H10 (XIX), b0.5 90-3°, n20D 1.4400. A reaction of 17.1 g. X and 29 g. XV afforded 75% XVIII and 66% (EtO)2P(O)OBu (XX) b0.5 79-80°, n20D 1.4131. By treatment of 10.2 g. I in Et2O with 19.6 g. (EtO)2P(O)OAc (XXI), b0.01 57-60°, n20D 1.4128, there was formed 81% XVI and 58% AcNMe2. Analogously, 18.2 g. IV and 19.6 g. XXI in Et2O afforded 71% XVIII and C5H10NAc. From 17.1 g. X and 19.6 g. XXI in Et2O, there was obtained 66% XVIII and 9.2 g. AcOBu. By the general procedure, 10.2 g. I and 25.8 g. (EtO)2P(O)OBz (XXII), b0.01 107-10°, n20D 1.4936, afforded in Et2O 81% XVI and 77% BzNMe2. Analogously, 18.2 g. IV and 25.8 g. XXII gave 78% XVIII and 85% C5H10NBz. Similarly, 17.1 g. X and 25.8 g. XXII afforded 71% XVIII and 81% BuOBz. A solution of 4.8 g. MeSO3H in 5 cc. Et2O was treated dropwise with a solution of 13.7 g. (EtO)2P(O)OP(OEt)2 (XXIII) in 20 cc. Et2O at 20-5°. After 25 hrs. at room temperature, the mixture was distilled to yield 57% (EtO)2POH, b0.05 38-40°, and 80% MeS(O)2OP(O)(OEt)2 (XXIV), b0.01 75°, n20D 1.4276. Treatment of 10.2 g. I with 23.2 g. XXIV in Et2O gave 79% III and 66% XVII; 18.2 g. IV with 23.2 g. XXIV gave 68% V and 57% XIX. A mixture of 10.2 g. I and 25.8 g. [(EtO)2P]2O (XXV) in Et2O reacted with evolution of heat to afford, on distillation,62% (EtO)2PNMe2 (XXVI), b12 46-8°, n20D 1.4260, and Me2NCH2P(O)(OEt)2 (XXVII) b1 85°, n20D 1.4288. Analogously, 18.2 g. IV and 25.8 g. XXV in Et2O afforded 61% (EtO)2PNC5H10 (XXVIII), b1 85°, n20D 1.4465, and 64% C5H10NCH2P(O)(OEt)2 (XXIX), b2 125°, n20D 1.4558. A reaction of 17.1 g. X and 25.8 g. XXV in Et2O also gave XXIX, b0.3 98°, n20D 1.4563, together with (EtO)2POBu. A solution of 15.6 g. (EtO)2PCl in Et2O was treated successively with 10.1 g. Et3N and 6 g. AcOH in dry Et2O. After 1 hr. at room temperature, the Et3N.HCl was filtered off, and the solution of (EtO)2POAc (XXX) was used as such in the following experiments The solution of XXX and 10.2 g. I in Et2O treated with evolution of heat to give EtOAc and 68% Me2NCH2P(O)(OEt)NMe2 (XXXI), b14 110-12°, n20D 1.4822. An analogous treatment of 18.3 g. IV with the ethereal solution of XXX gave EtOAc, and 62% C5H10NCH2P(O)(OEt)NC5H10 (XXXII), b0.01 125°, n20D 1.5088; XXX with 17.1 g. X furnished EtOAc and 65% C5H10NCH2P(O)(OEt)OBu (XXXIII), b0.01 105° n20D 1.4838. A solution of 24.2 g. (EtO)2POBz (XXXIV), b0.05 96°, n20D 1.4990, in Et2O was treated with 10.2 g. I to give, on rectification, EtOBz and 55% XXXI; 24.2 g. XXXIV and 18.2 g. IV furnished EtOBz and 56% XXXII; and analogously 24.2 g. XXXIV and 17.1 g. X in Et2O gave 61% XXXIII. A reaction of 10.2 g. I with 27.4 g. XXIII in Et2O resulted in formation of (EtO)3PO and 43% XXXI, b10 110°; also, 27.4 g. XXXIII and 18.2 g. IV in Et2O gave (EtO)3PO and 45% XXXII; and, by the same procedure, 27.4 g. XXXIII and 17.1 g. X afforded (EtO)3PO and 47% XXXIII. A solution of AcONO2 was prepared by adding dropwise 50 g. Ac2O into 9 g. 68% HNO3 at 15° and chilling to -20°. This reagent was added dropwise at -20° to a solution of 10.2 g. I in Et2O; the reaction mixture was distilled to give 92% Me2NCH2OAc (XXXV), b20 40°, n20D 1.4120; the distillation residue was poured into water, extracted with CH2Cl2, and the solvent evaporated to yield 67% Me2NNO2, m. 55-6°. In an analogous experiment with 18.2 g. IV and AcONO2 reagent, there was obtained 65% C5H10NCH2OAc (XXXVI), b1 56°, n20D 1.4506, and 50% C5H10NNO2, b1 90°, n20D 1.4950. A solution of 11.7 g. XXXV in MeCN was treated dropwise with a solution 17 g. AgNO3 in MeCN, the precipitate was collected and extracted with warm MeCN; [Me2N:CH2]+NO–3 deposited on cooling the extract A dropwise addition, with cooling, of 16.6 (EtO)3P to 11.7 g. XXXV furnished 85% EtOAc and 88% XXVII. Analogously, 8.3 g. XXVI and 5.9 g. XXXV afforded 68% EtOAc and 46% XXXI; and in the same manner, 16.6 g. (EtO)3P and 15.7 g. XXXVI gave rise to 82% EtOAc and 85% XXIX. A reaction of 10.3 g. XXVIII with 7.9 g. XXXVI afforded similarly 57% EtOAc and 62% XXXII.
Justus Liebigs Annalen der Chemie published new progress about 4972-31-0. 4972-31-0 belongs to piperidines, auxiliary class Piperidine,Benzene, name is 1-(Phenylsulfinyl)piperidine, and the molecular formula is C11H15NOS, Related Products of piperidines.
Referemce:
https://en.wikipedia.org/wiki/Piperidine,
Piperidine | C5H11N – PubChem