2,3-Dihydro-5,6-diphenyl-1,4-oxathiin 4-oxide | 58041-21-7

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: 2,3-Dihydro-5,6-diphenyl-1,4-oxathiin 4-oxide
• 英文别名: 5,6-Diphenyl-2,3-dihydro-4H-1,4lambda~4~-oxathiin-4-one；5,6-diphenyl-2,3-dihydro-1,4-oxathiine 4-oxide
• CAS: 58041-21-7
• 化学式: C₁₆H₁₄O₂S
• 分子量: 270.352
• InChiKey: NLFKQWFQBZQJAK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  45.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  2,3-二氢-5,6-二苯基-1,4-氧硫杂环己二烯 在 双氧水 作用下， 以 水 、 溶剂黄146 为溶剂， 以88%的产率得到2,3-Dihydro-5,6-diphenyl-1,4-oxathiin 4-oxide
  参考文献：
  名称：

  Substituted 2,3-dihydro-,4-oxathiin plant growth stunting agents

  摘要：

  2,3-二氢-1,4-噁硫烯（oxathiins）的替代物具有有用的植物生长调节效果，包括除草效果。例如，2,3-二氢-5,6-二苯基-1,4-噁硫烯和2,3-二氢-5-(4-甲基苯基)-6-苯基-1,4-噁硫烯-4-氧化物。这些化合物可用于选择性控制草本植物，作为矮化剂，抑制营养和生殖腋芽生长，以及增加生产糖类物种的糖含量。其中许多是新化合物。本发明涉及一种调节植物生长的方法，以及在该方法中有用的植物生长调节组合物，以及在这些组合物中有用的化合物。调节植物生长通常是出于多种原因而有必要的。例如，控制杂草对经济至关重要。杂草竞争会抑制农作物的叶片、果实或种子的产量。杂草的存在也可能降低收获作物的质量和收获效率。对于许多农艺和园艺作物，包括玉米（Zea mays L.）、水稻（Oryza sativa L.）和大豆（Glycine max (L.) Merr.）等，杂草控制对于最大产量是必不可少的。非耕地上的杂草可能导致火灾危险、沙土或积雪漂移不受欢迎、景观美观受损以及引起过敏者的刺激。本发明的某一方面基于发现，某些替代的2,3-二氢-1,4-噁硫烯是非常有效的前出苗除草剂，特别是对草本植物的选择性控制。另一种对植物生长的调节方式具有极大的经济重要性，涉及非除草剂生长调节效果。这些效果包括但不限于矮化、抗蒸发、抑制营养和生殖腋芽生长以及增加生产糖类物种的糖含量。在一个重要方面，本发明提供了一种高效的方法来产生这些效果，利用特定的替代的2,3-二氢-1,4-噁硫烯。在本发明中用于产生除草和其他植物生长调节效果的替代的2,3-二氢-1,4-噁硫烯是具有以下结构的：（详细结构见原文）。这些化合物可通过将2-巯基醇与适当取代的2-卤代-2-苯基乙酮在碱的存在下反应，并在对甲苯磺酸存在下去水环化所制备。2-苯基乙酮的制备可通过文献中已知的标准方法，如弗里德尔-克拉夫斯（Friedel-Crafts）酰化或格氏试剂与适当化学品的缩合反应等方法实现。在本发明中使用的2,3-二氢-1,4-噁硫烯可通过将2,3-二氢-1,4-噁硫烯氧化为相应的4-氧化物或4,4-二氧化物（n = 1或2）来制备。这些化合物可用于调节植物生长，具有前出苗除草效果、矮化、果实体抑制、增加糖含量等效果。

  公开号：

  US03947264A1

文献信息

• US3947264A
  申请人：——

  公开号：US3947264A

  公开（公告）日：1976-03-30
• US4043792A
  申请人：——

  公开号：US4043792A

  公开（公告）日：1977-08-23
• US4020168A
  申请人：——

  公开号：US4020168A

  公开（公告）日：1977-04-26
• US4127402A
  申请人：——

  公开号：US4127402A

  公开（公告）日：1978-11-28
• Substituted 2,3-dihydro-,4-oxathiin plant growth stunting agents
  申请人：Uniroyal, Inc.

