This is my first hypothetical write up. (It is still very much incomplete. First step to 1,4-cyclohexadione outlined but nothing further...yet)
Please lead me positively in the proper direction if i make any post errors.


I have also attached a few pdf's with further information:

1 & 2 - 2pdf's, same journal-->
Aryl4aminocyclohexanones-3-mHydroxyphenyl-derivatives & 4pBromophenyl4dimethylamino1phenethylcyclohexanol

3-->
4-amino-cyclohexanols, their pharmaceutical compositions and methods of use

5 & 6 - 2pdf's, same journal-->
Substituted_4_aminocyclohexanols & Substituted_4_aminocyclohexanols_2

1,4-CYCLOHEXANEDIONE
PRODUCT IDENTIFICATION
CAS NO.    637-88-7   

1,4-CYCLOHEXANEDIONE
EINECS NO.    211-306-0
FORMULA    C6H8(=O)2
MOL WT.    112.12
H.S. CODE
   

2914.29
TOXICITY
   
SYNONYMS    Tetrahydroquinone; 1,4-Dioxocyclohexane;
Cyclohexane-1,4-dione; Ciclohexano-1,4-diona (Spanish);
DERIVATION    
CLASSIFICATION
   
PHYSICAL AND CHEMICAL PROPERTIES
PHYSICAL STATE    

yellow to beige crystalline powder
MELTING POINT
   76 - 80 C
BOILING POINT    112 C at 26 mmHg (Decomposes)
SPECIFIC GRAVITY    
SOLUBILITY IN WATER
   
pH    
VAPOR DENSITY    
AUTOIGNITION
   
NFPA RATINGS
   Health: 1; Flammability: 0; Reactivity: 0
REFRACTIVE INDEX
   
FLASH POINT    132 C
STABILITY    Stable under ordinary conditions
APPLICATIONS

1,4-Cyclohexanedione is used as an intermediate for pharmaceuticals, herbicides, plant growth regulator and other organic products. Cyclohexanediones are related to the production of cyanocarbons ( tetracyanomethane, hexacyanoethane, tetracyanoethylene, hexacyanobutadiene, and hexacyanobenzene) and can be applicable for the industry of;

    * Transition-metal complex catalyst chemistry
    * Luminescence chemistry and spectrophotometric analysis
    * Organic synthesis
    * Crystallography and Crystal Chemistry
    * Organic low electrical resistance Chemistry
    * Colorimetry

SALES SPECIFICATION
APPEARANCE
   

yellow to beige crystalline powder
ASSAY    97.5% min
MELTING POINT
   76 - 80 C
TRANSPORTATION
PACKING    25kgs in Fiber Drum
HAZARD CLASS    
UN NO.    
OTHER INFORMATION
Hazard Symbols: n/a, Risk Phrases: n/a, Safety Phrases: 24/25-28A-37-45
GENERAL DESCRIPTION OF DIKETONE
Diketone is a molecule which contains two ketone carbonyl groups. Diacetyl (CH3COCOCH3), 2,3-butadione, is the simplest aliphatic diketone. It is an alpha-diketone which has two ketone groups side-by-side. Usually, alpha-diketone imparts a carmel like or buttery flavor. Diketone compounds take a role in creating various fragrances. Bezil (C6H5COCOC6H5) is an aromatic diketone, the fundamental structure of photo sensitive molecule which is broken down into free radicals upon exposure to ultraviolet radiation. Acetoacetone is a beta-diketone which two ketones are separated only by one carbon. The beta-ketone is stable as a conjugated enol rather than a diketone due to the delocalization which makes the counterion more stable and less likely to regain the proton. Ascorbic acid is an example of enol compound. Enol compounds form complexes with many transition metal ions. These compounds are readily soluble in organic solvents. They are widely used as chelating agents, ligands, and catalyst precursors. Acetoacetic acid and its esters contain active methylene groups which have relatively acidic alpha-protons due to H atom adjacent to two carbonyl groups. The reactivity of its methylene group provide the sequence of reactions of alkylation, hydrolysis of the esters and decarboxylation resulting in substituted ketones. Acetoacetic acid derivatives are important aliphatic parts adjoining azo dyes and pigments. Aacetoacetate is one of Ketone bodies which are the end-products of rapid or excessive fatty acid breakdown in the human body. Para-benzoquinone and its derivatives belong to 1,4-diketone family. Benzoquinone is used as an oxidizing agent in organic chemistry and is a common constituent of biologically molecules like Vitamin K1. Quinones serves as electron acceptors in electron transport chains such as in photosynthesis, and aerobic respiration. Diketene derivatives find versatile applications in making biomolecules, agrochemicals, dyes, pigments, pharmaceuticals including vitamins, and stabilizers for PVC and polyester. They are used as components for fragrances and as solvents. Diketones undergo the reversible and irreversible addition reactions include;

