V. V. Semenov, N. V. Zolotareva, B. I. Petrov, N. M. Lazarev, R. V. Rumyantsev, T. I. Lopatina, N. M. Khamaletdinova, T. I. Kulikova, T. A. Kovylina, E. N. Razov
{"title":"六亚甲基四胺与（1-羟乙基）二膦酸及其盐类的反应。二膦酸二铵（1-羟乙基乙烯）的分子结构","authors":"V. V. Semenov, N. V. Zolotareva, B. I. Petrov, N. M. Lazarev, R. V. Rumyantsev, T. I. Lopatina, N. M. Khamaletdinova, T. I. Kulikova, T. A. Kovylina, E. N. Razov","doi":"10.1007/s11172-025-4508-7","DOIUrl":null,"url":null,"abstract":"<div><p>The reaction of hexamethylenetetramine (CH<sub>2</sub>)<sub>6</sub>N<sub>4</sub> with sparingly soluble (1-hydroxyethylidene)diphosphonates M(H<sub>2</sub>L)•2H<sub>2</sub>O (M = Mn, Co, Zn; H<sub>4</sub>L is (1-hydroxyethylidene)diphosphonic acid) afforded water-soluble compounds of the composition [(CH<sub>2</sub>)<sub>6</sub>N<sub>4</sub>H<sub>2</sub>]ML•2H<sub>2</sub>O (M = Mn (<b>1</b>), Co (<b>2</b>), Zn (<b>3</b>)). Manganese derivative <b>1</b> lost its solubility during storage, whereas the cobalt and zinc compounds retained it. The tetrafunctional base hexamethylenetetramine reacts with tetrafunctional (1-hydroxyethylidene)-diphosphonic acid H<sub>4</sub>L in methanol to form hexamethylenetetraminium (1-hydroxyethylidene)diphosphonate dihydrate [(CH<sub>2</sub>)<sub>6</sub>N<sub>4</sub>H]<sup>+</sup>(H<sub>3</sub>L)•2H<sub>2</sub>O (<b>4</b>). When heated in an aqueous methanol medium, compound <b>4</b> dissociates to acid H<sub>4</sub>L and base (CH<sub>2</sub>)<sub>6</sub>N<sub>4</sub>, hexamethylenetetramine reacts with water to produce ammonia and formaldehyde, and the acid H<sub>4</sub>L and ammonia generate diammonium (1-hydroxyethylidene)diphosphonate (NH<sub>4</sub>)<sub>2</sub>H<sub>2</sub>L. The heating in an inert atmosphere causes the extensive decomposition of compound <b>4</b> giving a non-volatile water-soluble residue and a series of volatile organic compounds, such as amines, amides, amino alcohols, and amino acids. The obtained compounds were studied by IR spectroscopy, elemental analysis, powder X-ray diffraction, and thermogravimetric analysis. The molecular structure of diammonium (1-hydroxyethylidene)diphosphonate (NH<sub>4</sub>)<sub>2</sub>H<sub>2</sub>L was determined.</p></div>","PeriodicalId":756,"journal":{"name":"Russian Chemical Bulletin","volume":"74 1","pages":"125 - 136"},"PeriodicalIF":1.7000,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Reactions of hexamethylenetetramine with (1-hydroxyethylidene)diphosphonic acid and its salts. Molecular structure of diammonium (1-hydroxyethylidene)diphosphonate\",\"authors\":\"V. V. Semenov, N. V. Zolotareva, B. I. Petrov, N. M. Lazarev, R. V. Rumyantsev, T. I. Lopatina, N. M. Khamaletdinova, T. I. Kulikova, T. A. Kovylina, E. N. Razov\",\"doi\":\"10.1007/s11172-025-4508-7\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>The reaction of hexamethylenetetramine (CH<sub>2</sub>)<sub>6</sub>N<sub>4</sub> with sparingly soluble (1-hydroxyethylidene)diphosphonates M(H<sub>2</sub>L)•2H<sub>2</sub>O (M = Mn, Co, Zn; H<sub>4</sub>L is (1-hydroxyethylidene)diphosphonic acid) afforded water-soluble compounds of the composition [(CH<sub>2</sub>)<sub>6</sub>N<sub>4</sub>H<sub>2</sub>]ML•2H<sub>2</sub>O (M = Mn (<b>1</b>), Co (<b>2</b>), Zn (<b>3</b>)). Manganese derivative <b>1</b> lost its solubility during storage, whereas the cobalt and zinc compounds retained it. The tetrafunctional base hexamethylenetetramine reacts with tetrafunctional (1-hydroxyethylidene)-diphosphonic acid H<sub>4</sub>L in methanol to form hexamethylenetetraminium (1-hydroxyethylidene)diphosphonate dihydrate [(CH<sub>2</sub>)<sub>6</sub>N<sub>4</sub>H]<sup>+</sup>(H<sub>3</sub>L)•2H<sub>2</sub>O (<b>4</b>). When heated in an aqueous methanol medium, compound <b>4</b> dissociates to acid H<sub>4</sub>L and base (CH<sub>2</sub>)<sub>6</sub>N<sub>4</sub>, hexamethylenetetramine reacts with water to produce ammonia and formaldehyde, and the acid H<sub>4</sub>L and ammonia generate diammonium (1-hydroxyethylidene)diphosphonate (NH<sub>4</sub>)<sub>2</sub>H<sub>2</sub>L. The heating in an inert atmosphere causes the extensive decomposition of compound <b>4</b> giving a non-volatile water-soluble residue and a series of volatile organic compounds, such as amines, amides, amino alcohols, and amino acids. The obtained compounds were studied by IR spectroscopy, elemental analysis, powder X-ray diffraction, and thermogravimetric analysis. The molecular structure of diammonium (1-hydroxyethylidene)diphosphonate (NH<sub>4</sub>)<sub>2</sub>H<sub>2</sub>L was determined.</p></div>\",\"PeriodicalId\":756,\"journal\":{\"name\":\"Russian Chemical Bulletin\",\"volume\":\"74 1\",\"pages\":\"125 - 136\"},\"PeriodicalIF\":1.7000,\"publicationDate\":\"2025-03-25\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Russian Chemical Bulletin\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://link.springer.com/article/10.1007/s11172-025-4508-7\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Russian Chemical Bulletin","FirstCategoryId":"92","ListUrlMain":"https://link.springer.com/article/10.1007/s11172-025-4508-7","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Reactions of hexamethylenetetramine with (1-hydroxyethylidene)diphosphonic acid and its salts. Molecular structure of diammonium (1-hydroxyethylidene)diphosphonate
The reaction of hexamethylenetetramine (CH2)6N4 with sparingly soluble (1-hydroxyethylidene)diphosphonates M(H2L)•2H2O (M = Mn, Co, Zn; H4L is (1-hydroxyethylidene)diphosphonic acid) afforded water-soluble compounds of the composition [(CH2)6N4H2]ML•2H2O (M = Mn (1), Co (2), Zn (3)). Manganese derivative 1 lost its solubility during storage, whereas the cobalt and zinc compounds retained it. The tetrafunctional base hexamethylenetetramine reacts with tetrafunctional (1-hydroxyethylidene)-diphosphonic acid H4L in methanol to form hexamethylenetetraminium (1-hydroxyethylidene)diphosphonate dihydrate [(CH2)6N4H]+(H3L)•2H2O (4). When heated in an aqueous methanol medium, compound 4 dissociates to acid H4L and base (CH2)6N4, hexamethylenetetramine reacts with water to produce ammonia and formaldehyde, and the acid H4L and ammonia generate diammonium (1-hydroxyethylidene)diphosphonate (NH4)2H2L. The heating in an inert atmosphere causes the extensive decomposition of compound 4 giving a non-volatile water-soluble residue and a series of volatile organic compounds, such as amines, amides, amino alcohols, and amino acids. The obtained compounds were studied by IR spectroscopy, elemental analysis, powder X-ray diffraction, and thermogravimetric analysis. The molecular structure of diammonium (1-hydroxyethylidene)diphosphonate (NH4)2H2L was determined.
期刊介绍：
Publishing nearly 500 original articles a year, by leading Scientists from Russia and throughout the world, Russian Chemical Bulletin is a prominent international journal. The coverage of the journal spans practically all areas of fundamental chemical research and is presented in five sections:
General and Inorganic Chemistry;
Physical Chemistry;
Organic Chemistry;
Organometallic Chemistry;
Chemistry of Natural Compounds and Bioorganic Chemistry.
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