  公开号：US03947264A1

  公开（公告）日：1976-03-30

  Substituted 2,3-dihydro-1,4-oxathiins of the formula ##SPC1## Display useful plant growth regulant effects including herbicidal effects. Examples are 2,3-dihydro-5,6-diphenyl-1,4-oxathiin, and 2,3-dihydro-5-(4-methyl-phenyl)-6-phenyl-1,4-oxathiin 4-oxide. The compounds are useful for the selective control of grasses and as dwarfing agents, as well as for inhibition of vegetative and reproductive axillary growth, and for increasing the sugar content of sugar producing species. A number of these are new compounds. This invention relates to a method of regulating the growth of plants and to plant growth regulant compositions useful in such method, as well as to chemical compounds useful in such compositions. Regulation of the growth of plants is frequently desirable for a number of reasons. For example, the control of weeds is of great economic importance. Weed competition inhibits the production of foliage, fruit or seed of agricultural crops. The presence of weeds may also reduce the quality of the harvested crop and reduce harvesting efficiency. Weed control is essential for maximum production of many agronomic and horticultural crops, including corn (Zea mays L.), rice (Oryza sativa L.) and soybeans (Glycine max (L.) Merr.). Weeds on non-cropped areas may cause a fire hazard, undesirable drifting of sand or snow, impaired beauty of the landscape and irritation to persons with allergies. The invention, in one aspect, is based on the discovery that certain substituted 2,3-dihydro-1,4-oxathiins are remarkably effective preemergence herbicides, especially for the selective control of grasses. Another form of regulation of plant growth that is of great economic importance involves non-herbicidal growth regulant effects. These include, by way of nonlimiting example, such effects as dwarfing, antitranspiration, inhibition of vegetative and reproductive axillary growth and increasing the sugar content of sugar producing species. In one important aspect the invention provides a highly effective method for producing such effects, employing certain substituted 2,3-dihydro-1,4-oxathiins. The substituted 2,3-dihydro-1,4-oxathiins employed to produce herbicidal and other plant growth regulating effects in accordance with the invention are those of the formula ##SPC2## Wherein the R's are the same or different and are selected from the group consisting of hydrogen, lower alkyl (especially methyl and ethyl), halogen (e.g., chlorine, bromine, fluorine), lower alkoxy (e.g., methoxy), amino, lower alkylthio (e.g., methylthio), and lower acyloxy (e.g., acetyloxy), and n is zero, 1 or 2. The compound wherein all of the R's are hydrogen, and n is zero, namely, 2,3-dihydro-5,6-diphenyl-1,4-oxathiin, is known [Marshall and Stevenson, J. Chem. Soc. 2360 (1959)]; the other compounds are believed to be new. In a preferred class of compounds useful in the invention the R's have the following values: R.sub.1 = H R.sub.2 = H, CH.sub.3, C.sub.2 H.sub.5 R.sub.3 = H, Cl, CH.sub.3 R.sub.4 = H, Cl, CH.sub.3 ##EQU1## R.sub.6 = H, Cl, CH.sub.3 R.sub.7 = H, Cl, CH.sub.3, OCH.sub.3 R.sub.8 = H, Cl, Br, F, CH.sub.3, C.sub.2 H.sub.5, OCH.sub.3, NH.sub.2 R.sub.9 = H, CH.sub.3 R.sub.10 = H. Again, the members of this preferred class of compounds are new, except where all of the R's are hydrogen and n is zero (i.e., except for 2,3-dihydro-5,6-diphenyl-1,4-oxathiin). Of special interest are the compounds of the class described having substituents on one or both phenyls, or a substitutent on the dihydro portion of the 1,4-oxathiin ring, or a combination of both. Also of special note are such compounds with a para substituent on the 5-phenyl group. In one respect, the invention is concerned with chemicals of the kind described wherein n is 1 or 2, and use thereof in plant growth regulation. In another respect the invention is directed to chemicals of the above-stated formula in which at least one of the R's is other than hydrogen or lower alkyl, as well as plant growth regulant uses of such chemicals. The substituted 2,3-dihydro-1,4-oxathiins employed in the invention may be prepared by reacting a 2-mercaptoalkanol with an appropriately substituted 2-halo-2-phenylacetophenone in the presence of a base and cyclizing the resulting intermediate with water removal in the presence of p-toluenesulfonic acid as a catalyst. The preparation of the 2-halo-2-phenylacetophenones may be achieved using one of the following general procedures: a. Reaction of a substituted benzoin with thionyl chloride. b. Reaction of a substituted 2-phenylacetophenone with sulfuryl chloride. c. Reaction of a substituted 2-phenylacetophenone with bromine. The 2-phenylacetophenones may be prepared by the standard methods known in the literature, such as Friedel-Crafts acylation or Grignard condensation with the appropriate chemicals. The 2,3-dihydro-1,4-oxathiin in which n is zero may be oxidized to the corresponding 4-oxide or 4,4-dioxide (n = 1 or 2) by controlled addition of one or two equivalants respectively of a 30% hydrogen peroxide solution to one equivalent of the oxathiin in glacial acetic acid. In one aspect, the invention contemplates application of any of the substituted 2,3-dihydro-1,4-oxathiin compounds described, in amount effective to regulate growth, to a locus at which such growth regulant effects as preemergence herbicidal effects, dwarfing, fruiting body inhibition, increasing sugar content, etc., are desired. In another aspect, the invention is directed to a plant growth regulant composition comprising a chemical compound as described herein, in amount effective to regulate the growth of plants, in admixture with a carrier therefor. It will be understood that the term plants as used herein includes plant parts such as foliage, roots, flowers and seeds. The amount of substituted 1,4-oxathiin employed follows conventional practice for herbicidal use or other plant growth regulant uses and the chemical is suitably applied as a formulation in accordance with conventional agricultural chemical practice. Thus, the chemical may be impregnated on finely-divided or granular inorganic or organic carriers such as attapulgite clay, sand, vermiculite, corn