    * Aldol Reactions
    * Alkylation of Enolate Anions
    * Clemmensen Reduction
    * Cyanohydrin Formation
    * Enamine Formation
    * Hemiacetal and Acetal Formation
    * Hydration Formation
    * Imine Formation
    * Wolff-Kishner Reduction

-------------------------------------------------------------------------------------------------

4-(p-Bromophenyl)-4-(dimethylamino)-1-phenethylcyclohexanol

Molecular Weight   402.36782 [g/mol]
Molecular Formula   C22H28BrNO
XLogP3-AA   5
H-Bond Donor   1
H-Bond Acceptor   2
Rotatable Bond Count   5
Exact Mass   401.135427
MonoIsotopic Mass   401.135427
Topological Polar Surface Area   23.5
Heavy Atom Count   25
Formal Charge   0
Complexity   402
Isotope Atom Count   0
Defined Atom StereoCenter Count   0
Undefined Atom StereoCenter Count   0
Defined Bond StereoCenter Count   0
Undefined Bond StereoCenter Count   0
Covalently-Bonded Unit Count   1

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Organic Syntheses, Coll. Vol. 5, p.288 (1973); Vol. 45, p.25 (1965).

1,4-CYCLOHEXANEDIONE

Submitted by Arnold T. Nielsen and Wayne R. Carpenter1.
Checked by William G. Dauben and E. John Deviny.


1. Procedure

A. 2,5-Dicarbethoxy-1,4-cyclohexanedione. A solution of sodium ethoxide is prepared by adding small pieces of sodium (92 g., 4 g. atoms) as rapidly as possible to 900 ml. of commercial absolute ethanol contained in a 3-l., three-necked, round-bottomed flask equipped with two stoppers and a reflux condenser fitted with a drying tube packed with calcium chloride and soda lime. The reaction is completed by heating the mixture under reflux for 3–4 hours (Note 1). To the hot solution is added diethyl succinate (348.4 g., 2 moles) (Note 2) in one portion (Caution! Exothermic reaction), and the mixture is heated under reflux by maintaining the original bath temperature for 24 hours. A thick pink-colored precipitate is formed almost immediately and remains throughout the reaction.

At the end of the 24-hour period, the ethanol is removed under reduced pressure on a steam bath. A 2N sulfuric acid solution (2 l.) is added to the warm residue, and the mixture is stirred vigorously for 3–4 hours (Note 3). The solid is removed by suction filtration and washed several times with water. The air-dried product is a pale-buff powder weighing 180–190 g., m.p. 126–128°. The solid is added to 1.5 l. of ethyl acetate, the mixture is heated to boiling and is filtered rapidly while hot (Note 4). The filtrate is chilled, and it yields cream to pink-cream colored crystals of 2,5-dicarbethoxy-1,4-cyclohexanedione, 160–168 g., m.p. 126.5–128.5°. The filtrate is concentrated to one-tenth of its original volume in order to obtain a second crop of crystals, 5–7 g., m.p. 121–125°. The total yield is 165–175 g. (64–68%).

B. 1,4-Cyclohexanedione. The purified 2,5-dicarbethoxy-1,4-cyclohexanedione (170 g., 0.66 mole) (Note 5) and 170 ml. of water are placed in a glass liner (vented) of a steel pressure vessel of 1.5-l. capacity (fitted with a pressure-release valve). The vessel is sealed, heated as rapidly as possible to 185–195°, and kept at this temperature for 10–15 minutes (Note 6). The reaction vessel is immediately removed from the heater, placed in a large tub of ice water, and cooled to room temperature. The gas pressure then is carefully released. The resulting yellow to orange liquid is transferred to a distillation flask with the aid of a minimum volume of ethanol, and most of the water and ethanol is removed under reduced pressure by means of a rotary evaporator. The flask is attached to a short heated column fitted with a short air condenser. The remainder of the water and ethanol is removed under reduced pressure, and the 1,4-cyclohexanedione is distilled, b.p. 130–133° (20 mm.). The product solidifies to a white to pale-yellow solid, m.p. 77–79°, yield 60–66 g. (81–89% yield from 2,5-dicarbethoxy-1,4-cyclohexanedione). The compound may be conveniently recrystallized from carbon tetrachloride (7 ml. per gram of dione); the purified product is obtained as white plates, m.p. 77–79° (90% recovery).

2. Notes
1. A heating bath containing a liquid heat exchanger such as hydrogenated cottonseed oil should be used. Employment of an electric heating mantle may cause extreme charring in the later stages of the reaction.
2. The diethyl succinate was obtained from Eastman Organic Chemicals and used without purification.
3. The lumps of the sodium salt of 2,5-dicarbethoxy-1,4-cyclohexanedione should be completely reacted before the filtration step. If desired, the mixture may be stirred overnight at this point. The checkers found that in some runs a rock-like precipitate persisted on the bottom of the flask, and it had to be broken up manually by using a spatula with care.
4. A large fluted filter paper and a heated funnel are recommended for the filtration. The dark insoluble material which is removed by this process quickly fills the pores of the filter paper; more than one filter paper may be required. If a large amount of material remains in the filter, the material should be treated with additional ethyl acetate, the mixture filtered, and the filtrate combined with the first filtrate.
5. Use of unpurified ester results in a much lower yield of 1,4-cyclohexanedione.
6. An electrically heated pressure bomb, 4.5 in. in diameter, of 1.5-l. capacity, was employed (American Instrument Company, Model E 1143, cold-tested to 23,000 p.s.i.). About 90 minutes was required to raise the temperature from 25° to 185°.
3. Discussion
2,5-Dicarbethoxy-1,4-cyclohexanedione has been prepared by the self-condensation of diethyl succinate by use of sodium or sodium ethoxide catalyst (with or without a solvent)2,3,4,5,6,7,8,9,10 and by reaction of ethyl 4-bromo-3-ketobutanoate11 or ethyl 4-chloro-3-ketobutanoate12,13 with sodium ethoxide in ethanol.
1,4-Cyclohexanedione has been prepared by hydrolysis and decarboxylation of 2,5-dicarbethoxy-1,4-cyclohexanedione by using concentrated sulfuric acid,14 aqueous alcoholic phosphoric acid,15 or water at 195–200°,7,8,16 and by peroxyvanadic acid oxidation of cyclohexanone.17
4. Merits of the Preparation

The present procedure is simpler than others previously described and gives equally good yields. It is easily adapted to the preparation of large quantities of either the diester or the diketone. It can be extended to the preparation of various alkylated 1,4-cyclohexanediones18 and bicyclic diketodicarboxylic esters such as diethyl bicyclo[2.2.2]octane-2,5-dione-1,4-dicarboxylate.19,20 1,4-Cyclohexanedione is a useful intermediate for the preparation of 1,4-substituted cyclohexanes such as the dioxime,21 diamine,22 1,4-dichloro-1,4-dinitrosocyclohexane,23 and 1,4-dinitrocyclohexane.24 It is also the precursor of 7,7,8,8-tetracyanoquinodimethan.