cobs, activated carbon or other granular carriers known to the art. The impregnated granules may then be spread on the soil. Furthermore, the chemical may be formulated, for example, as a wettable powder by grinding it into a fine powder and mixing it with an inactive powdered carrier to which a surface active dispersing agent has been added. Typical powdered solid carriers are the various mineral silicates, e.g., mica, talc, pyrophyllite, and clays. The wettable powder may then be dispersed in water and sprayed on the soil surface, or on crop plants. Similarly, an emulsifiable concentrate may be prepared by dissolving the chemical in a solvent such as benzene, toluene, or other aliphatic or aromatic hydrocarbon to which a surface active dispersing agent has been added. The emulsifiable concentrate may then be dispersed in water and applied by spraying. Suitable surface active agents are well known to those skilled in the art, and reference may be had to McCutcheon's Detergents and Emulsifiers, 1970, Allured Publishing Corp., Ridgewood, N.J., or Hoffman et al. U.S. Pat. Nos. 2,614,916, cols. 2 to 4 and 2,547,724, cols. 3 and 4, for examples of appropriate surface active agents. The concentration of active chemical in the formulation may vary widely, e.g., from 1 to 95%. The concentration of active chemical in dispersions applied to the soil or foliage is almost invariably from 0.002% to 75%. The chemical is frequently applied at rates of 0.10 to 25 pounds per acre. For use as a preemergence herbicide, the chemical is applied to soil which contains weed and crop seed (either to the surface of the soil or incorporated into the upper one to three inches of soil). The chemicals may be employed individually, or as a mixture of two or more chemicals. The most suitable rate of application in any given case will depend on such factors as the particular response desired, soil type, soil pH, soil organic matter content, wind velocity, the quantity and intensity of rainfall before and after treatment, the air and soil temperature, light intensity and light duration per day. All of these factors can have an influence on the efficacy of the chemicals for a given plant growth control use. The herbicidal use may include selective weed control in crops such as soybeans, sugar beets, etc. Depending on crop, variety, dosage, time of application and certain cultural practices, growth regulating effects which are obtained include the following: a. dwarfing b. cessation of terminal growth c. inhibition of axillary and intercalary growth d. flowering inhibition e. fruiting body inhibition f. twisting and epinastic responses g. modification of root growth h. increasing sugar in sugar producing species i. antitranspiration to control water loss. The foregoing responses are general plant responses any one of which could contribute directly to yield increases. For example, a spray application may be made to tobacco after the flowers are removed to obtain excellent axillary growth control. It may be applied to cotton to facilitate a cut off spray or it may be applied on cotton early to retard the development of rank cotton. Chemicals described herein also may be used on ornamental plants. For example, a spray application may be made to chrysanthemums to obtain disbudding which, if done by hand, is very costly. It has been shown to increase the percent sugar in sugarcane. It can be postulated from the results on sugarcane that the chemicals may be preventing breakdown of sugars. The chemicals have also shown remarkable properties in inhibiting flower bud development on peaches. This is useful for preventing frost damage in marginal growth areas where late frosts are inevitable. Flower thinning may be accomplished also. Another plant growth regulant effect that the chemicals of the invention exhibit is that of antitranspiration. The chemicals control stomatal opening and hence prevent excessive water loss. Due to this response greater yields can be obtained with plants growing under stress. The following examples, in which all quantities are expressed by weight unless otherwise indicated, will serve to illustrate the practice of the invention in more detail. Examples 1-51 involve preparation of typical plant growth regulant chemicals of the invention, employing four different methods of preparation, identified by the letters A to D in TABLE I, as follows: A. Halogenation of the appropriate 2-phenylacetophenone followed by reaction with a 2-mercaptoalkanol and cyclization. B. Reaction of a purified 2-halo-2-phenylacetophenone with a 2-mercaptoalkanol followed by cyclization. C. Oxidation of the appropriate 1,4-oxathiin with one equivalent of oxidizing agent. D. Oxidation of the appropriate 1,4-oxathiin with two equivalents of oxidizing agent. The identity of each of the compounds in the working examples was established partly by nuclear magnetic resonance spectrum and partly by analytical data. The n.m.r. spectra of the compounds revealed the characteristic couplings due to the protons of the dihydro portion of the dihydro-1,4-oxathiin ring, thereby confirming the structure. In Examples 52-60 and TABLES II-IX the various substituted 1,4-oxathiins are identified by the Example numbers given in TABLE I. Preferred new chemicals of the invention are those selected from the group consisting of the chemicals of Examples 3, 4, 2, 20, 21, 22, 9, 10, 6, 12 and 16; especially preferred are the chemicals of Examples 3, 20 and 21. Plant growth regulant compositions of particular interest containing the present chemicals are those based on chemicals selected from the group consisting of 1, 3, 9, 12, 20, 21, 16, 17, 18, 29, 30 and 38, more preferably those based on chemicals 1, 3, 20, 21 and 12. For use in preemergence control of weeds the preferred chemicals are those of Examples 3, 20, 21, 30, 38, 10, 16, 18, 13, 24 and 43, more especially the chemicals of Examples 3, 21, 18, 10 and 13. Preferred plant growth retardant chemicals are those of Examples 1, 20, 29, 30, 38 and 9, more preferably Examples 1 and 20. For inhibition of axillary vegetative and reproductive growth, preferred chemicals are those of Examples 1, 3, 9, 12, 20, 21, 16, 17 and 18, more preferably 1, 3, 20, 21 and 12.

  2,3-二氢-1,4-噁硫烯（oxathiins）的替代物具有有用的植物生长调节效果，包括除草效果。例如，2,3-二氢-5,6-二苯基-1,4-噁硫烯和2,3-二氢-5-(4-甲基苯基)-6-苯基-1,4-噁硫烯-4-氧化物。这些化合物可用于选择性控制草本植物，作为矮化剂，抑制营养和生殖腋芽生长，以及增加生产糖类物种的糖含量。其中许多是新化合物。本发明涉及一种调节植物生长的方法，以及在该方法中有用的植物生长调节组合物，以及在这些组合物中有用的化合物。调节植物生长通常是出于多种原因而有必要的。例如，控制杂草对经济至关重要。杂草竞争会抑制农作物的叶片、果实或种子的产量。杂草的存在也可能降低收获作物的质量和收获效率。对于许多农艺和园艺作物，包括玉米（Zea mays L.）、水稻（Oryza sativa L.）和大豆（Glycine max (L.) Merr.）等，杂草控制对于最大产量是必不可少的。非耕地上的杂草可能导致火灾危险、沙土或积雪漂移不受欢迎、景观美观受损以及引起过敏者的刺激。本发明的某一方面基于发现，某些替代的2,3-二氢-1,4-噁硫烯是非常有效的前出苗除草剂，特别是对草本植物的选择性控制。另一种对植物生长的调节方式具有极大的经济重要性，涉及非除草剂生长调节效果。这些效果包括但不限于矮化、抗蒸发、抑制营养和生殖腋芽生长以及增加生产糖类物种的糖含量。在一个重要方面，本发明提供了一种高效的方法来产生这些效果，利用特定的替代的2,3-二氢-1,4-噁硫烯。在本发明中用于产生除草和其他植物生长调节效果的替代的2,3-二氢-1,4-噁硫烯是具有以下结构的：（详细结构见原文）。这些化合物可通过将2-巯基醇与适当取代的2-卤代-2-苯基乙酮在碱的存在下反应，并在对甲苯磺酸存在下去水环化所制备。2-苯基乙酮的制备可通过文献中已知的标准方法，如弗里德尔-克拉夫斯（Friedel-Crafts）酰化或格氏试剂与适当化学品的缩合反应等方法实现。在本发明中使用的2,3-二氢-1,4-噁硫烯可通过将2,3-二氢-1,4-噁硫烯氧化为相应的4-氧化物或4,4-二氧化物（n = 1或2）来制备。这些化合物可用于调节植物生长，具有前出苗除草效果、矮化、果实体抑制、增加糖含量等效果。