25 References and Notes

   1. Organic Branch, Chemistry Division, Naval Weapons Center, China Lake, California.
   2. H. Ebert, Ann., 229, 52 (1885).
   3. A. Jeanrenaud, Ber., 22, 1282 (1889).
   4. A. Piutti, Gazz. Chim. Ital., 20, 167 (1890).
   5. H. Liebermann, Ann., 404, 272 (1914).
   6. A. E. Uspenskii and I. Turin, J. Russ. Phys.-Chem. Soc., 51, 263 (1920) [C.A., 18, 1484 (1924)].
   7. J. R. Vincent, A. F. Thompson, and L. I. Smith, J. Org. Chem., 3, 603 (1938).
   8. H. Musso and D. Dopp, Ber., 97, 1147 (1964).
   9. D. S. Deorha and S. K. Mukerji, J. Indian Chem. Soc., 41, 604 (1964).
  10. C. R. Hauser and B. E. Hudson, Jr., Org. Reactions, 1, 283 (1942).
  11. W. Mewes, Ann., 245, 74 (1888).
  12. V. M. Rodionov and M. A. Gubareva, Zh. Obshch. Khim., 23, 1830 (1953) [C.A., 49, 926 (1955)].
  13. M. Sommelet and P. Couroux, Bull. Soc. Chim. France, [4] 29, 403 (1921).
  14. A. Baeyer, Ann., 278, 90 (1894).
  15. W. von E. Doering and A. A.-R. Sayigh, J. Org. Chem., 26, 1365 (1961).
  16. H. Meerwein, Ann., 398, 248 (1913).
  17. J. Vene, Bull. Soc. Sci. Bretagne, 23, 123 (1948) [C.A., 44, 6395 (1950)].
  18. A. Baeyer, Ber., 25, 2122 (1892); 26, 232 (1893).
  19. P. C. Guha, Ber., 72, 1359 (1939).
  20. J. D. Roberts, W. T. Moreland, Jr., and W. Frazer, J. Am. Chem. Soc., 75, 637 (1953).
  21. A. Baeyer and W. A. Noyes, Ber., 22, 2168 (1889).
  22. K. Hosino, J. Chem. Soc. Japan, 62, 190 (1941) [C.A., 36, 5140 (1942)].
  23. O. Piloty and H. Steinbock, Ber., 35, 3101 (1902).
  24. A. T. Nielsen, J. Org. Chem., 27, 1993 (1962).
  25. D. S. Acker and W. R. Hertler, J. Am. Chem. Soc., 84, 3370 (1962).

Appendix
Chemical Abstracts Nomenclature (Collective Index Number);
(Registry Number)

sodium salt of 2,5-dicarbethoxy-1,4-cyclohexanedione

ethanol (64-17-5)

sulfuric acid (7664-93-9)

ethyl acetate (141-78-6)

Cyclohexanone (108-94-1)

carbon tetrachloride (56-23-5)

sodium (13966-32-0)

phosphoric acid (7664-38-2)

sodium ethoxide (141-52-6)

ethyl 4-bromo-3-ketobutanoate

Diethyl succinate (123-25-1)

1,4-Cyclohexanedione (637-88-7)

2,5-dicarbethoxy-1,4-cyclohexanedione (787-07-5)

ethyl 4-chloro-3-ketobutanoate (638-07-3)

peroxyvanadic acid

diethyl bicyclo[2.2.2]octane-2,5-dione-1,4-dicarboxylate

1,4-dichloro-1,4-dinitrosocyclohexane

1,4-dinitrocyclohexane

7,7,8,8-tetracyanoquinodimethan

jon, if you could post with structures that would much be better! what do you mean by "energetically less favorable regio isomer"? Does it mean, BuLi can rearrange N-substituted piperidine to alpha- substituted?

i use hyperchem. try to google it, it should be avaliable for free. if you won't succeed, let me know and i'll send you my one
did you mean v-18 substance? didn't know this route to make it, thank you